Two‐Step Solvent‐Free Synthesis of Poly(hydroxybutyrate)‐Based Photocurable Resin with Potential Application in Stereolithography

A bio‐based polymeric ink for stereolithography developed through a two‐step solvent‐free process is herein proposed. Specifically, low‐molecular‐weight poly(hydroxybutyrate) (PHB)‐diol oligomers are prepared via molten transesterification of bacterial PHB with 1,4‐butanediol. Transesterification conditions such as diol concentration, catalyst amount, and reaction time are studied for optimizing the final oligomers’ molecular weight and structural features. In the second step, the oligomeric hydroxyl terminals are converted into methacrylate moieties through a solvent‐free end‐capping reaction and diluted in propylene carbonate in order to obtain a photo‐polymerizable ink with suitable viscosity. The ink is UV‐cured, and the obtained material properties are investigated by FT‐IR and differential scanning calorimetry measurements. The proposed method provides a valuable and environmentally friendly alternative to currently available synthetic routes, overcoming their typical disadvantages related to the used solvents and harsh conditions. Moreover, it opens up a sustainable route for converting polyesters into functionalized oligomeric derivatives, which can potentially find application in 3D printing of customized biomedical devices. This study presents a facile solvent‐free method to produce UV‐curable ink based on high molecular weight poly(hydroxybutyrate) that can find potential application in 3D printing by vat‐polymerization technology.