Rapidly Self‐Healable and Melt‐Extrudable Polyethylene Reprocessable Network Enabled with Dialkylamino Disulfide Dynamic Chemistry

Catalyst‐free, radical‐based reactive processing is used to transform low‐density polyethylene (LDPE) into polyethylene covalent adaptable networks (PE CANs) using a dialkylamino disulfide crosslinker, BiTEMPS methacrylate (BTMA). Two versions of BTMA are used, BTMA‐S2, with nearly exclusively disulfide bridges, and BTMA‐Sn, with a mixture of oligosulfide bridges, to produce S2 PE CAN and Sn PE CAN, respectively. The two PE CANs exhibit identical crosslink densities, but the S2 PE CAN manifests faster stress relaxation, with average relaxation times ∼4.5 times shorter than those of Sn PE CAN over a 130 to 160 °C temperature range. The more rapid dynamics of the S2 PE CAN translate into a shorter compression‐molding reprocessing time at 160 °C of only 5 min (vs 30 min for the Sn PE CAN) to achieve full recovery of crosslink density. Both PE CANs are melt‐extrudable and exhibit full recovery within experimental uncertainty of crosslink density after extrusion. Both PE CANs are self‐healable, with a crack fully repaired and the original tensile properties restored after 30 min for the S2 PE CAN or 60 min for the Sn PE CAN at a temperature slightly above the LDPE melting point and without the assistance of external forces. LDPE is upcycled into polyethylene covalent adaptable networks (PE CANs) via simple, catalyst‐free, radical‐based reactive processing with dynamic crosslinker BTMA. The nearly exclusively disulfide‐based BTMA exhibits fast dynamic chemistry, rendering the PE CANs rapidly reprocessable, melt‐extrudable, and self‐healable, with full property recovery after self‐healing achieved slightly above the LDPE melting temperature within 60 min.