IMIT   21220
INSTITUTO DE MODELADO E INNOVACION TECNOLOGICA
Unidad Ejecutora - UE
artículos
Título:
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
Autor/es:
NATALIA ZARYCZ; EDITH BOTEK; BENOÎT CHAMPAGNE; VALÉRIE SCIANNAMÉA; CHRISTINE JÉRÔME; CHRISTOPHE DETREMBLEUR
Revista:
JOURNAL OF PHYSICAL CHEMISTRY B
Editorial:
American Chemical Society
Referencias:
Lugar: Washington; Año: 2008 vol. 112 p. 10432 - 10442
ISSN:
1089-5647
Resumen:
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-R-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.