Polymer Handbook (4th Edition)

P O L Y M E R H F O U R T H A N D B O O K E D I T I O N Editors J. B R A N D R U P , E. H . I M M ...

Author: J. Brandrup | E. H. Immergut | E. A. Grulke

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A WILEY-INTERSCIENCE PUBLICATION JOHN WILEY & SONS, INC. New York • Chichester • Weinheim • Brisbane • Singapore • Toronto

G R U L K E

This book is printed on acid-free paper. @ Copyright © 1999 by John Wiley & Sons, Inc. All rights reserved. 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 Sections 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, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ @ WILEY.COM. Library of Congress Cataloging-in-Puhlication Data: Polymer Handbook / Editors: J. Brandrup, E. H. Immergut, and E. A. Grulke; Associate Editors, A. Abe, D. R. Bloch. - 4th ed. p. cm. "A Wiley-Interscience Publication." Includes index. ISBN 0-471-16628-6 (cloth : alk. paper) 1. Polymers—Tables. 2. Polymerization—Tables. I. Brandrup, J. II. Immergut, E. H. III. Grulke, Eric A. QD388.P65 1999 547.7-dc21 98-37261 Printed in the United States of America. 10 9 8 7 6 5 4 3 2

Contributors Abe, A. Tokyo Institute of Polytechnics, Atsugi, Japan Allegra, G. Dipartimento di Chimica del Politecnico, Milano, Italy Andreeva, L. N. Institute of High Molecular Weight Compounds, Russian Academy of Sciences, St. Petersburg, Russian Federation Andrews, R, J. Chemical and Materials Engineering Department, University of Kentucky, Lexington, Kentucky, USA Bai, F. The Maurice Morton Institute of Polymer Science, Univeristy of Akron, Akron, USA Bareiss, R. E. Editorial Office, Macromolecular Chemistry and Physics, Mainz, FR Germany Barrales-Rienda, J. M. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bello, A. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bello, P. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bloch, D. R. Lakeshore Research, Racine, Wisconsin, USA Brandrup, J. Wiesbaden, FR Germany Calhoun, B. H. The Maurice Morton Institute of Polymers Science, University of Akron, Akron USA Casassa, E. F. Department of Chemistry, Carneagfe-Mellon University, Pittsburgh, Pennsylvania, USA Cheng, S. Z. D. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA Chiu, F.-C. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA Cho, J. Polymer Science and Engineering Department, Dankook University, Seoul, South Korea Collins, E. A. Avon Lake, Ohio, USA Daniels, C. A. The Geon Company, Avon Lake, Ohio, USA DeLassus, P. T. The Dow Chemical Company, Freeport, Texas, USA Dixon, K. W. Akzo Nobel Chemicals, Inc., Dobbs Ferry, New York, USA

Elias, H.-G. Michigan Molecular Institute, Midland, Michigan, USA Fink, G. Max-Planck-Institut fur Kohlenforschung, Miilheim an der Ruhr, FR Germany Fink, H.-P. Fraunhofer Institut fiir angewandte Polymerforschung, TeltowSeehof, FR Germany Fouassier, J. P. Laboratoire de Photochimie Generate, Ecole Nationale Superieure de Chimie, Mulhouse, France Fu, Q. The Maurice Morton Institute and Department of Polymer Science, University of Akron, Akron, Ohio, USA Furuta, I. Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Ganster, J. Fraunhofer Institute for Applied Polymer Research, TeltowSeehof, Germany Greenley, R. Z. Monsanto Corporation (retired), St. Louis, Missouri, USA Grulke, E. A. Chemical and Materials Engineering, University of Kentucky, Lexington, Kentucky, USA Goh, S. H. Department of Chemistry, National University of Singapore, Singapore Guzman G. M. Instituto de Ciencia y Tecnologfa de Polfmeros, Madrid, Spain Hill, D. J. T. Department of Chemistry, University of Queensland, St. Lucia, Australia Hiltner, A. Department of Macromolecular Science, School of Engineering Case Western University, Cleveland, Ohio, USA Inomata, K. Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo, Japan Iwama, M. Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Jenkins, A. D. School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, UK Jenkins, J. School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, UK

Johnson, M. Chemistry/Physics Library, University of Kentucky, Lexington, Kentucky, USA Kamachi, M. Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan Kerbow, D. L. DuPont Fluoroproducts, Wilmington, Delaware, USA Kimura, S.-L Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Korte, S. Zentrale Ferschung, Bayer AG, Leverkunsen, FR Germany Krause, S. Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York, USA Kurata, M. Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan Lechner, M. D. Physikalische Chemie, Universitat Osnabriick, Osnabriick, FR Germany Leonard, J. Department de Chimie and CERSIM, Universite Laval, Quebec, Canada Li, F. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA

Muck, K.-F. Ticona GmbH, Kelsterbach, FR Germany Nagai, S. Plastics Technical Association, Osaka, Japan Nordmeier, E. Physikalische Chemie, Universitat Osnabriick, Osnabriick FR Germany Ogo, Y. Research Institute for Solvothermal Technology, Hayashi, Takamatsu, Kagawa, Japan Orwoll, R. A. College of William and Mary, Williamsburg, Virginia, USA Pauly, S. Fachlaboratorium fur Permeationspriifung, Wiesbaden, FR Germany Peebles, L. H., Jr. Chemistry Division, Naval Research Laboratory, Washington, DC, USA Perera, M. C. S. Magnetic Resonance Facility, School of Science, Griffith University, Nathan, Australia Porzio, W. Instituto di Chimica delle Macromolecole del C.N.R., Milano, Italy Pyda, M. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, USA

Liggat, J. Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland

Quirk, R. P. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA

Lindemann, M. Greenville, South Carolina, USA Luft, G. Institut fur Chemische Technologie, Technische Hochschule, Darmstadt, FR Germany

Riande, E. Instituto de Ciencia y Tecnologia de Polimeros, Madrid, Spain

Magill, J. H. School of Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania, USA McKenna, T. F. Centre Nationale de Ia Recherche Scientifique, Laboratoire de Chimie et Procedes de Polymerisation/Departement Genie des Procedes, Villeurbanne, France Mehta, R. H. Dupont Nylon, Chattanooga, Tennessee, USA Mettle, S. V. Dipartimento di Chimica del Politecnico, Milano, Italy Metanomski, W. V. Chemical Abstracts Service, Columbus, Ohio, USA Michielsen, S. School of Textile and Fiber Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA Miller, R. L. Michigan Molecular Institute, Midland, Michigan, USA Morita, Y. Japan Atomic Energy Research Institute, Takasaki, Gunma-ken, Japan

Richter, W. J. Max-Planck-Institut fur Kohlenforschung, Miilheim an der Ruhr, FR Germany Rothe, M. University of UIm, UIm, FR Germany Rule, M. Coca Cola Company, Atlanta, Georgia, USA Salort, J. F. Madrid, Spain Salom, C. Escuela Tecnica Superior de Ingenieros Aeronauticos, Universidad Politecnica, Madrid, Spain Sanchez, I. C. Chemical Engineering Department, University of Texas at Austin, Austin, Texas, USA Santos, A. M. Faculdade de Engenharia Quimica de Lorena - FAENQUIL, Lorena, Sao Paulo, Brazil Schoff, C. K. PPG Industries, Allison Park, Pennsylvania, USA Schuld, N. Institut fur Physikalische Chemie, Universitat Mainz, Mainz, FR Germany

Seferis, J. C. Chemical Engineering Department, University of Washington, Seattle, Washington, USA Seguchi, T. Japan Atomic Energy Research Institute, Takasaki, Gunma-ken, Japan

Wagener, K. B. Department of Chemistry and Center for Macromolecular Science and Engineering, University of Florida, Gainesville, Florida, USA Whiteman, N. F. The Dow Chemical Company, Freeport, Texas, USA

Schrader, D. The Dow Chemical Company, Midland, Michigan, USA

Witenhafer, D. E. Dublin, Ohio, USA

Sperati, C. A. Chemical Engineering Department, Ohio University, Athens, Ohio, USA

Wolf, B. A. Institut fur Physikalische Chemie, Universitat Mainz, Mainz, FR Germany

Steinmeier, D. G. Physikalische Chemie, Universitat Osnabriick, Osnabruck, FR Germany

Wu, S. E. I. DuPont de Nemours, Central Research and Development Department, Experimental Station, Wilmington, Delaware

Tsunashima, Y. Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan

Wunderlich, B. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, USA

Tsvetkov, N. V. Institute of High Molecular Weight Compounds, Russian Academy of Science, St. Petersburg, Russian Federation

Wunderlich, W. ROHM GmbH, Darmstadt, FR Germany

Tsvetkov, V. N. Institute of High Molecular Weight Compounds, Russian Academy of Science, St. Petersburg, Russian Federation

Yamada, B. Department of Applied Chemistry, Faculty of Technology, Osaka City University, Sumiyoshi, Osaka, Japan

Ueda, A. Osaka Municipal Technical Research Institute, Morinomiya, Joto-ku, Osaka, Japan

Zhu, L. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA

Preface The purpose of the Polymer Handbook is to bring together the data and constants needed in theoretical and experimental polymer research. All polymer researchers have experienced the frustration of searching for data in the everexpanding polymer literature and know the difficulties involved in trying to locate a particular constant that is buried in a long journal article. The contributors to this Handbook have taken on the arduous task of searching the literature and compiling the data and constants that polymer chemists, polymer physicists, and polymer engineers are likely to need. The 520 and odd tables in this Handbook are divided into eight sections. The first lists the IUPAC nomenclature rules for polymers and the International System of Units. Although several naming conventions exist in the technical literature, IUPAC names permit a consistent listing of all polymers. Section II contains data and constants needed for polymer synthesis, kinetic mechanisms, and thermodynamic studies of polymerization and depolymerization reactions. Sections III and IV contain physical constants of monomers, solvents, and oligomers. Section V lists the physical constants of many important commercial polymers. Section VI and VII cover the solid state properties of polymers and the properties of polymer solutions. Section VIII of the Handbook lists the commonly used abbreviations or acronyms for polymers and Chemical Abstract Registry Numbers, and gives suggestions for electronic data searching for polymer information. This section should also be consulted in the few cases where contributors have not used IUPAC nomenclature. As in the previous editions, the Polymer Handbook concentrates on synthetic polymers, poly(saccharides) and derivatives, and oligomers. Few data on biopolymers are included. Spectroscopic data as well as data needed by engineers and designers, such as mechanical and rheological data, are minimized, since many excellent compilations exist elsewhere. Only fundamental constants and parameters that refer to the polymer molecule, that describe the solid state of polymer molecules, or that describe polymer solutions, were compiled. Constants that depend on processing conditions or on sample history were not emphasized, as they can be found in existing plastics handbooks and encyclopedias.

A critical evaluation of the values published in the literature was not attempted, since such a task would have required an inordinate amount of time and a sizable staff. Therefore, the users of this Handbook should consult the original literature for details when in doubt about the validity of any data. (The authors of the individual tables were nevertheless requested to eliminate obviously erroneous data from otherwise complete compilations.) The Fourth Edition revisions have focused on data generated in the ten years since the publication of the Third Edition. Therefore, a completely revised Polymer Handbook has been prepared. We have added new tables and incorporated a large amount of new data into existing tables. As a result, the Fourth Edition contains approximately twenty-five percent more data, and the number of pages has increased from about 1850 in the Third Edition to about 2250. We hope that this new edition will be as useful to the polymer research community as the three earlier editions and that many of the Polymer Handbook's previous users will also obtain the Fourth Edition for their laboratory and library. The publisher plans a CD-ROM for the Polymer Handbook in the near future. We would be grateful if our contributors and users send us any new data they accumulate in the course of their research, and any errors, misprints, omissions and other flaws. We will pass on such data to the publisher, for the polymer database, and for future editions of this Handbook. We would like to thank all of the contributors to the Polymer Handbook for their help and continued patience. The staff at John Wiley, especially Carla Fjerstad, Shirley Thomas, and Jacqueline Kroschwitz, have provided excellent help and support in getting all the work done. We hope that the outstanding efforts of all these people will find due appreciation among the users of this Handbook. July, 1998

J. Brandrup E. H. Immergut E. A. Grulke A. Abe D. R. Bloch

Contents

Contributors .............................................................................................................................

v

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

ix

I.

Nomenclature Rules – Units

Nomenclature ...............................................................................................................................................

I/1

A. Introduction ........................................................................................................................

I/1

B. IUPAC Recommendations .................................................................................................. 1. Source-based Nomenclature .................................................................................. 1.1 Homopolymers ........................................................................................ 1.2 Copolymers ............................................................................................. 1.3 Nonlinear Macromolecules and Macromolecular Assemblies ................ 2. Structure-based Nomenclature ............................................................................... 2.1 Regular Single-strand Organic Polymers ............................................... 2.2 Regular Double-strand Organic Polymers .............................................. 2.3 Regular Single-strand Inorganic and Coordination Polymers ................. 2.4 Regular Quasi-single-strand Coordination Polymers .............................. 2.5 Irregular Single-strand Organic Polymers ...............................................

I/1 I/2 I/2 I/2 I/3 I/3 I/3 I/6 I/6 I/7 I/7

C. Use of Common and Semisystematic Names .....................................................................

I/8

D. Chemical Abstracts (CA) Index Names ...............................................................................

I/8

E. Polymer Class Names ........................................................................................................

I/11

F. References .........................................................................................................................

I/12

Units .............................................................................................................................................................

I/13

A. Introduction ........................................................................................................................

I/13

B. International Units ..............................................................................................................

I/13

C. SI-prefixes ..........................................................................................................................

I/14

D. Conversion Factors ............................................................................................................

I/14

E. Conversion Table for SI vs. English-american Units ...........................................................

I/17

II.

Polymerization and Depolymerization

Decomposition Rates of Organic Free Radical Initiators ............................................................................

II/1

A. Introduction ........................................................................................................................

II/1

B. Tables of Decomposition Rates of Organic Free Radical Initiators ..................................... Table 1. Azonitriles ............................................................................................................... Table 2. Miscellaneous Azo-derivatives ................................................................................

II/2 II/2 II/9

This page has been reformatted by Knovel to provide easier navigation.

xi

xii

Contents Table 3. Table 4. Table 5. Table 6. Table 7.

Alkyl Peroxides ....................................................................................................... Acyl Peroxides ........................................................................................................ Hydroperoxides and Ketone Peroxides .................................................................. Peresters and Peroxycarbonates ............................................................................ Miscellaneous Initiators ...........................................................................................

II/23 II/29 II/43 II/48 II/67

C. Notes ..................................................................................................................................

II/69

D. References .........................................................................................................................

II/70

Propagation and Termination Constants in Free Radical Polymerization ..................................................

II/77

A. Introduction ........................................................................................................................

II/77

B. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.

Propagation and Termination Constants ............................................................. Dienes ..................................................................................................................... Olefins ..................................................................................................................... Acrylic Derivatives ................................................................................................... Methacrylic Derivatives ........................................................................................... Itaconic Derivatives ................................................................................................. Fumaric Derivatives ................................................................................................ Vinyl Halides ........................................................................................................... Vinyl Esters ............................................................................................................. Vinyl Ethers ............................................................................................................. Styrene Derivatives ................................................................................................. Vinyl Heteroaromatics ............................................................................................. Aldehydes ............................................................................................................... Others .....................................................................................................................

II/79 II/79 II/79 II/80 II/82 II/85 II/87 II/87 II/87 II/88 II/88 II/90 II/90 II/90

C. References .........................................................................................................................

II/91

Transfer Constants to Monomers, Polymers, Catalysts and Initiators, Solvents and Additives, and Sulfur Compounds in Free Radical Polymerization ...........................................................................

II/97

A. Introduction ........................................................................................................................

II/97

B. Tables of Transfer Constants ............................................................................................. Table 1. Transfer Constants to Monomers ........................................................................... Table 2. Transfer Constants to Polymers ............................................................................. Table 3. Transfer Constants to Catalysts and Initiators ........................................................ Table 4. Transfer Constants to Solvents and Additives ........................................................ Table 5. Transfer Constants to Sulfur Compounds ...............................................................

II/98 II/98 II/103 II/106 II/110 II/150

C. Remarks .............................................................................................................................

II/157

D. References .........................................................................................................................

II/159

Photopolymerization Reactions ...................................................................................................................

II/169

A. Introduction ........................................................................................................................

II/169

B. Tables ................................................................................................................................ Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in Radical Photoinitiators ............................................................................................ Annex to Table 1. Photoinitiator Compound Chemistries ......................................

II/170


II/170 II/173

Contents Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with Various Monomers in Cyclohexane at Room Temperature .................................... Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with Various Olefinic Monomers at Room Temperature ................................................. Table 4. Bimolecular Rate Constants for the Reaction of Ph2P = O and Ph2P = S with Various Monomers .................................................................................................. Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts .................... Table 6. Electron Transfer Rate Constants (ke) between Photosensitizers and Cationic Photoinitiators and Quenching Rate Constants (kq) for Cyclohexene Oxide in Methanol (M) and Acetonitrile (AN) .......................................................... Table 7. Excitation Transfer Rate Constants (kT) for Thioxanthones and Photoinitiators ......................................................................................................... Annex to Table 7. Compound Chemistries ............................................................ Table 8. Triplet State Lifetimes (τT) of the Sensitizer (TXI) in Different Media, and Rate Constant (kT) of the Interaction between TXI and TPMK ............................... Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and Monomers ............................................................................................................... Table 10. Values of τ0T, τT, and kba in Solution ........................................................................ Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution .............. Annex to Table 11 ...................................................................................................

xiii II/176 II/176 II/176 II/176

II/177 II/178 II/178 II/179 II/179 II/179 II/179 II/179

C. References .........................................................................................................................

II/180

Free Radical Copolymerization Reactivity Ratios .......................................................................................

II/181

A. Introduction ........................................................................................................................

II/181

B. Tables ................................................................................................................................ Table 1. Copolymer Reactivity Ratios ................................................................................... Acenaphthalene to Fumarate, bis(3-chloro-2-butyl) ................................................ Fumarate, di-(2-chloroethyl) to N-N-divinylaniline ................................................... N-vinylimidazole to Styrene, p-2-(2-hydroxypropyl)- ............................................... Styrene, p-4-methoxyphenyl ketone to Vinylbenzoate, p-, sodium ......................... Vinylbenzoic acid, p- to Xanthate, S-methacryloyl O-ethyl ..................................... Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios .........


C. References .........................................................................................................................

II/290

Q and e Values for Free Radical Copolymerizations of Vinyl Monomers and Telogens ...........................

II/309

A. Introduction ........................................................................................................................

II/309

B. Q and e Table 1. Table 2. Table 3. Table 4.

Values for Free Radical Copolymerizations .......................................................... Monomers ............................................................................................................... Telogens ................................................................................................................. Monomers Arranged by Q Values ........................................................................... Monomers Arranged by e Values ...........................................................................

II/310 II/310 II/314 II/314 II/317

C. References .........................................................................................................................

II/319

Patterns of Reactivity (U,V) Parameters for the Prediction of Monomer Reactivity Ratios and Transfer Constants in Radical Polymerization ...................................................................................

II/321

A. Introduction ........................................................................................................................

II/321


xiv

Contents B. Example .............................................................................................................................

II/322

C. Transfer Constants .............................................................................................................

II/322

D. Tables of Parameters ......................................................................................................... Table 1. Monomers ............................................................................................................... Table 2. Transfer Agent ........................................................................................................

II/323 II/323 II/326

E. References .........................................................................................................................

II/327

Copolymerization Parameters of Metallocene-catalyzed Copolymerizations ............................................

II/329

A. Introduction ........................................................................................................................

II/329

B. A Brief Theoretical Outline of Copolymerization Reactions ................................................. 1. First-order Markov Model ........................................................................................ 2. Second-order Markov Model ...................................................................................

II/329 II/330 II/330

C. Calculation of the Copolymerization Parameters ................................................................ 1. First-order Markov Model ........................................................................................ 1.1. Copolymerization Parameters Deduced from the Mayo-lewis Equation .................................................................................................. 1.2. Determination of Copolymerization Parameters from the Sequence Distribution (Triad Distribution) .............................................. 2. Second-order Markov Model ................................................................................... 3. Example ..................................................................................................................

II/331 II/331

D. Table of Copolymerization Parameters ...............................................................................

II/333

E. List of Catalysts/Cocatalysts Used .....................................................................................

II/336

F. References .........................................................................................................................

II/336

Rates of Polymerization and Depolymerization, Average Molecular Weights, and Molecular Weight Distribution of Polymers .........................................................................................................

II/339

A. Introduction ........................................................................................................................

II/339

B. Reference Tables for the Calculation of Rates of Polymerization, Average Molecular Weights, and Molecular Weight Distributions of Polymers for Various Types of Polymerization .................................................................................................................... Table 1. Addition Polymerization with Termination ............................................................... Table 2. Addition Polymerization - "Living" Polymers with Partial Deactivation .................... Table 3. Linear Condensation Polymerization without Ring Formation ................................ Table 4. Equilibrium Polymerization ...................................................................................... Table 5. Nonlinear Polymerization Systems ......................................................................... Table 6. Degradation of Polymers - May Be Accompanied by Crosslinking ......................... Table 7. Influence of Reactor Conditions and Design on the Molecular Weight Distribution ..............................................................................................................

II/340 II/341 II/344 II/346 II/347 II/348 II/350

C. Some Distribution Functions and Their Properties .............................................................. 1. Normal Distribution Function (Gaussian Distribution) ............................................. 2. Logarithmic Normal Distribution Function ............................................................... 3. Generalized Exponential Distribution ...................................................................... 4. Poisson Distribution ................................................................................................

II/352 II/353 II/353 II/354 II/354


II/331 II/331 II/332 II/332

II/352

Contents

xv

D. Molecular Weight Distribution in Condensation Polymers: the Stockmayer Distribution Function ...........................................................................................................

II/354

E. References .........................................................................................................................

II/356

Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds ...................................................

II/363

A. Heats of Polymerization ...................................................................................................... Table 1. Monomers Giving Polymers Containing Carbon Atoms Only in the Main Chain ....................................................................................................................... 1.1 With Acyclic Carbons Only in the Main Chain ........................................

II/365

1.1.1 Dienes ..............................................................................................

II/365

1.1.2 Monomers Giving Polymers with or without Aliphatic Side Chains That Contain Only C, H ........................................................

II/365

1.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................

II/368

1.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................

II/371

1.1.5 Monomers Giving Polymers with Aromatic Side Chains and That Contain Heteroatoms ............................................................... 1.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 2. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 2.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................

II/365 II/365

II/371 II/372 II/373 II/373

2.1.1 Ethers and Acetals ...........................................................................

II/373

2.1.2 Cyclic Esters ..................................................................................... 2.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 2.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.5 Monomers Giving Polymers Containing N in the Main Chain, Bonded to Other Heteroatoms (P) .......................................................... 2.6 Other Monomers Giving Polymers Not Listed Above ............................. Table 3. Copolymers .............................................................................................................

II/376 II/377 II/378 II/378 II/379 II/379 II/380

B. Entropies of Polymerization ................................................................................................ Table 4. Monomers Giving Polymers Containing Main Chain Carbon Only ......................... 4.1 Main Chain Acyclic Carbon Only ............................................................

II/381 II/382 II/382

4.1.1 Dienes ..............................................................................................

II/382

4.1.2 Monomers Giving Polymers without or with Aliphatic Side Chains That Contain Only C, H ........................................................

II/382

4.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................

II/384


xvi

Contents 4.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................

II/385

4.1.5 Monomers Giving Polymers with Aromatic Side Chains That Contain Heteroatoms .......................................................................

II/385

4.1.6 Other Monomers Giving Polymers Not Listed Above ...................... 4.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 5. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 5.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................

II/386 II/386 II/387

5.1.1 Ethers and Acetals ...........................................................................

II/387

5.1.2 Cyclic Esters ..................................................................................... 5.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 5.3 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 5.4 Other Monomers Giving Polymers Not Listed Above ............................. Table 6. Copolymers .............................................................................................................

II/390

C. Ceiling Temperatures and Equilibrium Monomer Concentrations ....................................... 1. Equilibria Involving Pure Liquid Monomers ............................................................. Table 7. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only ............................................................................................ Table 8. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ...................................................................................................... 8.1


Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................

II/395

Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, P, Si) .........................................

II/396

Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................

II/396

Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...............................................

II/397

8.5 Other Monomers Giving Polymers Not Listed Above ...................... Equilibria Involving Gaseous Monomers ................................................................. Equilibria Involving Monomers in Solution .............................................................. Table 9. Monomers Giving Polymers Containing Main Chain Carbon Only .........

II/397 II/397 II/398 II/398

8.2 8.3 8.4

2. 3.

II/387

9.1

Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only .....................................................................................

II/398

9.2

Monomers Giving Polymers Containing Main Chain Cyclic Carbon .............................................................................................. Table 10. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ......................................................................................................

II/399

10.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................

II/399


II/399

Contents

xvii

10.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (Si, P) ..............................................

II/400

10.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................

II/400

10.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ............................................... Table 11. Copolymers .............................................................................................

II/400 II/401

11.1 1:1 Copolymers ................................................................................

II/401

11.2 General Copolymers ........................................................................

II/401

D. Polymerizability of 5-, 6-, and 7-membered Heterocyclic Ring Compounds ........................ Table 12. 5-membered Ring Compounds ............................................................................... Table 13. 6-membered Ring Compounds ............................................................................... Table 14. 7-membered Ring Compounds ............................................................................... Table 15. Comparison of Polymerizability (+ or -)of Unsubstituted 5-, 6- and 7-membered Ring Compounds ...............................................................................

II/401 II/402 II/403 II/404

E. Notes ..................................................................................................................................

II/406

F. References .........................................................................................................................

II/407

Activation Energies of Propagation and Termination in Free Radical Polymerization ...............................

II/415

A. Introduction ........................................................................................................................

II/415

B. Tables ................................................................................................................................ Table 1. Dienes ..................................................................................................................... Table 2. Olefins ..................................................................................................................... Table 3. Acrylic Derivatives ................................................................................................... Table 4. Methacrylic Derivatives ........................................................................................... Table 5. Vinyl Halogens ........................................................................................................ Table 6. Vinyl Ethers and Vinyl Esters .................................................................................. Table 7. Styrene and Derivatives .......................................................................................... Table 8. Vinyl Heteroaromatics ............................................................................................. Table 9. Miscellaneous Compounds .....................................................................................

II/416 II/416 II/416 II/417 II/418 II/420 II/421 II/421 II/422 II/423

C. References .........................................................................................................................

II/424

Activation Volumes of Polymerization Reactions ........................................................................................

II/429

A. Introduction ........................................................................................................................

II/429

3

II/405

B. Activation Volumes (sm /mol) of Some Polymerization Reactions ......................................

II/432

C. Activation Volumes of Initiator Decomposition ....................................................................

II/435

D. Activation Volumes of Chain Propagation ...........................................................................

II/435

E. Activation Volumes of Chain Termination ...........................................................................

II/436

F. Activation Volumes of Chain Transfer Reactions ................................................................

II/436

G. Influence of Pressure on Copolymerization ........................................................................ Table 1. Copolymerization Parameters ................................................................................. Table 2. Reactivity Ratios of Terpolymerization .................................................................... Table 3. Activation Volumes ................................................................................................. Table 4. Q, e Values .............................................................................................................

II/437 II/437 II/438 II/439 II/440


xviii

Contents H. References .........................................................................................................................

II/440

Activation Enthalpies and Entropies of Stereocontrol in Free Radical Polymerizations .............................

II/445

A. Introduction ........................................................................................................................

II/445

B. Tables ................................................................................................................................ Table 1. Ratios of Some i-ADS for Different Mechanisms .................................................... Table 2. Ratios of Rate Constants for Markov First Order Mechanisms ............................... Table 3. ∆H++s/i - ∆H++i/s and ∆S++s/i - ∆S++i/s of Free Radical Polymerizations in Different Solvents .................................................................................................... Table 4. Activation Enthalpy Differences (∆H++A - ∆H++B) Calculated from Various Literature Data ........................................................................................................ Table 5. Activation Entropy Differences (∆S++A - ∆S++B) Calculated from Various Literature Data ........................................................................................................ Table 6. Calculated Compensation Temperatures T0 and Compensation Enthalpies ∆∆H++0 for Various Monomers and Modes of Addition, Assuming Markov First Order Trials .....................................................................................................

II/446 II/446 II/446

C. References .........................................................................................................................

II/450

Products of Thermal Degradation of Polymers ...........................................................................................

II/451

A. Introduction ........................................................................................................................

II/451

B. Tables ................................................................................................................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... Table 5. Cellulose and Its Derivatives ...................................................................................

II/451 II/451 II/464 II/465 II/473 II/475

C. References .........................................................................................................................

II/475

Radiation Chemical Yields: G Values ..........................................................................................................

II/481

A. Introduction ........................................................................................................................

II/481

B. Tables of G Values ............................................................................................................. Table 1. Homopolymers ........................................................................................................ 1.1 Polydienes .............................................................................................. 1.2 Polyolefins .............................................................................................. 1.3 Polyacrylates .......................................................................................... 1.4 Poly(methacrylates) ................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Poly(vinyls) .............................................................................................


1.6.1 Acrylamides and Nitriles ...................................................................

II/486

1.6.2 Vinyl Monomers ................................................................................ Miscellaneous Polymers .........................................................................

II/486 II/487

1.7.1 Cellulose and Derivatives .................................................................

II/487

1.7.2 Poly(siloxanes) .................................................................................

II/487

1.7.3 Poly(amino Acids) ............................................................................

II/487

1.7.4 Polyesters .........................................................................................

II/488

1.7


II/447 II/448 II/449

II/449

Contents

III.

xix

1.7.5 Polysulfones .....................................................................................

II/488

1.7.6 Polyketones ......................................................................................

II/488

1.7.7 Fluoropolymers .................................................................................

II/488

1.7.8 Others ............................................................................................... Table 2. Copolymers ............................................................................................................. 2.1 Copolymers with Ethylene ...................................................................... 2.2 Copolymers with Methyl Methacrylate .................................................... 2.3 Copolymers with Styrene ........................................................................ 2.4 Copolymers with Sulfur Dioxide .............................................................. 2.5 Other Copolymers ................................................................................... Table 3. Polymers Blends ..................................................................................................... Table 4. Composites .............................................................................................................

II/489 II/490 II/490 II/490 II/491 II/491 II/492 II/493 II/493

C. References .........................................................................................................................

II/493

Physical Properties of Monomers and Solvents

Physical Properties of Monomers ................................................................................................................

III/1

A. Introduction ........................................................................................................................

III/1

B. Tables of Table 1. Table 2. Table 3. Table 4.

Table 5.

Table 6.

Table 7. Table 8. Table 9.

Table 10.

Table 11.

Physical Properties ............................................................................................. Acetylenes .............................................................................................................. Acid Dichlorides ...................................................................................................... Acroleins ................................................................................................................. Acrylamides/Methacrylamides ................................................................................ 4.1 Acrylamides ............................................................................................ 4.2 Methacrylamide ...................................................................................... Acrylates/Methacrylates .......................................................................................... 5.1 Acrylate, Acids/Esters ............................................................................. 5.2 Methacrylate, Acids/Esters ..................................................................... Alcohols .................................................................................................................. 6.1 Alkanediols ............................................................................................. 6.2 Ether Diols .............................................................................................. Allyl Functional ........................................................................................................ Amines, Difunctional ............................................................................................... Anhydrides .............................................................................................................. 9.1 Monoanhydrides ..................................................................................... 9.2 Dianhydrides ........................................................................................... Butadienes .............................................................................................................. 10.1 1,2-butadienes ........................................................................................ 10.2 1,3-butadienes ........................................................................................ Butenes ................................................................................................................... 11.1 1-butenes ................................................................................................ 11.2 2-butenes ................................................................................................


III/4 III/4 III/4 III/4 III/4 III/4 III/6 III/8 III/8 III/12 III/16 III/16 III/18 III/18 III/20 III/20 III/20 III/24 III/24 III/24 III/24 III/26 III/26 III/26

xx

Contents Table 12. Epoxides ................................................................................................................. 12.1 Monoepoxides ........................................................................................ 12.2 Diepoxides .............................................................................................. Table 13. Ethylene Halides ..................................................................................................... Table 14. Fumaric, Acids/Esters ............................................................................................. Table 15. lsocyanates ............................................................................................................. Table 16. Lactams .................................................................................................................. Table 17. Lactones ................................................................................................................. Table 18. Maleate, Acids/Esters ............................................................................................. Table 19. Propenes ................................................................................................................. Table 20. Styrenes .................................................................................................................. Table 21. Vinyl Functional ....................................................................................................... 21.1 Aryl .......................................................................................................... 21.2 Esters ...................................................................................................... 21.3 Ethers ..................................................................................................... 21.4 N-substituted ........................................................................................... 21.5 Sulfonates ...............................................................................................

III/26 III/26 III/28 III/28 III/30 III/30 III/32 III/32 III/32 III/32 III/34 III/36 III/36 III/36 III/38 III/38 III/40

Isorefractive and Isopycnic Solvent Pairs ....................................................................................................

III/43

A. Introduction ........................................................................................................................

III/43

B. Table of Isorefractive and Isopycnic Solvent Pairs ..............................................................

III/43

Refractive Indices of Common Solvents .....................................................................................................

III/55

A. Introduction ........................................................................................................................

III/55

B. Table of Refractive Indices of Common Solvents ...............................................................

III/55

Physical Constants of the Most Common Solvents for Polymers ...............................................................

III/59

IV.

Physical Data of Oligomers

Physical Data of Oligomers .........................................................................................................................

IV/1

A. Introduction ........................................................................................................................

IV/2

B. Oligomers Containing Main Chain Acyclic Carbon Only ..................................................... Table 1. Oligo(olefins) ........................................................................................................... 1.1. Oligo(methylenes) and Oligo(ethylenes) ................................................ 1.2. Oligo(perfluoromethylenes) and Oligo(perfluoroethylenes) .................... 1.3. Oligo(isobutenes) .................................................................................... 1.4. Oligo(1-alkenylenes) ............................................................................... References .............................................................................................................. Table 2. Oligo(dienes) ........................................................................................................... 2.1. Oligomers of 1,3-butadiene .................................................................... 2.2. Oligomers of lsoprene ............................................................................. 2.3. Oligomers of 1,3-butadiene Derivatives .................................................. 2.4. 1,4-oligo(alkadienes) .............................................................................. 2.5. Oligomers of Cyclopentadiene and 1,3-cyclohexadiene .........................

IV/3 IV/3 IV/3 IV/6 IV/8 IV/9 IV/9 IV/14 IV/14 IV/15 IV/16 IV/16 IV/17


Contents

xxi

2.6. Oligomers of Allene ................................................................................ References .............................................................................................................. Table 3. Oligo(acetylenes) .................................................................................................... 3.1. Linear Oligomers of Acetylene ................................................................ 3.2. Polyenyne Oligomers .............................................................................. 3.3. Oligomeric α-ω-diynes ............................................................................ 3.4. Oligo(alkynes) ......................................................................................... 3.5. Cyclic Oligo(alkynes) .............................................................................. 3.6. Pericyclynes ............................................................................................ References .............................................................................................................. Table 4. Oligomers with Aliphatic Side Chains Which in Addition Contain Heteroatoms ........................................................................................................... 4.1. Oligomeric Acrylic Derivatives ................................................................ 4.2. Oligomeric Methacrylic Derivatives ......................................................... 4.3. Oligomers of β-alkyl Substituted Vinyl Derivatives ................................. 4.4. Oligo(vinyl) Derivatives ........................................................................... References .............................................................................................................. Table 5. Oligo(styrenes) ........................................................................................................ References ..............................................................................................................

IV/17 IV/18 IV/19 IV/19 IV/20 IV/20 IV/20 IV/20 IV/21 IV/21

C. Oligomers Contaning Heteroatoms in the Main Chain ........................................................ Table 6. Oligomers Containing O in the Main Chain ............................................................. 6.1. Oligo(ethers) and Oligo(acetals) .............................................................

IV/33 IV/33 IV/33

6.2.

References .................................................................................................. Oligo(carbonates) ...................................................................................

IV/43 IV/47

6.3.

References .................................................................................................. Oligo(esters) ...........................................................................................

IV/47 IV/48

6.4.

References .................................................................................................. Oligo(urethanes) .....................................................................................

IV/56 IV/58

References .................................................................................................. Table 7. Oligo(sulfides) and Oligo(selenides) ....................................................................... 7.1. Cyclic Oligo(thiomethylenes) and Oligo(Selenomethylenes) .................. 7.2. Cyclic Oligo(thioalkylenes) ...................................................................... 7.3. Substituted Cyclic(thioethylenes) ............................................................ 7.4. Cyclic Co-oligomers of Formaldehyde and Thioformaldehyde ............... 7.5. Cyclic Oligo(ether Sulfides) .................................................................... 7.6. Thiacyclophanes ..................................................................................... References .............................................................................................................. Table 8. Oligomers Containing N in the Main Chain ............................................................. 8.1. Oligo(amides) .........................................................................................

IV/61 IV/62 IV/62 IV/62 IV/62 IV/62 IV/63 IV/63 IV/63 IV/64 IV/64

References .................................................................................................. Oligo(peptides) .......................................................................................

IV/70 IV/72

References ..................................................................................................

IV/84

8.2.


IV/22 IV/22 IV/24 IV/26 IV/27 IV/28 IV/30 IV/32

xxii

Contents 8.3.

Oligo(imines) ...........................................................................................

IV/88

8.4.

References .................................................................................................. Oligo(ureas) ............................................................................................

IV/89 IV/89

References ..................................................................................................

IV/90

D. Carbon Chain Oligomers Containing Main Chain Cyclic Units ............................................ Table 9. Oligo(cyclopentylenes) ............................................................................................ Table 10. Oligo(spiranes) ........................................................................................................ Table 11. Oligo(xylylenes) ...................................................................................................... 11.1. Linear Oligo(xylenes) .............................................................................. 11.2. Cyclic Oligo(xylylenes) ............................................................................ Table 12. Oligo(stilbenes) ....................................................................................................... Table 13. Oligo(benzyls) ......................................................................................................... Table 14. Oigo(2,5-dimethyl-benzyls) ..................................................................................... Table 15. Oligo(2,3,5,6-tetramethyl-benzyls) .......................................................................... Table 16. Oligo(p-phenylene Oxides) ..................................................................................... Table 17. Oligo(p-phenylene Sulfides) .................................................................................... Table 18. Oligo(p-phenoxyphenylmethanes) .......................................................................... Table 19. Oligo(diphenylmethanes) ........................................................................................ References .............................................................................................................. Table 20. Phenol-formaldehyde and Related Oligomers ........................................................ 20.1. Linear Phenol-formaldehyde Oligomers ................................................. 20.2. Oligomeric Phenol Alcohols .................................................................... 20.3. Cyclic Phenol-formaldehyde Oligomers .................................................. 20.4. Branched Phenol-formaldehyde Oligomers ............................................ 20.5. Hydroquinone Oligomers ........................................................................ References .............................................................................................................. Table 21. Oligo(phenylenes) ................................................................................................... 21.1. o-oligo(phenylenes) ................................................................................ 21.2. m-oligo(phenylenes) ............................................................................... 21.3. p-oligo(phenylenes) ................................................................................ 21.4. Oligo(p-quinones) ................................................................................... References ..............................................................................................................

IV/90 IV/90 IV/90 IV/90 IV/90 IV/90 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/92 IV/92 IV/93 IV/94 IV/94 IV/95 IV/95 IV/96 IV/96 IV/96 IV/97 IV/98 IV/98

E. Oligomers Containing Heterocyclic Rings in the Main Chain .............................................. Table 22. Heterocyclic Oligomers ........................................................................................... 22.1 Oligo(furan) Derivatives .......................................................................... 22.2. Oligo(thiophene) Derivatives .................................................................. 22.3. Oligo(pyrrole) Derivatives ....................................................................... 22.4. Oligo(pyridine) Derivatives ...................................................................... 22.5. Cyclic Oligo(heterocyclics) ...................................................................... References .............................................................................................................. Table 23. Oligo(saccharides) .................................................................................................. 23.1. Oligomeric Pentoses ...............................................................................

IV/99 IV/99 IV/99 IV/100 IV/100 IV/100 IV/101 IV/101 IV/102 IV/102


Contents

xxiii

23.2. Oligomeric Hexoses ................................................................................ IV/102 23.3. Oligomeric Amino Sugars ....................................................................... IV/103 References .............................................................................................................. IV/104

V.

Physical Constants of Some Important Polymers

Physical Constants of Rubbery Polymers ...................................................................................................

V/1

A. Introduction ........................................................................................................................

V/1

B. Tables ................................................................................................................................ Table 1. 1,4-cis(96-98%)Poly(butadiene) ............................................................................. Table 2. Poly(butadiene-co-acrylonitrile) .............................................................................. Table 3. Poly(butadiene-co-styrene) ..................................................................................... Table 4. Poly(chloroprene)(CR Neoprene) ........................................................................... Table 5. Poly(isobutene)-co-isoprene) Butyl Rubber (IIR) .................................................... Table 6. Polyisoprene, Natural Rubber ................................................................................. Table 7. Ethylene-propylene-diene-terpolymer (EPDM) .......................................................

V/1 V/1 V/2 V/3 V/3 V/4 V/5 V/6

C. References .........................................................................................................................

V/6

Physical Constants of Poly(ethylene) ..........................................................................................................

V/9

A. Crystallographic Data and Crystallographic Modifications ..................................................

V/9

B. Molecular Parameters and Solution Properties ...................................................................

V/9

C. Crystallinity, Crystal Size and Crystallization Kinetics .........................................................

V/10

D. Equilibrium Thermodynamic Properties ..............................................................................

V/11

E. Other General Physical Properties .....................................................................................

V/12

F. Effect of Chain Branching (Short) on Physical Properties ...................................................

V/15

G. Properties of a Series of Selected Poly(ethylene) Samples ................................................

V/16

H. Properties of Typical Poly(ethylenes) .................................................................................

V/17

I.

References .........................................................................................................................

V/17

Physical Constants of Poly(propylene) ........................................................................................................

V/21

A. Crystallographic Data and Modifications of Isotactic Polypropylenes ..................................

V/21

B. Crystallographic Data and Modifications of Syndiotactic Polypropylenes ............................

V/21

C. Dimensions of Poly(propylene) Molecules ..........................................................................

V/22

D. Crystallinity and Crystallization Kinetics ..............................................................................

V/22

E. Equilibrium Thermodynamic Properties ..............................................................................

V/23

F. Other General Properties ...................................................................................................

V/24

G. Properties of Typical Mainly Isotactic Poly(propylenes) ......................................................

V/26

H. Properties of Some Commercial Poly(propylene) Grades ...................................................

V/26

I.

Mechanical Properties of Poly(propylene) Homopolymers ..................................................

V/27

J. Mechanical Properties of Poly(propylene) Random Copolymers ........................................

V/28

K. Mechanical Properties of Poly(propylene) Impact Copolymers ...........................................

V/28

L. References .........................................................................................................................

V/28

Physical Constants of Fluoropolymers ........................................................................................................

V/31

A. Introduction ........................................................................................................................

V/31


xxiv

Contents B. Physical Constants of Poly(tetrafluoroethylene) ................................................................. Notes ....................................................................................................................................... Infrared Absorption Spectrum of Poly(tetrafluoroethylene) ..................................................... References ..............................................................................................................................

V/31 V/37 V/38 V/39

C. Physical Constants of Melt Processible Fluorocarbon Polymers PFA and FEP .................. Notes ....................................................................................................................................... References ..............................................................................................................................

V/41 V/44 V/45

D. Physical Constants of Modified Poly(ethylene-co-tetrafluoroethylene) ................................ Notes ....................................................................................................................................... References ..............................................................................................................................

V/45 V/48 V/48

E. Physical Constants of Poly(vinylidene Fluoride) ................................................................. Notes ....................................................................................................................................... References ..............................................................................................................................

V/48 V/51 V/52

F. Physical Constants of Amorphous Fluoropolymers ............................................................. Notes ....................................................................................................................................... References ..............................................................................................................................

V/52 V/54 V/54

G. Physical Constants of Poly(chlorotrifluoroethylene) ............................................................ Notes ....................................................................................................................................... References ..............................................................................................................................

V/55 V/57 V/58

Physical Constants of Poly(acrylonitrile) .....................................................................................................

V/59

A. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9.

Physical Constants ............................................................................................. Crystallinity/Crystallization Behavior ....................................................................... Electric and Electronic Properties ........................................................................... Fiber Properties ...................................................................................................... Further Properties of Acrylic Fibers ........................................................................ Optical Properties ................................................................................................... Polymerization: Kinetic and Thermodynamic Data ................................................. Solubility/Solution Properties .................................................................................. Special Solid State Properties ................................................................................ Thermal and Thermodynamic Data ........................................................................

V/59 V/59 V/60 V/61 V/61 V/61 V/62 V/62 V/63 V/64

B. References .........................................................................................................................

V/64

Physical Constants of Poly(vinyl Chloride) ..................................................................................................

V/67

Physical Constants of Poly(vinyl Acetate) ...................................................................................................

V/77

Physical Constants of Poly(methyl Methacrylate) .......................................................................................

V/87

Physical Constants of Poly(styrene) ............................................................................................................

V/91

Physical Constants of Poly(oxymethylene) .................................................................................................

V/97

Physical Constants of Poly(oxyethylene-oxyterephthaloyl), (Poly(ethylene Terephthalate)) .....................

V/113

Physical Constants of Poly(oxytetramethylene-oxyterephthaloyl) and Copolymers with Tetramethylene Oxide Thermoplastic Elastomers .............................................................................

V/119

Physical Constants of Various Polyamides: Poly[imino(1-oxohexamethylene)], (Polyamide 6) Poly(iminoadipoyl-iminohexamethylene), (Polyamide 66), Poly(iminohexamethyleneiminosebacoyl), (Polyamide 610), Poly[imino(1-oxododecamethylene)], Poly(amide 12) ................

V/121


Contents

xxv

Physical Constants of Cellulose ..................................................................................................................

V/135

A. Introduction ........................................................................................................................

V/135

B. Solid State Properties ......................................................................................................... Table 1. Unit Cell Dimensions ............................................................................................... Table 2. Density .................................................................................................................... Table 3. Average Ordered Fraction of Cotton and Linters Measured by Various Techniques ............................................................................................................. Table 4. Average Ordered Fraction Measured by Various Techniques ................................ Table 5. Degree of Crystallinity ............................................................................................. Table 6. Crystallite Sizes ...................................................................................................... Table 7. X-ray Orientation of Cellulose Fibers ...................................................................... Table 8. Heat Capacity ......................................................................................................... Table 9. Thermal Expansion Coefficient ............................................................................... Table 10. Other Thermal Properties ....................................................................................... Table 11. Refractive Index and Birefringence ......................................................................... Table 12. Resistivity ................................................................................................................ Table 13. Dielectric Constant and Loss Factor at 1 kHz ......................................................... Table 14. Other Electrical Properties ...................................................................................... Table 15. Crystal Elastic Modulus E1 in Chain Direction ......................................................... Table 16. Fiber Strength, Elongation and Modulus .................................................................

V/136 V/136 V/136

C. Solution Properties ............................................................................................................. Table 17. Typical Non-aqueous Cellulose Solvents ............................................................... Table 18. Other Solvents ........................................................................................................ Table 19. Viscosity - Molecular Weight Relationships ............................................................ Table 20. Second Virial Coefficients ....................................................................................... Table 21. Sedimentation and Diffusion Coefficients ............................................................... Table 22. Partial Specific Volumes, ν2 .................................................................................... Table 23. Geometrical Chain Characteristics ......................................................................... Table 24. Polymer-solvent Interaction Parameters .................................................................

V/147 V/147 V/148 V/148 V/150 V/150 V/151 V/151 V/152

D. References .........................................................................................................................

V/152

Physical and Mechanical Properties of Some Important Polymers ............................................................

V/159

A. Introduction ........................................................................................................................

V/159

B. Narrative Descriptions ........................................................................................................ 1. Multipurpose Polymers ........................................................................................... 2. Polyolefins and Barrier Polymers ............................................................................ 3. Styrenics and Engineering Thermoplastics ............................................................. 4. Elastomers ..............................................................................................................

V/159 V/159 V/160 V/160 V/161

C. Properties of Commercial Polymers ................................................................................... Table 1. Multipurpose Thermoplastics .................................................................................. Table 2. Polyolefins and Barrier Polymers ............................................................................ Table 3. Styrenics and Engineering Thermoplastics ............................................................. Table 4. Elastomers ..............................................................................................................

