臺灣博碩士論文加值系統

研究探討超音波與離子液體輔助雙活性基相間轉移觸媒於三液相系統中催化鄰-羥基苯甲酸鈉與2-苯氧乙基溴合成鄰-羥基苯甲酸2-苯氧乙基酯之酯化反應。研究內容包含探討第三液相的組成以及催化鄰-羥基苯甲酸2-苯氧乙基酯之動力學。雙活性基相間轉移觸媒以二溴對二甲苯與三己胺反應合成雙活性基觸媒溴化 1,4二(三己基銨基甲基)苯(BTHAMBB，QBr2)，利用核磁共振氫譜、核磁共振碳譜與元素分析驗證成功的合成出此觸媒。
第三液相生成與組成條件變數探討包括觸媒添加量、溶劑種類、鹽類添加量、鹽類種類、離子液體種類、離子液體添加量。觸媒使用量增加會生成較多的觸媒中間體與第三液相體積，此種觸媒於不添加鹽類就會有2毫升的第三液相生成，使用氯化鈉可以使第三液相中含有較多的觸媒中間體，但不會影響第三液相的體積，添加少量離子液體三己基十四烷基鏻二(三甲基戊基)鏻酸，觸媒中間體於第三液相中之轉化率為92%，此外離子液體添加量增加越容易於有機相中發現觸媒陽離子。
由觸媒陽離子的分布研究，發現觸媒都集中在第三液相中，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，此反應速率式能夠以擬一階線性反應動力式描述。此種觸媒只需要使用商用觸媒一半量，產率就可以優於商用觸媒，且不需加入鹽類即可形成第三液相；只有使用超音波(300 W、28 kHz)輔助比只有攪拌(250 rpm)輔助下反應速率有更好的提升；超音波輔助使用正庚烷作溶劑，產率為70.28%，而溶劑使用甲基異丁酮無超音波時產率為68.29%，超音波的使用可以避免毒化物溶劑的使用；反應溫度60℃無超音波輔助5小時後產率為51.32%，同樣反應溫度有超音波只需要3小時產率就有52.98%，反應5小時產率達72.32%。離子液體添加0.00015莫耳三己基十四烷基鏻二(三甲基戊基)鏻酸能夠提生產率約12%，同時使用超音波與離子液體輔助反應，反應5小時可以得到產率84.62%。利用Arrheniu’s方程式，計算得有超音波時視反應活化能Ea = 19.24 kcal/mol，無超音波時視反應活化能Ea = 22.21 kcal/mol。

In this study, the esterification of sodium salicylate with 2-phenoxyethyl bromide to synthesize 2-phenoxyethyl salicylate by ultrasound and ionic liquid promoted dual-site phase-transfer catalyst in third-liquid system was investigated. The investigations included the composition of the third-liquid phase and kinetics of synthesizing 2-phenoxyethyl salicylate. The dual-site phase-transfer catalyst 1,4-bis(trihexylammoniomethyl) benzene dibromide (BTHAMBB，QBr2) was synthesized from p-xylene dibromide and trihexylamine and proved by 1H NMR, 13C NMR and elemental analysis.
The operating parameters of forming the third-liquid phase and the composition of the third-liquid phase included the amounts of catalyst, types of organic solvent, amounts of inorganic salt, types of inorganic salt, types of ionic liquid, amounts of ionic liquid. The volume of third-liquid phase and amount of Q(Ph(OH)COO)2 would be raised by the increasement of the amounts of catalyst. Without adding inorganic salt, the system would separate out 2.0 ml of third-liquid phase. Adding NaCl would be raised amounts of Q(Ph(OH)COO)2, but could not enhance the volume of third-liquid phase. With the addition of ionic liquid(Trihexyl(tetradecyl)- phosphonium bis(2,4,4-trimethyl-pentyl)phos- phinate，[THTDP][TMPP]), the conversion of Q(Ph(OH)COO)2 can reach 92%. Furthermore, Q(Ph(OH)COO)2 can be carried to the organic phase by enhancing the amounts of ionic liquid [THTDP][TMPP].
