3D Printing of Poly(methyl methacrylate) by Interfacial Photopolymerization

Established light-based additive manufacturing (AM) processes, such as vat polymerization, utilize nonrecyclable thermoset polymers, posing sustainability concerns. This work presents a method for circular photopolymerization three-dimensional (3D) printing of thermoplastic parts, addressing the demand for low-waste production of complex, high-resolution polymer parts. This is achieved through interfacial photopolymerization (IPP), where linear polymer chains form layerwise into entangled networks at the interface between the immiscible organic and aqueous phases. IPP has previously been demonstrated, but with limited chemistries and without 3D structural control. We demonstrate herein a chemistry to form poly(methyl methacrylate) (PMMA) by IPP and a process for multilayer fabrication in a modified commercial projector-based 3D printer. Layer resolution and stability are enhanced using light-absorbing dye and a water-soluble polyethylene glycol (PEG) binder. Postprocessing with controlled air drying and thermal treatment with PEG infiltration preserves geometry and reduces cracking. The resulting composite comprises 75% PEG and 25% PMMA with mechanical properties akin to those of polymer foams. Circularity of the IPP-PMMA process is demonstrated by recycling and reincorporating printed objects across several cycles without significant degradation of properties. Although enhancements in geometric fidelity and mechanical properties are necessary, IPP 3D printing enables, for the first time, digital light processing of recyclable thermoplastic PMMA and PEG-based parts.