CN112876955A - Fluorine-containing polyarylether-based super-hydrophobic coating with scale-like morphology and preparation method thereof - Google Patents
Fluorine-containing polyarylether-based super-hydrophobic coating with scale-like morphology and preparation method thereof Download PDFInfo
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- 239000011737 fluorine Substances 0.000 title claims abstract description 49
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
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- 229910052681 coesite Inorganic materials 0.000 claims abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 11
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- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims abstract description 9
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 12
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- 238000000034 method Methods 0.000 claims description 9
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- 239000000126 substance Substances 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 3
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- 229910010272 inorganic material Inorganic materials 0.000 description 2
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
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Abstract
The invention belongs to the field of polymer composite materials, and relates to a fluorine-containing polyarylether-based super-hydrophobic coating with a scale-like shape and a preparation method thereof. Comprises (1) preparing fluorine-containing polyarylether by polycondensation of decafluorobiphenyl and hexafluorobisphenol A; (2) dissolving fluorine-containing polyarylether in polar aprotic solvent, and adding appropriate amount of SiO2Preparing the coating from nano microspheres and Carbon Nano Tubes (CNT); (3) and (3) spraying the coating on base materials such as an aluminum plate, a cement plate and the like, and drying to obtain the fluorine-containing polyarylether-based super-hydrophobic coating with the scaly appearance. The super-hydrophobic coating has the advantages of high water contact angle, high adhesive force, corrosion resistance, high temperature resistance and the like, and also has the self-cleaning performance similar to that of lotus leavesIt can prevent the adhesion of thick soil. The super-hydrophobic coating is simple to prepare, is suitable for industrial production, and has wide application prospects.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and relates to a fluorine-containing polyarylether-based super-hydrophobic coating with a scale-like shape and a preparation method thereof.
Background
The super-hydrophobic phenomenon is very common in the nature, for example, lotus leaves have natural super-hydrophobic performance, because the lotus leaves have a mastoid-shaped micro-nano structure on the surface and also have the combined action of horny layer wax-shaped substances. Besides lotus leaves, many insects also show super-hydrophobic characteristics, such as the ability of water flies to walk on the water surface is obtained by means of the super-hydrophobic property of bristles on legs, the ability of butterflies to be not wetted by rainwater by means of the super-hydrophobic property on wings, and the like.
The super-hydrophobic material has immeasurable application prospects in the directions of metal corrosion prevention, self-cleaning, anti-icing, oil-water separation and the like. Novel superhydrophobic functional materials have become one of the new hotspots of research in the field of materials. (Langmuir, 2005, 21(19): 8978-
Inorganic nano materials are doped in the organic polymer coating, so that the surface appearance of a micro-nano scale can be formed, and super-hydrophobicity is realized. Silicon-based materials, carbon-based materials, metal oxides and other inorganic materials can be used to form inorganic-organic hybrid superhydrophobic coatings with polymers. The polymer is often a general-purpose polymer material such as polyacrylate, polyurethane, epoxy resin, or the like. However, these polymers have low glass transition temperatures and cannot be used at high temperatures; meanwhile, the micro-nano morphology such as scaly shape is difficult to form, the micro-nano structure is almost completely formed by inorganic particles, and the obtained coating has low super-hydrophobicity and stability; in addition, they are easy to be corroded by acid and alkali, rubbed mechanically and the like during use, so that the super-hydrophobic property is damaged.
The polyarylether is a material with excellent performance, and has good thermal stability, high mechanical strength and good corrosion resistance. The fluorine-containing polyarylether introduces fluorine atoms into the molecular chain of the polyarylether, and the structure not only reduces the surface free energy, but also ensures that the super-hydrophobic material has stronger mechanical property, better thermal stability and more durable acid, alkali and salt resistance. The fluorine-containing polyarylether expands the application scene of the super-hydrophobic material, so that the super-hydrophobic material becomes more practical.
In the prior art, patent CN 110054884 a discloses a super-hydrophobic film and a preparation method thereof, the super-hydrophobic film has a polyaryletherketone film layer and a silica nanosphere hydrophobic layer which are stacked, a plurality of nanospheres are arranged in the silica nanosphere hydrophobic layer, each silica nanosphere is planted with a plurality of tridecafluorooctyl branched chains, a part of sphere of each silica nanosphere and an epitaxial part of a part of tridecafluorooctyl branched chain are embedded in the polyaryletherketone film layer, and the embedding of the silica nanospheres and the epitaxial part of the tridecafluorooctyl branched chains is utilized to improve the hydrophobic property and the impact resistance of the film. But the process of planting silicon dioxide with a tridecafluorooctyl branched chain is complicated, and the cost in actual production is high.
