Preface About the Authors PART Ⅰ SYNTHESIS AND REACTIONS OF POLYMERS 1 The Scope of Polymer Chemistry Introduction Definitions Different Types of Polymers Historical Overview Study Questions Suggestions for Further Reading 2 Condensation and Other Step-Type Polymerizations Introduction Specific Condensation Polymerizations Other Step-Type Polymerizations Conclusions Study Questions Suggestions for Further Reading 3 Free-Radical Polymerization Addition Reactions Free-Radical Addition Reactions Initiators for Free-Radical Polymerization Monomers for Free-Radical Polymerization Solvents and Systems Typical Experimental Procedures Chain Reactions Free-Radical Initiators Reactions of Initiator Radicals with the Monomer Radical Chain Propagation Chain Transfer Reactions Free-Radical Chain Termination Atom Transfer Radical Polymerizations Polymerizations in Supercritical Carbon Dioxide Study Questions Sugggestions for Further Reading 4 Ionic and Coordination Polymerization Introduction Stereoregular Polymers Anionic and Coordination Polymerization Group Transfer Polymerization Cationic Polymerization A Comparison of Polymers Prepared by Different Routes Study Questions Suggestions for Further Reading 5 Photolytic, Radiation, and Electrolytic Polymerization Introduction Photochemical Polymerization Radiation-Induced Polymerization Plasma Polymerization Electrochemically Initiated Polymerizations Study Questions Suggestions for Further Reading 6 Polymerization of Cyclic Organic Compounds Introduction Cyclic Compounds that Resist Polymerization General Mechanisms of Classical Ring-Opening Polymerizations Cyclic Ethers Lactones Glycolides and Lactides Cyclic Anhydrides Cyclic Carbonates Lactams Ethylenimine Cycloalkenes The Special Case of Oxazoline Polymerizations No-Catalyst Copolymerizations Free-Radical Ring-Opening Polymerization Cyclopolymerizations Poly（para-xylene ） Study Questions Sugggestions for Further Reading 7 Reactions of Synthetic Polymers Introduction Reactions Involving the Main Chain Reactions Involving the Side Groups Surface Reactions of Polymers Study Questions Suggestions for Further Reading 8 Biological Polymers and Their Reactions Introduction Polysaccharides Proteins and Polypeptides Polynucleotides Biological Synthesis of Polyesters Study Questions Suggestions for Further Reading 9 Inorganic Elements in Polymers Reasons for the Incorporation of Inorganic Elements into Polymers Scope of the Field 231 Organic Polymers with Inorganic Elements in the Side Groups Polymers with Inorganic Elements in the Main Chain Poly（organosiloxanes） （Silicone Polymers） Siloxane-Arylene and Siloxane-Carborane Polymers Phthalocyanine Shishkebab Polymers Polyorganosilanes and Polycarbosilanes Phosphazene Polymers Poly（carbo-, thio-, and thionyl-phosphazenes） Polymeric Sulfur Poly（sulfur nitride）（Polythiazyl） Polymers with Metal Coordination in the Main Chain Mineralogical and Preceramic Polymers Conclusions Study Questions Suggestions for Further Reading PART Ⅱ THERMODYNAMICS AND KINETICS OF POLYMERIZATION 10 Polymerization and Depolymerization Equilibria Introduction Monomer-Polymer Equilibria Examples of Ring-Polymer Interconversions “Unpolymerizable” Compounds The General Thermodynamic Problem Specific Thermodynamic Effects Standard Enthalpies, Entropies, and Free Energies of Polymerization Specific Monomer-Polymer Equilibria Influence of ΔH and ΔS on Ring-Chain Equilibria （Nonrigorous Approach） The Sulfur Equilibrium （Rigorous Approach） The Statistical Influence Molecular Structural Effects （Qualitative Approach） Skeletal Bond Energies Skeletal Bond Angles Aromaticity and Delocalization Side-Group Interactions The Mechanistic Aspect Study Questions Suggestions for Further Reading 11 Kinetics of Condensation （Step-Growth） Polymerization Introduction 306 The Reactivity of Large Molecules Rates of Polycondensation Reactions Kinetics of Polyesterification Time Dependence of the Average Degree of Polymerization and the Average Molecular Weight Molecular-Weight Distributions of Linear Condensation Polymers Effect of Nonstoichiometric Reactant Ratios on Linear Condensation Polymers Branched and Crosslinked Condensation Polymers Study Questions Suggestions for Further Reading 12 Kinetics of Free-Radical Polymerization Introduction Approximations Steady-State Concentrations of the Propagating Radicals Rate of Polymerization 339 Average Degree of Polymerization and Average Molecular Weight Distribution of the Degree of Polymerization and of Molecular Weight Chain Transfer 351 Dependence of the Degree of Polymerization on Temperature Absolute Propagation and Termination Rate Constants Copolymerization Study Questions Suggestions