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Synthesis of n-Octyl Salicylate by Ultrasound and Ionic Liquid Assisted Phase Transfer Catalyst in Tri-Liquid System
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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.
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