Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3135
標題: 超音波及離子液體輔助相間轉移觸媒於三液相系統合成鄰-羥基苯甲酸正辛酯之研究
Synthesis of n-Octyl Salicylate by Ultrasound and Ionic Liquid Assisted Phase Transfer Catalyst in Tri-Liquid System
作者: 楊峻瑋
Yang, Chun-Wei
關鍵字: 相間轉移觸媒
Phase-transfer catalyst
超音波
三液相
動力學
離子液體
鄰-羥基苯甲酸正辛酯
Ultrasound
Tri-liquid phase
Kinetics
Ionic liquid
N-Octyl salicylate
出版社: 化學工程學系所
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摘要: 本研究探討超音波與離子液體輔助相間轉移觸媒於三液相系統中催化鄰-羥基苯甲酸鈉與溴辛烷合成鄰-羥基苯甲酸正辛酯之酯化反應。研究內容包含探討超音波、溫度、觸媒種類、觸媒添加量、離子液體、鹽類的添加及攪拌速率對三液相之催化酯化反應的影響,其中比較單活性基及雙活性基相間轉移觸媒對本系統的催化效果,雙活性基觸媒是以二溴對二甲苯及三己胺反應合成雙活性基相間轉移觸媒溴化1,4-二(三己基銨基甲基)苯(BTHAMBB, QBr2)。 第三液相的形成變數探討包含觸媒添加量、鹽類添加量、有機溶劑種類、水量、水相反應物添加量,離子液體效應和溫度效應。從實驗結果可得到,當觸媒量、鹽類量、水相反應物添加量增加時,反應系統之第三液相體積及第三液相中觸媒中間體含量都會增加,在最佳化的條件下可以得到第三液相體積為2.1毫升,而使用溶劑為甲基異丁酮時,則無第三液相產生,因為甲基異丁酮為高極性溶劑,所以可以溶解第三液相,而觸媒中間體99%集中於有機相,而加入離子液體,因離子液體有高溶解範圍的特性,會使得觸媒中間體能夠被離子液體攜入有機相,有利於加速反應速率,升高溫度可以增加分子動能,使得觸媒中間體轉化率達到99%以上,第三液相中之觸媒中間體的量在70℃時可以達到接近觸媒總量的93%。 從反應機制來觀察,反應主要位於第三液相,有機相反應物與觸媒中間體在第三液相中進行本質反應,當加入離子液體時,則會同時於第三液相及有機相中產生反應。而加入超音波輔助催化,在同樣反應時間的情況下,可以提升反應產率4%~20%,所合成之雙活性基觸媒溴化1,4-二(三己基銨基甲基)苯於本系統在相同反應時間可得到與使用商用單活性基觸媒相近的催化效果,而雙活性基觸媒使用量僅為商用單活性基觸媒的1/10,且不需加入鹽類即可形成第三液相。加入鏻類離子液體(phosphonium-based ionic liquid)對本系統的催化有非常大的助益。在不添加離子液體及觸媒時產率為0%;而添加觸媒不加離子液體,反應5小時後產率僅有43.5%;添加觸媒及離子液體在相同反應時間產率可達99.5%;反應結果可用虛擬一階反應動力式來描述,以對環境溫和的正庚烷為溶劑,實驗結果可用動力學方程式-ln(1-Y) =kappt表示,式中 為視反應速率常數。經Arrhenius方程式計算可得活化能為20.14 kcal/mol。
In this study, the esterification of sodium salicylate and octyl bromide to synthesize n-octyl salicylate by ultrasound and ionic liquid promoted phase-transfer catalyst in tri-liquid system was investigated. The explored operating parameters included ultrasound, temperature, types of catalyst, addition catalyst and ionic liquid, addition of salt, agitation speed, etc..The novel dual-site phase transfer catalyst, 1,4’-bis(trihexyl ammoniomethyl) benzene dibromide (BTHAMBB, QBr2), was synthesized from P-xylene dibromide and trihexylamine in acetonitrile at 70˚C. Comparison of commercial catalysts with dual-site phase transfer catalyst in catalytic activity was performed.   The operating parameters of forming the third-liquid phase included the amounts of catalyst, addition of salt , organic solvent, the amount of aqueous reactant and water, ionic liquid and temperature effect. The results indicated that the volume of third-liquid phase and amount of Ph(OH)COOQ would be raised by the increasement of the amount of catalyst, aqueous reactant and salt. Under the optimum condition, the system would separate out 2.1ml of third-liquid phase. While using MIBK as an organic solvent, the third-liquid phase disappeared because with its highly chemical polarity, it will dissolve third-liquid phase and take Ph(OH)COOQ away form the third-liquid phase, thus, there are nearly 99% be concentrated in the organic phase. With the addition of ionic liquid, because of its highly solubility it can bring Ph(OH)COOQ to the organic phase, it’s beneficial to accelerate the rate of reaction. The molecular kinect energy will be raised when the temperature increase, the conversion of Ph(OH)COOQ can reach 99% and above. The amount of Ph(OH)COOQ in third-liquid phase comes to 93% of overall amount of catalyst while the temperature gets to 70℃.   In the kinetic part, the reactions dominate to conduct in the tri-phase; while adding ionic liquid in the reaction, the reactions occured in the tri – phase and organic phase simultaneously. The esterification was promoted to an increase of 4% to 20% in product yield under ultrasound irradiation. In the same reaction time, the dual-site phase transfer catalyst BTHAMBB resulted in an equivalent product yield when compared with commercial catalysts, merely with one tenth usage of BTHAMBB to the commercial catalyst Furthermore, the third-liquid phase was formed from BTHAMBB without adding any extra salt. Using ionic liquid would be beneficial to the present esterification, especially phosphonium-based ionic liquid. The product yield is 0% without adding both ionic liquid and catalyst. The yield goes to 43.5% while adding catalyst but without ionic liquid; marvelously, the yield is as high as 99.5% when using both ionic liquid and catalyst. Pesudo-first-order kinetic equation was applied to correlate experimental results. Using n-heptane as environmently friendly solvent, the kinetic results were correlated by using -ln(1-Y) =kappt equation successfully, where was the apparent reaction rate constant, and the apparent activation energy was 20.14 kcal/mol with high efficiency.
URI: http://hdl.handle.net/11455/3135
其他識別: U0005-3006201316363600
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