Poly(thiophosphazenes): New Inorganic Backbone Polymers

Harry R. Allcock; Jeffrey A. Dodge; Ian Manners

doi:10.1021/ma00053a002

Poly(thiophosphazenes): New Inorganic Backbone Polymers

Harry R. Allcock, Jeffrey A. Dodge, Ian Manners

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

The cyclic thiophosphazene N₃P₂SCl₅ undergoes thermal ring-opening polymerization when heated at 90 °C. The resultant polymer, [N₃P₂Cl₅]_n, is a hydrolytically sensitive, yellow, elastomeric material. This polymer reacts with aryloxide nucleophiles to give poly[(aryloxy)thiophosphazenes] of general structure [N₃P₂S(OAr)_xCl_y] (x > y). The structures of these polymers were examined with the use of ¹H and ³¹P NMR spectroscopy, elemental microanalysis and gel permeation chromatography. The glass transition temperatures of the polymers were measured by means of differential scanning calorimetry and were found to be in a range from −40 to +79 °C. These T_g values are compared to those of poly(carbophosphazene) and classical phosphazene analogues. Reactions of N₃P₂SCl₅ with NaOCH₂CF₃ and NaOPh—Ph-o are also described.

Original language	English (US)
Pages (from-to)	11-16
Number of pages	6
Journal	Macromolecules
Volume	26
Issue number	1
DOIs	https://doi.org/10.1021/ma00053a002
State	Published - 1993

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Poly(thiophosphazenes): New Inorganic Backbone Polymers",

abstract = "The cyclic thiophosphazene N3P2SCl5 undergoes thermal ring-opening polymerization when heated at 90 °C. The resultant polymer, [N3P2Cl5]n, is a hydrolytically sensitive, yellow, elastomeric material. This polymer reacts with aryloxide nucleophiles to give poly[(aryloxy)thiophosphazenes] of general structure [N3P2S(OAr)xCly] (x > y). The structures of these polymers were examined with the use of 1H and 31P NMR spectroscopy, elemental microanalysis and gel permeation chromatography. The glass transition temperatures of the polymers were measured by means of differential scanning calorimetry and were found to be in a range from −40 to +79 °C. These Tg values are compared to those of poly(carbophosphazene) and classical phosphazene analogues. Reactions of N3P2SCl5 with NaOCH2CF3 and NaOPh—Ph-o are also described.",

author = "Allcock, {Harry R.} and Dodge, {Jeffrey A.} and Ian Manners",

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journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "1",

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TY - JOUR

T1 - Poly(thiophosphazenes)

T2 - New Inorganic Backbone Polymers

AU - Allcock, Harry R.

AU - Dodge, Jeffrey A.

AU - Manners, Ian

PY - 1993

Y1 - 1993

N2 - The cyclic thiophosphazene N3P2SCl5 undergoes thermal ring-opening polymerization when heated at 90 °C. The resultant polymer, [N3P2Cl5]n, is a hydrolytically sensitive, yellow, elastomeric material. This polymer reacts with aryloxide nucleophiles to give poly[(aryloxy)thiophosphazenes] of general structure [N3P2S(OAr)xCly] (x > y). The structures of these polymers were examined with the use of 1H and 31P NMR spectroscopy, elemental microanalysis and gel permeation chromatography. The glass transition temperatures of the polymers were measured by means of differential scanning calorimetry and were found to be in a range from −40 to +79 °C. These Tg values are compared to those of poly(carbophosphazene) and classical phosphazene analogues. Reactions of N3P2SCl5 with NaOCH2CF3 and NaOPh—Ph-o are also described.

AB - The cyclic thiophosphazene N3P2SCl5 undergoes thermal ring-opening polymerization when heated at 90 °C. The resultant polymer, [N3P2Cl5]n, is a hydrolytically sensitive, yellow, elastomeric material. This polymer reacts with aryloxide nucleophiles to give poly[(aryloxy)thiophosphazenes] of general structure [N3P2S(OAr)xCly] (x > y). The structures of these polymers were examined with the use of 1H and 31P NMR spectroscopy, elemental microanalysis and gel permeation chromatography. The glass transition temperatures of the polymers were measured by means of differential scanning calorimetry and were found to be in a range from −40 to +79 °C. These Tg values are compared to those of poly(carbophosphazene) and classical phosphazene analogues. Reactions of N3P2SCl5 with NaOCH2CF3 and NaOPh—Ph-o are also described.

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JO - Macromolecules

JF - Macromolecules

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ER -

Poly(thiophosphazenes): New Inorganic Backbone Polymers

Abstract

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