An Efficient Monte Carlo Representation of Semi-Batch Starved-Feed Acrylate-Methacrylate Multicomponent Radical Polymerization

摘要

The introduction of functional groups through radical copolymerization under starved-feed conditions is a cost-effective means to produce acrylate resins for coatings applications. The semi-batch recipes often include a large fraction of nonfunctional acrylates and methacrylates, with a low percentage of functional comonomer added to become statistically distributed within the chains. A previous kinetic Monte Carlo representation is extended to efficiently consider multicomponent recipes consisting of both functional and nonfunctional acrylate (or methacrylate) components by taking advantage of the family type behavior of polymerization mechanisms and rate coefficients. The extended model is used to simulate the semi-batch production of a terpolymer consisting of 2-hydroxyethyl acrylate (HEA), butyl acrylate, and butyl methacrylate, examining the impact of recipe formulation as well as HEA preloading on the distribution of HEA units within the polymer chain sequences. The preload strategy does not provide significant improvement, as the most important factor for minimizing the amount of nonfunctional chains produced is to maintain constant copolymer composition and polymer molecular weight throughout the course of the entire reaction.