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9780130650566

Contemporary Polymer Chemistry

by ; ;
  • ISBN13:

    9780130650566

  • ISBN10:

    0130650560

  • Edition: 3rd
  • Format: Paperback
  • Copyright: 2003-02-12
  • Publisher: Prentice Hall
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List Price: $225.40

Summary

This book provides comprehensive, up-to-date, and accessible coverage of the relationship between fundamental chemistry and the uses of polymers.With help from new co-author James Mark, the book presents a complete overview of the synthetic, kinetic, structural, and applied aspects of modern polymer chemistry as well as coverage of industrial and medical applications.For chemists and chemical engineers involved in polymer chemistry.

Author Biography

Harry R. Allcock is Evan Pugh Professor of Chemistry at The Pennsylvania State University. He received his B.Sc. and Ph.D. degrees from the University of London. After holding postdoctoral positions at Purdue University and the National Research Council of Canada, he spent five years as a polymer research scientist in American industry before joining The Pennsylvania State University in 1966. Trained initially as a mechanistic organometallic chemist, his research interests have included the synthesis of new organic and inorganic polymers, the use of inorganic and organometallic compounds as polymerization initiators, radiation-induced polymerizations, ring-chain equilibria, organosilicon compounds, and the structural examination of polymers by X-ray diffraction, NMR, and conformational analysis techniques. A major interest throughout his career has been the design and synthesis of new biomedical materials. He and his coworkers synthesized the first stable polyphosphazenes, and his research group has been responsible for many of the major developments in this field. His pioneering research has been recognized by numerous awards including the American Chemical Society National Awards in Polymer Chemistry and Materials Chemistry, and the A.C.S Polymer Division Herman Mark Award in Polymer Science. He is also a Guggenheim Fellow and a recipient of the American Institute of Chemists Chemical Pioneer Award. He has held a number of visiting lectureships, has published three research monographs, co-authored three other volumes, and co-edited three additional books. Professor Allcock has authored or co-authored more than 440 research papers and reviews, holds 54 patents, and has trained more than 100 graduate students and postdoctoral students in his laboratory.

Frederick W Lampe (1927-2000) was a Professor of Chemistry at the Pennsylvania State University. Professor Lampe was born in Chicago. He served in the United States Navy from 1944 to 1946, and later received a B.S. degree from Michigan State University and a Ph.D. degree from Columbia University. He then spent seven years as a research scientist with the Humble Oil and Refining Company in Texas before moving to Penn State in 1960. Professor Lampe was a physical chemist whose polymer interests were in the areas of radiation-induced polymerizations, kinetics of polymerization processes, application of mass spectrometry to polymer degradation processes, statistical mechanics, and molecular weight methods. He was also interested in gaseous ion reactions, photochemistry, and the effects of ionizing radiation on materials. He was the author or co-author of over 160 research papers and review articles, and held five patents on polymer chemistry and radiation chemistry. He was also a visiting professor at the University of Freiburg, Germany, and at the Hahn-Meitner Nuclear Research Institute in Berlin. His honors included the Alexander von Humboldt Senior Scientist Award, a National Science Foundation Senior Postdoctoral Fellowship, and a Robert A. Welch Lecturship. Professor Lampe also served for five years as the Head of the Chemistry Department at Penn State.

James E. Mark was born in Wilkes-Barre, Pennsylvania. He received a B.S. degree in Chemistry from Wilkes College and his Ph.D. in Physical Chemistry from the University of Pennsylvania. After serving as a Postdoctoral Fellow at Stanford University with Professor Paul J. Flory, he was an Assistant Professor at the Polytechnic Institute of Brooklyn before moving to the University of Michigan, where he became a Full Professor in 1972. In 1977 he assumed the position of Professor of Chemistry at the University of Cincinnati, where he was Chairman of the Physical Chemistry division and Director of the Polymer Research Center. In 1987 he was named to the first Distinguished Professorship at Cincinnati. Dr. Mark's research interests include the physical chemistry of polymers, elasticity of polymer networks, liquid crystalline polymers, hybrid organic-inorganic composites, and a variety of computer simulations. He has lectured widely on polymer chemistry, is a consultant to industry, and has organized a number of polymer-related short courses. He has published over 600 research papers and has coauthored or coedited eighteen books. Among his awards are the A.C.S Applied Polymer Science Award and the A.C.S. Polymer Division Paul. J. Flory Polymer Education Award, the Whitby Award, and the Charles Goodyear Medal from the A.C.S Rubber Division. He is the founding Editor of the journal Computational and Theoretical Polymer Science and serves on the Editorial Boards of a number of other journals. He has also been a Turner Alfrey Visiting Professor and has received the Edward W Morley Award from the A.C.S. Cleveland Section.

