Kinetics of slurry phase polymerization of styrene to syndiotactic polystyrene with pentamethyl cyclopentadienyl titanium trimethoxide and methyl aluminoxane. I. Reaction rate analysis

The kinetics of syndiospecific slurry polymerization of styrene in heptane has been investigated with pentamethyl cyclopentactienyl titanium trimethoxide [Cp*Ti( OMe)(3)] catalyst with methylalmuninoxane. The experimental studies at different styrene/heptane ratios indicate that no global gelation occurs at low styrene/heptane ratios even at high styrene conversion. The effective propagation rate constant tends to decrease as polymerization rate is increased at higher initial styrene concentrations. To analyze the effect of catalyst deactivation, a novel three-stage polymerization experiment has been designed and carried out where monomer is added during the polymerization. The experimental results show that the catalyst activity is very high at the beginning of polymerization but it decreases significantly as catalyst sites are occluded in the solid phase. We also observe that the catalyst remains active for more than 3 h and the rate decay is not solely due to intrinsic catalyst deactivation. Our experimental data suggests that physical transport effects cause the decay in the polymerization rate. (C) 2003 Wiley Periodicals, Inc.