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研究生:許毓容
研究生(外文):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
論文名稱(外文):Application of Poly(Di(pyridin-2-yl)methyl acrylate) (PDPyMA) in Heterogeneous Catalysis
指導教授:彭之皓
指導教授(外文):Peng, Chi How
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
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 PolymerHeterogeneous CatalystsSuzuki-Miyaura ReactionsOxidation of Primary Alcohol to Aldehyde and KetoneFriedel-Crafts Alkylations
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  • 被引用被引用:0
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  • 下載下載:11
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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.

摘要 I
Abstract II
謝誌 III
目錄 IV
圖次 VI
式次 XI
表次 XII
第一章 緒論 1
1.1 前言 1
1.1.1 刺激感應型高分子 (Stimuli-Responsive Polymers) 3
1.1.2 自我修復高分子 (Self-Healing Polymers) 6
1.1.3 導電高分子 (Conductive Polymers) 9
1.1.4 金屬高分子 (Metallopolymers) 11
第二章 新穎功能性高分子的合成 14
2.1 研究動機 14
2.2 新穎功能性單體的製備 16
2.3 新穎功能性單體合成金屬錯合物 17
2.4 新穎功能性高分子的製備 25
2.5 新穎功能性高分子合成金屬錯合物 27
2.6 總結 29
第三章 新穎功能性高分子的應用 30
3.1 前言 30
3.2 醇氧化醛及酮 Oxidation of Alcohols to Aldehydes and Ketones 32
3.3 Suzuki-Miyaura Reaction 38
3.4 Friedel-Crafts Alkylations 45
3.5 總結 48
第四章 Di(pyridin-2-yl)methyl acrylate (DPyMA) 作為銅金屬配位基催化原子轉移自由基聚合 50
4.1 前言 50
4.2 研究動機 56
4.3 以 Di(pyridin-2-yl)methanol (BPyOH) 作為銅金屬配位基催化原子轉移自由基聚合 57
4.4 以 Di(pyridin-2-yl)methyl acrylate (DPyMA) 作為銅金屬配位基催化原子轉移自由基聚合 59
4.5 原子轉移自由基聚合 Di(pyridin-2-yl)methyl acrylate (DPyMA) 67
4.6 總結 71
第五章 實驗步驟及儀器鑑定 72
5.1 藥劑以及儀器 72
5.2 合成及光譜分析 75
5.2.1 Di(pyridin-2-yl)methanol (BPyOH) 的合成115 75
5.2.2 Di(pyridin-2-yl)methyl acrylate (DPyMA) 的合成 76
5.2.3 DPyMA-MX2 錯合物的合成 78
5.2.4 Poly(di(pyridin-2-yl)methyl acrylate) 的合成 78
5.2.5 PDPyMA-MX2 錯合物的合成 78
5.2.6 使用 Catalyst 2 催化醇氧化成醛與酮 79
5.2.7 使用 Catalyst 2 催化 Suzuki–Miyaura reactions 79
5.2.8 使用 Catalyst 3 催化 Friedel-Crafts alkylation 79
5.2.9 以 1H NMR 光譜分析催化反應之產率 80
5.2.10 聚合實驗步驟 91
5.3 晶體X-ray 92
第六章 參考文獻 118

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