Well‐defined poly(N,N‐dimethylacrylamide) from a fast Cu(0)‐mediated reversible‐deactivation radical polymerization in water

Copper‐catalyzed reversible deactivation radical polymerization (RDRP) of N , N ‐dimethylacrylamide (DMA) has been a significant challenge, particularly in aqueous environments, such as low yields, broad molecular weight distribution (MWD), and ill‐controlled molecular weights (MWs). In this work, we report the synthesis of well‐defined poly( N , N ‐dimethylacrylamide) (PDMA) via a facile Cu(0)‐mediated RDRP in water. The results show that, unlike other acrylamide monomers, for DMA with abundant tertiary amide groups, the sufficient deactivation—the key to realizing control in copper‐catalyzed RDRP—cannot be simply fulfilled by just increasing the amount of deactivator (i.e., Cu II species). The enhanced deactivation must be appropriately determined by also considering and selecting other reaction parameters. It is demonstrated that the use of methyl 2‐chloropropionate (MCP) as initiator and copper(II) chloride (CuCl 2 ) as the additional catalyst is an effective combination to simultaneously enhance the deactivation control and facilitate the chain growth in aqueous Cu(0)‐mediated RDRP of DMA. This strategy successfully achieved the fast and well‐controlled synthesis of PDMAs with high monomer conversion, narrow MWDs, and a range of predefined MWs, and the well‐controlled in situ chain extensions.