臺灣博碩士論文加值系統

在以四級銨鹽催化正溴丁烷與酚化鈉的反應中發現，當觸媒皆不易溶於有機相與水相時，若使用較多的觸媒與鹽類，則觸媒將析出聚集在水油兩相之間而形成第三液相。此第三液相不但有加速反應的特性，而且因大部分的觸媒存在於第三液相，可藉由第三液相的分離使用，而獲得重複利用，相當有實用性。
本論文冀望以價格便宜、毒性低的聚乙二醇-600（PEG-600）取代四級銨鹽形成第三液相進行正溴丁烷與酚化鈉的三液相催化反應。除探討PEG-600形成第三液相的條件，與第三液相對反應的影響外，也比較PEG-600與四級銨鹽形成第三液相的差異。
本論文分成兩個部分，第一部份探討PEG-600形成第三液相的條件及各項變因對第三液相性質的影響。第二部分則是根據第一部份的結果進行正溴丁烷與酚化鈉的三液相催化反應，並觀察不同條件下第三液相對批式反應的影響，希望藉由探討其原因而更進一步瞭解第三液相的形成機制。
在第一部份中探討酚化鈉與PEG-600的總量與莫耳分率比值、有機溶劑種類、溫度、PEG種類、鹽類種類及添加量等變因對系統形成第三液相的影響。
由實驗結果得知：使用PEG為相間轉移觸媒的系統必須利用強鹼性鹽類才能形成第三液相，並無法像四級銨鹽一樣能利用非鹼性鹽類將觸媒從水相中析出形成第三液相。PEG形成第三液相的原因不同於四級銨鹽是因為其他鹽類的鹽析作用，而是因其鏈上的親水基被金屬陽離子佔據，加上水中的水分子被OH-搶奪以致無法形成足夠氫鍵而失去親水性析出水相。
由第二部分之實驗結果得知：使用PEG-600為觸媒的系統與使用四級銨鹽觸媒時相同，當第三液相出現後，反應速率會明顯的提升。而且PEG有一最適當的分子量，並非分子量愈大、鏈愈長反應速率愈快。一般來說有利於第三液相中觸媒濃度提升的條件都有利於提升反應速率，因此非極性有機溶劑、高NaOH濃度、高反應溫度皆有利於轉化率的提升。

In a study on the reaction between n-butyl bromide (BuBr) and sodium phenolate (NaOPh) with quaternary ammonium salts as the phase transfer catalyst, we found that a third liquid phase appeared when the solubility of catalyst in both of aqueous phase and organic phase are poor, catalyst will be gathered between aqueous phase and organic phase and formed a third liquid phase. The appearance of the third liquid phase not only can increase the reaction rate but also provides the chance for reusing the catalyst simply by the reuse of itself.
The purpose of the present research is to investigate the possibility to replace quaternary ammonium salts with polyethylene glycols-600 (PEG-600), which is cheap and non-toxic, to form the third liquid phase. The conditions for forming a third liquid phase and the effect of the third liquid phase on the reaction were investigated. Besides, the discrepancy of quaternary salts and polyethylene glycols-600 on forming the third liquid phase was also compared.
This dissertation is divided into two parts. The first part reports the results of the experiments in exploring the conditions for forming a third liquid phase and investigating the factors influencing the characteristic of the third liquid phase. The second part presents the experimental results of the reaction between n-butyl bromide and sodium phenolate conducted under the conditions determined by referring the result obtained in the first part. By way of observing the effects of the third liquid phase in a batch reactor on the reaction rate and the fractional yield, the formation of the third liquid phase can be understood further.
In the investigation on the formation of a third liquid phase, we found that the total added amount and the individual mole fraction of NaOPh and QBr added, kinds of organic solvent, operating temperature, kinds of PEG, and kinds and amount of salt were the important influencing factors. We also found that the system using PEG-600 as the phase transfer catalyst without adding hard base (e.g., NaOH) would not generate a third liquid phase. The formation of a third liquid phase for PEG is due to that the hydrophilic groups PEG associate with cations, in addition to that the water molecules in the aqueous phase are attracted by OH- ions, hence there are not enough hydrogen bonds to maintain hydrophilic of PEG.
From experimental results of the second part, we find that PEG with a high molecular weight or a long chain does not facilitate a high reaction rate and there exits an optimal molecular weight. In this study, PEG-600 provides the best result. In general, a high concentration of catalyst in the third liquid phase would favor the reaction rate. So using a non-polar organic solvent, a high concentration of NaOH and a high reaction temperature would increase the conversion.

中文摘要 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ Ⅰ
英文摘要 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ Ⅲ
誌謝 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ Ⅴ
目錄 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ Ⅵ
圖目錄 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ Ⅷ
主文
第一章 緒論
1-1. 相間轉移催化技術 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 1
1-2. 相間轉移觸媒的種類 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 2
1-3. 三液相催化技術 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 6
第二章 實驗
2-1. 實驗藥品 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 7
2-2. 實驗方法 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 8
2-3. 分析方法 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 11
2-4. 校正曲線的製作 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 12
第三章 第三液相的形成條件與性質
3-1. 形成第三液相的原因 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 14
3-2. 第三液相的組成 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 16
3-3. 形成第三液相的因素探討 ‧‧‧‧‧‧‧‧‧‧‧‧‧ 18
3-3-1. NaOPh與PEG600的總量及莫耳分率比值效應 ‧‧‧‧ 18
3-3-2. 有機溶劑對第三液相的影響 ‧‧‧‧‧‧‧‧‧‧‧ 30
3-3-3. 溫度對第三液相的影響 ‧‧‧‧‧‧‧‧‧‧‧‧‧ 32
3-3-4. 添加鹽類種類及其用量的效應 ‧‧‧‧‧‧‧‧‧‧ 34
3-3-5. PEG分子量的效應 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 35
第四章 反應實驗的結果與討論
4-1. 前言 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 37
4-2. 可能的反應機構 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 37
4-3. 各項變因對反應的影響 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 39
4-4. NaOH在第三液相中扮演的角色 ‧‧‧‧‧‧‧‧‧‧‧ 52
4-5. PEG與四級銨鹽形成第三液相的比較 ‧‧‧‧‧‧‧‧‧ 54
第五章 結論與未來研究方向
5-1. 結論 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 59
5-2. 對未來研究方向的建議 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 61
參考文獻 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 62
自述 ‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧‧ 66

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