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[University of Namur (FUNDP) and Universidad Nacional del Nordeste, Corrientes, Argentina > Departamento de Física, (Argentina) > Laboratoire de Chimie Théorique Appliquée (Belgium) > >]
Botek, Edith[University of Namur (FUNDP) > > Laboratoire de Chimie Théorique Appliquée > >]
Champagne, Benoit[University of Namur (FUNDP) > > Laboratoire de Chimie Théorique Appliquée > >]
Sciannaméa, Valérie[University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Jérôme, Christine[University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
[en] 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-phenyl-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.
Center for Education and Research on Macromolecules (CERM)
Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy ; Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; The "Consejo Nacional de Investigaciones Cientificas y Técnicas"