•Perfluoropolyether derivatives was applied to fabricate superhydrophobic raspberry particles.•Fine raspberry-like morphology was constructed by Pickering emulsion polymerization.•Effect mechanism of silica charge on the film’s surface structure and fluorine content as well as the wettability was investigated in detail.•The dual structured particulate film exhibited excellent superhydrophobicity and self-cleaning property.A facile synthetic route for perfluoropolyether modified nanocomposite raspberry particles was designed. In this route, perfluoropolyether derivative, rather than the conventional but controversial long-chain perfluoroalkyl compounds, was applied to fabricate superhydrophobic raspberry particles. The fine dual-sized hierarchical surface structure and fluorine content can be tailored simultaneously by adjusting the silica sol charge at Pickering emulsion polymerization step. The superhydrophobic surface with a max contact angle of 156.4° was obtained by simply drop-casting the perfluoropolyether modified raspberry paticles onto glass substrate. Furthermore, the effects of the surface fluorine content, the hierarchical structure and roughness of the raspberry particles on the hydrophobicity were investigated.Monodisperse copolymer/SiO2 raspberry particles were first synthesized through the Pickering emulsion polymerization. PFPE chains were grafted onto the copolymer/SiO2 raspberry particles’ surfaces by a previous step of amine-surface-functionalization. By simple drop-casting the obtained perfluoropolyether modified raspberry particles onto a glass substrate, a fluorinate particulate film with fine dual-sized roughness surface were created. The particulate film maximum water contact angle reached 156.4° and the sliding angle was only 6.0°. By increasing the initial silica charge, the perfluoropolyether modified raspberry particles’ surface roughness and surface fluorine content increased simultaneously. Consequently, the corresponding particulate films surface become rougher and more fluorine enriched, as a result promoting its superhydrophobicity.Download high-res image (207KB)Download full-size image

•Fluorinated polyacrylate/silica nanocomposite particles were prepared.•Surface topography and chemical composition of the films were evaluated.•Transparency of the nanocomposite films was studied.•The film-forming mechanism of the nanocomposite particles was proposed.Fluorinated polyacrylate/silica nanocomposite particles were synthesized by methyl methacrylate (MMA), butyl acrylate (BA) and 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (FA) via in situ miniemulison polymerization. Morphology of nanocomposite particles, surface microstructure, chemical composition, hydrophobicity, transparency and thermal performance of the films were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), water contact angle, Fourier transform infrared spectra (FT-IR), ultraviolet–visible spectroscopy (UV–vis), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TGA) analyses. It is shown that the fluorinated polyacrylate/silica nanocomposite particles present “currunt-bun like” morphology. The hydrophobicity of fluorinated polyacrylate film was increased after incorporation of silica, which was due to the surface enrichment of fluorine and rough surface of the nanocomposite film. Moreover, the fluorinated polyacrylate/silica nanocomposite films exhibited high transparency in visible light range.“Currunt-bun like” PFA/SiO2 nanocomposite particles confer rough surface of the film. Due to the amount and dispersion condition of silica in PFA film, surface roughness and fluorine content at the film surface can be varied.

