Introduction to macromolecular science / Petr Munk, Tejraj M. Aminabhavi.

Format:

Book

Author/Creator:

Munk, Petr.

Contributor:

Aminabhavi, Tejraj Malleshappa.

Alumni and Friends Memorial Book Fund.

Language:

English

Subjects (All):

Macromolecules.

Physical Description:

xxi, 609 pages : illustrations ; 25 cm

Edition:

Second edition.

Place of Publication:

New York : Wiley, [2002]

Contents:

Prologue: Macromolecules Around Us xix

Natural Macromolecules xx

Man-Made Macromolecules xx

1 Structure of Macromolecules 1

1.1 Concept of a Macromolecule 1

1.2 Primary Structure

Covalent Bonds 2

1.2.1 Linear Polymers 2

1.2.1.1 Polymers with All-Carbon Backbones 3

1.2.1.2 Polymers with Heteroatoms in the Backbone 9

1.2.1.3 Polymers with Inorganic Backbones 12

1.2.2 Cyclolinear Polymers 14

1.2.3 Branched Polymers 18

1.2.4 Copolymers 21

1.2.4.1 Types of Copolymers 22

1.2.4.2 Some Important Copolymers 23

1.2.5 Isomerism of Polymer Chains and Tacticity 24

1.2.6 Nomenclature of Polymers 28

1.2.7 Macromolecular Networks 31

1.2.7.1 Loose Networks 31

1.2.7.2 Dense Networks

Thermosets 32

1.2.7.3 Two-Dimensional Networks 35

1.2.8 Natural Macromolecules 36

1.2.8.1 Polysaccharides 37

1.2.8.2 Proteins and Polypeptides 39

1.2.8.3 Nucleic Acids 42

1.3 Higher Structure

Conformations 45

1.3.1 Random Macromolecular Coils 46

1.3.1.1 Short-Range Interactions 49

1.3.1.2 Statistical Coils 52

1.3.1.3 Long-Range Interactions 53

1.3.1.4 Polyelectrolyte Effect 56

1.3.2 Secondary Structure

Regular Conformations 58

1.3.3 Tertiary Structure

Arrangement of Larger Segments 61

1.3.4 Enzymes

Tertiary Conformations in Action 62

1.4 Multimolecular Arrangements

Quaternary Structure 64

1.4.1 Multiunit Proteins 64

1.4.2 Double Helix of Nucleic Acids 66

1.4.3 Genetic Coding and Reproduction 68

1.4.4 Protein Synthesis 69

1.4.5 Natural Supportive Structures 71

1.5 Aggregates of Small Molecules 71

1.5.1 Colloids 72

1.5.2 Micelles 75

1.5.3 Block Copolymer Micelles 79

1.6 Molecular Weight 80

1.6.1 Molecular Weight Averages 81

1.6.2 Distribution of Molecular Weights 84

1.C Derivations 92

1.D Numerical Problems 93

2 Techniques for Synthesis of Polymers 95

2.1 Polycondensation 96

2.1.1 Carboxylic Acid Derivatives 97

2.1.1.1 Reaction Mechanisms 97

2.1.1.2 Cyclization Reactions 101

2.1.1.3 Kinetics of Polycondensation 102

2.1.1.4 Equilibrium; Distribution of Molecular Weights 105

2.1.1.5 Gel Point; Three-Dimensional Structures 108

2.1.1.6 Dendrimers and Hyperbranched Polymers 110

2.1.2 Isocyanates 115

2.1.3 Aldehydes 119

2.1.4 Condensations Forming Cycles 124

2.1.5 Siloxanes 127

2.1.6 Epoxy Resins 130

2.1.7 Miscellaneous Polycondensations 131

2.2 Radical Polymerization 135

2.2.1 Production of Radicals, Initiators 135

2.2.2 Reactions of Radicals 139

2.2.3 Reactivity of Radicals 142

2.2.4 Kinetics of Radical Polymerization 145

2.2.4.1 Initiation, Propagation, and Termination 145

2.2.4.2 Rate of Polymerization and Molecular Weight 149

