Olefin copolymerization with metallocene catalysts. III. Supported metallocene/methylaluminoxane catalyst for olefin copolymerization

Abstract Supported catalyst for fluidized bed polymerization processes has been prepared by reacting macroporous SiO 2 first with MAO (methylaluminoxane) and then with Et [Ind] 2 ZrCl 2 . It contains 0.60 wt % of Zr and an [Al]/[Zr] ratio of 50. This catalyst produces homogeneous E/P (ethylene/propylene) copolymers with truly random copolymerization behaviors and required to achieve the same copolymerization activity for the Et[Ind] 2 ZrCl 2 /MAO would be required a total [Al]/[Zr] of only 670. Several time larger amount of MAO would be required to achieve the same copolymerization activity for the Et [Ind] 2 ZrCl 2 /MAO catalyst in solution. This random copolymerization is independent of catalyst concentration and composition. Activation of the supported catalyst with i ‐butylaluminoxane, tri‐ i ‐butylaluminum, or trimethylaluminum resulted in lower activity and copolymers having high ethylene content and crystallinity.