Cyanate-Ester, Maleimide/Bismaleimide and Benzoxazine Photopolymers for Vat Photopolymerisation: Photo-Triggered Networks, Thermal Post-Cure and Qualification

Cyanate-ester, maleimide/bismaleimide and benzoxazine formulations extend vat photopolymerisation toward high-temperature thermosets, but they do not share one cure mechanism. Primary demonstrations include Hot Lithography of an unfilled cyanate-ester formulation through photo-induced catalytic polytrimerisation, stereolithography of a methacrylate-functionalised bismaleimide oligomer, and projection micro-stereolithography of photocurable benzoxazine precursors followed by thermal ring-opening polymerisation. In these routes, light may create the final network, activate a latent catalyst or only establish a shape-retaining intermediate. Post-cure temperature can increase conversion and properties while also causing diffusion, overgrowth, oxidation, warpage, cracking or volatile loss. Reported high glass-transition and decomposition temperatures remain formulation-, conversion-, method- and specimen-specific. This review defines an identity gate, stage-resolved conversion controls, vat-stability requirements and a qualification chain for geometry, residuals, mechanical performance, thermal service, dielectric claims and ageing.

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