Simultaneous Color‐ and Dose‐Controlled Thiol–Ene Resins for Multimodulus 3D Printing with Programmable Interfacial Gradients

Abstract

Drawing inspiration from nature's own intricate designs, synthetic multimaterial structures have the potential to offer properties and functionality that exceed those of the individual components. However, several contemporary hurdles, from a lack of efficient chemistries to processing constraints, preclude the rapid and precise manufacturing of such materials. Herein, the development of a photocurable resin comprising color‐selective initiators is reported, triggering disparate polymerization mechanisms between acrylate and thiol functionality. Exposure of the resin to UV light (365 nm) leads to the formation of a rigid, highly crosslinked network via a radical chain‐growth mechanism, while violet light (405 nm) forms a soft, lightly crosslinked network via an anionic step‐growth mechanism. The efficient photocurable resin is employed in multicolor digital light processing 3D printing to provide structures with moduli spanning over two orders of magnitude. Furthermore, local intensity (i.e., grayscale) control enables the formation of programmable stiffness gradients with ≈150× change in modulus occurring across sharp (≈200 µm) and shallow (≈9 mm) interfaces, mimetic of the human knee entheses and squid beaks, respectively. This study provides composition–processing–property relationships to inform advanced manufacturing of next‐generation multimaterial objects having a myriad of applications from healthcare to education.