Zhao Boyu, Pashley-Johnson Fred, Jones Bryn A, Wilson Paul
University of Warwick UK
Chem Sci. 2022 Apr 27;13(19):5741-5749. doi: 10.1039/d2sc01832b. eCollection 2022 May 18.
Simplified electrochemical atom transfer radical polymerization (seATRP) using Cu--propyl pyridineimine complexes (Cu(NPPI)) is reported for the first time. In aqueous solution, using oligo(ethylene glycol) methyl ether methacrylate (OEGMA), standard electrolysis conditions yield POEGMA with good control over molecular weight distribution ( < 1.35). Interestingly, the polymerizations are not under complete electrochemical control, as monomer conversion continues when electrolysis is halted. Alternatively, it is shown that the extent and rate of polymerization depends upon an initial period of electrolysis. Thus, it is proposed that seATRP using Cu(NPPI) follows an electrochemically-triggered, rather than electrochemically mediated, ATRP mechanism, which distinguishes them from other CuL complexes that have been previously reported in the literature.
首次报道了使用铜-丙基吡啶亚胺配合物(Cu(NPPI))的简化电化学原子转移自由基聚合(seATRP)。在水溶液中,使用聚乙二醇甲基醚甲基丙烯酸酯(OEGMA),标准电解条件下得到的聚乙二醇甲基醚甲基丙烯酸酯(POEGMA)具有良好的分子量分布控制(<1.35)。有趣的是,聚合反应并非完全受电化学控制,因为当电解停止时单体转化率仍在继续。另外,研究表明聚合反应的程度和速率取决于初始电解阶段。因此,有人提出使用Cu(NPPI)的seATRP遵循的是电化学引发而非电化学介导的原子转移自由基聚合(ATRP)机制,这使其有别于文献中先前报道的其他CuL配合物。