Modeling of Semibatch Solution Radical Copolymerization of Butyl Methacrylate and 2‐Hydroxyethyl Acrylate

Abstract Nonfunctional monomer feedstocks containing alkyl meth(acrylate) components such as butyl acrylate (BA) and butyl methacrylate (BMA) are replaced or augmented with functional monomers such as 2‐hydroxyethyl methacrylate (HEMA) and 2‐hydroxyethyl acrylate (HEA) to produce reactive polymer chains of lowered molar mass for application in solvent‐borne automotive coatings. The introduction of such polar and functional reactants affects the radical copolymerization kinetics and introduces solvent dependencies. A series of BMA/HEA experiments are performed to determine the influence of these changing kinetic parameters under starved‐feed semibatch operating conditions. A comparison with BMA/BA copolymerizations shows that the influence of hydrogen bonding is small, with the semibatch system well controlled to HEA contents of up to 50 wt%. Thus, the experiments are well represented by a comprehensive generalized copolymerization model that considers relevant methacrylate and acrylate side‐reactions and uses the chain growth parameters measured in previous kinetic investigations.