Article (Scientific journals)
Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides
Sciannamea, Valérie; Guerrero-Sanchez, Carlos; Schubert, Ulrich S. et al.
2005In Polymer, 46 (23), p. 9632-9641
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Keywords :
radical polymerization; nitroxide-mediated polymerization (NMP)
Abstract :
[en] The ability of several nitrones to control the radical polymerization of styrene at 110 °C has been investigated by high-throughput experimentation. The nitrone/free radical initiator pair dictates the structure of the nitroxide and the alkoxyamine formed in situ, which determines the position of the equilibrium between the active and the dormant species operating in the nitroxide-mediated polymerization. For the styrene polymerization to be controlled, the nitrone must be reacted with 2,2'-azo-bis-isobutyronitrile (AIBN) at 85 °C, prior to addition of styrene and polymerization at 110 °C. The effect of the nitrone structure on the kinetics of the styrene polymerization has been emphasized. Amongst all the nitrones tested, those of the C-phenyl-N-tert-butylnitrone (PBN) type are the most efficient in terms of polymerization rate, control of molecular weight and polydispersity. Electrophilic substitution of the phenyl group of PBN by either an electrodonor or an electroacceptor group has only a minor effect on the polymerization kinetics. Importantly, the polymerization rate is not governed by the thermal polymerization of styrene but by the alkoxyamine formed in situ during the pre-reaction step. The initiation efficiency is, however, very low, consistent with a limited conversion of the nitrone into nitroxide and alkoxyamine.
Research center :
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)
Guerrero-Sanchez, Carlos;  Eindhoven University of Technology and Dutch Polymer Institute (DPI), The Netherlands > Laboratory of Macromolecular Chemistry and Nanoscience
Schubert, Ulrich S.;  Eindhoven University of Technology and Dutch Polymer Institute (DPI), The Netherlands > Laboratory of Macromolecular Chemistry and Nanoscience
Catala, Jean-Marie;  Institut Charles Sadron, Strasbourg, France
Jérôme, Robert ;  University of Liège > 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 :
Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides
Publication date :
14 November 2005
Journal title :
Polymer
ISSN :
0032-3861
eISSN :
1873-2291
Publisher :
Elsevier Sci Ltd, Oxford, United Kingdom
Volume :
46
Issue :
23
Pages :
9632-9641
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE]
F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE]
The Dutch Polymer Institute (DPI), Technology Area ‘High-throughput experimentation’
Commentary :
The authors acknowledge Polymer (Elsevier) for allowing them to archive this paper.
Available on ORBi :
since 22 January 2009

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