Article (Scientific journals)
Investigation of methyl methacrylate and vinyl acetate polymerization promoted by Al(iBu)3/2,2'-bipyridine and Al(iBu)3/2,2'-bipyridine/TEMPO complexes
Granel, Claude; Jérôme, Robert; Teyssié, Philippe et al.
1998In Macromolecules, 31 (21), p. 7133-7141
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Keywords :
polymerization; (meth)acrylate; vinyl acetate
Abstract :
[en] Results of methyl methacrylate (MMA) and vinyl acetate (VOAc) polymerization using the Al(iBu)3/2,2‘-bipyridine/TEMPO initiating system at room temperature failed to confirm the “living” radical mechanism reported earlier. Several species apparently propagate without control in a normal free radical process and only above a critical initiator concentration. No evidence was found for the penta- and hexacoordinated aluminum species previously suggested, but high conversion to an alkoxyamine was observed. Additionally, mixing Al(iBu)3 and BIPY promotes a variety of reactions involving alkyl and hydride transfers to the aromatic rings forming reduced BIPY products, along with a persistent organoaluminum radical. All these results illustrate that the process is considerably more complicated than postulated before. Conversely, at −78 °C, a single active species excluding the participation of TEMPO has been put in evidence, displaying some “living” characteristics. Several experiments support its anionic nature, as previously suggested by Ikeda.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Chemistry
Materials science & engineering
Author, co-author :
Granel, Claude;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jérôme, Robert ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Teyssié, Philippe ;  Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Jasieczek, C. B.;  University of Warwick, UK > Department of Chemistry
Shooter, A. J.;  University of Warwick, UK > Department of Chemistry
Haddleton, D. M.;  University of Warwick, UK > Department of Chemistry
Hastings, J. J.;  University of Warwick, UK > Department of Chemistry
Gigmes, D.;  Centre de Saint Jérôme, Marseille, France > Laboratoire de Structure et Réactivité des Espèces Paramagnétiques
Grimaldi, S.;  Centre de Saint Jérôme, Marseille, France > Laboratoire de Structure et Réactivité des Espèces Paramagnétiques
Tordo, P.;  Centre de Saint Jérôme, Marseille, France > Laboratoire de Structure et Réactivité des Espèces Paramagnétiques
Greszta, D.;  Carnegie Mellon University, Pittsburgh, USA > Department of Chemistry
Matyjaszewski, K.;  Carnegie Mellon University, Pittsburgh, USA > Department of Chemistry
Language :
English
Title :
Investigation of methyl methacrylate and vinyl acetate polymerization promoted by Al(iBu)3/2,2'-bipyridine and Al(iBu)3/2,2'-bipyridine/TEMPO complexes
Publication date :
20 October 1998
Journal title :
Macromolecules
ISSN :
0024-9297
eISSN :
1520-5835
Publisher :
Amer Chemical Soc, Washington, United States - Washington
Volume :
31
Issue :
21
Pages :
7133-7141
Peer reviewed :
Peer Reviewed verified by ORBi
Funders :
BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique
Elf Atochem [FR]
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