Degradable and Reprocessable Resins from a Dioxolanone Cross-Linker

Chemically cross-linked polymers offer excellent temperature and solvent resistance, but their high dimensional stability precludes reprocessing. The renewed demand for sustainable and circular polymers from public, industry, and government stakeholders has increased research into recycling thermoplastics, but thermosets have often been overlooked. To address this need for more sustainable thermosets, we have developed a novel bis(1,3-dioxolan-4-one) monomer, derived from the naturally occurring l-(+)-tartaric acid. This compound can be used as a cross-linker and copolymerized in situ with common cyclic esters such as l-lactide, ε-caprolactone, and δ-valerolactone to produce cross-linked, degradable polymers. The structure-property relationships and the final network properties were tuned by both co-monomer choice and composition, with properties ranging from resilient solids with tensile strengths of 46.7 MPa to elastomers with elongations up to 147%. In addition to exhibiting properties rivalling those of commercial thermosets, the synthesized resins could be recovered at end-of-life through triggered degradation or reprocessing. Accelerated hydrolysis experiments showed the materials fully degraded to tartaric acid and the corresponding oligomers from 1 to 14 days under mild basic conditions and in a matter of minutes in the presence of a transesterification catalyst. The vitrimeric reprocessing of networks was demonstrated at elevated temperatures, and rates could be tuned by modifying the concentration of the residual catalyst. This work develops new thermosets, and indeed their glass fiber composites, with an unprecedented ability to tune degradability and high performance by creating resins from sustainable monomers and a bio-derived cross-linker.