臺灣博碩士論文加值系統

本研究探討雙活性基相間轉移觸媒與離子液體在多相系統中催化鄰-羥基苯甲酸鈉與溴化苯甲基之鄰-羥基苯甲酸苯甲酯之酯化反應。雙活性基相間轉移觸媒是以4,4’-二(氯甲基)-1,1’-聯苯與三丙胺反應生成氯化4,4’-二(三丙基銨基甲基)-1,1’-聯苯(BTPAMBC, QCl2)。

　　第三液相的形成變數探討包含觸媒添加量，水相反應物種類、水相反應物添加量、鹽類種類及添加量、有溶劑種類、水量和溫度。實驗結果顯示在水相反應物與觸媒莫耳數比值為4:1時所形成的第三液相中擁有較高的觸媒Q2+濃度；系統中若含有過量的溴離子則容易使第三液相為固體，用氯化鈉為添加鹽類則可避免第三液相為固體，在氯化鈉添加量為0.05莫耳時，第三液相觸媒Q2+濃度最高；選用極性高的甲基異丁酮及低極性的甲苯為溶劑皆能形成第三液相，其體積為0.8 cm3，但是使用甲基異丁酮有機相中會溶有部份的觸媒Q2+，而使用非極性的正庚烷第三液相體積為1 cm3，且其中的觸媒Q2+最多；溫度效應在本系統中對第三液相的組成有明顯的差異，當溫度為30°C時，第三液相體積為0.8 cm3，觸媒中間體濃度為0.426 mmol；當溫度升高至60°C時，第三液相體積為1 cm3，觸媒中間體濃度為0.648 mmol。

　　在反應機制上，反應區域主要位於第三液相，有機相反應物與觸媒中間體在第三液相中進行本質反應。所合成之雙活性基觸媒(BTPAMBC)較一般商用觸媒有較佳的催化效率，加入不同結構之離子液體對本系統的催化效果有顯著的增進。若都不添加離子液體及觸媒反應30分鐘產率僅有0.21%；僅添加觸媒而不加離子液體，反應30分鐘後產率僅有51.55%；加觸媒及離子液體在相同反應時間產率可達96.88%。攪拌速率250、350 rpm時，反應30分鐘產率已經十分接近，表示系統已克服質傳阻力造成產率的變化不大。以正庚烷為溶劑時，其實驗結果可用動力學方程式-ln(1-Y) =kappt表示，式中 為視反應速率常數。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18.78 kcal/mol。

The present study was to investgate esterification of sodium salicylate (Ph(OH)COONa) and benzyl bromide (RBr) to synthesize benzyl salicylate by dual-site phase transfer catalyst and ionic liquid in tri-liquid system. The novel dual-site phase transfer catalyst, 4,4’-bis tri(proplyammoniomethyl)-
1,1’-biphenyl dichloride (BTPAMBC, QCl2) was synthesized from the reaction of 4,4’-bis(chloromethyl)-1,1’-bisphenyl and tripropylamine.
　　The operating parameters of forming the third-liquid phase included the amounts of catalyst,salt and water, types of reactant, organic solvent and salt,and temperature.The results indicated that the third-liquid phase had higher quantity Q2+ under the molar ratio of Ph(OH)COONa to BTPAMBC being 4:1.The solution containing the same bromide ion could result in the common-ion effect, which made third liquid phase become solid.
　　Using NaCl could avoid the common-ion effect, and the tri-phase had highest Q2+ when adding 0.05 mole of NaCl. Both high polarity solvent,MIBK, and low polarity solvent, toluene, were used to form the third liquid phase, and the volumn were 0.8 cm3. However, Q2+ was distributed in MIBK phase but no Q2+ observed in the toluene phase. Using n-heptane as the solvent, the volumn of tri-phase was 1cm3 and had most Q2+ in tri-phase. In the system, the temperature effect influenced the amount of catalytic intermediate and composition of third liquid phase, the amount of catalytic intermediate,0.426 mmol, at 30°C, 0.648 mmol, at 60°C; the volume of third liquid phase,0.8 cm3, at 30°C, 1 cm3, at 60°C.
　　In the kinetic part, the result indicated the reactions dominate to conduct in the tri-phase. When compared with commercial catalysts, BTPAMBC had better catalytic efficiency. At 30 min, the product yield was 0.21% without adding both ionic liquid and catalyst. The yield was 51.55% by adding BTPAMBC but without ionic liquid, and was 96.88% using both ionic liquid and BTPAMBC. With different structures of ionic liquids the catalytic efficiency was significantly enhanced. Stirring at 350 rpm, mass transfer resistance had not a significant effect on the reaction rate. Using n-heptane as the solvent, the kinetic results were correlated by using -ln(1-Y) =kappt equation successfully, where was the apparent reaction rate constant, and the apparent activation energy was 18.78 kcal/mol with high efficiency.

