臺灣博碩士論文加值系統

本論文在探討以第三液相之相間轉移觸媒溴化四正丁基鏻催化鄰-羥基苯甲酸鈉與溴化苯甲基之酯化反應來生成鄰-羥基苯甲酸苯甲酯。第三液相主要由水相反應物與觸媒形成的觸媒中間體所組成。首先針對形成第三液相條件進行探討，包括水相反應物量、水量、觸媒量與種類、添加鹽類、溶劑種類等。在添加愈多的溴化鈉時，形成第三液相所需加入的觸媒量愈小，而第三液相體積則隨著觸媒量之增加體積隨之提升；但是當觸媒量高於某一定量，形成第三液相之體積就無顯著變化，在水量20~70毫升範圍鄰-羥基苯甲酸鈉0.02莫耳與溴化鈉0.125莫耳條件下皆能形成第三液相。
在含有相間轉移觸媒的系統中，其界面張力能以Gibbs與Langmuir 等溫吸附方程式來描述，此外界面過量與分子界面積皆能被計算。當水溶液中含有相間轉移觸媒其界面張力會降低，在系統中第三液相與水相的界面張力值約為1.2~2.8 mN/m；遠小於第三液相與正庚烷的介面張力8~12 mN/m，表示有機相與第三液相之間存在著質傳阻力。吸附界面的分子界面積為0.17~0.19 Å2，觸媒吸附活性以四級鏻鹽大於四級銨鹽。
本文亦定量出在不同操作條件下，第三液相中成分如鄰-羥基苯甲酸鈉、觸媒與觸媒中間體隨反應時間之變化情形，而其產物分佈在有機相與第三液相中。在批式操作變數中轉速350rpm以上可忽略質傳阻力，當溴化四正丁基鏻量為0.006莫耳呈現有機相產率高達85﹪，隨著觸媒量增加其產率隨之提高。建立反應動力學模式並以實驗數據得到符合虛擬一階反應來表示。
以正庚烷為有機溶劑與溴化正四丁基鏻催化酯化反應，可得視活化能為17.69 kcal/mol。第三液相系統最大優點為觸媒能再回收使用，隨著反應其第三液相體積減少至一定程度，再添加觸媒於更新水油兩相中，其反應速率仍可維持如新觸媒。

The kinetics of esterification of sodium salicylate with benzyl bromide to produce benzyl salicylate were investigated via third-liquid phase-transfer catalysis in a tri-liquid system. The conditions of forming the third-liquid phase were performed for different aqueous reactants, inorganic salts, organic solvents, and catalysts to find the dependence of the characteristics of the catalytic intermediate on producing the third-liquid phase. First, this work explores the formation of a third liquid in the organic phase/ tetrabutylphosphonium bromide (TBPB) /aqueous (sodium salicylate + NaBr) system. It is found that the minimum quantity of TBPB required to form the third-liquid is dependent on the amounts of NaBr added, but the variation of the third-phase by NaBr is insignificant with greater amount of TBPB used. The volume of third-liquid generated increases with increasing amounts of catalyst used. The regime of 20~70 mL- water in a 30mL-heptane favors forming third-liquid phase.
The interfacial tensions in a tri-liquid system were measured and could be well described by the Gibbs adsorption equation coupled with the Langmuir monolayer isotherm. In addition, the interfacial parameters such as surface excess and molecular area of the present liquid-liquid phase-transfer-catalyzed systems. It was found that the interfacial tensions was decreased with catalyst added. The interfical tension between water and third-liquid was 1.2~2.8 mN/m, much less than 8~12 mN/m for the third-liquid/heptane interface, exhibiting the dominating mass-transfer resistance to be in heptane side. The molecular area was estimated in the range of about 0.17~0.19 Å2. The surface activity of phosphonium salts is higher than ammonium salts.
The amount was agreed sodium salicylate, catalyst and catalytic intermediate in the third-liquid phase. The product is present in both organic phase and in the third but not in the aqueous phase due to its insolubility in the latter. The reaction mechanism and kinetic model is present and validated from the experimental results. When the agitation speed exceeds 350 rpm, the mass transfer resistance at the third-liquid phase interface can be ignored. Above 85﹪of product yield in the organic phase can be obtained for 0.006 moles of TBPB used to form the third-liquid phase, and the reactivity increase with increasing the amount of TBPB employed. The experimental data were well described by the pseudo-first-order kinetics .
The apparent activation energy in heptane was obtained 17.69 kcal/mol using tetrabutylphosphonium bromide as the catalyst. The most advantage of using third-liquid phase is the reuse of catalyst. After separating the third-liquid phase form the reaction mixture, the volume of the third-liquid phase was reduced to some extent, however, introducing additional amount of third-liquid phase, the reaction rate was still high enough as the fresh catalyst used.

