Poly[(aryloxy)carbophosphazenes]: Synthesis, Properties, and Thermal Transition Behavior

Harry R. Allcock; Suzanne M. Coley; Ian Manners; Oskar Nuyken; Gerhard Renner

doi:10.1021/ma00008a048

Poly[(aryloxy)carbophosphazenes]: Synthesis, Properties, and Thermal Transition Behavior

Harry R. Allcock, Suzanne M. Coley, Ian Manners, Oskar Nuyken, Gerhard Renner

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Abstract

The cyclic carbophosphazene N₃P₂CC1₅ undergoes thermal ring-opening polymerization at 120 °C to yield the poly(chlorocarbophosphazene) [N₃P₂CC1₅]_n as a hydrolytically sensitive elastomer. This polymer was allowed to react with a variety of aryloxide nucleophiles to afford a range of hydrolytically stable poly[(aryloxy)carbophosphazenes] [N₃P₂C(OAr)₅]_n. These macromolecules were characterized by ³¹P, ^lH, and ¹³C NMR spectroscopy, IR spectroscopy, elemental analysis, differential scanning calorimetry, gel permeation chromatography and, in one case, light scattering. Analogous, small-molecule model reactions, in which the cyclocarbophosphazene N₃P₂CC1₆ was allowed to react with the same aryloxide nucleophiles to yield the cyclic species N₃P₂C(OAr)₅, are also described. The glass transition temperatures of the poly-[(aryloxy)carbophosphazenes] are 16–42 °C higher than those of their classical polyphosphazene analogues [NP(OAr)₂]_n. Possible reasons for the lower skeletal flexibility of poly(carbophosphazenes) compared to classical polyphosphazenes are discussed.

Original language	English (US)
Pages (from-to)	2024-2028
Number of pages	5
Journal	Macromolecules
Volume	24
Issue number	8
DOIs	https://doi.org/10.1021/ma00008a048
State	Published - Apr 1 1991

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Poly[(aryloxy)carbophosphazenes]: Synthesis, Properties, and Thermal Transition Behavior",

abstract = "The cyclic carbophosphazene N3P2CC15 undergoes thermal ring-opening polymerization at 120 °C to yield the poly(chlorocarbophosphazene) [N3P2CC15]n as a hydrolytically sensitive elastomer. This polymer was allowed to react with a variety of aryloxide nucleophiles to afford a range of hydrolytically stable poly[(aryloxy)carbophosphazenes] [N3P2C(OAr)5]n. These macromolecules were characterized by 31P, lH, and 13C NMR spectroscopy, IR spectroscopy, elemental analysis, differential scanning calorimetry, gel permeation chromatography and, in one case, light scattering. Analogous, small-molecule model reactions, in which the cyclocarbophosphazene N3P2CC16 was allowed to react with the same aryloxide nucleophiles to yield the cyclic species N3P2C(OAr)5, are also described. The glass transition temperatures of the poly-[(aryloxy)carbophosphazenes] are 16–42 °C higher than those of their classical polyphosphazene analogues [NP(OAr)2]n. Possible reasons for the lower skeletal flexibility of poly(carbophosphazenes) compared to classical polyphosphazenes are discussed.",

author = "Allcock, {Harry R.} and Coley, {Suzanne M.} and Ian Manners and Oskar Nuyken and Gerhard Renner",

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T2 - Synthesis, Properties, and Thermal Transition Behavior

AU - Allcock, Harry R.

AU - Coley, Suzanne M.

AU - Manners, Ian

AU - Nuyken, Oskar

AU - Renner, Gerhard

PY - 1991/4/1

Y1 - 1991/4/1

N2 - The cyclic carbophosphazene N3P2CC15 undergoes thermal ring-opening polymerization at 120 °C to yield the poly(chlorocarbophosphazene) [N3P2CC15]n as a hydrolytically sensitive elastomer. This polymer was allowed to react with a variety of aryloxide nucleophiles to afford a range of hydrolytically stable poly[(aryloxy)carbophosphazenes] [N3P2C(OAr)5]n. These macromolecules were characterized by 31P, lH, and 13C NMR spectroscopy, IR spectroscopy, elemental analysis, differential scanning calorimetry, gel permeation chromatography and, in one case, light scattering. Analogous, small-molecule model reactions, in which the cyclocarbophosphazene N3P2CC16 was allowed to react with the same aryloxide nucleophiles to yield the cyclic species N3P2C(OAr)5, are also described. The glass transition temperatures of the poly-[(aryloxy)carbophosphazenes] are 16–42 °C higher than those of their classical polyphosphazene analogues [NP(OAr)2]n. Possible reasons for the lower skeletal flexibility of poly(carbophosphazenes) compared to classical polyphosphazenes are discussed.

AB - The cyclic carbophosphazene N3P2CC15 undergoes thermal ring-opening polymerization at 120 °C to yield the poly(chlorocarbophosphazene) [N3P2CC15]n as a hydrolytically sensitive elastomer. This polymer was allowed to react with a variety of aryloxide nucleophiles to afford a range of hydrolytically stable poly[(aryloxy)carbophosphazenes] [N3P2C(OAr)5]n. These macromolecules were characterized by 31P, lH, and 13C NMR spectroscopy, IR spectroscopy, elemental analysis, differential scanning calorimetry, gel permeation chromatography and, in one case, light scattering. Analogous, small-molecule model reactions, in which the cyclocarbophosphazene N3P2CC16 was allowed to react with the same aryloxide nucleophiles to yield the cyclic species N3P2C(OAr)5, are also described. The glass transition temperatures of the poly-[(aryloxy)carbophosphazenes] are 16–42 °C higher than those of their classical polyphosphazene analogues [NP(OAr)2]n. Possible reasons for the lower skeletal flexibility of poly(carbophosphazenes) compared to classical polyphosphazenes are discussed.

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Poly[(aryloxy)carbophosphazenes]: Synthesis, Properties, and Thermal Transition Behavior

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