Novel polybenzoxazine and polybenzoxazine/epoxy thermosetting copolymers containing polysilsesquioxane nanostructures for high-performance thermal protection systems

This work focuses on the development of novel thermosetting systems derived from a siloxane-based benzoxazine hybrid precursor [Pr(BA-3aptms)], a conventional benzoxazine (BA-a) and a commercial epoxy resin (DGEBA) based on bisphenol A, as a strategy to prepare benzoxazine/benzoxazine and epoxy/benzoxazine copolymers with different amounts of polysilsesquioxanes in their chemical structure. The effect of the siloxane composition on the morphology was investigated, and their influence on the thermal, dynamo-mechanical and flammability properties was elucidated. The obtained results allowed to conclude that an increase of the BA-a or DGEBA content in the copolymers, considerably affects the morphology of the materials. In this sense, the laminar arrangement changed to a nanocluster arrangement when the contents of Si were below 17% w/w for the epoxy/ benzoxazine and below 10% w/w for benzoxazine/benzoxazine systems, respectively. Also, the thickness of the organic sheets in the matrices was increased when increasing the content of BA-a or DGEBA in the materials. In addition, the incorporation of the polysilsesquioxane-based precursor in the crosslinked materials improved the investigated properties, such as: thermal, mechanical and flame resistance, and hydrophobic behavior.