| Abstract
| - Aminolysis of the chlorinated poly(thionylphosphazene) [NSOCl(NPCl2)2]n (2a) with severalsecondary amines NHR2 (diethylamine, piperidine, and pyrrolidine) yielded various hydrolytically stablepoly[(amino)thionylphosphazenes] [NSO(NR2){NP(NR2)2}2]n6 (a, NR2 = piperidine; b, NR2 = pyrrolidine)in which chlorine atoms at both the phosphorus center and sulfur were replaced. In addition, treatmentof 2a with different equivalents of several secondary amines (diethylamine, piperidine, and pyrrolidine),followed by addition of excess of n-butylamine, lead to a series of mixed-substituent poly[(amino)thionylphosphazenes] [NSO(NHR‘){NP(NR2)2}2]n7 (NHR‘ = n-butylamine; a−c, NR2 = diethylamine; d,e, NR2 = piperidine; f, NR2 = pyrrolidine). The new moisture stable polymers were characterized by 31P,13C, and 1H NMR spectroscopy and elemental analysis. The molecular weights of the polymers 6a,6band 7a−7f were in the range of M̄w = 3.4 × 104−1.1 × 105 and M̄n = 3.1 × 103−5.0 × 104 according toGPC analysis in THF versus polystyrene standards. The thermal transition behavior was investigatedby means of DSC. Glass transition temperatures (Tg's) of the poly[(amino)thionylphosphazenes] 6a,6band 7a−7f depend on the content of secondary amine versus primary amine and were in the range of−13 to +27 °C. No melt transitions were detected.
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