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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. [ABSTRACT FROM AUTHOR]

The terpolymerization of a non‐polar olefin (such as ethylene) and two different polar functional olefins in a controlled fashion is of great interest and importance but has hardly been explored to date. We report for the first time the terpolymerization of ethylene (E) and two different methoxyaryl‐substituted propylenes (AR1P=hexylanisyl propylene; AR2P=methoxynaphthyl propylene or methoxypyrenyl propylene) by a half‐sandwich scandium catalyst. The terpolymerization took place in a sequence‐controlled fashion, affording unique multi‐block copolymers composed of two different ethylene‐alt‐methoxyarylpropylene sequences E‐alt‐AR1P (soft segments) and E‐alt‐AR2P (hard segments) and relatively short ethylene–ethylene (EE) blocks (crystalline segments). The terpolymers exhibited excellent elasticity and unprecedented self‐healing as a result of microphase separation of nanodomains of the crystalline EE segments and the hard amorphous E‐alt‐AR2P segments from a very flexible E‐alt‐AR1P matrix, demonstrating unique synergy of the three different components. [ABSTRACT FROM AUTHOR]