CN111154344B - Super-hydrophobic and super-oleophobic coating and preparation method thereof - Google Patents

Super-hydrophobic and super-oleophobic coating and preparation method thereof Download PDF

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CN111154344B
CN111154344B CN202010067754.4A CN202010067754A CN111154344B CN 111154344 B CN111154344 B CN 111154344B CN 202010067754 A CN202010067754 A CN 202010067754A CN 111154344 B CN111154344 B CN 111154344B
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orthosilicate
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郝红
孙苗苗
赵夏
段延萍
高超权
薛甲
张冰冰
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Northwestern University
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D125/02—Homopolymers or copolymers of hydrocarbons
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    • C09D125/08—Copolymers of styrene
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Abstract

Adding deionized water, styrene, acrylic monomers, an initiator and divinyl benzene into a container, uniformly stirring, heating to 40-90 ℃, and preserving heat for 1-10 hours to obtain white St-AA copolymer emulsion; adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding ammonia water into the uniform emulsion, stirring and heating to 30-80 ℃, keeping the temperature for 0.5-8 h, then adding fluorosilicone, and keeping the temperature for 0.5-8 h to obtain the super-hydrophobic and super-oleophobic coating. The invention does not need post-processing to realize super-amphiphobicity; extreme or environment-unfriendly conditions are not needed in the synthesis process, water and ethanol are used as solvents in the preparation process, the environment is not easily polluted, and the method is suitable for large-scale production. The paint synthesized by the method has good stability, and the storage stability is more than 2 years.

Description

Super-hydrophobic and super-oleophobic coating and preparation method thereof
Technical Field
The invention belongs to the technical field of special coating, and relates to a super-hydrophobic and super-oleophobic coating and a preparation method thereof.
Background
The wettability of the solid surface is an important property of engineering materials, and plays an important role in the daily life of people and industrial production, such as waterproof cloth and self-cleaning glass in daily life; mineral froth flotation, oil exploitation, adhesion and bonding, washing, pesticide spraying, fluid conveying and the like in the industry are closely related to surface wettability. The super-amphiphobic surface has water and oil contact angles of more than 150 degrees respectively and has low contact angle hysteresis (rolling angle) with water and oil. Some animals and plants in nature also exhibit this phenomenon of super-amphiphobicity. Gorb and Rokitov reported a super amphiphobic property of leafhoppers. The surface of cicada wing has highly structured spherical particles, which are uniformly and densely coated on their outer skin, and these structures protect cicada wing from pollution. The spherical particles on the surface of the cicada wing have a hollow core and a honeycomb structure (pentagon or hexagon), and comprise a concave structure forming super-amphiphobicity, the contact angle theta of the outer skin formed by the spherical particles to water is 164.9-172.3 degrees, the contact angle theta to ethylene glycol is 152.7-164.18 degrees, and the contact angle theta to diiodomethane is 148.2-156.08 degrees.
Inspired by the surface structure of animals and plants, researchers use chemical methods to simulate similar structures to prepare super-hydrophobic/super-amphiphobic surfaces, such as template methods, photolithography, deposition methods, electrostatic spinning, sol-gel methods and the like, by manufacturing micro-nano roughness and reducing surface energy. For example, Ming et al first prepared raspberry-like SiO2The particles show a raspberry-shaped double-size morphology structure on the surface by an atomic force microscope, and the micro/nano surface morphology formed by the raspberry-shaped particles is similar to that of lotus leaves.
Although there are many ways to mimic such a super-amphiphobic surface, there are still significant challenges to building a super-amphiphobic surface. The super-amphiphobic surface has the problems of complex preparation method, high cost, dependence on a special base material and the like, so that the application range of the super-amphiphobic surface is narrow, and few products are put into the market. The construction of surfaces with controllable micro-morphology and chemical composition, and the search for simple and feasible preparation methods which can be applied to various base materials have become research hotspots in the field of super-hydrophobic/super-amphiphobic.
