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

Abstract

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.

Relationship between morphology and surface properties in polystyrene-block-poly(N-isopropylacrylamide) diblock copolymer films

“…Various ATRP systems, including normal ATRP, reverse ATRP, simultaneous reverse and normal initiation (SR & NI) ATRP, and activator regenerated by electron transfer (ARGET) ATRP, were used in the ATRP method [40,41]. In this work, the normal ATRP and ARGET ATRP methods were used for the synthesis of the macroinitiator PS-Br.…”

Fully Oxygen-Tolerant Visible-Light-Induced ATRP of Acrylates in Water: Toward Synthesis of Protein-Polymer Hybrids

“…Then, the generated activator Cu I /L reacts with a C­(sp 3 )–X polymer chain end to form a carbon radical and the X–Cu II /L deactivator. Oxygen tolerance in this approach can be achieved using an excess ligand. − However, photoinduced Cu-catalyzed ATRP typically requires the use of biocidal UV light. ,, In organocatalyzed ATRP (O-ATRP), the dormant polymer chain is directly activated by electron transfer from a photoredox catalyst (PC) in the excited state (Figure b). − O-ATRP is compatible with a wide range of visible light but is mainly limited to methacrylates and organic solvents. − ATRP with dual catalysis uses copper complexes to attain a controlled radical propagation and PCs to trigger and drive polymerization (Figure c). ,− The photoredox/copper dual catalysis overcomes the challenges of using biocidal UV light, poor oxygen tolerance, and limited monomer scope.…”

From non-conventional ideas to multifunctional solvents inspired by green chemistry: fancy or sustainable macromolecular chemistry?

“…When considering the introduction of green chemistry principles into ATRP processes, it should be mentioned that there are also limitations with these processes due to the necessary use of catalysts, 107 cocatalysts 108 or monomers, 109 sometimes classified as toxic substances. While the review answers questions related to selecting the right green solvent for the RDRP procedure, it is important to note that not only highly-toxic solvents, e.g.…”