•Surface composition of fluorinated poly(fluorinated styrene-acrylate)/silica hybrid film was investigated.•The effect of silica content on abrasion performance of the hybrid film was measured.•The hybrid film surface morphology was studied and correlated to silica content.Poly(fluorinated styrene-acrylate)/silica (PFSA/SiO2) nanocomposite latexes with different content of silica were prepared by seeded emulsion polymerization. Chemical composition of the PFSA nanocomposite was evaluated by Fourier transform infrared (FT-IR) spectrometry and energy dispersive spectrometry (EDS) analyses, respectively. Thermal performance of the nanocomposite particles was characterized by differential scanning calorimetry (DSC) and thermogravimetry (TG). Micromorphology of the nanocomposite latex film formed on glass substrate was observed by atomic force microscope (AFM). Furthermore, surface hydrophobicity of the latex film was examined by measurement of water contact angle. The results showed that although only small amount (no more than 1.0 wt% based on the PFSA nanocomposite) of silica contained in the composite, abrasion resistance and thermal properties of the PFSA films were improved significantly. More silica content will cause instability of polymerization. Moreover, dynamic light scattering (DLS) analysis revealed that the presence of silica nanoparticles led to smaller composite particle size as compared with pure PFSA latex particles containing no silica.Poly(fluorinated styrene-acrylate)/silica (PFSA/SiO2) nanocomposite latexes with different content of silica were prepared by seeded emulsion polymerization. Surface morphology and composition of the films were investigated. Abrasion property of the film containing silica was evaluated. The results showed that only small amount (no more than 1.0 wt% based on the PFSA nanocomposite) of silica contained in the composite, abrasion resistance and thermal properties of the PFSA films were improved significantly. The presence of silica nanoparticles led to smaller composite particle size as compared with pure PFSA latex particles containing no silica.

•Fluorine and silicon acrylic latexes were prepared.•Migration behavior of fluorine segment was investigated.•Silicon crosslinking reaction during film formation was studied.•Water resistant ability of fluorosilicone acrylic film was evaluated.A series of fluorine and silicon acrylic latexes have been prepared from acrylic monomers, 2,2,3,4,4,4-hexafluorobutyl acrylate (HFBA) and vinyltriethoxysilane (VTES) via emulsion polymerization. Morphology and particle size distribution were evaluated by transmission electron microscopy (TEM) and dynamic light scattering (DLS) methods. Surface properties of latex films were investigated in terms of ATR-FTIR spectrometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water resistance measurement. It is indicated that fluorine content at the surface of fluorosilicone acrylic film decreased as the film forming temperature was increased. A high temperature favored silicon condensation at the film surface, which limited migration ability of fluorine chains. Fluorine segment contributed to surface hydrophobicity while silicon component was beneficial to improve water repellency of the film bulk. Silicon containing particles were more difficult to coalesce than fluorine acrylic particles due to the rigid crosslinked network derived from silanol crosslinking.

Two kinds of fluorine-containing acrylic copolymers were prepared with an in situ radical polymerization fluorine modification method and a post-polymerization fluorine modification route, respectively. And a kind of common acrylic copolymer as the reference was synthesized. Acrylic polyurethane was prepared using the synthesized acrylic copolymers and a trimer of the hexamethylene diisocyanate curing agent. Different environments including an indoor atmospheric environment, a hygrothermal environment, a different temperature environment, as well as a xenon arc aging environment were employed to investigate the failure behavior of the coatings. Fourier transform infrared spectroscopy (FT-IR) and 19F NMR were employed to characterize the chemical structure of the copolymers. The glass transition temperature (Tg) of the copolymers was tested using differential scanning calorimetry (DSC). The water contact angles of the coatings were monitored during the failure process. The difference in hydrophobicity of the coatings was examined. The thermostability of the coatings was explored using thermogravimetric analysis (TGA). The elemental composition of the coating surface before and after the failure experiment was analyzed using an X-ray photoelectron spectrometer (XPS). The results showed that the fluorine-containing copolymers and the corresponding hydrophobic coatings were prepared as expected. The Copolymer b coating, from the fluorine-containing acrylic copolymer prepared with the in situ polymerization fluorine modification route, exhibited better hydrophobicity in all of the above environments compared with the hydrocarbon acrylic copolymer coating (Copolymer a). The Copolymer c coating, prepared with the fluorine-containing acrylic copolymer via the post-polymerization fluorine modification method, achieved the best hydrophobicity under moderate conditions and failed quickly in hostile environments. The different fluorine modification methods resulted in different failure behaviors.

