Synthesis and Properties of Poly(aminocarbophosphazenes)

Harry R. Allcock, Suzanne M. Coley, Christopher T. Morrissey

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18 Scopus citations


The cyclic carbophosphazene N3P2CCl5 undergoes thermal ring-opening polymerization at 120 °C to yield poly(pentachlorocarbophosphazene), [N3P2CCl5]n, as a hydrolytically sensitive elastomer. Treatment of this polymer in solution with primary and secondary alkylamines yielded poly(aminocarbophosphazenes) [N3P2C(NR1R2)5]n, where R1 = H, R2 = nPr or iPr, and R1 = R2 = Me or Et. These polymers are also sensitive to moisture. An anilino/dimethylamino mixed-substituent polymer, [N3P2C(NHPh)x(NMe2)y(Cl)z]n (x = 1.50, y = 3.34, z = 0.16), and a 2,6-diphenylphenoxy/dimethylamino mixed-substituent polymer, [N3P2C(2,6-OPh(Ph)2)x(NMe2)y]n (x = 1, y = 4), were synthesized via the same technique. A mixed-substituent polymer with regiospecific backbone carbon substitution, [(NP(OCH2CF3)2)2NC(N(Ph)2)]n, was also synthesized. These mixed-substituent polymers are stable to water. The macromolecules were characterized by 31P, 1H, and 13C NMR spectroscopy, IR spectroscopy, elemental analysis, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. Poly [(dimethylamino)carbophosphazene] undergoes a depolymerization reaction in solution and in the solid state to give small-molecule cyclic analogues, including N3P2C(NMe2)5. The depolymerization reaction was investigated by 31P NMR spectroscopy and thermogravimetric analysis in conjunction with mass spectrometry. Analogous small-molecule model reactions were undertaken in which the cyclocarbophosphazene N3P2CCl5 was allowed to react with primary and secondary alkylamines to yield the cyclic species N3P2C(NR1R2)5. The mixed-substituent cyclic species {[NP(OCH2CF3)2]2[NC(N(Ph)2)]} and {[NP(NMe2)2] [NP(2,6-OPh(Ph)2)(NMe2)] [NC(NMe2)]} were also synthesized.

Original languageEnglish (US)
Pages (from-to)2904-2911
Number of pages8
Issue number11
StatePublished - May 1 1994

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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