Recent Developments in Transition Metal-Catalyzed Polymerization I. Metallocene Catalysts Covalently Tethered on Silica Surfaces.

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A group 4 metallocene complex that serves as olefin polymerization catalyst was tethered on a solid support such as silica gel by covalent bonds. A zirconocene complex that has a vinyl group on its cyclopentadienyl ligand was hydrosilated or hydroborated to introduce a functional anchor for immobilization reactions. The complex with a Si-Cl group was tethered on a silica surface by the reaction with a surface Si-OH group. The zirconocene with a BH group was immobilized on a silica gel modified with chlorodimethylvinylsilane. Ethyl-ene polymerization using the tethered catalysts showed that the hydroboration-method seems more effective than the hydrosilation-method. It exhibited comparable catalytic activity to the corresponding homogeneous catalyst and produced polyethylene of a higher molecular weight.
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