Photocurable Vanillin-Derived Hybrid Methacrylate Resins with Tunable Properties for High-Resolution Light-Assisted 3D Printing

This work reports the development of photocurable hybrid resins based on methacrylated vanillin (MV) and glycidyl methacrylate-functionalized poly(ε-caprolactone) (PCL-GMA) for high-resolution light-assisted 3D printing. FTIR and 1H NMR analyses confirmed successful methacrylation of vanillin and methacrylate end-group incorporation into PCL–GMA, ensuring efficient photopolymerization. Systematic variation of MV/PCL ratios enabled precise control over resin behavior. Cure-depth studies showed that increasing MV content somewhat enhanced photoreactivity. Notably, rheological measurements revealed low viscosities suitable for light-assisted 3D printing, decreasing from 1.55 Pa·s at low MV to 0.10 Pa·s in the MV: PEG system. The 3D-printed specimens exhibited excellent dimensional fidelity, with dimensional errors of 2–3% for cylindrical parts and only 1.17% in height and 1.21% in width for porous diamond lattices. TGA indicated increased thermal stability with higher MV incorporation, while mechanical testing showed significant improvements in modulus and compressive strength across the MV-rich formulations. Taken together, MV/PCL hybrid resins constitute a versatile, low-error, and biocompatible platform for precision liquid crystal display (LCD) based fabrication.