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研究生:劉漢章
研究生(外文):Han-Chang Liu
論文名稱:合成鄰-羥基苯甲酸苯甲酯之固-液相相間轉移催化反應動力學研究
論文名稱(外文):Kinetic Study of Synthesizing o-Hydroxybenzoic Acid Benzyl Ester via Solid-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:2002
畢業學年度:90
語文別:中文
論文頁數:149
中文關鍵詞:相間轉移觸媒羧酸化鄰-羥基苯甲酸苯甲酯溴化四丁基銨
外文關鍵詞:Solid-liquid systemcarboxylationbenzyl salicylatePhase-transfer catalyst
相關次數:
  • 被引用被引用:1
  • 點閱點閱:155
  • 評分評分:
  • 下載下載:14
  • 收藏至我的研究室書目清單書目收藏:0
摘要
鄰-羥基苯甲酸苯甲酯可作為芳香劑及溶劑也可作為油溶性遮陽
劑。本研究是在固-液相中合成鄰-羥基苯甲酸苯甲酯,在反應系統中,
除了兩相反應物因素外,各項探討的變因包括:攪拌效應、觸媒添加
量效應、水量添加效應、有機溶劑種類效應、觸媒種類效應、溫度效
應等,並進一步研究反應機構及求得反應動力學速率常數。其主要內
容分為兩個部分,結果如下:
在四級銨鹽系統中,鄰-羥基苯甲酸鈉與溴化苯甲基在固-液相系統
中反應生成鄰-羥基苯甲酸苯甲酯,反應過程中相間轉移觸媒(TBAB)
和鄰-羥基苯甲酸鈉形成的觸媒中間體(Ph(OH)COOQ)也會被探討。實
驗結果:觸媒中間體在有機相中的濃度愈高則反應速率愈快。當攪拌
速率超過250 rpm 時,固-液相界面之間的質傳阻力可以忽略不計。不
同觸媒反應活性大小為TBAB@ TBAI>BTBAB@ TBPB >Aliquat 336 >
TBAHS >PEG1500 。水量愈多則反應速率愈慢。實驗結果可以用虛擬
一階方程式完整描述此一系統。經Arrhenius’s 方程式計算出,以溴化
四丁基銨為觸媒,氯苯溶劑中得到的視反應活化能為62.52 kJ/mol 。
另外為了考量四級銨鹽在高溫強鹼環境下可能會分解成三級胺而
影響活性,故考慮用較低廉的三級胺來進行溴化苯甲基之羧酸化反應。
三級胺會原地(in-situ)形成四級銨鹽後才具有催化能力,以三丁基胺的
催化能力較佳可達85 ﹪產率,此外添加碘離子一開始有助於反應速
率,到了一定量後會毒害觸媒,實驗結果,在氯苯溶劑中本質反應活化
能為88.80 kJ/mol 。整個三丁基胺反應可用下面式子描述。

- III -
In the present study, the kinetics of synthesizing benzyl salicylate,
which is used in perfume fixative, solvent for synthetic musk, sun-screening
lotions, and soap odorant, etc., from the carboxylation of benzyl
bromide via solid-liquid phase-transfer catalysis was investigated. The
operating conditions for investigation include agitation speeds 、reaction
temperatures 、catalyst amounts 、types of solvents 、molar ratio of reactants 、
type of phase-transfer catalysts 、volume ratio of aqueous to solvent, and so
on. The reaction mechanism and apparent reaction rate constants were
obtained from the experimental results.
In quaternary ammonium salts system, the product selectivity and kinetics
of sodium salicylate with benzyl bromide to produce benzyl salicylate via
solid-liquid phase-transfer catalysis were investigated. The behavior of
phase-transfer catalytic intermediate in the solid-liquid system was
explored.The concentraction of catalytic intermediate (Ph(OH)COOQ)
increased as increasing molar quantity of catalyst used after induction
period and has greater solubility in organic solvent and mostly exists as the
ion-pair, thus enhancing the intrinsic organic reaction effectively. When the
agitation speed exceeds 250 rpm, the mass transfer resistance at the
solid-liquid interface can be ignored. Different phase-transfer catalysts were
employed to compare their catalytic efficiency : TBAB @ TBAI >
BTBAB @ PBPB >Aliquat 336 >TBAHS >PEG1500.

