Ring-Ring and Ring-Chain Equilibration of Dimethylphosphazenes. Relation to Phosphazene Polymerization

H. R. Allcock; D. B. Patterson

doi:10.1021/ic50167a041

Ring-Ring and Ring-Chain Equilibration of Dimethylphosphazenes. Relation to Phosphazene Polymerization

H. R. Allcock, D. B. Patterson

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Abstract

Hexamethylcyclotriphosphazene, [NP(CH₃)₂]₃, and octamethylcyclotetraphosphazene, [NP(CH₃)₂]₄, participate in a ring-ring equilibration between 200 and 350 °C, but they do not polymerize. A ΔH value of 10.2 kcal and a ΔS value of 14.3 eu were determined for the tetramer-trimer interconversion. The equilibration is inhibited by base. Acids accelerate equilibration and also yield linear low molecular weight compounds: these species cyclize to III and IV when heated. The results are compared with the ring-high polymer and ring-ring interconversions in the halogenophosphazene, dimethylsiloxane, dimethylsilthiane, and polysulfur series.

Original language	English (US)
Pages (from-to)	197-200
Number of pages	4
Journal	Inorganic chemistry
Volume	16
Issue number	1
DOIs	https://doi.org/10.1021/ic50167a041
State	Published - Jan 1 1977

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Ring-Ring and Ring-Chain Equilibration of Dimethylphosphazenes. Relation to Phosphazene Polymerization",

abstract = "Hexamethylcyclotriphosphazene, [NP(CH3)2]3, and octamethylcyclotetraphosphazene, [NP(CH3)2]4, participate in a ring-ring equilibration between 200 and 350 °C, but they do not polymerize. A ΔH value of 10.2 kcal and a ΔS value of 14.3 eu were determined for the tetramer-trimer interconversion. The equilibration is inhibited by base. Acids accelerate equilibration and also yield linear low molecular weight compounds: these species cyclize to III and IV when heated. The results are compared with the ring-high polymer and ring-ring interconversions in the halogenophosphazene, dimethylsiloxane, dimethylsilthiane, and polysulfur series.",

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T1 - Ring-Ring and Ring-Chain Equilibration of Dimethylphosphazenes. Relation to Phosphazene Polymerization

AU - Allcock, H. R.

AU - Patterson, D. B.

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N2 - Hexamethylcyclotriphosphazene, [NP(CH3)2]3, and octamethylcyclotetraphosphazene, [NP(CH3)2]4, participate in a ring-ring equilibration between 200 and 350 °C, but they do not polymerize. A ΔH value of 10.2 kcal and a ΔS value of 14.3 eu were determined for the tetramer-trimer interconversion. The equilibration is inhibited by base. Acids accelerate equilibration and also yield linear low molecular weight compounds: these species cyclize to III and IV when heated. The results are compared with the ring-high polymer and ring-ring interconversions in the halogenophosphazene, dimethylsiloxane, dimethylsilthiane, and polysulfur series.

AB - Hexamethylcyclotriphosphazene, [NP(CH3)2]3, and octamethylcyclotetraphosphazene, [NP(CH3)2]4, participate in a ring-ring equilibration between 200 and 350 °C, but they do not polymerize. A ΔH value of 10.2 kcal and a ΔS value of 14.3 eu were determined for the tetramer-trimer interconversion. The equilibration is inhibited by base. Acids accelerate equilibration and also yield linear low molecular weight compounds: these species cyclize to III and IV when heated. The results are compared with the ring-high polymer and ring-ring interconversions in the halogenophosphazene, dimethylsiloxane, dimethylsilthiane, and polysulfur series.

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Ring-Ring and Ring-Chain Equilibration of Dimethylphosphazenes. Relation to Phosphazene Polymerization

Abstract

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