高耐热性酚醛环氧树脂的制备及其复合材料的性能研究
发布时间：2018-09-02 08:37
【摘要】：随着航空、航天等工业的迅速发展,对复合材料的耐热性能的要求越来越高,传统环氧树脂固化物的耐热性已不能达到所需的技术要求。因此,开发具有高耐热性的环氧基复合材料,有十分重要的研究意义。第一,本论文利用双酚A和甲醛溶液为原料,通过缩合反应先得到双酚A型酚醛树脂(Bis-ANR),所合成树脂经红外光谱、核磁共振氢谱、凝胶渗透色谱证实了其结构;然后利用合成的酚醛树脂和环氧氯丙烷(ECH),进一步合成得到双酚A型酚醛环氧树脂(Bis-ANER),合成树脂经红外光谱、核磁共振氢谱、凝胶渗透色谱等证实了其结构。通过对Bis-ANR和Bis-ANER树脂合成条件的探究,包括酚醛比、催化剂种类、醚化反应温度、醚化反应时间、闭环反应温度、闭环反应时间,及ECH比例,确定了Bis-ANER树脂的较佳合成工艺,所得树脂的环氧值达0.51,平均黏度为117Pa·s。第二,本论文利用双酚A、甲醛溶液和硼酸为原料,合成硼酸改性双酚A型酚醛树脂(Bis-ABNR),所合成树脂经红外光谱、核磁共振谱、凝胶渗透色谱证实了其结构。以Bis-ABNR为固化剂固化Bis-ANER,采用非等温DSC法研究了该体系的固化动力学。利用特征温度确定了体系较佳的固化工艺;利用Kissinger法及Ozawa法对固化反应活化能Ea、并对反应级数n、指前因子A、速率方程进行了计算。按照已确定的固化工艺进行固化,利用差热分析和热重分析测定了固化物的耐热性。研究结果表明,固化产物具有高的玻璃化转变温度(Tg),可达165℃,初始热分解温度(Td)为309.85℃,表现出良好的热稳定性和较高的残炭率。第三,本论文利用二甲基亚砜(DMSO)对高岭土(KL)进行插层改性,利用红外光谱法、X射线衍射分析等手段进行表征,表明DMSO已成功进入KL。以Bis-ANER为基体树脂,Bis-ABNR为固化剂,熔融复合法制备出Bis-ANER/Bis-ABNR/KL-DMSO复合材料,利用差热分析和热重分析测定了复合材料的耐热性。研究结果表明,当高岭土的添加量为5%时,复合材料的Tg为168.7℃,Td可达339.8℃,说明添加一定量的高岭土,可以提高复合材料的耐热性。
[Abstract]:With the rapid development of aviation and aerospace industry, the requirement of heat resistance of composite materials is more and more high. The heat resistance of traditional epoxy resin cured is not up to the required technical requirements. Therefore, it is of great significance to develop epoxy matrix composites with high heat resistance. Firstly, bisphenol A phenolic resin (Bis-ANR) was synthesized by condensation reaction using bisphenol A and formaldehyde solution as raw materials. The synthesized resin was confirmed by IR, NMR and gel permeation chromatography. Then the bisphenol A phenolic epoxy resin (Bis-ANER) was further synthesized by using the synthetic phenolic resin and epichlorohydrin (ECH),. The structure of the synthetic resin was confirmed by IR, NMR and gel permeation chromatography. The optimum synthetic conditions of Bis-ANR and Bis-ANER resins were studied, including phenolic ratio, type of catalyst, etherification temperature, etherification time, closed loop reaction temperature, closed loop reaction time and ECH ratio. The epoxy value of the resin was 0.51 and the average viscosity was 117Pa s. Secondly, bisphenol A phenolic resin (Bis-ABNR) modified by boric acid was synthesized by using bisphenol A, formaldehyde solution and boric acid as raw materials. The synthesized resin was confirmed by IR, NMR and gel permeation chromatography. The curing kinetics of Bis-ABNR curing Bis-ANER, was studied by non isothermal DSC method. The best curing process was determined by characteristic temperature, and the curing activation energy (Ea,) was calculated by Kissinger method and Ozawa method, and the reaction order n, preexponential factor A and rate equation were calculated. The heat resistance of the cured compounds was determined by differential thermal analysis and thermogravimetric analysis. The results show that the cured products have high glass transition temperature (Tg),) and initial thermal decomposition temperature (Td) of 309.85 鈩，
本文编号：2218831
[Abstract]:With the rapid development of aviation and aerospace industry, the requirement of heat resistance of composite materials is more and more high. The heat resistance of traditional epoxy resin cured is not up to the required technical requirements. Therefore, it is of great significance to develop epoxy matrix composites with high heat resistance. Firstly, bisphenol A phenolic resin (Bis-ANR) was synthesized by condensation reaction using bisphenol A and formaldehyde solution as raw materials. The synthesized resin was confirmed by IR, NMR and gel permeation chromatography. Then the bisphenol A phenolic epoxy resin (Bis-ANER) was further synthesized by using the synthetic phenolic resin and epichlorohydrin (ECH),. The structure of the synthetic resin was confirmed by IR, NMR and gel permeation chromatography. The optimum synthetic conditions of Bis-ANR and Bis-ANER resins were studied, including phenolic ratio, type of catalyst, etherification temperature, etherification time, closed loop reaction temperature, closed loop reaction time and ECH ratio. The epoxy value of the resin was 0.51 and the average viscosity was 117Pa s. Secondly, bisphenol A phenolic resin (Bis-ABNR) modified by boric acid was synthesized by using bisphenol A, formaldehyde solution and boric acid as raw materials. The synthesized resin was confirmed by IR, NMR and gel permeation chromatography. The curing kinetics of Bis-ABNR curing Bis-ANER, was studied by non isothermal DSC method. The best curing process was determined by characteristic temperature, and the curing activation energy (Ea,) was calculated by Kissinger method and Ozawa method, and the reaction order n, preexponential factor A and rate equation were calculated. The heat resistance of the cured compounds was determined by differential thermal analysis and thermogravimetric analysis. The results show that the cured products have high glass transition temperature (Tg),) and initial thermal decomposition temperature (Td) of 309.85 鈩，
本文编号：2218831
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