The global plastic waste problem has created an urgent need for the development of more sustainable materials and recycling processes. Polyurethane (PU) plastics, which represent 5.5% of globally produced plastics, are particularly challenging to recycle owing to their crosslinked structure. Covalent adaptable networks (CANs) based on dynamic covalent bonds have emerged as a promising solution for recycling PU waste. CANs enable the production of thermoset polymers that can be recycled using methods that are traditionally reserved for thermoplastic polymers. Reprocessing using hot-pressing techniques, in particular, proved to be more suited for the class of polyurethanes, allowing for the efficient recycling of PU materials. This Review paper explores the potential of CANs for improving the sustainability of PU recycling processes by examining different types of PU-CANs, bond types, and fillers that can be used to optimise the recycling efficiency. The paper concludes that further research is needed to develop more cost-effective and industrial-friendly techniques for recycling PU-CANs, as they can significantly contribute to sustainable development by creating recyclable thermoset polymers.

This study aims to deepen knowledge of the biodegradation of plastics, focusing on polypropylene (PP) fabric from surgical masks and polystyrene (PS) by larvae of Zophobas atratus as well as of specialized bacterial consortia from their gut, which were obtained in different enrichment conditions (aerobic, anaerobic, presence or absence of combined nitrogen). Plastics ingested by larvae obtained in Spain did not show any signs of oxidation but only limited depolymerization, preferably from the lowest molecular weight chains. Gut microbiota composition changed as an effect of plastic feeding. Such differences were more evident in bacterial enrichment cultures, where the polymer type influenced the composition more than by culture conditions, with an increase in the presence of nitrogen-fixers in anaerobic conditions. PS and PP degradation by different enrichment cultures was confirmed under aerobic and anaerobic conditions by respirometry tests, with anaerobic conditions favouring a more active plastic degradation. In addition, exposure to selected bacterial consortia in aerobiosis induced limited surface oxidation of PS. This possibly indicates that different biochemical routes are being utilized in the anaerobic gut and in aerobic conditions to degrade the polymer.

Until recently, recycling thermoset polyurethanes (PUs) was limited to degrading methods. The development of covalent adaptable networks (CANs), to which PUs can be assigned, has opened novel possibilities for actual recycling. Most efforts in this area have been directed toward inventing new materials that can benefit from CAN theory; presently, little or nothing has been applied to industrially producible materials. In this study, both an industrially available polyol (Sovermol780^®) and isocyanate (Tolonate X FLO 100^®) with percentages of bioderived components were employed, resulting in a potentially scalable and industrially producible material. The resultant network could be reworked up to three times, maintaining the crosslinked structure without significantly changing the thermal properties. Improvements in mechanical parameters were observed when comparing the pristine material to the material exposed to three rework processes, with gains of roughly 50% in elongation at break and 20% in tensile strength despite a 25% decrease in Young’s modulus and crosslink density. Thus, it was demonstrated that theory may be profitably applied even to materials that are not designed including additional bonds but instead rely just on the dynamic urethane bond that is naturally present in the network.

Thermoset polyurethanes invite industrial interest for their versatility and chemical and mechanical resistance due to their permanently crosslinked networks; yet this structural feature severely limits their recyclability. Recent advances in Covalent Adaptable Networks (CANs), enabled by Dynamic Covalent Chemistry (DCC), have demonstrated promising pathways toward reprocessability through bond-exchange mechanisms. However, no clear link has yet been identified between material properties and the retention of performance after reprocessing. This work investigates the role of crosslink density as a key factor in determining the reprocessability of polyurethane networks. Two model systems with comparable compositions but distinct crosslink densities were synthesised, reprocessed, and compared. Relaxation analysis based on the Maxwellian approach proved insufficient to predict reprocessing outcomes. Only the highly crosslinked network yielded homogeneous reprocessable films with significant retention of mechanical performance, whereas the less crosslinked network resulted in incoherent materials with markedly reduced properties. The application of Kohlrausch–Williams–Watts (KWW) fitting revealed that dynamic covalent exchange dominates relaxation in the highly crosslinked system, while in the looser network, relaxation is governed by soft segment mobility, hindering effective network reformation. These findings underscore the pivotal role of crosslink density in determining the recyclability of thermoset polyurethanes and provide new insights for the rational design of reprocessable materials.