This knowledge allows for precise control of printing parameters and the material's processing conditions, since the feeding material used in melt extrusion is subjected to different stresses during processing, such as heat transfer, fluid flow and solidification at different stages. The heating and cooling DSC thermograms of the synthesized copolymers are shown in Figures and, respectively. Numerical data are summarized in Table . At a glance, low temperature glass transition (Tg) and high melting temperature (Tm) can be seen for all copolymers what is typical for thermoplastic elastomers (TPE) . The low temperature Tg is assigned to the soft segments and the high Tm is ascribed to melting of the crystalline hard segments. In details, when the PBS-DLS copolymers of different hard to soft segments ratio were heated from -80°C, the glass transition occurred at around -47°C for PBS-DLS 70-30 and at -50°C for PBS-DLS 60-40. While the differences in Tg values were not significant, the differences in specific heat capacity (ΔCp) were notable, since copolymer with higher soft segments (40 wt%) showed higher ΔC p of 0.525 J/g•°C compared to 0.220 J/g•°C for PBS-DLS 70-30 wt.%. In case of PBS-DLS-PEG copolymer containing 70 wt.% of hard segments, the addition of PEG also slightly increases the ΔCp and shifted Tg to lower temperature reaching 1°C). This observation may seem contradictory given the incorporation of a flexible spacer, such as PEG, which conventionally tends to decrease the melting temperature (T m ). However, we used PEG of 6000 g/mol in our work which shows crystallization ability thus its flexibility is diminished. In the cooling process, substantial differences were observed between the copolymers with different segmental ratios (Figure ). The copolymer with higher soft segments content (40 wt.%) showed very broad and flat crystallization peaks at much lower crystallization temperature, Tc (17.2 °C) compared to material with 30 wt.% of soft segments where Tc=28.4 °C. This behavior suggests a slower and more prolonged crystallization process for the copolymer with higher soft segment content, potentially leading to differences in material properties such as thermal stability. The broader and flatter crystallization peaks imply a more extended period for the formation of ordered molecular structures in the copolymer, which can influence its overall crystalline properties. The PBS-DLS 60-40 material also showed very low crystallization enthalpy (ΔHc=7.24 J/g). Interestingly, an incorporation of 5 wt.% of PEG6000 resulted in increase of the crystallization temperatures from 28°C to 31°C for copolymer with 70 wt% of hard segments, and from 17°C to 23°C in copolymers with 60 wt% of hard segments, due to the crystallization ability of PEG 6000 similar to PE-PEG materials. By changing the hard segments ratio, the degree of crystallinity of hard segments varied and was about 5% higher for materials containing higher hard segments content.