溶胶—凝胶法制备耐热光固化有机—无机杂化材料
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摘要
传感技术是信息化时代的重要内容之一。传感器是新技术革命和信息社会的重要技术基础。光纤传感器在电力、石油化工、生医生化、航空航天、环保、国防等领域得到推广应用。光纤传感器在恶劣的环境当中对光纤的各项性能要求很高,主要取决于光纤的涂层。
因此本文研究耐热光纤涂层。首先采用不同分子量的聚丙二醇、2,4-二异氰酸酯、丙烯酸羟乙酯制备不同聚氨酯丙烯酸酯低聚体,利用丙酮-二正丁胺法测定异氰酸酯基的反应程度。通过热失重分析仪得到分子量为2000的聚丙二醇制备得到的聚氨酯丙烯酸酯的耐热温度最佳,热失重温度达到280℃。同时差示扫描仪得到聚氨酯丙烯酸酯预聚体存在两个玻璃化转变温度,一个在29.7℃,另外一个出现在104℃,分别表示为聚氨酯丙烯酸酯的软段部分和硬段部分。
然后通过PPG2000制备的聚氨酯丙烯酸酯与环氧丙烯酸酯按照一定的配方共混,通过硬度测试、固化度测试以及热失重分析得到,聚氨酯丙烯酸酯与环氧丙烯酸酯配比在2：1时共混体系表现出最佳的热稳定性。
最后通过溶胶-凝胶法,以正硅酸乙酯为硅源,酸或者碱作为催化剂,乙醇与水溶液作为介质,制备硅溶胶。然后与质量比为2：1聚氨酯丙烯酸酯与环氧丙烯酸酯体系共混。以硅烷偶联剂作为有机部分与无机部分的桥梁。然后通过紫外光引发固化,制备得到杂化材料。通过场发射扫描电镜图可以得到,酸作为催化剂时,二氧化硅的颗粒更小,粒径大约为80～100nm。硅烷偶联剂KH570防止二氧化硅团聚更好,制备得到的粒径比其他偶联剂要小,分散也更好。通过热失重对比,当TEOS:(PUA+EA)=0.4:1时,杂化材料里面二氧化硅颗粒大小在80～100nm之间,同时表面比纯树脂更加粗糙。热失重温度达到350℃,热分解温度也高达143.8℃,比纯树脂体系提高了大约70℃,杂化材料中的二氧化硅表现出良好的结晶性。
Sensor technique is one of the most important technologies during the information age. Sensor is the basement of the technological revolution and information society. Fiber optical sensor is paid more and more attention due to the wide application, such as power transmission system, petrochemical industry, biochemical engineering, aeronautics and space industry, environment engineering and national security et al. The properties of fiber optical sensor are more vital while is used in environmental extremes. The properties are depended on the coating of the fiber.
So the thesis was focused on the coating for optical fiber. First and foremost, the oligomer of polyurethane acrylate (PUA) was synthesized based on polypropylene glycol (PPG),2,4-toluene diisocynate (2,4-TDI) and hydroxyethyl acrylate (HEA). Content of isocyanate group in polyurethane acrylate prepolymer was tested with acetone dibutylamine method. Thermogravimetic analysis (TGA) showed that the oligomer synthesized by PPG2000exhibited the best thermal stability and the initial decomposition temperature (IDT) was about280℃. There were two glass-transition temperature (Tg),29.7℃and104℃respectively, appeared in the curve of differential scanning calorimeter (DSC). They respectively represented the soft segment and rigid part.
Secondly, polyurethane acrylate was blended with epoxy acrylate (EA) with different ratios. The hardness test, curing degree test and TGA all illuminated the system with the ratio of PUA:EA of2:1showed the best thermal property.
Last and not the least, the silica sol was produced by sol-gel reaction with tetraethoxysilane as the silicon resource, acid or base as catalyst and deionized water-ethanol as medium. Next, the silica sol was charged to the PUA and EA system with different ratios. Silane coupling agent connected organic part and inorganic part with chemical bond to obtain hybrid materials. The graphs from field emission scanning electron microscope (FESEM) showed the diameter of silica particles prepared by acid as catalyst was about80-100nm and KH-570was perfectly avoid the agglomeration and the particles was dispersed well in resin. According to TGA, the hybrid material made from the ratio of TEOS:(PUA+EA) of0.4:1started to lose weight at about350℃. Meanwhile, the thermal decomposition temperature was arriving at143.8℃, was approximately70℃higher than pure resin. The silica particles showed perfect crystallinity.
