Description
Contents Contributors xv Preface xvii Acknowledgments xxiii Acronyms xxv 1 Stereochemistry of Polymers 3 1.1 Configuration 3 1.2 Connection Type of Monomeric Units 6 1.3 Nitrogen Inversion 8 1.4 Conformation 10 1.5 Secondary Structure 12 1.6 Double Helix 14 2 Models for Polymeric Chains 17 2.1 Spatial Configuration of Polymeric Chain 17 2.2 Freely Jointed Chain 19 2.3 Freely Rotating Chain 20 2.4 Simple Chain with Rotational Barrier 21 2.5 Gaussian Chain 23 3 Lattice Model 29 3.1 Lattice Model of Small Molecules 29 vii 3.2 Flory-Huggins Theory 32 3.2.1 Entropy of Polymeric Chain 32 3.2.2 Enthalpy of Mixing 36 3.2.3 Chemical Potential 38 3.2.4 Excluded-Volume Effect I 40 3.2.5 Excluded-Volume Effect II 46 3.2.6 Phase Equilibrium 50 3.3 Intrinsic Viscosity 52 3.3.1 Stockmayer-Fixman Plot 54 4 Rubber Elasticity 59 4.1 Thermodynamics of Rubber Elasticity 61 4.2 Adiabatic Stretching: Gough-Joule Effect 65 4.3 Phenomenological Theory: Affine Model 67 4.4 Temperature Dependence of Chain Dimension in Rubber 70 5 Ab Initio Molecular Orbital Theory 77 5.1 Schr ? odinger Equation 77 5.2 Wave Function 79 5.3 Basis Set 80 5.4 Hartree-Fock Method 82 5.5 Roothaan-Hall Equation 83 5.6 Electron Correlation 84 6 Density Functional Theory 89 viii 6.1 Exchange and Correlation Functionals 91 6.2 Dispersion-Force Correction 94 7 Solvent E ect 97 8 Statistical Thermodynamics for Quantum Chemistry 105 8.1 Translational Motion 107 8.2 Rotational Motion 108 8.3 Vibrational Motion 110 8.4 Electronic Excitation 113 8.5 Thermochemistry 114 9 NMR Parameters 121 9.1 Chemical Shift 122 9.1.1 Example: Determination of Reaction Process from NMR Chemical Shifts 125 9.2 Indirect Spin-Spin Coupling Constant 131 9.2.1 Example 1: Calculation of Vicinal Coupling Constants of Cyclic Compound 132 9.2.2 Example 2: Derivation of Karplus Equation and Its Application : 136 10 Periodic Quantum Chemistry 139 10.1 Direct Lattice and Reciprocal Lattice 139 10.2 Bloch Function 141 10.3 One-Electron Crystal Orbital 143 ix 10.4 Structural Optimization 144 10.5 Crystal Elasticity 146 10.6 Vibrational Calculation 153 10.7 Thermal Chemistry 156 10.8 Cohesive (Interchain Interaction) Energy 159 11 Conventional RIS Scheme 165 11.1 Chain Dimension 171 12 Refined RIS Scheme 175 12.1 RIS Scheme Including Middle-Range Intramolecular Interactions 181 13 Inversional-Rotational Isomeric State (IRIS) Scheme 191 13.1 Pseudo-asymmetry for Polyamines 191 13.2 Inversional-Rotational Isomerization 191 13.3 Statistical Weight Matrices of Meso and Racemo di-MEDA 192 13.4 Statistical Weight Matrices of PEI 194 13.5 Diad Probability and Bond Conformation 200 13.6 Characteristic Ratio 202 13.7 Orientational Correlation between Bonds 205 13.8 Solubility of Polyamines 208 14 RIS Scheme Combined with Stochastic Process 211 14.1 Polymeric Chains with Internally Rotatable Side Chains 219 15 Nuclear Magnetic Resonance (NMR) 225 15.1 Conformational Analysis of Isotactic Poly(propylene oxide) 225 x 15.1.1 1H NMR