Vinyl group containing silica (MSiO2) nanoparticles were prepared by the co-condensation of tetraethoxysilane (TEOS) with 3-methacryloxypropyltrimethoxysilane (MPS) and applied in the miniemulsion polymerization of methyl methacrylate (MMA), butyl acrylate (BA) and 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (FA) to prepare fluorinated polyacrylate/silica nanocomposite particles. The morphology and particle size of MSiO2 was characterized by scanning electron microscopy (SEM). The nanocomposite films were investigated using atomic force microscopy (AFM), Fourier transform infrared (FT-IR) spectroscopy, water contact angle measurements, visible light spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetry analyses (TGA). The effect of the amount of MSiO2 on the surface properties of the nanocomposite films was studied. Results showed that the MSiO2 nanoparticles presented a rough surface with a mean particle size of 200 nm. The nanocomposite film showed high transparency and the surface hydrophobicity of the fluorinated polyacrylate film was increased significantly by the incorporation of 0.04 g (0.46 wt% of monomers) of MSiO2 nanoparticles. The presence of MSiO2 contributed to the surface enrichment of the fluorinated components, and the nanocomposite film formation mechanism was proposed.

•Surface properties of fluorosilicone polyacrylate latex film are studied.•Migration ability of fluorine is limited by silicon crosslinking reaction.•Migration behavior of fluorine and silicon is affected by polarity of the substrate.•Silicon containing groups are film–substrate interface enriched.•Silicon crosslinking reactions are favored by a high film forming temperature.Aggregation behavior of fluorine- and silicon-containing segments in fluorosilicone polyacrylate film formed on steel and PET (polyethylene terephthalate) substrates has been investigated. Surface composition and topography of the films were characterized by ATR-FTIR spectrometry, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Effect of film forming temperatures on surface morphology and water repellency has been evaluated. The results indicated that migration behavior of fluorine- and silicon-containing segments were significantly influenced by polarity of the substrates and film forming temperatures. Fluorine content at the film–steel interface was 0.45% while it reached to 1.69% at the film–PET interface, moreover, fluorinated segments were surface enriched while silicon-containing segments were enriched at film–substrate interface. As the film forming temperature was increased, fluorine content at the film surface decreased and silicon content increased, which was due to that a high film forming temperature favored silicon crosslinking at the film surface.Migration ability of fluorine-containing segments was limited by silicon crosslinking networks at a high film forming temperature.

•Core–shell fluorosilicone acrylic latex is prepared and characterized.•Surface morphology of the film annealed for different time is studied.•Migration behavior of fluorine is investigated in different conditions.•Annealing is beneficial for surface enrichment of fluorine.Core–shell fluorosilicone acrylic (FSiA) particles were prepared by two stage emulsion polymerization in the presence of common hydrocarbon acrylic monomers, trifluoroethyl methacrylate (TFEMA) and vinyltriethoxysilane (VTES). Morphology of latex particles was characterized by TEM. Surface properties of the film annealed at 100 °C for 1 h, 3 h, 5 h and 8 h were characterized by ATR–FTIR, AFM and SEM–EDS. Thermal properties of FSiA copolymer were investigated by TG–DSC analysis. TEM analysis indicated that two types of core–shell latex particles (CS-1 and CS-2) occurred in the process of emulsion polymerization, one is that fluorine-containing polymer existed at shell (CS-1), the other is that fluorine-containing polymer existed in the core (CS-2). ATR–FTIR and SEM–EDS data showed that as annealing time was increased, more fluorinated segments were found at the film surface. Fluorine content at the film surface increased from 2.25 wt.% (1.7 atom%) to 4.31 wt.% (3.22 atom%). AFM analysis suggested that the film surface topography was affected significantly by annealing time. The film showed excellent water resistant property due to the crosslinked network of SiOSi in the film.Fluorine content at film surface increased significantly as annealing time increased from 1 h to 8 h. While silicon-containing segments at the film surface remained almost unchanged in the process of annealing.

