Influence of the Chemical Structure of Urethane-Based Thickeners on the Properties of Waterborne Polyurethane Adhesives

To analyse the parameters that influence the thickening mechanism of waterborne polyurethane adhesives, different hydrophobically modified ethoxylated polyurethane based thickeners (HEUR) were used. The thickeners were characterized by proton nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC). The thickened adhesive solutions were characterized by flow rheology, pH, particle size measurements, solids content, and confocal microscopy. The thickened solid adhesive films were characterized by ATR-IR spectroscopy, parallel plate rheology, dynamic mechanical thermal analysis (DMTA), and differential scanning calorimetry (DSC). The adhesion was measured by a T-peel test of leather/polyurethane adhesive/SBR rubber joints. The addition of the different HEUR thickeners increased the viscosity of the polyurethane dispersion to different degrees. Furthermore, whereas the un-thickened polyurethane dispersion showed a Newtonian rheological behaviour, a shear-thinning rheological behaviour was observed in the thickened dispersions due to thickener-thickener and polyurethane-thickener interactions. The viscosity of the thickened polyurethane adhesive solutions increased with the degree of hydrophobicity and the molecular weight of the thickener. The addition of different thickeners increased the pH values due to the ionic adsorption, which is one of the interactions that contribute to the thickening mechanism of the polyurethane thickeners, besides hydrogen bonding and van der Waals hydrophobic interactions (micelles). The entanglement of the thickened polyurethane adhesives was studied by confocal microscopy. Although the addition of the thickeners did not affect the thermal properties of the polyurethanes, the T-peel strength of leather/adhesive/SBR rubber joints was influenced by the rheological properties of the thickened adhesives.