Ethylene and propylene were polymerized over the siloxy-substituted bis(indenyl) ansametallocenes, rac-[ethylenebis(2-(tert-butyldimethylsiloxy)indenyl)]zirconium dichloride (1), rac-[ethylenebis(2-(tert-butyldimethylsiloxy)-4,5,6,7-tetrahydroindenyl)] zirconium dichloride (2), and rac-[ethylenebis(2-(tert-butyldimethylsiloxy)indenyl)]hafnium dichloride (3), using methylaluminoxane (MAO) and trityl tetrakis(pentafluorophenyl)borate as cocatalysts. Especially complex 1 forms a highly active catalyst precursor for the polymerization of α-olefins. Synthesis and characterization of 2 and 3 are described. The 1/MAO and 3/MAO catalyst systems show high polymerization activities at exceptionally low [Al]: [Zr] ratios [(100-250):1]. For both catalysts, extensive chain transfer to aluminum is observed as the predominant chain-transfer mechanism. Preliminary results from copolymerization of ethylene with 1-hexene and 1-hexadecene over 1/MAO indicate a good comonomer response.
- activated metallocene catalysts
- ethylene/alpha-olefin copolymerization
- ethylene/propylene copolymerization
- methylaluminoxane cocatalyst
- siloxy-substituted metallocene