Conformations

Contents

Preface ...................................................................................................... ix

Authors ...................................................................................................xiii

Chapter 1 Polymer Physics or Why Polymers and Their Materials

Can Behave in Unique Ways ................................................ 1

Introduction .......................................................................... 1

References ............................................................................ 7

Discussion Questions ............................................................ 7

Chapter 2 Polymer Chemistry or the Detailed Microstructures

of Polymers ........................................................................... 9

Polymerization ...................................................................... 9

Step-Growth Polymers ..................................................... 9

Chain-Growth Polymers .................................................11

Chain-Growth Polymer Microstructures ................... 12

Branching and Cross-Linking ....................................14

Comonomer Sequences ...............................................17

References ...........................................................................18

Discussion Questions ...........................................................18

Chapter 3 Determining the Microstructural Dependent

Conformational Preferences of Polymer Chains .................19

Introduction .........................................................................19

References ...........................................................................41

Discussion Questions .......................................................... 42

Appendix: Fortran Program for Hexane "by-hand"

Conformational Populations and Distances ........................43

Chapter 4 Experimental Determination of Polymer

Microstructures with 13C-NMR Spectroscopy ................... 57

Introduction ........................................................................ 57

Substituents Effects ............................................................ 58

References .......................................................................... 67

Discussion Questions .......................................................... 67

Appendix 4.1: Polymer Macrostructures and the

Kerr Effect .......................................................................... 68

Appendix 4.2: Access to Program (FORTRAN) Used

to Calculate Molar Kerr Constants for Polymers ............... 84

Chapter 5 Connecting the Behaviors/Properties of Polymer

Solutions and Liquids to the Microstructural

Dependent Conformational Preferences of Their

Polymer Chains .................................................................109

Introduction .......................................................................109

Intrinsic Viscosities of Dilute Polymer Solutions ..............112

Polymer Entanglement ......................................................115

Dynamic Behaviors of Polymer Solutions and Melts ....... 120

References ........................................................................ 120

Discussion Questions .........................................................121

Chapter 6 Connecting the Behaviors/Properties of Polymer Solids

to the Microstructural Dependent Conformational

Preferences of Their Individual Polymer Chains ..............123

Introduction .......................................................................123

Solid Polymer Properties and Zconf ................................... 124

Copolymer Tgs and Their Comonomer-Sequence

Dependence ...................................................................... 125

Melting Temperatures of Semi-crystalline Polymers ........132

The Flexibilities of Polymers with

1,4-attached Phenyl Rings in Their Backbones ................140

Poly(ethylene phthalates) ...............................................140

Polymers with High Impact Strengths Well

Below Their Glass-Transition Temperatures .................144

Elastic Polymer Networks .................................................149

Thermodynamics of Polymer Networks .......................151

Polymer Network Topology ..........................................152

Modulus of a Polymer Network ....................................167

References .........................................................................174

Discussion Questions .........................................................177

Appendix 6.1 .....................................................................178

Chapter 7 Biopolymer Structures and Behaviors

with Comparisons to Synthetic Polymers ..........................179

Introduction .......................................................................179

Polysaccharides .................................................................179

Proteins ..............................................................................184

Polynucleotides ................................................................. 200

References .........................................................................212

Discussion Questions .........................................................215

Index ......................................................................................................217