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