Advances in Polymer Chemistry and Methods Reported in Recent US Patents

ADVANCES IN POLYMER CHEMISTRY AND METHODS REPORTED IN RECENT US PATENTS ADVANCES IN POLYMER CHEMISTRY AND METHODS REP...

Author: Thomas F. DeRosa

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ADVANCES IN POLYMER CHEMISTRY AND METHODS REPORTED IN RECENT US PATENTS

ADVANCES IN POLYMER CHEMISTRY AND METHODS REPORTED IN RECENT US PATENTS THOMAS F. DEROSA

Copyright 2008 by John Wiley & Sons, Inc. All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley.com/go/permission. Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com. Library of Congress Cataloging-in-Publication Data DeRosa, Thomas F. Advances in polymer chemistry and methods reported in recent US patents / Thomas F. DeRosa. p. cm. Includes index. ISBN 978-0-470-31286-5 (cloth) 1. Polymers. 2. Polymerization. I. Title. QD381.D47 2009 668.9–dc22 2008009439 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1

Dedicated in Loving Memory to My Father, John G. DeRosa November 27, 1921 – January 6, 1980

CONTENTS

Preface ................................................................................................ xix

I. ADDITIVES Controlled Radical Acrylic Copolymer Thickeners ............................... 1 Polymer-Filler Coupling Additives ..................................................... 5

II. ADHESIVES (Meth)acrylate Block Copolymer Pressure Sensitive Adhesives ............. 11 Absorbable a-Cyanoacrylate Compositions ......................................... 15 Use of Polybenzoxazoles (PBOS) for Adhesion ................................... 20

III. BIOACTIVE A. Bioabsorbables Segmented Urea and Siloxane Copolymers and Their Preparation Methods ............................................................... Functionalized Polymers for Medical Applications ......................... Degradable Polyacetal Polymers .................................................. Lactone Bearing Absorbable Polymers ..........................................

25 28 31 35

B. Contact Lenses Low Polydispersity Poly-HEMA Compositions .............................. 40 C. Drug Delivery Amphiphilic Block Copolymers and Nanoparticles Comprising the Same .............................................................. Heterofunctional Copolymers of Glycerol and Polyethylene Glycol, Their Conjugates and Compositions ............................... Polyalkylene Glycol Acid Additives ............................................. Thermosensitive Biodegradable Copolymer ................................... Polyamide Graft Copolymers ....................................................... Bioerodible Poly(Ortho Esters) from Dioxane-Based Di(Ketene Acetals) and Block Copolymers Containing Them ....... Water-Soluble Polymer Alkanals ..................................................

44 48 51 55 58 61 65 vii

viii

Contents

Biodegradable Aliphatic Polyester Grafted with Poly(Ethylene Glycol) Having Reactive Groups and Preparation Method Thereof ............................................... Coumarin End-Capped Absorbable Polymers ................................. Block Copolymers for Multifunctional Self-assembled Systems ........ Methods of Making Functional Biodegradable Polymers ................. Monofunctional Polyethylene Glycol Aldehydes ............................

69 72 76 80 84

IV. COATINGS A. Anionic Glycopolymers and Free Radical Polymerization Methods ............... 89 B. Aqueous Method of Making Novel Water-Soluble and Self-doped Polyaniline Graft Copolymers ............................ 93 Oxyfluorination ......................................................................... 97 Aqueous Dispersions of Crystalline Polymers and Uses ................... 99 C. Fluorine Multifunctional (Meth)Acrylate Compound, Photocurable Resin Composition and Article ............................ 102 D. Hydrophilic Polyoxyalkylene Phosphonates and Improved Process for Their Synthesis .................................................... 105 E. Hydrophobic Polymers and Polymer Coatings ................................................. 108 Photochemical Crosslinkers for Polymer Coatings and Substrate Tie-Layer............................................ 112 Use of Poly(Dimethyl Ketone) to Manufacture Articles in Direct Contact with a Humid or Aqueous Medium................. 116 F. Thermally Stable Polyaryleneetherketone Phosphine Oxide Compositions Incorporating Cycloaliphatic Units for Use as Polymeric Binders in Thermal Control Coatings and Method for Synthesizing Same ........................................................... 118 G. Vapor Deposition of Polymers Functionalization of Porous Materials by Vacuum Deposition of Polymers ......................................................... 121

Contents

ix

H. Succinic Anhydride Derivatives Light Absorbent Agent Polymer for Organic Anti-reflective Coating and Preparation Method and Organic Anti-reflective Coating Composition Comprising the Same ........ 124

V. COSMETICS Water-Soluble or Water-Dispersible Graft Polymers, Their Preparation and Use........................................................... 129

VI. DENTAL A. Cement (Meth)Acrylate-Substituted Iminooxidiazine Dione Derivatives ................................................................. 133 B. Dental Composites (Meth)Acrylic Ester Compound and Use Thereof ......................... 138

VII. ELECTROACTIVE A. Charge Transport Materials Hole Transport Polymers and Devices Made with Such Polymers ... 143 Acrylic Polymer and Charge Transport Material ........................... 147 B. Dielectric Materials Thermosetting Aromatic Dielectric Material ................................ 150 C. Donor-Acceptor Complexes Polyester Having p-Conjugated Group in Side Chain and Charge Transporting Material Using the Same .................... 155 D. Electroconductive Halogenated Thiophene Monomer for the Preparation of Regioregular Polythiophenes .............................................. Electrically Conductive Polymeric Biomaterials, the Process for Their Preparation and Use in Biomedical and Health Care Fields ................................................................ Dibenzodiazocine Polymers ....................................................... Redox-Active Polymer and Electrode Comprising the Same ............................................................

158

161 164 168

x

Contents

Use of Sulphonic, Phosphonic and Phosphoric Acids as Dopants for Polyaniline and for Conductive Polyaniline-Based Composite Materials ................................ 172 3,4-Alkylenedioxy-Thiophene Copolymers ............................... 177 E. Electroluminescence Electroactive Polymer, Device Made Therefrom and Method ...... 180 Polymers and Oligomers, Their Synthesis, and Electronic Devices Incorporating the Same........................................... 185 Process for Preparing Poly(Arylene Ethers) with Pendant Crosslinkable Groups ......................................................... 190 F. Semiconductors Mono-, Oligo-, and Polythieno[2,3-b]Thiophenes ...................... Poly(Arylene Ether) Dielectrics............................................... Polythiophenes and Devices ................................................... Mono-, Oligo- and Polymers Comprising Fluorene and Aryl Groups ................................................................

196 201 205 211

VIII. ENERGETIC POLYMERS Glycidyl Dinitropropyl Formal, Poly(Glycidyl Dinitropropyl Formal), and Preparation Method Thereof .................................. 217 Synthesis of Energetic Thermoplastic Elastomers Containing Both Polyoxirane and Polyoxetane Blocks ................. 220 IX. FIBERS Rigid-Rod Benzobisazole Polymers Incorporating Naphthalene-1,5-Diyl Structure Units ........................................ 223 Polybenzazole Fiber and Use Thereof ........................................... 227 X. FLUORINE A. Critical Polymerization Process for Producing Fluoropolymer ...................................... 231 B. High Strength Fluorinated Terpolymer.......................................................... 234 C. Low Molecular Weight Directly Polymerized Low Molecular Weight Granular Polytetrafluoroethylene....................................................... 237

Contents

xi

Fluoroelastomers Containing Copolymerized Units of Vinyl Esters ............................................................... 241 D. Low Surface Energy Amorphous Polyether Glycols Based on bis-Substituted Oxetane and Tetrahydrofuran Monomers............................... 244 E. Silicon Fluids Cyclic Siloxane Compounds and Making Method ...................... 247 F. Surfactants Fluorinated Organosilicon Compounds and Fluorochemical Surfactants ........................................... 251 XI. GELS A. Gelling Agent Ferrocene-Containing, Organic Gelling Compound, and Gel and Cast Film Using the Same ................................. 255 B. Hydrogels Random Block Copolymers .................................................... (Meth)Acrylic Esters of Polyalkoxylated Trimethylolpropane ...... Prepolymers for Improved Surface Modification of Contact Lenses .................................................................. Preparation of High Molecular Weight Polysuccinimides ............ Degradable Crosslinkers and Degradable Crosslinked Hydrogels Comprising Them...............................................

259 262 265 269 272

C. Sol-gel Thermosensitive Poly(Organophosphazenes), Preparation Method Thereof and Injectable Thermosensitive Polyphosphazene Hydrogels Using the Same ......................... 278 XII. IMAGING AGENT Polymerization Method for the Synthesis of Polypeptide Imaging Agents ...................................................................... 283 XIII. INK Process for Preparing Chain Extended Thermoplastic Guanidinium Polymers ............................................................ 289

xii

Contents

XIV. LIQUID CRYSTALS A. Liquid Crystal Aligner Diamines, Polyimide Precursors, and Polyimides Produced by Using the Diamines and Liquid Crystal Aligning Agents .... 293 Photosensitive Polyimides for Optical Alignment of Liquid Crystals .............................................................. 298 B. Liquid Crystal Materials Homopolymers That Exhibit a High Level of Photo-inducable Birefringence .................................................................... Liquid Crystalline Compound, Liquid Crystalline Composition, and Retardation Film ...................................... Perfluoroallyloxy Compound and Liquid Crystal Composition Containing the Same ....................................... Liquid Crystal Polymers.........................................................

303 307 315 318

XV. NANOPARTICLES A. Carbon Nanotubes Method of Coating a Substrate with a Polymer Having a Combination of Crown Ether and Carbon Nanotubes Having Guanidine Groups ................................................... Process for Derivatizing Carbon Nanotubes with Diazonium Species ..................................................... Carbon Nanotube Adducts and Methods of Making the Same...... Modification of Nanotubes by Oxidation with Peroxygen Compounds ................................................ Arylcarbonylated Vapor-Grown Carbon Nanofibers....................

325 329 333 336 339

B. Inorganic Nanotubes Polymeric and Carbon Compositions with Metal Nanoparticles ... 343 Metal Oxide Nanotube and Process for Production Thereof......... 347 C. Nanotube Dispersant Methods for the Synthesis of Modular Poly(Phenyleneethynlenes) and Fine-Tuning the Electronic Properties Thereof for the Functionalization of Nanomaterials ............................................................... 351 XVI. NEW SYNTHETIC METHODS A. Compounds Solid-Phase Preparation of [18F] Fluorohaloalkanes ................... 357

Contents

xiii

Vinyl Sulphone Modified Polymer .......................................... 362 Ketone Peroxide Derivatives, Their Preparation and Use............ 367 B. Polymers Simplified Method of Producing Biodegradable Aliphatic Polyesters .......................................................... Hydroaminomethylation of Olefins ......................................... Perdeuterated Polyiimides, Their Process of Preparation, and Their Use as Materials Which Are Transparent within the Region from 2500 to 3500 cm1 .................................... Polybutadiene (Meth)Acrylate Composition and Method ........... Soluble Aniline-Thiophene Copolymers .................................. Process for the Preparation of Di- and Polyamines of the Diphenylmethane Series ........................................... Method for Preparing Polymer Maleimides .............................. Method for Preparing Polymers Containing Cyclopentanone Structures ................................................. Polypropylene Having a High Maleic Anhydride Content .......... Polyamide Graft Copolymers ................................................. Guerbet Polymers................................................................. Polymerization Method ......................................................... Process for Producing Polymerizable Polybranched Polyester..... N-Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof ....................................................... Polymers............................................................................. Star-Shaped Polymer, Multiple Star Polymer, and Their Preparation Methods ......................................................... XVII.

371 373

376 379 381 384 386 389 392 395 398 401 406 409 413 417

OPTICAL MATERIALS Second-Order Nonlinear Optical Materials Polymers Having Pendant Nonlinear Optical Chromophores and Electrooptic Devices Therefrom.................................... 419

XVIII.

PHOTOACTIVE POLYMERS A. Photoluminscence Polymeric Compound and Organic Luminescence Device .......... Electroactive Fluorene Copolymers and Devices Made with Such Polymers .......................................................... Light-Emitting Polymers ....................................................... Modified Suzuki-Method for Polymerization of Aromatic Monomers .....................................................

427 432 437 444

xiv

Contents

Block Copolymer and Polymeric Luminescent Element ............ 448 Soluble Poly(Aryl-Oxadiazole) Conjugated Polymers ............... 453 B. Photorefraction Fullerene-Containing Polymer, Producing Method Thereof, and Photorefractive Composition ........................................ 458

XIX.

POLYMERIZATION METHODS A. Anionic Method for Anionic Polymerization of Oxiranes ...................... Amido-Organoborate Initiator Systems ................................... Process for Manufacturing Vinyl-rich Polybutadiene Rubber ............................................................................ Catalyst for Synthesizing High Transpolymers ......................... Method for the Preparation of Poly(a)-Methylstyrene ............... Use of Sulfur Containing Initiators for Anionic Polymerization of Monomers ................................................................... Production Method of Polyisocyanate by End-Capping with Acyl Chloride ...........................................................

463 465 467 469 472 474 478

B. Catalytic Agents Methods for Making Functionalized Polymers ......................... 481 C. Cationic Polymerization of i-Butene in Hydrocarbon Media Using bis(Borane) Co-Initiators .......................................... 486 Copolymers of Tetrahydrofuran, Ethylene Oxide, and an Additional Cyclic Ether ........................................... 489 D. Chain Transfer Agents Dithiocarbamic Esters .......................................................... 492 E. Emulsifing Agents Amphiphilic Copolymers Useful Especially as Emulsifiers ........ 497 Anionic Copolymers Prepared in an Inverse Emulsion Matrix and Their Use in Preparing Cellulosic Fiber Compositions ............................................ 501 F. Free Radical Polymerization Perfluorodiacylperoxides as Polymerization Initiators ............... 504 G. Macroinitators Polymeric Photoinitiators...................................................... 507

Contents

xv

Radical Polymerization Method Performed in the Presence of Disulfide Compounds .............................. 511 Copolymers of Maleic Anhydride by Stable Free Radical Polymerization...................................................... 514 H. Macromolecular Depolymerization Catalysts Catalysts and Methods for Polymerizing Macrocyclic Oligomers........................................................................ 517 Catalytic Systems................................................................ 520 I. Metallocene Catalysts Metallocene Catalysts Containing a Cyclopentadienyl Ligand Substituted by a Siloxy or Germiloxy Group Containing an Olefinic Residue........................................................... 523 J. Ring-Opening Metathesis Catalyst Photochromic Polymers and Methods of Synthesizing Same ...... 528 Synthesis of A,B-Alternating Copolymers by Olefin Metathesis Reactions of Cyclic Olefins or Olefinic Polymers with an Acyclic Diene .................................................................. 533 K. Ziegler–Natta High 1,4-cis Polybutadiene-Polyurethane Copolymer and Preparation Method Thereof ......................................... Process for Producing Polymer ............................................. Polymerization Catalyst Composition .................................... Synthetic Polyisoprenes and a Process for Their Preparation ..... Polymerization Catalyst ....................................................... Use of Stannylenes and Germylenes as Polymerization Catalysts for Heterocycles.................................................. Process for Producing Polar Olefin Copolymer and Polar Olefin Copolymer Obtained Thereby ................................... Carborane Trianion-Based Catalyst........................................ Catalyst for Polymerization of Norbornene ............................. XX.

539 542 546 550 552 557 560 565 569

REGULATORS A. Chain Transfer Agents Method for the Production of Homo-, Co-, and Block Copolymers ...................................................... 575 Method for Radical Polymerization in the Presence of a Chain Transfer Agent .................................................. 577 Use of C4-C6-Polymercaptopolyols as Regulators in Solution or Precipitation Polymerization .......................... 581

xvi

Contents

S-(a,a0 -Disubstituted-a00 -Acetic Acid) Substituted Dithiocarbonate Derivatives for Controlled Radical Polymerizations, Process, and Polymers Made Therefrom ...... 584 B. Chain Transfer Processes Chain Transfer Agents for RAFT Polymerization in Aqueous Media............................................................. Hindered Spiro-Ketal Nitroxides ............................................ Controlled Polymerization .................................................... N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidines as Radical Polymerization Inhibitors ...................................................

588 592 595 600

C. Photolytic Regulating Agents Method for Producing Polymers with Controlled Molecular Weight and End-Group Functionality Using Photopolymerization in Microemulsions .............................. 604 Ring-Opened Azlactone Photoiniferters for Radical Polymerization ................................................................. 606

XXI.

PHOTORESISTS A. Fluorine Containing Monomer Having Fluorine-Containing Acetal or Ketal Structure, Polymer Thereof, and Chemical-Amplification-Type Resist Composition as Well as Process for Formation of Pattern with Use of the Same ........................................ Polymers, Resist Compositions, and Patterning Process ............ Fluorine-Containing Polymerizable Cyclic Olefin Compound .... Photoresist Composition .......................................................

611 616 623 627

B. Norbornene Norbornene-Type Monomers and Polymers Containing Pendent Lactone or Sultone Groups .................................... 632 Photoresists Containing Sulfonamide Component..................... 636 C. Adamantane Tertiary (Meth)Acrylates Having Lactone Structure, Polymers, Resist Compositions, and Patterning Process ........................ 642 Chemical Amplification Type Positive Resist Composition ........ 647 D. Diamantane Acrylate Positive Photosensitive Composition and Pattern-Forming Method Using the Same .................................................... 651

Contents

XXII.

SEPARATIONS A. Gases Dithiolene Functionalized Polymer Membrane for Olefin/Paraffin Separation ............................................. B. Solutions Tethered Polymer Ligands .................................................... Isolatable, Water-Soluble, and Hydrolytically Stable Active Sulfones of Poly(Ethylene Glycol) and Related Polymers for Modification of Surfaces and Molecules ..................................................... Optically Active Maleimide Derivatives, Optically Active Polymaleimide Derivatives, Process for Their Production, Separating Media Comprising the Optically Active Polymaleimide Derivatives, and Method of Separating Optically Active Compounds Using Them............................ Polymeric Membranes and Uses Thereof ................................ Separating Agent Including a Polysaccharide Derivative Having a Polycyclic Structure............................................. Functionalized Polymers for Binding to Solutes in Aqueous Solutions ........................................................

XXIII.

xvii

657 662

665

669 674 678 683

THERMOSETS A. Poly(Ethyl a-Acetoxyacrylate) Acrylic Copolymer ............................................................. 687 B. Polyethersulfone High-Heat Polyethersulfone Compositions .............................. 689 C. Polynorborene Novel (Co)polymer, Process for Producing the Same, and Process for Producing Carboxylated (Co)polymer ........... 692 D. Polyformals Polyformals and Copolyformals with Reduced Water Absorption, Production, and Use Thereof .................... 695 E. Styrene and Zinc Diacrylate Ionomers Branched Ionomers .............................................................. 699 F. Polycyclodiene Copolymer of Conjugated Cyclodiene .................................... 702

xviii

Contents

G. a-Aromatic Ketones Poly(Aralkyl Ketone)s and Methods of Preparing the Same ....... 705 H. Polyimide Sulfones Polyimide Sulfones, Method and Articles Made Therefrom ....... 708 I. Benzoxazine Resins Method for Producing Benzoxazine Resin............................... 712 J. Acrylonitrile Block Copolymer ................................................................. 714 K. Polycarbonates Aliphatic Diol Polycarbonates and Their Preparation ................ 717 L. Poly(Silarylene-Siloxane-Acetylene) High-Temperature Elastomers from Linear Poly(Silarylene-Siloxane-Acetylene) ................................... 721 Contributors Academic Contributors ....................................................................... 725 Government Contributors .................................................................... 725 Industrial Contributors........................................................................ 726

Index ................................................................................................ 729

PREFACE

Much has changed in polymer chemistry since the first resin/polymer patent issued. US Patent 125 (February 10, 1817) describes a method of waterproofing boots and shoes reported by inventor Patrick G. Nagel. The method entailed: Taking two pounds of balsam-copiba, five pounds of the essence of the myrtletree, one pound of gum-copal, two pounds of rosin, and three pounds of rendered suet. The objective of this investigation has been to provide readers with current polymer chemistry research trends from academic, governmental, and industrial sources reported in US patents for the years 2006 to 2007. Twenty-three broad subject areas were reviewed as provided below: Additives Adhesives Bioactive Coatings Cosmetics Dental Electroactive Energetic polymers

Fibers Fluorine Gels Imaging agents Ink Liquid crystals Nanoparticles New synthetic methods

Optical materials Photoactive polymers Polymerization methods Regulators Photoresists Separations Thermosets

Another objective of this review have been to provide the reader with explicit laboratory methods for preparing agents/intermediates of interest, testing methods used to assay material efficacy, and analytical data for structural conformation. The text format has been designed to be used as a reference and synthetic guide for polymer and organic chemists as well as graduate students. The text, however, is not restricted to polymer chemistry. In many instances—and with only marginal modifications—intermediates and products are readily convertible into other agents in related or dissimilar research concentrations. To underscore this point, structural depictions of reagents, intermediates, and products are provided to allow the researcher to more easily visualize other/future material applications. Finally I thoroughly enjoyed compiling this review and trust the reader will find it useful. THOMAS F. DEROSA December, 2007

xix

I. ADDITIVES Title: Controlled Radical Acrylic Copolymer Thickeners Author:

S. C. Schmidt et al., US Patent Application 2007-0082827 (April 12, 2007)

Assignee:

Arkema, Inc. (Philadelphia, PA)

SIGNIFICANCE Di- and triblock polymers have been prepared by nitric oxide mediated polymerization using t-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide. Materials prepared from this process are useful as paint thickeners and viscosity index improvers in paint.

REACTION

a

b

c

i O

OCH3

Note 1

O

OCH3

O

OC12H25

O

OCH3

EXPERIMENTAL Preparation of Poly(Methacrylate-b-(Dodecyl Methacrylateco-Methacrylate)) A steel resin kettle was charged with t-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide (30.0 mmol) and methyl acrylate (6.97 mol) and then heated to 110 C for 3 hours, at which point the reaction had reached 50% conversion. The reaction mixture was cooled to ambient temperature and the Mw determined to be 12,600 daltons. In a

Advances in Polymer Chemistry and Methods Reported in Recent US Patents, by Thomas F. DeRosa Copyright Ó 2008 by John Wiley & Sons, Inc. 1

2

Controlled Radical Acrylic Copolymer Thickeners

glass reactor dodecyl methacrylate (159.4 mmol) was heated to 100 C and treated with the previously prepared polymer mixture (25.3 g) and methyl acrylate (25.3 mmol). This mixture was then treated with polymethacrylate (12.65 g) and methyl acrylate (4.83 g) and heated to 100 C to 105 C for several hours. The resultant viscous liquid was diluted with an equal volume of THF and precipitated into cold stirring methanol; the product was isolated having a Mw of 56,500 daltons and Mn of 39,600 daltons.

DERIVATIVES

TABLE 1. Selected di- and triblock polymers prepared by controlled free radical polymerization using t-butyl 1-diethylphosphono-2,2-dimethylpropyl nitroxide. Polymer*1

Mn

PDI

Notes

PDDMA-b-PS PDDMA-b-PS-b-PDDMA (PDDMA-co-PS)-b-PS-b-(PS-co-PDDMA) PDDMA-b-PMA-b-PDDMA PDDMA-b-PMA-b-PDDMA

28,000 31,600 31,600 23,000 76,000

1.6 1.7 1.7 1.5 2.0

PS ¼ 16% PS ¼ 35% PS ¼ 48% PMA ¼ 48% PMA ¼ 60%

Entry 1C 1D 1E 1F 1I

Note: All materials were used as viscosity index improvers in paint. *1

PDDMA ¼ Polydodecyl methacrylate PMA ¼ Polymethacrylate

NOTES 1. The nitric oxide mediated polymerization agent t-butyl 1-diethylphosphono2,2-dimethylpropyl nitroxide, (I), was prepared according to the method of Gillet [1] as illustrated below:

i t-C4H9

t-C4H9

t-C4H9

O H

t-C4H9

N H

P O

OC2H5 OC2H5

ii

t-C4H9

N

P

O

OC2H5 OC2H5

O

(I)

i: t-Butylamine, diethyl phosphate ii: 3-Chloroperbenzoic acid 2. Random copolymers effective as paint viscosity index improvers were prepared by Shoaf as provided in Table 2.

Notes

3

TABLE 2. Random copolymers used as viscosity index improvers and thickeners in paints. Polymer*1

Entry 1 5 7

Monomer Ratio*2 (wt%)

PS-co-PEHA-co-PAAEM-co-PMAA PS-co-PEHA-co-PAAEM-co-PMAA-co-PAA PS-co-PEHA-co-PMAA

51.8/22.7/8.0/2.5 45.9/21.1/8.0/1.25/3.75 63.7/18.9/2.5

*1 AA ¼ Acrylic acid AAEM ¼ Acetoacetoxy ethyl methacrylate EHA ¼ 2-Hydroxylethyl acrylate MMA ¼ Methylmethacrylate *2 The remainder of the composition consisted of alkyd.

3. Blankenship [3] prepared polyethylene glycol carbamate, (II), as paint thickeners containing poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) and either 1,6-hexamethylene diisocyanate or 4,40 -methylene bis-(isocyanatocyclohexane). Polycarbamates were also prepared by Bauer [4] using a block polymer initiated by stearyl alcohol and consisting of poly(ethylene oxide-bpropylene oxide-b-butylene oxide-b-dodecene oxide-b-tetradecene oxide) coupled with the diisocyanate, Desmodur NÒ.

H N 6

O O O

265

a

(II)

4. Polycarbamates, (III), prepared by Martin [5] consisting of toluene diisocyanate, methoxypolyethylene glycol, polypropylene glycol, and dihydroxymethyl propanoic acid were also effective as paint thickeners and viscosity index modifiers.

H N

O O

H N O

O

NH

O

O

O O

H3CO

a (III)

b c

4

Controlled Radical Acrylic Copolymer Thickeners

References 1. 2. 3. 4. 5.

J.-P. Gillet et al., US Patent 6,624,322 (September 23, 2003) G.L. Shoaf et al., US Patent Application 2006-0270769 (November 30, 2006) R.M. Blankenship et al., US Patent Application 2006-0106153 (May 18, 2006) S. Bauer et al., US Patent 7,189,772 (March 13, 2007) E. Martin et al., US Patent 7,144,945 (December 5, 2006)

Title:

Polymer-Filler Coupling Additives

Author:

A. Fukushima et al., US Patent 7,186,845 (March 6, 2007)

Assignee:

Bridgestone Corporation (Tokyo, JP)

SIGNIFICANCE A method for preparing and covalently bonding either 4-(2-oxazolyl)-phenyl- or methyl-N-phenylnitrone to natural rubber in automotive tires is described. The effect has been a 40% overall reduction in tire hysteresis and superior performance over existing polyamine formulations.

REACTION O Cl

H O

i

O

H

NH

O

ii

HO

O

H

N

O

iv

O

N

iii Notes 1,2

O

H

N

N O

O

N

Model reaction product

i: ii: iii: iv:

2-Aminoethanol, CCl3H Sulfuric acid, sodium hydroxide, CCl3H N-Phenyl-hydroxyamine, ethanol Cyclododecene

5

6


EXPERIMENTAL 1.

Preparation of 4-Formyl-N-(2-Hydroxyethyl)-Benzamide

A solution of 4-formyl-benzoylchloride (1 eq) in 300 ml of CCl3H was added dropwise at 10 C to a solution of 2-aminoethanol (2 eq), dissolved in 200 ml of CCl3H, and then stirred at 25 C for 2 hours. The mixture was filtered, dried, and concentrated, and 17.4 g of product were isolated as a yellow liquid. 2.

Preparation of 4-(2-Oxazolyl)-Benzaldehyde

The Step 1 product (17.4 g) was treated dropwise with 50 ml of 18 M H2SO4 and then heated to 100 C for 60 minutes. The mixture was added dropwise with stirring to 500 ml 20% sodium hydroxide and 500 ml of CCl3H while the solution temperature was kept below 15 C. The organic phase was separated and dried, and 6.3 g of product were isolated. 3.

Preparation of 4-(2-Oxazolyl)-Phenyl-N-Phenylnitrone

A mixture of the Step 2 product (1 eq) and N-phenyl-hydroxyamine (1 eq) was refluxed in 100 ml of ethanol for 30 minutes and then concentrated to 50 ml. The concentrate was treated with 50 ml of water and cooled in a refrigerator to 5 C overnight. White crystals were obtained; these were isolated by filtration, dried, and 6.7 g of product were isolated. 4. Model Reaction: Reactivity of 4-(2-Oxazolyl)-Phenyl-N-Phenylnitrone with Cyclododecene In selected amounts the Step 3 product was mixed with 1 ml cyclododecene and then heated to 171 C. The amount of recoverable Step 3 compound at various time periods during the reaction with cyclododecene was an indication of the reactivity of this product with unsaturated carbon–carbon bonds. Scoping results are provided in Table 1.

DERIVATIVES 4-(2-Oxazolyl)-phenyl-N-methylnitrone, (I), was also prepared:

O

H

N

N O

(I)

Testing

7

TESTING 1.

Reactivities

Reactivities of the Step 3 product and 4-(2-oxazolyl)-phenyl-N-methylnitrone, (I), with cyclododecene at 170 C are provided in Table 1.

O

H

N

N O R

TABLE 1. Percent incorporation of the Step 3 product and derivative into cyclododecene at 170 C.

Entry 2 4 5 7 9 10

R

Heating Time @ 170 C (min)

Nitrone Amount (mg)

Phenyl Phenyl Phenyl Methyl Methyl Methyl

5 15 30 5 15 30

5.52 5.65 5.60 4.09 3.83 4.05

Amount of Incorporated Experimental Nitrone (%) 97 100 100 39 78 98

Note: No characterization data for either experimental agents or cyclododecene addition products were provided by author.

2.

Tan d

The effect of the experimental agents on natural rubber hysteresis was determined by measuring tan d at 5% strain using an ARES-A Rheometer at 50 C and 15 Hz. Testing results are provided in Table 2.

8


TABLE 2. Effect of experimental additives on tan d of natural rubber at various treatment levels.

O

H

N

N O R

R

Nitrone Dosage (mmol)

Tan d

Unadditized Reference*1 Phenyl Phenyl Phenyl Phenyl Methyl Methyl Methyl Methyl

— 0.16 0.2 0.4 0.8 1.6 0.2 0.4 0.8 1.6

0.21 0.20 0.18 0.16 0.14 0.13 0.2 0.19 0.16 0.20

Note: Lower tan d values are preferred. *1 SumifineÒ 1162 ¼ (N,N0 -di(2-nitro-2-methyl-propyl)-hexamethylenediamine

NOTES 1. In a subsequent investigation by the author [1] styrene butadiene rubber functionalized with the Step 3 product was prepared and was effective in lowering tire hysteresis. 2. Bis-[2-2-thiazolyl-phenyl]disulfide, (I), derivatives were also prepared by the author [2] in a subsequent investigation and were effective in reducing tire hysteresis.

S N S S N S

(I)

Notes

9

3. Polymer nanostrings consisting of block terpolymers of butadiene, styrene, and divinyl-benzene having a Mn of 46,744 daltons were prepared Wang [3] and used as additives in natural and synthetic automotive tires. The nano strings were then postmodified to enhance tire surface and bulk performance. 4. Parker [4] end-group functionalized poly(1,3-butadiene) polymers with isopropyl hydroxyl-amines to improve the affinity and interaction with carbon black and silica fillers to extend tire lifetime.

References 1. 2. 3. 4.

A. Fukushima et al., US Patent Application 2006-0084730 (August 20, 2006) S. C. Schmidt et al., US Patent Application (2007-0161756 (July 12, 2007) X. Wang et al., US Patent 7,179,864 (February 20, 2007) D.K. Parker,US Patent Application 2007-0004869 (January 4, 2007)

II. ADHESIVES Title: (Meth)acrylate Block Copolymer Pressure Sensitive Adhesives Author:

A. I. Everaerts et al., US Patent 7,255,920 (August 14, 2007)

Assignee:

3M Innovative Properties Company (St. Paul, MN)

SIGNIFICANCE Block terpolymers consisting of butyl acrylate with either methylmethacrylate or methyl acrylate have been prepared where the end segments are at least 10,000 daltons and the center segment is at least 60,000 daltons. These materials were coated onto a polycarbonate surface and used to prepare an optical film and an optically clear pressure–sensitive adhesive layer that resists bubble formation when adhered to an outgassing substrate. REACTION

O O

i n-C4H9

60K

O

ii

10K

O

10K

O

O

O n-C4H9

60K

OCH3

O

OCH3

n-C4H9

i: Copper (I) bromide, 1,4-dibromoadipate, n-butyl acrylate, anisole, hexadecane, tris[2-(dimethyl-amino)ethyl]amine ii: Copper (I) chloride, n-butyl acetate, 1,1,4,7,10,10-hexamethyl-triethylenetetramine), methylethylketone, methylmethacrylate


12

(Meth)acrylate Block Copolymer Pressure Sensitive Adhesives

EXPERIMENTAL 1.

Preparation of a 60K Poly(Butyl Acrylate) Midblock Macroinitiator

A reactor was charged with a mixture consisting of CuBr (0.00478 g), 1,4-dibromoadipate (0.06 g), n-butyl acrylate (10.0 g), anisole (0.5 g), 0.5 ml of hexadecane, and 9.0 ml of tris[2-(dimethylamino)ethyl]amine. The mixture was heated to 60 C for 20 hours, and the product was isolated having a molecular weight of 60,000 daltons.

2. Preparation Poly[(Methylmethacrylate)-b-Poly(Butyl Acrylate)-bPoly(Methyl Methacrylate)] The Step 1 product was dissolved in roughly 10 ml of n-butyl acetate and then treated with CuCl (0.0396 g) complexed with 108.8 ml of 1,1,4,7,10,10-hexamethyl-triethylenetetramine), 2 ml of methylethylketone, and 4 ml of methylmethacrylate. The mixture was then heated to 60 C for 24 hours, cooled, dissolved in THF to 20% solids, and filtered through alumina to remove residual catalyst. The product poly(methylmethacrylate)-b-poly(butyl acrylate)-b-poly(methylmethacrylate) was isolated having molecular weight segments of 10,000/60,000/10,000 daltons, respectively.

DERIVATIVES TABLE 1. weights.

Selected block terpolymers and corresponding segmented molecular

Polymer*1

Segment Molecular Weights (daltons)

PolyMMA-b-polyBA-b-polyMMA PolyMMA-b-polyBA-b-polyMMA PolyMMA-b-polyBA-b-polyMMA pMMA-b-p(BA/MA)-b-pMMA (pBA-b-pMMA)3

10K–60K–10K 14K–120K–14K 14K–60K–14 10K–60K–10 (30K–10K)3

Entry 1 3 6 7 10

Note: Entry 10 is a tri-arm block copolymer. *1 MMA ¼ Methylmethacrylate BA ¼ n-Butyl acrylate MA ¼ Methyl acrylate

TESTING Accelerated aging testing and dynamic mechanical analysis were used to evaluate the stability of coated laminates. Testing results are provided in Table 2.

Notes

13

TABLE 2. Thermal aging stability and storage modulus analysis of laminates coated with selected experimental agents using PMMA or PC as the coating substrate.

Entry

Substrate

90 C Aging Test Results

1 1 3 3 6 6 7 7 10 10

PC*1 PMMA PC PMMA PC PMMA PC PMMA PC PMMA

Pass Pass Bubbles Bubbles Pass Pass Pass Marginal Bubbles Pass

80 C with 90% Humidity Test Results Marginal Pass Bubbles Bubbles Pass Pass Bubbles Pass Pass Pass

Log (G0 ) at 25 C (Pascals)

Log (G0 ) at 150 C (Pascals)

5.34 — 4.63 — —

4.84 — 4.22 — —

— — 5.60 —

— — 4.83 —

PC ¼ Polycarbonate

*1

NOTES 1. In an earlier investigation by Yang [1] triblock urethane acrylate oligomers terminated with acrylic acid were prepared and used in curable pressure sensitive adhesive compositions. 2. Additional block terpolymers containing propyl acrylate and star block terpolymers containing styrene were previously prepared by the author [2] and used in hot-melt pressure-sensitive and heat-activatable adhesives. 3. Random terpolymers consisting of ethyl, butyl, and behenyl acrylate were prepared by the author [3] and used as heat-activatable adhesives. Randon terpolymers consisting of iso-octyl/acrylic acid/styrene macromonomer, 92/4/ 4 mol%, respectively, were prepared by Joseph [4] and used as a reinforced pressure sensitive adhesive. 4. Linear and star diblock polymers consisting of methyl and n-butyl acrylates were prepared by Paul [5] and used as high performance, low viscosity hot-melt adhesives. A single star block terpolymer containing 2-ethylhexyl acrylate was also prepared. 5. Husemann [6] prepared UV-transparent adhesives consisting of acrylic acid, acrylamide, and 2-ethylhexyl acrylate that were effective as pressure-sensitive adhesives.

14

(Meth)acrylate Block Copolymer Pressure Sensitive Adhesives

References 1. J. Yang et al., US Patent 6,887,917 (May 3, 2005) 2. A.I. Everaerts et al., US Patent 7,084,209 (August 1, 2006) and US Patent 6,806,320 (October 19, 2004) 3. A.I. Everaerts et al., US Patent 7,008,680 (March 7, 2006) 4. E.G. Joseph et al., US Patent 6,994,904 (February 7, 2006) 5. C.W. Paul et al., US Patent Application 2004-0122161 (June 24, 2004) 6. M. Husemann et al., US Patent 7,144,928 (December 5, 2006)

Absorbable a-Cyanoacrylate Compositions

Title: Author:

H. Liu, US Patent 7,238,828 (July 3, 2007)

Assignee:

Ethicon, Inc. (Somerville, NJ)

SIGNIFICANCE Polymerizable 3-(2-cyano-acryloyloxy)-butyric acid ethyl ester has been prepared in a two-step process using 3-hydroxybutyrate and cyanoacetic acid followed by treatment with formaldehyde. This and related alkyl ester a-cyanoacrylate monomers are useful as tissue adhesives/sealants in surgical and related medical applications. REACTION CN

a

O OH

O

i O

O

NC

O

O

O

ii O

O

O

Oligomeric intermediate CN O O

O O

Note 1

i: Cyanoacetic acid, 4-dimethylaminopyridine, CH2Cl2, DMF, hexylcarbodiimide ii: Paraformaldehyde, piperidine, benzene, phosphorous pentoxide

dicyclo-

15

16


EXPERIMENTAL 1.

Preparation of 3-(2-Cyano-Acetoxy)-Butyric Acid Ethyl Ester

A reactor was charged with ethyl-3-hydroxybutyrate (194.0 g), cyanoacetic acid (149.83 g), 4-dimethylaminopyridine (10.76 g), and 1500 ml of CH2Cl2 and then treated with 75 ml of DMF. The solution was chilled in an ice-water bath and treated with dicyclohexylcarbodiimide (363.45 g) dissolved in 600 ml of CH2Cl2. A white precipitate formed within five minutes after the start of the addition, and the mixture was stirred overnight. The precipitate was then removed by filtration and the filtrate concentrated. The product was isolated in 73% yield after being distilled twice under vacuum, bp ¼ 100–109 C/0.20–0.27 mmHg. 1

H NMR (CDCl3) d 5.39(m, 1H), 4.16(q, 2H), 3.42(s, 2H), 2.62(m, 2H), 1.37(d, 3H), 1.27(t, 3H) GC-MS: 99.4%

2.

Preparation of 3-(2-Cyano-Acryloyloxy)-Butyric Acid Ethyl Ester

A mixture consisting of the Step 1 product (39.84 g), paraformaldehyde (6.6 g), 0.06 ml of piperidine, and 150 ml of benzene was stirred in a 250 ml round bottomed flask containing a Dean–Stark trap and refluxed overnight. The solution was then concentrated, and a viscous residue that turned into a solid gel after cooling to ambient temperature was isolated. The solid oligomer was de-polymerized by treating with hydroquinone (0.20 g) and phosphorous pentoxide and by heating to 160 C. The crude monomer was distilled under vacuum and the product isolated in 20% yield, bp ¼ 114– 115 C/0.17 mmHg A very small amount of this monomer product was placed between two moist fingertips and bonded the fingertips strongly within one minute. 1

H NMR (CDCl3) d: 7.03(s, 1H), 6.60(s, 1H), 5.43(m, 1H), 4.15(q, 2H), 2.65(m, 2H), 1.40(d, 3H), 1.23(t, 3H) GC-MS: 98.3%

TESTING 1.

General Procedure for Lap Shear Testing Using Pig Skin

Fresh pig skin was harvested from the back of a pig within 5 hours postsacrifice and the 00 00 fat attached to the inside skin surface trimmed away. The skin was cut into 2 1 coupons and covered by saline moist paper towels before use. The external surface of the skin was used as the bonding surface to prepare the lap shear joint samples. The coupons were dried prior to forming a lap shear joint. About 100 ml of the experimental adhesive was deposited to one coupon and smoothed to cover a 00 00 1=2 1 area. Another coupon was placed over the area of the initial coupon and a l lb weight placed on top. It was cured for 20 to 30 min and the strength of the joint

Testing

17

evaluated using an Instron (Model 5544) with a pulling rate of 5 mm/min. A summary of testing results is provided in Table 1. TABLE 1. Instron lap shear testing results for selected a-cyanoacrylate monomeric derivatives. Entry

Source

Structure

Load Strength (lb)

CN 1B

O

Invention

O

O

4.09

O

4.49

O

CN 2B

O

Invention

O

O

CN Et-e-CPL-CA

O O

Comparison

O

3.68

O

CN Et-a-CPL-CA

O O

Comparison

O

1.29

O

2.

In vitro Degradation Testing of Polymeric Films

A 1 1 inch Prolene mesh was rinsed with 0.5 wt% of NaHCO3 and dried. The mesh was then placed on a freshly prepared Agar plate in a petri dish and roughly 100 mg of a selected experimental adhesive applied across the mesh. The selected adhesive was cured overnight then sealed with parafilm; the film thickness was about 0.6 mm. The film was then placed into a hydrolysis chamber with 100 ml of water while the temperature of the solution was maintained at 75 C. The pH of the solution was maintained at 7.27 with addition of 0.05 M of a NaOH solution throughout the degradation of the polymer film. The degradation time was defined as the time required for the medium to consume 90% of the total consumed NaOH solution. The degradation and glass transition temperatures of each polymer are summarized in Table 2.

18


TABLE 2. In vitro degradation and glass transition temperatures of selected a-cyanoacrylate polymeric derivatives.

Entry

Source

Polymer Degradation Time (h)

Tg ( C)

O

54.6

32

O

39.4

11

49.4

52

Precursor Monomer

CN 1B

O

Invention

O

O

CN 2B

O

Invention

O

O

CN Bu-Lac-CA

O

Comparison

O

O O

Note: Polymers formed from compositions having Tg’s lower than body temperature (37 C) are particularly preferred for medical applications.

NOTES 1. The polymerization was conducted accorded to the method of Leung [1]. 2. Bioabsorbable adhesive compounds and compositions containing a polyalkylene oxide backbone having branched or multi-arm structure derived from reacting with two or more isocyanate substituents were prepared by Roby [2] and used as surgical adhesives and sealants. 3. Photochemical tissue bonding comprising a skin graft and Rose Bengal to form a skin tissue-RB complex with fibrin or a fibrinogen adhesive were prepared by Redmond [3]. The material was crosslinked by the application of electromagnetic energy having a wavelength of at least 488 nm and was used as an adhesive for repairing musculoskeletal tissue damaged by a laceration or rupture in humans.

Notes

19

4. An absorbable a-cyanoacrylate adhesive composition, (I), was prepared by Jonn [4] and used as a soft tissue adhesive.

CN O O O O C4H9 (I)


J.C. Leung et al., US Patent 5,928,611 (July 12, 1994) M.S. Roby,US Patent 7,241,846 (July 10, 2007) and US Patent 7,129,300 (October 31, 2006) R.W. Redmond et al., US Patent 7,073,510 (July 11, 2006) J.Y. Jonn et al., US Patent 6,620,846 (September 16, 2003)

Title: Use of Polybenzoxazoles (PBOS) for Adhesion Author:

A. Walter et al., US Patent 7,052,936 (May 30, 2006)

Assignee:

Infineon Technologies AG (Munich, DE)

SIGNIFICANCE A single-step method for preparing polybenzoxazole adhesives is described. These agents are particularly useful in the semiconductor industry for chip and wafer stack applications. REACTION

HO

OH

H2N

i

NH2 O

O

O

Notes 1, 2

HO H2N

O N O

O

O

O

N

N O

Not isolated

a

O

O OH

O

NH

N O

O

O

O

a

O

N

N O

O

i: Phosphorus (V) oxide, methane sulfonic acid, 4,40 -hydroxycarbonyl diphenylether, methacrylic acid

20

Derivatives

21

EXPERIMENTAL Preparation of Polybenzoxazole End-capped with Methacrylic Acid A reaction vessel was charged with 9,9-diphenyl-(4-amino-3-hydroxyl)diphenylether)fluorene (0.3 mol) and 800 ml of methane sulfonic acid and then treated with the dropwise addition of 4,40 -hydroxycarbonyl diphenylether (0.24) dissolved in 400 ml of methane sulfonic acid. The solution was heated for 5 hours at 80 C. After cooling to 40 C, the mixture was treated with the dropwise addition of methacrylic acid (0.12 mol) dissolved in 100 ml of methane sulfonic acid and heated an additional 6 hours at 100 C. The reaction product was isolated by filtering through a glass frit and the filtrate added dropwise to a mixture of 2 liter of water, 2 kg of ice, and 200 ml of this 12 M NH4OH; additional NH4OH was added during the filtration to ensure that the pH did not fall below 8. During the neutralization procedure the rate was such that the temperature did not exceed 30 C. The precipitated polymer was isolated by filtration and washed with 3 liter of cold water. Thereafter the solid was stirred in 3 liter 3% NH4OH at ambient temperature for 1 hour and then suspended repeatedly in water. After filtration and drying, 219 g of product were isolated.

DERIVATIVES

TABLE 1. Polybenzoxazole derivatives prepared using aminophenols and dicarboxylic acids with selected endcapping agents. Aminophenol Reagent

Entry

3

4

HO

F3C CF3

NH2

H2N

NH2

5

HO

OH

H2N

O2 S

O2 S

OH

H2N

HO

End-capping Agents

Diacid Reagent

OH

HO2C

HO2C

HO2C

— CO2H

N

CO2H

CO2H

HO2C

—

NH2

(continued)

22

Use of Polybenzoxazoles (PBOS) for Adhesion

TABLE 1.

(Continued) Aminophenol Reagent

Entry HO

6

F3C CF3

End-capping Agents

Diacid Reagent

O

OH

CO2H

HO2C

H2N

O

NH2 O

O

8

HO

HO2C

NH2 O

HO

10

—

OH

H2N

H2N

N

CO2H

O

F3C CF3

O2 S

OH NH2

HO2C

OH CO2H

O

TESTING A 4-inch silicon wafer was sputtered with a titanium nitride layer 50 nm thick and then a selected polybenzoxazole adhesive applied by spin-coating. Following a short softbake at 120 C for 1 minute and at 200 C for 2 minutes on a hotplate, a second 50 nm titanium nitride was sputtered onto the surface. A force of 2 N was then applied to the polybenzoxazole film at 340 C. The sample was further heated to 400 C in an oven under a nitrogen atmosphere for 60 minutes. After cooling to ambient temperature the adhesion test was carried out by means of a shear tester using a Dage Series 400. Testing results are provided in Tables 2 through 4.

TABLE 2. surface.

Average shear force of polybenzoxazole bonded to a titanium nitride

Polybenzoxazole 3 4 5

Adhesive Shear Force (N/mm2)

Coating Type

17.94 20.67 18.69

Spray Spin coat Spray

Notes

TABLE 3. surface.

Average shear force of polybenzoxazole bonded to a tantalum nitride Adhesive Shear Force (N/mm2)

Polybenzoxazole 6 8 10

Coating Type

17.03 18.47 17.26

TABLE 4.

23

Spray Spray Spin coat

Average shear force of polybenzoxazole bonded to a copper surface.

Polybenzoxazole

Adhesive Shear Force (N/mm2)

Coating Type

21.28 20.06

Brushing Powder melting

Step 1 product 3

NOTES 1. In an earlier investigation by the author [1] phenyl-linked polyoxazole derivatives, (I), were prepared and converted into cyanates by reacting with isocyanate derivates. Cyanate derivatives were used as dielectrics because of their good adhesive and filling properties. N O O

O

O

N

a O

HO H2N O

O

O

N

N b

N

O

O

O

(I)

2. Polyhydroxyamides, (II), prepared by Halik [2] were converted into polybenzoxazole-based adhesives by curing at 300 C to 350 C. Polyhydroxyamides, (III), were also prepared and converted into the corresponding

24

Use of Polybenzoxazoles (PBOS) for Adhesion

polybenzoxazoles by curing 60 minutes at 425 C. O

CH O

C

a O

O

OH

OH N H

N Ha

H N

H N

OH

OH

O O

N H

(II)

(III)

3. Hall [4] prepared crossliked polymers that were effective as adhesives by UV curing of the neutralization product of diallylamine with selected carboxylic acids, (IV). Additional UV curable diallyl amine adhesives, (V), were prepared by Milne [5].

NH2

O

O

N

N

O2C CO2H

(IV)


A. Walter et al., US Patent 6,824,642 (November 30, 2004) M. Halik et al., US Patent 7,064,176 (June 20, 2006) R. Sezi et al., US Patent 7,108,807 (September 19, 2006) A.W. Hall, US Patent 7,112, 639 (September 26, 2006) P.E. Milne et al., US Patent 7,026,419 (April 11, 2006)

(V)

III. BIOACTIVE A. Bioabsorbables

Title: Segmented Urea and Siloxane Copolymers and Their Preparation Methods Author:

I. Yilgor et al., US Patent 7,262,260 (August 28, 2007)

Assignee:

Virginia Tech Intellectual Properties, Inc. (Blacksburg, VA)

SIGNIFICANCE Copolymers and terpolymers containing siloxane-urea segments have been prepared by condensing a,o-N-methylaminopropyl terminated polydimethyl-siloxane with bis(4isocyanatocyclohexyl) methane then postreacting with a,o-N-methylaminopropyl terminated polypropylene oxide. Polymeric biocompatible materials including membranes and adhesives obtained in this process had controlled modulus, high ultimate tensile strength, and favorable refractive index properties.

REACTION N H

O

Si

O a

N H

i PPO

H N

H N O

O

O N H

N H

O

Si

O

a

N H

O N H

N H

N H

PPO

b

i: a,o N-Methylaminopropyl terminated polydimethylsiloxane, isopropylamine, bis (4-isocyanatocyclohexyl) methane, a,o N-methylaminopropyl terminated polypropylene oxide


26

Segmented Urea and Siloxane Copolymers and Their Preparation Methods

EXPERIMENTAL Preparation of Poly(Dimethylsiloxane-Urea-Propylene Oxide) A mixture consisting of a,o-N-methylaminopropyl terminated polydimethylsiloxane (80 mol%) having a Mn of 2500 daltons dissolved in isopropylamine and bis(4isocyanatocyclohexyl)-methane (20 mol%) were mixed at ambient temperature then posttreated with a,o-N-methylaminopropyl terminated polypropylene oxide. The reaction extent was determined by FTIR spectroscopy by monitoring the disappearance of the isocyanate peak at 2270 cm 1. Reaction mixtures were always homogeneous and usually clear throughout the reactions. No precipitation was observed.

DERIVATIVES AND TESTING TABLE 1. Comparison of tensile properties of bis(4-isocyanatocyclohexyl) methanebasedpolydimethylsiloxane-urea and polyether/polydimethylsiloxane-urea segmented copolymers.

Entry

Polyether

Polyether Mn (daltons)

1 3 4 6

PDMS*1 PDMS PEO PEO

2500 2500 2000 2000

Polymer Urea Content (wt%)

[Z] (dL/g)

Modulus (MPa)

Tensile Strength (MPa)

Elongation (%)

20 19 20 19

0.48 0.54 0.81 0.72

20.6 21.3 4.30 4.50

7.90 8.30 25.4 26.5

205 180 1320 1450

*1

Polydimethylsiloxane

NOTES 1. High purity and high molecular weight siloxane-urea/urethane copolymers, (I), were prepared by Kuepfer [1] at ambient temperature using dibutyl tin diacetate as catalyst under anhydrous conditions. Additional siloxane-urea/urethane copolymer derivatives were prepared by Schafer [2].

H N O

H N O O

O

Si

O

Si

N H

O N H

(I)

O O

N H

a

Notes

27

2. Mixed urea block copolymers consisting of amine-terminated polydimethylsiloxane were prepared by Sherman [3] and used as pressure sensitive adhesives. Other urea-based pressure sensitive adhesives containing polydimethylsiloxanes are described by Zhou [4]. 3. Brandt [5] prepared a nontacky spray on bandage—“patch in a bottle”— consisting of the reaction product of isophorone diisocyanate, polydimethylsiloxane diamine having a Mn of 5400 daltons, and polypropylene oxide diamine having a Mn of 2000 daltons. References 1. 2. 3. 4. 5.

J. Kuepfer et al., US Patent 7,153,924 (December 26, 2006) O. Schafer et al., US Patent 7,026,424 (April 11, 2006) A.A. Sherman et al., US Patent 7,012,110 (March 14, 2006) Z. Zhou et al., US Patent 7,090,922 (August 15, 2006) A. Brandt et al., US Patent 6,958,154 (October 25, 2005)

Title: Functionalized Polymers for Medical Applications Author:

A. Nathan, US Patent 7,253,248 (August 7, 2007)

Assignee:


SIGNIFICANCE Biodegradable and biocompatible a,b-unsaturated polyesters have been prepared by condensing maleic anhydride with monoleoyl glycerol alone or in combination with monoleoyl glycerol polyethylene glycol. Mercaptoethylamine was then free radically incorporated into the a,b-unsaturated site using azobisisobutyronitrile. These polymeric agents were used to prepare medical devices including sutures, staples, surgical tacks, clips, and plates.

REACTION O

O O

O O

C17H30

i

O

O

O

C17 H 30

O

ii

O

OH OH O

O O

O

O

C17 H 30

O

O

S

S

O

O

O

O O a

a

H2N

NH2

i: Monoleoyl glycerol, maleic anhydride ii: DMF, 2,20 -azobisisobutyronitrile, mercaptoethylamine

EXPERIMENTAL 1.

Preparation of Poly(Monooleoyl Glyceride-co-Maleic Anhydride)

A reactor was charged with monoleoyl glycerol (142.6 g) and then heated to 140 C and treated with maleic anhydride (39.2 g). The reaction mixture was further heated to 28

Notes

29

190 C for 3 hours and cooled to ambient temperature. The product was isolated as a pale yellow viscous liquid having a Mn of 1383 daltons and a Mw of 6435 daltons. 2. Addition of Mercaptoethylamine to Poly(Monooleoyl Glyceride-co-Maleic Anhydride) A mixture consisting of the Step 1 product (5.0 g), 0.85 ml of mercaptoethylamine, 11 ml of DMF, and 2,20 -azobisisobutyronitrile (54 mg) was heated to 60 C for 24 hours and then cooled to ambient temperature. The polymer was diluted with 10 ml of EtOAc, washed once with 0.01 M of NaOH, twice with brine, dried with MgSO4, and filtered. The solution was concentrated, and the product was isolated as a yellow, transparent viscous liquid. 1

HNMR (CD3Cl, ppm): d 0.86 triplet (3H), 1.26 multiplet (22H), 1.61 multiplet (2H), 2.00 multiplet (4H), 2.30 multiplet (2H), 2.80 multiplet (2H), 3.60 multiplet (2H), 4.20 multiplet (3H), 5.38 multiplet (2H); no a,b-unsaturated ester remaining in the polymer FTIR (ZnS, cm1): 3346, 2920, 2860, 1745, 1660, 1456, 1168

DERIVATIVES TABLE 1. Co-components used in reacting with maleic anhydride forming the corresponding a,b-unsaturated polyester and corresponding physical properties. Entry 2 3

Co-component – 1

Co-Component – 2

Mn (daltons)

Monooleoyl glycerol Monooleoyl glycerol

5 mol% PEG-400 25 mol% PEG-400

1122 1230

Mw (daltons) 5647 4481

NOTES 1. Poly(monostearoyl glycerol-co-succinate) containing upto 5% polyethylene glycol, (I), was prepared by Arnold [1] and Nathan [2] and used as a bioabsorbable and biocompatible polymeric wax. Poly(monostearoylglyceride-co-succinate) containing 5% N-methyl diethanoamine, (II), was prepared by the author [3] in an earlier investigation.

O O

O

O

5 mol%

O

O 95 mol% C17H35

O

(I)

O

30

Functionalized Polymers for Medical Applications

O O

O

N H

5 mol%

O

O

O

95 mol% C17H35

O

(II)

O

2. The biodegradable and biocompatible polymer poly(monostearoyl glycerideco-succinate-co-caprolactone), (III), was prepared by Nathan [4] and used in medical devices.

O

O O

O

O

O

N H

C17H35

a

O

(III)

3. Block copolymers, (IV), consisting of succinic acid coupled with propylene glycol and then capped with hexamethylene diisocyanate and reacted with polylactic acid were prepared by Imamura [5] and used as biodegradable containers.

O

O O O

O

O

O O

(IV)


O

H N

H N

O a

S. Arnold et al., US Patent 7,034,037 (April 25, 2006) A. Nathan et al., US Patent 7,030,127 (April 18, 2006) A. Nathan et al., US Patent 6,866,860 (March 15, 2005) A. Nathan et al., US Patent 6,967,234 (November 22, 2005) S. Imamura et al., US Patent 7,223,815 (May 29, 2007)

O

b

c

O

Title:

Degradable Polyacetal Polymers

Author:

S. J. Brocchini et al., US Patent 7,220,414 (May 22, 2007)

Assignee:

A. P. Pharma, Inc. (Redwood City, CA)

SIGNIFICANCE Polyacetal polymers containing polyethylene glycol have been prepared which are stable at physiological pH but which readily degrade at lower pH’s. Bolton Hunter reagent conjugates prepared from these materials showed a favorable biodistribution profile of the 125 I product.

REACTION HO HO

OH NH2

iv

i

O

OH HN

O

O

3

O

O

O

3

O

O

60

ii

O

O

O

O

O

O

3

O

3

a HN

O O

O

O

O

O

O

60

O

O

O

60

iii 3

3

a NH2

a HN

O

125 I

HO 125 I

i: Sodium hydroxide, N-(9-fluorenylmethoxycarbonyl)chloride, CH2Cl2 ii: Polyethylene glycol, p-toluene sulfonic acid, divinyl tri(ethylene glycol),THF, triethylamine 31

32


iii: Piperidine, CH2Cl2 iv: N-Succinimidyl 3-(4-hydroxy 5-[125I]iodophenyl) propionate), benzene, DMF, sodium hydroxide

EXPERIMENTAL 1.

Preparation of N-(9-Fluorenylmethoxycarbonyl) Intermediate

A reactor containing 2-amino-1,3-propanediol (10.0 mmol) and 25 ml of 1M NaOH was cooled to 0.2 C and treated with N-(9-fluorenylmethoxycarbonyl)chloride (13.1 mmol) dissolved in 10 ml of CH2Cl2 over a 1 hour period. The solution was stirred for 1 hour at 0 C and 4 hours at ambient temperature. The organic solvent was evaporated and the aqueous residue poured into 70 ml of EtOAc. The organic phase was isolated, washed with 5% aqueous HCl, dilute NaHCO3, brine, and dried. The mixture was concentrated, the residue re-crystallized in chloroform, and the product was isolated.

2.

Preparation of Polyether N-(9-Fluorenylmethoxycarbonyl) Intermediate

Polyethylene glycol having a Mn of 3400 daltons (1.47 mmol) and p-toluene sulfonic acid (0.012 g) were added to a 100-ml flask and heated to 80 C to 90 C for 3 hours at 0.5 to 1.0 torr. The mixture was cooled and treated with the Step 1 product (1.47 mmol) and 10.0 ml of THF; it was further treated with divinyl tri(ethylene glycol) (2.94 mmol) in 10 ml of THF. This reaction mixture was stirred for 2 hours at ambient temperature and then treated with 0.3 ml triethylamine. The reaction mixture was precipitated in 100 ml of hexane, and the product was isolated having a Mn of 25,000 daltons.

3.

Preparation of Polyether Acetal Amine Intermediate

A solution of the Step 2 product (2.050 g) in 20% piperidine containing 10 ml of CH2Cl2 was stirred at ambient temperature and monitored by thin layer chromatography. The amino functionalized polyacetal was then isolated by partitioning the piperidine into hexane and next CH2Cl2. The residue was dissolved in THF, and the polymer was precipitated by pouring into 100 ml of hexane. The product was isolated having a Mn of 23,000 daltons. 4.

Preparation of 125 I Polyether Acetal

The Step 3 product (50 mg) was dissolved in 10 mg/ml of 0.1M borate with a pH 8.5 buffer by the addition of a small amount of NaOH and then treated with N-succinimidyl 3-(4-hydroxy 5-[125 I]iodophenyl) propionate), 500 mCi, dissolved in benzene containing DMF, and stirred for 15 minutes at ambient temperature. The mixture was diluted

Notes

33

with phosphate buffer solution to 10 ml, transferred to dialysis tubing, and dialyzed against water until no radioactivity was found in the dialysate, and the product was isolated.

DERIVATIVES Three additional divinyl ether derivatives were prepared as illustrated below. O N H

O

H N

O

O N H

O

O O

O

N H

O N H

O

O

N H

NH2

N H

O

NOTES 1. Bleach resistant polyacetals consisting of 98% trioxane and 2% dioxolane was prepared by Notorgiacomo [1] and used in molding compositions. 2. Branched polyformals and copolyformals, (I), were prepared Heuer [2] and used in the production of molded articles.

O

O

(I)

a O

O

bc

3. Polyvinyl butyral resins, (II), were prepared by Miyake [3] and used in heatdevelopable photosensitive material film.

a O O

(II)

b

34


4. Polyacetal resin compositions having excellent wear resistance were prepared by Kim [4]. These resins consisted of polyoxymethylene polymer, ethylene vinylacetate, melamine, triethyleneglycol-bis-3-(3-t-butyl-4-hydroxy5-methylphenyl)-propionate, and hydroxyl pentaerythritol fatty acid ester. References 1. 2. 3. 4.

V.J. Notorgiacomo et al., US Patent 7,223,809 (May 29, 2007) H.-W. Heuer et al., US Patent 7,208,564 (April 24, 2007) and US Patent 7,199,208 (April 3, 2007) Y. Miyake, US Patent 7,176,257 (February 13, 2007) T.-K. Kim et al., US Patent 7,098,262 (August 29, 2006)

Title:

Lactone Bearing Absorbable Polymers

Author:

F. X Ingnatious, US Patent 7,205,378 (April 17, 2007)

Assignee:

Societe de Conseils de Recherches et d’Applications Scientifiques (Paris, FR)

SIGNIFICANCE A procedure for the slow and sustained release of the growth hormone inhibitor Lanreotide is described. The method entails incorporating Lanreotide to the isocitric acid lactone component on the backbone of a polyester block copolymer using sodium hydroxide as the saponification agent.

REACTION O HO2C

O

CO2H

H

O

HO

i

O

O O

O

O

O O

O

O

R H

O

iii Note 1

ii

a

HO

O

O

O

O

a

O

R

b

O

R = H or CH3

O O

O

O

R O

HO

O

O

Na O Lanreotide (R)

O NH3

O

O a R

H b

O

O

i: Propanediol, benzene ii: dl-Lactide, glycolide, stannous octanoate, toluene iii: Sodium hydroxide, acetone, Lanreotide 35

36


EXPERIMENTAL 1.

Preparation of Poly(isocitric Acid Lactone-co-Propanediol)

A reactor containing a Dean–Stark trap was charged with isocitric acid lactone (14.3 mmol), propanediol (15.7 mmol), and benzene was then refluxed at 90 C overnight. The mixture was concentrated and a viscous liquid isolated that solidified on cooling.

2. Preparation of Poly[(Isocitric Acid Lactone-co-Propanediol)block-(Glycolide-co-Lactide)] The reaction vessel containing the Step 1 product was transferred to a dry box and treated with dl-lactide (25.2 g), glycolide (7.25 g), and 0.2 ml of stannous octanoate solution in toluene. The polymerization reaction was performed at 160 C for 8 hours and then quenched in liquid nitrogen. The polymer was isolated, dissolved in acetone, and precipitated in cold water, with the product isolated having a Mn of 3790 daltons and Mw of 7040 daltons. 3. Preparation of Poly[(Isocitric Acid Lactone-co-Propanediol)block-(Glycolide-co-Lactide)] Ionically Complexed with LanreotideR The Step 2 product (1 g) was dissolved in acetone and treated with 0.45 ml of 1M NaOH, then stirred for 20 minutes, and further treated with Lanreotide (0.29 g) dissolved in 2 ml of 1:1 acetone/water. The polymer solution was left stirring for 2 hours and then precipitated in cold water. The product was filtered and dried; the product isolated had a 17.6% nitrogen content.

DERIVATIVES No additional derivatives were prepared.

TESTING In vivo Testing The Step 3 product was ground and sieved with a mortar and pestle and passed through a 125 m sieve. Rats were administered 6.75 mg of the experimental agent by injection in a medium consisting of 2% carboxymethylcellulose, 1% Tween 20, and saline. Blood samples were collected at various time intervals, and the plasma levels of Lanreotide was determined by radioimmuno assay. Test results for are provided in Table 1.

Notes

TABLE 1. assay.

In vivo test results for Lanreotide in plasma levels using radioimmuno

Sample Step 3 product Entry 4*1 *1

37

Lanreotide Levels after 6 Hours (ng/ml)

Lanreotide Levels after 8 Days (ng/ml)

Lanreotide Levels after 22 Days (ng/ml)

21 – 4.5 24.4 – 5.2

30.2 – 7.5 20.8 – 7.2

0.05 – 0.02 0.141 – 0.09

Entry 4 was obtained by replacing NaOH with an equivalent amount of NaHCO3 in Step 3.

NOTES 1. Lanreotide has the formula H-b-D-Nal-Cys-Tyr-D-Trp-Lys-Val-Cys-ThrNH2, where, the two Cys are bonded by a disulfide bond. Lanreotide is a somatostatin analogue that inhibits the release of growth hormones. 2. In a subsequent investigation by the author [1] biodegradable microparticles such as poly(l-lactic-co-glycolic-co-d,l-malic acid), (I), were prepared and used as a drug delivery agent for the acetate salt of Lanreotide.

O

O

R

O O O

R

O

a O

Lanreotide NH3

b

R = H or CH 3

O

OAc

(I) 3. Shalaby [2] prepared ionic molecular conjugates of the hydrolyzed drug delivery agent chitosan and Somatuline, (II), in the treatment of acromegaly.

38


HO O OH

HO OO a OH

HO OO OH

NH3

CO2

NH3

OH

CO2

CO2

NH3

Somatuline NH3

CO2 CO2

Somatuline NH3

Somatuline NH3 CO2

(II)

4. Li [3] prepared ionic complexes of aminated polyrotaxanes with bulky biocleavable end caps as a method for delivering nucleic acids. 5. Polyfunctional monomers, (III), prepared by Li [4] were used to synthesize cationic polymers having degradable crosslinks for therapy involving the delivery of nucleic acids into cells. O

O O

O

O

O

O

O

O

O

O

O

(III)

6. Leong [5] and Dang [6] used cyclic phosphate monomers, (IV), and either lactide or caprolactone monomers to prepared phosphate based biodegradable polymers, (V), illustrated below, that were then converted into microspheres and used as drug deliver agents for anti-neoplastic medicaments. O

O O

O H3CO

P

i

O

(IV) i: d,l-Lactide, benzene, methanol

P

O

O O

(V)

O a OCH3

O

b

Notes

References 1. 2. 3. 4. 5. 6.

F.X Ingnatious et al., US Patent Application 2006-0121120 (June 8, 2006) S.W. Shalaby et al., US Patent 7,005,420 (February 28, 2006) J. Li et al., US Patent Application 2006-0211643 (September 21, 2006) S. Li et al., US Patent 7,163,677 (January 16, 2007) K.W. Leong et al., US Patent 6,805,876 (October 19, 2004) W. Dang et al., US Patent 6,800,672 (October 5, 2004)

39

B. Contact Lenses

Title: Low Polydispersity Poly-HEMA Compositions Author:

T. Kindt-Larsen et al., US Patent 7,256,246 (August 14, 2007)

Assignee:

Johnson & Johnson Vision Care, Inc (Jacksonville, FL)

SIGNIFICANCE Cross-linked pre-polymers having fractionalized molecular weights between 35,000 and 70,000 daltons with polydispersity indexes of less than 3.4 have been prepared by the free radical addition of 2-hydroxethyl methacrylate, HEMA, with 2% methacrylic acid or glycerol methacrylate. Once crosslinked, these materials are particularly useful as contact lenses because of their limited shrinkage and expansion.

REACTION O i

O

Note 1

a

ii Fractionalization Note 2

O

O

O

b O

cd OH

O

OH OH

O

O

i: Ethanol, dodecyl mercaptan, methacrylic acid, 2,20 -azobis (2-methylbutyronitrile) ii: Ethanol, hexane

EXPERIMENTAL 1. Preparation of Poly(2-Hydroxethyl Methacrylate-co-Methacrylic Acid) (poly-HEMA) A 5-liter stainless steel reactor was charged with ethanol (1911.6 g), 2-hydroxethyl methacrylate (1056.6 g), dodecyl mercaptan (3.00 g), and methacrylic acid (21.00 g)

40

Experimental

41

at 25 C. The temperature was raised to 68 C and then the mixture treated with 2,20 -azobis(2-methylbutyronitrile) (7.50 g). After heating for 18 hours at 68 C the mixture was heated to 80 C an additional 22 hours then cooled. The product was isolated with a solid content of 37.2% with a Mn of 68,000 daltons and a PDI of 3.75.

2. Fractionalization of Poly(2-Hydroxethyl Methacrylate-co-Methacrylic Acid) Step 1 Fractionalization Process The Step 1 product was initially diluted with ethanol to give a 10% solution of polyHEMA in ethanol. The solution initially became turbid at 24 C and clear and homogeneous at 40 C. The solution was cooled to 21 C; the solution then separated into two clear phases after three days. The bottom fraction had a molecular weight of 144,000 daltons with a polydispersity of 3.34 and was discarded. The top soluble layer had a molecular weight of 64,000 daltons with a polydispersity of 2.28 and was further fractionated at 8 C. After 24 hours the solution was again separated into two phases. The bottom phase constituted 15 vol% of the total solution and contained 35.7 wt% of poly-HEMA having a molecular weight of 83,800 daltons with a polydispersity of 2.18 that was further fractionated. Step 2 Fractionalization Process After addition of 2% hexane to the lower layer, the solution had a cloud point at 31 C. The mixture was heated to 40 C to make it homogeneous, and then it stood at 28 C for five days before it separated into two clear phases. The top phase contained 77.1% of the polymer and was siphoned off, and the bottom phase was discarded. Step 3 Fractionalization Process The amount of hexane in the top phase was adjusted to 7%, which resulted in a cloud point of 54 C. The solution was re-heated to 57 C to make it homogeneous, and after four days at 29 C the solution separated into two clear phases. The top phase containing the low molecular weight fraction of the polymer was siphoned off, and the bottom phase was given a third fractionation. Step 4 Fractionalization Process In this procedure the hexane concentration was adjusted to 8%, and the solution stood for four days at 30 C. The top phase containing the low molecular weight fraction of the polymer was siphoned off, and the lower retained as the Step 1 fractionalized product.

42

Low Polydispersity Poly-HEMA Compositions

FRACTIONALIZATION PROFILE TABLE 1. Fractionalization effectiveness for poly(2-hydroxethyl methacrylateco-methacrylic acid) using selected extraction solvents.

Entry

Fractionalization Temperature ( C)

Fractionalization Solvent

Molecular Weight (daltons)

PDI

82 78 74 72 68

2-Propanol 2-Propanol Ethanol Ethanol Ethanol

35,000 40,000 50,000 60,000 70,000

3.4 3.4 2.6 3.6 3.3

5 6 7 8 9

DERIVATIVES Poly(2-hydroxethyl methacrylate-co-glycerol methacrylate) was also prepared having a molecular weight of 41,000 daltons with a PDI of 2.80.

NOTES 1. The preparation of molded contact lenses using the polymers of the current invention are described by the author [1] in an earlier investigation. 2. Ford [2] determined that isopropanol, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol methyl ether, and tripropylene glycol methyl ether were also effective in fractionating analogues of the current invention. 3. Wettable polymer silicon hydrogels were prepared by Laredo, (I), [3] and Zanini, (II), [4], respectively, and used in contact lenses. O O O

N H

O O

O

Si

O 26

O

O O CH2CF2(OCF2)aCF3

N H

NH

(I)

(H3C)3SiO Si O OSi(CH3)3

(H3C)3SiO O OH O

(II)

OH

Si OSi(CH3)3

Notes

43

4. Biocompatible contact lenses having high oxygen and water permeability were prepared by Nicolson [5] by reacting the polysiloxane macromonomer, (III), with ethylene glycol, and 2% 2-hydroxyethyl methacrylate. HN

O

O

Si

O a

O OCN

O

(III)


H N

O

T. Kindt-Larsen et al., US Patent 6,846,892 (January 25, 2005) J.D. Ford et al., US Patent 7,112,652 (September 26, 2006) W.R. Laredo et al., US Patent 7,249,848 (July 31, 2007) D. Zanini et al., US Patent 7,214,809 (May 8, 2007) P.C. Nicolson et al., US Patent 7,045,248 (October 4, 2005)

b NCO

C. Drug Delivery

Title: Amphiphilic Block Copolymers and Nanoparticles Comprising the Same Author:

M.-F. Hsieh et al., US Patent Application 2007-0104654 (May 10, 2007)

Assignee:

Industrial Technology Research Institute (Hsinchu, TW)

SIGNIFICANCE A biocompatible and biodegradable amphiphilic block copolymer consisting of hydrophobic and hydrophilic segments containing zwitterions has been prepared. This agent is useful as a drug delivery agent for water-insoluble drugs, including growth factors and genes, and in cosmetic formulations.

REACTION O O

i

H3CO

O

O O

Nanoparticles

iv

ii

bH

a

H3CO

H3CO

O

O

a

O

O a

O

O O b P O O

N(CH3)3

O P O O

iii

i: Poly(ethylene glycol), stannous 2-ethylhexanoate ii: Triethylamine, 2-chloro-2-oxo-1,3,2-dioxaphospholane, CH2Cl2 iii: Acetonitrile, trimethylamine, CH2Cl2

EXPERIMENTAL 1.

Preparation of Poly(Ethylene Glycol-b-Valerolactone)

A glass reactor was charged with poly(ethylene glycol) (60 g; 5000 daltons) and d-valerolactone (12 g), which was gradually heated until dissolved. This mixture was 44

Derivatives

45

then treated with 0.38 ml of stannous 2-ethylhexanoate and heated for 8 hours at 160 C. Thereafter the mixture was dissolved in CH2Cl2 and precipitated by adding diethyl ether. The white precipitate was washed and dried, and the block copolymer was isolated. 2. Preparation of Poly(Ethylene Glycol-b-Valerolactone)-2-oxo-1,3,2Dioxaphospholane The Step 1 product (5 g) and triethylamine (0.43 g) were dissolved in 70 ml of CH2Cl2 at 0 C, then added dropwise to 2-chloro-2-oxo-1,3,2-dioxaphospholane (3.5 g) dissolved in 30 ml of CH2Cl2 and stirred at 0 C for 6 hours. The resulting solution was warmed to ambient temperature, filtered through 0.45 mm filter paper, and concentrated, and the product was isolated. 3. Preparation of Poly(Ethylene Glycol-b-Valerolactone)Trimethylammonium Phosphate The Step 2 product was dissolved in 70 ml of acetonitrile at ambient temperature and then treated with 10 ml of 33% trimethylamine in ethanol and heated for 24 hours at 60 C. The solution was next concentrated and extracted three times with CH2Cl2/ water. After re-concentrating and drying, the product was isolated as a white solid. 4.

Preparation of Polymeric Nanoparticles

Ten milligrams of the Step 3 product were dissolved in 1 ml of dimethyl sulfoxide and then removed by freeze-drying. Thereafter 1 ml of 10% sucrose was added to the hydrate, and the freeze-dried solids were re-dissolved to form a suspension. After ultra-sonicating for 10 minutes, polymer nanoparticles were formed.

DERIVATIVES Two additional derivatives were prepared as illustrated below. O H3CO

O

O a

O NHR

b

O

R ________________ H2C

SO3

N

CO2H HC

N N

46

Amphiphilic Block Copolymers and Nanoparticles Comprising the Same

TESTING Micelle Formation A solution of 10 mg of a selected polymer dissolved in 1 ml THF was gradually added to 30 ml deionized water and stirred. The solution was placed in a dialysis membrane for 24 hours to form a micelle solution. Then the 3 to 5 ml micelle of the solution was placed in an acrylic cuvette to measure micelle sizes and their distribution by photon correlation spectroscopy. Testing results are provided in Table 1. TABLE 1. Effect of terminus and block segment composition in poly(ethylene-glycol-b-valerolactone) on CMC formation. Polymer Terminus Trimethylammonium phosphate Dimethylammonium sulfate

PEO Block (daltons)

Lactone Block (daltons)

CMC (10 2 wt%)

5000 5000 2000 2000 5000 5000

1900 1100 1000 2000 2500 3700

3.26 17.92 1.46 4.47 3.95 7.76

NOTES 1. Amphiphilic block copolymers consisting of polyethylene glycol and polylactide, (I), were prepared by Seo [1] and used as drug delivery agents for PaclitaxelÒ. O O

H3CO

O 44

O

O

24

(I)

O

2. Block cationomers, (II), consisting of polyisobutylene and poly(2-dimethylamino)ethyl methacrylate) were prepared by Kennedy [2] and used as timed release agents for pharmaceuticals. O Br Polyisobutylene

a O

(II)

O

N(CH3)3 I

Notes

47

3. Wang [3] prepared the amphiphilic biocompatible cyclodextrin graft polymer, poly(ethylene glycol-g-cyclodextrin), (III), containing modified cyclodextrin which was used as a bioactive drug delivery agent.

O

O b

a

O

NH

S

S

HN

Cyclodextrin

(III) 4. Dai [4] modified oxidized carbon nanotubes, (IV), and these were subsequently used as transporters for the delivery of biologically active agents into cells.

O

O N H

Oxidized nanotube

O

a

N H

(IV)


M.-H. Seo et al., US Patent 7,217,770 (May 15, 2007) J.P. Kennedy et al., US Patent 7,196,142 (March 27, 2007) L. Wang et al., US Patent 7,141,540 (November 28, 2006) H. Dai et al., US Patent Application 2006-0275371 (December 7, 2006)

O

H HN

NH S

H

Title: Heterofunctional Copolymers of Glycerol and Polyethylene Glycol, Their Conjugates and Compositions Author:

F. Ignatious, US Patent 7,196,145 (March 27, 2007)

Assignee:

SmithKline Beecham Corporation (Philadephia, PA)

SIGNIFICANCE Block- and copolymers consisting of ethylene oxide and glycidol were prepared anionically containing an d-hydroxy butyric acid terminus. The acidic terminus was then converted into a-succinimidyl and conjugated with the protein, Grob-t, and the lipid, di-stearoyl phosphatidyl-ethanolamine.

REACTION OH

OH O O

i Note 1

ii

O HO

O

O O

a

O

OH O

O N

O b

O

O

O O

iii

O

O a

b

iv

OH O

OH

OH

O

O t-Grob-HN

O O

i: ii: iii: iv: 48

O

O a

OH

b

Di-stearoyl phosphatidyl

O

OH

O

H N

O

O

O

4-Hydroxy butyric acid-sodium salt, potassium, glycidol, THF N,N0 -Dicyclohexyl carbodiimide, N-hydroxysuccinimide, CH2Cl2 Grob-t, Dulbeccu’s phosphate, hydrochloric acid Di-stearoyl phosphatidyl-ethanolamine, triethylamine, CCl3H

O a

b

Experimental

49

EXPERIMENTAL 1. Preparation of a-Carboxyl-d-Hydroxyl Poly(Ethylene Oxide-blockPolyglycidol) A reactor was charged with 4-hydroxy butyric acid-sodium salt (0.045 mol) and potassium (0.046 mol) in 400 ml of THF, refluxed 12 hours, and transferred to a high-pressure reactor. The reactor temperature was lowered to 10 C and treated with 95 ml of ethylene oxide using a stainless steel capillary and the solution stirred at 50 C for 24 hours. Glycidol previously dissolved in THF was slowly added through a stainless steel capillary, and the solution was stirred at 50 C for 12 hours. The reactor was cooled, and the contents were poured into 5 ml 35% hydrochloric acid whereupon KCl precipitated. The solution was filtered. Then the filtrate, was precipitated in cold 2-propanol containing 20% hexanes and a light yellow precipitate was isolated. The dried residue was dissolved in 500 ml distilled water and extracted with CH2Cl2 to remove the unreacted initiator. After removal of the solvent, the product was washed twice with water and isolated.

2. Preparation of d-Hydroxy-a-Succinimidyl Poly(Ethylene Oxide-block-Polyglycidol) A reactor was charged with the Step 1 product (0.011 mol), N,N0 -dicyclohexylcarbodiimide (0.0176 mol), and N-hydroxysuccinimide (0.0176 mol) dissolved in 150 ml of CH2Cl2 and then stirred overnight at ambient temperature. A cloudy heterogeneous white formed, which was removed by filtration and the filtrate concentrated. The residue was precipitated in cold diethyl ether and the product isolated after recrystallization with ethanol.

3. Conjugation of d-Hydroxy-a-Succinimidyl Poly(Ethylene Oxide-block-Glycidol) to Grob-t The Step 2 product was added to a 2.5 mg/ml solution of Grob-t in Dulbeccu’s phosphate buffered at pH 7.0 at a molar ratio of the Step 2 product/protein 2:1, 4:1, or 10:1, respectively. The reaction was stirred for 3 hours at 40 C and quenched with 0.5 M glycine, and then the pH was lowered to 4.5 with 3 M of hydrochloric acid. The conjugate was isolated after purification by diafiltration. 4. Conjugation of d-Hydroxy-a-Succinimidyl Poly(Ethylene Oxide-block-Polyglycidol) to a Lipid The Step 2 product (0.8 mmol) dissolved in CCl3H was treated with di-stearoyl phosphatidyl-ethanolamine (0.70 mmol) containing triethylamine (1.4 mmol) and heated to 40 C to 45 C for 2 hours. The conjugate was isolated after purification by diafiltration.

50

Heterofunctional Copolymers of Glycerol and Polyethylene Glycol

DERIVATIVES Poly(ethylene oxide-co-glycidol) was also prepared.

NOTES 1. In a subsequent investigation by the author [1], the aldehyde-terminated Step 1 analogue was prepared and used as a conjugate with selected biomolecules.

OH O

OH

O H

O O

O

a

(I)

O

OH b

2. Miyanaga [2] prepared moderate molecular weight polyglycidol ethers, (II), by polymerizing the corresponding glycidol ether with samarium triisopropoxide, samarium tris(tetramethyl heptanedionate), and yttrium tris(tetramethyl heptanedionate) with methyl aluminoxane. R OH CH3 Steryl CH2C8F17

O a

O

(II)

R

a 760 700 820 250

3. Polyglycidol containing cyanoethyl, (III), trimethylsilylacetyl, and cyanobenzoyl termini were prepared by Sata [3] and used as a component in ionconductive polymer electrolyte compositions.

CN

NC

O

O

(III)

aO

CN

References 1. F. Ignatious et al., US Patent Application 2005-0048650 (March 3, 2005) 2. S. Miyanaga et al., US Patent 6,906,167 (June 14, 2005) and US Patent 6,800,723 (October 5, 2004) 3. T. Sato, US Patent 6,472,106 (October 29, 2002) and US Patent 6,469,107 (October 22, 2002)

Title:

Polyalkylene Glycol Acid Additives

Author:

P. S. Bailon et al., US Patent 7,193,031 (March 20, 2007)

Assignee:

Hoffmann-La Roche, Inc. (Nutley, NJ)

SIGNIFICANCE A new class of activated biological conjugates has been prepared. Methoxy polyethylene glycol having a molecular weight of 2000 daltons was converted into the corresponding valeric acid succinimidyl ester then conjugated with AZT, T-20 polypeptide, and human erythropoietin. These conjugates materials produced biologically active agents useful in pharmaceutical applications.

REACTION H3CO

iv Note 1 H3CO

O

O

i

OH

O

H3CO

O

20

O

O O

O

O

O

20

O

iii H3CO

N

OC2H5

20

O

ii

O O

O 20

O

OH O

O HN N

O H3CO

i: ii: iii: iv:

O

O 20

O

O O

Toluene, ethyl-5-bromovalerate Sodium hydroxide N-hydroxy-succinimide, dicyclohexylcarbodiimide 30 -Azido-30 -deoxy-thymidine, 1-hydroxybenzotriazole, (4-dimethylamino)pyridine, dicyclohexylcarbodiimide

51

52


EXPERIMENTAL 1.

Preparation of Methoxy-Polyethylene Glycol Valeric Ethyl Ester

A reactor was charged with polyethylene glycol (0.5 mol; Mn 10,000), and treated with 50 ml of toluene, and azeotropically dried by refluxing for 2 hours. The resulting mixture was dissolved in 30 ml of THF and treated dropwise with sodium hydride (5 mmol) dissolved in 20 ml of THF and refluxed overnight. This mixture was then treated with ethyl-5-bromovalerate (5 mmol) and refluxed overnight and concentrated. The residue was precipitated by the addition of 2-propanol/diethyl ether, 1:1, and then filtered to yield 4.5 g of isolated product. 2.

Preparation of Methoxy-Polyethylene Glycol Valeric Acid

The Step 1 product (4 g) was dissolved in 100 ml of 1 M NaOH and stirred at ambient temperature overnight. The pH of the mixture was adjusted to 2.5 using 6 M hydrochloric acid; the mixture extracted using 50 ml, 40 ml, and 30 ml of CH2Cl2, dried with Na2SO4, and concentrated. The concentrate was precipitated in diethyl ether, and 3 g of product were isolated. 1

H-NMR (d6-DMSO) d 1.50 ppm (q, 2H, –CH2CH2–COOH); 2.21 ppm (t, 2H, –CH2CH2–COOH); 3.21 ppm (s, –OCH3); 3.5 ppm (s, –O–CH2CH2–O–).

3. Preparation of Methoxy-Polyethylene Glycol Valeric Acid Succinimidyl Ester The Step 2 product (0.2 mmol) was dissolved in 10 ml of CH2Cl2 and treated with N-hydroxy-succinimide (0.41 mmol) and dicyclohexylcarbodiimide (0.42 mmol). The mixture was stirred overnight at ambient temperature and then filtered and concentrated. The residue was precipitated in 2-propanol/diethyl ether, 1:1, and filtered to yield 1.6 g of isolated product. 1

H-NMR (d6-DMSO) d 1.58 1.67 ppm (m, 4H, –CH2CH2CH2–COO–); 2.69 ppm (t, 2H, –CH2CH2CH2– COO–); 2.81 ppm (s, 4H, NHS); 3.21 ppm (s, –OCH3); 3.5 ppm (s, –O–CH2CH2–O–).

4.

Preparation of PEG-AZT Conjugate

The Step 3 product (0.02 mmol) was dissolved in 2 ml of DMF and treated with 30 -azido30 -deoxy-thymidine (0.04 mmol), 1-hydroxybenzotriazole (0.04 mmol), 4-dimethylaminopyridine (0.042 mmol), and dicyclohexylcarbodiimide (0.046 mmol) and stirred overnight at ambient temperature. The mixturewas filtered, concentrated, precipitated in 2-propanol/diethyl ether, 1:1, and 0.17 g product was isolated. 1

H-NMR (d6-DMSO) d 1.18 ppm (m, 3H, H1); 1.51 ppm (m, 2H, H9); 2.23 ppm (m, 1H, H4); 2.37 ppm (t, 2H, H8); 3.21 ppm (s, H12); 3.5 ppm (s, H11). 4.2 ppm (m, 1H, H5); 6.12 ppm (m, H3, H6); 7.45 ppm (s, 1H, H2); 11.35 ppm (br, 1H, H10)

Notes

53

DERIVATIVES Two linear derivatives were prepared using the Step 4 product: H3CO

O

O

O

G = T-20 polypeptide, human erythropoietin

G

20

O

One branched derivative was also prepared.

H3CO

O 20 O

H3CO

O

NH

O

20

O

H N

O

N

O O

NOTES 1. In subsequent investigations by the author [1] and Ley [2] the Step 4 product was used as a conjugate for the granulocyte colony stimulating factor and Kunitz domain polypeptides, respectively. 2. In other investigations by the author [3–5] an aldehyde terminated Step 4 analogue (I) was prepared and used as conjugates for T-20 polypeptide, human erythropoietin, and T1249 polypeptide, respectively.

H3CO

O

O

O

CHO

20

(I) 3. A blended composition for facilitating delivery of a biologically active conjugated material was prepared by Kabanov [6] and consisted of a block copolymer of ethylene oxide and acrylic acid salt of cetylpyridinium bromide, (II).

O 176

O

186

O

(II)

N 14

4. Oh [7] prepared biodegradable lactide derivatives, (III), for conjugation with biologically active agents for use as drug delivery agents.

54


O O

HO

O O

a

O

O

O O

O

NO2

(III)

5. Roberts [8] prepared polyethylene glycol 2-pyridylthioester derivatives, (IV) for conjugating with a-amine polypeptides.

O H3CO

O

O a

S

(IV)

References 1. 2. 3. 4. 5. 6. 7. 8.

P.S. Bailon, US Patent Application 2005-0196378 (September 8, 2005) A.C. Ley, US Patent Application 2007-0041959 (February 22, 2007) P.S. Bailon et al., US Patent 7,049,415 (May 23, 2006) P.S. Bailon et al., US Patent 6,583,272 (June 24, 2003) P.S. Bailon et al., US Patent Application 2004-0171542 (September 2, 2004) A.V. Kabanov et al., US Patent 7,169,411 (January 30, 2007) J.E. Oh et al., US Patent 7,163,698 (January 16, 2007) J.H. Roberts et al., US Patent 7,078,496 (July 18, 2006)

N

Title:

Thermosensitive Biodegradable Copolymer

Author:

K.-Y. Chang et al., US Patent 7,179,867 (February 20, 2007)

Assignee:

Industrial Technology Research Institute (Hsinchu, TW)

SIGNIFICANCE A method for increasing the biodegradability of low cytotoxic poly(ethylene glycol-b(lactide-co-glycolide)) derivatives is described. The block copolymers are thermosensitive and can be easily implanted into the human body through injection for timed release of biologically active agents.

REACTION O O

O

O

O

i O

H3CO

O

Ob

a

OH

ii

c

H3CO

O

O

a

O b

O

O

c

11

O

i: Lactide, methoxypolyethylene glycol, tin octanate ii: Lauric acid, dicyclohexylcarbodiimide, CH2Cl2, CHCl3

EXPERIMENTAL 1.

Preparation of Poly(Ethylene Glycol-b-(Lactide-co-Glycolide))

A reaction vessel was heated under nitrogen until the temperature reached 110 C and then treated with lactide (50.0 g), glycolide (11.36 g), and methoxypolyethylene glycol (24.02 g). After the monomers had melted, the contents were treated with 0.05% tin octanate while the temperature slowly increased to 160 C for 9 hours; the vessel was then cooled to ambient temperature. The solid was dissolved in 80 ml of CH2Cl2, then poured into n-hexane/ether, 9:1, respectively, and stirred for 3 hours. The solution was next separated into two phases. The upper liquid was discarded, the bottom liquid was washed three times with n-hexane/diethyl ether, dried, and the product was isolated. 55

56

Thermosensitive Biodegradable Copolymer

2. Preparation of Poly(Ethylene Glycol-b-(Lactide-co-Glycolide)) Lauric Ester Separate solutions of lauric acid (1.53 g) and dicyclohexylcarbodiimide (1.58 g) were prepared by dissolving each into 30 ml and 20 ml of CH2Cl2, respectively. The two solutions were mixed and stirred for 30 minutes and then added to the Step 1 product (10 g) dissolved in 50 ml of CHCl3. This mixture was treated with triethylamine (1.5 g) and stirred for 24 hours. The mixture was filtered and washed with n-hexane/diethyl ether, and the product was isolated after drying. 1 1

H-NMR (CCl3D) d 1.58 (d, J ¼ 6.5 Hz, H-4), 3.39 (s, –OCH3), 4.29 (m, H-1,2), 4.80 (m, H-5), 5.14 (m, H-3) H-NMR (CCl3D) d 0.86 (t, J ¼ 6.8 Hz, H-8), 1.23 (m, H-7), 1.58 (d, J ¼ 6.5 Hz, H-4), 2.38 (m, H-6), 3.39 (s, –OCH3), 4.29 (m, H-1,2), 4.80 (m, H-5), 5.14 (m, H-3)

DERIVATIVES The cholic acid analogue of the Step 1 product was also prepared. OH

O O

H3CO

a

Ob

c

O

O

O HO

OH

TESTING Gel Formation Data collection were correlated with viscosity, time, thermocouple temperature, and rheometer torque. The rotation speed of the rheometer was adjusted so that torque value fell between 80% to 100%. The gel formation time was defined as the time needed for a sample to increase its viscosity up to 10000 cP from its starting viscosity. Viscosity testing results are provided in Table 1. TABLE 1. Time (s) 8 9 10 11 12 13

Gel formation for the Step 2 product at varying times and temperatures. Temperature ( C)

15 wt% Solution Viscosity (cp)



5 10 13 15 18 20

Fluid 7,500 17,000 — — —

Fluid Fluid Fluid Fluid 7,500 >25,000

Fluid Fluid Fluid Fluid 5,000 >25,000

Notes

57

NOTES 1. Amphiphilic block copolymers consisting of polylactic acid or poly(lactic acidb-glycolic acid) terminated with tocopherol or cholesterol were prepared by Seo [1] and used as drug delivery agents for PaclitaxelÒ. 2. Negatively charged amphiphilic block copolymers, (I), prepared by Seo [2] were effective as cationic drug carriers and provided the advantages of increased blood concentration and improved drug stability. Stable polymeric micelle-type drug compositions were prepared by Seo [3].

O H3CO

O

O a

Ob

X = PO 3- Na+ = SO 3- Na+

X

c

O

(I) 3. Thermosensitive block terpolymers consisting of poly(ethylene oxide-b-glycolide-b-dl-lactide) were prepared by Piao [4] and used as drug delivery agents for insulin. 4. Block terpolymers prepared by Cheng [5] consisting of poly(N-isopropyl acrylamide-b-polyethyleneoxide-b-N-isopropyl acrylamide), (II), were effective as thermally reversible gels and used as subcutaneous implants, joint or tissue spacers, and biological filler for wrinkles or cosmetic implants. Methacrylamide analogues were prepared by Gutowska [6].

O

a HN

O

O 113

NH

a

(II)

References 1. 2. 3. 4. 5. 6.

M.H. Seo et al., US Patent Application 2005-0201972 (September 15, 2005) M.H. Seo et al., US Patent 6,890,560 (May 10, 2005) M.H. Seo et al., US Patent 7,217,770 (May 15, 2007) A-Z. Piao et al., US Patent 7,135,190 (November 14, 2006) Y.-L. Cheng et al., US Patent 7,160,931 (January 9, 2007) A. Gutowska, US Patent 6,979,464 (December 27, 2005)

Title: Polyamide Graft Copolymers Author:

A. B. Brennan et al., US Patent 7,169,853 (January 30, 2007)

Assignee:

University of Florida Research Foundation, Inc. (Gainesville, FL)

SIGNIFICANCE Polyamide copolymers containing a macromolecular graft substituent were prepared by condensing 4-amino-benzoic acid or a mixture of 1,4-phenylene diamine and adipic acid with 33%, 66%, and 90% S-(poly(n-butylacrylate)cysteine macromonomer. A second macromolecular monomer, S-(poly(methyl methacrylate)-cysteine, was also prepared and free radically copolymerized with perfluoromethyl methacrylate.

REACTION O

O H2N

O

i O

n-C4H9

N H

OH S

O

ii

Poly(butyl acrylate)

N H a S


0

i: 2,2 -Azobisisobutyronitrile, cysteine, THF, hydrochloric acid ii: Triphenylphosphite, lithium chloride, pyridine, N-methyl-pyrrolidinone

EXPERIMENTAL 1.

Preparation of S-(Poly(n-Butyl Acrylate)-Cysteine Macromonomer

The synthesis of poly(butyl acrylate) in the presence of cysteine was carried out using THF, ethyl alcohol, and water where the molar ratio of butyl acrylate monomer/ cysteine/azobisisobutyronitrile was 1000:30:1, respectively. The mixture was then refluxed for 6 hours at 65 C while under constant stirring. After cooling the cysteinemodified product consisted of a white precipitate dispersed within poly(butyl acrylate). The precipitate was isolated from the polymer by dissolving the poly(butyl acrylate) in THF and filtering. 58

Notes

59

2. Preparation of Poly(4-Amino-Benzoic Acid-co-(Cysteine-g-Poly (n-Butyl Acrylate)) The Step 1 product (1.37 g; Mn 26,000 daltons), 4-aminobenzoic acid (2.24 mmol), triphenylphosphite (5 mmol), and LiCl (0.09 g) were dissolved in 30 ml N-methylpyrrolidinone/pyridine solution, 80:20, and heated to 100 C for 4 hours. The reaction mixture was then precipitated in an excess of water/methanol, 1:1, filtered, and washed with methanol. The material was dried overnight under vacuum at 40 C, and the product was quantitatively isolated.

DERIVATIVES TABLE 1. Selected comonomers reacted with cysteine macromolecular comonomer and corresponding macromolecular content. Cysteine Macromolecular Component Poly(butyl acrylate) Poly(butyl acrylate) Poly(butyl acrylate) Poly(butyl acrylate) Poly(methyl methacrylate)

Macromolecule Content In Copolymer (wt%)

Comonomer(s) 4-Amino-benzoic acid 4-Amino-benzoic acid 1,4-Phenylene diamine and adipic acid 1,4-Phenylene diamine/adipic acid Perfluoromethyl methacrylate

33 66 66 90 65

Note: Polymers derived from 4-amino-benzoic acid were insoluble in all solvents except concentrated sulfuric acid. Elemental analysis for all experimental agents supplied by author.

NOTES 1. Polylysine-g-histidine derivatives, (I), prepared by Pack [1] were effective as biocompatible endosomolytic delivery agents. NH2

O

H N

b = 10% –100%

b

O a

N N H

(I)

HN NH2

60

Polyamide Graft Copolymers

2. Kaneko [2] prepared compatibilizing agents consisting of methacrylate, (II), and styryl, (III), macromolecules. These materials were polymerized using titanium-based Ziegler–Natta catalysts.

O O

(II)

O

R

R

R = Polyethylene Polypropylene Poly(ethylene-co-propylene)

(III) 3. TEMPO-modified poly(ethylene-co-propylene-g-maleic anhydride), (IV), and poly((ethylene-co-1-decene)-g-alkylacrylates), (V), were prepared by Matsugi [3] and used as polymer blend compatibilizing agents. a

b

O

O b

a

O

O

O

O N

N

7

R O

c O

(V) (IV)

References 1. D.W. Pack et al., US Patent Application 2001-0006817 (July 5, 2001) 2. H. Kaneko et al., US Patent 7,067,587 (June 27, 2006) 3. T. Matsugi et al., US Patent 7,022,763 (April 4, 2006)

R = CH3 CH(CH 3)CH2CH3

Title: Bioerodible Poly(Ortho Esters) from Dioxane-Based Di(Ketene Acetals) and Block Copolymers Containing Them Author:

J. Heller et al., US Patent 7,163,694 (January 16, 2007)

Assignee:

A.P. Pharma, Inc. (Redwood City, CA)

SIGNIFICANCE Bioerodible poly(ortho ester) copolymers containing hydrophilic and hydrophobic blocks have been prepared from di(ketene acetals) and oligomeric diols. These materials form micelles in aqueous solution making them useful as hydrophobic encapsulation agents or as bioerodible matrices for the sustained release of medicaments.

REACTION C2H5

HO

O

C2H5

C2H5 OH

HO

i

OH

C2H5

C2H5 O

O

ii

O

O

O

O

O

O

C2H5 C2H5 O

C2H5 C2H5 O O 3

O

O

O

O

iii

O O

C2H5 O

O

3

a

O

i: Toluene, di(trimethylolpropane), acrolein diethyl acetal, pyridinium p-toluenesulfonate, potassium t-butoxide ii: Pentane, iron pentacarbonyl, triethylamine iii: Triethylene glycol, triethylene glycol monoglycolide, THF, salicylic acid, triethylamine

61

62

Bioerodible Poly(Ortho Esters) from Dioxane-Based Di(Ketene Acetals)

EXPERIMENTAL 1.

Preparation of Di[(5-Ethyl-2-Vinyl-[1,3]Dioxan-5-yl)Methyl]Ether

A reactor containing 300 ml of toluene was charged with di(trimethylolpropane) (120 mmol), 45.6 ml of acrolein diethyl acetal, and pyridinium p-toluenesulfonate (6 mmol), and then refluxed for 4 hours and cooled to ambient temperature. The mixture was further treated with potassium t-butoxide (6 mmol), and then concentrated under reduced pressure; the residue was distilled in a Kugelrohr apparatus to give 91% yield of the two crude isomers. The crude product was purified by chromatography using Silica Gel 60 and eluting with EtOAc/heptane, 20:80, and 71% yield of di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]ether isolated as a light yellow oil. This material was re-purified by a second chromatographic separation using Silica Gel 60 while eluting with EtOAc/heptane, 10:90, and the product was isolated in 42% yield. 2.

Preparation of Di[(5-Ethyl-2-Ethylidene-[1,3]Dioxan-5-yl)Methyl]Ether

The Step 1 product (43.9 mmol) was added to a photochemical reactor containing 220 ml pentane and degassed by refluxing vigorously for 20 minutes and then treating with iron pentacarbonyl (0.87 mmol). The mixture was further refluxed and irradiated for 1 hour until no evidence of vinyl signals were detected using 1 H-NMR. It was cooled to ambient temperature, treated with 0.5 ml triethylamine, and sparged with dry air for 4 hours. This mixture was concentrated under reduced pressure, distilled in a Kugelrohr apparatus, and a 63% yield of product was isolated as a colorless oil. 3.

Preparation of Poly(Ortho Esters) Containing Triethylene Glycol

A reactor was charged with the Step 2 product (3.5 mmol), triethylene glycol (4.95 mmol), triethylene glycol monoglycolide (0.05 mmol), and 5 ml of THF. The mixture was then polymerized using salicylic acid solution in THF as catalyst. After 30 minutes 0.1 ml of triethylamine was added, and the product was isolated in 99% yield after the mixture was concentrated. MS (observed): 363, 345 for C18H35O7 and C18H33O6 MS (calculated) 345 for C18H33O6

DERIVATIVES C2H5 C2H5 O

C2H5 C2H5 O

A

O O

O

O

O

3

O

a

Notes

63

TABLE 1. Selected poly(ortho ester) copolymers having bioerodible matrices used for the sustained release of medicaments. Entry

A

3 4 6

Mn (daltons)

Viscosity (poise)

5,700 4,700 11,400

78,000 32,000 —

—

—

O–(CH2)10–O (OCH2CH2)3

O O (OCH2CH2)45

7

Note: Only limited characterization data supplied by author.

NOTES 1. In other investigations by the author [1] bioerodible block copoly(ortho esters), (I), consisting of the Step 2 produce and polyethylene oxide were prepared and used as controlled drug release agents.

C2H5 C2H5 O

C2H5 C2H5 O O

O

O

O

45 O

45 a

(I)

2. Ng [2,3] prepared bioerodible copoly(ortho esters) consisting of the Step 2 product with monomethyl polyethylene glycol ether termini and 1,4-cyclohexanedimethanol and either an a-hydroxy carboxylic acid, (II), or N-methyl-diethanol amine (III), for use as bioerodible matrices for the sustained release of biologically active agents. Other dioxalane bioerodible analogues were prepared by Ng [4] in an earlier investigation. C2H5 C2H5 O H3CO

O

45

O

O C2H5 C2H5 O

O O

O

(II)

O

O

3O

a

64

Bioerodible Poly(Ortho Esters) from Dioxane-Based Di(Ketene Acetals)

C2H5 C2H5 O H3CO

O

45

O

O

C2H5 C2H5 O N O

O

O

(III)

O

a

3. Biocompatible ortho aromatic polyanhydrides, (IV), prepared by Uhrich [5] were used in drug delivery systems and as scaffolding implants for tissue reconstruction.

O

O

O

O O

aO

O

O

b

a = 6, 8

(IV)

References 1. J. Heller et al., US Patent 7,045,589 (May 16, 2006) and US Patent Application 2006-0155101 (July 13, 2006) 2. S.Y. Ng et al., US Patent Application 2003-0152630 (August 14, 2003) 3. S.Y. Ng et al., US Patent Application 2003-0138474 (July 24, 2003) and US Patent 6,946,145 (September 20, 2005) 4. S.Y. Ng et al., US Patent 6,822,000 (November 23, 2004) 5. K.E. Uhrich,US Patent 7,122,615 (October 17, 2006) and US Patent Application 2004-0096476 (March 20, 2004)

Title:

Water-Soluble Polymer Alkanals

Author:

A. Kozlowski US Patent 7,157,546 (January 2, 2007)

Assignee:

Nektar Therapeutics AL Corporation (Hunstville, AL)

SIGNIFICANCE A high yielding method for preparing methoxypolyethylene glycol alkylaldehydes through an acetal intermediate is described. Drug delivery conjugates were then prepared from these aldehydes by condensing with biologically active peptides or proteins such as IFNs-a, b, and j, factors VII, VIII, and IX, insulin, or erythropoietin.

REACTION H

O

H3CO

O

750

OC2H5

i

O

H3CO

O

O

OC2H5

750

ii O

H3CO

O

O

O 750

NH Erythropoietin

iii Note 1

H3CO

O

O

O 750

H

i: Toluene, butylated hydroxytoluene, potassium t-butoxide, t-butanol, 4-chlorobutyraldehyde diethyl acetal, potassium bromide, CH2Cl2, diethyl ether ii: Water, phosphoric acid, sodium chloride, sodium hydroxide iii: Erthropoietin, sodium acetate, sodium cyanoborohydride

EXPERIMENTAL 1. Preparation of Methoxypolyethylene Glycol-Butyraldehyde Diethyl Acetal A mixture consisting of methoxypolyethylene glycol (30,000 daltons; 60% solution in toluene; 3.30 g), 30 ml of toluene, and butylated hydroxytoluene (0.004 g) were azeotropically dried by distilling off toluene under reduced pressure. Dried methoxypolyethylene glycol was then dissolved in 15 ml toluene and treated with 4 ml of 1.0M potassium t-butoxide in t-butanol, 4-chloro-butyraldehyde diethyl acetal (0.00277 mol), and potassium bromide (0.05 g). The mixture was stirred overnight 65

66


at 105 C. The mixture was filtered, concentrated, and the crude was product was dissolved in 20 ml of CH2Cl2. The product was isolated by precipitation in 300 ml diethyl ether, and 1.92 g was isolated with a purity of 95%. 2.

Preparation of Methoxypolyethylene Glycol-Butyraldehyde

A mixture of the Step 1 product (1.0 g), 20 ml of deionized water, and 5% phosphoric acid was stirred for 3 hours at ambient temperature and then treated with sodium chloride (1.0 g) and sufficient 0.1M sodium hydroxide to obtain a pH of 6.8. The product was extracted three times with 20 ml of CH2Cl2, dried with MgSO4, concentrated, and 82 g of product were isolated. 1

H-NMR (d6-DMSO): d 1.09 ppm (t, CH3–C–) 1.52 ppm (m, C–CH2–CH2–), 3.24 ppm (s, –OCH3), 3.51ppm (s, PEG backbone), 4.46 (t, –CH, acetal)

3.

Preparation of Methoxypolyethylene Glycol-Butyl Amine-Erythropoietin

Erythropoietin (2 mg) was dissolved in 1 ml of 0.1 mM sodium acetate with a pH of 5, and then treated with the Step 2 product (10 mmol) and cyanoborohydride and stirred for 24 hours at 4 C. Confirmation of N-terminal modification was determined by peptide mapping. Increasing the ratio of methoxyPEG-butyraldehyde to eythropoietin increased the degree of erythropoietin incorporation. 1

H-NMR (d6-DMSO): d 1.75 ppm (p, –CH2–CH2–CHO–) 2.44 ppm (dt, –CH2–CHO), 3.24 ppm (s –OCH3), 3.51 ppm (s, PEG backbone), 9.66 ppm (t, –CHO)

NOTES 1. In an earlier investigation by the author [1] 1-benzotriazolyl carbonate esters of poly(ethylene glycol), (I), were prepared and used as drug delivery templates for lysine and lysozyme.

H3CO

O

O

O a

(I)

O O

N N N

a = 200–4000

Notes

67

2. A drug delivery template consisting of methoxypolyethylene glycol containing succinimidyl esters, (II), was prepared by Harris [2] and used to form amides from the amine portion of proteins.

O O O

H3CO

O a

O

N O

H N

O O

O O

(II)

O

N

O

3. Bhatt [3] prepared antineoplastic agents consisting of poly-L-glutamic acid-camptothecin conjugates, (III) and (IV), as a method for improving the limited solubility of 20(S)-camptothecin and analogues in aqueous medium.

Poly-L-glutamic acid

O N N

O O

O

O N N

O

O HO

O

Poly-L-glutamic acid

(III)

O

O

(IV)

4. Polydipeptides consisting of glutamic acid with alanine, asparagine, (V), glycine, or glutamine were prepared by Xu [4] and used as biodegradable polymeric carriers to which was covalently attached the cytotoxic agent, PaclitaxelÒ .

68


CO2H

O H N

N H

a

O

O

Biodegradable dipeptide

O

O O O

NH

OH

O O

O HO

HO O

O O

(V)


A. Kozlowski, US Patent 7,101,932 (September 5, 2006) J.M. Harris et al., US Patent 7,030,278 (April 18, 2006) R. Bhatt et al., US Patent 7,153,864 (December 26, 2006) J. Xu,US Patent Application 2001-0041189 (November 15, 2001)

Paclitaxel(R)

Title: Biodegradable Aliphatic Polyester Grafted with Poly(Ethylene Glycol) Having Reactive Groups and Preparation Method Thereof Author:

J.-K. Park et al., US Patent 7,151,142 (December 19, 2006)

Assignee:

Korea Advanced Institute of Science and Technology (Daejeon, KR)

SIGNIFICANCE Poly[lactide-g-butene)-g-poly(ethylene glycol)] has been prepared by initially copolymerizing L-lactide and 1,2-epoxy-5-hexene forming poly(lactide-g-butene) containing pendent 1-butene, then post-reacting with poly(ethylene glycol) methacrylate. The product was both hydrophilic and biodegradable and used as a drug delivery agent and in biochips.

REACTION O

O

i

O

O

O

O

O O

a b

ii

O O O

O O

O

a b O O

c OH

i: 1,2-Epoxy-5-hexene, toluene, triethylaluminum pentahydrate ii: Poly(ethylene glycol) methacrylate, THF, 2,20 -azobisisobutyronitrile 69

70

Biodegradable Aliphatic Polyester Grafted with Poly(Ethylene Glycol)

EXPERIMENTAL 1.

Preparation of Poly(Lactide-g-Butene)

Three 500-ml reflux flasks were each charged with a mixture of L-lactide (5.88 g) and 1,2-epoxy-5-hexene (4.12 g) dissolved in 50 ml of toluene, and then treated with triethylaluminum pentahydrate (98.6 mg). Each vessel was then sealed and heated to 90 C for 12, 24, and 36 hours, respectively, and the contents were precipitated in diethyl ether. The polymers obtained were washed with diethyl ether three times and dried in a vacuum oven for 1 day. The polymers were shown to have a double bond content of 7.0, 7.5, and 8.1 mol%, respectively, with a Mn of roughly 10,000 daltons. 2.

Preparation of Poly[Lactide-g-Butene)-g-Poly(Ethylene Glycol)]

Three 500-ml flasks were each charged with a mixture consisting of the Step 1 product (1 g) having an 8.1 mol% double bond content, poly(ethylene glycol) methacrylate (3.6 g; Mn ¼ 360 daltons), and 50 ml of THF. The flasks were placed into a bath heated to 70 C. Each mixture was then treated with 2,20 -azobisisobutyronitrile (2.7 mg, 9 mg, and 18 mg, respectively) and heated 25 hours and precipitated in methanol. The polymers were then washed three times with methanol, dried, and the poly(ethylene glycol) content determined to be 16.6, 18.4, and 7.0 mol%, respectively. Polyethylene glycol incorporation scoping reactions are provided in Table 1.

RESULTS TABLE 1. Scoping reactions to determine the effect of 2,20 -azobisisobutyronitrile and reaction times on the incorporation of poly(ethylene methacrylate) into the Step 1 product, poly(lactide-g-butene). Entry 1 2 3 4 5 6 7

Butene Content (mol%) 7.0 7.0 7.5 7.5 8.1 8.1 8.1

Reaction Time (h)

AIBN (mg)

Graft Ratio of PEG (mol%)

48 48 48 48 25 25 25

8 3.0 8.0 3.0 2.7 9.0 18.0

9.5 10.0 19.5 15.0 16.6 18.4 7.0

NOTES 1. Arnold [1] prepared the hydrophilic and bioabsorbable copolyester, poly (monostearoyl glycerol-co-succinate) (I), which was used in the sustained release of RisperidoneÒ.

Notes

71

O O

16

O

O a

(I)

O

2. Wilson [2] prepared biodegradable copolymers that were hydrolysable at pH > 10, consisted of ethylene and selected monomers, (II–V), and were used as components in disposable syringes. O

O O Si O O

O

Si

O

(III)

(II)

O O

(IV)

(V)

3. Polymer films prepared by Hayes [3] consisting of bis(2-hydroxyethyl)terephthalate, lactic acid, tris(2-hydroxyethyl)trimellitate, ethylene glycol, poly (ethylene glycol), and the colorant titanium dioxide were both biodegradable and compostable. 4. Biodegradable polymers, (VI), containing the hydrophobic biodegradable polyester block and hydrophilic polyethylene glycol block segment were prepared by Piao [4] and used as drug release agents. The gel matrix erosion rates reflected the hydrophobic/hydrophilic content, monomer ratios, and molecular weights. O O

H

O

O O

a

b

O

O

O

(VI) References 1. 2. 3. 4.

b O

c

S. Arnold et al., US Patent 7,034,037 (April 25, 2006) R.B. Wilson Jr. et al., US Patent 7,037,992 (May 2, 2006) R.A. Hayes, US Patent 7,144,972 (December 5, 2006) A.-Z. Piao et al., US Patent 7,018,645 (March 28, 2006)

OH a

Title: Coumarin End-Capped Absorbable Polymers Author:

T. Matsuda et al., US Patent 7,144,976 (December 5, 2006)

Assignee:


SIGNIFICANCE Poly(lactone-co-trimethylene carbonates) containing photocurable coumarin ester end groups have been prepared which are crosslinkable upon irradiation with ultraviolet light by a [2 þ 2] cycloaddition. These materials are useful in the preparation of in vivo implants.

REACTION O HO

O

O

O O

C2H5O

i

O

O O a

O

O

ii

O O

O

O O a

O

O

O

iv Note 1

O

Cl

O O

O

b cO

O

O

O O O

O

O

O O

O O

a

O

i: Ethyl bromoacetate, potassium carbonate, acetone ii: 1,4-Dioxane, sodium hydroxide, hydrochloric acid iii: Thionyl chloride 72

O

iii

O O

b cO

O

v

O

HO

b

c

O

O

O

Experimental

73

iv: Poly(e-caprolactone-co-trimethylene carbonate), pyridine, CH2Cl2 v: CH2Cl2

EXPERIMENTAL 1.

Preparation of 7-Coumarin Ethyl Acetate Ether

A mixture consisting of 7-hydroxycoumarin (0.125 mol), K2CO3 (0.179 mol), ethyl bromoacetate (0.150 mol), and 450 ml of acetone were refluxed for 2 hours and then filtered. The mixture was concentrated, the residue re-crystallized from ethanol, dried, and the product was isolated in 89% yield. 1

HNMR (270 MHz, DMSO-d6) d 1.18 (3H, triplet, J ¼ 8.1 Hz), 4.16 (2H, quartet, J ¼ 8.1 Hz), 4.91 (2H, singlet), 6.28 (1H, doublet, J ¼ 9.9 Hz), 6.96 (1H, doublet, J ¼ 2.0 Hz), 6.98 (1H, quartet, J ¼ 2.0, and 8.9 Hz), 7.61 (1H, doublet, J ¼ 8.9 Hz), 7.96 (1H, doublet, J ¼ 9.9 Hz)

2.

Preparation of 7-Coumarin Acetic Acid Ether

The Step 1 product (27.9 mmol), 280 ml of 1,4-dioxane, and NaOH (0.405 mol) were stirred overnight at ambient temperature then acidified with 12 M HCl. The mixture was extracted into a mixture of CCl3H and methanol and then concentrated by distillation under reduced pressure. The residue was re-crystallized from ethanol, and the product was isolated in 90% yield. 1

HNMR (270 MHz, DMSO-d6) d 4.83 (2H, singlet), 6.28 (1H, doublet, J ¼ 9.9 Hz), 6.95 (1H, doublet, J ¼ 2.0 Hz), 6.97 (1H, doublet, J ¼ 2.0, and 8.9 Hz), 7.62 (1H, doublet, J ¼ 8.9 Hz), 7.97 (1H, doublet, J ¼ 9.9 Hz), 13.13 (1H, s)

3.

Preparation of 7-Chlorocarbonylmethoxycoumarin

The Step 2 product (17.1 mmol) and thionyl chloride (0.277 mol) were refluxed 3 hours. Excess thionyl chloride was removed by distillation, and the crude product was isolated in 98% yield and used without additional purification. 1

HNMR (270 MHz, DMSO-d6) d 4.83 (2H, singlet), 6.28 (1H, doublet, J ¼ 9.9 Hz), 6.94(1H, doublet, J ¼ 2.0 Hz), 6.96 (1H, quartet, J ¼ 2.0, and 8.9 Hz), 7.62 (1H, doublet, J ¼ 8.9 Hz), 7.97 (1H, doublet, J ¼ 9.9 Hz)

4. Preparation of Coumarin Ester End-Capped Poly(-Caprolactone-co-Trimethylene Carbonate) A mixture consisting of poly(e-caprolactone-co-trimethylene carbonate) (0.129 mmol), the Step 3 product (1.79 mmol), pyridine (0.62 mmol), and 20.5 ml of CH2Cl2 were stirred overnight at ambient temperature. The end-capped polymer was precipitated in diethyl ether and then purified by fractionation using DMF and diethyl ether/methanol, 8:2; the product was isolated in 86% yield. FTIR (KBr, cm1) 2953, 2866, 1743, 1614, 1250, 1164, and 1036 1 HNMR coumarin groups (270 MHz, CDCl3) d 4.69 (2H, doublet), 6.26 (1H, doublet, J ¼ 9.3 Hz), 6.79 (1H, doublet, J ¼ 2.4 Hz), 6.87 (1H, quartet, J ¼ 2.4, and 8.3 Hz), 7.39 (1H, doublet, J ¼ 8.3 Hz), 7.62 (1H, doublet, J ¼ 9.3 Hz) UV Polymer equivalent weight 3.65 104 daltons

74

Coumarin End-Capped Absorbable Polymers

5. Photogelation of Coumarin Ester End-Capped Poly(-Caprolactone-co-Trimethylene Carbonate) Using Ultraviolet Light The Step 4 product (40 mg) was dissolved in 1.00 ml CH2Cl2 and 150 ml and placed onto a 14.5 mm diameter cover glass. CH2Cl2 was then removed under reduced pressure to prepare a thin film having a thickness of roughly 0.03 mm. The film was irradiated with ultraviolet light of varying intensities and times from a Hg–Xe lamp. The polymeric network or gel that formed was washed with CH2Cl2, dried under reduced pressure to constant weight, and isolated.

