AbstractA series of segmented polyurea urethane and polyurea block copolymers based on a hexane diisocyanate (HDI) modified aminopropyl terminated polydimethylsiloxane soft segment was synthesized. The hard segments consisted of 4,4′‐methylene diphenylene diisocyanate (MDI) which was chain extended with 1,4‐butanediol (BD),N‐methyldiethanolamine (MDEA), or ethylene diamine. Zwitterionomers were prepared by quaternizing the tertiary amine of the MDEA extended material with γ‐propane sultone. The effect of chemical structure on the extent of phase separation and physical properties was studied using a variety of techniques including thermal analysis, dynamic mechanical spectroscopy, tensile testing, and small‐angle x‐ray scattering. It was observed that the compatibility between the nonpolar polydimethylsiloxane soft segments and the polar urethane hard segments was improved by inserting HDI linkages into the polydimethylsiloxane soft segments. The aggregation of hard segments was enhanced by increasing hard‐segment content or by the introduction of ionic functionality. The tensile strength and modulus of these materials was higher than those of polyurethanes containing soft segments based on polydimethylsiloxane and