Initiator‐Free Photocuring 3D‐Printable PVA‐Based Hydrogel with Tunable Mechanical Properties and Cell Compatibility

Abstract Poly(vinyl alcohol) (PVA)‐based hydrogels have attracted great attention and been widely used in biological tissue engineering. With the development of modern medicine, precision medicine requires the customization of medical materials. However, lacking of photocurable functional groups or the performance of rapid phase transition makes PVA‐based hydrogels difficult to be customizable molded through photocuring 3D printing technique. In this research, customizable PVA‐based hydrogels with high performance through 3D photocurable printing and freezing‐thawing (F‐T) process are obtained. The ability of 3D‐printable is endowed by the introduction of polyvinyl alcohol–styrylpyridine (PVA‐SBQ), which can be photo‐crosslinked quickly without photoinitiator. Meanwhile, the tunable mechanical properties are achieved by adjusting the mass ratio of PVA‐SBQ to PVA, and PVA can offer the physical crosslinking points through freezing‐thawing (F‐T) process. The hydrogels with high resolution are prepared by digital light procession 3D printing with the mass ratio 1:1 of PVA‐SBQ to PVA solution. Attributed to the absence of initiator, and no small molecule residues inside the hydrogels, the hydrogels have good biocompatibility and have the potential to be applicated in the field of biological tissue engineering.