臺灣博碩士論文加值系統

本研究主要探討液-液相系統之鄰-羥基苯甲酸鈉與溴庚烷在相間轉移觸媒催化下，合成鄰-羥基苯甲酸正庚酯之取代反應。研究內容包含探討攪拌速率、超音波、溫度、觸媒種類、觸媒添加量、有機溶劑種類、離子液體、離子液體添加量。並進一步探討反應機制及反應動力學。
以鄰-羥基苯甲酸鈉與溴庚烷進行酯化反應合成鄰-羥基苯甲酸正庚酯，主要反應會在有機相中進行，以氯化甲基三辛基銨（Aliquat 336）有最佳的產率。由於Aliquat 336為油溶性物質，當使用高極性甲基異丁基酮（MIBK）會有最佳催化效果，使用低極性或無極性的溶劑如甲苯與正庚烷時反應性會較低，考量綠色反應需求，因此有機相溶劑可不用選擇極性強但具有毒性的甲基異丁基酮（MIBK），選用甲苯即可。
在液-液相系統中，利用氯化甲基三辛基銨較長團基親油的特性，可將水相反應物由水相質傳至油相。氯化甲基三辛基銨便可催化鄰-羥基苯甲酸鈉與溴庚烷進行酯化反應。實驗結果顯示反應速率隨著觸媒量的增加及溫度增加而增加。在有機溶劑效應方面，反應過程中，於具極性溶劑中反應3小時產率達74.37%；相反的，於低極性溶劑中反應3小時後產率不達50%以上。
在不添加離子液體及觸媒時產率為0%；而添加觸媒不加離子液體，反應3小時後產率74.37%；添加觸媒及離子液體在相同反應時間產率可達77.88%。加入超音波與攪拌輔助催化，在同樣反應時間的情況下，比沒有加超音波的產率相比較，可以提升反應產率18%。而超音波及攪拌速率同時輔助能達到最好的催化效果。反應結果可用虛擬一階反應動力式來描述，以甲苯為溶劑，實驗結果可用動力學方程式-ln(1-Y) = kapp t表示，式中kapp為視反應速率常數。經Arrhenius方程式計算可得有超音波的活化能為18.31 kcal/mol。

The study aimed at synthesizing n-heptyl o-hydroxybenzoate by using o-hydroxybenzoic acid sodium salt and 1-bromoheptane under the catalysis of phase transfer catalyst in liquid-liquid system. The operating parameters included 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 o-hydroxybenzoic acid sodium salt occurs in organic phase, and Aliquat 336 can be used to reach the highest yield among all catalysts employed in this study. Using low-polar or non-polar solvents such as toluene and heptane the yield would be lowered and indicated the influence of the level of solvent polarity on the rate. Due to the concern of green reaction, toluene was selected as the solvent, without using high polar and toxic organic solvent, methly isobutyl ketone (MIBK).
In this liquid-liquid phase transfer system, the aqueous-phase reactant can be transported from aqueous-phase to organic-phase by the hydrophobic characters of catalytic Aliquat336, which thus can catalyze esterification of sodium benzoate and benzyl bromide.
The experimental results showed that the more the mounts of catalyst, the faster the synthesizing reaction rate would be. Effects of different organic solvents and ionic liquids for Aliquat336 were carried out, and above 74% yield of benzyl benzoate is easily achieved within 3 hours.
At 3 hours, the product yield was 0% without adding both ionic liquid and catalyst.The yield was 74.37% by adding catalyst but without ionic liquid; adding both catalyst and ionic liquid would promote yield to 77.88%. Both ultrasound and stirring assisting liquid -liquid phase-transfer catalysis could be effectively applied in synthesizing ether-ester. Pesudo-first-order kinetic equation was applied to correlate experimental results. Using toluene as solvent, the kinetic results were correlated by using -ln(1-Y)=kappt equation successfully , where kapp was the apparent reaction rate constant, with ultrasound, the apparent activation energy was 18.31 kcal/mol.

