Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

In this work it is shown that catalytic chain transfer is a very efficient way of controlling molecular weight in the copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The experimental data are compared to a previously developed model based on copolymerization kinetics and the mechanisms for catalytic chain transfer and for cobalt‐mediated living radical polymerization that can describe the observed transfer constants. Secondly, it is shown that the presence of a catalytic chain transfer agent does not affect the reactivity ratios within the concentration range studied. Finally, the effect of conversion and therewith composition drift on the catalytic chain transfer polymerization of MMA and BA is investigated and it is shown that under the conditions employed in the experiments a certain degree of macromer copolymerization is present at high partial conversions of MMA. Evolution of MWD with conversion for the CCT copolymerization of MMA and BA in toluene at 60 °C, [AIBN] = 6 × 10−3 mol · L−1. magnified image Evolution of MWD with conversion for the CCT copolymerization of MMA and BA in toluene at 60 °C, [AIBN] = 6 × 10−3 mol · L−1.