臺灣博碩士論文加值系統

本研究探討Type II光起始劑氫受體噻吨酮 (Thioxanthone, TX)與5種不同之胺類氫予體N-苯甘胺酸 (N-phenyl glycine, NPG)、三乙胺 (Triethylamine, TEA)、三乙醇胺 (Triethanolamine, TEOA)、2,2′-(4-甲基苯基亞胺基)二乙醇 (2,2'-(4-Methylphenylimino)diethanol, p-TDEA)、N-苯基二乙醇胺 (n-Phenyldiethanolamine, N-PDEA)於三官能基單體三羥甲基丙烷三甲基丙烯酸酯 (Trimethylolpropane trimethacrylate, TMPTMA)下以Gel fraction方式進行光聚合轉化率之探討。發現以TEOA為氫予體之系統於固定重量比下其固化速率最快；在探討不同重量比TX/TEOA時，固含量從1:2 wt%、1.5:1.5 wt%到2:1 wt%時，隨著氫受體的增加，因無足夠之氫予體導致其反應速率逐漸下降。另外也探討TX/TEOA於固含量1:2 wt%下空氣與氮氣環境對期固化轉換率影響不大。
此外，本研究亦對光起始劑及氫予體以紫外光/可見光光譜 (UV/Visible spectra)和螢光光譜 (Fluorescence Spectrometry, PL)進行光化學性分析，其吸光波長大小分別為p-TDEA > n-PDEA > NPG > TEOA > TEA；並以光起始劑與胺類氫予體混合後，測量其放光強度，得知其放光強度為TX/p-TDEA > TX/n-PDEA > TX/ NPG > TX/TEA > TX/TEOA。另以循環伏安法 (Cyclic voltammetry, CV)量測其氧化還原電位得知其HOMO值與LUMO值，進一步以Rehm-Weller equation計算各別之ΔGET值，得知其ΔGET值，分別TEA為-3.06、NPG為-1.82、p-TDEA為-1.76、TEOA為-1.74及n-PDEA為-1.71皆為自發性反應，但由於氫予體之立體障礙與幾級胺而導致固化速率有所不同。

In this work, we investigated the double bonds conversion efficiencies (DC values) based on different Type II photoinitiator packages through gel fraction method. The formulations are including a trifunctional monomer of trimethylolpropane trimethacrylate (TMPTMA), hydrogen acceptor of Thioxathone (TX) and five amine-type hydrogen donors N-Phenylglycine (NPG), Triethylamine (TEA), Triethanolamine (TEOA), 2,2'-(4-Methylphenylimino)diethanol (p-TDEA), N-Phenyldiethanolamine (n-PDEA), respectively. Among those formulations, the TX/TEOA photoinitiator package showed the best DC values than others. The DC values are in the order of 1:2 wt% > 1.5:1.5wt% > 2:1 wt% for weight ratios investigation of TX/TEOA PI packages. In addition, the DC values are insignificant in either air or nitrogen under TX/TEOA at 1:2 wt%.
We also investigated their photochemical and photophysical properties. The hydrogen donors exhibited the absorption band at lower than 300 nm, which followed the trend p-TDEA > n-PDEA > NPG > TEOA > TEA. After mixing TX with various amine-type hydrogen donors, the PL intensity increased in the following order: TX/p-TDEA > TX/n-PDEA > TX/ NPG > TX/TEA > TX/TEOA. Based on the results of photochemical analysis, the measured molar extinction coefficient was TEA> TEOA> p-TDEA> n-PDEA> NPG. Though all the Type II series exhibited good electron transfer ability by cyclic voltammetry (CV) and free energy change ΔGET results. However, steric hindrance and secondary and tertiary of the amines hydrogen donors played the major factor on the rate of photopolymerization.

