含离子液体微乳液的构筑及其在硒催化领域的应用
发布时间：2018-08-29 11:13
【摘要】：今年距人类发现硒整整200年,硒原子由于存在空的4d轨道且可以参与成键,以及较大的原子半径,使其参与形成的化学键键能较低,从而导致硒化合物具有独特的氧化还原性能和抗氧化性能,可作为高效催化剂用于有机合成。微乳液是指由表面活性剂分子、助表面活性剂、油和水组成的热力学稳定体系,微乳液可显著提高互不相溶反应物的接触机率,从而提高化学反应的速率和转化率。本论文在研究了四甲基丁基酚聚氧乙烯醚非离子表面活性剂与不同分子结构的表面活性离子液体(C8ILs)在水溶液中的胶束化行为的基础上,进一步研究了 Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O体系的相行为和微乳液界面膜特性,最后将该微乳液体系引入到硒催化领域,利用二硒醚作为催化剂,系统研究了微乳液结构和组成对硒催化β-紫罗兰酮氧化反应的影响。本研究不但拓展了离子液体微乳液在催化领域的应用范围,还对硒在分子有序组合体中的应用奠定了基础。主要内容包括如下几方面:一、通过电导率研究了单尾([C8mim]Br)、双尾([C8C8im]2Br)和Gemini型([C8imC2C8im]Br2)咪唑类表面活性离子液体(C8ILs)与Triton X-114复配体系的临界胶束浓度、相互作用参数、胶束形成自由能。通过荧光和1H MNR等实验技术表征了不同结构C8ILs在复合胶束中的定位,还测定了各组成胶束的粒径和Zeta电位。研究结果表明:C8ILs对混合胶束的稳定性的影响以及C8ILs与Triton X-114之间的相互作用强度均按[C8C8im]Br[C8imC2C8im]Br2[C8mim]Br 变化。二、研究了 Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O体系的相行为,通过电导和流变法考察了微乳液由油包水(W/O)到双连续(Bicontinuous)再到水包油(O/W)的相转变过程。研究结果表明,C8ILs的加入抑制了助表面活性剂n-C4H9OH由油相进入微乳液的油水界面,而此效应如[C8mim]Br[C8imC2C8im]Br2[C8C8im]2Br 变化。三、合成了二辛基二硒醚(C8H17Se)2,在考察(C8H17Se)2在水溶液中的氧化刺激响应的基础上,将(C8H17Se)2 引入到 Triton X-114(或 TritonX-100)/C8ILs/n-C4H9OH/n-C7H16/H2O 微乳液体系中,考察不同微乳液体系对硒催化β-紫罗兰酮Baeyer-Villiger氧化反应效率的影响。研究结果显示,氧化反应发生在微乳液的界面膜相中,而最佳的微乳液反应体系是相对粘度较低的具有双连续结构的微乳液,其中,当加入[C8imC2C8im]Br2和[C8C8im]2Br时,产率高达92%。
[Abstract]:This year, exactly 200 years after the discovery of selenium, the energy of chemical bonds formed by selenium atoms is lower due to the existence of an empty 4d orbital and the ability to participate in bonding, as well as a larger atomic radius. As a result, selenium compounds have unique redox and oxidation resistance, which can be used as high efficient catalysts for organic synthesis. Microemulsion is a thermodynamically stable system composed of surfactant molecules, cosurfactants, oil and water. Microemulsion can significantly increase the contact probability of non-miscible reactants and thus increase the rate and conversion of chemical reactions. In this paper, the micellization behavior of tetramethyl Ding Ji polyoxyethylene ether Nonionic surfactants and surface active ionic liquids (C8ILs) with different molecular structures in aqueous solution was studied. The phase behavior and interfacial film characteristics of Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O system were further studied. Finally, the microemulsion system was introduced into the field of selenium catalysis, and diselenide was used as catalyst. The effect of structure and composition of microemulsion on the oxidation of 尾-ionone catalyzed by selenium was studied systematically. This study not only expands the application scope of ionic liquid microemulsion in the field of catalysis, but also lays a foundation for the application of selenium in molecular ordered combinations. The main contents are as follows: firstly, the critical micelle concentration, interaction parameters and free energy of micelle formation of [C8mim] Br), double tail ([C8C8im] 2Br) and Gemini ([C8imC2C8im] Br2) imidazole surface-active ionic liquids (C8ILs) with Triton X-114 are studied by electrical conductivity. The localization of C8ILs with different structures in the composite micelles was characterized by fluorescence and 1H MNR techniques. The particle size and Zeta potential of the micelles were also measured. The results show that the effect of C8C8im C8ILs on the stability of mixed micelles and the intensity of interaction between C8ILs and Triton X-114 vary according to [C8C8im] Br [C8imC2C8im] Br2 [C8mim] Br. Secondly, the phase behavior of Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O system was studied. The phase transition process of microemulsion from water in oil (W / O) to double continuous (Bicontinuous) to oil in water (O / W) was investigated by conductance and rheology. The results show that the addition of C8ILs inhibits the entry of cosurfactant n-C4H9OH from the oil phase into the oil-water interface of the microemulsion, and this effect is such as the change of [C8mim] Br [C8imC2C8im] Br2 [C8C8im] 2Br. Third, dioctyl diselenide (C8H17Se) 2 was synthesized. On the basis of investigating the oxidative stimulation response of (C8H17Se) 2 in aqueous solution, (C8H17Se) 2 was introduced into the Triton X-114 (or TritonX-100) / C 8ils / n-C 4H 9OH / n-C 7H 16H 2O microemulsion system. The effect of different microemulsion systems on the oxidation efficiency of 尾 -ionone Baeyer-Villiger catalyzed by selenium was investigated. The results show that the oxidation reaction takes place in the interfacial film phase of the microemulsion, and the optimum microemulsion reaction system is the microemulsion with low relative viscosity with double continuous structure. When [C8imC2C8im] Br2 and [C8C8im] 2Br are added, the yield is as high as 92%.
