Visible light-induced controlled radical polymerization of methacrylates with perfluoroalkyl iodide as the initiator in conjugation with a photoredox catalyst fac-[Ir(ppy)]3
Visible light-induced controlled radical polymerization of methacrylates with perfluoroalkyl iodide as the initiator in conjugation with a photoredox catalyst fac-[Ir(ppy)]3
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DOI：
10.1002/pola.27390
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发表时间：
2014-11
期刊：
影响因子：
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通讯作者：
Qian Liu;Lianying Liu;Yuhong Ma;Changwen Zhao;Wantai Yang
中科院分区：
文献类型：
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作者：
Qian Liu;Lianying Liu;Yuhong Ma;Changwen Zhao;Wantai Yang
在光氧化还原催化剂（fac-[Ir(ppy)3]）存在下，以全氟-1-碘己烷（CF3(CF2)5I）为引发剂，制备了一种可见光诱导甲基丙烯酸酯可控自由基聚合新方法。机理上，光激发的面-[Ir(ppy)3]*配合物与休眠的C-I物质反应生成链增殖自由基和IrIVI配合物，并可被增殖自由基可逆还原。在甲基丙烯酸甲酯（MMA）聚合过程中，控制了分子量（Mn）和相应的分布指数（Mw/Mn = 1.4）。对于聚合功能单体，如甲基丙烯酸缩水甘油酯（GMA）和甲基丙烯酸三氟乙酯，它们的单体转化率分别可达96%和94%。在没有外界光刺激的情况下没有发生聚合反应，表明该体系是一个理想的光“开-关”可切换体系。此外，以pmma - 1为宏观引发剂，成功合成了一种干净的二嵌段共聚物PMMA-b-PGMA。以CF3(CF2)5I为引发剂，在聚合物链上引入短CF3(CF2)5−基团标签。©2014 Wiley期刊公司j .变异较大。科学。A部分：Polym。化学，2014,52,3283-3291
A new visible light-induced controlled radical polymerization of methacrylate with perfluoro-1-iodohexane (CF3(CF2)5I) as the initiator in the presence of a photoredox catalyst (fac-[Ir(ppy)3]) was developed. Mechanistically, a photoexcited fac-[Ir(ppy)3]* complex reacted with dormant C-I species to generate the chain propagating radical and IrIVI complex, which could be reversibly reduced by the propagating radical. The molecular weight (Mn) and the corresponding distribution index (Mw/Mn = 1.4) were controlled in the polymerization of methyl methacrylate (MMA). For the polymerization of functional monomers, such as glycidyl methacrylate (GMA) and trifluoroethyl methacrylate, their monomer conversions could be up to 96 and 94%, respectively. No polymerization reaction took place without external light stimulation, indicating that the system was an ideal photo “on−off” switchable system. Furthermore, a clean diblock copolymer PMMA-b-PGMA was successfully synthesized with PMMA-I as the macroinitiator. With CF3(CF2)5I as the initiator, short CF3(CF2)5− group tags were introduced on the produced polymer chains. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 3283–3291