Q(Ph(OH)COO)2 which concentrated in the third-liquid phase was observed. In the kinetic part, the result indicated that the reactions dominate to conduct in the third-liquid phase. The rate of apparent reaction could be described by pseudo-frist-order kinetic equation. The catalytic activity dual-site phase transfer catalyst was better than commercial catalysts. In addition, the third-liquid phase was formed from BTHAMBB without adding any extra salt. Comparison of operating condition with ultrasound and stirring, overall reaction rate can be greatly enhanced by ultrasound. Using n-heptane as an organic solvent under ultrasound, the yield of product was obtained 70.28%; Using MIBK as an organic solvent without ultrasound, the yield was obtained 68.29%. The usage of toxic solvent can be reduced by using ultrasound. At 60℃, the yield was obtained 51.32% in 5 hours without ultrasound. At the same temperature with ultrasound, the yield goes to 52.98% under 3 hours, and yield was obtained 72.32%. Adding phosphonium-based ionic liquid [THTDP] [TMPP], the yield enhances 12%. The yield is as high as 84.62% with both ionic liquid and catalyst by ultrasound assisted. 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 19.24 kcal/mol. Without ultrasound, the apparent activation energy was 22.21 kcal/mol.

目錄
摘要 i
Abstract iii
致謝 v
目錄 vi
圖目錄 ix
表目錄 xii
符號說明 xiii
第一章 緒論 1
1.1前言 1
1.2相間轉移觸媒簡介 2
1.2.1相間轉移觸媒結構分類 3
1.2.2.相間轉移觸媒反應型態 10
1.3第三液相相間轉移觸媒催化反應 14
1.3.1.三液相相間轉移觸媒催化反應發展與回顧 15
1.3.2.第三液相相間轉移催化反應原理 17
1.4酯化反應 20
1.4.1.一般酯類合成方法 20
1.4.2.相間轉移觸媒催化反應合成酯類 21
1.5超音波原理與應用 22
1.5.1 超音波輔助反應原理 23
1.5.2 超音波在相間轉移催化反應的應用 24
1.6離子液體的簡介 25
1.6.1離子液體的發展與回顧 25
1.6.2離子液體的特性 27
1.7研究目的與方法 29
第二章 實驗設備與實驗方法 32
2.1實驗藥品 32
2.2.實驗設備與分析儀器 35
2.3產物合成 38
2.4觸媒中間體合成 38
2.5校正曲線 39
2.6觸媒中間體(Q (PH(OH)COO)2)定量方式 42
