臺灣博碩士論文加值系統

本論文所研究之反應系統為醇類對鹵烷(或鹵烯)在鹼性水溶液/有機溶劑中，藉由相間轉移觸媒之催化促進醚化反應。產物單醚類與雙醚類化合物之主要用途為液晶材料、香料、半導體晶片之環氧接著劑、光阻劑等。
在本研究過程中，主要探討利用相間轉移觸媒技術進行醚類的合成反應、反應機制、動力學、質傳效應、活性觸媒分佈及其理論之相關問題。由實驗中可獲得結論如下：
(a) 在本論文中，兩個主題之反應均為二次取代的醚化反應，第一部份之產物為4,4’-雙(氯甲基)-1,1’-聯苯的衍生物4,4’-(丁烷氧基甲基氯甲基)-1,1’-聯苯(4,4’-(butoxymethylchloromethyl)- 1,1’-biphenyl)，4,4’-雙(丁烷氧基甲基)-1,1’-聯苯(4,4’-bis(butoxymethyl)-1,1’-biphenyl)，4,4’-(氯甲基苯氧基甲基)-1,1’-聯苯(4,4’-(chloromethylphenoxymethyl)-1,1’-biphenyl)，4,4’-雙(苯氧基甲基)-1,1’-聯苯(4,4’-bis(phenoxymethyl)-1,1’-biphenyl)，包含單醚類與雙醚類產物皆可由反應中獲得。然而第二部份只可獲得雙醚類產物雙酚A雙丙烯醚(bisphenol A diallyl ether)。此顯示其第二步驟的有機相反應之反應速率極快。
(b) 以加壓管柱層析法利用適當的吸附劑及沖提劑，可成奶擢鰳瞻狗竄蚺妓ㄙ哄C
(c) 活性觸媒之兩相質量傳送皆具有臨界值，顯示所有的反應系統皆為萃取反應機制，當攪拌速率高於臨界值時，為有機相化學反應控制。
(d) 相間轉移觸媒技術可溫和且有效地加速兩液相醚化反應，尤其對於合成雙酚A雙丙烯醚之反應系統。在低溫操作下能夠避免高溫所導致的分子內重排副反應之發生。
(e) 利用擬穩態理論與雙膜理論可成它a推導出反應機制之數理模型。配合實驗數據與電腦程式之輔助，可成巨D取視反應速率常數(apparent rate constant)。
(f) 在動力學結果可知：增加觸媒用量、溫度與觸媒陽離子之油溶性及對稱性可加速度應。鹼鹽具有降低活性觸媒之水合效應與促進水相反應物的溶解與離子化等效用，但是在第一部份酚(phenol)與4,4’-雙(氯甲基)-1,1’-聯苯(4,4’-bis(chloromethyl)-1,1’-biphenyl)之反應與第二部份之反應系統中，過多的鹼鹽添加反而會使水相反應物析出，變為反應速率較低之固液形態，故其鹼鹽的添加有著最適值的存在。
(g) 利用添加適當的立體穩定劑，聚合所得之高分子擔體有著相當均一之粒徑。而於固定化後所得之三相觸媒，有著不錯催化特性及重覆使用性。
(h) 藉由便宜的4,4’-雙(氯甲基)-1,1’-聯苯(4,4’-bis(chloromethyl)-1,1’- biphenyl)與三級胺(tertiary amine)反應，製備所得之多活性點相間轉移觸媒，其於兩大反應系統內，皆有著相當優異之催化效能。
(i) 在催化反應系統內，藉由界面活性劑或共觸媒之添加將有效的更加助益反應之進行。

In this dissertation, the reaction of alcohol with haloalkane or haloalkene to synthesize ether compounds in a two-phase alkaline solution of KOH/organic solvent medium under phase transfer catalysis (PTC) was investigated. Those products from PTC reaction can be used as the liquid crystal materials, perfume, epoxidised adhesives for semiconductor chips, and photoresists etc. in industries.
The primary purposes of this dissertation are to study the phase-transfer catalytic reaction for ether compounds, reaction mechanism, kinetics, mass transfer effect, distribution of active catalyst and other related theories. Several rigid conclusions were obtained from the experimental results.
(a) In the present study, systems are confined within the di-substituted etherification reactions. In part 1, both mono-substituted and di-substituted of 4,4’-bis(chloromethyl)-1,1’- biphenyl-derived were obtained. However, only di-substituted product, bisphenol A diallyl ether, was obtained in part 2 reaction system. The result indicates that a rapid second organic reaction in the organic phase for the second reaction system.
(b) High purity products were obtained by using the pressurized column chromatography with appropriate choosing eluent species and adsorbing materials.
(c) A threshold value of two-phase mass-transfer rate would exist in the phase transfer catalytic reactions. All reaction systems were identified as the extraction mechanism. The reaction was organic reaction controlled when the agitation speed was higher than the threshold value.
(d) The biphasic etherification reactions were effectively enhanced in the mild conditions via phase-transfer catalysis, especially for the reaction system of bisphenol A diallyl ether. The etherification via phase-transfer catalyst could operate at lower temperature to avoid intramolecular rearrangement, which usually occurs at higher temperature.
(e) As the results of experiments, the rate was increased with the increase in amount of catalyst, temperature, as well as organophilicity and symmetry of catalyst cation. Alkali salt is used to decrease solvation of active catalyst. It enhances the solubility and ionization of the aqueous reactants. However, the aqueous reactants were precipitated by using larger amount of alkali salt in the reaction of phenol with 4,4’-bis(chloromethyl)-1,1’-biphenyl in part 1 and all reaction systems in part 2. For this reason, the addition of alkali salt exist an optimum value.
(f) The pseudo steady-state hypothesis (PSSH) and two-film theory are successfully applied to develop the reaction mechanism. The apparent rate constants were determined from the experimental data in conjunction with the computer program.
(g) The uniform polymer-supported particles were obtained by adding the steric stabilizer during polymerization. After tertiary amines were immobilized on polymer supported particles, the tirphase catalysts perform excellent catalytic activity and reusability.
(h) The synthesized multi-site phase-transfer catalysts, which were obtained from low cost 4,4’-bis(chloromethyl)-1,1’-bipehnyl with tertiary amines, show superior catalytic reactivity in both reaction systems.
(i) In catalytic reaction systems, the reaction is greatly enhanced with the addition of surfactants or co-catalyst.

