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Ultrasound-Assisted Catalytic Esterification for Synthesizing 4-Acetylphenyl Benzoate by Dual-Site Phase-Transfer Catalyst in Tri-Liquid Phases
|關鍵字:||Dual-Site phase-Transfer catalyst;雙活性基相間轉移觸媒;tri-liquid phase;sonochemistry;cavitation;benzoylation;third phase;第三液相;超音波化學;空穴效應;酯化反應;第三相狀態||出版社:||化學工程學系所||引用:|| C. M. Starks, C. L. Liotta, M. Halpern, Phase-Transfer Catalysis : Fundamentals(1994)  S. Naik, L. K. Doraiswamy, “Phase Transfer Catalysis:Chemistry and Engineering”, AICHE, 44 (1998) 612-646.  J. Jarrouse, “The Influence of quaternary chloride on the reaction of labike hydrogen compound and chlorine-substituted chlorine derivatives”, CR Heabd. Seances Acad. Scu., C332 (1951) 1424-1434.  C. M. Starks, “Phase Transfer Catalysis. I. Heterogeneous Reactions Involving Anion Transfer by Quaternary Ammonium and Phosphonium salts”, J. Am. Chem. Soc., 93(1) (1971) 195-199.  A. W. Herriott, D. Picker, “Phase transfer catalysis. An evaluation of catalysts”, J. Am. Chem. Soc., 97 (1975) 2345-2349  K. 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在反應機制上，反應區域在第三液相與有機相間的交界面，有機相反應物在界面與觸媒中間體行本質反應，並推得及證實速率表示式可用擬一階線性方程式描述。苯甲酸4-乙醯基苯酯的生成，可在攪拌(250 rpm)與超音波輔助(28 kHz、300 W)下在溫度30℃反應2分鐘可得到97.2%的產率。攪拌速率方面，提高攪拌速率可增加分子之間的碰撞機會，並由實驗中可知在攪拌速率為250rpm時，其質傳阻力對反應速率的影響較小，而能忽略質傳阻力之作用。在超音波方面，超音波在界面產生空穴效應帶來界面混亂的效果，對反應速率常數極為敏感，無超音波振盪時速率常數為0.0013 sec-1，在同樣條件下加入頻率28 kHz、功率為300 W的超音波振盪，使速率常數升為0.0075 sec-1，並藉由改變超音波頻率與功率來討論其變化，頻率越高將使超音波在傳遞時損失的能量越多，使系統獲得的能量越少，反應速率因而降低，故越低的頻率對反應會有越好的效果。
The study is to synthesize dual-site phase-transfer catalyst, and use it to form tri-liquid phases, and investigate the catalytic benzoylation of 4'-hydroxyacetophenone sodium salt and benzoyl chloride to produce 4-acetylphenyl benzoate in ultrasound-assisted tri-liquid-phase system. It includes investigating the changes of the composition and forming condition of the third phase, and the kinetics of synthesizing 4-acetylphenyl benzoate. The dual-site phase-transfer catalyst, 1,4-bis(tributylammoniomethyl)benzene dibromide, was synthesized in toluene solution at 70℃ from p-xylylene dibromide and tributylamine. The operating parameters were amount of catalyst, amounts of aqueous reactant, types of inorganic salt, amounts of sodium chloride, temperature, amounts of water, types and amounts of organic solvent.
The results indicate that the amount of catalyst, aqueous reactant and sodium chloride, different forming temperature, types of organic solvent have important influences to form the third phase. A small amount of catalyst or aqueous reactant added can only lead to a small amount of catalytic intermediate, and precipitate some solids in the third phase. However, too much catalyst and aqueous reactant would produce so much catalytic intermediate, as to be hardly dissolved in the third liquid, and that made the third phase forming some solid particles. The third liquid cannot be formed at 20℃, but the temperature effect is apparent between 20℃ and 30℃. There is a large difference to form the third phase when adding sodium chloride or sodium bromide. The catalyst would form the Br-Q2+ Br- style when sodium bromide was added. It cannot react with aqueous reactant to form catalytic intermediate because of its low solubility in water. n-Henptent and chlorobenzene were also used as the organic solvents. The results show these two solvents cannot dissolve the catalytic intermediate and the system did not form the third liquid.
In the kinetic part, the reactions dominate to conduct in the interface between the organic and the third-liquid phase. The interface reaction machanisu is thus suggested. The rate of apparent reaction can be described by pseudo-frist-order kinetic equation. The yield of the product of 4-acetylphenyl benzoate yield in the organic phase was obtained 97.2 % in 2 min at the reaction condition of temperature at 30 ℃, agitation speed at 150 rpm, ultrasonic frequency and power at 28 kHz and 300 W. Increasing the agitation speed above 250rpm can enhance the molecular to reduce the effect of mass transfer resistance. It is also sensitive on the catalytic reaction by the effect of ultrasonic irradiation.In the same reaction condition, the rate constant increased from 0.0013 sec-1 to 0.0075 sec-1 when the ultrasonic frequency and power at 28 kHz and 300 W were applied. And try to change the ultrasonic frequency to discuss the variation of product yield. When the higher frequency was used, the fewer energy would be got in the reaction system. A more energy was lost in the transport process when a higher ultrasonic frequency was used. So the lower ultrasonic frequency promotes the faster reaction rates.
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