Patent Applications: A Tool for Identifying Advances in Polymer Chemistry R & D

PATENT APPLICATIONS A Tool for Identifying Advances in Polymer Chemistry R & D THOMAS F. DEROSA PATENT APPLICATIONS ...

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PATENT APPLICATIONS A Tool for Identifying Advances in Polymer Chemistry R & D THOMAS F. DEROSA

PATENT APPLICATIONS

PATENT APPLICATIONS A Tool for Identifying Advances in Polymer Chemistry R & D THOMAS F. DEROSA

Copyright # 2009 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. Patent applications : a tool for identifying advances in polymer chemistry R & D / Thomas F. DeRosa. p. cm. Includes index. ISBN 978-0-470-47228-6 (cloth) 1. Polymers–Research. 2. Patents. I. Title. QD381.D474 2009 668.9072–dc22 2009005634 Printed in the United States of America 10 9

8 7

6 5

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Dedicated to my wife, Barbara for her patience and emotional support in the preparation of this book

CONTENTS

Preface . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . ..

xi

Introduction .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. xiii

I.

ADDITIVES A. B. C. D. E. F. G. H. I.

II.

Ink Dispersants . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Ink Dispersants and Colorants . . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Oil Dispersants. . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Oil Drilling Dispersants . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Fabric Additives . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Paint Additives. . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Paint Stabilizers . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Paper Additives . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Polymeric Additives . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. .

ADHESIVES A. Pressure Sensitive Adhesives .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . B. Surface Adhesives . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . C. Thermally Stable Adhesives . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . .

III.

81

CRYSTALLINE MATERIALS A. Liquid-Crystal Displays . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. .

V.

59 67 76

COSMETICS A. Topical. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. .

IV.

1 4 8 12 17 37 46 49 52

85

DYES A. Jet Printer Ink .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 111 vii

viii

Contents

VI.

ELECTRICALLY ACTIVE POLYMERS A. B. C. D. E. F.

VII.

Battery . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Conducting Polymers.. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Electrodes . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Photovoltaic Cells . . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Semiconductors . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Transistors . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. .

121 125 129 145 163 185

ENERGETIC POLYMERS A. Explosive Binder .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 191

VIII.

ENGINEERED PLASTICS A. B. C. D.

IX.

Blends . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Composites . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Crosslinking Agents . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . High-Performance Polymers . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. .

197 200 205 215

FIBERS A. High Strength .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 251

X. FUEL CELLS A. Fuel Cell Membranes. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 259 B. Proton Conducting. . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 262

XI.

IMPROVED SYNTHETIC METHODS A. Isocyanates . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 281 B. Organometallic Catalysts.. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 285

XII.

INITIATORS/MODIFIERS A. Free Radical Initiators . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 317 B. Free Radical Initiator Modifiers . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 322 C. Photoinitiators. . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 325

Contents

XIII.

ix

LIGHT-EMITTING POLYMERS A. Diodes . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 335

XIV.

MEDICAL POLYMERS A. B. C. D. E. F.

XV.

Biodegradable. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Biomaterials for Dental Applications . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Biomaterials for Diagnostics. .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Biomaterials for Drug Delivery Devices. . .. . . . .. . . .. . . . .. . . .. . . . .. . Biomaterials for Gene Therapy . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . Biomaterials for Membranes. .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. .

409 421 447 455 489 494

NITRIC-OXIDE-RELEASING AGENTS A. Antirestenosis Agents .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 499

XVI.

OPTICAL A. Intraocular Lenses . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 507 B. Optical Fibers . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 533 C. Optical Waveguides .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 536

XVII.

PHARMACEUTICALS A. Polypeptides.. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 541 B. Radiopharmaceuticals . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . 544

XVIII. PHOTORESISTS A. Resists . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 551

XIX.

PHOTOTHERAPY A. Oxygen Generators . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 599

XX.

RECORDING MATERIALS A. Anisotropic Films.. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 607

x

Contents

XXI.

STENTS A. Cardiovascular . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 613

XXII.

SUTURES A. Adsorbable . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 617

XXIII. TISSUE REPLACEMENT A. Tissue Engineering . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 621

XXIV.

VISCOELASTIC POLYMERS A. High Viscoelastic Materials. . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . 635

Contributors Academic Contributors . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. 641 Government Contributors. .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. 641 Industrial Contributors . . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. 642

Index . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. . . . .. . . . .. . . .. . . . .. . . .. . . . .. . . .. 645

PREFACE

There has never been a doubt that the US Patent and Trademark office consisting of a db of well over 7,500,000 records is one of the lesser utilized scientific resources. It is in this domain that the most commercially viable chemical/scientific inventions are described. In purely academic circles this db is shunned. From the moment a US Patent is filed, it may require two to five years before the document is issued as a Patent. Moreover, while only 70% of filed Applications issue as patents, the dominant reason is the chemistry of the Application is too current to that of the existing Patent. Nevertheless, the objective of this treatise is to provide the chemical researcher with a two to five “window” to assess the direction that industry/academia are pursuing. This work is further intended to allow chemical researchers the opportunity to avoid infringing on Applications and Patents. It is my intentions that the text of US Patent Application is easily followed and provides fruitful chemical leads and ideas. THOMAS F. DEROSA

xi

INTRODUCTION

The objective of this book is to identify and highlight significant state-of-the-art research in 24 active areas of polymer chemistry reported in current U.S. patent applications occurring in academic, government, and industrial centers. A further objective is to provide chemical researchers with descriptions of advances in these areas as well as detailing synthetic methods for preparing key intermediates and products provided from these technical centers. Wherever possible key references associated with each entry have been supplied to provide a chemical and evolutionary context for the reader. From its initial filing with the U.S. Patent and Trademark Office, a U.S. patent application issuing period is from 18 months to 5 years. Thirty percent of filed applications, however, do not issue as U.S. patents. While there are many reasons for this, the most cogent reason is that the application chemistry too closely resembles chemical material already described in an issued patent. U.S. patent applications that do not issue as U.S. patents are doomed to oblivion. In this book 24 academic and industrial subject areas of active research reported in U.S. patent applications are reviewed and summarized so that essential information is readily available to the researcher. The 24 polymeric categories include: Additives Cosmetics Dyes Energetic Polymers Fibers Improved Synthetic Methods Light-Emitting Polymers Nitric-Oxide-Releasing Agents Pharmaceuticals Phototherapy Stents Tissue Replacement

Adhesives Crystalline Materials Electrically Active Polymers Engineered Plastics Fuel Cells Initiators/Modifiers Medical Polymers Optical Photoresists Recording Materials Sutures Viscoelastic Polymers

It is impossible to determine with certainty whether a U.S. patent application will issue as a U.S. patent. Nevertheless relevant subject matter appearing in U.S. patents have been identified and reviewed to qualitatively gauge the patentability of U.S. patent applications contained in this book. The text format has been designed to be used as a reference and synthetic guide for polymer and organic chemists as well as for graduate students. The material described herein is not limited to polymer chemistry, however. In many instances—and with only marginal synthetic modifications—intermediates and products are readily

xiii

xiv

Introduction

convertible into agents outside the scope of this book. Extensive structural depictions of intermediates, products, and derivatives have been provided to allow the researcher to more easily visualize other material applications. Finally, I thoroughly enjoyed compiling this text and hope the reader finds it useful. THOMAS F. DEROSA

I. ADDITIVES A. Ink Dispersants a. Hyperbranched esters

Title: Method for the Production of Hyperbranched Water-Soluble Polyesters Author: Assignee:

Jean-Francois Stumbe et al. BASF Aktiengesellschaft (Ludwigshafen, DE)

U.S. Patent Application: Material Patentability: Anticipated Issuing Data: Research Focus:

Originality: Application: Observations:

20070293634 (December 20, 2007) Medium Mid-2010

Preparation of nondentrimeric hyperbranched polyesters that are watersoluble or water-dispersible from dicarboxylic acids and polyether polyols. Although dentrimeric hyperbranched polyesters have been reported in the patent literature, the agents in this application are novel. Ink dispersant This group has developed a single-step method for preparing ester-grafted hyperbranched polymers. These materials are not dentrimeric analogs, however. Although hyperbranched ureas, carbonates, and polyesters have previously been prepared, in this application water-dispersible or soluble linear polyesters containing pendant alcohols having acid numbers from 9 to 117 were produced. The single-step method for preparing these agents entailed condensing the oligomeric glycerol with selected dicarboxylic acids in the presence of either enzyme catalyst Novozymw435 or acid catalyst Fascatw.

Patent Applications: A Tool for Identifying Advances in Polymer Chemistry R & D. By Thomas F. DeRosa Copyright # 2009 John Wiley & Sons, Inc.

1

2

Method for the Production of Hyperbranched Water-Soluble Polyesters

REACTION

i. Adipic acid, Novozymw-435, toluene 1. Preparation of linear hyperbranched polyester using Novozymw-435 Adipic acid (0.60 mol) and an oligomeric glycerol having a repeat unit of three, PG-3 (0.44 mol), were dissolved at 708C in 80 ml of toluene and then treated with enzyme catalyst Novozymw-435 (14 g). The mixture was polymerized for 9 hours at 708C at 300 mbar to remove water formed during the reaction. The mixture was then concentrated and the product isolated as a honey-like, viscous, colorless to slightly yellowish polyester. The polyester was readily soluble in water.

DERIVATIVES A summary of water-dispersible or water-soluble linear polyesters prepared in this application containing hyperbranched alcohols and having acid numbers from 9 to 117 is provided in Table 1. Ester reactions were performed using either enzyme catalyst Novozymw-435 or acid catalyst Fascatw.

TABLE 1. Physical Properties of Selected Water-Soluble or Water-Dispersable Polyesters Prepared Using Enzyme Catalyst Novozymw-435 or Acid Catalyst Fascatw Entry 2 3 4 7 10 a

Reagents Adipic acid, PG-3, Fascatw Adipic acid, TMPEOa, Novozymw-435 Adipic acid, TMPEO, Fascatw Adipic acid, PG-3, stearic acid Phthalic anhydride, PG-3, Fascatw

Ethoxylated trishydroxymethylpropane.

Acid Number

Mw (Da)

Mn (Da)

117 9

2220 8000

1450 24,000

50 104 n.d.

2340 2300 n.d.

5860 3330 n.d.

Water Solubility Very good Good Good Dispersable Dispersable

Notes

3

NOTES 1. Additional hyperbranched polyesters based on either di-, tri-, or polycarboxylic acids or di-, tri-, or polyols are described by Bruchman et al. (1). For example, the reaction product of adipic acid, pentaerythritol and 1,4-cyclohexanedimethanol, was prepared using di-n-butyltin oxide as catalyst and then postreacted with selected diisocyanates and used as a paint additive. 2. By reacting hyperbranched polyesters with diethyl carbonate, Eipper et al. (2) prepared impact-modifing hyperbranched polyester – polycarbonates resins. 3. In an earlier investigation by the authors (3) hyperbranched polyamides were prepared by condensing adipic acid with polyamines at 1508C. 4. In related investigations hyperbranched polyureas and polycarbonates were prepared by Bruchmann et al. (4,5), respectively, while hyperbranched analogs containing ethylenically unsaturated substituents were prepared by the authors (6). References 1. B. Bruchmann et al., U.S. Patent Application 20070213501 (September 13, 2007). 2. A. Eipper et al., U.S. Patent Application 20070244227 (October 18, 2007). 3. J.-F. Stumbe et al., U.S. Patent Application 20070191586 (August 16, 2007). 4. B. Bruchmann et al., U.S. Patent Application 20070083030 (April 12, 2007). 5. B. Bruchmann et al., U.S. Patent Application 20060093885 (February 15, 2007). 6. J.-F. Stumbe et al., U.S. Patent Application 20070027269 (February 1, 2007).

B. Ink Dispersants and Colorants a. Azo-benzothiazole polyethers

Title:

Aqueous Inks Containing Colored Polymers

Author: Assignee:

Jeffery H. Banning et al. Xerox Corporation (Rochester, NY)

Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus: Originality: Application:

Observations:

20060074142 (April 6, 2006) High Mid-2008

Preparation of water-soluble organic ink colorants by incorporating chromophores onto oligomeric alkoxyethers. Very versatile synthetic design for water-solubilizing ink colorants. Jet printing ink Thermal ink jet process Two separate methods were used to solubilize colorants in an aqueous medium: a. Graft incorporation of the colorant onto a homophilic polymer substrate b. Incorporation of oligomeric hydrophilic substituents directly into the colorants The first method in this application, however, was limited to modifying alcohol-containing colorants onto polymers containing grafted succinic anhydride transesterification, and transaminated reactions were also reported. In the second method water-soluble colorants were prepared by azo coupling of colorants with alkoxyether functionalized aniline.

4

Derivatives

5

REACTION

i. Phosphoric acid, sulfuric acid, 2-ethylhexanol, 2-amino-4-methylbenzothiazole, nitrosyl sulfuric acid, sulfamic acid, POE(10)-N-ethyl aniline, urea, sodium hydroxide, CH2Cl2 EXPERIMENTAL 1. Preparation of water-soluble 4-methylbenzothiazole with alkoxyether functionalized aniline A vessel was charged with 85% H3PO4 (115 g), 95% H2SO4 (31 g), and 2 drops of 2-ethylhexanol. Stirring was then initiated and the kettle was placed in an ice/salt bath to cool the mixture to about 08C. This mixture was then treated with 2-amino4-methylbenzothiazole (10.2 g). A constant-pressure addition funnel was used to add nitrosyl sulfuric acid (21.7 g) dropwise over a period of about 1.5 hours and the mixture stirred an additional 90 minutes to ensure complete diazotization. Thereafter sulfamic acid (0.7 g) was added with stirring to neutralize any excess NOþ. The diazo mixture was then slowly added over 45 minutes to a 1-liter beaker containing ice, POE(10)-N-ethyl aniline (36.0 g), 150 ml water, and 2.0 g of urea. The mixture was then stirred at 08C for 2 hours followed by stirring at ambient temperature overnight. The diazo colorant was then neutralized to a pH of 7 using 50% aqueous NaOH while keeping the reaction temperature below 608C. Following neutralization, the colorant was poured into a 1-liter separatory funnel and allowed to phase separate. The bottom water/salt layer was discarded, and the colored organic product layer was isolated and dissolved in CH2Cl2 and then passed through a small plug of silica gel to remove any polar impurities. The methylene chloride layer was concentrated yielding a viscous red liquid.

DERIVATIVES

6

Aqueous Inks Containing Colored Polymers

NOTES 1. An alternative method for solubilizing a colorant through chemical grafting onto a functional polymer as indicated in Eq. (1) was also described in this application.

(1)

2. Additional colorant agents were previously prepared by the authors (1) and are described. 3. Beginning with quinizarin, Jaeger et al. (2) developed methods of making dimeric colorant agents as illustrated in Eq. (2).

(2)

i. 1,36-Hexatriacontane diisocyanate

Notes

7

4. An azo dye-colored composition, (I ), was prepared by Fujie et al. (3) in two synthetic steps and used as a heat-sensitive recording ink sheet.

5. A colorant containing a curable sulfonamide composition, (II), was prepared by Araki (4) and used on a support as a color filter.

References 1. J.H. Banning et al., U.S. Patent Application 20070123701 (May 31, 2007) and U.S. Patent Application 20060264674 (November 23, 2006). 2. C.W. Jaeger et al., U.S. Patent Application 20060178458 (August 10, 2006). 3. Y. Fujie et al., U.S. Patent Application 20080012930 (January 17, 2008). 4. K. Araki, U.S. Patent Application 20080014536 (January 17, 2008).

C. Oil Dispersants a. Polyacrylate amino succimides

Title: Alkyl Acrylate Copolymer VI Modifiers and Uses Thereof Author: Assignee:

Sanjay Srinivansan et al. Afton Chemical Corporation (Richmond, VA)

Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus: Originality: Application: Observations:

8

20080026964 (January 31, 2008) High Mid-2010

Preparation of polyacrylate viscosity improvers containing grafted N-phenyl-p-phenylenediamine as an antioxidant. Departure from using oil viscosity improvers based on poly(ethylene-copropylene)-g-succinic anhydride. Automotive oil viscosity improver Most automotive oil viscosity improvers are based on shear stable poly(ethylene-co-propylene) having Mn’s , 100,000 Da. Poly(ethyleneco-propylene) multifunctional viscosity improvers are prepared by free radical grafting of maleic anhydride and then imidizing with N-phenylp-phenylenediamine. While polymethacrylate viscosity index improvers are known, attempts to prepare them having a desirable balance of antioxidancy and high- and low-temperature viscometric shear stability have been elusive. This application has addressed that requirement.

Experimental

9

REACTION

i. Butyl methacrylate, lauryl methacrylate, maleic anhydride, lauryl mercaptan, 2,20 azoisobutyronitrile ii. N-Phenyl-p-phenylenediamine, ethoxylated lauryl alcohol

EXPERIMENTAL 1. Preparation of anhydride Butyl methacrylate, lauryl methacrylate, and cetyl methacrylate were combined with maleic anhydride, lauryl mercaptan, and process oil and then charged into a 2-liter reaction vessel equipped with two mixing impellers rotated at 300 rpm during the reaction. The mixture was preheated to 858C and then treated with 2,20 -azoisobutyronitrile and heated for 4 hours at 858C followed by 1 hour at 1008C. In some cases additional oil was added to make the product more easily pourable. Unreacted maleic anhydride and other low-molecular-weight products were removed by heating the reaction mass to 1208C while applying a vacuum. Reaction scoping results are provided in Table 1.

2. Preparation of imide The step 1 product was dissolved in process oil at 1358C and then treated with a mixture of N-phenyl-p-phenylenediamine and ethoxylated lauryl alcohol and further heated to 160– 1708C for 3 hours. The reaction mixture containing the multifunctionalized polymer reaction product was filtered where the nitrogen content was 0.36%.

10

Alkyl Acrylate Copolymer VI Modifiers and Uses Thereof

REACTION SCOPING TABLE 1.

Scoping Reaction for Preparation of Step 1 Producta Reagentsb

Entry 1 3 5 6

AIBN (wt%)

LSH (wt%)

MA (wt%)

BMA (wt%)

LMA (wt%)

CMA (wt%)

Mw (Da)

Mn (Da)

0.1 0.1 0.1 0.04

0.12 0.16 0.09 0.04

5.00 5.00 5.00 4.42

11.0 11.0 11.0 9.73

57.0 57.0 57.0 50.47

0.3 0.3 0.3 0.3

199,330 142,055 281,162 578,520

86,003 66,834 107,179 195,858

a

The viscosity index improver was prepared after reacting with N-phenyl-p-phenylenediamine. AIBN ¼ 2,20 -Azoisobutyronitrile, BMA ¼ butyl methacrylate, CMA ¼ cetyl methacrylate, LMA ¼ lauryl methacrylate, LSH ¼ lauryl mercaptan, and MA ¼ maleic anhydride.

b

TESTING High-Frequency Reciprocating Rig Film formation properties of lubricating fluids containing selected experimental VI improvers was determined using a high-frequency reciprocating rig (HFRR) according to the procedure outlined in SAE 2002-01-2793. Testing results are provided in Table 2. TABLE 2. HFRR Testing Results Reflecting Film Formation Properties of Polymers in the Presence of Abrasive Contaminantsa Carbon Black (%) 0 5 8

Comparative Example (%)

Imidized Entry 1 (%)

87 37 12

91 60 50

a

Higher results are preferred since it reflects a greater boundary film.

NOTES 1. In subsequent investigations by Loper et al. (1) and Mathur et al. (2) oil dispersant additives were prepared by reacting the step 1 product with triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and bis-aminopropyl piperazine. 2. Vinci et al. (3) prepared automotive oil viscosity index improvers that consisted of copolymers of C12 –C15 methacrylates with 2-ethylhexyl methacrylate and poly(ethylene-co-propylene) with 2-ethylhexyl methacrylate, then blended in 94.5 parts mineral oil.

Notes

11

3. Nanomaterials were used by Zhang et al. (4) as a replacement for polymer-based viscosity modifiers for automotive lubricants. Compared with traditional polymer-based viscosity modifiers, nanomaterials induce a more even viscosity increase across engine operating temperature ranges. In addition, nanomaterials provide a viscosity modifier that exhibits temporary shear loss that can contribute to fuel economy. References 1. J.T. Loper et al., U.S. Patent Application 20080027181 (January 31, 2008). 2. N.C. Mathur et al., U.S. Patent Application 20080026972 (January 31, 2008). 3. J.N. Vinci et al., U.S. Patent Application 20080015131 (January 17, 2008). 4. Z. Zhang et al., U.S. Patent Application 20070293405 (December 20, 2007).

D. Oil Drilling Dispersants a. Polymethacrylate betaines

Title: Zwitterionic Polymers Comprising Betaine-Type Units and Use of Zwitterionic Polymers in Drilling Fluids Author: Assignee:

Katerina Karagianni et al. Toyo Seikan Kaisha, Ltd. (Tokyo, JP)

Patent Application: Material Patentability: Anticipated Issuing Date: Observations:

12

20080045420 (February 21, 2008) Low 2010

The current application addresses the need for mineral agent inhibitors that prevent the aggregation of argillaceous rocks and prevent the swelling of clays during subterranean drilling. While acrylamide copolymers containing sulfobetaines or phosphobetaines are effective in addressing this problem, pollution concerns limit their application. Although this application has limited novelty since both (a) co-methacrylates and (b) betainelike materials terpolymer have previously been prepared, the use of these materials as drilling dispersants is novel.

Experimental

13

REACTION

i. a-Methoxy-v-methacrylate polyethylene glycol 1000, water, ethanol, ammonium persulfate

EXPERIMENTAL 1. Preparation of poly(sulfopropyldimethylammoniumethyl methacrylate-co-a-methoxy-v-methacrylate-polyethylene glycol) A reactor charged with sulfopropyldimethylammoniumethyl methacrylate (0.020 mol), a-methoxy-v-methacrylate polyethylene glycol 1000 (0.009 mol), water (398 g), and ethanol (261.90 g) was heated to 788C. The mixture was then simultaneously treated with ammonium persulfate (0.004 mol) dissolved in water (20 g) over 150 minutes, ammonium persulfate (2.5 g) dissolved in water (60 g) continuously over 120 minutes, sulfopropyldimethyl-ammoniumethyl methacrylate (0.182 mol) over 120 minutes, and a-methoxy-v-methacrylate polyethylene glycol (0.078 mol), and water (205.80 g). Thereafter the reaction was maintained at 708C for 90 minutes and then cooled. The solution was then treated with water and ethanol removed by distillation. The product was isolated with a solids content of 27.3%, a pH of 2, a Brookfield viscosity of 36 mPa . s, and an Mw of 65,000 Da with an Mn of 8000 Da.

14

Zwitterionic Polymers Comprising Betaine-Type Units and Use of Zwitterionic Polymers

DERIVATIVES TABLE 1. Selected Zwitterionic Polymers Containing Betaine-Type Units Used as Drilling Fluid Component

Entry

Repeat Unit

Brookfield Viscosity (mPa . s)

Mw (Da)

Mn (Da)

2

57,500

6500

31

4

30,000

4000

30

5

2,000,000

900,000

—

7

800,000

300,000

—

Notes

15

TESTING A. Recovery Test on the Cuttings Clay particles were used to simulate the cuttings having a size distribution between 2 and 4 mm. Sieved particles (30 g) were added to 350 ml of the test formulation containing the experimental agent. The flasks were placed in a rolling oven at 658C for 16 hours and then cooled and the particles recovered on a 2-mm sieve. Excess experimental agent was removed using absorbant paper. The particles were then weighed and dried in an oven at 508C until a stable weight was obtained. The particles were then reweighed and the percentage of moisture restoration calculated. High levels of restoration and low moisture contents are indicative of an inhibiting effect on clay swelling. Testing results are summarized in Table 2. TABLE 2. Recovery Test and Extrusion Testing Results for Selected Experimental Agentsa

Entry 4 4 2 Step 1 product 5 7 a

Dosage (%)

Moisture Content (%)

Moisture Restoration (%)

Pressure (bar)

1 3 1 1 1 1

29 33 28.7 — — —

99 94 101.4 — — —

26 35 36 55 29 33

High pressures and moisture restoration with low moisture content are preferred.

B. Extrusion Test Hot rolling particles from the recovery test on the cuttings were used. Samples were extruded in a CT 15 compressometer device at a rate of 40 mm/min where the pressure necessary to extrude the particles was recorded. The harder the particles, the higher the pressure, the better the protection with regard to penetration of water, and the better the inhibiting effect on clay swelling. Testing results are provided in Table 2.

NOTES 1. Cleaning compositions comprising polyether ammonium polymers, (I), were prepared by Schneiderman et al. (1) and used as a component in oil drilling compositions.

16

Zwitterionic Polymers Comprising Betaine-Type Units and Use of Zwitterionic Polymers

2. Oligomeric urea – formaldehyde resins prepared by Wright et al. (2) were as effective as surfactants in separating drill cuttings from oil drilling fluids. 3. Beckman et al. (3) prepared an oil drilling surfactant composition consisting of a resin blend of two 98% hydrolyzed polyvinyl alcohols where the viscosity of one of the resin components was at least 50% greater than the other. 4. Well drilling fluids having clay control properties were prepared by Hurd et al. (4) and consisted of the reaction product of tall oil and diethylenetriamine. 5. Orthoester derivatives (II), prepared by Funkhouser et al. (5) were effective as surfactants and used in oil drilling applications.

References 1. E. Schneiderman et al., U.S. Patent Application 20080045442 (February 21, 2008). 2. J.T. Wright et al., U.S. Patent Application 20080029460 (February 7, 2008) and U.S. Patent Application 20080017552 (January 24, 2008). 3. K.J. Beckman et al., U.S. Patent Application 20070284105 (December 13, 2007). 4. P.W. Hurd et al., U.S. Patent Application 20070167333 (July 19, 2007). 5. G.P. Funkhouser et al., U.S. Patent Application 20070066493 (March 22, 2007).

E. Fabric Additives 1. Antistatic Agents a. Polypropylene oxide ammonium salts

Title: Polyoxyalkylene Ammonium Salts and Their Use as Antistatic Agents Author: Assignee:

Patricia M. Savu et al. 3M Innovative Properties Company (St. Paul, MN)

Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus:


20080039654 (February 14, 2008) High 2010

Preparation of biodegradable salts derived from the reaction product of polypropylene ether amines and bis(perfluorobutylsulfonyl)-imine for use as antistatic agents. Two-year ongoing investigation. Antistatic agents for fabric and electronic devices In fabric applications there exists a need for fluorinated antistatic agents that exhibit a balance between thermal stability, hydrophobicity, and low volatility. To address this problem antistatic agents consisting of polyether amine salts of bis(perfluorobutanesulfonylimide were prepared having low volatility, minimal corrosion characteristics, and biodegradability greater than 99%. Antistatic agents were prepared in a single step in yields exceeding 90% by condensing polyether amines with bis(perfluorobutylsulfonyl)-imine. Bis(perfluorobutylsulfonyl)imide was prepared by reacting perfluorobutylsulfonylfluoride with triethylamine in the presence of ammonia followed by treatment with sulfuric acid.

17

18

Polyoxyalkylene Ammonium Salts and Their Use as Antistatic Agents

REACTION

i. Jeffaminew XJT-500, water

EXPERIMENTAL 1. Preparation of antistatic agent A reactor was charged with 96% active bis(perfluorobutylsulfonyl)imine (1.26 mol) dissolved in water (760 g) and then treated with Jeffaminew XJT-500 (0.66 mol) at 708C over 30 minutes. The mixture was stirred an additional 15 minutes and the pH adjusted to 7 – 8. The solution was then concentrated under reduced pressure and 1042 grams of product isolated as an amber honey-like liquid.

DERIVATIVES TABLE 1. Selected Polypropylene Ether Ammonium Salts Prepared Using Jeffaminew Polyether Amines and Bis(perfluoroalkylsulfonyl)imine

Entry

Jeffamine

Molecular Weight (Da)

1 2 6 7

XJT-500 T-406 XJT-506 XJT-500

600 440 — 600

Anion

Yield (%)

(C4F9SO2)2N2 (C4F9SO2)2N2 (CF3SO2)2N2 (CF3SO2)2N2

— — 91.7 99.7

Testing

19

TESTING TABLE 2. Concentration Effects on Surface Energy (dyn/cm) of Perflorinated Compounds and Step 1 Product Dosage

Agent C8F17SO3K (comparison) C4H9SO3K (comparison) C4H9SO2NKSO2C4H9 (comparison) Step 1 product

Surface Energy @ 0 ppm Treatment Level (dyn/cm)




72

67.68

54.09

33.17

72

70

67.5

53

72

61.85

41.61

34.02

72

34.3

33.4

28.6

TABLE 3. Surface Resistivity for Selected Antistatic Agents Dissolved in Methylethyl Ketone, Then Coated onto a Sheet of Polyester film at 6588 C

Entry Comparative 1 Comparative 2 Step 1 product Step 2 product Step 6 product Step 7 product

Surface Resistivity 1% MEK Solution (V/cm2)

Surface Resistivity 6% MEK Solution (V/cm2)

1.6 109 1.5 1012 8.5 109 2.4 1010 1.6 109 1.2 109

1.5 1011 1.6 1012 3.1 109 1.5 1011 7.8 109 3.7 108

TABLE 4. Bioelimination Properties of Selected Perfluorosulfonates and Step 1 Product Residual Sulfonate (ppm) Sulfonate

Day 1 (remaining)

Day 14 (remaining)

Day 28 (remaining)

C8F17SO2 3 C6F17SO2 3 Step 1 product

419 + 86 327 + 52 3.09 þ 1.58

309 + 34 61.9 + 11.7 0.126 þ 0.014

237 + 25 36.3 þ 7.7 0.025 þ 0.02

20

Polyoxyalkylene Ammonium Salts and Their Use as Antistatic Agents

NOTES 1. Jeffaminesw are materials that contain polypropylene glycol, poly(ethylene oxide-b-propylene oxide), or poly(propylene oxide-ethylene oxide-bpropylene oxide), which contain an amine terminus. 2. Additional polyetheramine antistatic agents are described by the authors (1) in an earlier investigation. 3. Antistatic agents consisting of trimethylalkylammonium halides such as trimethylhexadecyl ammonium chloride were used by Iyama et al. (2) in coatings on plastic plates. 4. The antistatic agent, N-di-[3-(stearoylamino)propyl]-N-methylamine oxide, (I), was prepared by Baik et al. (3) and used as a fabric softer in fabric detergent compositions.

5. A block copolymer consisting of poly(ethylene-b-butene) oligomer and N,N0 -dimethylpyrrolidinium chloride, (II), was prepared by Koroskenyi et al. (4) and used as an antistatic on polymeric finishs.

6. Polyetheresteramide antistatic agents consisting of the reaction product of undecanoic acid, hexamethylenediamine, dodecanedioic, and ethylene glycol were prepared by Linemann et al. (5) and blended with thermoplastic resins to form “breathable” polymer compositions.

References 1. P.M. Sauv et al., U.S. Patent Application 20080033078 (February 7, 2008). 2. H. Iyama et al., U.S. Patent Application 20080045636 (February 21, 2008). 3. I.S. Baik et al., U.S. Patent Application 20080039655 (February 14, 2008). 4. B. Koroskenyi et al., U.S. Patent Application 20080033115 (February 7, 2008). 5. R. Linemann et al., RE39,994 (January 1, 2008).

2. Coatings a. Polyaromatic urethanes

Title: Polymer Compositions of Carbonyl-Hydrated Ketone-Aldehyde Resins and Polyisocyanates in Reactive Solvents Author: Assignee:

Patrick Gloeckner et al. Degussa AG (Duesseldorf, DE)


20080027156 (January 31, 2008) High Mid-2010

Preparation of polyurethane coatings consisting of carbonyl-hydrogenated ketone and aldehyde resins and polyisocyanates. Ongoing investigation in preparing Norrish I and II inactive coatings. Fabric and film coatings A common feature of radiation curable products containing carbonyl function are Norrish type I or II degradation reactions. This group has addressed this concern by hydrogenating ketones in the base-catalyzed condensation of acetophenone and formaldehyde. In addition hydrogenated phenol-formaldehyde/mixed aldol condensation resins were also resistant to yellowing.

21

22

Polymer Compositions of Carbonyl-Hydrated Ketone-Aldehyde Resins

REACTION

i. Isophorone diisocyanate, 2,6-bis(tert-butyl)-4-methylphenol, dibutyltin dilaurate, acetone

EXPERIMENTAL 1. Preparation of crosslinked polyurethane The hydrogenated resin of acetophenone and formaldehyde (400 g, Mn 1000 Da) was condensed with isophorone diisocyanate (90 g) in the presence of 0.2% (on resin) 2,6-bis(t-butyl)-4-methylphenol and 0.1% of dibutyltin dilaurate (on resin) in 40% dilution with acetone. The mixture was refluxed until an NCO number of less than 0.1% was reached. The product was then isolated and had a melting range of from 171 to 1768C after the removal of acetone.

DERIVATIVES Only the step 1 product was prepared.

TESTING Resin solutions were prepared by mixing selected components illustrated in Table 1 with 1.5 wt% Darocur 1173 and then drawing down onto a glass plate using a doctor’s blade. The films were then cured using a 70 W ultraviolet (UV) light mercury lamp with an optical filter at 350 nm for approximately 16 seconds.

Notes

23

Sample Preparation TABLE 1. Sample preparation for Experimental Resin Compositionsa Component b

UV-20 (basic resin) Acetophenone– formaldehyde resin (unreduced ketone) Acetophenone– formaldehyde resin (reduced alcohol) Tripropylene glycol diacrylate

Sample A

Sample B

Sample C

100 —

60 40

60 — 100

40

64

4

a Each material was evaluated for enhance initial drying rate, gloss, and hardness or scratch resistance. b UV 20 ¼ Adduct of trimethylolpropane, isophorone diisocyanate, Terathane-650, and hydroxyethyl acrylate as a 70% strength solution in tripropylene glycol diacrylate.

TESTING TABLE 2. Physical Properties of Resin Compositions after Sample Exposure to UV Radiation for 16 seconds Testinga Entry A B C

FT (mm)

EC (mm)

HK (s)

Peugeot Test

MEK Test

Flow

30 –37 30 –33 30 –36

7 6 6.5

115 163 192

þþ þþ þþ

.150 .150 .150

Minimally Good flow Good flow

EC ¼ Erichsen cupping, FT ¼ film thickness, HK ¼ Konig pendulum hardness, MEK test ¼ resistance to butanone, and Peugeot test ¼ premium-grade gasoline resistance. a

NOTES 1. Cyclohexanone– formaldehyde resins, (I), were previously prepared by the author (1) and used in resin compositions having enhanced hardness. Cyclohexanol – formaldehyde resins, (II), were also prepared by the author (2) by hydrogenation of phenol –formaldehyde resins.

24

Polymer Compositions of Carbonyl-Hydrated Ketone-Aldehyde Resins

2. Baumgart et al. (3) prepared scratchproof, radiation-curable film-forming coatings by condensing siloxane tetraol, hydroxylethyl acrylate, and hexanediol diacrylate with excess hexamethylene diisocyanate catalyzed by dibutyltin dilaurate. 3. Radiation-curable liquid resin compositions were prepared by Takahashi et al. (4) consisting of the reaction product of 2,4-toluene diisocyanate, polypropylene oxide with an Mn of 2000 Da, and hydroxyethyl acrylate catalyzed by dibutyltin dilaurate. Products were used to coat optical fibers and as optical fiber ribbons.

References 1. P. Gloeckner et al., U.S. Patent Application 20060074217 (April 6, 2006). 2. P. Gloeckner et al., U.S. Patent 7,199,166 (April 3, 2007) and U.S. Patent 7,329,710 (February 12, 2008). 3. H. Baumgart et al., U.S. Patent Application 20080041273 (February 21, 2008). 4. A. Takahashi et al., U.S. Patent Application 20070191505 (August 16, 2007).

3. Hydrolysis Stabilizers a. Polypropylene oxide aromatic amide-urethanes

Title: Macrocyclic Carbodiimides (MC-CDI) and Their Derivatives, Syntheses, and Applications of the Same Author: Assignee:

Shenghong A. Dai et al. Great Eastern Resins Industrial Company, Ltd. (Taichung City, TW)


20080161554 (2003) Very high December, 2010

Method of preparing poly(amide-urethane) derivatives by ring-opening polymerization of macroscopic dicarbodiimides. New and novel macrocyclic monomers and polymers. Fiber hydrolysis stabilizer Polypropylene oxide macrocyclic carbodiimides were prepared by condensing with 2,4-toluene diisocyanate under high dilution with propylene glycol in the presence of 1,3-dimethyl-3-phospholene oxide. When the macroscopic diimide was postreacted with water and acetic acid, the urea acyclic acyl intermediate was generated. When further reacted with adipic acid or trimellitic anhydride, the corresponding poly(amide-urethane) and poly(urethane imide), respectively, were generated.

25

26

Macrocyclic Carbodiimides (MC-CDI) and Their Derivatives

REACTION

i. 2,4-Toluene diisocyanate ii. Toluene, 1,3-dimethyl-3-phospholene oxide iii. Acetic acid, ethanol

EXPERIMENTAL 1. Preparation of prepolymer containing isocyanate termini In a 250-ml three-necked flask, polypropylene glycol (0.02 mol) and 2,4-toluene diisocyanate (0.042 mol) were added and reacted under conditions provided in Table 1. When the reaction was completed, all products were isolated as transparent colorless liquids. TABLE 1. Reaction ID T2P192 T2P400 T2P700 T2P2000 a

Reaction Conditions Used in Preparing Step 1 Productsa Polypropylene Glycol (Mn)

Temperature (8C)

192 400 700 2000

45 50 50 65, 70

Reaction Time (minutes)

In all cases equimolar amounts of toluene diisocyanate and polypropylene oxide were used.

50 40 30 (65) 15 (70)

Physical Properties and Derivatives

27

2. Preparation of macrocyclic carbodiimides The step 1 product was diluted with 1500 ml toluene to a final concentration of 0.013 mol/L. The mixture was then treated with 1,3-dimethyl-3-phospholene oxide and heated to 908C while the cyclization reaction was monitored by Fouier transform infrared (FTIR). When the characteristic—NCO peak was eliminated in the macrocyclic carbodiimide (2134 cm21), the reaction was stopped, concentrated, dried, and the crude product isolated. The crude product was purified by liquid column chromatography on silica gel using either ethyl acetate or ethyl acetate/n-hexane, 9:1, respectively, and the product isolated. 3. Preparation of macroscopic acylurea The step 2 product was dissolved in 30 ml xylene containing acetic acid and the temperature slowly increased while monitoring the ring-opening reaction using FTIR. After heating to 1408C the solution was slowly treated with excess anhydrous ethanol. The solution was then stirred for an addition 30 minutes, concentrated, and the product isolated.

PHYSICAL PROPERTIES AND DERIVATIVES Physical properties for step 2 macrocyclic carbodiimides are provided in Table 2. TABLE 2. Physical Properties of Step 2 Macrocyclic Carbodiimides Prepared by Ring Closure of Step 1 Product Using 1,3-Dimethyl-3-phospholene Oxide

Sample CDI-T2P192 CDI-T2P400 CDI-T2P700 CDI-T2P2000

Cyclization Time (h)

Yield (%)

21 18 20 27

60 67 40 18

Appearance

Melting Point (8C)

Polyether Segment Tg (8C)

Faint yellow powder crystal Faint yellow colloid Faint yellow colloid Faint yellow colloid

80.5–85.2 16 and 22 — —

18.0 6.7 3.8 249.0

28

Macrocyclic Carbodiimides (MC-CDI) and Their Derivatives

NOTES 1. Poly(amide-urethane)derivatives, (I), were also prepared by reacting adipic acid with the step 2 product as illustrated in Eq. (1).

(1)

i. Adipic acid ii. Ethyl alcohol 2. In an earlier investigation by the authors (1) aryl N-acylureas were prepared and converted into polyamide-imides, (II), by heating to 1208C.

3. Water-dispersible polyisocyanate compositions containing polyethylene oxide were previously prepared by the authors (2) and used as aqueous resin adhesives. 4. Imashiro et al. (3) prepared polycarbodiimides using 4,40 -dicyclohexylmethane diisocyanate terminated with moisture-resistant diisocyanates.

References 1. S.A. Dai et al., U.S. Patent Application 20070282078 (December 6, 2007). 2. S.A. Dai et al., U.S. Patent 6,838,516 (January 4, 2005). 3. Y. Imashiro et al., U.S. Patent 5,889,096 (March 308, 1999) and U.S. Patent 5,912,290 (June 15, 1999).

4. Stain Repellants a. Polyfluorinated poly(4-vinylpyridine)

Title: Hydrophobic Fluorinated Polyelectrolyte Complex Films and Associated Methods Author: Assignee:

Joseph B. Schlenoff Florida State University Research Foundation, Inc. (Tallahassee, FL)

Patent Application: Material Patentability: Anticipated Issuing Date:

20070265174 (November 15, 2007) Very high Mid-2009

Research Focus: Originality: Application:

Preparation of ultrathin films of anionic and cationic polymers. Method for producing long-adhering chemically inert fabric modifiers. Stain repellant

Observations:

Hydrophobic fluorinated pyridinium iodide ionic solvents lack sufficient adhesiveness to remain affixed to a surface whether used as a powder or thin film. To address the lack of adhesion, this group prepared multilayered elements described in U.S. Patent 5,208,111, which remain affixed when applied to supports. This strategy was used to prepare adhesives consisting of poly(4-pyridinium) cationic perfluoro polyelectrolytes, which adhered to ultrathin films of selected anionic polyelectrolytes. Amorphous. complexes were also prepared by mixing solutions of polyelectrolytes bearing opposite charges. The driving force for this association or complexation of polyelectrolytes was the multiple ion pairing between oppositely charged repeat units on different molecules. In this manner ultrathin films with good mechanical ˚ and larger. adhesion were prepared having a thicknesses of 300 A

29

30

Hydrophobic Fluorinated Polyelectrolyte Complex Films and Associated Methods

REACTION

i. 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane, N,N 0 -dimethylformamide

EXPERIMENTAL 1. Preparation of perfluorovinylpyridinium iodide Poly(4-vinylpyridine) (10 mmol) having an Mn 300,000 Da was dried and then treated with 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-8-iodooctane (12 mmol) and the mixture reacted for 48 hours at 808C in 50 ml N,N 0 -dimethylformamide. The solution was precipitated by pouring into ethyl acetate and then washed with petroleum ether. The material was dried under vacuum for 24 hours at 608C and the product isolated in 90% yield.

TESTING A. Contact Angle Testing Contact angle testing was performed using a dynamic contact angle analyzer with the Wilhelmy technique. This method measures the forces that are present when a sample of solid is brought into contact with a test liquid. If the forces of interaction when the geometry of the solid and the surface tension of the liquid are known, the contact angle may be calculated. The sample was initially hung on a sensitive balance and the liquid raised to contact the sample. When the solid contacts the liquid, the change in forces are detected and the balance will record this elevation as zero depth of immersion. As the solid is lowered into the liquid, the forces on the balance are recorded. Results for contact angle measurements for experimentally layered agents are provided in Table 1.

Notes

31

TABLE 1. Dynamic and Static Contact Angle Measurements of Selected Experimental Agents Polyelectrolyte Multilayersa Blank Blank (PDADMA/PSS)10PDADMA (PDADMA/PSS)10PDADMA (PEPVP/PSS)10PFPVP (PEPVP/PSS)10PFPVP (PDADMA/Nafion)10 (PDADMA/Nafion)10 (PFPVP/Nafion)10PEPVP

Dynamic

Contact Angle

Advancing Receding Advancing Receding Advancing Receding Advancing Receding Advancing Receding

20.87 17.63 61.10 30.84 97.81 19.10 95.75 23.79 114.16 27.72

Advancing Contact Angle

15 75 112 118

a PDADMA ¼ poly(diallyldimethylammonium chloride), PSS ¼ poly(styrenesulfonic acid), PAMPS ¼ poly(2-acrylamido-2-methyl-1-propane sulfonic acid), and PFPVP ¼ 4-vinyl-trideca-fluoro-octyl pyridinium iodide-co-4-vinyl pyridine.

B. Thickness and Refractive Indices Selected polyelectrolyte multilayers were prepared and their thickness and refractive indices measured using ellipsometry. Testing results are reported in Table 2.

TABLE 2. Thickness and Refractive Indices Measurements of Selected Experimental Agents Polyelectrolyte Multilayersa (PDADMA/Nafion)10 (PFPVP/PSS)10 (PDADMA/PSS)10 (PFPVP/Nafion)10

Refractive Index

˚) Thickness (A

1.35 1.49 1.56 1.40

310 441 567 882

PDADMA ¼ poly(diallyldimethylammonium chloride) a positively, PSS ¼ poly(styrenesulfonic acid), PAMPS ¼ poly(2-acrylamido-2-methyl-1-propane sulfonic acid), and PFPVP ¼ 4-vinyl-trideca-fluorooctyl pyridinium iodide-co-4-vinyl pyridine.

a

NOTES 1. Ultrathin polyelectrolyte films were also prepared using macromolecules containing polyionic charged repeat units. Amorphous complexes were formed by mixing solutions of polyelectrolytes bearing opposite charges. The driving force for association or complexation of polyelectrolytes is multiple ion pairing between oppositely charged repeat units on different molecules. 2. Bureau et al. (1) developed a method for forming a polymer film that behaved as a conductor or semiconductor on its surface by layering using electrografting.

32

Hydrophobic Fluorinated Polyelectrolyte Complex Films and Associated Methods

3. Smela et al. (2) observed that some conjugated polyelectrolyte dopants caused a layering of polymer chains within a polymer. In other ionic electroactive material additives can be used for crystalline ordering. Such additives may include surfactants and/or liquid crystals. References 1. C. Bureau et al., U.S. Patent Application 20070281148 (December 6, 2007). 2. E. Smela et al., U.S. Patent Application 20070205398 (September 6, 2007).

5. Wetting Agents a. Polyacrylamide ionic solvents

Title: Polymerizable Sulfonate Ionic Liquids and Liquid Polymers Therefrom Author: Assignee:

Holly L. Ricks-Laskoski et al. United States Government as Represented by Secretary of the Navy


20080051605 (February 28, 2008) Very high 2010


Preparation of liquid phase methacrylamide ionic liquid polyethers. These agents are unreported in the patent literature. Fabric wetting agents

Observations:

A high-molecular-weight liquid-phase polymeric ionic liquid having a Tg of 2498C was prepared by neutralizing tris[2-(2-methoxyethoxy)-ethyl]amine with 2-acrylamido-2-methyl-1-propanesulfonic acid and then polymerizing with 2,20 -azobisisobutyronitrile. Although polymeric solvents have previously been prepared, they are usually based on pyridine, imidazole, or styrene and have the physical forms of a glass or a sticky rubber. Agents in the current application are liquids. Once dissolved poly(2-acrylamido-2-methyl-1-propanesulfonic acid) oxyethylene ammonium salts, however, can be directly converted into fabrics.

33

34

Polymerizable Sulfonate Ionic Liquids and Liquid Polymers Therefrom

REACTION

i. Tris[2-(2-methoxyethoxy)-ethyl]amine ii. 2,20 -Azobisisobutyronitrile

EXPERIMENTAL 1. Preparation of 2-acrylamido-2-methyl-1-propanesulfonic acid oxyethylene ammonium salt Equimolar amounts of 2-acrylamido-2-methyl-1-propanesufonic acid and freshly distilled tris[2-(2-methoxyethoxy)-ethyl]amine were mixed under an inert atmosphere and stirred for 8 hours at ambient temperature or until 2-acrylamido-2-methyl-1propanesulfonic crystals dissolved. The monomer salt consisted of a slightly yellow viscous clear liquid. The salt monomer was used in the next step without further purification. 2. Preparation of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) oxyethylene ammonium salt A mixture consisting of the step 1 product and 2,20 -azobisisobutyronitrile was heated to 708C for 18 hours. The transparent amber ionic liquid polymer salt was purified by dissolving in acetone and precipitating in cold diethyl ether. The precipitate was collected by cold suction filtration and the product isolated as a tacky transparent yellow liquid that had a Tg of 2498C and an intrinsic viscosity value of 0.3.

DERIVATIVES No additional derivatives prepared.

Notes

35

NOTES 1. Monomer and polymer electrolytes containing ion-exchangeable functional groups, (I), and an ionic liquid functional group, (II), were prepared by Best et al. (1) and used in fuel cells.

2. Giri et al. (2) prepared mixed ammonium and phosphonium polymeric ionic liquids, (III), from chloromethylated polystyrene, which were useful as enhancers in chemiluminescent systems.

3. Polymeric ionic liquids, (IV) and (V), were prepared by Schlenoff et al. (3) and used in polyelectrolyte membranes.

36

Polymerizable Sulfonate Ionic Liquids and Liquid Polymers Therefrom

4. Rodrigues et al. (4) prepared polymeric ionic liquid derivatives, (VI), by condensing poly(4-vinylpyridine) with propane sultone and products used as antidye transfer agents.

References 1. A.S. Best et al., U.S. Patent Application 20080045615 (February 21, 2008). 2. B.P. Giri et al., U.S. Patent 7,300,766 (November 27, 2007). 3. J.B. Schlenoff et al., U.S. Patent 7,223,327 (May 29, 2007). 4. K.A. Rodrigues et al., RE39,450 (December 26, 2006).

F. Paint Additives 1. Dispersants a. Acetoacetoxylethyl polymethacrylates

Title: Monomer Compound, Process for Producing the Same, Polymer Thereof, and Water-Based Curable Composition Author: Assignee:

Masami Kobata Kansai Paint Co., Ltd. (Amagasaki-shi, JP)


20080053835 (March 6, 2008) High 2010

Originality: Application:

Enhancing the hydrolytic stability of paints using the carbonylcontaining additive poly(N-(2-(methacryloyloxy)ethyl)-N-methylpyruvamide). This is a replacement additive for acetoacetoxy-based paint Additives. Paint additive

Observations:

Acetoacetoxylethyl methacrylate polymer, (a), and copolymer paint

Research Focus:

37

38

Monomer Compound, Process for Producing the Same

additives are hydrolytically unstable since they undergo a retro-Claisen condensation reaction. To address this concern the hydrolytically stable poly(N-(2-(methacryloyloxy)ethyl)-N-methyl-2,2-dimethoxypropionic acid amide), (b), was prepared. Although these derivatives are usually prepared by condensing acrylonitrile, concentrated sulfuric acid, and a carbonyl-containing compound, a less corrosive four-step route was used. Initially a triorthoester was converted into a ketal ester followed by hydroxylalkyl amidation, esterification, and hydrolysis to the target compound.

REACTION

i. Trimethyl orthoformate, methanol, paratoluenesulfonic acid monohydrate ii. N-Methyl-ethanolamine, methanol, sodium methoxide iii. Methyl methacrylate, 2,2,6,6-tetramethyl-1-piperidinyloxy intermediate, hydroquinone monomethyl ether, dioctyltin oxide, di-t-butyl methyl phenol iv. Hydrochloric acid v. Ethylene glycol monobutyl ether, 2,20 -azobis(2,4-dimethylvaleronitrile) EXPERIMENTAL 1. Preparation of 2,2-dimethoxymethyl propionate A flask was charged with methyl pyruvate (8.25 mol), trimethyl orthoformate (10 mol), methanol (1060 g), and para-toluenesulfonic acid monohydrate (0.041 mol) and then stirred at 588C for 10 hours. It was then treated with 28% methanol solution of sodium methoxide (8 g) and concentrated. After distillation the product was isolated as a colorless transparent liquid in 98% purity having a boiling point (bp) of 808C @ 40 mmHg. 1

H-NMR (CDCl3): d 3.82 (3H, s), 3.29 (6H, s), and 1.53 (3H, s) FTIR (cm21): 3632, 2999, 2953, 2837, 1749, 1455, 1437, 1373, 1293, 1216, 1192, 1144, 1046, 976, 892, 801, 761, and 676

Experimental

39

2. Preporation of N-(2-hydroxyethyl)-N-methyl-2,2-dimethoxypropionic acid amide A reaction kettle was charged with the step 1 product (7.5 mol) and N-methyl-ethanolamine (8.25 mol) and then treated with a 28% methanol solution of sodium methoxide (0.075 mol). This mixture was heated to 708C for 20 hours while distilling off methanol under reduced pressure. Thereafter, the mixture was treated with acetic acid (5 g) and then concentrated. After distillation 1146 g of product was isolated as a pale yellow transparent liquid with a 96% purity having a bp of 1358C @ 2 mmHg. 1 H-NMR (CDCl3): d 3.58 –3.84 (4H, m), 2.99 –3.32 (9H, m), 2.50–2.99 (1H, b), and 1.54–1.56 (3H, m) FTIR (cm21): 3445, 2945, 2837, 1634, 1498, 1456, 1437, 1404, 1375, 1226, 1149, 1106, 1041, 892, 747, and 655

3. Preparation of N-(2-(methacryloyloxy)ethyl)-N-methyl-2,2-dimethoxypropionic acid amide A mixture consisting of the step 2 product (0.71 mol), methyl methacrylate (3.3 mol), 2,2,6,6-tetramethyl-1-piperidinyloxy intermediate (0.23 g), hydroquinone monomethyl ether (0.23 g), and dioctyltin oxide (2.6 g) were added to a 500-ml flask equipped with a rectifying tower and stirred. The mixture was then heated to 1058C while introducing air. While maintaining the temperature at 1058C, methanol was distilled off over 12 hours during which the pressure was gradually reduced to 25 mmHg. Thereafter, the mixture was re-treated with 2,2,6,6-tetramethyl-1-piperidinyloxy intermediate (0.09 g), hydroquinone monomethyl ether (0.09 g), and di-t-butyl methyl phenol (0.09 g) and then distilled while introducing air. The product was isolated in 94% yield as a pale yellow transparent liquid with a 99% purity, which had a bp of 1428C @ 2 mmHg. 1

H-NMR (CDCl3): d 6.11 (1H, m), 5.59 (1H, m), 4.35 (2H, m), 3.68–3.90 (2H, m), 3.28 (6H, s), 3.03–3.28 (3H, m), 1.95 (3H, m), and 1.51 (3H, m) FTIR (cm21): 3498, 2946, 2834, 1719, 1652, 1455, 1400, 1373, 1319, 1296, 1164, 1104, 1040, 945, 892, 815, 746, and 651

4. Preparation of N-(2-(methacryloyloxy)ethyl)-N-methyl-pyruvamide A round-bottom flask was charged with the step 3 product (166 g) and 4% hydrochloric acid (495 g) and then stirred at ambient temperature for 5 hours and neutralized with a 10% aqueous NaHCO3 solution to pH 6. This solution was then treated with 400 ml of ethyl acetate and NaCl to extract the product, the cycle being repeated four times. The organic phases were concentrated and then treated with hydroquinone monomethyl ether (0.04 g), di-t-butyl methyl phenol (0.04 g), and N-oxyl derivative (0.14 g) and distilled while introducing air. The product was isolated in 90% yield as a pale yellow transparent liquid in 96% purity having a bp of 1388C @ 3 mmHg. 1

H-NMR (CDCl3): d 6.11 (1H, m), 5.61 (1H, m), 4.32–4.37 (2H, m), 3.66– 3.73 (2H, m), 3.05–3.09 (3H, m), 2.42 (3H, m), and 1.95 (3H, s) FTIR (cm21): 3518, 2959, 1718, 1644, 1492, 1453, 1408, 1354, 1318, 1296, 1163, 1103, 1019, 947, 815, 745, and 656

40

Monomer Compound, Process for Producing the Same

5. Preparation of poly (N-(2-(methacryloyloxy)ethyl)-N-methyl-pyruvamide) A 200-ml flask was charged with ethylene glycol monobutyl ether (30 g) and then heated to 858C and treated with the step 4 product (40 g) and 2,20 -azobis(2,4dimethylvaleronitrile) (1.5 g) over a period of 4 hours. Thereafter, a mixture of ethylene glycol monobutyl ether (30 g) and 2,20 -azobis(2,4-dimethylvaleronitrile) (0.5 g) was added over a period of 3 hours in the identical manner. After stirring an additional hour, the mixture was cooled to ambient temperature and a viscous liquid obtained. The percent solids of the liquid was 40.3% with a 98% reaction conversion. 6. Preparation of resin dispersion Water (28 g) and polyoxyethylene phenyl ether sulfuric acid ester emulsifier (0.08 g) were added to a 300-ml flask and heated to 858C while stirring. This solution was then treated with a mixture of the step 4 product (6.3 g), methyl methacrylate (41.6 g), styrene (14 g), butyl acrylate (23.5 g), 2-ethylhexyl acrylate (14.6 g), water (51.6 g), polyoxyethylene phenyl ether sulfuric acid ester emulsifier (6.6 g), and 0.3 g of sodium persulfate over 4 hours. Thereafter, a mixture of water (5.2 g) and ammonium persulfate (0.1 g) were added over 30 minutes and the mixture stirred for an additional 2 hours. It was then cooled to ambient temperature and a white resin isolated, which consisted of 52% solids with a polymerization conversion of 99%.

DERIVATIVES No additional derivatives were prepared.

TESTING Storage Stability Storage stability of the resin dispersion was determined using an accelerated decomposition test at 808C for 20 hours. The decomposition rate of N-methyl-pyruvamide in this dispersion after the test was less than 3%.

Notes

41

NOTES 1. The structure of the 2,2,6,6-tetramethyl-1-piperidinyloxy intermediate, (I), provided by the author is illustrated below.

2. A curable polypropylene glycol resin containing trimethoxysilyl termini, (II), having good adhesiveness and storage stability properties was prepared by Wakabayashi et al. (1) and used in water-based paint formulations.

3. Sakamoto et al. (2) prepared macromonomers consisting of poly(butyl acrylateb-methyl methacrylate), which were used as paint additives to enhance adhesiveness and storage stability properties.

References 1. K. Wakabayashi et al., U.S. Patent Application 20080051547 (February 28, 2008). 2. H. Sakamoto et al., U.S. Patent Application 20080009593 (January 10, 2008).

b. Poly(4-methyl-pentene) aldehyde

Title:

Functionalized Poly(4-Methyl-1-Pentene)

Author: Assignee:

John R. Briggs et al. Dow Global Technologies, Inc. (Midland, MI)


20080021172 (January 24, 2008) High Mid-2010

Hydroformylation of poly(4-methyl-1-pentene) terminus. Hydroformylation of poly(4-methyl-1-pentene) is unreported in the patent literature. Paint dispersant Although poly(4-methyl-1-pentene) was initially prepared over 40 years ago, its use has been restricted to polymer blends and paint-free additives. Copolymers of this agent are used for preparing multilayer films and film layers. The current application has developed a method using hafnium salts to prepare a polymer containing 95% chain-end unsaturation of which 80% comprises 1,2-olefinic unsaturation. This material was then hydroformylated with carbon monoxide. The hydroformylated polymer has broad applications including use in: a. Schiff base reactions to prepare amines b. Conversion to diols for use as component in polyurethanes and highperformance polycarbonates c. Mixed aldol condensations to generate a,b-unsaturated ketones d. Conversion to acids and used in making polyamides

42

Experimental

43

REACTION

i. Toluene, [N-(2,6-di(1-methylethyl)phenyl)amido)(2,4,6-trimethylphenyl(phenylen-2-diyl)(6-pyridin-2-diyl)methane)]hafnium dimethyl, [N-(2,6-di(1-methylethyl)phenyl)amido)(2,4,6-trimethylphenyl)(a-naphthalen-2-diyl)(6-pyridin-2diyl)methane)]hafnium dimethyl, ammonium dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate, MMAO-12, PMAO-IP, Irganoxw 1010, Irgafosw 168 ii. Carbon monoxide, hydrogen, dicarbonyl acetylacetonate, tris(2,4-di-t-butylphenyl)phosphate, toluene EXPERIMENTAL 1. Preparation of poly(4-methyl-1-pentene) An autoclave was charged with 4-methyl-1-pentene (6.89 mol) and then treated with toluene solutions of [N-(2,6-di(1-methylethyl)phenyl)amido)(2,4,6-trimethylphenyl)(phenylen-2-diyl)(6-pyridin-2-diyl)methane)]hafnium dimethyl [catalyst 1] and [N-(2,6-di(1-methylethyl)phenyl)amido)(2,4,6-trimethylphenyl)(a-naphthalen2-diyl)(6-pyridin-2-diyl)methane)]hafnium dimethyl [catalyst 2]. The amount of each catalyst was 6.0 mmol. The mixture was then treated with 6.6 mmol co-catalyst ammonium dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate. Polymerization modifiers used were the trialkylaluminum-modified methylalumoxanes MMAO-12 and PMAO-IP. After 15 minutes of reaction time, the reactor contents are placed into a resin kettle containing 1 g of a 50/50 mixture of the antioxidant Irganoxw-1010 and stabilizer Irgafosw-168. Following the reaction, the polymer was recovered by evaporating the majority of the solvent under ambient conditions and then further dried in a vacuum oven overnight at 908C. Polymerization reaction scoping studies and physical properties of polymers are provided in Tables 1 and 2, respectively. 2. Hydroformylation process A sample of the polymer of step 1 product was hydroformylated by reacting it with a mixture of carbon monoxide and hydrogen under 690 kPa for 4 hours catalyzed by rhodium dicarbonyl acetylacetonate (10.2 mg) and tris(2,4-di-t-butylphenyl)phosphite (48.2 mg) dissolved in toluene. 1H-NMR spectrum of this polymer showed the presence of carbonyl functional groups in place of ethylenic unsaturation.

44

Functionalized Poly(4-Methyl-1-Pentene)

SCOPING REACTIONS TABLE 1. Polymerization Scoping Studies for Poly(4-methyl-1-pentene) Using a Hafnium Salt Catalyst with Selected Polymerization Modifiers

Experiment 1 2 3 4

Catalyst

Polymerization Modifier

Polymerization Modifier (mmol)

Reaction Temperature (8C)

Yield (%)

Efficiency (gPP/mgHf)

Catalyst 1 Catalyst 1 Catalyst 2 Catalyst 2

MMAO PMAO MMAO PMAO

3.0 0.2 3.0 3.0

90 100 90 110

27 51 43 46

25 48 40 43

TABLE 2. Physical Properties of poly(4-methyl-1-pentene) Prepared Using Hafniumn-Based Catalystsa Experiment

Mn (Da)

Mw (Da)

Polydispersity

Tm (8C)

1 2 3 4

9,320 11,200 15,900 10,000

25,000 42,600 66,440 22,500

2.68 3.8 4.18 2.25

226 228 232 228

a

Scoping conditions are described in Table 1.

NOTES 1. 4-Methyl-1-pentene polymerization catalysts are illustrated below: a. [N-(2,6-di(1-methylethyl)phenyl)amido)(2,4,6-trimethylphenyl)(phenylen2-diyl)(6-pyridin-2-diyl)methane)]hafnium dimethyl, (I). b. [N-(2,6-di(1-methylethyl)phenyl)amido)(2,4,6-trimethylphenyl)(a-naphthalen-2-diyl)(6-pyridin-2-diyl)methane)]hafnium dimethyl, (II).

Notes

45

2. Propylene and 4-methyl-1-pentene were copolymerized by Colin et al. (1) using a Ziegler – Natta catalyst and the product characterized as having at least one fraction obtained by that had a block index greater than about 0.3 and up to about 1.0 with a polydispersity greater than 1.3. 3. Poly(ethylene-co-4-methyl-1-pentene) was prepared by Colin et al. (2) and used as fibers, thermoplastics, and as oil viscosity index improvers. 4. Methods for preparing and using compositions containing poly(4-methyl-1pentene) having a controlled molecular weight distribution are described by Patel et al. (3). Methods for preparing multilayer films and film layers are also described. 5. A method for controlling the molecular weight of poly(4-methyl-1-pentene) was devised by Hustad et al. (4) and entailed limiting the monomer concentration using a precatalyst and by adding a catalytic amount of a titanium(III)containing salt as an ethylene interceptor.

References 1. L.P.S. Colin et al., U.S. Patent Application 20070219334 (September 20, 2007). 2. L.P.S. Colin et al., U.S. Patent Application 20060199930 (September 7, 2007). 3. R.M. Patel et al., U.S. Patent Application 20070275219 (November 29, 2007). 4. P.D. Hustad et al., U.S. Patent Application 20070135575 (June 14, 2007).

G. Paint Stabilizers 1. Hydrolytically and oxidatively stable paint additives a. Oligomeric polyaromatic esters

Title: Polyester Oligomers, Methods of Making, and Thermosetting Compositions Formed Therefrom Author: Assignee:

Corrado Berti et al. General Electric Company, Global Research (Niskayuna, NY)


46

20070155946 (July 5, 2007) Moderate Mid-2009

Preparation of hydrolytically and oxidatively stable oligomeric polyaromatic esters. Continuation of an ongoing investigation in the development of phaseseparated weatherable oligomeric esters. Exterior paint additives Polymeric and oligomeric materials having good resistance to photo yellowing or weatherability are usually restricted to low-molecularweight polyarylates that form a stable composition that is permanent upon crosslinking. Photostable oligomeric esters containing both noncrystalline and crystalline domains and having carboxylic acid termini were prepared in this application and then crosslinked with polyacrylates. Oligomeric esters were prepared by initially forming an ester-carbonate prepolymer and then decarboxylating the intermediate. Products were formed in quantitative yields.

47

Reaction Scoping

REACTION

i. Isophthalic acid, diphenyl carbonate, resorcinol, polyethylene glycol, sodium hydroxide EXPERIMENTAL A reaction flask was charged with terephthalic acid (12.46 g), isophthalic acid (12.46 g), diphenyl carbonate (44.07 g), resorcinol (9.63 g), polyethylene glycol (7.50 g; Mn 600), and sodium hydroxide (0.02 g) as catalyst and then heated to 1708C. The reactor was then connected to a liquid nitrogen cooled condenser and immersed in a 2858C oil bath. Phenol formed as a reaction by product was distilled and then recovered in a condenser. Carbon dioxide evolution began after 15 minutes and stopped after 2 hours while heating was continued for an additional 3 hours. Thereafter a vacuum was slowly applied to the reactor to decrease the internal pressure from atmospheric pressure to 60 mbar in approximately 10 minutes. After 30 minutes from reaching this pressure, the internal pressure was further decreased to 0.1 mbar and the reaction stopped after 15 minutes. The oligomer was then transferred to a cooling tray while still molten and allowed to cool. REACTION SCOPING Scoping reaction studies designed to optimize carboxylic acid content are provided in Table 1. TABLE 1. Oligomer Scoping Reaction Studies and Physical Properties of Products Using 10 –40% Excess Diacid

Entry 1 6d 9 10

Catalysta

Catalyst Level (ppm)

Reaction Temp. (8C)

Molar Ratiob (TPA þ IPA)/ (RES þ PEG)

TBT þ NaH2PO4 C94 NaOH NaOH

100 74 350 350

275 270 280 280

1.3 1.5 1.5 1.5

Molar Ratioc (DPC/ (RES þ PEG)

Molar Ratio PEG/ (RES þ PEG

1.89 2.05 2.05 2.05

0.125 0.125 0.125 0.625

COOH End Mn Groups (%) (Da) 3900 4700 — 9300

66.1 70.7 92.5 67.8

TBT ¼ tetrabutyl titanate and C94 catalyst ¼ titanium and silica-based catalyst. IPA ¼ Isophthalic acid, PEG ¼ polyethylene glycol, RES ¼ resorcinol, and TPA ¼ terephthalic acid. c DPC ¼ diphenyl carbonate. d Entry 6 represents the optimum reaction conditions for preparing the thermosetting composition. a b

48

Polyester Oligomers, Methods of Making, and Thermosetting Compositions

NOTES 1. Carboxy-terminated oligomeric polyester compositions consisting of resorcinol, terephthalic isophthalic acid, diphenyl carbonate, and terephthalic acid catalyzed by titanium tetrabutoxide were prepared by Brunelle et al. (1) and used as thermosetting applications. 2. Poly(1,4-cyclohexylenedimethylene isophthalate) was prepared by Martin et al. (2) by condensing isophthalic acid and 1,4-cyclohexanedimethanol and the product used in packaging applications, textiles, sheeting, and film applications. 3. Thermoset polymeric esters consisting of neopentyl glycol, propylene glycol, trimethylol propane, adipic acid, maleic anhydride, and 2-ethyl hexanol were prepared by McAlvin et al. (3) and were used in blends containing styrene monomer. The mixture was cured by pultrusion and had improved weatherability characteristics. 4. Thermoset plastics having low permeability to fluids consisting of ethylene glycol, 4,40 -biphenol, terephthalic acid, 4-hydroxybenzoic acid, and 6-hydroxy2-napthoic acid were prepared by Doshi et al. (4) and used in piping and containers with high fluid barrier limits. References 1. D.J. Brunelle et al., U.S. Patent Application 20070027290 (February 1, 2007) and U.S. Patent Application 20060116487 (June 1, 2006). 2. D.L. Martin et al., U.S. Patent 7,211,634 (May 1, 2007). 3. J.E. McAlvin et al., U.S. Patent Application 20070032608 (February 8, 2007). 4. S.R. Doshi et al., U.S. Patent Application 20080020160 (January 24, 2008).

H. Paper Additives 1. Stabilizers a. Glyoxalated poly(vinylamide-co-diallyldimethylammonium chloride)

Title:

Glyoxalation of Vinylamide Polymer

Author: Assignee:

Matthew D. Wright Ciba Geigy Corporation (Tarrytown, NY)


20080064819 (March 13, 2008) Moderate 2011

Synthesis of glyoxalated poly(vinylamide-co-diallyldimethylammonium chloride) by free radical polymerization. Ongoing 4-year investigation by this group. Paper additive Although paper-strengthening additives have previously been prepared consisting of: i. Blends of polyvinylamide, polydiallyldimethylammonium chloride, and glyoxal ii. Glyoxalated poly(vinylamide-co-diallyldimethylammonium chloride) crosslinked with N,N0 -methylene bisacrylamide iii. Glyoxalated poly(vinylamide-co-diallyldimethylammonium chloride) containing 80% vinylamide storage stability of these consumer paper products is limited. To address this concern, glyoxalated poly(vinylamide-co-diallyldimethylammonium chloride) containing 91% vinyl amide was prepared in two steps and used as a storage-stable paper-strengthening additive. The method for its 49

50

Glyoxalation of Vinylamide Polymer

preparation entailed the free radical polymerization of vinylamide and diallyldimethyl ammonium chloride and then postreacting with glyoxal in the presence of sodium hydroxide. The preparation of these cellulose reactive adducts was performed slightly below the critical micelle concentration so that the risk of gelation was minimized and the amount of incorporated glyoxal was optimized.

REACTION

i. Water, glyoxal, sodium hydroxide EXPERIMENTAL 1. Preparation of glyoxalated poly(vinylamide-co-diallyldimethylammonium chloride) An aqueous solution of poly(vinylamide-co-diallyldimethylammonium chloride) consisting of 91 wt% acrylamide was treated with sufficient glyoxal so that an amide/glyoxal molar ratio of 4:1, respectively, was obtained. Thereafter the mixture was treated with the dropwise addition of 5 wt% aqueous sodium hydroxide until the pH of the solution reached 9.2. Small additions of sodium hydroxide were administered as needed to maintain a constant pH of 9.2 for 30 minutes. TESTING Critical Micelle Concentration To enhance the shelf life of finished paper product, the step 1 product was applied below its critical micelle concentration (CMC). Materials additized above the CMC formed insoluble gels when aged for 8 days at 738C. The CMC ranges was determined using glyoxalated poly(vinylamide-co-diallyldimethyl-ammonium chloride) containing 90 wt% vinylamide and are provided in Table 1. Tensile Strength Tensile strength testing was performed using 0.05 wt% of selected experimental agents on dry cellulose. Testing results are provided in Table 1.

Notes

51

TABLE 1. Critical Micelle Concentration and Tensile Strength Testing Results for Glyoxalated Poly(vinylamide-co-diallyldimethylammonium chloride) Entry B E G None Comparison

Mn (1 105 Da)

CMC Concentration Range (%)

Tensile Strength (kg/mm2)

1.60 105 1.40 105 1.30 104 — 1.00 104

0.6–0.8 1.5–1.75 3.2–3.6 — —

8.59 9.34 9.14 8.55 8.99

NOTES 1. Poly(vinylamide-co-diallyldimethylammonium chloride was prepared according to the method of Coscia et al. (1). 2. Blends of polyvinylamide, polydiallyldimethylammonium chloride, and glyoxal were previously prepared by Ballweber et al. (2) and used as paper fiber additives. 3. Glyoxalated poly(vinylamide-co-diallyldimethylammonium chloride) containing 80% vinylamide content and having a molecular weight of 1900 Da was previously prepared by Guerro et al. (3) and used as handsheet additives. 4. Glyoxalated copolymers consisting of acrylamide and diallyldimethylammonium chloride crosslinked with N,N0 -methylene bisacrylamide, (I), were prepared by Hagiopol et al. (4) and used as paper-strengthening agents.

References 1. A.S. Coscia et al., U.S. Patent 3,556,932 (January 17, 1971). 2. E.G. Ballweber et al., U.S. Patent 4,217,425 (August 12, 1980). 3. G.J. Guerro et al., U.S. Patent 4,605,702 (August 12, 1986). 4. C. Hagiopol et al., U.S. Patent Application 20050187356 (August 25, 2005).

I. Polymeric Additives 1. Anticraze agent a. 1,2,4,5-Benzenetetracarboxylic anhydride amic acid

Title:

Beta-crystalline Polypropylenes

Author: Assignee:

Qinggao Ma et al. Chemtura Corporation (Middlebury, CT)

U.S. Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus: Originality: Application: Observations:

52

20070293609 (December 20, 2007) Moderate Late 2009

Preparation of high-clarity, low-craze polypropylene with improved thermal properties. The use of imide additives to reduce haze in polypropylene is unreported in the patent literature. Preparation of transparent polypropylene films The reaction product of 1,2,4,5-benzenetetracarboxylic anhydride and cyclohexyl amine has been determined to be effective in reducing haze for extruded polypropylene. When an amic acid intermediate was dry blended with polypropylene powder and extruded at 2398C using a small co-rotating twin-screw extruder, produced the insite generate imide reduced crystallinity associated with reduced haze.

Derivatives

53

REACTION

i. Cyclohexylamine, xylene ii. Heat, propylene

EXPERIMENTAL 1. Preparation of amic acid intermediate At ambient temperature a reaction flask charged with cyclohexylamine (240.69 mmol) dissolved in 50 ml of xylene was added to a second flask containing 1,2,4, 5benzenetetracarboxylic anhydride (229.23 mmol) dissolved in 100 ml of xylene. The reaction was exothermic and a white solid then precipitated out upon mixing. Thereafter, the mixture was stirred at ambient temperature for 2 hours, filtered, and the precipitate washed with xylene. After being dried under vacuum the product was isolated as a white powder. 2. Polypropylene blending with amic acid intermediate A mixture consisting of powdered polypropylene (59.91 g) and the step 1 product (90 mg) were tumble-mixed in a glass container for 24 hours. Thereafter the mixture (4.5 g) was compounded at 2398C using a small co-rotating twin-screw extruder. The sample required 4 minutes at a screw speed of 40 rpm to be prepared. The extruded material only had a slight haze content.

DERIVATIVES A second amic acid derivative was prepared and is illustrated below.

54

Beta-crystalline Polypropylenes

TESTING A. Optical Characterization Transmission, clarity, and haze were measured with a haze-guard plus instrument at ambient temperature according to ASTM D-1003 protocol. Testing results are provided in Table 1. TABLE 1. Effect of Selected Additives on Crystallinity and Haze of Extruded Polypropylene Component None Nucleating agenta Hyperfoam HPN 68L Cyclopentyl amic acid derivative Cyclohexyl amic acid derivative a

Tcryst (8C)

Haze (%)

107.2 120.33 123.35 121.52 123.14

33.5 39.2 30.7 47.4 25.4

1,3:2,4-Bis(3,4-dimethylbenzylidene)sorbitol.

B. Crystallinity Determination Crystallinity was determined using differential scanning calorimetry. About 5 – 10 mg of an experimental agent was heated from 25 to 2008C at a heating rate of 208C/ minute. The sample was isothermed at 2008C for 1 minute and then cooled at a cooling rate of 208C/minute to ambient temperature. Crystallization data represents peak temperatures of exotherms in the cooling cycle and are summarized in Table 1.

NOTES 1. Jaaskelainen et al. (1) reports that polypropylene containing 3.3%, 3.7%, and 5 – 6% ethylene content were visbroken with Triganox 101 using a twinscrew lab extruder BF-50 and haze levels of less than five observed. 2. Stevens et al. (2) observed that the haze content of poly(ethylene-co-[isotactic]propylene) was directly related to the monomer content and whether the material was prepared using a metallocene catalyst. Low haze values were obtained for polymers prepared using nonmetallocene catalytic agents with polymers having moderately high ethylene levels. 3. Jaaskelainen et al. (3) demonstrated that polypropylene does not strictly fractionate according to tacticity but according to the longest crystallizable sequence in the chain. It was observed that polypropylene containing random amounts of 4.5% to 12.0 mol% ethylene using temperature rising elution fractionation isolated materials had high transparency, low haze, and high gloss with crystallinity greater than 21%.

Notes

55

4. Trexler et al. (4) report that when unmodified polyethylene terephthalate was additized with the nucleator nylon-6,6 and passed through a single-screw extruder at 2808C, crystallization rates were 50% faster. References 1. P. Jaaskelainen et al., U.S. Patent Application 20070287818 (December 13, 2007). 2. J.C. Stevens et al., U.S. Patent Application 20070249798 (October 25, 2007). 3. P. Jaaskelainen et al., U.S. Patent Application 20070203309 (August 30, 2007) and U.S. Patent Application 20070197743 (August 23, 2007). 4. J.W. Trexler, Jr et al., U.S. Patent 7,279,124 (October 9, 2007).

2. Polymeric Dispersants a. Polyaromatic ester amides

Title:

Preparation of Polyamide Block Copolymers

Author: Assignee:

David T. Williamson et al. E I DuPont De Nemours and Company (Wilmington, DE)

U.S. Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus:


56

20070293629 (December 20, 2007) Very high Mid-2009

Method of preparing random poly(amide-b-ester) derivatives through depolymerization/repolymerization of cyclic polyesters then coreacting with lactam derivatives using a nonmetallic carbene catalyst. This method for preparing polyester amides is unreported. Polymeric dispersants Poly(amide-b-ester) was prepared in two steps. Initially cyclic poly(diethyleneglycol terephthalate) was depolymerized and then repolymerized into its linear counterpart in the absence of a metallic catalyst. Once the polymerization was completed, it was co-polymerized with 1-caprolactam producing poly(nylon-6-b-diethyleneglycol terephthalate) using 1,3-di-1-adamantyl-imidazole-2-ylidene as the reaction catalyst. The copolymer had a block content of 85.8% with a molecular weight of 31,500 Da. This is the first instance in the patent literature where a nonmetallic N-heterocyclic carbene has been used as a catalyst in a polymerization reaction. 1H-NMR computational methods for determining the presence of monad, diads, triads, and so forth. content was also developed.

Notes

57

REACTION

i. Diethylene glycol, toluene, Novozyme 435 ii. Caprolactam, 1,3-di-1-adamantyl-imidazole-2-ylidene, toluene EXPERIMENTAL 1. Preparation of cyclic poly(diethyleneglycol terephthalate) A 22-liter resin kettle was charged with 9.246 liters of toluene, diethylene glycol (2.50 mol), and dimethylterephthalate (2.50 mol) then heated to 808C and treated with Novozyme 435. After heating and sparging the mixture for 24 hours at 808C, toluene was distilled from the mixture at 708C @ 50 torr. The resulting solids were divided into three equal portions and extracted with 11 liters of refluxing chloroform for 3 hours. The hot chloroform extract was then filtered to remove the enzyme catalyst and the filtrate concentrated to about 3.5 liters. The solution was then cooled to ambient temperature, refiltered, and the product isolated as a white solid in 83% yield with 99% purity. 2. Preparation of poly(nylon-6-block-diethyleneglycol terephthalate) A mixture of 1,3-di-1-adamantyl-imidazole-2-ylidene (45 mg) and caprolactam (454 mg) were heated at 2308C for 15 minutes. After cooling the number-average molecular weight was determined to be 31,500 Da with a polydispersity of 3.4 and with 86% product conversion. This material was then treated with the step 1 product (948 mg) and heated at 2308C for 30 minutes. Gas-phase chromatography (GPC) analysis indicated that the product had an Mn of 24,700 Da with a polydispersity of 3.4 and an 83% reaction conversion. The block incorporation in the polymer was 85.8%. NOTES 1. The IUPAC name for the step 1 product is 3,6,9,16,19,22-hexaoxatricyclo [22.2.2.211,14]-triaconta-11,13,24,26,27,29-hexaene-2,10,15,23-tetrone. 2. A model reaction where both reagents and catalyst Novozyme 435 were reacted together was also performed. The model reaction product had an Mn of 17,200 Da with a polydispersity of 1.7 and had 76.3% random monomer incorporation. 3. The use of the step 2 carbene reagent catalyst, 1,3-di-1-adamantyl-imidazole-2ylidene, (I), in preparing macrocyclic polyester oligomers is described by

58

Preparation of Polyamide Block Copolymers

Tam et al. (1). Ring-opening polymerization of cyclic amides using this agent are also reported by Tam et al. (2).

4. Depolymerization of macromolecular esters and repolymerization into linear polyesters is reported by Zhang et al. (3) using zinc alkoxide catalyst, (II).

References 1. W. Tam et al., U.S. Patent Application 20070252311 (November 1, 2007) and U.S. Patent Application 20060128935 (June 15, 2006). 2. W. Tam et al., U.S. Patent Application 20060100365 (May 11, 2006) and U.S. Patent Application 20060096699 (May 11, 2006). 3. D. Zhang et al., U.S. Patent Application 20070083019 (April 12, 2007).

II. ADHESIVES A. Pressure Sensitive Adhesives a. Polysilsesquioxane graft polymers

Title: Process for Producing Polysilsesquioxane Graft Polymer, Pressure-Sensitive Adhesive, and PressureSensitive Adhesive Sheet Author: Assignee:

Taketo Kumon et al. Lintec Corporation (Tokyo, JP)


20080051487 (February 28, 2008) High 2010

Synthesis of silsesquioxane ladder polymers effective as iniferters containing polymerizable grafted components. Silsesquioxane ladder derivatives effective as iniferters containing grafted polymerizable components are unreported. Heat-resistant pressure-sensitive adhesives Although silsesquioxane-containing pressure adhesives have previously been prepared, they lack sufficient heat resistance for broad applications. A polyhedron silsesquioxane ladder polymer containing polymerizable components was prepared in a three-step process to address this concern. The process initially entailed preparing the reversible additionfragmentation transfer (RAFT) ladder iniferter, polysilsesquioxane dithiocarbamate. This intermediate was then polymerized with methyl methacrylate at ambient temparature by irradiating with ultraviolet (UV) light and poly(silsesquioxane-g-methyl methacrylate) was obtained.


59

60

Process for Producing Polysilsesquioxane Graft Polymer

REACTION

i. Toluene, water, p-chloromethylphenyltrimethoxysilane, methanesulfonic acid ii. Tetrahydrofuran (THF), sodium diethyldithiocarbamate, methanesulfonic acid iii. Toluene, methyl methacrylate EXPERIMENTAL 1. Preparation of polysilsesquioxane intermediate A round-bottom flask was charged with 15 ml of a toluene and water, 2:1, respectively, phenyltrimethoxysilane (0.02 mol), p-chloromethylphenyltrimethoxysilane (0.02 mol), and methanesulfonic acid (5 mol%) and then stirred at ambient temperature for 12 hours. The organic layer was isolated, concentrated, and then added dropwise to a large quantity of n-hexane. The precipitated solid was filtered, dried, and the product isolated in 93% yield having an Mn of 1300 Da with a poly dispersity index (PDI) of 1.25. 2. Preparation of polysilsesquioxane dithiocarbamate iniferter A round-bottom flask was charged with 20 ml of THF, the step 1 product (2.2 mmol), sodium diethyldithiocarbamate (2.2 mmol), and methanesulfonic acid (5 mol%) and

Testing

61

then stirred at ambient temperature for 6 hours. The product was isolated in 90% yield having an Mn of 2100 Da with a PDI of 1.3 following the step 1 workup. 3. Preparation of poly(silsesquioxane-g-methyl methacrylate) A glass tube was charged with the step 2 product (0.45 mmol), 100 ml of toluene, and methyl methacrylate (0.50 mmol) and then stirred at ambient temperature for 3 hours while irradiating with UV light. Thereafter, the mixture was precipitated in a large quantity of n-hexane, filtered, dried, and the polymer isolated in 65% yield having an Mn of 45,000 Da with a PDI of 2.11. DERIVATIVES

TABLE 1. Entry 3 4 5 7 8 9 10

Physical Properties of Selected Graft Polysilsesquioxane Derivatives Ra

R (mmol)

Solvent

Yield (%)

Mn (Da)

PDI

DMA DMA DMAAm DMAAm MMA BA DMA/MMA

0.50 1.00 1.35 2.23 2.05 2.05 —

Toluene Toluene THF Toluene THF THF Toluene

68 69 81 64 68 63 70

20,000 35,000 3100 2800 4200 4600 20,000

2.16 2.24 2.1 1.4 2.2 1.6 2.6

BA ¼ n-butylacrylate, DMA ¼ dodecyl MMA ¼ methyl methacrylate.

a

methacrylate,

DMAAm ¼ N,N-dimethylacrylamide,

and

TESTING Adhesive Property Test The holding power, adhesion, and probe tack of selected pressure-sensitive adhesive sheets were evaluated in accordance with JIS Z0237. Testing results are provided in Table 2.

62

Process for Producing Polysilsesquioxane Graft Polymer

TABLE 2.

Adhesion and Thermal Properties of Selected Experimental Agents

Entry

Holding Power (s)

Adhesion (N/25 mm)

Probe Tact

TGAa Weight Loss at 3008C (%)

4 10 Comparative-10

100 11,800 800

15.0 6.5 4.8

412 156 173

7.3 6.9 53.2

a

TGA ¼ thermal gravimetric analysis.

NOTES 1. Silsesquioxane epoxide derivatives, (I), were prepared by Inagaki et al. (1) and used as pressure-sensitive polyether adhesives. Silsesquioxane methacrylate derivatives, (II), prepared by Morimoto et al. (2) were also used as pressuresensitive adhesives.

Notes

63

2. Lai et al. (3) prepared reactive polyhedral oligomeric silsesquioxane derivatives, (III), containing norbornenylethyl that were effective as adhesives and also in ophthalmic devices.

References 1. J-I. Inagaki et al., U.S. Patent Application 20050009982 (January 13, 2005). 2. Y. Morimoto et al., U.S. Patent 7,169,873 (January 30, 2007). 3. Y-C. Lai et al., U.S. Patent 7,198,639 (April 3, 2007).

b. Polymethacrylate ester derivatives

Title: Bimodal Acrylate PSA for Bonding Low-Energy and Rough Surfaces Author: Assignee:

Stephan Zollner et al. TESA AG (Hamburg, DE)


64

20080027179 (January 31, 2008) Medium Mid-2010

Preparation of (meth)acrylate derivative as pressure-sensitive adhesives for bonding to low-energy surfaces. While bimodal pressure-sensitive adhesives have been previously prepared, bimodal copolymers are unreported. Pressure-sensitive adhesives The challenge of developing pressure-sensitive adhesives as low-energy substrates lay in the requirement of obtaining a profile of properties that combine immediate, high-level, and uniform adhesion with a high level of static shearing resistance at elevated temperatures. In this application bimodal pressure-sensitive adhesives consisting of C1 – C18 polymethacrylates were prepared that exhibited high adhesion to low solubility threshold (LSE) substrates at ambient temperature and at elevated temperature. These materials were free radically prepared in a two-stage single-step polymerization process.

Derivatives

65

REACTION

i. 2-Ethylhexyl acrylate, boiling point Spirit 69/95, acetone, Vazo-67

EXPERIMENTAL A reactor was charged with acrylic acid (20 g), 2-ethylhexyl acrylate (380 g), boiling point Spirit 69/95 (133 g), and 133 g of acetone. The mixture was then heated to 588C and treated with Vazo-67 (0.2 g) and then further heated to 778C. After a reaction time of 2.5 hours additional acetone (100 g) was added. After 4 hours the mixture was treated with additional Vazo-67 (0.2 g). After a further polymerization time of 5 hours a second dilution with acetone (100 g) was made. Finally after an additional 6 hours the mixture was diluted with boiling point Spirit 60/95 (100 g). The polymerization was discontinued after 24 hours and the reaction vessel cooled to ambient temperature. The product was isolated having an Mw of 365,000 Da with a PDI of 16.46 with gasphase chromatography (GPC) peaks ranging from 79,400 to 697,000 Da.

DERIVATIVES TABLE 1. Properties of Pressure-Sensitive Adhesives Prepared Free Radically Using Vazo-67 Entry 1a

2b

3a

4a

Monomer 1 (wt) 2-Ethylhexyl acrylate (380 g) 2-Ethylhexyl acrylate (51.1 kg) 2-Ethylhexyl acrylate (33.95 kg) 2-Ethylhexyl acrylate (49.7 kg)

Monomer 2 (wt) Acrylic acid (20 g) Acrylic acid (0.7 kg) Acrylic acid (4.9 kg) Acrylic acid (4.9 kg)

Monomer 3 (wt)

Monomer 4 (wt)

Mw (Da)

PDI

—

—

386,000

9.10

Glycidyl methacrylate (1.4 kg) Methyl acrylate — (14.0 kg)

892,000

56.66

328,000

27.82

Methyl methacrylate (14.0 kg)

857,000

31.62

Butyl acrylate (3.95 kg)

Glycidyl methacrylate (1.4 kg)

66

Bimodal Acrylate PSA for Bonding Low-Energy and Rough Surfaces

TESTING TABLE 2. Entry

Holding Power 10N (ambient temperature) (min)

Shear Adhesive Failure Temperature

Bond Strength to Polyethylene (N/cm)

897 1547 10,000 10,000

1000 mm/1268C 436 mm/2008C 1000 mm/1678C 94 mm/2008C

3.9 4.8 1.4 1.3

1a 2b 3a 4a a

Adhesive Properties of Bimodal Polymers on a Nonpolar Substratea

Monomodal reference samples were consistently less effective despite identical compositions.

NOTES 1. Heat-activatable pressure-sensitive adhesives consisting of crosslinked C1 – C18 polymethacrylates were prepared by Husemann et al. (1) and used on polyester substrates. 2. A pressure-sensitive self-adhesive composition capable of compensating for substrate unevennesses was prepared by Massow et al. (2) and consisted of natural rubber and tackifier resins. 3. Bimodal pressure-sensitive adhesives consisting of C1 – C18 polymethacrylates and containing 2-hydroxyethyl methacrylate were prepared by Dollase et al. (3) and used in self-adhesive tapes. 4. Schumacher et al. (4) prepared adhesives for polyvinyl chloride (PVC) pipes having a Tg range from 260 to 2208C and consisting of C1 – C18 polymethacrylates, acrylic acid, and ionic emulsifers. References 1. M. Husemann et al., U.S. Patent Application 20070287807 (December 13, 2007). 2. K. Massow et al., U.S. Patent Application 20070212964 (September 13, 2007). 3. T. Dollase et al., U.S. Patent Application 20070270559 (November 22, 2007). 4. K-H. Schumacher et al., U.S. Patent Application 20070187033 (August 16, 2007).

B. Surface Adhesives a. Novolak-disulfide resins

Title: Novel Sulfur-containing Phenolic Resin, Process for Preparing the Same, Phenol Derivatives Having Thioether Structure or Disulfide Structure, Process for Preparing the Same and Epoxy Resin Composition Adhesive Author: Assignee:

Haruaki Sue et al. Hitachi Chemical Company, Ltd. (Tokyo, JP)



20080051550 (February 28, 2008) High 2010

Method of preparing surface adhesives using phenolic resins either modified with disulfides or free radically copolymerized with ethanedithol and then postreacted with epichlorohydrin. The use of phenolic disulfide resins and thio copolymers as adhesives alone or epoxidized is new and novel. Adhesives The objective of this application was to identify phenolic derivatives exhibiting strong adhesion to gold surfaces. It was empirically determined that phenolic derivatives or epoxy resins containing a thioether or disulfide component greatly contributed to the adhesiveness to gold. Phenolic derivatives were prepared and then converted into thioether analogs using ethanedithol followed by oxidation of this intermediate to the disulfide. Phenolic resins were prepared by electrophilic substitution of allyl phenol derivatives with formaldehyde and then free radically copolymerizing with ethanedithol. Epoxidation was performed using epichlorohydrine. 67

68

Novel Sulfur-containing Phenolic Resin, Process

REACTION

i. ii. iii. iv.

Formalin, oxalic acid Ethanedithol, benzoyl peroxide Ethanedithol Hydrogen peroxide, ethanol

EXPERIMENTAL 1. Preparation of 2,20 -dihydroxy-3,30 -dimethoxy-5,5-diallyl-diphenylmethane A flask containing 4-allyl-2-methoxyphenol (328 g), 37% formalin (81 g), and oxalic acid (3 g) was heated to 1008C for 3 hours. The mixture was then concentrated and the product isolated. 2. Preparation of phenolic resin The step 1 product (50 g), ethanedithol (11.3 g), and benzoyl peroxide (1.42 g) were mixed and heated to 1008C for 8 hours. Thereafter, the mixture was concentrated and the product isolated. 3. Preparation of phenolic monothiol A reaction flask was charged with 2-allylphenol (0.536 mol) and ethanedithol (0.536 mol) and then heated under reflux for 4 hours. GPC indicated the product was 65% active and the material used without purification.

Testing

69

4. Preparation of phenolic disulfide A flask was charged with the step 3 product (35 g) and then treated dropwise with 3.4 ml 30% aqueous hydrogen peroxide solution diluted with 6.8 ml of ethanol. The mixture was then heated to 708C and the reaction extent monitored by GPC. After completion of the reaction, the product was extracted with acetone and distilled water and then concentrated. The absence of an infrared absorbance at 2550 cm21 was understood to mean that the thiol was converted to the disulfide.

DERIVATIVES Phenolic disulfide derivatives are illustrated below.

where n ¼ 1 – 5 R1 ¼ OCH3, SCH3, SH, CO2H, C6H5, SO3H, NO2, NH2, CN, CH3

TESTING Formulations of selected experimental agents are provided in Table 1. Adhesion testing results are provided in Table 2.

TABLE 1. Formulation of Phenolic Disulfide Resins Used in Evaluating Surface Adhesion to a Gold Surface Component Phenolic disulfide resin MEH7800SS KA-7052 YX4000 BREN105 Curing accelerator PED153

Description

Weight (g)

Step 4 product Phenol-aralkyl resin Melamine-modified phenolic resin Biphenyl epoxy resin Brominated epoxy resin Polyethylene oxide Adduct of triphenylphosphine and p-benzoquinone

4.0 77.4 6.0 82.0 18.0 3.0 3.0

70

Novel Sulfur-containing Phenolic Resin, Process

TABLE 2. Results of 18088 Peeling Strength from a Polypropylene Film Substrate Using a Selected Experimental Agent Provided below Evaluated Item

Comparative Example 1

Example 6

Example 7

Example 8

Peeling strengh (N) Peeling energy (Nm)

10.5 5.8 1024

11.8 7.2 1024

10.9 6.6 1024

11.5 7.0 1024

Example

R1

6 7 8

OH SH CO2H

NOTES 1. Phenolic, (I), and naphtholic, (II), condensation polymers containing cyclopentane were previously prepared by Sue et al. (1). These materials were subsequently epoxidized with epichlorohydrin and used in electronic devices as ICs and Lumen solubility indexes (LSIs). In a subsequent investigation by Abe et al. (2) novolak resins functionalized with thiophene, (III), were prepared and used as adhesives.

2. Shinohara et al. (3) prepared epoxy resin compositions, (IV), by epoxidizing 3,30 ,5,50 -tetramethyl-4,40 -dihydroxyldiphenyl methane and using these

Notes

71

materials as adhesives. Bisphenol A, (V), was modified by Shinohara et al. (4) by functionalizing it with an epoxy resin using triphenylphosphine as catalyst and used the material as an adhesive.

References 1. H. Sue et al., U.S. Patent 6,713,589 (March 30, 2004) and U.S. Patent 6,329,492 (December 11, 2001). 2. T. Abe et al., U.S. Patent Application 20080044667 (February 21, 2008). 3. S. Shinohara et al., U.S. Patent 7,332,557 (February 19, 2008). 4. S. Shinohara et al., U.S. Patent 6,569,959 (May 22, 2003).

b. Polyimides

Title: Novel Polyimide Film with Improved Adhesiveness Author: Assignee:

Takashi Kikuchi et al. Kaneka Corporation (Osaka, JP)


72

20080097073 (April 24, 2008) High 2010

Synthesis of polyaromatic ether polyimides as adhesives by plasma or thermal treatment of the film surface. Ongoing 3-year investigation Adhesives Polyimide films prepared by (i) casting, (ii) volatilizing off a solvent to obtain a gel film, or (iii) or chemically imidizing are very poor adhesives. Adhesiveness can be improved by performing surface treatments such as corona treatment, plasma treatment, flaming treatment, or UV treatment before providing an adhesive layer on the polyimide films. Flexible copper-clad laminates with nonthermoplastic polyimides were prepared in a two-step process entailing isolating the polyamic acid and then thermally imidizing to the corresponding polyimide. Plasma or thermal treatments of selected polyimides generated materials with excellent bonding strength when evaluated on laminated copper foil.

Experimental

73

REACTION

i. N,N 0 -Dimethylformamide, 3,30 4,40 -biphenyltetracarboxylic dianhydride, 3,30 ,4,40 ethyleneglycol dibenzoate tetracarboxylic dianhydride

EXPERIMENTAL 1. Preparation of polyamic acid A 2000-ml glass flask was charged with N,N-dimethylformamide (780 g) and bis[4(4-aminophenoxy)phenyl]sulfone (117.2 g). While the mixture was stirring 3,30 4,40 biphenyltetracarboxylic dianhydride (71.7 g) was gradually added followed by 3,30 ,4,40 -ethyleneglycol dibenzoate tetracarboxylic dianhydride (5.6 g) and the mixture stirred in an ice bath for 30 minutes. A solution of 3,30 ,4,40 -ethyleneglycol dibenzoate tetracarboxylic dianhydride (5.5 g) dissolved in N,N-dimethylformamide (20 g) was then gradually added to the reaction mixture while monitoring the viscosity under stirring. The addition and the stirring were stopped when the viscosity reached 3000 poise and the product was isolated.

2. Preparation of nonthermoplastic polyimide The step 1 product was flow cast on a 25-mm positron emission tomography (PET) film so that the final film thickness was 20 mm then dried at 1208C for 5 minutes. The film was then peeled from the PET film, held onto a metal pin frame, and dried at 1508C for 5 minutes, 2008C for 5 minutes 2508C for 5 minutes, 3508C for 5 minutes, and the product isolated having a Tg of 2708C.

74

Novel Polyimide Film with Improved Adhesiveness

DERIVATIVES Monomers depicted below were used to prepare polyimide derivatives appearing in Table 1.

TABLE 1. Molar Ratios of Diamines and Dicarboxylic Anhydrides Used in Preparing Polyimides Entry 1 2 3 4 5 6

4,40 -ODA

BAPP

BTDA

PDMA (1st)

p-PDA

PDMA (2nd)

20 30 30 20 10 20

25 20 20 30 40 50

20 20 10 20 20 10

20 25 35 25 25 35

55 50 50 50 50 50

57 52 52 52 52 52

Abbreviations: ODA ¼ ortho dispersant index, BAPP ¼ butyl acetate poly propylene, PDMA ¼ poly dimethyl acrylate, and PDA ¼ phenylene diamine.

TESTING Bonding Strength Bonding strengths of experimental agents were evaluated on laminated copper foil after samples were subjected to plasma treatment or after being heated to 3808C. Testing results are provided in Table 2.