【学位授予单位】：扬州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O648.23;O643.3
本文编号：2211033
[Abstract]:This year, exactly 200 years after the discovery of selenium, the energy of chemical bonds formed by selenium atoms is lower due to the existence of an empty 4d orbital and the ability to participate in bonding, as well as a larger atomic radius. As a result, selenium compounds have unique redox and oxidation resistance, which can be used as high efficient catalysts for organic synthesis. Microemulsion is a thermodynamically stable system composed of surfactant molecules, cosurfactants, oil and water. Microemulsion can significantly increase the contact probability of non-miscible reactants and thus increase the rate and conversion of chemical reactions. In this paper, the micellization behavior of tetramethyl Ding Ji polyoxyethylene ether Nonionic surfactants and surface active ionic liquids (C8ILs) with different molecular structures in aqueous solution was studied. The phase behavior and interfacial film characteristics of Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O system were further studied. Finally, the microemulsion system was introduced into the field of selenium catalysis, and diselenide was used as catalyst. The effect of structure and composition of microemulsion on the oxidation of 尾-ionone catalyzed by selenium was studied systematically. This study not only expands the application scope of ionic liquid microemulsion in the field of catalysis, but also lays a foundation for the application of selenium in molecular ordered combinations. The main contents are as follows: firstly, the critical micelle concentration, interaction parameters and free energy of micelle formation of [C8mim] Br), double tail ([C8C8im] 2Br) and Gemini ([C8imC2C8im] Br2) imidazole surface-active ionic liquids (C8ILs) with Triton X-114 are studied by electrical conductivity. The localization of C8ILs with different structures in the composite micelles was characterized by fluorescence and 1H MNR techniques. The particle size and Zeta potential of the micelles were also measured. The results show that the effect of C8C8im C8ILs on the stability of mixed micelles and the intensity of interaction between C8ILs and Triton X-114 vary according to [C8C8im] Br [C8imC2C8im] Br2 [C8mim] Br. Secondly, the phase behavior of Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O system was studied. The phase transition process of microemulsion from water in oil (W / O) to double continuous (Bicontinuous) to oil in water (O / W) was investigated by conductance and rheology. The results show that the addition of C8ILs inhibits the entry of cosurfactant n-C4H9OH from the oil phase into the oil-water interface of the microemulsion, and this effect is such as the change of [C8mim] Br [C8imC2C8im] Br2 [C8C8im] 2Br. Third, dioctyl diselenide (C8H17Se) 2 was synthesized. On the basis of investigating the oxidative stimulation response of (C8H17Se) 2 in aqueous solution, (C8H17Se) 2 was introduced into the Triton X-114 (or TritonX-100) / C 8ils / n-C 4H 9OH / n-C 7H 16H 2O microemulsion system. The effect of different microemulsion systems on the oxidation efficiency of 尾 -ionone Baeyer-Villiger catalyzed by selenium was investigated. The results show that the oxidation reaction takes place in the interfacial film phase of the microemulsion, and the optimum microemulsion reaction system is the microemulsion with low relative viscosity with double continuous structure. When [C8imC2C8im] Br2 and [C8C8im] 2Br are added, the yield is as high as 92%.
【学位授予单位】：扬州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O648.23;O643.3
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相关期刊论文 前2条
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2 彭春玉;周海晖;曾伟;焦树强;罗胜联;旷亚非;;影响反相微乳液导电性能的因素[J];物理化学学报;2006年04期
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