Reference : Controlled radical polymerization of styrene mediated by the C-phenyl-N-tert-butylnitron...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
Engineering, computing & technology : Materials science & engineering
http://hdl.handle.net/2268/4302
Controlled radical polymerization of styrene mediated by the C-phenyl-N-tert-butylnitrone/AIBN pair: Kinetics and electron spin resonance analysis
English
Sciannamea, Valérie [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >]
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-Apr-2007
Journal of Polymer Science. Part A, Polymer Chemistry
Wiley
45
7
1219-1235
Yes (verified by ORBi)
International
0887-624X
1099-0518
Hoboken
[en] radical polymerization ; nitroxide-mediated polymerization (NMP)
[en] Kinetics of the free radical polymerization of styrene at 110 degrees C has been investigated in the presence of C-phenyl-N-tert-butylnitrone (PBN) and 2,2'-azobis(isobutyronitrile) (AIBN) after prereaction in toluene at 85 degrees C. The effect of the prereaction time and the PBN/AIBN molar ratio on the in situ formation of nitroxides and alkoxyamines (at 85 degrees C), and ultimately on the control of the styrene polymerization at 110 degrees C, has been investigated. As a rule, the styrene radical polymerization is controlled, and the mechanism is one of the classical nitroxide-mediated polymerization. Only one type of nitroxide (low-molecular-mass nitroxide) is formed whatever the prereaction conditions at 85 degrees C, and the equilibrium constant (K) between active and dormant species is 8.7 x 10(-10) mol L-1 at 110 degrees C. At this temperature, the dissociation rate constant (k(d)) is 3.7 x 10(-3) s(-1), the recombination rate constant (k(c)) is 4.3 x 10(6) L mol(-1) s(-1), whereas the activation energy (E-a,E-diss), for the dissociation of the alkoxyamine at the chain-end is similar to 125 kJ mol(-1). Importantly, the propagation rate at 110 degrees C, which does not change significantly with the prereaction time and the PBN/AIBN molar ratio at 85 degrees C, is higher than that for the thermal polymerization at 110 degrees C. This propagation rate directly depends on the equilibrium constant K and on the alkoxyamine and nitroxide concentrations, as well.
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 ; Commissariat Général aux Relations Internationales de la Communauté Wallonie-Bruxelles (CGRI) ; Centre National de la Recherche Scientifique (CNRS), France
Researchers
http://hdl.handle.net/2268/4302
10.1002/pola.21889
http://www3.interscience.wiley.com/cgi-bin/fulltext/114123153/PDFSTART
The authors acknowledge Journal of Polymer Science Part A-Polymer Chemistry (Wiley) for allowing them to archive this paper.

File(s) associated to this reference

Fulltext file(s):

FileCommentaryVersionSizeAccess
Restricted access
Sciannamea V 2007 JPS Polym Chem 1219.pdfNo commentaryPublisher postprint410.94 kBRequest copy

Bookmark and Share SFX Query

All documents in ORBi are protected by a user license.