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