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Journal Articles Polymer Chemistry Year : 2016

Trityl-based alkoxyamines as NMP controllers and spin-labels

Abstract

Recently, new applications of trityl-nitroxide biradicals were proposed. In the present study, attachment of a trityl radical to alkoxyamines was performed for the first time. The rate constants k(d) of C-ON bond homolysis in these alkoxyamines were measured and found to be similar to those for alkoxyamines without a trityl moiety. The electron paramagnetic resonance (EPR) spectra of the products of alkoxyamine homolysis (trityl-TEMPO and trityl-SG1 biradicals) were recorded, and the corresponding exchange interactions were estimated. The decomposition of trityl-alkoxyamines showed more than an 80% yield of biradicals, meaning that the C-ON bond homolysis is the main reaction. The suitability of these labelled initiators/controllers for polymerisation was exemplified by means of a successful nitroxide-mediated polymerisation (NMP) of styrene. Thus, this is the first report of a spin-labelled alkoxyamine suitable for NMP.
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Dates and versions

hal-01408195 , version 1 (28-03-2017)

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Attribution - NonCommercial

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Gérard Audran, Elena Bagryanskaya,, Paul Brémond, Mariya Edeleva, Marque S.R.A., et al.. Trityl-based alkoxyamines as NMP controllers and spin-labels. Polymer Chemistry, 2016, 7 (42), pp.6490-6499. ⟨10.1039/c6py01303a⟩. ⟨hal-01408195⟩
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