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university of Provence - Aix-Marseille I |  |
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university of Provence - Aix-Marseille I | |
| HAL: hal-00179162, version 1 |
| DOI: 10.1002/hlca.200690201 |
| Detailed view |  Export this paper |
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| Helvetica Chimica Acta 89, 10 (2006) 2119-2132 |
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| Intramolecular Hydrogen Bonding: The Case of beta-Phosphorylated Nitroxide (= Aminoxyl) Radical |
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| Sébastien Acerbis 1Denis Bertin 1 |
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| (2006-10-25) |
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| Alkoxyamines and persistent nitroxide (= aminoxyl) radicals are important regulators of nitroxide-mediated radical polymerization. Since polymerization times decrease with the increasing homolysis rate constant of the CON bond homolysis between the polymer chain and the aminooxy moiety, the factors influencing the cleavage rate constant are of considerable interest. It has already been shown that the value of the homolysis rate constant kd is very sensitive to the stabilization of both released radical species. X-Ray, EPR, and kinetic data showed that the intramolecular H-bonding radical in the 1-(diethoxyphosphoryl)-2,2-dimethylpropyl 2-hydroxy-1,1-dimethylethyl nitroxide (3a) (homologue of 2-hydroxy-1,1-dimethylethyl 1-phenyl-2-methylpropyl nitroxide (2a)) did not occur with the nitroxide moiety as expected but with the phosphoryl group. However, the polymerization rate of styrene (= ethenylbenzene) was significantly enhanced. |
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| 1: | Chimie, biologie et radicaux libres (CBRL) |
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CNRS : UMR6517 – Université de Provence - Aix-Marseille I – Université Paul Cézanne - Aix-Marseille III – Université de la Méditerranée - Aix-Marseille II |
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| 2: | Institut Charles Gerhardt - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICG ICMMM) |
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CNRS : UMR5253 – Université Montpellier I – Université Montpellier II - Sciences et techniques – Ecole Nationale Supérieure de Chimie de Montpellier |
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| Subject | : | Chemical Sciences/Polymers |
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| Hydrogen bonds – Polymerization – Nitroxides – EPR Spectroscopy – X-Ray spectroscopy |
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| hal-00179162, version 1 | |
| http://hal.archives-ouvertes.fr/hal-00179162 | |
| oai:hal.archives-ouvertes.fr:hal-00179162 | |
| From: Patrick Lacroix-Desmazes | |
| Submitted on: Saturday, 13 October 2007 18:10:11 | |
| Updated on: Friday, 9 November 2007 21:36:19 | |
