本研究以環庚三烯酮(Tropone)有機化合物調控劑調控活性/可控自由基聚合反應，為新穎的可逆－失活自由基聚合反應技術，此調控劑可直接購買，不用進行複雜的有機合成，且因為無金屬，也符合綠色化學，所以拓展其在聚合物合成上之應用範圍是值得研究的方向。能成功控制醋酸乙烯酯與其他單體的聚合反應，進而合成由不同單體組成的嵌段共聚物 (block copolymer)，也是此可控活性聚合的一大特點。
本研究成功合成之嵌端共聚物包含PVAc-b-PS，水解後PVA-b-PS，以及PVAc-b-PVP，和PVAc-b-PDMA，我們會鑑定嵌端共聚物的熱性質，從TGA儀器發現改變嵌段比例與分子量在熱裂解溫度改變不大，DSC儀器發現改變嵌段比例與分子量對玻璃轉化溫度在PVAc-b-PVP有較大影響，其他則改變不大。
在PVA膜研究上，將嵌端共聚物 (BCP)加入PVA後，以溶延法製成共混膜，機械性質分析上，若有氫鍵交聯則會上升，同樣，若有交聯亦會增加熱穩定性，若無，則會因破壞結晶性以及氫鍵，反而使機械性質及熱穩定性下降。UV-Vis上證明薄膜透明度可以維持，且對紫外光能有效阻隔。改變嵌段比例對整個趨勢不變，只改變增加嵌段比例之聚合物特性，如PS端剛性較強，若PS端比例上升則剛性較強且疏水性較高。

In this study, tropone, a novel organic compound mediator was used to mediate the living/controlled radical polymerization reaction This compound is commercially available with no need of complicated organic synthesis, and complies with green chemistry. Thus broadening the application of this method is the goal of my study. It can successfully control the polymerization of vinyl acetate and other monomers, and synthesizes the block copolymers composed of different monomers. My work focus on the block copolymers include PVAc-b-PS, PVA-b-PS, PVAc-b-PVP, and PVAc-b-PDMA. Their physical properties were characterized, including thermal properties measured by TGA, DSC, and block ratio determined by NMR spectroscopy.
And then add BCP mix with PVA to form a blend film, then measure its mechanical , such as tensile strength, DMA, etc. The mechanical properties of PVA film blended with different BCP were evaluated, the presence of hydrogen bonding leads to increased strength, while the presence of cross-linking enhances thermal stability. Conversely, the absence of cross-linking decreases mechanical properties and thermal stability due to the disruption of crystallinity and hydrogen bonding. UV-Vis analysis confirms that the addition of block copolymers retained the transparency of the film, with effective blocking of UV light.

摘要 i
Abstract ii
謝誌 iii
目錄 iv
圖目錄 vii
式目錄 xv
第一章 緒論 16
1-1 傳統聚合反應 16
1-2 自由基聚合反應(Radical Polymerization) 17
1-3 可逆－失活自由基聚合反應(Reversible-Deactivation Radical Polymerization, RDRP) 19
1-3-1 氮氧自由基聚合反應(Nitroxide Mediated Radical Polymerization, NMP) 22
1-3-2 可逆加成－斷裂鏈轉移聚合反應(Reversible Addition−Fragmentation Chain-Transfer Polymerization, RAFT) 23
1-3-3 原子轉移自由基聚合反應 (Atom Transfer Radical Polymerization, ATRP) 25
1-3-4 鈷錯合物調控自由基聚合反應 (Cobalt-mediated Radical Polymerization, CMRP) 27
1-3-5 有機化合物調控自由基聚合反應 29
1-4 聚乙烯醇簡介 35
1-5 研究動機 36
第二章 實驗及藥品 37
2-1 化學藥品 37
2-2 實驗儀器 38
2-2-1 核磁共振光譜儀 （Nuclear Magnetic Resonance Spectroscopy, NMR） 38
2-2-2 動態機械分析儀 (Dynamic Mechanical Analyzer, DMA) 38
2-2-3 凝膠滲透層析儀 （Gel permeation chromatography, GPC） 38
2-2-4 熱重分析儀 (Thermogravimetric analysis, TGA) 39
2-2-5 熱示差掃描分析儀 (Differential scanning calorimetry, DSC) 39
2-2-6 萬能拉力機 (Tensile Strenhth Tester) 40
2-2-7 接觸角儀 (Contact angle , CA) 40
2-2-8 紫外光-可見光光譜儀 (Ultraviolet-visible Spectrophotometry, UV-vis) 40
2-3 實驗步驟 41
2-3-1 聚合反應步驟 41
2-3-2 嵌端共聚物的合成 41
2-3-3 聚乙烯醇高分子膜的製備步驟 42
2-3-4 聚乙烯醇高分子膜動態機械測試 42
2-3-5 聚乙烯醇高分子膜拉伸強度測試 42
第三章 實驗討論與結論 43
3-1 以tropone為調控劑合成嵌端共聚物 43
3-1-1 嵌端共聚物PVAc-b-PS之合成與條件優化 44
3-1-2 嵌端共聚物PVAc-b-PVP之合成 49
3-1-3 嵌端共聚物PVA-b-PS之合成 52
3-1-4 嵌端共聚物PVAc-b-PDMA之合成 55
3-2 嵌端共聚物熱性質分析 58
3-2-1 熱重分析 58
3-2-2 熱示差掃描分析 65
3-3 聚乙烯醇高分子膜性質探討 70
3-3-1 熱重分析 72
3-3-2 動態機械分析 76
3-3-3 拉伸強度分析 83
3-3-4 Contact angle分析 90
3-3-5 UV-VIS透明度分析 94
第四章 結論 98
第五章 附錄 100
5-1 聚合反應之原始數據 100
5-2 嵌段共聚物之DOSY-NMR及NMR數據 102
參考文獻 110

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