A comprehensive stochastic simulator that considers all probable secondary reactions essential for the description of high-temperature radical copolymerization of acrylate/methacrylate is implemented based on previously established accelerating techniques. The comparisons between the predictions and six experimental datasets are detailed for semi-batch copolymerization of 2-hydroxyethyl acrylate (HEA) with n-butyl methacrylate (BMA) under starved-feed condition. Macroscopic properties -free monomer and molar mass (MW) average profiles, final polymer molecular mass distributions, and the variation of acrylate composition with time-are reasonably well predicted over the range of initiator and comonomer levels studied. The simulation output also predicts the weight fraction and MW averages of the polymer chains that contain no HEA functionality, results that are compared to the experimental extractables obtained after crosslinking the copolymer resin. The general trends are well-captured, indicating that the model can be utilized in the future to optimize recipe and operating conditions to minimize the production of the non-functional material.

2-Hydroxyethyl methacrylate (HEMA) is an important component of many acrylic resins used in coatings formulations, as the functionality ensures that the chains participate in the cross-linking reactions required to form the final product. Hence, the knowledge of their radical copolymerization kinetic coefficients is vital for both process and recipe improvements. The pulsed laser polymerization (PLP) technique is paired with size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) to provide kinetic coefficients for the copolymerization of HEMA with butyl methacrylate (BMA) in various solvents. The choice of solvent has a significant impact on both copolymer composition and on the composition-averaged propagation rate coefficient (kp,cop). Compared to the bulk system, both n-butanol and dimethylformamide reduce the relative reactivity of HEMA during copolymerization, while xylene as a solvent enhances HEMA reactivity. The magnitude of the solvent effect varies with monomer concentration, as shown by a systematic study of monomer/solvent mixtures containing 50 vol%, 20 vol%, and 10 vol% monomer. The observed behavior is related to the influence of hydrogen bonding on monomer reactivity, with the experimental results fit using the terminal model of radical copolymerization to provide estimates of reactivity ratios and kp,HEMA.