High-performance pan-tactic polythioesters with intrinsic crystallinity and chemical recyclability.

Three types of seemingly unyielding trade-offs have continued to challenge the rational design for circular polymers with both high chemical recyclability and high-performance properties: depolymerizability/performance, crystallinity/ductility, and stereo-disorder/crystallinity. Here, we introduce a monomer design strategy based on a bridged bicyclic thiolactone that produces stereo-disordered to perfectly stereo-ordered polythiolactones, all exhibiting high crystallinity and full chemical recyclability. These polythioesters defy aforementioned trade-offs by having an unusual set of desired properties, including intrinsic tacticity-independent crystallinity and chemical recyclability, tunable tacticities from stereo-disorder to perfect stereoregularity, as well as combined high-performance properties such as high thermal stability and crystallinity, and high mechanical strength, ductility, and toughness.