甲醇鈉之製備與其與二氯甲烷之液-固相轉移催化甲氧基取代

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姓名

王冠文(Guan-Wun Wang) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

甲醇鈉之製備與其與二氯甲烷之液-固相轉移催化甲氧基取代
(The preparation of Sodium Methoxide and the S-L Phase-Transfer Catalyzed Methoxy Substitution of Dichloromethane.)

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摘要(中)

本研究在探討甲醇鈉之製備與其及二氯甲烷之液-固相轉移催化甲氧基取代。理論推究兩相中之物理與化學程序，得知溶劑之種類與劑量、相轉移催化劑種類與劑量、攪拌速度以及反應溫度為影響總反應速率及產物分佈的因素，並遂一實驗求得最適反應條件如下：
甲醇鈉之製備：在甲醇1.2 mol、氫氧化鈉1 mol、催化劑（BzBu3NCl）劑量為甲醇的10％、氯化鈣0.1 mol、反應溫度50℃及攪拌速度200 rpm等條件下，反應八小時，抽氣過濾後，再以100～150℃蒸出甲醇則可得甲醇鈉固體約20 g（收率約60％）。
二甲氧基甲烷之製備有以下兩種方法：
I. 在甲醇鈉2 mol、二氯甲烷1 mol、溶劑THF約為0.6 mol、催化劑（BzBu3NCl）劑量為甲醇鈉的10％、反應溫度50℃及攪拌速度200 rpm等條件下於250mL之三頸圓底燒瓶，反應約一天半，可得二甲氧基甲烷產率達90％以上。
II. 在甲醇2.2 mol、氫氧化鈉3.2 mol、二氯甲烷1 mol、溶劑THF約為0.6 mol、催化劑（BzBu3NCl）劑量為甲醇的10％、反應溫度50℃及攪拌速度200rpm等條件下，反應約三小時，可得二甲氧基甲烷產率約85％。

摘要(英)

The preparation of sodium methoxide and the phase-transfer catalyzed methoxy substitution of dichloromethane were studied. The physical and chemical processes were considered to derive the overall production rate equation for methylal. The factors (the types and amounts of the solvents, the kinds and amounts of phase-transfer catalysts, the stirring speed and the reaction temperature) affecting the overall reaction rate and the product distributed were studied. The results can be explained with the overall rate equation.
Sodium methoxide was prepared as follows: methanol 1.2 mol, sodium hydroxide 1 mol and phase-transfer catalyst (BzBu3NCl) amounts of 10% methanol, reaction temperature 50℃and stirring speed 200 rpm. Reaction time about 8 hours, vacuum-filter and distillation in 100~150℃, we can recycle methanol and obtain pure sodium methoxide solid.
The dimethoxymethane was synthesized by method I and method II.
Method I: sodium methoxide 2 mol, dichloromethane 1 mol, solvent (THF) 0.6 mol and phase-transfer catalyst (BzBu3NCl) amounts of 10% sodium methoxide, reaction temperature 50℃and stirring speed 200 rpm. Reaction time about 30 hours, we can obtain about 90% dimethoxymethane.
Method II: methanol 2.2 mol, sodium hydroxide 3.2 mol, dichloromethane 1 mol, solvent (THF) 0.6 mol and phase-transfer catalyst (BzBu3NCl) amounts of 10% methanol, reaction temperature 50℃and stirring speed 200 rpm. Reaction time about 3 hours, we can obtain about 50% dimethoxymethane.

關鍵字(中)

★ 甲醇鈉
★ 二氯甲烷
★ 甲氧基取代
★ 相轉移催化

關鍵字(英)

★ Methoxy Substitution
★ Dichloromethane
★ Sodium Methoxide
★ Phase-Transfer Catalyzed

論文目次

中文摘要..............................i
英文摘要..............................ii
誌謝..............................iii
目錄..............................iv
圖目錄..............................v
符號說明..............................vi
第一章　　緒　論..............................1
1-1 相轉移催化之起源與定義..............................1
1-2 相轉移催化之原理及系統形態..............................1
1-2-1　相轉移催化之原理..............................1
1-2-2　相轉移催化之系統形態..............................2
1-3 相轉移催化劑之種類.............................. 3
1-4 甲醇鈉之經濟性、來源與用途..............................5
1-5 甲醇鈉之合成..............................6
1-6 二甲氧基甲烷之經濟性、來源與用途..............................6
1-7 二甲氧基甲烷之合成.............................. 7
1-8 本研究的動機與主旨 ..............................9
第二章　　理　論..............................10
2-1 親核取代反應..............................10
2-1-1　單分子親核取代反應..............................10
2-1-2　相轉移催化之系統形態 ..............................11
2-1-3　相轉移催化之親核取代反應..............................11
2-2 液-固反應系統之化學程序與質傳程序..............................11
2-3 液-固反應系統中二甲氧基甲烷之總生成速率方程式..............................12
2-4 液-固系統中影響二甲氧基甲烷之總生成速率之因素..............................16
2-4-1　相轉移催化劑結構之影響..............................16
2-4-2 相轉移催化劑劑量之影響..............................16
2-4-3 溶劑之影響..............................17
2-4-4 攪拌速率之影響..............................17
2-4-5 溫度之影響..............................17
第三章　　實驗部份..............................19
3-1 藥品..............................19
3-1-1　實驗及分析用之藥品..............................19
3-1-2　相轉移催化劑之製備..............................20
3-1-3　甲醇鈉之製備..............................21
3-2 實驗裝置及分析儀器.............................. 21
3-2-1　實驗裝置..............................21
3-2-2　氣相層析儀..............................22
3-3 樣品分析..............................22
3-3-1　氣相層析儀(GC)之校正曲線..............................22
3-3-2　氣相層析儀(GC)之分析條件..............................22
3-3-3　氣相層析儀(GC)之樣品分析..............................24
3-4 實驗之操作..............................24
3-5 二甲氧基甲烷製備程序之實驗步驟..............................24
3-5-1　相轉移催化劑結構之影響..............................24
3-5-2　溶劑之影響..............................24
3-5-3　相轉移催化劑劑量之影響..............................25
3-5-4　攪拌速率之影響..............................25
3-5-5　溫度之影響..............................25
3-5-6　適當實驗條件..............................25
第四章　　結果與討論..............................26
4-1 相轉移催化劑結構之影響..............................26
4-2 溶劑之影響..............................28
4-3 相轉移催化劑劑量之影響..............................30
4-4 攪拌速率之影響..............................30
4-5 溫度之影響..............................30
4-6 適當實驗條件..............................35
4-6-1　三頸圓底燒瓶系統..............................35
4-6-2　密閉式反應器系統..............................35
4-6-3　製備甲醇鈉法..............................35
第五章　　結論..............................40
參考文獻..............................41
附錄一..............................45
附錄二..............................46

參考文獻

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指導教授

王天財(Ten-Tsai Wang)

審核日期

2009-6-22

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