Abstract: In a recent article, we have showed that the nitroxide mediated polymerization of methyl methacrylate was possible up to 80% conversion for reasonable masses M-n = 60,000 g mol(-1) when 2,2-diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxyl nitroxide (DPAIO) was used as control agent. We have claimed that the success of this experiment relied on the absence of H-transfer reaction both in the alkoxyamine and between alkyl and nitroxyl radical. In this article, the decomposition of 4-nitrophenyl 2-(2,2,6,6-tetramethylpiperidine-1-yloxy)-2-methylpropionate (1a) and 4-nitrophenyl 2-(2,2-diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxy)-2-methylpropanoate (2a) has been studied by H-1 NMR in the presence and in the absence (persistent radical effect condition) of scavenger (thiophenol PhSH). At temperature lower than the one used for polymerization, fast and quantitative H-transfer reaction was observed for la whereas no H-transfer reaction was observed for 2a. The scavenging technique proved for the first time that the H-transfer was an intermolecular process for la. However, the slow side-reaction of N-OC bond homolysis, which did not impede the control of the polymerization but may exert a detrimental effect on the livingness, was observed and quantified for 2a. (c) 2008 Wiley Periodicals, Inc.

Cite: Edeleva M. , Marque S.R.A. , Bertin D. , Gigmes D. , Guillaneuf Y. , Morozov S.V. , Bagryanskaya E.G.
Hydrogen-Transfer Reaction in Nitroxide Mediated Polymerization of Methyl Methacrylate: 2.2-Diphenyl-3-phenylimino-2,3-dihydroindol-1-yloxyl Nitroxide (DPAIO) vs. TEMPO
Journal of Polymer Science, Part A: Polymer Chemistry. 2008. V.46. N20. P.6828-6842. DOI: 10.1002/pola.22991 WOS Scopus РИНЦ

Dates:

Published online:	Sep 15, 2008
Published print:	Oct 15, 2008

Identifiers:

Web of science	WOS:000260071300016
Scopus	2-s2.0-55349118819
Elibrary	13597294
OpenAlex	W2031877251

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