Homo- and Copolymerization of Ethylene and α-Olefins over 1- and 2-Siloxy-Substituted Ethylenebis(indenyl)zirconium and Ethylenebis(tetrahydroindenyl)zirconium Dichlorides

The influence of siloxy substitution of ethylene-bridged bis(indenyl)- and bis(tetrahydroindenyl)zirconium dichlorides on ethylene/α-olefin copolymerization and ethylene homopolymerization performance was investigated. Ethylene was copolymerized with 1-hexene and 1-hexadecene over rac-[ethylenebis(1-(tert-butyldimethylsiloxy)-3-indenyl)]zirconium dichloride (1), rac-[ethylenebis(1-(tert-butyldimethylsiloxy)-4,5,6,7-tetrahydro-3-indenyl)]zirconium dichloride (H1), rac-[ethylenebis(2-(tert-butyldimethylsiloxy)-1-indenyl)]zirconium dichloride (2), and rac-ethylenebis(1-indenyl)zirconium dichloride (EBI) using methylaluminoxane (MAO) as cocatalyst. 1-Siloxy substitution was found to remarkably improve the copolymerization ability and 2-siloxy substitution to enhance the polymerization activity of ethylenebis(indenyl)zirconium dichlorides. Optimum homo- and copolymerization performance was observed at a very low Al(MAO) concentration, which for 2 could be reduced to a level of 0.2 mmol/dm3 by using a small amount of triisobutylaluminum. The 1-siloxy-substituted metallocene catalysts 1 and H1 (hydrogenated 1) revealed decreasing comonomer incorporation and increasing induction times with increasing Al(MAO) concentration, which indicates the presence of unfavorable interactions between these metallocenes and MAO. Chain termination occurred mainly by chain transfer to the monomer and β-hydrogen transfer to the metal for catalysts with indenyl and tetrahydroindenyl ligands, respectively.