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研究生: 陳靜君
Chen, Ching-Chun
論文名稱: 冠狀醚於高分子聚合及醛醇縮合催化反應與離子輸送之應用
application of Crown Ethers in Polymerization, Aldol Condensation and Ion Transport
指導教授: 施正雄
Shih, Jeng-Shong
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
畢業學年度: 82
語文別: 中文
論文頁數: 123
中文關鍵詞: 冠狀醚離子輸送
論文種類: 學術論文
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  • 本研究利用各種冠狀醚(crown ether)如18冠6(18 crown 6)、單苯15冠5(monobenz0 15 crown 5)及12冠4 (12 crown 4 )做相轉移催化劑以催化甲基丙烯酸甲酯(methyl methhacrylate)烯類單體陰離子聚合反應(anionic polymerization)及促進醛醇縮合(Aldol condensation)反應並合成長鏈的羧基冠狀醚如癸烷羧基雙苯16冠5 (2-(sym-dibenz0-16-crown-5-oxy) dodecanoic aci )作為離子輸送載體(Ion transport carrier, Ionophores )以經液態膜輸送各種金屬離子及氨基酸離子。
    在甲基丙烯酸甲酯的陰離子聚合研究反應中,起始劑用醯胺鈉(sodium amide),並加入各種冠狀醚與起始劑之鈉離子發生錯合反應。而使起始劑在有機相中的溶解度及活性大為增強進而提高了甲基丙烯酸甲酯的聚合速率,在各種冠狀醚中,以15冠5的催化效果最佳,其催化效果的順序為:15C5>B15C5>18C6>12C4,在本研究中還探討起使劑種類及濃度效應,冠狀醚濃度效應,溫度效應及溶劑種類效應,並利用GPC (Gel permeation chromatography)液體層析探討此高分子聚合所得聚合物之分子量。
    在離子輸送研究方面,主要是合成長鏈的羧基冠狀醚(C10H21DB16C5COOH),癸烷羧基雙苯16冠5並作為液態膜離子輸送載體。實驗發現,此長鏈羧基冠狀醚(C10H21DB16C5COOH)對鉀離子的輸送比羧基冠狀醚DB16C5COOH及無羧基冠狀醚B15C5都來的有效。在本研究中探討此長鏈羧基冠狀醚對各種金屬離子如鹼金屬、鹼士金屬及過渡金屬與對胺基酸鈉鹽的輸送,亦研究水溶液陰離子及pH值對金屬離子輸送影響。發現來源層的鹼性越大或接受層的pH值愈小其傳輸的效果愈好,由這些實驗結果本研究提出一可能的長鏈羧基冠狀醚離子輸送機構。
    在本研究中,各種冠狀醚用來做催化劑(catalysts)促進苯乙醛及氫氧化物的醛醇縮合反應,本研究發現隨著溫度及溶劑極性的升高,此催化反應的產率及速率也升高,除此之外氫氧化物及催化劑冠狀醚的種類與冠狀醚的濃度,對反應的進行也有很大的影響。在本實驗中發現氫氧化物在有冠狀醚的催化下其反應的效果為NaOH>KOH>LiOH,而作為催化劑的各種冠狀醚催化反應進行的順序為15C5>B25C5>18C6>12C4。

    Crown ethers, e.p.18-crown-6 (18C6), monobenzo-15-crown-5 (B15c5) and 12-crown-4 (12C4), were applied as phase transfer catalysts for anionic polymerization of methyl methacrylate and Aldol condensation of phenyl acetaldehyde Lariat carboxylate crown ether, e,p. 2-(sym-dibenzo-16-crown-5oxy) dodecanoic acid (C10 H21 DB16C5 COOH), was synthesized and applied as ion transport carrier (Ionophore) for various metals ions and amino acids.
    The solubility and activity of sodium amide (NaNH2) as an initaitor can be enhanced in presence of crown ethers which were able to complex with sodium ion of initator adn thus promote the anionic polymeriation of methy1 methacrylate in organic phase the catalytic ability of crown cthers, the 15 crown5 seems to be the best one, are in the order:15C5>B15C5>18C6>12C4.Effects of initiators, concentration of crown ethers, temperature and solvents on the polymerization of methyl methacrylate were also investigated and discussed the molecular weight of polymethyl methacrylate was determined with GPC (Gel permeation chromatography) method.
    The lariat carboxylate crown ether alkyl substituted 2-(sym-dibenzxo-16-crown-5-oxy) was synthesized and applied as an ion transport carrier through liquid membrane for various metal ions such as alkali, alkali earth and transition metal ions and amino acid anions. the lariat carboxylate crown ether C10H21DB16C5COOH shhowed better ion transport ability than DB16C5COOH and B15C5 Effects of anion and pH in source layer were investigated An ion transport mechanism is proposed which included [OH-] and[H+] is strongly depended on the pH values of both source and target layer.
    Various crown ethers were also applied catalysts for Aldol condensation of phenyl acetaldehyde with hydroxide (MOH). The elevation of temperature the increase in polarity of the reation solvent resulted in the increase of the reation yield. Effects of hydroxide and crown ethers were also investigated The reactive ability of hydroxide with 15 crown 5 as a catalyst are in the order: NaOH>KOH>LiOH.The Catalytic ability of various crown ethers for the condensation with NaOH as a reactant are in the order:15C5>B15C5>18C6>12C4.

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