| 摘要: | 本研究探討氯化丙烯之液-固相轉移催化醋酸根取代以合成醋酸丙烯酯並探討醋酸丙烯酯之液-液相轉移催化水解以合成丙烯醇。考慮氯化丙烯、醋酸鈉、相轉移催化劑和溶劑之液-固相轉移催化系統之物理與化學程序，衍導得醋酸丙烯酯總生成速率方程式。該式中影響醋酸丙烯酯之生成速率因素包括季銨鹽相轉移催化劑結構(陽離子結構與陰離子結構)、相轉移催化劑劑量、攪拌速率、溫度等。將這些因素對總生成速率之影響詳加實驗，並以該總生成速率方程式解釋之。 醋酸丙烯酯之適當生產條件有兩組，其一為以三頸瓶為反應器在常壓下生產，此需添加溶劑以提高反應溫度，而採用醋酸丙烯酯(產物)為溶劑，可免去溶劑之分離。該適當生產條件為氯化丙烯0.5 mole，醋酸鈉0.55 mole，醋酸丙烯酯0.5 mole，碘化四丁基銨0.025 mole，攪拌速率500 rpm，溫度設定為起始溫度70 ℃，每隔半小時升5 ℃，1小時後溫度達80 ℃後維持此溫度至反應結束。在此組條件下反應4小時之產率達99 ％以上。其二為使用Parr 4564M型高壓反應器，不需添加溶劑。條件為氯化丙烯0.5 mole，醋酸鈉0.55 mole，碘化四丁基銨0.0025 mole，攪拌速率500 rpm，溫度設定為80 ℃並維持此溫度至反應結束。在此組條件下反應4小時之產率達99 %以上。 至於醋酸丙烯酯之水解合成丙烯醇方面，因為該反應速率很快，所以考慮以較為溫和的條件來生產，以溫度約30 ℃與常壓下來進行反應。適當生產條件為醋酸丙烯酯0.3 mole，氫氧化鈉0.3 mole，水1.8 mole，溫度30 ℃，轉速500 rpm。在此組條件下反應40分鐘後之產率達99 %以上。 The liquid-solid phase transfer catalyzed acetate substitution of allyl chloride to synthesize allyl acetate and the liquid-liquid phase transfer hydrolysis of allyl acetate to synthesizes allyl alcohol were studied. The physical and chemical processes were considered to derive the overall production rate equation of allyl acetate. The factors affecting the production rate of allyl acetate can be inspected with the overall rate equation. They are amounts and structures of phase transfer catalyst, stirring speed and reaction temperature. And the experimental results of the influences of the factors on the production rate of allyl acetate can be explained with the overall rate equation. A set of suitable conditions for producing allyl acetate using three-necked bottle under atmospheric pressure is allyl chloride 0.5 mole, sodium acetate 0.55 mole, allyl acetate 0.5 mole, tetra-n-butyl ammonium iodide 0.025 mole, stirring speed 500 rpm, reaction program as initial temperature 70 ℃, then increasing rate 5 ℃/ 30 min and final temperature 80 ℃ . Under this set of condition, 99 % yield can be achieved within the reaction time of 4 hours. Another set of suitable conditions without solvent for producing allyl acetate using Parr 4564M reactor is stirring speed 500 rpm, allyl chloride 0.5 mole, sodium acetate 0.55 mole, tetra-n-butyl ammonium iodide 0.0025 mole, reaction temperature 80 ℃. Under this set of condition, 99 % yield can be achieved at the reaction time of 4 hours. As for the liquid-liquid phase transfer catalyzed hydrolysis of allyl acetate to synthesize allyl alcohol. A set of the suitable conditions is allyl acetate 0.3 mole, sodium hydroxide 0.3 mole, water 1.8 mole, reaction temperature 30 ℃, stirring speed 500 rpm. Under this set of condition, reaction 40 minutes yield rate achieve 99 %. |
