Ring Expansion and Polymerization of Transannular Bridged Cyclotriphosphazenes and Their Spirocyclic Analogues

Harry R. Allcock, Michael L. Turner

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

The ring expansion and polymerization reactions of the transannular substituted cyclotriphosphazenes 1,3-[N3P3(OCH2CF3)4(X2R)] (X2R = 1,2-dioxyphenyl, 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl) are described and are compared to the behavior of the analogous spirocyclic cyclotriphosphazenes 1,1-[N3P3(OCH2CF3)4(X2R)] (X2R = 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl). When heated at temperatures above 200 °C, transannular 1,3-[N3P3(OCH2CF3)4(2,2′-O2C12H8)]and spirocyclic 1,1-[N3P3(OCH2CF3)4(2,2′-O2C12H8)], 1,1-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,1-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}] underwent ring-ring equilibration to yield higher cyclic species that ranged from the cyclic tetramer to dodecamer. When heated in the presence of 1% (NPCl2)3, as a polymerization initiator, small amounts of low molecular weight polymer are also formed. By contrast, thermolysis of transannular 1,3-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}], 1,3-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,3-[N3P3(OCH2-CF3)4(1,2-O2C6H4)] at temperatures above 200 °C, in the presence or absence of (NPCl2)3, resulted in ring-opening polymerization to give low molecular weight poly(organophosphazenes). The balance between ring-ring equilibration and ring-opening polymerization is discussed in relation to the ability of the transannular organic group to generate ring strain and destabilize the cyclic trimer with respect to the linear polymer.

Original languageEnglish (US)
Pages (from-to)3-10
Number of pages8
JournalMacromolecules
Volume26
Issue number1
DOIs
StatePublished - Jan 1 1993

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Ring opening polymerization
Polymers
Molecular weight
Polymerization
Thermolysis
Temperature

All Science Journal Classification (ASJC) codes

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

Cite this

@article{f186311f3ac0492f91ba8fa4d1fcb7f0,
title = "Ring Expansion and Polymerization of Transannular Bridged Cyclotriphosphazenes and Their Spirocyclic Analogues",
abstract = "The ring expansion and polymerization reactions of the transannular substituted cyclotriphosphazenes 1,3-[N3P3(OCH2CF3)4(X2R)] (X2R = 1,2-dioxyphenyl, 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl) are described and are compared to the behavior of the analogous spirocyclic cyclotriphosphazenes 1,1-[N3P3(OCH2CF3)4(X2R)] (X2R = 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl). When heated at temperatures above 200 °C, transannular 1,3-[N3P3(OCH2CF3)4(2,2′-O2C12H8)]and spirocyclic 1,1-[N3P3(OCH2CF3)4(2,2′-O2C12H8)], 1,1-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,1-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}] underwent ring-ring equilibration to yield higher cyclic species that ranged from the cyclic tetramer to dodecamer. When heated in the presence of 1{\%} (NPCl2)3, as a polymerization initiator, small amounts of low molecular weight polymer are also formed. By contrast, thermolysis of transannular 1,3-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}], 1,3-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,3-[N3P3(OCH2-CF3)4(1,2-O2C6H4)] at temperatures above 200 °C, in the presence or absence of (NPCl2)3, resulted in ring-opening polymerization to give low molecular weight poly(organophosphazenes). The balance between ring-ring equilibration and ring-opening polymerization is discussed in relation to the ability of the transannular organic group to generate ring strain and destabilize the cyclic trimer with respect to the linear polymer.",
author = "Allcock, {Harry R.} and Turner, {Michael L.}",
year = "1993",
month = "1",
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doi = "10.1021/ma00053a001",
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Ring Expansion and Polymerization of Transannular Bridged Cyclotriphosphazenes and Their Spirocyclic Analogues. / Allcock, Harry R.; Turner, Michael L.

In: Macromolecules, Vol. 26, No. 1, 01.01.1993, p. 3-10.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Ring Expansion and Polymerization of Transannular Bridged Cyclotriphosphazenes and Their Spirocyclic Analogues

AU - Allcock, Harry R.

AU - Turner, Michael L.

PY - 1993/1/1

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N2 - The ring expansion and polymerization reactions of the transannular substituted cyclotriphosphazenes 1,3-[N3P3(OCH2CF3)4(X2R)] (X2R = 1,2-dioxyphenyl, 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl) are described and are compared to the behavior of the analogous spirocyclic cyclotriphosphazenes 1,1-[N3P3(OCH2CF3)4(X2R)] (X2R = 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl). When heated at temperatures above 200 °C, transannular 1,3-[N3P3(OCH2CF3)4(2,2′-O2C12H8)]and spirocyclic 1,1-[N3P3(OCH2CF3)4(2,2′-O2C12H8)], 1,1-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,1-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}] underwent ring-ring equilibration to yield higher cyclic species that ranged from the cyclic tetramer to dodecamer. When heated in the presence of 1% (NPCl2)3, as a polymerization initiator, small amounts of low molecular weight polymer are also formed. By contrast, thermolysis of transannular 1,3-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}], 1,3-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,3-[N3P3(OCH2-CF3)4(1,2-O2C6H4)] at temperatures above 200 °C, in the presence or absence of (NPCl2)3, resulted in ring-opening polymerization to give low molecular weight poly(organophosphazenes). The balance between ring-ring equilibration and ring-opening polymerization is discussed in relation to the ability of the transannular organic group to generate ring strain and destabilize the cyclic trimer with respect to the linear polymer.

AB - The ring expansion and polymerization reactions of the transannular substituted cyclotriphosphazenes 1,3-[N3P3(OCH2CF3)4(X2R)] (X2R = 1,2-dioxyphenyl, 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl) are described and are compared to the behavior of the analogous spirocyclic cyclotriphosphazenes 1,1-[N3P3(OCH2CF3)4(X2R)] (X2R = 2,2′-dioxybiphenyl, 1,8-dioxynaphthyl, and 1,8-diaminonaphthyl). When heated at temperatures above 200 °C, transannular 1,3-[N3P3(OCH2CF3)4(2,2′-O2C12H8)]and spirocyclic 1,1-[N3P3(OCH2CF3)4(2,2′-O2C12H8)], 1,1-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,1-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}] underwent ring-ring equilibration to yield higher cyclic species that ranged from the cyclic tetramer to dodecamer. When heated in the presence of 1% (NPCl2)3, as a polymerization initiator, small amounts of low molecular weight polymer are also formed. By contrast, thermolysis of transannular 1,3-[N3P3(OCH2CF3)4{1,8-(NH)2C10H6}], 1,3-[N3P3(OCH2CF3)4(1,8-O2C10H6)], and 1,3-[N3P3(OCH2-CF3)4(1,2-O2C6H4)] at temperatures above 200 °C, in the presence or absence of (NPCl2)3, resulted in ring-opening polymerization to give low molecular weight poly(organophosphazenes). The balance between ring-ring equilibration and ring-opening polymerization is discussed in relation to the ability of the transannular organic group to generate ring strain and destabilize the cyclic trimer with respect to the linear polymer.

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