2.7觸媒正電荷離子(Q2+)的含量滴定 42
2.8反應動力學實驗步驟 43
第三章 雙活性基相間轉移觸媒形成第三液相探討 45
3.1 前言 45
3.2 雙活性基相轉移觸媒之合成與分析 45
3.2.1 雙活性基相間轉移觸媒BTHAMBB之合成與純化 45
3.2.2 雙活性基相間轉移觸媒之鑑定與分析 46
3.3 雙活性基相間轉移觸媒添加量對形成第三液相的影響 51
3.4有機溶劑種類對形成第三液相的影響 56
3.5鹽類效應對形成第三液相的影響 58
3.5.1鹽類添加量對形成第三液相的影響 58
3.5.2鹽類種類對形成第三液相的影響 63
3.6離子液體對形成第三液相的影響 65
3.6.1不同離子液體對第三液相的影響 65
3.6.2離子液體添加量對第三液相的影響 68
3.7結論 73
第四章 以超音波及離子液體輔助雙活性基相間轉移觸媒於三液相催化酯化 75
4.1前言 75
4.2反應機構與動力學模式推導 75
4.2.1反應機構 75
4.2.2反應動力學推導 76
4.3再現性測試 83
4.4不同相間轉移觸媒對催化反應的影響 85
4.5不同觸媒添加量對催化反應的影響 89
4.6不同溶劑對催化系統的影響 94
4.7有機相反應物添加量對催化反應的影響 98
4.8超音波效應 102
4.8.1不同超音波功率對反應的影響 102
4.8.2不同超音波頻率對反應的影響 105
4.9攪拌速率對催化反應的影響 108
4.9.1有超音波輔助，探討攪拌速率對催化反應的影響 108
4.9.2無超音波輔助，探討攪拌速率對催化反應的影響 111
4.10超音波與攪拌交互作用對催化反應的影響 115
4.11不同鹽類對催化反應的影響 118
4.12不同鹽類添加量對催化反應的影響 122
4.13溫度效應 125
4.13.1無超音波輔助下，溫度效應對反應的影響 125
4.13.2於超音波輔助下，溫度效應對反應的影響 128
4.13.3活化能計算 131
4.14離子液體種類對催化反應的影響 133
4.15觸媒與離子液體對催化反應的影響 138
4.16離子液體添加量對催化反應的影響 141
4.17超音波輔助不同時間對催化反應的影響 144
4.18結論 146
第五章 總結 149
參考文獻 152
附錄 161
 
圖目錄
圖1 1液-液相轉移萃取機制反應機構示意圖 2
圖1-2常見四級鹽類結構圖 4
圖1-3常見巨環醚結構圖 5
圖1-4對掌性相間轉移觸媒圖 7
圖1-5各種多活性基相間轉移觸媒 9
圖1-6相間轉移觸媒反應型態 10
圖1-7液-液正相相間轉移觸媒催化反應機構示意圖 11
圖1-8液-液反相相間轉移觸媒催化反應機構示意圖 12
圖1-9液-液逆相相間轉移觸媒催化反應機構示意圖 12
圖1-10 Makosza界面機制示意圖 13
圖1-11在超音波放射下液體中空泡的成長與崩裂示意圖 23
圖1-12 離子液體與一般固態酸及液態酸之酸強度比較 28
圖1-13實驗規畫圖 31
圖 2 1超音波批式反應實驗裝置圖 37
圖 2 2超音波振盪槽之發振示意圖 37
圖2-3鄰-羥基苯甲酸2-苯氧乙基酯(2-Phenoxyethyl salicylate)對內標物(Diphenyl methane)之校正曲線 40
圖2-4鄰-羥基苯甲酸化1, 4-二(三己基銨基甲基)苯(Q(Ph(OH)COO)2)對內標物(Diphenyl methane)之校正曲線 41
圖3 1合成溴化 1,4-二(三己基銨基甲基)苯樣品之核磁共振儀檢測報告(氫譜) 49
圖3 2合成溴化 1,4-二(三己基銨基甲基)苯樣品之核磁共振儀檢測報告(碳譜) 50
圖3-3第三液相體積對觸媒添加量作圖 53
圖3-4第三液相觸媒中間體含量對觸媒添加量作圖 54
圖3-5第三液相觸媒中間體含量與觸媒陽離子比例對觸媒添加量作圖 55
圖3-6第三液相體積與溴化鈉添加量作圖 60
圖3-7第三液相中間體與觸媒陽離子之比例與溴化鈉添加量作圖 61
圖3-8第三液相觸媒中間體與溴化鈉添加量作圖 62
圖3-9第三液相觸媒中間體含量與離子液體添加量作圖 70
圖3-10第三液相體積與離子液體添加量作圖 71
圖4-1超音波與離子液體輔助第三液相雙活性基相間轉移觸媒催化反應機構圖 76
