SiO2 / paa-b-pfade amphiphilic Janus nanospheres, and preparation method and application thereof

Abstract

The application discloses SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, a preparation method and application thereof, and is based on a RAFT reaction to prepare excellent amphiphilic fluorine-containing block copolymer PAA-b-PFADE, uses a silica monomer as a carrier, uses a silane coupling agent as a modifier, obtains modified surface partially modified silica nanospheres, uses the modified silica nanospheres as a carrier, modifies the amphiphilic fluorine-containing block copolymer PAA-b-PFADE, and prepares the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres. The Janus nanospheres have good amphiphilic performance, and effectively improve the durability of a coating.

Description

Technical Field

[0001] The invention belongs to the technical field of functional coating development and relates to SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and a preparation method and application thereof. Background Art

[0002] In recent years, super-amphiphobic surface technology, a cutting-edge scientific innovation, has gradually demonstrated its enormous application potential in multiple fields. Due to its unique water- and oil-repellent properties, this surface technology has demonstrated remarkable results in self-cleaning, surface corrosion protection, and anti-icing. It not only has broad application prospects in daily life, such as enabling self-cleaning functions in clothing, furniture, and building exteriors, thereby reducing manual maintenance costs; in the biomedical field, super-amphiphobic surface technology also shows great potential, such as in anti-fouling treatment of medical devices, improving the cleanliness and safety of surgical instruments. Furthermore, in the military, this technology can be used for surface treatment of aircraft, ships, and other equipment, effectively reducing corrosion and icing problems in marine environments or in adverse weather conditions, thereby improving the combat effectiveness and durability of equipment.

[0003] However, despite the promising prospects of super-amphiphobic surface technology, existing super-amphiphobic materials still face a series of challenges in practical application. Among them, the stability of low-surface-energy materials is particularly prominent. These materials are often susceptible to environmental factors such as temperature, light, and strong oxidants, leading to structural decomposition or performance degradation. This stability issue is particularly prominent under extreme climatic conditions, such as high temperatures and strong ultraviolet radiation, which undoubtedly limits the widespread application of super-amphiphobic surface technology.

[0004] Furthermore, the fragility of micro- and nanostructures is a major challenge facing current super-amphiphobic materials. Micro- and nanostructures are key to achieving the water- and oil-repellent properties of super-amphiphobic surfaces, but these delicate structures are extremely susceptible to damage from mechanical friction and abrasion. Once these micro- and nanostructures are damaged, the coating's adhesion and super-amphiphobic properties are significantly reduced or even completely lost, severely impacting the surface's lifespan and effectiveness. Summary of the Invention

[0005] In response to the problems existing in the prior art, the present invention provides a SiO2 / PAA-b-PFADE amphiphilic Janus nanosphere and its preparation method and application, thereby solving the technical problem of poor durability of superamphiphobic materials in the prior art.

[0006] The present invention is achieved through the following technical solutions:

[0007] A method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres comprises the following steps:

[0008] SiO2 nanospheres and hexadecyltrimethylammonium bromide were added to a two-phase solvent of water and toluene, and then the pH value of the system was adjusted to 7-8. γ-aminopropyltriethoxysilane was added to react to prepare γ-aminopropyltriethoxysilane-modified SiO2 nanospheres.

[0009] Acrylic acid, 4-cyano-4-(phenylthioformylthio)valeric acid and azobisisobutyronitrile are added to tetrahydrofuran for a primary reaction to obtain a first product; the first product, perfluorodecyl acrylate and azobisisobutyronitrile are added to tetrahydrofuran for a secondary reaction to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE;

[0010] The amphiphilic fluorinated block copolymer PAA-b-PFADE, a catalyst and ethanol are mixed and ultrasonically dispersed, and the γ-aminopropyltriethoxysilane-modified SiO2 nanospheres are added. After reaction, the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres are obtained.

[0011] Preferably, the particle size of the SiO2 nanospheres is 30-500 nm.

[0012] Preferably, the ratio of the SiO2 nanospheres to γ-aminopropyltriethoxysilane is (0.5-3.0) g: (100-600) μL.

[0013] Preferably, the mass ratio of acrylic acid to 4-cyano-4-(phenylthiocarbamoylthio)pentanoic acid and perfluorodecyl acrylate is 7:0.2:(15.5-51.8).

[0014] Preferably, during the primary reaction, the reaction temperature is 75-90° C., and the reaction time is 7-12 h; during the secondary reaction, the reaction temperature is 75-90° C., and the reaction time is 7-12 h.

[0015] Preferably, the mass ratio of the amphiphilic fluorinated block copolymer PAA-b-PFADE to the γ-aminopropyltriethoxysilane-modified SiO2 nanospheres is (0.03~0.18):(0.075~0.45).

[0016] SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres are prepared by the above method.

[0017] The above-mentioned SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres are used in the preparation of super amphiphobic coatings. First, a hydroxy acrylic resin prepolymer solution is coated on the surface of the substrate, and then a mixed solution of a crosslinker and the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is coated, and the super amphiphobic coating is obtained after drying.

