Superhydrophobic and oleophobic impermeable fluorine-containing coating and preparation method thereof, and superhydrophobic and oleophobic impermeable fluorine-containing coating layer and preparation method thereof

Abstract

The application provides a super-hydrophobic and oleophobic anti-permeation fluorine-containing coating and a preparation method thereof, and a super-hydrophobic and oleophobic anti-permeation fluorine-containing coating layer and a preparation method thereof, and belongs to the technical field of super-hydrophobic materials. The preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating comprises the following steps: S10, dispersing fluorine-containing monomers and non-fluorine monomers in a water solution with a (1.5-5) wt% emulsifier content according to (2-30) wt%:(2-30) wt%, adding (0.5-3) wt% AIBA, and performing polymerization reaction at 50-90 DEG C for 1-12 hours to obtain a fluorine-containing copolymer emulsion; S20, demulsifying the fluorine-containing copolymer emulsion with alcohol, filtering through qualitative filter paper to obtain demulsified precipitate; S30, repeatedly washing the demulsified precipitate with deionized water and alcohol; and S40, vacuum drying the washed precipitate, grinding into powder, and filtering through a 400-mesh sieve to obtain the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of super-hydrophobic materials, and particularly relates to a super-hydrophobic and super-oleophobic anti-permeation fluorine-containing coating material and a preparation method thereof, and a super-hydrophobic and super-oleophobic anti-permeation fluorine-containing coating and a preparation method thereof. BACKGROUND

[0002] Powder coating is a new type of coating material, which has many advantages in industrial and civil building fields. Firstly, powder coating is completely free of volatile organic solvents (VOC), which is more friendly to human health and environment. Secondly, the coating formed by powder coating has high hardness, corrosion resistance and wear resistance, and has a long service life. Moreover, powder coating is simple to use, and is convenient and safe to transport and store, and can be applied to coating of various common substrates such as metal, plastic and ceramic.

[0003] Fluorine-containing copolymer powder refers to a copolymer powder in which H atoms in the main chain or side chain of an organic polymer are partially or completely replaced by F atoms by covalent bond. Compared with small molecule fluorides and fluorine-containing emulsions, fluorine-containing copolymer powder has excellent chemical stability, thermal stability, weather resistance and low surface energy, and has good stability during use and does not contain VOC and surfactants. The powder coating prepared therefrom has good corrosion resistance, water resistance, oil resistance, stain resistance and weather resistance.

[0004] Chinese patent CN104245802B discloses a composite particle, a powder coating, a coated film, a laminated body and a method for manufacturing the composite particle, and the composite particle composed of a fluorine-containing polymer and an adhesive polymer is obtained by combining a particle composed of a fluorine-containing polymer and a particle composed of an adhesive polymer, and can be applied to common substrates as a powder coating. Chinese patent CN105694682A discloses a super-hydrophobic polyester resin powder coating, which is prepared by synthesizing fluorine-containing copolymer powder by solution polymerization and then mixing with other functional resins. The super-hydrophobic polyester resin powder coating has excellent hydrophobicity and is a powder coating with good rust resistance. However, the super-hydrophobic and super-oleophobic coating prepared therefrom has poor durability due to the poor adhesion of the hydrophobic powder coating attached to the surface of the substrate in a physical stacking manner and the large stacking gap of the powder, which cannot resist solution permeation. SUMMARY

[0005] The present application is carried out to solve the above problems, and aims to provide a super-hydrophobic and super-oleophobic anti-permeation fluorine-containing coating material and a preparation method thereof, and a super-hydrophobic and super-oleophobic anti-permeation fluorine-containing coating and a preparation method thereof.