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
1.2 光固化系統之簡介......................................2
第二章 文獻回顧與研究動機......................................4
2.1 紫外光之定義及種類......................................4
2.2 光固化工業之發展及應用......................................6
2.3 反應性寡聚物之簡介......................................7
2.4 反應性不飽和單體之簡介......................................8
2.4.1 單官能基反應性單體......................................8
2.4.2 雙官能基反應性單體......................................9
2.4.3 多官能基反應性單體......................................10
2.5 光固化反應機制之介紹......................................14
2.5.1 陽離子型聚合反應......................................14
2.5.2 自由基型聚合反應......................................15
2.6 光起始劑之簡介......................................16
2.6.1 陽離子型光起始劑之簡介......................................17
2.6.2 自由基型光起始劑之簡介......................................18
2.7光固化系統常用氫予體之介紹......................................23
2.7.1 常用二級胺之選擇......................................24
2.7.2 常用三級胺之選擇......................................27
2.8 氧阻聚之影響......................................30
2.9 研究動機與目的......................................31
第三章 實驗方法......................................33
3.1 實驗架構......................................33
3.2 實驗藥品及溶劑......................................34
3.3 儀器設備......................................38
3.3.1 分析儀器......................................38
3.3.2 實驗設備......................................41
3.4 實驗步驟......................................43
3.4.1 光固化反應動力學-凝膠過濾法 (Gel fraction)分析法......43
3.4.2 光固化反應動力學-傅立葉轉換紅外光譜分析方法............45
3.4.3 光化學性分析-紫外/可見光光譜方法.....................46
3.4.4 光化學性分析-螢光光譜分析方法......................47
3.4.5 電化學分析-循環伏安法分析方法......................48
3.4.6 氮氣/空氣對於反應速率之比較........................................49
3.4.7 TGA熱重分析......................................49
3.4.8 DSC示差掃描量熱法分析......................................50
第四章 結果與討論......................................51
4.1 TX與五種氫予體在TMPTMA下之光固化性質分析....................51
4.1.1 Gel fraction轉化率分析......................................51
4.1.2 以FT-IR之固化檢測分析......................................54
4.1.3 以DSC之固化檢測分析......................................54
4.1.4 以TGA之固化檢測分析......................................55
4.2光起始劑及胺類氫予體之光化學性質分析......................................56
4.2.1 紫外光/可見光光譜 (UV/Visible spectra) 之分析結果...............56
4.2.2 螢光光譜 (PL spectra) 之分析結果..............................59
4.2.3 循環伏安法 (CV) 電流-電壓圖的比較.............................62
4.3 在不同環境下反應固化之轉化率比較..............................69
第五章 結論與建議......................................71
第六章 參考文獻......................................72

1.王沛雯, 紫外光硬化丙烯酸酯的研究. 2010.
2.Roffey, C.G., Photopolymerization of surface coatings. 1982: Wiley New York.
3.Dietliker, K., et al. New developments in photoinitiators. in Macromolecular Symposia. 2004. Wiley Online Library.
4.Altinkok, C., et al., In situ synthesis of polymer/clay nanocomposites by type II photoinitiated free radical polymerization. Journal of Polymer Science Part A: Polymer Chemistry, 2011. 49(16): p. 3658-3663.
5.Fuchs, Y., et al., Photopolymerization and photostructuring of molecularly imprinted polymers for sensor applications—A review. Analytica chimica acta, 2012. 717: p. 7-20.
6.王心麟, 鏈轉移劑與活性稀釋劑對UV光固化塗料物性之研究, in 化學工程與材料工程系博碩士班. 2017, 國立高雄應用科技大學. p. 101.
7.O'Brien, J., et al., Advanced photoresist technologies for microsystems. Journal of Micromechanics and Microengineering, 2001. 11(4): p. 353.
8.陳奇毅 and 芮祥鵬. UV Curable 樹脂於不同波長之反應性探討.
9.楊建文, et al., 光固化塗料及應用. 2004, 北京, 化學工業出版社.
10.Endruweit, A., M.S. Johnson, and A.C. Long, Curing of composite components by ultraviolet radiation: A review. Polymer composites, 2006. 27(2): p. 119-128.
11.JCDowdy. Blak-Ray B-100 AP: Spectral Irradiance Chart. 2015; Available from: http://www.ultravioletphotography.com/content/index.php/topic/1249-blak-ray-b-100-ap-spectral-irradiance-chart/.
12.周子钧, 紫外光固化涂料专利发展历程. 科技展望, 2017 (2017 年 27): p. 157-157.
13.Crivello, J.V., UV and electron beam-induced cationic polymerization. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 1999. 151(1-4): p. 8-21.
14.郭政翰, 陽離子型環氧樹脂之光硬化動力學分析與機械性質探討. 臺北科技大學有機高分子研究所學位論文, 2006: p. 1-106.
