[en] The styrene polymerization initiated by benzoyl peroxide (BPO) in the presence of N-tert-butyl--isopropylnitrone as nitroxide precursor is well-controlled provided that a prereaction between the nitrone and BPO is carried out in suitable conditions prior to polymerization at a higher temperature. Electron spin resonance (ESR) spectroscopy was implemented to probe the nitroxides formed during both steps, that is, the prereaction and polymerization, and to get crucial information regarding the structure of the nitroxides responsible for the polymerization control. ESR studies combined with first principles calculations have evidenced that nitroxides observed during the prereaction in the presence of styrene and during the polymerization steps consist of a mixture of two macronitroxides. One is formed by the addition of a growing polystyrene chain to the nitrone as would be expected. However, the second one results from the addition of a polystyrene chain to tert-butyl nitroso that is in situ formed presumably by decomposition of the first macronitroxide type.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Clément, Jean-Louis; University of Aix-Marseille , CNRS, France > Institut de Chimie Radicalaire, UMR7273
Sciannaméa, Valérie; Institut Charles Sadron CNRS, Strasbourg, France > Chimie des Polymères
Jérôme, Christine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Catala, Jean-Marie; Institut Charles Sadron CNRS, Strasbourg, France > Chimie des Polymères
Gigmes, Didier; University of Aix-Marseille , CNRS, France > Institut de Chimie Radicalaire, UMR7273
Autissier, Laurent; University of Aix-Marseille , CNRS, France > Institut de Chimie Radicalaire, UMR7273
Botek, Edith; University of Namur > Laboratoire de Chimie Thèorique
Zarycz, Natalia; University of Namur and Universidad Nacional del Nordeste, Corrientes, Argentina > Departamento de Fisica (Argnetina) > Laboratoire de Chimie Théorique (Namur)
Champagne, Benoit; University of Namur > Laboratoire de Chimie Théorique
Language :
English
Title :
In situ nitroxide-mediated polymerization of styrene promoted by the N-tert-butyl-alpha-isopropylnitrone/BPO pair: ESR investigations
Publication date :
15 April 2013
Journal title :
Journal of Polymer Science. Part A, Polymer Chemistry
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