Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3923
標題: 超音波輔助相間轉移觸媒在含離子液體的三液相下合成鄰-羥基苯甲酸丁酯之研究
Synthesis of o-Hydroxybenzoic Acid Butyl Ester by Ultrasound-Assisted Phase Transfer Catalysis in Tri-Liquid System with Ionic Liquid
作者: 洪瑜鴻
Hung, Yu-Hung
關鍵字: Dual-site phase-transfer catalyst
雙活性基相間轉移觸媒
Third-liquid phase
Ionic liquid
Cavitation
Sonochemistry
第三液相
離子液體
空穴效應
酯化反應
超音波化學
出版社: 化學工程學系所
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摘要: 本研究探討以超音波輔助雙活性基相間轉移觸媒在含離子液體的三液相下催化鄰-羥基苯甲酸鈉與溴丁烷合成鄰-羥基苯甲酸丁酯之酯化反應。雙活性基相間轉移觸媒是由二溴對二甲苯及三己胺以乙腈為溶劑在70 oC下反應生成溴化1,4-二(三己基銨基甲基)苯(BTHAMBB)。 研究內容包含探討以雙活性基相間轉移觸媒(BTHAMBB)形成的第三液相以及催化合成鄰-羥基苯甲酸丁酯的酯化反應動力學探討。 第三液相形成的變數探討包含在有無超音波輔助反應進行下,雙活性基相間轉移觸媒添加量、有機溶劑種類、不同反應溫度、離子液體添加量。本系統中,第三液相的形成不需另外添加鹽類於水中,在操作條件為鄰-羥基苯甲酸鈉3毫莫耳,溴化1,4-二(三己基銨基甲基)苯0.375毫莫耳,去離子水 10毫升,正庚烷10毫升,攪拌速率 250 rpm,溫度70 oC的條件下,反應20分鐘即可形成體積1 cm3的第三液相。因為觸媒中間體的結構所致,其對水相及有機相的溶解度皆低,因此微量的觸媒即會與水相反應物形成觸媒中間體和第三液相,當觸媒添加量為0.375毫莫耳時,觸媒中間體與觸媒陽離子的比例最高,當觸媒添加量過多時,觸媒會集中於第三液相,降低觸媒中間體在第三液相的濃度,影響到反應速率的快慢。使用低極性的甲苯或是非極性的正庚烷皆能形成第三液相。而使用高極性的甲基異丁基酮(MIBK)時,則無法形成第三液相,這是因為觸媒與觸媒中間體皆會溶於甲基異丁基酮中,導致第三液相無法形成。 在反應機制上,反應區域主要是位於第三液相,有機相反應物與觸媒中間體在第三液相中進行本質反應,其反應速率表示式可用擬一階方程式描述。在超音波功率300 W,超音波頻率28 kHz,攪拌速率250 rpm,溫度70 oC反應四小時可得產率69.7%,如果沒有添加觸媒則產率為0 %。如果又額外添加離子液體,產率會提升至94.1%,有明顯的增加。超音波輔助催化方面,有使用超音波進行反應的系統,產率約會增加4%~12%。並且有超音波輔助反應的視反應速率常數會比無超音波輔助反應時高,由此可見超音波輔助有相當的助益。
In this study, o-hydroxybenzoic acid butyl ester was synthesized from the reaction of sodium salicylate and 1-bromobutane via a dual-site phase-transfer catalyst, 1,4-bis(trihexylammoniomethyl)benzenedibromide(BTHAMBB), under ultrasound irradiation in a tri-liquid batch system with ionic liquid. The catalyst BTHAMBB was synthesized from the reaction of p-xylylene dibromide and excess trihexylamine in acetonitrile at 70 oC. In this study, the investigation included the forming condition of the tri-liquid phase by BTHAMBB and kinetics of synthesizing sodium salicylate. The operating parameters of forming the third-liquid phase including the type of organic solvent, the amounts of ionic liquid and catalyst, the reaction temperature, and the ultrasound. In the conditions of 3mmol of sodium salicylate, 0.375 mmol of BTHAMBB, 10 ml of de-ionized water, 10 ml of heptane, temperature at 70 oC and stirring speed at 250 rpm, the volume 1 cm3 of the third-liquid phase was formed after 20 minutes of reaction without adding any extra inorganic salts in the reaction system. It is because the structure of the catalytic intermediate that made the third-liquid phase having low solubility in both water and heptane. The catalytic intermediate had the highest ratio in the third-liquid phase when the amount of BTHAMBB is 0.375 mmol. An excess addition of BTHAMBB might transfer more catalyst into the third-liquid phase and reduced the effective concentration of the catalytic intermediate for reaction. In this study, the third-liquid phase could be formed by using toluene or heptane as organic solvent. But the high-polarity solvent of methyl isobutyl ketone (MIBK) can not be used to form the third-liquid phase, because the catalyst and the catalytic intermediate can be dissolved by methyl isobutyl ketone. In the kinetic part, the result indicated the reactions dominate to conduct in the third-liquid phase. The rate of apparent reaction could be described by pseudo-first-order kinetic equation. The yield of the product of o-hydroxybenzoic acid butyl ester in the organic phase was obtained 69.7% by using BTHAMBB as phase-transfer catalyst in 4 hours in the condition of temperature at 70 oC, agitation speeg at 250 rpm, ultrasonic frequency and power at 28 kHz and 300 W, while the yield of the product was 0 % at the same condition without using BTHAMBB as phase-transfer catalyst. The yield of the product will raise to 94.1% by adding the ionic liquid to the reaction system. By using ultrasonic irradiation, the yield of the product will increase 4%~12%, and the kapp will be higher than without ultrasonic.
URI: http://hdl.handle.net/11455/3923
其他識別: U0005-2506201210241800
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-2506201210241800
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