文献类型：期刊文献

英文题名：An Environmentally Benign and pH-Sensitive Photocatalyst with Surface-Bound Metalloporphyrin for Heterogeneous Catalysis of Controlled Radical Polymerization

作者：Huang, Ya[1];Li, Xue[1];Li, Jia Le[1];Zhang, Bin[2];Cai, Tao[1]

机构：[1]Wuhan Univ, Coll Chem & Mol Sci, Key Lab Biomed Polymers, Minist Educ, Wuhan 430072, Hubei, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China

年份：2018

卷号：51

期号：20

起止页码：7974

外文期刊名：MACROMOLECULES

收录：;EI(收录号：20184105918473);WOS:【SCI-EXPANDED(收录号:WOS:000448753000008)】；

基金：Financial support from the National Natural Science Foundation of China (51503155, 51773156, and 51703167), the Natural Science Foundation of Jiangsu Province (BK20160384 and BK20170412), the Natural Science Foundation of Hubei Province (2016CFB381 and 2017CFB127), and the Pujiang Program (16PJ1402400) is acknowledged.

语种：英文

外文关键词：Microspheres - Polydispersity - Atom transfer radical polymerization - Catalysis - Dimethyl sulfoxide - Polyethylene terephthalates

摘要：The implementation of photocatalysts for controlled/living radical polymerization upon visible light harvesting has emerged as a robust and powerful technique for the user-friendly synthesis of well-structured polymers with composition, spatiotemporal, and sequence control. Nevertheless, the incompatibility of present synthetic protocols with environmentally benign media, such as water, still poses a detrimental threat to their practical applications. In this article, the adoption of hPGM-ZnTPP hollow microspheres with pH sensitivity and excellent dispersibility in various reaction media, which are firmly immobilized yet accessible catalytic metalloporphyrin components as heterogeneous photocatalysts for the photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, was demonstrated. Modulation of solution pH affected the performance of the catalysts, with the faster polymerization rate being observed in basic conditions rather than in acidic conditions. Besides, this strategy allowed the polymerization of a myriad of functional monomers to afford high polymerization yields and narrow polydispersities in different solvents including dimethyl sulfoxide and water, under a wide range of catalyst concentrations and without prior deoxygenation. By virtue of the robustness of hollow microspheres, multiple isolation and regeneration of the catalyst was accomplished through facile centrifugation with sustainable catalytic activity and negligible catalyst leaching, which in return largely mitigated or even eliminated the contamination and/or decomposition on the final polymer products.