中文摘要------------------------------------------------------Ⅰ
英文摘要------------------------------------------------------Ⅲ
誌謝----------------------------------------------------------Ⅴ
目錄----------------------------------------------------------Ⅵ
圖目錄 -------------------------------------------------------Ⅹ
表目錄--------------------------------------------------------Ⅶ
符號說明----------------------------------------------------ⅩⅣ
第一章 緒論--------------------------------------------------1
1.1 前言----------------------------------------1
1.2 相間轉移催化反應----------------------------1
1.2-1依相間轉移觸媒的反應方式分類-----------2
1.2-2依相間轉移觸媒的結構分類---------------4
1.3 第三液相催化反應----------------------------8
1.3-1第三液相催化反應的發展-----------------8
1.3-2第三液相催化反應原理-------------------9
1.4 多相系統之界面特性-------------------------10
1.5 酯化反應-----------------------------------14
1.5-1一般酯類合成方法----------------------14
1.5-2相間轉移催化方法合成酯類--------------15
1.6 研究目的與研究方法-------------------------16
1.6-1第三液相形成的變因探討----------------17
1.6-2各種成分在第三液相分佈情形探討--------17
1.6-3第三液相催化反應的變因探討------------18
第二章 實驗部分---------------------------------------------20
2.1 實驗藥品-----------------------------------20
2.2 實驗裝置與分析儀器-------------------------21
2.3 產物之合成---------------------------------22
2.4 觸媒中間體之製備---------------------------23
2.5 校正曲線-----------------------------------23
2.6 第三液相組成之定量方式---------------------24
2.7 界面張力與導電度分析-----------------------26
2.8 反應動力實驗步驟---------------------------27
第三章 鄰-羥基苯甲酸鈉與相間轉移觸媒形成第三液相之條件-----32
3.1. 鄰-羥基苯甲酸鈉用量之影響------------------32
3.2. 相間轉移觸媒觸媒種類之影響-----------------34
3.3 添加強鹼與其他鹽類之影響-------------------36
3.4 溫度與溶劑種類之影響-----------------------40
3.5 水量與溶劑之影響---------------------------41
3.6 第三液相之界面性質分析---------------------43
3.6-1水相與第三液相界面性質----------------44
3.6-2有機相與第三液相界面性質--------------55
3.7 結論---------------------------------------59
第四章 第三液相觸媒在兩液相間之分佈與催化活性--------------61
4.1 水相反應物在第三液相之分佈-----------------61
4.1-1不同水量------------------------------62
4.1-2不同水相反應物量----------------------63
4.1-3不同觸媒------------------------------64
4.1-3不同觸媒量----------------------------65
4.2 觸媒中間體在第三液相之分佈-----------------66
4.2-1不同觸媒量----------------------------67
4.2-2不同水相反應物量----------------------69
4.2-3不同水量------------------------------71
4.2-4不同觸媒------------------------------73
4.3觸媒在第三液相之分佈---------------------------------------75
4.3-1不同觸媒量-----------------------------76
4.3-2不同水相反應物量-----------------------76
4.2-3不同水量-------------------------------78
4.2-4不同觸媒-------------------------------80
4.3-5不同有機相反應物量---------------------82
4.4第三液相觸媒之催化活性-------------------85
4.4-1不同水量-------------------------------85
4.4-2不同水相反應物量-----------------------87
4.4-3不同水量-------------------------------88
4.4-4不同觸媒量-----------------------------90
4.5結論--------------------------------------------------92
第五章 第三液相催化鄰-羥基苯甲酸苯甲酯反應動力探討----------95
5.1前言--------------------------------------------------95
5.2反應動力模式探討--------------------------------------95
5.3操作變數對第三液相反應之效應--------------------------99
5.3-1定義M值--------------------------------99
5.3-2攪拌速率效應--------------------------101
5.3-3不同觸媒效應--------------------------103
5.3-4不同溫度效應--------------------------103
5.3-5不同鹽類效應--------------------------107
5.3-6不同觸媒量效應------------------------107
5.3-7不同水量效應--------------------------110
5.3-8不同水相反應物量效應------------------113
5.3-9不同溶劑效應--------------------------116
5.3-10不同鹽類效應-------------------------117
5.3-11不同有機相反應物量效應---------------117
5.3-12式活化能計算-------------------------120
5.4回收效率------------------------------------------123
5.5結論----------------------------------------------127
第六章 總結------------------------------------------------129
參考文獻-----------------------------------------------------131
附錄---------------------------------------------------------135
A 鄰-羥基苯甲酸苯甲酯之1HNMR圖譜------------135
B 鄰-羥基苯甲酸化四丁基銨1HNMR圖譜----------136

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