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

Harry R. Allcock; Michael L. Turner

doi:10.1021/ma00053a001

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

Harry R. Allcock
, Michael L. Turner

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

30 Scopus citations

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 language	English (US)
Pages (from-to)	3-10
Number of pages	8
Journal	Macromolecules
Volume	26
Issue number	1
DOIs	https://doi.org/10.1021/ma00053a001
State	Published - 1993

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1021/ma00053a001

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",

doi = "10.1021/ma00053a001",

language = "English (US)",

volume = "26",

pages = "3--10",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "1",

}

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

Y1 - 1993

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.

UR - https://www.scopus.com/pages/publications/0027908215

UR - https://www.scopus.com/pages/publications/0027908215#tab=citedBy

U2 - 10.1021/ma00053a001

DO - 10.1021/ma00053a001

M3 - Article

AN - SCOPUS:0027908215

SN - 0024-9297

VL - 26

SP - 3

EP - 10

JO - Macromolecules

JF - Macromolecules

IS - 1

ER -

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

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this