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
Dispersity(D)of polymers has a great effect on the properties of polymeric materials,and therefore how to control θ is very important but still a huge challenge in polymer synthesis,especially for reversible-deactiva...Dispersity(D)of polymers has a great effect on the properties of polymeric materials,and therefore how to control θ is very important but still a huge challenge in polymer synthesis,especially for reversible-deactivation radical polymerization(RDRP)strategy.Herein,we successfully developed a novel strategy to adjust D of polymers by visible light-controlled reversible complexation mediated living radical polymerizatio n(RCMP)and combi nation of single-electron transfer-degenerative chain tran sfer living radical polymerization(SET-DTLRP)at room temperature.In RCMP system,2-iodo-2-methylpropionitrile(CP-I)and ethyl 2-iodo-2-phenylacetate(EIPA)were used as alkyl iodide initiators,by using methyl methacrylate(MMA)as the model monomer and n-butylacrylate(BA)as the end-capping reagent to regulate D of polymers.Subsequently,we successfully prepared the block copolymer PMMA-b-PBA with adjustable D by reactivating the polymer end-chains via SET-DTLRP in the presence of copper wire,fully dem on strati ng that it is a promising strategy that can keep the"living"feature of polymers while regulating their molar mass dispersities easily.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.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22071168 and 21774082)the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD).
文摘Dispersity(D)of polymers has a great effect on the properties of polymeric materials,and therefore how to control θ is very important but still a huge challenge in polymer synthesis,especially for reversible-deactivation radical polymerization(RDRP)strategy.Herein,we successfully developed a novel strategy to adjust D of polymers by visible light-controlled reversible complexation mediated living radical polymerizatio n(RCMP)and combi nation of single-electron transfer-degenerative chain tran sfer living radical polymerization(SET-DTLRP)at room temperature.In RCMP system,2-iodo-2-methylpropionitrile(CP-I)and ethyl 2-iodo-2-phenylacetate(EIPA)were used as alkyl iodide initiators,by using methyl methacrylate(MMA)as the model monomer and n-butylacrylate(BA)as the end-capping reagent to regulate D of polymers.Subsequently,we successfully prepared the block copolymer PMMA-b-PBA with adjustable D by reactivating the polymer end-chains via SET-DTLRP in the presence of copper wire,fully dem on strati ng that it is a promising strategy that can keep the"living"feature of polymers while regulating their molar mass dispersities easily.
