<br/>Control over polymer features such as composition, architecture, molecular weight, and molecular weight distributions is critical for accessing well-defined materials with tailored properties. Despite significant advances in catalysis for ring-opening polymerization, the preparation of a large sets of well-defined, structurally precise materials for systematic structure–property and architecture–property remains a tedious, labor-intensive endeavor. To overcome these challenges, we have developed a new continuous flow platform for the rapid, programmatic synthesis of polyesters and polycarbonates. Using this platform, we can achieve highly controlled synthesis of a variety of homopolymers with residence times as short as 6 ms. By utilizing a suite of urea anion catalysts, monomers with disparate polymerization kinetics can be seamlessly copolymerized without deleterious transesterification side reactions. Control over the reactors via computer interface facilitates the rapid generation polymer libraries (up to 100 distinct block copolymers in 9 minutes) with excellent control over block lengths and dispersity. This platform also enables facile scale-up of polymer synthesis, with a demonstrated productivity of up to 16.5 g of material within a minute of runtime. Overall, this system represents a first step towards a truly programmatic, on demand and scalable synthesis of materials via ring-opening polymerization.

Programmable synthesis of polycarbonates and polyesters via continuous-flow ring-opening polymerization

2019 Fall National Meeting

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