Self-healing hydrophobic POSS-functionalized fluorinated copolymers via RAFT polymerization and dynamic Diels–Alder reaction

This investigation reports the preparation of a tailor-made copolymer of furfuryl methacrylate (FMA) and trifluoroethyl methacrylate (TFEMA) via reversible addition–fragmentation chain transfer (RAFT) polymerization. The furfuryl groups of the copolymer were modified via the Diels–Alder (DA) reaction using different molar content of polyhedral oligomeric silsesquioxane maleimide (POSS-M), yielding hydrophobic fluorinated copolymers with varying POSS content. The chemical composition, molar mass, and extent of grafting of POSS moieties were measured by 1H NMR spectroscopy, size exclusion chromatography (SEC), and FTIR analyses. Interestingly, compared to the parent fluoro copolymer with a water contact angle (WCA) of ≈101°, the DA modification with hydrophobic POSS molecules significantly improved the surface hydrophobicity of the modified DA polymers leading to a WCA of 135°. Moreover, as evidenced by differential scanning calorimetry (DSC), atomic force microscopy (AFM), and optical microscopy analyses, the thermoreversible behaviour of the dynamic covalent furan-POSS-M linkages facilitated the self-healing ability of these functional hybrid polymethacrylates. The developed self-healing hydrophobic POSS modified DA fluoropolymers are interesting materials that can find promising applications as specialty paints and coatings.