Synthesis and RAFT polymerization of a novel vinyl monomer containing both triarylimidazole and triazole moieties

A novel monomer consisting of a 4-vinyl-1,2,3-triazole unit directly linked to a triphenylimidazole unit, 1-(4-(4,5-diphenyl-1<i>H</i>-imidazol-2-yl)phenyl)-4-vinyl-1<i>H</i>-1,2,3-triazole (DVT), has been successfully synthesized using click chemistry followed by elimination reaction. Subsequently, poly(DVT) was prepared by the reversible addition-fragmentation chain transfer (RAFT) polymerization of DVT in dimethyl sulfoxide using <i>S</i>-dodecyl-<i>S′</i>-(<i>α</i>,<i>α′</i>-dimethyl-<i>α″</i>-acetic acid)-trithiocarbonate (DMP) as the RAFT agent and 2,2<i>′</i>-azobis(isobutyronitrile) (AIBN) as the initiator. Kinetic studies demonstrated that the polymerization process of DVT followed pseudo-first-order kinetics with respect to the monomer concentrations. The molecular weight of the resulting polymer increased linearly with monomer conversion, while a low polydispersity was maintained throughout. In addition, the poly(DVT) showed the characteristic of temperature-dependent absorbance in the near-ultraviolet (UV) spectral region, of which a linear dependence of UV absorbance on temperature was confirmed for the polymer both in solution and in solid states.

一种由4-乙烯基-1,2,3-三唑单元直接连接三苯基咪唑单元构成的新型单体——1-(4-(4,5-二苯基-1<i>H</i>-咪唑-2-基)苯基)-4-乙烯基-1<i>H</i>-1,2,3-三唑（DVT），通过点击化学结合后续消除反应成功合成。随后，以<i>S</i>-十二烷基-<i>S</i>′-(<i>α</i>,<i>α</i>′-二甲基-<i>α</i>″-乙酸)-三硫代碳酸酯（DMP）作为可逆加成-断裂链转移（RAFT）试剂、2,2′-偶氮二异丁腈（AIBN）作为引发剂，在二甲基亚砜中实现DVT的可逆加成-断裂链转移（RAFT）聚合，制备得到聚(DVT)。动力学研究表明，DVT的聚合过程遵循以单体浓度为基准的准一级动力学规律。所得聚合物的分子量随单体转化率呈线性增长，且整个聚合过程中始终保持较低的多分散性。此外，聚(DVT)在近紫外（UV）光谱区域展现出温度依赖性吸光特性，其在溶液与固态下的紫外吸光度均被证实与温度呈线性相关。