【作者】 翟永爱；

【导师】 高歌；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2009， 博士

【摘要】 本论文主要分为两部分的工作,一方面是制备功能性的离子液体,另一方面是将离子液体应用于纳米材料的制备当中。具体包括以下几个方面:1.设计并合成了在烷基咪唑类阳离子、吗啡啉类阳离子、氰乙基咪唑类阳离子和吡咯烷酮类阳离子的侧链上分别引入含烯丙基、羟乙基、乙酸基、乙酸乙酯基等官能团的功能化离子液体,以期得到具有新功能、低粘度、低成本的新型室温离子液体。并以新型的双功能型离子液体:1-烯丙基-3-氰乙基咪唑氯盐([ACNEIm]Cl)为研究对象,研究了其水溶液的过量性质。2.使用1-丁基-3-甲基咪唑六氟磷酸盐([BMIm]PF6)离子液体作为反应介质,制备了无需高温锻烧就含有锐钛相的纳米TiO2,并对其光催化降解性能进行了研究;进而在一种含羧基功能化的离子液体:1-乙酸基-3-甲基咪唑氯盐([AcMIm]Cl)中,低温水解制备了具有纳米结构的金红石型二氧化钛,并对其光催化降解性能进行了研究。3.以一种含丙烯酸阴离子的N-甲基咪唑丙烯酸盐(MImAA)离子液体为稳定剂,利用简便的方法制备了稳定的四氧化三铁(Fe3O4)纳米粒子的水溶液分散体。接着以这种磁性水溶液分散体为核,进行纳米包覆材料的研究,其目地在于方便地实现二氧化钛在光催化降解有机污染物时的磁性分离回收。4.将[BMIm]PF6与传统的阴离子型表面活性剂十二烷基硫酸钠(SDS)复配成离子液体微乳液,引入到乳液聚合体系中制备聚苯乙烯纳米粒子。更多还原

