Studies on thermoplastic polyurethanes based on new diphenylethane-derivative diols. I. Synthesis and characterization of nonsegmented polyurethanes from HDI and MDI

Abstract

New aliphatic–aromatic α, ω-diols containing sulfur in aliphatic chain: 4,4′-(ethane-1,2-diyl)bis(benzenethioethanol) [EBTE], 4,4′-(ethane-1,2-diyl)bis(benzenethiopropanol) [EBTP], 4,4′-(ethane-1,2-diyl)bis(benzenethiohexanol) [EBTH], 4,4′-(ethane-1,2-diyl)bis(benzenethiodecanol) [EBTD], and 4,4′-(ethane-1,2-diyl)bis(benzenethioundecanol) [EBTU] were prepared by the condensation reaction of 4,4′-(ethane-1,2-diyl)bis(benzenethiol) with suitable halogen alcohols in aqueous sodium hydroxide solution. Thermoplastic nonsegmented polyurethanes containing sulfide linkages were synthesized from these diols, and hexane-1,6-diyl diisocyanate (HDI) or 4,4′-methylenediphenyl diisocyanate (MDI) by solution and melt polymerization. The reaction was carried out at 1:1 or 1.05:1 molar ratios of isocyanate and hydroxy groups in the presence of dibutyltin dilaurate as a catalyst. The structures of the diols were determined by using elemental analysis, FTIR and 1H NMR spectroscopy, and X-ray diffraction analysis. Thermal characteristics of the diols were determined by using differential scanning calorimetry (DSC). The polymers were studied to describe their structures and physicochemical, thermal (by DSC and thermogravimetric analysis) and tensile properties as well as Shore A/D hardness. All the polyurethanes possessed partially crystalline structures. Their melting temperatures were in the range of 94–179 °C (HDI) and 105–207 °C (MDI). The MDI-based polyurethanes showed higher tensile strengths, up to ∼50 MPa.