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研究生:羅濟威
研究生(外文):Chi-Wei Lo
論文名稱:利用組合式化學法合成四級銨化觸媒
論文名稱(外文):Synthesis of Quaternary Ammonium Catalyst Using Cmbinatorial Cemistry
指導教授:吳和生吳和生引用關係
指導教授(外文):Ho-Shing Wu
學位類別:碩士
校院名稱:元智大學
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:2003
畢業學年度:91
語文別:中文
論文頁數:93
中文關鍵詞:組合式化學法相間轉移觸媒丙烯化氧化四級銨鹽液-固-液系統
外文關鍵詞:combinatorial chemistryphase transfer catalystallylationoxidationquaternaty ammonium saltliquid-solid-liquid system
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相間轉移催化系統在化學的製程以及工業上,應用十分的廣泛,但由於在觸媒的選用上常常會因反應的不同而必須改變,故本研究嘗試著利用組合式化學法以進行觸媒的製備並尋找出最佳化的條件。在實驗步驟上是利用固相合成方式中的mix-split法來合成。首先選擇5種不同的三級胺和5種環取代數和粒徑的聚苯乙烯擔體來合成25種以聚苯乙烯為擔體之季銨鹽類的相間轉移觸媒分子庫。並利用酚的醚化反應來作為檢測反應。而檢測方法則是利用iterative deconvolution法來檢測。最後我們得到結論:當利用酚的醚化反應做檢測反應時我們可以得到當擔體的環取代數為20%粒徑為0.177-0.25mm時並連結三己基胺所形成的季銨鹽將會是具有最佳催化效果的觸媒;以氯仿作為溶劑更使得反應效果變得更好。接著改變醚化反應的操作變因,轉速500rpm、溫度50℃、氫氧化鈉的增加,以及使油水比為4比1時會有最佳化的反應效果。
至於另一個檢測反應,本實驗選擇了有機反應中最常見的氧化反應來當作檢測反應,經過相同的固相合成後,緊接著利用苯甲醇的氧化反應來進行檢測,結果發現,當溶劑選用正己烷,活性基團選擇三乙基胺,並選用環取代數20%以及選用較小的粒徑mesh 60-80將會有最佳的氧化產率。
This study was tried to prepared the catalyst by using the combinatorial chemistry method and found the optimum conditions. The catalyst was synthesized by mix-split method. A phase transfer catalyst library with 25 kinds of polystyrene-supported quaternary ammonium salt catalyst was synthesized by the reaction of 5 kinds of chloromethlated crosslinked polystyrene with five tert-amines. The allylation of phenol were used as the reactions to screen out the most active catalyst for reaction by using the iterative deconvolution method. For the allylation, it could be have optimization process when chloroform and the most active catalyst were added at the reaction. The most active catalyst meant that triethyl amine was immobilized with several variables (500 rpm, 50oC, increased NaOH concentration and allybromide ratio) in the resin which was 20% ring substitution and 0.177-0.25 mm of pellet size.
The other reaction, we chose oxidation of benzyl alcohol to screen. For oxidation of benzyl alcohol, it could be have optimization process when n-hexane and the most active catalyst were added at the reaction. The most active catalyst meant that triethyl amine was immobilized in the resin which was 20% ring substitution and 0.177-0.25 mm of pellet size.
