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| 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  [University of Liège (ULg) > Department of Chemistry > Center for Education and Research on Macromolecules (CERM) > >] | |
| Detrembleur, Christophe [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. |
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