Homogeneous and heterogeneous metallocene/MAO-catalyzed polymerization of functionalized olefins

Ethylene was copolymerized with 10-undecene-1-ol, 5-norbornene-2-methanol and 5-(N,N-diisopropylamino)-1-pentene by utilizing Me2Si(Ind)2ZrCl2/MAO, iPr(CpInd)ZrCl2/MAO, iPr(3-Me-CpFlu)-ZrCl2/MAO and the corresponding heterogeneous silica supported catalysts. In the case of the copolymerization with 10-undecene-1-ol and 5-norbornene-2-methanol the rapid catalyst deactivation with the increasing amount of the comonomer in the feed was prevented through a prereaction of the comonomer with triisobutylaluminium (Tiba). Especially with the Tiba-protected 5-norbornene-2-methanol high comonomer contents were achieved. During the copolymerizations with heterogeneous metallocene/MAO/SiO2 catalysts the arising problem of a diffusion retardation exists for the Tiba-protected comonomers. For this reason the ethylene/10-undecene-1-ol copolymerization with the Me2Si(Ind)2ZrCl2/MAO/SiO2 catalyst yields satisfying 10-undecene-1-ol incorporations only at low ethylene concentrations. In comparison to this, the ethylene/5-(N,N-diisopropylamino)-1-pentene copolymerization with the homogeneous or heterogeneous Me2Si(Ind)2-ZrCl2/MAO catalyst yields comparable incorporation rates.