Intensifying the ATRP synthesis of statistical copolymers by continuous micromixing flow techniques1

The impact of micromixers on copolymers ’ characteristics in a continuous-flow microprocess was studied. A stainless steel coiled tube was used as the microreactor. Several micromixers with different working principles, like bilamination, multilamination and impact jet, were used to mix the reactants ’ streams before entering the reactor. (Co)polymers of 2-dimethyl amino ethyl methacrylate (DMAEMA) and benzyl methacrylate (BzMA) were synthesized by the atom transfer radical polymerization (ATRP) technique, with two different compositions of BzMA (20% and 40%). A faster polymerization rate was observed in case of microprocess, as compared to batch process, highlighting the inherent intensification nature of microfluidic-assisted processes. Despite equal conversion for the three micromixers, a remarkable difference in molecular weight was observed. The highest molecular weights with lowest polydispersity indices (PDIs) were obtained when the multilamination micromixer was used, while the bilamination gave polymers with high PDIs and low molecular weights. Diffusion constraints arising from the increase in viscosity was clearly visible for highest residence times in the microreactor, resulting in a deviation of molecular weight from the theoretical value