Self‐Healing Polycaprolactone Networks through Thermo‐Induced Reversible Disulfide Bond Formation

Abstract Polycaprolactone (PCL) networks with disulfide bonds are synthesized through a thiol‐ene “click” reaction. The PCL networks have various functional properties, including self‐healing, shape memory, reprocessability, and degradability. Pronouncedly, a healing efficiency of 92% on the yield strength of the PCL network is obtained after heating for 1 h at 60 °C. Meanwhile, the PCL networks show shape memory property with fixing ratio ( R f ) and recovery ratio ( R r ) at 98% and 95%, respectively. The PCL network still retains good mechanical properties after reprocessing cycles and can be fast‐decomposed through a thiol‐disulfide exchange reaction.