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Cu-Catalyzed Atom Transfer Radical Polymerization: The Effect of Cocatalysts

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/macp.202200347

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atom transfer radical polymerization; catalysts; cocatalysts; copper; reversible deactivation radical polymerization

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Cu-catalyzed atom transfer radical polymerization is a powerful method for preparing well-defined (co)polymers. This minireview summarizes the development of cocatalysts for regenerating Cu-I complex activators during polymerizations. Recent developments of photochemical cocatalysts and methods to study their properties and roles are also discussed.
Atom transfer radical polymerization (ATRP) is one of the most powerful methods to prepare well-defined (co)polymers. Cu-catalyzed ATRP methods are most commonly used because of the excellent control and tunable catalytic activities via ligand functionalization. This minireview summarizes the development of Cu-catalyzed ATRP in the presence of cocatalysts, which are used to regenerate Cu-I complex activators during polymerizations. Fundamentals of Cu-based ATRP catalysts are first introduced, followed by the discussion of different types of cocatalysts in different Cu-catalyzed ATRP methods. Recent developments of photochemical cocatalysts for oxygen-tolerant ATRP and ATRP using long-wavelength irradiation are highlighted, which significantly expand the applications of Cu-catalyzed ATRP. Methods to study the properties of cocatalysts and their roles in Cu-catalyzed ATRP are discussed, with an outlook for the future development of cocatalysts.

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