In this contribution a new class of aliphatic poly(butylene succinate) (PBS)-based poly(ester urethane)s has been synthesized and characterized from the molecular, thermal and mechanical point of view. Hydrolytic degradation studies under physiological conditions have been conducted to assess their biodegradation rate. To obtain copolymers showing both thermoplastic and elastomeric properties, the chain-linking strategy has been considered. In particular, two hydroxyl-terminated oligomers have been synthesized by melt polycondensation: poly(butylene succinate) (PBS), as a "hard segment", and two poly(butylene adipate/diglycolate) P(BAmBDGn) random copolymers as a "soft segment". The introduction of ether-linkages along the PBA chain permitted to depress its crystallinity degree and to enhance the wettability. Multiblock copolymers were finally obtained by chain extending with hexamethylene diisocyanate each P(BAmBDGn) copolymer with two different mass percentages of PBS: 30% and 50%. All copolymers maintained good thermal stability and were characterized by melting temperatures above 100 °C. Elastic modulus (E) and stress at break (σb) varied with the chemical composition: the higher the PBS amount, the higher E and σb. No yield and very high elongations at break were observed. Hydrolytic degradation studies highlighted an increase of the degradation rate with the increase of the BDG content.
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