文献类型：期刊文献

英文题名：Commodity Polymer Functionalization by a Combination of Hydrogen Atom Transfer Reversible Addition-Fragmentation Chain Transfer Polymerization and Pentafluorophenyl-Ester-Ligation Chemistry

作者：Huang, Guanwen[1];Wu, Zhuohan[1];Liu, Yichen[1];Chang, Lingjie[1];Wang, Zhongming[1];Du, Xinghao[1];Xu, Binbin[1];Jia, Zhongfan[2];Feng, Chun[1]

机构：[1]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai Key Lab Adv Polymer Mat, Shanghai 200237, Peoples R China;[2]Flinders Univ S Australia, Inst Nanoscale Sci & Technol, Coll Sci & Engn, Bedford Pk, SA 5042, Australia

年份：2025

卷号：14

期号：8

起止页码：1038

外文期刊名：ACS MACRO LETTERS

收录：;EI(收录号：20252918800212);WOS:【SCI-EXPANDED(收录号:WOS:001527073500001)】；

基金：The authors are thankful for financial support from National Natural Science Foundation of China (U22A20131 and 52361165657).

语种：英文

外文关键词：Activation analysis - Atom transfer radical polymerization - Atoms - Chains - Complexation - Esters - Ethylene - Hydrogen - Hydrogen bonds - Methyl ester - Polyethylene oxides

摘要：Development of highly efficient and versatile strategies for functionalization of commodity polymers direct from carbon-hydrogen (C-H) bonds has attracted growing interest due to the ubiquity of C-H bonds in various commodity polymers and the great desire for upcycle of commodity polymers. However, the efficiency of C-H activation is usually low (<20%) and only one (potential) functional unit was introduced into each activated C-H bond. The low content of introduced functional units could be one great hindrance to the improvement of performance of resulting polymers. Herein we report a photocatalytic hydrogen atom transfer reversible addition-fragmentation chain transfer (HAT-RAFT) grafting polymerization strategy to introduce polymeric side chains of activated pentafluorophenyl esters (PFEs) into commodity polymers of poly(ethylene glycol), poly(propylene oxide), polybutylene, polypropylene, and poly(vinylpyrrolidone) by using the C-H bonds of commodity polymers as the initiating sites. The grafting polymerization of pentafluorophenyl acrylate (PFA) exhibits living/controlled features and temporal controllability. With the amplification effect of grafting polymerization, each activated C-H bond allows to the introduction of tens of PFEs, leading to a high content of PFE groups. Owing to the high reactivity of PFEs toward amino- and hydroxyl-containing molecules under mild conditions with excellent efficiency and group tolerance, the introduced PFEs of PPFA chains enable quantitative transesterification and amidation for efficient functionalization of commodity polymers via PFE-ligation chemistry.