Kinetic Simulation of Living Carbocationic Polymerizations I. Simulation of Living Isobutylene Polymerization

ABSTRACTThe kinetic behaviour of living isobutylene polymerization initiated by TMPCI/TiCI4 at −80 °C in Hx/MeCl solvent mixture was simulated using the PREDICI® polymerization simulation software. The basis of the simulation was the newly developed comprehensive mechanistic scheme, involving a series of consecutive and competitive reactions. This scheme accounts for the interesting phenomenon that living isobutylene polymerization may display either first or second order dependence on [TiCl4]0, depending on reaction conditions. The complex mechanism of the system was simplified and the kinetics was described using composite rate constants. The simulation results showed good agreement with experimental data.