International Journal of Materials Science
International Journal of Materials Science. 2024; 6: (1) ; 10.12208/j.ijms.20240005 .
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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 北京
*通讯作者： 胡宏林,单位：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 北京；
针对热塑性酚醛树脂裂解反应机理随温度的演变机制不清晰等问题，采用热重-质谱联用技术分析了随裂解温度释放的气体产物种类，间接推导了热塑性酚醛树脂裂解反应机理，结果表明，在100~350℃主要为酚羟基之间的缩聚反应、酚羟基与羟甲基之间的缩聚反应、醚键断链反应、羰基断链反应和甲基断链反应；在350~700℃主要裂解反应机理是酚醛主体结构解离、稠环化；在700~1100℃，主要裂解反应机理为稠环脱氢释放氢气，残留的氧原子与氢气、碳原子二次反应生成水、一氧化碳，树脂由有机物向有机碳和无定形碳转变。本文基于热重-质谱分析研究了热塑性酚醛树脂的裂解化学结构演变，为耐烧蚀酚醛树脂基复合材料烧蚀机理提供理论指导和帮助。
To solve the problem that the pyrolysis mechanism of novolac phenolic resin remained unclear, the evolution of chemical structure of novolac phenolic was investigated. The gas products released with the increase of temperature were characterized by Thermogravimetry-Mass Spectrometry. The pyrolysis reaction mechanisms of the resin in the three main pyrolysis intervals of 100 ~ 350 °C, 350 ~ 700 °C, and 700 ~ 1100 °C were deduced. The results showed that at 100 ~ 350 °C, it was mainly the polycondensation reaction between phenolic hydroxyl groups, the polycondensation reaction between phenolic hydroxyl groups and hydroxymethyl groups, the ether bond breaking chain reaction, the carbonyl breaking chain reaction, and the methyl breaking chain reaction. The main reaction mechanism at 350 ~ 700 °C is the dissociation and cyclization of the main structure of phenolic resin. At 700 ~ 1100 °C, the main reaction is the dehydrogenation of the fused ring to release hydrogen. The residual oxygen atoms react with hydrogen and carbon atoms to form water and carbon monoxide, and the resin changes from organic to organic carbon and amorphous carbon. In this paper, the evolution of chemical structure of novolac phenolic resin was studied based on thermogravimetric-mass spectrometry analysis, which provided theoretical guidance and help for the ablation mechanism of ablation-resistant phenolic resin matrix composites.
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