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Part Ⅰ.Structure1

Chapter 1.Introduction3

1.1.Micro-and Macromolecular Chemistry3

1.2.The Molecular Concept12

1.3.Historical Development15

1.4.Nomenclature24

1.5.Commercial Classification and Significance28

Literature32

Chapter 2.Constitution37

2.1.The Concept of Structure37

2.2.Atomic Structure and Polymer Chain Bonds38

2.2.1.Isochains39

2.2.2.Heterochains42

2.3.Monomeric Unit Bonding47

2.3.1.Unipolymers47

2.3.2.Copolymers50

2.3.2.1.Composition51

2.3.2.2.Constitutional Heterogeneity52

2.3.2.3.Sequence58

2.3.3.Substituents62

2.3.4.End Groups63

2.4.Bonding in Individual Chains64

2.4.1.Branching64

2.4.2.Irregular Cross-Linked Structures66

2.4.3.Ordered Networks69

Literature72

Chapter 3.Configuration75

3.1.Ideal Structures75

3.1.1.Central Carbon Atom Asymmetry75

3.1.2.Tacticity78

3.1.3.Projections80

3.1.4.Monotactic Polymers81

3.1.5.Ditactic Polymers82

3.2.Real Structures84

3.2.1.J-ads84

3.2.2.Sequence Length86

3.3.Experimental Methods87

3.3.1.X-Ray Crystallography87

3.3.2.Nuclear Magnetic Resonance Spectroscopy87

3.3.3.Infrared Spectroscopy90

3.3.4.Other Methods90

Literature91

Chapter 4.Conformation93

4.1.Conformation of Single Molecules93

4.1.1.The Concept of Conformation93

4.1.2.Conformational Types97

4.1.3.Conformational Analysis99

4.1.4.Constitutional Influence100

4.2.Conformation in the Crystal102

4.3.Microconformation in Solution108

4.3.1.Low-Molecular-Weight Compounds108

4.3.2.Macromolecular Compounds110

4.4.Ideal Coil Molecules in Solution112

4.4.1.Phenomena112

4.4.2.Chain End-to-End Distance and Radii of Gyration114

4.4.2.1.The Random-Flight Model114

4.4.2.2.Chains with Constant Valence Angle115

4.4.2.3.Constant Valence Angle Chains with Hindered Rotation115

4.4.2.4.Radius of Gyration116

4.4.2.5.The Shape of Unperturbed Coils117

4.4.3.Steric Hindrance Parameter and Constitution117

4.4.4.The Characteristic Ratio119

4.4.5.Statistical Chain Element120

4.4.6.Wormlike Chain121

4.5.Excluded Volume123

4.5.1.Rigid Particles123

4.5.2.Unbranched Macromolecules124

4.5.2.1.Basic Principles124

4.5.2.2.Cluster Integrals126

4.5.2.3.Molecular-Weight Dependence of Coil Dimensions127

4.5.2.4.Concentration and Temperature Dependence of Coil Dimensions130

4.5.3.Branched Macromolecules131

4.6.Compact Molecules131

4.6.1.Helices131

4.6.2.Ellipsoids and Spheres132

4.7.Optical Activity133

4.7.1.Basic Principles133

4.7.2.Structural Effects135

4.7.2.1.General Considerations135

4.7.2.2.Poly(α-olefins)137

4.7.2.3.Poly(α-amino acids)140

4.7.2.4.Proteins141

4.8.Conformational Transitions142

4.8.1.Thermodynamics142

4.8.2.Kinetics145

A4.Appendix to Chapter 4146

A4.1.Calculation of the Chain End-to-End Distance146

A4.2.Relationship between the Radius of Gyration and the Chain End-to-End Distance for the Segment Model147

