O-to-S Substitution Enables Dovetailing Conflicting Cyclizability, Polymerizability, and Recyclability: Dithiolactone vs. Dilactone

Developing chemically recyclable polymers represents a greener alternative to landfill and incineration and offers a closed-loop strategy toward a circular materials economy. However, the synthesis of chemically recyclable polymers is still plagued with certain fundamental limitations, including trade-offs between the monomer's cyclizability and polymerizability, as well as between polymer's depolymerizability and properties. Here we describe the subtle O-to-S substitution, dithiolactone monomers derived from abundant feedstock alpha-amino acids can demonstrate appealing chemical properties different from those of dilactone, including accelerated ring closure, augmented kinetics polymerizability, high depolymerizability and selectivity, and thus constitute a unique class of polythioester materials exhibiting controlled molecular weight (up to 100.5 kDa), atactic yet high crystallinity, structurally diversity, and chemical recyclability. These polythioesters well addresses the formidable challenges of developing chemically recyclable polymers by having an unusual set of desired properties, including easy-to-make monomer from ubiquitous feedstock, and high polymerizability, crystallinity and precise tunability of physicochemical performance, as well as high depolymerizability and selectivity. Computational studies explain why O-to-S modification of polymer backbone enables dovetailing desirable, but conflicting, performance into one polymer structure.

Automated summary

The development of chemically recyclable polymers is essential for a more sustainable approach towards materials economy. This study introduces a unique class of polythioester materials derived from dithiolactone monomers, exhibiting desirable properties such as controlled molecular weight, high crystallinity, and chemical recyclability. The O-to-S substitution in the polymer backbone allows for a combination of conflicting yet beneficial performance characteristics, overcoming fundamental limitations in polymer synthesis.