The Polymer Society of Korea

Abstract

Sulfur-rich polymers (SRPs) represent a pivotal material class for sustainable manufacturing due to their unique dynamic properties. We report a 4D printing framework utilizing SRP composites derived from industrial waste elecmental sulfur. By incorporating magnetic fillers (Fe₃O₄ or CrO₂) into poly(phenylene polysulfide) networks (PSNs), we achieved solvent-free hot-melt extrusion 3D printing of these composites, leveraged by dynamic S-S bond exchange and shear-thinning behavior. These printed structures facilitate modular assembly, programmable shape-morphing, and full recyclability. Notably, PSN-CrO₂ composites enable NIR-triggered magnetic control through Curie transition-mediated demagnetization. We showcased this sulfur-rich platform via untethered soft robots with multi-responsive locomotion and intelligent stir bars for on-demand catalyst release. Our work establishes SRPs as a versatile, sustainable foundation for next-generation intelligent soft systems.