本研究藉由有機鈷金屬錯合物上官能基的變換以及結構的設計，合成出多種有機鈷金屬錯合物，包括CoII(acac)2、CoII(Salen*)、CoII(etSalen-OMe)、CoII(Salen-tBuOMe)、CoII(Salen-tBuNO2)、CoII(Salen-tBuNMe2)、CoII(etSalen-tBuNMe2)、CoII(TMP)，進而運用於調控丙烯酸甲酯(Methyl acrylate)、丙烯腈(Acrylonitrile)、苯乙烯(Styrene)及乙酸乙烯酯(Vinyl acetate)等單體之自由基聚合反應。
　　在聚合反應過程中，以紫外/可見光譜追蹤，並透過數值分析方法計算出平衡時CoII和CoIII-R的濃度。由觀察平衡時CoII和CoIII-R的比例(KCMRP)以及氧化還原半電位(E1/2)的關係，發現丙烯酸甲酯和丙烯腈的資料呈現線性關係。此線性關係可與結構、官能基以及有機鈷金屬錯合物性質相互進行探討，並有助於深入瞭解鈷調控自由基聚合反應機制、結構對反應影響的趨勢與效應，且提供了預測新型鈷錯合物機制的機會，可應用於未來的新單體、新錯合物其反應的設計與預測。

Cobalt mediated radical polymerization (CMRP) of methyl acrylate (MA), acrylonitrile (AN), vinyl acetate (VAc) and styrene (Sty) were performed with CoII(acac)2, CoII(Salen*), CoII(etSalen-OMe), CoII(Salen-tBuOMe), CoII(Salen-tBuNO2), CoII(Salen-tBuNMe2), CoII(etSalen-tBuNMe2) and CoII(TMP). The equilibrium constant had been calculated by using UV-Vis sperctroscopy to determine the concentration of cobalt species ([CoIII] and CoIII-P]) and the first kinetic plots to obtain the radical concentration ([P‧]). With the KCMRP values getting much more substantial, the linear correlation between E1/2 and log(KCMRP) was discovered in methyl acrylate and acrylonitrile polymerization. This linear correlation contributes to an in-depth understanding of CMRP process and the linear correlation between log(KCMRP) and E1/2 is helpful to predict the control mechanism of CMRP using a new cobalt complex.

摘要 I
Abstract II
謝誌 III
目錄 IV
圖目錄 VII
表目錄 XXVII
式目錄 XXXIV
第一章 緒論 1
1-1高分子聚合物的發展 1
1-2聚合反應 (Polymerization) 3
1-3 活性聚合反應(Living polymerization) 5
1-4 活性/可控自由基聚合反應 (Living / controlled radical polymerization) 6
1-4-1 氮氧自由基聚合反應 (Nitroxide-mediated radical polymerization，NMP) 8
1-4-2 原子轉移自由基聚合反應 (Atom transfer radical polymerization, ATRP) 9
1-4-3 可逆加成-斷裂鍊轉移聚合 (Reversible Addition-Fragmentation Chain Transfer，RAFT) 12
1-4-4 鈷調控自由基聚合反應 (Cobalt-Mediated Radical Polymerization，CMRP) 13
1-4-4-1 鈷調控自由基聚合反應機制 14
1-4-4-1 Cobalt-Porphyrin (Co(TMP)) 16
1-4-4-3 Cobalt-bisacetylacetonate (CoII(acac)2) 18
1-4-4-4 Cobalt salen complexes 19
1-5 實驗動機與目的 20
第二章 實驗方法 21
2-1 化學藥品 21
2-2儀器設備與鑑定方法 23
2-3 實驗方法 24
2-3-1鈷金屬錯合物CoII(Salen*)的製備 24
2-3-2鈷金屬錯合物CoII(etSalen-OMe)的製備 25
2-3-3鈷金屬錯合物CoII(Salen-tBuOMe)的製備 26
2-3-4鈷金屬錯合物CoII(Salen-tBuNO2)的製備 29
2-3-5鈷金屬錯合物CoII(Salen-tBuNMe2)的製備 32
2-3-6鈷金屬錯合物CoII(etSalen-tBuNM2)的製備 34
2-3-7鈷錯合物調控自由基聚合反應 36
2-3-8紫外/可見光譜待測樣品的配置 36
2-3-9鈷金屬錯合物氧化還原半電位的測定 36
第三章 研究丙烯酸甲酯在鈷金屬錯合物調控自由基聚合中，平衡常數與氧化還原半電位之關聯 37
3-1 以CoII(Salen*)進行丙烯酸甲酯的活性自由基聚合反應 39
3-2 以CoII(etSalen-OMe)進行丙烯酸甲酯的活性自由基聚合反應 46
3-3 以CoII(Salen-tBuOMe)進行丙烯酸甲酯的活性自由基聚合反應 53
3-4 以CoII(Salen-tBuNMe2)進行丙烯酸甲酯的活性自由基聚合反應 61
3-5 以CoII(etSalen-tBuNMe2)進行丙烯酸甲酯的活性自由基聚合反應 68
3-6 討論 70
第四章 研究丙烯腈在鈷金屬錯合物調控自由基聚合中，平衡常數與氧化還原半電位之關聯 74
4-1 以CoII(Salen*)進行丙烯腈的活性自由基聚合反應 76
4-2 以CoII(Salen-tBuNO2)進行丙烯腈的活性自由基聚合反應 84
4-3 以CoII(Salen-tBuOMe)進行丙烯腈的活性自由基聚合反應 92
4-4 以CoII(etSalen-OMe)進行丙烯腈的活性自由基聚合反應 99
4-5 以CoII(etSalen-tBuNMe2)進行丙烯腈的活性自由基聚合反應 108
4-6 以CoII(TMP)進行丙烯腈的活性自由基聚合反應 116
4-7 討論 120
第五章 研究乙酸乙烯酯在鈷金屬錯合物調控自由基聚合中，平衡常數與氧化還原半電位之關聯 122
5-1 以CoII(Salen-tBuNMe2)進行乙酸乙烯酯的活性自由基聚合反應 123
5-2 以CoII(Salen-tBuOMe)進行乙酸乙烯酯的活性自由基聚合反應 131
5-3 以CoII(etSalen-tBuNMe2)進行乙酸乙烯酯的活性自由基聚合反應 134
5-4 結論 136
第六章 鈷調控苯乙烯自由基聚合反應 139
6-1前言 139
6-2以CoII(TMP)進行苯乙烯的活性自由基聚合反應 140
6-2-1 [CoII(TMP)]0/[TPO]0/[Sty]0 = 0/10/1000 at 30 ˚C 140
6-2-2 [CoII(TMP)]0/[TPO]0/[Sty]0 = 1/10/1000 at 30 ˚C 141
6-2-3 [CoII(TMP)]0/[TPO]0/[Sty]0 = 1/20/1000 at 20 ˚C 143
6-2-4 [CoII(TMP)]0/[TPO]0/[Sty]0 = 1/10/1000 at 2 ˚C 145
6-3結論 147
第七章 延伸探討 148
7-1 平衡常數與氧化還原半電位之關聯 148
7-2 線性關係與電子效應 (Electronic effect) 150
7-3 線性關係與巨環效應 (Macrocyclic effect) 152
7-4 不同單體之線性關係 154
第八章 附錄 156
第九章 參考文獻 178

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