[0006] The application provides a preparation method of super-hydrophobic, oil-repellent and anti-permeation fluorine-containing paint, which has the following characteristics: the method comprises the following steps: S10, dispersing fluorine-containing monomers and non-fluorine monomers in a water solution with a content of (1.5-5) wt% emulsifier according to (2-30) wt%:(2-30) wt%, adding (0.5-3) wt% azobisdimethylamidin hydrochloride (AIBA), and carrying out polymerization reaction at a temperature of 50-90 DEG C for 1-12 h to obtain fluorine-containing copolymer emulsion; S20, demulsifying the fluorine-containing copolymer emulsion with alcohol, filtering through qualitative filter paper to obtain demulsified precipitate; S30, repeatedly washing and filtering the demulsified precipitate with deionized water and alcohol to obtain washed precipitate; S40, vacuum drying the washed precipitate, grinding into powder, and passing through a 400-mesh sieve to obtain fluorine-containing copolymer powder as the super-hydrophobic, oil-repellent and anti-permeation fluorine-containing paint.

[0007] In the preparation method of super-hydrophobic, oil-repellent and anti-permeation fluorine-containing paint provided by the application, the fluorine-containing monomers in step S10 can be any one or any multiple of perfluorononyl ethyl methacrylate, perfluorononyl ethyl acrylate, perfluorononyl ethylene, perfluorooctyl ethyl acrylate, perfluorooctyl ethyl methacrylate, perfluorooctyl ethylene, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, perfluorohexyl ethylene, perfluorobutyl ethyl methacrylate, perfluorobutyl ethyl acrylate, perfluorobutyl ethylene, hexafluorobutyl methacrylate and hexafluorobutyl acrylate.

[0008] In the preparation method of super-hydrophobic, oil-repellent and anti-permeation fluorine-containing paint provided by the application, the non-fluorine monomers in step S10 can be any one or any multiple of alkyl acrylate with a carbon chain length of 1-18 and alkyl methacrylate with a carbon chain length of 1-18.

[0009] In the preparation method of super-hydrophobic, oil-repellent and anti-permeation fluorine-containing paint provided by the application, the emulsifier in step S10 can be composed of non-ionic surfactant and / or anionic surfactant.

[0010] In the preparation method of super-hydrophobic, oil-repellent and anti-permeation fluorine-containing paint provided by the application, the alcohol in steps S20 and S30 can be any one or more of methanol, ethanol, propanol and isopropanol.

[0011] In step S30, the repeated washing is alternating washing with deionized water and alcohol, and the washing times of deionized water and alcohol are both not less than 3 times.

[0012] The application further provides the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating prepared by the preparation method.

[0013] The application further provides a preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating, which comprises the following steps: S50, brushing the adhesive on the surface of the cement-based material and waiting for it to be semi-dry, denoted as a semi-dry coating; and S60, spraying the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating on the semi-dry coating and curing to obtain the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating.

[0014] In the preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating, the adhesive in step S50 is 704 organic silicone adhesive, and the semi-dry condition is curing at room temperature for 0.5-1 h; and the curing condition in step S60 is curing at room temperature for 22-25 h.

[0015] The application further provides the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating prepared by the preparation method.

[0016] In the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating, the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating is composed of a low-surface-energy fluorine-containing copolymer surface layer and a dense silicone adhesive layer, the fluorine-containing copolymer surface layer has hydrophobic and oleophobic properties, can prevent water-based or oil-based substances from adhering to and wetting the coating, and the silicone adhesive layer can prevent solutions from permeating the coating and can also play a bonding role between the base material and the fluorine-containing copolymer surface layer.

[0017] Effects of the application

[0018] According to the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating and the preparation method thereof, and the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating and the preparation method thereof, the preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating comprises: dispersing fluorine-containing monomers and non-fluorine monomers in an emulsifier aqueous solution according to a specific ratio, then adding AIBA, and polymerizing at a specific temperature to obtain a fluorine-containing copolymer emulsion, and then performing alcohol demulsification, filtration and washing on the fluorine-containing copolymer emulsion, vacuum drying, grinding into powder and sieving to obtain the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating. The coating is a low-surface-energy polymer, has excellent hydrophobic and oleophobic properties of fluorine-containing compounds, has lower cost, better stability and is less likely to be lost during service, compared with low-surface-energy compounds (long-chain alkanes, fluorine alkanes, silanes, fluorosilanes, etc.) of small molecules.

