Microstructure Changes in Polyester Polyurethane upon Thermal and Humid Aging

The microstructure of compression molded Estane 5703 films exposed to 11%, 45%, and 80% relative humidity and 70 °C for 1 and 2 months has been studied by small-angle neutron scattering (SANS), Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). Scattering data indicated increase of the interdomain distance and domain size with a higher humidity and longer aging time. GPC data showed a progressive shortening of polyurethane chains with increasing humidity and aging time. The shortening of the polyurethane chains caused a drop of the glass transition temperature of soft segments, and promoted crystallization of the soft segments during long-time storage of the aged samples at room temperature. FTIR showed a substantial increase in the number of inter-urethane H-bonds in the aged samples. This correlates with the increase of the hard domain size and the degree of phase separation as measured by SANS. The data collected reveals that the reduced steric hindrance caused by hydrolysis of ester links in polybutylene adipate residues promotes the organization of hard segments into domains, leading to the increase of domain size and distance, as well as phase segregation in aged Estane. These findings provide insight into the effects of humidity and thermal aging on the microstructure of aged polyester urethane from molecular to nanoscale level.