Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3555
標題: 應用相間轉移觸媒催化丁二酸鈉之苯甲基化反應研究
Catalytic Benzylation of Succinic Acid Disodium Salt by Phase-transfer catalysis
作者: 楊育睿
Yang, Yu-Jui
關鍵字: Phase-transfer catalyst
相間轉移觸媒
kinetics
liquid-liquid phase
solid-liquid phase
dibenzyl succinate
動力學
液-液相
固-液相
丁二酸二苯甲酯
出版社: 化學工程學系所
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摘要: 本研究在以相間轉移觸媒在液-液相及固-液相反應系統中進行催化短鏈二羧酸鹽類(丁二酸鈉)之苯甲基化反應來合成丁二酸二苯甲酯,在液-液相系統中以親油性觸媒溴化苯甲基三丁基銨(BTBAB)來合成觸媒活性中間體丁二酸化苯甲基三丁基銨(R(OOQ)2),分析其在有機相隨反應時間之變化,探討其反應機構與動力學。並利用甲基三辛基銨(Aliquat 336)觸媒進行固-液及液-液相之反應,探討兩種不同相間轉移催化反應之差異。 在以BTBAB為主的液-液相相間反應系統中,反應速率會隨著水相反應物和觸媒的添加量增多而增快,觸媒中間體之量也隨之而增加並以二階動力式來描述之。在轉速方面,在此系統中,轉速超過300 rpm,反應速率則不受界面質傳阻力之影響,產率可達80%以上,在無攪拌時,反應3小時其產率可到8.6%左右,顯示此苯甲基化反應可在液-液界面進行。而在有機溶劑方面,以高極性的甲基異丁基酮優於正庚烷,在觸媒活性方面,其結果是溴化四丁基鏻=溴化苯甲基三丁基銨>溴化四丁基銨>Aliquat 336。 在以Aliquat 336為觸媒的固-液相及液-液相反應系統中,反應速率兩系統皆只隨著水相反應物和觸媒量的添加量增加而微增快,轉速方面,兩系統也在轉速超過200 rpm,便可克服質傳阻力,在有機溶劑方面,固液相反應中,以甲基異丁基酮優於正庚烷,但在液-液相方面,反而是庚烷優於甲基異丁基酮。而添加水量中,固-液相反應添加少量的水無助於形成omega相,在液-液相方面,水量越多,界面越多,反應越好。在固-液相的觸媒活性方面,其結果是Aliquat 336>溴化四丁基銨>溴化四丁基鏻>溴化苯甲基三丁基銨,並以虛擬一階動力式描述之。
The present syudy is to investigate the catalytic benzylation of succinic acid disodium salt by phase-transfer catalysis in liquid-liquid and solid-liquid system. In liquid-liquid system, we chose benzyltributylammonium bromide (BTBAB) to be the major catalyst. The experimental results show that the more the amounts of catalyst or aqueous reactant, the faster the reaction rate will be. When the agitation speed exceeds 300 rpm, the mass transfer resistance at the liquid-liquid interface can be neglected and the yield of product can reach to 80%. But without any agitation, the yield of product only can reach to 8.6%.Using MIBK as the solvent is better than using Heptane. Different phase-transfer catalysts were employed to compare their catalytic efficiency, and the reactivity order was found: tetrabutylphosphonium bromide ≈ benzyltributylammonium bromide > tetrabutylammonium bromide >Aliquat 336. The kinetics of second-order reaction can be applied to describe the overall reaction rate successfully. In comparing phase-transfer catalysis in solid-liquid and liquid-liquid systems, we chose Aliquat 336 to be the major catalyst. The experimental results show that both in solid-liquid system and liquid-liquid system, the more the amounts of catalyst or aqueous reactant, the faster the reaction rate will be. When the agitation speed exceeds 200 rpm, the mass transfer resistance at the interface can be neglected. Using MIBK as the solvent is better than using Heptane in solid-liquid system, but worse in liquid-liquid system. In solid-liquid system, adding some water can not produce the omega-phase to improve the reaction. In liquid-liquid system, adding more water makes more interfacial area than to have better reaction. Different phase-transfer catalysts in solid-liquid system were employed to compare their catalytic efficiency, and the reactiveity order was found: Aliquat 336> tetrabutylammonium bromide > tetrabutylphosphonium bromide > benzyltributylammonium bromide. The kinetics of pseudo-first-order reaction can be applied to describe the overall reaction rate successfully.
URI: http://hdl.handle.net/11455/3555
其他識別: U0005-0607200615162100
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-0607200615162100
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