本論文中共合成出了 10 種具可見光吸收之三苯胺肟酯衍生物 I 型光起始劑
(Peko、Miko 系列)，並使用核磁共振氫譜(1H-NMR)、碳譜(13C-NMR)及質譜法
(FT-MS)對其分子組成及結構上進行確認。Part-1 中，我們針對了肟酯末端位置進
行不同碳鏈之置換，探討不同種類、長度之烷基鏈對於光起始劑之影響，如末端
烷基鏈導入具異丙基之 Peko-A、具丁基之 Peko-B、具 11 碳之 Peko-C、具 15 碳
之 Peko-D 與參考樣品具甲基之 TP-1M。於 Part-2 中，則針對肟酯末端位置導入
不同的苯環衍生物，以苯環上含不同推、拉電子基團之結構，來探討此衍生光起
始劑之光聚合特性之影響，如具甲氧基苯之 Miko-MOB、具第三丁基苯之 Mikot-Bu，兩個化合物為推電子基團；具三氟甲基苯之 Miko-TFM，具硝基苯之 MikoNB 與具氯苯之 Miko-CB，此三化合物則為拉電子基團，並以具苯之 TP-1 為參
考結構。在 UV-Vis 吸收光譜中，Part-1 的莫耳消光係數以直烷鏈比較，由大至小
排列為: Peko-D > Peko-C > Peko-B > TP-1M，發現吸光強度與碳鏈長度有關。
經由 Photo-DSC 實驗，使用了 UV-lamp、LED@365 nm 及 LED@405 nm 三種不
同的光源以三羥甲基丙烷三丙烯酸酯(TMPTA)為單體進行光反應性探討，其中
Part-1 所有基於肟酯的配方在 LED@405 nm 作為輻射源時都顯示出更好的雙轉
換效率。另，基於 Peko-B 的配方在 UV 燈(最終雙鍵轉化率= 37%)、LED@365
nm (最終雙鍵轉化率= 35%)和 LED@405 nm (最終雙鍵轉化率= 42%)表面最為平
衡。而在 Part-2 中以 Miko-MOB 的配方表現出最佳之雙鍵轉化率，在 UV 燈(最
終雙鍵轉化率= 32%)和 LED@405 nm (最終雙鍵轉化率= 32%)。在本論文中，利
用烷基鏈長度與苯環衍生物之導入可對於三苯胺肟酯光起始劑的效能更加理解。

In this study, 10 of Type I visible-light-absorbing triphenylamine oxime esterderived photoinitiators (Peko, Miko series) for free radical photopolymerization were prepared. All the structures were confirmed through proton nuclear magnetic resonance (1H-NMR), and carbon-NMR (13C-NMR), and mass spectrometry (FT-MS). In Part-1, Peko series containing various alkyl chain lengths were designed, that is, an alkane segment contains isopropyl for Peko-A, butyl for Peko-B, undecane for Peko-C, pentadecane for Peko-D, and methyl for TP-1M, respectively. In Part-2, Miko series containing various benzene ring derivatives in the periphery were designed, that is, a methoxybenzene for Miko-MOB, tertiary butylbenzene for Miko-t-Bu, a trifluoromethylbenzene for Miko-TFM, a nitrobenzene for Miko-NB, a chlorobenzene for Miko-CB, and a phenyl only for TP-1. Compared to the linear alkyl chain length effect in Part-1, the molar extinction coefficient showed significantly decreasing in the following order: Peko-D > Peko-C > Peko-B > TP-1M. Peko-D containing the longest
alkyl chain exhibited the highest molar extinction coefficient among all. In addition, the oxime esters based photoinitiating systems were studied through photo-DSC experiment under the different light exposure wavelengths (UV lamp, LED@365 nm and LED@405 nm). In Part-1, all the formulations gave better double conversion efficiency under the irriadiation of LED@405 nm. Among all, the Peko-B based formulationhad the most balanced performance with the conversion efficiency of 37% under UV lamp, of 35% under LED@365 nm, and of 42% under LED@405 nm. In Part-2, Miko-MOB based formulation exhibits the best double conversion efficiency of 32% under UV lamp and LED@405 nm. In addition, the the double bond conversion rate under UV lamp from the highest to the lowest is Miko-MOB, Miko-t-Bu, MikoTFM, Miko-CB, TP-1, Miko-NB. In this study, The effect of terminal alkyl chain lenghts and benzene derivatives substituted triphenylamine oxime esters are explicitly studied and discussed.

