Variation of hydrogen bonding (HB) and dielectric properties of polybenzoxazines with different Mannich bridge structures at different temperatures are investigated by in-situ Fourier Transform Infrared (FTIR) Spectrometry, perturbation-correlation moving-window two-dimensional (PCMW2D) infrared spectroscopy and Broad Band Dielectric Spectrometer (BDS), respectively. It is found that in phenolic Mannich polybenzoxazine, –OH•••O HB tends to rearrange into thermally stable –OH•••N HB. In arylamine Mannich polybenzoxazine, –OH•••O HB is favorable at relatively low temperature and will dissociate at higher temperature. The PCMW2D infrared spectroscopy reveals that the massive dissociation temperature of –OH•••O HB occurs is generally higher than 100 °C and varies with different polybenzoxazines. The results from BDS suggest that the thermal responsiveness of dielectric properties is closely related to the HB and the thermal resistance of polybenzoxazines. The six-membered –OH•••N HB is beneficial for high frequency stability and thermal stability of dielectric properties, which makes the phenolic Mannich polybenzoxazine promising candidate as high-temperature dielectric material.

通过原位傅里叶变换红外（FTIR）光谱，微扰相关移动窗口二维（PCMW2D）红外光谱和宽光谱研究了在不同温度下具有不同曼尼希桥结构的聚苯并恶嗪的氢键（HB）和介电性能的变化。带电光谱仪（BDS）分别。发现在酚醛曼尼希聚苯并恶嗪中，–OH•••O HB倾向于重新排列成热稳定的–OH•••N HB。在芳胺曼尼希聚苯并恶嗪中，–OH•••O HB在较低温度下较为有利，而在较高温度下会解离。PCMW2D红外光谱显示，–OH•••O HB发生的大量解离温度通常高于100°C，并随不同的聚苯并恶嗪而变化。BDS的结果表明介电性能的热响应性与HB和聚苯并恶嗪的热阻密切相关。六元–OH•••N HB有利于提高介电性能的高频稳定性和热稳定性，这使得酚醛曼尼希聚苯并恶嗪有望成为高温介电材料。