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Principles of Polymerization
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Table of Contents

Preface xxiii 1 Introduction 1 1-1 Types of Polymers and Polymerizations 1 1-2 Nomenclature of Polymers 9 1-3 Linear, Branched, and Crosslinked Polymers 17 1-4 Molecular Weight 19 1-5 Physical State 24 1-6 Applications of Polymers 32 References 36 2 Step Polymerization 39 2-1 Reactivity of Functional Groups 40 2-2 Kinetics of Step Polymerization 44 2-3 Accessibility of Functional Groups 63 2-4 Equilibrium Considerations 65 2-5 Cyclization versus Linear Polymerization 69 2-6 Molecular Weight Control in Linear Polymerization 74 2-7 Molecular Weight Distribution in Linear Polymerization 80 2-8 Process Conditions 87 2-9 Multichain Polymerization 101 2-10 Crosslinking 103 2-11 Molecular Weight Distributions in Nonlinear Polymerizations 114 2-12 Crosslinking Technology 117 2-13 Step Copolymerization 135 2-14 High-Performance Polymers 144 2-15 Inorganic and Organometallic Polymers 168 2-16 Dendritic (Highly Branched) Polymers 174 2-17 Miscellaneous Topics 180 References 185 3 Radical Chain Polymerization 198 3-1 Nature of Radical Chain Polymerization 199 3-2 Structural Arrangement of Monomer Units 202 3-3 Rate of Radical Chain Polymerization 204 3-4 Initiation 209 3-5 Molecular Weight 236 3-6 Chain Transfer 238 3-7 Inhibition and Retardation 255 3-8 Determination of Absolute Rate Constants 264 3-9 Energetic Characteristics 271 3-10 Autoacceleration 282 3-11 Molecular Weight Distribution 289 3-12 Effect of Pressure 292 3-13 Process Conditions 296 3-14 Specific Commercial Polymers 300 3-15 Living Radical Polymerization 313 3-16 Other Polymerizations 330 References 332 4 Emulsion Polymerization 350 4-1 Description of Process 350 4-2 Quantitative Aspects 356 4-3 Other Characteristics of Emulsion Polymerization 363 References 369 5 Ionic Chain Polymerization 372 5-1 Comparison of Radical and Ionic Polymerizations 372 5-2 Cationic Polymerization of the Carbon-Carbon Double Bond 374 5-3 Anionic Polymerization of the Carbon-Carbon Double Bond 412 5-4 Block and Other Polymer Architectures 436 5-5 Distinguishing Between Radical, Cationic, and Anionic Polymerizations 443 5-6 Carbonyl Polymerization 444 5-7 Miscellaneous Polymerizations 449 References 452 6 Chain Copolymerization 464 6-1 General Considerations 465 6-2 Copolymer Composition 466 6-3 Radical Copolymerization 487 6-4 Ionic Copolymerization 506 6-5 Deviations from Terminal Copolymerization Model 512 6-6 Copolymerizations Involving Dienes 521 6-7 Other Copolymerizations 528 6-8 Applications of Copolymerization 529 References 533 7 Ring-Opening Polymerization 544 7-1 General Characteristics 545 7-2 Cyclic Ethers 548 7-3 Lactams 569 7-4 N-Carboxy-a-Amino Acid Anhydrides 578 7-5 Lactones 581 7-6 Nitrogen Heterocyclics 586 7-7 Sulfur Heterocyclics 588 7-8 Cycloalkenes 589 7-9 Miscellaneous Oxygen Heterocyclics 592 7-10 Other Ring-Opening Polymerizations 594 7-11 Inorganic and Partially Inorganic Polymers 595 7-12 Copolymerization 600 References 606 8 Stereochemistry of Polymerization 619 8-1 Types of Stereoisomerism in Polymers 620 8-2 Properties of Stereoregular Polymers 633 8-3 Forces of Stereoregulation in Alkene Polymerizations 637 8-4 Traditional Ziegler-Natta Polymerization of Nonpolar Alkene Monomers 644 8-5 Metallocene Polymerization of Nonpolar Alkene Monomers 665 8-6 Other Hydrocarbon Monomers 682 8-7 Copolymerization 684 8-8 Postmetallocene: Chelate Initiators 685 8-9 Living Polymerization 689 8-10 Polymerization of 1,3-Dienes 689 8-11 Commerical Applications 695 8-12 Polymerization of Polar Vinyl Monomers 699 8-13 Aldehydes 703 8-14 Optical Activity in Polymers 704 8-15 Ring-Opening Polymerization 707 8-16 Statistical Models of Propagation 708 References 713 9 Reactions of Polymers 729 9-1 Principles of Polymer Reactivity 729 9-2 Crosslinking 737 9-3 Reactions of Cellulose 745 9-4 Reactions of Poly(vinyl acetate) 748 9-5 Halogenation 748 9-6 Aromatic Substitution 750 9-7 Cyclization 751 9-8 Other Reactions 752 9-9 Graft Copolymers 752 9-10 Block Copolymers 759 9-11 Polymers as Carriers or Supports 760 9-12 Polymer Reagents 765 9-13 Polymer Catalysts 768 9-14 Polymer Substrates 771 References 777 Index 789

About the Author

GEORGE ODIAN received his PhD from Columbia University. He is currently Emeritus Professor of Chemistry at the College of Staten Island of the City University of New York. He has previously served as professor of chemistry and chairman, Division of Pure and Applied Sciences at Richmond College of CUNY, assistant professor at Columbia University, research director of RAI Research Company, and research chemist at Thiokol Chemical Company. He has written over sixty research publications and authored both taped and short courses for the American Chemical Society. He is also the coauthor of four books in general, organic, and biochemistry.

Reviews

"?this book would be useful?as a reference tool?" (IEEE Electrical Insulation Magazine, March/April 2006) "Chemists, chemical engineers, and material scientists who want to know more about the chemistry and structural control of polymers would find extensive information in this book?" (MRS Bulletin, February 2006) ??the most comprehensive treatment of this topic that I have encountered ? an essential component of the book collection of any research group involved in polymer synthesis.? (Advanced Materials, 2005; Vol., 17; 16) ??an excellent textbook for today?s students of polymer chemistry, chemical engineering and materials science, as well as a current reference for the researcher?.? (Apollit, 2005) "This is the fourth edition of what has not only become a classic textbook but is most useful as a reference book...the author...writes clear and precise sentences and makes what can be a dry subject interesting to read.? (E-STREAMS, October 2004) "...an admirable text for teaching...and also serves as a valuable reference...a real investment and an important desk reference for polymer synthesis chemists." (Polymer News)

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