Synthesis of Poly(dichlorophosphazene) by the Melt Phase Polymerization of P-Trichloro-N-(dichlorophosphoryl)monophosphazene
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A major barrier to commercialization of any of the many exciting applications of the poly(phosphazenes) has been the cost and ease of preparation of the most widely utilized starting polymer, poly(dichlorophosphazene) (Cl2PN)n (1). One attractive route is the thermal polycondensation reaction of P-trichloro-N-(dichlorophosphoryl)monophosphazene, Cl3P=N–P(O)Cl2 (2). We are reporting a modified bulk polymerization of 2 which represents a convenient route to laboratory scale amounts of (NPCl2)n with moderate molecular weights and polydispersity. GPC characterization data were obtained on the corresponding phenoxy derivatives, [(PhO)2PN]n. We also have developed a one pot synthesis of 1 from ammonium sulfate and phosphorus pentachloride which are the starting materials for the synthesis of 2 and examined the major variables, time and temperature, for this process. The resulting poly(phosphazene) exhibits more branching than the product of bulk polymerization of 1.
KeywordsPoly(dichlorophosphazene) P-trichloro-N-(dichlorophosphoryl)monophosphazene Melt phase synthesis
This work was supported by the Idaho National Engineering Lab University Research Consortium for the US Department of Energy under Contract No. DE-AC07-941D13223. Partial support from the National Science Foundation under the Vermont EPSCoR program is also gratefully acknowledged.
- 1.H.R. Allcock, Chemistry and Applications of Polyphosphazenes. (Wiley, Hoboken, 2003)Google Scholar
- 2.P. Wisian-Neilson, Phosphazenes for Biomedical Applications, ed. by A.K. Andrianov 155(2009)Google Scholar
- 6.H.R. Allcock, in Ambient Temperature Cationic Condensation Synthesis of Polyphosphazenes In: ed. by M. Geleria, R. De Jaeger Synthesis and Characterization of Poly(organophazenes) (Nova Science, New York, 2004), p. 49Google Scholar
- 12.R. De Jaeger and P. Potin Poly(Dichlorophsphazene) from P-Trichloro-N-(dichlorophosphoryl)monophosphazene, Cl2P(0) = NPCl3, ed. by M. Geleria, R. De Jaeger, In: Synthesis and Characterization of Poly(organophazenes) (Nova Science, New York, 2004), p. 25Google Scholar
- 15.C.W. Allen, A.Z. Hneihen and E.S. Peterson Solid State Synthesis of Poly(dichlorophosphazene) U.S. Patent 6,309,619, Bechtel BWXT Idaho LLC, 30 Oct 2001Google Scholar
- 16.J. Emsley and P.B. Udy J. Chem. Soc. A 2863 (1971)Google Scholar
- 17.R. DeJaeger, G. D’Halluin, G. Pagniez and P Potin, Polycondensation of impure P2NOCL5 into uncrosslinked poly(dichlorophosphazenes) in the Presence of PCl5, U.S patent # 5,132,389, Atochem, Puteaux, France, 21 Jul 1992Google Scholar
- 18.(15NH4)2SO4 (98%+ 15N) is available from Cambridge Isotope Lsaboratories.Google Scholar