Abstract
Kinetics of propene polymerizations have been studied for four ansa-zirconocene catalysts, derived from Me2Si(2-Me-benz[e]indenyl)ZrCl2, Me2(1PrC5H3)(flu)ZrCl2, Me2Si(tBuC5H3)(flu)ZrCl2 and Me2C(tBuC5H3)-(flu) ZrCl2 by activation with MAO. In all cases, a reaction order higher than one in propene concentration is observed at low monomer concentrations, while Saturation occurs at higher monomer concentrations. By use of a genetic algorithm, alternative kinetic schemes, involving various deactivation processes and/or the participation of a second olefin in the Insertion step, are analyzed with regard to ranges for their elementary rate constants which yield reasonable agreement with the experimental data.
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