Disclosure of Invention
The invention aims to provide a super-hydrophobic and super-oleophobic coating and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a super-hydrophobic and super-oleophobic coating comprises the following steps:
1) adding deionized water, styrene, an acrylic monomer, an initiator and divinyl benzene into a container, uniformly stirring, heating to 40-90 ℃, and preserving heat for 1-10 hours to obtain white St-AA copolymer emulsion;
2) adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding ammonia water into the uniform emulsion, stirring and heating to 30-80 ℃, keeping the temperature for 0.5-8 h, then adding fluorosilicone, and keeping the temperature for 0.5-8 h to obtain the super-hydrophobic and super-oleophobic coating.
The invention is further improved in that in the step 1), the mass ratio of the acrylic monomer to the styrene is (0.1-8.5): (0.1-6); the dosage of the initiator is 0.1 to 3 percent of the total mass of the styrene and the acrylic monomer.
The invention is further improved in that in the step 1), the dosage of the divinyl benzene is 0.1% -8% of the total mass of the styrene and the acrylic monomer.
A further development of the invention is that in step 1), acrylic monomers CRH2R-1One or more of COOH; wherein R is 2-4; the initiator is an inorganic peroxide.
The invention is further improved in that the inorganic peroxide is one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
The invention further improves that in the step 2), the mass ratio of the orthosilicate ester to the St-AA copolymer emulsion is (0.1-10): (0.1 to 8); the dosage of the fluorosilicone accounts for 0.08-10% of the total mass of the styrene and the acrylic monomers.
The further improvement of the invention is that in the step 2), the volume percentage of the ammonia water is 25 percent, and the dosage of the ammonia water is 0.5 to 10 percent of the total mass of the orthosilicate, the St-AA copolymer emulsion and the solvent.
The invention is further improved in that in the step 2), the orthosilicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; the solvent is ethanol, methanol, propanol or isopropanol.
The invention is further improved in that in the step 2), the fluorosilicone is one or more of trifluoropropyltrichlorosilane, 1H, 2H, 2H-perfluorohexyltrichlorosilane, 1H, 2H, 2H-perfluorooctyltrichlorosilane, trifluoropropyltriethoxysilane, 1H, 2H, 2H-perfluorohexyltriethoxysilane, 1H, 2H, 2H-perfluorooctyltriethoxysilane and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane.
A super-hydrophobic and super-oleophobic coating prepared according to the method.
Compared with the prior art, the invention has the following beneficial effects:
firstly, styrene and acrylic monomers are subjected to soap-free emulsion polymerization to synthesize spherical St-AA copolymer particles, then the copolymer emulsion and Tetraethoxysilane (TEOS) are subjected to hydrolytic polycondensation to form raspberry-shaped nano particles with regular binary size, and finally, fluorosilicone with low free energy is grafted on SiO2The surface of the nanoparticles. Wherein, the submicron copolymer particles and silicon dioxide nanoparticles generated by hydrolysis of tetraethyl orthosilicate (TEOS) form raspberry-shaped nanoparticles with binary sizes, the raspberry-shaped morphology can provide the surface roughness of the coating, and the fluorosilicone can reduce the surface free energy, thereby forming a super-amphiphobic surface.
The preparation method of the super-amphiphobic coating provided by the invention does not need post-treatment to realize super-amphiphobic property; the conditions in the whole reaction process are mild, the highest temperature in the reaction process is 78 ℃, extreme or environment-unfriendly conditions are not needed in the synthesis process, water and ethanol are used as solvents in the preparation process, the environment is not easily polluted, and the method is suitable for large-scale production. The coating synthesized by the method has good stability, the finally obtained product is uniform, and the storage stability is more than 2 years.
The raw materials needed by the product generated by the sol-gel method of the organic modified nano particles are cheap and easy to obtain, and large-scale equipment is not needed for synthesis, so the cost is low, the synthesis efficiency is high, and the uniformity is good. Because the super-amphiphobic coating film of the product has a rough microstructure and does not need to rely on a substrate to provide roughness, the amphiphobic property of the surface of the coating film is not greatly influenced by the substrate. The method can be widely applied to different base materials such as glass, plastic, fabric, paper, metal and the like, and avoids special requirements of etching or other methods on the base materials.
Drawings
FIG. 1 is a schematic diagram of the synthesis process of the present invention.
FIG. 2 shows the copolymer emulsion prepared in example 1, PFDTS-SiO2-infrared spectrum of the copolymer emulsion.
FIG. 3 shows the copolymer emulsion prepared in example 1, PFDTS-SiO2Thermogravimetry of coplymer emulsions.