RESULTS TABLE 1. Effect on molecular weight of poly(-caprolactone-co-trimethylene carbonate) end capped with coumarin after a [2 þ 2] photo cycloaddition using UV irradiation. Mn Poly(e-Caprolactoneco-Trimethylene Carbonate) (daltons) 2900 4200 6100 5900

OH value (mol/g)

Mn of Post UV Cured End-Capped Poly(e-Caprolactone-co-Trimethylene Carbonate) Coumarin Ester (daltons)

8.34 104 5.88 104 3.52 104 3.55 104

3600 5100 8500 8500

NOTES 1. The preparation of poly(e-lactone-co-trimethylene carbonate) is described by the author using the procedure of Bezwada [1]. 2. The preparation of other in vivo implants using photocurable coumarin endgroups and at least one lactone monomer selected from e-caprolactone, glycolide, or DL-lactide is described by the author [2]. 3. Additional crosslinkable macromolecules are described by the author [3] in an earlier investigation. 4. Crosslinkable monomers N-[3-(7-methyl-9-oxothioxanthene-3-carboxamido)propyl]methacrylamide, (I), and poly(e-caprolactone-co-trimethylene carbonate) (II), were prepared by Chudzik [4] and used in UV photo-crosslinkable implants. O O HN

S O

(I)

Notes

75

O

O O

O

O

a

O O

O

b O c

O

O

O

O O

(II) O

5. Rhee [5] prepared crosslinkable macromolecules containing collagens, (III), and glycosamino-glycans using a bi-succinimidyl intermediate, (IV); the macromolecules were then used in biomaterial compositions.

O

Collagen–NH

S O

NH–Collagen

S

(III)

O O N

O

O

S

S

O

O

N

O O

(IV)

6. Crosslinkable bioresorbable hydrogel block copolymer compositions, (V), were prepared by Loomis [6] for implantable prostheses and as scaffolding for tissue engineering applications.

O O

a O O

(V)

b O

a = 50–300 b = 10–100

References 1. 2. 3. 4. 5. 6.

R.S. Bezwada et al., US Patent 5,468,253 (November 21, 1995) T. Matsuda et al., US Patent 7,144,976 (December 5, 2006) T. Matsuda et al., US Patent 7,105,629 (September 12, 2006) S.J. Chudzik et al., US Patent 7,094,418 (August 22, 2006) and US Patent 6,924,370 (August 2, 2005) W. Rhee, US Patent 7,129,209 (October 31, 2006) G.L. Loomis et al., US Patent 7,109,255 (September 19, 2006)

Title: Block Copolymers for Multifunctional Self-assembled Systems Author:

J. A. Hubbell et al., US Patent 7,132,475 (November 7, 2006)

Assignee:

Ecole Polytechnique Federale de Lausanne (Lausanne, CH)

SIGNIFICANCE A block copolymer effective as a controlled release agents of biologically active materials have been prepared. This agent consisted of ethylene oxide-propylene sulfide-ethylene oxide terpolymer that had been end-capped with a selected cysteinecontaining peptide. These materials resist degradation prior to reaching their intended targets because they behave as multilamellar vesicles.

REACTION

H3CO

O 16

i

OH

iv

O

H3CO

O

H3CO

O

16

S

S

16

O2 S

O

ii

O 8

25

O

H3CO

16

S

iii

O O

Note 1 iv

H3CO

O 16

S

S 25

O

Cystein-containing peptide O

8

O

i: Triethylamine, p-toluene sulfonyl chloride, CH2Cl2 ii: Potassium thioacetate, acetone iii: Sodium methoxide, methanol, propylene sulfide, poly(ethylene glycol) monoacrylate iv: Triethanolamine, HEPES buffered saline, hydrochloric acid

76

Derivatives

77

EXPERIMENTAL 1.

Preparation of Methoxypoly(Ethylene Glycol) Tosylate

Methoxypoly(ethylene glycol) (7 103 mol) was dissolved in 30 ml of CH2Cl2 and then treated with triethylamine (0.016 mol) and p-toluene sulfonyl chloride (0.0135 mol). The mixture was stirred for 24 hours at ambient temperature. The mixture was then filtered to remove precipitated triethylammonium hydrochloride, concentrated, and the product was isolated after precipitation in cold diethyl ether. 2.

Preparation of Methoxypoly(Ethylene Glycol) Thioacetate

The Step 1 product (2.22 103 mol) was dissolved in 30 ml of acetone and treated with potassium thioacetate (6.67 103 mol), it was stirred overnight at ambient temperature. The mixture was filtered, concentrated, and precipitated in cold diethyl ether. The residue was dissolved in CH2Cl2, extracted with water, dried using Na2SO4, and the product was isolated after re-precipitation in cold diethyl ether.

3. Preparation of Methoxy-Poly[Ethylene Glycol-b-Propylene Sulfide-b-(Ethylene Glycol) Monoacrylate)] The Step 2 product was dissolved in THF and treated with one equivalent of 0.5 M sodium methoxide in methanol at ambient temperature. The mixture was then treated with between 25 and 50 equivalents of propylene sulfide and polymerized for 30 minutes. It was further treated with approximately 10 equivalents of poly (ethylene glycol) monoacrylate as the end-capping agent. The reaction mixture was stirred overnight at ambient temperature and isolated by precipitation in methanol.

4. Preparation of Methoxy-Poly[Ethylene Glycol-b-Propylene Sulfide-b-(Ethylene Glycol) Monoacrylate)]-Cysteine-Containing Peptide End Functionalized The Step 3 product (230 mmol) was dissolved in HEPES buffered saline (10 mmol HEPES; 8 g/l NaCl; pH ¼ 7.4) and then treated with triethanolamine (5.3 ml/ml), and the pH adjusted to pH 8 using 6 M HCl. Cysteine-containing peptides dissolved in 5 ml of HEPES buffered saline were next added to 40 ml of the Step 3 product with stirring and incubated for 6 hours. The solution was dialyzed against pure water for 24 hours and freeze-dried. The polymer was dissolved in 5 ml of CH2Cl2, and the product was isolated after precipitation in hexane.

DERIVATIVES Only the single derivative was prepared.

78

Block Copolymers for Multifunctional Self-assembled Systems

NOTES 1. Block copolymers containing acrylate termini, (I), were prepared by Cellesi [1], and they were subjected to either a Michael-type addition or were photopolymerized and used as drug delivery agents or biomaterials.

O O

O

O

O b

a

a

O

(I)

2. Polymers, (II) and (III), containing hydrolytically susceptible segments at a physiological pH between 6.5 and 7.5 were previously prepared by the author [2] and used as viscoelastic liquids containing gel microparticles.

O O

PEG

O O

O O

a

O

2

O

(II) O S

O

O

O

O

a

O

S 2

(III)

3. Poly(ethylene glycol)-poly(glutamic acid) block copolymers containing cisdiamine-dichloroplatinum, (IV), were prepared by Kataoka [3]. The micelle diameters were roughly 22 nm, and these block copolymers were used as antineoplastic drug delivery agents.

O O

N

a = 40, 79

H N

a

5 H

CO2 Pt(NH2)(NH3)Cl2

(IV)

Notes

79

4. Ho [4] prepared nanoscale helical microstructures and channels from poly(arylTEMPO-b-L-lactide) block copolymers, (V).

O O

a O

N

X

X = CH, N

O O

(V)


F. Cellesi et al., US Patent Application 2003-0044468 (March 6, 2003) J.A. Hubbell et al., US Patent 6,943,211 (September 13, 2005) K. Kataoka et al., US Patent 7,125,546 (October 24, 2006) R.-M. Ho et al., US Patent 7,135,523 (November 14, 2006)

O

b

Title: Methods of Making Functional Biodegradable Polymers Author:

Y. Huage et al., US Patent 7,037,983 (May 2, 2006)

Assignee:

Kimberly-Clark Worldwide, Inc. (Neenah, WI)

SIGNIFICANCE Acrylic acid and derivatives have been free radically grafted onto the backbone of biodegradable polycaprolactone and poly(lactic-co-glycolic acid). These functionalized biocompatible materials are useful as drug delivery agents.

REACTION O

OH

d

O

O O

O b

a

i

O O

O b

a

O

O c

O

i: Acrylic acid, 2,20 -azobisisobutyronitrile

EXPERIMENTAL 1.

Preparation of Poly[(Lactic-co-Glycolic Acid)-g-Acrylic Acid]

To prepare the graft copolymer, poly[(lactic-co-glycolic acid) (5.7 g) was dissolved in acrylic acid (5.7 g) and, upon dissolution, treated with 98% 2,20 -azobisisobutyronitrile (0.014 g). The mixture was then heated to 70 C and continued heating until the reaction mixture solidified. The solid was then placed into a vacuum oven to remove unreacted acrylic acid, and the product was isolated. 80

Notes

81

DERIVATIVES TABLE 1. Biodegradable poly[(lactic-co-glycolic acid) substrates free radically functionalized with grafted acrylic acid or 2-hydroxylethyl acrylate. Entry

Drug Delivery Agent

Structure

O 2

Polycaprolactoneg-acrylic acid

O

a

O O HO

O 3

Poly[(lacticco-glycolic acid)g-2-hydroxylethyl acrylate

O

c

b O

OH

d

O

O O

O

a

O

O b

c

TESTING The solution behavior of the Step 1 product was evaluated using a Coulter tester. In this test NaOH was used to raise the solution’s pH to 9.6 whereupon a milky solution with an average particle size of 2 mwas formed. By one additional day, particle aggregation and precipitation became significant. When the solution pH was raised to 13.7, a clear solution formed with an average particle size of 347 nm.

NOTES 1. In another investigation by the author [1], poly(acrylic acid)-g-poly(lactic acid), (I), was prepared and used as a bioadhesive conjugated with biodegradable components in drug delivery systems.

O

a

b

OH O

O

(I)

c

O

82

Methods of Making Functional Biodegradable Polymers

2. Wang used reactive-extrusion polymerization with 2,5-di-methyl-2,5-di-t-butylperoxy hexane to prepared a graft copolymer, (II), by free radically grafting polyethylene-glycol malonic acid onto the biodegradable substrate of poly(bhydroxybutyrate-co-b-hydroxyvalerate).

O O

O a O

O bO

c

O

O O

(II)

d

O

3. Langer [3] coupled 1,4-butanediol diacrylate with poly(N,N0 -dimethylethylenediamine), (III), piperazine, and 4,40 -trimethylenedipiperidine to prepare poly(b-amino esters) that were particularly suited for the delivery of polynucleotides. Nanoparticles containing polymer/polynucleotide complexes were also prepared. Hubbell [4] and Zhao [5] prepared polymeric biomaterials by the nucleophilic addition of cysteine, (IV), and polyethylenimine, (V), respectively, to a,b-unsaturated macromolecular diacrylates. O O

N O

N

O

n

(III)

O

H2N O

O

S

O

a

O

H

O

(IV)

7 NH2 O

O N a

N H b

O

7 N

O O c

(V)

Notes

83

4. Acrylated terminated multi-block micelle-forming biodegradable macromolecular hydrogels, (VI), prepared by Pathak [6], were used in drug delivery devices and as tissue coatings. O O O

O

O O

Oa

b

O

O

O 182

b O

(VI)

References 1. 2. 3. 4. 5. 6.

Y. Huage et al., US Patent Application 2003-0232088 (December 18, 2003) J.H. Wang et al., US Patent 7,053,151 (May 30, 2006) R.S. Langer et al., US Patent 6,998,115 (February 14, 2006) J.A. Hubbell et al., US Patent 7,119,125 (October 10,2006) G. Zhao et al., US Patent Application 2006-0258751 (November 16, 2006) C.P. Pathak et al., US Patent 7,094,849 (August 22, 2007)

O a

a = 4, b = 1 a = 3, b = 2 a = 2, b = 3 a = 1, b = 4

Title: Monofunctional Polyethylene Glycol Aldehydes Author:

P. Rosen et al., US Patent 7,041,855 (May 9, 2006)

Assignee:

Sun Bio, Inc. (Orinda, CA)

SIGNIFICANCE Monofunctional methoxypolypropylene glycol aldehydes were prepared in a five-step synthetic route. These materials are useful as protein conjugates, and they induce very mild immunogenic responses.

REACTION O O

H3CO

O

i

OH

452 O

iv

O

H3CO

O

O

452

O H3CO

i: ii: iii: iv: v:

O

O

O 452

O

H N

O

H3CO

O

O

O

452

ii

C2H5

O O

O

iii

N

O

H3CO

O

O

O

OH

452 O

OC2H5 OC2H5

v Notes 1,2

H3CO

O

O

O 452

O

H N

H O

Potassium t-butoxide, ethyl bromoacetate, t-butyl alcohol Sodium hydroxide CH2Cl2, N-hydroxysuccinimide, dicyclohexylcarbodimide CH2Cl2, 1-amino-3,3-diethoxypropane Phosphoric acid, sodium bicarbonate

EXPERIMENTAL 1.

Preparation of Polyethylene Glycol Ethyl Acetate

Methoxypolyethylene glycol and potassium t-butoxide were dissolved in t-butyl alcohol, stirred at 60 C, and then next treated with ethyl bromoacetate. The mixture was next stirred an additional 15 hours at between 80 C and 85 C, filtered, and 84

Alternative Synthetic Pathway Proposed by the Author

85

concentrated. The residue was dissolved in distilled water, washed with diethyl ether, and extracted twice with CH2Cl2. The extract was dried over MgSO4 and concentrated. Precipitation was induced by the addition of diethyl ether to the residue, and the mixture was filtered. The solid was dried under vacuum, and the product was isolated as a white powder. 2.

Preparation of Polyethylene Glycol Acetic Acid

The Step 1 product was dissolved in 1 M sodium hydroxide and stirred for 15 hours at ambient temperature. The reaction mixture pH was then adjusted to 2 using 1 M hydrochloric acid and extracted twice with CH2Cl2. The mixture was worked up as described in Step 1, and the product was isolated as a white powder. 3.

Preparation of Polyethylene Glycol Succinimidyl Acetate

A solution of the Step 2 product dissolved in CH2Cl2 was cooled up to 5 C and treated with N-hydroxysuccinimide followed by a solution of dicyclohexylcarbodimide dissolved in CH2Cl2. The mixture was stirred for 15 hours at ambient temperature and then filtered and concentrated, and the residue was re-crystallized from EtOAc. The product was washed twice with diethyl ether was dried, and the product was isolated as a white powder. 4.

Preparation of Polyethylene Glycol Diethyl Acetal

The Step 3 product was dissolved in CH2Cl2, treated with 1-amino-3,3-diethoxypropane dissolved in CH2Cl2, and stirred 2 hours at ambient temperature. Precipitation was then induced by the addition of diethyl ether. The mixture was filtered, recrystallized using EtOAc, and dried; the product was isolated as a white powder. 5.

Preparation of Polyethylene Glycol Aldehyde

The Step 4 product was dissolved in an aqueous solution containing phosphoric acid at pH 1 and stirred for 2 hours at between 40 C and 50 C. After cooling the reaction mixture to ambient temperature, the pH was raised to 6 using 5% aqueous NaHCO3 solution. Brinewas then added, and the resulting mixture extracted twicewith CH2Cl2. The extract was dried over MgSO4, filtered, and concentrated. Precipitation was induced by the addition of diethyl ether to the residue, and the product was isolated as a white powder.

ALTERNATIVE SYNTHETIC PATHWAY PROPOSED BY THE AUTHOR O HO

OH

i

HO

O2N O

O

OH

H3CO

O a

O

O

O

ii

iii

O O

H N

O O

iv H

H3CO

O a

O

O

H N

O O

O

86

Monofunctional Polyethylene Glycol Aldehydes

i: ii: iii: iv:

4-Toluene sulfonic acid, acetone, light petroleum ether 4-Nitrophenyl chloroformate, acetonitrile, 4-dimethylaminopyridine Polyethylene glycol 2-ethylamine, 4-dimethylaminopyridine, CH2Cl2 Hydrochloric acid, hydroperiodate acid

NOTES 1. In an earlier investigation by the author [1] methoxypolyethylene glycol derivatives containing pendant aldehydes, (I), were prepared as illustrated below. O

H3CO

O

OH

i

a

O

H3CO

O

O

OH

ii

a

OH O

H3CO O

O

OH

a

O

H3CO

NH

O

O

O

iv

OH

a

iii

O

NH C2H5 O

H

O

O

H3CO O

O

a

O N

C2H5

O

(I)

i: ii: iii: iv:

Acrylic acid, t-butyl peroxybenzoate CH2Cl2, N-hydroxysuccinimide, dicyclohexylcarbodimide CH2Cl2,1-amino-3,3-diethoxypropane Phosphoric acid, water

2. In a subsequent investigation by the author [2] bi-functional polyethylene glycol derivatives, (II), were prepared.

O

A

(II)

O a

A SO2CH=CH2 Malimide–CH2CO Malimide–CH2CO CONHCH2CH2CHO

B

B CONHCH2CH2CHO Malimide–CH2CO CONHCH2CH2CHO CONHCH2CH2CHO

3. Additional methoxypolyethylene glycol derivatives, (III), were prepared by Harris [3] in earlier investigations.

H3CO

O a

O

(III)

H N

R R

R CH2OCH2C6H5 CH2OH CH2SCH2CH2OH CH2SCH=CH 2

O H

Notes

87

4. Acid-terminated methoxypolyethylene glycol, (IV), was prepared by Whitlow [4] and used to conjugate single-chain polypeptides.

O H3CO

O

O

O

a

(IV)

OH O

5. Hydroxyl/carboxylic acid terminated polyethylene glycol derivatives, (V), were prepared by Varshney [5] and used as intermediates. O HO2C

3

OH

(V)

O a

6. Azide- and acetylene-terminated polyethylene glycol derivatives were prepared by Wilson [6] and used in biomedical applications. References 1. 2. 3. 4. 5. 6.

P. Rosen et al., US Patent 6,956,135 (October 18, 2005) P. Rosen et al., US Patent 7,217,845 (May 15, 2007) J.M. Harris et al., US Patent 6,541,543 (April 1, 2003) and US Patent 6,362,254 (March 26, 2002) M. Whitlow et al., US Patent 7,150,872 (December 19, 2006) S.K. Varshney et al., US Patent 7,009,033 (March 7, 2006) T.E. Wilson, US Patent 7,230,068 (June 12, 2007)

IV. COATINGS A. Anionic

Title: Glycopolymers and Free Radical Polymerization Methods Author:

E. L. Chaikof et al., US Patent 7,244,830 (July 17, 2007)

Assignee:

Emory University (Atlanta, GA)

SIGNIFICANCE Heparin-like copolymers containing up to 100 units of sulfonated glucose or lactose have been prepared by polymerizing with acrylamide using arenediazonium salts with cyanate anions to form a thrombo-resistant heparinized surface.

REACTION HO

HO

HO O

HO HO Ac

i

O

HO HO

NH OH

Ac

Cl

a H2N

O

b

NH O

Ac

O3SO O3SO

O

Separate

O

NH

O3SO

OCN

iii

HO O

O3SO O3SO Ac

O3SO

O

HO HO

+

NH O

ii

O

HO HO Ac

NH O

O NH Ac


90

Glycopolymers and Free Radical Polymerization Methods

i: 4-Penten-1-ol, 10-camphorsulfonic ii: Sulfur trioxide trimethylamine complex iii: 4-Chloroaniline, sodium nitrite, boron trifluoride hydrogen fluoride, cyanate ions

EXPERIMENTAL 1.

Preparation of N-Acetyl-d-Glucosamine Glycomonomer

N-Acetyl-d-glucosamine was treated with 4-penten-1-ol in the presence of 10-camphorsulfonic acid as catalyst. This provided an a- and b-anomeric mixture of the corresponding C4-spacer arm containing the glycomonomer. The a- and b-anomers were separated by column chromatography with CHCl3 and methyl alcohol and were isolated in 31% and 11% yields, respectively. 2.

Preparation of N-Acetyl-D-Glucosamine Glycomonomer Persulfates

Chemoselective sulfation of the hydroxy groups of the Step 1 a-anomer was obtained using SO3–NMe3 complex and the product purified by anion-exchange and sizeexclusion chromatography. 3.

Preparation of Glycopolymers

Cyanoxyl radicals were generated in situ by an electron-transfer reaction between cyanate anions and p-chlorobenzenediazonium cations; arenediazonium salts were previously prepared in water through the diazotization reaction of p-chloroaniline. Copolymerizations were performed using the Step 2 product and acrylamide at 50 C with ClC6H4N2þ BF4/NaOCN as the initiating system. Copolymers were isolated by precipitation in a 10-fold excess of methanol and characterized.

DERIVATIVES Lactose-based glycomonomers were also prepared as illustrated below.

O3SO

O3SO O

O3HSO O3SO

O3SO

O

O O3SO

O3SO

O

Notes

91

NOTES 1. In a subsequent investigation by the author [1] multivalent glycopolymers with chain-terminating binding groups, (I), were prepared and used in carbohydratemediated biomolecular recognition processes.

OH O

O H N

S

HN

O

O

O OH

HO

NH

HN

O

OH OH OH

HO

CONH2

O bc

a

NCO

(I) 2. Antithrombonic polymers consisting of poly(vinylidene fluoride-cohexafluoropropylene-co-vinyl pyrrolidone), (II), 80/15/5 molar ratio, respectively, were prepared by Pacetti [2] and used as shunts in treating atherosclerosis and thrombosis.

C F2 a

F2 C

CF

b CF3

c N

O

(II) 3. Antithrombonic esters, including co-poly-(N,N0 -sebacoyl-bis-(L-leucine)-1,6hexylene diester), (III), and polyethylene glycol derivatives, (IV), were prepared by Pacetti [3] and Hossainy [4], respectively, and used as bio-absorbable stent coatings.

O

O 8

N H

O O

(III)

O 6

O

N n H

92

Glycopolymers and Free Radical Polymerization Methods

O

O

O 4

O

PEG300 O

a

O 4

O

O b

(IV)


E.L. Chaikof et al., US Patent Application 2005-0180945 (August 18, 2005) S.D. Pacetti, US Patent 7,244,443 (June 17, 2007) S.D. Pacetti et al., US Patent 7,220,816 (May 22, 2007) and US Patent 7,202,325 (May 22, 2007) S.F.A. Hossainy et al., US Patent 7,186,789 (March 6, 2007) and US Patent 7,169,404 (January 30, 2007)

B. Aqueous

Title: Method of Making Novel Water-Soluble and Self-doped Polyaniline Graft Copolymers Author:

W.-H. Jo et al., US Patent 7,229,574 (June 12, 2007)

Assignee:

Seoul National University Industry Foundation (Seoul, KR) Cheil Industries, Inc. (Kyeonggi-do, KR)

SIGNIFICANCE Polyaniline has been grafted onto the poly(styrenesulfonic acid-co-aminostyrene) backbone using aniline, ammonium persulfate, and hydrochloric acid. The graft copolymer is water soluble and self-doping and can be used in electrical and marine anticorrosive applications.

93

94

Method of Making Novel Water-Soluble and Self-doped Polyaniline Graft Copolymers

REACTION

a

b

i Note 1 BOC

NH

BOC

b

a

ii NH

SO3Na

a

b

iii NH3Cl

NH

SO3H

SO3

Not Isolated NH

NH

...

NH

i: Styrene-4-sulfonic acid sodium, DMSO, 2,20 -azobisisobutyronitrile ii: Aniline, ammonium persulfate, hydrochloric acid

EXPERIMENTAL 1. Preparation of Poly(Styrene-4 Sulfonic Acid Sodium-co-Styrene4-Amino-Butyl Carbonate) A reactor was charged with styrene-4-sulfonic acid sodium (5 g), styrene-4-amino-tbutyl carbonate (0.5 g), and 2,20 -azobisisobutyronitrile (0.1 g) dissolved in 60 ml of DMSO and polymerized for 15 hours at 80 C. The mixture was then precipitated in acetone, filtered, washed several times with acetone, dried, and the product was isolated. 2.

Preparation of Self-doped Polyaniline Graft Copolymer

Aniline and the Step 1 product were mixed with water and then treated with the dropwise addition of 20 ml 1 M ammonium persulfate and hydrochloric acid at 80 C where the molar ratio of ammonium persulfate/aniline was 1.0. After standard workup the polymer was isolated. Aniline grafting lengths greater than 20 units could not be solubilized in water.

Notes

95

NOTES 1. Polyaniline was converted into N-t-BOC polyaniline, (I), by Lee [1] to reduce intermolecular hydrogen bonding when used in conductive polymer applications. BOC N

NH

a

N

N

b c

(I)

2. Hwang [2] grafted polyaniline onto carbon nanocapsules having a diameter between 3-100 nm using ammonium persulfate and hydrochloric acid. 3. Polyaniline-grafted carbon black was prepared by Srinivas [3] and then platinized with chloroplatinic acid, as illustrated below, and used as a fuel cell component. Sulfurized analogues, (II), were prepared by Srinivas [4] and were also used as fuel cell components. NH2

i ii H2PtCl6 NaBH4 / H2

NH

NH Pt

a

Pt

Carbon black

i: Ammonium persulfate, hydrochloric acid

HO3S NH

HO3S NH

(II) Carbon black

a

96

Method of Making Novel Water-Soluble and Self-doped Polyaniline Graft Copolymers


S.-H. Lee et al., US Patent 7,067,229 (June 27, 2006) G.-L. Hwang et al., US Patent 7,217,748 (May 15, 2007) B. Srinivas, US Patent 7,195,834 (March 27, 2007) B. Srinivas et al., US Patent Application 20040169165 (September 2, 2004)

Title:

Oxyfluorination

Author:

I. deVilliers Louw et al., US Patent 7,225,561 (June 5, 2007)

Assignee:

South African Nuclear Energy Corporation, Ltd. (ZA)

SIGNIFICANCE Polypropylene has been oxyfluorinated using a gas mixture consisting of fluorine, nitrogen, and water. When cured with mortar slurry, oxyfluorinated surfaces had 20% greater shear bond strength than fluorinated surfaces.

REACTION OF F

Polypropylene

OF F

OF

i Note 1

i: Fluorine, nitrogen, water

EXPERIMENTAL 1.

Preparation of Polypropylene-g-Hypofluorite

Monofilament polypropylene fibres were prepared by direct extrusion having a rectangular cross section of 0.5 1.3 mm, a length of 40 mm, a specific gravity of 0.91, a tensile strength of 120 MPa, and an elongation at break of 14%. The fibers were placed under 18% humidity at ambient temperature air and then treated with 20% F2 and 80% N2 at a pressure of 45 kPa at 38 C for 2.5 hours. Thereafter the reaction vessel was evacuated, and the product was isolated.

97

98

Oxyfluorination

TESTING TABLE 1. Shear bond testing of surface modified polypropylene after oxyfluorination curing in mortar slurry. Entry 1 Control

Shear Bond Strength at 7 Days (MPa)

Shear Bond Strength at 28 Days (MPa)

0.48 0.40

0.46 0.39

Note: The Control sample was prepared under anhydrous conditions.

NOTES 1. Oxyfluorination of polypropylene was previously done by Hruska [1], and the material was used as an oxidative surface treatment method in electrophotography. 2. Mori [2] developed a method for solid bonding without using a bonding agent by surface hydrofluorinating metal or glass in the presence of water vapor. 3. Oxyfluoropolymers-adhesive composites have also been prepared by Vargo [3] using a radio frequency glow discharge of polytetrafluorineethylene. 4. Surface oxyfluorination was also performed on poly(methyl methacrylate) by Jolet [4] as a method for manufacturing the outer panel of craze-resistant windows. References 1. Z. Hruska, US Patent 6,503,989 (January 7, 2003) 2. Y. Mori et al., US Patent Application 2001-0009176 (July 26, 2001) and US Patent 6,620,282 (September 16, 2003) 3. T.G. Vargo et al., US Patent 6,790,526 (September 14, 2004) 4. L. Joret et al., US Patent 7,211,290 (May 1, 2007)

Title: Aqueous Dispersions of Crystalline Polymers and Uses Author:

R. F. Stewart et al., US Patent 7,175,832 (February 13, 2007)

Assignee:

Landec Corporation (Menlo Park, CA)

SIGNIFICANCE Aqueous dispersions of crosslinked crystalline polymers containing both hydrophobic and hydrophilic components have been prepared. The hydrophobic components consist of C6-, C12-, C14-, and C16-acrylates while methyacrylic acid constituted the hydrophilic comonomer. These dispersions are useful as coatings, particularly on human hair.

REACTION OC16H33 O

O OC16H33

c

b

O

i

O

O

a

O

OC16H33

OC16H33

e

d

OC6H13

O O

O g

f

C16H33O

h

O

OC6H13

i

j

O

O

C16H330

C16H33O

O

i: Water, ethyl alcohol, hexyl acrylate, methyacrylic acid, 1,14-tetradecanediol, sodium dodecyl sulfate, ammonium dodecyl benzene sulfonate, potassium persulfate 99

100

Aqueous Dispersions of Crystalline Polymers and Uses

EXPERIMENTAL A mixture consisting of water (190 g), ethyl alcohol (10 g), hexadecyl acrylate (70 g), hexyl acrylate (25 g), methyacrylic acid (5 g), 3.2% sodium dodecyl sulfate, and ammonium dodecyl benzene sulfonate (5 g) was charged into a reactor and degassed for 30 minutes. Potassium persulfate (0.4 g) was then added, and the polymerization was conducted for 4 hours at 70 C under nitrogen. After the polymer was isolated, a sharp DSC endotherm was observed at 22.5 C.

REACTION SCOPING TABLE 1. Effects on terpolymer Tm for materials crosslinked with 1,14 tetradecyldiol using varying amounts of surfactant and co-solvents. Reaction Components Water (g) C16 Acrylate (g) C6 Acrylate (g) Methyacrylic acid (g) 1,14 Tetradecyldiol (g) Sodium dodecyl sulfate (g) Ammonium dodecyl benzene sulfonate (g) Potassium persulfate (g) Ethyl acetate (g) Ethanol (g) Tm ( C) Tm Peak appearance

Example 1

Example 3

Example 5

Example 7

200 70 25 5 2 5 5

190 70 25 5 1.5 5 5

200 70 25 5 — 2.5 2.5

180 70 25 5 — 2.5 2.5

0.4 — 10 30.7 Broad

0.4 20 — 21.9 Sharp

0.4 — — 33.0 Multiple peaks

0.4 20 — 32.6 Sharp

TABLE 2. Effects on the polymer Tm after eliminating the amorphorous effects of both of C6-acrylate and 1,14 tetradecyldiol. Reaction Components Water (g) C16 Acrylate (g) C14 Acrylate (g) C12 Acrylate (g) Methyacrylic acid (g) Sodium dodecyl sulfate (g) DOSS (g) Potassium persulfate (g) Ethyl acetate (g) Dodecyl mercaptan (g) Tm ( C) Tm Peak appearance

Example 9

Example 10

Example 11

Example 12

200 35 — 60 5 2 2 2 —

190 35 — 60 5 2 2 0.4 10 — 2.7 Broad peak

400 70 — 120 10 8 8 1.6 — — 13.9 Sharp peak

400 — 95 95 10 8 8 1.5 — 0.1 16.1 Sharp peak

2.0 and 33.7 Two peaks

Notes

101

NOTES 1. Bitler [1] prepared sharply melting crystalline polymers consisting of C8–C30 urea-ethyl-methacrylate, (I), and C22-acrylate, which reflected high side chain crystallinity and which were used as temperature-dependent coating agents.

O

H N

O

(I)

O

C8H17 - C30H61

O

2. Copolymers, (II), consisting of 75% to 80%–C16-acrylate and 2-hydroxyethyl acrylate having high side chain crystallinity were prepared by Bitler [2] and used as oil thickeners. OC16H33

OC16H33 O

O

OC16H33

O a

O

O

O

b

OC16H33 OC16H33

d

c

O

O

OH

O

OH

(II)

References 1. S.P. Bitler et al., US Patent 6,831,116 (December 14, 2004) 2. S.P. Bitler, US Patent 7,101,928 (September 5, 2006) US. Patent 6,989,417 (January 26, 2006)

C. Fluorine

Title: Multifunctional (Meth)Acrylate Compound, Photocurable Resin Composition and Article Author:

Y. Yoshikawa et al., US Patent Application 2007-0116971 (May 24, 2007)

Assignee:

Shin-Etsu Chemical Co., Ltd. (Annaka-shi, JP)

SIGNIFICANCE Trifunctional (meth)acrylate fluorine-containing cyclic and acyclic silane compounds have been prepared that form photocurable resin compositions. Coatings from these resins are anti-fouling and resist organic stains from oil mist and fingerprints without detracting from surface mar resistance.

REACTION CF3 F2C CF2 F2C CF2 F2C CF2 F2C

CF3 F2C CF2 F2C CF2 F2C CF2 F2C

Si H O

O O H

i

ii

O O

H

O

O

Si O

O

O

O O O

O O

Resin

O

O

i: 2-Hydroxyethyl acrylate, toluene, N,N-diethylhydroxylamine ii: g-Acryloxypropyltrimethoxysilane, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, DarocureRTM, UV irradiation 102

Notes

103

EXPERIMENTAL 1. Preparation of tri(2-Hydroxyethyl Acrylate) 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8Perfluoro-11-Decyl Cyclotrimethylsilane A reactor was charged with 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-perfluoro-11-decyl cyclotrimethyl-silane (0.1 mol), 2-hydroxyethyl acrylate (0.315 mol), and toluene (111.9 parts) and then treated with N,N-diethylhydroxylamine (0.0126 mol). Thereafter the reaction was heated for 8 hours at 70 C, cooled to ambient temperature, washed with water, and concentrated. The product was isolated having a viscosity of 93.0 mm2/s with a refractive index of 1.4018. 2.

Preparation of Photocurable Resin

A mixture consisting of silica (40 parts) previously treated with g-acryloxypropyltrimethoxysilane, trimethylolpropane triacrylate (40 parts), 1,6-hexanediol diacrylate (20 parts), the Step 1 product (0.5 parts), and DarocureRTM (5 parts) as the free radical initiator were spin-coated and irradiated with UV light to form a coating having a thickness of roughly 5 mm.

DERIVATIVES CF3 F2C CF2 F2C CF2 F2C CF2 F2C

F3C CF2 F2C O F3C CF CF2 O CF CF3 O NH

O O

O Si O O

O

O O

O

O O

O

O

O

Si

O Si O Si O

O Si

O

O O

O

O

O

O

NOTES 1. A crosslinkable silicone rubber coating composition, (I), was prepared by Azechi [1] and used in preparing automotive airbags.

104

Multifunctional (Meth)Acrylate Compound, Photocurable Resin Composition and Article

H O

Si O

O

O

Si

OSi

Si

O

O

O

H

(I) 2. Crosslinkable tetravinylsiloxane derivatives, (II), prepared by Hare [2] were used as low-viscosity materials in dental impressions.

O

Si

O Si

O

Si O

Si

Si

(II) 3. Morita [3] prepared silsesquioxane resins using crosslinkable vinyl monomers, (III), for use in semiconductor devices.

Si O Si O

O Si

O

O

O SiOSi Si O O Si O SiOSi O O

Si O

Si

O

O Si

O

(III) References 1. S. Azechi et al., US Patent 7,153,583 (December 26, 2006) 2. R.V. Hare, US Patent 6,561,807 (May 13, 2003) 3. K. Morita et al., US Patent Application 20070054135 (March 8, 2007)

D. Hydrophilic

Title: Polyoxyalkylene Phosphonates and Improved Process for Their Synthesis Author:

S. Wo et al., US Patent 7,208,554 (April 24, 2007)

Assignee:

Rhodia Inc. (Cranbury, NJ)

SIGNIFICANCE Hydrophilic surface active agents containing C1–C4 phosphoric acid derivatives provide limited benefits because of their short aliphatic chain. To address this concern, hydrophilic phosphonic acid derivative containing an oligomeric ethylene glycol component has been prepared.

REACTION H

O

10 O

O

i O

O

10

O

ii O

H

O

10O

O

10

P O

P O

OCH3 OCH3

iii Note 1

OH OH

i: Acetic anhydride ii: Di-t-butyl peroxide, dimethyl hydrogen phosphite iii: Water

EXPERIMENTAL 1.

Preparation of Acetyl Polyethylene Glycol Allyl Ether

A two-neck flask equipped with a Snyder distilling column and distilling head was charged with polyethylene glycol allyl ether (1.0 mol; Mw ¼ 498 daltons) and then

105

106

Polyoxyalkylene Phosphonates and Improved Process for Their Synthesis

treated with acetic anhydride (1.05 mol). The mixture was heated to 110 C for 3 hours during which time the acetic acid by-product was collected. At the end of the reaction excess acetic anhydride was removed under vacuum, and the product was isolated. 2.

Preparation of Acetyl Polyethylene Glycol Dimethyl Phosphite

The Step 1 product (1 mol) was mixed with di-t-butyl peroxide (0.1mol) and then added to a second flask containing dimethyl hydrogen phosphite (1.1 mol) and heated for 5.5 hours at between 130 C and 135 C. At the conclusion of the reaction excess dimethyl hydrogen phosphite was removed under vacuum, and the product was isolated. 3.

Preparation of Polyethylene Glycol Phosphonopropyl Ether

The entire Step 2 product was treated with excess water and hydrolyzed for 20 hours from 135 C to 150 C. During this time the volume ratio of the Step 1 product/water was kept at 1:1, and methanol and acetic acid by-products were continuously removed by distillation. Thereafter the product was isolated and was completely soluble in water.


NOTES 1. Baker [1] determined that both polyethylene glycol phosphonopropyl ether, (I), with repeat units of 4 and 10 were effective as cerium oxide nanoparticle dispersants.

H

O

aO

P

(I)

O

OH OH

a = 4, 10

2. Zeller [2] prepared anionic and nonionic surface-active agents, (II), consisting of fatty alcohols and ethylene oxide which were used as surfactants. O 13-15

X

O

(II)

a

X = OH, PO(OH) 2, SO 3H a = 3–11

Notes

107

3. In an earlier investigation by the author [3] sulfonated polyesters were prepared consisting of ethylene glycol and terephthalate acid capped with dimethyl-5sulfoterephthalate. References 1. J.M. Baker et al., US Patent Application 2006-0241008 (October 26, 2006) 2. E. Zeller et al., US Patent 7,183,446 (February 27, 2007) and US Patent 6,963,014 (November 8, 2005) 3. S. Wo, US Patent 6,576,716 (June 10, 2003)

E. Hydrophobic

Title: Polymers and Polymer Coatings Author:

C. Ober et al., US Patent Application 2007-0053867 (March 8, 2007)

Assignee:

Cornell Research Foundation, Inc. (Ithaca, NY)

SIGNIFICANCE A limited number of marine paint additives exist that can provide antifouling coatings that are nontoxic and “fouling repellant.” Silicon-free polyacrylates containing a pendant semifluorinated alkyl substituent have been prepared to address this need.

REACTION Br

i O

23

O

O

O

O

t-C4H9

Br

ii O

O

82

23

O

O

t-C4H9

t-C4H9

Br 23

O

O

iv

C y F2

23

O

O x F2 C

Br

82

O

iii

O

O

O

82

OH

x = 0–15 y = 1–7

i: Acetone, pentamethyldiethylene triamine, copper(I) bromide, copper(II) bromide, methyl 2-bromopropionate ii: Copper(I) bromide, styrene, pentamethyldiethylene triamine iii: Hydrochloric acid, dioxane iv: Pyridine, 1,3-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, ZonylÒ FSO-100, THF 108

Experimental

109

EXPERIMENTAL 1.

Preparation of Poly(t-Butylacrylate) Macroinitiator

A mixture containing 3 ml of acetone, t-butylacrylate (80 mmol), and pentamethyldiethylene-triamine (0.8 mmol) were added to CuBr (0.8 mmol) and CuBr2 (0.04 mmol). This mixture was then treated with methyl 2-bromopropionate (1.6 mmol) and heated for 6 hours at 60 C. It was cooled to ambient temperature and treated with 50 ml of acetone and neutral alumina. The acetone solution was concentrated and the residue purified by dissolving in diethyl ether. The purified material was precipitated in a methanol/water mixture, 1:1, at 0 C, dried, and the product was isolated having a Mn of 3000 daltons with a polydispersity index of 1.1. 1

H NMR (CDCl3): d 1.5 (s, 9H, –C(CH3)3); 1.85 and 2.35 (br s, –CH2, , >CH–); (s, 3H, –OCH3) 4.1 (m, 1H, >CH–Br) FTIR (film; cm1): 2977 (C–H stretching, t-butyl); 2929 (C–H stretching, backbone); 1727 (C¼O stretching, ester); 1367 (C–H bending, t-butyl).

2.

Preparation of Poly[(t-Butylacrylate)-block-Styrene]

A mixture consisting of the Step 1 product (0.67 mmol) and CuBr (0.95 mmol) mixed with styrene (95 mmol) was stirred until the polymer dissolved. Pentamethyldiethylene triamine (0.95 mmol) was added, and the mixture was heated for 2 hours at 100 C. After cooling to ambient temperature the viscous polymer was dissolved in 150 ml of THF and then passed through a column of neutral alumina. The solution was concentrated, the residue precipitated in methanol, and the polymer isolated having polydispersity index of 1.1. 1

H NMR (CDCl3): d 1.5 (s, 9H, –C(CH3)3); 1.85 and 2.35 (br s, –CH2, >CH–); 6.5 AND 7.1 (br s, 5H, styrene) FTIR (film; cm1): 3026 (C–H stretching, aromatic); 2976 (C–H stretching, t-butyl); 2926 (C–H stretching, backbone);1728(C¼Ostretching,ester);1493,1452(C¼Cstretching,aromatic);1367(C–Hbending,tbutyl); 758 and 700 (C–H bending, aromatic)

3.

Preparation of poly(Acrylic Acid)-block-Polystyrene

Two milliliters of concentrated hydrochloric acid solution was added to a 10% solution of the Step 2 product dissolved in dioxane and refluxed for 6 hours. After cooling to ambient temperature the polymer was precipitated in water, and the product was isolated after recovering by filtration. 1 H NMR (DMSO-d6): d 2.2 and 1.6 (br s, –CH2, >CH–); 6.5 and 7.1 (br s, 5H, styrene); 12.0 (br s, COOH) FTIR (film; cm1): 3600-2400 (O–H stretching, carboxylic acid); 3026 (C–H stretching, aromatic); 2926 (C–H stretching, backbone); 1716 (C¼O stretching, ester); 1492, 1452 (C¼C stretching, aromatic); 758 and 700 (C–H bending, aromatic)

110

4.

Polymers and Polymer Coatings

Preparation of poly(Ethoxylated Fluoroalkyl Acrylate)-block-Polystyrene

In the first vessel the Step 3 product (1 g) was dissolved in 5 ml of pyridine. In a second vessel 1,3-dicyclohexylcarbodiimide (6.57 mmol), 4-dimethylaminopyridine (0.823 mmol), and Zonyl FSO-100 (6 g) were dissolved in THF and then added dropwise to the first vessel. The reaction was stirred for 2.5 days at ambient temperature and filtered to remove dicyclohexylurea. The solution was concentrated and then precipitated by pouring into methanol. It was re-dissolved in THF and reprecipitated into methanol; the product was isolated after filtration. 1

H NMR (300 MHz, CDCl3): d 6.5 and 7.1 (5H, styrene); 4.16 (br s, 2H, –COOCH.sub.2–); 3.77 (t, 2H,– COOCH.sub.2CH.sub.2–); 3.64 (br s, –OCH.sub.2CH.sub.2O–); 2.42 (m, 2H, –CH.sub.2CF. sub.2–); 1.86, 1.43 (backbone) 19 F NMR (CDCl3, CF3COOH reference) d: 126.65, 124.16, 123.38, 122.41, 113.95, 81.27 (3F, –CF3) FTIR (film; cm1): 3026 (C–H stretching, aromatic); 2922 (C–H stretching, backbone); 1731 (C¼O stretching, ester); 1490, 1450 (C¼C stretching, aromatic); 1400–1000 (C–F stretching); 754 and 698 (C–H bending, aromatic)


TESTING Quantitative testing data on biofouling assays was not provided.

NOTES 1. Semifluorinated block copolymers, (I), were previously prepared by the author [1] and then blended with styrene-ethylene/butylene-styrene thermoplastic elastomers to provide surface-active block copolymers. z

y

x

O

x = 500 –1000 y = 200 –1000 z = 100 –1000 n = 4, 6

n

F

CF2

O

8

n

(I)

CF2 F

8

Notes

111

2. Biofouling-resistant surfactant compositions, (II), were prepared by Swedberg [2] that had a hydrophobic domain that promoted adsorption of the surfactant molecule to the surface of selected surface active materials.

(PEO)129

(PEO)129

(PPO)100

(II)

H N

O

SO3H

O

3. Pendant quaternary amine salts prepared by Price [3] were effective as antifouling additives in marine paint.

a O

N H

NH

(III)

References 1. C. Ober et al., US Patent 6,750,296 (June 15, 2004) 2. S.A. Swedberg et al., US Patent 7,201,834 (April 10, 2007) 3. C. Price, US Patent Application 2007-0082972 (April 12, 2007)

Palmitic

Title: Photochemical Crosslinkers for Polymer Coatings and Substrate Tie-Layer Author:

P. Guire et al., US Patent Application 2007-0003707 (January 4, 2007)

Assignee: SurModics, Inc. (Eden Prairie, MN)

SIGNIFICANCE Two trifunctional benzophenone derivatives have been synthesized that are UV photoactive at 254 nm and photolytically incorporated into poly(e-caprolactone) and poly(vinylpyrrolidone). These agents are designed to be used in photopolymerization reactions.

REACTION O HO

O

i

O O

N OH O

N N

O

O O

OH

OH

O

Photochemical curing agent

i: Glycerol triglycidyl ether, potassium carbonate, acetone

EXPERIMENTAL Preparation of tri(N-2-Hydroxy-3-(4-Benzophenoxy)Propyl))-s-Triazine A round bottom flask was charged with 4-hydroxybenzophenone (2.26 g), 0.532 ml of glycerol triglycidyl ether, potassium carbonate (3.3 g), and 50 ml of acetone and then refluxed 24 hours and concentrated. The residue was dissolved in CCl3H and filtered. The filtrate was washed three times with 4 M NaOH aqueous solution, once with water, 112

Testing

113

twice with 1 M HCl, and re-washed three times with water. The solution was dried over MgSO4, filtered, and concentrated. The residue was washed three times with diethyl ether and then re-dried, and the product was isolated.

TESTING Wettable Testing A coating solution was prepared in isopropanol using the Step 1 product (0.5 mg/ml) and poly-vinylpyrrolidone (50 mg/ml). A 100 ml of the coating solution was applied to polyvinylchloride coverslips and then dried overnight. All pieces were illuminated at 254 nm light from 0 to 10 minutes and rinsed with 30 minutes in water with gentle agitating. The static contact angle with water was taken on a goniometer with three 3 ml drops of water and measured three times. Contact angle testing results are provided in Table 1. TABLE 1. Contact angles of PVC coated with the Step 1 product followed by UV activation at 254 nm. Illumination Time at 254 nm (min) 0 0.5 1 2 5 10 Uncoated

Contact Angle (deg) 38.1 – 10.0 24.8 – 7.8 31.7 – 6.3 31.1 – 4.4 23.1 – 8.8 29.1 – 3.0 61.9 – 1.4

Photoreactive Surface Preparation and Testing A photoreactive polymer solution was prepared by mixing poly(e-caprolactone) (50 mg/ml) film with the Step 1 product (0.5 mg/ml) and then casting the mixture onto a glass slide. The film was treated with poly(vinylpyrrolidone) (10 ml 50 mg/ml, 30,000 daltons), dissolved in isopropanol solution, and the mixture was concentrated. The film was illuminated for 20 minutes using 254 nm light and then incubated in water on a shaker for 3 hours to remove unbound PVP. After staining with 0.5% w/v aqueous solution of Congo Red the components of a film consisting of poly(vinylpyrrolidone) and poly(e-caprolactone) was determined to be homogeneously distributed. By contrast, films prepared without the triazine crosslinker showed no stainings, suggesting that the unbound poly(vinylpyrrolidone) was removed by the rinse.

114

Photochemical Crosslinkers for Polymer Coatings and Substrate Tie-Layer

NOTES 1. Oxime derivatives were prepared by Kunimoto [1] containing both esteroxime and aryl ketone components, (I), were particularly effective in photopolymerization reactions.

S N

O O

O

(I) 2. Blood compatible surfaces were prepared by the author [2] by UV curing of benzophenone-containing polyethylene ether, (II).

O O O

4 N

13

CO2H

H

(II)

3. Swan [3] prepared a benzene 1,3-disulfonic acid derivative, (III), as a surface coating agent for polyvinylpyrrolidone for subsequent use as a surface modifier on polyvinylchloride urinary catheters.

KO3S

SO3K

O O

O

(III)

O

4. Swan [4] prepared terpolymers, (IV), containing photoreactive groups that covalently bond to nucleic acids for use in preparing nucleic acids microarrays.

Notes

O

a

b

NH O

NH2 O

c

O

HN

3

O

O

115

2

O

O O

(IV)


K. Kunimoto et al., US Patent 7,189,489 (March 13, 2007) P. E. Guire et al., US Patent 7,144,573 (December 5, 2006) and US Patent 7,071,235 (July 4, 2006) D. G. Swan, US Patent 7,138,541 (November 21, 2006) D. G. Swan et al., US Patent 6,762,019 (July 13, 2004)

Title: Use of Poly(Dimethyl Ketone) to Manufacture Articles in Direct Contact with a Humid or Aqueous Medium Author:

B. Brule et al., US Patent 7,011,873 (March 24, 2006)

Assignee:

Arkema (Puteaux, FR)

SIGNIFICANCE The low water permeability of polydimethyl ketone has been found to be effective in preparing hermetically sealed industrial food packaging that comes in direct contact with a humid or aqueous medium.

REACTION O

O

i

C O

O

ii Notes 1, 2

a O

O

b

a>b

i: Pyrolysis ii: Aluminium tribromide, carbon tetrachloride

EXPERIMENTAL 1.

Preparation of Dimethylketene

Isobutyric anhydride was pyrolysized between 550 C and 675 C under an absolute pressure of between 30 and 40 mmHg and while under a nitrogen stream of 1.5 ft3/h. Gaseous products from the pyrolysis chamber passed through a water-jacketed copper condenser and then through two glass cylinder separators. The residue vapors were next passed though a cold trap at 50 C and conducted to a cold condenser and receiver to collect the dimethylketene, BP ¼ 34 C.

116

Notes

2.

117

Preparation of Poly(Dimethyl Ketone)

Dimethylketene (15.2 g) enclosed in a tubular reactor was placed in an acetone Dewar flask at 30 C and treated with 38 ml of carbon tetrachloride and 2.5 ml of 0.86M aluminium tribromide solution. Thereafter the mixture was stirred for 5 hours at 30 C and at ambient temperature for 19 hours. The reaction was quenched by the addition of 20 ml of methanol, and the polymer was isolated after precipitation in 200 ml of methanol containing 4 ml of hydrochloric acid.

DERIVATIVES Only the Step 2 product was prepared.

TESTING Water Permeability Water permeability was determined at 38 C for 24 hours using a 50 mm thick film in accordance with the ASTM E96E standard. Testing results are provided in Table 1. TABLE 1. Water permeability testing results of selected polymers using the ASTM E96E standard. Water Permeability (g/m2 24 h)

Material Step 2 product

6

High-density polyethylene Polypropylene Low-density polyethylene Polyvinyl chloride Poly(ethylene-co-vinyl alcohol) [32 mol% ethylene] Polyaniline

3 5 5 18 35 50

NOTES 1. Linemann [1] prepared polydimethylketene by the Friedel-Craft cationic polymerization of dimethylketene using AlBr3. 2. The Step 2 product containing up to 30 mol% ether content was effective as an oxygen barrier under high relative humidity and used in pipes, bottles, and containers by Egret [2]. References 1. R. Linemann et al., US Patent 7,105,615 (September 12, 2006) 2. H. Egret et al., US Patent 6,793,995 (September 21, 2004), US Patent 6,528,135 (September 21, 2004), and US Patent 6,528,135 (March 4, 2003)

F. Thermally Stable

Title: Polyaryleneetherketone Phosphine Oxide Compositions Incorporating Cycloaliphatic Units for Use as Polymeric Binders in Thermal Control Coatings and Method for Synthesizing Same Author:

T. D. Dang et al., US Patent 7,208,551 (April 24, 2007)

Assignee:

University of Dayton (Dayton, OH)

SIGNIFICANCE The use of polymers as thermal control coatings in space environments is desirable, since they provide significant weight reduction, good mechanical strength, and exhibit thermal and thermooxidative stability. There still remains a need, however, for coatings that resist degradation by ultraviolet radiation and atomic oxygen. This investigation addresses that need using polyaryleneetherketone phosphine oxide materials.

REACTION H3CO O

HO

i

OH

O

Cl O

O

Cl

ii

O

Not isolated

OCH3 HO

O P

iii a

O

O

O

O O OH

118

Experimental

119

i: 4,9-Diamantanedicarboxylic acid, thionyl chloride, aluminum chloride, anisole ii: Pyridine hydrogen chloride iii: 4,40 -Difluorotriphenylphosphine oxide, potassium carbonate, DMAc, toluene

EXPERIMENTAL 1.

Preparation of 4,9-bis(4-Methoxybenzoyl)Diamantane

4,9-Diamantanedicarboxylic acid and excess thionyl chloride were refluxed until a clear solution was obtained and then concentrated. The crude 4,9-diamantanedicarboxylic acid chloride (0.0211 mole) was slowly added to a chilled solution of AlCl3 (6.75 g) and anisole (22.8 g), and the mixture was stirred overnight at ambient temperature. The product was precipitated by pouring into 0.1M aqueous HCl, then stirred, filtered, and the solid further stirred in methanol to remove unreacted anisole. The white solid was re-crystallized from a mixture of 700 ml toluene and 100 ml THF and the product was isolated in 72% yield, MP ¼ 213–214 C.

2.

Preparation of 4,9-bis(4-Hydroxybenzoyl)Diamantane

A round-bottomed flask was charged with the Step 1 product (0.0285 mol) and excess pyridine hydrochloride (0.2850 mol), then heated for 3 hours at 225 C and cooled. The reaction mixture was poured into 40 ml of concentrated HCl diluted with 200 ml of water, and a precipitate formed. The solid was isolated, dried, then dissolved in THF with hexane slowly added until the solution became slightly turbid. The solution was next slowly cooled, and the product was isolated in 57% yield, MP ¼ 313–315 C.

3. Preparation of 4,9-Diamantane-Based Polyaryleneetherketone Triphenylphosphine Oxide A reactionvessel equipped with a Dean–Stark trap was charged with the Step 2 product (1.3212 g), 4,40 -difluorotriphenylphosphine oxide (0.9689 g), potassium carbonate (1.022 g), 7.2 ml DMAc, and 15 ml of toluene and then refluxed for at least 4 hours. After removal of the azeotrope and toluene, the mixture was refluxed at 165 C for an additional 16 hours. The polymer was precipitated in water, shredded in a blender, filtered, dried, and the product was isolated in 92% yield.

120

Polyaryleneetherketone Phosphine Oxide Compositions Incorporating Cycloaliphatic Units

DERIVATIVES TABLE 1. Selected polyaryleneetherketone phosphine oxide derivatives prepared according to the current invention and corresponding viscosities at 30 C.

Entry

Structure

O P

O Step 1 product

Polymer Concentration (g/25 ml CCl3H)

[Z] (dl/g)

0.0632

0.27

0.25

1.18

0.25

0.38

n

O

O O

O

n

P

7

O O

O O 11

O P O

O

n

NOTE Resins prepared by Timberlake [1] consisting of benzoguanamine-modified phenolformaldehyde or melamine-phenol-formaldehyde resins were treated with tris(4methoxy- phenyl)phosphine oxide to prepare coatings in printed circuit boards. Isomeric mixtures of tris(2-hydroxyphenyl)-phosphine oxide compounds were also converted into resins by Brennan [2] by reacting with tris(4-methoxy-phenyl)phosphine oxide derivatives. References 1. L.D. Timberlake et al., US Patent 7,202,311 (April 10, 2007) and US Patent 7,201,957 (April 10, 2007) 2. D.J. Brennan et al., US Patent 6,740,732 (May 25, 2004) and US Patent 6,969,756 (November 29, 2005)

G. Vapor Deposition of Polymers

Title: Functionalization of Porous Materials by Vacuum Deposition of Polymers Author:

M. G. Mikhael et al., US Patent 7,157,117 (January 2, 2007)

Assignee:

Sigma Laboratories of Arizona, LLC (Tucson, AZ)

SIGNIFICANCE Vapor deposition has been used to prepare fibers such as woven and nonwoven synthetic and natural fibers having hydrophobic/oleophobic and biocide properties. This process entails flash evaporation of a perfluoroacrylate monomer and its radiation curing in a vacuum chamber onto a selected fiber surface.

REACTION O

...

... a

i Note 1

...

F2 C

CF3 b

b>5

...

a

F2C

O

b CF3

i: Perfluoroacrylate

121

122

Functionalization of Porous Materials by Vacuum Deposition of Polymers

EXPERIMENTAL Preparation of Polypropylene-g-Perfluoroacrylate Nonwoven Fabric with a Hydrophobic/Oleophobic Repellent Surface A perfluoroacrylate monomer was flash evaporated at 100 millitorr and exposed to polypropylene fibers pretreated in a plasma field within one second while the fabric was traveling at 50 m/min. The condensed monomer layer was then cured in-line by electron beam radiation within 100 milliseconds resulting in a 0.1 mm perfluoroacrylate coating on the material surface. The product had an adequate repellency for both water and oil and a surface energy of 27 dyne/cm.

DERIVATIVES TABLE 1. Water/alcohol and oil repellency testing of fabrics modified with perfluoroacrylate monomer to confer a hydrophobic/oleophobic repellent surface. Oil Repellency Test Fabric

Sample

Water/Alcohol Unwashed

Cotton

Control Treated Control Treated Control Treated

1 6 3 6 3 6

Polyester*1 Nylon*2

Repellency Test 10 Wash Cycles

Unwashed

10 Wash Cycles

1 4 3 5 3 5

1 5 1 6 1 6

1 3 1 4 1 4

Note: Higher testing values are preferred. Surface energies of fabrics were not provided by author. *1 Polyester not specified. *2 Nylon not specified.

NOTES 1. Color changing sensing coatings were prepared in the current invention using a mixture of phenolphthaleine and perfluoroacrylate monomer; heat-sensing coatings were prepared by grafting 4-pentyl-4-cyanobiphenyl; and strawberry odor smelling coatings were prepared by coating a surface with 4-(2,6, 6-trimethyl-1-cyclohexen-1-yl)-3-buten-2-one. 2. In an earlier investigation by the author [1], 0.3 to 0.8 m coatings of polyethylene and poly(a-methylstyrene) solid oligomers having Mn’s of roughly 4000 and 1300 daltons, respectively, were vapor deposited onto a polyester surface at 1 10 4 to 1 10 5 torr at 300 C. 3. Affinito [2] vapor coated hexanediol diacrylate, trimethylolpropane triacrylate, and tripropyleneglycol diacrylate liquid monomers at roughly 80 C and 1 10 4 torr onto polyethylene terephtholate and then radiation polymerized the surface using electron beam radiation.

Notes

123

4. Cured coatings having dielectric dissipation factors < 0.05 at 24 C at 600 Hz on conductors were prepared by Krongauz [3] by radiation curing a surface coating containing hydroxyl-terminated hydrogenated 1,2- and 1,4-polybutadiene, isophorone diisocyanate, and hydroxyethylacrylate. 5. Bilodeau [4] prepared barriers consisting of radiation cured N-vinyl-2-pyrrolidone and N-vinylcaprolactam that were impervious to migratory components in autmotive tires. References 1. 2. 3. 4.

M.G. Mikhael et al., US Patent 7,005,161 (February 28, 2006) J.D. Affinito, US Patent 7,112,351 (September 26, 2006) V.V. Krongauz et al., US Patent 7,109,253 (September 19, 2006) W.L. Bilodeau et al., US Patent 7,141,285 (November 28, 2006)

H. Succinic Anhydride Derivatives

Title: Light Absorbent Agent Polymer for Organic Anti-reflective Coating and Preparation Method and Organic Anti-reflective Coating Composition Comprising the Same Author:

J.-c. Jung et al., US Patent 7,033,729 (April 25, 2006)

Assignee:

Hynix Semiconductor, Inc. (Kyungki-do, KR)

SIGNIFICANCE In the fabrication process of ultra-fine patterns for photoresists using ArF light source (193 nm), few organic or inorganic anti-reflective coating currently exist. This art addresses this need using poly(maleic anhydride-co-4-dihydro-1,4-methano-naphthalene-5,8-diol) diacetate crosslinked with poly(styrene-co-vinyl dimethylacetal).

REACTION O

O

O

i

a O

O

O O

ii

b

Note 1

O O

Organic anti-reflective material

O

i: 4-Dihydro-1,4-methano-naphthalene-5,8-diol diacetate, propylene glycol methylether acetate, 2,20 -azobis isobutyronitrile ii: Poly(styrene-co-vinyl dimethylacetal), propylene glycol methylether acetate, methyl 3-methoxy propionate, 2-heptanone, THF, 2-hydroxycyclo-pentyl-1-trifluoromethylsulfonic acid

124

Notes

125

EXPERIMENTAL 1.

Preparation of Light-Absorbing Polymer Agent

A reaction vessel was charged with maleic anhydride (20 g), 1,4-dihydro-1,4-methano-naphthalene-5,8-diol diacetate (26 g), and propylene glycol methylether acetate (26 g), and then treated with 2,20 -azobissobutyronitrile (0.5 g). The mixture was reacted at 65 C for 7 hours, concentrated, precipitated in water, washed with diethyl ether, and the product was isolated in 40% yield, Mw of roughly 7000 daltons. 2.

Preparation of Organic Anti-reflective Coating Composition

The Step 1 product (1 g) and poly(styrene-co-vinyl dimethylacetal) (0.4 g) were dissolved in a mixture comprising propylene glycol methylether acetate (4 g), methyl 3-methoxy propionate, 2-heptanone (10 g), and THF (7 g). The solution was then treated with 2-hydroxycyclo-pentyl-1-trifluoromethylsulfonic acid (0.1 g), filtered, and the product was isolated. 3.

Preparation of Organic Anti-reflective Coating and Photoresist Pattern

The Step 2 product was spin-coated onto a silicone wafer and baked for 2 minutes at 215 C. Thereafter the anti-reflective mixture was coated with a Keum Ho petroleum photosensitive agent and baked for 90 seconds 110 C. After these processes the material was exposed to a light source by means of ASML/900 scanner apparatus and baked an additional 90 minutes at 130 C. The exposed wafer was developed using an aqueous solution of 2.38% tetramethyl-ammonium hydroxide.


NOTES 1. The Step 2 crosslinking agent, poly(styrene-co-vinyl dimethylacetal), (I), is illustrated below.

a

b O

(I)

O

126

Light Absorbent Agent Polymer for Organic Anti-reflective Coating and Preparation Method

2. An additional Step 1 light absorbing polymer agent, (II), was prepared by the author [1] in a subsequent investigation and used as an organic anti-reflective coating.

a O

O

O

b

O

O

HO

OH

(II) 3. Compositions for an anti-reflective light-absorbing layer using diazoquinones, (III), were prepared by Yoon [2] and used in forming patterns in semiconductor devices.

a O

O

O

O

CO2H

N2 O

(III) 4. Lee [3] prepared organic anti-reflective polymer coatings consisting of polyvinyl phosphoric acid and poly(vinyl acetate-co-ethylene).

Notes

127

5. Anti-reflective polymer coatings, (IV), prepared by the author [4] were used in forming ultra-fine patterns of photoresist for photolithography.

O

a

O

O

O

b N

O

CH2

O

O

O

O

a (IV)

N

O

b

References 1. J.-c. Jung et al., US Patent Application, 2005-0084798 (April 21, 2005), US Patent 7,205,089 (April 17, 2007), and US Patent Application, 2006-0004161 (January 5, 2006) 2. S.-w. Yoon et al., US Patent 6,838,223 (January 4, 2005) 3. G.-s. Lee et al., US Patent 7,198,887 (April 3, 2007) 4. J.-c. Jung et al., US Patent 7,186,496 (March 6, 2007)

V. COSMETICS Title: Water-Soluble or Water-Dispersible Graft Polymers, Their Preparation and Use Author:

S. N. Kim et al., US Patent 6,992,161 (January 31, 2006)

Assignee:

BASF Aktiengesellschaft (Ludwigshafen, DE)

SIGNIFICANCE Urethane and polyurea segments have been introduced into a polymer containing polyesters, polyethers, and casein. When blended into hair spray formulations containing upto 5 wt% solids, enhanced curl retention and flexural strength resulted.

REACTION O

CO2H

i CO2H

O HN

O O

O

20

O 4

O O

O

6

O O

H N

O 20

HN

O a

O O HN

NH Casein

i: Isophthalic acid, adipic acid, hexanediol, polyethylene glycol, dimethylolpropanoic acid, isophorone dissocyanate, triethanolamine, casein, 2-amino-2-methylpropanol

EXPERIMENTAL 1.

Preparation of Polyethylene Glycol Graft Copolymer

A reaction kettle was charged with polyesterdiol (0.5 mol; Mw 1000 daltons; prepared from isophthalic acid, adipic acid and hexanediol), polyethylene glycol (0.05 mol; MW ¼ 1500 daltons), and dimethylolpropanoic acid (1.25 mol) dissolved in methyl ethyl ketone. The mixture was heated to 80 C. When the reaction was completed the Advances in Polymer Chemistry and Methods Reported in Recent US Patents, by Thomas F. DeRosa Copyright Ó 2008 by John Wiley & Sons, Inc. 129

130

Water-Soluble or Water-Dispersible Graft Polymers, Their Preparation and Use

mixture temperature was lowered to 50 C and isophorone diisocyanate (1.9 mol) was added dropwise. At an internal temperature of 90 C the reaction mixture was stirred until the isocyanate group content remained constant. Thereafter the reaction mixture was cooled to ambient temperature and treated dropwise with 15% casein (116.5 g) dissolved in triethanolamine, and next stirred until isocyanate groups were no longer detectable. The mixture was then treated with water and the product was neutralized with 2-amino-2-methylpropanol. The solution was concentrated, and the product was obtained by spray drying under vacuum at 80 C. Hair Spray Formulation TABLE 1. Hand pump spray formulation with a volatile organic compounds content of 55%. Component

Charge (wt%)

Step 1 product (Solids content) Water Ethanol Fragrance/surfactant

5 40 55 q.s

Flexural Strength and Curl Retention

TABLE 2. Hair spray formulations of selected casein-containing Step 1 products and their effect on curl retention and flexural strength. Flexural Curl Polyesterdiol PEG E1500 DMPA MDEA IPDI Casein Retention Strength (cN) (%) Entry (mol) (mol) (mol) (mol) (mol) (wt%) 3 4 6

1 1 0.9

0.1 0.1 0.1

— 2.5 2.5

— — 0.1

— 3.8 3.8

50 10 5

51 65 73

312 356 452

NOTES 1. Polyurethanes containing polytetrahydrofuran, diethylene glycol, stearyl alcohol, and hexamethylene diisocyanate were prepared by Meffert [1] and used in hair compositions. 2. Alkali-swellable polymer compositions consisting of acrylic acid, methyl methacrylate, behenyl methacrylate, lauryl methacrylate, and sodium lauryl sulfate were prepared by Tamareselvy [2] and used as a hair rheology modifier and as a hair setting agent.

Notes

131

3. Rollat [3] prepared acrylate terpolymers consisting of 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, and methacrylic acid, 55, 50, 2.5, 2.5 parts, respectively, that were useful in hair styling compositions. 4. Polymers consisting of t-butyl acrylate, methacrylic acid, sodium ether dodecyl sulfate, and n-dodecylthiol were prepared by Drohmann [4] and used in hairsprays. References 1. 2. 3. 4.

H. Meffert et al., US Patent 7,019,061 (March 28, 2006) K. Tamareselvy et al., US Patent 7,153,496 (December 26, 2006) I. Rollat et al., US Patent 7,122,175 (October 17, 2006) and US Patent 7,048,916 (May 23, 2006) C. Drohmann et al., US Patent 7,147,842 (December 12, 2006)

VI. DENTAL A. Cement

Title: (Meth)Acrylate-Substituted Iminooxidiazine Dione Derivatives Author:

N. Moszner et al., US Patent 7,078,446 (July 18, 2006)

Assignee:

Ivoclar Vivadent AG (Schaan, LI)

SIGNIFICANCE UV-curable dental cement composites consisting of 20% asymmetrical 1,3,5oxadiazine-2,4-dione trimethacrylate derivatives have been prepared that have lower shear viscosities than their symmetric triazole counterpart. This property is particularly needed for preparing “flowable” pre-cured cement paste.

REACTION O

O O OCN

6

O

6

O

N

NCO 6 NCO

i Note 1

O

O

O

O N H

6

O

O

O 6N H N O 6N H

O

O O O O

i: 2-Hydroxylethyl methacrylate, 2,2,6,6-tetramethyl-piperidine-1-oxyl, hydroquinone monomethylether, dibutyltin dioctoate, CH2Cl2


134

(Meth)Acrylate-Substituted Iminooxidiazine Dione Derivatives

EXPERIMENTAL Preparation of 3,5-bis(6-(6-Hexyl Carbamate-Methacrylate)-6-[(6-Hexyl Carbamate-Methacrylate)Imino]-1,3,5-Oxadiazine-2,4-Dione 3,5-bis(6-Isocyanato-hexyl)-6-[(6-isocyanato-hexyl)imino]-1,3,5-oxadiazine-2,4dione (0.1 mol) was added dropwise at ambient temperature to a solution containing 2-hydroxylethyl methacrylate (0.3 mol), 2,2,6,6-tetramethyl-piperidine-1-oxyl (12 mg), hydroquinone monomethylether (25 mg), and dibutyltin dioctoate (0.2 g) dissolved in 100 ml of CH2Cl2 and then stirred for 20 hours. Next the reaction mixture was washed twice with 100 ml of 1.0M NaOH and three times with 100 ml of saturated brine. The organic phase was dried with Na2SO4 and concentrated, and the product was isolated in 67% yield. IR (ATR; cm 1): 3368 (w), 2930 (m), 2858 (w), 1785 (w), 1682 (s), 1522 (m), 1458 (s), and 1163 1 H-NMR (CDCl3): d 1.35 (br, 12 H, CH2), 1.51 (br, 6H, CH2), 1.63 (br, 6H, CH2), 1.94 (s, 9H, CH3), 3.17 and 3.34 (t, sat. 6H,CH2N), 3.84 (t, 6H, CH2N), 4.31 (br, 12H, CH2O), 5.02 5.03 (br, 3H, NH), 5.59 and 6.13 (2s, each 3H, .dbd.CH2) ppm

DERIVATIVES TABLE 1. Viscosity of UV-curable dental composites containing 20% experimental assymmetric additives or a symmetric reference. Entry

Paste Shear Viscosity (Pas)

Structure

O O

1

O

O

O N H

O 6N

6

O

O

N

H

O Symmetrical Reference

O

O

O N H

6N

O

O

O

H

2.21

O

O

6N

O

O

O

O

O N

N

6N

H

O

O

O

O O 6

N H

O

O O

3.36

Derivatives

135

Table 1. (Continued ) Entry

Paste Shear Viscosity (Pas)

Structure

O

O

O

O

O O

2

O N H

O 6N

6

O

O

O

N

O

O

H

2.20

O

6 NH

O

O O

O

O

O

O

O

O

O

O

O

O O

Symmetrical Reference

O N H

6N

6

O O

O H O

N

O

O O O

6 NH

O

O O

O

2.79

O O

O

Note: The remainder of the composit consisted of 80 wt% filler consisting of barium- aluminum-boron silicate glass powder, silicon dioxide-zirconium dioxide, and ytterbium fluoride. For dental composites lower viscosities are preferred because of their flowability.

136

(Meth)Acrylate-Substituted Iminooxidiazine Dione Derivatives

NOTES 1. The preparation of the triisocyanate Step 1 reagent is described by Richter [1]. 2. In an earlier investigation by the author [2] di-amides, (I) and (II), were prepared and used in dental adhesive composites. Materials based on acrylic-ester phosphonic acids, (III) and (IV), and used in dental cements were also prepared by the author [3]. O N O

N

(I)

O O

O

O

O P OH OH

O

H N

O

N H

N H

O

O

(II) O

O

O HO P HO

H N

O

O

O

O

(III)

O

O OH P OH

(IV)

3. In a subsequent investigation by the author [4] photopolymerizable bisacylphosphine oxides, (V), effective as Norrish type I cleavage agents at 400 to 500 nm, were prepared and used as self-conditioning dental fixing cements. Self-etching dental materials such as adhesives, coating materials, and composites consisting of (meth)acrylamide phosphates, (VI), were also prepared by the author [5] and used in restorative dentistry.

O O

O

O O

P

(V) O P O

OH OH

N O

N

(VI)

O

Notes

137

4. Polymerizable cyclopropyl acrylates, (VII), were prepared by the author [5] and used as components in dental cements and filling materials. O O

CO2C2H5 O O

C2H5O2C O

(VII)

O O

O


F.L. Richter et al., US Patent 5,914,383 (January 22, 1999) N. Moszner et al., US Patent 6,953,832 (October 11, 2005) N. Moszner et al., US Patent 6,953,832 (October 11, 2005) and US Patent 6,900,251 (May 31, 2005) N. Moszner et al., US Patent Application 2007-0027229 (February 1, 2007) N. Moszner et al., US Patent Application 2006-0178469 (August 10, 2006)

B. Dental Composites

Title: (Meth)Acrylic Ester Compound and Use Thereof Author:

A. Otsuji et al., US Patent Application 2007-0078198 (April 5, 2007)

Assignee:

Mitsui Chemicals, Inc. (Tokyo, JP)

SIGNIFICANCE Diacrylate monomers have been prepared that are photocurable in visible light and that have small polymerization shrinkage and high X-ray contrast properties. When polymerized with 0.01 to 0.04 mm glass powder, these dental composites were easily machined into artificial teeth.

REACTION i O

O

O

ii

O

O

O

O

OH

O O

O

OH

O

O

O O

O

Cl

Cl

iii Note 1

O O

O

O

O

i: 4-Phenylphenol, sodium hydroxide, DMAc 138

O

O O

O

Experimental

139

ii: 3-Chloropropionic acid chloride, DMAc iii: Acetone, triethyl amine

EXPERIMENTAL 1. Preparation of 1,3-di-[2-Hydroxyl-3-(4-Phenylphenoxy)-1-Propoxy] Benzene A reactor was charged with 4-phenylphenol (0.40 mol), NaOH (0.53 g), and DMAc (40 g) and then treated with the dropwise addition of a solution of resorcin diglycidyl ether (0.20 mol) in DMAc (40 g). The mixture was stirred for 6 hours at 100 C and diluted with 200 g of methanol/water, 1:1. Crystals that precipitated were collected, dried, and the product was isolated in 97% yield as a colorless powder. 2. Preparation of 1,3-di-[2-(Chloropropionic Acid Ester)-3(4-Phenylphenoxy)-1-Propoxy]Benzene The Step 1 product (0.10 mol) was dissolved in DMAc (60 g) and treated with the dropwise addition of 3-chloropropionic acid chloride (0.36 mole) at 60 C for over 60 minutes. The mixture was stirred for 4 hours at 60 C and cooled to ambient temperature. It was poured into ice water, extracted with of toluene (250 g), and washed with 3% aqueous NaHCO3. The organic layer was repeatedly washed with water until it was neutral and concentrated, and the product was isolated in 95% yield as a colorless, transparent, and viscous liquid. 3. Preparation of 1,3-di-[2-(Acrylic Ester)-3-(4-Phenylphenoxy)-1Propoxy]Benzene The Step 2 product (0.10 mol) was dissolved in acetone (100 g) and treated with triethyl amine (0.36 mol) at 5 C for over 1 hour and then stirred for 2 hours. The mix-ture temperature was warmed to ambient temperature and extracted with 200 g apiece toluene and water. The organic portion was isolated and treated with 5% hydrochloric acid, washed repeatedly with water until it was chloride free, and then concentrated. The residue was purified by silica gel column chromatography using toluene, and the product was isolated in 80% yield as a colorless and transparent liquid. 1

H-NMR (CDCl3) d 4.20–4.30 (m, 8H), 5.50–5.60 (m, 2H), 5.85 (d, 2H), 6.10–6.20 (m, 2H), 6.45 (d, 2H), 6.50–6.60 (m, 3H), 6.90–7.60 (m, 19H) FD-MS (m/z); 670 (Mþ)

140

(Meth)Acrylic Ester Compound and Use Thereof

DERIVATIVES

O O

O O

O O

O O

O

O

O

O O

O

O

O

O

O

O

O

O

O O

O

NOTES 1. Experimental dental fillers were cured by irradiation with visible rays for 60 seconds using a visible ray irradiator. 2. Nakamura [1] prepared UV-curable acyclic esters of 1,3-dithiolane, (I), for use as dental composites.

O S O

O O

S

a

a=2–4

(I)

3. Crosslinkable polyhedral oligomeric silsesquioxane, (II), prepared by Jin [2] were used as dental composites in restorative applications, especially in crown and bridge materials.

Notes

141

OY

R Si

O R

O O

Si

R

OY

R

Si

O

O O

Si

R = C1 – C 9 Y= acrylate

OY

Si

O

SI R

O

Si R

R

(II) 4. Methacrylate-substituted asymmetric trimers consisting of iminooxidiazine dione derivatives, (III), were prepared by Moszner [3] that had excellent mechanical properties and were used as dental cements. O O O

O

O

O N H

6

O

N

N

N 6H

N 6 H

(III)

O O

O

N

O

O

O

O O

5. Heilmann [4] prepared a dental material from the co-oligomerization of i-octyl acrylate and methacryloyloxyethylcarbamoyl-ethylmethylketonoxime, (IV). The copolymer had a Mn of roughly 21,000 daltons and a shrinkage of less than 2% after thermal curing.

O O O

N H

O

N

(IV)

6. Metathesis-curable compositions of polyethylene glycol monomers, (V), using ruthenium derivatives, (VI), were prepared by Angeletakis [5] and used as dental impression materials and orthodontic appliances.

142

(Meth)Acrylic Ester Compound and Use Thereof

O O O

O

O O

O

O

O

O

8

O

Mesityl

O

(V)

N

N

Mesityl

Cl Cl

Ru

(VI)


M. Nakamura et al., US Patent 6,835,844 (December 28, 2004) S. Jin et al., US Patent 7,160,941 (January 9, 2007) N. Moszner et al., US Patent 7,078,446 (July 18, 2006) S.M. Heilmann et al., US Patent 7,074,858 (July 11, 2006) and US Patent 7,015,286 (March 21, 2006) C. Angeletakis et al., US Patent 7,001,590 (February 21, 2006)

VII. ELECTROACTIVE A. Charge Transport Materials

Title: Hole Transport Polymers and Devices Made with Such Polymers Author:

G. D. Jaycox et al., US Patent 7,205,366 (April 17, 2007)

Assignee:

E.I. du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE Many electroluminescent materials have poor charge transport properties. The present invention is directed to polymeric agents containing grafted naphthalene or pyrene, which makes then effective as both hole transport and electroluminescent agents.

REACTION

a

i O

OCH3

O

OCH3

b O

O OH

a

ii O

b O

O

OCH3 O

O NH

i: 2-Hydroxyethyl methacrylate, VazoÒ 52, 2,20 -azobis(2,4-dimethyl pentane nitrile), acetone ii: 1,10 -Carbonyldiimidazole, 1-(1-naphthyl)ethylamine, THF


144

Hole Transport Polymers and Devices Made with Such Polymers

EXPERIMENTAL 1. Preparation of Poly(Methyl Methacrylate-co-2-Hydroxyethyl Methacrylate) A container was charged with a solution of VazoÒ 52 catalyst and 2,20 -azobis(2,4dimethyl pentane nitrile) (4.5 g) dissolved in acetone (600 g); a second container was charged with methyl methacrylate (540 g) and 2-hydroxyethyl methacrylate (180 g). The first and second containers were uniformly fed into a reactor for 330 and 240 minutes, respectively, and then refluxed for 1 hour. After standard workup the product was isolated in 100% yield, having a Mn of 30,308 daltons, Mw of 93,195 daltons, and a PDI of 3.07. 2. Preparation of Poly(Methyl Methacrylate-co-Ethyl-(Naphthyl Carbamate)Methacrylate) A reactor was charged with the Step 1 product (20 g), THF (445 g), and 1,10 carbonyldiimidazole (7.50 g) and then stirred for 1 hour at ambient temperature. The mixture was treated with the dropwise addition of 1-(1-naphthyl)ethylamine (7.9 g) dissolved in THF (67 g) over 20 minutes and then stirred for 48 hours at ambient temperature. The mixture was concentrated to one-third its volume and precipitated in 200 ml water. The residue was extracted five times with 200 ml of water, ground in a blender and dried, and the product isolated was in 84% yield. 1

H-NMR (DMSO-d6) d 6.7–8.1 (aromatic protons for pendant naphthylene group); ratio of aromatic H aliphatic H ¼ 0.20 (theoretical ¼ 0.19) UV-Vis (DMSO) lmax 305 nm

DERIVATIVES A pyrene polyamide derivative, (I), was also prepared.

HN H N

O

H N O

(I)

O

a

Notes

145

NOTES 1. By incorporating ethynyl functions into existing 1,3,4-oxadiazole-containing electroluminescent electron hole transport dyes, (II), Roberts [1] increased the device operating lifetime by inhibiting oxadiazole aggregation. Tokarski [2] prepared azine derivatives, (III), that were also effective as hole transport agents. C4H9

t-C4H9

C4H9

N N

O

O N C4H9

N t-C4H9

C4H9

(II)

N

HO N N N

O

OH S

S

S O

(III)

2. Electroluminescent polymeric 1,3,4-oxadiazole-containing agents, (IV), prepared by Roberts [3] were also effective as electron hole transport agents. C8H17

C8H17

C8H17

a O

(IV)

N N

OC 8H17

C8H17

146

Hole Transport Polymers and Devices Made with Such Polymers

3. Electron hole transport composites consisting of poly(aniline-co-2-acrylamido-2-methyl-propanesulfonic acid), (V), and silicon nanoparticles were prepared by Hsu [4] and then used to prepare light-emitting diodes and electrodes for thin film field effect transistors.

H N a O

b NH

SO3H

(V)

4. Tamao [5] prepared a light-emitting material effective as a charge transport agent containing boron, (VI), which was used as a luminescent element.

C8H17O

OC8H17

B

(VI)


R.R. Roberts et al., US Patent 7,192,657 (March 20, 2007) Z. Tokarski et al., US Patent 7,189,482 (March 13, 2007) R.R. Roberts et al., US Patent 7,094,902 (August 22, 2006) C.-H. Hsu et al., US Patent 7,189,771 (March 13, 2007) K. Tamao et al., US Patent 7,157,154 (January 2, 2007)

a

Title:

Acrylic Polymer and Charge Transport Material

Author:

H. Ishizawa et al., US Patent 7,012,123 (March 14, 2006)

Assignee:

Sekisvi Chemical Co., Ltd. (Osaka, JP)

SIGNIFICANCE Isotactic and syndiotactic poly(9-fluorenyl methacrylate)s have been prepared that are effective as hole mobility charge transport materials and as electrical conductors of charge transport materials.

REACTION O

a O

O

OH

i

O

ii Isotactic and syndiotactic prepared

i: Benzene, triethylamine, methacryloyl chloride ii: THF, t-butyllithiun

EXPERIMENTAL 1.

Preparation of 9-Fluorenyl Methacrylate

A 200 ml reaction flask charged with 9-fluorenol (11 mmol),180 ml of benzene, and triethylamine (13.75 mmol) was cooled to 6 C and then treated with the slow addition of methacryloyl chloride (13.75 mmol). Thereafter the mixture was stirred at ambient temperature for 24 hours. The solution was washed with water and saturated NaHCO3, and the organic layer was isolated, dried with MgSO4, and concentrated. The residue 147

148

Acrylic Polymer and Charge Transport Material

was purified by column chromatography using benzene, and the product was isolated in 40% yield as white solid, MP ¼ 61 C. 1

H-NMR (CDCl3) d 7.696 (2H, d), 7.580 (2H, d), 7.427 (2H, t), 7.306 (2H, t), 6.868 (1H, s), 6.166 (1H, s), 5.621 (1H, s) and 2.015 (3H,s)

2.

Preparation of Syndiotactic Poly(9-Fluorenyl Methacrylate)

A 25 ml reaction tube was charged with the Step 1 product (0.687 mmol), dissolved in 3.2 ml of THF, and then cooled to 78 C and treated with 0.07 ml of 1.36 M t-BuLi (0.095 mmol). The mixture reacted at 78 C and was quenched with 2 ml of methanol. The solution was precipitated in 30 ml of methanol and isolated. The precipitate was dissolved in 30 ml hexane, filtered, and concentrated, and 0.147 g product was isolated having a Mn of 2600 daltons with a PDI of 1.25. 1

H-NMR (CDCl3) d 6.988 7.501 (8H, m), 6.322 (1H, s), 2.108 (1.79H, s), 1.127 (2.9H, s)

DERIVATIVES The isotactic derivative was also prepared

TESTING 1. Measurement of Hole Mobility of Charge Transport Material (TOF Method) A CH2Cl2 solution consisting of 10 wt% of the Step 2 product and 1 wt% of 2,4,7trinitrofluorene malononitrile as dopant was prepared and cast onto an ITO glass substrate, dried; a 1 mm film was isolated. Aluminum was then vacuum deposited onto the film to a thickness of 1000 C forming a 5 5 mm aluminum electrode. Hole transfer time was measured by applying a voltage of 5 V to the electrode while simultaneously exposing it to a pulse laser beam at 337 nm. Hole mobility testing results are provided in Table 1. 2.

Electrical Conductivity of Charge Transport Material

The film prepared above was evaluated for electrical conductivity at an interelectrode distance of 90 mm. Testing results are provided in Table 1. TABLE 1. Hole mobility and electrical conductivity for syndiotactic and isotactic poly(9-fluorenyl methacrylate). Entry Syndiotactic Isotactic

Hole mobility (cm2 V1 s1) 1.02 104 8.02 104

Electrical Conductivity (S/cm) 1.13 105 5.13 105

Notes

149

NOTES 1. Electroactive fluorene copolymers, (I), were prepared by Uckert [1] using 2,7diiodo-9,9-di-2-ethylhexyl fluorine. This product was used as a component in light-emitting diodes.

C8H17

N a C6H13

C8H17

(I)

2. Chen [2] prepared electroluminescent conjugated polymers, (II), containing phosphorescent components that were used as light-emitting diodes. Boron analogues, (III), prepared by Tamao [3] were also used as light-emitting diode components.

a S

S

a

B

N

N

(III)

(II)

References 1. F.P. Uckert et al., US Patent 7,220,820 (May 22, 2007), US Patent 7,214,763 (May 8, 2007), and US Patent 7,211,643 (May 1, 2007) 2. S.-A. Chen et al., US Patent 7,220,819 (May 22, 2007) 3. K. Tamao et al., US Patent 7,157,154 (January 2, 2007)

B. Dielectric Materials

Title: Thermosetting Aromatic Dielectric Material Author:

J. Economy et al., US Patent 7,211,642 (May 1, 2007)

Assignee:

The Board of Trustees of the University of Illinois (Urbana, IL)

SIGNIFICANCE Although minimization in integrated circuits allows for faster device operation, propagation delays increase with increasing numbers of interconnects. To address this problem, lower dielectric constant materials have been prepared.

150

Experimental

151

REACTION

O

OH

i

O

O

O O

O

ii

O

O

O

O O

O

a

i: Benzenetricarboxylic acid chloride, pyridine, CH2Cl2 ii: 3-Diethynyl benzene, phenylacetylene, copper(I) chloride, oxygen, acetone, pyridine

EXPERIMENTAL 1.

Preparation of tris-(3-Ethynyl-Phenyl)Trimesate

A reaction flask was charged with 3-ethynyl phenol (0.017 mol), 5 ml of pyridine, and 20 ml of CH2Cl2 and treated with the dropwise addition of 1,3,5-benzenetricarboxylic acid chloride (0.0055 mol) dissolved in 10 ml of CH2Cl2 and refluxed for 6 hours at 45 C. The resulting yellow solution was washed 3 times apiece with 20 ml of 1 M HCl, 1M NaOH, and water. The mixture was then dried with Na2SO4, filtered, concentrated, and the product was isolated as a yellow powder in 58% yield.

152

Thermosetting Aromatic Dielectric Material

2. Preparation of Poly[3-Diethynyl Benzene-co-(tris-(3-Ethynyl-Phenyl) Trimesate)] A reactor was charged with CuCl (0.0135 mol) and 67 ml acetone and then slowly heated with stirring to 30 C and treated with 0.83 ml of acetone/pyridine, 1:1. The slurry was stirred for 10 minutes until oxygen bubbled through the mixture turning the light green slurry dark green. The flow of O2 was continued throughout the rest of the reaction. In a separate vessel, a mixture consisting of 3-diethynyl benzene (14.27 mmol), the Step 1 product (1.59 mmol), phenylacetylene (0.111 mol), and 0.83 ml of the acetone/ pyridine mixture in 40 ml of acetone was added to this vessel in a single portion. Heating was removed, an additional 5 ml of the acetone/pyridine was added over a period of 30 minutes, and the temperature was kept below 45 C via an ice bath. After the acetone/pyridine addition was completed, the reaction temperature was kept between 30 C and 40 C for 12 hours in the dark. The reaction mixture was precipitated in 400 ml of methanol containing 11 ml of 12M HCl, filtered, and washed with methanol. The light yellow paste was dissolved in 50 ml of CCl3H, washed 3 times apiece with 10 ml 10% HCl and then water, dried with MgSO4, filtered, and concentrated. The residue was dissolved in 20 ml of CCl3H and then re-precipitated from 600 ml of methanol. The mixture was re-filtered, washed with methanol, and dried, and 1.19 g of product was isolated as a white powder. 1 H-NMR d 9.2 (m, 3H), 7.2 7.5 (m, 12H) FTIR (cm1) 3300 ethynyl C–H stretch, 1750 C¼O

DERIVATIVES A second derivative was also prepared as shown below.

a O

O

O

O

NOTES 1. Low dielectric constant compositions consisting of adamantyl, (I), and diadamantyl derivatives with a porogen consisting of polyacenaphthylene homopolymer were prepared by Li [1] and used as substrate materials in microchips,

Notes

153

multichip modules, laminated circuit boards, and printed boards. Related adamantly and diadamantyl derivatives were prepared by Lau [2].

(I)

2. A low dielectric constant composition consisting of poly(divinylsiloxanebisbenzocyclobutene) having a Mw of roughly 50,000 daltons and poly(propylene glycol) biscinnamate having a Mw of roughly 2200 daltons, was prepared by Bruza [3] and used in electronic applications such as integrated circuits, multichip modules, and flat panel display devices. 3. You [4] prepared porous thermoset dielectric materials having low dielectric constants which were used in electronic component manufacture with crosslinked polymeric porogen particles as provided in Table 2.

TABLE 1. Components used in preparing porogen particles which were compatible with the B-staged benzocyclobutene dielectric materials after crosslinking with 10% trimethylol-propane triacrylate. Entry A B D G

Monomer A

Monomer B

Ratio A/B

Styrene N-Vinylpyrrolidone Styrene Styrene

N-Vinylpyrrolidone — Vinylanisole Vinylanisole

45/45 — 45/45 80/10

4. Pore-generating materials, particularly b-cyclodextrins, were used by Lyu [5] with silsesquioxane derivatives to prepare low dielectric constant materials.

154

Thermosetting Aromatic Dielectric Material

References 1. B. Li et al., US Patent 7,141,188 (November 28, 2006), US Patent 7,060,204 (July 13, 2006), and US Patent 6,740,685 (May 25, 2004) 2. K. Lau et al., US Patent 6,987,147 (January 17, 2006) 3. K.J. Bruza et al., US Patent 7,109,249 (September 19, 2006) 4. Y. You et al., US Patent 6,998,148 (February 14, 2006) 5. Y.Y. Lyu et al., US Patent 7,169,477 (January 30, 2007)

C. Donor-Acceptor Complexes

Title: Polyester Having p-Conjugated Group in Side Chain and Charge Transporting Material Using the Same Author:

T. Nakano, US Patent 7,235,620 (June 26, 2007)

Assignee:

Japan Science and Technology Corporation (Saitama, JP)

SIGNIFICANCE Beginning with 9-fluorene carboxylic acid, high molecular weight poly(9-hydroxy methyl-9-fluorene carboxylic acid) has been prepared by the homopolymerization of 9-hydroxymethyl-9-fluorene carboxylic acid using trifluoro methanesulfonate as the catalyst. This polymeric agent readily formed donor-acceptor complexes with 1,3-dinitrobenzene and is suitable as a charge transport material.

REACTION

ii

i CO2H

HO2C

OH

O

O O

a

i: THF, paraformaldehyde, CH2Cl2, butyl lithium ii: THF, methanol, tin(II), trifluoromethanesulfonate, diazomethane

155

156

Polyester Having p-Conjugated Group in Side Chain and Charge Transporting Material

EXPERIMENTAL 1.

Preparation of 9-Hydroxymethyl-9-Fluorene Carboxylic Acid

A reactor was charged with 9-fluorene carboxylic acid (23.7 mmol) and 300 ml of THF and then cooled to 78 C and treated with 41.0 ml of 1.6 M butyl lithium solution in hexane. The mixture was stirred for 30 minutes, treated with paraformaldehyde (75.0 mmol) dissolved in 100 ml of THF at 78 C, and stirred 13 hours at ambient temperature. Water was then added, the solution extracted with diethyl ether, and the pH of the aqueous layer lowered to 2 using 1M hydrochloric acid. The mixture was re-extracted with CCl3H, and the organic layer dried using anhydrous MgSO4. The low-boiling fraction was distilled under reduced pressure and 4.21 g of residue isolated. The CH2Cl2-insoluble fraction was collected, and the product isolated in 80.5% yield.

2.

Preparation of Poly(9-Hydroxymethyl-9-Fluorene Carboxylic Acid)

The Step 1 product (0.21 mmol) and (CF3SO3)2Sn (0.9 mg) were introduced into a reaction vessel; the mixture was shaken until uniform then heated for 3 hours at 180 C. The mixture was then separated by decantation into THF where 47.1 mg dissolved and 2.20 mg was insoluble. The THF-soluble portion was then redissolved in 3 ml THF and treated with diazomethane dissolved in 1 ml diethyl ether and stirred for 5 hours at ambient temperature. The mixture was concentrated and the residue divided into a methanol-soluble part (8.10 mg) and methanolinsoluble part (34.9 mg). The methanol-insoluble part was divided into a THFsoluble part (14.19 mg) and a THF-insoluble part (20.64 mg). The part that was insoluble in methanol but soluble in THF was identified as the product with a Mn of roughly 1.0 105 daltons. 1

H-NMR (CDCl3) d: 7.78 (d, J ¼ 7.5, 2H), 7.67 (d, J ¼ 7.5, 2H), 7.46 (dd, J ¼ 7.0, 2H), 7.54 (dd, J ¼ 8.0, 2H), 4.02(s, 4H).

DERIVATIVES 9-Hydroxy-9-fluorene carboxylic acid was also prepared.

HO2C

OH

Notes

157

TESTING Donor-Acceptor Testing The Step 2 product (2.98 mg) and 1,3-dinitrobenzene (1.80 mg) were dissolved in 10 ml of THF and then diluted 100 times. This stock solution was used for absorption spectrum measurements in a 10 mm quartz cell at ambient temperature. The intensity was 0.140 at 242 nm, which changed to 0.108 after the addition of 1,3-dinitrobenzene. By changing the 1,3-dinitrobenzene concentration from 2.5 105 M and 5.0 105 M at 242 nm, the absorption intensity changed from to 0.077 and 0.059, respectively. This hypochromic effect demonstrated that the fluorene ring of the polymer and 1,3dinitrobenzene formed a stacked complex.

NOTES 1. Donor-acceptor fluorene complexes were also prepared by Ishizawa [1] using the poly(9-fluorenyl methacrylate), (I), substrate.

a O

O

(I) 2. Fluorene monomers, (II), previously prepared by the author [2] then polymerized and, had a light emission peak at 400 nm, which was different from the polymer light emission peak wave length of 305 nm.

(II) References 1. H. Ishizawa et al., US Patent 7,012,123 (March 14, 2006) 2. T. Nakano et al., US Patent Application 2004-0132963 (July 8, 2004)

D. Electroconductive

Title: Halogenated Thiophene Monomer for the Preparation of Regioregular Polythiophenes Author:

C. Werner et al., US Patent 7,262,264 (August 28, 2007)

Assignee:

Honeywell International, Inc. (Morristown, NJ)

SIGNIFICANCE Poly(3-hexyl)thiophene has been prepared in 93.5% head-to-tail regioregularity by reacting 5-bromo-2-chloro-3-hexylthiophene with magnesium, t-butylmagnesium chloride, 1,2-bis(diphenylphosphino)ethane nickel(II) chloride, and triethylphosphite. Potential applications for these conducting polymers include field-effect transistors, sensors, capacitor coatings, battery electrodes, and light-emitting diodes.

REACTION C6H13 Br

S

Cl

C6H13

i Note 1

S

a

i: 2-Methyltetrahydrofuran, magnesium, t-butylmagnesium chloride, triethylphosphite, 1,2- bis(diphenylphosphino)ethane nickel(II) chloride

158

Notes

159

EXPERIMENTAL Preparation of Poly(3-Hexyl)Thiophene with a 93.5% 5-Bromo-2-chloro-3-hexylthiophene (0.0355 mol) was added over a period of 30 minutes to a mixture consisting of 75 ml of 2-methyltetrahydrofuran, magnesium (0.0355 mol), and 0.15 ml of 1M t-butylmagnesium chloride solution in THF at 60 C to 70 C. The mixture was stirred for 90 minutes at 70 C. It was then cooled to 60 C and treated with a suspension of 1,2-bis(diphenylphosphino)ethane nickel(II) chloride (0.177 mmol) in 12.5 ml of 2-methyltetrahydrofuran for over 30 minutes. The mixture was stirred an additional 3 hours at 80 C and further treated with triethylphosphite (3 mmol) and stirred for 30 minutes at 80 C. The mixture was then concentrated and the residue dissolved in 10 ml of toluene. This solution was poured into 100 ml of EtOAc, which created a suspension, and the suspension was stirred for 30 minutes at 80 C. The cooled suspension was filtered, the residue washed twice with 20 ml of EtOAc, and the product isolated in 81% yield having a Mn of 19,543 daltons with a Tm of 224 C. UV (CHCl3): max ¼ 450.79 nm; film: 521, 550, 602 nm

DERIVATIVES Only the Step 1 derivative was prepared.

NOTES 1. Poly(3-dodecylthiophene) having an 99% regiospecificity was prepared in 80% yield by McCullough [1] using 2,5-dibromo-3-dodecylthiophene with catalytic amounts of 1,3-diphenylphosphinopropane nickel(II) chloride. In a subsequent investigation by Koller [2], regiospecificity exceeding 90% for poly(3-hexyl) thiophene was obtained using 2,5-di-bromo-3-hexylthiophene with catalytic amounts of 1,3-diphenylphosphinopropane nickel(II) chloride. 2. Leclerc [3] prepared regioregular and water soluble polythiophenes by oxidizing thiophene derivatives with iron (III) chloride which were then used as optical and electrochemical detectors of double-stranded oligonucleotides.

+ N(C2H5)3

+ N(C2H5)3

O

O

i S i: Dimethyl ether, iron (III) Chloride

S

a

160

Halogenated Thiophene Monomer for the Preparation of Regioregular Polythiophenes

3. Regioregular poly(5,50 -(4,40 -dihexyl-2,20 -bithiazole)), (I), was prepared by Curtis [4] and used in electronic applications such as LED’s, rechargeable batteries, and electrolytic capacitors.

C6H13

N S

S N

(I)

n C6H13


R.D. McCullough et al., US Patent 6,166,172 (December 26, 2000) G. Koller et al., US Patent Application 2005-0080219 (April 14, 2005) M. Leclerc et al., US Patent 7,083,928 (August 1, 2006) D.M. Curtis et al., US Patent 5,536,808 (July 16, 1996)

Title: Electrically Conductive Polymeric Biomaterials, the Process for Their Preparation and Use in Biomedical and Health Care Fields Author:

S. Panero et al., US Patent 7,253,152 (August 7, 2007)

Assignee:

Fidia Advanced Biopolymers, s.r.l. (Abano Terme, IT)

SIGNIFICANCE Polypyrrole composite biomaterials having electrically conductive properties have been prepared using hyaluronic acid or its sodium salt by galvanostatic and potentiostatic methods. These agents are useful for preparing medical devices such as nerve and bone regeneration materials.

REACTION H N

i Note 1

H N

a

EXPERIMENTAL Preparation of Polypyrrole Using Hyaluronic Acid Conductive polymer films based on polypyrrole and hyaluronic acid were synthesized using both a galvanostatic method––by applying current at a constant intensity ranging between 0.5 and 10 mA for periods varying between 60 and 150 minutes––and a potentiostatic method with the constant potentials ranging between 0.3 and 0.75 V

161

162

Electrically Conductive Polymeric Biomaterials

versus SCE. The first method was the preferred method, however, because it produced films with even surfaces, thereby reducing reaction times. Polymer films were synthesized in aqueous solutions using concentrations of pyrrole varying from between 0.05M and 0.3M and concentrations of hyaluronic acid or sodium hyaluronate varying from between 0.9M and 5M.

POLYMERIZATION SCOPING TABLE 1.

Effect of experimental conditions on the film thickness of polypyrrole.

Pyrrole (M)

Hyaluronic Acid (mg/ml)

1

0.1

2

2

0.1

2

3

0.1

2

4

0.1

2

5

0.2

4

Entry

Film Thickness (mm)

Synthetic Method Potentiostatic V ¼ 720 mV vs. SCE, 0.19C Galvanostatic Total charge ! 1C Galvanostatic Total charge ! 5C Galvanostatic Total charge ! 6.24C Galvanostatic Total charge ! 6C

0.33 4.2 8.4 18 12

NOTES 1. Oxidized polypyrrole, (I), was used by Shastri [1] to induce biological activities within stem cells by electromagnetic stimulation.

...

H N

H N N H

N H

...

(I) 2. Hyaluronic acid succinylate, (II), was prepared by Rivarossa [2] by reacting succinic anhydride with sodium hyaluronate and the material used in either venous and arterial vascular anastomoses. This included creating a physical hemostatic barrier to prevent scar tissue formation or to prevent post surgical adherence of the vessels to the surrounding tissues. Laredo [3] prepared

Notes

163

musculoskeletal tissue repair agents consisting of tetraalkylammonium bromide hyaluronic acid salts, (III). O

O

O

OH O

HO

CO2H

O

HO

O NH

OH

(II)

O

a

OH

O N(C4H9)4

O HO

O

HO

O

(III)

O

a

NH

OH O

3. Heteroatom biodegradable and electrically conducting polymers, (IV), effective for tissue engineering applications were prepared by Schmidt [4] and used in spinal cord regeneration, wound healing, and bone repair.

O

O O

H N

H N S

(IV)


V. Shastri et al., US Patent 6,569,654 (May 27, 2003) A. Rivarossa et al., US Patent 7,202,230 (April 10, 2007) W.R. Laredo et al., US Patent 7,091,191 (August 15, 2006) C.E. Schmidt et al., US Patent 6,696,575 (February 24, 2004)

O

O O

O

O

a

Title: Dibenzodiazocine Polymers Author:

V. J. Lee et al., US Patent 7,238,771 (July 3, 2007)

Assignee:

Solvay Advanced Polymers, L.L.C. (Alpharetta, GA)

SIGNIFICANCE Polydibenzodiazocine materials have been prepared by polymerization of dibenzoylbenzidine derivatives using toluene sulfonic acid These agents are useful as electrically conducting artificial muscles.

REACTION NO2

NH2 O

i

ii

Br O

Br

N

i ii Br NH2 O

N N

iv a NH2 O

i: THF, methanol, potassium hydroxide, phenylacetonitrile ii: Acetic acid, iron

164

Experimental

165

iii: bis(1,5-Cyclooctadiene)nickel(0), DMF, hydrochloric acid iv: Toluene sulfonic acid monohydrate, 1,3-dichlorobenzene

EXPERIMENTAL 1.

Preparation of Heterocyclic Intermediate

A glass reactor was charged with 4-bromonitrobenzene (0.126 mol) dissolved in 300 ml of THF/methanol, 1:2, respectively, and then treated with potassium hydroxide (2.64 mol), phenylacetonitrile (0.126 mol), and 300 ml of methanol at 0 C. The mixture was stirred for 4.5 hours at 0 C poured into 1 liter of water. The resulting precipitate was collected by filtration, and purified by re-crystallization using methanol, and the product was isolated in 59.4% yield. 2.

Preparation of 5-Bromo-2-Aminobenzophenone

The Step 1 product (0.10 mol) was dissolved in 200 ml of acetic acid at 80 C and then treated with 50 ml of water and iron powder (0.5 mol) in 10 portions over a two-hour period. The mixture was stirred at 80 C for an additional hour and then cooled to ambient temperature. It was diluted with 1 liter of diethyl ether and extracted with 1 liter of water. The organic layer was separated, dried, concentrated, and re-crystallized from methanol, and the product was isolated in 81% yield. 3.

Preparation of 3,30 -Dibenzoylbenzidine

A slurry of bis(1,5-cyclooctadiene)nickel(0) (81.5 mmol) in 200 ml of DMF was added to the Step 2 product (54 mmol) in 150 ml of DMF. The mixture was stirred for 15 minutes at the ambient temperature, 90 minutes at 42 C, and then poured into 500 ml of 2% aqueous hydrochloric acid. It was extracted with CH2Cl2, and the organic layer was filtered, dried, and concentrated. The residue was purified by chromatography, and the product was isolated in 50% yield. 4.

Preparation of Polydibenzodiazocine

A round-bottomed flask fitted with a Dean–Stark trap was charged with the Step 3 product (5 mmol), toluene sulfonic acid monohydrate (1 mmol), and 20 ml of 1,3-dichlorobenzene and then refluxed 2 hours. The mixture was cooled to ambient temperature, neutralized with 0.5 ml of triethylamine, precipitated in 75 ml of methanol, dried, and 0.77 g of product was isolated having a Mn of 12,000 daltons.

166

Dibenzodiazocine Polymers

DERIVATIVES TABLE 1. Step 4 polydibenzodiazocine derivatives prepared according to the present invention and corresponding yields and number average molecular weights. Entry

Structure

Yield (%)

Mn (daltons)

N

O 2

N

10

29,000 and 5,000,000 (bimodal)

91

90,000

54

61,000

a

N 5

N

O

a

O N 16

N

a

NOTES 1. Mono- and dibendodiazocine analogues, (I) and (II), were previously prepared by Milkowski [1] and Johnson [2], respectively, and used in pharmaceutical applications. N Cl

Cl N N

(I)

H N

N N H

(II)

Notes

167

2. Electroactive polymer and rolled electroactive polymers having dielectric constants between 2.5 and about 12 were used by Kornbluh [3] and Rosenthal [4], respectively, to prepare artificial muscles. References 1. 2. 3. 4.

W. Milkowski et al., US Patent 4,243,585 (January 6, 1981) R.A. Johnson et al., US Patent 4,447,607 (May 8, 1984) R.D. Kornbluh et al., US Patent 7,211,937 (May 1, 2007) M.A. Rosenthal et al., US Patent 7,233,097 (June 19, 2007)

Title: Redox-Active Polymer and Electrode Comprising the Same Author:

T. Mitani et al., US Patent 7,214,762 (May 8, 2007)

Assignee:

Japan Science and Technology Agency (Kawaguchi-shi, JP)

SIGNIFICANCE A new high-energy density battery consisting of a redox-active polymer has been prepared that is effective at low temperatures. The polymer was prepared by the condensation of N,N0 -1,4-phenylene-bis-thiourea with phenylene-1,4-diisothiocyanate and is suitable as a cathode for secondary lithium batteries.

REACTION

H N

S H2N

S N

N H

N

S N

N

NH2 S

H2N

N S

N S

N

S

i

N

N a

ii

Note 1

S

iii

i: NMP, ethanol, benzyl chloride ii: Phenylene-1,4-diisothiocyanate, THF, benzene iii: Oxidant (unspecified)

168

NH2 S

N H

N H

H N

N

S N

S

H N S

a

Notes

169

EXPERIMENTAL 1.

Preparation of N,N0 -1,4-Phenylene-bis-Thiourea-S,S0 -Benzyl Ether

A reaction flask charged with N,N0 -1,4-phenylene-bis-thiourea (230 mg) was dissolved in a mixed solution of 4 ml apiece NMP and ethanol and then treated with benzyl chloride (270 mg) and refluxed for 30 minutes. The solution was cooled, treated with a solution of 10 ml water containing NaOH (80 mg), and then extracted with 40 ml of diethyl ether. The extract was dried with MgSO4, filtered, concentrated, and 400 mg of product were isolated. 2.

Preparation of S-Benzylized Poly(Phenyl-2,4-Dithiobiuret)

The Step 1 product (406 mg) was dissolved in 10 ml apiece THF and benzene and then treated with phenylene-1,4-diisothiocyanate (200 mg) dissolved in 5 ml apiece THF and benzene. This mixture was refluxed for 3 days and filtered, the solid rinsed with acetone, and 100 mg of product isolated. 3.

Preparation of Poly(1,2,4-Dithiazolium-Diaminobenzene)

The Step 3 product was prepared by reacting the Step 2 product with an with oxidant or electrochemically.


NOTES 1. A sample electrode was prepared by grinding the polymeric Step 2 product in a mortar with acetylene black and then adding polyvinylidene fluoride and mixing with DMF. The mixture was next printed on a titanium foil and heated for 3 hours at 80 C. 2. High-energy density batteries having superior stability were prepared Morioka [1] using polynitroxyl radicals components, (I). Sulfur, (II), and boron, (III), free radical analogues prepared by Bannai [2] were also effective as secondary battery components.

.

S N

.

O

(I)

N n O

.

.

B

S

(II)

(III)

170

Redox-Active Polymer and Electrode Comprising the Same

3. Kofinas [3] prepared a polymeric nanoscale solid-state battery system, (IV), consisting of electrochemical cells connected in series, that was used as a secondary battery.

a

t-C4H9

N

Co

N

O

O

O

O

c

b

O

O O

t-C4H9

Li

(IV)

OH

4. Indole trimer, (V), prepared by Nabuto [4] was used as an electrode component in an electrochemical cell.

NH

NH

N H

(V) 5. Nakanishi [5] prepared siloxane-modified cyclic carbonates, (VI), that when combined with a nonaqueous solvent and an electrolyte salt formed a nonaqueous electrolytic solution that was used to construct a secondary battery having improved temperature and cycle properties.

Si

Si

O

O O

O

(VI)

10 O

Si

Notes


Y. Morioka et al., US Patent 7,122,277 (October 17, 2006) Y. Bannai et al., US Patent 7,045,248 (May 16, 2006) P. Kofinas et al., US Patent 7,063,918 (January 20, 2006) T. Nobuta et al., US Patent Application 2007-0095656 (May 3, 2007) T. Nakanishi et al., US Patent Application 2007-0059597 (March 15, 2007)

171

Title: Use of Sulphonic, Phosphonic and Phosphoric Acids as Dopants for Polyaniline and for Conductive Polyaniline-Based Composite Materials Author:

A. Pron et al., US Patent 7,101,495 (September 5, 2006)

Assignee:

Commissariat A L’Energie Atomique (Paris, FR)

SIGNIFICANCE Polyaniline in the emeraldine base state doped with di(butoxyethoxyethyl) ester of sulphosuccinic acid had high film conductivity and an elongation at break of 195%. This high flexibility is particularly needed for elastomer coatings to impart elasticity on conductive materials.

172

Experimental

173

REACTION

NH2

i

HN

N

a

N

Intermediate O HO3S

O OH OH

ii

HO3S

O

O O

O

iii

O O

O

O

O O O

O O

SO3H

O

HN

O O

Dopant

N N

a

Polyaniline

i: Lithium chloride, hydrochloric acid, ethanol, ammonium persulfate, iron (II) chloride ii: 2-(2-Butoxy-ethoxy)ethanol, water iii: 2,2-Dichloroacetic acid

EXPERIMENTAL 1.

Preparation of Polyaniline (Emeraldine Base)

A mixture at 27 C consisting of freshly distilled aniline (0.1097 mol), 85 ml of 3M HCl, 95 ml of ethanol, and LiCl (16 g) was treated with ammonium persulphate (0.0274 mol), 60 ml of 2M HCl, and LiCl (8 g) also at 27 C. The mixture was reacted for roughly 2 hours while the potential of the reaction mixture was controlled by a standard calomel electrode. It was then treated with FeCl2 (0.0183 mol), LiCl (5 g), and 50 ml of 2M HCl. After an additional hour the reaction was terminated, and the polymer could be isolated by either filtration or by centrifuging. It was then washed with distilled water, dried, and converted to the emeraldine salt using 2M HCl. This salt was then converted to the emeraldine base by treatment with 2 liter of 0.3 M aqueous

174

Use of Sulphonic, Phosphonic and Phosphoric Acids as Dopants

ammonia solution for 48 hours. The product was washed with 5 liter of distilled water followed by 2 liter of methanol and then dried. The fractions with low molecular weights were removed by extracting the polymer with chloroform in a Soxhlet apparatus. The intrinsic viscosity of the emeraldine base as prepared was 2.5 dl/g in a 0.1 wt% solution in 96% sulphuric acid. 2.

Preparation Di(Butoxyethoxyethyl) Ester of Sulphosuccinic Acid Dopant

A 70 wt% aqueous solution of sulphosuccinic acid (50.5 mmol) was mixed with 2-(2butoxy- ethoxy)ethanol (151.5 mmol) at 110 C under a constant stream of nitrogen. The material was dried under vacuum at 70 C, and the product was isolated. 3.

Preparation of a Self-supported and Drawable Film of Doped Polyaniline

The Step 1 product (111 mg) and the Step 2 product (302 mg) were mixed in 2,2dichloroacetic acid (22.2 g) and stirred until no further change was observed in the UVVis-NIR spectrum. Self-supported films were prepared by pouring about 1 ml onto a polypropylene substrate and removing the solvent by evaporation at 45 C. The film was detached from its substrate and dried under vacuum; the film’s thickness was on the order of 20 to 30 mM. The film’s conductivity was measured at 90 S/cm by the 4-contact method at ambient temperature. The manually drawn film exhibited an elongation at break of 195% at ambient temperature.

DERIVATIVES TABLE 1. Effect of selected dopants on the film conductivity and elongation at break for polyaniline (emeraldine base). Elongation at Break (%)

Dopant Sulphosuccinic acid, di(2-ethylhexyl) ester Camphorsulphonic acid 2-Acrylamido-2-methyl-1-propanesulphonic acid, Sulphosuccinic acid, di(butoxyethyl) ester

36 2 115 195

Film Conductivity (S/cm) 115 230 90.5 125

Note: All doping was conducted in 2,2-dichloroacetic acid with 20 to 30 mM films prepared on a polypropylene substrate.

NOTES 1. Olinga [1] prepared and used the aromatic diester dopant, (I), with polyaniline and prepared flexible films having film conductivities between 100 to 200 S/cm.

Notes

175

Nanotubes using lignosulfonic acid-doped polyaniline were prepared by Viswanathan [2].

O HO3S

C2H5 O O

O

C2H5

(I)

2. Wang [3] prepared chiral polyaniline by amidating with the chiral dopant acid, (1R)–[ ]–camphor sulfonic acid, (II), which was used in nanomaterials having lengths of between 1 to 5 microns. When Wang [4] polymerized either aniline D- or L-tartrate, the corresponding water-soluble polyaniline derivative was isolated. The derivatives were readily doped with ammonium hydroxide (green) or hydrochloric acid (blue). Water-soluble polyaniline was also prepared by Angelopoulos [5] by polymerizing aniline in the presence of the polymeric dopant, polystyrene sulfonic acid.

O O3S NH HN

NH

a

(II)

3. Lee [6] observed that when polyaniline or polypyrrole were N-functionalized with N-t-butoxy carbonyl, these materials displayed enhanced physical and mechanical properties with higher solubility and electrical conductivity than the corresponding nonfunctionalized counterparts.

176

Use of Sulphonic, Phosphonic and Phosphoric Acids as Dopants

References 1. 2. 3. 4. 5. 6.

T. Olinga et al., US Patent 7,014,794 (March 21, 2006) T. Viswanathan et al., US Patent 7,063,808 (June 20, 2006) H.-L. Wang et al., US Patent 7,074,887 (July 11, 2006) H-L. Wang et al., US Patent 7,074,887 (July 11, 2006) M. Angelopoulos et al., US Patent 7,166,241 (January 23, 2007) S.-H. Lee et al., US Patent 7,067,229 (June 27, 2006)

Title:

3,4-Alkylenedioxy-Thiophene Copolymers

Author:

B. Groenendaal et al., US Patent 6,995,223 (February 7, 2006)

Assignee:

Agfa-Gevaert (Mortsel, BE)

SIGNIFICANCE An aqueous dispersion consisting of polyethylene glycol containing a (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)-methanol terminus has been prepared. This material exhibited electrical conductivities, visible light transmittances, and good processability. REACTION O OH O HO2C

O

S

OH

i Note 1,2 CO2H

O

O

a

O

ii Note 3

S

O

O

S

i: DMAc, copper (II) dichromate, quinoline ii: p-Toluenesulfonyl chloride, pyridine, polyethylene oxide, hydrochloric acid

EXPERIMENTAL 1.

Preparation of (2,3-Dihydro-Thieno[3,4-b][1,4]Dioxin-2-yl)-Methanol

A reaction vessel was charged with 2-hydroxymethyl-2, 3-dihydro-thieno[3,4-b][1,4] dioxine-5,7-dicarboxylic acid (0.184 mol) dissolved in 500 ml DMAc and then treated with copper dichromate (8.6 g) and 15 drops of quinoline. This mixture was stirred for 2 hours at 150 C and cooled to the ambient temperature. It was poured into EtOAc, and the catalyst was removed by filtration. The filtrate was washed with acidic water and brine, then concentrated, and the product was isolated by distillation at 115 C to 120 C at 0.05 mmHg. 177

178

3,4-Alkylenedioxy-Thiophene Copolymers

2. Preparation of Polyethylene Oxide Substituted (2,3-Dihydro-Thieno[3,4-b] [1,4]Dioxin-2-yl)-Methanol p-Toluenesulfonyl chloride (44 mmol) was dissolved in 20 ml of pyridine and treated dropwise with mexthoypolyethylene oxide (Mw ¼ 750 daltons; 20 mmol) dissolved in 30 ml of pyridine. The mixture was stirred for 2 hours at 25 C to 30 C and poured into ice-water containing hydrochloricacid. Thisaqueous phasewas extracted with CH2Cl2, after which the combined organic fractions were washed with 1 M of sodium hydrogen carbonate solution. Final purification was done by column chromatography using CH2Cl2/ethanol and polyethylene oxide tosylate isolated. The Step 1 product (5.8 mmol) was dissolved into 25 ml of THF and treated with sodium hydride (0.25 g) while stirring for 30 minutes and further treated with methoxypolyethylene oxide tosylate (5.3 g). The mixture refluxed for 2 hours, cooled to the ambient temperature, and poured into ice-water containing a few drops of concentrated hydrochloric acid. This mixture was extracted using CH2Cl2, and combined extracts were washed with a 1 M aqueous solution of sodium hydrogen carbonate and brine, dried, and concentrated. The residue was purified by column chromatography using CH2Cl2/methanol, 95:5, respectively, and the product was isolated. DERIVATIVES The following derivatives were prepared: O

3

CO2H

O O

O

S

SO3Na

O O

O

O

O

S

O

S

NOTES 1. Urethane derivatives, (I), of the Step 1 product were prepared by Reuter [1] and used in optical signal processing. O NH O C4H9

O

O

S

(I)

Notes

179

2. Additional Step 1 decarboxylation transformation methods are provided by Reynolds [2]. 3. Poly(3,4-alkylenedioxythiophenedioxide), (II), derivatives were prepared by the author [3] and used as an electroconductive layer in a light-emitting diode.

