RAFT Polymerization of Phenyl Vinyl Sulfide Using Trithiocarbonate Mediating Agents and Synthesis of Block Copolymers

Summary Reversible addition‐fragmentation chain transfer (RAFT) polymerization of phenyl vinyl sulfide (PVS), in which the thioether moiety is directly connected to the vinyl group, was investigated using trithiocarbonates as chain transfer agents (CTAs). A trithiocarbonate with a 2‐cyano‐2‐propyl group in the R moiety was found to be effective in achieving controlled radical polymerization of the S‐vinyl monomer. Reasonable control of the polymerization of PVS was indicated by the formation of a narrow dispersity polymer, molecular weight controlled by the monomer/CTA molar ratio, a linear increase in molecular weight with the conversion, and preserved chain end structure (determined by 1H NMR). Well‐defined block copolymers were synthesized by RAFT polymerization of PVS using polystyrene macro‐CTA.