FI catalysts for olefin polymerization--a comprehensive treatment.

All-Polyolefin Composites Markus Stürzel,† Shahram Mihan,‡ and Rolf Mülhaupt*,†,§ †Freiburg Materials Research Center (FMF) and Institute for Macromolecular Chemistry, Albert-Ludwigs-University Freiburg, Stefan-Meier-Strasse 31, D-79104 Freiburg, Germany ‡Basell Polyolefine GmbH, Catalyst Systems, Industriepark Hoechst, D-65926 Frankfurt am Main, Germany Sustainability Center Freiburg, Ecker-Strasse 4, D-79104 Freiburg, Germany

From Multisite Polymerization Catalysis to Sustainable Materials and All-Polyolefin Composites

More than 50 years have passed since Ziegler and Natta shared the Nobel Prize in Chemistry for their discovery of olefin polymerization catalysts. The field of metal-catalysed polymerization has since matured, in no small part owing to the development of several high-performance catalysts. Although polymerization research has in many ways been driven by catalyst development, this has often occurred as a result of trial and error discovery of a promising motif, followed by extensive tuning of the steric and electronic properties of the ligand(s) present in the lead complex. Recently, some alternative design strategies have emerged that afforded new classes of olefin polymerization catalysts. This Perspective highlights recently designed catalyst motifs and the novel reactivity patterns they enable. Special attention is given to methods specifically designed for the copolymerization of ethylene with polar-functionalized co-monomers — challenging reactions that showcase these creatively designed catalyst motifs. The development of high-performance olefin polymerization catalysts is a major driving force in polyolefin studies. This Perspective discusses some alternative strategies for catalyst design — strategies in which existing systems are tuned beyond merely modifying the electronic and steric properties.

Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning

Research on "post-metallocene" polymerization catalysis ranges methodologically from fundamental mechanistic studies of polymerization reactions over catalyst design to material properties of the polyolefins prepared. A common goal of these studies is the creation of practically useful new polyolefin materials or polymerization processes. This Review gives a comprehensive overview of post-metallocene polymerization catalysts that have been put into practice. The decisive properties for this success of a given catalyst structure are delineated.

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Post-metallocenes in the industrial production of polyolefins.

The Chemistry of Catalyst Activation: The Case of Group 4 Polymerization Catalysts†

Ethylene/Norbornene Copolymerization Behavior of Bis(phenoxy−imine)Ti Complexes Combined with MAO

Attractive interactions in olefin polymerization mediated by post-metallocene catalysts with fluorine-containing ancillary ligands

The ethylene and ethylene/α-olefin (co)polymerization behavior of bis(phenoxy−imine)Ti complexes 1−7 possessing a series of substituents ortho to the phenoxy O's (ortho substituents 1, iPr; 2, cyclohexyl; 3, cyclooctyl; 4, cyclododecyl; 5, tBu; 6, CMe2Ph; 7, Ph) with dried methylaluminoxane activation was investigated. At 50 °C, all complexes displayed some of the characteristics of living ethylene polymerization and produced polyethylenes (PEs) with very narrow molecular weight distributions (Mw/Mn 1.08−1.19, Mw 14 900−62 100), albeit under limited conditions. Generally, the Ti complexes with sterically bulkier ortho substituents exhibited higher activities [e.g., 6: activity 93.2 kg of PE/(mol of cat. min)]; the ortho substituents with quaternary α-C atoms attached to the phenoxy rings, providing higher activities than those with tertiary α-C atoms on the basis of the steric bulk of the entire ortho substituent. To our surprise, complex 7 incorporating an ortho phenyl group displayed the highest activit...

Ethylene and Ethylene/α-Olefin (Co)Polymerization Behavior of Bis(phenoxy−imine)Ti Catalysts: Significant Substituent Effects on Activity and Comonomer Incorporation

PROBLEM TO BE SOLVED: To provide a resin composition which is excellent in temporal stability of dielectric characteristics and heat resistance and provides a crosslinked body excellent in transparency, mechanical characteristics and a balance between dielectric characteristics and gas barrier propertiesSOLUTION: A resin composition comprises a cyclic olefin copolymer (P) containing a specified amount of a specified repeating unit and one or more polymers (A) which are selected from thermosetting resins, olefinic resins, acrylic resins, styrene resins, rubber resins, fluororesins, general-purpose engineering plastics, super-engineering plastics and biodegradable plastics and are different from the cyclic olefin copolymer (P)

Akihiko Iwashita

Papers

FI catalysts for olefin polymerization--a comprehensive treatment.

Ethylene/Norbornene Copolymerization Behavior of Bis(phenoxy−imine)Ti Complexes Combined with MAO

Attractive interactions in olefin polymerization mediated by post-metallocene catalysts with fluorine-containing ancillary ligands

Ethylene and Ethylene/α-Olefin (Co)Polymerization Behavior of Bis(phenoxy−imine)Ti Catalysts: Significant Substituent Effects on Activity and Comonomer Incorporation

Resin composition, crosslinked body and application of the resin composition