Polyurea Synthesis and Properties as a Function of Hard-Segment Content

Abstract

Abstract High-molecular-weight linear polyureas of different hard-segment content are obtained with a two-step solution polymerization. Elimination of water, careful choice of solvent, reactant concentration, and good control of reaction temperature are essential to obtain satisfactory results. We have studied the influence of the hard-segment content on the mechanical, dynamic-mechanical, and thermal properties of these solution polymerized amine-terminated polypropylene-oxide-based thermoplastic polyureas. Two-phase morphology is predominant within the range of the hard-segment concentration studied. Inversion of the continuous and dispersed phase might occur in the polyurea series at about 60 wt.% of hard segment. This changes the nature of the polyureas from a tough elastomeric material to a more brittle, high-modulus plastic. The modulus of the rubbery plateau measured from dynamic-mechanical spectra increases with hard-segment concentration due to the reinforcing effect of hard-segment domains. However, continuous improvement in dynamic-mechanical modulus is not significant when the hard segment is above 50 wt.% due to higher degree of phase mixing in high hard-segment concentration systems. The amount of solubilized hard segment in the soft-segment phase in these polyureas is limited as judged from the relatively constant soft-segment Tg. However, the extent of phase separation, as determined by the heat capacity change ΔCp across the soft-segment Tg, decreases with increasing hard-segment content. The same characterizations and analyses have also been carried out on a series of RIM produced polyurea samples of the same composition. Great difference in properties is observed in comparison of these two sets of samples due to their different synthesis routes. In general, samples produced by RIM exhibit lower molecular weight, lower dynamic-mechanical modulus, higher soft-segment Tg, more phase-mixed, and more tensile elongation than those synthesized by solution polymerization. The detailed comparison will be treated in a separate paper.