•Fluorinated acrylic/silica hybrid particles were prepared and studied.•Fluorinated acrylic copolymer has been grafted onto silica nanoparticles.•Functionalized silica in the polymerization favored the film hydrophobicity.•Fluorine content was increased at the film surface due to the presence of silica.Fluorinated acrylic/silica hybrid latexes have been prepared by mini-emulsion polymerization in the presence of silica nanoparticles functionalized by 3-(methacryloxy) propyltrimethoxysilane. The hybrid particle size and morphology were determined by transmission electron microscopy (TEM). Surface topography of the coating was investigated by atomic force microscopy (AFM) and chemical composition of the surface was analyzed by energy dispersive spectroscopy (EDS). Surface hydrophobicity of the coating was evaluated by water contact angle measurement. The results showed that polymeric latex particles were grafted onto silica. The presence of modified silica in fluorinated acrylic coating favored enrichment of fluorine at the film surface, which contributed to the hydrophobicity of the hybrid film.

•A fluorinated isocyanate acrylic monomer (FA) was synthesized.•Core–shell poly(fluorine acrylate) latexes with fluorine in shell were prepared and characterized.•Increasing FA monomer in emulsion polymerization affected latex film surface roughness and hydrophobicity.•Water contact angles increased with film surface roughness.•The FA monomer could enhance the abrasion resistance of the polymer films.A series of core–shell latexes were synthesized by seed emulsion polymerization with methyl methacrylate (MMA), butyl acrylate (BA), hydroxyethyl methacrylate (HEMA), methacrylic acid (MAA) and a novel fluorinated monomer, in which process, the novel fluorinated acrylic monomer (FA, reacting toluene diisocyanate with perfluorooctanol and HEMA) was applied in shell. FT–IR and 19F NMR spectra proved that the novel fluorinated acrylic monomer was incorporated into the copolymer chains. TEM and Dynamic light scattering (DLS) analyses demonstrated that latex particles with core–shell structure were obtained, and particle size distribution became broad after adding FA monomer. AFM measurement showed the films prepared from core–shell latexes exhibited different surface roughness; as amount of fluorinated acrylic monomer increased from 0 wt% to 12 wt% of total monomers in emulsion polymerization, the film surface roughness was enhanced from 0.33 nm to 1.67 nm, and water contact angle increased with film surface roughness. Thermogravimetric analysis demonstrated that a certain amount of FA monomer was preferable to improve thermal stability of the copolymer. Abrasion test of the films indicated that FA monomer was beneficial to increase abrasion performance of the films.A novel fluorinated acrylic monomer was synthesized (reacting toluene diisocyanate with perfluorooctanol and hydroxyethyl methacrylate) and applied in preparing core–shell latex. A series of core–shell latexes containing different amount of fluorinated acrylic monomer in shell were obtained and characterized.

Fluorinated acrylic latexes of methyl methacrylate (MMA), butyl acrylate (BA), methacrylic acid (MAA), hydroxyethyl methacrylate (HEMA), and trifluoroethyl methacrylate (TFMA) were synthesized by seed emulsion polymerization, and ammonium p-nonylphenol polyoxyethylene sulfate (CO-436), octylphenol polyoxyethylene ether (OP-10), perfluoroalkylpolyethers (Le-180s, RfCH2CH2O(CH2CH2O)nH, Rf = F(CF2CF2)4, Mn = 700) as well as C8F17SO3K (Le-003) were used as surfactants. One non-fluorinated (CO-436/OP-10) and two fluorinated (CO-436/OP-10/Le-180s, CO-436/OP-10/Le-180s/Le-003) surfactant systems were employed in this experiment. Effect of three surfactant systems on properties of the fluorinated acrylate latexes was investigated. Chemical composition and morphology of the copolymers were characterized by Fourier transform infrared spectroscopy (FT-IR), 19F NMR and transmission electron microscopy (TEM), respectively. The root-mean-square roughness of the latex film was investigated by atomic force microscopy (AFM) which revealed that the roughness was increased after employment of the fluorine-containing surfactants. TG and DSC analyse indicated that the polymer prepared in the presence of fluorine-containing surfactant had preferable thermal stability and high glass transition temperature. The average particle size of the latex prepared in the presence of fluorinated surfactant system was uniform and the particle distribution was narrow. Water hydrophobicity, dilution, refrigeration as well as Ca2+ stabilities were also investigated.Graphical abstractFluorinated acrylate latexes were prepared with MMA, BA, HEMA, MAA, and TFEMA by emulsion polymerization in three surfactant mixture systems, and the surface roughness and the hydrophobicity of the films were investigated. After adding fluorine containing surfactant, the surface roughness of the latex film was increased and hydrophobicity was improved. Also other characteristics such as thermal stability and conversion of fluorinated monomer were improved after employment of fluorinated surfactant in the experiment.Highlights► Different types of surfactants are used to synthesize fluorinated acrylate latex. ► Fluorine containing surfactant leads to an increase in latex stability. ► Conversion of fluorinated monomer is increased after addition of fluoro surfactant. ► Surface roughness increases as the addition of fluorine containing surfactant.