FIG. 4 is SEM images of different fluorosilicone-modified coating films of examples 1 and 2. Wherein (a) is PFDTS-SiO2A copolymer coating film, (b) PFOTS-SiO2-a biopolymer coating film.
FIG. 5 is PFDTS-SiO2-surface laser confocal mapping of the copolymer coating.
FIG. 6 shows the water drop in PFDTS-SiO2Photograph of the surface of the biopolymer film.
FIG. 7 shows diiodomethane droplets in PFDTS-SiO2Photograph of the surface of the biopolymer film.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Referring to fig. 1, the present invention firstly synthesizes spherical St-AA copolymer particles by soap-free emulsion polymerization of styrene and acrylic monomers, then the copolymer emulsion and Tetraethoxysilane (TEOS) undergo hydrolytic polycondensation to form raspberry-shaped nanoparticles with regular binary size, and finally, fluorosilicone with low free energy is grafted on SiO2The surface of the nanoparticles. Wherein, the submicron copolymer particles and silicon dioxide nanoparticles generated by hydrolysis of tetraethyl orthosilicate (TEOS) form raspberry-shaped nanoparticles with binary sizes, the raspberry-shaped morphology can provide the surface roughness of the coating, and the fluorosilicone can reduce the surface free energy, thereby forming a super-amphiphobic surface.
The preparation method of the super-hydrophobic and super-oleophobic coating provided by the invention comprises the following steps:
preparation of St-AA copolymer emulsion:
deionized water, styrene, an acrylic monomer, an initiator and a crosslinking monomer divinylbenzene are sequentially added into a three-neck flask, and after the mixture is fully and uniformly stirred at room temperature, the mixture is heated to 40-90 ℃ and is kept warm for 1-10 hours to obtain a white emulsion which is directly applied to the next reaction.
2.PFDTS-SiO2-biopolymer emulsion synthesis:
adding ethanol, orthosilicate ester and the copolymer emulsion into a three-mouth bottle in sequence, and stirring to obtain uniform emulsion. Then adding ammonia water, stirring and heating to 30-80 ℃, keeping the temperature for 0.5-8 h, then adding fluorosilicone, keeping the temperature for 0.5-8 h, and stopping the experiment to obtain the raspberry-shaped nanoparticle emulsion.
The specific process is that when the St-AA copolymer emulsion is prepared, the acrylic monomer: styrene ═ (0.1 to 8.5): (0.1-6); ortho-silicate ester: the mass ratio of the polymer emulsion (0.1-10) is as follows: (0.1 to 8); the adding amount of the divinyl benzene is 0.1-8% of the total mass of the styrene and the acrylic monomer; the initiator accounts for 0.1 to 3 percent of the mass of the polymerized monomer; wherein the inorganic peroxide initiator is one or more of potassium persulfate, sodium persulfate and ammonium persulfate; acrylic monomer is CRH2R- 1One or more of COOH (R ═ 2-4); the fluorosilicone accounts for 0.08-10% of the mass of the styrene and acrylic monomers; the ammonia water (volume percentage is 25%) accounts for 0.5% -10% of the total amount of the orthosilicate, the St-AA copolymer emulsion and the solvent. The solvent is ethanol, methanol, propanol or isopropanol; the orthosilicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; the fluorosilicone is one or more of trifluoropropyltrichlorosilane, 1H, 2H, 2H-perfluorohexyltrichlorosilane, 1H, 2H, 2H-perfluorooctyltrichlorosilane, trifluoropropyltriethoxysilane (PFPTS), 1H, 2H, 2H-Perfluorohexyltriethoxysilane (PFHTS), 1H, 2H, 2H-Perfluorooctyltriethoxysilane (PFOTS) and 1H, 1H, 2H, 2H-Perfluorodecyltriethoxysilane (PFDTS).
The following are specific examples.
