Synthesis of PLLA-b-PCL-b-PLLA linear tri-block copolymers and their corresponding poly(ester-urethane)s: effect of the molecular weight on their crystallisation and mechanical properties

With the general objective to design polymer based materials with specific thermal and mechanical properties, a systematic study on the crystallinity and the mechanical properties of synthesized linear triblock copolymers based on poly(L-lactic acid) and poly(epsilon-caprolactone) and of their corresponding poly(ester-urethane)s has been performed. In particular, eleven tri-block copolymers were synthesized varying both the molecular weight of the blocks as well as the relative content of each block in the copolymer, focusing the attention on the relationship between their chemical compositions and their tailored final properties in order to tune them taking into account their possible applications (i.e. as shape memory materials). From them, eleven poly(ester-urethane) s were synthesized by condensation with hexamethylene diisocyanate (HDI). The chemical composition of the synthesized polymers was studied and correlated with their thermal and crystalline properties obtained by both dynamic scanning calorimetry (DSC) and small angle X-ray diffraction (SAXS) experiments. The relationship between their crystalline structure, thermal and mechanical properties with the molecular weight as well as with the relative content of each comonomer in the copolymers and the amount of HDI in the poly(ester-urethane) was analysed. The results obtained demonstrate that these bio tri-block copolymers and the corresponding poly(ester-urethane)s can be tailored with interesting crystalline and mechanical properties. Future applications as shape memory systems are thus envisaged.