目錄
中文摘要 I
目錄 II
圖目錄 V
表目錄 VII
符號說明 VIII
第一章 緒論 1
1.1 前言 1
1.2組合式化學之簡介 2
1.2-1 組合式化學技術 2
1.2-2 固相合成法 4
1.2-3 混合-分離合成法 5
1.2-4 平行合成法 6
1.2-5 溶液相合成法 8
1.2-6 液相合成法 9
1.3 高倍速分析 10
1.3-1 On bead screening 11
1.3-2 Deconvolution 11
1.3-3 Iterative deconvolution 11
1.3-4 Positional scanning 13
1.3-5 Orthogonal libraries 14
1.4相間轉移催化技術脂簡介 14
1.4-1原理與機構 15
1.4-2三相相間轉移觸媒之介紹 16
1.4-3固體擔體之介紹 16
1.5實驗動機 17
1.6文獻回顧 20
1.6-1利用組合式化學法尋找最佳化的反應途徑 20
1.6-2利用組合式化學法檢測三相相間轉移觸媒 21
Chapter 2 Experimental 22
2.1 Materials 22
2.2 Experiment of apparatus 24
2.3 Analytical apparatus 24
2.4 Synthesis of quaternary ammonium polystyrene-co -chloromethylstyrene resin 25
2.4-1 Preparation of chloromethylated 25
2.4-2 Synthesis of the phase transfer catalyst library 27
2.5 Screen of the triphase catalyst for allylation of phenol 28
2.5-1 Screening out solvent from the most active sub-library 28
2.5-2 Screening of the most active sub-library 28
2.5-3 Screening of the most active catalyst in the library 29
2.5-4 Screening of optimization condition 30
2.6 Screen of the triphase catalyst for oxidation of benzyl
alcohol. 30
2.6-1 Screening out solvent from the most active sub-library 30
2.6-2 Screening out the most active sublibrary 30
2.6-3 Screening out the most active catalyst in the library 31
2.7 Calibration curve 31
2.8 Characterized property of quaternary ammonium poly (styrene-co-chloromethylstyrene) catalyst 34
2.6-1 Ion-exchange capacity by a Volhard methid 34
第三章 理論分析 35
3.1前言 35
3.2原理簡介 35
3.2-1組合式化學法 35
3.2-2高倍速分析方式 36
3.3實驗設計 37
3.3-1利用mix-split法合成樹脂 37
3.3-2利用Iterative deconvolution分析法分析之 39
3.4最佳化反應參數的實驗設計 41
第四章 組合式化學法分析酚丙烯化反應 42
4.1前言 43
4.2兩相反應動力學模式 43
4.3 分析結果與討論 45
4.3-1混合-分離法合成觸媒 45
4.3-1-1對不同烷基的三級胺進行固定化 45
4.3-2-2對不同環取代數以及粒徑進行固定化 46
4.3-2-3對不同粒徑進行固定化 47
4.3-2利用醚化反應對相間轉移觸媒進行檢測 48
4.3-2-1溶劑種類對反應速率的影響 48
4.3-2-2不同活性基團的結構對反應的影響 52
4.3-2-3高分子擔體的影響 54
4.3-3對溴丙烯的醚化反應進行最佳化條件之檢測 56
4.3-3-1觸媒固定化的變因 56
4.3-3-2反應的操作變因 58
4.3-3-2-1攪拌速率的影響 58
4.3-3-2-2溫度的效應 60
4.3-3-2-3鹽量的效應 63
4.3-3-2-4酚量對反應的影響 65
4.3-3-2-5有機相濃度的影響 67
4.3-3-2-6酚與氫氧化鈉的交互作用 69
4.3-4三乙醇胺在不同溶劑下對產率的影響 70
4.4 利用傳統的檢測方式驗證組合式化學 73
4.5結論 74
4.5-1 組合式化學法分析醚化反應之變因 74
4.5-2對溴丙烯的醚化反應進行最佳化的尋求 75
第五章 組合式化學法分析苯甲醇的氧化反應 78
5.1前言 78
5.2 分析結果與討論 80
5.2-1 mix-split 合成法合成觸媒 80
5.2-2 利用苯甲醇的氧化反應對相間轉移觸媒進行檢測 80
5.2-2-1溶劑種類對反應速率的影響 81
5.2-2-2 不同活性基團的結構對反應速率的影響 83
5.2-2-3 高分子擔體的影響 84
5.4 結論 85
第六章 總結與未來展望 86
6.1總結 86
6.2未來展望 87
參考資料 88
附錄 93
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