O

a

O O

O

S O2

(II)

4. Tahon [4] prepared poly(3,4-alkoxythiophene), (III), derivatives to enhance the conductivity in nonaqueous printing. The process for preparing aqueous and nonaqueous solution dispersions of this agent are described by Louwet [5].

O

O

S

a

(III)

References 1. K. Reuter et al., US Patent 6,852,831 (February 8, 2005) 2. J.R. Reynolds et al., US Patent 6,425,966 (March 11, 2004) 3. B. Groenendaal et al., US Patent 6,927,298 (August 9, 2005) and US Patent 7,105,620 (September 12, 2006) 4. J.-P. Tahon et al., US Patent 7,223,357 (May 29, 2007) and US Patent 7,122,130 (October 17, 2006) 5. F. Louwet et al., US Patent 6,425,966 (May 23, 2006)

E. Electroluminescence

Title: Electroactive Polymer, Device Made Therefrom and Method Author:

K. E. Litz et al., US Patent 7,217,774 (May 15, 2007)

Assignee:

General Electric Company (Niskayuna, NY)

SIGNIFICANCE High and low molecular weight electroactive polymers containing pendant 2-(7benzothiazolyl-9,90 -dioctylfluorene) units have been prepared. These materials display electroluminescent properties that are useful in electronic devices.

REACTION Br

Br C8H17

OHC

i

Br C8H17

C8H17

C8H17

iv

a

C8H17

N

i: Butyl lithium, THF, dimethylformamide ii: 2-Aminothiophenol, dimethyl sulfoxide

180

N

Br C8H17

S N

C8H17

S

S

ii Note 1

C8H17

iii C8H17 C8H17

Experimental

181

iii: Cesium fluoride, tris(dibenzylideneacetone)dipalladium, tri-t-butylphosphine, tributyl(vinyl)-stannane, tetraglyme, toluene iv: Benzoyl peroxide, benzene

EXPERIMENTAL 1.

Preparation of 2-Bromo-7-Formyl-9,90 -Dioctylfluorene

Butyl lithium (0.116 mol) was added dropwise to a solution of 2,7-dibromo-9,90 dioctylfluorene (0.0918 mol) in 200 ml of THF at 78 C over 45 minutes and then stirred for an additional 30 minutes. The mixture was treated with dimethylformamide (0.1539 mol) at 78 C, warmed to ambient temperature over 4 hours, and concentrated. The yellow residue was dissolved in 130 ml of hexanes/xylenes, 10:3, respectively, and then quenched with 5 ml 20% hydrochloric acid. After separating from the aqueous fraction, the organic layer was neutralized with NaHCO3, filtered, dried over MgSO4, and decolorized with activated carbon (10 g). The final solution was filtered and concentrated, yielding a colorless solid with a faint greenish hue. The light greenish color was removed by suspension in methanol, and the product was isolated in 83% yield as a colorless microcrystalline solid with MP ¼ 48–50 C. 2.

Preparation of 2-Bromo-7-Benzothiazolyl-9,90 -Dioctylfluorene

The Step 1 product (0.0603 mol) and 2-aminothiophenol (0.0693 mol) was dissolved in 80 ml of dimethyl sulfoxide and heated for 1 hour at 198 C and then quenched by pouring into 100 ml of cold water. The aqueous layer was decanted from the bright yellow oil and extracted twice with 25 ml of pentane. The organic layers were combined and quenched with 20 ml of 20% acetic acid. The layers were separated and the acidic solution extracted twice with 25 ml pentane. The organic fractions were combined and neutralized by washing twice with 100 ml of saturated NaHCO3 solution. The basic solution was extracted twice with 25 ml of pentane, and the organic fractions were combined and dried over MgSO4. The mixture was decolorized with activated carbon, leaving a bright yellow solution. The solution was then concentrated and a yellow residue purified by column chromatography using alumina with xylenes/cyclohexane, 4:1, respectively, followed by re-crystallization in methanol. The product was isolated in 53% yield as a colorless crystalline solid with MP ¼ 79–81 C. 3.

Preparation of 2-Vinyl-7-Benzothiazolyl-9,90 -Dioctylfluorene

A mixture consisting of the Step 2 product (0.0083 mol), cesium fluoride (0.0175 mol), tris(dibenzylideneacetone)dipalladium (0.041 mmol), tri-t-butylphosphine (0.123 mmol), and tributyl(vinyl)stannane (0.0087 mol) was dissolved in a mixture of tetraglyme (6 g) and 7 ml of toluene and then heated for 14 hours at 90 C in a sealed 30-ml vial. Once cooled to ambient temperature, a blue-green precipitate formed,

182

Electroactive Polymer, Device Made Therefrom and Method

which was extracted with 20 ml of diethyl ether and filtered. The filtrate was decolorized with activated charcoal (2.0 g) and dried using 4 A molecular sieves (2.0 g). The solution was then concentrated, and the residual oil was added dropwise into dry acetonitrile leaving a bright yellow solid. The bright yellow solid was extracted twice with 10 ml of diethyl ether leaving an insoluble white solid. The ether extract was concentrated, and the product was isolated in 61% yield in greater than 95% purity. 4.

Preparation of Poly(2-Vinyl-7-Benzothiazolyl-9,90 -Dioctylfluorene)

The Step 3 product (0.2 g) was combined with benzoyl peroxide (2.8 mg) in 1 ml of benzene, and the mixture was heated to 66 C overnight. The polymer was then precipitated by pouring into methanol, filtered, and vacuum dried. The product was isolated as a solid with a Mw of 8600 daltons, Mn of 5100 daltons, and a polydispersity index of 1.68.

DERIVATIVES Poly(styrene-co-2-vinyl-7-benzothiazolyl-9,90 -dioctylfluorene) was also prepared.

a

b C8H17 C8H17

S

1.

N

Electrical Activity Testing

Fluorescence quantum yields were determined using coumarin 540 in EtOAc as a reference. UV absorption maxima were determined in chloroform; HOMO and LUMO values were determined by cyclic voltammetry in acetonitrile/tetrabutylammonium fluoroborate solution. Optical and electrical properties of each derivative are provided in Table 1.

Notes

183

TABLE 1. Summary of electroactive properties of poly(2-vinyl-7-benzothiazolyl-9, 90 -dioctylfluorene) and poly(styrene-co-2-vinyl-7-benzothiazoly-9,90 -dioctyl-fluorene). Polymer

Homo Polymer

Lamda (abs), nm Lamda (PL), nm HOMO, eV LUMO, ev E gap, eV Quantum yield, % Mw (daltons) PDI

Styrene Copolymer

362 403 6.02 3.08 2.94 59 8,600 2.01

422 425 5.9 2.63 3.27 97 114,600 2.3

Note: Although both derivatives exhibited good blue luminescence, quantum yield differences were observed.

NOTES 1. Chen [1] prepared imidazole-fused phenanthroline derivatives, (I), that were effective as organic light-emitting devices.

N

N N

N

(I) 2. A highly efficient green light-emitting electroluminescent device was prepared by Brunner [2] using a carbazole trimer as the charge-transporting conjugated donor, (II). The corresponding electroactive polymeric carbazole, (III), was previously prepared by Leclerc [3]. H3CO

OCH3 N

N

OCH3

(II)

N

184

Electroactive Polymer, Device Made Therefrom and Method

a

N C8H17

(III) 3. Fryd [4] prepared organic emitting materials consisting of polymeric-metal complex salts, (IV). Their preparation is illustrated in below.

...... ......

......

N

F3C

F3C O

+

......

O

Eu(NO3)3

Eu O

O

F3C

F3C

NH

4

(IV)

4. Electroluminescent polymers containing grafted 1,3,4-oxadiazoles, (V), were prepared by Roberts [5] and were significantly red-shifted from the corresponding monomer. These agents were used in making organic light-emitting diodes.

15

N O

(V)

N

OC8H17


J.P. Chen et al., US Patent 7,179,542 (February 20, 2007) K. Brunner et al., US Patent Application 20060051611 (March 9, 2006) M. Leclerc et al., US Patent 6,833,432 (December 21, 2004) M. Fryd et al., US Patent 7,060,372 (June 13, 2006) and US Patent 6,869,693 (March 22, 2005) R.R. Roberts et al., US Patent 7,094,902 (August 22, 2006)

Title: Polymers and Oligomers, Their Synthesis, and Electronic Devices Incorporating the Same Author:

A. J. Epstein et al., US Patent 7,071,290 (July 4, 2006)

Assignee:

The Ohio State University (Columbus, OH)

SIGNIFICANCE Conjugated and nonconjugated block copolymers and oligomers have been prepared that have electroluminescing properties. The materials consist of polyaromatics and heteroaromatics and were prepared in a single synthetic step.

REACTION OCH3 OHC

O OCH3

H3CO 6 O

H3CO

H3CO

OCH3 CHO

i

O

O OCH3

6

O H3CO

OCH3 N

a

OCH3

i: 1,4-Pyridylylenebis(triphenylphosphonium), THF, potassium t-butoxide

EXPERIMENTAL 1.

Preparation of Polyaromatic Ether Containing a Conjugated Pyridine

To a stirred solution containing the dialdehyde (1.12 mmol) and 1,4-pyridylylenebis (triphenyl-phosphonium) (1.12 mmol) dissolved in 150 ml of THF was added dropwise 10 ml of 2 M potassium t-butoxide dissolved in THF, and the mixture refluxed 2 hours. The solution was then concentrated and the residue dissolved in CCl3H. The polymer was precipitated in methanol and purified by Soxhlet extraction with methanol for 12 hours. The purified polymer was isolated in 92% yield as a light-yellow solid. 1

H-NMR (CDCl3) d 1.4 (m, 4H), 1.6 (t, 4H), 3.7 (s, 12H), 3.9 (t, 4H), 6.7 (s, 4H), 7.0 (t, 1H), 7.1 (d, 4H), 7.5 (d, 2H). 185

186

Polymers and Oligomers, Their Synthesis, and Electronic Devices Incorporating the Same

DERIVATIVES TABLE 1. Product conversions for selected electroluminescing polyaromatic and heteroaromatic polymer agents. Entry

Structure

Yield (%)

OCH3 H3CO 2

6O

O

O H3CO

H3CO

OCH3

N

90

a

OCH3 H3CO 13

O

H3CO

O 14

OCH3

O

6

88

a

H3CO

OCH3 OCH3

O

6

90

a

H3CO

15

OCH3

OCH3

OCH3

O 6O

90

H3CO

a

H3CO 16

O

O

6

H3CO

OCH3

a

OCH3 Note: H-NMR characterization data provided by the author.

88

Notes

187

TABLE 2. Step 1 product yields for conjugated monomeric analogues effective as electroluminescing agents. Entry

4

Structure

Yield (%)

59

N N

5

OCH3

N

49

N

H3CO

N

6

52

N

10

OCH3

N

46

H3CO

N

50

12

Note: H-NMR characterization data provided by author.

NOTES 1. In an earlier investigation by the author [1] electroluminescing polymers were designed to remain in a de-aggregated state to prevent the redshifting. This was achieved by incorporating rotaxanes into experimental polymeric agents, (I).

188

Polymers and Oligomers, Their Synthesis, and Electronic Devices Incorporating the Same

(H2CCH2O)6

Rotaxane (I)

2. Biphenyl derivatives consisting of both carbazole, (II), and indolyl components were prepared by Takiguchi [2] and used as light-emitting agents; tricarbazole triphenylamine derivatives, (III), prepared by Iwakuma [3] were also effective as light-emitting agents.

N

N

N N

N N

(II)

(III)

3. Okada [4] determined that polymer materials having an arylamine repeating unit containing p-conjugation on its main chain, (IV), had excellent luminous properties and were particularly useful as organic electroluminescence elements.

N

S

S

a

C6H13

(IV)

Notes

189

4. Polymers containing benzotriazole repeating units, (V), which had high glass transition temperatures and good thermal stability, were fabricated into coatings and films by Rogers [5] and used in electroluminescent devices.

C8H17

C8H17

a C8H17

C8H17

H3CO

(V)

5. Egawa [6] prepared light-emitting stilbene derivatives, (VI), having a large energy gap suitable for use as a host material in a light-emitting layer.

a

a (VI)


A.J. Epstein et al., US Patent 6,962,757 (November 8, 2005) T. Takiguchi et al., US Patent Application 2007-0057250 (March 15, 2007) T. Iwakuma et al., US Patent Application 2007-0054151 (March 8, 2007) T. Okada et al., US Patent Application 2007-0048637 (March 1, 2007) J. Rogers et al., US Patent Application 2007-0043204 (February 22, 2007) and US Patent Application 2005-0175856 (August 11, 2005) 6. M. Egawa et al., US Patent Application 2007-0100180 (May 3, 2007)

Title: Process for Preparing Poly(Arylene Ethers) with Pendant Crosslinkable Groups Author:

B. Chen et al., US Patent 7,038,004 (May 2, 2006)

Assignee:

Lumera Corporation (Bothell, WA)

SIGNIFICANCE Two crosslinkable perfluorinated bisphenol A polymeric derivatives having nonlinear optical chromophores containing thiophene have been prepared. Both crosslinked polymers had higher Tg’s and greater mechanical stability than their noncrosslinked analogues and were used as light-emitting diodes.

190

Reaction

191

REACTION F5 F5

F4

F5 O

F5

F4

i

O

Not isolated O F5

F4

F5 O

a OH

F4 O

ii F5

O

F4

F5 O

a O

O

F4 O

O

F3

iii Note 1

F3

O O

F3

O O

OC4H9

C4H9O N

S C4H9O

S OC4H9

O NC NC

CN

Chromophore Crosslinked polymer

i: 4,40 -(1-Phenyl ethylidene)-bisphenol A, potassium carbonate, DMAc, 3,5dihydroxybenzylalcohol ii: N-Methylpyrrolidone, 4-trifluoro-vinyloxybenzoyl chloride, pyridine iii: Cyclopentanone

192

Process for Preparing Poly(Arylene Ethers) with Pendant Crosslinkable Groups

EXPERIMENTAL 1. Preparation of Poly(4,40 -(1-Phenyl Ethylidene-Bisphenol-4,40 Di(perfluorobiphenyl)-co-3,5-Dihydroxy-Benzyl Alcohol) A glass reactor was charged with decafluorobiphenyl (0.3 mol), 4,40 -(1-phenyl ethylidene)-bisphenol (0.15 mol), K2CO3 (26 g), and 400 ml of DMAc and then heated to 120 C for 20 hours. The temperature was lowered to 105 C over 1 hour and the mixture treated with 3,5-dihydroxy-benzylalcohol (0.15 mol) and K2CO3 (20 g). Over a 3-hour period the temperature was increased to 115 C where it remained for 1 hour. The mixture was hot filtered through a frit and the frit washed with 50 ml of THF. The solution was cooled to ambient temperature and precipitated into a mixture of 750 ml of methanol and 200 ml of water in a blender. The solid was re-dissolved in 250 ml of THF where it formed a viscous solution that was re-precipitated in a solution of 500 ml of methanol and 200 ml of water. The solid was then collected and air-dried on the frit for over 5 hours. It was further dried at 80 C at 87 torr on a rotary evaporator for 5 hours and the product isolated as a fine white powder in 30% yield. 2. Preparation of Poly(4,40 -(1-Phenyl Ethylidene-Bisphenol-4,40 Di(perfluorobiphenyl)-co-3,5-Dihydroxy-1-Benzyl (4-Trifluorovinyloxy Benzoate) A reaction vessel was charged with 350 ml of N-methylpyrrolidone, the Step 1 product (44.3 g), and 100 ml of pyridine and then stirred at ambient temperature for one hour and treated with of 4-trifluorovinyloxybenzoyl chloride (0.085 mol). This mixture was stirred for 20 hours when the solution color changed from light yellow to brown. The mixture was precipitated by pouring into 500 ml of methanol and 200 ml of water in a blender. The solid was isolated by filtering through a glass frit where a reasonable amount of emulsified polymer formed in the filtrate, suggesting a degree of polymer fractionation. The collected solid was washed with 2 liters of methanol and dried on a glass frit in air for 48 hours. The solid was dissolved in 250 ml of THF and precipitated in 750 ml of methanol and 200 ml of water in a blender. The solid was re-filtered and re-washed with 2 liters of methanol and air dried on the frit for 4 hours. It was re-dissolved in 250 ml of THF and re-precipitated in a solution of 750 ml of methanol and 200 ml of water in a blender, the process being repeated once; 40.0 g of product were isolated as a white powder. 3.

Preparation of the Crosslinked Polymer Containing a Chromophore

A 30 wt% solution of the chromophore was mixed with the Step 2 product dissolved in cyclopentanone and then spin-coated onto 200 glass wafers coated with indium tin oxide; the wafer soft baked at 100 C. A corona voltage of 5 kV was applied to the film while it was heated to 220 C for 10 minutes. While at this temperature the voltage was

Notes

193

increased to 5.5 kV, 6.5 kV, and 7.5 kV for 15, 23, and 30 minutes, respectively. After 40 minutes the wafer was cooled to ambient temperature under the 7.5 kV field. The product was then isolated and had a r33 of 24 pm/V measured at 1310 nm using the Teng–Man method.

DERIVATIVES One additional Step 2 crosslinkable polymer, (I), was prepared.

O F5

F4

F5 O

F3C

a O

O

F4 O

O

CF3

F3

(I)

NOTES 1. The preparation of the Step 3 crosslinking nonlinear optical chromophore coreagent is described by Huang [1]. Additional crosslinkable luminescent agents, (I) are provided below, (I).

F3

O

N F3

O O

OC4H9

C4H9O

O S C4H9O

S

R

OC4H9

(I)

H2C

CH2

NC

NH

R= O

NC

CN NC

CN CH2 CN

194

Process for Preparing Poly(Arylene Ethers) with Pendant Crosslinkable Groups

2. Poly(acrylic acid-co-butylmethacrylate) functionalized with cyclometalated luminescent complexes, (II), were prepared by Fryd [2] and used as high efficiency organic light-emitting devices.

n-C4H9 O O a

b

O

O

O

O Ir

CF3

F

(II)

3. Tamao [3] prepared a polymeric light-emitting agent consisting of poly(3,7dibromo-5-(2,4,6-triisopropylphenyl)-2,8-dioctyloxy-5H-dibenzo(b,d)borole), (III), which was used in electronic devices or as a charge transport material. Poly (9,9-di-(4-t-butyldimethylsilyloxy-phenyl)fluorene-2,70 -diyl), (IV), was prepared by Woo [4] and used as a light-emitting diode having the potential for subsequent crosslinking.

C8H17O

OC8H17 a

B i-C3H8

a

i-C3H8 O

O

Si i-C3H8

(III)

SI

t-C4H9

t-C4H9

(IV)

4. O’Neill [5] and Inbasekaran [6] prepared photopolymerizable and crosslinkable luminescent monomers, (V), and (VI), respectively, which were used as light emitters in displays, backlights, and electronic equipment.

Notes

C3H7 C3H7

S

S

O

N

N

O

O

195

O O

O O

(V)

O

(VI)

References 1. 2. 3. 4. 5. 6.

D. Huang et al., US Patent 6,995,884 (February 7, 2006) and, US Patent 7,019,453 (March 28, 2006) M. Fryd et al., US Patent 7,060,372 (June 13, 2006) K. Tamao et al., US Patent 7,157,154 (January 2, 2007) E.P. Woo et al., US Patent 6,900,285 (May 31, 2005) and US Patent 6,605,373 (August 12, 2003) M. O’Neill et al., US Patent 7,199,167 (April 3, 2007) M. Inbasekaran et al., US Patent Application 2007-0063191 (March 22, 2007)

F. Semiconductors

Title: Mono-, Oligo-, and Polythieno[2,3-b]Thiophenes Author:

M. Heeney et al., US Patent 7,183,418 (February 27, 2007)

Assignee:

Merck Patent Gesellschaft (Darmstadt, DE)

SIGNIFICANCE Polymers having a central core consisting of [2,3-b]-thienothiophene were prepared having a Mn > 6000 daltons and Mw > 9000 daltons and used as semiconductors or charge transport materials in electronic devices. By varying the aromatic or aliphatic content of this material, a lmax between 380 and 462 nm was obtained.

REACTION

HO2C

S

S

CO2H

i C8H17

Br

S

S

ii

Br

S

S

S

S S

S

S

C8H17

C8H17

iii

S

C8H17

a

i: NMP, N-bromosuccinimide ii: THF, Rieke zinc, 2,5-dibromo-3,4-dimethylthieno[2,3-b]thiophene, [1,10 -bis (diphenyl-phosphino)ferrocene]palladium(II) chloride iii: Ferric chloride, CCl3H

196

Experimental

197

EXPERIMENTAL 1.

Preparation of 2,5-Dibromo-3,4-Dimethylthieno[2,3-b]Thiophene

A solution of 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid (0.11 mol) dissolved in 800 ml of NMP and 50 ml of water was treated with the portionwise addition of N-bromosuccinimide (0.25 mol) for over 30 minutes. The mixture was stirred for 16 hours at ambient temperature and then poured into 1 liter of water. The resultant precipitate was dried, the residue purified by flash chromatography over silica using petrol, and the product isolated in 77% yield. 2. Preparation of 2,5-bis(3-Octylthiophen-2-yl)-3,4-Dimethylthieno[2,3-b] Thiophene The Step 1 product (14.5 mmol) dissolved in 20 ml of THF was treated with Rieke zinc (17 mmol) at 78 C, stirred 16 hours at ambient temperature. With the stirring stopped, the solution was allowed to settle for 2 hours, whereupon the solution was transferred by cannula into a flask containing 2,5-dibromo-3,4-dimethylthieno[2,3b]thiophene (3.9 mmol), 50 ml of THF, and [1,10 -bis(diphenylphosphino)ferrocene] palladium(II) chloride (64 mg) at 0 C. The mixture was warmed to ambient temperature for over 30 minutes and refluxed for 24 hours. The reaction was cooled and quenched with 5% hydrochloric acid and then extracted 3 times with 50 ml of EtOAc. Combined extracts were washed with brine, dried using Na2SO4, and concentrated. The residue was purified by flash chromatography over silica with petrol-followed by reverse, phase chromatography using CH3CN/THF, 2:1, respectively, and the product was isolated in 72% yield as a colorless oil. M/Z: 556 (Mþ) Elemental analysis: Found C, 69.1%, H, 7.6% Calc. for C32H44S4C, 69.0; H 8.0

3. Preparation of Poly(2,5-bis(3-Octylthiophen-2-Yl)-3,4-Dimethylthieno [2,3-B]thiophene) The Step 2 product (1.28 mmol) dissolved in 20 ml CCl3H was treated with the dropwise addition of ferric chloride (6. 2 mmol) dissolved in 100 ml CCl3H. A steady stream of nitrogen was passed through the solution to remove HCl formed during the reaction as it stirred 18 hours at ambient temperature. The mixture was then poured into 500 ml methanol and stirred for 30 minutes, filtered, and the precipitate washed with water and methanol. The yellow precipitate was stirred in 16 M of NH4OH for 60 minutes then filtered and dried. The solid was Soxhlet extracted with methanol, iso-hexane, and acetone. The material was then dissolved in CCl3H, re-precipitated in methanol, dried, and the product isolated. Mn (GPC) ¼ 17,000 daltons Mw (GPC) ¼ 20,000 daltons lmax ¼ 380 nm

198

Mono-, Oligo-, and Polythieno[2,3-b]Thiophenes

DERIVATIVES TABLE 1. Selected poly(thieno[2,3-b]thiophene) derivatives and corresponding physical properties. Entry

Mn (daltons)

Structure

2

S

S S

C8H17 4

C8H17 S

5

C12H25 S

S

Mw (daltons) lmax (nm)

9,000

22,000

380

6,400

9,400

414

14,000

22,000

414

13,000

40,000

462

a C8H17

S S C8H17

S

a

S S C12H25

S

a

6

S S

C6H13 1

S

a

H- and 13 C-NMR for intermediates supplied by author.

NOTES 1. Methods for preparing polymeric selenophene analogues of the current invention using selenophene-2,5-diyl derivatives have been proposed Tierney [1]. 2. Copolymers of 9-H,H-fluorene and thiophene, (I), were prepared by the author [2] and used as charge transport materials in electronic devices.

S

S

a

(I) 0

0

0

3. Poly(3,3 -dialkyl-2,2 :5 2-terthiophene) derivatives, (II), prepared by McCulloch [3] were also effective in electronic components as charge transport materials and semiconducters.

Notes

199

R

R S

S

S

R = CH3 - C8H17

a

(II) 4. Crosslinkable mesogenic azulenes, (III) and (IV), prepared by Farrand [4], and anthracenyl, (V), and tetracenyl, (VI), thiophenes, prepared by Gerlach [5], were used as semiconductors and charge transport agents in electronic devices. H2C=HCCO2(H2C)6O

O(CH2)6O2CCH=CH2

(III) O(CH2)6O2CCH=CH2

H2C=HCCO2(H2C)6O

(IV) S

S

S

S

S

(V)

S

S

S

(VI)

5. Trimeric thiophenes attached to a core-shell structure, (VII), were prepared by Kirchmeyer [6] and used as semiconductors. T

T

T

T

T

T

T= T

T

T

T

(VII)

S S

S

C10H21

200

Mono-, Oligo-, and Polythieno[2,3-b]Thiophenes

References 1. 2. 3. 4. 5. 6.

S. Tierney et al., US Patent Application 2007-0045592 (March 1, 2007) M. Heeney et al., US Patent 7,126,013 (October 24, 2006) I. McCulloch et al., US Patent 6,953,957 (October 11, 2005) L.D. Farrand et al., US Patent 7,115,755 (October 3, 2006) C.P. Gerlach,US Patent 6,998,068 (February 14, 2006) S. Kirchmeyer et al., US Patent 7,078,724 (July 18, 2006)

Title:

Poly(Arylene Ether) Dielectrics

Author:

C. Lim et al., US Patent 7,166,250 (January 23, 2007)

Assignee:

Chartered Semiconductor Manufacturing Ltd. (Singapore, SG)

SIGNIFICANCE Three polyarylene ethers having a Mn > 10,500 with dielectric constants of around 2.5 were prepared and used as low k dielectric layers in electronic applications. Polyarylene ethers were prepared using the Ullmann ether synthesis and had Td ‘s in air of at least 310 C. REACTION

HO

OH

S

O

i Note 1

O

S

a

i: Benzophenone, toluene, sodium hydroxide, 2,5-dibromo-thiophene, copper(I) chloride, acetic acid, methanol

EXPERIMENTAL 1.

Preparation of Poly(Arylene Ether)

The Ullmann ether catalyst was prepared by charging a 50-ml flask with copper(l) chloride (0.61 mmol) and 0.6 ml of quinoline and then stirring at 25 C for 48 hours. A mixture consisting of 9,9-bis(4-hydroxyphenyl)fluorene (2.86 mmol), benzophenone (5 g), and about 3 ml of toluene was charged to a 50-ml three-necked round bottom flask fitted with a distillation apparatus and heated to 60 C. The mixture was treated

201

202


with aqueous sodium hydroxide (5.72 mmol) and water azeotroped by vacuum distillation at an elevated temperature and then cooled. After re-heating to 80 C the mixture was treated with 2,5-dibromo-thiophene (2.86 mmol) and further heated to 180 C and treated with 0.6 ml of the Ullmann ether catalyst. Heating was continued at 180 C for 17 to 24 hours, and the mixture was next treated with a single portion of 0.02 g dry copper(I) chloride powder. The mixture temperature was increased to 190 C for 24 hours, treated with 0.3 g of 2-bromothiophene, and stirred an additional hour. It was cooled to 100 C, treated with roughly 5.5 ml of toluene, and precipitated in a solution of acetic acid and methanol. The polymer was Soxhlet extracted for 24 hours using methanol, acetone, and chloroform. The polymer was dissolved in a minimum amount of chloroform, re-precipitated in 100 ml of methanol, and the product was isolated.

DERIVATIVES TABLE 1. Summary of physical and dielectric properties of selected poly(arylene ethers) prepared using the Ullmann ether catalyst.

Entry

Structure

1

S

2

N

3

N

O

O

O

O

O

S

N

Mn (daltons)

Td ( C) (air)

Td ( C) (N2)

Tg ( C)

e (100 kHz)

25,000

310

355

312

2.43

11,000

345

325

214

2.65

450

450

227

a

a

32,000

O

N

2.35

a

NOTES 1. Additional derivatives of the current invention were prepared by the author [1] in a subsequent investigation.

Notes

203

2. Terahara [2] utilized the Ullmann ether catalyst of the current invention to prepare poly(arylene ethers), (I), for use as a component in fuel cells. O

O

n

(I) 3. Bai [3] surface modified polymeric low dielectric constant gate insulator films consisting of polystyrene/polyacrylate block copolymers, (II), having an e 4.6. Perfluoroether acyl oligothiophenes, (III), prepared by Gerlach [4] were also effective as low dielectric constant gate insulators.

O a O

O

N H

NC

O b

c

N

O

(II) CN O

S

R1

O a R1

R1 CF2(CF2CF2CF2O)3CF3 CF(CF3)CF2OCF(CF3)OCF3

a 5 6

(III) 4. Low dielectric constant gate insulators were prepared by Kelley [5] consisting of poly(stryene-co-vinyl phosphonic acid) and having termini consisting of either trimethyloxysilyl- or phosphinic acid. 5. Weber [6] devised a method for repairing porous low k dielectric films by sealing with polydentate ligands, such as ethylene diamine tetraacetic. 6. Burgoyne [7] prepared polyarylene ethers containing grafted furfuryl, (IV), that crosslinked at low temperatures and were useful as dielectric or super high

204


aperture enhancing materials with high glass transition temperatures and low moisture uptake. O HO O

O

O

O

a

(IV)

References 1. 2. 3. 4. 5. 6. 7.

C. Lim et al., US. Patent 7,179,879 (February 20, 2007) A. Terahara et al., US. Patent 7,081,497 (July 25, 2006) F. Bai et al., US. Patent 7,098,525 (August 29, 2006) C.P. Gerlach et al., US. Patent 7,151,276 (December 19, 2006) T.W. Kelley et al., US. Patent 6,946,676 (September 20, 2005) F. Weber et al., US. Patent 7,163,900 (January 16, 2007) W.F. BurgoyneJr. et al., US Patent 7,179,878 (February 20, 2007)

b

a:b =2:1

Title:

Polythiophenes and Devices

Author:

B. S. Ong et al., US Patent 7,141,644 (November 28, 2006)

Assignee:

Xerox Corporation (Stamford, CT)

SIGNIFICANCE Mechanically durable and structurally flexible polythiophene derivatives have been prepared that are useful as semiconducters in thin film field effect transistors and are soluble in chlorobenzene. Materials prepared from these agents have a bandgap between 1.5 and 3.0 eV that enhance their function as film transistors.

REACTION

S

Br

i S

S

S

S

ii S

S

S

S

a

i: THF, magnesium, 1,3-bis(diphenylphosphino]dichloronickel(II), 5,50 -dibromo2,20 -dithiophene, hydrochloric acid ii: Ferric chloride, CCl3H 205

206


EXPERIMENTAL 1.

Preparation 5,50 -Bis(3-Dodecyl-2-Thienyl)-2,20 -Dithiophene

A solution of 2-bromo-3-dodecylthiophene (34.92 mmol) dissolved in 40 ml of anhydrous THF was slowly added over a period of 20 minutes to a mechanically stirred suspension of magnesium turnings (51.83 mmol) in 10 ml of THF under an inert argon atmosphere. The mixture was stirred at ambient temperature for 2 hours and then at 50 C for 20 minutes before cooling down to ambient temperature. This mixture was added by cannula to 5,50 -dibromo-2,20 -dithiophene (13.88 mmol) and 1,3-bis(diphenylphosphino)dichloronickel (II) (0.35 mmol) in 80 ml of THF and refluxed for 48 hours. The reaction mixture was then diluted with 200 ml of EtOAc, washed twice with water and 5% HCl, dried with Na2SO4, and concentrated. The dark brown syrupy residue was purified by column chromatography on silica gel, and the product was isolated in 55% yield as a yellow crystalline solid, MP ¼ 58.9 C. 2.

Preparation of Poly[5,50 -bis(3-Dodecyl-2-Thienyl)-2,20 -Dithiophene]

A solution of the Step 1 product (0.75 mmol) in 7 ml of CCl3H was slowly added to a stirred mixture of FeCl3 (2.47 mmol) in 3 ml of CCl3H and heated to 50 C for 1 hour and then to 40 C for 24 hours. After the polymerization, the mixture was diluted with 20 ml of toluene and washed three times with water. The separated organic phase was stirred with 200 ml of 7.5% NH4OH, washed three times with water, and poured into methanol to precipitate the crude polythiophene. The residue was purified by Soxhlet extraction with methanol, hexane, and chlorobenzene, and the product was isolated with a Mw ¼ 27,300 daltons and Mn ¼ 16,900 daltons. 1

H NMR (CDCl3) d 7.18 (d, J ¼ 5.4 Hz, 2H), 7.13 (d, J ¼ 3.6 Hz, 2H), 7.02 (d, J ¼ 3.6 Hz, 2H), 6.94 (d, J ¼ 5.4 Hz, 2H), 2.78 (t, 4H), 1.65 (q, 1.65, 4H), 1.28 (bs, 36H), 0.88 (m, 6H)

DERIVATIVES Only poly[5,50 -bis(3-dodecyl-2-thienyl)-2,20 -dithiophene] in varying molecular weights was prepared. Testing Results Thin film transistor devices were fabricated by spin coating using a 1% solution of the selected polythiophene dissolved in chlorobenzene and drying in vacuo at 80 C for 20 hours. No precautions were taken to exclude oxygen, moisture, or light during device fabrication. From transistors with dimensions of 5000 60 m, electrical properties were determined as summarized in Table 1.

207

27,300 (16,900)

14,900 (9000) Then device annealed at 135 C 10 minutes 14,000 (11,400)

14,900 (9000)

3890 (3800)

Step 2 Product Mw (Mn) (daltons)

2.2–4.7 103 4.5–9.0 104

5.0–8.5 105 1.0–5.1 106

0.9–2.0 104 2.0–3.1 104 1.1–3.4 103

1.9–8.7 103 0.9–2.0 102

25 C (24 hours); precipitated from CH3OH 40 C (1 hour); 25 (48 hours); extracted with toluene 40 C (1 hour); 25 C (24 hours); extracted with CH3OH, hexane, and chlorobenzene 50 C (1 hour); then 40 C.

50 C (1 hour) then 40 C (24 hours); extracted with CH3OH, hexane, and chlorobenzene

1.2 103

Mobility (cm2/V.s)

Reactions/Purifications Conditions

Initial Current On/Off Ratio

1.1–2.5 105 1.9–3.2 105

0.7–1.1 104

––

––

Current On/Off after 5 Days

TABLE 1. Effect of poly[5,50 -bis(3-dodecyl-2-thienyl)-2,20 -dithiophene] of varying molecular weights of the current invention on mobility and current on/off ratio when spin casted onto thin film transistor devices.

208


NOTES 1. In earlier investigations by the author [1] polythiophene analogues containing phenylene, (I), were prepared and used as semiconducters in thin film field effect transistors.

Br

S

S

S

S

Br

i

S

S

a

S

S

(I)

i: 1,4-Benzenebis(pinacolboronate), toluene, Aliquot 336, tetrakis(triphenylphosphine)-palladium 2. Sotzing [2] prepared intrinsically conducting water-borne dispersions of poly (thieno[3,4-b]thiophene) homopolymer, (II), and copolymers of thieno[3,4-b] thiophene and 3,4-ethylenedioxythiophene, (III), for electroactive applications including electrochromic displays, optically transparent electrodes, and antistatic coatings. S S

S

O

b

S S

S S

(II)

S

S

a

S b

O

S

S

S

a O

O

(III)

S

Notes

209

3. Groenendaal [3] prepared water soluble 4-(2,3-dihydro thieno[3,4-b)][1,4] dioxin-2-yl-methoxy)-butane-1-sulfonic acid sodium salt, (IV), and copolymers with poly(styrenesulphonic acid) having a Mw of 290,000 daltons that were used in electroconductive devices.

SO3Na

O O

O S

(IV)

4. Additional polythiophene p-conjugated polymer precursors were prepared by Reuter [4], (V), and Groenendaal [5], (VI), and used in electroconductive devices as semiconductors.

HO O

O R

S S

O

R = C8H17 C10, H21 C12, H25

O

OO S

OH

(V)

(VI)

5. Kirchmeyer [6] prepared linear organic thiophenephenylene oligomers, (VII), that were effective as semiconductor coatings.

S C10H21

S

S

S S

(VII)

S

C10H21

210


6. Regioregular intriniscally conducting mono-, di-, and triblock moderate molecular weight polythiophenes containing a well-defined terminus, (VIII), were prepared by McCullough [7] and used in thin field-effect transitor applications.

H

S S

46

OH

(VIII) References 1. B.S. Ong et al., US Patent 7,132,500 (November 7, 2006) and US Patent 7,132,682 (November 7, 2006) 2. G.A. Sotzing,US Patent 7,125,479 (October 24, 2006), US Patent Application 2005-0124784 (June 9, 2005), and US Patent Application 2004-0010115 (January 15, 2004) 3. B. Groenendaal et al., US Patent 7,105,620 (September 12, 2006) 4. K. Reuter, US Patent 7,102,016 (September 5, 2006) 5. B. Groenendaal et al., US Patent 7,094,865 (August 22, 2006) 6. S. Kirchmeyer et al., US Patent 7,199,251 (April 3, 2007) 7. R.D. McCullough et al., US Patent 7,098,294 (August 29, 2006)

Title: Mono-, Oligo- and Polymers Comprising Fluorene and Aryl Groups Author:

M. Heeney et al., US Patent 7,126,013 (October 24, 2006)

Assignee:

Merck Patent GmbH (Darmstadt, DE)

SIGNIFICANCE Polymers and elastomers comprising at least one 9-H,H-fluorene group and at least one arylene group have been prepared. These materials are suitable for use as semiconductors or charge transport materials in optical, electrooptical, or electronic devices, including field-effect transistors, electroluminescent, photovoltaic, and sensor devices. REACTION

Br

Br

O

i

O B

O B

O

Intermediate S C12H25

C12H25

S

ii

S

C12H25

Br

C12H25

S S

C12H25

Br

iv Intermediate

C12H25

S C12H25

iii

S

a

i: Bis(pinacolato)diboron, potassium acetate, dichlorobis(tricyclohexylphosphine) palladium(II), 4-dioxane ii: BuLi, tetramethylethylenediamine, copper(II) chloride iii: N-Bromosuccinimide, CCl3H, acetic acid iv: Tetrakis(triphenylphosphine)palladium, Aliquat 336, toluene, sodium carbonate

211

212

Mono-, Oligo- and Polymers Comprising Fluorene and Aryl Groups

EXPERIMENTAL 1. Preparation of 2,7-Bis(4,4,5,5-Tetramethyl-1,3,2-Dioxaborolan-2-yl)Fluorene A flask was charged with 2,7-dibromofluorene (17.73 mmol), bis(pinacolato)diboron (44.33 mmol), potassium acetate (5.22 g, 53.20 mmol), dichlorobis(tricyclohexylphosphine)-palladium(II) (0.61 mmol), and 150 ml of 1,4-dioxane and stirred at 100 C for 24 hours. The reaction mixture was quenched with 100 ml of water and extracted twice with 200 ml of CCl3H. Combined extracts were washed with 100 ml of water, dried with Na2SO4, and concentrated. The residue was purified by column chromatography using CH2Cl2, and the product was isolated as a white solid in 76% yield. H-NMR (CDCl3, 300 MHz) d 6.97 (2H, s), 6.76 (2H, s), 2.56 (4H, t,3J.sub.HH ¼ 8.0 Hz), 1.61 (4H, m), 1.20 1.40 (36H, br), 0.88 (6H, t, .sup.3J.sub.HH ¼ 7.0 Hz) 13 C-NMR (CDCl3, 75 MHz) d 44.0, 137.4, 124.8, 118.7, 32.0, 30.6, 30.4, 29.7, 29.6, 29.5, 29.4, 29.3, 22.7, 14.2 1

2.

Preparation of 4,40 -Didodecyl-2,20 -Bithiophene

A solution of 3-dodecylthiophene (39.61 mmol) in 40 ml of THF at ambient temperature was treated dropwise with 18 ml of 2.5 M BuLi in hexanes (45.00 mmol) and 6.8 ml of tetramethylethylenediamine (45.06 mmol) and refluxed 1 hour. The mixture was cooled to 78 C and treated with copper(II) chloride (47.53 mmol) in a single portion. It was then stirred at ambient temperature for 18 hours and refluxed for 6 hours. The mixture was acidified with dilute hydrochloric acid and extracted twice with 200 ml of diethyl ether. Combined extracts were washed with 100 ml of water and dried with Na2SO4 and concentrated. The residue was purified by column chromatography using petroleum ether 40 60, re-crystallized from diethyl ether at 78 C, and the product was isolated as a yellow solid in 38% yield. H-NMR (CDCl3, 300 MHz) d 6.77 (2H, s), 2.51 (4H, t, .sup.3J.sub.HH ¼ 8.0 Hz), 1.57 (4H, m), 1.20 1.40 (36H, br), 0.88 (6H, t, sup.3J.sub.HH ¼ 7.0 Hz) 13 C-NMR (CDCl3, 75 MHz) d 142.8, 136.0, 124.3, 107.0, 31.8, 29.5, 29.4, 29.2, 29.0, 22.6 1

3.

Preparation of 5,50 -Dibromo-4,40 -Didodecyl-2,20 -Bithiophene

A vessel containing the Step 2 product (1.49 mmol) dissolved in 5 ml apiece of CCl3H and glacial acetic acid was treated portionwise with N-bromosuccinimide (2.98 mmol) and stirred overnight before being poured into water and extracted twice with 250 ml of CH2Cl2. Combined extracts were washed twice with 100 ml of water and concentrated. The residue was purified by column chromatography using petroleum ether, and the product was isolated as a yellow solid in 100% yield.

Derivatives

4.

213

Preparation of Poly(4,40 -Didodecyl-2,20 -Bithiophene-alt-Fluorene)

A flask was charged with the Step 1 (1.44 mmol) and Step 3 (1.44 mmol) products, tetrakis-(triphenylphosphine)palladium(0) 0.03 mmol), Aliquat 336 (0.25 g), and 20 ml toluene and then treated with 2.5 ml of 2 M aqueous Na2CO3. The mixture was refluxed for 48 hours and precipitated by pouring into 400 ml of methanol. The polymer was collected and washed with water followed by methanol and then dried. The dried polymer was Soxhlet extracted for 16 hours with methanol and six hours by iso-hexane. The polymer was re-dissolved in hot CCl3H and precipitated in 400 ml methanol and dried; the product was isolated as a green solid in 78% yield. Tm ¼ 130 C Tg ¼ 160 C Td ¼ 360 C Mn ¼ 32,000 daltons (bimodal) Mw ¼ 137,000 daltons Absorbance (lmax CDCl3) ¼ 405 nm 1 H-NMR (CDCl3, 300 MHz) d 7.84 (2H, d, .sup.3J.sub.HH ¼ 8.0 Hz), 7.66 (2H, s), 7.51 (2H, d, .sup.3J.sub. HH ¼ 8.0 Hz), 7.11 (2H, s), 4.02 (2H, s), 2.71 (4H, br), 1.67 (4H, br), 0.95 1.40 (36H, br), 0.87 (6H, br)

DERIVATIVES TABLE 1. Selected bisthiophene-fluorene copolymers and monomer prepared according to the current invention. Entry

Structure

1

C6H13

S S

C6H13 3

C6H13

Tm ( C)

Tg ( C)

MS (m/e)

122

199

—

a

>300 —

C6H13

—

a

4

O O

O

S

S

O

O O

Note: Extensive 1 H- and 13 C-NMR for all entries provided by author.

—

—

768 (M þ OH)

214

Mono-, Oligo- and Polymers Comprising Fluorene and Aryl Groups

NOTES 1. Conjugated polyazulene derivatives, (I) and (II), prepared by Farrand [1] were useful as components in optical, electro-optical, and electronic devices.

a

(I)

a

(II) 2. Jubran [2] and Tokarski [3] prepared photoreceptors comprising an electrically conductive substrate and a photoconductive element consisting of phenothiazines, (III) and (IV), and carbazole, (V), derivatives, respectively.

N N

S

S

S

OH

S

N OH N S

(III)

N R

N R

N N N N

S OH

S

N OH N

S

S

S

N

N

(IV)

N

O

N

OH

N

(V)

R = CH3, C2H5

Notes

215

3. Perfluoroacyl oligomeric thiophene derivatives, (VI), prepared by Gerlach [4] were effective as n-channel semiconductor thin film layers in electronic devices.

O

CF3 C3F7O

C F2

O

O 5

CF3

(VI)


CF3

O S

L.D. Farrand et al., US Patent 7,034,174 (April 25, 2006) N. Jubran et al., US Patent 7,169,520 (January 30, 2007) Z. Tokarski et al., US Patent 7,166,400 (January 23, 2007) C.P. Gerlach et al., US Patent 7,211,679 (May 1, 2007)

CF3

C F2

OC3F7

VIII. ENERGETIC POLYMERS Title: Glycidyl Dinitropropyl Formal, Poly(Glycidyl Dinitropropyl Formal), and Preparation Method Thereof Author:

J. S. Kim et al., US Patent 7,208,637 (April 24, 2007)

Assignee:

Agency for Defense of Korea (Daejeon, KR)

SIGNIFICANCE An energetic polyether containing grafted gem-nitro’s has been prepared having a decomposition temperature of 200 C or higher. This polymeric agent is useful as a stable energetic binder for insensitive and high-performance explosives.

REACTION OH O2N NO2

i

O

O

ii

O O2N NO 2

O

O

O iii O2N NO2

O

O

a O O NO2 NO2

i: Formaldehyde, allyl alcohol, CH2Cl2, boron trifluoride etherate ii: CCl3H, 3-chloroperbenzoic acid iii: 1,4-Butandiol, boron trifluoride etherate, CH2Cl2


218

Glycidyl Dinitropropyl Formal, Poly(Glycidyl Dinitropropyl Formal), and Preparation

EXPERIMENTAL 1.

Preparation Allyl Dinitropropyl Formal

A reactor was charged with 2,2-dinitropropanol (0.1 mol), formaldehyde (0.11 mol), allyl alcohol (0.3 mol), and CH2Cl2 (40 g) and treated with the slow addition of boron trifluoride etherate (0.3 mol) at 5 C. After the addition the mixture was stirred at 5 C for 40 minutes. Thereafter 100 ml of water was slowly added to the mixture, which was then stirred and the aqueous component discarded. The organic layer was washed 3 times with NaOH, once with water, once with brine, and again with water. The organic phase was then dried, concentrated, and the product was isolated in 73% yield.

2.

Preparation of Glycidyl Dinitropropyl Formal

The Step 1 product (0.15 mol) and CCl3H (400 g) were charged into a flask then treated with 3-chloroperbenzoic acid (0.18 mol) over 30 minutes. After the addition was complete, the mixture was refluxed for 3 hours, cooled to ambient temperature, and stirred an additional 12 hours. The mixture was cooled to 0 C, filtered, and the solution was washed twice with 5% sodium sulfite and with 5% sodium hydroxide. The solution was next washed with brine, dried, concentrated, and the product was isolated in 92% yield. 3.

Preparation of Poly(Glycidyl Dinitropropyl Formal)

1,4-Butandiol (2 mmol) was added to boron trifluoride etherate (1 mmol) and vacuum purified for 2 hours to remove diethyl ether. This mixture was then treated with CH2Cl2 (12 g) and the slow addition of the Step 2 product (50 mmol) dissolved in CH2Cl2 over 3 hours. The mixture was reacted an additional 30 minutes and washed with 50 ml of water, 30 ml of CH2Cl2, and three times with 50 ml of brine. It was dried using MgSO4 and then precipitated in 20 ml ethanol. The polymer was next heated to 80 C at 1 mmHg for 5 hours to purify, and the product isolated in 90% yield. The product had a Mw of 2,200 daltons, a polydispersity index of 1.12, a hydroxyl group of 0.621 eq/kg, a Tg of 23 C, and a decomposition temperature greater than 200 C. 1

HNMR(CDCl3) d 2.17(s, 3H), 2.60(t, 1H), 2.78(t, 1H), 3.1(m, 1H), 3.8(m, 1H), 4.3(s, 2H), 4.7(s, 2H)


Notes

219

NOTES 1. In an earlier investigation by the author [1] poly(glycidyl dinitropropyl carbonate), (I), was prepared and used as an energetic binder for insensitive and high-performance explosives. O

a O

O O NO2 NO2

(I)

2. Sanderson [2] prepared the energetic thermoplastic elastomer poly(3,3-bis (azidomethyl)-oxetane), (II), for use as a binder for a propellant, explosive, or gas generant for a supplemental restraint system in automobiles. Random block copolymers of poly(azidomethyloxirane) and poly(3,3-bis(azidomethyl)oxetane), (III), were also prepared by Sanderson [3] using toluene diisocyanate as the coupling agent. N3 N3 N3

N3

H N

O O

O

a (II)

N3

O

a

(III)

N H

O

b

3. Adams [4] prepared energetic fullerenes of the generic formula, C60(NO2)n, where n ¼ 1–60, and where at least 10% of the molecule consisted of nitrogen. References 1. 2. 3. 4.

J.S. Kim et al., US Patent 6,706,849 (March 16, 2004) A.J. Sanderson et al., US Patent 7,101,955 (September 5, 2006) A.J. Sanderson et al., US Patent Application 2006-0157173 (July 20, 2006) C. Adams, US Patent 7,025,840 (April 11, 2006)

Title: Synthesis of Energetic Thermoplastic Elastomers Containing Both Polyoxirane and Polyoxetane Blocks Author:

A. J. Sanderson et al., US Patent 7,101,955 (September 5, 2006)

Assignee:

Alliant Techsystems, Inc. (Edina, MN)

SIGNIFICANCE An energetic thermoplastic elastomer consisting of poly(azidomethyloxirane)-b(3,3- bis(azidomethyl)-oxetane) has been prepared that is suitable for use as a binder for a propellant, explosive, and/or gas generator. Block seqments were prepared using 2,4-diisocyanate toluene.

REACTION N3 Br

H N

O

Br

OH

b

i

O

ii O

Br N3

O N3

NH

a

N3 N3

O

i: Tribromoneopentylalcohol, toluene, tetrabutylammonium bromide, sodium hydroxide sodium azide ii: Poly(azidomethyloxirane), dibutyltin dilaurate, toluene-2,4-diisocyanate, CH2Cl2

EXPERIMENTAL 1.

Preparation of 3,3-bis(Azidomethyl)Oxetane

A reactor was charged with tribromoneopentylalcohol (600 g), 1200 ml of toluene and tetrabutylammonium bromide (6 g) then cooled to 12 C and slowly treated with a 40 wt% solution of sodium hydroxide (193 g). After 36 hours crude bis(bromomethyl) oxetane was washed with water until the pH was less than 9 and then distilled; the product was isolated in 65% yield. 220

Derivatives

221

2. Preparation of Poly[(Azidomethyloxirane)-b-(3,3-bis(Azidomethyl)Oxetane)] In a 250 ml round bottom flask poly(azidomethyloxirane) (19.62 g) and the Step 1 product (6.63 g) were dissolved in 80 ml of CH2Cl2; the solution concentrated sufficiently for the solution to become cloudy. This cloudy solution was then treated with 0.12 ml of dibutyltin dilaurate and toluene-2,4-diisocyanate (3.11 g). After 4 hours, butane-1,4-diol (0.805 g) was added, causing the solution to become steadily more viscous; after another 18 hours, the solution was too viscous to stir. The mixture was then diluted with 50 ml of CH2Cl2, precipitated, and the product was isolated having a Mn of 28,440 daltons, Mw of 219,500, and a polydispersity index of 7.7.

DERIVATIVES Poly(nitromethyloxirane)-b-(3,3-bis(azidomethyl)-oxetane) was also prepared.

N3 H N

O

b O O

N3

NH

a O O2N

NOTES 1. Sanderson [1] and Highsmith [2] prepared glycidyl nitrate and subsequently converted it into polyglycidyl nitrate (I) using calcium hydride and boron trifluoride. O

a ONO2 (I)

222

Synthesis of Energetic Thermoplastic Elastomers Containing Both Polyoxirane

2. Poly(glycidyl dinitropropyl formal), (II), was prepared by Kim [3] and used as a performance insensitive explosive. O

O O

a O O NO 2 NO 2

(II)

3. The energetic plasticizer, 2,2-dinitro-1,3-propanediol-diformate, (III), prepared by Highsmith [4] was used in explosive and propellant compositions.

O2N O

H

O

NO2 O

(III)

H

O


A.J. Sanderson et al., US Patent 6,861,501 (March 1, 2005) and US Patent 6,861,501 (May 4, 2004) T.K. Highsmith et al., US Patent 6,362,311 (March 26, 2002) J.S. Kim et al., US Patent 7,208,637 (April 24, 2007) T.K. Highsmith et al., US Patent 6,425,966 (July 30, 2002)

IX. FIBERS Title: Rigid-Rod Benzobisazole Polymers Incorporating Naphthalene-1,5-Diyl Structure Units Author:

T. D. Dang et al., US Patent 7,041,779 (May 9, 2006)

Assignee:

United States of America as Represented by the Secretary of the Air Force (Washington, DC)

SIGNIFICANCE Aromatic heterocyclic rigid-rod polymers that have exceptional thermal oxidative stability have been prepared using 1,5-naphthylene dicarboxylic acid and 2,5-diamino-1,4-benzenedithiol. These heterocyclic rigid-rod polymers materials are useful as protective garments in ballistic vests and abrasion- and flame-resistant fabrics.

REACTION N

S

S

N

CO 2H

i HO 2 C

a

Notes 1,2

i: 2,5-Diamino-1,4-benzenedithiol dihydrochloride, polyphosphoric acid, phosphorous pentoxide


224

Rigid-Rod Benzobisazole Polymers Incorporating Naphthalene-1,5-Diyl Structure Units

EXPERIMENTAL Preparation of Benzobisthiazole-Naphthalic Fibers A resin flask was charged with naphthalene-1,5-dicarboxylic acid (0.0116 mole), 2,5diamino-1,4-benzenedithiol dihydrochloride (0.0116 moles), and 77% polyphosphoric acid (20.8 g). The mixture was then dehydrochlorinated over a period of 24 hours under a nitrogen flow while slowly raising the temperature to 105 C. The mixture was then cooled and treated with P2O5 (11.37 g) and heated to 165 C and the polymerization reaction proceeded overnight. During this process, stir opalescence characteristic of the anisotropic phase was observed. The mixture was further heated to 180 C for a few hours, and roughly 3 g of the polymer dope were taken out for fiber spinning. Using polarizing optical microscopy a sample of the dope was sealed between two glass slides and found to exhibit optical birefringence; the persistence of the observed optical texture several days later was indicative of lyotropic liquid crystalline behavior of the material. The remaining dope was precipitated in water and the fibrous polymer shredded in a blender. The polymer was filtered off, Soxhlet extracted with hot water and dried, and the product was isolated as a dark yellow solid having an intrinsic viscosity of 13.2 dl/g measured in methanesulfonic acid at 30 C.


NOTES 1. The preparation of naphthalene-1,5-dicarboxylic acid is illustrated below. I

NH2

i NH2

iii

ii I

CO2H

CN

CN

CO2H

i: Hydrochloric acid, sodium nitrite, potassium iodide ii: Copper(I) cyanide, sodium cyanide, water iii: Hydrobromic acid, acetic acid, water 2. The Step 1 product was fabricated into fibers using the continuous dry jet–wet spinning method.

Notes

225

3. Kumar [1] demonstrated that the fiber strength of polyphenylenebenzobisthiazole, (I), increased by using compositions containing carbon nanotubes. N

S

S

N

a

(I)

4. Rigid-rod compositions consisting of polyphenylene derivatives were used by Goldberg [2] as advanced thermoplastics in preparing orthodontic wire. 5. Bazan [3] prepared conformationally flexible rigid rod cationic conjugated polymers, (II), comprising monomers that perturbed the polymer’s ability to form rigid-rod structures, thereby allowing them to form a greater range of three-dimensional structures.

b

a

(H3C)3N

c

N(CH3)3

Br

Br

N(CH3)3

(H3C)3N

Br

Br

(II)

6. Petschek [4] used heterocyclic rigid-rod polyionomers, including poly(pyridinium) salt, (III), and poly(benzimidazole-sulfonate), (IV), for coating directionally onto charged surfaces to impart planar alignment and pre-tilt to the surfaces.

N

N

a

N

H N

N H

N

(IV) (III)

a SO3

226

Rigid-Rod Benzobisazole Polymers Incorporating Naphthalene-1,5-Diyl Structure Units

References 1. S. Kumar et al., US Patent 6,900,264 (May 31, 2005) 2. A.J. Goldberg et al., US Patent 7,186,115 (March 6, 2007) 3. G.C. Bazan et al., US Patent 7,144,950 (December 5, 2006) and US Patent Application 2007-0088130 (April 19, 2007) 4. R.G. Petschek et al., US Patent 6,942,905 (September 13, 2005)

Title:

Polybenzazole Fiber and Use Thereof

Author:

Y. Abe et al., US Patent Application 2006-0083923 (April 20, 2006)

Assignee:

Canon Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE Polybenzazole fibers have been prepared containing blended organic pigments that are heat, moisture, and light resistant with thermal decomposition temperatures exceeding 200 C. These materials are useful as fibers for high-strength rope, cement/concrete reinforcers, and bullet proof vests.

REACTION H2 N

NH2

N

N

O

O

i HO

OH

a

i: Terephthalic acid, polyphosphoric acid

EXPERIMENTAL Preparation of Poly(p-Phenylenebenzobisoxazole) Under a stream of nitrogen gas, 4,6-diamino-resorcinol dihydrochloride (334.5 g), terephthalic acid (260.8 g), and polyphosphoric acid (2,078.2 g) were mixed and stirred at 60 C for 30 minutes. The temperature was gradually increased to 135 C for 20 hours, 150 C for 5 hours, 170 C for 20 hours, and then the material isolated. The product had an intrinsic viscosity of 30 dL/g at 30 C measured in methanesulfonic acid.

DERIVATIVES Only the single derivative was prepared. 227

228

Polybenzazole Fiber and Use Thereof

TESTING Filaments were subjected to storage testing at elevated temperatures and high humidity as well as light exposure testing. Testing results are provided in Table 1. TABLE 1. Effect of high temperature and humidity and light exposure on poly (p-phenylene-benzobisoxazole) film strength retention containing various dopants. Exposure to 80% Humidity at 80 C for 700 hours

Entry 1

4

12

15

Exposure to Light from Xenon Lamp for 100 hours

Final Final Initial Strength Strength Retention Strength Retention (GPa) (%) (GPa) (%) (GPa)

Dopant 29H,31HPhthalocyaninate(2-)N29,N30,N31,N32 copper 9,19-Dichloro-5,15diethyl-5,15dihydrodiindlo[2,3c:20 ,30 -n]triphenodioxazine Bisbenzimidazo[2,1b:20 ,10 -I]benzo[1mn][3,8]phenathroline8,17-dione 29H,31H-Phthalocyaninate(2-)N29, N30,N31,N32 copper

5.6

5.0

90

4.9

83

5.5

4.8

88

4.5

81

5.8

5.0

87

4.8

82

4.7

4.3

92

4.2

89

NOTES 1. Saitoh [1] prepared oriented polybenzazole, (I), films having high strength and high elastic modulus and heat and flame resistance. O

N

N

O

a

(I)

2. Kodama [2] prepared high molecular weight polybenzazoles, (I), using iron, (II), phosphate octahydrate as a reaction catalyst.

Notes

229

3. Polybenzazole block copolymer, (II), prepared by Kodama [3] and containing light-resisting m- or p-phenylenediamine had a 30% reflectance in the wavelength region of from 450 to 700 nm. N

c

N

O

O a

O

N

b

(II)

4. Polybenzazole fibers, (I), prepared by Kitagawa [4] had a compression strength of not less than 0.5 GPa when blended with 1% to 15% carbon nanotubes having a length of more than 20 nm and width of between 0.5 mm–10 mm. The resulting fibers had high strength, high elastic modulus, and fine fiber structure. 5. Adamantyl benzoxazole pre-polymers, (III) and (IV), were prepared by Takaragi [5] and Nagano [6], respectively, and used to prepare high molecular weight polymers with porous structures that were used in dielectric films associated with semiconductors. OH

OH

H2N

O

H2N N O

(III)

N

OH

a O

O

(IV)

References 1. 2. 3. 4. 5. 6.

OH

F. Saitoh et al., US Patent 7,122,617 (October 17, 2006) F. Kodama et al., US Patent 6,169,165 (January 2, 2001) T. Kodama et al., US Patent 6,818,734 (November 16, 2004) T. Kitagawa, US Patent 6,884,506 (April 26, 2005) A. Takaragi et al., US Patent Application 2007-0078256 (April 5, 2007) S. Nagano et al., US Patent Application 2007-0032556 (February 8, 2007)

OH

a O

X. FLUORINE A. Critical Polymerization

Title:

Process for Producing Fluoropolymer

Author:

M. Tsukamoto et al., US Patent 7,173,098 (February 6, 2007)

Assignee:

Daikin Industries, Ltd. (Osaka, JP)

SIGNIFICANCE An efficient method for preparing polyvinylidene fluoride by reacting above the monomer critical density and temperature is described. When polyvinylidene fluoride was prepared in this manner, molecular weights were at least four times greater than those noncritically prepared.

REACTION F

i Notes 1, 2

F

F2 C

i: Di-n-propyl peroxydicarbonate

EXPERIMENTAL Preparation of Polyvinylidene Fluoride A stainless steel autoclave with an internal volume of 1083 ml was charged with vinylidene fluoride (542 g) using a high-pressure plunger pump to establish a monomer density of 0.50 g/ml. Using a band heater the reaction temperature was raised to 40 C, which provided a reaction pressure of 5.72 MPa. The reaction


232

Process for Producing Fluoropolymer

was then initiated with 6.1 g of 50% di-n-propyl peroxydicarbonate solution in methanol; the polymerization continued for 1 hour. After venting, unreacted monomer, 29.5 g of a white-colored product was isolated with Mn ¼ 36,080 daltons and Mw ¼ 78,050 daltons.

SCOPING STUDIES TABLE 1. The effects of polymerization of vinylidene fluoride for one hour at 318 K at varying reaction pressures.

Entry

Monomer (g)

1 2 Noncritical Comparison

542 639 314

Monomer Reaction Density (g/ml)

Reaction Pressure (MPa)

Mn (daltons)

Mw (daltons)

5.72 6.62 5.13

36, 080 54,900 8,560

78,050 118,500 14,700

0.50 0.59 0.29

Note: Critical parameters for vinylidene fluoride are 4.430 MPa as a critical density and 303.30 K as a critical temperature.

TABLE 2.

Critical parameters for selected perfluoro monomers.

Monomer Vinylidene floride Hexafluoropropene Tetrafluoroethylene Chlorotrifluoroethylene

Critical Density (g/ml)

Critical Temperature (K)

4.430 2.900 3.940 3.960

303.30 367.10 306.00 379.00

Note: Critical parameters for perfluoro solvents were also provided by the author.

NOTES 1. In subsequent investigations by the author [1] when the Step 1 reaction of the current invention was continued for 120 to 150 minutes, the corresponding polymer had a Mn of 81,000 daltons and a Mw of 203,000 daltons. Additional critical polymerization reaction scoping studies using vinylidene fluoride are described by the author [2]. 2. Lee [3] polymerized vinylidene fluoride in supercritical water, namely T H2 O > 374 C and PH2 O > 218:2 atm, using either t-butyl peroxyacetate or t-butyl peroxy-2-ethylhexanoate and obtained Mn’s exceeding 1 million daltons with a crystalline content >50%. In an earlier investigation by Lee [4] showed

Notes

233

that when methyl methacrylate and glycidal methacrylate were copolymerized in supercritical water, a low polydispersed product was obtained. References 1. M. Tsukamoto et al., US Patent Application 2006-0122347 (June 8, 2006) 2. M. Tsukamoto et al., US Patent Application 2005-0043498 (February 24, 2005) 3. S. Lee et al., US Patent 7,091,288 (April 15, 2006)

B. High Strength

Title: Fluorinated Terpolymer Author:

S. Kurihara et al., US Patent 7,009,017 (March 7, 2007)

Assignee:

Unimatec Co., Ltd. (Tokyo, JP)

SIGNIFICANCE Perfluoro terpolymers consisting of tetrafluoroethylene, perfluoro(ethyl vinyl ether), and perfluoro(propyl vinyl ether) have been free radically prepared to have distinguished transparency and good mechanical strength at both ambient temperature and 372 C. These materials are particularly useful as high-strength moldings.

REACTION C2F5

C3F7 O

F2C

CF2

F2 C

i C F2

O

CF C F2

CF C F2

a

i: Isobutyryl peroxide, perfluoro-n-heptane, perfluoro(ethyl vinyl ether), perfluoro (propyl vinyl ether

EXPERIMENTAL Preparation of Poly[Tetrafluoroethylene-co-Perfluoro(Ethyl Vinyl Ether)-coPerfluoro-(Propyl Vinyl Ether)] A high-pressure reactor was charged with water (1200 g), perfluoro-n-heptane (690 g), perfluoro(ethyl vinyl ether) (22 g), perfluoro(propyl vinyl ether)(26 g), and methanol (0.1 g). After the temperature was increased to 30 C, tetrafluoroethylene (160 g) was added until a pressure of 0.85 MPa was obtained. The overall monomer ratio 234

Notes

235

of tetrafluoroethylene/perfluoro(ethyl vinyl ether)/perfluoro(propyl vinyl ether) was 77/10/13, respectively. The polymerization was initiated with 25 wt% isobutyryl peroxide (4.0 g) dissolved in CClF2CF2CHClF. Since the reaction pressure decreased with the reactions progress, additional reagent mixture was added to maintain a pressure of 0.85 MPa. Following the addition of these monomers, the mixture continued to react until the reaction pressure remained constant and the mixture aged. Unreacted gases were purged from the reactor at 0.5 MPa, and 231 g of product was isolated.

REACTION SCOPING TABLE 1.

Physical properties of perfluoro terpolymers as a function of composition.

Item

Sample 1

Sample 3

Sample 5

Sample 9

95 2 3

72 13 15

46 25 29

46 39 15

11

22

1.4

1.1

62 92

95 96

96 97

95 97

102

43

21

21

Composition (wt%) Tetrafluoroethylene Perfluoro(ethyl vinyl ether) Perfluoro(propyl vinyl ether) Tensile strength at break (372 C; 103 Pa.s) Light transittance 250 nm (%) 650 nm (%) Glass transition temperature ( C)

NOTES 1. Functionalized terpolymers, (I), consisting of vinylidene fluoride, hexafluoropropene, and silyl-modified tetrafluoroethylene were prepared by Chung [1] to increase the reactivity of perfluoropolymers to subsequent chemical modification.

H Si CF3

F2 C

CF C F2

CF C F2

(I)

a

236

Fluorinated Terpolymer

2. Perfluoro terpolymerss consisting of tetrafluoroethylene, hexfluoropropylene, and vinylidene fluoride were prepared by Park [2] using electron beam radiation. Perfluoro terpolymers were also prepared by Park [3] using 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane. 3. Liquid vulcanizable fluoroelastomers consisting of vinylidene fluoride, perfluoro(methyl vinyl ether), and tetrafluoroethylene were prepared by Kojima [4] and Park [5] and used for molding materials of low hardness. 4. Elastomers consisting of vinylidene difluoride/hexafluoropropylene or vinylidene difluoride/hexafluoropropylene/tetrafluoroethylene elastomers were prepared by Hochgesang [6] and cured using 4,40 -hexafluoroisopropylidene diphenol.

References 1. 2. 3. 4. 5. 6.

T.Z. Chung et al., US Patent 7,045,248 (May 22, 2007) E.H. Park et al., US Patent 7,230,038 (June 12, 2007) E.H. Park et al., US Patent 7,153,908 (December 26, 2006) Y. Kojima et al., US Patent 7,202,299 (April 10, 2007) E.H. Park et al., US Patent 7,230,038 (June 12, 2007) P.J. Hochgesang et al., US Patent 7,098,270 (August 29, 2006)

C. Low Molecular Weight

Title: Directly Polymerized Low Molecular Weight Granular Polytetrafluoroethylene Author:

R. A. Morgan, US Patent 7,176,265 (February 13, 2007)

Assignee:

E.I. du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE Tetrafluoroethylene polymerized in the presence of the chain transfer agent ethane was used to prepare elastomeric grandular polytetrafluoroethylene. The average reaction time was roughly 90 minutes and occurred in the absence of the surfactant perfluorooctanoic acid.

REACTION F F

F

F

i F

F

F F a

i: Ethane, ammonium persulfate, water

EXPERIMENTAL Preparation of Low Molecular Weight Polytetrafluoroethylene Specific concentrations and reaction parameters are provided in Table 1. All polymerizations were carried out in a stainless steel autoclave equipped with a two-bladed, 45 angled flat downdraft agitator mounted on a vertical shaft. An autoclave was charged with water (21.4 kg) and ammonium persulfate dissolved in water (0.3 to 0.6 kg). The vessel was then purged of air by alternately pressuring it with tetrafluoroethylene and evacuating. The chain transfer agent was 237

238

Directly Polymerized Low Molecular Weight Granular Polytetrafluoroethylene

added, and the autoclave heated to 65 C and then pressurized to 1.83 MPa with tetrafluoroethylene with an agitator speed at 600 rpm for the reaction. The initiator solution was next pumped into the autoclave and sufficient tetrafluoroethylene added to maintain a 1.83 MPa reaction pressure. The reaction was completed once the amount of tetrafluoroethyleneadded was between 6.4 and 8 kg. The autoclave was dismantled and the product was isolated.

REACTION SCOPING TABLE 1. Single-step experimental parameters used in preparing low molecular weight granular polytetrafluoroethylene using either ethane or chloroform as chain transfer agents.

Entry 1 2 3 4 5 8 10 11

Chain Transfer Agent*1 (mol%)

Ammonium Persulface Initiator (lb)

CHCl3 (2.0) CHCl3 (3.5) C2H6 (2.2) C2H6 (5.4) C2H6 (5.3) C2H6 (3.1) C2H6 (0.33) C2H6 (0.55)

0.013 0.019 0.033 0.053 0.066 0.033 0.010 0.013

Perfluorooctanoic Acid Surfactant (lb) None None None None 0.0048 None None None

TFE Added (lbs)

Reaction Time (min)

14.3 15.9 14.1 14.1 15.9 14.1 14.1 14.1

128 132 82 73 117 98 63 74

*1

Mol% of gas at the beginning of polymerization

REACTION SCOPING TABLE 2. Physical properties of polytetrafluoroethylene formed in the presence of chain transfer agents ethane and chloroform.

Entry 1 2 3 4 5 8 10 11

Viscosity Polymer Melt (Pa.S) 7.1 103 3.8 104 1.3 105 7.9 103 2.0 103 2.4 104 NA NA

Particle Size Specific Surface Area (m2/g) 3.58 4.24 4.35 — 4.99 — 4.49 4.40

Average Size (mm) 24.9 21.7 36.7 25.0 12.7 32.8 830 649

DSC Melting Point ( C) 125 148 296 148 105 176 1535 1535

Notes

239

NOTES 1. Albano [1] prepared oligomers consisting of 40% perfluoromethylvinylether and 60% tetrafluoroethylene using the surfactant CF2ClO(CF2CF(CF3) O)n(CF2O)mCF2COOH where n/m ¼ 10 with a Mn 600 daltons using 1,6-diiodoperfluorohexane as the chain transfer agent. In a subsequent investigation by Comino [2] perfluoro oligomers were prepared using 1,10-perfluorodecadiene, (I), as the crosslinking agent.

C F2 6

(I) 2. Perfluoroelastomers prepared by Bish [3] and Hung [4] containing roughly 3 wt% of the termonomer perfluoro(8-cyano-5-methyl-3,6-dioxa-1-octene), (II), or N,N0 -bis(2-propenyl)-4,40 -(hexafluoro-isopropylidene)diphthalimide, (III), respectively, were thermally cured and used as seals in high temperature automotive applications.

F C F2C

O

F2 C

CF

O

CF3

C F2

F2 C

CF3

O CN

N

N

CF3

O

(II)

O

O

(III)

3. Navarrini [5] prepared tetrafluoroethylene/fluorovinyl ether co- and terpolymers, (IV), and (V), respectively, that behaved as both plastomers having good thermal and mechanical properties at high temperatures and elastomers with improved properties at low temperatures. Tetrafluoroethylene and nonfluorinated vinyl ether co- and terpolymers were also prepared in the investigation.

F2 C

C F2 a

F2 C

F2C O (IV)

F2 C CF b O

F3C

CF O

C F2

CF3 F3C

CF a O

F2 C

C b F2

F2 C F2C O

CF2 O (V)

CF c O C F2

CF3

240

Directly Polymerized Low Molecular Weight Granular Polytetrafluoroethylene


M. Albano et al., US Patent 7,022,773 (April 4, 2006) C. Comino et al., US Patent Application 2005-0282969 (December 22, 2005) C.J. Bish et al., US Patent 6,638,999 (October 28, 2003) M.H. Hung et al., US Patent 6,794,455 (September 21, 2004) W. Navarrini, US Patent 6,963,013 (November 8, 2005)

Title: Fluoroelastomers Containing Copolymerized Units of Vinyl Esters Author:

M.-H. Hung et al., US Patent Application 2007-0100101 (May 3, 2007)

Assignee:

Dupont Performance Elastomers, L.L.C. (Wilmington, Del)

SIGNIFICANCE In order to fully develop physical properties such as tensile strength, elongation, and compression set, perfluoro elastomers must be cured. Perfluoro elastomers containing vinyl acetate units were prepared that, when saponified with sodium hydroxide, provide hydroxyl cure sites.

REACTION F2C

CF OCF3

i

F2 C

F2 C CF

a

OCF3

O

b

C F2

c

O i: Ammonium perfluorononante, disodium phosphate heptahydrate, ammonium persulfate, vinyl acetate, tetrafluoroethylene

EXPERIMENTAL 1. Preparation of Poly(Tetrafluorene-co-Perfluoro(Methylvinyl Ether)-coVinyl Acetate) A 1-liter stainless reactor was charged with 450 ml of water, ammonium perfluorononante (3.0 g), disodium phosphate heptahydrate (2.0 g), ammonium persulfate (0.4 g), and vinyl acetate (5.0 g). The reactor was sealed, treated with tetrafluoroethylene (45 g) and perfluoro(methylvinyl ether) (40 g), and heated to 70 C for 8 hours 241

242

Fluoroelastomers Containing Copolymerized Units of Vinyl Esters

with an agitation speed of 900 rpm. Thereafter the latex was coagulated with saturated MgSO4 solution, and the precipitate was collected by filtration. The solid was washed with warm water, dried, and 29.4 g of product were isolated as a white polymer. The product had a Tg of 0.2 C and a composition consisting of TFE/PMVE/ VAc, 60.0:32.0:8.0 mol%, respectively.

DERIVATIVES TABLE 1. Summary of random co-vinyl acetate derivatives prepared by emulsion polymerization using ammonium persulfate as the free radical initiator. Polymer*1

Entry 2 3 4 5

Tg ( C)

Composition

PMVE-VAc TFE-TFP-PVAc TFE-TFP-VA TFE-P-VAc-TFP TFE-PMVE-E-VAc

31.7 68.3 63.0:30.4:5.0 63.0:30.4:1.6 63.3:31.8:3.2:1.7 46.7:27.3:25.2:10.8

23 — — 6.9 11.1

Note: Vinyl acetate derivatives was saponified using sodium hydroxide. *1

E, Ethylene P, Propylene VA, Polyvinyl alcohol VAc, Vinyl acetate PMVE, Perfluoromethylvinyl ether TFE, Tetrafluoroethylene TFP, 3,3,3-Trifluoropropene

NOTES 1. In an earlier investigation by the author [1] a random polymer consisting of TFE-VF2-PVME-VAc, 30.4:41.9:27.0:0.7 mol%, respectively, was prepared having a Tg of 28.1 C. 2. A copolymer consisting of TFE and 24 mol% of perfluoro-3,5-dioxa-1-heptene, (I), with a Tg of 21.4 C was prepared by Navarrini [2] that had good high-temperature properties and elastomers with improved low-temperature properties when using perfluoropropenylperoxide as the free radical initiator. Arrigoni [3] used perfluoro-3,5-dioxa-1-heptene with vinylidene fluoride and 3,3,4,4,5,5,6,6,7,7,8,8-dodecylfluoro-1,10 decadiene, (II), to prepare perfluoroelastomers with enhanced low-temperature properties.

F2 C

F2 C F3C

O

F C O

(I)

CF2

F2 C

(II)

6

Notes

243

3. Perfluoro elastomers having improved low-temperature properties were prepared by Grootaert [4] and consisted of TFE-HFP-perfluorocyanopropyl perfluorovinyl ether, (III), 65.0:34.2:0.8, respectively,

F2 C

F2 C NC

C F2

F C O

CF2

(III)


M.-H. Hung et al., US Patent Application 2007-0100099 (May 3, 2007) W. Navarrini, US Patent Application 2007-0100100 (May 3, 2007) S. Arrigoni et al., US Patent Application 2007-0093625 (April 26, 2007) W.M.A. Grootaert et al., US Patent 7,094,839 (April 22, 2006)

D. Low Surface Energy

Title: Amorphous Polyether Glycols Based on bisSubstituted Oxetane and Tetrahydrofuran Monomers Author:

A. A. Malik et al., US Patent 6,998,460 (February 14, 2006)

Assignee:

Aerojet-General Corporation (Sacramento, CA)

SIGNIFICANCE Mono- and di-substituted oxetane monomers containing 2,2,2-trifluoroethoxy methyl substituents have been prepared. These agents were then used to prepare elastomers, thermoset plastics, and related articles where a very low surface energy was required.

REACTION Tosylate

F3CH2C

Tosylate O

CH2CF3 O

O

O

i

F3CH2C

O

O

CH2CF3

ii O

O

O

a

i: DMF, sodium hydride, trifluoroethanol ii: Trifluoroethanol, boron trifluoride etherate, CH2Cl2

EXPERIMENTAL 1.

Preparation of 3,3-bis-(2,2,2-Trifluoroethoxymethyl)Oxetane

Sodium hydride (0.383 mol) was suspended in 200 ml of DMF, treated with the dropwise addition of trifluoroethanol (0.383 mol), and stirred for 30 minutes. This mixture was further treated with a solution of 3,3-bis-(hydroxymethyl)oxetane di-ptoluenesulfonate (0.073 mol) in 50 ml of DMF. The mixture was then heated to 75 C for 64 hours, poured into water, and extracted twice with CH2Cl2. The combined extracts were washed with brine, 2% aqueous HCl, water, dried using MgSO4, and 244

Notes

245

concentrated. The residue was purified by bulb-to-bulb distillation at 42 C to 48 C at 0.1 mm, and the product was isolated in 79% yield as a colorless oil. 2.

Preparation of Poly[3,3-bis-(2,2,2-Trifluoroethoxymethyl)Oxetane]

A reaction vessel was charged with a solution of trifluoroethanol (0.058 mol) and boron trifluoride etherate (0.81 mol) dissolved in 900 ml of CH2Cl2 and treated with a solution of the Step 1 product (4.1 mol) dissolved in 485 ml of CH2Cl2 over 2.5 hours. The mixture was stirred at ambient temperature for 16 hours and then quenched with water. The organic layer was washed with brine and 2% aqueous HCl, concentrated, and the product was isolated in 91% yield having a DSC mp of 71.7 C, decomposition temperature >210 C, and a Mn of 27,000 daltons with a PDI of 2.2. H NMR d 3.87 (s 4H), 3.87 (q, J ¼ 8.8 Hz, 4H), 4.46 (s, 4H) CNMR d 43.69, 68.62 (q, J ¼ 35 Hz), 73.15, 75.59, 123.87 (q, J ¼ 275 Hz); 19 F NMR d 74.6(s) FTIR (KBr, cm1) 2960 2880, 1360 1080, 995, 840 1

13

DERIVATIVES CH2CF3

O

CH2C10F21

CH2C6F13

O

O

O

O

O

NOTES 1. In an earlier investigation by the author [1] the Step 2 product was converted into urethanes by reacting with toluene diisocyanate, (I).

F3CH2C

HN

O

O

CH2CF3

O

a

F3CH2C F3CH2C

O NH

O O

(I)

246

Amorphous Polyether Glycols Based on bis-Substituted Oxetane and Tetrahydrofuran Monomers

2. Thermoplastic polyurethane resins were also prepared by the author [2] from 4,40 -methylene diphenylisocyanate with poly(3,3-bis-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-co-3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-3-methyloxetane) using dibutyltin dilaurate as catalyst and used in low surface energy coating applications 3. Yamamoto [3] prepared perfluoroalkoxy methacrylate, (II), by reacting poly(2hydroxyethyl methacrylate), (III), with boron trifluoride-diethyl ether complex, which was then used to reduce water repellency on surfaces.

a

O

O O

O

C8F17

C8F17

(II)

(III)

4. Kaplan [4] prepared fluorochemical release agents, (IV), for use as fluoroelastomer fuser component in electrostatographic reproducing equipment.

CF3 F2C

F2C F2C

CF2 CF2

CF2 Si

O

Si a O

b

(IV)


A.A. Malik et al., US Patent 6,417,314 (June 9, 2002) A.A. Malik et al., US Patent Application 2006-0135729 (June 22, 2006) I. Yamamoto et al., US Patent 7,176,267 (February 13, 2007) S. Kaplan et al., US Patent 6,830,819 (December 14, 2004)

E. Silicon Fluids

Title:

Cyclic Siloxane Compounds and Making Method

Author:

K. Uehara et al., US Patent 7,189,868 (March 13, 2007)

Assignee:

Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)

SIGNIFICANCE Cyclic siloxane compounds containing an aliphatic unsaturation component and fluorinated alkyl groups were prepared in a two-step process with overall yields >53%. These polymerizable agents are characterized as having water and oil repellency in addition to weather, solvent, and chemical resistance.

REACTION Cl Si Si

F3C

O

O Si

Si O

CF3

i F3C

O Si

Cl

O

O

Si

Si

O Si CF3

ii Notes 1,2

F3C F3C

Si

O

O

Si

CF3

Si O CF3

F3C

i: Vinylmethyldichlorosilane, hexamethylphosphoric triamide ii: Water, isooctane

EXPERIMENTAL 1. Preparation of 1-Chloro-1-Methyl-1-Vinylsiloxy-3,5,7-Tris(30 ,30 ,30 Trifluoropropyl)-7-Chloro-7-Methylsiloxy-3,5,7-Hexamethylcyclotrisiloxane A flask was charged with 1,3,5-tris(30 ,30 ,30 -trifluoropropyl)-1,3,5-hexamethylcyclotrisiloxane (0.3 mol) that had been melted by heating the solid to 40 C to 50 C and then treated with vinylmethyldichlorosilane (0.3 mol). The mixture was further treated with the dropwise addition of hexamethylphosphoric triamide (0.0015 mol) and the 247

248


temperature kept at roughly 50 C for 2 hours. An analysis of the contents by gas chromatography indicated that the product yield was 91%. 2. Preparation of 1-Vinyl-3,5,7-Tris(30 ,30 ,30 -Trifluoropropyl)-1,3,5,7Tetramethylcyclotetra-Siloxane A flask was charged with 162 ml of water and slowly treated with the dropwise addition of the Step 1 product while the mixture stirred at 10 C. After the addition, the mixture was stirred 30 minutes at ambient temperature with IR monitoring until the reaction was complete. The mixture was extracted with 180 g of isooctane and then washed with water and concentrated under reduced pressure. The residue was purified by distillation at 101 C to 105 C under reduced pressure, and 114 g of a liquid fraction product was isolated in 68% yield.

DERIVATIVES O Si

R

Si O

CF3

O Si Si O

CF3 F3C TABLE 1. Step 1 and 2 product yields of tetramethylcyclotetrasiloxane derivatives. Entry 2 3

R

Step 1 Yield (%)

CH2¼C(CH3)CO2CH2CH2CH2 CF2¼CH2CH2

Step 2 Yield (%)

84 85

64 98

NOTES 1. Additional polymerizable cyclic siloxane derivatives, (I), were prepared by the author [1] in a subsequent investigation. O Si

O

Si O

O

O Si

CF3

Si O CF3

(I)

F3C

1 H-NMR (CDCl3) d 0.16 0.17, d, 9H; 0.20, s, 3H; 0.74 0.84, m, 6H; 1.96 2.16, m, 6H; 5.74 6.10, m, 3H MS ¼ 554

Notes

249

2. Cyclic oligosiloxanes were prepared by Shinbo [2] through a disproportionation reaction using tri(i-propoxy)aluminum as the catalyst as illustrated below.

(H3C)3SiO

OSi H

H Si O

i

Si(CH3)3 45

H

O

H Si

Si

O O

Si

H

i: Tri(i-propoxy)aluminum 3. Kiyomori [3] prepared a monofunctional polymerizable oligosiloxane cage, (II), which improved compatibility with solvents and was also polymerizable with other monomers.

O O

Si

O

(II)

Oligosiloxane cage

4. Fluorosilane monomers, (III), prepared by Kinsho [4] were converted into the corresponding terpolymer, (IV), by reacting with water and acetic acid then used in resist compositions. OC2H5

O Si3/2 30

O Si 3/2 20

C2H5O Si OC2H5

O

O

O CF2 O

(III)

OH CF3

O

O

O

O

CF2 O

O Si 3/2 50

OH CF3

O

t-C4H9

(IV)

5. Through the polymerization of pentamethylcyclopentasiloxane, (V), Kennedy [5] prepared new compositions of matter consisting of poly(cyclosiloxane) network derivatives, (VI), as illustrated below.

250


Si O O H SiH HSi O

H O Si

(V)

.....

.....

.....

Si O

Si O O

O

Si

Si

O

O

O Si O Si O

i

.....

O

Si

Si

O

Si

O O SiH O Si O Si O O

.....

Si

Si

.....

O O Si

O Si

.....

.....

(VI)

i: Platinum divinyl complex, toluene (Karstedt’s system) 6. Molding compositions were prepared by Fehn [6] by curing vinyldimethylsiloxy-terminated polydimethylsiloxane with rhodium(III) acetylacetonate. References 1. 2. 3. 4. 5. 6.

K. Uehara et al., US Patent Application 2006-0264649 (November 23, 2006) K. Shinbo et al., US Patent Application 2006-0223963 (October 5, 2006) A. Kiyomori et al., US Patent Application 2006-0074213 (April 6, 2006) T. Kinsho et al., US Patent Application 2007-0009832 (January 11, 2007) J. Kennedy et al., US Patent 7,071,277 (July 4, 2006) A. Fehn et al., US Patent Application 2006-0058484 (March 16, 2006)

F. Surfactants

Title: Fluorinated Organosilicon Compounds and Fluorochemical Surfactants Author:

H. Yamaguchi et al., US Patent Application 2006-0264596 (November 23, 2006)

Assignee:


SIGNIFICANCE Although fluorochemical surfactants containing perfluoroalkyl carbonyl fluorides currently exist in the art, it is difficult to obtain perfluoroalkyl derivatives containing six or more carbons. A method to address this problem using organosilicon compounds is described.

REACTION O ((H 3C) 2HSiO)

3

Si CH 2CH2 Si

(OSiH(CH3)2)3

CH3 CF3 CF3 Si (CH2)3 OCH2CF (OCF2CF) F 2 CH 3

i Note 1

0.75

CH 3 (H2C)2

Si O Si

(CH2)3 (CH2CHO)3 CH

CH 3

3

2.25 2

i: Di(perfluoroethylene oxide) allyl ether, toluene, platinum(0) 1,3-divinyl-1,1,3, 3-tetramethyldisiloxane, tri(ethylene oxide) allyl ether

EXPERIMENTAL Preparation of Polysiloxane A flask was charged with a siloxane (85.7 g) and toluene (105.6 g) containing platinum (0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.18 g; 0.9 mg Pt) and heated 251

252

Fluorinated Organosilicon Compounds and Fluorochemical Surfactants

to 80 C. This mixture was treated with the dropwise addition of di(perfluoroethylene oxide) allyl ether (125.4 g) and tri(ethylene oxide) allyl ether (147.1g) for over 2 hours. The mixture was then concentrated, and 320.0 g of product were isolated as a pale brown oil. 1

H-NMR d 0–0.1 (36H, Si–CH3), 0.1-0.2 (16H, Si–CH2–),1.3–1.5 (12H, –CH2–), 3.1 (27H, CH3O–), 3.2– 3.5 (72H, –CH2O–)

DERIVATIVES Derivatives corresponding to the Step 1 product with varying polyether/fluorine content are provided in Table 1. TABLE 1. Correlation of surface tension and HLB for Step 1 products containing varying amounts of polyether and fluorine contents. Entry

Fluorine Content (%)

1 2 3 4 5

21.6 24.7 11.5 5.9 27.1

Polyether Content (%) 26.6 37.3 49.4 56.0 22.2

HLB

Surface Tension (dynes-cm 1)

5.3 7.5 9.9 11.2 4.4

24.5 23.3 25.1 26.3 23.5

NOTES 1. Structures of the Step 1 co-reagents perfluoropolyether allyl ether, (I), and allyl polyether, (II), are provided below. CF3 F

CF3

(CFCF2OCF)2

CH3(CH2CH2O)3OCH2CH=CH2 CH2OCH2CH=CH2

(II)

(I) 2. The surface treatment agent perfluoropolyether-modified silane, (III), was prepared by the author [1] and had improved water/oil repellency, chemical resistance, and antifouling properties. OC2H5 C2H5O Si

(CH2)3O CH2CF2 (OC F ) (OCF ) OCF CH 2 4 21 2 24 2 2 O(CH2)3 OC2H5 (III)

OC2H5 Si

OC2H5

OC2H5

Notes

253

3. Copolymers consisting of N-methyl perfluorooctyl sulfonamidoethylacrylate and 3-trimethyl-silylpropyl methacrylate, (IV), were prepared by Dams [2] and used as oil and water repellents.

a

O

b

NH O

O

SO2

C8F17

(H3CO)3Si

(IV)

4. The polycondensate of FomblinÒ and 3-(trimethoxysilyl)propyl amine prepared by Moore [3] was used to provide resistance to water, oil, and stain repellency to a substrate or fabric. De Dominicis [4] used mono and difunctional perfluoropolyether phosphates and amidosilane derivatives as antistaining agents for ceramic materials. 5. A three-component, (V), (VI), and (VII), curable fluoropolyether useful in rubber compositions and rubber fabrics was prepared by Osowa [5]. The material exhibited solvent resistance, chemical resistance, weather resistance, water and oil repellency, and heat resistance. CF3 Si

N

CF

F2 C

O

CF

O

C8F17

O

CF3

CF3

F2 C aC

F2

O

CF

C F2

O O

a + b = 130 Si

O

Si

3

(VI)


H. Yamaguchi et al., US Patent 7,196,212 (March 27, 2007) R.J. Dams, US Patent 7,166,329 (January 23, 2007) G.G.I. Moore et al., US Patent 7,097,910 (August 29, 2006) M. De Dominicis et al., US Patent 7,045,016 (May 16, 2006) Y. Osawa et al., US Patent 6,979,710 (December 27, 2005)

Si

CF3

(V)

Si H Si

N

b CF

(VII)

XI. GELS A. Gelling Agent

Title: Ferrocene-Containing, Organic Gelling Compound, and Gel and Cast Film Using the Same Author:

N. Kimizuka et al., US Patent 7,041,842 (May 9, 2006)

Assignee:

Honda Giken Kogyo Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE Ferrocene compounds and polymers have been used as micelle-forming agents in electrochemical processes for producing organic films usable in electronic materials such as color filters. To increase the concentration of ferrocene in these processes, an ferrocene oligomer having gelling properties has been prepared.

REACTION O O

11

NH2

i

O

11

O 11

N H

O

H N

O O

H N

t-C4H9

O

11

ii

iii

H N

O 11

O

NH3 Cl

N H

O O

Gel

iv

O

11

O

11

NH

N H

O

Fe

H N O

i: Butyloxycarbonyl-l-glutamic acid, triethylamine, THF, diethyl phosphorocyanidate ii: Trifluoroacetic acid Advances in Polymer Chemistry and Methods Reported in Recent US Patents, by Thomas F. DeRosa Copyright Ó 2008 by John Wiley & Sons, Inc. 255

256

Ferrocene-Containing, Organic Gelling Compound, and Gel and Cast Film Using the Same

iii: CCl3H, triethylamine, ferrocene carboxylic acid, 2-oxo-3-oxazolidinyl)-phosphinic chloride iv: Acetonitrile, N-methyl-N0 -methoxymethyl-imidazolium bromide

EXPERIMENTAL 1.

Preparation of BOC Intermediate

A reaction vessel was charged with 3-lauryloxypropyl-1-amine (17.8 mmol), butyloxycarbonyl-l-glutamic acid (8.1 mmol), and triethylamine (17.8 mmol) dissolved in 150 ml of THF, and then ice-cooled. This mixture was slowly treated with diethyl phosphorocyanidate (17.8 mmol) and then stirred under ice cooling for 30 minutes and at ambient temperature for 3 days. It was concentrated and a pale-yellow oily residue isolated. The residue was dissolved in CCl3H, washed twice apiece with 5% aqueous NaHCO3 and water, and dried using Na2SO4. The solution was filtered, concentrated as a pale-yellow solid after recrystallization in acetone, and the product was isolated as a colorless powder in 60.2% yield.

2.

Preparation of Ammonium Chloride Intermediate

The Step 1 product (4.9 mmol) was dissolved in 100 ml of CH2Cl2, treated with 20% trifluoroacetic acid, and stirred overnight at ambient temperature. The mixture was concentrated, and an oily residue was isolated. The residue was dissolved in 50 ml of acetone and then treated with 1 ml concentrated hydrochloric acid with cooling until a precipitate was formed. The solid was re-crystallized twice from EtOAc, and the product was isolated as a colorless powder in 40.9% yield. 3.

Preparation of Ferrocene-Containing Gelling Compound

The Step 2 product (1.58 mmol) and triethylamine (1.8 mmol) were dissolved in CCl3H and treated with water, and then the mixture shaken. The CCl3H phase was isolated, dried with Na2SO4 and concentrated. The residue was dissolved in CH2Cl2 and treated with triethylamine (1.8 mmol), ferrocene carboxylic acid (1.73 mmol), and N,N-bis(2-oxo-3-oxazolidinyl)-phosphinic chloride (1.73 mmol). This mixture was stirred under ice-cooling for 30 minutes, stirred at ambient temperature 3 days, and then concentrated. The residue was dissolved in CCl3H, washed with 5% aqueous NaHCO3 and dilute with hydrochloric acid. The mixture was filtered and concentrated, and the residue was purified by chromatography with silica gel using CCl3H. Four components were identified. The first two components were discarded. The remaining two components were separated by silica gel column chromatography using CCl3H/ CH3OH, 10/1, respectively, to isolate the gel-forming third component. This component was then re-crystallized from hexane, and the product was isolated as a paleyellow solid in 31% yield, MP ¼ 82.1 C to 83.5 C.

Notes

4.

257

Preparation of Gel

A 20 mM solution of the Step 3 product in acetonitrile and N-methyl-N0 -methoxymethyl-imidazolium bromide was prepared. The mixture was heated and left to stand at ambient temperature for 30 minutes. An organogel and ionogel formed that were observed using a dark-field optical microscope. The organogel indicated the presence of microcrystals suggesting that they have an associated fibrous structure or that crystals were formed by the slide cover glass; the micron-level fibrous structures were not observed in the ionogel.


NOTES 1. A supramolecular hydrogel underwent a reversible gel-sol transformation that was formed by adding 9,10-dimethoxy-2-anthracenesulfonic acid to an aqueous dispersion of a cationic amphiphile, (I), as was previously prepared by the author [1]. The gel had a network with a bilayer-membrane and a nanofiber structure. O 11

11

N H

H N

N

OH

O

H N

(I)

O

2. Sugar-derived gelatinizers, (II), having gel-forming capability in both organic solvents and water were prepared by Jung [2], and agglomerates were systematically designed by altering the hydrocarbon tail.

OH HO HO

O OH

O

NH

(II)

3. Eagland [3] demonstrated that in the presence of acid, polyvinylalcohol and poly(4-(4-formylphenylethenyl)-1-methyl)-pyridinium methosulphonate,

258

Ferrocene-Containing, Organic Gelling Compound, and Gel and Cast Film Using the Same

(III), formed a hydrogel that could be used to encapsulate water-insoluble materials. Soybean-based materials prerpared by Liu [4] were also effective as hydrogels and used as drug delivery agents.

OH

O

O

a OH N

b

(III) References 1. 2. 3. 4.

N. Kimizuka et al., US Patent 6,576,679 (June 10, 2003) J.H. Jung et al., US Patent 7,196,178 (March 27, 2007) D. Eagland et al., US Patent 7,202,300 (April 10, 2007) Z. Liu et al., US Patent Application 2007-0077298 (April 5, 2007)

B. Hydrogels

Title:

Random Block Copolymers

Author:

N.B. Graham et al., US Patent 7,241,845 (July 10, 2007)

Assignee:

Ocutec Limited (Glasgow, GB)

SIGNIFICANCE A linear urea-urethane block copolymer containing polyethylene oxide and polypropylene oxide was prepared by reacting polyethylene glycol and polypropylene glycol with dicyclohexylmethane 4,40 - diisocyanate and 4,40 -diaminodiphenylmethane.These materials are particularly advantageous because of their high mechanical strength in the swollen state. Mechanical property testing indicated that the energy needed to break the copolymer hydrogel was at least 40% of that of the copolymer in the dry state.

REACTION HO

O 75

OH

i

O

O

O 75

O

O N H

N H

O

O

O 5

O

O

O N H

N H

NH

N H

O n

i: Polyethylene glycol, polypropylene glycol, 4,40 -diaminodiphenylmethane, dicyclohexylmethane 4,40 -di-isocyanate, ferric chloride

EXPERIMENTAL Random Urea-Urethane Copolymer of Polyether Glycol, Polypropylene Glycol, Dicyclohexylmethane 4,40 -Diisocyanate, and 4,40 -Diaminodiphenylmethane A reactor was charged with polyethylene glycol having a Mn 5830 daltons and polypropylene glycol with a Mn 425 daltons and then heated until melted and 259

260

Random Block Copolymers

thoroughly mixed. The mixture was next heated to 95 C to 100 C and treated with anhydrous ferric chloride and stirred until the catalyst dissolved. This mixture was treated with 4,40 -diaminodiphenylmethane (0.726 g) and again thoroughly mixed until the solution was homogeneouse; the solution was then posttreated with 12.67 ml dicyclohexylmethane 4,40 -diisocyanate and heated for 2 minutes at 90 C. The mixture was poured into preheated polypropylene test tube molds and placed into an oven at 95 C for 20 hours, and the product was isolated.

DERIVATIVES TABLE 1. Reagent variations in preparing poly(urea-urethane) derivatives using polyethylene glycol and polypropylene glycol. Entry 1 4 7 9

PEG-5380 (wt%)

PPG-425 (mol)

Diamine (mol)

72.0 21.0 8.0 4.0

3.554 1.310 0.736 0.560

10.01 27.19 48.34 63.55

Diisocyanate (mol) 80.320 24.476 10.223 5.838

TABLE 2. Equilibrium swelling for selected poly(urea-urethane) derivatives in water at 37 C.

Entry 1 4 7 9

Equilibrium Water Uptake (pph)

PEG-5380 (wt%) 10.01 27.19 48.34 63.55

21.0 82.0 183.0 298.0

Equilibrium Water Content (%) 17.36 45.05 64.66 74.87

Equilibrium PPG/Water 25.63 59.99 81.74 90.84

TABLE 3. Mechanical properties for water-swollen poly(urea-urethane) derivatives at 37 C.

Entry 1 4 7 9

PEG-5380 (wt%) 10.01 27.19 48.34 63.55

Water Content (%) 17.36 45.05 64.66 74.87

Young’s Modulus (MNm2) 0.764 0.830 1.500 0.507

Energy to Break Dry Film (MNm2) 48.719 57.626 172.934 299.697

Energy to Break Swollen Film (MNm2) 8.529 67.313 76.203 52.047

Notes

261

NOTES 1. Degradable difunctional poly(ethylene glycol) acrylates, (I), were prepared by Harris [1] and then photolytically converted into hydrogels and used in drug delivery systems. CH 2=CHCO2-PEO2-O-CH2CO2CH(CH3)CH2CONH-PEO2CCH=CH2

(I)

2. Muller [2] prepared hydrogels that were used in contact lenses with difunctional siliconecontaining crosslinkers, (II), with amphiphilic block prepolymers. Tetrafunctional crosslinkers, (III), prepared by Lewis [3] were used as biocompatible coating applications. H N

Si 3

O

O

H N

Si 54

OCN

O

(II)

O

N

3

N

b H

3

O

O Si a Si

3

O

(III)

N N H

b

NCO

3. Swellable hydrogels, (IV), used for sensor coatings were prepared by Van Antwerp [4] and were capable of water uptake of at least 200% by weight.

O

H N O N H

H N O

N H

N H

O O

N a H

O

b

O

c

N H

(IV)

References 1. J.M. Harris et al., US Patent 7,214,388 (May 8, 2007), US Patent 7,166,304 (January 23, 2007), and US Patent 7,018,624 (March 28, 2006) 2. B. Muller et al., US Patent 7,091,283 (August 16, 2006) 3. A.L. Lecvis et al., US Patent 7,064,174 (June 20, 2006) 4. W.P. Van Antwerp et al., US Patent 6,784,274 (August 31, 2004)

Title: (Meth)Acrylic Esters of Polyalkoxylated Trimethylolpropane Author:

A. Popp et al., US Patent 7,199,211 (April 3, 2007)

Assignee:


SIGNIFICANCE Oligomeric agents were prepared by condensing trimethylolpropane with ethylene and/or propylene oxides and capping with acrylic acid. These materials were subsequently crosslinked using 2,20 -azobisamidinopropane dihydrochloride, which formed superabsorbent swellable hydrogel addition polymers and were useful as components in diapers or in feminine hygiene products.

REACTION HO

OH

i

H

O

O

O

O

O

30

5

O

30

H 5

O

OH H

O

O

30

5

O

Superabsorbant hydrogel

ii Notes 1,2

O O

O 30

5

O

O

O 30

O

5

O

O O

O

30

5

i: Potassium hydroxide, ethylene oxide, propylene oxide ii: Acrylic acid, sulfuric acid, methylcyclohexane, hydroquinone monomethyl ether, triphenyl phosphate, hypophosphorous acid

262

Notes

263

EXPERIMENTAL 1. Preparation of Trimethylolpropane Ethoxylated/propoxylated (TMP-30EO-5PO) An autoclave was charged with trimethylolpropane (77 g) and 45% aqueous KOH (0.5 g) and then azeotroped at 80 C and 20 mbar. The mixture was next treated with ethylene oxide (759 g) at, 45 C to 155 C and reacted at elevated pressure until no further change in pressure was observed. The mixture was stirred an additional 30 minutes at 150 C and then treated with propylene oxide (167 g) at 120 C to 130 C. The reactor was purged, the contents cooled to 60 C, and the catalyst removed by filtration. The product was isolated and consisted of 30-tuply ethoxylated and 5tuply propoxylated trimethylolpropane. 2.

Preparation of Trimethylolpropane Ethoxylated/propoxylated Triacrylate

The Step 1 product (1427 parts) was converted into the corresponding acrylate ester by treating with acrylic acid (216 parts), sulfuric acid (5 parts) in methylcyclohexane (345 parts), hydroquinone monomethyl ether (3 parts), triphenyl phosphite (1 part), and hypophosphorous acid (1 part). The reaction continued until 44 parts of water were removed before beginning the vacuum distillation. The residue was purified by filtering through a K300 filter, and the acid number was determined. The product viscosity was adjusted to 330 mPas by the addition of 96 parts of acrylic acid, and a colorless product was isolated.

DERIVATIVES TABLE 1. Properties of hydrogels prepared by free radically polymerizing the corresponding triacrylate with 2,20 -azobisamidinopropane dihydrochloride. Entry 1b 1d 1f 1g

Hydrogel

Saponification Index

TMP-15E0 TMP-30EO-5PO TMP-5PO-30EO TMP-10PO-50EO

11.6 4.7 7.0 4.1

CRC-1*1 (g/g) 29.7 30.1 29.5 30.1

*1Centrifuge retention capacity test

NOTES 1. Step 2 products were subsequently converted into crosslinked superabsorbent hydrogels and used as components in diapers or in feminine hygiene products. The preparation of these superabsorbant hydrogels is described below.

264

(Meth)Acrylic Esters of Polyalkoxylated Trimethylolpropane

Preparation of a Superabsorbent Hydrogel Using Internal Crosslinkers A reactor containing acrylic acid (305 g), 37.3wt % aqueous sodium acrylate (3204 g), and water (1465 g) was treated with ethoxylated (15 EO) trimethylolpropane triacrylate (12.2 g), 2,20 -azobisamidinopropane dihydrochloride (0.61 g), and sodium persulfate (3.05 g). The mixture was purged for 30 minutes and further treated with hydrogen peroxide (0.244 g) dissolved in water (5 g) and ascorbic acid (0.244 g) also dissolved in water (5g). The mixture was then heated in a thermally insulated tub for about 30 minutes; the temperature at the start of the reaction was 113 C. The reaction started after a few minutes and proceeded under adiabatic conditions until the product was isolated and comminuted through a meat grinder equipped with a 6 mm breaker plate. The residue was dried at 80 C under reduced pressure and the produce, was isolated having a sieve fraction of 300 to 600 mm. 2. Additional superabsorbent hydrogel derivatives containing EO/PO ratios other than those of the current invention were prepared by the author [1] in a subsequent invention. 3. Smith [2] prepared a series of superabsorbent polymers with high permeability consisting of the reaction product of NaOH, water, acrylic acid, methoxypolyethyleneglycol (750), monomethacrylate of trimethylolpropanetriacrylate, TMP-3EO, and hydroxymonoallyl ether-10EO. These materials were useful in the transportation of liquids in the swollen state. 4. Funk [3] prepared hydrogels with different pH values by reacting 90 parts of hydrophilic polymeric agents with glacial acrylic acid, water, and pentaerythritol triallyl with 10 parts of acrylic acid, sorbitan monococoate, and allyl methacrylate. 5. Water absorbing polymers consisting of acrylic acid, polyethylene glycol monoallyl ether acrylate, and polyethylene glycol diacrylate were prepared by Brehm [4] containing interstitial agents such as zeolites high in silicon. References 1. 2. 3. 4.

A. Popp et al., US Patent 7,259,212 (August 21, 2007) S.J. Smith et al., US Patent 7,173,086 (February 6, 2007) and US Patent 7,169,843 (January 30, 2007) R. Funk et al., US Patent 7,144,957 (December 5, 2006) H.G. Brehm et al., US Patent 7,101,946 (September 5, 2006)

Title: Prepolymers for Improved Surface Modification of Contact Lenses Author:

Y.-C. Lai, et al., US Patent 7,176,268 (February 13, 2007)

Assignee:

Bausch & Lomb, Inc. (Rochester, NY)

SIGNIFICANCE Fumarate- and fumaramide-containing hydrogels have been prepared with silicone as a co-component that are highly oxygen permeable. These agents are biocompatible and useful as biomedical devices, particularly as contact lenses. REACTION HO

O

O

Si

O

Si

Si

O

22 H

OH

i O

O O

O

Si

O

O

Si

O

22 Si I

HO

O OH

Note 1 ii

O

O O

O O

O

Si

O

Si

O

O

H2N

Si

O

O

O O

O

O

a

O O

b

O

Si

O

Si

O

22

Si

3 3

O

O H N

NH2

O

Not Isolated

O N

22

O

O

O

N

c

O

O

d 3

NH

3

O

e

i: Fumaryl chloride, water 265

266

Prepolymers for Improved Surface Modification of Contact Lenses

ii: Hexanol, N,N-dimethylacrlyamide, DaracureÒ , tris(hydroxymethyl)aminomethane, water EXPERIMENTAL 1.

Preparation of Polydimethylsiloxane with Fumaric Acid Termini

A dried 500-ml round bottom flask was charged with bis(a,o-hydroxybutyl polydimethylsiloxane) (Mn 1624 daltons; 0.0185 mol) and fumaryl chloride (0.0418 mol) and then heated to 60 C for 2 hours and concentrated. The residue was treated with 3 mg of water and 30 ml of THF and refluxed until no IR evidence of acid chloride absorption was present. The mixture was next concentrated, the residue dissolved in 200 ml diethyl ether, extracted three times with 50 ml, dried with MgSO4, re-concentrated, and the product was isolated. 2.

Preparation of Hydrogel Films

A mixture consisting of the Step 1 product (32 parts), N,N-dimethylacrylamide (32 parts), tris(hydroxymethyl)aminomethane (36 parts), hexanol (27 parts), and Darocur Ò (0.3 parts) were cast between two silane-treated glass plates and cured for 1 hour at 70 C. The cured films were then released, extracted in isopropanol, and boiled for 4 hours in water. Hydrogel films were stored in borate buffered saline solution until needed. Mn ¼ 2001 daltons Mw ¼ 3141 daltons Pd ¼ 1.57 Water content ¼ 39%, Modulus ¼ 36 g/mm2 Tear strength ¼ 13 g/mm Oxygen permeability ¼ 93 Dk unit

DERIVATIVES TABLE 1. Selected Step 1 hydrogel pre-polymers converted into hydrogels by curing with tris(hydroxymethyl) aminomethane, hexanol, and DarocurR for 1 hour at 70 C. Entry 8 9

10

13

Monomer(s) Glycidyl methacrylate Octafluoropentyl methacrylate/glycidyl methacrylate Octafluoropentyl methacrylate/glycidyl methacrylate Methacrylic acid

Source: Very limited characterization data supplied by author.

N,N-Dimethylacrylamide: Monomer Ratio (mol) 6:1 5.7:1.07:1

2.85:1.07:1

3.60:1

Notes

267

NOTES 1. Additional Step 2 polymer analogues containing hydrophilic arylsiloxy-containing macro-monomers, (I), were prepared by Salamone [1]. O

O a

O

Si

O

Si

O

a

O

Si 3

O b

N O

(I) 2. Schmitt [2] prepared high-transparency lens materials by free radical polymerization of methacrylate monomers containing carbamate, (II), and ether, (III), segments. Free radical polymerization of 3-thietanyl derivatives, (IV)–(VI), using UV radiation was prepared by Kobayashi [3] and used in the manufacture of high-transparency lens. O

H N

O

O

O

H N

O

O

O

O

(II)

O

O

X

O

X

a

a = 2 – 20 X = O, S

Oa

(III) S S

S

S n

n = 1,2

S

(IV)

S S

S

(V) S S

(VI)

R

R = CH2NCO CH=CH2 S

268

Prepolymers for Improved Surface Modification of Contact Lenses

3. Polyisocyanates bicyclo[2.2.1]heptane-2,5(6)-diisocyanate, (VII), and tricyclo [5.2.1.0.2,6]-decane-3(4),8(9)-diisocyanate were used by Haseyama [4] to prepare high-transparency polythiourethane, (VIII), lens materials.

OCN

NCO n

HN

n = 1, 2

NH CO S

S

S

n

(VII)

S

S CO

(VIII)

4. Thioamino, (IX), and siloxy, (X), crosslinkable prepolymers were prepared by Muller [5] and used in the manufacture of contact lenses. H N

HS O

N H (IX)

H N

SH O

O

O N H

Si

O

Si

n

N H

(X)

References 1. J.C. Salamone et al., US Patent Application 2006-0287455 (December 21, 2006), US Patent Application 2006-0286147 (December 21, 2006), and US Patent Application 2006-0270749 (November 30, 2006) 2. B. Schmitt et al., US Patent 7,144,954 (December 5, 2006) 3. S. Kobayashi et al., US Patent Application 2005-0215757 (September 29, 2005) and US Patent 7,132,501 (November 7, 2006) 4. K. Haseyama et al., US Patent Application 2005-0049430 (March 3, 2005) 5. B. Muller et al., US Patent 7,091,283 (August 15, 2006)

Title: Preparation of High Molecular Weight Polysuccinimides Author:

C. S. Sikes, US Patent 7,053,170 (May 30, 2006)

Assignee:

Aquero Company (Eugene, OR)

SIGNIFICANCE L-Aspartic acid solubilized with hydrochloric was polymerized with 30% polyphosphoric acid at 180 C to prepare linear polysuccinimides having a Mw of 180,000 daltons. When the polysuccinimide was hydrolyzed with dilute sodium hydroxide an a,b-polysodium aspartate hydrogel was generated.

REACTION O HO O H2N

O

O

OH

i

N

a

ii Notes 1,2

Na

O

O

H N O

H N O

O

O

a Na

i: Hydrochloric acid, polyphosphoric acid ii: Sodium hydroxide, water EXPERIMENTAL 1.

Preparation of Polysuccinimide

Eleven 50-ml beakers was charged with L-aspartic acid (0.01 mol) and solubilized with 13.3 ml of 1M hydrochloric acid (0.013 mol) at ambient temperature. The first three beakers were treated with 0.066 ml of polyphosphoric acid (specific gravity 2.0) and then warmed to 80 C acid. The second three beakers was treated with 0.266 ml polyphosphoric acid; the last four beakers were treated with 0.399 g of polyphosphoric acid. Each solution was dried at 120 C, resulting in clear glassy pucks of intimate mixtures of aspartic acid and the polyphosphoric acid catalyst. The dried materials 269

270

Preparation of High Molecular Weight Polysuccinimides

were then thermally polymerized at 180 C, and aliquots were intermittently removed from between 1 to 7 hours. Aliquots were washed with water and centrifuged, the process being repeated 3 times, and the products isolated as light powders. Analytical results are provided in Table 1. 2.

Preparation of a,b-Poly Aspartate Sodium

The Step 1 product was ring-opened by mild alkaline hydrolysis using 1 equivalent of 0.1M of NaOH per equivalent of succinimide. The alkaline conditions were held at pH 10 by auto-titration at 80 C in water bath. Under these mild conditions polysuccinimides were converted to polyaspartates within 1 hour.

REACTION SCOPING TABLE 1. Summary of weight average molecular weights from the preparation of polysuccinimides using L-aspartic acid using polyphosphoric acid. L-Aspartic

Acid Catalyst

Reaction Time@ 180 C (h)

None Hydrochloric acid Polyphosphoric acid Hydrochloric acid þ 10% polyphosphoric acid Hydrochloric acid þ 20% polyphosphoric acid Hydrochloric acid þ 30% polyphosphoric acid Hydrochloric acid þ 30% polyphosphoric acid Hydrochloric acid þ 30% polyphosphoric acid

Mw (dalton)

2 4 7 7

7,400 12,000 178,000 12,000

7

38,000

3

136,000

4

172,000

6

178,000

NOTES 1. The procedure for preparing sodium polyaspartate by the basic hydrolysis of the Step 1 product using 0.1M, NaOH in this investigation was too vague to be experimentally useful. Instead the procedure was obtained from a subsequent publication by the author [1]. 2. In a subsequent investigation by the author [1] polysuccinimdes were prepared using phosphoric, metaphosphoric, and diphosphoric acids.

Notes

271

3. Poly(succinimide-co-sodium aspartate), (I), was previously prepared [2] by the author and used in biodegradable and personal product applications. O N

H N

a

b

O

NaO

O

O

(I)

4. Poly(sodium aspartate-co-asparagine-co-succinimide), (II), was prepared by the author [3] by hydrolysis of polysuccinimide with ammonium and sodium hydroxides. A method for preparing branched polysuccinimide derivatives of the current investigation was also provided. O H H N N N a

b

NaO

O

O

H2N

O

O

c

O

(II) 5. Swift [4,5] prepared poly(succinimide-co-sodium aspartate) by copolymerizing aspartic acid with monosodium aspartate and polysuccinimide using L-aspartic acid in supercritical CO2. 6. By initiating the polymerization of aspartic acid with a malimide end capping initiator, (III), Swift [6] prepared a functionalized polysuccinimide derivative. O

O

N O

O O

(III)

References 1. 2. 3. 4. 5. 6.

C.S. Sikes, US Patent Application 2006-0205918 (September 14, 2006) C.S. Sikes et al., US Patent 6,495,658 (December 7, 2002) C.S. Sikes, US Patent 7,091,305 (August 15, 2007) G. Swift et al., US Patent 6,903,181 (June 7, 2005) G. Swift et al., US Patent 6,919,421 (July 19, 2005) and US Patent 6,887,971 (May 3, 2005) G. Swift et al., US Patent Application 2006-0211843 (September 21, 2006)

Title: Degradable Crosslinkers and Degradable Crosslinked Hydrogels Comprising Them Author:

H. Zhang et al., US Patent 7,135,593 (November 14, 2006)

Assignee:

Biosphere Medical, Inc. (Rockland, MA)

SIGNIFICANCE Base-labile crosslinkering agents consisting of N,N0 -(dimethacryloyloxy)alkylamide derivatives were prepared and used in synthesizing degradable crosslinked polymers and hydrogels. The degradation rates of these hydrogels was controlled by co-reacting the crosslinking agent with selected acrylamides. REACTION Crosslinker Component H3CO

OCH3 O

i

HO

H N

O

H N O

O O

H N

H N O

O

Intermediate

272

O O O

OH

ii

Experimental

273

Hydrogel Crosslinking O

iii Intermediate

O

a O

O

O

O HN

OH

O

OH O HN O

O

b O

c O

OH

i: Dimethyl glutarate, hydroxylamine, methanol, ethanol ii: Pyridine, DMF, methacryloyl chloride, DMF, chloroform, water iii: DMF, glycerol, ammonium persulfate, N,N,N,N-tetramethylethylenediamine, ethanol

EXPERIMENTAL 1.

Preparation of Glutaroyl Dihydroxamic Acid

Dimethyl glutarate (0.6 mol) was added to 400 ml of methanol and treated with an aqueous solution of hydroxylamine (50 wt% in water; 1.34 mol). The reaction stirred for 85 hours at ambient temperature, and the product was precipitated by introducing 400 ml of ethanol. The precipitate was isolated, and washed three times with ethanol, and vacuum-dried at 40 C for 48 hours; the product was isolated in 66% yield as a white powder.

2.

Preparation of N,N0 -Dimethacryloyloxy)glutarylamide

A reactor was charged with the Step 1 product (0.20 mol), 50 of ml pyridine, and 260 ml of DMF and then treated dropwise with methacryloyl chloride (0.4 mol) diluted with 40 ml of DMF and stirred 3 hours at ambient temperature. The mixture was next treated with 300 ml of CCl3H and poured into 1000 ml of vigorously stirring water. The organic phase was washed three times with water, dried overnight using MgSO4, and concentrated. The residue was re-crystallized in diethyl ether/hexane, and the product was isolated in 34% yield.

274

3.

Degradable Crosslinkers and Degradable Crosslinked Hydrogels Comprising Them

Preparation of 2-Hydroxyethyl Acrylate Crosslinked Hydrogel

Ina100-mlround-bottom flasktheStep 2productwasdissolvedinDMFandtreatedwith 2-hydroxyethyl acrylate (2.0 g) followed by glycerol and water (20 g), 1:1. The reactor was placed in an oil bath kept at 55 C and the polymerization was initiated using ammonium persulfate (50 mg) and accelerated with 0.1 ml N,N,N,N-tetramethylethylenediamine. The hydrogel formed immediately and was immersed in ethanol overnight, washed with ethanol, vacuum-dried for 20 hours, and the product was isolated. DERIVATIVES A summary of base-labile crosslinking agents is provided in Table 1. Hydrolytic stability of homopolymer and copolymer hydrogels are provided in Tables 2 and 3, respectively. O O

O O

N H

n

N H

O O

TABLE 1. Summary of N,N0 -(dimethacryloyloxy)alkylamide derivatives effective as hydrogel crosslinking agents. Name

n

N,N0 -Dimethacryloyloxy)malonamide N,N0 -Dimethacryloyloxy)succinamide N,N0 -Dimethacryloyloxy)glutarylamide N,N0 -Dimethacryloyloxy)adipamide N,N0 -Dimethacryloyloxy)suberoylamide

1 2 3 4 6

Source: Limited 1 H-NMR data supplied by author.

