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New thermoplastic segmented polyurethanes were obtained by a one-step melt polyaddition using 40, 50 and 60 mol% poly(hexane-1,6-diyl carbonate) diol of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\bar{M}_{n} = 860$$\end{document}M¯n=860 g mol−1, 1,1′-methanediylbis(4-isocyanatobenzene) and 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol, 2,2′-[oxybis(benzene-1,4-diylsulfanediyl)]diethanol or 2,2′-[sulfanediylbis(benzene-1,4-diylsulfanediyl)]diethanol as a chain extender. FTIR, atomic force microscopy, differential scanning calorimetry and thermogravimetry were used to examine the polyurethanes’ structure and thermal properties. Moreover, their Shore A/D hardness, tensile, adhesive and optical attributes were determined. They were transparent high-molar-mass materials showing good tensile strength (up to 51.9 MPa). The polyurethanes exhibited improved adhesion to copper taking into consideration that of conventional ones, and middle or high refractive index values (1.57–1.60), and both these parameters increased with an increase of the content of sulfur atoms in the polyurethane chain. The newly obtained polyurethanes can be considered as materials for numerous medical and optical appliances.