Issue 20, 2022

Dual electrochemical and chemical control in atom transfer radical polymerization with copper electrodes

Abstract

In Atom Transfer Radical Polymerization (ATRP), Cu0 acts as a supplemental activator and reducing agent (SARA ATRP) by activating alkyl halides and (re)generating the CuI activator through a comproportionation reaction, respectively. Cu0 is also an unexplored, exciting metal that can act as a cathode in electrochemically mediated ATRP (eATRP). Contrary to conventional inert electrodes, a Cu cathode can trigger a dual catalyst regeneration, simultaneously driven by electrochemistry and comproportionation, if a free ligand is present in solution. The dual regeneration explored herein allowed for introducing the concept of pulsed galvanostatic electrolysis (PGE) in eATRP. During a PGE, the process alternates between a period of constant current electrolysis and a period with no applied current in which polymerization continues via SARA ATRP. The introduction of no electrolysis periods without compromising the overall polymerization rate and control is very attractive, if large current densities are needed. Moreover, it permits a drastic charge saving, which is of unique value for a future scale-up, as electrochemistry coupled to SARA ATRP saves energy, and shortens the equipment usage.

Graphical abstract: Dual electrochemical and chemical control in atom transfer radical polymerization with copper electrodes

Supplementary files

Article information

Article type
Edge Article
Submitted
06 apr 2022
Accepted
26 apr 2022
First published
05 may 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 6008-6018

Dual electrochemical and chemical control in atom transfer radical polymerization with copper electrodes

F. De Bon, F. Lorandi, J. F. J. Coelho, A. C. Serra, K. Matyjaszewski and A. A. Isse, Chem. Sci., 2022, 13, 6008 DOI: 10.1039/D2SC01982E

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