Creation of polymeric nanostructures by living coordination block copolymerization of allene derivatives with fluoroalkyl substituents under polymerization-induced self-assembly conditions and their application to superhydrophobic surfaces

The spontaneous formation, via living coordination block copolymerization, of polymeric nanostructures that possess outer fluorous segments and their application as transparent superhydrophobic coatings are described. The block copolymers (BCPs) consisting of both fluorous and hydrophobic segments were prepared via the π-allylnickel-catalyzed living coordination block copolymerization of a fluoroalkyl-substituted allene, 1-(1H,1H,2H,2H-heptadecafluorodecyoxy)-2,3-butadiene, and a hydrophobic allene, phenoxyallene, in a selective fluorous solvent, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane, via a polymerization-induced self-assembly (PISA) process. It was found that nanostructured materials were produced during the block copolymerization whose morphologies changed from spherical micelles to network micelles by reducing the length of the fluoroalkyl-containing (i.e., the solvophilic) segments. An optically transparent superhydrophobic surface with a static contact angle for a water droplet over 150° and a sliding angle below 5° was effectively obtained simply by dip-coating a glass substrate into the suspension of the resulting nanostructured block copolymers under appropriate conditions.