Notes

75

TABLE 2. Bonding Strength of Selected Thermoplastic Polyimides after Exposing Surfaces to Plasma Treatment or Heating Material to 38088 C 908 Peeling (Retention in Parentheses) Entry

1808 Peeling (Retention in Parentheses)

Postplasma Treatment (N/cm)

Postheating Treatment (N/cm)

Postplasma Treatment (N/cm)

Postheating Treatment (N/cm)

15.2 (95%) 14.7 (98%) 14.1 (97%) 14.0 (95%) 13.0 (98%) 12.5 (96%)

14.4 (96%) 14.4 (96%) 14.1 (97%) 14.1 (96%) 12.9 (97%) 12.6 (97%)

15.2 (95%) 15.3 (98%) 13.3 (95%) 13.5 (93%) 12.1 (97%) 11.5 (96%)

15.7 (97%) 15.3 (98%) 13.3 (95%) 13.5 (93%) 11.9 (95%) 11.5 (96%)

1 2 3 4 5 6

NOTES 1. Additional polyimide derivatives effective as adhesives are described by the authors (1) in earlier investigations. 2. High adhesive polyimide films were prepared by Kaneshiro et al. (2) consisting of 2,2-bisaminophenoxylphenylpropane and paraphenylene diamine, pyromellitic dianhydride, and 3,30 ,4,40 -benzophenone tetracarboxylic dianhydride. 3. Adhesive films consisting of thermoplastic polyimides were prepared by Yanagida et al. (3) consisting of 4,40 -oxydianiline, p-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane condensed with pyromellitic dianhydride. References 1. T. Kikuchi et al., U.S. Patent Application 20080050586 (February 28, 2008) and U.S. Patent Application 20070292701 (December 20, 2007). 2. H. Kaneshiro et al., U.S. Patent Application 20070260036 (November 8, 2007). 3. M. Yanagida et al., U.S. Patent Application 20070158869 (July 12, 2007).

C. Thermally Stable Adhesives a. Polyvinyl alcohol/ester copolymers

Title: Novel Poly(Vinylester) Copolymers and Poly(Vinyl alcohol) Copolymers and the Use Thereof Author: Assignee:

Monika Bruckmann et al. Celanese Ventures GmbH (Frankfurt am Main, DE)


20080027175 (January 31, 2008) High Mid-2010

Crosslinking polyvinyl alcohol as a method of enhancing its thermostability. Star polymers containing polyvinyl acetate and alcohols have previously been prepared. Adhesives Three- and four-stemmed polyvinyl acetate and alcohol star polymers have previously been prepared and used as adhesives. The objective of this application was to prepare new polyvinyl alcohol threedimensional geometries by crosslinking polyvinyl alcohol copolymers with bis(allyloxy)methane as a method for enhancing the thermal properties of these materials. The method for preparing crosslinked polyvinyl alcohols was by controlled radical copolymerization and consisted of three steps: a. The free radical polymerization of vinyl acetate in the presence of the free radical scavenger, tris(2,2,2-trifluorethyl) phosphite b. Addition of the crosslinking agent bis(allyloxy)methane c. Saponification of the copolymer with methanolic NaOH to prepare the crosslinked polyvinyl alcohol analogue This method avoids the use of extruding polyvinyl alcohol with additives.

76

Experimental

77

REACTION

i. Tris(2,2,2-trifluorethyl) phosphite, dibenzoyl peroxide, bis(allyloxy)methane ii. Methanol, sodium hydroxide EXPERIMENTAL 1. Preparation of poly(vinyl acetate-bis(allyloxy)methane)-poly(vinyl acetate) A 50-ml Schlenk tube containing a stirrer bar was charged with 3.4 ml of toluene, vinyl acetate (71 mmol), tris(2,2,2-trifluorethyl) phosphite (0.36 mmol), and dibenzoyl peroxide (0.18 mmol) successively at 608C. The reaction mixture was then stirred in the closed Schlenk tube at 708C for 2 hours and then treated with bis(allyloxy)methane (3.56 mmol) and stirred at 708C for 20 hours. All volatile components were then removed using an oil pump vacuum. The polymer was dissolved in acetone and then precipitated in heptane and 1.78 g product isolated as a white powder. 1

H-NMR (CDCl3) d 5.89 (t), 5.45 (s), 5.23 (d) poly(bis(allyloxy)methane), 4.83 (s, br, PVAc), 3.3 (s, br, poly(bis(allyloxy)methane)), 2.13, 1.98, 1.82, 1.72 (4, br, PVAc)

2. Preparation of poly(vinyl alcohol-bis(allyloxy)methane)-poly(vinyl alcohol) A flask containing 167 ml of 1% methanolic sodium hydroxide solution was heated to 508C and then treated with a solution of the step 1 product (50 g) dissolved in 333 ml of methanol dropwise over 30 minutes. The mixture was then stirred an additional 30 minutes and then filtered, washed to neutrality with methanol, dried under vacuum, and 25.0 g of product isolated. 1

H-NMR (D2O) d 5.89 (t), 5.45 (s), 5.23 (d), 3.3 (s, br, poly(bis(allyloxy)methane)), 4.65, 4.46, 3.89, 3.84, 3.31, 1.44–1.33 (4.times.s, 1.times.m, PVOH) ppm Tg ¼ 678C Tm ¼ 1808C

78

Novel Poly(Vinylester) Copolymers and Poly(Vinyl alcohol) Copolymers

DERIVATIVES Two additional derivatives were prepared using bis(N-acrylolyaminomethane and divinylbenzene as crosslinking agents as illustrated below.

NOTES 1. Additional crosslinked polyvinyl alcohol copolymers, (I), were prepared by Schulte et al. (1) and used as components in adhesives, emulsifiers, and detergents.

2. Polyvinyl acetate star polymers, (II), were previously prepared by Schulte et al. (2) and used as adhesive components.

Notes

79

References 1. J. Schulte et al., U.S. Patent Application 20080021185 (January 24, 2008) and U.S. Patent Application 20070032621 (February 8, 2007). 2. J. Schulte et al., U.S. Patent Application 20060160974 (July 20, 2006).

III. COSMETICS A. Topical a. (Methyl)acrylate terpolymers

Title: Novel Block (Co)polymers, Compositions Containing Them, Method of Treatment, and Method of Preparation Author: Assignee:

Celine Farcet L’Oreal S.A. (Paris, FR)



20080181859 (June 3, 2008) Medium January, 2010

Synthesis of poly(isobornyl methacrylate-co-isobornyl acrylate)-bmethacryloxypropyl-tris(trimethylsiloxy)silane and derivatives as topical cosmetic components having high shine and gloss. Isobornyl-siloxane containing polymers useful as cosmetics having high gloss and shine are unreported in the patent literature. Cosmetics Two modified poly(isobornyl-b-siloxane) copolymers were prepared consisting of poly(isobornyl methacrylate-co-isobornyl acrylate)-b-methacryl-oxypropyl-tris(trimethylsiloxy)silane and an acrylic acid derivative were free ionically prepared. When blended with a physiologically acceptable medium such as wax, both polymers exhibited enhanced shine and gloss. Although other high-gloss polymers such as poly(styrene-b-ethylene), polyurethanes, and polyether-amide block copolymers exist, the current materials do not require the use of fillers to alter gloss or high shine. In addition these polymeric agents are soluble in both organic and silicone solvents.


81

82

Novel Block (Co)polymers, Compositions Containing Them

REACTION

i. Isododecane, isobornyl acrylate, 2,5-bis(2-ethyl-hexanoylperoxy)-2,5-dimethylhexane, methacryloxypropyl-tris(trimethylsiloxy)silane EXPERIMENTAL 1. Preparation of poly(isobornyl methacrylate-co-isobornyl acrylate)-bmethacryloxypropyl-tris(trimethylsiloxy)silane A 250-ml reactor was charged with isododecane (30 g) and then heated to 908C and treated with isobornyl acrylate (4.5 g), isobornyl methacrylate (4.5 g), and 2,5-bis(2-ethyl-hexanoylperoxy)-2,5-dimethylhexane (0.37 g) over a period of 30 minutes. The mixture was then heated for 90 minutes at 908C and then treated with methacryloxypropyl-tris(trimethylsiloxy)silane (21 g) and 2,5-bis(2-ethylhexanoylperoxy)2,5-dimethylhexane (0.29 g) at 908C for 30 minutes and held at this temperature for 3 hours. The product was then cooled to ambient temperature and the product isolated. DERIVATIVE

TESTING Film stickiness, shine, and friability were determined by visual examination. Stickiness (resistance to olive oil) and the internal stresses of the polymer were also determined and are provided in Table 1.

Notes

83

TABLE 1. Physical Properties of Poly(isobornyl methacrylate-co-isobornyl acrylate)-co-methacryloxypropyl-tris(trimethylsiloxy)silane Prepared According to Current Application Variable Isobornyl acrylate (%) Isobornyl methacrylate (%) Methacryloxypropyltris(trimethylsiloxy)silane (%) Mw (Dal) Shine (film) Stickiness Internal stress

Example 1

Example 2

Example 3

15 15 70

25 25 50

35 25 30

67,700 Slightly shiny Sticky 0

61,900 Very slightly shiny Not sticky 0

67,800 White Not sticky Moderate

NOTES 1. In earlier investigations by the author (1, 2), poly((isobornyl methacrylate)-coisobornyl acrylate)-b-(isobornyl acrylate)-co-methacryloxypropyl-tris(trimethyl siloxy)silane)) and poly(isobornyl acrylate-b-isobornyl methacrylateb-isobutyl acrylate-b-acrylic acid), respectively, were prepared and used as a cosmetic agents to enhance gloss. 2. Bui et al. (3) prepared glossy cosmetics consisting of poly(styrene-b-ethylene) and poly(styrene-b-ethylene)-b-(butylene-b-styrene) blended with propyl silsesquioxane wax. 3. Fleissman et al. (4) prepared glossy cosmetics consisting of silicone-containing polyurethanes by condensing bis-polyethylene glycol dimethicone-polypropylene glycol with isophorone diisocyanate. 4. High-gloss silicone polyether-amide block copolymers were prepared by Nguyen et al. (5) by reacting polyetherdiamine with undecylenic acid and then postreacting with dimethylhydrogen endblocked polydimethylsiloxane using 1,3-diethenyl-1,1,3,3-tetramethyl-disiloxane platinum as catalyst and used in high gloss and shine cosmetics.

References 1. C. Farcet, U.S. Patent Application 20080175804 (July 24, 2008). 2. C. Farcet, U.S. Patent Application 20080031837 (February 7, 2008). 3. H.S. Bui et al., U.S. Patent Application 20070055029 (July 17, 2008). 4. L.G. Fleissman et al., U.S. Patent Application 20080107695 (May 8, 2008). 5. K.T. Nguyen et al., U.S. Patent Application 20080045687 (February 21, 2008).

IV. CRYSTALLINE MATERIALS A. Liquid-Crystal Displays a. Cholesterol derivatives

Title: Polymerizable Liquid-Crystal Composition and Uses for the Same Author: Assignee:

Mayumi Tanabe Chisso Corporation (Osaka, JP) Chisso Petrochemical Corporation (Osaka, JP)

U.S. Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus: Originality: Application:

Observations:

20080001121 (January 3, 2008) High Mid-2010

Cholesterol-containing liquid crystals that selectively reflect light of various wavelengths. While liquid-crystal cholesterol derivatives are reported in the literature, this is the first appearance of polymethacrytate-g-cholesterol. Liquid-crystal displays Coating materials Polymers that reflect specific colors such as red, green, and blue at a fixed temperature are unreported in the patent literature. To address this concern (meth)acrylic cholesterol monomers were prepared and then photopolymerized and isolated. The products had the following properties: a. A cholesteric phase at ambient temperature b. Reflected color variability by varying co- or terpolymer content c. Convertible to flake-shaped pigment that can be affixed to a substrate Poly(ethylene terephthalate-g-cholesterol) has been reported in the patent literature as having similar properties as those in the current application.


85

86

Polymerizable Liquid-Crystal Composition and Uses for the Same

REACTION

i. Sodium hydroxide, water, 1-caprolactone, hydrochloric acid ii. N,N0 -Dimethylaniline, 2,6-di-t-butyl-4-methylphenol, dioxane, acrylic chloride iii. Cholesterol, 4-dimethylamino-pyridine, CH2Cl2, N,N0 -dicyclohexylcarbodiimide iv. 2,2-Dimethoxy-1,2-diphenylethane-1-one

EXPERIMENTAL 1. Preparation of 6-hydroxyhexanoic acid A solution of sodium hydroxide (173 g) dissolved in water (867 g) was treated with the dropwise addition of 1-caprolactone (150 g) and then stirred at ambient temperature for 5 hours. The mixture was then neutralized with 6M hydrochloric acid, extracted with ethyl acetate, and the organic layer washed with water. The organic layer was dried using MgSO4 and concentrated. The residue was recrystallized from mixed solvents consisting of tetrahydrofuran (TH) and heptane and 106.47 g of product isolated. 1

H-NMR (CDCl3) d 3.68 (t, 2H), 2.38 (t, 2H), 1.57–1.72 (m, 4H), 1.39– 1.47 (m, 2H)

2. Preparation of 6-acryloyloxyhexanoic acid A reactor containing the step 1 product (106.47 g), N,N0 -dimethylaniline (109 g), 2,6di-t-butyl-4-methyl-phenol (0.9 g), and 1000 ml of dioxane at ambient temperature was treated with the dropwise addition of acrylic chloride (80 g) and then stirred at

Derivatives

87

608C for 2 hours. The mixture was then poured into ice and water and ethyl acetate added. The organic portion separated and was washed sequentially with 1M hydrochloric acid, aqueous Na2CO3, and water. The solution was dried using MgSO4, concentrated, and 148.56 g of product isolated. 1

H-NMR (CDCl3) d 6.38 (dd, 1H), 6.14 (dd, 1H), 5.83 (dd, 1H), 4.16 (t, 2H), 2.38 (t, 2H), 1.64– 1.73 (m, 4H), 1.40 –1.47 (m, 2H)

3. Preparation of 6-acryloyloxyhexanoic acid cholesterol ester A reactor containing the step 2 product (70 g), cholesterol (121 g), and 4-dimethylamino-pyridine (19 g) dissolved in 1500 ml of CH2Cl2 was treated with the dropwise addition of N,N0 -dicyclohexylcarbodiimide (19 g) dissolved in 80 ml CH2Cl2 while the mixture was being cooled with ice water. The solution was stirred at ambient temperature for 18 hours and then filtered and water added to the mixture. The organic component was isolated, washed sequentially with 1M hydrochloric acid, 2M sodium hydroxide solution, and water and then dried using MgSO4. The mixture was concentrated, the residue filtered through celite, and purified by silica gel chromatography using heptane/ethyl acetate, 9/1, respectively. After recrystallization from mixed solvents of diethyl ether and ethanol,100.35 g of produce was isolated having a melting point (mp) of 45.3 – 45.88C. 1

H-NMR (CDCl3) d 6.41 (dd, 1H), 6.12 (dd, 1 H), 5.37 (d, 1H), 4.59– 4.63 (m, 1H), 4.15 (t, 2H), 2.29 (t, 2H), 0.6–1.96 (m, 47H)

4. Preparation of poly(cholesterol-6-hexylacrylate) Although precise photopolymerization conditions were not supplied by the author, samples were irradiate 30 seconds using a high-pressure mercury lamp having a wavelength of between 300 and 400 nm. Samples were additized with 0.1 wt% 2,2-dimethoxy-1,2-diphenylethane-1-one as the photoinitiator.

DERIVATIVES Derivatives are illustrated below.

88


TESTING Reflected color testing results at 22 and 408C for selected copolymers photolytically and thermally are provided in Tables 1 and 2, respectively.

TABLE 1. Reflected Colors of Selected Copolymer Films at Varying Compositions at 22 and 4488 Ca

Entry

n¼5 Composition (wt%)


228C

408C

91 80 62 50

9 20 38 50

Green Green Orange Ruby red

Green Greenish yellow

A1 A3 A6 A8

Reflected Color

a Copolymers were photochemically prepared with UV light using 2,2-dimethoxy-1,2-diphenylethane-1-one as the photoinitiator.

TABLE 2. Reflected Colors of Selected Terpolymer Films at Varying Compositions at 22 and 4488 Ca

Entry B1 B2 B3 B4 C1 a


n ¼ 10 Composition (wt%)



44 40 36 33.3 44

11 20 27 33.3 —

44 40 36 33.3 44

— — — — 12

Films were prepared by heating in oven for 30 seconds at 1208C.

Reflected Color 228C

408C

Red Orange Green Blue Transparent (red)

Green Viridian Blue Blue —

Notes

89

NOTES 1. An optically active liquid crystalline composition consisting of low-molecularweight poly(ethylene terephthalate-g-cholesterol) was prepared by Mazaki et al. (1) and used as an optical material. 2. Optically active polymerizable liquid-crystal monomers, (I), providing polymeric cholesteric liquid-crystal films were prepared by Seki et al. (2) and used in optical applications.

3. Oomori et al. (3) polymerized di(meth)acrylate monomers, (II), containing liquid-crystal phases for use in liquid-crystal displays.

4. Goldfinger (4) proposed preparing an alkoxy(meth)acrylate cholesterol derivative, (III), as a liquid-crystal composition.

90


References 1. H. Mazaki et al., U.S. Patent 7,303,695 (December 4, 2007). 2. T. Seki et al., U.S. Patent Application 20070164255 (July 19, 2007) and U.S. Patent Application 20060157672 (July 20, 2006). 3. Y. Oomori et al., U.S. Patent Application 20080003382 (January 3, 2008). 4. M.B. Goldfinger, U.S. Patent Application 20070228326 (October 4, 2007).

b. Trans-isosorbide ester diacrylates

Title: Liquid-Crystal Compositions and Polymer Networks Derived Therefrom Author: Assignee:

Marc B. Goldfinger et al. E.I. DuPont De Nemours and Company (Wilmington, DE)



Observations:

20070267599 (November 22, 2007) Very high Mid/late 2009

Method for preparing polymerizable chiral intermediates containing optically active isosorbide to prepare twisted nematic or cholesteric phases. While isosorbide polymers have been previously prepared, the materials in the current application are unreported. Linear polarizers Lenses Collimators Diffusers Significant efforts have been directed to preparing materials exhibiting fixed cholesteric optical properties. The current application represents an ongoing investigation for preparing bisacrylate intermediates containing optically active isosorbide. Once polymerized, these materials generated twisted nematic phases in nematic liquid crystals and produced polymer networks that exhibited cholesteric optical properties. High-strength multilayer laminates comprising twisted nematic liquid crystals containing biaxially oriented poly(ethylene terephthalate) films were previously prepared by this group in an earlier investigation.

91

92

Liquid-Crystal Compositions and Polymer Networks Derived Therefrom

REACTION

i. Isosorbide, p-toluenesulfonic, xylenes ii. Triethylamine, 6-bromohexanoyl chloride, THF iii. Potassium bicarbonate, tetrabutylammonium iodide, 2,6-di-tert-butyl-4-methylphenol, THF, acrylic acid EXPERIMENTAL 1. Preparation of trans-isosorbide diester intermediate A mixture consisting of 4-hydroxybenzoic acid (80 g), isosorbide (40 g), p-toluenesulfonic acid (2 g), and 500 ml xylenes was refluxed for 7 hours and then treated with additional p-toluenesulfonic acid (1.0 g). The mixture was further refluxed an additional 2.5 hours and then cooled to ambient temperature. Xylenes were decanted and the solids dissolved in 500 ml EtOAc. The solution was then washed with 1% aqueous NaHCO3 solution, concentrated, and the product isolated.

Experimental 1

93

H-NMR (d6-DMSO) d 3.88 –3.98 (m, 4H), 4.58 (d, J ¼ 4.9 Hz, 1H), 4.93 (t, J ¼ 5.3 Hz, 1H), 5.27 (br s, 1H), 5.32 (q, J ¼ 4.5 Hz, 1H), 6.85 (d, J ¼ 8.8 Hz, 2H), 6.87 (d, J ¼ 8.8 Hz, 2H), 7.81 (d, J ¼ 8.8 Hz, 2H), 7.84 (d, J ¼ 8.8 Hz, 2H), 10.36 (s, 2H)

2. Preparation of trans-isosorbide diester bromo ether intermediate A mixture consisting of the step 1 product (30 g), 200 ml THF, and 48 ml triethylamine was cooled to 08C and then treated with the dropwise addition of 6-bromohexanoyl chloride (36.5 g) dissolved in 150 ml THF over 25 minutes. After stirring for 2 hours the reaction was partitioned between water and diethyl ether and the organic component washed with dilute hydrochloric acid, water, dried, filtered, and concentrated. The residue was crystallized from isopropyl alcohol and the product isolated. 1

H-NMR (CCl3D) d 1.59 (m, 4H), 1.80 (m, 4H), 1.93 (m, 4H), 2.60 (t, J ¼ 7.4 Hz, 2H), 2.61 (t, J ¼ 7.4 Hz, 2H), 3.43 (t, J ¼ 6.7 Hz, 2H), 3.44 (t, J ¼ 6.7, 2H), 4.07 (m, 4H), 4.66 (app d, 1H), 5.04 (app t, 1H), 5.41 (app q, 1H), 5.48 (app d, 1H), 7.16 (d, J ¼ 8.9 Hz, 2H), 7.18 (d, J ¼ 8.9 Hz, 2H), 8.04 (d, J ¼ 8.9 Hz, 2H), 8.11 (d, J ¼ 8.8 Hz, 2H)

3. Preparation of trans-isosorbide diacrylic acid A mixture consisting of the step 2 product (40 g), potassium bicarbonate (48.7 g), tetrabutylammonium iodide (8.0 g), 2,6-di-tert-butyl-4-methylphenol (1.74 g), and 500 ml THF was treated with acrylic acid (11.2 g) and then refluxed for 6.5 hours and stirred at ambient temperature for 16 hours. Thereafter it was diluted with diethyl ether, washed with water, dried, filtered, concentrated, and then dissolved in hot isopropyl alcohol. Upon cooling solids precipitated from the solution and the product isolated after filtering, mp ¼ 508C. 1

H-NMR (CCl3D) d 1.52 (m, 4H), 1.75 (m, 4H), 1.81 (m, 4H), 2.60 (t, J ¼ 7.4 Hz, 2H), 2.61 (t, J ¼ 7.4 Hz, 2H), 4.07 (m, 4H), 4.191 (t, J ¼ 6.5 Hz, 2H), 4.194 (t, J ¼ 6.5 Hz, 2H), 4.66 (app d, J ¼ 4.7 Hz, 1H), 5.05 (app t, J ¼ 5.2 Hz, 1H), 5.41 (app q, J ¼ 5.2 Hz, 1H), 5.48 (br s, 1H), 5.82 (br d, J ¼ 10.4 Hz, 2H), 6.12 (app dd, J ¼ 17.3, 10.4 Hz, 2H), 6.40 (app d, J ¼ 17.3 Jz, 2H), 7.16 (d, J ¼ 8.4, 2H), 7.18 (d, J ¼ 8.4 Hz, 2H), 8.04 (d, J ¼ 8.8 Hz, 2H), 8.10 (d, J ¼ 8.8 Hz, 2H)

94

Liquid-Crystal Compositions and Polymer Networks Derived Therefrom

DERIVATIVES

NOTES 1. Additional liquid-crystal compositions are described by the authors (1) in an earlier investigation. 2. Seki et al. (2) prepared polymerizable liquid crystalline compositions containing isosorbide, (I), which retained its orientation after alignment and mechanical strength when converted into films.

Notes

95

3. Optically active polymerizable isosorbide derivatives, (II) and (III), were prepared by Koyama et al. (3) and used in photoresist compositions.

4. Lub et al. (4) prepared polyisosorbide derivatives, (IV), having high helical twisting with improved thermal stability and alignment capability for use as an optical color filter.

References 1. M.B. Goldfinger et al., U.S. Patent Application 20070228326 (October 4, 2007). 2. T. Seki et al., U.S. Patent Application 20070164255 (July 19, 2007). 3. H. Koyama et al., U.S. Patent Application 20060058480 (March 16, 2006). 4. J. Lub et al., U.S. Patent 7,311,948 (December 25, 2007).

c. Polyacetylene derivatives

Title:

Novel Polyacetylene Derivatives

Author: Assignee:

Kento Okoshi Japan Science and Technology Agency (Saitama, JP)


20070260028 (November 8, 2007) Moderate Mid-2010

Preparation of materials having a helical rigid-rod shape that exhibit cholesteric or nematic crystal-phase behavior. Achiral polyacetylene analogs are reported in the literature. Liquid-crystal displays In an earlier investigation reported in the patent literature, a water-soluble polyacetylene was prepared that did not contain an asymmetric carbon and was used in biological research involving biomimesis. The current application is a follow-up to that study. In this study, however, optically active amino acids were incorporated onto helical polyacetylene to induce a cholesteric or nematic-phase change.

REACTION

96

Derivatives

97

i. Dimethylacetamide, 1-hydroxybenzotriazole, N,N0 -dicyclohexylcarbodiimide ii. THF, triethylamine, norbornadiene rhodium dichloride

EXPERIMENTAL 1. Preparation (S)-(1)-4-(decyloxyalanylcarbamoyl)phenylacetylene A reactor charged with 4-ethynylbenzoic acid (2.01 mmol) dissolved in dimethylacetamide was treated with 1-hydroxybenzotriazole (2.01 mmol) and N,N0 -dicyclohexylcarbodiimide (2.07 mmol) and stirred for 2 hours at ambient temperature. The mixture was then treated with (S )-(þ)-decylalaninate (2.13 mmol) and stirred at ambient temperature for 3 hours and then at 1208C for a further 3 hours. The reaction was filtered, concentrated, and the residue purified by a silica gel chromatography using chloroform and ethyl acetate. After recrystallization from hexane 0.33 g of product was isolated as a crystalline solid. 1

H-NMR (CDCl3) d 0.88 (t, 3H; CH), 1.21– 1.29 (m, 14H; CH2), 1.52 (d, 3H; CH3), 1.63–1.68 (m, 2H; CH2), 4.15–4.21 (m, 2H; CH2), 4.75–4.78 (m, 1H; CH), 6.72 (d, 1H; NH), 7.53 (d, 2H; aromatic), 7.80 (d, 2H; aromatic) 13 C-NMR (CDCl3) d 14.04, 18.78, 22.69, 25.90, 28.67, 29.24, 29.31, 29.54, 29.55, 31.93, 48.82, 65.92, 79.49, 82.87, 125.77, 127.07, 132.38, 134.29, 165.96, 173.24

2. Preparation of poly[(S )-(1)-4-(decyloxyalanylcarbamoyl)phenylacetylene A dry polymerization tube was charged with the step 1 product (0.28 mmol), 300 ml THF, and 100 ml triethylamine and then treated with a solution of norbornadiene rhodium dichloride (0.028 mmol) dissolved in THF. The mixture was stirred at 308C for 3 hours and was then poured into excess ethanol. The filtrate was separated by centrifugation and dried. After dissolving in benzene and freeze drying, the product was isolated having an Mn of 230,000 Da. 1

H-NMR (CDCl3) d 0.86 (singlet-like, 3H; CH3), 1.05–1.40 (singlet-like, 14H; CH2), 1.5 (broad, 3H; CH3), 1.6 (broad, 2H; CH2), 4.1 (broad, 2H; CH2), 4.7 (broad, 1H; CH), 6.1 (broad, 1H; .dbd.CH), 6.8 (broad, 2H; aromatic), 7.5 (broad, 2H; aromatic) 13 C-NMR (CDCl3) d 14.04, 18.02, 22.68, 25.96, 28.69, 29.33, 29.60, 31.94, 48.71, 65.47, 127.40, 132.79, 167.00, 173.23

DERIVATIVES Polyacetylene derivatives and corresponding number-average molecular weights are provided in Table 1.

98

Novel Polyacetylene Derivatives

TABLE 1. Polyacetylene Derivatives Prepared According to Current Inventiona Entry

Repeat Unit

Mn (Da)

5

460,000

7

350,000

a These materials had helical structures of rigid-rod shapes and exhibited a liquid-crystal phase either in an organic solvent or in the molten state.

TESTING Measurement of practical standard value of parallelism degree in the orientation of polymer main chains in an electric-field-oriented film. From half width of the intensity distribution measured along the Debye ring of reflection derived from a distance between polymer chains obtained by X-ray diffraction, the practical standard value of parallelism degree in orientation was determined to be 0.92.

NOTES 1. A water-soluble salt of the above synthetic helical polyacetylene derivative, (I), in the current application having no asymmetric carbon atom was prepared by Sakajiri et al. (1) and used in biological research associated with biomimesis.

2. Hyperbranched polyacetylenes were prepared by Tang et al. (2), which were curable into thermosets by heat or irradiation to provide patterns with nanometer resolution and were used in ceramics.

Notes

99

3. A new class of mesogen consisting of polyacetylene derivatives, (II), containing aliphatic spacers was prepared by et al. Tang (3), which had high solvent solubility, moderate melting points, and excellent tractability.

References 1. K. Sakajiri et al., U.S. Patent Application 20070145329 (July 28, 2007). 2. B.Z. Tang et al., U.S. Patent Application 20060247410 (November 2, 2006). 3. B.Z. Tang et al., U.S. Patent Application 20060022169 (February 2, 2006) and U.S. Patent 7,070,712 (July 4, 2006).

d. Poly(trans-di-hexyl-1,4-phenylene)

Title: Polymerizable Liquid-Crystal Compound, Liquid-Crystal Composition, Optical Anisotropic Material, and Optical Element Author: Assignee:

Hiromichi Nagayama et al. Asahi Glass Company (Chiyoda-Ku, JP)


20080204650 (August 28, 2008) Moderate May, 2011

Preparation of polymerizable liquid crystals containing trans-1,4cyclohexyl and 1,4-phenylene. The preparation of liquid crystals consisting of trans-1,4-cyclohexyl and 1,4-phenylene has been an ongoing 5-year investigation by this group. Polarizer for reading and recording on an optical disc Polymerizable liquid crystals containing trans-1,4-cyclohexyl and 1,4phenylene were prepared in six steps involving: i. Coupling of 4-bromo-iodobenzene with 4-methoxy-2-methyl-phenyl boronic acid using palladium acetate ii. Alcohol formation using the Grignard reaction iii. Olefin formation from an acid-catalyzed dehydration of the alcohol iv. Olefin reduction using 10% palladium-activated carbon v. Ether de-alkylation using boron tribromide vi. Ester formation Polymerizable liquid-crystal analogs of the current application containing an internal ester were previously prepared by this group. In addition, polymerizable liquid crystals containing only trans-1,4-cyclohexyl were also previously prepared and are described.

100

Experimental

101

REACTION

i. 4-Methoxy-2-methyl-phenyl boronic acid, palladium acetate, triphenyl phosphine acetone, sodium bicarbonate ii. Magnesium, THF, 4-(1-(4-n-propyl cyclohexyl))-cyclohexylketone iii. p-Toluene sulfonic acid monohydrate, toluene, molecular sieve 4A iv. 10% Palladium on carbon, hydrogen, hexane, t-butoxy potassium, N,N0 dimethylformamide v. CH2Cl2, boron tribromide vi. 6-Bromohexyl acrylate, potassium carbonate, potassium iodide, acetone EXPERIMENTAL 1. Preparation of bromo diphenyl intermediate A flask was charged with 4-bromo-iodobenzene (0.079 mol), 4-methoxy-2-methylphenyl boronic acid (0.087 mol), palladium acetate (0.004 mol), and triphenyl phosphine (0.008 mol) and then treated with 200 ml acetone and 250 ml 2M NaHCO3. The mixture was refluxed at 658C for 18 hours and was then treated with water and diethyl ether and the organic layer isolated. This layer was washed with 40 ml saturated sodium chloride solution and water, dried over MgSO4, filtered, and concentrated. The residue was purified by column chromatography using silica gel with CH2Cl2/ hexane, 1:1, and then recrystallized in CH2Cl2/hexane, 7:3, respectively, and 16.4 g of product isolated. 2. Preparation of alcohol diphenyl intermediate A 500-ml reactor was charged with magnesium (1.55 g) and then treated with the dropwise of the step 1 product (0.057 mol) dissolved in 50 ml THF and heated to 708C for 3 hours. The mixture was then cooled to 08C and treated over a period of

102

Polymerizable Liquid-Crystal Compound, Liquid-Crystal Composition

30 minutes with 4-(1-(4-n-propyl cyclohexyl))-cyclohexylketone (0.057 mol) dissolved in 100 ml THF. The mixture was then heated to 708C for 3 hours and then treated with 100 ml of 1M NH4Cl, concentrated, and purified as described in step 1 using ethyl acetate/hexane, 7:3, respectively, and 16.8 g of product isolated. 3. Preparation of cyclohexenyl diphenyl intermediate A 500 ml-eggplant flask was charged with the step 2 product (0.039 mol), p-toluene sulfonic acid monohydrate (0.002 mol), and 200 ml toluene. An isobaric dropping funnel containing 20 g molecular sieve 4A was then attached and the mixture refluxed at 1108C for 4 hours. After cooling the material was purified using the step 1 procedure and 14.9 g of product isolated. 4. Preparation of trans-cyclohexyl diphenyl intermediate A 5000-ml pressure-resistant reactor was charged with the step 3 product (0.036 mol) dissolved in 200 ml THF and 10% palladium on carbon (2.8 g). The reactor was then pressurized to 0.4 MPa with hydrogen and the reaction performed at 608C for 3 hours. The mixture was then filtered with Celitew, concentrated, and the cis and trans isomers isolated in 95%. The isomers were then recrystallized in 100 ml hexane and the trans isomer isolated. The filtrate was concentrated, treated with t-butoxy potassium (0.25 mol), and 300 ml N,N-dimethylformamide and then refluxed at 1008C for 6 hours to convert the cis isomer to the trans isomer. The reaction was stopped by the dropwise addition of 500 ml water and the material purified according to the step 1 procedure. After recrystallization 11.51 g of product was isolated. 5. Preparation of alcohol diphenyl dicyclohexyl intermediate A 500-ml flask equipped with a reflux condenser, stirrer, and a dropping funnel was treated with the step 4 product (0.027 mol) and 200 ml CH2Cl2. The solution was then treated with the dropwise addition of boron tribromide (0.135 mol) over 30 minutes at such a rate that the internal reaction temperature did not exceed 108C. The mixture was then stirred at ambient temperature for 3 hours and then treated with water to stop the reaction. Posttreatment was carried out in the same manner as described in step 1 and 10.01 g of product isolated. 6. Preparation of acrylic diphenyl dicyclohexyl A mixture consisting of the step 5 product (0.025 mol), 6-bromohexyl acrylate (0.027 mol), K2CO3 (0.043 mol), KI (0.0037 mol), and 500 ml acetone were refluxed at 608C for 24 hours and then purified as in the manner described in step 1 and 9.8 g of product isolated. The phase transition temperature from the crystal phase to the nematic phase was 1058C where the Dn of the compound using a laser beam having a wavelength of 589 nm at 808C was 0.1305 (extrapolation value). 1

H-NMR (CDCl3) d: 0.98 (t, 3H), 1.2–1.9 (m, 31H), 2.34 (s, 3H), 2.72 (m, 1H), 3.94 (t, 2H), 4.15 (t, 2H), 5.8– 6.4 (m, 3H), 6.64 (dd, 2H), 7.1–7.3 (dd, 5H)

Notes

103

DERIVATIVES TABLE 1. Physical Properties of Selected Liquid-Crystal Derivatives Derived Using Optical Anisotropic Materialsa Phase Transition (8C)

Dn

4

104

0.1639

5

96

0.1513

6

100

0.1589

10

98

0.1505

Entry

a

Structure

All Dn values were determined at 808C using a laser beam having a wavelength of 589 nm.

NOTES 1. Kaida et al. (1,2) prepared optically anisotropic polymerizable liquid-crystal derivatives, (I) and (II), respectively, containing internal esters that were used in optical disc applications.

2. trans-1,4-Cyclohexylene liquid-crystal derivatives, (III), prepared by Kumai et al. (3), were effective in blue laser light (300– 450 nm) and were used in optical disc applications.

104

Polymerizable Liquid-Crystal Compound, Liquid-Crystal Composition

3. Optically anisotropic liquid-crystal displays consisting of triphenylene, (IV), were prepared by Ushiyama et al. (4) and used in optical compensatory film.

4. Anisotropic oriented materials consisting of aromatic acrylate acid esters, (V), were prepared by Saitoh et al. (5) and used in optical film.

References 1. Y. Kaida et al., U.S. Patent Application 20070104894 (May 10, 2007). 2. Y. Kaida et al., U.S. Patent Application 20070102669 (May 10, 2007). 3. H. Kumai et al., U.S. Patent Application 20060124900 (June 15, 2006). 4. A. Ushiyama et al., U.S. Patent Application 20080199637 (August 21, 2009). 5. Y. Saitoh et al., U.S. Patent Application 20080211996 (September 4, 2008).

e. Poly(thieno[3,2-b]thiophene)

Title:

Polymerizable Thieno[3,2-b]thiophenes

Author: Assignee:

Martin Heeney Merck Patent Gesellschaft Mit Beschrankter Haftung (Darmstadt, DE)


Observations:

20070246704 (October 25, 2007) Moderate Mid-2009

Synthetic methods for preparing thieno[3,2-b]thiophene monomers. Ongoing 6-year investigation in preparing polythiophene derivatives effective as liquid crystals. Liquid crystals Optical films Organic field-effect transistors Electroluminescent devices This invention describes the preparation and polymerization of thieno[3,2-b]thiophene monomers using the Suzuki coupling reaction with tetrakis(triphenylphosphine)palladium(0). In this application six new thieno[3,2-b]thiophenes methacrylates and oxetane derivatives were prepared in five or fewer synthetic steps.

105

106


REACTION

i. ii. iii. iv. v.

N-Bromosuccinimide, N,N0 -dimethylformamide THF, n-butyllithium, 6-bromohexyloxy-t-butyl-dimethylsilane THF, n-butyllithium, pinacol boronate Tetrakis(triphenylphosphine)palladium(0), THF, potassium carbonate Methacrylic anhydride, tetrabutylammonium fluoride

EXPERIMENTAL 1. Preparation of 2,5-dibromo-thieno[3,2-b]thiophene N-Bromosuccinimide (6.94 mmol) was added to a solution of thieno[3,2-b]thiophene (6.94 mmol) dissolved in 30 ml N,N0 -dimethylformamide at ambient temperature and the mixture stirred for 3 hours. The mixture was then poured into 100 ml of water and the precipitate was isolated, washed with water, dried, and 1.87 g product isolated as a white solid. 1

H-NMR (CDCl3) d 7.14 (s, 2H, Ar ZH) C-NMR (CDCl3) d 138.3 (quat.), 121.8 (CH), 113.7 (quat.).

13

2. Preparation of (6-[2,20 ]bithiophenyl-5-yl-hexyloxy)-t-butyl-dimethylsilane A stirred solution of 2,20 -bithiophene (60.24 mmol) dissolved in 150 ml THF was treated with n-butyllithium (2.5M in hexanes; 50.0 mmol) dropwise at 2788C and then warmed to ambient temperature over 2 hours. The mixture was then treated with 6-bromohexyloxy-t-butyl-dimethylsilane (50.0 mmol) and stirred overnight at ambient temperature. The reaction was then quenched with aqueous NH4Cl and extracted three times with 70 ml ethyl acetate. Combined extracts were washed with water, brine, dried over MgSO4, and concentrated. The residue was purified by

Experimental

107

chromatography with silica gel using petroleum ether/ethyl acetate with a gradient of 100:0 – 20:1, respectively, and 15.07 g product isolated as a pale green oil. H-NMR (CDCl3) d 7.08 (m, 1H, ArZH), 7.03 (m, 1H, ArZH), 6.92 (m, 2H, ArZH), 6.61 (d, J ¼ 3.6 Hz, 1H, Ar ZH), 3.55 (t, J ¼ 6.2 Hz, 2H, OCH2), 3.34 (t, J ¼ 6.8 Hz, 2H, ArCH2), 1.25–1.85 (m, 8H, CH2), 0.86 (s, 9H, CH3), 0.01 (s, 6H, CH3) 13 C-NMR (CDCl3) d 145.1 (quat.), 138.0 (quat.), 134.8 (quat.), 127.6 (CH), 124.7 (CH), 123.7 (CH), 123.4 (CH), 122.9 (CH), 63.0 (OCH2), 33.8 (CH2), 32.9 (CH2), 32.7 (CH2), 28.0 (CH2), 26.0 (CH3) 25.1 (CH2), 18.4 (quat.), 5.2 (CH3) MS (m/e) 380 (Mþ, 27%), 323 (63), 179 (100), 75 (37) 1

3. Preparation of 2-f50 -[6-(t-butyl-dimethyl-silanyloxy)-hexyl]-[2,20 ]bithiophenyl-5-ylg-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane A reactor containing an ice-cooled solution of the step 2 product (19.76 mmol) dissolved in 150 ml THF was treated dropwise with n-butyllithium (2.5M in hexanes; 19.76 mmol) and after 2 hours treated with pinacol boronate (21.72 mmol). The ice bath was then removed and the mixture stirred overnight at ambient temperature. The reaction was quenched with aqueous NH4Cl and the mixture extracted three times with 70 ml of ethyl acetate. Combined extracts were then washed with brine, dried over MgSO4, and concentrated. The residue was purified by column chromatography on silica eluting with petroleum ether/ethyl acetate, 9:1, respectively, and 9.52 g of product isolated as a blue oil. H-NMR (CDCl3) d 7.46 (d, J ¼ 3.6 Hz, 1H, ArZH), 7.10 (d, J ¼ 3.6 Hz, 1H, ArZH), 6.99 (d, J ¼ 3.4 Hz, 1H, ArZH), 6.62 (d, J ¼ 3.4 Hz, 1H, ArZH), 3.56 (t, J ¼ 6.4 Hz, 2H, OCH2), 2.73 (t, J ¼ 7.4 Hz, 2H, ArCH2), 1.21– 1.70 (m, 20H, CH2 and CH3), 0.86 (s, 9H, CH3), 0.01 (s, 6H, CH3) 13 C-NMR (CDCl3) d 145.9 (quat.), 144.8 (quat.), 138.0 (CH), 134.7 (quat.), 125.0 (CH), 124.2 (CH), 124.1 (CH), 84.1 (quat.), 63.2 (OCH2), 32.8 (CH2), 31.6 (CH2), 30.2 (CH2), 28.9 (CH2), 26.0 (CH3) 25.6 (CH2), 24.8 (CH3), 18.4 (quat.), 25.2 (CH3) MS (m/e) 506 (Mþ þ, 32%), 331 (31), 305 (31), 279 (100), 261 (32), 205 (51), 83 (71) 1

4. Preparation of 2,5-bis-{50 [6-(t-butyldimethylsilanyloxy)-hexyl]-[2,20 ]bithiophenyl-5-yl}-thieno[3,2-b]thiophene Tetrakis(triphenylphosphine)palladium(0) (0.05 g) was added to a solution of the step 1 product (0.34 mmol) dissolved in 30 ml THF and after 20 minutes treated with the step 3 product (1.01 mmol) and a solution of K2CO3 (2.03 mmol) dissolved in 10 ml water. The mixture was refluxed for 90 minutes, cooled, and treated with 100 ml water. The precipitate that formed was filtered and then washed with water and diethyl ether. After recrystallization in toluene 0.17 g of product was isolated as yellow crystals. H-NMR (CDCl3) d 7.09 (d, J ¼ 3.7 Hz, 2H, Ar ZH), 7.01 (m, 6H, ArZH), 6.69 (d, J ¼ 3.4 Hz, 2H, Ar ZH), 3.60 (t, J ¼ 6.5 Hz, 4H, OCH2), 2.80 (t, J ¼ 7.3 Hz, 4H, ArCH2), 1.31– 1.84 (m, 16H, CH2), 0.90 (s, 18H, CH3), 0.05 (s, 12H, CH3) 13 C-NMR (CDCl3) d 145.8 (quat.), 138.8 (quat.), 138.4 (quat.), 137.2 (quat.), 134.3 (quat.), 128.0 (quat.), 125.0 (CH), 124.5 (CH), 123.63 (CH), 123.58 (CH), 115.5 (CH), 63.2 (OCH2), 32.8 (CH2), 31.6 (CH2), 30.2 (CH2), 28.9 (CH2), 26.0 (CH3) 25.6 (CH2), 18.4 (quat.), 25.2 (CH3). 1

108


5. Preparation of dimethacrylate monomer The experimental procedure for preparing the corresponding dimethacrylate not supplied by author. DERIVATIVES Selected derivatives and corresponding liquid-phase properties are provided in Table 1. TABLE 1. Properties Entry

Selected Thieno[3,2-b]thiophenes and Corresponding Liquid-Phase

Structure

Liquid Phase Propertiesa

Step 4 product

C ¼1588C SDSC ¼ 1828C SOPT ¼ 2438C

2

C ¼ 778C SDSC ¼ 1928C SOPT ¼ 2278C

6

C ¼ 988C SOPT ¼ 1088C

C ¼ Crystalline, SDSC ¼ smectic properties determined by DSC, and SOPT ¼ smectic properties determined by optical microscopy.

a

NOTES 1. A four-step method for preparing thieno[2,3-b]thiophene is described by He (1). 2. A method for preparing conjugated polymers, (I), having high molecular weights and high regioregularity using thiophene or selenophene with thieno[2,3-b]thiophene derivatives was developed by Tierney et al. (2) as illustrated in Eq. (1). The use of this polymer in semiconductor formulations is described by Shkunov et al. (3).

Notes

109

i. THF, tri-t-butylphosphonium tetrafluoroborate, tris(dibenzylidene)dipalladium(0) 3. In investigations by the authors (4) and Li et al. (5), polythieno[3,2-b]thiophenes, (II) and (III), respectively, were prepared and used as semiconductors and in electronics as organic thin-film transistors.

4. Poly(thiophene-co-selenophene) derivatives, (IV), were previously prepared by the authors (6) and used as semiconductors or charge-transport materials.

References 1. S. He, U.S. Patent Application 20070265418 (November 15, 2007). 2. S. Tierney et al., U.S. Patent Application 20070045592 (March 1, 2007). 3. M. Shkunov et al., U.S. Patent Application 20070221916 (September 27, 2007). 4. M. Heeney et al., U.S. Patent Application 20070232812 (October 4, 2007). 5. Y. Li et al., U.S. Patent Application 20070112171 (May 17, 2007). 6. M. Heeney et al., U.S. Patent Application 20060249712 (November 9, 2006).

V. DYES A. Jet Printer Ink a. Maleimide polymethacrylates

Title:

Maleimide-Containing Latex Dispersions

Author: Assignee:

Sivapackia Ganapathiappan et al. Hewlett Packard Company (Fort Collins, CO)



20080085950 (April 10, 2008) High 2011

Method of covalently incorporating the dye N-(2,4-dinitrophenyl)-1,4phenylenediamine into poly(methyl methacrylate-co-3-propylmalimide methyl methacrylate). Ongoing 7-year investigation involving methods for preparing emulsionbased organic dyes for use in ink jet ink printers. Dye formulations for ink jet ink printers Image fading occurs with ink jet ink printing systems since these materials exhibit poor durability when exposed to water or high humidity. Although the water-insoluble latex-encapsulated dye, 4-(4-nitro-1-diazo-phenyl)N,N-diethylaniline, has previously been used, the processing is lengthy and the amount of encapsulated dye is low. To address this problem water-insoluble latex copolymers containing the covalently bounded dye N-(2,4-dinitrophenyl)-1,4-phenylene-diamine have been prepared. When printed as ink jet ink, latex particulates formed a hydrophobic print film on the media surface, thereby entrapping and protecting the colorant within the film. The process for preparing these agents consisted of initially forming the Diels –Adler adduct with furan and maleimide followed by a transimidation with 3-amino-1-propanol.


111

112


The intermediate was esterified with methacryloyl chloride then copolymerized with methyl methacrylate followed by a retro Diels– Adler in situ to generate a pendant maleimide where the nucleophilic dye became covalently bonded to the reaction product.

REACTION

i. ii. iii. iv. v.

Furan, aluminum chloride, CH2Cl2 Methanol, 3-amino-1-propanol CH2Cl2, triethylamine, methacryloyl chloride Methyl methacrylate, Rhodafac RS 710 surfactant, water, potassium persulfate N-(2,4-Dinitrophenyl)-1,4-phenylenediamine (Disperse Yellow 9 dye), water, 2pyrrolidone, ethylene glycol EXPERIMENTAL

1. Preparation of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride A mixture of maleimide (0.2 mol), furan (0.2 mol), and aluminum chloride (0.25 mol) in 200 ml of CH2Cl2 was refluxed under a nitrogen atmosphere for 24 hours. After cooling to ambient temperature the mixture was poured onto 250 g of ice water and the pH value neutralized to 7. The organic layer was separated and the aqueous layer extracted twice with 50 ml CH2Cl2. Combined organic layers were washed

Experimental

113

with saturated NaHCO3 solution, water, and brine, then dried over Na2SO4, and concentrated. The residue was purified by flash chromatography and 28 g of product isolated as a white solid.

2. Preparation of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride-N-3propanol A reactor containing the step 1 product (0.1 mol) dissolved in 300 ml of methanol was treated with 3-amino-1-propanol (0.1 mol) and then refluxed for 48 hours. The mixture was then cooled to ambient temperature and concentrated and then redissolved into 200 ml of CH2Cl2. The mixture was washed three times with 100 ml water, dried with Na2SO4, rewashed three times with 100 ml water, and redried using Na2SO4. After reconcentration and recrystalization from methanol 14.5 g of product was isolated as a white solid.

3. Preparation of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride-N-3propylmethylmethacrylate A solution of the step 2 product (18 mmol) dissolved 30 ml of CH2Cl2 was treated with 3 ml triethylamine and methacryloyl chloride (18 mmol) at ambient temperature and then stirred overnight. The mixture was then diluted with 200 ml CH2Cl2, washed twice with 50 ml water, and 50 ml brine, and then dried over Na2SO4, concentrated, and 4.57 g of product isolated as a white solid. The material was used without further purification.

4. Preparation of latex incorporating maleimide surface groups The step 3 product (10 g) was mixed with methyl methacrylate (90 g) to form a monomer mixture, which was emulsified with Rhodafac RS 710 (2.5 g) (nonreactive surfactant) dissolved in 40 ml of water. The monomer emulsion was then added dropwise to 360 ml water at 608C containing potassium persulfate (0.4 wt% with respect to the monomers), heated for 2 hours and then cooled to ambient temperature, and the latex dispersion isolated.

5. Preparation of latex emulsion containing incorporated Disperse Yellow 9 surface groups The step 4 product (equivalent to 20 g solid polymer) was mixed with N-(2,4dinitrophenyl)-1,4-phenylenediamine (Disperse Yellow 9 dye) (1 g) containing 20 ml water and smaller amounts of 2-pyrrolidone and ethylene glycol. The product was isolated containing at least a portion of the dye covalently bound to the latex particulates.

114


DERIVATIVE The step 3 styrenyl analog was also prepared.

NOTES 1. A urethane latex composition, (I), was prepared by Kent et al. (1) and used as an in situ delivery agent for 4-hydroxyl-methyl benzoate, which was useful as an image stabilizer. Polyurea, (II), and polyurethane latex compositions were also prepared by the authors (2) containing pendant acid groups as latex stabilizers and as crosslinking sites.

2. In a separate investigation by Kent et al. (3) latex compositions containing poly(methyl methacrylate-co-hexyl acrylate) were prepared containing the ultraviolet absorber monomer Norblocw 7966. 3. Functionalized latex monomer particulates containing a photo labile component, (III), were prepared by Zhou et al. (4) that was sensitive to 350-nm light.

Notes

115

References 1. V. Kent et al., U.S. Patent Application 20080070038 (March 20, 2008). 2. S. Ganapathiappan et al., U.S. Patent Application 20060199007 (September 7, 2006). 3. V. Kent et al., U.S. Patent Application 20070298165 (December 27, 2007), U.S. Patent Application 20070296789 (December 27, 2007), and U.S. Patent Application 20070296784 (December 27, 2007). 4. Z-l. Zhou et al., U.S. Patent 6,995,206 (February 7, 2006).

b. Oxime esters

Title: Oxime Ester Compound and Photopolymerization Initiator Containing Such Compound Author: Assignee:

Mitsuo Akutsu et al. Adeka Corporation (Tokyo, JP)



Observations:

116

20070270522 (November 22, 2007) Very high Late 2009

Identification and preparation of oxime ester photopolymerization initiators that do not cause film discoloration or deteriorated by heat while remaining highly light sensitive. Ongoing investigation in preparing oxime photochemical initiators. Photocurable inks Photosensitive plates Carbazole-based photopolymerization initiators containing the sensitive photoactive N-acetyl oxime ester substituent were prepared, which were photosensitive at 405 –365 nm. When activated in compositions containing colorants, ethylenic unsaturated monomers and polymers, N-acetyl oxime esters did not cause resin or film discoloration, photograph blemishing, or material contamination. This is a result of the presence of thermally stable carbazole having a melting point of 2468C and a boiling point of 3558C. Although noncarbazole containing ketooximes have also been used as photopolymerization initiators, product quality is usually compromised.

Experimental

117

REACTION

i. Monochlorobenzene, zinc chloride, 4-fluoro-2-methylbenzoyl chloride, n-heptane, aluminum chloride, acetyl chloride, dichloroethane ii. 2,2-Dimethyl-1,3-dioxolane-4-methanol, tetrabutylammonium hydrogensulfate, dimethylacetamide, butyl acetate, acetic anhydride, hydroxylamine hydrochloride

EXPERIMENTAL 1. Preparation of acetyl intermediate A mixture consisting of monochlorobenzene (33.1 g), N-ethylcarbazole (0.11 mol), and zinc chloride (10 mmol) were heated at 808C and treated with the dropwise addition of 4-fluoro-2-methylbenzoyl chloride (0.10 mol) and stirred for 1 hour. The mixture was cooled to ambient temperature and treated with n-heptane (33.1 g) and then 16.5 ml of water added. The organic layer was isolated and neutralized with 8.30 ml of 1% aqueous sodium hydroxide and then washed with 40.0 ml of water in two portions. The mixture was concentrated to 50 ml and then treated with monochlorobenzene solution (90.0 g) and aluminum chloride (40.0 g) and cooled to 108C. The solution was treated with acetyl chloride (0.13 mol), stirred at ambient temperature for 1 hour, and then poured into a mixture of dichloroethane (224 g) and 134 ml of ice water. The organic layer was collected and then treated with 40 ml 5% hydrochloric acid, 40 ml of water, and 40 ml 2% aqueous NaOH solution. It was and then concentrated, the residue recrystallized in n-propyl acetate, and 22.4 g product isolated as a light yellow solid. 1

H-NMR d 8.70 (s, 1H), 8.52 (s, 1H), 8.17 (d, 1H), 8.09 (d, 1H), 7.50 (s, 1H), 7.48 (d, 1H), 7.39 (d, 1H), 7.05 (d, 1H), 7.00 (d, 1H), 4.45 (d, 2H), 2.73 (s, 3H), 2.37 (s, 3H) 1.49 (t, 3H) FTIR (cm21) 3448, 3054, 2064, 1662, 1625, 1589, 1567, 1484, 1386, 1305, 1245, 1153, 1124, 1022, 809

2. Preparation of oxime ester At ambient temperature a mixture consisting of the step 1 product (1.45 mol), 2,2dimethyl-1,3-dioxolane-4-methanol (2.90 mol), tetrabutylammonium hydrogensulfate (0.290 mol), and dimethylacetamide (2.11 kg) were treated with sodium hydroxide (3.63 mol). The mixture was then heated at 608C for 3 hours and then recooled to ambient temperature and treated with hydroxylamine hydrochloride (2.32 mol). The mixture was stirred at 808C for 2 hours and then cooled to 508C. Thereafter, it was treated with butyl acetate (1.45 kg) and 1.45 liters of water and the organic layer

118

Oxime Ester Compound and Photopolymerization Initiator Containing Such Compound

collected and washed with 1.45 liters of 5% aqueous sodium chloride solution. The organic layer was refluxed for 4 hours to remove water and butyl acetate and then treated with acetic anhydride (1.74 mol). It was stirred at 858C for 2 hours, recooled to ambient temperature, and treated with 5% aqueous sodium hydroxide (1.39 kg). The organic layer was isolated and washed with 1.57 liters of water in two portions. It was filtered, concentrated, the residue recrystallized from butyl acetate/butyl ether, 1.42 kg: 779 g, respectively, and 562 g of product isolated as a colorless crystalline solid, melting point (mp) ¼ 1238C. 1

H-NMR d 8.5–6.8 (aromatic, 9H), 4.6 (m, 1H), 4.4 (q, 2H), 4.2 (m, 1H), 4.1 (m, 1H), 4.0 (m, 1H), 2.5 (s, 3H), 2.4 (s, 3H), 22.3 (s, 3H), 1.5 (s, 3H), 1,4 (s, 6H) FTIR (cm21) 2981, 2932, 1751, 1650, 1627, 1591, 1570, 1488, 1459, 1375, 1276, 1239, 1215, 1152, 1129, 1050, 894, 849, 810, 773 UV spectrum (acetonitrile:water ¼ 7:3). lmax ¼ 268, 292, 332 nm

NOTES 1. Additional oxime ester derivatives, (I), effective as photopolymerization initiators were prepared by Sasaki (1) and are described.

2. Multifunctional oxime ester photoiniators, (II), were prepared by Kunimoto et al. (2), which were activated in the 150- to 600-nm range using ultraviolet (UV) and visible lasers and were used in imaging applications.

Notes

119

3. Oxman et al. (3) determined that cure speed and enthalpy were improved in photopolymerizable compositions when using anthracene derivatives containing electron donors as photoinitators for cationic curing. Dimethoxy-, diethoxy-, and diphenoxyanthracene were especially preferred. References 1. T. Sasaki, U.S. Patent Application 20070203255 (August 30, 2007). 2. K. Kunimoto et al., U.S. Patent 7,189,489 (March 13, 2007) and U.S. Patent 6,949,678 (September 27, 2005). 3. J.D. Oxman et al., U.S. Patent Application 20070287764 (December 13, 2007).

VI. ELECTRICALLY ACTIVE POLYMERS A. Battery a. Polypiperidine-4-vinyloxy-1-oxyl ethers

Title: Method for Manufacturing Polyradical Compound and Battery Author: Assignee:

Masahiro Suguro et al. NEC Corporation (Tokyo, JP)



20080038636 (February 14, 2008) High Mid-2010

Identification of polyradicals having a high capacity density from which a large current can be extracted for use as components in secondary batteries. Six-year ongoing investigation using polyradicals in secondary battery compositions. Secondary battery component Poly(2,2,6,6-tetramethyl piperidine-4-vinyloxy-1-oxyl) was prepared by cationic polymerization using Lewis acids as catalysts. The high discharge capacities of these materials makes them potentially usable as secondary batteries. Although electron spin resoance (ESR) values for polymers prepared using AlCl3, TiCl4, and FeCl3 were equivalent, optimum yield and conversion and charge density were obtained using AlCl3. The monomer, 2,2,6,6-tetramethyl piperidine-4-vinyloxy-1-oxyl, was prepared by condensing the corresponding alcohol and an alkyl vinyl ether in the presence of mercuric acetate or by heating the alcohol with vinyl acetate in the presence of an iridium catalyst. Polyradical


121

122

Method for Manufacturing Polyradical Compound and Battery

agents have previously been prepared by reacting 2,2,6,6-tetramethyl piperidine methacrylate with azobisisobutyronitrile and then oxidizing the polymer with m-chloroperbenzoic acid.

REACTION

i. Boron trifluoride diethyl ether, CH2Cl2 EXPERIMENTAL 1. Preparation of poly(2,2,6,6-tetramethyl piperidine-4-vinyloxy-1-oxyl) Under a protective nitrogen atmosphere, a reaction flask was charged with 2,2,6,6tetramethyl piperidine-4-vinyloxy-1-oxyl (50.4 mmol) and 100 ml of CH2Cl2 and then cooled to 2788C and treated with boron trifluoride diethyl ether complex (2 mmol). The mixture was stirred at 2788C for 20 hours and then warmed to ambient temperature. The solid was filtered, washed with methanol several times, dried in vacuum, and the product isolated in 70% yield as a red solid having an Mn of 89,000 Da with a polydispersity of 2.7, Tg of 1328C, and ESR spectrum of 3.05 1021 spin/g. DERIVATIVES Only the step 1 product was prepared. CATALYST SCOPING REACTIONS TABLE 1. Physical Properties of Poly(2,2,6,6-tetramethyl piperidine-4-vinyloxy-1oxyl) Prepared by Cationic Polymerization Using Different Lewis Acids as Catalystsa Entry 2 3 4 a

Catalyst AlCl3 TiCl4 FeCl3

Mn (Da) 91,000 86,000 86,000

Tg (8C) 128 135 130

Discharge Capacity (%)

ESR (spin/g)

Yield (%)

81.0 95.0 87.1

3.05 10 3.05 1021 3.05 1021

72 66 66

Discharge capacities were measured at 4.0 V at a constant current of 5.0 mA.

21

Notes

123

NOTES 1. Polydiazine-N,N 0 -dioxide analogs, (I) and (II), were prepared by Morioka et al. (1) and used to provide an electrode-active material having a high capacity density for use in secondary batteries.

2. Nakahara et al. (2) prepared radical polymeric agents, (III) and (IV), for use as active materials in anode layers to provide a stable secondary battery with a higher energy density and a large capacity. Radical agents prepared had a spin concentration of 1.0 1021 spins/g or more.

3. Secondary battery components containing pherdazl, (V), and triazine, (VI), free radicals were prepared by Nakahara et al. (3).

124

Method for Manufacturing Polyradical Compound and Battery

4. Nakahara et al. (4) prepared an electricity storage device consisting of poly(2,2,5,5-tetramethylpyrrolidinoxy methacrylate), (VII), for use as a negative electrode in lithium secondary batteries.

References 1. Y. Morioka et al., U.S. Patent Application 20050100787 (May 12, 2005), U.S. Patent 7,018,738 (March 28, 2006), and U.S. Patent 6,893,775 (May 17, 2005). 2. K. Nakahara et al., U.S. Patent Application 20050170247 (August 4, 2005). 3. K. Nakahara et al., U.S. Patent 6,866,964 (March 15, 2005). 4. K. Nakahara et al., U.S. Patent 7,226,697 (June 5, 2007).

B. Conducting Polymers a. Polythiophene

Title: Electrically Conductive Polymers and Method of Making Electrically Conductive Polymers Author: Assignee:

Steffen Zahn et al. Air Products and Chemicals, Inc. (Allentown, PA)


Observations:


Preparation of electrically conductive polymers using thiophene fused with imidazolone, dioxolone, and imidazolethione intermediates. Thiophene and selenium fused electroactive polymers are unreported in the literature. Electrochromic displays Electrolytic capacitors Optically transparent electrodes Antistatic coatings This application represents a continuing investigation by this group for identifying thiophene- and selenium-containing fused monomers that can be polymerized into electrically conductive polymers. Methods of optimizing the synthesis of these monomeric agents are also described. While other fused 1H-thieno derivatives have been prepared and polymerized by this group, their applications were limited to electronic applications.

125

126

Electrically Conductive Polymers and Method of Making Electrically Conductive Polymers

REACTION

i. Poly(styrenesulfonic acid), ammonium persulfate, iron(III) sulfate ii. Tetrabutylammonium hexafluorophosphate, acetonitrile EXPERIMENTAL 1. Chemical synthesis of poly(1H-thieno[3,4-d]imidazol-2(3H)-one) 1H-thieno[3,4-d]imidazol-2(3H)-one (0.36 mmol), poly(styrene sulfonic acid) (830 mg), and 10 ml of deionized water were added to a 25-ml one-neck flask. The mixture was stirred at 600 rpm and then treated with (NH4)2S2O8 (0.48 mmol) and Fe2(SO4)3 (2 mg) and the oxidative polymerization carried out in excess of 1 hour. After polymerization the aqueous solution was purified by treatment with Amberlite IR-120 and MP62 resulting in a deep black aqueous poly(1H-thieno[3,4-d]imidazol-2(3H)-one) and poly(styrene sulfonic acid) dispersion. Transparent films were prepared by spin coating the poly(1H-thieno[3,4-d]imidazol-2(3H)-one) and poly(styrene sulfonic acid) mixture onto glass substrates at 1000 rpm yielding an electrically conductive surface. 2. Electrochemical synthesis of poly(1H-thieno[3,4-d]imidazol-2(3H)-one) 1H-thieno[3,4-d]imidazol-2(3H)-one was dissolved in tetrabutylammonium hexafluorophosphate/acetonitrile solution to a concentration of 5 mM of monomer and 100 mM of electrolyte. The monomer was electrochemically polymerized using a three-electrode configuration with a platinum button working electrode 2 mm in diameter, a 1-cm2 platinum flag counter electrode, and a Ag/Agþ nonaqueous reference electrode at 4.82 V versus vacuum level. The monomer exhibited a low oxidation potential with an onset at 5.66 eV. Polymerization was apparent from the current response increase at a lower redox potential upon repetitive scans.

Notes

127

DERIVATIVE The copolymer, poly(1H-thieno[3,4-d]imidazol-2(3H)-one-co-3,4-ethylenedioxthiophene), was also electrochemically prepared.

TESTING Conductive Properties The step 2 product was evaluated in a 100-mM acetonitrile solution of tetrabutylammonium hexafluorophosphate at scan rates of 25, 50, 100, 200, and 400 mV/s. The peak current for the reductive process was found to scale linearly with the scan rate suggesting that the step 2 product had adhered to the surface of the electrode. Cyclic voltammetry indicated a highest occupied molecular orbital (HOMO) of 4.7 eV with an electrochemical band gap of 1.65 eV. Differential pulse voltammetry gave rise to a HOMO of 4.67 eV.

NOTES 1. Single-step methods for preparing 1H-thieno[imidazole] derivatives are described by the authors (1) in a subsequent investigation and illustrated for 1H-thieno-[3,4-d]1,3-dioxolan-2-one, (I), in Eq. (1).

(1)

i. Dimethyl carbonate 2. In other investigations by the authors (2,3), poly(thieno[3,4-d]isothiazole), (II), and 2-pentafluorosulfanyl-thieno[3,4-b]thiophene, (III), respectively, were prepared. Poly(thieno[3,4-d]isothiazole) was prepared using (NH4)2S2O8

128

Electrically Conductive Polymers and Method of Making Electrically Conductive Polymers

(0.48 mmol) and Fe2(SO4)3 while the pentafluoro derivative was electrochemically polymerized. Additional 2-substituted thieno[3,4-b]thiophene derivatives are described by Nordquist et al. (4).

3. Becker et al. (5) prepared polymeric organic light-emitting diodes by copolymerizing 4,7-dibromobenzo[1,2,5]-thiadiazole, (IV), and 4,7-dibromobenzofurazone, (V), with spirobifluorene derivatives. Polymerizations were performed under Yamamoto conditions.

References 1. S. Zahn et al., U.S. Patent Application 20070282099 (December 6, 2007). 2. S. Zahn et al., U.S. Patent Application 20070238854 (October 11, 2007) and U.S. Patent Application 20070278453 (December 6, 2007). 3. S. Zahn et al., U.S. Patent Application 20060074250 (April 6, 2006). 4. A.F. Nordquist et al., U.S. Patent Application 20060071200 (April 6, 2006). 5. H. Becker et al., U.S. Patent Application 20070265473 (November 15, 2007).

C. Electrodes a. Carboxylated nanotubes

Title:

Ozonolysis of Carbon Nanotubes

Author: Assignee:

Jun Ma et al. Hyperion Catalysis International (Cambridge, MA)


20080031802 (February 7, 2008) Moderate 2010


Preparation of carboxylated nanotubes by direct oxidation with ozone. Carboxylated nanotubes have previously been prepared using nitric oxide. Electrodes in electrochemical capacitors

Observations:

Single and multiwalled carbon nanotubes have previously been activated by amination, acrylation, carboxylation, esterification, hydroxylation, and sulfonation. A distinct disadvantage of hydroxyl carboxylation, however, is decarboxylation of the oxidation product when using concentrated nitric acid. The authors have determined that oxidation of nanotubes at ambient temperature using ozone avoids this problem. Hydroxy carboxylated nanotube aggregates are anticipated to be used as catalyst supports or rigid porous structures such as in electrochemical capacitors.

REACTION

i. Ozone, air 129

130

Ozonolysis of Carbon Nanotubes

EXPERIMENTAL 1. Ozonolysis of carbon nanotubes: General procedure Ozone was generated at 250 mg/hour and 0.29% ozone in air passed through a reactor tube packed with dry fibrils at 1200 ml/hour. The oxidation continued at ambient temperature for 3 – 45 hours and the product isolated.

REACTION SCOPING TABLE 1. Weight Changes and Acidity Profiles of Fibril Oxidation Products Prepared at Ambient Temperaturea Entry 1 2 3 4 5 6 7 8

Oxidant

Initial Weight (g)

Reaction Time (h)

Weight Change (%)

Titer (meq/g)

O3/Air O3/Air O3/Air O3/Air O3/Air 30% HNO3 60% HNO3 30% H2O2

3 3 10 9 3 20 20 20

20 20 45 45 25 6 4 2

13.9 8.0 10.4 10.2 12.1 26.4 215.3 21.7

1.45 1.07 1.57 — 1.16 0.58 0.13 1.20

a

Acidity testing was performed using 0.1 N NaOH at ambient temperature until a pH of 7.0 was obtained. Ozone was generated at 250 mg/hour and used in a 0.29% blend in air at a flow rate of 1200 ml/hour.

AGGREGATION TESTING Oxidized Fibril Aggregation Properties TABLE 2.

Aggregation Properties of Oxidized Fibrils in Water

Fibril Aggregate

Surface

Wetting Characteristics

Structural Retention

Untreated HNO3 oxidized O3 oxidized

Hydrophobic Hydrophilic Hydrophilic

Nonwetting Wetting Wetting

Retains structure Breaks apart Retains structure

NOTES 1. Graphite nanofibers functionalized by sulfonation with sulfuric acid containing 20% SO3 and aminated using ammonia or modified using acrloyl chloride or maleic anhydride were prepared by Tennent et al. (1) and used in electrochemical capacitors. In a separate investigation by Tennent et al. (2), fibrils were functionalized using acrylic acid at elevated temperatures.

Notes

131

2. Hydrogenated nanofibrils were prepared by Fisher et al. (3) by reacting with LiAlH4 at 708C for 2 hours. Massey et al. (4) postreacted these intermediates with n-butyllithium and formed the corresponding lithiated fibrils, which were hydrolyzed to hydroxyls by reacting with air. 3. Fibril aggregates randomly entangled were sulfonated at 3008C by reacting with sulfuric acid containing 20% SO3 by Fisher et al. (5). References 1. H. Tennent et al., U.S. Patent 6,031,711 (February 29, 2000). 2. H. Tennent et al., U.S. Patent 6,414,836 (July 2, 2002). 3. A. Fisher et al., U.S. Patent 6,203,814 (March 20, 2001). 4. R.J. Massey et al., U.S. Patent Application 20060160246 (July 20, 2006). 5. A. Fisher et al., U.S. Patent Application 20060193868 (August 31, 2006).

b. Ferrocene polymethacrylates

Title: Redox Polymers for Use in ElectrochemicalBased Sensors Author: Assignee:

Zuifang Liu et al. Johnson & Johnson (New Brunswick, NJ)

Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus: Originality:

Application: Observations:

132

20080035479 (February 14, 2008) Very high Mid-2010

Synthesis of oligo(N-vinylpyrrolidinone-co-vinylferrocenes) crosslinked with polymethylmethacrylate for use as redox polymers. The preparation of oligo(N-vinylpyrrolidinone-co-vinylferrocene) crosslinked with polymethylmethacrylate is unreported in the patent literature. Glucose electrode Ferrocene-modified oligomeric N-vinylpyrrolidinone was prepared and used as an enzyme electrode for amperometric determination of glucose. The method uses in vivo enzyme biosensors with miniature glucose sensors for subcutaneous measurement of glucose. Ferrocenebased redox mediators attached to oligomeric N-vinylpyrrolidinone and then crosslinked with methyl methacrylate were used. Polymers were made in two steps. Initially vinylferrocene and N-vinylpyrrolidinone were free radically copolymerized using 2,20 -azobisisobutyronitrile. This intermediate was subsequently crosslinked with methyl methacrylate.

Experimental

133

REACTION

i. Vinyl ferrocene, 2,20 -azobisisobutyronitrile, isopropoxyethanol ii. Methacryloylchloride, triethylamine, CH2Cl2 iii. Methyl methacrylate, 2,20 -azobis-isobutyronitrile, 1-pentanol

EXPERIMENTAL 1. Preparation of poly(N-vinylpyrrolidinone-co-vinyl ferrocene) ethanol ether A reactor was charged with N-vinylpyrrolidinone (10.2 g), vinyl ferrocene (0.88 g), and 2,20 -azobisisobutyronitrile (0.05 g) dissolved in 15 ml of isopropoxyethanol. Before initiating the polymerization, the reaction solution was deoxygenated by bubbling nitrogen through for 1 hour and then heating the mixture to 708C for 24 hours. The intermediate was then dissolved in CH2Cl2 and precipitated from the solution using diethyl ether, filtrated, dried, and the product isolated. 2. Preparation of poly(N-vinylpyrrolidinone-co-vinyl ferrocene) methylacrylate A mixture consisting of the step 1 product (2.0 g), methacryloylchloride (0.8 g), and triethylamine (1.2 g) dissolved in 20 ml of CH2Cl2 was stirrer overnight at ambient temperature and then washed with a solution containing 0.1 N HCl, 0.5 N potassium carbonate, and distilled water. The organic phase was then concentrated and the product isolated. 3. Preparation of the redox polymer A solution of the step 2 product (1.0 g), methyl methacrylate (6.2 g), and 2,20 -azobisisobutyronitrile (0.06 g) dissolved in 60 ml of 1-pentanol was deoxygenated and then heated to 708C for 24 hours. The product was isolated after precipitating from diethyl ether and drying in an oven at 508C.

134

Redox Polymers for Use in Electrochemical-Based Sensors


TESTING Electrochemical Evaluation A glassy carbon electrode was dipped into a solution containing the step 3 product dissolved in 2-isopropanol. The electrode was then immersed in phosphate buffer saline and tested using cyclic voltammetry at 20 mV/s between 20.1 and 0.5 V vs. Ag/AgCl. The presence of reduction and oxidation peaks between the tested voltage range indicated that electroactive ferrocene was immobilized onto the glassy carbon electrode. Sixty scans were performed and the results indicated that there was no significant decrease in the oxidation and reduction peaks, indicating that the step 3 product did not wash off the glassy carbon electrode.

NOTES 1. Redox-active substrates, (I), were prepared by Van Der Boom et al. (1) and used to detect changes in the optical response of the outer layer.

Notes

135

2. Ferrocene copolymers, (II) and (III), exhibiting redox potentials were prepared by Choi et al. (2) and used in organic memory devices.

3. Mobley et al. (3) prepared macroscopic complexes, (IV), containing ferrocene that were effective as redox substrates.

References 1. M.E. Van Der Boom et al., U.S. Patent Application 20070258147 (November 8, 2007). 2. T.L. Choi et al., U.S. Patent Application 20070197768 (August 23, 2007). 3. J.K. Mobley et al., U.S. Patent 7,324,385 (January 29, 2008).

c. C60 fullerene perfluoro sulfonic acids

Title:

Functionalized Carbon Materials

Author: Assignee:

Paul J. Krusic et al. E.I. DuPont de Nemours and Company (Wilmington, DE)


Observations:

20070293693 (December 20, 2007) Medium Mid/late 2009

Functionalization of fullerene molecule with perfluorosulfonic acid for use as a Nafionw-like fuel cell electrode. While C60 fullerene analogs of these products are reported in the literature, the synthetic methodology is new. Electroconductive materials in fuel cells Electrodes C60 fullerene surfaces were thermally functionalized with perfluoro(3-oxo-penta-4-ene)sulfonyl fluoride and then converted into sulfonic acid derivatives by basic hydrolysis. The product mimiced the electroconductive properties of perfluorosulfonyl Nafionw 1100 resins. When the modified fullerence was blended with platinum nanoparticles imbedded in Nafionw 1100 the material was effective as electrodes in fuel cells.

REACTION

136

Notes

137

i. 1,2,4-Trichlorobenzene, perfluoro(3-oxo-penta-4-ene)sulfonyl fluoride ii. Potassium hydroxide, cation exchange resin AG 50W X8 1. Preparation of C60 fullerene-g-perfluoro(3-oxo-penta-4-ene)sulfonyl fluoride A 70-ml stainless steel reactor was charged with C60 fullerene (50 mg), 20 ml of 1,2,4trichlorobenzene, and perfluoro(3-oxo-penta-4-ene)sulfonyl fluoride (3 g) and cooled to 2508C and then evacuated and filled with nitrogen and the mixture heated to 2008C for 18 hours. The solvent was then removed and the product isolated as a brown solid. MALDI 720, 19 F-NMR Confirms [2 þ 2] functionalized Solid State 19F: 2105, 2109 ppm (JAB ¼ 208 Hz; CNT-CF2Z); – 118.8 ppm (CNT-CF2ZCFZ); 276.5, 283.7 ppm (JAB ¼ 150 Hz; ZOZCF2Z); 2111.6 ppm (ZCF2ZSO2F); and þ45.5 ppm (SO2F)

2. Preparation of C60 fullerene-g-perfluoro(3-oxo-penta-4-ene)sulfonic acid The step 1 product (20 – 30 mg) was suspended in 10 ml 20% KOH/water/methanol/ dimethyl sulfoxide (DMSO), 5:4:1, respectively, and then heated to 808C for 3 hours. The homogeneous solution was neutralized to pH 7 with 10% nitric acid and then passed through a cation exchange column containing AG 50W X8 and washed with methanol and water. The eluted material was then lyophilized to yield 24.8 mg of product isolated as a brown solid.

NOTES 1. In the current application single-walled nanotubes were also cycloadditized with perfluoro(3-oxo-penta-4-ene)sulfonyl fluoride, base hydrolyzed, and converted into electrodes. 2. Terpolymer blends containing poly(tetrafluoroethylene-co-perfluoro-a-olefins) and platinum nanoparticles imbedded in Nafionw 1100 fluoropolymer resin were previously prepared by the authors (1) and used as electrodes in fuel cells. 3. A composition consisting of the step 2 product and platinum nanoparticles blended in perfluoro-aromatic cationic copolymers, (I), was prepared by the authors (2) and used in fuel cell applications.

138

Functionalized Carbon Materials

4. A fullerene network of proton conductive materials, (II), was prepared by Nuber et al. (3) and used in fuel cell applications as illustrated in Eq. (1).

(1)

i. 1,2,4-Trichlorobenzene, perfluoro(3-oxo-penta-4-ene)sulfonyl fluoride ii. Potassium hydroxide, 1,6-diiodo-perfluorohexane

References 1. P.J. Krusic et al., U.S. Patent Application 20060093885 (May 4, 2006). 2. P.J. Krusic et al., U.S. Patent Application 20060073370 (April 6, 2006). 3. B. Nuber et al., U.S. Patent Application 20070259977 (November 8, 2007), U.S. Patent Application 20070219385 (September 20, 2007), and U.S. Patent Application 20070087247 (April 19, 2007).

d. Polyaniline

Title: Chemical Synthesis of Chiral Conducting Polymers Author: Assignee:

Hsing-Lin Wang et al. Los Alamos National Laboratory (Los Alamos, NM)


20070129536 (June 7, 2007) High 2009


Preparation of helical polyaniline using chiral dopant acids. The preparation of helical polyaniline is unreported in the patent literature. Chemical separation materials Light-emitting devices Surface-modified electrodes

Observations:

The preparation of helical polyaniline nanofibers has been a 6-year ongoing area of interest from this research group. In this application it was discovered that when the oxidant rate of addition was incremental, both helical and nanofiber content of polyaniline were optimized. Their initial investigation for preparing helical polyaniline doped with 1S)(þ)-camphorsulfonic acid was performed using a single addition of ammonium peroxydisulfate resulting in a low degree of chirality and nanofiber content. When achiral polyaniline was prepared by placing aniline and methanesulfonic acid into permeable tubing and then submerging into an oxidant bath, an extensive network of nanofibers resulted.

139

140

Chemical Synthesis of Chiral Conducting Polymers

REACTION

EXPERIMENTAL 1. Preparation of chiral polyaniline A mixture consisting of aniline (0.2 g) and (1S)-(þ) camphorsulfonic acid (3.48 g) was dissolved in 10 ml of water and then treated with five separate portions of 0.1 g of ammonium peroxydisulfate dissolved in 1 ml water. Each successive portion was added when the solution turned from blue to green while the reaction mixture was maintained at 208C. After the additions were completed the mixture was centrifuged and the product washed with water. The circular dichroism spectrum of the product suspensed in water indicated a molar ellipticity of about 90 103 deg-cm2/dmol. Transmission electron micrographs showed that the product had a nanofibrous structure with fiber diameters from 30 to 70 nm and had a length of several hundred nanometers. NOTES 1. Generally speaking, if a chiral dopant acid is a strong acid, that is, pKa , 3, and soluble in water, N-methyl-2-pyrrolidinone, dimethyl sulfoxide, or N, N0 dimethylformamide can be used to generate helical polyaniline. 2. Chiral polyaniline was also prepared according to the method of MacDiarmid et al. (1) as described below: Approximately 2 ml of aniline was added to 200 ml of 1.0 M aqueous (1S)-(þ) camphorsulfonic acid solution and then treated with ammonium peroxydisulfate (1.15 g) dissolved in 10 ml aqueous solution of 1.0 M (1S)-(þ) camphorsulfonic acid. The solution of ammonium peroxydisulfate was quickly added over several seconds to the solution of aniline and then stirred for 90 minutes. After the reaction was completed, the precipitate was collected and washed with about 400 ml of an aqueous solution of 0.1 M (1S)-(þ) camphorsulfonic acid. Washing was repeated until the filtrate was colorless.

Transmission electron micrographs showed that the precipitate was in the form of particles, although some nanofibrous structures were observed. The circular dichroism indicated a molar ellipticity of 5 103 deg-cm2/dmol.

Notes

141

3. In an earlier investigation by the authors (2) helical polyaniline doped with (1S)-(þ) camphorsulfonic acid produced nanofibers with diameters from 30 to 120 nm with a length of 1 – 5 mm. 4. Polymer nanofiber networks consisting of achiral polyaniline were prepared by Epstein et al. (3) by oxidizing aniline with ammonium peroxydisulfate and then doping with methanesulfonic acid. References 1. A.G. MacDiarmid et al., U.S. Patent 6,090,985 (July 18, 2000). 2. H-L. Wang et al., U.S. Patent 7,074,887 (July 11, 2006) and U.S. Patent 6,514,432 (February 4, 2003). 3. A.J. Epstein et al., U.S. Patent Application 20070034836 (February 15, 2007).

e. Polypyridinium salts

Title:

Method for Producing Polypyridinium Salts

Author: Assignee:

Tomokazu Iyoda et al. Canon Kabushiki Kaisha (Tokyo, JP)



142

20080132676 (Sept 12, 2008) High June, 2010

Method of preparing polypyridinium salts with well-defined molecular weights that were soluble in aqueous and organic solvents. Although polypyridinium salts have been previously prepared, none had narrow molecular weight distributions while all have had limited organic solvent solubility. Electrode component Although 1,4-polypyridinium salts have previously been prepared using inorganic salts such as sodium tetrafluoroborate in an organic solvent, the molecular weight could not be determined because of limited solvent solubility of the product. To address this concern, a method of preparing polypyridinium salts having a polydispersity of 1.5 by using consecutive chain polymerization of 4-chloropyridine and N-(40 -tert-butylbenzyl)-4chloropyridinium with tetrabutylammonium tetrafluoroborate as accelerator is described. Materials prepared in this manner were completely soluble in DMSO and had an average molecular weights of 40,000 Da.

Notes

143

REACTION

i. 4-t-Butylbenzyl bromide ii. Tetrabutylammonium tetrafluoroborate, acetonitrile, 4-chloropyridine

EXPERIMENTAL 1. Preparation of N-(40 -t-butylbenzyl)-4-chloropyridinium 4-Chloropyridine (2.3 mmol) was added dropwise to 4-t-butylbenzyl bromide (23.0 mmol) and the reaction mixture agitated for 5 hours at ambient temperature. The yellow solids that separated out were filtered and washed with diethyl ether, recrystallized using ethanol, and the product isolated in 97% yield. 2. Preparation of polypyridinium bromide The step 1 product (0.009 mmol) and tetrabutylammonium tetrafluoroborate (0.598 mmol) were dissolved in 0.1 ml of acetonitrile and the solution added to a test tube containing 4-chloropyridine (0.50 mmol). After the mixture was heated for 30 minutes at 608C the conversion rate reached 80%. The reaction mixture was then cooled to ambient temperature and concentrated. A yellow brown residue was isolated and was washed with diethyl ether and then dried under vacuum at ambient temperature and the product isolated having an average degree of polymerization of 52.

DERIVATIVES No additional derivatives were prepared. NOTES 1. The same reaction was performed without using the accelerating agent tetrabutylammonium tetrafluoroborate by Schmidt (1). The yellow brown solids

144

Method for Producing Polypyridinium Salts

that separated out were filtered, washed using diethyl ether, and dried. The average molecular weight of the product could not be calculated using 1H-NMR because of the limited solubility of the product in both aqueous and organic solvents. 2. The weakly nucleophilic anion tetrafluoroborate has also been used to catalyze the nonaromatic cyclization of polyvinylamine to polytetrahydropyrimidinium by Schmidt (2) using ethyl orthoester as illustrated in Eq. (1).

(1)

i. Ethyl orthoester, tetrabutylammonium tetrafluoroborate 3. Harris et al. (3) used triphenylmethyl tetrafluoroborate to prepare the polypyridinium salt, (I), which was a stable conducting polymer when doped with TCNQ dianions.

References 1. F.G. Schmidt, U.S. Patent Application 20050143517 (June 30, 2005). 2. F.G. Schmidt, U.S. Patent Application 20050119431 (June 2, 2005). 3. F. Harris et al., U.S. Patent 5,863,651 (January 26, 1999) and U.S. Patent 5,763,563 (June 9, 1998).

D. Photovoltaic Cells a. Fluorene divinyl esters

Title: Liquid Crystalline Interpenetrating Polymer Networks Author: Assignee:

Mary O’Neill et al. University of Hull (Hull, GB)

U.S. Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus: Originality:



Synthesis of liquid crystalline interpenetrating polymer networks using photocrosslinkable mesogenic monomers. While the synthesis of photovoltaic cells using mesogenic agents is new, the preparation of these monomers exceeds 11 steps, limiting its commercial viability. Photovoltaic cells Most commercial photovoltaic devices consist of inorganic semiconductors because of their high quantum yields. In order for organic-polymer-based photovoltaic devices to achieve similar quantum efficiencies, two conjugated polymers of different electron affinities must interface. Although they are effective, components in photovoltaic cells containing fluorene are difficult to prepare. For example, beginning with fluorene, monomers of the current application (I) required 12 synthetic steps to prepare. Other mesogenic interpenetrating fluorene networks having good hole transporting properties were prepared in 11 steps. Three interconnecting liquid crystalline polymers have been prepared and the quantum efficiency of these agents evaluated.

145

146

Liquid Crystalline Interpenetrating Polymer Networks

REACTION

EXPERIMENTAL 1. Preparation of a photovoltaic cell comprising an interconnecting liquid crystalline polymer network of reactive mesogens The preparation of the photvoltic device was carried out in an oxygen- and water-free environment. An InSnO anode coated glass slide was used as the substrate. A 2 wt% chloroform solution of an electron-donating, (I), poly (ethylene dioxythiophene) [PEDOT], and an electron-accepting, (II), and poly (styrene sulphonate) [PSS] mesogens were used and transferred onto an InSnO-coated glass slide. The substrate was spun so that only a thin film of the blend was formed. The solvent was then evaporated and the reactive mesogens photopolymerized by irradiation with ultraviolet light using an HeCd laser at 325 nm until the film became insoluble (a mercury lamp could alternatively have been used). The absorbance of the film was compared before and after washing it to determine whether the crosslinked layer was completely insoluble. A LiF/Al film was then deposited on the product surface by thermal evaporation.

DERIVATIVES A third mesogenic monomer, (III), was also used to prepare liquid crystalline polymer networks and is illustrated below.

TESTING Photovoltaic devices were irradiated at 400 nm through the transparent substrate at a wavelength that gave significant absorption to determine the quantum efficiency, open voltage, and power conversion. Testing results for selected samples provided in Table 1.

Notes

147

TABLE 1. Physical Properties of Interconnecting Liquid Crystalline Polymer Networks of Reactive Mesogensa Entry 1 2 3 a

Mesogenic Monomers Used

Monomer Ratios

Quantum Efficiency (%)

Open Voltage (V)

Power Conversion (%)

1 and 2 2 and 3 1 and 3

1:1 1:1 1:3

3 — —

.1 — —

— — 0.1

Polymers 1 and 3 were photoinitiated while polymer 2 was thermally initiated at 808C.

NOTES 1. Liquid crystalline polymer networks were prepared by Kelly et al. (1) with mesogenic monomers, (IV), and used in forming networks charge-transporting or luminescent materials.

2. Interconnecting nematic liquid crystalline materials, (V), prepared by Alfred et al. (2) were effective as liquid crystalline emitter and as charge-transport organic light-emitting devices.

3. Crosslinkable reactive mesogens, (VI), were prepared by O’Neill et al. (3) for use in electroluminescent devices. Crosslinking occurred by cyclopolymerization as illustrated in Eq. (1).

148

Liquid Crystalline Interpenetrating Polymer Networks

(1)

4. Peglow et al. (4) prepared polymerizable mesogenic materials consisting of a dichromophoric dichroic network containing azo-chromophores, which were used for preparing dichroic polymer networks and gels.

References 1. S.M. Kelly et al., U.S. Patent Application 20060182899 (August 17, 2006) and U.S. Patent Application 20060113508 (June 1, 2006). 2. M.P. Alfred et al., U.S. Patent Application 20070197737 (August 23, 2007). 3. M. O’Neill et al., U.S. Patent 7,265,163 (September 4, 2007) and U.S. Patent Application 20070194277 (August 23, 2007). 4. T. Peglow et al., U.S. Patent Application 20080001120 (January 3, 2008).

b. Polydibenzothiophenes

Title: Polymer Compound, Polymer Thin-Film and Polymer Thin-Film Device Using the Same Author: Assignee:

Masato Ueda Sumitomo Chemical Company, Limited (Tokyo, JP)

U.S. Patent Application: Material Patentability: Anticipated Issuing Date: Research Focus: Originality: Applications: Observations:

20080003422 (January 3, 2008) High Early 2010

Synthesis of xanthone copolymers for use as electroactive components in thin films. Photovoltaic components consisting of xanthone polymers have not been reported in the patent literature. Organic solar batteries Electroactive thin films typically consist of polymers such as polythiophenes, polyphenylenevinylenes, polyfluorene, and polythienylenevinylene. The application prepared xanthone copolymers, which were effective as active electroactive thin films. Most of these agents performed well in organic thin-film transistor and solar battery property testing. Other aryl amine co- and terpolymers and pentacene derivatives were also identified as next-generation electroactive agents.

149

150

Polymer Compound, Polymer Thin-Film and Polymer Thin-Film Device Using the Same

REACTION

i. ii. iii. iv.

Trifluoroacetic acid, chloroform, sodium perborate monohydrate Magnesium, 1-bromooctane, tetrahydrofuran (THF) Toluene, p-toluenesulfonic acid monohydrate, sodium hydroxide Bis(pinacolate)diborone, [1,10 -bis(diphenyl-phosphino)-ferrocene]palladium 0 dichloride, 1,1 -bis(diphenylphosphino)ferrocene, 1,4-dioxane, potassium acetate v. 2,20 -Bipyridyl, THF, bis(1,5-cyclooctadiene)nickel(0)

EXPERIMENTAL 1. Preparation of lactone intermediate A 500-ml three-necked flask was charged with 2,7-dibromo-9-fluorenone (6.65 g), 140 ml trifluoroacetic acid/chloroform, 1:1, and sodium perborate monohydrate and then stirred for 20 hours. The reaction liquid was filtrated through Celite and then washed with toluene. The filtrate was washed with water, sodium hydrogen sulfite, and saturated saline and then dried over Na2SO4. After concentration 6.11 g of residue was obtained. After recrystallization from chloroform 1.19 g of product was isolated. 2. Preparation of tertiary alcohol using the Grignard reagent A 100-ml three-necked flask was charged with magnesium (1.33 g), 10 ml THF, 2.3 ml of 1-bromooctane and then refluxed for 2.5 hours. The mixture was then cooled and used immediately. A 300-ml flask was charged with the step 1 product (1.00 g) suspended in 10 ml of THF and then cooled to 08C and treated with the entire Grignard reagent and the mixture refluxed for 5 hours. The mixture was cooled and treated with 10 ml of water/hydrochloric acid and a two-phase solution obtained. The organic phase was isolated and washed with water and saturated saline, dried over Na2SO4, concentrated, and 1.65 g of residue obtained. The residue was purified by silica gel column

Derivatives

151

chromatography using hexane/ethyl acetate, 20:1, respectively, and 1.30 g of product isolated. 3. Preparation of xanthone intermediate A 25-ml flask was charged with the step 2 product (0.20 g), 4 ml of toluene, and p-toluenesulfonic acid monohydrate (0.06 mmol) and the mixture heated to 1008C for 11 hours and then cooled. The solution was washed sequentially with water, 4 M NaOH aqueous solution, water, and saturated saline, concentrated, and 0.14 g of product isolated. 4. Preparation of xanthone-borane intermediate A reaction vessel was charged with the step 3 product (1.77 mmol), bis(pinacolate)diborone (3.72 mmol), [1,10 -bis(diphenyl-phosphino)-ferrocene]palladium dichloride (0.11 mmol), 1,10 -bis(diphenylphosphino)ferrocene (0.11 mmol), and 15 ml of 1,4-dioxane. Argon gas was then bubbled into this mixture for 30 minutes. Thereafter, potassium acetate (10.6 mmol) was added and then the mixture heated to 958C for 13.5 hours and then cooled and filtered. The mixture was purified using an alumina short column, concentrated, the residue redissolved in toluene, and treated with activated carbon and filtered. The filtrate was repurified using an alumina short column, re-treated with activated carbon, and refiltrated. The solution was concentrated, the residue recrystallized in 2.5 ml of hexane, and 0.28 g of product isolated. 5. Preparation of xanthone polymer A reactor was charged with the step 4 product (0.96 g), 2,20 -bipyridyl (0.55 g), and THF (80 g). After deaeration, bis(1,5-cyclooctadiene)nickel(0) (1.05 g) was added and the mixture heated to 608C for 1.5 hours and then cooled and precipitated in 300 ml of ion exchange water. The precipitate was isolated and then dissolved in chloroform, filtered, and purified by passing through a column filled with alumina. The polymer was reprecipitated in methanol, reisolated, dried, and 0.5 g of product isolated having an Mn of 7.3 105 Da.

DERIVATIVES A summary of thiophene copolymer repeat units and corresponding Mn’s are provided in Table 1.

152


TABLE 1. Selected Xanthone Copolymers and Corresponding Molecular Weightsa Entry

Polymer Repeat Unit

Mn (Da)

A

1.2 106

B

3.9 105

D

1.0 106

a All copolymers were prepared by coupling dibromo-bithiophene derivatives with comonomers using tetrakis(triphenylphosphine) palladium.

TESTING Selected experimental agents were evaluated for organic thin-film transistor and solar battery properties. Testing results are provided in Table 2. A. Evaluation of Organic Thin-Film Transistor i. Polymer Thin-Film Preparation 1 A polymer thin film having a thickness of 50 nm containing the step 5 product was formed by a spin coating method. The polymer thin film contained an Au electrode that had been vapor deposited and where the source electrode and drain electrode had a channel width of 2 mm and a channel length of 20 mm. ii. Evaluation of Organic Thin-Film Transistor Properties On the polymer thin-film gate a voltage, VG, and source – drain voltage, VSD, were applied from 0 to 280 V. The drain current on the thin-film transistor was as low as 20.8 mA with a VG of 280 V and VSD of 260 V. Experimental results are summarized in Table 2. B. Evaluation of Solar Battery Properties i. Polymer Thin-Film Preparation 2 A glass substrate carrying an ITO film having a thickness of 150 nm was spin coated with 70 nm of poly(3,4)ethylenedioxythiophene/polystyrenesulfonic acid thin film and then dried at 2008C for 10 minutes. A 50-nm coating of a selected experimental agent was sprayed onto the initial film and dried. Lithium fluoride, calcium, and aluminum were then vapor-deposited at 0.4 nm, of 5 and 180 nm, respectively.

Notes

153

ii. Evaluation of Solar Battery Properties While irradiating the experimental agent A thin film with a xenon lamp, the voltage –current properties were measured. In this way solar battery properties of a short-circuit current of 43 mA/cm2 and a open-circuit voltage of 1.75 V for this material were obtained. Testing results are provided in Table 2.

TABLE 2. Organic Thin-Film Transistor and Solar Battery Properties Testing Results for Selected Experimental Agentsa Entry

Thin-Film Transistor Testing (drain current)

Solar Battery Properties

—

Short-circuit current of 43 mA/cm2 and a open-circuit voltage of 1.75 V

Step 5 product

20.8 mA with VG of 280 V and VSD of 260 V

—

D

20.6 mA with VG of 260 V and VSD of 260 V

—

A

a

All testing was conducted at ambient temperature.

NOTES 1. Additional polymer thin films, (I), and polymer thin-film devices were prepared by the authors (1) and used as organic solar batteries.

2. Hirai (2) prepared an organic semiconductor layer for an organic thin-film transistor consisting of pentacene derivatives, (II), having a thickness of 1 mm.

154


3. Aryl amine polymers were prepared by Sagisaka et al. (3) and Okada et al. (4), (III) and (IV), respectively, and used in the composition of organic thin-film transistors.

References 1. M. Ueda et al., U.S. Patent Application 20060043358 (March 2, 2006). 2. K. Hirai, U.S. Patent Application 20070221918 (September 27, 2007) and U.S. Patent Application 20070161163 (July 12, 2007). 3. T. Sagisaka et al., U.S. Patent Application 20070092760 (April 26, 2007). 4. T. Okada et al., U.S. Patent Application 20070048637 (March 1, 2007).

c. Poly(thiazole-thiphenes)

Title: Photovoltaic Cell with Thiazole-Containing Polymer Author: Assignee:

Russell Gaudiana et al. Konarka Technologies, Inc. (Lowell, MA)


20080121281 (May 29, 2008) Moderate December 2010

Synthesis of copolymers containing cyclopentadithiazole and dithiophene derivatives for use in photovoltaic cells. Continuation of a 4-year investigation in the preparation of photovoltaic cells with thiazole-containing polymers. Photovoltaic cells Copolymers containing cyclopentadithiazole were prepared that are effective as photovoltaic cells. Cyclopentadithiazole comonomers were prepared in a two-step process beginning with 2,4-thiazolidinedione in overall favorable yields. An advantage of preparing a copolymer containing a cyclopentadithiazole component is that the absorption wavelength can be shifted toward the red and near infrared (IR) portion of the electromagnetic spectrum, which is not accessible by most photovoltaic polymers. When incorporated into a photovoltaic cell, it enables the cell to absorb light in this region of the spectrum, thereby increasing the current and efficiency of the cell.

