含離子液體微乳液的構(gòu)筑及其在硒催化領(lǐng)域的應(yīng)用
發(fā)布時間：2018-08-29 11:13
【摘要】：今年距人類發(fā)現(xiàn)硒整整200年,硒原子由于存在空的4d軌道且可以參與成鍵,以及較大的原子半徑,使其參與形成的化學(xué)鍵鍵能較低,從而導(dǎo)致硒化合物具有獨(dú)特的氧化還原性能和抗氧化性能,可作為高效催化劑用于有機(jī)合成。微乳液是指由表面活性劑分子、助表面活性劑、油和水組成的熱力學(xué)穩(wěn)定體系,微乳液可顯著提高互不相溶反應(yīng)物的接觸機(jī)率,從而提高化學(xué)反應(yīng)的速率和轉(zhuǎn)化率。本論文在研究了四甲基丁基酚聚氧乙烯醚非離子表面活性劑與不同分子結(jié)構(gòu)的表面活性離子液體(C8ILs)在水溶液中的膠束化行為的基礎(chǔ)上,進(jìn)一步研究了 Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O體系的相行為和微乳液界面膜特性,最后將該微乳液體系引入到硒催化領(lǐng)域,利用二硒醚作為催化劑,系統(tǒng)研究了微乳液結(jié)構(gòu)和組成對硒催化β-紫羅蘭酮氧化反應(yīng)的影響。本研究不但拓展了離子液體微乳液在催化領(lǐng)域的應(yīng)用范圍,還對硒在分子有序組合體中的應(yīng)用奠定了基礎(chǔ)。主要內(nèi)容包括如下幾方面:一、通過電導(dǎo)率研究了單尾([C8mim]Br)、雙尾([C8C8im]2Br)和Gemini型([C8imC2C8im]Br2)咪唑類表面活性離子液體(C8ILs)與Triton X-114復(fù)配體系的臨界膠束濃度、相互作用參數(shù)、膠束形成自由能。通過熒光和1H MNR等實(shí)驗(yàn)技術(shù)表征了不同結(jié)構(gòu)C8ILs在復(fù)合膠束中的定位,還測定了各組成膠束的粒徑和Zeta電位。研究結(jié)果表明:C8ILs對混合膠束的穩(wěn)定性的影響以及C8ILs與Triton X-114之間的相互作用強(qiáng)度均按[C8C8im]Br[C8imC2C8im]Br2[C8mim]Br 變化。二、研究了 Triton X-114/C8ILs/n-C4H9OH/n-C7H16/H2O體系的相行為,通過電導(dǎo)和流變法考察了微乳液由油包水(W/O)到雙連續(xù)(Bicontinuous)再到水包油(O/W)的相轉(zhuǎn)變過程。研究結(jié)果表明,C8ILs的加入抑制了助表面活性劑n-C4H9OH由油相進(jìn)入微乳液的油水界面,而此效應(yīng)如[C8mim]Br[C8imC2C8im]Br2[C8C8im]2Br 變化。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響應(yīng)的基礎(chǔ)上,將(C8H17Se)2 引入到 Triton X-114(或 TritonX-100)/C8ILs/n-C4H9OH/n-C7H16/H2O 微乳液體系中,考察不同微乳液體系對硒催化β-紫羅蘭酮Baeyer-Villiger氧化反應(yīng)效率的影響。研究結(jié)果顯示,氧化反應(yīng)發(fā)生在微乳液的界面膜相中,而最佳的微乳液反應(yīng)體系是相對粘度較低的具有雙連續(xù)結(jié)構(gòu)的微乳液,其中,當(dāng)加入[C8imC2C8im]Br2和[C8C8im]2Br時,產(chǎn)率高達(dá)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%.
【學(xué)位授予單位】：揚(yáng)州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O648.23;O643.3
本文編號：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%.
【學(xué)位授予單位】：揚(yáng)州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O648.23;O643.3
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相關(guān)期刊論文 前2條
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