•The effects of fluorine and silicon components were studied in acrylic copolymers.•The two components had little influence on the latex particle size and morphology.•The fluorine component contributed better hydrophobicity.•The silicon component contributed better heat resistant property.•The two components resulted in a more rough and hydrophobic surface.A series of silicon-containing acrylic copolymers, fluorine-containing acrylic copolymers with two kinds of fluorinated acrylic monomers, as well as fluorosilicone acrylic copolymers were synthesized via seeded emulsion polymerization. Effects of fluorine and silicon components on properties of the copolymers were studied. Chemical structure of the copolymers was characterized by Fourier transform infrared spectrum (FT-IR) and 19F NMR. Glass transition temperature (Tg) of the copolymers was tested via differential scanning calorimetry (DSC). Molecular weight distribution of the copolymers was investigated by gel permeation chromatography (GPC). Morphology and particle size distribution of the copolymer latexes were investigated by transmission electron microscope (TEM) and particle size distribution analysis, respectively. Thermostability of the copolymers was explored by thermo gravimetric analysis (TGA). Hydrophobicity of the copolymer films was studied by the water contact angle data measured via sessile-drop method. Surface feature was investigated by atomic force microscope (AFM). The results showed that fluorine and/or silicon components which were incorporated chemically within the copolymers had little influence on the particle size and morphology of the latexes. The silicon component contributed better heat resistance, while the fluorine component contributed better hydrophobicity to the copolymers. The synergic effect of the two components resulted in a rough surface. The existence of both fluorine and silicon components, as well as the surface roughness, gave rise to a more hydrophobic film.A series of acrylic copolymers were synthesized via a seeding polymerization route. The effects of fluorine and silicon components were studied. Both the two components were helpful to the hydrophobicity of the copolymers. The synergic effect of the two components resulted in a roughness surface. The existence of fluorine and silicon components, as well as the surface roughness, gave rise a more hydrophobic film.

•Fluorine and silicon acrylic latexes were prepared.•Migration behavior of fluorine segment was investigated.•Silicon crosslinking reaction during film formation was studied.•Water resistant ability of fluorosilicone acrylic film was evaluated.A series of fluorine and silicon acrylic latexes have been prepared from acrylic monomers, 2,2,3,4,4,4-hexafluorobutyl acrylate (HFBA) and vinyltriethoxysilane (VTES) via emulsion polymerization. Morphology and particle size distribution were evaluated by transmission electron microscopy (TEM) and dynamic light scattering (DLS) methods. Surface properties of latex films were investigated in terms of ATR-FTIR spectrometry, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water resistance measurement. It is indicated that fluorine content at the surface of fluorosilicone acrylic film decreased as the film forming temperature was increased. A high temperature favored silicon condensation at the film surface, which limited migration ability of fluorine chains. Fluorine segment contributed to surface hydrophobicity while silicon component was beneficial to improve water repellency of the film bulk. Silicon containing particles were more difficult to coalesce than fluorine acrylic particles due to the rigid crosslinked network derived from silanol crosslinking.Download full-size image