β‐Hydrogen transfer from poly(methyl methacrylate) propagating radicals to the nitroxide SG1: Analysis of the chain‐end and determination of the rate constant

Charlotte Dire; Joël Belleney; Julien Nicolas; Denis Bertin; Stéphanie Magnet; Bernadette Charleux

doi:10.1002/pola.22945

journal article Aug 13, 2008

β‐Hydrogen transfer from poly(methyl methacrylate) propagating radicals to the nitroxide SG1: Analysis of the chain‐end and determination of the rate constant

Charlotte Dire Joël Belleney Julien Nicolas

Denis Bertin Stéphanie Magnet Bernadette Charleux

Journal of Polymer Science Part A: Polymer Chemistry Vol. 46 No. 18 pp. 6333-6345 · Wiley

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Abstract

AbstractMethyl methacrylate (MMA) was polymerized in bulk at 70 °C in the presence of an alkoxyamine initiator with low dissociation temperature (the so‐called BlocBuilder™) and increasing amounts of free N‐tert‐butyl‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl) nitroxide (SG1). Low final monomer conversions were reached, indicating a loss in radical activity due to side reactions such as irreversible homoterminations between the propagating radicals and β‐hydrogen transfer (also called disproportionation) from a propagating radical to a free‐SG1 nitroxide. Proton NMR and MALDI‐TOF mass spectrometry were used to analyze the polymer chain‐ends and to clearly identify the main mechanism of irreversible termination. In particular, it was shown that all polymer chains were terminated by an alkene function in the presence of a large excess of free SG1, meaning that β‐hydrogen transfer from PMMA propagating radicals to the nitroxide SG1 was the major chain‐stopping event. On the other hand, for a low excess of free SG1, the two termination modes coexisted. Kinetic modeling was then performed using the PREDICI software, and the rate constant of β‐hydrogen transfer, kβHtr, was estimated to be 1.69 × 103 L mol−1 s−1 at 70 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6333–6345, 2008

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Details

Published: Aug 13, 2008
Vol/Issue: 46(18)
Pages: 6333-6345
License: View

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Cite This Article

Charlotte Dire, Joël Belleney, Julien Nicolas, et al. (2008). β‐Hydrogen transfer from poly(methyl methacrylate) propagating radicals to the nitroxide SG1: Analysis of the chain‐end and determination of the rate constant. Journal of Polymer Science Part A: Polymer Chemistry, 46(18), 6333-6345. https://doi.org/10.1002/pola.22945

β‐Hydrogen transfer from poly(methyl methacrylate) propagating radicals to the nitroxide SG1: Analysis of the chain‐end and determination of the rate constant

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