Sepour/Carraher's Polymer Chemistry Sixth Edition Revised and Expanded Charles E Carraher, Jr College of Science Florida Atlantic University Boca Raton, and Florida Center for Environmental Studies Palm Beach Gardens, Florida, U.S.A MARCEL DEKKER, INC Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved NEW YORK • BASEL Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 0–8247–0806–7 This book is printed on acid-free paper Headquarters Marcel Dekker, Inc 270 Madison Avenue, New York, NY 10016 tel: 212–696–9000; fax: 212–685–4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41–61–260–6300; fax: 41–61–260–6333 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities For more information, write to Special Sales/Professional Marketing at the headquarters address above Copyright 2003 by Marcel Dekker, Inc All Rights Reserved Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher Current printing (last digit): 10 PRINTED IN THE UNITED STATES OF AMERICA Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved UNDERGRADUATE CHEMISTRY A Series of Textbooks Edited by J J LAGOWSKI Department of Chemistry The University of Texas at Austin Modern Inorganic Chemistry, J J Lagowski Modern Chemical Analysis and Instrumentation, Harold F Walton and Jorge Reyes Problems in Chemistry, Second Edition, Revised and Expanded, Henry O Daley, Jr., and Robert F O'Malley Principles of Colloid and Surface Chemistry, Paul C Hiemenz Principles of Solution and Solubility, Kozo Shinoda, translated in collaboration with Paul Becher Physical Chemistry: A Step-by-Step Approach, M K Kemp Numerical Methods in Chemistry, K Jeffrey Johnson Polymer Chemistry An Introduction, Raymond B Seymour and Charles E Carraher, Jr Principles of Colloid and Surface Chemistry, Second Edition, Revised and Expanded, Paul C Hiemenz 10 Problems in Chemistry, Second Edition, Revised and Expanded, Henry O Daley, Jr, and Robert F O'Malley 11 Polymer Chemistry: An Introduction, Second Edition, Raymond B Seymour and Charles E Carraher, Jr 12 Polymer Chemistry An Introduction, Third Edition, Revised and Expanded, Raymond B Seymour and Charles E Carraher, Jr 13 Seymour/Carraher's Polymer Chemistry: An Introduction, Fourth Edition, Revised and Expanded, Charles E Carraher, Jr 14 Seymour/Carraher's Polymer Chemistry: Fifth Edition, Revised and Expanded, Charles E Carraher, Jr 15 Principles of Thermodynamics, Myron Kaufman 16 Seymour/Carraher's Polymer Chemistry: Sixth Edition, Revised and Expanded, Charles E Carraher, Jr Additional Volumes in Preparation Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved To Raymond Seymour—educator, scientist, pioneer, prophet, historian, family man, and friend—we miss you Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved Foreword Polymer science and technology has developed tremendously over the last few decades, and the production of polymers and plastics products has increased at a remarkable pace By the end of 2000, nearly 200 million tons per year of plastic materials were produced worldwide (about 2% of the wood used, and nearly 5% of the oil harvested) to fulfill the ever-growing needs of the plastic age; in the industrialized world plastic materials are used at a rate of nearly 100 kg per person per year Plastic materials with over $250 billion dollars per year contribute about 4% to the gross domestic product in the United States Plastics have no counterpart in other materials in terms of weight, ease of fabrication, efficient utilization, and economics It is no wonder that the demand and the need for teaching in polymer science and technology have increased rapidly To teach polymer science, a readable and up-to-date introductory textbook is required that covers the entire field of polymer science, engineering, technology, and the commercial aspect of the field This goal has been achieved in Carraher’s textbook It is eminently useful for teaching polymer science in departments of chemistry, chemical engineering, and material science, and also for teaching polymer science and technology in polymer science institutes, which concentrate entirely on the science and technologies of polymers This sixth edition addresses the important subject of polymer science and technology, with emphasis on making it understandable to students The book is ideally suited not only for graduate courses but also for an undergraduate curriculum It has not become more voluminous simply by the addition of information—in each edition less important subjects have been removed and more important issues introduced Polymer science and technology is not only a fundamental science but also important from the industrial and commercial point of view The author has interwoven discussion of these subjects with the basics in polymer science and technology Testimony to the high acceptance of this book is that early demand required reprinting and updating of each Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved of the previous editions We see the result in this new significantly changed and improved edition Otto Vogl Herman F Mark Professor Emeritus Department of Polymer Science and Engineering University of Massachusetts Amherst, Massachusetts Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved Preface An explosive