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研究生： 李家齊
Li, Jia-Qi
論文名稱： 探討多種官能基之Bis(phenoxy-imine)鈷金屬錯合物在醋酸乙烯酯及丙烯酸甲酯之自由基聚合反應的調控
Polymerizaion of Vinyl Acetate and Methyl Acrylate by Various Bis(phenoxy-imine) Cobalt(II) Complexes
指導教授： 彭之皓
Peng, Chi-How
口試委員: 陳俊太
Chen, Jiun-Tai
王潔
Wang, Jane
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： 2017
畢業學年度： 106
語文別： 中文
論文頁數： 82
中文關鍵詞： 鈷金屬調控自由基聚合反應 、自由基聚合 、鏈轉移 、醋酸乙烯酯 、丙烯酸甲酯
外文關鍵詞： free radical polymerization, salen, acac, chain transfer
相關次數： 點閱：3  下載：0 
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    • 本研究探討與配位基salen*具有相似結構的配位基phenoxy-imine與鈷金屬形成CoII(phenoxy-imine)2。在結構方面有別於CoII(salen)*的平面四配位，但是和CoII(acac)2一樣同為四面體結構。將CoII(phenoxy-imine)2應用於單體醋酸乙烯酯以及丙烯酸甲酯的自由基聚合中，進行鈷調控自由基聚合反應 (Cobalt-mediated radical polymerization; CMRP)。我們選出了六種不同官能基的催化劑來當作探討的對象，並研究官能基影響自由基聚合的情形。
    從實驗結果來觀察，發現催化劑對醋酸乙烯酯聚合反應控制的效果會隨著配位基的立體障礙性增加而得到改善，若是增加了推電子基的官能基，則會讓催化劑的性質偏向鏈轉移試劑。在丙烯酸甲酯的聚合反應中，發現 CoII(phenoxy-imine)2系列催化劑對於分子量皆沒有控制以及恆定的傾向，在丙烯酸甲酯的聚合中沒有任何效果，推測是因為丙烯酸甲酯聚合速度較快，且丙烯酸甲酯的自由基較為穩定，推斷鈷-碳鍵之間的鍵結較弱，因此不易控制丙烯酸甲酯聚合時的分子量。在此也可以知道 CoII(phenoxy-imine)2系列催化劑就如同 CoII(acac)2一樣，無法控制丙烯酸甲酯的聚合。

    Ligand phenoxy-imine ligand is similar with salen*, but the structure of CoII(phenoxy-imine)2 and CoII(salen)* are different. The conformation of CoII(phenoxy-imine)2 is similar with CoII(acac)2 used in Cobalt-mediated radical polymerization are planar.
    CoII(phenoxy-imine)2 mediate the radical polymerization with vinyl acetate and methyl acrylate. We choose six type of CoII(phenoxy-imine)2 to study the effect on the radical polymerization.
    In the polymerization of vinyl acetate, the CoII(phenoxy-imine)2 with bulky ligand has better performance in controlling the molecular weight of the polymer during the polymerization.
    In polymerization of methyl acrylate, the CoII(phenoxy-imine)2 can not control the molecular weight during the polymerization. The polymerize rate of methyl acrylate kp is larger than vinyl acetate and the radical of methyl acrylate is more stable than vinyl acetate. In other words, the Co-C bond of methyl acrylate is weaker than the vinyl acetate. So the methyl acrylate prefer to react each other than CoII(phenoxy-imine)2

    摘要 I Abstract II 謝誌 III 目錄 IV 圖目錄 V 表目錄 IX 第一章 緒論 1 1-1 自由基聚合反應 1 1-2 活性自由基聚合反應 3 1-2-1 原子轉移自由基聚合反應 6 1-2-2可逆加成-斷裂鏈轉移聚合反應 7 1-2-3 氮氧自由基聚合反應 9 1-2-4有機鈷金屬錯合物調控自由基聚合反應 11 1-3 鏈轉移聚合反應 19 1-4 研究目的及動機 22 第二章 Phenoxy-imine二配位體螯合之鈷金屬錯合物合成與鑑定 23 (The synthesize and characterize of bis(phenoxy-imine) cobalt (II) complexes) 23 2-1 實驗 23 2-1-2 聚合反應 25 2-2 Phenoxy-imine以及 Phenoxy-imine二配位螯合之鈷金屬錯合物合成 26 2-3鈷金屬錯合物之光譜分析 30 第三章 Phenoxy-imine二配位體螯合之鈷金屬調控聚合反應 34 (The research of CMRP with bis(phenoxy-imine) cobalt (II) complexes) 34 3-1 Phenoxy-imine二配位體螯合之鈷金屬調控醋酸乙烯酯聚合反應 34 3-2 Phenoxy-imine二配位體螯合之鈷金屬調控丙烯酸甲酯聚合反應 53 3-3 結論 61 第四章 功能性高分子的金屬在異相催化反應前後之價數測定 63 (The valence of the metal in the functional polymer before/after used) 63 4-1 前言 63 4-2 實驗 63 4-2-1 化學藥品 63 4-2-2 功能性高分子合成 65 4-3 功能性高分子應用於異相催化反應及金屬價數之測定 68 4-4 結論 72 第五章 附錄 73 引用文獻 80

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