2.2.4.3 Chain Transfer 157

2.2.4.4 Inhibition and Retardation 162

2.2.4.5 Kinetics at High Conversions

Gel Effect 164

2.2.5 Radical Copolymerization 166

2.2.6 Thermodynamics of Radical Polymerization 172

2.2.7 Living Radical Polymerization 175

2.2.7.1 Atom Transfer Radical Polymerization (ATRP) 176

2.2.7.2 Nitroxide-Mediated Radical Polymerization 177

2.2.8 Industrial Polymerizations 178

2.2.8.1 Suspension Polymerization 179

2.2.8.2 Precipitation Polymerization 179

2.2.8.3 Emulsion Polymerization 180

2.2.8.4 Cross-Linked Structures 181

2.3 Ionic and Coordination Polymerization 184

2.3.1 Anionic Polymerization 184

2.3.1.1 Ions in Nonpolar Media 185

2.3.1.2 Anionic Initiators 187

2.3.1.3 Initiation and Propagation 189

2.3.1.4 Living Polymers and Block Copolymers 193

2.3.1.5 Ring-Opening Polymerizations 195

2.3.2 Cationic Polymerization 198

2.3.2.1 Cationic Initiators 199

2.3.2.2 Polymerization of Olefins 200

2.3.2.3 Living Cationic Polymerization 203

2.3.2.4 Polymerization of Aldehydes and Cyclic Monomers 204

2.3.3 Coordination Polymerization 205

2.3.3.1 Ziegler-Natta Initiators 206

2.3.3.2 Metallocene Catalysts 208

2.3.3.3 Metathesis Polymerization 214

2.3.3.4 Group Transfer Polymerization (GTP) 218

2.3.3.5 Miscellaneous Coordination Initiators 220

2.4 Reactions on Macromolecules 220

2.4.1 Reactions of Side Groups 221

2.4.2 Cyclization Reactions 222

2.4.3 Modifications of Cellulose 224

2.4.4 Cross-Linking and Vulcanization 226

2.4.5 Polymer Grafting 228

2.4.6 Polymer Degradation and Stabilization 230

2.B Review Questions and Derivations 235

2.C Numerical Problems 238

3 Macromolecules in Solution 241

3.1 Thermodynamics of Macromolecular Solutions 242

3.1.1 Flory-Huggins Model 244

3.1.1.1 Low-Molecular-Weight Mixtures 244

3.1.1.2 Macromolecular Solutions 248

3.1.1.3 Chemical Potentials 250

3.1.2 Excluded-Volume Theories 254

3.1.2.1 Compact Molecules 254

3.1.2.2 Macromolecular Coils 256

3.1.3 Equation-of-State Theories 261

3.1.4 Phenomenological Approach 269

3.1.5 Anisotropic Solutions and Liquid Crystals 271

3.1.5.1 Types of Liquid Crystals 272

3.1.5.2 Liquid Crystalline Polymers 275

3.2 Equilibrium Methods for the Study of Macromolecules in Solution 277

3.2.1 Osmometry 279

3.2.1.1 Macromolecular Solutions in Mixed Solvents 284

3.2.1.2 Osmometry of Polyelectrolytes 288

3.2.1.3 Technical Aspects of Osmometry 291

3.2.2 Equilibria in the Ultracentrifuge 293

3.2.2.1 The Ultracentrifuge 295

3.2.2.2 Sedimentation Equilibrium 298

3.2.2.3 Equilibrium in a Density Gradient 305

3.2.3 Phase Equilibria 308

3.2.3.1 Fractionation of Polymers 318

3.3 Hydrodynamics of Macromolecular Solutions 321

3.3.1 Viscous Flow of Liquids 322

3.3.2 Particles Moving Through a Liquid

Frictional Coefficients 326

3.3.3 Particles Suspended in a Flowing Liquid

Viscosity Increase 330

3.3.4 Hydrodynamic Interactions 332

3.3.5 Hydrodynamics of Macromolecular Coils 335

