The allylnickel-catalyzed living coordination polymerization of allene derivatives gives well-defined polymers containing various functional groups with controlled sequence and molecular weight. This living polymerization method can also be carried out under the dispersion polymerization conditions in polar protic solvents such as alcohols and water to produce well-defined functional polymer microspheres. Based on these remarkable features, we describe herein the block copolymerization of a perfluoroalkyl-substituted allene and a monofunctional hydrophobic allene or a bifunctional hydrophobic allene in fluorous solvents to produce well-defined polymeric nanostructures through the polymerization-induced self-assembly process (Scheme 1). For example, the living solution polymerization of 2-(perfluorooctyl)ethoxymethylallene (10 equiv.) was carried out by [(π-allyl)NiOCOCF3]2 in a fluorous solvent, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoro-methyl)-pentane, at ambient temperature for 24 h. To the resulting living polymer solution, phenoxyallene (50 equiv.) was subsequently added to conduct the block copolymerization at ambient temperature for additional 12 h. By the progress of the post-polymerization, the polymerization system gradually turned from the transparent solution to suspension to produce nanostructured polymeric materials. The static contact angle of the water (θwater) on the thin layer of the polymer micelles, which was prepared by the drop casting of the copolymer suspension onto a glass substrate, reached 153 degrees, which supported the superhydrophobic nature of the layered polymer micelles (Figure 1).

Superhydrophobic surface nanomaterials viaπ-Allylnickel-catalyzed living coordination block copolymerization of allene derivatives under polymerization-induced self-assembly conditions

ACS Spring Meeting 2021

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