TABLE 2. Degradation times for crosslinked homopolymer hydrogels hydrolyzed in a buffer solution at pH 7.4 at 37 C. Monomer*1 TS HEA PEG-macromer AA NaAA DMA AAm

Crosslinker N,N0 -Dimethacryloyloxy)glutarylamide N,N0 -Dimethacryloyloxy)glutarylamide N,N0 -Dimethacryloyloxy)adipamide N,N0 -Dimethacryloyloxy)glutarylamide N,N0 -Dimethacryloyloxy)adipamide N,N0 -Dimethacryloyloxy)adipamide N,N0 -Dimethacryloyloxy)adipamide

TS ¼ N-[Tris(hydroxymethyl)methyl]acrylamide HEA ¼ N-(Hydroxymethyl)methacrylamide PEG-macromer ¼ Poly(ethylene glycol)-methacrylate, MW 526 daltons AA ¼ Acrylic acid NaAA ¼ Sodium acrylate DMA ¼ N,N-Dimethylacrylamide AAm ¼ Acrylamide *1

Degration Time 22 days 26 days 31 days 8 hours 6 hours 32 hours 7 hours

Notes

275

TABLE 3. Degradation times for copolymer hydrogels crosslinked with N,N0 dimethacryloyloxy)glutarylamide hydrolyzed in a buffer solution at pH 7.4 at 37 C. Monomer 1*1

Comonomer*2

HEA, 90% HEA 80% HEA 90% TS, 90% TS, 80% TS, 90% TS, 80%

Degration Time

DMA DMA AA DMA DMA AA AA

13 days 9.5 days 4 days 7 days 4 days 23 hours 15 hours

*1 HEA ¼ N-(Hydroxymethyl)methacrylamide TS ¼ N-[Tris(hydroxymethyl)methyl]acrylamide *2 AA ¼ Acrylic acid DMA ¼ N,N-Dimethylacrylamide

NOTES 1. Goupil [1] prepared biomedical articles consisting of biodegradable poly(vinyl alcohol) hydrogels crosslinked with N-methacrylamidoacetaldehyde dimethyl acetal, (I), N-acrylamido-acetaldehyde dimethyl acetal, (II), and 1-(2,2-dimethoxyethyl)-3,4-dimethylpyrrole-2,5-dione, (III). OCH3 O

O

O

H3CO

HN

HN H3CO

OCH3

N

H3CO

(I)

OCH3

O

(II)

(III)

2. Hubbell [2] prepared biocompatible hydrogels consisting of poly(acrylic acid-bethylene oxide) crosslinked with hydrolytically susceptible carbonates, (IV), urethanes, (V), ureas, (VI), ester amides, (VII), and diamides, (VIII). O O

X

Y

O

O

O

Crosslinker IV V VI

X O O N

Y O N N

276

Degradable Crosslinkers and Degradable Crosslinked Hydrogels Comprising Them

O X

Y

O

Crosslinker VII VIII

X O N

Y N N

3. Frechet [3] prepared bioactive microgels by free radical polymerization of acrylamide with acid-labile crosslinkers such as bisacrylamide 4-methoxybenzaldehyde acetal, (IX), and bistrifluoroacetamide 4-(3-azidopropylether) benzaldehyde acetal, (X). N3

OCH3

H N O

O

O

(IX)

O

H N

H N

F3C O

O

O

H N

O

CF3 O

(X)

4. Hydrolytically unstable polyethylene was prepared by Wilson [4] by copolymerizing ethylene with acid-labile crosslinkers 1-allyloxy-penta-1,4-diene, (XI), tetraallyloxysilane, (XII), or 3,9-divinyl-2,4,8,10-tetraoxaspiro [5,5] undecane, (XIII).

O

O

O Si

O

O

O

O

O

O

(XI)

(XII)

(XIII)

5. Loomis [5] prepared poly(lactide-co-(ethylene oxide-co-propylene oxide-colactide) bioresorbable compositions for use in implantable prosthesis.

Notes

277


D.W. Goupil et al., US Patent 7,070,809 (July 4, 2006) J.A. Hubbell et al., US Patent 6,943,211 (September 13, 2005) J.M.J. Frechet et al., US Patent 7,056,901211 (June 6, 2006) R.B. Wilson Jr. et al., US Patent 7,037,992 (May 2, 2006) G.L. Loomis et al., US Patent Application 2007-0015844 (January 18, 2007) and US Patent 7,109,255 (September 19, 2006)

C. Sol-gel

Title: Thermosensitive Poly(Organophosphazenes), Preparation Method Thereof and Injectable Thermosensitive Polyphosphazene Hydrogels Using the Same Author:

S.-C. Song et al., US Patent 7,259,225 (August 21, 2007)

Assignee:

Korea Institute of Science and Technology (Seoul, KR)

SIGNIFICANCE Thermosensitive polyphosphazene polymers have been prepared by reacting polydichlorophosphazene with methoxypolyethylene glycol and isoleucineethyl ester. These materials are suitable for use as injectable thermosensitive biodegradable drug delivering system that have sol-gel behavior near human body temperature. REACTION

N

Cl

i

P Cl

O

HN

a

Note 1

N

P HN

N

O

O

HN

15

O CH(CH3)CHC2H5

P HN

O a

CO-lactose O

i: THF, triethylamine, isoleucineethyl ester hydrogen chloride, ethyl-2-(O-glycyl) lactate ammonium oxalate, poly(aminomethoxyethylene glycol

278

Notes

279

EXPERIMENTAL 1. Preparation of Poly[(Aminomethoxyethyleneglycol)(Isoleucineethylester)(Ethyl-2-(O-Glycyl)Lactate)] (NP(AMPEG550)0.78(IleOEt)1.18(GlyLacOEt)0.04) Poly(dichlorophosphazene) (17.26 mmol) was dissolved in THF and then put into a dry ice-acetone bath and treated with triethylamine (82.84 mmol) and isoleucineethyl ester hydrogen chloride salt (20.71 mmol). After the mixture was stirred for 48 hours at ambient temperature, it was treated with a solution of ethyl-2-(O-glycyl)lactate ammonium oxalate(0.69 mmol) and triethylamine (3.45 mmol) in 50 ml acetonitrile, and reacted a further 19 hours in an ice bath. Finally poly(aminomethoxy-ethylene glycol) (25.89 mmol, Mw 500 daltons) and triethylamine (51.78 mmol) were added and the mixture was reacted for 48 hours at 50 C. The reaction mixture was filtered, concentrated until a small quantity of solvent remained, and dissolved in THF. The mixture was precipitated by adding excessive hexane and filtered, the process being repeated 3 times. The solid was dissolved in a small amount of methanol and dialyzed using methanol and distilled water for 5 days apiece. The product isolated in 58% yield had a Mw of roughly 27,000 daltons, maximum viscosity of roughly 312.8 Pa-s, and a maximum gel temperature of 43 C.

DERIVATIVES TABLE 1. Physical properties of selected polyphosphazenes prepared according to the current invention.

Entry 1 2 3 4

Formula NP(AMPEG550)0.78(IleOEt)1.18 (GlyLacOEt)0.04 NP(AMPEG550)0.70(IleOEt)1.20 (GlyLacOEt)0.10 NP(AMPEG550)0.08(IleOEt)1.20 NP(AMPEG750)0.65(IleOEt)1.35

Mw (daltons)

Maxium Viscisity (Pa s)

Maxium Gel Temperature ( C)

27,000

312.8

43

41,000

550.0

39

42,000 22,000

400.0 680.0

40 47

NOTES 1. Additional biodegradable and thermosensitive polyphosphazenes derivatives, (I), were prepared by the author [1] in an earlier investigation. Thermosensitive cyclotriphosphazene analogues were also prepared by Sohn [2].

280

Thermosensitive Poly(Organophosphazenes)

O

O

N

P HN

N

a

O

O

7

P

N b

R

R Gly-Gly-OEt

O

O

7

P

HN

N

c

R' LeuOEt

P HN

R"

R'

NHR

NHR

NHR'

7

N

d

P

N e

R'

HN R"

P

f

g

R"

R" AlaOEt (I)

2. Multisubsituted linear polyphosphazene polymers, (II), having high ion conductivity at ambient temperature were prepared by Allcock [3] and used as gel polymer electrolytes.

O CF3

CF3

O

O

N P

O

O N P O

O N P a O

CF3

O

O O

O

(II) 3. Copolymers consisting of polyphosphazene norbornene derivatives, (III), were prepared by Allcock [4] and used as electrically conductive materials, biomedical materials, and as compatibilizing agents.

CF3 O

O PH O

CF3

CF3

O N P a O CF3

CF3

(III)

O N P O O CF3

CF3

Notes


S.-C. Song et al., US Patent 6,319,984 (November 20, 2001) Y.S. Sohn et al., US Patent 6,417,383 (July 9, 2002) H.R. Blankenship et al., US Patent 6,605,237 (August 12, 2003) H.R. Allcock et al., US Patent 6,392,008 (May 21, 2002)

281

XII. IMAGING AGENT Title: Polymerization Method for the Synthesis of Polypeptide Imaging Agents Author:

B. J. Grimmond et al., US Patent 7,205,385 (April 17, 2007)

Assignee:

General Electric Company (Niskayuna, NY)

SIGNIFICANCE Low molecular weight magnetic resonance imaging contrast-enhancing agents are widely used because they rapidly diffuse into plaques, but they disperse too rapidly from the body because of their low molecular weights. The compound gadolinium (III) diethylenetriaminepentaacetic acid is a typical example. To address this concern, moderate molecular weight polyamino acids have been prepared containing gadolinium (III) diethylenetriamine pentaacetic acid that are as effective as imaging agents which diffuse at much slower rates through the body.


284

Polymerization Method for the Synthesis of Polypeptide Imaging Agents

REACTION NH2

HN 4N(C2H5)3DTPA

NH2 O

O

i

O

ii

iii

OH HN

B

O

HN

B

O

NH2

O O

NH2

NH2

O

NH

v

O

iv

OH

O NH DTPA Gd(III)Na

NH

OH NH 4N(C2H5)3DTPA

DTPA Gd(III)Na

vi H

H N

O OH

N

0.8 H

0.2

O

NH DTPA.Gd(III).Na

i: Methanol, 9-borobicyclononane (9-BBN), THF ii: Diethylenetriaminepentaacetic acid (DTPA), triethylamine, isobutylchlorofomate iii: Ethylene diamine (EDA) iv: Gadolinium (III) chloride (Gd), trisodium citrate v: CH2Cl2, triethylamine, triphosgene vi: N-Carboxy anhydride (NCA)-valine, acetone, CH2Cl2

EXPERIMENTAL 1.

Preparation of 9-Borobicyclononanelysine Complex

A sample of lysine (1 eq) was stirred in methanol at ambient temperature, slowly treated with 9-borobicyclononane (9-BBN) (1 eq) in THF, and refluxed for 1 hour at 50 C. The clear and colorless mixture was concentrated to give a solid that was redissolved in THF at 40 C and then filtered and re-concentrated. The product was isolated as an off-white solid and used without further purification.

Experimental

2.

285

Preparation of 9-BBN-Lysine-Diethylenetriaminepentaacetic Acid

A sample of 0.1M solution diethylenetriaminepentaacetic acid (DTPA) (1 eq) in acetonitrile was treated with triethylamine (5 eq) and degassed for 20 minutes before heating for 1 hour at 50 C. The solution was then cooled to 45 C, treated with the dropwise addition of isobutylchloro-fomate (1.1 eq), and stirred for 1 hour. This mixture was next treated with the Step 1 product (1 eq) dissolved in acetonitrile and stirred 12 hours at ambient temperature. The solution was concentrated, the residue re-crystallized from THF and diethyl ether, and the product isolated as a white solid. 3.

Preparation of Lysine-N-å-DTPA

A mixture of the Step 2 product (1 eq) in THF and ethylene diamine (1.1 eq) was heated for 10 minutes at 60 C. The solution was then concentrated and the residue washed with pentanes, re-crystallized from warm THF and diethyl ether, and the product isolated.

4.

Preparation of Lysine-N-å-DTPA Gadolinium (III) Sodium (Gd.Na)

A 0.1M aqueous solution of the Step 3 product (1 eq) was added to a pH 6 buffer solution of GdCl3 (1.2 eq) and trisodium citrate (2.4 eq). The mixture was then stirred for 12 hours and the volume reduced; next it was filtered twice through a Sephadex plug. The volume was further reduced and poured into acetone. A white precipitate formed, and the product was isolated after filtration. 5.

Preparation of N-Carboxy Anhydride (NCA)-Lysine-N-å-DTPA.Gd.Na

A 0.1M CH2Cl2 solution of the Step 4 product (1 eq) and triethylamine (2 eq) was treated with triphosgene (0.3 eq) at 0 C. The mixture was stirred for 1 hour at ambient temperature and concentrated; the residue was extracted with EtOAc. The extract was filtered was re-concentrated, the residue re-crystallized in CH2Cl2/pentanes, and the product was isolated as a white solid.

6. Preparation of Poly(Lysine-N-å-DTPAGd.Na)-(Valine) Random Copolymer The Step 5 product (1 eq) and NCA-valine (0.25 eq) were dissolved in CH2Cl2 and acetone, 5:1, respectively, and the mixture was heated to 60 C. The mixture was then treated with triethylamine (0.01 eq) dissolved in CH2Cl2 and heated for 24 hours at 60 C. Thereafter the mixture was treated with 0.01M aqueous hydrochloric acid, and a white solid formed. The solid was washed with acetone, and the product was isolated.

286


DERIVATIVES Gadolinium-containing poly(lysine) homopolymer, (I), and biotin terpolymer, (II), were also prepared. O

H N

HO

H

H

O

H N

H N

N

0.66 H

NH-DTPA.Gd.Na

O

O OH 0.17

0.17

NH-DTPA.Gd.Na

(I)

NH-Biotin

(II)

NOTES 1. Compositions containing complexed gadolinium for enhancing transmembrane transport, (III), were prepared by Wedeking [1] and used as diagnostic or therapeutic treatment agents. O N

HN H2N

H N N

N CO2H O O

N

3

Gd N

O

3

Gd

N

N

N

N

N

CO2

N H

H N

O2C

O2C

O

N H

O

O2C

N CO2

N CO2

(III)

2. Lauffer [2] prepared gadolinium-containing contrast-enhancing imaging agents, (IV), containing an image-enhancing component and to monitor e chemoembolization by magnetic resonance imaging therapy.

Notes

O

O P

O

O

CO2 N

O2C

N

O2C

287

CO2

N

3

CO2

Gd (IV)

3. Giovenzana [3] prepared a novel class of multidentate aza ligands, (V), that formed complexes with gadolinium having particularly favorable stability and relaxation times.

CO2H CO2H

HO2C

HO2C

N

CO2H

N

(V) 4. Ranganathan [4] enhanced the stability of MRI contrast imaging agents by incorporating ascorbic acid, (VI), to diminish oxidation of substituents from free radical reactions induced by radionuclide decay. O2C

CO2 N

N

Gd

O N H N HO OH O O

N CO2

N H O

HO

3

(VI)

288


References 1. S. Wedeking et al., US Patent 7,175,829 (February 13, 2007) and US Patent 7,147,837 (December 12, 2006) 2. R.B. Lauffer et al., US Patent 7,182,934 (February 27, 2007) and US Patent 7,198,776 (April 3, 2007) 3. G.B. Giovenzana et al., US Patent 7,186,400 (March 6, 2007) 4. R.S. Ranganathan et al., US Patent 7,160,535 (January 9, 2007)

XIII. INK Title: Process for Preparing Chain Extended Thermoplastic Guanidinium Polymers Author:

D. Hall et al., US Patent 7,172,274 (February 6, 2007)

Assignee:

Fujifilm Imaging Colorants Limited (Manchester, GB)

SIGNIFICANCE A method for preparing guanidinium or biguanidinium pre-polymers and then chain extending them with tetraethyleneglycol diepoxide or isophorone diisocyanate is described. These agents are effective as fixing agents to reduce highlighter smear of prints prepared by ink jet printing.

REACTION NH . HCl H2N

NH2

NH

i Note 1

N H

H2N NH N H

HN OH

N H

NH a N H

N H

NH N H

NH a N H

NH

H H N N b NH

N H H H N N b NH

NH HO

NH2

ii Note 2

O

O

4

4

O

O

i: Hexamethylene diamine ii: Water, tetraethyleneglycol diepoxide


290

Process for Preparing Chain Extended Thermoplastic Guanidinium Polymers

EXPERIMENTAL 1.

Preparation of Polyhexamethyleneguanidine Pre-Polymer

A vessel was charged with guanidine and hydrochloride (200 parts) and hexamethylene diamine (292 parts) and heated 4 hours at 120 C and an additional 5 hours at 150 C to 170 C. The mixture was cooled and treated with water (400 parts) and then stirred at 80 C until dissolution occurred. When further cooled to ambient temperature, the solid remain dissolved in water. Mn ¼ 710 daltons Mw ¼ 1010 daltons NH2 termini content ¼ 4.7% Amine content ¼ 71.5 wt Triple substitution ¼ 12%

2.

Preparation of Polyhexamethyleneguanidine with Epoxy Termini

The Step 1 product (51.2 g) was mixed with water (78.83 g) and tetraethyleneglycol diepoxide (9.8 g) and reacted for 2 hours at 25 C. The prepolymer isolated had a Mn of 1520 daltons and Mw of 3190 daltons.

SCOPING REACTIONS TABLE 1. Physical properties of polyhexamethyleneguanidine with epoxy termini prepared by reacting the Step 1 pre-polymer with tetraethyleneglycol diepoxide. Entry 2 3 4

Epoxide : Prepolymer Ratio

Mn

Mw

0.80 0.95*1 0.60

1,970 2,330 1,250

9,420 26,440 2,160

*1

Reaction performed in 1,5-pentanediol

NOTE Polyhexamethyleneguanidine pre-polymers were also chain extended with isophorone diisocyanate and physical properties provided in Table 2. TABLE 2. Physical properties of polyhexamethyleneguanidine derivatives prepared by reacting the Step 1 pre-polymer with isophorone diisocyanate. Entry 13 14 14

Isocyanate : Prepolymer Ratio 0.60 0.80 0.95

Mn

Mw

1,650 1,770 1,800

82,490 96,120 310,930

Notes

291

NOTES 1. Ammonolysis of poly(hexamethylene urea), (I), was used by Miyamoto [1] to prepare guanidine polyhexamethyleneguanidine, (II), as illustrated below. Fitzpatrick [2] subsequently converted this material into a polyguanidine ethers, (III), by reacting with 1,2-dibromoethane and 1,4-butanediol. O H2N

6

NH2

+

OCN

N H

NCO 6

NH N H

NH3

6 a

N H

(I)

O 4

N H

6 a

(II)

NH O

N H

BrCH2CH2Br

N H

HOCH2CH2CH2CH2OH

6a

(III)

2. Imashiro [3] converted p-diphenylmethane diisocyanate, (IV), into the corresponding polycarbodiimide, (V), and then postreacted with dibutyl amine forming the corresponding polyguanidine derivative, (VI). H2 C

OCN

i

NCO

H2 C

N C N

(IV)

ii a

(V) H2 C

H N C N N

a

(VI)

i: THF, 3-methyl-1-phenyl-2-phosphorene-1-oxide

ii: THF, dibutyl amine

3. Although selected polyamines, (VII), functionalized with guanidine, (VIII), were prepared by Dhal [4] for use in the treatment of gastrointestional disorders; their application as a crosslinkable resin was also suggested by the author.

NH2

(VII)

a

N

+ HN

N HN NH2 HCl

NH NH2 HCl

(VIII)

a

292

Process for Preparing Chain Extended Thermoplastic Guanidinium Polymers

4. Polyamide resin components containing pendant guanidine, (IX), were prepared by Rothbard [5] to aid in the delivery of selected biological agents. H2N

NH

H2N

NH

NH O

HO O

NH

H N

N H

O

3

R

R = Therapeutic agent

NH HN

NH2

(IX)


K. Miyamoto et al., US Patent 7,157,534 (September 22, 2002) R.J. Fitzpatrick, US Patent 6,955,806 (October 18, 2005) Y. Imashiro et al., US Patent 6,225,417 (May 1, 2001) P.K. Dhal et al., US Patent 6,294,163 (September 25, 2001) J.B. Rothbard et al., US Patent 7,157,534 (July 6, 2004)

XIV. LIQUID CRYSTALS A. Liquid Crystal Aligner

Title: Diamines, Polyimide Precursors, and Polyimides Produced by Using the Diamines and Liquid Crystal Aligning Agents Author:

K. Hosaka et al., US Patent 7,169,878 (January 30, 2007)

Assignee:

Nissan Chemical Industries, Ltd. (Tokyo, JP)

SIGNIFICANCE Poly(amic acids) were prepared by the ambient temperature condensation of 1,2,3,4cyclobutane tetracarboxylic dianhydride with selected aromatic diamines. When the poly(amic acids) and liquid crystal alignment agents g-butyrolactone and N-methylpyrrolidone were spin-coated and cured onto an inert surface, the polyimide was effective as a liquid crystal aligner.


294

Diamines, Polyimide Precursors, and Polyimides

REACTION H2N

O

O

C12H25O

O

O2C

ii C12H25O

NH2

O NH2 CO2

O O2C H2N

i

NH2

H2N

O

O

a

O

CO2

O

CO2

NH2

HN

O2C

O

.... b

O

....

c

C12H25O

C12H25O

O

N

O

N

N a

O

N

O

O

O O

O

N O

O

O N

....

b

O

O

O

O

O

....

N O

c

O

i: N-Methylpyrrolidone, 3,5-di-dodecyloxybenzyl-3,5-diamino-benzoatediamine, 1,2,3,4-cyclobutane tetracarboxylic dianhydride ii: N-methylpyrrolidone, g-butyrolactone

EXPERIMENTAL 1.

Preparation of Poly(Amic Acid) Intermediate

A reaction flask was charged with 3,5-di-dodecyloxybenzyl-3,5-diamino-benzoatediamine (0.75 mmol), 1, 2, 2’-bis[4-(4-aminophenoxy)phenyl]propane (4.25 mmol), 1,2,3,4-cyclobutane tetracarboxylic dianhydride (5.00 mmol), and N-methylpyrrolidone (17.69 g) and then stirred at ambient temperature until a 15 wt% solid content polyimide precursor solution was obtained. Viscosity (25 C): 5184 MPas MW (GPC): 413,000 daltons

Testing

2.

295

Preparation of Mixed Polyimides as Liquid Crystal Aligning Films

The Step 1 product was diluted with N-methylpyrrolidone and g-butyrolactone then spin-coated on glass substrates having transparent electrodes. The mixture was heated at 80 C for 10 minutes and at 180 C or 250 C for 60 minutes to form a uniform polyimide coating film.

DERIVATIVES C12H25O H2N

O

O

NH2

H2N

C12H25O

Amine 1

O H2N

NH2

NH2 O

OC12H25 OC12H25

Amine 3

Amine 2

TABLE 1. Three amine co-reagents used in reacting with 5.00 mmol cyclobutane tetracarboxylic dianhydride.

Entry 4 5 6

Amine 1 (mmol)

Amine 2 (mmol)

Amine 3 (mmol)

4.75 2.50 3.75

0.25 — 1.25

5.00 2.50 —

NMP/c butyrolactone Aligning Agents, 8:2 (g) 17.17 19.35 18.13

Viscosity*1 (MPas)

Mw (daltons)

7,600 172*2 344*3

624,000 41,200 78,000

Note: Poly(amic acids) were prepared by mixing and stirring reagents at 25 C. Measured at 25 C 16% solids *3 15% solids *1 *2

TESTING Viscosity and contact angle testing results are provided in Tables 2 and 3, respectively.

TABLE 2. Physical properties of polyimides as liquid crystal aligning films prepared by heating N-methyl-pyrrolidone and c-butyrolactone, 8:2, respectively, with polyamic acids described in Table 1. Entry 4 5 6

Viscosity (MPas) 24.3 24.9 28.2

Solid Content (%) 4.10 3.98 2.80

296

Diamines, Polyimide Precursors, and Polyimides

TABLE 3. Results of water and methylene/iodine repellency testing of polyimide films obtained by reacting 1,2,3,4-cyclobutane tetracarboxylic dianhydride with amines described in Table 1. Contact Angle

Amine 3 Content (%)

Entry 4

Water ( )

50 50 25 25 15 15

5 6

Methylene/iodine ( )

Surface Energy (dyn/cm)

56.1 52.7 54.5 51.5 51.7 50.9

30.8 32.8 31.8 33.5 33.8 33.9

97.7 93.6 93.3 91.8 87.9 90.756.1

NOTES 1. Polyimides containing polyaromatic amines, (I) and (II), were previously prepared by the author [1] and used as electronic insulating agents. H2N

H N

NH2

H N

O

O O

C12H25O

O

H2N

NH2 C12H25O

O

O

(II)

(I)

In a subsequent investigation by the author [2] four additional amines, (III)–(VI), were prepared and used to prepared polyimides for coating applications. H2N

NH2

OC8H17

B O

Amine III IV V VI

A

A Cyclohexyl Cyclohexyl Phenyl Phenyl

B Cyclohexyl Phenyl Cyclohexyl Phenyl

Notes

297

2. Photo-crosslinkable malimide (VII) and styryl (VIII) derivatives were prepared by Nakata [3] and used as liquid crystal aligning agents and liquid crystal display elements.

Entry

R O

VII

N O

VIII

R

O

6

O

O

2

O O

CHCHC6H5

References 1. K. Hosaka et al., US Patent 6,740,371 (May 25, 2004) 2. K. Hosaka et al., US Patent Application 2006-0246230 (November 2, 2006) 3. S. Nakata et al., US Patent 7,074,344 (July 11, 2006) and US Patent Application 2004-0009310 (January 15, 2004)

Title: Photosensitive Polyimides for Optical Alignment of Liquid Crystals Author:

W. M. Gibbons et al., US Patent 7,005,165 (February 28, 2006)

Assignee:

Elsicon, Inc. (Newark, DE)

SIGNIFICANCE Polyimides derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride and selected aromatic diamines have been found effective as photosensitive materials. These materials have applications as liquid crystals aligners, liquid crystal displays, and related liquid crystal optical elements. The film preparation uses a noncontact method that can reduce dust and static charge buildup and improve resolution.

REACTION H2N Br

i

H N

H2N

ii

NO2

iii

O N O

i: ii: iii: iv:

298

O

O N O

a N

iv

NH2 N

N

v

NH2

CO2 O

CO2

H2N N

Methyl amine, methanol, diethyl ether 3-Fluoro-4-nitroaniline, triethyl amine, N-methylpyrrolidinone Tin (II) chloride dihydrate, ethanol, hydrochloric acid, potassium hydroxide 1,2,3,4-Cyclobutanetetracarboxylic dianhydride, N-methylpyrrolidinone)

Experimental

299

EXPERIMENTAL 1.

Preparation of N-(3-Methyl-2-Butenyl)-N-Methyl Amine

A reactor was charged with 4-bromo-2-methyl-2-butene (15.0 g) and then treated with 110 ml of 40% of aqueous methyl amine, 110 ml of diethyl ether, and 50 ml of methanol. The mixture was extracted, and the extracts were dried over potassium carbonate and distilled; 5.25 g of product were isolated, BP ¼ 80–89 C.

2. Preparation of 3 [N-(3-Methyl-2-Butenyl)-N-Methyl]Amino4-Nitroaniline The Step 1 product was stirred with 3-fluoro-4-nitroaniline (3.12 g), 6.2 ml of triethyl amine, and 30 ml of N-methylpyrrolidinone at 80 C to 85 C for 10 hours and then extracted with water and diethyl ether. The extract was purified by chromatography on silica gel; and the product was isolated.

3. Preparation of 1-(3-[N-(3-Methyl-2-Butenyl)-N-Methyl)-2,5Benzenediamine The Step 2 product (4.55 g) was treated with tin (II) chloride dihydrate (18.0 g) dissolved in 100 ml of ethanol and 16 ml of 10M hydrochloric acid and then stirred at ambient temperature for 9 hours. The mixture was basified with chilled 20 wt% potassium hydroxide (160 g), extracted with diethyl ether, and purified by chromatography on silica gel; the product was isolated as a light amber oil.

4.

Preparation Polyamic Acids: General Procedure

A mixture of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (0.58 mmol), a selected diamine (0.58 mmol), and 1.25 ml of N-methylpyrrolidinone were stirred at 18 C for 3 hours and then diluted to 5 wt% with c-butyrolactone (3.49 g). The product was used for spinning thin films.

5.

Preparation of Films: General Procedure

Two 0.9" 1.2" 1 mm thick soda lime glass substrates containing transparent indium-tin-oxide were spin-coated and cured with the Step 4 product by heating thin films in air for 15 minutes at 80 C and for 60 minutes at 200 C.

300

Photosensitive Polyimides for Optical Alignment of Liquid Crystals

DERIVATIVES TABLE 1. Optical alignment of polyimide compositions derived from 1,2,3,4cyclobutane-tetracarboxylic dianhydride and selected diamines.

Entry

Lamp Exposure (J/cm2)

Diamine

N

H2N

4

Alignment Quality

Holding Ratio (75 C)

Contrast

10

fair

0.911

10:1

20

good

0.835

179:1

20

fair

0.823

316:1

10

excellent

0.806

82:1

NH2 8

N

H2N

NH2 9

NH2

H2N N

12

N

H2N

NH2

NOTES 1. In a subsequent investigation by the author [1] additional Step 5 products, (I) and (II), were prepared and used in liquid crystal alignment layers. O N O

O

O N

(I)

O

OCH3 O

a O

O

(II)

Notes

301

2. The preparation of other aromatic diamines, (III), useful in preparing photosensitive polyimides effective as liquid crystal alignment agents is provided by the author [2].

NH2 H2N

N

O

C8H17

(III) 3. Polyimide esters, (IV), prepared Buchecker [3], containing a photoactive side chain were used as orientation layers for liquid crystals and in the construction of both unstructured and structured optical elements. H3CO n-C4H9-O

O

O

O

O O

N

N

O O

(IV)

a

O

4. Polyimides derived from diamines containing a steroid component, (V), were prepared by Hiraoka [4] and used as method for producing liquid crystal alignment layers.

O H2N

O

(V) NH2

302

Photosensitive Polyimides for Optical Alignment of Liquid Crystals


W.M. Gibbons et al., US Patent Application 2006-0051524 (March 9, 2006) W.M. Gibbons et al., US Patent 6,713,135 (March 30, 2004) and US Patent 6,380,432 (April 30, 2002) R. Buchecker et al., US Patent 6,831,148 (December 14, 2004) H. Hiraoka et al., US Patent 6,312,769 (November 6, 2001)

B. Liquid Crystal Materials

Title: Homopolymers That Exhibit a High Level of Photo-inducable Birefringence Author:

H. Berneth et al., US Patent 7,214,752 (May 8, 2007)

Assignee:

Bayer MaterialScience AG (Leverkusen, DE)

SIGNIFICANCE Homopolymers that are capable of absorbing visible light and that are structured so that in their thermodynamically stable state they are distended and strongly anisometric have been prepared. After absorbing electromagnetic radiation, the side group forms an angle of at least 30 with the longitudinal axis. These materials are suitable for storage of optically provided information.

303

304

Homopolymers That Exhibit a High Level of Photo-inducable Birefringence

REACTION O

a

O O

O

O

O

NH2 NH2 CN

i N

CN

N

ii Note 1

NC

iii HN

O

HN

O

CN N

N

NC

N

N

NC

CN

CN

i: Nitrosylsulphuric acid, sulfuric acid, aniline ii: Dioxane, 4-(2-methacryloyloxy)-ethoxy-benzoic acid chloride iii: DMF, azobis(isobutyronitrile)

EXPERIMENTAL 1.

Preparation of 4-Amino-20 ,40 -Dicyano-Azobenzene

2,4-Dicyanoaniline (31.4 g) was treated with nitrosylsulfuric acid (72 g) at 0 C to 5 C in 300 ml of 50% aqueous sulfuric acid, and the batch was stirred for 1 hour. This mixture was then slowly poured into a solution of aniline (20.4 g) and urea (4.5 g) dissolved in 300 ml of 50% aqueous sulfuric acid and then stirred for an additional hour at 0 C to 5 C. Thereafter the reaction mixture pH was raised to 5.5 with sodium carbonate. A precipitate formed that was filtered off under suction, washed with water, and dried; 34 g of product were isolated. This material was used in the next step without further purification. 2.

Preparation of Liquid Crystal Monomer

The Step 1 product (27.6 g) was dissolved in 500 ml dioxane and added to a solution of 4-(2-methacryloyloxy)-ethoxy-benzoic acid chloride (33 g) in 100 ml dioxane and then stirred for 2 hours. The product was precipitated by pouring the solution into 2 liters of water, purified by crystallization twice from dioxane, and 30.4 g of orangered crystals isolated with kmax ¼ 404.5 nm (DMF) and a mp ¼ 215–217 C.

Derivatives

3.

305

Preparation of the Liquid Crystal Homopolymer

The Step 2 product (7.9 g) was polymerized at 70 C in 75 ml DMF under argon using 2,20 -azobis(isobutyronitrile) (0.39 g) for 24 hours. The mixture was filtered, concentrated, and the residue boiled with methanol to remove unreacted monomer. The material was dried, and 7.18 g amorphous polymer were isolated having a glass transition temperature of 150 C.

DERIVATIVES TABLE 1.

Selected azo monomers and corresponding melting points and lmax.

Entry

Monomer Structure

11

O

O

O

O

HN

N N

O N

12

N N N S

N N

MP ( C)

lmax (DMF) (nm)

207-208

392

164

521

218–220

428

NO2

CN

NC

13

O

O

O

O

HN

N N

N(CH3)2

TABLE 2. Light-induced birefringence, Dn, at 250 mV at a wavelength of 514 nm using 0.9 lm thick polymer films. Entry 11 12 13

na

Dn

l (nm)

26,000 20,800 27,855; 19380

0.244 0.233 0.194

820 633 820

306

Homopolymers That Exhibit a High Level of Photo-inducable Birefringence

NOTES 1. Additional azoderivatives were previously prepared by the author [1] 2. Partially hydrogenated polymers derived from norbornene derivatives, [I], prepared by Miyaki [2] were low in birefringence, high in wavelength dependency birefringence, and excellent in transparency and heat resistance. Additional functionalized norbornene derivatives were prepared by Liaw [3].

O N

(I)

O

CO2CH3

References 1. H. Berneth et al., US Patent 6,875,833 (April 5, 2005) and US Patent 6,441,113 (August 22, 2002) 2. N. Miyaki et al., US Patent 7,230,058 (June 12, 2007) and US Patent 6,846,890 (January 25, 2005) 3. D.-J. Liaw et al., US Patent 7,045,248 (April 17, 2007)

Title: Liquid Crystalline Compound, Liquid Crystalline Composition, and Retardation Film Author:

H. Nishikawa et al., US Patent 7,169,325 (January 30, 2007)

Assignee:

Fuji Photo Film Co., Ltd. (Minami-Ashigara, JP)

SIGNIFICANCE Oligomeric phenylacetylene liquid crystalline derivatives capable of exhibiting a biaxial liquid crystal phase have been prepared. When these agents were functionalized with the polymerizable group 4-(4-acryloyloxybutyloxy)benzoic acid and then coated onto an alignment film and polymerized. An optically anisotropic retardation film was produced.

307

308

Liquid Crystalline Compound, Liquid Crystalline Composition, and Retardation Film

REACTION O

O

O

O

O

O

Br

i

ii

TMS O

O

O

O

O

O O

O

O O

O

O

O

O

iv

v O

O

O O

OH

OH

TMS

O

O

O

iii

O OH

OH

OH

vi

OH

vii

OR1

OR1

OR1

OR2

OR2

OR2

OR1

OR1

OR1

OR2

OR2

OR2

O

R1 =

7

O

R2 =

O O

4

O

O

O

i: 1,3-Dibromobenzene, triphenylphosphine, bis(triphenylphosphine)palladium (II) dichloride, copper(I) iodide, triethylamine ii: Trimethylsilyl acetylene, triphenylphosphine, bis(triphenylphosphine)palladium(II) dichloride, copper(I) iodide, triethylamine iii: THF, tetrabutylammonium fluoride iv: 2,6-Dibromo-1,4-diacetoxybenzene, triphenylphosphine, bis(triphenylphosphine)palladium(II) dichloride, copper(I) iodide v: THF, methanol, sodium methoxide vi: 4-Octyloxybenzoic acid chloride, THF, diisopropylethylamine, 4-dimethylaminopyridine vii: 4-(4-Acryloyloxybutyloxy)benzoic acid, THF, diisopropylethylamine, 4-dimethylaminopyridine

EXPERIMENTAL 1.

Preparation of 1-(2,5 Diacetoxyphenyl)-2-(3-Bromophenyl)Acetylene

A mixture consisting of 2,5 diacetoxyphenylacetylene (3 g), 1,3-dibromobenzene (10 g), triphenylphosphine (58 mg), bis(triphenylphosphine)palladium(II) dichloride

Experimental

309

(29 mg), and copper(I) iodide (10 mg) were dissolved in 50 ml of triethylamine and then refluxed for 10 hours under a nitrogen atmosphere. After cooling, water was added, and the reaction solution was extracted with EtOAc, washed with saturated brine, and concentrated. The residue was purified by column chromatography, and 2.8 g of product were isolated. 2. Preparation of 1-(2,5 Diacetoxyphenyl)-2-(3-Trimethylsilylethynylphenyl) Acetylene A mixture consisting of the Step 1 product (2.1 g), trimethylsilyl acetylene (0.83 g), triphenyl-phosphine (24 mg), bis(triphenylphosphine)palladium(II) dichloride (12 mg), and copper(I) iodide (4 mg) dissolved in 20 ml of triethylamine was refluxed for 10 hours under a nitrogen atmosphere. After cooling, water was added, and the reaction solution was extracted with EtOAc, washed with saturated brine, and concentrated. The residue was purified by column chromatography, and 1.5 g of product was isolated. 3.

Preparation of 1-(2,5 Diacetoxyphenyl)-2-(3-Ethynylphenyl)Acetylene

The Step 2 product (1.5 g) was dissolved in 200 ml of THF, treated with 5 ml of 1.0 M THF solution of tetrabutylammonium fluoride, and stirred at ambient temperature for 30 minutes. The solution was treated with water, extracted with EtOAc, and washed with saturated brine. The organic layer was concentrated under reduced pressure and then purified by column chromatography; 0.9 g of product was isolated. 4. Preparation of 1-[(2,5-Diacetoxyphenyl)-2-[3-(2,5Diacetoxyphenylethynylphenyl)] Acetylene (Product 4A) and 1-[(2,5Diacetoxyphenyl)-3-(2,5-Diacetoxyphenylethynylphenyl)]-2-[(2,5-Diacetoxyphenyl)-3-2,5-Diacetoxyphenylethynylphenyl)] Acetylene (Product 4B) A mixture consisting of the Step 3 product (0.7 g), 2,6-dibromo-1,4-diacetoxybenzene (0.37 g), triphenylphosphine (10 mg), 5 mg of bis(triphenylphosphine)-palladium(II) dichloride, and copper(I) iodide (2 mg) dissolved in 20 ml of triethylamine was refluxed for 10 hours under a nitrogen atmosphere. The mixture was cooled and then treated with water. The solution was extracted with EtOAc, washed with saturated brine, and concentrated. The residue was purified by column chromatography, and 0.21 g and 0.18 g of products 4A and 4B, respectively, were isolated. 5. Preparation of 1-[(2,5-Dihydroxyphenyl)-3-[2,5Dihydroxyphenylethynylphenyl)]-2-[(2,5-Dihydroxyphenyl)-3-(2,5Dihydroxyphenylethynylphenyl)]Acetylene The Step 4B product (0.18 g) was dissolved in 20 ml of THF, treated with 5 ml of methanol and 0.4 ml of sodium methoxide dissolved in 28% methanol, stirred for 1 hour at ambient temperature, and neutralized with dilute hydrochloric acid.

310


The mixture was extracted with EtOAc, concentrated, and 0.12 g of crystalline product was isolated. 6. Preparation of 1-[(2,5-(4-Octyloxybenzoxy))-3-(2,5-(4-Octyloxybenzoxy) Ethynylphenyl)]-2-[(2,5-(4-Octyloxybenzoxy)-3-(2,5-(4-Octyloxybenzoxy))] Acetylene The Step 5 product (0.06 g) and 4-octyloxybenzoic acid chloride (0.4 g) were dissolved in 10 ml of THF, treated with diisopropylethylamine (0.2 g) and 4-dimethylaminopyridine (0.01 g), and stirred 12 hours at ambient temperature. Water was added to the reaction mixture, and the mixture was extracted with EtOAc. The mixture was concentrated and then purified by column chromatography; 0.2 g of the crystalline product was isolated. 1

H-NMR (CDCl3) d (ppm): 0.85 0.95 (18H, m) 1.20 1.60 (60H, m) 1.70 1.90 (12H, m) 3.95 4.10 (12H, m) 6.90 7.00 (12H, m) 7.00 7.50 (16H, m) 8.10 8.25 (12H, m)

7. Preparation of 1-[(2,5-(4-(4-Acryloyloxybutyloxy)Benzoxy)-3-(2,5-(4Acryloyloxybutyl-oxy)-Benzoxy)Ethynylphenyl)]-2-[(2,5-(4Acryloyloxybutyloxy)Benzoxy)-3-(2,5-(4-Acryloyloxybutyloxy)Benzoxy)] Acetylene The Step 6 procedure was repeated using 4-(4-acryloyloxybutyloxy)benzoic acid, and the product was isolated. 1

H-NMR (CDCl3) d (ppm): 1.70 1.90 (12H, m) 1.90 2.00 (12H, m) 3.95 4.30 (24H, m) 5.75 5.80 (6H, m) 6.056.20 (6H, m) 6.35 6.50 (6H, m) 6.90 7.00 (12H, m) 7.00 7.50 (16H, m) 8.10 8.25 (12H, m)

DERIVATIVES Two additional derivatives, (I), were prepared. O OR

OR

R = H;

4 O

O O

OR

(I)

OR

BIAXIAL LIQUID CRYSTAL TESTING RESULTS Step 6 Product The phase transition temperature of the Step 6 product was examined by observing its texture through a polarizing microscope. When the temperature was elevated, the

Preparation of Retardation Film?

311

phase changed from crystal phase to isotropic liquid phase in the vicinity of 140 C. When the temperature was gradually lowered from 150 C, the phase changed to the N phase in the vicinity of 120 C. Finally, when the temperature was further lowered to ambient temperature, the material reverted to crystal phase. As a result this agent was judged to be a biaxial liquid crystal. Step 7 Product The phase transition temperature of the Step 7 product was also examined using a polarizing microscope. When the temperature was initially elevated, the crystal phase reverted to isotropic liquid phase in the vicinity of 80 C. Gradually lowering the temperature from 90 C resulted in an N phase at approximately 60 C. When the temperature was finally lowered to ambient temperature, the formation of a crystal phase was observed. As a result this agent was judged to be a biaxial liquid crystal.

PREPARATION OF RETARDATION FILM 8A.

Formation of Alignment Film

A polyvinyl alcohol containing 5% glutaraldehyde was dissolved in sufficient methanol/water, 20/80, respectively, to prepare a 5% solution. This solution was coated onto a cellulose triacetate film having a thickness of 100 mm and a size of 270 100 mm and then dried with hot air for 2 minutes at 100 C. The film was rubbed to form an alignment film having a thickness of 0.5 mm. 8B.

Formation of Optically Anisotropic Layer

On the alignment film obtained in Step 8A, a coating was evaluated for optically anisotropic properties by coating a #4 wire bar with the following components. Step 7 product, 100 parts Air interface orientation controlling agent, (II), 0.2 parts (unspecified) Photopolymerization initiator HJ-1, (III), 2.0 parts by mass Lucirin TPO-L, 2.0 parts Methyl ethyl ketone, 300 parts OC12H25 HN

C12H25O C12H25O

N N H

(II)

OC12H25 N

N

NH OC12H25 OC12H25

HO

N

HN

N

O

(III)

CCl3 N CCl3

312


8C.

Formation of Retardation Film

The Step 8B film was coated onto the optically anisotropic layer, placed in a thermostatic chamber at 80 C, and heated for 5 minutes 60 . Thereafter the film was cooled at 40 C for 30 seconds in a thermostatic chamber that had an oxygen content of 2% and then irradiated with ultraviolet radiation at 600 nm. The film was next cooled to ambient temperature, and the retardation film was isolated having an optically anisotropic layer thickness of 1.55 mm. The retardation in the direction perpendicular to the face of the retardation film was 150 nm parallel to the rubbing direction.

NOTES 1. Cinnamic acid liquid crystalline derivatives, (IV), capable of exhibiting a biaxial liquid crystal phase were also prepared by the author [1] and used as a component in retardation films.

RO

OR

OR

O R = CH2(CH2)3-OCO-CH=CH2

O

O O

RO

(IV)

OR

OR

2. Phenylacetylene derivatives, (V), were prepared by Tang [2] and converted into the corresponding polyacetylenes, (VI), as illustrated below, containing a sidechain liquid crystal molecular architecture of backbone þ spacer þ mesogenic group. These products were subsequently used in electronic and mechanical applications.

Notes

313

a 3O

3O

i O

O

O

O

O

O

5

5

(VI)

(V)

i: Rhodium(nitrobenzofuranzan chloride)dimer, THF, triethylamine 3. Coates [3] prepared liquid crystal films with a homeotropic alignment that was induced by an aligning perfluoropolymer substrate after UV irradiation of the three component phenylacetylene mixture, (VII)–(IX). Other cyano-analogues, (X), were prepared by Radcliffe [4].

O OR O Component

(VII) (VIII)

O

aO a

R O

O O CN

3

O

3 6

(IX)

C5H11

6

(X)

CN

2 or 6

314


4. Tanaka [4] prepared 30 mm-thick retardation films consisting of mixed esters of hydroxypropyl cellulose and acryloyl and n-butyryl chlorides, (XI), having a retardation value of 180 nm at a wavelength of 550 nm after photo polymerization.

O

O O

O O

a

O O

O O

O

O

(XI)


H. Nishikawa et al., US Patent 7,153,548 (December 26, 2006) B.Z. Tang et al., US Patent 7,070,712 (July 4, 2006) D. Coates et al., US Patent 7,170,575 (January 30, 2007) M.D. Radcliffe et al., US Patent 7,160,586 (January 9, 2007) K. Tanaka et al., US Patent 7,163,723 (January 16, 2007)

Title: Perfluoroallyloxy Compound and Liquid Crystal Composition Containing the Same Author:

H. Shinano et al., US Patent 7,001,647 (September 22, 2006)

Assignee:

Asahi Denka Co., Ltd. (Tokyo, JP)

SIGNIFICANCE Perfluoroalloxy liquid crystals were prepared by the Williamson ether synthesis using perfluoro iodopropene. These materials can be mixed with nematic liquid crystal materials to provide liquid crystal compositions having low viscosity, low refractive index anisotropy, high dielectric anisotropy, and broad nematic phase ranges.

REACTION F F F2C C3H7

OH

i

C3H7

O

F

i: Dimethylimidazolidinone, 3-iodoperfluoropropene, triethylamine

EXPERIMENTAL Preparation of Pentafluoro-3-(4-[4-(4-n-Propylcyclohexyl)Cyclohexyl] Phenoxy)-Propene A reactor was charged with 4-[4-(4-n-propylcyclohexyl)cyclohexyl]phenol (4 mmol) dissolved in dimethylimidazolidinone (7 g) and then treated with 3-iodoperfluoropropene (4 mmol) and triethylamine (4.8 mmol). The mixture was reacted for 2 hours, treated with EtOAc and hydrochloric acid, washed with water until neutral, and dried using MgSO4. The solvent was then exchange with toluene, treated with silica, and concentrated. The residue was purified by repeated kugel-rohr distillations followed by

315

316

Perfluoroallyloxy Compound and Liquid Crystal Composition Containing the Same

re-crystallization in EtOAc/methanol, 1/18, respectively, and then acetone; the product was isolated as white crystals in 47% yield. 1

H-NMR d 7.3 7.0 (m, 4H), 2.6 2.3 (m, 1H), 2.2 0.4 (m, 26H) FTIR (cm1) 2920, 2850, 1794, 1609, 1508, 1447, 1389, 1319, 1223, 1196

DERIVATIVES TABLE 1. Phase transition temperatures for perfluorooalloyloxy compounds and corresponding optical anisotropy (Dn) and dielectric anisotropy (Dee).

Entry

Phase Transition*1 Temperatures ( C)

Structure

F F2C

1

O

C3H7

F

F

F F

14

F2C

F

O

C5H11

F

Dn

De

Sm ¼ 157.3 N ¼ 174.2 ! I

0.0926 4.3

C ¼ 67.1 Sm ¼ 84.9 N ¼ 114.1 ! I

0.126

8.47

F

F F 18

F2C O

C3H7

F

F

Sm ¼ 41.2 N ¼ 166.6 ! I 0.1006 7.3

F F

19

F C5H11

F2 C O

F

Sm ¼ 44.4 N ¼ 170.8 ! I

F

Note: All experimental agents were prepared using the Williamson ether synthesis *1 Sm: smectic phase N: nematic phase I: isotropic phase

0.101

6.0

Notes

317

NOTES 1. Katoh [1] prepared a liquid crystal composition for use as electronic paper consisting of one dual-frequency switchable smectic liquid crystal, (I), and at least one dichroic dye. Cl

O

O C6H13

C5H11

O O

(I)

2. Liquid-crystalline phenol esters, (II), having a nematic phase of 30 C and a clearing point above 90 C were prepared by Reiffenrath [2] and used in thinfilm transistors. Naphthyl derivatives, (III), prepared by Takehara [3] were also effective in thin film transistor applications. F F OCHF2

O C3H7

C3H7

O

(II)

F

(III)

F

F

3. Perfluoropropenylcyclohexane-containing liquid crystals, (IV), prepared by Kato [4] were used as components in liquid crystal display elements.

F F C3H7

(IV)


T. Katoh et al., US Patent 7,220,466 (May 22, 2007) V. Reiffenrath et al., US Patent 7,179,511 (February 20, 2007) S. Takehara et al., US Patent 7,145,047 (December 5, 2006) T. Kato et al., US Patent 7,074,464 (July 11, 2006)

CF3

Title: Liquid Crystal Polymers Author:

B. Benicewicz et al., US Patent 7,148,311 (December 12, 2006)

Assignee:

Rensselaer Polytechnic Institute (Troy, NY)

SIGNIFICANCE Liquid crystal copolyesters were prepared using 4-phenylnaphthalene derivatives with 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, or other aromatic diacids. These materials display an improved balance of low melt viscosity, fast cycle time in molding, high tensile, low thermal expansion coefficient, and thermostability.

REACTION COOH

COOH Br H3CO

i

O

ii

O

H3CO O O

O O

a

iii

O

i: 4-Carboxyoxybenzene boronic acid, 1-propanol, palladium acetate, triphenylphosphine, sodium carbonate, acetic acid ii: Hydrobromic acid, acetic anhydride, sulfuric acid iii: 4-Hydroxybenzoic acid, tin (II) trifluoromethane sulfonate

EXPERIMENTAL 1.

Preparation of 2-(40 -Carboxyphenyl)-6-Methoxynaphthalene

A mixture consisting of 2-bromo-6-methoxynaphthalene (20 mmol), 4-carboxyoxybenzene boronic acid (20 mmol), and 40 ml of 1-propanol were mixed at ambient 318

Derivatives

319

temperature and then treated with palladium acetate (0.06 mmol), triphenylphosphine (0.009 mmol), 18 ml of 2M Na2CO3 solution, and 8 ml of water. The mixture was refluxed for 90 minutes then, with 25 ml of water while it was still hot, and refluxed with 50 ml of acetic acid for 45 minutes. It was then cooled to ambient temperature whereupon crystals formed. The crystals were filtered, washed with water, and re-crystallized from acetone; the product was isolated 83% yield as white crystals. 2.

Preparation of 2-(40 -Carboxyphenyl)-6-Acetoxynaphthalene

A mixture of the Step 1 pro[duct (10 mmol), 80 ml of 48% aqueous hydrobromic acid, and 150 ml of acetic acid were refluxed overnight and then poured into 400 ml water. The residue was mixed with 40 ml acetic anhydride with 1 to 2 drops of H2SO4 for 2 hours, and a pink solid was isolated. This material was re-crystallized from acetone or pentanone, and the product was isolated in 66% yield as light yellow crystals. MP ¼ 288–289 C IR (KBr) (cm1))[nujol] 2500 3000 (COOH, very broad, m), 1030 (OCH3, s), 1678 (C¼O, s). 1 H NMR (500 MHz, CDCl3) d 3.90 (s, 3H), 7.2 8.3 (m, 10H), 12.99 (s, 1H)

3.

Preparation of Polyesters by Bulk Polymerization

A mixture consisting of the Step 2 product and 4-hydroxybenzoic acid with approximately 500 ppm of potassium acetate or Sn(CF3S03)2 was charged into a polymerization tube with a side branch and then degassed and purged with nitrogen. While the mixture was purged with nitrogen, the reaction temperature was increased to 250 C for about 1.5 hours, 280 C for 30 minutes, 300 C for 30 minutes, and 320 C for 30 minutes. During the temperature gradient, acetic acid was collected in a testtube at the end of the side branch. At the final stage the temperature was kept at 320 C to 330 C, and a vacuum was applied for 60 minutes to remove residual acetic acid. MP ¼ 254–256 C DSC MP ¼ 262 C IR (KBr) (cm1)[nujol] COOH (2800 3100, broad, m), 1685 (C¼O, s), 1225 (COC, vs), 1365 (CH3CO, s) 1 H NMR (500 MHz, CDCl3) d 2.34 (s, 3H), 7.3 8.4 (m, 10H), 13.02 (s, 1H)

DERIVATIVES Monomers

Y

X

320

Liquid Crystal Polymers

TABLE 1. Transition temperatures for selected 4-phenylnaphthalene monomers of the current invention. Entry 1 2 3 4 5 6

X

Crystal Mp ( C)

Y

OCH3 OH COOH OCOCH3 OCOCH3 COOH

OCH3 COOH OCH3 OCOCH3 COOH COOH

196 296 269 182 263 >350

Neumatic Mp ( C)

Isotropic Mp ( C)

187 322 339 207 Polymerizes ––

142 –– –– –– –– ––

Note: Evidence for liquid crystal formation for meta- and ortho-phenylnaphthalene monomers was not detected.

Polyesters

O O

O O

a O

b TABLE 2. Thermal properties of copolyesters derived from 6-hydroxy-2-naphthoic acid and 6-(40 -acetoxyphenyl)-2-naphthoic acid. Monomer Ratio (a:b) 75:25 67.5:32.5 60:40 50:50 40:60

5% Weight Loss ( C) 378 373 426 420 425

10% Weight Loss ( C) 394 385 440 436 438

Crystal Mp ( C) 352 270 260 276 401

Note: Copolymers had limited solubility in perfluorophenol. Endothermic peaks for all materials corresponding to Tg’s were weak and ambiguous.

Notes

321

O O

O O

a O

b

TABLE 3. Thermal properties of copolyesters derived from 4-hydroxybenzoic acid and 6-(40 -acetoxyphenyl)-2-naphthoic acid. Monomer Ratio (a:b) 80:20 65:35 55:45 50:50 40:60

5% Weight Loss ( C) 405 426 409 450 423

10% Weight Loss ( C)

Tg ( C)

Crystal Mp ( C)

242 189 163 160 ––

435 430 417 420 408

425 430 424 460 435

Note: Although Tg’s provided by the author were reproducible, peaks were weak and ambiguous.

NOTES 1. Multireactive mesogenic triester derivatives, (I), containing at least two polymerizable components were prepared by Farrand [1] and used as synthetic resins with anisotropic mechanical properties.

O O O O O

C8H17

(I)

O

2. Mesogen-containing acetylene monomers, (II), were prepared by Tang [2] and polymerized into polyacetylenes, (III). These monomers had excellent tractability typically associated with polymers having flexible backbones.

322

Liquid Crystal Polymers

O

O O

O O

6

6

(II) i O

O O

O O

6

6

n

(III) i: Rhodium(2,5-norbornadiene)chloride dimer, THF, triethylamine 3. Liquid crystal polymers prepared by Wellinghoff [3] by UV-curing of mesogenic dimers such as methacrylate carboxylic acid esters, (IV), and diacrylate dimethylsiloxanes, (V), had good fracture toughness, limited shrinkage, mechanical strength, and four-point bending strength and were used in dental applications. Liquid crystal monomers, (VI), with ultra–low cure shrinkage were prepared by Norling [4] and were used in dental resin composites. O

t-C4H9

O

O

O

O

O

8 O

O

O

O t-C4H9

O

(IV) t-C4H9

t-C4H9

O

O

O

O

Si

O

Si

O

Si

O

O

O

O

O

(V) O O

6

O

O

O

O

O

(VI)

O O

6

O

Notes

323

4. Vaughn-Spickers [5] prepared chiral photoisomerizable mesogenic compounds, (VII), that retained their chirality upon photoinitation and were used in optical and electrooptical devices. O C5H11

O

O O

O O

O 3

O

O

(VII)

References 1. L. Farrand et al., US Patent 7,125,500 (October 24, 2006) 2. B.Z. Tang et al., US Patent 7,070,712 (July 4, 2006) 3. S.T. Wellinghoff et al., US Patent 7,098,359 (August 29, 2006) and US Patent 7,094,360 (August 22, 2006) 4. B.K. Norling et al., US Patent 7,135,589 (November 14, 2006) 5. J. Vaughn-Spickers et al., US Patent 7,122,227 (October 17, 2006)

XV. NANOPARTICLES A. Carbon Nanotubes

Title: Method of Coating a Substrate with a Polymer Having a Combination of Crown Ether and Carbon Nanotubes Having Guanidine Groups Author:

H. S. Lee, US Patent 7,261,924 (August 28, 2007)

Assignee:

Samsung Electro-Mechanics Co., Ltd. (Suwon, KR)

SIGNIFICANCE A functionalized carbon multi-walled nanotube, MWNT, was prepared in 2 steps by initially oxidizing the unfunctionalized nanotube with mixed acids followed by amidation with guanidine. When reacted with polystyrene-g-dibenzo-18-crown-6-ether, the polymer, polystyrene-g-dibenzo-18-crown-6-ether-g-(nanotube-g-guanidine), was formed having the nanotube component aligned perpendicular to the polystyrene backbone.


326

Method of Coating a Substrate with a Polymer Having a Combination of Crown Ether

REACTION i

H N

O

COOH

ii

NH 2 NH

Intermediate

Nanotube

a

a iv

iii

Intermediate

CO 2H

O

O

O O

O O

O O b c

a

O

O

O

O

NH

O

O

NH

HN O

O O

O

i: Sulfuric acid, nitric acid ii: Guanidine, CH2Cl2 iii: Polystyrene-g-carboxylic acid, hydroxylmethyl dibenzo-18-crown-6-ether, pyridine, water iv: Ethanol

EXPERIMENTAL 1.

Preparation of Multi-walled Carbon Nanotube-g-Carboxylic Acid

MWNTs (40 mg) were added to a mixture of 60 ml of H2SO4 and 20 ml of HNO3 and then reacted for 24 hours at 50 C with ultra-sonication at about 30 kHz. The strongly acidic reaction solution was diluted with water to a pH of roughly 7, filtered through of 0.5 to 1-mm filter paper, dried at 80 C for 6 hours, and the product was isolated. FTIR (cm1) 1700, C¼O, 3300, OH

Notes

2.

327

Preparation of Nanotube-g-Guanidine

A mixture consisting of the Step 1 product (10 mg), guanidine (20 mg), and 5 ml of 2M oxalic acid were dissolved in CH2Cl2 and heated for 6 hours at 50 C. The mixture was then filtered, and the product was isolated.

3.

Preparation of Polystyrene-g-Dibenzo-18-Crown-6-Ether

Polystyrene-g-carboxylic acid (5 g) and hydroxylmethyl dibenzo-18-crown-6-ether (1g) were dissolved in 500 ml of pyridine and reacted at ambient temperature for 5 hours. The mixture was then treated with water, and the layers were separated. The organic phase was concentrated, and the product was isolated.

4. Preparation of Polystyrene-g-Dibenzo-18-Crown-6-Ether-g(Nanotube-g-Guanidine) A 1-mm thick copper substrate was coated with a 200 -mm thick film consisting of the Step 3 product and then dried at 50 C. The film was coated with 200 mm of the Step 2 product (10 mg) dispersed in 100 ml of ethanol. Thereafter the coating was dried at 70 C, and the product was isolated having MWNTs aligned perpendicularly to the copper substrate at regular intervals.


NOTES 1. Hwang [1] prepared polymers, (I), of polyphenylenebisbenzothizaole and SWNT-g-carboxylic acid as a method of improving the solubility of nanotubes in organic solvents.

N

N

X

X

H N

O

X = O, S (I)

a

Nanotube

328

Method of Coating a Substrate with a Polymer Having a Combination of Crown Ether

2. Chen [2] enhanced the solubility of nanotubes in organic solvents by a noncovalent, nonwrapping approach using p-stacking with rigid-rod conjugated polymers, (II). OC10H21

OC10H21

S O

S

a C10H11O

(II)

C10H21O

3. Nanotube patterned films were prepared by Park [3] using surface-modified carbon nanotubes with polyoxetanes. References 1. W.-F. Hwang et al., US Patent 7,262,266 (August 28, 2007) 2. J. Chen et al., US Patent 7,244,407 (July 17, 2007) and US Patent 7,241,496 (July 10, 2007) 3. J.J. Park et al., US Patent 7,229,747 (June 12, 2007)

Title: Process for Derivatizing Carbon Nanotubes with Diazonium Species Author:

J. M. Tour et al., US Patent 7,250,147 (July 31, 2007)

Assignee:

William Marsh Rice University (Houston, TX)

SIGNIFICANCE Single-walled carbon nanotubes, SWNT, having a diameter of 0.7 nm were electrochemically derivatized on the sides and ends with diazonium tetrafluoroborate derivatives. In this process the estimated degree of functionality was about 1 out of every 20 to 30 carbons in the nanotube. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications, and sensor devices.

REACTION C14H29

C14H29

NH2

i

C14H29

+ _ N2BF4

ii

C14H29

C14H29

Nanotube

i: 4-Tetradecylaniline, acetonitrile, CH2Cl2, tetrafluoroborate ii: Bucky paper, 1,2-dichlorobenzene, acetonitrile, tetra-n-butylammonium tetrafluoroborate

329

330

Process for Derivatizing Carbon Nanotubes with Diazonium Species

EXPERIMENTAL 1.

Preparation of 4-Tetradecylbenzenediazonium Tetrafluoroborate

4-Tetradecylaniline (1 eq) was dissolved in a 1:1 mixture of acetonitrile and CH2Cl2 and then added to tetrafluoroborate (1.2 eq) at 30 C. Stirring was continued for 30 minutes, and the cooling bath was removed. After stirring for an additional 30 minutes, the solution was diluted with two times its volume with diethyl ether product. The precipitated that formed was filtered and isolated in 69% yield, MP ¼ 82 C. 2.

General Procedure for Electrochemical Derivatization of SWNT

A three-electrode cell with an Ag/AgNO3 reference electrode and platinum wire counterelectrode was used in the electrochemical derivatization experiments where bucky paper (1–2 mg) served as the working electrode. The bucky paper was prepared by filtering a 1,2-dichlorobenzene suspension of the bucky paper over a 0.2-mM Teflon 47 mm membrane. After drying under vacuum, the paper was peeled off the membrane and a piece was excised for use in the derivatization process. The paper was held with an alligator clip previously treated with colloidal silver paste and immersed in an acetonitrile solution of 0.5 mM diazonium salt and 0.05 M tetra-n-butylammonium tetrafluoroborate. A potential of 1.0 V was applied for a period of 30 minutes while nitrogen was bubbled through the solution. Thereafter the portion of the bucky paper that was not immersed in the solution was excised while the remainder was soaked in acetonitrile for 24 hours, washed with acetonitrile, chloroform, and ethanol. After drying, this material was sonicated in acetonitrile for 20 minutes, filtered, re-washed with acetonitrile, 2-propanol, and chloroform. The residue was dried under vacuum at ambient temperature, and the product was isolated. H NMR (400 MHz, CDCl3) d 8.02 (ABq, J ¼ 8.8 Hz, 2.76 (t, J ¼ 7.7 Hz, 2H), 1.61 (quin, J ¼ 7.8 Hz,2H), 1.23 (s, 22H), 0.85 (t, J ¼ 7.0 Hz, 3H) 13 C NMR (100 MHz, CDCl3) d 159.92, 133.26, 131.94, 110.96, 37.49, 32.34, 30.87, 30.12, 30.10, 30.07, 30.04, 29.91, 29.78, 29.75, 29.72, 23.11, 14.55 IR (KBr) (cm1) 3103.8, 2919.5, 2289.6, 1577.8, 1473.7, 1070.8, 1024.8, 844.5, 813.8, 716.9, 541.0, 510.2

1

DIAZONIUM TETRAFLUOROBORATE DERIVATIVES

R

_ + N2BF 4

Notes

331

TABLE 1. Summary of diazonium tetrafluoroborate derivatives prepared according to the Step 1 procedure. Entry

R

1 3 5 6 9

Melting Point ( C)

Yield (%)

138 160 142 113 —

85 79 67 80 52

Bromo Fluoro Nitro Methoxycarbonyl CH3O(CH2CH2O)2CH2CH2O

NOTES 1. Stoddart [1] noncovalently wrapped nanotubes with poly{(5-alkoxy-mphenylenevinylene)-co-[(2,5-dioctyloxy-p-phenylene)vinylene]}, (I), as a method of increasing the solubility of nanotubes in selected solvents.

OC8H17

a C8H17O OR

(I)

R = CH2OCH3 (CH2)6OH

2. Khabashesku [2] functionalized carbon nanotubes utilizing peroxides as illustrated below. Niu [3] introduced hydroxycarbonyl functions onto the surface of single-walled carbon nanotubes using ammonium persulfate and sulfuric acid. O HO

OH

O 2 O

O O

2

OH OH

.

2

O 2

O

OH

HO O

2

3. Sidewall-functionalized carbon nanotubes were prepared by Wong [4] using ozone with an oxygen carrier then postreacted with sodium hydride or DMS to decompose primary ozonides to form aldehydes and ketones.

332

Process for Derivatizing Carbon Nanotubes with Diazonium Species


J.F. Stoddart et al., US Patent 7,220,818 (May 22, 2007) V.N. Khabashesku et al., US Patent 7,125,533 (October 24, 2006) C. Niu et al., US Patent 7,045,248 (July 4, 2006) S. Wong et al., US Patent Application 2005-0147553 (July 7, 2005) and US Patent 7,122,165 (October 17, 2006)

Title: Carbon Nanotube Adducts and Methods of Making the Same Author:

S. S. Wong et al., US Patent 7,169,329 (January 30, 2007)

Assignee:

The Research Foundation of State University of New York (Albany, NY)

SIGNIFICANCE A method for covalently incorporating Wilkinson’s complex onto a multi-walled carbon nanotube is described. Semiconductor carbon nanotubes derived from these materials had mobilities and transconductance properties that were superior to those of existing semiconductors.

REACTION

(C6H5)3P Cl Rd (C6H5)3P O

(C6H5)3P HO

HO

i

CO 2H HO 2C

ii

P(C 6H5)3 Rd Cl P(C 6H5)3 O Rd P(C 6H5)3 O Cl OH

P(C 6H5)3 (C6H5)3P Rd O Cl

HO O OH Cl Rd P(C 6H5)3 (C6H5)3P

OH Cl O Rd P(C H ) 6 5 3 P(C 6H5)3

i: Potassium permanganate, hydrochloric acid ii: Wilkenson’s complex, DMSO

333

334

Carbon Nanotube Adducts and Methods of Making the Same

EXPERIMENTAL 1.

Preparation of Nanotube-g-Carboxylic Acid

Raw nanotubes having a mean diameter of 1.41 nm containing about 30 wt% metal catalysts, such as Ni and Co, were purified by oxidation with acidic KMnO4 solution and then washed with HCl and water. The purified tubes were dried at 100 C and dispersed in DMSO by mild sonication.

2.

Preparation of Nanotube-g-Carboxylic Acid/Wilkenson’s Catalyst

A Schlenk apparatus was charged with the briefly sonicated Step 1 product dispersed in DMSO and treated with the dropwise addition of 10 ml of a 10 mM solution of Wilkinson’s complex in DMSO. The reaction mixture was stirred at 55 C to 60 C for 80 hours and filtered through a 0.2 mm nylon membrane. Dissolved tubes were precipitated out by treating the solution with saturated brine. The precipitated material was purified by filtering over a 0.2 mm nylon membrane and washing in DMSO, ethanol, and water.

ANALYTICAL 1. Both scanning electron microscopy and atomic force microscopy of the functionalized multi-walled nanotubes indicated a high density of small nanotube bundles whose diameters were on the order of 15 to 20 nm. 2. Powder X-ray diffraction indicated that the tubes were able to coalesce together upon solvent removal. 3. 31 P-, 13 C-, and 1 H NMR spectroscopy confirmed the coordination of Wilkinson’s complex with the nanotubes.

NOTES 1. Massey [1] functionalized graphitic nanotubes including C60-fullerenes, (I), which were then used in electrogenerated chemiluminescence assays.

N

Chymotrypsin

Trypsin C60

Ru

N N

Gly

Lys

Phe

Gly

(I)

NH

N N N

Notes

335

2. Barraza [2] prepared single-walled nanotube/polystyrene composites by miniemulsion polymerization, using surfactants, styrene, and nanotubes grafted with varying degrees of glucosamine, (II).

O O OH HO

(II)

O H2N

References 1. R.J. Massey et al., US Patent 7,052,861 4 (May 30, 2006) 2. H.J. Barraza et al., US Patent 7,153,903 (December 26,2006)

OH

a

Title: Modification of Nanotubes by Oxidation with Peroxygen Compounds Author:

C. Nie et al., US Patent 7,070,753 (July 4, 2006)

Assignee:

Hyperion Catalysis International, Inc. (Cambridge, MA)

SIGNIFICANCE A method of preventing aggregation of nanotubes is described. The procedure entails the ambient temperature introduction of carboxylic acids onto the nanotube substrate using a mixture of ammonium persulfate and sulfuric acid. By this method up to 0.76 meq/g carboxylic acid was introduced onto a nanotube surface after two days.

REACTION HOOC

Nanotube

HOOC

COOH

i Notes 1,2

COOH

COOH

COOH

i: Ammonium persulfate, sulfuric acid

EXPERIMENTAL Oxidation was carried out by stirring the nanotubes in a mixture consisting of 1M (NH4)2S2O8 and 1M H2SO4 for between one to seven days at ambient temperature. The oxidation mixture was prepared by dissolving (NH4)2S2O8 in 1M H2SO4 solution. The nanotube concentrations ranged from 3.247 to 15 g in 300 ml of the oxidation agent mixture. During the oxidation thick nanotube slurries formed that were subsequently filtered, washed with water, and dried; the oxidized nanotubes were then isolated.

336

Scoping Studies

337

SCOPING STUDIES TABLE 1. Summary of surface oxidation of nanotubes in 300 ml 1M ammonium persulfate/sulfuric acid mixture. Entry

Fibrils (g)

1 2 3 4

Oxidation Duration (days)

15 7.521 7.492 3.247

Surface Groups (meq/g)

2 2 1 1

0.73 0.76 0.52 0.52

Note: Oxidized nanotubes had the appearance of weathered rope with many broken and loose ends.

Sample Preparation for Electrochemical Testing Electrodes with a diameter of 0.5 inch were prepared by sonicating a mixture of 0.3 g oxidized nanotubes with 300 ml of water and 5 drops Triton X-100 using a 400 W ultrasonic processor. A mat was initially prepared by drying the nanotubes at 100 C, the nanotubes were then further heated to 350 C in air for 4 hours. The final weight of the mat was 283 mg with a thickness of 0.0049 inch and a density of 0.41g/ml. Testing results provided in Table 2. TABLE 2.

Entry 1 2 3 4

Results of electrochemical testing of oxidized nanotubes.

Electrode Thickness (inch) 0.0049 0.0045 0.0049 0.0049

Density (g/ml)

Equivalent Series Resistance (ohm)

Specific Capacitance (F/g)

Knee Point Frequency (Hz)

Pore Resistance (ohm)

0.41 0.42 0.43 0.43

0.052 0.045 0.044 0.037

46.7 49.2 44.6 45.6

150 154 150 151

0.005 0.006 0.005 0.005

Note: The results indicate that other than specific capacitance, which increased slightly with higher surface oxidation, no significant differences were detected. All electrodes had excellent frequency responses.

NOTES 1. Nanotube oxidations using ClO2, CO2, NO, NO2, and O3 are described by the author [1]. 2. In a subsequent investigation by the author [2] functionalized nanotubes of the current invention were amidated with nylon-6 macromolecules so that the

338

Modification of Nanotubes by Oxidation with Peroxygen Compounds

polymer composite contained between 3 and 10 wt% polymer. Dai [3] modified amidated nanotubes of the current invention with conjugates containing oxidized-biotin-Strepavidin complexes, (I). O N H Nanotube

H HN

H N

S

O

O NH H

Alexa Fluor Streptavidin

(I)

3. Fisher [4] introduced sulfonic acid groups and tubular fullerenes onto graphitic nanotubes, using sulfuric acid in order to induce cyclic compounds to become adsorbed onto the surface. 4. Khabashesku [5] used selected peroxides to functionalize single-wall nanotubes, as indicated below. INTRODUCED ENTRY

2 3

REAGENT(S)

Benzoyl peroxide a-Iodoethyl acetate benzoyl peroxide

FUNCTIONALITY

Phenyl a-Ethyl acetate


C. Nie et al., US Patent Application 2006-0239891 (October 26, 2006) C. Nie et al., US Patent Application 2006-0249711 (November 9, 2006) H. Dai et al., US Patent Application 2006-0275371 (December 7, 2006) A. Fisher et al., US Patent Application 2006-0193868 (August 31, 2006) and US Patent 6,203,814 (March 20, 2001) 5. V.N. Khabashesku et al., US Patent 7,125,533 (October 24, 2006)

Title: Arylcarbonylated Vapor-Grown Carbon Nanofibers Author:

L.-S. Tan et al., US Patent 7,005,550 (February 28, 2006)

Assignee:

The United States of America as Represented by the Secretary of the Air Force (Washington, DC)

SIGNIFICANCE There is a continuing need for achieving a good dispersion of single-wall carbon nanotubes to ensure high performance of these materials. To address this concern, dispersed carbonyl-functionalized nanoscale tubes have been prepared by reacting 4(2,4,6-trimethylphenoxy)benzoic acid with vapor-grown carbon nanofibers in the presence of polyphosphoric acid.

339

340

Arylcarbonylated Vapor-Grown Carbon Nanofibers

REACTION CO 2H

CN OH

O

i

ii

O

O

iii

O O

Nanoscale tubes

O

O

O

O

O

i: Benzonitrile, potassium carbonate, toluene, NMP ii: Phosphoric acid iii: Vapor-grown carbon nanofiber, polyphosphoric acid, phosphorous pentoxide

EXPERIMENTAL 1.

Preparation of 4-(2,4,6-Trimethylphenoxy)Benzonitrile

A 250-ml round-bottomed flask was charged with 2,4,6-trimethylphenol (44.1 mmol), 4-fluoro-benzonitrile (44.1 mmol), potassium carbonate (52.8 mmol), and a mixture of 100 ml NMP and 60 ml of toluene and then heated to 140 C for 8 hours. The mixture was filtered, the filtrate poured into 5% hydrochloric acid, and the organic and aqueous layers separated. The organic layer was diluted with CH2Cl2 and concentrated. After the light brown oily residue was freeze-dried, the product was isolated in 97% yield. 1

H-NMR (CDCl3) d 2.05 (s, 6H, CH.sub.3), 2.30 (s, 3H, CH.sub.3), 6.81 6.84 (d, 2H, Ar), 6.91 (s, 2H, Ar), 7.53 7.56 (d, 2H, Ar) 13 C-NMR (CDCl3) d 16.10, 20.79, 115.48, 129.07, 129.15, 129.88, 130.48, 134.25, 147.84, 150.03, 161.44.

Notes

2.

341

Preparation of 4-(2,4,6-Trimethylphenoxy)Benzoic Acid

A reaction flask was charged with the Step 1 product (42.0 mmol) and 100 ml of phosphoric acid and heated to 150 C for 8 hours; the mixture was then poured into 5% hydrochloric acid. The resulting precipitate was collected, dried, and dissolved in warm heptane. The filtrate was cooled to ambient temperature, and the product was isolated in 42% yield as a white solid, MP ¼ 236–238 C. 3. Functionalization of Vapor-Grown Carbon Nanofiber with 4-(2,4,6-Trimethylphenoxy)Benzoic Acid A 250 ml resin flask equipped with a high-torque mechanical stirrer was charged with the Step 2 product (1.95 mmol), vapor-grown carbon nanofibers (0.50 g) having diameters and lengths of 100 to 200 nm and 30 to 100 mm, respectively, and 83% polyphosphoric acid. Thereafter the mixture was heated to 130 C for 3 hours, treated with phosphorous pentoxide (5.0 g) in one portion, and maintained at 130 C for 80 hours. After cooling to ambient temperature, water was added, and the resulting precipitate was collected and washed with diluted ammonium hydroxide. The precipitate was next Soxhlet extracted for three days apiece using water and then methanol. After drying over phosphorous pentoxide at 100 C for 72 hours at 0.05 mmHg, the product was isolated in 85% yield. 1

H-NMR (d6 -DMSO) d 2.00 (s, 6H, CH.sub.3), 2.67 (s, 3H, CH.sub.3), 6.74 6.77 (d, 2H, Ar), 6.98 (s, 2H, Ar), 7.82 7.86 (d, 2H, Ar) 13 C-NMR (d6 -DMSO) d 15.80, 20.41, 113.80, 127.65, 129.69, 129.81, 130.12, 134.47, 147.95, 159.95, 167.06 Elemental analysis Calcd. C, 92.63%; H, 2.36%; 0, 5.00%. Found: C, 90.93%; H, 2.82%; O, 4.89%. Calcd for VGCNF C, 100.00% Found: C, 98.67%; H, 1.10%; O, 0.20% (less than detection limit) FTIR (KBr cm1) 1240, 1590, 1646, 2922, 3434


NOTES 1. To increase the solubility of single-walled nanotube in selected solvents Stoddart [1] noncovalently wrapped tubes with poly(2,6-pyridinylenevinylene)-co-[(2,5-dioctyloxy-p-phenylene)vinylene], (I).

342

Arylcarbonylated Vapor-Grown Carbon Nanofibers

OC8H17

a N

C8H17O

(I)

2. Hwang [2] functionalized nanocapsules with polyaniline as a method for dispersing carbon nanocapsules. Nanocapsule

H N

O N H

H N a

N H

a

O O

HN NH a

(II) 3. Dennis [3] used end-capped nonfunctionalized nanotubes, (III), as delivery agents for human umbilical vein endothelial cells. Carbon nanotubes closed at either end by caps were used by Glatkowski [4] as sunscreen delivery agents. Nanotube

SH

SH

HS

Tube cap

SH

SH

Encapsulated endothelial cells


J.F. Stoddart et al., US Patent 7,220,818 (May 22, 2007) G-L. Hwang et al., US Patent 7,217,748 (May 15, 2007) D.M. Dennis et al., US Patent 7,195,780 (March 27, 2007) P.J. Glatkowski et al., US Patent 7,195,754 (March 27, 2007)

SH

B. Inorganic Nanotubes

Title: Polymeric and Carbon Compositions with Metal Nanoparticles Author:

T. M. Keller et al., US Patent 7,198,771 (April 3, 2007)

Assignee:

The United States of America as Represented by the Secretary of the Navy (Washington, DC)

SIGNIFICANCE The use of transition metals containing carbon or ceramic intermediates as a method for preparing nanoparticles is virtually unexplored. To address this deficiency, iron thermosets and nanoparticles were prepared by pyrolysis of ferrocene-containing compounds.

REACTION

Fe

i

Fe Br

Iron nanoparticles

ii Note 1

Fe

Thermoset

i: 1-Bromo-3-iodobenzene, palladium acetate, phosphine, THF, pyridine, diisopropylamine, copper (I) iodide ii: Phenylacetylene, palladium acetate, phosphine, THF, pyridine, diisopropylamine, copper (I) iodide

343

344

Polymeric and Carbon Compositions

EXPERIMENTAL 1.

Preparation of 1-(Ferrocenylethynyl)-3-Bromobenzene

A 50-ml round-bottomed flask was charged with 1-bromo-3-iodobenzene (0.114 mmol) and ethynylferrocene (2.38 mmol) and then treated with Pd(OAc)2 (2.27 mmol) and PPh3 (0.341 mmol) in a mixture consisting of 25 ml of THF, 5 ml of pyridine, and 5 ml of diisopropylamine at 25 C. The solution was stirred at ambient temperature for 20 minutes, treated with CuI (0.0568 mmol), and cooled to 78 C. It was then evacuated and backfilled with argon several times, warmed to ambient temperature, and stirred for 16 hours at 25 C. The mixture was concentrated, the residue purified using hexane/CH2Cl2 a 5:1, respectively, and the product isolated in 92% as an orange-red solid, MP ¼ 130 C. 2.

Preparation of 1-(Ferrocenylethynyl)-3-(Phenylethynyl)benzene

A 50-ml round-bottomed flask was charged with the Step 1 product (1.37 mmol) and phenylacetylene (0.0686 mmol) and then treated with Pd(OAc)2 (15.4 mg) and PPh3 (53.9 mg) in 25 ml of THF, 5 ml of pyridine, and 5 ml diisopropylamine at 60 C. It was stirred at ambient temperature for 20 minutes, treated with CuI (0.0568 mmol), and cooled to 78 C. The mixture was evacuated and backfilled with argon several times and then warmed to ambient temperature and stirred for 16 hours at 25 C. It was concentrated, the residue purified using hexane/CH2Cl2 a 5:1, respectively, and the product isolated in 92% as an orange-red solid, MP ¼ 181 C. IR (cm1, KBr): 3094 (C–H), 3057 (C–H), 2204 (C.ident.C), 1591 (C¼C, benzene), 1583 (C¼C, benzene), 1552 (C¼benzene), 1411 (C¼C, ferrocene) 1 HNMR (CDCl3): d 7.63 (t, J ¼ 1.7 Hz, 1H), 7.41 (m, 2H), 7.17 (t, J ¼ 7.8 Hz, 1H), 4.50 (t, J ¼ 1.9 Hz, 2H), 4.25 (t, J ¼ 1.9 Hz, 2H), 4.24 (s, 5H) Analysis C18H13FeBr Calcd: C, 59.22%; H, 3.59%. Found: C, 59.15%; H, 3.84%

3.

Preparation of Thermoset

The Step 2 product was placed into a TGA boat and polymerized by heating under a nitrogen atmosphere at 225 C for 5 minutes, 300 C for 30 minutes, and at 350 C for 30 minutes. The solid was then cooled, and a solid black material was isolated. IR (cm1, KBr): 3111 (C–H), 3097 (C–H), 2212 (C–C), 1597 (C¼C, benzene), 1570 (C¼C, benzene), 1491 (C¼C, benzene), 1411 (C¼C, ferrocene) 1 HNMR (CDCl3): d 7.67 (m, 1H), 7.53 (m, 2H), 7.44 (m, 2H), 7.34 (m, 3H), 7.29 (t, J ¼ 7.8 Hz, 1H), 4.50 (t, J ¼ 1.8 Hz, 2H), 4.24 (m, 7H) Analysis C26H18Fe) Calcd: C, 80.84%; H, 4.70%. Found: C, 80.31%; H, 4.63%.

4.

Carbonization of 1-(Ferrocenylethynyl)-3-(Phenylethynyl)Benzene

The Step 3 product was further heated in a TGA boat from 300 C to 1000 C at 10 C/min under a nitrogen atmosphere, which resulted in a char yield of 86%. In the

Derivatives

345

heat processing the Step 3 product lost 9% of its weight between 400 C and 600 C and 5% between 600 C and 1000 C, resulting in carbonization and the formation of iron nanoparticles. The iron nanoparticle carbon composition was attracted to a permanent magnet, indicating ferromagnetic behavior.

DERIVATIVES Additional Step 2 derivatives, (I)–(III), were prepared and converted into thermosets and iron nanoparticles as are illustrated below.

Fe (I)

Br

Fe

Fe (II)

Fe (III)

Fe

NOTES 1. In a subsequent investigation by the author [1] a pyrolysis of siloxane-ferrocene polymers, (IV), was used to prepare ceramic materials.

Si O

Si CH10B10C

Si O Si

Fe Si O Si

(IV)

CB10H10C

Si O

Si

a

2. Titanium oxynitride nanoparticles were prepared by Gole [2] and used in solar cells and as a semiconductor-based photocatalytic component in fuel cells. 3. Nanoparticles containing Fe2O3 were prepared by Li [3] and incorporated into cigarette filters as a method of lowering the amount of carbon monoxide and/or nitric oxide in inhaled tobacco smoke. 4. Peng [4] prepared monodispersed nanoparticles between 1 and 20 nm consisting of gold, silver, copper, and platinum, which were used as high efficiency industrial catalysts. 5. McCormick [5] prepared thiol-stabilized nanoparticles containing gold, platinum, palladium, rhodium, ruthenium, osmium, and iridium, which were used in optics, immunodiagnostics, and electronics.

346

Polymeric and Carbon Compositions

References 1. T.M. Keller et al., US Patent Application 2007-0073038 (March 29, 2007) and US Patent Application 2007-0073036 (March 29, 2007) 2. J.L. Gole et al., US Patent 7,186,392 (March 6, 2007) 3. P. Li et al., US Patent 7,168,431 (January 30, 2007) 4. X. Peng et al., US Patent 7,160,525 (January 9, 2007) 5. C.L. McCormick III et al., US Patent 7,138,468 (November 21, 2006)

Title: Metal Oxide Nanotube and Process for Production Thereof Author:

T. Shimizu et al., US Patent 7,172,747 (February 6, 2007)

Assignee:

National Institute of Advanced Industrial Science and Technology (Tokyo, JP)

SIGNIFICANCE Spiral shaped hollow nanofibers were formed from the reaction of p-aminophenylb-D-glucopyranoside and p-dodecanoylaminophenyl-b-D-glucopyranoside with excess tetraethoxysilane. The diameter distributions of these tubes ranged from 1 to 2 nm and from 3 to 7 nm. Metal oxide nanotubes derived from this process displayed excellent hydrogen adsorption and storage capacity for potential use in hydrogenpowered vehicles.

REACTION OH

OH O OH HO

O OH

O OH

i NO2

OH

HO

O OH

ii

O OH

NH2

HO

O OH

iii

Notes 1,2

H N

10

O

Silicon oxide nanotube cluster

i: Palladium on carbon, THF, methanol, hydrogen ii: Lauroyl chloride, triethylamine iii: p-Aminophenyl-b-D-glucopyranoside, water, methanol, benzylamine

tetraethoxysilane, 347

348

Metal Oxide Nanotube and Process for Production Thereof

EXPERIMENTAL 1.

Preparation of p-Aminophenyl-b-D-Glucopyranoside

p-Nitrophenyl-b-D-glucopyranoside (250 mg) was dissolved in 20 ml of methanol and 5 ml of THF and 10% palladium on carbon (250 mg) added to the solution. Hydrogen gas was introduced into the solution at ambient temperature for 3 hours. The mixture was then filtered and the solvent evaporated. The solid residue was purified by silica gel chromatography using THF/CCl3H, 1:1, and the product was isolated in 80% to 90% yield. H-NMR (300 MHz, DMSO-d6): d ¼ 3.44 4.10 (m, 6H), 4.76 (s, 2H), 5.25 5.31 (m, 3H), 5.60 (s, 1H), 6.70 (d, J ¼ 9.0 Hz, 2H), 6.95 (d, J ¼ 9.0 Hz, 2H), 7.37 7.46 (m, 5H) FT-IR (KBr, cm1) ¼ 3312, 2909, 1635, 1510, 1364, 1217, 1089, 1005, 1035, 999, 806, 706 MS (NBA): m/z: 360 [M þ H] 1

2.

Preparation of p-Dodecanoylaminophenyl-b-D-Glucopyranoside

The Step 1 product (250 mg) was dissolved in 20 ml of THF, treated with lauroyl chloride (300 mg) and triethylamine (1.0 g), and refluxed for 5 hours. The solution was filtered to remove solids, and the filtrate was concentrated under vacuum. The residue was purified using silica gel chromatography with methanol/CCl3H, 1:1, and the product was isolated in 80% yield. H-NMR (300 MHz, CCl3H): d ¼ . ¼ 0.9 (t, 3H), 1.5 3.0 (m, 15H), 3.50 4.13 (m, 6H); 4.76 (s, 2H), 5.25 5.31 (m, 3H), 5.63 (s, 1H), 6.70 (d, J ¼ 9.0 Hz, 2H), 6.98 (d, J ¼ 9.0 Hz, 2H), 7.30 (d, 2H) FT-IR (KBr, cm1) ¼ 3340, 2912, 1630, 1510, 1364, 1217, 1089, 1005, 1035, 999, 806, 706 MS (NBA): m/z: 452.27 [M þ H]

1

3.

Preparation of Metal Oxide Nanotubes

Three milligrams apiece of the Step 1 and Step 2 products were dissolved in 10 ml of water and 1 ml of methanol by heating the solution to 70 C. This mixture was then treated with tetraethoxysilane (20 mg) followed by benzylamine (6 mg). A gel that formed during gradual cooling of the mixture stood uninterrupted at ambient temperature for seven days. The sample was then sintered in a nitrogen gas atmosphere first for two hours at 200 C and then for four hours at 500 C, and metal oxide nanotubes were isolated.

ANALYTICAL 1. The metal oxide nanotubes were analyzed by scanning electron microscopy and field emission scanning electron microscopy, which indicated the presence of a double helix. 2. Hydrogen adsorption–desorption isothermal curves for the double-spiral silica nanotubes and cylindrical silica were not provided by the author.

Notes

349

NOTES 1. When hexylamine was used in place of benzylamine in Step 3, double–spiral silica nanotubes were also obtained. 2. Kornilovich [1] prepared linear aliphatic-, (I), and dimethylsiloxy-functionalized silicon oxide nanowire designed to adsorb and store up to 6.5% hydrogen. Grafted linear aliphatic chain

Adsorbed hydrogen

Silicon oxide nanowire

(I) 3. Kiang [2] prepared single-walled nanotubes consisting of up to 30% metallic bismuth and cobalt, which were thread-like at ambient temperatures and pressures. The synthetic method entailed heating a mixture of 90% graphite powder and 5% apiece of cobalt catalyst and bismuth co-catalyst in an electric arc. 4. Zhang [3] prepared iridium oxide nanotubes using metal-organic chemical vapor deposition with (methylcyclopentadienyl)(1,5-cyclooctadiene) iridium, (I), followed by heating from 200 C to 500 C. 5. Bronikowski [4] used poly(styrene-b-methylmethacrylate) to form iron-rich and iron-deficient nanowires. In this process poly(styrene-b-methylmethacrylate) and FeCl3 were dissolved in acetone and then spin-coated onto a substrate and heated so that the block copolymer formed pillars of PMMA in a PS matrix. Under these conditions Fe3þ migrated to the more polar PMMA region. Once this composite was heated, single-wall carbon and iron-rich nanotubes were formed. 6. Olesik [5] prepared high-yield low-dispersity nanospheres using selfpolymerizing end-capped 1,8-dihydroxymethyl-1,3,5,7-octatetrayne by heating to 70 C for 24 hours using 0.04 wt% phenyltrimethyl amine chloride as the surfactant. 7. Methods for monitoring the amount of adsorbed hydrogen on palladium mesowire are described by Monty [6] and Penner [7].

350

Metal Oxide Nanotube and Process for Production Thereof

References 1. 2. 3. 4. 5. 6. 7.

P. Kornilovich,US Patent 7,135,057 (November 14, 2006) C.-H. Kiang US Patent 7,112,315 (September 26, 2006) F. Zhang et al., US Patent 7,098,144 (August 29, 2006) M.J. Bronikowski et al., US Patent 7,115,305 (October 3, 2006) S.V. Olesik et al., US Patent Application 2006-0223947 (October 5, 2006) G. Monty et al., US Patent 7,104,111 (September 12, 2006) R.M. Penner et al., US Patent Application 2003-0079999 (May 1, 2003)

C. Nanotube Dispersant

Title: Methods for the Synthesis of Modular Poly (Phenyleneethynlenes) and Fine-Tuning the Electronic Properties Thereof for the Functionalization of Nanomaterials Author:

H. Ait-Haddau et al., US Patent Application 2006-0054866 (March 16, 2006)

Assignee:

Zyvex Corporation (Richardson, TX)

SIGNIFICANCE Carbon nanotubes have limited solubility in most organic solvents. Phenyleneethynylene derivatives have been prepared and used to noncovalently functionalize and solubilize these materials by means of the electron donor/electron acceptor characteristics of the polymer backbone.

351

352

Methods for the Synthesis of Modular Poly(Phenyleneethynlenes)

REACTION OH

OC 10H21

OC 10H21

i

OC 10H21

ii

OH

OC 10H21

I

I

iii

(H3C) 3Si

Si(CH 3)3 C10H21 O

C10H21 O

OC 10 H21

iv C10 H21 O

Intermediate Br

Br

Br CO 2H

COCl

v

HO 2C

ClOC Br

t-C 4H9-OOC

Br OC 10 H21

Br OC 10H21

viii

HO 2C

vii

Intermediate

CO 2H

a C10 H21 O

COO-t-C 4H9

vi

COO-t-C 4H9

a C10H21 O

t-C 4H9-OOC

i: 1,4-Hydroquinone, potassium carbonate, acetonitrile, 1-bromodecane ii: Potassium iodate, acetic acid, water, sulfuric acid, sodium thiosulphate iii: Diisopropylamine, copper (I) iodide, dichlorobis(triphenylphosphine)palladium(II), trimethyl-silylacetylene iv: Methanol, potassium hydroxide v: Oxalyl chloride, DMF vi: THF, t-butanol, pyridine, CH2Cl2 vii: Toluene, diisopropylamine, tetrakistriphenylphosphine palladium, copper(I) iodide viii: Water, potassium hydroxide, toluene, ethanol

EXPERIMENTAL 1.

Preparation of 1,4-Didecyloxybenzene

A flask was charged with 1,4-hydroquinone (0.4 mol), K2CO3 (1.2 mol), and 500 ml of acetonitrile and then treated with 1-bromodecane (1.0 mol). This solution was refluxed for 48 hours and poured while hot into a flask containing 1.5 liter water. The beige precipitate was collected by filtration using a Buchner funnel, washed with 1.0 liter water, and dried. The solid was dissolved in 250 ml of hot hexanes and re-precipitated in 1.5 liter of ethanol. The solid was then washed with cool ethanol, dried, and the product was isolated in 97% yield as a fluffy white solid. 1

HNMR (CDCl3) d 6.83 (s, 4H), 3.92 (t, J ¼ 6.6 Hz, 4H), 1.73 (m, 4H), 1.45 (m, 4H), 1.30 (m, 22H), 0.91 (t, J ¼ 6.7 Hz, 6H).

Experimental

2.

353

Preparation of 1,4-Didecyloxy-2,5-Diiodobenzene

A reaction vessel was charged with potassium iodate (0.066 mol), iodine (0.132 mol), 700 ml of acetic acid, 50 ml of water, and 15 ml of sulfuric acid and then treated with the Step 1 product (0.132 mol) and refluxed for 8 hours. The purple solution was cooled to ambient temperature and treated with a 100 ml saturated solution of sodium thiosulphate. The beige-brown precipitate was collected by filtration, washed with 700 ml of water and 500 ml of ethanol, and dried. This solid was dissolved in 300 ml of hot hexanes and precipitated in 1.5 liter of ethanol. The precipitate was collected by filtration, washed with 1.0 liter ethanol, and dried; the product was isolated in 92% yield as a white solid. HNMR (CDCl3) d 7.21 (s, Ph, 2H), 3.94 (t, J ¼ 6.4 Hz, OCH2, 4H), 1.82 (m, CH2, 4H), 1.47 (m, CH.sub.2, 4H), 1.29 (m, CH2, 22H), 0.90 (t, J ¼ 6.72 Hz, CH3, 6H) 13 CNMR (CDCl3) d 152.8, 122.7, 86.2, 70.3, 31.9, 29.5, 29.3, 29.2, 29.1, 26.0, 22.6, 14.1.

1

3.

Preparation of 1,4-Didecyloxy-2,5-bis-(Trimethylsilylethynyl)Benzene

A reaction vessel containing 1.5 liter of diisopropylamine was treated with the Step 2 product (0.1557 mol), CuI (7.78 mmol), and dichlorobis(triphenylphosphine)palladium(II) (7.78 mmol). The mixture was stirred for 10 minutes and then treated with the slow addition of trimethylsilylacetylene (0.342 mol) at ambient temperature and refluxed for 8 hours. After cooling, the mixture was diluted with 500 ml of hexanes, filtered through a 4 cm silica gel plug, concentrated, and precipitated in 3.0 liter of CCl3H/ethyl alcohol, 1:1. The solid was filtered, washed with 250 ml apiece of water and ethanol, and dried; the product was isolated in 91% yield. HNMR (CDCl3) d 6.85 (s, Ph, 2H), 3.93 (t, J ¼ 6.4 Hz, OCH2, 4H), 1.78 (m, CH2, 4H), 1.27 (m, CH2, 22H), 0.88 (t, J ¼ 6.42 Hz, CH.sub.3, 6H), 0.26 (s, 18H) 13 CNMR (CDCl3) d 154.0, 117.2, 113.9, 101.0, 100.0, 69.4, 31.9, 29.6, 29.5, 29.4, 29.3, 26.0, 22.6, 14.1, 0.17.

1

4.

Preparation of 1,4-Diethynyl-2,5-Didecyloxybenzene

A flask containing 200 ml of methanol and 120 ml of 20% KOH was added to the Step 3 product (137.21 mmol) dissolved in 500 ml of THF at ambient temperature and stirred overnight. The solution was concentrated, and the residue was diluted with 400 ml of ethanol whereupon a yellow solid formed. The solid was isolated, washed with 250 ml ethanol, and dried; the product was isolated in 99.7% yield as a yellow solid. HNMR (CDCl3) d 6.96 (s, Ph, 2H), 3.98 (t, J ¼ 6.58 Hz, OCH2, 4H), 3.34 (s, CCH, 2H), 1.82 (m, CH.sub.2, 4H), 1.52 (m, CH2, 4H), 1.31 (m, CH2, 22H), 0.88 (t, J ¼ 6.71 Hz, CH3, 6H) 13 CNMR (CDCl3) d 153.9, 117.7, 113.2, 82.4, 79.7, 69.6, 31.9, 29.5, 29.3, 29.1, 25.9, 22.6, 14.1

1

5.

Preparation of 1,4-Dibromo-2,5-Dicarboxylic Acid Chloride Benzene

At ambient temperature oxalyl chloride (1.244 mol) was slowly added to a suspension of the dibromo acid (0.518 mol) in CH2Cl2. This mixture was then treated with several

354


drops of dry DMF and refluxed for 12 hours. After the mixture was concentrated to half its original volume, it was treated with 500 ml of hexanes. A pale yellow precipitate formed, which was isolated and washed with 250 ml of hexanes, and the product was isolated in 98.8% yield. 6.

Preparation of 1,4-Dibromo-2,5-t-Butoxycarboxybenzene

A solution of the Step 5 product (272.72 mmol) dissolved in 25 ml of THF was added over 45 minutes to a solution of t-butanol (110.9 mmol) and pyridine (110.9 mmol) in 100 ml of CH2Cl2 at 5 C. The reaction mixture was gradually warmed to ambient temperature, stirred overnight, and then concentrated. The residue was diluted with a 100 ml mixture of water/methanol, 1:1, whereupon a white precipitated formed. The precipitate was washed with 100 ml 1.8M KOH and 100 ml of cooled water/methanol, 1:1, dried, and the product was isolated in 76% yield. 7. Preparation of Poly[1,4-Dibromo-2,5-t-Butoxycarboxybenzene)co-(1,4-Diethynyl-2,5-Didecyloxybenzene)Phenyleneethynylene] A flask was charged with 35 ml of toluene/diisopropylamine, 3:2, respectively, the Step 4 product (1.964 mmol), the Step 6 product (1.785 mmol), (Ph3P)4Pd (1 mol%), and CuI (2.5 mol%). The mixture was then stirred at ambient temperature for 30 minutes, warmed to 70 C for 90 minutes, and then added to a flask containing 250 ml of the stirring methanol. This mixture was stirred for 2 hours at ambient temperature and an orange precipitate was isolated. The solid was washed with 100 ml of a methanol/ammonium hydroxide solution, 1:1, 100 ml of methanol, and then dried, and 1.25 g product was isolated as an orange solid. The polymer repeat unit was estimated by 1 H NMR to be approximately 60 with a polydispersity index of about 1.4 as determined by GPC. 8. Preparation of Poly[1,4-Dibromo-2,5-Hydroxycarboxybenzene)co-(1,4-Diethynyl-2,5-Didecyloxybenzene)Phenyleneethynylene] Potassium hydroxide (1.0 g) was dissolved in a mixture of 30 ml of refluxing toluene/ ethanol, 1:1, and then treated with the Step 7 product (1.0 g) and refluxed 3 hours. The mixture was next treated with 10 ml of water, refluxed an additional 24 hours, cooled, and filtered, and the filtrate was acidified using 3M HCl. An orange precipitate was isolated, washed with 100 ml of water, and dried, and 0.75 g of product was isolated. The product was soluble in diethyl ether, THF, DMF, acetone, methyl ethyl ketone, isopropyl alcohol, methanol, ethanol, and related solvents having pH > 8.

DERIVATIVES A second donor/acceptor phenyleneethynylene derivative was also prepared.

Notes

O

355

O O

O

O O

O

O

O

O

C10H21O OC10H21

a

NOTES 1. Smalley [1] solubilized and separated metallic nanotubes by initially dispersing these materials with polyvinyl pyrrolidone or polyvinyl pyrrolidone copolymers and then separating them by electrophoresis. 2. Wise [2] prepared selected polyimides, (I), that formed dispersions of carbon nanotubes exhibiting long-term stability. Nanocomposites produced from these dispersions were useful in the fabrication of lightweight aerospace structures. O

CN O

O

N O

O

O N

n

O

(I) 3. Diner [3] demonstrated that RNA-dispersed carbon nanotubes were more readily oxidized than those dispersed in TritonÒ X405, a non-ionic surfactant. 4. Blanchet-Fincher [4] determined that when carbon nanotubes were dispersed in a conductive polyaniline matrix, fewer nanotubes were needed to increase electrical conductivity.

356


References 1. R.E. Smalley et al., US Patent 7,074,310 (July 11, 2006) and US Patent Application 2006-0231399 (October 19, 2006) 2. K.E. Wise et al., US Patent Application 2006-0270777 (November 30, 2006) 3. B.A. Diner et al., US Patent Application 2005-0232844 (October 20, 2005) 4. G.B. Blanchet-Fincher, US Patent Application 2005-0165155 7,169,535 (July 28, 2005)

XVI. NEW SYNTHETIC METHODS A. Compounds a.

18

F-Fluorobromomethane

Title: Solid-Phase Preparation of [18 F] Fluorohaloalkanes Author:

F. Brady et al., US Patent 7,223,891 (May 29, 2007)

Assignee:

Hammersmith Imanet, Ltd. (London, GB)

SIGNIFICANCE An eight-step method for the solid-phase preparation of 18 F-fluoro-bromoalkanes is described.


358

Solid-Phase Preparation of [18 F] Fluorohaloalkanes

REACTION F2 C

I

C F2

F2 C

C F2

i

I

ClO2S

O2 S

N

O2 S

C F2

F2 C

C F2

F2 C

F2 C

C F2

O

ii

SO2Cl

KO3S

iv

HO3S

SO2

a

C F2

C F2

F2 C

F2 C

C F2

C F2

SO3K

SO3H

iii

a viii

vii

N

F2 C

F2 C

SO3Na

vi

i: ii: iii: iv: v: vi: vii: viii:

C F2

F2C CF2 CF2 F2C

v

a

F2 C

O2 S

C F2

F2 C

C F2

F2 C

SO2Cl

N

O2 S

C F2

F2 C

C F2

F2 C

O SO2

18

FCH2Br

Br

Sodium dithionite, sodium hydrogen sulphate, water, acetonitrile, chlorine gas Potassium hydroxide, water Water, Amberlyst 15 resin Phosphorous pentoxide Polystyrene resin, di-isopropyethyl amine Phosphorous pentachloride, CH2Cl2 Bromomethanol, THF Acetonitrile, kryptofix, potassium carbonate, and [18 F]-fluoride

EXPERIMENTAL 1.

Preparation of Perfluorobutane-1,4-bis-Sulphonylchloride

A mixture consisting of 1,4 diiodoperfluorobutane (53.2 mmol), sodium dithionite (117.2 mmol), and sodium hydrogen sulphate (152.4 mmol) in 36 ml apiece of water and acetonitrile was stirred 2 hours at ambient temperature and then filtered. The filtrate was concentrated, and the residue was added to 100 ml water. The solution was then treated with chlorine gas at 0 C until the color of iodine disappeared. The mixture was extracted with 100 ml of CH2Cl2, and the organic phase was washed with water, dried, and concentrated. After re-crystallization from hexane the product was isolated as off-white needles. 19

F NMR (CDCl3) d

104.4,

119.1.

Experimental

2.

359

Preparation of Perfluorobutane-1,4-bis-Sulphonate Dipotassium Salt

A solution of potassium hydroxide (5 eq) in 19 ml of water was reacted with the Step 1 product (35 mmol) at 85 C to 90 C for 4 hours. It was cooled overnight and filtered; the solids were washed with cooled water and dried, and the product was isolated. 3.

Preparation of Perfluorobutane-1,4-bis-Sulphonic Acid

The Step 2 product (34.2 mmol) was dissolved in 100 ml of hot water and added to an ion exchange column containing an Amberlyst 15 resin. The column was slowly washed with distilled water and the first 300 ml of aqueous solution was collected. The solution was concentrated, the residue dried, and the product isolated in 88% yield. 19 1

F NMR (CDCl3) d 114.00, H NMR (CDCl3) d 8.00

4.

120.11

Preparation of Perfluorobutane-1,4-bis-Sulphonic Acid Anhydride

The Step 3 product (30 mmol) was mixed with P2O5 (10 eq), heated to between 140 C and 180 C, and distilled under reduced pressure. The crude product was isolated by distillation and purified by re-distillation. 19

F NMR (CDCl3) d

114.7,

121.3.

5. Preparation of Polystyrene-g-(Benzyl-Ethyl-Sulfonamide)OctafluoroButane-1-Sulfonic acid The polystyrene resin (202 mg) previously swollen in 2 ml of CH2Cl2 and then suspended in 2 ml of CH2Cl2 was treated with the Step 4 product (5 eq) and 0.174 ml di-isopropyethyl amine and stirred overnight at ambient temperature. The solvent was removed by filtration and the resin was washed with consecutive additions of 5 ml apiece with CH2Cl2, methanol, DMF, water, methanol, and CH2Cl2. The resin was then treated twice with 2 ml of 1M NaOH in THF and water before washing with consecutive 5 ml portions of methanol, CH2Cl2, and methanol. The product was isolated after drying under high vacuum. 19

F NMR (CDCl3) d

105.7,

121.8.

6. Preparation of Polystyrene-g-(Benzyl-Ethyl-Sulfonamide)OctafluoroButane-1-Sulfonyl Chloride A portion of the Step 5 product was swollen with 2 ml of CH2Cl2, washed consecutively with 5 ml of 1 M HCl, and 10 times with 5 ml of THF and water to give the free sulphonic acid. The resin was then washed consecutively with CH2Cl2, methanol, and THF before drying under high vacuum. The material was then suspended in CH2Cl2 and treated with excess phosphorous pentachloride. The mixture was suspended for 2 hours, filtered, and washed with CH2Cl2, and THF, and the product was isolated. 19

F NMR [gel phase] d

121.0,

114.8,

113.4

360

Solid-Phase Preparation of [18 F] Fluorohaloalkanes

7. Preparation of Polystyrene-g-(Benzyl-Ethyl-Sulfonamide) Octafluoro-Butane-1-Sulfonyl Bromomethane A solution of bromomethanol dissolved in THF was added to a portion of the Step 6 product previously swollen in THF. The mixture was then treated with potassium t-butoxide dissolved in THF, and the suspension was stirred overnight at ambient temperature. The mixture was next filtered, the resin washed consecutively with CH2Cl2 and THF, and dried, and the product was isolated. 8.

Preparation of 18 F-Fluorobromomethane

A cartridge was charged with the Step 7 product dissolved in acetonitrile containing kryptofix, potassium carbonate, and [18 F]-fluoride. The mixture was then heated to 85 C for 10 minutes and filtered. The solution was passed onto a C18 solid-phase extraction cartridge and washed with water to remove acetonitrile, kryptofix, and potassium carbonate. Additional acetonitrile was used to wash the radiofluorinated agent off the extraction cartridge, and the product was isolated. NOTES 1. Solid-phase electrophilic fluorination was previously used by Luthra [1] to prepare an 18 F-L-dopa analogue, (I), for the in situ release of 18 F-L-fluorodopa.

HO2C NH2

18

OH

F OH

(I)

2. Sn2 displacement of the corresponding tosylate intermediate with 18 F anion was used by Mertens [2] and Chen [3] to prepared 18 F-Alanine, (II), and 18 F-tyrosine, (III), derivatives, respectively.

NH2 NH2 18

CO2H

F

18

CO2H

(II)

F

O

(III)

Notes

References 1. S.K. Luthra et al., US Patent 7,115,249 (October 3, 2006) 2. J.J.R. Mertens, US Patent 7,189,383 (March 13, 2007) 3. J.T. Chen et al., US Patent 7,138,540 (November 21, 2006)

361

b. Nitrogen Heterocyclics

Title: Vinyl Sulphone Modified Polymer Author:

D. Gani et al., US Patent 7,183,367 (February 27, 2007)

Assignee:

N.V. Organon (Oss, NL)

SIGNIFICANCE A two-step method for the combinatorial synthesis of amines and amino alcohols using vinylsulfomethylpolystyrene is described. This solid-phase synthetic route requires very few reagents for the permutational synthesis of new heterocyclic amine derivatives. REACTION i

Cl

ii

OH

S

S O2 iv Notes 1,2

iii

OH

S O2

Merrifield resin

Br O vi

N S O2

Not isolated

S O2

N OH

vii

N S O2

+

N

362

+

N

OH

viii

v

S O2

_

Br

S O2

N

S O2

+

N N

Experimental

i: ii: iii: iv: v: vi: vii: viii:

363

2-Hydroxyethanethiol, potassium carbonate, pyridine, DMF 3-Chloroperbenzoic acid, CH2Cl2 Phosphorous tribromide, CH2Cl2 Tetrahydroquinoline, allyl bromide, DMF Potassium carbonate DMF, 4-piperazinoacetophenone Phenylmagnesium bromide, THF Potassium carbonate

EXPERIMENTAL 1.

Preparation of 2-Hydroxyethyl-Thiomethyl-Polystyrene

A slurry of the Merrifield resin (2.9 mmol) in 20 ml of dry DMF was treated with 2-hydroxy-ethanethiol (15.25 mmol), K2CO3 (14.5 mmol), and pyridine (12.9 mmol), and the suspension was stirred for 4 hours at 95 C. It was then left stirring overnight at 20 C. The resin was filtered and washed extensively with DMF, CH2Cl2, water, water/ methanol, 1:1, and methanol. The material was dried under vacuum at 50 C and 3.92 g of product were isolated. FTIR (cm1) in KBr): 3450 (br, OH), 1601, 1493, 1453 (st, polystyrene), 1060 (m), 1027 (m) Sulfur analysis: 2.12% (max 2.24%)

2.

Preparation of 2-Hydroxyethyl-Sulfomethyl-Polystyrene

The Step 1 product (0.7 mmol) in CH2Cl2 was treated with 3-chloroperbenzoic acid (5.2 mmol) and the suspension was heated at 35 C for a brief period and then stirred at 20 C for 2 days. After filtration the resin was washed with DMF, CH2Cl2, water, water/ methanol, 1:1, and finally methanol. After drying at 50 C under vacuum, 1.51 g of product was isolated. FTIR (cm1) in KBr): 3511 (br, OH), 1601, 1493, 1453 (st, polystyrene), 1317, 1119 (st, SO.sub.2), 1061 (m), 1029 (m). Sulfur analysis: 2.76% (max 2.19%)

3.

Preparation of 2-Bromoethyl-Sulfomethyl-Polystyrene

The Step 2 product (0.65 mmol) suspended in 25 ml of dry CH2Cl2 was treated with PBr3 (2.28 mmol) at ambient temperature for 12 hours and then filtered, washed with 200 ml of CH2Cl2, and air dried, and the product was isolated. FTIR (cm1) in KBr): 1727 (m), 1600, 1491, 1450 (st, polystyrene), 1320, 1119 (st, SO2)

364

Vinyl Sulphone Modified Polymer

4. Preparation of Vinylsulfomethylpolystyrene and N-Allyl Tetrahydroisoquinoline HBr The Step 3 product was mixed with 20 ml of DMF, and tetrahydroquinoline (5.7 mmol) was added. The mixture was stirred at ambient temperature for 24 hours. After filtering, the material was washed with DMF, methanol, CH2Cl2, and methanol and then dried. This material (0.5 mmol) was re-suspended in 10 ml of DMF, treated with allyl bromide (150 mm) and stirred 5 days at ambient temperature. It was then filtered and washed with 100 ml apiece of DMF and CH2Cl2. It was further treated with di-isopropylethyl amine (1.00 mmol) in 25 ml of CH2Cl2 and stirred 2 days at ambient temperature. The solid was isolated by filtration and then washed with CH2Cl2 and methanol; 59% analytical pure product was isolated. 5.

Preparation of N-Allyl Tetrahydroisoquinoline

The Step 4 product was liberated from its HBr salt by treatment with 10 ml of a 2M K2CO3 solution and then extracted using EtOAc. The organic layer was dried using K2CO3, filtered, and concentrated; the product was isolated in 68% yield. 6. Preparation of Sulfomethyl-2-(40 -Piperazinoacetophenone) Ethyl-Polystyrene The Step 3 product (0.36 mmol) slurried in 5 ml of DMF was treated with 4-piperazino-acetophenone (0.47 mmol) and agitated on a tube rotator for 24 hours. The resin was drained, washed with DMF, CH2Cl2, and methanol, and 278 mg of product were isolated. H-NMR (d 300 MHz, CDCl3): 12 (s, br, 1H, HBr), 7.30 7.08 (m, 4H, aromatics), 6.33 (ddt, 1H, Jcis ¼ 10.0 Hz, Jtrans ¼ 17.15 Hz, J¼7.14 Hz, CH2CH¼CH2), 5.61 5.5 (m, 2H, CH2—CH¼CH2), 4.35 (br m, 2H, NCH2-Ph), 3.76 (d, 2H, 3J¼7.14 Hz, CH2CH¼CH2), 3.42 (br m, 4H, NCH2CH2-Ph) 13 C-NMR (d 74.76 MHz, CDCl3): 130.54, 129.13 (.sup.2C, .sup.7C), 128.78, 127.74, 127.05, 126.44, 126.38, 126.25 (remaining aromatics and double bond), 57.53 (NCH.sub.2-Ph), 51.43 (NCH2CH.dbd.CH2), 48.33 NCH2— CH2-Ph), 24.22 (NCH2CH2-Ph) Elemental analysis Found C, 56.57; H. 6.57; N, 5.42%. C12H16BrN requires C, 56.71; H, 6.34; N, 5.51% MS m/z (CI) 174 (M.sup.þ-Br.sup., 100%). FTIR (KBr cm1): 1651 (st, C¼O), 1597, 1491, 1449 (st, polystyrene), 1305, 1114 (st, SO2) 1

7. Preparation of Sulfomethyl-2-[4-Piperazino-4-(a-Methyl-aPhenyl-Benzylalcohol-)]Ethylpolystyrene A slurry of the Step 6 product (0.36 mmol) in 5 ml of dry THF was treated with 0.36 ml of 1M phenyl-magnesium bromide in THF at 0 C and then stirred for 2 hours at ambient temperature. The mixture was next quenched with 5 ml of 50% aqueous NH4Cl, and the material isolated. The resin was washed four times with water, THF, CH2Cl2, and methanol and then dried; the product was isolated in quantitative yield. FTIR (KBr cm1): 3450 (vst, OH), 1600 (st, polystyrene), 1310, 1139 (st, SO2)

Notes

8.

365

Preparation of N-Allyl-4-Piperazino-4-(a-Methyl-a-Phenyl-Benzylalcohol)

The Step 7 product was treated with Na2CO3 and the product isolated after being worked up according to the Step 5 procedure.

DERIVATIVES The following derivatives utilized hydroxymethyl polystyrene as the polymeric substrate in preparing N-allyl derivatives. X Cl

O

X

S O2

N CO2C2H5 N

NOTES 1. Polymer-benzyl vinyl sulfone could either be trapped in situ or isolated and reacted separately. 2. The preferred dehydrohalogenation reagent was diisopropylethylamine. 3. In an earlier investigation by the author [1] polystyrene-g-acrylamide, (I), was used in the combinatorial synthesis of heterocyclic amines as illustrated below. H N

CO2C2H5

H N

i

ii

N O

O

(I)

CO2C2H5

O2N

iii

N

+ N

H N

CO2C2H5 _

Br

O NO2

i: 4-Piperidinecarboxylic acid, ethyl ester, DMF ii: 4-Nitrobenzyl bromide, DMF iii: THF, diethanolamine

366

Vinyl Sulphone Modified Polymer

4. Vaultier [2] prepared functionalized oxonium salts, (II), as soluble supports for preparing the higher amino acid intermediate, (III). In an earlier investigation functionalized soluble oxonium salts prepared by Vaultier [3] were used in Diels-Adler, trans-esterification, trans-amidation, Heck, and Suzuki reactions.

X

_

+ (H3C)HN

X

a OH

(II)

+ (H3C)HN

_

O

_

X

= Cl, BF4, PF6

a = 0–3

a O

(III)

References 1. D. Gani et al., US Patent 6,486,354 (November 26, 2002) and US Patent Application 2003-0138846 (July 24, 2003) 2. M. Vaultier et al., US Patent Application 2007-0043234 (February 22, 2007) 3. M. Vaultier et al., US Patent Application 2006-0128996 (June 15, 2006)

c. Nonsymmetrical Peroxides

Title: Ketone Peroxide Derivatives, Their Preparation and Use Author:

A. G. Van De Bovenkamp-Bouwman et al., US Patent 7,078,553 (July 18, 2006)

Assignee:

Akzo Nobel N.V. (Arnhem, NL)

SIGNIFICANCE A two-phase method for preparing up to 90% monoperoxy esters or carbonates using a 2:1 molar ratio of methyl isobutyl ketone peroxide and acid chloride, respectively, is described. Nonsymmetrical diperoxides were also prepared by reacting the monoperoxy esters or carbonates with a different second mole of acid chloride. REACTION O Cl

i

HOO

O

O

ii O

Note 1

O O

O

O

O O

i: Methylisobutyl ketone peroxide, diethyl ether, sodium hydroxide, potassium hydroxide, decane, sodium chloride, water ii: 2-Ethylhexanoyl chloride, decane, sodium chloride, water, potassium hydroxide, sodium sulfite EXPERIMENTAL 1. Preparation of 1-Hydroperoxy-1,3-Dimethyl Butyl Peroxy-2-Ethyl Hexanoate A 200-ml beaker was charged of 98.5% methylisobutyl ketone peroxide (50 g) in diethyl ether, decane(25 g), 25% aqueousNaCl(10 g),and20 mlofdemineralizedwater.ThepH was adjusted to 13.5 using 45% aqueous KOH at 8 C to 12 C and then treated with 367

368

Ketone Peroxide Derivatives, Their Preparation and Use

2-ethylhexanoyl chloride (0.107 mole) for over 25 minutes. Sufficient amount NaOH was added to maintain the pH >13.5, and the mixture stirred for 60 minutes at 5 C to 8 C. The two-phase system was separated, and the organic layer washed with 4M NaOH and 3% to 6% NaHCO3 and then dried over MgSO4. After evaporation of the solvent the productwasisolatedin85%yield,havinganactiveoxygencontentof5.02%withamono/ di peroxide product ratio of 80:20, respectively. 2.

