High-throughput generation of block copolymer libraries via click chemistry and automated chromatography

Designing block copolymers for specific applications is challenging because of the intricate relationship among molecular structure, self-assembly behavior, and bulk properties, which is compounded by a large design space that traditionally requires time-consuming, iterative synthesis. To overcome these challenges, here we report a library-based strategy leveraging an active ester-based block copolymer and automated chromatography which enables the high-throughput exploration of broad compositional and chemical landscapes without requiring sample-specific optimization. By integrating automated chromatography with robotic synthesis and orthogonal post-polymerization modification chemistry, we efficiently generated a diverse library of 90 well-defined block copolymers from a single as-synthesized “parent” copolymer. This adaptable method enables efficient access to materials with a wide range of compositions, molecular weights, functionalities, and properties. By integrating laboratory automation with click chemistry, these insights will accelerate the discovery and design of advanced block copolymers for high-performance applications.