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Conformational Analysis of Polymers

Methods and Techniques for Structure-Property Relationships and Molecular Design
1. Aufl.

von: Yuji Sasanuma
142,99 €
Verlag:	Wiley
Format:	PDF
Veröffentl.:	22.03.2023
ISBN/EAN:	9781119716594
Sprache:	englisch
Anzahl Seiten:	496

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Titelbeschreibung

Conformational Analysis of Polymers Comprehensive resource focusing on theoretical methods and experimental techniques to analyze physical polymer chemistry Connecting varied issues to demonstrate the impact on areas like biodegradability, environmental friendliness, structure-property relationship, and molecular design, Conformational Analysis of Polymers introduces theoretical methods and experimental techniques to analyze physical polymer chemistry. Opening with a description of fundamental concepts and then describing the conformational characteristics of various polymers, including different heteroatoms and chemical species, the text continues onto the applications of density functional theory (DFT) to polymer crystals and structure-property relationships. The book concludes by bringing these issues together to demonstrate their practical impact on different areas of the field. Various methods and techniques, including DFT, statistical mechanics, NMR, spectroscopy, and molecular orbital theory, are also covered. Written by a highly qualified author, Conformational Analysis of Polymers explores sample topics such as: <ul> <li>Fundamentals of polymer physical chemistry: stereochemistry of polymers, models for polymeric chains, Flory-Huggins theory, and rubber elasticity</li> <li>Quantum chemistry for polymers: ab initio molecular orbital theory, DFT, NMR parameters, and periodic DFT of polymer crystals</li> <li>Statistical mechanics of polymeric chains: basic rotational isomeric state (RIS) scheme, refined RIS method, inversional-rotational isomeric state method, and probability theory for RIS scheme</li> <li>Experimental techniques: NMR and scattering methods</li> </ul> Providing a timely update to the field of chain conformations of synthetic polymers and connecting fundamental theoretical approaches, experimental techniques, and case study applications; Conformational Analysis of Polymers is an essential resource for polymer chemists, physicists, and material scientists, industrial engineers who synthesize and process polymers, and academic researchers.

