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高压红外光谱研究离子液体与聚环氧乙烷-聚环氧丙烷-聚环氧乙烷嵌段共聚物和 1,4-二氧六环的相互作用。

A high-pressure infrared spectroscopic study on the interaction of ionic liquids with PEO-PPO-PEO block copolymers and 1,4-dioxane.

机构信息

Department of Chemical Engineering, National Taiwan University of Science and Technology, Taipei, Taiwan.

出版信息

J Phys Chem B. 2011 Feb 10;115(5):883-8. doi: 10.1021/jp109600c. Epub 2010 Dec 29.

Abstract

We have investigated the effect of pressure on imidazolium C-H---O interactions in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (EMI(+)TFSA(-))/L64 and EMI(+)TFSA(-)/1,4-dioxane mixtures. The addition of Pluronic L64 to EMI(+)TFSA(-) leads to appreciable changes in band frequencies and shapes of the imidazolium C-H stretching bands. A possible explanation is the formation of C-H---O interactions between imidazolium C-H groups and oxygen atoms of polyethylene oxides (PEOs). In other words, L64 can be added to change the relative contribution of the isolated and associated components of EMI(+)TFSA(-). In contrast to L64, the oxygen atoms of 1,4-dioxane cannot perturb the local structures of imidazolium C-H groups of EMI(+)TFSA(-) and the association configuration is still favored in the presence of 1,4-dioxane. As the pressure is elevated, 1,4-dioxane molecules tend to associate with themselves and TFSA(-) interacts with EMI(+) to form associated configurations. Our results suggest the formation of association between EMI(+) cation and L64 and the complexes are stable up to the pressure of 2.5 GPa.

摘要

我们研究了压力对 1-乙基-3-甲基咪唑双(三氟甲烷磺酰基)酰胺(EMI(+)TFSA(-))/L64 和 EMI(+)TFSA(-)/1,4-二氧六环混合物中咪唑 C-H---O 相互作用的影响。向 EMI(+)TFSA(-)中添加 Pluronic L64 会导致咪唑 C-H 伸缩带的带频率和形状发生明显变化。一种可能的解释是咪唑 C-H 基团和聚氧化乙烯(PEO)的氧原子之间形成了 C-H---O 相互作用。换句话说,L64 可以添加以改变 EMI(+)TFSA(-)的孤立和缔合组分的相对贡献。与 L64 相反,1,4-二氧六环的氧原子不能扰动 EMI(+)TFSA(-)中咪唑 C-H 基团的局部结构,并且在存在 1,4-二氧六环的情况下仍然有利于缔合构型。随着压力的升高,1,4-二氧六环分子倾向于自身缔合,并且 TFSA(-)与 EMI(+)相互作用形成缔合构型。我们的结果表明 EMI(+)阳离子与 L64 之间形成了缔合,并且这些配合物在 2.5 GPa 的压力下稳定。

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