Alkene polymerization reactions with transition metal catalysts

During the past 30 years, the field of alkene polymerization over transition metal catalysts underwent several major changes:
1. The list of commercial heterogeneous Ziegler-Natta catalysts for the synthesis of polyethylene and stereoregular polyolefins was completely renewed affording an unprecedented degree of control over the polymer structure.
2. Research devoted to metallocene and other soluble transition-metal catalysis has vastly expanded and has shifted toward complexes of transition metals with multidentate ligands.
3. Recent developments in gel permeation chromatography, temperature-rising fractionation, and crystallization fractionation provided the first reliable information about differences between various active centers in transition-metal catalysts.
4. A rapid development of high-resolution 13C NMR spectroscopy resulted in greatly expanded understanding of the chemical and steric features of polyolefins and alkene copolymers.
These developments require a new review of all aspects of alkene polymerization reactions with transition-metal catalysts. The first chapter in the book is an introductory text for researchers who are entering the field. It describes the basic principles of polymerization reactions with transition-metal catalysts, the types of catalysts, and commercially manufactured polyolefins.
The next chapter addresses the principal issue of alkene polymerization catalysis: the existence of catalyst systems with single and multiple types of active centers. The subsequent chapters are devoted to chemistry and stereochemistry of elemental reaction steps, structures of catalyst precursors and reactions leading to the formation of active centers, kinetics of polymerization reactions, and their mechanisms.

Preface	p. vii
Abbreviations and Definitions	p. xi
1 The Beginner's Course: General Description of Transition Metal Catalysts and Catalytic Polymerization Reactions	p. 1
1.1 Classifications of Transition Metal Catalysts	p. 2
1.2 Composition and Structure of Ziegler-Natta Catalysts	p. 6
1.3 Metallocene Catalysts	p. 11
1.4 Homogeneous Catalysts Containing Non-Metallocene Complexes of Early- and Late-Period Transition Metals	p. 14
1.5 Chromium Oxide Catalysts	p. 15
1.6 Main Features of Alkene Polymerization Reactions	p. 17
1.7 Classes of Polymers Produced with Transition Metal Catalysts	p. 28
2 Single-Center and Multi-Center Polymerization Catalysis	p. 35
2.1 Definition of Single Type of Active Center	p. 36
2.2 Molecular Weight Distribution of Polymers Produced with Single-Center Catalysts	p. 37
2.3 Structural Uniformity of Polymers and Copolymers Produced with Single-Center Catalysts	p. 46
2.4 Examples of Polymers and Copolymers Produced with Single-Center Catalysts	p. 63
2.5 Examples of Polymers and Copolymers Produced with Multi-Center Catalysts	p. 65
3 Chemistry and Stereochemistry of Polymerization and Copolymerization Reactions with Transition Metal Catalysts	p. 85
3.1 Chemistry and Stereochemistry of Polymerization Reactions	p. 86
3.2 Heterogeneous Titanium- and Vanadium-Based Ziegler-Natta Catalysts	p. 98
3.3 Metallocene Catalysts	p. 124
3.4 Homogeneous Catalysts Based on Early-Period Transition Metals	p. 166
3.5 Homogeneous Catalysts Based on Late-Period Transition Metals	p. 176
3.6 Chromium-Based Catalysts	p. 183
3.7 Stereoselective and Stereoelective Polymerization Reactions of Branched 1-Alkenes	p. 184
3.8 Copolymerization Reactions of Alkenes	p. 190
4 Synthesis, Chemical Composition, and Structure of Transition Metal Components and Cocatalysts in Catalyst Systems for Alkene Polymerization	p. 207
4.1 Early Solid Catalysts	p. 209
4.2 Supported Catalysts for Homopolymerization and Copolymerization of Ethylene	p. 211
4.3 Supported Ziegler-Natta Catalysts for Polymerization of Propylene and Higher 1-Alkenes	p. 224
4.4 Chemical Composition of Solid Components and Cocatalyst Mixtures of Ti-Based Ziegler-Natta Catalyst Systems	p. 236
4.5 Reactions Leading to Formation of Active Centers in Ziegler-Natta Catalysts	p. 243
4.6 Metallocene Catalysts	p. 253
4.7 Non-Metallocene Homogeneous Catalysts	p. 270
4.8 Supported Homogeneous Catalysts	p. 277
4.9 Bicomponent Catalysts	p. 284
4.10 Catalysts for Stereospecific Polymerization of Styrenes	p. 287
5 Kinetics of Alkene Polymerization Reactions with Transition Metal Catalysts	p. 291
5.1 Two Aspects of Polymerization Kinetics	p. 292
5.2 Role of Diffusion in Alkene Polymerization Reactions	p. 295
5.3 Formal Kinetic Description of Alkene Polymerization Reactions with Transition Metal Catalysts	p. 299
5.4 Polymerization Reactions with Metallocene Catalysts	p. 310
5.5 Polymerization Reactions with Non-Metallocene Homogeneous Catalysts	p. 334
5.6 Synthesis of Alkene Block-Copolymers	p. 343
5.7 Polymerization Reactions with Solid and Supported Ziegler-Natta Catalysts	p. 349
5.8 Polymerization Reactions with Pseudo-Homogeneous Catalysts	p. 412
5.9 Polymerization Reactions with Chromium Oxide Catalysts	p. 413
6 Active Centers in Transition Metal Catalysts and Mechanisms of Polymerization Reactions	p. 419
6.1 Catalysts Derived from Metallocene Complexes	p. 420
6.2 Non-Metallocene Homogeneous Catalysts	p. 476
6.3 Active Centers in Heterogeneous Ziegler-Natta Catalysts	p. 486
6.4 Active Centers in Chromium Oxide Catalysts	p. 515
References	p. 523
Subject Index	p. 571

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