Development of a quaternary photocurable system for 3D printing based on the addition of acrylate monomers to an epoxy/thiol-Ene system

The exothermic nature of acrylate photopolymerizations enables room temperature 3D printing of a quaternary formulation that incorporates an acrylate monomer, and an epoxy/thiol-ene system (ETES). The latter comprises an epoxy monomer, a multifunctional thiol and a tetraallyl functionalized ditertiary amine curing agent. Pristine ETES necessitates temperatures of 85–95 °C for curing. Several mechanisms operate simultaneously during this process: homopolymerization of acrylates, thiol-acrylate photopolymerization, thiol-ene photopolymerization between the double bonds of curing agent and the multifunctional thiol, the Michael addition between thiolates derived from ETES and the double bonds of acrylates, and the anionic polymerization of the epoxy resin via the tertiary amine groups. To optimize the quaternary formulations for printing, parameters, such as reactivity, exothermicity, and viscosity, was explored. Subsequently, the thermal and viscoelastic properties of the printed cross-linked polymers derived from these formulations were analyzed using Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA) and Thermogravimetric Analysis (TGA). The polymers derived from quaternary formulations exhibited lower crosslinked density compared to those obtained from the pristine acrylates. This reduction in crosslink density contributes to the improved toughness of the hybrid polymers.