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標題: | 兩性雙區塊共聚物擔負金屬錯合物的合成及催化反應之應用 The Synthesis and Catalytic Application of Amphiphilic Diblock Copolymer Supported Metal Complexes |
作者: | Sheng-Hsuan Wei 魏聖軒 |
指導教授: | 劉緒宗(Shiuh-Tzung Liu) |
關鍵字: | 兩性雙區塊共聚物,錯合物,催化, Amphiphilic Diblock Copolymer,Metal Complex,Catalysis, |
出版年 : | 2005 |
學位: | 碩士 |
摘要: | 在本篇論文中,以聚氧乙烯(PEG) (M.W.= 750&2000)作為親水端基團,經過官能基轉換使其成為以醯胺鍵連結的自由基起始劑後。再以原子轉移聚合(ATRP)的方式合成出不同長度的疏水端聚丙烯酸甲酯(PMA)區塊,形成具有狹小分子量分佈性質的兩性雙區塊共聚物。利用1-(3-丙胺)咪唑的胺基與聚乙二醇甲基醚-聚丙烯酸甲酯共聚物中的酯基作用得醯胺產物,以反應時間的長短控制1-(3-丙胺)咪唑修飾於共聚物疏水端的數量,其修飾基團多寡由氫核磁共振光譜積分比計算之。
修飾於共聚物的咪唑基團上的鈷(Co)及錸(Re)等兩金屬,係以金屬前驅物負載於兩性區塊共聚物中。含鈷的錯合物在乙酸乙酯/水兩相系統中以過硫酸氫鉀為氧化劑,於室溫可催化烯類環氧化反應,而且有不錯的催化效果;而含錸的錯合物可在乙酸乙酯/水與二氯甲烷/水兩種兩相系統中,有效地催化環烯類的氧化。此外,兩種金屬的催化劑回收再利用上也得到不錯的成效,可重複使用七次以上且無明顯金屬流失現象。 In this thesis, the hydroxy group of poly(ethylene glycol methyl ether) (M.W.= 750&2000) was transferred to an amide-linkage macroinitiator, as hydrophilic part. The hydrophobic part was introduced by polymerization of methyl acrylate via atom transfer radical polymerization. The obtained amphilic diblock copolymers were in different molecular weights with narrow molecular weight distribution. The ester functionality on poly(methyl acrylate) was modified with 1-(3-aminopropyl) imidazole to introduce the coordinating donors. By reaction time, the number of donors could be controlled. Cobalt and Rhenium were loaded into block copolymers to form polymer bound complexes by coordination with imidazole ligands. The Co complexes can catalyze the olefin epoxidation in ethyl acetate/ water biphase system under room temperature by using KHSO5 as the oxidation agent. On the other hand, the Re complexes showed excellent catalytic activities in both ethyl acetate/ water and dichloromethane/ water systems on the oxidation of cycloolefins. In recycle experiments, catalysts maintain activities after 7 run. |
URI: | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/34947 |
全文授權: | 有償授權 |
顯示於系所單位: | 化學系 |
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