Table of Contents

Preface xiii
About the Authors xvii
PART I SYNTHESIS AND REACTIONS OF POLYMERS
The Scope of Polymer Chemistry
1(26)
Introduction
1(1)
Definitions
2(14)
Different Types of Polymers
16(5)
Historical Overview
21(4)
Study Questions
25(1)
Suggestions for Further Reading
26(1)
Condensation and Other Step-Type Polymerizations
27(28)
Introduction
27(7)
Specific Condensation Polymerizations
34(15)
Other Step-Type Polymerizations
49(4)
Conclusions
53(1)
Study Questions
53(1)
Suggestions for Further Reading
54(1)
Free-Radical Polymerization
55(23)
Addition Reactions
55(1)
Free-Radical Addition Reactions
55(1)
Initiators for Free-Radical Polymerization
56(1)
Monomers for Free-Radical Polymerization
57(1)
Solvents and Systems
57(1)
Typical Experimental Procedures
58(1)
Chain Reactions
59(2)
Free-Radical Initiators
61(6)
Reactions of Initiator Radicals with the Monomer
67(1)
Radical Chain Propagation
68(1)
Chain Transfer Reactions
69(1)
Free-Radical Chain Termination
70(3)
Atom Transfer Radical Polymerizations
73(1)
Polymerizations in Supercritical Carbon Dioxide
74(1)
Study Questions
75(1)
Suggestions for Further Reading
76(2)
Ionic and Coordination Polymerization
78(38)
Introduction
78(1)
Stereoregular Polymers
79(2)
Anionic and Coordination Polymerization
81(21)
Group Transfer Polymerization
102(2)
Cationic Polymerization
104(8)
A Comparison of Polymers Prepared by Different Routes
112(1)
Study Questions
112(2)
Suggestions for Further Reading
114(2)
Photolytic, Radiation, and Electrolytic Polymerization
116(28)
Introduction
116(1)
Photochemical Polymerization
116(8)
Radiation-Induced Polymerization
124(14)
Plasma Polymerization
138(1)
Electrochemically Initiated Polymerizations
138(3)
Study Questions
141(1)
Suggestions for Further Reading
142(2)
Polymerization of Cyclic Organic Compounds
144(24)
Introduction
144(1)
Cyclic Compounds that Resist Polymerization
145(2)
General Mechanisms of Classical Ring-Opening Polymerizations
147(1)
Cyclic Ethers
147(8)
Lactones
155(1)
Glycolides and Lactides
155(1)
Cyclic Anhydrides
156(1)
Cyclic Carbonates
156(1)
Lactams
157(2)
Ethylenimine
159(1)
Cycloalkenes
160(1)
The Special Case of Oxazoline Polymerizations
160(1)
No-Catalyst Copolymerizations
161(1)
Free-Radical Ring-Opening Polymerization
162(1)
Cyclopolymerizations
163(2)
Poly(para-xylene)
165(1)
Study Questions
165(1)
Suggestions for Further Reading
166(2)
Reactions of Synthetic Polymers
168(23)
Introduction
168(1)
Reactions Involving the Main Chain
168(8)
Reactions Involving the Side Groups
176(9)
Surface Reactions of Polymers
185(3)
Study Questions
188(1)
Suggestions for Further Reading
189(2)
Biological Polymers and Their Reactions
191(38)
Introduction
191(1)
Polysaccharides
192(6)
Proteins and Polypeptides
198(18)
Polynucleotides
216(9)
Biological Synthesis of Polyesters
225(1)
Study Questions
226(1)
Suggestions for Further Reading
227(2)
Inorganic Elements in Polymers
229(48)
Reasons for the Incorporation of Inorganic Elements into Polymers
229(2)
Scope of the Field
231(1)
Organic Polymers with Inorganic Elements in the Side Groups
232(3)
Polymers with Inorganic Elements in the Main Chain
235(1)
Poly(organosiloxanes) (Silicone Polymers)
235(4)
Siloxane-Arylene and Siloxane-Carborane Polymers
239(2)
Phthalocyanine Shishkebab Polymers
241(1)
Polyorganosilanes and Polycarbosilanes
241(3)
Phosphazene Polymers
244(10)
Poly(carbo-, thio-, and thionyl-phosphazenes)
254(1)
Polymeric Sulfur
255(2)
Poly(sulfur nitride) (Polythiazyl)
257(2)
Polymers with Metal Coordination in the Main Chain
259(2)
Mineralogical and Preceramic Polymers
261(8)
Conclusions
269(1)
Study Questions
269(1)
Suggestions for Further Reading
270(7)
PART II THERMODYNAMICS AND KINETICS OF POLYMERIZATION
Polymerization and Depolymerization Equilibria
