Flow controlled synthesis of bottlebrush macromolecules

Shape, size and composition are nature's most fundamental design features, enabling highly complex functionalities. Despite recent advances, the independent control of shape, size and chemistry of macromolecules remains a synthetic challenge. Herein reported is a scalable methodology to produce large well-defined macromolecules with programmable shape, size and chemistry that combines reactor engineering principles and controlled polymerizations. Specifically, bottlebrush polymers with conical, ellipsoidal and concave architectures are synthesized using two orthogonal polymerizations. The chemical versatility is highlighted by the synthesis of a compositional asymmetric cone. The strong agreement between predictions and experiments validate the precision that this methodology offers.