含端乙焕基硅/氮树脂及其复合材料的研究
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摘要
随着航空航天领域的发展,对耐高温复合材料提出了更高的要求,硅/氮树脂作为性能优异的耐高温复合材料基体树脂,越来越受到科研工作者的重视,这种树脂可用作制备陶瓷前驱体、陶瓷纤维、橡胶添加剂等。本课题将乙炔基引入硅氮烷分子结构中,合成了一系列含乙炔基硅氮烷,使其既具有良好的耐热性,又具备较好的复合材料成型工艺性能。
本文通过三氯硅烷、四氯硅烷与3-乙炔基苯胺反应,制备了三种含端乙炔基硅氮烷单体：甲基-三(3-乙炔苯胺)基硅烷(MTEAS)、苯基-三(3-乙炔苯胺)基硅烷(PTEAS)和四(3-乙炔苯胺)基硅烷(TEAS)；并通过质谱、红外光谱、核磁共振氢谱、核磁共振碳谱等对其结构进行了表征,同时研究了其固化反应动力学,并对其固化物的耐热性进行了研究。结果表明：在氮气氛围中,MTEAS的Td5为510℃,900℃下的质量保留率为75.6%;PTEAS的Td5为540℃,900℃下的质量保留率为79.6%;TEAS的Td5为607℃,900℃下的质量保留率为85.9%。
通过双(N—间乙炔基苯基邻苯二甲酰亚胺)醚(DAIE)对其进行改性,制得复合材料基体树脂。用TEAS-DAIE与玻璃纤维复合制得复合材料,并研究了该复合材料的耐热性、力学性能、介电性能、吸水性、断面形貌等。研究结果表明：复合材料常温下的弯曲强度为385.7MPa,240℃下的弯曲强度达到373.1MPa,保留率为96.7%,复合材料的玻璃化转变温度362.5℃,常温下材料在水中浸泡96小时,其吸水率为1.06%,介电常数(ε)为3.95,介电损耗角正切值(tan6)为5.73×10-3。
With the development of aviation technology, better heat-resistant resins are required. As a kind of outstanding heat-resistant material, silazane is being focused on more and more by the scientists, which can be used to get precursor of ceramic, ceramic fiber, additive of rubber, etc. In this subject acetenyl was introduced into silazane to synthesize a series of acetenyl-silazane with better heat resistance and processability, which provided convenience as the matrix resin of heat-resistant composites.
In this paper, three types of silazane monomers containing terminal alkynyl groups: methyl-tri(3-ethylphenyl-amino)silanes(MTEAS), phenyl-tri(3-ethylphenyl-amino)silanes (PTEAS) and tetra-tri(3-ethylphenyl-amino)silanes(TEAS), whose structures were later characterized using MS、FTIR、1H-NMR and 13C-NMR spectroscopy, were synthesized from the reaction of trichlorosilane and tetrachlorosilane with 3-ethynylaniline. The curing reaction dynamics of the silazanes were also studied. The TGA results show that, in the atmosphere of nitrogen, Td5 for MTEAS, PTEAS and TEAS were 510℃,540℃and 607℃respectively and the mass reserved rate for the three silazanes at 900℃were 75.6%,79.6% and 85.9% respectively.
Di [(N-m-acetenylphenyl) phthalimide] ether (DAIE) was used to modify tetra(3-ethylphenyl-amino)-silanes (TEAS) and obtain the resin(TEAS-DAIE) as the matrix resin of composite. The heat resistance, mechanical strength, dielectric property, water adsorption and the fracture surface were studied. The results showed that the flexural strength of the composite was 385.7MPa at room temperature, which decreased to 373.1MPa at 240℃with the retention ratio 96.7%. Its glass transition temperature is up to 362.5℃. Soak the composite in water at room temperature for 96h and the adsorption ratio was only 1.06%, the dielectric constant was 3.95, and the tangent for the dielectric loss angle is 5.73×10-3.
本文通过三氯硅烷、四氯硅烷与3-乙炔基苯胺反应,制备了三种含端乙炔基硅氮烷单体：甲基-三(3-乙炔苯胺)基硅烷(MTEAS)、苯基-三(3-乙炔苯胺)基硅烷(PTEAS)和四(3-乙炔苯胺)基硅烷(TEAS)；并通过质谱、红外光谱、核磁共振氢谱、核磁共振碳谱等对其结构进行了表征,同时研究了其固化反应动力学,并对其固化物的耐热性进行了研究。结果表明：在氮气氛围中,MTEAS的Td5为510℃,900℃下的质量保留率为75.6%;PTEAS的Td5为540℃,900℃下的质量保留率为79.6%;TEAS的Td5为607℃,900℃下的质量保留率为85.9%。
通过双(N—间乙炔基苯基邻苯二甲酰亚胺)醚(DAIE)对其进行改性,制得复合材料基体树脂。用TEAS-DAIE与玻璃纤维复合制得复合材料,并研究了该复合材料的耐热性、力学性能、介电性能、吸水性、断面形貌等。研究结果表明：复合材料常温下的弯曲强度为385.7MPa,240℃下的弯曲强度达到373.1MPa,保留率为96.7%,复合材料的玻璃化转变温度362.5℃,常温下材料在水中浸泡96小时,其吸水率为1.06%,介电常数(ε)为3.95,介电损耗角正切值(tan6)为5.73×10-3。
With the development of aviation technology, better heat-resistant resins are required. As a kind of outstanding heat-resistant material, silazane is being focused on more and more by the scientists, which can be used to get precursor of ceramic, ceramic fiber, additive of rubber, etc. In this subject acetenyl was introduced into silazane to synthesize a series of acetenyl-silazane with better heat resistance and processability, which provided convenience as the matrix resin of heat-resistant composites.
In this paper, three types of silazane monomers containing terminal alkynyl groups: methyl-tri(3-ethylphenyl-amino)silanes(MTEAS), phenyl-tri(3-ethylphenyl-amino)silanes (PTEAS) and tetra-tri(3-ethylphenyl-amino)silanes(TEAS), whose structures were later characterized using MS、FTIR、1H-NMR and 13C-NMR spectroscopy, were synthesized from the reaction of trichlorosilane and tetrachlorosilane with 3-ethynylaniline. The curing reaction dynamics of the silazanes were also studied. The TGA results show that, in the atmosphere of nitrogen, Td5 for MTEAS, PTEAS and TEAS were 510℃,540℃and 607℃respectively and the mass reserved rate for the three silazanes at 900℃were 75.6%,79.6% and 85.9% respectively.
Di [(N-m-acetenylphenyl) phthalimide] ether (DAIE) was used to modify tetra(3-ethylphenyl-amino)-silanes (TEAS) and obtain the resin(TEAS-DAIE) as the matrix resin of composite. The heat resistance, mechanical strength, dielectric property, water adsorption and the fracture surface were studied. The results showed that the flexural strength of the composite was 385.7MPa at room temperature, which decreased to 373.1MPa at 240℃with the retention ratio 96.7%. Its glass transition temperature is up to 362.5℃. Soak the composite in water at room temperature for 96h and the adsorption ratio was only 1.06%, the dielectric constant was 3.95, and the tangent for the dielectric loss angle is 5.73×10-3.
引文
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