277(29)
Introduction
277(1)
Monomer-Polymer Equilibria
278(1)
Examples of Ring-Polymer Interconversions
278(1)
``Unpolymerizable'' Compounds
279(1)
The General Thermodynamic Problem
280(1)
Specific Thermodynamic Effects
281(1)
Standard Enthalpies, Entropies, and Free Energies of Polymerization
282(2)
Specific Monomer-Polymer Equilibria
284(2)
Influence of ΔH and ΔS on Ring-Chain Equilibria (Nonrigorous Approach)
286(4)
The Sulfur Equilibrium (Rigorous Approach)
290(2)
The Statistical Influence
292(4)
Molecular Structural Effects (Qualitative Approach)
296(1)
Skeletal Bond Energies
296(1)
Skeletal Bond Angles
297(1)
Aromaticity and Delocalization
298(1)
Side-Group Interactions
298(4)
The Mechanistic Aspect
302(1)
Study Questions
303(1)
Suggestions for Further Reading
304(2)
Kinetics of Condensation (Step-Growth) Polymerization
306(27)
Introduction
306(1)
The Reactivity of Large Molecules
307(3)
Rates of Polycondensation Reactions
310(1)
Kinetics of Polyesterification
310(4)
Time Dependence of the Average Degree of Polymerization and the Average Molecular Weight
314(4)
Molecular-Weight Distributions of Linear Condensation Polymers
318(5)
Effect of Nonstoichiometric Reactant Ratios on Linear Condensation Polymers
323
Branched and Crosslinked Condensation Polymers
235(93)
Study Questions
328(3)
Suggestions for Further Reading
331(2)
Kinetics of Free-Radical Polymerization
333(39)
Introduction
333(1)
Approximations
334(3)
Steady-State Concentrations of the Propagating Radicals
337(2)
Rate of Polymerization
339(6)
Average Degree of Polymerization and Average Molecular Weight
345(2)
Distribution of the Degree of Polymerization and of Molecular Weight
347(4)
Chain Transfer
351(6)
Dependence of the Degree of Polymerization on Temperature
357(2)
Absolute Propagation and Termination Rate Constants
359(1)
Copolymerization
360(8)
Study Questions
368(3)
Suggestions for Further Reading
371(1)
Kinetics of Ionic Polymerization
372(21)
Differences between Ionic and Free-Radical Kinetics
372(1)
Anionic Polymerization
373(9)
Cationic Polymerization
382(7)
Study Questions
389(1)
Suggestions for Further Reading
390(3)
PART III PHYSICAL CHARACTERIZATION OF POLYMERS
Determination of Absolute Molecular Weights
393(58)
Introduction
393(2)
Solubility of High Polymers
395(7)
End-Group Analysis, Colligative Properties, and Number Average Molecular Weights
402(1)
Colligative Properties and Number Average Molecular Weights
403(1)
Osmotic-Pressure Measurement of Absolute Molecular Weights
404(10)
Light Scattering for Measurement of Absolute Molecular Weight and Size
414(18)
Ultracentrifugation as a Method for Measurement of Absolute Molecular Weights
432(12)
Study Questions
444(5)
Suggestions for Further Reading
449(2)
Secondary Methods for Molecular-Weight Determination
451(41)
Introduction
451(1)
Solution Viscosity
452(16)
Vapor-Phase Osmometry
468(3)
Molecular Weight Distributions
471(7)
Gel Permeation Chromatography
478(9)
Study Questions
487(3)
Suggestions for Further Reading
490(2)
Thermodynamics of Solutions of High Polymers
492(29)
Introduction
492(1)
Definition of an Ideal Solution
493(1)
Entropy of Mixing of Solvent and Solute
494(8)
Enthalpy of Mixing of Solvent and Polymeric Solute
502(1)
Free Energy of Mixing of Polymeric Solute with Solvent
503(1)
Chemical Potential and Activity of Solvent
503(2)
The Osmotic Pressure of Polymeric Solutions
505(2)
Some Other Applications of the Flory-Huggins Theory
507(3)
Limitations of the Theory
510(1)
Dilute Solutions, and Chains Unperturbed by Excluded Volume Effects
511(4)
More Refined Theories
515(1)
Study Questions
516(3)
Suggestions for Further Reading
519(2)
Morphology, Glass Transitions, and Polymer Crystallinity
521(40)
Morphological Changes in Polymers
521(1)
