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研究生:王毓嵐
研究生(外文):Yu-Lan Wang
論文名稱:液-液相相間轉移催化2-甲氧基-4-丙烯基酚之苯甲化反應研究
論文名稱(外文):Benzylation of 2-Methoxy-4-propenylphenol via Liquid-Liquid Phase-Transfer Catalysis
指導教授:楊鴻銘楊鴻銘引用關係
指導教授(外文):Hung-Ming Yang
學位類別:碩士
校院名稱:國立中興大學
系所名稱:化學工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2005
畢業學年度:93
語文別:中文
論文頁數:116
中文關鍵詞:相間轉移催化反應液-液相界面張力反應動力學醚化反應苯甲基2-甲氧基-4-丙烯基苯基醚氯化甲基三辛基銨
外文關鍵詞:Phase-transfer catalysisliquid-kiquid phaseBenzyl 2-methoxy-4- propenylphenyl etherAliquat 336Kinticsinterfacial tensio
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本研究探討的是以液液相間轉移催化2-甲氧基-4-丙烯基酚之苯甲化反應。操作條件有:觸媒種類效應、觸媒添加量效應、水量添加效應、不同反應溫度效應、不同攪拌速率效應、不同反應物比例效應以及不同溶劑效應等。另外還探討了導電度與界面張力的現象,並且進ㄧ步去研究反應機構及求得其反應動力學的速率常數。
隨著觸媒Aliquat 336和水相反應物的添加量增加,其界面張力也會跟著下降,這是因為其結構都與界面活性劑相似的關係。從實驗結果來看,加入相間轉移觸媒對反應速率的提升是很有幫助的,在不添加觸媒時其反應性是相當低的,當添加Aliquat 336的量增加時,反應速率也會隨之上升,並且可以用虛擬一階方式來描寫此一反應。在液-液相系統中,利用氯化甲基三辛基銨親油的特性,可將水相反應物質傳到油相,當轉速超過50 rpm時便可忽略兩相間之質傳阻力。而NaOH的量對系統反應是沒影響的。在不同有機溶劑的影響方面,使用MIBK在30分鐘後其產率便可達到86%,而使用極性較低之Hexane在30分鐘後產率只能大約60%。由實驗結果顯示最佳的2-甲氧基-4-丙烯基酚鈉鹽使用量為為水相反應物與2-甲氧基-4-丙烯基酚鈉鹽的莫耳比例為1.5,在45分鐘後產率可達84%。在這個系統內最適的水量為55毫升,過多和過少的水量都對反應有不好的影響。
在不同觸媒活性比較方面,其結果是Aliquat 336>TBPB>BTBAB>TBAI>TBAB>PEG400>PEG600,求得的活化能為Aliquat 336:17.522(kcal/mol);TBPB:21.652(kcal/mol);BTBAB:15.996(kcal/mol);TBAI :16.055(kcal/mol);TBAB:14.665(kcal/mol)。
The present study is to investigate the benzylation of 2-methoxy-4 -propenylphenol via liquid-liquid phase-transfer catalysis. The operating conditions for investigation include agitation speed, reaction temperatures, catalyst amounts, type of catalyst, type of organic solvent, molar ration of reactant, types of solvents, and so on. The electric conductivity and interfacial tension were also measured. The reaction mechanism and apparent reaction rate constants were obtained from the experimental results.
The interfacial tension of two phases will be dreacreased with Aliquat 336 adding to the organic phase and sodium 2-methoxy-4- propenylphenoxide in the aqueous phase. From the experimental data shown, the reaction rate was greatly enhanced by applying phase-transfer catalysts. Without the addition of any catalyst, the product yield is very low, while the reaction rate increases with increasing the amount of Aliquat 336 catalyst added, and the overall reaction rate can be well described by the pseudo-first-order kinetics. In a liquid-liquid phase transfer syatem, the aqueous phase reactant can be transported from aqueous-phase to organic-phase by the hydrophobic characters of catalyst Aliquat 336. When the agitation speed exceeds 50 rpm, the mass transfer resistance at the liquid-liquid interface can be ignored, and NaOH cannot influence the reaction rate. Effects of different organic solvents for Aliquat 336 were carried out, and above 86% of yield of benzyl 2-methoxy-4- propenylphenyl ether is easily achieved within 30 minutes using MIBK as the solvent, and above 60% of yield of product is obtained within 30 minutes using hexane as the solvent. An optimal quantity of sodium 2-methoxy-4- propenylphenoxide is located on 1.5 of the molar ratio of 2-methoxy-4-propenylphenoxide to benzyl bromide to give above 84% of yield of benzyl 2-methoxy-4-propylphenyl ether is within 30 minutes. The best condition is 55 ml of water in this system, neither much more nor less use of water is good for this system.