scientific and technological revolution is underway and at its center are polymers This revolution is the result of a number of factors that complement one another These factors include a better understanding of the science of materials and availability of new and refined materials, synthetic techniques, and analytical tools Much of this revolution is of a fundamental nature and it is explored in the latest edition of this text These advances are often based on new and extended understanding and application of basic principles initially presented in the core chemistry courses (organic, physical, inorganic, analytical, and biological) Polymer Chemistry complies with the advanced course definition given by the American Chemical Society Committee on Professional Training, building on the foundations laid in general, organic, physical, analytical/instrumentation, and inorganic chemistry It also includes all the major and optional topics recommended in the syllabus adopted by the joint polymer education committee of the American Chemical Society (Appendix D: Syllabus) The text integrates and interweaves the important core topic areas The core topics are interrelated with information that focuses on polymer topics This assists students in integrating their chemical knowledge and illustrates the connection between theoretical and applied chemical information Also, industrial practices and testing procedures and results are integrated with the theoretical treatment of the various topics, allowing the reader to bridge the gap between industrial practice and the classroom It is written so that chapters can be taken out of order and not all the chapters need to be covered to gain an adequate appreciation of the science of polymers Many of the chapters begin with theory, followed by application Some readers will elect to read the more descriptive chapters dealing with polymer types before looking at the analytical/analysis/properties chapters This book is user friendly—it is appropriate as an advanced undergraduate text or an introductory-level graduate-level course text It can serve as the text for the initial Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved course in a series taken by a student, or it can be the lone polymer text read by a student in the study of polymers Students of chemistry, materials, engineering, medicine, biochemistry, physics, and geology will benefit from an understanding of the material found in this text The application and theory of polymers continues to expand This new edition reflects this growth and the continually expanding role of polymers There is an increased emphasis on pictorializing, reinforcing, integrating, and interweaving the basic concepts The first chapter is shorter in order to allow time for student orientation However, the other chapters should not require more than a week’s time each Each chapter is essentially self-contained, but each relates to the other chapters Whenever possible, difficult concepts are distributed and reinforced over several chapters A glossary, biography, suggested questions (and answers), and learning objectives/summary are included at the end of each chapter Application and theory are integrated so that they reinforce one another This is true for all the various important and critical types of polymers including synthetic, biological, organometallic, and inorganic polymers The principle that the basic concepts that apply to one grouping of polymers apply to all the other types of polymers is emphasized The updating of analytical, physical, and spectral characterization techniques continues, including expanded coverage of the theory and results arising from atomic force microscopy and scanning probe microscopy Special sections dealing with industrially important polymers are included, and the section dealing with soluble stereoregulating catalysis has been expanded There is still an emphasis on naturally occurring polymers, and discussions of supercoiling, replication, and compacting are included As before, the interplay between natural and synthetic polymers is emphasized A number of miscellaneous topics have been drawn together in one chapter, which includes sections on conductive polymers, smart materials, protomics, human genome, optical fibers, material selection charts, carbon nanotubes, and liquid crystals Emphasis on nanotechnology and nanomaterials remains with added or expanded sections dealing with zeolites, nanotubes, nanocomposites, molecular wires, dendrites, and self assembly The chapter on polymer technology and processing has been rewritten and expanded The section listing Web sites has been updated The nomenclature section has been enlarged, and a new appendix on the stereogeometry of polymers has been added Additional aids and appendixes are included: how to study, nomenclature, over 1500 trade names, about 400 citations to appropriate Journal of Chemical Education and Polymer News articles, Web sites dealing with polymer topics, and over 100 structures of common polymers Charles E Carraher, Jr Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved Acknowledgments I gratefully acknowledge the contributions of Herman Mark of the Polytechnic Institute of New York; Charles L McCormick, University of Southern