Polymerizations of propene and 1-hexene were conducted with two sets of catalyst systems with completely different stereospecificity : aspecific catalyst, TiC13/MgCI2/A12 (C2H 5)3C13/A1 (C2H 5) 3 (s°lid) and Cp2ZrCI2/MAO (soluble); isospecific catalyst, Solvay type TiCI3/Cp2Ti(CH3) 2 (solid) and rac- Et[IndH4]2ZrC12/MAO (soluble). The molecular mass distributions (MMDs) of both oligomers and high polymers obtained with these catalysts were measured by mass spectrometer and g.p.c. The pattern of oligomer distributions was found to be markedly different between the aspecific and isospecific catalysts. The aspecific catalyst gave a continuous distribution in a wide mass range, whereas the isospecific catalyst gave a discontinuous distribution, i.e. oligomers having more than 10-20 monomer units could not be detected. On the other hand, short periods of polymerization gave high polymers, the MMDs of which did not change so much with increasing the polymerization time. These results suggest that atactic polymerization proceeds steadily while the propagation rate of isotactic polymerization becomes very fast after the polymer chains grow to a critical number of monomer units (10-20).
Посилання на статтю:
Difference in propagation profiles between isotactic and atactic polymerizations with Ziegler-Natta catalysts / Kazuo Soga*, Dong Hee Lee and Yutaka Morikawa // Polymer. – 1992. – Vol 33. – P. 2408-2411.