Exploring the Kinetics of Solution Polymerization of Butyl Acrylate for Tailoring a Microstructure at Elevated Temperatures

The production of low molar mass polyacrylates commonly involves a starved-feed semibatch free radical polymerization process carried out at elevated temperatures. The kinetics of free radical polymerization of acrylates at higher temperatures introduces complexity, attributed to secondary reactions like backbiting and Beta-Scission, which affect the molecular structure and molar mass. In this study, the Monte Carlo method is utilized to simulate the free-radical solution polymerization of butyl acrylate at high temperature. The simulations modeled 32 reactions and produced data that were not feasible by experimental investigation. These data elucidate the effect of reaction parameters on the average molar mass, branching, and macromonomer content. The simulation results are also compared with the results of parallel experimental investigation, and good agreement is observed. These results can be utilized to gain deep insight into the mechanism of polymerization and facilitate the synthesis of acrylate polymers with predefined average molar mass, branching content, and macromonomer content, which has significant industrial importance.