因此本文研究耐热光纤涂层。首先采用不同分子量的聚丙二醇、2,4-二异氰酸酯、丙烯酸羟乙酯制备不同聚氨酯丙烯酸酯低聚体,利用丙酮-二正丁胺法测定异氰酸酯基的反应程度。通过热失重分析仪得到分子量为2000的聚丙二醇制备得到的聚氨酯丙烯酸酯的耐热温度最佳,热失重温度达到280℃。同时差示扫描仪得到聚氨酯丙烯酸酯预聚体存在两个玻璃化转变温度,一个在29.7℃,另外一个出现在104℃,分别表示为聚氨酯丙烯酸酯的软段部分和硬段部分。
然后通过PPG2000制备的聚氨酯丙烯酸酯与环氧丙烯酸酯按照一定的配方共混,通过硬度测试、固化度测试以及热失重分析得到,聚氨酯丙烯酸酯与环氧丙烯酸酯配比在2：1时共混体系表现出最佳的热稳定性。
最后通过溶胶-凝胶法,以正硅酸乙酯为硅源,酸或者碱作为催化剂,乙醇与水溶液作为介质,制备硅溶胶。然后与质量比为2：1聚氨酯丙烯酸酯与环氧丙烯酸酯体系共混。以硅烷偶联剂作为有机部分与无机部分的桥梁。然后通过紫外光引发固化,制备得到杂化材料。通过场发射扫描电镜图可以得到,酸作为催化剂时,二氧化硅的颗粒更小,粒径大约为80～100nm。硅烷偶联剂KH570防止二氧化硅团聚更好,制备得到的粒径比其他偶联剂要小,分散也更好。通过热失重对比,当TEOS:(PUA+EA)=0.4:1时,杂化材料里面二氧化硅颗粒大小在80～100nm之间,同时表面比纯树脂更加粗糙。热失重温度达到350℃,热分解温度也高达143.8℃,比纯树脂体系提高了大约70℃,杂化材料中的二氧化硅表现出良好的结晶性。
Sensor technique is one of the most important technologies during the information age. Sensor is the basement of the technological revolution and information society. Fiber optical sensor is paid more and more attention due to the wide application, such as power transmission system, petrochemical industry, biochemical engineering, aeronautics and space industry, environment engineering and national security et al. The properties of fiber optical sensor are more vital while is used in environmental extremes. The properties are depended on the coating of the fiber.
So the thesis was focused on the coating for optical fiber. First and foremost, the oligomer of polyurethane acrylate (PUA) was synthesized based on polypropylene glycol (PPG),2,4-toluene diisocynate (2,4-TDI) and hydroxyethyl acrylate (HEA). Content of isocyanate group in polyurethane acrylate prepolymer was tested with acetone dibutylamine method. Thermogravimetic analysis (TGA) showed that the oligomer synthesized by PPG2000exhibited the best thermal stability and the initial decomposition temperature (IDT) was about280℃. There were two glass-transition temperature (Tg),29.7℃and104℃respectively, appeared in the curve of differential scanning calorimeter (DSC). They respectively represented the soft segment and rigid part.
Secondly, polyurethane acrylate was blended with epoxy acrylate (EA) with different ratios. The hardness test, curing degree test and TGA all illuminated the system with the ratio of PUA:EA of2:1showed the best thermal property.
Last and not the least, the silica sol was produced by sol-gel reaction with tetraethoxysilane as the silicon resource, acid or base as catalyst and deionized water-ethanol as medium. Next, the silica sol was charged to the PUA and EA system with different ratios. Silane coupling agent connected organic part and inorganic part with chemical bond to obtain hybrid materials. The graphs from field emission scanning electron microscope (FESEM) showed the diameter of silica particles prepared by acid as catalyst was about80-100nm and KH-570was perfectly avoid the agglomeration and the particles was dispersed well in resin. According to TGA, the hybrid material made from the ratio of TEOS:(PUA+EA) of0.4:1started to lose weight at about350℃. Meanwhile, the thermal decomposition temperature was arriving at143.8℃, was approximately70℃higher than pure resin. The silica particles showed perfect crystallinity.
引文
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