Example 1
First 2.5g ofStyrene, 1.0g of acrylic acid, 0.015g of potassium persulfate, 150. mu.L of divinylbenzene and 50mL of deionized water were put into a three-necked flask, stirred at room temperature for 30min, then heated to 78 ℃ (200rpm), and kept for 6 hours to obtain a white emulsion. Then 15mL of ethanol, 1mL of ethyl orthosilicate and 6mL of white emulsion are sequentially added into a three-necked bottle, and the mixture is stirred for 30mins to obtain uniform emulsion. Adding 0.5mL ammonia water with volume percentage of 25%, stirring and heating to 60 deg.C, keeping the temperature for 90min, adding 50 μ L PFDTS, keeping the temperature for 90min, stopping the experiment to obtain PFDTS-SiO2-biopolymer emulsions for the preparation of coating films.
Example 2
1.5g of styrene, 2.0g of methacrylic acid, 0.020g of ammonium persulfate and 150. mu.L of divinylbenzene and 50mL of deionized water were added to a three-necked flask, stirred at room temperature for 50min, heated to 85 ℃ (300rpm) and kept for 9h to obtain a white emulsion. Then 20mL of methanol, 1.5mL of methyl orthosilicate and 6mL of white emulsion are sequentially added into a three-neck flask, and the mixture is stirred for 50mins to obtain uniform emulsion. Adding 0.5mL ammonia water with volume percentage of 25%, stirring and heating to 70 ℃, preserving heat for 60min, adding 100 mu L PFOTS, continuing preserving heat for 8h, stopping the experiment to obtain PFOTS-SiO2-biopolymer emulsions for the preparation of coating films.
Example 3
2.0g of styrene, 1.5g of acrylic acid, 0.015g of sodium persulfate and 150. mu.L of divinylbenzene, 50mL of deionized water were first added to a three-necked flask, stirred at room temperature for 30min, then heated to 70 ℃ (200rpm), and kept warm for 4h to obtain a white emulsion. Then 20mL of propanol, 2.0mL of ethyl orthosilicate and 8mL of white emulsion are sequentially added into a three-necked bottle, and stirred for 35mins to obtain uniform emulsion. Adding 0.8mL of ammonia water with volume percentage of 25%, stirring and heating to 70 ℃, preserving heat for 60min, adding 200 mu L of PFHTS, continuing preserving heat for 5h, stopping the experiment to obtain PFHTS-SiO2-biopolymer emulsions for the preparation of coating films.
Example 4
1.0g of styrene, 2.5g of ethacrylic acid, 0.018g of potassium persulfate and 150. mu.L of divinylbenzene, 40mL of deionized water were first placed in a three-necked flask and stirred at room temperature for 20min, thenThen heating to 50 ℃ (200rpm), and keeping the temperature for 8h to obtain white emulsion. Then 15mL of ethanol, 1.8mL of propyl orthosilicate and 5mL of white emulsion are sequentially added into a three-necked bottle, and stirred for 30mins to obtain uniform emulsion. Adding 0.5mL ammonia water with volume percentage of 25%, stirring and heating to 60 ℃, preserving heat for 60min, adding 300 mu L PFPTS, continuing preserving heat for 80min, stopping the experiment to obtain PFPTS-SiO2-biopolymer emulsions for the preparation of coating films.
Example 5
1.8g of styrene, 2.0g of methacrylic acid, 0.025g of ammonium persulfate and 150. mu.L of divinylbenzene, and 50mL of deionized water were first added to a three-necked flask, stirred at room temperature for 40min, heated to 85 ℃ (200rpm), and then kept warm for 5h to obtain a white emulsion. Then 25mL of isopropanol, 1.5mL of butyl orthosilicate and 5mL of white emulsion are sequentially added into a three-mouth bottle, and stirred for 30mins to obtain uniform emulsion. Adding 0.6mL of ammonia water with volume percentage of 25%, stirring and heating to 65 ℃, preserving heat for 100min, adding 300 mu L of trifluoropropyl trichlorosilane, continuing preserving heat for 3h, stopping the experiment, and obtaining the white super-hydrophobic and super-oleophobic coating for preparing the coating.
Example 6
2.5g of styrene, 1.0g of ethacrylic acid, 0.020g of potassium persulfate, 150 mu L of divinylbenzene and 50mL of deionized water are added into a three-neck flask, stirred for 40min at room temperature, heated to 80 ℃ (200rpm) and kept for 4h to obtain a white emulsion. Then 10mL of ethanol, 0.8mL of ethyl orthosilicate and 4mL of white emulsion are sequentially added into a three-necked bottle, and stirred for 30mins to obtain uniform emulsion. Adding 0.5mL of ammonia water with volume percentage of 25%, stirring and heating to 70 ℃, preserving heat for 60min, adding 60 muL of 1H, 1H, 2H, 2H-perfluorohexyl trichlorosilane, continuing preserving heat for 120min, and stopping the experiment to obtain the white super-hydrophobic and super-oleophobic coating for preparing the coating.