Vicinal Coupling Constant 227 15.1.2 Ab initio MO Calculation 232 15.1.3 RIS Analysis of Bond Conformations 237 15.1.4 Configuration-Dependent Properties 238 15.2 Carbon-13 NMR Chemical Shifts of Dimeric Propylene Oxides 240 15.2.1 Theoretical Basis 243 15.2.2 13C NMR Spectra and Assignment 245 15.2.3 Calculation of Chemical Shift by RIS Scheme 251 15.3 Model Compound of Poly(ethylene terephthalate) 253 16 Scattering Methods 263 16.1 Static Light Scattering (SLS) 264 16.1.1 Instrumentation and Sample Preparation for SLS 267 16.1.2 Application of SLS: Chain Dimensions of Polysilanes in the [1] State 270 16.2 Dynamic Light Scattering (DLS) 277 16.2.1 Application of DLS: Size Distribution of Polystyrene Latex Particles 280 16.2.2 Application of SLS and DLS to Poly(N-methylethylene imine) Solutions 283 16.3 Small-Angle Neutron Scattering (SANS) 288 16.3.1 Application of SANS to Amorphous PET 291 17 Polyethers 305 17.1 Poly(methylene oxide) (PMO) 305 xi 17.2 Poly(ethylene oxide) (PEO) 308 17.3 Poly(propylene oxide) (PPO) 323 17.4 Poly(trimethylene oxide) (PTrMO) 327 17.5 Poly(tetramethylene oxide) (PTetMO) 330 18 Polyamines 335 18.1 Poly(ethylene imine) (PEI) 336 18.2 Poly(N-methylethylene imine) (PMEI) 338 18.3 Poly(trimethylene imine) (PTMI) and Poly(N-methyltrimethylene imine) (PMTMI) 341 19 Polyphosphines 347 19.0.1 Possibility of Phosphorus Inversion 349 19.0.2 Intramolecular Interactions Related to Phosphorus 349 19.0.3 RIS Calculation 353 19.0.4 Functions and Stability 357 20 Polysulfides 359 20.1 Poly(methylene sulfide) (PMS) 359 20.1.1 Crystal Structure of PMS 365 20.2 Poly(ethylene sulfide) (PES) 368 20.3 Poly(propylene sulfide) (PPS) 375 20.4 Poly(trimethylene sulfide) (PTrMS) 384 21 Polyselenides 389 21.1 Poly(methylene selenide) (PMSe) 389 xii 21.1.1 Crystal Structures of PMSe 395 21.2 Poly(ethylene selenide) (PESe) 398 21.3 Poly(trimethylene selenide) (PTrMSe) 399 21.4 Summary 402 22 Alternating copolymers including ethylene-imine, ethylene-oxide, and ethylenesulfide units 403 22.1 Synthesis of P(EI-ES) 414 23 Aromatic polyester (PET, PTT, and PBT) 419 23.1 Correction for MP2 Energy of Interaction 421 23.2 Dipole Moment and Molar Kerr Constant 426 23.3 Configurational Properties 429 23.4 Crystal Structure 431 24 Aliphatic polyesters 437 24.1 Poly(glycolic acid) (PGA) and Poly(2-hydroxybutyrate) (P2HB) 438 24.2 Poly(lactic acid) (Poly(lactide) (PLA) 454 24.3 Poly((R)-3-hydroxybutyrate) (P3HB) 467 24.4 Poly(-caprolactone) (PCL) 476 24.5 Poly(ethylene succinate) (PES) and poly(butylene succinate) (PBS) 487 24.6 Biodegradability of Polyesters 497 25 Polycarbonates 505 25.1 Poly(ethylene carbonate) (PEC) and Poly(propylene carbonate) (PPC)507 25.2 Poly(cyclohexene carbonate) (PCHC) 519 26 Nylon 4 533 27 Aromatic Polyester, Polythionoester, Polythioester, Polydithioester, Polyamide, and Polythioamide 543 28 Polysilanes 557 29 Polyethylene (PE) 569 A FORTRAN computer program for refine RIS calculations on polyethylene 581 B Answers of Problems 607
