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Journal of the American Chemical Society, Vol.122, No.46, 11275-11285, 2000
Kinetics of propylene polymerization using bis(2-phenylindenyl)zirconium dichloride/methylaluminoxane
The kinetics of propylene polymerization in toluene solution by bis(2-phenylindenyl)zirconium dichloride/methylaluminoxane at 20 degreesC were investigated. As the structure and properties of elastomeric polypropylenes produced by these catalysts depend sensitively on the reaction conditions, a detailed study of the kinetics was carried out to evaluate the influence of these parameters on the polymerization behavior. Studies of the solubilities and mass-transfer rates reveal that dissolved atactic polypropylene has little effect on propylene solubility but influences the mass-transfer rate of propylene into solution. The rates of propylene polymerization reach a maximum after 10-20 min and then decrease. The decrease in rate over time is faster at higher monomer concentrations. Catalyst activity was negligible at [Al]/[Zr] = 1000 but constant from [Al]/[Zr] = 2500 to [Al]/[Zr] = 10 000. Analysis of molecular weights as a function of monomer concentration reveal P-hydride elimination to be the primary chain-transfer mechanism. Narrow molecular weight distributions (M-w/M-n = 2.0-2.6) were obtained. The increase of the isotactic dyads and pentads ([m] and [mmmm]) with increasing monomer concentration reveals an additional kinetic event which competes with the stereodifferentiating olefin insertion step. Modeling studies are more consistent with a mechanism involving interconversion of the catalyst between isospecific and aspecific states than a mechanism involving epimerization of the stereogenic centers of the growing polymer chain.