Cover
Half Title
Conformational Analysis of Polymers: Methods and Techniques for Structure-Property Relationships and Molecular Design
Copyright
Dedication
Contents
Preface
Acknowledgments
About the Author
Acronyms
Новая закладка
Part I. Fundamentals of Polymer Physical Chemistry
1. Stereochemistry of Polymers
1.1 Configuration
1.2 Connection Type of Monomeric Units
1.3 Nitrogen Inversion
1.4 Conformation
1.5 Secondary Structure
1.6 Double Helix
2. Models for Polymeric Chains
2.1 Spatial Configuration of Polymeric Chain
2.2 Freely Jointed Chain
2.3 Freely Rotating Chain
2.4 Simple Chain with Rotational Barrier
2.5 Gaussian Chain
3. Lattice Model
3.1 Lattice Model of Small Molecules
3.2 Flory–Huggins Theory
3.2.1 Entropy of Polymeric Chain
3.2.2 Enthalpy of Mixing
3.2.3 Chemical Potential
3.2.4 Excluded‐Volume Effect I
3.2.5 Excluded‐Volume Effect II
3.2.6 Phase Equilibrium
3.3 Intrinsic Viscosity
3.3.1 Stockmayer–Fixman Plot
Exercise
4. Rubber Elasticity
4.1 Thermodynamics of Rubber Elasticity
4.2 Adiabatic Stretching: Gough–Joule Effect
4.3 Phenomenological Theory: Affine Model
4.4 Temperature Dependence of Chain Dimension in Rubber
Part II. Quantum Chemistry
5. Ab Initio Molecular Orbital Theory
5.1 Schrödinger Equation
5.2 Wave Function
5.3 Basis Set
5.4 Hartree–Fock Method
5.5 Roothaan–Hall Equation
5.6 Electron Correlation
6. Density Functional Theory
6.1 Exchange and Correlation Functionals
6.2 Dispersion-force Correction
7. SolventEffect
8. Statistical Thermodynamics for Quantum Chemistry
8.1 Translational Motion
8.2 Rotational Motion
8.3 Vibrational Motion
8.4 Electronic Excitation
8.5 Thermochemistry
9. NMR Parameters
9.1 Chemical Shift
9.1.1 Example: Determination of Reaction Process from NMR Chemical Shifts
9.2 Indirect Spin–Spin Coupling Constant
9.2.1 Example 1: Calculation of Vicinal Coupling Constants of Cyclic Compound
9.2.2 Example 2: Derivation of Karplus Equation and Its Application
10. Periodic Quantum Chemistry
10.1 Direct Lattice and Reciprocal Lattice
10.2 Bloch Function
10.3 One‐electron Crystal Orbital
10.4 Structural Optimization
10.5 Crystal Elasticity
10.6 Vibrational Calculation
10.7 Thermal Chemistry
10.8 Cohesive (Interchain Interaction) Energy
Part III. Statistical Mechanics of Chain Molecules: Rotational Isomeric State Scheme
11. Conventional RIS Scheme
11.1 Chain Dimension
12 Refined RIS Scheme
12.1 RIS Scheme Including Middle-range Intramolecular Interactions
13. Inversional–Rotational Isomeric State (IRIS) Scheme
13.1 Pseudoasymmetry for Polyamines
13.2 Inversional–Rotational Isomerization
13.3 Statistical Weight Matrices of Meso and Racemo di‐MEDA
13.4 Statistical Weight Matrices of PEI
13.5 Diad Probability and Bond Conformation
13.6 Characteristic Ratio
13.7 Orientational Correlation Between Bonds
13.8 Solubility of Polyamines
14. RIS Scheme Combined with Stochastic Process
14.1 Polymeric Chains with Internally Rotatable Side Chains
Part IV. Experimental Methods
15. Nuclear Magnetic Resonance (NMR)
15.1 Conformational Analysis of Isotactic Poly(propylene oxide)
15.1.1 1H NMR Vicinal Coupling Constant
15.1.2 Ab initio MO Calculation
15.1.3 RIS Analysis of Bond Conformations
15.1.4 Configuration‐dependent Properties
15.2 Carbon‐13 NMR Chemical Shifts of Dimeric Propylene Oxides
15.2.1 Theoretical Basis
15.2.2 13C NMR Spectra and Assignment
15.2.3 Calculation of Chemical Shift by RIS Scheme
15.3 Model Compound of Poly(ethylene terephthalate)
