Kinetic Study of H-Atom Transfer in Imidazoline-, Imidazolidine-, and Pyrrolidine-Based Alkoxyamines: Consequences for Nitroxide-Mediated Polymerization

Kinetic Study of H-Atom Transfer in Imidazoline-, Imidazolidine-, and Pyrrolidine-Based Alkoxyamines: Consequences for Nitroxide-Mediated Polymerization Full article

Journal

Journal of Polymer Science, Part A: Polymer Chemistry
ISSN: 0887-624X , E-ISSN: 1099-0518

Output data

Year: 2009, Volume: 47, Number: 23, Pages: 6579-6595 Pages count : DOI: 10.1002/pola.23701

Tags

activation energy; alkoxyamine; diffusion; ESR/EPR; gel permeation chromatography (GPC); H-atom transfer reaction; initiators; kinetics (polym.); living radical polymerization (LRP); nitroxide; NMR

Authors

Edeleva Mariya V. ^1,2 , Kirilyuk Igor A. ³ , Zubenko Dmitry P. ¹ , Zhurko Irina F. ³ , Marque Sylvain R. A. ⁴ , Gigmes Didier ⁴ , Guillaneuf Yohann ⁴ , Bagryanskaya Elena G. ¹

Affiliations

1	(Данные Web of science) SB RAS, Int Tomog Ctr, Novosibirsk 630090, Russia
2	(Данные Web of science) Novosibirsk State Univ, Novosibirsk 630090, Russia
3	(Данные Web of science) SB RAS, Novosbiirsk Inst Organ Chem, Novosibirsk 630090, Russia
4	(Данные Web of science) Univ Aix Marseille 1, Unite Mixte Rech 6264, Lab Chim Provence, F-13397 Marseille 20, France

The H-atom transfer reaction was studied for a series of imidazoline, imidazolidine, and pyrrolidine-based alkoxyamines containing either isobutyrate-2-yl or 1-phenylethyl alkyl fragments. The C-O bond homolysis rate constants and activation energies were determined by H-1 NMR product analysis as a function of temperature. Inter- and intramolecular H-atom transfer reactions were distinguished by examination of alkoxyamine thermolysis products in the absence and in the presence of a radical scavenger (thiophenol or deuterated styrene). A correlation between the structure of the nitroxyl fragment of alkoxyamine and the H-transfer reaction was found. The high steric demands of the substituents on the nitroxyl part of the isobutyrate-2-yl alkoxyamine decrease both types of reaction. For alkoxyamines containing the 1-phenylethoxyamines, neither inter- nor intramolecular H-atom transfer was observed. Controlled polymerization of methylmethacrylate initiated with imidazoline-based alkoxyamine was observed, although the polymer obtained was not living. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6579-6595, 2009

Edeleva M.V. , Kirilyuk I.A. , Zubenko D.P. , Zhurko I.F. , Marque S.R.A. , Gigmes D. , Guillaneuf Y. , Bagryanskaya E.G.
Kinetic Study of H-Atom Transfer in Imidazoline-, Imidazolidine-, and Pyrrolidine-Based Alkoxyamines: Consequences for Nitroxide-Mediated Polymerization
Journal of Polymer Science, Part A: Polymer Chemistry. 2009. V.47. N23. P.6579-6595. DOI: 10.1002/pola.23701 WOS Scopus

Published online:	Oct 27, 2009
Published print:	Dec 1, 2009

Web of science	WOS:000272455900023
Scopus	2-s2.0-72449124703
OpenAlex	W2158038839