Synthesis of Tough and Fluorescent Self-Healing Elastomers by Scandium-Catalyzed Terpolymerization of Pyrenylethenylstyrene, Ethylene, and Anisylpropylene

The synthesis of fluorescent self-healing polymers by the incorporation of a fluorophore-containing olefin into a polyolefin backbone through catalyst-controlled multicomponent copolymerization is of fundamental interest and practical importance, but such an approach has remained unexplored to date. Herein, we report for the first time the synthesis of tough and fluorescent self-healing polymers by sequence-controlled terpolymerization of 4-[2-(1-pyrenyl)ethenyl]styrene (Pyr), ethylene (E), and anisylpropylene (AP) using a sterically demanding half-sandwich scandium catalyst. The resulting terpolymers consisted of relatively long alternating E-alt-AP sequences, isolated Pyr units, and short E-E blocks, which exhibited excellent tensile strength, remarkable self-healability, and high fluorescence quantum yield. The excellent mechanical and self-healing properties could be attributed to the nanophase separation of the crystalline E-E segments and the hard Pyr aggregates from a flexible E-alt-AP segment matrix, in which the Pyr units not only served as an efficient fluorophore but also played an important role in forming nanodomains and enhancing the polymer mobility. Furthermore, the styrenyl C═C bond of the Pyr unit in the terpolymers could undergo [2 + 2] cycloaddition under photoirradiation, which thus enabled the fabrication of a self-healable fluorescent two-dimensional image on a terpolymer film through photolithography. This work offers an unprecedented efficient protocol for the synthesis of a brand-new family of fluorescent self-healing materials, showcasing the high potential of catalyst-controlled sequence-regular copolymerization of different olefins for the creation of novel functional polymers.