离子液体嵌段共聚物的合成及其离子传导性
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摘要
采用可逆加成-断裂链转移自由基聚合法(RAFT)合成了三嵌段共聚物聚甲基丙烯酸丁酯-b-聚对氯甲基苯乙烯-b-聚苯乙烯(PBMA_(69)-b-PVBC_(92)-b-PS_(345), PDI=1.5); PBMA_(69)-b-PVBC_(92)-b-PS_(345)经N-甲基咪唑季铵化后与锂离子盐发生离子交换,两步分别制得两种离子液体嵌段共聚物PBMA-b-PVBMImCl-b-PS和PBMA-b-PVBMImTFSI-b-PS,其结构经~1H NMR, FT-IR和GPC确证。采用交流阻抗研究了两种离子液体嵌段共聚物的导电性能。结果表明:PBMA-b-PVBMImCl-b-PS和PBMA-b-PVBMImTFSI-b-PS的离子电导率分别为6.0×10~(-4)S·cm~(-1)和1.6×10~(-3)S·cm~(-1)。
The triblock copolymer poly(butyl methacrylate)-b-poly[1-(chloromethyl)-4-ethenylbenzene]-b-poly(styrene)(PBMA_(69)-b-PVBC_(92)-b-PS_(345), PDI=1.5) was prepared by continuously reversible addition-fragmentation chain transfer polymerization(RAFT). Two ionic liquid copolymers, PBMA-b-PVBMImCl-b-PS and PBMA-b-PVBMImTFSI-b-PS were synthesized by the quaternary ammonium reaction of the triblock with 1-methylimidazole and then via the anion-exchange with lithium bis(trifluoromethanesulphonyl) imide. The structures were confirmed by ~1H NMR, FT-IR and GPC. The ionic conducting properties of PBMA-b-PVBMImCl-b-PS and PBMA-b-PVBMImTFSI-b-PS were investigated by AC impedance. The results shown that the ionic conducting rate of PBMA-b-PVBMImCl-b-PS and PBMA-b-PVBMImTFSI-b-PS were 6.0×10~(-4) S·cm~(-1) and 1.6×10~(-3) S·cm~(-1), respectively.
The triblock copolymer poly(butyl methacrylate)-b-poly[1-(chloromethyl)-4-ethenylbenzene]-b-poly(styrene)(PBMA_(69)-b-PVBC_(92)-b-PS_(345), PDI=1.5) was prepared by continuously reversible addition-fragmentation chain transfer polymerization(RAFT). Two ionic liquid copolymers, PBMA-b-PVBMImCl-b-PS and PBMA-b-PVBMImTFSI-b-PS were synthesized by the quaternary ammonium reaction of the triblock with 1-methylimidazole and then via the anion-exchange with lithium bis(trifluoromethanesulphonyl) imide. The structures were confirmed by ~1H NMR, FT-IR and GPC. The ionic conducting properties of PBMA-b-PVBMImCl-b-PS and PBMA-b-PVBMImTFSI-b-PS were investigated by AC impedance. The results shown that the ionic conducting rate of PBMA-b-PVBMImCl-b-PS and PBMA-b-PVBMImTFSI-b-PS were 6.0×10~(-4) S·cm~(-1) and 1.6×10~(-3) S·cm~(-1), respectively.
引文
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[9] CHI W S,KOH J K,AHN S H,et al.Highly efficient I 2-free solid-state dye-sensitized solar cells fabricated with polymerized ionic liquid and graft copolymer-directed mesoporous film[J].Electrochemistry Communications,2011,13(12):1349-1352.
[10] SCHNEIDER Y,MODESTINO M A,MCCULLOCH B L,et al.Ionic conduction in nanostructured membranes based on polymerized protic ionic liquids[J].Macromolecules,2013,46(4):1543-1548.
[11] MCCULLOUGH L A,DUFOUR B,MATYJASZEWSKI K.Incorporation of poly(2-acrylamido-2-methyl- N-propanesulfonic acid) segments into block and brush copolymers by ATRP[J].Journal of Polymer Science Part A Polymer Chemistry,2009,47(20):5386-5396.
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[16] MEEK K M,SHARICK S,YE Y,et al.Bromide and hydroxide conductivity-morphology relationships in polymerized ionic liquid block copolymers[J].Macromolecules,2015,48(14):1507-1510.
[17] LAI J T,DEBBY FILLA A,SHEA R.Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents[J].Macromolecules,2002,35(18):6754-6756.