Preparation of 2,2-Bis(2-Ethylhexanoylperoxy)-4-Methyl Pentane

A 200-ml beaker was charged with the Step 1 product (50 g) dissolved in n-decane, 25% aqueous NaCl (10 g), and 20 ml of demineralized water. The mixture pH was adjusted to 13.5 using 45% aqueous KOH at 8 C to 12 C and then treated with 2-ethylhexanoyl chloride (9.8 g) for over25minutes. A sufficientamountNaOH was addedtomaintain the pH >13.5, and the mixture was stirred for 60 minutes at 5 C to 8 C. After the water layer was separated, the remaining hydroperoxide was reduced with sodium sulphite. The organic layer was washed with 3% to 6% NaHCO3 and dried using MgSO4. After evaporation of the solvent the product was isolated in 93% yield having a mono/di peroxide of 1:99, respectively, and an oxygen content of 3.77%. DERIVATIVES TABLE 1. Reaction scoping for the preparation of 1-hydroperoxyperesters prepared by condensing methylisobutyl ketone peroxide with an acid chloride at a 1:1 molar ratio.

Entry

2

Structure

HOO O O

Ratio Acid Chloride/Peroxide

Peroxy Product Ratio (mono/di)

Yield (%)

1:2

9:1

—

5:1

1:1

—

1.7:1

4:1

59

2:1

6:4

80

O

3

HOO O O O

5

6

HOO O O O

HOO O

O O

Notes

369

TABLE 2. Reaction scoping for the preparation of symmetrical and asymmetric diperesters prepared by reacting 1-hydroperoxyperester with a second mole of a selected acid chloride. Entry

Structure

O

8a

O

O

O

O

Application

90

Curing agent for unsaturated polyesters

90

Initiator in free radical polymerization of styrene

96

Used in the emulsion polymerization of polyvinyl chloride

O

O

8b

Yield (%)

O

O

O

O O

O

9

O

O

O

O O

NOTES 1. Additional mono- and diperoxide derivatives of the current invention are disclosed by the author [1] in an earlier investigation. 2. The mixed peroxides, t-butylperoxy 2-ethylhexyl, (I), and isobutanoyl-lauroyl peroxide, (II), were prepared by Overkamp [2] and Tammer [3], respectively, using t-butyl peroxide and isobutanoyl chloride with 30% hydrogen peroxide in the presence of sodium hydroxide in a two-phase system. Both agents were used in vinyl chloride polymerization.

O O

O

O O

(I)

O

O

C11H23

(II)

3. 3-Alkyl-3,7,7-trimethyl-1,2,4-trioxacycloheptane derivatives, (III), were used by Hogt [4] in preparing high-solid acrylic, styrenic, and LDPE-type resins.

370

Ketone Peroxide Derivatives, Their Preparation and Use

O R O

(III)

O

R = C2 H 5 , i- and n-C 3H7 i-C4H9

References 1. A.G. Van De Bovenkamp-Bouwman et al., US Patent 6,770,774 (August 3, 2004) 2. J.W.A. Overkamp et al., US Patent Application 2004-0049070 (March 11, 2004) and US Patent 6,610,880 (August 26, 2003) 3. M.C. Tammer et al., US Patent 7,087,693 (August 8, 2006) 4. A.H. Hogt et al., US Patent 6,720,398 (April 22, 2004) and US Patent 6,566,391 (May 20, 2003)

B. Polymers a. Biogradable Polyesters

Title: Simplified Method of Producing Biodegradable Aliphatic Polyesters Author:

F. Farachi et al., US Patent 7,253,250 (August 7, 2007)

Assignee: Ministero dell ‘Universita’e della Ricerca Scientifica e Technologica (Rome, IT)

SIGNIFICANCE High molecular weight biodegradable polyalkyl sebacate esters have been prepared using a 1:1 molar reagent ratio of diacid, diol, and monobutylstannoic acid as the reaction catalyst. The initial esterification entails heating the mixture to 190 C followed by deglycolation under vacuum by heating the reaction mixture to 230 C.

REACTION O HO2C

CO2H 8

i

HO

4O

O 8

O

O O

4O a

CO2H 8

Not isolated

ii Note 1

O 8

O

4O b

b >> a

i: Monobutylstannoic acid, sebacic acid, butanediol

EXPERIMENTAL Preparation of Polybutylene Sebacate A 25-liter steel reactor equipped with a mechanical stirrer, an inlet for a nitrogen stream, a condenser, and a connection to a vacuum pump was charged with sebacic acid 371

372

Simplified Method of Producing Biodegradable Aliphatic Polyesters

(5050 g), butanediol (2362.5 g), and monobutylstannoic acid (4 g) as reaction catalyst. The reaction was then gradually heated to 190 C and remained at this temperature for 210 minutes while 900 ml of water were collected. Thereafter the mixture was heated to 230 C over a period of 6 hours at 0.5 torr for deglycolation to occur. The reaction mixture was next cooled, and 6 kg of polymer was isolated having an inherent viscosity of 0.9 dl/g and a melt index of 40 g/10 min.

DERIVATIVES TABLE 1. High molecular weight polyalkyl sebacate esters prepared using a 1:1 molar reagent ratio of sebacis acid with a selected diol with monobutylstannoic acid as the reaction catalyst. Diol

Catalyst

Inherent Viscosity (dl/g)

Butanediol Hexanediol Ethanediol Decanediol

Dibutyl tin oxide Monobutylstannoic acid Monobutylstannoic acid Monobutylstannoic acid

0.58 1.13 1.24 1.2

Entry 1b 3 4 7

Melt Index (g/10 min) — 3 5 5

NOTES 1. Mixed biodegradable polysebacate esters containing hexandiol and neopentyl diol were previously prepared by the author [1] using monobutylstannoic acid as catalyst and the products used in film compositions. 2. Polybutandiol sebacate, polyhexandiol sebacate, polynonandiol sebacate, and polydecandiol sebacate esters were previously prepared by Bastioli [2] and used as biodegradable water vapor barriers. 3. Gross [3] prepared biodegradable polyoctamethylene sebacate containing 23 mol% blended glycolide by enzyme catalysis using Novozyme-435. References 1. F. Farachi et al., US Patent 6,562,939 (May 13, 2003) 2. C. Bastioli et al., US Patent 6,727,342 (April 27, 2004) 3. R.A. Gross et al., US Patent 6,972,315 (December 6, 2005)

b. Hydroaminomethylation Reactions

Title:

Hydroaminomethylation of Olefins

Author:

J. R. Briggs et al., US Patent 7,220,884 (May 22, 2007)

Assignee:

Dow Global Technologies, Inc. (Midland, MI)

SIGNIFICANCE Mono- and dihydroaminomethylation of olefins was performed with dicarbonyl-2,4pentanedionerhodium containing a monodentate phosphite ligand as the catalyst under moderate pressures. The reaction has high region-specificity with yields exceeding 90%.

REACTION N(CH3)2

i a

b

a

b

i: NeodeneRTM, THF, dicarbonyl-2,4-pentanedionerhodium, tris(2,4-di-t-butylphenyl)phosphite, dimethylamine

EXPERIMENTAL Aminomethylation Procedure A one gallon reactor was charged with the polyolefin NeodeneRTM (319 g) dissolved in 750 ml of THF. The reaction mixture was then treated with dimethylamine (222 g) and a solution of Rh(CO)2(acac) (3.7 g) and tris(2,4-di-t-butylphenyl)phosphite (46.2 g) dissolved in 400 ml of THF so that the final rhodium concentration was 900 ppm by weight. The mixture was heated to 80 C and pressurized to 600 psi with syngas and then stirred under these conditions for 7 hours. The reactor was cooled, excess 373

374

Hydroaminomethylation of Olefins

dimethylamine removed, and the product isolated in 99% yield as a colorless mobile liquid.

SYNTHETIC REACTIONS AND DERIVATIVES

a

i

a

HO

N

HO i: Diethanolamine

N(CH3)2

a

ii a

ii: Dimethylamine

iii

a

(C6H5CH2)N

a

iii: Dibenzylamine

NOTES 1. Riermeier [1] prepared amines in high yields by reductive amination of carbonyl-containing compounds using hydrogen and primary or secondary amines with [Rh(COD)Cl]2 and 2,20 -bis[[bis(3-sulfophenyl)phosphino]-methyl]-4,40 ,70 ,70 -tetrasulfo-1,10 -binaphthyl octasodium as catalysts as illustrated below. When the reaction was duplicated using [Ir(COD)Cl]2 alone, only 6% 2-butylamine was incorporated.

i O

+ OH

NH2

7:3 i: Hydrogen, ammonia, heptane, with [Rh(COD)Cl]2, 2,20 -bis[[bis(3-sulfophenyl)phosphino]-methyl]-4,40 ,70 ,70 -tetrasulfo-1,10 -binaphthyl octasodium

Notes

375

2. Donsbach [2] prepared 3,3-diarylpropylamines by hydroformylation/hydrocarbonylation followed by reductive amination using (acetylacetonate)dicarbonylrhodium as illustrated below, beginning with 4-hydroxybenzoic acid, ethyl ester. N

CO2C2H5

O

iii

ii

i CO2C2H5

O

OH

OH

CO2C2H5

CO2C2H5

i: Phenylene acetylene, tin tetrachloride, tributylamine, 1,2-dichloroethane ii: Benzyl bromide, potassium carbonate, acetone iii: Diisopropylamine, (acetylacetonate)dicarbonylrhodium, tributylphosphine, dioxane 3. Aminoalkylation of polyisoprene as viscosity index improvers for crankcase oil using (acetylacetonate)-dicarbonylrhodium with carbon monoxide and hydrogen with aminopropyl morpholine was used by Coolbaugh [3] to prepare oil dispersants. References 1. T. Riermeier et al., US Patent 6,884,887 (April 26, 2005) 2. M. Donsbach et al., US Patent 6,809,225 (October 26, 2004) 3. T.S. Coolbaugh et al., US Patent 6,228,817 (May 8, 2001) and US Patent 6,103,676 (August 15, 2000)

c. Perdeuterated Polyiimides

Title: Perdeuterated Polyiimides, Their Process of Preparation, and Their Use as Materials Which Are Transparent within the Region from 2500 to 3500 cm Author:

E. Anselmi et al., US Patent 7,211,632 (May 1, 2007)

Assignee:

Commissariat a L’Energie Atomique (Paris, FR)

1

SIGNIFICANCE Deuterated aromatic polyimides having excellent mechanical, thermal, and optical properties and exhibiting infrared absorption transparency between 2500 and 3500 cm 1 have been prepared. These materials are useful in optical transmission and optical signal processing because of minimum optical losses associated with absorption. REACTION O O O

O

O O D3

D3

O

i Note 1

O

N D4

O

N D3

D3

a

O

i: d8-4-Phenylenediamine, N-methylpyrrolidone

EXPERIMENTAL In stoichometric amounts, perdeuterated biphenyldianhydride was added to a reaction vessel containing perdeuterated 4-phenylenediamine dissolved in anhydrous N-methylpyrrolidone and stirred at ambient temperature for 24 hours. A film of the 376

Derivatives

377

poly(amic-acid) solution was deposited on a sheet of glass and heated from 50 C to 80 C to dry. The film was then cyclized and annealed by heating between 100 C and 300 C at a heating rate of between 1 C and 5 C per minute. The sheet was last immersed in a water bath in order to detach the polyimide film from the glass sheet.

DERIVATIVES TABLE 1. dn-Polyimides prepared from perdeuterated dianhydrides and diamines and physical properties of the corresponding polymer.

Entry

dn-Dianhydride

dn-Diamine

O

O

Product 1 O

O

O D3

C–D Young Elongation Modulus at Break Absorbance (cm 1) (%) E (GPa)

ND2 D4

D3 O

8

20

2247

8

20

2255

4

20

2254

7

10

2251

3

60

2256

ND2

2

O

O

O

O

O D3

3

D3 O

D2N O

O

O

O D2N D4

O D3

D3

O

O

O

ND2

O D3

D4

O

O

O O

ND2

ND2

O

O O

D4

D3 O O

O

7

D4

O O D3

6

ND2

D3

D2N

D4

D4

O

Note: Percent conversions were not supplied by author.

ND2

378

Perdeuterated Polyiimides, Their Process of Preparation, and Their Use as Materials

NOTES 1. The perfluoropolyimide analogue, (I), of the current invention was previously prepared by Kawamonzen [1] and used as an optical waveguide element.

O

O

N F4

N F3

O

F3

a

O

(I) 2. To minimize optical propagation caused by light absorption of a harmonic overtone vibration mode, Kim [2] and Ding [3] prepared polyether, (II), and polysulfone, (III), derivatives, respectively, where the majority of hydrogen atoms were replaced by fluorine. F O

F

F2 C

O

O

F

F

F2 C 4

4

F

F

F

F O

a F

F

F

F

(II) F

F

F3C CF3

F

O

O

F

F

O2 S

F

F3C CF3

O

O

F

a F

F

F

F

F

F

F

F

(III)

3. Perfluoropolyimides (IV) prepared by Ando [4] were useful as optical waveguide circuits for printed wire-board interconnections. O

F

F

F O

F F

F F

O

N

N O

O

F

F

F

O

F

F

X

a F

X = O, S

F

(IV)


Y. Kawamonzen et al., US Patent 7,092,608 (August 15, 2006) and US Patent 7,082,244 (July 25, 2006) J.-H. Kim et al., US Patent 7,202,324 (April 10, 2007) J. Ding et al., US Patent 7,049,393 (May 23, 2006) S. Ando et al., US Patent 5,750,731 (May 12, 1998)

d. Polybutadiene (Meth)acrylates

Title: Polybutadiene (Meth)Acrylate Composition and Method Author:

J. A. Klang et al., US Patent 7,192,688 (March 20, 2007)

Assignee:

Sartomer Technology, Inc. (Wilmington, DE)

SIGNIFICANCE A stable ester consisting of polybutadiene diol having a molecular weight of 2200 daltons with termini capped with two moles of ethylene oxide and acrylic acid has been prepared. In the absence of ethylene oxide, capping of acrylated polybutadiene diol gelled and produced molecular weights of at least 40,000 daltons. After crosslinking the stable polybutadiene-EO-acrylate composition materials were used as a photopolymer printing plates.

REACTION HO

O

O

O

a

b

O

OH

i O

O

O

O a

b

O

O O

O

i: Heptane, methanesulfonic acid, hydroquinone monomethyl ether, acrylic acid

EXPERIMENTAL Preparation of Polybutadiene-Ethylene Oxide Diacrylate A reaction flask containing a Dean-Stark trap was charged with heptane (157 g), acrylic acid (43 g), methanesulfonic acid (3.2 gm), hydroquinone monomethyl ether 379

380

Polybutadiene (Meth)Acrylate Composition and Method

(1.9 g), and a ethylene glycol terminated polybutadiene resin (424 g) with a Mn of 2244 daltons. The mixture was heated to reflux to remove water and continued refluxing until water collection stopped. After removal of the strong acid catalyst, solvent, and excess acrylic acid, the product was isolated as a viscous light brown liquid.

DERIVATIVES TABLE 1. Physical properties of derivatized polybutadiene diol containing a acrylic acid termini.

Entry 1 2 3 4

Polybutadiene Sample

Moles Ethylene Oxide on PolyBd Termini

Krason LBH 2000 Krason LBH 2000 PolyBD diol PolyBD diol

2 2 0 0

Mw (daltons)

Bookfield Viscosity (mPas s(cPs) @25 C)

3,200 3,000 247,000 40,000

5600 11,100 Semi-gelled 54,000

Color 70 APHA 150 APHA Very dark Very dark

Note: In the absence of ethylene oxide capping unregulated polymerization occurred.

NOTES 1. PolyBd diol capped with two moles of ethylene oxide has also been used to prepare stable isocyanate-terminated pre-polymers by Bechara [1] using isophorone diisocyanate. 2. Acevedo [2] prepared PolyBd diol pre-polymers terminated with isocyanate, acrylate, methacrylate, or organosilanes that were moisture or radiation curable for use in sealant compositions. 3. Bonnet [3] prepared aqueous dispersions of bitumen and asphaltenes using the urethane reaction product of 4,40 -diphenylmethane diisocyanate and PolyBd diol. References 1. I. Bechara et al., US Patent 7,160,944 (January 9, 2007) 2. M. Acevedo et al., US Patent 7,189,781 (March 13, 2007) 3. E. Bonnet et al., US Patent Application 2005-0124736 (June 9, 2005)

e. Poly(Aniline-co-Thiophene)

Title:

Soluble Aniline-Thiophene Copolymers

Author:

S. S. Xiao et al., US Patent 7,193,021 (March 20, 2007)

Assignee:

Organic Vision, Inc. (Brossard, CA)

SIGNIFICANCE Four solvent-soluble poly(aniline-co-thiophene) materials have been prepared by coupling thiophene derivatives with 4-n-butyl aniline using palladium acetate as catalyst. Mn’s of up to 17,500 daltons with a PDI of 1.1 were obtained.

REACTION

i S

Br

S

Br

ii Note 1

S

N

a

n-C4H9 i: DMF, N-bromosuccinimide ii: Toluene, palladium acetate, tri-t-butylphosphine, sodium t-butoxide, 4-nbutylaniline

EXPERIMENTAL 1.

Preparation of 2,5-Dibromothiophene

A reactor wrapped with aluminum foil to avoid light penetration was charged with 300 ml of DMF and thiophene (0.5 mol) and then treated with the dropwise addition of N-bromosuccinimide (1.1 mol) and stirred 48 hours in the dark. The mixture was poured into 300 ml of ice-water and stirred for 2 hours until a yellow suspension formed. The suspension was extracted 4 times with 200 ml diethyl ether, and the 381

382

Soluble Aniline-Thiophene Copolymers

combined ethereal solution was washed twice with 100 ml water and dried with MgSO4. The mixture was filtered, concentrated, the residue purified by silica gel chromatography, and the product isolated in 91.3% yield. 2.

Preparation of Poly(2,5-Thiophene-co-4-n-Butyl-2,6-Aniline)

Under continuous nitrogen flow, a reaction flask was dried with a propane torch flame and then cooled to ambient temperature. The flask was charged with 180 ml of toluene, palladium acetate (0.5 mmol), and tri-t-butylphosphine (2.0 mmol) and stirred at ambient temperature until a thick light yellow suspension was obtained. This mixture was then treated with 4-n-butylaniline (10 mmol), the Step 1 product (10 mmol), and sodium t-butoxide (22 mmol) and heated overnight at 80 C. The reaction mixture was poured into 1000 ml of methanol where a brownish precipitation slowly appeared, which was isolated by filtration. The brown solid was dissolved in 50 ml of CCl3H and re-precipitated in 500 ml of methanol, and the product was isolated in 45.0% yield as a brown powder having a Mw of 7728 daltons with a PDI of 2.12.


Physical properties of thiophene and aniline copolymers.

Entry

2

Structure N

S

S

a

Polymerization Yield (%)

Mw (daltons)

PDI

73.4

5,860

4.1

Black

64.1

17,500

1.1

Brownish

36.5

3,500

1.15

Black

Color

n-C4H9

C6H 13 N

S

3

a

n-C4H9

O

4

O S

N

a

n-C4H9 Note: Limited analytical information supplied by the author.

Notes

383

NOTES 1. The rationale for preparing this hybrid copolymer was to combine the desirable properties of polyaniline with those of polythiophene. For example, polythiophene has demonstrated thermo- and electrochromism, solvatochromism, luminescence, and photoconductivity while polyaniline has demonstrated reversible protonic dupability, excellent redox re-cyclability, and chemical stability. 2. Wu [2] coupled thiophene with aromatic diethers, (I), to improve the solubility of polythiophene in common solvents and to increase its flexibility in coating applications.

OC6H13 S S C6H13O

a

(I)

3. Angelopoulos [2] prepared a 5 wt% water-soluble electrically conducting polymer by polymerizing aniline with polystyrene sulfonic acid for use in organic discharge layers in electronic applications. In these materials the number of acidic groups exceeded the number of protonatable basic atoms in polyaniline. Water-soluble electrically conducting polymers were also prepared by Angelopoulos [3] using both polyvinylsulfonic and polyacrylic acids as the acidic blending component. References 1. Y. Wu et al., US Patent 7,169,883 (January 30, 2007) 2. M. Angelopoulos et al., US Patent 7,166,241 (January 23, 2007) and US Patent 6,830,708 (December 14, 2004) 3. M. Angelopoulos et al., US Patent 5,370,825 (December 23, 1994)

f. Aniline Formaldehyde Oligomers

Title: Process for the Preparation of Di- and Polyamines of the Diphenylmethane Series Author:

H. H. Muller et al., US Patent 7,186,857 (March 6, 2007)

Assignee:


SIGNIFICANCE Aniline was converted into its novolak analogue by reacting with formaldehyde and hydrochloric acid in the presence of divalent metal cations such as Caþ2 and Feþ2. The ratio of aniline/formaldehyde/hydrochloric acid was 7.5:1.0:0.3, respectively, using 0.00025 wt% metal ions. These oligomeric products are designed to be further modified to isocyanates by reacting with phosgene.

REACTION NH2

NH2

NH2

NH2

i a i: Hydrochloric acid, formaldehyde, iron(II) chloride

EXPERIMENTAL Preparation of Diphenylmethane, Di-, and Polyamines A reactor charged with aniline (931 g) at 80 C was treated with the dropwise addition of 32.1 wt% aqueous formaldehyde (389 g) over 20 minutes. After the addition was completed, the mixture was stirred for a further 5 minutes, and the organic phase was isolated. The organic phase was then treated with the dropwise addition of 12 M hydrochloric acid (114 g) over 20 minutes at 45 C and 0.00025 wt% iron(II) chloride. 384

Notes

385

The mixture was then stirred at 45 C for 30 minutes and an additional 30 minutes at 60 C. The reaction temperature was increased to 104 C for 10 hours and then neutralized with 33 wt% aqueous NaOH (62.3 g) at 90 C. A two-phase mixture formed, which was subsequently stirred at 90 C for 5 minutes, and the organic phase was obtained. After removal of unreacted aniline by distillation, the product mixture was isolated.

DERIVATIVES Only the Step 1 product mixture was described.

NOTES 1. Methylenedianiline was previously prepared by Klein [1] using an aniline/ formaldehyde ratio of 9:1, respectively, in the absence of a metallic salt at 60 C. Scale-up production for methylenedianiline using an aniline/formaldehyde ratio>2 and hydrochloric acid/aniline ratio of 0.05 is described by Steinbrenner [2]. 2. Hagen [3] prepared diphenylmethane and polyamines in the absence of metallic ions using an aniline/formaldehyde ratio of 4:1, respectively, at 80 C. 3. Polyamines prepared by Koch [4] were converted into the corresponding isocyanate derivatives, (I), using phosgene; methylenebis(phenyl isocyanate) was prepared by Strofer [5].

NCO

NCO

(I)

NCO

a


S. Klein et al., US Patent 6,649,798 (November 18, 2003) U. Steinbrenner et al., US Patent Application 2007-0010692 (January 11, 2007) D. Koch et al., US Patent 7,041,776 (May 9, 2006) D. Koch et al., US Patent 7,041,776 (May 9, 2006) E. Strofer et al., US Patent 6,831,192 (December 14, 2004)

g. Polymaleimides

Title: Method for Preparing Polymer Maleimides Author:

A. Kozlowski et al., US Patent Application 2007-0049688 (March 1, 2007)

Assignee:

Nektar Therapeutics (San Carlos, CA)

SIGNIFICANCE Methoxypolyethylene glycol maleimide has been prepared at ambient temperature by reacting the corresponding polyethylene oxide with N-methoxycarbonylmaleimide. Since malimide derivatives are ordinarily prepared at 140 C, this ambient temperature imidization procedure dramatically broadens the scope and utilization of this reaction.

REACTION O H3CO

O

O

NH2 450

i

H3CO

O

O 450 O

H3CO

O

O 450

N H

H N

OCH3

O

ii Note 1

N O

i: N-Methoxycarbonylmaleimide, N,N-diisopropylethylamine, CH2Cl ii: Acetonitrile, N,N-diisopropylethylamine

EXPERIMENTAL 1.

Preparation of Methoxypolyethylene Glycol Maleamic Acid

A solution of methoxypolyethylene glycol (0.0025 mol) dissolved in 350 ml of CH2Cl2, and N-methoxycarbonylmaleimide (0.0051 mol) was stirred at ambient temperature for one hour and then treated with 1 ml of N,N-diisopropylethylamine. The mixture was stirred overnight at ambient temperature and concentrated by 386

Notes

387

distilling off approximately 200 ml of CH2Cl2. The mixture was precipitated in diethyl ether, and 46.3 g of product were isolated. 1

H-NMR (d6-DMSO): d 3.24 (s, PEGOCH3), 3.51 (s, PEG backbone), 3.86 (s,CH3ONH), 6.20 (m, CH¼CH), 8.46 (NH).

2.

Preparation of Methoxypolyethylene Glycol Maleimide

The Step 1 product (10.0 g) was dissolved in 100 ml of acetonitrile containing 10 ml of N,N-diisopropyl-ethylamine and stirred for 48 hours at ambient temperature. The solution was concentrated by distilling off 80 ml of solvent and 8.5 g of product isolated by precipitating in diethyl ether. The product was 93.5% maleimide-functionalized. 1

H-NMR (d6-DMSO): d 3.24 (s, PEG–OCH3), 3.51 (s, PEG backbone), 7.01 ppm (s,–CH¼CH–, maleimide)


NOTES 1. The succinimidyl analogue, (I), of the current invention was previously prepared by Harris [1]. O O

H3CO

O

O O

O 450

O

N

O O

(I)

2. In an earlier investigation by the author [2] the reagent 4-chlorobutyaldehyde diethyl acetal, (II), was used to convert methoxypolyethylene glycol into the corresponding aldehyde, which was then used as a conjugate for lysozyme, (III), as illustrated below. O

H3CO

O

OH

+

675

OC2H5

Cl

i

OC2H5

(II) H3CO

O

O 675

iii

O

H3CO

O

OC2H5

ii

O

O 675

(III)

H3CO

O

O

O 675

NH-Lysozyme

O

OC2H5

388

Method for Preparing Polymer Maleimides

i: Toluene, potassium t-butoxide, t-butanol ii: Water, phosphoric acid, sodium chloride, sodium hydroxide, iii: Lysozyme, phosphate buffer (pH ¼ 7.6), sodium cyanoborohydride 3. Di(1-denzotriazolyl)carbonate, (IV), was also used by the author [2,3] for preparing 1-benzotriazolyl carbonate esters of polyethylene glycol, (V), which were then used to form urethane conjugates, (VI), with aminoacids as illustrated below. N

N N N O

H3CO

O

OH 450

N O

N O

+

i

O

N

(IV) O

H3CO

O

NH-Lysine

O 450

(VI)

N O

ii H3CO

O

N O

O

O 450

(V)

O

i: Pyridine, acetonitrile ii: Borate buffer, sodium hydroxide, sodium chloride, phosphoric acid. 4. Bifunctional polyethylene glycols, (VII), were prepared by Bentley [4] and used as bioconjugates.

A

O

O

(VII)

O a

B

A OH OH OH NH3+ClC6H5–CH=CH–CH=CH–CO2

B NH3+ClNH2 CH2CO2H CH2C02H CH(OC2H5)2


J.M. Harris et al., US Patent 7,030,278 (April 18, 2006) A. Kozlowski et al., US Patent 7,157,546 (January 2, 2007) and US Patent 6,710,125 (March 23, 2004) A. Kozlowski et al., US Patent 7,101,932 (September 5, 2006) M.D. Bentley et al., US Patent 6,864,327 (March 8, 2005) and US Patent 6,495,659 (December 17, 2002)

h. Poly(9-Fluroenone)

Title: Method for Preparing Polymers Containing Cyclopentanone Structures Author:

T. Umemoto, US Patent 7,182,850 (February 27, 2007)

Assignee:

IM&T Research, Inc. (Denver, CO)

SIGNIFICANCE A high-yielding single step method for preparing poly(9-fluroenone) by electrolytically polymerizing fluorene in the presence of propylene carbonate and lithium hexafluorophosphate is described.

REACTION

i O

a

i: Propylene carbonate, lithium hexafluorophosphate

EXPERIMENTAL Preparation of Poly(9-Fluroenone) In a vessel for electrolysis three parallel nickel plates were installed. The inner nickel plate was the working electrode (anode), and the two outer nickel plates were counter electrodes (cathode). A 1.2 liter mixture consisting of fluorene (0.01 mol) and LiPF6 (0.1 mol) dissolved in propylene carbonate were then added to the vessel. The three nickel plates were immersed in the mixture to a depth of 90 mm. Two lithium metal sheets were used as reference electrodes, with each sheet placed between the anode and the cathode. The electrolysis was carried out by a potential-sweep method for 4 hours under a potential width of 4.5 to 6.7 V with a sweep time of 50 mV/s. The inner 389

390

Method for Preparing Polymers Containing Cyclopentanone Structures

electrode (anode) on which the polymer had deposited was pulled out of the electrolyte mixture, and the polymer was isolated. The collected polymer was washed with propylene carbonate and acetonitrile, dried at 120 C for 5 hours, and 0.31 g of product were isolated as a dark brown to black solid, MP >400 C. FTIR (KBr, cm1): 3051(w), 2916(w), 1714(s)(C¼O), 1606(s), 1454(s), 1405(m), 1263(m), 815(s), 767(s), 735(s) Elemental analysis: Found: C, 85.94%; H, 4.29%; O, 8%; F; 0.31%; P, 0.21%: total 98.75% Calcd for C13H6O; C, 87.63%, H, 3.37%, O, 8.98%

SCOPING STUDIES TABLE 1. Experimental conditions for preparing poly(9-fluroenone) using 0.1 mol fluorene in the presence of varying amounts of propylene carbonate. Entry Electrolyte and concentration (mol) Propylene carbonate (mol) Working electrode (anode) (mm mm) Counter electrode (cathode) (mm mm) Conditions Polymer yield (mg)

5

8

16

LiPF6, 0.1

Et4BF4, 0.1

LiPF6, 0.1

0.1 Pt, 25 25

0.025 Pt, 25 20

0.05 GC, 25 25

Pt mesh, 40 35 1.6 V, 4 hours

Pt mesh, 35 30 2.4 V, 3 hour

Cu, 25 30

10.8

3.7

50 mV/s 0.5 – 2.7 V 12.3 hour 25.2

NOTES 1. Poly(9-fluroenone) has also been prepared by the oxidation of polyfluorene using acetic acid and sodium dichromate, as described by Rauth-Berthelot [1] and Umemoto [2]. 2. Methods for preparing poly(9-fluroenone) containing 35% polyfluorene content are described by the author in a subsequent investigation [3]. 3. A negative electrode was prepared by the author [4] that consisted of 70% poly (9-fluroenone) or poly(cyclopent[def]fluorene-4,8-dione), (I), with 25 wt% acetylene black and 5 wt% tetrafluoroethylene using LiAsF6 as the electrolyte in propylene carbonate.

Notes

391

O

O

(I) 4. Uckert [5,6] prepared electroactive poly(fluorene-co-fluroenone), (II), and aliphatic and perfluoroaliphatic derivatives for use in as light-emitting diodes. Light-emitting devices consisting of polyfluorene alkoxy derivatives, (III), were prepared by Mizuno [7]. O

R 2-Ethyl-n-hexane Perfluoron-decane

R

C7H15O

R

(II)

References 1. 2. 3. 4. 5. 6. 7.

a

a

J. Rauth-Berthelot et al., New J. Chem, 10, Sept 23, 1985 T. Umemoto, US Patent 7,087,681 (August 8, 2006) T. Umemoto, US Patent Application 2005-0045492 (March 3, 2005) T. Umemoto, US Patent Application 2006-0008703 (January 12, 2006) F.P. Uckert et al., US Patent 7,183,366 (February 27, 2007) F.P. Uckert et al., US Patent 7,183,365 (February 27, 2007) Y. Mizuno et al., US Patent 7,184,191 (February 27, 2007)

OC7H15

(III)

i. Polypropylene Succinic Anhydride

Title: Polypropylene Having a High Maleic Anhydride Content Author:

P. K. Hanna et al., US Patent 7,183,359 (February 27, 2007)

Assignee:

Baker Hughes Incorporated (Houston, TX)

SIGNIFICANCE A method of incorporating between 5% to 45% maleic anhydride into polypropylene without chain scission or viscosity increase is described. The method entails an initial thermally induced ene reaction followed by the free radical addition of the anhydride to the polymer backbone.

REACTION O

O

O

O

O

+

O

O

i

O

O

O O

Note 1

O O O O

(Ene reaction products) not isolated

i: Maleic anhydride, acetone, di-t-butyl peroxide

392

Notes

393

EXPERIMENTAL Preparation of Poly(Propylene-g-Maleic Anhydride) A reactor was charged with polypropylene containing an ene terminus (250 g), and the temperature was increased and maintained at 185 C. This material was then treated with maleic anhydride (20 g) dissolved in 24 ml of acetone followed by the dropwise addition of di-t-butyl peroxide (6 g). The reaction was maintained at this temperature for 3 hours and then gradually cooled over 60 minutes. The product was isolated having an 11.3% maleic anhydride content.

DERIVATIVES TABLE 1. Selected polypropylene succinic anhydrides prepared using polypropylene containing an ene terminus and maleic anhydride. Entry

Polypropylene-ene Copmponent

Final Maleic Anhydride Content (wt%)

1 12 13 14 15 16 17 20 21

EastmanÒ AP550 PP-ene-C Entry 12 product Entry 13 product PP-ene-D Entry 15 product Entry 16 product Octadecene-ene Entry 20 product

4.2 11.3 16.1 28.7 0.9 7.5 45 35.3 51.0

Note: Percent incorporation of maleic anhydride was determined by 13 C-NMR.

NOTES 1. The ene reaction of maleic anhydride with vinylidene-terminated polypropylene that results in a high molecular weight product, (I), and viscosity increase is illustrated below.

.

O

O

O

.

O

O

O

OO

O O

n

i

a

O a

Intermediate 1

a

Intermediate 2

a

a

a

(I)

i: Maleic anhydride 2. In the absence of a solvent and using dilaurylperoxide as the free radical initiator, Bortolon [1] grafted roughly 3 wt% maleic anhydride onto the

394

Polypropylene Having a High Maleic Anhydride Content

polypropylene backbone at 90 C under 3 atm of nitrogen pressure after allowing the mixture to react for two hours at 110 C. 3. High melt flow polypropylene-g-maleic anhydride has also been prepared by reactive extrusion methods. Flaris [2] reacted a mixture of polypropylene, maleic anhydride, and 2,5-dimethyl-2,5-di-(t-butyl peroxide)hexane in a twinscrew extruder having a barrel temperature profile of 175 C, 190 C, 215 C, 215 C, 215 C, 200 C, and 170 C. With this technique the grafted maleic anhydride content was about 2 wt%. Pradel [3] grafted 1.5 wt% maleic anhydride onto syndiotactic poly(polypropylene) while co-extruding polyethylene using 2,5-dimethyl-2,5-di-(t-butyl peroxide)hexane in an eight-zone extruder. 4. Harrison [4] prepared poly(isobutylene-g-succinic anhydride) by reacting a 1:1 mole ratio of polyisobutene/maleic anhydride using di-t-butylperoxide as catalyst where the ratio of di-t-butylperoxide/polyisobutene was 0.05:1, respectively. In this procedure polyisobutylene had a Mn of roughly 2300 daltons while the product had a SAP number of 26.2 mg for the KOH/g sample. Poly (isobutylene-g-succinic anhydride) has also been prepared in the simultaneous chlorination/maleation process described by Barini [5]. References 1. 2. 3. 4. 5.

V. Bortolon et al., US Patent 6,437,049 (August 20, 2002) V. Flaris et al., US Patent 6,228,948 (May 8, 2001) J.-L. Pradel et al., US Patent 7,067,196 (June 27, 2006) J.J. Harrison et al., US Patent 6,451,920 (September 27, 2002) G. Barini et al., US Patent 6,562,904 (May 13, 2003)

j. Cysteine Graft Copolymers

Title:


Author:

A. B. Brennan et al., US Patent 7,169,853 (January 30, 2007)

Assignee:


SIGNIFICANCE Polyamide copolymers containing a macromolecular graft substituent were prepared by condensing 4-amino-benzoic acid or a mixture of 1,4-phenylene diamine and adipic acid with 33%, 66%, and 90% S-poly(n-butylacrylate)cysteine macromonomer. A second macromolecular monomer, S-poly(methyl methacrylate)-cysteine, was also prepared and free radically copolymerized with perfluoromethyl methacrylate.

REACTION O O

O O O

n-C4H9

H2N

i

N H

OH S

ii


a N H

S Poly(butyl acrylate)

i: 2,20 -Azobisisobutyronitrile, cysteine, THF, hydrochloric acid ii: Triphenylphosphite, lithium chloride, pyridine, N-methyl-pyrrolidinone, 4-aminobenzoic acid

EXPERIMENTAL 1.

Preparation of S-(Poly-n-Butyl Acrylate)-Cysteine Macromonomer

The synthesis of poly(butyl acrylate) was carried out using THF, ethyl alcohol, and water where the molar ratio of butyl acrylate monomer/cysteine/azobisisobutyro-nitrile 395

396


was 1000:30:1, respectively. The mixture was then refluxed for 6 hours at 65 C while under constant stirring. After cooling, the cysteine-modified product consisted of a white precipitate dispersed within a poly(butyl acrylate) matrix. The precipitate was isolated from the polymer by dissolving the poly(butyl acrylate) in THF and filtering. 2. Preparation of Poly(4-Amino-Benzoic Acid-co-(Cysteine-g-Poly-n-Butyl Acrylate) The Step 1 product (1.37 g; Mn 26,000 daltons), 4-aminobenzoic acid (2.24 mmol), triphenyl-phosphite (5 mmol), and LiCl 0.09 g were dissolved in 30 ml of N-methylpyrrolidinone/pyridine solution, 80:20, respectively, and heated to 100 C for 4 hours. The reaction mixture was then precipitated in an excess of water/methanol, 1:1, filtered, and washed with methanol. The material was dried overnight under vacuum at 40 C, and the product was quantitatively isolated.

DERIVATIVES TABLE 1. Selected comonomer(s) reacted with cysteine-g-macromolecular intermediates and corresponding macromolecular content. Cysteine-g-Macromolecular Component Poly(butyl acrylate) Poly(butyl acrylate) Poly(butyl acrylate) Poly(butyl acrylate) Poly(methyl methacrylate)

Comonomer(s) 4-Amino-benzoic acid 4-Amino-benzoic acid 1,4-Phenylene diamine and adipic acid 1,4-Phenylene diamine/adipic acid Perfluoromethyl methacrylate

Macromolecule Content In Copolymer (wt%) 33 66 66 90 65

Note: Polymers derived from 4-amino-benzoic acid were insoluble in all solvents except concentrated sulfuric acid. Elemental analysis for all materials supplied by author.

NOTES 1. Polylysine-g-polyhistidine derivatives, (I), were prepared by Pack [1] and were effective as biocompatible endosomolytic delivery agents.

Notes

397

NH2

O

H N

b = 10 –100%

b

O a

N N H

HN

O N H c

(I)

2. Kaneko [2] prepared compatibilizing agents consisting of methacrylate, (II), and styryl, (III), macromolecules, which were polymerized using titaniumbased Ziegler–Natta catalysts.

O O

(II)

R

O R

R = Polyethylene Polypropylene Poly(ethylene-co-propylene)

(III)

References 1. D.W. Pack et al., US Patent Application 2001-0006817 (July 5, 2001) 2. H. Kaneko et al., US Patent 7,067,587 (June 27, 2006)

k. Guerbet Polymers

Title: Guerbet Polymers Author:

A. J. O’Lenick Jr., US Patent 7,049,476 (May 23, 2006)

Assignee:

SurfaTech Corporation (Dacula, GA)

SIGNIFICANCE Highly branched and saturated oily Guerbet polymers having primary alcohols have been prepared by condensing 1,9-, 1,10-, or 1,12-aliphatic diols with behenyl alcohol and zinc oxide. To control the molecular weight, each polymer was capped with a C12 or higher fatty alcohol.

REACTION HO

OH

6

HO

6

i

OH

6

OH 20 19

i: Zinc oxide, behenyl alcohol

EXPERIMENTAL Preparation of Polymeric Guerbet Alcohol A reaction vessel was charged with behenyl alcohol (0.652 kg), 1,10-decanediol (101 kg), and zinc oxide (6 g) and then heated to 230 C. The reaction began at about 170 C and was monitored by the amount of water generated and hydroxyl number of sample aliquots. When the reaction was completed, the product was used without purification. 398

Notes

399

DERIVATIVES TABLE 1. Selected Guerbet oligomers and polymers prepared using C9, C10, or C12 diols with behenyl alcohol and capping with a fatty alcohol. Entry

Capping Alcohol

1 3 5 7 9

Capryl Lauryl Palmityl Aracadinyl Beheny

Diol

Repeat Unit

1,10-Decanediol 1,12-Dodecyldiol 1,10-Decanediol 1,9-Nonyldiol 1,10-Decanediol

1 20 50 100 20

Note: The catalyst was 0.1 wt% zinc oxide based on capping agent. Very limited analytical data were supplied by the author.

NOTES 1. Guerbet alcohols were previously used by the author [1] to prepare controlled molecular weight polyesters derived from succinic acid and used in skin care formulations. 2. In a subsequent investigation by O’Lenick [2] Guerbet acids were converted into the corresponding oligomers by reacting with difunctional acids while using benzene sulfonic acid as catalyst. Products were used to prepare lipstick. 3. Guerbet triblock alkoxy sulfonates, (I), were prepared by the author [3] and used as emulsifying agents in skin care formulations.

9

O

7

O O a

b

O

O a

SO3 Na

(I) 4. Dimer quaternary compounds, (II), prepared by the author [4] were used as barrier agents in personal care products.

7

CO2H H N

C6H13 7

C6H13

O

(II)

N(CH3)3

400

Guerbet Polymers


A.J. O’Lenick Jr., US Patent A.J. O’Lenick Jr., US Patent A.J. O’Lenick Jr., US Patent A.J. O’Lenick Jr., US Patent

7,038,005 7,259,226 7,119,125 7,193,111

(May 2, 2006) (August 21, 2007) (October 10, 2006) (March 20, 2007)

l. Poly(1,4-Phenylene Vinylene) Derivatives

Title:

Polymerization Method

Author:

A. B. Holmes et al., US Patent 7,005,484 (February 28, 2006)

Assignee:

Cambridge Display Technology Limited (Cambridge, GB)

SIGNIFICANCE Beginning with tetra-N-ethyl-terephthalamide a five-step method for preparing poly [2-(dimethyloctylsilyl)-5-(dimethyldecylsilyl)-1,4-phenylene vinylene] is described. The conjugated polymers are useful in electric, electronic, optical, and optoelectronic devices such as LEDs.

REACTION C8H17 Si (C2H5)2N

N(C2H5)2

O

(C2H5)2N

i

O

O

ii

O

C8H17

C8H17

C8H17

Si

Si Cl

N(C2H5)2

Si

(C2H5)2N

Cl

N(C2H5)2

iv

iii

(C2H5)2N

N(C2H5 )2

O Si

Si

C10H21

C10H21

O Si

C10H21 C8H17 Si

v Note 1 Si

a

C10H21

401

402

i: ii: iii: iv: v:


THF, t-butyllithium, chlorodimethyloctylsilane Tetramethylethylenediamine, THF, sec-butyllithium, chlorodimethyloctylsilane THF, borane-tetrahydrofuran complex, hydrochloric acid CH2C12, vinyl chloroformate THF, potassium t-butoxide

EXPERIMENTAL 1.

Preparation of 2-Dimethyloctylsilyl-Tetra-N-Ethyl-Terephthalamide

Tetra-N-ethyl-terephthalamide (0.36 mmol) dissolved in 30 ml of THF was cooled to -78 C and treated with 253 ml of t-butyllithium (0.43 mmol), and after 30 minutes was treated with 102 ml of chlorodimethyloctylsilane (0.43 mmol). Thereafter the mixture was left to reach ambient temperature over a three-hour period. Brine was then added, and the mixture was extracted with CH2Cl2; it was subsequently dried and concentrated. The residue was purified using column chromatography with hexane/EtOAc, 60:40, respectively, and the product was isolated in 78% yield as a white solid, MP ¼ 46 C. H-NMR (CDCl3) d 7.40 (d, 1H, J ¼ 1.57 Hz), 7.22 (dd, 1H, J.sub.1 ¼ 7.75 Hz, J.sub.2 ¼ 1.57 Hz), 7.09 (d, 1H, J ¼ 7.75 Hz), 3.45 3.36 (m, 4H), 3.06 2.98 (m, 4H), 1.15 0.90 (m, 25H), 0.74 0.64 (m, 4H), 0.12 (s, 6H). 13 C-NMR (CDCl3) d 171.6, 171.0, 143.6, 137.4, 136.5, 132.8, 126.3, 125.6, 43.4, 38.9, 33.5, 31.8, 29.2, 29.1, 23.8, 22.5, 15.9, 14.0, 13.6, 12.7, -2.3. FTIR (KBr cm1) 2972, 2926, 2854, 1623, 1484, 1430, 1383, 1291, 1251, 1220, 1105, 1062, 842. 1

2. Preparation of 2-Dimethyloctylsilyl-5-Dimethyldecylsilyl-Tetra-N-EthylTerephthalamide Tetramethylethylenediamine (3.7 mmol) dissolved in 15 ml of THF at -78 C was treated with 2.9 ml of sec-butyllithium. This mixture was then treated with the dropwise addition of the Step 1 product dissolved in THF, and the mixture was stirred for 20 minutes. After treating this mixture with 1 ml of chlorodimethyloctylsilane, the reaction was left to react at ambient temperature while being stirred overnight. Following the Step 1 workup using hexane/EtOAc, 80:20, respectively, the product was isolated in 85% yield as a white solid. H-NMR (CDCl3) d 7.33 (s, 2H), 3.54 (q, 4H, J ¼ 7.15 Hz), 3.12 (q, 4H, J ¼ 7.15 Hz), 1.30 0.52 (m, 50H), 0.21 (s, 12H) 13 C-NMR (CDCl3) d 172.4, 142.2, 137.3, 132.2, 43.3, 38.9, 33.7, 31.9, 29.7, 29.4, 24.0, 22.7, 16.0, 14.1, 13.8, 12.8, -2.3 FTIR (KBr cm1) 2955, 2922, 28.2, 1635, 1482, 1455, 1424, 1380, 1276, 1247, 1129, 1086, 868, 839, 813. 1

3. Preparation of 2-Dimethyloctylsilyl-5-Dimethyldecylsilyl-Tetra-NEthyl-p-Xylylenediamine The Step 2 product (2.3 mmol) dissolved in 30 ml of THF was treated with a boranetetrahydrofuran complex (23 mmol) and then refluxed for 18 hours and quenched with water. The mixture was concentrated and treated with 6M hydrochloric acid and

Notes

403

refluxed for 4 hours. The solution was then cooled and the pH increased to 9 using sodium hydroxide. Thereafter the aqueous phase was extracted with CH2Cl2, dried with MgSO4, and re-concentrated. The residue was purified by column chromatography using hexane/EtOAc, 96/4, respectively, and the product isolated in 52% yield as a white solid, MP ¼ 26 C. 4. Preparation of 2-Dimethyldecylsilyl-5-Dimethyldecylsilyl-1,4-bis (Chloromethyl)Benzene The Step 3 product (1.09 mmol) dissolved in 20 ml of CH2Cl2 was cooled to 0 C and then treated with vinyl chloroformate (82.7 mmol) and stirred for 5 hours at ambient temperature. The mixture was next quenched with brine, and the aqueous phase was extracted with CH2Cl2 and combined extracts dried with MgSO4 and concentrated. The residue was purified by chromatography using hexane, and the product was isolated in 65% yield MP ¼ 40 C. FTIR (KBr cm1) 2963, 2922, 2852, 1466, 1370, 1248, 1203, 1166, 1121, 1057, 835 1 H-NMR (CDCl3) d 7.71 (s, 2H), 3.63 (s, 4H), 2.51 (q, 5H, J ¼ 7.10 Hz), 1.30 0.81 (m, 50H), 0.30 (s, 12H) 13 C-NMR (CDCl3) d 143.2, 137.821, 134.7, 58.6, 46.2, 33.7, 31.9, 29.7, 29.3, 24.2, 22.7, 16.6, 14.1, 11.7, 1.3

5. Preparation of Poly[2-(Dimethyloctylsilyl)-5-(Dimethyldecylsilyl)-1,4Phenylene Vinylene] The Step 4 product (0.2 mmol) dissolved in 15 ml of THF was added to potassium t-butoxide (112.5 mg) dissolved in 5 ml THF over 10 minutes and then stirred overnight. The polymer was precipitated in methanol, purified by re-dissolving in THF, and last precipitated in acetone. After drying, the product was isolated in 26% yield. FTIR (KBr cm1) 2923, 2854, 1466, 1411, 1377, 1344, 1254, 1192, 1172, 1140, 1108, 837, 792, 716 1 H-NMR (CDCl3) d 7.57 (s, 2H), 4.70 (s, 4H), 1.36 1.29 (m, 29H), 0.92 0.83 (m, 9H), 0.42 (s, 12H) 13 C-NMR (CDCl3) d 141.9, 140.2, 137.0, 46.5, 33.6, 32.0, 29.7, 29.6, 29.4, 29.3, 24.0, 22.7, 16.5, 14.1, -1.5. UV (CDCl3) dmax: 438 nm UV (film) dmax 430 nm Mn ¼ 289,000; Mw ¼ 1,065,000; PDI ¼ 3.7 TGA ¼ 350 C(dec); DSC ¼ 300 C (dec); no Tg or Mp


NOTES 1. Beginning with p-benzophenone Kreuder [1] devised a seven step method for preparing poly(1,4-phenylene vinylene) derivatives as illustrated below.

404


OC5H11

OH O

i

O

Br

ii

Br

Br C5H11O

HO

OC5H11

OC5H11 O

O B

iv

B

O

(HO)2B

OC5H11 Br

C5H11O

OC5H1

OC5H11

v

B(OH)2

O

C5H11O Intermediate

Br

iii

Br

Br

OC5H11

vi

CHO

1

Br Br C5H11O

C5H11O

C5H11O

C5H11O OC5H11

vii Intermediate

a

C5H11O

i: Br2/HBr ii: C5H11Br iii: BuLi, B(OCH3) 3, HCl iv: 1,3-Propanediol v: BuLi, DMF, HCl vi: TiCl4/Zn vii: NaHCO3 2. In an earlier investigation by the author [2] poly(phenylene-co-vinylene) containing 2,5-thienylene vinylene, (I), was prepared and used as semiconductors in luminescent devices.

H3CO

S c

a

d

OCH3

S b

(I) 3. Corma Canos [3] prepared electroluminescent materials by encapsulating polyphenylene-vinylene derivatives in an CsX zeolite.

Notes

405

4. Stilbene methacrylate esters prepared by Holmes [4] were useful in photoluminescent and electroluminescent optical devices.

a O

O

(II)


W. Kreuder et al., US Patent 6,114,490 (September 5, 2000) A.B. Holmes et al., US Patent 5,512,654 (April 30, 1996) A. Corma Canos et al., US Patent 7,108,802 (September 19, 2006) A.B. Holmes et al., US Patent 7,105,621 (September 12, 2006) and US Patent 6,919,415 (July 19, 2005)

m. Branched Polyesters

Title: Process for Producing Polymerizable Polybranched Polyester Author:

H. Hayakawa et al., US Patent 7,141,642 (November 28, 2006)

Assignee:

Dainippon Ink and Chemicals, Inc. (Tokyo, JP)

SIGNIFICANCE A new transesterification stanoxane catalyst, tin (di(chlorodimethylsiloxy)-tin chlorodimethylsilane), has been used to incorporate ethyl acrylate into the condensation polymer of 2,2-bis(hydroxymethyl)propionic acid. This catalyst is preferable because it allows the reaction to proceed under milder conditions than those using a condensation esterification reaction route and makes it likely for product crosslinking side reactions to occur.

REACTION HO

HO

HO

O

O

HO

HO

O

O OHO

O O

OH O

O b

HO

i Note 1

O

O

O

HO

O

a

HO

O

O

O

O

O O O

O O

OH O

O b

HO

O

O a

O O

i: Tin (di(chlorodimethylsiloxy)-tin chlorodimethylsilane), hydroquinone, ethyl acrylate

406

Notes

407

EXPERIMENTAL Preparation of Hyperbranched Polyacrylate Polyol A reaction vessel equipped with a Dean–Stark decanter was charged with 10 parts of the condensation polymer of 2,2-bis(hydroxymethyl)propionic acid having a Mn of 2920 daltons, a Mw of 4280 daltons, and a PDI of 1.47. This mixture was then treated with tin(di(chloro-dimethylsiloxy)-tin chlorodimethylsilane) (0.25 parts), ethyl acrylate (100 parts), and hydroquinone (0.05 parts). The mixture was then heated to between 92 C and 95 C so that the amount of distillate to the decanter was 15 to 20 parts per hour. Fresh ethyl acrylate was added to the reaction vessel as needed while the reaction continued for 20 hours. Following completion of the reaction, excess ethyl acrylate was removed by distillation and the residue dissolved in 70 parts of EtOAc. The solution was washed three times with 30 parts of hot water at 50 C to extract the catalyst. The solution was further washed four times with 20 parts of 5% aqueous NaOH to remove hydroquinone, followed by a single washing with 20 parts of 1% aqueous H2SO4 and twice with 20 parts of water. The mixture was last treated with 0.0045 parts of methoquinone and distilled; 13 parts of product were isolated having a Mn of 3880 daltons, Mw of 7730 daltons, which is equivalent to 25.5 vinyl groups/ molecule.

DERIVATIVES No other derivatives were prepared.

NOTES 1. The formula for the stanoxane catalyst is (ClSi(CH3)2O)2Sn-Sn(CH3)2Cl. 2. Hyperbranched polycarbonates, (I), with only marginal crosslinking side reactions were prepared by Bruchmann [1] by transesterification, using diethyl carbonate and trihydroxy methylmethane catalyzed by potassium carbonate. HO O

O O

O

(I)

a

3. A method for the mild catalysis for ester/transester reactions was developed by Siddiqui [2], using the polymeric titanium glycolate catalyst, (II).

408

Process for Producing Polymerizable Polybranched Polyester

O

O

O Ti O

Ti O

O

a

(II) 4. Gross [3] incorporated pendant polyalcohols onto polyacrylic acid, (III), and poly L-glutamic acid, (IV), without crosslinking side reactions, by catalyzing with the enzyme Novozyme-435. O

a O

O

H N

a

b

O

CHOH HOHC

H N

n CH2OH

(III)

CO2H

O O

n = 0–3

HOHC

(IV)

References 1. B. Bruchmann et al., US Patent Application 2007-0037957 (February 15, 2007) 2. J. Siddiqui et al., US Patent Application 2006-0205917 (September 14, 2006) 3. R.A. Gross et al., US Patent 6,924,129 (April 2, 2005)

CH2OH

n. Poly(N-Vinylformamide) Derivatives

Title: N-Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof Author:

E. J. Beckman et al., US Patent 7,135,598 (November 14, 2006)

Assignee:

University of Pittsburgh (Pittsburgh, PA)

SIGNIFICANCE N-Vinylformamide was converted into N-alkyl-N-vinylformamide derivatives by reacting it with an alkyl bromide in the presence of base. When N-vinylformamide intermediates were reacted with 2,20 -azobisisobutyronitrile, the polymer was obtained. Hydrolysis of poly(N-vinylformamide) generated an N-alkyl polyvinylamine, a versatile synthetic intermediate.

REACTION NH CHO

i

N

C6H13

CHO

ii Note 1

a

OHC

N

iii

a

HN C6H13

C6H13

i: THF, potassium t-butoxide, 1-bromohexane ii: 2,20 -Azobisisobutyronitrile

EXPERIMENTAL 1.

Preparation of N-Hexyl-N-Vinylformamide

A reactor was charged with N-vinylformamide (0.164 mol) and 200 ml of anhydrous THF and then cooled to 15 C using an ice bath. The solution was next treated with potassium t-butoxide (0.167 mol) in three portions over 45 minutes followed by the dropwise addition of 1-bromo-hexane (0.179 mol) over 30 minutes. The reaction was slowly warmed to ambient temperature and stirred overnight. The mixture was filtered to remove KBr and then concentrated, and the residue was diluted with 200 ml of water. 409

410

N-Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof

The organic layer was extracted three times with diethyl ether, and the combined extractions were washed twice with water and dried using MgSO4. The mixture was reconcentrated and then purified by chromatography on silica using diethyl ether/ petroleum ether, 3:7, respectively; the product was isolated in 63% yield. Other aliphatic derivatives were prepared according to this procedure and are provided in Table 1. 2.

Preparation of Poly(N-Hexyl-N-Vinylformamide)

The Step 1 product (1.0 g) and 2,20 -azobisisobutyronitrile (18 mg) were added to an ampoule and degassed before sealing. The polymerization was carried out in an oil bath at 65 C for 15 hours. The polymer was purified by Soxhlet extraction using petroleum ether for 8 hours and dried under reduced pressure at 60 C for 12 hours. Polymer properties of derivatives are provided in Table 2. IR (NaCl, v: cm1): 1698 (NHC¼O)H); 1630 (C¼C) 1 H-NMR (CDCl3, d, ppm): 8.31, 8.14 (2s, 1H, C(¼O)H); 7.25 7.16, 6.61 6.52 (m, 1H, H2C¼CH); 4.65 4.54 (m, 1H, HaHbCd¼CH); 4.45 4.42 (s, 1H, HaHbC¼CH); 3.60 3.44 (t, 2H, NCH2CH2); 1.65 1.56 (m, 2H, CH2CH2CH2); 1.31 (m, 6H, CH2(CH2)3CH3); 0.90 0.88 (t, 3H, NCH2CH2(CH2)3CH3)

3.

Preparation of N-Hexyl Polyvinyl Amine

Poly(N-n-hexyl-N-vinylformamide) (0.25 g), 10 ml of 2M hydrochloric acid, and 2 ml of dioxane were stirred under reflux at 80 C under a nitrogen atmosphere for 24 hours. The hydrolyzed polymer was recovered by filtering the suspension and washing 3 times with 50 ml of deionized water. The resulting polymer was dried under reduced pressure at 60 C for 12 hours and then isolated. IR (KBr, cm-1): 2957(CH3); 1671 (C¼O) 1 H-NMR (CDCl3, d, ppm): 8.03(b, C(¼O)H); 4.23, 3.1(b, H2CCHN and NCH2CH2); 2.0, 1.53 (b, H2CCHN– and NCH2CH2); 1.31(s, (CH2)3CH3); 0.91(s, CH2CH3)

DERIVATIVES N

R

CHO TABLE 1. Selected N-alkyl-N-vinylformamide derivatives prepared by reaction of the corresponding alkyl bromide with N-vinylformamide in the presence of potassium t-butoxide. Entry 1a 1c 1d 1e

R

Yield (%)

n-Butyl n-Decyl n-Dodecyl 2-Ethyl-phthalimide

56 89 75 —

Notes

411

POLYMER DERIVATIVES

a

N

OHC

R

TABLE 2. Results of bulk polymerization of N-alkylvinylformamide at 65 C using 2,20 -azobisisobutyronitrile as the free radical initiator. Entry

R

2a 2b 2c 2d

Reaction Time (h)

Mn 1 103 (daltons)

Mw 1 103 (daltons)

PDI

Conversion (%)

10 15 15 15

13.2 8.3 10.0 10.2

27.3 18.9 20.4 21.3

2.05 2.27 2.05 2.09

86 82 59 59

n-Butyl n-Hexyl n-Decyl n-Dodecyl

NOTES 1. Vinylformamide was previously prepared by the author [1] and illustrated below O OH O

OH

i

ii

O

H2N

O O

HN

HN O O HN

i: Acetaldehyde, triethyl amine, isooctane ii: Succinic anhydride, ethyl acetate, Amberlyst 15 acid catalyst. 2. The utility of N-alkyl-poly(N-vinylformamide) was illustrated in the current invention by the author in the preparation of N-hexyl-N-dihydroperfluorooctyl polyvinylamine (I). NH

i

ii

CHO

C6H13

N

iii

a

CHO

C6H13

N

C6H13

CHO

a NH

Intermediate

O N OH O

O

O n-C7F15

iv N O O

a

v

Intermediate

C6H13

N

a

vi O C6H13

C7F15

N (I) C7F15

412

N-Vinylformamide Derivatives, Polymers Formed Therefrom and Synthesis Thereof

i: THF, potassium t-butoxide, 1-bromohexane ii: Azobisisobutyronitrile iii: NaOH, dioxane iv: Perfluorooctanoic acid, methanol v: Polyvinylamine, methanol vi: Borane, THF 3. Copolymers of vinylformamide with acrylamide, methacrylic acid, (II), methacrylates, acrylonitrile, and acrylamide were prepared by Hund [2] and used as flocculants and coagulants in waste water treatment. Sommese [3] prepared poly(vinylamine-co-N-vinylformamide), (III), having molecular weights between 0.8 106 and 2.0 106 daltons, which were used as coagulants in wastewater treatment.

b

a O _

H2N+ O CHO

a NH2 HN

(II)

b CHO

a:b 1: 1 3: 7

(III)

4. Lindsay [4] used poly(vinylamine-co-N-vinylformamide), (II), containing roughly 70% amine content as a component in textile materials and paper to improve wet strength properties. References 1. 2. 3. 4.

E.J. Beckman et al., US Patent 7,026,511 (April 11, 2006) R. Hund et al., US Patent 6,797,785 (September 28, 2004) A.G. Sommese et al., US Patent 6,610,209 (August 26, 2003) J. Lindsay et al., US Patent 6,824,650 (November 30, 2004)

o. Oligonucleotide Preparation

Title:

Polymers

Author:

E. A. H. Hall et al., US Patent 7,022,808 (April 4, 2006)

Assignee:

The Secretary of State for Defence DSTL (Salisbury, GB)

SIGNIFICANCE Peptide nucleic acid derivatives containing s-triazine have been prepared that can act as DNA mimics and as supports for use in oligonucleotide preparation. Their anticipated use is in the preparation of naturally and unnaturally occurring oligonucleotides.

413

414

Polymers

REACTION H2N

i

NH2

H2N

H N

Intermediate 1 Cl

NH2

H2N

ii

H N Boc

H2N

N

i ii

Cl

N

N H Intermediate 2 N

H N Boc

O O

O NH

N H

N

iv

v

N

O

N H

N

O

Intermediate 2

O

N Cl

N N

N H

H N Boc

O N

vii

N N

H N

N H

vi

O

Intermediate 1

N N

H N Boc

N H

O

O

N O H Boc N

i: ii: iii: iv: v: vi: vii:

N N

N

NN N H

N

N H

H N

N

O N

N

N H

H N Boc

Benzylchloride, CH2Cl2 CH2Cl2, t-butoxy carbonyl ester anhydride Cyanuric chloride, acetone, sodium bicarbonate Thymine, acetonitrile, pyridine, benzoyl chloride Acetone, sodium bicarbonate THF CH2C12, trifluoroacetic acid, THF, triethylamine

EXPERIMENTAL 1.

Preparation of N-Benzyl-Ethylenediamine

Ethylene diamine (10 g) dissolved in 60 ml of CH2Cl2 was mixed with benzylchloride (21.01 g) in CH2Cl2 and then stirred at ambient temperature for several hours and concentrated. The residue was dissolved in 100 ml of EtOAc, washed twice with 100 ml apiece of 1M KHCO3 and 5% of NaHSO4, once with 100 ml of brine, and then

Experimental

415

dried over MgSO4. The solution was concentrated, and the product was isolated in 92% yield as a colorless oil. 2.

Preparation N-t-Butoxy Carbonyl Ethylenediamine

Ethylene diamine (10 g) dissolved in 60 ml of CH2Cl2 was added to a solution of t-butoxycarbonyl ester anhydride (4.90 g) in 60 ml of CH2Cl2 over a 2-hour period and then stirred for 22 hours at ambient temperature and concentrated. The residue was treated with 100 ml of water, and the insoluble product was removed by filtration. The aqueous solution was extracted three times with 100 ml of CH2Cl2, and the combined organic layers were re-concentrated. The product was isolated in 83% yield as a colorless oil. 3. Preparation of 1,3-Dichloro-5-[2-(1-N-t-Butoxy Carbonyl Ethylenediamine)]-s-Triazine The Step 2 product was added to a slurry of cyanuric chloride (75 mg) in 12 ml of acetone and then poured into ice water. NaHCO3 (262 mg) was added and stirred for 2 hours at 0 C; then a white solid was filtered off. This solid was washed with water and dried in vacuo over P2O5. After re-crystallization from pyridine the product was isolated in 93% yield as a white solid. 4.

Preparation of N-Benzyl-Thymine

Thymine (2.62 g) was dissolved in 33 ml of acetonitrile and 13.5 ml of pyridine. The mixture was then treated with benzoyl chloride (11.68 g), stirred at ambient temperature for 24 hours, and concentrated. The residue was extracted into 62 ml of a dioxane/ water mixture, 1:1, and treated with K2CO3 (4.86 g); the suspension was stirred at ambient temperature overnight. 1M of Hydrochloric acid was then added to the solution to reduce the pH to 3, whereupon a precipitate was collected and re-crystallized from ethanol. After drying, 2.5 g of product was isolated as pale yellow needles. 5. Preparation of 1-N-Benzyl Thymine-3-[2-(1-N-t-Butoxy Carbonyl Ethylenediamine)]-5-Chloro-s-Triazine A reactor was charged with the Step 4 product (0.4 g), Na2CO3 (0.2 g), and the Step 3 product (0.5 g) dissolved in 20 ml of acetone and 10 ml of water; this mixture was stirred at ambient temperature for 5 hours. The product was isolated after filtration, and 0.41 g of product was isolated as a yellow solid. 6. Preparation of 1-N-Benzyl Thymine-3-N-Benzyl-Ethylenediamine-5[2-(1-N-t-Butoxy Carbonyl Ethylenediamine)]-s-Triazine The Step 5 product (0.1 g) suspended in 5 ml of THF was treated with the Step 1 product (0.034 g) and then refluxed overnight. The off-white solid that resulted was filtered and washed with THF and then re-crystallized from pyridine and the product isolated in 63% yield.

416

7.

Polymers

Preparation of Dimer and Higher Analogues

The Step 6 product (0.50 mg) was suspended in 300 ml of CH2Cl2, treated with 0.5 ml of trifluoro-acetic acid, stirred for 1 hour, and then concentrated. The residue was dissolved in 5 ml of THF, then treated with 24.52 ml of triethylamine and the Step 5 product (34 mg). This mixture was stirred for 2 hours at 40 C and treated with triethylamine until the mixture was basic. The solution was then concentrated and the residue dissolved in EtOAc. The solution was washed twice with 5 ml of KHSO4, once with 5 ml of water, twice with 5 ml of NaHCO3 and brine, and then dried over MgSO4. The mixture was re-concentrated, and the product was isolated in 93% yield as an offwhite solid. The Step 7 process could be repeated with the same or different monomers until an optimum chain length was obtained.


NOTES 1. Nucleic acid mimics were developed by Nielson [1] and Turney [2] that will strand-invade DNA at purine rich sites to form triplex structures. 2. Peptide nucleic acids, (I), that are not polynucleotides will form complementary DNA and RNA strands stronger than the corresponding DNA, as reported by Nielson [3].

O NH N

O O

H2N

N

OH

(I) References 1. P.E. Nielson et al., Science, 254: 1497–1506, 1991 2. D.Y. Turney et al., Proc. Natl. Acad. Sci. USA, 1993, 90, 1667–1670 3. P. Nielson et al., US Patent 5,977,296 (November 2, 1999)

p. Multistar Polystyrene

Title: Star-Shaped Polymer, Multiple Star Polymer, and Their Preparation Methods Author:

H.-J. Lee et al., US Patent Application 2005-0209408 (September 22, 2005)

Assignee:

Korea Advanced Institute of Science and Technology (Daejeon, KR)

SIGNIFICANCE A method for preparing star-shaped polystyrene by either the incremental or single addition of divinyl benzene to a living polystyryl anion is described. Star-shaped polymers containing up to 34 arms were prepared with polydispersities of less than 1.1.

REACTION a

Li

b

c

i

d

e

i: Divinylbenzene

EXPERIMENTAL Preparation of Star Polystyrenes: Generic Procedure A living polystyryl anion having a Mn of 12,000 daltons was prepared by the addition of n-butyllithium dissolved in cyclohexane to styrene. This mixture was then treated incrementally with divinylbenzene (0.81eq). The material was precipitated in methanol and the product isolated with a linking efficiency of more than 95%. 417

418

Star-Shaped Polymer, Multiple Star Polymer, and Their Preparation Methods

STAR FORMATION LINKING PROFILE TABLE 1. Physical properties of star polystyrenes prepared by the incremental addition of divinylbenzene to a polystyrene anion having a Mn of roughly 26,000 daltons.

Entry

Increments of 0.74 ml of Divinyl Benzene

Star Polystyrene Mn 104 (daltons)

Linking Efficiency (%)

PDI

Number of Arms

2 5 7

31.2 67.3 88.8

93 98 99

1.05 1.07 1.09

13 26 34

1 2 3

TABLE 2. Physical properties of star polystyrenes prepared by the single addition of divinylbenzene to polystyrene anion having a Mn of roughly 26,000 daltons.

Entry

Single Addition of Divinyl Benzene (ml)

1 2 3

1.7 3.4 5.1

Star Polystyrene Mn 104 (daltons)

Linking Efficiency (%)

PDI

Number of Arms

68 75 79

1.05 1.05 1.08

16 21 27

42.3 54.1 69.5

NOTES 1. Hyperbranched water-soluble polyesters containing polyethylene glycol and adipic acid were prepared by Stumbe [1] and used as additives in paints. 2. An 8-pedal flower-like nanoparticle and nanostrings consisting of styrene and butadiene were prepared by Wang [2,3], respectively, and used as a component in tires. 3. Dendritic-based macromolecules containing polystyrene were prepared by Frechet [4] and used in specialty medical applications. Star-shaped conjugated dentrimers containing styrene were prepared by Burn [5] and used as components in light-emitting diodes. References 1. 2. 3. 4. 5.

J-F. Stumbe et al., US Patent 7,148,293 (December 12, 2006) X. Wang et al., US Patent 7,205,370 (April 17, 2007) X. Wang, US Patent 7,179,864 (February 20, 2007) J.M.J. Frechet et al., US Patent 7,101,937 (September 5 2006) P.L. Burn et al., US Patent 7,083,862 (August 1, 2006)

XVII. OPTICAL MATERIALS Second-Order Nonlinear Optical Materials

Title: Polymers Having Pendant Nonlinear Optical Chromophores and Electrooptic Devices Therefrom Author:

D. Huang et al., US Patent 7,019,453 (March 28, 2006)

Assignee:

Lumera Corporation (Bothell, WA)

SIGNIFICANCE A polymer containing the nonlinear optical chromophore trans-2,20 -formyl-3,30 , -4,40 -tetrabutoxyvinylthiophene was prepared and proved is effective as a waveguide.


420

Polymers Having Pendant Nonlinear Optical Chromophores and Electrooptic Devices Therefrom

REACTION OH

N

OAc

i

ii

N

OH

OAc

N

iii

N

CHO

CHO

O

vii

O

Si(CH3)2t-C4H9

vi

N

P(C6H5)3Br

iv

O

Si(CH3)2t-C4H9

v

N

N

CHO

OH

Si(CH3)2t-C4H9 O C4H9O

N

S

S

C4H9O

OC4H9 CHO

viii

OC4H9

Si(CH3)2t-C4H9 O

OH C4H9O

ix

N

S

S

C4H9O

OC4H9

O OC4H9

CN

NC NC

Si(CH3)2t-C4H9

Reaction

421

O Si(CH3)2t-C4H9 O

O C4H9O

OC4H9 O

N

S

S

C4H9O

F CN

NC

OC4H9

x

F

F O

NC O H O

O C4H9O

OC4H9 O

xi

N

S

S

C4H9O

F

F O

OC4H9

F CN

NC NC

CO2H

O

O

O C4H9O

O

OC4H9 O

N

S

S

C4H9O

OC4H9

F

F O

F CN

NC NC

xii

422


a

O

b

O

O

O O O

CO2H

N

C4H9O S C4H9O OC4H9 S OC4H9 NC NC

O O

CN

O F O F F

i: ii: iii: iv: v: vi:

Acetic anhydride DMF, phosphorous oxychloride Ethanol, potassium carbonate t-Butyldimethylsilyl chloride, imidazole, DMF Methanol, sodium borohydride, sodium hydroxide Triphenylphosphine.hydrogen bromide, CHCl3

O

F

F

F

Experimental

423

vii: Butyllithium, trans-2,20 -formyl-3,30 ,4,40 -tetrabutoxy-vinylthiophene, THF viii: 3-Cyano-4,5,5-trimethyl-2-(2,2-dicyanovinylidene)-2,5-hydrofuran, piperidine, CHCl3 ix: Pyridine, CH2Cl2, 4-(trifluorovinyloxy) benzoyl chloride x: THF, hydrochloric acid xi: N,N-Dimethylaminopyridine, triethylamine, CH2Cl2, phthalic anhydride xii: Poly(4-vinylphenol), 4-(dimethylamino)-pyridinium 4-toluenesulfonate (0.786 mmol), THF, CH2Cl2, 4-(trifluorovinyloxy) benzoyl chloride, di-isopropylethylamine, 1,2-dicyclohexyl-carbodiimide

EXPERIMENTAL 1.

Preparation N-Ethyl-N-(6-Hexylacetate)Aniline

N-Ethyl-N-(6-hydroxyhexyl)aniline (0.5 mol) and acetic anhydride (0.75 mol) were mixed and heated to 65 C for 20 hours. The reaction mixture was then poured into water and extracted with CH2Cl2. The crude oil was purified by flash column chromatography with hexane/EtOAc, 3:1, respectively, and the product was isolated in 84% yield. 2.

Preparation N-Ethyl-N-(6-Hexylacetate)-4-Formylaniline

DMF (0.624 mol) was placed in a reaction vessel and cooled to 0 C and then treated with the dropwise addition of POCl3 (0.499 mol). The Step 1 product (0.416 mol) was added and stirred 30 minutes at ambient temperature and 3 hours at 100 C. The reaction mixture was next poured into water and neutralized with NaHCO3. After extraction with CH2Cl2 the mixture was purified by flash column chromatography with hexane/EtOAc, 5:2, respectively, and the product was isolated in 80% yield. 3.

Preparation N-Ethyl-N-(6-Hydroxyhexyl)-4-Formylaniline

The Step 2 product (0.33 mol) was dissolved in 600 ml of ethanol and treated with K2CO3 (0.36 mol); the mixture was then stirred 4 hours at ambient temperature. The mixture was extracted with CH2Cl2 and dried with MgSO4. After the mixture was filtrated and concentrated, the residue was purified by flash column chromatography with EtOAc/CH2Cl2, 3:2, respectively, and the product was isolated in 66% yield. 4.

Preparation N-Ethyl-N-(6-t-Butyldimethylsilylhexyl)-4-Formylaniline

The Step 3 product (0.217 mol), t-butyldimethylsilyl chloride (0.282 mol), imidazole (0.563 mol), and 140 ml of DMF were mixed and heated for 10 hours at 50 C. The mixture was then poured into water and extracted with CH2Cl2. It was dried and concentrated, and the residue was purified by flash column chromatography with hexane/EtOAc, 3:1, respectively, and the product was isolated in 87% yield.

424


5. Preparation N-Ethyl-N-(6-t-Butyldimethylsilylhexyl)4-Hydroxylmethylaniline The Step 4 product (0.187 mol) was dissolved in 200 ml of methanol and treated at 0 C with the dropwise addition of NaBH4 mixed with 4 ml of 7% NaOH solution diluted with 30 ml of water. After the mixture was stirred at ambient temperature for 3 hours, it was poured into water and extracted with CH2Cl2. The product was purified by flash column chromatography with hexane/EtOAc, 2:1, respectively, and isolated in 84% yield. 6. Preparation N-Ethyl-N-(6-t-Butyldimethylsilylhexyl)4-(Triphenylphosphine Bromide) Methylaniline The Step 5 product (0.157 mol), PPh3HBr (0.142 mol), and 400 ml of CHCl3 were mixed and refluxed for 3 hours in a reactor containing a Dean–Stark apparatus. The mixture was then concentrated by removing most of the solvent and precipitating in diethyl ether; the product was isolated in 84% yield. 7.

Intermediate 7

The Step 6 product (0.103 mol) was dissolved in 2000 ml of THF and cooled to 40 C and then treated with the dropwise addition of butyllithium (0.113 mol). It was stirred at ambient temperature for 30 minutes and then treated with the dropwise addition of trans-2,20 -formyl-3,30 ,4,40 -tetrabutoxy-vinylthiophene (0.09 mol) dissolved in 1400 ml of THF. The reaction mixture was stirred for 10 hours and concentrated, and the residue was purified by flash column chromatography with CH2Cl2/hexane/EtOAc, 4:4:0.2, respectively; the product was isolated in 75% yield. 8.

Intermediate 8

A mixture consisting of the Step 7 product (34.5 mmol), 3-cyano-4,5,5-trimethyl-2(2,2-dicyanovinylidene)-2,5-hydrofuran (41.5 mmol), piperidene (catalytic amount), and 15 ml of CHCl3 were refluxed for 5 hours. The mixture was then purified by flash column chromatography with hexane/EtOAc/CH2Cl2, 4:1.2:4, respectively, and the product was isolated in 45% yield. 9.

Intermediate 9

The Step 8 product (6.52 mmol) and 1.32 ml pyridine were dissolved in 80 ml of CH2Cl2 and then treated with the dropwise addition of 4-(trifluorovinyloxy) benzoyl chloride (13.04 mmol) dissolved in 10 ml of CH2Cl2 at 0 C. The mixture was stirred at ambient temperature for 12 hours and poured into water. It was extracted with CH2Cl2 and purified by flash column chromatography with hexane/CH2Cl2/EtOAc, 4:4:0.4, respectively, and the product was isolated in 91% yield.

Testing

10.

425

Intermediate 10

The Step 9 product (5.875 mmol) dissolved in 150 ml of THF was treated with 50 ml of 1M HCl and then stirred at ambient temperature for 12 hours and neutralized with NaHCO3 solution. After being extracted with CH2Cl2, it was purified by flash chromatography using hexane/CH2Cl2/EtOAc, 1:2:1, respectively, and the product was isolated in 82% yield. 11.

Intermediate 11

The Step 10 product (0.848 mmol), N,N-dimethylaminopyridine (0.017 mmol), and triethylamine (1.7 mmol) were dissolved in 30 ml of CH2Cl2 and then treated with phthalic anhydride (1.06 mmol). The mixture was next stirred at ambient temperature for 12 hours. The solution was washed with 1M of HCl solution, extracted with CH2Cl2, and washed with NaHCO3 solution and water. The mixture was purified by flash chromatography using CH2Cl2/acetone, 2.5:1, respectively, and the product was isolated in 73% yield. 12.

Preparation of Polymer

Vacuum dried poly(4-vinylphenol) (0.9436 g), 4-(dimethylamino)pyridinium 4-toluenesulfonate (0.786 mmol), and the Step 11 product (1.044 g) were dissolved into 30 ml of THF and 10 ml of CH2Cl2. After the addition of 1,2-dicyclohexylcarbodiimide (1.965 mmol) the solution was stirred at ambient temperature for 40 hours. Thereafter 4-(trifluorovinyloxy) benzoyl chloride (17.12 mmol), 1,2-dicyclohexylcarbodiimide, and di-isopropylethylamine (14 mmol) were added, and the mixture stirred an additional 24 hours. The solution was then concentrated to about 10 ml and precipitated in methanol. The solid was isolated, re-dissolved in CH2Cl2, and reprecipitated in methanol, the process being repeated 10 times. The product was dried and 2.43 g were isolated as a dark blue powder.

DERIVATIVES Only the Step 12 derivative was prepared

TESTING A electrooptic polymer crosslinked film was formed by spin-coating a 25 wt% of the Step 12 product in cyclopentanone onto an ITO covered glass slide. The solution was filtered through a 0.2 mm nylon filter, spin-coated at 500 rpm for 6 seconds and 1000 rpm for 30 seconds, and then soft baked at 50 C overnight under vacuum to give a 3.2 mm thick film. The film was corona poled with a needle at 20 kVand heated to 220 C for 5 minutes for crosslinking. The film was then cooled to ambient temperature under the applied field to give an electro-optic film with an r33 of 36 pm/Vat 1.31 mm.

426


NOTES 1. Additional Step 12 polymeric nonlinear optical chromophores and electrooptic devices were prepared by the author [1] in earlier investigations. 2. Compositions comprising a crosslinkable perfluoro poly(aryl ether), (I), and a nonlinear optical chromophore were prepared by the author [2] and Chen [3]. F O

F

O

F O

CF3 O

O

O CF3

F4

F4

F4

O

a

F4

(I)

3. Nonlinear optical phenyldiazo chromophores, (II), and (III), were prepared by Gharavi [4] and Lindsey [5], respectively, and used as multifunctional optical switches.

OH

OH

O2N O2N

NO2

N

N N

N

N

N

(II)

OH

N N

H3CO

OCH3

(III)


D. Huang et al., US Patent 6,750,603 (June 15, 2004) and US Patent 6,716,995 (April 6, 2004) D. Huang et al., US Patent Application 2007-0032628 (February 8, 2007) B. Chen et al., US Patent 7,196,155 (March 27, 2007) A. Gharavi et al., US Patent 7,205,347 (April 17, 2007) G.A. Lindsay et al., US Patent 7,071,268 (July 4, 2006)

XVIII. PHOTOACTIVE POLYMERS A. Photoluminscence

Title: Polymeric Compound and Organic Luminescence Device Author:

J. Kamatani et al., US Patent 7,238,435 (July 3, 2007)

Assignee:

Canon Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE Iridium-containing copolymers have been prepared by postreacting fluorene-or biphenyl copolymers with a cyclic bidentate ligand iridium derivatives. These block copolymers demonstrate exceptionally high luminescent efficiency.

REACTION

O O

B

C8H17 C8H17

O B

C8H17 O

C8H17

i N

C8H17

C8H17

C8H17 N

a

ii

C8H17

a

N

N

b c

Ir N


428

Polymeric Compound and Organic Luminescence Device

i: 2,5-Dibromopyridine, THF, potassium carbonate, tetrakistriphenylphosphine palladium ii: Iridium acetylacetone complex, glycerol, hydrochloric acid

EXPERIMENTAL 1.

Preparation of Poly[2,7-(9,9-di-n-octyl-fluorene)-co-2,5-Pyridine]

A 20-ml flask was charged with a fluorene-borate complex (2.0 mmol), 2,5-dibromopyridine (2.0 mmol), and a mixture of 8 ml of THF and 6 ml of aqueous 2 M K2CO3. Once the mixture was dissolved, the solution was treated with Pd(PPh3)4 (0.0015 mmol) and refluxed for 48 hours. Thereafter methanol was added to the solution, causing a precipitate to form. The solid was washed with water and then Soxhlet was extracted with acetone for 24 hours; the product was isolated in 85% yield having a Mn of 11,000 daltons.

2.

Preparation of Poly[2,7-(9,9-di-n-Octyl-Fluorene)-co-2,5-Pyridine]

A 100-ml round bottomed flask containing 50 ml of glycerol was treated with the Step 1 product (1.0 mmol) and the iridium acetylacetone complex (0.2 mmol). The mixture was heated for 18 hours and then cooled to ambient temperature and poured into 300 ml of 1 M HCl. The resulting precipitate was isolated, washed with water, and dissolved in chloroform and filtered. The material was subjected to Soxhlet extraction with acetone for 24 hours, and 0.50 g of a yellow powder was isolated. The product had a Mn of 13,000 daltons with a polydispersity of 2.1.

LUMINESCENT TESTING A selected experimental agent was dissolved in chloroform and a 0.1 mm thick sample spin-coated onto a quartz substrate. Thereafter the sample was exposed to pulsative nitrogen laser light at an excitation wavelength of 337 nm at ambient temperature using a luminescence life meter. After completion of the excitation pulses, the decay time of luminescence intensity was measured. Testing results are provided in Table 1.

Notes

429

TABLE 1. Selected iridium-containing polymers and corresponding luminescent halftimes after excitation at 337 nm. Entry

Structure C8H17

C8H17

1a N

C8H17

1b N

C8H17

a

C8H17

C8H17

Luminscent Halftime (h)

N C8H17

350

b c

C8H17

a

N

337

b c

Ir

N

N C8H17

4

C 8H17

C8H17

C 8H17

b

O a

N

O O O Ir

c

700

(Acac)2

C6H13 C6H13

b

O

5

c

O

a

O

C6H13 C6H13

Ir

O

600

(Acac)2

NOTES 1. Polymerizable iridium-containing compounds, (I), were prepared by Takeuchi [1] and used in light-emitting devices.

O O

N

Ir

O O N

R = H, Cl, NO2

R

(I)

430

Polymeric Compound and Organic Luminescence Device

2. Fryd [2] prepared rhenium, (II), and iridium copolymers that exhibited photoluminescent and electroluminescent properties.

a

b O O

SO2 O N

N Re

OC

CO CO

(II)

3. Macromolecular quinoxaline, (III), and pyran derivatives, (IV), were prepared by Shitagaki [3] and Yamagata [4], respectively, and used in light-emitting elements.

N N

N N

N

N

N

N

(III)

Notes

NC

431

CN

O N

N (IV)

4. A polymeric fluorescent material exhibiting fluorescent properties was prepared by Noguchi [5] having an excellent fluorescence quantum yield and light emitting efficiency when used a light-emitting device.

C8H17

C8H17

N (IV)


M. Takeuchi et al., US Patent Application 20040247934 (December 9, 2004) M. Fryd et al., US Patent 7,060,372 (June 13, 2006) S. Shitagaki et al., US Patent 7,245,073 (July 17, 2007) S. Yamagata et al., US Patent 7,217,465 (May 15, 2007) T. Noguchi et al., US Patent 7,258,932 (August 21, 2007)

a

Title: Electroactive Fluorene Copolymers and Devices Made with Such Polymers Author:

F. P. Uckert et al., US Patent 7,211,643 (May 1, 2007)

Assignee:

E. I. du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE There is a continuing need for preparing photoactive compounds having both improved efficiency and processes associated with their production. To address this need, electroluminescent conjugated copolymers containing 2,7-fluorenyl units have been prepared in a single synthetic step that require limited processing efforts and that are suitable for emission in the blue and blue-green spectral region.

REACTION C6H13

I

I

C2H5

432

C2H5

N

i C2H5

C2H5

a

Derivatives

433

EXPERIMENTAL Preparation of Electroluminescing Copolymer A 50-ml Schlenck tube equipped with a stirring bar containing bis(1,5-cyclooctadiene)-nickel(0) (4.48 mmol), 2,20 -bipyridyl (4.48 mmol), and 1,5-cyclooctadiene (4.48 mmol) was treated with 5 ml of DMF and the ensuing deep blue/ purple solution stirred at 60 C for 30 minutes. The mixture was then treated with 2,7-diiodo-9,9-bis(2-ethylhexyl)fluorene (1.68 mmol) and 2,5-bis(p-bromophenyl)-N-(p-hexylphenyl)pyrrole (0.56 mmol) in 20 ml of toluene by syringe and then stirred for 5 days at 75 C. The solution was cooled to ambient temperature and precipitated into a mixture of 100 ml apiece of methanol and acetone and 5 ml concentrated hydrochloric acid. After of the mixture was stirred for 2 hours, it was filtered; the solid residue was dissolved in chloroform and re-precipitated in methanol and acetone solution, and re-filtered. The residue was successively washed with methanol, water and methanol, and dried; the product was isolated having a Mn of 47,200 daltons.


Monomers used in preparing fluorene copolymers.

Entry

Monomer 1

I 1

C2H5

Br 2

C2H5

Monomer 2

C6H13

I C2H5

Br

3

C2H5

Br

N

Br

68,700

C2H5

Br C2H5

47,200

CO2CH3 Br

Br

Mn (daltons)

Br

CO2CH3

98,488 Br

Br

(continued)

434

Electroactive Fluorene Copolymers and Devices Made with Such Polymers

TABLE 1.

(Continued)

Entry

Monomer 1

Br 4

C2H5

Br 5

Monomer 2

Br C2H5

NN O

Br

Br

67,300

Br Br

C2H5

Mn (daltons)

Br

60,900

C2H5

Note: Entry 1 was stirred for 5 days at 75 C and then cooled, while Entries 2 to 5 were capped with bromobenzene after 4 days of heating.

TESTING Fluorene copolymers were tested as light-emitters in a light-emitting diode. The anode used was indium tin oxide supported by a glass substrate where the hole injection/transport layer was spin-coated onto the indium tin oxide. The hole injection/transport layer was poly(3,4-ethylenedioxy-thiophene) at a thickness of about 2000 A or a bilayer of poly(3,4-ethylene-dioxythiophene) and polyvinylcarbazole at the same thickness. The experimental copolymer was dissolved in toluene to form a 2.0% solutionthen filtered through a 0.22 m filter and spincoated over the hole injection/transport layer. The target thickness of the copolymer layer was 800 A, with actual thicknesses typically in the range of 500 to 1000 A. Light-emitting test results are provided in Table 2. TABLE 2. Light-emitting testing for fluorene copolymers in a light-emitting diode using different hole injection/transport layers. Entry

Hole Injection/ Voltage at Cd/A*1 at Transport 100 Cd/m2 25 mA

1 2 3 4 5

PEDOT*2 PVK*3 PVK PEDOT/PVK PEDOT/PVK

*1

— 6.6 6.9 >10 >10

Candela Poly(3,4-ethylene-dioxythiophene) *3 Polyvinylcarbazole *2

— 0.06 0.2 0.68 1.14

Cd/A (at mA)

Cd/m2 (at V)

QE% (at V)

— 849 (12 V) 0.18 (12 V) 0.068 (55 mA) — — 0.22 (20 mA) — — 0.87 (3 mA) — — 3.74 (0.04 mA) — —

Notes

435

NOTES 1. Aluminium-pyrazol-5-one derivatives, (I), prepared by Kathirgamanathan [1] were effective as white light emitters and used in organic electroluminescent devices. Bis(2-phenylimidazo[1,2-a]pyridinato-N,C)iridium derivatives, (II), prepared by Lussier [2] were effective as phosphorescent emission agents.

O

O Ir

Al O N

O

N

N N 3

2

(II) (I) 2. Fluorene copolymers, (III), were prepared by Sohn [3] that offered improved emission efficiency and blue light color purity and were used in organoelectroluminescent devices.

N

C8H17

0.1

C8H17

N

C8H17

0.9

C8H17

(III) 3. Regiogegular fluorcene, (IV), and carbazole polymers, (V), prepared by Heeney [4] and Leclerc [5], respectively, were useful as electroluminescent devices because of their solubility in organic solvents and ease of processability. OC 8H17

C12 H25

C12 H25

C6H13 N

S

S

(IV)

S

n

(V)

n

436

Electroactive Fluorene Copolymers and Devices Made with Such Polymers

4. Light-emitting fluorene polymers, (VI), displaying blue electroluminescence were prepared by Mullen [6] and used in electronic devices.

C8H17

C8H17 C8H17

C8H17

n C8H17

C8H17 C8H17

C8H17

(VI)

References 1. 2. 3. 4. 5. 6.

P. Kathirgamanathan et al., US Patent 7,211,334 (May 1, 2007) B.B. Lussier et al., US Patent 7,147,937 (December 12, 2006) B.h. Sohn et al., US Patent 7,172,823 (February 6, 2007) M. Heeney et al., US Patent 7,126,013 (October 24, 2006) M. Leclerc,US Patent Application 2007-0069197 (March 29, 2007) K. Mullen et al., US Patent 7,119,360 (October 10, 2006)

Title:

Light-Emitting Polymers

Author:

M. O’Neill et al., US Patent 7,199,167 (April 3, 2007)

Assignee:

University of Hull (North Humberside, GB)

SIGNIFICANCE Conventional displays comprise twisted nematic liquid crystals that require intense backlighting, causing a heavy battery power drain. A process for preparing a new class of light-emitting polymers that require lower power consumption and have higher brightness is described. The combination of these new light-emitting polymers with existing LCD technology offers the prospect of low-cost, bright, portable displays with the benefits of simple manufacturing.

437

438


REACTION C3H7

C3H7

C3H7

C3H7

i Note 1

S

ii S Br

S

S

Br C3H7

iv Note 2

C3H7

C3H7

C3H7

iii S

S OH

S

OCH3

S

OH

OCH3 C3H7

C3H7 O O S

S

O

O

O

O

i: N-Bromosuccinimide, hydrochloric acid, CH2Cl2, CCl3H ii: 4-(Methoxyphenyl)boronic acid, tetrakis(triphenylphosphine)palladium, ethylene glycol dimethylether, sodium carbonate, hydrochloric acid iii: Boron tribromide, CCl3H iv: 1,6-Heptadienyl-6-bromohexanoate, potassium carbonate, acetonitrile

EXPERIMENTAL 1.

Preparation of 2,7-bis(5-Bromothien-2-yl)-9,9-Dipropylfluorene

A mixture consisting of 2,7-bis(thien-2-yl)-9,9-dipropylfluorene (5.55 mmol) dissolved in 25 ml of CCl3H was slowly treated with N-bromosuccinimide (12 mmol) and then refluxed for 1 hour. Thereafter the solution was diluted with 100 ml of CH2Cl2, washed with 100 ml of water, 150 ml of 20% hydrochloric acid, 50 ml of saturated aqueous sodium bisulphite solution, and dried with MgSO4. The mixture was concentrated then purified by re-crystallization using ethanol/CH2Cl2, and the product was isolated in 86% yield as yellow-green crystals, MP ¼ 160–165 C.

Experimental

439

2. Preparation of 2,7-bis[5-(4-Methoxyphenyl)Thien-2-yl]-9, 9-Dipropylfluorene A mixture of the Step 1 product (4.7 mmol), 4-(methoxyphenyl)boronic acid (14 mmol), tetrakis(triphenylphosphine)palladium(0) (0.3 mmol), Na2CO3 (29 mmol), and 20 ml of water in 100 ml of ethylene glycol dimethylether was refluxed for 24 hours. Once the mixture cooled, additional 4-(methoxyphenyl)boronic acid (6.5 mmol) was added and the mixture was again refluxed for 24 hours. Thereafter 20 ml of DMF was added to the solution, and it was further heated to 110 C for 24 hours, cooled, and treated with 100 ml 20% hydrochloric acid. The cooled reaction mixture was extracted with 250 ml of diethyl ether, and the combined ethereal extracts were washed with 100 ml of water, dried with MgSO4, and concentrated onto silica gel. The mixture was purified by chromatography using CH2Cl2/hexane, 1:1, re-crystallized from CH2Cl2/ hexane, and the product was isolated in 63% yield as a green crystalline solid. 1

HNMR (CDCl3): d 7.66 (2H, d), 7.49 (2H, dd), 7.46 (2H, d), 7.12 (2H, d), 7.05 (2H, d), 1.98 (4H, t), 0.69 (10H, m) IR (KBr cm1): 3481 (w), 2956 (s), 1468 (s), 1444 (m), 1206 (w), 1011 (w), 963 (w), 822 (m), 791 (s), 474 (w) MS (m/z): 572 (Mþ), 529, 500, 487, 448, 433, 420, 407, 375, 250, 126

3. Preparation of 2,7-bis[5-(4-Hydroxyphenyl)Thien-2-yl]-9, 9-Dipropylfluorene) The Step 2 product (2.1 mmol) was treated with the dropwise addition of 9 ml of 1 M solution boron tribromide in CCl3H at 0 C and then stirred at ambient temperature and quenched by adding it to 200 ml of ice-water. The product was extracted using 200 ml of diethyl ether and washed with 150 ml of 2 M aqueous sodium carbonate and dried using MgSO4. The mixture was purified by column chromatography with silica gel using CH2Cl2/diethyl ether/ethanol, 40:4:1, respectively, and the product was isolated as a green solid in 96% yield. 1

HNMR (CD2Cl2): d 7.71 (2H, dd), 7.61 (8H, m), 7.37 (2H, d), 7.24 (2H, d), 6.95 (4H, d), 3.84 (6H, s), 2.06 (4H, m), 0.71 (10H, m) IR (KBr pellet cm1): 2961 (w), 1610 (m), 1561 (m), 1511 (s), 1474 (s), 1441 (m), 1281 (m), 1242 (s), 1170 (s), 1103 (m), 829 (m), 790 (s) MS (m/z): 584 (Mþ -C3H7), 569, 555, 539, 525, 511, 468, 313, 277 Elemental analysis Calculated: wt % C 78.56%, H 6.11%, S 10.23%. Found: C 78.64%, H 6.14%, S 10.25%

4. Preparation of 2,7-bis(5-{4-[5-(1-allylbut-3-enyloxycarbonyl)pentyloxy] phenyl}thien-2-yl)-9,9-dipropylfluorene A mixture of the Step 3 product (1.0 mmol), 1,6-heptadienyl-6-bromohexanoate (2.7 mmol), and potassium carbonate (3.6 mmol) dissolved in 25 ml of acetonitrile was refluxed for 20 hours, filtered, and the precipitate isolated and rinsed with 230 ml of CH2Cl2. The solution was concentrated onto silica gel and purified by column chromatography using CH2Cl2/hexane, 1:1. The solid was re-crystallized

440


using CH2Cl2/ethanol mixture, and the product was isolated as a green-yellow solid in 21%yield. 1

HNMR (d-acetone): d 8.56 (2H, s), 7.83 (2H, dd), 7.79 (2H, d), 7.68 (2H, dd), 7.57 (4H, dd), 7.50 (2H, dd), 7.31 (2H, dd), 6.91 (4H, dd), 2.15 (4H, m), 0.69 (10H, m) IR (KBr pellet cm1): 3443 (s, broad), 2961 (m), 1610 (m), 1512 (m), 1474 (m), 1243 (m), 1174 (m), 1110 (w), 831 (m), 799 (s) MS (m/z): 598 (Mþ), 526, 419 (M100), 337

DERIVATIVES C3H7

C3H7 O S

R O

S

O

A

O O A O

TABLE 1. invention. Entry

R

Selected light-emitting pre-polymers prepared according to the current R

2

CH2(CH2)3CH2

3

CH2(CH2)2CH2

5

CH2(CH2)6CH2

1

A

CH2

CH2

N CH2

HNMR (CDCl3) d 7.68 (2H, d), 7.60 (2H, dd), 7.58 (2H, d), 7.57 (2H, d), 7.33 (2H, d), 7.20 (2H, d), 6.91 (2H, d), 5.75 (4H, m), 5.08 (8H, m), 5.00 (2H, quint), 4.00 (4H, t), 2.33 (12H, m), 2.02 (4H, t), 1.82 (4H, quint), 1.71 (4H, quint), 1.53 (4H, m), 0.72 (10H, m) IR (KBr pellet cm1): 3443 (s), 2955 (s), 1734 (s), 1643 (w), 1609 (m), 1512 (m), 1473 (s), 1249 (s), 1178 (s), 996 (m), 918 (m), 829 (m), 799 (s) APCI-MS (m/z): 1015 (Mþ, M100), 921 Elemental analysis Calculated: wt % C ¼ 76.89, wt% H ¼ 7.35, wt% S ¼ 6.32%. Found: wt% C ¼ 76.96, wt% H ¼ 7.42, wt% S ¼ 6.23

Notes

441

NOTES 1. The preparation of the Step 1 reagent, 2,7-bis(thien-2-yl)-9,9-dipropylfluorene, (I), was provided by the author [1] as illustrated below.

C3H7

C3H7

i

C3H7

iii

ii

C3H7

C3H7

C3H7

C3H7

iv S

Br

Br

S

i: Butyl lithium, THF, propyl bromide ii: Butyl lithium, THF, propyl bromide iii: Bromine, CCl3H iv: 2-(Tributylstannyl)thiophene, tetrakis(triphenylphosphine)-palladium, DMF 2. Photopolymerization of pre-polymers was conducted by the author using a 300 nm lamp having a constant intensity of 100 MWcm2. Polymer repeat units are illustrated in the two equations below.

O R

O

a O

O

R

R

O

a O

O R

O

O R

442


3. Additional light-emitting pre-polymer derivatives, (I), were prepared by the author [1] in an earlier investigation and are discussed. S N O

N O

O

O

O O

(I)

4. Ise [2] prepared a light-emitting element consisting of a light-emitting layer, (II), placed between a pair of electrodes containing a perfluoroaromatic s-triazine derivative, (III), layer. F5

N

N

F4

N

N F5

N F5

N

(III)

(II)

5. Fujii [3] prepared a five-component, (IV) – (VIII), organic light-emitting device that emitted a spectral component in the wavelength range of blue or shorter.

N

N

N

N

N

Ir (IV)

(VI)

(V)

N

N

O N

N

NC

(VII)

(VIII)

t-C4H9

CN

3

Notes

443

6. Swagger [4] prepared solid films of a new luminescent and conductive polymer composition, (IX), containing chromophores that exhibited increased luminescent lifetimes, higher quantum yields, and amplified emissions.

C8H17 N C8H17 O

O C8H17 N C8H17

(IX) 7. Organic light-emitting compounds, (X) and (XI), prepared by Lee [5] and Kim [6], respectively, had excellent electrical characteristics, thermal stability, and photochemical stability while providing a low turn-on voltage and color purity characteristics when used in organic light-emitting devices. t-C4H9 t-C4H9 N N

X = CH, N(CH3), O, S X

t-C4H9

(X)

(XI)

References 1. M. O’Neill et al., US Patent 7,166,239 (January 23, 2007) and US Patent Application 2005-0004252 (January 6, 2005) 2. T. Ise et al., US Patent 7,189,989 (March 13, 2007) 3. H. Fujii,US Patent 7,201,975 (April 10, 2007) 4. T.M. Swagger et al., US Patent Application 2007-0081921 (April 12, 2007) 5. D.H. Lee et al., US Patent Application 2007-0069203 (March 29, 2007) 6. M.S. Kim et al., US Patent Application 2007-0072002 (March 29, 2007)

Title: Modified Suzuki-Method for Polymerization of Aromatic Monomers Author:

C. Towns et al., US Patent 7,173,103 (February 6, 2007)

Assignee:

General Electric Company (Schenectady, NY)

SIGNIFICANCE A modified Suzuki coupling catalyst has been used for preparing high molecular weight aromatic copolymers derived from fluorene and triphenylamine or benzothiadiazole. The coupling reagent consists of a palladium (II) catalyst containing orthosubstituted phosphines and can be used to generate polymers with molecular weights exceeding 500,000 daltons. The polymeric materials are useful in electronic and optoelectronic applications.

REACTION

Br

N

Br

N

a

i C8H17 C8H17

i: 9,9-Di-n-octylfluorene-2,7-di(ethyleneborate), dichlorobis(tri-o-tolylphosphine)palladium(ll), toluene, tetraethylammonium hydroxide, bromobenzene, phenylboronic acid

444

Experimental

445

EXPERIMENTAL Preparation of Poly(N,N-bis(Phenyl)-4-sec-Butylphenylamine-4,0 4-di-yl)co-(9,9-di-n-Octylfluorene-2,7-di-yl) [Poly(TFB-co-F8)] A reaction vessel was charged with 285 ml of toluene, 9,9-di-n-octylfluorene-2,7di(ethyleneborate) diester, [F8], (15.17 g), and N,N-bis(4-bromophenyl)-4-secbutylphenylamine, [TFB], (13.12 g), the mixture was degassed by sparging with nitrogen at 25 C to 35 C for 60 minutes. The mixture was then treated with dichlorobis(tri-o-tolylphosphine)palladium(ll) (66.8 mg) and stirred for 15 minutes and further treated with 96 ml of 20% aqueous tetraethylammonium hydroxide. The mixture was then refluxed for 18 to 20 hours at 115 C. The product was end-capped by adding 3 ml of bromo-benzene and refluxing for 60 minutes at 115 C. It was further treated with phenylboronic acid (3 g) and refluxed for an additional hour. The reaction mixture was last cooled to ambient temperature and precipitated by pouring into 4 liter of methanol. The product was isolated and had a Mn of roughly 220,000 daltons.

DERIVATIVES TABLE 1. Effect on polymer formation using a modified Suzuki reaction with a palladium catalyst containing an ortho phosphine substitutent. Entry 2 3 4 8 10 11

F8*1 Diester Comonomer

Pd Catalyst Precursor

o-Tolylphosphine Reagent

Mn Polymer

TFB*2 TFB TFB BT*3 BT BT

Pd(BuCN)2Cl2 Pd2(dba) 2 Pd(BuCN)2Cl2 Pd(BuCN)2Cl2 Pd2(dba)2 Pd(BuCN)2Cl2

P(o-tol)3 P(o-tol)3 None P(o-tol)3 P(o-tol) 3 PPH3

169,000 241,000 No polymer 148,000 523,000 54,000

*1

9,9-di-n-Octylfluorene-2,7-di(ethyleneborate) diester N,N-bis(4-bromophenyl)-4-sec-butylphenylamine *3 2,7-dibromobenzothiadiazole *2

NOTES 1. In an earlier investigation by the author [1] an emulsion polymerization was used to prepare the products of the current invention using dichlorobis(triphenylphosphine) palladium(II) as the Suzuki catalyst. 2. Suzuki polymerization of 9,9-di-n-octylfluorene-2,7-di(ethyleneborate) diester, (I), with a biphenyl, (II), or triphenylamine derivative, (III), was used by

446

Modified Suzuki-Method for Polymerization of Aromatic Monomers

O’Dell [2,3] to prepare polyaromatic polymers, (IV) and (V), respectively, which were used in optoelectronic applications. Br O B O

C7H15

O B

Br

O

Br

Br

N

C7H15

C8H17 C8H17

(II)

(I)

(III)

C7H15 N

a C7H15

a

C8H17 C8H17

(IV)

(V)

C8H17 C8H17

3. Polyaromatic phosphine oxide, (VI), and diamines, (VII), were prepared by Towns [4] and coupled with fluorene derivatives, (VIII), to produce the corresponding polyaromatic polymers. Br

N n-C4H9

PO Br

n-C4H9 N

Br

(VI)

(VII)

Br

O B O

C8H17

C8H17

O B O

C8H17 C H 8 17

(VIII)

4. Hexaalkylated phenyl monomer derivatives and pentaaromatic diamines were used by O’Dell [5] to prepared conjugated polymers, (IX), which were used in electroluminescent devices. In a separate investigation by O’Dell [6], terpolymers, (X), were also prepared.

Notes

447

n-C4H9 C8H17 C8H17

C8H17

N

a C8H17

C8H17

C8H17

N

(IX) n-C4H9 n-C4H9

N

b N

a C8H17 C8H17 C5H11O C5H11O

OC5H11 OC5H11

(X)

References 1. 2. 3. 4. 5. 6.

C. Towns et al., US Patent 7,074,884 (July 11, 2006) R. O’Dell et al., US Patent 7,125,952 (October 24, 2006) R. O’Dell et al., US Patent 6,998,181 (February 14, 2006) C. Towns et al., US Patent Application 2007-0031698 (February 8, 2007) R. O’Dell et al., US Patent Application 2007-0034832 (February 15, 2007) R. O’Dell et al., US Patent Application 2006-0149016 (July 6, 2006)

n-C4H9

Title: Block Copolymer and Polymeric Luminescent Element Author:

T. Noguchi et al., US Patent 7,125,930 (October 24, 2006)

Assignee:

Sumitomo Chemical Company, Ltd. (Osaka, JP)

SIGNIFICANCE Block copolymers consisting of two or more blocks bonded through a conjugated bond have been prepared that fluoresce in the solid state. The molecular weight of at least one block is between 1.0 104 and 2.7 105 daltons. Unlike low molecular weight light-emitting materials, however, these light-emitting agents are soluble in a variety of organic solvents and are easily spin-coated as thin films onto selected surfaces for use in polymer light-emitting devices.

REACTION

C8H17

O

i

C8H17

OHC

O CHO

a O

O

C5H5 O

O

O

448

C8H17

O

OCH3

O

C8H17

a b

ii

Derivatives

449

i: 9,9-Dioctyl-2,7-dibromofluorene, 4-bromo-2,5-(3,7-dimethyloctyloxy)benzaldehyde, 2,20 -bipyridyl, THF, bis(1,5-cyclooctadiene)nickel (0) ii: 2-Methoxy-5-(2-ethylhexyloxy)-p-xylylene dichloride, triethyl phosphite, THF, potassium t-butoxide

EXPERIMENTAL 1. Preparation of 3,7-Dimethyloctyloxy)Benzaldehyde-Terminated Poly[9,9-Dioctyl)2,7-Fluorine] A mixture consisting of 9,9-dioctyl-2,7-dibromofluorene (2.7 g), 4-bromo-2,5-(3,7dimethyl- octyloxy)-benzaldehyde (2.3 g), 2,20 -bipyridyl (2.7 g), and 150 ml of THF was charged into a reaction container under argon. It was then treated with bis(1,5cyclooctadiene)nickel(0) (5.0 g), stirred for 10 minutes at ambient temperature, and reacted at 60 C for 7 hours. The mixture was cooled and precipitated into a solution of 25% NH4OH (aq)/methanol/water, 50 ml:100 ml:100 ml, respectively, and then stirred for 1 hour and isolated. The residue was dried, dissolved in chloroform, filtered, and reprecipitated in methanol. The solid was dried under reduced pressure, and 1.4 g of product was isolated. 2.

Preparation of Block Copolymer

2-Methoxy-5-(2-ethylhexyloxy)-p-xylylene dichloride and triethyl phosphate were initially reacted to generate the corresponding phosphonate. Thereafter a mixture of the phosphonate (0.016 g), the Sep 1 product (0.5 g), and 50 ml of THF was charged into a reactor and treated dropwise at ambient temperature with potassium t-butoxide (0.07 g) dissolved in 5 ml of THF over a 10 minute period. The mixture reacted for 2.5 hours at ambient temperature and was then neutralized with acetic acid. The polymer was precipitated by pouring into methanol and dried, and the product was isolated.

DERIVATIVES Three fluorescent polymeric derivatives, (I)–(III), are provided below.

C5H5 C8H17

O

C8H17

a OCH3

OCH3

OCH3

(I)

b

450

Block Copolymer and Polymeric Luminescent Element

C8H17 O

C8H17

O N

N O

O

a

1

t-C4H9

t-C4H9

C8H17 O

b

(II)

C8H17

O N

N O

O

0.3

0.7

b

(III)

TABLE 1. Physical properties of experimental polymers prepared according to the current invention. Entry Step 2 product I II III

Mn (daltons)

Mw (daltons)

Peak Fluorescence (nm)

3.7 104 1.1 104 1.0 104 2.1 104

9.6 104 2.7 105 2.5 104 6.3 104

504 456 470 474

NOTES 1. Bazan [1] prepared cationic conjugated flexible block copolymer derivatives, (IV), containing alkyl substituents along the main chain that disrupted extended-rod structure formation. These were then used in optoelectronic devices and biosensors.

Notes

451

a

(H3C)3N

N(CH3)3

2Br

b

c

(IV)

2. Jen [2] prepared thermally reversibly electrooptic polymers, (V), via a Diels– Alder reaction, as illustrated below, that were used in second-order nonlinear optical devices. a

a

O

O

Retro Diels–Adler

O O

O

O

O

O

O N

N

(V)

O

Diels–Adler

O

O

O

3. Grushin [3] prepared electroluminescent iridium compounds containing fluorinated phenyl-pyridines, (VI), phenylpyrimidines, and phenylquinolines for use in organic electronic devices such as a light-emitting layer.

F

CF3 H N

O Ir

Ir O

N

CF3

H 2

F

(VI)

2

452

Block Copolymer and Polymeric Luminescent Element

References 1. G.C. Bazan et al., US Patent 7,138,483 (December 5, 2006) 2. K.-Y. Jen et al., US Patent 7,144,960 (December 5, 2006) 3. V. Grushin et al., US Patent 7,132,681 (November 7, 2006)

Title: Soluble Poly(Aryl-Oxadiazole) Conjugated Polymers Author:

H. Wang et al., US Patent 7,105,633 (September 12, 2006)

Assignee:

E.I. Du Pont de Nemours and Company (Wilmington, DE)

SIGNIFICANCE A single-step preparation of a new class of soluble co- and terpoly(arylene-oxadiazole) polymers containing at least 20 repeat units have been prepared by the condensation of aromatic dicarboxylic acids with hydrazine hydro-chloride. Photoluminescence efficiencies of 50% were reported. Targeted applications include electroluminescent devices, photovoltaics, and diodes.

REACTION

C2H5 HO2C

C2H5

C2H5 CO2H

C2H5

i

N N O

a

i: Phosphorus pentoxide, methylsulfuric acid, 9,9-di-(2-ethylhexyl)-fluorene-2,7dicarboxylic acid, hydrazine hydrochloride

EXPERIMENTAL Preparation of Poly(9,9-di-(2-Ethylhexyl)-Fluorene-Oxadiazole) Phosphorus pentoxide (3.0 g) was dissolved in 50 ml of methylsulfuric acid at 110 C and then treated with a mixture of 9,9-di-(2-ethylhexyl)-fluorene-2,7-dicarboxylic acid (2.0 g) and hydrazine hydrochloride (286 mg). After the suspension was stirred 453

454

Soluble Poly(Aryl-Oxadiazole) Conjugated Polymers

over 5 hours, a homogeneous viscous solution formed and was cooled to ambient temperature and poured into 500 ml of water. The polymer was precipitated as a white fiber that was isolated by filtration and washed with aqueous Na2CO3, water, and methanol. The crude polymer was dried under vacuum at ambient temperature and then dissolved in 25 ml of THF. The solution was filtered through a 5 mm filter and re-precipitated in water. The polymer was re-isolated, re-washed in water and then methanol, and vacuum dried at ambient temperature. After repeating this purification process three times, the polymer was isolated in 78% yield. H-NMR (500 MHz, THF-d8) d 8.42 (s, 2H, fluorene ring), 8.26 (d, 2H, fluorene ring), 8.13 (d, J ¼ 8 Hz, 2H, fluorene ring), 2.2 2.5 (br, 4H, H-alkyl), 0.8 1.1 (br, 16H, H-alkyl), 0.59 0.65 (br, 14H, H-alkyl).

1

DERIVATIVES AND TESTING RESULTS TABLE 1. Photoluminescence efficiencies for selected experimental agents activated using a UV lamp at 365 nm. Photoluminesence Efficiency Entry Step 1 Product

Polymer Structure —

10

N N O

11

C2H5

C2H5

a

O

C2H5 N N O

14

N N

C2H5 N N O

O

S

a

Zfilm(%)

432

49

13

430

36

8

430

47

15

500

61

30

b

N N O

Zsolution(%)

b

N N

a

l(nm)

b

(continued)

Notes

TABLE 1.

455

(Continued) Photoluminesence Efficiency

Entry

Polymer Structure

l(nm)

Zsolution(%)

Zfilm(%)

454

10

—

O N N

17

O

a

O

NOTES 1. In a subsequent investigation by the author [2] additional poly(aromaticoxadiazole) agents were prepared using [1,2-d:4,5-d’]bisoxazole, (I), and derivatives.

C2H5 X

C2H5

C2H5 O

N

N

O

C2H5 X

X = Br, Cl

(I)

2. Poly(aryl-oxadiazole) conjugated polymers having tunable energy levels, (II), were prepared by the author [2] by adjusting HOMO and LUMO energy levels of precursors and used in light-emitting electronic devices.

456

Soluble Poly(Aryl-Oxadiazole) Conjugated Polymers

O a

N N

(II) 3. Kambe [3] prepared electroluminescent devices containing two or more stacked organic layers, one of which consisted of an electron injecting an organic layer of conjugated poly(aryl-oxadiazole) derivatives, (III) and (IV).

F3C O N N

(III)

Mw = 20,000

a F3C O

O

O O

a = 12

a

O N N

(IV) 4. Thin films containing electron injecting layers of low crystalline oxadiazole derivatives, (V) and (VI), were prepared by Saitoh [4] and used in electroluminescence device.

O

N N N

N

N

N

N O

N O

N

N O

O

(V)

t-C4H9

(VI)

t-C4H9

Notes

457

5. Arylamine polythiophene derivatives, (VII), were prepared by Okada [5] and used as thin film transitors. N

S

S

a

C8H17 C8H17

(VII)


H. Wang et al., US Patent 7,138,483 (November 21, 2006) H. Wang et al., US Patent 7,132,174 (November 7, 2006) E. Kambe et al., US Patent 7,018,724 (March 28, 2006) A. Saitoh et al., US Patent 7,129,386 (October 31, 2006) T. Okada et al., US Patent Application 2002-0048637 (March 1, 2007)

B. Photorefraction

Title: Fullerene-Containing Polymer, Producing Method Thereof, and Photorefractive Composition Author:

M. Yamamoto, US Patent 7,186,781 (March 6, 2007)

Assignee:

Nitto Denko Corporation (Osaka, JP)

SIGNIFICANCE A composition comprising a C60 fullerene-terminated poly(N-[(propylphenyl]-N,N0 , N0 -triphenyl-(1,10 - biphenyl)-4,40 -diamine)methacrylate has been prepared by living radical polymerization. When blended with a plasticizer and a nonlinear chromophore, photorefractive efficiencies were improved by up to 9% at a biased voltage of 60 V/mm.

REACTION a O O

a O O

O O

i

O

ii

O N

N N

O O O

O

N

N

N

N

N

i: Bis(2-bromo-2-methylpropionate), toluene, copper (I) bromide, bipyridine ii: Bipyridine (0.256 mmol), chlorobenzene, THF, C60 fullerene

EXPERIMENTAL 1. Preparation of Poly(N-[(Propylphenyl]-N,N0 , N0 -Triphenyl-(1,10 -Biphenyl) -4,40 -Diamine)Methacrylate The charge transport agent, N-[(meth)acroyloxypropylphenyl]-N,N0 , N0 -triphenyl-(1,10 biphenyl)-4,40 -diamine (2.6 mmol), bipyridine (0.525 mmol), ethylene bis(2-bromo-2458

Derivatives

459

methylpropionate) (0.105 mmol), and toluene (2.1 g) were charged into a flask and then purged with argon gas. The mixture was treated with Cu(I)Br (0.209 mmol), heated to 90 C and polymerized for 18 hours. 1 H NMR indicated that the reaction extent was 71%. The mixture was then diluted with toluene and filtered to remove insoluble impurities. The polymer was precipitated from the solution by adding methanol, filtering, and washing with diethyl ether and methanol to remove unreacted acrylate monomer. The product was dried, and the product isolated had a Mw of 8317 daltons. 2. Preparation of Poly{(N-[(Propylphenyl]-N,N0 , N0 -Triphenyl-(1,10 Biphenyl)-4,40 -Diamine)Methacrylate}-C60 Fullerene The Step 1 product (680 mg), bipyridine (0.256 mmol), and 4 ml of chlorobenzene were charged into a flask and then purged with argon gas for 1 hour. This mixture was next treated with Cu(I)Br (0.100 mmol) and C60 fullerene (0.111 mmol) and heated to 90 C for 18 hours and the residue dissolved in THF. The solution was filtered through a 0.2 mm pore size teflon filter to remove unreacted C60 fullerene. The polymer was precipitated from the solution by adding methanol; it was re-filtered and washed with methanol; the product was isolated as a black solid having a Mw of 10,413 daltons.

DERIVATIVES An additional nonlinear optical copolymer derivative, (I), plasticizer, (II), and nonlinear optical chromophore, (III), were also prepared.

