Copolymerizations of ethylene with 1-decene over various ANSA-metallocene complexes combined with Al(i-Bu)/sub 3//[CPh/sub 3/][B(C/sub 6/F/sub 5/)/sub 4/] cocatalyst

Copolymerizations of ethylene with 1-decene were carried out with a series of stereospecific metallocene compounds, C/sub 2/H/sub 4/[Ind]/sub 2/Zr(NMe/sub 2/)/sub 2/ (1), C/sub 2/H/sub 4/[Ind]/sub 2/Hf(NMe/sub 2/)/sub 2/ (2), (CH/sub 3/)/sub 2/Si(1-C/sub 5/H/sub 2/-2-CH/sub 3/-4-/sup t/C/sub 4/H/sub 9/)/sub 2/Zr(NMe/sub 2/)/sub 2/ (3), C/sub 2/H/sub 4/(Fluo)(Cp)Zr(NMe/sub 2/)/sub 2/ (4), (CH/sub 3/)/sub 2/C(Fluo)(Cp)Zr(NMe/sub 2/)/sub 2/ (5) (Cp = /spl eta//sup 5/-cyclopen-tadienyl, Ind = /spl eta//sup 5/-indenyl Fluo = /spl eta//sup 5/-fluorenyl), combined with Al(i-Bu)/sub 3//[CPh/sub 3/][B(C/sub 6/F/sub 5/)/sub 4/] cocatalyst. The copolymerization rate decreased in the order of 3 > 1 > 2 /spl sim/ 4 > 5 and the 1-decene reactivity decreased in the order of 2 > 5 > 1 /spl sim/ 4 > 3. The reactivity product of ethylene and 1-decene (r/sub E/ /spl times/ r/sub D/) was below 1 except 3 catalyst, corresponding to random copolymer structures with an alternating character. The melting point, crystallinity, intrinsic viscosity and density of the 1-decene/ethylene copolymers decreased markedly with an increase in the 1-decene content, regardless of the type of catalytic system.