Design and Performance of 3D-Printed Hybrid Polymers Exhibiting Shape Memory and Self-Healing via Acrylate–Epoxy–Thiol–Ene Chemistry

This study presents a novel strategy for designing photocurable resins tailored for the additive manufacturing of smart thermoset materials. A quaternary formulation was developed by integrating bis(2-methacryloyl)oxyethyl disulfide (DADS) with an epoxy/thiol-ene system (ETES) composed of diglycidyl ether of bisphenol A (EP), pentaerythritol tetrakis(3-mercaptopropionate) (PTMP), and 4,4′-methylenebis(N,N-diallylaniline) (ACA4). This unique combination enables the simultaneous activation of four polymerization mechanisms: radical photopolymerization, thiol-ene coupling, thiol-Michael addition, and anionic ring-opening, within a single resin matrix. A key innovation lies in the exothermic nature of DADS photopolymerization, which initiates and sustains ETES curing at room temperature, enabling 3D printing without thermal assistance. This represents a significant advancement over conventional systems that require elevated temperatures or post-curing steps. The resulting hybrid poly(acrylate–co-ether–co-thioether) network exhibits enhanced mechanical integrity, shape memory behavior, and intrinsic self-healing capabilities. Dynamic Mechanical Analysis revealed a shape fixity and recovery of 93%, while self-healing tests demonstrated a 94% recovery of viscoelastic properties, as evidenced by near-overlapping storage modulus curves compared to a reference sample. This integrated approach broadens the design space for multifunctional photopolymers and establishes a versatile platform for advanced applications in soft robotics, biomedical devices, and sustainable manufacturing.