臺灣博碩士論文加值系統

本論文主要是利用1,3-丙基磺內酯 (1,3-propanesultone) 或1,4-丁基磺內酯 (1,4-butanesultone) 與三級胺 (tertiary amine) 進行加成反應，得到一種兩性離子化合物，稱為磺酸兩性銨鹽 (quaternary ammonio- alkylsulfonate)。藉由1,3-丙基磺內酯及1,4-丁基磺內酯分別與七種不同種類的三級胺，在適當的操作條件下進行反應，再分別對各種產物做純化、鑑定與分析，合計共開發出十二種高純度之磺酸兩性銨鹽。此種兩性離子化合物在製備上相當容易，而且依其特性可以適用在相間轉移催化反應之多種系統上，做為一種高穩定性之相間轉移觸媒。
利用2-乙氧基乙醇 (2-ethoxyethanol) 與3-溴-1-丙烯 (allyl bromide) 分別為水相及有機相之反應物，且分別使用季銨鹽 (quaternary ammonium salt) 與磺酸兩性銨鹽 (quaternary ammonioalkylsulfonate) 做為相間轉移觸媒，進行丙烯化相間轉移催化反應，合成雙醚化合物2-乙氧基乙基丙烯基醚 (2-ethoxyethylallyl ether)。本系統採用相間轉移觸媒進行催化反應，能在溫和的反應條件下獲得高產率，有效地改進以往製造方法的缺點。在本研究中，一方面尋找最適當的操作條件，另一方面深入探討其化學反應動力學、推測反應機構、求出反應之視活化能，並觀察各種不同反應條件對反應速率之影響。
由實驗結果得知，當轉速高於400 rpm以上時，反應屬於化學反應控制，水相中氫氧化鈉濃度、氫氧化鈉水溶液用量、溫度及觸媒用量增加，均會使反應速率上升，尤其以鹼濃度與溫度的改變對轉化率之影響較為顯著。鹼性物質以解離常數較高之氫氧化鉀效果較佳，觸媒以溴化四丁基銨之催化能力最強，有機相溶劑則用量愈少、極性愈低，如辛烷，反應性愈好。2-乙氧基乙基丙烯醚之合成動力學行為，亦由實驗得知可用偽一次速率式 (pseudo-first-order rate law) 描述之，萃取反應機構將可被用來解釋本反應所進行的途徑。

In this dissertation, the zwitterions "quaternary ammonioalkylsulfonate", which was synthesized from the addition reaction of alkylsultone and tertiary amine in a liquid phase, was studied. Under the suitable operating conditions, twelve kinds of high purity zwitterions, which were carried out from the reaction of 1,3-propanesultone or 1,4-butanesultone and seven kinds of tertiary amines, were obtained. The characteristic of the quaternary ammonio- alkylsulfonate, which is stable and easy to produce, is suited for phase transfer catalysis system.
The allylation substitution of 2-ethoxyethanol and allyl bromide to synthesize acetal compounds by phase transfer catalysis was successfully developed in an alkaline solution/ organic solvent two phase medium. The main purpose of this study is to find the reaction conditions in such a way to search the kinetic behavior, reaction mechanism, activation energy etc.. Quaternary ammonium salts and quaternary ammonioalkylsulfonates were employed as the phase transfer catalyst.
The conclusions were obtained from the experiments. Beyond 400 rpm, the reaction is belonging to chemical reaction controlled. The reaction rate is increased with the increase of the concentration of NaOH in aqueous solution, temperature and the amount of catalyst. Especially, when the concentration of alkalinity and temperature are changed, the conversion is significantly increased. KOH and TBAB are the best alkaline substance and catalyst in this system. Low polarity and organic solvent in a small quantity are recommended to obtain higher a reaction rate. The reaction follows pseudo-first-order rate law, and it is described by the extraction mechanism.

致謝
中文摘要 ……………………………………………………………………. i
英文摘要 …………………....……………………………………………… ii
目錄 ……………………………………………………………………...… iii
圖目錄 ……………………………………………………..……………..… v
表目錄 …………………………………………………………..…..…...… ix
符號說明 ………………………………………..………………………… xii
第一章 緒論
§1.1 醚醇類之丙烯化反應合成雙醚 ……….…………...………….… 1
§1.2 相間轉移觸媒之緣起 ………………….………………………… 2
§1.3 相間轉移催化技術之基本原理 ……….…………..…………….. 4
§1.4 相間轉移觸媒之種類與價格 ………….………………………… 7
§1.5 磺酸兩性銨鹽簡介 ……………………...……………………… 10
§1.6 本論文研究目的及內容 ………………...……………………… 11
第二章 實驗藥品與儀器
§2.1 實驗藥品 …………...…………………………………………… 13
§2.2 實驗儀器 …………...…………………………………………… 14
§2.3 分析儀器 ……………..…………………………………………. 16
第三章 實驗方法與步驟
§3.1 磺酸兩性銨鹽之製備純化與鑑定 ………...…………………… 18
3.1-1 製備與純化 …………………………………………………… 18
3.1-2 分析與鑑定 …………………………………………...………. 19
§3.2 產物2-乙氧基乙基丙烯基醚之製備純化與鑑定 ….…..……… 60
3.2-1 製備與純化 …………………………………………………… 60
3.2-2 分析與鑑定 …………………………………………………… 60
§3.3 校正曲線 ……………………………………….…………….…. 64
第四章 丙烯化反應合成2-乙氧基乙基丙烯基醚之研究
§4.1 反應機構 ……………………………………..…………………. 67
§4.2 動力學模式 …………………………………..…………………. 68
§4.3 以季銨鹽進行催化反應之結果與討論 …………….………….. 69
4.3-1 轉速之影響 ………………………………………….………... 71
4.3-2 水相中氫氧化鈉濃度之影響 …………………...……………. 71
4.3-3 不同鹼性物質之影響 ………………………………...………. 72
4.3-4 氫氧化鈉水溶液用量之影響 ……………………………….... 81
4.3-5 溫度之影響 ………………………………………………...…. 81
4.3-6 有機相溶劑用量之影響 …………………………………....… 82
4.3-7 有機相溶劑種類之影響 …………………………………...…. 83
4.3-8 觸媒用量之影響 ……………………………………………… 95
4.3-9 觸媒種類之影響 ……………………………………………… 95
§4.4 以磺酸兩性銨鹽進行催化反應之結果與討論 ………...…….. 106
4.4-1 水相中氫氧化鈉濃度之影響 ………………………...…...… 106
4.4-2 轉速之影響 ………...…………………………….………….. 111
4.4-3 溫度之影響 ………………………………………………….. 115
4.4-4 觸媒用量之影響 ………………………………………..…… 115
第五章 結論與未來展望
§5.1 結論 …………………..……………………………………...… 123
§5.2 未來展望 ………………………………...…………………….. 125
參考文獻 ………………………………………………………………… 126

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