Polymerizations in Continuous Flow: Recent Advances in the Synthesis of Diverse Polymeric Materials.

The number of reports using continuous flow technology in tubular reactors to perform precision polymerizations has grown enormously in recent years. Flow polymerizations allow highly efficient preparation of polymers exhibiting well-defined molecular characteristics, and has been applied to a slew of monomers and various polymerization mechanisms, including anionic, cationic, radical, and ring-opening. Polymerization conducted in continuous flow offers several distinct advantages, including improved efficiency, reproducibility, and enhanced safety for exothermic polymerizations using highly toxic components, high pressures, and high temperatures. The further development of this technology is thus of relevance for many industrial polymerization processes. While much progress has been demonstrated in recent years, opportunities remain for increasing the compositional and architectural complexity of polymeric materials synthesized in a continuous fashion. Extending the reactor processing principles that have heretofore been focused on optimizing homopolymerization to include multisegment block copolymers, particularly from monomers that propagate via incompatible mechanisms, represents a major challenge and coveted target for continuous flow polymerization. Likewise, the spatial and temporal control of reactivity afforded by flow chemistry has and will continue to enable the production of complex polymeric architectures. This Viewpoint offers a brief background of continuous flow polymerization focused primarily on tubular (micro)reactors and includes selected examples that are relevant to these specific developments.