Mississippi; William Feld, Wright State University; Eli Pearce, Polytechnic Institute of New York; Fredinard Rodriguez, Cornell University; and Otto Vogl, University of Massachusetts, for their reviewing, advising, and counseling efforts; and Charles Carraher III and Shawn Carraher for their help in proofing and indexing I also thank the following for their special contributions to the book: Charles Gebelein, Les Sperling, Anglo Volpe, Stam Israel, Carl Wooten, Rita Blumstein, Eckhard Hellmuth, Frank Millich, Norman Miller, Rudy Deanin, Guy Donaruma, Leo Mandelkem, R V Subramanian, Charles Pittman, Brian Currell, C Bamford, Roger Epton, Paul Flory, Charles Overberger, William Bailey, Jim O’Donnell, Rob Burford, Edgar Hardy, John H Coates, Don Napper, Frank Harris, G Allan Stahl, John Westerman, William A Field, Nan-Loh Yang, Sheldon Clare, E N Ipiotis, D H Richards, G Kirshenbaum, A M Sarquis, Lon Mathias, Sukumar Maiti, S Temin, Yoshinobu Naoshima, Eberhard Neuse, John Sheats, George Hess, David Emerson, Kenneth Bixgorin, Thomas Miranda, M B Hocking, Marsha Colbert, Joseph Lagowski, Dorothy Sterling, Amanda Murphy, John Kloss, Qingmao Zhang, Bhoomin Pandya, Ernest Randolph, Alberto Rivalta, and Fengchen He This book could not have been written without the long-time efforts of Professor Herman Mark, who was one of the fathers of polymer science For the fourth edition, a special thanks for the assistance of Colleen Carraher I acknowledge the kind permission of Gerry Kirshenbaum and Polymer News for allowing us to use portions of articles that have appeared in Polymer News Finally, I thank Edward S Wilks for his help with the section on “Chemical Abstracts–Based Polymer Nomenclature.” Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved Comments on Health 875 Table 1.2 TWA Values for Selected Monomers and Additional Recognized Toxins Chemical Acetic anhydride Acrylonitnle Benzene 1,3-Butadiene Carbon monoxide Chloroprene ,2-Ethylenediamme Ethylene oxide Formaldehyde Hydra/me Hydrogen cyanide Phenol Styrene Vinyl chloride TWA (ppm) 20 10 1000 50 25 10 50 10 100 500 Such people must take special care to avoid exposure to dangerous chemicals, since many of these accumulate in our bodies over a long time, slowly building to levels that may be unhealthy Most of the toxic and undesirable chemicals of a decade ago have been eliminated from the common workplace This includes halogenated hydrocarbons such as carbon tetrachloride and aromatic hydrocarbons such as benzene Further, chemicals that are known to be potentially toxic, such as some monomers, are being eliminated from polymeric materials to within the limits of detection We are also becoming more aware of the effects of nonchemical hazards in the workplace These hazards are being dealt with as they become known Some of these possible hazards include exposure to certain radiations employed in materials processing, machine and other noise, machine operation, and exposure to other potential safety situations Industrial recognition of customer and employee safety is a major factor behind the international programs known as ISO 9000 and ISO 14000 (Appendix J) Further, a number of national agencies and associations deal with aspects of the environmental and personal safety issues, including the Environmental Protection Agency, National Fire Protection Association Occupational Safety and Health Administration, Department of Transportation, Food and Drug Administration, and the National Institute for Occupational Safety and Health ENVIRONMENT Today industry and business recognize that part of doing business is taking care of the environment Along with various government agencies and associated laws, business and industry are finding that good environmental practices are good business Advances continue with respect to lowering potentially harmful emissions as solid waste or into the water and air shared by all of us Chemical industries are taking the lead in this clean-up Copyright © 2003 by Marcel Dekker, Inc All Rights Reserved 876 Appendix I process (see also ISO 9000 and 14000; Appendix J) A combination of watchful vigilance and trust is needed to continue this effort Further readings are found in an ongoing series that appears in Polymer News Endocnnes-I Mimics and disrupters, 23(5):167-169 (1998) Endocnnes-II Fundamentals, 27(1 l)'382-385 (1998) Endocnnes-III Structural considerations, 24(4)-131-132 (1999) Fundamentals for human nsk assessments, 25(6): 198-200 (1998) Epidemiological contributions to nsk assessments, 23(9).311-312 (1998) Toxicity indicator values—ERPGs and WEELs, 24(l)-23-25 (1999) Toxicity indicator values—RfD, RfC, NOAEL, LOAEL, and other measures, 24(2).58-59 (1999) Fundamentals of toxicology—Basics, 24(5)'159-161 (1999) Basics of toxicology testing, 24(7)'233-234 (1999) Human responses to lexicological testing, 24(8).275-276 (1999) Biotransformations, 24(9) 311-312 (1999) Influence of route of exposure, 24(8) 250-253 (1999) Developmental toxicology, 25(1).20-22 (2000) Fundamentals of cancer—Risk assessments, 25(3) 90-91 (2000) Cancer bioassays, 25(5) 162-164 (2000) Short and long-term bioassays, 25(8).270-272 (2000) Cancer nsk assessment, 25(12) 414-415 (2000) Biomedical neurotoxicity, 26(8) 276-278 (2001) Immunotoxicity, 2