Plastics Technology Handbook Fifth Edition PDF

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Plastics Technology Handbook Fifth Edition Plastics Technology Handbook Fifth Edition Manas Chanda CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2018 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, ...

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Plastics Technology Handbook Fifth Edition

Plastics Technology Handbook Fifth Edition

Manas Chanda

CRC Press Taylor & Francis Group 6000 Broken Sound Parkway NW, Suite 300 Boca Raton, FL 33487-2742 © 2018 by Taylor & Francis Group, LLC CRC Press is an imprint of Taylor & Francis Group, an Informa business No claim to original U.S. Government works Printed on acid-free paper International Standard Book Number-13: 978-1-4987-8621-8 (Hardback) This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to publish reliable data and information, but the author and publisher cannot assume responsibility for the validity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this form has not been obtained. If any copyright material has not been acknowledged, please write and let us know so we may rectify in any future reprint. Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopying, microfilming, and recording, or in any information storage or retrieval system, without written permission from the publishers. For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://www.copyright .com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation without intent to infringe. Library of Congress Cataloging-in-Publication Data Names: Chanda, Manas, 1940- author. Title: Plastics technology handbook / Manas Chanda. Description: Fifth edition. | Boca Raton, FL : CRC Press, Taylor & Francis, 2018. | Series: Plastics engineering series | Includes bibliographical references. Identifiers: LCCN 2017035500| ISBN 9781498786218 (hardback : acid-free paper) | ISBN 9781315155876 (ebook) Subjects: LCSH: Plastics. Classification: LCC TA455.P5 C46 2018 | DDC 668.4–dc23 LC record available at https://lccn.loc.gov/2017035500 Visit the Taylor & Francis Web site at http://www.taylorandfrancis.com and the CRC Press Web site at http://www.crcpress.com

Dedicated to the hallowed memory of my father and mentor Narayan Chanda (1911–2005), a renowned author and a decorated teacher, who showed by example the value of dedication and perseverance in academic pursuits.

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Contents Preface ............................................................................................................................................. xxvii Author .............................................................................................................................................. xxxi

1

Characteristics of Polymers and Polymerization Processes 1.1 1.2

1.3

1.4

1.5 1.6 1.7 1.8 1.9

What Is a Polymer?.................................................................................................................................... 1 Molecular Weight of Polymers................................................................................................................ 3
n ) .............................................................................. 3 1.2.1 Number-Average Molecular Weight (M 1.2.1.1 End-Group Analysis .....................................................................................................3 1.2.1.2 Ebulliometry (Boiling-Point Elevation)....................................................................4 1.2.1.3 Cryoscopy (Freezing-Point Depression) ..................................................................4 1.2.1.4 Membrane Osmometry ................................................................................................4 1.2.1.5 Vapor-Phase Osmometry ............................................................................................5
w ) ............................................................................... 7 1.2.2 Weight-Average Molecular Weight (M 1.2.2.1 Light-Scattering Method ..............................................................................................7 1.2.2.2 Low-Angle Laser Light Scattering (LALLS) ............................................................9
v )............................................................................. 9 1.2.3 Viscosity-Average Molecular Weight (M 1.2.3.1 Dilute Solution Viscometry...................................................................................... 10 1.2.4 Polydispersity Index ...................................................................................................................12 1.2.4.1 Gel Permeation Chromatography........................................................................... 14 Polymerization Reactions........................................................................................................................ 20 1.3.1 Addition or Chain Polymerization .........................................................................................20 1.3.2 Coordination Addition Polymerization .................................................................................24 1.3.3 Step Polymerization....................................................................................................................28 1.3.4 Supramolecular Polymerization ...............................................................................................34 1.3.5 Copolymerization ........................................................................................................................35 Polymerization Processes ........................................................................................................................ 37 1.4.1 Process Characteristics...............................................................................................................37 1.4.1.1 Bulk, Solution, and Suspension Polymerization.................................................. 38 1.4.1.2 Emulsion Polymerization.......................................................................................... 39 1.4.1.3 Microemulsion Polymerization ............................................................................... 43 1.4.2 Industrial Polymerization..........................................................................................................49 1.4.2.1 Heat Removal .............................................................................................................. 49 1.4.2.2 Reactor Agitation........................................................................................................ 50 1.4.2.3 Residence Time ........................................................................................................... 50 1.4.2.4 Industrial Reactors ..................................................................................................... 51 Configurations of Polymer Molecules.................................................................................................. 58 Conformations of a Polymer Molecule................................................................................................ 58 Polymer Crystallinity ............................................................................................................................... 60 1.7.1 Determinants of Polymer Crystallinity ..................................................................................60 The Amorphous State.............................................................................................................................. 62 Structural Shape of Polymer Molecules............................................................................................... 63

