Phenolic, Lignin-Derived and Bio-Aromatic Photopolymers for Vat Photopolymerisation: Native Polycondensation, (Meth)acrylate Functionalisation, Optical Attenuation, Volatile Evolution and Qualification

Phenolic and lignin-derived materials enter vat photopolymerisation through several chemically different routes. Primary studies demonstrate photoacid-triggered polycondensation of a pure novolak formulation by Hot Lithography without a binder or matrix polymer; stereolithography of eugenol-, guaiacol- and vanillyl-alcohol-derived (meth)acrylates; direct laser writing of vanillin acrylate networks; Hot Lithography of methacrylated lignin containing more than 30% lignin without reactive diluent; and low-level lignin reinforcement of a methacrylate SLA resin. The native phenolic route produces water and can form bubbles if reaction and evaporation overlap above the stable process window. Functionalised bio-aromatics instead undergo radical chain growth, so their cured network is not a phenoplast even when the precursor originated from a phenol. Lignin additionally introduces feedstock heterogeneity, chromophores, radical activity, aggregation and uncertain functionalisation. Renewable origin does not establish biodegradability, low hazard, low migration, reduced climate impact or chemical recyclability. This review separates chemical identity, biogenic-carbon accounting, optical processability, conversion, volatile balance, extractables, reaction-to-fire evidence and final duty.

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