V/162 V/162 V/164 V/166 V/168


V/136 V/137 V/137 V/138 V/140 V/140 V/141 V/141 V/144 V/144 V/145 V/146 V/146 V/147

xxvi VI.

Contents Solid State Properties

Crystallographic Data and Melting Points for Various Polymers ................................................................

VI/1

A. Introduction ........................................................................................................................ 1. Nomenclature .......................................................................................................... 2. Examples of Polymer Names .................................................................................. 2.1. Polymer Names Based on Source .......................................................... 2.2. Polymer Names Based on Structure ...................................................... References for Introduction .....................................................................................

VI/1 VI/1 VI/2 VI/2 VI/3 VI/5

B. Crystallographic Data for Various Polymers ....................................................................... Table 1. Poly(olefins) ............................................................................................................ Table 2. Poly(vinyls) and Poly(vinylidenes) .......................................................................... Table 3. Poly(aromatics) and Poly(imides) ........................................................................... Table 4. Poly(dienes) and Poly(diynes) ................................................................................ Table 5. Poly(peptides) ......................................................................................................... Table 6. Poly(amides) ........................................................................................................... Table 7. Poly(esters) ............................................................................................................. Table 8. Poly(urethanes) and Poly(ureas) ............................................................................ Table 9. Poly(ethers) ............................................................................................................. Table 10. Poly(oxides) ............................................................................................................ Table 11. Poly(sulfides) and Poly(sulfones) ............................................................................ Table 12. Poly(saccharides) ................................................................................................... Table 13. Other Polymers .......................................................................................................

VI/5 VI/6 VI/13 VI/15 VI/22 VI/26 VI/33 VI/40 VI/49 VI/51 VI/52 VI/57 VI/59 VI/64

C. Melting Points of Polymers ................................................................................................. Cellulose, see Poly (1,4-β-D-glucose) to Poly(4,4'-methylenediphenylene isophthalamide) ....................................................................................................... Poly(4,4'-methylenediphenylene octadecamethylenediurea) to Poly(p-xylylene undecanediamide) ..................................................................................................

VI/71 VI/71 VI/94

D. Appendix: Formula Index to the Tables .............................................................................. VI/113 0 to 4 ....................................................................................................................................... VI/114 5 to 30 ..................................................................................................................................... VI/133 E. References ......................................................................................................................... VI/159 1 to 839 ................................................................................................................................... VI/159 840 to 1946 ............................................................................................................................. VI/174 Glass Transition Temperatures of Polymers ............................................................................................... VI/193 A. Introduction ........................................................................................................................ VI/194 1. Example of a Property Change at Tg ...................................................................... VI/194 2. Tg: a "Non-Equilibrium" Transition ........................................................................... VI/195 B. Tg Measurement Methods .................................................................................................. VI/195 1. Data Interpretation .................................................................................................. VI/195 2. Oscillating Load Methods ........................................................................................ VI/196 C. Other Factors Affecting Tg .................................................................................................. VI/196 1. Structure ................................................................................................................. VI/196 This page has been reformatted by Knovel to provide easier navigation.

2. 3. 4. 5. 6.

Contents

xxvii

Crystallinity/Crosslinking ......................................................................................... Diluents ................................................................................................................... Molecular Weight .................................................................................................... Thermal History ....................................................................................................... Pressure ..................................................................................................................

VI/196 VI/197 VI/197 VI/197 VI/197

D. Estimation Methods for the Glass Transition Temperature ................................................. VI/197 E. Classification, Nomenclature, and Abbreviations ................................................................ VI/197 1. Naming Conventions ............................................................................................... VI/198 2. Abbreviations .......................................................................................................... VI/198 F. Tables of Glass Transition Temperatures of Polymers ....................................................... VI/198 Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... VI/198 1.1 Poly(acrylics) and Poly(methacrylics) ..................................................... VI/198 1.1.1 Poly(acrylic acid) and Poly(acrylic Acid Esters) ............................... VI/198 1.1.2 Poly(acrylamides) ............................................................................. VI/201 1.1.3 Poly(methacrylic Acid) and Poly(methacrylic Acid Esters) .............. VI/201 1.1.4 Poly(methacrylamides) ..................................................................... VI/205 1.1.5 Other α- and β-substituted Poly(acrylics) and Poly(methacrylics) ............................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(dienes) ............................................................................................ 1.4 Poly(styrenes) ......................................................................................... 1.5 Poly(vinyl Alcohol) and Poly(vinyl Ketones) ............................................ 1.6 PoIy(vinyl Esters) .................................................................................... 1.7 Poly(vinyl Ethers) and Poly(vinyl Thioethers) ......................................... 1.8 Poly(vinyl Halides) and Poly(vinyl Nitriles) .............................................. 1.9 Others ..................................................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Others ..................................................................................................... Table 3. Main-chain Acyclic Heteroatom Polymers .............................................................. 3.1 Main-chain –C–O–C– Polymers .............................................................

VI/205 VI/205 VI/207 VI/209 VI/212 VI/213 VI/214 VI/215 VI/216 VI/218 VI/218 VI/218 VI/219 VI/219

3.1.1 Poly(anhydrides) .............................................................................. VI/219 3.1.2 Poly(carbonates) .............................................................................. VI/219 3.1.3 Poly(esters) ...................................................................................... VI/221 3.1.4 Poly(ether Ketones) ......................................................................... VI/226 3.1.5 Poly(oxides) ...................................................................................... VI/226 3.2

3.1.6 Poly(urethanes) ................................................................................ VI/229 Main-chain O-heteroatom Polymers ....................................................... VI/231 3.2.1 Nitroso-polymers .............................................................................. VI/231 3.2.2 PoIy(siloxanes) ................................................................................. VI/231 3.2.3 Poly(sulfonates) ................................................................................ VI/233


xxviii

Contents 3.3

Main-chain –C–(S)n–C- and –C–S–N– Polymers ................................... VI/233 3.3.1 Poly(sulfides) .................................................................................... VI/233 3.3.2 Poly(sulfones) and Poly(sulfonamides) ........................................... VI/234

3.4

3.3.3 Poly(thioesters) ................................................................................ VI/235 Main-chain –C–N–C Polymers ............................................................... VI/235 3.4.1 Poly(amides) .................................................................................... VI/235 3.4.2 Poly(anilines) .................................................................................... VI/241 3.4.3 Poly(imides) ...................................................................................... VI/241 3.4.4 Poly(imines) ...................................................................................... VI/241

3.4.5 Poly(ureas) ....................................................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(silanes) and Poly(silazanes) ........................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Carbohydrates ........................................................................................ 4.2 Liquid Crystals ........................................................................................ 4.3 Natural Polymers .................................................................................... 4.4 Poly(acetals) ........................................................................................... 4.5 Poly(anhydrides) ..................................................................................... 4.6 Poly(benzimidazoles) .............................................................................. 4.7 Poly(benzothiazinophenothiazines) ........................................................ 4.8 Poly(benzothiazoles) .............................................................................. 4.9 Poly(benzoxazlnes) ................................................................................ 4.10 Poly(benzoxazoles) ................................................................................ 4.11 Poly(carboranes) .................................................................................... 4.12 Poly(dibenzofurans) ................................................................................ 4.13 Poly(dioxoisoindolines) ........................................................................... 4.14 Poly(fluoresceins) ................................................................................... 4.15 Poly(furan Tetracarboxylic Acid Diimides) .............................................. 4.16 Poly(oxabicyclononanes) ........................................................................ 4.17 Poly(oxadiazoles) ................................................................................... 4.18 Poly(oxindoles) ....................................................................................... 4.19 Poly(oxoisoindolines) .............................................................................. 4.20 Poly(phthalazines) .................................................................................. 4.21 Poly(phthalides) ...................................................................................... 4.22 Poly(piperazines) .................................................................................... 4.23 Poly(piperidines) ..................................................................................... 4.24 Poly(pyrazinoquinoxalines) ..................................................................... 4.25 Poly(pyrazoles) ....................................................................................... 4.26 Poly(pyridazines) .................................................................................... 4.27 Poly(pyridines) ........................................................................................ 4.28 Poly(pyromellitimides) ............................................................................. 4.29 Poly(pyrrolidines) ....................................................................................


VI/242 VI/242 VI/243 VI/243 VI/243 VI/244 VI/244 VI/244 VI/244 VI/245 VI/245 VI/245 VI/245 VI/245 VI/245 VI/246 VI/246 VI/247 VI/247 VI/247 VI/248 VI/248 VI/248 VI/248 VI/248 VI/248 VI/249 VI/249 VI/249 VI/249 VI/249 VI/249 VI/250

Contents 4.30 Poly(quinones) ........................................................................................ 4.31 Poly(quinoxalines) .................................................................................. 4.32 Poly(triazines) ......................................................................................... 4.33 Poly(triazoles) ......................................................................................... Table 5. Copolymers .............................................................................................................

xxix VI/250 VI/250 VI/252 VI/252 VI/252

G. References ......................................................................................................................... VI/253 1 to 953 ................................................................................................................................... VI/253 954 to 1560 ............................................................................................................................. VI/268 Rates of Crystallization of Polymers ............................................................................................................ VI/279 A. Introduction ........................................................................................................................ 1. Background ............................................................................................................. 1.1 General Remarks .................................................................................... 1.2 Background ............................................................................................. 1.3 Morphological Outline/Growth Features ................................................. 2. General Principles and Techniques Involved in Crystallization Rate Studies ......... 2.1 Kinetics of Bulk Transformations ............................................................ 2.2 Thermodynamic Crystallization Models .................................................. 2.3 Growth Kinetics of Lamellar Structures: Crystals and Spherulites ......... 3. Other Significant Aspects of Crystallization ............................................................ 3.1 Nonisothermal Crystallization ................................................................. 3.2 Crystallization of Blends ......................................................................... 3.3 Solvent and Pressure-induced Crystallization ........................................ 3.4 Crystallization of Mesophases ................................................................ 3.5 Flow Induced Crystallization ................................................................... 3.6 Epitaxial Crystallization ........................................................................... 3.7 Orientational Crystallization .................................................................... 3.8 Crystallization of Copolymers ................................................................. 3.9 Computer Simulations ............................................................................

VI/280 VI/280 VI/280 VI/280 VI/281 VI/282 VI/282 VI/284 VI/284 VI/286 VI/286 VI/287 VI/288 VI/288 VI/289 VI/289 VI/289 VI/290 VI/290

B. Tables of Rates of Crystallization of Various Polymers ....................................................... VI/291 1. Rates of Crystal Growth .......................................................................................... VI/291 Table 1. Poly(alkenes), Poly(dienes), Poly(vinyls) ................................................ VI/291 1.1

2.

Homopolymer Melts ......................................................................... VI/291

1.2 Solutions ........................................................................................... Table 2. Poly(oxides) ............................................................................................ Rates of Radial Spherulitic Growth ......................................................................... Table 3. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ 3.1

VI/296 VI/300 VI/304 VI/304


3.2 Blends ............................................................................................... VI/312 Table 4. Poly(oxides) ............................................................................................ VI/315 4.1


4.2

Complexes ....................................................................................... VI/318

4.3

Blends ............................................................................................... VI/319


xxx

Contents Table 5. Poly(carbonates) ..................................................................................... VI/326 Table 6. Poly(esters) ............................................................................................. VI/327 6.1


6.2

Blends ............................................................................................... VI/329

6.3 Copolymers ...................................................................................... VI/331 Table 7. Poly(amides) ........................................................................................... VI/331 Table 8. Poly(siloxanes) ....................................................................................... VI/334 8.1


8.2 Copolymers ...................................................................................... VI/334 Table 9. Others ..................................................................................................... VI/336 9.1 3.

Homopolymers Melts ....................................................................... VI/336

9.2 lonomers ........................................................................................... VI/340 Rates of Bulk Crystallization (Avrami Constants) ................................................... VI/341 Table 10. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ VI/341 10.1 Melts and Solutions .......................................................................... VI/341 10.2 Blends and Copolymers ................................................................... VI/353 Table 11. Poly(oxides) ............................................................................................ VI/365 11.1 Homopolymer Melts ......................................................................... VI/365 11.2 Blends ............................................................................................... VI/371 Table 12. Poly(carbonates) ..................................................................................... VI/372 Table 13. Poly(esters) ............................................................................................. VI/373 13.1 Homopolymer melts ......................................................................... VI/373 13.2 Blends and Copolymers ................................................................... VI/377 Table 14. Poly(amides) ........................................................................................... VI/379 14.1 Blends of Poly(amides) .................................................................... VI/382 Table 15. Poly(urethanes) ...................................................................................... VI/383 Table 16. Table 17. Table 18. Table 19.

15.1 Blends of Poly(urethanes) ................................................................ Poly(siloxanes) ....................................................................................... Poly(phosphazenes) ............................................................................... Others ..................................................................................................... Composites .............................................................................................

VI/383 VI/384 VI/384 VI/385 VI/389

19.1 Composites of Blends ...................................................................... VI/390 C. References ......................................................................................................................... VI/391 Isomorphous Polymers Pairs ....................................................................................................................... VI/399 A. Introduction ........................................................................................................................ VI/399 B. Techniques ......................................................................................................................... VI/400 C. Tables of lsomorphous Pairs of Monomer Units ................................................................. Table 1. lsomorphous Units Within the Same Macromolecules (Copolymers) ..................... 1.1 lsomorphous Units with Different Chemical Constitution ........................ 1.2 lsomorphous Units with Different Configurations and/or with Headto-head, Head-to-tail Constitutional Disorder ..........................................


VI/401 VI/401 VI/401 VI/405

Contents

xxxi

Table 2. Isomorphism of Macromolecules ............................................................................ VI/405 D. References ......................................................................................................................... VI/406 Miscible Polymers ........................................................................................................................................ VI/409 A. Definition of Miscibility ........................................................................................................ VI/409 B. Data Collection ................................................................................................................... VI/410 C. Arrangement of the Tables ................................................................................................. VI/410 D. Tables ................................................................................................................................ Table 1. Chemically Dissimilar Polymer Pairs Miscible in the Amorphous State at Room Temperature ................................................................................................. Table 2. Polymer Pairs Containing One Monomer in Common, Miscible in the Amorphous State at Room Temperature ................................................................ Table 3. Chemically Dissimilar Polymer Triads (and Tetrads) Miscible in the Amorphous State at Room Temperature ................................................................ Table 4. Polymer Pairs Miscible in the Amorphous State at Room Temperature; Molecular Weight Dependence Investigated .......................................................... Table 5. Polymer Pairs That Appear to Have High Temperature Miscibility Although Immiscible at or Below Room Temperature ............................................................ Table 6. Polymer Pairs Miscible at Room Temperature That Appear to Have a Lower Critical Solution Temperature (LCST) Above Room Temperature ......................... Table 7. Polymer Pairs That Appear to Have Both a Lower Critical Solution Temperature and a Upper Critical Solution Temperature ....................................... Table 8. Polymer Pairs That Cocrystallize ............................................................................

VI/411 VI/411 VI/444 VI/448 VI/450 VI/452 VI/454 VI/458 VI/459

E. References ......................................................................................................................... VI/461 Heat Capacities of High Polymers ............................................................................................................... VI/483 A. Introduction ........................................................................................................................ VI/483 B. Experimental Curves .......................................................................................................... VI/485 C. Data Tables for Solids and Liquids ..................................................................................... Table 1. cis-1,4-Poly(butadiene) (PBDc) .............................................................................. Table 2. trans-1,4-Poly(butadiene) (PBDt) ............................................................................ Table 3. cis-1,4-Poly(2-methylbutadiene) (PMBD) ............................................................... Table 4. Poly(ethylene) (PE) ................................................................................................. Table 5. Poly(propylene) (PP) ............................................................................................... Table 6. PoIy(1-butene) (PB) ................................................................................................ Table 7. PoIy(1-pentene) (PPE) ............................................................................................ Table 8. PoIy(1-hexene) (PHE) ............................................................................................. Table 9. Poly(isobutene) (PIB) .............................................................................................. Table 10. Poly(4-methyl-1-pentene) (P4MPE) ........................................................................ Table 11. Poly(tetrafluoroethylene) (PTFE) ............................................................................ Table 12. Poly(vinyl Fluoride) (PVF) ....................................................................................... Table 13. Poly(vinylidene Fluoride) (PVF2) ............................................................................ Table 14. Poly(trifluoroethylene) (P3FE) ................................................................................. Table 15. Poly(vinyl Chloride) (PVC) ......................................................................................


VI/486 VI/486 VI/487 VI/488 VI/488 VI/489 VI/490 VI/490 VI/491 VI/492 VI/492 VI/493 VI/494 VI/494 VI/495 VI/496

xxxii

Contents Table 16. Table 17. Table 18. Table 19. Table 20. Table 21. Table 22. Table 23. Table 24. Table 25. Table 26. Table 27. Table 28. Table 29. Table 30. Table 31. Table 32. Table 33. Table 34. Table 35. Table 36. Table 37. Table 38. Table 39. Table 40. Table 41. Table 42. Table 43. Table 44. Table 45. Table 46. Table 47. Table 48. Table 49. Table 50.

Poly(vinylidene Chloride) (PVC2) ........................................................................... Poly(chlorotrifluoroethylene) (PC3FE) .................................................................... Poly(vinyl Alcohol) (PVA) ........................................................................................ Poly(vinyl Acetate) (PVAc) ...................................................................................... Poly(styrene) (PS) ................................................................................................... Poly(α-methylstyrene) (PMS) .................................................................................. Poly(vinyl Benzoate) (PVBZ) .................................................................................. Poly(methyl Acrylate) (PMA) ................................................................................... Poly(ethyl Acrylate) (PEA) ...................................................................................... Poly(n-butyl Acrylate) (PnBA) ................................................................................. Poly(iso-butyl Acrylate) (PIBA) ................................................................................ Poly(methacrylic Acid) (PMAA) ............................................................................... Poly(methyl Methacrylate) (PMMA) ........................................................................ Poly(ethyl Methacrylate) (PEMA) ............................................................................ Poly(n-butyl Methacrylate) (PnBMA) ....................................................................... Poly(iso-butyl Methacrylate) (PIBMA) ..................................................................... Poly(hexyl Methacrylate) (PHMA) ........................................................................... Poly(acrylonitrile) (PAN) .......................................................................................... Poly(methacrylamide) (PMAM) ............................................................................... Poly(oxy-1-oxoethylene) (PCL) ............................................................................... Poly(oxy-1-oxohexamethylene) (PCL) .................................................................... Poly(oxyethyleneoxyterephthaloyl) (PET) ............................................................... Poly(imino-(1-oxohexamethylene)) (Nylon 6) ......................................................... Poly(iminoadipoyliminohexamethylene) (Nylon 66) ................................................ Poly(iminoadipoyliminododecamethylene) (Nylon 612) .......................................... Poly(oxymethylene) (POM) ..................................................................................... Poly(oxyethylene) ................................................................................................... Poly(oxytrimethylene) (PO3M) ................................................................................ Poly(oxytetramethylene) (PO4M) ............................................................................ Poly(oxypropylene) (POPr) ..................................................................................... Poly(oxy-1,4-phenylene) (POPh) ............................................................................ Poly(oxy-2,6-dimethyl-1,4-phenylene) (PPO) ......................................................... Poly(oxy-2,6-diphenyl-1,4-phenylene) (POPPO) .................................................... Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene- 1,4-phenylene) (PC) ............ Trigonal Selenium (SeT) .........................................................................................

VI/496 VI/497 VI/498 VI/498 VI/499 VI/500 VI/500 VI/501 VI/502 VI/502 VI/503 VI/504 VI/504 VI/505 VI/506 VI/506 VI/507 VI/508 VI/508 VI/509 VI/510 VI/510 VI/511 VI/512 VI/512 VI/513 VI/514 VI/514 VI/515 VI/515 VI/516 VI/517 VI/517 VI/518 VI/519

D. References ......................................................................................................................... VI/519 Surface and Interfacial Tensions of Polymers, Oligomers, Plasticizers, and Organic Pigments ............... VI/521 A. Introduction ........................................................................................................................ 1. Definition ................................................................................................................. 2. Temperature Dependence ...................................................................................... 3. Macleod's Relation .................................................................................................. 4. Molecular Weight Dependence ............................................................................... 5. Effects of Glass and Crystal-melt Transitions ......................................................... This page has been reformatted by Knovel to provide easier navigation.

VI/521 VI/521 VI/522 VI/522 VI/522 VI/522

Contents 6. 7.

xxxiii

Effect of Surface Chemical Constitution ................................................................. VI/523 Dispersion (Nonpolar) and Polar Components ....................................................... VI/523

B. Tables ................................................................................................................................ VI/523 Table 1. Surface Chemical Constitution and Surface Tension ............................. VI/524 1.1

Hydrocarbon Surfaces ..................................................................... VI/524

1.2

Fluorocarbon Surfaces ..................................................................... VI/524

1.3

Chlorocarbon Surfaces .................................................................... VI/524

1.4 Silicane Surfaces .............................................................................. VI/524 Table 2. Surface Tension, Polarity, and Macleod's Exponent for Amorphous Surfaces .............................................................................. VI/524 2.1

Hydrocarbon Polymers ..................................................................... VI/524

2.2

Styrene Polymers ............................................................................. VI/525

2.3

Halogenated Hydrocarbon Polymers ............................................... VI/525

2.4

Vinyl Polymers - Esters .................................................................... VI/526

2.5

Vinyl Polymers - Others ................................................................... VI/526

2.6

Acrylic Polymers - Nonfluorinated .................................................... VI/526

2.7

Acrylic Polymers - Fluorinated ......................................................... VI/527

2.8

Methacrylic Polymers - Nonfluorinated ............................................ VI/527

2.9

Methacrylic Polymers - Fluorinated ................................................. VI/527

2.10 Methacrylic Hydrogels ...................................................................... VI/527 2.11 Poly(ethers) ...................................................................................... VI/528 2.12 Poly(ether) Copolymers ................................................................... VI/529 2.13 Poly(esters) ...................................................................................... VI/529 2.14 Poly(carbonates) .............................................................................. VI/530 2.15 Poly(sulfones) ................................................................................... VI/530 2.16 Phenoxy Resins ............................................................................... VI/530 2.17 Epoxy Resins ................................................................................... VI/530 2.18 Poly(amides) .................................................................................... VI/530 2.19 Poly(imides) ...................................................................................... VI/531 2.20 Poly(imines) ...................................................................................... VI/531 2.21 Poly(urethanes) ................................................................................ VI/531 2.22 Poly(siloxanes) ................................................................................. VI/531 2.23 Organosilanes - Hydrolyzed and Condensed Films ........................ VI/532 2.24 Cellulosics ........................................................................................ VI/533 2.25 Poly(peptides) .................................................................................. VI/533 2.26 Miscellaneous ................................................................................... VI/533 Table 3. lnterfacial Tension for Amorphous Interfaces ......................................... VI/535 3.1

Hydrocarbon Polymers vs. Others ................................................... VI/535

3.2

Styrene Polymers vs. Others ........................................................... VI/537

3.3

Vinyl Polymers vs. Others ................................................................ VI/537

3.4

Acrylic Polymers vs. Others ............................................................. VI/538


xxxiv

Contents 3.5

Methacrylic Polymers vs. Others ..................................................... VI/538

3.6

Poly(ethers) vs. Others .................................................................... VI/539

3.7

Poly(esters) vs. Others ..................................................................... VI/539

3.8

Poly(amides) vs. Others ................................................................... VI/539

3.9

Epoxy Resins vs. Others .................................................................. VI/539

3.10 Poly(Siloxanes) vs. Others ............................................................... VI/539 3.11 Miscellaneous ................................................................................... VI/540 C. References ......................................................................................................................... VI/540 Permeability and Diffusion Data .................................................................................................................. VI/543 A. Introduction ........................................................................................................................ VI/543 B. Conversion Factors for Various Units of the Permeability Coefficient ................................. VI/545 C. Tables ................................................................................................................................ Table 1. Permeability Coefficients, Diffusion Coefficients, and Solubility Coefficients of Polymers ............................................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(styrenes) ......................................................................................... 1.3 Poly(methacrylates) ................................................................................ 1.4 Poly(nitriles) ............................................................................................ 1.5 Poly(vinyls) ............................................................................................. 1.6 Fluorine Containing Polymers ................................................................. 1.7 Poly(dienes) ............................................................................................ 1.8 Poly(xylylenes) ........................................................................................ 1.9 Poly(oxides) ............................................................................................ 1.10 Poly(esters), Poly(carbonates) ............................................................... 1.11 PoIy(siloxanes) ....................................................................................... 1.12 Poly(amides), Poly(imides) ..................................................................... 1.13 Poly(urethanes) ...................................................................................... 1.14 Poly(sulfones) ......................................................................................... 1.15 Poly(aryl Ether Ether Ketone) ................................................................. 1.16 Cellulose and Derivatives ....................................................................... Table 2. Permeability Coefficients of Six Different Fluorinated Hydrocarbons through Polymers ................................................................................................................. Table 3. Permeability Coefficients of Various Organic Compounds through Lowdensity Poly(ethylene) ............................................................................................. Table 4. Permeability Coefficients and Diffusion Coefficients of an Equimolar Mixture of Various Compounds (1.25 M Each) through High-density Poly(ethylene) .......... Table 5. Permeability Coefficients of Various Organic Compounds through Highdensity Poly(ethylene) and Poly(propylene) ........................................................... Table 6. Permeability Coefficients of Various Organic Compounds through Irradiation Crosslinked Low-density Poly(ethylene) ................................................................. Table 7. Permeability Coefficients of Cases through Irradiation Crosslinked Lowdensity Poly(ethylene) .............................................................................................


VI/545 VI/545 VI/545 VI/547 VI/548 VI/549 VI/549 VI/552 VI/553 VI/555 VI/555 VI/555 VI/558 VI/559 VI/560 VI/560 VI/561 VI/561 VI/562 VI/562 VI/564 VI/564 VI/564 VI/565

Contents

xxxv

Table 8. Permeability Coefficients of Chemically Crosslinked Poly(oxypropylene) .............. Table 9. Permeability Coefficients of Gases through Various Elastomers ............................ Table 10. Permeability Coefficients of Gases through Various Commercial Elastomers at 35°C. ................................................................................................................... Table 11. Permeability, Diffusion and Solubility Coefficients of Alkanes through Santoprene™ (Blend of Ethylene-propylene Copolymer and lsotactic Poly(propylene)) ...................................................................................................... Table 12. Permeability, Diffusion and Solubility Coefficients of Esters through Poly(epichlorohydrin) (ECO) ...................................................................................

VI/565 VI/566 VI/566

VI/566 VI/567

D. References ......................................................................................................................... VI/568 Refractive Indices of Polymers .................................................................................................................... VI/571 A. Introduction ........................................................................................................................ VI/571 B. Molar Refraction ................................................................................................................. VI/571 C. Refractive Indices of Heterogeneous Polymers .................................................................. VI/572 D. Optical Anisotropy .............................................................................................................. VI/572 E. Applications ........................................................................................................................ Table 1. Intrinsic Optical Properties of Selected Polymers ................................................... Table 2. Average Refractive Indices of Polymers (in Order of Increasing n) ........................ Table 3. Average Refractive Indices of Polymers (in Alphabetical Order) ............................

VI/573 VI/573 VI/574 VI/578

F. References ......................................................................................................................... VI/582 Radiation Resistance of Plastics and Elastomers ....................................................................................... VI/583 A. Introduction ........................................................................................................................ 1. General Comments ................................................................................................. 2. Criterion for Radiation Resistance .......................................................................... 3. Factors of Influence and Their Consideration in Tables ......................................... 3.1 Type of Polymer and Formulation ........................................................... 3.2 Type of Radiation and Dosimetry ........................................................... 3.3 Dose Rate and the Atmosphere ............................................................. 3.4 Temperature ........................................................................................... 3.5 Other Stresses ........................................................................................

VI/583 VI/583 VI/583 VI/583 VI/583 VI/584 VI/584 VI/584 VI/584

B. List of Symbols Used .......................................................................................................... VI/584 C. Tables of Table 1. Table 2. Table 3. Table 4.

Radiation Resistance .......................................................................................... Thermoplastics ........................................................................................................ Elastomers .............................................................................................................. Aromatic Polymers .................................................................................................. Organic Composite Materials ..................................................................................

VI/585 VI/585 VI/586 VI/587 VI/588

D. References ......................................................................................................................... VI/588 PVT Relationships and Equations of State of Polymers ............................................................................. VI/591 A. Introduction ........................................................................................................................ VI/591 B. Isothermal Compressibility Equations ................................................................................. VI/592 C. Empirical or Semiempirical 3-Parameter Equations of State ............................................... VI/593 D. Lattice or Quasi Lattice Models .......................................................................................... VI/593 This page has been reformatted by Knovel to provide easier navigation.

xxxvi

Contents E. Continuum Models .............................................................................................................. VI/594 F. Tables ................................................................................................................................ Table 1. Zero Pressure Volume V0(T) and Bulk Modulus B0(T) ............................................ Table 2. Abbreviations of Polymer Names and the Experimental TemperaturePressure Range for Polymer Liquids ...................................................................... Table 3. PVT Properties of Other Polymers .......................................................................... Table 4. Characteristic Parameters for the Sanchez-cho Equation of State ......................... Table 5. Characteristic Parameters for the Hartmann-haque Equation of State ................... Table 6. Characteristic Parameters for the Simple Cell Model Equation of State ................. Table 7. Characteristic Parameters for the Flory, Orwoll and Vrij Equation of State ............ Table 8. Characteristic Parameters for the Simha-somcynsky Equation of State ................ Table 9. Characteristic Parameters for the Sanchez-lacombe Equation of State ................. Table 10. Characteristic Parameters for the AHS + vdW Equation of State ...........................

VI/595 VI/595 VI/596 VI/597 VI/597 VI/597 VI/598 VI/599 VI/599 VI/600 VI/600

G. References ......................................................................................................................... VI/601

VII. Solution Properties Viscosity – Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain Molecules ............................................................................................................................................

VII/1

A. Introduction ........................................................................................................................ 1. The Viscosity - Molecular Weight Relationship ....................................................... 2. Unperturbed Dimensions of Linear Chain Molecules ..............................................

VII/2 VII/2 VII/4

B. Effect of Molecular Weight Distribution on the Viscosity Constant K ...................................

VII/5

a

C. Tables of Viscosity - Molecular Weight Relationships, [η] = KM ........................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes), Poly(acetylenes) ............................................................. 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 1.5 Poly(vinyl Ethers) .................................................................................... 1.6 Poly(vinyl Alcohol), Poly(vinyl Halides) ................................................... 1.7 Poly(vinyI Esters) .................................................................................... 1.8 Poly(styrene) and Derivatives ................................................................. 1.9 Other Compounds .................................................................................. 1.10 Copolymers ............................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides), Poly(ethers) ....................................................................... 3.2 Poly(esters), Poly(carbonates) ............................................................... 3.3 Poly(amides) ........................................................................................... 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(ureas), Poly(urethanes), Poly(imines) ............................................ 3.6 Poly(sulfides) .......................................................................................... 3.7 Poly(phosphates) .................................................................................... This page has been reformatted by Knovel to provide easier navigation.

VII/5 VII/5 VII/5 VII/7 VII/10 VII/13 VII/17 VII/17 VII/18 VII/19 VII/24 VII/27 VII/31 VII/32 VII/32 VII/34 VII/36 VII/38 VII/39 VII/39 VII/39

Contents

xxxvii

3.8 Poly(siloxanes), Poly(silsesquioxanes) ................................................... 3.9 Poly(heterocyclics) .................................................................................. 3.10 Copolymers (Maleic Anhydride, Sulfones) .............................................. 3.11 Other Compounds .................................................................................. Table 4. Cellulose and Derivatives, Poly(saccharides) ......................................................... Table 5. Miscellaneous .........................................................................................................

VII/40 VII/41 VII/42 VII/42 VII/43 VII/46

D. Calculated Unperturbed Dimensions of Freely Rotating Chains .........................................

VII/46

E. Unperturbed Dimensions of Linear Polymer Molecules ...................................................... Table 6. Main-chain Acyclic Carbon Polymers ..................................................................... 6.1 Poly(dienes) ............................................................................................ 6.2 Poly(alkenes), Poly(acetylenes) ............................................................. 6.3 Poly(acrylic Acid) and Derivatives .......................................................... 6.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 6.5 Poly(vinyl Ethers), Poly(vinyl Alcohol), Poly(vinyl Esters), Poly(vinyl Halides) .................................................................................. 6.6 Poly(styrene) and Derivatives ................................................................. 6.7 Other Compounds .................................................................................. 6.8 Copolymers ............................................................................................. Table 7. Main-chain Carbocyclic Polymers ........................................................................... Table 8. Main-chain Heteroatom Polymers ........................................................................... 8.1 Poly(oxides), Poly(ethers) ....................................................................... 8.2 Poly(esters), Poly(carbonates) ............................................................... 8.3 Poly(amides) ........................................................................................... 8.4 Poly(amino Acids) ................................................................................... 8.5 Poly(urethanes) ...................................................................................... 8.6 Poly(sulfides) .......................................................................................... 8.7 Poly(phosphates) .................................................................................... 8.8 Poly(siloxanes), Poly(silsesquioxanes), Poly(silmethylenes) ................. 8.9 Poly(heterocyclics) .................................................................................. 8.10 Copolymers (Maleic Anhydride, Sulfones, Siloxanes) ............................ 8.11 Other Compounds .................................................................................. Table 9. Cellulose and Derivatives, Poly(saccharides) .........................................................


F. References .........................................................................................................................

VII/68

Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, Frictional Ratios, and Second Virial Coefficients of Polymers in Solution ............................................................................

VII/85

A. Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ............................................................................ 1. Introduction ............................................................................................................. 1.1. Sedimentation Coefficient ....................................................................... 1.2. Diffusion Coefficient ................................................................................ 1.3. Molar Mass Averages Determined from Sedimentation and Diffusion Coefficients .............................................................................. 1.4. Partial Specific Volumes ......................................................................... This page has been reformatted by Knovel to provide easier navigation.

VII/53 VII/54 VII/56 VII/58 VII/60 VII/60 VII/60 VII/61 VII/63 VII/63 VII/63 VII/63 VII/64 VII/64 VII/64 VII/65 VII/66 VII/66


xxxviii

Contents 1.5. 1.6. 1.7.

Frictional Ratios ...................................................................................... List of Symbols and Abbreviations .......................................................... Miscellaneous .........................................................................................

B. Tables of Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ...................................................... Table 1. Poly(alkenes) .......................................................................................................... Table 2. Poly(dienes) ............................................................................................................ Table 3. Acrylic Polymers ..................................................................................................... Table 4. Vinyl Polymers ........................................................................................................ Table 5. Styrene Polymers .................................................................................................... Table 6. (O, C)-Heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... Table 7. (N, C)- and (O, N, C)-Heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Table 8. Other Synthetic Polymers ....................................................................................... Table 9. Inorganic Polymers ................................................................................................. Table 10. Poly(saccharides) ................................................................................................... Table 11. Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................

VII/89 VII/90 VII/91 VII/92 VII/92 VII/94 VII/96 VII/105 VII/109 VII/134 VII/137 VII/140 VII/141 VII/144 VII/157

C. Second Virial Coefficients of Polymers in Solution .............................................................. 1. Introduction ............................................................................................................. 1.1. Colligative Properties .............................................................................. 1.2. Scattering Methods ................................................................................. 1.3. Sedimentation Velocity ........................................................................... 1.4. Sedimentation Equilibrium ...................................................................... 1.5. p–V–T Measurements ............................................................................ 1.6. Averages of the Second Virial Coefficient .............................................. 1.7. Second Virial Coefficient – Molar Mass Relationship ............................. 1.8. Temperature Dependence, Pressure Dependence ................................ 1.9. Abbreviations .......................................................................................... 1.10. Miscellaneous .........................................................................................

VII/163 VII/163 VII/163 VII/163 VII/163 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164

D. Tables of Table 12. Table 13. Table 14. Table 15. Table 16. Table 17. Table 18.

VII/165 VII/165 VII/168 VII/170 VII/177 VII/179 VII/188

Table 19. Table 20. Table 21. Table 22.

Second Virial Coefficients of Polymers in Solution .............................................. Poly(alkenes), Poly(alkynes) ................................................................................... Poly(dienes) ............................................................................................................ Poly(acrylics) ........................................................................................................... Poly(vlnyls) .............................................................................................................. Poly(styrenes) ......................................................................................................... (O, C)-heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... (N, C)- and (O, N, C)-heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Other Synthetic Polymers ....................................................................................... Inorganic Polymers ................................................................................................. Poly(saccharides) ................................................................................................... Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................

VII/191 VII/192 VII/192 VII/194 VII/196

E. References ......................................................................................................................... VII/198 This page has been reformatted by Knovel to provide easier navigation.

Contents

xxxix

Polymolecularity Correction Factors ............................................................................................................ VII/215 A. List of Symbols Used .......................................................................................................... VII/216 B. Introduction ........................................................................................................................ VII/217 Table 1 .................................................................................................................................... VII/223 C. Polymolecularity Correction Factors for Intrinsic Viscosity Versus Molecular Weight Relationship ....................................................................................................................... Table 2 .................................................................................................................................... Table 3 .................................................................................................................................... Table 4 .................................................................................................................................... Table 5 .................................................................................................................................... Table 6 .................................................................................................................................... Table 7 .................................................................................................................................... Table 8 .................................................................................................................................... Table 9 .................................................................................................................................... Table 10 .................................................................................................................................. Table 11 .................................................................................................................................. Table 12 .................................................................................................................................. Table 13 .................................................................................................................................. Table 14 .................................................................................................................................. Table 15 .................................................................................................................................. Table 16 .................................................................................................................................. Table 17 .................................................................................................................................. Table 18 .................................................................................................................................. Table 19 ..................................................................................................................................

VII/223 VII/223 VII/223 VII/223 VII/224 VII/224 VII/224 VII/224 VII/224 VII/225 VII/225 VII/225 VII/225 VII/225 VII/226 VII/226 VII/226 VII/226 VII/226

D. Polymolecularity Correction Factors for Sedimentation Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 20 .................................................................................................................................. Table 21 .................................................................................................................................. Table 22 .................................................................................................................................. Table 23 .................................................................................................................................. Table 24 .................................................................................................................................. Table 25 .................................................................................................................................. Table 26 .................................................................................................................................. Table 27 ..................................................................................................................................

VII/227 VII/227 VII/227 VII/227 VII/227 VII/228 VII/228 VII/228 VII/229

E. Polymolecularity Correction Factors for Diffusion Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 28 .................................................................................................................................. Table 29 .................................................................................................................................. Table 30 .................................................................................................................................. Table 31 .................................................................................................................................. Table 32 .................................................................................................................................. Table 33 .................................................................................................................................. Table 34 ..................................................................................................................................

VII/229 VII/229 VII/229 VII/229 VII/230 VII/230 VII/230 VII/230


xl

Contents Table 35 Table 36 Table 37 Table 38 Table 39 Table 40 Table 41

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


F. Polymolecularity Correction Factors for Mean-Square Radius of Gyration versus Molecular Weight Relationship ........................................................................................... Table 42 .................................................................................................................................. Table 43 .................................................................................................................................. Table 44 .................................................................................................................................. Table 45 .................................................................................................................................. Table 46 .................................................................................................................................. Table 47 ..................................................................................................................................


G. Polymolecularity Correction Factors for Second Virial Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 48 .................................................................................................................................. Table 49 .................................................................................................................................. Table 50 .................................................................................................................................. Table 51 ..................................................................................................................................


H. Polymolecularity Correction Factors for the Determination of the Dimensions of Macromolecules ................................................................................................................. 1. Fox-flory Relationship ............................................................................................. Table 52 .................................................................................................................. Table 53 .................................................................................................................. Table 54 .................................................................................................................. Table 55 .................................................................................................................. 2. Interconversion of Different Averages of the Mean-square Radius of Gyration .................................................................................................................. Table 56 .................................................................................................................. Table 57 .................................................................................................................. Table 58 .................................................................................................................. Table 59 .................................................................................................................. 3. Interconversion of Different Averages of the Mean-square End-to-end Distance .................................................................................................................. Table 60 .................................................................................................................. Table 61 .................................................................................................................. Table 62 .................................................................................................................. Table 63 .................................................................................................................. Table 64 .................................................................................................................. Table 65 ..................................................................................................................



Contents 4.

I.

xli

The Effect of Polymolecularity on the Radius of Gyration of Stiff Polymer Chains ..................................................................................................................... VII/240 Table 66 .................................................................................................................. VII/240 Table 67 .................................................................................................................. VII/240

Polymolecularity Correction Factors for the Determination of Unperturbed Dimensions of Macromolecules .......................................................................................... 1. Burchard-stockmayer-fixman Procedure ................................................................ Table 68 .................................................................................................................. Table 69 .................................................................................................................. Table 70 .................................................................................................................. 2. Cowie-bywater Procedure ....................................................................................... Table 71 .................................................................................................................. Table 72 .................................................................................................................. Table 73 .................................................................................................................. Table 74 .................................................................................................................. 3. Baumann-stockmayer-fixman Procedure ................................................................ Table 75 .................................................................................................................. Table 76 .................................................................................................................. Table 77 .................................................................................................................. Table 78 .................................................................................................................. 4. Baumann-kurata-stockmayer Procedure ................................................................ Table 79 .................................................................................................................. Table 80 .................................................................................................................. Table 81 .................................................................................................................. Table 82 ..................................................................................................................

VII/240 VII/240 VII/240 VII/240 VII/241 VII/241 VII/241 VII/241 VII/241 VII/241 VII/242 VII/242 VII/242 VII/242 VII/242 VII/243 VII/243 VII/243 VII/243 VII/244

J. References ......................................................................................................................... VII/244 Polymer-solvent Interaction Parameters ..................................................................................................... VII/247 A. Introduction ........................................................................................................................ VII/247 B. Concentration Variables ..................................................................................................... VII/247 C. Conversion of Concentration Variables .............................................................................. VII/247 D. Basic Equations .................................................................................................................. VII/247 E. Methods of Determination .................................................................................................. VII/248 F. Temperature Dependence .................................................................................................. VII/249 G. Concentration Dependence ................................................................................................ VII/249 H. Molecular Weight Dependence ........................................................................................... VII/250 I.

Polymer-solvent Interaction Parameters, χ ......................................................................... VII/250

J. References ......................................................................................................................... VII/262 Concentration Dependence of the Viscosity of Dilute Polymer Solutions: Huggins and Schulzblaschke Constants ............................................................................................................................ VII/265 A. Introduction ........................................................................................................................ VII/265 B. Tables ................................................................................................................................ VII/266


xlii

Contents Table 1. Huggins Constants ................................................................................................. 1.1 Poly(dienes) and Poly(alkenes) .............................................................. 1.2 Poly(acrylic Acid) and Poly(methacrylic Acid) Derivatives ...................... 1.3 Vinyl Polymers ........................................................................................ 1.4 Poly(oxides) ............................................................................................ 1.5 Poly(esters) ............................................................................................. 1.6 Polyamides ............................................................................................. 1.7 Other Compounds .................................................................................. 1.8 Cellulose, Cellulose Derivatives, and Polysaccharides .......................... Table 2. Schulz-blaschke Constants .....................................................................................

VII/266 VII/266 VII/268 VII/272 VII/277 VII/278 VII/279 VII/280 VII/282 VII/284

C. References ......................................................................................................................... VII/285 Theta Solvents ............................................................................................................................................. VII/291 A. Introduction ........................................................................................................................ 1. Fundamentals ......................................................................................................... 1.1 Thermodynamics .................................................................................... 1.2 Unperturbed Dimensions ........................................................................ 2. Methods to Determine Theta Solvents .................................................................... 2.1 Phase Equilibrium (PE) ........................................................................... 2.2 Second Virial Coefficient (A) ................................................................... 2.3 Cloud Point Titration (CP) ....................................................................... 2.4 Cloud Temperature Titration (CT) ........................................................... 2.5 Unperturbed Dimensions (RGM, VM, DM, SM) ...................................... 2.6 Other Methods ........................................................................................

VII/291 VII/291 VII/291 VII/292 VII/293 VII/293 VII/293 VII/294 VII/294 VII/294 VII/294

B. Tables of Theta Solvents for Polymers ............................................................................... Table 1. Homochain Polymers .............................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(styrenes) ......................................................................................... 1.4 Poly(vinyls) ............................................................................................. 1.5 Poly(acrylics) and Related Compounds .................................................. 1.6 Poly(methacrylics) and Related Compounds .......................................... 1.7 Other Carbon Chains .............................................................................. Table 2. Heterochain Polymers ............................................................................................. 2.1 Poly(acetals) and Poly(ethers) ................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly(amides) ........................................................................................... 2.4 Polyureas and Polyurethanes ................................................................. 2.5 Polysaccharides ...................................................................................... 2.6 Carbon-sulfur Chains .............................................................................. 2.7 Silicon-oxygen Chains ............................................................................ 2.8 Phosphorus-oxygen Chains ....................................................................


C. References ......................................................................................................................... VII/318


Contents

xliii

Fractionation of Polymers ............................................................................................................................ VII/327 A. Principles of Polymer Fractionation .................................................................................... VII/327 B. Fractionation Methods ........................................................................................................ 1. Fractionation by Solubility ....................................................................................... 2. Fractionation by Chromatography ........................................................................... 3. Cross Fractionation ................................................................................................. 4. Fractionation by Sedimentation .............................................................................. 5. Fractionation by Diffusion ....................................................................................... 6. Fractionation by Ultrafiltration through Porous Membranes .................................... 7. Fractionation by Zone Melting ................................................................................. 8. Electron Microscopic Counting Method ..................................................................

VII/328 VII/328 VII/330 VII/332 VII/333 VII/333 VII/333 VII/333 VII/333

C. Tables of Fractionation Systems for Different Polymers ..................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- and β-Substituted Poly(acrylics) and Poly(methacrylics) ......... 1.6 Poly(vinyl Ethers) .................................................................................... 1.7 Poly(vinyl Alcohol), Poly(vinyl Ketones), Poly(vinyl Halides), Poly(vinyl Nitriles) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. 1.11 Random and Alternating Copolymers ..................................................... 1.12 Block Copolymers ................................................................................... 1.13 Graft Copolymers .................................................................................... 1.14 Mixture of Polymers ................................................................................ Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Formaldehyde Resins ............................................................................. Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(carbonates) ..................................................................................... 3.3 Poly(esters) ............................................................................................. 3.4 Poly(urethanes) and Poly(ureas) ............................................................ 3.5 Poly(amides) and Poly(imines) ............................................................... 3.6 Poly(amino Acids) ................................................................................... 3.7 Poly(sulfides), Poly(sulfones), Poly(sulfonamides) ................................. 3.8 Poly(silanes) and Poly(siloxanes) ........................................................... 3.9 Poly(phosphazenes) and Related Polymers ........................................... 3.10 Other Compounds .................................................................................. 3.11 Random Copolymers ..............................................................................

VII/333 VII/333 VII/333 VII/336 VII/344 VII/346 VII/351 VII/353


VII/353 VII/355 VII/356 VII/363 VII/366 VII/382 VII/389 VII/395 VII/397 VII/397 VII/397 VII/398 VII/398 VII/404 VII/405 VII/410 VII/411 VII/414 VII/416 VII/418 VII/422 VII/423 VII/425

xliv

Contents 3.12 Block Copolymers ................................................................................... 3.13 Graft Copolymers .................................................................................... Table 4. Poly(saccharides) ................................................................................................... 4.1 Poly(saccharides) ................................................................................... 4.2 Graft Copolymers .................................................................................... 4.3 Mixtures of Polymers ..............................................................................


D. References ......................................................................................................................... 1 to 1188 ................................................................................................................................. 1189 to 2452 ........................................................................................................................... 2453 to 3608 ...........................................................................................................................

VII/438 VII/438 VII/458 VII/478

Solvents and Non Solvents for Polymers .................................................................................................... VII/497 A. Introduction ........................................................................................................................ VII/498 B. Abbreviations ..................................................................................................................... VII/498 C. Tables of Solvents and Nonsolvents ................................................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes), Poly(acetylenes) ............................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics), Poly(methacrylics) ...........................................................