O O

a O O

O O CHO

O

O O CHO

O N

N

O O O

N

N

N N

N

(I)

N

(II)

Nonlinear optical copolymer

N

OH CN

(III) Nonlinear optical chromophore

Plasticizer

460

Fullerene-Containing Polymer, Producing Method Thereof, and Photorefractive Composition

Photorefractive Efficiency Testing Photorefractive evaluation of experimental agents was done by initially dissolving samples in toluene, evaporating off the solvent, and then heating to 150 C to make 200 to 300 mm thick films. Samples were sandwiched between indium tin oxide and separated by a 105 mm spacer. The diffraction efficiency was measured at 633 nm using four-wave mixing experiments. Steady-state and transient four-wave mixing experiments were done using two writing beams making an angle of 20.5 in air; the bisector of the writing beams make a 60 -degree angle relative to the sample normal. The four-wave mixing experiments consisted of two s-polarized writing beams with equal intensity of 0.2 W/cm2 in the sample with a spot diameter of 600 mm. Testing results are provided in Table 1. TABLE 1. Photo diffraction efficiency testing results for sample blends at a biased voltage of 60 V/lm. Sample Blend

Diffraction Efficiency (%)

Step 1 product, 30% Step 2 product, 30% Nonlinear optical copolymer, 25% Plasticizer, 15% Step 1 product, 45% Step 2 product, 15% Nonlinear optical copolymer, 25% Plasticizer, 15%

8

9

NOTES 1. In earlier investigations by the author [1,2] an additional nonlinear optical chromophore, (IV), and charge transport agent, (V), respectively, were prepared and used in photorefractive applications.

O O

N CN CN

(IV)

N

(V)

Notes

461

2. Photorefractive carbazolyl-functionalized cyclic oligosiloxanes, (VI), were prepared by Xu [3] and used in organic light-emitting diodes.

N Si O O Si Si O O Si

N

N N

(VI) 3. Hyperbranched polyester crosslinked photorefractive polymers were prepared by Nishikata [4] consisting of Dispersant Red-19, (VII), and trimesic acid or trimesic acid containing isophthalic acid. Perfluorobenzoate Dispersant Red19 derivatives, (VIII), were also prepared by the author [5]. F C HO

OH N

O O

N

NO2

NO2

(VII)

(VIII)


M. Yamamoto et al., US Patent Application 2006-0235163 (October 9, 2006) M. Yamamoto et al., US Patent 6,653,421 (November 25, 2003) S. Xu,US Patent Application 2006-0232201 (October 19, 2006) Y. Nishikata et al., US Patent Application 2006-0214140 (September 28, 2006) M. Yamamoto,US Patent Application 2006-0094845 (May 4, 2006)

CF2

XIX. POLYMERIZATION METHODS A. Anionic

Title:

Method for Anionic Polymerization of Oxiranes

Author:

P. Desbois et al., US Patent Application 2007-0100097 (May 22, 2007)

Assignee:

BASF Aktiengellschaft

SIGNIFICANCE A method for preparing homopolymers or copolymers of oxiranes by anionic polymerization using s-butyl lithium and triisobutylaluminum but without crown ethers or cryptands during the polymerization process is described.

REACTION a

O

Li

i

a

O

OH

b

ii

i: Cyclohexane, s-butyl lithium ii: Triisobutylaluminum, oxirane

EXPERIMENTAL 1.

Preparation of Polystyryllithium

A reaction vessel was charged with 3.5 ml of styrene diluted with 14 ml of cyclohexane and then treated with 1.25 ml of 1M s-butyl lithium and polymerized at 0 C for 2 hours. The polystyryl lithium block obtained had a polydispersity index of 1.1 and a Mn of 1700 daltons.


464

2.

Method for Anionic Polymerization of Oxiranes

Preparation of Poly(Oxirane-b-Styrene)

A second vessel was charged with 1.75 ml of triisobutylaluminum and 4 ml of the Step 1 product and then treated with 6 ml of oxirane where the aluminum/lithium molar ratio was 5:1, respectively. The mixture was polymerized at 0 C for 60 minutes and 20 C for 15 hours and then terminated. The results for the PS-PPO block copolymerization was an 98% conversion, a polydispersity index of 1.7, and a Mn of 7700 daltons.

NOTES 1. Knoll [1] anionically prepared styrene-butadiene block copolymer mixtures using sec-butyllithium followed by hydrogenation, and the material was then used as transparent films. 2. The author [2] prepared poly(a-methylstyrene-b-styrene) copolymers using s-butyl lithium and triisobutylaluminum. References 1. K. Knoll et al., US Patent 7,064,164 (June 20, 2006) 2. P. Desbois et al., US Patent 7,101,941 (September 5, 2006)

Title:

Amido-Organoborate Initiator Systems

Author:

S. Feng et al., US Patent Application 2007-0083051 (April 12, 2007)

Assignee:

The Dow Chemical Company (Midland, MI)

SIGNIFICANCE A new free radical class of polymerization agents consisting of amido-borate compounds have been prepared by reacting an organoborate with a hydrocarbyl amine. These reagents are particularly useful as hardeners in polymer formulations.

REACTION Li

N N

i Notes 1,2

(C2H5)3B

Na

N N B(C2H5)3

i: THF, triethylborane

EXPERIMENTAL Preparation lithium dimethylamidotriethylborate A slurry of sodium imidazole (50 mmol) in 30 ml of THF was treated with the slow addition of triethylborane (100 mmol) and then stirred for 5 hours at ambient temperature. The mixture was next concentrated and a brown oil isolated. The crude product was isolated in 98% yield and used without additional purification.

465

466

Amido-Organoborate Initiator Systems

DERIVATIVES

N

B(C2H5)3

Li

(C2H5)3B

Li

(C2H5)3B

N N

N N B(C2H5)3

P((CH2)2CH3)4

NOTES 1. The amido-organoborates were used as hardeners in formulations as illustrated below: A mixture of 633 parts of methyl methacrylate, 180 parts of poly(methylmethacrylate), and 45 parts of styrene butadiene styrene block copolymer were placed in a half gallon paint can and rolled on a roller mill overnight. Once the polymers were dissolved, 85.8 parts were placed into an 8 oz plastic container and treated with 2 parts fumed silica and 2 parts of glass beads then mixed by hand using a tongue depressor. Finally 10 parts of amido-borate hardener were added to the container and mixed and the resulting cement packaged in an 8 oz plastic cup.

2. Comprehensive hardening formulations using amido-organoborates are described by the author [1] in an earlier investigation. 3. Organboranes such as sodium tetraethyl borate, lithium phenyl triethyl borate, and tetramethylammonium phenyl triethyl borate were prepared by Kneafsey [2] and Maandi [3], respectively, and used as initiators and adhesive agents for low surface energy substrates. 4. An initiator system consisting of triethylborane and hexamethylenediamine was prepared by Deviny [4] and used in adhesives. References 1. 2. 3. 4.

S. Feng et al., US Patent Application 2007-0079931 (April 12, 2007) B.J. Kneafsey et al., US Patent 7,189,463 (March 13, 2007) E. Maandi et al., US Patent 7,098,279 (August 26, 2006) E.J. Deviny et al., US Patent 7,189,303 (March 13, 2007)

Title: Process for Manufacturing Vinyl-rich Polybutadiene Rubber Author:

L. Jiang et al., US Patent 7,186,785 (March 6, 2007)

Assignee:

Changchun Institute of Applied Chemistry Chinese Academy of Science (Changchun, CN)

SIGNIFICANCE A method for converting 1,3-butadiene into polybutadiene having at least an 88.4% vinyl content using iron isooctanoate, triisobutylaluminum, and ethyl phosphite is described. The optimum weight ratio of reagents of aluminum/iron was 5:100 with a phosphite/iron ratio of 1:20, respectively.

REACTION i Notes 1, 2, 3

a

i: Hexane, iron isooctanoate, triisobutylaluminum, ethyl phosphite

EXPERIMENTAL 1.

Preparation of Polybutadiene Having an 88.4% Vinyl Content

A reactor was charged with 84 ml of hexane and butadiene (10 g) and then treated sequentially with iron isooctanoate (0.0124 mmol), triisobutylaluminum (0.19 mmol), and ethyl phosphite (0.0295 mmol). The mixture was placed into a 50 C water bath and polymerized for 4 hours. Thereafter an aqueous alcohol solution containing 2,6-di(t-butyl)-4-cresol was added to precipitate the rubber sample. The material was dried, and the product was isolated.

467

468

Process for Manufacturing Vinyl-rich Polybutadiene Rubber

SCOPING REACTIONS TABLE 1. Conversion of 1,3-butadiene into poly(butadiene) having a high vinyl content using iron isooctanoate, triisobutylaluminum, and ethyl phosphite.

Entry

Reagent Addition Iron Isooctanoate (A) Triisobutylaluminum (B) Ethyl Phosphate (C)

1 2 3 4

A, A, A, A,

B, C C, B B, C B, C

Conversion (%)

[Z] (dL/g)

Gel Formation (%)

Vinyl Content (%)

95 98 95 99

6.54 –– 8.0 ––

1.4 –– 5.0 ––

88.4 86.4 83.8 ––

Tg ( C) –– 38 –– 23

Note: The sequential reagent addition marginally impacted the overall vinyl incorporation levels.

NOTES 1. In a subsequent investigation by the author [1], high cis-content polybutadiene having a controlled molecular distribution was prepared using neodymium neodecanoate, AlH(i-C4H9)2, methylaluminoxane, and Al(i-C4H9)2Cl. 2. Luo [2] prepared syndiotactic polybutadiene having a high vinyl content using iron(III) 2-ethylhexanoate, bis(2-ethylhexyl) hydrogen phosphate, and tri-nbutylaluminum. 3. Using diisobutylaluminum hydride and triisobutylaluminum, 20:80, respectively, with neodymium [III] neodecanoate, Luo [3] also prepared poly(butadiene) having a 98.7% 1,4-linkage. By using only diisobutylaluminum hydride with neodymium (III) versatate, Luo [4] also prepared high cis-content polybutadiene having an 98.4% 1,4-linkage. References 1. 2. 3. 4.

L. Jiang et al., US Patent Application 2005-0113544 (May 26, 2005) S. Luo, US Patent 6,720,397 (April 13, 2004) and US Patent 6,620,760 (September 16, 2003) S. Luo et al., US Patent 7,094,849 (August 22, 2006) S. Luo et al., US Patent 7,008,899 (March 7, 2006) and US Patent 6,699,813 (March 2, 2004)

Title:

Catalyst for Synthesizing High Transpolymers

Author:

A. F. Halasa et al., US Patent 7,189,792 (March 13, 2007)

Assignee:

The Goodyear Tire and Rubber Company (Akron, OH)

SIGNIFICANCE A catalyst combination consisting of the barium salt of tri(ethyleneglycol)ethyl ether, Ba(OCH2CH2OCH2CH2OCH2CH3)2, with tri-n-octyl aluminum and n-butyl lithium has been used to prepare random poly(styrene-co-butadiene) containing a high butadiene transcontent. These polymers were designed to be co-cured with natural rubber and used as components in automotive tires.

REACTION a i

b

Notes 1, 2, 3, 4

a>b c>d

c d

0

00

i: bis[2-(2-Ethoxyethoxy)-ethanolato-O,O ,O ] barium, ethyl benzene, tri-n-octyl aluminum, n-butyl lithium, butadiene

EXPERIMENTAL 1.

Preparation of Catalyst

The catalyst was prepared by treating a 37.33% solution of bis[2-(2-ethoxyethoxy)ethanolato-O,O0 ,O00 ] barium dissolved in ethyl benzene with 50% tri-n-octyl aluminum in hexane so that the aluminum/barium ratio was 4:1, respectively. This mixture was then treated with sufficient 15% n-butyl lithium so that the lithium/barium ratio was 3:1, respectively. The catalyst was used immediately.

469

470

2.

Catalyst for Synthesizing High Transpolymers

Preparation of Poly(Styrene-co-Butadiene)

A 500-gall reactor was charged with a 40:60 pre-mix of styrene/butadiene, respectively, at a total weight of 862 kg. The mixture was then treated with the Step 1 catalyst (0.325 mmol of barium per 100 mmol of butadiene) at 66 C. The polymerization occurred immediately and had a peak exotherm of 118 C within 45 minutes with a maximum pressure of 541 Pas within 38 minutes. After two hours the reactor was cooled, and the polymer cement was de-solventized to recover the product.

OPTIMIZATION STUDIES TABLE 1. Physical properties of copolymers prepared by bulk polymerization using bis[2-(2-ethoxyethoxy)-ethanolato-O,O0 ,O00 ] barium, ethyl benzene, and tri-n-octyl aluminum as the high trans catalyst mixture.

Entry 11 13 14 19

Ratio Styrene/ butadiene

Ratio Barium/ Butadiene

33/67 28/72 22/78 37/63

0.325 0.325 0.325 0.400

Tg ( C)

Styrene Incorporation (%)

Cis (%)

Trans (%)

Vinyl (%)

73.1 71.1 74.6 68.8

27.4 21.3 18.5 32.9

12.7 18.8 13.8 11.0

55.5 62.0 63.6 51.7

4.4 3.9 4.1 4.3

Note: All percentages were determined by 1 H-NMR; molecular weights were not supplied by author.

NOTES 1. Poly(styrene-co-butadiene) was previously prepared by Weydert [1] containing a high butadiene trans content using tri-n-butylaluminum and the barium salt of tri(ethyleneglycol)ethyl ether, Ba(OCH2CH2OCH2CH2OCH2CH3)2, 4:1 respectively. 2. High trans poly(styrene-co-butadiene) was also prepared by the author [2] in a subsequent investigation using a catalyst derived from the barium salt of (a) di(ethylene glycol) ethyl ether and di(N,N-dimethyl/amino ethylene glycol) ethyl ether or di(ethylene glycol) hexyl ether and triisobutyl aluminum. Materials prepared using this catalyst mixture were used as components automotive tires. 3. Standstrom [3] improved the elongation at break properties of tires by blending 70% cis-poly(1,4-isoprene) with 30% poly(butadiene) containing a high trans content. The latter was prepared using barium di(ethylene glycol) ethyl ether, tri-octyl aluminum, and n-butyllithium as the reaction catalyst mixture. 4. High trans content copolymers of styrene and butadiene were also obtained by Halasa [4] using the calcium salt of tetrahydrofurfuryl alcohol and n-butyl lithium.

Notes

471

5. Poly(styrene-b-butadiene) was anionically prepared by the author [5] using n-butylithium and tetramethylethylenediamine. The product was used as a component in automotive tires. 6. Dendrimeric rubbery copolymers having a molecular weight of roughly 250,000 daltons and containing siloxane linkages were prepared by the author [6] by copolymerizing 12% styrene and 88% butadiene in combination with of 2-butyl lithium, hexachlorodisiloxane, and N,N,N0 ,N0 -tetramethyl1,2-ethanediamine. References 1. M. Weydert et al., US Patent 6,889,737 (May 10, 2005) 2. A.F. Halasa et al., US Patent Application 2006-0149010 (July 6, 2006) 3. P.H. Sandstrom et al., US Patent Application 2005-0245688 (November 3, 2005) and US Patent Application 2005-0272852 (December 8, 2005) 4. A.F. Halasa et al., US Patent 7,087,549 (August 8, 2006) 5. A.F. Halasa et al., US Patent 7,064,171 (June 20, 2006) 6. A.F. Halasa et al., US Patent Application 2007-0010629 (January 11, 2007) and US Patent Application 2006-0247360 (November 2, 2006)

Title: Method for the Preparation of Poly(a)-Methylstyrene Author:

A. Balland-Longeau, US Patent 7,179,870 (February 20, 2007)

Assignee:

Commissariat A L’Energie Atomique (Paris, FR)

SIGNIFICANCE Poly(a-methylstyrene) having a Mn > 300,000 daltons with of PDI < 1.06 was prepared using sec-butyl lithium. The process entails initially treating the monomer with sec-butyl lithium to dry and to neutralize impurities while monitoring this process by UV. The monomer was then re-treated with butyl lithium, THF, and toluene and polymerized 24 hours. The material is intended for inertial confinement chambers in fusion experiments.

REACTION a i Note 1

i: s-Butyl lithium, toluene, THF

EXPERIMENTAL A 100-ml reactor connected to a cryostat equipped with a UV cell was charged with 55 ml of toluene and a-methylstyrene (22 g). While monitoring by UV, the monomer was dried by the dropwise addition of s-butyl lithium at ambient temperature, resulting in a slightly yellow coloring of the monomer. The mixture was then cooled to 25 C, treated with s-butyl lithium (0.073 mmol), stirred for 4 hours after which 10 ml of THF 472

Notes

473

and toluene were added. The mixture became a vivid red and was stirred an additional 24 hours at 25 C, until the solution became viscous. The reaction was quenched by adding 1 ml of ethanol and gradually warmed to ambient temperature. The mixture was precipitated in methanol, and the product was isolated by filtration in 91% yield having a Mn of 312,000 daltons with a polydispersity index of 1.06.

NOTES 1. Moore [1] prepared polystyrene having a Mn of 130,000 daltons with a PDI of 1.05 by initially drying the monomer and neutralizing impurities with n-butyllithium prior to polymerization. n-Butyl-lithium was also used with potassium t-amyloxide by Malanga [2] in preparing ultra-pure poly(amethylstyrene). 2. Andrekanic [3] prepared poly(a-methylstyrene) using tin(IV) chloride as initiator in toluene with unpurified plant grade a-methylstyrene. 3. Poly(butadiene-b-a-methylstyrene-b-styrene) was prepared by Tung [4] using sec-butyl-lithium and 1,3-di(1-phenylethenyl)benzene. 4. Poly(a-methylstyrene-co-styrene) was previously prepared by Desbois [5] using s-butyl lithium and triisobutylaluminum. References 1. 2. 3. 4. 5.

E.R. Moore et al., US Patent 4,883,846 (November 28, 1989) M.T. Malanga et al., US Patent 7,045,248 (May 31, 1988) R.A. Andrekanic et al., US Patent 6,649,716 (November 18, 2003) L.U. Tung et al., US Patent 4,431,777 (February 14, 1984) P. Desbois et al., US Patent 7,101,941 (September 5, 2006)

Title: Use of Sulfur Containing Initiators for Anionic Polymerization of Monomers Author:

T. E. Hogen et al., US Patent 7,153,919 (December 26, 2006)

Assignee:

Bridgestone Corporation (Tokyo, JP)

SIGNIFICANCE Sulfur-vulcanizable elastomers have been prepared that are designed to reduce hysteresis in tires by reducing the number of polymer free ends. The method for this preparation entails anionically preparing poly(styrene-co-butadiene) using a lithium thioacetal initiator followed by incorporation of a vulcanization agent into the elastomer terminus.

REACTION

S

i S

S

_

+

ii Li S Notes 1, 2

S

S

a

b

c

H d

e

f

Vulcanize

i: THF, butyllithium ii: Styrene, butadiene, hexane, cyclic oligomeric oxolanyl alkane (Note 1) isopropanol

EXPERIMENTAL 1.

Preparation of 2-Lithio-2-Methyl-1,3-Dithiane

A reactor was charged with 350 ml of THF and 2-methyl-1,3-dithiane (83.5 mmol) and then cooled to 78 C and treated with 55.83 ml of 1.51M butyllithium (84.3 mmol) in

474

Derivatives

475

hexane. The mixture was stirred at 78 C for 3 hours and stored at 25 C overnight. Titration of the resulting solution indicated that the solution contained 0.234M active lithium. 2. Preparation of Poly(Styrene-co-Butadiene) with 2-Lithio-2-Methyl1,3-Dithiane A 1.75 liter reactor was charged with 1.12 kg of hexane, 0.48 kg of 33 wt% styrene in hexane, and 2.89 kg of 22.0 wt% butadiene in hexane. The reactor was then heated to 24 C and treated with 0.5 ml of 1.6 M of a selected cyclic oligomeric oxolanyl alkane modifier (Note 1) in hexane and 22.63 ml of the Step 1 dissolved in THF. The mixture was heated to 54 C for 15 minutes, and an exotherm peaking at 76.5 C was observed. After an additional 25 minutes the mixture was removed from the reactor and coagulated in isopropanol containing butylated hydroxy toluene. After drying, the product was isolated, and it consisted of 21.7% styrene, 1.3% block styrene, 32.1% vinyl, and 46.2% 1,4 butadiene having a Mn of 15,300 daltons, Mw of 16,700 daltons, and a Tg ¼ 44.4 C.

DERIVATIVES TABLE 1. Effect of lithium thioacetal anionic initiators on poly(styrene-cobutadiene) properties. Poly(styrene-co-butadiene) Properties Mn (kg/mol)

Mw (kg/mol)

Tg ( C)

Li

208.0

240.0

43.8

Li

135.8

137.2

69.0

123.0

135.0

34.3

110.6

114.8

29.9

Initiator

S

S

S

S N(CH3)2

S

S

Li

BuLi (Reference)

476

Use of Sulfur Containing Initiators for Anionic Polymerization of Monomers

TABLE 2. Physical properties of styrene-butadiene elastomers initiated with selected thioacetals and terminated with vulcanization agents. Poly(styrene-co-butadiene) Properties

Initiator

S

Mn Mw Tg (kg/mol) (kg/mol) ( C)

Terminator

Li

Si(OC2H5)4

219

285

31.5

20.6 (2.0)

31.8

45.6

Li

Sn(C2H5)3Cl

106

113

31.3

21.0 (2.0)

31.4

45.6

108.5

117.6

29.7

—

—

—

111

126

30.9

20.7 (1.9)

31.8

45.6

S

S

Styrene (Block) Vinyl Budiene (%) (%) (%)

S N(CH3)2

N O N

S

S

S

Li

Li S

S

S

NOTES 1. Cyclic oligomeric oxolanyl alkanes were used when diene polymerization utilized a lithium-based initiator. Cyclic oligomeric oxolanyl alkanes are described by Lin [1] and include 2-20 -di(tetrahydrofuryl) propane, dipiperidyl ethane, hexamethyl phosphoramide, N-N0 -dimethyl piperazine, and diazabicyclooctane. 2. Halasa [2] reduced hysteresis in tires by anionically copolymerizing functionalized butadiene, (I), and styrene, (II), to enhance elastomer compatibility with carbon black and silica fillers.

N N (I)

(II)

Notes

477

3. Tires having reduced hysteresis were prepared by Kerns [3] by vulcanizing high vinyl content poly(styrene-co-butadiene) using butadienyllithium or styryllithium as the catalyst. 4. Tire tread rubber formulations were prepared by Parker [4] and consisted of poly(styrene-co-butadiene) rubber terminated with N-isopropylphenylnitrone, (III), to promote interaction between the polymer end-groups and carbon black and silica fillers to reduce hysteresis.

O

N

(III) 5. Obrecht [5] prepared rubber vulcanizates consisting of poly(styrene-co-butadiene) containing 2-t-butylamino-ethylmethacrylate, (IV), which were used in automotive tire applications.

O

t-C4H9 NH O

(IV)


C.J. Lin et al., US Patent 7,119,150 (October 10, 2006) A.F. Halasa et al., US Patent 7,041,761 (May 9, 2006) and US. Patent 6,995,224 (February 7, 2006) M.L. Kerns et al., US Patent 7,153,920 (December 26, 2006) D.K. Parker, US Patent 7,125,934 (October 24, 2006) W. Obrecht et al., US Patent 7,134,466 (November 14, 2006)

Title: Production Method of Polyisocyanate by End-Capping with Acyl Chloride Author:

Jae-Suk Lee et al., US Patent 7,135,536 (November 14, 2006)

Assignee:

Gwangju Institute of Science and Technology (Gwangju, KR)

SIGNIFICANCE Anionic polymerization of hexylisocyanate has been used to prepare polyamidates having controlled molecular weights and polydispersites. The method entailed using sodium N-phenyl benzyl amine as the anionic catalyst acyl chloride derivatives as end-capping agents. End-capping efficiencies of more than 90% of the living polymer were observed.

REACTION O C6H13 O C

N

N

i Note 1

O N a

O

O

O

_ N

C6H13 C6H13

N

ii Note 2

N a

N

C6H13 C6H13

Not isolated

i: Sodium N-phenyl benzyl amine, THF ii: Pyridine, methacryloyl chloride

EXPERIMENTAL Anion Polymerization of Poly(n-Hexylisocyanate) End-Capped with Methacryloyl Chloride n-Hexylisocyante was polymerized for 50 minutes at 1 10 6 torr at 98 C in THF using sodium N-phenyl benzyl amine as catalyst and end-capping for 10 minutes with pyridine and methacryloyl chloride. Specific stoichometries and polymer characteristics are provided in Table 1. 478

Notes

479

SCOPING REACTIONS TABLE 1. Polymer properties from four 50 minute anionic polymerization reactions using n-hexyl isocyante in THF with sodium N-phenyl benzyl amine as initiator and then quenching for 10 minutes using methacryloyl chloride dissolved in pyridine. Catalyst Monomer End-Capping Pyridine Calculated Measured Entry (mmol) (mmol) Agent (mmol) (mmol) Mn (daltons) Mn (daltons) PDI 1 2 3 4

0.10 0.11 0.07 0.05

4.04 6.60 6.76 6.71

0.81 0.62 0.65 0.53

1.75 1.60 1.44 1.58

5,000 7,000 12,500 15,500

5,600 6,900 12,800 15,700

1.07 1.13 1.14 1.17

NOTES 1. Living poly(n-hexylisocyanate) was previously prepared by titanium-catalyzed coordination polymerization as described by Pattan [1]. 2. Other encapping agents were used to functionalize poly(n-hexylisocyanate) in the current investigation. (s)-( )Acetopropionyl chloride was used to prepare an optically active terminus, (I), while suberoyl chloride was used to prepare the corresponding acid chloride terminus, (II). O O

O

O

N a N C6H13 C6H13

N N

O

O

O

N a N C6H13 C6H13 O

6

Cl

(II)

(I)

3. Optically active polyhexylisocyanates were prepared by Gu [2] by copolymerizing 1- and 2-deuterium-hexylisocyanatewith with hexylisocyanate, (III) and (IV), respectively. O

D

O

O N a

N

O N a

b D

H H

(III)

(IV)

N

b

480

Production Method of Polyisocyanate by End-Capping with Acyl Chloride

4. Azo-functionalized polyhexylisocyanate, (V), was prepared by Se [3] by endcapping with 4-(phenylazo)benzoyl chloride. O

O N

a

C 6 H 13

N N

(V)

References 1. T.F. Pattan et al., J. Am. Chem. Soc. 113: 5065, 1991, and Macromolecules 26: 436, 1993 2. H. Gu et al., Marcomolecules, 1998, 31, 6362 3. K. Se et al., Marcomolecules, 2003, 36, 5878

B. Catalytic Agents a. Acyclic Diene Metathesis Catalyst

Title:

Methods for Making Functionalized Polymers

Author:

K. B. Wagener et al., US Patent 7,172,755 (February 6, 2007)

Assignee:


SIGNIFICANCE A new acyclic diene metathesis polymerization method has been developed using 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene ruthenium(II) dichloride as catalyst. This reaction catalyst was used for preparing oligomers and polymers containing amino acids or polypeptides.

REACTION a HN

O

HN i Note 1

O OCH 3

O

O OCH 3

i: 1,3-Dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene tricyclopentylphosphine ruthenium(II) dichloride, CH2Cl2

EXPERIMENTAL 1.

Polymerization of Methyl N-[2-(3-Butenyl)-6-Heptenoyl]-L-Leucinate

Polymerization reactions were conducted under a protective argon atmosphere. A vesselwaschargedwithmethylN-[2-(3-butenyl)-6-heptenoyl]-L-leucinate(1.62 mmol) 481

482


and 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene ruthenium(II) dichloride (0.016 mmol) and then placed in a Shlink flask with a stirring bar and a condenser. Argon was next flowed through the system and then vented through a bubbler. The mixture was heated to 60 C with rapid stirring for 5 days; when the solution became too viscoustostir,additionalCH2Cl2 wasadded.Theproductwasisolatedfollowingvacuum removal of the reaction solvent. Tm ¼ 114 C Mn ¼ 31,000 daltons 1 H NMR d 0.75 0.90(dm, 6H, C.sub.C,D–H), 1.20 1.70(m, 9H, C.sub.A,B,4,6,7–H), 1.85 2.10(m, 4H, C5, 8–H), 2.15 2.30(m, 1H, C5–H), 3.60(s, 3H, OCH3), 4.25 4.35(m, 1H, C.sub.A–H), 5.30 5.50(m, 2H, C.sub.1,2–H), 8.20(m, 1H, NH). C,H,N Analysis: Theoretical C68.5H9.7N4.9; Found C66.21H9.01N4.67

DERIVATIVES

a

O

H N

O

O

a

b

R

TABLE 1. Selected acyclic diene metathesis polymers prepared using optically active monomers. Entry

a

R

2 3 4 5 6

2 2 3 8 8

i-Propyl i-Butyl i-Butyl i-Propyl i-Butyl

O H3CO i-C4H9 HN O a

b

c

TABLE 2. Selected acyclic diene metathesis polymers prepared using optically active monomers. Entry

a

b

7 8

2 3

3 3

Notes

483

TABLE 3. Physical properties of acyclic diene metathesis polymers illustrated in Tables 1 and 2. Entry

[a] Monomer ( )

[a] Polymer ( )

Mn (daltons)

PDI

Tm ( C)

32 32 32 34 –– 13 13

–– –– 32 20 40 64 7

900 900 4,700 27,000 33,000 31,000 26, 000

1.49 1.13 1.73 1.77 1.64 202 210

–– –– –– 29 –– 114 135

2 3 4 5 6 7 8

Note: Mn values were calculated by GPC using polystyrene standards.

NOTES 1. In an earlier investigation by the author [1] an additional acyclic diene metathesis ruthenium polymerization catalyst, (I), was identified and used in the metathesis of alkenyl alcohols.

N

N

Cl Ru Cl P

3 (I)

2. Angeletakis [2] prepared metathesis-curable dental compositions using 1,3bis-(2,4,6-trimethylphenyl)-2-(imidazolidinylidene) dichloro(o-isopropoxyphenylmethylene) ruthenium, (II), with norbornene-terminated siloxane macromolecules, (III).

N

N

Si

O

Si

O

a Si

O

Si b

Si

Ru a = 30–1500 b = 1–100

O

(II)

(III)

484


3. Grubbs [3] prepared high activity metathesis ruthenium metal carbene complexes, (IV), that were effective as depolymerization catalysts of unsaturated polymers and synthetic agents in preparing telechelic and alkene polymers. Other high activity metathesis ruthenium carbene metal complexes, (V), were prepared by Fogg [4].

R = C6H 5 C 5H 9

PR 3

Cl

Ru

X= H Cl N(CH 3 ) 2 OCH3 CH 3 F Cl NO 2

Ru

PR 3

OC 6 X 5 X

N X

(IV)

X

X = F, Cl, Br

(V)

4. Piccinelli [5] used (tricyclopentylphosphine)dichloro(3-methyl-butenylidene), (VI), or related cyclic derivatives, (VII), to prepared anti-fog agents, (VIII), by coupling 2-norbornene and allyl-terminated oligomeric ethylene oxide using ring opening metathesis polymerization as illustrated in (VIII) below. t-C4H9

t-C4H9

Cl

Cl P Ru Cl

(C5H9)3P Ru Cl

(VI)

t-C4H9

O

+ O a

O

O

6

O

(VIII)

i: Toluene, VI or VII

6

t-C4H9

(VII)

i

O

a

a =5–10

Notes

485

5. An azo-free method for preparing the ruthenium metathesis catalysts was developed by Nolan [6]. P(C6H5)3

RuCl2P(C6H5)3

i

Cl Ru Cl

PCy3

ii

Cl Ru Cl

P(C6H5)3

PCy3

i: 3,3-Diphenylpropargyl alcohol ii: Triscyclopentadienyl phosphine References 1. 2. 3. 4. 5. 6.

K. Wagener et al., US Patent 6,605,748 (August 12, 2003) C. Angeletakis, US Patent 7,173,097 (February 6, 2007) and US Patent 7,060,770 (July 13, 2006) R.H. Grubbs et al., US Patent 7,102,047 (September 5, 2006) D.E. Fogg et al., US Patent 7,094,898 (August 22, 2006) P. Piccinelli et al., US Patent 7,160,969 (January 9, 2007) S.P. Nolan, US Patent 7,205,424 (April 17, 2007)

C. Cationic

Title: Polymerization of i-Butene in Hydrocarbon Media Using bis(Borane) Co-Initiators Author:

S. Collins, US Patent 7,196,149 (March 27, 2007)

Assignee:


SIGNIFICANCE A polymerization method for cationically polymerizing liquefied isobutylene using the initiator pair 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluoro-fluorenyl)-3,4,5,6tetrafluorobenzene and tri-n-octylaluminum is described. The method is particularly unique in that the polymerization occurs in a nonchlorinated solvent. Isobutylene catalyzed using these co-reagents had molecular weights upto 258,000 daltons.

REACTION

i Note1

a

i: Tri-n-octylaluminum, 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6tetrafluorobenzene, toluene

486

Notes

487

EXPERIMENTAL Preparation of Polyisobutylene Isobutene was condensed at 78 C into a graduated cylinder under nitrogen, and 12 ml were transferred into a reaction vessel containing 1 g of tri-n-octylaluminum. The mixture was stirred for 30 minutes at 78 C and then transferred to a second reaction vessel. It was then treated with 48 mml of 0.05M 1,2-bis(9-bora1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetrafluorobenzene dissolved in toluene, which resulted in an uncontrolled, exothermic polymerization accompanied by rapid gelation of the solution. The mixture was quenched with 1 ml of 0.2M NaOCH3 in methanol. The volatiles were removed and the residue washed with methanol then dissolved in hexane. The solution was filtered, concentrated, and the product isolated. Reaction scoping results are provided in Table 1.

REACTION SCOPING TABLE 1. Isobutylene polymerization scoping reactions using tri-n-octylaluminum and 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetra fluorobenzene as the catalyst pair. Entry 1 3 4 5

Co-catalyst (mmol) 0.20 0.64 2.00 2.00

Isobutylene (mol)

Mw 1 103 (daltons)

PDI

14.6 0.56 3.3 3.3

69.0 97.8 195 258

3.16 2.22 3.18 2.28

Note: In all cases the conversion was 100%.

NOTES 1. The co-catalyst, 1,2-bis(9-bora-1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6tetrafluorobenzene, (I), was prepared according to the method of Williams [1]. 2. In a subsequent investigation by Kennedy [2], the co-catalyst, 1,2-bis(9-bora1,2,3,4,5,6,7,8-octafluorofluorenyl)-3,4,5,6-tetrafluorobenzene, was also used to polymerize 1-butene. 3. Wang [3] polymerized ethylene using boron containing activators tris(pentafluorophenyl)-borane, (II), and lithium tetrakis(pentafluorophenyl)borate, (III). Using tris(pentafluorophenyl)-borane, (II), with alumoxane, Arriola [4] prepared poly(ethylene-co-propylene) and polypropylene.

488

Polymerization of i-Butene in Hydrocarbon Media Using bis(Borane) Co-Initiators

F F

F

F

F F F

F

B

F

F

F

F

F

F F F F

F F

F F

F

F F

B

F

Li

F

F F

F

F

F

F

F

F

F

(III)

(II)

4. Using 2-chloro-2,4,4,-trimethylpentane as the initiator and ethylaluminum dichloride as the Lewis acid, McDonald [5] and Shaffer [6] prepared high molecular weight polyisobutylene with perfluorinated alkanes as polymerization solvents. 5. Goodall [7] polymerized norbornene using the cationic chromium-palladium/ boron pair complex, (IV) to a Mw of roughly 1,200,000 daltons with a PDI index of 1.2. F

F (C 6 H 5 ) 3P

F

F

Pd

F

F

Cl O

Cr

F F

(NCCH 3 ) 2

F

B

F F

F

F

F F F

F

F F

F

(IV)


W. Williams et al., J. Am. Chem. Soc. 1991, 121, 3244–3245 J.P. Kennedy et al., US Patent 7,202,317 (April 7, 2007) S. Wang et al., US Patent 7,196,147 (March 27, 2007) D.J. Arriola et al., US Patent 7,193,024 (March 20, 2007) M.F. McDonald et al., US Patent Application 2006-0111522 (May 25, 2006) and US Patent Application 20060089467 (April 27, 2006) 6. T.D. Shaffer et al., US Patent Application 2006-0100398 (May 11, 2006) 7. B.L. Goodall et al., US Patent 7,172,986 (February 6, 2007)

Title: Copolymers of Tetrahydrofuran, Ethylene Oxide, and an Additional Cyclic Ether Author:

G. Pruckmayr et al., US Patent 6,989,432 (January 24, 2006)

Assignee:

Invista North America S.a.r.l. (Wilmington, DE)

SIGNIFICANCE Terepolymers having Mn’s less than 3200 daltons have been prepared consisting of THF, 3-ethyl-tetrahydrofuran, and ethylene oxide, which were catalyzed by the acid resin NAFIONÒ NR-50. Terpolymer hydrophobic/hydrophilic properties were controlled by the ethylene oxide content.

REACTION O i

O

a

O b

O

c d

i: 3-Ethyl-tetrahydrofuran, 1,4-butanediol, NAFIONÒ NR-50

EXPERIMENTAL A reactor was charged with THF (2.22 mol), 3-ethyl-tetrahydrofuran (0.4 mol), 1,4butanediol (0.01 mol), and NAFIONÒ NR-50 (10 g) cryoground to less than 80 mesh. The mixture was heated to 50 C and treated with ethylene oxide (0.19 mols) over a 4 hour period. Heating was continued for an additional 15 minutes and then cooled to 30 C and filtered. The polymer solution was concentrated, and the product was isolated in 24% yield as a viscous liquid having a Mn of 3,100 daltons with a THF content of 72 mol%, ethylene oxide content of 25 mol%, and a 3-ethyl-tetrahydrofuran content of 3 mol%.

489

490

Copolymers of Tetrahydrofuran, Ethylene Oxide, and an Additional Cyclic Ether

REACTION SCOPING TABLE 1. Summary of terepolymers produced when catalyzed by the solid perfluorosulfonic acid resin NAFIONR NR-50. Reaction Charge

Polymer Properties

THF (g)

Ethylene Oxide (g)

Co-component (g)

2

26

6.5

3 4

10 800

3-Ethyl-THF (13) Oxepane (10) 3-Ethyl-THF (100)

Entry

9 55

Polymer Mn (daltons)

THF Content (%)

Co-component (%)

Ethylene Oxide Content (%)

1075

49

20

31

2430 2700

45 68.1

20 3.9

35 28

TABLE 2. Summary of terepolymers produced when catalyzed by the compound fluorosulfonic acid. Reaction Charge

Entry 5 9 13

THF (g) 663 1,448 2,768

3-Ethyl THF (g) 176 385 792

Polymer Properties Ethylene Oxide (g)

Polymer Mn (daltons)

THF Content (%)

3-Ethyl THF Content (%)

Ethylene Oxide Content (%)

37.1 81 204

1,804 1,778 1,497

85.7 85.7 80.1

9.5 9.6 8.1

4.8 4.7 11.8

NOTES 1. PolyTHF was prepared by Meier [1] using a catalyst mixture consisting of SiO2 containing 21 wt% NiO, 7.3 wt% CuO, and 2 wt% Mn3O4 and then polymerized using Montmorillonite Catalyst K 306. Calcined TiO2 VKR 611 containing ammonium paratungstate and oxalic acid dihydrate were used by Steinbrenner [2] to polymerize the THF. 2. THF was copolymerized with 3-methyl-THF in the presence of 1,4-butanediol by Pinkos [3] using the catalyst dodecatungstophosphoric acid. 3. Schlitter [4] demonstrated that catalysts of the montmorillonite/saponite group, the kaolin/serpentine group, and the palygorskite/sepiolite group were effective as the THF polymerization agents.

Notes


A. Meier et al., US Patent 7,148,318 (December 12, 2006) U. Steinbrenner et al., US Patent 7,074,944 (July 11, 2006) R. Pinkos et al., US Patent 7,098,349 (August 29, 2006) S. Schlitter et al., US Patent 7,041,752 (May 9, 2006)

491

D. Chain Transfer Agents

Title: Dithiocarbamic Esters Author:

D. Achten et al., US Patent 7,169,937 (January 30, 2007)

Assignee:

Bayer Aktiengesellschaft (Leverkusen, DE)

SIGNIFICANCE A method for the controlled emulsion polymerization of chloroprene using dithiocarbamic esters as sulfur-based chain transfer agents is described. The method provides industrially relevant molar masses with Mn’s > 50,000 daltons with good yields in acceptable times. It was further determined that when pKa values for the dithiocarbamic acid precursors were less than 12, the thioester was ineffective as a regulator.

REACTION i

N

ii

N

Not isolated iii Cl

Regulator

......

Polymerization regulator

Cl

...... a

1,2-addition

Cl

S

S

S Na

S H N

+

...... Cl

...... b

3,4-addition

+

......

Cl

......

c 1,4-addition

i: THF, potassium, carbon disulfide, 1,3-dichloro-2-butene ii: Dresinate 731, water, naphthalenesulphonic acid, sodium hydroxide

EXPERIMENTAL 1. Preparation of 3-Chloro-2-Butenyl-1H-Pyrrole-1-Carbodithioate Regulator A 1-liter reaction vessel was charged with 500 ml of THF and potassium (1 mol) under nitrogen at ambient temperature and then treated with 1H-pyrrole (1 mol) dissolved in 492

Derivatives

493

150 ml of THF over 30 minutes. This mixture was treated with carbon disulphide (1 mol) dissolved in 240 ml of THF and stirred for 1 hour. It was then posttreated with 1,3-dichloro-2-butene (1.5 mol) with the reaction extent monitored using GC. The reaction solution was concentrated in vacuo, the residue slurried with 500 ml of pentane, and the product isolated by filtration. 2.

Preparation of Polychloroprene by Emulsion Polymerization

A 3-liter glass reactor was charged with 125 parts of deionized water (1250 g), 2.80 parts of Dresinate 731 in the form of 70% strength solution (40 g), 0.3 part of condensed naphthalenesulphonic acid in the form of 30% strength solution (10 g), and 0.65 part of NaOH (6.5 g). This aqueous mixture was then treated with 100 parts of chloroprene and the Step 1 product (15 mmol). The polymerization was conducted at 45 C using a 2.5% strength solution of formamidinesulphinic acid as the initiator and continued for 90 minutes until a 60% product conversion was obtained.

DERIVATIVES TABLE 1. Effect on the polymerization of chloroprene using selected dithiocarbamic esters as sulfur-based chain transfer agents.

Entry

Regulator

S 1

Polychloroprene Mn (daltons)

Cl

S N

S

S 2

Polychloroprene Solution Viscosity (mPas)

14

50,000

35

101,000

Gelled

—

Cl

N N

S 3

N

S

S 5

N

OCH3

S

Gelled

—

O (continued)

494

Dithiocarbamic Esters

TABLE 1. (Continued)

Entry

Polychloroprene Solution Viscosity (mPas)

Regulator

S N

6

Polychloroprene Mn (daltons)

Cl S

Gelled

—

67

168,000

Gelled

—

O O 7

S O

S

S

S

O O

O

S 9

O

OCH3

S O

Note: Very limited characterization data were provided by the author.

TABLE 2. Entry

Acidity constants for selected dithiocarbamic acids. R

pKa

N 1

17.0

N 2

N

14.5

N 3,5,6

5.1

Note: An aliphatic dithiocarbamic ester acid precursor having a pKa value less than 12 was ineffective as a sulfur-based chain transfer agents.

Notes

495

NOTES 1. Chiefari [1] prepared sulfur-containing chain transfer agents, (I) and (II), to control the polydispersity and multimodal molecular weight distribution of methyl methacrylate during free radical polymerization. The synthesis of a polymeric chain transfer agent analogue, (III), was also proposes by the author.

a S

S

S S

S

S

(I) R

(II)

R> C1

S

(III)

2. Dithiocarbonylated ethyl xanthates, (IV), dithiophosphorylates, (V), and azo derivatives, (VI), prepared by Wilczewska [2], Destarac [3], and Charmot [4], respectively, and were effective as chain transfer agents in free radical polymerization reactions. S

S

O C2H5

S H3CO

O

S O

(IV)

O

OC2H5 P OC2H5

S

C2H5O

N

O

(V)

S N

(VI)

3. Charmot [5] developed a method for removing the thiocarbonylthio or thiophosphorylthio end group of polymers and re-functionalizing it with N-methylmalimide. N

O S

........

N

........

O

a

S O

O

i

O O

CN O

O

O O

i: Methyl ethyl ketone, N-methyl-malimide, 2,20 -azobisisobutyronitrile

496

Dithiocarbamic Esters


J. Chiefari et al., US Patent Application 2004-0024132 (February 5, 2004) Z.A. Wilczewska et al., US Patent 7,109,276 (September 19, 2006) M. Destarac et al., US Patent Application 2003-0045661 (March 6, 2003) D. Charmot et al., US Patent 7,012,119 (March 14, 2006) D. Charmot et al., US Patent 6,919,409 (July 19, 2005)

E. Emulsifing Agents a. Polymeric

Title: Amphiphilic Copolymers Useful Especially as Emulsifiers Author:

E. Camus et al., US Patent 7,144,947 (December 5, 2006)

Assignee:

Laboratories d’Hygiene et de Dietetique (Chenove, FR)

SIGNIFICANCE Amphiphilic copolymers have been prepared that have reduced surface contact angles and are effective as emulsifying agents or absorbents. These materials were prepared by reacting poly[styrene-b-poly(ethylene-butylene)-g-succinic anhydride-b-polystyrene)] [Kraton G 1901Ò] with methoxypolyethylene glycols having Mn’s between 2000 and 8000 daltons.

REACTION Polyethylene/butylene a

Polyethylene/butylene b

O

O

O

a

i

a

b

O

O O

O H3CO

45

a

O

O 45

OCH3

i: Toluene, polyethylene glycol methyl ether, sulfuric acid, ethanol, water

497

498

Amphiphilic Copolymers Useful Especially as Emulsifiers

EXPERIMENTAL Preparation of (Polystyrene-b-((Polyethylene-co-Butylene)-g-(Diethyleneglycol Succinate)-b-Styrene) A reactor was charged with 150 ml of toluene and 20 g poly[polystyrene-b-poly (ethylene-co-butylene-g-succinic anhydride)-b-styrene] containing 2% grafted succinic anhydride and then heated until the polymer dissolved. The mixture was next treated with a solution of 32 g polyethylene glycol methyl ether having a Mn of 2000 daltons dissolved in 100 ml of toluene containing 20 drops of sulfuric acid and then refluxed for 30 to 40 minutes. The material was isolated by precipitating in 1.5 liter of water/ethanol, 1:1, at 90 C to 100 C. The rubber was dried at 40 C to 50 C under vacuum and purified by dissolving in 100 to 150 ml of toluene at 90 C to 100 C and re-precipitating in 1.5 liter of water/ethanol, 1:1; the process was repeated until all unreacted polyethylene glycol methyl ether was removed.

DERIVATIVES AND TESTING TABLE 1.

Contact angles of selected KratonR-containing amphiphilic pendants.

Entry Kraton G 1901Ò (Reference) 2 3 4 6 7 8 1 10

Polyether*1

Contact Angle (deg)

None

95

PEG-200 PEG-600 PEG-2000 PEG-8000 PEGME-350 PEGME-500 PEGME-2000 PEO/PPO/PEO-1900

86 85 76 72 87 86 75 75

Note: These polyesters were subsequently used in the manufacture of skin care products. PEG ¼ Polyethylene glycol PPO ¼ Polypropylene oxide PEGME ¼ Polyethylene glycol monomethyl ether *1

Notes

499

TABLE 2. Emulsion stability of selected amphiphilic copolymers prepared by adding 1.5 g of a selected experimental polymer to an oil/water mixture and blending at 90 C to 100 C. Entry

Water/Oil Distribution (g)

Emulsion Appearance

50/50

Unstable, immediate demixing

50/50 25/75 75/25 25/75 75/25

Stable, no change after 3 weeks Stable, no change after 3 weeks Stable, no change after 3 weeks Unstable, degrades over time Stable, no change after 3 weeks

Kraton G 1901Ò (Reference) 1 1 1 6 6

Note: The targeted applications for these materials was in moisturizing creams.

NOTES 1. Wang [1] prepared biocompatible cyclodextrin grafted polymers, (I), consisting of hydrophobically modified cyclodextrin with a biocompatible hydrophilic polymer backbone that were used as drug delivery agents. O

O

N H

a

O b

O

O

O R2O O

R1O

OR1 OR2

O

O

1) R1 = R2 = CH3CO 2) R1 = C2H5, R2 = H

6

R1O

(I)

2. Ekwuribe [2] prepared amphiphilic mono-dispersed polymers, (II), consisting of polyethylene oxide with one terminus consisting of a hydrophobic ester and the other containing insulin. These materials were effective at surviving an in vitro model of intestinal digestion.

500

Amphiphilic Copolymers Useful Especially as Emulsifiers

O

O O

15

O

8

O

Insulin

(II)

3. Nonionic amphiphilic telechelic polymers consisting of polyethylene oxide with polyhedral oligosilsesquioxane, POSS, termini were prepared by Mather [3] and used as surfactants and thickening agents. The hydrophobicity of these amphiphilic telechelics, (III), was controlled by varying the molecular weight of the polyethylene oxide component. O O POSS

H N

O Si

N H

O

Si

POSS O

a

O

(III)

a = 20, 24, 72, 160, 200

4. Nathan [4] prepared poly(monostearoyl glycerol-co-glyceryl monooleatesuccinate), (IV), to prepare amphiphilic block polyester microdispersions that were bioabsorbable and biocompatible and useful as drug delivery agents. O O

O

O

a O

O O

O O

O

O

C17H35

O C11H23

(IV)


L. Wang et al., US Patent 7,141,540 (November 28, 2006) N.N. Ekwuribe et al., US Patent 7,084,114 (August 1, 2006) P.T. Mather et al., US Patent 7,067,606 (June 27, 2006) A. Nathan et al., US Patent 7,026,374 (August 11, 2006)

b

a:b = 1:1, 1:3

b. Inverse Emulsion

Title: Anionic Copolymers Prepared in an Inverse Emulsion Matrix and Their Use in Preparing Cellulosic Fiber Compositions Author:

B. Walchuk et al., US Patent 7,250,448 (July 31, 2007)

Assignee:

Hercules Incorporated (Wilmington, DE)

SIGNIFICANCE Linear water-soluble anionic poly(acrylamide-co-ammonium acrylate) has been prepared by a water-in-oil polymerization. These materials are characterized by a Huggins’ constant in brine greater than 0.75 and a storage modulus for a 1.5 wt% actives polymer solution at 4.6 Hz greater than 175 Pa. These agents are particularly useful as drainage aids and contamination control aids in papermaking.

REACTION O NH2

i O

a

b c

NH2 O

O NH4

i: Paraffin oil, sorbitan monooleate, fatty acids of poly(ethyleneoxide), acrylamide, acrylic acid, water, ammonium hydroxide, 2,20 -azobisisobutyronitrile

501

502

Anionic Copolymers Prepared in an Inverse

EXPERIMENTAL Preparation of Poly(Acrylamide-co-Ammonium Acrylate) A reaction flask was charged with an oil phase consisting of paraffin oil and surfactants sorbitan monooleate (4.5 g) and fatty acid esters of poly(ethyleneoxide) (9.0 g) and heated to 37 C. In a separate vessel an aqueous phase was prepared and consisted of 53 wt% acrylamide solution in water (126.5 g), acrylic acid (68.7 g), deionized water (70.0 g), and Versenex 80 solution (0.7 g). The solution pH was adjusted to pH 5.4 using 29.4% ammonium hydroxide solution (33.1 g). The aqueous phase was then added to the oil phase while simultaneously mixing with a homogenizer to obtain a stable water-in-oil emulsion. This emulsion was mixed while being sparged with nitrogen for 60 minutes at 50 C. Thereafter the nitrogen sparge was discontinued; and a nitrogen blanket was implemented. The mixture was next treated with 3 wt% 2,20 azobisisobutyronitrile dissolved in toluene (0.213 g) over a period of 2 hours corresponding to an initial initiator charge of 250 ppm and stirred for 60 minutes at 62 C. Thereafter an additional 3 wt% initiator dissolved in toluene (0.085 g) was added in under 60 seconds, corresponding to a 2,20 -azobisisobutyronitrile charge of 100 ppm, and the temperature was held at 62 C for 2 hours. The reactor was cooled to ambient temperature, and the product was isolated.

REACTION SCOPING TABLE 1. Experimental conditions used in preparing poly(acrylamide-coammonium acrylate) with sorbitan monooleate as a surfactant. Entry

Acrylic acid (%)

Medium pH

Initiator

50 50 50 40

3.0 6.0 5.4 5.4

2,20 -Azobisisobutyronitrile 2,20 -Azobisisobutyronitrile t-Butylhydroperoxide 2,20 -Azobisisobutyronitrile

2 4 10 11

TABLE 2.

Entry 2 4 10 11

Performance testing of poly(acrylamide-co-ammonium acrylate).

G0 at 4.4 Hz (Pa)

Intrinsic Viscosity (dL/g)

Huggins’s Constant

Viscosity Average Molecular Weight (daltons)

237 205 189 328

32 43 50 42

2.0 1.9 1.1 2.3

3.1 7.6 12.9 6.6

Note: Storage modulus, G0 , testing was evaluated using 1.5 wt% polymer at 25 C at 4.6 Hz.

Notes

503

NOTES 1. Anionic copolymers consisting of acrylamide and styrene sulfonic acid sodium were prepared by Harrington [1] and used as drainage aids for cellulosic fiber compositions. Doherty [2] anionically prepared high molecular weight poly (acrylamide-co-styrene sulfonic acid sodium), which was also effective as a drainage aid. 2. Cationic copolymers consisting of acrylamide and quaternary ammonium salts such as [2-(acryloyloxy)ethyl]trimethyl ammonium chloride, (I), prepared by Hollomon [3] were effective as drainage aids. In the absence of crosslinking these cationic materials were characterized by a Huggins constant greater than 0.3 with a storage modulus at 6.3 Hz of over 50 Pa.

b

a O

O

NH2

c

O

Cl

N

(I)

3. Doherty [4] prepared water compatible hydrophobic polymers such as poly (acrylamide-co-t-octylacrylamide), (II), that were used as components in cellulosic fiber compositions.

b

a

O

NH 2

O

c

NH t-C 8 H 17

(II)


J.C. Harrington, US Patent Application 2006-0185806 (August 24, 2006) E.A.S. Doherty et al., US Patent Application 2006-0127351 (June 15, 2006) M. Hollomon et al., US Patent Application 2004-0143039 (June 22, 2004) E.A.S. Doherty et al., US Patent Application 2006-0266488 (November 30, 2006)

F. Free Radical Polymerization

Title: Perfluorodiacylperoxides as Polymerization Initiators Author:

W. Navarrini et al., US Patent 7,135,599 (November 14, 2006)

Assignee:

Solvay Solexis, S.p.A. (Milan, IT)

SIGNIFICANCE Four perfluorodiacylperoxide free radical initiators were prepared by condensing perfluoroacyl chloride derivatives with hydrogen peroxide and sodium hydroxide. When the product bis(2-fluoro-2-trifluoromethyl-perfluoropropionyl) peroxide was used to polymerize vinylidene fluoride, a 90% conversion was observed.

REACTION F

F Cl

F 3C F 3C O

i

O O

F3 C F3C

O O

F CF 3 CF 3

i: Sodium hydroxide, 1,1,2,-trichloro-1,2,2-trifluoroethane, hydrogen peroxide

EXPERIMENTAL 1. Preparation of bis(2-Fluoro-2-Trifluoromethyl-Perfluoropropionyl) Peroxide A four-necked flask containing a mechanical stirrer, a solid CO2 condenser, a thermometer, and a dropping funnel was charged with NaOH (48.7 mmol) and 15 ml

504

Derivatives

505

of distilled water. The solution was then treated with 50 ml of 1,1,2,-trichloro-1,2,2trifluoroethane and cooled to roughly 0 C before being treated with 4.6 ml of 57.5% H2O2 (94 mmol). Using the dropping funnel, 2-fluoro-2-trifluoromethyl-perfluoropropionyl chloride (10.2 g) was slowly introduced to control the reaction exotherm and then transferred into a separatory funnel after around 10 minutes. The organic phase was washed with distilled water until a neutral pH was observed and then dried with Na2SO4. The perfluoro-peroxide assay was determined using iodometric titration, and the product was isolated in 70% yield. FNMR (CFCl3 ¼ 0): 184 ppm 1F; 75 ppm 6F IR (main bands (cm1): 1853 (m), 1824 (m), 1309 (m), 1264 (s) Mass spectrum (main peaks and intensities): 319 (3), 281 (3), 231 (5), 181 (5), 131 (5), 69(100) Decomposition Constants: Kd (s1): 4.4 105 (60 C), 16.21 105 (70 C), and 57.81 105 (80 C) 19

2.

Preparation of Polyvinylidene Fluoride

The Step 1 product (0.12 mmol) dissolved in 1.2 ml of 1,1,2,-trichloro-1,2,2trifluoroethane and 20 ml of distilled water were introduced into a 50 ml steel reactor equipped with a magnetic stirrer. The reactor contents were cooled with liquid nitrogen and evacuated to 1 103 mbar to remove trace amounts of oxygen. The reactor was next charged with 22 atm of vinylidene fluoride and the reactor temperature, raised to 57 C. Once the autoclave pressure decreased to 15 atm, additional vinylidene fluoride was added to maintain the reaction pressure at 20 atm. The polymerization was stopped after 48 hours, and the product was isolated in 90% yield.

DERIVATIVES TABLE 1. Selected perfluoroalkyl peroxides and their effectiveness in initiating the polymerization of vinylidene fluoride. Entry 4 6 10

Fluoro Initiator [(CF3)2CFCOO]2 [(CF3O)(CF3)2CCOO]2 [(CF3O)2CF3CCOO]2 O

12

Polymer conversion (%)

F7

O

90 65 78 F7

O

55 O

Note: 19 F-NMR, MS, Td, and IR for each entry were provided by author.

506

Perfluorodiacylperoxides as Polymerization Initiators

NOTES 1. Perfluoroether monomers 3,5-dioxa-1-heptene, (I), and 3,5,8-trioxa-1-nonene, (II), were prepared by the author [1] and polymerized with tetrafluoroethylene using perfluoropropionyl-peroxide as the reaction initiator. F

F F3 C

O

C F2

O

C F

F

F3 C

O

C F2

(I)

O

C F2

O

C F

F

(II)

2. In an earlier investigation the author [2] converted 2,2,5,5-tetrafluoro-4-trifluoromethoxy-1,3-dioxolane into the corresponding peroxide initiator, (III), using the method described in Step 1. Brothers [3] converted 3-oxa-perfluorohexanoyl fluoride into the corresponding peroxide, (IV), using sodium percarbonate. F2C

O CF 2 O

O F3CO

O

O

O

O

(III)

O

OCF3

F2C O

n-C3F7

CF2

O

CF

CF3 O

O

CF

CF3

O

n-C3F7

O

(IV)

3. Fontana [4] prepared the free radical pro-initiator perfluoroethyether acyl fluoride, (V), by florination of the precursor alcohol having a Mn of roughly 460 daltons with CsF. F2 C

O F3C

C F2

F2 C O a

(V)

F2 C O

F

b O


W. Navarrini et al., US Patent 7,160,967 (January 9, 2007) W. Navarrini et al., US Patent 7,135,599 (November 14, 2006) P.D. Brothers et al., US Patent 7,112,314 (September 26, 2006) G. Fontana et al., US Patent Application 2004-0147778 (July 29, 2004) and US Patent Application 20040147780 (July 29, 2004)

G. Macroinitators a. Photoinitators

Title:

Polymeric Photoinitiators

Author:

D. E. Herr et al., US Patent Application 2007-0078246 (April 5, 2007)

Assignee:

National Starch and Chemical Company, Bridgewater, NJ)

SIGNIFICANCE A key drawback for using photoinitators is the residual photochemical by-products. To address this problem, polybutadiene photoinitators containing grafted benzophenone have been prepared where both photoinitiator and photochemical by products are completely miscible with hot melt processable resins.

REACTION O

O

O

i

ii O

HO

H Si

O

Si

O

O

Polyisobutylene

Si

O

iii Si

O

i: 4-Hydroxybenzophenone, 2-butanone, potassium carbonate, allyl bromide ii: THF, 1,1,3,3-tetramethyldisiloxane, chlorotris(triphenylphosphine) rhodium iii: Polybutadiene, toluene, platinum 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane

507

508


EXPERIMENTAL 1.

Preparation of 4-Allyloxybenzophenone

A reaction vessel was charged with 4-hydroxybenzophenone (940 mmol) dissolved in 700 ml of 2-butanone and then treated with K2CO3 (1.41 mol) and heated to 65 C. This mixture was next treated with the dropwise addition of allyl bromide (1.41 mol) and stirred for 6.5 hours at 65 C. The slurry was filtered, and the filtrate was extracted with 500 ml of 1% hydrochloric acid. The organic layer was isolated, dried over MgSO4, and concentrated. The product was isolated in 92% yield a pale yellow solid. 2.

Preparation of Siloxy-Functionalized Benzophenone

The Step 1 product (840 mmol) was dissolved with warming in 150 ml of THF and then transferred into an addition funnel. A reaction vessel was charged with 1,1,3,3-tetramethyldisiloxane (4.18 mol) and 100 ml of THF, and the temperature was raised to 50 C. This mixture was then treated with chlorotris(triphenylphosphine) rhodium (22 mg), and 5 ml of the Step 1 THF solution. Thereafter the reaction temperature was raised to 60 C, and the mixture was treated with the dropwise addition of the remainder of the Step 1 product. Following this addition, the mixture was stirred an additional 15 minutes, cooled to 35 C, and treated with three scoops of activated carbon. The slurry was stirred for 30 minutes then filtered, the filtrate concentrated, and 329 g product isolated as a yellow oil. 3.

Preparation of Poly(Butadiene)-Grafted Benzophenone

A mixture consisting of polybutadiene (734 g) dissolved in 1100 ml toluene and the Step 2 product was placed into an addition funnel. Additional polybutadiene (0.88 mol) dissolved in toluene was warmed to 50 C, treated with a solution of 3.0 to 3.5 wt% platinum 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane (1.8 g), and then heated to 80 C. This mixture was treated with the dropwise addition of polybutadiene and the Step 2 product over 90 minutes. The solution was then cooled to 35 C, treated with 7 small scoops activated charcoal, and then filtered and concentrated. The product was isolated as a viscous pale yellow oil in quantitative yield.

DERIVATIVES A thioxanthone, (I), and an amide-containing benzophenone, (II), derivative were also prepared. Polyisobutylene

S

O

O

O

O CO2H O

O

(I)

S

Polyisobutylene

N H

(II)

Notes

509

TESTING Experimental agents were evaluated for their UV curing behavior effectiveness as photoinitiators using a UV curable composition consisting of tetraallyl bisphenol A and Tetrathiol 10. The testing results are summarized in Tables 1 and 2, respectively.

TABLE 1. UV curing behavior of the Step 3 product as a photoinitiator in a UV curable composition consisting of tetraallyl bisphenol A and Tetrathiol 10. Treatment Level (wt%)

Initiator None Benzophenone Step 3 product

DHp (J/g)

–– 2 8

Dt (s)

Conversion (%)

18 117 132

6 40 45

8.4 7.8 7.8

TABLE 2. Effectiveness of the Step 3 as a photoinitiator in a UV curable composition consisting of tetraallyl bisphenol A and Tetrathiol 10 with a UV cutoff of 300 nm. Treatment Level (wt%)

Initiator None Step 3 product Step 3 product

DHp (J/g)

–– 2 8

Dt (s)

Conversion (%)

63 182 244

21 69 79

6.6 9.0 6.0

NOTES 1. UV- and thermally curable cycloaliphatic vinyl ethers, (III), and maleimide derivatives, (IV), were previously prepared by the author [1,2], respectively, and used in resins as moisture barrier sealants. O O

O

(III)

N O

O

O O

O

(IV)

O

O N O

2. Bradley [3] coated circuit boards with a reactive substrate as a method of activating a latent photoinitiator, (V), for subsequent crosslinkable reactions as illustrated below. Multi-layered circuits were also prepared by Kawasaki [4] using benzophenone as the photoinitiator.

510


O

Short wavelength

O +

I

O

S

S

(V)

3. A photosensitive agent, (VI), used as a lithographic printing plate was prepared by Matsumura [5] as a method for improving image resolution and print quality. Br O

Br O

Br

OK

Br CO 2 C 2 H 5

(VI)


D.E. Herr et al., US Patent Application 2006-0223937 (October 5, 2006) D.E. Herr et al., US Patent Application 2006-0009539 (January 12, 2006) G. Bradley, US Patent 7,183,333 (February 27, 2007) Y. Kawasaki et al., US Patent 7,178,234 (February 20, 2007) T. Matsumura et al., US Patent 7,169,535 (January 30, 2007)

b. Reactivatable Polymerization

Title: Radical Polymerization Method Performed in the Presence of Disulfide Compounds Author:

J.-M. Catala, US Patent 7,214,751 (May 8, 2007)

Assignee:

Rhodia Chimie (Aubervilliers, FR)

SIGNIFICANCE A method for preparing isolatable and re-activatable polymethyl methacrylate using the chain transfer agent bis(ethoxythiocarbonyl)disulfane with 2,20 -azobis(isobutyronitrile) is described. Reactivation of this macroinitiator with 2,20 -azobisisobutyronitrile was then used to prepare block copolymers.

REACTION S

a

i O

OCH3

O

OCH3 O

OC2H5

S OCH3

ii

a

b O

O

OCH3 O

i: Benzene, bis(ethoxythiocarbonyl)disulfane, 2,20 -azobisisobutyronitrile, 1,10 azobis(cyclo-hexanecarbonitrile) ii: Benzene, 2,20 -azobisisobutyronitrile, vinyl acetate

EXPERIMENTAL 1.

Preparation of Reactivatable Poly(Methyl Methacrylate)

A reaction vessel was charged with 50 ml of benzene solution containing methyl methacrylate (0.236 mol), bis(ethoxythiocarbonyl)disulfane (1.53 mmol), 2,20 -azobisisobutyronitrile (1.18 mmol), and 1,10 -azobis(cyclohexanecarbonitrile) (1 mmol). The mixture was heated for 4 hours at 80 C and cooled, and the polymer was 511

512

Radical Polymerization Method Performed in the Presence of Disulfide Compounds

precipitated in heptane. After drying the product was isolated in 97.3% yield having a Mn of 11,200 daltons and a polydispersity index of 1.9. 2.

Preparation of Poly(Methyl Methacrylate-block-Vinyl Acetate)

The Step 1 product (8 g) was dissolved in 50 ml of benzene and then treated with 2,20 azobisisobutyronitrile (14.6 mg) and 13.8 g of vinyl acetate and heated to 60 C for 72 hours. The mixture was cooled, and the polymer was precipitated in heptane. After drying the block copolymer was isolated in 47.8% yield having a Mn of 21,500 daltons and a polydispersity index of 1.6.

DERIVATIVES Only the single macroinitiator was prepared.

NOTES 1. S,S0 -bis-(a,a0 -Dimethyl-a00 -acetic acid)-trithiocarbonate, (I), previously prepared by Lai [1], was effective as a chain transfer agent and used in controlled radical polymerizations. S

HO2C

S

S

CO2H

(I)

2. The chain transfer activity of dithiocarbamate reagents, (II) and (III), prepared by Chiefari [2] and Charmot [3], respectively, was impacted by the substituent selection, (IV) and (V), and was effective in conferring living characteristics to a free radical polymerization. These agents were also used in introducing novel end group functionalities into polymers. O S

S N

N

S

S O

(II)

(III)

CO 2 C 2 H 5

Notes

513

S

N

CN

N

S

S

S CN

N N

(IV) (V)

3. Polyfunctional dithiocarbamate derivatives, (VI) and (VII), were prepared by charmot [4] and used as chain transfer reagents in free radical polymerization reactions.

S NC

S S

N N

N

N N

CN S S

N

O

S

S

S

S

S

N N

N

S

S

O

S

S CN

(VII)

(VI)

References 1. J.T. Lai, US Patent Application 2005-0267274 (December 1, 2005), US Patent 7,205,368 (April 17, 2007), and US Patent 6,962,961 (November 8, 2005) 2. J. Chiefari et al., US Patent Application 2004-0024132 (February 5, 2004) and US Patent 6,747,111 (July 8, 2004) 3. D. Charmot et al., US Patent 7,012,119 (March 14, 2006) and US Patent 6,919,409 (July 19, 2005) 4. D. Charmot et al., US Patent Application 2004-0019163 (January 29, 2004)

Title: Copolymers of Maleic Anhydride by Stable Free Radical Polymerization Author:

B. Keoshkerian, US Patent 7,009,011 (March 7, 2007)

Assignee:

Xerox Corporation (Stamford, CT)

SIGNIFICANCE A stable free radical polymerization using 2,2,6,6-tetramethyl-1-piperidinyloxy with maleic anhydride and styrene was used to prepared moderate molecular weight copolymers with polydispersities less than 1.5. Thermal re-activation of these copolymers in the presence of other monomers produced block polymers.

REACTION O

O

O

i Note 1

a O

O

O

ii Note 2

a O

O

O

b CN

i: Styrene, 2,2,6,6-tetramethyl-1-piperidinyloxy ii: Styrene, acrylonitrile

EXPERIMENTAL 1.

Preparation of Poly(Styrene-co-Maleic Anhydride)

A 1-liter reaction vessel was charged with 425 ml of styrene, maleic anhydride (100.2 g), and 2,2,6,6-tetramethyl-1-piperidinyloxy (0.0205 moles) and then treated dropwise with a mixture of 72 ml of styrene and 2,2,6,6-tetramethyl-1-piperidinyloxy (0.0782 moles). The reaction was heated to 135 C for 45 minutes and cooled, and the mixture was dissolved in 500 ml of THF. The polymer was precipitated in 3 liter of hexane, and 125.3 g solid product were isolated having a Mn of 3523 daltons and a polydispersity of 1.48.

514

Notes

515

2. Preparation of Poly(Styrene-co-Maleic Anhydride-b-Styrene-coAcrylonitrile) The Step 1 product was dissolved in 118 ml of styrene and 47 ml of acrylonitrile and then heated to 135 C for 100 minutes and cooled. After the workup described in Step 1, the product was isolated having a Mn of 62,000 daltons with a polydispersity of 1.41.

NOTES 1. Additional free radical polymerization regulating agents were provided by Anderson [1], (I)–(III). O

O HN

HN t-C4 H 9

t-C4H 9 N

N

O

O

O

(I)

(II)

(III)

N

2. Styrene macroinitiator having a Mn of 9300 daltons and terminated with 2,2,6,6-tetramethyl-1-piperidinyloxy was thermally re-activated in the presence of styrene to prepare a polymer having a Mn of 178,000 daltons in an earlier investigation by the author [2]. 3. Fischer prepared poly(styrene-co-acrylonitrile) and polystyrene by stable free radical emulsion polymerization using 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy with potassium peroxodisulfate at 120 C under elevated pressures. Polystyrene samples prepared in this manner had molecular weights of up to 35,000 daltons with polydispersities of less than 1.5. 4. Bifunctional stable free radical polymerization reactions were prepared by Georges [4] using divinylbenzene. TEMPO Initiator

i Initiator Initiator TEMPO

i: 4-Hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy

516

Copolymers of Maleic Anhydride by Stable Free Radical Polymerization

References 1. A.G. Anderson et al., US Patent Application 20020061989 (March 23, 2002) 2. B. Keoshkerian et al., US Patent 6,156,858 (December 5, 2000) and US Patent 5,739,229 (April 14, 1998) 3. M. Fischer et al., US Patent 6,696,533 (February 24, 2004) 4. M.K. Georges et al., US Patent 7,045,248 (July 10, 2001)

H. Macromolecular Depolymerization Catalysts

Title: Catalysts and Methods for Polymerizing Macrocyclic Oligomers Author:

R. P. Dion et al., US Patent 7,196,160 (March 27, 2007)

Assignee:

Dow Global Technologies, Inc. (Midland, MI)

SIGNIFICANCE A method for polymerizing macrocyclic butylene terephthalate oligomers using 1,3diacetoxy-1,1,3,3-tetrabutyldistannoxane is described.

REACTION O

O

O

O

a

O

O

O

O

i Note 1

O HOOC

O

b

OH

b >> a

a>8

i: 1,3-Diacetoxy-1,1,3,3-tetrabutyldistannoxane

EXPERIMENTAL Preparation of Polybutylene Terephthalate Cyclic butylene terephthalate oligomers were heated for 3 minutes in a bowl of a Haake mixer to 230 C and 100 rpm. This was then treated with 0.003 mol of 1,3diacetoxy-1,1,3,3-tetrabutyldistannoxane per mole of cyclic butylene terephthalate. The mixture was heated for 4.5 minutes, and the resulting polymer was recovered. 517

518

Catalysts and Methods for Polymerizing Macrocyclic Oligomers

The polymer was then cooled to ambient temperature, crushed, ground to pass through a 4 mm screen, and dried at 90 C. Molecular weight profiles are provided in Table 1.

POLYMERIZATION MOLECULAR WEIGHT PROFILE TABLE 1. Polymerization of marcocyclic butylene terphthalate using 1,3-diacetoxy1,1,3,3-tetrabutyldistannoxane as catalyst and corresponding molecular weigh profiles. Catalyst (mol%) 0.3 0.6

Mn 1 104 (daltons)

Mw 1 104 (daltons)

Mz 1 105 (daltons)

Mzþ1 1 105 (daltons)

4.16 2.50

9.58 6.17

1.58 1.00

2.34 1.45

NOTES 1. Macrocyclic esters were prepared according to the method of Brunelle [1], which cyclo-oligomerizes terephthaloyl chloride and 1,4-butanediol with triethylamine dissolved in CH2Cl2. 2. Commercially available polybutylene terephthalate was depolymerized by Phelps [2] and Faler [3] into 96% by weight of the tetramer by heating in o-dichlorobenzene. 3. Winckler [4] and Dion [5] polymerized cyclic butylene terephthalate oligomers using the 1,6-distanna-2,5,7,10-tetraoxacyclodecane derivative, (I), as the depolymerization and repolymerization catalyst.

O

O O

O O Sn

Sn O

O

O O

O O

O

(I)

4. A method of re-cycling polytrimethylene terephthalate containing up to 0.5 wt% acrolein by depolymerizing at 210 C for 60 minutes to re-generate 1,3propanediol and terephthalic acid was developed by Kato [6]. In this process the conversion was 100%. 5. Polyvinyl chloride and polyethylene terephthalate were re-cycled by Guffey [7] by heating to between 285 C and 360 C for 15 to 60 minutes to re-generate the corresponding monomers.

Notes

References 1. 2. 3. 4. 5. 6. 7.

D.J. Brunelle et al., US Patent 5,231,161 (July 27, 2003) P.D. Phelps et al., US Patent 6,713,601 (March 30, 2004) G.R.Faler., US Patent 7,022,806 (April 4, 2006) and US Patent 6,525,164 (February 25, 2003) S.J. Winckler et al., US Patent Application 2004-0011992 (January 22, 2004) R.P. Dion et al., US Patent Application 2005-0059768 (March 17, 2005) J. Kato et al., US Patent 6,867,322 (March 15, 2005) F.D. Guffey et al., US Patent 6,861,568 (March 1, 2005)

519

Title: Catalytic Systems Author:

Y.-F. Wang et al., US Patent 7,186,666 (March 6, 2007)

Assignee:

Cyclics Corporation (Schenectady, NY)

SIGNIFICANCE Tetraphenoxyl titanates such as 4-isopropyl-, 2-isopropyl-6-t-butyl-, and 2-di-t-butylhave been prepared and used as catalysts for the rapid depolymerization and repolymerization of macrocyclic oligomers. In this manner macrocyclic co-esters consisting of (butylene terephthalate-co-ethylene terephthalate) were re-polymerized to molecular weights of up to 120,000 daltons.

REACTION t-C4H9

OH

i Note 1

t-C4H9

O Ti 4

Polymer

i: Toluene, tetraisopropyl titanate ii: Macrocyclic(butylene terephthalate-co-ethylene terephthalate)co-ester

EXPERIMENTAL 1.

Preparation of tetra(4-t-Butylphenoxy) Titanate

A reactor was charged with 4-t-butylphenol (199.7 mmol) and 100 ml of toluene and then heated to reflux under nitrogen during which time roughly 20 ml of toluene were removed by distillation. The mixture was then cooled to 100 C, treated with the syringe-addition of tetraisopropyl titanate (47.43 mmol), and refluxed 30 minutes. Isopropanol was then removed by distillation at up to 90 C. Thereafter an additional 50 ml of isopropanol was distilled over at 140 C, and a dark red liquid was isolated. Upon cooling the liquid crystallized to a red solid at ambient temperature. The crystals were dried overnight at 80 C, and the product was isolated in 94.8% yield.

520

Notes

521

2. Polymerization of a oligo(Butylene Terephthalate-co-Ethylene Terephthalate) Macrocyclic Co-ester Macrocyclic(butylene terephthalate-co-ethylene terephthalate) co-ester (8.91 mmol) containing about 95 mol% butylene terephthalate was charged into a vial and then heated to 190 C at 1 torr for 5 minutes in an oil bath. This mixture was then treated with 0.30 mol% of the Step 1 product. The mixture was re-heated to the melt phase at 190 C for 10 minutes and polymerized for 15 minutes. Thereafter the polymer began to crystallize, and a white solid product was isolated.

DERIVATIVES AND RESULTS TABLE 1. Oligomer re-polymerization of macrocyclic oligomers using 0.3 mol% tetraphenoxy titanates. Entry

Catalyst

Oligomer

Polymerization Time (minutes)

Polymer Yield (%)

Mw (daltons)

i-C3H7 O

2

4

Ti

t-C4H9

O

3

4

Ti

t-C4H9

4

t-C4H9

O

4

Ti

t-C4H9

C6H5

O

5 C6H5

4

Ti

Terathane 2900*1

16

95

112,900

Cyclic Poly (ethyleneco-butylene) diol

15

99

21,200

Terathane 2900

15

90

107,000

Terathane 2900

15

90

114,600

Note: Polymerization time represents the time interval when stirring began and ended because of reaction mixture solidification. *1

Polytetramethyleneether ester with a Mn of 2,900 daltons

NOTES 1. The preparation and use of organotin compounds as re-polymerization agents for linear polyesters and macrocyclic oligomers is provided by Faler [1] and Winckler [2], respectively.

522

Catalytic Systems

2. Paquette [3,4] re-polymerized macrocyclic butylene terephthalate oligomers containing fibers using 1,1,6,6-tetrabutyl-1,6-distanna-2,5,7,10-tetraoxacyclodecane as the reaction catalyst. 3. Kuhlman [5] re-polymerized macrocyclic ester oligomers in the presence of di-n-butyl tin oxalate, which had up to a 2 minute latency period and was followed by a rapid polymerization similar to that of di-n-butyltin glycolate. References 1. 2. 3. 4.

G.R. Faler, US Patent 7,022,806 (April 4, 2006) and US Patent 6,525,164 (February 25, 2003) S.J. Winckler et al., US Patent 6,369,157 (April 9, 2002) M.S. Paquette, US Patent Application 2006-0004135 (January 5, 2006) M.S. Paquette, US Patent Application 2006-0003887 (January 5, 2006) and US Patent Application 2005-0288420 (December 29, 2005) 5. R.L. Kuhlman et al., US Patent Application 2005-0288176 (December 29,2005)

I. Metallocene Catalysts

Title: Metallocene Catalysts Containing a Cyclopentadienyl Ligand Substituted by a Siloxy or Germiloxy Group Containing an Olefinic Residue Author:

M. Aubert et al., US Patent 7,037,872 (May 2, 2006)

Assignee:

Borealis Technology Oy (Porvoo, FI)

SIGNIFICANCE The metallocene pre-catalyst, ethylene-bis2-(4-butenyldiisopropylsiloxy)-1-indenyl) zirconium dichloride, has been prepared. When blended with co-catalyst methylalumoxane forming an aluminum/zirconium ratio of 300:1, respectively, the catalytic mixture had very high ethylene polymerization activity.

REACTION

Br

n

i

Cl

v

ii

Si

Si

iii

Si

iv

Si

ZrCl2 Si

Si

523

524

i: ii: iii: iv: v:

Metallocene Catalysts Containing a Cyclopentadienyl Ligand Substituted by a Siloxy

Magnesium, THF, diisopropyldichlorosilane, copper (I) cyanide 2-Indanone, 1,8-diazobicyclo[5.4.0]undec-7-ene, benzene THF, n-butyllithium, 1,2-dibromoethane Zirconium tetrachloride, diethyl ether, n-butyllithium Methylalumoxane, ethylene

EXPERIMENTAL 1.

Preparation of (4-Butenyldiisopropylchloro)Silane

A suspension of magnesium turnings (0.11 mol) in 50 ml of THF was treated dropwise with 4-bromo-1-butene (0.11 mol), and the mixture was stirred for 12 hours. The solution was then cooled to 10 C, and CuCN (1 mmol) was added followed immediately by the dropwise addition of diisopropyldichlorosilane (0.11 mol). The reaction mixture was then gradually warmed to ambient temperature and stirred for 12 hours, filtered, and concentrated; 14.5 g of product were isolated. 2.

Preparation of 2-(4-Butenyldiisopropylsiloxy)Indene

A solution of the Step 1 product (73.2 mmol) and 2-indanone (73.2 mmol) dissolved in 30 ml of benzene was added dropwise to a solution of 1,8-diazobicyclo[5.4.0]undec7-ene (73.2 mmol) in 25 ml of benzene at ambient temperature, and the reaction mixture was stirred for 12 hours. The mixture was then quenched with water and extracted with diethyl ether. The ethereal solution was dried using MgSO4, concentrated, and purified using flash chromatography with hexane; 12.9 g of product was isolated. 3.

Preparation of bis-2-(4-Butenyldiisopropylsiloxy)1-Indenyl)Ethane

To a solution of the Step 2 product (43.9 mmol) dissolved in 50 ml of THF was added dropwise to n-butyllithium (22 mmol; 2.5 M in hexane) at 15 C, and the mixture was stirred for 2 hours at ambient temperature. It was then treated with the dropwise addition of 1,2-dibromoethane (22 mmol) in 10 ml of THF at 78 C and stirred an additional 12 hours at ambient temperature. This solution was quenched by pouring into water and extracted with diethyl ether. The workup was identical to that in Step 2, and 2.0 g of product were isolated. 4. Preparation [Ethylene-bis-2-(4-Butenyldiisopropylsiloxy)-1-Indenyl)] Zirconium Dichloride A solution of the Step 3 product (3.2 mmol) dissolved in 20 ml of diethyl ether was added dropwise to n-butyllithium (6.4 mmol; 2.5 M in hexane) at 15 C, and the reaction mixture was stirred for 2 hours at ambient temperature. The mixture was then concentrated, and ZrCl4 (3.2 mmol) was added to the residue. The solid was then

Notes

525

treated with 30 ml of cold CH2Cl2, and the suspension was stirred at 80 C for 15 minutes before being slowly warmed to ambient temperature and stirred an additional 12 hours. The suspension was filtered through celite and concentrated, and the product was isolated in 44% yield after re-crystallization in hexane at 78 C. 5.

Preparation of Polyethylene

Methylalumoxane (3.32 g) and the Step 4 product (38.2 mmol) were thoroughly mixed and placed in a burette. A stirred 1-liter Buchi autoclave reactor was charged with 150 ml of toluene and methylalumoxane, and the Step 4 product mixture added; the aluminium/zirconium ratio was 300. The reaction was conducted under an ethylene pressure of 0.3 bar at 20 C for 2 hours. The reactor was then purged with nitrogen to remove ethylene, and the reactor temperature was raised to 80 C. Thereafter 2.85 bar of ethylene pressure was applied, and the polymerization was conducted for 30 minutes while maintaining the ethylene pressure and temperature at this level. The ethylene consumption was 0.7082 mol, and the product was isolated having a MP ¼ 127 C.

DERIVATIVES One derivative, (I), was prepared.

(H3C)2Si

Si ZrCl2

Si

(I)

NOTES 1. Metallocene catalysts of the current invention containing siloxy or germyloxy group in the 4-, 5-, 6- or 7-indene position, (II), were prepared by Ekhom [1] and used in preparing HDPE, LDPE, and LLDPE.

526

Metallocene Catalysts Containing a Cyclopentadienyl Ligand Substituted by a Siloxy

OSi(CH3)2-t-C4H9

(H3C)2Si ZrCl2

t-C4H9-(H3C)2SiO

(II) 2. Other pre-catalysts have been prepared that are effective in polymerizing ethylene and a-olefins to high molecular weights with low crystallinity. Kucha [2] prepared phenoxy/amine derivatives of hafnium, titanium, and zirconium, (III), while Kol [3] and Shih [4] prepared ultra-high activity, (IV) and (V), respectively, pre-catalysts useful in polymerizing a-olefins having very high molecular weights and low polydispersities.

C6H5

t-C4H9

O

M

t-C4H9 Zr O O N

N

N

M = Hf, Ti, Zr

t-C4H9

N

(IV) (III)

Cl

Cl Fe N

N N

(V)

t-C4H9

t-C4H9

Notes

527

3. Metallocene derivatives containing azulenyl rings, (VI), were prepared by Iwama [5] and used to polymerized propylene.

Cl

(H3C)3Si

Cl

Si(CH3)2

Cl2Hf

Cl Cl

Si(CH3)3

(VI) 4. Monocyclopentadienyl metallocene catalysts, (VII), not requiring methylalumoxane as a co-catalyst were prepared by Canich [6] and used to prepare ethylene/a-olefin copolymers.

(H3C)2Si

Zr

B(pfp)4

t-C4H9

(VII) References 1. 2. 3. 4. 5. 6.

P. Ekhom et al., US Patent Application 2004-052882 (August 5, 2004) M.C. Kuchta et al., US Patent 7,045,583 (May 16, 2006) M. Kol et al., US Patent 6,596,827 (July 22, 2003) K.-Y. Shih, US Patent 6,943,224 (September 13, 2005) N. Iwama et al., US Patent 7,189,790 (March 13, 2007) J.A.M. Canich et al., US Patent 7,163,907 (January 16, 2007)

J. Ring-Opening Metathesis Catalyst

Title: Photochromic Polymers and Methods of Synthesizing Same Author:

N. R. Branda et al., US Patent 7,041,763 (May 9, 2006)

Assignee:

Simon Fraser University (Burnaby, CA)

SIGNIFICANCE There are a limited number of photochromic polymers as a result of the relatively harsh methods used to prepare them. A mild method for preparing these materials using ring-opening metathesis polymerization at ambient temperature is described.

528

Experimental

529

REACTION H O

O

H

H

O

i

O

N H

O

O OH

O

Intermediate

iii Intermediate

ii Cl

S

Cl

Cl

S

S

S

CO2H

O

iv Cl

S

S

O Cl

S

S

O O

O O

H

N O

O H

H

N O

H

a H

i: ii: iii: iv:

4-Aminophenol, glacial acetic acid THF, t-butyllithium, carbon dioxide DMF, CH2Cl2, oxalyl chloride, triethylamine, acetone CH2Cl2, bis(tricyclohexylphosphine)benzylidine ruthenium(IV)dichloride, ethylvinyl ether

EXPERIMENTAL 1. Preparation of exo-N-(p-Hydroxyphenyl)-3,6-Epoxy-4-Cyclohexene-1,2Dicarboximide A mixture consisting of 7-oxa-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (12 mmol) and 4-aminophenol (12 mmol) were refluxed for 10 minutes in 3 ml of glacial acetic acid after which time a precipitate formed. The reaction mixture was cooled to ambient temperature and the precipitate isolated by filtration. The solid was washed with water and dried, and the product was isolated in 68% yield as a white solid.

530

Photochromic Polymers and Methods of Synthesizing Same

H NMR (d6-DMSO) d 9.71 (s, 1H), 6.95 (d, J ¼ 8.75 Hz, 2H), 6.83 (d, J ¼ 8.75 Hz, 2H), 6.58 (s, 2H), 5.21 (s, 2H), 3.02 (s, 2H) 13 C NMR (d6-DMSO) d 175.95, 157.27, 136.53, 127.98, 123.19, 115.38, 80.66, 47.20; EIMS (m/z): 257 FTIR (cm1) 3334 (s, broad), 3143, 3102, 3076, 3049, 3029, 2973, 1697, 1612, 1594 1

2. Preparation of Acid 1-(2-Methyl-5-Chloro-Thiophen-3-yl)-2-(2-Methyl-5Hydroxycarboxy-Thiophen-3-yl)Cyclopentene A solution of 1,2-bis(2-methyl-5-chloro-thiophen-3-yl)cyclopentene (1.17 mmol) in 50 ml of THF was cooled to 78 C and treated with t-butyllithium (1.17 mmol); it was then stirred for 15 minutes and excess CO2 was bubbled through the solution. Thereafter the reaction mixture was warmed to ambient temperature, quenched with dilute hydrochloric acid, and extracted 3 times with 50 ml of diethyl ether. The ethereal solution was dried, concentrated, purified by column chromatography using silica with 5% CH3OH/CH2Cl2, and the product was isolated in 80% yield as a pale yellow solid. 1

H NMR (CDCl3) d 7.55 (s, 1H), 6.52 (s, 1H), 2.72 (m, 4H), 1.99 (m, 5H), 1.80 (s, 3H)

3. Preparation of Acid 1-(2-Methyl-5-Chloro-Thiophen-3-yl)-2-(2-Methyl-5Hydroxycarboxy-Thiophen-3-yl)Cyclopentyl-3,6-Epoxy-4-Cyclohexene-1,2Dicarboximide exo-N-(4-Phenylate) A stirred solution of the Step 2 product (0.4 mmol) and 5 drops of DMF in 4 ml of CH2Cl2 at 0 C were treated with the dropwise addition of oxalyl chloride (2.0 mmol), dissolved in 6 ml CH2Cl2, and then stirred at ambient temperature for 2 hours. The mixture was concentrated and the residue dissolved in 10 ml of CH2Cl2; it was then added dropwise to a solution of the Step 1 product (0.6 mmol) and 0.5 ml of triethylamine dissolved in acetone and cooled to 0 C. The mixture was stirred overnight, concentrated, purified by column chromatography using silica with 2% CH3OH/CHCl3, and the product was isolated in 82% yield as a pale yellow solid. 1

H NMR (CDCl3) d 7.67 (s, 1H), 7.31 (m, 4H), 6.56 (s, 3H), 5.38 (m, 2H), 3.00 (s, 2H), 2.76 (m, 4H), 2.05 (m, 5H), 1.87 (s, 3H) 13 C NMR (CDCl3) d 175.22, 159.95, 150.56, 144.60, 137.19, 136.78, 136.02, 135.33, 134.75, 134.14, 133.36, 129.16, 128.03, 127.62, 126.66, 125.59, 122.38, 81.51, 47.59, 38.61, 38.52, 22.89, 14.98, 14.30 ESMS(+ive): 600.0 (M + Na+), 532 (M Cl)

4.

Polymerization Reaction

A 0.1M solution of the Step 3 product dissolved in CH2Cl2 was charged into a Schlenk tube followed by a CH2Cl2 solution of bis(tricyclohexylphosphine)benzylidine ruthenium(IV)dichloride (0.04 eq). The solution was then stirred for 14 hours at ambient temperature. Excess ethylvinyl ether was added, and the solution was stirred while exposed to the atmosphere for 30 minutes. Thereafter the polymer was precipitated into cold diethyl ether, and the product was isolated in 75% yield.

Notes

531

FTIR (KBr-cast; cm1) 3050 (w), 2951 (w), 2843 (w), 1713 (s), 1202 (s). 1 H NMR (CDCl3) d 7.6 (br s), 7.3 (br s), 6.6 (br s), 6.1 (br s), 5.8 (m), 5.2 (m), 4.6 (m), 3.4 (br s), 2.7 (br s), 2.0 (m), 1.8 (br s)

DERIVATIVES Two additional derivatives were prepared as illustrated below. F6

O O

Cl

S

H

N

O

S O

O

H

a H

H

O

O N

O

O S

H

a

N

S O

O

O

H

O

H

H

a H

NOTES 1. In an earlier investigation by Kim [1] benzothiophene derivatives, (I), were prepared and used as components in photochromic polymers.

O

O O O

S

S

(I)

532

Photochromic Polymers and Methods of Synthesizing Same

2. Photochromic polymers, (II), prepared by Kim [2] had a fluorescence quantum yield of 53% at 290 nm as well as excellent solubility in organic solvents and were used in information processing devices. Tanaka [3] prepared the nonpolymeric analogue, (III), of this agent, which was used in irradiation detectors. F6

F6

S

t-C4H9

a

S

S

S

t-C4H9

(III)

(II)

3. Photochromic [1,2-b] naphthopyran derivatives, (IV), prepared by Hughes [4] exhibited absorption in the 400-550 nm (brown) range and were used in graft copolymer reactions.

H3CO

N

H3CO X F

X = CH2OH; COOCH3

(IV)


E.-K. Kim et al., US Patent 6,479,604 (November 12, 2002) E. Kim et al., US Patent 7,135,132 (November 14, 2006) Y. Tanaka et al., US Patent 7,101,497 (September 5, 2006) F.J. Hughes et al., US Patent 6,863,843 (March 8, 2005)

Title: Synthesis of A,B-Alternating Copolymers by Olefin Metathesis Reactions of Cyclic Olefins or Olefinic Polymers with an Acyclic Diene Author:

T.-L. Choi et al., US Patent 6,987,154 (January 17, 2006)

Assignee:

California Institute of Technology (Pasadena, CA)

SIGNIFICANCE Ring-opening metathesis polymerization, ROMP, using a cyclic and acyclic olefin monomer was used to prepare co-polymers with monomer alternation exceeding 95%. Monomer-to-ruthenium catalyst studies were also performed to minimize polydispersities and maximize molecular weights.

REACTION O

i Note 1

O 4

a

i: CH2Cl2, 1,4-butanediol diacrylate, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) benzylidene-tricyclopentylphosphine ruthenium(II) dichloride, methanol

EXPERIMENTAL A small flask was charged with 1,4-butanediol diacrylate (0.45 mmol) dissolved in 2 ml of CH2Cl2 then treated with 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene-tricyclopentyl-phosphine ruthenium(II) dichloride (2.7 mg) and cyclooctene (0.45 mmol), the total monomer-to-catalyst ratio being 290:1. The mixture was

533

534

Synthesis of A,B-Alternating Copolymers by Olefin Metathesis Reactions of Cyclic Olefins

degassed and the flask refluxed for 6 hours under argon. The reaction contents were precipitated in 50 ml of methanol, and a white polymer was isolated. The crude polymer was washed several times with methanol and dried, and the product was isolated in 84% yield with 99% alternation. MW (GPC) ¼ 90,100 daltons 1 H-NMR (300 MHz, CDCl3): d ¼ 6.93 (dt, J ¼ 7.2, 15.9 Hz, 1H), 577 (d,J ¼ 15.9 Hz, 1H), 4.13 (br s, 2H), 2.12 (m, 2H), 1.73 (m, 2H), 1.43 (m, 2H), 1.30 ppm (m, 2H) 13 C-NMR (75 MHz, CDCl3): d ¼ 166.8, 149.6, 121.3, 64.0, 32.5, 29.3, 28.2, 25.8 ppm

DERIVATIVES TABLE 1. Ring-opening metathesis polymerization cyclic and acyclic monomers in preparing copolymers using catalyst 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) benzylidene-tricyclopentylphosphine ruthenium(II) dichloride.

Entry

Monomer 1

Monomer 2

Mn MonomerMonomer (1 103 Catalyst Polymer Alternation daltons) Ratio Yield (%) (%) (PDI)

O 1A

O O

100

87

95

90.0 (1.73)

N H H N

—

99

97

9.7 (1.45)

75

96

20.3 (1.58)

97

14.1 (1.80)

O

O 1B

O

2

Same

125

3

Same

125

93

(continued)

Notes

535

TABLE 1. (Continued )

Entry Monomer 1

Mn Monomer (1 103 MonomerCatalyst Polymer Alternation daltons) (%) Ratio Yield (%) (PDI)

Monomer 2 (n-C4H9)3SiO

5

Same

250

69

94.5

21.4 (1.43)

100

98

97

25.2 (2.06)

O O 7

O O Note: 1 H- and

13

C-NMR product characterization provided by the author.

NOTES 1. The ROMP catalyst of the current invention, (I), is illustrated below.

N

N

Cl Ru Cl (C5H9)3P

(I)

2. In subsequent investigations by the author [1] the catalyst of the current invention was used to prepare macrocycles, (II). Morgan [2] observed a similar effect using 1, 5-cyclooctadienes, which underwent a ring-opening crossmetathesis reaction forming linear compounds, (III), without polymerizing as illustrated in the second equation.

536


O O

+

R

R

O

i

a, b = 4 - 12 c=1-7

R b

a

c

O

(II) OCH3

O

+

i

OCH3

O O OCH3

(III)

i: CH2Cl2, 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene)benzylidene-tricyclopentylphosphine ruthenium(II) dichloride 3. Using the ROMP catalyst bis(tricyclopentylphosphine)dichloro-(3-methyl2-butenylidene)-ruthenium, (IV), Piccinelli [3] prepared low molecular weight polynorbornene derivatives functionalized with hydrophilic polyethers, (V), which were subsequently hydrogenated, (VI), as illustrated in the second equation. P(C5H9)3 Cl Ru Cl P(C5H9)3

(IV)

O

i

OCH3 a

b

(VI)

b

O

OCH3

a

O

(V)

a

OCH3 ii

a = 3, 7 b = 5–15

4. Liaw [4] synthesized norbornene monomers containing crosslinkable side chains (VII), which underwent a ROMP reaction with a ruthenium-based

Notes

537

catalyst, (VIII), forming polynorbornene, (IX), or forming a polymethacrylate derivative, (X) by free radical polymerization as illustrated below. a

O O HN

O O

P(C6H11)3 Cl Cl O O

N H

(VII)

C6H5

(IX)

Ru P(C6H11)3

(VIII)

O O

a

O O

NH O O

(X)

5. Mather [5] prepared elastomeric materials having excellent shape recovery properties by polymerizing cyclooctene using the dihydroimidazolylidenemodified Grubbs catalyst, (I), and then crosslinking the intermediate with dicumyl peroxide.

538


References 1. T.-L. Choi et al., US Patent 7,034,096 (April 25, 2005) and US Patent Application 2003-0236367 (December 25, 2003) 2. J.P. Morgan, US Patent 6,803,429 (October 12, 2004) 3. P. Piccinelli et al., US Patent 7,160,969 (January 9, 2007) 4. D.-J. Liaw et al., US Patent 7,132,565 (November 7, 2006) 5. P.T. Mather et al., US Patent 7,173,096 (February 6, 2006)

K. Ziegler–Natta

Title: High 1,4-cis Polybutadiene-Polyurethane Copolymer and Preparation Method Thereof Author:

G. H. Kwag et al., US Patent 7,247,695 (July 24, 2007)

Assignee:

Korea Kumho Petrochemical Co., Ltd. (Chongno-gu, Seoul, KR)

SIGNIFICANCE 1,3-Butadiene has been converted into poly-1,4-(cis-butadiene) in greater than 98.3% by Ziegler–Natta catalysis comprising neodymium versatate, diethyl aluminum chloride, diisobutylaluminum hydride, and triisobutylaluminum. The polymer was then converted into a polybutadiene-polyurethane copolymer by reacting with a diisocyanate and diol. This copolymer exhibited low cold flow and high affinity for silica or carbon black, excellent elasticity, and abrasion resistance.

REACTION

i Note 1

H N

a

O

H N b O

O O

cO

N d e H

i: Neodymium versatate, diethylaluminum chloride, diisobutylaluminum hydride, triisobutylaluminum, polymethylene diphenyl diisocyanate, ethylene glycol

EXPERIMENTAL Preparation of Poly-1,4-(cis-Butadiene-co-Urethane) The Ziegler–Natta catalyst used for the reaction consisted of 1.0% neodymium versatate dissolved in cyclohexane solution, 1M of diethylaluminum chloride 539

540

High 1,4-cis Polybutadiene-Polyurethane Copolymer and Preparation Method Thereof

dissolved in cyclohexane solution, 15% diisobutylaluminum hydride in hexane solution, and 1M of triisobutylaluminum dissolved in heptane solution in a molar ratio of 1/25/4/2.5, respectively. Approximately 1.0 10 4 mol of the neodymium catalyst mixture was used per 100 g of 1,3-butadiene. A reactor was charged with the Ziegler–Natta catalyst mixture and then treated with butadiene (400 g) and polymerized at 70 C for 1 hour. This mixture was next treated with polymethylene diphenyl diisocyanate (0.3 phr) and ethylene glycol (0.6 phr) and stirred for 1 hour. Finally, 2,6di-t-butyl-p-cresol and ethanol were added to terminate the reaction, and the product was isolated.

REACTION SCOPING TABLE 1. Reaction stoichometry used in preparing poly-1,4-(cis-butadiene-courethane) at 70 C.

Entry 1 4 7 9

Nd Catalyst (10 4 mol) 1.0 1.2 1.5 1.5

Molar Ratio of Nd:TIBA: DIBAL:DIEC*1

Added Isocyanate (phr)*2

Added Alcohol (phr)

1:25:4:2.5 1:20:7:2 1:30:5:3 1:30:5:3

0.3 0.3 0.3 10.0

0.3 1.2 0.6 4.0

*1 Neodymium versatate, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, respectively *2 Parts by weight of resin

TABLE 2. Physical properties of 1,4-cis-poly(polybutadiene-co-urethane) prepared at 70 C using the stoichometry described in Table 1.

Entry 1 4 7 9

Polyisobutylene cis Content (%) 98.7 98.4 98.3 98.3

Mw (daltons)

PDI

Urethane Copolymer Mw (daltons)

851,300 613,500 583,600 573,200

2.70 2.86 2.64 2.55

872,500 664,800 620,600 823,700

PDI 2.89 3.80 2.84 3.25

NOTES 1. Jang [1] prepared high cis-1,4-polybutadiene having controlled cold flow without causing a significant increase in the Mooney viscosity using the Ziegler–Natta catalyst of the current invention. In an earlier investigation by

Notes

541

Jang [2] a Ziegler–Natta catalyst consisting of nickel naphthenate, boron trifluoride dibutylether, and triethylaluminum was used to control 1,2-branching in 1,4-butadiene polymerization. 2. Polybutadiene-co-urea-, (Ia), and co-polyurethane, (Ib), polymers were prepared by Wu [3] and Cavallaro [4], respectively, and used as a component in high-performance golf balls. O

O a

b

c

d

X

N H

N H

e

Ia X = NH Ib X = O

(I)

3. Wu [5] prepared co-urea polyisoprene copolymers consisting of polyisoprenediamines with 4-methylene-bis(cyclohexyl isocyanate). References 1. 2. 3. 4. 5.

Y.C. Jang et al., US Patent 6,908,975 (June 21, 2005) and US Patent 6,562,917 (May 13, 2003) Y.C. Jang et al., US Patent 6,586,542 (July 1, 2003) S. Wu et al., US Patent 7,217,764 (May 15, 2007) and US Patent 7,214,738 (May 8, 2007) C. Cavallaro et al., US Patent 7,226,368 (June 5, 2007) S. Wu et al., US Patent 7,253,242 (August 7, 2007)

Title: Process for Producing Polymer Author:

T. Arai et al., US Patent 7,214,745 (May 8, 2007)

Assignee:

Denki Kagaku Kogyo Kabushiki Kaisha (Tokyo, JP)

SIGNIFICANCE rac-Phenylboranediylbis{1-(2-methyl-cyclopenta[1]phenanthryl)}-zirconium dichloride has been found effective as a high-activity ethylene polymerization catalyst when used with triisobutylaluminum co-catalyst in a reduced amount.

REACTION

i

B

ii Note 1

Cl2Zr B

i: Diethyl ether, dichlorophenyl borane, n-butyllithium ii: Toluene, tetrakis(dimethylamino)zirconium, trimethylsilyl chloride

EXPERIMENTAL 1.

Preparation of bis(1-(2-Methyl-Cyclopenta[1]Phenanthryl))Phenylborane

Under an argon stream, 50 ml of a diethyl ether solution of 1H-(2-methyl-cyclopenta [1]-phenanthrene) (21.7 mmol) was cooled to 0 C and then treated with n-butyllithium in hexane solution (21.7 mmol) and stirred at ambient temperature for 3 hours. This solution was added dropwise to 50 ml of a diethyl ether solution of dichlorophenyl 542

Derivatives

543

borane (10.8 mmol) cooled to 75 C and stirred overnight while gradually returning to ambient temperature. Thereafter the mixture was concentrated, and the crude product was isolated in quantitative yield. 2. Preparation of rac-Phenylboranediylbis{1-(2-Methyl-Cyclopenta[1] Phenanthryl)}-Zirconium Dichloride In an argon atmosphere 40 ml of toluene containing the Step 1 product (5.65 mmol) was added to a 40 ml of the toluene solution containing tetrakis(dimethylamino) zirconium (5.77 mmol) and then refluxed for 4 hours. The mixture was concentrated and treated with 80 ml of toluene containing trimethylsilyl chloride (92.3 mmol) and stirred overnight. The mixture was re-concentrated, and the residue was washed with pentane and extracted with CH2Cl2. The extract was then concentrated, and precipitated crystals were collected by filtration. Crystals were washed with diethyl ether and dried under reduced pressure at from 70 C to 120 C. The crystals were re-extracted with methylene chloride, the solution concentrated, and 0.2 g of a clear yellow solid product was isolated. 3.


A 10-liter reactor was charged with 4.8 liter of toluene, heated to 70 C, and treated with triisobutylaluminum (8.4 mmol). The temperature was then increased to 90 C, and ethylene was introduced. After the pressure was stabilized at 1.1 MPa, 50 ml of a toluene solution containing the Step 2 product (0.3 mmol) and triisobutylaluminum (0.84 mmol) were added. The polymerization duration was 5 minutes. Thereafter the reaction was quenched with methanol, and 215 g of product were isolated. 1

HNMR (CDCl3) d 1.71 ppm (methyl group s, 6H), 7.26 (d, 2H), 7.12 8.79 ppm (21H)

DERIVATIVES Two additional derivatives were prepared by the author as illustrated below.

Cl2Zr

R R

i-C3H7 B

N i-C3H7

R = H, CH3

544

Process for Producing Polymer

CATALYST REACTIVITY PROFILE A summary of the 5-minute catalyst scoping polymerization reactions conducted at 90 C using ethylene and triisobutylaluminum is provided in Table 1.

Cl

Cl Zr

R1 R1 B R2 TABLE 1. Catalyst scoping at 90 C with 1.1 MPa ethylene in toluene using triisobutylaluminum as co-catalyst for 5-minute polymerization reactions. Entry 1 2 3

R1

R2

Catalyst Amount (mmol)

Polyethylene (g)

Catalyst Activity (g/mol-Zr h)/106

H CH3 H

Phenyl Di-isopropylamino Di-isopropylamino

0.3 1.0 2.1

215 214 222

8,600 2,568 1,269

NOTES 1. rac-Diisopropylaminoboranediylbis(4,5-benz-1-indenyl)zirconium dichloride, (I), was previously prepared by the author [1] using methyl aluminoxane as a co-catalyst and used to prepare poly(ethylene-co-styrene). Under analogous reaction conditions, the author [2] terpolymerized ethylene, styrene, and divinylbenzene using rac-dimethylmethylenebis(4,5-benzo1-indenyl)zirconium dichloride, (II).

i-C3H7

Cl2Zr B

Cl2Zr

N i-C3H7

(I)

(II)

Notes

545

2. Fluoroaluminoxane-containing co-catalysts, (III), prepared by Sangokoya [3] were equivalent to or better than nonhalogenated MAO compositions.

F Al O

O

(III) 3. Solid-state hydroxyisobutylaluminoxane co-catalysts prepared by Wu [4] were as effective in activating metallocenes in olefin polymerization as the corresponding alkyl aluminoxanes but at a lower aluminum/metal ratio.


T. Arai et al., US Patent 6,891,004 (May 10, 2005) T. Arai et al., US Patent 6,878,779 (April 12, 2005) and US Patent 6,803,422 (October 12, 2004) S.A. Sangokoya et al., US Patent 7,193,100 (March 20, 2007) F.-J. Wu et al., US Patent 6,812,182 (November 2, 2004)

Title: Polymerization Catalyst Composition Author:

S.W.-Y. Chow et al., US Patent 7,176,158 (February 13, 2007)

Assignee:

ExxonMobil Chemical Patents, Inc. (Houston, TX)

SIGNIFICANCE A high-activity ethylene polymerization catalyst [bis(4-allyl-2,6-diisopropylphenylimino)acenaphtheno]nickel(II) dibromide has been prepared. When used in conjunction with methylalumoxanes, high polymers were produced.

REACTION

i O

N

ii

N

O

a

iii

N

N

Ni Br

i: 4-Allyl-2,6-diisopropylaniline, acetic acid ii: Nickel bromide ethylene glycol dimethyl ether, CH2Cl2 iii: Ethylene, toluene, methyl alumoxane

546

Br

Reaction Scoping

547

EXPERIMENTAL 1.

Preparation of bis(4-Allyl-2,6-Diisopropylphenylimino)Acenaphthene

A mixture consisting of acenaphthoquinone (5.5 mmol) and 4-allyl-2,6-diisopropylaniline (11.1 mmol) dissolved in 10 ml of acetic acid was refluxed one hour and then cooled to ambient temperature and filtered. The solid was washed with 5 ml of acetic acid, four times with 10 ml of hexane, and dried; the product was isolated in 82% yield. 1

H-NMR (400 MHz, CDCl3): d 7.86 (d, 2H, H.sub.o-Ace-C.dbd.N), 7.37 (t, 2H, H.sub.m-Ace-C.dbd.N), 7.07 (s, 4H, H–Ar–N.dbd.C), 6.65 (d, 2H, H.sub.p-Ace-C.dbd.N), 6.15 (m, 2H, CH.dbd.C), 5.15 (m, 4H, C.dbd.C–H), 3.50 (d, 4H, CH2–C.dbd.C), 3.00 (m, 4H,CH(Me)2),1.22 (d,12H, C(CH3)2), 0.96 (d, 12H, C(CH3)2 Elemental Analysis Calcd for C42H48N2: C, 86.86; H, 8.32; N, 4.82. Found: C, 87.75; H, 7.35; N, 4.82

2. Preparation of [bis(4-Allyl-2,6-Diisopropylphenylimino)Acenaphtheno] Nickel(II)Dibromide Nickel bromide ethylene glycol dimethyl ether (0.25 mmol) and the Step 1 product (0.32 mmol) were combined in a Schlenk flask under an argon atmosphere and 20 ml of CH2Cl2 added. The mixture was stirred 24 hours at ambient temperature and then concentrated. The residue was washed three times with 10 ml of diethyl ether and dried; the product was isolated as a dark-red powder in 85% yield. Elemental analysis Calcd for C42H48Br2N2Ni: C, 63.11 H, 6.05; N, 3.50. Found: C, 63.45; H, 5.60; N, 3.37

3.


The Step 2 product was added to a flame-dried Schlenk flask with a stirrer and then backfilled three times with ethylene and 50 ml of toluene added. Stirring was begun, and methyl alumoxane dissolved in heptane added by syringe. After 30 minutes the reaction was quenched with acidified ethanol, filtered, dried in vacuum at 40 C for 10 hours, and the product was isolated.

REACTION SCOPING TABLE 1. Ethylene polymerization results using the Step 2 product with an Al/Ni ratio of 2500. Entry

T ( C)

1 2 3

25 0 15

Catalyst Activity (106 g PE mol1 Ni h1)

Polyethylene Mn (daltons)

Polyethylene Mw (daltons)

PDI

2.67 3.32 2.83

110,832 193,660 221,695

195,796 478,735 504,193

1.767 2.472 2.274

Note: All polymerization reactions had a duration of 30 minutes in 50 ml of toluene with an ethylene pressure of 0.1 MPa.

548

Polymerization Catalyst Composition

NOTES 1. Phenol imine derivatives, (I), prepared by the author [1] in an earlier investigation were used to polymerize styrene when activated with 2,20 azobis(2-methylpropanenitrile).

i-C3H7 (C6H5)3P O

Ni

N i-C3H7

(I)

2. Nickel-based azo-phenoxides, (II), prepared by Hinkle [2] and iron-based pyridinyl diimines, (III), prepared by Razavi [3] were used to synthesize high molecular weight ethylene and ethylene/1-hexene copolymers, respectively, when activated with methylalumoxane. t-C4H9

i-C3H7

(C6H5)3P

Cl

Cl

Ni O

N N i-C3H7

N

Fe

N

N

(II)

t-C4H9

(III)

3. a-Diimine transition metal catalysts, (IV), prepared by Zhao [4] and catecholate derivatives, (V), prepared by Cherkasov [5] were effective as ethylene oligomerizing agents when activated with methylalumoxane.

Notes

n-C4H9

N

N

n-C4H9

M X

X

(IV)

N

O Ni Ni O

(V) References 1. 2. 3. 4. 5.

S.W.-Y. Chow et al., US Patent 7,119,155 (October 10, 2006) P.V. Hinkle et al., US Patent 7,094,848 (August 22, 2006) A. Razavi et al., US Patent 7,176,950 (February 13, 2007) B. Zhao et al., US Patent 7,161,018 (January 9, 2007) V.K. Cherkasov et al., US Patent Application 2006-0047094 (March 2, 2006)

M Ni Pd

X Br Cl

549

Title: Synthetic Polyisoprenes and a Process for Their Preparation Author:

P. Laubry, US Patent 6,992,157 (January 31, 2007)

Assignee:

Michelin Recherche et Technique S.A. (Granges-Paccot, CH)

SIGNIFICANCE A synthetic method for preparing polyisoprene having a cis-1,4 linkage of 99.0% or greater using diethylaluminium chloride with the rare earth salt neodymium tris(bis (2-ethylhexyl)phosphate) is described. Reproducible Mooney viscosities of 85 and higher were also observed.

REACTION

i a i: Cyclohexane, acetylacetone, N-1,3-dimethylbutyl-N0 -phenyl-p-phenylenediamine, neodymium tris(bis(2-ethylhexyl)phosphate), diethylaluminium chloride

EXPERIMENTAL 1.

Preparation of cis-1,4-Polyisoprene

A 250-ml reaction vessel was used as the polymerization reactor. Each polymerization reaction was carried out either under static conditions in a freezer, where the container was placed in a bath of glycol, or dynamically, by subjecting the container to agitation in a tank of glycol. Isoprene monomer having a purity of 99.2% was used. All polymerizations were conducted in 10-g containers and cyclohexane at 15 C with a solvent/monomer mass ratio of 9. In a typical polymerization the neodymium catalyst/diethyl aluminium chloride base varied from 150 to 500 mmol per 100 g of isoprene. 550

Notes

551

At the end of polymerization the mixture was treated with an additional 100 ml of cyclohexane solvent to fluidify the medium, 1 ml of 1 M acetylacetone in cyclohexane added to stop the reaction, and N-1,3-dimethylbutyl-N0 -phenyl-p-phenylenediamine (0.02 g) added as an antioxidant. Polyisoprene was then extracted by steam stripping for 30 minutes in the presence of calcium tamolate. Each extraction was then dried for approximately 18 hours in an oven at 50 C under 200 mmHg vacuum for 72 hours. Reaction scoping results are provided in Table 1.

POLYMERIZATION SCOPING TABLE 1. Dynamic reaction scoping results for the polymerization of isoprene using a solvent/molar ratio of 9 with the rare catalyst neodymium tris(bis(2-ethylhexyl)phosphate) diethylaluminium chloride.

Entry

Quantity of Neodymium Catalyst (mmol)

1 2 3 4

130 300 700 700

Reaction Time (h) 48 18 1.5 18

Conversion Rate (%)

Inherent Viscosity (dl/g)

Mooney Viscosity

cis-1, 4-Content Using MIR (%)

100 100 50 100

–– 7.6 –– 6.0

97 97 –– 86

–– 99.0 –– 99.0

Note: Entry 1 had an Mn of 930,299 daltons with a polydispersity index of 2.46.

NOTES 1. Polybutadiene and random copolymers of butadiene and isoprene both having cis-1,4-isoprene content exceeding 95% were prepared by the author [1,2], respectively, using the catalytic composition of the current invention. 2. Polybutadiene chloride having a cis-1,4-content of not less than 90% was previously prepared by Sone [3] using methylaluminoxane, hydro genated diisobutylaluminum, neodymium tris(bis(2-ethylhexyl)phosphate), and magnesium. 3. Low molecular weight high cis-butadiene content oligomers were prepared by Miller [4] using methylaluminoxane, neodymium(III) versetate, and diisobutyl aluminum hydride. References 1. 2. 3. 4.

P. Laubry et al., US Patent 7,169,870 (January 7, 2007) and US Patent 7,115,693 (October 3, 2006) P. Laubry et al., US Patent 7,056,998 (June 2, 2006) T. Sone et al., US Patent 6,255,416 (July 3, 2001) and US Patent 6,130,299 (October 10, 2000) H.J. Miller et al., US Patent 6,437,205 (August 20, 2002)

Title: Polymerization Catalyst Author:

S. M. Green et al., US Patent 7,163,990 (January 16, 2007)

Assignee:

BP Chemicals, Ltd. (London, GB)

SIGNIFICANCE A Ziegler–Natta polymerizing procatalyst consisting of a transition metal and a ligand containing at least two nitrogen donor atoms forming a five-membered heterocyclic intermediate has been prepared. When these bisiminidato metal complexes were activated with trimethylaluminium, they were effective as high-activity 1-olefin polymerization catalysts.

REACTION

N

N NH2 N

N

i N

N

a

N

N N

N

b c

N

ii

N

iv

Cl

Fe

N

Cl N

N

N

iii

N N

n-C4H9 N

Fe

N

Al(CH3)3Cl

Cl N

N

N

i: Acetic acid, diacetylpyridine, 4-amino-1,3,5-trimethylpyrazole, ethanol, petroleum ether ii: Iron (II) chloride, THF iii: Trimethylaluminium, toluene iv: Ethylene, 1-hexane

552

Experimental

553

EXPERIMENTAL 1. Preparation of 2,6-Di-(1,3,5-Trimethyl-4-Pyrazolyl)Ethanimidoyl Pyridine A catalytic amount of glacial acetic acid was added to a solution of diacetylpyridine (1 mmol) and 4-amino-1,3,5-trimethylpyrazole (4 mmol) in 10 ml of absolute ethanol and then refluxed 16 hours in a test tube containing a suspended Soxhlet thimble filled with activated 3A molecular sieves. The mixture was next concentrated, and an oily orange solid was isolated. The crude material was triturated with petroleum ether, and the product was isolated as a sandy-colored solid.

2. Preparation 2,6-Di-(1,3,5-Trimethyl-4-Pyrazolyl)Ethanimidoyl Pyridine Iron Dichloride Under a nitrogen atmosphere the Step 1 product (0.05 mmol) was mixed with FeCl2 (0.05 mmol), and 2 ml of THF was added. The mixture was then stirred for 1 hour at ambient temperature. The reaction solvent was removed under reduced pressure, and a light green powder was isolated.

3. Preparation 2,6-Di-(1,3,5-Trimethyl-4-Pyrazolyl)Ethanimidoyl Pyridine Iron Chloride Chlorotrimethylaluminium A 0.5-ml aliquot (0.004 mmol) of a stirred suspension of the Step 2 product and 6.25 ml of toluene was transferred to a Schlenk tube and treated with 0.5 ml of 10% trimethylaluminium in toluene. The resulting pink solution was further diluted with 20 ml of toluene and used directly.

4.

