Recyclable Polyolefin‐Like Polymers With Backbone Disulfide and O‐Thiocarbamate Linkages

ABSTRACT Introducing cleavable linkages into polyolefin backbones offers a promising route toward chemically recyclable polyolefin‐like materials. Disulfide linkages are particularly attractive because they undergo reversible cleavage and re‐formation under mild redox conditions, yet remain rarely explored in this context. Herein, this work reports redox‐recyclable polyolefin‐like polymers prepared by direct oxidative coupling of aminolysis‐generated thiol‐terminated macromonomers. Bio‐derived diamine‐terminated poly(cyclooctene)s were reacted with five‐membered cyclic dithiocarbonates prepared from CS 2 and epoxides to afford O‐thiocarbamate‐bearing thiol‐terminated macromonomers, which were oxidatively coupled without isolation to yield high‐molecular‐weight polymers containing backbone disulfides. Mild reduction regenerated the thiol‐terminated macromonomers, enabling oxidative repolymerization and recovery of molecular weight. After hydrogenation, the materials retained the orthorhombic crystal packing characteristic of polyethylene and exhibited melting temperatures up to 125°C. A representative polymer showed an elongation at break of 495%, a Young's modulus of 368.8 MPa, and a toughness of 54.2 MJ m −3 , together with enhanced adhesion and dielectric properties relative to commercial polyolefin references. This work provides a modular route to recyclable and functional polyolefin‐like materials.