BEA/DGEBA/MSMA/TiO2耐熱有機／無機奈米複合材料合成及其性質之研究

Synthesis and Properties of Thermal Resistant BEA/DGEBA/MSMA/TiO2Organic/Inorganic Nanocomposites

本研究目的是利用溶膠—凝膠法來合成具優異耐熱性之BEA/DGEBA/MSMA/TiO2有機／無機奈米複合材料。於實驗中先將MSMA矽氧烷耦合劑在酸性環境下pH2~3水解形成矽醇（silanol）中間物，以利進行經前處理之TiO2無機金屬微粒與矽醇中間物的有機化改質反應，使其能順利共價鍵結至有機基材上形成MSMA/TiO2複合物。接著將MSMA/TiO2複合物中活性羥基與Epoxy環氧樹脂預聚物以進行熱縮開環聚合反應形成DGEBA/MSMA/TiO2複合物，最後加入有機壓克力BEA單體與DGEBA/MSMA/TiO2複合物上的活性烯基進行自由基光聚合反應使有機／無機複合材料上之聚合物鏈具備理想之網狀共價鍵結，以利於提升複合材料之耐熱性和機械抗性，製備理想符合光電高科技產業應用之奈米複合材料。合成過程中以FT-IR傅立葉轉換光譜儀來確定反應最佳條件以及最佳組成配方用量比、利用熱重分析儀TGA進行耐熱測試、利用UV-Vis光譜儀來觀測材料在紫外光區和可見光區之透光性測試、最後對進行附著力、鉛筆硬度等機械物理性質測試且分析。結果顯示耐熱性熱裂解溫度Td值最高可達465.2℃，相較於純DGEBA環氧樹脂與DGEBA/MSMA/TiO2複合物最多提升約182.4℃與54.2℃，在可見光區透光性可達到85%以上並UV光區也有遮蔽效果，最後奈米光學薄膜藉由掃描式電子顯微鏡（SEM）檢測，確認無機粉體微粒均勻分佈，且平均粒徑為15~40nm符合奈米材料範圍。 The principal objective in this research is to developeBEA/DGEBA/MSMA/TiO2 organic/inorganic nanocomposites materialswith high thermal resistance, UV-shielding and hightransmittance properties. The MSMA (Methacryloxypropyl-trimethoxysilane)coupling agent was treated the silanol intermediates by acid hydrolysisfor 45minin pH 2~3tetrahydrofuran solution. These silanol intermediates have some active Si-OH functional groups that could form covalent bond between organicmatrixand inorganic titanium oxide colloids. Afterward, the MSMA-modified titanium oxoclusters graft polymerized with epoxide groups ofDGEBA(Diglycidyl ether of bisphenol A) resins monomer to form DGEBA/MSMA/TiO2 complexes by the epoxide ring-opening polycondensation mechanism. After mixingBEA acrylate monomer, the final compound BEA(Bisphenol A ethoxylate diacrylate)/DGEBA/MSMA/TiO2 nanocomposites were synthesized by free radical photopolymerization.TheBEA/DGEBA/MSMA/TiO2organic/inorganic nanocompositeswillenhance the thermal resistant, optical properties.The chemical covalent bonding formation and the best weight contents of reaction components wereidentified by FT-IR spectra. The thermal resistance,hardnessandoptical transmittanceof these nanocomposites weremeasured by TGA,pencil hardness tester and UV-Vis respectively.Experimental results showed that these nanocomposites have85% transmittance in the visible regionsand UV-shielding properties.The best Td valueis 465.2℃which is 182.4℃ and 54.2℃ higher than those of pure DGEBAresin andDGEBA/MSMA/TiO2hybrid material respectively.The morphology structures of the hybrid thin films are estimates by SEM that show inorganic colloidsparticles and the average particle size of thesenanocomposites is about 15~40nm.

The principal objective in this research is to developeBEA/DGEBA/MSMA/TiO2 organic/inorganic nanocomposites materialswith high thermal resistance, UV-shielding and hightransmittance properties. The MSMA (Methacryloxypropyl-trimethoxysilane)coupling agent was treated the silanol intermediates by acid hydrolysisfor 45minin pH 2~3tetrahydrofuran solution. These silanol intermediates have some active Si-OH functional groups that could form covalent bond between organicmatrixand inorganic titanium oxide colloids. Afterward, the MSMA-modified titanium oxoclusters graft polymerized with epoxide groups ofDGEBA(Diglycidyl ether of bisphenol A) resins monomer to form DGEBA/MSMA/TiO2 complexes by the epoxide ring-opening polycondensation mechanism. After mixingBEA acrylate monomer, the final compound BEA(Bisphenol A ethoxylate diacrylate)/DGEBA/MSMA/TiO2 nanocomposites were synthesized by free radical photopolymerization.TheBEA/DGEBA/MSMA/TiO2organic/inorganic nanocompositeswillenhance the thermal resistant, optical properties.The chemical covalent bonding formation and the best weight contents of reaction components wereidentified by FT-IR spectra. The thermal resistance,hardnessandoptical transmittanceof these nanocomposites weremeasured by TGA,pencil hardness tester and UV-Vis respectively.Experimental results showed that these nanocomposites have85% transmittance in the visible regionsand UV-shielding properties.The best Td valueis 465.2℃which is 182.4℃ and 54.2℃ higher than those of pure DGEBAresin andDGEBA/MSMA/TiO2hybrid material respectively.The morphology structures of the hybrid thin films are estimates by SEM that show inorganic colloidsparticles and the average particle size of thesenanocomposites is about 15~40nm.