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 H-1 NMR spectroscopy, size exclusion chromatography (SEC), and FTIR analyses. Interestingly, compared to the parent fluoro copolymer with a water contact angle (WCA) of approximate to 101 degrees, the DA modification with hydrophobic POSS molecules significantly improved the surface hydrophobicity of the modified DA polymers leading to a WCA of 135 degrees. 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.

Automated summary

This study reports the preparation of a tailor-made copolymer of FMA and TFEMA via RAFT polymerization, followed by modification of the furfuryl groups through DA reaction using different POSS-M contents to yield hydrophobic fluorinated copolymers with improved surface hydrophobicity and self-healing ability. The modified DA fluoropolymers showed a significant increase in water contact angle from approximately 101 degrees to 135 degrees, making them promising materials for specialty paints and coatings.