Reference : Ability of nitrones of various structures to control the radical polymerization of st...
Scientific journals : Article
Engineering, computing & technology : Materials science & engineering
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/2268/4506
Ability of nitrones of various structures to control the radical polymerization of styrene mediated by in situ formed nitroxides
English
Sciannamea, Valérie [University of Liège (ULg) > 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 mailto [University of Liège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Detrembleur, Christophe mailto [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
14-Nov-2005
Polymer
Elsevier Sci Ltd
46
23
9632-9641
Yes (verified by ORBi)
International
0032-3861
Oxford
[en] radical polymerization ; nitroxide-mediated polymerization (NMP)
[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.
Center for Education and Research on Macromolecules (CERM)
Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy ; Fonds pour la formation à la Recherche dans l'Industrie et dans l'Agriculture (Communauté française de Belgique) - FRIA ; Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; The Dutch Polymer Institute (DPI), Technology Area ‘High-throughput experimentation’
Researchers
http://hdl.handle.net/2268/4506
10.1016/j.polymer.2005.07.074
http://www.sciencedirect.com/science?_ob=MImg&_imagekey=B6TXW-4GV8TF6-J-12&_cdi=5601&_user=532038&_orig=browse&_coverDate=11%2F14%2F2005&_sk=999539976&view=c&wchp=dGLbVzz-zSkWz&md5=ae56ec21366af27e7b1b83925f537ee8&ie=/sdarticle.pdf
http://www.elsevier.com/wps/find/journaldescription.cws_home/30466/description#description
The authors acknowledge Polymer (Elsevier) for allowing them to archive this paper.

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