In situ nitroxide-mediated polymerization of styrene promoted by the N-tert-butyl-α-isopropylnitrone/bpo pair: ESR investigations

C. Detrembleur, J.-L. Clément, V. Sciannaméa, C. Jérôme, J.-M. Catala, D. Gigmes, L. Autissier, E. Botek, N. Zarycz, B. Champagne

Research output: Contribution to journalArticle

Abstract

The styrene polymerization initiated by benzoyl peroxide (BPO) in the presence of N-tert-butyl-α-isopropylnitrone as nitroxide precursor is well-controlled provided that a prereaction between the nitrone and BPO is carried out in suitable conditions prior to polymerization at a higher temperature. Electron spin resonance (ESR) spectroscopy was implemented to probe the nitroxides formed during both steps, that is, the prereaction and polymerization, and to get crucial information regarding the structure of the nitroxides responsible for the polymerization control. ESR studies combined with first principles calculations have evidenced that nitroxides observed during the prereaction in the presence of styrene and during the polymerization steps consist of a mixture of two macronitroxides. One is formed by the addition of a growing polystyrene chain to the nitrone as would be expected. However, the second one results from the addition of a polystyrene chain to tert-butyl nitroso that is in situ formed presumably by decomposition of the first macronitroxide type.
Original languageEnglish
Pages (from-to)1786-1795
Number of pages10
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume51
Issue number8
DOIs
Publication statusPublished - 15 Apr 2013

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Styrene
Paramagnetic resonance
Polymerization
Benzoyl Peroxide
Benzoyl peroxide
Polystyrenes
Electron spin resonance spectroscopy
Decomposition
Temperature

Cite this

Detrembleur, C. ; Clément, J.-L. ; Sciannaméa, V. ; Jérôme, C. ; Catala, J.-M. ; Gigmes, D. ; Autissier, L. ; Botek, E. ; Zarycz, N. ; Champagne, B. / In situ nitroxide-mediated polymerization of styrene promoted by the N-tert-butyl-α-isopropylnitrone/bpo pair : ESR investigations. In: Journal of Polymer Science, Part A: Polymer Chemistry. 2013 ; Vol. 51, No. 8. pp. 1786-1795.
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In situ nitroxide-mediated polymerization of styrene promoted by the N-tert-butyl-α-isopropylnitrone/bpo pair : ESR investigations. / Detrembleur, C.; Clément, J.-L.; Sciannaméa, V.; Jérôme, C.; Catala, J.-M.; Gigmes, D.; Autissier, L.; Botek, E.; Zarycz, N.; Champagne, B.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 51, No. 8, 15.04.2013, p. 1786-1795.

Research output: Contribution to journalArticle

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T1 - In situ nitroxide-mediated polymerization of styrene promoted by the N-tert-butyl-α-isopropylnitrone/bpo pair

T2 - ESR investigations

AU - Detrembleur, C.

AU - Clément, J.-L.

AU - Sciannaméa, V.

AU - Jérôme, C.

AU - Catala, J.-M.

AU - Gigmes, D.

AU - Autissier, L.

AU - Botek, E.

AU - Zarycz, N.

AU - Champagne, B.

PY - 2013/4/15

Y1 - 2013/4/15

N2 - The styrene polymerization initiated by benzoyl peroxide (BPO) in the presence of N-tert-butyl-α-isopropylnitrone as nitroxide precursor is well-controlled provided that a prereaction between the nitrone and BPO is carried out in suitable conditions prior to polymerization at a higher temperature. Electron spin resonance (ESR) spectroscopy was implemented to probe the nitroxides formed during both steps, that is, the prereaction and polymerization, and to get crucial information regarding the structure of the nitroxides responsible for the polymerization control. ESR studies combined with first principles calculations have evidenced that nitroxides observed during the prereaction in the presence of styrene and during the polymerization steps consist of a mixture of two macronitroxides. One is formed by the addition of a growing polystyrene chain to the nitrone as would be expected. However, the second one results from the addition of a polystyrene chain to tert-butyl nitroso that is in situ formed presumably by decomposition of the first macronitroxide type.

AB - The styrene polymerization initiated by benzoyl peroxide (BPO) in the presence of N-tert-butyl-α-isopropylnitrone as nitroxide precursor is well-controlled provided that a prereaction between the nitrone and BPO is carried out in suitable conditions prior to polymerization at a higher temperature. Electron spin resonance (ESR) spectroscopy was implemented to probe the nitroxides formed during both steps, that is, the prereaction and polymerization, and to get crucial information regarding the structure of the nitroxides responsible for the polymerization control. ESR studies combined with first principles calculations have evidenced that nitroxides observed during the prereaction in the presence of styrene and during the polymerization steps consist of a mixture of two macronitroxides. One is formed by the addition of a growing polystyrene chain to the nitrone as would be expected. However, the second one results from the addition of a polystyrene chain to tert-butyl nitroso that is in situ formed presumably by decomposition of the first macronitroxide type.

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