Mechanism and modelling of thermally initiated RAFT step-growth polymerization

Here we report the modelling of thermally initiated RAFT step-growth polymerization kinetics of maleimide and acrylate monomers with bifunctional RAFT agents bearing tertiary carboxyalkyl-stabilized fragmentable R groups. By analytically solving the governing equations of our model, derived from the proposed mechanism, we demonstrate that the kinetics of these polymerizations follows first order with respect to monomer concentration. Furthermore, the obtained apparent rate constant (k_app) values indicate that acrylate monomers polymerize at slower rates compared to maleimide monomers during thermally initiated RAFT step-growth polymerization.