Joint theoretical experimental investigation of the electron spin resonance spectra of nitroxyl radicals

Application to intermediates in in situ nitroxide mediated polymerization (in situ NMP) of vinyl monomers

Natalia Zarycz, Edith Botek, Benoît Champagne, Valérie Sciannaméa, Christine Jérôme, Christophe Detrembleur

Research output: Contribution to journalArticle

Abstract

Density functional theory (DFT) calculations have been performed to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated hyperfine coupling constants (HFCCs) to experimental data for a set of linear and cyclic alkylnitroxyl radicals. Considering this tested approach, the nature of different nitroxides has been predicted or confirmed for (a) the reaction of C-pnenyl-N-tert-butylnitrone and AIBN, (b) N-tert-butyl-α-isopropylnitrone and benzoyl peroxide, (c) tert-butyl methacrylate polymerization in the presence of sodium nitrite as mediator, and (d) for the reaction of a nitroso compound with AIBN. Values of HFCC experimentally determined have been confirmed by DFT calculations.

Original languageEnglish
Pages (from-to)10432-10442
Number of pages11
JournalJournal of physical chemistry B
Volume112
Issue number34
DOIs
Publication statusPublished - 28 Aug 2008

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Density functional theory
Paramagnetic resonance
electron paramagnetic resonance
nitroso compounds
polymerization
monomers
Monomers
Polymerization
Benzoyl Peroxide
Nitroso Compounds
density functional theory
Sodium Nitrite
Benzoyl peroxide
nitrites
peroxides
Free radical polymerization
Sodium
sodium
nitroxyl
azobis(isobutyronitrile)

Cite this

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abstract = "Density functional theory (DFT) calculations have been performed to address the structure of nitroxide intermediates in controlled radical polymerization. In a preliminary step, the reliability of different theoretical methods has been substantiated by comparing calculated hyperfine coupling constants (HFCCs) to experimental data for a set of linear and cyclic alkylnitroxyl radicals. Considering this tested approach, the nature of different nitroxides has been predicted or confirmed for (a) the reaction of C-pnenyl-N-tert-butylnitrone and AIBN, (b) N-tert-butyl-α-isopropylnitrone and benzoyl peroxide, (c) tert-butyl methacrylate polymerization in the presence of sodium nitrite as mediator, and (d) for the reaction of a nitroso compound with AIBN. Values of HFCC experimentally determined have been confirmed by DFT calculations.",
author = "Natalia Zarycz and Edith Botek and Beno{\^i}t Champagne and Val{\'e}rie Sciannam{\'e}a and Christine J{\'e}r{\^o}me and Christophe Detrembleur",
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month = "8",
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Joint theoretical experimental investigation of the electron spin resonance spectra of nitroxyl radicals : Application to intermediates in in situ nitroxide mediated polymerization (in situ NMP) of vinyl monomers. / Zarycz, Natalia; Botek, Edith; Champagne, Benoît; Sciannaméa, Valérie; Jérôme, Christine; Detrembleur, Christophe.

In: Journal of physical chemistry B, Vol. 112, No. 34, 28.08.2008, p. 10432-10442.

Research output: Contribution to journalArticle

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