End-Terminated Poly(urethane–urea) Hybrid Approach toward Nanoporous/Microfilament Morphology

[Image: see text] In the present work, the effect of heteroatomic hydrogen bonding on the properties of −OH/–NH-terminated soft-segment-free polymers, viz, polyurethane (P-UT), polyurea (P-UR), and their hybrid (P-UT–UR), is explored. P-UT was synthesized from phloroglucinol and P-UR was synthesized from 1,3,5-triazine-2,4,6-triamine by employing hexamethylene diisocyanate as a counterpart. P-UT exhibited a spherulitic structure with varying sizes, whereas P-UR displayed a fibrillar structure characteristic as that of crystalline hard segments. The P-UT–UR hybrid exhibited a fine nanospherulitic structure with a high order of interconnectivity. Negative surface skewness values of −0.47 and −0.18 were measured (by AFM) for P-UT and P-UT–UR, respectively, which revealed that the surface is not smooth and is covered with features. Due to the increased H-bonding (−N–H···O–H) in P-UT–UR, its transparency decreased. A block copolymer hybrid of urethane–urea was synthesized, which preferred homoatomic H-bonding, whereas random urethane/urea bridges favored hetreoheteroatom H-bonding. A pentafluorophenyl end-functional hybrid (PFI–P-UT–UR) was synthesized, which displayed filaments of ∼2–3 μm length in contrast to the interconnected nanospherulitic structure observed for P-UT–UR. The self-aggregation and end folding led to the formation of a filament structure. By altering the chemical structure slightly, nano-ordered polyurethanes or their hybrids can be achieved.