Disclosure of Invention
The invention aims to provide a fluorine-containing polyarylether-based super-hydrophobic coating with a scale-like shape and a preparation method thereof, wherein the fluorine-containing polyarylether with excellent chemical stability and corrosion resistance and inorganic nano-filler are used for preparing a super-hydrophobic coating, so that the coated base materials such as aluminum plates, cement plates and the like have the capacity of resisting viscous soil pollution.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a fluorine-containing polyarylether-based super-hydrophobic coating with a scaly appearance comprises the following steps:
(1) dissolving decafluorobiphenyl and hexafluorobisphenol A in a molar ratio of 1:1 in N-methylpyrrolidone to prepare a solution with a mass concentration of 10-50%, adding cesium fluoride in an amount which is 2-10 times that of hexafluorobisphenol A under the protection of argon, magnetically stirring at room temperature for 10-20 hours, then pouring into deionized water to separate out a precipitate, collecting the precipitate, dissolving with dichloromethane to prepare a solution with a mass concentration of 1-10%, pouring into methanol to separate out the precipitate, filtering, collecting the precipitate, and drying in a vacuum oven at 60 ℃ for 12-48 hours to obtain the fluorine-containing polyarylether.
The fluorine-containing polyarylether has the following chemical structural formula:
wherein n =10~ 200.
(2) Dissolving fluorine-containing polyarylether into a polar aprotic solvent to prepare a uniform solution, and adding SiO with the diameter of 5-10 nm2And magnetically stirring the nano microspheres and Carbon Nano Tubes (CNT) with the diameter of 10-15 nm for 3-5 h, and then ultrasonically dispersing for 20-40 min to obtain the coating.
(3) And (3) uniformly spraying the coating on the surface of the base material by using a spray gun, and drying in a drying oven at the temperature of 60-80 ℃ for 3-6 h to obtain the fluorine-containing polyarylether-based super-hydrophobic coating.
In the step (1), the volume of the deionized water is 5-50 times of the volume of the N-methylpyrrolidone; the volume of the methanol is 5-50 times of that of the dichloromethane.
In the step (2), the polar aprotic solvent includes any one of N, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
In the step (2), the mass ratio of the fluorine-containing polyarylether to the polar aprotic solvent is 1: 20-50.
In the step (2), the SiO2The mass ratio of the nano-microspheres to the fluorine-containing polyarylether solution is 1: 10-50.
In the step (2), the mass ratio of the CNT to the fluorine-containing polyarylether solution is 1: 20-100.
In the step (3), the base material comprises an aluminum plate, paper or a cement plate and the like.
In the step (3), the thickness of the coating is 30-200 μm.
The invention utilizes the polycondensation reaction of hexafluorobisphenol A and decafluorobiphenyl to obtain fluorine-containing polyarylether, then the fluorine-containing polyarylether is dissolved in a polar aprotic solvent, and inorganic nanoparticles are added to obtain the fluorine-containing polyarylether-based super-hydrophobic coating. The coating is sprayed on different base materials such as an aluminum plate and the like to obtain the fluorine-containing polyarylether-based super-hydrophobic coating with the scaly appearance.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fluorine-containing polyarylether-based super-hydrophobic coating has the advantages of high temperature resistance, corrosion resistance, high mechanical strength, good film-forming property and the like.
(2) The fluorine-containing polyarylether-based super-hydrophobic coating has a scaly micro-nano scale rough structure, and is high in water contact angle and small in water sliding angle.
(3) The fluorine-containing polyarylether-based super-hydrophobic coating can resist the adhesion of viscous soil and can effectively promote the soil to roll off from the surface of the base material, thereby preventing the base material from being polluted by the viscous soil.
Drawings
FIG. 1 is a graph of water contact angle for the superhydrophobic coating in example 5.
FIG. 2 is a Scanning Electron Microscope (SEM) image of the surface of the superhydrophobic coating of example 5.
FIG. 3 is a graph of water contact angles of the superhydrophobic coating of example 5 tested at different pH values.
Fig. 4 is an SEM image of the surface of the superhydrophobic coating of example 5 after soaking in a solution of pH =1 for 10 days.
