H-transfer reaction during decomposition of N-(2-methylpropyl)- N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines

H-transfer reaction during decomposition of N-(2-methylpropyl)- N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines Full article

Journal

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

Output data

Year: 2013, Volume: 51, Number: 6, Pages: 1323-1336 Pages count : 14 DOI: 10.1002/pola.26500

Tags

initiators; kinetics (polym; ); living polymerization; radical polymerization; reactive processing

Authors

Edeleva Mariya ¹ , Marque Sylvain R.A. ² , Kabytaev Kuanish ² , Guillaneuf Yohann ² , Gigmes Didier ² , Bagryanskaya Elena ^1,3

Affiliations

1	(Данные Web of science) Int Tomog Ctr SB RAS, Novosibirsk 630090, Russia
2	(Данные Web of science) Aix Marseille Univ, CNRS, UMR 7273, ICR, F-13397 Marseille 20, France
3	(Данные Web of science) NN Vorozhtsov Novosibirsk Inst Organ Chem SB RAS, Novosibirsk 630090, Russia

Thermal decomposition of four tertiary N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines (SG1-C(Me)2-C(O)-OR, R = Me, tBu, Et, H) has been studied at different experimental conditions using 1H and 31P NMR spectroscopies. This experiment represents the initiating step of methyl methacrylate polymerization. It has been shown that H-transfer reaction occurs during the decomposition of three alkoxyamines in highly degassed solution, whereas no products of H-transfer are detected during decomposition of SG1-MAMA alkoxyamine. The value of the rate constant of H-transfer for alkoxyamines 1 (SG1-C(Me)2-C(O)-OMe) and 2 (SG1-C(Me)2-C(O)-OtBu) has been estimated as 1.7 x 103 M1s1. The high influence of oxygen on decomposition mechanism is found. In particular, in poorly degassed solutions, nearly quantitative formation of oxidation product has been observed, whereas at residual pressure of 105 mbar, the main products originate from H-atom transfer reaction. The acidity of the reaction medium affects the decomposition mechanism suppressing the H-atom transfer. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Edeleva M. , Marque S.R.A. , Kabytaev K. , Guillaneuf Y. , Gigmes D. , Bagryanskaya E.
H-transfer reaction during decomposition of N-(2-methylpropyl)- N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines
Journal of Polymer Science, Part A: Polymer Chemistry. 2013. V.51. N6. P.1323-1336. DOI: 10.1002/pola.26500 WOS Scopus РИНЦ

Published online:	Dec 22, 2012
Published print:	Mar 15, 2013

Web of science	WOS:000314975700008
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