基于变温FTIR光谱和热重质谱的树脂固化机理研究

H. Hu, W. Wang, Liqin Jiang, Liang Liu, Y. Zhang, Y. Yang, Jinming Wang
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引用次数: 4

摘要

为解决Ba(OH)2催化酚醛树脂固化机理演化不明确的问题,引入p-p亚甲基指数、o-p亚甲基指数、o-o亚甲基指数、羟基甲基指数和醚指数,定量研究了90 ~ 230℃固化温度范围内树脂的化学结构。利用变温红外光谱对其化学结构进行了表征。采用热重质谱法对随固化温度升高而释放的气体产物进行了表征。最后总结了90 ~ 230℃的固化机理。结果表明,在90 ~ 120℃范围内,p-p亚甲基的生成是主要反应。在这个阶段很难形成o-p亚甲基桥。在120 ~ 160℃范围内,主要反应是p-p亚甲基的生成。从160℃到190℃,主要反应是醚键断裂,羰基和丙基桥的形成。在190℃以上,主要反应为酚羟基之间的缩聚反应和羰基的形成反应。在230℃以上,醚键完全断裂。这项工作为研究硫化机理提供了一种新的方法。这对合理设计酚醛树脂基复合材料的固化工艺具有一定的指导意义。
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Curing mechanism of resole phenolic resin based on variable temperature FTIR spectra and thermogravimetry-mass spectrometry
To solve the problem that the curing mechanism evolution of phenolic resin catalyzed by Ba(OH)2 remained unclear, the p-p methylene index, o-p methylene index, o-o methylene index, hydroxymethyl index, and ether index were introduced to quantitatively investigate the chemical structure of resin in the curing temperature range of 90–230°C. The chemical structures were investigated by variable temperature FT-IR. The gas products released with the increase of curing temperature were characterized by Thermogravimetry-Mass Spectrometry. The curing mechanism from 90°C to 230°C was concluded finally. The results show that the main reaction is the formation of the p-p methylene group in the range of 90–120°C. It is difficult to form the o-p methylene bridge at this stage. In the range of 120–160°C, the main reaction is the formation of the p-p methylene group. From 160°C to 190°C, the main reactions are the breaking of the ether bond, the formation of the carbonyl group and the propyl bridge. Above 190°C, the main reactions are polycondensation reaction among phenolic hydroxyl groups, and the formation reaction of carbonyl groups. The ether bond breaks completely above 230°C. This work provides a new method to investigate the curing mechanism. It is a benefit for the rational design of the curing process of phenolic resin-based composites.
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