Chain transfer in degenerative RAFT polymerization revisited: a comparative study of literature models

Under the validity of the degenerative transfer mechanism, the activation/deactivation process in reversible addition-fragmentation chain transfer (RAFT) polymerization can be formally quantified by transfer coefficients, depending on the chemical structure of the participating radicals and dormant species. In the present work, the different literature methods to experimentally determine these RAFT transfer coefficients are reviewed and theoretically re-evaluated. The accuracy of each method is mapped for a broad range of reaction conditions and RAFT transfer reactivities. General guidelines on when which method should be applied are formulated