Preparation of Poly(Ethylene-co-1-Hexene)

A Schlenk tube was weighed before being evacuated and refilled with the Step 3 product, ethylene, and 1-hexane. The gas mixture supply was regulated to 1 bar pressure while being polymerizing for 1 hour. After this time a weight gain of 4.79 g was observed, corresponding to an activity of 1198 g/mmol hour bar. The reaction mixture was quenched using acidified methanol, and a white solid polymer product was isolated. GPC Mn ¼ 500 daltons, Mw ¼ 1500 daltons, Mw/Mn ¼ 2.9 13 C NMR (1000C): C2H5 branches 2.2; C4H9 branches 1.4; internal olefin branches 2.0

554

Polymerization Catalyst

DERIVATIVES AND CATALYST ACTIVITY

R

R N N N

M

N

Al(CH3)3Cl

Cl N

N

N

TABLE 1. Catalyst activity for metal complexes used in the polymerization of ethylene and ethylene/1-hexene. Entry

R

1 2 6 7 9 10

H H H H C6H5 C6H5

Metal

Support

Monomer(s)

Fe Fe Fe Co Fe Fe

None None Silica None None None

C2H4/C6H12 C2H4 C2H4 C2H4 C2H4 C2H4/C6H12

Catalyst Activity (g/mmol hour bar) 1198 1123 786 70 614 860

NOTES 1. The Ziegler–Natta catalyst 2,6-diacetylpyridinebisiron(II) chlorotrimethylaluminium, (I), and procatalyst 2,4-{[N-(2,6-dimethylphenyl)]phenylimidoyl}6methyl pyrimidine iron dichloride, (II), were prepared by Kimberley [1] and Gibson [2], respectively, and used as high-activity 1-olefin polymerization catalysts.

N N N

N

Fe

Al(CH3)3Cl

N N

N

Fe Cl

(I)

Cl

(II)

Cl

Notes

555

2. Thorman [3] observed that when di-sec-butyldimethoxysilane, (III), cyclohexylmethyl-dimethoxysilane, (IV), or dicyclopentyldimethoxysilane, (V), were used as external electron donors for titanium-based Ziegler–Natta catalysts with triethyl aluminum as the co-catalyst, catalyst activities ranged between 31,000 g/g/h and 44,000 g/g/h. Representative homopolymerization results for propene are provided in Table 2. TABLE 2. Homopolymerization of propene using a titaniumbased Ziegler–Natta catalyst with triethyl aluminum as cocatalyst and dialkyldimethoxysilanes as electron donors. Silane

Al/Si

III III IV IV V V

Activity (g/g/h)

Polydispersity

10 50 10 50 10 50

7.5 6.5 6.7 6.7 — 7.8

31,000 34,500 32,300 46,000 48,600 45,800

3. Zhao [4] prepared pro-catalysts, (VI) and (VII), consisting of a transition metal and two nitrogen donor atoms forming five-membered heterocyclic intermediates. When the pro-catalysts were activated with trimethylaluminium, they were used to prepare ethylene dimers and oligomers.

N N

M Ni Pd

N N

M X

X Br Cl

N N

Ni Br

X

(VI)

N N Br

(VII)

4. Boussie [5] prepared five-membered heterocyclic titanium pro-catalysts, (VIII), that were activated with methylaluminoxane and used to polymerized styrene and ethylene.

Cl N Cl

Ti

N

N

(VIII)

556

Polymerization Catalyst

References 1. B.K. Kimberley et al., US Patent 7,148,304 (December 12, 2006) and US Patent 6,657,026 (December 2, 2003) 2. V.C. Gibson et al., US Patent 6,828,398 (December 7, 2004) 3. J. Thorman, US Patent 7,163,905 (January 16, 2007) and US. Patent 7,078,468 (July 18, 2006) 4. B. Zhao et al., US Patent 7,160,834 (January 9, 2007) 5. T.R. Boussie et al., US Patent 7,157,400 (January 2, 2007)

Title: Use of Stannylenes and Germylenes as Polymerization Catalysts for Heterocycles Author:

A. Dumitrescu et al., US Patent 7,084,237 (August 1, 2006)

Assignee:

Societe de Conseils de Recherches et d’Applications Scientifiques (FR) Centre National de la Recherche Scientifique (FR)

SIGNIFICANCE Di-[di-(trimethylsilyl)amine]stannate has been used to prepare biocompatible poly (lactide-co-glycolide) containing up to an 88% lactide composition. When the molar ratio of catalyst/lactide was 41.9:17.9, respectively, a polymer was formed which had a molecular weight of 164,700 daltons having a polydispersity of 1.8. All other ratios generated molecular weights less than 78,000 daltons.

REACTION O

O O

O

i Note 1

O O n

O O

3n

i: Di-[di-(trimethylsilyl)amine]stannate, glycolide, mesitylene

EXPERIMENTAL 1.

Preparation of Poly(Lactide-co-Glycolide)

A Schlenk tube was charged with di-[di-(trimethylsilyl)amine]stannate (0.05 mmol), d,l-lactide (39.3 mmol), glycolide (13.1 mmol), and 15 ml of mesitylene and then heated to 160 C for 3 hours. 1 H-NMR analysis indicated that the conversion was complete and that the copolymer consisted of 75% d,l-lactide and 25% glycolide. GPC analysis indicated the product had a Mw of 77,500 daltons with a polydispersity of 1.67. 557

558

Use of Stannylenes and Germylenes as Polymerization Catalysts for Heterocycles

REACTION SCOPING TABLE 1. Scoping reactions for preparing random poly(lactide-co-glycolide) copolymers using the experimental catalyst di-[di-(trimethylsilyl)amine]stannate.

Entry

d,l-Lactide (mmol)

1 2 3 4 5 6

33.9 17.9 54.7 55 14 34

Glycolide (mmol)

Catalyst (mmol)

d,l-Lactide Composition (%)

Glycolide Composition (%)

13.1 –– –– 55 –– ––

0.05 41.9 54.7 0.36 0.09 0.11

25 –– 50 47 88 50

75 –– 50 53 12 50

Mw (daltons) 77,500 164,700 39,000 39,400 21,500 33,140

PDI 1.67 1.8 1.7 1.5 1.89 1.71

NOTES 1. In a subsequent investigation by the author [1] di-[di-(trimethylsilyl)amine] zinc was prepared and used to polymerize d,l-lactide. 2. Chang [2] prepared the thermosensitive biodegradable block copolymer poly [ethylene glycol-b-(lactide-co-glycolide)] end-capped with cholic acid, (I), using catalytic amounts of Snþ2 ion. The product showed improved biodegradability when implanted into the human body with diminished overall polymer cytotoxicity.

O O

O

C12H25

a O

O

b O

(I)

O

c

Cholic acid

3. Heller [3] prepared bioerodible block copolymers using pyridinium ptoluenesulfonate consisting of ortho esters and ethylene glycol, (II), endcapped with triethylene glycol monoglycolide. C2H5 C2H5 C2H5 C2H5 O

O O O

O

O

O O

(II)

O

O

a b

Triethylene glycol monoglycolide

Notes

559

4. Seo [4] prepared poly(d,l-lactide-b-e-caprolactone), (III), and poly(d,llactide-b-ethylene glycol) using stannous octanate. Both polymers were used as PaclitaxelÒ delivery agents.

O H N O

a O

b

(III)

5. Hayes [5] prepared a five component biodegradable blend that was used in melt blown containers consisting of bis(2-hydroxyethyl)-terephthalate, (IV), lactic acid, tris(2-hydroxyethyl)-trimellitate, (V), ethylene glycol, and poly(ethylene glycol) using manganese (II) acetate tetrahydrate and antimony(III) oxide as initiators. O

O

O

OH

O

OH

O O

OH HO

O

O

HO

(IV) References 1. 2. 3. 4. 5.

A. Dumitrescu et al., US Patent 7,169,729 (January 30, 2007) K.-Y. Chang et al., US Patent 7,179,867 (February 20, 2007) J. Heller et al., US Patent 7,163,694 (January 16, 2007) M.-H. Seo et al., US Patent 7,153,520 (December 26, 2006) R.A. Hayes,US Patent 7,144,972 (December 5, 2006)

O

O

(V)

Title: Process for Producing Polar Olefin Copolymer and Polar Olefin Copolymer Obtained Thereby Author:

Y. Inoue et al., US Patent 7,053,159 (May 30, 2006)

Assignee:

Mitsui Chemicals, Inc. (Tokyo, JP)

SIGNIFICANCE Poly(ethylene-co-norbornene-2,3-dicarboxylic acid anhydride) was prepared by co-polymerizing the respective monomers with the transition metal catalyst, di(3-t-butyl-2-hydroxy-1-(N-phenylimino)benzene) titanium(IV). The polymerization was conducted at ambient temperature using methylaluminoxane as co-catalyst. After a 10 minute polymerization reaction scoping period 0.02 mol% of norbornene2,3-dicarboxylic acid anhydride was incorporated into the co-polymer.

REACTION

CHO OH t-C4H9

i

N OH t-C4H9

ii

Cl

N O 2 t-C4H9

Ti Cl

iii

a O

b O

O

a >> b

i: Ethanol, aniline ii: Diethyl ether, n-butyllithium, titanium tetrachloride iii: Ethylene, norbornene dicarboxylic acid anhydride, methylaluminoxane, isobutanol

560

Experimental

561

EXPERIMENTAL 1.

Preparation of 3-t-Butyl-2-Hydroxyl-1-(N-Phenylimino)Benzene

A reactor was charged with 40 ml of ethanol, aniline (7.62 mmol), and 3-t-butylsalicylaldehyde (7.58 mmol) and then stirred 24 hours at ambient temperature and concentrated. The residue was purified using silica gel chromatography, and the product was isolated in 95% yield as an orange oil. 1 H-NMR(CDCl3): d 1.47(s, 9H), 6.88(dd,1H), 7.24 7.31(m,4H), 7.38 7.46(m,3H), 8.64(s,1H), 13.95(s,1H) IR(neat; cm1): 1575, 1590, 1610 MS: 253 (Mþ)

2. Preparation of Di(3-t-Butyl-2-Hydroxy-1-(N-Phenylimino)Benzene) Titanium(IV) Dichloride The Step 1 product (7.05 mmol) was dissolved in 100 ml of diethyl ether and then cooled to 78 C and treated with 4.78 ml of n-butyllithium (1.55M in hexane solution; 7.40 mmol) dropwise for over 5 minutes. The mixture was slowly returned to ambient temperature and stirred for 4 hours. This solution was then re-cooled to 78 C and treated with the dropwise addition of 7.05 ml of titanium tetrachloride (0.5M in heptane solution; 3.53 mmol) and 40 ml of diethyl ether. The solution was then gradually warmed to ambient temperature, stirred for another 8 hours, and filtered through a glass filter. The solid was dissolved in 50 ml of CH2Cl2, and insolubles were removed. The filtrate was concentrated and the residue re-crystallized in 10 ml of CH2Cl2 and 70 ml of pentane. The product was isolated as reddish brown crystals in 61% yield after filtration and drying. 1

H-NMR(CDCl3): d 1.35(s,18 H), 6.82 7.43(m,16H) 8.07(s, 2H) IR(KBr, cm1): 1550, 1590, 1600 MS 622 (Mþ) Elemental analysis: Ti, 7.7% (7.7); C, 65.8% (65.5); H, 6.0% (5.8); N, 4.5% (4.5).

3. Preparation of Poly(Ethylene-co-Norbornene Dicarboxylic Acid Anhydride) A glass autoclave was charged with 250 ml of toluene, the liquid and gas phase saturated with norbornene-2,3-dicarboxylic acid anhydride (0.5 mmol), and 100 liter/h of ethylene. Methylaluminoxane (2.50 mmol) and the Step 2 product (0.005 mmol) were then added to initiate the polymerization. The reaction was conducted at 25 C for 10 minutes in an ethylene gas atmosphere at atmospheric pressure and terminated using isobutanol. After the polymerization was completed, the reaction product was precipitated by pouring into methanol. Hydrochloric acid was then added, and the mixture filtered through a glass filter. The resulting polymer was washed with methanol and dried to obtain 1.15 g of a polymer. Analytical evaluation indicated that the copolymer contained 0.02 mol% of norbornene-2,3-dicarboxylic acid anhydride.

562

Process for Producing Polar Olefin Copolymer and Polar Olefin Copolymer Obtained Thereby

DERIVATIVES TABLE 1. Entry

Imine ligand derivatives used in preparing titanium procatalysts. N-Phenylimino Ligand Derivatives

N

3

6

N

7

N

Step 1 Yield (%)

H N

66

H N

85

98

OH

N N 11

61

OH t-C4H9

NOTES 1. High-activity analogues of the current invention were previously prepared by Suzuki [1] and used in the homopolymerization of ethylene as provided in Table 2.

R Cl

N Ti

O 2

t-C4H9

Cl

Notes

563

TABLE 2. Selected high-activity Ziegler–Natta titanium catalysts used in the homopolymerization of ethylene.

Entry

Activity (g/mmol Ti hour)

R

5 6 7

Phenyl 2,6-Dimethylphenyl Pentafluorophenyl

5784 1204 1150

2. In a subsequent investigation by the author poly(ethylene-co-norbornene dicarboxylic acid anhydride) containing 0.03 mol% norbornene-2,3-dicarboxylic acid anhydride was prepared using the Step 2 vanadium analogue, (I).

N O

V 3

(I) 3. Bidentate ligands prepared by Mackenzie [3,4], (II) and (III), respectively, were effective in preparing highly branched polyethylene.

t-C4H9

t-C4H9

[B(C6F5)4] O

i-C3H7 S

O Ni

C6H5

S

N

N

N

S

S

i-C3H7

N

C6H5 i-C3H7

i-C3H7

Pd Cl

t-C4H9

t-C4H9

(III)

(II)

4. Moody [5,6] prepared highly branched ultra-high molecular weight polyethylene using the bidentate ligard, (II). Branched oligomeric ethylene was also prepared using an N-pyrrolyl substituted an imino derivative, (IV).

564

Process for Producing Polar Olefin Copolymer and Polar Olefin Copolymer Obtained Thereby

t-C4H9

t-C4H9 N N

O Ni (C6H5)3P

P(C6H5)3

(IV)

References 1. 2. 3. 4. 5. 6.

Y. Suzuki et al., US Patent 7,009,014 (March 7, 2006) Y. Inone et al., US Patent Application 2006-0063898 (March 23, 2006) P.B. Mackenzie et al., US Patent 7,056,996 (June 6, 2006) P.B. Mackenzie et al., US Patent Application 2005-0090630 (April 28, 2005) L.S. Moody et al., US Patent 6,946,532 (September 20, 2005) L.S. Moody et al., US Patent Application 2006-0178490 (August 10, 2006)

Title:

Carborane Trianion-Based Catalyst

Author:

Y. Zhu, US Patent 7,053,158 (May 30, 2006)

Assignee:

Agency for Science, Technology and Research (SG)

SIGNIFICANCE The Ziegler–Natta catalyst trimethylammonium o-methyl-1-(2-hydroxylcyclo hexyl)-carborane zirconium chloride has been prepared and affixed to a Merrifield resin. When used as a polymerization catalyst for vinyl chloride, t-butyl acrylate, styrene, or ethylene, oligomers with molecular weights 200 C. 1

H-NMR (400 MHz in CDCl3) d 3.40 (CH–O), 1.80 (–CH.sub.3), 0.63 2.90 (BH, CH, OH) IR (KBr pellet, cm1), 3062(s), 2588(vs), 1447(m), 1390(m), 1229(w), 1133(m), 1094(m), 1017(s), 934(m), 722(s)

3. Preparation of Trimethylammonium o-Methyl-1-(2-Hydroxylcyclohexyl)Carborane Zirconium Chloride The Step 2 product (4.92 mmol) was dissolved in 75 ml of dry THF and then cooled to 0 C and treated with sodium hydride (29.52 mmol; 60% dispersion in mineral oil). The mixture was next stirred at ambient temperature for 30 minutes and refluxed for 3 hours. Complete removal of trimethylamine was achieved by passing a stream of argon over the solution and through the condenser during the final 30 minutes of refluxing. Once at ambient temperature stirring was stopped and the clear THF solution was decanted under argon to another vessel. This solution was then treated with ZrCl4 (4.93 mmol) and stirred for 72 hours at ambient temperature. The mixture was filtered

Catalyst Scoping

567

and concentrated. The residue was re-crystallized in a mixture of CH2Cl2/n-pentane, 1:1, and the product was isolated in 79% yield. 1

H-NMR (400 MHz in DMSO, ppm) d 9.4(NH), 3.56(OH), 3.18(CH–O), 2.52(NCH3), 2.00 0.95(BH), 2.81(BH) IR (KBr pellet, cm1), 3524(vs), 3040(m), 2931(s), 2857(s), 2497(vs), 1477(s), 1449(s), 1388(s), 1273(m), 1212(m), 1036(vs), 978(s), 860(m), 472(m)

4. Preparation of Polystyrene-Supported Trimethylammonium o-Methyl-1(2-Hydroxyl-Cyclohexyl)-Carborane Zirconium Chloride The Step 3 product (4.00 mmol) was dissolved in 100 ml of THF and then cooled to 78 C and treated with 2.7 ml of n-BuLi (4.32 mmol; 1.6 M in hexane). It was stirred for 30 minutes, followed by 4 additional hours of stirring at ambient temperature, and then concentrated. The residue was washed twice with 15 ml of n-hexane, dissolved in 150 ml of THF containing 1% Merrifield’s resin (2.0 g; 3.94 mmol Cl), and stirred at ambient temperature for two days. The mixture was refluxed for 4 hours and then quenched with 3.0 ml of methanol and re-concentrated. The residue was washed twice with 10 ml of deionized water and twice with 20 ml of n-hexane. The solid was dried, and 2.40 g polystyrene-supported ortho-carborane were isolated as a pale yellow solid. HNMR (400 MHz in DMSO, ppm) d 3.10 (CH–O), 1.66 (–CH3), 0.43 1.90 (BH, CH, OH) IR (KBr pellet, cm1), 3413(s), 2919(vs), 2851(s), 1637(m), 1457(s), 1305(s), 963(m), 423(m) 1

5.

Preparation of Polyvinyl Chloride

The polymerization of vinyl chloride catalyzed by the Step 4 product in THF was performed at ambient temperature without the use of a co-catalyst. The reaction conversion was 43.8%.


CATALYST SCOPING TABLE 1. Effectiveness of polystyrene-supported zirconium-ortho-carborane as a polymerization catalyst for selected monomers. Monomer Vinyl chloride t-Butyl acrylate Polystyrene Ethylene

Catalyst Activity (kg polymer/mol catalyst hr)

Mw 1 103 (daltons)

PDI

40 35 64 33

5.6 4.2 3.6 2.7

1.6 1.6 1.8 1.7

568

Carborane Trianion-Based Catalyst

NOTES 1. An alternative method for preparing carborane anions using n-butyl lithium or sodium hydride in dimethyl ether or diglyme is described by Frankel [1]. 2. Tinker [2] prepared 1,3-, (I), and 1,3,5-triacarborane benzene derivatives that were useful as hydrogenation catalysts.

Rh(P(C6H5)3)3

Rh(P(C6H5)3)3

(I)

References 1. A. Frankel et al., US Patent 7,161,040 (January 9, 2007) and US Patent 6,180,829 (January 30, 2001) 2. N.D. Tinker et al., US Patent 6,492,570 (December 10, 2002) and US Patent 6,423,199 (January 23, 2002)

Title:

Catalyst for Polymerization of Norbornene

Author:

J.-H. Lipian, US Patent 7,148,302 (December 12, 2006)

Assignee:


SIGNIFICANCE Norbornene and norbornene methyl ester have been polymerized forming a polymer that lacks backbone carbon–carbon double-bond unsaturation. The polymerization catalyst mixture consisted of palladium acetate, a phosphine such as tricyclohexylphosphine, a Lewis acid such as dimethyl zinc, and hexafluoroisopropanol. Polynorbornenes prepared in this manner typically had Mn’s > 200,000 daltons with polydispersies less than 2, while poly(norbornene methyl ester) had Mn’s of roughly 100,000 daltons.

REACTION

i Notes 1,2 a

i: Palladium acetate, tricyclohexylphosphine, dimethyl zinc, hexafluoroisopropanol, toluene

EXPERIMENTAL Preparation of Polynorbornene Generic Procedure In a typical experiment a reactor was charged with palladium acetate (8.5 106 mol), tricycle-hexylphosphine (8.5 106 mol), and norbornene (0.0213 mol). The components were dissolved in 5 ml of toluene and then treated with dimethyl zinc (2.5 105 mol) where a color change was observed. This mixture was next treated 569

570


with hexafluoroisopropanol (2.12 104 mol), and rapid polymerization occurred with a high exotherm. The mixture was concentrated, and the product was isolated in 100% yield.

POLYMERIZATION STUDIES

a TABLE 1. Effect of varying the Lewis acid and hexafluoroisopropanol catalyst compositions on the polymerization of norbornene while keeping both palladium acetate and tricyclohexylphosphine concentrations constant at 8.5 106 mol. Entry 1 2 3 5 11

Lewis Acid Dimethyl zinc Tri-isobutyl aluminum None Dimethyl zinc nickel octanoate

Lewis Acid (mol)

Hexafluoroisopropanol (mol)

Conversion (%)

(2.5 105) (2.5 105)

2.12 104 2.12 104

100 100

–– (2.5 105) (2.5 105)

2.12 104 None 1.01 103

96 0 Not quantified

H3CO

a

H3CO O

O

TABLE 2. Effect on the polymerization of norbornene methyl ester by varying the catalyst composition ratios of hexafluoroisopropanol and palladium acetate while keeping di-t-butylcyclohexylphosphine and diethyl zinc levels constant. Entry 53 55 56 58 59

Hexafluoroisopropanol/ Palladium Acetate Ratio 2714:1 3619:1 4071:1 4976:1 5881:1

Conversion (%) Trace Trace 86 91 96

Mn (1 103) — — 84 104 134

Mw (1 103) — — 54 59.5 78.5

Note: The monomer ratio of norbornene methyl ester-to-di-t-butylcyclohexylphosphine was 10,000:1.25, respectively.

Notes

571

NOTES 1. Additional catalyst compositions utilizing di-t-butyl- and di(2-norbonyl)phosphine as the phosphine component and titanium tetrabutylrate as the Lewis acid are described by the author [1] in an earlier investigation. 2. Grubbs [2] quantitatively prepared polynorborene, (I), containing 90% trans unsaturation from norborene using the high yielding ring-opening metathesis polymerization catalyst, benzylidene di(triphenylphosphine)ruthenium dichloride, RuCl2(¼CH–C6H4X)(P(C6H5)3)2, (II).

i (I)

a

i: CH2Cl2, benzylidene di(triphenylphosphine)ruthenium dichloride, (II)

X Cl Cl

X=H N(CH3)2 OCH3 CH3 F, Cl NO2

P(C6H5)3 Ru P(C6H5)3

(II) 3. Taguchi [3] polymerized the cyclopentadiene-itaconic anhydride Diels–Alder addition product, (III), using the ring-opening metathesis polymerization catalyst benzylidene(1,3-dimesitylimidazolydin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride. The polyunsaturated intermediate, (IV), was then hydrogenated using bis(tricyclohexylphosphine)benzylideneruthenium dichloride obtaining the polynorborene diacid derivative, (V), having a Mw of roughly 18,000 daltons. a

a

O

i

ii

CO2H

O O

O

(III)

O

a

CO2H

O

(IV)

(V)

572


i: THF, benzylidene(1,3-dimesitylimidazolydin-2-ylidene)(tricyclohexylphosphine)ruthenium dichloride ii: Bis(tricyclohexylphosphine)benzylideneruthenium dichloride, hydrogen, ethyl vinyl ether, toluene 4. Weck [4] prepared photoluminescent polynorborene derivatives, (VII), by polymerizing aluminum-8-hydroxyquinoline-functionalized norborene, (VI), using benzylidene (1,3-dimesitylimidazolydin-2-ylidene)-(tricyclohexylphosphine)ruthenium dichloride.

a

HN

6

i HN

N

N O

O Al N

6

O

O Al

N N

O

(VI)

N

O

(VII)

i: Benzylidene (1,3-dimesitylimidazolydin-2-ylidene)-(tricyclohexylphosphine) ruthenium dichloride. 5. Milne [5] prepared polypyrrolidine, (VIII), by the cyclopolymerization of 1,10(di-N,N-diallyl)decane by UV or thermal radiation.

NH

NH 10

NH

HN 10

(VIII)

Notes


J.-H. Lipian, US Patent 7,122,611 (October 17, 2006) R.H. Grubbs et al., US Patent 7,102,047 (September 5, 2006) K. Taguchi et al., US Patent 7,037,993 (May 2, 2006) M. Weck et al., US Patent 7,105,617 (September 12, 2006) P.E. Milne et al., US Patent 6,608,120 (August 19, 2003)

573

XX. REGULATORS A. Chain Transfer Agents a. Poly(2-Hydroxyethyl Methacrylate)

Title: Method for the Production of Homo-, Co-, and Block Copolymers Author:

I. Stefan et al., US Patent 7,199,200 (April 3, 2007)

Assignee:

Construction Research and Technology GmbH (Trostberg, DE)

SIGNIFICANCE A method for preparing polymers in a narrow molecular weight distribution by controlled radical polymerization in an aqueous solution using b-cyclodextrin as the macroinitiator intermediate and 1,1-diphenylethylene as the regulator is described. Since this method requires considerably lower amounts of both initiator and regulator, polymers contain limited amounts of regulator and initiator decomposition products.

REACTION O a

i

O

O OH

O OH

i: Water, hydroxypropylated b-cyclodextrin, 1,1-diphenylethylene, ammonium peroxodisulfate


576

Method for the Production of Homo-, Co-, and Block Copolymers

EXPERIMENTAL Preparation of Poly(2-Hydroxyethyl Methacrylate) An aqueous solution of 17.68 ml of water and hydroxypropylated b-cyclodextrin (1.6 mmol) was treated with 1,1-diphenylethylene (1.6 mmol). This solution was then treated with 150 g of water and 2-hydroxyethyl methacrylate (538 mmol), heated to 85 C, and further treated with the dropwise addition of ammonium peroxodisulfate (4.8 mmol) dissolved in 10 g of water. The solution temperature was next raised to 90 C, and the mixture was reacted for 5 hours. A clear orange solid was obtained having a Mw of 5200 daltons with a polydispersity of 1.21.

DERIVATIVES TABLE 1. Effect of varying reaction components and treatment levels on the molecular weight and polydispersities of selected polymers. Entry

b-Cyclodextrin (mmol)

Regulator (mmol)

Monomer (g)

2

Methylated (2.2)

1,1-Diphenylethylene (2.2)

Acrylic acid (40)

4

Methylated (1.5) Hydropropylated (2.22)

1,1-Diphenylethylene (1.5) 1,1,2,2-Tetraphenyl-1,2dicyanoethane (1.8)

2-Hydroxyethyl methacrylate (35) 2-Hydroxyethyl methacrylate (60) and Styrene (10)

6

Initiator (mmol)

Mw (daltons)

PDI

Ammonium peroxodisulfate (5.0) AIBN (3)

28,900

1.4

14,900

1.7

AIBN (3.7)

6,400

1.6

NOTES 1. Rogers [1] and Blokzijl [2] used substituted polysaccharides as macroinitiator intermediates for the preparation of polysaccharide graft polymers and in the preparation of macroinitiators. The polysaccharide graft polymers were designed to impart soil release and/or fabric care benefits to laundry detergent or fabric treatment compositions. 2. A controlled free radical polymerization process used by White [3] entailed preparing the monofunctional iniferter 2,3-dicyano-2,3-dimethyl butane by thermally decomposing azobisiso-butyronitrile and then heating the iniferter sufficiently to form two carbon centered radical residues. In this manner polymers were prepared having moderate molecular weights but narrow polydispersities. References 1. S.H. Rogers et al., US Patent 7,041,730 (May 9, 2006) 2. W. Blokzijl et al., US Patent 7,153,821 (December 26, 2006) 3. D. White et al., US Patent 6,875,832 (April 5, 2005)

b. 1-Benzyl-2,5-Cyclohexadiene-1-Carboxylic Acid

Title: Method for Radical Polymerization in the Presence of a Chain Transfer Agent Author:

W. Gaschler, US Patent 7,196,150 (March 27, 2007)

Assignee:


SIGNIFICANCE 1-Benzyl-2,5-cyclohexadiene-1-carboxylic acid is a new chain transfer agent that was used to modulate the emulsion terpolymerization of styrene, butadiene, and acrylic acid. Its use resulted in 7% less gel formation than in an equivalent terpolymerization lacking this additive.

REACTION a

i Note 1

b

c

O

OH

i: Water, sodium disulfonated monododecyl diphenyl ether, sodium dodecylbenzenesulfonate, 1-benzyl-2,5-cyclohexadiene-1-carboxylic acid, butadiene, acrylic acid, sodium hydroxide, sodium peroxodisulfate

EXPERIMENTAL Preparation of Poly(Styrene-co-Butadiene-co-Acrylic Acid) by Emulsion Polymerization A polymerization vessel was charged with water (300 g), 33% polymer styrene latex (62 g, d50 of 30 nm), 10% of the initiator solution, and sodium peroxodisulfate and then heated to 95 C. Using two separate feeds, the monomer emulsion present in 577

578

Method for Radical Polymerization in the Presence of a Chain Transfer Agent

feed 1 and the initiator solution in feed 2 were simultaneously introduced into the polymerization vessel for over 2.5 hours at 95 C. A description of feed 1 and feed 2, is provided below. Feed 1 400 g deionized water 33 g emulsifier solution 45 wt% sodium disulfonated monododecyl diphenyl ether 7 parts of 15 wt% sodium dodecylbenzenesulfonate solution 0.8 g 1-benzyl-2,5-cyclohexadiene-1-carboxylic acid [chain transfer agent] 675 g styrene 310 g butadiene 30 g acrylic acid 10 g 25% strength by weight aqueous sodium hydroxide solution Feed 2 10.2 g sodium peroxodisulfate in 200 g of water When both feed lines were empty, the mixture temperature was cooled to 70 C, and an aqueous solution of 4 g of t-butyl hydroperoxide dissolved in 40 ml of water and a solution of acetone (1.7 g) and sodium disulfite (2.8 g) dissolved in 38 ml of water were added over 2 hours at 70 C. Thereafter 22% aqueous NaOH (22 g) was added, and the mixture was cooled to ambient temperature. The solid content of the dispersion was approximately 50 wt% having a light transmission of 70% with a particle size of 124 nm, a pH of 6.8, and a product Tg of 27 C.

DERIVATIVES Emulsion polymerization with the chain transfer agent 1-benzyl-2,5-cyclohexadiene1-carboxylic acid was also used to prepare poly(ethyl acrylate-co-methacrylic acid). Poly(N-vinylpyrrolidone) was prepared using the chain transfer agent 1-i-propyl-2,5cyclohexadiene-1-carboxylic acid.

NOTES 1. Additional regulators were identified by the author [1] in a subsequent investigation and used in emulsion polymerization reactions: Methyl 1-methyl-2,5-cyclohexadiene-1-carboxylate 1-Isopropyl-2,5-cyclohexadiene-1-carboxylic acid 1-t-Butyl-2,5-cyclohexadiene-1-carboxylic acid

Notes

579

1-Allyl-2,5-cyclohexadiene-1-carboxylic acid 1-Cyanomethyl-2,5-cyclohexadiene-1-carboxylic acid 2. g-Terpinene, (I), terpinolene, and a-methyl styrene dimer were used by Manders [2] as chain transfer agents in the emulsion polymerization of styrene, butadiene, and acrylic acid. In a subsequent investigation by Gaschler [3] these three chain transfer agents were used in the emulsion polymerization of styrene and butadiene.

i-C3H7

(I) 3. Chain transfer functionalization of cysteine was used by Brennan [4] to prepare macromonomer polybutyl acrylate end-functionalized with cysteine, (II), which was then polymerized with 4-aminobenzoic acid (III). HN H2N

H N

CO2H

O

i

a O

S

S

Polybutyl acrylate

Polybutyl acrylate

(II)

(III)

i: 4-Aminobenzoic acid, triphenylphosphine, lithium chloride, N-methyl-2pyrrolidinone, pyridine 4. Organotungsten reversible addition-fragmentation chain transfer reagents, (IV), prepared by Lo [5] were used with AIBN to polymerize isobutyl acrylate. O (OC) 5 W

O S

S

W(CO) 5

(IV)

5. Hayashi [6] prepared styryl alkoxyamine comonomers, (V), that behaved as high molecular regulators by releasing CO2 and 2,2,6,6-tetramethyl-4hydroxy-1-piperinyloxy at elevated temperatures.

580

Method for Radical Polymerization in the Presence of a Chain Transfer Agent

OH O

O O

O

N

(V)

References 1. 2. 3. 4. 5. 6.

W. Gaschler, US Patent Application 2006-0058478 (March 16, 2006) L. Manders et al., US Patent 7,196,146 (March 27, 2007) W. Gaschler et al., US Patent Application 2004-0242767 (December 2, 2004) A.B. Brennan et al., US Patent 7,169,853 (January 30, 2007) Y.-H. Lo et al., US Patent 7,132,491 (November 7, 2006) M. Hayashi et al., US Patent 6,919,481 (July 19, 2005)

c. Polymercaptopolyols

Title: Use of C4-C6-Polymercaptopolyols as Regulators in Solution or Precipitation Polymerization Author:

K. Michl et al., US Patent 7,084,224 (August 1, 2006)

Assignee:


SIGNIFICANCE 1,4-Dimercaptobutane-2,3-diol has been used to control the molecular weight of polymers during free radical polymerization. Polymers having 1,4-dimercaptobutane2,3-diol incorporated into their structure had weak “mercaptan” odors.

REACTION O OH

i

a HO

a ~ 100

O

i: Sodium hydroxide, sodium persulfate, water, 1,4-dimercaptobutane-2,3-diol

EXPERIMENTAL A reactor was filled with water (350 g) and heated to 90 C. Over the course of 5 hours three separate feeds of methacrylic acid (200 g), 50% solution of NaOH (55 g), water (350 g), sodium persulfate dissolved in water (100 g) and a mixture of 1,4-dimercaptobutane-2,3-diol and water (100 g) were added. When the feeds were emptied, the mixture was polymerized for 90 minutes at 95 C, resulting in a clear solution with 18% solids and a pH of 4.7. After the workup the polymer was isolated, having an Mw of 15,000 daltons.

581

582

Use of C4-C6-Polymercaptopolyols as Regulators in Solution or Precipitation Polymerization

RESULTS TABLE 1. Effect on molecular weights and odor using selected thiol derivatives as polymerization regulators. Entry

Monomer

Regulator

1.1

Acrylic acid

1.2 1.3 2.1

Acrylic acid Acrylic acid Methacrylic acid

2.2 2.3

Methacrylic acid Vinylimidazole

Initiator

1,4-dimercaptobutane2,3-diol Mercaptoethanol Dodecylmercaptan 1,4-dimercaptobutane2,3-diol None 1,4-dimercaptobutane2,3-diol

Mercaptan Odor

Mw (daltons)

AIBN

Weak

7,700

Na2S2O7 Na2S2O7 Na2S2O7

Strong Strong Weak

8,400 790,000 15,000

Na2S2O7 AIBN

— Weak

80,000 40,000

NOTES 1. Tamura [1] used thiiranes, (I), to control the polymerization rate of bis(bepithiopropyl) derivatives, (II), which were subsequently converted into optical materials. S

S

S

A

A = H, CH3, Cl, Br, I B = O, S

B

(I)

(II)

2. Thiocarbamate derivatives, (III), prepared by Rink [2] were effective as free radical regulators in the 2,2-azobisisobutyronitrile-initiated polymerization of styrene.

O

O S

S HN

HO

NH

(III)

OH

3. Emulsion terpolymerization of t-butyl acrylate, methacrylic acid, and dimethicone in the presence of n-decanethiol resulted in an odorless product that was used in cosmetic formulations by Drohmann [3]. 4. Bremser [4] free radically copolymerized methacrylate and acrylic acid using 1,1-diphenylethylene and mercaptoethanol as regulators.

Notes

583

5. Imino-N-alkoxy-polyalkyl-piperidine derivatives, (IV), prepared by Nesvadba [5] were effective as regulators in the free radical polymerization of styrene.

N

OR

R = H, CH3, t-C4H9

N O

(IV)


M. Tamura et al., US Patent Application 2005-261467 (November 24, 2005) H.-P. Rink et al., US Patent 7,153,917 (December 26, 2006) C. Drohmann et al., US Patent 7,147,842 (December 12, 2006) W. Bremser et al., US Patent 7,151,130 (December 19, 2006) P. Nesvadba et al., US Patent 7,199,245 (April 3, 2007)

d. S-(a,a0 -Disubstituted-a00 -Acetic Acid) Derivatives

Title: S-(a,a0 -Disubstituted-a00 -Acetic Acid) Substituted Dithiocarbonate Derivatives for Controlled Radical Polymerizations, Process, and Polymers Made Therefrom Author:

J.T.-Y. Lai, US Patent 7,205,368 (April 17, 2007)

Assignee:

Noveon, Inc. (Cleveland, OH)

SIGNIFICANCE A single-step method for preparing S-(a, a0 -disubstituted-a00 -acetic acid) substituted dithiocarbonate derivatives is described. These agents are effective as modulators in free radical polymerization reactions.

REACTION a

S

CS2

i

HO2C

S

S

CO2H

ii

O

O

i: Acetone, CCl3H, tetrabutylammonium bisulfate, toluene, sodium hydroxide ii: 2,20 -Azobisisobutyronitrile, 2-ethylhexylacrylate, acetone

EXPERIMENTAL 1.

Preparation of S,S0 -bis-(a, a0 -Dimethyl-a00 -Acetic Acid)-Trithiocarbonate

A 500-ml jacketed flask was charged with carbon disulfide (22.9 g), tetrabutylammonium bisulfate (2.0 g), and 100 ml of toluene and then treated with the dropwise addition of 50% sodium hydroxide solution (168 g) at such a rate the temperature did 584

Derivatives

585

not exceed 30 C. After the addition the mixture was further treated with acetone (43.6 g) and chloroform (89.6 g) at such a rate the temperature remained between 20 C and 30 C. This mixture was then stirred overnight at ambient temperature and treated with 500 ml of water. The two layers were separated, and the aqueous layer was acidified with concentrated hydrochloric acid to precipitate the product as a yellow solid. The solid was washed with 50 ml of toluene and filtered, and 22.5 g of product was isolated. 2.

Preparation of Poly(2-Ethylhexyl)Acrylate (Generic Procedure)

S-(a,a0 -Dimethyl-a00 -acetic acid) dithiocarbonate (5.33 mmol), 2-ethylhexylacrylate (135.7 mmol), 2,20 -azobisisobutyronitrile (0.3 mmole), and 25 ml of acetone were mixed and stirred for 7 hours at 52 C. Thereafter the solution was filtered and concentrated, and the product was isolated.

POLYMERIZATION SCOPING TABLE 1. Percent conversion for selected monomers using a Step 1 reaction regulator and 2,20 -azobisisobutyronitrile as the free radical initiator. Entry

Polymerization Monomer

5 7 9

2-Ethylhexylacrylate n-Butylacrylate Styrene

Reaction Time (min)

Mn (daltons)

Mw (daltons)

Conversion (%)

420 360 360

1614 3532 2537

2059 4066 2956

26.9 65.7 84.5

DERIVATIVES S S S

N

S

CO2H

C2H5O

C2H5O

S

S S

CO2H

CO2H

CO2H

S N

S

S C2H5

O N

HO2C

N

CO2H S C2H5

586

S-(a,a0 -Disubstituted-a00 -Acetic Acid) Substituted Dithiocarbonate Derivatives

NOTES 1. Tougheners for thermsettable polymers using polymeric thiocarbonate derivatives, (I), were previously prepared by the author [1].

S HO2C

Polyacrylate

S

S

Polyacrylate

CO2H

(I) 2. Favier [2] used t-butyl dithiobenzoate, (II), as the chain transfer agent with 2,20 azobisisobutyronitrile to prepare poly(N-acryloyl morpholine), (III), having a Mn > 200,000 daltons with a polydispersity of 1.4.

O O

O S

S

n

O O

N O

(III) (II) 3. Polystyrene was prepared by Benicewicz [3] by bulk polymerization with 2,20 azobisisobutyronitrile and had a polydispersity of 1.07 using either the low odor thioester, (IV), or thiourethane, (V), as chain transfer agents.

S

CN S

N

S S

(IV)

CN

(V)

4. Rink [4] prepared thiocarbamate derivatives, (VI), that were used as regulators in the (co)polymerization of styrene using 2,20 -azobisisobutyronitrile as the free radical initiator.

Notes

H N

S

587

OH

O

HO

H N

S O

(VI)

References 1. J.T.-Y. Lai et al., US Patent 6,894,116 (January 30, 2007) 2. A. Favier et al., US Patent 7,205,362 (April 17, 2007) and US Patent Application 2007-0073011 (March 29, 2007) 3. B. Benicewicz et al., US Patent Application 2007-0088140 (April 19, 2007) 4. H.-P. Rink et al., US Patent 7,153,917 (December 26, 2006)

B. Chain Transfer Processes a. Reversible Addition-Fragmentation Chain Transfer

Title: Chain Transfer Agents for RAFT Polymerization in Aqueous Media Author:

C. L. McCormick et al., US Patent 7,179,872 (February 20, 2007)

Assignee:

University of Southern Mississippi (Hattiesburg, MS)

SIGNIFICANCE Reversible addition-fragmentation chain transfer (RAFT) polymerization using 2,20 -azobisisobutyronitrile and either N,N-dimethyl-S-thiobenzoylthiopropionamide or N-dimethyl-S-thiobenzoylthioacetamide as chain transfer agents has been used to prepare low polydispersity poly(N,N-dimethylacrylamide). The chain transfer agents were unusually effective in suppressing free radical termination reaction, thereby mimicking a “living” polymerization reaction.

REACTION O N

i Note 1

a N

O

i: 2,20 -Azobisisobutyronitrile, benzene, N,N-dimethyl-S-thiobenzoylthiopropionamide or N,N-dimethyl-S-thiobenzoylthioacetamide

EXPERIMENTAL Preparation of Poly(N, N-Dimethylacrylamide) 1.93M N,N-Dimethylacrylamide dissolved in benzene was free radically polymerized at 60 C in a flame-sealed ampoule equipped with a magnetic stir bar using 588

Reaction Scoping

589

2,20 -azobisisobutyronitrile (1.0 mmol) and either N,N-dimethyl-s-thiobenzoylthiopropionamide (5.0 mmol) or N,N-dimethyl-s-thiobenzoyl-thioacetamide (5.0 mmol) as the chain transfer agent. Prior to polymerization the ampoule was subjected to three freeze-pump-thaw cycles to remove oxygen. The polymerization reaction was terminated by initially freezing the reaction in a dry ice/acetone bath followed by precipitation in hexane.

REACTION SCOPING TABLE 1. RAFT polymerization of N-N0 -dimethylacrylamide using selected chain transfer agents in benzene at 60 C with a chain transfer agent/AIBN ratio of 5:1, respectively.

Entry

Chain Transfer Agent

Reaction Time (h)

Conversion (%)

Mn 1 105 (daltons)

Mw 1 105 (daltons)

PDI

S 1a

S

14.5

80

3.2

5.1

1.22

S

36.6

90

3.6

5.1

1.22

S

8.1

59

2.4

3.6

1.25

S

36.6

86

3.4

4.6

1.24

19.0

78

3.3

3.5

1.14

36.6

82

3.7

4.3

1.14

S 1a

S 1b

S 1b

S N

S

1c

O S 1c

N

S O

Note: The targeted Mn for poly(N,N-dimethylacrylamide) was 40,000 daltons.

590

Chain Transfer Agents for RAFT Polymerization in Aqueous Media

NOTES 1. Structural depictions for N,N-dimethyl-S-thiobenzoylthiopropionamide, (I), and N,N-dimethyl-S-thiobenzoylthioacetamide, (II), respectively, are provided below.

S N

S

(I) X = O (II) X = S

X

2. Dithioester-terminated macromolecular transfer agents, (III), were previously prepared by the author [1] and used to modify metallic nanoparticle surfaces. S Polydimethylacrylamide S

(III)

S Polydimethylacrylamide

i Polydimethylacrylamide

S

Gold nanoparticle

i: Sodium borohydride, water, gold nanoparticle 3. Moderately high molecular weight polymers with narrow polydispersities were prepared by Lo [2] using tungsten-containing organometallic RAFT reagents, (IV) and (V).

S (CO)3W P

(IV)

S S

CN

(CO)3W P

O S

t-C4H9 O

a

CN

a>2

(V)

4. Using the RAFT chain transfer agent dibenzyltrithiocarbonate with oleic acid, tripotassium phosphate, potassium hydroxide, and potassium persulfate, Parker [3] prepared polystyrene by emulsion polymerization. The polystyrene latex was obtained in roughly 90 minutes and had a solid content of 20.6%, while purified polystyrene had a Mn of 54,000 daltons with a PDI of 1.17. 5. Mercapto-terminated block copolymers and block terpolymers prepared by Tsuji [4] such as poly(acrylonitrile-b-butyl acrylate) and poly(acrylonitrile-bbutyl acrylate-b-ethyl acrylate), respectively, used the RAFT chain transfer agent cumyl dithiobenzoate. The block copolymer had a Mw of 48,600 daltons,

Notes

591

Mn of 34,500 daltons, and a polydispersity index of 1.41, while the terpolymer had a Mw of 48,700 daltons, Mn of 31,300 daltons, and a polydispersity index of 1.56. 6. In a subsequent investigation by the author [5], N,N-dimethyl-s-thiobenzoylthioacetamide, (VI), was prepared as a RAFT chain transfer agent and used in the polymerization of N, N-dimethyl-acrylamide.

S S

S

N

(VI) References 1. 2. 3. 4. 5.

C.L. McCormick et al., US Patent 7,157,534 (November 21, 2006) Y.-H. Lo et al., US Patent 7,132,491 (November 7, 2006) D.K. Parker et al., US Patent 7,098,280 (August 29, 2006) and US Patent 6,992,156 (August 29, 2005) R. Tsuji et al., US Patent 7,094,833 (August 22, 2006) C.L. McCormick et al., US Patent 7,186,786 (March 6, 2007)

b. Nitroxide-Mediated Polymerization

Title: Hindered Spiro-Ketal Nitroxides Author:

M. Jawdosiuk et al., US Patent 7,132,540 (November 7, 2006)

Assignee:

Nova Molecular Technologies, Inc. (Janesville, WI)

SIGNIFICANCE Spiro-ketal nitroxides have been prepared that are effective as regulators in nitroxide mediated polymerizations. These agents have high hydrocarbon and monomer solubility over existing nitroxides, particularly in styrene, and are also effective as regulators in vinyl acetate and acetonitrile polymerizations.

REACTION

O

O

O

O

i Notes 1, 2 N H

N O

i: Methanol, hydrogen peroxide, sodium tungstate dehydrate

EXPERIMENTAL Preparation of 1,5-Dioxa-9-Aza-8,8,10,10Tetramethylspiro[5,5]Undec-9-Yloxy A 500-ml Erlenmeyer flask was charged with1,5-dioxa-9-aza-8,8,10,10-tetramethylspiro[5,5]-undecane (0.04 mole) dissolved in 150 ml of methanol and then treated with 40 ml of 35% aqueous hydrogen peroxide followed by sodium tungstate dehydrate (0.4 g). The mixture was left for 3 days at ambient temperature where after one day the color became dark orange. It was then extracted with three 50-ml portions of t-butyl methyl ether and dried with an anhydrous Na2SO4. The solution was concentrated, and 592

Derivatives

593

9 g of a dark orange solid product was isolated, MP ¼ 59–62 C. The use of this material and related nitroxide regulators in polymerization reactions are provided in Table 1.

DERIVATIVES TABLE 1. Effectiveness of nitric oxide polymerization regulators on the polymerization of vinyl acetate and acetonitrile at 70 C using 10 ml of monomer, 0.35 g of benzoyl peroxide, and 0.1 g of selected nitroxide regulators.

Entry —

Regulator None

Inhibition Time for Vinyl Acetate Polymerization (min)

Inhibition Time for Acetonitrile Polymerization (min)

8

4

205

40

145

60

>300

305

250

135

385

60

130

180

O HN 1

N O O O 2

N O

O 3

N O 4

Step 1 product

5

N O O

6

t-C4H9

N

t-C4H9

594

Hindered Spiro-Ketal Nitroxides

NOTES 1. The Step 1 reagent 1,5-dioxa-9-aza-8,8,10,10-tetramethylspiro[5,5]-undecane was prepared according to the method of Murayama [1]. 2. Nesvadba [2] used both aromatic and cyclohexene spiro-ketal derivatives, (I) and (II), respectively, as free radical polymerization reaction regulators.

O

O

O

O

N

N

O

O

(I)

(II)

3. Polystyrene having a Mw of 61,00 daltons and Mn of 35,000 daltons was prepared by Parker [3] by emulsion polymerization mediated by phenyl t-butyl nitrone. Under identical experimental conditions a Mw of 860,000 and a Mn of 440,000 were observed in the absence of this regulator. 4. Nitroxide mediated polymerization using 1- and 2-nitroso-naphthol were used by Ma [4] to regulate the free radical polymerization of styrene. References 1. 2. 3. 4.

K. Murayama et al., US Patent 3,790,525 (February 5, 1974) P. Nesvadba et al., US Patent Application 2006-0149011 (July 6, 2006) D.K. Parker et al., US Patent Application 2006-0241258 (October 26, 2006) Q. Ma et al., US Patent Application 2006-0283699 (December 21, 2006)

Title:

Controlled Polymerization

Author:

D. K. Parker et al., US Patent 6,992,156 (January 31, 2006)

Assignee:


SIGNIFICANCE The controlled emulsion polymerization of styrene using nitroxide-mediated polymerization (NMP), reversible addition-fragmentation transfer polymerization (RAFT), stable free radical polymerization (SFR), and atom transfer radical polymerization (ATRP) methods is described. The chain transfer agent associated with each process was phenyl-t-butylnitrone, nitric oxide, dibenzyl trithiocarbonate, 1,1diphenylethylene, and ethyl 2-bromo-isobutyrate, respectively. Polydispersities between 1.17 and 1.80 were observed.

REACTION a

EXPERIMENTAL 1. Controlled Polymerization of Styrene Using Phenyl-t-Butyl Nitrone and 4,4-Azobis(4-Cyanovaleric Acid) [Nitrooxide-Mediated Polymerization; NMP] In a typical reaction a 750-ml reactor was charged with styrene (962 mmol), oleic acid (21.2 mmol), and phenyl-t-butyl nitrone and then flushed with nitrogen. The mixture was treated with a solution of K3PO4 (18.8 mmol), KOH (29.3 mmol þ 2 mmol KOH per initator), and 4,4-azobis(4-cyanovaleric acid) (2.62 mmol) dissolved in 400 ml of water. In all cases an emulsion formed immediately. Reactors were flushed with nitrogen, sealed, and circulated on a rotating wheel in a water bath at 75 C, and the 595

596


reaction extend was monitored hourly. The solid polymer was obtained by coagulating 100 ml of the latex with dilute hydrochloric acid, filtering, washing with water, and then air-drying at 25 C. Reaction scoping results are provided in Table 1. 2. Controlled Polymerization of Styrene Using In situ Generated Nitric Oxide [Nitrooxide-Mediated Polymerization; NMP] A reactor was charged with styrene (0.48 mol), dodecylbenzenesulfonic acid (0.0092 mol), and 1 ml of distilled water. This mixture was stirred and treated with sodium nitrite (0.002485 mol), and the mixture immediately turned a light bluegreen color that faded to pale yellow within minutes. It was then treated with an aqueous solution comprising water (200 g), K2S2O8 (0.00762 mol), K3PO4 (0.01 mol), and 87.5% pure KOH (0.0115 mol), whereupon a fine microemulsion immediately formed. The mixture was rapidly heated with stirring to 75 C where complete conversion to a stable emulsion occurred in 3 hours. After isolation the product had a Mn of 97,000 daltons, a Mw of 147,000 daltons, and a PDI of 1.51. 3. Controlled Polymerization of Styrene Using Dibenzyltrithiocarbonate [Reversible Addition-Fragmentation Transfer Polymerization; RAFT] A reaction vessel was charged with styrene (1000 g), oleic acid (60.0 g), and dibenzyltrithiocarbonate (7.2 g) and then flushed with nitrogen. The mixture was next treated with an aqueous solution comprising water (4000 g), K2S2O8 (40.0 g), K3PO4 (40.0 g), and KOH (16.4 g), whereupon a fine microemulsion instantly formed. The reaction mixture was heated to 65 C where complete conversion to a stable, slightly yellow polystyrene latex was achieved in roughly 90 minutes; solids comprised 20.6%. After workup the polymer had an Mn of 54,000 daltons with a PDI of 1.17. 4. Controlled Polymerization of Styrene Using 1,1-Diphenylethylene as Controlling Agent [Stable Free Radical Polymerization; SFR] A reaction flask was charged with styrene (0.48 mol), oleic acid (0.0106 mol) and 1,1-diphenylethylene (0.002485 moles) and then flushed with nitrogen. The mixture was next treated with water (200 g), K2S2O8 (0.00762 mol), K3PO4 (0.01 mol), and 87.5% KOH (0.0143 mol), whereupon a fine microemulsion formed. The mixture was rapidly heated with stirring to 75 C where complete conversion to a stable emulsion occurred in 2 hours. After isolation the product had a Mn of 51,000 daltons, a Mw of 92,000 daltons, and a PDI of 1.80. 5. Controlled Polymerization of Styrene Using n-Butyl Acrylate and 1-Hexene [Atom Transfer Radical Polymerization; ATRP] A reactor was charged with 1-hexene (25 g), n-butyl acrylate (25 g), dipyridyl (0.38 g), oleic acid (4.0 g), and ethyl 2-bromoisobutyrate (0.47 g) and then stirred until homogeneous. The mixture was next treated with 85% KOH (1.7 g) dissolved in

Notes

597

139 ml of water, whereupon an emulsion immediately formed. After approximately 2 minutes, 1% CuSO45H2O (60.9 g) was added and formed a bluish emulsion. This was then treated with 2 drops of hydrazine hydrate, and the mixture was heated to around 67 C for 90 minutes where solids comprised 10.9%. After workup 27.5 g of product were isolated.

REACTION SCOPING TABLE 1. Reaction scoping for styrene polymerization conducted at 75 C using 962 mmol styrene monomer and phenyl-t-butyl nitrone as the reaction regulator.

Entry

Ratio Initiator/ Phenyl-t-Butyl Nitrone

Phenyl-t-Butyl Nitrone (mmol)

1 2 4 6

4.24 5.65 7.06 4.24

Ratio Styrene/ Phenyl-t-Butyl Nitrone

Mn (daltons)

227 170 136 227

53,780 39,910 39,490 59,840

3.5 3.5 3.5 2.62

Note: The initiator in all cases was 4,4-azobis(4-cyanovaleric acid).

NOTES 1. In a subsequent investigation by the author [1] additional controlled polymerization reactions for preparing homo-, A-B diblock, and A-B-A triblock styrene polymers by emulsion polymerization are disclosed. 2. In another investigation by the author [2] a selected bis-oxathiazaphospholine derivative, (I), was prepared and used as a free radical regulator in aqueous and nonaqueous emulsion polymerizations of styrene. _

O

+

N i-C3H7 N + O_

i-C3H7

S

+

H3CO

S

OCH3

i

i-C3H7

i-C3H7 O N

N O

PS

H3CO

PS

PS

PS

(I)

OCH3

i: THF 3. The author [3] developed a method for preparing cyclic trithiocarbonates, (II), using epoxides in the ionic solvent 1-butyl-3-methylimidazolium

598


hexafluorophosphate. Trithiocarbonates were subsequently used as RAFT chain transfer agents in the controlled emulsion polymerization of styrene.

S O

i

S

S

(II) i: 1-Butyl-3-methylimidazolium hexafluorophosphate, carbon disulfide, potassium thiocyanate, water 4. The author [4] prepared surfactant pairs as provided in Table 3 for the RAFT polymerization of styrene using dibenzyltrithiocarbonate as the chain transfer agent. TABLE 3. Selected emulsion surfactant pairs used in the controlled RAFT polymerization of styrene monomer with dibenzyltrithiocarbonate as the chain transfer agent. Entry

Latent Surfactant

Surfactant Activator

1 2 3 5 7 9 13 14

Palmitoyl chloride Palmitoyl chloride Palmitoyl chloride Palmitoyl chloride Hexadecylamine Hexadecylamine 4-Dodecylphenol dodecanol

KOH Diethanolamine/KOH glycine 2-Aminopropanesulfonic acid/KOH succinic anhydride HCl KOH Maleic anhydride/KOH

5. Wunderlich [5] utilized nitroxyether derivatives, (III), as free radical transfer agents for controlling the molecular weight of polymers during free radical polymerization.

RO

N O

(III)

R = H, CH3CO

Notes

599

References 1. D.K. Parker et al., US Patent Application 2006-0241258 (October 26, 2006) 2. D.K. Parker et al., US Patent Application 2006-0160774 (July 20, 2006) 3. D.K. Parker et al., US Patent Application 2006-0004210 (January 5, 2006) and US Patent 7,038,062 (May 2, 2006) 4. D.K. Parker et al., US Patent Application 2005-0256253 (November 17, 2005) and US Patent 7,098,280 (August 29, 2006) 5. W. Wunderlich et al., US Patent 7,074,860 (July 11, 2005)

Title: N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidines as Radical Polymerization Inhibitors Author:

F. Fuso et al., US Patent 7,235,663 (June 26, 2007)

Assignee:

Ciba Specialty Chemicals Corp. (Tarrytown, NY)

SIGNIFICANCE Free radical polymerization inhibitors have been prepared by reacting tetramethylpiperidive oxyl derivatives with selected glycidyl intermediates. When used as a styrene polymerization regulator in 1.0 mol% and 0.1 mol% at 120 C, molecular weights of 2400 and 43,400 daltons, respectively, were obtained.

REACTION O N OH O

i

O O

N O O

O

i: 2-(4-Ethylphenoxymethyl)-oxiran, copper(II)chloride, t-butylhydroperoxide

EXPERIMENTAL Preparation of 7,7,9,9-Tetramethyl-8-[1-(4-Oxiranylmethoxy-Phenyl)-Ethoxy]1,4-Dioxa-8-Aza-Spiro[4.5]Decan A mixture of 7,7,9,9-tetramethyl-1,4-dioxa-8-aza-spiro[4.5]decan-8-oxyl (50 g) and 2-(4-ethylphenoxymethyl)oxiran (124.75 g) was heated to 60 C and then treated with of 0.32 g of copper(II) chloride dissolved in 1.6 ml of ethanol. This mixture was further treated with the dropwise addition of 70% aqueous tbutylhydroperoxide (45 g), reacted for 16 hours at 60 C, and cooled to ambient temperature. Excess t-butylhydroperoxide was decomposed by the dropwise addition of 20% aqueous sodium pyrosulfite solution. The mixture was then treated with 100 ml of EtOAc, and the organic and aqueous phases were separated. The organic 600

Regulator Scoping Profile

601

phase was washed twice with 200 ml of saturated NaCl solution, dried, and concentrated. Excess 2-(4-ethylphenoxymethyl)oxiran was removed by distillation; the residue was dissolved in hexane, filtered over aluminium oxide, and reconcentrated. The product was isolated as white crystals after re-crystallization from hexane having a MP ¼ 73.5–74.2 C.

DERIVATIVES TABLE 1. Experimental N-alkoxy-4,4-dioxy-polyalkyl-piperidine regulators and corresponding melting points. Entry

Mp ( C)

Structure

O 1

O

O NO

124–125

O

O 2

O

NO

133–134

OH

O 5

O

NO

O O

88.5–93

O 7

O

NO

O

56–59

O

64.5–67

O

O 8

O

NO

O

REGULATOR SCOPING PROFILE O O

NO

O

Regulator

O

602

N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidines as Radical Polymerization Inhibitors

TABLE 2. Effect on the free radical polymerization of styrene in the presence of the free radical regulator, 7,7,9,9- tetramethyl-8-[1-(4-oxiranylmethoxy-phenyl)ethoxy]-1,4-dioxa-8-aza-spiro-[4.5]decan. Temperature ( C) 120 120 130 130

Inhibitor (mol%)

Polymer Yield (%)

1.0 0.1 1.0 0.1

Mn (daltons)

20 41 41 55

2,400 43,400 4,700 58,000

PDI 1.25 1.59 1.29 1.39

NOTES 1. Additional nitroxyl ether derivatives of the current invention are provided by DeDecker [1]. 2. Wunderlich [2] and Nesvadba [3] prepared long alkyl chain 2,2,6,6 tetraalkylpiperidine-N-oxy radicals and N-alkoxy derivatives, (II), and (III), respectively, that were effective as polymerization regulators. O

.

O C17H35

O

N

O

N

C18H37 NH

O

(II) (III)

3. Nesvadba [4] prepared 4-imino-piperidine-N-oxyl derivatives, (IV) and (V), for use as polymerization regulators.

O N

OC2H5 P OC2H5 O

N O

N

O

N O

(V)

(IV)

Notes

603

4. Dimeric piperidine-N-oxyl derivatives, (VI), were prepared by Roth [5] to control the molecular weight of polypropylene.

O

O

N

N

O

O

O

O

(VI)


M.N. DeDecker et al., US Patent 6,967,228 (November 22, 2005) W. Wunderlich et al., US Patent 6,864,313 (March 8, 2005 and US Patent 6,569,940 May 22, 2003) P. Nesvadba et al., US Patent 7,199,245 (April 3, 2007) P. Nesvadba et al., US Patent 7,160,966 (January 9, 2007) M. Roth et al., US Patent 7,030,196 (April 18, 2006)

C. PHOTOLYTIC REGULATING AGENTS

C. Photolytic Regulating Agents

Title: Method for Producing Polymers with Controlled Molecular Weight and End-Group Functionality Using Photopolymerization in Microemulsions Author:

A. Scranton et al., US Patent 7,226,957 (June 5, 2007)

Assignee:

University of Iowa Research Foundation (Iowa City, IA)

SIGNIFICANCE A method for producing oligomeric butyl acrylate having a controlled molecular weight containing diethanolamine termini by photopolymerization in microemulsions is described. The sensitizer consisted of methylene blue while the photoinitiator consisted of the diethanolamine free radical.

REACTION

.

*

N

N

i S

S

Cl

Cl HO

N

OH

n N O

OH

OH

N

OH

O C4H9 OH

i: N-Methyldiethanolamine, butyl acrylate, water, sodium dodecylsulfate

604

Notes

605

EXPERIMENTAL Oil-in-water microemulsions were prepared using butyl acrylate as the monomer, sodium dodecylsulfate as surfactant, and 1-pentanol as co-surfactant. In a typical reaction, methylene blue and N-methyldiethanolamine were irradiated at 31 C, and the product characterized by GPC.

SCOPING EXPERIMENTS TABLE 1. Effect of sensitizer concentration on the molecular weight of polybutyl acrylate using 0.0349M N-methyldiethanolamine as the photoinitiator. Entry

Polybutylacrylate Mn (daltons)

Concentration of Methylene Blue (M 105)

1 2 3 4

2.246 2.635 2.951 3.209

740 540 390 160

NOTES 1. In an earlier investigation by the author [1] a method was developed for eliminating singlet oxygen in the free radical polymerization of 2-hydroxyethylmethacrylate using 9,10-dimethylanthracene as the singlet oxygen trapper. 2. Fukushige [2] developed a method of microemulsion photopolymerization using organic dyes, (I) and (II). C6H13O

O

OC6H13 O H3CO2C

O N

S

H3CO2C

N O

(II) (I) References 1. A. Scranton et al., US Patent 7,141,615 (November 28, 2006) 2. Y. Fukushige et al., US Patent 7,229,737 (June 12, 2007)

C2H5 N

C2H5

Title: Ring-Opened Azlactone Photoiniferters for Radical Polymerization Author:

K. M. Lewandowski et al., US Patent 7,041,755 (May 9, 2006)

Assignee:

3M Innovative Properties Company (St. Paul, MN)

SIGNIFICANCE Dithiocarbamic-5-oxo-4,5-dihydro-oxazole derivatives have been prepared that are useful in controlled free radical polymerization reactions. When these azlactone photoiniferters were used in the polymerization of styrene or methyl methacrylate, the Mn as a function of reaction time was constant.

REACTION OH OH H2N

O

i

O

ii

NH O

O N

Cl

iii

O

S

O N

S

N

Cl O O S N

i: ii: iii: iv:

O S

n

N

iv

Note 1

Sodium hydroxide, water, chloroacetyl chloride, hydrochloric acid Triethylamine, acetone, ethyl chloroformate Diethyl dithiocarbamate, acetonitrile Styrene

EXPERIMENTAL 1.

Preparation of 2-(2-Chloro-Acetylamino)-2-Methyl Propionic Acid

A reaction vessel containing 2-aminoisobutyric acid (1.61 mol), sodium hydroxide (1.61 mol), and 800 ml of water was cooled to 5 C and treated with chloroacetyl 606

Derivatives

607

chloride (1.77 mol) and 143 ml of aqueous sodium hydroxide (1.77 mol) while maintaining the temperature between 5 C to 10 C. The reaction mixture was then warmed to ambient temperature, and the solution was acidified with 165 ml of 12M HCl. The precipitated solid was filtered and dried under vacuum, and the product was isolated in 62% yield. 2.

Preparation of 2-Chloromethyl-4,4-Dimethyl-4H-Oxazol-5-One

A mixture consisting of the Step 1 product (0.100 mol), triethylamine (0.110 mol), and 100 ml of acetone was cooled in an ice bath and then treated with ethyl chloroformate (0.110 mol) over a period of 10 minutes. The reaction mixture was warmed to ambient temperature and stirred for 2 hours. The mixture was filtered and the filtrate concentrated. The residue was treated with 200 ml of hexane, re-filtered, and re-concentrated. It was distilled, and the product was isolated as a colorless oil in 82% yield, BP ¼ 59–60 C at 7 mmHg. 3. Preparation of Diethyl-Dithiocarbamic Acid 4,4-Dimethyl-5-Oxo-4,5Dihydro-Oxazol-2-Ylmethyl Ester A mixture of 10 g of sodium diethyl dithiocarbamate trihydrate dissolved in 100 ml of toluene was dried using a Dean–Stark trap and then concentrated, and anhydrous dithiocarbamate was isolated. The anhydrous dithiocarbamate (0.039 mol) was then added to a solution of the Step 2 product (0.037 mol) dissolved in 130 ml of acetonitrile, and the mixture was stirred 2 hours at ambient temperature. The mixture was then filtered and the filtrate concentrated. The residue was distilled, and the product was isolated in 74% yield as a yellow-green oil, BP ¼ 170–180 C at 0.25 mmHg. 4.

Preparation of Polystyrene [Az-Polystyrene-DC]

A solution of the Step 3 product (0.00044 mol) dissolved in styrene (0.384 mol) was prepared and then divided into five equal 8.0 g portions. The solutions were placed in vials with screw caps having an integral valve and rubber septum. The solutions were degassed by three successive freeze-pump-thaw cycles and then placed on rollers under a UV lamp (Sylvania F40/350BL-blacklight) 10 cm from the bulb. Each vial was then irradiated for 2.5, 6, 10, 16, and 20 hours with a light intensity of 1.25 mW. Scoping results are summarized in Table 1.

DERIVATIVES A second derivative, (I), was also prepared and used in reaction scoping studies for the preparation of methyl methacrylate star polymers. Testing results are summarized in Table 2.

608

Ring-Opened Azlactone Photoiniferters for Radical Polymerization

O N

N H

S

H N

S

N

O

3

(I) REACTION SCOPING TABLE 1. Physical properties of polymers in the controlled polymerization of styrene using the Step 3 product. Tube 1 2 3 4 5

Reaction Time (h)

Conversion (%)

2.5 6 10 16 20

7.3 16.4 23.2 32.7 36.1

Mn 1 104 (daltons) 1.55 1.77 2.23 2.78 3.10

TABLE 2. Physical properties of polymers in the star polymerization of methyl methacrylate using the trifunctional photoiniferter, (I). Tube 1 2 3 4 5

Reaction Time (h) 1 2 4 6 8

Conversion (%) 1.2 6.5 12.2 15.1 20.3

Mn 1 105 (daltons) 1.83 2.49 2.97 3.04 3.24

Note: Star azlactone were prepared by reacting the Step 2 product with tris(2-aminoethyl)amine.

NOTES 1. In an earlier investigation by the author [1] poly(styrene-b-methymethacrylate) was prepared by postreacting polystyrene with methyl methacrylate in the presence of selected azlactones 2. Fansler [2] used the bromomethyl analogue, (II), of the Step 2 product in the atom transfer radical polymerization of methyl methacrylate. Lewandowski [3] prepared the tribromomethyl analogue, (III), by reacting with trimethylolpropane and then used this reagent to prepare methyl methacrylate star polymers. A reaction profile is provided in Table 3.

Notes

609

O O

O

O N

Br O

(II)

Br

3

(III)

TABLE 3. Reaction profile for controlled free radical polymerization of methyl methacrylate using the star atom transfer radical agent, (III), prepared by Lewandowski [3]. Reaction Time (min) 10 20 30 40 50 60 70

Mw 1 103 (daltons)

Mn 1 103 (daltons)

1.87 2.86 2.97 3.29 3.51 3.95 5.10

1.73 2.45 2.38 2.57 2.71 3.05 3.90

PDI 1.08 1.17 1.25 1.28 1.29 1.29 1.31

3. Lusten [4] prepared macroiniferter polymers, (IV), that were used in electronic devices and in molecular recognition.

N S S

a

b

(IV)

4. Destarac [5] polymerized 4-vinylbenzeneboronic acid using O-ethyl S-(1methoxycarbonyl)-ethyl xanthate, (V), as the free radical polymerisation controlling agent.

O C2H5O

S S

OC2H5 OCH3

(V)

610

Ring-Opened Azlactone Photoiniferters for Radical Polymerization


K.M. Lewandowski et al., US Patent 6,908,952 (June 21, 2005) D.D. Fansler et al., US Patent 6,992,217 (January 31, 2005) K.M. Lewandowski et al., US Patent Application 2005-0065300 Application (May 9, 2005) L. Lutsen et al., US Patent Application 2006-0079648 (April 13, 2006) M. Destarac et al., US Patent Application 2005-0203256 (September 15, 2005)

XXI. PHOTORESISTS A. Fluorine Containing a. Fluorine Acetals

Title: Monomer Having Fluorine-Containing Acetal or Ketal Structure, Polymer Thereof, and ChemicalAmplification-Type Resist Composition as Well as Process for Formation of Pattern with Use of the Same Author:

K. Maeda et al., US Patent 7,232,639 (June 19, 2007)

Assignee:

NEC Corporation (Tokyo, JP)

SIGNIFICANCE Perfluoroacetal or perfluoroketal polymethacrylates containing norbornene substituents and having improved transparency were prepared and were suitable for use in photolithography with far-ultraviolet light at a wavelength of 180 nm or shorter. These materials are particularly useful in the formation of a fine resist patterns. REACTION OH F3 C

CHF2

O

i

O F3 C

a O CHF2

ii O

O F3 C

O CHF2

i: Hexane, diethyl ether, 2-norbornanemethanol, pentafluoroisopropanol, n-butyllithium, hydrochloric acid, ii: Hexane, 2,20 -azobisisobutyronitrile


612

Monomer Having Fluorine-Containing Acetal

EXPERIMENTAL 1.

Preparation of Methacrylate Intermediate

A flask containing 70 ml of THF and 8.56 g of pentafluoroisopropanol was cooled to 78 C and then treated dropwise with 67 ml of 1.6 M n-butyllithium hexane and stirred for 1 hour at 0 C. The mixture was next treated with 2-norbornanemethanol (5 g) dissolved in dry THF and stirred 4.5 hours at ambient temperature. It was poured into ice-water and made acidic with dilute hydrochloric acid. The organic layer was extracted with diethyl ether, washed with saline solution, dried, and concentrated. The residue (2 g) was dissolved in 20 ml of dry CH2Cl2 containing triethylamine (2.56 g) and phenothiazine (8 mg). Under ice cooling this solution was treated with the dropwise addition of methacryloyl chloride (2.21 g) dissolved in 4 ml of CH2Cl2 and stirred 4 hours at ambient temperature. The mixture was diluted with 100 ml of diethyl ether, sequentially washed with 0.5M hydrochloric acid, 3% aqueous NaHCO3 solution, saline solution, and dried over MgSO4; the product was isolated in 65% yield. 1

HNMR (CDCl3) d 0.52 1.82 (9H, m), 1.97 (3H, s), 2.05 2.32 (2H, m), 3.35 3.83 (2H, m), 5.78 (1H, s), 6.27 (1H, s), 6.57 (1H, t) FTIR (KBr; cm1): 2874, 2958 (C–H), 1749 (C¼O) 1638 (C¼C), 1210, 1180, 1141, 1118, 1041

2.

Preparation of Polymethacrylate Ketal

A 50-ml eggplant-shaped flask was charged with the Step 1 product (6.4 g) dissolved in 16 ml of dry toluene and then treated with 2,20 -azobisisobutyronitrile (123 mg). This mixture was stirred 12 hours at 80 C, cooled, and poured into 200 ml of hexane. The precipitate was collected by filtration and further purified by re-precipitation. The product was isolated in 10% yield having a Mw of 7800 daltons and polydispersity index of 1.98.

DERIVATIVES

R1 O O

OR2

F3C

CHF2

Notes

613

TABLE 1. Selected monomers prepared by condensing pentafluoropropyl alcohol with methacryloyl or acryloyl chloride. Entry 1 2 3 4

R1

R2

Methyl Methyl Hydrogen Hydrogen

Benzyl 2-Norbornanemethyl Isobutyl Methyl

Yield (%) 67 65 18 32

Note: Polymers were free radically prepared using 2,20 -azobisisobutyronitrile.

TABLE 2. Selected Step 1 norbornene pentafluoroketal derivatives that were converted into the corresponding polybornene derivative using di-l-chlorobis[(g-allyl) palladium(II)]and silver hexafluoroantimonate. Entry

6

Structure

O

Yield (%)

—

O

O F3C CHF2

24

8

O

O

O F3C CHF2

24

9

O

O

O F3C CHF2

NOTES 1. Additional polymerizable perfluoromethacrylates and polybornenes, (I) and (II), respectively, were prepared by Inoue [1] and used in photoresist compositions.

614

Monomer Having Fluorine-Containing Acetal

O O

CF3 O

F

F3C

F

(I)

OH

O

(II)

2. Polymerizable polycyclic perfluoromonomers, (III), prepared by Sumida [2] were suitable as resist components having high transparency in the ultraviolet region and near-infrared light region.

CF3 F3C

F3 C

O

O

CF3

O

(III) 3. Polymerizable perfluorinated methacrylates, (IV), prepared by Khojasteh [3] were effective as photoresist materials with improved etch resistant properties.

O O

O a=2-6

a

CF3 F3C OH

(IV) 4. Polymerizable perfluoromonomers, (V), prepared by Feiring [4] had high UV transparency at 157 nm and were used in lithography. CF 3 OH O

(V)

CF 3

Notes


K. Inoue, US Patent Application 20030059710 (March 27, 2003) S. Sumida et al., US Patent 7,232,917 (June 19, 2007) M. Khojasteh et al., US Patent 7,217,496 (May 15, 2007) A.E. Feiring et al., US Patent 7,217,495 (May 15, 2007)

615

b. Fluoro Vinylsulfones

Title: Polymers, Resist Compositions, and Patterning Process Author:

Assignees:

Y. Harada et al., US Patent 7,169,869 (January 30, 2007)

Shin-Etsu Chemical Co., Ltd. (Tokyo, JP) Matsushita Electric Industrial Co., Ltd. (Kadoma, JP) Central Glass Co., Ltd. (Ube, JP)

SIGNIFICANCE Novel terpolymer compositions containing 4-(di-trifluoromethyl-hydroxymethyl)-1(di-trifluoromethy)methyl)cyclohexyl] vinylsulfonate have been prepared having excellent transparency, substrate adhesion, and plasma etching resistance. The introduction of perfluoronorbornene resulted polymers that were especially suitable for deep UV lithography.

616

Experimental

617

REACTION CF3 O2S F3C F3C

O2S

O

i

F3C F3C

a

O

O

F3C

O t-C4H9

F3C F3C CF3 HO

c d

b

CF3 OH

CF3 OH

i: 5-(2,2-Trifluoromethyl-2-hydroxy)ethyl-norbornene, t-butyl trifluoromethylacrylate, 1,4-dioxane azobisisobutyronitrile

EXPERIMENTAL 1. Preparation of [4-(di-Trifluoromethyl-Hydroxymethyl)-1-((diTrifluoromethy) Methyl)-Cyclohexyl] Vinylsulfonate Terpolymer A 300-ml flask was charged with 4-(di-trifluoromethyl-hydroxymethyl)-1-((di-trifluoromethyl) methyl)cyclohexyl] vinylsulfonate (7.00 g), 5-(2,2-trifluoromethyl2-hydroxy)ethyl-norbornene (7.58 g), and t-butyl trifluoromethylacrylate (5.42 g) dissolved in 1,4-dioxane (5.0 g). This mixture was then treated with 2,20 -azobisisobutyronitrile (0.34 g) and polymerized at 60 C for 24 hours. The reaction mixture was poured into 1 liter of hexane, and the precipitated was isolated. The polymer was purified by dissolving in THF and re-precipitating in hexane, this process being repeated twice, and 12.5 g of a white polymer product were isolated. Mw (light scattering method) ¼ of 5100 daltons PDI ¼ 1.4 1 H-NMR (monomer ratio, a:b:c) ¼ 16:43:41

618

1

2

O2S F3C O F3C

F3C CF3 HO

O2S F3C O F3C

F3C CF3 HO

Monomer 1

Entry

CF3

F3C CF3 HO

HO

F3C

Monomer 2

O

O

CF3

O O t-C4H9

CF3

Monomer 3

17:42:41

16:43:41

Monomers 1: 2: 3 Ratio in Polymer

5.2

5.1

Mw 1 103 (daltons)

Polymer

TABLE 1. Summary of perfluoromonomers used in the 2,20 -azobisisobutyronitrile initiated free radical terpolymerization and the corresponding polymer physical properties.

DERIVATIVES

1.4

1.4

PDI

619

5

4

3

F3C CF3 HO

O2S F3C O F3C

F3C CF3 HO

O2S F3C O F3C

F3C CF3 HO

O2S F3C O F3C

3

F3C HO CF 3

CF3 CF OH

F3C CF3 HO

F3C CF3 HO

CF3

O

O O t-C4H9

O

CF3

O O t-C4H9

CF3

19:41:40

19:41:40

20:42:38

9.3

9.9

9.3

(continued)

1.6

1.6

1.6

620

HO

F3C

CF3

O2S F3C O F3C

F3C CF3 HO

O2S F3C O F3C

Monomer 1

(Continued)

3

F3C HO CF

3

F3C HO CF 3

3

CF3 CF OH

CF3 CF OH

Monomer 2

CF3

O

O O t-C4H9

O

CF3

Monomer 3

18:41:41

18:41:41

Monomers 1: 2: 3 Ratio in Polymer

9.5

9.5

Mw 1 103 (daltons)

Polymer

1.6

1.6

PDI

Note: In all cases the initial monomer feed ratio of monomers 1, 2, and 3 was 20 : 40 : 40, respectively. Additional perfluoro monomers are described by the author [1] in a subsequent investigation.

7

6

Entry

TABLE 1.

Notes

621

TESTING TABLE 2. Effect of resist polymers on the transmission of 157 nm from an F2 laser. Entry

248 nm Transmission (%)



99 99 99 99 99 99 99 90 82

93 83 10 10 11 11 11 5 6

69 65 60 57 66 60 55 15 17

1 2 3 4 5 6 7 Comparative Polymer 1*1 Comparative Polymer 2*2

Note: All experimental entries were assessed as favorable. *1 *2

Polyhydroxystyrene, Mw ¼ 10,000 daltons, polydispersity index ¼ 1.1 Novolak resin, meta/para ¼ 40/60, Mw ¼ 9,000 daltons, polydispersity index ¼ 2.5

NOTES 1. In other investigations by the author [2,3] polymer resist compositions containing perfluoro oxetene, (II), and cyclohexane, (III), monomers were also effective on the transmission of 157 nm from an F2 laser. CF3 O

O O

O

CF3

O

CF3

(II)

F3C HO

CF3 OH CF3

CF3

(III)

2. Hatakeyama [4] and Harada [5] polymerized monomers containing a-trifluoromethylacrylic carboxylates having acid labile groups, (IV) and (V), respectively, that were used as polymer resists with high surface adhension and alkali dissolution sensitive to high-energy radiation below 200 nm.

622

Polymers, Resist Compositions, and Patterning Process

CF3 CF3 O

O

O

O O O O

O

(IV)

(V)

3. Hatakeyama [6] reduced the number of alcohol groups by approximately 50% in perfluoro terpmonomer resists to modify surface adhesion and transparency by postreacting with methoxymethyl chloride. CF3 CF3 a

O

O

O F3C

CF3 OH CF3

HO F3C

i

+

F3C

F3C CF3 HO

(VI)

HO F3C

b

O CF3 OH

F3C HO

F3C

(VIII)

(VII) ii

CF3

CF3 a

O F3C HO F3C

c

b

O

O

CF3 O F3C

F3C

CF3 HO F3C HO CF3

OCH3

F3C CF3 CF3 O O CF3 H3CO OCH3

(IX)

i: 1,4-Dioxane, 2,20 -azobisisobutyronitrile ii: THF, methoxymethyl chloride References 1. 2. 3. 4. 5. 6.

d

O

Y. Harada et al., US Patent Application 2006-0269871 (November 30, 2006) Y. Harada et al., US Patent 7,125,643 (October 24, 2006) Y. Harada et al., US Patent 7,125,641 (October 24, 2006) J. Hatakeyama et al., US Patent 7,005,228 (January 30, 2007) Y. Harada et al., US Patent Application 2006-0177765 (August 10, 2006) J. Hatakeyama et al., US Patent Application 2005-0084796 (April 21, 2005)

CF3

c. Fluoro Norbornene

Title: Fluorine-Containing Polymerizable Cyclic Olefin Compound Author:

T. Watanabe et al., US Patent 7,012,161 (March 14, 2006)

Assignee:


SIGNIFICANCE Hydrophobic fluorine-containing polymerizable cyclic olefin derivatives have been prepared that are transparent to irradiation at 160 nm or less. These monomers have excellent development characteristics and appear useful as components in a base resin of photoresist compositions. REACTION

i Note 1

ii OH

OH

CHO

F2C

F2C HO

O

OH

F3C

F3C

i: 1,1,1,3,3,3-Hexafluoro-2-propanol, THF, butyllithium ii: Toluene

623

624

Fluorine-Containing Polymerizable Cyclic Olefin Compound

EXPERIMENTAL 1. Preparation of 1-(5-Norbornene-2-yl)-2,2,4,4,4-Pentafluorobutane-1,3,3Triol A reaction vessel containing 1,1,1,3,3,3-hexafluoro-2-propanol (168 g) and THF (1200 g) at 70 C was treated with 1290 ml of 1.6M of butyllithium, and the temperature was gradually increased to 0 C. The mixture was stirred at this temperature for 30 minutes and then treated with of 5-norbornene-2-carboxaldehyde (134 g) and stirred for an additional 60 minutes. After quenching with dilute hydrochloric acid, the mixture was subjected to standard aqueous workup. The crude product was purified by silica gel column chromatography, and the product was isolated in 80% yield. 1

H- NMR (d6-DMSO): d 0.72 (1H, m), 1.18 (1H, br.d, J ¼ 8.0 Hz), 1.29 (1H, br.d, J ¼ 8.0 Hz), 1.74 (1H, ddd, J ¼ 12.0, 9.0, 3.7 Hz), 2.44 (1H, m), 2.77 (1H, m), 3.02 (1H, m), 3.52 (1H, ddd, J ¼ 22.0, 10.6, 7.4 Hz), 6.02 (1H, dd, J ¼ 5.7, 2.8 Hz), 6.19 (1H, dd, J ¼ 5.7, 3.0 Hz), 6.29 (1H, d, J ¼ 7.4 Hz), 7.37 (1H, s), 7.96(1H, d, J ¼ 1.9 Hz). 19 F- NMR (CDCl3): d 130.0 (1F), 120.6 (1F), 82.0 (3F) FTIR (KBr cm1) 3409, 3288, 3062, 2979, 2946, 2923, 2879, 1486, 1454, 1423, 1338, 1311, 1255, 1241, 1207, 1172, 1153, 1112, 1076, 1025, 900, 842, and 711

2. Preparation of 1-Hydroxy-1-(5-Norbornene-2-yl)-2,2,4,4,4Pentafluorobutane-3-One A mixture consisting of the Step 1 product (288 g) and toluene (1500 g) was refluxed, and water was removed during this period. The mixture was cooled and concentrated, and the product was isolated in quantitative yield. 13 C- NMR (d6-DMSO) 182.3 (C¼O) FTIR (film cm1) 1785

Derivatives

625

DERIVATIVES TABLE 1. Entry

Selected perfluoro alcohols and corresponding Step 1 product yields. Step 1 Product Yield (%)

Structure

OH

2

F2C HO F3C

OH

OH

4

F2C HO F3C

F2C HO F3C

100

SCH3

OH

6

65

100

NHSO2CH3

7

OH

91

F2C OH F3C

OH

8

F2C OH F3C

93

626

Fluorine-Containing Polymerizable Cyclic Olefin Compound

NOTES 1. Fluorine-containing photosensitive polymers, (I), containing a gemdiol component were prepared by Yoon [1] and used in resist compositions. CF3

a

OH HO

c

b

O

O t-C4H9

CF2 F3C

HO

CF3

OH

CF3

(I)

2. Photoresist compositions consisting of pentafluoromethylvinyl carbonate derivatives, (II), were prepared by Yoon [2] and used in photosensitive polymers for exposure to light sources having a dominant wavelength of less than 157 nm. Perfluorovinyl ether, (III), monomers were prepared by DiPietro [3] and used in lithographic photoresist polymer compositions.

CF3 OH

F O

O

F O

O

t-C4H9

(II) References 1. K.-S. Yoon et al., US Patent 6,800,418 (October 5, 2004) 2. K.-S. Yoon et al., US Patent 7,202,011 (April 10, 2007) 3. R.A. DiPietro et al., US Patent 7,150,957 (December 19, 2006)

(III)

CF3

CF3

d. Fluoroacrylates

Title:

Photoresist Composition

Author:

R.D. Allen et al., US Patent 7,135,595 (November 14, 2006)

Assignee:

International Business Machines Corporation (Armonk, NY)

SIGNIFICANCE A new family of perfluoroacrylate and methacrylate based positive and negative tone photoresist compositions activated at 193 nm has been prepared by free radical homoor co-polymerization of acrylate or methacrylate derivatives. Polymeric agents prepared in this manner had Mn’s between 5,000 and 50,000 daltons and were readily soluble in organic solvents. REACTION CF3 F3C

CF3

CF3

i

OH F3C

OH

+

F3C

OH

OH Separate

OH

Preferred

a O

O O

CF3

b O

iii

ii

O F3C

OH O

F3C HO CF3 OH

i: Borane-dimethylsulfide complex, 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2ol, THF, hydrogen peroxide, diethyl ether, ii: n-Butyllithium, methacryloyl chloride, THF iii: 2,20 -Azobisisobutyronitrile, THF, 2-(6-hydroxylmethyl)naphthalene methacrylate ester 627

628


EXPERIMENTAL 1. Preparation of 1,1,1-Trifluoro-2-Trifluoromethyl-2,5-Pentanediol (Preferred) and 1,1,1-Trifluoro-2-Trifluoromethyl-2,4-Pentanediol A flask was charged with 974 ml of borane-dimethylsulfide complex (1.95 mol; 2.0M in THF) and treated with 1,1,1-trifluoro-2-trifluoromethyl-4-penten-2-ol (1.7 mol) dissolved in 400 ml of anhydrous THF at such a rate that the temperature did not exceed 15 C. The mixture was stirred at ambient temperature for two days, cooled, and quenched with 750 ml of 3M NaOH. The solution volume was reduced by coevaporation twice with 500 ml of diethylether, and an oil was isolated. The residue was dissolved in 300 ml of cooled THF, slowly treated with 250 ml of 30% hydrogen peroxide, and stirred overnight at ambient temperature. The mixture was diluted with 1 liter of diethyl ether, and the pH was lowered to 6 with 5% HCl. The ether layer was separated, and the aqueous layer was extracted twice with 500 ml of diethyl ether. The combined organic phases were washed twice with 500 ml of saturated aqueous NH4Cl and brine and then dried with MgSO4. The residue was concentrated, and a 379 g mixture of a 45 : 55, 2 /1 alcohol mixture, respectively, was isolated and purified by distillation through a 1200 Vigreux. The 2 alcohol had BP ¼ 47 C at 1.0 mmHg and was a low melting solid, while the preferred 1 alcohol had a BP ¼ 55 C at 1.0 mmHg, which was isolated as a viscous oil.

2. Preparation of 1,1,1-Trifluoro-2-Trifluoromethyl-2-Hydroxy-5-Pentyl Methacrylate A reaction vessel containing n-butyllithium (0.944 mol; 1.6M in hexane) was treated with the Step 1 product dissolved in 300 ml of THF at such a rate that the reaction temperature did not exceed 15 C and then stirred 2 hours. Methacryloyl chloride (0.52 mol) dissolved in 200 ml of anhydrous THF was added dropwise over 1 hour at 10 C, and the mixture was stirred overnight at ambient temperature. The mixture was next diluted with 500 ml of diethyl ether, washed twice with 500 ml of saturated aqueous NH4Cl and brine, and dried with MgSO4. The product was isolated in 79% yield by distillation at 74 C at 1.0 mmHg (0.5 g of phenothiazine was added to the pot prior to distillation).

3. Preparation of Poly(1,1,1-Trifluoro-2-Trifluoromethyl-2-Hydroxy-5-Pentyl Methacrylate-co-2-Methacryloxy-6-Hydroxymethylnaphthalene) A reaction vessel was charged with the Step 2 product (0.018 mol), 2-methacryloxy6-hydroxymethyl naphthalene (0.002 mol), 15 ml of THF, and 2,20 -azobisisobutyronitrile (0.8 mmol) and then refluxed 18 hours. The solution was poured into 500 ml hexanes from which the polymer precipitated. The precipitated polymer was filtered, washed twice with 50 ml hexanes and dried at 60 C, and the product was isolated.

Notes

629

MONOMER DERIVATIVES

O CF3 OH CF3

O O

CF3 OH CF3

O

O CF3 F3C

O

(I)

(II)

(III) O

O O

O

OH

(IV)

O O

(V)

(VI)

O

Polymeric positive and negative tone photoresists activated at 193 nm were prepared using methacrylate monomers, (I–VI), and are illustrated in Table 1.

TABLE 1. Selected polymeric positive and negative tone ptotoresists activated at 193 nm prepared by free radical polymerization using selected methacrylate monomers. Entry 6 7 8 13 15 19 20

Photoresist Tone Positive Negative Negative Negative Positive Negative Positive

Polymer Composition III-co-I-co-V I-co-VI II-co-VI III II III-co-IV IV-co-V-co-VI

NOTES 1. In a subsequent investigation by the author [1] molecular positive tone photoresist blends consisting of nonpolymeric octakis(dimethylsilyloxy)silsesquioxane, (VII), and acid-labile bulky substiutents including 2-t-butyl tetracyclo-dodec-3-ene-5-carboxylate, (VIII), N-(2-tetrahydro-2H-pyran-2yloxy)-5-norbornene-2,3-dicarboximide, (IX), and norbornene anhydride, (X), were prepared and activated at 248 nm, 193 nm, 157 nm, and 134 nm, respectively.

630


R Si O

O

Si R R Si R O O Si O O

R O Si R O

Si

Si

O O Si R O

R

(VII)

R

Entry (VIII)

O O-t-C4H9

O(CH3)2SiO

O

(IX)

O(CH3)2SiO

N O O O

O

(X)

O(CH3)2SiO

O O

2. Carr [2] prepared positive tone photoresists activated below 200 nm by copolymerizing fluorinated bridged carbocyclic compounds, (XI) and (XII), with other fluorinated unsaturated bridged carbocyclic monomers.

Notes

O

C2F5 O

CF3 OH

CF3 a

C2F5 HO

631

CF3

CF3

a=0-4

C2F5

(XII)

(XI)

3. Positive tone photoresist resins activated below 200 nm were prepared by Inoue [3] by copolymerizing polycyclic monomers, (XIII) and (XIV), with t-butyltrifluoromethyl acrylate, (XV).

CF3 S

O

S

F3C

O

CF3

X

(XIII)

X= O,S

O-t-C4H9

(XV)

(XIV)

4. Kodama [4] and Wada [5] prepared positive photosensitive materials consisting of poly(3-hydroxyadamantyl) methacrylate, (XVI), and terpolymers, (XVII), respectively, that were activated at 193 nm.

20

O

42

O

O

27

31

O O

O

O OH

OH

(XVI)

O O

(XVII)


R.D. Allen et al., US Patent 7,141,692 (November 28, 2006) R.V.C. Carr et al., US Patent 7,138,550 (November 21, 2006) K. Inoue, US Patent Application 2003/0059710 (March 27, 2003) K. Kodama, US Patent Application 2006/0204890 (September 14, 2006) and US Patent Application 2005-0287473 (December 29, 2006) 5. K. Wada et al., US Patent Application 2005-123859 (January 9, 2005)

B. Norbornene a. Norborene Lactones and Sultones

Title: Norbornene-Type Monomers and Polymers Containing Pendent Lactone or Sultone Groups Author:

X. Wu et al., US Patent 7,101,654 (September 5, 2006)

Assignee:

Promerus LLC (Brecksville, OH)

SIGNIFICANCE A norbornene terpolymer containing a lactone or sulton substituent has been prepared that is effective in photoresist compositions in the 193 and 157 nm ranges in photolithography. An improvement in etch resistance was also observed. REACTION

O2 S

OH O

i

b

a O2 S

O

ii Note 1

O

OH O SO2

t-C4H9

O

i: THF, n-butyl lithium, 5-norbornene-2-carboxaldehyde, ethyl acetate ii: t-Butyl 5-norbornene-2-carboxylate, bis(toluene)bis(perfluorophenyl) nickel (II) EXPERIMENTAL 1.

Preparation of Hydroxyl Containing Sultone Norbornene

A reactor containing 4-butane sultone (0.20 mol) dissolved in 150 ml of THF was cooled 70 C and treated dropwise with 21.0 ml of 10M n-butyl lithium followed by 632

Etch Resistance Testing

633

the slow addition of 5-norbornene-2-carboxaldehyde (0.20 mol) by syringe. The reaction mixture was stirred overnight at ambient temperature and then poured into water and extracted with EtOAc. It was dried using MgSO4 and concentrated, and the residue was purified by re-crystallization in EtOAc. The product was isolated in 40.6% yield with an endo/exo isomer ratio of 89:11, respectively. H-NMR (500 MHz, CDCl3) [endo isomer]: 6.20 (dd, 1H), 6.04 (dd, 1H), 4.47 (m, 2H), 3.73 (m, 1H), 3.08 (m, 1H), 3.04 (m, 1H), 2.84 (m, 1H), 2.2 2.35 (m, 3H), 1.97 (m, 2H), 1.74 (m, 1H), 1.46 (m, 1H), 1.24 (m, 1H), 0.5 (d, 1H) 13 C-NMR (125 MHz, CDCl3) [endo isomer]: 138.06, 132.63, 74.21, 70.86, 62.32, 49.22, 44.15, 42.46, 41.51, 28.87, 24.40, 21.94 FI-MS m/e [endo isomer]: 258 1

2. Preparation of Poly(t-Butyl 5-Norbornene-2-Carboxylate-co-Carboxy-tButoxy Sultone Norbornene) In a 100-ml crimped vial, t-butyl 5-norbornene-2-carboxylate (17.5 mmol) and the Step 1 product (7.5 mmol) were dissolved in 40 ml of toluene and then sparged with nitrogen for 30 minutes. The mixture was next treated with the slow addition of freshly prepared bis(toluene)bis(perfluoro-phenyl) nickel (II) catalyst (0.5 mmol) in 10 ml of dry toluene and stirred overnight. The polymer was precipitated into hexane and filtered, and 3.5 g of white powder were isolated. 13

C-NMR (125 MHz, CDCl3): (173.4, (C¼O); 79.24, (t-C of t-butyl ester); 62 78 (br),m, (3C-alcohol, and C next to sultone), 43.7 (br), 28.52 s, t-butyl groups) GPC: Mn ¼ 12,460 daltons, Mw ¼ 18,100 daltons.

DERIVATIVE The lactone terpolymer, (I), was also prepared.

a

c

b

O

OSi(CH 3)3 F3C O

O

OH

O

CF 3

(I) ETCH RESISTANCE TESTING A 25% solution of terpolymer (I) dissolved in propylene glycol methylether was prepared and thin films spun onto 4-inch silicon wafers to test for etch resistance and photolithography performance. Etch resistance testing was conducted in a plasma

634

Norbornene-Type Monomers and Polymers Containing Pendent Lactone or Sultone Groups

therm reactive ion etching unit operating at 150 W and 50 mTorr using a CHF3/O2 etchant. The gas flow rates for CHF3 and O2 were 22.5 and 2.5 standard cubic centimeters per minute, respectively. Testing results are provided in Table 1. TABLE 1. Testing results for etching rates for experimental terpolymer (I) and two reference agents. Higher etching levels are preferred. Entry

Etch Rate (A=minÞ

Description

Terpolymer (I) Reference 1 Reference 2

Experimental Agent Novolac SiO2

Etch/Novolac Ratio

604.91 447.17 104.89

1.35 1.00 0.23

NOTES 1. Additional norbornene copolymers, (II), effective in photoresist compositions in the 193 and 157 nm ranges were prepared by the author [1] in a subsequent investigation.

a

H C

b c O O

SO2 O

(II) 2. Amoroso [2] prepared norbornene co-polymers, (III) and (IV), which were used in photosensitive dielectric resin compositions and as films in electronic and optoelectronic devices.

b

a

F3C

OH

O

CF 3

n n = 0,1

b

a O

O

HN

HO

OH

(III)

OH

(IV)

Notes

635

3. Sato [3] and Koyama [4] prepared lactone copolymers, (V) and (VI), respectively, that were effective in positive resist compositions suitable for use in super-microlithography processes such as the manufacture of super-LSI and high-capacity microchips.

a

a

b O

O

O

b

O

O

O

O O-t-C4H9

O

O

(V)

O

(VI) 4. Methacrylate-styryl terpolymers, (VII), and perfluoronorbornene copolymers prepared by Taylor [5] were used in photoresist compositions and were effective at 157 nm and used in short wavelength imaging. a

O

C5F11

c

b

O

F5

F4 OH

C5F11

(VII) 5. Photoresists prepared by Afzali-Ardakani [6] consisting of crosslinkable calix [4]arenes had resolutions of less than 100 nm. References 1. 2. 3. 4. 5. 6.

X. Wu et al., US Patent Application 2005-00153240 (July 14, 2005) D. Amoroso et al., US Patent Application 2006-0008734 (January 12, 2006) K. Sato et al., US Patent Application 2007-0042291 (February 22, 2007) H. Koyama et al., US Patent Application 2006-0281022 (December 14, 2006) G. N. Taylor et al., US Patent 7,132,214 (November 7, 2006) A. Afzali-Ardakani et al., US Patent 7,037,638 (May 2, 2006)

b. Norborene Silsesquioxanes

Title: Photoresists Containing Sulfonamide Component Author:

S. Kanagasabapathy et al., US Patent 7,189,490 (March 13, 2007)

Assignee:

Shipley Company, L.L.C. (Marlborough, MA)

SIGNIFICANCE Photoresist compositions have been prepared that consist of silsesquioxanes containing sulfonamide substituents. These materials are useful in multilayer resist systems that provide contrast upon exposure to photogenerated acid. REACTION SiCl3

i H2N

ii HN

HN SO2CF3

SO2CF3 Intermediate SO2CF3 O

HN SiCl3

iii

O-t-C4H9

iv Intermediate

O t-C4H9-O

i: ii: iii: iv: 636

O t-C4H9-O

Si O O

Si O O

THF, pyridine, trifluoromethanesulfonylchloride, Platinum-divinyltetramethyldisiloxane, toluene, trichlorosilane Palladium acetate, triphenylphosphene, trichlorosilane, toluene, Diethyl amine, water, toluene, potassium hydroxide

Experimental

637

EXPERIMENTAL 1.

Preparation of 5-Norborene- 2-Aminomethyltrifluorosulfonamide

A dry 250-ml flask was charged with 80 ml of THF, pyridine (9.7 g), and norbornene amine (12.3 g) and then cooled to 0 C, treated with trifluoromethanesulfonylchloride (16.9 g) and stirred 4 hours. The mixture was filtered and the THF evaporated. The residue was dissolved in diethyl ether and washed with 3.5% hydrochloric acid, followed by water until a pH of 7 was obtained. Diethyl ether mixture was dried using Na2SO4 and concentrated, and an oily material was isolated. 2. Preparation of Norbornyl-1-Trichlorosilyl-3Aminomethyltrifluorosulfonamide A 100-ml flask was flushed with nitrogen, charged with platinum-divinyltetramethyldisiloxane (200 mg) and 25 ml of toluene, and then stirred at ambient temperature. This mixture was treated with the Step 1 product (10.0 g) followed by the dropwise addition of trichlorosilane (20 g) at ambient temperature. The reaction mixture was stirred at 50 C for 48 hours and distilled, and the product was isolated in >95% yield. 3.

Preparation of t-Butyl-Norbornyl-1-Trichlorosilyl-3-Carboxylate

A 100-ml flask was flushed with nitrogen and charged with palladium acetate (60 mg), triphenylphosphene (180 mg), 25 ml of toluene, and norbornene t-butylester (10.0 g) and then stirred at ambient temperature. This mixture was next treated with the dropwise addition of trichlorosilane (20 g) and stirred at 50 C for 48 hours. After distillation the product was isolated in >95% yield. 4. Preparation of Poly(t-Butyl-Norbornyl-1-Siloxy-3-Carboxylate)-coNorbornyl-1-Siloxy-3-Aminomethyltrifluorosulfonamide) A flask was charged with diethyl amine (11 g), 17 ml of water, and 10 ml of toluene, and the temperature lowered to between 0 C and 5 C. This mixture was treated with the Step 2 and Step 3 products followed by the dropwise addition of toluene (40 g). Thereafter the mixture was warmed to ambient temperature and stirred for 90 minutes. The two layers were separated by the addition of extra water to dissolve the quaternary ammonium salt. Oily materials/residue present in the mixture were dissolved in toluene upon heating to 50 C. The toluene layer was washed three times with 1500 ml of water, once with 50 ml of 10% acetic acid, and additional water until a pH of 7 was obtained. The toluene layer was added into a 250-ml flask and treated with KOH (0.21 g) dissolved in 1 ml of water followed by a 1-ml water rinse. The mixture was refluxed for 2 hours to azeotrope off the water and washed twice with 50 ml of 20% acetic acid and de-ionized water until a pH of 7 was obtained. The toluene solution was washed with IRN-150 for 2 hours to remove toluene, and the product was isolated.

638

Photoresists Containing Sulfonamide Component

DERIVATIVES The terpolymer, (I), was also prepared.

SO2CF3 HN

O O-t-C4H9 CH3

Si O O

Si O O

a (I)

Si O O

b

c

TESTING Photoresist Preparation and Lithographic Processing (Darkfield Formulation) A resist formulation solution was prepared by dissolving terpolymer (I) derivative (1.79 g), triphenylsulfonium perfluorobutanesulfonate (0.082 g), Troeger’s base (0.013 g), and surfactant (0.002 g) in 2-heptanone (17.9 g) and then filtering through a 0.1 micron teflon filter. Using a TEL ACT 8 Coater/Developer Track, the resist was coated onto 8 inch silicon wafers, which were coated with a 510-nm underlayer and heated to 90 C for 60 seconds to form a 150-nm resist film. The coated wafers were then exposed through a mask pattern using an ASM PAS 5500/1100 193 nm scanner. The exposed wafers were heated to 90 C for 120 seconds and developed for 60 seconds at 20 C using 0.26M aqueous alkaline developer solution. Finally, the wafers were rinsed with deionized water and dried. Extremely good focus latitude of this photoresist for 90-nm contact holes were reported by the author. NOTES 1. Silsesquioxane oligomers, (II), were prepared by Barclay [1] and used in optoelectronics, particularly waveguides including polarizers, spectral filters, and wavelength division multiplexing structures. Polymerizable silsesquioxane cage structures containing 8, 10, or 12 components, (III), were prepared by Morita [2] as a method for forming an insulating film having desirable dielectric characteristics. Polymeric silsesquioxane cubanes, (IV), prepared by Hatakeyama [3] demonstrated improved alkali solubility under the action of an acid. In addition the material remained sensitive to high-energy radiation and had high sensitivity and resolution up to 300 nm.

Notes

R

HO

R

O

Si

Si

O

O

Si O

R

R = Norbornyl

OH

Si

O

Si

HO

R

O

639

Si OH

R

R

(II) Si

O

O

Si

O O

Si

O

Si O

O Si O Si

O

O Si

O

Si

O

Si

O

Si O Si O O

O

Si

(III) C5H9

C5H9

Si

O C5H9

O Si C5H9

O

O

Si Si

O

Si

O

O O

Si

O

O

O

Si

C5H9 C5H9

O Si C5H9

(IV) 2. Photoresist compositions containing fluorinated silicon components within a silsesquioxane resin, (V), were prepared by the author [4] and Barclay [5] that exhibited reduced outgasing when exposed to laser radiation, including ArF exposures.

640

Photoresists Containing Sulfonamide Component

HO

CF3

F3C

O O-t-C4H9

Si O O

Si O

O

(V) 3. A positive resist composition containing a silsesquioxane resin, (VI), was prepared by Tamura [6] that exhibited increased alkali solubility under the action of acid.

O HO

O

....

SiO3/2 ....

SiO3/2 ....

SiO3/2 ....

(VI) 4. Norbornene photoresist monomers, (VII), effective for deep UV applications were prepared by Rahman [7].

O

O

O O

(VII)

Notes

641


G.G. Barclay et al., US Patent 7,008,750 (March 7, 2006) K. Morita et al., US Patent Application 2007-0054135 (March 8, 2007) J. Hatakeyama et al., US Patent 6,994,946 (February 7, 2006) S. Kanagasabapathy et al., US Patent Application 2004-0229159 (November 18, 2004) and US Patent Application 2004-0224255 (November 11, 2004) 5. G.G. Barclay et al., US Patent Application 2004-0209187 (October 21, 2004) 6. K. Tamura et al., US Patent Application 7,094,849 (August 22, 2007) 7. M.D. Rahman, US Patent 7,189,491 (March 13, 2007)

C. Adamantane a. Adamantane Methacrylates

Title: Tertiary (Meth)Acrylates Having Lactone Structure, Polymers, Resist Compositions, and Patterning Process Author:

F. Watanabe et al., US Patent 7,037,995 (March 2, 2006)

Assignee:


SIGNIFICANCE A terpolymer consisting of approximately equal ratios of norbornane-2,6- carbolactone and 1- and 2-adamantly derivatives was free radically prepared using N,N0 azobisisobutyronitrile. These materials had improved transparency at the exposure wavelength of an excimer laser and dry etching resistance. Positive resist compositions comprising this polymer were sensitive to high-energy radiation and lend themselves to micropatterning with electron beams or deep-UV radiation.

642

Experimental

643

REACTION

OH

O

O

CO2CH3

i

ii O

O

iii Note 1

O O

O

O

O

O

0.30

0.35

0.35

O

O

O

O

O HO

O

i: THF, methylmagnesium chloride ii: CH2Cl2, triethylamine, methacryloyl chloride iii: 2-Ethyl-2-adamantyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, N,N0 azobis isobutyronitrile, THF

EXPERIMENTAL 1.

Preparation of 3-(1-Hydroxy-1-Methylethyl)-2,6-Norbornanecarbolactone

While stirring under nitrogen at 0 C, a THF solution containing methylmagnesium chloride (860 mmol) was added to a solution of methyl 2,6-norbornanecarbolactone3-carboxylate (80 g) dissolved in 500 ml of THF and then stirred for one hour. The mixture was quenched with an aqueous solution of NH4Cl followed by a conventional aqueous workup. The product was isolated after distillation of the solvent. 2. Preparation of 3-(1-Methacryloyloxy-1-Methylethyl)-2,6Norbornanecarbolactone Under ice cooling a reactor was charged with the entire Step 1 product, triethylamine (70 g), and CH2Cl2 (400 g) and then treated with methacryloyl chloride (55 g) and stirred 12 hours at ambient temperature. The reaction was quenched by adding water followed by a conventional aqueous workup. The mixture was concentrated, and the residue was washed with hexane and dried; 86 g of product were isolated. FTIR (KBr, cm1) 2971, 2960, 2951, 1763, 1711, 1637, 1463, 1450, 1388, 1373, 1331, 1311, 1273, 1203, 1167, 1144, 1126, 1115, 1049, 1012, 968, 957, 945 1 H-NMR (270 MHz in CDCl3) d 1.32 (3H, s), 1.50 (1H, m), 1.54 (3H, s), 1.65 1.80 (2H, m), 1.90 (3H, m), 2.20 (1H, m), 2.45 (1H, m), 2.53 (1H, m), 3.05 3.15 (2H, m), 5.03 (1H, m), 5.57 (1H, m), 6.17 (1H, m)

644

Tertiary (Meth)Acrylates

3. Preparation of Poly(3-(1-Methacryloyloxy-1-Methylethyl)-2,6Norbornanecarbolactone-co-2-Ethyl-2-Adamantyl Methacrylate-co-3Hydroxy-1-Adamantyl Methacrylate) A reactor was charged with the Step 2 product (9.2 g), 2-ethyl-2-adamantyl methacrylate (7.4 g), 3-hydroxy-1-adamantyl methacrylate (8.3 g), N,N0 -azobisisobutyronitrile (60 mg), and 80 ml of THF and then stirred 20 hours at 60 C. After cooling the reaction mixture was added dropwise to 2 liter of methanol, and the precipitate was isolated by filtration. The solids were washed with methanol and dried; 19.9 g of product were isolated having a Mw of 9800 daltons with a polydispersity of 1.80. DERIVATIVES No additional derivatives prepared. TESTING Polymer Transparency The Step 3 product was dissolved in cyclohexanone (6.0 g) and filtered through a 0.2 mm pore diameter teflon filter. The solution was then spin-coated onto a quartz substrate and heated 60 seconds at 90 C, forming a 500 nm thick film. Transmittance was measured at 193 nm using a UV-visible spectrophotometer where it was determined the film had a transmittance of 78% per 500 nm thickness. This result demonstrates that this material was sufficiently transparent for use as a photoresist base polymer in excimer laser photolithography. Resist Pattern Formation Using Polymer A resist material was prepared consisting of: 1. 80 parts by weight of the Step 3 product, 2. 1.0 part by weight of triphenylsulfonium trifluoromethanesulfonate as a photoacid generator, 3. 480 parts by weight of propylene glycol monomethyl ether acetate as a solvent, and 4. 0.08 part by weight of tributylamine as a basic compound. The mixture was initially filtered through a 0.2 mm pore diameter teflon filter. It was spin-coated onto a silicon wafer previously sprayed with hexamethyldisilazane and baked for 40 seconds at 90 C and 90 seconds at 110 C, forming a 500 nm resist film. The resist film was exposed to ArF excimer laser light, heat treated for 90 seconds at 110 C, and cooled to ambient temperature. It was then dipped in 2.38% aqueous tetramethylammonium hydroxide solution for 60 seconds for development where it formed a 1 : 1 line-and-space pattern. The wafer as developed was

Notes

645

observed under SEM, which showed that patterns down to a line width of 0.13 mm were left unstripped and thus resolved. This demonstrates that the photoresist material has improved substrate adhesion and resolution. NOTES 1. Additional positive resist adamantyl polymers, (I), were prepared by the author [1] in a subsequent investigation.

O

O

O

O

0.20

0.20

0.40

0.20

O

O

O

O

O O HO

O

(I) 2. In other investigations by the author [2,3] additional positive resists compositions were prepared containing either imidazole, (II), or tertiary amine derivatives, (III), respectively, and then blended with the select copolymer, (IV), as illustrated.

O O N

N

O

CO2CH3

O N

O

(III)

(II)

0.27

0.73

O

OH

(IV)

O

O

646

Tertiary (Meth)Acrylates

3. A positive resist silicon-containing polymer, (V), was prepared by Kinsho [4] having a resolution wavelength of less than 300 nm that was resistant to oxygen plasma etching. Si(CH3)3 0.4

O

0.5

O

O

Si(CH3)3

Si(CH3)3

O

0.1

O

O

O

Si(Si(CH3)3)3

O

O

(V) 4. Positive resist terpolymeric ester derivatives, (VI), prepared by Hasegawa [5] were sensitive to high-energy radiation while having improved sensitivity, resolution, and etch resistance. They were especially useful in micropatterning with electron beams or deep-UV radiation.

O

0.35

0.30

0.35

O

O

O

O

O

O OH

O O

(VI) References 1. 2. 3. 4. 5.

T. Watanabe et al., US Patent 7,135,270 (November 14, 2006) T. Watanabe et al., US Patent Application 2005-0008968 (January 13, 2005) T. Watanabe et al., US Patent 7,084,303 (August 1, 2006) T. Kinsho et al., US Patent 7,192,684 (March 20, 2007) K. Hasegawa et al., US Patent 7,132,215 (November 7, 2006)

b. Adamantane 4-Hydroxyphenyl Methacrylates

Title: Chemical Amplification Type Positive Resist Composition Author:

A. Yamada et al., US Patent 7,202,010 (April 10, 2007)

Assignee:

Sumitomo Chemical Company, Ltd. (Osaka, JP)

SIGNIFICANCE As a consequence of needing higher integration in existing integrated circuits a requirement for formation of submicron patterns has become necessary. Chemical amplification using positive resist resins containing adamantane have been prepared that have particularly good resolution to meet this latest requirement with only a nominal cost increase. REACTION

0.3

0.7 O

i O O

O

0.3

0.7 O

ii

O

O

OH

O

EXPERIMENTAL 1. Preparation of Poly(2-Ethyl-2-Adamantyl Methacrylate-cop-Acetoxystyrene) A reaction flask was charged with 2-ethyl-2-adamantyl methacrylate (0.24 mol), p-acetoxystyrene (0.56 mol), and isopropanol (279 g) and then heated to 75 C. This mixture was next treated with dimethyl-2,20 -azobis(2-methylpropionate) (0.048 mol) dissolved in isopropanol (22.11 g), stirred 20 minutes, and finally refluxed for 647

648

Chemical Amplification Type Positive Resist Composition

12 hours. The solution was diluted with acetone and then precipitated in methanol; 250 g of the copolymer were isolated. 2. Preparation of Poly(2-Ethyl-2-Adamantyl Methacrylate-co-pHydroxystyrene) The entire Step 1 product was mixed with 4-dimethylaminopyridine and 239 g of methanol and then refluxed 20 hours. After cooling the mixture was neutralized with glacial acetic acid (0.133 mol) and precipitated in water. The precipitate was dissolved in acetone and then re-precipitated in water, the process being repeated three times. The precipitate was dried, and 102.8 g of polymer product were isolated, consisting of 70% p-hydroxystyrene and 30% 2-ethyl-2-adamantyl methacrylate with a Mw of 8200 daltons and polydispersity of 1.68. DERIVATIVES Three additional p-hydroxylstyrene copolymers were prepared.

0.2

0.8

0.31

0.69

0.35

0.65

O

O

O

OH

HO

O

O

HO

NOTES 1. In an earlier investigation by the author [1] a sulfonium salt pair, (I), was used as a chemical amplification type resist that utilized the catalytic action of an acid generated from a sulfonium salt. In a subsequent investigation by Kamabuchi [2] an acid generator salt pair, (II), was prepared and was effective as a chemical amplification type positive resist. Pair #1

Pair #2 O S

O

I

t-C 4H9

t-C 4H9

O

O

O

O

1

2

1

O

O

O

O

O

S

(I)

O O O O

(II)

Notes

649

2. Ester derivatives of 4-hydroxyl polystyrene, (III), prepared by Suetsugu [3] were effective as chemical amplification type positive photoresists.

0.76

0.24

O

HO

O

OCH3

(III)

3. Positive photoresist amplifier perfluoro polymers, (IV), (V), (VI), and (VII), prepared by Kanna [4], Hohle [5], DiPietro, [6], and Allen, [7], respectively, were effective with an exposed light source of 160 nm and thus usable with an F2 excimer laser beam.

F2 F2 C C

a

50

25

25

O

F

F3C HO

CF3

F F

O t-C4H9

F

F3C

(IV)

CF3 OH

(V)

O F3C

(VI)

a

a CF3

O

O

b O

O

HO

OH

HO O

F3C

(VII)

CF3

650

Chemical Amplification Type Positive Resist Composition

References 1. 2. 3. 4. 5. 6. 7.

A. Yamada et al., US Patent 7,160,669 (January 9, 2007) A. Kamabuchi et al., US Patent 7,135,268 (November 14, 2006) M. Suetsugu et al., US Patent 6,828,079 (December 7, 2004) S. Kanna et al., US Patent 7,202,015 (April 10, 2007) C. Hohle et al., US Patent 7,169,531 (January 30, 2007) R.A. DiPietro et al., US Patent 7,150,957 (December 19, 2006) R.D. Allen et al., US Patent 7,014,980 (March 21, 2006)

D. Diamantane Acrylate

Title: Positive Photosensitive Composition and Pattern-Forming Method Using the Same Author:

F. Nishiyama et al., US Patent Application 2007-0072118 (March 29, 2007)

Assignee:

Fuji Photo Film Co., Ltd. (Tokyo, JP)

SIGNIFICANCE When an emitting light at a wavelength of 200 nm is used as the light source, a satisfactory pattern cannot be formed using photosensitive compositions containing aromatic substituents. To address this concern, non-aromatic photosensitive polymeric compositions containing diamantane have been prepared. REACTION O OH

O

i

ii

Note 1

O

O

20

40

20

O

O

O

O

20

O

O

O O

OH

i: Methacrylic anhydride, sulfuric acid, toluene ii: Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 3-hydroxyadamantane methacrylate, 2-methyl-2-adamantyl methacrylate, g-butyrolactone methacrylate 651

652

Positive Photosensitive Composition

EXPERIMENTAL 1.

Preparation of Diamantyl Methacrylate

Hydroxydiamantane (9.8 g), methacrylic anhydride (3.7 g), and 0.5 g of 18M H2SO4 were dissolved in 150 ml of toluene and refluxed for 2 hours. The reaction solution was then washed with aqueous NaHCO3, dried using Na2SO4, and concentrated. The residue was purified by column chromatography, and 6.3 g of product were isolated.

2.

Preparation of Diamantyl-Containing Positive Photoresist Resin

A reaction kettle was charged with propylene glycol monomethyl ether acetate (5.1 g) and propylene glycol monomethyl ether (3.4 g) and then heated to 80 C. This mixture was next treated dropwise with the Step 1 product (2.7 g), 3-hydroxyadamantane methacrylate (4.7 g), 2-methyl-2-adamantyl methacrylate (7.0 g), g-butyrolactone methacrylate (6.8 g), and the free radical initiator V-601. Thereafter the reaction proceeded for 2 hours at 80 C and was then cooled and poured into a 720 ml mixture of hexane containing 80 ml of EtOAc. The precipitate was collected, and 18 g of product were isolated having a Mw of 10,700 daltons with a polydispersity of 1.81. DERIVATIVES

O

O

20

40

20

O

O

O

20

O

O

O

OH O O

(I)

OH

O

O

10

40

10

O

O

O

40

O

O

O O

O O

(II)

O

OH

O

O

Notes

O

OH

20

30

10

O

O

O

653

40

O

O

O

O

O

OH

(III) NOTES 1. Terpolymer photoresist devoid of diadamantyl or aromatic components but containing adamantyl substituents, (IV), were prepared by Tarutani [1] and were effective at 157 and 193 nm.

20

40

O

O

O

40

O

O

O

O OH

O

(IV) 2. Eda [2] cyclopolymerized 1,6-perfluorohepadiene derivative, (V), to prepare a photoresist copolymer composition having the repeat unit, (VI), and it was effective at 157 and 193 nm.

F2C

F3C HO

(V)

F2 C CF

CF a

CF2

CF2

CF3

F3C HO

(VI)

CF3

654

Positive Photosensitive Composition

3. Choi [3] prepared photoresist resins useful at 157 and 193 nm containing polyhedral silsesquioxane substituents as illustrated (VII) below.

