含双螺环三聚磷腈单元的苯并噁嗪树脂的结构和热稳定性

以双螺环取代三聚磷腈基双苯甲酰氯和4-氨基(N-苯基)苯并噁嗪单体为原料合成了一种含双螺环取代三聚磷腈结构单元的苯并噁嗪树脂单体(HCP-5);采用傅立叶变换红外光谱仪(FT-IR)和核磁共振谱仪(1 H NMR,13 C NMR,31P NMR)表征了苯并噁嗪树脂单体的结构,基于FT-IR和示差扫描量热法研究了其固化行为,并利用热重分析和示差热重分析研究了HCP-5树脂单体、均聚物及其与双酚A型苯并噁嗪树脂(Bz)共聚物的热稳定性.结果表明,HCP-5均聚物具有很好的热稳定性和成炭性,其在317℃下的热失重为5%,在800℃下的残炭率为50%,可用于普通苯并噁嗪树脂改性.此外,HCP-5/Bz(1∶1;质量分数)共聚物在332℃下的热失重为5%,在800℃下的残炭率为48%.

Structure and thermal stability of benzoxazine resin containing bis-spiro-substituted cyclotriphosphazene unit

A benzoxazine resin monomer （coded as HCP-5） containing bis-spiro-substituted cyclotriphosphazene structural unit was synthesized with hexachlorocyclotriphosphazene-2,2＇-biphenol formyl chloride and 4 amino N phenyl benzoxazine as the starting materials. The structure of as-synthesized HCP-5 resin monomer was confirmed by Fourier transform infrared spec trometry （FT-IR） and nuclear magnetic resonance spectroscopy （1H NMR, 13C NMR and 31p NMR）. The curing behavior of HCP-5 resin monomer was investigated based on FT-IR analysis and differential scanning calorimetric analysis, while the thermal stability of HCP-5 resin monomer and homopolymer as well as the copolymer of HCP-5 monomer with bisphenol-based benzoxazine （Bz） was evaluated by thermogravimetric analysis and differential thermogravimet ric analysis. Results show that the homopolymer of HCP-5 has excellent thermal stability and char-formation ability. Namely, it loses 5% of weight at 317 ℃ under nitrogen atmosphere and has a char yield of 50% at 800 ℃, showing potential for the modification of conventionalbenzoxazine resin. Besides, the copolymer of HCP-5 monomer with Bz, HCP-5/Bz （1 ： 1; mass ratio）, loses 5% of weight at 332 ℃ and yields 48% of char at 800 ℃.