H-transfer reaction during decomposition of N-(2-methylpropyl)- N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1)-based alkoxyamines - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Journal of Polymer Science Part A: Polymer Chemistry Année : 2013

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

Résumé

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

Domaines

Chimie

Dates et versions

hal-01460448 , version 1 (07-02-2017)

Identifiants

Citer

Mariya Edeleva, Sylvain R.A. Marque, Kuanish Kabytaev, Yohann Guillaneuf, Didier Gigmes, et al.. 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, 51 (6), pp.1323--1336. ⟨10.1002/pola.26500⟩. ⟨hal-01460448⟩
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