Comparison of Mechano- and PhotoATRP with ZnO Nanocrystals

Zinc oxide (ZnO) was previously reported as an excellent cocatalyst for mechanically controlled atom transfer radical polymerization (mechanoATRP), but its photocatalytic properties in photoinduced ATRP (photoATRP) have been much less explored. Herein, well-defined ZnO nanocrystals were prepared via microwave-assisted synthesis and applied as a heterogeneous cocatalyst in mechano- and photoATRP. Both techniques yielded polymers with outstanding control over the molecular weight, but ZnO-cocatalyzed photoATRP was much faster than analogous mechanoATRP (conversion of 91% in 1 h vs 54% in 5 h). The kinetics of photoATRP was tuned by loadings of ZnO nanocrystals. PhotoATRP with ZnO did not require any excess of ligand versus Cu, in contrast to mechanoATRP, requiring an excess of ligand, acting as a reducing agent. ZnO-cocatalyzed photoATRP proceeded controllably without prior deoxygenation, since ZnO was involved in a cascade of reactions, leading to the rapid elimination of oxygen. The versatility and robustness of the technique were demonstrated for various (meth)acrylate monomers with good temporal control and preservation of end-group functionality, illustrated by the formation of tailored block copolymers.