Hybrid copolymerization of acrylate and thiirane monomers mediated by trithiocarbonate

The composition and structure of polymers have great influence on their performances. Copolymerization of different monomers is a straightforward method for the fabrication of polymers with different compositions. Generally, such different monomers have similar structures to meet the criterion of one type of polymerization mechanism. Copolymerization of two or more monomers with extremely different structures is very difficult, because the polymerization mechanisms of these monomers are quite different. Herein, we report the hybrid copolymerization of oligo(ethylene glycol) methyl ether acrylate (OEGA) and 2-(phenoxymethyl) thiirane (POMT) mediated by trithiocarbonate in one pot to generate hybrid copolymers via an interconvertible mechanism between reversible addition–fragmentation chain transfer (RAFT) polymerization of OEGA and anionic ring-opening polymerization (AROP) of POMT. Trithiocarbonate acts as an intermediate between the anionic propagating species of thiirane monomers and the radical growing species of vinyl monomers, and the different polymerization mechanisms do not interfere with each other. The universality of such a strategy has been demonstrated by the hybrid copolymerization of various acrylate and thiirane monomers. The hybrid copolymers with similar compositions but different sequence-structures exhibit different self-assembly behaviors. This hybrid copolymerization expands the chemical diversity of artificial polymers, which may provide new opportunities for functional optimization of polymeric materials.