A novel acceleration approach for free radical polymerization simulation: Coupled pre‐sequencing Monte Carlo model

Abstract

Monte Carlo (MC) simulation is one of the most powerful methods for predicting the detailed molecular architecture of free radical polymerization products, but its efficiency is severely limited by stepwise random selection of massive elementary reactions. To address this challenge, we propose an accelerated approach termed the coupled pre‐sequencing MC model. Unlike previous hybrid models, the proposed approach first completes the deterministic calculation of reaction rates throughout the entire reaction process and converts the elementary reaction rates into reaction counts within each coarse‐grained unit. The detailed chain structure information lost in the deterministic model is then recovered through MC simulation. To further enhance the efficiency of this process, a unique pre‐sequencing strategy is designed, which includes executing initiator decomposition in advance, treating propagation reactions as a queue, and inserting low‐frequency reactions. Simulation results for LDPE and EVA production demonstrate high accuracy and substantially reduced computational cost.