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. 01igo(ethylene ...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. 01igo(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, Me6-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 Me6-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 Me6-TREN. The high chain-end fidelity of resulting polymer was experimentally verified by thiol-Michael addition reaction at the a-Br chain end and subsequent chain extension with methyl acrylate.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 21774107, 21774029, and 21801217)the Natural Science Foundation of Jiangsu ProvinceGeneral Program (No. BK20171273)+2 种基金"Six Talent Peak" High-level Talent Project (JNHB-068)Qing Lan Project of Jiangsu Provincethe Initial Scientific Research Foundation of Yancheng Institute of Technology (No. KJC2014002)
文摘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. 01igo(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, Me6-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 Me6-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 Me6-TREN. The high chain-end fidelity of resulting polymer was experimentally verified by thiol-Michael addition reaction at the a-Br chain end and subsequent chain extension with methyl acrylate.