155

156

Photovoltaic Cell with Thiazole-Containing Polymer

REACTION

i. Butyl lithium, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, THF ii. 5,50 -Bis(5-bromo-2-thienyl)-4,40 -dihexyl-2,20 -bithiazole, tris(dibenzylideneacetone)-dipalladium(0), triphenylphosphine, Aliquot 336, sodium carbonate, THF, phenylboronic acid, sodium diethyldithiocarbamate EXPERIMENTAL 1. Preparation of 2,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4H4,4-bis(20 -ethylhexyl)cyclopenta [2,1-b: 3,4-b0 ]thiophene A 100-ml Schlenk flask was charged with 4H-4,4-bis(20 -ethylhexyl)cyclopenta[2,1b:3,4-b0 ]dithiophene (2.72 mmol) and then evacuated and purged with argon three times. The flask was then treated with 20 ml THF and then cooled to 2788C and further treated with the dropwise addition of 4.35 ml of 2.5 M BuLi (10.88 mmol). The reaction was then stirred for 1 hour at 2788C and then warmed to ambient temperature and stirred for an additional 3 hours. The solution was recooled again to 2788C and treated with 2.77 ml 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (13.6 mmol) in one portion using a syringe and then stirred at 2788C for 1 hour and warmed to ambient temperature overnight. The solution was poured into water and extracted four times with 150 ml of methyl t-butyl ether. The organic layers were then washed twice with 150 ml of brine, dried with MgSO4, and filtered. The mixture was concentrated and an orange oil isolated. After being purified by column chromatography using 5% EtOAc/hexanes, the product was isolated in 75% yield as a colorless, viscous oil in 75% yield. 2. Preparation of polymer A 100-ml Schlenk flask was charged with the step 1 product (0.231 mmol), 5,50 -bis(5-bromo-2-thienyl)-4,40 -dihexyl-2,20 -bithiazole (0.231 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.00231 mmol), triphenylphosphine (0.0162 mmol), and Aliquot 336 (0.0855 mmol). The flask was evacuated and refilled with argon

Notes

157

three times with 20 ml of THF and 15 ml of toluene. The solution was then treated with 2 ml of 2 M aqueous Na2CO3 and heated for 3 days at 908C. A 1-ml THF solution of phenylboronic acid (0.1155 mmol) and tris(dibenzylideneacetone)-dipalladium(0) (0.00231 mmol) was added while heating continued for an additional 24 hours. After cooling the mixture to 808C 10 ml of a 7.5% sodium diethyldithiocarbamate solution in water was added and the mixture heated at 808C for 18 hours. The reaction was then cooled to ambient temperature and the organic layer separated and washed three times with 100 ml of warm water. The toluene solution was concentrated and then poured into 750 ml of stirring methanol and a dark precipitate isolated and washed with methanol. The precipitate was transferred to a Soxhlet thimble and extracted with acetone overnight. After drying under vacuum, the product was isolated as a brown solid in 84% yield. 1

H-NMR (CDCl3) d 7.2–7.1 (br, 6H), 3.0 (m, 4H), 1.86 (m, 8H), 1.6 (br, 16H), 1.20– 0.65 (br, 32H)

DERIVATIVES No additional derivatives prepared. NOTES 1. The structure for the step 2 reagent, 5,50 -bis(5-bromo-2-thienyl)-4,40 -dihexyl2,20 -bithiazole, (I), is indicated below.

2. Additional photovoltaic cell derivatives are prepared by the authors (1) and are discussed. 3. Polymers containing thiazole components, (II), were prepared by Berke et al. (2) for use in tandem photovoltaic cells.

158

Photovoltaic Cell with Thiazole-Containing Polymer

4. Benzothiadiazole-containing polymers, (III), were prepared by Brabec et al. (3) and used as a component in photovoltaic cells. Benzothiadiazole copolymers were also prepared by the authors (4).

References 1. R. Gaudiana et al., U.S. Patent Application 20070267055 (November 22, 2007). 2. H. Berke et al., U.S. Patent Application 20080006324 (January 10, 2008). 3. C. Brabec et al., U.S. Patent Application 20070246094 (October 25, 2007) and U.S. Patent Application 20070181179 (August 9, 2007). 4. R. Gaudiana et al., U.S. Patent Application 20080087324 (April 17, 2008).

d. Porphyrin thiophenes

Title: Conducting Polymers with Porphyrin Crosslinkers Author: Assignee:

Chee On Too Los Alamos National Laboratory (Los Alamos, NM)


20070295398 (December 27, 2007) Very high End 2009

Development of high-efficiency porphyrin hybrid conducting polymers. Although polyporphyrins have been previously prepared, poly (porphyrins-co-thiophene) copolymers are unreported. Solar panels The first multistep synthesis of polyporphorins was reported in the U.S. patent literature in 1988. The homopolymer was prepared by interfacial condensation where the material was photochemically and electrochemically active. In the current application polyporphorphrin copolymers was prepared in two steps using electroactive terthiophene as the crosslinker agent. This produced conjugated polymers that were photovoltaic. Furan and pyrrole derivatives were also described by the author as crosslinkers for preparing conjugated polyporphyrin analogs.

159

160

Conducting Polymers with Porphyrin Crosslinkers

REACTION

i. 3,30 -Di-n-butyl-4,40 -dimethyl-2,20 -dipyrrylmethane, CH2Cl2, trifluoroacetic acid, DBU, p-chloranil, triethylamine ii. CH2Cl2, tetrabutylammonium perchlorate

EXPERIMENTAL 1. Preparation of 5,15-bis([20 ,200 :500 ,20000 -terthiophen]-300 -yl)-2,8,12,18-tetra-nbutyl-3,7,13,17-tetramethylporphine 30 -Formyl-2,20 :50 ,200 -terthiophene (349 mmol) and 3,30 -di-n-butyl-4,40 -dimethyl-2,20 dipyrrylmethane (349 mmol) were dissolved in 35 ml CH2Cl2 at ambient temperature and then treated with 26.9 mL of trifluoroacetic acid. At the first sign of baseline material by thin-layer chromatography (TLC) using silica gel and CH2Cl2, the reaction was quenched by adding 52.2 mL of DBU and p-chloranil (873 mmol) and the solution stirred for 4 hours at ambient temperature. The mixture was then treated with 36 mL of triethylamine and stirred for 1 hour. Excess triethylamine (5.190 mmol) was then added and mixture stirred for 15 minutes. The reaction mixture was then precipitated in methanol and 76.9 mg product isolated as a brownish-purple solid. 2. Preparation of crosslinked copolymer The step 1 product and 2,20 :50 ,200 -terthiophene were reacted to form the copolymer using cyclic voltammetry and electro-copolymerization. Cyclic voltammetry in CH2Cl2 containing 0.1 M tetrabutylammonium perchlorate supporting electrolyte indicated that the co-monomer oxidation began at approximately 0.70 V vs. Ag/Agþ.

NOTES 1. Nanoscale discotic liquid crystalline porphyrins, (I), were prepared by Li et al. (1), which were effective as high-efficiency photovoltaic materials, organic

Notes

161

semiconducting materials, and organic light-emitting materials. Other discotic liquid crystalline porphyrins, (II), were prepared by Rosselli et al. (2).

2. Tetrametric thiophenes, (III), were prepared by Tomino et al. (3) and used in organic semiconductors.

162

Conducting Polymers with Porphyrin Crosslinkers

3. Oligomeric, (IV), and polymeric alkylthiophenes prepared by Ong et al. (4) were effective as thin-film transistors.

References 1. Q. Li et al., U.S. Patent Application 20070151600 (July 5, 2007). 2. S. Rosselli et al., U.S. Patent Application 20060260669 (November 23, 2006). 3. K. Tomino et al., U.S. Patent Application 20070128763 (June 7, 2007). 4. B.S. Ong et al., U.S. Patent Application 20070117963 (May 24, 2007).

E. Semiconductors a. Adamantane imidazole amides

Title: Prepolymers, Prepolymer Compositions, High-Molecular-Weight Polymers with Pore Structure, and Dielectric Films Author: Assignee:

Akira Takaragi et al. Hitachi, Ltd. (Tokyo, JP)


20070078256 (April 5, 2007) High Early 2010

Synthetic method for preparing semiconductors containing adamantane cores with imidazole thermal barriers. Polyadamantyl cores containing pendant benzimidazoles are unreported in the patent literature. Semiconductors The present application relates to dielectric films used in the production of semiconductors It also relates to the preparation of dielectric films having high heat resistance that show low dielectric properties. Although semiconductors have previously been prepared with polybenzimidazole derivatives, those containing an adamantyl core are not reported. In addition other adamantyl polyamide analogs were prepared by this group and used in photoresist resin compositions. Heat curing adamantane polyamide cores generated the corresponding polybenzimidazole derivatives. Silicon wafers were then spin coated and imidazated at elevated temperatures. Materials produced in this process had favorable dielectric properties and were used as semiconductors.

163

164

Prepolymers, Prepolymer Compositions, High-Molecular-Weight Polymers

REACTION

i. 3,30 -Diaminobenzidine, N, N-dimethylacetamide ii. Adamantanetetracarbonyl chloride, N, N-dimethylacetamide EXPERIMENTAL 1. Preparation of imidazole prepolymer An aliquot of 3,30 -diaminobenzidine (119 mmol) was placed in a three-neck flask and then dissolved in N,N-dimethylacetamide (200 g) and purged with nitrogen. This mixture was then treated with adamantanetetracarbonyl chloride (7.8 mmol) as a 1.5 % solution in N,N-dimethylacetamide over 1 hour under ice-cooling. Thereafter the solution was stirred an additional hour and then placed into an eightfold excess of water. The precipitate that formed was separated by filtration, washed, dried, and then redissolved in N, N-dimethylacetamide and reprecipitated in water. The precipitate was isolated by filtration, dried, and 5.93 g of product isolated having an Mn 1 104 Da. 1

H-NMR (d6-DMSO) d 1.51 –2.60 (m, adamantane ring), 4.63 (b, NH2), 6.45–7.58 (m, aromatic ring), 8.71– 8.88 (q, ZCONHZ)

Notes

165

2. Preparation of benzoimidazole high polymer A coating composition was prepared by dissolving the step 1 product (3.00 g), and 1,3,5,7-adamantanetetracarboxylic acid (0.552 g) in N,N-dimethylacetamide (20.13 g) and then filtering through 0.2 mm membrane. The coating solution was then spin coated onto an 8-inch silicon wafer and heated to 3008C for 30 minutes and then further heated to 4008C for an additional 30 minutes. The film that formed had a thickness of 298 nm, a density of 1.05 g/cm3, and a dielectric constant of 2.3. FTIR (cm21) 806 (s), 1279 (m), 1406 (m), 1450 (s), 1517 (w), 1623 (w), 2854 (s), 2904 (s), 3419 (w)

DERIVATIVES

NOTES 1. Furukawa et al. (1) prepared a functional resin composition containing disubstituted adamantane, (I), which was used as a resist in semiconductor production processes. Monosubstituted analogs, (II), were prepared by Kodama et al. (2). Cyano-containing adamantyl derivatives, (III) and (IV), were prepared by Ito et al. (3) and Bae et al. (4), respectively, and used in preparing semiconductor devices.

166

Prepolymers, Prepolymer Compositions, High-Molecular-Weight Polymers

2. Tetra-, (V), and tri-substituted, (VI), adamantyl derivatives were prepared by Hatakeyama et al. (5) and used as components in semiconductors.

References 1. K. Furukawa et al., U.S. Patent 7,078,562 (July 18, 2006). 2. K. Kodama et al., U.S. Patent 7,273,690 (September 25, 2007) and U.S. Patent 6,808,862 (October 26, 2004). 3. H. Ito et al., U.S. Patent 7,312,354 (December 25, 2007). 4. Y.C. Bae et al., U.S. Patent 7,309,750 (December 18, 2007). 5. J. Hatakeyama et al., U.S. Patent 7,232,641 (June 19, 2007).

b. Adamantoxy polymethacrylates

Title: Polymer Compound, Positive Resist Composition and Process for Forming Resist Pattern Author: Assignee:

Yohei Kinoshita et al. Tokyo Ohka Kogyo Co., Ltd. (Kawasaki-Shi, JP)


20080096126 (April 24, 2008) Moderate 2010

Synthesis of terpolymers containing an acetal adamantoxy methacrylate. While terpolymer-positive resists containing acetal components are documented in the literature, adamantoxy derivatives are unreported. Semiconductor devices The current application pertains to positive resist compositions that contain at least one acetal component that has a very low deprotection energy acetal. Adamantoxy methacrylate was prepared in a single step by a displacement reaction of 2-adamanthyl chloromethyl ether with methacrylic acid under basic conditions. Photoresist compositions containing adamantoxy methacrylate had improved resolution and resist pattern shape were dramatically improved.

REACTION

167

168

Polymer Compound, Positive Resist Composition and Process for Forming Resist Pattern

i. THF, triethylamine, 2-adamanthyl chloromethyl ether ii. g-Butyolactone methacrylate, tricyclodecyl methacrylate, THF, 2,20 -azobisisobutyronitrile, n-heptane

EXPERIMENTAL 1. Preparation of adamantoxy methacrylate A reaction flask was charged with methacrylic acid (6.9 g) dissolved in 200 ml THF containing triethylamine (8.0 g) at ambient temperature and then treated with the dropwise addition of 2-adamanthyl chloromethyl ether dissolved in 100 ml of THF. The solution was stirred for 12 hours and then filtered to remove the precipitated salt. It was then concentrated and the residue dissolved in 200 ml of ethyl acetate. The solution was washed once with water, reconcentrated, and the product isolated as a white solid. FTIR (cm21): 2907, 2854 (CZH stretching), 1725 (CZO stretching), 1638 (CvC stretching) 1 H-NMR (CDCl3) d 1.45– 2.1 (m, 17H), 3.75 (s, 1H), 5.45 (s, 2H), 5.6 (s, 1H), 6.12 (s, 1H)

2. Preparation of positive resist terpolymer composition The step 1 product (20.0 g), g-butyolactone methacrylate (13.6 g), and tricyclodecyl methacrylate (8.8 g) were dissolved in 200 ml of THF and treated with 2,20 -azobisisobutyronitrile and refluxed for 12 hours. The resin was precipitated by pouring the solution into 2 liters of n-heptane. It was then isolated and dried under reduced pressure and the product isolated as a powder having a Mw of 10,800 Da, polydispersity of 2.14, and molar ratio composition of 40:40:20 of adamantoxy methacrylate, g-butyolactone methacrylate, and tricyclodecyl methacrylate, respectively.

DERIVATIVE A comparative terpolymer was also prepared having a molar ratio composition of 40:40:20, respectively, as illustrated below.

Notes

169

TESTING A. Sensitivity The exposure time at which the line and space of 140 nm formed at a ratio of 1:1 was measured as sensitivity. B. Limiting Resolution Limiting resolution of sensitivity was assessed by scanning electron micrography (SEM) micrographs. C. Pattern Collapse The exposure time in selective exposure increases as the pattern becomes thinner, causing pattern collapse as observed by SEM. The results indicate the size of the width of the pattern at which the pattern collapse occurs. D. Contact Angle The contact angle was measured using a FACE contact angle meter Model CA-X150.

TESTING PROCEDURE A solution was prepared by dissolving the experimental agent or comparative into 750 parts by mass of propylene glycol monomethyl ether acetate/ethyl lactate, 6:4, respectively, and coating onto an 8-inch silicone. The coating was heated to 958C for 90 seconds to form a resist film having a thickness of 225 nm. Testing results are provided in Table 1. TABLE 1.

Physical Properties of Positive Resist Compositions

Entry Step 2 product Comparative

Sensitivity (mJ/cm2)

Limiting Resolution (nm)

Pattern Collapse (nm)

Contact Angle (8)

16 19

110 130

71 102

55.7 44.2

NOTES 1. Positive-type resist compositions, (I), were prepared by Ishiduka et al. (1) containing adamanthyl, g-butyolactone, and a perfluoroalcohol component for use in liquid immersion lithography. Perfluoro acetal and ketal, (II), monomers

170

Polymer Compound, Positive Resist Composition and Process for Forming Resist Pattern

were prepared by Maeda et al. (2) and used in chemical-amplification-type resist compositions.

2. A resist pattern composition, (III), was prepared by Kubota et al. (3) that prevented a fine resist pattern from collapsing in the drying step after treatment with a developing agent.

3. Chemically amplified resist compositions having a high transparency to light with a wavelength of 220 nm or less were prepared by Maeda et al. (4) containing alicyclic g-lactone, (IV).

References 1. K. Ishiduka et al., U.S. Patent Application 20070190448 (August 16, 2007). 2. K. Maeda et al., U.S. Patent Application 20050164119 (July 28, 2005). 3. N. Kubota et al., U.S. Patent 7,232,639 (July 19, 2007). 4. K. Maeda et al., U.S. Patent 7,192,682 (March 20, 2007).

c. Polybenzoxazole amide dimethylhexafluoride precursor

Title: Polybenzoxazole Precursor, Photosensitive Resin Composition Using the Same, and Manufacturing Method of Semiconductor Device Author: Assignee:

Kenichiro Sato et al. Fujifilm Corporation (Tokyo, JP)



20080076849 (March 27, 2008) Moderate 2010

Synthesis of perfluoro polybenzoxazole derivatives for use in semiconductor devices. Although the preparation of polybenzoxazole precursors has been an ongoing 5-year investigation with this research group, the introduction of imides at the polymer termini to enhance photosensitivity is unreported in the patent literature. Semiconductors Photosensitive compositions containing polybenzoxazole precursors are characterized as having high sensitivity, a large film remaining rate, and high resolution. It is also desired, however, to prepare polybenzoxazole films having a longer breaking elongation. To address this concern polybenzoxazole precursors were prepared by condensing isophthaloyl chloride and 4,40 -oxy-bisbenzoyl chloride with hexafluoro-2,2-bis-(3amino-4-hydroxyphenyl)propane at ambient temperature. These agents were then converted into the polybenzoxazole derivatives by curing at 3508C or by photoreaction with naphthoquinone-diazide photosensitizer derivatives. To further improve the photosensitivity of these agents, compositions were also prepared from materials containing both imides and alkynyl functions.

171

172

Polybenzoxazole Precursor, Photosensitive Resin Composition Using the Same

REACTION

i. N-Methyl-2-pyrrolidone, isophthaloyl chloride, 4,40 -oxy-bisbenzoyl chloride

EXPERIMENTAL 1. Preparation of Resin A-1 A flask was charged with hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane (0.8 mol), pyridine (1.6 mol), and N-methyl-2-pyrrolidone (1.2 kg) and then stirred at ambient temperature, cooled to 2258C with a dry ice/acetone bath and treated with the dropwise addition of a solution consisting of isophthaloyl chloride (0.364 mol), 4,40 -oxy-bisbenzoyl chloride (0.364 mol), and N-methyl-2-pyrrolidone (700 g). The mixture was stirred at ambient temperature for 16 hours and then diluted with 2 liters of acetone and poured into 50 liters of deionized water. The precipitated white powder was recovered by filtration and washed with a mixture of deionized water and water/methanol, 1:1. The polymer was dried under vacuum at 408C for 24 hours to obtain the product in quantitative yield having a Mw of 6400 Da with a polydispersity is 2.1.

DERIVATIVES

Testing

173

TESTING A. Evaluation of Breaking Elongation Each resin was coated on a silicon wafer by spin coating, baked on a hot plate at 1208C for 3 minutes, and cured by further heating at 1508C for 30 minutes and at 3508C for 60 minutes under nitrogen gas. The film was then peeled off the wafer and cut to a 3-mm width and 7-mm length. The sample was then fixed and stretched with a TENSILON (1 mm/min) and the coefficient of elongation until breaking measured at 238C in accordance with JIS K 6760. Testing results are provided in Table 1. B. Evaluation of Thermal Expansion Coefficient The thermal expansion coefficients of experimental agents were obtained using a 10 mm 3 mm sample and measured with a TMA Q400. Testing results are provided in Table 1.

174

Polybenzoxazole Precursor, Photosensitive Resin Composition Using the Same

C. Photosensitizers Three photosensitizers, P-1, P-2, and P-3, were used in polymerizing resins and are depicted below.

TABLE 1. Physical Properties of Selected Polybenzoxazole Films after Curing for 60 minutes at 35088 C

Entry A-1 A-2 A-3 A-4 A-6

Photosensitizer

Film Remaining Rate (%)

Pattern Deforming Rate (%)

Breaking Elongation (%)

Thermal Expansion (%)

P-1 P-2 P-3 P-1 P-1

92 84 97 95 81

1 2 1 1 11

91 85 90 85 59

55 38 — — —

NOTES 1. Additional polybenzoxazole photosensitizers, (I), were prepared by Yamanaka et al. (1) and are discussed.

Notes

175

2. Other photosensitive polybenzoxazole resins, (II), were prepared by the authors (2) and used in the manufacturing of semiconductor devices.

References 1. T. Yamanaka et al., U.S. Patent Application 20080081294 (April 3, 2008) and U.S. Patent Application 20070212899 (September 13, 2007). 2. K. Sato et al., U.S. Patent Application 20070048656 (March 1, 2007), U.S. Patent Application 20070172753 (July 16, 2007), and U.S. Patent Application 20070166643 (July 19, 2007).

d. Poly(dithienylbenzo[1,2-b:4,5-b0 ]dithiophenes

Title: Poly(dithienylbenzo[1,2-b:4,5-b0 ]dithiophene) Polymers Author: Assignee:

Beng S. Ong et al. Xerox Corporation (Rochester, NY)



20080103286 (May 1, 2008) Moderate November, 2010

Synthesis of poly(4,8-didodecyl-2,6-bis-(3-methyl-thiophen-2-yl)benzo[1,2-b;4,5-b0 ]dithiophene) derivatives for use as semiconductors in polymer thin-film transistors. Poly(dithienylbenzo[1,2-b:4,5-b0 ]dithiophene) and monomeric analogs are reported in the patent literature. Semiconductors Poly(dithienylbenzo[1,2-b:4,5-b0 ]dithiophene)s were prepared in a onestep process and used as semiconductors in thin-film transistors. The effectiveness of these materials as semiconductors is attributed to the presence of two thienylene groups in the polymer. These components assist in enhancing transistor performance, particularly field-effect mobility, in thin-film transistor configurations. Thin-film transistor fieldeffect mobility of 1022 cm22/v.s. were reported with poly(dithienylbenzo[1,2-b:4,5-b0 ]dithiophene) derivatives.

REACTION

176

Notes

177

i. 3-Methylthiophene-2-boronic acid pinacol ester, toluene, tetrakis(triphenylphosphine palladium (0), Aliquot 336, sodium carbonate ii. Iron(III) chloride, chlorobenzene EXPERIMENTAL 1. Preparation of 4,8-didodecyl-2,6-bis-(3-methyl-thiophen-2-yl)-benzo[1,2b:4,5-b0 ]dithiophene A reactor was charged with 2,6-dibromo-4,8-didodeclybenzo[1,2-b:4,5;b0 ]dithiophene (1 g), 3-methylthiophene-2-boronic acid pinacol ester (0.37 g), and 25 ml of toluene and then thoroughly stirred and was purged with argon. The mixture was then treated with tetrakis(triphenylphosphine palladium (0)) (0.04 g), Aliquot 336 (0.3 g) dissolved in 5 ml toluene, and 3.5 ml of 2 M aqueous Na2CO3 and then heated to 1058C for 26 hours. After cooling to ambient temperature 100 ml toluene was added and the organic layer was isolated, washed three times with water, dried using anhydrous MgSO4, filtered, and concentrated. The crude material was purified by column chromatography using silica gel with hexane/CH2Cl2, 7/1, respectively. After being recrystallized using 2-propanol 0.57 g of product was isolated as yellow needle-like crystals. H-NMR (CDCl3) d 7.46 (s, 2H), 7.26 (d, J ¼ 5 Hz, 2H), .6.96 (d, J ¼ 5 Hz, 2H), 3.17 (t, 4H), 2.55 (s, 6H), 1.86 (m, 4H), 1.27 (br, 36H), 0.90 (t, 6H) 13 C-NMR (CDCl3) d 137.92, 136.77,136.37, 135.49, 132.04, 128.86 (2C), 124.72, 120.26, 33.74, 32.31, 30.33, 30.08, 30.04, 29.97 (X2), 29.94, 29.91, 29.74, 23.08, 15.97, 14.55 1

2. Preparation of poly(4,8-didodecyl-2,6-bis-(3-methyl-thiophen-2-yl)benzo[1,2-b:4,5-b0 ]dithiophene) The step 1 product (0.412 g) was dissolved in 10 ml of chlorobenzene and treated with iron(III) chloride (0.46 g) in 10 ml of chlorobenzene and then heated to 658C for 48 hours. After cooling to ambient temperature 15 ml of chlorobenzene was added and the solution poured into 200 ml methanol where it was ultrasonicated for 2 minutes. After being stirred at ambient temperature for 1 hour, a precipitate was isolated that was added to a mixture of 200 ml of methanol and 50 ml 12 M ammonium hydroxide solution. The mixture was then ultrasonicated for 30 minutes and a dark red solid precipitated. The solid was purified by Soxhlet extraction using methanol for 3 hours, hexane for 24 hours, heptane for 24 hours, and then chlorobenzene for 24 hours. After filtration 0.12 g of product was isolated as a dark red solid having an Mn ¼ 16,550 Da, Mw ¼ 65,300 Da, with a polydispersity of 3.95. NOTES 1. The step 1 precursor, 2,6-dibromo-4,8-didodecylbenzo[1,2-b:4,5;b0 ]dithiophene, was prepared according to the method of Pan et al. (1).

178

Poly(dithienylbenzo[1,2-b:4,5-b 0 ]dithiophene) Polymers

2. Li et al. (2) prepared dithiophene analogues, (I) and (II), of the current invention, which were effective as thin-film transistors.

3. Thiophene electronic devices, (III), were prepared by Liu et al. (3) containing thiophene, which was found to be more stable than polyacene-based semiconducting materials.

References 1. H. Pan et al., Chem. Mater, Vol. 18, p. 3237 (2006). 2. Y. Li et al., U.S. Patent Application 20080142788 (June 19, 2008). 3. P. Liu et al., U.S. Patent Application 20080146776 (June 19, 2008).

e. Poly(thiazole-thiophenes)

Title: Composition Containing Thiazole Rings, Organic Semiconductor Polymer Containing the Composition, Organic Active Layer Containing the Organic Semiconductor Polymer, Organic Thin-Film Transistor Containing the Organic Active Layer, Electronic Device Containing the Organic Thin-Film Transistor, and Method of Preparing the Same Author: Assignee:

Bang Li Lee et al. Samsung Electronics Co., Ltd. (Suwon-si, KR)


20080191201 (August 14, 2008) Moderate June, 2011

Method of synthesizing oligomeric and polymeric thiophene-thiophenethiazole derivatives for use in semiconductors. Polythiophene, polythiazole, and poly(thiophene-thiazole) derivatives are reported in the patent literature. Organic and polymeric semiconductors Although thin-film transistors usually consist of an inorganic semiconductor material containing silicone, the use of these materials is economically unfavorable because of material processing requirements. To address this processing concern thiophene-thiophene-thiazole monomers were synthesized in seven steps and then head-to-tail coupled using tetrakis(triphenylphosphine) palladium(0) to polymers having Mn’s 25,000 Da. Dimethyl formamide soluble materials were then converted into thin-film transistors by solution processes.

179

180

Composition Containing Thiazole Rings, Organic Semiconductor Polymer

REACTION

i. ii. iii. iv. v. vi. vii.

Copper cyanide Dithiophosphoric acid diethyl ether Bromooctanone N-Chlorosuccinimide Sodium thiosulfate Chloroform, acetic acid, mercury(II) acetate, iodine Bis(trimethylstenyl)bithiophene, dimethyl formamide, tetrakis(triphenylphosphine) palladium(0), hydrochloric acid, N-bromosuccinimide viii. Tetrakis(triphenylphosphine) palladium(0), bis(trimethylstenyl)bithiophene, dimethyl formamide EXPERIMENTAL 1. Preparation of 2-cyano-3-dodecylthiophene A reaction flask was charged with 2-bromo-3-dodecylthiophene (81 mmol) and excess copper cyanide and the product obtained in 34% yield. 2. Preparation of 2-thioamino-3-dodecylthiophene The entire step 1 product was heated in a THF solution of dithiophosphoric acid diethyl ether (2.5 eq) for 12 hours and the product obtained in 45% yield.

Experimental

181

3. Preparation of 2-thiazole(30 -dodecyl)-3-dodecylthiphene The entire step 2 product was reacted with bromooctanone (1.2 eq) to obtain the product in 32% yield. 4. Preparation of 2-thiazole-thiophene intermediate The step 3 was reacted with N-chlorosuccinimide and the heterocyclic intermediate isolated in 82% yield. 1

H-NMR (CDCl3) d 0.89 (6H), 1.35 (12H), 1.68 (4H), 2.73 (2H), 2.83 (2H), 6.92 (1H), 7.26 (1H)

5. Preparation of thiazole-thiophene iodo intermediate The step 4 product (223 mmol) was added to a reaction flask containing 600 ml apiece of CHCl3 and acetic acid and then treated with mercury(II) acetate (134 mmol). The mixture was agitated for 20 minutes and then treated with iodine (245 mmol) and reacted for 3 hours and then filtered to remove red precipitates. The organic layer was isolated and then washed successively with 500 ml water, three times with 500 ml NaHCO3, three times with 500 ml Na2S2O3, and 500 ml brine. The organic layer was then dried with MgSO4, filtered, and concentrated. The residue was purified by chromatography using hexane and 134 g of product isolated. 1

H-NMR (CDCl3) d 0.88 (t, 6H), 1.26 (m, 36H), 1.65 (m, 4H), 2.73 (m, 4H), 7.07 (s, 1H)

6. Preparation of thiophene-thiophene-thiazole intermediate A reactor was charged with the step 5 product (14.2 mmol) and 1-borotetramethylpinacol-2-dodecylthiophene (14.2 mmol), 50 ml THF, tetrakis(triphenylphosphine) palladium(0) (2.8 mmol), and 60 ml toluene and then refluxed for 2 hours. After cooling the mixture was treated with 200 ml of hexane, washed with 100 ml water, dried with MgSO4, filtered and concentrated. The residue was dissolved in 80 ml CH2Cl2, redried with MgSO4, refiltered, and reconcentrated. It was purified by chromatography using a hexane/chloroform solution and 4.4 g of product isolated as a yellow solid. 1

H-NMR (CDCl3) d 0.88 (t, 9H), 1.26 (m, 54H), 1.64 (m, 6H), 2.79 (m, 6H), 6.94 (d, 2H), 7.19 (d, 1H)

7. Preparation thiophene-thiophene-thiazole monomer The step 6 product (12 mmol) and bis(trimethylstenyl)bithiophene (12 mmol) were added to a reactor under a nitrogen atmosphere and dissolved in anhydrous dimethyl formamide (DMF) with gentle heating. The solution was then treated with tetrakis(triphenylphosphine) palladium(0) (about 10 mol% based on the total amount of reagents) and reacted at 88C for 6 hours. The mixture was then treated with dilute hydrochloric acid solution and extracted with CHCl3 and then concentrated by

182


distillation under vacuum. The residue was washed with methanol, dried, and then reacted with N-bromosuccinimide in chloroform, and 10.1 g of product isolated. 1

H-NMR (CDCl3) d 0.87 (t, 18H), 1.25 (m, 108H), 1.70 (m, 12H), 2.75 (t, 4H), 2.92 (m, 8H), 6.90 (s, 4H), 7.07 (d, 2H), 7.16 (d, 2H)

8. Preparation of thiophene-thiophene-thiazole polymer The step 7 monomer (0.61 mmol) and bis(trimethylstenyl)bithiophene (0.61) were dissolved in anhydrous DMF with gentle heating and then treated with tetrakis(triphenylphosphine) palladium(0) (about 10 mol% based on the total amount of reagents) and the mixture reacted at 858C for 6 hours. The solution was cooled to ambient temperature, filtered, and the polymer isolated. It was then successively washed twice with hydrochloric acid/chloroform, twice with ammonia solution/CHCl3, and twice with water/CHCl3. The polymer was then precipitated in methanol, dried, and 0.38 g of product isolated as a red polymer having an Mn of 25,000 Da. 1

H-NMR (CDCl3) d 0.87 (18H), 1.26 (108H), 1.71 (8H), 1.73 (4H), 2.80 (4H), 2.92 (8H), 6.99 (4H), 7.06 (4H), 7.16 (2H) [0076] 0.86 (18H), 1.26 (108H), 1.71 (8H), 1.84 (4H), 2.80 (4H), 2.93 (8H), 6.99 (4H) 7.07 (4H), 7.16 (4H)

DERIVATIVES Selected thiazole-thiophene monomers are illustrated below:

Notes

183

Polymeric derivatives are depicted below.

NOTES 1. Heteroacene derivatives, (I), were prepared by Park et al. (1), which were effective as organic thin-film transistors. Low-molecular-weight thiophene oligomers were also prepared by Hahn et al. (2) and used as organic semiconductors.

2. In an earlier investigation by the authors (3) thiophene-quinoxaline polymers, (II), were prepared and used in organic thin-film transistors.

3. Organic thin-film transistor comprising perfluorimide copolymer thin films, (III), were prepared by Kim et al. (4) and used in gate electrode, a gate insulating layer, an organic semiconductor layer, and in source/drain electrodes applications.

184


References 1. J.I. Park et al., U.S. Patent Application 20080142792 (June 19, 2008). 2. J.S. Hahn et al., U.S. Patent Application 20080076872 (March 27, 2008). 3. B.L. Lee et al., U.S. Patent Application 20080099758 (May 1, 2008). 4. J.Y. Kim et al., U.S. Patent Application 20070194305 (August 23, 2007).

F. Transistors a. Hydroxycoumarin polysuccinimides

Title: Copolymer, Organic Insulating Layer Composition, and Organic Insulating Layer and Organic Thin-Film Transistor Manufactured Using the Same Author: Assignee:

Joo Young Kim et al. Samsung Electronics Co., Ltd. (Seoul, KR)



20080197345 (August 21, 2008) High December, 2010

Synthesis of poly(hydroxymaleimide-co-hydroxystyrene) compolymer containing pendant 7-hydroxycoumarin and aliphatic or perfluoaliphatic esters. Poly(hydroxymaleimide-co-hydroxystyrene) copolymers modified with 7-hydroxycoumarin derivatives are unreported in the patent literature. Organic thin-film transistors Copolymers with diminished surface energy were prepared in a single step by esterification of poly(hydroxymaleimide-co-hydroxystyrene) with coumarin-oxyhexylbenzoyl chloride and hydrophobic octanoy- or perfluoroanoyl chloride. Other poly(hydroxymaleimide-co-hydroxystyrene thin-film derivatives containing octanoy- and perfluorooctanoylchloride side chains or 3,4-difluorobenzoic ester side chains were also prepared. In all cases charge mobilities, current on/off ratios, and threshold voltages were improved using derivatives containing coumarinmodified poly(hydroxymaleimide-co-hydroxystyrene).

185

186

Copolymer, Organic Insulating Layer Composition, and Organic Insulating Layer

REACTION

i. ii. iii. iv. v.

Potassium carbonate, acetone, 1,6-dibromohexane Potassium carbonate, ethyl-4-hydroxybenzoate, acetone Ethanol, sodium hydroxide, hydrochloric acid CH2Cl2, thionylchloride Poly(hydroxymaleimide-co-hydroxystyrene), N-methylpyrrolidone, amine, octanoyl chloride

triethyl-

EXPERIMENTAL 1. Preparation of coumarin-oxy-bromohexane A reactor was charged with 7-hydroxycoumarin (0.308 mol) dissolved in 1 liter of acetone and then treated with K2CO3 (0.616 mol) and 1,6-dibromohexane (0.616 mol) and refluxed for 24 hours. The mixture was filtered, concentrated, and treated with diethyl ether and water. The organic phase was extracted with diethyl ether, recrystallized, and 64.89 g of product isolated.

Experimental

187

2. Preparation of ethyl coumarin-oxyhexylbenzoate The step 1 product (0.15 mol) was dissolved in 750 ml of acetone and then treated with K2CO3 (0.75 mol) and ethyl-4-hydroxybenzoate (0.15 mol) and refluxed for 24 hours. The reaction solution was then filtered, washed with chloroform, and concentrated. After recrystallization from ethanol 53.74 g of product were isolated. 3. Preparation of coumarin-oxyhexylbenzoic acid The step 2 product (53.74 g) was dissolved in 600 ml of ethanol and then treated with 600 ml 1 M NaOH solution and stirred for 48 hours and then acidified with 10% hydrochloric acid solution and filtered. The material was recrystallized using ethanol and 40 g of product isolated. 4. Preparation of coumarin-oxyhexylbenzoyl chloride Under a protective blanket of nitrogen the step 3 product (13.075 mmol) was dissolved in 100 ml of CH2Cl2 and then treated with thionylchloride (14.383 mmol) and then stirred at 358C for 5 hours and concentrated. After recrystallizing the residual in ethyl acetate/hexane the product was isolated. 5. Preparation of coumarin-modified poly(hydroxymaleimide-cohydroxystyrene) Poly(hydroxymaleimide-co-hydroxystyrene) (5.60 mmol) was dissolved in 20 ml of N-methylpyrrolidone and then cooled to 08C. The solution was then treated with triethylamine (20.16 mmol) and stirred for 60 minutes and then further treated with the step 4 product (0.656 g) and octanoyl chloride (4.03 mmol). The mixture was heated to ambient temperature and stirred for 24 hours and then precipitated by pouring in methanol and water. It was filtered, extracted with methanol, and 5.3 g product isolated.

188


DERIVATIVES A perfluoroalkyl-modified poly(hydroxymaleimide-co-hydroxystyrene) analog was also prepared.

TESTING Contact Angle The surface energy of a thin film was indirectly determined by measuring the contact angle with water. General insulating layers have a contact angle with water of about 608C while an organic insulating layer formed using the modified poly(hydroxymaleimide-co-hydroxystyrene) derivative had a contact angle with water between 85 and 958C. The insulating organic polymer of the current invention may be used to form an insulating layer having a decreased contact angle because of the presence of TABLE 1.

Organic Thin-Film Transistor Properties of Step 5 Producta

Entry Step 5 product Comparativea a

Contact Angle (distilled water) (8C)

Charge Mobility (cm2/Vs)

Current On/Off Ratio

Threshold Voltage VTH at VDS ¼ 210 V

88 65

0.038 0.018

2.1 105 1.3 105

þ2 þ7

Where the comparative consisted of unmodified poly(hydroxymaleimide-co-hydroxystyrene).

Notes

189

highly hydrophobic insulating layers. Contact angle and electronic testing results of the step 5 product are provided in Table 1. NOTES 1. The preparation of additional poly(hydroxymaleimide-co-hydroxystyrene) insulating and thin-film derivatives, (I) and (II), are described by the authors (1,2), respectively, in earlier investigations.

2. Jeong et al. (2) prepared crosslinked copolymers consisting of methyl trimethoxysilane and dipentaerythritol penta-/hexa-acrylate, which were effective as organic thin-film transistors and used in liquid-crystal display devices. 3. Compositions consisting of poly(oligothiophene-thiazole), (III), having an Mn of 40,000 Da were prepared by Hanh et al. (3) and used as organic insulating films in thin-film transistors in liquid-crystal display devices.

190


4. Thiophene-quinoxaline derivatives, (IV), prepared by Lee et al. (4) were also effective as organic thin-film transistors.

References 1. J.Y. Kim et al., U.S. Patent Application 20080067503 (March 20, 2008). 2. E.J. Jeong et al., U.S. Patent Application 20080111129 (May 15, 2008). 3. J.S. Hahn et al., U.S. Patent Application 20080111128 (May 15, 2008). 4. B.L. Lee et al., U.S. Patent Application 20080099758 (May 1, 2008).

VII. ENERGETIC POLYMERS A. Explosive Binder a. Polyphosphazene nitrates

Title:

Novel Energetic Polyphosphazenes

Author: Assignee:

Peter Golding et al. Not provided


20080108784 (February 10, 2008) High December, 2009

Synthesis of noncrystalline energetic perfluoroalkyl nitrate and azido polyphosphazenes. Energetic poly(organophosphazene)s have not been prepared using the synthetic method of the current investigation. Explosive binder and co-binder agent The objective of this investigation was to prepare energetic polyphosphazenes useful as binders that are noncrystalline, malleability, and shock insensitivity as well as having a high-energy density. Although trimeric cyclic phosphazenes functionalized with energetic substituents and 1,5-diamino-1,3,3,5,7,7-hexaazidocyclotetra-phosphazene have previously been prepared, they were ineffective as binders. Polyphosphazenes are inorganic macromolecules containing a phosphorus–nitrogen backbone with each phosphorus atom having two pendant side groups. Polyphosphazene derivatives were prepared by nucleophilic displacement of either fluoroalkoxy or chloro substituents using a nucleophile that consisted of a ketal alkoxide, which was subsequently oxidized using concentrated nitric acid or an azido alkoxide.


191

192


REACTION

i. ii. iii. iv.

Toluene Trifluoroethanol, tetrahydrofuran (THF), sodium hydride Lithium (2,2-dimethyl-[1,3]-dioxolan-4-yl)-methoxide, THF Nitric acid

EXPERIMENTAL 1. Preparation of poly(dichlorophosphazene) Freshly sublimed hexachlorocyclotriphosphazene (17 g) was placed into a dry Pyrex tube and sealed under vacuum and then heated to 2258C for 1 hour and then at 2508C for 16 hours. The tube was cooled to ambient temperature, broken open, and the contents dissolved in a minimum amount of anhydrous toluene. The product was isolated as a colorless rubbery material after precipitation in an excess hexane. 2. Preparation of poly[(bis-trifluoroethoxy)phosphazene] Sodium trifluoroethoxide was prepared by adding a solution of trifluoroethanol (0.05 mol) dissolved in 32 ml THF to a stirred suspension of sodium hydride (0.05 mol)

Experimental

193

in 20 ml THF under an inert atmosphere. This solution was then treated with tetran-butylammonium bromide (0.1 g) and an anhydrous toluene solution of the step 1 product (0.021 mol) and then refluxed for 6 hours before adding it to water. After precipitation in water the product was isolated and purified by redissolving in acetone and reprecipitating in toluene. FTIR (cm21; neat) 1292, 1168, 1080, 962, 897, 845, 662 1 H-NMR (d6-acetone) d 4.55 ppm (m) [CH2CF3] 31 P-NMR (d6-acetone) d26.28 ppm (bs)

3. Preparation of trifluoroethoxy/(2,2-dimethyl-[1,3]-dioxolan-4-yl)-methoxy polyphosphazene To a stirred solution of the step 2 product (4.12 mmol) dissolved in 20 ml THF was added a solution of the lithium salt of (2,2-dimethyl-[1,3]-dioxolan-4-yl)-methanol in 10 ml THF and the mixture refluxed for 18 hours. Upon cooling to ambient temperature, THF was partically removed and a concentrated solution/suspension of the crude product added dropwise to water. The aqueous mixture was then acidified to pH 5 –6 and the precipitated polymer isolated. The polymer was redissolved in 50 ml CH2Cl2 and then dried in vacuo at 508C for several hours. The organic solution was extracted twice with 30 ml saturated sodium chloride solution and once with 30 ml of water. The material was dried using MgSO4, filtered, concentrated, and redissolved in a minimum amount of acetone and then precipitated into 100 ml hexane. Hexane was decanted, dried in vacuo, and the product isolated as a pale yellow viscous liquid in 60 – 90% yield. FTIR (cm21; neat) 2990, 2969, 1281, 1255, 1171, 1084, 964, 879, 843, 660, 562 1 H-NMR (d6-acetone) d 1.29 (s), 1.36 (s) ppm; 3.81 (b), 4.09 (b), 4.36 (b); 4.55 (b) [CH2CF3] 31 P-NMR (d6-acetone) d 27.0 ppm (b)

4. Preparation of trifluoroethoxy/2-nitratoethoxy polyphosphazene A reactor containing 5 ml of 95% nitric acid was cooled to between 0 and 58C in an ice/water bath and then treated with the step 3 product (200 mg) and the mixture stirred for 15 minutes while maintaining the temperature below 58C. The solution was then added dropwise to 60 ml of water, cooled, and the nitrated product isolated as a white, oily solid precipitate. Water was decanted, the precipitate washed with water, and in vacuo at 508C for 2 – 3 hours, and the product isolated as a pale yellow viscous liquid in 80 – 90% yield. FTIR (cm21; neat) 2965, 2904, 1638, 1423, 1373, 1282, 1172, 1073, 965, 904, 853, 758, 705, 654 1 H-NMR (d6-acetone) d 4.46 ppm (b), 4.84 (b) [CH2CF3] 31 P-NMR (d6-acetone) d27.25 ppm, 26.70, 23.07 (vb), ca. 22.0 (vb)

194


DERIVATIVES

POLYMER PROPERTIES TABLE 1.

Physical Properties of Polyphosphazene-Based Energetic Polymers

Sample Step 1 product I II

Energetic Side Groups (%)

Mn (Da)

Number of Energetic Repeat Units

Density (g/cc)

Tg (8C)

72 51 28

— 12,080 —

— 46 —

— 1.31 1.51

220.8 251.5 241.5

Notes

195

NOTES 1. A polyphosphazene azide, (V), derivative were also prepared as illustrated in Eq. (1).

(1)

i. Sodium 6-azido-n-hexoxide 2. Kim et al. (1) prepared the energetic agent poly(glycidyl dinitropropyl formal), (VI), by polymerizing the epoxide precursor, (VII), as illustrated in Eq. (2). The preparation of reaction intermediates is discussed by the authors (2).

(2)

i. Borone trifluoride etherate, 1,4-butandiol 3. Polyurethane energetic block copolymers, (VIII), consisting of toluene diisocyanate, 1,4-butanediol, and dihydroxyl poly(3-azidomethyl-3-methyloxetane) were prepared by Sanderson et al. (3) and used as binders in high-energy compositions, especially rocket propellants. Poly(glycidyl nitrate) urethanes were previously prepared by the authors and are discussed (4).

196


4. Energetic fullerenes, C60(NO2)12, consisting of buckyballs, carbon nanotubes, or buckypaper were prepared by Adams (5) and used as explosives.

References 1. J.S. Kim et al., U.S. Patent Application 20070056663 (March 15, 2007). 2. J.S. Kim et al., U.S. Patent 7,288,681 (October 30, 2007). 3. A.J. Sanderson et al., U.S. Patent Application 20060074215 (April 6, 2006) and U.S. Patent Application 20050133128 (June 23, 2005). 4. A.J. Sanderson et al., U.S. Patent Application 20050133128 (June 23, 2005). 5. C. Adams, U.S. Patent Application 20070055029 (March 8, 2007).

VIII. ENGINEERED PLASTICS A. Blends a. Poly(4-phenylene sulfide) blends

Title:

Polyphenylene Sulfide Resin Composition

Author: Assignee:

Atsushi Ishio et al. Toray Industries, Inc. (Tokyo, JP)


Observations:

20070265375 (November 15, 2007) Moderate Mid/late 2009

Method for preparing intimately mixed polymer blends of nylon-66 and polyphenylene sulfide. Intimate blends of poly(4-phenylene sulfide) and nylons have not previously been prepared. High-performance resins suitable for injection molding Compatibilizing agent for polyamide resins When poly(4-phenylene sulfide) was prepared and used to form intimate blends with nylon, crystalline and noncrystalline domains formed that had an average polyamide dispersion particle size of 200 nm or higher. Although other nylon derivatives have been used to prepare blends with sulfur-based vulcanizing agents, none have generated intimate mixing levels. To address this concern poly(4-phenylene sulfide) was prepared having excellent flowability and impact properties, low-temperature roughness, and injection moldability. When this agent was blended with nylon-66, a resin was produced that had excellent chemical resistance and barrier properties usually associated with poly(4phenylene sulfide).


197

198

Polyphenylene Sulfide Resin Composition

REACTION

i. Sodium hydrosulfide, sodium hydroxide, N-methyl-2-pyrrolidone (NMP), sodium acetate ii. Nylon-66 EXPERIMENTAL 1. Preparation of poly(4-phenylene sulfide) A 70-liter autoclave with a stirrer was charged with sodium hydrosulfide (70.00 mol), sodium hydroxide (70.97 mol), N-methyl-2-pyrrolidone (115.50 mol), sodium acetate (31.50 mol), and 10.5 kg of water and then gradually heated to 2458C over 3 hours. After 14.7 kg of water and 280 g of NMP were distilled off and the reaction vessel was cooled to 1608C. 1,4-Dichlorobenzene (69.63 mol) and NMP (91.00 mol) were added and the vessel hermetically sealed under nitrogen gas. While stirring at 240 rpm, the mixture was heated to 2388C at 0.68C/minute for 95 minutes and then to 2708C at 0.88C/minute for 100 minutes. The mixture was treated with water (70 mol) and then cooled to 2508C at 1.38C/minute. It was further cooled to 2008C at 1.08C/minute and then quickly cooled to ambient temperature. The resin was removed from the reaction chamber and then mixed with 26.3 kg of NMP and isolated after passing through an 80-mesh sieve. The polymer was washed with 32 kg of NMP and then filtered and rewashed with ion exchange water (56 kg) and refiltered. It was further washed with of 0.05 wt% aqueous acetic acid solution (70 kg), filtered, and then rewashed with water and refiltered. The resin was dried in 1208C hot air and the product isolated having a melt viscosity of 200 Pa-s at 3108C with a shear rate of 1000/s. 2. Preparation of poly(4-phenylene sulfide)-nylon-66 blend A blend consisting of the step 1 product (90 weight parts) and nylon-66 (10 weight parts) was dry-blended and the mixture melt-kneaded using a TEX30-a doublescrew extruder. The unit had a L/D of 45.5 with three kneading portions and a screw speed of 300 rpm. The temperature was set to ensure that the resin emerging from the cylinder was 3308C. Strands were cut into pellets and then dried overnight at 1208C and the product isolated. NOTES 1. The preparation of poly(4-phenylene sulfide) with varying molecular weights is described by Horiuchi et al. (1).

Notes

199

2. Blends consisting of poly(4-phenylene ether) and nylon-66 were prepared by Miyoshi et al. (2) and used to prepare automotive interior components. Extruder conditions were virtually identical to those described in step 2. 3. Phase-separated blends consisting of poly(4-phenylene sulfide) and poly(ethylene-co-propylene) or poly(ethylene-co-1-butylene) were prepared by Matsuoka et al. (3) and are discussed. 4. Multilayered blends consisting of poly(4-phenylene sulfide) and nylon-6, nylon 11, nylon-12, and nylon-66, were prepared by Tateyama et al. (4). These resins had good heat, chemical, and abrasion resistance as well as excellent interlayer adhesion. 5. Poly(4-phenylene sulfide) copolymers were prepared by Shiraishi et al. (5) containing 1 – 20% N-(2,5-dichlorophenyl)phthalimide comonomer, (I), that reduced flash generation when injection molded at temperatures exceeding 3208C.

References 1. S. Horiuchi et al., U.S. Patent 7,115,704 (October 3, 2006). 2. T. Miyoshi et al., U.S. Patent Application 20070235893 (October 11, 2007). 3. H. Matsuoka et al., U.S. Patent 6,960,628 (November 1, 2005). 4. M. Tateyama et al., U.S. Patent 6,485,806 (November 6, 2002). 5. K. Shiraishi et al., U.S. Patent 6,787,631 (September 7, 2004).

B. Composites a. Poly(fluorine-co-triaryl amines)

Title: Novel Aromatic/Aliphatic Diamine Derivatives for Advanced Compositions and Polymers Author: Assignee:

D.M. Delozier United States of America as Represented by the Administrator of the National Aeronautics and Space Administration (Washington, DC)


Observations:

200

20080004419 (January 3, 2008) Very high Late 2009

Next-generation high-performance polyfluorene resins for space exploration. Poly(fluorine-co-nitro-aromatic triamines) derivatives have not been reported in the patent literature. Structural composite matrices Radiation shielding materials Optical and electronic devices The current application has synthesized high-performance resins having excellent mechanical and thermal resistance. In addition to being used as a co-reagent for preparing high-performance resins, 2,7-diamino-9,9diocty-fluorene was also used by this group to prepare heavy ion radiation shields associated with space travel. These high-performance radiation shields were prepared by reacting the diamine with 3,4epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate. Additional modifications to the diamine to further enhance its thermal properties are proposed by the author. This group recently prepared a highperformance fiber by filling the interior of a nanotube with 100-nmsized silver powder. The material demonstrated outstanding thermal properties.

Experimental

201

REACTION

i. Acetic acid, nitric acid ii. Ethanol, tetrahydrofuran (THF), 5% palladium on carbon iii. Cetyltrimethylammonium bromide, bis(tri-t-butylphosphine)palladium(0), 1,4bromonitrobenzene, potassium hydroxide iv. Potassium hydroxide, cetyltrimethylammonium bromide, bis(tri-t-butylphosphine)palladium(0) EXPERIMENTAL 1. Preparation of 2,7-dinitro-9,9-dioctylfluorene A reactor was charged with 9,9-dioctylfluorene (26.56 mmol) and 150 ml glacial acetic acid and then cooled to 08C and treated with the dropwise addition of 150 ml fuming nitric acid over 45 minutes. The mixture was slowly warmed to 558C over 2 hours and then recooled to ambient temperature and reacted overnight. A tacky orange precipitate, which formed, was poured into 1200-ml ice water and stirred for 1 hour. The water was decanted and the product washed several times with water. The product was dissolved in 400 ml chloroform and washed sequentially with 200 ml each of water, brine, and water. The organic layer was isolated, dried over MgSO4, concentrated, and an orange liquid isolated. The residue was dissolved in 200 ml hexanes and precipitated by submersing the flask in a dry ice/acetone bath and 27.84 g of product isolated as a yellow solid; mp ¼ 69– 738C. 1

H-NMR (CDCl3) d 0.5 (m, 4H), 0.8 (t, 6H), 1.0– 1.3 (m, 20H), 2.1 (m, 4H), 7.9 (s, 1H), 8.0 (s, 1H), 8.3 (d, 2H), 8.3 (d, 1H), 8.3 (d, 1H) 13 C-NMR (CDCl3) d 14, 23, 24, 29, 29, 29, 30, 32, 40, 57, 119, 122, 124, 145, 149, 154

2. Preparation of 2,7-diamino-9,9-diocty-fluorene The step 1 product (57.93 mmol) was dissolved in 90 ml of absolute ethanol and 50 ml THF and mixed with 5% palladium on carbon (0.5 g) and then hydrogenated in a Parr

202

Novel Aromatic/Aliphatic Diamine Derivatives for Advanced Compositions and Polymers

reactor at 40 psi of hydrogen for 4 hours at ambient temperature. The mixture was then filtered through Celitew and concentrated. The red-brown liquid residue was dissolved in chloroform and stirred with decolorizing charcoal for 1 hour at ambient temperature. The solution was filtered, concentrated, and a red liquid isolated that slowly solidified into needle-like crystals, mp ¼ 58 –638C. 1

H-NMR (CDCl3) d 0.7 (m, 4H), 0.8 (t, 6H), 1.0– 1.3 (m, 20H), 1.9 (m, 4H), 3.6 (s, 4H), 6.6 (m, 4H), 7.3 (d, 2H) 13 C-NMR (CDCl3) d 15, 23, 24, 30, 30, 31, 32, 41, 55, 111, 114, 119, 134, 145, 152

3. Preparation of nitro intermediate A Schlenk flask was charged with cetyltrimethylammonium bromide (0.29 mmol) and bis(tri-t-butylphosphine)palladium(0) (0.57 mmol) and then treated with the step 2 product (57.1 mmol) and 1,4-bromonitrobenzene (57.6 mmol) dissolved in toluene while bubbling in nitrogen. After stirring until the contents dissolved, 45 wt% KOH (85.6 mmol) was added and the vessel heated to 908C for 24 hours. Upon cooling, a red precipitate formed that was isolated, dried under vacuum at 1008C, dissolved in THF, and filtered through a Celitew bed. THF was removed using a rotary evaporation leaving a bright red solid. The solid was recrystallized from toluene and the product isolated as a bright red powder in 65% yield. Elemental Analysis Calc. C, 74.29%; H, 7.60%; N, 8.45%; Found C, 73.01%; H, 6.77%; N, 8.63%

4. Preparation of high-performance polymer A Schlenk flask was charged with cetyltrimethylammonium bromide (8.3 mg) and bis(tri-t-butyl-phosphine)palladium(0) (23.4 mg) and then treated with the step 3 product (2.28 mmol) and 1,4-dibromobenzene (2.28 mmol) dissolved in 15 ml toluene. The mixture was then treated with 45 wt% KOH solution in water (0.8528 g) and heated to 908C for 48 hours. The contents of the vessel were filtered, concentrated, and a reddish oil isolated. The residue was dissolved in chloroform, filtered through Celite, and reconcentrated. The solid was placed into a Soxhlet thimble and extracted for 20 hours with acetone. The polymer was redissolved in chloroform and then precipitated in hexanes and 1.567 g of product isolated.

Notes

203

DERIVATIVES Two fluorene derivatives were prepared as illustrated below:

Entry

R1

Product

4

n-Octyl

Red tacky solid

5

Hydrogen

White solid

NOTES 1. High-performance ahybrid resins were prepared by Yamada et al. (1) having excellent heat resistance and thermal properties. These consisted of hyperbranched polyamide resins derived from the pyromellitic dianhydride with triamines such as 1,3,5-triamino benzene that were postreacted with 3-aminopropyltriethoxysilane. 2. High-performance resins were prepared by Kanada et al. (2) containing the crosslinking co-reagent, 4-naphthoquinonediazidesulfonate, (I).

204

Novel Aromatic/Aliphatic Diamine Derivatives for Advanced Compositions and Polymers

3. High-performance polyimide-positive photosensitive heat resistance resins, (II), were prepared by Yamanaka et al. (3) and used in photosensitive compositions.

4. Pretzer et al. (4) prepared high-performance resins consisting of trimellitic anhydride imide esters derived from ethanol amine, ethylene glycol, and pyromellitic dianhydride that were used in applications requiring good mechanical properties and heat and fire resistance. 5. A high-performance material was prepared by Watson et al. (5) by dry blending multiwalled carbon nanotubes with 100 nm silver particles for three hours at 3008C. In this process upto 23% silver was deposited in the interior of the nanotubes. These materials are intended to be used in those applications requiring high-strength fibers.

References 1. Y. Yamada et al., U.S. Patent Application 20070149759 (June 28, 2007). 2. T. Kanada et al., U.S. Patent Application 20070154843 (July 5, 2007). 3. T. Yamanaka et al., U.S. Patent 7,189,488 (March 13, 2007). 4. W.R. Pretzer et al., U.S. Patent Application 20070027292 (February 1, 2007). 5. K.A. Watson et al., U.S. Patent Application 20070292699 (December 20, 2007).

C. Crosslinking Agents a. 7-Methylene-1,5-dithaoctan methacrylate

Title: Dental Compositions Containing Hybrid Monomers Author: Assignee:

Ahmed S. Abuelyaman et al. 3M Innovative Properties Company (St. Paul, MN)


20080194722 (August 14, 2008) High June, 2010

Synthesis of polymerizable hybrid monomers containing a methacrylate and a 7-methylene dithiane terminus. Monomers containing a methacrylate and dithiane terminus are unreported in the patent literature. Restorative dentistry Typical dental composite resins contain low-viscosity dimethacrylate monomers such as triethyleneglycol dimethacrylate, which shrink substantially upon polymerization because of their low molecular weight. To address this concern linear hybrid monomers containing a methyacrylate and dithiane terminus were photopolymerized and had a Watts shrinkage of less than 1.6%. Watts shrinkage rates of 2% or less were previously observed for dimethacrylate dithiane monomers. Photopolymerized carbosilane dimethacrylates monomers used in dental compositions also had Watts shrinkage rates of less than 2%.

205

206

Dental Compositions Containing Hybrid Monomers

REACTION

i. Mono-2-methacryloyloxyethyl phthalate, CH2Cl2, 4-(N,N-dimethylamino)pyridine, N,N-dicyclohexyl carbodiimide ii. Diphenyl iodonium diglycidyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethlyene hexafluorophosphate, ethoxylated bisphenol A diglycidyl dimethacrylate, bisphenol A glycol dimethacrylate

EXPERIMENTAL 1. Preparation of 1-(2-methacryloyloxyethyl)-2-(7-methylene-1,5dithiaoctan-3-yl) phthalate Mono-2-methacryloyloxyethyl phthalate (31 mmol) and 7-methylene-1,5-dithiacyclooctan-3-ol (31 mmol) were dissolved in 50 ml CH2Cl2 and then treated with 4-(N,N-dimethylamino)pyridine (400 mg). The mixture was cooled in an ice bath for 20 minutes and then treated with dropwise addition of N,N-dicyclohexyl carbodiimide (34 mmol) dissolved in 50 ml CH2Cl2 over a period of 60 minutes. It was then stirred for 60 minutes in an ice bath and then at ambient temperature overnight. A precipitate that formed was removed by vacuum filtration using a Buchner funnel and the filtration aid Celitew and then washed with 100 ml 0.1 M HCl, 100 ml 5% NaOH, and with 100 ml water. The organic layer was dried and concentrated to give a slightly cloudy viscous liquid and 11.4 g of product isolated. 2. Preparation of hybrid polymer The step 1 product, bisphenol A diglycidyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethlyene glycol dimethacrylate, bisphenol A diglycidyl dimethacrylate, and diphenyl iodonium hexafluorophosphate were mixed with diphenyl iodonium hexafluorophosphate and then heated to 858C for 5 minutes and mixed in a DAC 150 FV speed mixer for 1 minute at 3000 rpm. Silane-treated, nano-sized silica and zirconia particle filler were then added and the mixture reheated to 1858C for 5 minutes. It was then remixed in a DAC 150 FV speed mixer an additional 1 minute at 3000 rpm and the dental composition isolated.

Testing

207

DERIVATIVES

TESTING A. Diametral Tensile Strength Diametral tensile strength of experimental agents were measured using an uncured composite sample that was injected into a 2-mm tube and then capped with a silicone rubber plug and compressed axially at approximately 2.88 kg/cm2 pressure for 5 minutes. The sample was then light cured for 80 seconds by exposure to a XL 1500 dental curing light followed by irradiation for 90 seconds in a Kulzer UniXS curing box. Cured samples then stood for 1 hour at 378C at 90%þ relative humidity and then cut with a diamond saw to form 8-mm long cylindrical plugs for measuring diametral tensile strength using an Instron tester. Testing results of selected experimental samples are provided in Table 2.

208


B. Watts Shrinkage Test The Watts shrinkage test method measures shrinkage of a test sample in terms of its volumetric change after curing. Sample preparation and procedures are described in Determination of Polymerization Shrinkage Kinetics in Visible-Light-Cured Materials: Methods Development, Dental Materials, October 1991, pages 281– 286. Testing results of selected experimental agents are provided in Table 2. C. Barcol Hardness Test Barcol hardness testing was measured according to the following procedure. An uncured composite sample was cured in a 2.5-mm-thick Teflon mold sandwiched between a sheet of poly(ethylene terphalate) and a glass slide for 30 seconds with an ELIPAR Freelight 2 dental curing light. After irradiation, the poly(ethylene terphalate) film was removed and the hardness of the sample at both the top and the bottom of the mold were measured using a Barber-Coleman Impressor equipped with an indenter. Testing results of selected experimental agents are provided in Table 2.

TABLE 1.

Dental Composition Prepared Using the Step 1 Product Dental Composition

Component (parts by weight) a

BisGMA BisEMA-6b UDMAc Step 2 product CPQd EDMABe DPIHEF f BHTg Filler a

Entry 5

Entry 7

Entry 8

Entry 9

4.99 4.35 4.75 9.50 0.04 0.22 0.11 0.03 76

4.87 0 4.24 13.54 0.04 0.21 0.11 0 77

9.32 0 4.21 9.12 0.04 0.21 0.10 0 77

13.8 0 4.14 4.73 0.03 0.20 0.10 0 77

2,2-Bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane. Ethoxylated bisphenol A dimethacrylate. c Diurethane dimethacrylate. d Camphorquinone. e Ethyl 4-(N,N-dimethylamino)benzoate. f Diphenyl iodonium hexafluorophosphate. g 2,6-Di-t-butyl-4-methylphenol. b

209

Notes

TABLE 2. Hardened Dental Composition Testing Results Using Step 1 Product as Hybrid Monomer Watts Entry 5 7 8 9 Referenceb a b

Barcol Hardness a

Visual

Shrinkage (%)

DTS (MPa)

Top

Bottom

Opacity

1.58 1.3 1.36 1.33 1.93

71 74 68 65 76

83 80 80 80 86

81 76 76 75 85

0.35 0.30 0.27 — 0.35

Dimetral tensile strength. FILTEK SUPREME restorative.

NOTES 1. Additional curable compositions containing dithiane monomers, (I), were prepared by Lewandowski et al. (1) and are discussed.

2. Lewandowski et al. (2) prepared containing polymers of carbosilane and methacrylate derivatives, (II), which were effective in dental compositions and had a Watts shrinkage of less than 2%. Crosslinkable carbosilane methacrylate monomers, (III), effective in dental compositions were also prepared by Lewandowski et al. (3) in an earlier investigation that had a Watts shrinkage of less than 2%. Carbosilane derivatives effective in dental compositions were prepared by Bissinger et al. (4) and are described.

210


3. Nozawa et al. (5) prepared reactive methacrylate monomers containing isocyanate functions, (IV), which were used in dental compositions.

References 1. K.M. Lewandowski et al., U.S. Patent Application 20070066748 (March 22, 2007). 2. K.M. Lewandowski et al., U.S. Patent Application 20080045626 (February 28, 2008). 3. K.M. Lewandowski et al., U.S. Patent Application 20070276059 (November 19, 2007). 4. P. Bissinger et al., U.S. Patent Application 20080070193 (March 20, 2008). 5. K. Nozawa et al., U.S. Patent Application 20080132597 (June 5, 2008).

b. Polystyrenealkoxy epoxides

Title: Method for Preparing Glycidyloxystyrene Monomers and Polymers Thereof Author: Assignee:

Keith Kunitsky et al. E.I. Du Pont De Nemours and Company (Wilmington, DE)



20080167433 (July 10, 2008) Moderate April, 2001

Method of preparing 4-hydroxystyrene by de-carboxylation of 4-hydroxylcinnamic acid for use in preparing poly(4-glycidyloxystyrene). While the thermal decarboxylation of cinnamic acid as a method of preparing styrene is well documented in the literature, the preparation of poly(4-glycidyloxystyrene) is novel. Intermediate Thermal decarboxylation of 4-hydroxycinnamic acid followed by the base-catalyzed condensation with epichlorohydrin was used in a singlestep process for preparing 4-glycidyloxystyrene. The intermediate, 4-hydroxystyrene, was prepared in situ and not isolated. Free radical polymerization of this monomer in either THF or toluene produced poly(4-glycidyloxystyrene) with number-average molecular weights exceeding 100,000 Da. In a subsequent investigation by this group, the thermal decomposition of N,N-dimethyltyrosine N-oxide was used to prepare 4-hydroxystyrene.

211

212

Method for Preparing Glycidyloxystyrene Monomers and Polymers Thereof

REACTION

i. N,N-Dimethylacetamide, potassium acetate ii. Potassium hydroxide, epichlorohydrin iii. THF or toluene, 2,20 -azobis(isobutyrylnitrile) or 1,10 -azobis(cyclohexanecarbonitrile)

EXPERIMENTAL 1. Preparation of 4-hydroxystyrene p-Hydroxycinnamic acid (1.100 mol) and N,N-dimethylacetamide (562.8 g) were charged into a round-bottom flask and then stirred at ambient temperature for 10 minutes. The mixture was then heated to 1538C and then treated with a single addition of anhydrous potassium acetate (1.508 g). The mixture was then heated to 1508C for 210 minutes where high-performance liquid chromatography (HPLC) indicated an essentially quantitative conversion of p-hydroxycinnamic acid to 4-hydroxystyrene. The mixture was then cooled to ambient temperature and distilled to remove 282.62 g of N,N-dimethylacetamide. HPLC analysis of this sample indicated that 34.46 wt% of 4-hydroxy-styrene was present and used in step 2 without purification. 2. Preparation of 4-glycidyloxystyrene Finely ground anhydrous potassium hydroxide (16.7 mmol) was charged into a 25-mL round-bottom flask and then treated with the step 1 product (15.14 mmol) and epichlorohydrin (0.224 mol). The mixture was then heated to 908C for 60 minutes where the reaction solution became thick with solids and where the absence of the step 1 product was confirmed by gas chromatography (GC). The mixture was filtered through a glass-fritted filter and then washed with a minimum amount of N,Ndimethylacetamide and concentrated at 608C @ 300 mtorr. A slightly turbid, yellow oil was formed that was stored in a refrigerator at 08C where it solidified. It was then thawed and dissolved in 25 ml diethyl ether where it was filtered through a Celitew pad and rinsed with diethyl ether then and reconcentrated and 2.112 g of solid isolated. Upon redistillation two fractions were isolated. Fraction 1 had a boiling point of 69 – 718C; fraction 2 had a boiling point of 75– 808C.

213

Reaction Scoping

3. Preparation of poly(4-glycidyloxystyrene) A 25-ml Schlenk tube was charged with the step 2 product mixture (1.76 or 2.00 g) dissolved in 2 or 9 ml of either THF or toluene. All samples were free radically initiated using either 2,20 -azobis(isobutyrylnitrile) (Vazow 64) or 1,10 -azobis(cyclohexanecarbonitrile) (Vazow 88). Each tube was then sealed with a rubber septum and then degassed by three cycles of freeze – thaw pumping and then heated to 608C for selected times. After cooling to ambient temperature, the mixture was precipitated in 20 ml petroleum ether and then isolated and washed with cold petroleum ether and the product isolated. DERIVATIVE

REACTION SCOPING TABLE 1. Selected Polymerization Scoping Reaction Studies Conducted at 6088 C Using 2.00 g of 4-Glycidyloxystyrene Reaction Number 1 4 5 6 11 13

Vazow 64 (mg)

Vazow 88 (mg)

THF (ml)

Toluene (ml)

Reaction Time (h)

Yield (%)

93.2 18.64 9.32 0 9.32 9.32

0 0 0 138.6 0 0

9 9 0 9 0 3

0 0 9 0 2 0

3 3 3 3 16 18

18.9 5.25 5.9 3.75 100 53

TABLE 2. Physical Properties of Poly(4-glycidyloxystyrene) Prepared Using Table 1 Polymerization Reaction Parameters Reaction Number

Mn (Da)

Mw (Da)

Mz (Da)

Polydispersity

1 4 5 6 11 13

7,954 19,191 26,113 13,897 106,321 32,209

16,312 35,770 42,754 28,978 252,572 86,289

36,108 50,672 59,296 47,896 573,812 153,172

2.051 1.871 1.637 2.085 2.332 2.741

214

Method for Preparing Glycidyloxystyrene Monomers and Polymers Thereof

NOTES 1. Authur et al. (1) prepared 4-(2-hydroxyethoxy)-styrene monomers and oligomers, (I), by the base-catalyzed reaction of 4-acetoxystyrene with ethylene oxide as illustrated in Eq. (1).

(1)

i. Methanol, potassium carbonate, ethylene oxide 2. Poly(4-hydroxystyrene) was previously prepared by the authors (2) by the decarboxylation of 4-hydroxycinnamic acid followed by the free radical polymerization using Vazow 67. 3. Decarboxylation of N,N-dimethyltyrosine N-oxide, (II), was used by Shuey et al. (3) as a method of preparing 4-hydroxylstyrene as illustrated in Eq. (2).

(2)

i. N,N-Dimethylacetamide, potassium acetate

References 1. S.D. Arthur et al., U.S. Patent Application 20050234266 (October 20, 2005). 2. K. Kunitsky et al., U.S. Patent Application 20080033126 (February 7, 2008) and U.S. Patent Application 20080033126 (October 13, 2005). 3. S.W. Shuey et al., U.S. Patent Application 20080167493 (July 10, 2008).

D. High-Performance Polymers a. Novolaks

Title: Phenol-Formaldehyde Resins Having Low Concentration of Tetradimer Author: Assignee:

Ramji Srinivasan et al. Georgia-Pacific Resins, Inc. (Atlanta, GA)


Observations:

20080064799 (March 13, 2008) High 2011

Method for minimizing the formation of phenol-formaldehyde tetramers in phenol-formaldehyde condensation reactions. The use of sodium sulfite as an agent to lower tetramer formation in Novolak resins is unreported in the literature. Engineered plastics High-performance resins In the process of preparing novolak resins, phenol-formaldehyde tetramer are undesirable reaction side products because they diminsh the storage stability of the resins. Several methods have been used to control their formation including: i. Preparing resins in a two-stage base and acid-phase condensation process. ii. Using small amounts of sodium tetraborate early in the reaction process to control the formation of tetramers and to stablize the resin. iii. Using strongly basic tertiary amines such as 2-dimethylamino-2methyl-1-propanol as reaction catalysts. The current application has determined that tetramer formation can be minimized using amounts low in sodium sulfite as a reaction catalyst.

215

216

Phenol-Formaldehyde Resins Having Low Concentration of Tetradimer

REACTION

i. Water, sodium sulfite, formaldehyde EXPERIMENTAL 1. Preparation of phenol-formaldehyde resin A reaction vessel consisting of phenol (1040 ppw), water (226 ppw), and sodium sulfite (305 ppw) was warned to 578C and treated with 50% aqueous formaldehyde (532 ppw) over 25 minutes where the mixture exothermed to 808C. After the addition the mixture was warmed to 1008C for 60 minutes and then cooled to 808C and additional 50% formaldehyde (1094 ppw) added to the reaction mixture over 30 minutes. The reaction extent was monitored by determining the concentration of free phenol in the mixture. When the free phenol content was about 0.7% by weight the mixture was cooled to ambient temperature and a third quantity of formaldehyde (850 ppw) added. The isolated resin had a total solids content of 47 wt%, a free formaldehyde content of 12.6 wt%, and a free phenol content of 0.3 wt%. REACTION SCOPING TABLE 1.

Entry 2 3 4 8

Tetramer Content for Phenol-Formaldehyde Resins Prepared at 8088 C

Phenol (ppw)

Sodium Sulfite (ppw in water)

50% Formaldehyde (ppw)

Water (ppw)

1040 1104 1236 565

305 324 182 200

226 1126 631 207

532 475 532 200

Co-catalyst None None None Sodium Hydroxide

Tetradimer Content (ppw) 5 –7 5 –7 7.2 8.2

Notes

217

NOTES 1. The preparation of otherl phenol-formaldehyde resins using sodium sulfite as catalyst is described by the authors (1). 2. Durairaj et al. (2) prepared unsaturated novolaks, (I), using resorcinol, formaldehyde, and 1,4-dihydroxy-2-butene with p-toluene sulfonicacid as catalyst that contained 8.7% tetramer.

3. Resorcinol/phenol-formaldehyde condensation products prepared by Durairaj et al. (3) using zinc acetate as the reaction catalyst contained 2% p-p0 -phenolic, 16% o-p0 -phenolic, 64% o-o0 -phenolic-4-40 -resorcinolic, 16% 2-40 -resorcinolic, and 2% 2-20 -resorcinolic methylene bridges. 4. Karasawa et al. (4) prepared a tetramer-free condensation carboxylic acid resin, (II), by the reacting methyl salicylate with 1,2-dimethoxyxylene catalyzed by trifluoromethanesulfonic acid.

References 1. R. Srinivasan et al., U.S. Patent Application 20080064284 (March 13, 2008). 2. R.B. Durairaj et al., U.S. Patent 7,196,156 (March 27, 2007) and U.S. Patent 7,074,861 (July 11, 2006). 3. R.B. Durairaj et al., U.S. Patent 6,828,383 (December 7, 2004). 4. A. Karasawa et al., U.S. Patent 6,040,111 (March 21, 2000).

b. Polyaromatic Alkenes

Title: Modified Conjugated Diene Polymer, Polymerization Intitiator, Method of Producing the Same, and Rubber Composition Author: Assignee:

Eiju Suzuki et al. Bridgestone Corporation (Tokyo, JP)


20080033110 (February 7, 2008) Moderately high 2010

Preparation of amine-containing polymerization initiators for synthesis of high interaction poly(styrene-co-butadiene). Six-year ongoing investigation in preparing low hysteresis automotive tires. Automotive tires A method of lowering automotive tire heat buildup or hysteresis is by increasing the interaction of poly(styrene-co-butadiene) with the filler. In this application, a method has been developed for preparing high interaction poly(styrene-co-butadiene) by initiating with an anionic organo reagent lithium in the presence of silylated mono- or diamines. In this process the terminus becomes amine-functionalized. This method has also been used with lithiated piperidine, 1,3-dimethylimidazolidinone, and piperazine to lower tire hysteresis.

REACTION

218

219

Reaction Scoping

i. n-Butyllithium, chlorotrimethylsilane, tetramethylethylene diamine ii. Cyclohexane, butadiene, styrene, 2,6-di-t-butyl-p-cresol

EXPERIMENTAL 1. Preparation of anionic initiator A Kjeldahl flask was charged with N,N0 -dimethyl-1,6-diaminohexane (5.75 mmol) dissolved in 10 ml of THF and then treated with the dropwise addition of n-butyllithium (5.75 mmol) while vigorously stirring. This solution was then treated with chlorotrimethylsilane (5.75 mmol) and stirred at ambient temperature for 30 minutes and then filtered off through a poly(tetrafluoroethylene) (PTFE) filter and 15 mL of the filtrate charged into a 150-ml glass bottle. This aliquot was then treated with tetramethylethylene diamine (4.23 mmol) and n-butyllithium (4.23 mmol) and used immediately as a polymerization initiator. 2. Preparation of poly(styrene-co-butadiene) A pressure glass vessel was charged with a cyclohexane solution of butadiene (60 g) and styrene (15 g) and treated with 11.7 ml of the step 1 product and the mixture polymerized at 508C for 2.5 hours. The conversion was approximately 100%. Thereafter, 0.5 ml of 5% 2,6-di-t-butyl-p-cresol dissolved in isopropanol was added and the mixture precipitated in an isopropanol solution containing slight amounts of hydrochloric acid and BHT. The mixture was dried and the product isolated having an Mn of 1.74 105 Da with a polydispersity index (PDI) of 1.02 and ML1þ4 (1008C) of 22.

REACTION SCOPING TABLE 1. Entry A B C D E F

Initiator Compositions Used in Preparing Poly(styrene-co-butadiene) Initiator Composition Step 1 product Hexamethylene imine and butyl lithium Butyl lithium Tin tetrachloride and butyl lithium Step 1 product and tin tetrachloride Hexamethylene imine, butyl lithium, and tin tetrachloride

Mn (Da 105)

PDI

ML1þ4 (1008C)

1.74 1.95

1.20 1.08

22 28

3.82 2.11 3.19

1.62 1.04 1.87

80 24 76

3.57

1.71

74

220

Modified Conjugated Diene Polymer, Polymerization Intitiator

TESTING Low Loss Factor Testing (Loss Due to Hysteresis). Testing results for tan d measured at 508C at a frequency of 15 Hz with 3 or 10% strain are provided in Table 2. TABLE 2. Low Loss Factor Testing Results for Compounded Poly(styrene-butadiene) Rubber a Sample A B C D E F a

Type

tan d (3%, 508C)

Experimental Comparative Comparative Comparative Experimental Comparative

69 87 73 100 54 65

Lower tan d values are preferred.

NOTES 1. In an earlier investigation by the authors (1) an initiator mixture consisting of neodymium neodecanoate, methylaluminoxane, diisobutylaluminum, and diethylaluminum chloride was used to prepare poly(styrene-co-butadiene) having greater than a 99% cis-1,4 bond content. 2. A styrene/butadiene initiator consisting of diisobutylaluminum hydride, triisobutylaluminum, neodymium(III) neodecanoate, and ethylaluminum dichloride was prepared by Luo et al. (2) and used to prepare polybutadiene containing a cis-1,4-linkage content of 98.7%, a trans-1,4-linkage content of 1.0%, and a 1,2-linkage content of 0.3%. 3. Poly(styrene-b-butadiene-b-styrene) flower-like nanoparticles having a molecular weight of 56,700 Da with a polydispersity of 1.04 were prepared by Wang et al. (3) using equimolar amounts of triethylamine and butyllithium with butadiene, styrene, and divinylbenzene. References 1. E. Szuki et al., U.S. Patent Application 20070179267 (August 2, 2007) and U.S. Patent Application 20070055029 (March 8, 2007). 2. S. Luo et al., U.S. Patent 7,094,849 (August 22, 2006). 3. X. Wang et al., U.S. Patent 7,205,370 (August 17, 2007).

c. Polycarbonates

Title: (Co)polycarbonates Having Improved Adhesion to Metals Author: Assignee:

Helmut-Werner Heuer Bayer Material Scientific LLC. (Pittsburgh, PA)



20080081896 (April 3, 2008) Moderate 2009

Synthesis of high Tg co-polycarbonates containing 3,3-bis(4hydroxyphenyl)-1-phenyl-1H- indol-2-one and bisphenol A biphenols, which adhere to aluminum. Ongoing 6-year-old investigation. Engineering plastics Co-polycarbonates having Tg’s . 2048C have been prepared by interfacial polymerization of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1Hindol-2-one and bisphenol A biphenols with phosgene at moderately elevated temperature in the presence of alkaline solution. These condensation polymers had Mn’s and Mw’s averaging 9000 and 19,000 Da, respectively, with polydispersities of 2.0 that adhered to aluminum surfaces. The bisphenol 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one was prepared in a single step from N-phenylisatin and molten phenol and not through the use of a phenolphthalein derivative. Although phenylisatin could have also been prepared through a modified isonitrosoacetanilide isatin process, it was formed in a one-pot process by reacting oxalic acid dichloride and aluminum chloride with diphenylamine.

221

222

(Co)polycarbonates Having Improved Adhesion to Metals

REACTION

i. Oxalic acid dichloride, toluene, aluminum chloride ii. Phenol, 3-mercapto-propionic acid, hydrogen chloride iii. Bisphenol A, sodium hydroxide, water, CH2Cl2, chlorobenzene, phosgene, 4-tbutylphenol, N-ethylpiperidine

EXPERIMENTAL 1. Preparation of N-phenylisatin A reactor charged with oxalic acid dichloride (5.20 mol) dissolved in 1600 ml toluene and diphenylamine (4.72 mol) dissolved in 1200 ml toluene was heated for 1.5 hours at 458C. The cyclization was carried using anhydrous aluminum chloride (15 g) and refluxing for 3 hours. The mixture was precipitated in water and the crude product isolated and washed three times with distilled water and then dried. The product was isolated in 92.7% yield as an orange-colored solid having an mp of 1388C with a GC purity of 98.7%. 1

H-NMR (CDCl3) d 7.71– 7.69 (d, 1H), 7.58– 7.52 (m, 3H), 7.47– 7.41 (m, 3H), 7.19–7.15 (t, 1H), 6.91–6.88 (d, 1H)

2. Preparation of 3,3-bis(4-hydroxyphenyl)-1-phenyl-1H-indol-2-one The step 1 product (6.27 mol), freshly distilled and molten phenol (37.6 mol), and 3-mercaptopropionic acid (0.66 mol) were charged into a reactor and heated to 40 – 458C and then treated with hydrogen chloride gas for 25 minutes with moderate stirring during which time the temperature exothermed to 678C. The dark brown batch was then cooled to ambient temperature and a beige suspension which formed filtered. The crude product was washed eight times with 1 liter of CH2Cl2 and the product isolated in 97.2% purity in 33.6% yield.

Notes 1

223

H-NMR (d6-DMSO) d 9.47 (s, 2H), 7.60– 7.57 (t, 2H), 7.50– 7.45 (m, 3H), 7.30–7.35 (d, 1H), 7.28–7.20 (t, 1H), 7.15– 7.10 (t, 1H), 7.09– 7.04 (d, 4H), 6.81–6.79 (d, 1H), 6.77– 6.71 (d, 4H)

3. Preparation of polycarbonate A mixture consisting of 15% bisphenol A (52.0 g) and the step 2 product (89.5 g) dissolved in 81.8 g of concentrated sodium hydroxide and 720 ml water was combined with 736.9 g of a solvent mixture consisting of CH2Cl2/chlorobenzene, 1:1, containing dissolved phosgene (63.0 g). To regulate the molecular weight of the polycarbonate, 4-t-butylphenol (2.461 g) was added to the solvent mixture of CH2Cl2/ chlorobenzene. To mainjtain the pH 12 – 13, 46.7% strength sodium hydroxide (66.0 g) solution was metered in. At the end of the reaction, N-ethylpiperidine (0.515 g) dissolved in the solvent mixture CH2Cl2/chlorobenzene, 1:1, was added. The product was isolated having a Mn ¼ 8417 Da, Mw ¼ 18,666 Da, PDI of 2.22, with a Tg of 2108C. SCOPING REACTIONS Polymerization reactions were duplicated four times using the step 3 procedure and the following results obtained and are summarized in Table 1. TABLE 1. Physical Properties of Polycarbonate Prepared Using Bisphenol A, 3,3-bis(4-hydroxy-phenyl)-1-phenyl-1H-indol-2-one, and Phosgene Dissolved in CH2Cl2/Chlorobenzene at Ambient Temperature Entry

Mn (Da)

Mw (Da)

PDI

Oligomer Content (%)

Tg (8C)

4 5 6 7

10,497 10,052 8,280 8,633

22,972 24,666 16,777 17,407

2.19 2.23 2.03 2.02

1.41 1.41 1.82 1.65

210 212 207 204

NOTES 1. Branched polycarbonates consisting of 2,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]phenol, (I), and phosgene were previously prepared by the authors (1) and used in engineered plastics.

224

(Co)polycarbonates Having Improved Adhesion to Metals

2. Horn et al. (2) prepared branched polycarbonate resins by reacting 1,1,1-tris(4hydroxyphenyl)ethane and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3dihydroindole, (II), with phosgene.

3. Mahood et al. (3) prepared co-polycarbonates having Tg’s . 2508C by reacting cyclohexane-bisphenol, (III), and phosgene capped with bischloroformate. 4,4-Bis-(4-hydroxyphenyl)-2,6-diphenyl-cyclohexane-1,1-dicarboxylic acid dimethyl ester was also converted into the thermally stable polycarbonate, (IV), by Kamps et al. (4) by condensing with phosgene.

References 1. H.-W. Heuer et al., U.S. Patent 7,345,133 (March 18, 2008). 2. K. Horn et al., U.S. Patent 6,613,869 (September 2, 2003). 3. J.A. Mahood et al., U.S. Patent Application 20070123686 (May 31, 2007) and U.S. Patent Application 20070123688 (May 31, 2007). 4. J.H. Kamps et al., U.S. Patent 7,326,763 (February 5, 2008).

d. Poly(dicyclopentadienes)

Title:

Method for Preparing Poly(dicyclopentadiene)

Author: Assignee:

Wayde V. Konze et al. The Dow Chemical Company (Philadelphia, PA)


20080023884 (January 31, 2008) Moderate Mid-2010

The preparation of high yielding poly(dicyclopentadiene) containing minimal residual monomer for subsequent crosslinking into thermplastics. The procedure for removing residual monomer prior to crosslinking in an extruder in novel. High-performance materials Although poly(dicyclopentadiene) has been previously prepared using ruthenium-based ring-opening metathesis polymerization methods, the product contained an excess amount of odorous monomer. The current method of preparing high poly(dicyclopentadiene) using tungsten oxychloride with diallyldimethylsilane produces a product containing approximately 10 ppm residual monomer. Extruder crosslinking using a Lewis acid or other ROMP catalysts produces a material having a gel content of at least 95%.

225

226


REACTION

i. Tungsten oxychloride, toluene, diallyldimethylsilane, dicyclopentadiene ii. Phenol, borontrifluoride diethyletherate

EXPERIMENTAL 1. Preparation of poly(dicyclopentadiene) A polymerization vial maintained under dry nitrogen in a drybox was charged with tungsten oxychloride (209 mg) and 50 ml of toluene and then stirred for 10 minutes producing a deep red color. This mixture was treated with diallyldimethylsilane (12.25 mmol) and then stirred for 5 minutes. Thereafter 50 ml of 1.69 M solution of dicyclopentadiene dissolved in toluene was added and the vial stirred for 4 hours. The mixture was then treated with 20 ml of 2% sodium hydroxide solution dissolved in methanol and stirred overnight. The mixture was placed in a separatory funnel and washed four times with 100 ml of water and then concentrated to 75 ml. The solution was treated with 200 ml of methanol and then stirred vigorously for several days to produce a viscous oily polymer. The solvent was decanted and the oil washed four times with 40 ml methanol. The oil was placed under high vacuum and 10.5 g of product isolated as a nearly odorless white powdery solid having an Mn of 2319 Da. 2. Preparation of crosslinked poly(dicyclopentadiene) The step 1 product (200 mg) was treated with phenol (100 mg) and heated to 808C and then further treated with borontrifluoride diethyletherate (0.09 mmol). The mixture immediately turned red and increased in viscosity. The vial was then heated to 1058C for 1 hour and then treated with 10 ml of distilled water and stood overnight at ambient temperature. The mixture was dissolved in 3 ml of toluene and sonicated. The soluble fraction did not show any polymer resonances by 1H-NMR spectroscopy indicating that the polymer has become crosslinked.

Notes

227

REACTION SCOPING TABLE 1. Polymerization Reaction Scoping for Preparation of Polycyclopentadiene Using Tungsten Oxychloride as Catalyst and Corresponding Physical Properties Entry 1 2 3 4

Dicyclopentadiene (mmol)

Diallyldimethylsilane (mmol)

Conversion (%)

Mn (Da)

84.3 84.3 84.3 42.1

12.25 6.12 3.06 6.12

81.5 93.3 91.4 80

2,319 3,467 6,709 2,150

NOTES 1. Multicoordinated metal complex comprising a multidentate Schiff base ligand with ruthenium, (I) and (II), were prepared by Schaubroeck et al. (1) and Verpoort et al. (2), respectively, and used to prepare poly(dicyclopentadiene).

2. Liaw et al. (3) prepared polynorborene macroinitiators, (III), using the ruthenium-based ring-opening metathesis polymerization catalyst, Ru(¼CHC H )[P(C H ) ]. Cl2 6 5 6 11 3

228


3. Monomers, (IV), which were crosslinkable using free radical polymerization with azoisobutyronitrile or with ring-opening metathesis polymerization catalyst, Cl2Ru(¼CHC6H5)[P(C6H11)3] were prepared by Liaw et al. (4) and used in thermosets.

References 1. D. Schaubroeck et al., U.S. Patent Application 20070043188 (February 22, 2007). 2. F.W.C. Verpoort et al., U.S. Patent Application 20070185343 (August 9, 2007). 3. D.J. Liaw et al., U.S. Patent Application 20070173609 (July 26, 2007) and U.S. Patent Application 20070173608 (July 26, 2007). 4. D.J. Liaw et al., U.S. Patent Application 20070073079 (March 29, 2007).

e. Polyester sulfonates

Title: Use of Copolymerizable Sulfonate Salts to Promote Char Formation in Polyesters and Copolyesters Author: Assignee:

Eastman Chemical Company (Kingsport, TN) Deanna L. Pickel



20080167440 (June 18, 2008) Medium November, 2009

Synthesis of polyethylene terephthalate esters containing up to 4.6 mol% sulfurized terephthalate derivatives as a method of increasing char formation. These sulfurized copolymers are unreported in the patent literature. Injection-molded articles 0.1–4.6 Mol% sulfonated phosphosulfonated terephthalate and isoterephthalate acids were prepared and incorporated as additive monomers in the polyester backbone consisting of terephthalate acid and ethylene glycol. When heated to 6008C high char formation was observed. Copolymers containing phosphorus oxyacid in the main chain have previously been prepared and used as flame retardants.

229

230

Use of Copolymerizable Sulfonate Salts to Promote Char Formation

REACTION

i. Dimethyl terephthalate, ethylene glycol, titanium tetraisopropoxide EXPERIMENTAL 1. Preparation of sulfurized polyethylene terephthalate A mixture of dimethyl terephthalate (0.495 mol), 5-sodiosulfoisophthalic acid (0.005 mol), ethylene glycol (1.0 mole), and titanium tetraisopropoxide (100 ppm) was placed in a 500-ml flask equipped with an inlet for nitrogen, a metal stirrer, and a short distillation column. The flask was placed in a heated metal bath and the contents heated at 1858C for 2 hours, 2008C for 2 hours, and then up to 2508C under high vacuum for 2 hours. The temperature was finally increased to 2708C and a vacuum of 0.45 mmHg maintained for for 2 hours to remove unreacted diol. A high melt viscosity polymer was obtained with a glass transition temperature of 778C with an inherent viscosity of 0.77 dl/g. SULFURIZED COMONOMERS

TESTING PROCEDURE Poly(ethylene terephthalate)s modified with increasing amounts of 5-sodiosulfoisophthalic acid were prepared and char formation analyzed by thermogravimetric analysis at 6008C. Samples were heated at a rate of 208C/min under a nitrogen flow of 50 ml/min. Char testing results are provided in Table 1.

Notes

231

TABLE 1. Char Formation of Polyethylene Terphthalate Modified with 5-sodiosulfoisophthalic Acid 5-Sodiosulfoisophthalic (mol%) 0 0.1 0.4 0.9 2.5 4.6

Temperature 10% Loss (8C)

Char at 6008C (wt%)

Tg (8C)

418 410 410 401 408 403

10.0 16.2 16.6 18.7 18.2 19.3

— 83.4 81.2 76.5 70.6 64.3

NOTES 1. DeSchryver et al. (1) prepared polybrominated polystyrene that was effective as a flame-retardant fiber. Polyarylene sulfide oxide prepared by Muraoka et al. (2) was also effective as a heat-resistant agent. 2. Polymer blends, (I), prepared by Williams et al. (3) were effective in achieving flame retardancy while retaining physical properties.

3. A flame-resistant copolymer consisting of 40 -biphenol polysulfone and biphenol A was prepared by El-Hibri et al. (4) and used as a medical or dental device as a steam sterilizable medical tray container. References 1. D.A. De Schryver et al., U.S. Patent Application 20080139752 (June 12, 2008). 2. H. Muraoka et al., U.S. Patent Application 20080081899 (April 3, 2008). 3. M.K. Williams et al., U.S. Patent Application 20080064833 (March 13, 2008). 4. M.J. El-Hibri et al., U.S. Patent Application 20070155871 (July 5, 2007).

f. Poly(ethylene-co-5-ethylidene-2-norbornene)

Title:

Preparation of Curable Polymers

Author: Assignee:

Lin Wang et al. E.I. Du Pont De Nemours and Company (Wilmington, DE)



232

20080058485 (March 6, 2008) High 2010

Synthesis of curable poly(ethylene-co-5-ethylidene-2-norbornene) copolymers using a catalyst pair consisting of iron and zirconium metal complexes. The preparation of poly(ethylene-co-5-ethylidene-2-norbornene) using this catalyst pair is unreported in the patent literature. Vulcanizable elastomers Ethylene-propylene diene monomers (EPDM) elastomers consisting of ethylene alone or in conjunction with propylene and a nonconjugated diene, such as ethylidene norbornene, or dicyclopentadiene have previously been prepared using titanium and vanadium transition metal catalysts. In order to be useful, however, the ethylene and propylene orientation in the material must be nonbranched and nonblocky. These requirements have met using a mixed catalystic system consisting of an iron catalyst complex that can oligomerize ethylene and a zirconium transition metal complex that can copolymerize ethylene and the nonconjugated monomer 5-ethylidene-2-norbornene. Using this catalytic pair nonbrancy poly(ethylene-co-5-ethylidene-2-norbornene) and poly (ethylene-co-1,4-hexadiene) were prepared.

Derivative

233

REACTION

i. Toluene, dichlorozirconium complex, biphenyl iron derivative, ethylene

EXPERIMENTAL 1. Preparation of poly(ethylene-co-5-ethylidene-2-norbornene) A 600-ml Parrw reactor was charged with 5 ml toluene and 4.2 ml of 13.5 wt% toluene solution of methylaluminoxane. This was sequentially treated with a zirconium complex (2.0 mg) dissolved in 2 ml toluene, 0.1 wt% toluene solution of iron biphenyl derivative (433 mg), 30 ml 5-ethylidene-2-norbornene, and 120 ml 2,2,4-trimethylpentane. The autoclave was sealed and heated to 658C and then pressurized with ethylene to 1.24 MPa. The reaction mixture was heated to 908C for 2 hours, cooled to ambient temperature, and vented. The mixture was slowly poured into 400 ml of methanol and then treated with 6 ml of 12 M hydrochloric. It was stirred for 25 minutes at ambient temperature, filtered, washed with methanol six times, and 3.06 g of product isolated as a white powdery solid.

DERIVATIVE The curable copolymer, poly(ethylene-co-1,4-hexadiene), was also prepared as illustrated below.

234

Preparation of Curable Polymers

NOTES 1. The catalyst pair consisted of a mixture of a dichlorozirconium (I), and biphenyl iron, (II), complexes.

2. The biphenyl iron complex, 2,6-diacetylpyridinebis(4-chloro-2,6-dimethylphenylimine)iron dichloride, (III), was prepared by Kristen et al. (1) and used to prepare polyethylene.

3. A curable terpolymer consisting of ethylene, propylene, and 5-ethylidene-2norbornene, (IV), was prepared by Murakami et al. (2) using (t-butylamido)dimethyl(tetramethyl-h5-cyclopentdienyl)silanetitanium dichloride as a main catalyst, (C6H5)3CB(C6F5)4 as a co-catalyst, and triisobutylaluminum as the organoaluminum compound. The product was used in preparing automotive tire treads. It was also prepared by Ravishankar (3) using vanadium tetrachloride and ethyl aluminum sesquichloride as co-catalyst.

Notes

235

4. Curable poly(dicyclopentadiene), (V), was prepared by Konze et al. (4) using ring-opening metathesis polymerization with tungsten oxychloride and diallyldimethylsilane.

References 1. M.-O. Kristen et al., U.S. Patent Application 20080027192 (January 31, 2008). 2. H. Murakami et al., U.S. Patent Application 20080064818 (March 13, 2008). 3. P.S. Ravishankar, U.S. Patent 7,135,533 (November 15, 2006). 4. W.V. Konze et al., U.S. Patent Application 20080023884 (January 31, 2008).

g. Polyimides

Title: Modifiable Polyunsaturated Polymers and Processes for Their Preparation Author: Assignee:

Anbanandam Parthiban Agency for Science, Technology, and Research (Singapore, SG)


20060189774 (August 24, 2006) Medium Mid/late 2009

Single-step method for preparing linear multifunctional copolyolefin imides. While multifunctional copolyolefin imides have been previously reported in the patent literature, this synthetic route in this application is novel. Thermoplastics A versatile condensation method for preparing alternating linear polymers by nucleophilic condensation with trans-1,4-dibromo-2-butene is described.

REACTION

236

Derivatives

237

i. Ammonium hydroxide, acetic acid ii. Potassium t-butoxide, N,N-dimethylacryamide, trans-1,4-dibromo-2-butene, hexane

EXPERIMENTAL 1. Preparation 4,40 -(4,40 -Isopropylidene diphenoxy)bis(phthalimide) 4,40 -(4,40 -Isopropylidene diphenoxy)bis(phthalic anhydride) (0.01 mol) was suspended in 25 ml of glacial acetic acid then treated with the dropwise addition of 30 ml 28% ammonium hydroxide over 30 minutes. After the addition the solution color became yellow and the mixture stirred for 30 minutes and was then refluxed overnight. Once cooled to ambient temperature it was poured into water, filtered, dried, and the product isolated in 60% yield as a white solid, mp ¼ 2488C. FTIR (KBr, cm21) 3258, 3069, 2971, 1769, 1718, 1600, 1501, 1476, 1364, 1312, 1271, 1234, 1168, 1086, 1040, 927, 837, 749, 646

2. Preparation of poly(trans-2-butene-co-imide) The step 1 product (0.004 mol) and potassium t-butoxide (0.008 mol) were heated to 1108C in a solvent mixture of 25 ml DMAc and 10 ml hexane overnight in a flask containing a Dean –Stark apparatus. After hexane was removed, the mixture was cooled to ambient temperature and treated with trans-1,4-dibromo-2-butene (0.004 mol) and then stirred at ambient temperature for 48 hours. The mixture was then poured into 800 ml of water and a white solid isolated that was air dried and the product isolated in 91% yield. FTIR (KBr, cm21: 2967, 2934, 1773, 1711, 1623, 1600, 1503, 1476, 1443, 1391, 1360, 1272, 1233, 1173, 1097, 1080, 1014, 947, 905, 841, 748, 544 Mn (GPC) 10,167 Da Tg 1878C

DERIVATIVES Poly(nucleoplilc-co-olefin) polymers prepared according to the specifications of this application are summarized in Table 1.