Example 7
1.0g of styrene, 2.5g of ethacrylic acid, 0.029g of sodium persulfate, 150. mu.L of divinylbenzene and 50mL of deionized water were added to a three-necked flask, stirred at room temperature for 30min, heated to 85 ℃ (200rpm), and then kept warm for 3h to obtain a white emulsion. Then 15mL of methanol, 2mL of ethyl orthosilicate and 6mL of white emulsion are sequentially added into a three-necked bottle, and the mixture is stirred for 40mins to obtain uniform emulsion. Adding 0.5mL of ammonia water with volume percentage of 25%, stirring and heating to 50 ℃, preserving heat for 100min, adding 80 mu L of 1H, 1H, 2H, 2H-perfluoro octyl trichlorosilane, continuing preserving heat for 4H, and stopping the experiment to obtain the white super-hydrophobic and super-oleophobic coating for preparing the coating.
Example 8
1.5g of styrene, 2.0g of acrylic acid, 0.015g of potassium persulfate and 150. mu.L of divinylbenzene, 50mL of deionized water were first added to a three-necked flask, stirred at room temperature for 30min, heated to 60 ℃ (200rpm) and kept for 8h to obtain a white emulsion. Then 18mL of isopropanol, 1.0mL of butyl orthosilicate and 5mL of white emulsion are sequentially added into a three-mouth bottle, and stirred for 30mins to obtain uniform emulsion. Adding 0.65mL of ammonia water with volume percentage of 25%, stirring and heating to 70 ℃, preserving heat for 60min, adding 120 mu L of PFPTS, continuing preserving heat for 8h, stopping the experiment to obtain PFPTS-SiO2-biopolymer emulsions for the preparation of coating films. TABLE 1St-AA copolymer emulsion, PFDTS-SiO2Indices of copolymer emulsion
Figure BDA0002376461560000081
TABLE 2St-AA copolymer emulsion coating, PFDTS-SiO2Indices of the coating of the copolymer emulsion
Figure BDA0002376461560000082
St-AA copolymer emulsion, PFDTS-SiO prepared in example 12The performance indexes of the copolymer emulsion are shown in Table 1.St-AA copolymer emulsion, PFDTS-SiO2The performance criteria of the coating of the biopolymer emulsion on the glass slide are shown in Table 2.
For St-AA copolymer emulsion and PFDTS-SiO2The biopolymer emulsion was subjected to infrared characterization, the results of which are shown in FIG. 2. At 3066cm-1，2902cm-1，1718cm-1And 1461cm-1OfThe absorption bands are due to-OH, -CH, respectively2-C ═ O and-C ═ C-groups on the phenyl ring vibrate asymmetrically and telescopically; 1461cm-1And 695cm-1The absorption band observed can be attributed to the bending vibration mode of the C-H group on the benzene ring; in addition, at 1159cm-1And 1494cm-1The characteristic absorption bands recorded are due to C-C stretching vibrations and stretching vibrations of the C-O group; in addition to the absorption bands given above, the fluorinated copolymer was found to be 1234-872cm-1An additional absorption peak was generated, which is mainly caused by overlapping of absorption peaks of fluorocarbon bond and siloxane, and Si-O stretching vibration occurred at 1080cm-1The stretching vibration of the C-F key occurs at 1350-1100 cm-1). From the infrared spectrum it can be shown that fluorocarbon bonds have been successfully grafted onto the surface of raspberry-like nanoparticles.
