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The negative effect that a RAFT agent with a poor leaving group has on the evolution of molecular dispersity in a RAFT-mediated polymerization was shown to be mitigated by performing the polymerization in semi-batch mode. The result is attributed to an increase in the probability of transfer between the propagating radical and the leaving group during the polymerization. Also for RAFT-mediated polymerizations that use RAFT agents with efficient leaving groups, the evolution of molecular dispersity during a semi-batch polymerization improves compared to that for an analogous batch-mode reaction.

Improved control through a semi-batch process in RAFT-mediated polymerization utilizing relatively poor leaving groups