238

Modifiable Polyunsaturated Polymers and Processes for Their Preparation

TABLE 1. Copolymers of Trans-1,4-bromo-2-butene Formed by Condensing with Selected nucleophiles in N,N-dimethyl Acrylamide Using a 1:1 Reagent Chargea Entry

Copolymer Category

Nucleophile

Tg (8C)

Tm (8C)

Mn (Da)

Yield (%)

1

Poly(ether-co-olefin)

147

211

—

91

2

Poly(ester-co-olefin)

108

—

—

92

3

Poly(ester/ether-co-olefin)

115

—

53,323

—

5

Poly(amine-co-olefin)

—

—

—

—

9

Poly(amino/ether-co-olefin)

—

—

—

94

10

Poly(thioether-co-olefin)

—

—

—

—

11

Poly(ketone-co-olefin)

—

—

—

—

a

Multistep (Note 1) 1

All products were characterized by H- and

13

C-NMR and FTIR by the author.

NOTES 1. Nonalternating single-step olefinic ketones, (III), were also prepared by this group in the current application.

2. In an earlier investigation by the author (1), polymeric ketones, (II), were prepared at ambient temperature by acid dehydration of a-phenyl acetic acid using phosphorus pentoxide and methane sulfonic acid as illustrated in Eq. (1). Aromatic polyketones formed from this process are provided in Table 2.

(1)

239

Notes

TABLE 2. Selected Aromatic Polyketones Prepared by Dehydration of a-Phenyl Acetic Acid Using Phosphorus Pentoxide and Methane Sulfonic Acida Entry

Yield (%)

Mw (Da)

5

86.0

—

7

85.5

15,777

a

Structure

Extensive FTIR characterization supplied by the author.

3. Condensation polymers consisting of the Michael addition product of aminoethylpiperazine with 1,4-butanediacrylate, (I), as illustrated in Eq. (2) were prepared by Liu et al. (2) and used as vectors for delivery of DNA (deoxyribonucleic acid) to a cell.

(2)

4. Dendritic polymers with enhanced amplification and interior functionality were prepared by Tomalia et al. (3) by slow step-growth polymerization techniques including polyimine formation followed by rapid ring-opening reactions.

References 1. A. Parthiban U.S. Patent 7,034,187 (April 25, 2006). 2. Y. Liu et al., U.S. Patent 7,309,757 (December 18, 2007). 3. D.A. Tomalia et al., U.S. Patent Application 20070298006 (December 27, 2002).

h. Polyketones

Title:

Process for Preparing Polyketone

Author: Assignee:

Jae-Yoon Shim et al. Hyosung Corporation (Anyang-si, KR)



20080058494 (March 6, 2008) High 2011

Preparation of poly(ethylene-co-carbon monoxide) using the organometallic mixture consisting of palladium acetate and 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane. 1,3-Bis[bis(2-methoxy-phenyl) phosphino]-propane is an especially active insertion catalyst and is unreported in the patent literature. Engineering plastics Although poly(ethylene-co-carbon monoxide) has previously been prepared using nickel-based catalysts with methyl alumoxane,

1,3-bis[bis(2-methoxy-phenyl) phosphino]propane, and 1,3-bis[bis(2methoxy-5-methylphenyl)phosphino]propane in acetic acid, catalyst activity has not been robust. To address this concern, high-molecularweight poly(ethylene-co-carbon monoxide) was inexpensively prepared using palladium acetate and 1,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane in either acetone or methanol additized with 1000– 10,000 ppm of water. The process also requires the presence of an acid having a pKa of 4 or less and benzothiazole.

240

Polymerization Scoping Studies

241

REACTION

i. Palladium acetate, 1,3-bis[bis(2-methoxy-5-methyl-phenyl)phosphino]propane, trifluoroacetic acid, benzothiazole, acetone, carbon monoxide EXPERIMENTAL 1. Preparation of poly(ethylene-co-carbon monoxide) An autoclave was charged with palladium acetate (0.0140 g), 1,3-bis[bis(2-methoxy5-methylphenyl)phosphino]propane (0.0398 g), trifluoroacetic acid (0.0499 g), benzothiazole (0.4225 g), and 100 ml of acetone. The solution was then treated with 2497.5 ml of methanol and water (1000 ppm) and then sealed and stirred at 800 rpm. The mixture was heated to 708C and carbon monoxide and ethylene having a molar ratio of 1:1.8, respectively, added until the internal pressure of the autoclave was 100 bar. The mixture was then stirred for 2 hours while the internal temperature and the internal pressure were maintained at 100 bar and 708C. After cooling the contents were removed, degassed, filtered, washed with methanol several times, and 51.5 g of product isolated. POLYMERIZATION SCOPING STUDIES TABLE 1. Poly(ethylene-co-carbon monoxide) Scoping Reactions Using the Step 1 Reaction Stoichometry

Entry 2

3

4

5

Solvents (amount) Acetone (2497.5 ml) Water (1000 ppm) Acetone (2497.5 ml) Water (1000 ppm) Methanol (2497.5 ml) Water (25 ml) Methanol (2200 ml) Water (300 ml)

Acid (g)

Ethylene/ Catalyst CO (molar Temperature Pressure Activity Polymer ratio) (8C) (bar) (kg/g.Pd.h) h (dl/g)

TFA (0.049 g)

1:2

80

100

5.4

15.7

TFA/H2SO4 (0.029 g)

1:1.8

70

70

6.7

13.5

H2SO4 (0.1226)

1:1.8

70

80

32.7

4.5

H2SO4 (0.0429)

1:1

70

90

36.3

4.3

242

Process for Preparing Polyketone

NOTES 1. The structure for the step 1 reagent, 1,3-bis[bis(2-methoxy-5-methyl-phenyl)phosphino]propane, (I), is illustrated below.

2. Poly(ethylene-co-carbon monoxide) was also prepared by Kwon et al. (1) using acetic acid and water as the reaction solvent. It was also prepared by Taniguchi et al. (2) using 1,3-bis[bis(2-methoxy-5-phenyl)phosphino]-propane, (II), with palladium acetate and 1,4-benzoquinone.

3. Shigematsu et al. (3) prepared aliphatic polymers containing ketone and ether components in the main chain, (III), by the dehydration of glycerol followed by treatment with 1,10-decane diol and sulfuric acid at 1658C.

4. MacKenzie (4) prepared poly(ethylene-co-carbon monoxide) at low pressure using a nickel-based catalyst, (IV), with methyl alumoxane.

Notes

243

References 1. I.-H. Kwon et al., U.S. Patent Application 20080058493 (March 6, 2008). 2. R. Taniguchi et al., U.S. Patent Application 20060135738 (June 22, 2006). 3. T. Shigematsu et al., U.S. Patent Application 20060287470 (December 21, 2006) and U.S. Patent Application 20060252907 (November 9, 2006). 4. P.B. MacKenzie, U.S. Patent 6,797,792 (September 28, 2004).

i. Poly(styrene-co-pyrrolidinium chloride)

Title: Block Copolymers of Diallyldialkylammonium Derivatives Author: Assignee:

Balint Koroskenyi et al. CIBA Specialty Chemicals Corporation (Tarrytown, NY)


244

20080033115 (February 7, 2008) High Mid-2010

Preparation of amphiphilic block copolymers to increase the wettability and printability of a plastic surface containing thermoplastic blends. Thermoplastics containing amphiphilic block copolymers as antistatic agents is novel. Thermoplastic Although block copolymers of diallydialkylammonium salts containing polyethylene glycol block and cetyl acrylate have been prepared, there still exists a need for preparing aromatic amphiphilic block copolymers. To address this concern amphiphilic block copolymers were prepared by esterification of hydroxyl-terminated polystyrene with mercaptoacetic acid and then free radically coupled with the cationic monomer, diallyldimethyl ammonium chloride, forming the methyl pyrrolidinium chloride block. The coupling phase was unique since quaternization is usually performed as a separate step after the block copolymer has been prepared. Blending the amphiphilic block copolymer with polystyrene resulted in increased surface wettability with antistatic properties.

Derivatives

245

REACTION

i. Toluene, mercaptoacetic acid, sulfuric acid ii. Toluene, diallyldimethyl ammonium chloride, 2,20 -azobis(2-amidinopropane) dihydrochloride

EXPERIMENTAL 1. Preparation of thiol end-functional polystyrene A mixture consisting of hydroxyl end-functional polystyrene (25.80 g; Mw 4000– 5000 Da), 40 ml toluene, 1.37 ml mercaptoacetic acid, and 1 drop sulfuric acid were sparged with nitrogen for 30 minutes and then refluxed for 2 hours. The mixture was cooled in an ice bath and precipitated in methanol and the product isolated. 2. Preparation of poly(styrene-b-methyl pyrrolidinium chloride) The step 1 product (1.0 g) was dissolved in 2.0 ml toluene and then treated with diallyldimethylammonium chloride (1.0 g) dissolved in 4.0 ml of toluene containing 2,20 azobis(2-amidinopropane) dihydrochloride (51 mg). The mixture was then sparged with nitrogen for 30 minutes and then stirred at 708C for 24 hours. The solution was then cooled and precipitated with acetone and the product isolated.

DERIVATIVES Only the step 2 product was prepared.

246

Block Copolymers of Diallyldialkylammonium Derivatives

TESTING Contact Angles The antistatic properties of the step 2 product were evaluated by preparing tapes of blends with polystyrene by extruding in a twin-screw extruder using a flat die at 2008C. The contact angle of the tapes was measured using the sessile drop method and water as the measuring liquid. Testing data not supplied by author.

NOTES 1. Additional antistatic block copolymers such as poly[(ethylene-co-propylene)-bmethyl pyrrolidinium chloride] were prepared by the authors (1) in an earlier investigation. 2. Polyquaternary organosilicon materials, (I), prepared by Ochs et al. (2) exhibited good biocidal properties while also exhibiting good washfastness, hydrophilicity, and softness.

3. Polyisobutylene-based block anionomers and cationomers, (II), were prepared by Kennedy et al. (3) and used in drug release devices. Poly(2-dimethylamino)ethyl methacrylate was quaternized after the block copolymer was synthesized to form a cationic block copolymer.

4. A neutral diblock copolymer consisting of poly[(butyl acrylate)-b-(2-dimethylaminoethyl acrylate)] was prepared by Bavouzet et al. (4) and used in cosmetic formulations.

Notes

247

5. Dubief et al. (5) prepared cationic block copolymers of poly(styrene-co-Nmethyl-4-vinylpyridinium iodide), which were used in washing compositions.

References 1. B. Koroskenyi et al., U.S. Patent Application 20080033106 (February 7, 2008). 2. C. Ochs et al., U.S. Patent Application 20070212326 (September 13, 2007). 3. J.P. Kennedy et al., U.S. Patent 7,196,142 (March 27, 2007). 4. B. Bavouzet et al., U.S. Patent 7,235,231 (June 27, 2007). 5. C. Dubief et al., U.S. Patent Application 7,232,561 (June 19, 2007).

j. Polysulfides

Title:

Process for Producing Polyarylene Sulfide

Author: Assignee:

Mitsuhiro Matsuzaki et al. Kureha Corporation (Tokyo, JP)



20080097075 (April 24, 2008) Moderate 2011

Method of preparing high-molecular-weight polyphenylenesulfide by the base-catalyzed reaction of paradichlorobenzene with anhydrous sodium sulfide. Ongoing 4-year investigation. Engineering plastics The process for producing polyphenylenesulfide has consistently faced the problem of increased ionic impurities and the presence of polyphenylene sulfide oligomers in the product Dry product contaminated with these materials is powdery and difficult to purify. To resolve this problem several logistical operations were put into place including: i. Subjecting the polymerizate slurry to continuous countercurrent washing with water and N-methyl pyrrolidone ii. Washing the product with an upward flow of countercurrent contacting washing liquid of water, N-methyl pyrrolidone, and acetone iii. Drying the product on a upward shaking platform

248

Notes

249

REACTION

i. N-Methyl pyrrolidone, sodium sulfide pentahydrate, water, sodium hydroxide

EXPERIMENTAL 1. Preparation of polyphenylenesulfide A 200-liter autoclave was charged with 60 kg of N-methyl pyrrolidone and sodium sulfide pentahydrate containing 46.30 wt% of sodium sulfide (38 kg). After aeration with nitrogen gas, the temperature was gradually elevated to 2008C under stirring within 3.5 hours to distill out water (16.5 kg) and N-methyl pyrrolidone (11 kg) while H2S (5.0 mol) was removed by vaporization. After the dehydration step the reaction vessel contained Na2S (220.4 mol) and was cooled to 1808C and treated with paradichlorobenzene (34.35 kg), N-methyl pyrrolidone (28.15 kg), water (1.83 kg), and NaOH (133 g). Under stirring the system was subjected to polymerization for 4.5 hours at 2208C and then further charged with 4.17 kg of pressurized water as a phase separation agent followed by heating to 2558C for 2.0 hours. After completion of the polymerization the crude product was isolated having an average particle size of 400 mm and was purified by washing with acetone and N-methyl pyrrolidone and the product isolated.

DERIVATIVES No additional derivatives were prepared.

NOTES 1. Additional polyphenylenesulfide scale up specifications are provided by this group (1) in an earlier investigation. 2. Other methods for removing impurities from crude polyphenylenesulfide are discussed by Miyahara et al. (2). 3. Geibel devised a novel treatment and recovery method for producing commercially viable high-molecular-weight polyphenylenesulfide using lowmolecular-weight intermediates and by retreating with recycled N-methyl pyrrolidone and paradichlorobenzene.

250

Process for Producing Polyarylene Sulfide

4. Kohler et al. (4) extruder processed polyphenylenesulfide containing the bisazomethine of 4-nitrobenzaldehyde and bis-(4-aminophenyl)methane with 40 wt% glass fibers and the product used molding compositions. References 1. M. Matsuzaki et al., U.S. Patent 7,220,817 (March 22, 2007). 2. M. Miyahara et al., U.S. Patent 7,094,867 (August 22, 2006). 3. J.F. Geibel et al., U.S. Patent 6,201,097 (March 13, 2001). 4. B. Kohler et al., U.S. Patent 5,240,988 (August 31, 1993).

IX. FIBERS A. High Strength a. Aliphatic nylon-1

Title: Metal Carbonate Initiator and Method for Polymerizing Isocyanates Using the Same Author: Assignee:

Jae-Suk Lee et al. Gwangju Institute of Science and Technology (Gwangju, KR)



Polymerization of n-hexylisocyanate using novel anionic polymerization agent. Ongoing investigation of anionic initiators. Fibers An initiator was prepared that forms a cluster upon initiation and protects the stability of the terminal anions at the end of the chain. This results in a controlled polymerization that prevents depolymerizaton and improves reaction time and efficiency without the use of a separate additive. Other initiators including sodium-benzanilide and sodium diphenylmethane have also demonstrated polymerization initiation and regulator properties.


251

252

Metal Carbonate Initiator and Method for Polymerizing Isocyanates Using the Same

REACTION

i. Tetrahydrofuran (THF), sodium benzyl phenyl ketone

EXPERIMENTAL 1. Preparation of poly(n-hexylisocyanate) A polymerization unit containing separate glass ampoules of purified n-hexylisocyanate, the initiator, and a reaction terminator, was connected to a vacuum and then sealed. The reaction conditions were 2988C and 1 1026 torr with a reaction time between 5 and 15 minutes. To set the reaction temperature, liquid nitrogen was added to methanol contained in a constant temperature bath to freeze the methanol and the temperature measured using a low-temperature thermometer. The initiator, sodium-benzyl phenyl ketone, was obtained by reacting sodium metal with an equivalent amount of benzyl phenyl ketone in THF and used immediately. The terminator consisted of hydrochloric acid – methanol mixture solution. Reaction scoping results are provided in Table 1.

SCOPING REACTIONS TABLE 1. Reaction Scoping for Anionic Polymerization of n-Hexylisocyanate Using Sodium-Benzyl Phenyl Ketone as Initiator

Entry 1-1 1-3 1-5 a

Initiator (mmol)

n-Hexylisocyanate (mmol)


Mn (Da)

PDIa

Conversion (%)

0.244 0.271 0.277

5.18 5.45 5.31

5 10 15

8300 8710 8770

1.17 1.09 1.09

89 100 96

PDI ¼ poly dispersity index.

Notes

253

DERIVATIVES The following two polymeric derivatives were also prepared:

NOTES 1. In an earlier investigation by the authors (1), sodium benzanilide was used to anionically polymerize n-hexylisocyanate. 2. Poly(2-vinylpyridine)-b-poly(n-hexylisocyanate), (I), was prepared by the authors (2) by living polymerization using potassium diphenylmethane as initiator and then adding sodium tetraphenylborate to replace the counter cation with a sodium ion. The product was used in optical applications such as an optical switch device.

3. Functionalized poly(n-hexylisocyanate) was prepared by the authors (3) by endcapping with methacryloyl, (s)-(-)acetopropionyl chloride, or suberoyl chloride.

References 1. J.-S. Lee et al., U.S. Patent Application 20040034186 (February 19, 2004). 2. J.-S. Lee et al., U.S. Patent Application 20050215755 (September 29, 2005). 3. J.-S. Lee et al., U.S. Patent Application 20050209426 (September 22, 2005).

b. Nanotube benzobisoxazole copolymers

Title: Copolymerization and Copolymers of Aromatic Polymers with Carbon Nanotubes and Products Made Therefrom Author: Assignee:

Wen-Fang Hwang et al. William Marsh Rice University (Houston, TX)

U.S. Patent Application: Material Patentability: Anticipated Issuing Date:

20070118937 (May 24, 2007) High Mid-2010


Functionalizing nanotubes/fullerenes for use as advanced composites. Ongoing 10-year investigation by the Rice University group. Fibers

Observations:

By virtue of the Halpin –Tsai equation, there is an inherent strength benefit by incorporating nanotubes into aromatic block copolymers. This was demonstrated by the enhanced tensile modulus of poly(styrene-co-nanotube). The anticipated use of polybenzobisoxazole and polyphenylene amide nanotubes as fibers, possibly in ballistic applications. Other directions the Rice University group is heading to are in advanced polymer composites prepared from glasswool, poly(propylene-co-nanotube) synthesis, and condensation products prepared using acid functionalizated nanotubes.

254

Derivatives

255

REACTION

i. Terephthaloyl chloride, polyphosphoric acid, phosphorous pentoxide ii. Polyphosphoric acid, SWNT-dicarboxylate, methanesulfonic acid, polyphosphoric acid, phosphorous pentoxide

EXPERIMENTAL 1. Preparation of p-phenylene benzobisoxazole oligomer A reactor was charged with diaminoresorcinol dihydrochloride (21.01 mmol) and terephthaloyl chloride (19.70 mmol) and then dissolved in polyphosphoric acid (33.1529 g; 84.5% P2O5) and phosphorous pentoxide (0.4331 g; 84.7 wt%). The mixture was dehydrochlorinated for 16 hours at 458C and then oligomerized at 958C for 8 hours, 1508C for 16 hours, and 1908C for 24 hours. The product was isolated having an inherent viscosity of 1.96 dL/g. 2. Preparation of poly( p-phenylene benzobisoxazole-co-nanotube) A polyphosphoric acid (0.2 g) solution of the step 1 product (25 mg) was treated with a suspension of SWNTs (50 mg; 60 nm length), methanesulfonic acid (10 g), polyphosphoric acid (10 g; 84.5% P2O5), and phosphorous pentoxide (0.15 g). This mixture was then reacted for three days at 1008C and the copolymer product isolated.

DERIVATIVES An aromatic polyamide copolymer composites was also prepared as illustrated below:

256

Copolymerization and Copolymers of Aromatic Polymers

POLYMERIZATION SCOPING TABLE 1. Poly( p-phenylene Benzobisoxazole-co-nanotube) Properties Prepared at 10088 C Using a 1:1 Weight Ratio of Methanesulfonic Acid and Polyphosphoric Acid

Entry 1 2 3

Weight Ratio of SWNT/PBOa

Molar Ratio of PBO/SWNT

Product Concentration of PBOc

Product Concentration of SWNTc

67/33 33/67 33/67b

16 64 64

0.12 0.24 0.24

0.24 0.12 0.12

a

Poly( p-phenylene benzobisoxazole). Prepared using benenesulfonic acid functionalized tubes (II). c PBO ¼ bis benzoyl peroxide, SWNT ¼ spherical nanotube. b

NOTES 1. A p-phenylene benzobisoxazole oligomer composite with a repeat unit of 44 was also prepared. 2. Short nanotubes, (I), having a length of 60 nm containing carboxylic acid termini were used in all synthetic procedures. In a previous investigation by this group (1) the acid chloride nanotube was used as the comonomer. These materials were prepared by oxidizing the nanotube with nitric acid and then postreacting with thionyl chloride. Sulfanilic analogs of (II) were also prepared by diazonium incorporation of sulfanilic acid and are described.

3. Tour et al. (2) prepared polystyrene having an Mn of 60,000 Da reinforced with nanotubes and observed that composites displayed an enhancement in their tensile modulus without a large reduction in their strain-at-break properties.

Notes

257

4. Barrera et al. (3) sidewall functionalized carbon nanotubes with organosilanes for polymer composites, (III), with glass fibers for use in advanced cylindrical nanotube (CNT)-polymer composites.

5. Polypropylene was grafted onto a nanotube surface using benzoyl peroxide and is discussed by Khabashesku et al. (4).

References 1. W.-F. Hwang et al., U.S. Patent Application 20050171281 (April 4, 2005). 2. J.M. Tour et al., U.S. Patent Application 20070259994 (November 8, 2007). 3. E.V. Barrera et al., U.S. Patent Application 20070298669 (December 27, 2007). 4. V.N. Khabashesku et al., U.S. Patent Application 20070099792 (May 3, 2007).

X. FUEL CELLS A. Fuel Cell Membranes a. Polytriazole

Title: Production of a Functionalized Polytriazole Polymer Author: Assignee:

Mariela Leticia Ponce et al. Gkss-Forschungszentrum Geesthacht GMBH (Geesthacht, DE)


20080182964 (July 31, 2008) High April, 2010

Single-step synthesis of poly((4-phenylsulfonic acid)-1,2,4-triazole)-cooxadiazole containing at least 85% polytriazole. Although poly(1,2,4-triazole)-co-oxadiazole are unreported in the U.S. patent literature, their application as fuel cells is limited. Fuel cells A method for preparing poly(1,2,4-triazole)-co-oxadiazole containing at least 85% 1,2,4-triazole content and having an Mw of 860,000 Da in a one-pot three-step process is described. The process entails: i. Formation of aromatic hydrazine polyamide ii. In situ formation of amino alcohol using a heteroaromatic primary amine iii. Nucleophilic attack by the amino alcohol intermediate forming the corresponding 1,2,4-triazole or oxadiazole. Only one single pot preparation of a 1,2,4-triazole copolymer is reported in the literature.


259

260

Production of a Functionalized Polytriazole Polymer

REACTION

i. Hydrazinesulfate, polyphosphoric acid, 4-aminobenzenesulfonic acid

EXPERIMENTAL 1. Preparation of poly((4-phenylsulfonic acid)-1,2,4-triazole)-co-oxadiazole A reactor charged with 4,40 -diphenylether-dicarboxylic acid, hydrazinesulfate, and polyphosphoric acid were mixed and reacted for 1 hour at 1608C and then further heated to 1808C. This mixture was then treated with 4-aminobenzenesulfonic acid and heated for an additional 2 hours. The molar solubility ratio of polyphosphoric acid/hydrazinesulfate and the molar monomer ratio of hydrazinesulfate/4,40 -diphenylether-dicarboxylic acid were kept constant at 10 and 1.2, respectively. The mixture was further treated with sufficient 4-aminobenzenesulfonic acid so that the molar ratio of in situ formed polyhydrazide was maintained at 1:1. After heating was stopped, the mixture was poured into warm water containing 5 wt% sodium hydroxide solution and a dark blue fiber obtained. The fiber was washed in distilled water and then dried in a vacuum furnace for 48 hours at 1008C. The dried material had a nitrogen/carbon ratio of 0.174 and a sulfur/carbon ratio of 0.058. The product had an Mw of 560,000 Da with triazole rings comprising 88% of the molecule.


NOTES 1. The mechanism for this reaction is illustrated below. Step 1. Amidation

Notes

261

Step 2. Amino Alcohol Formation

Step 3. Nucleophilic Attack by Oxygen or Nitrogen on Carbonyl Amide

2. Copolymers were subsequently converted into 90-mm-thick membranes using N-methylpyrrolidone and were used as fuel cell components. 3. The single-step synthesis of monomeric 1,2,4-triazole derivatives using N-methylhydrazine is described by Podhorez et al. (1). 4. Composite membranes containing 1,2,4-polytriazoles were previously prepared by Jones et al. (2) and used in fuel cells.

References 1. D.E. Podhorez et al., U.S. Patent 6,096,898 (April 1, 2000). 2. R.S. Jones, Jr. et al., U.S. Patent 4,933,083 (July 12, 1990).

B. Proton Conducting a. Polyamidic acid sulfamic acids

Title: Proton Conductive Electrolyte and Fuel Cell Comprising the Same Author: Assignee:

Hiroko Endo et al. Samsung SDI Co., Ltd. (Suwon-si, KR)


262

20070212585 (September 13, 2007) Very high Mid-2009

Synthesis of sulfamic acid electrolytic polymers for fuel cells requiring high proton conductivity and open circuit voltages. This application provides a method for preparing polyamidic acid sulfamic acids effective as fuel cells unreported in the patent literature. Fuel cells In order to be effective as a solid polymer electrolyte fuel cell, the material must have high proton conductivity, heat resistance, and good mechanical strength. To achieve the high proton conductivity, objective sulfonated or phosphonated substituents are incorporated into the polymer. Sulfonic acid substituents have been introduced using sulfonated comonomers, sultones, or by grafting vinyl sulfonic acid. Although fuel cells containing sulfamic acid have never been prepared, these materials have excellent proton conductivities at 1508C and one of the higher levels of proton conductivities and open-circuit voltages. This application has addressed this synthetic shortcoming by preparing eight sulfamic polymeric agents.

Derivatives

263

REACTION

i. N,N 0 -Dimethylformamide, acetone, hexane, hydrochloric acid, 1,10-diaminodecane ii. Thionyl chloride, dimethylformamide, sulfamic acid, triethylamine EXPERIMENTAL 1. Preparation of polyamidic acid derivative A reactor was charged with 1,10-diaminodecane (20 mmol) dissolved in 170 ml of N,N 0 -dimethylformamide containing pyromellitic anhydride (20 mmol) and the mixture stirred at ambient temperature for 60 hours. It was then precipitated in 4 liters of acetone/hydrochloric acid, 1:4, respectively, and collected. The solid was washed with aqueous hydrochloric acid solution and acetone and then heated and dried in vacuum at 608C for 36 hours and 7.65 g of product isolated as a white powder. H-NMR (d6-DMSO) d 1.20–1.38 (br, ZCH2Z), 1.43– 1.57 (br, ZCH2Z), 3.13– 3.24 (br, ZCH2Z), 7.34, 7.68, 8.08 (s, Ph), 8.39, 8.44 (m, NH) FTIR (cm21) 1719, 1655 (vC¼O ) 1

2. Preparation of polyamidic acid sulfamic acid derivatives The step 1 product (3 mmol) was dissolved in 100 ml of N,N 0 -dimethylformamide and then treated with thionyl chloride (15 mmol) and the mixture stirred at ambient temperature for 6 hours. This mixture was then treated with sulfamic acid (30 mmol) and triethylamine (30 mmol) dissolved in 15 ml of CH2Cl2 and stirred at ambient temperature for 16 hours. The mixture was then concentrated at 508C and stirred at ambient temperature for 1 hour. It was then centrifuged, the solid isolated and dissolved in 100 ml of N,N 0 -dimethylformamide, and then passed through the cation exchange resin AMBERLYSTw 15JWET. Thereafter the solution was concentrated to 10 ml and precipitated in 200 ml of water. The precipitate was heated and dried in vacuum at 708C for 24 hours and 0.68 g product isolated as a light brown powder. H-NMR (d6-DMSO) d 1.20–1.35 (br, ZCH2Z), 1.49– 1.65 (br, ZCH2Z), 3.20– 3.30 (m, ZCH2Z), 3.52– 3.64 (m, ZCH2Z) FTIR (cm21) 1716, 1635 (vC¼O); 1192, 1055 (vC¼s)

1

DERIVATIVES Selected derivatives are provided in Table 1.

264

Proton Conductive Electrolyte and Fuel Cell Comprising the Same

TESTING Proton conductive electrolyte properties of step 2 membranes were determined at 1508C by the impedance measurement using a 13-mm circular-plate-shaped platinum electrode. Testing results are provided in Table 1.

TABLE 1. Proton Conductivity and Open-Circuit Testing Results for Electrolytic Membranes Consisting of Selected Polyamidic Acid Sulfamic Acid Derivatives Conducted at 15088 Ca

A:B

Proton Conductivity (S/cm)

OpenCircuit Voltage (V)

3

2:1

2.2 1023

0.985

4

4:1

2.8 1023

0.978

6

4:1

2.2 1023

0.969

8

4:1

1.7 1023

0.943

13

5:1

8.8 1024

0.844

Entry

a

Polymer A Repeat Unit

Polymer B Repeat Unit

Vinyl sulfamic acid derivatives were used to enhance the thermal stability of membranes.

NOTES 1. In a subsequent investigation by the authors (1) proton-conductive electrolyte membranes consisting of poly(phosphophenylene oxide) derivatives, (I),

Notes

265

were prepared and converted into membranes using polytetrafluoroethylene as a reinforcing agent.

2. Brunell et al. (2) prepared sulfonated poly(polyetherketone-block-polyethersulfone) derivatives, (II), which had high proton conductivity at 808C and were used in fuel cells. Random copolymers,

(III), were prepared by Yamada et al. (3) having Mn’s of 30,000 Da and proton conductivities of 4.64 1021 dimethyl sulfoxide (DMSO).

3. Kiefer et al. (4) prepared proton-conductive electrolytes for use in fuel cells by free radically grafting vinyl-phosphonic acid and vinylsulfonic acid onto a polyether ketone substrate.

References 1. H. Endo et al., U.S. Patent Application 20070259239 (November 8, 2007). 2. D.J. Brunelle et al., U.S. Patent Application 20080004443 (January 3, 2008). 3. T. Yamada et al., U.S. Patent Application 20080004360 (January 3, 2008). 4. J. Kiefer et al., U.S. Patent Application 20070292734 (December 20, 2007).

b. Polyaromatic sulfonic acids

Title: Multiblock Copolymers Containing Hydrophilic and Hydrophobic Segments for Proton Exchange Membrane Author: Assignee:

James E. McGrath et al. University of Virginia (Blacksburg, VA)



266

20070292730 (December 20, 2007) High Late 2009

Development of bipolar polymer electrolytes, which are thermally and hydrolytically stable, flexible, and exhibit low methanol permeability and high proton conductivity. Proton-conducting membranes consisting of aromatic sulfonic acid block copolymers are unreported in the patent literature. Fuel cells The introduction of ionic groups into high-performance polymers has attracted much interest because its potential usefulness as hightemperature-operating ion exchange resins and polymer electrolyte membranes for fuel cells. Although Nafionw perfluoro resins are used as proton exchange membranes at ambient temperature, they display poor conductivity at elevated temperatures. The current application addresses this limitation. By preparing a cyano copolymer that has a proton, with a conductivity of at least 0.10 S/cm at 908C and is thermally stable in air up to 1 hour at about 3008C was prepared. In this application a block copolymer containing florine and sulfonates was prepared that had high activity at elevated temperature.

Experimental

267

REACTION

i. Decafluorobiphenyl, N,N-dimethylacetamide, benzene, potassium carbonate ii. 4,40 -Difluorodiphenylsulfone, potassium carbonate, DMSO, toluene, biphenyl iii. DMSO, benzene EXPERIMENTAL 1. Preparation of poly(decafluorobiphenyl-co-perfluorobisphenol A) A reactor was charged with decafluorobiphenyl (9.0 mmol) and perfluorobisphenol A (8.0 mmol) and then dissolved in 40 ml N,N-dimethylacetamide and 4 ml of benzene and treated with excess K2CO3 (24 mmol). The reaction bath was heated to 1208C over a 2-hour period and kept at that temperature for 4 hours and then the material was precipitated into 200 ml of acidic water/methanol, 1:1. The precipitated polymer was filtered and washed with deionized water and then dried at 808C under vacuum. The product was isolated in quantitative yield as a white solid. 1

H-NMR (CDCl3) d 7.10 (d, 2H), 7.45 (d, 2H) F-NMR (CDCl3) d 264.0 (CF3), 2137.5, 2152.4 (ArZF), 2137.2, 2149.8, 2160.2. (ArZF) 13 C-NMR (CDCl3) d 115.4, 128.8, 132.0, 157.1 (6FZBPA), 118.4, 122.1, 125.8, 129.7 (ZCF3), 103.1, 134.7, 140.1, 143.3, 146.4 Molecular weight [perfluorobisphenol A segment]: Mn of 8.0K, Mw of 15.9K, with a polydispersity of 1.97 19

2. Preparation of poly(biphenyl-co-4,40 -difluorodiphenylsulfone) A 100-ml reactor was charged with biphenol (2.0 mmol), 4,40 -difluorodiphenylsulfone (1.66 mmol), K2CO3 (6 mmol), 7 ml DMSO, and 5 ml toluene as an azeotroping agent and the mixture refluxed 4 hours while the remaining toluene was distilled off at 1608C. Thereafter the reaction mixture remained at this temperature for an additional hour and then cooled and the product isolated.

268

Multiblock Copolymers Containing Hydrophilic and Hydrophobic Segments

3. Preparation of block copolymer A solution of the step 2 product was treated with the step 1 product (0.3 mmol) dissolved in 10 ml DMSO and 5 ml benzene and heated at 908C for 2 hours and at 1118C for 8 hours. The viscosity of the solution increased sufficiently so that an additional 45 ml of DMSO was added to allow for further stirring. The reaction product was then precipitated into 600 ml of water/methanol, 1:1, and then filtered, treated in boiling water for 24 hours, and then treated in boiling tetrahydrofuran (THF) for 4 hours. The product was dried at 808C for 48 hours in a conventional oven and isolated in 75 – 80% yield.

DERIVATIVES Only the single derivative was prepared.

TESTING The results of conductivity testing are provided in Table 1.

TABLE 1. Effect on Conductivity of Step 3 Product Containing Different Sulfonated and Fluorinated Block Sizes Sulfonated Block (Da) 5,000 15,000 5,000

Fluorinated Block (Da)

Water Uptake (%)

Conductivity (Scm21)

2,800 15,000 5,000

470 260 130

0.32 0.16 0.12

NOTES 1. In an early investigation by this group (1) ion-conducting sulfonated polymeric material containing aromatic nitrile substituents, (I), were prepared and used to form membranes for use in fuel cells and in ion exchange technologies. Ether nitrile block copolymers containing sulfonic acid, (II), were prepared by McGrath et al. (1) and were intended for fuel cell applications as protonconducting membrane materials.

Notes

269

2. Polybenzazole block copolymers, (III), prepared by Martin et al. (2) were suitable in solid polymer electrolyte membrane applications as a solid polymer electrolyte doped membranes and in fuel cells derived from them.

3. Block naphthyl polyethers, (IV), were prepared by Masui et al. (3) and found effective as polymer electrolyte for fuel cells. The block copolymer had one segment containing ion exchange groups having an ion exchange group density of at least 4.0 meq/g.

4. Polyphosphazenes block copolymers containing sulfonimide side groups, (V), were prepared by Allcock et al. (4) and used in membrane blends in fuel cells.

270

Multiblock Copolymers Containing Hydrophilic and Hydrophobic Segments

References 1. J.E. McGrath et al., U.S. Patent Application 20060258836 (November 16, 2006). 2. R. Martin et al., U.S. Patent Application 20080003480 (January 3, 2008). 3. K. Masui et al., U.S. Patent Application 20070281195 (December 6, 2007). 4. H.R. Allcock et al., U.S. Patent Application 20070043188 (November 15, 2007).

c. Polyperfluorosulfonic acids

Title: Monomers Comprising Superacidic Groups, and Polymers Therefrom Author: Assignee:

David Roger Moore et al. General Electric Company (Schenectady, NY)



20080114183 (May 15, 2008) High 2010

Preparation of copolymers containing perfluorosulfonate functions useful as superacids. Although perfluorosulfonate polymeric agents effective as superacids have previously been prepared, the synthetic route of the current invention is novel and versatile. Fuel cell membranes Polymer compositions containing superacidic functional groups were prepared in this application by polymerizing bisphenol monomers functionalized with a perfluorosulfonate metal salt of 4,40 -difluorodiphenylsulfone and used as electrolytic membranes in fuel cells. Bisphenol monomers were prepared by coupling 2-(4-bromophenoxy)tetrafluoroethane-sulfonyl-4-tbutylphenyl sulfonate with 3,4-dihydro-2H-pyran-protected biphenol intermediates. While fuel cells have been prepared using mainly Nafionw and/or related perfluorosulfonic acid polymer membranes, which are effective at high humidity, the current agents are effective at relatively low humidity.

271

272

Monomers Comprising Superacidic Groups, and Polymers Therefrom

REACTION

i. ii. iii. iv. v. vi. vii.

4-t-Butylphenol, triethylamine, acetonitrile Sulfuric acid, phenol Pyridinium p-toluenesulfonate, chloroform, 3,4-dihydro-2H-pyran THF, n-butyl lithium, 2-isopropoxy-4-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Tetrakistriphenylphosphine palladium, cesium carbonate, dimethylformamide THF, methanol, hydrochloric acid, potassium hydroxide 4,40 -Difluorodiphenylsulfone, potassium carbonate, DMSO, toluene EXPERIMENTAL

1. Preparation of 4-t-butylphenyl sulfonate A flask charged with 4-tert-butylphenol (57.1 mmol), triethylamine (59.6 mmol), and 25 ml of acetonitrile was then cooled to 2308C and treated with a solution of

Experimental

273

2-(4-bromophenoxy)-tetrafluoroethanesulfonyl fluoride (11.5 mmol) dissolved in 25 ml acetonitrile over 30 minutes. The reaction mixture was warmed to 08C and stirred for 6 hours. The colorless solution was gradually warmed to ambient temperature and stirred an additional 16 hours and then concentrated and treated with 100 ml of water. The mixture was extracted four times with 100 ml diethyl ether and organic layers combined, washed twice with 100 ml 0.05 M NaOH, brine, dried, and concentrated. The product was purified by silica-gel column chromatography using 5% ethyl acetate/hexane as eluent and 24.9 g of a colorless liquid isolated. 1

H-NMR (CDCl3) d 7.54 (2H, d, J ¼ 8.4 Hz, ArH), 7.46 (2H, d, J ¼ 9.2 Hz, ArH), 7.25 (2H, d, J ¼ 9.2 Hz, ArH), 7.14 (2H, d, J ¼ 8.8 Hz, ArH), 1.34 (9H, s, CH3)

2. Preparation of bisphenol A 500-ml round-bottom flask was charged with 4-bromoacetophenone (0.236 mol), phenol (1.471 mol), and 75 ml of 75% H2SO4 at 508C for 2.5 days and then extracted four times with 200 ml with diethyl ether. Combined organic layers were washed twice with 500 ml saturated sodium bicarbonate, dried over MgSO4, and concentrated. The product was isolated using gradient silica-gel column chromatography using 5 – 50% ethyl acetate/hexane and then recrystallized in solution of 400 ml toluene/heptane, 1:4, respectively, at 2208C and 39.9 g of product isolated. 1

H-NMR (CDCl3) d 7.39 (2H, d, J ¼ 8.8 Hz, BrZArH), 6.98 (2H, d, J ¼ 8.4 Hz, BrZArH), 6.95 (4H, d, J ¼ 8.8 Hz, OHZArH), 6.75 (4H, d, J ¼ 8.8 Hz, OHZArH), 4.78 (2H, s, OH), 2.11 (3H, s, CH3)

3. Preparation of protected bisphenol The step 2 product (14.9 mmol) and pyridinium p-toluenesulfonate (0.477 mmol) were treated in 150 ml chloroform with 3,4-dihydro-2H-pyran (110 mmol) and the protected isolated. 1

H-NMR (CDCl3) d 7.38 (2H, d, J ¼ 8.8 Hz, BrZArH), 6.97 (10H, m, ArH), 5.41 (2H, t, J ¼ 3.2 Hz, CH), 3.95 (2H, m, CHO), 3.62 (2H, m, CHO), 2.11 (3H, s, CH3), 1.5– 2.1 (12H, bm, CH2)

4. Preparation of boronate ester The step 3 product (52.3 mmol) was dissolved in 200 ml THF and then cooled to 2788C and treated with 22.0 ml of 2.5 M in hexane n-butyl lithium. The mixture was slowly warmed to 2308C and stirred for 15 minutes and then recooled to 2788C and treated with 2-isopropoxy-4-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (61.3 mmol). The solution was warmed to ambient temperature and stirred overnight after which a white precipitate formed. The mixture was then treated with 300 ml apiece of CH2Cl2 and water and the organic layer collected. The aqueous layer was washed three times with 100 ml CH2Cl2 and the combined organic layers washed twice with 150 ml brine, dried over MgSO4, filtered, and concentrated. The crude white solid was triturated with cold methanol, filtered, washed with cold methanol, and 26.2 g product isolated.

274 1


H-NMR (CDCl3) d 7.72 (2H, d, J ¼ 8.4 Hz, BrZArH), 7.14 (2H, d, J ¼ 8.4 Hz, BrZArH), 7.00 (4H, d, J ¼ 8.8 Hz, OZArH), 6.94 (4H, d, J ¼ 8.8 Hz, OZArH), 5.40 (2H, t, J ¼ 3.2 Hz, CH), 3.95 (2H, m, CHaHbO), 3.61 (2H, m, CHaHbO), 2.14 (3H, s, CH3), 1.6–2.1 (12H, bm, CH2), 1.35 (12H, s, CH3) (J ¼ 8.8 Hz, ArH), 1.34 (9H, s, CH3)

5. Preparation of protected monomer A flask was charged with the step 4 product (17.9 mmol), the step 1 product (14.5 mmol), Pd(PPh3)4 (0.072 mmol), and Cs2CO3 (29.9 mmol) and then treated with 50 ml of dimethylformamide and heated to 808C for 24 hours. It was then cooled to ambient temperature and treated with 400 ml apiece water and CH2Cl2 and then filtered through Celite. The aqueous phase was extracted five times with 100 ml CH2Cl2, combined, washed twice with 300 ml of brine, dried, concentrated to a light yellow oil, and 50 ml of 10% ethyl acetate/hexanes and 100 methanol added to solubilize the oil. White crystals started forming within 30 minutes and the flask was placed in a freezer at 2208C overnight and 9.45 g of product isolated. 1

H-NMR (CDCl3) d 7.61 (2H, d, J ¼ 8.8 Hz, ArH), 7.46 (4H, m, ArH), 7.29 (4H, m, ArH), 7.20 (2H, d, J ¼ 8.0 Hz, ArH), 7.05 (4H, d, J ¼ 9.2 Hz, ArH), 6.97 (4H, d, J ¼ 8.8 Hz, ArH), 5.42 (2H, t, J ¼ 3.2 Hz, CH), 3.96 (2H, m, CHaHbO), 3.62 (2H, m, CHaHbO), 2.18 (3H, s, CH3), 1.6–2.1 (12H, bm, CH2), 1.35 (9H, s, CH3)

6. Preparation of monomer, potassium salt The step 5 product (9.33 mmol) was dissolved in 80 ml THF and 20 ml methanol and treated with concentrated hydrochloric acid (25 drops) and stirred at ambient temperature for 2 hours. Potassium hydroxide (334 mmol) dissolved in 100 ml water was added to the solution, which was stirred vigorously at 808C for 5 hours. The basic solution was neutralized with hydrochloric acid to pH 8 and the solution concentrated to a brown oil. The oil was treated with 100 apiece of ethyl acetate and brine and the organic layer collected. The brine layer was washed twice with 100 ml ethyl acetate. Combined organic layers were washed once with 100 ml brine, dried over MgSO4, and a white solid isolated after the mixture was concentrated. The solid was triturated with hot CHCl3 for 5 minutes, filtered, washed with additional hot CHCl3, dried under vacuum overnight at 808C, and the product isolated. 1

H-NMR (d6-DMSO) d 9.28 (2H, s, OH), 7.73 (2H, d, J ¼ 8.8 Hz, ArH), 7.58 (2H, d, J ¼ 8.4 Hz, ArH), 7.29 (2H, d, J ¼ 8.4 Hz, ArH), 7.11 (2H, d, J ¼ 8.4 Hz, ArH), 6.85 (4H, d, J ¼ 8.4 Hz, ArH), 6.67 (4H, d, J ¼ 8.4 Hz, ArH), 2.05 (3H, s, CH3)

7. Preparation of polyethersulfone The step 6 product (3.80 mmol), 4,40 -difluorodiphenylsulfone (3.58 mmol), and K2CO3 (14.6 mmol) were added to the reaction flask and treated with 10 ml DMSO and 5 ml toluene and then stirred at 1508C for 6 hours with azeotropic water removal. The mixture was treated with additional step 6 product (1.84 mmol)

Notes

275

and 4,40 -difluorodiphenylsulfone (2.063 mmol) with 5 ml and 2 ml toluene added and stirred a further 4.75 hours at 1508C. Gas-phase chromatography (GPC) determined that the weight-average and number-average molecular weights of the polymer were 125,000 and 30,700 Da, respectively. The polymer was precipitated into 400 ml vigorously stirred isopropanol, filtered, washed with methanol and water, and dried in vacuo at 1008C overnight.

DERIVATIVES (BISPHENYL)

NOTES 1. Additional superacid monomers, (I), were prepared by the authors (1) in an earlier investigation.

2. 2,5-Di(pyridine-3-yl)benzene-1,4-diol, (II), was prepared by Geormezi et al. (2) and used to prepare polyether sulfones, (III), useful as electrolytes in high-temperature fuel cells.

276


3. Sasaki et al. (3) prepared superacid sulfonic acid polysulfone block copolymers, (IV), which were effective as components in fuel cells.

4. Superacid sulfonic acid fluoropolymers, (V), were prepared by Luzinay et al. (4) and used as membranes in fuel cell applications.

References 1. D.R. Moore et al., U.S. Patent Application 20080114149 (March 15, 2008). 2. M. Geormezi et al., U.S. Patent Application 20080113227 (May 15, 2008). 3. S. Sasaki et al., U.S. Patent Application 20070148518 (June 28, 2007). 4. P. Luzinay et al., U.S. Patent Application 20080051479 (February 28, 2008).

d. Polyperfluorosulfonic acids

Title: Polyarylene, Process for Producing the Same, Solid Polyelectrolyte, and Proton-Conductive Film Author: Assignee:

Yoshitaka Yamakawa et al. JSR Corporation (Tokyo, JP)


Observations:


An ongoing 7-year investigation in the development of cation exchange resins. Similar perfluoropolyether derivatives have been reported in the patent literature. Solid polyelectrolyte Proton-conductive film Polyether resins designed to mimic Nafionw fluorocarbon resins were having an excess amount of sulfonic acids present in the polymer. These materials were prepared in three steps and in high yields. These highly sulfonic acid functionalized polymers have optimized solid polyelectrolyte and a proton-conductive film properties. The synthetic method for preparing resins having high sulfonic acid was through the electrophilic introduction of propane sulfone.

277

278

Polyarylene, Process for Producing the Same, Solid Polyelectrolyte

REACTION

i. 2H-Dihydropyrane, toluene, Amberlistw 15 ii. Poly(4,40 -dichlorobenzophenone-2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(triphenylphosphine) nickel dichloride, sodium iodide, triphenylphosphine, zinc, N,N-dimethylacetamide iii. N,N-Dimethylacetamide, lithium hydride, propanesultone EXPERIMENTAL 1. Preparation of 2,5-dichloro-20 ,40 -di(tetrahydro-2-pyranyloxy)benzophenone A reaction flask was charged with 2,5-dichloro-20 ,40 -dihydroxybenzophenone (100 mmol), 2H-dihydropyrane (2400 mmol), and 100 ml of toluene. While the mixture was stirring, it was treated with cation exchange resin Amberlistw 15 (3.0 g) and then stirred an additional 5 hours at ambient temperature. At this point the cation exchange resin was removed and the filtrate washed with aqueous solutions of sodium hydroxide and brine The mixture was dried using MgSO4, concentrated, the residue recrystallized from toluene, and 21.2 g of product isolated.

Derivatives

279

2. Preparation of poly(aryl ether) containing of 2,5-dichloro-20 ,40 -di(tetrahydro-2-pyranyloxy)benzophenone A 500-ml reaction flask was charged with the step 1 product (43.1 mmol), the polycondensate of 4,40 -dichlorobenzophenone-2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (Mn 11,200 Da; 1.80 mmol), bis(triphenylphosphine) nickel dichloride (1.35 mmol), sodium iodide (5.85 mmol), triphenylphosphine (18 mmol), and zinc (108 mmol). The mixture was dried under vacuum and then treated with 87 ml of N,Ndimethylacetamide and kept in the temperature range of 70– 908C. After 3 hours the mixture was diluted with 200 ml of N,N-dimethylacetamide and insoluble components removed by filtration. The filtrate was then added to 1.5 liters of methanol containing 10 vol% concentrated hydrochloric acid to precipitate the polymer. After collecting, the precipitate was dried to obtain 28.5 g of product having polyhydroxyl groups. 3. Preparation of poly(aryl ether) containing sulfonic acid group The step 2 product (29.1 g) was dissolved in 500 ml of N,N-dimethylacetamide by heating the mixture to 1008C and then treated with lithium hydride (258 mmol) followed by 2 hours of stirring. This solution was then treated with propane sultone (258 mmol) and then stirred for 8 hours. The insoluble components in the reaction mixture were collected by filtration and the solution added to 1 M hydrochloric acid to cause the polymer to precipitate. The precipitated polymer was washed with 1 M hydrochloric acid and distilled water until the pH became neutral. The polymer was dried at 758C and 38.2 g of product isolated as a powder. DERIVATIVES

280

Polyarylene, Process for Producing the Same, Solid Polyelectrolyte

NOTES 1 1. The preparation of the step 3 poly(aryl ether) is illustrated in Eq. (1).

(1)

2. Analogs of the step 3 product were prepared by Rozhanskii et al. (1) and used in solid electrolytes and proton-conductive membranes.

3. In earlier investigations by the authors (2,3) solid sulfonic acid resins containing polyarylether and cyano substituents, (II) and (III), respectively, were prepared and used as proton-conductive membranes, electrode electrolytes, electrode paste, and in membrane electrode assemblies.

References 1. I. Rozhanskii et al., U.S. Patent 7,163,988 (January 16, 2007). 2. Y. Yamakawa et al., U.S. Patent Application 20060216566 (September 26, 2006). 3. Y. Yamakawa et al., U.S. Patent 7,115,699 (October 3, 2006).

XI. IMPROVED SYNTHETIC METHODS A. Isocyanates a. Uretonimines

Title: Method of Producing a Uretonimine-Modified Isocyanate Composition Author: Assignee:

Thomas Savino et al. BASF Corporation (Ludwigshafen, DE)



20080085987 (April 10, 2008) Moderate 2011

Synthesis of oligomeric uretonimine-modified polyisocyanates. Although oligomeric dicarbodiimide and uretonimine-modified polyisocyanate have been reported in the literature, the use of 3-methyl1-phenyl-3-phospholene-1-oxide as catalyst is novel. Isocyanates with improved low-temperature tolerance 4,40 -Diphenylmethane diisocyanate is known to have a limited shelf life because of the formation of diphenylmethane uretdione.

Over time, uretdione continues to form in 4,40 -diphenylmethane diisocyanate until it precipitates from melted 4,40 -diphenylmethane diisocyanate. For example, pure 4,40 -diphenylmethane diisocyanate compositions


281

282

Method of Producing a Uretonimine-Modified Isocyanate Composition

maintained at 438C for 14 days had uretdione concentrations exceeding 0.45%, resulting in the precipitation of uretdione from solution as insoluble white solids. The formation of high concentrations of uretdione renders 4,40 -diphenylmethane diisocyanate nonusable in many polyurethane applications. To address this concern uretonimine-modified isocyanates with improved low-temperature properties were prepared using 4,40 diphenylmethane diisocyanate catalyzed with 3-methyl-1-phenyl-3phospholene-1-oxide. The formation of uretonimine was consistently higher than uretdione formation using this catalyst. The uretoniminemodified isocyanate can be stored at temperatures substantially lower than ambient temperature while still remaining liquid. In addition it is soluble in melted 4,40 -diphenylmethane diisocyanate.

REACTION

i. 4,40 -Diphenylmethane diisocyanate, 2,40 -diphenylmethane diisocyanate, 3-methyl1-phenyl-3-phospholene-1-oxide EXPERIMENTAL 1. Preparation of uretonimine-modified isocyanate compositions: Generic procedure A reactor was charged with 93.80% 4,40 -diphenylmethane diisocyanate, 6.20% 2,40 -diphenylmethane diisocyanate, and 3-methyl-1-phenyl-3-phospholene-1-oxide (6 ppm) as catalyst and then heated for 6 hours at 1108C. Trifluoromethanesulfonic acid (50 ppm) was then added to quench the reaction. The mixture was then cooled to 508C and the product isolated having a 29.5% isocyanate content.

283

Testing

DERIVATIVES A second oligomeric derivative was also prepared as illustrated below.

SCOPING REACTIONS The results of reaction scoping studies are provided in Table 1. TABLE 1. Scoping Reactions for Preparation of Uretonimine-Modified Isocyanate Using 93.80% 4,40 -Diphenylmethane Diisocyanate Containing 6.20% 2,40 -Diphenylmethane Diisocyanate Conducted at 105–10888 C Using 3-Methyl-1-phenyl-3-phospholene-1-oxide as Catalyst Experimental Variable 3-Methyl-1-phenyl-3phospholene 1-oxide (ppm) Reaction time (h) Final Percent Isocyanate Stability (days) at 58C

Experiment 2

Experiment 3

Experiment 4

Experiment 5

5.1

5.1

6.0

6.0

4.2 29.4 6

5.3 29.7 2

2.3 29.3 5

2.4 29.3 6

TESTING Selected experimental agents were subjected to an accelerated low-temperature stability test to determine the sensitivity of each sample to form solids. Samples that

284

Method of Producing a Uretonimine-Modified Isocyanate Composition

survived the longest number of solids-free days at 58C exhibited the best low-temperature stability. Testing results are provided in Table 1.

NOTES 1. Additional uretonimine-modified isocyanates were prepared by the authors (1) in an earlier investigation and are discussed. Uretonimine-modified isocyanates were also prepared by Richter et al. (2) using cyclopentyldimethylphosphine as the reaction catalyst. 2. Hannig et al. (3) prepared carbodiimide- and uretonimine-modified polyisocyanates using microwave radiation. These oligomeric isocyanates were subsequently used to prepare polyurethane articles. 3. Rosthauser et al. (4) used 1-methyl-3-phospholene-1-oxide to prepare and isolate oligomeric diisocyanates containing dicarbodiimides using 4,40 -diphenylmethane diisocyanate. Diisocyanates containing dicarbodiimides were also prepared by Takahashi et al. (5) using 3-methyl-1-phenyl-2-phospholene-1oxide as the reaction catalyst. References 1. T. Savino et al., U.S. Patent Application 20080021176 (January 24, 2008), U.S. Patent Application 20070213496 (September 13, 2007), and U.S. Patent Application 20070213432 (September 13, 2007). 2. F. Richter et al., U.S. Patent 7,067,654 (June 27, 2006). 3. F. Hannig et al., U.S. Patent Application 20070135608 (June 14, 2007). 4. J.W. Rosthauser et al., U.S. Patent 7,030,274 (April 18, 2006). 5. I. Takahashi et al., U.S. Patent 6,866,934 (March 15, 2005).

B. Organometallic Catalysts a. Epoxidation reactions

Title: Direct Epoxidation Process Using a Mixed Catalyst System Author: Assignee:

Mark P. Kaminsky et al. Lyondell Chemical Company (Newtown Square, PA)


20080015372 (January 17, 2008) Very high Late 2009

Epoxidation of propylene using palladium/titanium zeolite-1 as catalyst. This propene epoxidation method occurs in a neutral medium and is unreported in the patent literature. Chemical intermediate A unique method for preparing propylene oxide using unprotected organic reagents. Extensions of this method include the selective epoxidation of terminal double bonds in the presence of internal double bonds.

REACTIONS

i. Palladium/titanium zeolite-1 catalyst, hydrogen, methanol, phosphate, oxygen, propylene ii. Oxygen, ammonium phosphate, hydrogen, propylene, methane

ammonium

285

286

Direct Epoxidation Process Using a Mixed Catalyst System

EXPERIMENTAL 1. Preparation of palladium/titanium zeolite-1 catalyst Spray-dried titanium zeolite-1 (15.778 pounds, 20 wt% silica binder, 2.1 wt% Ti, calcined at 5508C was added to 17.89 liters of deionized water in a 50-liter mixing tank and stirred at 500 rpm. The pH of the slurry was adjusted to 7.0 using 3% ammonium hydroxide and then treated with aqueous tetraamine palladium nitrate (0.166 lb Pd diluted to 1 liter) over 1-minute period through a subsurface injector. The pH of the slurry was maintained at 7.0 during the palladium addition by adding additional 3% ammonium hydroxide solution. After the palladium addition the pH was adjusted to 7.5 with ammonium hydroxide and the slurry agitated at 308C for 60 minutes maintained at pH at 7.4. The slurry was then filtered and washed three times with 17 liters of water. The solids were then dried in vacuum at 508C, calcined at 3008C in air for 1 hour and then treated with 4% hydrogen in nitrogen for 1 hour. The solids were then recalcined in air in a muffle furnace at 4008C for 8 hours and at 20 – 1108C for 4 hours. The ramp temperature was further increased to 4008C and held there for 8 hours. The solid was recooled to ambient temperature and then held from 110 to 4008C for 8 hours in a quartz tube vertically mounted in an electric tube furnace with 5% hydrogen in nitrogen and then recooled under hydrogen/ nitrogen and the product isolated. 2. Preparation of propylene oxide and propylene glycol A reactor was charged with the step 1 product (100 g) and 13 g of 0.1 M aqueous ammonium phosphate and then charged with 300 psig of 2% hydrogen, 4% oxygen, 5% propylene, 0.5% methane, and the balance nitrogen. The pressure of the reactor was maintained at 300 psig with the feed gases passed continuously through the reactor at 1600 m/min. In order to maintain a constant solvent level in the reactor during the run, the oxygen, and nitrogen and propylene feeds were passed through a 2-liter stainless steel vessel preceding the reactor containing 1.5 liters of methanol. The reactor was stirred at 1500 rpm at 608C and the products monitored by offline gas chromatography. A summary of scoping reactions is provided in Table 1.

TABLE 1. Reaction Scoping Using the Palladium/Titanium Zeolite Catalyst in the Epoxidation/Glycolization of Propylene

Entry 4a 4b 4c 4d

Catalyst Productivity

Propylene Oxide/ Polyethylene Glycol Selectivity (%)

Propylene Selectivity (%)

0.38 0.33 0.34 0.4

91 92 91 90

73 78 84 88

Notes

287

NOTES 1. In an earlier investigation by Le-Khac et al. (1) propylene epoxidation were prepared using the cation resin Amberlyst 36 and Pd(NH3)4Cl2. 2. The evaluation and performance of similar propylene epoxidation catalysts using oxygen and hydrogen was performed by Kaminsky et al. (2) and is described. 3. A method of rejuvenating epoxidation catalysts is described by Grey et al. (3). References 1. Bi Le-Khac et al., U.S. Patent Application 20070093668 (April 26, 2007). 2. M.P. Kaminsky et al., U.S. Patent Application 334455666 (March 4, 2006). 3. R.A. Grey et al., U.S. Patent 7,256,149 (August 14, 2007).

b. Ethylene oligomerization

Title: Aluminum Phosphate-Supported Group VI Metal Amide Catalysts for Oligomerization of Ethylene Author: Assignee:

John R. Briggs el al. Union Carbide Chemicals and Plastic Technology (Midland, MI)


Observations:

288

20070161503 (January 12, 2007) High Late 2009

Method for oligomerizing ethylene using alkylaluminum and trialkylaluminum as activators. Unique method for forming trimer and tetramer ethylene oligomers. Additives Alcohols This application addresses the need for a process that operates at mild temperatures and pressures to produce trimers (1-hexene) and tetramers (1-octene) while minimizing the formation of less valuable butene, C10-30 a-olefins, and low-molecular-weight polymers. Oligomeric products of the current application are particularly useful as industrial chemicals for preparing alcohols, high-molecular-weight plastics, and linear low-density polyethylene.

Experimental

289

REACTION

i. Ethylene, aluminum catalyst AlPO-1, heptane, chromium(III) tris(bis(trimethylsilyl)amide), nonane, chromium(III) tris(bis(trimethylsilyl)amide) ii. Ethylene, aluminum catalyst AlPO-1, heptane, chromium(III) tris(bis(trimethylsilyl)amide), nonane, chromium(III) tris(bis(trimethylsilyl)amide), chromium(III) tris(bis(trimethylsilyl)amide

EXPERIMENTAL 1. Preparation of oligomeric ethylene using Activator 1 An automated pressure reactor comprising eight pressure cells each with a 6-ml volume were used to oligomerize ethylene. Each of the eight glass inserts was charged with 100 mg of the supported aluminum calalyst AlPO-1 having a particle size between 63 and 125 mm and placed in a 2008C oven overnight. The tubes were then inserted into pressure cells in the reactor located in a dry box. Each tube was treated sequentially treated with 4.9 ml heptane, 0.8 ml of a 0.01 M heptane solution of chromium(III) tris(bis(trimethylsilyl)amide), and 40 mg nonane as an internal standard. These mixtures were then heated to 408C with stirring for 30 minutes. In all cases, the supernatant was a pale green color indicating incomplete deposition of the chromium compound. Each tube was then treated with 0.48 ml of 0.05 M solution chromium(III) tris(bis(trimethylsilyl)amide) in heptane (24 mmol) and then heated to 708C before pressurizing with ethylene. Thereafter, the reactors were vented and the liquid analyzed by gas chromatography/mass spectroscopy (GC/MS). Solids were dried and weighed and ethylene oligomers isolated having molecular weights between 200 and 550 Da. 2. Preparation of oligomeric ethylene using Activator 2 The reaction conditions of example 1 were repeated using a different hydrocarbyl aluminum activator in a 4:1 molar ratio to chromium(III) tris(bis(trimethylsilyl)amide). Reactions were conducted at an ethylene pressure of 100 psi at 708C for 60 minutes. Neither 1-butene nor 1-decene was detected in the product mixture. A summary of reaction scooping is provided in Table 1.

290

Aluminum Phosphate-Supported Group VI Metal Amide Catalysts for Oligomerization

REACTION SCOPING TABLE 1.

Entry

Reaction Scoping for Oligomerizing Ethylene Using Different Activators

Activator

Total 1-Hexane (mg)

Total 1-Octene (mg)

Total Polyethylene (mg)

Polymer (%)

1-Octene 1-Octane þ Hexene (mg)

TMAa TiBAb 385 375

507 481 186 163

227 235 732 714

607 839 56 57

45 54 56 57

0.31 0.33 0.32 0.30

2 3 TEAc MMMOd a

Trimethylaluminums. Triisobutylaluminum. c Triethylaluminum. d Methylalumoxane. b

NOTES 1. Poly(ester-amide) elastomers were prepared by Pacetti et al. (1) and used with implantable medical devices. 2. Thermoplastic elastomers were prepared by Kim et al. (2) and used in decorative sheets. 3. Waddell et al. (3) prepared elastomeric compositions effective as air barriers from novel C4 to C7 isoolefin oligomers and were free of long-chain branching. References 1. S.D. Pacetti et al., U.S. Patent Application 20080014236 (January 17, 2008). 2. J.-W. Kim et al., U.S. Patent Application 2007455666 (November 12, 2007). 3. W.H. Waddell et al., U.S. Patent Application 2007455351 (November 5, 2007).

c. Ethylene polymerization

Title: Catalyst for Ethylene Polymerization, Preparation Thereof, and Method for Controlling the Polymerization Kinetic Behavior of Said Catalyst Author: Assignee:

Mingwei Xiao et al. China Petroleum and Chemical Corporation (Beijing, CN)



Development of Ziegler –Natta polymerization catalysts containing magnesium and titanium for polymerizing ethylene. Although this is an ongoing investigation, composition ratios of magnesium/titanium and magnesium/aluminum are unique. Polymerization catalyst While Ziegler– Natta catalysts are composed of a transition metal and a Groups I –III metal, it is the unique ratio of magnesium and titanium that defines the catalyst efficacy. In earlier studies Ziegler –Natta catalysts containing varying titanium/magnesium ratios were prepared and then used to polymerize ethylene. This application has determined that three different types of ethylene polymerization kinetic curves can be obtained by (a) adjusting the temperature for thermally activating the silica support or by (b) varying the ratio of titanium to magnesium in the main catalyst component. Kinetic curves include: (1) the slowly rising and slowly falling type, (2) the quickly rising and damping type, and (3) the quickly rising and stable type.

291

292

Catalyst for Ethylene Polymerization

REACTION

i. (C4H9)2Mg0.21Et3Al, triethylaluminum chloride, titanium tetrachloride, hydrogen, n-hexane

EXPERIMENTAL 1. Preparation catalyst Step 1 Magnesium powder (6.12 g) and 250 ml of heptane were charged into a reaction flask and then refluxed and treated with iodine (0.05 g) and 1.0 ml of n-butyl chloride. After refluxing for 1 hour n-butyl chloride (19.5 g) was added dropwise over 3 hours and the mixture further heated for 2 hours. This mixture was then treated with 2.1 ml triethylaluminum and maintained at this temperature for 2 hours and then cooled to 508C and filtered. The filter cake was washed with fresh heptane several times and the filtrate concentrated to give a heptane solution of (C4H9)2Mg0.21Et3Al and the catalyst isolated. Step 2 In a 250-ml reaction flask thermally activated silica (7.67 g) was slurried in 40 ml of hexane and then treated with 9 ml of the step 1 product and the temperature maintained at 358C for 3 hours and the product isolated. Step 3 The step 2 product was treated with a 50 wt% solution of 2-ethylhexanol (4.68 g) dissolved in hexane over 15 minutes and the temperature maintained at 408C for 4 hours and the product isolated. Step 4 Step 3 was treated with 0.24 ml of diethylaluminum chloride and n-butyl chloride (3.4 g) and the reaction maintained at 408C for 6 hours. This mixture was then treated with titanium tetrachloride (1.05 g; Ti/Mg ratio ¼ 0.59) and the mixture warmed to 508C for 3 hours and the product isolated. Step 5 The step 4 product was concentrated at 708C and the solid catalyst isolated. The weight percent composition of the solid catalyst component was: Mg, 1.82%; Ti, 2.10%; Al, 3.38%; Cl, 11.76%.

293

Notes

2. Polymerization of ethylene A reactor was charged with 1000 ml hexane and a specified amount of the step 5 catalyst and triethylaluminum so that the Al/Ti ratio was at 200. The reaction temperature was raised to 758C and a sufficient amount of hydrogen gas necessary to provide a molar ratio of hydrogen/ethylene of 0.2/0.8 for the low-hydrogen level condition and 0.7/0.3 for the high-hydrogen level added so that a total pressure of 1.0 MPa was obtained. The temperature was further elevated to 858C and maintained at this temperature for 2 hours. At the end of polymerization the ethylene feed was stopped and the reactor quickly cooled, vented, and polyethylene powder isolated from hexane. Polymerization scoping reactions studies are provided in Table 1.

SCOPING STUDIES Polymerization scoping reactions at low- and high-hydrogen levels are provided in Tables 1 and 2, respectively. TABLE 1. Ethylene Polymerization Scoping Reactions Using the Step 5 Catalyst with Hydrogen/Ethylene Molar Ratio of 0.2/0.8 Entry 1 2 3 4 5

Ti/Mg Ratio

Catalyst Efficiency (g PE/g catalyst)

Polymer Bulk Density (g/cm3)

Melt Index (g/10 min)

0.59 0.70 0.27 0.35 0.38

5889 5410 6045 5739 5276

0.395 0.387 0.369 0.371 0.372

1.52 1.17 2.11 1.74 1.37

TABLE 2. Ethylene Polymerization Scoping Reactions Using the Step 5 Catalyst with a Molar Ratio of Hydrogen/Ethylene of 0.7/0.3 Entry 1 2 3 4 5

Ti/Mg Ratio

Catalyst Efficiency (g PE/g catalyst)

Polymer Bulk Density (g/cm3)

Melt Index (g/10 min)

0.59 0.70 0.27 0.35 0.38

2716 2618 2573 2629 2412

0.332 0.342 0.320 0.331 0.316

176.3 169.4 180.4 185.6 169.4

NOTES 1. In an earlier investigation by the authors (1) ethylene polymerization catalysts were prepared consisting of (C4H9MgCl)0.3 (MgCl2), 2-ethylhexanol, ethyl aluminum chloride, and titanium tetrachloride.

294

Catalyst for Ethylene Polymerization

2. A catalyst composition consisting of magnesium chloride, 1-butanol, titanium tetrachloride, and diisobutylphthalate was prepared by Yang et al. (2) and used in the polymerization of a-olefins. 3. An ethylene copolymerization catalyst was prepared by Baita et al. (3) consisting of magnesium chloride/ethyl alcohol adduct, triethyl aluminum, and titanium tetrachloride. 4. Methods for identifying additional Ziegler – Natta co-catalysts in a catalyst system containing procatalysts magnesium and titanium are described by Campbell et al. (4). References 1. M. Xiao et al., U.S. Patent Application 20070213482 (September 13, 2007) and U.S. Patent 7,300,902 (November 27, 2007). 2. C.-B. Yang et al., U.S. Patent Application 20070298964 (December 27, 2007). 3. P. Baita et al., U.S. Patent Application 20070282083 (December 6, 2007). 4. R.E. Campbell, Jr., et al., U.S. Patent Application 20070276102 (November 29, 2007).

d. Ethylene polymerization

Title: Polyethylene and Catalyst Composition for Its Preparation Author: Assignee:

Shahram Mihan Basell, Inc. (Elkton, MD)


20070213205 (September 13, 2007) High Late 2009

Synthesis of high-activity Ziegler –Natta chromium polymerization catalysts. An unusually high-activity ethylene catalyst unreported in the literature. Industrial polymers This current application represents at least a 7-year investigation for preparing ultrareactive Ziegler –Natta ethylene polymerization catalysts. In this process, silicon, indene, and iron, containing bridged zirconium and chromium Ziegler –Natta catalysts were prepared with activities exceeding 1800 g/g of catalyst. Polymerizations in the current application were limited to preparing polyethylene and poly(ethylene-co-1-hexene).

295

296

Polyethylene and Catalyst Composition for Its Preparation

REACTION

i. Water, hydrochloric acid, tetrahydrofuran (THF), ammonium hydroxide ii. Potassium hydride, chromium tris(THF), THF EXPERIMENTAL 1. Preparation of 2-methyl-3-phenyl-1-(8-quinolyl)cyclopentadiene A mixture consisting of 5 ml of water and 5 ml of 12 M hydrochloric acid was added to a solution of 3-hydroxy-2-methyl-3-phenyl-1-(8-quinolyl)cyclopentene (5.7 mmol) dissolved in 100 ml of THF. The mixture was stirred at ambient temperature for 90 minutes and ammonium hydroxide added until the pH was 12. The aqueous phase was then extracted twice with diethyl ether. The organic phases were combined, dried over MgSO4, filtered, and concentrated. The residue was distilled at 157 – 1708C @ 2 1022 mbar and 1.12 g product isolated. 1

H-NMR (CDCl3) d 1.2 (3H, d, Me); 2.01 (3H, m, Me); 2.10 (3H, m, Me); 3.65 (2H, m, CH2); 3.9 (2H, m, CH2); 4.78 (1H, s, CHMe); 6.58 (1H, m, CpH); 6.64 (1H, m, CpH); 7.01 (1H, m, CpH); 7.03 (1H, m, CpH); 7.23 –7.87 (27H, m, CHquinolylþphenyl ); 8.13–8.22 (3H, m, H4); 8.97– 9.05 (3H, m, H2)

2. Preparation of (2-methyl-3-phenyl-1-(8-quinolyl)cyclopentadienyl) chromium dichloride A solution of the step 1 product (3.85 mmol) dissolved in 40 ml of THF was added to a suspension of potassium hydride (3.85 mmol) in 20 ml of THF and then stirred at ambient temperature for 6 hours. This was then added to a solution of chromium trichloride tris(THF) (3.85 mmol) dissolved in 50 ml of THF. The mixture was stirred at ambient temperature for 12 hours, concentrated, and the residue washed three times with hexane and three times with toluene. The soluble components were dissolved in CH2Cl2 and the solution filtered. The filtrate was concentrated, dried under reduced pressure, and 0.969 g of the catalyst isolated. 1

H-NMR (CDCl3) d 253.3 (1H, H4); 216.5 (1H, H5 – 7); 11.2 (3H, Me); 14.8 (1H, H5); 49.4 (1H, H3)

297

Notes

3. Polymerizations were carried out in a fluidized-bed reactor having a diameter of 0.5 m A summary of catalysis are provided in Table 1 while polymer properties are provided in Table 2. TABLE 1. Catalyst Compositions Used in Polymerization of Ethylene and 1-Hexene Described in Table 2 Catalyst 8 9 (1st) 9 (2nd) 10

11

Catalyst Name 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(II)dichloride and bis(n-butylcyclopentadienyl)hafnium dichloride 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(II)dichloride 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(II)dichloride and [1-(8-quinolyl)indenyl]chromium(III) dichloride 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(II)dichloride and mmol of (2-methyl-3-(4-benzotrifluoride)-1-(8-quinolyl)cyclopentadienyl)chromium dichloride 2,6-Bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(II)dichloride and (2-methyl-3-(4-benzotrifluoride)-1-(8-quinolyl)cyclopentadienyl)chromium dichloride

TABLE 2. Properties of Polyethylene Containing 1-Hexene Prepared Using High-Activity Ziegler –Natta Catalysts Catalyst

Output (g/h)

Reaction Temp. (8C)

Prod (g/g of cat)

Ethene (% by volume)

Hexene (% by volume)

H2 (vol%)

8 9 (1st) 9 (2nd) 10 11

3.5 3 2.7 3.4 3.1

94 94.4 94 94 93.9

1807 639 504 798 623

41.97 35.78 32.27 33.46 30.63

0.17 1.68 1.65 1.94 1.98

— 0.62 1.61 0.42 —

NOTES 1. In subsequent investigation by the authors (1) other high-activity monocyclopentadienyl complexes were prepared, (I), and used in the preparation of polyethylene and poly(ethylene-1-hexene).

298

Polyethylene and Catalyst Composition for Its Preparation

2. High-activity monocyclopentadienyl complexes, (II), containing indene were prepared by the authors (2) and used in the polymerization of ethylene.

3. Kipke et al. (3) prepared 2,6-bis[1-(2,4-dichloro-6-methylphenylimino)ethyl]pyridine iron(II) dichloride and bis(n-butylcyclopentadienyl)hafnium dichloride which when blended with an MAO were effective in preparing polyethylene for injection moldings. 4. Semicrystalline polypropylene composition was prepared by Suhm et al. (4) using racdimethylsilanediylbis(2-methyl-4-phenylindenyl)zirconium dichloride and racdimethylsilanediylbis(2-methylindenyl)zirconium dichloride. References 1. S. Mihan et al., U.S. Patent Application 20070213483 (September 13, 2007) and U.S. Patent Application 20070213484 (September 13, 2007). 2. S. Mihan et al., U.S. Patent Application 20070155918 (July 5, 2000). 3. J. Kipke et al., U.S. Patent Application 20070255033 (November 1, 2007). 4. J. Suhm et al., U.S. Patent Application 20070117940 (May 24, 2007).

e. Metathesis reactions

Title: Metal Complexes for Use in Olefin Metathesis and Atom Group Transfer Reactions Author: Assignee:

Francis Walter Cornelius Verpoort Universiteit Gent (Gent, BE)



20070185343 (August 9, 2007) Very high Early 2009

Air-stable and high-activity ruthenium-based catalysts containing Schiff base ligands useful in olefin metathesis agents or in atom or group transfer reactions. The preparation of high-activity and air-stable olefin metathesis catalysts is unreported in the patent literature. Single and cross-coupling polymerization agents The next generation of ruthenium metathesis catalysts have been prepared that are highly active, easily prepared, and require considerably less protective conditions. The three-step preparation is described below: a. Schiff bases were initially prepared in yields exceeding 85% b. Schiff bases were then quantatively converted into thalium phenoxide salts c. The high yielding coupling reaction of thalium phenoxide with [RuCl2(p-cymene)]2 When the ruthenium Schiff base olefin metathesis catalyst was used to polymerize cyclooctadiene Mw’s . 100,000 Da were obtained. Although only 12 Schiff bases were identified as effective in these polymerizations, additional analogs are anticipated to be reported from the University of Ghent group.

299

300

Metal Complexes for Use in Olefin Metathesis and Atom Group Transfer Reactions

REACTION

i. Thallium ethoxide, THF ii. THF, [RuCl2( p-cymene)]2 iii. Methyllithium, THF EXPERIMENTAL 1. Generic Method for the preparation of Schiff-base-substituted ruthenium complexes Ruthenium complexes with Schiff bases were prepared in three steps. In the first step a selected Schiff base (3 mmol) was dissolved in 15 ml THF and then added dropwise to a solution of thallium ethoxide in 5 ml THF at ambient temperature. Immediately after the addition, a pale yellow solid formed; the reaction mixture was stirred for 2 hours at 208C and then used immediately. In the second step the step 1 product dissolved in 5 ml THF was added a solution of [RuCl2(p-cymene)]2 in 5 ml THFand the reaction mixture stirred at ambient temperature for 6 hours. The thallium chloride by-product was then removed by filtration. The filtrate was concentrated, the residue recrystallized at 08C from a CH2Cl2/pentane mixture, and the product isolated and then dissolved in 15 ml diethyl ether and cooled down to 08C. In the third step an ethereal solution of the step 2 product was added to a solution of either 2.3 ml methyllithium (1.4 M in diethyl ether), 1.75 ml phenylmagnesium chloride (2 M in THF), or 7 ml of pentafluorophenylmagnesium chloride (0.5 M in diethyl ether). The reaction mixture was then slowly warmed to ambient temperature and stirred for 4 hours. The salt that formed was filtered and the filtrate concentrated. The residue was recrystallized from ether/pentane and the catalyst isolated from between 60 and 70% yield.

301

Derivatives

DERIVATIVES A summary of Schiff bases and olefin metathesis catalysts are provided in Tables 1 and 2, respectively.

TABLE 1. Summary of Schiff Bases Used to Prepare Ruthenium Salts as Precursors in Preparing Olefin Metathesis Catalysts a Entry A B C D E a

R1

R2

R3

R4

R5

t-Butyl t-Butyl Hydrogen Hydrogen Hydrogen

Hydrogen Hydrogen Hydrogen Nitro Hydrogen

i-Propyl Methyl Methyl Methyl i-Propyl

Hydrogen Bromo Bromo Bromo Hydrogen

i-Propyl Methyl Methyl Methyl i-Propyl

Extensive 1H-, 13C-NMR, and FTIR characterization data supplied by author of the current invention.

TABLE 2. Summary of Olefin Metathesis Catalysts Prepared by Reacting a Selected Schiff Bases with RuCl2( p-cymene)2 and then Postreacting with Alkyl or Aromatic Lithium Salt a Entry 2 3 4 5 6 7 a

R1

R2

R3

R4

R5

Hydrogen Hydrogen t-Butyl t-Butyl t-Butyl t-Butyl

Methyl Hydrogen Methyl i-Propyl i-Propyl i-Propyl

Methyl i-Propyl Hydrogen Hydrogen Hydrogen Hydrogen

Methyl i-Propyl Methyl i-Propyl i-Propyl i-Propyl

Methyl Methyl Methyl Phenyl Chloro Pentafluorophenyl

Extensive 1H-, 13C-NMR, and IR characterization data supplied by author of the current invention.

302

Metal Complexes for Use in Olefin Metathesis and Atom Group Transfer Reactions

NOTES 1. Norbornadiene- and cyclooctadiene-containing bridged olefin metathesis catalyst were also prepared by the author in the current application and are illustrated below.

2. Additional Schiff bases used in forming ruthenium metathesis catalysts, (I), are provided by Schaubroeck et al. (1).

3. Walter et al. (2) prepared the heterogeneous Schiff base ruthenium complex, (II), on a mesoporous support having a hexagonal unit cell. The catalyst was used to prepare 5-norbornene and cyclooctadiene copolymers by ring-opening metathesis polymerization.

Notes

303

4. Pawlow et al. (3) prepared multifunctionalized high-trans-content elastomeric polymers using Grubbs’ second-generation ruthenium catalyst in the metathesis polymerization of cyclooctadiene, cyclopentene, and 1,4-bis(trimethoxysilyl)2-butene. 5. The Schiff base ruthenium complex, (III), prepared by Fogg et al. (4) was effective in ring-closing metathesis reactions and used in polar protic solvents at elevated temperatures.

References 1. D. Schaubroeck et al., U.S. Patent Application 20070043188 (February 22, 2007). 2. F. Walter et al., U.S. Patent Application 20050043541 (February 24, 2005). 3. J.H. Pawlow et al., U.S. Patent Application 20060173145 (August 3, 2006). 4. D.E. Fogg et al., U.S. Patent Application 20050131233 (June 16, 2005).

f. Olefin metathesis reactions

Title: Alkylidene Complexes of Ruthenium Containing N-Heterocyclic Carbene Ligands: Use as Highly Active, Selective Catalysts for Olefin Metathesis Author: Assignee:

Wolfgang Anton Herrmann et al. Degussa AG (Hanau-Wolfgang, DE)


Application:

Observations:

20080009598 (January 10, 2008) Moderately high Mid-2010

Identification of high-activity ruthenium alkylidene catalysts for ringopening and ring-closing metathesis reactions. Although ruthenium polymerization catalysts containing Schiff bases are reported in the patent literature, these catalysts remain active despite the presence of bulky groups. Polymer intermediates Chemical intermediates Improved synthetic method The objectives of this study were to prepare metathesis catalysts that: a. Remained highly active in the presence of bulky ligands b. Expanding the type of olefins that could be used in methathesis reactions Metathesis reactions involving the metal-alkylidene catalyst component as the active species nonbulky monomers are more active than their bulky counterpart. To address this limitation, 5-norbornene monomer containing an unhindered or bulky 2-substituents were metathesized with favorable reaction kinetics using ruthenium-containing complexes illustrated below.

304

Derivatives

305

REACTION

i. Benzylidenedichloro-(1,3-dicyclohexylimidazolin-2-ylidene)(tricyclohexylphosphine)ruthenium, CH2Cl2

EXPERIMENTAL 1. Polymerization of cyclooctene: Generic procedure Cyclooctene (3.13 mmol) was added to a solution of benzylidenedichloro-(1,3dicyclohexylimidazolin-2-ylidene)(tricyclohexylphosphine)ruthenium (6.3 mmol) dissolved in 0.5 ml of CH2Cl2. After approximately 10 minutes a highly viscous gel formed that could no longer be stirred and required the addition of 1 ml of CH2Cl2, this process being repeated three times. After 1 hour an additional 5 ml of CH2Cl2 containing small amounts of t-butyl ether and 2,6-di-tert-butyl-4-methylphenol were introduced to the mixture. After a further 10 minutes, the solution was precipitated by slowly adding it to a large excess of methanol and 291 mg of product isolated.

DERIVATIVES Polymerization metathesis catalyst derivatives are illustrated below

306

Alkylidene Complexes of Ruthenium Containing N-Heterocyclic Carbene Ligands

Catalyst Entry

R1

R2

1

iso-Propyl

Hydrogen

2

(R)-1-Phenyl ethyl

Hydrogen

3

(R)-1-Naphthyl ethyl

Hydrogen

4

iso-Propyl

Chloro

5

Cyclohexyl

Hydrogen

REACTION SCOPING Polymerization conversions of norbornene and cyclooctene using complexes 1 and 5 were performed and results summarized in Table 1. Polymerization conversion using 5-norbornene-2-substituted derivatives using complex 1 are provided in Table 2. TABLE 1. Polymerization Conversion Rates Observed for Norbornene and Cyclooctene Varying Reaction Conditions a Entry

Catalyst

Monomer

Ratio (Monomer)/ (Catalyst)

2.1a 2.1b 2.1c 2.1d 2.1e

1 5 1 1 5

Norbornene Norbornene Cyclooctene Cyclooctene Cyclooctene

100:1 100:1 500:1 500:1 500:1

a

Reaction Time 1 1 1 2 1

Conversion (%)

minute minute hour hours hour

91 92 84 97 87

Extensive 1H-NMR data supplied by author (current invention) for catalysts.

TABLE 2. Polymerization of 5-Norbornene-2-Substituted Derivatives Using Catalyst 1 in CH2Cl2a Entry

R

Temperature (8C)

Reaction Time (h)

Conversion (%)

2.1f 2.1g 2.1h 2.1i 2.1j

O2CCH3 CH2OH CHO CHO CO2H

25 25 25 50 25

0.5 2 2 2 2

99 15 36 52 98

a

All reactions were conducted at 508C in CH2ClCH2Cl.

Notes

307

NOTES 1. The structure for the step 1 ring-opening metathesis polymerization catalyst, (I), is illustrated below.

2. Ring-closing methathesis reactions were also performed using the step 1 Catalyst as illustrated in Eq. (1). (1)

i. Catalyst, CH2ClCH2Cl 3. Perfluoro methathesis oligomers, (II), were prepared by Lazzari et al. (2) and were useful in increasing repellency of oil and water on fibers by using bis(tricyclopentyl-phosphine)dichloro(3-methyl-2-butenylidene)ruthenium, (III), as the ringopening methathesis catalyst as illustrated in Eq. (2). This catalyst was also prepared by Liaw et al. (3) and used to prepare functionalized polynorborenes, (IV), by ringopening metathesis polymerization as illustrated in Eq. (2).

(2)

308

Alkylidene Complexes of Ruthenium Containing N-Heterocyclic Carbene Ligands

(3)

4. Ring-opening metathesis polymerization was conducted by Verpoort et al. (4) using cyclooctene with a ruthenium Schiff base complex, (V), and proceeded with a monomer-to-catalyst ratio of 150,000:1, respectively.

References 1. J. Berlin et al., U.S. Patent Application 20070282148 (December 6, 2007). 2. D. Lazzari et al., U.S. Patent Application 20070037940 (February 15, 2007). 3. D.-J. Liaw et al., U.S. Patent Application 20070173609 (July 26, 2007). 4. F.W.C. Verpoort et al., U.S. Patent Application 20070185343 (August 9, 2007).

g. 5-Norbornen-2-ol polymerization

Title: Metal Catalyst for Olefin Polymerization and Copolymerization with Functional Monomers Author: Assignee:

Guillermo C. Bazan et al. The Regents of the University of California (Oakland, CA)


20080051533 (February 28, 2008) High 2010

Ambient temperature copolymerization of ethylene with 5-norbornen-2-yl acetate or with ethylene and 5-norbornen-2-yl alcohol. Four-year ongoing investigation. Olefin polymerization catalyst for industrial polymers There is a continuing effort to address the shortcomings of existing metal olefin polymerization catalysts. For example, methylaluminoxanes and Lewis acid catalysts are thermally unstable and the activity of methylaluminoxane-activated catalysts decay rapidly at 608C; borane catalysts are decomposed at ambient temperature. Neutral catalyst agents that do not require an activator are prone to long induction periods and have lower activites than compared with cationic systems. The current application has determined that these concerns are best resolved using Group VIII transition metals. The catalyst system consists of N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamide benzyltrimethyl-phosphine nickel and bis(1,5-cyclooctadiene)nickel. The catalyst is effective at ambient conditions producing high-molecularweight polyolefins and copolymers with functional groups.

309

310

Metal Catalyst for Olefin Polymerization and Copolymerization

REACTION

i. N-(2,6-Diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamide-benzyltrimethylphosphine nickel, toluene, bis(1,5-cyclooctadiene)nickel, ethylene EXPERIMENTAL 1. Preparation of poly(ethylene-co-5-norbornen-2-ol) A glass reactor was charged with N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamide-benzyltrimethylphosphine nickel (20 mmol) in toluene, bis(1,5-cyclooctadiene)-nickel (50 mmol) in toluene, and 5-norbornen-2-ol (4.49 mmol) were dissolved in toluene, and additional toluene (18.45 g) added so that the total volume of the toluene solution was 30 ml. The glass reactor was then sealed and ethylene continuously fed into the reactor at 100 psi and the mixture stirred for 20 minutes at 208C. Acetone was then added to quench the polymerization and the precipitated polymer isolated by filtration, dried, and 0.518 g of product isolated. The activity of the catalyst was 105 kg mol21h21. DERIVATIVES Ethylene and 5-norbornen-2-yl-acetate were also copolymerized using N-(2,6diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamide-benzyltrimethylphosphine nickel.

POLYMERIZATION SCOPING REACTIONS TABLE 1. Physical Properties of Poly(ethylene-co-5-norbornen-2-ol) Prepared Using 50 mmol Ni(COD)2 and 20 mmol N-(2,6-diisopropylphenyl)-2-(2,6diisopropylphenylimino)propanamide Benzyltrimethylphosphine Nickel at 100 psi Ethylene Entry 10 12 13 16 a

Norborene Derivative (mmol) 4.49 0.91 9.12 3.99

PDI ¼ poly dispersity index.

Product (g) 0.518 0.102 0.498 0.619

Norborene Content (%)

Mn (Da)

15.8 4.7 18.5 12.5

2.56 10 2.09 104 1.80 104 6.57 104 4

PDIa

Tm (8C)

2 1.9 2.9 1.4

72.9 87.9 87.8 —

Notes

311

TESTING Contact Angles Thin films of polyethylene, poly(ethylene-co-5-norbornen-2-yl acetate), and poly(ethylene-co-5-norbornen-2-ol) were prepared on glass slides and contact angle measurements of water droplets determined. Testing results are provided in Table 2. TABLE 2. Contact Angle Testing Results Indicating the Increased Hydrophilicity when Ethylene was Copolymerized with Either 5-Norbornen2-yl Acetate or 5-Norbornen-2-ol, According to Current Application Entry 1 9 16

Polymer Surface

Contact Angle (8)

Polyethylene, Poly(ethylene-co-5-norbornen-2-ol) Poly(ethylene-co-5-norbornen-2-yl-acetate)

124(4) 101(4) 100(4)

NOTES 1. The step 1 co-catalyst, (I), is depicted below.

2. Polyethylene was previously prepared by the authors (1) using catalyst, (II), consisting of the co-catalyst with bis(1,5-cyclooctadiene)-nickel. Polyethylene was also prepared by Salon et al. (2) and Baugh et al. (3) using iron- and nickel-based organometallic catalysts, (III) and (IV), respectively.

312

Metal Catalyst for Olefin Polymerization and Copolymerization

3. 5-Norbornen-2-yl 4-(1-(3-(2,2,5-trimethyl-4-phenyl-3-azahexoxy))ethyl)benzyl ether, (V), was previously prepared by the authors (4) and used in the controlled free radical copolymerization of ethylene and 5-norbornen-2-ol. Polymerization were carried out in the presence of the two component catalyst mixture of the current application.

References 1. G.C. Bazan et al., U.S. Patent Application 20070225456 (September 27, 2007) and U.S. Patent 7,259,214 (August 21, 2007). 2. G.A. Solan et al., U.S. Patent 7,317,057 (January 8, 2008). 3. L.S. Baugh et al., U.S. Patent 7,285,609 (October 23, 2007). 4. G.C. Bazan et al., U.S. Patent Application 20070149732 (June 28, 2007).

h. Poly(propene-1-butene-1-hexene) preparation

Title:

Propylene-Based Terpolymers

Author: Assignee:

Luigi Resconi et al. Basell Polyolefine GmbH (Wesseling, DE)

U.S. Patent Application: Material Patentability: Anticipated Issuing Date:

Research Focus: Originality:

Application:

Observations:

20070293641 (December 20, 2007) Medium Early/mid-2009

Method for preparing poly(propene-1-butene-1-hexene) using a silyl/ zirconium-based Ziegler –Natta procatalyst. Only limited information has been reported in the patent literature on utilizing silyl-zirconium Ziegler– Natta procatalysts in terpolymerization reactions. Films Food containers Molding Metallocene-driven terpolymeration usually relies upon hafnium-based catalysts. In this application, poly(propene-1-butene-1-hexene) was prepared using a silyl-zirconium-based Ziegler –Natta procatalyst in conjunction with co-catalysts triisobutylaluminium and methylalumoxane and in the absence of a reaction solvent. The incorporation of C3, C4, and C6 monomers into the terpolymer were 75.8, 19.5, and 4.7%, respectively, and where the terpolymer had a Tm and Tg of 94.2 and 2208C, respectively. The material formed was flexibility and soft and was used in films and moldings.

313

314


REACTION

i. Triisobutylaluminium, methylalumoxane, isododecane ii. Triisobutylaluminium, 1-butene, propylene, 1-hexene EXPERIMENTAL 1. Preparation of catalyst A 20-liter reactor was charged with 3.11 liters of triisobutylaluminum isododecane solution (110 g/l) and 800 ml of 30 wt% methylalumoxane toluene solution and then stirred at 508C for 1 hour. This mixture was then treated with dimethylsilylf(2methyl-1-indenyl)-7-(2,5-dimethylcyclopenta[1,2-b:4,3-b-0 ]-dithiophene)gzirconium dichloride (13.1 mmol) suspended in isododecane (500 g) and stirred 1 hour at 508C. The reaction mixture was then diluted with 520 ml of isododecane so that the final concentration of the catalyst mixture was 100 g/l. The catalyst was then used immediately. 2. Terpolymerization At ambient temperature a reactor was charged with triisobutylaluminium (6 mmol; 1 M solution in hexane), 1-butene (334 g), propylene (817 g), and 1-hexene (119) and then heated to 708C . The solution was then treated with 1 ml of the step 1 product and stirred for 1 hour. The mixture was cooled to ambient temperature and the polymer isolated having C3, C4, and C6 monomer incorporations of 75.8, 19.5, and 4.7%, respectively, with a Tm and Tg of 94.2 and 2208C, respectively. DERIVATIVES No additional terpolymers were prepared. NOTES 1. Semicrystalline poly(ethylene-co-propylene) was prepared by the authors (1) using a Zr/Si procatalyst, (I), supported on an organic porous substrate having pore sizes of 0.1 and 2 mm. The catalyst was prepared after activating

Notes

315

with triisobutylaluminium and methylalumoxane. Other preparations of semicrystalline polypropylene are described by Pelliconi et al. (2).

2. Additional high-activity propylene polymerization catalysts, (II), are described by Nifant’evi et al. (3).

3. The preparation of poly(1-butene) containing isotactic pentads using procatalyst (III) is described by the authors (4,5).

316


References 1. L. Resconi et al., U.S. Patent Application 20070276095 (November 29, 2007). 2. A. Pelliconi et al., U.S. Patent Application 20060287436 (December 21, 2006). 3. I. Nifant’evi et al., U.S. Patent Application 20070112152 (May 17, 2007). 4. L. Resconi, U.S. Patent Application 20070149729 (June 28, 2007). 5. L. Resconi et al., U.S. Patent Application 20070276076 (November 29, 2007).

XII. INITIATORS/MODIFIERS A. Free Radical Initiators a. Acyloxime esters

Title:

N-Substituted Imides as Polymerization Initiators

Author: Assignee:

Peter Nesvadba et al. Ciba Corporation (Tarrytown, NY)


20080132600 (June 5, 2008) Moderate June, 2011

Preparation of N-substituted imide dialkyl-thiocarbamic acid esters as high-activity polymerization initiators. This has been an ongoing 6-year investigation by the Ciba Geigy group. Free radical polymerization initiator N-Substituted imide acid esters were prepared by the nucleophilic attack of N-hydroxyphthalimide on N-methyl benzimidoyl chloride or on a dialkyl-thiocarbamic derivative. These N-substituted imides were effective as high-yielding thermal polymerization initiators. Although N-alkoxyphthalimides and succinimides thermal initiators have previously been prepared and used to polymerize acrylates and methacrylates, relatively low polymer conversions were observed. Photopolymerizable acyloxime ester initiators have been prepared by this group in previous investigations.


317

318


REACTION

i. Ethanol, sodium ii. Dimethyl formamide (DMF), N-methyl-benzimidoyl chloride

EXPERIMENTAL 1. Preparation of N-hydroxyphthalimide sodium salt N-Hydroxyphthalimide (0.723 mol) was suspended in 700 ml of absolute ethanol and then treated with the dropwise addition of sodium (0.723 mol) dissolved in 400 ml of absolute ethanol and stirred for 19 hours at ambient temperature. A red solid was isolated by filtration and after washing and drying 133 g of a red product isolated. 2. Preparation of N-methyl-benzimidic acid 1,3-dioxo-1,3-dihydroisoindol-2-yl ester The step 1 product (0.25 mol) was dissolved in 220 ml DMF and the mixture treated with N-methyl benzimidoyl chloride (0.25 mol) at ambient temperature and then stirred for 19 hours and precipitated in 1500 ml of water. The solid was isolated by filtration and dried in vacuo. The crude product (66.06 g) was dissolved in 250 ml of acetonitrile, refiltered, and 58.7 g product isolated as colorless crystals having an mp ¼ 174 – 1768C.

Testing

319

DERIVATIVES TABLE 1.

Melting Points of Selected Dialkylthiocarbamic Acid Esters

Entry

Structure

Melting Point (8C)

5

—

7

148–151

10

135–138

11

73– 75

12

148–150

TESTING A. Pendulum Hardness and Cross-Hatch Tests Pendulum hardness (Koenig 53157) and cross-hatch tests (DIN 53 151) were performed on polymers prepared using selected initiators described in this application and results provided in Table 2.

TABLE 2. Pendulum Hardness and Cross-Hatch Testing Results for Polymers Prepared Using Selected DialkylThiocarbamic Acid Esters Entry 5 7

Pendulum Hardness (s)

Cross Hatch

207.2 207.2

1 0

320


B. Oven Testing Oven testing was performed using 0.4 g of a selected polymer sample that were dissolved in screening formulation (20.00 g) and then applied to white coil-coat aluminum and baked in an oven at 1608C for 30 minutes and a tack free dry film with a thickness of approximately 25 cm obtained. After curing for 45 minutes, the pendulum hardness testing was conducted and results summarized in Table 3. TABLE 3. Pendulum Hardness Testing Results for Cured Polymers Prepared Using Selected Dialkylthiocarbamic Acid Esters as Initiators Entry

Pendulum Hardness (s)

5 10 11 12

126 133 137 137

NOTES 1. Medina et al. (1) photodimerized maleimide derivatives, (I), as a method for preparing semitelechelic silicone hydrogel polymers useful as for lens coatings as illustrated in Eq. (1).

(1)

2. Oxime photoinitiators, (II), were prepared by Tanabe et al. (2) and used in preparing photosensitive polymeric materials.

Notes

321

3. Photopolymerizable acyloxime ester initiators, (III), were prepared by Sasaki et al. (3) and used to produce color film.

4. Heteroaromatic oxime ester photoinitiators, (IV), were prepared by Tanabe et al. (4) and used in photopolymerization reactions.

