1-烷基-4-氨基-1,2,4-三唑类含能离子液体的溶解性能

doi:10.11944/j.issn.1000-0518.2019.09.190036

摘要/Abstract

摘要：

基于NO3-、ClO4-、N(CN)2-、[2,4,5-TNI]^-和[3,5-DNTZ]^-阴离子,以及1-烷基-4-氨基-1,2,4-三唑阳离子合成了系列环境友好型含能离子液体,通过¹H NMR对其进行了结构表征;采用ab initio结合MP2/6-311G++(2d,p)方法计算了1-烷基-4-氨基-1,2,4-三唑类含能离子液体和溶剂之间的分子间作用能以及含能离子液体的偶极距;系统研究了分子结构、极性以及分子间作用能对该系列含能离子液体的溶解性能的影响。结果表明:当阳离子不同时,[BATZ]NO₃与水的ΔE绝对值最大为40.7 kJ/mol,当阴离子不同时,[BATZ][3,5-DNTZ]与水的ΔE绝对值最大为45.1 kJ/mol;上述含能离子液体的极性大小顺序为[BATZ][3,5-DNTZ]>[BATZ][2,4,5-TNI]>[BATZ]N(CN)₂>[BATZ]ClO₄>[RATZ]NO₃;最后,1-烷基-4-氨基-1,2,4-三唑类含能离子液体的溶解度随着溶剂介电常数ε的减小、取代烷基链长的增加、阴离子体积的增大以及分子间作用能的减小而降低,即含能离子液体在溶剂中的溶解度大小顺序为[BATZ][3,5-DNTZ]>[BATZ][2,4,5-TNI]>[BATZ]NO₃>[BATZ]ClO₄>[BATZ]N(CN)₂>[PATZ]NO₃>[HATZ]NO₃>[DATZ]NO₃,其中,[BATZ][2,4,5-TNI]在水中溶解度最大为10.0327 g/10 g。

关键词: 含能离子液体, 密度泛函理论, 溶解性能, 介电常数

Abstract:

Based on NO3-, ClO4-, N(CN)2-, [2,4,5-TNI]^-, [3,5-DNTZ]^- anions, a series of 1-alkyl-4-amino-1,2,4-triazolium energetic ionic liquids(EILs) were synthesized. The structures were characterized by ¹H NMR spectroscopy. The interaction energies of EILs-solvents and dipole moment of the 1-alkyl-4-amino-1,2,4-triazolium EILs were calculated using ab initio at MP2/6-311G++(2d,p). The relationships between the solubility and molecular structure, common solvents, and the interaction energies of EILs-solvents, etc., were discussed systematically. The results showed that the |ΔE| between [BATZ]NO₃ and water had the biggest value of 40.7 kJ/mol with the different cations and the |ΔE| of [BATZ][3,5-DNTZ] and water possessed the biggest value of 45.1 kJ/mol with the same cation. The dipole moment of the above EILs was in the following order:[BATZ][3,5-DNTZ]>[BATZ][2,4,5-TNI]>[BATZ]N(CN)₂>[BATZ]ClO₄>[RATZ]NO₃. The solubility of the title energetic ionic liquids increased with decreasing dielectric constant of solvent. With the increase of the alkyl chain length, the interaction energies of EILs-solvents, the anion size , and the solubility in polar solvents all decreased. The solubility in polar solvents was in the following order:[BATZ][3,5-DNTZ]>[BATZ][2,4,5-TNI]>[BATZ]NO₃>[BATZ]ClO₄>[BATZ]N(CN)₂>[PATZ]NO₃>[HATZ]NO₃>[DATZ]NO₃, and [BATZ][2,4,5-TNI] had the highest solubility of 10.0327 g/10 g in water.

Key words: energetic ionic liquids, density functional methods, solubility, dielectric constant

高博, 杨宏伟, 田少鹏, 赵玉真, 田甜. 1-烷基-4-氨基-1,2,4-三唑类含能离子液体的溶解性能[J]. 应用化学, 2019, 36(9): 1044-1052.

GAO Bo, YANG Hongwei, TIAN Shaopeng, ZHAO Yuzhen, TIAN Tian. Solubility Properties of 1-Alkyl-4-amino-1,2,4-triazolium Energetic Ionic Liquids[J]. Chinese Journal of Applied Chemistry, 2019, 36(9): 1044-1052.

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