Ziegler-Natta Catalysts Polymerizations

Description

Ziegler-Natta Catalysts and Polymerizations reviews the general aspects of Ziegler-Natta catalysts and polymerizations of olefins, dienes, and many other types of monomers. Topics covered include the physical state of the polymer during polymerization; modification of Ziegler-Natta catalysts by third components; and termination of polymer chain growth. The oxidation state of catalysts and active centers is also discussed, along with copolymerizations and block polymerizations.
This book is comprised of 23 chapters and begins with an overview of Ziegler-Natta catalysts and polymerizations, their historical origins, scientific and commercial importance, and major advances in polymer science. The next chapter focuses on definitions and stereochemistry of Ziegler-Natta catalysts, together with analytical methods used to identify and quantitatively measure their structures. Some of the polymers produced commercially with Ziegler-Natta catalysts are considered. The discussion then turns to mechanisms for initiating and propagating olefins; mechanisms for stereochemical control of conjugated and nonconjugated dienes; and the basic kinetic parameters that characterize Ziegler-Natta polymerizations.
This monograph is written especially for chemistry and engineering graduate students and for industrial chemists, engineers, and managers who may become involved in a Ziegler-Natta problem.

Front Cover 2
Ziegler–Natta Catalysts and Polymerizations 5
Copyright Page 6
Deditation 7
Table of Contents 9
Foreword 15
Preface 17
John Boor 19
CHAPTER1. HIGHLIGHTS OF ZIEGLER–NATTA CATALYSTS AND POLYMERIZATIONS 21
- I. Highlights 21
- II. Collected Reviews 32
- References 32
CHAPTER 2. GENESIS OF ZIEGLER–NATTA CATALYSTS 39
- I. Scientific and Commercial Importance 39
- II. Historical Origins 41