References 1. A.N. Medina et al., U.S. Patent Application 20080143958 (June 19, 2008). 2. J. Tanabe et al., U.S. Patent Application 20080096115 (April 24, 2008). 3. T. Sasaki et al., U.S. Patent Application 20070203255 (August 30, 2007). 4. J. Tanabe et al., U.S. Patent Application 20060241259 (October 26, 2006).

B. Free Radical Initiator Modifiers a. Piperidine N-oxide derivatives

Title: N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidine Compounds, Their Corresponding N-Oxides, and Controlled Radical Polymerization Therewith Author: Assignee:

Peter Nesvadba et al. Ciba Specialty Chemicals Corporation (Tarrytown, NY)


322

20080015276 (January 17, 2008) Very high Mid-2010

Synthesis of N-alkoxy-4,4-dioxy-piperidine and N-oxide derivatives for use as controlling agents in free radical polymerization reactions. The investigation is both original and extensive. Free radical chain transfer agents A wide range of synthetic methods for preparing N-alkoxy-4,4-dioxypiperidine and N-oxide derivatives were provided by this group in this application. In addition experimental methods for optimizing the use of these agents in preparing polymers with customized properties are also described. Related N-alkoxy-4,4-dioxy-piperidine and N-oxide derivatives were also prepared and used to prepare polymethacrylate macromolecules. Finally, many of these agents can be used to prepare thermally or ultraviolet (UV) curable polymeric materials useful as coatings and films.

Derivatives

323

REACTION

i. Ethylbenzene, t-butyl-hydroperoxide, copper(II) chloride, lithium chloride, ethanol

EXPERIMENTAL 1. Preparation of 8,10-diethyl-3,3,7,8,10-pentamethyl-9-(1-phenyl-ethoxy)15-dioxa-9-aza-spiro[5.5]undecane A solution of 7,9-diethyl-6,7,9-trimethyl-1,4-dioxa-8-aza-spiro[4,5]decan-8-oxyl (0.04 mol) dissolved in 40 ml ethylbenzene containing 8.3 ml of 70% t-butyl-hydroperoxide (0.06 mol) dissolved in water was treated with 0.7 ml of the catalyst solution consisting of CuCl2 (13.44 g) and LiCl (4.24 g) dissolved in 153 ml ethanol. The mixture was stirred at 658C for 90 minutes where it became colorless and was cooled and treated with 25 ml of water containing Na2S2O5 (5 g) and then stirred for 10 minutes. The organic phase was separated, washed with water, and concentrated. The residue was purified by chromatography using silica gel with hexane/ethylacetate, 19:1, respectively, and 10.3 g of product isolated as a colorless oil.

DERIVATIVES

324

N-Alkoxy-4,4-Dioxy-Polyalkyl-Piperidine Compounds

NOTES 1. All N-alkoxy-4,4-dioxy-piperidine derivatives were converted into the corresponding N-oxides. 2. Additional derivatives of the current invention are described by Nesvadba et al. (1). 3. Alkoxyamines containing a polymerizable group, (I), were prepared by Nesvadba et al. (2) and used to prepare macroinitiators.

4. Wolf et al. (3) prepared coating compositions using hydroxylamine esters, (II) and (III), that were curable by thermal and ultraviolet radiation.

5. Nesvadba et al. (4) converted secondary amines into the corresponding nitroxides using 40% peracetic acid, calcium carbonate, water, and toluene.

References 1. P. Nesvadba et al., U.S. Patent Application 20060149011 (July 6, 2006), U.S. Patent 7,288,613 (October 30, 2007), and U.S. Patent 7,199,245 (April 3, 2007). 2. P. Nesvadba et al., U.S. Patent Application 20070232768 (October 4, 2007). 3. J.P. Wolf et al., U.S. Patent Application 20060172080 (April 3, 2006). 4. P. Nesvadba et al., U.S. Patent Application 20060229452 (October 12, 2006).

C. Photoinitiators a. a-Aminoketones

Title:

Functionalized Photoinitiators

Author: Assignee:

Kurt Dietliker Ciba Specialty Chemicals Corporation (Tarrytown, NY)



20080021126 (January 24, 2008) Low Mid-2010

The preparation of a-aminoketones having high initiator activity, low odor, low migration, and that are reactive with acids, aldehydes, and ketones. This application represents a chemical modification to a 17-year-old existing photoinitiator reported in the patent literature. Photoinitiator Although modified a-aminoketones were prepared in a single step, four steps were needed to prepare the step 1 reagent, 2-benzyl-1-(4fluorophenyl)-2-dimethylamino-1-butanone beginning with 2-dimethylbutyl acid chloride. The value of this application, however, resides in the ability to convert the product into ester and Schiff base derivatives while the material still remains photoactive.

REACTION

i. Ethanolamine, potassium carbonate, N,N-dimethylacetmide 325

326


EXPERIMENTAL 1. Preparation of 2-benzyl-1-[4-(2-hydroxyethylamino)phenyl]-2-dimethylamino-1-butanone A reactor charged with 2-benzyl-1-(4-fluorophenyl)-2-dimethylamino-1-butanone (0.15 mol) and ethanolamine (1.05 mol) were dissolved in 400 ml dimethylacetamide and then treated with potassium carbonate (0.3 mol) and then heated to 1408C for 16 hours, cooled, and diluted with water. The aqueous phase was extracted several times with ethyl acetate and combined extracts washed with water and dried using magnesium sulfate. The mixture was then concentrated and the residue isolated as a yellowish-brown oil. It was purified using chromatography on silica gel with petroleum ether/ethyl acetate 2:1 to 1:1, respectively. The product was isolated as a yellow solid after recrystallization from ethyl acetate/hexane having an mp ¼ 109– 1118C.

DERIVATIVES TABLE 1. Entry

Selected Functionalized Photoinitiators Prepared in a Selected Stepa Structure

Yield (%)

2

37

5

38

8

30

16

57

a

All products were isolated as viscous yellow liquids. 1H- and current invention.

13

C-NMR supplied by the author of the

Notes

327

NOTES 1. An ultraviolet radiation activated initiator consisting of 2,2-diethoxy-acetophenone, (I), was used by Hyde (1) to prepare pressure-sensitive adhesives.

2. The cationic photoinitiator triarylsulfonium, diaryliodonium, and related aryl diazonium salts containing nonnucleophilic counterions, were used by Konarski et al. (2) to prepare adhesives. 3. Cyclohexyl phenyl ketone was used by Johnson et al. (3) to photocure intermediates for three-dimensional articles using rapid prototyping techniques. The product exhibited stable tensile properties over time. 4. Husler et al. (4) prepared photoactive ketones, (II) – (IV), which were activated in the ultraviolet and visible radiation range.

5. Melikechi et al. (5) developed a method for curing polymerizable compositions using camphorquinone, (V), as the photoinitiator by irradiating with light emitted from a light-emitting diode (LED). This method is especially preferred for curing dental compositions.

328


References 1. P.D. Hyde, U.S. Patent Application 20070276108 (November 29, 2007). 2. M.M. Konarski et al., U.S. Patent Application 20070267134 (November 22, 2007). 3. D.L. Johnson et al., U.S. Patent Application 20070256781 (November 8, 2007). 4. R. Husler et al., U.S. Patent Application 20070240609 (October 18, 2007). 5. N. Melikechi et al., U.S. Patent 7,321,004 (January 22, 2008).

b. Oximes

Title:

Oxime Ester Photoinitiators

Author: Assignee:

Junichi Tanabe et al. Ciba Speciality Chemical Corporation (Tarrytown, NY)



20080096115 (April 24, 2008) Moderate 2011

Synthesis of N-ethylcarbazole oxime ester photoinitiators containing heteroatoms. While N-ethylcarbazole oxime ester photoinitiator analogs containing heteroatoms have previously been prepared, these agents show unusually high Stepwedge sensitivity. Manufacture of display panels N-Ethylcarbazole oxime ester derivatives were prepared that are effective as photoinitiators in photoresist applications. These chemical agents were prepared in four steps entailing: i. Acylation of N-ethylcarbazole using 4-fluorobenzoyl chloride with aluminum chloride ii. Secondary amine displacement of fluorine via a Meisenheimer intermediate iii. Formation of an oxime using hydroxylammonium chloride iv. Ester formation by O-acylation of the oxime Although other heteroatom and heteroaryl N-ethylcarbazole oxime ester analogs have previously, the agents of the current invention have unusually high Stepwedge sensitivity.

329

330


REACTION

i. ii. iii. iv.

4-Fluorobenzoyl chloride, aluminum chloride, acetyl chloride N,N-Dimethylacetamide, morpholine N,N-Dimethylacetamide, hydroxylammonium chloride, sodium acetate Triethylamine, acetyl chloride EXPERIMENTAL

1. Preparation of 1-[9-ethyl-6-(4-fluoro-benzoyl)-9H-carbazol-3-yl]-ethanone N-Ethylcarbazole (25.60 mmol) dissolved in 40 ml in CH2Cl2 was added to 4-fluorobenzoyl chloride (25.60 mmol) and AlCl3 (25.6 mmol) at 08C and then stirred 4 hours at ambient temperature. It was further treated with acetyl chloride (25.60 mmol) and AlCl3 (25.6 mmol) at 08C and then stirred at ambient temperature overnight and poured into ice water and extracted with CH2Cl2. The organic layer was washed with water, saturated aqueous NaHCO3, brine, and then dried using MgSO4. The mixture was concentrated and then washed with methyl-t-butyl ether and 7.2 g of product isolated as a gray solid and used without further purification. 1

H-NMR (CDCl3) d 1.50 (t, 3H), 2.73 (s, 3H), 4.45 (q, 2H), 7.21 (d, 2H), 7.49 (dd, 2H), 7.89 (dd, 2H), 8.05 (dd, 1H), 8.19 (dd, 1H), 8.59 (d, 1H), 8.78 (d, 1H)

2. Preparation of 1-[9-ethyl-6-(4-morpholin-4-yl-benzoyl)-9H-carbazol3-yl]-ethanone The step 1 product (25.6 mmol) dissolved in 10 ml N,N-dimethylacetamide was treated with morpholine (12.3 mmol) at 1008C and then stirred at 1408C for 15 hours and

Derivatives

331

the mixture poured into water and a beige solid obtained. The solid was dissolved in CH2Cl2, dried with MgSO4, and concentrated. The residue was purified by silica gel column chromatography using ethyl acetate/hexane, 1/3 to 1/1, respectively, and 1.03 g product isolated as a beige solid. 1

H-NMR (CDCl3) d 1.50 (t, 3H), 2.72 (s, 3H), 3.36 (t, 4H), 3.89 (t, 4H), 4.44 (q, 2H), 6.96 (d, 2H), 7.48 (dd, 2H), 7.86 (dd, 2H), 8.05 (dd, 1H), 8.16 (dd, 1H), 8.58 (d, 1H), 8.73 (d, 1H)

3. Preparation of 1-[9-ethyl-6-(4-morpholin-4-yl-benzoyl)-9H-carbazol3-yl]-ethanone oxime The step 2 product (12.41 mmol) dissolved in 10 ml N,N-dimethylacetamide was treated with a mixture of hydroxylammonium chloride (2.90 mmol) and sodium acetate (2.90 mmol) dissolved in 5 ml water and then stirred at 1008C for 4 hours. The mixture was treated with water and a brownish yellow solid isolated. This material was washed with water, dissolved in CH2Cl2, and dried using MgSO4. It was concentrated, repurified by precipitation in CH2Cl2/hexane solution, and 0.81 g product isolated. 1

H-NMR (CDCl3) d 1.47 (t, 3H), 2.42 (s, 3H), 3.35 (t, 4H), 3.89 (t, 4H), 4.42 (q, 2H), 6.96 (d, 2H), 7.45 (dd, 2H), 7.86 (m, 3H), 8.05 (dd, 1H), 8.33 (dd, 1H), 8.58 (d, 1H)

4. Preparation of 1-[9-ethyl-6-(4-morpholin-4-yl-benzoyl)-9H-carbazol-3-yl]ethanone oxime O-acetate The step 3 product (1.81 mmol) was dissolved in 20 ml tetrahydrofuran (THF) and then treated with triethylamine (2.17 mmol) and acetyl chloride (2.17 mmol) at 108C and then stirred at ambient temperature and poured into water. The mixture was extracted with ethyl acetate, and then washed with saturated NaHCO3 and brine and then dried with MgSO4 and concentrated. The residue was washed with CH2Cl2 and then methyl-t-butylether and 0.70 g of product isolated. 1

H-NMR (CDCl3) d 1.47 (t, 3H), 2.30 (s, 3H), 2.52 (s, 3H), 3.36 (t, 4H), 3.90 (t, 4H), 4.44 (q, 2H), 6.97 (d, 2H), 7.48 (dd, 2H), 7.87 (dd, 2H), 7.96 (dd, 1H), 8.05 (dd, 1H), 8.49 (dd, 1H), 8.58 (d, 1H); mp ¼ 180 –1838C

DERIVATIVES

332


TABLE 1. Experimental Oxime Ester Photoinitiators and Corresponding Melting Points Entry

R

180–183

Step 4 product

N(C2H5)2

2

Melting Point (8C)

78–82

3

78–80

4

195–197

TESTING Sensitivity Testing A. Formulation A photocurable composition for sensitivity testing was prepared by mixing the following components: i. ii. iii. iv. v.

Benzylmethacrylate and methacrylic acid copolymer (200.0 parts) Propylene glycol 1-monomethyl ether 2-acetate solution (25%) Dipentaerythritol hexaacrylate (50.0 parts) Experimental photoinitiator (2.0 parts) Propylene glycol 1-monomethyl ether 2-acetate solution (150.0 parts)

B. Testing Protocol A dry film thickness of approximately 2 mm was prepared by adding the formulated composition to an aluminum plate using an electric applicator and removing the solvent by heating at 1008C for 2 minutes in a convection oven. A standardized test negative film with 21 steps of different optical densities was placed within a 100-mm air gap between the film and the resist. Exposure was carried out using a 250-W super-high-pressure mercury lamp at a distance of 15 cm. After exposure the film was developed and the sensitivity of the initiator characterized by indicating the highest number of steps remaining polymerized after developing. Sensitivity testing results are provided in Table 2.

Notes

333

TABLE 2. Sensitivity Testing of Selected Oxime Ester Photoinitiators Using a 250-W High-Pressure Mercury Lamp at a Distance of 15 cma Entry

Stepwedge Sensitivity Number of Steps

Step 4 product 3

20 20

a

The higher the number of steps, the more sensitive is the system tested.

NOTES 1. Oxime ester derivatives with heteroaryl components, (I), were previously prepared by the authors (1) and used in photoresist applications.

2. Photopolymerizable naphthyl oxime ester, (II), derivatives prepared by Kunimoto et al. (2) were effective in the radiation range of from 150 to 600 nm or with an electron beam or X rays.

334


3. Additional oxime ester photoiniators, (III), were prepared by Kunimoto et al. (3) and used in photoresist applications.

References 1. J. Tanabe et al., U.S. Patent Application 20060241259 (October 26, 2006). 2. K. Kunimoto et al., U.S. Patent Application 20050191567 (September 1, 2005). 3. K. Kunimoto et al., U.S. Patent 7,189,489 (March 13, 2007) and U.S. Patent 6,949,678 (September 27, 2005).

XIII. LIGHT-EMITTING POLYMERS A. Diodes a. Conjugated Aromatic Dendrimers

Title:

Dendrimers

Author: Assignee:

Paul Leslie Burn et al. Isis Innovation Limited (Oxford, GB)



Development of conjugated dendrimers for use as electrically actuated light-emitting diodes. This has been a 5-year ongoing investigation by this group. Organic and polymer light-emitting diodes (LEDs) This current project represents a continuation of an extensive investigation by this group to identify and prepare dendrimers that are effective as lightemitting diodes. The core chemical polyconjugated component was tris[4(40 -formylstyryl)phenyl]amine and was used in Wittig reagents to prepare conjugated dendrimers. Polyconjugated charge-neutral metallic dendrimers were also prepared that were luminescent in the solid state. By replacing the alkoxide function on these luminescent agents with diphenylamine derivatives phosphorescent dendrimers were prepared.


335

336

Dendrimers

REACTION

i. 1-(Methylenedimethylphosphonate)-3,5-di-tert-butylbenzene, tris[4-(40 -formylstyryl)phenyl]amine, potassium t-butoxide, tetrahydrofuran (THF)

EXPERIMENTAL 1. Preparation of G(O) dendrimer A reactor was charged with 1-(methylenedimethylphosphonate)-3,5-di-tert-butylbenzene (3.16 mmol), tris[4-(40 -formylstyryl)phenyl]amine (0.78 mmol), and potassium t-butoxide (3.15 mmol) dissolved in 80 ml THF and then stirred at ambient temperature under argon for 16 hours. The mixture was then treated with 25 ml water and 175 ml CH2Cl2 and the organic layer isolated. The organic layer was dried using Na2SO4, filtered, and concentrated to give a yellow solid residue. Purification by column chromatography using CH2Cl2-light petroleum, 1:4, respectively, to CH2Cl2 alone provided 804 mg of product isolated as a bright yellow solid, mp ¼ 1828C. lmax (CH2Cl2)/nm (log 1) 241 (4.72), 341 (4.91) and 421 (5.13) 1 H-NMR (CDCl3) d 1.38 (54H, s, t-Bu), 7.05 and 7.19 (6H, ABq, J 16.5, 70 , 80 -H), 7.09 and 7.14 (6H, ABq, J 6, 700 , 800 -H), 7.14 and 7.45 (12H, AA0 BB0 , 2,3,5,6-H), 7.37 (3H, dd, J 1.5, 400 -H), 7.39 (6H, d, J 1.5, 200 , 600 -H), 7.53 (12H, AA0 BB0 , 20 30 50 60 -H) m/z (FAB) 1194.8 (Mþ, 100%)

Notes

337

NOTES 1. The step 1 co-reagent, tris[4-(40 -formylstyryl)phenyl]amine, (I), illustrated in Eq. (1), was prepared by the authors (1) in an earlier investigation.

(1)

i. Bromine, chloroform ii. Palladium-based catalyst, sodium carbonate, dibenzyl carbonate (DBC), dimethyl acetamide (DMA) 2. Charge-neutral metallic dendrimer complexes, (II), were prepared by Samuel et al. (2), which were luminescent in the solid state. In separate investigations phosphorescent dendrimers were prepared by Lo et al., (III), and Burn et al. (4), respectively, and used in light-emitting devices.

3. Tomalia et al. (5) develop a synthetic method for preparing functionalized dendritic compositions having high thermal stability that did not undergo a reversible Michael addition reaction.

338

Dendrimers

References 1. P.L. Burn et al., U.S. Patent Application 20060252963 (November 9, 2006) and U.S. Patent 7,276,299 (October 2, 2007). 2. I.D.W. Samuel et al., U.S. Patent Application 20060119254 (June 8, 2006). 3. S.-C. Lo et al., U.S. Patent Application 20050116622 (June 2, 2005). 4. P.L. Burn et al., U.S. Patent Application 20070009759 (January 11, 2007). 5. D.A. Tomalia et al., U.S. Patent Application 20070298006 (December 27, 2007).

b. Conjugated aromatic polymers

Title:

p-Conjugated Polymer

Author: Assignee:

Masaomi Sasaki et al. Ricoh Company, Ltd. (Yokohama, JP)


Observations:

20070213503 (September 13, 2007) High Mid-2009

Synthesis of p-conjugated organic polyfluorenes. The synthesis of polyfluorenes having lateral high electron field-effect mobility is unreported in the patent literature. Electrophotographic photoconductors Thin-film transistors Organic light-emitting devices Intrinsically conducting materials containing extended p-conjugation along the molecular backbone are extensively reported in the patent literature. They include polyacetylene, poly(phenylenevinylene), poly(paraphenylene), and polyfluorenes. The current art has used the Suzuki cross-coupling reaction to prepare modified polyfluorenes that extended laterally p-conjugation. Although p-extentions of this type have been used in making oxadiazole, thiophene, and fluorenenone, none have demonstrated this extent of favorable electron field-effect mobility.

339

340


REACTION

i. Triethyl phosphate, o-xylene ii. 4-(2-Ethylhexyloxy)-40 -formyltriphenylamine, THF, sodium methylate iii. 2,7-Dipinacol boron-9,9-di-octyl-fluorene, sodium carbonate, tetrakistriphenylphosphine palladium, tricaprylmethylammonium chloride, bromobenzene, phenyl boronic acid

EXPERIMENTAL 1. Preparation of 2,7-dibromo-9-fluorenylphosphonate diethyl A reactor charged with 50 ml triethyl phosphite was heated to 1408C and then treated with the dropwise addition of 2,7,9-tribromofluorene (30.63 g) dissolved in 100 ml of hot o-xylene. The mixture was heated to 1598C for 30 minutes while distilling off ethylbromide and o-xylene. The mixture was then cooled to ambient temperature, excess triethyl phosphite removed under reduced pressure, and a light orange color residue obtained. The product was isolated after recrystallization in cyclohexane as colorless crystals, mp ¼ 119.0 – 119.58C. 2. Preparation of fluorene intermediate The step 1 product (5.67 g) and 4-(2-ethylhexyloxy)-40 -formyltriphenylamine (5.20 g) were dissolved into 30 ml of THF and then treated with the dropwise addition of 28% sodium methylate (3.47 g) dissolved in methanol and then refluxed 1 hour and neutralized with acetic acid. The mixture was poured into water and extracted with toluene, washed with water, dried with MgSO4, and concentrated. The residue was purified using silica gel chromatography with toluene/hexane, 1:2, respectively, and 5.60 g of product isolated as an orange-red glassy solid, mp ¼ 93.0 – 93.58C.

Derivatives

341

3. Preparation of p-conjugated polymer A reactor containing 10 ml of toluene and 10 ml of aqueous Na2CO3 was treated with the step 2 product (1.0 mmol), 2,7-dipinacol boron-9,9-di-octyl-fluorene (1.0 mmol), tetrakis triphenylphosphine palladium (0.01 mmol), and 0.16 ml of tricaprylmethylammonium chloride. The mixture was then treated with a few drops of bromobenzene and then refluxed for 1 hour and treated with a few drop of phenyl boronic acid and then further refluxed 15 hours and cooled. The mixture was diluted with toluene and isolated toluene layer washed with water. The mixture was filtered after adding 40 mg of the palladium scavenger 3-mercaptopropyl modified silica gel. The solution was then poured into methanol and a yellow polymer isolated. The polymer was redissolved in toluene and then purified using a short column of silica gel. The solution was rewashed with water, reprecipitated in ethanol, and 0.80 g of polymer isolated having an Mn of 32,800 Da. DERIVATIVES Step 2 fluorene derivatives and selected polymers are provided in Tables 1 and 2, respectively. TABLE 1. Selected Step 2 Products and Corresponding Melting Pointsa Entry

Structure

Melting Point (8C)

2

96.5 –97.0

9

213.0–213.5

11

176.5–177.0

14

—

a

Limited structural characterization was supplied by the authors of the current invention.

342


TABLE 2. Entry

Physical Properties of Selected p-Conjugated Polymersa Repeat Unit

Mn (Da)

1

19,554

4

14,994

9

146,600

15

Gelled

a

Polymers were prepared using Suzuki cross coupling with tetrakis triphenylphosphine palladium (0).

NOTES 1. Additional p-conjugated polymers, (I), were prepared by the authors (1) and used as photoelectric conversion elements.

Notes

343

2. p-Conjugated organoboron polymers were prepared by DeVito Luebben et al. (2) and used in thin-film organic polymer electronic devices. These p-conjugated organoboron polymers exhibited n-type semiconducting properties, photoluminescence, and electroluminescence.

3. Jacob et al. (3) and Uckert (4) prepared p-conjugated polymers based on 2,7-poly(phenanthrene) derivatives, (III), by polycondensation using Yamamoto cross coupling. Polymeric agents were exemplary organic lightemitting diodes.

4. You et al. (5) prepared organic electroluminescent p-conjugated polymers that contained the 9,9-di(fluorenyl)-2,7-fluorenyl repeat unit, (IV), and that had Mw’s . 175,000 Da.

344


5. p-Conjugated polymers containing spirobifluorene and fluorene units, (V), were prepared by Treacher et al. (6) and used in thin-film transistors and solar cells.

References 1. M. Sasaki et al., U.S. Patent Application 20060247413 (November 2, 2006). 2. S. DeVito Luebben et al., U.S. Patent Application 20070287818 (September 20, 2007). 3. J. Jacob et al., U.S. Patent Application 20070191583 (August 16, 2007). 4. F.P. Uckert, U.S. Patent Application 20070152209 (July 5, 2007). 5. H. You et al., U.S. Patent Application 20070093643 (April 26, 2007). 6. K. Treacher et al., U.S. Patent 7,288,617 (October 30, 2007).

c. Iridium-containing polymers

Title: Polymer Light-Emitting Material and Organic Light-Emitting Element Author: Assignee:

Yoshiaki Takahashi et al. Showa Denko K.K. (Tokyo, JP)


20080050604 (February 28, 2008) High 2010

Preparation of high phosphorescence quantum yield iridium-containing organic light-emitting elements. Organic light-emitting elements consisting of iridium terpolymers with high quantum yields are novel. Organic light-emitting elements Polyvinylcarbazole derivatives containing a substituted phenylpyridine iridium complex or polyethylene modified with {tris[2-(2-pyridyl)phenyl]iridium} are polymeric light-emitting materials previously prepared by this group. Since both materials were characterized as having low phosphorescence quantum yields, limited solvent solubility, and poor film-formability properties, neither has found broad commercial applications. To address the need for solvent-soluble and high-yielding phosphorescence agents, styryl and methacrylate {tris[2-(2-pyridyl)phenyl]iridium} derivatives terpolymerized with holetransporting and electron-transporting materials having high phosphorescence quantum yields and enhanced durability were prepared.

345

346

Polymer Light-Emitting Material and Organic Light-Emitting Element

REACTION

i. ii. iii. iv.

2-Ethoxyethanol, iridium chloride(III) trihydrate (2-Pyridyl) benzaldehyde, toluene, silver trifluoromethanesulfonate Methyl triphenyl phosphonium bromide, THF, n-butyl lithium, hydrochloric acid Triphenylamine intermediate, oxadiazole intermediate, toluene, V-601 EXPERIMENTAL

1. Preparation of iridium complex A reactor was charged with 150 ml of 2-ethoxyethanol, 50 ml of water, and 2-phenylpyridine (58 mmol) and then treated with iridium chloride(III) trihydrate (28 mmol) and refluxed for 12 hours under nitrogen. The solution was slowly cooled to ambient temperature and a precipitate isolated, which was washed with methanol, dried, and 13.5 g of product isolated. 2. Preparation of iridium complex intermediate A mixture consisting of the step 1 product (4.7 mmol), 4-(2-pyridyl) benzaldehyde (9.3 mmol), and 500 ml of toluene was stirred at ambient temperature for several hours and then treated with silver trifluoromethanesulfonate (9.3 mmol). The mixture refluxed for 3 hours and was then cooled to ambient temperature and filtered through Celite and then concentrated. The residue was purified by silica gel column chromatography using chloroform/ethyl acetate, 19:1, respectively, and then recrystallized in CH2Cl2/methanol and 0.95 g of product isolated.

Derivatives

347

3. Preparation of polymerizable iridium complex intermediate Methyl triphenyl phosphonium bromide (0.56 mmol) was dissolved in 10 ml of THF and treated with 1.6 M n-butyl lithium (0.64 mmol) in hexane solution at 08C. The solution was stirred for 30 minutes at 08C and then treated with the step 2 product (0.36 mmol) and stirred an additional 2 hours at ambient temperature. The solution was treated with dilute hydrochloric acid, extracted with chloroform, dried over MgSO4, and concentrated. The residue was purified by silica gel column chromatography using chloroform/hexane, 2:1, respectively, recrystallized using CH2Cl2/ methanol, and 100 mg of product isolated. 1

H-NMR: d 7.79 (m, 3 H), 7.46 (m, 9 H), 6.90 (m, 11 H), 6.55 (dd, 1 H), 5.44 (d, 1 H), 5.00 (d, 1 H)

4. Terpolymerization of iridium complex intermediate A mixture consisting of the step 3 product (80 mg), a polymerizable triphenylamine (460 mg), and an oxadiazole (460 mg) derivative were placed into an airtight vessel and dissolved in 9.9 ml of toluene. This solution was treated with 198 ml of 0.1 M toluene solution of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) and then stirred at 608C for 60 hours. It was then precipitated in 500 ml acetone, redissolved in toluene, and reprecipitated in acetone, the process being repeated twice. The product was isolated in 78% yield having an Mw of 4.2 103 Da. DERIVATIVES TABLE 1. Physical Properties of Iridium Polymers Terpolymerized with Selected Triphenylamine Comonomers Prepared According to the Current Invention Iridium Complex Incorporated (%)

Polymer Yield (%)

Mn (Da)

1-1(a)

7.5

78

4.2 103

1-1(c)

7.4

77

6.4 103

Entry

Iridium Monomer

(Continued)

348


TABLE 1. Continued Iridium Complex Incorporated (%)

Polymer Yield (%)

Mn (Da)

1-1(f)

7.3

80

4.8 103

1-1(g)

7.3

76

5.5 103

Entry

Iridium Monomer

TESTING Organic light-emitting elements were produced using an indium-tin-oxide coated substrate consisting of a 25-mm square glass substrate with two 4 mm-width indium tin oxide (ITO) electrodes and used as an anode and surface of the substrate. Poly[(3,4-ethylenedioxythiophene)-co-styrene sulfonate] was initially applied onto the ITO anode to form an anode buffer layer. Thereafter 90 mg of a selected experimental agent dissolved in toluene was applied by spin coating and then dried. Electronic testing results are provided in Table 2.

Notes

349

TABLE 2. Light Emission and Durability Properties of Selected Organoiridium Light-Emitting Elements Entry 1-1(a) 1-1(a) Comparative 1-1(c) 1-1(c) Comparative 1-1(f) 1-1(f) Comparative 1-1(g) 1-1(g) Comparative

Maximum External Quantum Efficiency (%)

Maxium Luminance (cd/m2)

Brightness Half-life (h)

7.6 4.1 4.7 1.4 6.2 3.0 5.9 1.6

72,000 31,000 59,000 16,000 65,000 20,000 22,000 7,000

2,200 500 1,300 200 3,300 500 1,700 200

NOTES 1. Polymerizable triphenylamine and oxadiazole comonomers are illustrated below.

2. A luminescent unit was prepared by the Shinozaki et al. (1) by mixing iridium complexes, (I) and (II), with bisphenol A diglycidyl ether and 5-methylhexahydrophthalic anhydride. Additional luminescent derivatives, (III) and (IV), were prepared by Igarashi (2).

350


3. In a previous investigation by the authors (3) polymerizable gold complexes, (V) and (VI), were prepared and used in organic polymer light-emitting elements.

4. Ma et al. (4) prepared organic light-emitting devices (OLED) where the organic layer consisted of an iridium derivative having two or three bidentate ligands, (VII), which showed improved stability and efficiency when incorporated into an OLED.

Notes

351

References 1. K. Shinozaki et al., U.S. Patent Application 20070292631 (December 20, 2007). 2. T. Igarashil, U.S. Patent 7,329,898 (February 12, 2008). 3. Y. Takahashi et al., U.S. Patent Application 20060269779 (November 30, 2006) and U.S. Patent Application 20060009629 (January 12, 2006). 4. B. Ma et al., U.S. Patent 7,332,232 (February 19, 2008).

d. Polybiphenylheterocyclics

Title: New Polymer and Polymer Light-Emitting Device Using the Same Author: Assignee:

Satoshi Kobayashi et al. Sumitomo Chemical Company, Ltd. (Tsukuba-shi, JP)


352

20080103278 (May 1, 2008) High 2010

Synthesis of high-molecular-weight biphenylpolyheterocyclics useful as polymer light-emitting devices. Biphenyl-based polyheterocyclics are unreported in the patent literature. Polymer LEDs High-molecular-weight polyheterocyclics were prepared by Suzuki coupling of biphenyl dihaloheterocyclic derivatives that had excellent electronic transporting properties. These materials were then used as components in polymer light-emitting device materials or as chargetransporting agents. Unlike low-molecular-weight analogs, these highmolecular-weight light-emitting materials were soluble in organic solvents and could be converted into light-emitting layers or chargetransporting layers by coating methods.

Experimental

353

REACTION

i. ii. iii. iv. v.

N,N-Dimethylformamide, N-bromosuccinimide Magnesium, THF, 1,2-dibromoethane Trimethyl phosphate, iodine, bromine Diethyl ether, n-butyl lithium, sulfur N,N 0 -Bis(4-bromophenyl)-N,N 0 -bis(4-n-butyl phenyl)-1,4-phenylenediamine, 2,20 -bipyridyl, THF, bis(1,5-cyclo octadiene) nickel EXPERIMENTAL

1. Preparation of 2,20 -dibromo-5,50 -dioctyloxy-1,10 -biphenyl 3,30 -Dioctyloxy-1,10 -biphenyl (133 g) was dissolved in 1820 ml of N,N-dimethylformamide at 08C and treated with the dropwise addition of N-bromosuccinimide (117.5 g) dissolved in 910 ml N,N-dimethylformamide over 60 minutes. Thereafter the mixture was warmed to ambient temperature and stirred overnight. It was then treated with water, extracted with n-hexane, and concentrated. The residue was recrystallization in 2-propanol and 122 g of product isolated. 1

H-NMR (CDCl3) d 0.88 (t, 6H), 1.2 1.8 (m, 24H), 3.95 (t, 4H), 6.7 6.8 (m, 4H), 7.52 (d, 2H)

2. Preparation of 2,20 -di-iodo-5,50 -dioctyloxy-1,10 -biphenyl A flask was charged with magnesium (4.05 g) under a nitrogen atmosphere. A separate flask was charged with 200 ml THF solution containing the step 1 product (45 g) and where 20 ml of this solution was added in the flask containing magnesium. The magnesium flask was then treated with five drops of 1,2-dibromoethane as the initiator and heated. When the exothermic reaction started, the remaining THF solution containing the step 1 product was added dropwise over 30 minutes and then refluxed for 1 hour. The solution was then cooled to 08C and treated with the dropwise addition of 150 ml THF solution containing iodine (44.2 g) and then stirred overnight. It was then treated with water, extracted with chloroform, washed with aqueous sodium thiosulfate and saturated NaCl aqueous solution, dried, and concentrated. After recrystallization using 2-propanol, 43 g of product was isolated. 1 H-NMR (CDCl3) d 0.90 (t, 6H), 1.2 1.8 (m, 24H), 3.93 (t, 4H), 6.6 6.8 (m, 4H), 7.74 (d, 2H) MS (APCI(þ)): Mþ 662

354

New Polymer and Polymer Light-Emitting Device Using the Same

3. Preparation of 4,40 -dibromo-2,20 -di-iodo-5,50 -dioctyloxy-1,10 -biphenyl A mixture consisting of the step 2 product (37 g) and 800 ml trimethyl phosphate were charged into a flask and treated with iodine (10.6 g) and the dropwise addition of bromine (19 g) dissolved in 70 ml trimethyl phosphate. After stirring for 4 hours additional bromine (9.5 g) dissolved in 35 ml of trimethyl phosphate was added and the mixture stirred overnight. The reaction liquid was then poured into water, extracted with chloroform, and washed with aqueous solutions of sodium thiosulfate and brine. The solution was then dried, concentrated, the residue purified by silica gel chromatography using cyclohexane/toluene, 20:1, respectively, and 20.5 g of product isolated. H-NMR (CDCl3) d 0.88 (t, 6H), 1.2 1.9 (m, 24H), 3.99 (m, 4H), 6.70 (s, 2H), 8.03 (s, 2H) MS (APCI(þ)): Mþ 820

1

4. Preparation of polymer precursor A flask was charged with the step 3 product (6.1 mmol) and 50 ml diethyl ether and then cooled to 2908C and treated with the dropwise addition of 8.4 ml n-butyl lithium (1.6 M n-hexane solution; 13.4 mmol). After 1 hour of stirring the mixture was treated with sulfur (6.1 mmol). The temperature was then raised to ambient temperature for 1 hour and then treated with additional sulfur (6.1 mmol) and stirred for 3.5 hours. The mixture was then treated with the dropwise addition of 15 ml of 1 M hydrochloric acid. The aqueous phase was extracted with diethyl ether, the organic layer collected, washed with water and saturated brine aqueous solution, and dried. The mixture was concentrated and the residue purified by silica gel column chromatography using hexane/ethyl acetate, 20:1, respectively, and 0.91 g of product isolated. 1

H-NMR (CDCl3) d 7.69 (s, 2H), 7.08 (s, 2H), 4.09 (t, 4H), 1.92–1.81 (m, 4H), 1.58–1.26 (m, 20H), 0.88 (t, 6H)

5. Preparation of polymer A mixture consisting of the step 4 product (0.35 g), N,N 0 -bis(4-bromophenyl)-N,N 0 bis(4-n-butyl phenyl)-1,4-phenylenediamine (0.16 g), 2,20 -bipyridyl (0.37 g), and 28 ml of THF containing bis(1,5-cyclo octadiene) nickel(0) (0.70 g) was heated to 608C for 3 hours. The solution was then cooled and poured into a solution of 25% aqueous ammonia 10 ml/methanol 120 ml and 50 ml of ion-exchanged water, stirred for 1 hour, and the precipitate collected by filtration. The precipitate was then washed with ethanol, dried, dissolved in 30 ml toluene, treated with 30 ml 1 M hydrochloric acid, and stirred for 1 hour. The aqueous layer was isolated and then treated with 30 ml 4% aqueous ammonia, stirred for 1 hour, and the aqueous layer removed. The organic layer was added dropwise to 200 ml methanol, stirred for 1 hour, and the precipitate isolated. It was dried and redissolved in 30 ml toluene and then purified by passing through an alumina column (20 g) and then reprecipitated in 250 ml methanol. The precipitate was filtered, dried, and 0.13 g of product isolated having an Mn of 6.2 103 Da and Mw of 5.1104 Da.

Testing

355

DERIVATIVES

TESTING Fluorescence Evaluation Experimental agents were evaluated for fluorescent properties using thin films prepared from 2 wt% chloroform solutions and results summarized in Table 1.

TABLE 1. Fluorescent Properties of Experimental Agents Obtained Using Thin Films Prepared Using Chloroform Entry Step 5 product Polymer 1 Polymer 2 Polymer 3

Fluorescence Peak Wavelength (nm) 516 468 466 458

356

New Polymer and Polymer Light-Emitting Device Using the Same

NOTES 1. A fluorescence light was emitting polymeric iridium complex, (I), and a copolymer containing a fluoreneyl component, (II), was prepared by Nakatani et al. (1) and used as a polymer light-emitting device.

2. Luminescent polymer compositions, (III), were prepared by Uetani et al. (2) and used as polymer light-emitting devices.

3. Noguchi et al. (3) prepared 9(10H )-acridone polymers, (IV), for use in light-emitting devices that showed fluorescence in the solid state.

Notes

357

4. Functionalized polynorbornene derivatives, (V), prepared by Liaw et al. (4) using ring-opening metathesis polymerization exhibited strong carbazole fluorescence. Monomer emissions occurred in the near ultraviolet (UV) at approximately 380 nm and extended into the blue-violet region at 330 nm.

References 1. T. Nakatani et al., U.S. Patent Application 20070051922 (March 8, 2007). 2. Y. Uetani et al., U.S. Patent Application 20070020479 (January 25, 2007). 3. T. Noguchi et al., U.S. Patent Application 20080088228 (April 17, 2008). 4. D.-J. Liaw et al., U.S. Patent 7,368,509 (May 6, 2008).

e. Polycarbazoles

Title:

Carbazolyl Monomers and Polymers

Author: Assignee:

Qing Ye et al. General Electric Company (Schenectady, NY)


358

20080138625 (June 12, 2008) High December, 2009

Synthesis of carbazole poly(terephthate ester-co-carbonate) and sulfone derivatives. Although LEDs containing polycarbazole have been prepared carbazole terephthate esters, carbonates, and sulfones are new and unreported. Organic light-emitting devices The application relates to the preparation of high quantum yielding carbazole polymers. Monomers 9-(3,5-hydroxyphenyl)- and 9-(2,5-hydroxyphenyl)-carbazole were prepared by halide displacement and then condensed with 1,4-terephthaloyl dichloride to form the polyester. Halide displacement reactions of 9-(3,5-hydroxyphenyl)- and 9-(2,5hydroxyphenyl)-carbazoles was also used to prepare polyethers, polycarbonates, polyester carbonates, polyetherketones, and polyethersulfones. Carbazole polymers have also shown promise as host molecules in the presence of metal containing emissive guest molecules.

Experimental

359

REACTION

i. Bromo-3,5-dimethoxybenzene, potassium phosphate, copper iodide, dioxane, dimethylethylene diamine ii. CH2Cl2, boron tribromide iii. 1,4-Terephthaloyl dichloride, CHCl3, triethylamine, cumylphenol EXPERIMENTAL 1. Preparation of 9-(3,5-dimethoxyphenyl)-carbazole A flask was charged with 1-bromo-3,5-dimethoxybenzene (7.1 mmol), carbazole (7.1 mmol), potassium phosphate (14.2 mmol), and copper iodide (0.7 mmol) and then treated with 40 ml dioxane. Dimethylethylene diamine (1.6 mmol) was then added to the flask under a strong purge of argon and the mixture heated to 958C for 48 hours. After the reaction was complete [as indicated by thin-layer chromatography (TLC) monitoring], the solution was cooled to ambient temperature and treated with 10 ml of water. The mixture was then extracted with CH2Cl2 and the organic and aqueous phases separated. The organic phase was washed twice with 100 ml of water and once with 100 ml of brine and then dried over Na2SO4. The mixture was concentrated and the residue redissolved in CH2Cl2 and treated with hexanes until colored residues precipitated from solution. After filtration the product was isolated as a yellow oil in 46.5% yield. 1

H-NMR (CDCl3) d 7.98 (d, 2H), 7.35 (d, 2H), 7.23 (d, 2H), 7.11 (t, 2H), 6.6 (s, 2H), 6.43 (s, 1H), 3.65 (s, 6H) EI-MS: 303(Mþ)

2. Preparation of 9-(3,5-hydroxyphenyl)-carbazole A flask was charged with the step 1 product (103 mmol) and then treated with 200 ml of CH2Cl2 and cooled in a dry ice-acetone bath. It was then treated with 1 M boron

360


tribromide (180 mmol in CH2Cl2) and the flask chilled in the dry ice bath, which equilibrated to ambient temperature overnight. The solution was decanted into 100 ml of ice water while stirring. After 30 minutes of hydrolysis the organic layer was extracted twice with 200 ml of CH2Cl2 and the organic layer washed twice with 200 ml of cold water to neutralize excess BBr3. The solution was then dried with Na2SO4, concentrated, and after recrystallization from THF/hexanes, the product was isolated in 44.98% yield. 1

H-NMR (CDCl3) d 8.15 (d, 2H), 7.52 (d, 2H), 7.44 (t, 2H), 7.32 (t, 2H), 6.66 (s, 2H), 6.47 (s, 1H)

3. Preparation of carbazole copolymer A mixture consisting of the step 2 product (1.441 mmol), 1,4-terephthaloyl dichloride (1.456 mmol), and 4 ml of CHCl3 were charged into a flask and the milky solution immersed in an ice-salt bath for 15 minutes. This mixture was then treated with 0.533 ml of dry triethylamine whereupon the solution immediately became clear. The solution was maintained at 0 – 58C for 1 hour and then warmed to ambient temperature and stirred an additional hour. It was then treated with cumylphenol (0.0032 g) and then diluted with 5 ml of CH2Cl2 and washed successively twice with equal volumes of 1 M HCl and water and then precipitated in 40 ml of methanol. The polymer was redissolved in 10 ml of CH2Cl2 and then slowly added to 100 ml of boiling water. Solids were again collected, air-dried, redissolved in 4 ml CH2Cl2, and reprecipitated into methanol. The polymer was dried at 808C overnight and 0.3747 g of product isolated having an Mn of 4,241 Da with a poly dispersity index (PDI) of 1.61.

DERIVATIVES Other step 3 derivatives prepared using 9-(2,5-hydroxyphenyl)-carbazole and 9-(3,5hydroxyphenyl)-carbazole as comonomers are illustrated below.

Notes

361

NOTES 1. Additional polycarbazole derivatives, (I), were prepared by the authors (1) in an earlier investigation and are discussed.

2. A polymerizable carbazole composition, (II), was prepared by Kanno et al. (2) that was radiation cured and used as an adhesive.

3. Anionic carbazole derivatives, (III), were prepared by Frampton et al. (3) and used in light-emitting devices.

362


4. Tetraphenylsilane carbazole derivatives, (IV), were prepared by Chen et al. (4) and used as host material for dopants in organic light-emitting diodes.

5. Thiophene containing carbazole polymers, (V), were prepared by Leclerc (5) and used as light-emitting diodes.

References 1. Q. Ye et al., U.S. Patent Application 20080135806 (June 12, 2008). 2. M. Kanno et al., U.S. Patent Application 20080044149 (February 21, 2008). 3. M. Frampton et al., U.S. Patent Application 20080036368 (February 14, 2008). 4. C.-T. Chen et al., U.S. Patent Application 20070173657 (July 26, 2007). 5. M. Leclerc, U.S. Patent Application 20070069197 (March 29, 2007).

f. Polydibenzosilols

Title: Dibenzosilol Polymers, Their Preparation and Uses Author: Assignee:

Carl R. Towns Cambridge Display Technology, Limited (GB)

U.S. Patent Application Material Patentability: Anticipated Issuing Date: Research Focus: Originality: Application:

Observation:

20070248839 (October 25, 2007) High Late 2009

Preparation of dibenzosilole copolymers as light-emitting devices with enhanced oxidative degradative resistance. Solvent-soluble dibenzosiloles having enhanced oxidative resistance are unreported in the patent literature. Organic light-emissive device Polymer light-emissive device Photovoltaic device Electroluminescent materials A novel class of solvent-soluble conjugated dibenzosilole copolymers have been prepared by Suzuki coupling. Several of these conjugated and nonconjugated light-emitting devices were initially prepared by the author in earlier investigations using high-activity Suzuki coupling agents. Cyclic voltammetry demonstrated that dibenzosilole copolymers of the current application have higher electron affinities and were more electrochemically stable. Cyclic voltammetry also confirmed that these copolymers were less prone to oxidative degradation, which would be reflected in LEDs having longer lifetimes. In addition since oxidative degradation and associated polymer aggregation causes blue electroluminescent materials to shift over time toward longer wavelengths, this effect would be absent in these dibenzosilole copolymers.

363

364

Dibenzosilol Polymers, Their Preparation and Uses

REACTION

i. ii. iii. iv.

Hydrochloric acid, sodium nitrite, potassium iodide t-Butyllithium, THF, dichlorodihexylsilane t-Butyllithium, THF, 2-isopropoxy-4,40 ,5,50 -tetramethyl-1,3,2-dioxaboralane 2,7-Bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-dihexy-fluorene, palladium(II) acetate, tricyclohexylphosphine, toluene, tetraethylammonium hydroxide EXPERIMENTAL

1. Preparation of 4,40 -dibromo-2,20 -diiodo-biphenyl 4,40 -Dibromo-biphenyl-2,20 -diamine (14.6 mmol) was suspended in 16 ml of 16% aqueous hydrochloric acid at 08C and treated with sodium nitrite (31.9 mmol) while maintaining the temperature at 08C. After an additional hour of stirring 5 ml of KI solution (30.1 mmol) was added dropwise to the reaction mixture at 2108C. The reaction mixture was slowly warmed to ambient temperature and then heated to 508C for 2 hours. It was then cooled to ambient temperature and basified with 90 ml of 10% aqueous NaOH and the product extracted into diethyl ether. The organic layer was washed with brine, dried with anhydrous MgSO4, and concentrated. After purification by chromatography using hexane 1.4 g of product was isolated as an off-white solid, mp ¼ 898C. FTIR (neat, cm21) 710, 817, 993, 1086, 1448, 1565 1 H-NMR (CDCl3) d 7.03 (2H, d, J 8.2, ArH), 7.55 (2H, dd, J 8.2 1.9, ArH), 8.08 (2H, d, ArH) 13 C-NMR (CDCl3) d 99.8, 122.5, 130.7, 131.4, 141.0, 146.8

Experimental

365

2. Preparation of 2,7-dibromo-9,90 -dihexyl-9H-9-dibenzosiloledibenzosilole t-Butyllithium (10.6 mmol; 1.7 M in pentane) was added over 2 hours to a solution of the step 1 product (2.66 mmol) dissolved in 30 ml THF at 2908C and then stirred an additional hour at 2908C. This solution was then treated with dichlorodihexylsilane and the mixture stirred at ambient temperature overnight and then quenched with distilled water. The mixture was concentrated to remove THF and the residue dissolved in diethyl ether. The organic layer was washed with brine, dried with anhydrous MgSO4, and concentrated. After purification by chromatography using hexane 0.7 g of product was isolated as a colorless oil. FTIR (neat, cm21) 720, 813, 1001, 1072, 1384, 2855, 2923, 2956 1 H-NMR (CDCl3) d 0.84– 0.97 (10H, m, CH2þCH3), 1.22– 1.36 (16H, m, CH2), 7.55 (2H, dd, J 8.3, 2.0, ArH), 7.64 (2H, d, J 8.3, ArH), 7.70 (2H, ArH) 13 C-NMR (CDCl3) d 12.0, 14.0, 22.5, 23.7, 31.3, 32.9, 122.2, 122.5, 133.0, 140.4, 146.0

3. Preparation of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)9,9-dihexyl-9H-9-dibenzosiloledibenzosilole t-Butyllithium (2.02 mmol; 1.7 M in pentane) was added over 30 minutes to a solution of the step 2 product (0.49 mmol) dissolved in 3 ml THF at 2788C and then stirred for an additional hour and treated dropwise with 2-isopropoxy-4,40 ,5,50 -tetramethyl1,3,2-dioxaboralane (2.02 mmol). The mixture stirred overnight at ambient temperature and was then quenched with distilled water and concentrated to remove THF. The product was extracted into diethyl ether and the organic layer washed with brine, dried, and concentrated. The residue was purified by chromatography with hexane and 0.22 g of product isolated as a white solid. FTIR (neat, cm21) 1093, 1143, 1345, 1597, 2922 13 C-NMR (CDCl3) d 12.3, 14.1, 22.6, 23.8, 24.9, 31.3, 33.0, 83.7, 120.5, 136.8, 137.5, 139.7, 151.0 29 Si (CDCl3) d 3.2

4. Preparation of poly(9,9-dihexyl-2,7-fluorenyl-co-9,9-dihexyl-2,7silafluorenyl) A Schlenk tube was charged with the step 3 product (0.17 mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)-9,9-dihexy-fluorene (0.17 mmol), palladium(II) acetate (45 mmol), and tricyclohexylphosphine (178 mmol). This mixture was then treated with 2.5 ml of toluene and then stirred at 908C for 5 minutes and further treated with 1 ml of 20% aqueous tetraethylammonium hydroxide solution. After stirring an hour the mixture became viscous and was treated with an additional 1 ml of toluene and then further stirred for 1 hour. It was treated then with phenylboronic acid (17 mmol), stirred 1 hour, and then treated with bromobenzene (17 mmol). After stirring an additional hour, the mixture was cooled to ambient temperature and precipitated by pouring into 30 ml of stirring methanol. The precipitate was isolated, redissolved in 10 ml toluene, and reprecipitated in 50 ml stirring methanol. The precipitated material was filtered, dried, and 100 mg of product isolated as a pale grayish green solid.

366


Mw ¼ 4.24 105 Mw ¼ 1.09 105 FTIR (neat, cm21) 734, 815, 1064, 1252, 1378, 1426, 1452, 2854, 2923, 2954 1 H-NMR (CDCl3) d 0.74 –0.89 (m, CH2þCH3), 1.00– 1.20 (m, CH2), 1.20–1.55 (m, CH2), 2.10 (brs, CCH2), 7.50 –8.00 (m, ArH) 13 C-NMR (CDCl3) d (125 MHz, CDCl3) 12.4, 14.0, 14.1, 22.56, 22.59, 23.8, 24.0, 29.7, 31.4, 31.5, 33.1, 40.4, 55.3, 120.0, 121.2, 121.4, 125.3, 128.2, 129.2, 131.9, 138.9, 140.1 (2 signals), 140.3, 147.1, 151.7 29 Si (CDCl3) d 3.02

DERIVATIVES A summary of UV –Vis measurements and cyclic voltammetry testing results for silafluorenyl copolymers are provided in Tables 1 and 2, respectively. TABLE 1.

Absorption Maxima and Optical Bandgaps for Experimental Polymersa lmax (soln)b (nm)

lmax (film) (nm)

Egopt (soln)c (eV, nm)

Egopt (soln) (eV, nm)

PF6

394

390

2.98 (416)

2.93 (423)

A

332

334

3.30 (376)

3.23 (383)

B

400

394

2.87 (432)

2.92 (425)

Entry

a

Repeat Unit

UV–Vis absorption was measured in hexane. Optical band gap, Egopt (eV) ¼ 1240/absorption edge (nm). c Band gaps of the polymers measured from the UV absorption onsets. b

Notes

367

TABLE 2. Cyclic Voltammetry Testing for Selected Silafluorenyl Polymersa Entry A B

Eonset(ox) (V)

Eopt g (eV)

HOMOb (eV)

LUMOc (eV)

1.57 1.48

3.23 2.92

26.00 25.91

22.77 22.99

a Testing was conducted by spin-coating experimental agents onto a gold working electrode in a solution of acetonitrile containing Bu4NClO4 at a scan rate of 50 mV/s. b HOMO ¼ highest occupied molecular orbital. c LUMO ¼ lowest unoccupied molecular orbital.

NOTES 1. The modified Suzuki polymerization catalyst, dichlorobis(tri-o-tolylphosphine) palladium(II), was also used to prepare poly(2,7-(9,9-di-n-octylfluorene)-3,6benzothiadiazole), (I).

2. Towns et al. (1,2) prepared light-emissive terpolymers, (II), where the first monomer comprised a region for transporting negative-charge carriers and having a first bandgap defined by a first LUMO level and a first HOMO level. The second monomer comprised a region for transporting positive-charge carriers and having a second bandgap defined by a second LUMO level and a second HOMO level. Finally, a third monomer comprised a medium for accepting and combining positive and negative charge carriers to generate light having a third bandgap defined by a third LUMO level and a third HOMO level.

368


3. A method for preparing silacyclopentadiene derivations, (III), and (IV), effective as electroluminescence elements is described by Uchida et al. (3).

References 1. C. Towns et al., U.S. Patent 7,173,103 (February 6, 2007). 2. C. Towns et al., U.S. Patent 6,887,973 (March 3, 2005) and U.S. Patent 6,861,502 (March 1, 2005). 3. M. Uchida et al., U.S. Patent 6,051,319 (April 18, 2000) and U.S. Patent 5,986,121 (November 16, 1999).

g. Poly(fluorene-co-triphenylamines)

Title:

Hole Transport Polymers

Author: Assignee:

Nora Sabina Radu et al. E.I. DuPont De Nemours and Company (Wilmington, DE)


20080071049 (March 20, 2008) Moderate 2011

Synthesis of poly(fluorene-co-triphenylamine) derivatives as hole transport polymers. Ongoing 5-year investigation. Organic light-emitting diodes Two poly(fluorene-co-triphenylamine) derivatives effective as organic light-emitting diodes in organic photoactive layers were prepared in five steps. Polymers were prepared by Yamamoto polymerization using bis(1,5-cyclooctadiene)-nickel-(0), 2,20 -bipyridyl and 1,5-cyclooctadiene. Materials in this application were also prepared by Suzuki polymerization using nickel chloride–biphenyl complex, zinc, and triphenyphosphine. Similar hole transport properties were also observed for triphenylamine macromolecules, oligomers, and polymers.

369

370


REACTION

i. Phenylboronic acid, palladium dibenzanthracene, t-butylphosphine, toluene, potassium fluoride ii. Palladium dibenzanthracene, t-butylphosphine, toluene, sodium t-butoxide iii. Palladium dibenzanthracene, t-butylphosphine, toluene, sodium t-butoxide iv. 1-Bromo-4-iodobenzene, palladium dibenzanthracene, DPPF, toluene, sodium t-butoxide v. Bis(1,5-cyclooctadiene)-nickel(0), dimethylformamide, 2,20 -bipyridyl, 1,5cyclooctadiene, toluene, 2,7-dibromo-9,90 -( p-vinylbenzyl)-fluorine

EXPERIMENTAL 1. Preparation of 9,9-dioctyl-2,7-diphenylfluorene Under an atmosphere of nitrogen a 250-mL round bottom was charged with 9,9dioctyl-2,7-dibromofluorene (45.58 mmol), phenylboronic acid (100.28 mmol), palladium dibenzanthracene (0.46 mmol), t-butylphosphine (1.09 mmol), and 100 ml toluene. The reaction mixture was stirred for 5 minutes and then treated with potassium fluoride (150.43 mmol) in two portions and the solution stirred at ambient temperature overnight. It was then diluted with 500 ml of THF, filtered through a plug of silica and celite, volatiles removed under reduced pressure, and a yellow oil isolated. The residue was purified by flash column chromatography on silica gel using hexanes as eluent and 19.8 g of product isolated as a white solid.

Experimental

371

2. Preparation of 9,9-dioctyl-2,7-(4-bromophenyl)fluorene A flask was charged with the step 1 product (36.48 mmol) dissolved in 100 ml CH2Cl2 and then cooled to 2108C and treated with the dropwise addition of bromine (76.60 mmol) dissolved in 20 ml CH2Cl2. It was stirred for 1 hour at 08C and then overnight at ambient temperature. The mixture was then treated with 100 ml of 10% Na2S2O3 solution and stirred an additional hour. The organic layer was extracted and the water layer washed three times with 100 ml CH2Cl2, extracts combined, dried with Na2SO4, and then concentrated and precipitated in acetone. After filtration and drying 13.3 g of product were isolated as a white powder. 3. Preparation of 9,9-dioctyl-2,7-(4-N-phenylamino)phenyl)fluorene Under an atmosphere of nitrogen a flask was charged with the step 2 product (18.70 mmol), aniline (39.27 mmol), palladium dibenzanthracene (0.37 mmol), tbutylphosphine (0.75 mmol), and 100 ml toluene. The reaction mixture stirred for 10 minutes and was then treated with sodium t-butoxide (38.33 mmol) and continued stirring for 24 hours. The mixture was diluted with 3 liters of toluene and filtered through a plug of silica and celite, concentrated, and a dark brown oil obtained. The residue was purified by flash column chromatography on silica gel using a mixture of ethyl acetate/hexanes, 1:10, respectively, and 6.8 g product isolated as a pale yellow powder. 4. Preparation of 9,9-dioctyl-2,7-(N-40 -bromophenyl)(4-N-phenylamino) phenyl)fluorene A 250-ml flask was charged with the step 3 product (5.52 mmol), 1-bromo-4-iodobenzene (16.55 mmol), palladium dibenzanthracene (0.33 mmol), DPPF (0.66 mmol), and 80 ml toluene. The mixture stirred for 10 minutes and was then treated with sodium t-butoxide (12.14 mmol) and heated to 808C for 4 days. It was then diluted with 1 liter of toluene and 1 liter of THF, filtered through a plug of silica and celite to remove insoluble salts, and concentrated to a brown oil. The residue was purified by flash column chromatography on silica gel using CH2Cl2/hexanes, 1:10, respectively, and 4.8 g product isolated as a yellow powder. 5. Preparation of fluorene polymer Bis(1,5-cyclooctadiene)-nickel(0) (3.03 mmol) was added to 6 ml of N,N-dimethylformamide containing 2,20 -bipyridyl (3.03 mmol) and 1,5-cyclooctadiene (3.03 mmol) and then heated to 608C for 30 minutes. A solution of 24 ml toluene containing the step 4 product (1.50 mmol) was then quickly added to the catalyst mixture and stirred at 608C for 7 hours and then cooled to ambient temperature. It was then poured into 250 ml methanol and stirred overnight and then treated with 15 ml 12 M hydrochloric acid and stirred an additional hour. The precipitate was filtered, dissolved in 50 ml of toluene, and reprecipitated in 500 ml of methanol and then isolated by filtration. The solid was purified by chromatography using silica gel and toluene and then

372


reprecipitated in ethyl acetate. After drying 1.08 g of product was isolated as a yellow solid having an Mn of 148,427 Da, Mw of 477,886 Da, with a PDI of 3.25.

DERIVATIVES A second fluorene copolymer was also prepared and illustrated below.

TESTING Initial current, voltage, luminance, color coordinate properties, and luminance degradation properties were evaluated for the step 5 product and a styryl comparative. Testing results are provided in Table 1. TABLE 1. Effects of Constant and Prolonged Current on Electronic Properties of Step 5 Product and Distyryl Comparative


Color Curr. Coordinate Eff’cy Lum Properties (cd/A) Voltage (cd/m2) (x)

Color Coordinate Properties ( y)

4.4

5.1

426

0.133

0.148

4.4

5.8

371

0.134

0.156

Lum Half Life (h) 1100 (projected) 215

Life Test Lum (cd/m2) 2245 2093

Notes

373

NOTES 1. Other aromatic amines, (I), and perfluoropolyaromatic amines, (II), were previously prepared by the authors (1,2), respectively, and were used in hole transport layers.

374


2. Monomers, (III) and (IV), having pendant triarylmethane groups were prepared by Herron et al. (3) and then free radically polymerized and used as hole transport polymers.

3. Polythiophene derivatives, (V), were prepared by Towns et al. (4) and used in hole transport layers.

4. Mizusaki et al. (5) prepared triphenylamine copolymers, (VI), which had hole transport properties that were used in organic electroluminescent devices.

Notes

375

References 1. N.S. Radu et al., U.S. Patent Application 20070232782 (October 4, 2007). 2. N.S. Radu et al., U.S. Patent Application 20070228364 (October 4, 2007). 3. N. Herron et al., U.S. Patent Application 20050187364 (August 25, 2005) and U.S. Patent Application 20070194698 (August 23, 2007). 4. C. Towns et al., U.S. Patent Application 20080053520 (March 6, 2008). 5. M. Mizusaki et al., U.S. Patent 7,345,141 (March 18, 2008).

h. Polyconjugated phenoxazines

Title: Polymer Compound and Organic Light-Emitting Device Using the Same Author: Assignee:

Sang-Hoon Park Samsung Electronics Co., Ltd. (Suwon-si, KR)


Observations:

376

20070278455 (December 6, 2007) Very high Mid-2010

Development of polyconjugated phenoxazines effective as organic lightemitting devices. Ongoing 7-year investigation. Organic light-emitting devices Polymer light-emitting devices Organic light-emitting diodes are self-luminescent devices that emit light when electrons and holes are recombined in a fluorescent or phosphor organic layer when current flows to the fluorescent or phosphor organic layer. In 2007 this group filed 15 significant U.S. patent applications associated with light-emitting devices. This included the development of blue and white organic electroluminescent devices from phenoxazole, spirobiphenylene, 1,4-dimethylene-cyclohexanes, azole, and cyclopentaphenanthrene derivatives. Film preparation of experimental materials using spin coating with accuracies of 2–5 nm and with light-emitting efficiencies exceeding 6% using phenoxazine-based polymers having Mn’s of 35,000 Da.

Reaction

377

REACTION

i. Phenoxazine, sodium t-butoxide, tris(dibenzylidene acetone)dipalladium(0), tri(tbutyl)-phosphine, xylene ii. Bromine, chloroform iii. Oxygen, acetone, 4-bromophenylacetylene, copper chloride, N, N,N0 , N0 tetramethylethylenediamine iv. p-Toluidine, copper(I) chloride v. Aluminum trichloride, chloroform, octanoylchloride vi. Bis(1,5-cyclooctadiene)nickel(0), bipyridal, dimethylfuran, 1,5-cyclooctadiene, toluene 1. Preparation of phenoxazine derivative A mixture consisting of phenoxazine (54 mmol), sodium t-butoxide (77 mmol), tris(dibenzylidene acetone)dipalladium(0) (1.1 mmol), and tri(t-butyl)-phosphine (1.1 mmol) were dissolved in 250 ml of xylene and then heated to 808C for 12 hours. Thereafter, the reaction mixture was cooled to ambient temperature, quenched with 200 ml of distilled water, and extracted with xylene/water, 1:1.

378

Polymer Compound and Organic Light-Emitting Device Using the Same

The organic layer was dried with MgSO4, concentrated, and purified by silica gel column chromatography using toluene/hexane, 1:2, respectively. After reconcentrating 18.5 g of product was isolated. 2. Preparation of phenoxazine intermediate The step 1 product (13 mmol) was dissolved in 150 ml of CHCl3 and then slowly treated with bromine (2.1 eq) at 08C. After stirring for 10 minutes, excess bromine was quenched by adding a small quantity of acetone to the reaction mixture. Thereafter the organic layer was extracted with water/CHCl3, 2:1, respectively, and the organic layer dried with MgSO4. The mixture was then concentrated, precipitated in methanol, and 6 g of product isolated. 1

H-NMR (CDCl3) d 0.91 (m, 6H); 1.45 (m, 8H); 1.82 (m, 1H); 3.89 (d, 2H); 5.82 (d, 2H); 6.5–7.5 (m, 8H)

3. Preparation of 1,4-diphenyl-1,4-butadiyne derivative A reactor was charged with 500 ml of acetone, 4-bromophenylacetylene (225 mmol), copper chloride(I) (14 mmol), and N, N,N0 , N0 -tetramethylethylenediamine (14 mmol) and stirred for 1 hour at ambient temperature while bubbling in oxygen. The mixture was then concentrated, precipitated in 5% hydrochloric acid, and a light-yellow solid isolated. The solid was recrystallized in CHCl3, dried, and 39.8 g of product isolated as a light-yellow solid product, mp ¼ 264– 2658C. 4. Preparation of triphenyl pyrrole derrivative A reactor was charged with the step 3 product (88 mmol), p-toluidine (88 mmol), and copper(I) chloride (22 mmol) and then stirred for 5 hours at 2008C. It was cooled to ambient temperature and then dissolved in CHCl3 and washed several times with 5% hydrochloric acid, water, and then dried with MgSO4. Thereafter the mixture was concentrated, the residue purified by recrystallization in ethyl acetate, and 28.5 g product isolated as a white solid. 5. Preparation of triphenyl pyrrole intermediate At ambient temperature a reactor was charged with aluminum trichloride (5.1 mmol), 50 ml of CHCl3, octanoylchloride (5.1 mmol) diluted in 10 ml of CHCl3, and treated with the step 4 product (4.8 mmol) dissolved in 20 ml CHCl3. The mixture was heated to 508C for 24 hours and then poured onto 100 g of ice. The organic layer was isolated, washed several times with water, and dried using MgSO4. The solution was then concentrated and the residue purified by chromatography using ethyl acetate/ hexane, 1:5, respectively, and 1.97 g product isolated as a viscous light-yellow oil. 1

H-NMR (CDCl3) d 0.86 (t, 3H, ZCH3), 1.13– 1.75 (m, 10H, ZCH22), 2.21 (s, 3H, ZCH3), 2.38 (t, 2H, ZCOCH22), 6.81– 7.23 (m, 15H, ZCHZ and aromatic)

Testing

379

6. Preparation of poly(phenoxazine-co-pyrrole) A nitrogen-flushed Schlenk flask was charged with bis(1,5-cyclooctadiene)nickel(0) (3.2 mmol) and bipyridal (3.2 mmol) and then refluxed under nitrogen. Thereafter the mixture was treated with 10 ml of dimethylfuran, 1,5-cyclooctadiene, and toluene and then stirred for 30 minutes at 808C. The mixture was then treated with a mixture of the step 5 product (1.0 mmol) and the step 2 product (1.0 mmol) dissolved in 10 ml of toluene and heated for 4 days at 808C. Thereafter the mixture was cooled to 608C and precipitated in hydrochloric acid/methanol, 1:1.2, respectively. The precipitate was isolated, redissolved in CHCl3, and then reprecipitated in method, and 0.4 g product isolated having an Mn of 120,000 Da.

DERIVATIVES Selected poly(phenoxazine-co-pyrrole) derivatives are provided in Table 1.

TESTING Turn-on Voltage and Light-Emitting Efficiency Testing A transparent electrode substrate was prepared by coating indium tin oxide (ITO) on a glass substrate and washing the substrate. ITO was then patterned using a photoresist resin and an etchant to specified patterns and the substrate washed. A hole injection layer was formed by coating a selected experimental agent dissolved in toluene to a thickness of about 50 nm and baking at 1108C for 1 hour. Emissive layer forming materials were prepared by dissolving in 0.8 wt% of a selected experimental agent into m-xylene and then filtered through a 0.45-mm filter. The solution was then spin coated on the hole injection layer and baked to form an 80-nm-thick polymer layer. Thereafter 2.7 nm of a Ca layer and an Al layer were vapor deposited on the electroluminescent polymer. Turn-on voltage, color coordinates, and light-emitting efficiency testing results are provided in Table 1.

380


TABLE 1. Turn-on Voltages and Light Efficiencies for Selected Experimental Copolymersa Turn on Voltage (V)

Light-Emitting Efficiency (cd/A)

1

4.2

3.1

2

3.5

4.6

3

2.6

5.3

Entry

a

Repeat Unit

In all cases the color coordinates (x,y) were 0.16 and 0.28.

NOTES 1. In other investigations by the authors (1) and Choi et al. (2) cyclopentaphenanthrene, (I), and 1,4-dimethylenecyclohexane derivatives, (II), respectively, were prepared and were effective as organic light-emitting devices having good thermal stability and charge-transport agents.

Notes

381

2. Electroluminescent polymers, (III) and (IV), both having improved emission and oxidative stability properties were prepared by Son et al. (3) and Park et al. (4), respectively, which offered high charge mobility and blue light emission.

382


3. Blue electroluminescent polymers and electroluminescent device were prepared by Sohn et al. (5) using poly(dioctylfluorene-co-indolocarbazole), (V).

References 1. S.-H. Park et al., U.S. Patent Application 20070290610 (December 20, 2007). 2. B.-K. Choi et al., U.S. Patent Application 20070043188 (November 15, 2007). 3. J.-M. Son et al., U.S. Patent Application 20070173633 (July 26, 2007). 4. S.-H. Park et al., U.S. Patent Application 20070043188 (July 5, 2007). 5. B.-h. Sohn et al., U.S. Patent 7,172,823 (February 6, 2007).

i. Polynaphthalanes

Title:

Synthesis of Polynaphthalenes and Their Use

Author: Assignee:

Florian Doetz et al. BASF Aktiengesellschaft (Ludwigshafen, DE)


Observations:

20070287821 (December 13, 2007) High Early 2010

Improved synthesis of poly(2,6-naphthalene) derivatives. This is the first example of preparing poly(2,6-naphthalene) derivatives using a coupling reaction. Organic light-emitting diode in printers, laptops, kitchen appliances, liquid-crystal displays, etc. Cathode ray tube replacements Polynaphthalenes were initially prepared by the thermolysis of dialkynylbenzenes. In this application poly(2,6-naphthalene) derivatives were prepared by using the Yamamoto coupling catalyst, bis(1,5cyclooctadiene)nickel (0), with 2,6-dibromo-naphthalene derivatives. In this manner 1,5-hexyloxy poly (2,6-naphthalene) and analogs were prepared. 1,5-Hexyloxy poly(2,6-naphthalene) had a quantum yield greater than 50% with lmax (film) of 445 and lmax (THF) of 390 nm while quantum yields for other derivatives ranged from 17 to 57%. As a result of their light-emitting diode properties, poly(2,6-naphthalene) derivatives represent potential alternatives to cathode ray tubes and liquid-crystal displays in the production of visual display units (VDUs).

383

384


REACTION

i. Acetic acid, iodine, bromine ii. Sodium ethoxide, ethanol, bromohexane iii. Bis(1,5-cyclooctadiene)nickel (0), 2,20 -bipyridine, 1,5-cyclooctadiene, dimethylformamide, toluene

EXPERIMENTAL 1. Preparation of 2,6-dibromo-naphthalene-1,5-diol 1,5-Dihydroxynaphthalene (15 g) was dispersed in 350 ml of acetic acid and then heated to 808C. The mixture was treated with a spatula tip of iodine and the dropwise addition of 30 ml of bromine over a period of 90 minutes and then stirred at 808C for an additional hour. After decanting off the green solution and recrystallizing the solid twice in acetic acid 28 g of product was isolated as brownish crystals.

2. Preparation of 2,6-dibromo-1,5-bishexyloxynaphthalene Sodium ethoxide (5.35 g) was dissolved in 50 ml of ethanol and then treated with the step 1 product and the mixture heated to 958C for 35 minutes. This solution was then treated with bromohexane (13 g) and then heated at 908C for an additional 2 hours. After concentrating the residue was purified by chromatography using aluminum oxide with ethanol/CH2Cl2, 1:1, and 1.7 g product isolated as a yellow solid.

3. Polymerization of 2,6-dibromo-1,5-bishexyloxynaphthalene The step 2 product (0.35 g), bis(1,5-cyclooctadiene)nickel (0) (0.46 g), 2,20 -bipyridine (0.26 g), and 1,5-cyclooctadiene (0.11 g) were heated in 10 ml apiece of dimethylformamide and toluene under argon for 3 days at 808C and then cooled. The reaction mixture was then precipitated in a mixture of acetone/methanol/hydrochloric acid and then washed in methanol and the product isolated as a beige-brown solid. Quantum yield (film) ¼ 54% Mw ¼ 4200 lmax (toluene) ¼ 385 nm; lmax (film) ¼ 480 nm

Notes

385

DERIVATIVES Physical and optical properties of selected polynaphthalenes are provided in Table 1. TABLE 1.

Physical and Optical Properties of Selected Polynaphthalenesa Mw (Da)

Quantum Yield (%)

lmax (nm)

2

3,000

—

445 (film)

3

3,800

17

473 (film)

4

4,300

57

397 (THF)

6

20,600

28

387 (THF)

Entry

a

Polymer Repeat Unit

Limited characterization data were supplied by author of the current invention.

NOTES 1. Copolynaphthalene ester films were prepared by transesterification/esterification of dimethyl naphthalene dicarboxylate and dimethyl isophthalate with aliphatic diols by Hebrink et al. (1) and used in optical polarizing films with color shifts. 2. Poly(polyethylene glycol-co-naphthalate), (I), was previously prepared by Hebrink et al. (2) and used in multilayered polymer films as a reflective polarizer or mirror.

386


3. Syndiotactic polynaphthalene was used by Ruff et al. (3) as a birefringent component in multilayer p-polarizing optical films.

References 1. T.J. Hebrink et al., U.S. Patent 7,064,897 (June 20, 2006) and U.S. Patent 7,138,173 (November 21, 2006). 2. T.J. Hebrink et al., U.S. Patent 7,150,907 (December 19, 2006). 3. A.T. Ruff et al., U.S. Patent 7,094,461 (August 22, 2006).

j. Polynaphthylanthracenes

Title: Electroluminescent Devices Having Pendant Naphthylanthracene-Bases Polymers Author: Assignee:

Shiying Zheng et al. Eastman Kodak Company (Rochester, NY)


20070187673 (August 16, 2007) Low Late 2009

Development of polymeric naphthylanthracene derivatives suitable for use in organic electroluminescent devices. Ongoing 3-year-old investigation. Polymer-based light-emitting diodes This investigation is a continuation of an earlier study by the author in preparing anthracenyl-containing polymers for use as

light-emitting diodes. Synthetic steps of the current study were modifications of the earlier investigation by this group. Photoluminscence (lmax) and UV (lmax) properties of both the earlier and current polymeric materials were comparable despite the higher molecular weighs generated in this application.

387

388

Electroluminescent Devices Having Pendant Naphthylanthracene-Bases Polymers

REACTION

i. 2-Ethylhexyl bromide, N,N-dimethyl formamide, potassium carbonate ii. 2-Bromo-6-hydroxynaphthalene, imidazole, N, N-dimethylformamide, t-butyldimethylsilyl chloride iii. THF, n-BuLi, 2,6-di(2-ethylhexyloxy)anthraquinone iv. Imidazole, N, N-dimethylformamide, t-butyl-dimethylsilyl chloride v. Triethylamine, methacryloyl chloride, CH2Cl2 vi. Toluene, 2,20 -bisiosbutyronitrile.

Experimental

389

EXPERIMENTAL 1. Preparation of 2,6-di(2-ethylhexyloxy)anthraquinone A reactor charged with 2,6-dihydroxyanthraquinone (0.42 mol) and 2-ethylhexyl bromide (0.86 mol) dissolved in 1 liter of dimethyl formamide (DMF) was treated with anhydrous K2CO3 (0.87 mol) and then heated to 908C overnight. After most of DMF was removed and 500 mL of water added, the mixture was extracted three times with 400 ml diethyl ether and then washed with 200 ml brine and dried using MgSO4. The mixture was then concentrated and 125.21 g product isolated after recrystallizing the residue in methanol, mp ¼ 49– 518C. 1

H-NMR (CDCl3) d 0.92– 0.98 (m, 12H, CH3), 1.34– 1.54 (m, 16H), 1.75– 1.81 (m, 2H, CH(CH3)), 4.02 (d, J ¼ 5.5 Hz, 4H, OCH2), 7.19 (d, J ¼ 8.4 Hz, 2H), 7.70 (s, 2H), 8.19 (d, J ¼ 8.5 Hz, 2H) 13 C-NMR (CDCl3) d 11.12, 14.06, 23.04, 23.88, 29.08, 30.51, 39.34, 71.34, 110.64, 120.84, 127.00, 129.62, 135.88, 164.29, 182.27

2. Preparation of 2-bromo-6-t-butyldimethylsiloxynaphthalene 2-Bromo-6-hydroxynaphthalene (0.45 mol) and imidazole (1.10 mol) were dissolved in 300 ml of N,N-dimethylformamide and then treated with t-butyl-dimethylsilyl chloride (0.53 mol) and stirred at ambient temperature overnight. The mixture was then poured into water and the precipitate isolated. After washing with water and cold ethanol, it was recrystallized from ethanol and 97.2 g of product isolated as off-white crystals, mp ¼ 62 – 648C. H-NMR (CDCl3) d 0.24 (s, 6H), 1.01 (s, 9H), 7.07 (dd, J1 ¼ 8.8 Hz, J2 ¼ 2.3 Hz, 1H), 7.14 (s, 1H), 7.45 (dd, J1 ¼ 8.8 Hz, J2 ¼ 2.3 Hz, 1H), 7.53 (d, J ¼ 8.8 Hz, 1H), 7.60 (d, J ¼ 8.8 Hz, 1H), 7.90 (s, 1H) 13 C-NMR (CDCl3) d 24.34, 18.24, 25.68, 114.86, 117.26, 123.05, 128.29, 128.42, 129.39, 129.57, 130.24, 133.04 1

3. Preparation of 2,6-bis(2-ethylhexyloxy)-9,10-bis(2-(6-hydroxynaphthyl))anthracene The step 2 product (0.14 mol) dissolved in 130 ml of THF was cooled to 2788C and then treated with n-BuLi (2.5 M in hexane; 0.14 mol) and stirred at this temperature for 1 hour. This solution was then treated with the step 1 product (0.048 mol) dissolved in 120 ml THF and then stirred for 3 hours. The reaction was quenched with 85 ml of 47% aqueous HI solution and then refluxed for 1 hour. The mixture was extracted with CH2Cl2 and combined extracts washed with saturated sodium meta bisulfite solution and then dried using MgSO4. The residue was purified by chromatography using silica gel and 25.5 g of product isolated after recrystallization from CH3CN as a light greenish yellow solid, mp ¼ 174 – 1768C. 1

H-NMR (CDCl3) d 0.73– 0.84 (m, 12H, CH3), 1.16–1.35 (m, 16H, alkyl), 1.54–1.60 (m, 2H, CH(CH2CH3)), 3.66 (d, J ¼ 5.5 Hz, 4H, OCH2), 6.90 (d, J ¼ 2.3 Hz, 2H), 6.98 (dd, J1 ¼ 9.5 Hz, J2 ¼ 2.5 Hz, 2H), 7.21 (dd, J1 ¼ 8.8 Hz, J2 ¼ 2.4 Hz, 2H), 7.33 (d, J ¼ 2.3 Hz, 2H), 7.56 (d, J ¼ 9.4 Hz, 2H), 7.84 (d, J ¼ 8.8 Hz, 2 7.90 (s, 2H), 7.91 (d, J ¼ 8.8 Hz, 2H)

390


13

C-NMR (CDCl3) d 11.07, 14.00, 22.94, 23.78, 28.98, 30.51, 39.00, 70.09, 103.96, 109.54, 118.09, 120.11, 126.55, 127.22, 128.27, 129.08, 129.79, 129.99, 130.08, 130.24, 133.86, 134.71, 134.93, 153.60, 155.69

4. Preparation of 2,6-bis(2-ethylhexyloxy)-9-(2-(6-t-butyldimethylsiloxynaphthyl))-10-(2-(-6-hydroxynaphthyl))anthracene The step 3 product 3 (4.2 mmol) and imidazole (8.0 mmol) were dissolved in 15 ml of N,N-dimethylformamide and treated with t-butyl-dimethylsilyl chloride (6.6 mmol) and then stirred at ambient temperature overnight. The mixture was then poured into water, extracted with CH2Cl2, and the combined organic phase dried with MgSO4. The crude product was purified by column chromatography on silica gel using hexane/CH2Cl2, 15/85, respectively, and 1.79 g of product isolated as a greenish yellow solid, mp ¼ 125 – 1278C. H-NMR (CDCl3) d 0.33 (s, 6H), 0.75–0.84 (m, 12H), 1.08 (s, H), 1.16– 1.34 (m, 18H), 3.66 (d, J ¼ 5.3 Hz, 4H), 6.89–6.91 (m, 2H), 6.98 (dd, J1 ¼ 9.5 Hz, J2 ¼ 2.4 Hz, 2H), 7.16–7.22 (m, 2H), 7.34 (dd, J1 ¼ 9.5 Hz, J2 ¼ 2.4 Hz, H), 7.54– 7.60 (m, 4H), 7.797.93 (m, 6H) 13 C-NMR (CDCl3) d 24.243, 11.07, 14.01, 22.94, 23.78, 25.76, 28.98, 30.52, 39.00, 70.07, 70.13, 103.96, 104.03, 109.50, 114.84, 118.19, 120.09, 122.40, 126.53, 126.82, 127.23, 128.28, 128.33, 128.99, 129.37, 129.52, 129.81, 129.88, 129.99, 130.18, 133.91, 134.61, 134.80, 134.94, 135.04, 153.75, 153.82, 155.68 1

5. Preparation of 2,6-bis(2-ethylhexyloxy)-9-(2-(6-t-butyldimethyl-siloxynaphthyl))-10-(2-(-6-methacryloylnaphthyl))anthracene The step 4 product (2.9 mmol) and triethylamine (3.5 mmol) was dissolved in 30 ml of CH2Cl2 and then cooled to 08C and treated with methacryloyl chloride (3.5 mmol). The mixture stirred at ambient temperature overnight and was then washed with water and dried using MgSO4. The residue was purified by column chromatography on silica gel using hexane/ethyl acetate, 98/2, respectively, and 2.01 g product isolated as a bright yellow solid, mp ¼ 213– 2158C. 1

H-NMR (CDCl3) d 0.33 (s, 6H), 0.75– 0.85 (m, 12H), 1.08 (s, 9H), 1.18–1.38 (m, 18H), 2.16 (s, 3H), 3.64– 3.67 (m, 4H), 5.84– 5.85 (m, 1H, vinyl), 6.47 (s, 1H, vinyl), 6.85 (d, J ¼ 1.9 Hz, 1H), 6.92 (s, 1H), 6.97–7.01 (m, 2H), 7.16– 7.20 (m, 1H), 7.35–7.38 (m, 2H), 7.50– 7.64 (m, 4H), 7.77– 7.8 (m, 2H), 7.89– 8.06 (m, 5H) 13 C-NMR (CDCl3) d 24.25, 11.07, 14.02, 18.32, 18.48, 22.94, 23.82, 25.77, 28.99, 29.03, 30.54, 30.58, 39.00, 39.15, 69.98, 103.58, 104.06, 114.81, 118.67, 120.21, 121.63, 122.41, 126.82, 127.14, 127.18, 127.49, 127.87, 128.06, 128.34, 129.36, 129.52, 129.65, 129.70, 129.80, 129.83, 129.87, 129.96, 130.00, 130.29, 131.67, 133.11, 133.94, 134.46, 134.75, 135.26, 135.92, 137.05, 148.83, 153.79, 155.69, 155.89, 166.21

6. Preparation of polymer The step 5 product was dissolved in 7 ml of toluene and polymerized using 2,20 -bisiosbutyronitrile (6 mg) by heating to 608C overnight. The solution was poured into 60 ml of methanol and the precipitated material isolated. It was dried, redissolved in toluene, reprecipitated in hexane, and the product isolated as a yellow solid.

Notes

391

DERIVATIVES A styrene intermediate, (I), was also prepared and polymerized using 2,20 -bisiosbutyronitrile.

NOTES 1. Electrolunimnescnt devices having conjugated arylamines, (I), were prepared by the authors (1) and used in light-emitting diodes and optoelectronic devices.

2. Electroluminescent devices, including conjugated polymers containing an azole component, (II), were prepared by the authors (2) and were effective as organic light-emitting displays and liquid-crystal displays. In addition these agents required less power to operate, offered higher contrast and wide viewing

392


angle (.1658), and have tremendous industrial potential since they are less expensive to manufacture, especially the polymer-based LEDs (PLED).

References 1. S. Zheng et al., U.S. Patent Application 20070278941 (December 6, 2007). 2. S. Zheng et al., U.S. Patent Application 20050186445 (April 25, 2005).

k. Polynorbornenes

Title: Norbornene-Based Polymer, Film, Polarizing Plate and Liquid-Crystal Display Device Author: Assignee:

Yutaka Nozoe et al. Fuji Film Corporation (Tokyo, JP)


20080081890 (April 3, 2008) Moderately high 2010

Synthesis of poly(norbornene-co-fluorene) derivatives having a low negative thickness direction. Two-year ongoing investigation. Plasma displays The objective of this application was to prepare poly (norbornene-cofluorene) films that had a small or negative thickness direction for use in plasma displays, polarizing plates, or in liquid-crystal display devices. Poly(norbornene-co-fluorene) were prepared using a parallel synthesis of monomers. Norbornene acetate was prepared using the Diels–Alder addition product of cyclopentadiene and allyl acetate. Norbornene –fluorene derivatives were prepared by Sn2 displacement reactions of exo, exo-norbornenedimethyl tosylate with selected fluorenes. Copolymers were prepared using a modified Suzuki reaction.

393

394

Norbornene-Based Polymer, Film, Polarizing Plate and Liquid-Crystal Display Device

REACTION

i. ii. iii. iv.

Pyridine, p-toluenesulfonyl chloride, THF Fluorene, THF, butyllithium Dicyclopentadiene, allyl acetate, hydroquinone Bis(2,4-pentanedionato)palladium, tricyclohexylphosphine, toluene, dimethylanilinium tetrakispentafluorophenyl borate, CH2Cl2 EXPERIMENTAL

1. Preparation of exo, exo-norbornenedimethyl tosylate A three-neck flask was charged with exo, exo-norbornenedimethanol (0.324 mol) and 404 ml of pyridine and then treated with the dropwise addition of p-toluenesulfonyl chloride (0.712 mol) dissolved in 210 ml of THF at 08C. After the addition was completed, the mixture was warmed to ambient temperature and stirred for 4.5 hours and then quenched with 0.12 M hydrochloric acid. It was washed three times apiece with 0.12 M hydrochloric acid, saturated aqueous NaHCO3 solution, and water and then dried with MgSO4. The mixture was filtered, concentrated, dried under vacuum, and 51.6 g of product isolated. 2. Preparation of norborene – fluorene intermediate A 2-liter three-neck flask fitted with a thermometer and a cooling tube was charged with fluorene (0.237 mol) and 210 ml of THF and then cooled to 2788C and treated dropwise with 297 ml butyllithium (0.432 mol). The mixture was stirred for 1 hour at 2788C and then treated with the dropwise addition of the step 1 product dissolved in THF. The mixture was warmed to ambient temperature and stirred for 3 hours and then quenched with a saturated aqueous solution of brine, washed with water three times, and the organic layer dried using MgSO4. The mixture was filtered, concentrated, recrystallized from methanol, and 13.7 g product isolated.

Scoping Reactions

395

3. Preparation of norbornene acetate derivative A 1-liter autoclave was charged with dicyclopentadiene (1.75 mol), allyl acetate (4.2 mol), and hydroquinone (1 g) and then stirred at 1808C for 9 hours in a closed system at 300 rpm. It was then filtered and volatile components evaporated. The residue was distilled twice at 868C @ 10 mmHg and 358 g of product isolated. 4. Preparation of norbornene copolymer A 500-ml flask was charged with the step 2 product (0.105 mol), the step 3 product (0.245 mol), and 70 ml of toluene, and then stirred at ambient temperature. Thereafter the solution was treated with bis(2,4-pentanedionato)palladium (0.070 mmol) and tricyclohexylphosphine (0.070 mmol) dissolved in 10 ml of toluene and dimethylanilinium tetrakispentafluorophenyl borate (0.28 mmol) dissolved in 5 ml of CH2Cl2. The mixture was stirred at 808C for 1 hour, during which time toluene was suitably added as the viscosity of the reaction solution increased. After the reaction was completed, the solution was diluted with toluene and the mixture precipitated in excess methanol. The precipitate was filtered off and washed with a large amount of methanol, the polymer dried in vacuo at 1108C for 6 hours, and 61.4 g of product isolated.

DERIVATIVES The following step 3 norbornene monomeric agents were prepared:

SCOPING REACTIONS

396

Norbornene-Based Polymer, Film, Polarizing Plate and Liquid-Crystal Display Device

TABLE 1. Compositional Ratio and Corresponding Physical Properties of Selected Norbornene Copolymers Polymer

Fluorene Monomer (mol%)

Norbornene Monomer N (mol%)

Mw (Da)

Mn (Da)

0 100 2 10 30 30

100 0 98 90 70 70

278,000 724,000 349,000 299,000 283,000 280,000

81,000 181,000 102,000 90,000 70,000 69,000

P-1 (comparative) P-2 P-3 P-4 P-5 O-1 (comparative)

TESTING A. Preparation of Polymer Films Fifty grams of a selected polymer were dissolved in 200 g of CH2Cl2 and then pressure filtered and the resulting dope cast onto a hydrophobic glass plate and dried at 258C for 5 minutes in a closed system and for 10 minutes in an air-blowing dryer at 408C. The film was then released from the glass plate and held in a stainless frame and dried for 30 minutes at 1008C and for 30 minutes in a dryer at 1338C and then isolated. B. Stretching Each film was cut into a 5-cm width strip and stretched by 10% at 2308C to 2808C using an automatic biaxial stretching device. C. Measurement of Physical Properties Re and Rth of films at 589 nm were measured using film stretch by 10% at 230 – 2808C using an automatic biaxial stretching machine. Film thickness was assayed at any three points by means of a digital micrometer and an average value reported. Testing results are provided in Table 2. TABLE 2. Effect of Stretching Selected Norbornene Copolymers on Thickness Direction, Rth, and retardation, Rea Polymer Film P-1 (comparative) P-2 P-3 P-4 P-5 P-9 (comparative) a

Re (nm)

Rth (nm)

10 210 1 0 21 220

200 21800 20 2100 2410 4

Small or negative Rth values are preferred.

Notes

397

NOTES 1. Additional norbornene polymers, (I), were previously prepared by Watanabe et al. (1) and used in films, polarizing plates, and liquid-crystal devices.

Reference 1. S. Watanabe et al., U.S. Patent Application 20080033133 (February 7, 2008).

l. Polyspirobifluorene

Title: Conjugated Polymers Containing Spirobifluorene Units and Use Thereof Author: Assignee:

Heinrich Becker Covion Organic Semiconductors GmbH (Wiesbaden, DE)


Observations:

398

20070265473 (November 15, 2007) High Late 2009

Preparation of optoelectronic devices using copolymers containing spirobifluorene derivatives. Electroactive modified polymeric spirobifluorene derivatives are unreported in the patent literature. Optoelectronic devices Polymeric organic light-emitting diodes This current application represents another advancement in the ongoing investigation for materials usable as polymeric organic light-emitting diodes. Previous studies have determined that copolymers containing heterospirofluorenes, carbazoles, coumarin, quinolinone, and amines were also effective as organic light-emitting diodes. It was only recently reported that diindenofluorene monomers were effective as electroluminescent polymers without the debits associated with polyfluorene materials.

Experimental

399

REACTION

i. 2-Bromo-4,40 -di-t-butylbiphenyl, potassium carbonate, tetrakis(triphenylphosphine) palladium ii. Ethyl acetate, N-bromosuccinimide iii. Magnesium, iodine, THF, 2,7-dibromfluoren-9-one, glacial acetic acid, hydrochloric acid iv. Bis(cyclooctadiene)nickel(0), 2,20 -bipyridyl, dimethylformamide, toluene, 1,5cyclooctadiene EXPERIMENTAL 1. Preparation of 50 -t-butyl-20 -(400 -t-butylphenyl)-2,3-bis(2methylbutyloxy)biphenyl 2-Bromo-4,40 -di-t-butylbiphenyl (0.595 mol), 3,4-bis(2-methylbutyloxy)benzeneboronic acid (0.641 mol), and K2CO3 (1.282 mol) were suspended in 840 ml of toluene and 840 ml of water and the mixture saturated with nitrogen for 1 hour. Thereafter Pd(PPh3)4 (1.28 mmol) was added and the mixture refluxed for 8 hours. The cooled solution was then treated with 630 ml of 1% NaCN and stirred for 2 hours. The organic phase was isolated, dried over Na2SO4, and concentrated. The residue consisted of 300.2 g of a light-brown oil having a 97% purity. 1

H-NMR (CDCl3) d 7.5– 7.3 (m, 3H); 7.23 (m, 2H); 7.08 (m, 2H); 6.81–6.87 (m, 2H); 6.51 (d, 1H); 3.87–3.7 (m, 2H, OCH2); 3.44 –3.30 (m, 2H, OCH2); 1.88 (m, 1H, HZC); 1.71 (m, 1H,

400

Conjugated Polymers Containing Spirobifluorene Units and Use Thereof HZC); 1.62– 1.42 (m, 2H, CH2); 1.39 (s, 9H, C(CH3)3); 1.29 (s, 9H, C(CH3)3); 1.10– 1.33 (m, 4H, CH2); 1.07– 0.83 (m, 12H, 4.times.CH3)

2. Preparation of 2-bromo-50 -t-butyl-20 -(400 -t-butylphenyl)-4,5-bis(2-methylbutyloxy)biphenyl The step 1 product (0.583 mol) was dissolved in 500 ml of ethyl acetate, cooled to 08C, and treated with N-bromosuccinimide (0.583 mol) and then warmed to ambient temperature and stirred for 1 hour. The organic phase was washed three times with water, dried, concentrated, and recrystallized using ethanol. The product was isolated in 85% as a colorless solid that had a .99% purity. 1

H-NMR (CDCl3) d 7.45– 7.35 (m, 3H); 7.19 (m, 2H); 7.06 (m, 3H); 6.50 (d, 1H); 3.87–3.70 (m, 2H, OCH2); 3.55–3.25 (m, 2H, OCH2); 1.88 (m, 1H, HZC); 1.67 (m, 1H, HZC); 1.62–1.42 (m, 1H, CH2); 1.38 (sþm, 10H, C(CH3)3þ1H); 1.27 (sþm, 10H, C(CH3)3þ1H); 1.15 (m, 1H, CH2); 1.12 (d, 3H, CH3); 0.95 (t, 3H, CO3); 0.9–0.8 (m, 6H, 2.times.CH3).

3. Preparation of 2,7-dibromo-80 -t-butyl-50 -(400 -t-butylphenyl)-20 ,30 -bis(2methylbutyloxy)spirobifluorene (S-US1) The step 2 product (0.495 mol) was dissolved in 700 ml of THF and treated with magnesium while another vessel was treated with magnesium turnings (0.510 mol) and a few crystals of iodine. Thereafter, 10% of the amount of starting material in THF was added to the first vessel and the remainder added at such a rate that the reaction mixture refluxed without external heat. After 1 hour the addition was completed and the mixture refluxed for an additional 3 hours and then diluted with 100 ml THF. The Grignard reagent was then cooled to 08C and treated with suspension of 2,7-dibromfluoren-9-one (561.2 mmol) in 500 ml of THF. After the addition was completed, the mixture refluxed for 90 minutes, and then cooled, and poured into a mixture of 600 ml of ice water, 33.2 ml of hydrochloric acid, and 900 ml of ethyl acetate. The organic phase was isolated and washed twice with NaHCO3 solution, water, and then dried and concentrated. This light brown oily residue was then heated to boiling for 1 hour in 3-liter glacial acetic acid and 21 ml of 37% hydrochloric acid. The mixture was further heated for another 2 hours, cooled, and a solid isolated. A single recrystallization using 2-butanone provided 310.1 g of product having a purity of .99.5%. 1

H-NMR (CDCl3) d 7.67 (d, 2H); 7.55 (d, 2H); 7.53 –7.43 (m, 5H); 7.26 (d, 1H); 6.97 (s, 1H); 6.27 (s, 1H); 5.60 (s, 1H), 3.40– 3.21 (m, 4H, OCH2); 1.67– 1.55 (m, 2H, HZC); 1.42 (sþm, 11H, C(CH3)3þ2H); 1.19 –1-01 (m, 2H); 1.27 (sþm, 10H, C(CH3)3þ1H); 1.15 (m, 1H, CH2); 1.12 (d, 3H, CH3); 0.95 (t, 3H, CH3); 0.82 (sþm, 21H, 1.times.C(CH3)3þ4.times.CH3).

4. Polymerization by Yamamoto coupling: Generic method A Schlenk flask was charged with Ni(COD)2 (5.57 mmol) and 2,20 -bipyridyl (5.57 mmol) and then 25 ml of dimethylformamide and 80 ml of toluene were added. The mixture was heated to 808C and after 30 minutes treated with 1,5-cyclooctadiene (3.51 mmol) and a solution of a selected spirobifluorene (2.11 mmol) and a selected comonomer (0.242 mmol) dissolved in 20 ml of toluene added. After 144 hours the

Derivatives

401

mixture was cooled and treated with 5 ml of hydrochloric acid in dioxane and then stirred for 15 minutes. The mixture was further treated with 50 ml of chloroform and stirred an additional 15 minutes. The organic phase was washed twice with 100 ml 5 M of hydrochloric acid and once with 100 ml of saturated NaHCO3 solution. The polymer was dissolved in THF and then precipitated in 450 ml of methanol, the process being repeated twice. The polymer was dried and 1.30 g product isolated as a fibrous, light yellow material.

DERIVATIVES Spirobifluorene monomers and spirobifluorene copolymers are provided in Tables 1 and 2, respectively. TABLE 1. Selected Spirobifluorene Monomers Prepared in Three Reaction Steps for Subsequent Conversion into Spirobifluorene Copolymer by Yamamato Coupling Entry S-SY3

S-US2

S-US3

S-US4

Spirobifluorene Monomer

402

Conjugated Polymers Containing Spirobifluorene Units and Use Thereof

TABLE 2. Spirobifluorene Copolymers Prepared by Yamamoto Coupling of Monomers Using Ni(COD)2, 1,5-cyclooctadiene, and 2,20 -bipyridyl with Dimethylformamide and Toluene as Reaction Solvents Entry

Spirobifluorene

Comonomer

Mn (Da)

MX-3

155,000

MX-4

—

NOTES 1. The preparation of additional spirofluorene monomers are described by Parham et al. (1). 2. Tsai et al. (2) determined that blue phosphorescent organic light-emitting devices consisting of 2,20 -bis(N, N-disubstituted amino)-9,90 -spirobifluorenes, (I), were effective as hole transporting materials and had efficiencies of up to 16%, 30.6 cd/A and 26.7 lm/W.

3. Although effective as electroluminescent polymers, fluorene-containing polymers have limited hole transporting properties because of the tendency of fluorene units to aggregate. To impede aggregration Mckiernan et al. (3) prepared diindenofluorene monomers, (II), which were readily processable and had excellent electrical and optical properties.

