Handbook of Transition Metal Polymerization Catalysts

RAY HOFF is a former research scientist in polymerization catalysts for B.F. Goodrich, Chemplex Company, and Quantum Chemical Corporation and was a member of the adjunct faculty at Roosevelt University in Schaumburg, Illinois.

Notes on Contributors xvii

Preface xxix

Acknowledgments xxxiii

1 Industrial Metal Alkyls and Their Use in Polyolefin Catalysts 1
Dennis B. Malpass

1.1 Introduction 1

1.2 Metal Alkyls in Ziegler–Natta Catalysts 2

1.3 Aluminum Alkyls 4

1.4 Manufacturers of Aluminum Alkyls 10

1.5 Pricing and Selection Criteria for Aluminum Alkyls 11

1.6 Methylaluminoxanes 13

1.7 Magnesium Alkyls 18

1.8 Organoboron Compounds 24

1.9 Organozinc Compounds 26

References 27

2 Porous Silica in Transition Metal Polymerization Catalysts 31
Thomas J. Pullukat and Robert E. Patterson

2.1 Introduction 31

2.2 Production of Silica Gel Catalysts 33

2.3 Influence of Silica Gel Properties and Polymerization Conditions on Catalyst Performance 36

2.4 Conclusions 52

References 53

3 Activator Supports for Metallocene and Related Catalysts 57
Ray Hoff

3.1 Introduction 57

3.2 Activator Support Studies 58

3.3 Activator Support Patents 60

3.4 Conclusion 62

References 64

4 Computational Modeling of Polymerization Catalysts 67
Monika Srebro Hooper and Artur Michalak

4.1 Introduction 67

4.2 Computational Modeling of Chemical Reactions 68

4.3 Modeling the Catalyst Properties and the Polymerization Processes 76

4.4 Concluding Remarks 116

Acknowledgment 117

References 117

5 Computational Studies of Chromium: Silica Catalysts 131
Zhen Liu and Boping Liu

5.1 Introduction 131

5.2 Mechanistic Proposals for Phillips Catalyst 132

5.3 Theoretical Study on Phillips Catalyst 137

5.4 The Limitation of the Current Computations and a Prospect for the Future 156

References 157

6 Laboratory Reactors and Procedures for Catalyst Evaluation 161
Rinaldo Schiffino

6.1 Introduction 161

6.2 Setup in the Fume Hood 162

6.3 Autoclave Reactors and Safety Relief Devices 163

6.4 Purification Methods 164

6.5 Modular Reactor System 165

6.6 Catalyst Addition 168

6.7 Temperature Control 170

6.8 Autoclave Reactor Setup 172

6.9 Copolymerization 173

6.10 Gas-Phase Laboratory Reactors 175

References 176

7 Scale-Up of Catalyst Recipes to Commercial Production 177
Chung Ping Cheng

7.1 Introduction 177

7.2 Fundamental of Process Scale-Up 178

7.3 Considerations in Scaling Up a Laboratory Recipe 180

7.4 A Modern Polymerization Catalyst Production Facility 182

7.5 Other Scale-Up Considerations 187

References 187

8 Supported Titanium/Magnesium Ziegler Catalysts for the Production of Polyethylene 189
Yury V. Kissin, Thomas E. Nowlin, and Robert I. Mink

