本研究探討六芳雙基咪唑(HABI)衍生物光聚合動力學，在六芳雙基咪唑加入三苯胺結構和一對或兩對甲氧基結構，以氫譜核磁共振 (1H-NMR)、質譜法(Mass)和元素分析(EA)鑑定分析其衍生物之結構、分子量和碳、氫、氮組成的比例，成功合成可作為自由基型光起始劑HABI1-3，而HABI1-3在近紫外光光區具有優異的吸收特性，其最大波長接近300 nm且延伸至450 nm，其吸收波長較市售ocl-HABI (2-Chloro-hexaarylbiimidazole)紅位移且具有較高的莫耳消光係數，以ESR光譜量測ocl-HABI與HABI1-3自由基濃度，由於HABI1-3在近紫外光吸光能力強，使得產出自由基濃度遠大於ocl-HABI，以Rehm–Weller equation計算，HABI衍生物/N-苯基甘氨酸(NPG)系統，此系統具有良好的電子傳遞能力，能使單體產生交聯聚合反應，將HABI衍生物與NPG在等莫耳比下，並搭配三羥甲基丙烷三甲基丙烯酸酯(TMPTMA)以Photo-DSC量測其光固化轉化效率，在UV光源下HABI1 > HABI2 >ocl-HABI，而在LED光源下，HABI1 > ocl-HABI，說明HABI1所衍生之系統可於未來應用於UV及LED等不同光源下之光固化應用。

In this study, three triphenylamine-based hexaaryldiphenylimidazole (HABI) derivatives featuring different numbers of methoxy groups (none for HABI1, two for HABI2, and four for HABI3) have been synthesized and identified by proton Nuclear Magnetic Resonance Spectroscopy (1H-NMR), Mass Spectrometry (Mass) and Elemental Analysis (EA). Their optical properties and photopolymerization reactions were investigated in this work. For comparison, a commercial photoinitiator of the hydrogen acceptor, ocl-HABI (2-Chloro-hexaarylbiimidazole), was also applied in a corresponding photopolymerization. The HABIs display rather red-shifted and larger molar extinction coefficient than ocl-HABI that exhibited the absorption from 300 to 450 nm. In addition, larger free radical concentraction of the HABIs than ocl-HABI through Electron Paramagnetic Resonance (ESR) spectroscopy. These HABIs were selected in combination with N-phenyl glycine (NPG) for Type II free radical polymerization (FRP). Cyclic voltammetry (CV) and free energy change ΔG results of all the Type II series exhibited good electron transfer ability. For FRP, besides HABI3 showed poor stability under UV light source, the trend of the photocuring conversion efficiency were in the order of HABI1 > HABI2 > ocl-HABI. In addition, the HABI1 and ocl-HABI were also subjected in LED light source for further comparision. As a results, the HABI1 had better photocuring conversion efficiency than ocl-HABI, indicating that the system derived from HABI1 can be applied to light curing applications under different light sources such as UV and LED in the future.

目錄
摘要 I
Abstract III
致謝 V
目錄 VI
表目錄 X
圖目錄 XI
第一章 緒論 1
1-1前言…………………………………………………………………….1
第二章 文獻回顧與研究動機 2
2-1光源簡介 2
2-1-1 UV光源分類 2
2-1-2發光二極體(Light-emitting diode, LED) 3
2-2光固化系統 4
2-2-1寡聚物 5
2-2-2反應性單體 6
2-2-3光起始劑 7
2-2-3-1陽離子型光起始劑 8
2-2-3-2自由基型光起始劑 8
2-3六芳雙基咪唑(Hexaarylbiimidazole, HABI) 10
2-3-1 HABI性質 10
2-3-2 ocl-HABI/NPG系統 17
2-3-3 HABI衍生物 21
2-4三苯胺 29
2-5研究動機 30
第三章 實驗方法 32
3-1實驗架構 32
3-2儀器設備 33
3-3 實驗藥品 36
3-4有機溶劑 41
3-5 HABI衍生物之合成 44
2A0之合成 (圖3-3) 45
3A0之合成 (圖3-4) 45
1A之合成 (圖3-5) 46
2A之合成 (圖3-6) 47
3A之合成 (圖3-7) 47
1B之合成 (圖3-8) 48
2B之合成 (圖3-9) 49
3B之合成 (圖3-10) 50
HABI1之合成 (圖3-11) 50
HABI2之合成 (圖3-12) 51
HABI3之合成 (圖3-13) 52
3-6實驗方法 53
3-6-1 HABI衍生物溶解度測量 53
3-6-2 HABI衍生物之熱性質分析 53
TGA測量 53
DSC測量 54
3-6-3 HABI衍生物紫外/可見光光譜儀測量 54
3-6-4 HABI衍生物螢光光譜儀測量 55
3-6-5 HABI衍生物電子順磁共振光譜儀測量 55
3-6-6 HABI衍生物循環伏安法測量 56
3-6-7 HABI衍生物Photo-DSC測量 57
第四章 結果與討論 58
4-1 HABI衍生物合成與鑑定 58
4-1-1 HABI1合成與鑑定 58
1A鑑定 59
1B鑑定 60
HABI1鑑定 62
4-1-2 HABI2合成與鑑定 64
2A0鑑定 65
2A鑑定 66
2B鑑定 67
HABI2鑑定 69
4-1-3 HABI3合成與鑑定 71
3A0鑑定 72
3A鑑定 73
3B鑑定 74
HABI3鑑定 76
4-2物理性質測試 78
4-2-1溶解度測試 78
4-2-2熱重分析 79
4-2-3熱示差掃描分析 80
4-3光化學性質分析 82
4-3-1 UV/visible分析 82
4-3-2 HABI1光化學反應 84
4-3-3螢光光譜(PL spectra)分析 86
4-3-4電子順磁共振光譜儀 (EPR)分析 88
4-4電化學分析 92
4-4-1循環伏安法測量 92
4-5光聚合測試 94
第五章 結論 100
第六章 參考文獻 102
附錄 A 109

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