[0018] Preferably, the coating amount of the hydroxy acrylic resin prepolymer solution, the crosslinking agent and the SiO2 / PAA-b-PFADE amphiphilic Janus nanosphere mixed solution is 0.05-0.06 mL / cm 2 The concentration of the hydroxy acrylic resin prepolymer solution is 0.1 to 0.6 g / mL, and the concentration of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the mixed solution of the crosslinker and SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is 0.01 to 0.035 g / mL.

[0019] A super-amphiphobic coating is prepared by the above method; the super-amphiphobic coating has an oil contact angle of 150°~157°, an oil sliding angle of 2.6°~9.4°, a water contact angle of 152°~160°, and a water sliding angle of 1.9°~9°.

[0020] Compared with the prior art, the present invention has the following beneficial technical effects:

[0021] The present invention discloses a method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres. At the water-organic two-phase interface, hydrophilic amino groups are grafted onto a portion of the surface of the SiO2 nanospheres, while the original hydroxyl groups are retained on a portion. An amphiphilic fluorinated block copolymer is further grafted onto the amino groups to provide superphobic segments, thereby preparing an amphiphilic coating. During the preparation process, acrylic acid and perfluorodecyl acrylate are used as hydrophilic and hydrophobic monomers, respectively, in the presence of 4-cyano-4-(phenylthioformylthio) pentanoic acid, and the hydrophilic and hydrophobic monomers are synthesized by RAFT polymerization. An amphiphilic fluorinated block copolymer (PAA-b-PFADE) was prepared. The reactive carboxyl groups in its hydrophilic segments reacted with the reactive amino groups at one end of NH2-SiO2 nanospheres modified with γ-aminopropyltriethoxysilane in an ethanol solution to form SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres. This process transformed the SiO2 nanospheres' surfaces into partially hydrophilic and partially hydrophobic, achieving the construction of amphiphilic nanoparticles. When these amphiphilic nanoparticles were used to construct a coating, the inorganic ends oriented toward the hydroxyl acrylic coating, while the organic lyophobic segments oriented toward the air. The micro-nano rough structure of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and the low surface energy provided by the organic lyophobic segments achieved superamphiphobic properties. Furthermore, the reactive hydroxyl groups on the inorganic ends chemically crosslinked with a crosslinker, improving the coating's wear resistance and effectively enhancing its durability.

[0022] Furthermore, the particle size of the SiO2 nanospheres is 30~500nm. By regulating the particle size of the nanospheres, different micro-nano dual-scale rough structures can be formed, thereby giving the coating differentiated super-amphiphobic properties, including changes in water contact angle, oil contact angle and rolling angle, to adapt to the specific requirements of super-amphiphobic properties in different application scenarios.

[0023] Furthermore, the ratio of the SiO2 nanospheres to γ-aminopropyltriethoxysilane is (0.5~3.0) g:(100~600) μL. By adjusting the ratio of the two, the grafting rate of γ-aminopropyltriethoxysilane on the surface of the SiO2 nanospheres can be controlled, thereby affecting the number and distribution of reactive groups on the surface of the SiO2 nanospheres, providing a regulatory basis for subsequent functional modification.

[0024] Furthermore, the mass ratio of acrylic acid to 4-cyano-4-(phenylthiocarbamoylthio)pentanoic acid and perfluorodecyl acrylate is 7:0.2:(15.5-51.8). By adjusting the ratio of the three, the length of the fluorinated monomer chain at the hydrophobic end of the fluorinated block copolymer can be precisely controlled, thereby obtaining a fluorinated block copolymer with excellent performance. This copolymer can significantly enhance the superamphiphobic properties of the coating, including higher water and oil contact angles and lower sliding angles.

[0025] Furthermore, during the primary reaction, the reaction temperature is 75-90°C and the reaction time is 7-12 hours; during the secondary reaction, the reaction temperature is 75-90°C and the reaction time is 7-12 hours. By controlling the reaction temperature and reaction time, the hydrolysis environment of γ-aminopropyltriethoxysilane can be adjusted, thereby affecting its grafting rate on the surface of the SiO2 nanospheres. Variation in the grafting rate further regulates the number and distribution of reactive groups on the SiO2 nanosphere surface, providing scientific basis and technical support for subsequent functional modification.

[0026] Furthermore, the mass ratio of the amphiphilic fluorinated block copolymer PAA-b-PFADE to the γ-aminopropyltriethoxysilane-modified SiO2 nanospheres is (0.03~0.18):(0.075~0.45). By regulating this mass ratio, the performance of the obtained SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is optimized, and the superamphiphobic properties of the coating are improved, including higher water contact angles and oil contact angles, and lower sliding angles, thereby enhancing the waterproof, oil-proof and anti-fouling capabilities of the coating.

[0027] Furthermore, the present invention also discloses an application of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the preparation of a super-amphiphobic coating, wherein a hydroxylated acrylic resin prepolymer solution is first coated on the surface of the substrate, followed by coating with a crosslinking agent and a mixed solution of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, and drying to obtain a super-amphiphobic coating. The coating amount of the hydroxylated acrylic resin prepolymer solution and the mixed solution of the crosslinking agent and the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is 0.05-0.06 mL / cm 2 The concentration of the hydroxyl acrylic resin prepolymer solution is 0.1~0.6g / mL, and the concentration of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the mixed solution of the crosslinker and SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is 0.01~0.035g / mL. The optimized design of the above parameters can enhance the crosslinking effect of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the coating, thereby giving the super-amphiphobic coating excellent durability, including higher wear resistance and long-term water and oil repellency properties.

