Prediction of Chain Length Distribution of Polystyrene Made in Batch Reactors with Bifunctional Free-Radical Initiators Using Dynamic Monte Carlo Simulation

The objective of this paper is to present a dynamic Monte Carlo model that is able to simulate the polymerization of styrene with bifunctional free-radical initiators in a batch reactor. The model can predict the dynamic evolution of the chain length distribution of polystyrene in the reactor. The model includes all relevant polymerization mechanistic steps, including chemical and thermal radical generation, and diffusion-controlled termination. The model was applied to styrene polymerization and the Monte Carlo estimates for chain length averages were compared to those obtained with the method of moments. Excellent agreement was obtained between the two methods. Although styrene polymerization was used as a case study, the proposed methodology can be easily extended to any other polymer type made by free-radical polymerization.