本文選題：聚合型離子液體 + 自由基聚合�。� 參考：《南京理工大學(xué)》2017年碩士論文

【摘要】：針對(duì)傳統(tǒng)溫控兩相體系催化劑回收過(guò)程中存在流失量大、易失活的缺點(diǎn),本文利用溫控兩相離子液體的自分離特性及聚合物大分子在反應(yīng)體系中性能穩(wěn)定、不易流失的優(yōu)點(diǎn),以聚乙二醇為主鏈,雙鍵取代咪唑型離子液體為交聯(lián)劑,采用自由基聚合方法,設(shè)計(jì)合成出具有溫控兩相性能的聚合型離子液體(PIL)。同時(shí),利用該聚離子液體協(xié)同納米金制備聚合型離子液體-納米金(PIL@-Au)催化劑。具體研究?jī)?nèi)容如下:研究了PIL在水與常用有機(jī)溶劑中的溶解性能,PIL能與甲苯構(gòu)成的"高溫均相、低溫分相"的PIL/甲苯溫控兩相體系,該溫控體系具有良好的溫控性能,PIL在甲苯中的臨界溶解溫度(CST)為60℃,滿足常見(jiàn)有機(jī)反應(yīng)所需溫度要求。研究了PIL/甲苯溫控兩相體系酸催化苯胺與苯甲醛的胺醛縮合反應(yīng),采用單因素法探討了反應(yīng)過(guò)程中PIL添加量、反應(yīng)物配料比、反應(yīng)時(shí)間、反應(yīng)溫度等因素對(duì)反應(yīng)結(jié)果的影響。最佳反應(yīng)條件:PIL添加量1 g,配料比1:1.2(苯甲醛10 mmol,苯胺12 mmol),溶劑甲苯4 mL,100℃下反應(yīng)2 h,此時(shí),產(chǎn)物N-亞芐基苯胺的收率達(dá)到最大,為93.4%。底物拓展試驗(yàn)中進(jìn)一步考察了不同取代基對(duì)反應(yīng)結(jié)果的影響,產(chǎn)物收率57.2%～82.9%,表明該溫控體系對(duì)胺醛縮合反應(yīng)具有廣泛的適用性。研究了PIL@-Au/甲苯溫控兩相體系催化苯乙烯環(huán)氧化反應(yīng),采用單因素法探討了反應(yīng)過(guò)程中催化劑用量、反應(yīng)時(shí)間、反應(yīng)溫度、引發(fā)劑用量、溶劑用量等因素對(duì)反應(yīng)物的轉(zhuǎn)化率和產(chǎn)物的選擇性影響。最佳反應(yīng)條件:PL@-Au添加量80mg,0.624 g苯乙烯,反應(yīng)溫度110℃,5 mL甲苯溶液,8%TBHP引發(fā)劑(與苯乙烯的摩爾比),O2流速25 mL·min-1,此時(shí),苯乙烯的轉(zhuǎn)化率為97.8%,環(huán)氧苯乙烷的選擇性為81.9%。分別研究了最佳反應(yīng)條件下溫控體系中催化劑PIL和PIL@-Au的分離及循環(huán)使用過(guò)程,均顯示出較高的催化活性、較好的催化穩(wěn)定性和較低的損失率。聚合離子液體酸催化應(yīng)用及聚合離子液體協(xié)同金屬及金屬化合物催化劑催化應(yīng)用對(duì)聚離子液體的發(fā)展和催化劑循環(huán)利用起到重要的應(yīng)用價(jià)值。
[Abstract]:In view of the disadvantages of large loss and inactivation in the recovery process of the traditional temperature controlled two phase catalyst system, this paper uses the self separation characteristics of the temperature controlled two-phase ionic liquid and the stability of the polymer macromolecules in the reaction system, and is not easy to lose. The polymeric ionic liquid (PIL) with temperature controlled two phase properties was designed and synthesized by free radical polymerization. At the same time, the polymerization type ionic liquid nano gold (PIL@-Au) catalyst was prepared by using the polyionic liquid to coordinate the nanoscale gold. The specific content of the study was as follows: the solubility of PIL in water and common organic solvents, PIL and toluene composition were studied. The temperature control system of PIL/ toluene temperature controlled two phase system has good temperature control system. The temperature control system has good temperature control performance. The critical dissolution temperature (CST) of PIL in toluene is 60 C, which meets the requirement of temperature for common organic reactions. The condensation reaction between aniline and benzaldehyde in PIL/ toluene temperature controlled two phase system is studied, and the single factor is used. The effect of PIL addition, reactant proportioning, reaction time and reaction temperature on the reaction results was discussed. The optimum reaction conditions were as follows: PIL added 1 g, the proportioning ratio 1:1.2 (benzaldehyde 10 mmol, aniline 12 mmol), solvent toluene 4 mL, and 2 h at 100 C, at this time, the yield of N- benzyl aniline reached the maximum, 93.4%.. It was 93.4%.. In the substrate expansion test, the effect of different substituents on the reaction results was further investigated. The yield of the product was 57.2% ~ 82.9%, indicating that the temperature control system has a wide applicability to the condensation reaction of amino aldehyde. The epoxidation of styrene in PIL@-Au/ toluene temperature controlled two phase system was studied. The single factor method was used to discuss the catalyst in the reaction process. Quantity, reaction time, reaction temperature, dosage of initiator, solvent amount and other factors on the conversion of the reactant and the selectivity of the product. The best reaction conditions: PL@-Au addition 80mg, 0.624 g styrene, reaction temperature 110, 5 mL toluene solution, 8%TBHP initiator (the molar ratio of phenyl ethylene), O2 flow rate 25 mL. Min-1, at this time, the transformation of styrene The rate is 97.8%. The selectivity of epoxy benzyl ethane is 81.9%.. The separation and recycling process of PIL and PIL@-Au in the temperature control system under the optimum reaction conditions are studied respectively. It shows high catalytic activity, better catalytic stability and lower loss rate. The catalytic applications of metal compound catalysts play an important role in the development of polyionic liquids and the recycling of catalysts.
【學(xué)位授予單位】：南京理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O643.36

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