15.蔡三元 and 葉金泉, 紫外線硬化型環氧寡聚體的合成與物性研究. 成功大學學報, 1990. 24: p. 85-100.
16.黃錫裕, UV Curable PU樹脂之光硬化, in 有機高分子研究所. 2004, 國立臺北科技大學: 台北市. p. 78.
17.周洺偉, 陽離子型紫外光硬化樹脂之研究. 臺北科技大學化學工程研究所學位論文, 2007: p. 1-117.
18.Wu, X., et al., Study on tribological properties of UHMWPE irradiated by electron beam with TMPTMA and TPGDA as crosslinking agents. Wear, 2013. 297(1-2): p. 742-751.
19.李海燕 and 谢川, 阳离子光引发剂研究进展. 信息记录材料, 2004. 5(4): p. 37-41.
20.ZHOU, J., et al., The development of onium salt cationic photoinitiators. Materials Review, 2011. 1: p. 003.
21.ZHONG, Y., et al., Research Progress of Onium Salt Photoinitiators for Cationic Polymerization [J]. Information Recording Materials, 2010. 2: p. 009.
22.Allen, N.S., Photoinitiators for UV and visible curing of coatings: mechanisms and properties. Journal of Photochemistry and Photobiology A: chemistry, 1996. 100(1-3): p. 101-107.
23.Decker, C., Kinetic study and new applications of UV radiation curing. Macromolecular Rapid Communications, 2002. 23(18): p. 1067-1093.
24.洪偉毅, 以光聚合法與化學縮合法製備有機/無機奈米複合材料及其性質研究. 中原大學化學研究所學位論文, 2007: p. 1-168.
25.劉建良, UV Curing 發展簡介及應用. 2003, 化工科技與商情.
26.Crivello, J.V. and J. Lam, Diaryliodonium salts. A new class of photoinitiators for cationic polymerization. Macromolecules, 1977. 10(6): p. 1307-1315.
27.Crivello, J.V. and J. Lam, Photoinitiated cationic polymerization with triarylsulfonium salts. Journal of Polymer Science Part A: Polymer Chemistry, 1979. 17(4): p. 977-999.
28.Crivello, J. and J. Lam, Dye‐sensitized photoinitiated cationic polymerization. Journal of Polymer Science Part A: Polymer Chemistry, 1978. 16(10): p. 2441-2451.
29.HAN, J., et al., Effect of photoinitiator on free radical UV-curing reaction [J]. Applied Science and Technology, 2006. 4: p. 018.
30.Ley, C., et al., Application of High Performance Photoinitiating Systems for Holographic Grating Recording, in Holographic Materials and Optical Systems. 2017, InTech.
31.Andrzejewska, E., et al., Heteroaromatic thiols as co-initiators for type II photoinitiating systems based on camphorquinone and isopropylthioxanthone. Macromolecules, 2006. 39(11): p. 3777-3785.
32.Davidson, R.S., The chemistry of photoinitiators—some recent developments. Journal of Photochemistry and Photobiology A: Chemistry, 1993. 73(2): p. 81-96.
33.Kecici, Z., et al., Temel, Methacrylated benzophone as triple functional compound for the synthesis of partially crosslinked copolymers. Progress in Organic Coatings, 2018. 115: p. 138-142.
34.Karaca, N., et al., Chapter 1. Thioxanthone Photoinitiators with Heterocyclic Extended Chromophores, in Photopolymerisation Initiating Systems. 2018. p. 1-13.
35.Karaca, N., et al., Thioxanthone-benzothiophenes as photoinitiator for free radical polymerization. Journal of Photochemistry and Photobiology A: Chemistry, 2016. 331: p. 22-28.
36.Yilmaz, G., et al., Thioxanthone–carbazole as a visible light photoinitiator for free radical polymerization. Journal of Polymer Science Part A: Polymer Chemistry, 2010. 48(22): p. 5120-5125.
37.钱蓁 and 陈景荣, 新型水溶性硫杂蒽酮类光引发剂的光化学性能研究. 1999.
38.钱蓁 and 王金娣, 新型水溶性硫杂蒽酮类光引发剂的光引发性能研究. 2000.
39.Karaca, N., et al., Mechanistic studies of thioxanthone–carbazole as a one-component type II photoinitiator. Journal of Luminescence, 2014. 146: p. 424-429.
