N,N-二乙基硫代氨基甲酰硫基团(S_2CNEt_2)为假卤原子转移的原子转移自由基聚合新体系

综述了原子转移自由基聚合 (ATRP)中 ,以N ,N 二乙基硫代氨基甲酰硫基团 (S2 CNEt2 )转移实现活性聚合、控制聚合物结构的 4种新方法 :非卤化物 ,N ,N 二乙基二硫代氨基甲酸亚铜 Cu(S2 CNEt2 ) ]催化甲基丙烯酸甲酯 (MMA)的正向ATRP ;2 ,2′ 联吡啶存在的条件下 ,过氧化苯甲酰 (BPO)与Cu(S2 CNEt2 )的氧化还原反应控制MMA的本体反向ATRP;同时含可转移卤原子、基团的氯化二乙基二硫代氨基甲酸铜 Cu(S2 CNEt2 ) Cl]成功地用于偶氮二异丁腈或BPO引发的乙烯类单体反向ATRP.假卤原子S2 CNEt2 转移的ATRP得到窄分布的精确结构聚合物分子链ω 端含有光敏基团S2 CNEt2 ,可引发乙烯类单体的常温光聚合 ,实现ATRP与光聚合相结合制备嵌段共聚物

NEW ATRP SYSTEMS REALIZED WITH PSEUDO-HALOGEN N,N-DIETHYLTHIOCARBAMOYLTHIYL (S2CNEt2) TRANSFER

This review describes four methods for functionalizing vinyl polymers with photo-labile S 2CNEt 2 as ω- end groups.The normal atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) with a p-toluenesulfonyl chloride/Cu(S 2CNEt 2)/bpy initiation system was performed regardless of the original feed ratio of monomer/initiator,reaction temperature or solvent polarity.In conjunction with 2,2′-bipyridine (bpy), Cu(S 2CNEt 2) catalyzed the BPO-initiated radical polymerization of MMA in bulk.The reverse ATRP of MMA and styrene (St) with the AIBN or BPO initiator could be successfully carried out in the presence of Cu(S 2CNEt 2)Cl/bpy complex.S 2CNEt 2 groups were demonstrated to ω- end-cap the obtained polymeric chains via the pseudo-halogen transfer reaction between the active and dormant species.Photo-polymerization of vinyl monomers under UV irradiation initiated by the resulting PMMA progressed at ambient temperature yielding extended PMMA and PMMA-b-PSt copolymers.Well-defined extended PMMA could be produced with the obtained PMMA and CuCl/bpy complex via the normal ATRP procedure.