Hsin-Chen Chen, Gilles Sèbe, Thomas Vidil, Lars. A. Berglund, Audrey Llevot, Henri Cramail, Qi Zhou
High Resolution Image Download MS PowerPoint Slide Polyurethanes are widely used in adhesive applications, but their conventional synthesis relies on hazardous isocyanates and often solvent-based formulations. In this work, waterborne polyhydroxyurethanes (PHUs) were synthesized from 1,6-hexanediol bis(cyclic carbonate) and bio-based Priamine 1075 via catalyst-free suspension polymerization in water. Pristine cellulose nanocrystals (CNCs) acted as the sole stabilizers, eliminating the need for petroleum-derived surfactants while simultaneously serving as reinforcing nanofillers. Stable monomer-in-water emulsions were obtained with CNC loadings up to 200 mg mL –1 per monomer, corresponding to ∼17 wt % CNCs in the final dried nanocomposites. In the latex state, CNCs were located at the particle surfaces, ensuring colloidal stability, while in the dried PHU/CNC nanocomposites they were uniformly distributed throughout the matrix, yielding adhesives with markedly enhanced performance. The nanocomposites exhibited up to 680% and 340% increases in probe tack adhesion strength and lap-shear strength, respectively, compared with surfactant Tween 80-stabilized waterborne PHUs, reaching performance levels comparable to commercial pressure-sensitive adhesives. These findings demonstrate that combining bio-based monomers with CNC stabilization offers a robust strategy for producing sustainable, high-performance PHU adhesives consistent with green chemistry principles.