SG1 Nitroxide Analogues: a Comparative Study

Jessica Marchand; Laurent Autissier; Yohann Guillaneuf; Jean-Luc Couturier; Didier Gigmes; Denis Bertin

doi:10.1071/CH10123

RESEARCH FRONT

SG1 Nitroxide Analogues: a Comparative Study

Jessica Marchand ^A , Laurent Autissier ^A , Yohann Guillaneuf ^A , Jean-Luc Couturier ^B , Didier Gigmes ^A and Denis Bertin ^A ^C

+ Author Affiliations

- Author Affiliations

^A UMR 6264 Laboratoire Chimie Provence. Université de Provence. Avenue Escadrille Normandie-Niemen, Case 542, Marseille 13397, Cedex 20, France.

^B ARKEMA, Centre de Recherche de Rhône Alpes, rue H. Moissan, 69493 Pierre Bénite Cedex, France.

^C Corresponding author. Email: denis.bertin@univ-provence.fr

Australian Journal of Chemistry 63(8) 1237-1244 https://doi.org/10.1071/CH10123
Submitted: 16 March 2010 Accepted: 10 June 2010 Published: 10 August 2010

Abstract

Due to a specific balance between steric, polar, and stabilization effects, SG1 nitroxide and its corresponding alkoxyamine BlocBuilder MA are now well recognized as two of the most potent compounds in nitroxide-mediated polymerization (NMP). In this work, alternatives to SG1, based on various aldehydes, were targeted using structure–reactivity relationships already developed by our group. Compared with SG1, we show that the substitution of the tert-butyl group on the carbon α to the aminoxyl function by a 2-ethylhexyl group led to a new nitroxide (ETHEXNO), which exhibited an half-life time at 120°C similar to SG1 and a slightly slower k_d for the alkoxyamine (2–3 times lower than the SG1). The styrene polymerization mediated by the ETHEXNO nitroxide has a similar behaviour to the one mediated by the SG1 in terms of livingness and control but the kinetics is affected (2–3 times lower). Concerning the n-butyl acrylate polymerization, an unexpected overheating occurred at 120°C, which led us to perform the polymerization in toluene at 100°C. The slow kinetics impedes the use of this nitroxide as a good alternative to SG1 and shows that the structure of the SG1 nitroxide is already delicately optimized and finding good alternatives is not straightforward.

Acknowledgements

The authors acknowledge ARKEMA, the University of Provence and the CNRS for financial support.

References

SG1 Nitroxide Analogues: a Comparative Study

Abstract

Acknowledgements

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