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Ionic Conductivity and Assembled Structures of Imidazolium Salt-Based Block Copolymers with Thermoresponsive Segments
Kazuhiro Nakabayashi1,2, Yu Sato3, Yuta Isawa4
1Department of Polymer Science and Engineering, Graduate School of Science and Engineering, Yamagata University, 4-3-16, Jonan, Yonezawa 992-8510, Japan. nakabayashi.k@yz.yamagata-u.ac.jp.
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.
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