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Thermal, structural and spectroscopic behavior of the blends of poly(ethylene oxide)glycol (PEO) with a model urethane compound bis(4-butylcarbamatocyclohexyl)methane and 1,3-dimethylurea (DMU) were investigated by differential scanning calorimetry (DSC) and hot-stage optical microscopy (HOM). Blends with a wide range of compositions were prepared in tetrahydrofuran (THF) solutions and dried. DSC results indicated the formation of two-phase structures consisting of a pure polyether phase and a highly mixed DMU–polyether phase. As the amount of polyether in the blends was increased, the melting endotherm of DMU became much broader and shifted to lower temperatures, indicating extensive mixing with PEO. The mixed phase was also crystalline. This was strongly supported by HOM results. While pure PEO and DMU crystals showed spherulitic structures, mixed DMU–PEO phase showed fibrillar crystals. Consecutive heating–cooling cycles of the blends did not result in any changes in the blend morphologies. Formation of strong hydrogen bonding between DMU and PEO was also demonstrated by FTIR spectroscopy from the shifts in (N–H and C&z.dbnd6;O) absorption peaks. [Copyright &y& Elsevier]

Quantum mechanical calculations (QMC) and dissipative particle dynamics (DPD) simulations were utilized to understand the nature of the short and long-range hydrogen bonding and its influence on the microphase morphology in segmented polyurethanes and segmented polyureas prepared without chain extenders through the stoichiometric reactions of hydroxy or amine terminated poly(tetramethylene oxide) (PTMO-1000) with 1,4-phenylene diisocyanate (PPDI) and 1,3-phenylene diisocyanate (MPDI). The possibility of long-range connectivity due to a network of well-ordered hydrogen bonds between symmetrical PPDI and kinked MPDI based model urethane and urea compounds were also investigated. Special emphasis was given on the understanding of the influence of diisocyanate symmetry and nature of the hydrogen bonding between hard segments on the morphology development. QMC results obtained clearly indicated the possibility of long-range ordering of hydrogen bonds between PPDI based urethane and urea groups, while MPDI based systems did not display such a behavior. DPD results strongly supported the QMC studies and clearly demonstrated the possibility of long-range connectivity of hydrogen bonds between urethane and urea groups in PPDI based segmented copolymers, leading to the formation of microphase separated morphologies in these systems, which was not observed in the kinked MPDI based segmented urethane and urea copolymers. Computational results obtained strongly supported the experimental observations reported on the morphology and thermal and mechanical properties of these segmented polyurethanes and polyureas based on PPDI and MPDI. [ABSTRACT FROM AUTHOR]