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研究生:蔣治全
研究生(外文):Jhih-Cyuan Jiang
論文名稱:紫外線硬化奈米塗料之有機無機界面改質研究紫外線硬化奈米塗料之有機無機界面改質研究
論文名稱(外文):Study the effect of organic / inorganic interface on the properties of a UV curable resin
指導教授:黃永慈
指導教授(外文):Yeong-Tsyr Hwang
學位類別:碩士
校院名稱:南台科技大學
系所名稱:化學工程與材枓工程系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2008
畢業學年度:96
語文別:中文
論文頁數:117
中文關鍵詞:奈米二氧化鈰紫外線硬化樹脂奈米複合材料
外文關鍵詞:UV curable resinPUCeO2
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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
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