A method for the synthesis of an amine-containing epoxy resin curing agent by dissolving hexakis-[(4-formyl)phenoxy]cyclotriphosphazene in an excess of isophoronediamine was developed. The curing agent was characterized via NMR and IR spectroscopy and MALDI-TOF mass spectrometry, and its rheological characteristics were studied. Compositions based on DER-354 epoxy resin and the synthesized curing agent with different amounts of phosphazene content were obtained. The rheological characteristics of these compositions were studied, followed by their curing. An improvement in several thermal (DSC), mechanical (compression, tension, and adhesion), and physicochemical (water absorption and water solubility) characteristics, as well as the fire resistance of the obtained materials modified with phosphazene, was observed, compared with unmodified samples. In particular, there was an improvement in adhesive characteristics and fire resistance. Thus, compositions based on a curing agent containing a 30% modifier were shown to fulfill the V-1 fire resistance category. The developed compositions can be processed by contact molding, winding, and resin transfer molding (RTM), and the resulting material is suitable for use in aircraft, automotive products, design applications, and home repairs.

The influence of epoxy active diluents, 1,4-butanediol diglycidyl ether (BD) and furfuryl glycidyl ether (FUR), in the mixtures with benzoxazine monomer based on bisphenol A, formaldehyde and m-toluidine (BA-mt), on the properties of a matrix was disclosed in this work. Resins were modified to achieve good tackiness at room temperature and reduced viscosity. The influence of mono- and difunctional modifiers on the process of curing was studied by way of differential scanning calorimetry and oscillatory rheology. The addition of BD and FUR shifted the curing peak to higher temperatures and significantly reduced viscosity. Preferable tackiness at ambient temperature was achieved with 10 phr of epoxy components in mixtures. However, cured blends with difunctional epoxy BD had an advantage over monofunctional FUR in enhanced tensile strength with remaining glass transition temperature at the level of neat benzoxazine (217 °C).

This work is devoted to the influence of phosphazene modifiers with different substituents on the curing process, thermal properties and flammability of benzoxazine resin. Novel catalysts with m-toluidine substituents were introduced. The catalytic activity of studied phosphazene compounds decreased in the row: hexachlorocyclotriphosphazene (HCP) > tetra m-toluidine substituted phosphazene PN-mt (4) > hexa m-toluidine substituted phosphazene PN-mt (6) > hexaphenoxycyclotriphosphazene (HPP), where HPP is totally inactive. Two types of catalysis: basic and acid were proposed. A brief study of resulting properties of polybenzoxazines was presented. The addition of any studied modifier caused the decrease of glass transition temperature and thermal stability of polymers. The morphology of cured compositions was characterized by matrix-dispersion phase structure. All phosphazene containing polybenzoxazines demonstrated the improved flame resistance.