摘要 i
Abstract iii
致謝 vi
目錄 vii
表目錄 x
圖目錄 xi
一、緒論 1
二、文獻回顧與研究動機 2
2-1 光源介紹(定義與應用) 2
2-1-1 UV光源 2
2-1-2 發光二極體(Light-emitting diode, LED) 2
2-2 光固化 4
2-3 深度聚合 7
2-4 肟酯固化系統 8
2-4-1 針對肟酯結構中R1與R2之文獻回顧 8
2-4-2 針對肟酯結構中R3之文獻回顧 12
2-5 肟酯R3位置取代基選擇 16
2-6 研究動機 19
三、實驗方法 20
3-1 實驗架構 20
實驗流程圖(圖3-1) 20
3-2 儀器設備 21
3-3 實驗藥品 23
3-4 溶劑 25
3-5 三苯胺衍生肟酯之合成 26
3-5-1 三苯胺衍生肟酯末端碳鏈之合成(Part-1) 26
Peko-A-D與TP-1M結構示意圖(圖3-2) 26
A1之合成(圖3-3) 27
A2 之合成(圖3-4) 28
TP-1M 之合成(圖3-5) 29
Peko-A 之合成(圖3-6) 30
Peko-B 之合成(圖3-7) 31
Peko-C 之合成(圖3-8) 32
Peko-D 之合成(圖3-9) 33
3-5-2 三苯胺肟酯末端苯環衍生物之合成(Part-2) 34
Miko系列與TP-1光起始劑之結構示意圖(圖3-10) 34
Miko-TFM之合成(圖3-11) 35
Miko-t-Bu之合成(圖3-12) 36
Miko-NB之合成(圖3-13) 37
Miko-MOB之合成(圖3-14) 38
Miko-CB之合成(圖3-15) 39
3-6 實驗方法 40
3-6-1熱性質分析 40
TGA 測量 40
DSC 測量 40
3-6-2紫外光/可見光光譜儀測量 40
3-6-3螢光光譜儀測量 41
3-6-4循環伏安法測量 41
3-6-5 Photo-DSC (UV lamp, LED@365 nm及LED@405 nm)測量 41
3-6-6光解測量 42
3-6-7電子順磁共振儀測量 42
3-6-8 理論計算 42
3-6-9 深度固化 43
3-6-10 3D列印 43
四、結果與討論 44
4-1 三苯胺衍生肟酯之結構鑑定 44
4-1-1 TP-1M之結構鑑定 44
4-1-2 Peko-A之結構鑑定 47
4-1-3 Peko-B之結構鑑定 50
4-1-4 Peko-C之結構鑑定 53
4-1-5 Peko-D之結構鑑定 56
4-1-6 Miko-CB之結構鑑定 59
4-1-7 Miko-MOB之結構鑑定 62
4-1-8 Miko-NB之結構鑑定 65
4-1-9 Miko-t-Bu之結構鑑定 68
4-1-10 Miko-TFM之結構鑑定 71
4-2 熱性質 74
Part-1 74
Part-2 76
4-3 光化學分析 78
4-3-1 UV/Vis及PL分析 78
市售光起始劑 78
Part-1 79
Part-2 81
4-3-2 光解(Photolysis)分析 83
Part-1 83
Part-2 85
4-3-3 電子自旋共振(ESR)分析 86
Part-1 86
Part-2 87
4-4 電化學分析 88
Part-1 88
Part-2 91
4-5 理論計算 93
4-6 光聚合性質 95
4-6-1 Part-1光聚合 96
UV-lamp@180 mW/cm2 96
UV-lamp@50 mW/cm2 98
LED@365 nm 50 mW/cm2 100
LED@405 nm 50 mW/cm2 102
4-6-2 Part-2光聚合 104
UV-lamp 180 mW/cm2 104
LED@405 nm 180 mW/cm2 106
4-7 深度固化 108
4-8 3D列印 109
五、結論 111
六、參考文獻 112

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