Polymers with Sulfur(VI)−Nitrogen−Phosphorus Backbones:  Synthesis, Characterization, and Properties of Poly[(dialkylamino)thionylphosphazenes]

• Published in: Macromolecules Vol. 33; no. 21; pp. 7707 - 7712
• Main Authors: Nobis, Markus N, McWilliams, Andrew R, Nuyken, Oskar, Manners, Ian
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 17.10.2000
• Subjects: Applied sciences; Chemical modifications; Chemical reactions and properties; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Chemical modification; Aminolysis; Phosphazene copolymer; Preparation; Humidity resistance; Piperidine derivatives; Chlorine containing copolymer; Experimental study; Sulfur copolymer; Secondary amine; Pyrrolidine derivatives
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma000830x

Aminolysis of the chlorinated poly(thionylphosphazene) [NSOCl(NPCl2)2] n (2a) with several secondary amines NHR2 (diethylamine, piperidine, and pyrrolidine) yielded various hydrolytically stable poly[(amino)thionylphosphazenes] [NSO(NR2){NP(NR2)2}2] n 6 (a, NR2 = piperidine; b, NR2 = pyrrolidine) in which chlorine atoms at both the phosphorus center and sulfur were replaced. In addition, treatment of 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] n 7 (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,6b and 7a−7f were in the range of M̄ w = 3.4 × 104−1.1 × 105 and M̄ n = 3.1 × 103−5.0 × 104 according to GPC analysis in THF versus polystyrene standards. The thermal transition behavior was investigated by means of DSC. Glass transition temperatures (T g's) of the poly[(amino)thionylphosphazenes] 6a,6b and 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.