Dk2044 index

FUNDAMENTALS OF

Second EditionRevised and Expanded

Anil KumarIndian Institute of TechnologyKanpur, India

Rakesh K. GuptaWest Virginia UniversityMorgantown, West Virginia, U.S.A.

M A R C E L

MARCEL DEKKER, INC. NEW YORK • BASEL

Copyright © 2003 Marcel Dekker, Inc.

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.

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or by any information storage and retrieval system, without permission in writing from

the publisher.

Current printing (last digit):

10 9 8 7 6 5 4 3 2 1

PRINTED IN THE UNITED STATES OF AMERICA


PLASTICS ENGINEERING

Founding Editor

Donald E. HudginProfessor

Clemson UniversityClemson, South Carolina

1. Plastics Waste Recovery of Economic Value, Jacob Letdner2 Polyester Molding Compounds, Robert Burns3 Carbon Black-Polymer Composites The Physics of Electrically Conducting

Composites, edited by Enid Keil Sichel4 The Strength and Stiffness of Polymers, edited byAnagnostis £ Zachanades

and RogerS Porter5 Selecting Thermoplastics for Engineering Applications, Charles P Mac-

Dermott6 Engineering with Rigid PVC Processabihty and Applications, edited by I Luis

Gomez7 Computer-Aided Design of Polymers and Composites, D H Kaelble8 Engineering Thermoplastics Properties and Applications, edited by James

M Margolis9 Structural Foam A Purchasing and Design Guide, Bruce C Wendle

10 Plastics in Architecture A Guide to Acrylic and Polycarbonate, RalphMontella

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

12 Plastics Technology Handbook, Manas Chanda and Salil K Roy13 Reaction Injection Molding Machinery and Processes, F Melvin Sweeney14 Practical Thermoforming Principles and Applications, John Flonan15 Injection and Compression Molding Fundamentals, edited by Avraam I

Isayev16 Polymer Mixing and Extrusion Technology, Nicholas P Cheremismoff17 High Modulus Polymers Approaches to Design and Development, edited by

Anagnostis E Zachanades and Roger S Porter18 Corrosion-Resistant Plastic Composites in Chemical Plant Design, John H

Mallinson19 Handbook of Elastomers New Developments and Technology, edited by Anil

K Bhowmick and Howard L Stephens20 Rubber Compounding Principles, Materials, and Techniques, Fred W

Barlow21 Thermoplastic Polymer Additives Theory and Practice, edited by John T

Lutz, Jr22 Emulsion Polymer Technology, Robert D Athey, Jr23 Mixing in Polymer Processing, edited by Chns Rauwendaal24 Handbook of Polymer Synthesis, Parts A and B, edited by Hans R

Kncheldorf


25. Computational Modeling of Polymers, edited by Jozef Bicerano26. Plastics Technology Handbook: Second Edition, Revised and Expanded,

Manas Chanda and Salil K. Roy27. Prediction of Polymer Properties, Jozef Bicerano28. Ferroelectric Polymers: Chemistry, Physics, and Applications, edited by Hari

Singh Nalwa29. Degradable Polymers, Recycling, and Plastics Waste Management, edited

by Ann-Christine Albertsson and Samuel J. Huang30. Polymer Toughening, edited by Charles B. Arends31. Handbook of Applied Polymer Processing Technology, edited by Nicholas P.

Cheremisinoff and Paul N. Cheremisinoff32. Diffusion in Polymers, edited by P. Neogi33. Polymer Devolatilization, edited by Ramon J. Albalak34. Anionic Polymerization: Principles and Practical Applications, Henry L. Hsieh

and Roderic P. Quirk35. Cationic Polymerizations: Mechanisms, Synthesis, and Applications, edited

by Krzysztof Matyjaszewski36. Polyimides: Fundamentals and Applications, edited by Malay K. Ghosh and

K. L. Mittal37. Thermoplastic Melt Rheology and Processing, A. V. Shenoy and D. R. Saini38. Prediction of Polymer Properties: Second Edition, Revised and Expanded,