A4.3.Calculation of the Chain End-to-End Distance for Valence Angle Chains149

A4.4.Distribution of Chain End-to-End Distances151

Literature152

Chapter 5.Supermolecular Structures155

5.1.Phenomena155

5.2.Crystallinity Determination158

5.2.1.X-Ray Crystallography158

5.2.2.Density Measurements163

5.2.3.Calorimetry165

5.2.4.Infrared Spectroscopy165

5.2.5.Indirect Methods166

5.3.Crystal Structure167

5.3.1.Molecular Crystals167

5.3.2.Elementary and Unit Cells167

5.3.3.Polymorphism171

5.3.4.Isomorphism172

5.3.5.Lattice Defects172

5.4.Morphology of Crystalline Polymers174

5.4.1.Fringed Micelles174

5.4.2.Polymer Single Crystals176

5.4.3.Spherulites182

5.4.4.Dendrites and Epitaxial Growth184

5.5.The Amorphous State186

5.5.1.Free Volumes186

5.5.2.Morphology188

5.5.3.Polymer Alloys190

5.5.4.Block Copolymers190

5.6.Orientation191

5.6.1.Definition191

5.6.2.X-Ray Diffraction193

5.6.3.Optical Birefringence194

5.6.4.Infrared Dichroism195

5.6.5.Polarized Fluorescence195

5.6.6.Sound Propagation196

Literature197

Part Ⅱ.Solution Properties202

Chapter 6.Solution Thermodynamics203

6.1.Basic Principles203

6.2.Solubility Parameter205

6.2.1.Basic Principles205

6.2.2.Experimental Determination207

6.2.3.Applications209

6.3.Statistical Thermodynamics211

6.3.1.Entropy of Mixing211

6.3.2.Enthalpy of Mixing212

6.3.3.Gibbs Energy of Mixing for Nonelectrolytes213

6.3.4.Gibbs Energy of Mixing for Polyelectrolytes215

6.3.5.Chemical Potential of Concentrated Solutions215

6.3.6.Chemical Potential of Dilute Solutions217

6.4.Virial Coefficients218

6.4.1.Definitions218

6.4.2.Excluded Volume219

6.5.Association222

6.5.1.Basic Principles222

6.5.2.Open Association224

6.5.3.Closed Association227

6.5.4.Concentrated Solutions and Melts229

6.6.Rhase Separation230

6.6.1.Basic Principles230

6.6.2.Upper and Lower Critical Solution Temperatures231

6.6.3.Quasibinary Systems233

6.6.4.Fractionation and Microencapsulation237

6.6.5.Determination of Theta States238

6.6.6.Incompatibility241

6.6.7.Swelling242

6.6.8.Crystalline Polymers244

Literature246

Chapter 7.Transport Phenomena249

7.1.Effective Quantities249

7.2.Diffusion in Dilute Solution250

7.2.1.Basic Principles250

7.2.2.Experimental Methods253

7.2.3.Molecular Quantities255

7.3.Permeation through Solids256

7.3.1.Basic Principles256

7.3.2.Experimental Methods257

7.3.3.Constitutional Influence258

7.4.Rotational Diffusion and Streaming Birefringence260

7.5.Electrophoresis261

7.6.Viscosity263

7.6.1.Concepts263

7.6.2.Methods266

7.6.3.Flow Curves270

7.6.4.Viscosities of Melts271

7.6.5.Viscosity of Concentrated Solutions275

Literature275

Chapter 8.Molecular Weights and Molecular-Weight Distributions277

8.1.Introduction277

8.2.Statistical Weights278

8.3.Molecular-Weight Distributions280

8.3.1.Representation of the Distribution Functions280

8.3.2.Types of Distribution Functions282

8.3.2.1.Gaussian Distribution282

8.3.2.2.Logarithmic Normal Distribution284

8.3.2.3.Poisson Distribution286

8.3.2.4.Schulz-Flory Distribution287

8.3.2.5.Tung Distribution288

8.4.Moments288

8.5.Averages289

8.5.1.General Relationships289

8.5.2.Simple One-Moment Averages290

8.5.3.One-Moment Exponent Averages291

8.5.4.Multimorment Averages291

8.5.5.Polydispersity Parameters294

Literature295

Chapter 9.Determination of Molecular Weight and Molecular-Weight Distribution297

9.1.Introduction and Survey297

9.2.Membrane Osmometry299

9.2.1.Semipermeable Membranes299

9.2.2.Experimental Methods301

9.2.3.Nonsemipermeable or Leaky Membranes304

9.3.Ebulliometry and Cryoscopy307

9.4.Vapor-Phase Osmometry308

9.5.Light Scattering309

9.5.1.Basic Principles309

9.5.2.Small Particles310

9.5.3.Copolymers314

9.5.4.Concentration Dependence317

9.5.5.Large Particles320

9.5.6.Experimental Procedure324

9.6.Small-Angle X-Ray and Neutron Scattering325

9.7.Ultracentrifugation326

9.7.1.Phenomena and Methods326

9.7.2.Basic Equations329

9.7.3.Sedimentation Velocity330

9.7.4.Equilibrium Sedimentation333

9.7.5.Sedimentation Equilibrium in a Density Gradient334

9.7.6.Preparative Ultracentrifugation337

9.8.Chromatography338

9.8.1.Elution Chromatography338

9.8.2.Gel-Permeation Chromatography338

9.8.3.Adsorption Chromatography342

9.9.Viscometry343

9.9.1.Basic Principles343

9.9.2.Experimental Methods345