- VI -
目錄
中文摘要----------------------------------------------------------------------Ⅰ
英文摘要----------------------------------------------------------------------Ⅲ
誌謝----------------------------------------------------------------------------Ⅴ
目錄----------------------------------------------------------------------------Ⅵ
圖目錄------------------------------------------------------------------------Ⅸ
表目錄-------------------------------------------------------------------------ⅩⅣ
符號說明----------------------------------------------------------------------ⅩⅤ
第一章 緒論--------------------------------------------------------------- 1
1.1. 前言----------------------------------------------------------- 1
1.2.相間轉移催化反應簡介----------------------------------- 1
1.3.固-液相反應------------------------------------------------- 7
1.3-1 皇冠醚與四級鹽類-------------------------------- 7
1.3-2 反應機構回顧-------------------------------------- 9
1.3-3 反應動力學模式回顧----------------------------- 15
1.4.相間轉移催化酯化反應----------------------------------- 19
1.5.本研究之目的與研究方法-------------------------------- 21
第二章 實驗部分--------------------------------------------------------- 26
2.1. 實驗藥品----------------------------------------------------- 26
2.2.實驗裝置與分析儀器------------------------------------- 27
2.3.產物之合成-------------------------------------------------- 28
2.4.觸媒中間體之製備----------------------------------------- 28
2.5.電導度計之校正-------------------------------------------- 29
2.6.校正曲線----------------------------------------------------- 30
2.7.實驗步驟----------------------------------------------------- 36
第三章 鄰-羥基苯甲酸鈉及四級銨鹽在有機相之特性----------- 38
3.1.固相鹽類之表面解離反應-------------------------------- 38
- VII -
3.2.有機溶劑中之鹽類導電分析----------------------------- 38
3.2-1 添加四級銨鹽之影響---------------------------- 39
3.2-2 溶劑極性對鹽類解離之影響------------------- 47
3.3 觸媒中間體在溶劑之導電度分析----------------------- 49
第四章 以四級銨鹽催化鄰-羥基苯甲酸酯化反應----------------- 50
4.1.前言----------------------------------------------------------- 50
4.2.反應動力模式推導----------------------------------------- 51
4.3.實驗結果與討論-------------------------------------------- 54
4.3-1 攪拌速率的影響---------------------------------- 54
4.3-2 水用量效應---------------------------------------- 56
4.3-3 觸媒添加量的影響------------------------------- 59
4.3-4 觸媒中間體之生成------------------------------- 64
4.3-5 有機相本質反應---------------------------------- 64
4.3-6 鄰-羥基苯甲酸不同量的影響------------------ 67
4.3-7 溴化苯甲基不同量------------------------------- 67
4.3-8 觸媒結構的影響---------------------------------- 72
4.3-9 溶劑的影響---------------------------------------- 75
4.3-10 鹽類效應------------------------------------------- 78
4.3-11 溫度的影響---------------------------------------- 83
4.3-12 視活化能計算------------------------------------- 83
4.4.結論----------------------------------------------------------- 109
第五章 以三級胺催化鄰-羥基苯甲酸酯化反應-------------------- 110
5.1.前言----------------------------------------------------------- 110
5.2.反應動力模式推導----------------------------------------- 111
5.3.實驗結果與討論-------------------------------------------- 115
5.3-1 三級胺與溴化苯甲基之反應------------------- 115
5.3-2 觸媒中間體之變化行為------------------------- 120
5.3-3 不同溶劑對反應的影響------------------------- 123
5.3-4 溴化苯甲基添加量的影響---------------------- 123
5.3-5 攪拌速率的影響---------------------------------- 127
5.3-6 鹽類添加的影響---------------------------------- 127
5.3-7 溫度的影響---------------------------------------- 130
5.3-8 活化能計算---------------------------------------- 130
5.4.結論----------------------------------------------------------- 138
第六章 總結--------------------------------------------------------------- 140
參考文獻---------------------------------------------------------------------- 143
附錄---------------------------------------------------------------------------- 147
1.鄰-羥基苯甲酸苯甲酯之1 HNMR 圖譜---------------- 147
2.鄰-羥基苯甲酸化四丁基銨1 HNMR 圖譜------------- 148
3.鄰-羥基苯甲酸化苯甲基三丁基銨1 HNMR 圖譜---- 149

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