Ziegler-Natta Catalysts Polymerizations

1st Edition - December 2, 2012
Author: John Jr. Boor
Language: English
Paperback ISBN:
9 7 8 - 0 - 1 2 - 4 1 2 4 2 6 - 4
eBook ISBN:
9 7 8 - 0 - 3 2 3 - 1 4 3 4 1 - 7

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… Read more

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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.

Foreword

Preface

John Boor, Jr. (1930-1974)

1 Highlights of Ziegler-Natta Catalysts and Polymerizations

I. Highlights

II. Collected Reviews

References

2 Genesis of Ziegler-Natta Catalysts

I. Scientific and Commercial Importance

II. Historical Origins

III. Anticipation of the Catalyst and Contemporary Discoveries

IV. The Golden Age of Polymer Science

References

3 Definitions, Stereochemistry, Experimental Methods, and Commercial Polymers

I. Introduction

II. Definition of Ziegler-Natta Catalysts

III. Stereochemical Structures of Polymers and Methods of Characterization

IV. Experimental Methods

V. Commercial Polymers

References

4 Chemical Description of Ziegler-Natta Catalysts for Olefins

I. Introduction

II. Factors Determining Behavior of Catalysts for Olefins

III. Some Important Classes of Catalysts for Olefins

IV. Conclusion

References

5 The Chemical Description of Catalysts for Conjugated Dienes

I. Introduction

II. Factors Determining Isomerism

III. Important Catalysts Identified for Specific Conjugated Dienes

IV. Conclusion

References

6 Initial Physical State of the Catalyst

I. Introduction

II. Importance of the Physical State of the Catalyst

III. Soluble Catalyst

IV. Colloidal Catalysts

V. Heterogenous Catalysis Including Supported Types

VI. Conclusion

References

7 Physical State of the Polymer during Polymerization

I. Introduction

II. The Solution Process

III. The Slurry Process

IV. Vapor Phase Process

V. Conclusion

References

8 Growth of the Polymer Particle

I. Introduction

II. Replication

III. Architecture of TiCl3 Particles

IV. How Does the Polymer Particle Grow?

V. Practical Importance

VI. Conclusion

References

9 Modification of Ziegler-Natta Catalysts by Third Components

I. Introduction

II. Discussion of Donors: Types of Third Components Added

III. Conclusion

References

10 Termination of Polymer Chain Growth

I. Introduction

II. Chain Termination by Organic and Inorganic Compounds

III. Chain Termination by Metal Alkyls

IV. Chain Termination by Molecular Hydrogen

V. Chain Termination by Unsaturated Hydrocarbons

VI. Chain Termination by Thermal Cleavage

VII. Chain Termination by Mechanical Forces

References

11 Oxidation State of Catalysts and Active Centers

I. Introduction

II. Catalysts Containing Selected Period 2 Transition Metal Salts

III. Conclusion

References

12 Metal Alkyl-Free Catalysts

I. Introduction

II. Phillips and Standard of Indiana Catalysts

III. Metal Alkyl-Free Catalysts Discovered after 1955

IV. Relationship to Ziegler-Natta Catalysts

References

13 Mechanisms for Initiation and Propagation of Olefins

I. Introduction

II. Nomenclature

III. Proposed Mechanisms

IV. Experimental Evidence

V. Conclusion

References

14 Mechanisms for Initiation and Propagation of Dienes

I. Introduction

II. Proposed Mechanisms

III. Experimental Evidence

IV. Conclusion

References

15 Mechanisms for Stereochemical Control of α-Olefins

I. Introduction

II. Mode of Addition

III. Isotactic Propagation

IV. Syndiotactic Propagation

V. Steric Purity of Isotactic and Syndiotactic Polypropylenes

VI. Conclusion

References

16 Mechanisms for Stereochemical Control of Conjugated and Nonconjugated Dienes

I. Introduction

II. Conjugated Dienes

III. Nonconjugated Dienes

IV. Conclusion

References

17 Mechanisms for Stereochemical Control of Stereoselective and Stereoelective Isotactic Propagations

I. Introduction

II. Stereoselection

III. Stereoelection

IV. Proposed Mechanisms

References

18 Kinetics

I. Introduction

II. Basic Kinetic Results

III. Proposed Kinetic Models and Schemes

IV. Operational Factors That Can Affect Kinetic Results

V. Growth of Polymer Chain and Particle

VI. Conclusion

References

19 Polymerization of Monomers

I. Introduction

II. Ethylene

III. 1-Olefins

IV. 1,1-Disubstituted Ethylene

V. 1,2-Disubstituted Ethylenes

VI. Cycloolefins

VII. Bicyclo[n.1.0]alkanes

VIII. Polar Monomers

IX. Allenes

X. Acetylenes

XI. Conjugated Cyclic and Acyclic Dienes

XII. Nonconjugated Acyclic and Cyclic Diolefins

References

20 Copolymerizations

I. Introduction

II. Copolymerization Equation and Nomenclature

III. Experimental Control over the Architecture of Copolymer Chains

IV. Copolymerizations of Selected Comonomer Pairs

V. Conclusion

References

21 Block Polymerizations

I. Introduction

II. Pioneering Work

III. Other Studies Aimed at Block Polymers

IV. Conclusion

References

22 Other uses of the Ziegler-Natta Catalyst

I. Introduction

II. Radical and Cationic Polymerizations

III. Metathesis of Acyclic and Cyclic Olefins

IV. Oligomerization of Olefins and Acetylenes

V. Isomerization of Olefins

VI. Hydrogenation of Olefins and Unsaturated Polymers

VII. Alkylation of Aromatic Nuclei by Unsaturated Systems

VIII. Examples of Other Competing Side Reactions

References

23 Final Comments and Outlook

Supplementary Bibliography

Subject Index

Life Sciences

Physical Sciences & Engineering

Social Sciences & Humanities

Health

Ziegler-Natta Catalysts Polymerizations

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