40.Tar, H., et al., Panchromatic Type II Photoinitiator for Free Radical Polymerization Based on Thioxanthone Derivative. Macromolecules, 2013. 46(9): p. 3266-3272.
41.Arsu, N., et al., One component thioxanthone based Type II photoinitiators. Photochemistry and UV curing: new trends. Kerala: Research Signpost, 2006: p. 1-13.
42.Jiang, X., et al., Polymeric photoinitiators containing in-chain benzophenone and coinitiators amine: effect of the structure of coinitiator amine on photopolymerization. Journal of Photochemistry and Photobiology A: Chemistry, 2005. 174(2): p. 165-170.
43.Angiolini, L., et al., Synthesis and photoinitiation activity of radical polymeric photoinitiators bearing side‐chain camphorquinone moieties. Macromolecular Chemistry and Physics, 2000. 201(18): p. 2646-2653.
44.胡建琪, et al., 六芳基双咪唑复合光引发体系的研究及其在液态光致抗蚀剂中的应用. 2008.
45.薛敏钊, et al., 硫杂蒽酮类光引发剂的电子自旋共振研究. 影像科学与光化学, 1993. 11(3): p. 236-243.
46.维基百科编者. 三乙胺. Available from: https://zh.wikipedia.org/wiki/%E4%B8%89%E4%B9%99%E8%83%BA.
47.维基百科编者. 三乙醇胺. Available from: https://zh.wikipedia.org/wiki/%E4%B8%89%E4%B9%99%E9%86%87%E8%83%BA.
48.朱国巍, 紫外光固化涂料的制备及其氧阻聚的研究. 2006.
49.Cheng, L.-l., et al., Photoinitiating characteristics of benzophenone derivatives as type II macromolecular photoinitiators used for UV curable resins. Chem. Res. Chinese Universities, 2011. 27(1): p. 145-149.
50.Kou, H., et al., Photopolymerization kinetics of hyperbranched acrylated aromatic polyester. Journal of applied polymer science, 2003. 89(6): p. 1500-1504.
51.Kunwong, D., et al., Curing behavior of a UV-curable coating based on urethane acrylate oligomer: the influence of reactive monomers. Sonklanakarin Journal of Science and Technology, 2011. 33(2): p. 201.
52.Park, Y.-J., et al., UV-and thermal-curing behaviors of dual-curable adhesives based on epoxy acrylate oligomers. International Journal of Adhesion and Adhesives, 2009. 29(7): p. 710-717.
53.张小兵, et al., 新型 1, 3, 4-噁二唑衍生物的合成与性质研究. 2009.
54.Shi, Y., et al., Photoinitiation properties of heterocyclic hexaarylbiimidazoles with high UV‐vis absorbance. Journal of applied polymer science, 2007. 105(4): p. 2027-2035.
55.何娜, HOMO-LUMO 能隙对分子稳定性的判定. 都市家教: 下半月, 2014(5): p. 179-179.
56.Kissinger, P.T., et al., Electrochemical studies of thioxanthene, thioxanthone, and related species in nonaqueous media. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, 1971. 33(1): p. 1-12.
57.Dadashi-Silab, S., et al., Shining a light on an adaptable photoinitiator: advances in photopolymerizations initiated by thioxanthones. Polymer Chemistry, 2015. 6(37): p. 6595-6615.
58.Bagdasar'Ian, K.S. and Z.A. Sinitsina, Polymerization inhibition by aromatic compounds. Journal of Polymer Science, 1961. 52(157): p. 31-38.
59.Jiang, X., et al., Polymeric amine bearing side-chain thioxanthone as a novel photoinitiator for photopolymerization. Polymer, 2004. 45(1): p. 133-140.
60.张南哲, 叔胺对 UV 固化胶表面氧阻聚抑制作用的研究. 精细石油化工, 2005. 1: p. 33-35.
61.Xiao, B., et al., Study of oxygen inhibition effect on radiation curing. 2000.
62.Chen, Y.-C. and Y.-T. Kuo, Photocuring Kinetic Studies of TMPTMA Monomer by Type II Photoinitiators of Different Weight Ratios of 2-Chlorohexaaryl Biimidazole (o-Cl-HABI) and N-Phenylglycine (NPG). Journal of Photopolymer Science and Technology, 2018. 31(4): p. 487-492.