1-烷基-4-氨基-1,2,4-三唑类含能离子液体的溶解性能  

Solubility Properties of 1-Alkyl-4-amino-1,2,4-triazolium Energetic Ionic Liquids

作　　者：高博[1] 杨宏伟 田少鹏[1] 赵玉真[1] 田甜 GAO Bo;YANG Hongwei;TIAN Shaopeng;ZHAO Yuzhen;TIAN Tian(School of Science,Xijing University,Xi′an 710123,China;Materials Science and Engineering,Hebei University of Engineering,Handan,Hebei 056038,China)

机构地区：[1]西京学院理学院,西安710123 [2]河北工程大学材料科学与工程学院,河北邯郸056038

出　　处：《应用化学》2019年第9期1044-1052,共9页Chinese Journal of Applied Chemistry

基　　金：陕西省教育厅专项科研计划(18JK1205);河北省自然科学基金青年基金项目(E2018402211)资助~~

摘　　要：基于NO-3、ClO-4、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1 H 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]ClO 4>[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]ClO 4>[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。Based on NO-3,ClO-4,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 1 H 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]ClO 4>[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]ClO 4>[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.

关 键 词：含能离子液体 密度泛函理论 溶解性能 介电常数 

分 类 号：O645[理学—物理化学]