The investigation of biobased systems as photocurable resins for optical 3D printing has attracted great attention in recent years; therefore, novel vanillin acrylate-based resins were designed and investigated. Cross-linked polymers were prepared by radical photopolymerization of vanillin derivatives (vanillin dimethacrylate and vanillin diacrylate) using ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate as photoinitiator. The changes of rheological properties were examined during the curing with ultraviolet/visible irradiation to detect the influences of solvent, photoinitiator, and vanillin derivative on cross-linking rate and network formation. Vanillin diacrylate-based polymers had higher values of yield of insoluble fraction, thermal stability, and better mechanical properties in comparison to vanillin dimethacrylate-based polymers. Moreover, the vanillin diacrylate polymer film showed a significant antimicrobial effect, only a bit weaker than that of chitosan film. Thermal and mechanical properties of vanillin acrylate-based polymers were comparable with those of commercial petroleum-derived materials used in optical 3D printing. Also, vanillin diacrylate proved to be well-suited for optical printing as was demonstrated by employing direct laser writing 3D lithography and microtransfer molding techniques.
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