For copolymer emulsion and PFDTS-SiO2Thermogravimetric analysis of the copolymer emulsion gave the result of FIG. 3. The St-AA copolymer lost 97.48% by weight at 385 deg.C, with a small amount of residual solids being mainly incomplete combustion, impurities and inorganic salts. PFDTS-SiO2The copolymer emulsion had two significant weight losses, the first at around 395 ℃ and a weight loss of 37.68%. Mainly due to the cleavage of the C-C and C-O bonds. The second weight loss was 34.07 wt% at 495-510 deg.C. Mainly due to the breaking of the C-F and Si-O bonds. The results confirm that the fluorine-containing long carbon chain is grafted on the SiO2A surface. PFDTS-SiO relative to St-AA copolymer2The copolymer emulsion has high residual content, PFDTS-SiO2The residual content of copolymer was 28.25 wt%, the residue was mainly SiO2。
PFDTS-SiO2The biopolymer emulsion was prepared as a super-amphiphobic coating and subjected to SEM measurements, see FIG. 4. As can be seen from the figure, the coating film is composed of particles with binary sizes, wherein the diameter of the large sphere is between 220-400nm, the particle diameter of the small sphere is between 20-30nm, and the small spheres are densely distributed on the surface of the large sphere to form raspberry-shaped particles.
Characterization of PFDTS-SiO by laser confocal method2Surface roughness of the copolymer coating film, the results are shown in FIG. 5. The blank glass substrate has a surface roughness value of5.4 nm. Raspberry-like PFDTS-SiO2After the copolymer coating is coated on a glass substrate, the measured surface roughness is 5.790um, and the increase of the surface roughness is beneficial to enhancing the combined action of the surface hydrophobicity, the fluorocarbon chain with low surface energy and the raspberry-shaped appearance, so that the surface has super-amphiphobicity and lower drop adhesion.
Water and diiodomethane in PFDTS-SiO2Contact angles on the copolymer coating films, as shown in FIGS. 6 and 7. PFDTS-SiO2A copolymer surface, contact angle of water 167.30 ° (fig. 6), rolling angle 4.11 °; the contact angle of diiodomethane was 153.55 ° (fig. 7) and the roll angle was 4.92 °. Indicating PFDTS-SiO2The biopolymer surface has excellent non-wetting properties, it has achieved super-amphiphobicity to water and diiodomethane, and the rolling angle reaches below 5 °.
Examples 2-8 produced emulsions similar in performance to the emulsion produced in example 1.
Example 9
1) Preparation of St-AA copolymer emulsion:
adding deionized water, styrene, acrylic monomers, an initiator and divinyl benzene into a container, uniformly stirring, heating to 40 ℃, and preserving heat for 10 hours to obtain white St-AA copolymer emulsion; wherein, the mass ratio of styrene to acrylic monomer is 0.1: 0.1; the dosage of the initiator is 0.1 percent of the total mass of the styrene and the acrylic monomer, and the dosage of the divinyl benzene is 8 percent of the total mass of the styrene and the acrylic monomer.
The acrylic monomer is ethyl acrylic acid;
the inorganic peroxide is potassium persulfate.
2)PFDTS-SiO2-biopolymer emulsion synthesis:
adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding 25% ammonia water by volume percentage into the uniform emulsion, stirring and heating to 30 ℃, keeping the temperature for 8 hours, adding fluorosilicone, and keeping the temperature for 0.5 hour to obtain the super-hydrophobic and super-oleophobic coating.
Wherein the mass ratio of the orthosilicate to the St-AA copolymer emulsion is 0.1: 8;
the amount of fluorosilicone was 0.08% of the total mass of styrene and acrylic monomers.
The dosage of the ammonia water is 2 percent of the total mass of the orthosilicate, the St-AA copolymer emulsion and the solvent.
The orthosilicate is methyl orthosilicate; the solvent is ethanol.
The fluorosilicone is trifluoropropyltrichlorosilane.
Example 10
1) Preparation of St-AA copolymer emulsion:
adding deionized water, styrene, acrylic monomers, an initiator and divinyl benzene into a container, uniformly stirring, heating to 90 ℃, and preserving heat for 1h to obtain white St-AA copolymer emulsion; wherein, the styrene accounts for 1.5g, and the mass ratio of the acrylic monomer to the styrene is 8.5: 1; the amount of the initiator is 3% of the total mass of the styrene and the acrylic monomer, and the amount of the divinylbenzene is 0.1% of the total mass of the styrene and the acrylic monomer.
The acrylic monomer is a mixture of methacrylic acid and acrylic acid;
the inorganic peroxide is a mixture of sodium persulfate and ammonium persulfate.
