Polar-Functionalized, Crosslinkable, Self-Healing, and Photoresponsive Polyolefins

The nonpolar nature of polyolefins is one of their biggest limitations. Now, an efficient route to generate polar-functionalized, crosslinkable, self-healing, photoresponsive polyolefins with thermoplastic, elastomeric, and thermosetting properties is reported. Tunable amounts of carboxylic acid and a cyclic comonomer are installed onto polyolefins by palladium-catalyzed terpolymerization reactions. The incorporated carboxylic acid unit can alter the surface properties of polyolefins. The subsequently introduced Fe3+/citric acid combination induces dynamic crosslinking and enables self-healing. Under UV light irradiation, citric acid reduces Fe3+ to Fe2+ and decreases the crosslinking density. The Fe2+ moiety can be easily oxidized back to Fe3+, making the process reversible at the expense of citric acid. The incorporated cyclic comonomer modulates the crystallinity of polyolefins, provides elastic properties, and installs carbon-carbon double bonds for sulfur-induced vulcanization.