Synthesis of Telechelic Polyphosphazenes via the Ambient Temperature Living Cationic Polymerization of Amino Phosphoranimines

Harry R. Allcock, James M. Nelson, Robbyn Prange, Chester A. Crane, Christine R. De Denus

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Abstract

A method for the synthesis of well-defined mono-, di-, and mixed-telechelic polyphosphazenes produced via a living cationic polymerization of phosphoranimines is described. Amino phosphoranimines R-NH(CF3CH2O)2P=NSiMe3 (R = Ph-, p-BrPh-, p-H3CPh-, CH2=CHCH2-, and CH2=CHPh-) were synthesized via a reaction between a bromophosphoranimine and the appropriate organic amine. Ditelechelic polymers [R-NH]2-[Cl2P=N]n were prepared by quenching living poly(dichlorophosphazene) chains, [Cl3P=N(Cl2P=N)n-PCl3] +[PCl6]- with small quantities of the amino phosphoranimines. Cationic initiators of the amino phosphoranimines were also generated using PCls and were used to polymerize Cl3P=NSiMe3, to give monotelechelic poly(dichlorophosphazenes). In addition, a mixed telechelic system was produced by the termination of an allylamino monotelechelic poly(dichlorophosphazene) chain with a bromoanilino phosphoranimine. In all cases, displacement of the chlorine atoms with sodium trifluoroethoxide yielded hydrolytically stable telechelic polymers with controlled molecular weights and low polydispersities.

Original languageEnglish (US)
Pages (from-to)5736-5743
Number of pages8
JournalMacromolecules
Volume32
Issue number18
DOIs
StatePublished - Sep 7 1999

All Science Journal Classification (ASJC) codes

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

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