[0019] In addition, the preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating has the characteristics of simple method, convenient operation and suitability for large-scale production.

[0020] Further, the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating of the present application is composed of a low-surface-energy fluorine-containing copolymer surface layer and a dense silicone gel layer. The fluorine-containing copolymer surface layer has hydrophobic and oleophobic properties, which can prevent water-based or oil-based substances from adhering to and wetting the coating. The silicone gel layer can prevent the permeation of solutions into the coating, and also serves as a good adhesive between the substrate and the fluorine-containing copolymer surface layer. Therefore, the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating of the present application has excellent water-proof, oil-proof and anti-permeation capabilities. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is a flow chart of the preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating of Example 1 of the present application;

[0022] Figure 2 is a hydrophobic and oleophobic photo of the fluorine-containing copolymer powder (super-hydrophobic and oleophobic anti-permeation fluorine-containing coating) in Example 2 of the present application (blue is methyl blue dyed water droplets, and red is dyed mineral oil droplets). DETAILED DESCRIPTION

[0023] In order to make the technical means, creative features, purposes and effects achieved by the present application easy to understand, the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating and its preparation method, as well as the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating and its preparation method of the present application are specifically described below in conjunction with the drawings.

[0024] Example 1

[0025] The present embodiment provides a super-hydrophobic and oleophobic anti-permeation fluorine-containing coating and its preparation method, as well as a super-hydrophobic and oleophobic anti-permeation fluorine-containing coating and its preparation method.

[0026] Figure 1 is a flow chart of the preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating of Example 1 of the present application.

[0027] As shown in Figure 1 , the preparation method of the super-hydrophobic and oleophobic anti-permeation fluorine-containing coating includes the following steps:

[0028] Step S10, dispersing the fluorine-containing monomer and the non-fluorine monomer in a water solution with a (1.5-5) wt% emulsifier content according to (2-30) wt% : (2-30) wt%, adding (0.5-3) wt% azobisdimethylaminoformamide hydrochloride (AIBA), and polymerizing at a temperature of 50-90°C for 1-12h to obtain a fluorine-containing copolymer emulsion.

[0029] In this step, the fluorine-containing monomer is selected from any one or more of perfluorononyl ethyl methacrylate, perfluorononyl ethyl acrylate, perfluorononyl ethylene, perfluorooctyl ethyl acrylate, perfluorooctyl ethyl methacrylate, perfluorooctyl ethylene, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, perfluorohexyl ethyl acrylate, perfluorohexyl ethyl methacrylate, perfluorohexyl ethylene, perfluorobutyl ethyl methacrylate, perfluorobutyl ethyl acrylate, perfluorobutyl ethylene, hexafluorobutyl methacrylate, hexafluorobutyl acrylate; the non-fluorine monomer is selected from any one or more of alkyl acrylate with carbon chain number of 1-18 and alkyl methacrylate with carbon chain number of 1-18; and the emulsifier is composed of non-ionic surfactant and / or anionic surfactant.

[0030] In step S20, the alcohol and the fluorine-containing copolymer emulsion are mixed for demulsification at a mass ratio of (2-10):1, and after demulsification, the demulsified precipitate is obtained by filtration.

[0031] In this step, the alcohol is any one or more of methanol, ethanol, propanol, and isopropanol.

[0032] In step S30, the demulsified precipitate is washed alternately with deionized water and alcohol, with each of water washing and alcohol washing being performed for 3 times. In this step, the type of alcohol used is the same as that in S20.

[0033] In step S40, the washed precipitate is vacuum dried at 40°C for 72h, ground into powder, and passed through a 400-mesh sieve to obtain a fluorine-containing copolymer powder (i.e., a super-hydrophobic, oleophobic, and anti-permeation fluorine-containing coating).