Fig. 5 is an SEM image of the surface of the superhydrophobic coating of example 5 after soaking in a solution of pH =13 for 10 days.
FIG. 6 is a graph comparing the effect of example 5 on fouling by sticky soil of a superhydrophobic coated surface (left panel) with an uncoated surface (right panel).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the scope of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1 fluorine-containing polyarylether based on decafluorobiphenyl and hexafluorobisphenol A
1.6706 g (5 mmol) of decafluorobiphenyl, 1.6812 g (5 mmol) of hexafluorobisphenol A and 10mL of N-methylpyrrolidone were added to the three-necked flask, and the reaction mixture was completely dissolved by magnetic stirring. Adding 5 g of cesium fluoride under the protection of argon, reacting at room temperature for 12 hours, then pouring into 100mL of deionized water to separate out a precipitate, filtering and collecting the precipitate, dissolving with 50mL of dichloromethane, pouring into 300mL of methanol to separate out the precipitate, filtering and collecting the precipitate, and drying in a vacuum oven at 60 ℃ to obtain the fluorine-containing polyarylether.
Example 2 fluorine-containing polyarylether-based superhydrophobic coating FPAE/SiO2Preparation of/CNT-1
0.5 g of the fluorine-containing polyarylether prepared in example 1 was dissolved in a beaker containing 6.5 g N-methylpyrrolidone. Weigh 0.14 g SiO again2Adding the nano microspheres and 0.07 g of CNT into the beaker, and stirring for 8 hours by magnetic force to uniformly mix the inorganic materials in the solution to obtain the required coating. Finally, the prepared coating is uniformly coated on the surface of an aluminum plate in a spraying mode and dried in an oven at 80 ℃ for 4 hours. The water contact angle of the cured coating was measured to be 151 ° using a contact angle tester.
Example 3 fluorine-containing polyarylether-based super-hydrophobic coating FPAE/SiO2Preparation of/CNT-2
0.5 g of the fluorine-containing polyarylether prepared in example 1 was dissolved in 6.5 g N-methylpyrrolidone, and the procedure of example 2 was followed except that 0.14 g of CNT was added. The water contact angle of the cured coating was 153 ° as measured by a contact angle tester.
Example 4 fluorine-containing polyarylether-based super-hydrophobic coating FPAE/SiO2Preparation of/CNT-3
0.5 g of the fluorine-containing polyarylether prepared in example 1 was dissolved in 6.5 g N-methylpyrrolidone, and the procedure of example 2 was followed except that 0.21 g of CNT was added. The water contact angle of the cured coating was 157 ° using a contact angle tester.
Example 5 fluorine-containing polyarylether-based super-hydrophobic coating FPAE/SiO2Preparation of/CNT-4
0.5 g of the fluorine-containing polyarylether prepared in example 1 was dissolved in 6.5 g N-methylpyrrolidone, and the procedure of example 2 was followed except that 0.28 g of CNT was added. The water contact angle of the cured coating was measured to be 175 ° using a contact angle tester (fig. 1). The morphology of the coating is characterized by using SEM, and a large number of sheet structures are formed on the surface of the coating, and the sheet structures are gathered together to construct the surface roughness with a micro-nano scale (figure 2).
Example 6 fluorine-containing polyarylether-based super-hydrophobic coating FPAE/SiO2Contact angle test of/CNT-4 in acid-base environment
The product obtained in example 5 was subjected to a water contact angle test procedure at different pH values.
(1) Diluting concentrated hydrochloric acid in a quantity of water to a solution of pH =1, pH =3, pH =5, respectively; deionized water as a liquid at pH = 7; dissolving a certain amount of sodium hydroxide in water to prepare solutions with pH =9, pH =11 and pH =13 respectively; 3.5 wt% sodium chloride water solution is prepared as artificial seawater.
(2) The product of example 2 was subjected to water contact angle test using different pH solutions prepared in step (1), respectively (fig. 3).
Example 7 fluorine-containing polyarylether-based super-hydrophobic coating FPAE/SiO2Chemical stability test of/CNT-4
The product obtained in example 5 was subjected to a chemical stability test.
(1) Dissolving a certain amount of concentrated hydrochloric acid in water to prepare a solution with pH = 1; a solution of pH =13 was prepared by dissolving a certain amount of sodium hydroxide in water.
(2) Immersing the sample in the embodiment 2 into the solution prepared in the step (1) for 10 days, taking out the sample, washing the excessive impurities on the surface of the sample, and drying.
