WPU／H12MDI／SR-399／MSMA／WO3耐黃變與抗輻射有機／無機奈米複合材料合成及其性質之研究

Sythesis and properties of WPU/H12MDI/SR-399/MSMA/WO3 Yellowing-resistant and Radiation- resistant Organic/Inorganic Nanocomposites

本研究主要目的是利用溶膠—凝膠法製備具高耐熱性、耐黃變與抗輻射等功能性之WPU／H12MDI／SR-399／MSMA／WO3奈米複合材料。首先將MSMA矽氧烷偶合劑經pH4～5酸性水溶液形成矽醇中間物，以利進行無機金屬氧化物WO3的親有機化改質反應，使能順利化學共價鍵結至有機基材上。接著將此MSMA／WO3複合物中活性Si-OH官能基與有機壓克力SR-399單體上的活性-OH官能基行縮合脫水反應，合成出SR-399／MSMA／WO3複合物，並利用H12MDI改質劑將WPU預聚物末端改質為活性-NCO官能基。最後利用WPU／H12MDI複合物上活性-NCO官能基與SR-399／MSMA／WO3複合物行脲酯化反應以及自由基光聚合反應，使合成的複合物上聚合鏈存在理想網狀化學共價鍵結結構，以提升複合材料的耐熱性及機械性質，合成理想光電高科技產業使用之奈米複合材料。合成時，利用FT-IR光譜儀來確定其最佳反應條件及最佳組成配方比；並利用TGA和DSC之耐熱性測試、UV-Vis透光性測試、抗靜電測試、附著力及塊材硬度等對其熱性質、透明性、導電性及機械物性等性質進行分析。實驗結果顯示這些複合材料在可見光區光穿透度達85％以上且其耐熱性Td值最高可達535.18℃，較純WPU樹脂與有機壓克力SR-399樹脂的Td值高約182.65℃與96.02℃，且在200℃以下並無玻璃轉化溫度（Tg）的存在；而表面電阻值從3.57×1011Ω／cm2降為9.52×109Ω／cm2；硬度可達8H，且黃變指數（YI）小於1.0％，並有輻射遮蔽之效果；最後奈米光學薄膜經SEM檢測結果確認粉體無機微粒均勻分佈且平均粒徑為55～80nm都符合奈米材料的範圍。

This main object of this research is to develop the novel WPU/H12MDI/SR-399/ MSMA/WO3 nanocomposite materials with highly thermal resistance, yellowing-resistance and radiation-resistance characters by sol-gel reaction processes. Firstly, the MSMA coupling agent performed the silanol. These silanol intermediates could couple with WO3. The remained active Si-OH functional groups of the MSMA/WO3 could covalently couple bonding with SR-399 acrylate. Therefore, the SR-399/MSMA/WO3 will be successfully prepared. The WPU/H12MDI prepared from the condensation between WPU prepolymer and H12MDI diisocyanate components. Finally, in order to improve the thermal resistance and mechanical properties, the WPU/H12MDI complexes and the SR-399/MSMA/WO3 complexes were covalently bonded by urethane carbonyl linkages and free radical polymerization to achieve perfectly cross-linking structure of organic/inorganic nanocomposite. The bonding formation were identified by FT-IR spectra. The thermal resistance properties, transmittance, surface resistances, and hardness of these nanocomposites were measured by TGA, DSC, UV-Vis, surface resistance meter and hardness tester respectively. The yellowing index(YI) is less than 1.0%. The morphology structure of the hybrid thin films were estimated by SEM. The results show that the optical thin films distributed with inorganic colloidal particles and the average particle size of these nanocomposites is 55~80 nm.