Front Cover 2
Ziegler–Natta Catalysts and Polymerizations 5
Copyright Page 6
Deditation 7
Table of Contents 9
Foreword 15
Preface 17
John Boor 19
CHAPTER1. HIGHLIGHTS OF ZIEGLER–NATTA CATALYSTS AND POLYMERIZATIONS 21
- I. Highlights 21
- II. Collected Reviews 32
- References 32
CHAPTER 2. GENESIS OF ZIEGLER–NATTA CATALYSTS 39
- I. Scientific and Commercial Importance 39
- II. Historical Origins 41
- III. Anticipation of the Catalyst and Contemporary Discoveries 46
- IV. The Golden Age of Polymer Science 48
- References 49
CHAPTER 3. DEFINITIONS, STEREOCHEMISTRY, EXPERIMENTAL METHODS, AND COMMERCIAL POLYMERS 52
- I. Introduction 52
- II. Definition of Ziegler–Natta Catalysts 53
- III. Stereochemical Structures of Polymers and Methods of Characterization 55
- IV. Experimental Methods 81
- V. Commercial Polymers 87
- References 97
CHAPTER 4. CHEMICAL DESCRIPTION OF ZIEGLER–NATTA CATALYSTS FOR OLEFINS 100
- I. Introduction 100
- II. Factors Determining Behavior of Catalysts for Olefins 101
- III. Some Important Classes of Catalysts for Olefins 128
- IV. Conclusion 144
- References 145
CHAPTER 5. THE CHEMICAL DESCRIPTION OF CATALYSTS FOR CONJUGATED DIENES 150
- I. Introduction 150
- II. Factors Determining Isomerism 151
- III. Important Catalysts Identified for Specific Conjugated Dienes 161
- IV. Conclusion 168
- References 169
CHAPTER 6. INITIAL PHYSICAL STATE OF THE CATALYST 174
- I. Introduction 174
- II. Importance of the Physical State of the Catalyst 174
- III. Soluble Catalyst 176
- IV. Colloidal Catalysts 176
- V. Heterogenous Catalysis Including Supported Types 180
- VI. Conclusion 185
- References 186
CHAPTER 7. PHYSICAL STATE OF THE POLYMER DURING POLYMERIZATION 188
- I. Introduction 188
- II. The Solution Process 189
- III. The Slurry Process 192
- IV. Vapor Phase Process 193
- V. Conclusion 198
- References 198
CHAPTER 8. GROWTH OF THE POLYMER PARTICLE 200
- I. Introduction 200
- II. Replication 201
- III. Architecture of TiCl3 Particles 204
- IV. How Does the Polymer Particle Grow? 210
- V. Practical Importance 229
- VI. Conclusion 231
- References 231
CHAPTER 9. MODIFICATION OF ZIEGLER–NATTA CATALYSTS BY THIRD COMPONENTS 233
- I. Introduction 233
- II. Discussion of Donors: Types of Third Components Added 235
- III. Conclusion 259
- References 260
CHAPTER 10. TERMINATION OF POLYMER CHAIN GROWTH 264
- I. Introduction 264
- II. Chain Termination by Organic and Inorganic Compounds 265
- III. Chain Termination by Metal Alkyls 267
- IV. Chain Termination by Molecular Hydrogen 271
- V. Chain Termination by Unsaturated Hydrocarbons 276
- VI. Chain Termination by Thermal Cleavage 278
- VII. Chain Termination by Mechanical Forces 279
- References 279
CHAPTER 11. OXIDATION STATE OF CATALYSTS AND ACTIVE CENTERS 281
- I. Introduction 281
- II. Catalysts Containing Selected Period 2 Transition Metal Salts 282
- III. Conclusion 296
- References 297
CHAPTER 12. METAL ALKYL–FREE CATALYSTS 299
- I. Introduction 299
- II. Phillips and Standard of Indiana Catalysts 300
- III. Metal Alkyl–Free Catalysts Discovered after 1955 305
- IV. Relationship to Ziegler–Natta Catalysts 336
- References 338
CHAPTER 13. MECHANISMS FOR INITIATION AND PROPAGATION OF OLEFINS 345
- I. Introduction 345
- II. Nomenclature 346
- III. Proposed Mechanisms 347
- IV. Experimental Evidence 361
- V. Conclusion 381
- References 382
CHAPTER 14. MECHANISMS FOR INITIATION AND PROPAGATION OF DIENES 386
- I. Introduction 386
- II. Proposed Mechanisms 386
- III. Experimental Evidence 389
- IV. Conclusion 399
- References 400
CHAPTER 15. MECHANISMS FOR STEREOCHEMICAL CONTROL OF α–OLEFINS 402
- I. Introduction 402
- II. Mode of Addition 403
- III. Isotactic Propagation 410
- IV. Syndiotactic Propagation 431
- V. Steric Purity of Isotactic and Syndiotactic Polypropylenes 438
- VI. Conclusion 439
- References 439
CHAPTER 16. MECHANISMS FOR STEREOCHEMICAL CONTROL OF CONJUGATED AND NONCONJUGATED DIENES 442
- I. Introduction 442
- II. Conjugated Dienes 442
- III. Nonconjugated Dienes 456
- IV. Conclusion 459
- References 460
CHAPTER 17. MECHANISMS FOR STEREOCHEMICAL CONTROL OF STEREOSELECTIVE AND STEREOELECTIVE ISOTACTIC PROPAGATIONS 462
- I. Introduction 462
- II. Stereoselection 463
- III. Stereoe lection 468
- IV. Proposed Mechanisms 474
- References 482
CHAPTER 18. KINETICS 484
- I. Introduction 484
- II. Basic Kinetic Results 485
- III. Proposed Kinetic Models and Schemes 494
- IV. Operational Factors That Can Affect Kinetic Results 500
- V. Growth of Polymer Chain and Particle 510
- References 528
- VI. Conclusion 528
CHAPTER 19. POLYMERIZATION OF MONOMERS 532
- II. Ethylene 532
- I. Introduction 532
- III. 1-Olefins 533
- IV. 1,1-Disubstituted Ethylene 540
- V. 1,2-Disubstituted Ethylenes 541
- VI. Cycloolefins 543
- VII. Bicyclo[n.1.0]alkanes 551
- VIII. Polar Monomers 551
- IX. Alienes 559
- X. Acetylenes 560
- XI. Conjugated Cyclic and Acyclic Dienes 563
- XII. Nonconjugated Acyclic and Cyclic Diolefins 567
- References 574
CHAPTER 20. COPOLYMERIZATIONS 583
- I. Introduction 583
- II. Copolymerization Equation and Nomenclature 584
- III. Experimental Control over the Architecture of Copolymer Chains 585
- IV. Copolymerizations of Selected Comonomer Pairs 596
- V. Conclusion 603
- References 604
CHAPTER 21. BLOCK POLYMERIZATIONS 607
- I. Introduction 607
- II. Pioneering Work 608
- III. Other Studies Aimed at Block Polymers 615
- IV. Conclusion 618
- References 620
CHAPTER 22. OTHER USES OF THE ZIEGLER–NATTA CATALYST 622
- I. Introduction 622
- II. Radical and Cationic Polymerizations 622
- III. Metathesis of Acyclic and Cyclic Olefins 623
- IV. Oligomerization of Olefins and Acetylenes 624
- V. Isomerization of Olefins 626
- VI. Hydrogenation of Olefins and Unsaturated Polymers 627
- VII. Alkylation of Aromatic Nuclei by Unsaturated Systems 628
- VIII. Examples of Other Competing Side Reactions 628
- References 629
CHAPTER 23. FINAL COMMENTS AND OUTLOOK 631
Supplementary Bibliography 635
Subject Index 679

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