Jozef Bicerano39. Practical Thermoforming: Principles and Applications, Second Edition,

Revised and Expanded, John Florian40. Macromolecular Design of Polymeric Materials, edited by Koichi Hatada,

Tatsuki Kitayama, and Otto Vogl41. Handbook of Thermoplastics, edited by Olagoke Olabisi42. Selecting Thermoplastics for Engineering Applications: Second Edition,

Revised and Expanded, Charles P. MacDermott and Aroon V. Shenoy43. Metallized Plastics: Fundamentals and Applications, edited by K. L Mittal44. Oligomer Technology and Applications, Constantin V. Uglea45. 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 TakeoAraki, 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 YusufYagci

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 Brown51. Handbook of Polypropylene and Polypropylene Composites, edited by Har-

utun G. Karian52. Polymer Blends and Alloys, edited by Gabriel O. Shonaike and George P.

Simon53. Star and Hyperbranched Polymers, edited by Munmaya K. Mishra and Shi-

ro Kobayashi54. 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 GLeGrand and John T Bendler

57 Handbook of Polyethylene Structures, Properties, and Applications, AndrewJ Peacock

58 Polymer and Composite Rheology Second Edition, Revised and Expanded,Rakesh K Gupta

59 Handbook of Polyolefms Second Edition Revised and Expanded, editedby Cornelia Vasile

60 Polymer Modification Principles, Techniques, and Applications, edited byJohn J Meister

61 Handbook of Elastomers Second Edition, Revised and Expanded, editedby Anil K Bhowmick and Howard L Stephens

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

63 Practical Injection Molding, Bernie A Olmstea and Martin E Davis64 Thermosetting Polymers, Jean-Pierre Pascault, Henry Sautereau, Jacques

Verdu, and Roberto J J Williams65 Prediction of Polymer Properties Third Edition, Revised and Expanded, Jozef