O

c

b

a

OH O

O

O

O

OH

(VII) Silicon Cage 4. Chemical amplification type positive resist compositions provided in Table 1 were prepared by Takemoto [4] and were suitable for excimer laser lithography using ArF and KrF lasers. TABLE 1. Aromatic-free photoresists suitable for excimer laser lithography using ArF and KrF lasers prepared by Takemoto [4]. Entry

Monomer ID

1

A

2

B

3

C

4

D

Structure

O

O

O

O

O

O

O

O O

O

Polymer Composition and Monomer Ratio

Mw (daltons)

PDI

A/C/D/E ¼ 25/25/25/25

10,030

1.87

A/C/D/F ¼ 25/25/25/25

9,610

1.74

A/C/DE/F ¼ 20/25/30/20/5

9,897

1.88

A/C/DE/F ¼ 30/15/30/20/5

9,240

1.54

TABLE 1. Entry

O

O

O

F

Polymer Composition and Monomer Ratio

Structure

E

6

655

Mw (daltons)

PDI

(Continued)

Monomer ID

5

Notes

O

A/C/DE/F ¼ 20/25/30/15/10

8,600

1.44

A/H/DE/F ¼ 20/20/30/15/15

7,590

1.64

O

O OH

7

G

8

H

O

O

B/G ¼ 50/50

7,860

1.77

O

O

A/G ¼ 50/50

9,920

1.95


S. Tarutani, US Patent Application 2007-0077519 (April 5, 2007) M. Eda et al., US Patent Application 2007-0083021 (April 12, 2007) S.-J. Choi et al., US Patent Application 2007-0082297 (April 12, 2007) I. Takemoto et al., US Patent 7,205,090 (April 17, 2007)

XXII. SEPARATIONS A. Gases

Title: Dithiolene Functionalized Polymer Membrane for Olefin/Paraffin Separation Author:

W. J. Koros et al., US Patent 7,160,356 (January 9, 2007)

Assignee:

Board of Regents, The University of Texas System (Austin, TX)

SIGNIFICANCE Blended polyimide composites containing 11% neutral dithiolene nickel(II) derivatives were selective for propene in propene/propane stream feeds. Evidence of propene absorption was indicated by a color change of the composite. The selectivity ratio was between about 1.1 and 2.0.


658

Dithiolene Functionalized Polymer Membrane for Olefin/Paraffin Separation

REACTION a

O

O

O O

O F3C

O

i

Note 1

O

CF3

O

N

N

O

F3C

ii

CF3 CF3

O

CF3

a

O F3C

H S

H S

CF3

S

CF3

iii

O

N

N

Ni F3C

S

Olefinic complex in blend

O

F3C

O

CF3 F3C S S S

F3C CF3

CF3 Ni

S S S

Blend

i: 4,40 (Hexafluoroisopropylidene)dianiline, DMAc, triethylamine, acetic anhydride, CH2Cl2 ii: bis[(1,2-Trifluoromethyl)ethylene-1,2-dithiolato] nickel(II), toluene iii: Toluene, propene/propane

EXPERIMENTAL 1. Preparation of Poly[(4,40 -(Hexafluoroisopropylidene)(4,40 -(Hexafluoroisopropylidene)-Phthalimide] 4,40 -Hexafluoroisopropylidene dianiline was dissolved in DMAc and then treated with the dropwise addition of 4,40 -hexafluoroisopropylidene diphthalic anhydride at ambient temperature. The 20 to 25 wt% solution was next stirred 6 to 8 hours until high molecular polyamic acids were formed. The mixture was treated with a large excess of triethylamine and acetic anhydride and dehydrated by heating to 50 C for 2 to 3 hours and at 100 C to 110 C for 10 to 20 minutes then cooled to ambient temperature. The viscous solution was slowly poured into methanol, and the precipitate was homogenized in a blender. It was then filtered and washed several times with fresh methanol. The material was dried for 12 hours at ambient temperature and 24 hours under vacuum at 250 C, and the product was isolated.

Derivatives

659

2. Poly[(4,40 -(Hexafluoroisopropylidene)-(4,40 -(Hexafluoro-Isopropylidene)Phthalimide] Film Blend Containing bis[(1,2-Trifluoromethyl)Ethylene1,2-Dithiolato] Nickel(II) A blend was prepared by mixing an 11 wt% solution of bis[(1,2-trifluoromethyl) ethylene-1,2-dithiolato] nickel(II) in toluene with the Step 1 product. After the mixture had been stirred for at least 20 minutes, the solution was filtered through a 0.2-m teflon syringe filter. The filtered solution was then dispensed on a clean level Teflon dish covered with a casting funnel to control the rate of solvent removal. After approximately 8 hours films were isolated. These material were further dried in a vacuum oven at 100 C for at least 24 hours, and the product was isolated as a clear film. 3. Selective Solubility of C3H6/C3H8 through Poly [(4,40 -(Hexafluoroisopropylidene)-(4,40 -(Hexafluoro-Isopropylidene)Phthalimide] Film Blend Containing 11% bis[(1,2-[TrifluoroMethyl)ethylene-1,2-Dithiolato] Nickel(II) A C3H6/C3H8 mixture was bubbled through a solution of the Step 2 product in toluene at atmospheric prressure. In approximately 30 minutes the film turned yellowish green, which is indicative of complexation with propylene. DERIVATIVES Neutral and ionic dithiolene derivatives that were prepared and used in polyimide composites are provided in Tables 1 and 2, respectively. X

S

X

S

S

X

S

X

Ni

TABLE 1. Neutral dithiolene derivatives blended in polyimide composites. Entry 1 2 3

X CH3 CF3 4-C4H4OCH3

Note: Only entry 2 was effective in separating propene from propene/ propane mixtures.

660

Dithiolene Functionalized Polymer Membrane for Olefin/Paraffin Separation

A

TABLE 2.

S

X

S

X

M

Ionic dithiolene derivatives used in polyimide composite blends.

Entry 6 7 8 9

Aþ

X

M

N(n-C4H9)4 N(n-C4H9)4 N(n-C4H9)4 N(C2H5)4

CH3 CH3 CH3 CN

Ni Pt Fe Co

Note: None of the blends were effective in selectively adsorping propene from propene/propane mixtures.

TESTING Results of polyimide dithiolene blends on the selective adsorption of propene from propene/propane mixtures are provided in Table 3. TABLE 3. Results of polyimides membrane blends containing 11% dithiolene on the selective adsorption of propene from propene/propane mixtures.

Entry 1 2 3 6 7 8 9

Absorption Solvent

Pre-C3H6 Adsorption Polymer Composite Color

Post-C3H6 Adsorption Polymer Composite Color

Toluene Toluene Toluene Toluene Toluene DMAc DMAc

Dark purple Dark with a purple tint Dark forest green Green with blue tint light blue light red Yellow

Color unchanged Yellowish green Color unchanged Color unchanged Color unchanged Color unchanged Color unchanged

Duration of C3H3/C3H8 Introduction (hours) 3 0.5 3 3 3 3 3

Note: A polymer blend color change is indicative of propene adsorption. Only entry 2 was effective.

NOTES 1. Selective polyimide membranes, (I), for helium, carbon dioxide, and oxygen were previously prepared by the author [1] by condensing 4,40 -(hexafluoroisopropylidene) diphthalic anhydride with a 3:2 ratio of 2,4,6-trimethyl-1,3phenylene diamine and diamino benzoic acid, respectively.

Notes

O

F3C

CF3

N

O

O

O

CF3

N

a N

N

O

F3C

O

O

O

661

(I)

b CO2H

2. When poly(2,20 -(m-phenylene)-5,5-bibenzimidazole) having a Mn of 2.0 104 daltons was crosslinked with tetrahydrothiophene-1,1-dioxide, (II), or 1,4phenylene, (III), by Young [2] and Jorgensen [3], respectively, each membrane was selective for hydrogen, carbon dioxide, nitrogen, and methane. H N N

a

CH2

N CH2

A

O2S

A=

CH2

N N N H

(II)

a

CH2

(III)

3. Benzimidazole-containing sulfonated polyimides, (IV), prepared by Brunelle [4] were effective as proton exchange membranes for fuel cells.

O

O N

O a

O

O HO3S

O

NH

N O

O

(IV)


b

N

W.J. Koros et al., US Patent 6,755,900 (June 29, 2004) J.S. Young et al., US Patent 6,997,971 (February 14, 2006) B.S. Jorgensen et al., US Patent 6,946,015 (September 20, 2005) D.J. Brunelle et al., US Patent Application 2007-0112170 (May 17, 2007)

SO3H

B. Solutions a. Amine Separation

Title: Tethered Polymer Ligands Author:

R. F. Hammen et al., US Patent 7,220,703 (May 22, 2007)

Assignee:

Hammen Corporation (Missoula, MT)

SIGNIFICANCE A method for preparing polyisobutylene-g-acrolein and then converting into polyisobutylene-g-alkylamines is described. These polymeric agents are designed for binding biomacromolecules and metal ions to the amine surface.

662

Experimental

663

REACTION Cl 3Si

a

Not isolated

Blocking groups O O O

a

i

a ii

Silica

Blocking groups

Blocking groups O O O

O

O

O

a

Silica iii

NHR NHR NHR Blocking groups O O O Silica

Blocking groups

R= CH 2(CH 2)4CH 2NH 2

..... a

Blocking groups

i: Trichlorosilane, chloroplatinic acid, silica gel, pyridine, bis(trichlorosilyl)ethane ii: Acrolein, 2,20 -azobis(2-methylpropioniamidine) dihydrochloride, water iii: Pentaethylene hexamine, acetic acid, ethanol, sodium borohydride

EXPERIMENTAL 1.

Preparation of Polybutadiene Silica

Phenyl terminated polybutadiene (Mn 1300 daltons, 45% vinyl) was reacted with trichlorosilane and chloroplatinic acid and then mixed with a slurry of 105 m particle size silica gel having a 250 A average pore diameter in dry toluene for 24 hours. The quantity of trichlorosilane used was 2 mol per mole of polybutadiene. Pyridine was added to remove HCl, and the slurry was gently shaken for 18 hours at ambient temperature. The surface of the silica was blocked by addition of 1,2-bis(trichlorosilyl)ethane, and the mixture was treated with pyridine. After three hours of shaking the reaction was worked up by vacuum filtration in a sintered glass funnel and washed with toluene and methanol. The modified silica gel was dried in the filter funnel by continued application of vacuum to the filter funnel.

664

2.

Tethered Polymer Ligands

Preparation of Polyacrolein Silica

The Step 1 product was packed into a 4.6 100 mm high-pressure liquid chromatography column and treated with 1.0M acrolein and 0.025M 2,20 -azobis(2-methylpropioniamidine) dihydrochloride dissolved in water. This mixture was injected into the column, and both ends of the column were plugged. The column was then immersed in a 78 C water bath for 2 hours to complete the reaction. 3.

Reductive Amination of Polyacrolein Silica with Pentaethylene Hexamine

The Step 2 product was packed into an HPLC column and 1M solution pentaethylene hexamine and 0.1M acetic acid in anhydrous ethanol injected into the column. After 2 hours a 0.6M sodium borohydride solution in anhydrous ethanol was injected into the column. After an additional hour unreacted reagents were flushed from the column. The resulting polypentaethylene hexamine silica was able to hold about 800 mmol copper per gram of silica gel. NOTES 1. Additional derivatives of the current invention are provided by the author [1] in an earlier investigation. 2. In a previous investigation by the author [2] composite matrices consisting of polyethylene glycol microspheres containing pendant polyacrolein having solid spaces, interstitial spaces, and interstitial polymer networks were prepared and used to isolate the protein, repligen. Worms-becher [3] developed affinity chromatographic solid compositions for selective adsorption of proteins from complex mixtures. 3. Solid supports consisting of oligonucletoides were prepared by Ravikumar [4] and used in the preparation of substituted pixyl alcohol and analogues. References 1. R.F. Hammen et al., US Patent 6,689,715 (February 10, 2004) 2. R.F. Hammen et al., US Patent 7,201,844 (April 10, 2007) 3. R.F. Wormsbecher., US Patent 7,166,213 (January 23, 2007) and US Patent 6,998,042 (February 14, 2006) 4. V. Ravikumar et al., US Patent 7,202,264 (April 10, 2007)

b. Sulfones

Title: Isolatable, Water-Soluble, and Hydrolytically Stable Active Sulfones of Poly(Ethylene Glycol) and Related Polymers for Modification of Surfaces and Molecules Author:

J. H. Harris, US Patent 7,214,366 (May 8, 2007)

Assignee:

Nektar Therapeutics AL Corporation (Huntsville, AL)

SIGNIFICANCE Poly(ethylene glycol) chloroethyl sulfone and -vinyl sulfone have been prepared in essentially quantitative yields, beginning with polyethylene glycol. Both products selectively reacted with Cys-SH while remaining inert toward Lys-NH2, suggesting their usefulness as chromatography substrates. REACTION O

v

i

OH 67

O

O 67

iv

SO2CH2CH2Cl 67

O

i: ii: iii: iv: v:

OSO2CH3

ii

O 67

O 67

SCH2CH2OH

SO2CH2CH2OH

iii

SO2CH=CH2 67

Methanesulfonyl chloride, toluene, triethylamine, CH2Cl2 Mercaptoethanol, sodium hydroxide, water Hydrogen peroxide, water, tunstic acid Thionyl chloride Sodium hydroxide, CH2Cl2

665

666

Isolatable, Water-Soluble, and Hydrolytically Stable Active Sulfones of Poly(Ethylene Glycol)

EXPERIMENTAL 1.

Preparation of Polyethylene Glycol Mesylate

A reaction vessel was charged with polyethylene glycol (25 g; Mn ¼ 3400 daltons) and dried by azeotropic distillation in 150 ml of toluene. The solution was then treated with 40 ml of CH2Cl2 followed by cooling in an ice bath; it was further treated with 1.230 ml methanesulfonyl chloride and 2.664 ml of dry triethylamine. Thereafter the mixture was stirred overnight at ambient temperature and then filtered. The solvent volume was reduced to 20 ml whereupon the product was precipitated from solution, isolated after filtration, and washed with 100 ml of cold diethyl ether.

2.

Preparation of Poly(Ethylene Glycol) Mercaptoethanol

The Step 1 product (25 g) was dissolved in 150 ml of distilled water and then cooled by immersion in an ice bath and treated with 2.366 ml of mercaptoethanol and 16.86 ml of 2 M NaOH solution. The mixture was refluxed for 3 hours, extracted 3 times with 25 ml of CH2Cl2, and dried with MgSO4 in 25 ml of CH2Cl2. The solvent volume was reduced to 20 ml whereupon the product was precipitated from solution, isolated after filtration, and washed with 150 ml of cold diethyl ether. 1

H-NMR (d6-DMSO) d PEG–SCH2CH2OH 2.57 ppm, triplet, –CH2–S–; 2.65 ppm, triplet, –S–CH2–; 3.5 backbone singlet; and 4.76 ppm, triplet, –OH

3.

Preparation of Poly(Ethylene Glycol) Ethanol Sulfone

The Step 2 product (25 g) was dissolved in 30 ml of 0.123 M tungstic acid solution and cooled in an ice bath. The mixture was treated with 2.876 ml of 30% hydrogen peroxide and stirred overnight at ambient temperature. The mixture was then extracted 3 times with 25 ml of CH2Cl2, washed with dilute aqueous NaHCO3, and dried using MgSO4. The product was isolated as described in Step 1. 1

H-NMR (d6-DMSO) d PEG–SO2CH2CH2OH: 3.25 ppm, triplet, –CH2–SO2–; 3.37 ppm, triplet, –SO2– 3.50 ppm, backbone; 3.77 ppm, triplet, –CH2OH; 5.04 ppm, triplet, –OH

4.

Preparation of Poly(Ethylene Glycol) Chloroethyl Sulfone

The Step 3 product (25 g) was dissolved in 100 ml of thionyl chloride and then refluxed overnight and concentrated. The residue was dissolved in 50 ml apiece of toluene and CH2Cl2 and re-concentrated by distillation. The product was isolated after recrystallization from 50 ml of ethyl acetate. 1

H-NMR (d6-DMSO) d 3.50 ppm, backbone; 3.64 ppm, triplet, –CH2SO2–; 3.80 ppm, triplet, –SO2CH2–

Notes

5.

667

Preparation of Polyethylene Vinyl Sulfone

Polyethylene glycol vinyl sulfone was prepared by dissolving the Step 4 product in CH2Cl2 and treating with two equivalents of NaOH base The solutions were separated, concentrated, and the product was isolated. 1

H-NMR (d6-DMSO) d 3.50 ppm, backbone; 3.73 ppm, triplet, –CH2SO2–; 6.21 ppm, triplet, C¼CH 6.97 ppm, doublet of doublets, –SO2CH–.

DERIVATIVES No additional derivatives were prepared. TESTING Only qualitative information was supplied by the author concerning the selectivities of the Step 4 and Step 5 products with Lys-NH2 and Cys-SH at pH 8 and 9. After 24 hours at either pH neither reagent reacted with Lys-NH2; reactions with Cys-SH were completed within 15 minutes. NOTES 1. In other investigations by the author [1], an additional polyethylene glycol derivative, (I), was prepared and used to modify lucifer-yellow modified lysozyme and bovine serum albumin.

O

O

O

O 67

O

O O

(I)

O N O

O

2. Isothiocyanate-terminated polyethylene glycol derivatives, (II) and (III), were prepared by Smith [2] and Acharya [3], respectively, and were effective in selectively reacting with biomolecules including antibodies, enzymes, and proteins.

668

Isolatable, Water-Soluble, and Hydrolytically Stable Active Sulfones of Poly(Ethylene Glycol) NCS O H3CO

O

O

O

a

O N H

(II)

N H

O

O

aO

OCH3

O O

O

112

O

N H

NCS

(III)

3. A multi-branched compound consisting of mixed polyethylene oxide segments, (IV), was prepared by Davis [4] for use in diagnostics and therapeutics of biologically active molecules. PEG11 PEG4 PEG11 PEG11 O

PEG4 PEG11

O

PEG11 PEG4 PEG11 PEG11 PEG4 PEG11

(IV)

References 1. J.H. Harris et al., US Patent 7,214,388 (May 8, 2007), US Patent 7,166,304 (January 23, 2007) US Patent 7,030,278 (April 18, 2006), and US Patent Application 2006-0155059 (July 13, 2006) 2. P.K. Smith et al., US Patent 7,084,112 (August 1, 2006) 3. S. Acharya et al., US Patent Application 2005-0159339 (July 21, 2005) 4. P.D. Davis et al., US Patent Application 2006-0020134 (January 26, 2006)

c. Optically Active Polymaleimide Derivatives

Title: Optically Active Maleimide Derivatives, Optically Active Polymaleimide Derivatives, Process for Their Production, Separating Media Comprising the Optically Active Polymaleimide Derivatives, and Method of Separating Optically Active Compounds Using Them Author:

T. Miyata et al., US Patent 7,186,750 (March 6, 2007)

Assignee:

Tosoh Corporation (Yamaguchi-ken, JP)

SIGNIFICANCE Optically active malimides have been prepared by condensing succinic anhydride with either (1R, 2R)- or (1S,2S)-2-benzyloxycyclopentylamine and then polymerizing into the corresponding polysuccinimide. When used on a silica gel support in a packed chromatographic column, the polysuccinimide separated selected racemic mixtures. REACTION

i O

O

O

O O

N

O

ii

O

N

O

O

i: Benzene, (1S,2S)-2-benzyloxycyclopentylamine, zinc chloride, hexamethyldisilazane, ethyl acetate ii: Diethylzinc, (-)-sparteine, and toluene

669

670

Optically Active Maleimide Derivatives

EXPERIMENTAL 1.

Preparation of N-[(1S,2S)-2-Benzyloxycyclopentyl]Maleimide

A reactor was charged with maleic anhydride dissolved in 140 ml of benzene and then cooled in an ice bath to 0 C and treated dropwise with (1S,2S)-2-benzyloxycyclopentylamine (26.0 mmol) in 80 ml of benzene. The mixture was warmed to ambient temperature and stirred for 1 hour. This mixture was treated with zinc chloride (26.0 mmol), heated to 80 C, and then further treated with the dropwise addition of hexamethyldisilazane (52.0 mmol) in 70 ml of benzene. Thereafter the reaction mixture was refluxed for 5 hours. It was then cooled to ambient temperature and washed with 2 M hydrochloric acid and extracted with EtOAc. The extract was washed with saturated aqueous NaHCO3, and the saturated brine was dried with MgSO4. The mixture was concentrated, the residue purified by column chromatography using n-hexane/EtOAc, 9:1, respectively, and the product isolated as a pale yellow oil in 91% yield. 2.

Preparation of Poly{N-[(1S,2S)-2-Benzyloxycyclopentyl]Maleimide}

A reactor was charged with diethylzinc (1.0 mmol), (-)-sparteine (1.2 mmol), and toluene and then stirred for 30 minutes at 10 C. This mixture was added to the Step 1 product (10.0 mmol) dissolved in 18 ml of dry toluene and stirred at 10 C for 168 hours. Thereafter the mixture was poured into 200 ml of methanol, and the precipitate was collected by filtration. The reddish solid was washed with 1 M hydrochloric acid and water and dried at ambient temperature under reduced pressure. The product was isolated as a white solid in 82% yield. ½aD25 ¼ þ36:6 (C ¼ 1.0, THF, I ¼ 10 cm) 1 H-NMR (CDCl3) d 7.32-7.21 (m, 5H), 6.61 (s, 2H), 4.51 4.25 (m, 4H), 2.20 1.63 (m, 6H) 13 C-NMR (CDCl3) d 170.39, 138.29, 133.77, 128.13, 127.34, 127.30, 81.62, 71.20, 56.66, 30.97, 27.82, 21.94 MS (m/z) 272 ([M þ H]+) IR (KBr, cm1) 3099, 3065, 3031, 2962, 2874, 1768, 1705, 1595, 1496, 1454, 1404, 1203, 1176, 1140, 1027, 913, 827, 738, 696 Elemental analysis: Found C 70.69; H, 6.31; N, 5.04; Calc: C, 70.83; H, 6.32; N, 5.16 Mn ¼ 2.05 104 daltons PDI ¼ 7.0 ½aD25 ¼ 209:6.degree. (C ¼ 1.0, CHCl3)

3. Preparation of 10% Poly{N-[(1S,2S)-2-Benzyloxycyclopentyl]Maleimide} on a Silica Gel Support in a Packed Column The Step 2 product (500 mg) was dissolved in 10 ml of CCl3H containing silica gel (4.5 g) and having an average particle size of 5 mm and average pore size of 100 A . The CCl3H was distilled off under reduced pressure by means of a rotary evaporator, and 5 g of 10% optically active Step 2 product was loaded onto silica gel. This blend was then dispersed in isopropanol and packed into a stainless steel column of 4.6 mm

Notes

671

ID 150 mm L by means of a high-pressure pump under a pressure of 300 kg/cm2. The theoretical plate number of the packed column was 4470. 1

H-NMR (CDCl3) d 7.35 (br, 5H), 4.50 4.02 (br, 4H), 2.04 1.74 (br, 6H). C-NMR (CDCl3) d 176.27, 138.24, 128.28, 127.78, 127.44, 82.96, 71.38, 58.35, 43.48, 32.45, 28.13, 23.41 IR (KBr, cm1) 3063, 3031, 2960, 2876, 1773, 1686, 1496, 1454, 1395, 1212, 1152, 1095, 1028, 911, 847, 815, 738, 697, 646 Elemental analysis: Found: C, 71.02; H, 6.24; N, 5.29; Calc: C, 70.83; H, 6.32; N, 5.16 13

TESTING The effectiveness of the Step 3 optically active agent in separating selected racemates is provided in Table 1. TABLE 1. Enantionmer separation of selected compounds using the Step 2 optically active agent in a GC column having a flow rate of 1.0 ml/minute and using n-hexane/ isopropinol, 9:1, respectively, as the mobile phase. Entry

Enantiomeric Mixture

k1*1

k2*2

a*3

6 7 8 9

2-Methyl-1-tetralone Benzoin Methyl 2-chloropropionate 2-Benzoxymethyl-2,3-dihydro-4H-pyran-4-one

0.95 0.74 0.40 4.34

1.08 1.45 0.50 4.74

1.14 1.97 1.23 1.09

*1

Retention coefficient of the first eluded enantiomer Retention coefficient of the second eluded enantiomer *3 Separation factor *2

NOTES 1. Additional racemic mixture separations of trans 1,2- and 2,3-epoxy derivatives are provided by co-author Kagawa [1]. 2. Enantioselective polyelectrolyte materials suitable for use as capillary tube and chromato-graphic packing material and consisting of polyvinyl pyridinium salts, (I), were prepared by Schlenoff [2] for use in analytical and membrane separations of chiral agents.

672

Optically Active Maleimide Derivatives

a _ Br

+

N

* (I)

3. Lindsey [3] prepared phosphono-substituted porphyrin derivatives, (II), for attachment to metal oxide surfaces for use as a chromatographic column packing agent. Surface separation methods using 9-borabicyclo[3.3.1]nonane derivatives, (III), are described by Lindsey [4].

O RO RO

NH HN

O P

P NH

(II)

N

OR OR

R = H; O-t-C4H9

Notes

N N

O B

O


T. Kagawa et al., US Patent 6,777,526 (August 17, 2004) J.B. Schlenoff et al., US Patent Application 2007-0037948 (February 15, 2007) J.S. Lindsey et al., US Patent 7,148,361 (December 12, 2006) J.S. Lindsey et al., US Patent 7,153,975 (December 26, 2006)

673

d. Protein Separations

Title: Polymeric Membranes and Uses Thereof Author:

D. H. Solomon et al., US Patent 7,169,847 (January 30, 2007)

Assignee:

Life Therapeutics, Inc. (Clarkston, GA)

SIGNIFICANCE Electrophoresis protein separation membranes have been prepared by step-growth condensation of water-soluble polyvinyl alcohol with selected water-soluble difunctional crosslinking agents. These membranes have broad pore size ranges, restricted pore size distribution, greater resistance to hydrolysis in an alkaline medium, and improved gel clarity when higher amounts of crosslinkers are used.

REACTION OH OH

OH

OH

OH

OH

OH

O

i Note 1

OH

OH

OH O

O

HO

a

O HO

O

HO HO

OH

c

O

HO O OH

O OH

i: Hydrochloric acid, glutaraldehyde

674

b

Testing

675

EXPERIMENTAL 1. Preparation of Polyvinyl Alcohol Membrane Crosslinked with Glutaraldehyde A reaction vessel was charged with 10 ml 5% of solution polyvinyl alcohol having a Mw of roughly 20,000 daltons of which 97.5% to 99.5% were hydrolyzed and 0.333 mL of 6.0M hydrochloric acid and then treated with 91.5 mL of 25% solution of glutaraldehyde. The solution was then poured across a PET support and allowed to stand at ambient temperature for 30 minutes. The membranes were washed with excess distilled water to remove residual catalyst prior to use.

DERIVATIVES A summary of membrane derivatives is provided in Table 1. TABLE 1. Membranes prepared by reacting selected crosslinking agents with 10 ml of 5% solution of polyvinyl alcohol having a Mw of roughly 20,000 daltons and 97.5% to 99.5% hydrolyzed. Entry 3 5 10 14

Crosslinker Glutaraldehyde Glutaraldehyde Divinyl sulfone Polyethylene glycol diglycidyl ether

Crosslinker (mL) 9.2 4.5 317 5664

Note: Very limited characterization data supplied by author.

TESTING Electrophoresis Separations Electrophoresis separations were conducted in a membrane-based electrophoresis apparatus under electrophoretic conditions. Protein samples used to conduct a protein transfer were bovine serum albumin (BSA, 67,000 daltons), chicken egg ovalbumin (Ovalb, 45,000 daltons), and human serum cryo-precipitate. These agents were obtained from plasma containing a mixture of proteins including Fibrinogen (340,000 daltons), human serum albumin (HSA, 67,000 daltons), and immunoglobulin G (IgG, 47,000–56,000 daltons). The cryoprecipitate was diluted with 20 ml of buffer solution prior to separation. A summary of selected separation conditions is provided in Table 2.

676

Polymeric Membranes and Uses Thereof

TABLE 2. Experimental electrophoresis protein separation conditions using membranes prepared by reacting polyvinyl alcohol having a Mw of roughly 20,000 daltons 97.5% to 99.5% hydrolyzed and selected crosslinking agents. Entry 3 3 5 10

Crosslinker

Buffer (nM)

pH

Glutaraldehyde Glutaraldehyde Glutaraldehyde Divinyl sulfone

Tris-Borate Buffer Tris-Glycine Buffer Mes-BisTris Buffer Mes-BisTris Buffer

8.5 9.0 6.85 6.85

NOTES 1. In an earlier investigation by the author [1] electrophoresis protein separation membranes were prepared using triacryloyl-tris(2-aminoethyl)amine, (I), trimethacryloyl-tris(2-aminoethyl)amine, (II), and polyethylenimine acrylates, (III). These agents were polymerized either by using ammonium persulphate or photolytically. R HN O R

R

O

R = H, CH 3

O N H

N

N H

O R

R

O N H

O N

N H

R

(II)

(I)

O N

(III)

a

2. In a subsequent investigation by the author [2] hydrogels were prepared using styryl derivatives, (IV) and (V), with ethylene glycol diacrylate, (VI), as the crosslinking agent. These materials had a hetero-microphase structure characterized by a plurality of highly crosslinked loci or cores interconnected by relatively linear polymer chains. They were useful both as intraocular lenses and as biological separation matrices.

Notes

677

O O

(IV)

O

(VI)

O

OH

O

O

HO

(V)

3. Pathak [3] prepared polyalkoxyether hydrogels, (VII) and (VII), that absorbed a substantial portion of water present in whole blood so that when the swollen hydrogel phase was removed a fibrinogen-rich phase was isolated.

O

O O

O

(VII) O

O

a

a = 280

O

O

a

O

(VIII)

O

b

O a

a = 105 b = 30

O

4. Harris [4] prepared degradable crosslinked hydrogels with controllable halflives using hydrolytically unstable imine linkages, (IX). -PEO]-...

...-[PEO-

N N

O

N

O ...-[PEO-

(IX)

N N

N

-PEO]-...

-PEO]-...


-PEO]

N

N

b

a

-PEO]-...

N

D.H. Solomon et al., US Patent 6,585,873 (July 1, 2003) D.H. Solomon et al., US Patent Application 2003-0027965 (February 6, 2003) C.P. Pathak et al., US Patent 7,057,019 (June 6, 2007) J.M. Harris, US Patent Application 2004-0076602 (April 22, 2004)

c a = 11 b=5

e. Polysaccharide Derivatives

Title: Separating Agent Including a Polysaccharide Derivative Having a Polycyclic Structure Author:

Y. Okamoto et al., US Patent 7,156,989 (January 2, 2007)

Assignee:

Daicel Chemical Industries, Ltd. (Sakai, JP)

SIGNIFICANCE Polysaccharides containing grafted 9H-fluorenyl- or 5-indanyl-carbamates have been prepared that are effective in the separation of aromatic racemic mixtures when used as filler in gas chromatography column.

REACTION

H N

O O OH O O HO

OH

O O

O

i a

N H

O

a

O O HN

i: Lithium chloride, dimethylacetamide, pyridine, 9H-fluorenyl isocyanate ii: THF, silica gel 678

Derivatives

679

EXPERIMENTAL 1.

Preparation of Cellulose-g-tris-(9H-Fluorenyl Carbamate)

Cellulose (0.30 g) and lithium chloride (0.21 g) were dried for 3 hours and then treated with 2.0 ml of dimethylacetamide and swollen at 90 C to 100 C overnight. The mixture was next treated with 6.0 ml of pyridine and 9H-fluorenyl isocyanate (1.3 eq) and reacted for 6 hours. The carbamated cellulose was precipitated, filtered through a glass filter, and dried, and 1.16 g of cellulose product was isolated. Fabrication of a Filler for Coating Cellulose-g-tris-(9H-Fluorenyl Carbamate) onto Silica Gel The Step 1 product (0.75 g) was dissolved in 10 ml of THF, and the solution was perfused uniformly onto silica gel (3 g) of particle size 7 mm with a thin-pore diameter of 1,000 A . The solvent was then distilled off to fabricate a filler on which the Step 1 product was attached. Fabrication of a Column Filled with Silica Gel Coated with Cellulose-g-tris (9H-Fluorenyl Carbamate The Step 2 product (2.5 g) was pressed and filled into a stainless steel column with F 0.46 cm L25 cm by the slurry filling method and used directly for enantiomeric isomer separations.

DERIVATIVES TABLE 1. Elemental analysis of polysaccharides functionalized with 9H-fluorenyl- and 5-indanyl carbamates. Entry

Isocyanate

IA IB IIB

9H-fluorenyl5-Indanyl5-Indanyl-

Isocyanate Equivalents 1.5 1.5 1.6

Elemental Analysis C (%) H (%) N (%) 71.95 65.49 66.19

4.98 5.75 5.76

5.13 6.23 6.44

680

Separating Agent Including a Polysaccharide Derivative Having a Polycyclic Structure

SEPARATIONS Results of enantiomeric isomer separations for the six compounds below using entries IA, IB, and IIB provided in Table 2.

OH O

OH

(b)

(a)

HO

(c)

CF3

O

N O

N

(d)

(e)

(f)

TABLE 2. Effectiveness of enantiomeric separations for racemates (a)–(f) using carbamate-functionalized polysaccharides entries IA, IB, and IIB described in Table 1 with hexane/2-propanol, 90:10, v/v, as the mobile phase at a flow rate of 0.5 ml/min at 25 C. Racemate a b c d e f

Entry IA*1 (a)

Entry IB (a)

Entry IIB (a)

Comparative Example 1*2 (a)

1.56 to 1 1.26 to 1 to 1 to 1

1.41 1.25 1.78 1.12 1.5 1.57

1.46 1.49 1.30 1.41 to 1 1.21

1.19 1.0 1.47 to 1 1.0 to 1

0

0

0

0

The separation coefficient factor, a, is defined as a ¼ k2 =k1 where k1 and k2 are the holding coefficients of the weakly and strongly held enantiomer, respectively. *2 The comparative example consisted of cellulose functionalized with triphenyl carbamate. *1

Notes

681

NOTES 1. Additional carbamate-modified polysaccharides, (I), were prepared by Ohnishi [1] and used in separating enantiomeric racemates of both non-aromatic heterocyclics and aromatic derivatives. OR O O RO

R=

n

CO HN

CO HN

;

OR

(I) 2. Duval [2] prepared three-dimensional chromatographic polysaccharide supports for use in asymmetric synthesis by crosslinking cellulose-g-(4-alloxyphenyl-carbamate), (II), with mercaptopropyl silica, (III).

O

OC

NH

O H N

O O CO O

O

HN

O CO

HS a

O

O

SH

Silica

(III)

O

(II)

3. Roussel [3] prepared chiral polysaccharide esters by grafting a-phenylpropionic acid, (R)-, (IV), and (S)-ibuprofen, or (R)- and (S)-naproxen onto cellulose. These agents were then used for isolating optically active acids.

682

Separating Agent Including a Polysaccharide Derivative Having a Polycyclic Structure

O O O O O O

O

O

(IV)

References 1. A. Ohnishi, US Patent 7,090,775 (August 15, 2006) 2. R. Duval et al., US Patent 7,067,640 (June 27, 2006) 3. C. Roussel et al., US Patent 7,012,138 (March 14, 2006)

n

f. Metal Ion Chelators

Title: Functionalized Polymers for Binding to Solutes in Aqueous Solutions Author:

B. F. Smith et al., US Patent 7,138,462 (November 21, 2006)

Assignee:

Los Alamos National Security, LLC (Los Alamos, NM)

SIGNIFICANCE A method for extracting cadmium, copper, europium, and nickel metal ions from aqueous solution using modified polyethyleneimine is described. The polymer modification consists of grafting an imide, diol, triol, carboxylic acid, or thiocarboxylic acid function to poly(ethyleneimine), which then forms stable metal complexes that are readily removed from solution.

REACTION N a H

H N

i

N

O

HO

a

N

O

OH

i: Ethanol, diethyl tartrate acid

683

684

Functionalized Polymers for Binding to Solutes in Aqueous Solutions

EXPERIMENTAL Preparation of Poly(Ethyleneimine-g-3,4-Dihydroxysuccinimide) Areactorcontainingpolyethyleneimine(43.75 mmol)dissolvedin150 mlofethanolwas treatedwithdiethyltartrate(43.75 mmol)andthenrefluxedfor15hours.Themixturewas cooled to ambient temperature, filtered, and concentrated. The residue was dissolved in water and purified by diafiltration and 9.5 g product isolated. FTIR (cm1): 1654 cm1 indicative that the starting ester (C¼O, 1734 cm1) consumed.

DERIVATIVES H N

N

n

HN R TABLE 1. Modified polyethyleneimine derivatives effective for chelating copper, zinc, nickel, cadmium, europium, and lead metal ions in aqueous solution. Entry 16 32 34 36

R

Polymer Functionalization (%)

CH2CH(OH)CH(OH)CH2OH CH2CSSH CH2COOH CH2CH(OH)CH2OH

36 1% — 49

TESTING TABLE 2. Effectiveness of a 20% solution of polyethyleneimine-g-1,2-dihydroxyprop-3-yl (Table 1, entry 36) as a metal ion chelating agent at pH ¼ 7. Metal Ion Cdþ2 Cuþ2 Euþ3 Niþ2

Initial Solution Concentration (ppm)

Final Solution Concentration (ppm)

Metal Ions Complexed in Resin (%)

224.8 127.2 304.0 117.4

152.3 19.41 114.5 87.46

32.25 84.74 62.34 25.50

Notes

685

NOTES 1. In an earlier investigation by the author [1] polyethyleneimine-g-1,2dihydroxy-prop-3-yl was used to chelate boric acid as a function of temperature. Results from this investigation are provided in Table 3.

TABLE 3. Effectiveness of polyethyleneimine-g-1,2-dihydroxy-prop-3-yl (Table 1, entry 36) in removing boric acid from solution at various temperatures. Temperature ( C)

Final Solution Concentration*1 (ppm)

Metal Ions Complexed in Resin (%)

64.3 69.7 53.4 56.3 35.3 35.5

75.5 73.4 79.6 78.5 86.5 86.5

40 40 20 20 4 4 *1

Reference solution 262 ppm.

2. Frecht [2] prepared Generation-0 polyhydroxyl dendrimeric monomers, (I), for use as diagnostic agents in metal chelate-based contrast materials.

O O

OH OH

Core O HO HO

O O

O

(I)

OH OH

3. Solid phase extraction systems containing surfaces with dicarboxylic acid termini, (II), were prepared by Bakry [3] and used to extract biomolecules such as viruses, proteins, antigens, and RNA and DNA complexes. A similar extraction system was prepared by Gierde [4] using polyglutarmic acid.

686

Functionalized Polymers for Binding to Solutes in Aqueous Solutions

Polystyrene

CO2 O

Surface

O

Si

N H

O OH

O

N

O

CO2

O

(II)

4. Raymond [5] prepared salicylamide derivatives (III), that upon complexation with lanthanide metal ions became luminescent.

N

a

NH

a = 1–3

O HO O O

H2N

(III)

5. Using low molecular urea-formaldehyde resins, Wright [6] selectively extracted mercury from mineral ore containing platinum, gold, palladium, titanium, molybdenum, copper, uranium, chromium, and zinc. References 1. 2. 3. 4. 5. 6.

B.F. Smith et al., US Patent Application 2005-0040109 (February 24, 2005) J.J. Frechet et al., US Patent 7,097,856 (August 29, 2006) R. Bakry et al., US Patent Application 2007-0036685 (February 15, 2007) D.T. Gierde et al., US Patent Application 2006-0286599 (December 21, 2006) K.N. Raymond et al., US Patent 2006-0286567 (December 21, 2006) J.T. Wright et al., US Patent Application 2007-0012630 (January 18, 2007)

XXIII. THERMOSETS A. Poly(Ethyl a-Acetoxyacrylate)

Title:

Acrylic Copolymer

Author:

M. Mouri et al., US Patent 7,230,062 (June 12, 2007)

Assignee:

Kabushiki Kaisha Toyota Chuo Kenkyusho (Aichi-gun, JP)

SIGNIFICANCE Alkyl a-acetoxyacrylate intermediates were prepared by condensing pyruvate derivatives with acetic anhydride and then free radically converting them into the corresponding homo- or copolymers. All copolymers had thermal properties that were superior to that of polymethyl methacrylate. In addition poly(ethyl a-acetoxyacrylate) homopolymers were injection moldable at 250 C.

REACTION O O

O

O OC2H5 O

i

OC2H5 O

ii Note 1

O

a O

OC2H5

O

O

b O

OC4H9

i: Acetic anhydride, p-toluenesulfonic acid monohydrate ii: Butyl a-acetoxyacrylate, 2,20 -azobisisobutyronitrile, xylene

EXPERIMENTAL 1.

Preparation of Ethyl a-Acetoxyacrylate

A mixture consisting of ethyl pyruvate (2.7 mol) and acetic anhydride (5.4 mol) was treated with p-toluenesulfonic acid monohydrate (8 g) and then heated to 120 C for Advances in Polymer Chemistry and Methods Reported in Recent US Patents, by Thomas F. DeRosa Copyright Ó 2008 by John Wiley & Sons, Inc. 687

688

Acrylic Copolymer

24 hours. The mixture was next concentrated under reduced pressure, and 250 g of product were isolated after distillation at 90 C to 103 C at 35 to 40 mmHg. 2.

Preparation of Poly(Butyl a-Acetoxyacrylate-co-Ethyl a-Acetoxyacrylate)

The Step 1 product (60 g), butyl a-acetoxyacrylate (40 g), and 2,20 -azobisisobutyronitrile (0.4 mol%) were dissolved in xylene to form an 80 wt% solution and then heated for 10 hours at 60 C. The reaction mixture was next dissolved in 300 ml of CH2Cl2 and slowly precipitated into 5 liter of methanol. The precipitated material was recovered and dried, and the product was isolated having a Mn of 80,000 daltons with a Mw of 160,000 daltons.

TESTING TABLE 1. Storage modulus testing of homopolymers and a-acetoxyacrylate copolymers. Polymethyl methacrylate is provided as a reference. Storage Modulus (Pa) Polymer Polymethyl methacrylate (Reference) Poly(ethyl a-acetoxyacrylate) Poly(propyl a-acetoxyacrylate-co-octyl a-acetoxyacrylate Poly(ethyl a-acetoxyacrylate-co-stearyl a-acetoxyacrylate)

100 C

200 C

250 C

3.2 106 2 109 2.8 109

170 (dec) 3.6 107 3.2 106

— 2.2 107 4.5 105

1.4 109

3.1 106

4.1 105

NOTES 1. a-Acetoxyacrylate copolymers were initially prepared by Kenyon [1] and used as molding components. 2. Rau [2] prepared terpolymers of ethyl a-acetoxyacrylate, acrylic acid, and vinyl acetate that were used as bleach stabilizers in phosphate-free laundry detergent formulations. References 1. W.O. Kenyon et al., US Patent 2,559,635 (July 10, 1951) 2. I. Rau et al., US Patent 6,921,746 (July 26, 2005)

B. Polyethersulfone

Title:

High-Heat Polyethersulfone Compositions

Author:

D. Steiger et al., US Patent Application 2007-0117962 (May 24, 2007)

Assignee:


SIGNIFICANCE High-performance polyfluorene derivatives consisting of 9,9-bis(4-hydroxyphenyl)fluorene and 4,40 -bis((4-chlorophenyl)sulfonyl)-1,10 -biphenyl have been prepared using reagent ratios from 100:0 to 0:100. When poly(9,9-bis(4-hydroxyphenyl)fluorene) was prepared it had a Mn of 58,000 daltons with a glass transistion temperature greater then 300 C. When copolymers of 9,9-bis(4-hydroxyphenyl)fluorene and 4,4-hydroxybiphenyl were prepared, however, the glass transition temperature was lowered by up to 30 C.

REACTION

i HO

OH

O2 S O

O

O S O2

a

i: bis((4-Chlorophenyl)sulfonyl)-1,10 -biphenyl, potassium carbonate, sulfolane

689

690

High-Heat Polyethersulfone Compositions

EXPERIMENTAL Preparation of Poly(9,9-bis(4-Hydroxyphenyl)Fluorene-co-40 -bis ((4-Chlorophenyl)-Sulfonyl)-1,10 -Biphenyl) A N2 purged reactor was charged with 9,9-bis(4-hydroxyphenyl)fluorene (0.02854 moles), 4,40 -bis((4-chlorophenyl)sulfonyl)-1,10 -biphenyl (0.02854 moles), potassium carbonate (0.03256 moles), and 50 ml of sulfolane. Toluene was added to the mixture then azotropically distilled to make the final water concentration in the mixture less than 80 ppm. The two components were then heated for 9.25 hours at 200 C and cooled to ambient temperature, and 150 ml of orthodichlorobenzene were added. The mixture was then heated to 120 C to dissolve the polymer, which was filtered, and the filtrate was precipitated by adding 500 ml of stirring methanol. The solid was isolated, re-dissolved in 250 ml of hot chloroform, and re-precipitated in 500 ml of methanol, and the product was isolated having a Mw of 54,000 daltons with a polydispersity index of 2.9 and a Tg of 292 C.

DERIVATIVES TABLE 1. The effect of sulfone/fluorene copolymer composition on the glass transition temperature and number average molecular weight. Entry 1 2 3 4

Ratio of Sulfone/Fluorene 0/100 50/50 75/25 100/0

Mn 1 104 (daltons)

Tg ( C)

58 56 52 55

301 292 289 271

NOTES 1. Polyethersulfone compositions, (I), having high heat tolerance, good impact resistance, and Tg’s greater than 235 C were prepared by Brunelle [1] and used as trays in steam autoclave sterilization units and as microwave cookware. Johnson [2] determined that the impact strength of this composition was greater than the commercially available polyethersulfone, RADELÒ .

O2 S O

(I)

a

Notes

691

2. Hung [3] incorporated benzimidazole derivatives, (II), into sulfonated polyethersulfones as a method for preventing filler leaching, improving mechanical properties, and decreasing methanol permeability.

HO

OH

N

NH

(II) 3. Crosslinked polyether sulfone membranes containing pendant sulfonic acid groups were prepared by Michot [4] and used in electrochemical cells. References 1. 2. 3. 4.

D.J Brunelle et al., US Patent Application 2006-0069236 (May 30, 2006) D.S. Johnson et al., US Patent Application 2006-0167216 (July 27, 2006) J. Hung et al., US Patent Application 2007-0100131 (May 3, 2007) C. Michot et al., US Patent 7,045,248 (May 16, 2006)

C. Polynorborene

Title: Novel (Co)polymer, Process for Producing the Same, and Process for Producing Carboxylated (Co)polymer Author:

T. Hayakawa et al., US Patent Application 2007-0112158 (May 17, 2007)

Assignee:

JSR Corporation (Tokyo, JP)

SIGNIFICANCE Thermoplastic resin compositions consisting of ethylene, propylene, 5-ethylidene-2norborene, and trimethylsilyl 4-methyl-tetracyclo[6.2.1.13,6. 02,7]-dodec-9-ene-4carboxylate were prepared and hydrolyzed into the corresponding carboxylic acid. These materials are useful as transparent resins in automotive components.

REACTION a

i

CO2H

b

c

ii

CO2Si(CH3)3

a

b

c

iii

CO2Si(CH3)3

CO2H

i: THF, pyridine, trimethylchlorosilane ii: 5-Ethylidene-2-norbornene, ethylene, propylene, hydrogen, hexane, vanadium (V) oxytrichloride, triethylaluminum trichloride, acetic acid iii: Toluene, hydrochloric acid

EXPERIMENTAL 1. Preparation of Trimethylsilyl 4-Methyl-Tetracyclo[6.2.1.13,6. 02,7] Dodec-9-Ene-4-Carboxylate A reactor was charged with 4-methyltetracyclo[6.2.1.13,6. 02,7]dodec-9-ene-4-carboxylic acid (68.7 mmol), 100 ml of THF, and pyridine (75.6 mmol) and then treated 692

Derivatives

693

with the dropwise addition of trimethylchlorosilane (75.6 mmol) at 0 C. Thereafter the mixture was stirred at this temperature for 5 hours and filtered and concentrated. The residue was treated with 50 ml of n-hexane and stirred for 1 hour, re-filtered, and re-concentrated. The residue was then distilled between 129 C and 132 C at 3 mmHg, and the product was isolated. 2. Preparation of Poly(Ethylene-co-Propylene-co-Trimethylsilyl-4-MethylTetracyclo-[6.2.1.1.sup.3,6.0.sup.2,7]Dodec-9-Ene-4-Carboxylate) A 2000-ml reactor was purged with nitrogen and charged with 1000 ml of hexane and 3.5 ml of the 1.0M hexane solution of the Step 1 product. This mixture was treated with 2 ml of 5-ethylidene-2-norbornene and a gaseous mixture of ethylene (feed rate 5.0 L/ min), propylene (feed rate 4.5 L/min), and hydrogen (feed rate 0.6 L/min) was continuously fed to the mixture at 28 C. This reaction mixture was initially treated with 3.66 ml of a 0.32M hexane solution of VOCl3 and further treated with 20.7 ml of a 0.41 M hexane solution of Al2(C2H5)3Cl3. After polymerizing for 10 minutes, the reaction was quenched with 4.8 ml of acetic acid. The polymer was then washed with water, and 24.1 g of a white solid was isolated. The product consisted of ethylene 67.5 mol%, propylene 32.14 mol%, and trimethylsilyl 4-methyltetracyclo[6.2.1.13,6. 02,7] dodec-9-ene-4-carboxylate 0.33 mol% having a Mw of 31.6 104 daltons. 3. Preparation of Poly(Ethylene-co-Propylene-co-4-Methyl-Tetracyclo [6.2.1.13,6. 02,7]Dodec-9-Ene-4-Carboxylic Acid) The Step 2 product was hydrolyzed by dissolving 20 g into 1000 ml of toluene and then treating with 40 ml of hydrochloric acid and stirring for 3 hours. The reaction mixture was washed with 500 ml of water, precipitated in a copious amount of methanol, and dried, and the product was isolated.

DERIVATIVES TABLE 1. Summary of Mw’s obtained using silyl monomers after 10 minutes of polymerization with ethylene and propylene. Silyl Monomer

Comonomer

Mw 104 (daltons)

None

31.6

5-Ethylidene-2-norborene

29.0

CO2Si(CH3)3

CO2Si(CH3)3 (continued)

694

Novel (Co)polymer, Process for Producing the Same and process

TABLE 1.

(Continued) Comonomer

Mw 104 (daltons)


25.5


22.2

Silyl Monomer

CO2Si(C2H5)3

CO2Si(CH3)2t-C4H9

NOTES 1. In conjunction with an antioxidant and colorant, Kanae [1] used the Step 3 products as thermoplastic elastomers in automobile moldings. Thermoplastic elastomers having good tensile and impact strength were also prepared by Datta [2] by blending isotactic polypropylene with ethylene-propylene rubber. 2. In an earlier investigation by the author [3] Step 2 analogues containing 2-hydroxyethyl methacrylate were prepared and used as rubber components in engineered plastics for automotive applications. 3. Functionalized norborene derivatives, (I) and (II), were prepared by Liaw [4] and used in preparing norborene block copolymers, (III), using RuCl2(CHC6H5) [P(C6H11)] as the polymerization catalyst.

a +

Br

b

i Br

(II) (I) (III)

i: RuCl2(CHC6H5)[P(C6H11)] References 1. K. Kanae et al., US Patent 7,163,983 (January 16, 2007), US Patent 6,982,302 (January 3, 2006), and US Patent Application 20050096437 (May 5, 2005) 2. S. Datta et al., US Patent 7,056,982 (June 6, 2006) 3. T. Hayakawa et al., US Patent 6,803,423 (October 12, 2004) 4. D-J. Liaw et al., US Patent 7,205,359 (April 17, 2007)

D. Polyformals

Title: Polyformals and Copolyformals with Reduced Water Absorption, Production, and Use Thereof Author:

H.-W. Heuer et al., US Patent 7,199,208 (April 3, 2007)

Assignee:


SIGNIFICANCE Linear (co)polyformals consisting of biphenyl derivatives have been prepared having Mw’s of at least 10,000 daltons and reduced moisture absorption. These thermosets are used in molding components and related applications where low moisture absorption is required.

REACTION

HO

OH

i Note 1

t-C4H9

t-C4H9 O

O

O

a

O

i: 4-t-Butylphenol, NMP, CH2Cl2, sodium hydroxide

EXPERIMENTAL Preparation of Poly(3,3,5-Trimethylcyclohexane Bisphenol) A reactor was charged with CH2Cl2 (28.7 kg) and NMP (40.18 kg) and treated with 3,3,5-trimethylcyclohexane bisphenol (22.55 mol), sodium hydroxide (56.38 mol), 4-t-butylphenol (0.34 mol), and 500 liter of CH2Cl2 and then refluxed for 1 hour. The mixture was cooled to ambient temperature and diluted with 35 liter of CH2Cl2 and 20 liter of water; it was washed with water in a separator until a neutral pH and salt free mixture was obtained. The organic phase was transferred to an evaporator tank where a solvent exchange was performed, CH2Cl2 being replaced with chlorobenzene. The 695

696

Polyformals and Copolyformals with Reduced Water Absorption, Production, and Use Thereof

mixture was next extruded at 270 C with subsequent pelletization, the process being performed twice. After discarding the initial material, a total of 9.85 kg of crude product was isolated as transparent pellets. This material was divided into two parts where each part was swollen overnight with 5 liter of acetone to remove low molecular weight material. The purified material was re-dissolved in chlorobenzene and then reextruded, and 7.31 kg of product were isolated.

DERIVATIVES TABLE 1. Physical properties of polyformal derivatives prepared according to the present invention. Entry

1

Mn Tg Mw (daltons) (daltons) ( C) PDI

Structure

t-C4H9

t-C4H9 38,345 O O

O aO

39,901

19,538

89 2.04

t-C4H9 10,644

7,400

158 1.44

3 O

14

20,138 170 1.90

O

O O

t-C4H9 O O

a

O aO

Note: The copolyformal in Entry 3 was prepared using 30 wt% of bisphenol A.

NOTES 1. Additional polyformals, (I), used as protective coatings on polycarbonate surfaces were prepared by the author [1] in a subsequent investigation.

O2 S O

O

(I)

O

a b

Notes

697

2. In an earlier investigation by the author [2], polycarbonates, (II), were prepared that had reduced water uptake and improved flowability.

O O

O

(II)

a

3. Polyindanebisphenol, (III), thermosetting polymers were prepared by McCarthy [3] and were characterized as having a low dielectric constant, low moisture absorption, and a low coefficient of expansion. These materials were used in the production of epoxy-based laminates.

a HO

OH

(III)

4. Cyclic oligomeric formals, (IV), characterized by a lowered water absorption were prepared by Wehrmann [4] and blended with polycarbonates for use in optical data storage media. Copolyformals, (V), were prepared by the author [5] and also used in optical data storage media applications.

O

O

O a O

(IV) t-C4H9

t-C4H9 O

O

O

(V)

O

O

a O

698

Polyformals and Copolyformals with Reduced Water Absorption, Production, and Use Thereof

5. Branched (co)polyformals were prepared by the author [6] that had reduced water uptake, improved hydrolytic stability, and they were used in the preparation of molded articles. References 1. 2. 3. 4.

H.-W. Heuer et al., US Patent Application 2006-0251900 (November 9, 2006) H.-W. Heuer et al., US Patent 7,132,497 (November 7, 2006) T.F. McCarthy et al., US Patent 6,858,304 (February 22, 2005) R. Wehrmann et al., US Patent Application 2006-0025559 (February 2, 2006) and US Patent Application 2006-0089483 (April 27, 2006) 5. H.-W. Heuer et al., US Patent Application 2006-0100389 (March 11, 2006) 6. H.-W. Heuer et al., US Patent 7,028,564 (April 24, 2006)

E. Styrene and Zinc Diacrylate Ionomers

Title:

Branched Ionomers

Author:

J. Reimers et al., US Patent 7,179,873 (February 20, 2007)

Assignee:

Fina Technology, Inc. (Houston, TX)

SIGNIFICANCE Ionomers were prepared that consisted of styrene and zinc diacrylate or acrylic acid neutralized by sodium-, calcium-, or aluminum bases. Homo- and copolymers displayed sufficient flex strength and elongation as well as enhanced melt flow index properties for use in microwave ovens as dishes and utensils.

REACTION

a

i

b O

O

O

Zn

O

2

i: LUPERSOL® 233, zinc dimethacrylate

EXPERIMENTAL 1.

Preparation of Poly(Styrene-co-Zinc Diacrylate)

The free radical polymerization was initiated at 131 C using styrene and LUPERSOLÒ 233 (170 ppm). This mixture was then treated incrementally with sufficient amounts of zinc dimethacrylate dissolved in styrene monomer to prepared copolymers having a zinc diacrylate contents of 400 ppm, 600 ppm, and 800 ppm. The results of copolymer physical testing of these experimental agents is provided in Table 1. 699

700

Branched Ionomers

TESTING TABLE 1. Properties of poly(styrene-co-zinc dimethacrylate) prepared using LUPERSOLR 233. Parameter

Copolymer IA

Zinc dimethacrylate (ppm) Melt flow index Flex strength Elongation Viscosity index Mn (daltons) Mw (daltons)

Copolymer 1B

400 — — — — 94 249

600 3.84 13,808/95.2 3.0 220/104 95 298

Copolymer IC 800 3.51 13,377/95.2 2.5 220/104 94 315

Note: Copolymers 1B and 1C were subsequently used as microwave utensils.

NOTES 1. Muramoto [1] prepared the polymeric solid ionomer, (I), that had high thermal and strong physical properties and were used in electrochemical devices such as batteries, capacitors, and sensors.

a

b O

O

O

O OCH3

O

Li

(I)

2. Macrocyclic ionomers consisting of fullerenes containing grafted NafionÒ acidic termini, (II), were prepared by Wudl [2] and used in composites for conducting membranes. Rao [3], however, used NafionÒdirectly in membranes in electrode assemblies in fuel cells.

Notes

701

CF2(CH2)aSO3

a>3

CF2(CF2)aSO3 (II) 3. Poly(ethylene terephthalate) functionalized with hyperbranched polyamine cations was prepared by Rao [3] and used to splay layered materials in a matrix in polymer-layered nanotubes. 4. Chen [4] prepared a bimodal terpolymer poly(ethylene-co-n-butylacrylate-comethacrylic acid) that was converted into a sodium salt and used as a component in gold balls.

a C4H9O

O

b

c

O

O Na

(III) 5. Smith [5] prepared polyurethanes ionomers, (IV), where the material remained elastic between 20 C and 76 C by reacting isocyanate-terminated prepolymers with acid salt diols.

O

O N H

O

O

a

(IV)

N H

O O

Na


H. Muramoto et al., US Patent Application 2007-0040145 (February 22, 2007) F. Wudl et al., US Patent Application 2007-0003807 (January 4, 2007) Y.Q. Rao et al., US Patent 7,166,657 (January 23, 2007) J.C. Chen., US Patent 7,037,967 (May 2, 2006) W.M. Smith Jr et al., US Patent 6,949,604 (September 27, 2005)

O O

b

F. Polycyclodiene

Title: Copolymer of Conjugated Cyclodiene Author:

J. Shishiki et al., US Patent 6,995,228 (February 7, 2006)

Assignee:

Asahi Kasei Kabushiki Kaisha (Osaka, JP)

SIGNIFICANCE Poly(1,3-cyclohexadiene-co-styrene) having a Mn of 63,603 daltons and containing up to 86% 1,3-cyclohexadiene has been anionically prepared using 1,3-bis(1-lithio1,3,3-trimethyl-butyl)benzene as catalyst. When hydrogenated, the material is converted into a high-performance resin.

REACTION

b

i a

i: Cyclohexane, 1,1-dimethoxycyclohexane, 3-bis(1-lithio-1,3,3-trimethyl-butyl)benzene, triethylamine, styrene

EXPERIMENTAL A N2 purged high-pressure reactor was charged with cyclohexane (2,219 g), 1,1dimethoxycyclo-hexane (346 g), 1,3-cyclohexadiene (600 g), and 40.44 ml of 0.82 M cyclohexane solution consisting of an equimolar mixture of 1,3-bis(1-lithio-1,3,3trimethyl-butyl)benzene and triethylamine. Immediately after the polymerization began, cyclohexane (45 g) containing 33% styrene was charged into the reactor; a second addition was made 3 minutes later. Sample aliquots were removed 5, 10, 20, 30, 702

Notes

703

60, 120, and 240 minutes for analytical evaluation. The reaction was continued for 4 hours and was then quenched with methanol (1.39 g). The polymer solution was precipitated in methanol and washed with acetone, and the product was isolated having a Mn of 63,600 daltons.

REACTION SCOPING TABLE 1. Physical properties of poly(1,3-cyclohexadiene-co-styrene) as a function of reaction extend use of 1,3-bis(1-lithio-1,3,3-trimethyl-butyl)benzene as a catalyst. Aliquot 1 2 3 4 5 6 7

Reaction Time (min)

Amount of 1,3Cyclohexadiene in Copolymer (%)

5 10 20 30 60 120 240

67 75 76 82 85 86 86

Mn (daltons)

PDI

5,507 9,092 31,673 44,085 56,595 62,065 63,603

2.87 2.70 1.63 1.65 1.73 1.76 1.81

NOTES 1. Bicyclic conjugated diene polymers were anionically prepared by Watanabe [1] using bicyclo[4.3.0]-2,9-nonadiene and bicyclo[4.3.0]-1,8-nonadiene and products used in high-performance resins. The polymer product of dicyclopentadiene and 1,3-cyclohexadiene was also prepared by Oshima [2] and used in optical applications. 2. Poly(1,3-cyclohexadiene) homopolymers were previously prepared by Natori [3] using n-BuLi and tetramethylethylenediamine and had excellent thermal and mechanical properties. 3. Poly((1,3-cyclohexadiene)-g-maleic anhydride), (I), was prepared by Imaizumi [4] by postreacting poly(1,3-cyclohexadiene) with maleic anhydride in 1,2,4-trichlorobenzene. Up to 1.4 wt% maleic anhydride was incorporated using this method.

a

O

(I)

O

O

704

Copolymer of Conjugated Cyclodiene

4. Poly((1,3-cyclohexadiene)-co-butadiene), (II), and the hydrogenation product, poly((1,3-cyclohexadiene)-co-butane), (III), were prepared by Nakano [5].

a (II)

b

i

a (III)

i: Hydrogen, dicyclopentadienyltitanium dichloride, triisobutylaluminum References 1. 2. 3. 4. 5.

S. Watanabe et al., US Patent 7,034,095 (April 25, 2006) N. Oshima et al., US Patent 7,015,293 (March 21, 2006) I. Natori., US Patent 5,795,945 (April 18, 1998) K. Imaizumi et al., US Patent 5,830,965 (November 3, 1998) M. Nakano et al., US Patent 6,426,396 (July 30, 2002)

b

G. a-Aromatic Ketones

Title: Poly(Aralkyl Ketone)s and Methods of Preparing the Same Author:

A. Parthiban, US Patent 7,034,187 (April 25, 2006)

Assignee:

Agency for Science, Technology, and Research (Singapore, SG)

SIGNIFICANCE A single-step method for converting a-aromatic carboxylic acids into poly(a-aromatic ketones) using phosphorus pentoxide and methane sulfonic acid is described. These agents are useful as high-performance engineering thermo-plastics having good chemical resistance and high temperature properties.

REACTION OH

a

i O

O i: Phosphorus pentoxide, methane sulfonic acid

EXPERIMENTAL Preparation of Poly(4-Benzylketone) Phosphorus pentoxide (0.0367 mol) was dissolved in 50 ml of methane sulfonic acid by heating the mixture to 80 C and then cooling to ambient temperature. The solution was next treated with phenyl acetic acid (0.0367 mol) and stirred for 4 days at ambient temperature. The solution was subsequently precipitated in 1000 ml water, isolated, and repeatedly washed with water until a neutral pH was observed. After drying the

705

706

Poly(Aralkyl Ketone)s and Methods of Preparing the Same

solid, it was dissolved in THF, re-precipitated in hexane, and dried, and 2 g of product were isolated having a Mw of 5500 daltons and Mn of 2275 daltons. FTIR (KBr) cm 1: 3440(b), 3059(s), 3028(s), 1758(s), 1711(ss), 1600(ss), 1495(ss), 1444(s), 1412(w), 1370(w), 1332(w), 1223(ss), 1181(w), 1113(ss), 1028(w), 755(s), 699(ss) and 521(w)

DERIVATIVES TABLE 1. invention.

Selected aromatic polyketones prepared according to the present

Entry

Structure

Yield (%)

Mw (daltons)

86.0

—

85.5

15,777

O 5

S

7

O

a O

N O

a

Note: Extensive FTIR characterization supplied by the author.

NOTES 1. Poly(ethylene-co-carbon monoxide) and poly(ethylene-co-carbon monoxideco-vinyl acetate), (I), were prepared by Patil [1] and used as adhesive additives and solvents.

O O

(I)

OCH3

a

2. Poly(propylene-co-carbon monoxide) was prepared by Queisser [2] using [Pd (1,3-bis(diphenylphosphino)propane)(NCCH3)2](BF4)2. Fagon [3] used 1,2bis(2,3,4,5-tetramethylphospholyl)ethane for preparing poly(ethylene-cocarbon monoxide. 3. Taniguchi [4] prepared high molecular weight poly(ethylene-co-carbon monoxide) using a catalytic mixture consisting of palladium acetate, 1,3-bis[di(2methoxyphenyl)-phosphino]-propane, sulfuric acid, and 1,4-benzoquinone.

Notes

707

4. Shigematsu [5] observed that by treating glycerin with 96% sulfuric acid and then heating to 160 C for 15 minutes, a polymeric ketone, (II), was produced.

O O

(II)

a


A.O. Patil et al., US Patent 6,677,279 (January 13, 2004) J. Queisser et al., US Patent 7,169,535 (January 30, 2007) and US Patent 6,573,226 (June 3, 2003) P.J. Fagan et al., US Patent 6,579,999 (June 17, 2003) R. Taniguchi et al., US Patent Application 2006-0135738 (June 22, 2006) and US Patent Application 2005-0075475 (April 7, 2005) 5. T. Shigematsu et al., US Patent Application 2006-0252907 (November 9, 2006)

H. Polyimide Sulfones

Title: Polyimide Sulfones, Method and Articles Made Therefrom Author:

R. R. Gallucci et al., US Patent 7,041,773 (May 9, 2006)

Assignee:

General Electric Company (Pittsfield, MA)

SIGNIFICANCE A polyimide sulfone resin has been prepared having a Tg of roughly 250 C and a Mn of roughly 35,000 daltons while still remaining melt processable. When extruded and converted into molded articles at 370 C to 390 C, the molecular weight of the polyimide was diminished by less than 30%.

REACTION O2 S H2N

O

i NH2

N

O O2 S

O

N O

O N

n

O

i: Bisphenol A dianhydride, phthalic anhydride, dichlorobenzene, sodium phenyl phosphinate

EXPERIMENTAL Preparation of Polyetherimide Sulfone A vessel was charged with bisphenol A dianhydride (490 kg), diaminodiphenyl sulfone (245 kg), phthalic anhydride (11.0 kg), 1,287 liters of o-dichlorobenzene, and sodium phenyl phosphinate (360 g) as the reaction catalyst. The mixture was heated to 150 C to 180 C with removal of water, and the reaction was analyzed for residual amine and anhydride end groups. Additional bisphenol A dianhydride or 708

Notes

709

diaminodiphenyl sulfone was added to keep the total amine and anhydride end group concentrations below 20 meq/kg of resin. The reaction mixture was then moved to a holding tank kept at 170 C, and the solvent was removed using two evaporators in series to reduce o-dichlorobenzene to less than 500 ppm. The molten polymer was extruded into strands, cooled in a water bath, and then chopped to give finished pellets. The polymer product had a Mw of 34,000 daltons, a polydispersity index of 2.3, and a Tg of 248 C.

DERIVATIVES No additional derivatives prepared.

RESIN PROCESSING Polyimide sulfone resins were melt processed using a single screw extruder with an 80m filter, extruded into strands, cooled, and then cut into pellets. Pellets were injection molded into parts at 370 C to 390 C. The resins in the molded parts showed less than a 30% thermal deterioration in molecular weight.

NOTES 1. Ohno [1] prepared a polyaromatic ether containing an imide termini, (I), that had a lower dielectric and moisture absorption properties and ease of processability than the imide-free precursor. The imide-functionalized product was used to prepare molding.

O N O

O

O

O

a

(I)

O

O

b

N O

2. An easily processable polyimide was prepared by Mercado [2] from the condensation of bisphenol A dianhydride and bis[4-(4-amino-phenoxy)phenoxy]sulfone that had a Mn of 76,300 daltons and was used in making thin films.

710

Polyimide Sulfones, Method and Articles Made Therefrom

O2 S

O

O

O

O

O

N

a O

(II)

O N O

3. Photosensitive resins consisting of pre-imidized aromatic polyamic acids, (III), having a light transmittance of 365 nm and a low residual stress after cure were prepared by Dueber [3] and used for coating silicon wafers.

O

O

O2 S

NH2 O2C HO

OH

H2N CO2 a

(III)

4. Cured polyimide resins, (IV), used as coatings for semiconductor devices were prepared by Akiba [4] that had good heat resistance, improved adhesion to substrates, and resistance to thermal deterioration. O O OSi

N

9 Si

O N

O

a O

(IV) 5. Matsuwaki [5] prepared polyimide films, (V), having molecular orientation in the machine direction that were used in high-density mounting of flexible printed circuit boards.

Notes

O

O

O N

711

a

N O

O

O

N

(V)

O N b c H

6. A new class of cyclic polyimides, (VI), was prepared by Ding [6] and used in electronic applications.

O N O

O N O

(VI) References 1. 2. 3. 4. 5. 6.

D. Ohno et al., US Patent 7,193,030 (March 20, 2007) R.-M.L. Mercado et al., US Patent 7,192,999 (March 20, 2007) T.E. Dueber et al., US Patent Application 2007-0083016 (April 12, 2007) H. Akiba et al., US Patent Application 2007-0066796 (March 22, 2007) T. Matsuwaki et al., US Patent Application 2007-0045895 (March 1, 2007) J. Ding et al., US Patent Application 2007-0066734 (March 22, 2007)

a

I. Benzoxazine Resins

Title: Method for Producing Benzoxazine Resin Author:

T. Aizawa et al., US Patent 7,041,772 (May 9, 2006)

Assignee:

Hitachi Chemical Co., Ltd. (Tokyo, JP)

SIGNIFICANCE A method for preparing thermosets by modifying o,p-phenol-formaldehyde resins using paraformaldehyde and aniline to provide N-phenyl benzoxazine having a melt viscosity between 2 and 4 poise at 125 C is described.

REACTION

O

OH

N

i Note 1 a

a i: Methyl ethyl ketone, paraformaldehyde, aniline

EXPERIMENTAL Preparation of Benzoxazine A 5-liter resin kettle was charged with o,p-phenol-formaldehyde resin (1040 g) having a Mn of roughly 400 daltons dissolved in methyl ethyl ketone (560 g) and treated with paraformaldehyde (600 g). This mixture was treated with the dropwise addition of 712

Notes

713

aniline (931 g) andthen refluxed for7 hours.Themixturewas concentrated,and the resin and isolated having a softening point of 115 C with a melt viscosity of 40 poise at 150 C.


NOTES 1. The preparation of the o,p-phenol-formaldehyde reagent is described by Hirai [1]. In this preparation oxalic acid was used as the catalyst to ensure high orthopara methylene content. 2. Benzoxazine Step 1 analogues containing s-triazine as a crosslinker, (I), were prepared by Johnson [2] and Gerber [3] as used as thermosets with enhanced high temperature properties. a

O N N O

N

N N

N

O c

b

(I)

References 1. Y. Hirai et al., US Patent 6,005,064 (December 21, 1999) 2. C.K. Johnson et al., US Patent 5,910,521 (June 8, 1999) 3. A.H. Gerber et al., US Patent 7,169,535 (July 15, 2007)

J. Acrylonitrile

Title: Block Copolymer Author:

R. Tsuji et al., US Patent 7,094,833 (August 22, 2006)

Assignee:

Kaneka Corporation (Settsu, JP)

SIGNIFICANCE Economically produced block copolymers containing acrylonitrile or methacrylonitrile as the principal component have been prepared that are heat resistant, weatherable, and oil and flame resistant. These materials were prepared using reversible addition-fragmentation chain transfer polymerization.

REACTION HS

O

O-n-C4H9

i Note 1

a

O

CN O-n-C4H9

b

c

a

ii O

b

SH

c

CN O-n-C4H9

i: Water, sodium dodecyl sulfate, acrylonitrile, cumenyl thiobenzoic acid, 4,40 -azobis (4-cyanovaleric acid) ii: Toluene, ethylamine

EXPERIMENTAL 1.

Preparation of Poly(Acrylonitrile-b-n-Butyl Acrylate)

A reactor was charged with water (490 g), sodium dodecyl sulfate (0.56 g), acrylonitrile (8.8 g), and cumenyl thiobenzoic acid (1.09) and then heated to 80 C for 20 minutes. This solution was treated with 4,40 -azobis(4-cyanovaleric acid) (0.93 g) and additional water (25 g) and then stirred for 30 minutes. Thereafter additional acrylonitrile (45.0 g) was added dropwise over 1 hour, and the mixture heated for approximately 5 hours. A sample wastakenthatindicatedthe polymer had a Mw of13,700daltonsand Mn of10,300daltons with a polydispersity index of 1.33. The mixture was then treated with n-butyl acrylate (20.0 g), 4,40 -azobis(4-cyanovaleric acid) (0.40 g), and water (10 g) and stirred 1 hour at 80 C. The mixture was further treated with n-butyl acrylate (80.0 g) over 2 hours and 714

Testing

715

stirred an additional 5 hours. After the mixture cooled to ambient temperature it was saltied-out and the block copolymer isolated having a Mw of 48,600 daltons and Mn of 34,500 daltons with polydispersity index of 1.41. 2. Preparation of Mercapto-Terminated Poly(Acrylonitrile-b-n-Butyl Acrylate) The Step 1 product (50 g) was dissolved in 200 ml of toluene and treated with ethylamine (15 g) and stirred 8 hours at 30 C. The toluene solution was washed with water and then poured into methanol to precipitate and the product isolated. 1 H-NMR and FTIR analyzes confirmed that the end groups had been quantitatively converted into mercapto groups.

DERIVATIVES Selected diblock polymers are provided in Table 1. Izod impact strength and flame retardancy testing are provided in Table 2. Flame retardancy was measured according to the UL-94 standard.

DERIVATIVES TABLE 1. Selected mercapto-terminated di- and tri-block polymers prepared using either cumenyl thiobenzoic acid, (I), or 1,4-bis(thiobenzoyl-thiomethyl)benzene, (II), as the polymerization regulator. Block Polymer

Mw (daltons)

Mn (daltons)

PDI

Acrylonitrile-butyl acrylate-acrylonitrile Acrylonitrile-vinyl chloride (Acrylonitrile-methyl methacrylate)-butyl acrylate (Acrylonitrile-methyl methacrylate)-vinyl chloride

127,000 71,100 62,900 68,200

84,500 49,400 45,200 46,200

1.50 1.44 1.39 1.48

Entry 15 17 18 21

TESTING TABLE 2. Selected Izod impact strength and flame retardancy for block polymers having mercapto termini. Entry Step 1 product 15 17 18 21

Izod Impact Strength (kJ/m2)

Flame Retardancy

10.5 13.3 7.2 8.8 7.7

V-2 V-2 V-0 V-2 V-0

Note: Flame retardancy testing was measured according to the UL-94 standard.

716

Block Copolymer

NOTES 1. Polymerization regulators consisted of either cumenyl thiobenzoic acid, (I), or 1,4-bis(thiobenzoyl-thiomethyl)benzene, (II). S S S

S S

(I)

S

(II)

2. In other investigations by the author [1] curable di- and tri-block copolymers were prepared containing an allyl terminus that had good thermal stability and weatherability properties. 3. Moisture curable n-butyl acrylate oligomers materials containing a dimethoxymethyl hydrosilane termini were prepared by Ohshiro [2] and the author [3] that had good heat resistance, weatherability, oil resistance, and low staining properties. 4. Polyurethane-based materials having hot water resistance, strength, and chlorine and chemical resistance were prepared by the author [4] by reacting poly(nbutyl acrylate) containing mercapto termini with 4,40 -diphenylmethane diisocyanate and 1,4-butanediol. 5. Nakagawa [5] prepared poly(styrene-b-isobutylene) through atom transfer radical polymerization that had good weatherability properties. References 1. R. Tsuji et al., US Patent 7,081,503 (July 25, 2006), US Patent 7,009,004 (March 7, 2006), and US Patent Application 2006-0004171 (January 5, 2006) 2. N. Ohshiro et al., US Patent Application 2005-0004318 (January 6, 2005) 3. R. Tsuji et al., US Patent 6,914,110 (January 5, 2005) 4. R. Tsuji et al., US Patent 6,992,138 (January 31, 2006) 5. Y. Nakagawa et al., US Patent 7,056,983 (January 6, 2006)

K. Polycarbonates

Title: Aliphatic Diol Polycarbonates and Their Preparation Author:

D. Dhara et al., US Patent 7,138,479 (November 21, 2006)

Assignee:


SIGNIFICANCE Polycarbonate resins were prepared by reacting diphenyl carbonate with bisphenol A and isosorbide. These resins had light transmissions exceeding 90% with little or no haze. As a result of the favorable elastic modulus and hardness properties, these resins were scratch resistant.

REACTION HO O O

i Note 1

O

O

OH

O

a

O

O

O

O

O

b c

O

i: Bisphenol A, diphenyl carbonate, sodium hydroxide, tetramethylammonium hydroxide

EXPERIMENTAL Preparation of Poly[(Isosorbide-co-Bisphenol A)Carbonate)] A glass reactor was passivated by soaking in a bath containing 1M aqueous hydrochloric acid solution for 24 hours and then thoroughly rinsed and dried. The reactor was charged with isosorbide, bisphenol A, and diphenyl carbonate where the number of moles of diphenyl carbonate to the sum of number of moles of bisphenol A and 717

718

Aliphatic Diol Polycarbonates and Their Preparation

isosorbide was 1.12, respectively. The catalyst consisted of a combination of sodium hydroxide and tetramethylammonium hydroxide in a mole ratio of 1:100, respectively. In all cases, however, the molar ratio of tetramethylammonium hydroxide to the total moles of isosorbide and bisphenol Awas 5.0 10 4. The reactor was heated to 180 C with stirring at 40 to 60 revolutions per minute then further heated to 210 C at 18,000 Pa. After stirring for 30 minutes, the pressure was reduced to 10,000 Pa, and stirring continued an additional 50 minutes. The temperature was then raised to 240 C while lowering the pressure to about 1500 Pa and the reaction continued for an additional 30 minutes. Finally the reaction temperature was further raised to 260 C while the pressure was lowered to 150 Pa. The mixture was then brought to atmospheric pressure, the reactor was cooled to ambient temperature, and the product was isolated.

DERIVATIVES AND TESTING Physical properties of polycarbonates derived from diphenyl carbonate, and isosorbide and/or bisphenol and those derived from bismethylsalicylcarbonate, (I), bisphenol A and/or isosorbide are provided in Tables 1 and 2, respectively.

TABLE 1. Polycarbonates prepared by reacting diphenyl carbonate with isosorbide and bisphenol A.

Entry

Composition

1

Isosorbide, 100% Isosorbide, bisphenol A, 50:50 Isosorbide, bisphenol A, 25:75 Isosorbide, bisphenol A, 83:17

3

5

7

Tg ( C)

Elastic Modulus (Gpa)

Hardness (Mpa)

Yellowness Index

8,728

151.0

4.95

311.8

10.54

27,879

15,832

152.0

3.34

234.3

4.53

38,795

21,597

152.0

3.63

222.7

9.74

25,767

15,358

—

—

—

—

Mw (daltons)

Mn (daltons)

16,060

Note: Light transmittance for all materials exceeded 90% with excellent scratch resistance.

Notes

719

TABLE 2. Physical properties of polycarbonates obtained from the reaction of bisphenol A and isosorbide with bismethylsalicylcarbonate, (I).

CO2CH3

CO2CH3

O

O O

(I)

Entry 2 4

6

Composition Isosorbide, 100% Isosorbide, bisphenol A, 50:50 Isosorbide, bisphenol A, 25:75

Mw (daltons)

Mn (daltons)

Tg ( C)

Elastic Modulus (Gpa)

Hardness (Mpa)

Yellowness Index

20,678

10,147

152.0

4.83

313.8

0.44

28,991

15,955

152.8

3.29

232.7

0.343

33,588

17,696

151.0

3.45

219.8

0.62

Note: Light transmittance exceeded 90% for all experimental agents and had high scratch resistance.

NOTES 1. Optically active poly[(isosorbide-co-bisphenol A) carbonate)], (II), was also prepared and consisted of 90% isosorbide and 10% bisphenol A with diphenyl carbonate and had an optical rotation of 140 with excellent scratch resistance.

O

O O

O

O

a

O

O O

b

O

(II) 2. Glasgow [1] prepared a blend consisting of the reaction product of bisphenol A and diphenyl carbonate with poly(caprolactone-b-dimethylsiloxane-b-polycaprolactone) terpolymer that showed superior resistance to scratching and haze while having excellent transmittance properties. Food and medical articles derived from this blend were readily sterilized by steam at atmosphere pressure as taught by Chatterjee [2].

720

Aliphatic Diol Polycarbonates and Their Preparation

3. Polycarbonates prepared by reacting phosgene and bisphenol A and capping with a perfluoroalcohol, (III), were prepared by Davis [3] and used as the surface layer of molded articles in flame retardant and weatherable articles. C9H17

O

O O

O O

O

(III)

O

O

O

O a

O

C9H17

O

4. McCloskey [4] prepared high molecular weight polymer carbonates consisting of bis(methyl salicyl) carbonate, bisphenol A, and an oligomeric carbonate of methyl salicylate using the transesterification catalyst, tetrabutylphosphonium acetate. 5. Boven [5] prepared polycarbonates consisting of dimethyl bisphenol cyclohexane and phosphine. Copolymers of dimethyl bisphenol cyclohexane with bisphenol and interfacial phosgene, (V), were also prepared and were used as glass panes because they exhibited enhanced scratch and molecular weight degradation resistance.

O O

O

O O

(IV) References 1. 2. 3. 4. 5.

K. Glasgow et al., US Patent 7,135,538 (November 14, 2006) G. Chatterjee et al., US Patent Application 2006-0002814 (January 5, 2006) G.C. Davis et al., US Patent Application 2006-0135737 (June 22, 2006) P.J. McCloskey et al., US Patent Application 2006-0069228 (March 30, 2006) G. Boven et al., US Patent Application 2007-0009741 (January 11, 2007)

O

a

L. Poly(Silarylene-Siloxane-Acetylene)

Title: High-Temperature Elastomers from Linear Poly(Silarylene-Siloxane-Acetylene) Author:

T. M. Keller et al., RE39,428 (December 12, 2006) [formally US Patent 6,362,289]

Assignee:

The United States of America as represented by the Secretary of the Navy (Washington, DC)

SIGNIFICANCE Flexible and oxidatively stable thermosets were prepared by thermally curing linear poly(silarylene-siloxane-acetylene) elastomers at up to 450 C. Thermooxidative weight loss of 3.69% to 7.69% was observed for these crosslinked inorganic-organic hybrid polymers when isothermed at 350 C under air flow. REACTION Cl

Cl Cl

Cl Cl

HO Si

vi Postcuring Notes 1,2

i

Li

Li

ii

Si OH

v Curing

Si N

N Si

Cl

Intermediate iii

O Si O Si

HO Si

Si

Si

O

Si

Si O

3

O Si O Si

H

iv Intermediate

Si O

3

H

i: THF, butyl lithium ii: Dimethylaminodimethylchlorosilane iii: Bis(dimethylamino)dimethylsilane, toluene iv: Toluene, diethyl ether, 1,4-bis(dimethylaminodimethylsilyl)butadiyne 721

722

High-Temperature Elastomers from Linear Poly(Silarylene-Siloxane-Acetylene)

EXPERIMENTAL 1.

Preparation of Di-lithium 1,4-Butadiyne

A 250-ml Schlenk flask containing 20 ml of THFand 20 ml of 2.4M n-butyl lithium was cooled to 78 C and then treated dropwise with hexachlorobutadiene (12.0 mmol) over 10 minutes. After the addition was completed, the mixture stirred 3 hours at ambient temperature and used directly without purification. 2.

Preparation of 1,4-bis(Dimethylaminodimethylsilyl)Butadiyne

The entire Step 1 product was re-cooled to 78 C and treated dropwise with dimethylaminodimethylchlorosilane (24 mmol) and stirred 16 hours at ambient temperature. The mixture was concentrated, and the residue was dissolved in a small amount of pentane, filtered, and re-concentrated. The product was isolated in 96% yield. 3.

Preparation of Hydroxyl Terminated Silarylene-Siloxane Prepolymer

A mixture consisting of 1,4-bis(hydroxydimethylsilyl)benzene (11.7 mmol) and 10 ml of toluene was treated with bis(dimethylamino)dimethylsilane (8.81 mmol) and then refluxed until there was no evidence of dimethylamine evolution as determined using moist red litmus paper. The mixture was then refluxed an additional hour and used without further purification. 4. Preparation of High-Temperature Elastomer Precursor, Linear Poly(Silarylene-Siloxane-Acetylene) The entire Step 3 product was treated with a 4.0 ml of aliquot consisting of 5.0 ml of toluene containing the Step 2 product (3.28 mmol) and then refluxed for 1 to 2 hours. The mixture was next treated with 50 to 100 ml of toluene containing 1,4-bis (dimethylaminodimethylsilyl)butadiyne every 15 to 30 minutes until the viscosity of the solution visibly increased and dimethylamine evolution ceased. The mixture was concentrated, treated with excess diethyl ether, and washed twice with 100 ml of a saturated solution of NH4Cl; and the ethereal solution was dried using Na2SO4. Diethyl ether was vacuum removed, and the product was isolated in 67% yield. 5.

Thermal Curing

A platinum thermogravimetric analyzer pan containing 28.7410 mg of the Step 4 product was heated under nitrogen at 150, 200, 350, and 450 C for 60, 60, 120, and 120 minutes, respectively. After completion of the isothermal curing experiment, the sample was void free and exhibited the characteristics of an elastomeric material. IR (cm 1) 2074 (w), (–C.ident.C–C.ident.C–), 1052 (vs, broad), (Si–O) 1 H NMR (CDCl3) d 7.50 (s), (C6H4), 0.35 (s), 0.30 (s), 0.28 (s), 0.22 (s), 0.02 (s), (Si(CH3)2) 13 C NMR (CDCl3) d 140.7, 140.2, 132.2, (C6H4) 86.9, 85.3, (–C.ident.C–C.ident.C–), 2.11, 1.40, 0.96, 0.77,), (Si(CH3)2)

Notes

6.

723

Postcure Thermo-Oxidative Stability

Following the isothermal curing cycle in Step 5 the sample was cooled to ambient temperature and then further isothermed on a thermogravimetric analyzer for 120 minutes at 200, 250, 300, and 350 C in an air atmosphere with a 50 cc/min flow rate. In this experiment the plastic sample exhibited only a 3.69% weight loss as determined by TGA. DERIVATIVES No additional derivatives were prepared. TESTING RESULTS Si

Si

O

Si

O Si O Si

Si O

a b

H

TABLE 1. Physical and oxidative stability of poly(silarylene-siloxane-acetylene) elastomers after isothermal curing. n

Postcured Properties

Oxidative Stability (% weight loss)

0 1 2 3

Solid plastic material Soft and flexible Soft and flexible Soft and flexible

0.17 3.26 7.69 3.96

NOTES 1. Additional fexible and oxidatively high-temperature stable elastomers were prepared by the author [1,2] by thermal curing modified linear poly(silarylene-siloxane-acetylene) prepolymers, (I), and (II), respectively. Si

Si

O

Si

Si

O Si

Si

a

O

a=0–3

b

(I)

Si

Si

O

Si

Si

O Si

(II)

Si

O

Si

Si

O

a b

a=0–4

724

High-Temperature Elastomers from Linear Poly(Silarylene-Siloxane-Acetylene)

2. In earlier investigations by the author [3,4] high-temperature oxidatively stable eastomers containing 1,7-dodecacarboranyl (carborane), (III), or borate-terminated derivatives, (IV), respectively, were prepared that could be thermally crosslinked to a cured polymer or pyrolyzed to a ceramic surface.

Si O Si

Si

a

O

Si

a

Carborane

Si O Si

Carborane

b

c

a, b = 0, 1 c = 1– 10

(III) HO B

O

Si

a

O Si

Si

O

a

Si

(IV)

a>0

3. Rantala [5] prepared hybrid organic-inorganic polymers by condensing pentafluorophenyl-vinyl-dichlorosilane, (V), and pentafluorotrichlorosilane, (V), with water and then free radically initiating the mixture.

SiCl 2

SiCl 3

F5

F5 (V)

(VI)


T. M. Keller et al., RE39,332 (October 16, 2006) T. M. Keller et al., US Patent 6,787,615 (September 7, 2004) and US Patent 6,784,259 (August 31, 2004) T. M. Keller et al., US Patent 6,967,233 (November 22, 2005) T. M. Keller et al., US Patent 6,784,270 (August 31, 2004) J. Rantala et al., US Patent 7,144,827 (December 5, 2006)

CONTRIBUTORS

Academic Contributors Board of Regents, The University of Texas System (Austin, TX) Board of Trustees of the University of Illinois (Urbana, IL) Changchun Institute of Applied Chemistry Chinese Academy of Science (Changchun, CN) California Institute of Technology (Pasadena, CA) Centre National de la Recherche Scientifique (FR) Cornell Research Foundation, Inc. (Ithaca, NY) Ecole Polytechnique Federale de Lausanne (Lausanne, CH) Emory University (Atlanta, GA) Industrial Technology Research Institute (Hsinchu, TW) Korea Advanced Institute of Science and Technology (Daejeon, KR) Korea Institute of Science and Technology (Seoul, KR) Ministero dell ‘Universita’e della Ricerca Scientifica e Technologica (Rome, IT) National Institute of Advanced Industrial Science and Technology (Tokyo, JP) Ohio State University (Columbus, OH) Rensselaer Polytechnic Institute (Troy, NY) Research Foundation of State University of New York (Albany, NY) Rice University (Houston, TX) Seoul National University Industry Foundation (Seoul, KR) Simon Fraser University (Burnaby, CA) Societe de Conseils de Recherches et d’Applications Scientifiques (Paris, FR) University of Dayton (Dayton, OH) University of Florida Research Foundation, Inc. (Gainesville, FL) University of Hull (North Humberside, GB) University of Iowa Research Foundation (Iowa City, IA) University of Pittsburgh (Pittsburgh, PA) University of Southern Mississippi (Hattiesburg, MS) Virginia Tech Intellectual Properties, Inc. (Blacksburg, VA) Government Contributors Agency for Defense of Korea (Daejeon, KR) Agency for Science, Technology, and Research (Singapore, SG) Commissariat a L’Energie Atomique (Paris, FR) Japan Science and Technology Agency (Kawaguchi-shi, JP) Advances in Polymer Chemistry and Methods Reported in Recent US Patents, by Thomas F. DeRosa Copyright Ó 2008 by John Wiley & Sons, Inc. 725

726

Contributors

Laboratories d’Hygiene et de Dietetique (Chenove, FR) Los Alamos National Security, LLC (Los Alamos, NM) Secretary of State for Defense DSTL (Salisbury, GB) United States of America as Represented by the Secretary of the Air Force (Washington, DC) United States of America as Represented by the Secretary of the Navy (Washington, DC) Industrial Contributors Aerojet-General Corporation (Sacramento, CA) Agfa-Gevaert (Mortsel, BE) Akzo Nobel N.V. (Arnhem, NL) Alliant Techsystems, Inc. (Edina, MN) A.P. Pharma, Inc. (Redwood City, CA) Aquero Company (Eugene, OR) Arkema, Inc. (Philadelphia, PA) Arkema, Inc. (Puteaux, FR) Asahi Denka Company, Ltd. (Tokyo, JP) Asahi Kasei Kabushiki Kaisha (Osaka, JP) Baker Hughes, Inc. (Houston, TX) BASF Aktiengesellschaft (Ludwigshafen, DE) Bausch and Lomb, Inc. (Rochester, NY) Bayer MaterialScience AG (Leverkusen, DE) Biosphere Medical, Inc. (Rockland, MA) Borealis Technology Oy (Porvoo, FI) BP Chemicals, Ltd. (London, GB) Bridgestone Corporation (Tokyo, JP) Cambridge Display Technology, Ltd. (Cambridge, GB) Canon Kabushiki Kaisha (Tokyo, JP) Central Glass Co., Ltd. (Ube, JP) Chartered Semiconductor Manufacturing, Ltd. (Singapore, SG) Cheil Industries, Inc. (Kyeonggi-do, KR) Ciba Specialty Chemicals Corporation (Tarrytown, NY) Construction Research and Technology, GmbH (Trostberg, DE) Cyclics Corporation (Schenectady, NY) Daicel Chemical Industries, Ltd. (Sakai, JP) Daikin Industries, Ltd. (Osaka, JP) Dainippon Ink and Chemicals, Inc. (Tokyo, JP) Denki Kagaku Kogyo Kabushiki Kaisha (Tokyo, JP) Dow Global Technologies, Inc. (Midland, MI) DuPont de Nemours and Company (Wilmington, DE) Dupont Performance Elastomers, LLC (Wilmington, DE) Elsicon, Inc. (Newark, DE) Ethicon, Inc. (Somerville, NJ)

Contributors

ExxonMobil Chemical, Inc. (Houston, TX) Fidia Advanced Biopolymers s.r.l. (Abano Terme, IT) Fina Technology, Inc. (Houston, TX) Fujifilm Imaging Colorants Limited (Manchester, GB) Fuji Photo Film Company, Ltd. (Tokyo, JP) General Electric Company (Niskayuna, NY) General Electric Company (Pittsfield, MA) General Electric Company (Schenectady, NY) Goodyear Tire and Rubber Company (Akron, OH) Hammen Corporation (Missoula, MT) Hammersmith Imanet, Ltd. (London, GB) Hercules, Inc. (Wilmington, DE) Hitachi Chemical Company, Ltd. (Tokyo, JP) Hoffmann-La Roche, Inc. (Nutley, NJ) Honda Giken Kogyo Kabushiki Kaisha (Tokyo, JP) Honeywell International, Inc. (Morristown, NJ) Hyperion Catalysis International, Inc. (Cambridge, MA) Hynix Semiconductor, Inc. (Kyungki-do, KR) IM&T Research, Inc. (Denver, CO) Infineon Technologies AG (Munich, DE) International Business Machines Corporation (Armonk, NY) Invista North America S.a.r.l. (Wilmington, DE) Ivoclar Vivadent AG (Schaan, LI) Japan Science and Technology Corporation (Saitama, JP) Johnson and Johnson Vision Care, Inc. (Jacksonville, FL) JSR Corporation (Tokyo, JP) Kabushiki Kaisha Toyota Chuo Kenkyusho (Aichi-gun, JP) Kaneka Corporation (Settsu, JP) Kimberly-Clark Worldwide, Inc. (Neenah, WI) Korea Kumho Petrochemical Company, Ltd. (Chongno-gu, Seoul, KR) Landec Corporation (Menlo Park, CA) Life Therapeutics, Inc. (Clarkston, GA) Lumera Corporation (Bothell, WA) 3M Innovative Properties Company (St. Paul, MN) Matsushita Electric Industrial Company, Ltd. (Kadoma, JP) Merck Patent Gesellschaft (Darmstadt, DE) Michelin Recherche et Technique S.A. (Granges-Paccot, CH) Mitsui Chemicals, Inc. (Tokyo, JP) National Starch and Chemical Company Bridgewater, NJ) NEC Corporation (Tokyo, JP) Nektar Therapeutics (San Carlos, CA) Nektar Therapeutics AL Corporation (Hunstville, AL) Nissan Chemical Industries, Ltd. (Tokyo, JP) Nitto Denko Corporation (Osaka, JP) Nova Molecular Technologies, Inc. (Janesville, WI)

727

728

Contributors

Noveon, Inc. (Cleveland, OH) Ocutec, Ltd. (Glasgow, GB) Organic Vision, Inc. (Brossard, CA) Organon, Inc. (Oss, NL) Promerus LLC (Brecksville, OH) Rhodia Chimie (Aubervilliers, FR) Rhodia, Inc. (Cranbury, NJ) Samsung Electro-Mechanics Company, Ltd. (Suwon, KR) Sartomer Technology, Inc. (Wilmington, DE) Sekisvi Chemical Company, Ltd. (Osaka, JP) Shin-Etsu Chemical Company, Ltd. (Tokyo, JP) Shin-Etsu Chemical Company, Ltd. (Annaka-shi, JP) Shipley Company, LLC (Marlborough, MA) Sigma Laboratories of Arizona, LLC (Tucson, AZ) SmithKline Beecham Corporation (Philadephia, PA) Solvay Advanced Polymers, LLC (Alpharetta, GA) Solvay Solexis, S.p.A. (Milan, IT) South African Nuclear Energy Corporation, Ltd. (ZA) Sumitomo Chemical Company, Ltd. (Osaka, JP) Sun Bio, Inc. (Orinda, CA) SurfaTech Corporation (Dacula, GA) SurModics, Inc. (Eden Prairie, MN) Tosoh Corporation (Yamaguchi-ken, JP) Unimatec Company, Ltd. (Tokyo, JP) Xerox Corporation (Stamford, CT) Zyvex Corporation (Richardson, TX)

INDEX

Adhesives Biochips Poly[(lactide-g-butene)-g-poly(ethylene glycol)] as a hydrophilic and biodegradable adhesive, 69 Biocompatible adhesives a-Cyanoacrylate adhesives, 15, 19 Computer chips Polybenzoxazoles, 20, 21 Pressure sensitive adhesives Polymetharylate block terpolymers, 11 Automotive Tire hysteresis Covalently bound rubber additives bis-[2-(2Thiazolyl)-phenyl]disulfide, 8 Methyl-N-phenylnitrone, 6 4-(2-Oxazolyl)-phenylnitrone, 6 Thermoplastic resins useful as transparent resins in automotive components Polynorborene terpolymers containing ethylene and propylene, 692 Vulcanization methods Poly(styrene-co-butadiene) initiated with a thioacetal initiator and terminated with a vulcanization agent, 474 Battery Cathode for lithium secondary batteries Condensation product of N,N 0 -1,4-phenylenebis-thiourea with phenylene-1,4diisothiocyanate, 169 Electrodes Poly(3-hexyl)thiophene with high head-to-tail regioregularity, 158 Self-doped polyaniline graft copolymers, 93 Bioabsorbables polymers Conjugates Poly(ethylene oxide-co-glycidol-butyric acid conjugated with Grob-t and di-stearoyl phosphatidyl-ethanolamine, 48–49 Poly(ethylene oxide)-succinimidyl ester conjugated with AZT, T-20 polypeptide, and human erythropoietin, 52

Poly(ethylene oxide-co-propylene sulfide-co-ethylene oxide) conjugated with cysteine containing peptides, 76 Polymethoxypolyethylene oxide alkylaldehydes conjugated with IFNs-a, b, and , factors VII, VIII, and IX, insulin, or erythropoietin, 65 Diminished cytotoxicity Methoxypolypropylene glycol aldehyde drug delivery systems, 84 Poly(ethylene glycol-b-(lactide-coglycolide)) implants, 55 Drug delivery Amphiphilic poly(ethylene glycol-bvalerolactone) derivatives for delivery of water insoluble drugs, 44 Injectable thermosensitive biodegradable drug delivering system, 278 125 I-Polyacetals, 31 Polylactones for delivering LanreotideÒ, 35 Poly(ortho esters) with bioerodible matrices for the sustained release of medicaments, 61 Implants Coumarin end-capped absorbable polymers as in vivo implants, 72 High molecular weight poly(lactide-coglycolide), 557 Injectable implants, 55 Injectable thermosensitive biodegradable drug delivering systems, 278 Staples consisting of mercaptoethylaminemodified poly(monooleoyl glyceride-comaleic anhydride), 29 Polymer modification Free radical functionalization of polycaprolactone with poly(lactic-coglycolic acid), 80 Biocompatible materials Bone regeneration materials Polypyrrole films prepared using hyaluronic acid, 161


730

Index

Biocompatible materials (continued) Contact lenses Fumarate- and fumaramide-containing hydrogels, 265 High tensile strength poly(dimethylsiloxaneurea-propylene oxide), 25, 26, 27 Poly(2-hydroxethyl methacrylate) modified with methacrylate acid and glycerol methacrylate, 40 Hemocompatible Thromboresistant heparinized surfaces, 89 Bullet proof vests Heterocyclic rigid-rod polymers Benzobisthiazole-naphthalic fibers, 224 Polybenzazole fibers, 227 Catalysts Acyclic diene metathesis catalyst 1,3-Dimesityl-4,5-dihydroimidazol-2ylidene)benzylidene ruthenium(II) dichloride, 481 Ethylene polymerization catalysts Merrifield resin containing grafted carborane trianion, 566 Nickel(II) dibromide salts, 546 Siloxy/zirconium derivatives, 523 Zirconium metallocene derivatives, 542 Macromolecular depolymerizationrepolymerization catalysts 1,3-Diacetoxy-1,1,3,3-tetrabutyldistannoxane, 517 Tetraphenoxyl titanates, 520 a-Olefin polymerization 2,6-Di-(1,3,5-trimethyl-4-pyrazolyl) ethanimidoyl pyridine iron chloride procatalyst, 553 Merrifield resin containing grafted carborane trianion, 566 Norbornene polymerization Mixture comprising palladium acetate, tricyclohexylphosphine, dimethyl zinc, and hexafluoroisopropanol, 569 Transesterification method for preparing polybranched polyesters Tin(di(chlorodimethylsiloxy)tinchlorodimethylsilane), 406 Ziegler–Natta catalysis Preparation of high cis poly(1,4-butadiene) using neodymium versatate as the cocatalyst, 539, 540 Charge transport materials Donor acceptor polymeric complexes 1,3-Dinitrobenzeneandpoly(9-hydroxymethyl9-fluorene carboxylic acid), 156

Liquid crystal displays Low molecular weight [2,3-b]thienothiophene derivatives, 196 Chain transfer polymerization agents Acrylic acid, butadiene, and styrene terpolymerization 1-Benzyl-2,5-cyclohexadiene-1-carboxylic acid, 577 Acrylonitrile Cumenyl thiobenzoic acid, 714 Chloroprene Dithiocarbamic esters, 492 N,N-dimethylacrylamide N,N-Dimethyl-Sthiobenzoylthiopropionamide, 588 2-Ethylhexylacrylate S,S0 -bis-(a,a0 -dimethyl-a 00 -acetic acid)trithiocarbonate, 584 2-Hydroxyethyl methacrylate 1,1-Diphenylethylene, 575, 595 Methacrylic acid 1,4-Dimercaptobutane-2,3-diol, 581 Reactivation of polymethyl methacrylate polymerization bis(Ethoxythiocarbonyl)disulfane, 511 Tetrafluoroethylene Chloroform, 238 Ethane, 237 Crosslinking agents Degradable N,N0 -(Dimethacryloyloxy)glutarylamide and derivatives, 274 Superabsorbent swellable hydrogels Crosslinked polyethers capped with acrylic acid, 262 Dispersion Aqueous Oligomeric ethylene oxide phosphonic acid derivatives, 105 Non-aqueous nanotube dispersant Noncovalent dispersion of nanotubes using electron donor/electron interactions acceptor characteristics of the polymer backbone, 351 Dental cements Pre-cured cement paste Low shear viscosity UV curable dental composite containing of 1,3,5-oxadiazine2,4-dione trimethacrylate, 133 Visible light curable diacrylate derivatives which have small polymerization shrinkage and high X-ray contrast properties, 138

Index

Dielectric constant materials Low dielectric constant polymeric agents Poly1,3-butadiynyl derivatives, 150 Elastomers Perfluoro elastomers containing hydroxyl cure sites Basic hydrolysis of poly(tetrafluorene-coperfluoro(methylvinyl ether)-co-vinyl acetate), 241–242 Very low surface energy elastomers Oxetanes containing 2,2,2-trifluoroethoxymethyl substituents, 244 Electroconductive Battery electrodes Poly(3-hexyl)thiophene with high head-to-tail regioregularity, 158 Electrically conducting artificial muscles Dibenzodiazocine polymers, 164 Electroconductive layer in a light-emitting diode 3,4-Alkylenedioxy-thiophene copolymers, 177 Film conductivity Polyaniline doped with di(butoxyethoxyethyl) ester of sulphosuccinic acid, 172 Electroluminescence Photovoltaic device Polyether containing polyaromatics and polyheteroaromatic, 185 Polyethylene-g-2-(7-benzothiazolyl-9,90 dioctylfluorene), 180 Electroluminescent materials Hole transport and electroluminescent agents Isotactic and syndiotactic poly(9-fluorenyl methacrylate), 147 Poly(methyl methacrylate-co-naphthyl carbamate) and pyrene polyamides, 144, 145 Emulsifing agent Polymeric Kraton G-1901Ò esterified with methoxypolyethylene glycol, 497 Emulsion Inverse emulsion Mixture consisting of paraffin oil, sorbitan monooleate, and poly(ethyleneoxide) fatty acid esters, 501 Energetic polymers Propellant binder and explosive Elastomers containing polyoxirane and polyoxetane blocks with azides, 220 Stable energetic binder Poly(glycidyl dinitropropyl formal), 217

731

Fibers Hydrophobic/oleophobic Vapor deposition of perfluoroacrylate onto nonwoven fabrics, 121 Heterocyclic rigid-rod polymers comprising ballistic vests Benzobisthiazole-naphthalic fibers, 224 Polybenzazole fibers, 227 Vapor-grown carbon nanofibers Dispersion of vapor-grown nanoscale tubes using 4-(2,4,6-trimethylphenoxy)benzoic acid, 339 Fluorine Very low surface energy polymers Polyoxetanes containing 2,2,2-trifluoroethoxymethyl substituents, 244 Gas chromatography columns Binding of biomacromolecules and metal ions Silica-g-polybutadiene-g-(polyamine), 663 Functionalized polymers for binding metal ions in aqueous solutions Poly(ethyleneimine-g-3,4-dihydroxysuccinimide) and related derivatives, 684 Selective binding of cysteine while remaining inert to lysine Poly(ethylene glycol) chloroethyl sulfone and -vinyl sulfone, 665 Separation of racemic mixtures Optically active malimides prepared by condensing succinic anhydride with either (1R, 2R)- or (1S,2S)-2benzyloxycyclopentylamine, 669 Polysaccharides containing grafted 9Hfluorenyl- or 5-indanyl-carbamates, 678 Gels Cosmetic Hairspray consisting of crosslinked C6-, C12-, C14-, and C16-polyacrylates, 99 Polyethylene oxide urethane/urea hairspray containing casein, 129 Electrochemical processes Ferrocene amide polyethers, 255 Implants Thermosensitive implants, 55 Photogelation of coumarin ester end-capped polylactones, 72 Graft copolymers Anticorrosive Self-doped polyaniline graft copolymers, 93 Polyamide graft copolymers Poly(4-amino-benzoic acid-co-(cysteine-gpoly(n-butyl acrylate)), 59

732

Index

High-performance polymers Engineered thermoplastic with chemical resistance and favorable high temperature properties Poly(a-aromatic ketones), 705 High-performance resin with high heat resistance and high transparency Hydrogenated poly(1,3-cyclohexadiene-costyrene), 702 High temperature stable flexible thermosets Poly(silarylene-siloxane-acetylene) elastomers stable to 450 C with nominal weight loss, 721 High temperature injection moldable polymers Moderate molecular weight polyimide sulfones, 708 Poly(ethyl a-acetoxyacrylate) homo- and alkyl a-acetoxyacrylate copolymers, 687– 688 Ionomer resins with enhanced flex strength, elongation, and low melt flow index properties Styrene and zinc diacrylate copolymers, 699 Moderate molecular weight materials having very high glass transition temperatures Polyfluorene, polysulfonyl, and poly (fluorene-co-sulfonyl) copolymers, 689 Resins with enhanced light transmissions exceeding 90% with little or no haze Polycarbonates containing bisphenol A and isosorbide, 717 Resins with reduced water absorption used as molding components Polyformals and copolyformals thermosets, 695 Thermoplastic resins useful as transparent resins in automotive components Polynorborene terpolymers containing ethylene and propylene, 692 Thermoset Resins Benzoxazines prepared using o,p-Novolak resins, formaldehyde, and aniline, 712 Hydrogels Degradable crosslinked hydrogels N,N0 -(Dimethacryloyloxy)glutarylamide crosslinking agents and derivatives for 2hydroxyethyl acrylate, 272 Moderate strength copolymer hydrogel Linear urea-urethane block copolymer, 259 Oxygen permeable Fumarate- and fumaramide-containing hydrogels, 265

Superabsorbent swellable hydrogels Crosslinked polyethers capped with acrylic acid, 262 a,b-Poly aspartate sodium salt, 273 Ink jet printing Fixing agents Chain-extended thermoplastic guanidinium polymers, 289 Light emitting Light-emitting diodes 3,4-Alkylenedioxy-thiophene copolymers, 177 Crosslinkable perfluorinated bisphenol A polymeric derivatives, 190 Liquid crystals Biaxial liquid crystals Oligomeric phenylacetylene liquid crystalline derivatives, 307 Liquid crystal aligners Polyimides spin-coated with g-butyrolactone and N-methylpyrrolidone, 293 Polyimides containing pendant 2-butenyl substituents, 299 Nematic liquid crystal materials Perfluoroalloxy aromatic derivatives, 316 Photo-inducable birefringence Polymethacrylates containing azo substituents, 303 Processable, high tensile strength, and low melt viscosity Polynaphthyl esters, 318 Macromonomers S-(Poly(n-butyl acrylate)-cysteine, 58 Polyethylene-methylmethacrylate, 59 Magnetic resonance Imaging contrast-enhancing agents Polypeptide imaging agents containing gadolinium(III) diethylenetriamine pentaacetic acid, 283 Mechanical strength Adhesives and membranes High tensile strength poly (dimethylsiloxane-urea-propylene oxide), 26, 27 Enhancing polyolefin strength Incorporation of 0.02 mol% norbornene-2,3-dicarboxylic acid anhydride, 560

Index

High strength fluorinated terpolymer Terpolymers consisting of tetrafluoroethylene, perfluoro(ethyl vinyl ether), and perfluoro (propyl vinyl ether), 234 Moderate strength copolymer hydrogel Linear urea-urethane block copolymer, 259 Membranes Hydrophobic Poly(dimethyl ketone) as industrial packaging for water-containing foods, 117 Membrane blend of dithiolene and perfluoro polyphthalimide Selective removal of propene from propene/ propane streams, 531 Membranes having broad pore size ranges and restricted pore size distribution Polyvinyl alcohol membrane crosslinked with glutaraldehyde for use in separating proteins, 675 Nanofibers Inorganic Spiral shaped hollow silicon oxide nanofibers, 347 Vapor-grown carbon nanofibers Dispersion of vapor-grown nanoscale tubes using 4-(2,4,6-trimethylphenoxy)benzoic acid, 339 Nanoparticles Catalytic agents Nanotubes functionalized with Wilkinson0 s complex, 333 Drug delivery Nanoparticles derived from poly(ethylene glycol-b-valerolactone) derivatives, 44 Inorganic nanotubes Pyrolysis of 1-(ferrocenylethynyl)-3(phenylethynyl)benzene thermosets as a method for preparing iron nanoparticles, 344 Nanotubes Dispersants Carbon nanotubes electrochemically derivatized with diazonium 4-alkylaromatics, 329 Noncovalent dispersion of nanotubes using electron donor/ acceptor interactions characteristic of the polymer backbone, 351 Enhanced mobilities and transconductance properties Nanotubes functionalized with Wilkinson0 s complex, 333

733

Enhanced water solubility Multi-walled nanotube amidated with guanidine containing polystyrene-gdibenzo-18-crown-6-ether, 325 Oxidation reactions Introduction of carboxylic acids on nanotubes using ammonium persulfate and sulfuric acid, 336 Nonlinear optical chromophores Light-emitting diodes Crosslinkable perfluorinated bisphenol A polymeric derivatives, 192 Method of improving photorefractive efficiencies Composition consisting of C60 fullereneterminated polymethacrylate derivative, plasticizer, and a nonlinear chromophore, 458 Waveguides Polystyrene containing pendant thiophenes, 419 Oxidative stability Atomic oxygen-resistant materials for use in space exploration Polydiamantane derivatives containing phosphine oxide, 119 Fire resistant materials Polybenzazole derivatives, 227 Polymeric benzobisthiazole-naphthalic derivatives, 224 High temperature stable flexible thermosets Linear poly(silarylene-siloxane-acetylene) elastomers cured 450 C with around 7 weight loss, 721 Paint additives Latex paint Terblock methacrylate as viscosity index improver, 1 Marine paint Nontoxic polyacrylates containing pendant semifluorinated substituents, 108 Photoactive materials Curing agents Benzophenone s-triazine derivatives, 112 Photoactive coumarin end-capped polymers, 72 Photo-inducable birefringence Polymethacrylates containing azo substituents, 304 Photoluminscence Blue and blue-green spectral emission materials Fluorene copolymers containing pyrrole, 432

734

Index

Photoluminscence (continued) High efficiency Biphenyl copolymers containing a cyclic bidentate iridium substituent, 427 Lower power consumption with higher brightness and ease of material processing Poly(thiophene-co-fluorene) derivatives, 437 Solvent-soluble light-emitting agents Conjugated fluorene block, co-, and terpolymers, 448 Conjugated poly(fluorene-oxadiazole) polymers, 453 Photorefraction Method of improving photorefractive efficiency Composition consisting of C60 fullereneterminated polymethacrylate derivative, plasticizer, and a nonlinear chromophore, 458 Photoresists Anti-reflective coating and photoresist pattern Crosslinked product of polysuccinic anhydride and polyvinyl dimethylacetal, 125 Chemical amplification type resist composition Perfluoroacetal or perfluoroketal polymethacrylates containing norbornene substituents, 611 Photoresist compositions effective in the 193 and 157 nm useful in photolithography and having enhanced etch resistance Norborene lactones and sultones copolymers, 632 Photoresists useful in multilayer resist systems that provide contrast upon exposure to photogenerated acid Norborene silsesquioxanes copolymers, 636 Photoresist compositions that are transparent to irradiation at 160 nm or less Polymerizable perfluoro norbornene, 623 Positive and negative tone photoresist compositions activated at 193 nm Solvent-soluble fluoroacrylates copolymers, 627 Positive photosensitive composition effective at 200 nm or less Diamantane acrylate terpolymers containing lactones and diadamantane, 651 Positive resists sensitive to electron beams or deep UV radiation Adamantane methacrylates terpolymers having lactone substituents, 642 Adamantane 4-hydroxyphenyl methacrylates copolymers, 647 Resist compositions and patterning process suitable for deep UV lithography Fluoro vinylsulfones terpolymers, 616

Polymer fractionalization Poly(2-hydroxethyl methacrylate-comethacrylic acid) using ethanol and n-hexane, 41 Polymerization methods Anionic Anionic polymerisation of oxiranes without the use of crown ethers or cryptands, 463 Amido-organoborate initiator systems, 465 Polyisocyanates end-capped with acyl chlorides, 478 Preparation of high molecular weigh poly(a)-methylstyrene using sec-butyl lithium, 472 Atom transfer radical polymerization Polymerization of styrene using ethyl 2bromo-isobutyrate, 596 Cationic Polymerizing of liquefied isobutylene using 1,2-bis(9-bora-1,2,3,4,5,6,7,8octafluorofluorenyl)-3,4,5,6tetrafluorobenzene, 487 Terpolymerization of THF, 3-ethyltetrahydrofuran, and ethylene oxide using NAFIONÒ NR-50 acidic resin, 489 Critical polymerization Polymerization of vinylidene fluoride above its critical density and temperature, 231 Free radical Dithiocarbamic-5-oxo-4,5-dihydro-oxazole derivatives, 606 Macromolecular photoinitiators containing polyisobutylene, 507 Polymerization of perfluoromonomers using perfluorodiacylperoxides, 504 Nitric oxide mediated N-Alkoxy-4,4-dioxy-polyalkyl-piperidines, 600 t-Butyl 1-diethylphosphono-2,2dimethylpropyl nitroxide, 1 Nitric oxide, 595 Phenyl-t-butylnitrone, 595 Spiro-ketal nitroxide, 592 Photolytically mediated Polymerization using diethanolamine with methylene blue, 605 Reactivatable polymerization Reactivatable polymethyl methacrylate using bis(ethoxythiocarbonyl)disulfane as the chain transfer agent, 511 Reactivatable poly(styrene-co-maleic anhydride) with 2,2,6,6-tetramethyl-1piperidinyloxy, 514

Index

Reversible addition–fragmentation chain transfer Block copolymers of acrylonitrile and butyl acrylate using cumenyl thiobenzoic acid, 714 Low molecular weight polystyrene using dibenzyl trithiocarbonate, 596 Preparation of low polydispersity poly(N,Ndimethylacrylamide) using N,N-dimethylS-thiobenzoylthiopropionamide, 588 Ring-opening metathesis polymerization Catalyst comprising bis(tricyclohexylphosphine)benzylidine ruthenium(IV) dichloride, 529 Use of ruthenium salts in preparing high A,Balternating copolymers, 533 Semiconductors Enhanced mobilities and transconductance properties Nanotubes functionalized with Wilkinson0 s complex, 333 Film transistors Polythiophenes, 205 Poly(fluorene-co-thiophene), 209 Insulator films Polyarylene ethers, 201 Liquid crystal displays Low molecular weight [2,3-b]thienothiophene derivatives, 196 Silicon Fluids Water and oil repellency with weather, solvent, and chemical resistance Cyclic siloxane compounds containing an unsaturated substituent, 247 Surfaces Biological Thromboresistant heparinized surfaces, 89 Cosmetic Hair sprays consisting of crosslinked C6-, C12-, C14-, and C16-polyacrylates, 99 Polyethylene oxide urethane/urea derivatives containing casein, 129 Mechanical Oxyfluorination for improving shear bond strength, 97 Very low surface energy Acrylate fluorocyclic silanes furniture polish additives, 102

735

Polyoxetanes containing 2,2,2-trifluoroethoxymethyl substituents, 244 Surfactants Very low surface tension Perfluoro organosilicons, 251 Synthetic methods Aniline formaldehyde oligomers, 384 Biodegradable aliphatic polyesters by deglycolation, 371 Cysteine graft copolymers containing S-poly (n-butylacrylate), 395 N,N0 -Dialkylpolyvinylamines using poly(Nvinylformamide), 409 Guerbet polymers, high molecular weight, 398 Hydroaminomethylation of polyolefins, 373 Method for preparing high trans content poly (styrene-co-butadiene) using barium salt of tri(ethyleneglycol)ethyl ether, 469 Method for preparing vinyl-rich polybutadiene rubber using iron isooctanoate, 467 Multistar polystyrene containing 34 arms, 417 Natural and unnatural oligonucleotide preparation, 413 Nonsymmetrical peroxides, 367 Perdeuterated polyiimides, 376 Permutational synthesis of new heterocyclic amines, 362 Poly(aniline-co-thiophene), 381 Polybutadiene (meth)acrylates, 379 Polyether maleimides, 386 Poly(9-fluroenone), 389 Poly(1,4-phenylene vinylene) derivatives, 401 Polypropylene containing high graft levels of succinic anhydride without viscosity increase, 392 Preparation of high cis-1,4-polyisoprene using neodymium tris(bis(2-ethylhexyl)phosphate), 550 Preparation of polypropylene-gperfluoroacrylate by vapor deposition of perfluoroacrylate monomer, 122 S-Poly(n-butylacrylate)cysteine macromonomer, 395 Solid state synthesis of 18Ffluorobromomethane, 357 Suzuki method for polymerization of aromatic monomers, 444

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