Macromolecular

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PRINCIPLES OF POLYMERIZATION
Fourth Edition

GEORGE ODIAN
College of Staten Island City University of New York Staten Island, New York

A JOHN WILEY & SONS, INC., PUBLICATION

PRINCIPLES OF POLYMERIZATION
Fourth Edition

PRINCIPLES OF POLYMERIZATION
Fourth Edition

GEORGE ODIAN
College of Staten Island City University of New York Staten Island, New York

A JOHN WILEY & SONS, INC.,PUBLICATION

Copyright # 2004 by John Wiley & Sons, Inc. All rights reserved. Published by John Wiley & Sons, Inc., Hoboken, New Jersey. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400, fax 978-750-4470, or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed to the PermissionsDepartment, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, e-mail: permreq@wiley.com. Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specificallydisclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any othercommercial damages, including but not limited to special, incidental, consequential, or other damages. For general information on our other products and services please contact our Customer Care Department within the U.S. at 877-762-2974, outside the U.S. at 317-572-3993 or fax 317-572-4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print,however, may not be available in electronic format. Library of Congress Cataloging-in-Publication Data: Principles of Polymerization, Fourth Edition George Odian ISBN 0-471-27400-3 Printed in the United States of America 10 9 8 7 6 5 4 3 2 1

CONTENTS

PREFACE 1 INTRODUCTION 1-1 Types of Polymers and Polymerizations / 1 1-1a Polymer Composition and Structure / 2 1-1b Polymerization Mechanism / 6 1-2Nomenclature of Polymers / 9 1-2a Nomenclature Based on Source / 10 1-2b Nomenclature Based on Structure (Non-IUPAC) / 11 1-2c IUPAC Structure-Based Nomenclature System / 11 1-2d Trade Names and Nonnames / 16 1-3 Linear, Branched, and Crosslinked Polymers / 17 1-4 Molecular Weight / 19 1-5 Physical State / 24 1-5a Crystalline and Amorphous Behavior / 24 1-5b Determinants of Polymer Crystallinity /27 1-5c Thermal Transitions / 29 1-6 Applications of Polymers / 32 1-6a Mechanical Properties / 32 1-6b Elastomers, Fibers, and Plastics / 35 References / 36

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STEP POLYMERIZATION 2-1 Reactivity of Functional Groups / 40 2-1a Basis for Analysis of Polymerization Kinetics / 40 2-1b Experimental Evidence / 41 2-1c Theoretical Considerations / 43 2-1d Equivalence ofGroups in Bifunctional Reactants / 44 2-2 Kinetics of Step Polymerization / 44 2-2a Self-Catalyzed Polymerization / 46 2-2a-1 Experimental Observations / 47 2-2a-2 Reasons for Nonlinearity in Third-Order Plot / 48 2-2a-3 Molecular Weight of Polymer / 50 2-2b External Catalysis of Polymerization / 51 2-2c Step Polymerizations Other than Polyesterification: Catalyzed versus Uncatalyzed / 53 2-2d...
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