Reference : Kinetics and electron spin resonance study of the radical polymerization of n-butyl a...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
Engineering, computing & technology : Materials science & engineering
http://hdl.handle.net/2268/4504
Kinetics and electron spin resonance study of the radical polymerization of n-butyl acrylate mediated by a nitroxide precursor: C-phenyl-N-tert-butylnitrone
English
Sciannamea, Valérie [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
Bernard, Maxime [Institut Charles Sadron, Strasbourg, France > > > >]
Catala, Jean-Marie [Institut Charles Sadron, Strasbourg, France > > > >]
Jérôme, Robert mailto [University of Liège (ULg) > 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) > >]
1-Nov-2006
Journal of Polymer Science. Part A, Polymer Chemistry
Wiley
44
21
6299-6311
Yes (verified by ORBi)
International
0887-624X
1099-0518
Hoboken
[en] radical polymerization ; nitroxide-mediated polymerization (NMP)
[en] The C-phenyl-N-tert-butylnitrone/azobisisobutyronitrile pair is able to impart control to the radical polymerization of n-butyl acrylate as long as a two-step process is implemented, that is, the prereaction of the nitrone and the initiator in toluene at 85 degrees C for 4 h followed by the addition and polymerization of n-butyl acrylate at 110 degrees C. The structure of the in situ formed nitroxide has been established from kinetic and electron spin resonance data. The key parameters (the dissociation rate constant, combination rate constant, and equilibrium constant) that govern the process have been evaluated. The equilibrium constant between the dormant and active species is close to 1.6 x 10(-12) mol L-1 at 110 degrees C. The dissociation rate constant and the activation energy for the C-ON bond homolysis are 1.9 x 10(-3) s(-1) and 122 +/- 15 kJ mol(-1), respectively. The rate constant of recombination between the propagating adical and the nitroxide is as high as 1.2 x 10(9) L mol(-1) s(-1). Finally, well-defined poly(n-butyl acrylate)-b-polystyrene block copolymers have been successfully prepared.
Center for Education and Research on Macromolecules (CERM)
Politique Scientifique Fédérale (Belgique) = Belgian Federal Science Policy ; Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; Centre National pour la Recherche Scientifique, France ; Communauté Wallonie-Bruxelles: Commissariat Général aux Relations Internationales ; Fonds pour la formation à la Recherche dans l'Industrie et dans l'Agriculture (Communauté française de Belgique) - FRIA
Researchers
http://hdl.handle.net/2268/4504
10.1002/pola.21698
http://www3.interscience.wiley.com/cgi-bin/fulltext/113378811/PDFSTART
The authors acknowledge Journal of Polymer Science Part A-Polymer Chemistry (Wiley) for allowing them to archive this paper.

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