Fundamentals of Polymer Engineering Part 1 pdf

FUNDAMENTALS OFSecond Edition Revised and Expanded Anil Kumar Indian Institute of Technology Kanpur, India Rakesh K.. Plastics Waste Recovery of Economic Value, Jacob Letdner 2 Polyester

FUNDAMENTALS OF

Second Edition

Revised and Expanded

Anil Kumar

Indian Institute of Technology

Kanpur, India

Rakesh K Gupta

West Virginia University

Morgantown, West Virginia, U.S.A.

M A R C E L

MARCEL DEKKER, INC NEW YORK • BASEL

Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress

ISBN: 0-8247-0867-9

The first edition was published as Fundamentals of Polymers by McGraw-Hill, 1997 This book is printed on acid-free paper

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Current printing (last digit):

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PRINTED IN THE UNITED STATES OF AMERICA

PLASTICS ENGINEERING

Founding Editor

Donald E Hudgin

Professor Clemson University Clemson, South Carolina

1 Plastics Waste Recovery of Economic Value, Jacob Letdner

2 Polyester Molding Compounds, Robert Burns

3 Carbon Black-Polymer Composites The Physics of Electrically Conducting

Composites, edited by Enid Keil Sichel

4 The Strength and Stiffness of Polymers, edited byAnagnostis £ Zachanades and RogerS Porter

5 Selecting Thermoplastics for Engineering Applications, Charles P Mac-Dermott

6 Engineering with Rigid PVC Processabihty and Applications, edited by I Luis Gomez

7 Computer-Aided Design of Polymers and Composites, D H Kaelble

8 Engineering Thermoplastics Properties and Applications, edited by James

M Margolis

9 Structural Foam A Purchasing and Design Guide, Bruce C Wendle

10 Plastics in Architecture A Guide to Acrylic and Polycarbonate, Ralph Montella

11 Metal-Filled Polymers Properties and Applications, edited by Swapan K Bhattacharya

12 Plastics Technology Handbook, Manas Chanda and Salil K Roy

13 Reaction Injection Molding Machinery and Processes, F Melvin Sweeney

14 Practical Thermoforming Principles and Applications, John Flonan

15 Injection and Compression Molding Fundamentals, edited by Avraam I Isayev

16 Polymer Mixing and Extrusion Technology, Nicholas P Cheremismoff

17 High Modulus Polymers Approaches to Design and Development, edited by Anagnostis E Zachanades and Roger S Porter

18 Corrosion-Resistant Plastic Composites in Chemical Plant Design, John H Mallinson

19 Handbook of Elastomers New Developments and Technology, edited by Anil

K Bhowmick and Howard L Stephens

20 Rubber Compounding Principles, Materials, and Techniques, Fred W Barlow

21 Thermoplastic Polymer Additives Theory and Practice, edited by John T Lutz, Jr

22 Emulsion Polymer Technology, Robert D Athey, Jr

23 Mixing in Polymer Processing, edited by Chns Rauwendaal

24 Handbook of Polymer Synthesis, Parts A and B, edited by Hans R Kncheldorf

25 Computational Modeling of Polymers, edited by Jozef Bicerano

26 Plastics Technology Handbook: Second Edition, Revised and Expanded,

Manas Chanda and Salil K Roy

27 Prediction of Polymer Properties, Jozef Bicerano

28 Ferroelectric Polymers: Chemistry, Physics, and Applications, edited by Hari Singh Nalwa

29 Degradable Polymers, Recycling, and Plastics Waste Management, edited

by Ann-Christine Albertsson and Samuel J Huang

30 Polymer Toughening, edited by Charles B Arends

31 Handbook of Applied Polymer Processing Technology, edited by Nicholas P Cheremisinoff and Paul N Cheremisinoff

32 Diffusion in Polymers, edited by P Neogi

33 Polymer Devolatilization, edited by Ramon J Albalak

34 Anionic Polymerization: Principles and Practical Applications, Henry L Hsieh and Roderic P Quirk

35 Cationic Polymerizations: Mechanisms, Synthesis, and Applications, edited

by Krzysztof Matyjaszewski

36 Polyimides: Fundamentals and Applications, edited by Malay K Ghosh and

K L Mittal

37 Thermoplastic Melt Rheology and Processing, A V Shenoy and D R Saini

38 Prediction of Polymer Properties: Second Edition, Revised and Expanded,

Jozef Bicerano

39 Practical Thermoforming: Principles and Applications, Second Edition,

Revised and Expanded, John Florian

40 Macromolecular Design of Polymeric Materials, edited by Koichi Hatada, Tatsuki Kitayama, and Otto Vogl

41 Handbook of Thermoplastics, edited by Olagoke Olabisi

42 Selecting Thermoplastics for Engineering Applications: Second Edition,

Revised and Expanded, Charles P MacDermott and Aroon V Shenoy

43 Metallized Plastics: Fundamentals and Applications, edited by K L Mittal

44 Oligomer Technology and Applications, Constantin V Uglea

45 Electrical and Optical Polymer Systems: Fundamentals, Methods, and

Applications, edited by Donald L Wise, Gary E Wnek, Debra J Trantolo, Thomas M Cooper, and Joseph D Gresser

