Kinetic model for short‐cycle bulk styrene polymerization through bifunctional initiators

Abstract A model describing the kinetics of bulk styrene polymerization through bifunctional initiators has been developed. The diffusion‐controlled propagation and termination reactions at high monomer conversions are modeled with the free volume theory for polymer solutions. Three different commercially available bifunctional initiators were experimentally evaluated for a wide range of polymerization conditions to study the effect of the reaction rate on the molecular weight and molecular weight distribution. The model predictions for the same polymerization conditions show excellent agreement with the experimental data, for the whole range of conversions, for both reaction rate and molecular weight distribution development, under all the conditions tested. It is demonstrated throughout this study that high molecular weights, very high reaction rates, and narrow molecular weight distributions can be achieved simultaneously by using bifunctional initiators. A comparison between monofunctionally initiated systems with the bifunctionally initiated ones shows that short‐cycle reactions with reductions in polymerization time of up to 75% may be achieved with the bifunctional initiators for a wider range of conditions without significantly affecting the molecular weight and molecular weight distribution of the final product.