圖4-2再現性測試，產率對時間作圖 83
圖4-3再現性測試，產率平均值對時間作圖 84
圖4-5不同觸媒種類，-ln(1-Y)對時間作圖 88
圖4-6不同觸媒添加量，產率對時間作圖 90
圖4-7不同觸媒添加量，-ln(1-Y)對時間作圖 91
圖4-8視反應速率常數kapp與觸媒添加量作圖 92
圖4-9視反應速率常數kapp與觸媒中間體生成量作圖 93
圖4-10不同溶劑，產率對時間作圖 95
圖4-11不同溶劑，-ln(1-Y)對時間作圖 97
圖4-12有機相反應物添加量，產率對時間作圖。 99
圖4-13有機相反應物添加量，-ln(1-Y)對時間作圖 100
圖4-14視反應速率常數kapp對有機相反應物添加量作圖 101
圖4-15不同超音波功率，產率對時間作圖 103
圖4-16不同超音波功率，-ln(1-Y)對時間作圖 104
圖4-18不同超音波頻率，-ln(1-Y)對時間作圖 107
圖4-19攪拌速率於有超音波輔助下，產率對時間作圖 109
圖4-20攪拌速率於有超音波輔助下，-ln(1-Y)對時間作圖 110
圖4-21攪拌速率於無超音波輔助下，產率對時間作圖 111
圖4-22攪拌速率於無超音波輔助下，-ln(1-Y)對時間作圖 112
圖4-23視反應速率常數kapp對攪拌速率作圖 114
圖4-24攪拌速率與超音波效應交叉對比，產率對時間作圖 116
圖4-25攪拌速率與超音波效應交叉對比，-ln(1-Y)對時間作圖 117
圖4-26不同鹽類，產率對時間作圖 119
圖4-27不同鹽類，-ln(1-Y)對時間作圖 120
圖4-28鹽類添加量，產率對時間作圖 123
圖4-29鹽類添加量，-ln(1-Y)對時間作圖 124
圖4-30同溫度無超音波輔助下，產率對時間作圖 126
圖4-31不同溫度無超音波輔助下，-ln(1-Y)對時間作圖 127
圖4-32溫度於超音波輔助下，產率對時間作圖 129
圖4-33不同溫度於超音波輔助下，-ln(1-Y)對時間作圖 130
圖4-34 Arrheniu’s方程式，-ln(kapp)對1000/T作圖 131
圖4-35離子液體結構(I) 133
圖4-35離子液體結構(II) 134
圖4-35離子液體結構(III) 135
圖4-36不同離子液體，產率對時間作圖 136
圖4-37不同離子液體，-ln(1-Y)對時間作圖 137
圖4-38觸媒與離子液體交叉比對，產率對時間作圖 139
圖4-39觸媒與離子液體交叉比對，-ln(1-Y)對時間作圖 140
圖4-40離子液體添加量，產率對時間作圖 142
圖4-41離子液體添加量，-ln(1-Y)對時間作圖 143
圖4-42 不同超音波輔助時間，產率對時間作圖 145
附錄A. 鄰-羥基本甲酸2-苯氧乙基酯之1HNMR圖譜 161
附件B. 鄰-羥基本甲酸化 1,4-二(三己基銨基甲基)苯之1HNMR圖譜 162

表目錄
表3- 1合成溴化 1,4-二(三己基銨基甲基)苯樣品之N、C、H元素分析 47
表3- 2合成溴化 1,4-二(三己基銨基甲基)苯樣品之NNR圖譜其氫原子實際個數與理論個數之比較 48
表3-3觸媒添加量對第三液相體積與組成的影響 52
表3-4有機溶劑種類對第三液相的形成與組成影響 57
表3-5鹽類添加量對第三液相的形成與組成影響 59
表3-6鹽類種類對第三液相的形成與組成影響 64
表3-7離子液體分子式、名稱與代號 66
表3-8不同離子液體對第三液相的形成與組成影響 67
表3-9離子液體添加量對第三液相的形成與組成影響 69
表4-1不同相間轉移觸媒對產率之影響 86
表4-2 kapp視反應常數對有機溶劑之關係 96
表4-3攪拌速率對視反應速率常數kapp的影響 113
表4-4超音波與攪拌速率交互作用對視反應常數kapp及產率 115
表4-5 kapp視反應常數對不同鹽類之關係 121
表4-6溫度對視反應常數kapp與產率影響 128
表4-7有無超音波之活化能與頻率因子 132
表4-8 超音波輔助不同時間對產率與視反應速率常數之影響 144
附件C. 文獻整理表 163

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