Accelerated Process Modelling for Light-Mediated Controlled Radical Polymerization

Mathematical modelling and simulation are pivotal components in process systems engineering. Focusing on polymerization process systems, identifying microscopic properties of polymers is highly sought after for advancing kinetic comprehension and facilitating industrial applications. Among various computational methods predicting polymeric properties microscopically, kinetic Monte Carlo (kMC) offers a stochastic framework to characterize individual polymer chains and track dynamic system evolution, providing mechanistic insights into complex polymerization kinetics. In this study, an accurately accelerated Superbasin-aided kMC model is developed for enhancing the kinetic understanding of the advanced photo-iniferter RAFT (PI-RAFT) polymerization. The contribution is twofold, presenting advancements in both the mathematical modelling techniques for complex dynamic process systems and the mechanistic understanding of photo-induced polymerizations. Leveraging the increased computational performance and the gained kinetic understanding, batch blending is examined as a viable approach to produce polymers with desired microscopic properties. This work bridges stochastic molecular simulations with scalable polymerization processes, laying groundwork for multiscale modelling in polymer engineering, and also the foundation for process design, control, and optimization.