Iron-Catalyzed Atom Transfer Radical Polymerization of Semifluorinated Methacrylates
Iron-Catalyzed Atom Transfer Radical Polymerization of Semifluorinated Methacrylates
复制标题
铁催化原子转移自由基聚合半氟甲基丙烯酸酯
DOI：
10.1021/acsmacrolett.9b00579
复制
发表时间：
2019-09-01
影响因子：
7.015
通讯作者：
Matyjaszewski, Krzysztof
中科院分区：
文献类型：
--
作者：
Dadashi-Silab, Sajjad;Matyjaszewski, Krzysztof
氟化聚合物是一类重要的功能材料，具有高耐化学性、热稳定性和低表面能等独特性能。铜催化剂催化半氟单体的原子转移自由基聚合（ATRP）往往需要开发特殊的条件来控制聚合，防止碱催化的含氟单体与溶剂之间的酯交换反应等副反应。本文将光诱导铁催化的ATRP应用于多种半氟化甲基丙烯酸酯单体的聚合。聚合是通过在蓝光照射下光化学生成Fe催化剂活化剂引发的，可以对聚合物链的生长进行时间控制，并且在各种溶剂（包括氟化和非氟化溶剂）中得到很好的控制，而不会发生任何副反应。此外，原位链延伸和嵌段共聚实验证明了链端官能团的保存，使得易于合成控制良好的嵌段共聚物。
Fluorinated polymers are an important class of functional materials that exhibit unique properties such as high chemical resistance, thermal stability, and low surface energy. Atom transfer radical polymerization (ATRP) of semifluorinated monomers catalyzed by copper catalysts often requires development of special conditions to control the polymerization and prevent side reactions such as base-catalyzed transesterification between the fluoro-containing monomers and solvents. In this paper, photoinduced iron-catalyzed ATRP was applied to the polymerization of a variety of semifluorinated methacrylate monomers. Polymerizations were initiated by photochemical generation of the Fe catalyst activator under blue light irradiation, enabling temporal control over the growth of polymer chains, and were well-controlled in various solvents, including fluorinated and nonfluorinated solvents, without undergoing any side reactions. Moreover, in situ chain extension and block copolymerization experiments demonstrated the preservation of chain end functionality, enabling facile synthesis of well-controlled block copolymers.