Characteristics of the Viscoelastic State
522(10)
Transition Thermodynamics
532(2)
The Glass Transition Temperature
534(2)
Detection of Glass Transitions
536(7)
Microcrystallinity
543(2)
Influence of Crystallinity on Physical Properties
545(1)
Enhancement of Crystallinity
546(2)
Kinetics of Crystallization
548(4)
Detection and Measurement of Crystallinity
552(3)
Polymer Single Crystals
555(2)
Study Questions
557(1)
Suggestions for Further Reading
557(4)
Conformational Analysis of Polymers
561(39)
The Role of Conformational Analysis
561(2)
Polymer Conformations
563(1)
Small-Molecule Models for Polymers
564(7)
Short-Chain Models for Polymers
571(8)
Relationship to the Statistical Coil Concept
579(4)
Influence of the Boltzmann Distribution
583(1)
The Statistical Matrix Approach
584(2)
Applications of Conformational Analysis
586(8)
Polypeptides and Proteins
594(1)
Molecular Graphics
595(1)
Study Questions
596(1)
Suggestions for Further Reading
597(3)
Polymer Structure by Diffraction, Scattering, and Spectroscopy
600(31)
Introduction
600(1)
X-Ray Diffraction
600(1)
Experimental Aspects
601(7)
Determination of Molecular Structure and Conformation
608(14)
Scattering
622(2)
Spectroscopy
624(1)
Study Questions
625(1)
Suggestions for Further Reading
626(5)
PART IV FABRICATION AND TESTING OF POLYMERS
Fabrication of Polymers
631(32)
Introduction
631(1)
Preparation of Films
631(7)
Fibers
638(8)
Chain Orientation and Reinforcement
646(3)
Fabrication of Shaped Objects
649(7)
Expanded Polymers
656(1)
Reinforced Polymers
657(1)
Elastomer Technology
658(1)
Surface Coatings
659(1)
Study Questions
660(1)
Suggestions for Further Reading
661(2)
The Testing of Polymers
663(26)
Introduction
663(1)
Fundamental Physicochemical Tests
663(1)
Mechanical Tests
664(5)
Rubberlike Elasticity
669(12)
Thermal Properties
681(1)
Electrical Tests
682(1)
Environmental Stability
683(1)
Additional Properties
684(1)
Study Questions
685(1)
Suggestions for Further Reading
686(3)
PART V MOLECULAR STRUCTURE, PROPERTIES, AND USES
Relationship between Macromolecular Structure and Properties
689(28)
Introduction
689(1)
Influence by the Macromolecular Skeleton
690(6)
Influence of Different Side Groups
696(9)
Relationsip to Surface Properties
705(1)
Structural Influences on Solid State Properties
705(8)
How Scientists Design New Polymers and Polymeric Materials
713(1)
Study Questions
714(1)
Suggestions for Further Reading
715(2)
Electroactive and Electro-Optical Polymers
717(37)
Introduction
717(1)
Ionic Conduction in Solid Polymers
718(6)
Pyrolysate Polymers and Composite Polymers with Conducting Domains
724(1)
Electronically Conducting Polymers
724(17)
Optical and Electro-Optical Devices
741(9)
Comment
750(1)
Study Questions
750(1)
Suggestions for Further Reading
751(3)
Biomedical Applications of Synthetic Polymers
754(39)
Uses for Polymers in Biomedicine
754(1)
Biostable Materials
755(3)
Cardiovascular Applications
758(4)
Tissue Adhesives and Artificial Skin
762(1)
Bones, Joints, and Teeth
762(1)
Contact Lenses and Intraocular Lenses
763(1)
Artificial Kidney and Hemodialysis Materials
764(1)
Oxygen-Transport Membranes
764(1)
Bioerodible Polymers
764(1)
Surgical Sutures
765(1)
Tissue Engineering Polymers
765(1)
Controlled Release of Drugs
766(4)
Polymeric Blood Substitutes
770(1)
Study Questions
770(1)
Suggestions for Further Reading
771(3)
APPENDICES
Appendix I Polymer Nomenclature
774(5)
Introduction
774(1)
Structural and Source Names
774(1)
Parentheses
775(1)
End Groups
775(1)
Polymers Prepared from Unsaturated Monomers
775(1)
Polymers Prepared by Step-Type Processes
776(1)
Inorganic Polymers
777(1)
Abbreviations, Acronyms, and Trade Names
778(1)
Appendix II Properties and Uses of Selected Polymers
779(14)
Author Index 793(11)
Subject Index 804