[0034] In step S50, an adhesive is applied to the surface of the substrate in an amount of (0.2-1) L / m 2 and cured at room temperature for 0.5h, denoted as a primer. In this step, the adhesive is K-704 silicone sealant.

[0035] In step S60, the fluorine-containing copolymer powder is sprayed onto the primer in an amount of (100-500) g / m 2 and cured at room temperature for 24h to obtain a super-hydrophobic, oleophobic, and anti-permeation fluorine-containing coating.

[0036] Example 2

[0037] This example provides a super-hydrophobic, oleophobic, and anti-permeation fluorine-containing coating prepared by the method for preparing a super-hydrophobic, oleophobic, and anti-permeation fluorine-containing coating of Example 1.

[0038] Specifically, the specific parameters for each step are as follows:

[0039] In step S10, the fluorine-containing monomer is 150 g of perfluorohexyl ethyl acrylate, the non-fluorine monomer is 150 g of octadecyl methacrylate, the aqueous solution is 1000 g of deionized water containing 15 g of sodium dodecyl sulfate (SDS), the amount of azobis isobutyramidine hydrochloride (AIBA) is 5 g, the polymerization temperature is 80℃, and the polymerization time is 6 h; in step S20, the alcohol is 500 g of ethanol, and the fluorine-containing copolymer emulsion is 100 g; in step S50, the amount of the adhesive is 0.6 L / m 2 ; in step S60, the amount of the fluorine-containing copolymer powder is 300 g / m 2 .

[0040] In the process of preparing the above-mentioned super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coating, step S40 also prepared a super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coating, and the hydrophobic and oleophobic properties of the super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coating were detected, and the results are as follows:

[0041] Figure 2 is a hydrophobic and oleophobic photo of the fluorine-containing copolymer powder (super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coating) in Example 2 of the present application (blue is a water droplet dyed with methyl blue, and red is a mineral oil droplet dyed with methyl blue).

[0042] As shown in Figure 2 , the fluorine-containing copolymer powder in the surface layer of the super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coating provided by the present embodiment has significant hydrophobic and oleophobic properties.

[0043] Example 3

[0044] In this example, 35 super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coatings were prepared using the preparation method of the super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coating in Example 1, and the 35 super-hydrophobic and super-oleophobic and anti-permeation fluorine-containing coatings were respectively marked as samples 1-35. Among them, the specific parameters in the preparation process of the 35 samples are shown in Table 1.

[0045] Table 1 (specific parameters in the preparation process of samples 1-35)

[0046]

[0047]

[0048]

[0049]

[0050] In this example, three kinds of coatings were respectively prepared by referring to the prior art Chinese patents CN104245802B, CN105694682A, and CN109504239B, and were respectively marked as sample 36, sample 37, and sample 38.

[0051] The prepared samples 1-38 were also subjected to the following performance characterization:

[0052] (1) The coating sample was coated on the surface of concrete, and the static water contact angle (WCA) and mineral oil contact angle value (OCA) of the coating were measured by a contact angle instrument;

[0053] (2) The coating sample was coated on the surface of concrete, and the water absorption rate and mineral oil absorption rate of the coated concrete were tested according to the standard JC474-2008 "Waterproofing agent for mortar and concrete";

[0054] (3) The coating sample was coated on the surface of concrete, and the water (WCA) and mineral oil contact angle (OCA) of the coating surface were tested after 50 times of friction on the super-hydrophobic and oil-repellent impermeable fluorine-containing coating surface with 1500 mesh sandpaper.

[0055] The corresponding performance characterization results are shown in Table 2.

[0056] Table 2 (performance characterization results of samples 1-35)

[0057]

[0058]

[0059] As shown in Tables 1 and 2, in combination with the performance characterization tests of samples 1-35, the super-hydrophobic and oil-repellent impermeable fluorine-containing coating of the present application has a hydrophobicity greater than 150° and an oil-repellent property of about 150°, has super-hydrophobic and strong oil-repellent properties, and can prevent water-based or oil-based substances from adhering and wetting the coating. The super-hydrophobic and oil-repellent impermeable fluorine-containing coating of the present application still has super-hydrophobic and strong oil-repellent properties after 50 times of friction with 1500 mesh sandpaper, and has good wear resistance.