Inhaltsverzeichnis

Preface xii Acknowledgments xvi About the Author xvii Acronyms xviii Part I Fundamentals of Polymer Physical Chemistry 1 1 Stereochemistry of Polymers 3 1.1 Configuration 3 1.2 Connection Type of Monomeric Units 5 1.3 Nitrogen Inversion 5 1.4 Conformation 8 1.5 Secondary Structure 9 1.6 Double Helix 11 2 Models for Polymeric Chains 13 2.1 Spatial Configuration of Polymeric Chain 13 2.2 Freely Jointed Chain 13 2.3 Freely Rotating Chain 15 2.4 Simple Chain with Rotational Barrier 16 2.5 Gaussian Chain 17 3 Lattice Model 21 3.1 Lattice Model of Small Molecules 21 3.2 Flory–Huggins Theory 22 3.2.1 Entropy of Polymeric Chain 22 3.2.2 Enthalpy of Mixing 25 3.2.3 Chemical Potential 26 3.2.4 Excluded-Volume Effect I 28 3.2.5 Excluded-volume Effect II 32 3.2.6 Phase Equilibrium 35 3.3 Intrinsic Viscosity 36 3.3.1 Stockmayer–Fixman Plot 37 Exercise 38 4 Rubber Elasticity 41 4.1 Thermodynamics of Rubber Elasticity 41 4.2 Adiabatic Stretching: Gough–Joule Effect 45 4.3 Phenomenological Theory: Affine Model 46 4.4 Temperature Dependence of Chain Dimension in Rubber 48 Part II Quantum Chemistry 51 5 Ab Initio Molecular Orbital Theory 55 5.1 Schrödinger Equation 55 5.2 Wave Function 56 5.3 Basis Set 57 5.4 Hartree–Fock Method 58 5.5 Roothaan–Hall Equation 59 5.6 Electron Correlation 60 6 Density Functional Theory 63 6.1 Exchange and Correlation Functionals 65 6.2 Dispersion-force Correction 67 7 Solvent Effect 69 8 Statistical Thermodynamics for Quantum Chemistry 75 8.1 Translational Motion 76 8.2 Rotational Motion 77 8.3 Vibrational Motion 78 8.4 Electronic Excitation 80 8.5 Thermochemistry 81 9 NMR Parameters 85 9.1 Chemical Shift 86 9.1.1 Example: Determination of Reaction Process from NMR Chemical Shifts 88 9.2 Indirect Spin–Spin Coupling Constant 92 9.2.1 Example 1: Calculation of Vicinal Coupling Constants of Cyclic Compound 93 9.2.2 Example 2: Derivation of Karplus Equation and Its Application 95 10 Periodic Quantum Chemistry 99 10.1 Direct Lattice and Reciprocal Lattice 99 10.2 Bloch Function 100 10.3 One-electron Crystal Orbital 101 10.4 Structural Optimization 102 10.5 Crystal Elasticity 104 10.6 Vibrational Calculation 108 10.7 Thermal Chemistry 110 10.8 Cohesive (Interchain Interaction) Energy 112 Part III Statistical Mechanics of Chain Molecules: Rotational Isomeric State Scheme 115 11 Conventional RIS Scheme 117 11.1 Chain Dimension 121 12 Refined RIS Scheme 125 12.1 RIS Scheme Including Middle-range Intramolecular Interactions 129 13 Inversional–Rotational Isomeric State (IRIS) Scheme 137 13.1 Pseudoasymmetry for Polyamines 137 13.2 Inversional–Rotational Isomerization 137 13.3 Statistical Weight Matrices of Meso and Racemo di-MEDA 138 13.4 Statistical Weight Matrices of PEI 139 13.5 Diad Probability and Bond Conformation 142 13.6 Characteristic Ratio 144 13.7 Orientational Correlation Between Bonds 145 13.8 Solubility of Polyamines 148 14 RIS Scheme Combined with Stochastic Process 151 14.1 Polymeric Chains with Internally Rotatable Side Chains 153 Part IV Experimental Methods 161 15 Nuclear Magnetic Resonance (NMR) 163 15.1 Conformational Analysis of Isotactic Poly(propylene oxide) 163 15.1.1 1 H NMR Vicinal Coupling Constant 164 15.1.2 Ab initio MO Calculation 168 15.1.3 RIS Analysis of Bond Conformations 171 15.1.4 Configuration-dependent Properties 172 15.2 Carbon-13 NMR Chemical Shifts of Dimeric Propylene Oxides 173 15.2.1 Theoretical Basis 175 15.2.2 13 C NMR Spectra and Assignment 176 15.2.3 Calculation of Chemical Shift by RIS Scheme 179 15.3 Model Compound of Poly(ethylene terephthalate) 181 16 Scattering Methods 187 16.1 Static Light Scattering (SLS) 187 16.1.1 Instrumentation and Sample Preparation for SLS 189 16.1.2 Application of SLS: Chain Dimensions of Polysilanes in the Θ State 191 16.2 Dynamic Light Scattering (DLS) 195 16.2.1 Application of DLS: Size Distribution of Polystyrene Latex Particles 197 16.2.2 Application of SLS and DLS to Poly(N-methylethylene imine) Solutions 198 16.3 Small-angle Neutron Scattering (SANS) 201 16.3.1 Application of SANS to Amorphous PET 204 Part V Applications: Conformational Analysis and Elucidation of Structure–property Relationships of Polymers 207 17 Polyethers 215 17.1 Poly(methylene oxide) (PMO) 215 17.2 Poly(ethylene oxide) (PEO) 217 17.3 Poly(propylene oxide) (PPO) 226 17.4 Poly(trimethylene oxide) (PTrMO) 228 17.5 Poly(tetramethylene oxide) (PTetMO) 229 18 Polyamines 235 18.1 Poly(ethylene imine) (PEI) 236 18.2 Poly(N-methylethylene imine) (PMEI) 237 18.3 Poly(trimethylene imine) (PTMI) and Poly(N-methyltrimethylene imine) (pmtmi) 238 19 Polyphosphines 241 19.1 Possibility of Phosphorus Inversion 241 19.2 Intramolecular Interactions Related to Phosphorus 243 19.3 RIS Calculation 244 19.4 Functions and Stability 248 20 Polysulfides 249 20.1 Poly(methylene sulfide) (PMS) 249 20.1.1 Crystal Structure of PMS 253 20.2 Poly(ethylene sulfide) (PES) 253 20.3 Poly(propylene sulfide) (PPS) 260 20.4 Poly(trimethylene sulfide) (PTrMS) 265 21 Polyselenides 269 21.1 Poly(methylene selenide) (PMSe) 269 21.1.1 Crystal Structure of PMSe 270 21.2 Poly(ethylene selenide) (PESe) 274 21.3 Poly(trimethylene selenide) (PTrMSe) 276 21.4 Summary 277 22 Alternating Copolymers Including Ethylene-imine, Ethylene-oxide, and Ethylene-sulfide Units 279 22.1 Synthesis of P(EI-ES) 286 23 Aromatic Polyester (PET, PTT, and PBT) 289 23.1 Correction for MP2 Energy of π–π Interaction 290 23.2 Dipole Moment and Molar Kerr Constant 293 23.3 Configurational Properties 296 23.4 Crystal Structure 297 24 Aliphatic Polyesters 301 24.1 Poly(glycolic acid) (PGA) and Poly(2-hydroxybutyrate) (P2HB) 301 24.1.1 MO Calculation and NMR Experiment 302 24.1.2 RIS Calculation 305 24.1.3 Periodic DFT Calculation on PGA Crystal 309 24.2 Poly(lactic acid) (Poly(lactide), PLA) 312 24.2.1 MO Calculation and NMR Experiment 313 24.2.2 RIS Calculation 317 24.3 Poly((R)-3-hydroxybutyrate) (P3HB) 321 24.3.1 NMR Experiment 321 24.3.2 MO Calculation 323 24.3.3 RIS Calculation and Comparison with Experiment 325 24.3.4 Crystal Structure 326 24.4 Poly(ε-caprolactone) (PCL) 327 24.4.1 MO Calculation 328 24.4.2 NMR Experiment 330 24.4.3 RIS Calculation 330 24.4.4 Crystal Structure 332 24.4.5 Crystal Elasticity 333 24.5 Poly(ethylene succinate) (PES) and Poly(butylene succinate) (PBS) 336 24.5.1 NMR Experiment 337 24.5.2 MO Calculation 338 24.5.3 RIS Calculation 339 24.5.4 Crystal Structure 340 24.6 Biodegradability of Polyesters 342 25 Polycarbonates 347 25.1 Poly(ethylene carbonate) (PEC) and Poly(propylene carbonate) (ppc) 348 25.1.1 NMR Experiment 351 25.1.2 MO Calculation 351 25.1.3 RIS Calculation 353 25.2 Poly(cyclohexene carbonate) (PCHC) 357 25.2.1 MO Calculation 358 25.2.2 NMR Experiment 360 25.2.3 RIS Calculation 361 25.2.4 Coherence Number 364 26 Nylon 4 367 26.1 MO Calculation 368 26.2 NMR Experiment 370 27 Aromatic Polyester, Polythionoester, Polythioester, Polydithioester, Polyamide, and Polythioamide 373 27.1 MO Calculation 375 27.2 Bond Conformation 377 27.3 RIS Calculation, Thermal Properties, and Solubility 380 28 Polysilanes 383 28.1 Molecular Dynamics 384 28.1.1 General Procedures 384 28.1.2 PDBS and PDHS 384 28.1.3 PMPrS 387 28.2 RIS Calculation 387 28.3 Physical Properties 388 29 Polyethylene (PE) 391 A FORTRAN Computer Program for Refined RIS Calculations on Polyethylene 399 B Answers of Problems 423 Bibliography 431 Index 465

