Korea Polymer Journal, Vol.7, No.4, 223-228, August, 1999
Ethylene Polymerizaion over Stereorigid rac-Me2Si(1-C5H2-2-Me-4-t-Bu)2Zr(NMe2)2 Compound
Ethylene polymerization have been carried out by using stereorigid diamide rac-Me2Si(CMB)2Zr(NMe2)2(rac-1,CMB=1-C5H2-2-Me-4-t/Bu) compound in the presence of methylaluminoxane(MAO) or AIR3/[CPh3][B(C6F5)4] (2). Both catalytic systems are highly active and their activities are strongly dependent on the polymerization temperature (Tp). The polymerizaion especially at low Tp results in a precipitation of polymer during the initial stage of polymerizaion and a change of polymerization medium to heterogeneous phase. The curved Arrhenius plot of activity and the dissimilarity of the Arrhenius plot of initial rate of polymerizaion from the Arrhenius plot of the rate of long-time polymerization indicate the present catalytic systems are experiencing mass transfer limitations from the early period of polymerizaion. The rac-1/AIR3/2 system also shows very high activity, when AIR3 is A(i-Bu)3,Al(i-Bu)2H, and AlEt3, but the rac-1/AlMe3/2 system shows very low activity. The molecular weight(MW) of polymer decreases sharply as Tp increases, and the high MW of polymers formed especially at low Tp causes the precipitation of polymers.
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