Acyclic β-phosphonylated nitroxides: a new series of counter-radicals for 'living'/controlled free radical polymerization

Sandra Grimaldi; Jean Pierre Finet; François Le Moigne; Abdelhamid Zeghdaoui; Paul Tordo; Didier Benoit; Michel Fontanille; Yves Gnanou

doi:10.1021/ma9913414

Acyclic β-phosphonylated nitroxides: a new series of counter-radicals for 'living'/controlled free radical polymerization

Sandra Grimaldi, Jean Pierre Finet, François Le Moigne, Abdelhamid Zeghdaoui, Paul Tordo, Didier Benoit, Michel Fontanille, Yves Gnanou

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

229 Scopus citations

Abstract

Oxidation of α-(N-alkylamino) phosphonic acid esters, carrying one or two alkyl groups as substituents on their α-carbon, by m-chloroperbenzoic acid afforded the corresponding stable β-phosphonylated nitroxides. The nitroxides derived from α-mono-tert-butyl α-alkylaminophosphonic acid esters are stable compounds despite the presence of a hydrogen atom on the α-carbon bound to the nitroxyl group. The ESR study of these nitroxides in solution showed that this β-hydrogen atom lies in the nodal plane to the nitroxyl function. These β-phosphonylated nitroxides were found to efficiently control the free radical polymerization reaction of styrene, with a much faster rate of propagation than that observed in TEMPO-mediated systems.

Original language	English (US)
Pages (from-to)	1141-1147
Number of pages	7
Journal	Macromolecules
Volume	33
Issue number	4
DOIs	https://doi.org/10.1021/ma9913414
State	Published - 2000
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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title = "Acyclic β-phosphonylated nitroxides: a new series of counter-radicals for 'living'/controlled free radical polymerization",

abstract = "Oxidation of α-(N-alkylamino) phosphonic acid esters, carrying one or two alkyl groups as substituents on their α-carbon, by m-chloroperbenzoic acid afforded the corresponding stable β-phosphonylated nitroxides. The nitroxides derived from α-mono-tert-butyl α-alkylaminophosphonic acid esters are stable compounds despite the presence of a hydrogen atom on the α-carbon bound to the nitroxyl group. The ESR study of these nitroxides in solution showed that this β-hydrogen atom lies in the nodal plane to the nitroxyl function. These β-phosphonylated nitroxides were found to efficiently control the free radical polymerization reaction of styrene, with a much faster rate of propagation than that observed in TEMPO-mediated systems.",

author = "Sandra Grimaldi and Finet, {Jean Pierre} and {Le Moigne}, Fran{\c c}ois and Abdelhamid Zeghdaoui and Paul Tordo and Didier Benoit and Michel Fontanille and Yves Gnanou",

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doi = "10.1021/ma9913414",

language = "English (US)",

volume = "33",

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journal = "Macromolecules",

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TY - JOUR

T1 - Acyclic β-phosphonylated nitroxides

T2 - a new series of counter-radicals for 'living'/controlled free radical polymerization

AU - Grimaldi, Sandra

AU - Finet, Jean Pierre

AU - Le Moigne, François

AU - Zeghdaoui, Abdelhamid

AU - Tordo, Paul

AU - Benoit, Didier

AU - Fontanille, Michel

AU - Gnanou, Yves

PY - 2000

Y1 - 2000

N2 - Oxidation of α-(N-alkylamino) phosphonic acid esters, carrying one or two alkyl groups as substituents on their α-carbon, by m-chloroperbenzoic acid afforded the corresponding stable β-phosphonylated nitroxides. The nitroxides derived from α-mono-tert-butyl α-alkylaminophosphonic acid esters are stable compounds despite the presence of a hydrogen atom on the α-carbon bound to the nitroxyl group. The ESR study of these nitroxides in solution showed that this β-hydrogen atom lies in the nodal plane to the nitroxyl function. These β-phosphonylated nitroxides were found to efficiently control the free radical polymerization reaction of styrene, with a much faster rate of propagation than that observed in TEMPO-mediated systems.

AB - Oxidation of α-(N-alkylamino) phosphonic acid esters, carrying one or two alkyl groups as substituents on their α-carbon, by m-chloroperbenzoic acid afforded the corresponding stable β-phosphonylated nitroxides. The nitroxides derived from α-mono-tert-butyl α-alkylaminophosphonic acid esters are stable compounds despite the presence of a hydrogen atom on the α-carbon bound to the nitroxyl group. The ESR study of these nitroxides in solution showed that this β-hydrogen atom lies in the nodal plane to the nitroxyl function. These β-phosphonylated nitroxides were found to efficiently control the free radical polymerization reaction of styrene, with a much faster rate of propagation than that observed in TEMPO-mediated systems.

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DO - 10.1021/ma9913414

M3 - Article

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JO - Macromolecules

JF - Macromolecules

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ER -

Acyclic β-phosphonylated nitroxides: a new series of counter-radicals for 'living'/controlled free radical polymerization

Abstract

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