Properties and phase separation of reaction injection molded and solution polymerized polyureas as a function of hard block content

A series of amine terminated polypropylene oxide based thermoplastic polyureas with hard segment contents of 30%, 50%, and 70 percent were synthesized via solution polymerization and reaction injection molding (RIM). Amine terminated polypropylene oxide (PPO‐NH₂) of M_n = 2000 was used as the soft segment and 4,4′‐diphenylme‐thanediisocyanate (MDI) extended with diethyltoluenediamine (DETDA) as the hard segment. These polyureas are linear, amorphous, and phase separated. Polymers were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC), dynamic mechanical spectroscopy (DMS), small angle X‐ray scattering (SAXS), and tensile testing. RIM polyureas had significantly lower molecular weights than solution polymerized polyureas, but their mechanical properties did not suffer, RIM polyureas have poorer phase separation than solution polyureas as evidenced by DSC, DMS, and SAXS, especially at high hard segment levels. SAXS shows phase separation levels of up to 100 percent for low hard segment polyureas and down to 10 percent for high hard segment RIM polyurea. DSC found no evidence of a hard segment glass transition, and the evidence from DMS was inconclusive. In addition to polymer characterization, demolding behavior was studied. The 30 percent hard segment was always tough and elastomeric, while the 70 percent hard segment was always very brittle. The 50 percent hard segment showed the greatest variation in properties, ranging from very brittle to very though as mold temperature and in‐mold time were increased. Demold brittleness is explained by the presence of low molecular weight DETDA/MDI oligomers on demolding, which continue to react on aging.