降冰片烯与乙炔基官能化苯并恶嗪单体研究

Study on the benzoxazine monomer containing norbornene and acetylene groups

采用溶剂法合成了含有降冰片烯和乙炔基团的苯并恶嗪单体(oHPNI-ac)。通过核磁共振氢谱(~1H-NMR)和傅里叶变换红外光谱(FT-IR)证实了其分子结构,并以示差扫描量热分析(DSC)和原位红外图谱(in situ FT-IR)揭示了其固化行为。结果表明,oHPNI-ac的起始固化温度为205℃,固化峰值温度为224℃。oHPNI-ac中降冰片烯的碳碳双键与乙炔基的碳碳三键可在恶嗪环开环聚合过程中交联,从而降低了降冰片烯双键的固化温度。通过Kissinger方法和Ozawa方法计算得到该苯并恶嗪活化能分别为94.6,97.1 kJ/mol,且推测得到该单体的固化反应动力学方程。

The benzoxazine monomer containing norbornene and acetylene groups(oHPNI-ac)was synthesized by solution method.The chemical structure of synthesized monomer was confirmed by ~1H-NMR and FT-IR. The curing behaviors were monitored by DSC and in situ FT-IR. The results showed that the starting polymerization temperature was 205 ℃ and the curing peak temperature was 224 ℃.The carbon-carbon double bond of norbornene in oHPNI-ac and the carbon-carbon triple bond of ethynyl group could cross-link during the ring-opening polymerization of oxazine ring,thereby reducing the curing temperature of the norbornene double bond. The activation energy of the benzoxazine calculated by Kissinger method and Ozawa method was 94.6 and 97.1 kJ/mol,respectively,and the curing kinetic equation of the monomer was presumed.