Orthogonal photoreactions provide a unique way to locally and independently control (thermo)mechanical properties and functionality of polymer networks simply by choice of the wavelength. Herein, a library of acrylate functional coumarin monomers is synthesized, which are cured by sequence-dependent wavelength orthogonality. In the presence of a long wavelength absorbing photoinitiator, the monomers undergo rapid curing by visible light induced radical chain growth polymerization. Subsequent irradiation with light in the UV-A region selectively initiates the [2+2] photocycloaddition of the coumarin chromophores, which is confirmed by FTIR and UV-vis experiments. Through a well-targeted design, acrylate-based and thiol-acrylate resin formulations are prepared, whose fast curing rate, low viscosity, and prolonged storage stability enable the one-step fabrication of multi-material structures by digital light processing (DLP) 3D printing. By using a dual-wavelength printer, which operates at two different wavelengths (405 and 365 nm), objects comprising soft (ε = 22%, σ = 7.5 MPa) and stiff (ε = 2%, σ = 8.3 MPa) domains are printed with a single resin vat. Along with tensile properties, the wavelength selective change in the network structure features a local control of the glass transition temperature (ΔTg = 17 °C) in the 3D-printed objects. Soft active devices are fabricated by dual-wavelength DLP 3D printing, with distinct domains having a higher Tg and the local programming of multi shapes is demonstrated.
Keywords: coumarin; multi-material properties; orthogonal photoreactions; soft active devices; vat photopolymerization 3D-printing.
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