Poly(β-amino ester) Photoresins for Projection Micro-Stereolithography: Aza-Michael Macromer Identity, Hydrolytic Degradation, Surface-to-Bulk Transition, Resolution and Qualification

PBAE-diacrylate photoresins offer a chemistry-controlled route to hydrolytically degradable micro-stereolithography objects. A systematic primary study synthesised eleven macromers from PEG or butane diacrylates and primary amines or hydrazides under solvent- and catalyst-free aza-Michael conditions. The reported networks ranged from complete mass loss in 90 min to minimal loss at 45 days under accelerated conditions, while all produced 55 µm patterned features and selected formulations printed complex objects with 45 µm features. Hydrophilic networks behaved as bulk-degrading systems; hydrophobic networks could appear surface-like before water penetration caused bulk degradation. These results do not establish universal formulations, surface degradation, biodegradability, biocompatibility or environmental superiority. Qualification must close macromer distribution, residual starting diacrylate, vat kinetics, spatial cure, water transport, product identity and retained performance.

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