[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0029] Figure 1 Transmission electron microscopy images of silver-labeled NH2-SiO2Janus nanospheres;

[0030] Figure 2 Transmission electron microscopy image of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres

[0031] Figure 3 This is a photo of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres stabilized emulsion;

[0032] Figure 4 Contact angle test results of different liquids on the super-amphiphobic coating prepared in Example 2 of the present invention after thirty friction tests;

[0033] Figure 5 The water contact angle and rolling contact angle test results of the super amphiphobic coating constructed based on SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres prepared in Example 2 of the present invention after different cyclic friction tests;

[0034] Figure 6 These are the hexadecane contact angle and rolling contact angle test results of the super amphiphobic coating constructed based on SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres prepared in Example 2 of the present invention after different cyclic friction tests. DETAILED DESCRIPTION

[0035] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0036] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0037] All features, such as values, amounts, contents, and concentrations, described herein as numerical ranges or percentage ranges are provided for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to include and specifically disclose all possible subranges and individual values ​​within the range (including integers and fractions).

[0038] In this document, unless otherwise specified, “include,” “including,” “contains,” “has” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0039] In this document, for the sake of brevity, not all possible combinations of the various technical features in each embodiment or example are described. Therefore, as long as there are no contradictions in the combination of these technical features, the various technical features in each embodiment or example can be combined in any way, and all possible combinations should be considered to be within the scope of this specification.

[0040] The present invention provides a method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, comprising the following steps:

[0041] S1: SiO2 nanospheres and hexadecyltrimethylammonium bromide are added to a two-phase solvent of water and toluene, and stirred at 20-40°C for 20-40 minutes to stably disperse the SiO2 nanospheres at the interface between the water and toluene phases. Ammonia water is then added to adjust the pH value of the system to 7-8, and the system is stirred at 85-95°C for 1-6 hours to stabilize the system. Finally, γ-aminopropyltriethoxysilane is added and reacted at 85-95°C for 1-6 hours to obtain γ-aminopropyltriethoxysilane-modified SiO2 nanospheres.

[0042] Specifically: The particle size of SiO2 nanospheres is 30~500nm, and they are solid nanospheres.

[0043] The SiO2 nanospheres are prepared by adding 10 mL of aqueous ammonia, 50-250 mL of anhydrous ethanol, and 30 mL of deionized water to a three-necked flask equipped with a digital stirrer. After stirring for 20 minutes at 30°C, 10 mL of ethyl orthosilicate is added and the reaction is continued for 5 hours. After the reaction is complete, SiO2 nanospheres with a particle size of 30-500 nm are obtained through centrifugation, washing, and drying.

[0044] The ratio of SiO2 nanospheres to γ-aminopropyltriethoxysilane is (0.5~3.0) g: (100~600) μL;

[0045] The ratio of SiO2 nanospheres to dispersant water and toluene is (0.5~3.0) g: (50~300) mL: (10~60) mL;

[0046] The mass ratio of SiO2 nanospheres to hexadecyltrimethylammonium bromide is (0.5~3.0):(0.31~1.86).

[0047] Preferably, the ratio of SiO2 nanospheres to γ-aminopropyltriethoxysilane is (0.5-2.5) g: (100-500) μL;

[0048] The ratio of SiO2 nanospheres to dispersant water and toluene is (0.5~2.5) g: (50~250) mL: (10~50) mL;

[0049] The mass ratio of SiO2 nanospheres to hexadecyltrimethylammonium bromide is (0.5~2.5):(0.31~1.55).

[0050] S2: adding acrylic acid, 4-cyano-4-(phenylthioformylthio)valeric acid, and azobisisobutyronitrile to tetrahydrofuran for a primary reaction to obtain a first product; adding the first product, perfluorodecyl acrylate, and azobisisobutyronitrile to tetrahydrofuran for a secondary reaction to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE;

[0051] In a specific process, step S2 is:

[0052] S21: Acrylic acid, 4-cyano-4-(phenylthiocarboxymethylthio)valeric acid, a first volume of azobisisobutyronitrile, and a first volume of tetrahydrofuran are mixed, reacted at 75-90° C. for 7-12 hours to obtain a first mixed solution, and the mixture is distilled under reduced pressure and then vacuum dried at 25-35° C. for 24-48 hours to obtain a first product;

[0053] S22: Mix the first product, perfluorodecyl acrylate, a second volume of azobisisobutyronitrile and a second volume of tetrahydrofuran, react at 75-90°C for 7-12 hours to obtain a second mixed solution, distill under reduced pressure, and vacuum dry at 25-35°C for 24-48 hours to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE.

