Conformational Analysis of Polymers: Methods and Techniques for Structure-Property Relationships and Molecular Design

ISBN-13: 9781119716358 / Angielski / Twarda / 2023 / 500 str.

Sasanuma

Spis treści

Preface xiiAcknowledgments xviAbout the Author xviiAcronyms xviiiPart I Fundamentals of Polymer Physical Chemistry 11 Stereochemistry of Polymers 31.1 Configuration 31.2 Connection Type of Monomeric Units 51.3 Nitrogen Inversion 51.4 Conformation 81.5 Secondary Structure 91.6 Double Helix 112 Models for Polymeric Chains 132.1 Spatial Configuration of Polymeric Chain 132.2 Freely Jointed Chain 132.3 Freely Rotating Chain 152.4 Simple Chain with Rotational Barrier 162.5 Gaussian Chain 173 Lattice Model 213.1 Lattice Model of Small Molecules 213.2 Flory-Huggins Theory 223.2.1 Entropy of Polymeric Chain 223.2.2 Enthalpy of Mixing 253.2.3 Chemical Potential 263.2.4 Excluded-Volume Effect I 283.2.5 Excluded-volume Effect II 323.2.6 Phase Equilibrium 353.3 Intrinsic Viscosity 363.3.1 Stockmayer-Fixman Plot 37Exercise 384 Rubber Elasticity 414.1 Thermodynamics of Rubber Elasticity 414.2 Adiabatic Stretching: Gough-Joule Effect 454.3 Phenomenological Theory: Affine Model 464.4 Temperature Dependence of Chain Dimension in Rubber 48Part II Quantum Chemistry 515 Ab Initio Molecular Orbital Theory 555.1 Schrödinger Equation 555.2 Wave Function 565.3 Basis Set 575.4 Hartree-Fock Method 585.5 Roothaan-Hall Equation 595.6 Electron Correlation 606 Density Functional Theory 636.1 Exchange and Correlation Functionals 656.2 Dispersion-force Correction 677 Solvent Effect 698 Statistical Thermodynamics for Quantum Chemistry 758.1 Translational Motion 768.2 Rotational Motion 778.3 Vibrational Motion 788.4 Electronic Excitation 808.5 Thermochemistry 819 NMR Parameters 859.1 Chemical Shift 869.1.1 Example: Determination of Reaction Process from NMR Chemical Shifts 889.2 Indirect Spin-Spin Coupling Constant 929.2.1 Example 1: Calculation of Vicinal Coupling Constants of Cyclic Compound 939.2.2 Example 2: Derivation of Karplus Equation and Its Application 9510 Periodic Quantum Chemistry 9910.1 Direct Lattice and Reciprocal Lattice 9910.2 Bloch Function 10010.3 One-electron Crystal Orbital 10110.4 Structural Optimization 10210.5 Crystal Elasticity 10410.6 Vibrational Calculation 10810.7 Thermal Chemistry 11010.8 Cohesive (Interchain Interaction) Energy 112Part III Statistical Mechanics of Chain Molecules: Rotational Isomeric State Scheme 11511 Conventional RIS Scheme 11711.1 Chain Dimension 12112 Refined RIS Scheme 12512.1 RIS Scheme Including Middle-range Intramolecular Interactions 12913 Inversional-Rotational Isomeric State (IRIS) Scheme 13713.1 Pseudoasymmetry for Polyamines 13713.2 Inversional-Rotational Isomerization 13713.3 Statistical Weight Matrices of Meso and Racemo di-MEDA 13813.4 Statistical Weight Matrices of PEI 13913.5 Diad Probability and Bond Conformation 14213.6 Characteristic Ratio 14413.7 Orientational Correlation Between Bonds 14513.8 Solubility of Polyamines 14814 RIS Scheme Combined with Stochastic Process 15114.1 Polymeric Chains with Internally Rotatable Side Chains 153Part IV Experimental Methods 16115 Nuclear Magnetic Resonance (NMR) 16315.1 Conformational Analysis of Isotactic Poly(propylene oxide) 16315.1.1 1 H NMR Vicinal Coupling Constant 16415.1.2 Ab initio MO Calculation 16815.1.3 RIS Analysis of Bond Conformations 17115.1.4 Configuration-dependent Properties 17215.2 Carbon-13 NMR Chemical Shifts of Dimeric Propylene Oxides 17315.2.1 Theoretical Basis 17515.2.2 13 C NMR Spectra and Assignment 17615.2.3 Calculation of Chemical Shift by RIS Scheme 17915.3 Model Compound of Poly(ethylene terephthalate) 18116 Scattering Methods 18716.1 Static Light Scattering (SLS) 18716.1.1 Instrumentation and Sample Preparation for SLS 18916.1.2 Application of SLS: Chain Dimensions of Polysilanes in the