One-pot synthesis for gradient copolymersviaconcurrent tandem living radical polymerization: mild and selective transesterification of methyl acrylate through Al(acac)₃with common alcohols

A series of gradient copolymers were synthesized by the ruthenium-catalyzed living radical polymerization (LRP) of methyl acrylate (MA) and aliphatic alcohols using aluminum acetylacetonate Al(acac)₃. In this polymerization system, Al(acac)₃was successfully used not only as an additive for the Ru-catalyzed LRP but also as a catalyst for the selective transesterification of an unsaturated ester monomer in mild conditions in a process known as concurrent tandem living radical polymerization. The resulting MA-based gradient copolymers showed well-controlled molecular weight and distribution in a one-pot reaction and exhibited a well-controlled gradient sequence in their polymer chain. Control of transesterification and the metal-catalyzed living radical polymerization (Mt-LRP) rate varied depending on the concentration of the Al(acac)₃and the structure of varying alcohols, which were confirmed by¹H NMR, SEC, and DSC analysis. In particular, this research opens a new synthetic methodology for preparing acrylate-based gradient copolymersviaconcurrent tandem LRP not limited to the synthesis of methyl methacrylate types of gradient copolymers.