[0054] The mass ratio of acrylic acid to 4-cyano-4-(phenylthioformylthio)pentanoic acid and perfluorodecyl acrylate is 7:0.2:(15.5~51.8); the length of the lyophobic segment is adjusted by adjusting the mass ratio of the lyophilic and lyophobic monomers acrylic acid to perfluorodecyl acrylate. When the mass is low, the super amphiphobic performance of the coating is poor. As the length of the lyophobic block increases, the super amphiphobic performance of the coating increases. When the length of the lyophobic block increases to a certain size, the length continues to increase, the entanglement between molecules becomes greater, and it affects the activity of the carboxyl group. Therefore, the reactivity of the γ-aminopropyltriethoxysilane-modified NH2-SiO2 nanospheres is reduced, resulting in a weakening of the super amphiphobic performance.

[0055] Further preferably, the ratio (feed ratio) of acrylic acid, 4-cyano-4-(phenylthiocarboylthio) valeric acid, the first volume of azobisisobutyronitrile, the first volume of tetrahydrofuran, perfluorodecyl acrylate, the second volume of azobisisobutyronitrile, and the second volume of tetrahydrofuran is 7.206 g:0.19 g:0.055 g:70 mL: (15.544-51.817) g:0.016 g:70 mL;

[0056] S3: The amphiphilic fluorinated block copolymer PAA-b-PFADE, catalyst and ethanol are mixed, and after ultrasonic dispersion, the system is treated at 40°C for 0.5~3h to activate the carboxyl groups on the amphiphilic fluorinated block copolymer PAA-b-PFADE, and then the γ-aminopropyltriethoxysilane-modified SiO2 nanospheres are added and reacted at 50~70°C for 2~10h to obtain the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres.

[0057] The mass ratio of the amphiphilic fluorinated block copolymer PAA-b-PFADE to the γ-aminopropyltriethoxysilane-modified SiO2 nanospheres is (0.03-0.18):(0.075-0.45).

[0058] The catalyst is 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and N-hydroxysuccinimide;

[0059] Further preferably, the mass ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-hydroxysuccinimide, amphiphilic fluorinated block copolymer PAA-b-PFADE and γ-aminopropyltriethoxysilane modified SiO2 nanospheres is (0.01~0.06):(0.005~0.030):(0.03~0.18):(0.075~0.45).

[0060] The feed ratio of amphiphilic fluorinated block copolymer PAA-b-PFADE and ethanol is (0.03~0.18)g:180mL.

[0061] The present invention also discloses a SiO2 / PAA-b-PFADE amphiphilic Janus nanosphere prepared by the above method. A portion of the surface of the SiO2 nanosphere is modified with hydrophilic amino groups for grafting the amphiphilic block copolymer PAA-b-PFADE.

[0062] The present invention discloses a method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres. The preparation method comprises: (1) preparing an amphiphilic fluorinated block copolymer PAA-b-PFADE with excellent performance based on a RAFT reaction; (2) using a silica monomer as a carrier and a silane coupling agent as a modifier to obtain silica nanospheres with partially modified surfaces; and (3) using the modified silica nanospheres as a carrier and modifying the amphiphilic fluorinated block copolymer PAA-b-PFADE to obtain amphiphilic silica Janus nanospheres. The Janus particles have excellent performance and strong applicability, and have great application value in enhancing the lyophobic properties and lyophobic types of super-amphiphobic particles.

[0063] Also disclosed is the application of the above-mentioned SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the preparation of a super-amphiphobic coating. First, a hydroxy acrylic resin prepolymer solution is coated on the surface of the substrate, and then a mixed solution of a crosslinker and the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is coated, and the super-amphiphobic coating is obtained after drying.

[0064] In a preferred embodiment, the coating amount of the hydroxy acrylic resin prepolymer solution, the crosslinking agent and the SiO2 / PAA-b-PFADE amphiphilic Janus nanosphere mixed solution is 0.05-0.06 mL / cm 2 The concentration of the hydroxy acrylic resin prepolymer solution is 0.1 to 0.6 g / mL, and the concentration of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the mixed solution of the crosslinker and SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is 0.01 to 0.035 g / mL.

[0065] Here, the solvent used to dissolve the hydroxylated acrylic resin prepolymer is ethyl acetate, and the solvent used to disperse the crosslinking agent and the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is ethyl acetate.

[0066] In addition, the present invention also discloses a super-amphiphobic coating prepared by the method.

[0067] The present invention discloses a SiO2 / PAA-b-PFADE amphiphilic Janus nanosphere. A portion of the surface of the SiO2 nanosphere retains the original hydroxyl groups, while the other portion is grafted with hydrophilic amino groups. An amphiphilic fluorinated block copolymer is further grafted onto the surface to provide superphobic segments, thereby preparing an amphiphobic coating.

[0068] The invention discloses a method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres. In the presence of 4-cyano-4-(phenylthioformylthio) valeric acid, acrylic acid and perfluorodecyl acrylate are used as hydrophilic and hydrophobic monomers, respectively, to prepare an amphiphilic fluorinated block copolymer by RAFT polymerization. After purification and drying by reduced pressure distillation, the amphiphilic fluorinated block copolymer PAA-b-PFADE is obtained. The SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres are obtained by acylation reaction in an ethanol solution using a reactive carboxyl group of a hydrophilic chain segment and a reactive amino group at one end of a γ-aminopropyltriethoxysilane-modified NH2-SiO2 nanosphere.

