Covalent adaptable networks (CANs) represent a pioneering advance in polymer science, offering unprecedented versatility in materials design. Unlike conventional adhesives with irreversible bonds, CAN-based polyurethane adhesives have the unique ability to undergo chemical restructuring through reversible bonds. One of the strategies for incorporating these types of reactions in polyurethanes is by functionalisation with Diels–Alder (DA) adducts. By taking advantage of the reversible nature of the DA chemistry, the adhesive undergoes controlled crosslinking and decrosslinking processes, allowing for precise modulation of bond strength. This adaptability is critical in applications requiring reworkability or recyclability, as it allows for easy disassembly and reassembly of bonded components without compromising the integrity of the material. This study focuses on the sustainable synthesis and characterisation of a solvent-based polyurethane adhesive, obtained by functionalising a polyurethane prepolymer with DA diene and dienophiles. The characterisation of the adhesives was carried out using different experimental techniques: nuclear magnetic resonance spectroscopy (NMR), Brookfield viscosity, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and T-peel strength testing of leather/adhesive/rubber joints to determine the adhesive properties, both before and after the application of external stimuli. The conversion of both the DA and retro-Diels–Alder (r-DA) reactions was confirmed by ¹H-NMR. The adhesive properties were not altered by the functionalisation of the adhesive prepolymer, showing similar thermal resistance and good rheological and adhesive properties, even exceeding the most demanding technical requirements for upper-to-sole joints in footwear. After the application of an external thermal stimuli, the bonded materials separated without difficulty and without damage, thus facilitating their separation, recovery and recycling.

This study aimed to enhance the initial adhesion performance of reactive polyurethane hot-melt adhesives by using a bio-based polycarbonate polyol instead of traditional polyester or polyether polyols and by incorporating thermoplastic polyurethane (TPU) in varied proportions. Adhesives synthesized from bio-based polycarbonate polyols and polypropylene glycol with MDI as the isocyanate were characterized chemically, thermally, and mechanically (FTIR, DSC, plate–plate rheology, DMA, and T-peel strength test). Adding 10–15 wt.% TPU significantly improved green strength and initial adhesion at room temperature and after accelerated cooling. The bio-based polycarbonate polyol promotes superior flexibility at low temperatures compared to fossil-derived alternatives, aligning with sustainability objectives. The results showed that 10 wt.% TPU maximized green strength without compromising flexibility, whereas 15 wt.% TPU, though enhancing adhesion, reduced flexibility due to increased crystallinity. T-peel tests on footwear materials indicated that all the adhesives exceeded the EN 15307:2015 requirements, with the highest peel strength achieved after curing. These findings highlight the benefit of bio-based polycarbonate polyols and TPUs in achieving strong, flexible, and eco-friendly adhesives suitable for demanding applications.

1. The increasing global consumption of polyurethane (PU) materials – particularly within the automotive, construction footwear and mattress manufacturing sectors – is projected to continue growing...