Part Ⅰ.Structure 1
Chapter 1.Introduction 3
1.1.Micro-and Macromolecular Chemistry 3
1.2.The Molecular Concept 12
1.3.Historical Development 15
1.4.Nomenclature 24
1.5.Commercial Classification and Significance 28
Literature 32
Chapter 2.Constitution 37
2.1.The Concept of Structure 37
2.2.Atomic Structure and Polymer Chain Bonds 38
2.2.1.Isochains 39
2.2.2.Heterochains 42
2.3.Monomeric Unit Bonding 47
2.3.1.Unipolymers 47
2.3.2.Copolymers 50
2.3.2.1.Composition 51
2.3.2.2.Constitutional Heterogeneity 52
2.3.2.3.Sequence 58
2.3.3.Substituents 62
2.3.4.End Groups 63
2.4.Bonding in Individual Chains 64
2.4.1.Branching 64
2.4.2.Irregular Cross-Linked Structures 66
2.4.3.Ordered Networks 69
Literature 72
Chapter 3.Configuration 75
3.1.Ideal Structures 75
3.1.1.Central Carbon Atom Asymmetry 75
3.1.2.Tacticity 78
3.1.3.Projections 80
3.1.4.Monotactic Polymers 81
3.1.5.Ditactic Polymers 82
3.2.Real Structures 84
3.2.1.J-ads 84
3.2.2.Sequence Length 86
3.3.Experimental Methods 87
3.3.1.X-Ray Crystallography 87
3.3.2.Nuclear Magnetic Resonance Spectroscopy 87
3.3.3.Infrared Spectroscopy 90
3.3.4.Other Methods 90
Literature 91
Chapter 4.Conformation 93
4.1.Conformation of Single Molecules 93
4.1.1.The Concept of Conformation 93
4.1.2.Conformational Types 97
4.1.3.Conformational Analysis 99
4.1.4.Constitutional Influence 100
4.2.Conformation in the Crystal 102
4.3.Microconformation in Solution 108
4.3.1.Low-Molecular-Weight Compounds 108
4.3.2.Macromolecular Compounds 110
4.4.Ideal Coil Molecules in Solution 112
4.4.1.Phenomena 112
4.4.2.Chain End-to-End Distance and Radii of Gyration 114
4.4.2.1.The Random-Flight Model 114
4.4.2.2.Chains with Constant Valence Angle 115
4.4.2.3.Constant Valence Angle Chains with Hindered Rotation 115
4.4.2.4.Radius of Gyration 116
4.4.2.5.The Shape of Unperturbed Coils 117
4.4.3.Steric Hindrance Parameter and Constitution 117
4.4.4.The Characteristic Ratio 119
4.4.5.Statistical Chain Element 120
4.4.6.Wormlike Chain 121
4.5.Excluded Volume 123
4.5.1.Rigid Particles 123
4.5.2.Unbranched Macromolecules 124
4.5.2.1.Basic Principles 124
4.5.2.2.Cluster Integrals 126
4.5.2.3.Molecular-Weight Dependence of Coil Dimensions 127
4.5.2.4.Concentration and Temperature Dependence of Coil Dimensions 130
4.5.3.Branched Macromolecules 131
4.6.Compact Molecules 131
4.6.1.Helices 131
4.6.2.Ellipsoids and Spheres 132
4.7.Optical Activity 133
4.7.1.Basic Principles 133
4.7.2.Structural Effects 135
4.7.2.1.General Considerations 135
4.7.2.2.Poly(α-olefins) 137
4.7.2.3.Poly(α-amino acids) 140
4.7.2.4.Proteins 141
4.8.Conformational Transitions 142
4.8.1.Thermodynamics 142
4.8.2.Kinetics 145
A4.Appendix to Chapter 4 146
A4.1.Calculation of the Chain End-to-End Distance 146
A4.2.Relationship between the Radius of Gyration and the Chain End-to-End Distance for the Segment Model 147
A4.3.Calculation of the Chain End-to-End Distance for Valence Angle Chains 149
A4.4.Distribution of Chain End-to-End Distances 151
Literature 152
Chapter 5.Supermolecular Structures 155
5.1.Phenomena 155
5.2.Crystallinity Determination 158
5.2.1.X-Ray Crystallography 158
5.2.2.Density Measurements 163
5.2.3.Calorimetry 165
5.2.4.Infrared Spectroscopy 165
5.2.5.Indirect Methods 166
5.3.Crystal Structure 167
5.3.1.Molecular Crystals 167
5.3.2.Elementary and Unit Cells 167
5.3.3.Polymorphism 171
5.3.4.Isomorphism 172
5.3.5.Lattice Defects 172
5.4.Morphology of Crystalline Polymers 174
5.4.1.Fringed Micelles 174
5.4.2.Polymer Single Crystals 176
5.4.3.Spherulites 182
5.4.4.Dendrites and Epitaxial Growth 184
5.5.The Amorphous State 186
5.5.1.Free Volumes 186
5.5.2.Morphology 188
5.5.3.Polymer Alloys 190
5.5.4.Block Copolymers 190
5.6.Orientation 191
5.6.1.Definition 191
5.6.2.X-Ray Diffraction 193
5.6.3.Optical Birefringence 194
5.6.4.Infrared Dichroism 195
5.6.5.Polarized Fluorescence 195