[0069] The present invention utilizes SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres to orient them on the coating surface, with the inorganic end facing the hydroxyl propylene coating on the coating surface, and the organic lyophobic segment facing the air, and the micro-nano rough structure constructed by the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and the low surface energy material provided by the organic lyophobic segment are used to realize the super-amphiphobic performance of the coating. In addition, the reactive group hydroxyl group of the inorganic end and the isocyanate group on the hydroxyl propylene crosslinking agent hexamethylene diisocyanate molecular chain produce chemical crosslinking, thereby improving the wear resistance of the coating. The super-amphiphobic coating prepared by the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres of the present invention has an oil contact angle of 150°~153°, an oil rolling angle of 4°~8°, a water contact angle of 150°~153°, and a water rolling angle of 4°~8°.

[0070] Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiments are only used to illustrate the present invention and are not used in limiting the scope of the present invention.In addition, should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall equally within the scope limited by the appended claims of the application.

[0071] The following examples were prepared using conventional instruments and equipment in the art. Experimental methods in the following examples, where specific conditions are not specified, were generally performed under conventional conditions or according to the conditions recommended by the manufacturer. The various raw materials used in the following examples, unless otherwise specified, were conventional commercially available products, with specifications conventional in the art. In the present specification and the following examples, unless otherwise specified, "%" indicates percentage by weight, "part" indicates parts by weight, and "ratio" indicates weight ratio.

[0072] Example 1

[0073] A method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, comprising the following steps

[0074] Step 1: Mix 0.50 g of SiO2 nanospheres with a particle size of 30 nm, 0.31 g of hexadecyltrimethylammonium bromide, 50 mL of deionized water, and 10 mL of toluene, then ultrasonically disperse them, heat them to 20°C, treat them for 20 minutes, then add 1.5 mL of deionized water and 1.5 mL of ammonia water, heat them to 85°C, keep them warm for 1 hour, then add 100 μL of γ-aminopropyltriethoxysilane, keep them warm at 85°C for 1 hour, wash them with toluene, ethanol, and deionized water in turn, and dry them to obtain γ-aminopropyltriethoxysilane-modified NH2-SiO2 nanospheres.

[0075] Step 2: After mixing 7.206 g of acrylic acid, 0.19 g of 4-cyano-4-(phenylthiocarboxylthio) valeric acid, 0.055 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 75 ° C., stirred for 7 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 25 ° C. and dried for 24 hours to obtain a first product. The first product was mixed with 15.544 g of perfluorodecyl acrylate, 0.016 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 75 ° C., stirred for reaction for 7 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 25 ° C. and dried for 24 hours to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE.

[0076] Step 3: 0.03 g of amphiphilic fluorinated block copolymer PAA-b-PFADE, 0.01 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 0.005 g of N-hydroxysuccinimide were mixed with ethanol, ultrasonically dispersed, and then heated to 40°C for activation for 0.5 h. Finally, 0.075 g of γ-aminopropyltriethoxysilane-modified SiO2 nanospheres were added thereto. The mixture was heated to 50°C for reaction for 2 h, centrifuged, washed, and dried to obtain SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres.

[0077] Preparation of super amphiphobic coating based on the above-mentioned SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres:

[0078] Spray 0.1 g / mL ethyl acetate solution of hydroxy acrylate prepolymer on the substrate surface at a spraying volume of 0.05 mL / cm 2 Then, a solution of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and hexamethylene diisocyanate in ethyl acetate with a concentration of 0.01 g / mL was sprayed on the surface of the substrate at a spraying volume of 0.05 mL / cm 2 , and dried to obtain a super-amphiphobic coating.

[0079] Example 2

[0080] A method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, comprising the following steps

[0081] Step 1: 3.00 g of SiO2 nanospheres with a particle size of 500 nm, 1.86 g of hexadecyltrimethylammonium bromide, 300 mL of deionized water, and 60 mL of toluene were mixed and ultrasonically dispersed, heated to 40°C and treated for 40 minutes, then 9 mL of deionized water and 9 mL of ammonia water were added and heated to 95°C and kept warm for 6 hours, then 600 μL of γ-aminopropyltriethoxysilane was added and the mixture was kept warm at 95°C for 6 hours, and then washed with toluene, ethanol, and deionized water in sequence, and dried to obtain γ-aminopropyltriethoxysilane-modified NH2-SiO2 nanospheres.

[0082] Step 2: After mixing 7.206 g of acrylic acid, 0.19 g of 4-cyano-4-(phenylthioformylthio) valeric acid, 0.055 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 90 ° C., stirred for 12 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 35 ° C. and dried for 48 hours to obtain a first product. The first product was mixed with 51.817 g of perfluorodecyl acrylate, 0.016 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 90 ° C., stirred for reaction for 12 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 35 ° C. and dried for 48 hours to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE.

[0083] Step 3: 0.18 g of the amphiphilic fluorinated block copolymer PAA-b-PFADE, 0.06 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 0.030 g of N-hydroxysuccinimide were mixed with ethanol, ultrasonically dispersed, and then heated to 40°C for activation for 3 h. Finally, 0.45 g of γ-aminopropyltriethoxysilane-modified SiO2 nanospheres were added thereto. The mixture was heated to 70°C for reaction for 10 h, centrifuged, washed, and dried to obtain SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres.

