Que Yurong, Huang Zhong, Feng Chun, Yang Yang, Huang Xiaoyu
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, People's Republic of China.
ACS Macro Lett. 2016 Dec 20;5(12):1339-1343. doi: 10.1021/acsmacrolett.6b00732. Epub 2016 Nov 17.
Graphite fluoride (GiF) and graphene fluoride (GeF) showed interesting electrochemical, electronic, and mechanical properties in comparison with their derivatives of graphite and graphene, respectively. Due to the chemical inertness of GiF and GeF, as far as we are aware, no report can be found on the modification of GiF and GeF with polymeric chains. Herein, we reported that photoredox-mediated atom transfer radical polymerization (ATRP) is able to directly introduce methacrylate-based polymers, including poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA), poly(methyl methacrylate) (PMMA), poly(pentafluorophenyl methacrylate) (PPFMA), and poly(methacrylic acid) (PMAA), onto the surface of GiF and GeF by utilizing C-F bonds of GiF and GeF as initiating sites and Ir(ppy) as a photoredox catalyst under low intensity blue LED light strips (10 W, 460-470 nm) in DMF for graft polymerization without a tedious deoxygenation procedure. Owing to the attractive properties of GiF and GeF, along with the capacity of spatial control over the formation of polymeric chains on the surface of GiF and GeF endowed by the inherent nature of photoredox-mediated ATRP, there is no doubt that the strategy developed in the current work shows a great potential in the preparation of polymer-decorated GiF and GeF and the corresponding functional materials.
与石墨和石墨烯的衍生物相比，氟化石墨（GiF）和氟化石墨烯（GeF）分别展现出有趣的电化学、电子和机械性能。据我们所知，由于GiF和GeF的化学惰性，尚未发现有关用聚合物链修饰GiF和GeF的报道。在此，我们报道了光氧化还原介导的原子转移自由基聚合（ATRP）能够在低强度蓝色LED灯带（10 W，460 - 470 nm）下，于N,N - 二甲基甲酰胺（DMF）中，以GiF和GeF的C - F键为引发位点，以Ir(ppy)为光氧化还原催化剂，通过接枝聚合直接将基于甲基丙烯酸酯的聚合物，包括聚（寡聚（乙二醇）甲基醚甲基丙烯酸酯）（POEGMA）、聚甲基丙烯酸甲酯（PMMA）、聚（五氟苯基甲基丙烯酸酯）（PPFMA）和聚甲基丙烯酸（PMAA）引入到GiF和GeF的表面，而无需繁琐的脱氧程序。由于GiF和GeF具有吸引人的性能，以及光氧化还原介导的ATRP的固有性质赋予了在GiF和GeF表面形成聚合物链的空间控制能力，毫无疑问，当前工作中开发的策略在制备聚合物修饰的GiF和GeF以及相应的功能材料方面具有巨大潜力。
