本研究以不同的有機鈷金屬錯合物CoII(salen), CoII(H2O)2(dmgBF2)2, CoII(salen-OMe)及CoII(salen-NO2)調控丙烯酸甲酯(MA)的自由基聚合反應。在反應過程中我們利用紫外可見光譜追蹤聚合反應，並透過數值分析方法計算出在平衡時CoII及CoIII-R的濃度。藉由平衡時CoII與CoIII-R的比例以及從一級反應動力學曲線圖得到聚合反應時自由基的濃度我們可以推算各個鈷金屬錯合物在調控丙烯酸甲酯的自由基聚合反應時的平衡常數Keq = 9.5 × 107 M-1(CoII(salen))、7.9 × 107 M-1(CoII(H2O)2(dmgBF2)2)、2.7 × 107 M-1(CoII(salen-OMe))及1.1 × 109 M-1(CoII(salen-NO2))。同時我們也發現平衡常數與其對應的有機鈷金屬錯合物的氧化還原半電位呈現線性關係。平衡常數、氧化還原半電位與調控機制之間的關聯性可以幫助我們對鈷調控自由基聚合反應有更深入的了解。

Cobalt mediated radical polymerization (CMRP) of methyl acrylate was performed with CoII(salen), CoII(H2O)2(dmgBF2)2, CoII(salen-NO2) ,and CoII(salen-OMe) at 60 °C and its CoII/CoIII equilibrium constant have been measured by using UV-vis spectroscopy to determine the concentration of cobalt species ([CoII] and [CoIII-P]) and the first order kinetic plots to obtain the radical concentration ([P•]). With the increasing information of Keq values in different CMRP systems, a linear correlation between the CoII/CoIII reduction potential (E1/2) and log(Keq) was discovered. The connection of reduction potential, equilibrium constant, and control mechanism would contribute to the understanding of CMRP process.

目錄
中文摘要 I
英文摘要 II
謝誌 III
目錄 IV
圖目錄 VII
表目錄 XIII
式目錄 XV
第一章 緒論 1
1-1聚合反應( Polymerization) 1
1-2 活性聚合反應(Living polymerization) 2
1-3 活性/可控自由基聚合反應 (Living / controlled radical polymerization) 3
1-3.1 氮氧自由基聚合反應 (Nitroxide-mediated radical polymerization，NMP) 5
1-3.2 原子轉移自由基聚合反應 (Atom transfer radical polymerization, ATRP) 6
1-3.3 可逆加成-斷裂鍊轉移聚合 (Reversible Addition-Fragmentation Chain Transfer，RAFT) 7
1-3.4 鈷調控活性自由基聚合 (Cobalt-Mediated Radical Polymerization，CMRP) 8
1-4 實驗動機與目的 12
第二章 實驗方法 13
2-1 化學藥品 13
2-2儀器設備與鑑定方法 14
2-3 實驗方法 15
2-3.1鈷金屬錯合物Cobalt(II) [N,N’-bis(3,5-di-tert-butyl salicylidene) ethylenediamine] (CoII(salen))的製備 15
2-3.2鈷金屬錯合物CoII(H2O)2(dmgBF2 )2的製備 17
2-3.3鈷金屬錯合物CoII(salen-NO2)的製備 18
2-3.4鈷金屬錯合物Cobalt(II)[N,N-bis(2-hydroxy-5- methoxysalicylidene)ethylenediamine] (CoII(salen –OMe))的製備 21
2-3.5以鈷錯合物進行丙烯酸甲酯 (MA)可控自由基聚合 22
2-3.6紫外可見光譜待測樣品的配置 22
2-3.7鈷金屬錯合物半電位的測定 22
第三章 鈷錯合物進行丙烯酸甲酯的活性自由基聚合反應 23
3-1 以CoII(salen) 進行丙烯酸甲酯的活性自由基聚合反應 25
3-2 以CoII(H2O)2(dmgBF2 )2 進行丙烯酸甲酯的活性自由基聚合反應 36
3-3 以CoII(salen-NO2)進行丙烯酸甲酯的活性自由基聚合反應 47
3-4 以CoII(salen-OMe)進行丙烯酸甲酯的活性自由基聚合反應 55
3-5. 結論 67
第四章 附錄 68
第五章 參考文獻 73

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