【摘要】：隨著航空、航天等工業(yè)的迅速發(fā)展,對復(fù)合材料的耐熱性能的要求越來越高,傳統(tǒng)環(huán)氧樹脂固化物的耐熱性已不能達(dá)到所需的技術(shù)要求。因此,開發(fā)具有高耐熱性的環(huán)氧基復(fù)合材料,有十分重要的研究意義。第一,本論文利用雙酚A和甲醛溶液為原料,通過縮合反應(yīng)先得到雙酚A型酚醛樹脂(Bis-ANR),所合成樹脂經(jīng)紅外光譜、核磁共振氫譜、凝膠滲透色譜證實了其結(jié)構(gòu);然后利用合成的酚醛樹脂和環(huán)氧氯丙烷(ECH),進(jìn)一步合成得到雙酚A型酚醛環(huán)氧樹脂(Bis-ANER),合成樹脂經(jīng)紅外光譜、核磁共振氫譜、凝膠滲透色譜等證實了其結(jié)構(gòu)。通過對Bis-ANR和Bis-ANER樹脂合成條件的探究,包括酚醛比、催化劑種類、醚化反應(yīng)溫度、醚化反應(yīng)時間、閉環(huán)反應(yīng)溫度、閉環(huán)反應(yīng)時間,及ECH比例,確定了Bis-ANER樹脂的較佳合成工藝,所得樹脂的環(huán)氧值達(dá)0.51,平均黏度為117Pa·s。第二,本論文利用雙酚A、甲醛溶液和硼酸為原料,合成硼酸改性雙酚A型酚醛樹脂(Bis-ABNR),所合成樹脂經(jīng)紅外光譜、核磁共振譜、凝膠滲透色譜證實了其結(jié)構(gòu)。以Bis-ABNR為固化劑固化Bis-ANER,采用非等溫DSC法研究了該體系的固化動力學(xué)。利用特征溫度確定了體系較佳的固化工藝;利用Kissinger法及Ozawa法對固化反應(yīng)活化能Ea、并對反應(yīng)級數(shù)n、指前因子A、速率方程進(jìn)行了計算。按照已確定的固化工藝進(jìn)行固化,利用差熱分析和熱重分析測定了固化物的耐熱性。研究結(jié)果表明,固化產(chǎn)物具有高的玻璃化轉(zhuǎn)變溫度(Tg),可達(dá)165℃,初始熱分解溫度(Td)為309.85℃,表現(xiàn)出良好的熱穩(wěn)定性和較高的殘?zhí)柯�。第�?本論文利用二甲基亞砜(DMSO)對高嶺土(KL)進(jìn)行插層改性,利用紅外光譜法、X射線衍射分析等手段進(jìn)行表征,表明DMSO已成功進(jìn)入KL。以Bis-ANER為基體樹脂,Bis-ABNR為固化劑,熔融復(fù)合法制備出Bis-ANER/Bis-ABNR/KL-DMSO復(fù)合材料,利用差熱分析和熱重分析測定了復(fù)合材料的耐熱性。研究結(jié)果表明,當(dāng)高嶺土的添加量為5%時,復(fù)合材料的Tg為168.7℃,Td可達(dá)339.8℃,說明添加一定量的高嶺土,可以提高復(fù)合材料的耐熱性。
[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，

本文編號：2218831