Notes

403

4. Hetero spirofluorenes, (III), were prepared by the author et al. (4) in an earlier investigation and used in polymer organic light-emitting diodes having extended lifetimes.

References 1. A. Parham et al., U.S. Patent Application 20070123690 (May 31, 2007) and U.S. Patent Application 20060149022 (July 6, 2006). 2. M.-H. Tsai et al., U.S. Patent Application 20070262703 (November 15, 2007). 3. M. Mckiernan et al., U.S. Patent Application 20070252139 (November 1, 2007). 4. H. Becker et al., U.S. Patent Application 20070060736 (March 15, 2007).

m. Polythiophenes

Title: Conjugated Thiophenes Having Conducting Properties and Synthesis of Same Author: Assignee:

William G. Skene Universite de Montreal (Montreal, CA)


Observations:

404

20070287842 (December 13, 2007) High Mid-2009

Simplified method for preparing conjugated aromatic polyazomethine thiophene derivatives. Although polyazomethines are extensively reported in the patent literature, the synthetic method in this application is novel. Organic light-emitting diodes Polymer light-emitting diodes Conducting wires Thin films Photosensitive resin compositions containing polyazomethines are extensively reported in the patent literature. Poly(imide-co-azomethine) and poly(amic acid-co-azomethine) are typical examples. In their preparation, however, anhydrous conditions are used. In the current application a one-pot Gewald batch process containing a diamine with an aldehyde were used without the need for anhydrous solvents or other stringent reaction conditions. The driving force for this reaction was the formation of conjugated polymers, which is also the thermo dynamic force that renders these Schiff bases resistant to acid-catalyzed hydrolysis. In this process fluorene-, stilbene-, and thiophene polyazomethine derivatives were prepared by condensing aromatic diamines with aromatic aldehydes. Products were characterized as

Derivatives

405

having solution lmax of approximately 490 nm, yields exceeding 85%, and Mw’s between 85,000 and 1,500,000 Da. Once doped, these materials were used as p-type or n-type conductors in organic and polymer light-emitting diodes and conducting wires.

REACTION

i. 2,5-Diamino-thiophene-3,4-dicarboxylic acid diethyl ester, trifluoroacetic acid

EXPERIMENTAL 1. Preparation of thiophene polyazomethine A reaction vessel was charged with 2,5-thiophenedicarboxaldehyde (0.046 mmol), 2,5-diaminothiophene-3,4-dicarboxylic acid diethyl ester (0.041 mmol), and 5 –10 mol% of trifluoroacetic acid and then heated under nitrogen for 12 hours without solvent. The oil that formed was cooled and low-molecular-weight oligomers removed by washing with ethanol. The product was isolated as a dark purple solid having an Mn of 87,541 Da with lmax dimethyl sulfoxide (DMSO) ¼ 497 and 542 nm.

DERIVATIVES Selected polyazomethines prepared according to the current application and their corresponding physical properties are provided in Table 1. Model compounds were prepared to assist in 1H-NMR peak assignment and are provided in Table 2.

406

Conjugated Thiophenes Having Conducting Properties and Synthesis of Same

TABLE 1.

High-Molecular-Weight Polyazomethines and Corresponding lmaxa Mw (Da)

lmax (nm)

21

148, 094

305, 338 (water)

31

—

Entry

Repeat Unit Structure

85,000

45

a

319, 323, 335

500 (butanol)

Extensive 1H-NMR structural characterization provided by author of the current invention.

TABLE 2. Physical Properties of Model Compounds Used to Assist in 1H-NMR Peak Assignments of Polyazomethinesa Entry

Model Compound

lmax mp (8C) (acetonitrile)

14

128

418

15

255

381

24

—

—

25

—

—

27

—

424

30

—

—

a

All samples were analyzed using a 400-MHz spectrophotometer in d6-DMSO.

Notes

407

TESTING A. Preparation of p-Type Doped Pellets Iodine doping was done by the addition of iodine crystals to a chamber containing a pellet of a selected polyazomethine. The chamber was then evacuated, which caused the immediate sublimation of iodine. Gaseous iodine remained in contact with the pellet for a period ranging from about 1.5 to about 17 hours, whereupon the doped pellet was removed and stored under nitrogen until being tested. Testing data for p-doped experimental agents was not supplied by the author of the current invention. B. Preparation of n-Doped Pellets Sodium naphthalide doping was performed using a selected polyazomethine with a THF slurry of sodium naphthalide and stirring for 24 hours. Thereafter the mixture was concentrated and the doped polymer stored at ambient temperature until needed. Testing data for n-doped experimental agents not supplied by the author of the current invention.

NOTES 1. Hasegawa et al. (1) prepared conjugated pyromellitic dianhydride polyazomethines, (I), and converted them into a pyromellitic polyimide ladder, (II), by reacting with two equivalents of benzidine.

2. Nonconjugated polyazomethines, (III), were prepared by Udea et al. (2) and then converted into polybenzoxazoles by heating from 250 to 4008C for 25 minutes as illustrated in Eq. (1). Polybenzoxazoles were effective as highperformance resins.

408

Conjugated Thiophenes Having Conducting Properties and Synthesis of Same

(1)

i. Isophthalic dialdehyde ii. Heat

References 1. M. Hasegawa et al., U.S. Patent Application 20070254245 (November 1, 2007) and U.S. Patent Application 20060269868 (November 30, 2006). 2. M. Ueda et al., U.S. Patent 6,780,561 (August 24, 2004).

XIV. MEDICAL POLYMERS A. Biodegradable a. Polyesters

Title:

Degradable Polymers

Author: Assignee:

Krzysztof Matyjaszewski et al. Carnegie Mellon University (Pittsburgh, PA)


Observations:

20070155926 (July 5, 2005) High Early 2008

Development of ring-opening polymerization monomers that are susceptible to hydrolytic and photolytic degradation. Ongoing 4-year investigation. Biodegradable polymers Environmentally degradable packaging Six 5-methylene-2-phenyl-1,3-dioxolan-4-one derivatives were prepared then co- and terpolymerized by atom transfer radical polymerization with methyl methacrylate or styrene. Each monomer contained an internal ester that rendered them susceptible to hydrolysis. Whether these copolymers are also photosensitive was inclusive since photolysis studies were performed on hydrolytic fragments. Reagents and experimental conditions used in radical ring-opening polymerization were identical to those used by this group in earlier atom transfer radical polymerizations. In a subsequent investigation by this group heterogeneous initiators for atom transfer radical/radical ring-opening polymerization were prepared.


409

410

Degradable Polymers

REACTION

i. Methyl methacrylate, copper(I) bromide, copper(II) bromide, anisole, ethyl 2-bromoisobutyrate, N,N,N0 ,N00 ,N00 -pentamethyldiethylenetriamine ii. Potassium hydroxide, isopropanol, 2-butanone EXPERIMENTAL 1. Preparation of poly(5-methylene-2-phenyl-1,3-dioxolan-4-one-co-methyl methacrylate): Generic method A 10-ml Schlenk flask was charged with CuBr (0.10 mmol), CuBr2 (0.005 mmol), N,N,N0 ,N00 ,N00 -pentamethyldiethylenetriamine (0.105 mol), 5-methylene-2-phenyl1,3-dioxolan-4-one (1.50 mmol), methyl methacrylate (15.0 mmol), and 2 ml of anisole and purged with nitrogen and evacuated to remove oxygen. The mixture was then stirred at ambient temperature until it was homogeneous and then treated with 14.7 mL of ethyl 2-bromoisobutyrate (0.10 mmol) and then immersed in an oil bath maintained at a selected temperature. Thereafter sample aliquots were intermittently removed and analyzed in order to follow the polymerization kinetics of the reaction. At the end of the reaction the polymer was found to have an Mn of 15,760 Da. 2. Hydrolysis of poly(5-methylene-2-phenyl-1,3-dioxolan-4-one-co-methyl methacrylate) The hydrolysis of the step 1 product (100 mg) was performed with potassium hydroxide dissolved in 5 ml isopropanol/2-butanone, 1:1, at 308C for 18 hours. After hydrolysis the number-average molecular weight was reduced to 1620 Da with a polydispersity of 1.89. 3. Photolysis of oligomeric(5-methylene-2-phenyl-1,3-dioxolan-4-one-co-methyl methacrylate) The photodegradation was conducted for 2 hours. After photolysis the polymer provided fragments with a number-average molecular weight of 1480 Da with a polydispersity of 1.96.

411

Derivatives

SCOPING REACTIONS Scoping studies were performed by analyzing sample aliquots removed from a 10-ml Schlenk flask and are provided in Table 1. TABLE 1. Copolymerization Scoping Reactions Using the Radical Ring-Opening Polymerization Monomer, 5-Methylene-2-phenyl-1,3-dioxolan-4-one, with Methyl Methacrylate

Run 1 2b 3 a

Reaction Temp (8C)

Feed Ratio [MPDQ]a:[MMA]


MMA Conversion (%)

MPDQ Conversion (%)

Mn (Da)

90 70 50

1:10 1:5 1:10

30 90 180

88 83 83

89 88 88

15,760 14,260 14,980

5-methylene-2-phenyl-1,3-dioxolan-4-one.

DERIVATIVES 5-Methylene-2-phenyl-1,3-dioxolan-4-one derivatives that underwent radical ringopening polymerization and the corresponding repeat units are illustrated in Table 2.

TABLE 2. Structures of 5-Methylene-2-phenyl-1,3-dioxolan-4-one Derivatives that Underwent Radical Ring-Opening Polymerization and Corresponding Repeat Units Entry

Monomer

Repeat Unit

1

2

3

(Continued)

412

Degradable Polymers

TABLE 2. Continued Entry

Monomer

Repeat Unit

4

5

6

NOTES 1. The preparation of the radical ring-opening polymerization monomer, 5-methylene-2-phenyl-1,3-dioxolan-4-one, (I), is illustrated in Eq. (1).

(1)

i. Nitric acid ii. Benzaldehyde, benzene, p-toluenesulfonic acid iii. Diisopropylamine 2. The terpolymer of the radical ring-opening polymerization monomer, 5-methylene-2-phenyl-1,3-dioxolan-4-one, (I), with styrene, and methyl methacrylate was also prepared. 3. Guelcher et al. (1) prepared a hydrolyzable polyurethane foam under physiological conditions by condensing a polyester triol with 1-caprolactone/glycolide and then postreacting the intermediate ester with the biocompatible diocyanate, lysine methyl ester diisocyanate. 4. An 1H-NMR method to determine the kdecay of selected biodegradable polymers was developed by Benz et al. (2). In this experiment the biodegradable polyketal formed using 5,6-epoxy-2-one-hexane and having an Mn of 13,350 Da was hydrolyzed at 258C for 16 hours using formic acid in d8-THF (tetrahydrofuran) while collecting spectra at 60 minutes/spectrum.

Notes

413

5. Modified caprolactone monomer polymers, (I), were prepared by Chen et al. (3) and then converted into biodegradable polymers and used in the controlled release of pharmaceutical agents.

6. Physiologically hydrolyzable polyorthoesters, (II), containing polyethylene glycol segments were prepared by Shah et al. (4) and used as drug delivery agents for mepivacaine and granisetron.

References 1. S.A. Guelcher et al., U.S. Patent Application 20070299151 (December 27, 2007). 2. M.E. Benz et al., U.S. Patent Application 20070265355 (November 15, 2007). 3. M. Chen et al., U.S. Patent Application 20070264307 (November 15, 2007). 4. D. Shah et al., U.S. Patent Application 20070264339 (November 15, 2007).

b. Poly(propylene fumarates)

Title: Block Copolymers of Polycarpolactone and Poly(Propylene Fumarate) Author: Assignee:

Shanfeng Wang et al. Mayo Foundation for Medical Education and Research (Rochester, MN)


Application:

Observations:

414

20080004368 (January 3, 2008) High Early 2010

Synthesis of poly(propylene fumarate) derivatives as biocompatible agents. Methods for preparing high-strength poly(propylene fumarate) and block copolymers for use as biocompatible materials are unreported in the patent literature. Biocompatible polymers Biodegradable polymers Bioresorbable polymers Poly(propylene fumarate) and block copolymers are biodegradable and are used in prostheses and as drug delivery agents. The first of these copolymers, poly(propylene funarate-co-ethylene oxide), was originally prepared at Rice University and used as a vascular implant. Although crosslinking of these copolymers has produced polymeric networks useful for in vivo applications, there remains a need to improve the mechanical strength. In the current application at the Mayo Foundation for Medical Education and Research a polymeric agent was designed and prepared to address that specific need. Although newer methods exist for preparing block copolymers that use transesterification reactions with diethyl fumarate have previously been prepared by this group, efforts are also being focused on identifying high-density crossliking agents. These agents will be used as in situ hardening agents for injectable copolymers and used in scaffolds in tissue engineering applications. Finally, newer synthetic methods for preparing porous substrates are also being investigated by this group as a method for preparing resorbable polymers.

Experimental

415

REACTION

i. 1,2-Propylene glycol, hydroquinone, zinc chloride ii. Polypropylene glycol iii. Poly(1-caprolactone), poly(caprolactonediol), antimony trioxide

EXPERIMENTAL 1. Preparation of bis(hydroxypropyl) fumarate A reactor was charged with diethyl fumarate (259 g) and1,2-propylene glycol (342 g) containing hydroquinone (0.33 g) and zinc chloride (2.04 g) as catalyst and then heated to 1008C for 1 hour and then further heated to 1508C for 7 hours. The product was then isolated and used without further purification. 2. Preparation of poly(propylene fumarate) The step 1 product was transesterified to form linear poly(propylene fumarate) containing hydroxyl groups on the termini. The polymerization was performed using propylene glycol under vacuum at 1008C and then at 1308C for 3 hours where the molecular weight was modulated by the reaction extent. The product was then isolated and used without further purification. 3. Preparation of poly(propylene fumarate)-block-1-caprolactone) A reaction vessel was charged with the step 2 product, poly(1-caprolactone), poly(caprolactone) diol (100 g), and antimony trioxide (0.2 g) heated to 1008C for 30 minutes and the temperature gradually increased to 1608C under a very high vacuum for TABLE 1. Molecular Weights and Physical Properties of Crosslinkable Poly(propylene-fumarate)-block-1-caprolactone)s of the Current Invention Entry 1 2 3

Mw (Da)

Mn (Da)

Tg (8C)

Td (8C)

20,800 25,200 8230

6010 6180 4030

222.9 220.5 224

350 346 359

416

Block Copolymers of Polycarpolactone and Poly(Propylene Fumarate)

5 hours. The block polymer was purified by dissolving in CH2Cl2 and then washed twice with 600 ml of 10% hydrochloric acid, distilled water, and brine. The solution was filtered in diethyl ether, dried, and the product isolated in 70% yield as waxlike material at ambient temperature.

NOTES 1. All block copolymers were crosslinked to construct tissue engineering scaffolds using the method of Yaszemski et al. (1) as described below. Thermal crosslinking was performed using benzoyl peroxide and N-dimethyl toluidine as the free radical initiator and accelerator, respectively. The polymerizing scaffold was transferred into various Teflon molds placed in a convection oven overnight to facilitate crosslinking. Photocrosslinking was initiated with ultraviolet (UV) light with l ¼ 315– 380 nm using bisacylphosphine oxide. The mixture was then poured into a mold formed by two glass plates separated by a spacer and the mold placed directly under UV light for 30 minutes to facilitate crosslinking. 2. He et al. (2) prepared a hydrolyzably crosslinked biodegradable network consisting of poly(propylene fumarate) crosslinked with the diacrylate derivative of poly(propylene fumarate), (I).

References 1. M.J. Yaszemski et al., U.S. Patent Application 20070043202 (February 22, 2007). 2. S. He et al., U.S. Patent 6,423,790 (July 23, 2002).

c. Polypropylene glycol esters

Title: Biodegradable and Biocompatible Peg-Based Poly(Ester-Urethanes) Author: Assignee:

Patrick F. Kiser et al. University of Utah Research Foundation (Salt Lake City, UT)


20080140185 (June 12, 2008) High December, 2010

Synthesis of biodegradable and biocompatible polyethylene oxide derivatives containing poly(ester-urethanes) for use as medical implants. This has been a 3-year ongoing investigation by this group in the preparation of biodegradable elastomers. Biodegradable elastomers Although poly(urethane) elastomers have been used extensively in medical applications, their ability to biodegrade is not an inherent property. Degradation rates of these materials when used in vivo testing were less than optimum. To address this concern the current application describes a method for preparing biodegradable elastomers by initially forming a stable prepolymeric block by condensing poly(ethyleneglycol) with 6,6-dimethyl-1,4-dioxane-2,5-dione. The intermediate diol is then converted to an elastomer by reacting with selected diisocyanates as the difunctional linker.

417

418

Biodegradable and Biocompatible Peg-Based Poly(Ester-Urethanes)

REACTION

i. Toluene, poly(ethylene glycol), tin(II)-2-ethylhexanoate ii. Tin(II)-2-ethylhexanoate, 4,40 -methylenebis(cyclohexyl isocyanate), ethylene glycol, N,N-dimethylacetamide EXPERIMENTAL 1. Preparation of a,v-dihydroxylactide-poly[(tetrahydrofuran)-co-(lactide)] prepolymer A reactor was charged with 100 ml of toluene, 6,6-dimethyl-1,4-dioxane-2,5-dione (0.138 mol), poly(ethylene-glycol) (0.00578 mol; 1000 Da), and tin(II)-2-ethylhexanoate (90% in 2-ethylhexanoic acid (0.141 mmol) and then refluxed for 24 hours using a Soxhlet extractor. The mixture was then cooled and concentrated. 2. Preparation of a,v-dihydroxylactide-poly[(tetrahydrofuran-co-urethane)] A 25-ml scintillation vial was charged with the step 1 product (7 g), tin(II)-2-ethylhexanoate, and ethylene glycol (7.507 mmol) and then thoroughly shaken using a KEM-Lab vortex mixer at 35 rpm. This mixture was then treated with 4,40 -methylenebis(cyclohexylisocyanate) (11.262 mmol) and then further shaken by the vortex mixer for 1 minute. The vial was then placed into a heat shaker for 15 minutes and stirred to ensure its consistency and then returned to the heat shaker for 3.45 hours. Half of the hot mixture was removed from the vial and placed into a second vial, which was treated with 15 ml of N,N-dimethylacetamide and put onto the shaker until the biodegradable elastomer was dissolved. This solution was then precipitated in 1000 ml of water, the dissolution/precipitation process being repeated twice. Thereafter the precipitated polymer was isolated and purified by lyophilization. DERIVATIVES Additional poly(ester-urethane) derivatives were prepared by reacting the step 1 prepolymer diol with selected diisocyanate as indicated below: Hexamethylene diisocyanate 2,2,4-Trimethylhexamethylene diisocyanate

Notes

419

Cyclohexyl-1,4-diisocyanate Cyclohexyl-1,2-diisocyanate Isophorone diisocyanate Methylenedicyclohexyl diisocyanate L-Lysine diisocyanate methyl ester

NOTES 1. Other poly(ester-urethanes) derivatives were prepared by the authors (1) in an earlier investigation and are discussed. 2. Biocompatible materials consisting of poly(ester-amides), (I), were prepared by DesNoyer et al. (2) and used in cardiovascular medical devices.

3. Wagner et al. (3) prepared elastomeric materials consisting of biodegradable poly(urea-urethanes), (II), containing microintegrated cells that were useful as pulmonary valves, vocal chords, and blood vessels.

4. Katsarava et al. (4) prepared biodegradable hydrogels, (III), consisting of epoxy-containing poly(ester amides), which were used as implantable medical devices for delivery of biologically active agents.

420

Biodegradable and Biocompatible Peg-Based Poly(Ester-Urethanes)

References 1. P.F. Kiser et al., U.S. Patent Application 20080140185 (June 12, 2008). 2. J.R. DesNoyer et al., U.S. Patent Application 20080177008 (July 24, 2008), U.S. Patent Application 20080175886 (July 24, 2008), and U.S. Patent Application 20080167712 (July 10, 2008). 3. W.R. Wagner et al., U.S. Patent Application 20080109070 (May 8, 2008). 4. R. Katsarava et al., U.S. Patent Application 20080050419 (February 28, 2008).

B. Biomaterials for Dental Applications a. Acylgermane-containing polymers

Title: Polymerizable Compositions with Acylgermanes as Initiators Author: Assignee:

Norbert Moszner et al. Ivoclar Vivadent AG (Schaan, LI)


20080076847 (March 27, 2008) Substantial 2010

Synthesis of mono- and bisacylgermane derivatives useful as polymerization initiators in dental cements. Acylgermane derivatives as polymerization initiatiors have not been reported in the technical literature. Dental materials The commercial Norrish Type I photoinitiator Irgacurew-819, bis(2,4,6trimethylbenzoyl)-phenyl phosphine oxide, has the longest wave absorption maxima at 397 nm. Norrish Type I photoinitiators benzoyltrimethylgermanium and bisbenzoyl diethylgermanium derivatives were prepared having absorption maxima at 411.5 nm and at 418.5 nm, respectively, which are more bathochromic and which significantly improve the curing depth of the photoreactive dental products. While titanocenes have an absorption maximum at approximately 480 nm, these agents are reported to have inadequate photobleaching that results in orange-colored polymers. Although the Norrish Type II photoinitiator camphorquinone has an absorption maximum at 468 nm, it requires an additional component for efficient radical formation.

421

422

Polymerizable Compositions with Acylgermanes as Initiators

REACTION

i. Allyl palladium(II) chloride dimer, triethylphosphite, benzoyl chloride

EXPERIMENTAL 1. Preparation of benzoyltrimethylgermanium A reactor was charged with allyl palladium(II) chloride dimer (4.49 mmol), triethylphosphite (8.97 mmol), and hexamethyldigermanium (98.7 mmol) and then stirred for 5 minutes at ambient temperature and treated with the dropwise addition of freshly distilled benzoyl chloride (89.7 mmol). After stirring for 4 hours at 1108C the mixture was filtered and concentrated. The residue was purified by column chromatography using petroleum ether/ethyl acetate, 40:1, respectively, and 7.8 g of product isolated as a yellow liquid having a lmax of 411.5 nm with 1 ¼1374 dm2/mol. H-NMR (CDCl3) d: 7.78– 7.82 (m, 2H, ArZH2,6), 7.48– 7.58 (m, 3H, ArZH3,4,5), 0.51 (s, 9H, ZCH3) C-NMR (CDCl3) d: 234.39 (ZCvO), 140.61 (ArZC1), 132.90 (ArZC4), 128.75 (ArZC2,6), 127.71 (ArZC3,5), 21.14 (ZCH3) 21 FTIR (cm ): 2979, 2916, 1628 (CvO), 1582, 1448, 1310, 1239, 1207, 1172, 905, 827, 770, 732

1

13

DERIVATIVES

423

Testing

TESTING A. Composite Preparation Composite fixing cements were prepared based on a standard methacrylate mixture and incorporating either the step 1 product or a mixture of camphorquinone and p-N,N-dimethylaminobenzoic acid ethyl ester using an Exakt Apparatebau model roll mill. Testing results are summarized in Table 1. B. b Value b Values for uncured and cured composite fixing cements were determined according to the DIN standard 5033 Farbmessung Test using a Minolta CR-300 L a b color measurement system. Testing results are provided In Table 2. TABLE 1. Cement Fixing Compositions for Evaluation of Bonding Exothermic Time, Strength, and Elastic Modulus Component

Cement A

Cement B

Cement C

Comparison Cement D

0.10 — —

0.32 — —

0.50 — —

— 0.24 0.23

32.11 7.81

31.89 7.81

31.71 7.81

31.80 7.81

41.27 18.71

41.27 18.71

41.28 18.70

41.23 18.69

Step 1 product Camphorquinone Ethyl 4-N,Ndimethylaminobenzoate UMDAa Triethyleneglycol dimethacrylate Aerosil OX-50 Ytterbium trifluoride a

Addition product of 2 mol 2-hydroxylethylmethacrylate and 1 mol 2,2,4-trimethylhexamethylene diisocyanate.

TABLE 2.

Cement Composites and Their Effect on Physical Properties of Cementsa

Component Exothermic time (s) Bonding strength (MPa) after 24 hours WIb Elastic modulus (MPa) after 24 hours WIb b Value of paste before curingc b Value of paste after curing

Cement A

Cement B

Cement C

Comparison Cement D

13 102

12 116

11 129

8 118

3230

5420

5560

5580

7.7 25.8

16.0 21.9

19.6 0.7

27.4 4.5

a The use of the step 1 product in the cement composition resulted in shorter exothermic times and faster curing. Lower b values are indicative of nondiscolored dental pastes. b Water immersion of the test piece at 378C. c Testing according to DIN standard 5033 Farbmessung.

424

Polymerizable Compositions with Acylgermanes as Initiators

NOTES 1. Photopolymerizable dental materials were previously prepared by the authors (1) using bisacylphosphine oxide derivatives, (I), as initiators.

2. Multifunctional photoinitiators, (II), were prepared by Sommerlade et al. (2) for radiation-curable dental compositions using UV light. A Norrish Type II visible-light-sensitive multifunctional ketopinic amide derivative attached to a modified amino-silanated resin, (III), was prepared by Condon et al. (3) and used as a macroinitiator in dental applications.

3. Organopolysiloxanes hydroxyalkylphenone macromolecular photoinitiators, (IV), and related monomers, (V), useful as radiation curing agents were prepared by Brand et al. (4) and used in adhesives.

Notes

425

4. To extend the storage stability of diketo photoinitiators, (VI), Ulrich et al. (5) converted them into a-hydroxyketones, (VII), which were activated at ,500 nm as illustrated in Eq. (1).

(1)

i. Morpholine, THF ii. 4-Methylbenzyl magnesium bromide, THF

References 1. N. Moszner et al., U.S. Patent Application 20070027229 (February 1, 2007). 2. R. Sommerlade et al., U.S. Patent Application 20060270748 (November 30, 2006). 3. J.R. Condon et al., U.S. Patent Application 20050065227 (March 24, 2005). 4. M. Brand et al., U.S. Patent Application 20070055029 (July 31, 2007). 5. T. Ulrich et al., U.S. Patent Application 7,291,654 (November 6, 2007).

b. Carbosilane methacrylate oligomers

Title: Dental Compositions Containing Carbosilane Polymers Author: Assignee:

Kevin M. Lewandowski et al. 3M Innovative Properties Company (St. Paul, MN)


426


Synthesis of dental compositions containing carbosilane methacrylate oligomers that have low shrinkage upon crosslinking. Four-year ongoing investigation preparing crosslinkable carbosilane oligomers. Dental compositions and prostheses Volume shrinkage of 2–4% in cured dental compositions results in high stress and microfractures in the composite that can lead to clinical failure of the composite material. To address this problem carbosilane methacrylate oligomers were prepared that have shrinkage rates less than 1.5% upon thermal curing while retaining compressive strength and viscosity. Carbosilane methacrylate oligomers were prepared in a two-step process. Initially a di-allyloxy intermediate was methacrylated using methacrylic anhydride to introduce a thermal crosslinker. Hydrosilation of this product was performed using chloroplatinic acid and symdivinyltetramethyldisiloxane with 1,3- or 1,4-bis-dimethylsilylbenzene. The cationic photoinitiator diphenyl iodonium hexafluorophosphate was used to polymerize all blended compositions.

Experimental

427

REACTION

i. Methacrylic anhydride, triethylamine, 4-dimethylaminopyridine, THF ii. 1,4-Bis-dimethylsilylbenzene, toluene, platinum-divinyltetramethyldisiloxane, xylene iii. Bisglycidylacrylate, ethoxylated bisphenol A dimethacrylate, diurethane dimethacrylate, triethyleneglycol dimethacrylate, tricycle[5.2.1.02,6]decanedimethanol diacrylate, camphorquinone, ethyl 4-(N,N-dimethylamino)benzoate, diphenyl iodonium hexafluorophosphate, 2,6-di-t-butyl-4-methylphenol, benzotriazole

EXPERIMENTAL 1. Preparation of 2-methylacrylic acid 2-allyloxy-1-allyloxymethyl-ethyl ester A mixture consisting of glycerol diallyl ether (0.17 mol), methacrylic anhydride (0.19 mmol), triethylamine (0.17 mol), 4-dimethylaminopyridine (8.6 mmol), and 70 ml THF was stirred at ambient temperature for 4 hours. It was then treated with additional 4-dimethyl-aminopyridine (8.6 mmol) and then stirred at ambient temperature for an additional 48 hours and then concentrated. The residue was dissolved in 400 ml ethyl acetate and then extracted once with 200 ml saturated aqueous sodium bicarbonate and three times with 100 ml saturated aqueous sodium chloride. The organic layer was then dried over MgSO4, concentrated, and the residue distilled under reduced pressure. Two fractions were collected. The first (7.48 g) was collected at 60– 808C @ 0.15 mmHg and the second fraction (8.57 g) was collected between 80 and 858C @ 0.15 mm. The higher boiling fraction was combined with 4.6 g of the lower boiling fraction and then purified by column chromatography over silica gel using 30 wt% ethyl acetate in hexane and 8.90 g of product isolated as a colorless oil. 2. Carbosilane oligomer containing 1,4-disubstituted phenyl A mixture of 1,4-bis-dimethylsilylbenzene (7.9 mmol), the step 1 product (2 mmol), 10 ml toluene, and two drops of a solution of platinum-divinyltetramethyldisiloxane

428

Dental Compositions Containing Carbosilane Polymers

complex in xylene was stirred at ambient temperature for 90 minutes. It was then purified using silica gel column chromatography with ethyl acetate/hexane, 4:6, respectively. After evaporating the solvent 4.20 g of product was isolated as an oil with a viscosity of 812 cP. 3. Polymerization of carbosilane oligomer containing 1,4-disubstituted phenyl: General procedure Polymerizable compositions were prepared according to the following general procedure. Camphorquinone (0.176 phr), ethyl 4-(N,N-dimethylamino)-benzoate (1.55 phr), diphenyl iodonium hexafluorophosphate (0.517 phr), 2,6-di-t-butyl-4-methylphenol (0.155 phr), and benzotriazole (1.552 phr) were dissolved in bisglycidylacrylate and combined with 6 mol ethoxylated bisphenol A dimethacrylate, diurethane dimethacrylate, triethyleneglycol dimethacrylate,tricycle[5.2.1.02,6]-decanedimethanol diacrylate, and the step 2 product. The blended components plus the filler component consisting of silane-treated zirconia-silica were weighed in a MAX 20 plastic mixing cup having a screw cap and heated in an oven at 858C for 30 minutes. The cup was placed in a speed mixer and spin mixed for 1 minute at 3000 rpm. The cup was then reheated for 30 minutes 858C followed by another minute of mixing at 3000 rpm to yield the final composition.

DERIVATIVES

TESTING Physical properties of polymerized carbosilane methacrylate oligomers are provided in Table 1.

429

Notes

TABLE 1.

Entry

Physical Properties of Polymerized Carbosilane Methacrylate Oligomersa Comprehensive Shrinkage Strength (vol%) (MPa)

Structure

Diametral Tensile Strength (MPa)

1

1.48

—

—

2

1.2

—

—

3

—

305

72

a

All polymerizations were performed 858C for 1 hour with bisglycidylacrylate, ethoxylated bisphenol A dimethacrylate, diurethane dimethacrylate, triethyleneglycol dimethacrylate, and tricycle[5.2.1.02,6] decanedimethanol diacrylate.

NOTES 1. Additional curable carbosilane oligomers useful in dental applications containing a 1,4-disilyl aromatic component, (I), were previously prepared by the authors (1) and are discussed.

430

Dental Compositions Containing Carbosilane Polymers

2. Curable dental compositions containing dithiane, (II), which had low shrinkage rates were previously pepared by the authors (2).

3. Halogenated 1,4-disubstituted phenyl ether derivatives, (III), were prepared by Eckert et al. (3) and used as low shrinkage components in dental compositions.

4. Dental compositions prepared by Bissinger et al. (4) consisting of an aromatic carbosilane component, (IV), and an unsaturated alkenyl or epoxy component, initiator, and filler had a volumetric shrinkage of less than 2 vol% after polymerization.

Notes

431

5. Moszner et al. (5) prepared low shrinkage dental compositions containing bicyclic cyclopropane derivatives, (V).

References 1. K.M. Lewandowski et al., U.S. Patent Application 20070276059 (November 29, 2007). 2. K.M. Lewandowski et al., U.S. Patent Application 20070066748 (March 22, 2007). 3. A.S. Eckert et al., U.S. Patent Application 20080051488 (February 28, 2008). 4. P. Bissinger et al., U.S. Patent Application 20070238803 (October 11, 2007). 5. N. Moszner et al., U.S. Patent Application 20070232719 (October 4, 2007).

c. Crosslinked polysilicones

Title: Dental Compositions Containing Carbosilane Monomers Author: Assignee:

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


Observations:

432

20070276059 (November 29, 2007) High Mid-2010

The preparation of hardenable and inert dental compositions containing silicone and multiple crosslinkable sites. This is a continuation of an ongoing investigation for preparing thermally or photochemically curable inert dental components by this group. Viscosity modifier Thixotropic agent Polymeric thickener The objective of this investigation was to prepare polymeric dental materials having a shrinkage rate of less than 2% while maintaining compressive strength and viscosity. This was achieved using monomers containing two Si-arylene substituents and treating with diurethane dimethacrylate, triethyleneglycol dimethacrylate, and allyl methacrylate. Using this method an average shrinkage value of 1.57 was obtained. In addition when dithiane derivatives were used a shrinkage of 1.43 was observed.

Experimental

433

REACTION

i. 1,4-Bisdimethylsilylbenzene, allyl methacrylate, toluene, platinum divinyltetramethyldisiloxane, xylene ii. 2,2-Bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane, 6 mol ethoxylated bisphenol A, diurethane dimethacrylate, triethyleneglycol dimethacrylate, camphorquinone, ethyl-(4,4dimethylamino)benzoate, diphenyl iodonium hexafluorophosphate, 2,6-di-t-butyl-4-methyl phenol, benzotriazole

EXPERIMENTAL 1. Preparation of 1,4-bis-(dimethyl-[3-(methacryloyloxy)propyl]silyl)benzene A round-bottom flask consisting of a mixture of 1,4-bis-dimethylsilylbenzene (25.7 mmol), allyl methacrylate (51.4 mmol), 20 ml of toluene, and two drops of platinum divinyltetramethyldisiloxane complex dissolved in xylene were stirred at ambient temperature for 17 hours. The mixture was then loaded onto a silica gel column and eluted with a mixture of ethyl acetate/hexane, 20,80, respectively, and then concentrated and 7.8 g product isolated as a colorless oil having a viscosity of 136 cP. 2. Preparation of crosslinked polymer containing poly(1,4-bis-(dimethyl[3-(methacryloyloxy)propyl]silyl)benzene) The step 1 product was photopolymerized by dissolving in 2,2-bis[4-(2-hydroxy-3methacryloxypropoxy)phenyl]propane dissolved in xylene and mixing with 6 mol ethoxylated bisphenol A, diurethane dimethacrylate, triethyleneglycol dimethacrylate, camphorquinone (0.176 phr), ethyl-(4,4dimethylamino)benzoate (1.55 phr), diphenyl iodonium hexafluorophosphate (0.517 phr), 2,6-di-t-butyl4-methyl phenol (0.155 phr), and benzotriazole (1.552 phr). The blended components plus the filler component STZ were weighed into a MAX 20 plastic mixing cup and having a screw cap and then sealed and heated to 858C for 30 minutes. The cup was placed in a DAC 150 FV speed mixer and spin mixed for 1 minute at 3000 rpm. The cup was then reheated for 30 minutes at 858C followed by another minute of mixing at 3000 rpm and the blended composition isolated.

434

Dental Compositions Containing Carbosilane Monomers

DERIVATIVES Selected step 1 crossing agents and corresponding viscosities are provided in Table 1. TABLE 1. Summary of Preferred Crosslinkable Step 1 Carbosilane Monomers and Corresponding Viscosities Entry

Monomer Structure

Viscosity (cP)

2

7411

3

3879

4

32

5

127

TESTING Polymerization Shrinkage Test Method The Watts shrinkage test method measures shrinkage of a test sample in terms of volumetric change after curing. The sample preparation consisted of using 90 mg of an

Notes

435

uncured composite test sample and the test procedure carried out as described in Determination of Polymerization Shrinkage Kinetics in Visible-Light-Cured Materials. Only limited polymer shrinkage data were supplied by the author in the current application.

NOTES 1. Anderson et al. (1) prepared curable dental compositions consisting of the reaction products of amine-terminated polyethers, methacrylate-terminated polyethers, 2-hydroxyethyl(meth)-acrylate, and N-vinyl pyrrolidone. 2. Low shrinkage curable compositions containing dithiane monomers, (I), were prepared by the authors (2) and used in polymerizable dental components.

3. Dietliker et al. (3) prepared photoinitiators, (II), that were used in dental compositions as filling materials and to seal cavities.

4. Falsafi et al. (4) prepared polymerizable compositions of arylsulfinate salts containing ethylenically unsaturated substitiuents that were used as hardenable agents in dental compositions.

References 1. K.S. Anderson et al., U.S. Patent Application 20070275042 (November 29, 2007). 2. K.M. Lewandowski et al., U.S. Patent Application 20070066748 (March 22, 2007). 3. D. Dietliker et al., U.S. Patent Application 20080021126 (January 24, 2008). 4. A. Falsafi et al., U.S. Patent Application 20080014560 (January 17, 2007).

d. Gemini aromatic epoxides

Title: Dental Compositions Containing Oxirane Monomers Author: Assignee:

Roger M. Mader et al. 3M Innovative Properties Company (St. Paul, MN)



436

20080085494 (April 10, 2008) Moderate 2011

Synthesis of ether-linked gemini aromatic epoxides. While the use of expoxide derivatives as dental materials is well documented in the literature, those materials having good mechanical strength and low shrinkage are limited. Restorative dental materials Except for glass ionomers, most organic-based dental restoratives have been based on methacrylate/acrylate chemistries. Many of these polymers exhibit high stress upon curing because of excessively high polymerization shrinkage. Although oxirane chemistries have demonstrated lower shrinkage and lower polymerization stress than the best existing methacrylate-based materials, the refractive index of oxiranes systems do not match refractive index of quartz/radiopaque melt glasses/radiopaque sol gel fillers. To address this concern, aromatic oxirane-based dental compositions have been prepared that have good aesthetics, mechanical properties, and low shrinkage.

Derivatives

437

REACTION

i. 1,10-Dibromodecane, potassium carbonate, methyl ethyl ketone ii. CH2Cl2, 3-chloroperbenzoic acid, sodium hydroxide iii. Photocure EXPERIMENTAL 1. Preparation of 1,10-bis[2-(allylphenoxy)decane] A mixture consisting of 2-allylphenol (35 g), 1,10-dibromodecane (39 g), and potassium carbonate (36 g) dissolved in 150 ml of methyl ethyl ketone was heated to 808C for 24 hours and then treated with 200 ml of water and 200 ml of hexane. The resulting mixture separated into an organic phase and an aqueous phase. The organic phase was washed with water, dried over Na2SO4, and then concentrated. After distillation at 210– 2158C @ 0.1 mmHg, 26 g of product was isolated as a liquid. 2. Preparation of 1,10-bis[2-(2,3-epoxypropyl)phenoxy]decane The step 1 product (21 g) was dissolved in 210 ml of CH2Cl2 and then treated with 77% m-chloroperbenzoic acid (41.6 g) at ambient temperature for 6 hours. The mixture was then poured into a solution of sodium hydroxide (40 g) dissolved in 150 ml of water and 200 ml of hexane and then stirred and cooled to 108C using an ice bath. The organic layer was isolated and washed once with 100 ml of 5% Na2S2O4 and three times with 100 ml of 10% KCl solution. The mixture was concentrated and the residue purified using silica gel column chromatography with hexane/ ethyl acetate, 3:1, respectively. An oil, which was obtained, was dissolved in 100 ml of 10% ethyl acetate in hexane and treated with basic aluminum oxide (3 g) to remove color on the product. After filtration 13 g of product were isolated as a liquid. DERIVATIVES

438

Dental Compositions Containing Oxirane Monomers

TESTING A. Photo Differential Scanning Calometer (DSC) Test Method A test sample of a resin containing a selected experimental agent was weighed in a DSC pan to +0.0.00001 g. The uncured sample was placed on a sample cell and a precured sample of the same weight was placed in the same type of DSC pan on the reference cell set and maintained at 378C while being irradiated for 1 hour. From the resulting heat flow (watts/g vs. time curve), the time of maximum reaction rate (peak maximum time), onset of reaction (induction time), and enthalpy of reaction were recorded. These testing results are provided in Table 1.

TABLE 1. Polymerization Properties of Photochemically Prepared Using Resin Compositions Containing the Step 2 Product Entry

Average EEWa (g/mol)

Average Induction Time (minute)

Average Energy (J/mol)

216 216 201 191 203

0.19 0.17 0.27 0.31 0.19

43,783 57,253 58,646 67,257 63,531

Comparison-C3-R 5R 6R 7R 8R a

Epoxy equivalent weight determined using HClO4.

B. ACTA 3-Body Wear Test Method (ACTA) The ACTA 3-body wear testing for experimental polymers was performed according to the method of Pallav et al. (1). Testing results are provided in Table 2.

TABLE 2. Physical Properties of Experimental Polymers Photochemically Prepared Containing the Step 2 Product Entry Comparison-C3 5 6 7 8 a

Gel Time (s)

Postgel Shrinkagea

Flexural Modulus (MPa)

ACTA

2 1 7 8 2

520 1158 793 1212 937

9358 9457 10,449 9339 9328

2.00 2.21 2.85 2.20 2.02

Average microstrain at 3600 seconds.

Notes

439

NOTES 1. Eckert et al. (2) prepared curable dental compositions consisting of epoxy functionalized carbosilane derivatives, (I). Carbosilanes, (II), were prepared by Chappelow et al. (3) and used in dental matrix resin systems, such as restorative composites.

2. Polymerizable oligomers, (III), were prepared by Shuhua et al. (4) and used as a component in dental restorative materials.

3. Dental composites containing thermally labile components, (IV) and (V), were prepared by Kalgutkar et al. (5) and used for reducing bond strength of orthodontic appliances that were adhered to tooth structures.

4. Photopolymerizable compositions containing dioxiranyl tetraoxaspiro-[5.5]undecanes, (VI), were prepared by Chappelow et al. (6) and used as dental restorative materials.

440

Dental Compositions Containing Oxirane Monomers

References 1. P. Pallav et al., Journal of Dental Research, January 1993. 2. A.S. Eckert et al., U.S. Patent Application 20080031830 (February 7, 2008). 3. C.C. Chappelow et al., U.S. Patent Application 20070072954 (March 29, 2007). 4. J. Shuhua et al., U.S. Patent Application 20070173558 (July 26, 2007). 5. R.S. Kalgutkar et al., U.S. Patent Application 20070142494 (June 21, 2007). 6. J C.C. Chappelow et al., U.S. Patent 7,232,852 (June 19, 2007).

e. 7-Methylene dithiane terminated methacrylate

Title: Dental Compositions Containing Hybrid Monomers Author: Assignee:

Ahmed S. Abuelyaman et al. 3M Innovative Properties Company (St. Paul, MN)


20080194722 (August 14, 2008) High June, 2010

Synthesis of polymerizable hybrid monomers containing equivalent amounts of methacrylate and 7-methylene dithiane termini. Monomers containing methacrylate and dithiane termini are unreported in the patent literature. Restorative dentistry Typical dental composite resins contain low-viscosity dimethacrylate monomers such as triethyleneglycol dimethacrylate shrink substantially upon polymerization because of their low molecular weight. To address this concern linear hybrid monomers containing methyacrylate and dithiane termini were photochemically polymerized and had a Watts shrinkage of less than 1.6%. Watts shrinkage rates of 2% or less were previously reported for dimethacrylate dithiane monomers by this group in an earlier investigation. Photoinitiated carbosilane dimethacrylate monomers were also prepared by this group used in dental compositions also had Watts shrinkage or less than 2%.

441

442


REACTION

i. Mono-2-methacryloyloxyethyl phthalate, CH2Cl2, 4-(N,N-dimethylamino)pyridine, N,N-dicyclohexyl carbodiimide ii. Diphenyl iodonium hexafluorophosphate, bisphenol A diglycidyl dimethacrylate, bisphenol A diglycidyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethlyene glycol dimethacrylate

EXPERIMENTAL 1. Preparation of 1-(2-methacryloyloxyethyl)-2-(7-methylene1,5-dithiaoctan-3-yl) phthalate Mono-2-methacryloyloxyethyl phthalate (31 mmol) and 7-methylene-1,5-dithiacyclooctan-3-ol (31 mmol) were dissolved in 50 ml CH2Cl2 and treated with 4-(N,N-dimethylamino)pyridine (400 mg). The mixture was cooled in an ice bath for 20 minutes and then treated with the dropwise addition of N,N-dicyclohexyl carbodiimide (34 mmol) dissolved in 50 ml CH2Cl2 over a period of 60 minutes. The mixture was stirred for 60 minutes in the ice bath and then at ambient temperature overnight. A precipitate that formed was removed by vacuum filtration using a Buchner funnel with filtration aid Celitew and then washed with 100 ml of 0.1 M HCl, 100 ml of 5% NaOH, and finally with 100 ml of water. The organic layer was dried, concentrated, and 11.4 g product isolated as a slightly cloudy viscous liquid. 2. Preparation of hybrid polymer A mixture consisting of the step 1 product, bisphenol A diglycidyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, triethlyene glycol dimethacrylate, bisphenol A diglycidyl dimethacrylate, and diphenyl iodonium hexafluorophosphate were thoroughly mixed with diphenyl iodonium hexafluorophosphate and then heated to 858C for 5 minutes and mixed in a DAC 150 FV speed mixer for 1 minute at 3000 rpm. Silane-treated, nanosized silica and zirconia particle filler was added and the mixture reheated to 1858C for 5 minutes, remixed in a DAC 150 FV and an additional 1 minute at 3000 rpm, and the dental composition isolated.

Testing

443

DERIVATIVES

TESTING A. Diametral Tensile Strength Diametral tensile strength of experimental agents was measured using an uncured composite sample that was injected into a 2-mm container and then capped with silicone rubber plugs and compressed axially at approximately 2.88 kg/cm2 pressure for 5 minutes. The sample was then light cured for 80 seconds by exposure to an XL 1500 dental curing light followed by irradiation for 90 seconds in a Kulzer UniXS curing box. Cured samples then stood for 1 hour at 378C with 90%þ relative humidity.

444


They were then cut with a diamond saw to form 8-mm-long cylindrical plugs and evaluated for diametral tensile strength using an Instron tester. Testing results of selected experimental agents are provided in Table 2. B. Watts Shrinkage Test The Watts shrinkage test method measures shrinkage of a test sample in terms of volumetric change after curing. The sample preparation and procedure are described in Determination of Polymerization Shrinkage Kinetics in Visible-Light-Cured Materials: Methods Development, Dental Materials, October 1991, pages 281– 286. Testing results of selected experimental samples are in Table 2. C. Barcol Hardness Test Barcol hardness testing was measured according to the following procedure. An uncured composite was cured in a 2.5-mm-thick Teflon mold sandwiched between a sheet of poly(ethylene terphalate) and a glass slide for 30 seconds and then with an ELIPAR Freelight 2 dental curing light. After irradiation the poly(ethylene terphalate) film was removed and the hardness of the sample at top and the bottom of the mold measured using a Barber-Coleman impressor equipped with an indenter. Testing results of selected experimental samples are in Table 2. TABLE 1. Photopolymerizable Dental Compositions Prepared Containing the Step 1 Product Dental Composition Component (parts by weight) a

BisGMA BisEMA-6b UDMAc Step 2 product CPQd EDMABe DPIHEFf BHTg Filler a

Entry 5

Entry 7

Entry 8

Entry 9

4.99 4.35 4.75 9.50 0.04 0.22 0.11 0.03 76

4.87 0 4.24 13.54 0.04 0.21 0.11 0 77

9.32 0 4.21 9.12 0.04 0.21 0.10 0 77

13.8 0 4.14 4.73 0.03 0.20 0.10 0 77

2,2-Bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane. Ethoxylated bisphenol A dimethacrylate. c Diurethane dimethacrylate. d Camphorquinone. e Ethyl 4-(N,N-dimethylamino)benzoate. f Diphenyl iodonium hexafluorophosphate. g 2,6-Di-t-butyl-4-methylphenol. b

Notes

445

TABLE 2. Physical Properties of Cured Dental Compositions Containing Step 1 Hybrid Monomera Watts Entry 5 7 8 9 Referencec

Barcol Hardness b

Visual

Shrinkage (%)

DTS (MPa)

Top

Bottom

Opacity

1.58 1.3 1.36 1.33 1.93

71 74 68 65 76

83 80 80 80 86

81 76 76 75 85

0.35 0.30 0.27 — 0.35

a

Dental compositions are provided in Table 1. Dimetral tensile strength. c FILTEK SUPREME restorative. b

NOTES 1. Additional curable compositions containing dithiane monomers, (I), were prepared by Lewandowski et al. (1) and are discussed.

2. Lewandowski et al. (2) prepared carbosilane-containing polymer-containing methacrylate components, (II), which were effective in dental compositions and had a Watts shrinkage of less than 2%. Crosslinkable carbosilane methacrylate monomers, (III), used in dental compositions were also prepared by Lewandowski et al. (3) and had a Watts shrinkage of less than 2%. Additional low-shrinkage carbosilane derivatives effective in dental compositions are described by Bissinger et al. (4).

446


3. Nozawa et al. (5) prepared reactive methacrylate monomers containing isocyanate functions, (IV), which were used in dental compositions for preparing low-shrinkage polymers.

References 1. K.M. Lewandowski et al., U.S. Patent Application 20070066748 (March 22, 2007). 2. K.M. Lewandowski et al., U.S. Patent Application 20080045626 (February 28, 2008). 3. K.M. Lewandowski et al., U.S. Patent Application 20070276059 (November 19, 2007). 4. P. Bissinger et al., U.S. Patent Application 20080070193 (March 20, 2008). 5. K. Nozawa et al., U.S. Patent Application 20080132597 (June 5, 2008).

C. Biomaterials for Diagnostics a. Polymers containing acylsulfonamide amine-reactive groups

Title: Soluble Polymers as Amine Capture Agents and Methods Author: Assignee:

Karl E Benson et al. 3M Innovative Properties Company (St. Paul, MN)



20080132665 (June 5, 2008) High June, 2011

Synthesis of copolymers containing pendant acylsulfonamide aminereactive groups that are suitable for isolating recombinant protein P. Very limited U.S. patent art exists on the use of pendant polymers containing acylsulfonamide that contain amine-reactive group as capture agents. Medical diagnostics Terpolymers were synthesized in four steps containing pendant acylsulfonamide amine-reactive groups that bind to the terminus of recombinant protein P with high specificity. The binding reaction consists of a trans-acylsulfonamidation. Polymers derivatized with pendant malimide or saccharin sulfonamides are particularly active in binding recombinant protein P. In an earlier investigation by this group solvent-soluble crosslinked acylsulfonamide amine-reactive terpolymers were prepared and used to covalently bind to recombinant protein P and in medical diagnostics.

447

448

Soluble Polymers as Amine Capture Agents and Methods

REACTION

i. ii. iii. iv.

Dimethylformamide (DMF), succinic anhydride, triethylamine, acetic anhydride Acetonitrile, thionyl chloride, DMF, toluene N-Methyl-pyrrolidone, 2-hydroxyethyl methacrylate, hydrochloric acid Methyl methacrylate, 3-meth-acryloxypropyl trimethoxysilane, ethyl acetate, VAZO 67

EXPERIMENTAL 1. Preparation of 4-carboxyhydroxybenzenesulfosuccinimide In a glass reaction vessel a mixture consisting of 154 ml DMF, 4-carboxybenzenesulfonamide (30.0 g), succinic anhydride (16.41 g), and triethylamine (33.19 g) were heated to 508C under a nitrogen atmosphere for 4 hours. The mixture was cooled to ambient temperature, treated with 18.27 ml of acetic anhydride, and stirred at ambient temperature for an additional 3 hours. The mixture was precipitated by pouring into 400 ml of 1 M aqueous hydrochloric and filtered. After washing with deionized water and drying, 36.94 g of product was isolated. 2. Preparation of 4-chlorocarboxybenzenesulfosuccinimide A reaction vessel containing a stirred mixture of the step 1 product (20.0 g) and acetonitrile (85 g) was treated with thionyl chloride (10.0 g) and DMF (1 drop) and then

Notes

449

refluxed for 1 hour and cooled to ambient temperature. The mixture was then further cooled in an ice bath and a precipitate isolated. The solution was filtered and the solid isolated was washed sequentially with cold acetonitrile and cold toluene, dried overnight in a vacuum oven at 508C, and 17.7 g of product isolated. 3. Preparation of carboxyethyl benzenesulfosuccinimide methacrylate A reactor was charged with N-methyl pyrrolidone, 2-hydroxyethyl methacrylate (0.78 g), and the step 2 product (1.50 g) and then stirred overnight at ambient temperature. The mixture was precipitated by pouring into 0.1 M hydrochloric acid and the solid isolated. The precipitate was washed with deionized water, dried in a vacuum oven at ambient temperature overnight @ 1 mmHg, and 1.53 g of product isolated. 4. Preparation of terpolymer A reactor was charged with the step 3 product (1.0 g), methyl methacrylate (8.0 g), 3-meth-acryloxypropyl trimethoxysilane (1.0 g), and ethyl acetate (30 g) and then treated with 102 ml of VAZO 67. The reactor was sealed and tumbled for 24 hours at 608C and the polymer isolated.

MONOMER DERIVATIVES

NOTES 1. Additional monomers, (I), of the current invention were prepared by the authors (1) in an earlier investigation and are discussed.

450

Soluble Polymers as Amine Capture Agents and Methods

2. Organic soluble terpolymers, (II), containing pendant acylsulfonamide aminereactive groups that were effective in selectively capturing recombinant protein P were also prepared by the authors (2) and are described.

3. Crosslinkable monomers including 1,2-ethanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, and 1,4 butanediol di(meth)acrylate were reacted with step 2 monomers of the current application by Moore et al. (3) to create biological amine-reactive materials useful in medical diagnostics. Additional crosslinked amine-reactive materials were prepared by Leir et al. (4) and are discussed.

References 1. B.K. Benson et al., U.S. Patent Application 20080145907 (June 19, 2008). 2. B.K. Benson et al., U.S. Patent Application 20080132665 (June 5, 2008) and U.S. Patent Application 20070154937 (June 5, 2007). 3. G.G.I. Moore et al., U.S. Patent Application 20070078243 (April 5, 2007). 4. C.M. Leir et al., U.S. Patent Application 20070078242 (April 5, 2007).

b. Rhenium-containing polymers

Title: Polymerization Using Ligand Initiators and Ligand Terminators Author: Assignee:

Urs Hafeli et al. The Cleveland Clinic Foundation (Cleveland, OH) Case Western Reserve University (Cleveland, OH)


20080064841 (March 13, 2008) Very high 2010

Preparation of rhenium-based nucleotides by ligand-initiated ring-opening polymerization. Ligand-initiated ring-opening polymerization is novel and unreported in the patent literature. Diagnostic imaging A biocompatible polylactide has been prepared that contains a 2-bis(picolylamine)ethanol terminus that is useful as a ligand for delivering rhenium-based nucleotides in diagnostic imaging. The “tailored” ligandterminated polymer was prepared using a ring-opening polymerization of 3,6-dimethyl-1,4-dioxane-2,5-dione with 2-bis(picolylamine)functionalized alcohols that were then used to selectively chelate 188Re metal ions. Chelator ligands used to initiate the polymerization reaction—rather than being incorporated onto an end chain of an existing polymer—are introduced at every polymer chain. By incorporating more chelating ligands, the metal atom labeling of the polymer is more efficient. Furthermore, using a “one-pot” synthesis method both simplifies the reaction and optimizes the product yield.

451

452

Polymerization Using Ligand Initiators and Ligand Terminators

REACTION

i. 2-Bis(picolylamine)ethanol, toluene, stannous octoate ii. Ammonium rhenium tribromide tricarbonyl, CH2Cl2

EXPERIMENTAL 1. Preparation of a polylactide containing a 2-bis(picolylamine)ethanol terminus A reactor was charged with 3,6-dimethyl-1,4-dioxane-2,5-dione (8 mmol), 2-bis(picolylamine)-ethanol (0.5 mmol), 10 ml of toluene, and 50 ml of 50% stannous octoate in toluene and then immersed into a preheated oil bath at 1258C for 3 hours. The mixture was then cooled to ambient temperature, concentrated, and the residue dissolved in 10 ml of CH2Cl2. The solution was then washed with 10 ml of 0.1 M HCl, 10 ml saturated brine, and twice with15 ml of water and then dried using Na2SO4. The product was isolated in 72% yield after filtration and solvent removal. 1

H-NMR (CDCl3): d. 1.45 (d, CH3CHOH), 1.5 (d, CH3), 2.85 (t, CH2, H7,70 ), 3.84 (s, CH2, H5,50 /6,60 ), 4.2 (m, CH2, H8,80 ), 4.34 (q, CH3CHOH), 5.15 (q, CH), 7.15 (t, py H2,20 ), 7.48 (d, py H4,40 ), 7.65 (t, py H3,30 ), 8.5 (d, py H1,10 ) FTIR (KBr cm21): 3490 (b, OH), 1758 (CvO) MS (MALDI-TOF): m/z 1399, 1543, 1687, 1832, 1976, 2120, 2264, 2408, 2250, 2694

2. Preparation of a polylactide containing a 2-bis(picolylamine) rhenium tricarbonyl terminus The step 1 product (35 mmol) was dissolved in 5 ml of CH2Cl2 and then treated with the dropwise addition of (NH4)2ReBr3(CO)3 (35 mmol) dissolved in 0.5 ml of methanol and diluted with 9.5 ml of CH2Cl2 and then refluxed at 458C for 3 hours. The solution was concentrated and the residue stirred with methanol, filtered, and the product isolated in 89% yield as a beige solid. 1

H-NMR (CDCl3): d. 1.47 (d, CH3CHOH), 1.56 (d, CH3), 4.03 (m, CH2, H8,80 ), 4.36 (q, CH3CHOH), 4.47 (d, CH2, H5,50 ), 4.80 (t, CH2, H7,70 ), 5.15 (q, CH), 6.30 (d, CH2, H6,60 ), 7.19 (t, py H2,20 ), 7.80 (t, py H3,30 ), 7.95 (dd, py H4,40 ), 8.6 (d, py H1,10 ) FTIR (KBr cm21): 3418 (OH), 2033 (CO), 1930 (CO), 1758 (CvO) MS (MALDI-TOF): m/z 1376, 1522, 1666, 1810, 1954, 2098, 2242, 2388, 2532, 2676, 2820

Notes

453

DERIVATIVES Additional ligands, (I), and ring-opening polymerization ligand polymers, (II), prepared in the current application are illustrated below.

NOTES 1. Methoxypolyethylene glycol terminated with thioester chelating agents, (III), were prepared by Schellenberg et al. (1) and used as a protective coating against tissue damage by chelating with metals that react with peroxides to produce reactive hydroxyl radical.

2. Murray et al. (2) prepared permeable membranes for selectively removing phosphate, nitrate, and ferric cations by polymerizing and crosslinking with the modified matrix monomer, (bis-acrylamindo-phenanthroline)dinitrate, (IV), to produce an ion permeability substrate. Kulkarni et al. (3) selectively removed cobalt cations from solution using 2-hydroxy ethyl methacrylate copolymers, (V), crosslinked with trimethylol propane acrylate.

454

Polymerization Using Ligand Initiators and Ligand Terminators

References 1. K.A. Schellenberg et al., U.S. Patent Application 20080039524 (February 14, 2008). 2. G.M. Murray et al., U.S. Patent 7,279,096 (October 9, 2007). 3. M.G. Kulkarni et al., U.S. Patent 7,001,963 (February 21, 2006).

D. Biomaterials for Drug Delivery Devices a. Amphiphilic terpolymers

Title: Biodegradable Triblock Copolymers, Synthesis Methods Therefore, and Hydrogels and Biomaterials Made Therefrom Author: Assignee:

Jun Li et al. Omeros Corporation (Seattle, WA)


20080057128 (March 6, 2008) Moderate 2010

Synthesis of amphiphilic terpolymers containing ethylene oxide and (R)-3-hydroxybutyrate and hydrogels containing cyclodextrin. Ongoing 3-year investigation. Drug delivery devices Poly[(R)-3-hydroxybutyrate] is an optically active biodegradable polyester synthesized as an energy storage material by many microorganisms. Biocompatible amphiphilic polyfethylene oxide-b-[(R)-3-hydroxy-butyrate] diol-b-ethylene oxideg was prepared and then converted into an injectable hydrogel using b-cyclodextrin for use as a drug delivery device. Although hydrogel systems consisting of polyrotaxanes have been prepared, the current application is considerably more commercially viable. Poly[(R)-3hydroxybutyrate] was initially converted into tele-chelic poly(3-hydroxyalkanoate)-diol by transesterification with ethylene glycol. Subsequent esterification of the termini with methoxy polyethylene glycol using 1,3dicyclohexylcarbodiimide was then used to prepare the product.

455

456

Biodegradable Triblock Copolymers, Synthesis Methods

REACTION

i. Dibutyltin dilaurate, diglyme, diethylene glycol ii. Methoxy polyethylene glycol, 1,3-dicyclohexylcarbodiimide, CH2Cl2 EXPERIMENTAL 1. Preparation of poly[(R)-3-hydroxybutyrate] diol A reactor was charged with poly[(R)-3-hydroxybutyrate], diethylene glycol, dibutyltin dilaurate, and diglyme and then heated overnight and the telechelic hydroxylated prepolymer isolated and used without further purification. 2. Preparation of poly{ethylene oxide-b-[(R)-3-hydroxybutyrate] diol-b-ethylene oxide} Under a protective nitrogen blanket, the step 1 product was coupled with methoxy polyethylene glycol prepolymers (Mn 1820 and 4740 Da) using 1,3-dicyclohexylcarbodiimide dissolved in CH2Cl2. The product was isolated after being purified by precipitation and fractionation from mixed solvents of chloroform/diethyl ether or methanol/diethyl ether. DERIVATIVES A summary physical properties of terpolymers are provided in Table 1. TABLE 1. Physical Properties of Poly{ethylene oxide-b-[(R)-3-hydroxybutyrate] diol-b-ethylene oxide} Prepared by Transesterification of [(R)-3-hydroxybutyrate] with Methoxy Polyethylene Glycol Entry 2 4 5 6

Mn PEO– PHB–PEO Terpolymers (Da)

Mn (Da)

PDI

PHB Content (wt%)

2000 –500 –2000 2000 –5200–2000 5000 –800 –5000 5000 –5200–5000

4500 8120 10,390 13,390

1.05 1.14 1.08 1.21

11.4 59.0 7.6 36.7

Abbreviations: PEO ¼ poly ethylene oxide, PHB ¼ poly hydrobutyrate, and PDI ¼ poly dispersity index.

Testing

457

TESTING A. Critical Micelle Formation Critical micelle concentration in aqueous solutions was determined by fluorescence using pyrene as a probe. The driving force for micelle formation is the strong hydrophobic interactions between [(R)-3-hydroxybutyrate] block. It was previously determined by this group that terpolymers with longer PHB blocks have much lower critical micelle concentrations because of PHB block aggregation in aqueous solution. Testing results are provided in Table 2.

TABLE 2. Critical Micelle Concentration of Poly{ethylene oxide-b-[(R)-3-hydroxybutyrate] diol-bethylene oxide} Determined at 2388 C in Aqueous Solution Entry

Mn PEO–PHB– PEO Terpolymers (Da)

Critical Micelle Formation (g/L)

2000–500 –2000 5000–800 –5000 5000–3800– 5000

2.0 1021 4.0 1022 1.3 1022

2 5 7

B. Inclusion Complexes with a- or g-Cyclodextrins A selected terpolymer (20 mg) of the current application was soaked with 0.06 ml of H2O overnight at ambient temperature and then treated with 3.0 ml of a saturated aqueous solution of either a- or g-cyclodextrin. It was then sonified for 10 minutes and remained undisturbed for 2 days at ambient temperature. The precipitated product was collected by centrifugation and washed alternately with water and acetone and the product dried in a vacuum at 708C for 2 weeks. Physical property testing results are provided in Table 3.

TABLE 3. Physical Properties of Inclusion Complexes of a- or g-Cyclodextrins with Poly{ethylene oxide-b-[(R)-3-hydroxybutyrate] diol-b-ethylene oxide} Derivatives Entry 5 8 9

Mn PEO–PHB –PEO Terpolymers (Da)

Mn (Da)

PDI

Tm PEO (8C)

Tm PHB (8C)

2000– 5200–2000 2000– 3900–2000 5000– 6800–5000

8100 7200 9690

1.14 1.10 1.28

23.3 25.4 25.3

153.6 142.3 155.2

458

Biodegradable Triblock Copolymers, Synthesis Methods

NOTES 1. Additional derivatives of the current invention were prepared by the authors (1) and are discussed. 2. In an earlier investigation by the authors (2) b-cyclodextrin complexes with poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) capped with picric acid, (I), were prepared that formed complexes with nucleic acids and were used in gene therapy.

3. Bioabsorbable star polymers consisting of p-dioxanone, glycolide, and pentaerythritol were prepared by Bennett et al. (3) and used as surgical adhesives and as bone putty.

References 1. J. Li et al., U.S. Patent Application 20060211643 (September 21, 2006) and U.S. Patent Application 20020019369 (February 14, 2002). 2. J. Li et al., U.S. Patent 7,297,348 (November 20, 2007). 3. S.L. Bennett et al., U.S. Patent 7,321,008 (June 22, 2008).

b. Dithiocarbonate macromers

Title: Dithiocarbonate-Containing Macromers and Polymers Derived Therefrom Author: Assignee:

Ankur S. Kulshrestha et al. Johnson & Johnson (New Brunswick, NJ)


Observations:

20070225460 (September 27, 2007) High Mid-2009

Synthesis of dithiocarbonate and thioether macromers and polymers to deliver reactants to a body cavity in a fluid form. Ongoing 4-year investigation. Drug delivery agents Biodegradable sutures In the current application two categories of biodegradable materials were prepared. In the first case water-soluble dithiocarbonate containing polymers having thioether and 1,3-oxathiolanyl linkages were prepared. This current investigation differs from earlier work by this group where polyoxaesters containing pendant thiols were prepared. Polymers in this category were used to deliver in situ medicaments to a body cavity in fluid form. The second category consisting of this investigation of preparing highly crosslinked thioether polymers that were hydrolysable under physiological conditions. These materials were used as drug delivery devices.

459

460

Dithiocarbonate-Containing Macromers and Polymers Derived Therefrom

REACTION

i. Lithium bromide, THF, carbon disulfide ii. Ethoxylated pentaerythritol tetrakis(3-mercaptopropionate), azobisisobutyronitrile iii. Spermidine

dioxane,

2,2-

EXPERIMENTAL 1. Preparation of (2-thioxo-1,3-oxathiolan-5-yl)methyl acrylate A flame-dried 2-liter reactor was charged with (oxiran-2-yl) methyl acrylate (312 mmol), lithium bromide (1 g), and 300 ml THF and then treated with the dropwise addition of carbon disulfide (410 mmol). The mixture was stirred at ambient temperature for 4 hours and then at 458C for 30 hours and concentrated. The residue was purified by column chromatography using silica gel with hexane/acetone, 70:30, respectively, and the product isolated as an orange-colored liquid. 1

H-NMR (CDCl3) d: 6.5 (dd,1H), 6.2 (m,1H), 5.9 (dd,1H), 5.4 (dd,1H), 4.5 (bm,1H), 3.5–3.75 (bm,1H), 2.9 (m,1H), 2.7 (m,1H)

2. Preparation of 4-armed dithiocarbonate A flame-dried 1-liter reactor was charged with ethoxylated pentaerythritol tetrakis(3-mercaptopropionate) (46.3 mmol), the step 1 product (185 mmol), and 300 ml of dioxane and then treated with 2,20 -azobisisobutyronitrile (4 mmol). The mixture was then heated to 708C for 36 hours and concentrated. The residue was purified by column chromatography with hexane/acetone, 30:70, respectively, and the product isolated as a dark orange viscous liquid. 1

H-NMR (CDCl3) d: 6.5 (dd,1H), 6.2 (m,1H), and 5.9 (dd,1H)

Notes

461

3. Preparation of 4-armed dithiocarbonate crosslinked macromer A 20-ml vial was charged with the step 2 product (5.5 mmol) and spermidine (11 mmol) and then stirred at ambient temperature for 2 minutes. After concentrating, the product was isolated as a crosslinked polymeric gel.

DERIVATIVES Only the single derivative was prepared.

NOTES 1. The structure for the step 2 reagent, ethoxylated pentaerythritol tetrakis(3mercaptopropionate), (I), is illustrated below.

2. The (oxiran-2-yl)-methyl acrylate phenolic derivative, (II), was polymerized to the corresponding polydithiocarbonate, (III), with trifluoromethanesulfonate by Ohta et al. (1) and used in high oxygen-permeable contact lenses. Additional crosslinkable analogs are described by Kamata et al. (2) and Honda et al. (3).

3. Absorbable polyoxaesters containing pendant thio substituents, (IV), were prepared by the authors (4) and used in tissue engineering scaffolds and as drug delivery agents.

462

Dithiocarbonate-Containing Macromers and Polymers Derived Therefrom

References 1. K. Ohta et al., U.S. Patent Application 20070208149 (September 6, 2007). 2. H. Kamata et al., U.S. Patent Application 20070021571 (January 25, 2007). 3. Y. Honda et al., U.S. Patent 7,049,350 (May 23, 2006). 4. A.S. Kulshrestha et al., U.S. Patent Application 20070225452 (September 27, 2007).

c. Hydrogels

Title: Methods for the Formation of Hydrogels Using Thiosulfonate Compositions and Uses Thereof Author: Assignee:

Zhihao Fang et al. Nektar Therapeutics (San Carlos, CA)


20080033105 (February 7, 2008) Moderately high End 2010

Development of hydrogels that selectively crosslink in the presence of base. Ongoing investigation on hydrogels as drug delivery devices. Drug delivery device Polyethylene glycol hydrogels are water-swollen gels. They are prepared by incorporating polyethylene glycol into a chemically crosslinked network so that the addition of water produces an insoluble, swollen gel. The current application describes a method for preparing hydrogels using thiosulfonate-containing multiarm polyethylene glycols that crosslink when exposed to aqueous base. Polyethylene glycol hydrogels have also been prepared by crosslinking with acrylic acid, copolymerizing with (meth)acrylate derivatives, and by using diisocyanates. Linear polyethylene glycol modified with p-nitrophenylcarbonate have also crosslinked by reacting with bovine serum albumin.

463

464

Methods for the Formation of Hydrogels Using Thiosulfonate Compositions and Uses Thereof

REACTION

i. ii. iii. iv.

Sulfur, methanol, sodium methane sulfonite Chloroform, triethylamine, methanesulfonyl chloride Ethanol Sodium phosphate buffer EXPERIMENTAL

1. Preparation of sodium methanethiosulfonate Sodium methane sulfinate (3.0 g) and sulfur (1.41 g) were mixed in 180 ml of methanol and then refluxed under argon for 45 minutes. The mixture was then cooled to ambient temperature, filtered, the filtrate concentrated, and 3.2 g product isolated. 1

H-NMR (d6-DMSO) d 2.97 (s, CH3SO2SNa); peak at 1.82 (s, CH3SO2Na) absent

2. Preparation of 4-arm polyethylene glycol methanesulfonate A 4-arm polyethylene glycol having an Mn of 10,000 Da (8 mmol of hydroxyl groups) was dried by azeotropic distillation using 400 ml of chloroform. The residue was then redissolved in 300 ml chloroform and cooled to 48C and then treated with triethylamine (14.4 mmol) and methanesulfonyl chloride (13.2 mmol). The mixture was stirred overnight at ambient temperature and then treated with 5 ml of ethanol and stirred an additional 30 minutes. It was dried using sodium carbonate (10.0 g), concentrated, and filtered. The filtrate was concentrated to dryness and treated with 400 ml of 2-propanol. The precipitate was collected and 20.0 g product isolated having a 95.3% methanesulfonate substitution. 1

H-NMR (d6-DMSO) d (s, PEG backbone), 4.31 (t, ZCH2OSO2Z)

3. Preparation of 4-arm polyethylene glycol methanethiosulfonate The step 2 product (2.0 mmol) was dried by azeotropic distillation, redissolved in 80 ml ethanol, and treated with the step 1 product (7.2 mmol). The mixture was

Gel Formation Scoping

465

refluxed under argon overnight and then concentrated at 408C until dry. It was treated with 100 ml 2-propanol and the precipitated product was then dried under high vacuum overnight. The dried product (4.0 g) was dissolved in 100 ml of CH2Cl2 and then washed with 100 ml of sodium phosphate buffer having a pH of 5.0 (10% w/v NaH2PO4ZNa2HPO4). The aqueous solution was back extracted with three aliquots of 200 ml CH2Cl2 and then combined and dried over anhydrous sodium sulfate. The mixture was filtered, the filtrate concentrated to near dryness, and the material precipitated by the addition of 100 ml of 2-propanol and 100 ml diethyl ether. After drying, 3.1 g of product was isolated. 1

H-NMR (d6-DMSO) d 3.51 (s, PEG backbone); absence of peak at 4.31 ppm (t, ZCH2OSO2Z) indicated all mesylate groups had been substituted

4. Hydrogel formation from four-arm polyethylene glycol methanethiosulfonate A 5% w/v solution of the step 3 product was prepared in 100 mM sodium of phosphate buffer having a pH of 8. The solution formed a hydrogel in about 3 hours at 238C and in about one hour at 378C.

DERIVATIVES

TABLE 1.

Selected Step 3 Four-Arm Polyethylene Glycol Derivativesa

Entry

R1

R2

Percent Substituted

C6H5 CH3 CH3

None ZOCONHCH2CH2Z Z(OCONHCH2CH2)2Z

95 90 —

2 3 4

a All experimental agents were effective in producing hydrogels when mixed with a buffered solution having a pH ¼ 8.

GEL FORMATION SCOPING Gel formation efficacy was evaluated using 1000 mg of the step 3 product with a solution pH ¼ 8. Testing results are provided in Table 2.

466

Methods for the Formation of Hydrogels Using Thiosulfonate Compositions and Uses Thereof

TABLE 2. Effects of Polymer Concentration, Buffer Solution pH, and Incubation Temperature on Gel Formation Entry 1 4 10 16

Gel Time (min)

Concentration (%wt/vol)

pH

Incubating Temperature (8C)

585 81 40 35

2 2 5 10

7.50 8.00 8.00 8.00

24 37 37 37

NOTES 1. In an earlier investigation by the authors (1) hydrogels were prepared from 4-arm polyethylene glycol alkylthiosulfonate derivatives and used in drug delivery applications. 2. Four-arm hydrogel hydrogen containing nonsteroidal anti-inflammatory drug (NSAID) compositions were prepared by Burton et al. (2) and used to deliver Ketorolacw, (I).

3. Eight-arm star polyethylene glycol amines having Mn’s of 10,000 Da were prepared by Chenault (3) and used as hydrogels in drug delivery applications. In this procedure 8-arm star polyethylene glycol was initially chlorinated using thionyl chloride and then treated with 12 M ammonium hydroxide. 4. Aldol crosslinked polymeric hydrogel adhesives, (II), were prepared by Arthur (4) by reacting poly(hydroxylic) polymers with diketene as illustrated in Eq. (1).

Notes

467

(1)

i. Diketene, dimethylacrylamide, lithium chloride 5. A method for preparing branched functionalized polymers containing polyol cores, (III), useful in the preparation of hydrogels, is described by McManus et al. (5).

References 1. Z. Fang et al., U.S. Patent 7,312,301 (December 25, 2007). 2. K. Burton et al., U.S. Patent Application 20080004461 (February 1, 2007). 3. H.K. Chenault, U.S. Patent Application 20070249870 (October 25, 2007). 4. S.D. Arthur, U.S. Patent Application 20070048337 (March 1, 2007) and U.S. Patent Application 20070048251 (March 1, 2007). 5. S.P. McManus et al., U.S. Patent Application 20070031371 (February 8, 2007).

d. Oligomeric styrene

Title: Storage-Stable Polymer-Oligomer Particles and Their Use in Seed Polymerization Author: Assignee:

Steinar Pedersen et al. Norsk Hydro ASA (Oslo, NO)


20080021171 (January 24, 2008) Moderately high Mid-2010


Formation of oligomeric polystyrene with a narrow size distribution. Ongoing investigation. Drug delivery devices

Observations:

Emulsion polymerization of styrene has been used to prepare a latex for seed polymerization. When it was used to initiate styrene polymerization, the seed latex produced a polymer that was storage stable, swellable, and that had a particle size distribution between 1 and 10 mm. It is especially desirable to have high swelling particles since their size increases to the cube root of the volume. In addition any monomer capable of forming a latex is a potential seed polymerization agent, and any seed latex may be used to initiate the polymerization of any latex-formable monomer.

REACTION

i. Deionized water, sodium chloride, potassium persulfate 468

Notes

469

EXPERIMENTAL 1. Preparation of polystyrene seed by emulsion polymerization Deionized water (2700 g), sodium chloride (2.29 g), potassium persulfate (1.76 g), and styrene (267 g) were mixed and added to a glass reactor where oxygen was removed from the solution by bubbling nitrogen through it. The temperature was then increased to 758C, the agitation speed set to 200 rpm, and the polymerization took place over night. Polystyrene particles having a diameter of 0.82 mm with a narrow size distribution were isolated. 2. Preparation of polystyrene by seed polymerization Deionized water (720 g), sodium lauryl sulfate (4.3 g), dioctanoyl peroxide (40 g), and acetone (133 g) were emulsified using an ultrasonic probe for 10 minutes. The step 1 polystyrene seed (48.0 g seed, 578 g latex) was added to the emulsion together with lauryl sulfate (0.8 g) and acetone (29.6 g). The mixture was transferred to a flask and left to agitate at approximately 258C for 48 hours. Acetone was then removed and the solution added to a 5-liter double-walled glass reactor. The temperature was increased to 408C while styrene (336 g) and divinyl benzene (0.88 g) were added dropwise over approximately 60 minutes. After 4 hours the mixture was treated with deionized water (1200 g), potassium iodide (1.28 g), and polyvinyl pyrrolidone (18.48 g) with the temperature increased to 708C. The polymerization continued for 6 hours at 708C and 1 hour at 908C. Styrene-based oligomer particles with a diameter of 1.7 mm and with a narrow size distribution were obtained.

SCOPING REACTIONS TABLE 1. Storage Stability Testing Results Indicating Acceptable Storage Stability is Obtainable if Initiator/Monomer Ratio Is Less Than 0.07a

Entry 4 5 6 Comparative a

Diameter (mm)

Initiator Monomer (mol/mol)

Degree of Polymerization (monomer units)

Storage Stability (days)

3.5 2.3 5.2 4.2

0.04 0.04 0.04 0.08

71 73 72 49

.40 .40 .40 13

Swelling capacities for all entries exceeded 100 vol%.

NOTES 1. Leth-Olsen et al. (1) prepared single-stage seed polymerization to form polymer particles having a size distribution between 10 and 100 mm with a narrow size

470

Storage-Stable Polymer-Oligomer Particles and Their Use in Seed Polymerization

distribution. Narrowly dispersed particles were produced by dispersion polymerization of methyl methacrylate in methanol with polyvinyl pyrrolidone as the stabilizer and either 2,20 -azobisisobutyronitrile or dioctanoyl peroxide as the initiator. 2. Burghart et al. (2) prepared acrylic lattices consisting of acrylamide, styrene, 2-ethylhexylacrylate, and n-butyl acrylate by seed polymerization using a polystyrene latex. Materials produced by this process were used as vapor barriers. 3. Seed polymerization using a polystyrene latex was used by Gaschler et al. (3) to prepare aqueous styrol-butadiene polymer dispersions. 4. A seed latex consisting of styrene and a-methylstyrene was prepared by Mestach et al. (4) and used to polymerize styrene and methylacrylate. References 1. K.-A. Leth-Olsen et al., U.S. Patent 6,949,601 (September 27, 2005). 2. A. Burghart et al., U.S. Patent Application 20070238820 (October 11, 2007). 3. W. Gaschler et al., U.S. Patent Application 20070191531 (April 16, 2007). 4. D.E.P. Mestach et al., U.S. Patent Application 20070043156 (February 22, 2007).

e. Poly(ester-amides)

Title: Epoxy-Containing Poly(ester amides) and Method of Use Author: Assignee:

Ramaz Katsarava et al. MediVas, LLC (San Diego, CA)


20080050419 (February 28, 2008) High 2010

Synthesis of biocompatible poly(ester-amides) containing linear a-amino acid amides. Biocompatible poly(ester-amides) containing linear a-amino acid amides are unreported in the patent literature. Drug delivery devices Condensation polymerization was used to prepare poly(ester-amides) containing hydrophobic a-amino acid linear building blocks. Their low enzymatic degradation profile renders them attractive in drug delivery devices and provides advantages over the rapid hydrolytic degradation rates of polylactic acid and polyglycolic acid. The key monomer intermediate, di-p-nitrophenyl-trans-epoxy succinate, was prepared by interfacial condensation of the epoxy dichloride and p-nitrophenol according to the Shotten-Bauman reaction. Poly(ester-amides) were prepared by amidation of diamino acid alkyl diesters. A method of studying the interaction of poly(ester-amides) with primary amines by incorporating the photometrically monitorable 2,4-dinitroaniline chromophore was also prepared.

471

472

Epoxy-Containing Poly(ester amides) and Method of Use

REACTION

i. ii. iii. iv.

Hydrogen peroxide, sodium tungstate Phosphorous pentachloride p-Nitrophenol, water, sodium carbonate Di-p-toluene-sulfonic acid salt, bis-(L-leucine)-1,6-hexylene diester, N,Ndimethylacetamide, triethylamine v. 2,4-Dinitrofluoro benzene, dimethylformamide EXPERIMENTAL

1. Preparation of trans-epoxysuccinic acid The oxidation of fumaric acid with hydrogen peroxide in the presence of sodium tungstate was used to prepare this intermediate and the product isolated in 60% yield. H-NMR (d6-DMSO) d: 11.55 (s, broad, 2H, ZCOOH), 3.41 (s, 2H) Elemental analysis Calcd. C: 36.38%, H: 3.05%; Found C: 36.63%, H: 3.45% 1

2. Preparation of trans-epoxysuccinic acid chloride The reaction of the step 1 product with phosphorous pentachloride was used to to prepare this intermediate. After concentrating and removing POCl3 under reduced pressure, the dichloride crystallized at ambient temperature. It was recrystallized from light petroleum and the product isolated in 80% having an mp of 51– 538C. 3. Preparation of di-p-nitrophenyl-trans-epoxysuccinate This compound was prepared by the interfacial reaction of a chloroform solution of the step 2 product with p-nitrophenol in water containing Na2CO3. The product was

Notes

473

obtained in 90% yield having an mp of 182 – 1848C after recrystallization from light petroleum ether. Elemental analysis Calcd. C: 51.35%, H: 2.69%, N: 7.49%; Found C: 51.01%, H: 2.43%, N: 7.30% 1 H-NMR (d6-DMSO/CDCl3, 1:3, respectively) d: 8.33 (d, 4H, J ¼ 9.1 Hz), 7.54 (d, 4H), 4.23 (s, 2H)

4. Preparation of poly[bis-(L-leucine)-1,6-hexylene] diester-co-transepoxysuccinic amide The polymerization reaction was performed at ambient temperature by stirring the step 3 product, di-p-toluene-sulfonic acid salt, and bis-(L-leucine)-1,6-hexylene diester dissolved in N,N-dimethylacetamide containing triethylamine and the product isolated. 5. Preparation of poly[bis-(L-leucine)-1,6-hexylene] diester-co-transepoxysuccinic dinitroaniline The step 4 product (1.0 mol) was converted into the corresponding dinitroaniline derivative by condensing with 2,4-dinitrofluoro benzene (1.0 mol) in dimethylformamide.

DERIVATIVES The step 5 derivative was also prepared using bis-(L-phenylalanine)-1,6-hexylene diester.

NOTES 1. To investigate the interaction of the step 5 product with a primary amine, the 2,4-dinitroaniline chromophore was incorporated into the step 5 product for photometric monitoring at 360– 400 nm. 2. Biogradable hydrogels were also prepared by modifying step 5 derivatives with acryloyl chloride, (I). In a typical reaction 20% solution of the step 5 product (1.0 mol) dissolved in N,N-dimethylformamide was treated with acryloyl chloride (1.2 mol) at 08C. The polymer was then precipitated in water and dried. The formation of acrylic ester was confirmed by a UV absorbance at 265 nm.

474

Epoxy-Containing Poly(ester amides) and Method of Use

3. Three-dimensional hybrid hydrogel networks were also prepared by the authors in the current application by functionalizing the step 5 derivatives with methacryloyl dextran. 4. In an earlier investigation by the authors (1) biodegradable poly(ester-amides) were prepared and used as drug delivery devices for internally administered bioactive agents. Unsaturated analogs, (II), were prepared by Chu et al. (2).

5. Biocompatible aromatic poly(ester-amide), (III), were prepared Gomurashvili et al. (3) and used as stents in internal fixation devices.

by

6. Elastomeric biodegradable copolyester amides, (IV), and copolyester urethanes were prepared by Chu et al. (4) and were effective as drug delivery agents.

Notes

References 1. R. Katsarava et al., U.S. Patent Application 20070287987 (December 13, 2007). 2. C.-C. Chu et al., U.S. Patent Application 20070167605 (July 19, 2007). 3. Z.D. Gomurashvili et al., U.S. Patent Application 20070106035 (May 10, 2007). 4. C.-C. Chu et al., U.S. Patent Application 20070027293 (February 1, 2007).

475

f. Poly(a-glutamic acid)

Title: Process for the Preparation of Poly-a-Glutamic Acid and Derivatives Thereof Author: Assignee:

Marc McKennon et al. Cell Therapeutics, Inc. (Seattle, WA)


476


Development of polypeptide drug delivery devices containing pendant carboxylic acids. This demonstrates a novel three-step method for preparing poly-aglutamic acid derivatives. Drug delivery devices Poly-a-glutamic acid containing amine and carboxylic acid end groups was prepared by the polycondensation of g-esters of a-glutamic acid N-carboxy anhydride followed by acid hydrolysis of the intermediate. The termini of the polypeptide were then endcapped by condensing with selected amino- or carboxylic acid derivatives. Poly-a-glutamic acids were then used in drug delivery devices in the preparation of conjugate derivatives containing a primary or secondary amino group or primary, secondary, or tertiary hydroxy group.

Experimental

477

REACTION

i. ii. iii. iv.

Triphosgene, THF 1,8-Diazabiciclo[5.4.0]undec-7-ene, 1,4-dioxane Formic acid, sodium hydroxide, sulfuric acid THF, 4-dimethylamino-pyridine, 2-thiophenebutyric carbodiimide

acid,

diisopropyl-

EXPERIMENTAL 1. Preparation of a-L-glutamic acid-g-(t-butyl)ester N-carboxy anhydride A reactor was charged with triphosgene (0.135 mol) dissolved in 862.5 ml of THF and then treated with a single portion of L-a-Glu-g-t-butyl ester (0.148 mol) and stirred for 2 hours at 208C. The mixture was then concentrated and 80 ml of an oily residue obtained. This material was recrystallized in 750 mL of n-heptane and then washed three times with 90 ml heptane, dried, and 23.3 g of a solid product isolated.

478

Process for the Preparation of Poly-a-Glutamic Acid and Derivatives Thereof

2. Preparation of poly-a-L-glutamic acid-g-(t-butyl)ester 1,8-Diazabiciclo[5.4.0]undec-7-ene (3.84 mmol) was dissolved in 5 ml of 1,4-dioxane and mixed with the step 1 product (96 mmol), dissolved in 550 ml of 1,4-dioxane and then stirred for 4 hours at 258C. This mixture was treated with 1100 ml of water over 40 minutes and the precipitate isolated and washed three times with 50 ml water. The white solid was then dried and 16.4 g of product isolated having an Mn of 25,400 Da and containing approximately 1 mol% free amino groups at the N-terminus. 3. Preparation of poly-a-L-glutamic acid The step 2 product (4 g) was suspended in 80 ml of 99% formic acid and then stirred at 608C for 5 hours. After 30 minutes of heating the suspension dissolved and a solid began to precipitate. The mixture was concentrated and residual formic acid removed by azeotropic distillation with toluene. The residue was then suspended in 40 ml of water and cooled to 3 – 58C treated with 30% NaOH to reach pH 8 and then filtered through a 0.22-mm microfilter. The clear solution was acidified using sulfuric acid up to a pH 2.5 and the suspension stirred for 2 hours. The precipitated solid was filtered off, dried, and 2.7 g of a white solid isolated having an Mw of 13,900 Da with a polydispersity of 1.04. 4. Preparation of N-Capped poly-a-L-glutamic acid: General procedure The step 3 product was dissolved in THF (20 ml/g) and 5 –10 mol% of 4-dimethylaminopyridine added. The mixture was then treated with 2-thiophenebutyric acid (10 eq) and diisopropylcarbodiimide (50 mol% excess) and stirred for 2 hours. Two volumes of water were then added to the solution and the mixture stirred for 30 minutes and a precipitate isolated. The solid was suspended in formic acid and then stirred for 2 hours at 608C. Two additional volumes of water were added and the mixture stirred an additional 30 minutes and then filtered. After washing the solid with water and drying, the product was isolated.

DERIVATIVES The step 4 product was also amidized with L-pyroglutamic acid and naphthylen-2-yl acetic acid.

NOTES 1.

D-Glutamic acid-g-(t-butyl)ester N-carboxy anhydride was previously polymerized by Fujimoto et al. (1) in a 1,2-dichloroethane/1,4-dioxane mixture using sodium 4-methyl-2-pyrrolidone as initiator. Additional derivatives were

Notes

479

prepared by Bichon et al. (2) using N-carboxyanhydride methyl g-glutamate in methylene chloride with triethylamine as the polymerization initiator. 2. Pharmaceutical formulations consisting of poly-a-L-glutamic acid derivatives were prepared by Bonnet-Gonnet (3) and used in the prolonged release of D,L-a-tocopherol. 3. Poly-a-L-glutamic acid derivatives prepared by Piccariello et al. (4) were functionalized with N-octanoyl-L-triiodothyronine and used in the treatment of thyroid disorders. References 1. Y. Fujimoto et al., U.S. Patent 3,635,909 (January 18, 1972). 2. D. Bichon et al., U.S. Patent 4,976,962 (December 11, 1990). 3. C. Bonnet-Gonnet, U.S. Patent Application 20080026070 (January 31, 2008). 4. T. Piccariello et al., U.S. Patent 7,163,918 (January 16, 2007).

g. Poly(hydroxyl alkanoic acids)

Title: Polyhydroxyalkanoic Acid Having Vinyl, Ester, Carboxyl, or Sulfonic Acid Group and Producing Method Therefore Author: Assignee:

Takashi Kenmoku et al. Canon Kabushiki Kaisha (Tokyo, JP)


20080064828 (March 13, 2008) Moderate 2011

Synthesis of biocompatible amide and sulfonate functionalized polyhydroxyalkanoates. The existing prior art on polyhydroxyalkanoates is extensive. Drug delivery agents Polymalic acid is the simplest biocompatible polyhydroxyalkanoic acid and exist in a- (a) and b-acid (b) forms. They are prepared by ringopening polymerization of glycolic acid ester (c) and b-malolactone (d) derivatives, respectively.

In this application oxidative degradation of a-polymalic vinyl derivatives using potassium permanganate was used to prepare higher acid homologs (e) with only marginal chain disintegration.

480

Experimental

481

These intermediates were then amidated with selected aminobenzene sulfonic acids. Materials produced in this process were used as biocompatible materials and in drug delivery devices.

REACTION

i. L-Lactide, toluene, tin 2-ethylhexanoate, p-t-butylbenzyl alcohol ii. Acetone, acetic acid, 18-crown-6-ether, potassium permanganate iii. 2-Aminobenzenesulfonic acid phenyl ester, pyridine, triphenyl phosphite EXPERIMENTAL 1. Preparation of poly(3,6-di(2-propenyl)-1,4-dioxane-2,5-dione-co-L-lactide) 3,6-Di(2-propenyl)-1,4-dioxane-2,5-dione (5.0 mmol), L-lactide (45.0 mmol), 20 ml of 0.01 M toluene solution of tin 2-ethylhexanoate, and 20 ml of 0.01 M toluene solution of p-t-butylbenzyl alcohol were charged in a polymerization ampoule and then sealed and heated at 1508C for 1 hour. The polymer was then dissolved in chloroform, precipitated in excess methanol, filtered, and 6.55 g of product isolated containing 9 mol% 3,6-di(2-propenyl)-1,4-dioxane-2,5-dione and having an Mn of 17,400 Da with an Mw of 23,300 Da. 2. Oxidation of poly(3,6-di(2-propenyl)-1,4-dioxane-2,5-dione-co-L-lactide) The step 1 product was dissolved in 360 ml of acetone and then cooled on an iced bath and treated with 60 ml of acetic acid and 18-crown-6-ether 5.75 g and stirred.

482

Polyhydroxyalkanoic Acid Having Vinyl, Ester, Carboxyl, or Sulfonic Acid Group

Potassium permanganate (4.59 g) was then slowly added and the mixture stirred for 2 hours on an iced bath for 18 hours at ambient temperature. The solution was then treated with 720 ml of ethyl acetate, 540 ml of water, and sodium hydrogensulfite and the pH raised to 1 using 1.0 M hydrochloric acid. The organic layer was separated and washed three times with 1.0 M hydrochloric acid and then concentrated and the residue washed successively with 600 ml of water, 600 ml of methanol, and three times with 600 ml of water. The residue was then dissolved in THF and reprecipitated in excess methanol, dried, and 5.30 g of product isolated having an Mn of 13,200 Da with an Mw of 18,300 Da and containing 8 mol% carboxylic acid. 3. Preparation of 2-aminobenzenesulfonic acid phenyl ester graft copolymer The step 2 product (0.40 g) and 2-aminobenzenesulfonic acid phenyl ester (0.53 g) were charged into a flask and then treated with 15.0 ml of pyridine and 1.10 ml of triphenyl phosphite and heated for 6 hours at 1208C. The solution was then precipitated in 150 ml of ethanol and washed with 1 M hydrochloric acid for one day and then stirred in water for one day. The material was isolated, dried, and 0.34 g of product isolated having an Mn of 11,300 Da and an Mw of 16,800 Da containing 8 mol% amide.

DERIVATIVES TABLE 1. Physical Properties of Selected Polyhydroxyalkanoate Derivatives Containing Amide or Sulfonic Acid Components Prepared According to the Current Invention Entry

Structure

Mn (Da)

Mw (Da)

30

11,300

16,000

44

9900

14,100

(Continued)

Derivatives

483


Structure

Mn (Da)

Mw (Da)

55

10,900

17,200

56

9900

14,500

103

37,400

78,500

107

26,800

42,900

484

Polyhydroxyalkanoic Acid Having Vinyl, Ester, Carboxyl, or Sulfonic Acid Group

NOTES 1. To quantify the amount of carboxylic acid in the side chain of the step 2 product, the material was methyl esterified using trimethylsilyl diazomethane. 2. Additional derivatives of the current were prepared by the authors (1) in an earlier investigation and are discussed. 3. Williams et al. (2) prepared biocompatible poly-co-hydroxyalkanoates, (I), containing long and short alkyl pendants that were used as sutures, rivets, tacks, staples, and screws in humans.

4. Injectable liquid polyhydroxyalkanoate compositions consisting of the transesterification product of poly(3-hydroxyoctanoate-co-3-hydroxyhexanoate) with 1,3-butanediol were prepared by Williams et al. (3) and used in soft tissue repair, augmentation, and viscosupplementation in humans. 5. Biodegradable carboxy aromatic polyhydroxyalkanoate resins, (II), having high thermal stability were prepared by Fukui et al. (4) and used as toners in electrophotographic processes.

References 1. T. Kenmoku et al., U.S. Patent Application 20070155912 (July 5, 2007), U.S. Patent Application 20070117937 (May 24, 2007), and U.S. Patent Application 20070073006 (March 29, 2007). 2. S.F. Williams et al., U.S. Patent 7,268,205 (September 11, 2007) and U.S. Patent 7,179,883 (February 7, 2007). 3. S.F. Williams et al., U.S. Patent 7,025,980 (April 11, 2006). 4. T. Fukui et al., U.S. Patent Application 20060079662 (April 13, 2006).

h. Poly(N-vinyl-2-pyrrolidone) block copolymers

Title: Process for the Preparation of Amphiphilic Poly(N-vinyl-2-pyrrolidone) Block Copolymers Author: Assignee:

Laibin Luo et al. Labopharm, Inc. (Quebec, CA)



Replacement of polyethylene oxide with poly(N-vinyl-2-pyrrolidone) derivatives in drug delivery devices. Ongoing investigation. Drug delivery device Although polyethylene glycol is widely used as a hydrophilic arm on the surface of nanoparticles, liposomes, and polymeric micelles in drug delivery systems, there are inherent limitations associated with its use. The objective of this application was to prepare well-defined poly(Nvinyl-2- pyrrolidone) analogs as a replacement for poly(ethylene oxide) in drug delivery devices. The basis for selecting poly(N-vinyl-2-pyrrolidone) is its biocompatibility and its extensive use in the pharmaceutical industry. Hydroxyl-terminated poly(N-vinyl-2-pyrrolidone) was prepared using an initiator containing hydroxyl end groups. Anionic polymerization of this intermediate with D,L-lactide was used to prepare the target polymer. During the polymerization, higher ratios of isopropanol-to-vinyl-2-pyrrolidone produced polymers with low molecular weights.

485

486

Process for the Preparation of Amphiphilic Poly(N-vinyl-2-pyrrolidone)

REACTION

i. 2,20 -Azobis(2-methyl-N-(2-hydroxyethyl)-propionamide), 2-propanol ii. THF, sodium hydride, D,L-lactide

2-mercaptoethanol,

EXPERIMENTAL 1. Preparation of poly(N-vinyl-2-pyrrolidone) containing a hydroxyl chain terminus N-Vinyl-2-pyrrolidone (1.8 mol), 2,20 -azobis(2-methyl-N-(2-hydroxyethyl)-propionamide) (0.018 mol), and 2-mercaptoethanol (0.072 mol) were dissolved in 3000 ml of 2-propanol degassed for 1 hour. The free radical polymerization was carried out at reflux while stirring for 44 hours. The mixture was concentrated and then dissolved in 400 ml of 4-methyl-2-pentanone and slowly precipitated into 5000 ml of t-butyl methyl ether. The suspension was filtered and the filter cake washed twice with 200 ml of t-butyl methyl ether. The solid was purified by dissolving in 400 ml of 4-methyl-2-pentanone containing 100 ml of 2-propanol and then precipitated in 5000 ml of t-butyl methyl ether. The product was isolated after drying as a white powder having an Mn of 2060 Da, Mw of 2600 Da, with a PDI of 1.3. 2. Preparation of poly(N-vinyl-2-pyrrolidone)-b-poly(D,L-lactide) The step 1 product (48.5 mmol) was dissolved in 600 ml of THF and treated with sodium hydride (75 mmol) and then stirred for 30 minutes at ambient temperature and treated with D,L-lactide (125 g). The anionic polymerization was carried out at ambient temperature with stirring for 26 hours and excess sodium hydride removed by filtration. The volume of filtrate was adjusted to 900 ml using THF and the solution precipitated in 4500 ml of t-butyl methyl ether. The precipitate was then filtered and the cake washed twice with 100 ml of t-butyl methyl ether. The slightly yellow powder was purified by dissolving in 1215 ml of THF containing 40.5 g of activated charcoal and then stirring for 16 hours at ambient temperature and filtering over Celite. The polymer was precipitated in 6000 ml of t-butyl methyl ether, filtered, and washed twice with 100 ml of t-butyl methyl ether. The solid was dried and 62 g of product isolated as a white solid having an Mn of 3140 Da, Mw of 3445 Da, and a polydispersity index of 1.1.

