Structural, thermal and surface characterization of thermoplastic polyurethanes based on poly(dimethylsiloxane)

In this study, the synthesis, structure and physical properties of two series of thermoplastic polyurethanes based on hydroxypropyl terminated poly(dimethylsiloxane) (HP-PDMS) or hydroxyethoxy propyl terminated poly(dimethylsiloxane) (EO-PDMS) as a soft segment, and 4,4?-methylenediphenyl diisocyanate and 1,4-butanediol as a hard segment were investigated. Each series is composed of samples prepared with a different soft segment. The polyurethanes were synthesized by two-step polyaddition in solution. The effects of the type and content of PDMS segments on the structure, thermal and surface properties of copolymers were studied by 1H NMR, 13C NMR and two-dimensional NMR (HMBC and ROESY) spectroscopy, GPC, DSC, TGA, WAXS, SEM, water contact angle and water absorption measurements. Thermal properties investigated by DSC indicated that the presence of soft PDMS segments lowers the glass transition and melting temperatures of the hard phase as well as the degree of crystallinity. SEM analysis of copolymers with a lower soft segment content confirmed the presence of spherulite superstructures, which arise from the crystallization of the hard segments. When compared with polyurethanes prepared from HP-PDMS, copolymers synthesized from EO-PDMS with the same content of the soft segments have higher degree of crystallinity, better thermal stability and less hydrophobic surface. Our results show that the synthesized polyurethanes have good thermal and surface properties, which could be further modified by changing the type or content of the soft segments. nema