Conformations Connecting the Chemical Structures and Material Behaviors of Polymers

Among the materials found in Nature’s many diverse living organisms or produced by human industry, those made from polymers are dominant. In Nature, they are not only dominant, but they are, as well, uniquely necessary to life. Conformations: Connecting the Chemical Structures and Material Behaviors of Polymers explores how the detailed chemical structures of polymers can be characterized, how their microstructural-dependent conformational preferences can be evaluated, and how these conformational preferences can be connected to the behaviors and properties of their materials.The authors examine the connections between the microstructures of polymers and the rich variety of physical properties they evidence. Detailed polymer architectures, including the molecular bonding and geometries of backbone and side-chain groups, monomer stereo- and regiosequences, comonomer sequences, and branching, are explicitly considered in the analysis of the conformational characteristics of polymers.This valuable reference provides practicing materials engineers as well as polymer and materials science students a means of understanding the differences in behaviors and properties of materials made from chemically distinct polymers. This knowledge can assist the reader design polymers with chemical structures that lead to their desired material behaviors and properties.

ContentsPreface ...................................................................................................... ixAuthors ...................................................................................................xiiiChapter 1 Polymer Physics or Why Polymers and Their MaterialsCan Behave in Unique Ways ................................................ 1Introduction .......................................................................... 1References ............................................................................ 7Discussion Questions ............................................................ 7Chapter 2 Polymer Chemistry or the Detailed Microstructuresof Polymers ........................................................................... 9Polymerization ...................................................................... 9Step-Growth Polymers ..................................................... 9Chain-Growth Polymers .................................................11Chain-Growth Polymer Microstructures ................... 12Branching and Cross-Linking ....................................14Comonomer Sequences ...............................................17References ...........................................................................18Discussion Questions ...........................................................18Chapter 3 Determining the Microstructural DependentConformational Preferences of Polymer Chains .................19Introduction .........................................................................19References ...........................................................................41Discussion Questions .......................................................... 42Appendix: Fortran Program for Hexane “by-hand”Conformational Populations and Distances ........................43Chapter 4 Experimental Determination of PolymerMicrostructures with 13C-NMR Spectroscopy ................... 57Introduction ........................................................................ 57Substituents Effects ............................................................ 58References .......................................................................... 67Discussion Questions .......................................................... 67Appendix 4.1: Polymer Macrostructures and theKerr Effect .......................................................................... 68Appendix 4.2: Access to Program (FORTRAN) Usedto Calculate Molar Kerr Constants for Polymers ............... 84Chapter 5 Connecting the Behaviors/Properties of PolymerSolutions and Liquids to the MicrostructuralDependent Conformational Preferences of TheirPolymer Chains .................................................................109Introduction .......................................................................109Intrinsic Viscosities of Dilute Polymer Solutions ..............112Polymer Entanglement ......................................................115Dynamic Behaviors of Polymer Solutions and Melts ....... 120References ........................................................................ 120Discussion Questions .........................................................121Chapter 6 Connecting the Behaviors/Properties of Polymer Solidsto the Microstructural Dependent ConformationalPreferences of Their Individual Polymer Chains ..............123Introduction .......................................................................123Solid Polymer Properties and Zconf ................................... 124Copolymer Tgs and Their Comonomer-SequenceDependence ...................................................................... 125Melting Temperatures of Semi-crystalline Polymers ........132The Flexibilities of Polymers with1,4-attached Phenyl Rings in Their Backbones ................140Poly(ethylene phthalates) ...............................................140Polymers with High Impact Strengths WellBelow Their Glass-Transition Temperatures .................144Elastic Polymer Networks .................................................149Thermodynamics of Polymer Networks .......................151Polymer Network Topology ..........................................152Modulus of a Polymer Network ....................................167References .........................................................................174Discussion Questions .........................................................177Appendix 6.1 .....................................................................178Chapter 7 Biopolymer Structures and Behaviorswith Comparisons to Synthetic Polymers ..........................179Introduction .......................................................................179Polysaccharides .................................................................179Proteins ..............................................................................184Polynucleotides ................................................................. 200References .........................................................................212Discussion Questions .........................................................215Index ......................................................................................................217

Alan Tonelli, born in Chicago in 1942,received a BS in Chemical Engineeringfrom the University of Kansas, in 1964 anda PhD in Polymer Chemistry from Stanfordin 1968, where he was associated with thelate “Father of Polymer Science” andNobelist Professor Paul J. Flory. He was amember of the Polymer Chemistry ResearchDepartment at AT&T-BELL Laboratories,Murray Hill, NJ for 23 years. In 1991, hejoined the Textile Engineering, Chemistry, & Science Department and theFiber & Polymer Science Program in the College of Textiles at NorthCarolina State University in Raleigh, where he is currently theINVISTA Prof. of Fiber & Polymer Chemistry. Professor Tonelli’s researchinterests include the conformations, configurations, and structures of syntheticand biological polymers, their determination by NMR, and establishingtheir effects on the physical properties of polymer materials. Morerecently, the formation, study, and use of inclusion complexes formed withpolymers and small molecule guests, such as urea and cyclodextrins, tonanostructure and safely deliver biologically active molecules to polymermaterials have been the focus of his research.Jialong Shen, born in Hangzhou, China, in1987, received a PhD in Fiber and PolymerScience from North Carolina StateUniversity, North Carolina, United States,in 2017. His research interests include themolecular basis of polymer glass transitions,host-guest supramolecular chemistry, andthe applications of bio-macromoleculessuch as carbohydrate polymers and enzymes.He is currently a postdoctoral researchscholar in the Textile Engineering, Chemistry, & Science Department atNorth Carolina State University.