Double Crystalline Multiblock Copolymers with Controlling Microstructure for High Shape Memory Fixity and Recovery.

The shape memory performance of double crystalline poly(butylene succinate)-co-poly(ε-caprolactone) (PBS-co-PCL) multiblock copolymers with controlling microstructure was studied, and the corresponding microstructure origin was further quantitatively analyzed by wide and small-angle X-ray scattering (WAXS and SAXS) experiments. It was found that the multiblock copolymer with higher PCL content, proper deformation strain, and inhibited crystallization of PBS (lower crystallinity and smaller crystal size, which could be realized by quenching from the melt) would exhibit better shape memory fixity and recovery performance. WAXS and SAXS results revealed that the shape fixity ratio (Rf) was closely related with the relative crystallinity of the PCL component, while the shape recovery ratio (Rr) strongly relied on the deformation and recovery behavior of the PBS and PCL components that changed along with compositions and deformation strains. For the copolymer with higher PCL content (BS30CL70), at the lower deformation strain (0% ∼ 90%), both the PBS and PCL components after recovery had no orientation (labeled as stage I), resulting in almost complete recovery; with the deformation strain increasing (90% ∼ 200%), it was the irreversible deformation of the PCL component that largely took responsibility for the decreased Rr (stage II). On the contrary, when the PCL content decreased to 50 wt % (BS50CL50), stage I (0% ∼ 50%) and stage II (50% ∼ 100%) appeared in much lower strains; with the deformation strain increasing (100% ∼ 200%), the irreversible deformation of both PBS and PCL components was mainly responsible for the further reduction of Rr (stage III). It could exhibit excellent shape memory performance for biodegradable double crystalline multiblock copolymers by controlling the composition, deformation strain, and crystallization, which might have wide application prospects in biomedical areas.