Random bi-functional copolymers bearing fluorinated units and sol-gel forming units were prepared and used together with silica particles in a one-pot process for preparing superamphiphobic coatings. The copolymers P(FOEA-r-IPSMA) were prepared by atom transfer radical polymerization (ATRP) of 2-(perfluorooctyl)ethyl acrylate (FOEA) and 3-(triisopropyloxy)silylpropyl methacrylate (IPSMA). The uniform silica particles were prepared using a modified Stöber process. Stirring P(FOEA-r-IPSMA), silica, water, and HCl together with substrates triggered the sol-gel reactions of the IPSMA units. These involved first the hydrolysis of IPSMA to yield silanol groups and then the condensation of the IPSMA silanol groups among themselves, and with silanol groups on silica or glass surfaces or with hydroxyl groups on cotton or filter paper. At optimized mass ratios of P(FOEA-r-IPSMA) to silica, the resultant coatings consisted of lightly covered silica particles that were embedded in a crosslinked P(FOEA-r-IPSMA) film. By optimizing the molar ratio between FOEA and IPSMA in P(FOEA-r-IPSMA), the rough particulate coatings on cotton, filter paper, and glass plates exhibited superamphiphobicity. More importantly, the particulate coatings were resistant to solvent extraction and NaOH etching.

Reported herein is the preparation of poly((glycidyl methacrylate)-co-(ethylene glycol dimethacrylate)) raspberry-like colloidal particles (also denoted as RPs) bearing micro-/nano-scale surface roughness and the fabrication of superhydrophobic films with tunable adhesion derived from the RPs after their fluorination. The RPs were prepared via the one-pot dispersion polymerization of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA). The size and the surface roughness of the RPs can be readily tuned by adjusting the polymerization parameters, including the temperature, the feed monomer mole ratio, the initiator concentration, and so on. A possible mechanism of the formation of RPs was proposed according to the morphological evolution observed during the polymerization process as monitored via transmission electron microscopy (TEM), scanning electron microscopy (SEM), and size variation as evaluated with dynamic light scattering (DLS) measurements. Fluorinated RPs (also denoted as FRPs) with various fluorination degrees were further prepared by reaction between the epoxy groups of the RPs and the thiol group of perfluorodecanethiol (PFDT). The raspberry-like morphology of the FRPs was maintained as confirmed via SEM observation. By only changing the surface chemistry rather than the roughness, superhydrophobic films with tunable superhydrophobic properties capable of mimicking wettabilities ranging from those of lotus leaves to those of rose petals were easily prepared by dropcasting dispersions of FRPs onto glass substrates. † Electronic supplementary information (ESI) available. See

Many strategies have been developed to prepare superamphiphobic fabrics that strongly repel water‐ and oil‐borne contaminants and etchants. However, the common drawback in these reported strategies is the use of organic solvents, which should be eliminated or reduced for practical applications. In this paper, the diblock copolymer of poly(2‐perfluorooctylethyl acrylate)‐block‐poly(glycidyl methacrylate‐ radom‐methoxy oligoethyleneglycolyl methacrylate) [PFOEA‐b‐P(GMA‐r‐mOEGMA)]is synthesized via atom transfer radical polymerization and used to coat cotton and poly(ethylene terphthalate) fabrics from an aqueous process. It is found that fabrics with tunable and robust wettablity can be prepared from copolymer solution at different concentrations. For example, fabrics coated at a copolymer solution concentration of 22.8 mg mL‐1 are superamphiphobic. This process of current stratey is environment‐friendly, simple, and reproducible, and may find commercial applications.