Advanced Polyolefins: Ethylene, Styrene, and Butadiene Terpolymers with Toughness, Self-Healing, and Enhanced Adhesion via Bifunctional Dual-Site Polymerization

Polyethylene is one of the most widely used plastic materials, and its recycling efficiency and properties can be greatly improved by copolymerizing ethylene with α-olefins, styrene, and/or conjugated dienes. Although such copolymerization is challenging, advancements in organometallic chemistry have allowed for the straightforward and cost-effective production of highly functional polyolefins. We develop a new polyolefin combining ethylene, styrene, and butadiene by applying the novel bifunctional dual-site polymerization method, wherein two simultaneous polymerization pathways exchange growing polymer chains to form terpolymers. The polymer strength, toughness, and elongation depend on monomer block chain lengths and polymerization conditions. The catalyst design determines the polyolefin structures, ranging from multiblock to random configurations. Moreover, the precisely controlled terpolymers exhibit excellent puncture resistance and self-healing abilities. Owing to the presence of ethylene and butadiene, the terpolymer thermally bonds with polyethylene and natural rubber to show unexpected adhesiveness with polypropylene. These enhanced properties inspire new adhesion technologies, promoting the mechanical recycling of waste polyolefins. The method can be widely applied to plastic–rubber composites.