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

Research output: Contribution to journalArticle

39 Citations (Scopus)

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

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Cationic polymerization
Living polymerization
Polymers
Chlorine
Polydispersity
Amines
Quenching
Sodium
Molecular weight
Atoms
Temperature

All Science Journal Classification (ASJC) codes

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

Cite this

Allcock, Harry R. ; Nelson, James M. ; Prange, Robbyn ; Crane, Chester A. ; De Denus, Christine R. / Synthesis of Telechelic Polyphosphazenes via the Ambient Temperature Living Cationic Polymerization of Amino Phosphoranimines. In: Macromolecules. 1999 ; Vol. 32, No. 18. pp. 5736-5743.
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Synthesis of Telechelic Polyphosphazenes via the Ambient Temperature Living Cationic Polymerization of Amino Phosphoranimines. / Allcock, Harry R.; Nelson, James M.; Prange, Robbyn; Crane, Chester A.; De Denus, Christine R.

In: Macromolecules, Vol. 32, No. 18, 07.09.1999, p. 5736-5743.

Research output: Contribution to journalArticle

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T1 - Synthesis of Telechelic Polyphosphazenes via the Ambient Temperature Living Cationic Polymerization of Amino Phosphoranimines

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