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

陳彥秀

指導教授 ： 劉陵崗

國立臺灣師範大學/理學院/化學系/碩士(2009年)

摘要

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。

關鍵字

醇的氧化 ； 離子性聚合物

並列摘要

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.

參考文獻

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