ix

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Contents

1.10 Thermal Transitions in Polymers ......................................................................................................... 65 1.10.1 Tg and Tm ....................................................................................................................................65 1.10.2 Regions of Viscoelastic Behavior ...........................................................................................68 1.10.3 Factors Affecting Tg ..................................................................................................................70 1.10.3.1 Chain Flexibility ...................................................................................................... 70 1.10.3.2 Steric Effects.............................................................................................................. 71 1.10.3.3 Configurational Effects ........................................................................................... 71 1.10.3.4 Effect of Cross-Linking .......................................................................................... 71 1.10.4 Factors Affecting Tm .................................................................................................................71 1.10.4.1 Symmetry .................................................................................................................. 72 1.10.4.2 Intermolecular Bonding......................................................................................... 72 1.10.4.3 Tacticity ..................................................................................................................... 73 1.10.4.4 Branching, Chain Flexibility, and Molecular Weight ..................................... 74 1.10.5 Relation between Tm and Tg ...................................................................................................74 1.11 Designing a Polymer Structure for Improved Properties................................................................ 74 1.12 Cross-Linking of Polymer Chains......................................................................................................... 76 1.12.1 Reactions of Functional Groups.............................................................................................76 1.12.2 Vulcanization..............................................................................................................................78 1.12.3 Radiation Cross-Linking ..........................................................................................................83 1.12.4 Photochemical Cross-Linking.................................................................................................84 1.12.5 Ionic Cross-Linking ..................................................................................................................85 1.13 Solubility Behavior of Polymers ............................................................................................................ 86 1.13.1 Solubility Parameter..................................................................................................................86 1.14 Effects of Corrosives on Polymers ........................................................................................................ 94 1.15 Thermal Stability and Flame Retardation ........................................................................................... 94 1.15.1 Thermal Degradation ...............................................................................................................98 1.15.2 Ablation .....................................................................................................................................102 1.15.3 Flame Retardation ...................................................................................................................103 1.16 Deterioration of Polymers .................................................................................................................... 103 1.16.1 Chemical Deterioration..........................................................................................................104 1.16.2 Degradation by Radiation......................................................................................................106 1.16.3 Microbiological Deterioration...............................................................................................106 1.17 Stabilization of Polymers ...................................................................................................................... 107 1.17.1 Antioxidants and Related Compounds ..............................................................................109 1.17.2 Chemical Structures of Antioxidants ..................................................................................110 1.17.3 Stabilization of Selected Polymers .......................................................................................110 1.17.3.1 Polypropylene.........................................................................................................112 1.17.3.2 Polyethylene............................................................................................................114 1.17.3.3 Polystyrene..............................................................................................................115 1.17.3.4 Acrylonitrile–Butadiene–Styrene Copolymers................................................115 1.17.3.5 Polycarbonate .........................................................................................................115 1.17.3.6 Nylons......................................................................................................................116 1.17.3.7 Thermoplastic Elastomers ...................................................................................116 1.17.3.8 Polyacetal.................................................................................................................117 1.17.3.9 Poly(Vinyl Chloride) ............................................................................................117 1.17.3.10 Rubber......................................................................................................................118 1.18 Metal Deactivators.................................................................................................................................. 119

Contents

xi

1.19 Light Stabilizers ....................................................................................................................................... 120 1.19.1 Light Stabilizer Classes ...........................................................................................................121 1.19.1.1 UV Absorbers.........................................................................................................122 1.19.1.2 Quenchers ...............................................................................................................123 1.19.1.3 Hydroperoxide Decomposers .............................................................................124 1.19.1.4 Free-Radical Scavengers.......................................................................................124 1.20 Light Stabilizers for Selected Plastics ................................................................................................. 128 1.20.1 Polypropylene...........................................................................................................................128 1.20.2 Polyethylene..............................................................................................................................128 1.20.3 Styrenic Polymers ....................................................................................................................129 1.20.4 Poly(Vinyl Chloride) ..............................................................................................................130 1.20.5 Polycarbonate ...........................................................................................................................130 1.20.6 Polyacrylates .............................................................................................................................131 1.20.7 Polyacetal...................................................................................................................................131 1.20.8 Polyurethanes ...........................................................................................................................131 1.20.9 Polyamides ................................................................................................................................131 1.21 Diffusion and Permeability................................................................................................................... 131 1.21.1 Diffusion ....................................................................................................................................132 1.21.2 Permeability ..............................................................................................................................132 1.22 Polymer Compounding ......................................................................................................................... 133 1.22.1 Fillers ..........................................................................................................................................135 1.23 Plasticizers ................................................................................................................................................ 137 1.23.1 Phthalic Acid Esters................................................................................................................139 1.23.2 Phosphoric Acid Esters ..........................................................................................................140 1.23.3 Fatty Acid Esters......................................................................................................................140 1.23.4 Polymeric Plasticizers .............................................................................................................141 1.23.5 Miscellaneous Plasticizers......................................................................................................142 1.24 Antistatic Agents..................................................................................................................................... 142 1.24.1 External Antistatic Agents.....................................................................................................143 1.24.2 Internal Antistatic Agents .....................................................................................................144 1.24.3 Chemical Composition of Antistatic Agents.....................................................................144 1.24.3.1 Antistatic Agents Containing Nitrogen............................................................144 1.24.3.2 Antistatic Agents Containing Phosphorus ......................................................146 1.24.3.3 Antistatic Agents Containing Sulfur.................................................................146 1.24.3.4 Betaine-Type Antistatic Agents..........................................................................147 1.24.3.5 Nonionic Antistatic Agents.................................................................................147 1.25 Flame Retardants .................................................................................................................................... 147 1.25.1 Halogen Compounds..............................................................................................................148 1.25.2 Phosphorus Compounds .......................................................................................................149 1....