Versatile acrylate-epoxy hybrid formulations are becoming widespread in photo/thermal dual-processing scenarios, especially in 3D printing applications. Usually, parts are printed in a stereolithography or digital light processing (DLP) 3D printer, after which a thermal treatment would bestow the final material with superior mechanical properties. We report the successful formulation of such a hybrid system, consisting of a commercial 3D printing acrylate resin modified by an epoxy-anhydride mixture. In the final polymeric network, we observed segregation of an epoxy-rich phase as nano-domains, similar to what was observed in a previous work. However, in the current work, we show the effectiveness of a coupling agent added to the formulation to mitigate this segregation for when such phase separation is undesired. The hybrid materials showed significant improvement of Young's modulus over the neat acrylate. Once the flexible, partially-cured material was printed with a minimal number of layers, it could be molded into a complex form and thermally cured. Temporary shapes were readily programmable on this final material, with easy shape recovery under mild temperatures. Inspired by repairable 3D printed materials described recently, we manufactured a large object by printing its two halves, and then joined them covalently at the thermal cure stage with an apparently seamless union.
Keywords: digital light processing; dual-curing; interpenetrating polymer network.