A new route for poly(organophosphazene) synthesis. Polymerization, copolymerization, and ring-ring equilibration of trifluoroethoxy- and chloro-substituted cyclotriphosphazenes

H. R. Allcock; J. L. Schmutz; Karen M. Kosydar

A new route for poly(organophosphazene) synthesis. Polymerization, copolymerization, and ring-ring equilibration of trifluoroethoxy- and chloro-substituted cyclotriphosphazenes

H. R. Allcock, J. L. Schmutz, Karen M. Kosydar

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

Abstract

The phosphazene cyclic trimer, [NP(OCH₂CF₃)₂]₃ (X), copolymerizes with (NPCl₂)₃ (I) to yield a new series of elastomers and also undergoes ring-expansion reactions at elevated temperatures. The copolymers were characterized by means of substitution reactions and ³¹P NMR analysis. The possibility that the polymerization involves a prior ligand exchange was investigated through studies of the thermal behavior of the cyclic phosphazenes, N₃P₃Cl₅(OCH₂CF₃) (V), N₃P₃Cl₄(OCH₂CF₃) ₂ (trans nongem) (VI), N₃P₃Cl₃(OCH₂CF₃) ₃ (trans nongem) (VII), N₃P₃Cl₂(OCH₂CF₃) ₄ (cis nongem) (VIII), and N₃P₃Cl(OCH₂CF₃)₅ (IX). All these mixed substituent trimers underwent ring expansion reactions when heated, but only compounds V, VI, and VII yielded linear-type polymers. The gas CF₃CH₂Cl, was detected as a product from all systems that contained both P-Cl and P-OCH₂CF₃ bonds, with substantial quantities being released at temperatures above 250°C. This process was apparently connected with the formation of trans-annular-linked cyclic compounds, cross-linked linear chains, or cyclolinear or cyclomatrix-type products. The mechanisms of these reactions are discussed.

Original language	English (US)
Pages (from-to)	179-186
Number of pages	8
Journal	Macromolecules
Volume	11
Issue number	1
State	Published - Dec 1 1978

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

Cite this

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title = "A new route for poly(organophosphazene) synthesis. Polymerization, copolymerization, and ring-ring equilibration of trifluoroethoxy- and chloro-substituted cyclotriphosphazenes",

abstract = "The phosphazene cyclic trimer, [NP(OCH2CF3)2]3 (X), copolymerizes with (NPCl2)3 (I) to yield a new series of elastomers and also undergoes ring-expansion reactions at elevated temperatures. The copolymers were characterized by means of substitution reactions and 31P NMR analysis. The possibility that the polymerization involves a prior ligand exchange was investigated through studies of the thermal behavior of the cyclic phosphazenes, N3P3Cl5(OCH2CF3) (V), N3P3Cl4(OCH2CF3) 2 (trans nongem) (VI), N3P3Cl3(OCH2CF3) 3 (trans nongem) (VII), N3P3Cl2(OCH2CF3) 4 (cis nongem) (VIII), and N3P3Cl(OCH2CF3)5 (IX). All these mixed substituent trimers underwent ring expansion reactions when heated, but only compounds V, VI, and VII yielded linear-type polymers. The gas CF3CH2Cl, was detected as a product from all systems that contained both P-Cl and P-OCH2CF3 bonds, with substantial quantities being released at temperatures above 250°C. This process was apparently connected with the formation of trans-annular-linked cyclic compounds, cross-linked linear chains, or cyclolinear or cyclomatrix-type products. The mechanisms of these reactions are discussed.",

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T1 - A new route for poly(organophosphazene) synthesis. Polymerization, copolymerization, and ring-ring equilibration of trifluoroethoxy- and chloro-substituted cyclotriphosphazenes

AU - Allcock, H. R.

AU - Schmutz, J. L.

AU - Kosydar, Karen M.

PY - 1978/12/1

Y1 - 1978/12/1

N2 - The phosphazene cyclic trimer, [NP(OCH2CF3)2]3 (X), copolymerizes with (NPCl2)3 (I) to yield a new series of elastomers and also undergoes ring-expansion reactions at elevated temperatures. The copolymers were characterized by means of substitution reactions and 31P NMR analysis. The possibility that the polymerization involves a prior ligand exchange was investigated through studies of the thermal behavior of the cyclic phosphazenes, N3P3Cl5(OCH2CF3) (V), N3P3Cl4(OCH2CF3) 2 (trans nongem) (VI), N3P3Cl3(OCH2CF3) 3 (trans nongem) (VII), N3P3Cl2(OCH2CF3) 4 (cis nongem) (VIII), and N3P3Cl(OCH2CF3)5 (IX). All these mixed substituent trimers underwent ring expansion reactions when heated, but only compounds V, VI, and VII yielded linear-type polymers. The gas CF3CH2Cl, was detected as a product from all systems that contained both P-Cl and P-OCH2CF3 bonds, with substantial quantities being released at temperatures above 250°C. This process was apparently connected with the formation of trans-annular-linked cyclic compounds, cross-linked linear chains, or cyclolinear or cyclomatrix-type products. The mechanisms of these reactions are discussed.

AB - The phosphazene cyclic trimer, [NP(OCH2CF3)2]3 (X), copolymerizes with (NPCl2)3 (I) to yield a new series of elastomers and also undergoes ring-expansion reactions at elevated temperatures. The copolymers were characterized by means of substitution reactions and 31P NMR analysis. The possibility that the polymerization involves a prior ligand exchange was investigated through studies of the thermal behavior of the cyclic phosphazenes, N3P3Cl5(OCH2CF3) (V), N3P3Cl4(OCH2CF3) 2 (trans nongem) (VI), N3P3Cl3(OCH2CF3) 3 (trans nongem) (VII), N3P3Cl2(OCH2CF3) 4 (cis nongem) (VIII), and N3P3Cl(OCH2CF3)5 (IX). All these mixed substituent trimers underwent ring expansion reactions when heated, but only compounds V, VI, and VII yielded linear-type polymers. The gas CF3CH2Cl, was detected as a product from all systems that contained both P-Cl and P-OCH2CF3 bonds, with substantial quantities being released at temperatures above 250°C. This process was apparently connected with the formation of trans-annular-linked cyclic compounds, cross-linked linear chains, or cyclolinear or cyclomatrix-type products. The mechanisms of these reactions are discussed.

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A new route for poly(organophosphazene) synthesis. Polymerization, copolymerization, and ring-ring equilibration of trifluoroethoxy- and chloro-substituted cyclotriphosphazenes

Abstract

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