46 Structure and Properties of Multiphase Polymeric Materials, edited by Takeo Araki, Qui Tran-Cong, and Mitsuhiro Shibayama

47 Plastics Technology Handbook: Third Edition, Revised and Expanded,

Manas Chanda and Salil K Roy

48 Handbook of Radical Vinyl Polymerization, Munmaya K Mishra and Yusuf Yagci

49 Photonic Polymer Systems: Fundamentals, Methods, and Applications,

edited by Donald L Wise, Gary E Wnek, Debra J Trantolo, Thomas M Cooper, and Joseph D Gresser

50 Handbook of Polymer Testing: Physical Methods, edited by Roger Brown

51 Handbook of Polypropylene and Polypropylene Composites, edited by Har-utun G Karian

52 Polymer Blends and Alloys, edited by Gabriel O Shonaike and George P Simon

53 Star and Hyperbranched Polymers, edited by Munmaya K Mishra and

Shi-ro Kobayashi

54 Practical Extrusion Blow Molding, edited by Samuel L Belcher

55 Polymer Viscoelasticity Stress and Strain in Practice, Evaristo Riande, Ricardo Diaz-Calleja, Margarita G Prolongo, Rosa M Masegosa, and Cat-alma Salom

56 Handbook of Polycarbonate Science and Technology, edited by Donald G LeGrand and John T Bendler

57 Handbook of Polyethylene Structures, Properties, and Applications, Andrew

J Peacock

58 Polymer and Composite Rheology Second Edition, Revised and Expanded,

Rakesh K Gupta

59 Handbook of Polyolefms Second Edition Revised and Expanded, edited

by Cornelia Vasile

60 Polymer Modification Principles, Techniques, and Applications, edited by John J Meister

61 Handbook of Elastomers Second Edition, Revised and Expanded, edited

by Anil K Bhowmick and Howard L Stephens

62 Polymer Modifiers and Additives, edited by John T Lutz, Jr, and Richard F Grossman

63 Practical Injection Molding, Bernie A Olmstea and Martin E Davis

64 Thermosetting Polymers, Jean-Pierre Pascault, Henry Sautereau, Jacques Verdu, and Roberto J J Williams

65 Prediction of Polymer Properties Third Edition, Revised and Expanded, Jozef Bicerano

66 Fundamentals of Polymer Engineering Second Edition, Revised and

Expanded, Anil Kumar and Rakesh K Gupta

Additional Volumes in Preparation

Handbook of Plastics Analysis, edited by Hubert Lobo and Jose Bonilla Metallocene Catalysts in Plastics Technology, Anand Kumar Kulshreshtha

To the memory of my father.

Anil Kumar

To the memory of my father Rakesh Gupta

Preface to the Second Edition

The objectives and organization of the second edition remain essentially unchanged The major difference from the first edition is the inclusion of new material on topics such as dendrimers, polymer recycling, Hansen solubility parameters, nanocomposites, creep in glassy polymers, and twin-screw extrusion New examples have been introduced throughout the book, additional problems appear at the end of each chapter, and references to the literature have been updated Additional text and figures have also been added The first edition has been successfully used in universities around the world, and we have received many encouraging comments We hope the second edition will also find favor with our colleagues, and be useful to future generations of students of polymer science and engineering

Anil Kumar Rakesh K Gupta

v

Preface to the First Edition

Synthetic polymers have considerable commercial importance and are known

by several common names, such as plastics, macromolecules, and resins These materials have become such an integral part of our daily existence that

an introductory polymer course is now included in the curriculum of most students of science and engineering We have written this book as the main text for an introductory course on polymers for advanced undergraduates and graduate students The intent is to provide a systematic coverage of the essentials of polymers

After an introduction to polymers as materials in the first two chapters, the mechanisms of polymerization and their effect on the engineering design

of reactors are elucidated The succeeding chapters consider polymer char-acterization, polymer thermodynamics, and the behavior of polymers as melts, solutions, and solids both above and below the glass transition temperature Also examined are crystallization, diffusion of and through polymers, and polymer processing Each chapter can, for the most part, be

vii

read independently of the others, and this should allow an instructor to design the course to his or her own liking Note that the problems given at the end of each chapter also serve to complement the main text Some of these problems cite references to the literature where alternative viewpoints are introduced We have been teaching polymer science for a long time, and we have changed the course content from year to year by adopting and expanding on ideas of the kind embodied in these problems

Since polymer science is an extremely vast area, the decision to include

or exclude a given subject matter in the text has been a difficult one In this endeavor, although our own biases will show in places, we have been guided

by how indispensable a particular topic is to proper understanding We have attempted to keep the treatment simple without losing the essential features; for depth of coverage, the reader is referred to the pertinent technical literature Keeping the student in mind, we have provided intermediate steps in most derivations For the instructor, lecturing becomes easy since all that is contained in the book can be put on the board The future will tell to what extent we have succeeded in our chosen objectives