【Abstract】 Ionic liquids (ILs) comprised entirely of cations and anions are liquids at room temperature, which also called low-melting salts. They are deserved for research as new types of media or“soft”functional materials, which have shown special physical and chemical properties compared with other solid or liquid materials. Due to their designable, ionic liquids are“task-specific”or“tailor-making”materials by tuning the combination between anions and cations or grafting proper functional groups. They have shown promising applications in separation and purification, reclaiming nuclear scraps, preparing special optics materials. It is one of the researching emphases in synthesis of new types and given functions of ionic liquids through molecular designing according to the special requirements.We have prepared functional ionic liquids by introducing several functional groups including allylic, ethyl-hydroxide, acetic acid, ethyl acetate into the cations of N-methylimidazole, N-methylmorpholine, N-cyanoethylimidazole, N-methyl-2-pyrrolidinonium, respectively. There are seven new types of ionic liquids which haven’t been reported before, that is, 1-allyl-3-cyanoethylimidazole, N’-allyl-N-methyl-2-pyrrolidinonium, 1-2-ethylhydroxide-3-cyanoethylimidazole, N’-acetic acid-N-methylmopholine, 1-acetic acid-3-cyanoethylimidazole, N’-ethyl acetate-N-methylmorpholine, 1-ethyl acetate-3-cyanoethylimidazole. We have studied their prepared methods and characterized them by IR, 1H NMR and mass spectra (MS). Furthermore, we have tested their solubility with some solvents.The thermodynamic properties of mixtures for ionic liquid with solvents were indispensable basic data for their industrialization process. In this paper, we have studied densities and viscosities for the binary mixtures of 1-allyl-3-cyanoethylimidazolium chloride ([ACNEIm]Cl) with water from 298.15 K to 323.15 K, including their excess properties.There are many prepared methods for nanomaterials, for example, template, microemulsion, precipitation, hydrothermal or solvent-thermal, and microwave methods et al. However, some of these methods need to use volatile organic solvent or rigorous reaction conditions, which might pollute environment or increase production cost. Ionic liquids as environment-friendly green solvents have many kinds and high thermostability, which can dissolve many inorganics and organics. Therefore, they might be used to prepare nanomaterials as reaction media instead of volatile organic solvents. Searching application of ionic liquids in preparing nanomaterials will favor to develop green preparation methods which have simple technics and friendly to environment.In this work, nanostructured TiO2 particles have been synthesized at low temperature using 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), a water immiscible room temperature ionic liquid, as an effective reaction medium by sol-gel method. The as-prepared TiO2 particles present anatase crystal morphology and have favorable photocatalytic performance even without being calcined at high temperature.In general, rutile titania is always prepared by phase transformation of TiO2 from anatase at several hundred high temperatures, which often results in particle agglomeration and grain growth. Therefore, developing a method to prepare nanorutile structure TiO2 at low temperature is of significance. In this work, we have reported a hydrolysis method at low temperature to prepare rutile titania in a carboxyl-containing ionic liquid, 1-methylimidazolium-3-acetate chlorine ([AcMIm]Cl). This method avoided high temperature and high pressure. The as-prepared rutile TiO2 also shows photocatalytic performance in the degradation of methyl orange. The template-directing performance of ionic liquid is due to the bidentate chelating complexation between the carboxylic functional group of ionic liquid and titania.Magnetic nanoparticles as a new type of materials have been extensively studied in many fields. Magnetic attractive forces combined with inherently large surface energies favor nanoparticle aggregation in magnetic dispersions. In this work, we have reported a simple method to prepare stable water-soluble iron oxide dispersions by using an ionic liquid containing acrylic acid anion, viz., N-methylimidazolium acrylic acid (MImAA) as stabilizer. The size of the as-prepared magnetite nanoparticles could be tuned from 12 nm to 20 nm depending on the concentration of MImAA in the medium. The ionic liquid can efficiently prevent interparticle aggregation and tune the particle growth.Following above work, we tried to use the prepared magnetite nanoparticle dispersion without adding other surfactants as core material for coating with silica from the hydrolyzation of tetraethyl orthosilicate (TEOS). The resulting Fe3O4/SiO2 nanocomposite has core-shell structure and the thickness of silica shell could be tuned simply by varying the concentration of TEOS precursor. The Fe3O4/SiO2/TiO2 nanocomposite have been prepared by coating Fe3O4/SiO2 with titania for its easy to magnetic separation in photocatalytic degradation of organic pollution. It has shown that its photocatalytic performance was higher than Fe3O4/TiO2 and still maintained 72 % when it was used repeating for three times.In recent years, it was increasing regards to prepare many novel microemulsions containing ionic liquid instead of water or traditional organic solvent. The influence of ionic liquids to the traditional surfactants was also arousing the chemists’attention. It was found that ionic liquids can tune critical micelle concentration (CMC) of surfactants and the amount of micellar aggregates. The hydrophilic ionic liquids can increase the CMC of surfactant and the hydrophobic ILs can decrease the CMC. Sodium dodecyl sulfate (SDS) as a traditional anionic surfactant is extensively used. It will not only pay attention to the basic chemistry but also bring larger impacts to the industry when SDS is combined with ionic liquids, and finally this will bring potential values in applications.In this work, an ionic liquid microemulsion have been prepared by combining [BMIm]PF6 with SDS, and polystyrene (PS) nanospheres have been prepared by introducing this microemulsion into traditional emulsion polymerization. As a result, we have obtained well dispersing and steady PS nanospheres with size around 70 nm.In summary, we have prepared a series of functional ionic liquids and characterized their structure including their solubility with solvents. Then we have used some ionic liquids in preparing nanomaterials. As a result, nanostructured anatase and rutile titania, stable water-soluble magnetite nanopaticels dispersions, and polystyrene nanosphere were obtained. In addition, the obtained magnetite dispersion as core materials in preparing inorganic nanocomposites also has been studied.更多还原