(3) And (5) using the SEM to characterize the surface appearance of the dried sample.
Fig. 4 shows the surface morphology of the coating after being immersed in a solution with pH =1 for 10 days to be corroded, and it can be seen that the coating still has a micro-nano double-rough structure, which is similar to the surface morphology of the coating which is not corroded. This demonstrates that the coating is less affected and that the coating is chemically very stable under strong acid conditions.
Fig. 5 shows the surface morphology of the coating after being soaked in a solution with pH =13 for 10 days to be corroded, and it can be seen that the coating still has a micro-nano double-rough structure, which is similar to the surface morphology of the coating which is not corroded. This demonstrates that the coating is less affected under strong alkaline conditions and that the coating has good chemical stability.
Example 8 fluorine-containing polyarylether-based super-hydrophobic coating FPAE/SiO2Anti-fouling performance test of/CNT-4
The sample of example 5 and the sample that was not treated with the coating were placed on the same platform, then a certain amount of viscous soil was poured on the surface of both samples, and the platform was gently tilted. It can be seen that at a very small angle of inclination, the soil rolled off the surface of the sample of example 5, whereas the soil on the surface of the sample that was not treated with the coating had almost no rolling (fig. 6).
Claims (10)
1. A fluorine-containing polyarylether-based super-hydrophobic coating with a scale-like shape is characterized in that the coating of the coating comprises fluorine-containing polyarylether and SiO2The coating is scaly in microscopic appearance, the width of the scales is 30-60 nm, the thickness of the scales is 5-8 nm, and silicon dioxide nanoparticles and carbon nanotubes are contained among the scales.
2. The preparation method of the fluorine-containing polyarylether-based super-hydrophobic coating with the scale-like morphology according to claim 1, is characterized by comprising the following steps:
(1) dissolving decafluorobiphenyl and hexafluorobisphenol A in N-methylpyrrolidone to prepare a solution with the mass concentration of 10-50%, adding cesium fluoride under the protection of argon, magnetically stirring at room temperature for 10-20 hours, then pouring into deionized water to separate out a precipitate, collecting the precipitate, dissolving with dichloromethane to prepare a solution with the mass concentration of 1-10%, pouring into methanol to separate out the precipitate, filtering, collecting the precipitate, and drying in a vacuum oven at 60 ℃ for 12-48 hours to obtain the fluorine-containing polyarylether;
the fluorine-containing polyarylether has a chemical structural formula as follows:
wherein n = 10-200;
(2) dissolving the obtained fluorine-containing polyarylether in a polar aprotic solvent to prepare a uniform solution, and adding SiO2Magnetically stirring the nano microspheres and the carbon nano tubes for 3-5 hours, and then performing ultrasonic treatment for 20-40 min to uniformly disperse the nano microspheres and the carbon nano tubes to obtain a coating;
(3) and (3) uniformly spraying the obtained coating on the surface of the base material by using a spray gun, and drying in an oven at the temperature of 60-80 ℃ for 3-6 h to obtain the fluorine-containing polyarylether-based super-hydrophobic coating with the scaly appearance.
3. The production method according to claim 2, wherein in the step (1), the molar ratio of decafluorobiphenyl to hexafluorobisphenol A is 1:1, and the molar ratio of cesium fluoride to hexafluorobisphenol A is 2 to 10: 1.
4. the method according to claim 2, wherein in the step (1), the volume of the deionized water is 5 to 50 times that of the N-methylpyrrolidone; the volume of the methanol is 5-50 times of that of the dichloromethane.
5. The method according to claim 2, wherein in the step (2), the polar aprotic solvent is any one of N, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
6. The preparation method according to claim 2, wherein in the step (2), the mass ratio of the fluorine-containing polyarylether to the polar aprotic solvent is 1: 10-50.
7. The production method according to claim 2, wherein in the step (2), the SiO is2The mass ratio of the nano microspheres to the fluorine-containing polyarylether solution is 1: 10-50; the mass ratio of the CNT to the fluorine-containing polyarylether solution is 1: 20-100.
8. The method according to claim 2, characterized in thatCharacterized in that in the step (2), SiO is used2The diameter of the nano microsphere is 5-10 nm, and the diameter of the carbon nano tube is 10-15 nm.
9. The method according to claim 2, wherein in the step (3), the substrate is an aluminum plate, paper or cement plate.
10. The method according to claim 2, wherein in the step (3), the thickness of the coating layer is 30 to 200 μm.
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