Polymerization of ethene initiated with a mixture of siloxane-bridged mono- and dinuclear zirconocenes

In the polymerization of ethene cocatalyzed with modified methylaluminoxane, the catalyst activities of the siloxane-bridged dinuclear zirconocenes, tetramethyldisiloxanediylbis(cyclopentadienylindenylzirconium dichloride) (3) and hexamethyltrisiloxanediylbis(cyclopentadienylindenylzirconium dichloride) (4) were lower than that obtained with the siloxane-bridged mononuclear zirconocene, tetramethyldisiloxanediyldicyclopentadienyldimethylzirconium (1). On the other hand, weight-average molecular weight M̄_w and ratio of weight- to number-average molecular weights M̄_w/M̄_n of polyethene (PE) obtained with 3 or 4 were higher than those of PE obtained with 1. For a binary mixture of 1/3 or 1/4, it was found that the obtained PE exhibits a bimodal molecular weight distribution for an appropriate composition of the mixed zirconocenes. M̄_w/M̄_n of PE could be adjusted by changing the relative concentrations of the two zirconocenes.