Additive Manufacture of Dynamic Thiol–ene Networks Incorporating Anhydride-Derived Reversible Thioester Links

A photoprintable dynamic thiol–ene resin was developed based on commercially available anhydride, thiol, and ene monomers. The dynamic chemistry chosen for this study relied on the thermal reversibility of the in situ generated thioester-anhydride links. The resin’s rheological and curing properties were optimized to enable 3D printing using the masked stereolithography (MSLA) technique. To achieve a desirable depth of cure of 200 μm, a combination of radical photoinitiator (BAPO) and inhibitor (pyrogallol) were used at a weight ratio of 0.5 to 0.05, resulting in more than 90% thiol–ene conversion within 12 s curing time. In a series of stress relaxation and creep experiments, the dynamic reversible exchange was characterized and yielded rapid exchange rates ranging from minutes to seconds at temperatures of 80–140 °C. Little to no exchange was observed at temperatures below 60 °C. Various 3D geometries were 3D printed, and the printed objects were shown to be reconfigurable above 80 °C and depolymerizable at or above 120 °C. By deactivation of the exchange catalyst (DMAP), the stimuli responsiveness was demonstrated to be erasable, allowing for a significant shift in the actuation threshold. These highly enabling features of the dynamic chemistry open up new possibilities in the field of shape memory and 4D printable functional materials.