1.3.1 Poly(acrylic Acids) ............................................................................ VII/501 1.3.2 Poly(acrylates) .................................................................................. VII/501 1.3.3 Poly(methacrylates) ......................................................................... VII/501 1.3.4 Poly(disubstituted Esters) ................................................................ VII/502 1.3.5 Poly(acrylamides), Poly(methacrylamides) ..................................... 1.4 Poly(vinyl Ethers) .................................................................................... 1.5 Poly(vinyl Alcohols), Poly(acetals), Poly(vinyl Ketones) ......................... 1.6 Poly(vinyl Halides) .................................................................................. 1.7 Poly(vinyl Nitrites) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Other Compounds .................................................................................. Table 3. Main-chain Carbonyl Polymers ............................................................................... Table 4. Main-chain Acyclic Heteroatom Polymers .............................................................. 4.1 Main-chain –C–O–C– Polymers .............................................................

VII/503 VII/503 VII/504 VII/505 VII/506 VII/506 VII/507 VII/508 VII/509 VII/509 VII/510 VII/510 VII/511 VII/511

4.1.1 Poly(oxides) ...................................................................................... VII/511 4.1.2 Poly(carbonates) .............................................................................. VII/513 4.1.3 Poly(esters) ...................................................................................... VII/513 4.1.4 Poly(anhydrides) .............................................................................. VII/515 4.1.5 Poly(urethanes) ................................................................................ VII/515


Contents 4.2

xlv

Main-chain –O– Heteroatom Polymers ................................................... VII/515 4.2.1 Poly(sulfonates) ................................................................................ VII/515

4.3

4.2.2 Poly(siloxanes) ................................................................................. VII/516 Main-chain –C–S–C– and –C–S–N– Polymers ...................................... VII/516 4.3.1 Poly(sulfides) .................................................................................... VII/516 4.3.2 Poly(sulfones) ................................................................................... VII/517

4.4

4.3.3 Others ............................................................................................... VII/518 Main-chain –C–N–C– Polymers ............................................................. VII/518 4.4.1 Poly(amides) .................................................................................... VII/518 4.4.2 Poly(hydrazides) ............................................................................... VII/520 4.4.3 Poly(ureas) ....................................................................................... VII/521 4.4.4 Poly(carbodiimides) .......................................................................... VII/521

4.4.5 Other Compounds ............................................................................ 4.5 Poly(phosphazenes) and Related Compounds ...................................... 4.6 Poly(silanes), Poly(silazanes) ................................................................. Table 5. Main-chain Heterocyclic Polymers .......................................................................... 5.1 Poly(benzoxazoles), Poly(oxadiazoles), Poly(oxadiazolidines) .............. 5.2 Poly(dithiazoles), Poly(benzothiazoles) .................................................. 5.3 Poly(imides) ............................................................................................


5.3.1 Poly(benzimides) .............................................................................. VII/524 5.3.2 Poly(pyromellitides) .......................................................................... VII/525 5.3.3 Others ............................................................................................... 5.4 Poly(quinoxalines) .................................................................................. 5.5 Poly(benzimidazoles) .............................................................................. 5.6 Poly(piperazines) .................................................................................... 5.7 Poly(anhydrides) ..................................................................................... 5.8 Poly(thiophenes) ..................................................................................... 5.9 Others ..................................................................................................... Table 6. Formaldehyde Resins ............................................................................................. Table 7. Natural Polymers and Modified Natural Polymers .................................................. 7.1 Natural Rubber and Derivatives .............................................................. 7.2 Cutta Percha ........................................................................................... 7.3 Cellulose and Derivatives .......................................................................

VII/525 VII/526 VII/526 VII/526 VII/527 VII/527 VII/527 VII/528 VII/528 VII/528 VII/529 VII/529

7.3.1 Cellulose ........................................................................................... VII/529 7.3.2 Cellulose Ethers ............................................................................... VII/529 7.3.3 Cellulose Esters ............................................................................... VII/530 7.3.4 Cellulose Nitrate and Sulfate ........................................................... 7.4 Starch and Derivatives ............................................................................ 7.5 Other Poly(saccharides) ......................................................................... 7.6 Natural Resins ........................................................................................ Table 8. Inorganic Polymers ................................................................................................. Table 9. Poly(electrolytes) .................................................................................................... This page has been reformatted by Knovel to provide easier navigation.


xlvi

Contents Table 10. Block Polymers ....................................................................................................... VII/533 Table 11. Dendrimers ............................................................................................................. VII/534 D. References ......................................................................................................................... VII/536

Specific Refractive Index Increments of Polymers in Dilute Solution ......................................................... VII/547 A. Introduction ........................................................................................................................ VII/547 B. Introduction from the Third Edition ...................................................................................... VII/547 C. Refractometric Calibration Data .......................................................................................... VII/550 D. Tables of Specific Refractive Index Increments of Polymer Solutions ................................. Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- or β-Substituted Poly(acrylics) and Poly(methacrylics) ............ 1.6 Poly(styrenes) ......................................................................................... 1.7 Other Compounds .................................................................................. Table 2. Main-chain Cyclic Carbon Polymers ....................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 C–O–C Polymers (Poly(oxides), Poly(esters), and Others) .................... 3.2 C–S–C Polymers (Poly(sulfones) and Others) ....................................... 3.3 C–N–C Polymers (Poly(amides), Poly(isocyanates), Poly(urethanes), and Others) ................................................................. 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(silanes) and Poly(silazanes) ........................................................... 3.6 Poly(heterocyclics) and Others ............................................................... Table 4. Cellulose and Derivatives ....................................................................................... Table 5. Poly(saccharides) ...................................................................................................

VII/551 VII/551 VII/551 VII/553 VII/557 VII/561 VII/573 VII/574 VII/588 VII/594 VII/594 VII/594 VII/599 VII/599 VII/604 VII/606 VII/608 VII/609 VII/611

E. References ......................................................................................................................... VII/615 Particle Scattering Factors in Rayleigh Scattering ...................................................................................... VII/629 A. Introduction: General Relations for a Homogeneous Solute ............................................... VII/629 B. Scattering Factors for Various Molecular Models ................................................................ VII/630 C. Effects of Dispersion in Molecular Weight .......................................................................... VII/631 D. Determination of Molecular Weight and Radius of Gyration ................................................ VII/632 E. Calculation of Scattering Factors ........................................................................................ VII/633 F. Particle Scattering Factors and Dissymmetries .................................................................. VII/633 Table 1. Dissymmetries for Monodisperse Systems ............................................................. VII/634 Table 2. Dissymmetries for Monodisperse and Polydisperse Coils ...................................... VII/634 G. References ......................................................................................................................... VII/635 Dipole Moments of Polymers in Solution ..................................................................................................... VII/637 A. Introduction ........................................................................................................................ VII/637 B. Dipole Moments of Polymers In Solution ............................................................................ VII/638 Table 1. Polyoxides (Polyethers) .......................................................................................... VII/638 This page has been reformatted by Knovel to provide easier navigation.

Contents Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.

Polysulfides (Polythioethers) ................................................................................... Hydroxyl Terminated Oxide/Sulfide Copolymers .................................................... Polyesters Derived from Aromatic Diacids .............................................................. Aliphatic and Cycloaliphatic Polyesters .................................................................. Polycarbonates ....................................................................................................... Vinyl Polymers ........................................................................................................ Acrylic Polymers ..................................................................................................... Methacrylic Polymers .............................................................................................. Itaconate Polymers ................................................................................................. Polydienes .............................................................................................................. Silicon Based Polymers .......................................................................................... Styrene Copolymers ...............................................................................................

xlvii VII/639 VII/640 VII/640 VII/641 VII/641 VII/642 VII/643 VII/644 VII/644 VII/644 VII/645 VII/645

C. References ......................................................................................................................... VII/646 Heat, Entropy and Volume Changes for Polymer-liquid Mixtures .............................................................. VII/649 A. Introduction ........................................................................................................................ VII/649 1. Scope of the Table .................................................................................................. VII/649 2. Experimental Methods ............................................................................................ VII/649 B. Key for the Tables .............................................................................................................. VII/650 C. Tables of Literature References for Heat, Entropy, and Volume Changes for Polymer-solvent Mixtures ................................................................................................... Table 1. Main-chain Carbon Polymers .................................................................................. 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics) .......................................................................................... 1.4 Vinyl Polymers ........................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Other Compounds .................................................................................. Table 2. Main-chain Carbon Heteroatom Polymers .............................................................. 2.1 Poly(oxides) and Poly(esters) ................................................................. 2.2 Poly(amides) ........................................................................................... 2.3 Poly(siloxanes) ....................................................................................... 2.4 Derivatives of Cellulose .......................................................................... 2.5 Other Compounds ..................................................................................

VII/650 VII/650 VII/650 VII/651 VII/654 VII/655 VII/657 VII/659 VII/659 VII/659 VII/661 VII/661 VII/662 VII/663

D. References ......................................................................................................................... VII/663 Heats of Solution of Some Common Polymers ........................................................................................... VII/671 A. Introduction ........................................................................................................................ VII/671 B. Table of Heats of Solution .................................................................................................. VII/671 C. References ......................................................................................................................... VII/673 Solubility Parameter Values ......................................................................................................................... VII/675 A. Introduction ........................................................................................................................ VII/675 B. Miscibility of Solvents and Polymers ................................................................................... VII/676 1. Cohesive Energy Density and the Solubility (Hildebrand) Parameter ..................... VII/676 This page has been reformatted by Knovel to provide easier navigation.

xlviii

Contents 2. 3.

Cohesive Energy Parameters for Polar Systems .................................................... VII/677 Relationship Between Solubility Parameters and Other Thermodynamic Parameters ............................................................................................................. VII/677

C. Solubility Parameter Measurements, Calculations, and Correlations .................................. 1. Solvents .................................................................................................................. 2. Polymers ................................................................................................................. 2.1 Indirect Measurements ........................................................................... 2.2 Correlation Methods ............................................................................... Table 1. Selected Solvents for Use in Polymer Solvency Testing ........................................ Table 2. Group Contribution to Cohesive Energy Density .................................................... 2.1 Carbon-containing Groups ...................................................................... 2.2 Oxygen-containing Groups ..................................................................... 2.3 Nitrogen-containing Groups .................................................................... 2.4 Other Groups .......................................................................................... 2.5 Structural Features ................................................................................. Table 3. Contribution to Ecoh and V ....................................................................................... Table 4. Solubility Parameter I: Component Group Contributions ........................................ Table 5. Solubility Parameter II: Component Group Contributions ....................................... Table 6. Equations to be Used for Hoy's System .................................................................

VII/679 VII/679 VII/680 VII/680 VII/682 VII/683 VII/684 VII/684 VII/684 VII/684 VII/684 VII/685 VII/685 VII/686 VII/686 VII/687

D. Solubility Table 7. Table 8. Table 9.

VII/688 VII/688 VII/694 VII/698 VII/698 VII/698 VII/698 VII/699 VII/699 VII/699 VII/699 VII/700 VII/700 VII/700 VII/700 VII/701 VII/701 VII/701 VII/701 VII/702 VII/702 VII/708 VII/709 VII/710

Parameter Tables ................................................................................................ Solubility Parameters of Solvents in Alphabetical Order ......................................... Solubility Parameters of Solvents in Increasing Order of δ ..................................... Hansen Solubility Parameters of Liquids at 25°C ................................................... 9.1 Paraffinic Hydrocarbons ......................................................................... 9.2 Aromatic Hydrocarbons .......................................................................... 9.3 Halohydrocarbons ................................................................................... 9.4 Ethers ..................................................................................................... 9.5 Ketones ................................................................................................... 9.6 Aldehydes ............................................................................................... 9.7 Esters ...................................................................................................... 9.8 Nitrogen-containing Compounds ............................................................ 9.9 Sulfur-containing Compounds ................................................................ 9.10 Acid Halides and Anhydrides .................................................................. 9.11 Alcohols .................................................................................................. 9.12 Acids ....................................................................................................... 9.13 Phenols ................................................................................................... 9.14 Water ...................................................................................................... 9.15 Polyhydric Alcohols ................................................................................. Table 10. Solubility Parameters of Polymers .......................................................................... 10.1 Main Chain Carbon Polymers ................................................................. 10.2 Main Chain C–O Polymers ..................................................................... 10.3 Main Chain C–N Polymers ..................................................................... 10.4 Other Polymers ....................................................................................... This page has been reformatted by Knovel to provide easier navigation.

Contents

xlix

E. References ......................................................................................................................... VII/711 Optically Active Polymers ............................................................................................................................ VII/715 A. Abbreviations Used ............................................................................................................ VII/715 B. Optically Active Polymers from Chiral Monomers ............................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(alkenes) .......................................................................................... 1.2 Poly(acrylics) and Related Polymers ...................................................... 1.3 Poly(methacrylics) and Related Polymers .............................................. 1.4 Poly(vinyl Ethers), Poly(vinyl Ketones), and Poly(vinyl Esters) .............. 1.5 Poly(styrenes), Poly(carbazoles) ............................................................ 1.6 Poly(dienes) ............................................................................................ 1.7 Poly(isonitriles) ....................................................................................... 1.8 Poly(alkynes) .......................................................................................... 1.9 Poly(maleimides) and Related Polymers ................................................ 1.10 Other Compounds .................................................................................. Table 2. Main-chain Acyclic Heteroatom Polymers .............................................................. 2.1 Poly(oxides) ............................................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly (sulfides), Poly(thioesters) .............................................................. 2.4 Poly(urethanes), Poly(ureas) .................................................................. 2.5 Poly(amides) ........................................................................................... 2.6 Poly(isocyanates) ................................................................................... 2.7 Poly(imines) ............................................................................................ 2.8 Poly(amino Acids) ................................................................................... Table 3. Poly(saccharides) ...................................................................................................

VII/716 VII/716 VII/716 VII/716 VII/717 VII/718 VII/719 VII/720 VII/720 VII/721 VII/722 VII/723 VII/723 VII/723 VII/724 VII/725 VII/725 VII/726 VII/728 VII/728 VII/729 VII/732

C. Optically Active Polymers from Achiral Monomers .............................................................. Table 4. Main-chain Acyclic Carbon Polymers ..................................................................... 4.1 Poly(acrylics) and Related Polymers ...................................................... 4.2 Poly(methacrylics) and Related Polymers .............................................. 4.3 Poly(vinyl Ethers) .................................................................................... 4.4 Poly(styrenes) ......................................................................................... 4.5 Poly(dienes) ............................................................................................ 4.6 Poly(isonitriles) ....................................................................................... 4.7 Poly(maleimides) .................................................................................... 4.8 Other Compounds .................................................................................. Table 5. Main-chain Acyclic Heteroatom Polymers .............................................................. 5.1 Poly(oxides) and Poly(sulfides) .............................................................. 5.2 Poly(isocyanates) ...................................................................................

VII/733 VII/733 VII/733 VII/734 VII/735 VII/735 VII/735 VII/736 VII/736 VII/737 VII/737 VII/737 VII/738

D. References ......................................................................................................................... VII/739 Anisotropy of Segments and Monomer Units of Polymer Molecules ......................................................... VII/745 A. Introduction ........................................................................................................................ VII/745


l

Contents B. Tables of Anisotropy of Segments and Monomer Units of Polymer Molecules ................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Poly(acrylic Acid) Derivatives with Mesogenic Side Groups ................... 1.6 Poly(methacrylic Acid) Derivatives with Mesogenic Side Groups ........... 1.7 Vinyl Polymers ........................................................................................ 1.8 Poly(vinyl) Derivatives with Mesogenic Side Groups .............................. 1.9 Copolymers, Graft and Block Copolymers .............................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(esters) ............................................................................................. 3.3 Poly(amides) ........................................................................................... 3.4 Poly(peptides) and Nucleic Acids ........................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(siloxanes) ....................................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Poly(imides) ............................................................................................ 4.2 Poly(pyrromellitimides) ........................................................................... 4.3 Poly(quinoxalines) .................................................................................. 4.4 Poly(benzimidazoles), Poly(benzoxazoles) ............................................ 4.5 Poly(saccharides) ...................................................................................

VII/746 VII/746 VII/746 VII/747 VII/747 VII/748 VII/748 VII/749 VII/750 VII/751 VII/751 VII/752 VII/752 VII/752 VII/752 VII/755 VII/755 VII/755 VII/756 VII/756 VII/756 VII/756 VII/757 VII/757 VII/758

C. References ......................................................................................................................... VII/760 Gelation Properties of Polymer Solutions .................................................................................................... VII/765

VIII. Abbreviations of Polymer Names and Chemical Abstract Numbers Abbreviations for Thermoplastics, Thermosets, Fibers, Elastomers and Additives ...................................

VIII/1

A. Introduction ........................................................................................................................

VIII/1

B. Abbreviations in Alphabetical Order ....................................................................................

VIII/2

C. Abbreviations and Acronyms Based on Poly(monomer) Names ......................................... VIII/15 D. Abbreviations for Polymers Named after a Characteristic Polymer Croup .......................... VIII/17 E. Abbreviations for Polymers Produced by Chemical Transformation of Other Polymers ............................................................................................................................ VIII/18 F. Abbreviations for Blends, Reinforced Polymers, etc. .......................................................... VIII/19 G. ISO Codes for Thermoplastic Materials .............................................................................. 1. Codes for ISO Data Blocks 1-5 ............................................................................... 1.1 ISO and DIN Codes for Data Block 1 ..................................................... 1.2 ISO Codes for Items in Data Block 2 ...................................................... 1.3 ISO Codes for Items in Data Block 3 ......................................................


VIII/19 VIII/19 VIII/19 VIII/20 VIII/20

Contents 1.4 1.5

li

ISO Codes for Extending and Reinforcing Fillers (Data Block 4) ........... VIII/20 ISO Codes for Data Block 5 .................................................................... VIII/21

H. SPI Codes for the Recycling of Plastics .............................................................................. VIII/21 I.

Recommended Abbreviations and Acronyms for Names of Elastomers ............................. VIII/21

J. Abbreviations for Textile Fibers .......................................................................................... VIII/22 Chemical Abstract Registry Numbers and Online Database Searching for Polymer Literature ................ VIII/25 A. Nomenclature ..................................................................................................................... VIII/25 B. CAS Registry Numbers ...................................................................................................... VIII/25 C. Indexing and CAS Registry Number Assignment ................................................................ VIII/26 D. Example Searches ............................................................................................................. 1. Example of a Search Using the Polymer CAS Registry Number ............................ 2. Example of a Search Using the Monomer CAS Registry Number .......................... 3. Example of a Combined Search ............................................................................. 4. Example of a Copolymer Search ............................................................................ 5. Example of an Engineering Database Search ........................................................ 6. Example of a Search with Punctuation in the Polymer Name ................................. 7. Example of an Engineering Materials Abstracts Search ......................................... 8. Example of a Polymer Trademark Search ..............................................................

VIII/26 VIII/26 VIII/26 VIII/26 VIII/28 VIII/29 VIII/29 VIII/29 VIII/29

E. List of CAS Regisry Numbers of Common Polymers .......................................................... VIII/32

Index .......................................................................................................................................


IX/1

S E C T I O N

N

O

M

E

N

C

L

A

T

U

R

E

I

R U L E S

—

U

N

I

T

S

N o m e n c l a t u r e

W . V. Metanomski Chemical Abstracts Service, Columbus, Ohio, USA

A. Introduction B. IUPAC Recommendations 1. Source-Based Nomenclature 1.1. Homopolymers 1.2. Copolymers 1.3. Nonlinear Macromolecules & Macromolecular Assemblies 2. Structure-Based Nomenclature 2.1. Regular Single-Strand Organic Polymers 2.2. Regular Double-Strand Organic Polymers 2.3. Regular Single-Strand Inorganic and Coordination Polymers 2.4. Regular Quasi-Single-Strand Coordination Polymers 2.5. Irregular Single-Strand Organic Polymers C. Use of Common and Semisystematic Names D. Chemical Abstracts (CA) Index Names E. Polymer Class Names F. References A.

1-1 1-1 I-2 I-2 I-2 I-3 I-3 I-6 I-6 I-7 I-7 I-8 I-8 1-11 1-12

INTRODUCTION

Macromolecular (polymer) nomenclature has an almost 50-year history. As early as 1949 there existed a Subcommission on Nomenclature within the International Union of Pure and Applied Chemistry (IUPAC) under the chairmanship of Maurice L. Huggins. The Subcommission was part of the IUPAC Commission on Macromolecules, chaired then by Herman F. Mark. Other notable pioneers in polymer science, Jan Joseph Hermans, Otto Kratky, Harry W. Melville, and George J. Smets, were members of the Commission. The Subcommission produced its first official report in 1952. It recognized then, what is just as true today, that the practice in the field of small molecules of providing rigorous definitions is impractical for polymers. The latter consist of molecules not necessarily exactly of the same size, chemical composition, or structure. The differences result from the presence of end groups, branches, variation in orientation of monomeric units, and irregularity in the sequence of different types of units. The American Chemical Society (ACS) Division of Polymer Chemistry established its Nomenclature Commit-

tee in 1963 to try to unify earlier attempts to name polymers in some coherent way. Their first major project resulted in a structure-based nomenclature for regular linear polymers, first published in ACS Polymer Preprints in 1967, adopted by Chemical Abstracts in 1968, and incorporated in IUPAC recommendations in 1975 [I]. When the IUPAC Commission on Macromolecules was elevated to become the IUPAC Division of Macromolecular Chemistry, the latter in turn established its Commission on Macromolecular Nomenclature in 1968. The Commission in the course of its nearly 30 years of existence produced a series of major documents that have shaped modern nomenclature and terminology of polymer science. The recommendations are being published in the IUPAC official journal, Pure and Applied Chemistry, and occasionally are republished in the form of a "Compendium" which groups all the currently valid documents in a single volume. The Commission published its "Compendium of Macromolecular Nomenclature" in 1991 [2]. The book, which IUPAC has designated the "Purple Book", in analogy to other IUPAC books ("Blue" - organic, "Red" - inorganic, "Orange" - analytical, "Green"- physical, and "Gold" - overall chemistry), has the two most basic macromolecular nomenclature recommendations: "nomenclature of regular single-strand organic polymers" and "source-based nomenclature for copolymers". In more recent years, the Commission extended that basic nomenclature to double-strand (ladder and spiro) organic polymers, irregular and crosslinked polymers, and polymer blends and interpenetrating networks. In this article, the basic structure-based and source-based nomenclature of polymers is explained and illustrated in some detail. The continuing use of common and semisystematic nomenclature with reference to specific tables in this Handbook is highlighted. The current Chemical Abstracts (CA) index names [3] are compared and contrasted with the IUPAC practice and typical names employed in the polymer journals and textbooks. B.

IUPAC RECOMMENDATIONS

Since polymers, unlike low-molecular-weight compounds, have no uniform structure and are mixtures of macromolecules of different length and different structural

arrangement, their graphical representation and their names require a special approach. Often enough, the structure of the polymer has not been sufficiently characterized and the researcher cannot draw its chemical structure. Consequently, no name of the polymer reflecting its structure is possible. A polymerization reaction for a polymer formed from a monomer such as vinyl chloride can schematically be represented by

polybutadiene polyethylene poly(methyl methacrylate) poly(methyl vinyl ether) polystyrene poly(tetrafluoroethylene) poly(vinyl alcohol) poly(vinyl acetate) poly(vinyl chloride) poly(vinylidene dichloride)

That shows an idealized product. In fact, however, the polymer consists of long-chains of various lengths. The repeating units, - C H 2 - C H C l - , are not necessarily all uniquely oriented and joined in a regular fashion as shown in the idealized structure above. In addition to "head-totail" links

Parentheses are used when the name of the monomer consists of two or more words, and when the monomer has substituents. These are all olefinic type reactants, from which two carbon atoms originally linked by a double bond form a bivalent group:

other links such as "head-to-head"

where R and R [ represent a hydrogen atom or a substituent group. Many of these are joined, in turn, to each other but their exact orientation or sequence is seldom known. On the other hand, different polymers derived from a single monomer and having identical constitutional units can still be differentiated by additional information, such as average molecular weight and other chemical and physical characteristics.

and "tail-to-tail"

can occur, and the exact sequence of all these repeating units usually is not known. This becomes even more complicated when a copolymer is derived from more than one monomer, such as styrene and methyl acrylate, which contribute two constitutional or monomeric units:

They can combine into a polymeric chain, resulting in many types such as unspecified, statistical, random, alternating, periodic, block, or graft copolymers. Because the exact structure of the polymer is not always known, two systems of naming polymers exist: source-based nomenclature, structure-based nomenclature. 1.

Source-Based Nomenclature

1.1. Homopolymers Homopolymers are derived from only one species of monomer, which may be the actual starting reactant (or source), or be a hypothetical monomer if the homopolymer is formed by a modification of another homopolymer. The name of the polymer is formed by attaching the prefix "poly" to the name of the actual or assumed monomer, or the starting reactant (source), from which the polymer is derived. Examples: poly (acrylic acid) polyacrylonitrile

1.2. Copolymers For copolymers, the names of monomers are cited after the prefix "poly". In addition, an italicized connective (infix) is placed between the names of monomers to denote the kind of sequential arrangement by which the constitutional (monomeric) units, derived from each monomer, are related in the structure [4]. Seven types of sequence arrangements are listed with their corresponding connectives:

Type

Connective

unknown or unspecified statistical (obeying known statistical laws) random (obeying Bernoullian distribution) alternating (for two monomeric units) periodic (ordered sequence of more than two) block (linear arrangement of blocks) graft (side blocks chains connected to main chain)

Examples:

-co-stat-raft-alt-per-block-graft-

poly[styrene-C(?-(methyl methacrylate)! poly^tyrene-statf-acrylonitrile-statf-butadiene) poly[ethylene-ran-(vinyl acetate)] poly[(ethylene glycol)-tf/r-(terephthalic acid)] poly[formaldehyde-/?er-(ethylene oxide)-per(ethylene oxide)] polystyrene-&/oc&-polybutadiene polybutadiene-gra/f-polystyrene

The names of the monomers are those common or semisystematic names that are encountered most often in the literature of polymer science. The order of citation of monomers in copolymer names is arbitrary. An equally acceptable alternative scheme for naming copolymers utilizes the prefix "copoly", followed by citation of the names of the monomers, separated by an oblique stroke (a solidus). Parentheses are not needed to enclose monomer names consisting of two or more words. Examples:

the constituent macromolecules with an italicized connective between them. Examples:

copoly(styrene/methyl methacrylate) j"tatf-copoly(styrene/acrylonitrile/butadiene) ran-copoly(ethylene/vinyl acetate) a/f-copoly(ethylene glycol/terephthalic acid) per-copoly(formaldehyde/ethyleneoxide/ethylene oxide) Wtfc/:-copoly(styrene-butadiene) gra/£-copoly(butadiene-styrene)

1.3. Nonlinear Macromolecules and Macromolecular Assemblies Most recently, the source-based nomenclature has been extended for non-linear macromolecules and macromolecular assemblies [5], The non-linear macromolecules comprise branched, graft, comb, star, cyclic, and network macromolecules. The macromolecular assemblies comprise polymer blends, interpenetrating polymer networks, and polymer-polymer complexes. The following italicized qualifiers can be used as both prefixes (e.g., blend-, net-) and infixes (connectives) (e.g., -blend-, -net-) to designate the skeletal structure of nonlinear macromolecules or macromolecular assemblies:

Type cyclic branched, unspecified short-chain-branched long-chain-branched branched with branch point of functionality / comb star star with / arms network crosslink polymer blend interpenetrating polymer network semi-interpenetrating polymer network polymer-polymer complex

Connective cyclo branch sh-branch l-branch f-branch comb star f-star net t (Greek iota) blend ipn sipn compl

2.

poly styrene-com£>-poly aery lonitrile com&-poly(styrene~statf-acrylonitrile) poly styrene-comZ?- [poly acrylonitrile; poly(methyl methacrylate)] 4-sfar-polystyrene star-(po\yA-block-polyB-block-polyC) star-(polyA; polyB; polyC) star-(polyacrylonitrile; polystyrene) (M1 100000:20000) fte£-polystyrene-£-divinylbenzene n^-poly[styrene-(2.00 x 10 ~4)

1

130 130

150

2.35 x 10"3

1

130

150

1.017 x 10 ~3

1

130

145 T (K) 160 160 160 148 158 103.2 111.9

1.5 x 10~ 4 6.8 x 10 16 1.05 xlO" 3 1.25 x l 0 ~ 3 1.27 xlO" 3 9.OxIO- 5 2.5 xlO" 4 5.6xlO" 7 2.03 XlO" 6

exp[- U6A/RT] exp[- 154.6/RT]

u

exp[-146.4//?7]

155.2

h

z (0.98) z (2000) z (2850) z (5170)

exp[- 15S3/RT] 169.9

h

165.3 exp[- 1653/RT] 1

165.3 exp[- 1653/RT] 113.0

a,i(2.6) a,i(33) a,i(100)

192 192 192 192 123 143 376 270 270 270 140 301 270 270 140 143 140 123 270 270 270 192 192 192 192 140 197 33 33 33 33 140 143 376 192 192 192 192 238 238 238 238 238 238 125 125 130

125 125 117 117 117 88 88 227 227

Notes page 11-69; References page II - 70

TABLE 3. cont'd Number of C atoms S (cont'd)

Initiator tert-Butyl peroxide

Solvent Vapor

Vapor (He)

KBr pellets

terf-Butyl 2-chloro-l,l-dimethylethylperoxide

Cumene

sec-Butyl peroxide

Toluene Vapor Decane Dodecane Heptane Hexadecane Octane Styrene Tetradecane Chlorobenzene Chlorobenzene Chlorobenzene Chlorobenzene

Butyl peroxide

Bromo-terf-butyl peroxide Chloro-terf-butyl peroxide Bis(chloro-tert-butyl) peroxide 2-terf-Butyl peroxy-2-methyl1-propanol

T( 0 C) 120.2 129.5 138.5 145.4 125 135 145 129.6 141.0 152.5 166.8 130 140 150 160 170 129 138 149 152 139.7 147.2 154.6 159.8 T (K) 145 T(K) 149.5 160 160 160 130 140 150 160 280 290 300 310 320 330 340 350 109 127 149 120 130 140 150 100 100 80 80 80 80 80 60 80 150 150 150 150

A^(S" 1 ) 6.39 x 10 " 6 1.98 XlO- 5 6.0OxIO- 5 1.24 x l O ~ 4 1.1 x K r 5 3.6 XlO- 5 1.15 x l O - 4 1.64 x l 0 ~ 5 6.28 XlO" 5 2.25 x l O - 4 8.92 x l O - 4 1.82 x l O - 5 5.75 x l O " 5 1.75 x l O - 4 4.88 x l O " 4 1.35 x l O - 3 1.97 x l O - 5 4.3 x l O - 5 1.30 x l O ~ 4 1.62 XlO" 4 6.OxIO- 5 1.43 x l O - 4 3.22 x l O - 4 5.53 x l O - 4 3.2 x 10 16 1.3 x l O - 4 1.9xlO 1 6 1.79 XlO" 4 4.0OxIO- 4 4.53 XlO" 4 4.83 x l O - 4 1.91 x 10" 5 5.95 x l 0 ~ 5 1.78 x l O " 4 4.96 x l 0 ~ 4 7.7 1.5IxIO 1 2.77X10 1 4.87XlO 1 8.34XlO 1 1.38 x l O 2 2.13 x l O 2 3.22 x l O 2 3.8 x 10" 7 2.96 x l O - 5 4.4 x l O " 4 8.82 x 10~6 2.8OxIO- 5 9.26 x l 0 ~ 5 2.78 x l O - 4 2.7 x 10 ~6 1.5 x 10" 6 1.43 x 10 " 8 1.17 x l O " 8 2.04 x 10~8 8.8 x 10 ~9 1.58 x l O " 8 3.3 x 10 ~9 9.6xlO-9 3.63 x 10 " 4 4.15 x 10 ~A 3.11 x 10 ~4 1.16 x 10 " 3

Ea (kj/mol)

159.0

Notes

a a a a a

163.6

exp[- 163.6/RT] 161.5 exp[-161.5//?7] 156.5 i(37-132) 154.8 a,i(2.6) a,i(33) a,i(100) 156.7 U3 U3 U3 U3 154.8 i(10) i(10) i(10) i(10) i(10) KlO) i(lO) i(lO) 159.0 h

t6 t6 t6 t6 t6 142.3 t6

Refs. 227 227 227 227 64 64 64 86 86 86 86 96 96 96 96 96 88 88 88 88 63 63 63 63 63 125 175,125 83 117 117 117 277 277 277 277 111 111 111 111 111 111 111 111 241 241 241 363 363 363 363 197 197 270 270 270 270 270 92 270 346 346 346 346

TABLE 3. cont'd Number of C atoms

J(0C)

Initiator

Solvent

2-tert-Buty\ peroxy-2-methyl1-propanol-di l-Hydroxybutyl-«-butyi peroxide

Chlorobenzene

150

a-Methylstyrene

1-Hydroxyisobutyl-isobutyl peroxide

a-Methylstyrene

1-Hydroxyisobutyl-l-di-isobutyll,l-d 2 peroxide

a-Methylstyrene

Dimethylaminomethylterf-amyl peroxide

Styrene

Diethylaminomethylterf-butyl peroxide

Styrene

N-Piperidinomethyltert-buty\ peroxide

Styrene

9

tert-Butyl tert-amyl peroxide

Cumene

10

tert-Amyl peroxide

Bulk

79.4 99.4 109.9 79.4 99.4 109.9 99.5 109.8 122.0 110 120 130 110 120 130 110 120 130 110 120 130 140 125 132.2 108 128 150 T (K) 125 125 125 132.2 136.7 142.2 149.2 136.7 142.2 149.7 110 120 130 140 110 120 130 140 150 127.5 130 132.5 135 137.5 140 142.5 145 147.5 150 80 85 100 115

8 (cont'd)

Chlorobenzene

Decalin Octane Triethylamine Vapor

11 12

tert-Butyl 1,1-dimethylbutyl peroxide

Cumene

ter/-Butyl 1,1,2-trimethylpropyl peroxide

Cumene

2-Methyl-2-tert-butyl-peroxyacetate Ethyl 2-terf-butylperoxymethylpropenoate

Chlorobenzene Triisopropylbenzene

Apocamphane-1-formyl peroxide 2,2-Bis(tert-butylperoxybutane)

Benzene Benzene

A:d (s" 1 )

Ea (kj/mol)

Notes

1.23 x 10" 3 1.7 x 10~5 1.06 x l O - 4 2.9 x l O - 4 3.7 x 10" 5 2.OxIO" 4 4.8 x l O - 4 6.9xlO~ 5 1.8 x 10~4 4.2 x l O - 4 4.9xlO"5 1.19 x 10" 4 3.76 x l O " 4 4.IxIO-5 1.35 x 10~4 3.25 x l O - 4 5.5 x 10" 5 2.66 x 10 ~4 4.16 x l O - 4 3.86 x 10" 6 1.287 x l O - 5 4.3OxIO- 5 1.406 x l O - 4 5.7xlO- 5 1.15 XlO" 4 1.93 x 10 ~5 1.93 x l O " 4 1.93 x 10- 3 4.02 xlO 1 5 2.8xl0-5 3.0xl0"5 3.5 x 10 ~5 7.2 x 10~5 1.15 XlO" 4 2.16 xlO~ 4 4.8 x l O " 4 1.34 x l O - 4 2.4IxIO- 4 5.61 x 10" 4 4.38 x l O " 6 1.537 x l O " 5 4.99 x l 0 ~ 5 1.544 x l O - 4 7.07 x 10 " 6 2.374 x 10 ~5 7.62 x l 0 ~ 5 2.308 xlO~ 4 4.12 x 10 " 4 1.63 x 10~4 1.95 x l O " 4 2.16 x l O " 4 2.56 x l O - 4 3.47 XlO" 4 3.92 x l O - 4 4.68 x l O - 4 5.37 x l O - 4 6.3OxIO- 4 7.76 x l O ~ 4 2.3 x 10 ~4 3.OxIO- 6 1.9 x l 0 ~ 5 9.36 x l 0 ~ 5

Refs. 346

102.9

83.7

c c c

89.5

130.7

132.4

130.7

tn tn tn tn tn tn tn tn tn

exp[- US35/RT]

154.8-171.5

i(200-225) i(200-225) i(200-225) i(100-200) i(440-610) i(440-610) i(440-610)

C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 151

a a a

32 32 32 32 32 32 25 25 25 303 303 303 303 303 303 303 303 303 363 363 363 363 202 202 344 344 344 344 202 202 202 63 63 63 63 63 63 63 363 363 363 363 363 363 363 363 346 353 353 353 353 353 353 353 353 353 353 244 337 337 337


TABLE 3. cont'd Number of C atoms 12 (cont'd)

13

Initiator

Solvent

tert-Butyl 1,1,3,3-tetramethylbutyl peroxide

Cumene

1-Hydroxy-l-hydroperoxydicyclohexyl peroxide

Benzene

Di-(I -hydroxycyclohexyl)peroxide Diisopropylaminomethyltert-amyl peroxide

Chlorobenzene

1-Phenylethyl terf-butyl peroxide terf-Butyla-cumyl peroxide

Chlorobenzene terf-Butylbenzene

Styrene

Chlorobenzene

Cumene

Dodecane

14

15 16

terf-Butyl />-chlorocumyl peroxide tert-Butyl p-nitrocumyl peroxide tert-Butyl l,l-dimethyl-2-phenylethyl peroxide

Cumene Cumene Cumene

U-Di-(terf-butylperoxy)cyclohexane Ethyl-3,3-di-tert-butylperoxy)-butyrate l-[4-(Dimethylamino)phenyl]ethyl tert-butyl peroxide

Benzene Benzene Chlorobenzene

tert-Butyl /?-methoxycumyl peroxide tert-Butyl p-methylcumyl peroxide terf-Butyl m-methoxycumyl peroxide Bis(l, 1,2,2-tetramethylpropyl) peroxide 2-[4-(Dimethylamino)phenyl]propyl tert-buty\ peroxide l,l-Di-(terf-amylperoxy)cyclohexane tert-Butyl 3-isopropenylcumyl peroxide

Cumene Cumene Cumene Cumene Chlorobenzene

2,5-Dimethyl-2,5-di(tert-butylperoxy)-hexane

Benzene

Benzene Chlorobenzene

Chlorobenzene

2,5-Dimethyl-2,5-di(terr-butylperoxy)-3-hexyne

Benzene

T( 0 C)

kd (s" 1 )

110 120 130 140 85 100 115 130 105 120 110 120 130 129.2 138 158 115 136 159 T(K) 138 158 125 128 138 148 158 125 125 110 120 130 140 93

1.085 x 10~5 3.73 x 10 ~5 1.141 x 10~4 3.40xl0~ 4 9.6xlO~ 6 5.1 x 10 ~5 1.9 xlO~ 4 5.2 x l O - 4 ~1.9xl0~5 ~1.9xlO~4 3.9xl0"5 1.21 x 10~4 3.OxIO" 4 3.09 x 10~5 1.48 xlO~ 4 9.62 XlO" 4 1.93 x 10 ~5 1.93 xlO~ 4 1.93 x l 0 ~ 3 1.17 xlO 1 5 1.44 xlO~ 4 8.88 xlO~ 4 3.04 x l 0 ~ 5 4.44 x 10 ~5 1.39 xlO~ 4 3.21 x 10 ~4 8.88 xlO~ 4 2.42 x 10 ~5 2.20 x 10 ~5 4.35 x 10 ~6 1.458 x 10~5 4.70xl0~ 5 1.463 xlO~ 4 1.9xlO~ 5

111 100.4 110.8 120.9 129.2 129.2 125 125 125 125 129.2

1.9xl0" 5 1.82 xlO~ 6 6.97 x 10 ~6 2.18 x l 0 ~ 5 6.18 x l 0 ~ 5 5.22 x l 0 ~ 5 3.72 x 10 ~5 3.22 x 10 ~5 2.84 x 10 ~5 4.84 xlO~ 4 1.51 x 10~4

90 104 126 152 T(K) 115 130 145 115 134 156 T (K) 115 130 145 160

1.9xl0~ 5 1.93 x 10 ~5 1.93 x 10 ~4 1.93x10-3 1.161xl0 13 1.15 x l 0 ~ 5 6.86 x 10 ~5 4.75 xlO~ 4 1.93 x l 0 ~ 5 1.93 xlO~ 4 1.93 x l 0 ~ 3 1.68 x 1016 3.91 x 10 ~6 2.35 x 10 ~5 1.14 xlO~ 4 6.17 xlO~ 4

Ea (kj/mol)

Notes

a,c2 a,c2 a,c2 a,c2

132.4

tn tn tn a a

exp[-146.98//?7] a a 146.4

a a a a

a a 151.7

m2

m2

a

exp[-128.33/#7] 166.9

exp[- 155.49/RT] 156.9

a a a

a a a a

Refs. 363 363 363 363 337 337 337 337 344 344 303 303 303 282 80 80 344 344 344 344 80 80 352 80 80 80 80 352 352 363 363 363 363 338 338 282 282 282 282 282 352 352 352 352 282

338 344 344 344 344 126,337 126,337 126,337 344 344 344 344 126,337 126,337 126,337 126,337


17

18

Initiator 2,5-Dimethyl-2,5-di(terf-butylperoxy)-3-hexyne

rc-Butyl-4,4-bis(terf-butylperoxy)valerate

Solvent Chlorobenzene

Dodecane

1,1 -Bis-(terr-butylperoxy)3,3,5-trimethylcyclohexane

Benzene

Cumyl peroxide

Benzene

terr-Butylbenzene Chlorobenzene

Cumene

Dodecane

Diisopropylcarbinol Neat

Bicyclo[2.2.2]octane1-formyl peroxide

20

a,a'-Bis(tert-butyrperoxy)diisopropyl benzene

Carbon tetrachloride

Chlorobenzene Cyclohexane Isooctane Toluene Benzene

Chlorobenzene

Neat

24

TABLE 4. Number of C atoms 4

2,5-Dimethyl-2,5-di-(2-ethylhexanoylperoxy) hexane

Benzene

T( 0 C)

^d(S" 1 )

Ea (kj/mol)

Notes

Refs.

