Electrochemistry for Atom Transfer Radical Polymerization

Atom Transfer Radical Polymerization (ATRP) is the most powerful and most employed technology of Controlled Radical Polymerization (CRP) to produce polymers with well‐defined architecture, that is, composition, topology, and functionality. Several hundreds of papers are published every year on ATRP processes, mainly based on empiric experimental procedures. Electrochemistry powerfully entered in the field of ATRP about 10 years ago, providing important contributions both to the further development of the process and to a better understanding of its mechanism. Five main issues took advantage of electrochemistry and/or its synergism with ATRP: i) understanding the mechanism of ATRP activation; ii) determination of thermodynamic parameters; iii) determination of activation and deactivation rate constants; iv) the SARA ATRP vs SET‐LRP dispute: the role of Cu0; v) electrochemically‐mediated ATRP. In the last decade, the synergism between Organic Molecular Electrochemistry and Atom Transfer Radical Polymerization has developed both science and technology into and around both fields.