Impact of moisture curing conditions on the chemical structure and rheological and ultimate adhesion properties of polyurethane adhesives based on castor oil and cellulose acetate

On account of the heavy reliance of the adhesive industry on petrochemical derivatives, there is a particular interest in the development of bio-sourced poly-urethane adhesives. In this context, a moisture-curable polyurethane adhesive has been synthesized from cellulose acetate and castor oil, using 1,6-hexamethylene diisocyanate as a crosslinker. In particular, this research delves into the rheological and adhesion properties achieved by bio-inspired polyurethanes cured at 20 degrees C and under different relative humidity conditions (11, 33, 64, and 90.4%). Green shear and peeling strengths on wood and stainless steel as well as chemical structure variations were monitored over curing time. Moreover, fully cured polyurethane-urea adhesives were thermally (thermogravimetric and differential scanning calorimetric analyses) and rheologically characterized within the linear viscoelastic region. The results corroborated the noteworthy impact of environmental humidity throughout the curing process of the synthesized bio-sourced adhesives, favoring the formation of urea linkages, while sharply reducing the crystalline/amorphous ratio. All the bio-based polyurethane-urea copolymers showed a predominant elastic behavior and the time-Temperature superposition principle was found to be applicable up to around 120 degrees C, due to the thermal rearrangement of the hard segment units. The crosslinking density of the resulting supramolecular structure depends on the humidity-driven balance between the urethane and urea linkages production. As a consequence of the balance between the establishment of bidentate hydrogen bonds and the curing rate, moisture curable polyurethane adhesive cured at 33% relative humidity exhibited the most appropriate shear adhesion performance on wood, while the debonding shear strength on stainless steel increased with the relative humidity due to the higher urea:urethane ratio and larger proportions of non-bonded urethane and urea groups, thus enhancing secondary interactions. Therefore, on the basis of the present study results, it might be concluded that the synthesis of bio-inspired moisture-curable polyurethane can be tuned according to its end-use application through the control of the environmental conditions, and thereby optimizing their adhesion performance, while meeting the Green Chemistry tenets.