With the aim of obtaining halogen-free polybenzoxazazines with reduced flammability, phosphazene-containing benzoxazines (PhBZ) were synthesized in a two-stage method. In the first stage of the reaction of hexachlorocycotriphosphazene with bisphenol A at molar ratios of 1:12, 1:16, and 1:24, respectively, mixtures of bisphenol and hydroxyaryloxycyclotriphosphazenes were obtained, which mainly contained P₃N₃[OC₆H₄C(CH₃)₃C₆H₄OH]₆. In the second stage, when these mixtures interacted with aniline and an excess of paraformaldehyde in toluene at 80–90 °C, PhBZ containing 20–50% of the phosphazene component with M_w 1200–5800 were formed. According to ¹H and ¹³C NMR spectroscopy, PhBZ contain a small amount of oligomeric compounds with Mannich aminomethylene bridges. With an increase of the content of the phosphazene component, the curing temperature of PhBZ decreases from 242 °C to 215 °C. Cured PhBZ samples with a phosphorus content of more than 1.5% have increased flammability resistance according to UL-94.

Phosphazene-containing epoxy oligomers (PEO) were synthesized by the interaction of hexachlorocyclotriphosphazene (HCP), phenol, and bisphenol A in a medium of excess of epichlorohydrin using potassium carbonate and hydroxide as HCl acceptors with the aim of obtaining a product with lower viscosity and higher phosphazene content. PEOs are mixtures of epoxycyclophosphazene (ECP) and a conventional organic epoxy resin based on bisphenol A in an amount controlled by the ratio of the initial mono- and diphenol. According to ³¹P NMR spectroscopy, pentasubstituted aryloxycyclotrophosphazene compounds predominate in the ECP composition. The relative content in the ECP radicals of mono- and diphenol was determined by the MALDI-TOF mass spectrometry method. The organic epoxy fraction, according to gas chromatograpy-mass spectrometry (GC-MS), contains 50–70 wt % diglycidyl ether of bisphenol A. PEO resins obtained in the present work have reduced viscosity when compared to other known phosphazene-containging epoxy resins while phosphazene content is still about 50 wt %. Resins with an epoxy number within 12–17 wt %, are cured by conventional curing agents to form compositions with flame-retardant properties, while other characteristics of these compositions are at the level of conventional epoxy materials.

To reveal the effect of chlorine substituents in the ring of aromatic amine on the synthesis process of benzoxazine monomer and on its polymerization ability, as well as to develop a fire-resistant material, a previously unreported benzoxazine monomer based on 3,3′-dichloro-4,4′-diaminodiphenylmethane was obtained in toluene and mixture toluene/isopropanol. The resulting benzoxazine monomers were thermally cured for 2 h at 180 °C, 4 h at 200 °C, 2 h at 220 °C. A comparison between the rheological, thermal and fire-resistant properties of the benzoxazines based on 3,3′-dichloro-4,4′-diaminodiphenylmethane and, for reference, 4,4′-diaminodimethylmethane was made. The effect of the reaction medium on the structure of the oligomeric fraction and the overall yield of the main product were studied and the toluene/ethanol mixture was found to provide the best conditions; however, in contrast to most known diamine-based benzoxazines, synthesis in the pure toluene is also possible. The synthesized monomers can be used as thermo- and fire-resistant binders for polymer composite materials, as well as hardeners for epoxy resins. Chlorine-containing polybenzoxazines require more severe conditions for polymerization but have better fire resistance.

With the use of ³¹P NMR spectroscopy and gas chromatography-mass spectrometry, the partial ammonolysis of PCl₅ by ammonium chloride in chlorobenzene in the presence of zinc chloride is investigated. The use of zinc chloride reduces the reaction time to 1.5 h and increases the yield of oligomeric chlorophosphazenes up to 95%. Some assumptions are made about the role of ZnCl₂ in the process and about the feasibility of the mechanism of formation of higher cyclic chlorophosphazenes, the hexamer and the octamer.

Phosphazene-containing epoxy-resorcinol oligomers (PERO) are synthesized in one stage with the direct interaction of hexachlorocyclotriphosphazene (HCP), resorcinol, and epichlorohydrin in the presence of solid NaOH. Depending on the initial ratio of HCP:resorcinol, PERO contains from 20 to 50 wt.% phosphazene component (2.0–4.8% of phosphorus) and have an epoxy group content up to 30 %. Products are characterized using ¹H and ³¹P NMR spectroscopy, MALDI-TOF mass spectrometry, and elemental analysis. According to mass spectrometry, the phosphazene fractions of PERO include up to 30 individual compounds with a predominance of cyclotriphosphazenes with one unsubstituted chlorine atom and four or five glycidyl groups. PERO has a lower viscosity in comparison with similar resins based on bisphenol A, which can simplify their use as a binder for polymer composites, adhesives, and paints.

The synthesis of eugenol derivatives of octachlorocyclotetraphosphazene and mixtures of oligomer chlorocyclophosphazenes [NPCl₂]_3–8 was performed. Not yet described octakis(4-allyl-2-methoxyphenoxy)cyclotetraphosphazene was isolated in the crystalline form and identified via ³¹P and ¹H NMR spectroscopy, laser mass spectrometry, DSC, and TGA. Oligomers with epoxy numbers of 15–16% and molecular masses from 1400 to 1800 were prepared via epoxidation of the synthesized eugenol derivatives with m-chloroperbenzoic acid. Some assumptions on the nature of side reactions occurring in the course of epoxidation were made.