Self‐Healable Hydrophobic Material Based on Anthracenyl Functionalized Fluorous Block Copolymers via Reversible Addition‐Fragmentation Chain Transfer Polymerization and Rapid Diels–Alder Reaction

Abstract Recently, among the available approaches to develop self‐healable materials, 1,2,4‐triazoline‐3,5‐dione (TAD)‐based Diels–Alder (DA) chemistry has gained tremendous attention, becuase this DA reaction is very rapid under ambient conditions. This study delineates developing a self‐healing hydrophobic fluorinated polymer utilizing dynamic and rapid TAD‐DA chemistry. For this purpose, block copolymers of 2‐hydroxyethyl methacrylate (HEMA) and 2,2,2‐trifluoroethylmethacrylate (TFEMA) are prepared via reversible addition‐fragmentation chain transfer polymerization. Subsequently, the pendant hydroxyl groups of the HEMA repeat units are modified with anthracenyl functionality via esterification with 9‐anthracenecarboxylic acid. The tailor‐made polymer‐bearing anthracenyl pendants are subsequently crosslinked via a rapid DA reaction using a bifunctional TAD derivative at room temperature (r.t.). Differential scanning calorimetry (DSC) analysis is performed to interpret the thermoreversible behavior of the TAD‐derived DA polymer. The self‐healing characteristics of this TAD‐derived DA conjugate are studied by monitoring the healing of a notched surface via AFM analysis. Interestingly, the TAD conjugated fluoropolymers are hydrophobic, as evidenced by the water contact angle analysis. Such TAD‐derived DA fluoropolymer conjugates with remarkable hydrophobic characteristics and excellent self‐healing features can pave a new direction in the potential materials for specialty paints, coatings, and adhesives.