臺灣博碩士論文加值系統

本研究為製備一有機無機奈米混成紫外光硬化塗膜，主要以壓克力多元醇為主體，藉由導入具高度UV吸收性之CeO2來增加該塗料的耐候性質。首先針對合成PU-acrylate oligomer預聚物的進料順序加以探討，實驗中改變進料順序，且得到不同分子量的高分子，進而影響塗膜的黏度與Tg。
在高分子中添加CeO2 溶膠會有CeO2粒子聚集而造成穩定性不佳的問題。以直接添加市售奈米級CeO2溶膠的方式，雖然高分子鏈中含眾多的OH基與CeO2溶膠中的OH可形成氫鍵，發現添加無機物後Tg會有所提升，但CeO2顆粒分散效果極差，嘗試以有機酸鹼改變預聚物溶液的pH值，pH值調高或低，CeO2聚集度略有改善，但其改善效果有限。
為了加強有機/無機之間的界面強度，分別探討離子-離子偶極作用力(ion-ion dipole interaction)與共價鍵結作為界面改質的影響，其中離子-離子偶極作用力的建立方式，是在PU-acrylate oligomer上導入含酸的官能基(2,2-dimethylolpropionic acid, DMPA)，且以鹼液調整pH值，使DMPA分子上之COOH解離成COO¯，以此負離子去穩定CeO2奈米粒子進而達到加強有機無機界面強度的效果，研究顯示，隨著DMPA含量增加對CeO2無機顆粒的分散性有明顯提升，塗膜的透光度也獲得改善。
另一方面，以polyisocyanate與CeO2進行銜接反應形成共價鍵結，並由滴定法控制polyisocyanate之-NCO與CeO2表層之-OH基反應的程度，最佳條件為使polyisocyanate上1/3之-NCO接至CeO2上，其餘2/3作為與polyol聚合用，所得改質之有機/無機的塗膜其透光度與CeO2分散性有大幅度的提升。此外，以共價鍵改質不會影響原純高分子塗膜的Tg、耐溶劑性與硬度，以及能保有本身高分子的吸收，並同時擁有較高的UV吸收的效能。

In this research, an organic/inorganic hybrid UV curable resin was prepared. An acrylic polyol reacting with isocyanate was used as organic backbone which was then end capped with HEMA (Hydroxyethyl Methacrylate) to provide a C = C for subsequent UV curing.
Incorporating CeO2 particle into this organic resin usually leads to CeO2 particles aggregation which dramatically reduce the transparency of the resultant coating. In this study we fist adjust the pH of the organic media to enhance H-bonding between polymer and CeO2 .It improves CeO2 dispersion but only to a small degree. An approach was taken by incorporating DMPA (2,2-dimethylolpropionic acid) to the polymer backbone(ion-ion dipole interaction). An ion-ion dipole interaction was encouraged to occur via adjusting pH of the resin which results in dissociation of COOH in DMPA to COO-. With this approach, the dispersibility is unproved. However, TEM still indicate minor CeO2 aggregation.
An ultimate solution is to establish a covalent bond between organic phase and CeO2. A polyisocyanate with three -NCO group was used to react with the –OH group on the surface of CeO2. The extent of –NCO reaction was monitored through –NCO titration. The between –NCO and –OH was proceed until 1/3 of –NCO is consumed. The remaining 2/3 of –NCO are used to attach to the polymer backbone. The resultant polymer/CeO2 composite show a nano-dispersed CeO2 particle with excellent transmission in visible spectroscopy.

中文摘要．．．．．．．．．．．．．．．．．．．．．．．．I
英文摘要．．．．．．．．．．．．．．．．．．．．．．．．．III
誌謝．．．．．．．．．．．．．．．．．．．．．．．．．．．V
目錄．．．．．．．．．．．．．．．．．．．．．．．．．．VI
表目錄．．．．．．．．．．．．．．．．．．．．．．．．．IX
圖目錄．．．．．．．．．．．．．．．．．．．．．．．．XII

