Making Polyisoprene Self‐Healable through Microstructure Regulation by Rare‐Earth Catalysts

The creation of self-healing polymers from commodity olefins is of great interest and importance but has remained a challenge to date. We report here for the first time the synthesis of self-healing polymers by catalyst-controlled polymerization of a simple commodity diene, isoprene. We found that polyisoprenes having an appropriate mixture (ca. 70/30) of 3,4- and cis-1,4-microstructures synthesized by using a half-sandwich scandium catalyst could act as excellent self-healing elastomers without any external intervention. The unprecedented self-healability could be ascribed to nanoscale heterogeneities formed by microphase separation of the relatively hard 3,4-segments from a flexible cis-1,4-segment matrix. The hydrogenated polyisoprenes (without C=C bonds) with the analogous microstructures also exhibited excellent mechanical and self-healing properties, further demonstrating that even simple polyolefins can be made self-healable if the microstructures are appropriately regulated.