120

1.93 x 10~5

344

141 164 T (K) 100 115 130

1.93 xlO~ 4 1.93 x l O - 3 1.90 x 1015 5.83 x 10" 6 3.53 x 10 ~5 2.9IxIO-4

344 344 344 8 8 8

85 100 115 115 130 145 158 112 132 154 T (K) T (K) 138 158 128 138 148 158 138 150 155 160 165 30

6.9xlO~ 6 138 5.05 x l O - 5 2.7IxIO-4 2.05 x 10 ~5 159 1.05 x l O - 4 6.86 x l O - 4 1.72 x 10 ~3 1.93 x IO" 5 1.93 xlO~ 4 1.93 x l O - 3 9.24 x 1015 exp[- 152.61/RT] 4.31 x 1014 exp[- 1443/RT] 2.57 x l O - 4 1.52 x l O - 3 8.75XlO" 5 2.31 x 10- 4 5.37 xlO~ 4 1.83 x l O - 3 3.16 x 10~4 3.98 x 10~3 4.81 x 10- 3 9.63 x l O - 3 1.16 x l O - 2 1.71 x 10 " 4 1.73 x 10 " 3 1.68 x l O - 4 6.2OxIO" 4 6.IxIO-5 5.OxIO- 5 3.66 x 10 " 4 1.9 x l O " 5 147 4.91 x 10 ~5 9.61 x 10- 5 1.93 x 10~5 1.93 x l O - 4 1.93 x l O - 3 7.65 xlO 1 5 exp[- 152.69 kJ/RT] 3.61 x 10~3 4.44 x l O " 3 4.62 x l O - 3 1.9xlO- 5

30 30 30 30 115 125 130 114 134 156 T(K) 155 160 165 68

exp[- 150.61/RT] a a a a a a a a a a

a a a a a a a a a a a n vi

a a a

a a a a

337 337 337 337 126,337 126,337 80 344 344 344 344 67 80 80 80 80 80 80 80 371 371 371 371 244 244 244 244 244 244 244 337 337 337 344 344 344 344 371 371 371 338

ACYL PEROXIDES

Initiator Acetyl peroxide

Solvent Acetic acid

T( 0 C) 55.2 64.9 75.2 85.2 73.2

kd (s"1) 2.8 x 10~6 9.9xlO~ 6 3.75 x l O - 5 1.3OxIO- 4 2.62 x l O - 5

£ a (kj/mol)

Notes

126.4

d,e d,e d,e d,e a

Refs. 106,176 106,176 106,176 106,176 100


Table 4. cont'd Number of C atoms 4 (cont'd)


Solvent Benzene

H-Butanol seoButanol tert-Butanol Carbon tetrachloride

Chloroform Cyclohexane

Cyclohexene

Cyclopentene

Cumene Decane n-Dodecane Ethanol Heptane Hexadecane «-Hexane 1-Hexene

2-Methyl-l-pentene

rc-Octadecane n-Octane Isooctane

1-Pentene

Propionic acid

J( 0 C) 35 55 65 50 70 85 70 60.3 80 55.2 64.9 75.2 85.2 60.3 60.3 60.3 80.3 26 46 65 80 80.3 55.2 64.9 75.2 85.2 60 70 80 90 100 70 80 90 100 80 80 60 80 60.3 80.3 80 80 60 70 80 90 100 80 90 100 60 60 80 60 55.2 64.9 75.2 85.2 70 80 90 64.9 85.2

A^(S"1) 9.5 x 10 ~7 3.14 XlO" 6 1.27 x l O - 5 1.1 x l O " 6 2.39X10" 5 1.73 x l O " 4 2.38 XlO" 5 5.OxIO" 6 8.7xl0-5 2.6 XlO" 6 1.07x10-5 4.65x10-5 1.62 XlO" 4 3.4xlO" 5 3xl0~5 3.1xl0"6 4.9x10-5 1.08 x 10 " 7 4.84 XlO" 7 2.11 x l O " 6 5.5x10-5 ~5 2.1 x 10"6 8.3 XlO" 6 3.6OxIO- 5 1.27 XlO" 4 4.5xlO~ 6 1.77x10-5 7.0x10-5 2.28 xlO" 4 7.61X10" 4 1.6OxIO-5 7.0x10-5 2.55 XlO" 4 7.25 xlO" 4 7.6xl0-5 6.85 x l 0 ~ 5 2.3xlO" 6 6.15x10-5 1.01 x 10 " 4 1.4OxIO-3 7.72 x 10 " 5 5.39 x l O " 5 3.4xlO~ 6 2.35 x 10" 5 8.7x10-5 3.05 XlO" 4 9.83 x l O " 4 9.OxIO" 5 3.12 XlO" 4 9.81 x 10 " 4 1.9xlO" 6 2.9xlO" 6 7.34x10-5 2.9xlO~ 6 2.35 x l O " 6 9.4 XlO" 6 4.03x10-5 1.49 XlO" 4 2.45 x 10 " 5 9.4 x 10"5 3.22 XlO" 4 1.4 x l O " 5 1.66 XlO" 4

Ea (kj/mol)

Notes

134

a a a a

135.1

c,e c,e c,e c,e

133.9

131.4

c,e c,e c,e c,e

133.5

137.2

129.7

132.6

126.8

134.7

c,e c,e c,e c,e

d,e

Refs. 68 68 68 337 126,337 126,337 16 4 20 106,176 106,176 106,176 106,176 4 4 4 4 68 68 68 20 4 106,176 106,176 106,176 106,176 20 20 20 20 20 20 20 20 20 20 168 70 168 4 4 168 168 70 20 20 20 20 20 20 20 70 70 168 70 106,176 106,176 106,176 106,176 20 20 20 106,176 106,176



Solvent n-Tetradecane Toluene

Vapor (toluene)

6

Propionyl peroxide

Acetic acid Acetic anhydride Benzene

Benzonitrile Dioxane n-Hexane Isooctane Nitrobenzene Toluene Vapor

2-Iodopropionyl peroxide

Perfluoropropionyl peroxide

8

2,2,3,3-Tetrafluoropropionyl peroxide tert-Butyl permaleic acid Butyryl peroxide

Acetone Benzene

H-Butyl vinyl ether Cyclohexene 95%Ethanol Freon 113

Isooctane Freon 113 Acetone Acetic acid Acetic anhydride

J( 0 C) 60 80 60.3 55.2 64.9 75.2 85.2 73.2 85.5 90 88.0 134.7 150.7 161.7 170.7 184.2 65.0 85.0 65.0 85.0 65.0 85.0 50 70 85 65.0 85.0 65.0 85.0 65.0 85.0 65.0 86.5 65.0 85.0 65.0 85.0 65.0 85.0 99.4 134.4 152.2 176.4 190.9 T (K) 56 62.5 62.5 62.5 62.5 62.5 62.5 20 30 40 T (K) T(K) 25 35 87 65.0 85.0 65.0 85.0

^d(S1) 2.OxIO" 6 5.9OxIO" 5 5xlO"6 2.7 xlO~ 6 1.14 x l O " 5 4.70xl0~ 5 1.59 xlO~ 4 3.06 XlO" 5 1.72 XlO" 4 7.33 x l O " 5 3.12 x l O " 4 3.1 x 10" 2 1.18XlO"1 2.77XlO" 1 6.10X10" 1 1.76 3.8xlO~ 5 4.3 XlO" 4 3.5 x l O " 5 4.5 x l O " 4 1.88 x KT 5 2.4OxIO" 4 2.72 x l O " 6 4.3OxIO" 5 2.89 XlO" 4 3.9xl0"5 5.IxIO"4 4.5 x 10~5 4.5 x l O " 4 1.50x 10" 5 1.72 x l O " 4 9.8 x l O " 6 1.44 x l O " 4 3.7xl0"5 4.1 x 10 " 4 1.87 x l O " 5 2.54 x l O " 4 1.0 x l O " 5 1.6 xlO~ 4 8 xlO"4 2.6 XlO" 2 1.22XlO- 1 8.OxIO" 1 2.33 2.5 x 10 " 4 2.19 x 10 ~4 (2.40-2.81) x 10 ~4 7.12 XlO" 4 (2.36 ±0.07) x 10 ~4 2.47 x 10" 4 2.7xlO" 4 4.OxIO" 4 2.19 x 10 " 5 8.5OxIO- 5 3.26 XlO" 4 1.8 x 109 1.5xlO 17 2.26 x 10 " 4 7.17 x 10 " 4 1.9xlO~ 5 4.7 x 10" 5 5.6 x l O " 4 4.3 x 10 " 5 5.5 x l O " 4

Ea (kj/mol)

129.7 133.9

138.1 129.7 123.4

123.0 128.9 129.3 127.6

130.5 116.7

Notes

c,e c,e c,e c,e a a a

c,e c,e d,e c,e c,e c,e a a a d,e d,e c,e c,e

123.8 130.5 120.9

c,e c,e c,e

130.1 125.5 125.5

exp[- 125.5/RT]

100.1

s s n,s p s s s h

exp[- 83.8//?7] exp[- 121.5/RT} 86.3

h

108.8

125.1

a c,e c,e c,e

Refs. 70 168 4 106,176 106,176 106,176 106,176 100 100 113 105 105 105 105 105 105 51 51 51 51 51 51 126,337 126,337 126,337 51 51 51 51 51 51 51 51 51 51 51 51 51 51 85 85 85 85 85 85 77 77 77 77 77 77 77 283 283 283 304 304 283 283 338 51 51 51 51

Notes page II - 69; References page II - 70


Initiator Butyryl peroxide

Solvent Benzene Benzonitrile Dioxane Hexane Isooctane Toluene Vapor

Isobutyryl peroxide

Acetonitrile Benzene

Benzonitrile tert-Butanol Carbon tetrachloride

Chlorobenzene

Chloroform Cyclohexane Fluorobenzene Isooctane

Cyclopropane formyl peroxide

Isopropanol Nitrobenzene Nujol Tetralin Toluene Vapor p-Xylene Carbon tetrachloride

Diacetyl succinoyl diperoxide

Styrene

Succinoyl peroxide

Acetone

T( 0 C) 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 96.7 127.4 158.9 178.9 T(K) 40 20 30 40 40 40 40 40 40 45 50 55 60 40 23 39 57 T (K) 40 40 40 40 25 35 45 55 T (K) 40 40 40 40 40 40 40 40 64.5 70.4 77.8 60 73.5 85 70 85 100

â(S1) 2.24 x 10~5 3.02 x l O - 4 4.3 x 10~5 5.8 x l O - 4 4.6xlO~ 5 4.6 x l O - 4 1.14 x 10~5 1.53 x l O - 4 1.11 x 10~5 1.56 x l O " 4 2.14 x l O " 5 2.87 x l O - 4 1.6 x l O " 5 2.OxIO- 4 8.6 x l O " 4 1.5 XlO" 2 3.OxIO" 1 1.27 1.9 xlO~ 4 6.81 x 10 " 4 1.6 x l O " 5 6.75 x l O - 5 2.59 x l O - 4 2.38 XlO" 4 2.4OxIO- 4 4.2xlO~ 4 2.5IxIO" 4 7.8xl0"5 1.58 XlO" 4 3.05 x l O - 4 5.61 x 10~4 7.67 xlO~ 4 1.73 x 10 " 4 1.93 x l O - 5 1.93 x l O - 4 1.93 XlO" 3 3.37 xlO 1 4 7.5 x 10 ~5 4.5 x 10 ~5 4.7OxIO- 5 1.23 x 10 " 4 3.35 x 10 ~6 1.54 XlO" 5 6.14 x l O - 5 2.26 x l O - 4 2.8 x 1014 3.2 x l O " 5 3.05 x 10~4 5.8OxIO- 4 4.63 XlO" 5 1.75 x 10 ~4 1.43 x 10 ~4 -1 x 10 ~5 1.4OxIO- 4 4.4xlO" 6 9.3 x 10 ~6 2.31 x 10- 5 5.2xlO~~6 2.3 x l O - 5 9.3 x 10- 5 2.8OxIO- 5 1.21 x 10- 4 4.36 x l O - 4

Ea (kj/mol)

Notes

131.4

d,e c,e d,e

131.4 116.3 131.4 133.5 130.5

c,e c,e c,e c,e c,e c,e d,e c,e

123.8 123.8

exp[-123.8//?7] 109

1113 a a a In3

exp[- 109.06//?7]

114.2

exp[- 1H2/RT]

125.5

99.6

a a a

Refs. 51 51 51 51 51 51 51 51 51 51 51 51 51 51 85 85 85 85 85 167 337 337 337 167 148,244 148 148 148 148 148 148 148 148 344 344 344 344 148 148 167 148 84 84 84 84 84 148 148 148 167 148 148 167 148 34 34 34 215 215 215 126,337 126,337 126,337

Table 4. cont'd Number of C atoms 9

10

11

Initiator Acetyl benzoyl peroxide

T( 0 C)

Chlorobenzene

70 96 96 75 75 75 41 41 65 70 75 14 25 44.5 56.5 44.5 60 73.5 85 50 60 70

5-Bromo-2-thenoyl peroxide 4-Bromo-2-thenoyl peroxide 5-Chloro-2-thenoyl peroxide a-Chloropropionyl m-chlorobenzoylperoxide Cyclobutane formyl peroxide

Carbon tetrachloride Carbon tetrachloride Carbon tetrachloride Acetonitrile Cyclohexane Carbon tetrachloride

Cyclopropane acetyl peroxide


Diacetyladipoyl diperoxide

Styrene

Difuroyl peroxide

styrene

2,2,3,3,4,4,5,5-Octafluoropentanoyl peroxide

Freon 113

Perfluoro-2-(2-ethoxysulfinic acid) propionyl peroxide Pivaloyl peroxide 2-Thenoyl peroxide 3-Thenoyl peroxide Benzoyl isobutyryl peroxide

m-Chlorobenzoyl isobutyryl peroxide

12

Solvent

Freon 113 Carbon tetrachloride Carbon tetrachloride Carbon tetrachloride Acetonitrile Cyclohexane

Acetonitrile Cyclohexane

p-Chlorobenzoyl isobutyryl peroxide

Cyclohexane

p-Fluorobenzoyl isobutyryl peroxide

Cyclohexane

5-Methyl-bis-2-thenoyl peroxide p-Nitrobenzoyl isobutyryl peroxide

Carbon tetrachloride Cyclohexane

P-Allyloxypropionyl peroxide

Toluene

p-Xylene

m-Chlorobenzoyl 2-methylbutanoyl peroxide

Acetic acid Acetonitrile

kd (s"1) 2xl0~5 5.12 x l O " 4 4.08 XlO" 4 1.53 x 10 " 5 1.14 x 10 ~5 1.58 x 10 ~5 3.05 x 10 ~5 1.51xl0~ 5 5.15 x 10 " 5 8.95,6.63 x l O " 5 1.41 x 10" 4 9.45 x 10 ~5 9.75,10.57 x 10" 4 5.01 x 10 " 5 2.64 XlO" 4 6.5-8.OxIO" 4 6.6xlO" 6 4.73 XlO" 5 1.84 x l O " 4 7.0xl0"7 2.9 xlO~ 6 1.03 XlO" 5

20 30 40 T(K)

3.29 x 10 " 5 1.27 XlO" 4 5.01 x 10 " 4 2.8xlO 1 4

10 75 75 41 41 70 40 50 60 70 41 40 50 41 50 55 60 65 55 60 65 70 75 40 45 50 55 60 70 80 90 70 80 90 40 40

1.9xlO~ 4 2.21 x 10 ~~5 2.14 x 10 " 5 4.06 x 10 " 4 1.63 x l O " 5 3.05 xlO~ 4 1.45 x l O - 5 5.398 XlO" 5 1.924 x l O " 4 6.872 x l O " 4 1.03 x 10 ~3 3.486 x 10 " 5 1.362 x l O " 4 4.4OxIO- 5 1.029 x 10 ~4 1.651 x 10- 4 3.21 x 10- 4 5.638 x l O - 4 1.117 x 10 " 4 2.038 XlO" 4 4.893 x l O - 4 9.603 x l O " 4 2.92 x 10 " 5 8.1xl0"5 1.336 x l O " 4 2.889 x l O - 4 4.725 X l O ' 4 8.921 x 10 ~4 2.0IxIO" 5 8.62 x l O " 5 2.53 x l O " 4 2.32 x l O " 5 8.88 x l O " 5 2.95 x l O " 4 1.60 x 10 ~3 1.72 x 10 " 3

Ea (kj/mol)

Notes

z(25),vi3 z(19),vi3 a,mi a,mi a,mi ni3 ni3

101.7 n

125.7

h

100.6

h

exp[-95.1//?7]

a,mi a,mi

112.5

h,j j j j

111.3

h,j j j

a

a a a a a a

Refs. 155 284 284 232 232 232 167 167 34 34 34 34 34 24 24 24 215 215 215 287 287 287 283 283 283 304 244 232 232 167 167 167 164 164 164 164 167 164 164 167 164 164 164 164 164 164 164 164 232 164 164 164 164 164 191 191 191 191 191 191 256 256



14

Initiator m-Chlorobenzoyl 2-methylbutanoyl peroxide

Solvent

Cyclobutane acetyl peroxide

2-Butanol Carbon tetrachloride Cyclohexane Carbon tetrachloride

Cyclopentane formyl peroxide


Hexanoyl peroxide 5-Hexenoyl peroxide

Toluene Toluene

4-Methoxybenzoyl isobutyrylperoxide

Cyclohexane

4-Methylbenzoyl isobutyrylperoxide

Cyclohexane

4-Methyl-2-thenoyl peroxide 5-Methyl-2-thenoyl peroxide Perfluoro-2-furnanacetyl peroxide Perfluoro-2-propoxypropionylperoxide Perfluoro-2-n-propoxypropionylperoxide

Carbon tetrachloride Carbon tetrachloride Freon 113 Freon 113 perF-ether mix. Freon 113

Perfluoro-2-iso-propoxypropionylperoxide

Freon 113

2-Azidobenzoyl peroxide

Benzene

Benzoyl peroxide

Acetic acid Acetone

Acetonitrile Acetophenone

Allyl alcohol Anisole Benzaldehyde Benzene

T( 0 C) 40 40 40 65 70 75 40 45 50 55 77 60.1 70.4 76.4 85.0 55 60 65 70 40 50 60 70 75 75 T (K) T(K) T (K) 20 30 40 20 30 40 50 80 75 50 70 85 100 70 70 80 94.5 80 30 80 90 25 30 55 60 60 80 70 78 78 79.8 80 66 72.5 78 70

kd (s"1) 9.0xl0~4 1.32 x 10 ~4 6.OxIO" 5 1.37 x 10 ~5 2.13,3.08 x 10- 5 3.83 x l O - 5 1.50 x 10 ~5 2.55 XlO" 5 4.96 XlO" 5 8.17,7.85 x 10" 5 1.186 x 10 ~4 1.06 x 10 " 5 4.15 XlO" 5 8.59 x l O " 5 2.668 x l O - 4 5.465 x 10 ~5 1.024 x l O " 4 1.876 XlO" 4 3.208 XlO" 4 9.6IxIO" 6 3.619 x l 0 ~ 5 1.305 XlO" 4 4.772 x l O " 4 2.92 x 10 " 5 4.21 x 10 ~5 1.2 x 1011 4.4xlO 1 4 8.9 x 1016 4.81 x 10 ~5 1.96 x 10 ~4 7.16 XlO" 4 8.32 x 10 ~5 3.43 x 10 ~4 1.34 x l 0 ~ 3 2.5 x 10~5 9.4 XlO" 4 7.53 x 10 " 5 2.25 x 10 ~6 2.63X10- 5 1.34 xlO~ 4 5.83 xlO~ 4 1.76 x 10 ~5 1.15 x 10~5 4.32xlO- 5 2.30xl0~ 4 3.80 x 10 ~4 1.42 x 10 ~7 5.50xl0~ 5 1.71 x 10- 4 6.4xlO~ 5 4.80 xlO~ 8 1.14 xlO~ 6 2.76 xlO~ 6 2.0xl0~6 2.5xlO-5 1.38x10-5 2.3OxIO- 5 1.67x10-5 3.48x10-5 4.8x10-5 7.72 x 10 ~6 1.87x10-5 3.77x10-5 1.17x10-5

Ea (kj/mol)

129.3

Notes

c c c c

j j j j a,mi ^m1 exp[- 11A/RT] exp[- 9Z.5/RT] exp[-110.2/RT] 100.1

h

102.7

h

111.3

126.4

116.3

124.3

129.7

133.9

d2 d2 a,r a a a a tj a a a a,r a a,r a,r p2 a a,r a,r m2 m2 a c X9

a a a a

Refs. 256 256 256 34 34 34 34 34 34 34 209 209 209 209 209 164 164 164 164 164 164 164 164 232 232 304 304 304 283 283 283 283 283 283 161 161 74 126 126 126 126 124 5 5 5 74 109 74 74 279 109 74 74 14 14 213 230 230 170 20 131 131 131 73


Initiator Benzoyl peroxide

Solvent Benzene

Benzyl alcohol Bromobenzene

Butanol Butanone Di-n-butyl phthalate

Carbon tetrachloride Chlorobenzene

Chloroform Cumene

Cyclohexane Decane Decalin Dioxane

J( 0 C) 75 80 80 50.8 54.9 60.9 65.6 71.0 75.8 70 85 100 70 70 75 75 85 85 100 100 79 80 80 80.2

80 80 117 127 137 147 75 79 70 80 80.2 80.2 80.2 80.2 71 91 113 T (K) 30 80 85 90 30 45 60 80 T (K) 100 80 80 80 70 80 80 80

kd (s"1) 2.62 x 10 " 5 4.39 XlO" 5 3.27 XlO" 5 4.28 XlO" 7 8.53 x l O - 7 1.66 x l O - 6 3.22 XlO" 6 5.94 x l O - 6 1.19 XlO" 5 1.27 XlO" 5 8.94 x l O - 5 4.96 x l O - 4 1.03 x l O - 5 1.18 XlO" 5 1.48 x l O - 5 1.66 x l O - 5 4.7 x l O - 5 5.5 XlO" 5 2.28 x l O - 4 2.56 x l O " 4 2.58 x l O - 5 3.35 x l O " 5 4.44 x 10 " 4 8.15 x l O " 5 2.19 x l O " 5 3.84 x l O - 5 3.55 x l 0 ~ 5 4.34 x l O - 5 6.06 x 10 " 4 4.64 x 10 " 5 2.78 x 10 ~3 7.44 X l O " 3 1.72 x l O - 2 3.89 X l O " 2 1.07 x 10 " 5 1.69 X l O " 5 1.35 x 10 ~5 4.64 x l O - 5 2.85 x l O " 5 2.36 x l O - 5 3.52 x l 0 ~ 5 2.62 X l O " 5 1.93 x l O - 5 1.93 x l O " 4 1.93 XlO" 3 6.94 x l O 1 3 5.47 x 10 ~8 3.69 x 10 ~5 6.39 XlO" 5 1.19 x l O - 4 7.3OxIO- 8 1.85 x l O 7 1.45 x l O - 6 1.70 XlO" 5 1.20 x 10 13 2.5 XlO" 4 7.72 x 10 ~5 2.53 x 10 " 5 2.26 x 10 " 4 1.30 x 10 " 5 6.72 x l O - 4 4.2OxIO- 4 4.18 x l 0 ~ 5

Ea (kj/mol)

123.8

130

128.0 124.3

Notes a a a,b 2 a,t2 a,t2 a,t2 a,t2 a,t2 a,t2 a a a a,m2 t2 m3 m3 m3 a,t6 a a,r t9

Hi1 m3 m5

120.1

a,r a,r yi6

a,r t 6 ,a I1 a,r t9 Cm 1 c,m 3

exp[- 12235/RT] a a,r a,r a,r a 120.5

exp[- 120.5/RT] a,t7 a,r a,r ti a,r a,r a,m!

Refs. 73 73 347 69 69 69 69 69 69 337 126,337 126,337 16 124 12 12 12 12 12 12 120 7 74 231 231 231 231 231 74 74 236 236 236 236 74 121 124 74 231 231 231 231 344 344 344 344 109 74 74 74 109 67 67 67 67 122 74 270 74 74 74 6 232

Notes page 11-69; References page 11-70



Solvent Ethanol

Ethylbenzene

90% Formic acid H-Heptane

Hexadecane Hexane Isooctane Isopropylbenzene Methyl acetate Methylcyclohexane 4-Methyl-2pentanone a-Methylstyrene Mineral oil Neat Nitrobenzene PEG 400

90% aq. PEG 400

80% aq. PEG 400

70% aq. PEG 400

rt-Pentanol Phenol Propionic acid Propylene glycol

Styrene

T( 0 C) 25 40 50 30 75 80 85 90 80 80 80 80 130 135 140 145 145 145 145 150 155 160 80 80 80 80 80 49.2 53.9 80 80 70 80 105 80 30 25 40 50 70 25 40 50 70 25 40 50 70 25 40 50 70 80 80 80 25 40 50 34.8 49.4 61.0 74.8 100.0

^d(S1) 3.02 x l O ~ 8 2.77 x l O " 7 4.72 x l O - 7 3.61 x 10 " 8 1.8IxIO- 5 3.33 XlO" 5 5.56 XlO" 5 1.01 x 10- 4 3.15 x l 0 ~ 5 6.94 x 10 " 4 3.11 x 10 ~5 2.7IxIO-5 5.73 XlO" 3 1.02 x l O " 2 1.54 x l O - 2 2.25 XlO" 2 2.22xlO-2 2.21 x 10~2 2.12 x l O - 2 3.47 x l O " 2 5.21 x 10- 2 7.87 x l O - 2 2.51 x 10 " 5 2.85 x 10 ~5 2.79 x 10 ~5 2.7OxIO" 5 3.34 x 10~5 6.28 x 10 ~7 1.0 XlO" 6 5.25 x 10 ~5 4.28 x 10 ~5 3.02 x 10 " 5 2.89 x 10~5 7.22 x 10 ~3 4.58 x 10 ~5 6.6IxIO-8 5.0IxIO-7 5.73 x l O - 6 1.15 x l 0 ~ 5 1.15 XlO" 4 3.65 x 10~7 5.35 x l O " 6 1.15 x l O - 5 1.15 x l O " 4 2.77 x 10 ~7 3.09 x l O " 6 7.29 x l O - 6 1.15 x l O - 4 1.71 x 10 ~7 2.1IxIO-6 5.01 x 10- 6 1.15 x l O " 4 1.48 x 10 ~4 6.25 x 10 " 4 3.19 x 10~5 3.25 x 10 ~8 1.51 x l O ~ 7 3.16 x l O - 7 3.89 x 10 ~8 5.28 XlO" 7 2.58 x l O - 6 1.83 x l 0 ~ 5 4.58 x l O " 4

£ a (kj/mol)

Notes a a a a a,r a,r a,r a,r c a,r a,r z (1500) z (1500) z (1500) z (500) z (1000) z (1500) z (2000) z (1500) z (1500) z (1500)

123.8

117.6

m2 c a,t2 a,t2 a,r a,r a m2 a a,r a a a a a a a a a a a a a a a a a a,r a,r a,r a a a a a a a a

Refs. 351 351 351 109 74 74 74 74 239 74 74 270 377 377 377 377 377 377 377 377 377 377 270 270 270 308 229 69 69 74 74 213 308 371 74 109 351 351 351 351 351 351 351 351 351 351 351 352 351 351 351 351 74 74 74 351 351 351 10 10 10 10 10



Solvent Poly(styrene)

Tetradecane Tetralin Toluene

Poly(vinylchloride)

Styrene

3-Bromobenzoyl peroxide

4-Bromobenzoyl peroxide 4-terr-Butylbenzoyl peroxide 2-Chlorobenzoyl peroxide 3-Chlorobenzoyl peroxide 4-Chlorobenzoyl peroxide

p-Xylene Benzene

Dioxane Dioxane Dioxane Acetophenone Benzene Acetophenone Dioxane Acetophenone Benzene

Dioxane Styrene

Cyclohexane formyl peroxide

Benzene


Cyclopentane acetyl peroxide


Diacetylsebacoyl diperoxide


T( 0 C) 56.4 64.6 76.7 83.4 98.5 70.9 80.1 89.5 80 80 30 49.0 55.1 60.2 65.1 70.3 60.00 64.6 76.7 83.4 98.5 50 60 70 80 60 80 80 80 80 80 80 80 80 80 80 80 50 85 100 80 34.8 49.4 61.0 74.8 100.0 30 35 40 45 50 35 45 50 60 35 40 45 65 70 75 60 73.5 85

^d(S"1) 3.8 x 10~7 1.47 x l O - 6 9.27 x l O " 6 2.5OxIO- 5 1.41 x l O " 4 2.86 x l O - 6 1.11 x l O - 5 3.33 x l O - 5 2.64 x 10 ~5 3.72 x 10 " 5 4.94 x l O " 8 6.OxIO- 7 1.31 x 10- 6 2.83 x l O - 6 5.69 x l O - 6 1.10 x l O - 5 2.24 x l O " 6 6.3xlO" 7 5.11 XlO" 6 1.44 x l O - 5 9.33 x l O " 5 7 x IO" 7 7.7 x l O - 6 9.9 x l O " 6 3.1OxIO- 5 1.1 x 10 " 6 1.22 x l O - 5 2.6OxIO- 5 2.57 x 10 ~5 3.23 x 10 ~5 6.06 x 10 ~5 3.88 x 10 " 4 3.12 x 10 " 4 2.85 x 10 ~5 2.63 x 10 ~5 3.83 x 10 " 5 2.17 x 10 ~5 6.2 x l O " 7 6.64 x l O - 5 3.86 x l O - 4 3.62 x 10 " 5 8.3xl0-8 8.3 x l O " 7 3.33 x l O - 6 2.22 x l O - 5 4.17 x l O - 4 9.64 x 10 ~5 1.46 x l O " 4 3.1OxIO- 4 5.11xlO" 4 7.77 x l O - 4 6.6xlO~~5 2.1IxIO-4 4.45 xlO~ 4 1.3OxlO" 3 2.87 x l O - 5 5.22,5.29 x 10 " 5 9.67 x l O - 5 1.48 x 10" 5 3.2OxIO" 5 4.97 x l O - 5 1.04 x 10 ~5 5.20xl0~5 2.3OxIO- 4

E a (kj/mol)

120.5 123.8

Notes

Refs.

a a a a a a a a

17 17 17 17 17 15 15 15 270 74 109 69 69 69 69 69 291 17 17 17 17 287 287 287 229 116 116 7 6,232 6,232 232 5 7 5 6 5 7 126 126 126 6 10 10 10 10 10 219 219 219 219 219 148 148 148 148 34 34 34 34 34 34 215 215 215

a,r a a,t2 a,t2 a,t2 a,t2 a,t2 e,m3 a a a a

125.7

c

123.0 128.4 127.2 128.9

84.5

a a,mi a,mi a,m a a a a,mi a a a a a ^m1 a a a a a a,h

Xi X1 xi



Initiator 2,4-Dichlorobenzoyl peroxide

Solvent Benzene

Styrene

2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptanoyl peroxide Heptanoyl peroxide 6-Heptenoyl peroxide

2-Iodobenzoyl peroxide 2-Iodobenzoyl 4-nitrobenzoyl peroxide

3-Methylbenzoyl peroxide 4-Methylbenzoyl peroxide 2-Nitrobenzoyl peroxide

Freon 113 Toluene Toluene

Chloroform Acetone Acetonitrile Benzene Carbon tetrachloride Chloroform Nitrobenzene Dioxane Dioxane Acetophenone Methyl iodide

15

16

3-Nitrobenzoyl peroxide 4-Nitrobenzoyl peroxide 3,5-Dinitrobenzoyl peroxide Perfluoroheptanoyl peroxide

Acetophenone Acetophenone Acetophenone Freon 113

Benzoyl phenylacetyl peroxide

Benzene

4-terf-Butylbenzoyl isobutyryl peroxide

Cyclohexane

3-Cyanobenzoyl benzoyl peroxide 3-Methoxybenzoyl benzoyl peroxide 4-Methoxybenzoyl benzoyl peroxide 4-Methoxybenzoyl 3-bromobenzoyl peroxide 4-Methoxybenzoyl-3,5-dinitrobenzoyl peroxide

Dioxane Dioxane Dioxane Dioxane Benzene Nitrobenzene

J( 0 C) 70 70 50 70 85 34.8 49.4 61.0 74.8 100.0 30 40 77 70 70 77 85 22 25 25 25 25 25 25 80 80 59.3 80 24.95 45.05 80 80 80 20 30 40 20 25 25 25 30 35 55 60 65 70 80 80 80 80

^d(S" 1 ) 9.7OxIO" 5 1.24 xlO~ 4 1.08 xlO~ 5 1.37 xlO~ 4 7.69 XlO" 4 3.88 x 10 " 6 2.39 x l 0 ~ 5 7.78 xlO~ 5 2.78 xlO~ 4 4.17 x l 0 ~ 3 1.14 x 10~4 4.06 x 10 ~4 1.24 x 10 ~4 5.33 x 10 ~5 5.01 x 10 ~5 1.07 xlO~ 4 2.88 xlO~ 4 1.86 x 10 ~3 3.0xl0~4 2.1x 10 ~4 5.7xl0~5 3.4xl0~5 2.8xlO~ 4 6.2xlO~ 4 4.38 x 10 ~5 6.11 x 10 ~5 5.80xl0~ 5 1.34 x l 0 ~ 3 1.78 xlO~ 5 1.50xl0~ 4 3.80xl0"5 4.33 x 10 " 5 1.87 x l 0 ~ 5 3.01 x 10 ~5 1.11 xlO~ 4 4.20xl0~4 1.10 x 10~4 2.05 xlO~ 4 3.15 xlO~ 4 6.38 xlO~ 4 3.88 xlO~ 4 6.67 xlO~ 4 6.543 x 10 ~5 1.171 x 10~4 2.663 xlO~ 4 5.016 xlO~ 4 2.73 x 10 ~2 4.82 x 10 ~2 7.57 x 10 ~5 4.43 x 10 ~2

£ a (kj/mol)

117.6

100.6

Notes a,j a,k a a a a a a a a h a a,k a,j a,j a,k

119.7 81.2 126.4 126.8 130.5 98.0

a,mi a,mi a a h a a a

90.8 vi n

ti 0 tio t 10 tio a,m\ a,mi a,mi a,mi

Refs. 16 16 126,337 126,337 126,337 10 10 10 10 10 283 283 19 19 19 19 19 82 78 78 78 78 78 78 232 232 5 5 82 82 5 5 5 283 283 283 222 222 222 222 222 222 164 164 164 164 6 6 6 6

51 51 51

1.02 x 10 ~5 9.61 x 10 ~4 1.67 XlO" 3

t5

108 108 108

a a

89 89

a a a

95 116 116 126 126 126

4-Methoxybenzoyl 4-nitrobenzoyl peroxide

Benzene

70 70

2.08 x 10 ~5 8.03 x l 0 ~ 5

3,5-Dibromo-4-methoxybenzoyl peroxide

Benzene

Caprylyl peroxide

Benzene

60 60 80 50 70 85

9.5 x 10 ~7 6.1 xlO~ 7 9.4 x 10 ~6 3.44 x 10 ~6 5.78 x l 0 ~ 5 3.78 xlO~ 4

128.9


Initiator

Solvent

Caprylyl peroxide /7-(Chloromethyl)benzoyl peroxide

Mineral oil Acetone

3-Cyanobenzoyl peroxide 4-Cyanobenzoyl peroxide Cycloheptane formyl peroxide

THF Toluene Dioxane Acetophenone Dioxane Carbon tetrachloride

Cyclohexane acetyl peroxide


2-Ethyl-4-methyl-2-pentenoyl peroxide 2-Ethylhexanoyl peroxide 2-Ethyl-2-hexenoyl peroxide 2-Iodophenylacetyl peroxide

2-Methoxybenzoyl peroxide 3-Methoxybenzoyl peroxide 4-Methoxybenzoyl peroxide 2-Methylbenzoyl peroxide 3-Methylbenzoyl peroxide 4-Methylbenzoyl peroxide Endo-norbornane-2-carbonylperoxide

Mineral oil Mineral oil Mineral oil Acetone Chloroform Toluene Acetophenone Acetophenone Dioxane Acetophenone Dioxane Acetophenone Acetophenone Dioxane Acetophenone Dioxane Carbon tetrachloride

Exo-norbornane-2-carbonylperoxide


Endo-norbornene-5-carbonylperoxide


Exo-norbornene-5-carbonylperoxide


Dioctanoyl peroxide

w-Heptane

T( 0 C) T (K) 70 70 70 70 80 80 80 35 40 45 65 70 75 54.4 64.3 71.8 T(K) T(K) T (K) 0 0 0 50 80 80 80 80 80 70 80 80 80 80

A^(S"1)

Ea (kj/mol)

9.8 x 1015 2.07 x 10 ~5 1.82 x l O " 5 1.15 XlO" 5 8.8xl0"6 1.70 x 10 ~2 2.43 x 10 ~5 2.03 x 10 " 5 7.85 x 10 ~5 1.63,1.34XlO"5 2.02 XlO" 4 1.27 x 10 " 5 2.76 XlO" 5 3.61 x 10 " 5 3.1 x 10 " 6 1.19 x l O " 5 2.95 XlO" 5

exp[- UOA/RT]

7.IxIO16 1.2xlO 14 1.6 x 1016 2.6OxIO" 5 3.98 x 10 ~5 1.3xlO" 5 6.0xl0"5 2.15 XlO" 3 6.42 x 10 " 5 5.75 x 10 ~5 1.56 x 10 " 4 1.18 x 10 ~A 9.02 x 10 " 5 4.7OxIO" 5 4.4OxIO" 5 5.92 x 10 " 5 6.13 x 10~5

exp[-138.4//?7] exp[- 106A/RT] exp[-136.3//?7]

Notes

m7

a,mi a a,mi

113.8 120.9 120.1 126.4 126.4 125.1

Refs. 1 307 307 307 307 6 5 6 34 34 34 34 34 34 24 24 24

c,e,q q a a a a,mi a a,mi a a a,mi a a,mi

1 1 1 79 79 79 5 5 5 6 5 6 5 5 6 5 6

44.5 53.9 65.9

6.IxIO"6 2.83 XlO" 5 1.25 XlO" 4

j j j

23 23 23

44.5 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 445 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 70 80 80

9.1 x 10" 6 4.33 x l O " 5 1.28 x l O " 4 4.68 x 10 " 5 2.05 x 10 " 4 8.18 xlO~ 4 7.2 XlO" 5 1.6OxIO"4 8.48 XlO" 4 6.30xl0~ 5 1.2IxIO" 4 7.18 x l O " 4 2.22 x l O " 5 4.52 XlO" 5 2.37 x l O " 4 6.58 x 10 " 5 1.2IxIO- 4 8.42 XlO" 4 2.58 xlO~ 5 1.2OxIO"4 7.1OxIO- 4 1.70xl0" 5 7.0IxIO-5 6.8OxIO- 5

j,m 2 j , m2 j,m 2 j j j j , m2 j,m 2 j , m2 j j j j,m 2 j,m 2 j,m 2 j j j j,m 2 j,m 2 j,m 2 z (1500) z (500) z (1000)

23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 377 377 377


Table 4. Number of C atoms 16 (cont'd)

18

cont'd

Initiator

Solvent

T( 0 C)

^d(S1)

Ea (kj/mol)

Notes

Refs.

80 80 80 90 95 100 63 80 100 T (K) 20 20 20 20 0 0 18 80 80 80

6.27 x 10~5 6.01 x l 0 ~ 5 5.77xlO-5 2.13 x l O ~ 4 3.8OxIO- 4 6.79 x l O ~ 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 2.30 x 10 15 1.02 x 10 ~3 4.76 x 10 ~4 1.86 x 10 ~4 1.6OxIO- 4 7.8xl0~5 2.5OxIO- 5 3.34 XlO" 4 1.42 x 10 ~4 1.4 x l O ~ 4 2.3 x 10 ~4

Acetonitrile 2-Butanol Carbon tetrachloride Cyclohexane

40 40 40 40

5.9xl0~3 4.4xlO~ 3 6.7 x 10 ~4 4.4xlO~ 4

256 256 256 256

5-terf-Butylthenoyl peroxide Cinnamoyl peroxide

Acetonitrile 2-Butanol Carbon tetrachloride Cyclohexane Carbon tetrachloride Styrene

Dibenzoyl succinoyl diperoxide

Unknown

Nonanoyl peroxide Isononanoyl peroxide (3,5,5trimethylhexanoyl peroxide)

Mineral oil

40 40 40 40 75 50 70 70 75 85 T(K)

4.2xlO~ 3 2.8 x 10 ~3 6.5 x 10 ~4 3.9xlO~ 4 4.03 x 10 ~5 1.2OxIO- 5 1.67 x l O - 4 7.7 x 10 ~6 1.42 x l O - 5 5.4 x l O - 5 8.4xlO 1 4

256 256 256 256 232 316 316 214 214 214 1

50 70 85 60 59 77 96 T (K) 60 70 80 80 80 80 80 80 90 100 120 125 130 135 140 145 150 T (K)

6.IxIO-6 8.02 x l 0 ~ 5 5.3OxIO- 4 1.9 x l O - 5 1.93 x 10 ~5 1.93 XlO" 4 1.93 x l O - 3 2.84 x 1015 5.28 x 10 ~6 2.06 x l 0 ~ 5 9.53 x l O - 5 9.1OxIO- 5 8.62 x l O - 5 8.24 x l O - 5 7.86 x l O - 5 7.46 x l O - 5 2.52 x l O - 4 8.8IxIO-4 6.98 x l O - 3 1.27xl0- 2 2.15 XlO" 2 2.6OxIO- 2 5.7IxIO- 2 8.62xl0-2 1.17XlO- 1 1.6 x 1015

Dioctanoyl peroxide

^-Heptane

Dioctanoyl peroxydicarbonate

Chlorobenzene

Phenylacetyl peroxide

Acetonitrile Benzene Carbon tetrachloride Cyclohexane Styrene Toluene

Triptoyl peroxide

Benzene

Apocamphoyl peroxide ds-5-rm-Butylcyclohexylformylm-chlorobenzoyl peroxide

Benzene

fra«5-4-^rf-Butylcyclohexylformylm-chlorobenzoyl peroxide

Benzene

Chlorobenzene

n-Heptane

2-Nonenoyl peroxide

Mineral oil

z z z z z z

(1500) (2000) (2500) (1500) (1500) (1500)

exp[- 129.05/RT]

96.2

f,u2 f,uj

a,mi

125.5

X1 xi xi

exp[-121A/RT] 126

a a a a

exp[- 128.34/^7] z (1500) z (1500) z(l) z (500) z (1000) z (1500) z (2000) z (2500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) exp[-128.8//?7]

377 377 377 377 377 377 344 344 344 344 167 167 167 167 316 59 59 102 244 102

337 337 337 338 344 344 344 344 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 1

Table 4. cont'd Number of C atoms

Initiator

18 (cont'd)

3-Nonenoyl peroxide 2-Phenylpropionyl peroxide

19

Dibenzoyl itaconyl diperoxide

Solvent Mineral oil Cyclohexane On silica Styrene Unknown

J(0C) T (K) 55.8 49.4 70 70 75 85

Dibenzoyl a-methylsuccinoyldiperoxide

Unknown

70 75 85

20

Decanoyl peroxide

Benzene

Chlorobenzene

Dioctanoyl a-bromosuccinoyldiperoxide

Mineral oil Unknown

60 70 85 63 80 100 T (K) T(K) 70 75 85

Dioctanoyl a-chlorosuccinoyldiperoxide

Unknown

70 75 85

21

Dioctanoyl a-chlorosuccinoyldiperoxide 4-Ethyl-2-octenoyl peroxide Dioctanoyl itaconoyl diperoxide

Chlorobenzene

70

Chlorobenzene THF Chlorobenzene

70 70 70

1.18 x 10 " 4 6.2xl0"5 1.54 x 10 " 5

Chlorobenzene

35 70 35 50 55 65 T(K) 55

9.42 x 10 " 5 3.02 x 10" 3 9.77 x 10" 4 7.92 x l O " 5 1.45 x l O " 4 4.13 x l O " 4 1.07 x l O 1 2 1.38 x l O " 4

85 T (K) 70

85 Unknown

70 75 85

22

Benzoyl 2-[mms-2-(3-nitrophenyl)vinyljbenzoyl peroxide Benzoyl 2- [frans-2-(4-nitrophenyI)vinyl]benzoyl peroxide Benzoyl 2-[fra«s-2-(4-nitrophenyI)vinyl]-4-nitrobenzoyl peroxide Benzoyl 2-[frans-2-(phenyl)vinyl]benzoyl peroxide 4-Benzylidenebutyryl peroxide

3.7 x 10 14 6.8xlO~ 6 7.5 x 10 " 5 5.5 x 10" 5 5.63 x 10~ 4 1.87 XlO" 5 8.63xlO- 4 3.62 xl0~ 5 1.69 X l O " 3 1.00 X l O - 4 2.74 x 10 " 4 1.26 x l O " 5 4.26 X l O " 4 2.40xl0~5 9.6OxIO"4 8.7 x l O " 5 1.53 x 10~5 5.67 XlO" 5 3.8OxIO- 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l 0 ~ 3 3.64 x 10 15 2.7xl015 1.52 x 10 ~~4 1.82 x l O " 5 2.74 XlO" 4 3.83 xlO- 5 6.97 x l O " 4 1.15 X l O " 4 2.02 x 10 ~A 2.42 x l O " 5 3.23 x l O " 4 4.83 xlO~ 5 8.5OxIO-4 1.58 x 10~ 4 8.2 x 10 1 4 3.23 x 10 ~4 2.8OxIO-5 5.47 x l O " 4 5.6OxIO"5 1.28 x l O " 3 1.92 X l O " 4 5.48 x 10 ~4 5.88 x l 0 ~ 5 9.58 x l O " 4 1.06 x l O " 4 2.61xl0"3 3.84 x l O " 4 1.87 x 10~4

Unknown Mineral oil Unknown

75

Dioctanoyl a-methyl succinoyldiperoxide

* d (s" 1 )

Methanol Acetophenone

E31 (kj/mol)

Notes

exp[- 10S.0/RT]

83.7 115.1

82.8 116.3

127.2

exp[- 130.48//?7] exp[- 131.9/K7] 96.2 126.4

95.4 126.4

X2 X2 X2 X2 X2 X2 X2 X2 X2 X2 X2 x2 a a a

X2 X2 X2 X2 x2 X2 X2 X2 X2 X2 X2 X2

e x p [ - 121A/RT] 92.9 127.6

96.2 131.0

84.5

1 258 258 316 214 214 214 214 214 214 214 214 214 214 214 214 126,337 126,337 126,337 344 344 344 344 1 214 214 214 214 214 214 214 214 214 214 214

X2 X2 X2 X2 X2 X2 X2 x2 X2 x2 x2 x2 t9

214 1 214 214 214 214 214 214 214 214 214 214 214 214 175

t9 t9 t9

175 175 175

h,t 9 t9 t9

175 175 175 133 133 133 133 133

99.6

exp[-99.6//?7] 98.7

Refs.

m2



Initiator 4-Benzylidenebutyryl peroxide

Solvent Acetophenone Benzene


Nitrobenzene Propylene carbonate

4-ter/-Butylbenzoyl peroxide cis-4-tert-Butylcyclohexane formylperoxide

Toluene Dioxane Butane Carbon tetrachloride

frarcs-4-te7t-Butylcyclohexane formylperoxide


fra«s-4-(4-Chlorobenzylidene)butyryl peroxide

Benzene

Propylene carbonate

frarcs-4-(4-Fluorobenzylidene)butyryl peroxide

Benzene

Propylene carbonate

1-Naphthoyl peroxide

Benzene

4-Nitrobenzoyl-2-[rra«5-2-(4-nitrophenyl)vinyl] benzoyl peroxide 2-Phenylisovaleryl peroxide

Chlorobenzene

5-Phenylpenta-2,4-dienoyl-peroxide 5-Phenylpentanoyl peroxide

Acetonitrile Cyclohexane On silica Styrene Acetophenone Benzene Carbon tetrachloride

Propylene carbonate 24

Dibenzoyl 2-bromosebacoyldiperoxide

Unknown

J( 0 C) 65 T(K) 50 60 70 60 70 T(K) 60 40 50 T (K) 50 40 50 60 70 80 40 40 40.0 45.45 50.7 40.0 44.7 48.9 50 60 70 40 50 60 50 60 70 40 50 60 54.6 59.9 64.5 70 55.0 55.0 50 70 77 77 70 77 85 T(K) 60 60 70 75 85

Dioctanoyl 2-bromosebacoyldiperoxide

Unknown

70 75

A^(S"1) 4.02 x 10 " 4 7.14xlOn 2.40xl0~ 5 6.8OxIO- 5 1.845 x l O - 4 3.47 x 10~5 1.06 XlO" 4 1.42xlO 13 3.38 x 10~4 7.36 x 10~5 2.13 XlO- 4 5.93 x 1010 2.08 XlO" 4 7.23 x l O - 5 2.093 x l O " 4 5.117 x l O - 4 1.64 x 10~4 6.08 x 10 ~2 1.25 x 10 ~5 1.69 x l O " 5 (8.65 ± 0.35) x 10 ~5 (1.32 ±0.04) x 10- 4 (2.35 ±0.05) x 10- 4 (4.25 ±0.23) x 10~5 (7.10 ± 0.38) x 10 ~5 (1.14±0.04)x 10~4 2.10xl0"5 6.56 x 10 ~5 1.75 x l O " 4 5.33 x 10 ~5 1.448 x 10~4 2.791 x 10~4 2.67 x 10 " 5 8.44 x 10 ~5 2.119 x l O - 4 6.53 x 10 ~5 1.685 x l O - 4 4.54OxIO- 4 1.01 x 10~4 1.86 x l O - 4 3.OxIO" 4 6.06 x 10~5 2.27 x 10 " 5 6.4xlO-6 2.56 x 10 ~4 2.18 x l O " 4 2.37 x 10 ~4 1.054 x l O " 5 2.76 x l O " 5 7.19 x l O - 5 1.87 x l O - 4 1.76xlO 15 4.41 x 10 ~5 2.8Ox 10" 5 4.80xl0~4 3.87 x 10~5 7.64 x l O - 4 7.22 XlO" 5 2.0OxIO" 3 2.02 x l O - 4 6.46 x 10 ~4 5.23 x 10~5 1.17IxIO- 3

Ea (kj/mol)

Notes

exp[- 98.1/RT] 91.2

m2 m2 h

112.5 exp[-112.5 /RT]

m2 m2 m2

89.5 exp[- 89.5/RT] 82.0

m2 h

76.1

a,mi z (0.98) z (1010) h

81.6

h

95.0

h

94.1

h

t9

n2

127.6 130.1

exp[-130.1/i?7]

87.9 110.8

99.6 129.7

h,m2 m2 m2 m2 m2 m2 X2 X2 x2 X2 x2 X2 X2 X2 x2

Refs. 133 133 194 194 194 133 133 133 133 133 133 133 133 194 194 194 133 6 145 145 35 35 35 35 35 35 194 194 194 194 194 194 194 194 194 194 194 194 170 170 170 175 258 258 258 316 133 194 133 133 133 133 133 133 214 214 214 214 214 214 214 214 214

Next Page


Initiator

Solvent


Unknown

Lauroyl peroxide

Benzene

Chlorobenzene

Ethyl acetate

Ethyl ether Mineral oil Styrene

26 28 36 x


2-Phenoxybenzoyl peroxide Myristoyl peroxide Menthylphthaloyl peroxide Aliphatic polymeric diacyl peroxide

kd(s'1)

Benzene Benzene

Acetophenone Benzene Dioxane Chlorobenzene

Ea (kj/mol)

30 40 50 60 70 60 70 85 70 40 50 60 70 61 79 99 T (K) 40 50 61 70 30 T (K) 34.8 49.4 61.0 74.8 100.0 50 60 65 70 50

1.08 x 10 " 4 3.0OxIO" 3 3.72 x l 0 ~ 4 2.56 x 10 " 7 4.91 x 10~7 2.19 x l O - 6 9.17 xlO~ 6 2.86 x l O - 5 1.51 x 10~5 5.58 x l 0 ~ 5 3.75 x l O - 4 4.33 x l O - 5 2.91 x 10 ~7 1.15 XlO" 6 4.75 x l O - 6 1.87 xlO~ 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 3.92 xlO 1 4 6.03 x 10 ~7 2.7OxIO- 6 1.05 x l 0 ~ 5 3.99 x l 0 ~ 5 1.97 x 10 " 6 2.2 x 1016 2.06 x 10 ~7 2.25 x l O " 6 1.42 x l 0 ~ 5 1.00 x l O - 4 2.39 x l O - 3 3.1 x 10" 6 1.2OxIO- 5 2.22 x l O - 5 4.32 x l O - 5 2.03 x 10 ~4

50 60 70 65 70 55 75 75 80

6.58 x 10 ~5 1.815 x 10 ~4 4.729 x l O " 4 8.18x10 ~5 3.38 x 10 ~5 1.15 x 10~4 9.04 x 10 ~5 9.00 x 10 " 5 1.720xl0" 4

85


rraw5-4-(4-Methoxybenzylidene)butyryl peroxide frarcs-4-(4-Methylbenzylidene)butyryl peroxide

T( 0 C)

Notes X2 X2 X2 a

127.2

a a a a,j

exp[- 12337/RT]

a exp[- 137.9/RT] a a a a a 121.1

90.4

121.3

c,h c c a a Vu Vi5 V 15

Refs. 214 214 214 99 68 68 68 68 126,337 126,337 126,337 16 68 68 68 68 344 344 344 344 68 68 68 68 99 1 10 10 10 10 10 287 287 287 287 194 194 194 194 5 16 65 302 302 302

HYDROPEROXIDES AND KETONE PEROXIDES

Initiator

Solvent

sec-Butyl hydroperoxide

Toluene

ter/-Butyl hydroperoxide

Benzene

T( 0 C) 172.0 182.3 130 145 160 154.5 161.7 169.3 174.6

fcd

(s"1) 2.65 x 10 ~5 4.9 XlO" 5 3 x 10 ~7 1.6 XlO" 6 6.6 x l O - 6 4.29 XlO" 6 9.27 x l O - 6 2.OxIO- 5 4.OxIO- 5

Ea (kj/mol)

138

170.7

Notes

a a a h

Refs. 199 199 337 337 337 76 76 76 76


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Initiator

Solvent


Unknown

Lauroyl peroxide

Benzene

Chlorobenzene

Ethyl acetate

Ethyl ether Mineral oil Styrene

26 28 36 x


2-Phenoxybenzoyl peroxide Myristoyl peroxide Menthylphthaloyl peroxide Aliphatic polymeric diacyl peroxide

kd(s'1)

Benzene Benzene

Acetophenone Benzene Dioxane Chlorobenzene

Ea (kj/mol)

