Influence of the chemical structure of poly(urea-urethane-siloxane)s on their morphological, surface and thermal properties

Segmented poly(urethane-urea-siloxane)s (PUUS) were synthesized using 4,4'-methylenediphenyl diisocyanate (MDI) and ethylene diamine (ED) as the hard segment components and hydroxypropyl-terminated poly(dimethylsiloxane) (PDMS) as the soft segment component, where the hard segment content ranged from 38 to 65 wt%. Segmented PUUSs were prepared by a two-step polymerization procedure in tetrahydrofuran/N-methylpyrrolidone (THF/NMP) mixture with a large proportion of polar solvent. The structure, composition and hard segment length were determined by C-13 NMR and two-dimensional correlation spectroscopy. Thermal, mechanical, small-angle X-ray scattering and hydrogen bonding analyses indicated the formation of the microphase-separated copolymers with high tensile strength. Globular superstructures observed in the copolymer films by scanning electron microscopy (SEM) and atomic force microscopy (AFM) were probably arisen from the microstructural organization of the MDI-ED segments, depending on their content and length. The PUUS copolymers showed high water resistance and became more hydrophobic with increasing weight fraction of PDMS.