本實驗室先前的研究中，成功地利用傳統的偶氮類熱引發劑及只含碳、氫、氧的有機調控劑－環庚三烯酮，進行N,N-二甲基丙烯醯胺在水中的可逆－失活自由基聚合反應。在本研究中，借助黃暄益教授的半導體材料專長，利用4-硝基苯乙炔修飾之氧化亞銅立方體優異的光催化能力，結合環庚三烯酮進行N,N-二甲基丙烯醯胺的光催化可逆－失活自由基聚合反應，並利用高分子鏈尾端活性合成嵌段共聚物，值得注意的是，水溶液環境及可見光波段之光源即可驅動反應，為綠色化學帶來一些助益。
在進一步探討在聚合反應調控機制時，發現巨分子起始劑結構帶有原子轉移自由基聚合反應之中間物特徵。因此引入原子轉移自由基聚合反應的概念，將反應物更換為文獻中原子轉移自由基聚合反應常用之引發劑及配基，但是結果呈現的分子量分布皆不如預期，更無法符合可逆－失活自由基聚合反應的特徵，藉此可以推斷反應調控機制與原子轉移自由基聚合反應不同，但確切機制尚未明確，待後人釐清。

In our previous works, we successfully conducted a reversible-deactivation radical polymerization (RDRPs) of N,N-dimethylacrylamide in water using traditional azo-based thermal initiators and an organo-mediators containing only C, H and O atoms namely tropone. In this study, leveraging Professor Michael Hsuan-Yi Huang’s expertise in semiconductor materials, we utilized 4-nitrophenylacetylene-modified Copper(I) oxide cubes (4-NA-Cu2O cubes) with excellent photocatalytic capability, combining them with tropone to carry out a photo-catalyzed reversible-deactivation radical polymerization of N,N-dimethylacrylamide, and synthesized block copolymers to verify the fidelity of end-groups in the polymer chains. Notably, the reaction could be driven by visible light sources in an aqueous environment, contributing to green chemistry practices.
Further investigation into the polymerization controlled mechanism revealed that the structure of the macroinitiator exhibited characteristics of atom transfer radical polymerization (ATRP) intermediates. Therefore, we introduced the concept of ATRP. The reaction was carried out by replacing the reactants with commonly used initiators and ligands for literature-known ATRP. Unfortunately, the resulting molecular weight distributions did not meet the expected outcomes and deviated significantly from the concept of RDRP. This suggests that the reaction mechanism is incompatible with ATRP. However, the exact mechanism remains unclear and requires further investigation by future researchers to elucidate.

摘要 i
Abstract ii
謝誌 iii
目錄 iv
圖目錄 vi
表目錄 x
式目錄 xii
第一章 緒論 1
1-1 傳統聚合反應 1
1-2 自由基聚合反應 (Radical Polymerization) 3
1-3 可逆－失活自由基聚合反應 (Reversible-Deactivation Radical Polymerization, RDRP) 5
1-3-1 氮氧自由基聚合反應 (Nitroxide Mediated Radical Polymerization, NMP) 8
1-3-2 原子轉移自由基聚合反應 (Atom Transfer Radical Polymerization, ATRP) 10
1-3-3 可逆加成－斷裂鏈轉移聚合反應 (Reversible Addition−Fragmentation Chain-Transfer Polymerization, RAFT) 12
1-4 有機化合物應用於可逆－失活自由基聚合反應 14
1-5 奈米半導體材料應用於光催化聚合反應 17
1-6 研究動機 21
第二章 實驗及藥品 23
2-1 化學藥品 23
2-2 實驗儀器 24
2-3 實驗步驟 26
第三章 實驗結果與討論 29
3-1 4-NA-Cu2O cubes奈米粒子的鑑定 29
3-2 4-NA-Cu2O cubes於光催化聚合反應之應用 32
3-2-1 討論4-硝基苯乙炔對聚合反應的影響 35
3-2-2 氧化亞銅溶解度對光催化效果的影響 40
3-3 4-NA-Cu2O cubes結合環庚三烯酮應用於可逆－失活自由基聚合反應 44
3-3-1 環庚三烯酮與自由基之比例對可逆－失活自由基聚合反應的影響 45
3-3-2 4-NA-Cu2O cubes結合環庚三烯酮調控之聚合反應機制探討 50
3-3-3 合成嵌段共聚物 61
3-3-4 時間控制光催化可逆－失活自由基聚合反應 64
3-4 結論 65
第四章 附錄 66
4-1 原始聚合數據 66
4-2 Cu2O cubes原始SEM影像 69
第五章 參考文獻 75

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