5.6.6.Sound Propagation 196
Literature 197
Part Ⅱ.Solution Properties 202
Chapter 6.Solution Thermodynamics 203
6.1.Basic Principles 203
6.2.Solubility Parameter 205
6.2.1.Basic Principles 205
6.2.2.Experimental Determination 207
6.2.3.Applications 209
6.3.Statistical Thermodynamics 211
6.3.1.Entropy of Mixing 211
6.3.2.Enthalpy of Mixing 212
6.3.3.Gibbs Energy of Mixing for Nonelectrolytes 213
6.3.4.Gibbs Energy of Mixing for Polyelectrolytes 215
6.3.5.Chemical Potential of Concentrated Solutions 215
6.3.6.Chemical Potential of Dilute Solutions 217
6.4.Virial Coefficients 218
6.4.1.Definitions 218
6.4.2.Excluded Volume 219
6.5.Association 222
6.5.1.Basic Principles 222
6.5.2.Open Association 224
6.5.3.Closed Association 227
6.5.4.Concentrated Solutions and Melts 229
6.6.Rhase Separation 230
6.6.1.Basic Principles 230
6.6.2.Upper and Lower Critical Solution Temperatures 231
6.6.3.Quasibinary Systems 233
6.6.4.Fractionation and Microencapsulation 237
6.6.5.Determination of Theta States 238
6.6.6.Incompatibility 241
6.6.7.Swelling 242
6.6.8.Crystalline Polymers 244
Literature 246
Chapter 7.Transport Phenomena 249
7.1.Effective Quantities 249
7.2.Diffusion in Dilute Solution 250
7.2.1.Basic Principles 250
7.2.2.Experimental Methods 253
7.2.3.Molecular Quantities 255
7.3.Permeation through Solids 256
7.3.1.Basic Principles 256
7.3.2.Experimental Methods 257
7.3.3.Constitutional Influence 258
7.4.Rotational Diffusion and Streaming Birefringence 260
7.5.Electrophoresis 261
7.6.Viscosity 263
7.6.1.Concepts 263
7.6.2.Methods 266
7.6.3.Flow Curves 270
7.6.4.Viscosities of Melts 271
7.6.5.Viscosity of Concentrated Solutions 275
Literature 275
Chapter 8.Molecular Weights and Molecular-Weight Distributions 277
8.1.Introduction 277
8.2.Statistical Weights 278
8.3.Molecular-Weight Distributions 280
8.3.1.Representation of the Distribution Functions 280
8.3.2.Types of Distribution Functions 282
8.3.2.1.Gaussian Distribution 282
8.3.2.2.Logarithmic Normal Distribution 284
8.3.2.3.Poisson Distribution 286
8.3.2.4.Schulz-Flory Distribution 287
8.3.2.5.Tung Distribution 288
8.4.Moments 288
8.5.Averages 289
8.5.1.General Relationships 289
8.5.2.Simple One-Moment Averages 290
8.5.3.One-Moment Exponent Averages 291
8.5.4.Multimorment Averages 291
8.5.5.Polydispersity Parameters 294
Literature 295
Chapter 9.Determination of Molecular Weight and Molecular-Weight Distribution 297
9.1.Introduction and Survey 297
9.2.Membrane Osmometry 299
9.2.1.Semipermeable Membranes 299
9.2.2.Experimental Methods 301
9.2.3.Nonsemipermeable or Leaky Membranes 304
9.3.Ebulliometry and Cryoscopy 307
9.4.Vapor-Phase Osmometry 308
9.5.Light Scattering 309
9.5.1.Basic Principles 309
9.5.2.Small Particles 310
9.5.3.Copolymers 314
9.5.4.Concentration Dependence 317
9.5.5.Large Particles 320
9.5.6.Experimental Procedure 324
9.6.Small-Angle X-Ray and Neutron Scattering 325
9.7.Ultracentrifugation 326
9.7.1.Phenomena and Methods 326
9.7.2.Basic Equations 329
9.7.3.Sedimentation Velocity 330
9.7.4.Equilibrium Sedimentation 333
9.7.5.Sedimentation Equilibrium in a Density Gradient 334
9.7.6.Preparative Ultracentrifugation 337
9.8.Chromatography 338
9.8.1.Elution Chromatography 338
9.8.2.Gel-Permeation Chromatography 338
9.8.3.Adsorption Chromatography 342
9.9.Viscometry 343
9.9.1.Basic Principles 343
9.9.2.Experimental Methods 345
9.9.3.Concentration Dependence for Nonelectrolytes 350
9.9.4.Concentration Dependence for Polyelectrolytes 352
9.9.5.The Staudinger Index and the Molecular Weight of Rigid Molecules 354
9.9.6.The Molecular Weight and Staudinger Index of Coil-like Molecules 357
9.9.7.Calibration of the Viscosity-Molecular Weight Relationship 362
9.9.8.Influence of the Chemical Structure on the Staudinger Index 364
9.9.9.Temperature Dependence of the Staudinger Indices 366
Literature 367
