Alkene Polymerization Reactions with Transition Metal Catalysts
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Table of contents
- Cover
- Prefacevii
- Abbreviations and Definitionsxi
- Contentsxiii
- Chapter 1. The Beginner’s Course: General Description of Transition Metal Catalysts and Catalytic1
- 1.1. Classifications of Transition Metal Catalysts2
- 1.2. Composition and Structure of Ziegler–Natta Catalysts6
- 1.3. Metallocene Catalysts11
- 1.4. Homogeneous Catalysts Containing Non-Metallocene Complexes of Early- and Late-Period Transition14
- 1.5. Chromium Oxide Catalysts15
- 1.6. Main Features of Alkene Polymerization Reactions17
- 1.7. Classes of Polymers Produced with Transition Metal Catalysts28
- Chapter 2. Single-Center and Multi-Center Polymerization Catalysis35
- 2.1. Definition of Single Type of Active Center36
- 2.2. Molecular Weight Distribution of Polymers Produced with Single-Center Catalysts37
- 2.3. Structural Uniformity of Polymers and Copolymers Produced with Single-Center Catalysts46
- 2.4. Examples of Polymers and Copolymers Produced with Single-Center Catalysts63
- 2.5. Examples of Polymers and Copolymers Produced with Multi-Center Catalysts65
- Chapter 3. Chemistry and Stereochemistry of Polymerization and Copolymerization Reactions with Trans85
- 3.1. Chemistry and Stereochemistry of Polymerization Reactions86
- 3.2. Heterogeneous Titanium- and Vanadium-Based Ziegler–Natta Catalysts98
- 3.3. Metallocene Catalysts124
- 3.4. Homogeneous Catalysts Based on Early-Period Transition Metals166
- 3.5. Homogeneous Catalysts Based on Late-Period Transition Metals176
- 3.6. Chromium-Based Catalysts183
- 3.7. Stereoselective and Stereoelective Polymerization Reactions of Branched 1-Alkenes184
- 3.8. Copolymerization Reactions of Alkenes190
- Chapter 4. Synthesis, Chemical Composition, and Structure of Transition Metal Components and Cocatal207
- 4.1. Early Solid Catalysts209
- 4.2. Supported Catalysts for Homopolymerization and Copolymerization of Ethylene211
- 4.3. Supported Ziegler–Natta Catalysts for Polymerization of Propylene and Higher 1-Alkenes224
- 4.4. Chemical Composition of Solid Components and Cocatalyst Mixtures of Ti-Based Ziegler–Natta Ca236
- 4.5. Reactions Leading to Formation of Active Centers in Ziegler–Natta Catalysts243
- 4.6. Metallocene Catalysts253
- 4.7. Non-Metallocene Homogeneous Catalysts270
- 4.8. Supported Homogeneous Catalysts277
- 4.9. Bicomponent Catalysts284
- 4.10. Catalysts for Stereospecific Polymerization of Styrenes287
- Chapter 5. Kinetics of Alkene Polymerization Reactions with Transition Metal Catalysts291
- 5.1. Two Aspects of Polymerization Kinetics292
- 5.2. Role of Diffusion in Alkene Polymerization Reactions295
- 5.3. Formal Kinetic Description of Alkene Polymerization Reactions with Transition Metal’Catalysts299
- 5.4. Polymerization Reactions with Metallocene Catalysts310
- 5.5. Polymerization Reactions with Non-Metallocene Homogeneous Catalysts334
- 5.6. Synthesis of Alkene Block-Copolymers343
- 5.7. Polymerization Reactions with Solid and Supported Ziegler–Natta Catalysts349
- 5.8. Polymerization Reactions with Pseudo-Homogeneous Catalysts412
- 5.9. Polymerization Reactions with Chromium Oxide Catalysts413
- Chapter 6. Active Centers in Transition Metal Catalysts and Mechanisms of Polymerization Reactions419
- 6.1. Catalysts Derived from Metallocene Complexes420
- 6.2. Non-Metallocene Homogeneous Catalysts476
- 6.3. Active Centers in Heterogeneous Ziegler–Natta Catalysts486
- 6.4. Active Centers in Chromium Oxide Catalysts515
- References523
- Subject Index571
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.
The book describes the latest commercial polymerization catalysts for the synthesis of polyethylenes and polypropylene
The book provides a detailed description of the multi-center nature of commercial Ziegler-Natta catalysts.
The book devotes specialized chapters to the most important aspects of transition metal polymerization catalysts: the reactions leading to the formation of active centers, the chemistry and stereochemistry of elemental polymerization steps, reaction kinetics, and the polymerization mechanism.
The book contains an introductory chapter for researchers who are entering the field of polymerization catalysis. It describes the basic principles of polymerization reactions with transition-metal catalysts and the types of commercially manufactured polyolefins and copolymers
The book contains over 2000 references, the most recent up to end of 2006.
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.
The book describes the latest commercial polymerization catalysts for the synthesis of polyethylenes and polypropylene
The book provides a detailed description of the multi-center nature of commercial Ziegler-Natta catalysts.
The book devotes specialized chapters to the most important aspects of transition metal polymerization catalysts: the reactions leading to the formation of active centers, the chemistry and stereochemistry of elemental polymerization steps, reaction kinetics, and the polymerization mechanism.
The book contains an introductory chapter for researchers who are entering the field of polymerization catalysis. It describes the basic principles of polymerization reactions with transition-metal catalysts and the types of commercially manufactured polyolefins and copolymers
The book contains over 2000 references, the most recent up to end of 2006.