New homo-and block copolymers composed of polyacrylate and epoxy resin with hexafunctional cyclotriphosphazene core were synthesized and characterized by FT-IR and 1 H-, 13 C-, and 31 P-NMR. The first homopolymer, PN-polyacry was prepared from the direct condensation of 2-hydroxyethylacrylate with acyl chloride of hexakis(4-carboxyphenoxy)cyclotriphosphazene, PN-acyl. The second homopolymer, PN-Ep, was prepared in a direct reaction of catalyzed carboxyl groups of hexakis(4-carboxyphenoxy)cyclotriphosphazene PN-COOH with epoxy resin via an oxirane ring opening re action. The block copolymer, PN-Ep/polyacry, was prepared from the partial coupling of 2-hydroxyethyl acrylate with the PN-acyl, followed by the reaction of unreacted carboxyl groups with epoxy resin. Differential scanning calorimetry (DSC) analysis of the PN-Ep/polyacry copolymer exhibited good compatibility between polyacrylate and cured epoxy resin. Thermal gravimetric analysis (TGA) revealed that the prepared polymeric systems accumulate 30-38 wt % char at elevated temperatures, compared to neat polyacrylate and cured epoxy resin, which accumulate negligible char at 700 °C. The limiting oxygen index (LOI) exhibited significant enhancement of fire retardant properties of the prepared polymeric systems. A scanning electron microscopy (SEM) morphology study revealed that PN-polyacry and PN-Ep/polyacrylate produced intumescent char residues while PN-Ep produced solid dense char with a nonporous surface.
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