研究生: |
陳彥秀 |
---|---|
論文名稱: |
含過釕酸咪唑共聚合物在催化醇之部分氧化反應上的應用 Partial Oxidation of Alcohols Mediated by Immobilized Perruthenate on Polyimidazolium Materials |
指導教授: |
劉陵崗
Liu, Ling-Kang |
學位類別: |
碩士 Master |
系所名稱: |
化學系 Department of Chemistry |
論文出版年: | 2009 |
畢業學年度: | 97 |
語文別: | 中文 |
論文頁數: | 52 |
中文關鍵詞: | 醇的氧化 、離子性聚合物 |
論文種類: | 學術論文 |
相關次數: | 點閱:116 下載:0 |
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我們設計出一個催化劑,以乙烯吡咯酮(NVP)聚合物當做基底,結合了來自[VBIM][Cl]的離子液體單元,使共聚合物成為一個高極性的介質,以幫助催化反應的進行。
上述的共聚合物是利用自由基聚合反應來合成的,將不同比例[VBIM][Cl]的單體與乙烯吡咯酮的單體,利用AIBN當引發劑,在甲醇中加熱,60 ℃之下,反應16小時,即可得到共聚合物。最後共聚合物上的Cl-陰離子再以陰離子交換方式轉化成為RuO4-陰離子,就可得到催化劑Ru-1 ~ Ru-4。
過釕酸根(RuO4-)是一個已知的氧化劑。我們將過釕酸根固定在含離子液體的共聚合物上,並將之拿來進行部分氧化反應,期許此類催化劑能應用在使苯甲醇轉換成苯甲醛的部分氧化上。
我們微調了一些參數,使反應轉換率和反應選擇性變好;我們也選擇了NaOCl水溶液來當成最終氧化劑,讓反應後低價Ru氧化回補成為RuO4-,以維持很好的催化性能。
The polymer supported ionic liquid, as derived from the 1-vinyl-3-butylimidazolium chloride ([VBIM][Cl]) monomer, incorporates a very high polarity in the polymer skeleton, which is applied in this work as a support for the oxidation catalyst. The polymers were synthesized by free radical copolymerization of the [VBIM][Cl] monomer and the N-vinyl-2-pyrrolidone (NVP) monomer using azobisisobutyronitrile (AIBN) as the initiator at 60 ℃ for 16 h in methanol. The Cl- anions in polymer were then exchanged with the RuO4- anions. A RuO4- moiety was a known oxidizing reagent and it is the goal of this thesis to see if the RuO4- immobilized on the polymer supported ionic liquid could be made catalytic for partial oxidation. The polymer was used towards the selective oxidation of benzyl alcohol to benzyl aldehyde. A number of parameters were fine-tuned, for instance, the selection of aqueous NaOCl as the ultimate oxidizing reagent in order to convert the lower valent Ru back to RuO4- on polymer during the catalytic cycle so that the increase of reactivity and selectivity was achieved.
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