臺灣博碩士論文加值系統

本研究主要探討液-液相系統之 4-羥基苯甲酸鈉與溴庚烷在相間轉移觸媒催化下，合成 4-羥基苯甲酸庚酯之取代反應。在反應系統中，除兩相反應物外，各項影響產率及反應速率的變因探討包括：攪拌效應、超音波、溫度、觸媒種類及觸媒添加量、有機溶劑種類、離子液體及離子液體添加量，並進一步探討反應機制及求得反應動力學常數。

以對-羥基苯甲酸鈉與溴庚烷進行酯化反應合成對-羥基苯甲酸正（Aliquat 336）庚酯，主要反應會在有機相中進行，以氯化甲基三辛基銨有最佳的產率，由於 Aliquat 336 為油溶性物質，故有機相溶劑可不用選擇極性強但具有毒性的甲基異丁酮（MIBK），選用正庚烷即可；反應初期由於觸媒溶解度關係，反應會有一誘導期，添加離子液體可克服此問題，進而縮短反應時間。反應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，實驗結果經 Arrhenius 方程式計算可得活化能為 Ea= 6.19 kcal/mol 。

實驗結果顯示，以 Aliquat 336 為觸媒，反應 3 小時後產率可達54%，且反應溫度只有 60℃，並使用非毒性有機溶劑，改善了以往用強酸強鹼觸媒，及使用有毒性之有機溶劑，甚至需要高溫下才可進行反應的系統，可降低生產成本極後續不必要的危害。

The study aimed at synthesizing n-heptyl 4-hydroxybenzoate by using 4-hydroxybenzoic acid sodium salt and 1-bromoheptane under the catalysis of phase transfer catalyst in liquid-liquid system. In addition to reactants, the operating parameters in the reaction system include agitation rate, ultrasonic effect, reaction temperature, type and amount of catalyst, type of solvent, type and amount of ionic liquid. The reaction mechanism and kinetics of reaction were obtained from experimental results.

The esterification reaction Between 1-bromoheptane and 4-hydroxybenzoic acid sodium salt occurs in organic phase, and using Aliquat 336 can reach the highest yield among all catalysts employed in this study. Because Aliquat 336 is oil-soluble, n-heptane could be selected without using high polar and toxic organic solvent, methly isobutyl ketone (MIBK). In general, there is an induction period in the beginning of reaction due to the catalyst solubility. Ionic liquid can be added to overcome this problem and reduce the reaction time. The experimental result shows that activation energy Ea= 6.19 kcal/mol by Arrhenius equation. Adding more organic phase reactant can further improve the reaction rate.

The result shows that after reacting 3 hours, the yield is 54% by using Aliquat 336, and the reaction temperature is only 60℃, the non-toxic organic solvents can be used. Instead of using strong acid and alkali as catalyst and toxic organic solvents. The system that needs high reaction temperature also can be improved. By doing so, we can reduce the production cost and danger as well.

致謝.......................I
摘要 .......................II
Abstract .......................III
目錄 .......................IV
圖目錄 .......................VII
表目錄 .......................IX
符號說明.......................X
第一章 緒論.......................1
1.1 前言.......................1
1.2 相間轉移觸媒之簡介.......................3
1.2.1 相間轉移觸媒的分類.......................5
1.2.2 相間轉移觸媒的型態.......................9
1.3 液-液相催化反應文獻回顧 .......................14
1.4 離子液體的簡介 .......................15
1.4.1 離子液體的簡介 .......................15
1.4.3 離子液體的特性.......................17
1.4.4 離子液體在催化應用中的技術問題 .......................18
1.5 酯化反應.......................19
1.5.1 一般酯類合成方法 .......................19
1.5.2 相間轉移觸媒催化反應合成酯類 .......................21
1.6 超音波原理及應用 .......................22
1.6.1 超音波化學原理 .......................23
1.6.2 超音波在相間轉移觸媒催化之應用 .......................24
1.7 研究目的與方法 .......................25
1.7.1 研究目的 .......................25
1.7.2 研究方法 .......................26
第二章 實驗設備與實驗方法 .......................28
2.1 實驗藥品 .......................28
2.2 實驗設備與分析儀器 .......................30
2.3 產物之合成 .......................33
2.4 校正曲線.......................34
2.5 反應動力學實驗步驟 .......................37
第三章 合成對-羥基苯甲酸正庚酯之酯化反應 .......................38
3.1 前言 .......................38
3.2 反應機構與動力學模式推導 .......................38
3.2.1 反應機構.......................38
3.2.2 反應動力模式推導 .......................43
3.3 再現性測試 .......................48
3.4 觸媒種類對催化反應影響 .......................49
3.5 觸媒添加量對催化反應影響 .......................51
3.6 不同溶劑系統對催化反應影響 .......................53
3.7 不同攪拌速率對催化反應影響 .......................57
3.8 超音波對催化反應影響 .......................62
3.8.1 不同超音波頻率對催化反應的影響 .......................62
3.8.2 不同超音波功率對催化反應的影響 .......................64
3.9 超音波與攪拌效應的交叉比較 .......................68
3.10 不同離子液體種類對催化反應的影響 .......................70
3.10.1 離子液體種類對催化系統的影響 .......................70
3.10.2 離子液體添加量對催化系統的影響 ..................74
3.11 離子液體與觸媒的交叉比較 .......................79
3.12 不同溫度對催化系統的影響 .......................81
3.12.1 溫度對催化反應的影響 .......................81
3.12.2 視活化能計算 .......................85
第四章 總結.......................87
參考文獻 .......................91
附錄.......................95

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