30 40 50 60 70 60 70 85 70 40 50 60 70 61 79 99 T (K) 40 50 61 70 30 T (K) 34.8 49.4 61.0 74.8 100.0 50 60 65 70 50

1.08 x 10 " 4 3.0OxIO" 3 3.72 x l 0 ~ 4 2.56 x 10 " 7 4.91 x 10~7 2.19 x l O - 6 9.17 xlO~ 6 2.86 x l O - 5 1.51 x 10~5 5.58 x l 0 ~ 5 3.75 x l O - 4 4.33 x l O - 5 2.91 x 10 ~7 1.15 XlO" 6 4.75 x l O - 6 1.87 xlO~ 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 3.92 xlO 1 4 6.03 x 10 ~7 2.7OxIO- 6 1.05 x l 0 ~ 5 3.99 x l 0 ~ 5 1.97 x 10 " 6 2.2 x 1016 2.06 x 10 ~7 2.25 x l O " 6 1.42 x l 0 ~ 5 1.00 x l O - 4 2.39 x l O - 3 3.1 x 10" 6 1.2OxIO- 5 2.22 x l O - 5 4.32 x l O - 5 2.03 x 10 ~4

50 60 70 65 70 55 75 75 80

6.58 x 10 ~5 1.815 x 10 ~4 4.729 x l O " 4 8.18x10 ~5 3.38 x 10 ~5 1.15 x 10~4 9.04 x 10 ~5 9.00 x 10 " 5 1.720xl0" 4

85


rraw5-4-(4-Methoxybenzylidene)butyryl peroxide frarcs-4-(4-Methylbenzylidene)butyryl peroxide

T( 0 C)

Notes X2 X2 X2 a

127.2

a a a a,j

exp[- 12337/RT]

a exp[- 137.9/RT] a a a a a 121.1

90.4

121.3

c,h c c a a Vu Vi5 V 15

Refs. 214 214 214 99 68 68 68 68 126,337 126,337 126,337 16 68 68 68 68 344 344 344 344 68 68 68 68 99 1 10 10 10 10 10 287 287 287 287 194 194 194 194 5 16 65 302 302 302

HYDROPEROXIDES AND KETONE PEROXIDES

Initiator

Solvent

sec-Butyl hydroperoxide

Toluene

ter/-Butyl hydroperoxide

Benzene

T( 0 C) 172.0 182.3 130 145 160 154.5 161.7 169.3 174.6

fcd

(s"1) 2.65 x 10 ~5 4.9 XlO" 5 3 x 10 ~7 1.6 XlO" 6 6.6 x l O - 6 4.29 XlO" 6 9.27 x l O - 6 2.OxIO- 5 4.OxIO- 5

Ea (kj/mol)

138

170.7

Notes

a a a h

Refs. 199 199 337 337 337 76 76 76 76



Initiator tert-Butyl hydroperoxide

Solvent Benzene Chlorobenzene

Cumene Cyclohexane Dodecane Heptane w-Octane

Toluene

Vapor

tert-Butyl hydroperoxide/cobalt 2-Ethyl hexanoate

Chlorohenzene

tert-Butyl hydroperoxide/cobalt stearate Methyl ethyl ketone peroxides

Benzene

5

tert-Amyl hydroperoxide

Ethyl acetate Chlorobenzene

6

Acetone cyclic diperoxide

Benzene

3,3,6,6-Tetramethyl-1,2,4,5tetroxane

Toluene Benzene

Toluene Vapor

Cyclohexyl hydroperoxide

Benzene Benzene/styrene (50/50) Cyclohexane

T( 0 C) 172.3 182.6 171 199 231 182.6 100 172 86.1 98.5 172 149.8 159.9 169.6 179.6 100 172.5 181.5 192.6 204.5 214.9 570 670 773 873 973 0 0 0 25 25 45 45 100 115 130 70 153 190 228 135.5 145.5 165.0 165.0 135.5 140.5 145.5 150.5 165.0 165.0 130.1 150.1 170.1 177.1 185.1 194.1 207.1 215.1 250.1 70 70 130 140 150

#d ( s 1 ) 1.09 x l O " 5 3.1 x 10~5 1.93 x 10~5 1.93 x l O " 4 1.93 x l O " 3 8.1 x 10" 5 1.2xlO- ? 1.4IxIO- 4 1.32 xlO~ 6 5.55 x l O - 6 1.41 x 10" 4 8xlO"6 2.5 XlO" 5 6.9 x l 0 ~ 5 1.82 x l 0 ~ 5 5.7xl0"8 9.2 x l O " 6 2.69 XlO" 5 8.3 x l O " 5 1.52 XlO" 4 3.24 xlO~ 4 3.4XlO 1 4.95 8.4XlO 1 5.66 x 102 2.58 x 103 1.01 x 10" 3 8.29 x 10 ~5 5.4OxIO" 4 2.3 XlO" 3 1.1 x l O " 3 1.4xlO" 3 l.OxlO" 3 1.3 x 10 " 5 4.80xl0"5 1.60xl0" 4 1.28 x 10~6 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l O " 3 6.25 x l O " 7 2.09xl0-6 1.41 x 10" 5 1.37 x l O " 5 6.25 x l O " 7 1.19 x 10~6 2.09 x l O " 6 2.83 XlO" 6 1.41 x 10" 5 1.37 x l O " 5 1.8 x l O " 6 3.4xlO- 6 3.5xl0-6 4.6x10-6 1.3 x l 0 ~ 5 2.4 x l O - 5 8.5 x l O " 5 1.66 x l O " 4 4.88 x l O - 4 0 1.27 x 10~3 2.38 x l 0 ~ 3 1.16 x l O - 2 3.20xl0" 2

Ea (kj/mol)

Notes

c

128.4

163.2

c b b f f f

c

Vi0 V7 V1

101

147.1

Vi a a a

h

a a a a a

Refs. 199 199 344 344 344 199 199 199 41 41 199 118 118 118 118 199 199 199 199 199 199 188 188 188 188 188 190 190 190 198 198 198 198 337 337 337 13 344 344 344 286 286 286 286 373 373 373 373 373 373 365 365 365 365 365 365 365 365 365 91 91 91 91 91


Initiator Cyclohexyl hydroperoxide

Solvent Benzene

80

Cyclohexane

80

Cyclohexene

80

Dimethylheptadiene

80

1-Octene

80

7

Benzyl hydroperoxide

Styrene

8

1,4-Dimethylcyclohexanehydroperoxide 1,1,3,3-Tetramethylbutylhydroperoxide

1,4-Dimethylcyclohexane

Benzene

Chlorobenzene

2,5-Dimethyl-2,5-di(hydroperoxy)hexane

(S)x

9

Benzene

n-Octyl hydroperoxide 2,4,4-Trimethylpentyl2-hydroperoxide Poly(phenyleneethyl hydroperoxide)/manganese resinate

White oil White oil

Cumene hydroperoxide

Benzene

Chlorobenzene

Chlorobenzene

Cumene

Mesitylene Styrene Toluene

Cumyl hydroperoxide

10

p-Cymene hydroperoxide

T( 0 C)

White oil Acetone-d6

/?-Cymene

^d(S" 1 )

60 60 120

Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 9xlO~6 1.8 x l O - 5 1.4xlO" 5

130 145 160 135 153 173

1.7xlO~ 5 7.41 x 10- 5 2.83 XlO" 4 1.93 x 10 ~5 1.93xlO- 4 1.93 x l O - 3

130 145 160 150 150

2.7xlO~ 6 1.0 x l O - 5 3.16 x l O - 5 9.29 x 10 ~5 9.29 x 10 " 5

26 30 35 115 130 145 159 193 253 110 120 132 T(K)

2.0OxIO- 4 2.75 x 10" 4 3.67 XlO" 4 4xlO"7 1.7 x l O - 6 6.6 x l O ~ 6 1.93 x 10 ~5 1.93 x l O " 4 1.93xl0-3 2.742 x 10 ~6 5.194 x l O - 6 9.305 x l O - 6 2.1OxIO 11

125 139 182.3 150 -33.0 -23.0 -12.0 -18.0 -8.0

9xlO~6 3 xlO-5 6.45 x l O " 5 1.34 x 10~4 7.0xl0~5 2.28 XlO" 4 1.2IxIO- 3 8.3 x l O - 5 4.23 x l O - 4

-3.0 110 120 132 T(K)

1.65xlO- 3 5.50OxIO" 6 1.20OxIO- 5 2.089 XlO" 5 1.23 x l O 1 2

Ea (kj/mol)

Notes

Refs. 119

119

119

119

119

C3 C4 c

276 276 224

134

a a a

337 337 337 344 344 344

113

a a a a a

337 337 337 177 177

t3 t3 t3 a a a

212 212 212 337 337 337 344 344 344 367 367 367 367 58 58 199 199 199 177 264 264 264 264 264

137.2

112.5 112.5 46.0

122

exp[- S0.0/RT] 98.7 101.3

121.3 62.0

a

110.2

tu tM tu

exp[-85.48//?71

264 367 367 367 367



Initiator Decalin hydroperoxide

Solvent

Pinane hydroperoxide

Acetic acid Chlorobenzene Decalin 1,2-Dichlorobenzene Ethylene glycol Nitrobenzene Pyridine Benzene

2-Phenylbutyl 2-hydroperoxide

sec-Butylbenzene

l-Phenyl-2-methylpropylhydroperoxide

Benzene

l-Phenyl-2-methylpropyl-2hydroperoxide

Benzene

Tetralin hydroperoxide

Poly(butene) n-Butyl stearate 2-Ethyl-l-hexene 1-Hexadecene Mineral oil

/i-Octadecane Isooctane Octyl ether Poly(propylene) «-Tetradecane Tetralin 2,2,4-Trimethyl-l-pentene white oil Toluene

(1O)n

Poly(cumyleneethylhydroperoxide) (MWIlOO)

11

2,2-Bis(terf-butyldioxy)propane

Cumene

l-Methoxy-l-(terf-butylperoxy) cyclohexane

Cumene

s£c-Butyltoluene hydroperoxide

^c-Butyl toluene

2,2-Di-(tert-butylperoxy)butane

Chlorobenzene

2,2-Bis(ter/-butyldioxy)butane Diisopropylbenzene monohydroperoxide

Cumene Chlorobenzene

l-Methoxy-l-(terr-amylperoxy) cyclohexane

Cumene

12

T( 0 C) 130 130 130 130 130 130 130 130 145 160 110 120 132 T(K) 133.8 143.9 153.9 163.7 174 144.2 154.5 165.6 176.0 170 170 130 170 170 135.6 150.6 170 170 170 170 170 170 T(K) 170 150 130 140 150 90 100 110 120 80 90 100 110 100 110 120 T(K) 98 116 136 T(K) 100 150 182 218 80 90

^d(S"1) 5.5xl0~4 10% in 3 h 1.4IxIO- 5 4.48 x l O " 5 1.65 x 10 ~4 4.73 x 10 ~5 (2.31-2.89) x 10 ~4 7.08 x 10 " 6 2.72 x l 0 ~ 5 9.17 x l O - 5 2.944 x 10 ~6 6.61IxIO- 6 1.089 XlO" 5 4.06 xlO 1 2 3.18 x l O " 6 8.95 x 10 " 6 2.OxIO" 5 4.03 XlO" 5 9.77 x l O " 5 5.04 x 10 " 6 1.21 x IO"5 2.92 x l O " 5 6.97 XlO" 5 2.17 x l O " 3 1.47 x l O " 4 1.08 x l O " 4 1.26 x l O " 3 7.92 x l O " 4 4.2 x l O " 5 1.00 XlO" 4 4.82 x l O - 4 2.54 x 10~4 1 31 x 10" 4 1.45 x l 0 ~ 3 2.5OxIO" 3 2.32 x 10~4 2.27 x 109 1.67 x 10~3 1.34 x 10~4 2.79 x 10" 5 4.OxIO- 5 5.78 XlO" 5 2.16 x 10~6 9.14 x l O " 6 2.97 XlO" 5 9.56 x l O " 5 4.79 x 10 ~6 1.898 x 10 ~5 6.57 x l 0 ~ 5 2.139 x l O - 4 4.11IxIO- 6 8.194 XlO" 6 1.9555 x l O - 5 1.02 xlO 1 6 1.93 x 10 ~5 1.93 x l O - 4 1.93 xlO" 3 9.3OxIO 16 1.84 x 10 ~5 1.93XlO" 5 1.93 x 10 ~4 1.93 x l O - 3 7.82 xlO~ 6 3.07 x 10 " 5

£ a (kj/mol)

Notes

124.3 176.4 117.2

123.8

a a a

exp[-87.15//?7] 122.2

h

125.5

h

78.2 125.5 82.8

t3 t3 e,t3 t3 t3 t3 e,t3 t3 t3 t3 t3 t3 t3

117.2 131.4

119.2 121.3

exp[-102.1 /RT] t3 121.3

txp[-\W2/RT]

exp[-154.08/^7]

Refs. 228 228 228 228 228 228 228 18 18 18 367 367 367 367 76 76 76 76 76 76 76 76 76 71 71 71 71 71 71 71 71 71 71 71 71 71 112 71 177 210 210 210 361 361 361 361 348 348 348 348 367 367 367 367 344 344 344 344 361 344 344 344 348 348

TABLE 5. cont'd Number of C atoms 12 (cont'd) 13

14

Initiator

Solvent

l-Methoxy-l-(te/Y-amylperoxy) cyclohexane l-Methoxy-l-(terf-hexylperoxy) cyclohexane

Cumene

U-Bis(tert-butylperoxy)cyclopentane

Cumene

2,2-Bis(terf-butyldioxy)-3-methylbutane

Diphenylmethane

U-Bis(terf-butylperoxy)cyclohexane

Cumene

Cumene Cumene

Chlorobenzene

l,l-Bis(terr-butylperoxy)-2-methylcyclopentane

15

16

17

w-Dodecane n-Hexadecane H-Hexane n-Nonane Cumene

1,1-Diphenylethyl hydroperoxide

Chlorobenzene

l-Methoxy-l-(rm-octylperoxy)cyclohexane

Cumene

U-Bis(^-butylperoxy)-2-methylcyclohexane

Cumene

U-Bis(terf-amylperoxy)cyclohexane

Cumene

l,l-Bis(terf-butylperoxy)cyclooctane

Cumene

l,l-Bis(^rr-butylperoxy)-2-n-propylcyclohexane

Cumene

l,l-Bis(terf-butylperoxy)2-isopropylcyclohexane

Cumene

l,l-Bis(ferf-butylperoxy)3,3,5-trimethylcyclohexane

Cumene

T( 0 C) 100 110 80 90 100 110 80 90 100 110 90 100 110 120 100 80 90 100 110 94 113 134 T (K) 100 100 100 100 80 90 100 110 90 110 130 150 T (K) 70 80 90 100 80 90 100 110 80 90 100 110 90 100 110 120 80 90 100 70 80 90 100 80 90 100 110

A:d (s"1) 1.058 xlO~ 4 3.450 x 10 " 4 8.34 x 10~6 3.17 x l O " 5 1.12Ox 10" 4 3.653 x l O - 4 4.98 x l O " 6 1.80xl0~ 5 6.67 x l O " 5 2.17 XlO" 4 1.08 x 10 ~5 3.75 x 10 ~5 1.29 XlO" 4 4.1IxIO-4 3.17 x l O " 5 3.47 x 10~6 1.45 x 10 ~5 5.06 x l O " 5 1.62 XlO" 4 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l 0 ~ 3 3.47 x 1015 3.51 x 10 ~5 3.15 x l O " 5 3.82 x 10 " 5 3.62 x 10 ~5 1.55 x 10~5 5.82 x 10~5 1.85 x l O " 4 6.0OxIO" 4 2.OxIO" 9 1.007 XlO" 6 1.034 XlO" 6 1.223 XlO" 6 1.38 x 108 5.9xlO~ 6 2.3OxIO" 5 8.18 x l O " 5 2.84OxIO" 4 1.29 x 10~5 4.51 x 10 " 5 1.43 XlO" 4 4.58 x l O " 4 5.34 x l O " 6 2.02 x 10 " 5 7.32 x l O " 5 2.44 XlO" 4 1.11 x 10 " 5 4.15 x 10~5 1.36 x l O - 4 4.24 xlO~ 4 1.2OxIO- 5 4.19 x 10 " 5 1.38 XlO" 4 2.59 x 10" 5 4.86 x 10 ~5 1.98 x l O " 4 7.46 XlO" 4 3.82 x 10~6 1.50 x 10 " 5 5.31 x 10 " 5 1.75 XlO" 4

Ea (kj/mol)

exp[- 142A/RT]

exp[- 105A/RT]

Notes

Refs. 348 348 348 348 348 348 349,364 349,364 349,364 349,364 358 358 358 358 361 349,350 349,350 349,350 348,349,350 344 344 344 344 364 364 364 364 349 349 349 349 374 374 374 374 374 348 348 348 348 349 349 349 349 348 348 348 348 364 364 364 364 349 349 349 349 349 349 349 349,364 349,364 349,364 349,364


TABLE 5. cont'd Number of C atoms Il (cont'd)

Initiator

Solvent

U-Bis(tert-butylperoxy)3,3,5-trimethylcyclohexane

Chlorobenzene

rc-Butyl 4,4-di-(terf-butylperoxy) valerate

Chlorobenzene

18

l,l-Bis(terr-hexylperoxy)cyclohexane

Cumene

20

U-Bis(tert-butylperoxy)cyclododecane

Cumene

22

U-Bis(tert-octylperoxy)cyclohexane

Cumene

31

2,2-Bis[4,4-di-(tert-butylperoxycyclohexyl)propane

Chlorobenzene

TABLE 6. Number of C atoms 4 5

85 105 128 T (K) 102 121 143 T(K) 80 90 100 110 90 100 110 80 90 100 110 87 106 128 T(K)

kd (s"1) 1.93 x ICT5 1.93 x 10 ~4 1.93 X l O - 3 7.59 x 10 13 1.93 x 10 " 5 1.93 x 10 ~4 1.93 XlO- 3 1.91 x 1015 5.38 x 10~6 2.06 x 10 ~5 7.48 XlO" 5 2.48 XlO- 4 8.14 x l O " 6 3.22 x 10~5 9.93 XlO" 5 1.513 x 10~5 5.62 x 10 ~5 1.983 X l O - 4 6.26 x l O - 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 x l O - 3 8.79 x l O 1 4

Ea (kj/mol)

Notes

Refs. 344 344 344 344 344 344 344 344 348 348 348 348 364 364 364 348 348 348 348 344 344 344 344

exp[- 127.52/RT]

exp[- 143.51/RT]

exp[-135.56//?7]

PERESTERS AND PEROXYCARBONATES

Initiator Dimethyl peroxalate tert-Butyl percarbamate tert-Butyl performate

Solvent

J( 0 C)

Pentane Chlorobenzene Chlorobenzene

25 90 130.8 140.8 140.6 140 140 140.6 140 140.6 140 79.5 88.4 92.8 64 64 64 64 79.6 87.8 92.6 88.2 92.8 99.4 75 85 85 100 115 130 75

4-Chlorotoluene Cumene 6

J( 0 C)

Isobutyl peracetate

a-Methylstyrene

tt-Butyl peracetate

a-Methylstyrene

sec-Butyl peracetate

terr-Butyl peracetate

a-Methylstyrene

terf-Amyl

alcohol Benzene

n-Butanol

A^(S"1) 1.7xlO~ 5 6.6xlO" 6 5.43 x 10 ~5 1.7OxIO- 4 1.8OxIO- 4 2.12 XlO" 3 5.06 x l O - 4 1.61 x 10~4 1.62 x l O - 3 1.77 x 10~4 1.02 XlO" 3 1.36 x l O " 5 3.61xl0" 5 5.58 x l O - 5 ~9.6xl0~3 8.2 x l O - 3 6.5 x l O - 4 1.2 x l O - 3 1.57 x l O - 5 3.27 x l O - 5 5.38 x l O - 5 1.79XlO"5 3.19 x l O - 5 5.37 x l O - 5 2.8 x 10 " 6 1.2xlO~ 6 2.18 x l O - 6 1.54 x 10- 5 1.02 XlO" 4 5.69 x l O - 4 2.65 x 10 ~5

Ea (kj/mol)

Notes

159.0

h

64.0

m2 V8 V1 v8 b b,v6

115.2

g2,vi6 g2,vi7 g2,vi8 g2,vi9 101.0

104.3

151.9

a a a a

Refs. 203 141 218 218 218 218 218 218 218 218 218 253 253 253 253 253 253 253 253 253 253 253 253 253 193 193 126,337 126,337 126,337 126,337 193


Initiator rm-Butyl peracetate

Solvent 2-Butanol

Chlorobenzene

Decane

rm-Butyl trichloroperacetate

Diethyl peroxydicarbonate

Dodecane Hexadecane Hexane Octane Paraffin Tetradecane Chlorobenzene

terr-Butanol 2,2'-Oxydiethylene bis(allyl carbonate)

7

Diethyl peroxalate ten-Amyl peracetate

Pentane Chlorobenzene

tert-Butyl methoxyperacetate

Ethylbenzene

terf-Butyl peracrylate

Benzene

terr-Butylperoxy isopropyl

Chlorobenzene

terr-Butyl perpropionate carborate

Benzene Decane Dodecane Hexadecane a-Methylstyrene

8

rm-Butyl 2-acetoxyperacetate tert-Buty\ cyclopropanepercarboxylate

Octane Tetradecane Ethylbenzene «-Dodecane rc-Hexadecane 2,2,4-Trimethylpentane

ferf-Butyl ethoxyperacetate

Ethylbenzene

T (0C)

£ d (s" 1 )

75 75 75 60 100 119 139 T (K) 100 115 125 100 100 100 130.1 100 130.1 100 60 66.8 77.0 45 55 40 50 60 25 90 108 129 T(K) 40.0 39.6 50.2 60.1 90 100 110 98 117 137 T(K) 80 90 100 100 100 70 90 100 100 91.8

1.13 x 10" 4 5.3 XlO" 5 4 xlO-7 2.3IxIO"8 1.93 XlO" 5 1.93 XlO" 4 1.93 x l O " 3 1.57 x 10 16 1.5 x IO" 5 7.9IxIO-5 2.45 XlO" 4 1.95 x 10- 5 1.78 x 10 ~5 1.55 x 10 " 5 5.08 x 10~4 2.07 x 10 ~5 3.13 x 10~4 1.55 x 10 ~5 1.19 x 10 " 5 2.75 x l O - 5 1.00 XlO" 4 1.25 x 10 " 5 5.7 x l 0 ~ 5 6.94 x l O " 6 2.86 x 10 " 5 1.28 x l O - 4 2.6xlO"5 1.93 x 10 " 5 1.93 x l O " 4 1.93xl0- 3 4.13 x l O 1 5 2.2xlO"4 1.94 x l O - 4 8.24 x l O - 4 2.35 x l O - 3 1.12 x l O " 5 1.5IxIO- 5 4.85 x l O - 5 1.93 x 10 " 5 1.93 XlO" 4 1.93 x l O - 3 2.49 x l O 1 6 1.53 x 10~6 6.04 x 10 " 6 1.82 x 10 ~5 1.78 x IO" 5 1.58 x 10 ~5 3.02 x 10~7 4.85 x l O " 6 2.03 x 10 ~5 1.68 x 10 ~5 2.73 x 10 ~5

113.0 102.6 113.0 102.6 113.0 120.4 40.0 40.6 46.0 55.6

5.48 x 10 ~5 1.28XlO" 5 4.92 x l O - 5 1.7IxIO- 5 6.19 x 10~5 1.505 XlO" 4 2.96 x 10 ~4 2.89 x l O - 4 5.58 x l O - 4 1.94 XlO" 3

E31 (kj/mol)

Notes

159.0

c t7 m3 a,h

exp[- 149.36/RT] 134

125.9 126.8

a,h h

133.9-138.1

c c a a a

127.2

exp[-141.1/#n 104.7 103.9

86.2

a,h h

a a a

exp[-150.15//?7] a a

a a

b

153.8

h

146.2

h

105 102.7

a m 2 ,h

Refs. 193 193 193 81 344 344 344 344 337 337 337 270 270 270 169 270 169 270 81 28 28 18 18 90 90 90 203 344 344 344 344 315 328 328 328 211 211 211 344 344 344 344 213 213 270 270 270 213 213 270 270 328 255 255 255 255 255 255 315 328 328 328



Initiator tert-Butyl heptafluoroperoxybutyrate

Solvent Benzene

Methanol

Methoxybenzene

Nitrobenzene

Octane

Pyridine

Toluene

terf-Butyl methoxyperpropionate terr-Butyl perisobutyrate

Ethylbenzene Benzene

Bulk Chlorobenzene

Cumene

Decane

terf-Butyl percrotonate

Dodecane Hexadecane Iso-octane Nujol Octane Tetradecane Benzene

T( 0 C) 65.0 70.0 75.0 80.0 60.0 65.0 70.0 75.0 80.0 60.0 65.0 70.0 75.0 10.0 15.0 19.6 30.0 55.0 60.2 65.0 70.0 40.0 45.0 50.0 85.0 90.0 95.0 100.0 30.0 40.0 50.0 65.0 75.0 80.0 85.0 40.3 78 70 85 100 70 90.6 100.7 110.0 79 98 118 T(K) 90.6 100.7 110.0 70 85 100 100 100 100 103.4 103.4 100 100 100 115 130

^d(S"1) 1.56 x 10 " 5 3.09 x 10 ~5 5.27 XlO" 5 9.08 x l O " 5 9.5 x l O " 6 1.61 x 10~5 2.7OxIO- 5 5.23xl0-5 9.18 x l 0 ~ 5 9.6 XlO" 6 1.93 x l O - 5 3.57 XlO" 5 6.35 x l 0 ~ 5 7.19 x 10~5 9.37 x l 0 ~ 5 1.304 x l O - 4 2.604 x l O - 4 5.01 x 10 ~5 8.56 x l O " 5 1.378 x l O - 4 2.444 XlO" 4 3.26 x 10 ~5 6.36 x l O " 5 9.31 x 10 " 5 5.1 x 10 ~6 9.5 xlO~ 6 1.75 x l O - 5 3.41 x 10 " 5 2.74 x 10 " 5 7.66 x l O " 5 1.868 x l O " 4 1.88 x 10 " 5 4.66 XlO" 5 7.06 x l O " 5 1.203 x l O " 4 4.30xl0~ 3 3.77 x 10~5 6.69 x l O " 5 5.33 x l O - 5 3.5OxIO- 4 4.12 XlO" 5 8.13 x 10" 5 2.75 x l O " 4 8.92 x l O " 4 1.93 xlO~ 5 1.93 x l O - 4 1.93 x l O " 3 2.07 xlO 1 5 6.9 x l O " 5 2.35 x l O " 4 6.57 x l O " 4 4.7 x l O " 6 2.6 x l O - 5 1.55 x l O " 4 1.46 x l O " 4 1.56 x 10 " 4 1.47 x 10 " 4 2.16 xlO~ 4 2.23 x l O " 4 1.59 x 10 ~4 1.52 x 10 " 4 2.5xlO" 5 1.5OxIO- 4 7.39 x l O - 4

Ea (kj/mol)

Notes v 24 V24 V24 V24 V25 V25 V25 V25 V25 V26 V26 V26 V26

140.6

a a a a a h

exp[-135.16/,RrI 133.1

h

140.6

122

a a a

138

a a a

Refs. 370 370 370 370 370 370 370 370 370 370 370 370 370 369 369 369 369 370 370 370 370 370 370 370 370 370 370 370 370 370 370 369 369 369 369 328 37 126,337 126,337 126,337 37 136 136 136 344 344 344 344 136 136 136 337 337 337 270 270 270 251 251 270 270 337 337 337


Initiator

Solvent

tert-Butyl permaleic acid

Acetone

tert-Butyl permethacrylate

Benzene

tert-Butyl peroxyisopropyl carbonate

Benzene

Cyclohexyl peracetate

a-Methylstyrene

Diisopropyl peroxalate Diisopropyl peroxydicarbonate

Pentane Benzene Di-rc-butyl phthalate

Decane

Ethylbenzene Mineral spirits

2,2/-Oxydiethylenebis(allyl carbonate)

9

Ethyl tert-butyl peroxalate

Toluene Benzene

tert-Butyl 2-acetoxyperpropionate ter/-Butyl 5-bromo-2-perthenoate

Ethylbenzene Carbon tetrachloride

tert-Butyl 5-chloro-2-perthenoate


tert-Butyl cyclobutanepercarboxylate

n-Hexadecane 2,2,4-Trimethylpentane

T( 0 C)

^d(S"1)

70 85 101 90 100 110 90 100 110 88.6 93.0 99.3 25 54.0 77 87 97 107 117 35 45 60 54.3 54.3 30 45 60 75 40 50 60 50 45 55 65 91.4 99.2 112.0 124.5 99.2 112.0 124.5

2.7xlO~ 6 1.6 x l O " 5 6.77 x l O " 5 1.92 x l O ' 5 7.66 XlO- 5 1.92 x l O " 4 6.64 x 10 " 6 2.21 x 10~5 6.87xl0-5 1.63 x l O " 5 2.30xl0"5 4.75 XlO" 5 6.0xl0~ 5 5.0xl0"5 1.39 x 10 ~3 4.09 x l O " 3 1.25 x l O " 2 3.54xl0-2 7.98 x l O " 2 6.3 x l O " 6 2.7xlO-5 1.85 x l O " 4 4.5 x 10 " 5 5.2x10-5 2xlO"6 1.8xl0-5 1.28 XlO" 4 7.55 x l O " 4 6.39 x 10~6 2.28 x 10 " 5 9.44xlO- 5 3.03 x 10 " 5 4.48 x 10~5 1.63 x l O " 4 5.93 x l O " 4 3.6OxIO" 4 2.24 x 10 " 6 1.18x10-5 4.30x10-5 2.29 x 10 " 6 9.56 XlO" 6 4.42x10-5

102.6 92.9 102.6 113.0

4.33 x 10~5 1.2IxIO- 5 4.84 x 10 " 5 1.668 XlO" 4

E2, (kj/mol)

Notes

113

a a a a a a a a a

137.0

109.4

113

113

117.6

112.5

143.5

143.5

ni2 yi 6 yi 6 y 16 yi6 y!6 a a a m2 a a a a a a a a c,h

a a a a a a

150.4

h

Refs. 337 337 337 211 211 211 9 9 9 253 253 253 203 60 236 236 236 236 236 337 337 337 60 60 337 337 337 337 90 90 90 90 31 31 31 328 176 176 176 176 176 176 255 255 255 255

ter/-Butyl 2,2-dimethyl3-bromoperpropionate

Cyclohexane

55 65 75

9.50xl0~ 6 3.58xl0-5 1.23 x l O " 4

118.2

h,t6 t6 t6

320 320 320

tert-Butyl 2,2-dimethyl3-chloroperpropionate

Cyclohexane

55 65 75

3.55 x 10" 6 1.48x10-5 5.65x10-5

128.6

h,t6 t6 t6

320 320 320

tert-Butyl 2,2-dimethyl3-iodoperpropionate

Cyclohexane Ethylbenzene

2.91 x 10" 5 3.76 x l O - 4 4.8 x 10~4 4.22 x l O - 4 1.39 x 10 " 3 2.68 x l O " 3

116.9

tert-Butyl isopropoxyperacetate

55 75 40.0 39.9 49.9 55.3

h,t6 t6 a,h h,m2

320 320 315 328 328 328

100.6 98.9



Initiator tert-Butyl 1-methylcyclopropylpercarboxylate Di-(tert-butylperoxy)-carbonate

terf-Butylperoxy isopropyl carbonate terf-Butyl perpivalate

Solvent 2,2,4-Trimethylpentane Chlorobenzene

1,2-Dichlorobenzene Cumene Isopropyl ether Benzene

Benzene

Chlorobenzene

Cumene

Cyclohexane

Decane

Dioxane/water (90/10) Dodecane Hexadecane Hexane

Heptane Isooctane Mineral spirits

tert-Buty\ perpivalate-d6

Octane Tetradecane Chlorobenzene

T(0C) 102.6 113.0 99.95 110.1 120.1 120.1 99.95 99.95 85 100 115 50 70 85 50 55 60 65 70 48.9 58.6 64.3 57 75 94 T(K) 74.8 60 60.6 74 45 55 60 65 64.6 75.6 84.6 70.3 55 65 75 50 70 80 60.6 80 80 55 60 65 70 80 60.6 73.9 55 60 65 70 75 T (K) 80 80 60.6 74.0

* d (s"1) 2.30 x 10 " 5 7.47 x l O " 5 6.72 x 10~5 2.13 xlO~ 4 6.05X10- 4 5.98 x 10 ~4 6.72 x 10 " 5 2.76 x 10 ~4 3.3xlO" 6 2.2xlO" 5 1.36xlO- 4 9.77 x 10 " 6 1.24X10- 4 7.64X10- 4 1.03 XlO" 5 1.94 XlO" 5 3.92 x l 0 ~ 5 7.31 x 10~5 1.30x10-4 8.4xlO" 6 3.35xlO- 5 7.0IxIO- 5 1.93 x l 0 ~ 5 1.93xlO- 4 1.93 x l O " 3 7.09 XlO 14 2.79xlO- 4 3.85 XlO" 5 4.0OxIO- 5 1.93X10- 4 3.53 x 10 ~6 1.73 x l O " 5 2.95 XlO" 5 4.53 x l O - 5 5.8IxIO- 5 2.1OxIO- 4 5.94 x l O " 4 1.11 x l O - 4 1.03 x 10 ~5 4.02 x l O - 5 1.45 x l O - 4 4.IxIO"6 5.52 XlO" 5 2.18 x l O - 4 6.26 x 10~5 2.38 x 10 ~4 2.39 x 10 " 4 8.42 x 10 '6 1.59 XlO" 5 3.39 x l O - 5 6.19 XlO" 5 2.33 x 10 ~4 1.97 x 10 ~5 8.82 x l O " 5 1.01 x 10 ~5 2.15 x l 0 ~ 5 4.14 x l O - 5 7.58 XlO" 5 1.47X10- 4 3.56 x 1014 2.34 x 10 ~4 2.27 x 10 ~A 3.24 x 10~5 1.57 xlO~ 4

£ a (kJ/mol)

Notes

Refs.

133.7

h

255 255 27 27 27 27 27 27 337 337 337 126,337 126,337 126,337 359 359 359 359 359 249 28 28 344 344 344 344 28 81 156 156 160 160 362 160 159 159 159 267 320 320 320 337 337 270 156 270 270 359 359 359 358 270 165 165 359 359 359 359 359 376 270 270 156 156

133.1

138

119.7

125.5

a a a a a a

k h

exp[- 123.59/RT] 128.0

106.7

a,h t9 t9 h

115.5

122.8

h

117

a a t9

t9 t9

exp[- 123/RT]

t9 t9


Initiator tert-Butyl

perpivalate-d6

tert-Butyl 2-perthenoate

tert-Butyl 1-pyrollidinepercarboxylate tert-Butyl Af-succinimidopercarboxylate

10

tert-Amyl

perpivalate

Solvent

(s"1) 5.05 x 10" 5 1.62 x 10~5 8.82 x l O - 5 3.3 x 10 " 6 1.66 x l 0 ~ 5 6.87 x l O - 5

Chlorobenzene

90

7.59 x 10 ~5

Acetonitrile Benzene Chlorobenzene

100 100 90 100 90 100 100 100 90 100 51 55 72 91 T (K) 50 60 70 80 35 45 60 47 63 82 T(K) 30 40 60 49 65 83 T (K) 74.7 80.7 90.8 40.3 99.8 116.6 129.9

9.9xlO~ 4 3.79 x 10~5 1.32 x 10 ~5 4.9IxIO-5 3.3xl0-6 1.10 x 10~5 9.OxIO- 6 6.00xl0"3 9.24 x 10 ~5 3.4IxIO-4 1.9XlO" 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 4.12 x 1015 1.05 x 10 ~5 3.5IxIO-5 1.309 XlO" 4 4.239 XlO" 4 6.9xlO~ 6 2.6xlO" 5 1.8OxIO- 4 1.93 x 10 ~5 1.93 XlO" 4 1.93 XlO" 3 3.19 xlO 1 5 2xlO"6 1.0 x l O - 5 1.34 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 XlO" 3 7.00 x 1015 1.98 xlO~ 4 4.37 x 10 " 4 1.25 x l O - 3 2.91 x 10 " 4 1.65 x 10 ~5 1.38 x 10~4 6.83 x l O - 4

113.0 92.9 102.6 113.0 75 93 113 T (K) 42.42 50.30 57.95 44.85 50.10 60.20

3.02 x 10 ~4 2.47 x 10 ~5 8.87 x 10 " 5 2.89 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l 0 ~ 3 2.45 x 1015 9.04 x 10 ~5 2.349 x l 0 ~ 5 5.66OxIO- 5 1.874 x 10 ~5 3.609 x l O - 5 1.306 x l O - 4


Cumene Cyclohexane Cyclohexene Methanol Methylene chloride Nitrobenzene Benzene Chlorobenzene

Decane

Chlorobenzene

Mineral spirits

Di-w-butyl peroxydicarbonate

Chlorobenzene

tert-Butyl 2-acetoxy-2methyl perpropionate

Ethylbenzene

tert-Butyl tert-butoxyperacetate tert-Butyl 4-carbomethoxyperbutyrate

Ethylbenzene Cumene

tert-Butyl cyclopentylpercarboxylate

fcd

60.6 60.6 73.9 99.2 112.0 124.5

Dioxane/water (90/10) Isooctane

Cumene

Di-(sec-butyl)peroxydicarbonate

T( 0 C)

n-Hexadecane 2,2,4-Trimethylpentane

tert-Butyl peroxydiethyl acetate

Chlorobenzene

tert-Butyl 2,2-dimethylperbutenoate

Cumene

tert-Butyl 2,2-dimethylperbutyrate

Cumene

Ea (kj/mol)

147.3

Notes t9 t9 t9 m2 m2 m2

Refs. 156 165 165 176 176 176 141

113.4

h,m2 m2 t9

m2 a

exp[- 121J6/RT]

113

exp[-123.85//?7] 113

a a a

a a a

exp[- 126.65/RT] m2

151.3

h

140.8

h

exp[- 134.00/RT] 100.7

h

142 142 141 142 141 142 142 142 141 142 338 344 344 344 344 362 362 362 362 337 337 337 344 344 344 344 337 337 337 344 344 344 344 328 328 328 328 257 257 257 255 255 255 255 344 344 344 344 274 274 274 274 274 274



Initiator Di(tert-butylperoxy)-oxalate

Solvent Benzene

tert-Butanol Decane Dodecane Octane n-Pentane Tetradecane Styrene

11

tert-Butyl 5-methyl-7-perthenoate


P-Methyl-P-phenyl-P-peroxypropiolactone


Bis(2-nitro-2-methylpropyl)-peroxydicarbonate 1-Phenylethylperacetate tert-Butyl 4-chloroperbenzoate

tert-Butyl-JV-(2-chlorophenylperoxy)carbamate

Toluene Benzene Phenyl ether

Carbon tetrachloride Toluene

tert-Butyl-AK3-chlorophenylperoxy> carbamate

Toluene

tert-Butyl-AH4-chlorophenylperoxy)carbamate

Toluene

tert-Butyl cyclohexylperoxycarboxylate

«-Hexadecane 2,2,4-Trimethylpentane

tert-Butyl-iV-(2,5-dichlorophenylperoxy) carbamate

Toluene

tert-Butyl 2,2-dimethylperpentanoate

Cyclohexane

Cumene tert-Butyl 5-ethyl-2-perthenoate


tert-Butyl 2-iodoperbenzoate

Chlorobenzene

tert-butyl 4-nitroperbenzoate

Phenyl ether

tert-Butyl 3,5-dinitroperbenzoate

Carbon tetrachloride Carbon tetrachloride

T( 0 C)

kd (s"1)

Ea (kj/mol)

Notes c,h c c

35.0 45.0 55.0 25.0 41 41 41 37.8 41 35 45 55 99.2 112.0 124.5 106.8 126 134 50

6.77 x 10" 5 2.6IxIO" 4 9.3 XlO" 4 1.83 x l O " 5 1.75 x 10 " 4 1.81 x 10" 4 1.79 x 10 " 4 1.01 x 10" 4 1.71 x 10~4 5.5xl0"5 1.71 x 10" 4 6.0IxIO" 4 4.6xlO~ 6 1.94 x l 0 ~ 5 7.95 XlO" 5 5.65 x 10 " 6 4.59 x 10 " 5 9.71 x 10" 5 2.22 x 10 ~5

106.7

100 100.0 110.1 120.2 130.9 80 87.0 95.5 103.3 78.0 87.0 96.6 102.7 73.0 78.5 87.0 92.5 92.9 102.6 82.2 92.9 102.6 113.0 88.0 95.0 103.3 114.5 55 65 75 45 55 99.2 112.0 124.5 85.0 102.4 118.8 110.1 120.2 130.9 141.5 80 80

1.14 x l O " 4 3.89 x 10 ~6 1.85 x l 0 ~ 5 6.39 XlO" 5 2.42 xlO~ 4 4.2xlO~ 7 3.5xl0"5 1.48 x 10 ~4 3.3 XlO" 4 2.6 x l O " 5 7.8xl0"5 2.03 xlO~ 4 4.62 XlO" 4 5.57 x 10 ~5 1.42 x 10 ~4 2.75 xlO~ 4 5.37 x l O " 4 6.70xl0~ 5 2.046 x 10 ~4 1.57 x l O " 5 6.13 x l 0 ~ 5 2.046 xlO~ 4 6.58 x l O " 4 2.75 x 10 ~5 5.58 x 10 ~5 1.48 xlO~ 4 4.82 xlO~ 4 1.66 x 10 ~5 6.31 x 10~5 2.23 xlO~ 4 6.2xlO~ 6 2.15 x l 0 ~ 5 5.39 x 10 ~6 2.12 x l 0 ~ 5 7.91 x 10~5 4.02 x 10 ~5 2.58 xlO~ 4 1.32 xlO~ 3 7.56 x 10 " 6 3.19 x l 0 ~ 5 1.11 xlO~ 4 3.92 xlO~ 4 2.9xlO~ 7 1.1 x 10 ~7

138.7 164.4

h a a a a

157.3

h

115.5

h

119.7

h

136.6

h

135.8

h

128.9

h

120.7

h

105.4

h

75.3

137.7

131.8

a,m2 a,m2 a,m2 h,v 9 c,v9 a

130.5

172.8

Refs. 30 30 30 197 270 270 270 197 270 215 215 215 176 176 176 195 195 195 90 259 53 53 53 53 354 36 36 36 36 36 36 36 36 36 36 36 255 255 255 255 255 255 36 36 36 36 320 320 320 160 160 176 176 176 134 134 134 53 53 53 53 354 354

TABLE 6. cont'd Number of C atoms W (cont'd)

Initiator

Solvent

/m-Butyl-AH3-nitrophenylperoxy)carbamate

Toluene

fm-Butyl-AK4-nitrophenylperoxy)carbamate

Toluene

terf-Butyl perbenzoate

Acetic acid Benzene

Bromobenzene rc-Butanol «-Butyl acetate

tert-Butylbenzene w-Butyl ether Carbon tetrachloride Chlorobenzene

4-Chlorotoluene

Cumene

Decane

Dodecane Ethylbenzene Heptane Hexadecane Methyl benzoate Octane Phenyl ether

Tetradecane Trimethylbenzene Xylene

T( 0 C) 78.0 88.7 98.0 106.0 73.0 87.0 98.0 106.0 100.0 110.0 100 115 130 110.0 119.4 130.0 119.4 90.0 100.0 110.0 119.4 110.0 1194 119.4 100.0 110.0 80 110.0 119.4 120 135 150 103 122 142 T(K) 110.0 119.4 130.0 60 79.6 85.0 99.3 115.0 130.2 100 115 130 115 115 119.4 115 115 119.4 115 100.0 110.1 120.2 130.9 115 T (K) 119.4 130.0

A:d (s"1) 8.4 x l O " 6 2.43 x 10 " 5 1.01 x 10- 4 2.36 x l O " 4 6.4xlO~ 6 3.11 x 10~5 8.75 x l O " 5 2.38 xlO~ 4 3.83 x 10 ~5 1.14 x 10~4 1.07 x KT 5 6.22 x l 0 ~ 5 3.5OxIO- 4 3.50xl0" 5 1.04 XlO" 4 3.30xl0~ 4 1.37 x 10 ~4 9.27 x 10 " 5 2.7OxIO- 4 1.06 x 10~4 2.67 x l O " 4 3.6IxIO- 5 1.10 xlO~ 4 1.03 x 10 ~4 7.8OxIO- 5 1.80 XlO" 4 8.8xl0"7 3.83 x 10~5 1.11 x l O " 4 1.3IxIO- 4 6.74 x l O - 4 3.12 x l O - 3 1.93 XlO" 5 1.93 x l O - 4 1.93 x l O " 3 2.23 xlO 1 6 3.25 x 10 " 5 9.80xl0"5 3.06 x l O - 4 3.85 XlO" 7 7.21 x 10 ~5 1.320xl0" 6 9.37 x l O - 6 5.8IxIO- 5 3.24 x l O " 4 1.4xlO- 5 8.05 XlO" 5 3.56 x l O - 4 6.77 XlO" 5 6.44 x KT 5 1.07 x 10~4 7.21 x 10~5 5.97 x 10 ~5 7.8OxIO" 5 7.06 x 10 " 5 6.94 x 10 ~6 2.28 x l O " 5 9.0OxIO- 5 2.92 x l O " 4 6.03 x 10 ~5 2.62 x 1016 1.09 x 10~4 3.42 x l O - 4

E2, (kj/mol)

Notes

133.1

h

113.8

h

130.1

a a a a a a a a a a a a a a,m2 a,m2 a a a

145.2

144.3

120.5 123.4 148.5

99.2

141.8

exp[- 151.59/RT\ 144.3

140.2

134

a a m2 m2 m2

c c c a,h

a a a

a

a 156.9

exp[-152.0/RT] 141.4

a a a a

a a

Refs. 36 36 36 36 36 36 36 36 56 56 126,337 126,337 126,337 56 56 56 56 56 56 56 56 56 56 56 56 56 354 56 56 22 22 22 344 344 344 344 55 55 55 81 272 345 345 345 345 337 337 337 270 270 56 270 270 56 270 53 53 53 53 270 376 56 56



Initiator

Solvent

terf-Butyl-AK4-bromophenylperoxy)carbamate

Toluene

tert-Butyl percarboxycyclohexane

Chlorobenzene

Cumene

12

tert-Butyl per-2-methylphenylacetate

Isooctane

tert-Butyl-N-(phenylperoxy) carbamate

Toluene

tert-Hexyl peroxypivalate

Chlorobenzene Cumene

1,1,2-Trimethylpropyl perpivalate

Cumene

Cumyl peracetate tert-Amyl peroxybenzoate

Carbon tetrachloride Toluene Chlorobenzene

4-Bromocumyl perpropionate

Benzene

oc-Methylstyrene

tert-Butyl bicyclo[2.2.1]lheptane2-percarboxylate

terf-Butyl endo-bicyclo[2.2.1]heptane percarboxylate

Cumene

Chlorobenzene

Cumene

terf-Butylexo-bicyclo[2.2.11]heptane-2-percarboxylate

Chlorobenzene

T( 0 C) 70.8 79.8 84.0 96.0 100.1 111.4 120.0 79.6 79.6 79.6 60.6 73.9 51.2 67.7 77.7 90.7 T(K) 40 50 60 70 80 40 50 60 70 100 100 99 118 139 T (K) 70 80 90 70 80 90 85 100 110 110 120 130 94.0 101.9 109.6 120.5 94.5 101.9 111.9 100.1 111.4 120.0 94.0 101.9 109.6 120.3 94.5 101.9 111.9 94.5 101.9 112.1

