Reference : Synthesis and evaluation of sterically hindered 1,1-diamantyl nitroxide as a low-temp...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
http://hdl.handle.net/2268/18563
Synthesis and evaluation of sterically hindered 1,1-diamantyl nitroxide as a low-temperature mediator for the stable free radical polymerization process
English
Debuigne, Antoine mailto [University of Toronto at Mississauga, Canada > > Department of Chemical and Physical Sciences > >]
Chan-Seng, Delphine [University of Toronto at Mississauga, Canada > > Department of Chemical and Physical Sciences > >]
Li, Lichun [University of Toronto at Mississauga, Canada > > Department of Chemical and Physical Sciences > >]
Hamer, Gordon K. [University of Toronto at Mississauga, Canada > > Department of Chemical and Physical Sciences > >]
Georges, Michael K. [University of Toronto at Mississauga, Canada > > Department of Chemical and Physical Sciences > >]
21-Aug-2007
Macromolecules
American Chemical Society
40
17
6224-6232
Yes (verified by ORBi)
International
0024-9297
Washington
DC
[en] radical polymerization
[en] An efficient procedure for the oxidation of 1,1-diadamantylamine with m-chloroperbenzoic acid (m-CPBA) to the corresponding sterically hindered nitroxide in high yield (72%) is reported. The corresponding styrene-based alkoxyamine was synthesized by an atom transfer radical addition (ATRA) reaction. Because of the bulkiness of the adamantyl substituents, the cleavage of the C−ON bond of the alkoxyamine occurred readily at temperatures below 100 °C. However, in spite of the low bond dissociation temperature of the alkoxyamine, the (co)polymerizations of styrene and n-butyl acrylate proceeded poorly. The results in this paper support the argument that the most important determinant in a nitroxide-mediated polymerization of styrene and acrylate is the ability to control the excess concentration of nitroxide in solution either by an inherent instability of the nitroxide or by the use of additives that destroy the excess nitroxide. Thus, for the 1,1-diadamantyl nitroxide case, and maybe more generally, while a lower C−O bond dissociation energy of an alkoxyamine moiety at the end of the chain may allow lower polymerization temperatures and faster reactions rates, it does not enable polymerizations to proceed to high conversions if the excess nitroxide is not controlled in some manner.
Fonds de la Recherche Scientifique (Communauté française de Belgique) - F.R.S.-FNRS ; the Natural Sciences and Engineering Research Council of Canada (NSERC)
Researchers
http://hdl.handle.net/2268/18563
10.1021/ma070691k
http://pubs.acs.org/doi/pdf/10.1021/ma070691k
http://pubs.acs.org/doi/suppl/10.1021/ma070691k

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