A new route for poly(organophosphazene) synthesis. Polymerization, copolymerization, and ring-ring equilibration of trifluoroethoxy- and chloro-substituted cyclotriphosphazenes

H. R. Allcock, J. L. Schmutz, Karen M. Kosydar

Research output: Contribution to journalArticle

31 Scopus citations

Abstract

The phosphazene cyclic trimer, [NP(OCH2CF3)2]3 (X), copolymerizes with (NPCl2)3 (I) to yield a new series of elastomers and also undergoes ring-expansion reactions at elevated temperatures. The copolymers were characterized by means of substitution reactions and 31P NMR analysis. The possibility that the polymerization involves a prior ligand exchange was investigated through studies of the thermal behavior of the cyclic phosphazenes, N3P3Cl5(OCH2CF3) (V), N3P3Cl4(OCH2CF3) 2 (trans nongem) (VI), N3P3Cl3(OCH2CF3) 3 (trans nongem) (VII), N3P3Cl2(OCH2CF3) 4 (cis nongem) (VIII), and N3P3Cl(OCH2CF3)5 (IX). All these mixed substituent trimers underwent ring expansion reactions when heated, but only compounds V, VI, and VII yielded linear-type polymers. The gas CF3CH2Cl, was detected as a product from all systems that contained both P-Cl and P-OCH2CF3 bonds, with substantial quantities being released at temperatures above 250°C. This process was apparently connected with the formation of trans-annular-linked cyclic compounds, cross-linked linear chains, or cyclolinear or cyclomatrix-type products. The mechanisms of these reactions are discussed.

Original languageEnglish (US)
Pages (from-to)179-186
Number of pages8
JournalMacromolecules
Volume11
Issue number1
StatePublished - Dec 1 1978

All Science Journal Classification (ASJC) codes

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

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