The aim of this study was to estimate the structure of new polyurethanes with the potential to be used in medicine. Atactic poly[(R,S)-3-hydroxybutyrate], obtained via a ring-opening polymerization, and polycaprolactonediol or polyoxytetramethylenediol were used to built the soft segments. 4,4 0 -methylene dicyclohexyl diisocyanate and 1,4-butanediol were the components to form hard segments. At FTIR spectra of obtained polyurethanes the bands attributed to AN¼ ¼C¼ ¼O groups completely disappeared, similarly as these of AOH groups and the new band characteristic for stretching vibrations of bonded urethane ANH groups appeared. Polyurethanes with low-mo-lecular weight were obtained. The observation of FTIR and 1 H-NMR spectra had been suggested that NH groups form two types of hydrogen bonds: with C¼ ¼O urethane (possibly with ester group) and ether groups. An addition of poly[(R,S)-3-hydroxybutyrate] caused the slight increase in number of urethane-urethane hydrogen bonds. For some of polyurethanes (based on polyoxytetramethylenediol) the allophanate structures were obtained. V C 2012 Wiley Periodicals, Inc. J Appl Polym Sci 125: [4285][4286][4287][4288][4289][4290][4291] 2012