Autorenportrait

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.

Back cover copy

Comprehensive resource focusing on theoretical methods and experimental techniques to analyze physical polymer chemistry Connecting varied issues to demonstrate the impact on areas like biodegradability, environmental friendliness, structure-property relationship, and molecular design, Conformational Analysis of Polymers introduces theoretical methods and experimental techniques to analyze physical polymer chemistry. Opening with a description of fundamental concepts and then describing the conformational characteristics of various polymers, including different heteroatoms and chemical species, the text continues onto the applications of density functional theory (DFT) to polymer crystals and structure-property relationships. The book concludes by bringing these issues together to demonstrate their practical impact on different areas of the field. Various methods and techniques, including DFT, statistical mechanics, NMR, spectroscopy, and molecular orbital theory, are also covered. Written by a highly qualified author, Conformational Analysis of Polymers explores sample topics such as: <ul><li>Fundamentals of polymer physical chemistry: stereochemistry of polymers, models for polymeric chains, Flory-Huggins theory, and rubber elasticity</li> <li>Quantum chemistry for polymers: ab initio molecular orbital theory, DFT, NMR parameters, and periodic DFT of polymer crystals</li> <li>Statistical mechanics of polymeric chains: basic rotational isomeric state (RIS) scheme, refined RIS method, inversional-rotational isomeric state method, and probability theory for RIS scheme</li> <li>Experimental techniques: NMR and scattering methods</li></ul> Providing a timely update to the field of chain conformations of synthetic polymers and connecting fundamental theoretical approaches, experimental techniques, and case study applications; Conformational Analysis of Polymers is an essential resource for polymer chemists, physicists, and material scientists, industrial engineers who synthesize and process polymers, and academic researchers.