Impact of Catalyzed Radical Termination (CRT) and Reductive Radical Termination (RRT) in Metal‐Mediated Radical Polymerization Processes

Atom Transfer Radical Polymerization (ATRP), a metal‐catalyzed process, is a most powerful method for macromolecular engineering, producing polymers with targeted and low‐dispersity molar masses and with high chain‐end fidelity. This is due to the persistent radical effect, which dramatically reduce...

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Bibliographic Details
Published in:European journal of inorganic chemistry 2019-11, Vol.2019 (42), p.4489-4499
Main Authors: Thevenin, Lucas, Fliedel, Christophe, Matyjaszewski, Krzysztof, Poli, Rinaldo
Format: Article
Language:English
Subjects:
Addition polymerization
Catalysis
Chemical Sciences
Controlled radical polymerization
Copper
Inorganic chemistry
Polymerization
Radical termination
Termination (polymerization)
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Summary:Atom Transfer Radical Polymerization (ATRP), a metal‐catalyzed process, is a most powerful method for macromolecular engineering, producing polymers with targeted and low‐dispersity molar masses and with high chain‐end fidelity. This is due to the persistent radical effect, which dramatically reduces the spontaneous radical terminations, prolonging the lifetime of radical chains and the concurrent growth of all polymer chains. Two additional reaction modes that involve metals and organic radicals, however, may negatively affect the controlled polymerization. These are the Catalyzed Radical Termination (CRT) and the Reductive Radical Termination (RRT) and were shown to be particularly important for the polymerization of acrylate monomers. The scope and the mechanistic investigations carried out to elucidate how these processes interplay with ATRP and with each other are outlined in this Minireview. Transition metal complexes [L/Mtx] are efficient moderating agents in reversible‐deactivation radical polymerization processes (ATRP, OMRP) for the production of well‐defined polymeric materials of various kinds, but active radical species may also display other kinds of reactions, as in catalyzed radical termination (CRT) and reductive radical termination (RRT).
ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.201900901