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

Name: Conformational Analysis of Polymers - Methods and Techniques for Structure-Property Relationships and Molecular Design | Methods and Techniques for Structure-Property Relationships and Molecular Design
Brand: Wiley-Blackwell
Price: 180.5 EUR
Availability: BackOrder

Methods and Techniques for Structure-Property Relationships and Molecular Design

Sasanuma(Autor*in)

Wiley-Blackwell (Verlag)

1. Auflage

Erschienen am 5. April 2023

Buch

Hardcover

496 Seiten

978-1-119-71635-8 (ISBN)

180,50 €inkl. 7% MwSt.

Versand in 15-20 Tagen

Beschreibung

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:

Fundamentals of polymer physical chemistry: stereochemistry of polymers, models for polymeric chains, Flory-Huggins theory, and rubber elasticity
Quantum chemistry for polymers: ab initio molecular orbital theory, DFT, NMR parameters, and periodic DFT of polymer crystals
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
Experimental techniques: NMR and scattering methods

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.

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.

Weitere Details

Weitere Ausgaben

Person

Inhalt

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 Schroedinger 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 1H 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 13C 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 ? 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