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研究生： 黃鵑
Huang, Chuan
論文名稱： 新型半salen鈷金屬錯合物調控的熱/光引發之聚合反應
Thermal- and Photo-induced Cobalt-Mediated Radical Polymerization with a Novel Half-Salen Type Cobalt(II) Complex
指導教授： 彭之皓
Peng, Chi How
口試委員: 王潔
Wang, Jane
陳俊太
Chen, Jiun Tai
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： 2016
畢業學年度： 104
語文別： 中文
論文頁數： 156
中文關鍵詞： 鈷調控自由基聚合反應 、醋酸乙烯酯 、半salen二配位體螯合之鈷金屬錯合物 、光刺激聚合反應
外文關鍵詞： Cobalt-mediated radical polymerization, vinyl acetate, CoII(half-salen*), photo-initiated polymerization
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    • 合成新型半salen二配位體螯合之鈷金屬錯合物以進行鈷調控自由基聚合反應 (Cobalt-mediated radical polymerization; CMRP)。實驗分別使用熱引發及光刺激促使自由基生成。在熱引發醋酸乙烯酯聚合中，以降低反應溫度且提高起始劑當量的方式，可以使控制效果增進。在低溫的熱引發聚合中，分子量高於理論分子量，分子量對單體轉換率呈線性增加，PDI值較大 (PDI = 1.62-1.72)，顯示調控效果仍有進步空間，因此改進行光刺激醋酸乙烯酯聚合。
    研究發現在光刺激醋酸乙烯酯聚合中，當起始劑當量上升，分子量會符合理論分子量線。此外，在實驗中探討光照強度和溫度對光刺激聚合反應的影響，發現在高照光強度下，可使用較低的起始劑當量進行聚合，分子量會符合理論分子量。而使用不同溫度進行聚合反應發現，溫度提高有助於PDI值下降，但分子量會大於理論分子量，推測為在高溫中鈷二價金屬比例上升導致。

    The study of CMRP (Cobalt-mediated radical polymerization) has been developed rapidly. Here, we synthesized a half-salen type bidentate ligand to chelate cobalt(II) metal. This novel cobalt complex we called CoII(half-salen*) differed from CoII(salen*) in its structure but same in its composition. The structure of CoII(half-salen*) was similarly tetrahedral while the structure of CoII(salen*) was square planar. Due to CoII(salen*) have been applied in CMRP of vinyl acetate successfully that might indicate CoII(half-salen*) also have potential to mediate radical polymerization of vinyl acetate.
    The polymerization was initiated by either heat or light. In thermo-initiation, the control of CoII(half-salen*) could be improved via reducing temperature or increasing the ratio of initiator. At low temperature, the molecular weight was higher than theoretical molecular weight and the PDI value was large (PDI = 1.62-1.72) in CMRP. To improve the control of CoII(half-salen*), the CMRP was carried out under 365 nm irradiation with photo-initiator of TPO.
    As the ratio of initiator rose, the molecular weight would fit theoretical molecular weight more closely. However, it occurred chain transfer reaction during polymerization servely with low light intensity and high ratio of initiator in polymerization.
    As light intensity was high, the molecular weight fit the theoretical molecular weight better with low ratio of initiator. However, higher light intensity gave higher PDI value. To lower the PDI value, we have tried to change the temperature during the polymerization. The PDI values reduced as we increased temperature, however, the molecular weight deviated from the theoretical molecular weight at the same time.

    Abstract I 摘要 III 謝誌 IV 目錄 V 圖目錄 VII 表目錄 XIV 第一章 緒論 1 1-1 活性自由基聚合反應 2 1-2 活性自由基聚合技術 6 1-2-1 原子轉移自由基聚合反應 (Atom transfer radical polymerization; ATRP) 6 1-2-2 可逆加成-斷裂鏈轉移聚合反應 (Reversible addition-fragmentation chain-transfer radical polymerization; RAFT polymerization) 13 1-2-3 氮氧自由基聚合反應 (Nitroxide-mediated radical polymerization; NMP) 15 1-2-4 有機鈷金屬錯合物調控自由基聚合反應 (Cobalt-mediated radical polymerization; CMRP) 17 1-3 光刺激可控自由基聚合反應 26 1-4 研究目的及動機 33 第二章 新型半salen二配位體螯合之鈷金屬調控聚合反應 (The research of CMRP with novel half-salen type cobalt complex) 34 2-1 實驗 35 2-1-1 化學藥品 35 2-1-2 聚合反應 35 2-2 半salen二配位體為基底之鈷錯合物合成 37 2-3 鈷錯合物之光譜與電位分析 40 2-4 熱引發鈷錯合物調控醋酸乙烯酯聚合反應 46 2-5 光刺激鈷錯合物調控醋酸乙烯酯聚合反應 60 2-5-1 光起始劑比例對醋酸乙烯酯聚合反應之影響 60 2-5-2 光強度對醋酸乙烯酯聚合反應之影響 79 2-5-3 溫度對醋酸乙烯酯聚合反應之影響 81 2-6 結論 94 第三章 芳杯單體自由基聚合反應 (Radical polymerization of calixarene monomer) 95 3-1 實驗 96 3-1-1 化學藥品 97 3-1-2 自由基聚合反應 97 3-2 芳杯單體合成 98 3-3 丙烯基苯聚合反應 101 3-4 芳杯單體聚合反應 103 3-5 結論 106 第四章 乳膠態鈷金屬調控丙烯腈聚合反應 (Cobalt-mediated radical emulsion polymerization of acrylonitrile) 107 4-1 實驗 108 4-1-1 化學藥品 110 4-1-2 乳膠態聚合反應 110 4-2 乳膠態鈷金屬錯合物調控聚合反應 115 4-3 結論 134 附錄 135 儀器 150 引用文獻 150

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