第一章 緒論．．．．．．．．．．．．．．．．．．．．．．．．1
1-1 前言．．．．．．．．．．．．．．．．．．．．．．．．．1
1-2 PU樹脂 ．．．．．．．．．．．．．．．．．．．．．．．3
1-2.1 PU簡介．．．．．．．．．．．．．．．．．．．．．3
1-2.2 PU基本構造與物性之關係．．．．．．．．．．．．．4
1-2.3 PU在塗料方面的用途．．．．．．．．．．．．．．．7
1-3 二氧化鈰．．．．．．．．．．．．．．．．．．．．．．．7
1-4 有機/無機奈米複合材料．．．．．．．．．．．．．．．．8
1-5 有機/無機奈米複合塗料．．．．．．．．．．．．．．．．．10
1-6 光硬化型塗料樹脂．．．．．．．．．．．．．．．．．．．11
1-6.1 簡介．．．．．．．．．．．．．．．．．．．．11
1-6.2 光硬化型樹脂的種類．．．．．．．．．．．．．．．13
1-6.3 紫光硬化型樹脂組成．．．．．．．．．．．．．．．14
1-6.4 光硬化型樹脂反應過程．．．．．．．．．．．．．．18
1-6.5 影響光硬化反應的因素．．．．．．．．．．．．．．19
1-7 CeO2相關文獻回顧．．．．．．．．．．．．．．．．．．．20
1-8 研究目的與架構．．．．．．．．．．．．．．．．．．．．23
第二章 實驗藥品與分析儀器之簡介．．．．．．．．．．．．．26
2-1 實驗藥品．．．．．．．．．．．．．．．．．．．．．．．26
2-2 實驗儀器．．．．．．．．．．．．．．．．．．．．．．．31
2-2.1 實驗器材．．．．．．．．．．．．．．．．．．．．31
2-2.2 分析儀器．．．．．．．．．．．．．．．．．．．．33
第三章 紫外光硬化型PU-acrylate-氧化鈰奈米複合材料之製備．38
3-1 PU-acrylate oligomer的製備．．．．．．．．．．．．．．38
3-1.1合成PU-acrylate oligomer (I)過程．．．．．．．．．38
3-1.2合成PU-acrylate oligomer (II)過程．．．．．．．．．47
3-1.3 PU-acrylate oligomer黏度探討．．．．．．．．．．．47
3-2紫外光硬化條件．．．．．．．．．．．．．．．．．．．．52
3-2.1 硬化環境的影響．．．．．．．．．．．．．．．．．52
3-2.2 硬化時間與光起始含量對C = C的影響．．．．．．．．56
3-2.3 添加不同比例TMPTA對薄膜的性質影響．．．．．．．58
3-3導入奈米氧化鈰塗膜性能之影響．．．．．．．．．．．．．62
3-3.1探討CeO2直接導入PU-acrylate oligomer之分散性．．62
3-3.2探討CeO2直接導入PU-acrylate oligomer之機械性質．69
3-3.3探討改變pH值對有機無機之界面之影響．．．．．．． 71

第四章 探討有機/無機界面間建立不同化學鍵結對奈米複合塗膜性
能之影響．．．．．．．．．．．．．．．．．．．．．75
4-1探討以離子鍵結強化界面對複合塗膜性能之影響．．．．．．75
4-2探討以共價鍵結強化界面對複合塗膜性能之影響．．．．．．93
4-3 複合塗膜硬度與耐溶劑性．．．．．．．．．．．．．．．．104
4-4 複合塗料光學性質．．．．．．．．．．．．．．．．．．．105
第五章 結論．．．．．．．．．．．．．．．．．．．．．．110
參考文獻．．．．．．．．．．．．．．．．．．．．．．．．114

1. 張光偉，化工資訊，第3期，36-45，1998
2. 賴宏仁，工業材料，153期，94-101，1999
3. 張豐志，應用高分子手冊，五南圖書出版，2003
4. 徐國財、張立德，奈米複合材料，五南圖書出版，2004
5. 朱屯、王福明、王習東，奈米材料技術，五南圖書出版，2003
6. Gnter Oertel, ”Polyurethane Handbook” , Hanser Publisher, Munich
Vienna, New York, 1985
7. C.S. Schollenberger, ”Polyurethane Technology”, Ed., P.F. Bruin,
Interscience Publishers, New York, 1979
8. M. V. Pandya, D. D. Seshande and D. G. Hundiwale, J. of Appl.
Polym. Sci, 1986, 32, 4945
9. A. A. R. Sayigh, H. Ulrich & W. J. Farrissey, ”Diisocyanate” , John
Wiley, 1990
10. 工業技術研究院奈米研討會資料，2003
11. 柯楊船、[美]皮特．斯壯，聚合物－無機奈米複合材料，五南圖
書出版，2004
12. H. Huang, B. Orler, G. L.Wilkes, Macromolecules, 1987, 20, 1322
13. J. D. Mackenzie in Hybrid Organic-Inorganic Composites, edited by
J. E. Mark, C. Y-C Lee, P. A. Bianconi ( Maple Press, New York,
1995 ), p226.

