Organosiloxyphosphazene polymers: Synthesis via aminosiloxane reagents

Harry R. Allcock; William D. Coggio

doi:10.1021/ma00208a011

Organosiloxyphosphazene polymers: Synthesis via aminosiloxane reagents

Harry R. Allcock, William D. Coggio

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Abstract

Cyclic and high polymeric phosphazenes have been synthesized with aminosiloxane side groups either as the sole substituent or with cosubstituents such as OCH₂CF₃, OCH₂CH₂OCH₂CH₂OCH₃, or OC₆H₅. Small-molecule model compound reactions were first carried out between N₃P₃(OPh)₅Cl and H₂N(CH₂)₃SiMe₂OSiMe₃ or H₂N(CH₂)₃Si(OSiMe₃)₃ to yield the pentaphenoxymonoaminosiloxy derivatives N₃P₃(OPh)₅NH(CH₂)₃SiMe₂OSiMe₃ and N₃P₃(OPh)₅NH(CH₂)₃Si(OSiMe₃)₃. Following the structural identification of these species, similar reactions were carried out between the high polymeric phosphazenes [NP(R)_xCl_y]_n, where R = OCH₂CF₃, OPh, or OCH₂CH₂OCH₂CH₂OCH_3> χ = 0, 0.5, or 1.5, y = 2 -χ, and η = 15 000, and the same two aminosiloxanes. The molecular structures of the final polymers were deduced from a combination of elemental analysis and¹H NMR integration. The substituent distribution and thermal-, surface-, and solid-state properties of the aminosiloxyphosphazene polymers are described.

Original language	English (US)
Pages (from-to)	1626-1635
Number of pages	10
Journal	Macromolecules
Volume	23
Issue number	6
DOIs	https://doi.org/10.1021/ma00208a011
State	Published - 1990

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Organosiloxyphosphazene polymers: Synthesis via aminosiloxane reagents",

abstract = "Cyclic and high polymeric phosphazenes have been synthesized with aminosiloxane side groups either as the sole substituent or with cosubstituents such as OCH2CF3, OCH2CH2OCH2CH2OCH3, or OC6H5. Small-molecule model compound reactions were first carried out between N3P3(OPh)5Cl and H2N(CH2)3SiMe2OSiMe3 or H2N(CH2)3Si(OSiMe3)3 to yield the pentaphenoxymonoaminosiloxy derivatives N3P3(OPh)5NH(CH2)3SiMe2OSiMe3 and N3P3(OPh)5NH(CH2)3Si(OSiMe3)3. Following the structural identification of these species, similar reactions were carried out between the high polymeric phosphazenes [NP(R)xCly]n, where R = OCH2CF3, OPh, or OCH2CH2OCH2CH2OCH3> χ = 0, 0.5, or 1.5, y = 2 -χ, and η = 15 000, and the same two aminosiloxanes. The molecular structures of the final polymers were deduced from a combination of elemental analysis and1H NMR integration. The substituent distribution and thermal-, surface-, and solid-state properties of the aminosiloxyphosphazene polymers are described.",

author = "Allcock, {Harry R.} and Coggio, {William D.}",

year = "1990",

doi = "10.1021/ma00208a011",

language = "English (US)",

volume = "23",

pages = "1626--1635",

journal = "Macromolecules",

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T1 - Organosiloxyphosphazene polymers

T2 - Synthesis via aminosiloxane reagents

AU - Allcock, Harry R.

AU - Coggio, William D.

PY - 1990

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N2 - Cyclic and high polymeric phosphazenes have been synthesized with aminosiloxane side groups either as the sole substituent or with cosubstituents such as OCH2CF3, OCH2CH2OCH2CH2OCH3, or OC6H5. Small-molecule model compound reactions were first carried out between N3P3(OPh)5Cl and H2N(CH2)3SiMe2OSiMe3 or H2N(CH2)3Si(OSiMe3)3 to yield the pentaphenoxymonoaminosiloxy derivatives N3P3(OPh)5NH(CH2)3SiMe2OSiMe3 and N3P3(OPh)5NH(CH2)3Si(OSiMe3)3. Following the structural identification of these species, similar reactions were carried out between the high polymeric phosphazenes [NP(R)xCly]n, where R = OCH2CF3, OPh, or OCH2CH2OCH2CH2OCH3> χ = 0, 0.5, or 1.5, y = 2 -χ, and η = 15 000, and the same two aminosiloxanes. The molecular structures of the final polymers were deduced from a combination of elemental analysis and1H NMR integration. The substituent distribution and thermal-, surface-, and solid-state properties of the aminosiloxyphosphazene polymers are described.

AB - Cyclic and high polymeric phosphazenes have been synthesized with aminosiloxane side groups either as the sole substituent or with cosubstituents such as OCH2CF3, OCH2CH2OCH2CH2OCH3, or OC6H5. Small-molecule model compound reactions were first carried out between N3P3(OPh)5Cl and H2N(CH2)3SiMe2OSiMe3 or H2N(CH2)3Si(OSiMe3)3 to yield the pentaphenoxymonoaminosiloxy derivatives N3P3(OPh)5NH(CH2)3SiMe2OSiMe3 and N3P3(OPh)5NH(CH2)3Si(OSiMe3)3. Following the structural identification of these species, similar reactions were carried out between the high polymeric phosphazenes [NP(R)xCly]n, where R = OCH2CF3, OPh, or OCH2CH2OCH2CH2OCH3> χ = 0, 0.5, or 1.5, y = 2 -χ, and η = 15 000, and the same two aminosiloxanes. The molecular structures of the final polymers were deduced from a combination of elemental analysis and1H NMR integration. The substituent distribution and thermal-, surface-, and solid-state properties of the aminosiloxyphosphazene polymers are described.

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Organosiloxyphosphazene polymers: Synthesis via aminosiloxane reagents

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