Exploitation of the Degenerative Transfer Mechanism in RAFT Polymerization for Synthesis of Polymer of High Livingness at Full Monomer Conversion

We report the synthesis by the reversible addition–fragmentation chain transfer process of well-defined decablock polymers with a final dispersity as low as 1.15 and a fraction of living chain as high as 97% after 10 successful block extensions, each taken to >99% monomer conversion. By using model decablock homopolymers of poly( N, N -dimethylacrylamide) and poly(4-acryloylmorpholine) of relatively low DP (10 units per block in average), we describe the theoretical and experimental considerations required to access high-order multiblock copolymers with excellent control over molecular weight distributions and high livingness.