Copper mediated controlled radical polymerization of methyl acrylate in the presence of ascorbic acid in a continuous tubular reactor

Controlled radical polymerization of methyl acrylate catalyzed by copper was conducted in a continuous tubular reactor. A length of copper tubing was used to initiate polymerization and generate soluble copper species, while the bulk of polymerization took place in inert stainless steel tubing. To mediate polymerization in the absence of copper surface, environmentally benign ascorbic acid was used for the first time in single electron transfer-living radical polymerization (SET-LRP) as a reducing agent to regenerate activating copper species. Polymerizations were conducted at ambient temperature with 30 wt% DMSO as solvent, producing well defined living polymer at a steady state conversion of 78% for a residence time of 62 min. Chain extensions using outlet polymer solutions were well-controlled and proceeded to high conversion in a short period of time, with a final concentration of 10 ppm of residual copper. The results illustrate the significant potential of using a continuous tubular reactor with ascorbic acid as a reducing agent as an efficient means to scale-up production of well controlled polyacrylics and other multiblock copolymers.