誌謝 i
中文摘要 iii
英文摘要 v
目錄 vii
表目錄 xi
圖目錄 xiv
符號說明 xxvii
第一章 緒論
§1.1 前言 1
§1.2 相間轉移觸媒之源起與分類 3
§1.3 相間轉移觸媒之反應機構 9
§1.4 醚類之應用與合成緣起 12
§1.5 研究目的及大綱 15
第二章 相間轉移觸媒催化反應合成醚類(Ⅰ)-以正丁醇與4,4’-雙(氯甲基)- 1,1’-聯苯合成4,4’-雙(丁烷氧基甲基)-1,1’-聯苯
§2.1 實驗藥品 17
§2.2 實驗設備 20
§2.3 分析儀器及條件 22
§2.4 產物的製備與純化 22
§2.5 產物的分析與鑑定 27
§2.6 校正曲線與反應質量守恆檢驗 36
§2.7 理論與反應機構 40
§2.8 反應機構之推導 44
§2.9 動力學因素之探討 50
§2.10 觸媒與活性觸媒之探討 93
第三章 相間轉移觸媒催化反應合成醚類(Ⅰ)-以三相觸媒促進正丁醇與4,4’-雙(氯甲基)-1,1’-聯苯合成4,4’-雙(丁烷氧基甲基)-1,1’-聯苯
§3.1 實驗藥品 108
§3.2 實驗設備 110
§3.3 分析儀器及條件 110
§3.4 高分子觸媒載體之合成法 110
§3.5 高分子擔體合成及觸媒固定化之實驗步驟 112
§3.6 三相觸媒活性點之檢測 117
§3.7 三相觸媒反應之動力式推導 120
§3.8 動力學因素之探討 125
第四章 相間轉移觸媒催化反應合成醚類(Ⅰ)-以酚與4,4’-雙(氯甲基)-1,1’-聯苯合成4,4’-雙(苯氧基甲基)-1,1’-聯苯
§4.1 實驗藥品 154
§4.2 實驗設備 156
§4.3 分析儀器及條件 156
§4.4 產物的製備與純化 156
§4.5 產物的分析與鑑定 158
§4.6 校正曲線與反應質量守恆檢驗 167
§4.7 理論與反應機構 170
§4.8 反應機構之推導 176
§4.9 動力學因素之探討 180
第五章 相間轉移觸媒催化反應合成醚類(Ⅰ)-以多活性點相間轉移觸媒促進正丁醇與4,4’-雙(氯甲基)-1,1’-聯苯合成4,4’-雙(丁烷氧基甲基)- 1,1’-聯苯
§5.1 實驗藥品 216
§5.2 實驗設備 217
§5.3 分析儀器及條件 217
§5.4 多活性點相間轉移觸媒之合成 217
§5.5 多活性點相間轉移觸媒之分析與鑑定 218
§5.6 理論與反應機構 226
§5.7 反應機構之推導 228
§5.8 動力學因素之探討 234
第六章 相間轉移觸媒催化反應合成醚類(Ⅱ)-以雙酚A與溴丙烯合成雙酚A雙丙烯醚
§6.1 實驗藥品 268
§6.2 實驗設備 269
§6.3 分析儀器及條件 269
§6.4 產物的製備與純化 269
§6.5 產物的分析與鑑定 270
§6.6 校正曲線與反應質量守恆檢驗 271
§6.7 反應機構之推導 280
§6.8 動力學因素之探討 284
第七章 相間轉移觸媒催化反應合成醚類(Ⅱ)-以多活性點相間轉移觸媒促進雙酚A與溴丙烯合成雙酚A雙丙烯醚
§7.1 實驗藥品 322
§7.2 實驗設備 324
§7.3 分析儀器及條件 324
§7.4 多活性點相間轉移觸媒之合成 324
§7.5 多活性點相間轉移觸媒之分析與鑑定 324
§7.6 反應機構之推導 324
§7.7 動力學因素之探討 329
第八章 結論與未來展望
§8.1 各反應系統之結論 369
§8.2 未來展望 372
附錄 A 福傳程式 376
參考文獻 378
自述 390

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