Straightforward Synthesis of Poly(Vinyl Acetate)‐<i>b</i>‐Polystyrene Copolymers Through Sequential Reversible Addition−Fragmentation Chain‐Transfer (<scp>RAFT</scp>) Polymerization: A Case Study With a Commercially Available Iniferter Agent

ABSTRACT Although reversible addition‐fragmentation chain‐transfer (RAFT) polymerization has shown great ability for the synthesis of block copolymers through sequential polymerization, some limits have been encountered for the block copolymers from a more activated monomer (MAM) and a less activated monomer (LAM) due to the unsuitability of transfer agents for the both classes of monomers. In this work, an effective case of synthesis of block copolymers of vinyl acetate (VAc, a LAM) and styrene (a MAM) through sequential VAc and styrene RAFT polymerizations within one commercially available RAFT agent (BM1481) has been demonstrated. A PVAc‐b‐PS block copolymer having a molecular weight and a polydispersity index of 15,270 Da and 1.24 has been obtained. Nevertheless, the opposite sequential RAFT polymerizations of styrene and VAc are not effective for the targeting block copolymers. The prepared PVAc‐b‐PS block copolymer has shown amphiphilic characteristics with formation of core‐shell particles in selective solvents and the application of macro‐surfactants for the polymer blends of PS and PVAc. The results associate to attractive advances in both polymer chemistry and polymer materials.