High-Throughput Generation of Block Copolymer Libraries via Click Chemistry and Automated Chromatography
Elizabeth A. Murphy, Katherine G. Roth, Morgan W. Bates, Megan C. Murphy, Jerrick Edmund, Christopher M. Bates, Craig J. Hawker
Macromolecules July 2025
Abstract: 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 postpolymerization 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.
