POLYMERS FROM THE INSIDE OUT An Introduction to Macromolecules

ALAN E. TONELLI with MOHAN SRINIVASARAO

WILEY-INTERSCIENCE

A John Wiley & Sons, Inc., Publication

New York • Chichester • Weinheim • Brisbane • Singapore • Toronto

CONTENTS

Preface ix

Acknowledgments xiii

Chapter Summary xv

1 INTRODUCTION 1

Long-Chain Molecules / 1 Conformations, Sizes, and Shapes / 3 Polymers and Time / 7 Polymer Physics and Chemistry / 9 Discussion Questions / 9 References / 10

2 STEP-GROWTH POLYMERIZATION 11

General Characteristics / 11 Molecular Weights of Step-Grown Polymers / 15 Step-Growth Monomers / 17 Step-Growth Polymers / 18

Polyesters / 18 Polyamides / 20

CONTENTS

Polyurethanes and Polyureas / 22 Formaldehyde Thermosets / 23

Step-Growth Polymerization in an Open System / 23 Stoichiometric Control of Step-Growth

Polymerization / 25 Molecular Weights and Their Distribution / 29 Kinetics of Step-Growth Polymerization / 30 Discussion Questions / 34 References / 36

CHAIN-GROWTH POLYMERIZATION

General Characteristics / 37 Contrast Between Chain- and Step-Growth

Polymerizations / 39 Details of Chain-Growth Polymerization / 42 Chain-Grown Polymer Sizes / 44 Transfer of Chain Growth / 45 Chain-Grown Polymers / 46 Kinetics of Chain-Growth Polymerization / 46 Chain-Grown Copolymers and the Copolymer

Equation / 51 Emulsion Polymerization / 56 Living Chain-Growth Polymerization / 57 Discussion Questions / 59 References / 60

THE MICROSTRUCTURES OF POLYMERS

Introduction / 62 Elements of Polymer Microstructure / 63 Copolymer Sequences / 68 Organization of Polymer Chains / 69 Polymer Microstructures and Properties / 70 Determination of Polymer Microstructure-NMR

Spectroscopy / 72

CONTENTS VII

Connecting Polymer Microstructures with Their NMR Spectra / 76

Discussion Questions / 85 References / 86

5 THE CONFORMATIONAL CHARACTERISTICS OF POLYMERS 87

Rotational Isomeric State Model / 87 Polymer Microstructures and Conformations / 93 Polymer Conformations and Sizes / 97 RIS Model and Polymer Dimensions / 100 Environmental Effects on Polymer Conformations / 105 Discussion Questions / 107 References / 108

6 SOLUTION PROPERTIES OF POLYMERS 110

Polymer Excluded Volume / 110 Volume Influenced by a Randomly Coiling Polymer / 112 Intrinsic Viscosity of a Polymer Solution / 114 Turbulent Flow of Polymer Solutions / 116 Polymer Solubility / 118 Anisotropie, Liquid Crystalline Polymer Solutions / 119 Polymer Molecular Weights Measured in Solution / 120

Osmotic Pressure of Polymer Solutions / 122 Light Scattering from Polymer Solutions / 122

Estimation of Polymer Dimensions in Solution / 125 Size-Exclusion Chromatography / 128 Time-Dependence of Flowing Polymer Solutions / 131 Discussion Questions / 133 References / 134

7 BULK PROPERTIES OF POLYMERS 137

Introduction / 137 Polymer Liquids / 138

VÜi CONTENTS

Polymer Glasses / 141 Polymer Elastomers / 148 Crystalline Polymers / 156 Melting of Polymer Crystals / 162 Polymer Fibers / 164 Melt Viscosity / 167 Polymer Glass-Transition Temperatures / 171 Impact Strength of Polymers / 174 Modulus of an Elastomeric Polymer Network / 177 Polymer Melting / 180 Discussion Questions / 184 References / 186

8 NATURALLY OCCURRING BIOPOLYMERS 189

Polysaccharides / 189 Polypeptides and Proteins / 195 Poly(Nucleic Acids) / 213 DNA-Directed Protein Synthesis / 218 Protein Folding / 223 DNA Replication and Transcription / 231 The Genetic Code / 233 Discussion Questions / 237 References / 239

Index 243