Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3797
標題: 超音波輔助雙活性基相間轉移觸媒在三液相合成對-甲氧基苯基乙酸丁酯之研究
Synthesis of 4-Methoxyphenylacetic Acid Butyl Ester by Ultrasound-Assisted Dual-Site Phase Transfer Catalyst in Tri-Liquid Phases
作者: 陳盈君
Chen, Ying-Chun
關鍵字: Dual-site phase-transfer catalyst;雙活性基相間轉移觸媒;Third-liquid phase;Sonochemistry;Ether-esters;第三液相;超音波化學;醚酯類
出版社: 化學工程學系所
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摘要: 
本研究探討超音波輔助雙活性基相間轉移觸媒在第三液相中催化對-甲氧基苯基乙酸鉀與溴丁烷合成對-甲氧基苯基乙酸丁酯之酯化反應。雙活性基相間轉移觸媒是以二溴對二甲苯與三丁胺反應,並以乙腈為溶劑在溫度70˚C下反應生成溴化1,4-二(三丁基銨甲基)苯 (QBr2)。應用此觸媒在本系統中探討內容包括第三液相的形成條件與組成的改變及合成對-甲氧基苯基乙酸丁酯的反應動力探討。

形成第三液相的探討,操作變數包括觸媒添加量、鹽類種類、氯化鈉添加量、溶劑種類、水量及溶劑添加量及溫度。實驗結果顯示在水相反應物與觸媒莫耳數比值為2:1時所形成的第三液相觸媒中間體含量較高,過量添加觸媒或水相反應物對第三液相中觸媒中間體含量的提升沒有太大的影響;系統中若含有過量的溴離子則容易使第三相變為固體且大多以QBr2的形態存在,用氯化鈉作為鹽類添加劑可避免第三相形成固體,在氯化鈉添加量為0.05莫耳時第三液相觸媒中間體含量最高;而選用極性高的溶劑甲基異丁酮或極性低的溶劑甲苯皆能形成第三液相,但是使用甲苯時有機相中不含有Q2+離子,而使用甲基異丁酮時有機相則含有Q2+離子存在;溫度效應在本系統中對第三液相的組成有明顯差異,在溫度為70˚C時無論使用甲苯或甲基異丁酮為溶劑,第三液相中觸媒中間體的含量較低溫時高;水的添加量僅在使用9~13毫升時能形成第三液相,而甲基異丁酮的添加因為其具有極性而會影響第三液相的組成,不添加有機溶劑時則無法使系統形成第三液相。

在反應機制上,觸媒中間體與有機相反應物所進行的本質反應發生在第三液相與有機相的界面處。反應過程中隨著產物對-甲氧基苯基乙酸丁酯的生成,則同時有副產物溴化鉀鹽類的生成會影響第三相的形態,使第三相成為固體而使反應速率減慢,其實驗結果可用動力學方程式 (t > 0)表示之,式子中 為初始反應速率常數, 為衰退常數。實驗於不添加觸媒的雙液相系統中則沒有產物的生成;在相同條件下以超音波28 kHz/300 W及攪拌速率200 rpm輔助下,在液-液相系統中反應4小時僅能達到39.3%的產率,而若添加0.05莫耳的氯化鈉使系統形成第三液相則可使產率提升至94.2%。系統中以水相反應物為限量試劑,過量添加有機相反應物可使反應速率提升,添加過量15倍的溴丁烷時系統達最高產率。反應過程中以超音波28 kHz/300 W輔助,以100 rpm攪拌即能使系統克服質傳阻力;超音波及攪拌同時輔助才能使系統達到催化的效果。

The study is to use potassium 4-methoxyphenylacetate (ArCOOK) and 1-bromobutane to synthesize of 4-methoxyphenylacetic acid butyl ester by ultrasound-assisted dual-site phase transfer catalyst in tri-liquid phases. In the present study, dual-site phase transfer catalyst, 1,4-bis(tributylammoniomethyl)benzene dibromide (BTBAMBB, QBr2), was synthesized from p-xylylene and butylamine in acetonitrile at 70˚C. Investigations included conditions of forming and changes of composition in the third-liquid phase and kinetics of synthesizing 4-methoxyphenyl acetic acid butyl ester.

The operating parameters of forming the third-liquid phase included quantities of catalyst, types of inorganic salt, amounts of sodium chloride, types of solvent, quantities of water and organic solvent, and temperature effect. The results indicated that the third-liquid phase had higher quantity of catalytic intermediate under the molar ratio of ArCOOK to BTBAMBB being 2:1. An excess of catalyst couldn't enhance the quantities of catalytic intermediate in third-liquid phase. The solution containing the same bromide ion could result in the common-ion effect, which made tri-phase become solid and exist a large amount of catalyst. Using NaCl could avoid the common-ion effect. Moreover, the addition of 0.05 mol of NaCl had the highest catalytic intermediate in the third-liquid phase. Both of high polarity solvent, MIBK, and low polarity solvent, toluene, were use to form the third-liquid phase. However, Q2+ was distributed in the MIBK phase but no catalyst was observed in the toluene phase. In this system, temperature was an significant effect, no matter which solvent was selected. It had high quantity of catalytic intermediate at 70˚C better than at low temperature, 50˚C. Only addition of 9 ml to 13ml of water could form the third-liquid phase. Because of solvent's polarity, quantities of MIBK affected the composition in the third-liquid phase.

In the kinetic part, the reactions dominate to conduct in the interface between the organic and third-liquid phase. During the progress of the reaction, the product KBr was in situ increased to change the environment of reaction. Parts of the third-liquid phase were gradually transformed into the solid type to reduce the overall reaction rate. The kinetic results were correlated by using (t > 0) equation successfully, where is the initial reaction rate constant and is deactivation constant. Without adding catalyst in liquid-liquid system, the reaction rate was very small and neglected. Liquid-liquid system and tri-liquid system were compared for the same reaction conditions, but with extra addition of 0.05 mol of NaCl for tri-liquid system. Under ultrasound irradiation at 28 kHz/300W and stirring at 200 rpm, the product yields in 4 h of reaction were 39.3% for liquid-liquid system and 94.2% for tri-liquid system. In the experiment, using ArCOOK as the limiting reagent could enhance the reaction rate, adding 0.045 mol of 1-bromobutane had the highest product yield. Under ultrasound irradiation at 28 kHz/300Wand stirring at 100 rpm, mass transfer resistances had not a significant effect on the reaction rate. Both ultrasound and stirring assisted third-liquid phase-transfer catalysis can be effectively applied in synthesizing ether-esters.
URI: http://hdl.handle.net/11455/3797
其他識別: U0005-0607201006454900
Appears in Collections:化學工程學系所

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