14. 劉建良，「UV Curing發展簡介及應用」，化工科技與商情，第
四十一期，2003，第1-4頁
15. 張上鎮，「紫外光硬化塗料與塗裝(1)」，塗料與塗裝技術，第二
十一期，2001，第22-30頁
16. 吳丁凱，光硬化型樹脂的發展動向，專題調查報告，工業技術研
究院化學工業研究所，新竹，1987
17. 宋維孝，「UV硬化塗料/印墨最近動向」，高分子工業，第四期，
2002，第23頁
18. 陳奇毅，UV Curable PU樹脂於不同波長之反應性探討，碩士論
文，國立臺北科技大學有機高分子研究所，台北，2002
19. 王德海，紫外光固化材料-理論與應用，北京：科學出板社，2001，
第97，127-130頁
20. UV curing, science and technology. Ed. S. Peter Pappar. Technology
marketing corporation. 1980
21. C. Decker, Kinetic Study and New Application of UV Radiation Curing,
Macromol. Rapid. Commium. 2002, 23, 1067
22. C. G. Roffey, John Wiley & Sons ”Photopolymerization of surface
coating” , 1988
23. L. Keller, C. Decker, K. Zahouily, S. Benfarhi, J. M. Le Meins, J.
Miehe-Brendle, Synthesis of Polymer Nanocomposites by UV-curing
of Organoclay-Acrylic resins, Polymer, 2004, 45, 7437
24. C. Decker, S. Birty, K. Zahouily, Polymer. Degrad. Stabil, 1995, 49,
111
25. C. Decker, K. Zahouily, A. Valet, Macromol. Mater. Eng, 2001, 286, 5
26. C. Decker, K. Zahouily, A. Valet, J. Coat. Technol. 2002, 74, 87
27. A. Sehgal, Y. Lalatonne, J-F. Berret and M. Morvan, Precipitation
-Redispersion of Cerium Oxide Nanoparticles with Poly ( acrylic
acid ): Toward Stable Dispersion, Lamgmuir, 2005, 21, 9359
28. S. Yabe, M. Yamashita, S. Momose, K. Tahira, S. Yoshida, R. Li, Shu Yin, T. Satok, Synthesis and UV-shielding properties of metal oxide doped ceria via soft solution chemical processes, International Journal of Inorganic Materials, 2001, 3, 1003
29. S. Yabe and T. Sato, Cerium oxide for sunscreen cosmetics, J of solid State chem., 2003, 171, 7
30. T. Morimoto, H. Tomonaga, A. Mitani, Ultraviolet ray absorbing coatings on glass for automobiles, Thin solid Films, 1999, 351, 61
31. Norman S. Allen, Michele Edge, A. Ortega, G. Sandoval,
Christopher M. Liauw, J. Verran, John Stratton, Robert B. Mcintyre,
Degradation and Stabilization of Polymers and Coatings: Nano Versus
Pigmentary Titania Particles, Polymer degradation and stability, 2004,
85, 927
32.E. Tang, G. Cheng, X. Ma, Preparation of nano-ZnO /PMMA composite particles via grafting of the copolymer onto surface of zinc oxide nanoparticles, Power technology, 2006, 161, 209-214
33. T. Masui, H. Hirai, N. Imanaka, G. Adachi, New Sunscreen Materials Based on Amorphous Cerium and Titanium Phosphate, J. of Alloys and Compounds, 2006, 408-412, 1141
34. A. Mohamed El-Toni, S. Yin, S. Yabe, T. Sato, Coating of Calcia -Doped Ceria with Amorphous Silica Shell by Seeded Polymerization Technique, Materials Research Bulletin, 2005, 40, 1059
35.張育圖，新型聚三烷基噻吩衍生物的合成與光電性質的探討，碩士論文，國立中央大學化學研究所，台北，2004
36. K. S. Chung, J.C. Lee, H. Lee, S. Y. Eom, E. A. Yoo, Synthesis of highly concentrated TiO2 nanocolloids and coating on boron nitride powders, colloids and surfaces, 2008, 175-178