Part Ⅲ.Solid-State Properties 372
Chapter 10.Thermal Transitions 373
10.1.Basic Principles 373
10.1.1.Phenomena 373
10.1.2.Thermodynamics 374
10.2.Special Parameters and Methods 378
10.2.1.Expansion 378
10.2.2.Heat Capacity 380
10.2.3.Differential Thermal Analysis 381
10.2.4.Nuclear Magnetic Resonance 383
10.2.5.Dynamic Methods 384
10.2.6.Industrial Testing Methods 384
10.3.Crystallization 386
10.3.1.Morphology 386
10.3.2.Formation of Nuclei 387
10.3.3.Crystal Growth or Crystallization 390
10.3.4.The Influence of Additives 395
10.3.5.Recrystallization 395
10.4.Melting 396
10.4.1.Melt Processes 396
10.4.2.Melting Temperature and Molecular Weight 399
10.4.3.Melting Point and Constitution 400
10.4.4.Melting Point of Copolymers 405
10.5.Glass Transitions 405
10.5.1.Phenomena 405
10.5.2.Static and Dynamic Glass-Transition Temperatures 406
10.5.3.Glass-Transition Temperature and Constirution 408
10.5.4.Glass-Transition Temperature and Configuration 410
10.5.5.Glass-Transition Temperature ofCopolymers 410
10.5.6.Plasticizers 412
10.6.Other Transitions 414
10.7.Thermal Conductivity 416
Literature 417
Chapter 11.Mechanical Properties 421
11.1.Phenomena 421
11.2.Energy-Elasticity 424
11.2.1.Basic Parameters 424
11.2.2.Structural Influences 425
11.3.Entropy-Elasticity 427
11.3.1.Phenomena 427
11.3.2.Phenomenological Thermodynamics 431
11.3.3.Statistical Thermodynamics 433
11.3.4.Elastoosmometry 437
11.4.Viscoelasticity 438
11.4.1.Basic Principles 438
11.4.2.Relaxation Processes 440
11.4.3.Retardation Processes 441
11.4.4.Combined Processes 442
11.4.5.Dynamic Loading 443
11.5.Deformation Processes 444
11.5.1.Tensile Tests 444
11.5.2.Necking 447
11.5.3.Hardness 450
11.6.Fracture 451
11.6.1.Concepts and Methods 451
11.6.2.Theory of Brittle Fracture 452
11.6.3.Impact Strength 455
11.6.4.Reinforcement 457
11.6.5.Plasticization 458
11.6.6.Stress Cracking 459
11.6.7.Durability 459
Literature 461
Chapter 12.Compounding and Processing of Plastics 463
12.1.Compounding 463
12.1.1.General 463
12.1.2.Fillers 464
12.1.3.Dyes and Pigments 466
12.1.4.Piasticizers 468
12.1.5.Release Agents,Lubricants,Stabilizers,and Antistatics 468
12.2.Processing of Thermoplasts,Thermosets,and Elastomers 469
12.2.1.Classification 469
12.2.2.Processing via the Viscous State 470
12.2.3.Processing via the Elastoviscous State 472
12.2.4.Processing via the Elastoplastic State 475
12.2.5.Processing via the Viscoelastic State 477
12.2.6.Processing via the Solid State 478
12.3.Fiber Processing 479
12.3.1.Introduction 479
12.3.2.Fiber Formation 481
12.3.3.Spinning Techniques 482
12.3.4.Spin Processes 484
12.3.5.Drawing 486
12.3.6.Fiber Properties 487
12.4.Finishing(Surface Treatment) 491
12.4.1.Metallizing 491
12.4.2.Glass Coating 491
Literature 492
Chapter 13.Interfacial Phenomena 495
13.1.Spreading 495
13.2.Interfacial Tensions 496
13.2.1.Surface Tension of Liquid Polymers 496
13.2.2.Interfacial Tension of Solid Polymers 498
13.2.2.1.Basic Principles 498
13.2.2.2.Critical Surface Tension 499
13.3.Adsorption of Polymers 501
13.4.Adhesives and Glues 503
13.4.1.Adhesion 503
13.4.2.Gluing 505
Literature 507
Chapter 14.Electrical Properties 509
14.1.Dielectric Properties 509
14.1.1.Polarizability 510
14.1.2.Behavior in an Alternating Electric Field 510
14.1.3.Dielectric Field Strength 512
14.1.4.Tracking 513
14.1.5.Electrostatic Charging 513
14.1.6.Electrets 515
14.2.Electronic Conductivity 516
14.2.1.Influence of Chemical Structure 516
14.2.2.Measuring Techniques 520
Literature 521
Chapter 15.Optical Properties 523
15.1.Light Refraction 523
15.2.Light Interference and Color 525
15.2.1.Basic Principles 525
15.2.2.Iridescent Colors 526
15.3.Light Transmission and Reflection 527
15.3.1.Total Reflection 527
15.3.2.Transparency 528
15.3.3.Gloss 529
15.4.Light Scattering 530
15.4.1.Phenomena 530
15.4.2.Opacity 531
Literature 532