Heat-resistant thermosetting polymers based on a novel tetrakisaminophenoxycyclotriphosphazene

Two heat-resistant thermosetting polymers ( IX and X ) have been developed based on a new cyclotriphosphazene containing tetrakisamine. These polymers were synthesized by the reaction of tetrakisamine ( IV ) with maleic anhydride followed by in situ cyclodehydration and polymerization of the maleimides ( VII and VIII ) at 235–240°C for 1.5 h and 290°C for 0.5 h. The thermogravimetric analyses (TGA) of the developed cyclotriphosphazene containing cyclomatrix polymers showed their thermal stability up to 350°C and char yield of 71% in nitrogen at 800°C and 65% in air at 700°C. The monomer, 2,2,4,4-tetrakis(4′-aminophenoxy) -6,6-diphenylcyclotriphosphazene ( IV ), useful for producing a variety of heat- and fire-resistant polymers, has been synthesized in good yield. Its syntheses involve Friedel-Crafts reaction of hexachlorocyclotriphosphazene ( I ) with benzene followed by the reaction of 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene ( II ) with potassium 4-nitrophenoxide. The reduction of the obtained 2,2,4,4-tetrakis(4′-nitrophenoxy)-6,6-diphenylcyclotriphosphazene ( III ) with molecular hydrogen in presence of PtO₂ gave the tetrakisamine ( IV ). The structure of the synthesized monomer and intermediates were characterized by FT-IR, ¹H-NMR, ³¹P-NMR, mass spectroscopy, differential scanning calorimetry (DSC), and elemental analysis. These resins are potential candidates for the development of heat- and fire-resistant composites, laminates, and adhesives, useful for space, aerospace, and electronic application. © 1993 John Wiley & Sons, Inc.