A^(S"1) 3.32 x 10 " 5 1.04 x 10 ~4 1.75 x l O - 4 7.70xl0~ 4 2.75 x 10 ~4 9.65 XlO- 4 2.39 XlO- 3 1.86 x l O " 5 1.42 x l 0 ~ 5 1.15xl0- 5 6.60 x 10 ~5 3.233 x l O - 4 3.4xlO-6 2.31 x 10 " 5 1.15 x l O - 4 6.41 x 10 ~4 1.51 x 1016 2.39 x 10 ~6 8.83 x l O - 6 3.37xl0-5 1.226 x l O - 4 4.166 x l O - 4 3.6xlO" 6 1.59x10-5 5.14x10-5 1.921 x 10- 4 4.68 x 10 " 5 3.43 x 10 ~5 1.93 x 10 ~5 1.93 x 10~4 1.93 x l O - 3 8.38 x 1015 1.48 x 10 " 6 5.73 x l O - 6 1.8IxIO- 5 1.99 x 10~6 4.93 x l O - 6 1.55x10-5 1.16 x 10~6 1.02 x 10 ~5 3.76xlO- 5 4.6x10-5 1.56 XlO" 4 4.99 x l O " 4 1.75XlO" 5 6.20xl0"5 1.7 x l O - 4 5.72 x l O - 4 9.69x10-5 1.96xlO- 5 6.53x10-5 4.6IxIO-5 1.96 xlO~ 4 5.4OxIO- 4 1.87 x l O " 5 5.3OxIO- 5 1.10 x l O " 4 4.3 x l O - 4 5.27xl0-5 1.12 x l O - 4 3.57 x l O - 4 8.86 x 10 ~5 2.28 x 10 ~4 8.85 x l O - 4

Ea (kj/mol)

Notes

177.6

h

131.0

h

139.7

z (1) z (2030) z (4050) ni2 m2 h

exp[- 136.0/RT]

c p

exp[- 147.02/RTl 129.7

121.3

a a a a a

155.2 160

h

150.2

h

137.2

h

149.0

h

154.0

h

130.1

h

Refs. 36 36 36 36 181 181 181 163 163 163 165 165 36 36 36 36 40 362 362 362 362 362 362 362 362 362 271 271 344 344 344 344 213 213 213 213 213 213 160 160 223 223 223 147 147 147 147 147 182 182 181 181 181 147 147 147 147 182 182 182 182 182 182

TABLE 6. Number of C atoms

cont'd

Initiator

Solvent

12 (cont'd)

Cumene

tert-Butyl endo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate

Cumene

tert-Butyl exo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate

Chlorobenzene

Cumene

tert-Butyl 4-bromophenoxyperacetate tert-Butyl 4-chlorophenoxyperacetate tert-Butyl 3-chlorophenylperacetate

Ethylbenzene Ethylbenzene Chlorobenzene

Cumene tert-Butyl 4-chlorophenyl peracetate

Chlorobenzene

Cumene tert-Butylcycloheptyl percarboxylate

rc-Hexadecane 2,2,4-Trimethylpentane

tert-Butyl 2,4-dichlorophenoxyperacetate tert-Butyl 2,2-diethyl perbutyrate

Ethylbenzene Cumene

tert-Butyl per-2-ethylhexanoate


tert-Butyl 2-methoxy-2-methylperpropionate

Chlorobenzene

tert-Butyl 4-methoxyperbenzoate

Phenyl ether

tert-Butyl peroxy-2-methylbenzoate

Chlorobenzene

tert-Butyl 4-methoxyperbenzoate tert-Butyl 4-methylperbenzoate

Carbon tetrachloride Phenyl ether

T( 0 C)

£ d (s"1)

96.0 100.1 111.4 120.0 84.4 94.7 100.1 108.6 113.5 94.5 101.9 112.1 94.5 101.9 112.0 94.5 101.9 112.1 94.5 101.9 112.1 70.5 70.5 79.6 90.7 100.5 79.6 79.6 79.6 90.7 100.5 79.6 79.6 92.9 102.6 92.9 102.6 70.5

1.33 x 10"4 1.90xl0" 4 6.79 xlO" 4 1.64 xlO" 3 2.19 xlO" 5 7.29 x l 0 ~ 5 1.37 xlO~ 4 3.6 XlO" 4 6.19 XlO" 4 6.05 x l O " 5 1.53 x l O " 4 4.72 XlO" 4 3.11 x l O " 5 7.35 x 10 ~5 2.48 x l O " 4 5.59 x l O " 5 1 25 x 10" 4 5.0OxIO" 4 4.48 x l O " 5 1.18 x l O - 4 3.97 x l O " 4 2.6xlO~ 4 2.9xlO~ 4 4.05 x 10 ~5 1.44 x l O - 4 4.38 x l O " 4 2.98 x 10 " 5 1.99 x l O " 5 8.44 x 10 " 5 2.95 x l O - 4 8.19 x l O " 4 6.54 x 10 " 5 4.45 x 10 " 5 1.801 x 10 " 4 5.17 x l O " 4 1.703 x 10 " 4 5.07 x l O " 4 9.4xlO" 5

45 55 65 72 72 91 113 T(K) -14.0 -7.0 -1.0 15.0 100.0 110.1 120.2 130.9 96 115 136 T (K) 80 100.0 110.1 120.2

1.23 x 10 " 5 4.92 x l O " 5 1.46 x l O - 4 1.9xlO" 5 1.93 x 10 ~5 1.93 x l O " 4 1.93xl0- 3 1.54 xlO 1 4 2.05 x 10 " 5 6.73 x 10" 5 1.67 XlO" 4 1.28 XlO" 3 1.07 x 10 " 5 4.17 x l O " 5 1.28 x l O - 4 4.28 x l O " 4 1.93 x 10 " 5 1.93 x 10 " 4 1.93 x l O " 3 8.56 x 1015 l.OxlO" 6 9.42 x 10 " 6 3.19 XlO" 5 1.06 XlO" 4

Ea (kj/mol)

Notes

129.3

h

129.3

h

131.4

h

136.4

h

138.1

h

123.0

a a h

117.2

z (0.98) z (6090) h

121.5

z (0.98) z (6090) h

125.7

h a

100.3

h

a

exp[- 124.90/RT] 86.3

149.8

m2 m2 m2 m2 a a a a

expr[- 145.97/RT] 151.0

a a a

Refs. 147 181 181 181 147 147 147 147 147 182 182 182 182 182 182 182 182 182 182 182 182 315 315 178 178 178 207 207 178 178 178 207 207 255 255 255 255 315 160 160 160 338 344 344 344 344 275 275 275 275 53 53 53 53 344 344 344 344 354 53 53 53


TABLE 6. cont'd Number of C atoms 12 {cont'd)

Initiator terr-Butyl 4-methylperbenzoate rm-Butyl 2-methyl-2-terfbutylperoxyperpropionate

Solvent Phenyl ether Benzene

terf-Butyl 2-methylsulfonyl perbenzoate

Chlorobenzene

tert-Butyl 2-(methylthio)perbenzoate

Chlorobenzene

tert-Butyl 4-(methylthio)perbenzoate terf-Butyl 4-nitrophenoxyperacetate /m-Butyl 4-nitrophenylperacetate

Chlorobenzene Ethylbenzene Chlorobenzene

terf-Butyl 4-nitrophenylperacetate

Decane Dodecane Hexadecane Octane

Di-terf-butyl per-2-chlorosuccinoate

Tetradecane Unknown

T( 0 C) 130.9 9.0 19.0 30.0 42.0 105 120 135 150.6 60 39.4 50.1 50.2 69.8 120.4 70.5 79.6 90.7 100.5 80 77.5 77.5 100 77.5 77.5 100 77.5 105 115 125

tert-Butyl peroctoate

Benzene

Decane

Di-rm-butyl persuccinoate

Styrene

/m-Butyl phenoxyperacetate rm-Butyl phenylperacetate

Ethylbenzene Chlorobenzene

Cumene

Decane Dodecane Hexadecane Isooctane

70 85 100 70 85 100 105 115 125 70.5 60 77.0 88.6 79.6 90.7 100.5 79.6 79.6 79.6 79.6 85.0 79.6 79.6 79.6 79.6 79.61 77.5 77.5 77.5 85.0 95.2

^d(S"1) 3.25 x 10~A 6.66 xlO~ 5 1.99 x 10 ~4 6.94 xlO~ 4 2.43 x l 0 ~ 3 6.68 x 10 ~6 5.57 x 10~5 2.76 xlO~ 4 2.05 x l 0 ~ 3 8.08 x 10~A 2.59 x l O - 5 2.42 XlO- 4 1.88 x l O - 4 1.96 XlO" 3 1.75 x 10 ~4 6.7xlO" 5 2.5xlO" 5 8.9 XlO" 5 2.83 xlO~ 4 3.77 XlO" 5 6.3OxIO- 6 5.8IxIO" 6 1.3IxIO- 4 5.11 x 10" 6 6.42 x 10 " 6 1.6OxIO- 4 5.56 x 10 " 6 2.74 x 10 " 4 1.22 x l O - 5 5.9OxIO" 4 3.83 x l O - 5 1.52 XlO" 3 1.00 x l O - 4 1.4xlO" 5 8.55 x l O - 5 4.55 x l O - 4 6.9xlO~ 6 4.39 x l O - 5 2.64 x l O - 4 1.93 x 10 " 5 6.7 x l O - 5 2.53 XlO" 4 4.4xlO" 4 6.79 x 10~6 6.85 x l O - 5 2.45 x l O - 4 1.05 x l O - 4 3.53 XlO" 4 1.003 XlO" 3 1.07 x l O - 4 9.1 x 10 " 5 1.02 XlO" 4 9.0 x 10- 4 1.945 XlO" 4 6.6xlO- 5 5.6 xlO~ 5 6.78 x l O - 5 4.73 x l O - 5 1.1 x l 0 ~ 5 3.0OxIO- 5 2.75 x l 0 ~ 5 2.6OxIO- 5 1.08 x l O " 4 3.527 x l O - 4

E2, (kj/mol)

Notes

78.8

a m2

95.0

a,h b c m2

129.9 124.7

a,h h

102.9 143.5

X2 X2 X2 x2 X2 x2 a a a a a a Xi X1 X1 a,h a,h h m2 h

130

130

154.8

113.1 120.1 117.6 116.7

z (0.98) z (4050) z (0.98) z (4050) m2 z (0.98) z (4050) z (0.98) z (6090)

Refs. 53 275 275 275 275 22 22 22 22 97 134 134 134 134 134 315 178 178 178 169 168 168 168 168 168 168 168 214 214 214 214 214 214 337 337 337 337 337 337 215 215 215 315 81 28 28 178 178 178 157 157 163 163 165 157 157 163,207 163,207 274 168 168 168 165 165


Initiator tert-Butyl phenylperacetate

tert-Buty\ 2-propylperpenten-2-oate (cw)

(trans)

Solvent Octane Paraffin oil Tetradecane Cumene

Cumene

tert-Butyl 2,2,3,3-tetramethylperpropionate

Cumene

tert-Butyl thiophenylperacetate tert-Butyl per-o-toluate ferf-Butyl per-paratoluate

Ethylbenzene Benzene Cumene

tert-Butyl-AH3-tolylperoxy)carbamate

Toluene

tert-Butyl 2,4,5-trichlorophenoxyperacetate 4-Chlorocumyl perpropionate

Ethylbenzene Benzene

a-Methylstyrene

Cumyl perpropionate

Benzene

a-Methylstyrene

4-Iodocumyl perpropionate

Benzene

a-Methylstyrene

4-Nitrocumyl perpropionate

Benzene

a-Methylstyrene

13

1,1,3-Trimethylbutyl perpivalate

Cumene

tert-Amyl per-2-ethylhexanoate


Benzyl(ter?-butylperoxy)oxalate

Benzene

T( 0 C) 77.5 85.0 77.3 94.9 100.1 100.1 100.1 110.1 94.9 100.1 100.1 100.1 110.1 42.2 54.9 70.3 70.5 97 84.0 99.3 115.0 64.0 70.7 78.0 88.5 70.5 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 40 50 60 70 70 73 91 111 T(K) 45 55 65

A^(S"1) 3.1IxIO"5 1.150 x 10~4 2.66 x 10 ~5 2.78 x 10 ~5 5.4 XlO" 5 4.26 x l 0 ~ 5 2.31 x 10~5 1.72 x l O - 4 2.47 x 10 ~5 4.7 x l O - 5 3.13 x l O - 5 1.42 x-K) - 5 1.64 x l O - 4 8.76 x l O " 6 5.84 x 10 ~5 3.36 x l O - 4 3.8 x 10 ~4 1.9xl0"5 1.660 x 10 ~6 1.139 x l O - 5 6.77 XlO" 5 4.58 x 10 " 5 9.17 x l O " 5 2.03 x l O - 4 5.78 x l O - 4 5.8 x l O " 5 1.46 x 10 " 6 5.68 x l O - 6 1.79 x l O " 5 1.50x 10" 6 4.54 x l O - 6 1.47 x l O - 5 2.6OxIO- 6 6.15 x l O - 6 1.90 x l O " 5 6.31 x 10 ~6 1.7IxIO- 5 4.94 x l O " 5 1.37 x 10~6 5.76 x l O - 6 1.79 x l O - 5 1.54 x 10~6 4.96 x l O - 6 1.62 x l O - 5 1.36 x 10 " 6 5.32 x l O " 6 1.78 x l O - 5 1.35 x 10~6 4.07 x l O - 6 1.43 x l O - 5 4.8OxIO- 6 1.77 x l O - 5 6.18 x l O " 5 2.344 x l O - 4 1.9xl0-5 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 1.77 x l O 1 5 3.65 x 10 " 5 1.33 x l O - 4 4.69 x l O - 4

Ea (kj/mol)

Notes

137.2

h z (0.98) z (1100) z (4000)

143.9

h z (0.98) z(llOO) z (3830)

114

h

a a

102.9

h

a 129.3

118.8

101.7

106.7

133.1

125.5

133.5

124.7

a a a a a a a a a a a a a a a a a a a a a a a a

a

exp[- 132.1 l/RT] 111.3

c,h c c

Refs. 168 165 168 172 172 172 172 172 172 172 172 172 172 267 267 267 315 338 345 345 345 36 36 36 36 315 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 362 362 362 362 338 344 344 344 344 31 31 31



Initiator

Solvent

tert-Butyl benzyloxyperacetate

Ethylbenzene

tert-Butyl benzylthioperacetate

Ethylbenzene

tert-Butyl bicyclo[2.2.2]octane1-percarboxylate

Cumene

ter/-Butyl endo-bicyclo[2.2.1j-2methylheptane-2-percarboxylate

Cumene

tert-Butyl exo-bicyclo[2.2.1]2-methylheptane-2-percarboxylate

Cumene

tert-Butyl 1,4-dimethylcyclohexane1-percarboxylate (cis)

Cumene

(trans)

Cumene

tert-Butyl 3-methoxyphenylperacetate

Chlorobenzene

terf-Butyl 4- methoxyphenylperacetate

Chlorobenzene

Cumene

tert-Butyl 4-methylphenyl peracetate

Decane Dodecane Ethylbenzene Isooctane Octane Paraffin oil Tetradecane Chlorobenzene

Cumene

Di-terr-butyl perglutarate

terf-Butylperoxy 2-ethylhexylcarbonate

Decane Dodecane Ethylbenzene Hexadecane Octane Tetradecane Styrene

Chlorobenzene

T( 0 C) 40.0 40.0 51.0 60.7 40.0 60.0 70.0 65 75 85 80 90 100 75 80 85 90 95 60 65 70 75 80 60.0 70.0 80.0 60.0 70.0 80.0 79.6 90.7 100.5 56.0 60.3 70.2 79.3 48.9 60 60 79.6 77.5 77.5 70.5 60.5 77.5 60.5 77.5 70.4 79.6 90.7 79.6 79.6 77.5 77.5 70.5 77.5 77.5 77.5 105 115 125 99 117 137

A:d (s"1) 1.3 x 10" 4 1.45 x l O - 4 5.03 XlO" 4 1.62 x l O - 3 2.60xl0~~5 3.31 x 10- 4 1.14 XlO" 3 7.5 x 10 ~6 2.82 x l O " 5 8.47 x l O " 5 5.IxIO"5 1.67 x l O - 4 4.86 XlO" 4 7.35 x 10 ~5 1.39 x 10 " 4 2.64 x l O - 4 4.81 x 10 " 4 8.41 x 10- 4 7.78 x 10 " 5 1.44 x 10 " 4 2.75 x l O " 4 4.89 XlO" 4 8.93 XlO" 4 7.52 x l O " 5 2.66 x 10 " 4 8.49 xlO~ 4 6.93 x 10 ~5 2.52 x l O " 4 7.79 x l 0 ~ 4 9.9xl0~5 3.45 x 10 ~4 1.051 x 10" 3 4.57 x 10 ~5 9.9xlO~ 5 3.06 x l O " 4 7.99 xlO~ 4 1.93 XlO" 5 6.85 x 10 ~5 5.31 x 10 ~5 5.942 x l O - 4 2.52 x 10 ~4 2.60xl0~ 4 1.4xlO~ 3 4.72 x 10 ~5 2.53 x 10 ~4 4.20 x l 0 ~ 5 2.68 x 10 ~4 8.67 x 10 ~5 2.37 xlO~ 4 7.95 xlO~ 4 1.649 x 10 ~4 1.180xl0~ 4 9.08 x 10 ~5 8.57 x l 0 ~ 5 7.2xlO~ 4 1.032 x 10 ~4 8.83 x 10 ~5 7.75 x 10 ~5 2.65 x 10 ~5 1.06 xlO~ 4 3.0OxIO- 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 x l 0 ~ 3

Ea (kj/mol)

Notes

100.6 101.8

a,h h,m2

108.1

h,m2

119.2

h

120.1

h

126.8

h

116.7

h

115.2

c h

116.3

c c,h c

122.2

h

105.4

h

k z (0.98) z (4050)

Refs. 315 328 328 328 328 328 328 160 160 160 223 223 223 206 206 206 206 206 206 206 206 206 206 206 206 206 206 206 206 178 178 178 178 178 178 178 249 207 207

207

104.8

a,h

110.9

h

z (0.98) z (6080)

a

Xi X1

168 168 315 169 168 169 168 178 178 178 207 207 168 168 315 168 168 168 215 215 215 344 344 344

TABLE 6.

cont'd

Number of C atoms 13 (cont'd)

14

Initiator terf-Butylperoxy 2-ethylhexylcarbonate terr-Butyl 2-phenylperpropionate

Solvent

T(K)

4.07 xlO 1 6

Cumene

40.7 60.1 80.1 40.8 54.7 70.7 40.0 95 114 135 T(K) 45 55 65 95 113 134 T (K) 54.7 70.2 85.4 70.8 85.4 101.0 40.0

7.88 x 10 " 6 8.44 x l O - 5 8.1OxIO- 4 6.15 x 10~6 3.82 x 10 ~5 2.73xlO- 4 2.62 x 10 " 5 1.93 x 10 " 5 1.93XlO" 4 1.93 x l O - 3 1.94 xlO 1 5 1.3OxIO" 5 4.89 x 10 " 5 1.89 x l O - 4 1.93 x 10 ~5 1.93 x l O " 4 1.93 x l O " 3 2.22 x 1016 4.38 x 1O -6 3.56 x l O - 5 2.44 x l O - 4 1.48 x 10 " 5 8.07 x 10" 5 4.38 x l O " 4 7.2xlO-4

50.0 50.0 50.0 60.0 67.0 50.0 60.0 67.0 50.0 60.0 67.0 99.6 109.8 99.6 109.8 34.1 39.7 47 46 64 84 T (K) 50.0 50.0 50.0 60.0 67.0 67.0 84.0 99.3 115.0 113.0 120.0 130.0 140.0

2.55 x 10 " 4 2.03 x 10 " 4 7.98 x 10~5 2.68 x l O - 4 6.36 x l O - 4 8.0OxIO- 5 2.56 x l O " 4 5.96 x l O - 4 8.1OxIO- 5 2.65 x l O - 4 5.95 x l O " 4 1.23 x 10 " 4 3.7OxIO- 4 3.5 x 10~5 1.03 x l O - 4 3.26 x 10 ~5 5.63 x 10" 5 1.9xlO- 5 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l O " 3 1.52 x 1014 7.5OxIO- 5 6.4OxIO" 5 2.63 x 10- 5 9.27 x l O - 5 2.03 x l O " 4 1.98 x 10 - 4 1.464 x 10 " 5 9.94 XlO" 5 6.7 x l O - 5 8.67 x l O " 5 2.49 x 10 ~4 7.49 x l O " 4 2.22 x l O - 3

Cumene

terf-Butylthiobenzylperacetate tert-Butyl peroxy-3,5,5-trimethylhexanoate

Ethylbenzene Chlorobenzene

4-Nitrobenzyl(terf-butylperoxy)oxalate

Benzene

2-ethylhexyl-

Chlorobenzene

tert-Butyl di-terf-butylperacetate

Cumene

terf-Butyl 2-carbomethoxyphenylperacetate

Cumene

terf-Butyl 2-(4-chlorophenoxy)2-methylperpropionate tert-Butyl 2-(4-chlorophenyl)2-methylperpropionate

Ethylbenzene Acetonitrile Benzene Dodecane

Hexadecane

Octane

tert-Butyl a-methylpercinnamate (cis) (trans)

kd (s'1)

Chlorobenzene

tert-Butyl 2,2,4,4-tetramethylperbutyrate

terf-Amylperoxy carbonate

T(0C)

Cumene Cumene

tert-Butyl 2-methyl-2-phenylperpropionate tert-Butyl perneodecanoate

Chlorobenzene Cumene Benzene Chlorobenzene

tert-Butyl 2-(4-nitrophenyl)2-methylperpropionate

Acetonitrile Benzene Dodecane

tert-Butyl permesitoate

Octane Cumene

tert-Butyl 1-phenylcyclopropylpercarboxylate

rc-Dodecane Ethylbenzene

Ea (kj/mol)

Notes

exp[-151.72/RT]

344

111

h

100.6

a,h

exp[- 140.78/K7] 116.7

c,h c c

exp[- 148.41/#7] 125.3

h

116.9

h

a

108.1

h

128.0

f,h f f,h f

125.5

exp[- 115 A7/RT] 105.2

147.5

Refs.

h

h,t i ti ti

273 273 273 267 267 267 315 344 344 344 344 31 31 31 344 344 344 344 245 245 245 257 257 257 315 265 265 265 265 265 265 265 265 265 265 265 150 150 150 150 249 249 338 344 344 344 344 265 265 265 265 265 265 345 345 345 255 323 323 323



Initiator tert-Butyl 1-phenylcyclopropylpercarboxylate

Solvent 2,2,4-Trimethyl pentane

tert-Butyl phenyldimethylperacetate

Chlorobenzene Isooctane

tert-Butyl 2-phenyl-3-perbutenoate tert-Butyl 4-phenyl-3-perbutenoate tert-Butyl 2-phenyl-2-methylperpropionate

Chlorohenzene Chlorobenzene Acetonitrile Benzene Benzophenone Benzyl benzoate Butyl phthalate Chlorobenzene Cumene Dodecane

tert-Butyl 4-vinylphenylperacetate

Hexadecane Methyl benzoate Octyl phthalate Toluene Cumene

Dibenzyl peroxalate Di-tert-butyl adipate

Pentane Styrene

Dicyclohexyl peroxydicarbonate


a-Methylstyrene Mineral spirits

15

4-Methoxybenzyl (tert-butylperoxy)oxalate

Benzene

1-Methyl-1-phenylethyl 2,2-dimethylperoxyporpionate

Cumene

tert-Amy\ perneodecanoate


Dibenzoyl monopercarbonate tert-Butyl 1-adamantylpercarboxylate

Benzene Cumene

T( 0 C) 102.6 113.0 120.4 60 40.6 60.6 60.6 60 60 50.0 50.0 60 60 60 60 60 50.0 60.0 67.0 60 60 60 60 60 70.9 85.4 100.3 25 105 115 125 50 44 60 77 T (K) 50 45 50 60 45 55 65 40 50 60 70 45 43 61 81 T (K) 60.00 45 55 65 64.6 74.6 84.6 60 70 80

^d(S" 1 ) 2.53 x 10 ~5 8.96 x 10 ~5 2.04 xlO~ 4 9.6xlO~ 4 2.95 x 10 ~5 3.059 xlO~ 4 4.064 xlO~ 4 2.9xlO~ 3 1.15 x 10 ~4 3.08 x 10 " 4 2.18 xlO~ 4 7.73 x 10 ~A 7.92 x 10 ~4 6.5 x 10 ~4 7.00xl0~ 4 5.25 x 10 ~4 8.77 x 10 ~5 3.00xl0~ 4 7.13 xlO~ 4 2.88 xlO~ 4 3.53 x 10 ~4 7.55 x 10 ~4 5.70xl0~ 4 5.66 x 10 ~4 5.54 x 10 " 5 3.00xl0~ 4 1.48 x l 0 ~ 3 6.7 x 10 ~5 3.50xl0~ 5 1.23 xlO~ 4 3.05 xlO~ 4 5.4xlO~ 5 1.93 x 10 ~5 1.93 x l 0 ~ 4 1.93 x l 0 ~ 3 3.3 x 1016 5.9xlO~ 5 2.78 x 10 ~5 5.58 xlO~ 4 2.07 xlO~ 4 6.69 x 10 ~5 2.48 x 10 ~A 8.27 xlO~ 4 6.91 x 10 ~6 2.80 x 10 ~5 1.032 xlO~ 4 3.57 x l O - 4 1.9xl0~ 5 1.93 x 10 ~5 1.93 xlO~ 4 1.93 x l O - 3 1.47 x 1014 8.05 x 10 ~5 5.15 x 10 ~5 2.05 x 10 ~5 7.4OxIO- 5 6.87xl0-5 2.44 xlO~ 4 7.78 x l O - 4 5.4 x l O - 5 2.12 x l O - 4 7.20xl0~ 4

Ea (kj/mol)

Notes

141.2

h

109.2

96.2 98.3

c,h t9 t9 m2 c,h c,h,g

109.3

h

t 12

116.5

h,k k

151.0

X2 X1 X1 c

exp[- 129.0/RT] 117

109.6

a a a c,h c c

a

exp[- 114.38/K7] 116.5 115.5

h h

116.7

h

124.7

h

Refs. 255 255 255 81 165 165 165 81 81 265 265 334 334 334 334 334 265 265 265 334 334 334 334 334 254 254 254 203 215 215 215 201 344 344 344 344 201 337 337 337 31 31 31 368 368 368 368 338 344 344 344 344 280 160 160 160 159 159 159 223 223 223

TABLE 6. Number of C atoms 15 (cont'd)

cont'd

Initiator tert-Butyl 4-(carboethoxy)phenoxyperacetate tert-Butyl a,p-dimethylpercinnamate (cis)

Solvent Ethylbenzene

(trans)

tert-Butyl 1-pernaphthoate tert-Butyl 2,2-dimethyl3-phenylthio perpropionate

Chlorobenzene Cyclohexane

tert-Butyl 2-(4-methoxyphenyl)2-methylperpropionate


tert-Butyl 1-phenylcyclo-n-Dodecane butylpercarboxylate

tert-Butyl 4-tert-butylperbenzoate

Chlorobenzene

Di-tert-butyl perpimelate

Styrene

tert-Butyl 2-(4-tolyl)2-methylperpropionate


tert-Butyl triisopropylperacetate

16

Octane 52.3 Ethylbenzene n-Hexadecane 2,2,4-trimethyl pentane

Octane Cumene

l,l-Dimethyl-2-phenylethylperpivalate

Cumene

1-Phenylethyl 4-methoxyperacetate 1-Phenylethyl 3-nitroperbenzoate 1-Phenylethyl 4-nitroperbenzoate 1-Phenylethyl perbenzoate Dibenzyl peroxydicarbonate

Benzene Benzene Benzene Benzene Benzene

Di-tert-butyl2-iodoperisophthalate

Chlorobenzene

Di-tert-butyl perphthalate

Benzene

Di-n-butyl phthalate

Chlorobenzene

T( 0 C) 70.5 95.0 103.2 110.1 85.1 95.0 103.7 110.0 110.0 110.1 55 65 75 50 50 40 50 57 50 7.89 x 10 ~5 60.0 52.3 52.3 61.6 100.1 119.8 135.9 105 115 125 50.0 50.0 50.0 60.0 67.0 60.0 24.8 41.6 55.2 40 50 60 70 99.7 100 100 100 40 50 60 68.4 85.4 101.6 100 115 130 100 115 130 107 125 146 T(K)

A^(S"1)

Ea (kj/mol)

1.6xlO~ 4 1.02 xlO~ 4 2.29 x 10 ~4 5.15xlO- 4 3.9xl0~5 1.17xlO- 4 2.84xlO~4 6.05xl0-4 7.9OxIO- 4 8.69 x l 0 ~ 5 1.63 x 10 ~5 1.61 x 10 ~5 1.98xlO- 4 1.675 x 10 ~3 9.96 x 10 ~A 1.49 x l O " 4 4.21 x IO- 4 1.028 XlO" 3 4.18 xlO~ 4 3.62 x 10 " 4 8.80xl0~ 5 7.69 x 10 ~5 2.46x10-4 3.81 x 10 ~5 4.5OxIO- 4 2.38 x l 0 ~ 3 4.45 x 10 ~5 1.05x10-4 5.06x10-4 6.0OxIO" 4 3.85 x 10 " 4 1.9OxIO- 4 5.58 xlO~ 4 1.32OxlO" 3 5.43 x 10 " 4 5.32 x 10~6 6.84 x l O - 5 3.78 XlO" 4 4.56 x 10~6 1.833 x 10~5 6.1 x 10 ~5 2.5IxIO-4 3.50xl0"4 5.97 x 10 ~4 4.10xl0~4 4.03 x 10 ~4 2.0xl0"5 6.25 x l O - 5 2.67 x l O - 4 8.24 x 10~5 4.45 x l O - 4 1.68 x l O " 3 1.1 x 10 ~5 7.8IxIO-5 4.8IxIO"4 1.08 x 10 " 5 7.8 x l O " 5 4.8 XlO" 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 9.39 xlO 1 6

118.8

122.6

116.9

Notes a

315

a,h a a a,h a a a a,v6

151 151 151 151 151 151 151 151 154 320 320 320 265 265 265 265 265 265

h,t6 t6

93.0

h

255 ti 110.6

h

150.6

Xi X1 X1

100.6

h

111.5

h

134.1 136.2 146.2 123.6 117

h h h h a a a h

93.9

159

155.0

exp[-157.85/^7]

Refs.

a a a h

323 255 255 255 134 134 134 215 215 215 265 265 265 265 265 265 267 267 267 362 362 362 362 259 259 259 259 337 337 337 248 248 248 337 337 337 269 269 269 344 344 344 344



Initiator Di-tert-butyl perphthalate

Cumene

terr-Butyl 1-phenyl-l-cyclopentane percarboxylate terf-Butyl 2,3-dimethyl2-phenylperbutyrate Cumyl 7V-phenylperoxy carbamate Dibenzyl peroxydicarbonate Di-terr-butyl perphthalate

Di-tert-bxxty\ persuberate

17

Solvent

^d(S1) 6

Ethylbenzene

99.9 115.0 130.1 60.0

8.34 x 10" 4.68 XlO- 5 2.6OxIO- 4 1.52 x 10 ~3

Ethylbenzene

50

4.3OxIO- 5

T(K) 50 100 115 130 115 125 43.5 52.3 60 70 80 10 35 10 10 100

1.26 x l O 1 4 2.92 x 10 " 5 1.08 x 10 " 5 7.83 x l O - 5 4.8OxIO- 4 7.86 x 10 ~5 2.8IxIO-4 1.184 x l O " 4 3.51 x 10 ~4 1.9xlO~ 5 5.3OxIO- 5 1.38 x l O " 4 4.5 x 10~4 1.9 x l O - 3 6.4X10" 4 5.IxIO"4 2.16 x l O " 3

79.6 70.6 80.3 100.5 60.0 43.5 52.3 61.6 25 40 25 40 25 40 39.3 53.8 53.8 70.0 25 40 25 40 25 40 25 40 25 40 25 40 105 119.4 135.1 105 115 125 98 116 137 T (K)

2.38 x 10 " 5 9.44 x 10 ~6 2.8OxIO- 5 3.09 x l O - 4 1.9OxIO- 3 1.27 x 10 ~4 3.91 x 10 ~4 1.218 x l O - 3 1.89 x 10 ~5 1.22 x l O - 4 1.01 x 10 ~4 5.44 XlO" 4 5.26 x 10~5 3.24 x l O - 4 4.98 x 10 ~5 5.23 x l O ~ 4 4.58 x l O - 4 2.62 x l O " 3 1.76 XlO" 5 1.03 x l O - 4 9.8X10" 7 6.9 x l O - 6 1.11 x l O ~ 4 6.02 x 10 " 4 2.31 x 10~4 1.65 x l O " 3 1.33 x 10" 4 7.25 XlO" 4 8.21 x 10~4 4.75 x l O " 3 2.79 x 10 ~5 1.29 x 10 " 4 6.07 x l O - 4 5.13 x 10~5 1.2OxIO- 4 5.1OxIO- 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 1.35 x 10 16

Xylene Toluene Benzene

Styrene

tert-Butyl 1-phenylcyclopentylpercarboxylate 1,1,3,3-Tetramethylbutylper-2-ethylhexanoate

2,2,4-Trimethylpentane Benzene

2-Phenylazo-2-propylperbenzoate

Chlorobenzene

1-Phenylethyl 4-dimethylaminoperbenzoate Di-terf-butylperhomoterephthalate

J( 0 C)

/7-Chlorotoluene Chloroform-di Benzene Cumene Toluene

tert-Butyl 1-phenylcyclohexanepercarboxylate

Ethylbenzene 2,2,4-Trimethylpentane

tert-Butyl 2-(phenylthio)perbenzoate

Acetone Acetonitrile terf-Butanol Chlorobenzene

Cyclohexane DMSO Ethanol Isopropanol Methanol terf-Butyldibenzothiophene-4-percarboxylate

Chlorobenzene

Di-tert-butyl perazelate

Styrene

Chlorobenzene

E* (kj/mol)

Notes

140.8

h

ti

Refs. 269 269 269 323 324

exp[- U1.6/RT] 157.7

159.0 103.5

a a a a Xi Xi h

101

a a a

111.5

h

122.3

h

107.7

h

m2 ITi2 m2 m2 m2 m2 b m2

128.0

154.8

exp[- 141.95/RT]

m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 h

40 90 126 126 126 215 215 255 255 337 337 337 260 260 260 260 259 272 272 272 272 323 255 255 255 22 22 22 22 22 22 134 134 134 134 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 215 215 215 344 344 344 344

TABLE 6. cont'd Number of C atoms 18

Initiator tert-Butyl 4-benzoylperbenzoate terf-Butyl diphenylperacetate

2,4,4-Trimethylpentyl2-perneodecanoate

a,co-Di-0,O-ter?-butyl-(bispersuccinyl)ethylene glycol

tert-Buty\ 1-phenyl-l-cycloheptanepercarboxylate Di-tert-buty\ /?-phenylenediperacetate

tert-Buty\ 2-(phenylthiomethyl)perbenzoate tert-Buty\ thioxanthone-4-percarboxylate Di-tert-butyl persebacate

Di-(2-ethylhexyl)peroxydicarbonate

Solvent Benzene Chlorobenzene Chlorobenzene Cumene

Decane Dodecane Hexadecane Octane tetradecane Chlorobenzene

Ethylbenzene

Ethylbenzene Cumene

Chlorobenzene Chlorobenzene Styrene


Decane

Mineral spirits

19

Di-«-heptyl persuccinate

Styrene

tert-BxAy\ diphenylmethylperacetate terr-Butyl diphenylperglycidate (cis)


(trans)

tert-Buty\ 2,2-diphenylperpropionate tert-Butyl 4-hydroxy-3,5-di(tert-butyl)perbenzoate tert-Butyl 4-(4-methylbenzoyl)perbenzoate

Cumene

Chlorobenzene Benzene Carbon tetrachloride Benzene Chlorobenzene

T( 0 C)

kd (s"1)

Ea (kj/mol)

25 110 60 40.3 49.6 59.9 70.4 77.5 77.5 77.5 77.5 77.5 40 57 76 T (K)

1.84 x 10 ~4 2.88 x 10 ~5 4.44 x 10 ~4 2.75 x 10 " 5 9.81xl0"5 3.10xl0"4 1.04 XlO- 3 1.66 x l O " 3 1.688 x l O " 3 1.632 x 10~3 1.651 x 10" 3 1.627 x 10 ~3 1.93 x 10 ~5 1.93 x 10 " 4 1.93 XlO" 3 3.97 x 1014

95 105 115

2.68 x 10 " 6 9.10xl0"6 2.97 XlO" 5

60.0

2.75 x 10 ~3

70.9 85.4 100.3 98.7 120.1 120 135 105 115 125

3.69 x 10 ~5 2.08 XlO" 4 8.83 x l O " 4 4.64 x 10 " 5 4.2OxIO" 4 1.89 x 10 " 4 1.15 x l O " 3 5.10xl0~ 5 1.2Ox 10" 4 5.0OxIO" 4

40 47 64 83 T (K) 30 45 60 40 50 60 60 73.5 85

1.9xlO~ 5 1.93 x 10 " 5 1.93 XlO" 4 1.93 XlO" 3 1.83 x 1015 5.3xl0"6 3.31xl0~ 5 2.32 XlO- 4 1.3xl0" 5 6.14 xlO" 5 2.3IxIO- 4 6.IxIO"" 6 3.85xl0- 5 1.70 XlO" 4

60 60.0 70.0 80.0 60.0 70.0 80.0 34.1 100 100 25 110

1.9xl0" 3 2.8xl0"5 5.5 x l 0 ~ 5 1.68 x l O " 4 1.6 x l O " 5 3.9 XlO" 5 1.20 XlO" 4 7.76 x 10 ~5 3.18 x 3.60 x 1.45 x 3.03 x

10 ~5 10 ~5 10 " 4 10 ~5

Notes p2

101.7 104.6

a,h h

exp[- 115.19/RT\ 147.5

Refs. 279 279 81 136 136 136 136 168 168 168 168 168 344 344 344 344 306 306 306 323

112.7

134.7 156.5 154.8

h,k k k h h,m2 m2 Xi Xi Xi a

exp[- 122.45//?7] 105

126

131.0

a a a a a a Xi X1 X1

103.3 112.1

a,h h

117.2

h

c,e c,e p2

254 254 254 154 154 22 22 215 215 215 338 344 344 344 344 337 337 337 337 337 337 215 215 215 81 204 204 204 204 204 204 249 246 246 279 279



20

21

22

23

Initiator ten-Butyl a-phenylpercinnamate (cw) (trans)

Cumene Cumene

Cumyl perneodecanoate


Di-rc-heptyl peradipate

Styrene

tert-Butyl 2-carbobenzoxyphenylperacetate

Cumene

tert-Butyl 2-methyl-2-phenylperhexanoate oc,co-Di-0,O-tert-butyl-(bispersuccinyl)diethylene glycol

Ethylbenzene Ethylbenzene

tert-Butyl 8-(phenylthio)1-pernaphthoate

Chlorobenzene

tert-Butyl 4-(2,4,6-trimethylbenzoyl)perbenzoate tert-Butyl 2,2-diphenyl3,3-dimethylperbutanoate

Benzene Chlorobenzene Toluene (?)

Di-tert-butyl 2-thiophenylperisophthalate

Chlorobenzene

2,5-Dimethylhexyl 2,5-di(peroxybenzoate)

Benzene

Di-(4-tert-butylcyclohexyl)peroxydicarbonate

Chlorobenzene

tert-Butyl 2,6-di(phenylthio)perbenzoate tert-Butylperoxy stearyl carbonate

Chlorobenzene

tert-Butyl 2,4,6-tri-tert-butylperbenzoate

24

Solvent

tert-Butyl

triphenylperacetate

Chlorobenzene

Cumene


Di-tert-butyl 2,3-diphenylpersuccinate

Cumene

Di-rc-heptyl persebacate

Styrene

2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane

Benzene

Chlorobenzene

T( 0 C)

A:d (s"1)

Ea (kj/mol)

Notes

136.8

h

133.9

h

99.6 109.8 99.6 109.8 39 39 56 75 T(K) 60 73.5 85 71.0 85.4 102.4 50

1.52 x 10~4 4.4IxIO"4 8.2 x 10~5 2.59 x 10 ~4 1.9xl0~ 5 1.93 x 10 " 5 1.93 xlO~ 4 1.93 x l 0 ~ 3 3.12 xlO 1 4 1.02 x 10 ~5 6.57 x l O " 5 2.98 x l O - 4 8.84 x 10" 6 5.46 x 10 ~5 4.23 x l O - 4 5.01 x 10 " 5

95 105 115 50 70 70 80 25 110 30 39.7 50 12.1 25.0 40.0 100 115 130 48 64 82 T (K) 40.1

2.34 x 10 ~6 155.0 8.88 x 10 ~6 3.27 x l O - 5 3.83 x 10 ~5 99.2 3.44 x 10~4 3.12 x l O " 4 9.82 x l O - 4 1.34 x 10 ~4 1.8OxIO- 5 2.76 x 10 ~5 • 114.8 1.15 x 10 ~4 5.45 x l O - 4 1.68 x l O " 4 73.7 6.45 x 10 ~4 3.09 x l O - 3 1.87 x l 0 ~ 5 154.0 1.25 x 10 ~4 7.14 xlO~ 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 XlO" 3 7.44 x 1015 exp[- 12639/RT] 7.07 x l O " 5

98 117 137 T (K) 70.4 84.0 99.3 115.0 34.9 25.7 34.9 45.5 70.1 79.9 90.0 60 73.5 85 60 70 80 68 86

1.93XlO" 5 1.93 x l O - 4 1.93 XlO" 3 3.94 x 1016 5.84 x 10 " 6 3.54 x 10 " 5 2.67 x l O - 4 1.656 x l O " 3 7.8xlO" 4 1.7 x l O " 4 5.8 XlO" 4 2.3 XlO" 3 9.83 x 10 ~5 3.29 x 10 " 4 1.20 x l O " 3 1.17xlO" 5 7.13 x l O - 5 3.03 xlO~ 5 6.7xlO~ 6 2.92 x 10 " 5 1.14 XlO" 4 1.93 x 10 " 5 1.93 x l O " 4

a

exp[-114.59//?7] 133.1

129.5

Xi Xi X1 h

h

h,m2 m2 m2 p2 J2 J2 k h

a a a

exp[- 151.59/RT]

100.8

h

125.5

c,h c c xi Xi X1 a a a

131.0

142

Refs. 150 150 150 150 338 344 344 344 344 215 215 215 257 257 257 324 306 306 306 154 154 154 154 279 279 250 250 250 248 248 248 126,337 126,337 126,337 344 344 344 344 154 344 344 344 344 345 345 345 345 153 153 153 153 196 196 196 215 215 215 337 337 337 344 344

TABLE 6. cont'd Number of C atoms 24 (cont'd) 25

Initiator

Solvent

2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane tert-Butyl 2-(2,2-diphenylvinyl)perbenzoate

Chlorobenzene Chlorobenzene

Cyclohexane Methanol tert-Butyl 2-percarboxybenzalfluorene 26

30

oc,co-Di-0,0-caprylyl-(bis succinyl)ethylene glycol

Chlorobenzene Methanol Ethylbenzene

oc,co-Di-0,O-caprylyl-(bispersuccinyl)triethylene glycol

Ethylbenzene

Dimyristyl peroxydicarbonate

Chlorobenzene

34

Dicetyl peroxydicarbonate

Chlorobenzene

36

oc,0)-Di-0,0-heptanoyl-(bisperphthaloyl)triethylene glycol

Ethylbenzene

42

oc,co-Di-0,0-caprylyl-(bispersuccinyl)nonaethylene glycol

Ethylbenzene

46

a,oo-Di-0,0-heptanoyl-(bisperphthaloyl)tridecaethylene glycol a,ca-Di-O,O-caprylyl-(bispersuccinyl)tridecaethylene glycol

Ethylbenzene

50

TABLE 7.

