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题名	咪唑、季鏻类离子液体的合成及应用研究
作者	张延强
学位类别	博士
答辩日期	2008-05-28
授予单位	中国科学院过程工程研究所
授予地点	过程工程研究所
导师	张锁江
关键词	离子液体 纯度 双水相 碳纳米管 功能化 氨基 CO2
其他题名	Synthesis and Application of Imidazolium and Phosphonium Ionic Liquids
学位专业	应用化学
中文摘要	离子液体（ILs）是完全由阴、阳离子构成的在室温或室温附近呈液态的有机盐类物质，其结构特点决定了离子液体的种类繁多，潜在的数目高达1018。伴随着新型离子液体的不断涌现和相关研究的逐步深化，离子液体已不再仅仅是一种绿色溶剂，更是一类性能优良的功能材料，已被广泛地应用于催化反应、有机合成、分离过程和电化学等领域。开发新型离子液体和拓展离子液体新的应用始终是离子液体研究的主要方向。 鉴于此，本文针对咪唑类和季鏻类离子液体的合成及应用做了如下工作： （1）合成了系列常规咪唑类离子液体，提出并验证了高效液相色谱法（HPLC）是测定该系列离子液体含量和纯度的一种通用、快捷、精确的方法，并把该方法很好地用于常规咪唑类离子液体大规模制备过程中产品的质量控制。 （2）研究了常规咪唑类离子液体（[Bmim]Cl、[Bmim]Br和[Bmim]BF4）-果糖-水体系，发现只有[Bmim]BF4和果糖能很好地形成双水相体系。系统地测定了[Bmim]BF4和果糖双水相体系的相平衡随温度（25~45 ℃）的变化，包括浊点线、连结线和临界点，结果表明[Bmim]BF4和果糖的两相区范围很宽，且随温度的升高而减小，当果糖质量组成在3~40％时减小明显。用Othmer-Tobias和Bancroft方程关联了连结线，关联系数均大于0.99，并对体系的成相机理进行了合理地解释。 （3）研究了常规咪唑类离子液体[Bmim]BF4分散原始的和羧基修饰的碳纳米管（CNTs），结果表明[Bmim]BF4可以很好地分散羧基修饰的CNTs，[Bmim]BF4和CNTs之间的静电和氢键作用明显地提高了分散体系的稳定性。此外，发现高压CO2对该分散体系中的CNTs具有抗溶作用，可作为CNTs回收利用的一种绿色方法。 （4）合成了阴、阳离子都带功能化氨基的咪唑类和季鏻类离子液体，系统地表征了得到的20种双氨基功能化季鏻离子液体（[aP4443][AA]）的结构，并测定了其物化性质（密度、粘度、电导率、玻璃转化温度和热分解温度），结果表明得到的[aP4443][AA]在热化学性质方面明显优于相应的咪唑类、吡啶类和季铵类离子液体。 （5）研究了双氨基功能化季鏻离子液体[aP4443][Gly]和[aP4443][Ala]对CO2的吸收，结果表明，[aP4443][Gly]和[aP4443][Ala]负载SiO2吸收CO2克服了直接用离子液体吸收CO2效率低的缺点，能在100 min内达到CO2吸收平衡，且化学吸收量接近1 mol CO2/1 mol IL。吸收的CO2可在60 ℃、负压下解吸，解吸后的[aP4443][Gly]和[aP4443][Ala]重复4次循环使用对CO2吸收速率和吸收量没有明显减弱。
英文摘要	Ionic liquids (ILs) composed entirely of ions are fluid around room temperature or below 100 ℃. Considering so many different cations and anions, at least 1018 ILs are potentially possible. With the more ILs and the deeper studies, ILs are not only regarded as a kind of novel and green solvents, but a kind of functional materials which are widely applied in catalytic reactions, organic syntheses, separations, electrochemistry, and so on. Synthesizing new kinds of ILs and exploiting ILs’ new applications are always the main tasks of ILs’ studies. As mentioned above, synthesis and application of imidazolium and phosphonium ILs are investigated as follows: (1) A series of imidazolium ILs was synthesized. High performance liquid chromatography (HPLC) was firstly proposed and demonstrated as a convenient and efficient method for determining content and purity of the imidazolium ILs quantitatively, which was also applied as an efficient method for the quality control of imidazolim ILs produced in large scale. (2) The system of imidazolium ILs ([Bmim]Cl, [Bmim]Br, and [Bmim]BF4, respectively) + fructose + water was investigated. It was found that only [Bmim]BF4 can form aqueous biphasic systems (ABSs). The ABSs were measured systematically, including binodal curves and tie lines. It was shown that the liquid-liquid equilibria can be formed over a wide component range, which decreases with the temperature increase, especially within the fructose concentration (w/w) changing from 3 to 40 percent. The tie lines can be well fitted with the Othmer-Tobias and the Bancroft equations. Moreover, the mechanism of ABSs formation was discussed. (3) Imidazolium IL ([Bmim]BF4) was selected to disperse the pristine and the carboxyl-functionalized carbon nanotubes (CNTs). It was shown that [Bmim]BF4 can disperse the carboxyl-functionalized CNTs well. The [Bmim]BF4 + CNTs system has a good stability, mainly because of the static and hydrogenic interactions. Furthermore, CO2 with high pressure can separate CNTs from [Bmim]BF4, which can be applied as a green way for CNTs recycle. (4) Functional imidazolium and phosphonim ILs whose both cation and anion have the appended amine group were synthesized. Especially, structures and physicochemical properties (density, viscosity, conductivity, glass transition point and decomposition point) of the 20 dual amino-functionalized phosphonium ILs ([aP4443][AA]) were characterized systematically. It was obviously shown that [aP4443][AA] have better thermal properties than the imidazolium, pyridinim and ammonium ILs correspondingly. (5) CO2 absorption by [aP4443][Gly] and [aP4443][Ala] was investigated. It was shown that the CO2 absorption supported with SiO2 by [aP4443][Gly] and [aP4443][Ala] can reach the equilibrium within 100 min. The chemical absorption of CO2 by [aP4443][Gly] and [aP4443][Ala] was determined to approach 1 mol CO2/1 mol IL. The CO2 desorption can be completed at 60 ℃ and reduced pressure. [aP4443][Gly] and [aP4443][Ala] can be repeatedly recycled for CO2 uptake with no obviously observed loss of absorption rate and absorption capacity.
语种	中文
公开日期	2013-09-13
页码	159
内容类型	学位论文
源URL	[http://ir.ipe.ac.cn/handle/122111/1185]
专题	过程工程研究所_研究所（批量导入）
推荐引用方式 GB/T 7714	张延强. 咪唑、季鏻类离子液体的合成及应用研究[D]. 过程工程研究所. 中国科学院过程工程研究所. 2008.

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