The influence of phthalonitrile monomer containing oxazine ring on the properties of epoxy/amine system: Curing behavior and thermal stability

Abstract Phthalonitrile monomer containing oxazine ring (BPS‐Ph) was synthesized using bisphenol‐S, aniline, paraformaldehyde, and 4‐nitrophthalonitrile via a two‐step method. The differential scanning calorimetry (DSC) data of the curing process of BPS‐Ph monomer indicates that the peak polymerization temperature of the cyan group is about 250°C and that confirms the promoting effect of oxazine ring on the curing reaction of phthalonitrile. The rheological data of E51/DDS containing BPS‐Ph indicates that the BPS‐Ph monomer also has promoting effect on the curing process. The activation energy was studied via the iso‐conversional method principle. The activation energy corresponding to the E51/DDS crosslinking reaction is 75.79 and 60.54 kJ mol −1 , respectively, for pure E51/DDS and E51/DDS/BPS‐Ph. Moreover, the activation energy of the crosslinking of phthalhydrazine is 74.1 kJ mol −1 which is rather lower than that in pure BPS‐Ph, and that implies the synergistically catalytic effect of the oxazine ring and the amine. The addition of BPS‐Ph monomer significantly improves the thermal behaviors of the thermoset. The char yield in N 2 atmosphere increased from 15.6% to 53.9% when adding 30% BPS‐Ph to the E51/DDS. Moreover, the peak weight loss temperature decreased from 407 to 385°C. The phase separation size of poly‐BPS‐Ph in E51/DDS is about tens to hundreds nanometers according to the atomic force microscopy (AFM) phase diagram. It is indicated that incorporation of phthalonitrile monomer containing oxazine ring into epoxy/amine system is an applicable and effective way to promote the thermal behavior of the thermoset.