[0084] Preparation of super amphiphobic coating based on the above-mentioned SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres:

[0085] Spray 0.6 g / mL ethyl acetate solution of hydroxy acrylate prepolymer on the substrate surface at a spraying volume of 0.06 mL / cm 2 Then, a solution of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and hexamethylene diisocyanate in ethyl acetate with a concentration of 0.035 g / mL was sprayed thereon at a spraying volume of 0.06 mL / cm 2 , and dried to obtain a super-amphiphobic coating.

[0086] Example 3

[0087] A method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, comprising the following steps

[0088] Step 1: Mix 1 g of SiO2 nanospheres with a particle size of 150 nm, 0.62 g of hexadecyltrimethylammonium bromide, 100 mL of deionized water, and 20 mL of toluene, then ultrasonically disperse them, heat them to 25°C, treat them for 25 minutes, then add 3 mL of deionized water and 3 mL of ammonia water, heat them to 88°C, keep them warm for 2 hours, then add 200 μL of γ-aminopropyltriethoxysilane, keep them warm at 88°C for 2 hours, wash them with toluene, ethanol, and deionized water in sequence, and dry them to obtain γ-aminopropyltriethoxysilane-modified NH2-SiO2 nanospheres.

[0089] Step 2: After mixing 7.206 g of acrylic acid, 0.19 g of 4-cyano-4-(phenylthioformylthio) valeric acid, 0.055 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 80 ° C., stirred for 8 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 28 ° C. and dried for 30 hours to obtain a first product. The first product was mixed with 20.725 g of perfluorodecyl acrylate, 0.016 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 80 ° C., stirred for reaction for 8 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 28 ° C. and dried for 30 hours to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE.

[0090] Step 3: 0.06 g of amphiphilic fluorinated block copolymer PAA-b-PFADE, 0.02 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 0.01 g of N-hydroxysuccinimide were mixed with ethanol, ultrasonically dispersed, and then heated to 40°C for activation for 1 hour. Finally, 0.150 g of γ-aminopropyltriethoxysilane-modified SiO2 nanospheres were added thereto. The mixture was heated to 55°C for reaction for 4 hours, then centrifuged, washed, and dried to obtain SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres.

[0091] Preparation of super amphiphobic coating based on the above-mentioned SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres:

[0092] Spray 0.2 g / mL of ethyl acetate solution of hydroxy acrylate prepolymer on the substrate surface at a spraying volume of 0.05 mL / cm 2 Then, a solution of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and hexamethylene diisocyanate in ethyl acetate with a concentration of 0.015 g / mL was sprayed thereon at a spraying volume of 0.06 mL / cm 2 , and dried to obtain a super-amphiphobic coating.

[0093] Example 4

[0094] A method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, comprising the following steps

[0095] Step 1: 1.5 g of SiO2 nanospheres with a particle size of 250 nm, 0.93 g of hexadecyltrimethylammonium bromide, 150 mL of deionized water, and 30 mL of toluene were mixed and ultrasonically dispersed, heated to 30°C, treated for 30 min, then 4.5 mL of deionized water and 4.5 mL of ammonia water were added and heated to 90°C, kept warm for 3 h, then 300 μL of γ-aminopropyltriethoxysilane was added, and the mixture was kept warm at 90°C for 3 h. The mixture was washed with toluene, ethanol, and deionized water in sequence, and dried to obtain γ-aminopropyltriethoxysilane-modified NH2-SiO2 nanospheres.

[0096] Step 2: After mixing 7.206 g of acrylic acid, 0.19 g of 4-cyano-4-(phenylthioformylthio) valeric acid, 0.055 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 83 ° C., stirred for 9 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 30 ° C. and dried for 36 hours to obtain a first product. The first product was mixed with 25.907 g of perfluorodecyl acrylate, 0.016 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 83 ° C., stirred for reaction for 9 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 30 ° C. and dried for 36 hours to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE.

[0097] Step 3: 0.09 g of amphiphilic fluorinated block copolymer PAA-b-PFADE, 0.03 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 0.015 g of N-hydroxysuccinimide were mixed with ethanol, ultrasonically dispersed, and then heated to 40°C for activation for 1.5 h. Finally, 0.225 g of γ-aminopropyltriethoxysilane-modified SiO2 Janus nanospheres were added thereto. The mixture was heated to 60°C for reaction for 6 h, then centrifuged, washed, and dried to obtain SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres.

[0098] Preparation of super amphiphobic coating based on the above-mentioned SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres:

[0099] Spray 0.5 g / mL ethyl acetate solution of hydroxy acrylate prepolymer on the substrate surface at a spraying volume of 0.06 mL / cm 2 Then, a solution of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and hexamethylene diisocyanate in ethyl acetate with a concentration of 0.030 g / mL was sprayed thereon at a spraying volume of 0.05 mL / cm 2 , and dried to obtain a super-amphiphobic coating.

