Aminolysis of the halogenated poly(thionylphosphazene) [NSOCl(NPCl2)2]n (2a), which possesses a novel S(VI)-N-P backbone, with a series of primary amines NH2R (R ) Me, Et, n Pr, allyl, n Bu, n Hex, and Ph) afforded the hydrolytically stable poly[(aminoPh) in which both the chlorine substituents at the phosphorus center and at sulfur were replaced. Treatment of 2a with a mixture of amines, NH2R (R ) allyl and n Bu), yielded a series of mixed substituent copolymers 5a-5c of which 5a and 5b were thermally and UV cross-linkable. These new polymers were structurally characterized by 31 P, 1 H, and 13 C NMR and IR spectroscopy and by elemental analysis. The stereochemistry of the poly[(amino)thionylphosphazenes] was investigated by 31 P NMR which indicated the polymers are atactic. Molecular weights of the polymers 4a-4g and 5a-5c were in the range Mw ) 5.0 × 10 3 to 1.3 × 10 5 , Mn ) 3.3 × 10 3 to 7.4 × 10 4 according to GPC analysis in THF versus polystyrene standards. An absolute value of Mw ) 1.0 × 10 5 was obtained by low-angle laser light scattering for 4e, which was approximately double that obtained by GPC (Mw ) 4.9 × 10 4 ). The thermal transition behavior of the polymers was investigated by DSC. Glass transition temperatures (Tg's) of the poly[(amino)thionylphosphazenes] 4a-4g and 5a-5c were in the range of -40 to +82 °C. No melt transitions were detected and wide-angle X-ray scattering studies also indicated that poly[(amino)thionylphosphazenes] were amorphous. TGA analysis showed that the poly[(amino)thionylphosphazenes] were stable to weight loss up to 200-250 °C under nitrogen at a heating rate of 10 °C/min.

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