Macro-RAFT agent,poly(methyl methacrylate) was synthesized by reversible addition-fragmentation chain transfer(RAFT) polymerization using S-dodecyl-S′-(α,α′-dimethyl-α″-acetic acid)-trithiocarbonate as the chain transfer agent,AIBN as the initiator.PMMA205-b-PBMA136-b-PDMAEMA128(poly(methyl methacrylate)-b-poly(butyl methacrylate)-b-poly(2-(dimethy lamino)ethyl meth-acrylate)(subscript was polymerization degree),triblock copolymer was synthesized by a sequentially initiating of BMA and DMAEMA,in the precence of macro-RAFT agent.Index of molecular weight distribution of triblock copolymer was 1.32.The triblock copolymer was also characterized by 1H-NMR and FT-IR.Then,triblock ionic liquid copolymers with different counterion(Br-,BF-4,TFSI-) were synthesized by the quaternary ammonium reaction with bromobutane and then anion-exchange with Lithium bis (trifluoromethanesulphonyl) imide (LiTFSI) or sodium fluoborate (NaBF4).The electroconductivity of triblock ionic liquid copolymers was also studied by AC impedance,PMMA-b-PBMA-b-PILS membranes showed the ionic conductivity was up to 10-3S/cm at room temperature.
[1] Shaplov A S,Marcilla R,Mecerreyes D.Recent advances in innovative polymer electrolytes based on poly(ionic liquid)s[J].Electrochimica Acta,2015,175(3):18-34.
[2] Qian W,Texter J,Yan F.Frontiers in poly(ionic liquid)s:syntheses and applications[J].Chemical Society Reviews,2017,46(4):1124.
[3] Zhao J,Deng C L,Du S L,et al.Synergistic flame-retardant effect of halloysite nanotubes on intumescent flame retardant in LDPE[J].Journal of Applied Polymer Science,2014,131(7):2540-2540.
[4] Li M,Wang L,Yang B,et al.Facile preparation of polymer electrolytes based on the polymerized ionic liquid poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) for lithium secondary batteries[J].Electrochimica Acta,2014,123(10):296-302.
[5] Yin K,Zhang Z,Yang L,et al.An imidazolium-based polymerized ionic liquid via novel synthetic strategy as polymer electrolytes for lithium ion batteries[J].Journal of Power Sources,2014,258(258):150-154.
[6] Wojnarowska Z,Knapik J,Díaz M,et al.Conductivity mechanism in polymerized imidazolium-based protic ionic liquid [HSO3-BVIm][OTf]:dielectric relaxation studies[J].Macromolecules,2014,47(12):4056-4065.
[7] Díaz M,Ortiz A,Vilas M,et al.Performance of PEMFC with new polyvinyl-ionic liquids based membranes as electrolytes[J].International Journal of Hydrogen Energy,2014,39(8):3970-3977.
[8] 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.
[9] Wang G,Wang L,Zhuo S,et al.An iodine-free electrolyte based on ionic liquid polymers for all-solid-state dye-sensitized solar cells[J].Chemical Communications,2011,47(9):2700-2702.
[10] Rong Y,Ku Z,Xu M,et al.Efficient monolithic quasi-solid-state dye-sensitized solar cells based on poly(ionic liquids) and carbon counter electrodes[J].RSC Advances,2014,4(18):9271-9274.
[11] 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.
[12] 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):4850-4862.
[13] Wiesenauer E F,Nguyen P T,Newell B S,et al.Imidazolium-containing,hydrophobic-ionic-hydrophilic ABC triblock copolymers:synthesis,ordered phase-separation,and supported membrane fabrication[J].Soft Matter,2013,9(33):7923-7927.
[14] 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.
基金资助
国家自然科学基金(21544008)
PDF
(1364KB)
