Preparation of vinyl polymers bearing photo-labile diethylthiocarbamoylthiyl (S2CNEt2) groups via ATRP

Direct synthesis of vinyl polymers functionalized with photo-labile diethylthiocarbamoylthiyl (S2CNEt2) groups was reviewed via three living polymerization procedures: normal atom-transfer radical polymerization (ATRP), reverse ATRP and photo ATRP. The S(2)CNEt2 group was transferred by mediating the dormant-active species equilibrium in the course of polymerization and eventually omega-terminating the resulting polymer chain. ATRP of methyl methacrylate (MMA) was successfully performed with a p-toluenesulfonyl chloride/Cu(S2CNEt2)/2,2-bipyridine(bpy) or benzoyl peroxide (BPO)/Cu(S2CNEt2)/bpy initiation system. The oxidized complex, Cu(S2CNEt2)Cl/bpy, catalyzed the reverse ATRP of vinyl monomers initiated with BPO or 2,2'-azobisisobutyronitrile (AIBN), producing tailor-made polymers with omega-S2CNEt2 groups and a narrow molecular-weight distribution. Without external ligands, the living polymerization of vinyl monomers was achieved under the thermal initiation of diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS) in conjunction with Fe(S2CNEt2)(3) catalyst. Photo ATRP of MMA and styrene was first realized in the presence of 2,2-dimethoxy-2-phenylacetophenone (DMPA)/Fe(S2CNEt2)(3) under UV irradiation at ambient temperature. (C) 2004 Society of Chemical Industry.Polymer ScienceSCI(E)EI0ARTICLE6756-7655