Influence of reaction parameters on the living cationic polymerization of phosphoranimines to polyphosphazenes

Harry R. Allcock, Scott D. Reeves, Christine R. De Denus, Chester A. Crane

Research output: Contribution to journalArticle

60 Scopus citations

Abstract

A new approach to the synthesis of poly(dichlorophosphazene) and poly(organophosphazenes) has been developed via the cationic condensation polymerization of phosphoranimines. The effects of solvent, temperature, concentration, and initiator on the cationic condensation polymerization of Cl3P = NSiMe3 and PhCl2P = NSiMe3 are described. The ambient temperature polymerization of PhCl2P = NSiMe3 is faster in toluene, benzene, and dioxane than in methylene chloride or chloroform. The polymerizations of Cl3P = NSiMe3 and PhCl2P = NSiMe3 were monitored by both NMR (31P and 1H) and GPC methods. The initial polymerization rates are slow, presumably because of the precipitation of phosphazene short chain salts, RCl2P = N-[PR(Cl) = N]n-PCl3+PCl6- (where R = Cl or Ph; n = 0, 1, 2, ...). After the chains redissolve (approximately 15-60 min), polymerization proceeds, with the propagation rates following pseudo-first-order kinetics for both monomers. The reactions in toluene, benzene, or dioxane yielded polymers with controlled molecular weights in the range of 105, with narrow polydispersities (<1.3). The usefulness of this approach for the synthesis of a biomedically important polyphosphazene has also been demonstrated.

Original languageEnglish (US)
Pages (from-to)748-754
Number of pages7
JournalMacromolecules
Volume34
Issue number4
DOIs
StatePublished - Feb 13 2001

All Science Journal Classification (ASJC) codes

  • Materials Chemistry

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