Xolography for the Production of Polymeric Multimaterials

Abstract Three‐dimensional (3D) printed multimaterials have quickly grown in interest as researchers aim to mimic the material chemistry and geometric complexity of natural materials. While some exceptional multimaterial 3D printing systems have been developed, there is still a shortfall in the scope and production of these materials. More recently, the introduction of xolography as a single‐step, auxiliary‐free additive manufacturing approach has enabled rapid production of materials with geometries inaccessible via other additive manufacturing techniques. However, previous systems required resins with high transparency for effective material formation, and multimaterial formation has not been demonstrated. In this work, reversible deactivation radical polymerization is used and resin composition, viscosity, and processing parameters are explored to develop new resins capable of application to visible light‐mediated xolography. After optimization, non‐transparent resins containing thiocarbonylthio species are applied to xolography to manufacture geometrically complex, auxiliary‐free materials. The resulting 3D printed polymer network materials can be functionalized via the embedded thiocarbonylthio moieties to impart new functionality to the printed materials. Finally, the unique 3D printing capabilities of xolography are demonstrated to manufacture multimaterials featuring chemically disparate domains with high 3D‐spatial control. This two‐step overprinting approach is operationally simple and provides a new avenue for manufacturing polymeric multimaterials via 3D printing.