Ring-Opening Polymerization of Metallocene Cyclophosphazene Derivatives

Harry R. Allcock, Karen D. Lavin, Geoffrey H. Riding

Research output: Contribution to journalArticle

68 Citations (Scopus)

Abstract

New and unusual metallocenylphosphazene high Dolvmers have been Prepared by the thermal ring-opening polymerization of metallocene-substituted cyclotriphosphazene derivatives. The transannular-linked cyclic trimers [N3P3F4(η-C5H4)2M] (la, M = Fe; lb, M = Ru) and the monosubstituted compounds [N3P3F5(η-C5H4)M(η-C6H5)] (2a, 2b) serve both as reaction model compounds and as “monomers” for the analogous high polymeric derivatives 3a, 3b, and 8a, 8b. The hydrolytically unstable P—F bonds in the trimers and high polymers were replaced by treatment with sodium trifluoroethoxide to yield the corresponding air-stable trimeric and polymeric metallocenyl(trifluoroethoxy)phosphazenes (4a, 4b, 9a, 9b). Compounds la and lb were also copolymerized to yield a 1:1 copolymer which, after reaction with sodium trifluoroethoxide, yielded [N3P3(OCH2CF3)4(η-C5H4)2Fe-N3P3(OCH2CF3)4(ηC5H4)2Ru]n (7). The properties, structure, and characterization of these new organometallic polyphosphazenes are discussed, together with the mechanism of thermal polymerization of cyclic phosphazenes.

Original languageEnglish (US)
Pages (from-to)1340-1345
Number of pages6
JournalMacromolecules
Volume18
Issue number6
DOIs
StatePublished - Jan 1 1985

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Ring opening polymerization
Sodium
Derivatives
Organometallics
Polymers
Copolymers
Monomers
Polymerization
Air
Hot Temperature
metallocene

All Science Journal Classification (ASJC) codes

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

Cite this

Allcock, Harry R. ; Lavin, Karen D. ; Riding, Geoffrey H. / Ring-Opening Polymerization of Metallocene Cyclophosphazene Derivatives. In: Macromolecules. 1985 ; Vol. 18, No. 6. pp. 1340-1345.
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Ring-Opening Polymerization of Metallocene Cyclophosphazene Derivatives. / Allcock, Harry R.; Lavin, Karen D.; Riding, Geoffrey H.

In: Macromolecules, Vol. 18, No. 6, 01.01.1985, p. 1340-1345.

Research output: Contribution to journalArticle

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N2 - New and unusual metallocenylphosphazene high Dolvmers have been Prepared by the thermal ring-opening polymerization of metallocene-substituted cyclotriphosphazene derivatives. The transannular-linked cyclic trimers [N3P3F4(η-C5H4)2M] (la, M = Fe; lb, M = Ru) and the monosubstituted compounds [N3P3F5(η-C5H4)M(η-C6H5)] (2a, 2b) serve both as reaction model compounds and as “monomers” for the analogous high polymeric derivatives 3a, 3b, and 8a, 8b. The hydrolytically unstable P—F bonds in the trimers and high polymers were replaced by treatment with sodium trifluoroethoxide to yield the corresponding air-stable trimeric and polymeric metallocenyl(trifluoroethoxy)phosphazenes (4a, 4b, 9a, 9b). Compounds la and lb were also copolymerized to yield a 1:1 copolymer which, after reaction with sodium trifluoroethoxide, yielded [N3P3(OCH2CF3)4(η-C5H4)2Fe-N3P3(OCH2CF3)4(ηC5H4)2Ru]n (7). The properties, structure, and characterization of these new organometallic polyphosphazenes are discussed, together with the mechanism of thermal polymerization of cyclic phosphazenes.

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