Notes

487

SCOPING REACTIONS TABLE 1. Physical Properties of Poly(N-vinyl-2-pyrrolidone) Containing Hydroxyl Terminus Prepared Under Various Reaction Conditionsa Prepared According to the Current Invention Materialsb Entry

VP (g)

AMPAHE (% mol)

MCE (% mol)

IPA/VP (vol ratio)

Mn (Da)

Mw (Da)

PDI

1 3 6 9

5 5 50 50

1.0 1.0 2.0 4.0

0.75 0.75 2.0 4.0

10 20 16 16

10,290 6,300 2,510 2,170

21,300 12,460 3,470 3,190

2.1 2.0 1.4 1.5

a

Generally lower Mn and Mw values were observed when solvent/VP ratios were high. AMPAHE ¼ 2,20 -azobis(2-methyl-N-(2-hydroxyethyl)-propionamide), IPA ¼ 2-propanol, 2-mercaptoethanol, and VP ¼ N-vinyl-2-pyrrolidone. b

MCE ¼

TABLE 2. Physical Properties of Selected Poly(N-vinyl-2-pyrrolidone)-b-poly(D,L-lactide) Copolymers Prepared According to the Current Invention Entry 1 2 3

Mn PVP (Da) 2060 1850 2220

Mn PVP-b(Da)

Mw PVP-b(Da)

D,L-Lactide

D,L-Lactide

D,L-Lactide

PDI

3140 3350 3680

3445 3690 4050

1.1 1.1 1.2

Content (% mol) 38 38 37

NOTES 1. Amphiphilic poly[(N-vinyl-2-pyrrolidone)-b-poly(D,L-lactide)] was previously prepared by the authors (1) and used in drug device applications. 2. Lenaerts et al. (2) prepared a biphasic drug delivery device for tramadol consisting of polyvinyl acetate and polyvinylpyrrolidone having a sustained release for 24 hours. Polyvinylpyrrolidone was also used by Midha et al. (3) in the transdermal delivery of atomoxetine. 3. Leroux et al. (4) prepared micelle-forming compositions comprising poly(Nvinyl-2-pyrrolidone)-b-poly(D,L-lactide), which was used in drug delivery of antineoplastic agents. Prior to this disclosure only random graft copolymer poly(N-vinyl-2-pyrrolidone)-g-poly(D-lactide) had been described in the literature by Eguiburu et al. (5).

488

Process for the Preparation of Amphiphilic Poly(N-vinyl-2-pyrrolidone)

References 1. L. Luo et al., U.S. Patent 7,262,253 (August 28, 2007). 2. V. Lenaerts et al., U.S. Patent Application 20070003618 (January 4, 2007) and U.S. Patent Application 20060240107 (October 26, 2006). 3. K.K. Midha et al., U.S. Patent Application 20080031932 (February 7, 2002). 4. J.-C. Leroux et al., U.S. Patent 6,338,859 (January 15, 2008). 5. R. Eguiburu et al., Polymer, 37, 3615–3622 (1996).

E. Biomaterials for Gene Therapy a. Amidoamine oligomers

Title:

Hyperbranched Polyamidoamine

Author: Assignee:

Lance Twyman et al. CellTran Limited (Sheffield, GB)


20070265468 (November 15, 2008) Moderately high 2009

Development of high-efficiency biocompatible amidoamine dentrimeric transfection agents. Although dentrimeric transfection agents are commercially available, the preparation of hyperbranched analogs is unreported in the patent literature. Gene therapy Although a limited number of nonviral vectors are available in the marketplace, they are linear and require thermal activation. Hyperbranched amidoamine polymers have been prepared that do not require thermal activation and can be selectively expanded. These materials were prepared by successive Michael additions and amidations using excess reagents. Hyperbranched polymers were obtained from the statistical polymerization of G(1) and G(2) products and were characterized as exhibiting broad molecular weight distributions, irregular shapes, and a multitude of end groups.

489

490


REACTION

i. ii. iii. iv. v.

Methyl acrylate, triethylamine, methanol Methanol, ethylene diamine Methyl acrylate, methanol Ethylene diamine, methanol Heat EXPERIMENTAL

1. Preparation of intermediate 1 A 250-ml round-bottomed flask was charged with b-alanine (0.225 mol), methyl acrylate (0.9 mol), and 65 ml triethylamine and then dissolved in 250 ml anhydrous methanol. The solution was cooled to 08C and stirred for 1 hour and for 2 days at ambient temperature. The mixture was then concentrated and the product isolated as a free-flowing honey-colored oil in 99% yield. 1

H-NMR (CDCl3) d H 2.37 (t, 2H, CH2COOH); 2.47 (t, 4H, CH2CO); 2.74 (t, 2H, CH2CH2COOH); 2.80 (t, 4H, NCH2); 3.63 (s, 6H, OCH3); 9.11 (bs, 1H, COOH) 13 C-NMR d C 31.5, 32.3, 48.3, 49.1, 51.2, 172.2, 175.6 FTIR (cm21) 3410, 2955, 2844, 2622, 2490

Experimental

491

2. Preparation of intermediate 2 The step 1 product (0.203 mol) was dissolved in 150 ml anhydrous methanol and then added dropwise over a period of 1 hour to a stirred solution of 81 ml ethylene diamine dissolved in 200 ml methanol at 08C. After the addition was complete, the reaction was stirred at ambient temperature for 7 hours and then concentrated. Final traces of ethylene diamine were removed by placing the oil under a high vacuum for 5 days @ 0.2 mmHg and the product isolated as a thick orange oil in 98% yield. 1

H-NMR (d6-DMSO) d H 2.08 (bt, 2H, CH2COOH); 2.19 (bt, 4H, CH2CO); 2.50–2.70 (bm, 10H, residual CH2’s); 3.10 (bq, 4H, CH2NH); 8.22 (bt, 2H, NH) 13 C-NMR d 34.4, 37.0, 40.7, 40.9, 50.8, 51.3, 173.5, 178.9 FTIR (cm21) 3270, 3068, 2938, 2169, 1651 cm21

3. Preparation of intermediate 3 The step 2 product (3.84 1022 mol) dissolved in 50 ml anhydrous methanol was added dropwise to a stirred solution of 21 ml methyl acrylate dissolved in 50 ml methanol over a period of 30 minutes at 08C and then stirred for 2 days at ambient temperature. The mixture was then concentrated and the product isolated as a thick orange oil in 98% yield. 1

H-NMR (CDCl3) d H 2.25–2.47 (m, 18H, CH2N); 2.55– 2.85 (series of triplets, 14H, CH2CO); 3.15 (bq, 4H, NHCH2); 3.52 (s, 12H, OCH3); 7.02 (bt, 2H, NH); 7.68 (bs, 1H, COOH) 13 C-NMR d 31.2, 32.1, 32.2, 32.4, 36.6, 48.7, 48.9, 51.4, 52.4, 61.9, 171.0, 172.7, 174.6 FTIR (cm21) 3297, 2952, 2829, 2045

4. Preparation of intermediate 4 The step 3 product (3.54 1022 mol) was dissolved in 100 ml of anhydrous methanol and then added dropwise over 1 hour to a stirred solution of 190 ml ethylene diamine dissolved in 100 ml of methanol at 08C. Thereafter the reaction was stirred at ambient temperature for 9 days and then concentrated and the product isolated as a thick orange oil in quantitative yield. 1

H-NMR (d6-DMSO) d H 2.10– 2.30 (series of broad triplets, 14H, CH2CO); 2.40– 2.75 (bm, 26H, residual CH2’s); 3.00 –3.25 (bq, 12H, CH2NH); 8.06 (bt, 2H, NH); 8.36 (bt, 4H, NH) 13 C-NMR d 34.6, 37.1, 38.0, 42.4, 43.3, 50.7, 51.1, 51.6, 52.2, 53.2, 172.9, 177.7 FTIR (cm21) 3271, 3063, 2935, 2863, 2359, 2341

5. Polymerization of intermediate 4 The step 4 product was placed in a reaction tube and heated to 2008C @ 0.5 mmHg for 24 hours. The crude polymer was isolated as glassy orange solid and was purified using membrane filtration with a 2.4-nm cut-off and the product isolated in 40 – 70% yield. 1

H-NMR (d6-DMSO) d H 1.00–4.50 (series of broad multiplets, NH), 1.0–2.8 (CH2N and CH2O H), 2.8–4.5 (CH2NH H); 7.70 –8.80 (broad singlet, NH)

492


13

C-NMR (d6-DMSO) d C 29.3, 29.5, 31.5, 31.9, 32.6, 33.2, 33.4, 34.0, 36.5, 37.8, 38.5, 38.8, 39.5, 43.3, 43.7, 44.2, 45.7, 49.6, 49.8, 50.0, 50.3, 50.6, 51.0, 51.4, 51.8, 52.0, 52.2, 52.7, 53.0, 53.5, 54.1, 158.8, 168.2, 168.9, 171.3, 171.7, 172.5, 172.7, 173.0, 173.3, 173.4 Mw 5828 Da, PD 2.4, Mzþ1 15, 707 Da TGA degradation onset 2728C; 10% wt loss 3318C

DERIVATIVES The step 2 intermediate was also thermally polymerized.

TESTING Transfection testing data for hyperbranched amidoamine polymers are provided in Table 1. TABLE 1. Transfection Efficiencies for Selected Carriers Using EAhy 926, HSVEC 1, and HEK 293 Cell Lines and the Step 2 and Step 5 Products Entry A B C D

E

Description

Transfection Efficiency (%)

Intermediate 2 Intermediate 4 SUPERFECTw Polyamidoamine (PAMAM dentrimer with 64 termini) Control (unspecified)

20 40 40 2.5 ,1

NOTES 1. Although transfection efficiencies was low, Lim et al. (1) prepared hyperbranched polyaminoesters, (I), using Michael addition of ethanolamine with methyl acrylate followed by bulk polymerization.

Notes

493

2. Hyperbranched polymers consisting of 1,4-butanediol diacrylate and 1-(2-aminoethyl)-piperazine were prepared by Liu et al. (2) and used as nucleotide carriers. 3. Banerjee et al. (3) prepared hyperbranched dendrons consisting of polyethyleneimine and 2-chloroethylamine hydrochloride for use as transfection agents. 4. Biocompatible dendrimers were prepared by Tomalia et al. (4) and are discussed.

References 1. Y-B. Lim et al., J. Am. Chem. Soc., 123, 2460–2461 (2001). 2. Y. Liu et al., U.S. Patent 7,309,757 (December 18, 2007). 3. P. Banerjee et al., U.S. Patent 7,153,905 (December 26, 2006). 4. D.A. Tomalia et al., U.S. Patent 7,078,461 (July 18, 2006).

F. Biomaterials for Membranes a. Polyethylene glycol polyacrylate derivatives

Title:

Barrier Membrane

Author: Assignee:

Aaldert Rens Molenberg Straumann Holding AG (Basel, CH)


494

20080039577 (February 14, 2008) Moderately High Late 2010

Cell-occlusive membranes prepared from aliphatic thiols and polyethylene glycol polyacrylate crosslinkers. Ongoing investigation using polyethylene glycol polyacrylate crosslinkers as resorbable medical implants. Resorbable medical implants Cell-occlusive polyethylene glycol containing biodegradable barrier membranes were prepared by thermally crosslinking polyethylene glycol polyacrylate with polyethylene glycol and mercaptans in the presence of water. These materials were then used to augment tissue and in bone regeneration. Other crosslinked polymer compositions for tissue augmentation were prepared from polyethylene glycol polyamines and tetrafunctional polyethylene glycol succimidyl glutatate. Since these experimental membrane are of nonanimal origins, the risk of inflammation and pathogen transmission is eliminated.

Experimental

495

REACTION

i. THF, acryloylchloride, CH2Cl2 ii. a,v-Bis(3-mercapropropyl)-polyethylene chloride

glycol,

triethanolamine

hydrogen

EXPERIMENTAL 1. Preparation of polyethylene glycol triacrylate A 3-arm polyethylene glycol (Mn of 14,763 Da) was dissolved in 150 ml of dry THF under an argon atmosphere and refluxed over molecular sieves until the water content was less than 100 ppm. It was then cooled to ambient temperature and treated with triethylamine (7.7 mmol) and the dropwise addition of acryloylchloride (7.7 mmol) dissolved in 20 ml of CH2Cl2 at such a rate that the temperature remained below 308C. The suspension was filtered through 1 cm of Celitew 545 and a pale yellow clear solution obtained to which 4-methoxy-phenol (44 mg) was added. The mixture was then concentrated and the residue redissolved in 150-ml of water and NaHCO3 added until a pH of 8 was obtained. The aqueous solution was washed twice with 40 ml of diethyl ether and then treated with NaCl (10 g) and the product extracted with four 50-ml portions of CH2Cl2. Combined organic layers were dried with Na2SO4, filtered, treated with 4-methoxy-phenol (30 mg), and concentrated to 35 ml. The solution was precipitated in 800 ml of cold diethyl ether, isolated by filtration, dried, and 11.5 g of product isolated as a white powder having a degree of functionalization of 97%. 2. Gelation a,v-Bis(3-mercapropropyl)-polyethylene glycol (4.0 meq) and the step 1 product (4.0 meq) dissolved in equal amounts of aqueous 0.30 M triethanolamine/HCl buffer at pH 8.0 were cooled to 08C and quickly mixed and then placed between the plates of a parallel-plate rheometer. While the plates were kept at 378C, the storage (G0 ) and loss (G00 ) moduli were measured as a function of time at a frequency of 10 Hz. The gel point, defined as the crossover point of G0 and G00 , was determined for several polyethylene glycol derivatives and are provided in Table 1.

496

Barrier Membrane

TABLE 1. Gelation Properties of Reaction Product of a,v-bis(3-mercapropropyl)polyethylene Glycol and Polyethylene Glycol Triacrylate and 3788 C at 10 Hz as a Function Poly(ethylene Glycol Content) Polyethylene Glycol (wt%) 9.2 10.3 12.3 14.9

Gel Point (s)

Storage Modulus at 30 min (kPa)

632 486 316 289

2.9 4.3 8.4 9.6

DERIVATIVES Gels were also prepared using polyethylene-tetrathiol, (I), and polyethylene-tetraacrylate, (II), with the step 1 product and had molecular weights between of 2000 and 10,000 Da, respectively.

TESTING A. Material Preparation Membranes of polyethylene glycol gels were cast at ambient temperature under sterile conditions in cylindrical stainless steel molds using membrane kits containing equimolar amounts of 4-arm polyethylene glycol-thiol (2000 Da) and 8-arm polyethylene glycol-acrylate (2000 Da) using triethanolamine/HCl buffer as a viscosity modifier. Before gelation set in, a fibrin sponge was placed in the center of each membrane gel and the molds covered and cured for 1 hour. These materials were then transferred to sterile 10 mM phosphate- buffered saline (PBS) and stored in an incubator overnight at 378C. B. Cell Occlusivity Testing Results After one month the polyethylene glycol shielded implants were basically cell free, whereas in unshielded implants the fibrin phase of the sponge was completely invaded by densely packed cells. Statistical analysis showed significant differences (P ¼ 0.00004) between samples and positive controls. NOTES 1. In an earlier investigation by the authors (1) crosslinked compositions consisting of 1,1,1-tris(hydroxylmethyl)propane-tris(butylitaconate), (III), and

Notes

497

1,2,4-tris(2-mercapto ethyl)-cyclohexane, (IV), were prepared and used in tissue augmentation.

2. Hydrogels prepared from poly(ethylene glycol) diacrylate macromonomer having an Mn of 20,000 Da were used by Sawhney et al. (2) for hydrogel articles for sealing or for augmentation of tissue or vessels. 3. A photoreactive macromer consisting of the reaction product of poly(caprolactone-co-lactide) and pentaerythritol ethoxylate was prepared by Chudzik et al. (3) and used as tissue implants. 4. Block copolymers consisting of polyethylene glycol and a di-peptide, (V), were prepared by Hossainy (4) and used as a drug delivery device and to treat chronic total occlusion.

References 1. A.R. Molenberg et al., U.S. Patent Application 20030232944 (December 18, 2003). 2. A.S. Sawhney et al., U.S. Patent Application 20080017201 (January 24, 2008). 3. S.J. Chudzik et al., U.S. Patent Application 20060240072 (October 26, 2006). 4. S.F.A. Hossainy, U.S. Patent Application 20060142541 (June 29, 2006).

XV. NITRIC-OXIDE-RELEASING AGENTS A. Antirestenosis Agents a. Diazeniumdiolation agents

Title:

Nitric-Oxide-Releasing Polymers

Author: Assignee:

Ernst V. Arnold et al. Government of the United States of America as Represented by the Secretary, Department of Health (Rockville, MD)


Observations:

20070286840 (December 13, 2007) Extremely high Early 2009

Preparation of nitric-oxide-releasing polymers by diazeniumdiolation of isocyanides followed by nitric oxide absorption. There is very limited patent literature on nitric-oxide-releasing polymers. Antirestenosis therapy Catheters Wound dressings and bandages Blood collection bags Nitric-oxide-releasing amidine diazeniumdiolates first appeared in the U.S. patent literature in 2005 and were reported as stable nitric-oxidereleasing compounds. The current application represents an extention of an earlier investigation by this group. In the current application diazeniumdiolation was performed on a polymeric substrate containing a cyanomethylated substituent. The only requirement for polymer selection was that it remain inert during the diazeniumdiolation process. Diazeniumdiolation was performed under high nitric oxide pressure under basic conditions to avoid producing nitrosamine intermediates. Once prepared diazeniumdiolated modified polymers released nitric


499

500

Nitric-Oxide-Releasing Polymers

oxide spontaneously under physiological conditions without nitrosamine formation. Shunts prepared from diazeniumdiolated polymers are particularly directed for use in antirestenosis therapy and at implantation sites.

REACTION

i. N,N-Dimethylformamide, potassium cyanide, potassium iodide ii. Sodium trimethylsilanolate, N,N-dimethylformamide, nitric oxide

EXPERIMENTAL 1. Preparation of cyanomethylated polystyrene A sample of 50 ml of N,N-dimethylformamide was used to swell chloromethylated polystyrene (2.37 g; 4.42 mmol Cl per g), and after 30 minutes the material was treated with potassium cyanide (52 mmol) and potassium iodide (1.4 mmol). It was then heated to 608C overnight during which the resin color changed from whitish to brick red. The resin was then washed consecutively with 20 ml portions of N,N-dimethylformamide, N,N-dimethylformamide/water, water, ethanol, EtOH, and diethyl ether and the product isolated. 2. Preparation of diazeniumdiolated polystyrene A Parr reactor charged with the step 1 product and 20 ml N,N-dimethylformamide was treated with 20 ml of 1.0 M sodium trimethylsilanolate (20 mmol) dissolved in tetrahydrofuran (THF). The vessel was then degassed and charged with 54 psi nitric oxide. When the reaction was completed, the product was washed, dried, and the product isolated.


Notes

501

NOTES 1. Diazeniumdiolated derivatives were initially prepared by the authors (1) as nitric-oxide-releasing compounds as illustrated in Eq. (1) for the formation of benzyl diazeniumdiolate methoxy imidate, (I).

(1)

i. Methyl alcohol, sodium methoxide, nitric oxide 2. In an earlier investigation by Kalivretenos et al. (2), 4-acetyl-polystyrene was converted into diazeniumdiolated polystyrene, (II), using the reagents of the current application.

3. Diazeniumdiolation methods for eneamines and thioimidate are described by Hrabie et al. (3) and Arnold et al. (4), respectively. References 1. E.V. Arnold et al., U.S. Patent 7,105,502 (September 12, 2006) and U.S. Patent 6,673,338 (January 4, 2004). 2. A.G. Kalivretenos et al., U.S. Patent Application 20070196327 (August 23, 2007). 3. J.A. Hrabie et al., U.S. Patent 6,911,478 (June 28, 2005). 4. E.V. Arnold et al., U.S. Patent 6,673,338 (January 6, 2004).

b. Hindered amines

Title: Hindered Amine Nitric-Oxide-Donating Polymers for Coating Medical Devices Author: Assignee:

Peiwen Cheng et al. Medtronic Vascular, Inc. (Santa Rosa, CA)



502

20070264225 (November 15, 2007) Very high Mid-2009

Preparation of diazeniumdiolated copolymers as nitric-oxide-releasing agents. Although diazeniumdiolated polymers have been used in vascular stents, the synthesis of these agents from hindered amines is unreported in the patent literature. Antirestenosis therapy Diazeniumdiolates are nitric-oxide-releasing agents that are prepared in a single step using high-pressure nitric oxide on imine and acrylonitrile derivatives. The current application extends this list to include hindered amines. The only reported requirement for the substrate is that it remain inactive during the diazeniumdiolation process. Diazeniumdiolated materials were used as coatings on vascular stents to slowly release nitric oxide without the release of nitrosamines during antirestenosis therapy at the implantation site.

Experimental

503

REACTION

i. n-Butyl methacrylate, n-propyl alcohol, 2-butanone, 2,20 -azobis(2-methylpropionitrile) ii. Sodium methoxide, methanol, nitric oxide iii. Sodium methoxide, methanol, nitric oxide, vascular stent EXPERIMENTAL 1. Preparation of poly(n-butyl methacrylate-co-2-(t-butylamino)ethyl methacrylate) A 500-ml reactor was charged with 2-(t-butylamino)ethyl methacrylate (0.54 mmol) and n-butyl methacrylate (0.54 mmol) in a mixture of 300 ml n-propyl alcohol/ 2-butanone, 70:30, respectively, and then treated with 2,20 -azobis(2-methylpropionitrile) (1.36 g). A net positive pressure of nitrogen was introduced and the reaction heated at 608C for 5 hours and then cooled to ambient temperature. The solution was poured into methanol at 2608C precipitating a white solid. The solid was isolated and redissolved in chloroform and then reprecipitated in methanol, the process being repeated three times. The polymer was dried in vacuo and the product isolated. 2. Preparation of diazeniumdiolated copolymer The step 1 product (10 mg) dissolved in 50 ml THF was placed in a high-pressure reaction vessel purged with nitrogen gas. Sodium methoxide in methanol was then added in 150 mol% excess and stirred while the reactor was purged with nitric oxide at 15 psi. Thereafter, the mixture stirred at ambient temperature for 24 hours and was then purged and the mixture precipitated in hexane. After filtering and drying, the product was isolated. 3. Preparation of a diazeniumdiolated polymer-coated vascular stent A vascular stent was coated with the step 1 product and then placed in a 13 mm 100 mm glass test tube and treated with 10 ml 3% sodium methoxide in methanol.

504

Hindered Amine Nitric-Oxide-Donating Polymers for Coating Medical Devices

It was then placed into a 250-ml Parrw reactor and then pressurized/depressurized 10 times with nitrogen at 10 atmospheres. The reactor was then treated with two pressurization/depressurizations with nitric oxide at 30 atmospheres. Finally, the vessel was filled with nitric oxide at 30 atmospheres and left at ambient temperature for 24 hours. The vessel was then repeatedly pressurized/depressurized with nitrogen gas at 10 atmospheres. The test tube was removed from the vessel and sodium methoxide solution decanted. The stent was then washed with 10 ml of methanol and three times with 10 ml diethyl ether and then dried under a stream of nitrogen gas and the diazeniumdiolated stent isolatedt. NOTES 1. Chen et al. (1) prepared water-insoluble diazeniumdiolated polyethyleneimines by condensing C1 – C8 aliphatic anhydrides with polyethyleneimine and then postreacting with nitric oxide at 10 atmospheres of pressure.

2. Polyethyleneimine crosslinked with 2,5-dinitro-1,4-difluorobenzene and 3-aminopropyltrimethoxysilane was diazeniumdiolated by Fitzhugh et al. (2) using NO and used in medical applications. 3. Nitric-oxide-releasing diazeniumdiolated acrylonitrile polymers, (II), were prepared by Hrabie et al. (3) and used in medical devices as illustrated in Eq. (1).

(1)

Notes

505

4. Nitric-oxide-releasing compounds were prepared by Assaf et al. (4) so that when NO was released a nonirritating residual, (III), formed.

References 1. M. Chen et al., U.S. Patent Application 20070053952 (March 8, 2007). 2. A.L. Fitzhugh et al., U.S. Patent Application 20070014828 (January 18, 2007). 3. J.A. Hrabie et al., U.S. Patent Application 20070292471 (December 20, 2007). 4. P. Assaf et al., U.S. Patent Application 20070021382 (January 25, 2007).

XVI. OPTICAL A. Intraocular Lenses a. Polyazo derivatives

Title: Copolymerizable Azo Compounds and Articles Containing Them Author: Assignee:

Jason Clay Pearson et al. Eastman Chemical Company (Kingsport, TN)



Synthesis of polymerizable light-absorbing azo dyes useful as intraocular lenses covalently bonded to other unsaturated ethylene monomers. This has been an ongoing 6-year investigation. Intraocular lenses Azo intermediates that effectively absorb ultraviolet A (UV-A) radiation have been prepared by coupling diazonium salts with either heterocyclics or heteroaromatics. To prepare these materials diazo-containing monomers were then free radically copolymerized with 2-phenylethyl acrylate, 2-phenylethyl methacrylate, or 1,4-butanediol diacrylate. Since only marginal amounts of unbound azo dye was detected, this process eliminated dye leaching problems associated with polymer blends containing light-absorbing dyes.


507

508

Copolymerizable Azo Compounds and Articles Containing Them

REACTION

i. Hydrochloric acid, water, sodium nitrite, 3-methyl-1-phenyl-2-pyrazolin-5-one, sodium hydroxide ii. 4-Dimethylaminopyridine, hydroquinone, triethylamine, acetone methacrylic anhydride iii. 2-Phenylethyl acrylate, 2-phenylethyl methacrylate, 1,4-butanediol diacrylate, 2,20 -azobisisobutyronitrile EXPERIMENTAL 1. Preparation of azo intermediate To a solution of 36 ml of 12 M hydrochloric acid and 100 ml of water was added 4-aminophenethyl alcohol (0.12 mol) and then cooled and treated with a solution of sodium nitrite (0.15 mol) dissolved in 32 ml water at 0 –38C. Stirring was continued for 2 hours while a mixture of 3-methyl-1-phenyl-2-pyrazolin-5-one (0.12 mol) dissolved in 800 ml water containing 50% aqueous sodium hydroxide (26.5 g) was prepared. This second solution was then added dropwise to the diazonium salt with stirring while cooling was continued to maintain the temperature at about 3 – 58C. Stirring was continued at about 58C for an additional hour and the solid yellow product collected by vacuum filtration. The product was then washed with water, dried in air, and isolated in 97.9% yield which assayed at 96.2%. lmax ¼ 403 nm [dimethyl formamide (DMF)]

Experimental

509

2. Preparation azo acrylate monomer The step 1 product (0.11 mol), 4-dimethylaminopyridine (0.06 mmol), hydroquinone (0.35 g), and triethylamine (0.375 mol) were added to 275 ml dry acetone and then treated with methacrylic anhydride (0.14 mol). The mixture was refluxed for 90 minutes while the reaction progess was monitored by thin-layer chromatography. Since some hydroxyl starting material still remained, an additional 5 ml of methacrylic anhydride was added and the mixture refluxed an additional hour. Once the reaction was completed, the solution was cooled to ambient temperature and a yellow solid isolated. The solution was further treated with 100 ml cold methanol to further precipitate the product. The material was collected, washed with cold methanol, air dried, and 78.3% product isolated with a 96% purity. lmax ¼ 408 nm (DMF) 1 ¼ 22,100

3. Preparation of A. Stock Monomer Mixture A stock mixture (50 g) of monomers suitable for preparing intraocular lens material was prepared by thoroughly mixing 2-phenylethyl acrylate (66 wt%), 2-phenylethyl methacrylate (30.5 wt%), and 1,4-butanediol diacrylate (3.5 wt%). B. Intraocular Lenses A 20-ml vial was charged with the step 2 product (10.7 mg) and stock mixture (10 g) to give an azo concentration of about 0.1 wt%. The mixture was stirred to 508C until a solution was obtained and then cooled to ambient temperature and treated with 2,20 azobisisobutyronitrile (52.3 mg). About 2 g of the resulting solution was added to an 18 mm 150 mm test tube by syringe and polymerization was initiated by heating the test tube to 658C in an oven under nitrogen for 17 hours and then further heated to 1008C for an additional 3 hours. The tube was then removed from the oven and cooled to ambient temperature. The polymer was removed using a spatula and placed in a vial containing 25 ml acetone. The solid was then crushed into small pieces using a spatula and then placed into a Soxhlet thimble and extracted with acetone for 5 hours. No color change was observed in the Soxhlet, indicating that the azo compound was polymerized with the stock monomer mixture. The polymer was removed, dried on a watch glass overnight, and isolated.

510

Copolymerizable Azo Compounds and Articles Containing Them

DERIVATIVES TABLE 1. Selected Step 2 Azo Methacrylate Intermediates and Corresponding Maximum Absorption, lmax, and Molar Absorpitivity, 1, (DMF) Properties

lmax (nm)

1

5

380.8

24,400

7

380.0

45,000

8

384.0

25,900

Entry

Structure

NOTES 1. Additional azo intermediates, (I), were previously prepared by the authors (1) and used in ophthalmic lenses and are discussed.

2. The reaction product of dimethyl malonate and 1,6-hexanediol with dimethylaminobenzaldehyde, 4-methoxy-benzaldehyde, and 3-nitrobenzaldehyde was previously prepared by the authors (2) and used in ophthalmic applications.

Notes

511

3. Functionalized diazo dye monomers, (II), were prepared by Hagting et al. (3) and used to prepare ophthalmic lenses that absorbed light between 400 and 550 nm.

4. The polymerizable azo monomer, (III), was copolymerized with selected benzotriazoles, (IV), and used by Lai et al. (4) to prepare ophthalmic materials that absorbed at 475 mn.

References 1. J.C. Pearson et al., U.S. Patent Application 20070207331(September 6, 2007) and U.S. Patent Application 20060110430 (May 25, 2006). 2. J.C. Pearson et al., U.S. Patent Application 20070287822 (December 13, 2007). 3. J.G. Hagting et al., U.S. Patent Application 20070100018 (May 3, 2007). 4. Y.-C. Lai et al., U.S. Patent Application 20070100018 (April 26, 2007).

b. Poly(dimethacrylate thiophene disulfide-co-2-hydroxyethyl methacrylate)

Title: High Refractive Index Monomers, Compositions, and Uses Thereof Author: Assignee:

Liliana Craciun et al. Ciba Specialty Chemicals Corporation (Tarrytown, NY)



20080200582 (April 21, 2008) High July, 2010

Synthesis of high refractive index monomers of mono- and dimethacrylates containing thiophene and disulfide for crosslinking with 2-hydroxyethyl methacrylate. Monomers consisting mono- and dimethacrylate thiophenes and disulfides are unreported in the patent literature. Optical lens Dimethacrylate aromatic disulfide monomeric derivatives were prepared in three steps entailing: i. Chloromethylation of thiophene using the Blanc reaction ii. SN2 displacement of this intermediate using selected mercaptoalkoxides iii. Conversion to the target methacrylate monomer by reacting with methacryloyl chloride Photopolymerization with 2-hydroxyethyl methacrylate was then used to prepare the crosslinked copolymer. While other high refractive index crosslinkable methacrylate monomers are reported in the patent literature, this application entails polymerizing four monomers one of which contains a crosslinkable siloxane or fluoro-containing component.

512

Experimental

513

REACTION

i. ii. iii. iv.

Hydrogen chloride, formaldehyde, hydrochloric acid Sodium mercaptoethanol Triethylamine, CH2Cl2, methacryloyl chloride 2-Hydroxyethyl methacrylate, tetrapropoxy zirconium EXPERIMENTAL

1. Preparation of 2,5-bis(chloromethyl)thiophene A stream of dry hydrogen chloride was bubbled through an aqueous solution of 37% formaldehyde (2.24 mol) and 147 ml 12 M hydrochloric acid when the reaction temperature rose to 608C. The mixture was then cooled to 308C and then treated with the slow addition of thiophene (1.79 mol) at such a rate the temperature did not exceed 308C. When the addition was completed, the mixture was stirred an additional 20 minutes and a lower oily layer was separated. It was washed with cold water and distilled on a Vigreux column. The first fraction distilled at 308C @ 1.2 mbar and was identified as 2-chloromethylthiophene. The second fraction distilled at 808C @ 1.2 mbar and identified as the target compound and 120.4 g of product were isolated having an mp ¼ 36 – 378C. 2. Preparation of 2,5-bis(hydroxyethylthiomethyl)thiophene The step 1 product (0.55 mol) was added dropwise to an aqueous solution of 45% sodium mercaptoethanol (1.16 mol) and heated to 508C for 5 hours. The mixture was then extracted with diethyl ether, washed with 5% aqueous NaOH, cold water, and dried using sodium sulfate. The solution was concentrated and 136.5 g of product isolated as a thick liquid. 3. Preparation of 2,5-bis(methacryloyloxyethylthiomethyl)thiophene A reaction vessel containing the step 2 product (0.23 mol) and triethylamine (0.64 mol) dissolved in 500 ml CH2Cl2 was treated with the dropwise addition of methacryloyl chloride (0.58 mol) at 0 – 58C. The mixture was stirred for 3 hours and then quenched by adding 100 ml of water. The organic phase was extracted with

514

High Refractive Index Monomers, Compositions, and Uses Thereof

CH2Cl2, washed with 5% aqueous NaOH, and dried over MgSO4. The mixture was then concentrated and 76 g of product isolated as a pale yellow, clear liquid. 4. Preparation of polymer The step 3 product (9 mmol), 2-hydroxyethyl methacrylate (4.8 mmol), and tetrapropoxy zirconium (35 mg) were blended together and the solution cast into molds then UV-cured to give clear, hard plastic parts.

DERIVATIVES TABLE 1.

Physical Properties of Selected High Refractive Index Monomersa

nD

Tg (8C)

Rockwell Hardness (R scale)

3

1.61

107

124

5

1.65

95

123

7

1.64

75

117

13

1.60

130

120

23

—

45

—

Entry

a

Structure

No “acrylate” odor was exhibited from any of these experimental agents during processing.

Notes

515

TESTING A. Rockwell Hardness Hardness was measured on the Rockwell hardness scale according to the method described in ASTM D785-93. Test results are reported as a Rockwell hardness number, which is directly related to the indentation hardness of a plastic material where higher values reflect greater hardness. Measurements were done on the R scale using a minor load of 10 kg or major load of 60 kg. Testing results are provided in Table 1. B. Odor Measurement Cast UV-cured plastic parts were qualitatively assessed for odor while cutting and grinding.

NOTES 1. High refractive index optical lenses were prepared by Your et al. (1) consisting of trifluoroethyl methacrylate, butyl acrylate, phenyl ethyl acrylate, and ethylene glycol dimethacrylate. 2. Medina et al. (2) prepared a high refractive index monomer component, (I), for use in optical lenses by the photoinduced [2 þ 2] dimerization of dimethylmaleiimide, (I), as illustrated in Eq. (1).

(1)

3. Pearson et al. (3) prepared high refractive index copolymerizable azo compounds, (III), which were used to prepare intraocular lenses.

516

High Refractive Index Monomers, Compositions, and Uses Thereof

4. The low refractive index monomer, diethylene glycol bis allyl carbonate, was prepared by Khandel et al. (4) and used in plastic ophthalmic lenses.

References 1. J. Your et al., U.S. Patent Application 20080200982 (August 21, 2008). 2. A.N. Medina et al., U.S. Patent Application 20080143958 (June 19, 2008). 3. J.C. Pearson et al., U.S. Patent Application 20080182957 (July 31, 2008). 4. R.K. Khandel et al., U.S. Patent Application 20080182916 (July 31, 2008).

c. Polymethylmethacrylate-g-exo-methylene lactone

Title:

Compound, Polymer, and Optical Component

Author: Assignee:

Hiroshi Abe Mitsubishi Rayon Co., Ltd. (Tokyo, JP)


20080074753 (March 27, 2008) Moderate 2010

Preparation of polymethylmethacrylate derivatives containing pendant sulfonyl or exo-methylene lactone functions. Considerable prior art exists attempting to prepare optical components that have a low refractive index and high Abbe number. Optical lenses Resins having a refractive index 1.51 and an Abbe number 57 are required to prepare lens materials. For example, lens materials consisting of polymethylmethacrylate require an enlarged curvature resulting in thickened lenses because the refractive index is only 1.492. While thioglycidyl sulfide resins having a refractive index of 1.71 exist, they only have an Abbe number of 36 so that these lens would be subject to color blurring due to wavelength dispersion. While copolymers of methyl methacrylate and 3-methylene-dihydrofuran-2-one or 4-methyl3-methylenedihydrofuran-2-one have also been prepared, the Abbe number is slightly lower than that of polymethylmethacrylate. The current application addresses these limitations using polymethacrylate polymers containing pendant 3,3-dioxide-3-thiatricyclopentane. The monomers, 3,3-dioxide-3-thiatricyclo[5.2.1.026]decyl-8- and -9-methacrylates, were prepared in four steps consisting of: i. Ring isomerization of 2,3-dihydrothiophene 1,1-dioxide using potassium t-butoxide ii. Diels –Alder coupling with cyclopentadiene iii. Esterification of this intermediate with formic acid iv. Transesterification using methyl methacrylate 517

518


REACTION

i. ii. iii. iv. v.

Potassium t-buthoxide, hydrochloric acid Cyclopentadiene, toluene Formic acid, sulfuric acid Butyl titanate, methyl methacrylate 2,20 -Azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl sulfoxide EXPERIMENTAL

1. Preparation of 2,3-dihydrothiophene-1,1-dioxide A flask was charged with 2,5-dihydrothiophene-1,1-dioxide (0.85 mol) and heated to 668C for 30 minutes and then treated with potassium t-buthoxide (0.25 mol) and reacted for 6 hours. The solution was then cooled and neutralized by adding 35% hydrochloric acid and concentrated. The residue was treated with 1 liter of toluene, filtered, and reconcentrated. The residue was distilled at 130 –1358C @ 2 mmHg and 22.0 g of product isolated. 2. Preparation of 3-thiatricyclo[5.2.1.0.sup.2,6]dec-8-ene 3,3-dioxide The step 1 product (0.13 mol), cyclopentadiene (0.19 mol), and toluene (0.54 mol) were put into an autoclave and heated to 1808C for 8 hours at 0.3 mPa. The mixture was then concentrated, the residue purified by column chromatography, and 15.2 g of product isolated. 3. Preparation of 3,3-dioxide-3-thiatricyclo[5.2.1.02,6]decyl-8and -9-formates A 50-ml egg-type flask equipped with a reflux cooling tube and a stirrer bar was charged with the step 2 product (0.0543 mol) and then treated with formic acid (0.380 mol) and sulfuric acid (0.0136 mol) and heated to 1008C for 2 hours. The

Testing

519

flask was then cooled and the mixture diluted with 300 ml toluene and then neutralized with NaHCO3 solution. Under reduced pressure the mixture was concentrated and 10.0 g of a mixture of 3,3-dioxide-3-thiatricyclo-[5.2.1.02,6]-decyl-8- and -9-formates isolated. 4. Preparation of a mixture of 3,3-dioxide-3-thiatricyclo[5.2.1.02,6]decyl-8and -9-methacrylates A 50-ml flask was charged with the step 3 product mixture (0.0218 mol), butyl titanate (0.00218 mol), and methyl methacrylate (0.152 mol) and heated to 958C for 2 hours and treated with water (0.157 mol). The precipitate that formed was isolated by filtration and excess methyl methacrylate removed by vacuum distillation. The residue was purified by column chromatography and 5.86 g of product isolated as a mixture. 1

H-NMR (CDCl3) d (6.06– 6.07 (H2CvC,, 1H, s), 5.54–5.58 (H2CvC,, 1H, s), 5.42–5.44, 4.92– 4.94, 4.62– 4.64, 4.51 –4.53 (COOZCHZ, 1H, d), 3.30–3.42 (.CHSO2CH2Z, 1H, m), 2.68– 3.26 (CHSO2CH2Z, 2H, m), 1.96– 1.98 (H22CvC(CH3)Z, 3H, s), 2.20–2.40, 1.95– 1.38 (.CHZ, ZCH2Z, 9H, m)

5. Preparation of polymethacrylate polymer containing a 3,3-dioxide-3thiatricyclo-[5.2.1.02,6]decyl pendant A glass reactor was charged with the step 4 product (4.0 g), 2,20 -azobis(4-methoxy2,4-dimethylvaleronitrile) (0.0024 g), and dimethyl sulfoxide (12 g) under a nitrogen blanket and then heated to 558C for 6 hours and 708C for 2 hours. The reaction mixture was then poured into 1000 ml of water and the precipitate collected by filtration. The precipitate was dried and 3.02 g of product isolated as a white solid having an Mn was 74,500 Da, Mw of 124,000 Da, and a poly dispersity index (PDI) of 1.66.

DERIVATIVES Additional polymerizable monomers were prepared and illustrated below.

TESTING Refractive Index The refractive index of experimental agents was measured at 258C at 589 nm using an Abbe refractometer. The Abbe number was determined by measuring the

520


refractive index at 258C at 486, 589, and 656 nm. Testing results are provided in Table 1.

TABLE 1. Physical Properties of Selected Polymers Prepared According to Current Application Indicating the Favorable Balance between Refractive Index and Abbe Number

Entry

PolyDTTCMA

1 2 3 4 Comparative

PolyDTHTMA

PolyTHPMBL

PMMA

Refractive Index (nD)

Abbe Number (nD)

Water Absorption (%)

82 100

1.524 1.514 1.532 1.505 1.491

60 61 58 57 56

— 2.3 2.4 0.9 0.5

100 100 100 18

NOTES 1. Polythiocarbonate urethanes, (I), prepared by Watanabe et al. (1) having molecular weights 2500 Da had favorable refractive indexes and Abbe numbers and were used in plastic lenses.

2. Crosslinked poly(urea-urethane)s consisting of tris(4-isocyanatophenyl)methane, trimethylolethane, and 4,40 -methylenebis(3-chloro-2,6-diethylaniline) were prepared by Rukavina et al. (2) and used in optical lenses. Polycaprolactone diol derivatives were also prepared by Rukavina et al. (3) and used in optical lenses. 3. Bojkova et al. (4) prepared high-impact poly(urethane-urea) polysulfides having a refractive index of at least 1.57, an Abbe number of at least 32, and a density .1.3 g/cm3, which consisted of the reaction product of

Notes

521

4,40 -methylenebis(cyclohexyl isocyanate), polycaprolactone diol having a molecular weight between 400 and 750 Da, trimethylol propane, and butylamine. 4. Free radically polymerizable sulfur-containing compounds, (II), were used by Ohta et al. (5) to prepared polymers, (III), useful in optical lenses as illustrated in Eq. (1).

(1)

i. Toluene, methyl trifluoromethanesulfonate

References 1. M. Watanabe et al., U.S. Patent Application 20080058477 (March 6, 2008). 2. T.G. Rukavina et al., U.S. Patent Application 20070256597 (November 8, 2007). 3. T.G. Rukavina et al., U.S. Patent Application 20070225468 (September 27, 2007). 4. N.V. Bojkova et al., U.S. Patent Application 20070238848 (October 11, 2007). 5. K. Ohta et al., U.S. Patent Application 20070208149 (September 6, 2007).

d. Polysiloxane derivatives

Title:

Carboxylic M2Dx-Like Siloxanyl Monomers

Author: Assignee:

Derek Schorzman et al. Bausch & Lomb Incorporated (Rochester, NY)


Observations:

522

20080004413 (January 3, 2008) High Mid-2010

Preparation of polymeric siloxanes having high oxygen permeability, high water and ion transport rates, and a low modulus. Contact lenses consisting of oligomeric siloxane amines and isaconic anhydride are unreported in the patent literature. Contact lenses Membranes Soft contact lens materials represent a balance between hydrophilic monomers predisposed to form hydrogels and siloxane monomers, which are poorly soluble in hydrophilic solvents. This application has determined that the reaction of isaconic anhydride with a siloxane amine could be used to improve the solubility of the siloxane in hydrophilic solvents. This prepolymer, which was initially formed, was converted into a hydrogel and used in making soft contact lens materials. While other hydrophilic monomers such as star polymers containing ethylene glycol, crown ethers, and 2-hydroxyethyl-(meth)acrylic acid have been used as contact lenses, this application balances hydrogel oxygen permeability and water and ion transport rates with the film modulus.

Testing

523

REACTION

i. Isaconic anhydride, chloroform ii. 2,20 -Azobis(2-methylpropionitrile)

EXPERIMENTAL 1. Preparation of polymerizable end-capped siloxanyl prepolymer A stirred solution of itaconic anhydride (71.8 mmol) dissolved in 70 ml CHCl3 at 08C was treated with the dropwise addition of 3-aminopropyl terminated poly(dimethylsiloxy)silane (Mn 1000 Da; 32.36 g) dissolved in 35 ml CHCl3 over 1 hour. After an additional hour of stirring at 08C, the cooling bath was removed, the solution warmed to ambient temperature, and stirred an additional 1 hour. The product was isolated after the solution was concentrated. 2. Polymerizable of end-capped siloxanyl prepolymer The step 1 product combined with ophthalmic agents and 2,20 -azobis(2-methylpropionitrile) was clamped between two silanized glass plates and polymerized by heating to 1008C for 2 hours. The film was isolated and hydrated in deionized water for at least 4 hours and then autoclaved for 30 minutes at 1218C. The cooled films were analyzed for mechanical properties according to ASTM D-1708a and oxygen permeability.

DERIVATIVES Only the step 1 product prepared.

TESTING Testing data not supplied by the author.

524

Carboxylic M2Dx-Like Siloxanyl Monomers

NOTES 1. In other investigations by the authors (1,2) carboxylic siloxanyl monomers, (I), and carboxylic trissiloxanyl monomers, respectively, were synthesized and used in preparing contact lenses.

2. Salamone et al. (3) prepared star macromonomers, (II) and (III), having multiple methacrylate sites that when polymerized had improved oxygen permeability and water and ion transport rates and were used in contact lenses.

3. Rigid gas-permeable polymers containing perfluorocyclobutane substituents, (IV), were prepared by Schorzman et al. (4) and used in contact or intraocular lenses.

Notes

525

4. Kunzler et al. (5) prepared silicone hydrogels containing vinyl carbonate endcapped with fluorinated polysiloxanes that had an oxygen permeability of at least about 120 Barrers, a water content of at least about 20 wt%, and high modulus. 5. Copolymers having enhanced oxygen permeability and water transport properties consisting of 3-methacryloxypropyltris(trimethyl-siloxy)silane, (V), and 2-methacryloyloxymethyl-18-crown-6, (VI), were prepared by Salamone et al. (6) and used as contact lenses.

References 1. D. Schorzman et al., U.S. Patent Application 20080004414 (January 3, 2008). 2. D. Schorzman et al., U.S. Patent Application 20080000201 (January 3, 2008). 3. J.C. Salamone et al., U.S. Patent Application 20070197733 (August 23, 2007). 4. D. Schorzman et al., U.S. Patent Application 20070004867 (January 4, 2007). 5. J.F. Kunzler et al., U.S. Patent Application 20070270561 (November 22, 2007). 6. J.C. Salamone et al., U.S. Patent Application 20070049713 (March 1, 2007).

e. Poly(thiocarbonate-co-thiourethane) derivatives

Title:

Polythiourethane

Author: Assignee:

Masanori Watanabe et al. Ube Industries, Ltd. (Yamaguchi, JP)


526

20080058477 (March 6, 2008) High 2011

Synthesis of poly(thiocarbonate-co-thiourethane) derivatives having a high refractive index and Abbe number. Ongoing 3-year investigation. Eyeglasses lenses Poly(carbonate-co-urethane) derivatives consisting of 1,6-hexanediol, dimethyl carbonate, and a nonaromatic diisocyanate were previously prepared by this group and used as contact lenses. The objective of this application was to prepare poly(thiocarbonate-co-thiourethane) derivatives having both a high refractive index and high Abbe number that could be used in preparing eyeglass lenses. While the thiol-terminated polythiocarbonate component was prepared by transesterification of diphenyl carbonate with 1,6-hexanedithiol, the patent literature reports its preparation using phosgene and an alkyl dithiol. Thiocarbonate intermediates prepared were then reacted with 2,4-tolylene diisocyanate and the thiourethane isolated.

Experimental

527

REACTION

i. Diphenyl carbonate, tetrabutyl ammonium hydroxide, methanol ii. Dimethylacetamide, 2,4-tolylene diisocyanate

EXPERIMENTAL 1. Preparation of polythiocarbonate A reactor was charged with 1,6-hexanedithiol (1.10 mol), diphenyl carbonate (0.728 mol), and 10 wt% tetrabutyl ammonium hydroxide in methanol (0.331 mmol) and then heated for 2 hours at 27 kPa while refluxing at 1608C. After reducing the pressure to 6.7 kPa over 8 hours while distilling off phenol, the pressure was further reduced from 4.0 to 2.0 kPa over 3 hours to distillate off both 1,6-hexanedithiol and phenol and the product isolated. 1

H-NMR (CCl3D) d: 1.33 ppm (t, J ¼ 7.3 Hz, SH), 1.39 ppm (m, CH2), 1.62 ppm (m, CH2), 2.52 ppm (q, J ¼ 7.3 Hz, CH2SH), 2.53 ppm (q, J ¼ 7.3 Hz, CH2SH), 2.97 ppm (t, J ¼ 7.3 Hz, CH2SCO), 2.98 ppm (t, J ¼ 7.3 Hz, CH2SCO)

2. Preparation of poly(thiocarbonate-co-thiourethane) The step 1 product (70.88 mmol) was dissolved in dimethylacetamide (157 g) at 708C and then treated with 2,4-tolylene diisocyanate (71.08 mmol) and reheated for 3 hours. The mixture was then treated with additional 2,4-tolylene diisocyanate (2.24 mmol) and heated to 808C for 4 hours where the solution viscosity increased to 20.7 Pa . s at 508C. The solution was then heated to 608C and cast on a releasable glass substrate followed by heat treatment for 2 hours at 608C and for 3 hours at 1108C to obtain a film having a thickness of 200 mm.

528

Polythiourethane

DERIVATIVES TABLE 1. Physical Properties of Step 1 Products Prepared by Condensing Diphenyl Carbonate with Selected Thiols Prepared According to the Current Invention

Entry 1 2 3

Thiol 1,6-Hexanedithiol 2-Mercaptoethyl sulfide 2-Mercaptoethyl sulfide and 1,6-hexanedithiol 1,6-Hexanedithiol and 2,5,-bis(mercaptomethyl) cyclohexane

5

Mn (Da)

SH Value (meq KOH/g)

Melting Point (8C)

Crystallization Temperature (8C)

560 625 524

200.3 179.5 214.1

57.5 85.5 13.2

37.5 54.3 29.0

576

194.9

15.5

—

MATERIAL TESTING TABLE 2. Physical Properties of Poly(thiocarbonate-co-thiourethane) Step 2 Derivatives Prepared by Condensing 2,4-Tolylene Diisocyanate with Step 1 Polythiocarbonates Described in Table 1 Prepared According to the Current Invention

Entry 1 2 3

Initial Modulus of Elasticity

Tensile Strength (MPa)

Elongation 100%

300%

Refractive Index

Abbe No.

448.3 2778.6 577.4

49.28 70.91 24.98

9.85 — 10.27

45.00 — —

1.62 1.62 1.65

32.5 28.8 31.1

NOTES 1. Additional polythiocarbonate polythiol derivatives of the current invention were prepared by the authors (1) and are described. 2. In an earlier investigation by the authors (2) poly(carbonate-co-urethane) resins consisting of 1,6-hexanediol, dimethyl carbonate, and 4,40 -diphenylmethanediisocyanate were prepared and used as flexible thermoplastic polyurethane resins. 3. Optical lenses were prepared by Bojkova et al. (3) by reacting 1,1,1-tris(hydroxymethyl)propane with 4,40 -methylenebis(cyclohexyl isocyanate) and then postreacting with 2-mercaptoethyl sulfide. 4. Poly(urethane urea)polysulfide resins consisting of polycaprolactone diol, 4,40 -methylenebis(cyclohexyl isocyanate), and bis-epithiopropyl sulfide, were prepared by Bojkova et al. (4) and used as optical lenses having good refractive index and good impact resistance/strength.

Notes

References 1. M. Watanabe et al., U.S. Patent Application 20070129530 (June 7, 2007). 2. M. Watanabe et al., U.S. Patent Application 20070155933 (July 5, 2007). 3. N. Bojkova et al., U.S. Patent Application 20070142604 (June 11, 2007). 4. N. Bojkova et al., U.S. Patent Application 20060241273 (October 26, 2006).

529

f. Polyvinyl(2-hydroxyl pyrrolidine)carbazoles

Title:

Lactam Polymer Derivatives

Author: Assignee:

Stephen C. Arnold et al. Johnson & Johnson (New Brunswick, NJ)



20070290174 (December 20, 2007) Moderate Mid-2010

Synthesis of polyvinyl(2-hydroxyl-pyrrolidine)-carbazole esters for use in contact lenses and in biocompatible implants. Although polyvinyl(2-hydroxyl-pyrrolidine) derivatives have previously been prepared, the use of sodium borohydride as reducing agent to minimize loss of alcoholic content is novel. Contact lenses Polyvinylpyrrolidone has been modified in a two-step process and then used in preparing contact lenses or biocompatible implants. Initially a high-yielding method for reducing polyvinylpyrrolidone using sodium hydride to polyvinyl(2-hydroxyl-pyrrolidine) was used. In this reduction process a minimum loss of hydroxyl content was observed. Pendant carbazoles esters were then prepared and the polymer made polymerizable with crosslinking agents and fluorescent probes.

REACTION

530

Derivatives

i. Isopropanol, sodium borohydride, acetone ii. 1,4-Dioxane, 9-carbonyl chloride, methacryloyl 4-dimethylaminopyridine, hydroquinone

chloride,

531

triethylamine,

EXPERIMENTAL 1. Preparation of polyvinyl(2-hydroxyl pyrrolidine) A 4-liter beaker equipped with a mechanical stirring apparatus containing polyvinylpyrrolidone (100 g) having an Mw of 360,000 Da was dissolved in 900 ml of 2-propanol and then treated with sodium borohydride (0.45 mol) over 1 hour and then stirred at ambient temperature for 24 hours. The polymer was precipitated in 2208C acetone and then dried under vacuum. The polymer was redissolved in 2 liters of 2-propanol and the solution centrifuged at 7500 rpm for 15 minutes to remove excess borate salts. The salts were discarded and the polymer was precipitated in cold hexane/diethyl ether, 1:1, and the product isolated as a white solid having an Mn of 86,000 Da with an Mw of 332,000 Da. The hydroxyl number was determined by titration and had an equivalent weight of 1700 g/mol. 2. Preparation of polyvinyl(2-hydroxyl pyrrolidine) carbazole ester A flask was charged with the step 1 product (3.0 gm) dissolved in 300 ml of 1,4-dioxane and then treated with carbazole-9-carbonyl chloride (0.9 mmol) and methacryloyl chloride (2 mmol). Triethylamine (2 mmol), 4-dimethylaminopyridine (0.2 mmol), and hydroquinone (10 mg) were then added and the reaction mixture stirred at 608C for 6 hours. The polymer solution was filtered and the polymer precipitated in diisopropyl ether three times. The product was isolated as an off-white solid containing 0.4 mol% fluorescentgroups and 2 mol% photopolymerizable groups. DERIVATIVES

532

Lactam Polymer Derivatives

NOTES 1. Additional derivatives of the current invention were prepared by the authors (1) and are described. 2. Cooper et al. (2) prepared polyvinylpyrrolidine alcohol and then crosslinked it with pentaerythritol tetrathioglycolate for use as biocompatible implants. 3. Polymeric crosslinked polyvinylpyrrolidine alcohol was prepared using acrylic acid as described by Kulshrestha et al. (3).

References 1. S.C. Arnold et al., U.S. Patent Application 20060069235 (March 30, 2006). 2. K. Cooper et al., U.S. Patent Application 20070299206 (December 27, 2007). 3. A.S. Kulshrestha et al., U.S. Patent Application 20070299210 (December 27, 2007).

B. Optical Fibers a. Polycyclic ethers

Title: Copolymer Having Cyclic Ether Structure in Main Chain, Optical Member Comprising the Copolymer, and Method of Producing the Same Author: Assignee:

Hiroki Sasaki et al. Fujifilm Corporation (Tokyo, JP)


20080139768 (June 12, 2008) High March, 2011

Synthesis of heat- and water-resistant noncrystalline perfluorocopolymers containing 1,4-dioxane in the polymer backbone. Perfluoro-1,4-dioxane copolymers are not reported in the patent literature. Optical fibers The purpose of synthesizing the copolymer poly(chlorotrifluoroethyleneco-1,4-dioxene was to obtain a material that had a very high glass transition temperature for use in optical fibers. While 1,4-dioxene copolymers functionalized with norbornene derivatives can also be used to achieve this goal, they are prepared in multistep processes. To address this concern a single inexpensive process has been used to prepare copolymers useful in optical applications. Materials and derivatives that were prepared had high Tg’s and were heat- and water-resistant.

533

534

Copolymer Having Cyclic Ether Structure

REACTION

i. Ethyl acetate, t-butylperoxypivalate, chlorotrifluoroethylene EXPERIMENTAL 1. Preparation of poly(chlorotrifluoroethylene-co-1,4-dioxene) A 100-ml autoclave was charged with ethyl acetate (24 parts), 1,4-dioxene (20 parts), and t-butylperoxypivalate (0.3 parts) and then treated with chlorotrifluoroethylene (31 parts) and polymerized at 558C for 13 hours. The precipitated polymer was isolated and dissolved in 150 ml of tetrahydrofuran (THF) and then precipitated in methanol, the process being repeated twice. Thirty-five grams of product were isolated having a Tg of 1548C and an Mn of 28,000 Da with a refractive index of 1.459. The material was soluble in most organic solvents and formed transparent films. DERIVATIVES 1,4-Dioxene derivatives used in the step 1 copolymerization process.

Copolymers containing 1,4-dioxene derivatives are illustrated below.

Notes

535

NOTES 1. The preparation of benzodioxene, (I), is illustrated in Eq. (1).

(1)

i. Ethylene glycol, 1,2-dibromoethane, potassium carbonate ii. Carbon tetrachloride, N-bromosuccinimide, 2,20 -diazobisisobutylnitrile, sodium iodide, acetone 2. Other polymerizable noncrystalline heat- and water-resistant monomers, (II), useful in optical fibers were prepared by the authors (1,2) and are discussed.

3. Takada (3) and Nozoe et al. (4) prepared cyclic polyolefin resins and norbornene-containing polymers, (III), respectively, which were effective as optical fibers and which demonstrated adhesive properties.

References 1. H. Sasaki et al., U.S. Patent Application 20070055029 (December 27, 2007). 2. H. Sasaki et al., U.S. Patent Application 20070299204 (December 27, 2007). 3. R. Takada, U.S. Patent Application 20080113121 (March 15, 2008). 4. Y. Nozoe et al., U.S. Patent Application 20080081890 (April 3, 2008).

C. Optical Waveguides a. Deuterated polyimides

Title:

Deuterated Polyimides and Derivatives Thereof

Author: Assignee:

Kazushige Muto et al. Wako Pure Chemical Industries, Ltd. (Osaka, JP)



536

20080045724 (February 21, 2008) Moderate Mid-2010

Preparation of perdueterated polyaromatic polyimides for use as waveguides. Although the use of perdeuterated polymers as waveguides is well documented, the preparation of reagents in this investigation is novel, simple, and high yielding. Optical waveguides Direct perdeuteration of aromatics has previously been prepared under basic conditions using supercritical D2O, at elevated temperatures using D2O with hydrochloric acid with a nonactivated catalyst. In the present application these materials were prepared by refluxing o-tolidine in deuterated water. In the current application perdeuterated polyimides were prepared in a two-step process. Initially polyamic acids having molecular weights of at least 100,000 Da were prepared by reacting pyromellitic dianhydride with deuterated o-tolidine at ambient temperature followed by ring closure forming the corresponding polyimide at elevated temperatures. Perdeuterated polymers were characterized as having heat resistance, transparent, good substrate adhesion, and favorable processability.

Experimental

537

REACTION

i. Deuterated water, 10% palladium on carbon, 5% platinum on carbon ii. Pyromellitic dianhydride, dimethylacetamide iii. Heat EXPERIMENTAL 1. Preparation of deuterated o-tolidine o-Tolidine (20 g) and a mixed catalyst consisting of 10% Pd/C (4 g) and 5% Pt/C (2 g) were added to 680 ml deuterated water and then heated to 1808C for 24 hours. The mixture was then extracted with ethyl acetate followed by filtration. The filtrate was dried using MgSO4, concentrated, purified by column chromatography, and 15.4 g of product isolated having a deuteration ratio of 82%. 2. Preparation of deuterated polyamic acid The step 1 product (10 mmol) and pyromellitic dianhydride (10 mmol) were added to dimethylacetamide (41 g) and stirred at 258C for 2 hours. After standard workup 4 g of product was isolated having an Mn of 168,000 Da with a average deuteration ratio of 70%. 3. Preparation of deuterated polyimide A 10 wt% dimethylacetamide solution of the step 2 product (1 g) was cast on a glass Petri dish, heated to 2008C for 1 hour and then further heated to 3008C for an additional hour and 0.09 g of product isolated.

538

Deuterated Polyimides and Derivatives Thereof

DERIVATIVES TABLE 1. Physical Properties of d-Polyimides Prepared by Condensing Pyromellitic Dianhydride with Deuterated o-Tolidine and then Heating to 200– 30088 C Mn Precursor Polyamic Acid (Da)

Yield (%)

4

156,000

90

5

127,000

90

12

185,000

100

14

113,000

93

16

105,000

86

Entry

Structure

NOTES 1. Other methods for direct dueteration of aromatic and heterocyclic rings using platinum, rhodium, ruthenium, nickel, and cobalt catalysts are described by Ito et al. (1,2). 2. Sugano et al. (3) prepared and polymerized d8-methyl methacrylate for use as a waveguide. 3. Copolycarbonates, (I), consisting of isosorbide, bisphenol A, and diphenyl carbonate were prepared by Dhara et al. (4) and used as optical waveguides.

Notes

539

4. A photosensitive perfluoroacrylate monomer, (II), was prepared by Wang et al. (5) and used as a waveguide device.

5. Crosslinkable polymethacrylate copolymers, (III), prepared by Yamamoto (6) were effective as optical waveguide devices.

References 1. N. Ito et al., U.S. Patent Application 20070255076 (November 1, 2007) and U.S. Patent Application 20060116535 (June 1, 2006). 2. N. Ito et al., U.S. Patent Application 20060025596 (February 2, 2006). 3. Y. Sugano et al., U.S. Patent Application 20070043242 (February 22, 2007). 4. D. Dhara et al., U.S. Patent 7,138,479 (November 21, 2006). 5. F. Wang et al., U.S. Patent 7,327,925 (February 5, 2008). 6. M. Yamamoto, U.S. Patent 7,317,058 (January 8, 2008).

XVII. PHARMACEUTICALS A. Polypeptides a. Glatiramer acetate

Title:

Process for the Preparation of Copolymer

Author: Assignee:

Mani S. Iyer Momenta Pharmaceuticals, Inc. (Cambridge, MA)


Application:

Observations:

20080021192 (January 24, 2008) Low N/A

Improved method for preparing glatiramer acetate. Although there are stoichometric advantages to the current. Application similar synthetic methods have been reported in the patent literature for preparing glatiramer acetate. Pharmaceuticals Intermediate Until a method not requiring N-carboxyanhydride for the formation of polypeptides is obtained synthetic methods will remain undistinguished. In addition, the lengthy protection/deprotection reaction requirements in this application and others reported in the patent literature will remain synthetic obstacles in its preparation. Although the work in this application was comprehensive and thorough, it is unlikely to issue as a U.S. patent.


541

542

Process for the Preparation of Copolymer

REACTION

i. Dioxane, diethylamine, alanine, g-methoxyglutamate, 1-N-Boc-lysine ii. Sodium hydroxide, water, hydrobromic acid iii. Hydrobromic acid, acetic acid

EXPERIMENTAL 1. Intermediate 1 A flask charged with N-carboxyanhydrides of tyrosine (14.5 mmol), alanine (72.1 mmol), g-methoxyglutamate (22.2 mmol), and 1-N-Boc-lysine (51.5 mmol) were treated with 583.3 ml of dioxane and then stirred for 30 minutes and treated with 116 mL of diethyl amine. Within the first hour the mixture became viscous and very cloudy. After 24 hours the mixture was quenched by pouring into a second flask containing 1.58 liter of water and a white colored solid collected. The precipitate was dried by vacuum filtration and washed six times with 250 ml of water and then dried overnight and the product isolated. 2. Intermediate 2 The step 1 product (1.8 g) was charged into a 250-ml flask and then treated with 1 M aqueous sodium hydroxide and stirred for 24 hours at a temperature ranging from between 4 and 158C. After the reaction was complete, the mixture was neutralized to pH of 7 using aqueous HBr, filtered, and the product isolated. 3. Preparation of glatiramer acetate The step 2 product (22 g) was treated with 177.2 ml of 33% of HBr in acetic acid and stirred at 208C for 20 – 30 hours. The reaction mixture was then dialyzed and lyophilized to obtain the product as a white to off-white colored solid.

Notes

543

NOTES 1. In the above example R1 ¼ (Glu-Ala-Lys-Tyr)x. 2. Carubia et al. (1) developed a single-step method for preparing N-carboxyanhydrides, (I), as illustrated in Eq. (1).

(1)

i. Phosgene, tetrahydrofuran (THF), sodium hydroxide 3. A polyamino acid imaging agent of an glatiramer derivative, (II), was prepared by Grimmond et al. (2) and used in magnetic resonance imaging as a contrastenhancing agent for detecting and imaging artherosclerotic plaque,

where DOTA is 1,4,7,10-tetraazacyclododecane-N, N0 , N00 , N000 -tetraacetic acid and Gd is gadolinium. 4. An alternative method for preparing glatiramer acetate was proposed by Ray et al. (3) and entailed: a. Polymerizing a mixture of N-carboxyanhydride of L-tyrosine, N-carboxyanhydride of L-alanine, N-carboxyanhydride of a protected L-glutamate, and N-carboxyanhydride of a protected L-lysine, in a polar aprotic solvent in the presence of an initiator to form a protected polypeptide b. Mixing an acid with the protected polypeptide intermediate c. Mixing a base with the step (b) product References 1. J.M. Carubia et al., U.S. Patent Application 20060106229 (May 18, 2006). 2. B.J. Grimmond et al., U.S. Patent Application 20060104908 (May 18, 2006). 3. A.K. Ray et al., U.S. Patent Application 20080021200 (January 24, 2008).

B. Radiopharmaceuticals a. Radiolabeled haloaromatics

Title: Preparation of Radiolabeled Haloaromatics via Polymer-Bound Intermediates Author: Assignee:

Duncan H. Hunter et al. The University of Western Ontario (Ontario, CA)


544

20080085984 (April 10, 2008) High 2012

Synthesis of 3-131iodobenzylguanidinium derivatives using polymerbound intermediates. Additional 3-131iodobenzylguanidinium derivatives were previously prepared by this group in an ongoing 5-year investigation Radiopharmaceuticals Although 3-131iodobenzylguanidinium derivatives were prepared by this group in earlier investigations using other synthetic routes, the use of the reaction product of 1-(3-bromobenzyl)-2,2,5,5-tetramethyl-1,2,5azadisilolidine and polystyrene-g-2-ethyl-di-n-butylchlorostannane as the key intermediate is new and novel. When condensed with cyanamide it is converted into a guanidinium group that readily undergoes a displacement by sodium 131iodine forming 3-131iodobenzylguanidinium acetate.

Experimental

545

REACTION

i. Sodium hydroxide, CH2Cl2, triethylamine, 1,2-bis(chlorodimethyl-silyl)ethane ii. Di-n-butyidichlorostannane, dibutylstannane, 2,20 azobisisobutyronitrile, divinylbenzene, 1-octanol, methyl cellulose, water iii. THF, n-butyllithium, methanol, hydrochloric acid iv. Cyanamide, triethylamine, toluene v. Methanol, potassium dihydrogen orthophosphate, sodium 131iodide, acetic acid, hydrogen peroxide EXPERIMENTAL 1. Preparation of 1-(3-bomobenzyl)-2,2,5,5-tetramethyl-1,2,5-azadisilolidine Bromobenzylamine hydrochloride (112.3 mmol) was converted to the free base by neutralization with sodium hydroxide and extracted with CH2Cl2. Drying and solvent removal resulted in 20.3 g of a brown liquid that was used with further purification. A reactor charged with 3-bromobenzylamine (109 mmol), 150 ml of CH2Cl2, and triethylamine (217 mmol) was cooled in an ice bath and treated with 109 ml of 1 M 1,2-bis(chlorodimethylsilyl)ethane dissolved in CH2Cl2. During the addition, considerable precipitate formed. The ice bath was removed and the mixture stirred for 6.5 hours at ambient temperature. A white solid was isolated by filtration

546

Preparation of Radiolabeled Haloaromatics via Polymer-Bound Intermediates

and washed twice with 30 ml CH2Cl2. The filtrate was concentrated resulting in further precipitate formation and then treated with 100 ml hexanes and filtered and then washed twice with 20 ml hexanes. After hexane removal from the filtrate, 29.0 g of product was isolated as a light yellowish liquid, bp ¼ 93– 958C @ 0.05 mmHg. IR (cm21) (neat) 3068 (aromatic CZH stretch); 2949, 2903, 2857 (aliphatic CZH stretch); 1604, 1484 (aromatic CvC vibrations); 849 (asymmetric (SiZNZSi stretching), 784(CH3), 678 (SiZC). (aromatic CZH bending)

2. Preparation of polystyrene-g-2-ethyl-di-n-butylchlorostannane Divinylbenzene (225 mmol) and di-n-butyidichlorostannane (115 mmol) were reacted overnight under nitrogen with dibutylstannane (115 mmol) and 2,20 azobisisobutyronitrile (4.6 mmol) near or below 308C. Thereafter divinylbenzene (40.6 mmol), 2,20 azobisisobutyronitrile (7.6 mmol), 1-octanol (85.5 g), and methyl-cellulose (0.63 g) dissolved in 250 ml water were added and the mixture refluxed 8 hours in a resin kettle under nitrogen with rapid stirring. It was then cooled and water added to the resin kettle and granular polymer particles isolated. After the polymer was washed five times with 200 ml acetone, it was filtered through a coarse sinteredglass funnel and washed twice with 200 ml methanol, three times with 200 ml toluene, and three times with 200 ml THF. After drying 66.5 g of product was isolated as a white grainy solid. FTIR (cm21) 3036, 3060 (aromatic CZH); 2968, 2938, 2879, 2860 (aliphatic CZH); 1604, 1510 (aromatic CvC vibrations), 1486, 1450.2968, 2938, 2879, 2860 (aliphatic CZH); 1604, 1510 (aromatic CvC vibrations), 1486, 1450

3. Preparation of polystyrene-g-2-ethyl-di-n-butyl-3-benzylaminostannane A round-bottom flask containing the step 1 product (28.6 g) and step 2 product (76.1 mmol) were treated with 250 ml freshly distilled and dried THF and then cooled to 2788C and treated with 30.5 ml 2.5 M n-butyllithium. The initially colorless solution turned purple then brownish after 25 minutes and was stirred for 7 hours in a dry-ice –acetone bath. Thereafter the temperature slowly rose to ambient temparature over 2 hours and continued stirring for another hour. The solution was then treated with 10 ml methanol and sufficient 1 M hydrochloric acid to obtain a pH of 4 – 5 and then stirred overnight. After the upper cloudy solution was decanted and 200 ml of methanol added, the upper cloudy layer was again decanted, and this process was repeated four times. The polymer was filtered through a coarse sintered glass funnel and washed with 100 ml 50% CH2Cl2/water solution, three times with 100 ml methanol, and 50 ml 95% ethanol. After vacuum drying at ambient temperature, 30.1 g of product was isolated as a white grainy material. IR (cm21) (KBr): 3435 (broad, ZNH3 þ stretches); 3027 (aromatic CZH stretch); 2927, 2857 (aliphatic CZH stretches); 1611, 1498 (aromatic CvC vibrations)

Reaction Scoping

547

4. Preparation of polymer-supported 3-benzylguanidinium chloride Under an argon atmosphere the step 3 product (20.0 g), cyanamide (360 mmol), triethylamine (0.72 mmol), and 250 ml of toluene were added to a flask and heated to 548C for 25 hours and then filtered. The polymer was washed four times with 100 ml acetonitrile, four times with 100 ml methanol, and twice with 100 ml acetonitrile. After vacuum drying at ambient temperature, 20.7 g of product was isolated as a white grainy material. FTIR (cm21) (KBr): 3340, 3271, 3174 (NZH stretch); 3066, 3027 (aromatic CZH stretch); 2978, 2929, 2880, 2860 (aliphatic CZH stretch); 1677, 1658 (CvN stretch); 1521, 1496 (aromatic CvC vibrations); 719 (aromatic CZH bend).

5. Preparation of 3-131iodobenzylguanidinium acetate A 2-ml vial was charged with the step 4 product (0.5 mg), 300 ml of methanol, 100 ml of 0.1 M potassium dihydrogen orthophosphate, 45.5 MBq of Na131I solution, and a 100-ml aliquot of a solution prepared from 2 ml of acetic acid and 2 ml of 50% hydrogen peroxide solution diluted to 50 ml with water. The mixture was occasionally shaken for 2 hours at ambient temperature and then treated with 200 ml of 0.1 M sodium metabisulfite. After filtration through a syringe filter the filtrate was analyzed by high-pressure liquid chromatography (HPLC) and the product isolated in 97.6% yield.


REACTION SCOPING TABLE 1. Radiochemical Yield of 3-131Iodobenzylguanidinium by Reacting the Step 5 Product with Na131I and H2O2/HOAc

Entry 1 2 3 4 5

Reaction Time (min) 30 60 120 150 180

Na131I and H2O2/HOAc (mM) 50/0

20/24

37/42

50/57

60/68

30 45

30 70 80

63 90

98

0

56 85

548

Preparation of Radiolabeled Haloaromatics via Polymer-Bound Intermediates

NOTES 1. The step 2 product was prepared according to the method of Gerlack et al. (1) and is described. 2. 3-131Iodobenzylguanidinium was also prepared by this group (2) according to the following method as illustrated in Eq. (1).

(1)

i. 131Iodine, acetonitrile 3. The preparation of the step 5 product without the use of polymeric support is described by this group (3) in an earlier investigation and illustrated in Eq. (2).

(2)

i. Acetic acid, hydrogen peroxide, sodium 131iodide 4. Polymer precursors of radiolabeled 4-131iodine benzoic, (I), and amide derivatives were previously prepared by the authors (4) as illustrated in Eq. (3).

(3)

i. Methanol, acetic acid, water ii. 131Iodine, toluene iii. 3-Chloroperbenzoic acid 5. Radiolabeled 11C-acid chlorides were synthesised by Turton et al. (5) by reacting a radiolabeled carboxylic acid with a solid-phase supported chlorinating agent. In this method a solution of 11C-labeled carboxylic acid and Grignard reagent were passed through a column containing polystyrene-supported

Notes

549

acyl chloride where an exchange reaction occurred with excess polystyrenesupported acyl chloride and 11C-carboxylic acid to produce a solution of 11 C-labeled acid chloride.

References 1. U. Gerlack et al., Synthesis, 448 (1990). 2. D.H. Hunter et al., U.S. Patent 5,565,185 (October 15, 1996). 3. D.H. Hunter et al., U.S. Patent 7,273,601 (September 25, 2007). 4. D.H. Hunter et al., U.S. Patent Application 20060104900 (May 18, 2006). 5. D.R. Turton et al., U.S. Patent Application 20070287837 (December 13, 2007).

XVIII. PHOTORESISTS A. Resists a. Adamantane derivatives

Title: Adamantane Derivative, Process for Producing the Same, and Photosensitive Material for Photoresist Author: Assignee:

Naoyoshi Hatakeyama Idemitsu Kosan Co., Ltd. (Chiyoda-ku, JP)


20080009647 (January 10, 2008) High Mid-2009

Preparation of photosensitive adamantane resins for use in photoresists. This is the first example of using dimethyl sulfoxide to prepare 3methylthiomethyloxy functionalized adamantyl methacrylate. Lithography This group has used the most direct method for preparing methacrylate adamantane derivatives by begining with 3-hydroxy-1-adamantyl methacrylate. Methylthiomethylation using dimethylsulfoxide was then used to prepare analogs of the current application. Other modifications of 3-hydroxy-1-adamantyl methacrylates reported in the patent literature include chloromethylation, condensation with epoxides, and SN2 displacement reactions. All of these modifications were designed to prepare photoresist resins that could be postmodified after polymerization.


551

552

Adamantane Derivative, Process for Producing the Same, and Photosensitive Material

REACTION

i. Methylquinone, dimethylsulfoxide, acetic anhydride

EXPERIMENTAL 1. Preparation of 3-methylthiomethyloxy-1-adamantyl methacrylate A glass reactor was charged with 3-hydroxy-1-adamantyl methacrylate (220 mmol), methylquinone (1000 ppm), dimethylsulfoxide (6.3 mol), and acetic anhydride (3.2 mol) and then stirred for 48 hours at ambient temperature. The reaction was monitored by gas chromatography (GC) and was terminated after the conversion was 100%. The mixture was then transferred to a separatory funnel and treated with 500 ml diethyl ether and 200 ml of water and then shaken and separated, the process being repeated five times. Thereafter 100 ml of 10% NH4OH was added to the organic layer and then shaken and separated, this process being repeated twice. The final aqueous layer had a pH of about 6. The organic layer was dried with Na2SO4, concentrated, and the mixture distilled at 508C @ 0.1 kPa. The distillation residue was slowly poured into 300 ml methanol and a precipitate formed. The precipitated material was isolated by filtering through a 0.5-mm membrane filter and concentrated. The residue was dissolved in 200 ml hexane and then decolorized using activated carbon (5 g) and refiltered through the membrane filter. The solution was concentrated, dried under reduced pressure, and 47.09 g of product isolated having a gas-phase chromatography (GPC) purity of 99%. H-NMR (CDCl3) d 1.56 (dd, J ¼ 13.0 Hz, 32.9 Hz, 2H, h or i), 1.80 (dd, J ¼ 11.1 Hz, 37.9 Hz, 4H, f or j), 1.89 (s, 3H, a), 2.09 (dd, J ¼ 11.5 Hz, 40.5 Hz, 4H, j or f), 2.19 (s, 3H, m), 2.23 (s, 2H, g), 2.36 (br-s, 2H, i or h), 4.60 (s, 2H, l), 5.49 (t, J ¼ 1.5 Hz, 1H, b1), 6.01 (s, 1H, b2) 13 C-NMR (CDCl3) d 127 MHz): 14.29 (m), 18.23 (a), 30.90 (h), 34.93 (g or i), 40.01 (f or j), 40.45 ( j or f), 45.33 (i or g), 65.95 (l), 75.72 (k), 81.10 (e), 124.58 (b), 137.63 (c), 166.25 (d) [F11] 1

DERIVATIVES No additional monomers were prepared.

NOTES 1. Additional adamantane monomers, (I)– (IV), were previously prepared by the authors (1) for use in photolithography. Perfluoro acrylates, (V), and

Notes

553

chloromethyl derivatives, (VI), were prepared by Tanaka et al. (2,3), respectively, and used in photosensitive resins.

2. Bis(3-amino-4-hydroxyphenyl)adamantane, (VI), was prepared by Tanaka et al. (4) and used in semiconductor applications.

References 1. N. Hatakeyama et al., U.S. Patent Application 20070129532 (June 7, 2007). 2. S. Tanaka et al., U.S. Patent Application 20050131247 (June 16, 2005) and U.S. Patent 7,084,295 (August 1, 2006). 3. S. Tanaka et al., U.S. Patent Application 20060149073 (July 6, 2006). 4. S. Tanaka et al., U.S. Patent Application 20060161016 (July 20, 2006).

b. Poly(anthracene-co-4-hydroxy-styrene)

Title: Positive-Working Photoimageable Bottom Antireflective Coating Author: Assignee:

Hengpeng Wu et al. Clariant Corporation (Somerville, NJ)


554

20080038666 (February 14, 2008) Moderate Mid-2010

Antireflective copolymer coatings consisting of poly(4-hydroxylstyrene) and polymethacrylate-9-anthracene ester. Copolyester antireflective coatings containing butanetetracarboxylic acid dianhydride were previously prepared by this group. Lithography Cured coatings designed to be insoluble in an aqueous developer solution must be removed by dry etching. In cases where the material substrate is sensitive to etch damage, there is a need for an organic bottom antireflective coating that does not require dry etching and that can also provide good lithographic performance. The approach in the current application has been to use an absorbing, positive image-forming bottom antireflective coatings that can be developed in aqueous alkaline solution. Polymers soluble in alkaline medium consist of at least 50% 4-hydroxystyrene and methacrylate chromophoric esters containing methacrylic acid ester. These antireflective coatings were prepared using 4-acetoxystyrene and selected co- or termonomers and then hydrolyzed using acetic acid. Number-average molecular weights of these materials were less than 15,000 Da with refractive indexes and absorptions were less than 2.00 and 1.00, respectively.

Experimental

555

REACTION

i. 2,20 -Azobisisobutylonitrile, 4-acetoxystyrene, propyleneglycol monomethylether, tetramethylammonium, acetic acid

EXPERIMENTAL 1. Preparation of poly(hydroxystyrene-9-anthracene methacrylate) A reactor flask was charged with methacrylate ester of 9-anthracene methanol (4.2 g), 4-acetoxystyrene (13.8 g), 2,20 -azobisisobutylonitrile (0.8 g), and propyleneglycol monomethylether and then vented for 15 minutes. The reaction mixture was then heated to 708C for 5 hours and then cooled to ambient temperature and treated with 26 wt% aqueous tetramethylammonium hydroxide (7 g). The reaction temperature was then raised to 408C for 3 hours and then further raised to 608C for 8 hours. The mixture was then recooled to ambient temperature and acidified to a pH of 6 using acetic acid. The polymer was precipitated in 600 ml of methanol and the solid filtered, washed with methanol and deionized water, and dried. The precipitated polymer was redissolved in propyleneglycol monomethylether (60 g) and reprecipitated in 600 ml methanol. The solid was refiltered, rewashed, dried at 408C, and the product isolated having an Mw of 12,800 Da with an Mn of 5400 Da.

556

Positive-Working Photoimageable Bottom Antireflective Coating

DERIVATIVES

TESTING Bottom Antireflective Coating Test The absorption parameter, k, and the refractive index, n, were measured using variable angle spectrophotometric ellipsometry. The bottom antireflective coating of test solutions were spin coated onto primed silicon wafers and baked to get selected film thickness. The coated wafers were then measured using an ellipsometer to obtain k and n values. Testing Results The bottom antireflective coating solution test consisted of the step 1 product, poly(4hydroxystyrene-9-anthracenyl-methacrylate) (1.5 g), 55/45 molar ratio, respectively, oxalic acid/triethylamine (0.075 g) 1:1, triphenylsulfonium triflate (0.06 g), and Vectomerw 5015 (0.225 g) dissolved in ethyl lactate (98.5 g) and then filtered through 0.2-mm filter. At 193 nm the coating gave a refractive index and absorption of 1.59 and 0.62 nm, respectively.

NOTES 1. Antireflective polyester compositions for photoresists consisting of butanetetracarboxylic acid dianhydride and styrene glycol, (I), and tetramethylglycol uril,

Notes

557

(II), effective at 193 nm were prepared by the authors (1,2), respectively, and used in the fabrication of semiconductor devices by photolithographic techniques.

2. Polymeric barbituric acid derivatives, (III), prepared by Kishioka et al. (3) were effective as antireflective coatings for semiconductors.

3. Poly(2-acrylamido-2-methyl-1-propanesulfonic acid and isopropylhexafluoroalcohol), (IV), was prepared by Khojasteh et al. (4) and used as a top antireflective coating and barrier layer for immersion lithography.

4. Antireflective siloxane polymers coating compositions consisting of the reaction product of 2-(3,4-epoxycyclohexyl)-ethyl-trimethoxysilane, phenyltrimethoxysilane, methyltrimethoxysilane, and water were prepared by Zhang et al. (4) and used in photoresist compositions that were sensitive at 157 nm.

558

Positive-Working Photoimageable Bottom Antireflective Coating

References 1. H. Wu et al., U.S. Patent Application 20080038659 (February 14, 2008). 2. H. Wu et al., U.S. Patent Application 20060058468 (March 16, 2006). 3. T. Kishioka et al., U.S. Patent Application 20080038678 (February 14, 2008) and U.S. Patent Application 20080003524 (January 3, 2008). 4. M. Khojasteh et al., U.S. Patent Application 20080032228 (February 7, 2008). 5. R. Zhang et al., U.S. Patent Application 20070298349 (December 27, 2007).

c. Polyhexafluoro-oxacyclopentane norborane methacrylates

Title: Fluorinated Cyclic Compound, Polymerizable Fluoromonomer, Fluoropolymer, Resist Material Comprising the Same, and Method of Forming Pattern with the Same Author: Assignee:

Haruhiko Komoriya et al. Central Glass Company Ltd. (Ube-shi, JP)



20080194764 (August 14, 2008) High April, 2011

Synthesis of polynorbornane derivatives containing pendant hexafluoro oxacyclopentane. Although photoresists containing fluorinated norbornanes are reported in the patent literature, hexafluorooxacyclopentane derivatives are new and novel. Photoresist materials Norbornane derivatized with oxacyclopentane were prepared in a single step by condensation of norbornadiene and hexafluoroacetone. Florinated norbornaneols were then prepared by acid hydrolysis of perfluorooxacyclo–pentanenorbornane, which were then esterified with methyl methacrylate. Florinated norbornane polymers and copolymers were free radically prepared using 2,20 -azobisisobutyonitrile and had Mn’s 25,000 Da. While other polymerizable florinated norbornane derivatives are reported in the patent literature, the presence of pendant hexafluorooxacyclopentane is unique.

559

560

Fluorinated Cyclic Compound, Polymerizable Fluoromonomer, Fluoropolymer

REACTION

i. ii. iii. iv.

Hexafluoroacetone Sulfuric acid, water Methacrylic acid, sulfuric acid n-Butyl acetate, 2,20 -azobisisobutyonitrile

EXPERIMENTAL 1. Preparation of florinated norbornane intermediate A sealed 2000-ml autoclave charged with 2,5-norbornadiene (220 g) was treated with hexafluoroacetone (396 g) and then heated to 1308C for 16 hours. After cooling to ambient temperature the mixture was distilled under reduced pressure and 585 g of a colorless transparent liquid product isolated having a bp ¼ 638C @10 mmHg. 1

H-NMR (CDCl3) d 1.43–1.47 (m, 2H), 1.54– 1.58 (m, 1H), 1.68– 1.72 (m, 2H), 2.52 (s, 1H), 2.79 (s, 1H), 4.58 (s, 1H) 19 F-NMR (CDCl3) d 275.38 (q, 3F, J ¼ 10.9 Hz), 269.12 (q, 3F, J ¼ 10.9 Hz)

2. Preparation of florinated norbornaneol A reactor was charged with sulfuric acid (26.6 g) and then cooled in an iced water bath and treated with the dropwise addition of the step 1 product (35 g) at such a rate that the temperature never exceeded 308C. Stirring was then continued at ambient temperature for 1 hour. The mixture was then recooled in an iced water bath and treated with the dropwise addition of 100 ml water. Thereafter the mixture refluxed for 1 hour and was then recooled to ambient temperature where it separated into two phases. The lower organic phase was isolated and then washed with water and dried with MgSO4. The

Derivatives

561

solution was concentrated under reduced pressure and 24.9 g of a white crystalline product isolated having a bp ¼ 898C @ 1 mmHg. H-NMR (CDCl3) d 1.23 (d, 1H, J ¼ 14.4 Hz), 1.37 (d, 1H, J ¼ 10.8 Hz), 1.64– 1.73 (m, 1H), 2.09 (d, 1H, J ¼ 10.8 Hz), 2.22 (s, 1H), 2.51 (d, 1H, J ¼ 4.4 Hz), 3.04 (s, 1H), 4.17 (s, 1H), 4.41 (s, 1H), 4.66–4.72 (m, 1H) 19 F-NMR (CDCl3) d 275.39 (q, 3F, J ¼ 11.9 Hz), 266.93 (q, 3F, J ¼ 11.9 Hz) 1

3. Preparation of florinated norbornane methacrylate A 300-ml flask was charged with the step 2 product (10.0 g), methacrylic acid (5.0 g), and 18 M sulfuric acid (0.2 g) and then heated to 1508C for 5 hours. The solution was cooled and then treated with a saturated aqueous solution of Ca(OH)2 and extracted with diethyl ether. The ethereal solution was washed with saturated brine and then dried with MgSO4, filtered, concentrated, and 7.2 g of product isolated. 4. Preparation of florinated norbornane polymethacrylate A flask was charged with the step 3 product (10.0 g), n-butyl acetate (20.0 g), and 2,20 azobisisobutyonitrile (150 mg) and then heated to 608C for 20 hours. The reaction mixture was then cooled to ambient temperature and precipitated in 400 ml nhexane. The polymer was isolated by filtration and then vacuum dried at 508C for 18 hours and 8.9 g of a white solid product obtained.

DERIVATIVES Other norbornane monomers containing a pendent hexafluorooxacyclopentane component are illustrated below.

562


Polymeric florinated norbornane co- and terpolymers are illustrated below.

PHYSICAL PROPERTIES OF POLYMERS TABLE 1. Physical Properties of Selected Florinated Norbornane Polymers Containing a Pendant Hexafluorooxacyclopentane Component Prepared According to the Current Invention Entry Step 4 product I II III

Formed Polymer (g)

Mn (Da)

Polydispersity

8.9 7.3 8.0 4.8

33,000 20,100 26,000 32,000

1.5 1.4 1.5 1.6

TESTING Light Transmittance Selected florinated norbornane copolymers were dissolved in propylene glycol methyl acetate to form 14 wt% solutions and then treated with two weight parts of triphenylsulfonium triflate as the acid generator. These solutions were then spin coated and light transmittance measured using a 100-nm-thick film at 157 nm. Testing results are summarized in Table 2.

Notes

563

TABLE 2. Light Transparency in Vacuum Ultraviolet Wavelength Region for Selected Florinated Norbornane Polymers Entry

Light Transmission (%)

Step 4 product I II III

52 35 38 55

NOTES 1. Additional florinated norbornane derivatives, (IV), were prepared by the authors (1) in an earlier investigation and used in resist compositions.

2. Florinated norbornane ester monomers, (V), prepared by Harada et al. (2) were effective in resist compositions when processed by ArF lithography with advantages that included improved resolution, transparency, minimal line edge roughness, and etch resistance.

564


3. Maeda et al. (3) prepared florinated norbornane copolymers, (VI), which were effective in photoresist compositions.

4. Sumida et al. (4) prepared cyclic polymerizable florinated norbornane monomers, (VII), suitable for photoresist materials which had high transparency in the light wavelength region from ultraviolet to near-infrared.

References 1. H. Komoriya et al., U.S. Patent Application 20080003517 (January 3, 2008). 2. H. Harada et al., U.S. Patent Application 20070128555 (June 7, 2007). 3. K. Maeda et al., U.S. Patent Application 20070105044 (May 10, 2007). 4. S. Sumida et al., U.S. Patent Application 20060270864 (November 30, 2006).

d. Polylactones

Title: Lactone-Containing Compound, Polymer, Resist Composition, and Patterning Process Author: Assignee:

Koji Hasegawa et al. Shin-Etsu Chemical Co., Ltd.


20080026331 (January 31, 2008) High Mid-2009

Synthesis of lactone containing positive resist copolymer compositions having improved line edge roughness resolution. Ongoing investigation developing lactone containing positive resist copolymers. Lithographics This application relates to the synthesis of novel lactone containing compounds useful as intermediates in the synthesis of positive-resist copolymer compositions that are transparent to ArF excimer laser light. Polymers were designed to exhibit high resolution with minimized pattern edge roughness when processed photolithography using highenergy radiation. Lactone intermediates were prepared in two steps. Initially, methyl 6hydroxy-2-oxohexahydro-3,5-methano-2H-cyclopenta- [b]furan-7-carboxylate or an analog was esterified using 2-chloroacetic acid chloride ester and then converted into the corresponding (meth)acrylate using sodium (meth)acrylate. The combined yield for this two-step process exceeded 80%. Free radical polymerization using 2,20 -azobis-isobutyronitrile as the initiator generated polymers having averaged Mn’s of 7000 Da.

565

566

Lactone-Containing Compound, Polymer, Resist Composition, and Patterning Process

REACTION

i. 2-Chloroacetic acid chloride, tetrahydrofuran (THF) ii. N,N-Dimethylformamide, methacrylic acid, potassium carbonate iii. 3-Ethyl-3-exo-tetracyclo-[4.4.0.12,5.17,10]dodecanyl methacrylate, methyl ethyl ketone, 2,20 -azobisisobutyronitrile

EXPERIMENTAL 1. Preparation of 7-methoxycarbonyl-2-oxohexahydro-3,5-methano-2Hcyclopenta[b]furan-6-yl 2-chloroacetate A reactor was charged with methyl 6-hydroxy-2-oxohexahydro-3,5-methano-2Hcyclopenta-[b]furan-7-carboxylate (25.0 g) and 2-chloroacetic acid chloride (16.0 g) dissolved in 180 ml of THF and then cooled to below 208C and treated with the dropwise addition of pyridine (10.7 g). The solution was stirred at ambient temperature for 1 hour and then combined with 5% aqueous solution of sodium hydrogen carbonate (40 g). Following an ordinary posttreatment workup, 31.5 g of product were isolated after recrystallization from isopropyl ether. 1

H-NMR (CDCl3) d 1.69 (1H, dd), 2.07 (1H, d), 2.80 (1H, m), 2.84 (1H, dd), 3.11 (1H, dd), 3.35 (1H, t-like), 3.73 (3H, s), 4.06 (2H, s), 4.63 (1H, d), 5.34 (1H, s)

Monomer Derivatives

567

2. Preparation of 7-methoxycarbonyl-2-oxohexahydro-3,5-methano-2Hcyclopenta[b]-furan-6-yl 2-(methacryloyloxy)acetate A mixture of the step 1 product (28.9 g) and dimethylformamide (40 g) was added dropwise to a mixture of methacrylic acid (9.2 g), potassium carbonate (16.2 g), sodium iodide (3.0 g), and dimethylformamide (50 g) below 308C. The mixture was stirred at this temperature for 8 hours and then treated with 100 ml of water. Following an ordinary posttreatment workup, 28.1 g of product were isolated after recrystallization from toluene and n-hexane. FTIR (thin film) cm21 3002, 2958, 1779, 1758, 1733, 1722, 1436, 1371,1340, 1220, 1205, 1199, 1155, 1052, 1006 1 H-NMR (CDCl3) d 1.67 (1H, dd), 1.96 (3H, m), 2.01 (1H, d,), 2.80 (1H, m), 2.82 (1H, dd), 3.08 (1H, dd), 3.32 (1H, t-like), 3.72 (3H, s), 4.61 (1H, d), 4.66 (2H, s), 5.33 (1H, s), 5.66 (1H, m), 6.20 (1H, s)

3. Preparation of copolymer The step 2 product (22.1 g) and 3-ethyl-3-exo-tetracyclo-[4.4.0.12,5.17,10]dodecanyl methacrylate (17.9 g) were dissolved in methyl ethyl ketone (70.0 g) and treated with 2,20 -azobisisobutyronitrile (858 mg). This solution was then added dropwise over 4 hours to methyl ethyl ketone (23.3 g) at 808C and stirred for 2 hours. The reaction solution was then cooled to ambient temperature and treated with the dropwise addition of methanol (640 g). Precipitated solids were collected by filtration and dried in vacuum at 508C for 15 hours and 32.4 g product isolated as a white solid having an Mn of 7100 Da.

MONOMER DERIVATIVES

568


POLYMER DERIVATIVES TABLE 1. Resist Composition of Selected Copolymers and Corresponding Molecular Weights a Entry

Repeat Unit

Mw (Da)

2.1

6900

2.6

7100

2.30

6800

a

Only limited characterization data supplied by the author.

TESTING Evalution of Resolution and Line Edge Roughness Resist compositions were prepared using selected experimental agents as the base resin, an acid generator, and a quencher base in a solvent mixture consisting of 1methoxyisopropyl acetate and cyclohexanone containing 0.01 wt% surfactant. Acid generators included triphenylsulfonium nonafluorobutanesulfonate, 4-t-butoxyphenyldiphenylsulfonium nonafluorobutanesulfonate or triphenylsulfonium 1,1,3,3,3pentafluoro-2-cyclohexylcarboxypropanesulfonate while quenchers consisted of

569

Notes

tri(2-methoxymethoxyethyl)amine or 2-(2-methoxyethoxymethoxy)ethylmorpholine. Testing results provided in Table 2. TABLE 2. Resolution Properties of Lactone-Containing Polymers in Resist Compositions When Exposed to an ArF Excimer Laser a

Entry 2.1 2.6 2.30 Comparison 1 a

Postexposure Baked Temperature (8C)

Optimum Exposure (mJ/cm2)

Maximum Resolution (nm)

Mask Fidelity (nm)

Line Edge Roughness (nm)

95 105 105 105

41.0 40.0 40.0 38.0

75 70 70 80

85 84 84 78

5.4 5.0 5.1 7.8

Lower resolution values are preferred.

NOTES 1. Additional lactone containing positive-resist compositions, (I), are described by Watanabe et al. (1), the authors (2), and Funatsu et al. (3), respectively.

570


2. Perfluoroalcohol containing monomers were previously prepared by the authors (4) and Komoriya et al. (5) and used in preparing radiation-sensitive resist compositions, (II) and (III), respectively.

3. Hatakeyama et al. (6) prepared hydroxy vinylnaphthalene positive-resist compositions, (IV), that exhibited unusually high-resolution properties.

References 1. T. Watanabe et al., U.S. Patent Application 20080008962 (January 10, 2008). 2. K. Hasegawa et al., U.S. Patent Application 20070160929 (July 12, 2007). 3. K. Funatsu et al., U.S. Patent Application 20070148594 (June 28, 2007). 4. K. Hasegawa et al., U.S. Patent Application 20070179309 (August 2, 2007). 5. H. Komoriya et al., U.S. Patent Application 20080003517 (January 3, 2008). 6. J. Hatakeyama et al., U.S. Patent Application 20080020289 (January 24, 2008).

e. Poly(4-oxatricyclo[5.2.1.0.2,6]) methacrylates

Title: Ester Compounds and Their Preparation, Polymers, Resist Compositions and Patterning Process Author: Assignee:

Masaki Ohashi et al. Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)


20080008965 (January 10, 2008) Medium Early 2010

Development of photoresist esters that generate a sufficient high level of photoacid to keep irradiation minimized. A series of recent publications in this subject area were filed in the patent literature. Photoresists using the KrF or ArF excimer laser The rationale for generating monomers producing high levels of photoacids was to generate a sufficient quantity of photoacids so that irradiation exposure can be kept relatively short. To achieve this objective an ester having good photoacid decomposition properties and high thermal stability was prepared. At the filing of this application, however, three additional applications were filed by others reporting the preparation of similar esters with the identical objective.