目錄
摘要 I
Abstract III
致謝 V
目錄 VI
圖目錄 IX
表目錄 XI
符號說明 XII
第一章　緒論 1
1.1前言 1
1.2相間轉移觸媒之簡介 2
1.2.1相間轉移觸媒的分類 3
1.2.2相間轉移觸媒的型態 8
1.3液-液相催化反應文獻回顧 13
1.4離子液體 14
1.4.1離子液體的簡介 14
1.4.2離子液體的特性 15
1.4.3離子液體的種類 16
1.5酯化反應 18
1.5.1一般酯類合成方法 18
1.5.2相間轉移觸媒催化反應合成酯類 20
1.6超音波原理與應用 22
1.6.1 超音波化學原理 22
1.6.2 超音波在相間轉移催化之應用 24
1.7研究目的與方法 24
1.7.1 研究目的 24
1.7.2 研究方法 25
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 35
2.5反應動力學實驗步驟 37
第三章 合成鄰-烴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 39
3.3再現性測試 44
3.4不同觸媒種類對催化反應影響 45
3.5觸媒添加量對催化反應影響 48
3.6不同溶劑系統對催化反應影響 51
3.7不同攪拌速率對催化反應影響 55
3.8超音波效應對催化反應影響 59
3.8.1不同超音波頻率對催化反應的影響 59
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影響 70
3.10.1離子液體種類對催化反應的影響 70
3.10.2離子液體添加量對催化反應的影響 75
3.11離子液體與觸媒的交叉比較 79
3.12不同溫度對催化反應影響 81
3.12.1溫度對催化反應的影響 81
3.12.2視活化能計算 86
3.13本章節結論 88
第四章 總結與未來方向 92
參考文獻 95
附錄 101


圖目錄
圖1 1液-液相離子對萃取機制反應機構圖 2
圖1 2對掌性相間轉移觸媒 5
圖1 3各種多活性基相間轉移觸媒 7
圖1 4相間轉移觸媒催化反應之分類 8
圖1 5咪唑類離子液體 17
圖1 6?啶類離子液體 17
圖1 7季銨類離子液體 17
圖1 8季鏻類離子液體 18
圖1 9空穴效應示意圖 23
圖1 10實驗規劃圖 27
圖2 1超音波批式反應實驗裝置圖 32
圖2 2超音波振盪槽之發振示意圖 32
圖2 3鄰-羥基苯甲酸正庚酯（n-Heptyl o-hydroxybenzoate）對內標物（Diphenyl methane）之校正曲線 36
圖 3 1液-液相相間轉移觸媒催化反應機制圖 39
圖 3 2再現性測試，產率對時間作圖 44
圖 3 3不同觸媒種類，產率對時間作圖 46
圖 3 4不同觸媒種類，-ln(1-Y)對時間作圖 47
圖 3 5不同觸媒添加量，產率對時間作圖 49
圖 3 6不同觸媒添加量，-ln(1-Y)對時間作圖 50
圖 3 7不同有機溶劑，產率對時間作圖 53
圖 3 8不同有機溶劑，-ln(1-Y)對時間作圖 54
圖 3 9不同攪拌速率，產率對時間作圖 57
圖 3 10不同攪拌速率，-ln(1-Y)對時間作圖 58
圖 3 11不同超音波頻率，產率對時間作圖 61
圖 3 12不同超音波頻率，-ln(1-Y)對時間作圖 62
圖 3 13不同超音波功率，產率對時間作圖 65
圖 3 14不同超音波功率，-ln(1-Y)對時間作圖 66
圖 3 15超音波與攪拌交叉比較，產率對時間作圖 69
圖 3 16不同離子液體添加，產率對時間作圖 73
圖 3 17不同離子液體添加，-ln(1-Y)對時間作圖 74
圖 3 18不同離子液體添加量，產率對時間作圖 77
圖 3 19不同離子液體添加量，-ln(1-Y)對時間作圖 78
圖 3 20離子液體與觸媒交叉比較，產率對時間作圖 80
圖 3 22不同溫度，產率對時間作圖 83
圖 3 23不同溫度，-ln(1-Y)對時間作圖 84
圖 3 24不同溫度， kapp×100對時間作圖 85
圖 3 25由Arrhenius’s方程式，-lnkapp 對103/T作圖 87


表目錄
表 2 1合成鄰-羥基苯甲酸正庚酯之NMR圖譜其氫理論原子個數與 實際個數之比較 34
表 3 1 kapp視反應速率常數與溶劑種類之關係 52
表 3 2 kapp視反應速率常數與攪拌速率之關係 56
表 3 3 kapp視反應速率常數與超音波頻率之關係 63
表 3 4 kapp視反應速率常數與超音波功率之關係 67
表 3 5 kapp視反應速率常數與離子液體添加量之關係 76
表 3 6 kapp視反應速率常數與不同溫度之關係 82

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