ThetaState 19116.2 Dynamic Light Scattering (DLS) 19516.2.1 Application of DLS: Size Distribution of Polystyrene Latex Particles 19716.2.2 Application of SLS and DLS to Poly(N-methylethylene imine) Solutions 19816.3 Small-angle Neutron Scattering (SANS) 20116.3.1 Application of SANS to Amorphous PET 204Part V Applications: Conformational Analysis and Elucidation of Structure-property Relationships of Polymers 20717 Polyethers 21517.1 Poly(methylene oxide) (PMO) 21517.2 Poly(ethylene oxide) (PEO) 21717.3 Poly(propylene oxide) (PPO) 22617.4 Poly(trimethylene oxide) (PTrMO) 22817.5 Poly(tetramethylene oxide) (PTetMO) 22918 Polyamines 23518.1 Poly(ethylene imine) (PEI) 23618.2 Poly(N-methylethylene imine) (PMEI) 23718.3 Poly(trimethylene imine) (PTMI) and Poly(N-methyltrimethylene imine) (pmtmi) 23819 Polyphosphines 24119.1 Possibility of Phosphorus Inversion 24119.2 Intramolecular Interactions Related to Phosphorus 24319.3 RIS Calculation 24419.4 Functions and Stability 24820 Polysulfides 24920.1 Poly(methylene sulfide) (PMS) 24920.1.1 Crystal Structure of PMS 25320.2 Poly(ethylene sulfide) (PES) 25320.3 Poly(propylene sulfide) (PPS) 26020.4 Poly(trimethylene sulfide) (PTrMS) 26521 Polyselenides 26921.1 Poly(methylene selenide) (PMSe) 26921.1.1 Crystal Structure of PMSe 27021.2 Poly(ethylene selenide) (PESe) 27421.3 Poly(trimethylene selenide) (PTrMSe) 27621.4 Summary 27722 Alternating Copolymers Including Ethylene-imine, Ethylene-oxide, and Ethylene-sulfide Units 27922.1 Synthesis of P(EI-ES) 28623 Aromatic Polyester (PET, PTT, and PBT) 28923.1 Correction for MP2 Energy of pi-pi Interaction 29023.2 Dipole Moment and Molar Kerr Constant 29323.3 Configurational Properties 29623.4 Crystal Structure 29724 Aliphatic Polyesters 30124.1 Poly(glycolic acid) (PGA) and Poly(2-hydroxybutyrate) (P2HB) 30124.1.1 MO Calculation and NMR Experiment 30224.1.2 RIS Calculation 30524.1.3 Periodic DFT Calculation on PGA Crystal 30924.2 Poly(lactic acid) (Poly(lactide), PLA) 31224.2.1 MO Calculation and NMR Experiment 31324.2.2 RIS Calculation 31724.3 Poly((R)-3-hydroxybutyrate) (P3HB) 32124.3.1 NMR Experiment 32124.3.2 MO Calculation 32324.3.3 RIS Calculation and Comparison with Experiment 32524.3.4 Crystal Structure 32624.4 Poly(epsilon-caprolactone) (PCL) 32724.4.1 MO Calculation 32824.4.2 NMR Experiment 33024.4.3 RIS Calculation 33024.4.4 Crystal Structure 33224.4.5 Crystal Elasticity 33324.5 Poly(ethylene succinate) (PES) and Poly(butylene succinate) (PBS) 33624.5.1 NMR Experiment 33724.5.2 MO Calculation 33824.5.3 RIS Calculation 33924.5.4 Crystal Structure 34024.6 Biodegradability of Polyesters 34225 Polycarbonates 34725.1 Poly(ethylene carbonate) (PEC) and Poly(propylene carbonate) (ppc) 34825.1.1 NMR Experiment 35125.1.2 MO Calculation 35125.1.3 RIS Calculation 35325.2 Poly(cyclohexene carbonate) (PCHC) 35725.2.1 MO Calculation 35825.2.2 NMR Experiment 36025.2.3 RIS Calculation 36125.2.4 Coherence Number 36426 Nylon 4 36726.1 MO Calculation 36826.2 NMR Experiment 37027 Aromatic Polyester, Polythionoester, Polythioester, Polydithioester, Polyamide, and Polythioamide 37327.1 MO Calculation 37527.2 Bond Conformation 37727.3 RIS Calculation, Thermal Properties, and Solubility 38028 Polysilanes 38328.1 Molecular Dynamics 38428.1.1 General Procedures 38428.1.2 PDBS and PDHS 38428.1.3 PMPrS 38728.2 RIS Calculation 38728.3 Physical Properties 38829 Polyethylene (PE) 391A FORTRAN Computer Program for Refined RIS Calculations on Polyethylene 399B Answers of Problems 423Bibliography 431Index 465

O autorze

Yuji Sasanuma, PhD was an associate professor in the Department of Applied Chemistry and Biotechnology and presided over the Environmentally-Friendly Polymeric Materials Laboratory at Chiba University. He had given lectures on statistical mechanics and polymer physical chemistry for both undergraduate and graduate courses.