Fully Recyclable Pluripotent Networks for 3D Printing Enabled by Dissociative Dynamic Bonds

Additive manufacturing (AM) has risen in popularity due to its ability to produce complex shapes in a material-efficient way. However, to produce objects with advanced properties, complex multimaterial strategies are often employed. This one-polymer-one-property paradigm significantly slows down the application of AM, and in particular of fused deposition modeling (FDM), for manufacturing of functional objects. In this study advantage of pluripotency in materials is taken, i.e., the ability to attain different properties from a single stock, to afford mechanically tunable 3D printed dynamic thermosets (moduli from 2 MPa - 3 GPa, 1500× increase, Stress at break from 2 to 70 MPa, 35× increase). To do so, FDM-compatible CO₂-derived dissociative polymer networks are designed that undergo a dynamic reaction-induced phase-separation (DRIPS). This strategy enables the control of the size of the rigid phase with a simple post-printing thermal treatment, cascading in spatially patterned mechanical properties. This study showcases new directions for the 3D printing communities, with deep implications in soft robotics and compliant mechanics.