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Excerpts

This third edition ofContemporary Polymer Chemistry,like the two preceding editions, is designed as an introduction to polymers for students of chemistry, physics, chemical engineering, materials science, and biomaterials. It assumes a basic knowledge of subjects taught in university undergraduate programs in the above disciplines. Specifically, the book aims to broaden the perspective of specialists in different technical areas to the point where they can appreciate the scope, importance, and future potential of polymer chemistry and technology. Thus, in writing this book we have kept in mind the individual who has a sound knowledge of basic science but needs to know more about polymers for future academic research or teaching or for entry into the polymer industry. For this reason, many topics that are well-known to practicing polymer scientists are handled here from first principles.More rigorous and more comprehensive treatments exist for nearly all of the topics discussed in this book. However, few attempts have been made to bring together synthetic, structural, kinetic, thermodynamic, and use-oriented material in one volume. Our aim has been to provide a broad, coherent introduction to modern polymer chemistry and to direct the reader to more detailed sources for advanced study.This edition has undergone an appreciable expansion compared to the earlier volumes. This reflects the widening scope of the field and the need to include recent advances in polymer synthesis as well as to broaden the treatment of polymer characterization methods and the physics and materials science aspects of the subject. Contributions by new co-author James E. Mark have added considerably to this widened perspective. A number of new topics have also been introduced, including insights into rubberlike elasticity, viscoelasticity, biomimicry, and the materials science of structure-property relationships. The list of references for further reading and the study questions, problems, and solutions have been updated extensively throughout the book.The book is divided into five parts.Part I(Chapters 1-9) provides an introduction to the different classes of polymers and the ways in which they are synthesized and modified. Individual chapters deal with condensation, free-radical, and ionic or coordination polymerization, with photolytic, high energy radiation, and electrolytic polymerization, polymerization of cyclic compounds, biological macromolecules, with the ways that synthetic polymers can be modified chemically, and with polymers that contain inorganic elements. Several of the chapters in this section have been revised to reflect recent developments. For example, new sections have been included on molecular weight distributions, dendrimers and telechelic polymers, polymer surface chemistry, organometallicinitiated polymerizations, atom transfer radical reactions, polymerizations in supercritical carbon dioxide, and inorganic polymers. Thus, the emphasis in these chapters is on descriptive chemistry, general principles, and synthetic issues. The material is this section should be understandable to students who have taken undergraduate courses in general chemistry, and organic, inorganic, or biological chemistry. These chapters form the groundwork for the sections that follow.Part II(Chapters 10-13) deals with thermodynamics, equilibria, and polymerization kinetics. Chapter 10 provides an elementary overview of the underlying principles that determine whether a monomer or a cyclic compound will polymerize or if a polymer will depolymerize. Chapters 11,12, and 13 deal respectively with the kinetics of condensation, free-radical, and ionic polymerizations. A unique feature of these chapters is the full derivation of the kinetic expressions, with every attempt made to explain the underlying principles for each step. This should enable the treatments to be understood by anyone with a basic background

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