Tailoring intermolecular interactions in ion gels with rationally designed phosphonic acid polymers,Polymer Chemistry

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Tailoring intermolecular interactions in ion gels with rationally designed phosphonic acid polymers
Polymer Chemistry ( IF 4.1 ) Pub Date : 2022-06-22 , DOI: 10.1039/d2py00646d
Sejong Kang ₁ , Moon Jeong Park ₁

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Ideal ion gels exhibit high ionic conductivities and mechanical strengths, but developing such ion gels is challenging, as a high ionic conductivity generally requires a high ionic liquid content, which inevitably reduces the mechanical strength. Herein, we report the controlled syntheses of poly(4-styrenephosphonic acid) (PS4P) and poly(3-styrenephosphonic acid) (PS3P) polymers to achieve challenging goals via the modulation of intermolecular interactions in ion gels containing ionic liquids. Less steric hindrance and increased rotational freedom in PS4P enabled effective swelling and facilitated self-healing of the PS4P-based block copolymer ion gels via robust hydrogen bond formation. Meanwhile, the adjacent chain packing with restricted swelling of the PS3P-based ion gels enabled high toughness and concerted proton hopping. To form dual-crosslinked ion gels, the type of ionic liquid anion was changed to promote ionic interactions, which yielded elastic gels with improved conductivities. Varying the types of ionophobic blocks used in the syntheses of the phosphonated block copolymers allowed the control of the chain stretching in ionic domains. This determined the local ion concentration, thereby modifying the ionic conductivities of the ion gels. Our approach establishes the design of phosphonic acid polymers that exhibit a configurable balance of ionic and hydrogen bonding interactions at the molecular level, which should be a platform for developing advanced ion gels.

中文翻译：

使用合理设计的膦酸聚合物调整离子凝胶中的分子间相互作用

理想的离子凝胶表现出高离子电导率和机械强度，但开发这种离子凝胶具有挑战性，因为高离子电导率通常需要高离子液体含量，这不可避免地会降低机械强度。在这里，我们报告了聚（4-苯乙烯膦酸）（PS4P）和聚（3-苯乙烯膦酸）（PS3P）聚合物的受控合成，以通过调节含有离子液体的离子凝胶中的分子间相互作用来实现具有挑战性的目标。PS4P 中较少的空间位阻和增加的旋转自由度使基于 PS4P 的嵌段共聚物离子凝胶通过以下方式有效膨胀并促进自愈强大的氢键形成。同时，基于 PS3P 的离子凝胶膨胀受限的相邻链堆积实现了高韧性和协调的质子跳跃。为了形成双交联离子凝胶，改变离子液体阴离子的类型以促进离子相互作用，从而产生具有改善电导率的弹性凝胶。改变在膦酸化嵌段共聚物的合成中使用的疏离子嵌段的类型，可以控制离子域中的链拉伸。这确定了局部离子浓度，从而改变了离子凝胶的离子电导率。我们的方法建立了膦酸聚合物的设计，该聚合物在分子水平上表现出离子和氢键相互作用的可配置平衡，这应该是开发先进离子凝胶的平台。

更新日期：2022-06-22

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