臺灣博碩士論文加值系統

本研究探討相間轉移觸媒在固-液相系統中催化4-胺基苯甲酸鈉與溴丁烷合成4-胺基苯甲酸丁酯；操作變因包括觸媒種類與添加量、離子液體種類與添加量、攪拌速率、水添加量、KOH添加量、溶劑種類、有機相反應物添加量、鹽類添加、溫度，並探討這些變因對催化反應的影響。

　　實驗結果顯示，以溴化四丁基銨觸媒的催化效果最好，這是因為其具有在鹼性環境下穩定性較高的特點；在不添加觸媒及離子液體的情況下幾乎無產物生成，而添加0.3毫莫耳的觸媒及離子液體在反應30分鐘後產率達到94.79%。攪拌速率300rpm時產率達到最大值，再往上提升則因溶液噴濺至瓶壁上而下降。添加少量的水可形成Omega相有效提升產率，添加2.5毫升水時的產率為無水情況下的6.08倍，繼續添加水至15毫升時則因系統轉為液-液相而使產率下降。添加KOH有助於觸媒中間體的生成，在添加27毫莫耳KOH時的產率為無KOH情況下的2.97倍；使用高極性的甲基異丁基酮較低極性的甲苯有較佳的催化效果，顯示溶劑的極性高低亦是影響催化反應進行的因素之一。本實驗以固相反應物為限量試劑，添加過量有機相反應物可使其在有機相的濃度提高，添加過量8倍的溴丁烷時擁有最高效率的催化效果。

　　反應機制上，觸媒中間體與有機相反應物主要於中間相與有機相交界處發生本質反應，其實驗結果可用虛擬一階線性方程式-ln(1-Y)=kappt表示，式中kapp為視反應速率常數，經Arrhenius方程式計算可得本反應之活化能為11.79 kcal/mol。

　　The thesis was to investgate esterification of 4-amino benzoic acid sodium salt (Ph(NH2)COONa) and 1-bromobutane(RBr) to synthesize 4-minobenzoic acid butyl ester by phase transfer catalyst and ionic liquid in solid-liquid System. The operating parameters included type of catalyst, amount of catalyst, type of ionic liquid, amount of ionic liquid, agitation speed, amount of water, amount of KOH, type of organic solvent, amount of organic reactants, salts effect, and temperature.

　　The results indicated tetrabutylammonium bromide(TBAB) had best catalytic effect, because it is with more stable characteristics in alkaline. The reaction can not be conducted without adding any catalysts and ionic liquid, when adding 0.3 mmol catalysts and ionic liquid the yield increases to 94.79%. When the agitation speed was 300rpm, the yield had a maximum, more than 300rpm due to the solution splashed on the sidewall. Adding a little water can compose omega phase to improve the yield. When adding 2.5 ml of water the yield was 6.08 times to that in anhydrous condition, adding water to 15 ml the yield declined due to system becoming liquid-liquid type. When 0.27 mmol of KOH was used, the yield was 2.97 times that without KOH. When using highly polar solvent such as methyl isobutyl keton (MIBK), there would be the best catalytic effect than toluene, which indicated that the level of solvent effect is one of factors in the catalytic reaction. In this experiment, using (Ph(NH2)COONa) as limiting reagent, excess organic reactants could enhance the concentration in organic phase, adding excess 1-bromobutane up to 8 times would have the highest yield.

　　In the kinetic part, catalytic intermediate and organic reactants reaction dominated to conduct in the interface between the organic and middle phase. The kinetic results were correlated by us -ln(1-Y)=kappt equation successfully, where kapp was the apparent reaction rate constant, and the activation energy was 11.79 kcal/mol.

誌謝 I
摘要 II
Abstract III
目錄 V
圖目錄 VIII
表目錄 X
符號說明 XI
第一章、 緒論 1
一、前言 1
二、相間轉移觸媒簡介 2
(一)相間轉移觸媒的種類 3
(二)相間轉移觸媒的反應型態 6
三、離子液體的簡介 12
(一)離子液體的特性 12
(二)離子液體的發展與回顧 13
四、固-液相相間轉移催化系統 14
(一)固-液相相間轉移催化反應的發展與回顧 14
(二)固-液相相間轉移催化系統的反應模型 16
(三)固-液相相間轉移催化的反應原理 19
五、酯化反應 23
(一)一般酯類的合成方法 23
(二)相間轉移催化反應合成酯類 25
六、研究目的與方法 27
第二章、實驗藥品、設備與方法 29
一、實驗藥品 29
二、實驗設備 31
三、產物合成方法 32
四、校正曲線 34
五、觸媒正電荷離子(Q+)含量滴定方法 37
六、觸媒中間體合成方法 37
七、觸媒中間體定量方法 39
八、反應動力學實驗步驟 39
第三章、以相間轉移觸媒搭配離子液體在固-液相系統合成4-胺基苯甲酸酯 40
一、前言 40
二、反應機構與動力學模式推導 40
(一)反應機構 40
(二)動力學模式推導 41
三、反應機制驗證 44
四、再現性驗證 45
五、不同觸媒對催化反應的影響 47
六、觸媒添加量對催化反應的影響 50
七、不同離子液體對催化反應的影響 54
八、離子液體添加量對催化反應的影響 58
九、觸媒與離子液體對催化反應的交互影響 61
十、攪拌速率對催化反應的影響 65
十一、水添加量對催化反應的影響 69
十二、KOH添加量對催化反應的影響 74
十三、不同溶劑對催化反應的影響 79
十四、有機相反應物添加量對催化反應的影響 82
十五、鹽類添加對催化反應的影響 86
十六、溫度對催化反應的影響 90
(一)溫度對催化反應的影響 90
(二)視活化能計算 95
十七、結論 96
第四章、總結 100
參考文獻 104
附錄 109

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