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典型结构钡酚醛树脂热解非等温动力学及热稳定性研究
张莹, 胡宏林, 蒋丽琴, 刘亮, 李阳
航天材料及工艺研究所先进功能复合材料技术国防科技重点实验室
摘要:
酚醛树脂指纹结构与热稳定性的相关性对于耐烧蚀材料用树脂基体的选择具有重要指导意义。本文采用核磁氢谱定量描述钡酚醛树脂的典型结构,研究了不同典型结构酚醛树脂的热解活化能、反应机理函数、热稳定性。结果表明,不同结构钡酚醛树脂热解反应活化能在162~240 KJ?mol-1之间,核磁F/P值在1.2~1.5之间时热解反应活化能最高,树脂热稳定性最好;钡酚醛树脂在570°C时的热解最概然机理函数g(a)=(1-α)-b-1(b=5.2~6.7),为化学反应机制,通过酚醛树脂裂解气相色谱-质谱分析和复合材料电弧加热烧蚀性能分析验证了树脂核磁F/P值在1.2-1.5之间时热稳定性最好。本文建立了酚醛树脂典型指纹结构和热稳定性之间的相关性,为开发新型耐烧蚀酚醛树脂提供了有益的帮助。
关键词:  酚醛树脂,本征结构,热解机理,活化能
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Non-Isothermal Pyrolysis Kinetic Mechanism and Thermal stabilization of Phenolic Resin with Different Characteristic Structure
Ying Zhang, Honglin Hu, Liqin Jiang, Liang Liu, Yang Li
Science and Technology on Advanced Functional Composites Laboratory,Aerospace Research Institute of Materials Processing Technology
Abstract:
The relationship between the characteristic structure and thermal stability of phenolic resin is of great significance for the selection of resin matrix for ablative materials. In this paper, the typical structure of phenolic resin was quantitatively described by 1H Nuclear Magnetic Resonance spectroscopy. The activation energy, reaction mechanism function, and thermal stability of different typical structure phenolic resins were studied. The results show that the activation energy of phenolic resin with different structures is 162~240 KJ?mol-1. The activation energy of the pyrolysis reaction is the highest and the thermal stability of the resin is optimum when the F/P value is 1.2~1.5. The most probable mechanism function of pyrolysis at 570 °C is g(a)=(1-α)-b-1(b=5.2~6.7), which is the chemical reaction mechanism. The results of pyrolysis kinetics were verified by qualitative and quantitative analysis of pyrolysis gas products using Py-GC/MS. The high-temperature thermal stability of phenolic resin with different structures was further proved by electric arc heating ablation of carbon fiber reinforced phenolic resin composites.
Key words:  Phenolic resin, Characteristic structure, Pyrolysis Kinetic Mechanism, Activation energy