Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr

Kulis, Jakov, Bell, Craig A., Micallef, Aaron S., & Monteiro, Michael J. (2010) Kinetic analysis of nitroxide radical coupling reactions mediated by CuBr. Journal of Polymer Science, Part A: Polymer Chemistry, 48(10), pp. 2214-2223.

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Abstract

In a previous paper, we described the room temperature rapid, selective, reversible, and near quantitative Cu-activated nitroxide radical coupling (NRC) technique to prepare 3-arm polystyrene stars. In this work, we evaluated the Cu-activation mechanism, either conventional atom transfer or single electron transfer (SET), through kinetic simulations. Simulation data showed that one can describe the system by either activation mechanism. We also found through simulations that bimolecular radical termination, regardless of activation mechanism, was extremely low and could be considered negligible in an NRC reaction. Experiments were carried out to form 2- and 3-arm PSTY stars using two ligands, PMDETA and Me6TREN, in a range of solvent conditions by varying the ratio of DMSO to toluene, and over a wide temperature range. The rate of 2- or 3-arm star formation was governed by the choice of solvent and ligand. The combination of Me6TREN and toluene/DMSO showed a relatively temperature independent rate, and remarkably reached near quantitative yields for 2-arm star formation after only 1 min at 25 °C.

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ID Code: 90677
Item Type: Journal Article
Refereed: Yes
Keywords: ‘‘click’’ chemistry, living radical polymerization, star polymers, single electron transfer (SET), nitroxide
DOI: 10.1002/pola.23991
ISSN: 0887-624X
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > MACROMOLECULAR AND MATERIALS CHEMISTRY (030300) > Nanochemistry and Supramolecular Chemistry (030302)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > MACROMOLECULAR AND MATERIALS CHEMISTRY (030300) > Synthesis of Materials (030306)
Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > MACROMOLECULAR AND MATERIALS CHEMISTRY (030300) > Theory and Design of Materials (030307)
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 02 Dec 2015 03:04
Last Modified: 10 Dec 2015 02:25

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