功能化吡啶类离子液体的设计合成、性质及其应用研究

发布时间：2018-03-23 10:17

本文选题：离子液体功能化　切入点：设计合成　出处：《西安工程大学》2015年硕士论文

【摘要】：功能化离子液体是完全由阴阳离子组成的,在阴阳离子中引入一个或多个官能团,使得其具有某种功能或特性的盐类化合物。这种特定的分子结构使得功能化离子液体具有特定功能、宽液态范围、宽电化学窗口等独特性质,其应用领域涉及新型导电功能材料、有机合成、分离纯化及生物催化等诸多领域。然而,离子液体分子的结构解析、结构与性质之间的构效关系等研究相对滞后,新型功能化离子液体的设计合成及选择性应用存在较大的难度。本论文首先从分子结构设计的角度出发,以吡啶、二乙烯吡啶、卤代酯、卤代酸和卤代烷烃为反应物,设计合成了多种吡啶类功能化离子液体,即含酯基的吡啶类功能化离子液体、含羧基的吡啶类功能化离子液体、聚吡啶类功能化离子液体单体及其聚合物,并系统研究了反应温度、反应配比、反应时间对吡啶类功能化离子液体合成过程的影响,确定其适宜反应条件。其次,通过傅里叶红外光谱技术以及核磁共振光谱技术等分析了功能化吡啶类离子液体的结构,并用单晶X射线衍射技术,对[MEPy][PF6]的大单晶体结构进行解析,该化合物的空间群为P2(1)/n,晶型属于单斜晶系,晶胞参数为a=14.30(2)nm,b=8.281(14)nm,c=29.48(5)nm,β=95.06o,Z=4,V=3.477(2)nm3,Dc=1.641 Mg/m3,μ=0.308 mm-1,F(000)=1676。进一步对功能化吡啶类离子液体的导电性分析表明,含酯基和含羧基的功能化离子液体的电导率相对较大,聚离子液体的电导率相对较小,与单体相比较其电导率相差1个数量级,且电导率导电行为符合Arrhenius方程。同时对其溶解性和热稳定性的研究表明,其极性接近于醇、酮,其中含酯基的吡啶类功能化离子液体的热稳定性相对较好。最后,将吡啶类功能化离子液体引入苯乙烯悬浮聚合体系成功制备了聚苯乙烯微球。研究表明,在体系中引入含酯基的离子液体时,所制备的聚苯乙烯微球粒径分布较为均匀,微球平均粒径最小。同时,吡啶类功能化离子液体在聚苯乙烯微球的成球过程中具有降低体系表面能,减弱微球间的团聚等多重作用。通过对吡啶类离子液体的功能化研究,设计合成了含酯基的吡啶类功能化离子液体、含羧基的吡啶类功能化离子液体、聚吡啶类功能化离子液体单体及其聚合物,并将其首次引入苯乙烯聚合体系中制备了多孔结构的聚合物微球,这将为多孔聚合物材料的制备提供一种新的思路。
[Abstract]:Functionalized ionic liquids are composed entirely of anions, in which one or more functional groups are introduced. A salt compound that has certain functions or properties. This particular molecular structure gives functionalized ionic liquids unique properties such as specific functions, wide liquid ranges, wide electrochemical windows, etc. Its applications include novel conductive functional materials, organic synthesis, separation and purification, biocatalysis and so on. However, the studies of structure resolution and structure-activity relationship between structure and properties of ionic liquids are relatively lagging behind. The design, synthesis and selective application of new functionalized ionic liquids are difficult. In this paper, pyridine, divinylpyridine, halogenated esters, halogenated acids and halogenated hydrocarbons are used as reactants from the point of view of molecular structure design. Several kinds of pyridine functionalized ionic liquids were designed and synthesized, including ester containing pyridine functionalized ionic liquids, carboxyl pyridine functional ionic liquids, polypyridine functionalized ionic liquids and their polymers. The effects of reaction temperature, reaction ratio and reaction time on the synthesis of pyridine functionalized ionic liquids were studied systematically. The structure of functionalized pyridine ionic liquids was analyzed by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR). The large single crystal structure of [MEPy] [PF6] was analyzed by single crystal X-ray diffraction technique. The space group of the compound is P2N / 1 / n, and the crystal form belongs to monoclinic system. The cell parameters of the compound are as follows: a ~ (14.30) m ~ (-1) ~ (2) ~ (-) ~ (-) ~ (8) nmb ~ (1) C ~ (29) 485nm ~ (m), 尾 _ (95.06oC) ~ (3.4772nm) ~ (1.641)% Mgm ~ (3), 渭 ~ (0.308) m ~ (-1) ~ (-1) F ~ (000N) ~ (-1), and the conductivity of functionalized ionic liquids containing ester and carboxyl group is relatively large, the results show that the conductivity of functionalized ionic liquids containing ester and carboxyl group is relatively large. The results show that the ionic conductivity of functionalized ionic liquids containing ester group and carboxyl group is relatively large. The conductivity of polyionic liquids is relatively small, and the conductivity of polyionic liquids is 1 order of magnitude lower than that of monomers. The conductivity of polyionic liquids conforms to the Arrhenius equation. The solubility and thermal stability of polyionic liquids are similar to those of alcohols and ketones. The thermal stability of pyridine functionalized ionic liquids containing ester group was relatively good. Finally, polystyrene microspheres were successfully prepared by introducing pyridine functionalized ionic liquids into styrene suspension polymerization system. When the ester containing ionic liquid was introduced into the system, the particle size distribution of the prepared polystyrene microspheres was more uniform, and the average diameter of the microspheres was the smallest. Pyridine functionalized ionic liquids can reduce the surface energy of polystyrene microspheres, weaken the agglomeration of microspheres, etc. The functionalization of pyridine ionic liquids is studied. The functional ionic liquids containing ester group pyridine group, pyridine functional ionic liquid containing carboxyl group, polypyridine functional ionic liquid monomer and its polymer were designed and synthesized. The polymer microspheres with porous structure were prepared by introducing them into styrene polymerization system for the first time, which will provide a new way of thinking for the preparation of porous polymer materials.
【学位授予单位】：西安工程大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O645.1

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