Visible-light induced controlled radical polymerization of methacrylates with Cu(dap)(2)Cl as a photoredox catalyst
Visible-light induced controlled radical polymerization of methacrylates with Cu(dap)(2)Cl as a photoredox catalyst
复制标题
Cu(dap)(2)Cl作为光氧化还原催化剂的可见光诱导甲基丙烯酸酯受控自由基聚合
DOI：
10.1039/c6py00687f
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发表时间：
2016
影响因子：
4.6
通讯作者：
Yang Wantai
中科院分区：
文献类型：
--
作者：
Ma Wenchao;Chen Dong;Ma Yuhong;Wang Li;Zhao Changwen;Yang Wantai
以α-溴苯乙酸乙酯（EBPA）为引发剂，以 Cu(dap)2Cl（dap = 2,9-双（对茴香基）-1,10-菲咯啉）为光氧化还原催化剂，证明了聚乙二醇甲醚甲基丙烯酸酯（PEGMA）和甲基丙烯酸甲酯（MMA）的受控自由基聚合 在LED灯照射下（4500 μW cm−2@420 nm）。催化循环在 N,N-二甲基苯胺 (DMA) 或三[2-(二甲基氨基)乙基]胺 (Me6TREN) 存在下进行，它们可以作为还原剂从氧化的 Cu(II) 络合物再生 Cu(I) 络合物。此外，Me6TREN 作为甲基丙烯酸酯单体铜基光聚合的有效配体发挥着另一个重要作用。在优化条件下观察到分子量 (Mn) 随单体转化率的良好线性变化。具体来说，当 [PEGMA] : [EBPA] : [Cu(dap)2Cl] : [Me6TREN] = 31 : 1 : 0.015 : (0.15–0.45) 时，聚(PEGMA) (PPEGMA) 的多分散指数 (PDI) 低至得到1.15。为了进一步验证该系统的活性，使用 PPEGMA-Br (Mn,GPC = 1.44) 制备了具有高分子量和窄分子量分布的 PPEGMA-b-PMMA 嵌段共聚物 (Mn,GPC = 59 200 g mol−1, PDI = 1.28 和 Mn,GPC = 93 700 g mol−1, PDI = 1.44)。 11 600 g mol−1; PDI = 1.13) 作为大分子引发剂。以Cu(dap)2Cl/Me6TREN为催化剂生产的聚合物和以Cu(dap)2Cl/DMA为催化剂获得的PMMA都是无色的，这与多相催化的ATRP不同，其存在臭名昭著的Cu金属残留物。
With ethyl-α-bromophenylacetate (EBPA) as an initiator and Cu(dap)2Cl (dap = 2,9-bis(p-anisyl)-1,10-phenanthroline) as a photoredox catalyst, controlled radical polymerizations of poly(ethylene glycol)methyl ether methacrylate (PEGMA) and methyl methacrylate (MMA) are demonstrated under LED light lamp irradiation (4500 μW cm−2@420 nm). The catalysis cycles proceed in the presence of N,N-dimethylaniline (DMA) or tris[2-(dimethylamino)ethyl]amine (Me6TREN), which could serve as reductants to regenerate a Cu(I) complex from the oxidized Cu(II) complex. In addition, Me6TREN plays another important role as an efficient ligand for the copper-based photopolymerization of methacrylate monomers. Good linear evolution of molecular weight (Mn) with monomer conversion is observed under the optimized conditions. Specifically, with [PEGMA] : [EBPA] : [Cu(dap)2Cl] : [Me6TREN] = 31 : 1 : 0.015 : (0.15–0.45), poly(PEGMA) (PPEGMA) with polydispersity indexes (PDI) as low as 1.15 are obtained. To further verify the living nature of this system, block copolymers of PPEGMA-b-PMMA with high molecular weights and narrow molecular weight distributions (Mn,GPC = 59 200 g mol−1, PDI = 1.28 and Mn,GPC = 93 700 g mol−1, PDI = 1.44, respectively) are prepared using PPEGMA-Br (Mn,GPC = 11 600 g mol−1; PDI = 1.13) as a macroinitiator. The polymers produced with Cu(dap)2Cl/Me6TREN as a catalyst and the PMMA obtained with Cu(dap)2Cl/DMA as a catalyst are colorless which is different from the heterogeneously catalyzed ATRP for its notorious Cu metal residue.