Bicerano66 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

viii Preface to the First Edition


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 First Edition ix


Contents

Preface to the Second Edition v

Preface to the First Edition vii

1. Introduction 1

1.1 Defining Polymers 1

1.2 Classification of Polymers and Some Fundamental

Concepts 4

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

1.8 Conclusion 38

xi


References 39

Problems 39

2. Effect of Chemical Structure on Polymer Properties 45

2.1 Introduction 45

2.2 Effect of Temperature on Polymers 45

2.3 Additives for Plastics 50

2.4 Rubbers 61

2.5 Cellulose Plastics 66

2.6 Copolymers and Blends 68

2.7 Cross-Linking Reactions 72

2.8 Ion-Exchange Resins 80

2.9 Conclusion 89

References 90

Problems 91

3. Step-Growth Polymerization 103

3.1 Introduction 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

Polymerization 118

3.7 Experimental Results 125

3.8 Conclusion 140

Appendix 3.1: The Solution of MWD Through the

Generating Function Technique in Step-Growth

Polymerization 140

References 143

Problems 145

4. Reaction Engineering of Step-Growth Polymerization 153


xii Contents


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

4.5 Conclusion 174

Appendix 4.1: Similarity Solution of Step-Growth

Polymerization in Films with Finite Mass Transfer 175

References 181

Problems 181

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

Polymerization 230

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

Polymerization 238

5.15 Diffusional Effect in Ziegler-Natta Polymerization 240

5.16 Newer Metallocene Catalysts for Olefin Polymerization 242

5.17 Conclusion 244

References 244

Problems 248

6. Reaction Engineering of Chain-Growth Polymerization 255


6.2 Design of Tubular Reactors 256

6.3 Copolymerization 273

Contents xiii


6.4 Recycling and Degradation of Polymers 285

6.5 Conclusion 287

Appendix 6.1: Solution of Equations Describing

Isothermal Radical Polymerization 287

References 293

Problems 294

7. Emulsion Polymerization 299


7.2 Aqueous Emulsifier Solutions 300

7.3 Smith and Ewart Theory for State II of Emulsion

Polymerization 304

7.4 Estimation of the Total Number of Particles, Nt 313

7.5 Monomer Concentration in Polymer Particles, [M] 315

7.6 Determination of Molecular Weight in Emulsion

Polymerization 319

7.7 Emulsion Polymerization in Homogeneous

Continuous-Flow Stirred-Tank Reactors 324

7.8 Time-Dependent Emulsion Polymerization 326

7.9 Conclusions 334

References 335

Problems 336

8. Measurement of Molecular Weight and Its Distribution 340


8.2 End-Group Analysis 342

8.3 Colligative Properties 343

8.4 Light Scattering 350

8.5 Ultracentrifugation 354

8.6 Intrinsic Viscosity 358

8.7 Gel Permeation Chromatography 364

8.8 Conclusion 369

References 369

Problems 371

9. Thermodynamics of Polymer Mixtures 374


xiv Contents


9.2 Criteria for Polymer Solubility 376

9.3 The Flory-Huggins Theory 379

9.4 Free-Volume Theories 396

9.5 The Solubility Parameter 398

9.6 Polymer Blends 401

9.7 Conclusion 403

References 403

Problems 405

10. Theory of Rubber Elasticity 407


10.2 Probability Distribution for the Freely Jointed Chain 408

10.3 Elastic Force Between Chain Ends 415

10.4 Stress-Strain Behavior 418

10.5 The Stress Tensor (Matrix) 420

10.6 Measures of Finite Strain 423

10.7 The Stress Constitutive Equation 427

10.8 Vulcanization of Rubber and Swelling Equilibrium 429

10.9 Conclusion 432

References 433

Problems 434

11. Polymer Crystallization 437


11.2 Energetics of Phase Change 443

11.3 Overall Crystallization Rate 447

11.4 Empirical Rate Expressions: The Avrami Equation 450

11.5 Polymer Crystallization in Blends and Composites 456

11.6 Melting of Crystals 459

11.7 Influence of Polymer Chain Extension and Orientation 462

11.8 Polymers with Liquid-Crystalline Order 464

11.9 Structure Determination 467

11.10 Working with Semicrystalline Polymers 479

11.11 Conclusion 480

References 481

Problems 484

Contents xv


12. Mechanical Properties 487


12.2 Stress-Strain Behavior 488

12.3 The Glass Transition Temperature 497

12.4 Dynamic Mechanical Experiments 501

12.5 Time-Temperature Superposition 504

12.6 Polymer Fracture 508

12.7 Crazing and Shear Yielding 511

12.8 Fatigue Failure 516

12.9 Improving Mechanical Properties 518

References 520

Problems 523

13. Polymer Diffusion 526


13.2 Fundamentals of Mass Transfer 527

13.3 Diffusion Coefficient Measurement 531

13.4 Diffusivity of Spheres at Infinite Dilution 542

13.5 Diffusion Coefficient for Non-Theta Solutions 546

13.6 Free-Volume Theory of Diffusion in Rubbery Polymers 547

13.7 Gas Diffusion in Glassy Polymers 552

13.8 Organic Vapor Diffusion in Glassy Polymers:

Case II Diffusion 557

13.9 Polymer-Polymer Diffusion 560


References 565

Problems 569

14. Flow Behavior of Polymeric Fluids 573


14.2 Viscometric Flows 576

14.3 Cone-and-Plate Viscometer 578

14.4 The Capillary Viscometer 584

14.5 Extensional Viscometers 589

14.6 Boltzmann Superposition Principle 592

14.7 Dynamic Mechanical Properties 595

14.8 Theories of Shear Viscosity 598

xvi Contents


14.9 Constitutive Behavior of Dilute Polymer Solutions 605

14.10 Constitutive Behavior of Concentrated Solutions and

Melts 615


References 622

Problems 626

15. Polymer Processing 630


15.2 Extrusion 631

15.3 Injection Molding 651

15.4 Fiber Spinning 667

15.5 Conclusion 680

References 680

Problems 684

Contents xvii


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Dk2044 index