Different phase-transfer catalysts were employed to compare their catalytic efficiency, and the reactivity order was found :Aliquat 336>TBPB>BTBAB>TBAI>TBAB>PEG400>PEG600. The activation energies for five catalysts were:Aliquat 336:17.522(kcal/mol);TBPB:21.652(kcal/mol);BTBAB:15.996(kcal/mol);TBAI :16.055(kcal/mol);TBAB:14.665(kcal/mol)
中文摘要-------------------------------------------------------------------------- Ⅰ
英文摘要-------------------------------------------------------------------------- Ⅱ
誌謝-------------------------------------------------------------------------------
目錄-------------------------------------------------------------------------------- IV
V
圖目錄 --------------------------------------------------------------------------- VIII
表目錄----------------------------------------------------------------------------- X
符號說明-------------------------------------------------------------------------- XI
第一章 緒論------------------------------------------------------------------ 1
1.1 前言------------------------------------------------------------- 1
1.2 相間轉移催化反應------------------------------------------- 2
1.2-1 相間轉移觸媒催化技術--------------------------- 2
1.2-2 液-液相反應系統----------------------------------- 5
1.2-3 界面催化反應--------------------------------------- 13
1.3 液-液相催化反應文獻回顧-------------------------------- 17
1.3-1液-液相催化反應回顧-------------------------------- 17
1.4 醚化反應------------------------------------------------------- 19
1.4-1醚類的製備-------------------------------------------- 19
1.4-2醚類的相間轉移催化合成-------------------------- 23
1.5 研究目的與研究方法---------------------------------------- 25
第二章 實驗部分------------------------------------------------------------ 28
2.1 實驗藥品------------------------------------------------------- 28
2.2 分析儀器------------------------------------------------------ 29
2.3 實驗裝置------------------------------------------------------ 30
2.4 產物之合成--------------------------------------------------- 31
2.5 校正曲線------------------------------------------------------- 31
2.6 反應動力實驗步驟------------------------------------------- 32
2.7 液-液相界面界面張力------------------------------------- 32
2.8 兩液相導電度測量------------------------------------------- 33
第三章 反應動力模式--------------------------------------------------------- 36
3.1. 液-液相催化醚化反應機制--------------------------------- 36
3.2. 批式反應器之反應動力模式推導------------------------- 36
弟四章 實驗結果與討論--------- ------------------------------------------------ 41
4.1 液-液相界面特性分析--------------------------------------- 41
4.1-1界面張力分析----------------------------------------- 41
4.1-2比導電度分析------------------------------------------ 48
4.1-3不同觸媒量比導電度--------------------------------- 48
4.1-4不同觸媒比導電度分析------------------------------ 52
4.1-5不同溶劑比導電度影響----------------------------- 56
4.1-6添加不同鹽類對比導電度影響--------------------- 60
4.1-7添加不同NaI量對導電度影響--------------------- 61
4.2 不同轉速效應------------------------------------------------- 66
4.3 不同相間轉移觸媒對催化醚化反應之效應------------- 70
4.3-1觸媒量之效應----------------------------------------- 73
4.4 溶劑種類對催化醚化反應之效應------------------------- 78
4.4-1不同溶劑不同溫度之催化效應--------------------- 81
4.5 反應物量對催化醚化反應之影響------------------------- 88
4.5-1不同水量對催化醚化反應之效應------------------ 88
4.6 溫度對催化醚化反應之效應------------------------------- 95
4.7 添加鹽類對催化醚化反應之效應------------------------- 103
4.7-1 NaI添加量對催化醚化反應之影響--------------
4.7-2NaOH添加量對催化醚化反應之影響------------ 103
107
第五章 結論---------------------------------------------------------------------
參考文獻---------------------------------------------------------------------------
附 錄---------------------------------------------------------------------------
A.產物 苯甲基2-甲氧基-4-丙烯基苯基醚1HNMR圖譜---------- 109
112
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116
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