2)PFDTS-SiO2-biopolymer emulsion synthesis:
adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding 25% ammonia water by volume percentage into the uniform emulsion, stirring and heating to 40 ℃, keeping the temperature for 7 hours, adding fluorosilicone, and keeping the temperature for 2 hours to obtain the super-hydrophobic and super-oleophobic coating.
Wherein the mass ratio of the orthosilicate to the St-AA copolymer emulsion is 1: 4;
the amount of fluorosilicone was 10% of the total mass of styrene and acrylic monomers.
The dosage of the ammonia water is 5 percent of the total mass of the orthosilicate, the St-AA copolymer emulsion and the solvent.
The orthosilicate is a mixture of ethyl orthosilicate and propyl orthosilicate; the solvent is methanol.
The fluorosilicone is a mixture of 1H, 1H, 2H, 2H-perfluorohexyltrichlorosilane and 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane.
Example 11
1) Preparation of St-AA copolymer emulsion:
adding deionized water, styrene, acrylic monomers, an initiator and divinyl benzene into a container, uniformly stirring, heating to 50 ℃, and preserving heat for 5 hours to obtain white St-AA copolymer emulsion; wherein, the styrene accounts for 1.5g, and the mass ratio of the acrylic monomer to the styrene is 3: 3; the dosage of the initiator is 1 percent of the total mass of the styrene and the acrylic monomer, and the dosage of the divinyl benzene is 1 percent of the total mass of the styrene and the acrylic monomer.
Acrylic monomer is CRH2R-1COOH; wherein, R is 4;
the inorganic peroxide is ammonium persulfate.
2)PFDTS-SiO2-biopolymer emulsion synthesis:
adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding 25% ammonia water by volume percentage into the uniform emulsion, stirring and heating to 80 ℃, keeping the temperature for 0.5h, adding fluorosilicone, and keeping the temperature for 4h to obtain the super-hydrophobic and super-oleophobic coating.
Wherein the mass ratio of the orthosilicate to the St-AA copolymer emulsion is 3: 0.1;
the amount of fluorosilicone was 1.5% of the total mass of styrene and acrylic monomers.
The dosage of the ammonia water is 10 percent of the total mass of the orthosilicate, the St-AA copolymer emulsion and the solvent.
The orthosilicate is n-butyl orthosilicate; the solvent is propanol.
The fluorosilicone is a mixture of trifluoropropyltriethoxysilane and 1H, 1H, 2H, 2H-perfluorohexyltriethoxysilane.
Example 12
1) Preparation of St-AA copolymer emulsion:
adding deionized water, styrene, acrylic monomers, an initiator and divinyl benzene into a container, uniformly stirring, heating to 70 ℃, and preserving heat for 3 hours to obtain white St-AA copolymer emulsion; wherein, the styrene accounts for 1.5g, and the mass ratio of the acrylic monomer to the styrene is 1: 6; the amount of the initiator is 0.7 percent of the total mass of the styrene and the acrylic monomer, and the amount of the divinyl benzene is 83 percent of the total mass of the styrene and the acrylic monomer.
Acrylic monomer is CRH2R-1COOH; wherein, R is 2;
the inorganic peroxide is one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
2)PFDTS-SiO2-biopolymer emulsion synthesis:
adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding 25% ammonia water by volume percentage into the uniform emulsion, stirring and heating to 50 ℃, keeping the temperature for 5 hours, adding fluorosilicone, and keeping the temperature for 7 hours to obtain the super-hydrophobic and super-oleophobic coating.
Wherein the mass ratio of the orthosilicate to the St-AA copolymer emulsion is 8: 2;
the amount of fluorosilicone was 4% of the total mass of styrene and acrylic monomers.
The dosage of the ammonia water is 0.5 percent of the total mass of the orthosilicate, the St-AA copolymer emulsion and the solvent.
The n-silicate is a mixture of propyl orthosilicate and butyl orthosilicate; the solvent is isopropanol.
The fluorosilicone is a mixture of 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane.
