Organometallic Catalysts and Olefin Polymerization: Catalysts for a New Millennium

✍ Scribed by Ulrich Wieser, Hans-Herbert Brintzinger (auth.), Dr. Richard Blom, Arild Follestad, Prof. Erling Rytter, Prof. Mats Tilset, Prof. Martin Ystenes (eds.)

• Publisher: Springer-Verlag Berlin Heidelberg
• Year: 2001
• Tongue: English
• Leaves: 447
• Edition: 1
• Category: Library

✦ Synopsis

"Catalysis is more art than science", probably all of you have heard and even used this expression. Whether it is true or not, it alludes to the experience that new catalysts are hard to find, and near impossible to predict. Hard work and a lifetime of experience is invaluable. However, a keen mind might give insight into where to search, but not necessarily about where to find the answers. Historically, "quantum leaps" have often arisen from serendipity - we all know the story about the nickel-contaminated reactor that triggered further research towards the first coordination catalyst for ethene polymerization. Taking advan­ tage of this event, Karl Ziegler became the first chemist to earn both a Nobel prize and a fortune for the same invention. A broken NMR tube helped Walter Kaminsky discover the effect of high concentrations of methylaluminoxanes as co catalysts for metallocenes. When air reacted with the concentrated trim ethyl aluminum solution, sufficient amounts of methylaluminoxanes were formed, and the lazy catalyst dormant in the NMR tube suddenly became sensationally active. Ziegler and Kaminsky were lucky and had the genius needed to take advantage of their luck.

✦ Table of Contents

Front Matter....Pages I-XII
Front Matter....Pages 1-1
UV/VIS Studies on the Activation of Zirconocene-Based Olefin-Polymerization Catalysts....Pages 3-13
Activation of Siloxy-substituted Compounds and Homopolymerisation of Ethylene by Different Soluble Alumoxane Cocatalysts....Pages 14-22
Methylaluminoxane as a Cocatalyst for Olefin Polymerization. Structure, Reactivity and Cocatalytic Effect....Pages 23-36
Olefin Polymerization under High-pressure: Formation of Super-high Molecular Weight Polyolefins....Pages 37-45
Higher-order Kinetics in Propene Polymerizations by Zirconocene Catalysts. Analysis of Alternative Reaction Mechanisms via a Genetic Algorithm....Pages 46-62
Structures of MAO: Experimental Data and Molecular Models According to DFT Quantum Chemical Simulations....Pages 63-71
A DFT Study of Ethylene Polymerization by Zirconocene-boron Catalytic Systems....Pages 72-85
Activation Reactions of Cp 2 ZrCl 2 and Cp 2 ZrMe 2 with Aluminium Alkyl Type Cocatalysts Studied by in situ FTIR Spectroscopy....Pages 86-96
Single Component Zirconocene Catalysts for the Stereospecific Polymerization of MMA....Pages 97-108
Modeling Methylaluminoxane (MAO)....Pages 109-123
Front Matter....Pages 125-125
Phosphinoalkyl-Substituted Cyclopentadienyl Chromium Catalysts for the Oligomerization of Ethylene....Pages 127-136
1-Hexene Polymerization Initiated by α-Diimine [N,N] Nickel Dibromide / MAO Catalytic Systems : Influence of the α-Diimine Ligand Structure....Pages 137-146
1,3,5-Triazacyclohexane Complexes of Chromium as Homogeneous Model Systems for the Phillips Catalyst....Pages 147-155
Rare Earth Half-Sandwich Catalysts for the Homo- and Copolymerization of Ethylene and Styrene....Pages 156-165
Front Matter....Pages 167-167
The New Revolutionary Development Of Catalysis As The Driving Force For The Commercial Dynamic Success Of Polyolefins....Pages 169-195
Basic Approaches for the Design of Active Sites on the Traditional Ziegler Catalysts....Pages 196-205
Surface Analytical Approaches for the Phillips Catalyst by EPMA and XPS....Pages 206-216
Main Kinetic Features of Ethylene Polymerization Reactions with Heterogeneous Ziegler-Natta Catalysts in the Light of Multi-Center Reaction Mechanism....Pages 217-228
Hydrogen Effects in Propylene Polymerization with Ti-Based Ziegler-Natta Catalysts. Chemical Mechanism....Pages 229-239
Elementary Steps of Ziegler-Natta Catalyst Intermediates Formation. Incorporation of Magnesium Alkoxides with [Ti(dipp) 4 ], Ph 3 SiOH, [AL(CH 3 ) 3 ], and MCL (3) 4 (M = V, Zr)....Pages 240-250
Front Matter....Pages 251-251
Mechanistic Aspects of Olefin Polymerization with Metallocene Catalysts: Evidence from NMR Investigations....Pages 253-266
Syndiotactic Specific Structures, Symmetry Considerations, Mechanistic Aspects....Pages 267-279
The Particularities of Isospecific Polypropylene Synthesis in Bulk with Ansa-metallocene Catalysts....Pages 280-288
Ethene Polymerization Catalyzed by Monoalkyl and Methyl Substituted Zirconocenes. Possible Effects of Reaction Barriers and Ligand-Metal Agostic Interactions....Pages 289-298
A Density Functional Theory Study of the Syndiotactic-Specific Polymerization of Styrene....Pages 299-306
Influence of Ligands on the Deactivation of Group IV Metallocene Catalysts in the High-Temperature Polymerization of Ethene....Pages 307-314
Front Matter....Pages 315-315
Correlations Between Chain Branching, Morphology Development and Polymer Properties of Polyethenes....Pages 317-326
Heterogenized Bifunctional Catalysts in Olefin Polymerization....Pages 327-334
Long-Chain Branched Polyethene via Metallocene-Catalysis: Comparison of Catalysts....Pages 335-345
New Half-Sandwich Titanocenes for the Polymerization of Butadiene....Pages 346-352
Metallocene Catalyzed Copolymerization of Propene with Mono- and Diolefins....Pages 353-364
A Comparison of the Behavior of Nickel/MAO Catalytic Systems in the Polymerization of Styrene and 1,3-Cyclohexadiene....Pages 365-374
Front Matter....Pages 375-375
Activity Limits of Heterogeneous Polymerization Catalysts....Pages 377-386
Reversibly Crosslinked Polystyrene as a Support for Metallocenes Part I: Covalently Bonded Metallocenes and Functionalized Supports....Pages 387-395
Reversibly Crosslinked Polystyrene as a Support for Metallocenes Part II: Non-Covalent Bonding for the Immobilization....Pages 396-403
An Intrinsic Defect of Slow Monomer Diffusion Theory for Explaining Broad MWDs....Pages 404-413
Prepolymerization and Copolymerization Studies Using Homogeneous and Silica-supported Cp 2 ZrCI 2 /MAO Catalyst Systems....Pages 414-426
Unique Flowability Behavior of Ethylene Copolymers Produced by a Catalyst System Comprising Ethylenebis(indenyl)hafnium Dichloride and Aluminoxane....Pages 427-433
Diffusion Measurements in Porous Polymer Particles....Pages 434-443

✦ Subjects

Polymer Sciences; Industrial Chemistry/Chemical Engineering; Organic Chemistry; Inorganic Chemistry; Condensed Matter Physics