[0100] Example 5

[0101] A method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, comprising the following steps

[0102] Step 1: Mix 2.00 g of SiO2 nanospheres with a particle size of 350 nm, 1.24 g of hexadecyltrimethylammonium bromide, 200 mL of deionized water, and 40 mL of toluene, then ultrasonically disperse them. Heat the mixture to 33°C and keep it warm for 33 minutes. Then add 6 mL of deionized water and 6 mL of ammonia water and heat the mixture to 92°C. Keep it warm for 4 hours. Then add 400 μL of γ-aminopropyltriethoxysilane and keep it warm at 92°C for 4 hours. Wash with toluene, ethanol, and deionized water in sequence, and dry them to obtain γ-aminopropyltriethoxysilane-modified NH2-SiO2 nanospheres.

[0103] Step 2: After mixing 7.206 g of acrylic acid, 0.19 g of 4-cyano-4-(phenylthioformylthio) valeric acid, 0.055 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 85 ° C., stirred for 10 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 32 ° C. and dried for 42 hours to obtain a first product. The first product was mixed with 25.907 g of perfluorodecyl acrylate, 0.016 g of azobisisobutyronitrile and 70 mL of tetrahydrofuran, the mixture was heated to 88 ° C., stirred for reaction for 10 hours, and then subjected to reduced pressure distillation and purification. The purified product was placed in a vacuum oven at a temperature of 32 ° C. and dried for 42 hours to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE.

[0104] Step 3: 0.12 g of amphiphilic fluorinated block copolymer PAA-b-PFADE, 0.040 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and 0.020 g of N-hydroxysuccinimide were mixed with ethanol, ultrasonically dispersed, and then heated to 40°C for activation for 2 h. Finally, 0.30 g of γ-aminopropyltriethoxysilane-modified SiO2 nanospheres were added thereto. The mixture was heated to 65°C for reaction for 6 h, followed by centrifugal washing and drying to obtain SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres.

[0105] Preparation of super amphiphobic coating based on the above-mentioned SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres:

[0106] Spray 0.4 g / mL ethyl acetate solution of hydroxy acrylate prepolymer on the substrate surface at a spraying volume of 0.055 mL / cm 2 Then, a solution of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and hexamethylene diisocyanate in ethyl acetate with a concentration of 0.025 g / mL was sprayed thereon at a spraying volume of 0.055 mL / cm 2 , and dried to obtain a super-amphiphobic coating.

[0107] Taking Example 2 as an example, the NH2-SiO2Janus nanospheres prepared in Example 2 were used for silver labeling. The NH2-SiO2Janus nanospheres were dispersed in a silver nitrate solution, and the silver ions were reduced after adding water and hydrazine. The micromorphology of the labeled NH2-SiO2Janus nanospheres was characterized, and the TEM results were as follows: Figure 1 As shown. Figure 1 It can be seen that the NH2-SiO2Janus nanospheres contain silver particles only at one end and have a significant asymmetric structure, indicating that the NH2-SiO2Janus nanospheres were successfully prepared using this method.

[0108] Figure 2 The SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres were formed by grafting the amphiphilic fluorinated block copolymer PAA-b-PFADE onto NH2-SiO2Janus nanospheres. The micromorphology of the nanospheres was characterized. The TEM results are shown in Figure 2. Figure 2 As shown. Figure 2 It can be seen that only a part of the surface of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres contains the amphiphilic fluorinated block copolymer PAA-b-PFADE, which has a significant asymmetric structure, indicating that the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres were successfully prepared by this method.

[0109] Figure 3 This is an optical microscope photograph of the emulsion stabilized by SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres. SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres were added to a mixed emulsion of dodecane and dimethyl sulfoxide, and ultrasonic cell disruption and emulsification were performed for ten minutes. The emulsion was placed under an upright microscope, and its stable emulsion droplets could be observed, indicating that it has amphiphilic properties.

[0110] Figure 4 Contact angle test results of different liquids on the super-amphiphobic coating prepared in Example 2 of the present invention after thirty friction tests; Figure 4 It can be seen that the super-amphiphobic coating prepared by the present invention still has good super-amphiphobic performance after several friction tests, wherein the water contact angle is 152°±0.9° and the oil contact angle is 151±0.4°, and has excellent liquid-repellent performance.

[0111] Figure 5The water contact angle and rolling contact angle test results of the super double-repellent coating constructed for the embodiment of the present invention 2 after different cyclic friction experiments by the amphiphilic Janus nanospheres of PAA-b-PFADE are shown in the figure. As shown in the figure, when not rubbed, the super double-repellent coating shows excellent super-hydrophobicity, and its water contact angle and rolling angle are respectively 159.7 ± 1.1 ° and 1.9 ± 0.3 °. As the number of frictions increases, the water contact angle of coating decreases gradually, and rolling angle increases gradually. After 50 friction cycles, the water contact angle and rolling angle of coating are respectively 152.2 ± 3.2 ° and 8.9 ± 0.2 °, showing that coating still possesses significant super-hydrophobicity. The superiority of this wear resistance is due to SiO2 / chemical crosslinking and physical bonding between PAA-b-PFADE amphiphilic Janus nanospheres and hydroxy acrylic resin, effectively suppressing the coming off of nanospheres during friction, thereby ensuring the micro-nanostructure stability of coating surface, significantly improving its wear-resistant super-hydrophobicity.

