The effect of type and concentration of external donor and hydrogen concentration on oligomer formation and chain end distribution were studied. Bulk polymerization of propylene was carried out with two different Ziegler-Natta catalysts at 70°C, one a novel self-supported catalyst (A) and the other a conventional MgCl2-supported catalyst (B) with triethyl aluminum as cocatalyst. The external donors used were dicyclopentyl dimethoxy silane (DCP) and cyclohexylmethyl dimethoxy silane (CHM). The oligomer amount was shown to be strongly dependent on the molecular weight of the polymer. Catalyst A gave approximately 50% lower oligomer content than catalyst B due to narrower molecular weight distribution in case of catalyst A. More n-Bu-terminated chain ends were found for catalyst A indicating more frequent 2,1 insertions. Catalyst A also gave more vinylidene-terminated oligomers, suggesting that chain transfer to monomer, responsible for the vinylidene chain ends, was a more important chain termination mechanism for this catalyst, especially at low hydrogen concentration. Low site selectivity, due to low external donor concentration or use of a weak external donor (CHM), was also found to increase formation of vinylidene-terminated oligomers.