Ethylbenzene

T( 0 C) 106 T(K) 90.0 90.3 100.0 105.5 119.3 90.0 90.4

*d (s" 1 ) 1.93 2.19 1.32 7.45 3.27 4.64 1.54 3.5 2.3

x 10 ~3 x 1015 x 10~4 x 10~5 xlO"4 XlO" 4 xlO-3 x 10 ~5 x 10~3

90 90

3.75 x 10 ~4 2.47 x 10 ~3

65 75 85 95 65 75 85 95 48 65 84 T (K) 48 65 84 T (K) 65 75 85 95 65 75 85 95 75 85 95 65 75 85

1.48 x 10~5 4.10xl0"5 2.19 x l O - 4 6.92 x l O - 4 2.74 x 10 ~5 8.47 x 10 " 5 2.95 x l O - 4 8.92 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l O " 3 2.82 x 10 15 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 3.02 x 1015 5.02 x IO ~5 1.420 x 10 ~4 5.19 x l O - 4 1.410 x l O " 3 1.66 x 1O~5 6.57 x 10 " 5 1.78 XlO" 4 9.72 x l O - 4 1.13OxIO- 4 3.5OxIO" 4 8.80xl0~ 4 1.28 x l 0 ~ 5 4.46 x 10 ~5 1.91 x l O ~ 4

Ea (kj/mol)

Notes

Refs. 344 344 175 175 175 175 175 175 175

exp[- 130.SS/RT] t9 t9 t9 t9

175 175 120.7

h

306 306 306 306 306 306 306 306 344 344 344 344 344 344 344 344 306 306 306 306 306 306 306 306 306 306 306 306 306 306

116.9

exp[- 124.10/RT]

exp[- 124.30/RT] 124.4

116.9

122.3

128.2

MISCELLANEOUS INITIATORS

Initiator

Solvent

Acetyl cyclohexyl sulfonyl peroxide

Benzene

AH1-Cyanocyclohexyl)pentamethylene keteneimine

Chlorobenzene

Dibenzyl hyponitrite

Paraffin

T ( 0 C) 30 40 45 80.0 89.2 100.1 61.5 68.5 75.5 80.5 132

^d(S1) 1.4XlO" 5 9.42 x l 0 ~ 5 2.10xl0~4 3.25 x 10 ~6 1.007 x l 0 ~ 5 4.025 XlO" 5 6.5 x 10~4 3.7 x l 0 ~ 3 8.3 x l O - 3 1.45 x l O ~ 2 8.7XlO- 1

£ a (kj/mol)

Notes

147

a a a

Refs. 337 337 337 179 179 179 240 240 240 240 240


TABLE 7. cont'd Initiator Di-terf-butyl hyponitrite

Peroxybenzoylnitrate

Solvent tert-Butanol rc-Butyl ether Ethanol(95%) Isooctane

Nujol Vapor

Vapor + NO

Vapor + NO

2,3-Dimethyl-2,3-diphenylbutane

Chlorobenzene

3,4-Dimethyl-3,4-diphenylhexane

Chlorobenzene

l,4-Dimethyl-l,4-diphenyl-tetrazene-2

Benzophenone Cumene Paraffin

Siliconeoil Potassium persulfate

0.1 M NaOH

Water (pH 3) Water

1-Pentanesulfonylazide 1,4-Butanedisulfonyl azide 1,6-Hexanedisulfonyl azide 1,9-Nonanedisulfonyl azide

Diphenyl ether Diphenyl ether Diphenyl ether Diphenyl ether

1,10-Decanedisulfonyl azide l,4-Dimethylcyclohexane-a,a'-disulfonyl azide

Diphenyl ether Diphenyl ether

T( 0 C) 65 65 65 45 55 65 75 65 7.6 19.9 30.4 40.6 50.1 60.5 T(K) 18.1 30.4 40.6 T (K) 30.4 50.2 68.5 T(K) 237 259 284 T(K) 201 226 254 T(K) 121 149 120 130 140 164.2 174.3 186 194 126 139 50 60 70 80 90 50 80 80 40 50 60 50 60 70 50 166 163 163 150 160 170 163 163

kd (s" 1 )

Ea (kj/mol)

4.68 x 10 " 4 4.50 x 10 " 4 3.93 x 10 ~4 2.72 xlO~ 5 116.9 1.07 x l O - 4 4.0OxIO" 4 1.33OxIO-3 5.17 x 10~4 2.79 x 10 ~6 69.1 1.05 x l O - 5 2.02 XlO" 5 3.64 x l O - 5 1.21 x 10- 4 2.74 XlO" 4 1 x 107 exp[-69.1//?7] 8.18 xlO" 5 108.5 3.62 XlO" 4 1.42 x l O - 3 1.6 x 1015 exp[- 108.5/RT] 1.34 x l 0 ~ 5 79.2 7.22 x l O - 5 3.41 x 10" 4 6.3 x l O - 8 exp[-79.2/i?n 1.93 x 10 ~5 1.93 x l O " 4 1.93 x l O - 3 7.34 xlO 1 8 exp[-230.19//?n 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l 0 ~ 3 1.45 xlO 1 5 exp[- IS032/RT] 3.3xl0"4 3.45 x l 0 ~ 3 2.3xlO" 4 6.5 x l O - 4 1.67 XlO" 3 2.6xlO- 2 5.6 x l O - 2 1.43XlO"1 2.5XlO- 1 3.7xlO" 4 1.92 x l O - 3 9.5 x 10 ~7 140.2 3.16 xlO~ 6 2.33 x l O - 5 9.16 XlO" 5 3.5 x l O - 4 1.66 x 10 ~6 6.89 x 10~5 5.78 x l O - 5 1.65 xlO" 2 83.4 4.02 x l O " 2 1.08XlO"1 3.78 XlO" 3 121.5 2.18 x l O - 2 5.01xl0~ 2 1.1 x 10- 6 4.46 x 10 " 4 5.02 x 10 " 4 5.02 x 10 ~4 8.84 x 10 " 5 2.25 xlO" 4 4.45 x l O - 4 4.45 x 10 ~4 4.82 x 10" 4

Notes

h

h

h

h

a a a a a a a,vn a,v u d 3 ,v 22 d 3 ,v 22 d 3 ,v 22 d 3 ,v 23 d 3 ,v 23 d 3 ,v 23

Refs. 317 317 317 317 317 317 317 317 261 261 261 261 261 261 261 261 261 261 261 261 261 261 261 344 344 344 344 344 344 344 344 240 240 240 240 240 240 240 240 240 240 240 242 242 242 242 242 242 115 115 262 262 262 262 262 262 262 166 166 166 166 166 166 166 166

ro-Xylene-a,a'-disulfonyl azide p-Xylene-oôc'-disulfonyl azide Benzenesulfonyl azide

Diphenyl ether Diphenyl ether Naphthalene

/7-Bromobenzenesulfonyl azide p-Chlorobenzenesulfonyl azide p-Methoxybenzenesulfonylazide p-Nitrobenzenesulfonyl azide p-Toluenesulfonyl azide

Naphthalene Naphthalene Naphthalene Naphthalene 1,4-Dichlorobutane Dimethyl terephthalate Diphenyl ether

p-Toluenesulfonyl-p-tolylsulfone

Hexanoic acid Naphthalene Nitrobenzene 1-Octanol Tetradecane Acetonitrile

Dioxane

163 163 110 120 125 130 175 120 120 120 120 145 155 130 145 155 155 120 155 155 155 29.3 39.1 49.3 29.3 39.5 49.3

6.09 x 10 ~4 5.78 x 10 ~4 3.6xlO" 6 1.07 x l O - 5 1.97xlO- 5 3.41xl0"5 6.08 x l O - 5 1.36 x 10 ~5 1.15 x 10 " 5 1.31 x 10 ~5 1.6OxIO" 5 1.7OxIO- 4 3.23 x 10 ~4 3.30 x 10~5 1.44 XlO" 4 3.43 x l O " 4 2.97 x 10 ~4 1.12 x l O " 5 3.97 x 10 ~4 3.63 x 10" 4 3.80 x 10 ~4 3.9xl0-5 1.45 x l O - 4 5.4 XlO" 4 2.IxIO-5 1.01 x l O - 4 3.9 x 10 ~4

152.3

103.8

h

115.5

h

166 166 235 235 235 235 235 235 235 235 235 166 166 166 166 166 166 235 166 166 166 144 144 144 144 144 144

C. NOTES a /cd converted to s" 1 from author's units b kd values for several concentrations averaged t)2 analyzed from nonisothermal conditions c kd increases with increasing initiator concentration c 2 rate non-linear c3 hydroperoxide concentration 7.83 x 10~ 3 mol/1 C4 hydroperoxide concentration 2.50 x 10~ 3 mol/1 d kd decreases with increasing initiator concentration d2 after 1st half life; rate slower initially d3 rate is second order: units are 1/mol sec. e fcd listed is for lowest initiator concentration f &d is extrapolated value for zero initiator concentration g kd ^ has been corrected for induced decomposition g2 corrected for uncatalysed reaction (7 x 10 ~5 s" 1 ) h AH (not E2) i pressure (number gives mbar) j iodometric analysis j 2 manometer measurement k infrared analysis 1 kd is limiting value with respect to additive concentration mi 3,4-dichlorostyrene added to minimize induced decomposition m2 styrene added to minimize induced decomposition ni3 methyl methacrylate added to minimize induced decomposition ni4 isobutene added to minimize induced decomposition m5 acenaphthalene added to minimize induced decomposition m 6 1 mol/1 oc-methylstyrene added to minimize induced

decomposition mj butadiene added to minimize induced decomposition mg acrylonitrile added to minimize induced decomposition n trichloroacetic acid added n2 3.2wt.% or about 0.1 monolayer o addition of trichloroacetic acid did not affect kd p degassed p 2 photochemical benzophenone added: 6.56 x 10 17 quants/min @ 366 nm q addition of trichloroacetic acid increased kd several fold q 2 pH 2.90 q 3 pH 7.05 r not inhibited, but initiator concentration low enough (0.01-0.09 M) so that higher order decomposition is unimportant s solvent not degassed 11 2,6-di-terr-butylphenol added to inhibit induced decomposition t2 oc,a-diphenyl-P-picrylhydrazyl added to inhibit induced decomposition t3 phenyl-oc-naphthylamine added to inhibit induced decomposition t4 tetrachloroquinone added to inhibit induced decomposition t5 1,3,5-trinitrobenzene added to inhibit induced decomposition t6 12 added to inhibit induced decomposition tj O 2 added to inhibit induced decomposition t8 5-20% NO 2 added to inhibit decomposition References page II - 70

t9 tio

vi V2 V3 V4 V5 v6 v7 Vg v9

galvanoxyl added to inhibit induced decomposition a,y-bisdiphenylene-p-phenylallyl added to inhibit induced decomposition oc-naphthylamine added to minimize induced decomposition 2,3 / ,5 / ,6 / -tetra-te7t-butyl indophenoxy added benzoquinone added 2,6-di-teJt-butyl-4-methylphenol added in absence of oxygen from initiation data in multisurface reaction vessel rate reduced when nujol layer used to exclude Hg vapor rate increased when nujol layer used to exclude Hg vapor acetic acid added CuCl 2 added CuCl added 0.1 mol AgClO 4 /mol AIBN added 3.9 mol thiophenol added tert-bxxtyl mercaptan added 2.5 mol cyclohexane added ~ 4 x l O ~ 2 mol pyridine added 2 x 10~ 2 mol pyridine added

D.

REFERENCES

tn ti2 ti3 114 ui u2 u3 U4 U5

1. J. E. Guillet, T. R. Walker, M. F. Meyer, J. R Hawk, E. B. Towne, Ind. Eng. Chem., Prod. Res. Develop., 3, 257 (1964). 2. L. M. Arnett, J. Am. Chem. S o c , 74, 2027 (1952). 3. L. M. Arnett, J. H. Peterson, J. Am. Chem. Soc, 74, 2031 (1952). 4. W. M. Thomas, M. T. O'Shaughnessy, J. Polym. Sci., 11,455 (1953). 5. A. T. Blomquist, A. J. Buselli, J. Am. Chem. S o c , 73, 3883 (1951). 6. C. G. Swain, J. T. Parke, W. H. Stockmeyer, J. Am. Chem. Soc, 72, 5426 (1950). 7. D. J. Brown, J. Am. Chem. Soc, 70, 1208 (1948). 8. S. W. Butaka, L. L. Zabrocki, M. F. McLaughlin, J. R. Kolcznski, O. L. Mageli, Ind. Env. Chem. Prod. Res. Develop., 3, 261 (1964). 9. W. A. Strong, Ind. Eng. Chem. Prod. Res. Develop., 3, 264 (1964). 10. L. E. Redington, J. Polym. Sci., 3, 503 (1948). 11. B. Baysal, A. V. Tobolsky, J. Polym. Sci., 8, 529 (1952). 12. A. Conix, G. Smets, J. Polym. Sci., 10, 525 (1953). 13. M. R. Gopalan, M. Santhappa, J. Polym. Sci., 25,333 (1957). 14. J. C. Bevington, J. Toole, J. Polym. Sci., 28, 413 (1958). 15. H. C. Haas, J. Polym. Sci., 39, 493 (1959). 16. A. I. Lowell, J. R. Price, J. Polym. Sci., 43, 1 (1960). 17. H. C. Haas, J. Polym. Sci., 55, 33 (1961). 18. D. F. Doehnert, O. L. Mageli, Mod. Plastics., 36, (6), 142 (1959). 19. R. C. Lamb, P W. Ayers, M. K. Toney, J. Am. Chem. Soc, 85, 3483 (1963).

v 10 Vn v 12 v 13 v 14 v 15 v 16 v 17 v is v 19 V 20 v2i V 22 v23 v24 v25 v 26 w x1 x2 y z

2.5 mol cumene added buffered with sodium pyrophosphate saturated with ethyl acetate 3.11 mol CCl4 present peroxide in P(MMA) peroxide in P(sty.) 0.26 mol piperidine 0.24 mol triethylamine 0.21 mol AT,Af-diethylaniline 0.22 mol pyridine 0.9 mol Z n C l 2 in presence of 1 5 N O 0.12 mol 18 crown 6 added 0.24 mol diglyme added 0.02 M pyridine added 0.10 M pyridine added 0.10 M 2,6-lutidine added stereoisomers actual rate divided by 2 because of two identical peroxide groups each peroxide group has different k^ measured in differential scanning calorimeter: subscript is heating rate in deg/min pressure (in bar)

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P r o p a g a t i o n i n

F r e e

a n d

T e r m i n a t i o n

R a d i c a l

C o n s t a n t s

P o l y m e r i z a t i o n

M. Kamachi Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan B. Y a m a d a Department of Applied Chemistry, Faculty of Technology Osaka City University, Sumiyoshi, Osaka, Japan A. Introduction B. Tables of Propagation and Termination Constants Table 1. Dienes Table 2. Olefins Table 3. Acrylic Derivatives Table 4. Methacrylic Derivatives Table 5. ltaconic Derivatives Table 6. Fumaric Derivatives Table 7. Vinyl Halides Table 8. Vinyl Esters Table 9. Vinyl Ethers Table 10. Styrene Derivatives Table 11. Vinyl Heteroaromatics Table 12. Aldehydes Table 13. Others C. References

11-77 11-79 II-79 II-79 II-80 II-82 II-85 U-87 II-87 II-87 II-88 II-88 II-90 II-90 II-90 11-91

The rate constants kv and kt have usually been assumed to be independent of chain length. In this chapter termination constants depending on the length of the polymer radicals are also reported. In American literature the right hand side of (A4) is written as 2£t[P#] . In this chapter the definition given in Eq. (A4) has been used. Simultaneous determination of absolute values of both kv and kt from a single experiment has not been reported. In practice, the ratio k^/kt is determined from measurements of molecular weight as a function of rate of polymerization for a low conversion polymerization or from measurements of initiation rate and polymerization rate in a low conversion. The ratio kp/kt is determined from nonsteady-state measurements of the average lifetime, r, of the growing polymer chain in a photochemically initiated polymerization. This lifetime may be defined by noting that the concentration of chains present must be related to their average lifetime and rate of disappearance by (A6)

A.

INTRODUCTION

In free radical polymerization the propagation and termination rate constants describe the reactions

which, from (A3) and (A4), yields (A7)

(Al) dead polymer

(A2)

where P^ is a propagating chain of any length n and M is the monomer. The rate constants are defined by the following equations:

By combining the separately determined ratios, k^/kt and kp/kt, the individual propagation and termination rate constants may be calculated. Alternatively, the rate of initiation, R[, may be measured as the rate of initiator disappearance and equated to R1. This gives (from (A6) and (A3))

(A3) (A4) where (A5)

(A8) There is a large degree of imprecision inherent in measuring r and in combining data from different experiments, which helps to explain the scatter in the data tabulated here.

/Ct(XiO"6)

kp

/C1(XiO-6)

Figure 1. Arrhenius plots of all bulk polymerization data for styrene for kp (•) and /ct (+). Solid lines are least squares obtained by assuming all points to be of equal value.

The two monomers styrene and methyl methacrylate have been so extensively studied that their data are presented as Arrhenius plots (Figs. 1 and 2). Because of the influence of solvents on the rates, only data of bulk polymerizations are shown. It remains a wide scatter, which should serve as a warning against casual acceptance of any single number. Solid lines are the least squares that have been calculated assuming all points to be of equal value. For the termination rate of methyl methacrylate the leastsquares line results in a positive slope and is not shown. In this case a temperature-independent kt could be a better representation of the experiments. The pulse laser polymerization (PLP) method has been developed as a new method of obtaining kp. In the PLP method, the value of kp can be estimated from the degree of polymerization of polymer formed, vp, a knowledge of the monomer concentration, [M], and tf the time between pulses: (A9) The reproducibility of the PLP method has been recognized by an IUPAC Working Party on Modeling of Kinetic and Process of Polymerization, which is establishing a critical review of the literature values of kp.

K9

1000 T Figure 2. Arrhenius plots of all bulk polymerization data for methyl methacrylate for /cp (•) and /ct(+). Solid lines are least squares obtained by assuming all points to be of equal value. The line for kx is not shown since a horizontal line for a temperature independent kt could be a better representation. Classification of the methods for the determination of rate constants The tabulated data refer to seven different methods. Method A uses the following four methods for the measurement of the lifetime r: Al -rotating sector or a "flashing" laser A2 - flow through a tube with spatially separated light and dark sections A3 - spacial intermittent polymerization (SIP) A4 - intermittent illumination method Method B effectively measures only a single decrease (increase), in the radical concentration by the following methods: B l - dilatometry B 2 - dielectric constant B 3 - interferomety B4 - temperature change B5 - viscosity B6 - light scattering B7 - monomer pressure

B 8 - cathetometer B9-inhibitor BlO-scavenger

Method F uses pulse laser photopolymerization (PLP) method

Method C uses electron spin resonance (ESR) for the determination of the radical concentration Method D refers to values obtained in emulsion polymerization by application of the Smith-Ewart theory

Fl - PLP F2 - PLP-GPC (MWD) F3 - PLP-MALDI TOF (-GPC) Method G refers to the method of measuring molecular weight (MW) and molecular weight distribution (MWD) by Gl - gel permeation chromatography (GPC) G2 - high performance liquid chromatography (HPLC)

Method E refers to recalculated values

B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS TABLE 1. DIENES Monomer 1-Acetoxybutadiene Butadiene

k9 (1/mol/s)

M x I O " 6 ) (l/mol/s)

Temp. (0C)

Method

18.0 &p = 1 . 2 x l 0 8 x exp(- 39000/RT) 150 ± 4 0

281

25 10

Al D

152 23

kt = 1.13 x l O 4 xexp(-711/r)

5 45-60

C Gl

223 202

50

Fl

221

-

50

Fl F2

Solvent: chlorobenzene Solvent: chlorobenzene

-

40

D D

Quoted in Ref. 86

l n * p = l n (3.873 x 1010) - 53400/RT 111.6 kp = 8.05 x 107 xexp(-35710//?7) Chloroprene 220 fcp = 2 . 9 x l 0 9 x exp(-41000/^7) *p = 1.95 x l O 7 x exp(- 26630/RT) 2,3-Dimethyl-l,3-butadiene &p = 8 . 9 x l 0 7 x exp(- 38000//?7) Ethyl 4-ethoxy-2,4-pentadienoate 9.9 Ethyl 4-methyl-2,4-pentadienoate 29.7 Ethyl pentadienoate 30.9 1,3-Hexadiene 20 ± 1 0 2,4-Hexadiene 16 ± 1 2 Isoprene 2.8

2-Methyl-l,3-pentadiene

Remarks

Refs.

221 187 59 84

Fl

198

D

71 152 152 152 223 223 24

9.3 23 19 -

25 25 25 5 5 5

Al Al Al C C D

125 ± 3 0 35 ± 10

-

5 5

C C

k p (1/mol/s)

M x I O 6 ) (1/mol/s)

Temp. (° C)

Method

1050 ± 5 0 455 ± 5 0 200

83 -20.01 130

Al Al Al

3.9 (7.8) x 102 1.99 x 102 -

130 190 230

Al C Fl

3.2 x 103

190

Fl

Calalyst system: diisopropylbenzene, monohydroperoxidetetraethylenepentamine

223 223

TABLE 2. OLEFINS Monomer Ethylene

Propylene

470 ± 3 0 18.6 ± 2 5400 £ p = 4.8x 107 x exp[(- 4450 + 3.Ix 10~6p)/T] 1.2 x 104 1.09 x 104 3.08 x 104

&p = 2 x l 0 6 x exp(- 32000/RT)

50-150

Remarks Solvent: benzene Pressure 1.8 x 10 8 Pa Pressure (5-17.5) x 10 7 Pa, using results of Ref. 141 Pressure 1.9 x 108 Pa Initial pressure 2.27 x 108 Pa Pressure 2.55 x 108 Pa, at low or moderate conversion Pressure 2.50 x 108 Pa, at conversion 0 Radical telomerization

Refs. 53 66 139 142 135 151 167 167 129

References page 11-15

TABLE 3. ACRYLIC DERIVATIVES Monomer

kp (1/mol/s)

kt (xlO~ 6 ) (1/mol/s)

Acrylamide

6000 ± 1000 18000 ±1500 8200 220 (7.9 ±0.5) x 10 4 (4.3 ±0.2) x 104 (3.3 ±0.2) x 104 (2.3 ±0.1) x 10 4 fcp=7xl06 x exp[(- 21000 ± 2000)/RT]

3.3 ±0.6 14.5 ±2.0 5.5 1.0 660 ± 4 0 350 ± 2 0 230 ± 2 0 160 ± 1 0

650

2.6

3150

2.6

Temp. (0C)

25 19 26 30 30

Method Al, Bl Al A A Al Al Al Al Fl

Remarks Solvent: water, pH 5.5 Solvent: water Solvent: water Solvent: DMSO Solvent: water 0.38M H 2 O : DMSO (90:10) H 2 O:dioxane (90:10) H 2 O : THF (92:8)

Refs. 79 41 89 89 126 119 119 119 197

Acrylic acid

-,butyl ester

- , cyclohexyl ester -,ethyl ester

6600 2.7 13 0.018 2100 330 1977 3.84 679±66 6.4±0.6 log 10 fcp = 6.0123-748.4/7 ln[(*t[p]/(1.00 + OMp)] = l n * t [I]-0.6Op 1360 1.28 963 1.18 1320 1.07 360 0.36 2722 ±248 3.2 ±0.3 800 1.76 12.39 x 10 3 139.2

- , 2-ethylhexyl ester - , methyl ester

23

Al Al

30 25-80 30

Al Al B4 Al Al Fl B5

30

Al

30 50 50

Al Al Al

25 25

155 1300

0.233 75

50 15

Al Al

880

260

15

Al

25 25

Al Bl Al

1580 580 fcp = 1 . 0 x l 0 8 x exp(- 30000/RT) 1000 11680 21300 (1.5 ±0.2) x 10 4 (3.7 ±0.6) x 104 6.3 x 104 (1.4 ±0.2) x 104

55 6.5 fct = 2.8xl0n x exp(- 22000/RT) 3.5550 194 -

60

Al Al Al G2

-

60 60 60

G2 G2 G2

- , 2-(acetoacetoxy-methyl)-, ethyl ester - , 2-cyano-, ethyl ester

300 1622 1610 1613 1607

1.0 411 404 411 404

60 30 30 30 30

C Al Al Al Al

- , 2-chloro-, ethyl ester

1660 1408 1120 978 350

333 244 4.8 x 102 435 2.1

30 30 30 30 60

Al Al Al Al C

- , 2-fluoro-, ethyl ester - , 2-acetoxymethyl-, methyl ester

Solvent: Water, pH 7.9, (with 1.2MNaOH) Solvent: water, pH 7.9 (with 1.5NNaCl) Solvent: water, pH 11

Pressure 5.0 x 107 Pa Solvent: benzene 1.76M kt \p\; kt for pressure p (bar), kt [l] = 3.5x 106 Solvent: anisole 2.00M Solvent: benzene 2.00M Solvent: chlorobenzene 2.00M Solvent: benzonitrile 2.00 M Solvent: benzene 1.76M Solvent: toluene 1.84 M Solvent: benzene x\ molar fractions of monomer, x = 0.401, kp and kt also given by other [M] Solvent: toluene 1.94M From unpublished results of Ross and Melville From unpublished results of Matheson

99 99 99 10 57 107 137 201 122 138 138 138 138 137 108 171

108 22 22 19 48 21

Solvent: benzene 2.69 M Primary propagating step (jfcpl), Ph-MA* PhCO 2 -MA' tert-BuO-MAm Secondary propagating step (kp2), Ph-MA-MA*, PhCO 2 -MA-MA', tert-BuO-MA-MA* Solvent: benseme AcOH 7 wt.% 1,3-propanesulfone 0.5 wt.% Optimum value, solvent: AcOH Optimum value Solvent: propanesulfone AIBN 4.88 x 10" 2 M Optimum value Optimum value Solvent: benzene LOOM, MAIB 0.050 M

50 144 144 190 190 190

170 143 143 123 123 140 123 146 123 225

TABLE 3. cont'd Monomer

fep

(1/mol/s)

fct(x..l0-6)

(l/mol/s)

Temp. ( 0 C)

Method

- , 2-acetyloxy-, methyl ester

430

-

60

C

- , 2-benzoyloxy-, ethyl ester - , 2-(benzyloxymethyl)-, methyl ester

990 182

2.9 1.6

60 60

C C

- , 2-[2,2-bis(carbomethoxy) ethyl], methyl ester

4.0

0.038

60

C

- , 2-butoxy-, methyl ester

298 184

8 -

60 60

C C

- , 2-butyroxymethyl-, methyl ester

360

1.4

60

C

19

0.51

60

C

8.6 1.6 300

21 1.8 1.1

60 60 60

C C C

11

0.08

50

C

0.57

0.11

60

C

0.76

1.4

60

C

- , 3-methyl, dimethyladamantyl ester

0.41 0.71

0.081 1.1

60 60

C C

- , 3-methyl, terf-butyl ester

0.90 LO

2.3 4.7

60 60

C C

- , 2-naphthoyloxymethyl-, ethyl ester

320

0.37

60

C

- , 2-pivaroxymethyl-, methyl ester

230

0.59

60

C

- , trans-2-vinyl-, methyl ester

125

-

60

C

3000-5000 127 52 51 20000 24

12.2 5 1.8

OD 25 25 25 40 50

B4 B4 B4 D

1960 15400 28000 1910 382 ±230 3300 ± 300 3200 ±400 3000 ± 600 (6.5 ± 1.3) x 103 28.2

782 2700 3700 290 47.6 ± 2 2 1200 ± 170 300 ± 5 0 240 ± 70 4700± 1300 0.20

60 25 25 25 25 50 50 50 50 60

Al Al Al Al Al Al Al Al Al C

273 273 8267

17.9 11.9 2200

30 30 30

Al Al Al

- , 2-(2-carbomethoxy)- ethyl-, methyl ester - , 2-ethyl-, methyl ester - , 2-ethyl-, cyclohexyl ester - , 2-isobutyroxymethyl-, methyl ester -,-2-(methoxycarbonylmethyl)-, phenetyl ester - , 3-methyl, adamantyl ester

Acrylonitrile

Ar-Acryloyl-2,2-dimethyl5 (R)-phenyl-l,3-dioxazoline 7V-Acryloylpiperidine N-Acryloylpyrrolidine

23

Remarks Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene 1.56M Solvent: benzene 2.0M, AIBN 5 ^ x IQ^ 3 M Bulk AVN 0.05 M, Ic p and kt also given by other temp. Solvent: benzene 2 M Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene LOOM, MAIB 0.050 M Bulk MAIB 0.05 M, kp and kt also given by other temp. Bulk AIBN 0.10M Bulk AIBN 0.10M Solvent: benzene LOOM, MAIB 0.050 M Solvent: benzene 2.22 M, kp and kt also given by other temp. and [M] Bulk 4.8 M MAIB 0.05 M Solvent: benzene 2.4 M, MAIB 0.05 M, kp also given by other [M] Bulk 4.0 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Bulk 5.9 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene LOOM, MAIB 0.01 M Solvent: benzene LOOM, MAIB 0.005 M Solvent: benzene LOM, AIBN 0.25 M

Solvent: DMF

Refs. 224

172 206 228

176 224

225 229 230 230 225 157

232 232

232 232 232 232 226 225 227 42 49 63 75 42 35

Primary radical termination in a precipitating medium Solvent: DMF 43 Solvent: water 54 Solvent: water 55 Solvent: DMSO 70 Solvent: DMF 68 Solvent: DMF 3.8 M 88 Solvent: DMSO 3.8 M 88 Solvent: Ethylene carbonate 3.8 M 88 Solvent: Mg (C1O4)2 • 12H2O 3.04M 88 Solvent: benzene 1.08 M, 231 MAIB 0.05 M, kp and kt also given by other temp. 145 Optimum value 123 Optimum value 123



kp (1/mol/s)

ifetCxlO"6) (1/mol/s)

Temp. (0C)

Method

JVW'-Dimethylacrylamide

11000 27200 29198 15 x 10 3 2330 ±230

38 3540 4080 0.540 ±0.053

50 30 30 25 30

Al Al Al Fl A4

2760 ±342

0.452 ±0.056

30

9.9 x 10 3

-

25

Fl

kp (1/mol/s)

kt (x 10 ~6) (1/mol/s)

Temp. (0C)

Method

79.6 ±5.6 1.1 x 10 3 ~21 26

16.5 ± 1 . 4 ~27 21

25 25 30 25

Al Fl Al

670

2.1

23

Al

1950 1410 110 895 1250 510

2.25 41.9 80 40 41.9 2.87

30 32.5 32.5 30 20

Al Al C C Al Al

- , bornyl ester

580

3.3

60

C

- , n-butyl ester

369 573 360 lnfcp = 6 . 1 3 + 6.33 x 10 ~9 p lnfcp = 15.8-2751/7

10.2 18.0 10

30 30 30 30 12-93 70 30

Al Al Al F2 F2 B5 B5

10-90

Fl Fl A3 Al

3-Dimethyl-(acryloyloxyethyl)ammonium propane sulfonate

N-Methylacrylamide

Remarks

Optimum value Solvent: water, pH 1.4 Solvent: formamide: 1,4-dioxane (3:1 (v/v)) Solvent: formamide: 1,4-dioxane (3:1 (v/v)), NaCl 0.1 M Solvent: water, pH 1.9

Refs. 74 121 123 197 192 192 197

TABLE 4. METHACRYLIC DERIVATIVES Monomer Methacrylamide Methacrylonitrile £p

Remarks Solvent: water Solvent: water, pH 1

Refs. 69 197 26 39

106.43±0.26

=

xexp[(-29700±1500)//?n Methacrylic acid

- , benzyl ester

- , terf-butyl ester

2.6 In [(kt\p]/(\M + 0.0lp)] = InJt1[I] - 0.73/7 ln*p = (14.41 ±0.09) - (2472±29)/T jfcp = 3.44 x 10 6 exp(- 23300/RT) 1576 9.74 350 14 £p

=

1O7.4±o.4

30 25 9

_66

Solvent: water, pH 8.0 (with 0.22MNaOH) pH=13.6

kp and kt also given as a function of viscosity Solvent: benzene 1.0 M, AIBN 0.05 M Pressure: 5.0 x 10 7 Pa

Pressure 1.0 x 10 8 Pa 77=1.92cp kt \p]\ kt for pressure p (bar), kt[l] = 13.4 x 10 6

99 99 101 153 153 87 103 193 27 106 109 216 216 212 122 219 169 225 52 203

F 1

xexp[-(27.7±2.5)x IO3/RT] - , trans-4-tert-buty\cyclohexyl ester

- , cetyl ester - , p-Ip-(cetyloxy)benzoyloxy]phenyl ester - , 2-chloroethyl ester - , 2-cyclohexylethyl ester - , cyclohexyl ester - , 2-decahydronaphthyl ester

550

1.9

60

C

510 570 ± 1 0 300 ± 9 0 300

1.9 0.5-2.3 0.16 ±0.04 0.25

60 60 30 50

C C Al Al

170 254 1190

0.30 6.71 32.8

50 30 30

Al Al Al

510

5.4

60

C

570

3.1

60

C

Solvent: benzene LOM, AIBN 0.05 M, trans 100% trans 28.9% Solvent: benzene Solvent: dioxane 0.2 M

Solvent: toluene 0.2M

Solvent: benzene LOM, AIBN 0.05 M Solvent: benzene LOM, AIBN 0.05 M

194 194 210 109 97

97 87 87 193 193

TABLE 4. cont'd Monomer - , 2,6-dimethylphenyl ester - , dodecyl ester -,ethyl ester

- , hexadecyl ester - , isobornyl ester - , isobutyl ester - , isopropyl ester - , lauryl ester

- , 2-methoxyethyl ester - , methyl ester

kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

68

2.1

30

Al

72 126

2.4 0.6 7.35 10

30 70 30 70

Al B5 Al B5 Fl

0.16 3.5

10-90 70 60

Fl B5 C

10-90 30 30

Fl Al Al Fl

219 87 109 169

30 23.6

Al Al Al

87 9 7

32.5 40 50 -30 20

C Bl E Bl Al

* p = 1.50 XlO 6 x exp(- 20460/RT) ln* p = (15.11±0.17)-(2753±55)/r 390

lnfcp = (14.72±0.13)-(2590±42)/7 121 4.52 460 ±140 0.6 ±0.2 kp = 2.93 x l O 5 x exp(- 16190/RT) 249 9.30 310 ± 2 0 66 ± 4 fcp = 5 . 1 3 x l 0 6 kt = 1.36 x l O 3 x exp(- 26400/RT) x exp(- 11900/flT) 187 72.1 404 17.6 410 24 13.2 0.488 390 517 527 28 260 270 280 285 310 330 340 240 335 270 330 250 240 280 320 390 ± 4 0 410 ± 40 410 ± 4 0 180±50

37 23 4.4 21 21 19.5 17.5 17 17 17 11.5 9 22 16 29 25 14 28 42 ± 4 29 ± 3 26 ± 3 20 ± 6

10 10 10 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20

Bl Bl Bl Al Al Al Al Al Al B5 B5 B5 B5 B5 B5 B5 B5 B5 Al Al Al E

500 ±250 41.6 62 200 128 364

63 ± 3 2 2.69 8.44 41.8

20 0 5 20 22 22.5

B6 B5 D B6 Bl B4

512.6 410

46.6 42.7

25 25

Al Al

248 141 106 140

22.7 11.6 5.7 -

30 30 32 40

Al A B4 D

Remarks

Refs. 120

Optimum value r? = 3.96cp

123 212 87 212 169

7^ = 0.91 cp

rj = 7.52cp Solvent: benzene 1.0 M, AIBN 0.05 M

Solvent: ethyl acetate Using results of Ref. 7 Solvent: ethyl acetate kp also given as a function of temp. and of viscosity for other solvents Solvent: methanol Solvent: pyridine Solvent: DMF Solvent: benzene 4.69 M Solvent: fluorobenzene 4.69 M Solvent: chlorobenzene 4.69 M Solvent: anisole 4.69 M Solvent: bromobenzene 4.69M Solvent: benzonitrile 4.69 M Solvent: methyl benzoate 4.69 M Solvent: methylphenyl acetate 4.69 M Solvent: dimethyl phthalate 4.69 M Solvent: dimethyl carbonate 4.69 M Solvent: diethyl oxalate 4.69 M Solvent: methyl formate 4.69 M Solvent: methyl propionate 4.69 M Solvent: diethyl succinate 4.69 M Solvent: acetonitrile 4.69 M Solvent: methanol 50% by vol. Solvent: n-octane 5% by vol. Solvent: «-nonane 20% by vol. DP = (2-8) x 10 3 using results of Ref. 86 DP = ( 3 - 5 ) x l 0 4 Assuming biradical initiation Jfcp found as a linear function of Mw Rate of initiation; 1.20 x 10 " 8 (moles/1/s) kp and kt also given as a function of viscosity for other solvents

219 212 193

153 51 62 72 92 94 94 94 85 85 85 85 85 85 90 90 90 90 90 90 90 90 90 104 104 104 96 96 11 65 91 29 60 30 93 14 87 58 65



A:p (1/mol/s)

M x l O ~ 6 ) (1/mol/s)

Temp. (0C)

Method

0.224 573

2.0

45 60

D E

573

11.9

60

E

995 ± 83 506 ±48 450 ± 3 3 456±29 448 ±47 498 ± 39 614±43 427 ±38 290 1020 530 550

43.6 ± 4.9 35.6 ±3.9 42.0 ±3.0 43.8±2.0 47.2 ±6.6 42.9 ± 4.7 39.9±3.3 30.9 ±3.7 21 292 55 68

80 30

kp= 4.92 XlO 5 x exp(- U210/RT) 315

kt = 9S x exp(- 2930/RT) 33.9

15-30

A2

25

A2

336 ± 9 0 441 fcp = 2 . 5 x l 0 6 x exp[(- 23000 ± 2500)/RT] kp=k® (0.33 < Wp < 0.84) = ££exp[-29.8(Wp-0.84)] (0.84 < w p < 0.99)

28 ± 12 19.7 720

25 30 25-60

Al Al C

50

C

w p (weight fraction of polymer)

150

At high conversions ( ~ 65%) Special evaluation from steady-state and Mn Solvent: toluene

148 134

30 60

Al Al Al Al Al Al Al Al Al Al Al

Remarks

Refs.

Termination by combinat. using results of Refs. 7 and 31 Termination by disprop. using results of Refs. 7 and 31 Solvent: benzene 4.7 M Solvent: anisole 2.0M Solvent: benzene 2.0M Solvent: C 6 D 6 2.0M Solvent: fluorobenzene 2.0M Solvent: chlorobenzene 2.0 M Solvent: benzonitrile 2.0M Solvent: benzene 1.0 M Addition of 1 x 10 " 3 mol pyridine Addition of 1 x 10" 3 mol acetone Addition of 1 x 10 " 3 mol triethanolamine P n = IO4 kp and kt also given as a function of P n Pressure 5.0 x 106 Pa Pressure 5.0 x 10 7 Pa

67 33 33 111 133 133 133 133 133 133 133 118 118 118 118 114 110 127 105 45

(*J= 790 ±300) 130 705.6

20.7 ±1.0 25

0 60

Al

170 306 292

-

0.2 25 25

F3 Fl Fl

60 20-90

C Fl

30

B5

670 ± 3 0 22 InATp = 14.69-2670/7+ 0.201/7x(1.0x 1 0 " 5 P - I ) \nkt[p] = InA:t[l] -0.57/7 26.6

1.4

5

BlO

5.8

0.017

5

BlO

kt(m,n) = 1.22 x W2(n x m)~ 0075

25

A3

21

70

B5

0.034

50

D

0.16

50

D

- 1 to - 70 60

Fl C

- 8 30

F3 Fl

fcp = 106 694 exp(- 23940/RT) lnJfcp (VmoVmin) = ln*p,-(3.86 [AIBME]0 + 0.8) x (l-(f>m)- 1.6 (l-cj)m)60

131 680- 820

-

690-810

-

Fl

222 196

Solvent: ethanol (50%) 4.67 M, kv also given by other [M] and solvents 175 207 kt\p\\ kt for pressure/? (bar), fct[l] = 15.4x 106 Scavenger DPPH, solvent: DMF, blank polymn. Scavenger DPPH, solvent: DMF, template polymn., template; it-MMA n: n-mer; m: m-mer, coupling with rt-mer and m-mer 77 = 0.53 cP No addition of chain-transfer agent, Time 7.5-20.5 min. Addition of 2% CBr4, Time 7.5-20.5 min. AIBME (dimethyl 2,2'azodiisobutyrate) 0.0434M, m; monomer volume fraction £pX) = 700(l/mol/min) Benzoin 7 x 10 " 4 M Solvent: toluene, pressure 1.0 x 108 Pa, k p also given by other pressures Solvent/2-butanone, pressure 1.OxIO 8 Pa

122 115 115

147 212 149 149 217 158

199 208

208


kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

313±8.1 794.0 815.0 957.0

39±4 62.4 51.6 38.2 25(±3)

25 60

Fl B5

60

C

21 ± 2 45 50

60 25 40

C Al

191 160 160

-

25 50

Fl Fl C

198 220 184

510 ±100 299 431 )tp = 2.39 x 106 x exp(- 22000/#D 359 12

135 292 200 135 ± 5 0 170

-, octyl ester

35 2960 *p = 1.9068 x 106 xexp(-21181.07//?D kp = 1.2169 x 106 x exp(- 25203.59//?D kp = 3.0598 x 107 x exp(-28008.18/RT) 35 1710 240 ± 8 0

0 25 28 0 50

29.1

50 30

Al Fl Bl Al C

Values from Chem. Abstr.

159 164 83 165 155

30% MMA in benzyl alcohol

227

Fl

30% MMA in NMP

227

p.s. 500 nm Pressure 5.0 x 10 7 Pa

155 113 109 122

30 30 30 60

Al Al Al Al Al Al Al Al Al Al C

26 1470 ±170

0.301 0.499 ±0.058

32.5 30

C A4

2760 ±342

0.452 ±0.056

30

185

0.034

20

B8

230

0.053

20

B8

kp (1/mol/s)

£ t ( x l 0 ~ 6 ) (1/mol/s)

Temp. (0C)

Method

1.7 3.9

2.5 x 10" 3 3.4xl0~3

60 60

C C

Polyhydroxytetramethylene-a, co-methacrylate of MW = 700

particle size 260 nm, kp also given by other particle sizes kp; average value

Fl

411 230 ± 1 5 176±8 180±9 223 ±11 235 ± 8 273 ± 8 228 149 467 590

30 30

Emulsion polymn.,

161 204 204 204 166

A3 Fl

50 30 30

Solvent: benzene 3 M Solvent: chlorobenzene 3 M Solvent: benzonitrile 3 M

Refs.

Emulsion polymn., n-butyl aery late: MMA: methacrylic acid (8:91:1), particle size (p.s.) 50 nm, kp also given by other temp, and particle sizes p.s. 500 nm 155 225 227

62.6 2.6 ±0.9 ln[(fct[p]/(1.00- 0.19)] = \nkt[l]-l.01p 11.9 2.02 ±0.22 2.06±0.21 2.16±0.19 2.26 ± 0.22 1.72 ±0.11 1.96 ±0.12 1.88 0.813 45.1 2.6

-, phenyl ester

- , 2-phenylethyl ester - , 3-phenylpropyl ester - , rc-propyl ester - , 3-tetracyclo-[4.4.02'5.l7'10]dodecyl ester -, triphenylmethyl ester 3-Dimethyl-(methacryloyloxy-ethyl) ammonium propane sulfonate

25.6 -

Remarks

Al Al B5

kt[p]\ kt for pressure p (bar), ikt[l] =40.0 x 106 Solvent: Solvent: Solvent: Solvent: Solvent: Solvent:

anisole 2.00M benzene 2.00M fluorobenzene 2.00M chlorobenzene 2.00M bromobenzene 2.00M benzonitrile 2.00M

Solvent: benzene 1.0M, AIBN 0.05 M

87 116 116 116 116 116 116 87 87 28 193

153 Solvent: formamide: 192 1,4-dioxane (3 :1 (v/v)) Solvent: formamide: 192 1,4-dioxane (3 : 1 (v/v)), NaCl 0.1 M Calcd. from nonstationary 125 state kinetics Calcd. from stationary state kinetics 125

TABLE 5. ITACONIC DERIVATIVES Monomer Itaconic acid - , bis (4-terf-butyl-cyclohexyl) ester - , bis (cyclohexyl-methyl) ester

Remarks

Solvent: benzene 0.5M Solvent: benzene 1.5M, MAIB 0.02 M

Refs.

213 182


TABLE 5. cont'd kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

- , bis (3,5-dimethyl-l-adamantyl) ester - , bis (2-ethylhexyl) ester

0.92 6.8 3.4 2.0 2.1 2.2 2.1 2.1 1.4 3.0

0.32 x 10~3 0.001

60 50 50 50 50 50 50 50 50 50

C C C C C C C C C C

- , diadamantyl ester

0.56

0.30 x 10~3

60

C

- , di-n-butyl ester

3.5

1.59 x l O " 2

60

C

13

0.11

50

C

11 6.8 9.4 6.7 3.4 3.2

0.13 0.07 0.11 0.083 0.068 0.13 1.0 x l O " 3

50 50 50 50 50 50 50

C

5.3

8.5 x l O " 2

50

C

5.9

0.053

50

C

- , di-sec-butyl ester

0.6

4.0 x 10 ~3

60

C

- , di-terf-butyl ester

0.2

5.6 x 10~3

60

C

- , dicyclohexyl ester

2.3

1.4xlO" 3

60

C

- , diethyl ester

7.7

0.24

50

C

3.7

6.41 x l 0 ~ 2

60

C

- , diisobutyl ester

2.7

1.56 x 10~2

60

C

- , diisopropyl ester

1.1

5.0xl0~~ 3

60

C

- , dimethyl ester

5.2

0.36

60

C

10

0.59

50

C

- , a-ethyl-P-hexarluoropropyl ester

5.0

0.28

60

C

- , a-methyl-P-isopropyl ester - , a-methyl-P-tert-butyl ester - , a-isopropyl-P-methyl ester - , a-fm-butyl-P-methyl ester AT(2,6-dimethylphenyl)itaconimide

3.4 4.2 1.9 0.91 26

0.06 0.051 0.07 0.056 0.082

60 60 60 60 50

C C C C C

15

0.29

60

C

Monomer

Methyl N-phenyl-itaconamate

Remarks Solvent: benzene 1.5 M Solvent: hexane 1.03 M Solvent: cyclohexane 1.03 M Solvent: toluene 1.03 M Solvent: benzene 1.03 M Solvent: chlorobenzene 1.03 M Solvent: ethyl acetate 1.03 M Solvent: THF 1.03 M Solvent: acetone 1.03 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, kp and kt also given by other [M] Solvent: benzene 1.5M, MAIB 0.02 M Solvent: cyclohexane 1.33 M, MAIB 5.00 x 10~2 M, kp and kt also given by other temp. Solvent: n-hexane 1.33 M Solvent: chlorobenzene 1.33 M Solvent: methyl benzoate 1.33 M Solvent: benzene 1.33 M Solvent: acetone 1.33 M Solvent: acetonitrile 1.33 M Solvent: benzene 0.794M, AIBN 0.05 M kt also given by other [M] Solvent: benzene 0.794M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M, kp and kt also given by other [M] and temp.

Solvent: THF 0.44 M, AIBN 0.05 M, J^p andfct also given by other [M] Solvent: DMF 1.4 M, AIBN 0.05 M, jfcp andfct also given by other [M] and temp.

Refs. 213 185 185 185 185 185 185 185 185 177 213 182 162

162 162 162 162 162 162 154

154 177 182 182 182 177 182 182 182 195 177 233

195 195 195 195 234

235

TABLE 6. FUMARIC DERIVATIVES Monomer Fumaric acid - , bis (2-methoxy-ethyl) ester - , bis (2-chloro-ethyl) ester - , tert-butyl methyl ester - , tert-buty\ isopropyl ester

- , di-terf-butyl ester - , dicyclohexyl ester - , diethyl ester

- , diisopropyl ester

- , dimethyl ester - , dineopentyl ester Ethyl o-formylphenyl fumarate

TABLE 7.

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

0.19 0.26 0.23 0.51 0.35 0.39 0.61 0.60 0.21 0.015

330 x 10~6 320 x 10~6 150xl0~6 26xlO"6

60 60 60 60 60

C C C C C

1.75 x l O - 5 30 x 10~6 40 x 10~6 (510-560) x 10" 6 1.64 x l O - 4

60 60 60 30

C C C Al

0.029 ±0.003

8 xlO-6

30

BlO

0.46 0.31 ±0.07

(80-100) x 10~6 0.84 x l O - 6

60 30

C BlO

0.058 0.028 4.0

430 x 10~6 44xlO~6 1.4

60 60 60

C C C

k p (1/mol/s)

M x I O " 6 ) (1/mol/s)

Temp. (0C)

Method

7400

7.4xlO"5

40

22.7 570 kp = 3.3 x 106 x exp(- 15000/RT) 11000 3130 8.6 kp = 10 9 x exp(- 4540/7)

92 385 kt = 1.3 x 106 x exp(- 4200/RT) 2100 2300 0.175 kt = 106 x exp(- 2670/7)

-30 20

kp (1/mol/s) 4600 795 556-586 670-770 700 559 1100 1000 895 kp = 2.43 x l O 8 x exp(- 30600/RT) 9500-19000 (15-26) x 102

Remarks

Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AIBN MAIB Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AVN (2,2'-azobis-2,4dimethylvaleronitrile), ACN (l.l'-azobiscyclo-hexane1 -carbonitrile) ACN, scavenger TPV (1,3,5-triphenylverdazyl), sovent: benzene Solvent: benzene l.OM ACN, scavenger TPV, solvent: benzene Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene 1.16 M, MAIB 0.100 M, kp and ^ t also given by other [M]

Refs.

211 211 211 211 181 181 211 211 211 173

179

211 180 211 211 236

VINYL HALIDES

Monomer Tetrafluoroethylene

Vinyl bromide Vinyl chloride

Vinylidene chloride

TABLE 8.

kp (1/mol/s)

Remarks Large active chain end concentration measured by addition of inhibitor in aqueous solution polymn.

Al

Refs. 81

Al

80 44 32

25 25 25 22-75

Al Al Al Al

56 77 18 117

M x I O " 6 ) (1/mol/s)

Temp. (0C)

Method

220 46 2860-3040 2500-3100 2600 51.8 80 59 24 kt =4.16 x 105 x exp(- 21900/RT) 380-760 25

25 15 15.9 15.9 15.9 20 25 25 25

B5 Bl Al Al Al B4 Al Al B4 Al

60 50

E Al

Quoted in Ref. 80

Solvent: N-methylpyrrolidone 2.0M

VINYL ESTERS

Monomer Vinyl acetate

Remarks

Solvent: «-hexane

At 4% conversion

Using results of Refs. 8 and 15

Refs. 13 47 1 3 4 37 2 15 36 8 64 128



Vinyl benzoate

TABLE 9.

kv (1/mol/s)

£ t (xIO~ 6 ) (1/mol/s)

Temp. (0C)

Method

Remarks

117zb 12 113±10 48 ± 5 97 ± 10 61 ± 9 37 ± 5 8± 1 637 ± 101 78 #

319±61 351±54 239 ± 4 5 311 d= 59 266 ± 7 5 412 ± 104 258 ± 76 94.2 ± 23.7 -

30

Al Al Al Al Al Al Al Al

32.5 32.5 32.5 32.5 30 15-60

Al C C C Al C

Solvent: benzene 2.00M Solvent: C 6 D 6 2.00M Solvent: anisole 2.00M Solvent: fluorobenzene 2.00M Solvent: chlorobenzene 2.00M Solvent: ethyl benzoate 2.00M Solvent: benzonitrile 2.00M Solvent: ethyl acetate 2.00M Solvent: ethyl acetate: ethyl benzoate (1:1 (v/v)) Solvent: benzene Solvent: benzene 5.41 M Solvent: ethyl acetate 5.43 M

120 310 530 630 1900 280 1400 4435 64.4 £ p = 2.0 XlO 6 27.5 x exp[(- 19000 ± 2900)/RT] Jcp = 2 . 1 x l O 8 x exp(- 27820//?7) ln[(*t|>]/(1.00-0.07/?)] = lnJfct[l]-0.50p 106 ± 1 4 253 ± 6 3 185 ± 8 402 ± 3 2 245 ± 13 522 ± 48 168 ± 18 383 ± 76 69 ± 13 257 ± 72 33 ± 3 299 ± 4 4 267±33 451 ± 6 5

Monovinyl ether of ethylene glycol Monovinyl ether of diethylene glycol

Monomer Styrene

Pressure 5.0 x 10 7 Pa

Fl 30

B5

30

Al Al Al Al Al Al Al

130 130 130 130 130 130 130 130 130 153 153 153 153 112 45 209

kt\p]; kt for pressure p (bar) £ t [l] = 52.0x 106 Solvent: anisole 1.01 M Solvent: benzene 1.01 M Solvent: fluorobenzene 1.01 M Solvent: chlorobenzene 1.01 M Solvent: ethyl benzoate 1.01 M Solvent: benzonitrile 1.01 M Solvent: ethyl acetate 1.01 M

122 116 116 116 116 116 116 116

VINYL ETHERS

Monomer

TABLE 10.

