Alkene Polymerization Reactions with Transition Metal Catalysts (eBook)

Yury Kissin (Autor)

eBook Download: PDF

2008 | 1. Auflage
495 Seiten
Elsevier Science (Verlag)
978-0-08-055799-1 (ISBN)

Infos

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.

Inhalt

Cover 1
Preface 8
Abbreviations and Definitions 12
Contents 14
Chapter 1. The Beginner’s Course: General Description of Transition Metal Catalysts and Catalytic Polymerization Reactions 16
1.1. Classifications of Transition Metal Catalysts 17
1.2. Composition and Structure of Ziegler–Natta Catalysts 21
1.3. Metallocene Catalysts 26
1.4. Homogeneous Catalysts Containing Non-Metallocene Complexes of Early- and Late-Period Transition Metals 29
1.5. Chromium Oxide Catalysts 30
1.6. Main Features of Alkene Polymerization Reactions 32
1.7. Classes of Polymers Produced with Transition Metal Catalysts 43
Chapter 2. Single-Center and Multi-Center Polymerization Catalysis 50
2.1. Definition of Single Type of Active Center 51
2.2. Molecular Weight Distribution of Polymers Produced with Single-Center Catalysts 52
2.3. Structural Uniformity of Polymers and Copolymers Produced with Single-Center Catalysts 61
2.4. Examples of Polymers and Copolymers Produced with Single-Center Catalysts 78
2.5. Examples of Polymers and Copolymers Produced with Multi-Center Catalysts 80
Chapter 3. Chemistry and Stereochemistry of Polymerization and Copolymerization Reactions with Transition Metal Catalysts 100
3.1. Chemistry and Stereochemistry of Polymerization Reactions 101
3.2. Heterogeneous Titanium- and Vanadium-Based Ziegler–Natta Catalysts 113
3.3. Metallocene Catalysts 139
3.4. Homogeneous Catalysts Based on Early-Period Transition Metals 181
3.5. Homogeneous Catalysts Based on Late-Period Transition Metals 191
3.6. Chromium-Based Catalysts 198
3.7. Stereoselective and Stereoelective Polymerization Reactions of Branched 1-Alkenes 199
3.8. Copolymerization Reactions of Alkenes 205
Chapter 4. Synthesis, Chemical Composition, and Structure of Transition Metal Components and Cocatalysts in Catalyst Systems for Alkene Polymerization 222
4.1. Early Solid Catalysts 224
4.2. Supported Catalysts for Homopolymerization and Copolymerization of Ethylene 226
4.3. Supported Ziegler–Natta Catalysts for Polymerization of Propylene and Higher 1-Alkenes 239
4.4. Chemical Composition of Solid Components and Cocatalyst Mixtures of Ti-Based Ziegler–Natta Catalyst Systems 251
4.5. Reactions Leading to Formation of Active Centers in Ziegler–Natta Catalysts 258
4.6. Metallocene Catalysts 268
4.7. Non-Metallocene Homogeneous Catalysts 285
4.8. Supported Homogeneous Catalysts 292
4.9. Bicomponent Catalysts 299
4.10. Catalysts for Stereospecific Polymerization of Styrenes 302
Chapter 5. Kinetics of Alkene Polymerization Reactions with Transition Metal Catalysts 306
5.1. Two Aspects of Polymerization Kinetics 307
5.2. Role of Diffusion in Alkene Polymerization Reactions 310
5.3. Formal Kinetic Description of Alkene Polymerization Reactions with Transition Metal’Catalysts 314
5.4. Polymerization Reactions with Metallocene Catalysts 325
5.5. Polymerization Reactions with Non-Metallocene Homogeneous Catalysts 349
5.6. Synthesis of Alkene Block-Copolymers 358
5.7. Polymerization Reactions with Solid and Supported Ziegler–Natta Catalysts 364
5.8. Polymerization Reactions with Pseudo-Homogeneous Catalysts 427
5.9. Polymerization Reactions with Chromium Oxide Catalysts 428
Chapter 6. Active Centers in Transition Metal Catalysts and Mechanisms of Polymerization Reactions 434
6.1. Catalysts Derived from Metallocene Complexes 435
6.2. Non-Metallocene Homogeneous Catalysts 491
6.3. Active Centers in Heterogeneous Ziegler–Natta Catalysts 501
6.4. Active Centers in Chromium Oxide Catalysts 530
References 538
Subject Index 586

Produkt-Details

• Erscheint lt. Verlag: 10.3.2008
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Technische Chemie
• Themenwelt: Technik ► Umwelttechnik / Biotechnologie
• ISBN-10: 0-08-055799-6 / 0080557996
• ISBN-13: 978-0-08-055799-1 / 9780080557991