3.3.6 Concentration Effects in Macromolecular Hydrodynamics 340

3.3.7 Orientation and Deformation of Particles in a Flowing Liquid 343

3.4 Hydrodynamic Methods for the Study of Macromolecules in Solution 346

3.4.1 Diffusion 346

3.4.1.1 Experimental Diffusimetry 349

3.4.1.2 Interpretation of Diffusion Coefficients 351

3.4.2 Sedimentation Velocity 352

3.4.2.1 Homogeneous Solutes 352

3.4.2.2 Heterogeneous Solutes 358

3.4.2.3 Archibald Method 359

3.4.3 Viscometry 360

3.4.3.1 Viscometers 361

3.4.3.2 Intrinsic Viscosity 364

3.4.3.3 Molecular Weight and Coil Dimensions 365

3.4.3.4 Unperturbed Dimensions, Thermodynamic Parameters 367

3.4.3.5 Branched Chains 370

3.4.3.6 Polydisperse Polymers 370

3.4.3.7 Concentration Dependence of Viscosity 371

3.4.3.8 Non-Newtonian Viscosity 372

3.4.4 Flow Birefringence 374

3.4.4.1 Optical Properties of Dielectrics 374

3.4.4.2 Molecular Anisotropy 376

3.4.4.3 Birefringence of Systems Oriented by Flow 377

3.4.4.4 Birefringence and Stress 382

3.4.4.5 Experimental Arrangements 383

3.4.4.6 Interpretation of Flow Birefringence Data 385

3.5 Light Scattering 386

3.5.1 Scattering by a Single Small Isotropic Particle 386

3.5.2 Light Scattered by an Anisotropic Particle 390

3.5.3 Interference of Light Waves 392

3.5.4 Scattering by Large Particles 393

3.5.5 Scattering by Macroscopic Systems 398

3.5.5.1 Theory of Fluctuations 400

3.5.5.2 Scattering by Gases and Liquids 401

3.5.6 Light Scattering by Polymer Solutions 403

3.5.6.1 Measurement of Molecular Weight and Size 403

3.5.6.2 Effect of Polydispersity 406

3.5.6.3 Polymers in Mixed Solvents 406

3.5.6.4 Turbidity 408

3.5.7 Quasi-Elastic Light Scattering 409

3.5.8 Experimental Arrangements 411

3.5.9 Small-Angle X-Ray Scattering (SAXS) 413

3.6 Spectral Methods 417

3.6.1 Ultraviolet Spectrophotometry 417

3.6.2 Fluorescence 418

3.6.3 Infrared Spectra 419

3.6.4 Nuclear Magnetic Resonance (NMR) 421

3.6.5 Mass Spectrometry 425

3.7 Separation

Techniques 426

3.7.1 Electrophoresis 428

3.7.1.1 Free Electrophoresis 429

3.7.1.2 Paper Electrophoresis 430

3.7.1.3 Gel Electrophoresis 432

3.7.1.4 Capillary Electrophoresis 433

3.7.1.5 Electrofocusing 434

3.7.1.6 SDS Electrophoresis 435

3.7.2 Gel Permeation Chromatography (GPC) 435

3.7.2.1 Principles of GPC 438

3.7.2.2 Molecular Weight and Universal Calibration Curve 440

3.7.2.3 Molecular Weight Distribution 443

3.7.2.4 Critical Point GPC 443

3.7.2.5 Selection of Columns 444

3.7.2.6 Detectors Used in GPC 445

3.7.3 Field Flow Fractionation 447

3.7.4 Supercritical Fluid Chromatography 449

3.8 Techniques for the Study of the Structure of Nucleic Acids 449

3.8.1 Polymerase Chain Reaction 450

3.8.2 Separation of DNA Fragments 452

3.8.2.1 Pulsed Field Gel Electrophoresis (PFGE) 452

3.8.2.2 Southern Transfer Technique 453

3.8.2.3 DNA Profile Analysis 454

3.8.3 Sequencing of DNA Fragments 455

3.A.2 Thermodynamics 457

3.A.3 Equilibrium Methods (Osmometry, Sedimentation Equilibrium, and Phase Equilibria) 458