Example 13
1) Preparation of St-AA copolymer emulsion:
adding deionized water, styrene, acrylic monomers, an initiator and divinyl benzene into a container, uniformly stirring, heating to 60 ℃, and preserving heat for 4 hours to obtain white St-AA copolymer emulsion; wherein, the styrene accounts for 1.5g, and the mass ratio of the acrylic monomer to the styrene is 7: 5; the dosage of the initiator is 2 percent of the total mass of the styrene and the acrylic monomer, and the dosage of the divinyl benzene is 6 percent of the total mass of the styrene and the acrylic monomer.
The acrylic monomer is a mixture of acrylic acid and ethacrylic acid;
the inorganic peroxide is a mixture of potassium persulfate, sodium persulfate and ammonium persulfate.
2)PFDTS-SiO2-biopolymer emulsion synthesis:
adding a solvent, orthosilicate and St-AA copolymer emulsion into a container, and stirring to obtain uniform emulsion; and then adding 25% ammonia water by volume percentage into the uniform emulsion, stirring and heating to 60 ℃, keeping the temperature for 6 hours, adding fluorosilicone, and keeping the temperature for 8 hours to obtain the super-hydrophobic and super-oleophobic coating.
Wherein the mass ratio of the orthosilicate to the St-AA copolymer emulsion is 10: 1;
the amount of fluorosilicone was 7% of the total mass of styrene and acrylic monomers.
The dosage of the ammonia water is 8 percent of the total mass of the orthosilicate, the St-AA copolymer emulsion and the solvent.
The orthosilicate is tetraethoxysilane; the solvent is isopropanol.
The fluorosilicone is a mixture of trifluoropropyltrichlorosilane and trifluoropropyltriethoxysilane.

Claims (7)

1. A preparation method of a super-hydrophobic and super-oleophobic coating is characterized by comprising the following steps:
1) adding deionized water, styrene, acrylic monomers, an initiator and divinyl benzene into a container, uniformly stirring, heating to 40-90 ℃, and preserving heat for 1-10 hours to obtain white copolymer emulsion; wherein, the dosage of the divinyl benzene is 0.1 to 8 percent of the total mass of the styrene and the acrylic monomer; acrylic monomer is CRH2R-1One or more of COOH, R is 2-4;
2) adding a solvent, orthosilicate and copolymer emulsion into a container, and stirring to obtain uniform emulsion; then adding ammonia water into the uniform emulsion, stirring and heating to 30-80 ℃, keeping the temperature for 0.5-8 h, then adding fluorosilane, and keeping the temperature for 0.5-8 h to obtain the super-hydrophobic and super-oleophobic coating; wherein the mass ratio of the orthosilicate ester to the copolymer emulsion is (0.1-10): (0.1 to 8); the consumption of the fluorosilane accounts for 0.08 to 10 percent of the total mass of the styrene and the acrylic monomer; the fluorosilane is one or more of trifluoropropyltrichlorosilane, 1H, 2H, 2H-perfluorohexyltrichlorosilane, 1H, 2H, 2H-perfluorooctyltrichlorosilane, trifluoropropyltriethoxysilane, 1H, 2H, 2H-perfluorohexyltriethoxysilane, 1H, 2H, 2H-perfluorooctyltriethoxysilane and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane.
2. The preparation method of the super-hydrophobic and super-oleophobic coating according to claim 1, characterized in that in step 1), the mass ratio of acrylic monomers to styrene is (0.1-8.5): (0.1-6); the dosage of the initiator is 0.1 to 3 percent of the total mass of the styrene and the acrylic monomer.
3. The method for preparing the super-hydrophobic and super-oleophobic coating according to claim 1, characterized in that in step 1), the initiator is inorganic peroxide.
4. The preparation method of the super-hydrophobic and super-oleophobic coating according to claim 3, characterized in that the inorganic peroxide is one or more of potassium persulfate, sodium persulfate and ammonium persulfate.
5. The preparation method of the super-hydrophobic and super-oleophobic coating according to claim 1, characterized in that in step 2), the volume percentage of ammonia water is 25%, and the amount of ammonia water is 0.5% -10% of the total mass of the orthosilicate, the copolymer emulsion and the solvent.
6. The preparation method of the super-hydrophobic and super-oleophobic coating according to claim 1, characterized in that in step 2), the orthosilicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate; the solvent is ethanol, methanol, propanol or isopropanol.
7. A super-hydrophobic and super-oleophobic coating prepared according to the preparation method of any one of claims 1-6.
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