Effect of comonomer composition on the controlled free-radical copolymerization of styrene and maleic anhydride by reversible addition–fragmentation chain transfer (RAFT)

Controlled free-radical copolymerization of styrene and maleic anhydride was performed in 1,4-dioxane or tetrahydrofurane solution at 60 °C using the RAFT technique. The effect of monomer feed ratio on copolymerization kinetics and on control over molar mass distribution was examined. It was shown that polymerization was faster and quality of control was poorer when the proportion of maleic anhydride in the monomer feed was larger. These features were assigned to a decrease in the chain transfer constant of the polymeric RAFT agent, most probably due to an increase in the apparent rate constant of propagation with the proportion of maleic anhydride.