[0112] Figure 6 The super double-repellent coating constructed based on SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres prepared in Example 2 of the present invention is subjected to hexadecane contact angle and rolling contact angle test results after different cyclic friction experiments. As shown in the figure, when not rubbed, the super double-repellent coating shows excellent super oleophobic performance, and its hexadecane contact angle and rolling angle are 157.8 ± 0.9 ° and 2.6 ± 0.7 ° respectively. As the number of frictions increases, the oil contact angle of the coating gradually decreases, and the rolling angle gradually increases. After 50 friction cycles, the oil contact angle and rolling angle are 150.3 ± 0.7 ° and 9.4 ± 0.5 ° respectively, indicating that the coating still has super oleophobic ability. This excellent wear resistance is attributed to the chemical crosslinking reaction and physical bonding force between SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres and hydroxy acrylic resin, which effectively hinders the shedding of nanospheres during friction, thereby maintaining the super oleophobic properties and stability of the coating.

[0113] The friction test described above specifically evaluates the wear resistance of a super-amphiphobic coating constructed with SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres. A hydroxyl acrylic resin was used as a primer and the coating was spray-coated onto a glass slide. The coating was then tested using a sandpaper friction test. The specific method involved placing the coating sample on 400-grit sandpaper, loading a 50g weight onto the glass slide, and performing a friction cycle of 10 cm horizontally and 10 cm vertically. The slide was then moved at a constant speed, and the changes in the water contact angle, oil contact angle, and rolling angle of the coating after each friction cycle were recorded to evaluate the super-amphiphobic performance and wear stability of the coating under friction.

[0114] In summary, the present invention successfully prepared NH2-SiO2Janus nanospheres by the emulsion interface method, and then successfully prepared SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres by acylation reaction with amphiphilic fluorinated block copolymers. Then, by layer-by-layer spraying, the hydrophilic end was chemically cross-linked with the substrate to obtain a super-amphiphobic coating.

[0115] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres, characterized in that: The following steps are involved: SiO2 nanospheres and hexadecyltrimethylammonium bromide were added to a two-phase solvent of water and toluene, and then the pH value of the system was adjusted to 7-8. γ-aminopropyltriethoxysilane was added to react to prepare γ-aminopropyltriethoxysilane-modified SiO2 nanospheres. Acrylic acid, 4-cyano-4-(phenylthioformylthio)valeric acid and azobisisobutyronitrile are added to tetrahydrofuran for a primary reaction to obtain a first product; the first product, perfluorodecyl acrylate and azobisisobutyronitrile are added to tetrahydrofuran for a secondary reaction to obtain an amphiphilic fluorinated block copolymer PAA-b-PFADE; The amphiphilic fluorinated block copolymer PAA-b-PFADE, a catalyst and ethanol are mixed and ultrasonically dispersed, and the γ-aminopropyltriethoxysilane-modified SiO2 nanospheres are added. After reaction, the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres are obtained.

2. The method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres according to claim 1, characterized in that: The particle size of the SiO2 nanospheres is 30-500 nm.

3. The method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres according to claim 1, wherein: The ratio of the SiO2 nanospheres to γ-aminopropyltriethoxysilane is (0.5-3.0) g: (100-600) μL.

4. The method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres according to claim 1, characterized in that: The mass ratio of the acrylic acid to 4-cyano-4-(phenylthioformylthio)pentanoic acid and perfluorodecyl acrylate is 7:0.2:(15.5-51.8).

5. The method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres according to claim 1, characterized in that: During the primary reaction, the reaction temperature is 75-90° C. and the reaction time is 7-12 h; during the secondary reaction, the reaction temperature is 75-90° C. and the reaction time is 7-12 h.

6. The method for preparing SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres according to claim 1, characterized in that: The mass ratio of the amphiphilic fluorinated block copolymer PAA-b-PFADE to the γ-aminopropyltriethoxysilane-modified SiO2 nanospheres is (0.03-0.18):(0.075-0.45).

7. A SiO2 / PAA-b-PFADE amphiphilic Janus nanosphere, characterized in that: Prepared by the method according to any one of claims 1 to 6.

8. Use of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres according to claim 7 in the preparation of a super-amphiphobic coating, characterized in that: First, a hydroxy acrylic resin prepolymer solution is coated on the surface of the substrate, and then a mixed solution of a crosslinking agent and the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is coated, and the super amphiphobic coating is obtained after drying.

9. The use of SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the preparation of super-amphiphobic coatings according to claim 8, characterized in that: The coating amount of the hydroxy acrylic resin prepolymer solution, the crosslinking agent and the SiO2 / PAA-b-PFADE amphiphilic Janus nanosphere mixed solution is 0.05~0.06mL / cm 2 The concentration of the hydroxy acrylic resin prepolymer solution is 0.1 to 0.6 g / mL, and the concentration of the SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres in the mixed solution of the crosslinker and SiO2 / PAA-b-PFADE amphiphilic Janus nanospheres is 0.01 to 0.035 g / mL.

10. A super-amphiphobic coating, characterized in that: Prepared by the method according to any one of claims 8 to 9; the super amphiphobic coating has an oil contact angle of 150°~157°, an oil sliding angle of 2.6°~9.4°, a water contact angle of 152°~160°, and a water sliding angle of 1.9°~9°.

Images