[0060] As shown in Tables 1 and 2, the samples 1-35 in the present embodiment have very low water absorption rate and oil absorption rate compared to the samples 36-38 prepared according to the prior art, which indicates that the super-hydrophobic and oil-repellent impermeable fluorine-containing coating of the present application has excellent impermeability.

[0061] It should be understood by those skilled in the art that the present application is not limited by the above embodiments, and the above embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection of the present application is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a super-hydrophobic, oleophobic and anti-seepage fluorine-containing coating, characterized in that: The following steps are involved: Step S10, dispersing the fluorine-containing monomer and the non-fluorine-containing monomer in an aqueous solution containing an emulsifier, adding azobisisobutylamidine hydrochloride, and polymerizing at a temperature of 50° C. to 90° C. for 1 to 12 hours to obtain a fluorine-containing copolymer emulsion; Step S20, demulsifying the fluorine-containing copolymer emulsion with alcohol, and filtering through qualitative filter paper to obtain a demulsified precipitate; Step S30, repeatedly washing and filtering the demulsified precipitate with deionized water and alcohol to obtain a washed precipitate; Step S40, vacuum drying the washed precipitate, grinding it into powder, and passing it through a 400-mesh sieve to obtain a fluorine-containing copolymer powder as a super-hydrophobic, oleophobic, and anti-permeability fluorine-containing coating; Step S50, applying an adhesive to the surface of the cement-based material and waiting for it to be semi-dry, which is referred to as a semi-dry coating, wherein the adhesive is an organic silicone adhesive; Step S60: spraying the super-hydrophobic, oleophobic and anti-permeable fluorine-containing coating onto the semi-dry coating and curing the coating to obtain a super-hydrophobic, oleophobic and anti-permeable fluorine-containing coating.

2. The method for preparing a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating according to claim 1, wherein: in, In step S10, the fluorine-containing monomer is selected from any one or more of perfluorononylethyl methacrylate, perfluorononylethyl acrylate, perfluorononylethylene, perfluorooctylethyl acrylate, perfluorooctylethyl methacrylate, perfluorooctylethylene, dodecafluoroheptyl methacrylate, dodecafluoroheptyl acrylate, perfluorohexylethyl acrylate, perfluorohexylethyl methacrylate, perfluorohexylethylene, perfluorobutylethyl methacrylate, perfluorobutylethyl acrylate, perfluorobutylethylene, hexafluorobutyl methacrylate, and hexafluorobutyl acrylate.

3. The method for preparing a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating according to claim 1, wherein: in, In step S10, the non-fluorine monomer is selected from any one or more of alkyl acrylates having a carbon chain number of 1-18 and alkyl methacrylates having a carbon chain number of 1-18.

4. The method for preparing a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating according to any one of claims 1 to 3, characterized in that: in, In step S10, the emulsifier is composed of a nonionic surfactant and / or an anionic surfactant.

5. The method for preparing a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating according to any one of claims 1 to 3, characterized in that: in, In step S20 and step S30, the alcohol is any one or more of methanol, ethanol, propanol, and isopropanol. In step S30, the repeated washing is washing with deionized water and alcohol alternately, and the number of washing times with deionized water and alcohol is not less than 3 times.

6. The method for preparing a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating according to claim 1, wherein: in, In step S50, the adhesive is 704 organic silicone adhesive, and the semi-drying condition is to cure at room temperature for 0.5-1h. In step S60, the curing condition is curing at room temperature for 22-25 hours.

7. A super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating, characterized by: The super hydrophobic, oleophobic and anti-seepage fluorine-containing coating is prepared by the preparation method of any one of claims 1 to 6.

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