Reactions between Hexachlorocyclotriphosphazene and Hexamethylcyclotrisiloxane: Polymerization, Ring Cleavage, and Cross-Linking

Harry R. Allcock; David J. Brennan; Robert W. Allen

doi:10.1021/ma00144a004

Reactions between Hexachlorocyclotriphosphazene and Hexamethylcyclotrisiloxane: Polymerization, Ring Cleavage, and Cross-Linking

Harry R. Allcock, David J. Brennan, Robert W. Allen

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22 Scopus citations

Abstract

The reactions between (NPCl₂)₃and (OSiMe₂)₃at 250 °C have been investigated. Three main processes occur: siloxane ring-ring equilibration, homopolymerization of (NPCl₂)₃ to high polymeric (NPCl₂)_n, and siloxane skeletal cleavage by P-Cl bonds to yield cyclic phosphazenes bearing one or two w-chlorosiloxane side groups. The formation of phosphazene polymers cross-linked by P-O-P bonds also occurs at later stages of the reaction. α, ω-Dichlorosiloxanes are liberated in this latter process. Similar reactions are evident when (NPCl₂)₃reacts with (OSiMe₂)₄ or (Me₃Si)₂O. The interconnected reaction pathways that lead to these products are discussed.

Original language	English (US)
Pages (from-to)	139-144
Number of pages	6
Journal	Macromolecules
Volume	18
Issue number	2
DOIs	https://doi.org/10.1021/ma00144a004
State	Published - Mar 1985

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Reactions between Hexachlorocyclotriphosphazene and Hexamethylcyclotrisiloxane: Polymerization, Ring Cleavage, and Cross-Linking",

abstract = "The reactions between (NPCl2)3and (OSiMe2)3at 250 °C have been investigated. Three main processes occur: siloxane ring-ring equilibration, homopolymerization of (NPCl2)3 to high polymeric (NPCl2)n, and siloxane skeletal cleavage by P-Cl bonds to yield cyclic phosphazenes bearing one or two w-chlorosiloxane side groups. The formation of phosphazene polymers cross-linked by P-O-P bonds also occurs at later stages of the reaction. α, ω-Dichlorosiloxanes are liberated in this latter process. Similar reactions are evident when (NPCl2)3reacts with (OSiMe2)4 or (Me3Si)2O. The interconnected reaction pathways that lead to these products are discussed.",

author = "Allcock, {Harry R.} and Brennan, {David J.} and Allen, {Robert W.}",

year = "1985",

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language = "English (US)",

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pages = "139--144",

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publisher = "American Chemical Society",

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T1 - Reactions between Hexachlorocyclotriphosphazene and Hexamethylcyclotrisiloxane

T2 - Polymerization, Ring Cleavage, and Cross-Linking

AU - Allcock, Harry R.

AU - Brennan, David J.

AU - Allen, Robert W.

PY - 1985/3

Y1 - 1985/3

N2 - The reactions between (NPCl2)3and (OSiMe2)3at 250 °C have been investigated. Three main processes occur: siloxane ring-ring equilibration, homopolymerization of (NPCl2)3 to high polymeric (NPCl2)n, and siloxane skeletal cleavage by P-Cl bonds to yield cyclic phosphazenes bearing one or two w-chlorosiloxane side groups. The formation of phosphazene polymers cross-linked by P-O-P bonds also occurs at later stages of the reaction. α, ω-Dichlorosiloxanes are liberated in this latter process. Similar reactions are evident when (NPCl2)3reacts with (OSiMe2)4 or (Me3Si)2O. The interconnected reaction pathways that lead to these products are discussed.

AB - The reactions between (NPCl2)3and (OSiMe2)3at 250 °C have been investigated. Three main processes occur: siloxane ring-ring equilibration, homopolymerization of (NPCl2)3 to high polymeric (NPCl2)n, and siloxane skeletal cleavage by P-Cl bonds to yield cyclic phosphazenes bearing one or two w-chlorosiloxane side groups. The formation of phosphazene polymers cross-linked by P-O-P bonds also occurs at later stages of the reaction. α, ω-Dichlorosiloxanes are liberated in this latter process. Similar reactions are evident when (NPCl2)3reacts with (OSiMe2)4 or (Me3Si)2O. The interconnected reaction pathways that lead to these products are discussed.

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Reactions between Hexachlorocyclotriphosphazene and Hexamethylcyclotrisiloxane: Polymerization, Ring Cleavage, and Cross-Linking

Abstract

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