RAFT Polymerization of S-Vinyl Sulfide Derivatives and Synthesis of Block Copolymers Having Two Distinct Optoelectronic Functionalities

Abstract

Well-defined sulfur-containing polymers and block copolymers were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization of S-vinyl sulfide derivatives, in which the thioether moiety is directly connected to the vinyl group. We initially investigated RAFT polymerization of four different S-vinyl sulfide derivatives, phenyl vinyl sulfide (PVS), 4-chlorophenyl vinyl sulfide (CPVS), 2,4-dichlorophenyl vinyl sulfide (DCPVS), and 4-bromophenyl vinyl sulfide (BPVS). Three xanthate-type chain transfer agents (CTAs), a dithiocarbamate-type CTA, and a dithioester-type CTA were compared for these RAFT polymerizations. Reasonable control of the polymerization of PVS was confirmed by an observed linear increase in the molecular weight with the conversion, feasibility to control molecular weight based on the ratio of monomer consumed to the amount of CTA used, chain end structure determined by 1H NMR, and chain extension experiment. The RAFT polymerization of the bromo-substituted monome...