Cu(0) Wire-mediated Single-electron Transfer-living Radical Polymerization of Oligo(ethylene oxide) Methyl Ether Acrylate by Selecting the Optimal Reaction Conditions
Cu(0) Wire-mediated Single-electron Transfer-living Radical Polymerization of Oligo(ethylene oxide) Methyl Ether Acrylate by Selecting the Optimal Reaction Conditions
复制标题
选择最佳反应条件的Cu(0)线介导单电子转移活性自由基聚合环氧乙烷甲基醚丙烯酸酯
DOI：
10.1007/s10118-019-2263-7
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发表时间：
2019-11-01
影响因子：
4.3
通讯作者：
Zhu, Lei
中科院分区：
文献类型：
--
作者：
Ding, Liang;Li, Juan;Zhu, Lei
研究了Cu（0）线催化的有机溶剂及有机溶剂与水的混合物中的单电子转移活性自由基聚合（SET-LRP）。低聚（环氧乙烷）甲基醚丙烯酸酯被用作一个示例性的低聚物单体，以确定最佳的聚合条件，快速，控制和定量生产的明确定义的聚合物。已经评估了Cu（0）-线长度（12.5或4.5 cm）、配体类型（三（二甲基氨基乙基）胺，Me-6-TREN或三（2-氨基乙基）胺，TREN）和溶剂类型（偶极非质子溶剂，环醚，醇或丙酮）对聚合的影响。对所有聚合进行动力学实验以评估所采用的每个系统的“活性”行为。重要的是，TREN可以用作低聚物单体的Cu（0）线催化的SET-LRP中Me-6-TREN的替代物，这可能提供最经济和有效的方法，因为TREN比Me-6-TREN便宜80倍。通过在α-Br链端的硫醇-迈克尔加成反应和随后的丙烯酸甲酯扩链实验验证了所得聚合物的高链端保真度。
The efficient Cu(0) wire-catalyzed single-electron transfer-living radical polymerization (SET-LRP) in organic solvents and mixtures of the organic solvents with water has been thoroughly investigated. Oligo(ethylene oxide) methyl ether acrylate was used as an exemplar oligomer monomer to determine the optimum polymerization conditions for rapid, controlled, and quantitative production of well-defined polymers. The effects of Cu(0)-wire length (12.5 or 4.5 cm), ligand type (tris(dimethylaminoethyl)amine, Me-6-TREN, or tris(2-aminoethyl)amine, TREN), and solvent type (dipolar aprotic solvents, cyclic ethers, alcohol, or acetone) on the polymerization have been evaluated. Kinetic experiments were performed for all polymerizations to assess the "living" behavior of each system employed. Importantly, TREN could be used as a replacement for Me-6-TREN in Cu(0) wire-catalyzed SET-LRP of oligomer monomer, which probably provides the most economical and efficient methodology since TREN is 80 times less expensive than Me-6-TREN. The high chain-end fidelity of resulting polymer was experimentally verified by thiol-Michael addition reaction at the alpha-Br chain end and subsequent chain extension with methyl acrylate.