Influence of chain topology on gel formation and direct ink printing of model linear and star block copolymers with poly(ethylene oxide) and poly(ε-caprolactone) semi-crystalline blocks

• DOI: 10.1016/j.eurpolymj.2023.112526
• Publication Date: 2023-10-27T10:58:58Z
• Authors: Edward Centeno; Mario Iván Peñas; Pengfei Zhang; Viko Ladelta; Jorge Mercado-Rico; Eider Matxinandia...; Manuela Zubitur; Agurtzane Mugica; Nikos Hadjichrist...; Alejandro J. Müller; Rebeca Hernández
• Keywords: Caprolactone

In this work, a set of well-defined linear triblock copolymers and star block (3 4-arms) with semi-crystalline blocks consisting poly(ethylene oxide) (PEO) poly(ε-caprolactone) (PCL), synthesized by combining ring-opening polymerization organic catalyst switch strategy, were studied as thermosensitive gel-forming biomaterials for applications in 3D extrusion printing. The hydrogels derived from underwent temperature-dependent sol–gel–sol transition, behaving flowing sol at room temperature transforming into non-flowing gel upon heating. On the other hand, 4-arm experienced gel-sol transition did not flow temperature. This behavior allowed them to be used printing inks results revealed that could only extruded printed high shape fidelity, but they also exhibited favorable dissolution profile their use sacrificial biomaterial inks. Additionally, we thoroughly investigated crystalline organization PCL PEO within through comparison obtained bulk. demonstrated evident structural ordering associated crystallization blocks. Unexpectedly, DSC combined SAXS experiments presence crystals 30 % w/v copolymers, addition crystals. Hence, remarkable double have been first time.