571

572

Ester Compounds and Their Preparation, Polymers, Resist Compositions

REACTION

i. Pyridine, acetic anhydride ii. Methacrylic acid, 2,20 -methylene-bis(6-t-butyl-p-cresol) iii. Triphenylsulfonium nonafluorobutanesulfonate, tri(2-methoxymethoxyethyl)amine, 1-methoxyisopropyl acetate, cyclohexanone

EXPERIMENTAL 1. Preparation of 2-methyl-4-oxatricyclo[5.2.1.0.sup.2,6]decan-3-yl acetate A mixture of 2-methyl-4-oxatricyclo[5.2.1.0.2,6]-decan-3-ol (63 g), pyridine (42 g), and acetic anhydride (51 g) were heated to 508C for 5 hours and then concentrated. The residue was purified by distillation and 74 g product isolated as a colorless oil, bp ¼ 848C @ 40 Pa. FTIR (film): cm21 2966, 2879, 1739, 1479, 1463, 1375, 1241, 1222, 1195, 1116, 1083, 1035, 1004, 973, 952, 925, 908 1 H-NMR (CDCl3) d 1.03 (3H, s), 1.24– 1.36 (3H, m), 1.44 (1H, m), 1.52 (1H, m), 1.70 (1H, m), 2.00 (2H, m), 2.02 (3H, s), 2.20 (1H, m), 3.83 (1H, dd, J ¼ 27.1, 9.3 Hz), 3.84 (1H, dd, J ¼ 32.6, 9.3 Hz), 6.14 (1H, s) 13 C-NMR (CDCl3) d 21.22, 21.51, 21.97, 23.33, 40.35, 41.19, 47.02, 51.70, 54.14, 68.33, 100.6, 170.5

2. Preparation of 2-methyl-4-oxatricyclo[5.2.1.0.sup.2,6]decan-3-yl methacrylate The step 1 product (73 g), methacrylic acid and (150 g), and 2,20 -methylene-bis(6-tbutyl-p-cresol) (40 mg) were heated to 508C for 30 minutes and then for 18 hours at 0.20 kPa where acetic acid was collected. The product was purified by distillation at 918C @ 13 Pa and 72 g of product was isolated as a colorless liquid. FTIR (film): cm21 2964, 2879, 1722, 1637, 1461, 1380, 1321, 1295, 1170, 1157, 1112, 1079, 1006, 971, 954, 939, 917 1 H-NMR (CDCl3) d 1.07 (3H, s), 1.23– 1.37 (3H, m), 1.56 (1H, m), 1.47 (1H, m), 1.72 (1H, m), 1.91 (3H, m), 2.03 (2H, m), 2.22 (1H, m), 3.85 (1H, dd, J ¼ 28.4, 9.6 Hz), 3.86 (1H, dd, J ¼ 33.7, 9.6 Hz), 5.54 (1H, m), 6.08 (1H, m), 6.20 (1H, s) 13 C-NMR (CDCl3) d 18.32, 21.85, 22.13, 23.52, 40.50, 41.35, 47.17, 51.97, 54.58, 68.45, 100.9, 125.7, 136.8, 166.7

Derivatives

573

3. Polymerization of 2-methyl-4-oxatricyclo[5.2.1.0.sup.2,6]decan-3-yl methacrylate Resist compositions were prepared consisting of the step 2 product (80 g), the photoacid generator, triphenylsulfonium nonafluorobutanesulfonate, (4.4 g), the base, tri(2-methoxymethoxyethyl)amine (0.94 g), and solvents 1-methoxyisopropyl acetate 560 g) and cyclohexanone (240). Compositions were filtered through a Teflonw filter with a pore diameter of 0.2 mm and then heated to 508C for 20 hours and cooled. A polymer having an Mn of 7200 Da was then isolated.

DERIVATIVES Selected step 2 monomers are provided in Table 1. TABLE 1. Selected Step 2 Photoresist Esters and Corresponding Second-Step Conversions Entry

Monomer Structure

Second-Step Yield (%)

3.3

80

5.2

91

7.2

—

11.2

—

574

Ester Compounds and Their Preparation, Polymers, Resist Compositions

NOTES 1. Phororesist ester monomers, (I)– (III), prepared by Watanabe et al. (1) were used to produce homopolymers.

2. Polymerizable perfluoroesters, (IV) and (V), were prepared by Hasegawa et al. (2) and then converted into photoresist active homopolymers.

3. Kobayashi et al. (3) developed unique sulfate salts and derivatives as photoacid generators, (VI), for use in resist compositions and patterning processes.

4. Additional ester monomers convertible into homopolymers were prepared by Taniguchi et al. (4) and are discussed.

Notes

References 1. T. Watanabe et al., U.S. Patent Application 20080008962 (January 10, 2008). 2. K. Hasegawa et al., U.S. Patent Application 20070179309 (August 2, 2007). 3. K. Kobayashi et al., U.S. Patent Application 20070099113 (May 3, 2007). 4. R. Taniguchi et al., U.S. Patent Application 20080008960 (January 10, 2008).

575

f. Polyperfluoroalcohols methacrylates

Title: Polymer, Resist Protective Coating Material, and Patterning Process Author: Assignee:

Yuji Harada et al. Shin-Etsu Chemical Co., Ltd. (Tokyo, JP)



576

20080085466 (April 10, 2008) Moderate 2010

Synthesis of fluorine containing photopolymer positive-resist compositions effective as protective coats in immersion photo-lithographic processes. This is an ongoing 5-year investigation for introducing high fluorine levers into terpolymers. Photolithography The object of this application was to prepare resist protective coating materials as protective coatings on photoresist layers for use in immersion photolithography in microfabrication of semiconductor devices. These materials were used in directing ArF excimer laser radiation having a wavelength of 193 nm. To be effective the protective coating material must demonstrate enhanced water repellency and water slip and must also be effective in preventing water penetration and leaching of additives from the resist. To achieve this objective, perfluoromethacrylate co- and terpolymer ester protective coatings were free radically prepared having water sliding angles less than 138 and receding contact angles greater than 748. In all instances perfluoroacrylate monomers were prepared by transesterification of methyl methacrylate with the corresponding perfluoroalcohol.

Derivatives

577

REACTION

i. 1-(1-Cyclohexyl-2,2-ditrifluoromethyl-2-hydroxyl)ethyl methacrylate, dimethyl 2,20 -azobisisobutyrate, isopropyl alcohol EXPERIMENTAL 1. Preparation of perfluoro copolymer protective coating A flask was charged with 1-(1,1-dimethyl-2,2-ditrifluoromethyl-2-hydroxyl)ethyl methacrylate (176.46 g), 1-(1-cyclohexyl-2,2-ditrifluoromethyl-2-hydroxyl)ethyl methacrylate (23.54 g), dimethyl 2,20 -azobisisobutyrate (3.74 g), and isopropyl alcohol (100.0 g) and then cooled to 20 – 258C. In a separate flask isopropyl alcohol (50.0 g) was heated to 808C and then added dropwise to the monomer solution over 4 hours and then stirred for 3 hours at 808C. The solution was then cooled to ambient temperature and then precipitated in 4 liters of water and then isolated. The copolymer was washed four times with 600 g of isopropyl ether/hexane, 9:1, respectively, and a white solid isolated. After vacuum drying 90.1 g of the product was isolated having an Mw of 9600 Da with a polydispersity of 1.6 and consisting of 80/20 mol% 1(1,1-dimethyl-2,2-ditrifluoromethyl-2-hydroxyl) ethyl methacrylate and 1-(1-cyclohexyl-2,2-ditrifluoromethyl-2-hydroxyl)ethyl methacrylate, respectively. DERIVATIVES TABLE 1. Compositions of Perfluoro Resist Protective Copolymer Coating Monomers Useful in Immersion Photolithography Processes a Prepared According to the Current Invention Entry 2

Monomers

Monomer Ratio

Mw (Da)

79/11/10

9200

(Continued )

578

Polymer, Resist Protective Coating Material, and Patterning Process

TABLE 1. Continued Monomer Ratio

Mw (Da)

3

80/20

9500

4

80/10/10

9300

5

70/30

9100

6

80/10/10

9200

Entry

a

Monomers

All polymers had a polydispersity of 1.6.

TESTING Contact Angles Contact angle measurement were obtained on an inclination contact angle meter on wafers with the resist protective coatings kept horizontal using a 50 ml of deionized water droplet. When wafers were gradually inclined both the sliding angle and receding contact angles were obtained. Testing results are provided in Table 2.

Notes

TABLE 2.

579

Water Repellency and Water Slip Testing Results for Selected Polymers a

Entry Step 1 product Polymer 2 Polymer 3 Polymer 4 Polymer 5 Polymer 6

Refractive Index @ 193 nm

Sliding Angle (8)

Receding Contact Angle (8)

1.54 1.53 1.54 1.53 1.54 1.54

12 12 12 13 12 12

74 75 74 74 74 74

a Smaller sliding angles indicate an easier water flow on the coating while a larger receding contact angle indicates that fewer liquid droplets are left during the high-speed scan exposure.

NOTES 1. Additional step 1 resist protective coating monomer derivatives, (I) and (II), are provided by Hatakeyama et al. (1,2), respectively, and by the authors, (III), (3).

2. In an earlier investigation by this group (4) novel comonomers, (IV) and (V) were prepared that exhibited good ArF immersion lithography with liquid interposed between a projection lens and a wafer. Advantages of these resist polymers when used in immersion lithography included improved resolution, transparency, minimal line edge roughness, and etch resistance.

580

Polymer, Resist Protective Coating Material, and Patterning Process

3. Positive-resist compositions consisting of perfluoro homopolymer derivatives, (VI) and (VII), were prepared by Hatakeyama (5) which were effective as resist protective coating materials.

References 1. J. Hatakeyama et al., U.S. Patent Application 20080090172 (April 17, 2008). 2. J. Hatakeyama et al., U.S. Patent Application 20080096131 (April 24, 2008) and U.S. Patent Application 20070178407 (August 7, 2007). 3. Y. Harada et al., U.S. Patent Application 20080090173 (April 17, 2008). 4. Y. Harada et al., U.S. Patent Application 20070128555 (June 7, 2007). 5. J.J. Hatakeyama et al., U.S. Patent 20070055029 (February 19, 2008).

g. Polyperfluoro norbornanes

Title: Fluorine-Containing Cyclic Compound, Fluorine-Containing Polymer Compound, Resist Material Using Same, and Method for Forming Pattern Author: Assignee:

Haruhiko Komoriya Central Glass Company, Limited (Ube-shi, JP)



Synthesis of postive photoresists effective in the 157-nm range. This investigation reflects a 5-year effort by this group in synthesizing photoresist materials. Photolithography There has been at least a 5-year effort by this group to develop new positive photoresists containing the 1,1,1,3,3,3-hexafluoro propyl substituent effective in the 157-nm range. In this application two synthetic pathways leading to poly-merizable perfluoro (a) methacrylate or (b) norborene 1,1,1,3,3,3-hexafluoro monomers were prepared beginning with 2-acetyl-5-norbornene.

581

582

Fluorine-Containing Cyclic Compound, Fluorine-Containing Polymer Compound

Each material was free radically polymerized and provided photosensitive agents useful in photolithography using ArF excimer lasers. Other alkaline-susceptible 1,1,1,3,3,3-hexafluoroisopropy resins containing ester and acetal substituents have been prepared by this group were effective in the 157-nm range in earlier investigations.

REACTION

i. ii. iii. iv. v.

Palladium on carbon, methyl alcohol, hydrogen Sulfuric acid, hexafluoroacetone Ruthenium on carbon, diisopropyl ether, hydrogen Methacrylic anhydride, methanesulfonic acid, toluene 2,20 -Azobisisobutyronitrile, methyl ethyl ketone, n-dodecylmercaptane EXPERIMENTAL

1. Preparation of 2-acetyl-5-norbornane An autoclave was charged with 2-acetyl-5-norbornene (64 g), 5 wt% palladium on carbon (3.4 g), and 200 ml of methyl alcohol and then filled with a hydrogen atmosphere. The mixture was stirred at ambient temperature for 14 hours and then filtered through Celitew, concentrated, and 53.3 g of product isolated. 2. Preparation of the hexafluoroalcohol intermediate A 50-ml autoclave was charged with the step 1 product (50.0 g) and 18 M sulfuric acid (0.41 g) and then sealed and treated with hexafluoroacetone (73.0 g) and heated to 608C for 41 hours. The mixture was added to aqueous NaHCO3 and extracted with 200 ml diisopropyl ether. The organic layer was washed with brine, concentrated, and 92.4 g of a colorless liquid isolated as a mixture of two isomers. The isomer 1 (preferred) to isomer 2 ratio was 70:30, respectively.

Experimental

583

FTIR (cm21) (Isomers 1 and 2): 3301, 2960, 2877, 1696, 1455, 1367, 1322, 1273, 1238, 1194, 1163, 1027, 977, 719, 697, 651 1 H-NMR (CDCl3) d (Isomer 1) 1.10–1.70 (m, 7H), 1.91 (m, 1H), 2.35 (t, 1H), 2.50 (m, 2H), 2.91 (d, 1H), 3.01 (d, 1H), 7.07 (s, 1H) (Isomer 2) 1.10–1.70 (m, 7H), 1.73 (m, 1H), 2.32 (t, 1H), 2.65 (t, 1H), 2.81 (d, 1H), 2.95 (m, 1H), 3.01 (d, 1H), 7.06 (s, 1H) 19 F-NMR (CFCl3, CDCl3) d (Isomer 1) 278.82 (q, 3H), 278.65 (q, 3H) (Isomer 2) 279.07 (q, 3H), 278.49 (q, 3H) GC-MS (EI) (Isomer 1) m/e 304 (M þ ), 286 (ZH2O), 263, 237 (Isomer 2) m/e 304 (M þ ), 286 (ZH2O), 263, 237

3. Preparation of norbornane alcohol intermediate An autoclave was charged with the step 2 product mixture (91.0 g), 5 wt% ruthenium on carbon (9.1 g), and 300 ml diisopropyl ether and then sealed and heated to 1008C. Hydrogen was then introduced and the reaction continued for 14 hours at 0.7 –1.0 mPa. The mixture was then filtered by Celitew, concentrated, and 82.7 g of product isolated as white crystals after recrystallization. Analysis of the mixture indicated it consisted of four isomers (Isomers 1 – 4) in an isomeric ratio of Isomer 1 (preferred):Isomer 2:Isomer 3:Isomer 4 of 37:36:17:10, respectively. FTIR (cm21) (Isomers 1, 2, 3, and 4): 3448, 3093, 2958, 2915, 2867, 1457, 1281, 1227, 1204, 1162, 1152, 1138, 1051, 1019, 994, 930, 850, 716, 671 1 H-NMR (CDCl3) d (Isomer 1) 0.90 –2.42 (m, 14H), 3.89 (t, 1H), 6.33 (s, 1H) (Isomer 2) 0.90 –2.42 (m, 14H), 3.75 (t, 1H), 6.33 (s, 1H) (Isomer 3) 0.90 –2.42 (m, 14H), 4.00 (t, 1H), 6.29 (s, 1H) (Isomer 4) 0.90 –2.42 (m, 14H), 4.03 (t, 1H), 6.44 (s, 1H) 19 F-NMR (CFCl3, CDCl3) d (Isomer 1) 279.98 (q, 3H), 276.08 (q, 3H) (Isomer 2) 280.00 (q, 3H), 275.99 (q, 3H) (Isomer 3) 280.00 (q, 3H), 276.02 (q, 3H) (Isomer 4) 279.93 (q, 3H), 275.99 (q, 3H) GC-MS (EI) (Isomer 1) m/e 306 (Mþ), 288 (ZH2O), 260, 237 (Isomer 2) m/e 306 (Mþ), 288 (ZH2O), 260, 237 (Isomer 3) m/e 306 (Mþ), 305, 288 (ZH2O), 260, 237 (Isomer 4) m/e 306 (Mþ), 304, 288 (ZH2O), 259, 246

4. Preparation of methacrylate prepolymer A reactor was charged with the step 3 product and mixture (64.9 g), methacrylic anhydride (36.0 g), methanesulfonic acid (5.3 g), and 325 ml toluene and then heated to 908C for 3 hours. The mixture was then added to aqueous NaHCO3 and treated with 500 ml of toluene. The organic layer was isolated and then washed with brine and additized with phenothiazine (0.33 g) and then concentrated and 63.2 g of product isolated as a colorless liquid. Analysis indicated it was a mixture of four isomers in an isomeric ratio of Isomer 1 (preferred):Isomer 2:Isomer 3:Isomer 4 of 38:34:17:11, respectively. FTIR (cm21) (Isomers 1, 2, 3, and 4): 3301, 2955, 2874, 1688, 2634, 1455, 1203, 1171, 1143, 1050, 1022, 1009, 946, 815, 715, 660 1 H-NMR (CDCl3) d (Isomer 1) 0.75– 1.55 (m, 8H), 1.75 (m, 1H), 1.95 (t, 3H), 2.09–2.45 (m, 4H), 4.91 (m, 1H), 5.67 (m, 1H), 6.18 (m, 1H), 6.21 (s, 1H)

584


(Isomer 2) 0.75–1.55 (m, 8H), 1.75 (m, 1H), 1.97 (t, 3H), 2.09– 2.45 (m, 4H), 4.82 (m, 1H), 5.57 (s, 1H), 5.67 (m, 1H), 6.18 (m, 1H) (Isomer 3) 0.75–1.55 (m, 8H), 1.75 (m, 1H), 1.96 (t, 3H), 2.09– 2.45 (m, 4H), 4.98 (m, 1H), 5.67 (m, 1H), 6.05 (s, 1H), 6.18 (m, 1H) (Isomer 4) 0.75–1.55 (m, 8H), 1.75 (m, 1H), 1.96 (t, 3H), 2.09– 2.45 (m, 4H), 5.11 (m, 1H), 5.67 (m, 1H), 5.80 (s, 1H), 6.18 (m, 1H) 19 F-NMR (CFCl3, CDCl3) d (Isomer 1) 279.29 (q, 3H), 277.00 (q, 3H) (Isomer 2) 279.09 (q, 3H), 277.14 (q, 3H) (Isomer 3) 279.00 (q, 3H), 277.34 (q, 3H) (Isomer 4) 279.09 (q, 3H), 277.65 (q, 3H) GC-MS (EI) (Isomer 1) m/e 374 (Mþ), 359, 314, 305 (ZCF3), 288 (Isomer 2) m/e 374 (Mþ), 359, 333, 316, 305 (ZCF3) (Isomer 3) m/e 374 (Mþ), 356 (ZH2O), 305 (ZCF3), 288 (Isomer 4) m/e 374 (Mþ), 356 (ZH2O), 305 (ZCF3), 288

5. Preparation of norborane polymer A 300-ml round-bottom flask was charged with the step 4 product (10.0 g) mixture, 2,20 -azobisisobutyronitrile (0.18 g), 50 ml methyl ethyl ketone, and n-dodecylmercaptane (0.11 g) and then heated to 708C for 18 hours. The mixture was then precipitated in 430 ml n-hexane, dried, and 8.7 g of product isolated as a white solid having an Mn of 10,200 Da with a polydispersity of 1.64.

DERIVATIVES Polymeric derivatives with accompanying physical properties are provided in Table 1. TABLE 1. Physical Properties of Selected Step 5 Polymers Used as Resist Materials in Lithographic Applications a Entry 8

11

Repeat Unit

Mn (Da)

Polydispersity

6400

1.42

16,500

1.38

(Continued )

Notes

585


Mn (Da)

Polydispersity

12

16,600

1.37

13

14,900

1.35

a

Repeat Unit

Free radical polymerizations were performed in the presence of a chain transfer agent.

NOTES 1. Additional photoresist materials containing 1,1,1,3,3,3-hexafluoroisopropyl alcohol, (I) and (II), were prepared by Harada et al. (1) and Maeda et al. (2), respectively, and used in lithographic applications.

2. Ditrifluoromethyl oxetane derivatives, (III), prepared by Sumida Lindsey et al. (3) and containing di(trifluoro)methyl oxetane had high transparency in a wide wavelength region but were particularly suitable as photoresist materials in the vacuum ultraviolet wavelength region. Octafluoro resist materials, (IV),

586


prepared by Hatakeyama et al. (4) were used as a resist film protective coating. The film was water-insoluble, dissolvable in alkaline developer, and was immiscible with the resist film.

3. Crosslinked positive photoresist compositions, (V), were prepared by Ogata et al. (5), which exhibited a significant change in alkali solubility prior to exposure and formed fine patterns with a high level of resolution.

4. Wada et al. (6) prepared positive-resist acetal photosensitive compositions, (VI), having an Mn 3000 Da, which were used in pattern-forming processes.

Notes

References 1. Y. Harada et al., U.S. Patent Application 20070128555 (June 7, 2007). 2. K. Maeda et al., U.S. Patent Application 20070105044 (March 10, 2007). 3. S. Sumida Lindsey et al., U.S. Patent Application 20060270864 (November 30, 2006). 4. J. Hatakeyama et al., U.S. Patent Application 20070026341 (February 1, 2007). 5. T. Ogata et al., U.S. Patent Application 20070224520 (September 27, 2007). 6. K. Wada et al., U.S. Patent Application 20070148592 (June 28, 2007).

587

h. 4-Terphenyl-based oximes

Title: Oxime Derivatives and Use Thereof as Latent Acids Author: Assignee:

Hitoshi Yamato et al., Ciba Specialty Chemical Corporation (Tarrytown, NY)



588

20080085458 (April 10, 2008) Moderate 2010

Preparation of p-terphenyl-based oxime derivatives for use as latent acids activated by irradiation with actinic electromagnetic radiation and electron beams. Latent acids consisting of oxime has been an ongoing 15-year area of active research by this group. Positive photoresists There continues to be a need for reactive nonionic latent acid donors that are thermally and chemically stable after being activated by light, ultraviolet (UV) radiation, X-ray irradiation, or electron beams. A particular need exists for latent acid catalysts that have high stability and high sensitivity not only in the deep-UV range but also at longer wavelengths such as the i-line (365 nm). To address this need thermally stable p-terphenyl and fluorine oxime derivatives were prepared that are highly active against both deep-UV light and i-line. These agents were prepared in three steps entailing acylation using 7H-dodeca-fluoroheptanoyl chloride followed by conversion to the corresponding oxime and esterification using ptoluenesulfonyl chloride.

Experimental

589

REACTION

i. CH2Cl2, aluminum chloride, 7H-dodecafluoroheptanoyl chloride ii. Hydroxyl ammonium chloride, pyridine iii. CH2Cl2, triethylamine, p-toluenesulfonyl chloride EXPERIMENTAL 1. Preparation of p-terphenyl 7H-dodeca-fluoroheptanyl ketone A round-bottom flask was charged with p-terphenyl (0.27 mol) and 550 ml of CH2Cl2 and then cooled in an ice bath and treated with AlCl3 (0.30 mol) followed by the dropwise addition of 7H-dodecafluoroheptanoyl chloride (0.27 mol). The reaction mixture was stirred at ambient temperature overnight, poured into ice water, and extracted with CH2Cl2. The organic phase was washed with water, dried over MgSO4, concentrated, and the crude product used in the next step without further purification. 1

H-NMR (CDCl3). d 6.07 (tt, 1H), 7.39 (t, 1H), 7.48 (t, 2H), 7.65 (d, 2H), 7.74 (s, 4H), 7.81 (d, 2H), 8.17 (d, 2H)

2. Preparation of p-terphenyl 7H-dodeca-fluoroheptanyl oxime The step 1 product (0.22 mol) was dissolved in 650 ml of ethanol and treated with hydroxylammonium chloride (1.10 mol) and pyridine (2.64 mol) and then refluxed overnight and concentrated. The residue was poured into water and extracted with CH2Cl2 and the organic phase washed with 1 M HCl, water, brine, and dried over MgSO4. After MgSO4 was removed by filtration, 220 ml of 1 M HCl/CH3CO2H was added to the solution and then stirred overnight at ambient temperature. The reaction mixture was washed with water and brine, dried over MgSO4, and concentrated. The residue was purified by recrystallization from toluene and 65.7 g of product isolated as a yellow solid having an E conformation. 1

H-NMR (CDCl3) d 6.05 (tt, 1H), 7.35 –7.52 (m, 5H), 7.63– 7.77 (m, 8H), 8.55 (br s, 1H) F-NMR (CDCl3) d 2137.45 (d, 2F), 2129.92 (s, 2F), 2123.87 (s, 2F), 2121.64 (s, 2F), 2120.43 (s, 2F), 2110.13 (s, 2F).

19

590

Oxime Derivatives and Use Thereof as Latent Acids

3. Preparation of p-terphenyl 7H-dodeca-fluoroheptanyl p-toluene sulfonate oxime The step 2 product (3.49 mmol) was dissolved in 40 ml of CH2Cl2 and then cooled in an ice bath and treated with triethylamine (5.23 mmol) followed by the dropwise addition of p-toluenesulfonyl chloride (3.84 mmol) dissolved in 5 ml of CH2Cl2. The reaction mixture was stirred for 90 minutes at 08C and then poured into ice water and extracted with CH2Cl2. The organic phase was washed with 1 M HCl and water, dried over MgSO4, and concentrated. The residue was purified by recrystallization from 2-propanol and 1.91 g product isolated as a beige solid having an mp ¼ 138 – 1408C. 1

H-NMR (CDCl3) d 2.48 (s, 3H), 6.03 (tt, 1H), 7.36 –7.41 (m, 5H), 7.48 (t, 2H), 7.63–7.75 (m, 8H), 7.89 (d, 2H)

DERIVATIVES

Testing

591

TESTING Dose to Clear, E0 A chemically amplified positive-resist formulation was prepared by mixing the following components: 1. 50.00 parts of a resin consisting of 62 mol% of p-hydroxystyrene and 38 mol% of p-(1-ethoxyethoxy)styrene, (I), Mw ¼ 11,900 Da

2. m-Cresol Novolak resin, (II), Mw ¼ 6592 Da

3. 400 parts of propylene glycol methyl ether acetate. 4. 4.00 parts of a selected experimental photoacid generator. The resist formulation was spin-coated onto a silicone wafer on which a bottom antireflective coating had been previously applied and then soft-baked for 60 seconds at 908C on a hot plate to obtain a film thickness of 1000 nm. The resist film was then exposed to i-line radiation of 365 nm through a narrowband interference filter using a high-pressure mercury lamp and a mask aligner. Experimental samples were then baked for 60 seconds at 908C on a hot plate and developed. The dose to clear, E0, which is the dose just sufficient to completely remove the resist film after 60 seconds immersion development in 2.38% aqueous tetramethyl ammonium hydroxide, was then determined from the measured contrast curve. Testing results are provided in Table 1.

592

Oxime Derivatives and Use Thereof as Latent Acids

TABLE 1. Effectiveness of Experimental Photoacid Generators as Latent Acids a Entry

Dose to Clear (mJ/cm2)

Step 3 product 2 3 9

2.7 14.2 4.6 0.9

a Smaller dosages indicate higher sensitivity in the resist formulation.

NOTES 1. Additional p-terphenyl halogenated oxime latent acids, (III), were prepared by this group (1) in an earlier investigation and had an E0 of 1.51 mJ/cm2. Tetrahalogenated oxime derivatives, (IV), were also prepared by this group (2) having an E0 of 1.00 mJ/cm2.

Notes

593

2. Heterocyclic oxime derivatives, (V) and (VI) were also prepared by Matsumoto et al. (3,4) and had an E0 of 1.27 and 0.81 mJ/cm2, respectively.

3. A particularly photosensitive oxime sulfonate surface coating composition was prepared by this group (5) consisting of an oxime tetrabutylammonium sulfonate salt, (VI), which had an E0 of 0.17 mJ/cm2.

References 1. H. Yamato et al., U.S. Patent Application 20060246377 (November 20, 2006). 2. H. Yamato et al., U.S. Patent Application 20060068325 (March 30, 2006). 3. A. Matsumoto et al., U.S. Patent 7,026,094 (April 11, 2006). 4. A. Matsumoto et al., U.S. Patent 7,326,511 (February 5, 2008). 5. H. Yamato et al., U.S. Patent 7,244,544 (July 17, 2007).

i. Poly(ureylene methacrylates)

Title: IR Radical Polymerization-Type Photopolymer Plate Using Specific Binder Polymer Author: Assignee:

Hideo Sakurai et al. Kodak Polychrome Graphics Japan Ltd. (Tokyo, Japan)


Observations:

594

20080044765 (February 21, 2008) Moderately high 2009

Synthesis of methacrylate monomers curable by irradiation from infrared light. Six-year ongoing investigation by this group. Color filter Photoresist Free radically prepared polymethacrylate co- and terpolymers containing pendant phenolic derivatives were effective as negative-working photosensitive composition and were curable by infrared light. These materials were also resistant to polymerization inhibition because of oxygen. Infrared sensitizers included hexaarylbiimidazoles, ketoco-umar-ines, and polymethines. Although the reason is not clear, but by using organic boron compounds of the type (C6H5)3(C4H9)B N(C4H9)4 as the polymerization initiator, polymerization inhibition due to oxygen was less likely to occur. Finally, for each mole of boron derivative and infrared absorber that reacted, 2 mol of radicals were generated.

Experimental

595

REACTION

i. Dimethylacetamide, 2-aminophenol-4-sulfonamide, 2-methacryloyloxyethyl isocyanate, hydrochloric acid ii. Dimethylacetamide, allyl methacrylate, 2,20 -azobisisobutyronitrile

EXPERIMENTAL 1. Preparation of 2-(N0 -(2-hydroxy-5-sulfamoylphenyl)ureylene)ethylmethacrylate A flask was charged with dimethylacetamide (500 g) and 2-aminophenol-4-sulfonamide (1.2 mol) and then ice cooled and treated hourly with the dropwise addition of 2-methacryloyloxyethyl isocyanate (1.1 mol). Thereafter the mixture was stirred for 5 hours at ambient temperature and was then treated with 20 ml 12 M hydrochloric acid and stirred an additional 15 minutes. The solution was precipitated in 4.5 liters of water, washed with water, dried, and 356 g product isolated. 2. Preparation poly(allyl methacrylate-co-2-(N0 -(2-hydroxy-5sulfamoylphenyl)ureylene)-ethylmethacrylate) A 300-ml flask containing dimethylacetamide (100.00 g) was heated to 808C and then treated with the dropwise addition of allyl methacrylate (13.00 g), the step 1 product (7.00 g), and 2,20 -azobisisobutyronitrile (0.40 g) dissolved in dimethylacetamide (80.00 g) over 2 hours. One hour after dropwise addition was completed the mixture was treated with additional 2,20 -azobisisobutyronitrile (0.20 g) and then heated for 5 hours. The reaction solution was then precipitated into 1 liter of water, washed with water, dried, and the product isolated as a yellowish white polymer in 95% yield.

596

IR Radical Polymerization-Type Photopolymer Plate Using Specific Binder Polymer

DERIVATIVE A single derivative was prepared as illustrated below.

TESTING Quality and Storage Stability Properties A. Image Experimental agents were evaluated on dot reproducibility of the lithographic printing plate after development. Testing results are provided in Table 1 where the symbol A indicates good dot reproducibility and where reproducibility deteriorates in order of the symbols B, C, D, and E. B. Storage Stability Storage stability was evaluated by storing photosensitive lithographic printing plates at 388C and 80% relative humidity for 1 week and then evaluating development properties. These results are provided in Table 1, where the symbol A indicates excellent storage stability, and where storage stability deteriorates in order of the symbols B, C, D, and E. TABLE 1. Image Quality Testing Results of Negative Working Photosensitive Compositions after Storage Stability Testing a Samples

Comparatives

Results

1

2

3

4

5

X

Y

Image Storage stability

A A

B A

A A

A A

B A

A E

E —

a

Samples 1, 3, 4, and 5 contained the step 2 product while sample 3 contained a derivative.

Notes

597

NOTES 1. The infrared absorber, (I), and photoinitiator, (II), which were used in polymerization reactions present are illustrated below.

2. Additional negative photosensitive compositions, (I) and (II), were prepared by Hayashi et al. (1) that had excellent image quality and storage stability properties.

3. Acyclic negative working photosensitive compositions consisting of allyl methacrylate and acrylonitrile was prepared by this group (2) in an earlier investigation. A negative working photosensitive resist consisting of a polyurethane composed of 2,2-bis(hydroxymethyl)propionic acid, diethylene glycol, glycerol monoallyl ether, and 4,4-diphenylmethane diisocyanate using di-n-butyltin dilaurate as the catalyst was also prepared. In a separate investigation by Shimada et al. (3) negative working photosensitive compositions consisting of 4,4-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 2,3-dihydroxylpropyl methacrylate, 2,2-bis(hydroxymethyl)propionic acid, and polyethylene glycol using di-n-butyltin dilaurate as the initiator were also prepared. 4. Miyamoto et al. (4) used the step 2 product of the current application as a photosensitive component in a lithographic printing plate. The plate had excellent workability and good image resolution properties and could be used in the absence of laminated paper.

598

IR Radical Polymerization-Type Photopolymer Plate Using Specific Binder Polymer

5. Infrared absorbers containing a polymethine component, (III), were prepared by Iwai et al. (5) and used in photographic printing plate compositions.

6. Polymerizable compositions, (IV) and (V), used as binder polymers in planographic printing plate compositions were prepared by Sugasaki et al. (6) and showed excellent printing durability test results.

References 1. K. Hayashi et al., U.S. Patent Application 20070148582 (June 28, 2007). 2. H. Sakurai et al., U.S. Patent 7,291,438 (November 6, 2007) and U.S. Patent 6,514,657 (February 4, 2003). 3. K. Shimada et al., U.S. Patent Application 20070298351 (December 27, 2007). 4. Y. Miyamoto et al., U.S. Patent Application 20080035000 (February 14, 2008). 5. Y. Iwai et al., U.S. Patent Application 20070212643 (September 13, 2007). 6. A. Sugasaki et al., U.S. Patent Application 20070202439 (August 30, 2007).

XIX. PHOTOTHERAPY A. Oxygen Generators a. Fullerenes

Title: Novel Water-Soluble Fullerene, Process for Producing the Same and Active Oxygen Generator Containing the Fullerene Author: Assignee:

Yasuhiko Tabata et al. CMIC Company, Ltd. (Tokyo, JP)


Observations:

20080004345 (January 3, 2008) High Mid-2009

Preparation of superoxide anions generated using water-soluble fullerenes by irradiating with ultraviolet –visible (UV-Vis) light. Although water-soluble fullerences have previously been prepared, modified fullerenes have never been used as superoxide anion generators. Photodynamic therapy Sonodynamic therapy Although singlet oxygen was previously prepared by milling fullerene solids in an oxygen atmosphere, the use of these materials in the solution phase as superoxide generations by irradiating with UV-Vis light is unreported. Several synthetic aspects are worth highlighting: a. A method was developed to incorporate one polyethylene glycol chain per fullerene molecule. b. Segments of polyethylene glycol could be attached to the fullerene using L-aspartic acid as the linking agent.


599

600

Novel Water-Soluble Fullerene

c. Although superoxide anion was generated across a continuum of wavelengths from 220 to 800 nm, optimum levels were generated at 370 nm. Initial anticancer activity of superoxide anions generated from fullerenes appear favorable.

REACTION

i. Toluene, 4-toluenesulfonic acid monohydrate ii. Bromobenzene, methoxypolyethylene glycol aminopropyl, 1-hydroxybenzotriazole, N,N0 -diisopropylcarbodiimide

EXPERIMENTAL 1. Preparation of (1,2-methano[60]fullerene)-61-carboxylic acid t-Butyl ester of (1,2-methano[60]fullerene)-61-carboxylic acid was dissolved in 380 ml toluene and then treated with 4-toluenesulfonic acid monohydrate (1.17 mmol) and refluxed 10 hours. A brown precipitate formed that was filtered and sequentially washed with toluene, distilled water, and ethanol. It was dried under reduced pressure and 338 mg of product isolated as a brown crystal. FAB-MS: m/z 779 (MþH)þ H-NMR (CDCl3/d6-DMSO) d 5.15 (1H, s)

1

2. Preparation of fullerene linked to a single molecule of polyethylene glycol A solution of 14.7 ml of 0.33 mM bromobenzene containing the step 1 product was added to 2 ml of bromobenzene containing a molar equivalent of polyethylene glycol (Mn 5000 Da), which had a methoxy group at one terminus and an aminopropyl group at the other terminus. This mixture was then treated with two molar equivalents of 1-hydroxybenzotriazole and N,N 0 -diisopropylcarbodiimide and then stirred at ambient temperature for 24 hours under light shielding conditions. The reaction liquid was extracted with distilled water and then passed through a cation exchange resin column and the effluent freeze-dried. The product had a molecular weight 5800 Da and 24.4 mg of product isolated.

Notes

601

DERIVATIVES A fullerence derivative attached to polyethylene glycol having an Mn of 12,000 Da was also prepared.

TESTING Measurement of Amount of Active Oxygen Generated by Modified Fullerene. The amount of generated active superoxide anion was measured using the cytochrome method. A mixture of 200 mL containing cytochrome c was dissolved in Hanks’ balanced salt solution so that the final concentration was 50 mM. In addition, 200 mL of the experimental agent containing polyethylene glycol having an Mn 12,000 Da was added so that the final concentration in cytochrome c was 200 mM. This mixture was then irradiated with light at various wavelengths at 308C for 20 minutes. After irradiation at 550 nm the amount of oxygenated anion was 0.06 mM/minute.

NOTES 1. The step 1 reagent was prepared via a sulfonium ylide as illustrated in Eq. (1).

(1)

2. Lebovitz (1) and Hirsch et al. (2) prepared water-soluble dendritic fullerenes, which were used to oxidize reduced proteins and as drug delivery agents, respectively. 3. Tour et al. (3) dispersed single-walled nanotubes in water by functionalizing with aromatic sulfonates. 4. Senna et al. (4) observed that when powdery fullerene was milled in an oxygen atmosphere singlet oxygen was produced. This was due to the mechanical impact that caused fullerene cage distortion and the subsequent energy released from that process.

602

Novel Water-Soluble Fullerene

5. Kronholm et al. (5) prepared water-soluble fullerenes, (I), which was effective as free radical scavengers.

References 1. R. Lebovitz, U.S. Patent Application 20080020977 (January 24, 2008). 2. A. Hirsch et al., U.S. Patent Application 20080003293 (January 3, 2008). 3. J.M. Tour et al., U.S. Patent Application 20070280876 (December 6, 2007). 4. M. Senna et al., U.S. Patent Application 20070286791 (December 13, 2007). 5. D.F. Kronholm et al., U.S. Patent Application 20050245606 (November 3, 2005).

b. Pyridine-substituted porphyrins

Title: Pyridine-Substituted Porphyrin Compounds and Methods of Use Thereof Author: Assignee:

William Williams et al. Inotek Pharmaceuticals Corporation (Beverly, MA)


Observations:

20080009473 (January 10, 2008) Medium Mid-2010

Synthesis of oligomeric porphyrins for use as free radical traps in humans. The preparation of oligomers and polymerizable porphorins for use in treating radiation exposure is unreported in the patent literature. Treatment of exposure to reactive including O3, HO2, and radiationinduced injury Treatment of inflammatory lung disease Pyridinyl porphorin derivatives were prepared in two steps in moderate yields by condensing 2-pyridine carboxaldehyde with pyrrole. After encapsulating ferric chloride, they were converted into pyridinium salts by reacting with a-bromo-toluic acid. These free radical traps were effective in treating humans exposed to HO2, O3, and other radication exposure.

603

604

Pyridine-Substituted Porphyrin Compounds and Methods of Use Thereof

REACTIONS

i. Propionic acid, pyrrole, toluene ii. Ferric chloride iii. N-Methyl pyrrolidinone, a-bromo-p-toluic acid

EXPERIMENTAL 1. Preparation of pyridiyl-substituted porphyrin A 50-liter three-neck reaction flask containing 30 liters of propionic acid was mixed with a solution of pyrrole (6.0 mol) dissolved in 583 ml of toluene and 2-pyridinecarboxaldehyde (6.0 mol) dissolved in 432 ml toluene and then refluxed for 1 hour. The dark red-brown mixture was then stirred for 18 hours at ambient temperature and then filtered and concentrated. The residue was diluted with 5 ml toluene and then reconcentrated, this process being repeated three times. The residue was then added to 5 ml ethyl acetate and stirred 18 hours, filtered, diluted in CH2Cl2, and purified with flash column chromatography on silica gel using CH2Cl2/triethylamine, 98:2, respectively. Relevant fractions were combined and concentrated and a black granular solid isolated, which was diluted with 10% aqueous ammonium hydroxide, and then stirred for 2 hours and filtered. The washed solids were dried and the product isolated as a deep metallic purple solid in 2% yield.

Derivative

605

2. Preparation of iron encapsuled pyridiyl-substituted porphyrin Ferric chloride (88.89 mmol) was added to a suspension of the step 1 product (80.39 mmol) in 245 ml 1 M of hydrochloric acid and then refluxed for 18 hours. The dark-brown mixture was cooled to ambient temperature and then basified with 160 ml of sodium hydroxide. The precipitate was vacuum filtered through Whatman #50 filter paper and then washed sequentially four times with 1.5 liters of water and 1.5 liters of diethyl ether. The solid was dried for 3 days at 1008C and then dissolved in 200 ml CH2Cl2 and filtered through a 1-inch pad of Celitew. The filtrate was then concentrated and the product isolated as the monohydrate as a purple-black iridescent powdered solid in 47% yield. 3. Preparation of iron-encapsuled pyridiyl-substituted porphyrin toluic acid derivative The step 2 product (25 g) was diluted with 250 ml N-methyl pyrrolidinone and stirred to form a slurry whereupon a-bromo-p-toluic acid (20 eq) was added to the slurry and stirred at 1308C for 70 hours. The cooled mixture was slowly poured stirring 2.75 liters of chloroform and then filtered through a 3-inch pad of Celitew. A darkbrown precipitate was extracted with 1.5 liters of chloroform in a Soxhlet extractor for 55 hours. The extracted solid was removed and diluted with methanol/water, 1:1, and then filtered through a medium porosity glass fritted funnel. The filtrate was mixed with Dowexw Marathon WBA-2 weakly basic anion exchange resin and then stirred for 20 minutes and filtered. The residue was then mixed with Amberlitew IRA-402 chloride, a strongly basic anion exchange resin, and stirred for 4 hours and then filtered through a coarse porosity glass fritted funnel. The residue was rewashed with 500 ml of methanol/water, 1:1, and eluted down a 1-inch outer diameter glass column containing 340 ml of Dowexw Marathon WBA-2 resin followed by a second column containing Amberlitew IRA-402 chloride resin and the product isolated. DERIVATIVE

606

Pyridine-Substituted Porphyrin Compounds and Methods of Use Thereof

NOTES 1. The porphyrin photodynamic precursor, (I), was prepared by Love et al. (1) and oligomerized and used in photodynamic therapy.

2. Additional porphyrin pre-ologomeric derivatives, (II) and (III), were prepared by Love et al. (2) and use in photodynamic therapy.

References 1. W. Love et al., U.S. Patent Application 20070281915 (December 6, 2007). 2. W. Love et al., U.S. Patent 7,244,841 (January 17, 2007).

XX. RECORDING MATERIALS A. Anisotropic Films

Title: Trifunctional Compound, Composition and Polymer Thereof Author: Assignee:

Takashi Kato Chisso Petroleum Corporation


Application:

Observations:

20080081133 (April 3, 2008) Moderate 2011

Synthesis of anisotropic films using polymerizable aromatic acrylate esters. While the preparation of anisotropic films using acrylate intermediates is reported in the patent literature, these materials and their preparation are new. Display materials Optical materials Recording materials Liquid-crystal aromatic compounds containing polymerizable triacrylate groups were prepared and photochemically converted into optically anisotropic films using ultraviolet radiation. Monomers were prepared by transesterification of the acrylate with 2,5-dihydroxybenzaldehyde. Following oxidation with the Jones reagent, esterification with 2-hydroxyethyl acrylate was used to prepare monomeric derivatives. Polyacrylates of the current application demonstrated an improvement heat resistance, shrinkage, adhesive property, close adhesiveness, and mechanical strength.


607

608

Trifunctional Compound, Composition and Polymer Thereof

REACTION

i. 2,5-Dihydroxybenzaldehyde, 4-dimethylaminopyridine, CH2Cl2, 1,3-dichlorohexylcarbodimide ii. Chromium trioxide, sulfuric acid, acetone iii. 2,5-Dihydroxybenzaldehyde, 4-dimethylaminopyridine, CH2Cl2, 1,3-dichlorohexylcarbodimide 2-hydroxyethyl acrylate iv. Cyclopentanone, Irgacure 907, 2,7-bis(4-(6-acryloyloxyhexyloxy)-benzoyloxy)9-methylfluorene, 4’-(6-acryloyloxyhexyloxy)-4-cyanobiphenyl

EXPERIMENTAL 1. Preparation of diacrylate aldehyde intermediate A reactor was charged with a benzoic acid – acrylic ether derivative (81 mmol), 2,5dihydroxybenzaldehyde (37 mmol), 4-dimethylaminopyridine (22 mmol), and 200 ml of CH2Cl2 and then treated with the dropwise addition of 1,3-dichlorohexylcarbodimide (81 mmol) dissolved in 100 ml of CH2Cl2. After the addition the mixture was stirred at ambient temperature for 10 hours and a precipitate formed that was removed and the organic layer was washed with water, dried with MgSO4, and concentrated. The residue was purified by column chromatography, recrystallized from ethanol, and 27 mmol of product isolated.

Experimental

609

2. Preparation of diacrylate acid intermediate The step 1 product (26 mmol) and the Jones reagent (51 mmol) were added to 200 ml of acetone and stirred on an ice bath for 15 hours. Water was added and the mixture extracted with ethyl acetate. The organic phase was washed with water, dried using MgSO4, and concentrated The residue was purified by column chromatography, recrystallized from heptane, and 20 mmol of product isolated. 3. Preparation of triacrylate A mixture consisting of the step 2 product (3.4 mmol), 2-hydroxyethyl acrylate (4.3 mmol), and 4-dimethylaminopyridine (1.1 mmol) was added to 30 ml of CH2Cl2 and then treated with the dropwise addition of 1,3-dichlorohexylcarbodimide (3.9 mmol) dissolved in 10 ml CH2Cl2. After the addition was completed, the mixture was stirred at ambient temperature for 10 hours. The subsequent workup was identical to that described in step 1 and 1.6 mmol of product isolated. 1

H-NMR (CDCl3): d 1.44–1.58 (m, 8H), 1.70– 1.77 (m, 4H), 1.82– 1.88 (m, 4H), 4.05 (t, 2H), 4.06 (t, 2H), 4.19 (t, 4H), 4.22– 4.24 (m, 2H), 4.40– 4.43 (m, 2H), 5.79–5.85 (m, 3H), 6.02–6.16 (m, 3H), 6.36–6.43 (m, 3H), 6.96 (d, 2H), 6.99 (d, 2H), 7.28 (d, 1H), 7.48 (d, d, 1H), 7.91 (d, 1H), 8.15 (d, 4H)

4. Photopolymerization A 25 wt% cyclopentanone solution containing Irgacurew 907 (3 ppw), the step 3 product (60 ppw), 2,7-bis(4-(6-acryloyloxyhexyloxy)-benzoyloxy)-9-methylfluorene (20 ppw), and 40 -(6-acryloyloxyhexyloxy)-4-cyanobiphenyl (20 ppw) was prepared and then applied to a glass substrate having a polyimide alignment film. The thickness of the solution was controlled to about 12 mm by a bar coater. The glass substrate was then heated to 708C for 120 seconds to vaporize the solvent and then polymerized by irradiating with light having an intensity of 30 mW/cm2 with a central wavelength of 365 nm at ambient temperature for 30 seconds using a 250-W high-pressure mercury lamp. The orientation of the thin film was fixed and displayed A plate optical characteristics. The thin film obtained had a pencil hardness of H.

610


DERIVATIVES Set 1 and Set 2 photopolymerizable monomer compositions containing three or four components prepared and polymerized in this application are illustrated below.

Notes

611

NOTES 1. The step 3 product was also terpolymerized with other co-reagents, (I) and (II), illustrated below.

2. Additional oxirane derivatives, (III), of the current invention were previously prepared by this group (1) and are discussed.

3. Liquid-crystal compositions consisting of benzoic acid ester pairs, (IV) and (V), were prepared by Takaku et al. (2) and used in liquid-crystal material blends.

612


4. In an earlier investigation by this group (3) liquid-crystal compositions, (VI), were prepared in a mixture containing a crosslinkable monomer having liquid crystalline group side chains.

References 1. T. Kato et al., U.S. Patent Application 20070134440 (June 14, 2007). 2. K. Takaku et al., U.S. Patent Application 20070278449 (December 6, 2007). 3. T. Kato et al., U.S. Patent Application 20070007492 (January 11, 2007).

XXI. STENTS A. Cardiovascular a. Phase-separated poly(L-lactide-co-glycolides)

Title: Degradable Polymeric Implantable Medical Devices with a Continuous Phase and Discrete Phase Author: Assignee:

Yunbing Wang et al. Advanced Cardiovascular Systems, Inc. (Santa Clara, CA)


20080063685 (March 13, 2008) Moderately high 2010

Enhancing the fracture toughness of poly(L-lactide-co-glycolide) by introducing phase separation using g-caprolactone. Ongoing investigation by this group. The modifications described in this application are unreported in the literature. Biocompatible materials Polycaprolactone and poly(tetramethyl carbonate) are biodegradable polymers having high fracture toughness. While poly(L-lactide-co-glycolide) has better fracture toughness than poly(L-lactide), the fracture toughness of this composition is still lower than that desired for use in implantable stents. Two methods have previously been used to increase fracture toughness of poly(L-lactide-co-glycolide) in other investigations and include: i. Blending with a second polymer that has high fracture toughness and that is immiscible and forms discrete phases. ii. Chemically incorporating a second polymeric component having a Tg below body temperature that has good interfacial adhesion between discrete and continuous phases.


613

614

Degradable Polymeric Implantable Medical Devices

Two terpolymers of poly(L-lactide-co-glycolide) were prepared in this application that had enhanced fracture toughness by incorporating g-caprolactone by ring-opening polymerization using either stannous octoate or stannous trifluoromethane sulfonate as the catalyst. The products synthesized by this method were: i. Poly[(glycolide-co-g-caprolactone)-b-(L-lactide-co-glycolide)] ii. Poly[(L-lactide-co-glycolide)-b-(glycolide-co-caprolactone)]

REACTION

i. g-Caprolactone, dodecanol, xylene, stannous octoate ii. L-Lactide, glycolide, stannous octoate

EXPERIMENTAL 1. Preparation of poly(glycolide-co-g-caprolactone) A reaction kettle equipped with mechanical stirrer was placed in a glove box filled with nitrogen and heated to 1208C for 1 hour to remove moisture. The reactor was then charged with glycolide (200 g), g-caprolactone (200 g), 0.27 ml dodecanol, 700 ml of xylene, and 1.12 ml of stannous octoate and where glycolide component was added over four portions in 2-hour intervals. The mixture was then stirred at 1208C for 90 hours and the product isolated after dissolving in chloroform and precipitated in methanol. 2. Preparation of poly[(glycolide-co-g-caprolactone)-b-(L-lactide-co-glycolide) The entire step 1 product was treated with L-lactide (170 g), glycolide (30 g), and 48 ml stannous octoate and then heated to 1208C for 70 hours. Once the

Notes

615

polymerization was completed, the solid was dissolved in chloroform and then precipitated in 8 liters of methanol and the product dried to constant weight.

DERIVATIVES Poly[(L-lactide-co-glycolide)-b-(glycolide-co-g-caprolactone)] was also prepared as illustrated below.

NOTES 1. This group (1) previously prepared stents consisting of blends of poly(L-lactide) and poly(glycolide-co-g-caprolactone) containing phase-separated poly[(glycolide-co-g-caprolactone)-co-L-lactide], (I), as the compatibilizer. This group (2) also prepared branched polymeric stents consisting of glycerol, tetramethylene carbonate, and g-caprolactone.

2. Semicrystalline implantable poly(ester-amide) derivatives, (II), containing phenylalanine were prepared by Trollsas et al. (3) and used medical devices.

3. Gale et al. (4) prepared the polymeric reaction product of benzyl malolactonate, (III) and L-lactide using stannous octoate as catalyst and then hydrogenated it

616

Degradable Polymeric Implantable Medical Devices

into the corresponding carboxylic acid, (IV), for use as a stent with accelerated degregation properties as illustrated in Eq. (1).

(1)

i. L-Lactide, stannous octoate ii. Palladium on carbon, hydrogen

References 1. Y. Wang et al., U.S. Patent Application 20080033540 (February 7, 2008) and U.S. Patent Application 20070231365 (October 4, 2007). 2. Y. Wang et al., U.S. Patent Application 20070282435 (December 6, 2007). 3. M.O. Trollsas et al., U.S. Patent Application 20080014238 (January 17, 2008). 4. D.C. Gale et al., U.S. Patent Application 20080015686 (January 17, 2008).

XXII. SUTURES A. Adsorbable a. Poly(spiroacetals)

Title:

Dihydroxyacetone-Based Polymers

Author: Assignee:

David A Putnam et al. Cornell Research Foundation, Inc. (Ithaca, NY)



20080194786 (August 14, 2008) Very high March, 2010

Synthesis of polycarbonates, poly(acetal carbonate)s, poly(spiroacetal)s, polyesters, and polyurethanes using dihydroxyacetone. While dihydroxyacetone-based polymers have previously been prepared, the scope of dihydroxyacetone-based polymers in this application exceeds those reported in the patent literature. Biomaterials Dihydroxyacetone is not subject to facile polymerization because the monomer is in equilibrium with its dimer. Despite this limitation, it has been used as a comonomer in cationic polymerization reactions using p-toluenesulfonic acid as the reaction catalyst with either dimethylsulfoxide or dimethoxytetraoxyethylene as the reaction solvent. In this application using p-toluenesulfonic acid as the catalyst, polycarbonates, poly(acetal carbonate)s, poly(spiroacetal)s, polyesters, and polyurethanes were prepared. Dihydroxyacetone-based polymers are particularly attractive as a biomaterial agent because dihydroxyacetone is a glucose precursor in the metabolism of glucose in humans.


617

618

Dihydroxyacetone-Based Polymers

REACTION

i. Sodium carbonate, trimethylorthoformate, p-toluenesulfonic acid, methanol ii. Dimethylsulfoxide or dimethoxy-tetraoxyethylene, p-toluenesulfonic acid

EXPERIMENTAL 1. Preparation of 2,2-dimethoxy-propane-1,3-diol A reactor was charged with 2,2-dimethoxy-propane-1,3-diol (0.139 mol), trimethylorthoformate (0.278 mol), p-toluenesulfonic acid (100 mg), and 300 ml of methanol and then stirred for 12 hours. The mixture was then treated with Na2CO3 (300 mg) and stirred for an additional 12 hours and then filtered and concentrated. The solid was recrystallized in diethyl ether and 17.5 g of product isolated. 1

H-NMR (D2O) d 3.58 (s; 4H), 3.24 (s; 6H)

2. Preparation of poly(spiroacetal) The step 1 product (1 g) was diluted with 400 nl of dimethylsulfoxide or dimethoxytetraoxyethylene and then heated to 1008C and treated with p-toluenesulfonic acid (5 mg) while heating continued and the mixture was concentrated. The residue was dissolved in 1 ml CH2Cl2 and then precipitated in diethyl ether and the product isolated having an Mw ¼ 0.9– 3.0 103 Da with a polydispersity of 1.5. 1

H-NMR (CDCl3 or d6-DMSO) d 3.0–4.2 (br) C-NMR (CDCl3 or d6-DMSO) d 89–99 (ring apex carbons), 62– 64 (ring ZCH2Zgroups), 49 (terminal ZOCH3)

13

DERIVATIVES

Notes

619

NOTES 1. The step 1 reagent, 2,2-dimethoxy-propane-1,3-diol, was previously prepared by Ferroni et al. (1) and is described. 2. Dihydroxyacetone is used in cosmetic compositions for artificially tanning. Self-tanning skin formulations containing dihydroxyacetone are described by Pfluecker et al. (2).

References 1. E.L. Ferroni et al., J. Org. Chem., 64, 4943– 4945 (1999). 2. F. Pfluecker et al., U.S. Patent Application 20080166308 (July 13, 2008).

XXIII. TISSUE REPLACEMENT A. Tissue Engineering a. N-Ethyl tyrosine amide polycarbonates

Title:

N-Substituted Monomers and Polymers

Author: Assignee:

Joachim B. Kohn et al. Rutgers, The State University of New Jersey (New Brunswick, NJ)


20080187567 (August 7, 2008) High June, 2011

Synthesis of N-ethyl tyrosine amide polycarbonates to limit the hydrogen bonding to improve processibility. This is first example of designing a polymer to lower its melt viscosity for use in tissue engineering. Tissue-implantable medical devices Previously prepared N-unalkylated tyrosine amide polycarbonates had high melt or solution viscosities resulting in poor processibility. As a result of inter/intrahydrogen bonding among these polymers, higher processing temperatures were required that can degrade the polymer or any biological or pharmaceutical component attached. To address this concern, N-alkyl tyrosine polycarbonates were prepared in five steps that impede hydrogen bonding that results in lower material processing temperatures.


621

622


REACTION

i. ii. iii. iv.

Dimethyl formamide, sodium carbonate, ethyl bromide Dimethyl formamide, sodium carbonate, thiophenol Chloroiodide Dimethylaminopropyl-N0 -ethylcarbodiimide hydrochloride, boron tribromide, methylene chloride v. Methylene chloride, pyridine, phosgene

EXPERIMENTAL 1. Preparation of protected N-ethyl tyrosine intermediate A pressure vessel containing a tyrosine derivative dissolved in dimethyl formamide containing K2CO3 (2 eq) was treated with the dropwise addition of ethyl bromide (1.1 eq) and then heated to 608C for 30-minute intervals while being monitored by thin-layer chromatography (TLC). The reaction was then quenched with water and the aqueous layer extracted and then dried over Na2SO4. The mixture was filtered, concentrated, and the product isolated.

Derivatives

623

2. Preparation of N-ethyl tyrosine intermediate The entire step 1 product was redissolved in dimethyl formamide containing excess K2CO3 and then treated with thiophenol and the mixture stirred at ambient temperature while being monitored by TLC. It was then filtered, concentrated under reduced pressure, and the residue dissolved in wet methanol/tetrahydrofuran (THF) containing a catalytic amount of NaOH. After hydrolysis the mixture was concentrated and the residue dissolved in water at pH 5, extracted with ethyl acetate, and the product isolated. 3. Preparation of 3-(4-hydroxy-3,5-diiodophenyl)propanoic acid A flask containing 3-(4-hydroxyphenyl) propionic acid was treated with chloroiodide and the product isolated. 4. Preparation of 3-(4-hydroxy-3,5-diiodophenyl)propanoic acid tyrosine monomer A flask was charged with the step 2 product, the step 3 product, and N-(3-dimethylaminopropyl)-N0 -ethylcarbodiimide hydrochloride and then treated with boron tribromide dissolved in CH2Cl2 to remove the phenol protecting group. 5. Preparation of polycarbonate of 3-(4-hydroxy-3,5-diiodophenyl)propanoic acid tyrosine monomer A reactor charged with the step 4 product, 75 ml of CH2Cl2, and 10.8 ml of pyridine was treated with dropwise addition of 22.5 ml of 1.94 M solution of phosgene in toluene (43.6 mmol) at ambient temperature. The mixture stirred for 3.5 hours and was then diluted with 500 ml of CH2Cl2 and transferred into a separatory funnel. The mixture was extracted with 0.2 M hydrochloric acid, the organic phase dried over MgSO4, concentrated to 150 ml, and precipitated by pouring into 750 ml of hexane and the product isolated.

DERIVATIVES The thio-tyrosine monomer was also prepared using Lawesson’s reagent.

624


NOTES 1. The step 5 polycarbonate procedure was based on an experimental procedure provided by this group (1) in an earlier investigation. 2. Additional derivatives of the current invention are provided by the authors (2) and are discussed. 3. Functionalized nonphenolic polyaminoacids, (I), were prepared by Bezwada et al. (3) and used to prepare absorbable polymers.

4. Functionalized diphenolic monomers, (II), were prepared by Bezwada (4) and used in absorbable polymers.

References 1. J.B. Kohn et al., U.S. Patent 5,099,060 (March 24, 1992). 2. J.B. Kohn et al., U.S. Patent Application 20080187567 (August 7, 2008). 3. R.S. Bezwada et al., U.S. Patent Application 20080057127 (March 6, 2008). 4. R.S. Bezwada, U.S. Patent Application 20070135355 (June 14, 2007).

b. Glycoengineered polymers

Title: Oxylamino Group-Containing Compound and Polymer Author: Assignee:

Shinichiro Nishimura et al. Nagoya Industrial Science Research Institute (Nagoya-shi, JP)


20080097061 (April 24, 2008) Very high 2010

Method of trapping monosaccharides to the oxylamino component of a methacrylate copolymer. The patent literature does not contain material related to that described in this application. Glycoengineering biopolymers Crosslinked biopolymers effective in forming oximes with mono- and polysaccharides has been prepared that are useful as qualitative and quantitative assay tools and for the preparation of hydrogels useful in tissue augmentation. While these materials are insoluble in most organic solvents, they are soluble and stable in aqueous medium. The agent is readily prepared in four steps comprising: i. ii. iii. iv.

Amidation of maleic anhydride using ethylenedioxy-bis(ethylamine) BOC protection of the terminal amine with Boc-aminooxyacetic acid Crosslinking copolymerization with ethylene glycol dimethacrylate Removal of the BOC protecting group using trifluoroacetic acid to release the biopolymer

625

626

Oxylamino Group-Containing Compound and Polymer

REACTION

i. Ethylenedioxy-bis(ethylamine), chloroform ii. Chloroform, Boc-aminooxyacetic acid,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide iii. Chloroform, polyvinyl alcohol, ethylene glycol dimethacrylate, water, 2,20 azobisisobutyronitrile iv. Methanol, trifluoroacetic acid EXPERIMENTAL 1. Preparation of (ethylenedioxy)(ethylamine) methacrylic ethylamide A solution of methacrylic anhydride (0.03 mol) dissolved in 100 ml of chloroform was added dropwise to an ice-cooled solution of (ethylenedioxy)bis(ethylamine)

Notes

627

(0.17 mol) dissolved in 100 ml of chloroform and then stirred overnight. The mixture was concentrated and the residue purified by chromatography using silica gel with chloroform/methanol 90:10, respectively, and 5.0 g of product isolated. 2. Preparation of BOC-protected (ethylenedioxy)(ethylamine) methacrylic ethylamide A solution of the step 1 product (0.023 mol) dissolved in 100 ml of chloroform was treated with Boc-aminooxyacetic acid (1.5 eq) and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (1.5 eq) and then stirred overnight under nitrogen. The mixture was concentrated, the residue was chromatographed as described in step 1, and 4.6 g of product isolated. 3. Preparation of BOC-protected polymer A three-necked flask was charged with 25 ml of 5% aqueous polyvinyl alcohol and then treated with a mixture of the step 2 product (2.6 mmol), ethylene glycol dimethacrylate (5 mol%), and 1 ml of chloroform. The mixture was vigorously stirred while the temperature was maintained at 608C and then treated with 2,20 -azobisisobutyronitrile and polymerized at 608C for 16 hours. The polymer particles were collected by centrifugation and washed with methanol and water. 4. Preparation of polymer After washing the step 3 product with 20 ml of methanol and 10 ml of trifluoroacetic acid the mixture was stirred at 408C for 16 hours to remove the BOC protecting group. The polymer was isolated by centrifugation and washed with methanol and water and then stored in water. The average particle size of the polymer was 80 mm with a Tm of 50.98C and with no observed Tg.


NOTES 1. Although U.S. patent art does not describe polymers useful in glycoengineering, an earlier version of the current application is discussed by Smithers et al. (1). Reference 1. W. Smithers et al., WO 2004058687 (September 12, 2004).

c. Poly (o-carboxy anhydrides)

Title: Method for Controlled Polymerization of o-Carboxy Anhydrides Derived from a-Hydroxy Acids Author: Assignee:

Didier Bourissou et al. Isochem (Paris, FR) Centre National de la Recherche Scientifique (Paris, FR) Universite Paul Sabatier Toulouse III (Toulouse, FR)


Originality:

Application:

Observations:

628

20070249654 (October 25, 2007) Medium Mid-2010

Method for preparing polylactic acid derivatives through the polymerization of o-carboxy anhydrides including (1,3-dioxolane-2,4-diones) using of 4-diaminomethylpyridine as catalyst. Although polymers prepared in this application have also been reported in the patent literature, the use of 4-diaminomethyl-pyridine as the polymerization catalyst is unreported in the patent literature. Vectoring active ingredient Temporary skin substitute The novelty of this application is the use of 4-diaminomethylpyridine as reaction catalyst. Mono- and di-substituted 1,3-dioxolane-2,4-dione derivatives were converted into poly(lactic acid) by catalyzing with 4-diaminomethylpyridine at ambient temperature. In a previous investigation by this group, poly(lactic acid) and poly(d,l-lactide/glycolide) were prepared in quantitative yields using [(Me3SiNCH2CH2)2NMe]SmCl as catalyst and where products had Mn’s exceeding 34,000 Da. Scoping reactions using 4-diaminomethylpyridine as the reaction catalyst required 30 –90 minutes of reaction time for preparing polymers having Mn’s exceeding 30,000 Da. Copolymers poly(Lac)20poly-(BnGlu)10 and poly(Lac)10poly(Glu)2OAc were also prepared.

Reaction Scoping

629

REACTION

i. 4-Dimethylaminepyridine, CH2Cl2

EXPERIMENTAL 1. Preparation of poly(lactic acid) The o-carboxy anhydride of (D,L) lactic acid (4.0 mmol) was dissolved in 1.7 ml CH2Cl2 and then treated with 4-dimethylamine pyridine (0.018 mmol) at an [anhydride]/[amine] ratio of 220. The mixture was reacted for 30 minutes at 258C and then concentrated. The product was isolated in 98% yield having an Mn of 30,400 Da with a polydispersity of 1.18. Duplicate and triplicate polymerizations were also performed and Mn’s and polydispersities were found to be 30,300 and 34,900 Da with polydispersities of 1.18 and 1.13, respectively.

REACTION SCOPING The effect of different reaction solvents on the physical properties of poly(1,3-dioxolane-2,4-dione) derivatives are summarized in Table 1.

TABLE 1. Effects of Reaction Solvent on Physical Properties of Poly(1,3-dioxolane2,4-dione) Derivatives Using 4-Dimethylaminopyridine as Catalyst Entry 4 5 7

R1

R2

R3

Reaction Solvent

Mw (Da)

Mn (Da)

Hydrogen Hydrogen n-Pentyl

Phenyl Methyl Hydrogen

Hydrogen Methyl Hydrogen

CH2Cl2 Toluene 1-Pentanol

1520 7265 1675

1490 5600 1320

630

Method for Controlled Polymerization of o-Carboxy Anhydrides

NOTES 1. (5,5-Dimethyl-1,3-dioxolane-2,4-dione) derivatives, (I), were also prepared in this application as illustrated in Eq. (1). Reaction scoping of physical properties of this material as function of reaction time is provided in Table 2.

(1) i. n-Hexanol, 4-dimethylaminopyridine TABLE 2. Physical Properties of Poly(5,5-dimethyl-1,3-dioxolane-2,4-dione) Monohexyl Ester Prepared by Polymerizing 5,5-Dimethyl 1,3-Dioxolane-2,4-dione Monomer in CH2Cl2 in Presence of n-Hexyl Alcohol Using 4-Dimethylaminoaniline as Catalyst Time (min) 30 60 90 145 180

Mn

Mw

Polydispersity

Conversion (%)

4000 5300 5600 6200 6100

4500 6400 7200 7500 7200

1.14 1.21 1.30 1.21 1.17

75 92 100 — —

2. Frederic et al. (1) and Martin-Vaca et al. (2) used the strongly acidic ion exchange Amberlystw 15 resin and trifluoromethanesulphonic, respectively, to catalytically ring-open lactide and glycolide to prepare d,l-lactide oligomers. 3. Varshney et al. (3) prepared biocompatible and bioerodable poly(lactide-cosuccinic anhydride) derivatives having a Young’s modulus between about 1.5 and 3, which had enhanced surface degradation rates. 4. Copolyesters prepared by Chen et al. (4) by the bulk polymerization of N-acetyl1-caprolactone, (II), with 1,8-octanediol using tin octanate were used as a biodegradable drug delivery agents.

Notes

References 1. B. Frederic et al., U.S. Patent Application 20070185304 (August 9, 2007). 2. B. Martin-Vaca et al., U.S. Patent Application 20060149030 (January 6, 2006). 3. S.K. Varshney et al., U.S. Patent Application 20070225472 (September 27, 2007). 4. M. Chen et al., U.S. Patent Application 20070264307 (November 15, 2007).

631

d. Poly(hydroxyl-thiols)

Title:

Degradable Thiol-ene Polymers

Author: Assignee:

Christopher Bowman et al. The Regents of the University of Colorado (Denver, CO)


20080070786 (March 20, 2008) Moderate 2012


Preparation of degradable hydrogels by thiol-ene photopolymerization. Ongoing 6-year investigation by this group. Tissue engineering

Observations:

Photopolymerization of poly(vinyl alcohol)-g-thiol) with co-reagent triallyl-1,3,5-triazine-2,4,6-trione was used to prepare degradable hydrogels. The mechanistic pathway for the photopolymerization is illustrated below. This initiation can be either chemical or photolytic: RSH þ R0 CHvCH2 ! [CT complex] ! RS: þ R0 CH: CH3 light

: 0 RS: þ R0 CHvCH2 ! RSCH 2 CHR : 0 0 : RSCH 2 CHR þ RSH ! RSCH2 CH2 R þ RS : 0 RSCH2 CHR þ O2 ! RSCH(OOH)ZCH2 R0 þ RS:

These materials were designed to be used in polymeric biomaterials as cell scaffolds to provide cells with a three-dimensional support on which to grow.

632

Experimental

633

REACTION

i. ii. iii. iv. v.

Pyridine, p-toluenesulfonic acid Pyridine, dithiothreitol Pyridine, potassium thioacetate Methyl alcohol Triallyl-1,3,5-triazine-2,4,6-trione

EXPERIMENTAL 1. Preparation of poly(vinyl alcohol)-g-thiol): General procedure Poly(vinyl alcohol) was tosylated in anhydrous pyridine at 858C and then reacted with dithiothreitol potassium thioacetate and stirred overnight. The mixture was then reacted with dithiothreitol at ambient temperature to form poly(vinyl alcohol)-gdithiothreitol. It was hydrolyzed by methanolysis and the thiol macromer isolated. 2. Preparation of a crosslinked hydrogel network: General procedure The step 1 product was photopolymerized in the presence of triallyl-1,3,5-triazine2,4,6-trione in aqueous solution to provide a crosslinked hydrogel network.

634

Degradable Thiol-ene Polymers

Hydrogel degradation time was controlled by the molecular weight obtained and the crosslink density of the material.

DERIVATIVE The thiol polylactide macromer was also prepared and is illustrated below.

NOTES 1. Scoping reaction described in this application are discussed by this group (1) in an earlier investigation. 2. Addition polymers consisting of pentaerythritol triallyl ether, (I), and pentaerythritolntetrakis(3-mercaptopropionate), (II), were previously prepared by the authors (2) and used in dental restorative materials. Other photosensitive addition polymer mixtures using triallyl 1,3,5-triazine-2,4,6-trione, (III), are also described by the authors (3).

References 1. C.N. Bowman et al., U.S. Patent 7,288,608 (October 30, 2007). 2. C.N. Bowman et al., U.S. Patent Application 20070185230 (April 9, 2007). 3. C.N. Bowman et al., U.S. Patent Application 20070082966 (April 12, 2007).

XXIV. VISCOELASTIC POLYMERS A. High Viscoelastic Materials

Title: Polymeric Material Having Polyrotaxane and Process for Producing the Same Author: Assignee:

Kohzo Ito et al. The University of Tokyo (Bunkyo-ku, JP)



20080097039 (April 24, 2008) High 2010

Method of preparing viscoelastic polymers using crosslinked polyrotaxane inclusion complexes consisting of polyethylene glycol (PEG)carboxylic acid and a-cyclodextrin. The preparation and use of polyvinyl alcohol –polyethylene glycol– carboxylic acid and a-cyclodextrin polyrotaxane complexes are novel. Viscoelastic agents This application provides a material that combines properties of crosslinked polymers with enhanced stretchability or viscoelasticity. The material consists of an oxidized polyethylene oxide looped with a-cyclodextrin and containing bulky adamantly termini to prevent diffusion of the polyrotaxane inclusion complex. This material was then crosslinked with polyvinyl alcohol. Polyrotaxane derivatives were prepared in five steps summarized below: i. Conversion of polyethylene glycol diol into polyethylene dicarboxylic acid using tetramethyl-1-piperidinyloxy radical sodium hypochlorite oxidation ii. Diffusion of a-cyclodextrin into the polyethylene dicarboxylic string


635

636

Polymeric Material Having Polyrotaxane and Process for Producing the Same

iii. Locking the a-cyclodextrin into the string by amidation of the polyethylene oxide dicarboxylic acid string using adamantane amine iv. Partial O-methylation of the a-cyclodextrin hydroxyl groups using methyl iodide v. Anchoring the modified polyrotaxane to polyvinyl alcohol by crosslinking with divinyl sulfone.

REACTION

Experimental

637

i. 2,2,6,6-Tetramethyl-1-piperidinyloxy radical, sodium bromide, water, sodium hypochlorite, sodium hydroxide ii. a-Cyclodextrin, water iii. Adamantane amine, benzotriazol-1-yl-oxy-tris(dimethylamino)phosphonium hexafluorophosphate, diisopropylethylamine, dimethylformamide iv. Dimethylsulfoxide, sodium methoxide, methanol v. Polyvinyl alcohol, sodium hydroxide, divinyl sulfone.

EXPERIMENTAL 1. Preparation of polyethylene glycol carboxylic acid Polyethylene glycol (10 g; Mw 35,000 Da), 2,2,6,6-tetramethyl-1-piperidinyloxy radical (100 mg) and sodium bromide (1 g) were dissolved in 100 ml of water and then treated with 5 ml of commercially available aqueous solution of sodium hypochlorite [effective chlorine concentration: approx. 5%] and reacted at ambient temperature. Immediately after adding sodium hypochlorite, the pH of the reaction mixture rapidly decreased with the progress of the reaction and was adjusted by adding 1 M NaOH so that pH of the reaction mixture was kept between 10 and 11. The pH decrease was scarcely noticeable within 3 minutes while the reaction continued to stir for 10 minutes. The mixture was quenched with 5 ml ethanol and extracted three times with 50 ml of CH2Cl2 and then concentrated. The residue was dissolved in 250 ml of hot ethanol and then placed into a freezer at 248C overnight to precipitate out the product, which was isolated by centrifugation. Isolated PEG-carboxylic acid was then dissolvied in hot ethanol, precipitated, and centrifuged several times. It was dried in vacuum and the product isolated in 95% yield with a degree of carboxylation of 95% or more. 2. Preparation of inclusion complex of polyethylene glycol – carboxylic acid and a-cyclodextrin The step 1 product (3 g) and a-cyclodextrin (7.5 g) were dissolved in 50 ml of hot water at 708C and placed into a refrigerator at 48C overnight. The inclusion complex precipitated from solution in a pasty state and was then freeze-dried and isolated. 3. Capping of inclusion complex with adamantane amine A mixture consisting of the step 2 product and a solution of adamantane amine (0.13 g), benzotriazol-1-yl-oxy-tris(dimethylamino)phosphonium hexafluorophosphate (0.38 g), and 0.14 ml of diisopropylethylamine dissolved in 50 ml of anhydrous dimethylformamide was shaken and then placed into a refrigerator overnight. Thereafter 50 ml of methanol was added and the mixtures stirred, centrifuged, and the supernatant discarded. This solid was washed twice with 100 ml of dimethyl formamide (DMF)/methanol, 1:1, followed by washing with 100 ml of methanol and

638

Polymeric Material Having Polyrotaxane and Process for Producing the Same

centrifuging twice. The precipitate was dried in vacuum and then dissolved in 50 ml of dimethylsulfoxide, precipitated in 700 ml of water, collected by centrifugation, and 9 g of product isolated having a 22% degree of inclusion. 4. O-Methylation of polyethylene glycol a-cyclodextrin polyrotaxane The step 3 product (5.0 g) was dissolved in 100 ml of anhydrous dimethylsulfoxide and then treated with 28% solution of sodium methoxide in methanol (3.8 g) followed by removing methanol under a reduced vacuum. This mixture was then treated with methyl iodide (2.8 g), stirred for 24 hours, and then diluted with purified water to 150 ml total volume. The diluted mixture was then dialyzed for 48 hours with a dialysis tube in flowing tap water. It was further dialyzed for 12 hours in 1000 ml of purified water four times and then freeze-dried to give the methylated polyrotaxane in which 30% of hydroxyl groups were O-methylated and 4.6 g of product isolated. 1

H-NMR (CDCl3) d 3.0–4.2 (m, 18.4H), 4.8– 5.2 (m, 3.8H), 5.3–6.0 (m, 1H)

5. Preparation of crosslinked polyethylene glycol a-cyclodextrin polyrotaxane Polyvinyl alcohol having a 2000 degree of polymerization was dissolved in aqueous 0.03 M NaOH to prepare 1.0 ml of 5 wt% solution and then treated with the step 4 product (10 mg) and 10 ml of divinyl sulfone. After remaining at 258C for 20 hours, a gelated body was isolated having a weight ratio of polyvinyl alcohol to the step 4 product of 5:1, respectively. 6. Comparative example for preparing crosslinked polyethylene glycol a-cyclodextrin polyrotaxane Using the step 3 product and the step 5 crosslinking procedure at 58C and stirring for 20 hours generated a gelated material.

DERIVATIVES The hydroxypropylated step 4 product was also prepared using polypropylene oxide.

TESTING Viscoelasticity Testing results for the extension maximum stress stiffness test for gelated bodies for the step 5 product and comparative are provided in Table 1.

Notes

TABLE 1.

639

Viscoelastic Properties of Gelated Polyrotaxane Solidsa


Extension Ratio (%)

Maximum Stress (kPa)

Stiffness (kPa)

320 149

35 25

12 20

a A higher degree of divinylsulfone crosslinking was observed in the comparative sample because of the absence of O-methylation of a-cyclodextrin polyrotaxane.

NOTES 1. Nakajima et al. (1) prepared liquid crystalline polyrotaxane derivatives containing the mesogenic group 4-cyano-40 -hydroxybiphenyl attached to the a-cyclodextrin component of linear polyethylene glycol containing an a-cyclodextrin inclusion complex with an adamantane termini. 2. Cyanuric chloride was used by Okumura et al. (2) to crosslink the a-cyclodextrin portion of linear polyethylene glycol polyrotaxane containing an ethylene amine termini. References 1. T. Nakajima et al., U.S. Patent Application 20070205395 (September 6, 2007). 2. Y. Okumura et al., U.S. Patent 6,828,378 (December 7, 2004).

CONTRIBUTORS

Academic Contributors Carnegie Mellon University (Pittsburgh, PA, USA) Case Western Reserve University (Cleveland, OH, USA) Cornell Research Foundation, Inc. (Ithaca, NY, USA) Florida State University Research Foundation, Inc. (Tallahassee, FL, USA) Gwangju Institute of Science and Technology (Gwangju, KR) Mayo Foundation for Medical Education and Research (Rochester, MN, USA) Nagoya Industrial Science Research Institute (Nagoya-shi, JP) Rutgers, The State University of New Jersey (New Brunswick, NJ, USA) The Cleveland Clinic Foundation (Cleveland, OH, USA) The Regents of the University of California (Oakland, CA, USA) The Regents of the University of Colorado (Denver, CO, USA) The University of Tokyo (Bunkyo-ku, JP) The University of Western Ontario (Ontario, CA) University of Utah Research Foundation (Salt Lake City, UT, USA) Universiteit Gent (Gent, BE) Universite de Montreal (Montreal, CA) University of Hull (Hull, GB) Universite Paul Sabatier Toulouse III (Toulouse, FR) University of Virginia (Blacksburg, VA, USA) William Marsh Rice University (Houston, TX, USA)

Government Contributors Agency for Science, Technology, and Research (Singapore, SG) Centre National De La Recherche Scientifique (Paris, FR) Government of the United States of America as Represented by the Secretary, Department of Health (Rockville, MD, USA) Japan Science and Technology Agency (Saitama, JP) Los Alamos National Laboratory (Los Alamos, NM, USA) United States of America as Represented by the Administrator of the National Aeronautics and Space Administration (Washington, DC, USA) U.S. Government as Represented by Secretary of the Navy (Washington, DC, USA)


641

642

Contributors

Industrial Contributors Adeka Corporation (Tokyo, JP) Advanced Cardiovascular Systems, Inc. (Santa Clara, CA, USA) Afton Chemical Corporation (Richmond, VA, USA) Air Products and Chemicals, Inc. (Allentown, PA, USA) Asahi Glass Company (Chiyoda-Ku, JP) Basell, Inc. (Elkton, MD, USA) Basell Polyolefine GmbH (Wesseling, DE) BASF Aktiengesellschaft (Ludwigshafen, DE) Bausch & Lomb Incorporated (Rochester, NY, USA) Bayer Material Scientific LLC (Pittsburgh, PA, USA) Bridgestone Corporation (Tokyo, JP) Cambridge Display Technology, Limited (GB) Canon Kabushiki Kaisha (Tokyo, JP) CellTran Limited (Sheffield, GB) Cell Therapeutics, Inc. (Seattle, WA, USA) Covion Organic Semiconductors GmbH (Wiesbaden, DE) Eastman Kodak Company (Rochester, NY, USA) Central Glass Company Limited (Ube-shi, JP) Chemtura Corporation (Middlebury, CT, USA) China Petroleum and Chemical Corporation (Beijing, CN) Ciba Geigy Corporation (Tarrytown, NY, USA) CIBA Specialty Chemicals Corporation (Tarrytown, NY, USA) Celanese Ventures GmbH (Frankfurt am Main, DE) Chisso Corporation (Osaka, JP) Chisso Petrochemical Corporation (Osaka, JP) Clariant Corporation (Somerville, NJ, USA) CMIC Company, Ltd. (Tokyo, JP) Degussa AG (Duesseldorf, DE) Degussa AG (Hanau-Wolfgang, DE) Dow Chemical Company (Philadelphia, PA, USA) Dow Global Technologies, Inc. (Midland, MI, USA) Eastman Chemical Company (Kingsport, TN, USA) E I DuPont De Nemours and Company (Wilmington, DE, USA) Fujifilm Corporation (Tokyo, JP) General Electric Company, Global Research (Niskayuna, NY, USA) Georgia-Pacific Resins, Inc. (Atlanta, GA, USA) Gkss-Forschungszentrum Geesthacht GMBH (Geesthacht, DE) Great Eastern Resins Industrial Company, Ltd. (Taichung City, TW) Hewlett Packard Company (Fort Collins, CO, USA) Hitachi Chemical Company, Ltd. (Tokyo, JP) Hitachi, Ltd. (Tokyo, JP) Hyosung Corporation (Anyang-si, KR) Hyperion Catalysis International (Cambridge, MA, USA)

Contributors

Idemitsu Kosan Co., Ltd. (Chiyoda-ku, JP) Inotek Pharmaceuticals Corporation (Beverly, MA, USA) Isis Innovation Limited (Oxford, GB) Isochem (Paris, FR) Ivoclar Vivadent AG (Schaan, LI) Johnson & Johnson (New Brunswick, NJ, USA) JSR Corporation (Tokyo, JP) Kaneka Corporation (Osaka, JP) Kansai Paint Co., Ltd. (Amagasaki-shi, JP) Kodak Polychrome Graphics Japan Ltd. (Tokyo, JP) Konarka Technologies, Inc. (Lowell, MA, USA) Kureha Corporation (Tokyo, JP) Labopharm, Inc. (Quebec, CA) Lintec Corporation (Tokyo, JP) L’Oreal S.A. (Paris, FR) Lyondell Chemical Company (Newtown Square, PA, USA) 3M Innovative Properties Company (St. Paul, MN, USA) MediVas, LLC (San Diego, CA, USA) Medtronic Vascular, Inc. (Santa Rosa, CA, USA) Merck Patent Gesellschaft Mit Beschrankter Haftung (Darmstadt, DE) Mitsubishi Rayon Co., Ltd. (Tokyo, JP) Momenta Pharmaceuticals, Inc. (Cambridge, MA, USA) NEC Corporation (Tokyo, JP) Nektar Therapeutics (San Carlos, CA, USA) Norsk Hydro ASA (Oslo, NO) Omeros Corporation (Seattle, WA, USA) Ricoh Company, Ltd. (Yokohama, JP) Samsung Electronics Co., Ltd. (Seoul, KR) Samsung Electronics Co., Ltd. (Suwon-si, KR) Samsung SDI Co., Ltd. (Suwon-si, KR) Shin-Etsu Chemical Co., Ltd. (Tokyo, JP) Showa Denko K.K. (Tokyo, JP) Straumann Holding AG (Basel, CH) Sumitomo Chemical Company, Ltd. (Tokyo, JP) Sumitomo Chemical Company, Ltd. (Tsukuba-shi, JP) TESA AG (Hamburg, DE) Tokyo Ohka Kogyo Co., Ltd. (Kawasaki-Shi, JP) Toray Industries, Inc. (Tokyo, JP) Toyo Seikan Kaisha, Ltd. (Tokyo, JP) Ube Industries, Ltd. (Yamaguchi, JP) Union Carbide Chemicals and Plastic Technology (Midland, MI, USA) Wako Pure Chemical Industries, Ltd. (Osaka, JP) Xerox Corporation (Rochester, NY, USA)

643

INDEX

Adhesives Pressure sensitive Heat-resistant poly(silsesquioxane-g-methyl methacrylate)s, 59 Poly(acrylate-co-2-ethylhexyl acrylate) for bonding to low-energy surfaces, 64 Surface adhesives Plasma treatment of polyimides to improve surface adhesion, 75 Sulfur-modified Novolak resins exhibiting strong adhesion to gold surfaces, 67 Thermally stable Polyvinyl alcohol crosslinked with bis(allyloxy)methane, 77 Catalysts Decyclization of cyclic poly(diethyleneglycol terephthalate) 1,3-di-1-adamantyl-imidazole-2-ylidene, 56 Oligomeric uretonimine modified polyisocyanates 3-Methyl-1-phenyl-3-phospholene-1-oxide, 281 Organometallic catalysts Aluminum phosphate/Group VI metal amide catalysts for oligomerization of ethylene, 288 Epoxidation of propylene using palladium/titanium zeolite-1, 285 Cosmetics Topical Poly(isobornyl methacrylate-co-isobornyl acrylate)-b-methacryloxypropyltris(trimethylsiloxy)silane, 81 Crystalline polymers Liquid Crystal Displays Polymethacrytate-g-cholesterol which reflect light of various wavelengths, 85 t-Isosorbide ester diacrylates exhibiting fixed cholesteric optical properties, 91

Polyacetylene derivatives having a helical rigid-rod shape which exhibit cholesteric or nematic crystal phase behavior, 96 Poly(trans-di-hexyl-1,4-phenylene) exhibiting optical anisotropic behavior, 100 Thieno[3,2-b]thiophene monomers, 105 Dyes Jet-printer ink Maleimide polymethacrylates containing grafted N-(2,4-dinitrophenyl)-1,4phenylenediamine, 111 Oxime ester photopolymerization initiators that do not cause film discoloration, 95 Electrically active polymers Conducting polymers Poly(1H-thieno[3,4-d]imidazol-2(3H)-one), 126 Electrodes Chiral polymers consisting of helical polyaniline prepared using chiral dopant acids, 139 Hydroxycarboxylation of nanotubes using ozone, 129 Oligomeric N-vinylpyrrolidinone-covinylferrocenes crosslinked with polymethylmethacrylate, 132 C60 fullerene perfluoro sulfonic acids as a Nafionw replacement, 136 Poly(1,4-pyridinium) bromide soluble in DMSO, 142 Photovoltaic cells Copolymers containing cyclopentadithiazole and dithiophene derivatives, 155 Crosslinked poly(porphyrin-co-thiophene)s, 159 Liquid crystalline IPN’s using photocrosslinkable mesogenic monomers, 145 Xanthone copolymers for use as electroactive components in thin films, 149


645

646

Index

Electrically active polymers (continued) Secondary battery Polypiperidine-4-vinyloxy-1-oxyl ethers polyradicals, 121 Semi-conductors Highly processable poly(thiazolethiophenes), 179 Polybenzoxazole amide dimethylhexafluoride derivatives, 171 Poly(dithienylbenzo[1,2-b:4,5-b0 ] dithiophenes with enhancing transistor performance, 176 Semiconductors containing adamantane cores with imidazole thermal barriers, 163 Terpolymers containing an acetal adamantoxy methacrylate, 167 Transistors Polysuccinimides containing grafted hydroxycoumarin, 185 Energetic polymers Explosive binder Shock insensitive polyphosphazene nitrates and azides, 191 Engineered plastics Blends Poly(4-phenylene sulfide)/nylon-66 blends, 197 Composites Poly(fluorene-co-triaryl amines) for use in advanced composites for space exploration, 200 Crosslinking agents 7-Methylene-1,5-dithaoctan methacrylate for use in dental compositions, 205 Poly(4-glycidyloxystyrene), 211 High performance polymers Amine terminated poly(styrene-cobutadiene) to lower tire hysterosis, 218 Co-polycarbonates containing 3,3bis(4-hydroxyphenyl)-1-phenyl1H- indol-2-one and bisphenol A biphenols, 221 Crosslinkable poly(dicyclopentadienes) containing low residual monomer, 225 Curable poly(ethylene-co-5-ethylidene2-norbornene), 232 High char polyesters containing 5-sodiosulfoisophthalic acid as a comonomer, 229 High purity polyphenylenesulfide, 248 Linear multifunctional unsaturated polyimides, 236

Novolak resins containing low tetramer content, 215 Poly(ethylene-co-carbon monoxide), 240 Poly(styrene-co-pyrrolidinium chloride) to enhance wetability, 244 Fabrics Antistatic Polypropylene oxide bis(perfluorobutylsulfonyl)imide, 17 Coatings Norrish type I or II type inactive, 21 Hydrolysis stabilizers Macroscopic acylureas, 25 Stain repellants Hydrophobic N-perfluoalkylatedpoly(4-vinylpyridine), 29 Wetting agents Polyacrylamide ionic solvents, 33 Fibers High strength Poly(n-hexylisocyanate) prepared using sodium benzyl phenyl ketone as the initiator, 252 Poly( p-phenylene benzobisoxazole-conanotube), 255 Fuel cells Fuel cell membranes Poly(1,2,4-triazole)-co-oxadiazole containing 85% 1,2,4-triazole content, 259 Proton conducting Polyamidic acid sulfamic acid derivatives, 262 Polyaromatic sulfonic acids containing hydrophilic and hydrophobic segments, 266 Polyaromatic perfluorosulfonic acids, 271 Polyaromatic ether perfluorosulfonic acids, 277 Improved synthetic methods Epoxidation of propylene using palladium/titanium zeolite-1 as catalyst, 285 Ethylene polymerization using (2-methyl-3-phenyl-1-(8-quinolyl)cyclopentadienyl)chromium dichloride, 296 Ethylene polymerization using Ziegler– Natta catalysts composed of a transition metal and a unique ratio of magnesium and titanium, 291 Olefin metathesis catalysts prepared using selected schiff bases, 301

Index Oligomeric uretonimine modified polyisocyanates using 3-methyl-1-phenyl-3phospholene-1-oxide as catalyst, 281 5-Norbornen-2-ol polymerization using N-(2,6-diisopropylphenyl)-2-(2,6diisopropyl-phenylimino)propanamide benzyltrimethyl-phosphine nickel and bis(1,5-cyclooctadiene)nickel, 309 Preparation of poly(propene-1-butene-1hexene) using silyl-zirconium-based Ziegler– Natta catalysts with triisobutylaluminium and methylalumoxane in the absence solvent, 313 Ring opening metathesis catalysts using ruthenium N-heterocyclic carbene ligands, 304 Storage stable polymerstyrene for use in seed polymerization, 468 Trimer and tetramer ethylene oligomers, 288 Initiators/modifiers Free radical initiators Acyloxime esters, 317 Free radical modifiers N-Alkoxy-4,4-dioxy-piperidine and N-oxide derivatives, 322 Photoinitiators 2-Benzyl-1-[4-(2-hydroxyethylamino) phenyl]-2-dimethylamino-1-butanone, 326 N-Ethylcarbazole oxime esters, 329 Photoinitiators consisting of benzoyltrimethylgermanium and bisbenzoyl diethyl-germanium derivatives, 421 Ink Dispersants Hyperbranched esters, 1 4-Methylbenzothiazole polyalkoxyethers, 5 Light emitting polymers Diodes Carbazole poly(terephthate esterco-carbonate) derivatives, 358 Conjugated aromatic dendrimers, 335 Conjugated aromatic polyazomethine thiophene polymers, 404 p-Conjugated organic polyfluorenes, 339 Conjugated polymers containing spirobifluorene, 398 Dibenzosilole copolymers having enhanced oxidative resistance, 363 Polybiphenylheterocyclics, 352 Polyconjugated phenoxazines, 376

647

Poly(fluorene-co-triphenylamine) derivatives, 369 Poly(2,6-naphthalenes), 383 Polymeric naphthylanthracenes, 387 Poly(norbornene-co-fluorene), 393 Solvent soluble styryl and methacrylate {tris[2-(2-pyridyl)phenyl]iridium} polymers, 345 Macrocyclic carbodiimides Polymerization, 25 Preparation using 1,3-dimethyl-3phospholene oxide, 25 Medical polymers Biodegradable Block copolyesters of polycarpolactone and poly(propylene fumarate), 414 Polyesters composed of 5-methylene-2phenyl-1,3-dioxolan-4-one derivatives and methylmethacrylate or styrene, 409 Poly(ester-urethanes) of polypropylene glycol, 417 Biomaterials for dental applications Acylgermane-containing polymers, 421 Carbosilane methacrylate oligomers having low shrinkage upon crosslinking, 426 Ether linked gemini aromatic epoxides having good mechanical strength and low shrinkage, 436 Hardenable and inert dental compositions using crosslinked polysilicones, 432 7-Methylene-1,5-dithaoctan methacrylates for use in dental compositions, 205 Biomaterials for diagnostics Polymers containing acylsulfonamide amine-reactive groups for isolating recombinant protein P, 447 The use of polylactides containing chelated 188Re metal ions for enhancing magnetic resonance imaging, 451 Biomaterials for drug delivery devices Amphiphilic terpolymers containing ethylene oxide and (R)-3-hydroxybutyrate, 455 Dithiocarbonate and thioether macromers and polymers to deliver reactants to a body cavity in a fluid form, 459 Hydrogels that selectively crosslink in the presence of base, 463 Poly(ester-amides) containing linear a-amino acid amides, 471 Poly(a-glutamic acid) polypeptide drug delivery devices containing pendant carboxylic acids, 476

648

Index

Medical polymers (continued ) Polyhydroxyalkanoic acids modified with aminoaromatics, 480 Replacement of polyethylene oxide with poly(N-vinyl-2-pyrrolidone) derivatives for use in drug delivery devices, 485 Biomaterials for gene therapy Amidoamine dentrimeric transfection agents, 489 Biomaterials for membranes Cell occlusive membranes prepared from aliphatic thiols and polyethylene glycol polyacrylate crosslinkers, 494 Glycoengineered polymers for trapping monosaccharides, 625 Biomaterials for implants Polyvinyl(2-hydroxyl-pyrrolidine)carbazoles for use in contact lenses and in biocompatible implants, 530 Nitric oxide releasing polymeric agents Diazeniumdiolation agents Diazeniumdiolation of polymeric isocyanides, 499 Diazeniumdiolation of polymeric hindered amines, 502 Oil drilling Dispersants Low polluting polymethacrylate betaines, 12 Optical Intraocular lenses High refractive index poly(dimethacrylate thiophene disulfide-co-2-hydroxyethyl methacrylate), 512 Polymeric siloxanes having high oxygen permeability, high water and ion transport rates, and a low modulus, 522 Polymerizable light absorbing azo dyes, 507 Poly(methylmethacrylate-g-exo-methylene lactone) having a low refractive index and high Abbe number, 517 Poly(thiocarbonate-co-thiourethane) derivatives having a high refractive index and Abbe number, 526 Polyvinyl(2-hydroxyl pyrrolidine) carbazoles for use in contact lenses and in biocompatible implants, 530

Optical fibers Heat and water resistant non-crystalline perfluorocopolymers containing 1,4-dioxane in the polymer backbone, 533 Optical waveguides Perdueterated polyaromatic polyimides prepared using o-tolidine and deuterated water, 536 Paint Hydrolytic stable Poly(N-(2-(methacryloyloxy)ethyl)-Nmethyl-pyruvamide) as a replacement paint additive for acetoacetoxy derivatives, 37 Poly(4-methyl-pentene) aldehyde, 42 Stabilizers Oligomeric polyaromatic esters to oxidatively stabilize paint, 46 Paper Stabilizers Glyoxalated poly(vinylamide-codiallyldimethyl-ammonium chloride), 50 Polymer Anti-craze agent Craze reduction in extrudes polypropylene using 1, 2, 4, 5-benzenetetracarboxylic anhydride amic acid, 52 Dispersants Poly(nylon-6-block-diethyleneglycol terephthalate), 57 Polymer synthesis Chemical and electrochemical synthesis of poly(1H-thieno[3,4-d]imidazol2(3H)-one), 126 Cyclic poly(diethyleneglycol terephthalate), 56 Hydroformylation of poly(4-methyl-1pentene) terminus, 42 Poly(ethylene-co-carbon monoxide), 240 Pharmaceuticals Polypeptides Improved method for preparing Glatiramer acetate using N-carboxyanhydride, 541 Radiopharmaceuticals Preparation of 3-131iodobenzylguanidinium derivatives using polymer-bound intermediates, 547 Photoresists Antireflective agents Antireflective copolymer coatings consisting of poly(4-hydroxylstyrene) and polymethacrylate-9-anthracene ester, 554

Index Latent acids High photoacid yielding poly(4-oxatricyclo [5.2.1.0.2,6]) methacrylates, 571 p-Terphenyl-based oximes for use as latent acids activated by irradiation with actinic electromagnetic, 588 Positive resists Photosensitive poly(3-methylthiomethyloxy-1-adamantyl methacrylate) resins, 551 Poly(hexafluoro-oxacyclopentane norborane methacrylate) resins, 559 Polylactones copolymer compositions which are transparent to ArF excimer laser light, 565 Polymethacrylate norbornane photoresists containing a 1,1,1,3,3,3-hexafluoro propyl substituent effective in the 157-nm range, 581 Polyperfluoroalcohols methacrylates, 576 Poly(ureylene methacrylates) curable by irradiation from infrared light, 594 Phototherapy Oxygen generators Method of preparing superoxide anions using water soluble fullerenes by irradiating with UV-Vis light, 599 Free Radical Traps Oligomeric porphyrins for use as free radical traps for humans exposed to O3, HO2, and radiation-induced injury, 603 Recording materials Anisotropic films

649

Photopolymerizable tri-acrylate aromatic esters having improved heat resistance, shrinkage, adhesive property, and mechanical strength, 607 Stents Cardiovascular Phase-separated poly(L-lactide-co-glycolides), 613 Sutures Adsorbable The use of dihydroxyacetone in preparing poly(spiroacetals), 617 Tissue replacement Tissue engineering N-Ethyl tyrosine amide polycarbonates with diminished hydrogen bonding, 621 Glycoengineered polymers for trapping monosaccharides, 625 Polymerization of (1,3-dioxolane-2,4diones) using 4-diaminomethylpyridine for use as a temporary skin substitute, 628 Preparation of degradable hydrogels by thiol-ene photopolymerization, 632 Viscoelastic polymers High viscoelastic materials Polyrotaxane inclusion complexes consisting of PEG-carboxylic acid and a-cyclodextrin, 635 Viscosity index improvers Polyacrylate-g-N-phenyl-p-phenylenediamine, 8

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