9.9.3.Concentration Dependence for Nonelectrolytes350

9.9.4.Concentration Dependence for Polyelectrolytes352

9.9.5.The Staudinger Index and the Molecular Weight of Rigid Molecules354

9.9.6.The Molecular Weight and Staudinger Index of Coil-like Molecules357

9.9.7.Calibration of the Viscosity-Molecular Weight Relationship362

9.9.8.Influence of the Chemical Structure on the Staudinger Index364

9.9.9.Temperature Dependence of the Staudinger Indices366

Literature367

Part Ⅲ.Solid-State Properties372

Chapter 10.Thermal Transitions373

10.1.Basic Principles373

10.1.1.Phenomena373

10.1.2.Thermodynamics374

10.2.Special Parameters and Methods378

10.2.1.Expansion378

10.2.2.Heat Capacity380

10.2.3.Differential Thermal Analysis381

10.2.4.Nuclear Magnetic Resonance383

10.2.5.Dynamic Methods384

10.2.6.Industrial Testing Methods384

10.3.Crystallization386

10.3.1.Morphology386

10.3.2.Formation of Nuclei387

10.3.3.Crystal Growth or Crystallization390

10.3.4.The Influence of Additives395

10.3.5.Recrystallization395

10.4.Melting396

10.4.1.Melt Processes396

10.4.2.Melting Temperature and Molecular Weight399

10.4.3.Melting Point and Constitution400

10.4.4.Melting Point of Copolymers405

10.5.Glass Transitions405

10.5.1.Phenomena405

10.5.2.Static and Dynamic Glass-Transition Temperatures406

10.5.3.Glass-Transition Temperature and Constirution408

10.5.4.Glass-Transition Temperature and Configuration410

10.5.5.Glass-Transition Temperature ofCopolymers410

10.5.6.Plasticizers412

10.6.Other Transitions414

10.7.Thermal Conductivity416

Literature417

Chapter 11.Mechanical Properties421

11.1.Phenomena421

11.2.Energy-Elasticity424

11.2.1.Basic Parameters424

11.2.2.Structural Influences425

11.3.Entropy-Elasticity427

11.3.1.Phenomena427

11.3.2.Phenomenological Thermodynamics431

11.3.3.Statistical Thermodynamics433

11.3.4.Elastoosmometry437

11.4.Viscoelasticity438

11.4.1.Basic Principles438

11.4.2.Relaxation Processes440

11.4.3.Retardation Processes441

11.4.4.Combined Processes442

11.4.5.Dynamic Loading443

11.5.Deformation Processes444

11.5.1.Tensile Tests444

11.5.2.Necking447

11.5.3.Hardness450

11.6.Fracture451

11.6.1.Concepts and Methods451

11.6.2.Theory of Brittle Fracture452

11.6.3.Impact Strength455

11.6.4.Reinforcement457

11.6.5.Plasticization458

11.6.6.Stress Cracking459

11.6.7.Durability459

Literature461

Chapter 12.Compounding and Processing of Plastics463

12.1.Compounding463

12.1.1.General463

12.1.2.Fillers464

12.1.3.Dyes and Pigments466

12.1.4.Piasticizers468

12.1.5.Release Agents,Lubricants,Stabilizers,and Antistatics468

12.2.Processing of Thermoplasts,Thermosets,and Elastomers469

12.2.1.Classification469

12.2.2.Processing via the Viscous State470

12.2.3.Processing via the Elastoviscous State472

12.2.4.Processing via the Elastoplastic State475

12.2.5.Processing via the Viscoelastic State477

12.2.6.Processing via the Solid State478

12.3.Fiber Processing479

12.3.1.Introduction479

12.3.2.Fiber Formation481

12.3.3.Spinning Techniques482

12.3.4.Spin Processes484

12.3.5.Drawing486

12.3.6.Fiber Properties487

12.4.Finishing(Surface Treatment)491

12.4.1.Metallizing491

12.4.2.Glass Coating491

Literature492

Chapter 13.Interfacial Phenomena495

13.1.Spreading495

13.2.Interfacial Tensions496

13.2.1.Surface Tension of Liquid Polymers496

13.2.2.Interfacial Tension of Solid Polymers498

13.2.2.1.Basic Principles498

13.2.2.2.Critical Surface Tension499

13.3.Adsorption of Polymers501

13.4.Adhesives and Glues503

13.4.1.Adhesion503

13.4.2.Gluing505

Literature507

Chapter 14.Electrical Properties509

14.1.Dielectric Properties509

14.1.1.Polarizability510

14.1.2.Behavior in an Alternating Electric Field510

14.1.3.Dielectric Field Strength512

14.1.4.Tracking513

14.1.5.Electrostatic Charging513

14.1.6.Electrets515

14.2.Electronic Conductivity516

14.2.1.Influence of Chemical Structure516

14.2.2.Measuring Techniques520

Literature521

Chapter 15.Optical Properties523

15.1.Light Refraction523

15.2.Light Interference and Color525

15.2.1.Basic Principles525

15.2.2.Iridescent Colors526

15.3.Light Transmission and Reflection527

15.3.1.Total Reflection527

15.3.2.Transparency528

15.3.3.Gloss529

15.4.Light Scattering530

15.4.1.Phenomena530

15.4.2.Opacity531

Literature532