Olefin polymerization on immobilized zirconocene catalysts containing alkylaluminoxanes synthesized on the support surface

Ethylene and propylene polymerization on immobilized catalysts of composition MMT-H2O/AlR3/Zr-cene (MMT = montmorillonite) and on the corresponding homogeneous catalysts of composition Zr-cene-MAO (Zr-cene = rac-Et(Ind)(2)ZrCl2, rac-Me2Si(Ind)(2)ZrCl2, rac-Me2Si(2-Me-4-Ph-Ind)(2)ZrCl2, rac-1-(9-eta(5)-Flu)2-(5,6-Cp2-Me-1-eta(5)-Ind)Et]ZrCl2) is considered. Here, the activating support for the zirconocenes is montmorillonite containing methylaluminoxane or isobutylaluminoxane synthesized directly on the monmorillonite surface by the partial hydrolysis of an alkylaluminum (AlMe3, Al(i-Bu)(3), Al(i-Bu)(2)H) with the mobile water of the support (MMT-H2O/AlR3). The MMT-H2O/AlR3 supports are demonstrated to be effective activators for ansa-zirconocenes. The catalytic properties of the immobilized systems (process kinetics and efficiency, the molar mass of the resulting polymer, and the structure of the macromolecules) depend on the activating support and the zirconocene precatalyst. The complexes of the MMT-H2O/Al(i-Bu)(3) support with all zirconocene precatalysts are more active in propylene polymerization than the same complexes of MMT-H2O/AlMe3. The zirconcenes immobilized on MMT-H2O/AlR3 afford polyethylene and polypropylene with a higher molar mass than the corresponding homogeneous systems. Furthermore, immobilization causes active site heterogeneity. As compared to the homogeneous single-site catalysts of composition Zr-cene-MAO, the corresponding catalysts immobilized on MMT-H2O/AlR3/Zr-cene are more stereospecific in the case of rac-Me2Si(Ind)(2)ZrCl2 (C-2 symmetry) and are less stereospecific in the case of rac-[1-(9-eta(5)-Flu)2-(5,6-Cp-2-Me-1-eta(5)-Ind)Et]ZrCl2 (C-s symmetry).