16. Scattering Methods
16.1 Static Light Scattering (SLS)
16.1.1 Instrumentation and Sample Preparation for SLS
16.1.2 Application of SLS: Chain Dimensions of Polysilanes in the Θ State
16.2 Dynamic Light Scattering (DLS)
16.2.1 Application of DLS: Size Distribution of Polystyrene Latex Particles
16.2.2 Application of SLS and DLS to Poly(N‐methylethylene imine) Solutions
16.3 Small‐angle Neutron Scattering (SANS)
16.3.1 Application of SANS to Amorphous PET
Part V. Applications: Conformational Analysis and Elucidation of Structure–Property Relationships of Polymers
17. Polyethers
17.1 Poly(methylene oxide) (PMO)
17.2 Poly(ethylene oxide) (PEO)
17.3 Poly(propylene oxide) (PPO)
17.4 Poly(trimethylene oxide) (PTrMO)
17.5 Poly(tetramethylene oxide) (PTetMO)
18. Polyamines
18.1 Poly(ethylene imine) (PEI)
18.2 Poly(N‐methylethylene imine) (PMEI)
18.3 Poly(trimethylene imine) (PTMI) and Poly(N‐methyltrimethylene imine) (PMTMI)
19. Polyphosphines
19.1 Possibility of Phosphorus Inversion
19.2 Intramolecular Interactions Related to Phosphorus
19.3 RIS Calculation
19.4 Functions and Stability
20. Polysulfides
20.1 Poly(methylene sulfide) (PMS)
20.1.1 Crystal Structure of PMS
20.2 Poly(ethylene sulfide) (PES)
20.3 Poly(propylene sulfide) (PPS)
20.4 Poly(trimethylene sulfide) (PTrMS)
21. Polyselenides
21.1 Poly(methylene selenide) (PMSe)
21.1.1 Crystal Structure of PMSe
21.2 Poly(ethylene selenide) (PESe)
21.3 Poly(trimethylene selenide) (PTrMSe)
21.4 Summary
22. Alternating Copolymers Including Ethylene‐imine, Ethylene‐oxide, and Ethylene‐sulfide Units
22.1 Synthesis of P(EI‐ES)
23. Aromatic Polyester (PET, PTT, and PBT)
23.1 Correction for MP2 Energy of π–π Interaction
23.2 Dipole Moment and Molar Kerr Constant
23.3 Configurational Properties
23.4 Crystal Structure
24. Aliphatic Polyesters
24.1 Poly(glycolic acid) (PGA) and Poly(2‐hydroxybutyrate) (P2HB)
24.1.1 MO Calculation and NMR Experiment
24.1.2 RIS Calculation
24.1.3 Periodic DFT Calculation on PGA Crystal
24.2 Poly(lactic acid) (Poly(lactide), PLA)
24.2.1 MO Calculation and NMR Experiment
24.2.2 RIS Calculation
24.3 Poly((R)‐3‐hydroxybutyrate) (P3HB)
24.3.1 NMR Experiment
24.3.2 MO Calculation
24.3.3 RIS Calculation and Comparison with Experiment
24.3.4 Crystal Structure
24.4 Poly(ϵ‐caprolactone) (PCL)
24.4.1 MO Calculation
24.4.2 NMR Experiment
24.4.3 RIS Calculation
24.4.4 Crystal Structure
24.4.5 Crystal Elasticity
24.5 Poly(ethylene succinate) (PES) and Poly(butylene succinate) (PBS)
24.5.1 NMR Experiment
24.5.2 MO Calculation
24.5.3 RIS Calculation
24.5.4 Crystal Structure
24.6 Biodegradability of Polyesters
25. Polycarbonates
25.1 Poly(ethylene carbonate) (PEC) and Poly(propylene carbonate) (PPC)
25.1.1 NMR Experiment
25.1.2 MO Calculation
25.1.3 RIS Calculation
25.2 Poly(cyclohexene carbonate) (PCHC)
25.2.1 MO Calculation
25.2.2 NMR Experiment
25.2.3 RIS Calculation
25.2.4 Coherence Number
26. Nylon 4
26.1 MO Calculation
26.2 NMR Experiment
27. Aromatic Polyester, Polythionoester, Polythioester, Polydithioester, Polyamide, and Polythioamide
27.1 MO Calculation
27.2 Bond Conformation
27.3 RIS Calculation, Thermal Properties, and Solubility
28. Polysilanes
28.1 Molecular Dynamics
28.1.1 General Procedures
28.1.2 PDBS and PDHS
28.1.3 PMPrS
28.2 RIS Calculation
28.3 Physical Properties
29. Polyethylene (PE)
A. FORTRAN Computer Program for Refined RIS Calculations on Polyethylene
B. Answers of Problems
Bibliography
Index