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 1
1.2.1 相間轉移觸媒的分類 3
1.2.2相間轉移觸媒的反應型態 8
1.3離子液體的簡介 13
1.3.1離子液體的發展與回顧 13
1.3.2離子液體的特性 14
1.4第三液相相間轉移觸媒催化反應 17
1.4.1第三液相相間轉移催化反應的發展與回顧 17
1.4.2第三液相相間轉移催化反應原理 19
1.5酯化反應 21
1.5.1一般酯類合成方法 22
1.5.2相間轉移觸媒催化反應合成酯類 24
1.6研究目的與方法 25
第二章　實驗設備與實驗方法 29
2.1實驗藥品 29
2.2實驗設備與分析儀器 31
2.3產物之合成 33
2.4校正曲線 34
2.5觸媒正電荷離子(Q2+)的含量滴定 36
2.6第三液相觸媒中間體(Q(Ph(OH)COO)2)定量方式 36
2.7反應動力學實驗步驟 37
第三章 以雙活性基相間轉移觸媒形成第三液相條件之探討 38
3.1前言 38
3.2雙活性基相間轉移觸媒之合成與分析 39
3.2.1雙活性基相間轉移觸媒的合成與純化 39
3.2.2雙活性基相間轉移觸媒之鑑定與分析 40
3.3雙活性基相間轉移觸媒添加量對形成第三液相之影響 46
3.4鹽類的種類及添加量對形成第三液相之影響 48
3.4.1不同鹽類對形成第三液相之影響 48
3.4.2不同氯化鈉添加量形成第三液相之影響 49
3.5水相反應物的結構與添加量對形成第三液相的影響 51
3.5.1 水相反應物結構對第三液相形成的影響 51
3.5.2不同水相反應物添加量對第三液相形成的影響 54
3.6有機溶劑種類對形成第三液相的影響 57
3.7水量對成第三液相的影響 58
3.8溫度對成第三液相的影響 62
3.9結論 65
第四章 雙活性基相間轉移觸媒搭配離子液體在三液相催化合成鄰-羥基苯甲酸苯甲酯 68
4.1前言 68
4.2反應機構與動力學模式推導 68
4.2.1反應機構 68
4.2.2反應動力學推導 69
4.3再現性測試 75
4.4雙活性基相間轉移觸媒與離子液體的對催化反應的影響 77
4.4.1 離子液體與雙活性基相間轉移觸媒添加量對產率的交互作用 77
4.4.2 不同離子液體對催化反應的影響 80
4.4.3 不同觸媒對催化反應的影響 82
4.5不同有機溶劑 84
4.6攪拌速率對催化反應的影響 86
4.7添加鹽類對催化系統的影響 91
4.7.1 添加鹽類對催化系統的影響 91
4.7.2 氯化鈉添加量對催化系統的影響 93
4.8溫度對催化系統的影響 95
4.8.1 溫度對催化反應的影響 95
4.8.2 視活化能計算 101
4.9結論 103
第五章 總結 106
參考文獻 108
附錄 113




圖目錄
圖1-1 對掌性間轉移觸媒 6
圖1-2多活性基相間轉移觸媒 8
圖1-3相間轉移觸媒催化反應之分類 9
圖1-4 離子液體與一般固態酸及液態酸之酸強度比較 16
圖1-8 實驗規劃圖 28
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 33
圖2-3 鄰-羥基苯甲酸苯甲酯(Benzyl Salicylate)對內標物(Diphenyl methane)之校正曲線 35
圖3-1 合成氯化4,4’-二(三丙基銨基甲基)-1,1’-聯苯樣品之核磁共振儀 氫譜圖 42
圖3-2 合成氯化4,4’-二(三丙基銨基甲基)-1,1’-聯苯樣品之核磁共振儀碳譜圖 44
圖3-3第三液相體積對觸媒添加量作圖 47
圖3-4第三液相體積對氯化鈉添加量作圖 50
圖3-5第三液相體積對水相反應物添加量作圖 55
圖3-6第三液相觸媒陽離子對水相反應物添加量作圖 56
圖3-7第三液相體積對水添加量作圖 60
圖3-8第三液相中觸媒Q2+比例對水添加量作圖 61
圖3-8溫度對第三液相體積作圖 63
圖4-1 三液相雙活性基相間轉移觸媒催化反應機制圖 69
圖4-2再現性測試，產率對時間作圖 76
圖4-3 離子液體與觸媒添加量的交互作用，產率對時間作圖 78
圖4-4 不同離子液體種類，產率對時間作圖 81
圖 4-5不同觸媒，產率對時間作圖 83
圖 4-6不同有機溶劑，產率對時間作圖 85
圖 4-7不同攪拌速率，產率對時間作圖 88
圖 4-8不同攪拌速率，-ln(1-Y)對時間作圖 89
圖 4-9不同攪拌速率，kapp對時間作圖 90
圖4-10不同鹽類，產率對時間作圖 92
圖4-11不同氯化鈉添量，產率對時間作圖 94
圖4-12不同溫度，產率對時間作圖 97
圖4-13不同溫度，-ln(1-Y)對時間作圖 98
圖4-14不同溫度，觸媒中間體莫耳數對時間作圖 99
圖4-15 由Arrhenius’s方程式，-lnkapp對103/T作圖 102









表目錄
表3-1 合成氯化4,4’-二(三丙基銨基甲基)-1,1’-聯苯樣品之NNR圖譜其氫原子實際個數與理論個數之比較 43
表3-2 合成氯化4,4’-二(三丙基銨基甲基)-1,1’-聯苯樣品之C、H、N之元素分析 45
表3-2 第三液相觸媒Q2+離子隨觸媒添加量之變化 48
表3-3 不同無機鹽類形成第三液相相態及觸媒Q2+離子之變化 49
表3-4第三液相體積對氯化鈉添加量作圖 51
表3-5 不同水相反應物所形成之第三液相體積比較 53
表3-6 水相反應物添加量對第三液相體積及組成的影響 54
表3-7有機溶劑的種類對第三液相體積及組成的影響 58
表3-8水添加量對第三液相體積及組成的影響 62
表3-9溫度對第三液相體積及組成的影響 64
表4-1離子液體與觸媒的添加量對第三相的相態影響 79
表4-2 kapp視反應常數對不同種類溶劑之關係 86
表4-3 反應前不同溫度下的觸媒陽離子分布 100
表4-4 反應後不同溫度下的觸媒陽離子分布 100
表4-5 kapp視反應常數對反應溫度之關係 101

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