Refs.

k p (1/mol/s)

kt (x 10 6 ) (1/mol/s)

5.0 ±1.0 3.0 ± 0.8

1.5 ±0.3 1.4 ± 0.3

Temp. ( C )

Method

50 50

Al Al

Refs. 136 136

STYRENE DERIVATIVES k p (1/mol/s)

kt (x 10 ~6) (1/mol/s)

Temp. (0C)

Method

40 ± 20 24

80 ± 40 14

15 20

Al Al

51.9 108 106 102 390 209 18.7 39.5 £p = 2 . 1 6 x l 0 7 x exp(- 32500/RT) 22

10.5 32.5 108 -

30 30 30 40 50 50 25 25

Al Al Al D D E B5 Bl Al

5

D

40 50 50

D D D

139 223 206

115 2.79 5.96 2£t = 2 . 5 9 x l 0 3 x exp(- 9920/RT) -

Remarks Dimension of kp and kt: kg/mol/s From copolymn. data with sulfur dioxide

Quoted in Ref. 86 Using results of Ref. 20

Catalyst: cumene hydroperoxidetriethylenetetramine Catalyst: persulfate

Refs. 46 25 16 38 78 59 5 61 6 17 20 24 24 40 67


kp (1/mol/s)

M x l O " 6 ) (l/mol/s)

Temp. (0C)

* p = 2.24 XlO 14 xexp(-73510//?r) 50 80 64 370 915 25 ± 3 9 ± 1.5 35 ± 7 19 ± 4 35 ± 5 19 ± 3 29 ± 7 15 ± 4 23±8 11 ± 2 27 ± 4 31 ± 0.4 *p = 1.09 XlO 7 * t = 1.703 x l O 3 x exp(- 31380/K7) x exp(- 9489/RT) 66.6 22.4 66.5 £ p = 2.4 XlO 8 x exp(- 38000 ± 11OO)/RT 187.1 29.4

84

-,p-bromo-,/?-chloro-,/7-cyano-,p-fluoro-,/7-methoxy-

25 60

D Al

25 25 25 25 25 25 15-30

Al Al Al Al Al Al A2

65 118 Addition of 1 x 10 " 3 mol pyridine 118 Solvent: dodecane 40% by vol 104 100 Solvent: bromobenzene 20% by vol 100 Solvent: diethyl malonate 20% by vol 100 Solvent: diethyl phthalate 20% by vol 100 Solvent: dinonyl phthalate 60% by vol 100 DP = 2500 114

30 25 50-90

Al C

60 F2 Fl

25 25 40 70

Fl Fl Fl C

16.6-17.0

100

C

190 -

50 25

C Gl

kt (m,/i) = 1.97 x 102 (n x m) " ° 1 2

30

A3

5 30-90

C Fl F2

25 25 60

Fl Fl B5

91.2 25 30 25 25 28

Gl Al Fl Fl Fl Bl Fl

180 ± 1 0 £ p = 1.99xl0 7 exp(-30780//?D In kp = 17.14-1.873 x 10" 9 p - 3748/r + 2.02 x 10 " 6 p/T 77 ±4.1 79 ±5.1 187.0 201.0 167.0 641 ±48 89 107 92 78 23 In kp = 16.09-28950//?r (overall) = 16.47-3003/KT (chain length > 4) * p = 107-1±0-5 xexp[-(29±3)xlO3/*r] fcp = 1.8861 x 107 x exp(- 30737.52//?r) kp = 4.2060 x l O 8 x exp(- 37468.93/RT) kp = 4.2458 x 108 xexp(-39014.90//?7) 186 150 219 112 2.92 71

-

78 ± 1 2 96 ± 9 63.2 51.1 37.9 132 0.6

46 77 35 127 1.06 33

Refs. 73

-

256 107

Remarks

Bl

kp = 107-630 x exp(- 32510/RT) - 1 2 - 93 25

76 70 380 ±110 480 ± 1 0

Method

30 30 30 30 0 30

Pressure 5.0 x 10 7 Pa

102 98 98

Special evaluation from steady-state kinetics and Mn

134

215 kp also given by other [M] and 196 solvents Solvent/ethanol(25%)6.52M 196 Solvent: methanol (25%) 6.52 M 196 Pressure 2.0 x 108 Pa 186 Over a range of degree of polymn. 188 of the polymer radical from 40 to 410 Conversion 0-20% 174 TBP (terf-butyl peroxide) kp and kt also given by other temp. 189 Laser-flash-initiated polymn. by 156 benzoin n: n-mer, m: m-mer, 147 coupling with n-mer and m-mer 223 169 Pressure 1 x 10 5 -2.8 x 108 Pa 214

Solvent: Solvent: Solvent: Solvent: Solvent:

toluene 50% (v/v) benzene 3 M chlorobenzene 3 M benzonitrile 3 M toluene

kp also given by other temp.

Solvent: benzene 4.33 M

161 161 204 204 204 178 160 198 220 164 83 200

Bl

131

Fl

227

Fl

30% styrene in benzylalcohol

227

Fl

30% styrene in NMP

227

Al Al Al Al B5 Al

Solvent: dimethylacetamide

78 78 78 78 12 78



kv (l/mol/s) kp = 1.67 x 1 0 n x exp(- 58240/RT) 84 kp = 2.27 XlO 7 x exp(- 32060/RT) kp = 10 5 7 7 x exp(- 23.0/RT) &p = 3 . 6 3 x l 0 7 x exp(- 31500/RT)

- , o-methyl- , p-methyl-

Styrene-d8

TABLE 11.

A: t (xl0~ 6 ) (l/mol/s)

66

Temp. (0C)

Method Bl

73

30

Al Bl

78 73

24-55

Fl

£t = 2 . 5 5 x l 0 4 x exp(- 14200/7?7)

Solvent: toluene 2M

Al

kp (l/mol/s)

Ict (x 10~ 6 ) (l/mol/s)

Temp. (0C)

Method

6.0 186 96.6 12 47 122

0.306 33 8.9 3 3.5 66

10 25 25 25 25 20

Al Al B4 B5 B4 Bl

209 17.3 953 22000 ± 4000

43 1.2 65 600 db 200

20 20 20 25

Bl Bl B4 Al

k p (l/mol/s)

M x 10 ~6) (l/mol/s)

Temp. (0C)

Method

-

(7-10) x 10 ~3

—190

B4

kp (l/mol/s)

kt(x 10~ 6 ) (l/mol/s)

Temp. (0C)

Method

Maleimide - , N-tert-amyl- , N-tert-butyl-

69 100

0.048a,0.017b 0.021 a ,0.023 b

60 60

C C

-, -, -, -,

120 23 120 49

0.20a 0.027 a ,0.015 b 0.15 a ,0.23 b 0.054

60 60 60 50

C C C C

55

0.069

W-Vinylcarbazole 2-Vinylpyridine 4-Vinylpyridine 5-Vinylpyridine - , 2-methyl-

Af-Vinylpyrrolidone

226 168

Remarks

Refs. 80 76 76 34 75 94

Solvent: methanol 1.95 M, kp also given as a function of [M] Solvent: 50% (molar) aqueous methanol 94 Solvent: acetic acid 94 82 Solvent: water 132

ALDEHYDES

Monomer Formaldehyde

TABLE 13.

Refs.

VINYLHETEROAROMATICS

Monomer

TABLE 12.

Remarks

Remarks Solid monomer, gamma irradiation

Refs. 95

OTHERS

Monomer

A^m-butyl-dimethylsilylN-tert-octylN-trimethylsilylN-cyclohexyl-

Remarks

Solvent: benzene 1M (a) Determined from steady-state equation kt = (2kdf[l])/[P']2, AIBN 0.005 M; (b) determined from second order plot of the decay curve of the radical concentration, ATMP (2,2 '-azobis-(2,4,4-trimethylpentane)) 0.02 M, for tert-BMl, ATMP 0.01 M

Solvent: benzene 0.559 M, AIBN 1.39 x 10" 2 M Solvent: benzene 0.698 M, AIBN 1.00 x 10~2 M, kp and kt also given by other [M] and [I]

Refs.

205 205

205 205 205 163 163

TABLE 13. cont'd A: p (1/mol/s)

Jt t (xl0" 6 ) (1/mol/s)

Temp. (0C)

- , AH2,6-diethylphenyl-

2.0

0.0078

60

C

- , Af-(2,6-dimethylphenyl)-

14

0.034

60

C

- , AH4-ethylphenyl)-

1200

3.9

60

C

- , #-(2-methylphenyl)-

190

0.59

60

C

- , Af-(2-carboethoxyphenyl)- , N-dodecyl-

96 54 104 175 80 128 149

0.10 0.12 0.45 1.0 0.40 0.064 0.17

60 50 50 50 50 50 50

C C C C C C C

386 250 235 196

0.55 -

50 50 50 50

C C C C

33

0.10

50

C

400

0.07

50

B9

Monomer

- , iV-octadecylOligotetramethylene glycol dimethacrylic ester (MW 600)

Method

Remarks Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene MAIB 0.005 M Solvent: benzene MAIB 0.01 M Solvent: toluene MAIB 0.01 M Solvent: anisole MAIB 0.01 M Solvent: chlorobenzene MAIB 0.01 M Solvent: bromobenzene MAIB 0.01 M Solvent: methyl benzoate MAIB 0.01 M Solvent: THF, MAIB 0.01 M Solvent: dioxane, MAIB 0.01 M Solvent: ethyl acetate MAIB 0.01 M Solvent: methyl ethyl ketone MAIB 0.01 M Solvent: benzene AIBN 0.20M, kp and k[ also given by other [I]

Refs. 183 183 183 183 237 238 238 238 238 238 238 238 238 238 238 239 124

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T r a n s f e r

C o n s t a n t s

P o l y m e r s ,

C a t a l y s t s

S o l v e n t s S u l f u r

a n d

t o a n d

I n i t i a t o r s ,

A d d i t i v e s ,

C o m p o u n d s

R a d i c a l

M o n o m e r s ,

i n

a n d F r e e

P o l y m e r i z a t i o n

A. Ueda Osaka Municipal Technical Research Institute, Osaka, Japan S. Nagai Plastics Technical Association, Osaka, Japan

A. Introduction B. Tables Table 1. Transfer Constants Table 2. Transfer Constants Table 3. Transfer Constants Initiators Table 4. Transfer Constants Additives Table 5. Transfer Constants Compounds C. Remarks D. References A.

to Monomers to Polymers to Catalysts and

11-97 11-98 II-98 11-103 11-106

to Solvents and 11-110 to Sulfur 11-150 11-157 11-159

INTRODUCTION

The transfer reaction in radical polymerization describes a process in which the polymer radical reacts with another molecule (monomer, polymer, catalyst, solvent, modifier, etc.) forming a dead polymer and new radical. This new radical can continue the kinetic chain:

If it is assumed that (a) all new radicals X# react only by formation of growing polymer radicals; (b) all polymer radicals have equal reactivities independent of their size; (c) all rate constants are independent of solvent; (d) the consumption of monomer by initiation and transfer is negligible compared with propagation; (e) a steady-state concentration of polymer radicals is quickly established (d[P#]/dr = 0). The application of these assumptions to the common reaction scheme results in the following relationship of ideal kinetics (Ref. 145):

P n , p n 0 = number-average degree of polymerization obtained in the presence or absence, respectively, of transfer agent X. [M], [X] = concentration of monomer or transfer agent, respectively.

The dimensionless transfer constant is defined by the ratio

where kv is the rate constant of propagation. Based on the tables in the third edition, by K. C. Berger and G. Brandrup.

The left-hand side of this equation is obtained by measuring the number average molecular weight of polymer at different concentrations of the transfer agent X, all other variables being kept constant. In many cases the degree of polymerization was determined by measurement of viscosity (Remark R). It should be noted that the ratio of

viscosimetric to number average molecular weight shows a considerable dependence on the molecular weight distribution. The first term P n 0 of the right-hand side of this equation is the number average molecular weight measured in the absence of transfer agent X. This is limited to cases where the transfer agent is a modifier. In all other cases, Pno is calculated by combination of several kinetic expressions and used with its numerical value:

This decrease of the transfer agent concentration with increasing monomer conversion is important in practice because very reactive transfer agents are used up preferentially, giving a broad molecular weight distribution if they cannot be replenished. In analogy to quickly decomposing initiators with their criterion of "half-life", one can define, in addition to the transfer constant Cx, a "half-conversion" U\/2 as that monomer conversion where the transfer agent is half consumed:

Initiation Termination Propagation Number-average molecular weight where ku fct,d, and k^c are the rate constants of termination, termination by disproportionation, and termination by combination, respectively.

The second term of the right-hand side of the above equation is given by the following expression:

where Cp is the constant of chain transfer with added polymer before starting polymerization. The transfer constant of very reactive molecules can be determined from the rate of disappearance of both transfer agent and monomer:

The following table demonstrates (with some examples for a calibration curve) that the "half-conversion" IZ1^2 decreases with increasing transfer constant Cx: The "Half-Conversion" of Transfer Agents Cx

U1/2(%)

Cx

Ul/2(%)

0.1 0.2 0.5 1 2

99.9 96.8 75.0 50.0 29.3

5 10 20 50 100

13.0 6.7 3.4 1.4 0.7

The transfer agent must be replenished at this monomer conversion at the latest, if polymerization is to proceed, still yielding a narrow molecular weight distribution. Numerous examples are known of polymerization systems that possibly do not satisfy basic assumptions: retardation (Remark J), induced decomposition and primary radical termination by peroxide or hydroperoxide initiation (Remarks C and B), diffusion control of termination (Remark X), electron donor/acceptor complexes (Remarks JJ), etc. Corresponding data in this table have to be used with caution.

B. TABLES OF TRANSFER CONSTANTS TABLE 1. TRANSFER CONSTANTS TO MONOMERS Monomer

T( 0 C)

Acetic acid, allyl ester

80

Acrylamide

25

Acrylamide, AT,iV-dimethylAcrylic acid, benzyl ester

50 60 60 50 55 60 60 60

- , butyl ester

C M (xlO 4 ) 170 700 0.12 0.16 0.2 0.2 0.558 0.651 0.6 1.5 0.883 0.905 0.333 1.05

Remarks

D E C2, F13, LL C2, F13, LL E

Cl, H, KK Cl, H, KK

Refs. 29 27 92 74 75 103 560 560 103 272 291 291 561 561

TABLE 1. cont'd Monomer Acetic acid, butyl ester (cont'd) -,ethyl ester

T( 0 C) 60 65 50 60 65 70

- , - 2 ethylhexyl ester - , methyl ester

70 80 50 55 60 65

70

75 -, tetrahydrofurfuryl ester -, 2-chloro-, ethyl ester - , thio-, methyl ester Acrylonitrile

40 60 60 20 25 30 40 50 60

Allyl bromide Ammonium chloride, A^-diallyl-MJV-diethyl- , Ar,Ar-diallyl-AW-dimethylAnisole, p-\iny\ Anthranilic acid, vinyl ester Benzoic acid, vinyl ester

1,3-Butadiene, 2-chloro- , 1,1,2-trichloro1-Butene 2-Butene, cis- , trans3-Butene-2-one, 3-methyl-

60 60 60 60 60 60 0 60 70 60 80 95 50 25 40 50 60 40 50 60 40 50 60 80

C M (xlO 4 )

Remarks

1.25 0.955 0.193 0.90 0.41 0.579 0.332 0.351 0.789 6.28 3.79 0.80 0.275 0.036 0.325 0.10 0.11 0.11 0.37 0.01 0.072 0.16 0.18 0.405 0.224 0.25 0.25 4.0 3.0 560 0.18 0.105 1.5 0.17 0.050 0.27 8.2 0.26 0.3 0.333 0.57 1.02 30 18 7 0.198 0.74 80 6.0 7.0 2.0 4.0 2.32 16 3.1 5.1 7.3 3.2 4.9 11.2 3.0 5.2 10.8 4.00

Cl, H, KK

F7 C, F17, R C, F17, R C, F17, R C, F17, R C, F17, R F7 C,AA B, AA C, AA C,AA CFlO CAA C, AA CFlO B, AA CAA C AA C, AA CAA C, FlO C AA C, F2 E F8 F18 F17 F16 Cl, H, KK Cl, H, KK Cl, H, KK C, R, HH Cl, F30 Cl, F30

F2 E

C

Refs. 561 291 306 510 512 512 306 306 512 512 512 510 221 221 221 221 123 221 221 322 221 221 221 221 221 123 221 319 342 140 299 284 196 284 410 376 362 95 23 561 561 561 505 538 538 13 53 139 321,393 26 321 213 153 230 334 334 334 334 334 334 334 334 334 84

Remarks page 11-157; References page 11-159

TABLE 1. cont '6 Monomer Butyric acid, vinyl ester Carbamic acid, vinyl-, ethyl ester Carbazole, A^-vinyl-7H-benzo(2)Decanoic acid, vinyl ester Ethylene

T( 0 C) 50 80 60 70 50 60

70

26.7 22.3 0.25 11 45.5 0.4 1.4 4.2 5.0 5.32 1.1 3.5 9.0 0.0 1.6 4.7 11.2 5 3.2 3.2 7.0 6.25 19.4 50 6.4 7.8 8.5 11 13.5 10.8 12.3 12.8 23.8

60

42

83 110

130

- , chloro-

50-70 20 25 30 40 50

60

Glutaramic acid, MA^-diisobutyl-, vinyl ester - , AW-diisopentyl-, vinyl ester

Hexanoic acid, vinyl ester 5-Hexen-3-yn-2-ol, 2-methylIsobutyric acid, vinyl ester Laurie acid, vinyl ester Maleic anyhydride Maleic anhydride/methyl methacrylate Maleimide, A^-(3-dimethylamino-6-methyl-phenyl) Methacrylamide Methacrylic acid, bornyl ester - , butyl ester

-, -, -, -, -, -,

tert-butyl ester o-r-butylphenyl ester /?-?-butylphenyl ester n-dodecyl ester 2,3-epoxypropyl ester ethyl ester

-, -, -, -, -,

0-ethylphenyl ester p-ethylphenyl ester glycidyl ester hexadecyl ester isobornyl ester

C M (xlO 4 )

60 70 80 80 60 80 50 75 60 50 60 60 50 60 70 60 60 60 60 45 60 80 90 60 60 60 70 60

51 51 51 36 5.0 46 45.5 750 100 720 10 x 105 2.85 0.54 120 x 105 0.14 0.35 30.41 2.01 80xl05 0.59 0.248 0.259 0.456 0.442 3.63 1.36 45 x 105 0.14 1.85

Remarks

Refs.

F4 Y

71 200 117 522 71 102 102 102 204 205 102 102 102 259 102 102 102 218 94 315 425 58 463 246 379 379 379 392 58 379 379 379 58

C, FlO

106

C, FlO C, FlO CFlO

107 107 107 200 226 200 71 175 367 542 515 162 233 515 264 9 550 550 515 198 193 193 193 193 550 550 515 138 162

R, F2 W5 W4, W5 W4 D, W D, W W4, W5 W4, W5 W4 C, F21,W5 W4, W5 W4, W5 W4 W3

Y F5 F3 F4 C, F26 Y F3

C F2 JJl

JJl

C C JJl CC CC CC CC C C JJl

TABLE 1. cont'd Monomer Methacrylic acid, isobutyl ester

- , n-nonyl ester - , phenyl ester - , o-tolyl ester - , p-tolyl ester Methacrylonitrile

Methyl methacrylate

J( 0 C) 35 50 60 80 100 60 27 60 60 60 25 60 70 80 0 30

40 50

60

65 70

75

80

Naphthalene, 1-vinyl1,4-Pentadiene, 1,1,2,3,3,4,5,5-octafluoroPhernol, o-vinyl2-Picoline, 5-vinyl1-Propene, 2-chloro-, 2-methylPropionic acid, vinyl ester

90 100 120 50 60 70 110 70 70 80 40 50 60 50

C M (xlO 4 ) 0.189 0.179 0.14 0.165 0.224 0.301 0.382 105 x 105 400 0.61 1.13 1.06 2.08 5.81 8.00 10.05 0.128 0.148 0.117 0.260 0.15 30 x 105 242 x 105 0.10 0.15 0.477 241 x 105 0.85 0.07 0.10 0.103 0.18 240 x 105 0.20 0.17 0.20 0.23 0.265 0.29 0.30 0.45 0.807 1.37 240 x 105 0.27 0.33 0.60 0.70 0.25 0.40 0.10 0.38 0.58 290 310 300 500 130 6.7 1600 2.5 4.4 6.9 3.6 48.9

Remarks DD DD F2 DD DD DD JJl R C C C Z Z Z Z

D JJ2 JJl F2 D JJl

C JJO CFlO

C, F17 D JJl CFlO C CFIl C, F2

WlO

Refs. 193 193 264 264 193 193 193 515 534 550 550 550 125 125 125 125 69 18 69 224 508 525 528 147,327 145 224 528 69 274 34,290,317 316 145 556 123 123 267 145 440 123 123 104 224 459 528 123 123 123 123 145 123 147 145 145 216 216 216 68 186 11 27 334 334 334 158 71

Remarks page II-157; References page II-159

TABLE 1. cont'd Monomer Pyridine, 2-vinyl- , 4-vinyl2-Pyrrolidinone, 1-vinylStearic acid, vinyl ester Styrene

T( 0 C) 15-35 25 20 50 O 25 27 30 45 50

60

67.8 70

75

80 80.3 90

99 100

110 117 132

Styrene, p-boromo-, o-chloro-

50 30 50

C M (xlO 4 ) O 6.7 4.0 69.8 O

Remarks D

BB 0.108 0.279 0.358 0.31 0.2 0.32 0.3 0.35 0.40 0.50 0.6 0.62 0.65 0.78 0.07 0.6 0.6 0.6 0.75 0.79 0.85 0.92 1.1 1.37 20 x 10 5 1.0 O 0.6 0.6 0.8 0.96 1.16 1.35 2.0 O 1.6 5.0 5.00 0.7 0.75 1.00 4.0 0.85 1.25 1.47 1.79 1.5 1.72 1.8 1.83 2.80 1.40 2.45 3.0 3.4 5.33 23 0.25 0.25 0.28

A BB BB H F2 C, H C A, K B, C, H A C C BB A A, F

C JJl CFlO BB B, H A A C, F2 C,F10 C C, F2 CFIl BB BB CF A A A A, F A A A A, F A A

C C, H

Refs. 38 283 59 71 360 17,69 69,245 17 145 318,360 245 360 354,355 318,327 388 145 145 388 146 467 34,171,223 145,240 318,360 467 145 145 447 53 234 515 34 123 104 360 388 67 145 145 123 123 123 123 123 98 360 318 34 360 145 145 145 98 145 145 145 145 318 145 145 145 145 192 62 60 60

TABLE 1. cont'd Monomer Styrene, p-iodoSuccinimide, JV-vinylValeric acid, 4-methyl-, vinyl ester Vinyl acetate

T( 0 C) 50 55 80 -60 -40 -20 -20 O 20 25

40 45 50

60

65 70 Vinylidene chloride

50 60

C M (xlO 4 )

Remarks

Refs.

1.9 0.55 24.8 1.9 0.40 0.60 0.70 0.30 0.50 0.90 0.96 0.94 0.90 1.3 1.45 2.4 10.7 1.29 1.32 2.0 0.25 0.41 0.54 0.61 1.29 2 4.55 20 1.75 1.8 1.9 1.91 1.93 2.0 2.1 2.4 2.5 2.5 2.6 2.8 2.1 2.4 2.9 22 38

Fl C

113 R R

56 93 200 158 464 464 464 241 241 86 464 328 241 86 86 202 69 12 328 51 466 265 265 265 12 552 71 225 12 466 124 328 348 231 145 294 86 167 167 80 466 403 86 541 541

C P (xlO 4 )

Remarks

Refs.

D D D D D 14 D D 17 17 D

W14 W15 C

112 C

C C

TABLE 2. TRANSFER CONSTANTS TO POLYMERS Polymer Acrylamide, N,N-dimethylPoIy(N, Af-dimethylacrylamide) Acrylic acid, ethyl ester Poly(methyl methacrylate) - , methyl ester Poly(isoprene) - , chlorinated Poly (methyl acrylate) Poly (methyl methacrylate) Acrylonitrile Cellulose

T( 0 C) 50

0.61

272

60

12800

M6

120

75 60

12.6 0.5 1.0 18000

C, F2 L L M6

308 212 105 120

1.0 11 20

L, N L, M4 L, M5

361 361 361

60 60


TABLE 2. cont'd Polymer Acrylonitrile, (cont'd) Poly(acrylonitrile) Poly(methyl methacrylate)

Poly(sarcosine) 1,3-Butadiene PoIy(1,3-butadiene) Ethylene

-, chloro Poly(vinyl chloride) Hexanoic acid, vinyl ester Poly(oxyethylene), dodecyl ether Methacrylic acid, butyl ester Poly(methyl methacrylate) -, dodecyl ester Poly (methyl methacrylate) -, ethyl ester Poly(isoprene), chlorinated Poly (vinyl chloride) Methyl methacrylate Poly(ethylene) Poly(isoprene), chlorinated Poly(methyl methacrylate)

T(0C)

50 60 60

60

Poly(vinyl chloride) Poly(vinyl urethane) Rubber, natural 2-Pyrrolidinone, 1-vinyl-dextran Dextran

376 135 25 25 25 25 23

C, C, C, C, C, C, C, C, C, C,

50

5

L

60

780

60

7700

M6

120

60

12800

M6

120

C, F2 C, F28

308 308

70 70

18.3 21.0

50 80 40

0.6 23.4 1.5 360 0.22 1.5 1.5 360 360 1000 0.1 1.5 2.1 360 2.48 0.22 1000 0.04 1.0 0.42 0.75 2.20 2.95 2.0 2.8 11 10.0 17 10.9 11.0

80 90

Poly(vinyl acetate)

F14 L N M2 M3 M

Refs.

11 108.40 150.70 194.81 214.46 337.31 256.85 195.81 199.89 155.78 348.46

60

Poly(styrene)

4.7 3.5 0.2 240 900 1270 400

Remarks

50 174.8 201.6 215.0 231.2 230.3 229.2 230.3 230.4 230.5 256.0

50

Poly(propylene)

C P (xlO 4 )

50 130 50 60 80 60 80 70 50 50 50

5 5.87

W20, F32 W20, F32 W20, F32 W20, F32 W22, F32 W21, F32 W20, F32 W19, F32 W18, F32 W20, F32

142 540 540 540 540 540 540 540 540 540 540 211 278

C, F17 N M N N M M N M N M N M C

C, F28 C, F8 C

209 307 326 326 147 326 327 326 327 147 105 326 262 326 262 147 147 292 209 292 148 262 262 263 263 250 308 157 258 258 333 203

TABLE 2. cont'd Polymer Styrene Poly(oxyadipoyloxy-2,2-dibromomethyl trimethylene) Poly(oxyethylene) - , dodecyl ether Poly(oxythexamethyleneoxy sebacoyl) Poly(methyl methacrylate)

T( 0 C)

60 70 70 60 80 50

60

Poly(propylene)

Poly(styrene)

80 100 60 66 130 50

55 60

73.5 85 90 100 110

Poly(vinyl acetate) Poly(vinyl chloride) Poly(2-vinylpyridine) Vinyl acetate Poly(oxyethylene) - , dodecyl ether Poly (methyl methacrylate) Poly(styrene) Poly(vinyl acetate)

130 154 100 130 50 60 60 60 75 40 60 75 -15 0 11 21 31 40 50

C P (xlO 4 ) 4.05 19 14 20 13 0.4 104 6000 >4xlO5 6303 4 1230 2300 2600 34760 700 9.0 10.0 10.5 3.4 2.26

Remarks

C

C F2 C C C C C C, J J C,J C C J C, J A, R A, R A, R A, R F2 C J J J J C C

C C J J D, S C C C C F2, J J C

Refs.

80

145,232 328 86 420 390 86 390 389 389 389 389 390 86 390 390 86 71 86 86 390 539 539 539 539 86 208 442 232 71 338 338 338 338 289 390 289 71 145,232 420 86 86 390 86 86 71 86 86 338 39 39 39 389 86 389 86 86 389 45 5 5 5 190 145,231

Remarks page II-157; References page 11-159

TABLE 4. cont'd Solvent/Additive

T (0C)

Vinyl acetate (cont'd) Methanol (cont'd) Naphthacene Naphthalene

70 50 50

- , decahydroNaphtho[l,2,3,4-def]chrysene Nonanoic acid, ethyl ester 2,6-Octadiene, 2,7-dichloro- , 2,6-dimethyl-

70 60 50 50 50 60

Octanoic acid, ethyl ester Oleic acid, methyl ester

50 60

Oxalic acid, diethyl ester - , dimethyl ester

90 30 60 60

Paraldehyde Pentane, 2,2,4-trimethyl2,4-Pentanedione 1-Pentanol, n 2,2,3,3,4,4,5,5-octafluoro2-Pentanone, 4-methyl3-Pentanone

70 50 60 60 60 60

Pentyl acetate

70 75 75 50 50

Orthoformic acid, trimethyl ester

Pentyl alcohol Perylene Phenanthrene

Phenol

70 45 50 60

- , m-chloro-,p-chloro- , p-nitro- , 2,3,4,6-tetramethylPhenol-D -,m-chloro-,p-chloro-,2,3,4,6-tetramethylPhosphorus trichloride Propane, 2-bromo-2-methyl- , 2-chloro-2-methyl 1-Propanol, 2,2,3,3-tetrafluoro1-Propene, 3-chloro- , 3-chloro-2-methylPropionaldehyde

45 45 50 45 45 45 45 45 60 60 60 60 60 60 60

Propionic acid, ethyl ester - , methyl ester

70 50 60

Pyrene Pyrocatechol, 4-(l,l,3,3,-tetramethylbutyl)Pyrogallol Salicylic acid Silane, dimethylphenyl-

50 50 50 70 60

C s (xlO 4 )

4.3 6.0 5.5 8.62 x 106 1150 1457 1715 48 1.35 x 105 80 3200 430 700 70 217 1000 358 7.6 8.0 4.0 1.0 2.0 136 8.0 10 26.1 34.52 10.0 114.39 7.2 87.0 56 2.88 x 105 870 5600

3380 215 120 600 205 400 8.86 x 104 1.13 x 104 35 70 80 800 1.5 x 104 150 26 7.11 3100 400 950 1000 457 40 23 26 11500 11000 50000 296 2200

Remarks

J J C,J J C F2 C J

C F2 19 C C C J J

C,J J J J J J J J J J C, D F2 J J F2 C C J J J C A, R

Refs.

320 86 320 370 370 15 390 86 41 71 152 324 7 71 441 86 441 345 346 86 86 145,232 390 208 86 442 289 145 289 390 184 184 41 370 15

390 51 15 86 51 51 15 51 51 51 51 51 214 86 86 442 86 86 86 86 390 71 232 420 370 338 338 390 539

TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Silane, methyldichloro- , trichloro- , triethyl- , triphenylStearamide, N-allylStearic acid, ehtyl ester - , methyl ester Succinic acid, diethyl ester - , dihexyl ester - , dimethyl ester m-Tolualdehyde p-Tolualdehyde Toluene

T( 0 C)

60 60 60 60 90 50 60 60 60 60 60 60

75 80 50 70 70 60 70 75 50 50 50 50 50 50 60 50 60 50 70 75 60 60 60

280 290 400000

Q(3) Q(3) Q(3)

511 511 511

50 60

20 20

R R

541 541

60 60 60 60 60

5400 8600 12000 2000 4000

A, R A, R A, R A, R A, R

539 539 539 539 539

C, Q(I-2)

572

60 70

Triphenylene Veratraldeyhyde Xylene Vinyl chloride Carbon tetrachloride Chloroform Bromotrichloromethane Vinylidene chloride Af-Methylpyrolidone 2-Vinylpyridine Silane, diethylchloro- , Methyldichloro-,trichloro-,triethyl-,triphenylVinyltrimethylsilane Bromoform

Refs.

A, R A, R A, R A, R C, J C

60

Toluene, p-nitrop-Toluidine -, N,Ar-dimethyl-, AT-methylToluonitrile Triethylamine

Remarks

5800 8800 1200 2700 620.1 140 38.2 41 40 31 570 440 3.3 12.0 14.9 100 123 17.8 20.75 20.89 21.6 34 35 49.0 69.0 21.1 21.8 29.2 66 91.6 20.6 92.86 195 450 584 118 106300 750 380 830 38.3 360 370 160 550 14.9 278 166

50

- , bromo- , o-chloro-,p-chloro- , a-chloro-

C s (xlO 4 )

1200000

J J R C R C J F2 W15 R C C C C J C C F2 F2 F2 F2 J J J C C

539 539 539 539 173 71 441 420 420 420 86 86 158 15 357 71 71 357 80 21,59,289 357 86 86 265 265 357 390 357 184 273 15 389 389 86 389 184 15 154 154 154 15 154 24,145 370 86 15 390 184


TABLE 5. TRANSFER CONSTANTS TO SULFUR COMPOUNDS Modifier Acrylamide, A/-octadecyl-/acrylonitrile (1:1 mol ratio) 1-Dodecanethiol Acrylic acid 1-Dodecanethiol - , methyl ester 1-Butanethiol

J( 0 C)

Cx

Remarks

Refs.

60

0.539

C, F24

174

45

1.9

C, F31

549

Ethanethiol

30 60 50

2-Propanethiol

60

1.53 1.69 0.78 0.94 ±0.07 1.65 ±0.12 1.57 ±0.09 1.57 ±0.18 1.79 5.00 0.544 0.668 0.700 0.656

A A Ql Ql Q2 Q3 Q4 Q2 Q3 Ql Q2 Q3 Q4

Acrylonitrile 1-Dodecanethiol Hydrogen sulfide Methyl sulfoxide

Methyl tetrasulfide p-Toluenethiol Acrylonitrile/1,3-butadiene (10-90%) 1-Hexanethiol, - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol, - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (20-80%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (30-70%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/styrene (38.5-61.5 mol%) 1-Pentanethiol - , 1,1,3,3,4-pentamethylButadiene Xanthogendisulfide, dibutyl- , diethyl- , di-2-ethylhexyl- , di-isopropyl1,3-Butadiene 1-Butanethiol, 1,1,3,3-tetramethyl1-Octanethiol - , 1,1,3,3,5,5,7,7-octamethyl1-Tetradecanethiol 1,3-Butadiene/styrene 1-Dodecanethiol Formic acid, thio-, dithiobis_, _, _, ao'-dibutyl ester

50 50 20 30 40 50 80 50 5

0.73 0.13 0.1 0.47 0.0000812 0.11 0.29 0.795 0.69 0.97

C, F8 E

J

397 69,397 330 478,507 478,507 508 330,509 330 330 477 477 477 477 378 378 248 196 458 404 197 375 85 378

1.5

C, H

380

53.3

C, H

380

5

1.2

C, H

380

5

2.1

C, H

380

5

1.1

C, H

380

5

1.8

C, H

380

50

1.02

C, H

380

60 60 60 60

6.9 8.1 7.5 8.3

J J J J

532 532 532 532

5 50 5 50

5.3 3.7 21.8 16.0 19.0 3.0 19.5

H H H H H H H

242 242 242 242 243 242 242

50 50 5

0.66

B, H, J

384

5

2.42

B, H, J

383

TABLE 5. cont'd Modifier

T( 0 C)

1,3-Butadiene/styrene {cont'd)

- , - , ao'-diisopentyl ester

-5 50 5 -5 5 50 5 -5 50 5 50 5 50 5 -5 50 5

- , - , - , 0,O'-diisopropyl ester

-5 50 5

- , - , - , O,O'-di-sec-butyl ester - , - , - 0,O'-dicyclohexyl ester _, _, _, 0,0'-diethyl ester - , - , - , 0,O'-diheptyl ester - , - , - , 0,6>'-dihexyl ester - , - , - , 0,O'-diisobutyl ester

- , - , - , 0,O'-dimethyl ester - , - , - , 0,O'-dineopentyl ester - , - , - , 0,0'-dioctyl ester - , - , - , 0,O'-dipentyl ester - , - , - , 0,0'-dipropyl ester 1-Heptanethiol - , 1,1,3,3,5,5,6-heptamethyl1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Octanethiol - , 1,1,3,5,5,7,7-octamethyl/7-Dioxin, 2,3-dihydro/maleic anhydride 1-Butanethil Ethylene 1-Butanethiol Ethyl sulflde Methyl sulfoxide 2-Propanethiol, 2-methylSulfur hexafluoride Methyl methacrylate Acetic acid, dithiodi-, diethyl ester - , mercapto-, methyl ester Acetophenone, 3'-mercapto- , 4'-mercapto-

-5 50 5 -5 50 5 50 5 50 5 -5 50 5 -5 50

Cx 1.75 5.34 1.65 1.565 1.78 3.71 8.43 4.23 16.04 0.41 1.12 0.74 1.78 1.87 1.573 6.43 1.21 7.0 1.85 4.38 2.83 3.4 12.5 0.40-1.31 0.80-3.01 1.40-3.70 1.80-3.50 1.80-6.0 9.78 1.185 9.78 16.43 15.86 27.04 1.01 3.40 0.23 0.64 1.45 1.70 3.20 4.42 1.815 9.20

Remarks H C, H, J B, H, J H B, H, J C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J B, H, J H C, H, J B, H, J B, H, J B, H B, H, J, B, H, J, B, H, J, B, H, J, B, H, J,

Refs. 180 382

H C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J H C, H, J

180 383 383 383 180 382 383 382 383 382 383 180 382 383 341 180 382 383 341 100 100 100 100 100 100 179 180 382 383 180 382 383 382 383 382 383 180 382 383 180 382

GG4 GG3 GG2 GGl GG5

5

0.64

B, H, J

384

5

1.22 4.1 2.7-4.7

B, H, J H H

384 54,55 54

5

0.34

B, H, J

384

R

169

C, W5 C, W5 C, F21, W5 C, W5 C, F21, W5

457 454 259 457 259

60 130 130 130 130 130 60 60 45 45

6300 5.8 0.027 12 15.0 0.0000 0.00065 0.63 4.2 2.6

86 274 30 30

Remarks page II-157; References page 11-159

TABLE 5. cont'd Modifier Methyl methacrylate {cont'd) Anisole, 4,4'-dithiodip-Anisoyl disulfide Benzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , m-bromo- , /7-bromo- , m-chloro-,p-chloroBenzoyl disulfide Benzyl disulfide Benzyl sulfide

J( 0 C) 50 60 60

0.0044 0.0052 14.6

60 60 45 60 70 45 45 45 45 60 25 50 60 25 50

0.00365 0.0196 4.7 2.7 15 3.8 5.6 3.5 4.6 10.0 0.134 0.016 0.00627 0.0183 0.0098 0.0098 0.00154 0.0040 0.0039 0.084 0.021 0.66 0.67 0.008 0.22 0.09 0.35 0.33 0.21 0.13 0.55 0.00007 0.00258 16.7 0.0046 0.0098 10.0 0.0072 0.0117 290 0.0115 694 0.0176 0.0508 0.0127 0.0193 0.7 0.55 0.42 0.33 0.17 0.15 0.43 0.62 0.40 0.00013

Benzyl sulfone Benzyl sulfoxide Benzyl tetrasulfide Benzyl trisulfide 1-Butanethiol

60 50 50 50 50 60

Carbanilide, thio-

50

_, _, 4,4/-bis(dimethylamino)- , - , 4,4'-dichloro- , - , 3,3/-dimethoxy-, -, 3,3'-dimethyl- , -, 4,4'-dimethyl- , - , 3,3'-dinitroCarbon disulfide 2,13-Dioxa-7,8-dithia-3,12-disila-tetradecane, 3,3,12,12-tetrameth oxyDisulfide, bis(p-bromobenzoyl)- , bis (p-bromophenyl)-

50 50 50 50 50 50 60 79.5 60 50 60 60 50 60 60 70 60 50 60 50 60 60 70 80 90 50 70 50 60 70 60

- , bis(p-chlorobenzoyl)- , bis(p-chlorophenyl)-, -, -, -,

bis(p-cyanobenzoyl)bis(dimethylthiocarbamoyl)bis(p-nitrobenzoyl)bis(onitrophenyl)-

- , bis(/?-nitrophenyl)1-Dodecanethiol

Ethanethiol, 2-amino-, hydrochloride Ethanol, 2-mercaptoEthyl disulfide Formamidine, AÂf'-diphenyl- , - , U'-dithiobisMethyl sufoxide

Cx

50 60

0.22 0.0000071

Remarks

Refs. 285 285 369

A

F2 D F2

F2, J F2, J A F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 A

F7 F7 F2 F2 C, F2 A

490 491 30 274 566 30 30 30 30 369 368 354 368 368 252 354 368 252 252 354 354 274 69,397 251 251 251 251 251 251 251 251 288 474 369 285 285 369 285 285 369 104 369 285 285 285 285 573 573 573 573 473 473 473 274 473 310 251 438

TABLE 5. cont'd Modifier Methyl methacrylate (cont'd) 2-Naphthalenethiol 1-Penthanethiol Phenyl disulfide

Phenyl disufone Phenyl sulfide Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-[l,3,3,3-tetramethyl-l-(trimethylsiloxy)disiloxanyl]- , 3-(trimethoxy)2-Propanethiol - , 2-methylPropionic acid, 3-mercaptoSulfide, benzoyl dimethylthiocarbamoyl Sulfur Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester - , - , sodium salt - , S-phenyl ester - , - , compound with pyridine - , - , potassium salt - , S-propyl ester - , - , sodium salt m-Toluenethiol p-Toluenethiol a-Toluenethiol p-Toluoyl disulfide p-Tolyl disulfide Styrene Acetic acid, dithiodi-, -, -, -, -, -,

-, -, -, -, -, -,

diethyl ester dimethyl ester mercaptobutyl ester ethyl ester methyl ester

- , phenyl- , - , /?,/?'-dithiodi- , thio Aniline, 2,2' dithiodi-

-, 4,4'-dithiodi- , N-dodecyl-, 4,4'-dithiodiAnisole, 2,2'-dithiodi- , 4,4'-dithiodi- , p-methyl-, a,a'-dithiobis-

T( 0 C) 45 60 50 25 50 60

Cx

Remarks

Refs.

60 25 50 60 50 50 79.5 79.5 60 60 50 70 20 60 44.1 50

1.3 3.1 0.8 0.0174 0.0038 0.0007 0.00176 0.0085 0.0110 0.0003 0.00554 0.0064 0.00132 0.0006 0.0013 0.128 0.693 0.38 0.18 0.39 0.38 5.5 0.08 1.3 0.075 0.106

60

0.00226

490

60

0.00167

490

60 60

0.374 0.00537

490 490

60 45 45 50 60 50 60

0.00190 4.7 7.4 0.027 11.0 0.0031 0.0044

490 30 30 354 369 285 285

50 99 60 99 99 50 60 60 99

< 0.005 0.2 0.015 0.1 >14.0 26.0 58.0 0.63 27.6

50 99 25 50

0.24 >14.7 3.8 3.0 3.4 3.0 0.24 0.21 3.0 0.18 0.021

75 50 50 50 50 99

H D

A A D

F2 F2 D A C F2, J

F2, J

J, R A A

J

30 274 344 368 285 310 368 285 491 491 368 252 368 252 252 474 474 274 274 473 473 280 280 118 194 354

297 96 86 96 96 146 126 323 96 89 96 297 297 297 297 89 89 89 89 96


TABLE 5. cont'd Modifier Styrene {cont'd) /7-Anisoyl disulfide Anthranilic acid, 4,4'-dithiobisArylbenzene thiolsulfonate - , /?-chloro - , p-methoxy- , p-methylBenzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , o-ethoxy-,p-ethoxyBenzene thiosulfonate - , aryl-p-chloro- , aryl-p-methoxy- , aryl-p-methyl 2-Benzimidazolethiol Benzoic acid, 2,2/-dithiodi- , - , diethyl ester - , -,dimethyl ester -, 4,4'-dithiodi- , - , diethyl ester - , o-mercapto- , -, methyl ester -,thioBenzothiazole, 2,2/-dithiobis-

- , 2,2'-thiobis2-Benzothiazolethiol Benzo[B]thiophene, 4,5,6,7-tetrahydro-4(2-thienyl)Benzoyl disulfide

Benzyl alcohol, ô'-dithiobis-,/vAdithiobisBenzyl diselenide Benzyl disulfide

T( 0 C) 60 50 60 60 60 60

96.0 3.0 0.95 2.22 1.872 1.237

60 50 60 99 99 99

0.00617 1.60 1.67 0.08 25.1 0.13

60 60 60 99 50 50 99 50

2.597 1.475 1.099 0.21 0.01 < 0.005 0.2 0.11 0.17 0.11 >14.7 17.0 6.23 2.3 2.1 2.3 2.4 2.73 < 0.005 0.03 0.26 0.011 < 0.005 0.010 0.0107 36.0 0.11 0.58 0.09 2.0 0.02 0.03 0.00878 0.01 0.011 0.548 0.069 0.00335 0.052 0.051 5.4 13.2 21.0 22.0 25 15.0 17.0 15.4

50 99 99 99 25 50 75 99 50 50 99 60 50 60 99 50 50 60 50 60

Benzyl sulfide Benzyl sulfone Benzyl sulfoxide 1-Butanethiol

Cx

99 25 50 60 50 50 25 60

70 80 99

Remarks

R, F2 R, F2 R, F2 R, F2 A A

R, F2 R, F2 R, F2

J

A

A D

D, Ql D A A A A

Refs. 369 89 544 544 544 544 490 491 491 96 96 96 544 544 544 96 89 89 96 297 89 89,297 96 96 96 297 297 297 297 96 297 297 96 419 89 545 304 369 96 89 297 128 89 297 368 128 96 368 252 368 252 252 340 340 395 69,397 131 395 395 96

TABLE 5. cont'd Modifier Styrene (cont'd) 1-Butanethiol, 1,1,3,3-tetramethyl-

1-Butanethiol-D

Butyl disulfide

sec-Butyl disulfide tert-Butyl disulfide Butyl sulfide tert-Butyl sulfide Carbanilic acid, /?,/?'-dithiodi-diethyl ester Carbon disulfide Carbonic acid, dithio- , - , S,S'-bis(carboxymethyl)ester - , trithio- , - , S,S'-bis(carboxymethyl) ester 1-Decanethiol 2,13-Dioxa-7,8-dithia-3,12-disilatetradecane, 3,3,12,12-tetramethoxyDiphenyldisulfide Disulfide, bis(/?-bromobenzoyl) - , bis(a-bromo-o-tolyl) - , bis(/?-chlorobenzoyl) - , bis(chlorobenzyl) - , bis(2-chloroethyl) - , bis(a-chloro-o-tolyl) - , bis(>-cyanobenzoyl) - , bis(diethylthiocarbamoyl) - , bis(dimethylthiocarbamoyl)

T( 0 C)

5 50 60 70 80 25 55 60 99 150 50 50 60 60 60 50 60 50 50 80 80 79.5 60 60 50 60 50 50 50 60 60 60 70 80 95 115 130

- , bis(2-ethylhexyl) - , bis(Aêthyl-A^phenylthio-carbamoyl) - , bis(l-methylheptyl) - , bis(morpholinothiocarbonyl) - , bis(l-naphthylmethyl) - , bis(/?-nitrobenzoyl - , bis(o-nitrophenyl) - , bis(l-phenylethyl) - , bis(P-(2-pyridyl)ethyl) - , bis(2,3,5,6-tetramethylphenyl) - , bis(2,4,6-triisopropylphenyl) 1-Dodecanethiol

50 60 99 60 99 60 50 50 50 50 50 60 70 70 90 100 110

Cx

5.5 6.4 4.3 5.2 4.0 7.0 0.00079 0.00154 0.0024 0.0068 0.022 < 0.005 < 0.005 0.00014 0.0022 0.025 0.24 0.00066

Remarks

H H H A A A

A

A

0.36 0.21 4.3 4.2 0.0118 0.147 745 1.0 196 < 0.005 0.01 1.3 3190 0.724 1.11 0.0136 0.568 0.620 0.780 0.860 0.939 1.035 0.984 1.150 < 0.005 1.75 0.0104 6.1 0.033 6650 5

Mi5AHi5S1

6

Si

7

M2, S2

7

Mi, S 2

7

M3, S2

7

M4, S2

7

Mj5S1 Mi, AHi, Si

8 9 9

«10 ~4

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