In situ ethylene homopolymerization and copolymerization catalyzed by zirconocene catalysts entrapped inside functionalized montmorillonite

Ethylene homopolymerizations and copolymerizations were catalyzed by zirconocene catalysts entrapped inside functionalized montmorillonites that had been rendered organophilic via the ion exchange of the interlamellar cations of layered montmorillonite with hydrochlorides of L ‐amino acids (AAH⁺Cl^?) or their methyl esters (MeAAH⁺Cl^?), with or without the further addition of hexadecyltrimethylammonium bromide (C₁₆H₃₃N⁺Me₃Br^?; R₄N⁺Br^?). In contrast to the homogeneous Cp₂ZrCl₂/methylaluminoxane catalyst for ethylene homopolymerizations and copolymerizations with 1‐octene, the intercalated Cp₂ZrCl₂ activated by methylaluminoxane for ethylene homopolymerizations and copolymerizations with 1‐octene proved to be more effective in the synthesis of polyethylenes with controlled molecular weights, chemical compositions and structures, and properties, including the bulk density. The effects of the properties of the organic guests on the preparation and catalytic performance of the intercalated zirconocene catalysts were studied. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2187–2196, 2003