We have benefited from the comments of several friends and colleagues who read different parts of the book in draft form Our special thanks go to Ashok Khanna, Raj Chhabra, Deepak Doraiswamy, Hota V S GangaRao, Dave Kofke, Mike Ryan, and Joe Shaeiwitz Professor Khanna has used the problem sets of the first seven chapters in his class for several years After finishing my Ph.D from Carnegie-Mellon University, I (Anil Kumar) joined the Department of Chemical Engineering at the Indian Institute

of Technology, Kanpur, India, in 1972 My experience at this place has been rich and complete, and I decided to stay here for the rest of my life I am fortunate to have a good set of students from year to year with whom I have been able to experiment in teaching various facets of polymer science and modify portions of this book continuously

Rakesh Gupta would like to thank Professor Santosh Gupta for introdu-cing polymer science to him when he was an undergraduate student This interest in polymers was nurtured by Professor Art Metzner and Dr K F Wissbrun, who were his Ph.D thesis advisors Rakesh learned even more from the many graduate students who chose to work with him, and their contribu-tions to this book are obvious Kurt Wissbrun reviewed the entire manuscript and provided invaluable help and encouragement during the final phases of writing Progress on the book was also aided by the enthusiastic support of Gene Cilento, the Department Chairman at West Virginia University Rakesh adds that these efforts would have come to nought without the determined help

of his wife, Gunjan, who guarded his spare time and allowed him to devote it

entirely to this project According to Rakesh, ‘‘She believed me when I told her it would take two years; seven years later she still believes me!’’

I doubt that this book would ever have been completed without the constant support of my wife, Renu During this time there have been several anxious moments, primarily because our children, Chetna and Pushkar, were trying to choose their careers and settle down In taking care of them, my role was merely helping her, and she allowed me to divide my attention between home and work Thank you, Renu

Anil Kumar Rakesh Gupta

Preface to the Second Edition v Preface to the First Edition vii

1.1 Defining Polymers 1 1.2 Classification of Polymers and Some Fundamental

1.3 Chemical Classification of Polymers Based on

Polymerization Mechanisms 16 1.4 Molecular-Weight Distributions 19 1.5 Configurations and Crystallinity of Polymeric Materials 22 1.6 Conformation of Polymer Molecules 27 1.7 Polymeric Supports in Organic Synthesis 29

xi

References 39

2 Effect of Chemical Structure on Polymer Properties 45

2.2 Effect of Temperature on Polymers 45 2.3 Additives for Plastics 50

2.5 Cellulose Plastics 66 2.6 Copolymers and Blends 68 2.7 Cross-Linking Reactions 72 2.8 Ion-Exchange Resins 80

3 Step-Growth Polymerization 103

3.2 Esterification of Homologous Series and the Equal

Reactivity Hypothesis 105 3.3 Kinetics of A–R–B Polymerization Using Equal

Reactivity Hypothesis 107 3.4 Average Molecular Weight in Step-Growth Polymerization

of ARB Monomers 111 3.5 Equilibrium Step-Growth Polymerization 116 3.6 Molecular-Weight Distribution in Step-Growth

3.7 Experimental Results 125

Appendix 3.1: The Solution of MWD Through the

Generating Function Technique in Step-Growth

4 Reaction Engineering of Step-Growth Polymerization 153

4.2 Analysis of Semibatch Reactors 156 4.3 MWD of ARB Polymerization in Homogeneous

Continuous-Flow Stirred-Tank Reactors 166 4.4 Advanced Stage of Polymerization 169

Appendix 4.1: Similarity Solution of Step-Growth

Polymerization in Films with Finite Mass Transfer 175

5 Chain-Growth Polymerization 188

5.2 Radical Polymerization 192 5.3 Kinetic Model of Radical Polymerization 197 5.4 Average Molecular Weight in Radical Polymerization 199 5.5 Verification of the Kinetic Model and the Gel Effect

in Radical Polymerization 201 5.6 Equilibrium of Radical Polymerization 210 5.7 Temperature Effects in Radical Polymerization 215 5.8 Ionic Polymerization 216 5.9 Anionic Polymerization 222 5.10 Ziegler-Natta Catalysts in Stereoregular Polymerization 226 5.11 Kinetic Mechanism in Heterogeneous Stereoregular

5.12 Stereoregulation by Ziegler-Natta Catalyst 232 5.13 Rates of Ziegler-Natta Polymerization 233 5.14 Average Chain Length of the Polymer in Stereoregular

5.15 Diffusional Effect in Ziegler-Natta Polymerization 240 5.16 Newer Metallocene Catalysts for Olefin Polymerization 242

6 Reaction Engineering of Chain-Growth Polymerization 255

6.2 Design of Tubular Reactors 256 6.3 Copolymerization 273