3.A.4 Hydrodynamics and Hydrodynamic Methods 458

3.A.5 Light Scattering and Spectral Methods 458

3.A.6 Separation Techniques 459

3.A.7 Techniques to Study the Structure of Nucleic Acids 459

3.B Thermodynamics 459

3.B.2 Derivations and Numerical Problems 460

3.C Osmometry, Sedimentation Equilibrium, and Phase Equilibria 461

3.C.2 Derivations and Numerical Problems 462

3.D Hydrodynamics and Hydrodynamic Methods 464

3.D.2 Derivations and Numerical Problems 465

3.E Light Scattering 467

3.E.2 Derivations and Numerical Problems 468

3.F Spectral Methods 470

3.G Separation Methods 471

3.G.2 Derivations and Numerical Problems 472

3.H Techniques to Study the Structure of Nucleic Acid 473

4 Bulk Polymers 474

4.1 Properties of Bulk Polymers 474

4.1.1 Stress and Strain 476

4.1.2 Glassy Polymers 479

4.1.3 Elastic Networks 481

4.1.3.1 Theory of Rubber Elasticity 482

4.1.3.2 Swelling of Gels 488

4.1.4 Polymer Melts 489

4.1.5 Viscoelastic Materials 492

4.1.5.1 Creep and Stress Relaxation 493

4.1.5.2 Dynamic Experiments 498

4.1.6 Crystalline Polymers 504

4.1.6.1 Morphology of Crystalline Polymers 506

4.1.6.2 Mechanical Properties of Crystalline Polymers 511

4.1.7 Multicomponent and Multiphase Materials 512

4.1.7.1 Plasticization of Polymers 512

4.1.7.2 Polymer Blends 514

4.1.7.3 Heterophase Materials 516

4.1.8 Electrical and Optical Properties of Polymers 519

4.1.9 Transport Through Polymers 522

4.2 Techniques for the Study of Bulk Polymers 525

4.2.1 Mechanical Methods 525

4.2.2 Differential Scanning Calorimetry (DSC) 528

4.2.3 Inverse Gas Chromatography (IGC) 531

4.2.4 X-Ray Diffraction 535

4.2.5 Neutron Scattering 539

4.3 Techniques for the Study of Polymer Surfaces 542

4.3.1 Optical Microscopy 542

4.3.2 Electron Microscopy 543

4.3.3 Atomic Force Microscopy (AFM) and Scanning Tunneling Microscopy (STM) 545

4.3.4 Electron Spectroscopy for Chemical Analysis (ESCA) 547

4.C Numerical Problems 554

5 Technology of Polymeric Materials 557

5.1 Fabrication of Polymers 557

5.1.1 Compounding and Mixing 558

5.1.2 Casting 559

5.1.3 Extrusion 559

5.1.4 Bubble Blown Film Extrusion 561

5.1.5 Cast Film Extrusion 563

5.1.6 Coating 563

5.1.7 Fiber Spinning 564

5.1.8 Calendering 567

5.1.9 Molding 567

5.1.10 Foam Fabrication 570

5.2 Testing of Polymers 571

5.2.1 Mechanical Testing 571

5.2.2 Thermal Testing 573

5.3 Barrier Properties of Polymers 574

5.3.1 Membrane Types 575

5.3.2 Membrane Preparations 576

5.3.2.1 Symmetric Porous Membranes 576

5.3.2.2 Asymmetric Membranes 577

5.3.2.3 Ion-Exchange Membranes 579

5.3.3 Membrane-Based Separation Processes 580

5.3.3.1 Reverse Osmosis and Filtration Techniques 580

5.3.3.2 Electrodialysis 583

5.3.3.3 Gas Separation 583

5.3.3.4 Pervaporation 585

5.3.4 Polymeric Devices for Drug Delivery 588

Epilogue: Literature About Macromolecules 593

A. Textbooks About Macromolecules 593

B. Monograph Series and Encyclopedias 594

C. Handbooks and Reference Sources 594

D. Macromolecular Journals 595.

Notes:

Includes bibliographical references (pages 593-595) and index.

Local Notes:

Acquired for the Penn Libraries with assistance from the Alumni and Friends Memorial Book Fund.

ISBN:

0471417165

OCLC:

47705834