研究生: |
許毓容 Hsu, Yu Jung |
---|---|
論文名稱: |
新穎功能性高分子 Poly(Di(pyridin-2-yl)methyl acrylate) (PDPyMA) 的合成以及在異相催化反應的應用 Application of Poly(Di(pyridin-2-yl)methyl acrylate) (PDPyMA) in Heterogeneous Catalysis |
指導教授: |
彭之皓
Peng, Chi How |
口試委員: |
韓建中
陳俊太 彭之皓 |
學位類別: |
碩士 Master |
系所名稱: |
理學院 - 化學系 Department of Chemistry |
論文出版年: | 2015 |
畢業學年度: | 103 |
語文別: | 中文 |
論文頁數: | 122 |
中文關鍵詞: | 功能性高分子 、異相催化劑 、Suzuki-Miyaura 反應 、醇氧化成醛與酮 、Friedel-Crafts烷基化反應 |
外文關鍵詞: | Functional Polymer, Heterogeneous Catalysts, Suzuki-Miyaura Reactions, Oxidation of Primary Alcohol to Aldehyde and Ketone, Friedel-Crafts Alkylations |
相關次數: | 點閱:2 下載:0 |
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我們成功地合成出新穎功能性單體di(pyridin-2-yl)methyl acrylate (DPyMA) 和新穎功能性高分子poly(di(pyridin-2-yl)methyl acrylate) (PDPyMA),PDPyMA可以和不同金屬配位形成異相催化劑,並應用到三種不同類型的催化反應,分別為醇氧化成醛與酮、Suzuki-Miyaura 反應以及Friedel-Crafts烷基化反應。在各反應當中,所使用的催化劑分別為PDPyMA-CuBr2、PDPyMA-Pd(OAc)2和PDPyMA-Cu(OTf)2。
在這些催化反應當中,使用以PDPyMA當作配位基的異相催化劑時,催化活性與使用DPyMA當作配位基的勻相催化劑相差不大,表示以PDPyMA當作催化劑的配位基時,PDPyMA上的吡啶造成的立體阻礙不大。而異相催化劑可以經過簡單過濾後,以乙酸乙酯 (EtOAc) 和水清洗即可回收。催化劑經重複使用十次後,反應效率仍維持一致,且濾液中的金屬含量以ICP-AES檢測後低於0.011 %,表示幾乎沒有金屬離子從催化劑上剝落。因此PDPyMA可做為不同金屬的載體形成異相催化劑並可以重複回收且催化活性不會下降。
The multifunctional plateform of poly(di(pyridin-2-yl)methyl acrylate) (PDPyMA), which can coordinate with different metal ions to form the heterogeneous catalysts for various reactions, was obtained by the free radical polymerization of designed functional monomer of di(pyridin-2-yl)methyl acrylate (DPyMA).
The insoluble powders formed from PDPyMA and metal salts like Pd(OAc)2 and Cu(OTf)2 have been used to catalyze different reactions such as oxidation of primary alcohol to aldehyde and ketone, Suzuki-Miyaura reactions, and Friedel-Crafts alkylations. The performance of these heterogeneous catalysts was similar or only slightly lower than the soluble monomeric complexes that formed by DPyMA and corresponding metal salts, indicating that the steric hindrance caused by polymeric plateform was not significant. The catalysts based on PDPyMA were recycled by simple filtration and rinse with no observable weight loss nor activity decline.
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