Catalytic Halogen Exchange in Miniemulsion ARGET ATRP: A Pathway to Well-Controlled Block Copolymers

Halogen exchange in atom transfer radical polymerization (ATRP) is an efficient way to chain-extend from a less active macroinitiator (MI) to a more active monomer. This has been previously achieved by using CuCl/L in the equimolar amount to P_n -Br MI in the chain extension step. However, this approach cannot be effectively applied in systems based on regeneration of activators (ARGET ATRP), since they operate with ppm amounts of catalysts. Herein, a catalytic halogen exchange procedure is reported using a catalytic amount of Cu in miniemulsion ARGET ATRP to chain-extend from a less active poly(n-butyl acrylate) (PBA) MI to a more active methyl methacrylate (MMA) monomer. Influence of different reagents on the initiation efficiency and dispersity is studied. Addition of 0.1 m NaCl or tetraethylammonium chloride to ATRP of MMA initiated by methyl 2-bromopropionate leads to high initiation efficiency and polymers with low dispersity. The optimized conditions are then employed in chain extension of PBA MI with MMA to prepare diblock and triblock copolymers.