耐高温复合材料论文含端乙焕基硅-氮树脂及其复合材料的研究.doc

耐高温复合材料论文：含端乙焕基硅/氮树脂及其复合材料的研究【中文摘要】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()为3.95,介电损耗角正切值(tan6)为5.7310-3。【英文摘要】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 510,540and 607respectively and the mass reserved rate for the three silazanes at 900were 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 240with 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 5.7310-3.【关键词】耐高温复合材料 硅氮烷 树脂改性 玻璃纤维增强复合材料【英文关键词】heat-resistant composites silazanes resin modification glass fiber reinforced composites【目录】含端乙焕基硅/氮树脂及其复合材料的研究摘要5-6Abstract6第1章 前言9-251.1 耐高温材料的研究现状9-101.2 耐高温有机硅树脂的研究现状10-141.3 含碳碳叁键的耐高温有机硅树脂14-241.3.1 主链含碳碳叁键的聚碳硅烷14-201.3.2 主链含碳碳叁键的聚碳硅氧烷20-221.3.3 主链含碳碳叁键的聚碳硅氮烷22-241.4 课题研究的目的和创新性24-25第2章 实验部分25-302.1 实验原料及仪器252.2 反应原料的提纯25-262.2.1 间氨基苯乙炔(APA)的提纯252.2.2 四氢呋喃(THF)的提纯25-262.2.3 三乙胺(Et_3N)的提纯262.3 MTEAS、PTEAS和TEAS的合成26-272.4 MTEAS、PTEAS和TEAS固化物的制备272.5 复合材料基体树脂及其固化物的制备27-282.6 分析测试28-30第3章 结果与讨论30-693.1 MTEAS、PTEAS和TEAS的表征30-403.1.1 MTEAS、PTEAS和TEAS的质谱分析30-313.1.2 MTEAS、PTEAS和TEAS的红外分析31-333.1.3 MTEAS、PTEAS和TEAS核磁分析33-383.1.4 MTEAS、PTEAS和TEAS结构的确定38-403.2 MTEAS、PTEAS和TEAS的溶解特性40-413.3 MTEAS、PTEAS和TEAS的固化反应分析41-433.3.1 MTEAS、PTEAS和TEAS的DSC放热曲线41-423.3.2 MTEAS、PTEAS和TEAS的升温流变曲线42-433.4 MTEAS、PTEAS和TEAS的固化反应动力学研究43-513.4.1 MTEAS、PTEAS和TEAS固化反应的表观活化能43-503.4.2 MTEAS、PTEAS和TEAS固化反应级数的确定503.4.3 MTEAS、PTEAS和TEAS固化反应动力学小结50-513.5 MTEAS、PTEAS和TEAS固化制度的确定51-563.5.1 MTEAS固化制度的确定51-533.5.2 PTEAS固化制度的确定53-543.5.3 TEAS固化制度的确定54-563.6 MTEAS、PTEAS和TEAS固化物的耐热性研究56-583.6.1 MTEAS、PTEAS和TEAS的TGA曲线56-573.6.2 MTEAS、PTEAS和TEAS三者耐热性的总结比较57-583.7 TEAS-DAIE的性能研究58-613.7.1 TEAS-DAIE的固化反应59-603.7.2 TEAS-DAIE固化物的耐热性研究60-613.8 TEAS-DAIE基复合材料的性能研究61-693.8.1 TEAS-DAIE基复合材料的层间剪切性能613.8.2 TEAS-DAIE基复合材料的力学性能研究61-6