[en] In this article, we compare two routes for carrying out in situ nitroxide-mediated polymerization of styrene using the C-phenyl-N-tert-butylnitrone (PBN)/2,2-azobis(isobutyronitrile) (AIBN) pair to identify the best one for an optimal control. One route consists in adding PBN to the radical polymerization of styrene, while the other approach deals with a prereaction between the nitrone and the free radical initiator prior to the addition of the monomer and the polymerization. The combination of ESR and kinetics studies allowed demonstrating that when the polymerization of styrene is initiated by AIBN in the presence of enough PBN at 110 °C, fast decomposition of AIBN is responsible for the accumulation of dead polymer chains at the early stages of the polymerization, in combination with controlled polystyrene chains. On the other hand, PBN acts as a terminating agent at 70 °C with the formation of a polystyrene end-capped by an alkoxyamine, which is not labile at this temperature but that can be reactivated and chain-extended by increasing the temperature. Finally, the radical polymerization of styrene is better controlled when the nitrone/initiator pair is prereacted at 85 °C for 4 h in toluene before styrene is added and polymerized at 110 °C.
Research Center/Unit :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry Materials science & engineering
Author, co-author :
Sciannamea, Valérie; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Catala, Jean-Marie; Institut Charles Sadron, Strasbourg, France
Jérôme, Robert ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Christine ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Detrembleur, Christophe ; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Language :
English
Title :
Relevance of a prereaction for the in situ NMP of styrene using the C-phenyl-N-tert-butylnitrone/2,2’-azobis(isobutyronitrile) pair
Publication date :
15 February 2009
Journal title :
Journal of Polymer Science. Part A, Polymer Chemistry
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