Conformations-Connecting the Chemical Structures and Material Behaviors of Polymers

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