硼改性酚醛树脂的固化及裂解  

Curing and pyrolysis of boron-modified phenolic resin

作　　者：陈孝飞[1] 李树杰[1] 闫联生[2] 远玉凤[1] 

机构地区：[1]北京航空航天大学材料科学与工程学院,北京100191 [2]中国航天科技集团公司第四研究院第四十三研究所,西安710025

出　　处：《复合材料学报》2011年第5期89-95,共7页Acta Materiae Compositae Sinica

基　　金：国家自然科学基金(51172011)

摘　　要：采用DSC、Ozawa法、固态13C核磁共振（13C NMR）、红外光谱（IR）、裂解-气相色谱（Py-GC）和XRD研究了硼改性酚醛树脂的固化动力学、固化机制和裂解行为。结果表明：硼改性酚醛树脂的近似凝胶温度、固化温度和后处理温度分别为350.0 K、386.2 K和433.3 K,固化反应峰顶的活化能为152.4 kJ/mol;硼改性酚醛树脂的固化反应主要包括PhCH2—OH之间的反应、PhCH2—OH与B—OH之间的反应、PhCH2—OH与酚环上活泼氢之间的反应,以及醚键的歧化反应。硼改性酚醛树脂的剧烈分解温度为500~800℃,失重为14.9%;裂解生成的挥发物有CO、CO2、H2O、苯和甲苯等;在1000℃时的残碳率为67.2%;硼改性酚醛树脂在1000℃高温裂解30 min后生成了玻璃碳。The curing kinetics,curing mechanism and pyrolysis of boron-modified phenolic resin were investigated by means of non-isothermal DSC technique,Ozawa method,solid-state 13C nuclear magnetic resonance（NMR）,infrared spectrum（IR）,pyrolysis-gas chromatography（Py-GC）and XRD.The results show that the approximate theoretical temperatures of gel,cure and post-treatment are 350.0 K,386.2 K and 433.3 K,respectively.Its apparent activation energy at exothermic peak is 152.4 kJ/mol.The curing process involves the reactions of PhCH2—OH to itself,PhCH2—OH to B—OH,PhCH2—OH to H of phenol ring as well as disproportionation of ether link.The mass loss at the range of 500 ℃ to 800 ℃ in the pyrolysis is 14.9%,and the pyrolysis products are mainly volatile compounds,such as CO,CO2,H2O,benzene and toluene.The residual carbon value at 1000 ℃ is 67.2%.The boron-modified phenolic resin is pyrolyzed into glass carbon after the heat-treatment at 1000 ℃ for 30 min.

关 键 词：硼改性酚醛树脂 固化动力学 裂解 差示扫描量热法 固态13C核磁共振 

分 类 号：TB332[一般工业技术—材料科学与工程] TQ323.1[化学工程—合成树脂塑料工业]