Pendent Sulfonylimide Ionic Liquid Monomers and Ionoelastomers via SuFEx Click Chemistry
Pendent Sulfonylimide Ionic Liquid Monomers and Ionoelastomers via SuFEx Click Chemistry
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DOI：
10.1021/acs.chemmater.3c02038
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发表时间：
2023-11
影响因子：
8.6
通讯作者：
Owen A. Lee;M. K. McBride;Matthew Ticknor;Joshua Sharpes;R. C. Hayward
中科院分区：
文献类型：
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作者：
Owen A. Lee;M. K. McBride;Matthew Ticknor;Joshua Sharpes;R. C. Hayward
具有固定磺酰亚胺基团的阴离子聚合离子液体由于其高度离域的阴离子电荷而成为用于能量存储应用、机电装置和气体分离膜的有前景的材料。然而，合成的挑战限制了大规模生产高纯度聚（磺酰亚胺），并阻碍了其性能的系统评价。我们报告了使用硫（VI）氟化物交换（SuFEx）点击反应以>10 g规模生产高纯度磺酰亚胺单体的合成路线。合成了含1-乙基-3-甲基咪唑反离子的侧基磺酰亚胺丙烯酸酯单体，并将其与不同长度的全氟侧基交联形成离子弹性体。该网络是可拉伸的（约120%断裂应变），显示出高的无溶剂离子电导率（>3.8 × 10- 3 mS/cm），并且是疏水的，水接触角>105°。咪唑抗衡离子强烈地与全氟化侧链相互作用，产生相对于玻璃化转变温度（Tg）的离子电导率和模量的非单调趋势。广角X-射线散射和振动光谱表明，较短的全氟侧基促进阳离子解离，而较长的链引起离子聚集。我们预计，这种SuFEx方法将扩大获得下一代聚（磺酰亚胺）电解质的各种应用，并在这里证明其实用性，为聚（磺酰亚胺）离子弹性体的分子水平设计提供新的见解。
Anionic polymerized ionic liquids with a fixed sulfonylimide group have emerged as promising materials for energy storage applications, electromechanical devices, and gas separation membranes due to their highly delocalized anionic charges. However, synthetic challenges have limited the production of high-purity poly(sulfonylimide)s at scale and hindered systematic evaluation of their properties. We report a synthetic route for the production of high-purity sulfonylimide monomers at >10 g scales using a sulfur(VI) fluoride exchange (SuFEx) click reaction. Pendent sulfonylimide acrylate monomers with 1-ethyl-3-methylimidazolium counterions were synthesized with perfluorinated side groups of different lengths and cross-linked to form ionoelastomers. The networks were stretchable (≈120% strain at break), showed high solvent-free ionic conductivity (>3.8 × 10–3mS/cm), and were hydrophobic with water contact angles >105°. The imidazolium counterions interact strongly with the perfluorinated side chains, yielding nonmonotonic trends in ionic conductivity and modulus relative to the glass transition temperature (Tg). Wide-angle X-ray scattering and vibrational spectroscopies reveal that shorter perfluorinated side groups promote cation dissociation, while longer chains cause ionic aggregation. We expect that this SuFEx approach will expand access to next-generation poly(sulfonylimide) electrolytes for a variety of applications and here demonstrate its utility for providing new insight into the molecular-level design of poly(sulfonylimide) ionoelastomers.