Structure and adhesion properties before and after hydrolytic ageing of polyurethane urea adhesives made with mixtures of waterborne polyurethane dispersions

Several waterborne polyurethane urea dispersions (WPUUs) were prepared by mixing different amounts of two waterborne polyurethane urea dispersions made with polyester (WPUU-Polyester) and polycarbonate diol (WPUU-PCD). Their crystallinity, thermal, rheological, viscoelastic and adhesion properties depended on the segmented structure and degree of phase separation which were determined by the different content of the parent dispersions. The PUU films made with WPUU-Polyester+WPUU-PCD mixtures containing more than 50 wt% of WPUU-PCD showed higher hard segments content and lower degree of phase separation, and the addition of 25 wt% of WPUU-Polyester imparted crystallinity to the polyurethane urea due to the interactions between the carbonate groups in the soft segments. The differences in the degree of phase separation and crystallinity of the PUU films made with WPUU-Polyester+WPUU-PCD mixtures were evidenced by the increase in the glass transition temperature associated to the alpha relaxation of the soft segments, and the higher modulus at the cross-over between the storage and loss moduli. Excellent adhesion was obtained in plasticized PVC/WPUU/plasticized PVC joints, and a cohesive failure of PVC was always obtained, irrespective of the composition of WPUU-Polyester+WPUU-PCD mixtures. Furthermore, the adhesion of surface-chlorinated vulcanized styrene-butadiene (SBR) rubber/WPUU+5 wt% hardener/roughened leather joints were high and similar in all joints and a dominant cohesive failure in the rubber substrate was produced. The accelerated ageing by immersion in water at 70 °C during different times showed that the polyurethane urea film and the surface-chlorinated vulcanized SBR rubber/WPUU+5 wt% hardener/roughened leather joint made with WPUU-PCD dispersion were not affected, but noticeable hydrolytic degradation of the ester units in the soft segments was produced in PUU-Polyester and, to a less extent, in PUU-50Polyester/50PCD films and adhesive joints.