Thermosets are an important class of materials that provide excellent temperature and solvent resistance; however, their high dimensional stability precludes degradation or reprocessing. While traditional thermoplastics can be mechanically and...

Conspectus Poor waste management and unchecked consumption underpin our current paradigm of plastics use, which is demonstrably unsustainable in the long term. Nonetheless, the utility and versatility of plastics suggest that the notion of a plastic-free society is also unsustainable. Responses to this conundrum are increasing, and among these are research efforts focused on the development of more sustainable plastics. This Account, written by trained chemists, reflects an academic research journey culminating in an appreciation of the importance of improving and enabling the overarching systems that plastics exist within. Our primary initial focus was on catalyst development because catalysts are key drivers of sustainability by improving the efficiency and ease of polymerization. Metal catalysts ranging in ligand structure and the incorporated metal(s) were developed for the preparation of traditional polyesters such as poly(lactic acid) and polycaprolactone. The central themes in these works were stereocontrol (tacticity), efficiency (polymerization rate), and versatility (monomer scope). Alongside insights gained by systematically varying catalyst structure came impressive results gained through collaboration, including the remarkably high activity of novel heterometallic zinc catalysts toward various cyclic esters. This catalysis work was complemented by and slowly transitioned to a focus on polymer functionality and monomer design. Several fundamental studies focus on polymer topology, specifically star-shaped polyesters, tuned arm number, length, and tacticity. These reports feature emphases on the end of life (solvolysis) and physical properties of polymers, which were increasingly important themes as work shifted toward new methods of incorporating functionality in polymers produced by ring-opening polymerization. Three key highlights demonstrate this shift: the first two rely upon the exploitation of olefin metathesis (cross- and ring-closing) to functionalize polyesters or polyethers, and the third involves the manipulation of ring-opening polymerization equilibrium to enable selective monomer recovery from a polyester. Our foundational work on 1,3-dioxolan-4-one (DOX) monomers is then discussed because this emerging class of molecules offers a distinct synthetic pathway toward functional polyesters, both conventional and novel. With this DOX framework, polyesters that are usually challenging to synthesize (e.g., poly(mandelic acid)) are accessible because polymerization is driven by the concomitant, controlled extrusion of small molecules (acetone or formaldehyde). After these polyester-focused highlights, the foundation of our ongoing work is presented, namely, that polymer sustainability must be viewed from a systems-level perspective, including economic and social components alongside the environmental considerations. Material design must be driven by practice, and we have to involve key players in academia, industry, and government in a concerted effort t...

Ring-opening polymerisation of cyclopentyl-decorated dioxaneone rings accesses fully alicyclic polyesters through elimination of formaldehyde.

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.