Abstract
Ionic liquid-based block copolymers composed of ionic (solubility tunable)–nonionic (water-soluble and thermoresponsive) segments were synthesized to explore the relationship between ionic conductivity and assembled structures. Three block copolymers, comprising poly(N-vinylimidazolium bromide) (poly(NVI-Br)) as a hydrophilic poly(ionic liquid) segment and thermoresponsive poly(N-isopropylacrylamide) (poly(NIPAM)), having different compositions, were initially prepared by RAFT polymerization. The anion-exchange reaction of the poly(NVI-Br) in the block copolymers with lithium bis(trifluoromethanesulfonyl)imide (LiNTf2) proceeded selectively to afford amphiphilic block copolymers composed of hydrophobic poly(NVI-NTf2) and hydrophilic poly(NIPAM). Resulting poly(NVI-NTf2)-b-poly(NIPAM) exhibited ionic conductivities greater than 10−3 S/cm at 90 °C and 10−4 S/cm at 25 °C, which can be tuned by the comonomer composition and addition of a molten salt. Temperature-dependent ionic conductivity and assembled structures of these block copolymers were investigated, in terms of the comonomer composition, nature of counter anion and sample preparation procedure.
Highlights
Polymeric ionic liquids, which combine the advantages of macromolecules with various attractive features of ionic liquids, have been the subject of significant and sustained research [1,2,3,4,5]
Synthesis and Anion-Exchange Reaction of Imidazolium Salt-Based Block Copolymers nonionic segments were employed as double-hydrophilic and amphiphilic block types of salt-based block copolymers having ionicof(solubility tunable) and of the copolymersTwo
We focused on the design and manipulation assembled structures nonionic segments were employed as double-hydrophilic and amphiphilic imidazolium salt-based block copolymers and their ion conductivity
Summary
Polymeric ionic liquids, which combine the advantages of macromolecules with various attractive features of ionic liquids, have been the subject of significant and sustained research [1,2,3,4,5]. A diverse range of ionic liquid-based block copolymers having various substituent groups and counterions has been developed using various controlled radical polymerizations, which involve atom-transfer radical polymerization [17,18], reversible addition–fragmentation chain transfer (RAFT) polymerization [19,20,21,22,23] and cobalt-mediated radical polymerization [24,25,26] of imidazolium-containing monomers This has resulted in an understanding of the structure–morphology property correlation, including the ionic conductivity and nanostructured morphologies of self-assembled architectures [6,7,8,9]. We describe the investigation of temperature-dependent ionic conductivity and assembled structures of ionic liquid-based block copolymers having a thermoresponsive segment, in terms of the comonomer composition, counteranion and sample preparation procedure. To the lower critical solution temperature, LCST, of the poly(NIPAM) segment (around 32 ◦ C)
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