Investigation of polymerization of benzoxazines and thermal degradation characteristics of polybenzoxazines via direct pyrolysis mass spectrometry

Polymerization of benzoxazines and thermal degradation mechanisms of polybenzoxazines were investigated using the direct pyrolysis mass spectrometry (DP-MS) technique. The benzoxazine structures were based on phenol and aniline and on bisphenol-A and methylamine or aniline. Polymerizations of the benzoxazines were carried out by curing them at elevated temperatures without addition of initiator or catalyst. DP-MS data showed the presence of chains generated by opposing polymerization reaction pathways indicating quite complex structures for the polybenzoxazines under investigation. Thermal decomposition of polybenzoxazines was started by the cleavage of methylamine or aniline linkages. It was determined that polybenzoxazines based on phenol were more stable than the corresponding bisphenol-A-based polybenzoxazines, while those based on methylamine were more stable than the corresponding polybenzoxazines incorporating aniline. Thus, it can be concluded that the presence of bulky groups decreased the extent of crosslinking which in return decreased the thermal stability. © 2012 Society of Chemical Industry.