8.1 Introduction 189

8.2 Particle-Form Technology 192

8.3 General Architecture and Preparation of Supported Catalysts 193

8.4 Nonuniformity of Active Centers in Supported Ziegler Catalysts 205

8.5 Kinetics and Mechanism of Ethylene Polymerization Reactions with Ziegler Catalysts 209

8.6 Kinetic Interpretation of Ethylene Polymerization Reactions 217

8.7 Active Centers in Ziegler Catalysts 221

References 224

9 Stereospecific α-Olefin Polymerization with Heterogeneous Catalysts 229
John Severn and Robert L. Jones, JR

9.1 Introduction 229

9.2 Traditional Ziegler–Natta Catalyst Systems 241

9.3 Stereospecific Single Site Catalysts 266

9.4 Conclusion 295

References 296

10 Olefin Polymerization by Vanadium Complex Catalysts 313
Kotohiro Nomura and Xiaohua Hou

10.1 Introduction: Classical Ziegler-Type Vanadium Catalyst Systems 313

10.2 Vanadium Complexes Designed for Olefin Coordination Insertion Polymerization 315

10.3 Outlook 332

References 333

11 MgCl2-Supported Ti Catalysts for the Production of Morphology-Controlled Polyethylene 339
Long Wu and Sieghard Wanke

11.1 Introduction 339

11.2 Preparation of Morphology-Controlled MgCl2/TiCl4 Catalysts 342

11.3 Polymerization Processes 345

11.4 Effect of Prepolymerization on Activity Profiles and Prepolymer Properties 349

11.5 Polymerization Behavior 358

11.6 Summary and Conclusions 364

References 365

12 Product Morphology in Olefin Polymerization with Polymer-Supported Metallocene Catalysts 369
Long Wu and Sieghard Wanke

12.1 Introduction 369

12.2 Preparation of Polymer-Supported Metallocene Catalysts 371

12.3 Factors Affecting Morphology of Product Particles 379

12.4 Factors Affecting Product Morphology 389

12.5 Product Fines and Densities 394

12.6 Conclusions 396

References 396

13 A Review of the Phillips Chromium Catalyst for Ethylene Polymerization 401
Max P. McDaniel

13.1 Historical and Commercial Background 401

13.2 Catalyst Preparation 404

13.3 Control of Catalyst Activity 414

13.4 Control of Molecular Weight and MW Distribution 439

13.5 Control of Crystallinity 482

13.6 Control of Elasticity 509

13.7 Concluding Remarks 542

References 546

14 Silica-Supported Silyl Chromate-Based Ethylene Polymerization Catalysts 573
Kevin Cann

14.1 Introduction 573

14.2 Silyl Chromate Catalyst Development 573

14.3 Catalyst Structure 575

14.4 Polymerization Process 578

14.5 Product Characterization and Applications 579

14.6 Silica-Supported Reduced Silyl Chromate Catalyst Advancements 582

Acknowledgements 588

References 588

15 Late Transition Metal Catalyzed Co- and Terpolymerization of α-Olefins with Carbon Monoxide: Synthesis and Modification 591
Timo M. J. Anselment, Manuela Zintl, Maria Leute, Rüdiger Nowack, and Bernhard Rieger

15.1 Introduction and Historical Overview 591

15.2 Polyketone Synthesis: General Concept and Mechanism 593

15.3 Influence of the Catalyst on the Polymer Structure in α-Olefin/CO Copolymerization Reactions 599

15.4 Other Olefins for the Copolymerization with CO 610

15.5 Chemical Modification of Polyketones 616

References 618

16 Ethylene Polymerization and α-Olefin Oligomerization Using Catalysts Derived from Phosphoranes and Ni(II) or Ni(0) Precursors 623
Scott Collins

16.1 Introduction 623

16.2 Starting Materials 626

References 629

17 Overview of Ring-Opening Metathesis Polymerizations (ROMP) and Acyclic Diene Metathesis (ADMET) Polymerizations with Selected Ruthenium and Molybdenum Complexes 631
Robert T. Mathers

17.1 Introduction 631

17.2 Ruthenium Catalysts 634

17.3 Molybdenum Complexes 646

17.4 Summary 651

References 651

18 Copolymerization of Ethylene with Conjugated Dienes 661
Islem Belaid, Vincent Monteil, and Christophe Boisson

18.1 Introduction 661

18.2 Conventional
Ziegler–Natta Catalysts 663

18.3 Group

4 Metallocene Systems 665

18.4 Group 4 Post-metallocene Catalysts 670

18.5 Vanadium Bis(imino)pyridyl Catalysts 673

18.6 Group 8-, 9-, and 10-Based Catalysts 674

18.7 Rare Earth Catalysts 675

18.8 Conclusion 686

References 687

Appendix A: Pyrophoricity of Metal Alkyls 693
Dennis B. Malpass

Appendix B: Rheological Terms for Polymerization Catalyst Chemists 705
Gregory W. Kamykowski

Index 711