三甲胺类非对称双阳离子型离子液体的合成及其物理化学性质研究  

Study on Synthesis and Physicochemical Properties of Trimethylaminium Related Asymmetrical Dicationic Ionic Liquids

作　　者：王军[1] 武金超[1] 杨许召[1] 王满满[1] 苗进辉 

机构地区：[1]郑州轻工业学院河南省表界面科学重点实验室,河南郑州450002

出　　处：《高校化学工程学报》2014年第5期944-950,共7页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(21176228)

摘　　要：研究了一类新型的非对称双阳离子型离子液体的合成及物理化学性质,为该类离子液体的工业应用奠定理论基础。以3-溴丙基三甲基溴化铵、吡啶和4-甲基吗啉为阳离子母体设计合成了一类非对称双阳离子型离子液体,产品进行了IR和H1 NMR表征。通过差示扫描量热仪(DSC)测定了离子液体1-(4-甲基吗啉鎓基)-3-(三甲胺鎓)丙烷双三氟磺酰亚胺盐([MpC3N111][NTf2]2)和1-(吡啶鎓基)-3-(三甲胺鎓)丙烷双三氟磺酰亚胺盐([PyC3N111][NTf2]2)的热力学性质,得到了其熔点、相变焓和相变熵的值。对热容数据进行多项式拟合,得到了以298.15 K为参考温度的固相区和液相区的热力学方程。利用非等温热重分析法(TG),研究了高纯氮气气氛下离子液体[MpC3N111][N(CN)2]2和[PyC3N111][N(CN)2]2的热分解动力学,通过ASTM法和Ozawa-Flynn-Wall法对不同升温速率下的热分解数据进行关联,得到了反应活化能Ea和指前因子lgA,两种方法得到的结果基本一致。A series of asymmetrical dicationic ionic liquids based on trimethylaminium cation using （3-bromoproryl）trimethylammonium bromide, pyridinium and 4-methylmorpholinium as cation matrices were synthesized. These asymmetrical dicationic ionic liquids were characterized by IR and 1H NMR. The heat capacities of these dicationic ionic liquids were determined by differential scanning calorimeter （DSC） and the melting points, molar enthalpies and entropies of fusion were obtained. Moreover, the molar heat capacities of [MpC3N111][NTf2]2 and [PyC3N111][NTf2]2 were fitted to polynomials, and the thermodynamic functions of [MpC3N111][NTf2]2 and [PyC3N111][NTf2]2 relative to a reference temperature of 298.15 K were derived based on the heat capacities. The thermal decomposition kinetics of [MpC3N111][N（CN）2]2 and [PyC3N111][N（CN）2]2 were studied using non-isothermal thermogravimetric analysis （TG） under nitrogen atmosphere, and the heating curves at different rates were correlated with ASTM and Ozawa-Flynn-Wall equations, respectively. In addition, the activation energy, Ea, and logarithmic pre-exponential factor, lgA, were obtained,and the results of the two methods are consistent.

关 键 词：非对称双阳离子型离子液体 合成 热容 热分解动力学 

分 类 号：TQ150.1[化学工程—电化学工业] O646.1[理学—物理化学]