for Further Reading 13 Kinetics of Ionic Polymerization Differences between Ionic and Free-Radical Kinetics Anionic Polymerization Cationic Polymerization Study Questions Suggestions for Further Reading PART Ⅲ PHYSICAL CHARACTERIZATION OF POLYMERS 14 Determination of Absolute Molecular Weights Introduction Solubility of High Polymers End-Group Analysis, Colligative Properties, and Number Average Molecular Weights Colligative Properties and Number Average Molecular Weights Osmotic-Pressure Measurement of Absolute Molecular Weights Light Scattering for Measurement of Absolute Molecular Weight and Size Ultracentrifugation as a Method for Measurement of Absolute Molecular Weights Study Questions Suggestions for Further Reading 15 Secondary Methods for Molecular-Weight Determination Introduction Solution Viscosity Vapor-Phase Osmometry Molecular Weight Distributions Gel Permeation Chromatography Study Questions Suggestions for Further Reading 16 Thermodynamics of Solutions of High Polymers Introduction Definition of an Ideal Solution Entropy of Mixing of Solvent and Solute Enthalpy of Mixing of Solvent and Polymeric Solute Free Energy of Mixing of Polymeric Solute with Solvent Chemical Potential and Activity of Solvent The Osmotic Pressure of Polymeric Solutions Some Other Applications of the Flory-Huggins Theory Limitations of the Theory Dilute Solutions, and Chains Unperturbed by Excluded Volume Effects More Refined Theories Study Questions Suggestions for Further Reading 17 Morphology, Glass Transitions, and Polymer Crystallinity Morphological Changes in Polymers Characteristics of the Viscoelastic State Transition Thermodynamics The Glass Transition Temperature Detection of Glass Transitions Microcrystallinity Influence of Crystallinity on Physical Properties Enhancement of Crystallinity Kinetics of Crystallization Detection and Measurement of Crystallinity Polymer Single Crystals Study Questions Suggestions for Further Reading 18 Conformational Analysis of Polymers The Role of Conformational Analysis Polymer Conformations Small-Molecule Models for Polymers Short-Chain Models for Polymers Relationship to the Statistical Coil Concept Influence of the Boltzmann Distribution The Statistical Matrix Approach Applications of Conformational Analysis Polypeptides and Proteins Molecular Graphics Study Questions Suggestions for Further Reading 19 Polymer Structure by Diffraction, Scattering, and Spectroscopy Introduction X-Ray Diffraction Experimental Aspects Determination of Molecular Structure and Conformation Scattering Spectroscopy Study Questions Suggestions for Further Reading PART IV FABRICATION AND TESTING OF POLYMERS 20 Fabrication of Polymers Introduction Preparation of Films Fibers Chain Orientation and Reinforcement Fabrication of Shaped Objects Expanded Polymers Reinforced Polymers Elastomer Technology Surface Coatings Study Questions Suggestions for Further Reading 21 The Testing of Polymers Introduction Fundamental Physicochemical Tests Mechanical Tests Rubberlike Elasticity Thermal Properties Electrical Tests Environmental Stability Additional Properties Study Questions Suggestions for Further Reading PART V MOLECULAR STRUCTURE, PROPERTIES, AND USES 22 Relationship between Macromolecular Structure and Properties Introduction Influence by the Macromolecular Skeleton Influence of Different Side Groups Relationsip to Surface Properties Structural Influences on Solid State Properties How Scientists Design New Polymers and Polymeric Materials Study Questions Suggestions for Further Reading 23 Electroactive and Electro-Optical Polymers Introduction Ionic Conduction in Solid Polymers Pyrolysate Polymers and Composite Polymers with Conducting Domains Electronically Conducting Polymers Optical and Electro-Optical Devices Comment Study Questions Suggestions for Further Reading 24 Biomedical Applications of Synthetic Polymers Uses for Polymers in Biomedicine Biostable Materials Cardiovascular Applications Tissue Adhesives and Artificial Skin Bones, Joints, and Teeth Contact Lenses and Intraocular Lenses Artificial Kidney and Hemodialysis Materials Oxygen-Transport Membranes Bioerodible Polymers Surgical Sutures Tissue Engineering Polymers Controlled Release of Drugs Polymeric Blood Substitutes Study Questions Suggestions for Further Reading APPENDICES Appendix I Polymer Nomenclature Introduction Structural and Source Names Parentheses End Groups Polymers Prepared from Unsaturated Monomers Polymers Prepared by Step-Type Processes Inorganic Polymers Abbreviations, Acronyms, and Trade Names Appendix H Properties and Uses of Selected Polymers AUTHOR INDEX SUBJECT INDEX
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