Synthesis and Properties of High Polymerie Phosphazenes with (Trimethylsilyl) methyl Side Groups

Harry R. Allcock, William D. Coggio

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Poly(organophosphazenes) that bear Me3SiCH2 side groups were prepared via the reaction of [(trimethylsilyl)methyl]lithium with poly(phenylfluorophosphazene) ([NP(Ph)F(NPF2)2]n). Fluorine replacement occurred under mild conditions to yield polymers that contained up to 70% of the side groups as alkylsilyl units. Subsequent reaction with CF3CH2ONa gave air- and moisture-stable polymers with the basic stoichiometry of [NP(Ph)0.34(OCH2CF3)1.66−x(CH2SiMe3)x]n. The polymers were analyzed by 31P, 1H, and 19F NMR spectroscopy, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Replacement of the fluorine atoms by Me3SiCH2 side groups was accompanied by some skeletal cleavage. However, high molecular weight polymers were obtained by limiting the reaction time and temperature. Evidence was obtained that the organosilicon side groups are the sites of cross-linking reactions when the polymers are heated at temperatures above 200 °C.

Original languageEnglish (US)
Pages (from-to)764-771
Number of pages8
JournalMacromolecules
Volume26
Issue number4
DOIs
StatePublished - Jan 1 1993

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Polymers
Fluorine
Gel permeation chromatography
Lithium
Stoichiometry
Nuclear magnetic resonance spectroscopy
Differential scanning calorimetry
Moisture
Molecular weight
Atoms
Temperature
Air

All Science Journal Classification (ASJC) codes

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

Cite this

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abstract = "Poly(organophosphazenes) that bear Me3SiCH2 side groups were prepared via the reaction of [(trimethylsilyl)methyl]lithium with poly(phenylfluorophosphazene) ([NP(Ph)F(NPF2)2]n). Fluorine replacement occurred under mild conditions to yield polymers that contained up to 70{\%} of the side groups as alkylsilyl units. Subsequent reaction with CF3CH2ONa gave air- and moisture-stable polymers with the basic stoichiometry of [NP(Ph)0.34(OCH2CF3)1.66−x(CH2SiMe3)x]n. The polymers were analyzed by 31P, 1H, and 19F NMR spectroscopy, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Replacement of the fluorine atoms by Me3SiCH2 side groups was accompanied by some skeletal cleavage. However, high molecular weight polymers were obtained by limiting the reaction time and temperature. Evidence was obtained that the organosilicon side groups are the sites of cross-linking reactions when the polymers are heated at temperatures above 200 °C.",
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Synthesis and Properties of High Polymerie Phosphazenes with (Trimethylsilyl) methyl Side Groups. / Allcock, Harry R.; Coggio, William D.

In: Macromolecules, Vol. 26, No. 4, 01.01.1993, p. 764-771.

Research output: Contribution to journalArticle

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N2 - Poly(organophosphazenes) that bear Me3SiCH2 side groups were prepared via the reaction of [(trimethylsilyl)methyl]lithium with poly(phenylfluorophosphazene) ([NP(Ph)F(NPF2)2]n). Fluorine replacement occurred under mild conditions to yield polymers that contained up to 70% of the side groups as alkylsilyl units. Subsequent reaction with CF3CH2ONa gave air- and moisture-stable polymers with the basic stoichiometry of [NP(Ph)0.34(OCH2CF3)1.66−x(CH2SiMe3)x]n. The polymers were analyzed by 31P, 1H, and 19F NMR spectroscopy, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Replacement of the fluorine atoms by Me3SiCH2 side groups was accompanied by some skeletal cleavage. However, high molecular weight polymers were obtained by limiting the reaction time and temperature. Evidence was obtained that the organosilicon side groups are the sites of cross-linking reactions when the polymers are heated at temperatures above 200 °C.

AB - Poly(organophosphazenes) that bear Me3SiCH2 side groups were prepared via the reaction of [(trimethylsilyl)methyl]lithium with poly(phenylfluorophosphazene) ([NP(Ph)F(NPF2)2]n). Fluorine replacement occurred under mild conditions to yield polymers that contained up to 70% of the side groups as alkylsilyl units. Subsequent reaction with CF3CH2ONa gave air- and moisture-stable polymers with the basic stoichiometry of [NP(Ph)0.34(OCH2CF3)1.66−x(CH2SiMe3)x]n. The polymers were analyzed by 31P, 1H, and 19F NMR spectroscopy, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Replacement of the fluorine atoms by Me3SiCH2 side groups was accompanied by some skeletal cleavage. However, high molecular weight polymers were obtained by limiting the reaction time and temperature. Evidence was obtained that the organosilicon side groups are the sites of cross-linking reactions when the polymers are heated at temperatures above 200 °C.

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