Thermal, mechanical, and fracture properties of copolyureas formed by reaction injection molding: Effects of hard segment structure

A series of copolyureas containing 50% by weight hard segment have been formed by RIM. The hard segment structure was systematically varied to investigate the effects of urea group density, hard segment crosslinking, relative reaction rates, and to compare the properties of aromatic and aliphatic hard segment materials. In each case the soft segment was based on a 2000 molecular weight polyether diamine. The RIM materials formed ranged from flexible elastomers to brittle plastics depending on composition and were characterized by SAXS, DSC, DMA, tensile stress–strain and fracture mechanics studies. SAXS, DSC, and DMA showed that microphase separation had occurred to give materials with a non‐equilibrium morphology. DMA and tensile stress–strain studies showed the small strain properties to be very sensitive to the volume fraction of glassy material whereas the ultimate properties were dependent on chemical structure of the hard segment. Fracture properties were determined using the single‐edge notch technique. In most cases ductile failure occurred with G_c > 2.5 kJ m⁻² and the fracture surfaces showed gross yielding and tearing. In the case of the copolyurea with the highest urea group content, brittle fracture occurred with G_c = 0.06 kJ m⁻².