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The development of renewable vinyl-based photopolymer resins offers a promising solution to reducing the environmental impact associated with 3D printed materials. This study introduces a bifunctional lipoate cross-linker containing a dynamic disulfide bond, which is combined with acrylic monomers ( n -butyl acrylate) and conventional photoinitiators to develop photopolymer resins that are compatible with commercial stereolithography 3D printing. The incorporation of disulfide bonds within the polymer network's backbone imparts the 3D printed objects with self-healing capabilities and complete degradability. Remarkably, the degraded resin can be fully recycled and reused for high-resolution reprinting of complex structures while preserving mechanical properties that are comparable to the original material. This proof-of-concept study not only presents a sustainable strategy for advancing acrylate-based 3D printing materials, but also introduces a novel approach for fabricating fully recyclable 3D-printed structures. This method paves the way for reducing the environmental impact while enhancing material reusability, offering significant potential for the development of eco-friendly additive manufacturing.

We report a facile benchtop process for the synthesis of cross-linked polymeric nanoparticles by exploiting wavelength-selective photochemistry to perform orthogonal photoinduced polymerization-induced self-assembly (Photo-PISA) and photo-crosslinking processes. We first established that the water-soluble photocatalyst, zinc meso-tetra( N -methyl-4-pyridyl) porphine tetrachloride (ZnTMPyP) could activate the aqueous PET-RAFT dispersion polymerization of hydroxypropyl methacrylate (HPMA). This photo-PISA process could be conducted under low energy red light (λ max = 595 nm, 10.2 mW/cm 2 ) and without deoxygenation due to the action of the singlet oxygen quencher, biotin (vitamin B 7 ), which allowed for the synthesis of a range of nanoparticle morphologies (spheres, worms, and vesicles) directly in 96-well plates. To perform wavelength selective nanoparticle cross-linking, we added the photoresponsive monomer, 7-[4-(trifluoromethyl)coumarin] methacrylamide (TCMAm) as a comonomer without inhibiting the evolution of the nanoparticle morphology. Importantly, under red light, exclusive activation of the photo-PISA process occurs, with no evidence of TCMAm dimerization under these conditions. Subsequent switching to a UV source (λ max = 365 nm, 10.2 mW/cm 2 ) resulted in rapid cross-linking of the polymer chains, allowing for retention of the nanoparticle morphology in organic solvents. This facile synthesis of cross-linked spheres, worms, and vesicles demonstrates the utility of orthogonal light-mediated chemistry for performing decoupled wavelength selective chemical processes.

A novel and facile method, involving enzymatic monomer synthesis and a photocontrolled polymerization technique, has been successfully employed for the preparation of high-order multiblock copolymers. New acrylate monomers were synthesized via enzymatic transacylation between an activated monomer, i.e., 2,2,2-trifluoroethyl acrylate (TFEA), and various functional alcohols. These synthesized monomers were successfully polymerized without further purification via photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization under low energy blue LED light (4.8 W) in the presence of an iridium-based photoredox catalyst ( fac -[Ir(ppy) 3 ]). In this condition, PET-RAFT allows us to achieve high monomer conversion (∼100%) with excellent integrity of the end group (>80%). Different multiblock (co)polymers, including poly(hexyl acrylate) pentablock homopolymer, poly(methyl acylate- b -ethyl acrylate- b - n -propyl acrylate- b-n -butyl acrylate- b - n -pentyl acrylate) pentablock copolymer, and poly(3-oxobutyl acrylate- b -methyl acrylate- b -3-(trimethylsilyl)prop-2-yn-1-yl acrylate) triblock copolymer containing functional groups were rapidly prepared via sequential addition of monomers without purification steps.