Super-hydrophobic oleophobic impermeable fluorine-containing coating and preparation method thereof, and super-hydrophobic oleophobic impermeable fluorine-containing coating and preparation method thereof

Abstract

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

Description

Technical Field

[0001] The present invention belongs to the technical field of super-hydrophobic materials, and in particular relates to a super-hydrophobic, oleophobic, anti-seepage fluorine-containing coating and a preparation method thereof, as well as a super-hydrophobic, oleophobic, anti-seepage fluorine-containing coating and a preparation method thereof. Background Art

[0002] Powder coating is a new type of coating material with many advantages in the industrial and civil construction fields. First of all, powder coating does not contain volatile organic solvents (VOC) at all, which is more friendly to human health and the environment. Secondly, the coating formed by powder coating has high hardness, corrosion resistance, wear resistance, and a long service life. In addition, powder coating is easy to use, convenient and safe to transport and store, and can be applied to the coating of various common substrates such as metals, plastics, and ceramics.

[0003] Fluorinated copolymer powder refers to a copolymer powder in which the H atoms directly connected to the carbon atoms by covalent bonds in the main chain or side chain of an organic polymer are partially or completely replaced by F atoms. Compared with small molecule fluorides and fluorinated emulsions, fluorinated copolymer powder has excellent chemical stability, thermal stability, weather resistance, low surface energy, and is stable during use, not easy to lose, and does not contain VOC and surfactants. The powder coating prepared with it has good corrosion resistance, waterproof, oil-proof, anti-fouling, and weather resistance.

[0004] Chinese patent CN104245802B discloses the manufacture method of composite particles, powder coating, coating film, laminate and composite particles, by making the particles consisting of fluoropolymer and the particles consisting of adhesive polymer combined and the composite particles consisting of fluoropolymer and adhesive polymer, the composite particles can be used as powder coating and applied to common substrates. Chinese patent CN105694682A discloses a super hydrophobic polyester resin powder coating, first using solution polymerization method to synthesize fluorinated copolymer powder, then by mixing with other functional resins to prepare, the hydrophobic polyester resin powder coating has excellent hydrophobicity, is a kind of powder coating with good rust resistance. However, due to the hydrophobic powder coating mainly attached to the substrate surface in a physical accumulation mode, poor adhesion is easy to fall off, and the accumulation gap of powder is large and not resistant to the penetration of solution, resulting in the poor durability of the super hydrophobic oleophobic coating prepared by it, it is necessary to develop a super hydrophobic oleophobic fluorine-containing coating with good adhesion and strong impermeability. Summary of the invention

[0005] The present invention is made to solve the above-mentioned problems, and aims to provide a super hydrophobic, oleophobic, anti-seepage fluorine-containing coating and a preparation method thereof, as well as a super hydrophobic, oleophobic, anti-seepage fluorine-containing coating and a preparation method thereof.

[0006] The invention provides a method for preparing a super-hydrophobic, oleophobic and anti-seepage fluorine-containing coating, which has the following characteristics and comprises the following steps: step S10, dispersing a fluorine-containing monomer and a non-fluorine-containing monomer in an aqueous solution with an emulsifier content of (1.5-5) wt% according to (2-30) wt%: (2-30) wt%, adding (0.5-3) wt% of azobisisobutylamidine hydrochloride AIBA, and polymerizing for 1-12 hours at a temperature of 50 DEG C-90 DEG C to obtain a fluorine-containing copolymer emulsion; step S20, demulsifying the fluorine-containing copolymer emulsion with alcohol, filtering with qualitative filter paper, and obtaining 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-seepage fluorine-containing coating.

[0007] In the preparation method of the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating provided by the present invention, it can also have the following characteristics: wherein, in step S10, 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 acrylate, perfluorohexyl ethylene, perfluorobutyl ethyl methacrylate, perfluorobutyl ethyl acrylate, perfluorobutyl ethylene, hexafluorobutyl methacrylate, and hexafluorobutyl acrylate.

[0008] The method for preparing the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating provided by the present invention may also have the following characteristics: wherein, in step S10, the non-fluorine monomer is selected from any one or any combination of alkyl acrylates having a carbon chain number of 1-18 and alkyl methacrylates having a carbon chain number of 1-18.

[0009] The method for preparing the super-hydrophobic, oleophobic and anti-seepage fluorine-containing coating provided by the present invention may also have the following characteristics: wherein, in step S10, the emulsifier is composed of a non-ionic surfactant and / or an anionic surfactant.

[0010] In the preparation method of the super-hydrophobic, oleophobic and anti-seepage fluorine-containing coating provided by the present invention, the following characteristics may also be provided: wherein, in step S20 and step S30, the alcohol is any one or more of methanol, ethanol, propanol and isopropanol,

[0011] In step S30, the repeated washing is washing with deionized water and alcohol alternately, and the washing times with deionized water and alcohol are both no less than 3 times.

[0012] The present invention also provides a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating, which has the following characteristics: it is prepared by using the above-mentioned preparation method of the super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating.

[0013] The present invention also provides a method for preparing a super hydrophobic, oleophobic, and anti-seepage fluorine-containing coating, which has the following characteristics and comprises the following steps: S50, brushing an adhesive on the surface of a cement-based material and waiting for it to be semi-dry, referred to as a semi-dry coating; S60, spraying the super hydrophobic, oleophobic, and anti-seepage fluorine-containing coating on the semi-dry coating and curing it to obtain a super hydrophobic, oil-repellent, and anti-seepage fluorine-containing coating.

[0014] The method for preparing the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating provided by the present invention may also have the following characteristics: wherein, in step S50, the adhesive is 704 organic silicone adhesive, and the semi-drying condition is curing at room temperature for 0.5-1h, and in step S60, the curing condition is curing at room temperature for 22-25h.

[0015] The present invention also provides a super hydrophobic, oleophobic, anti-seepage fluorine-containing coating, which has the following characteristics: it is prepared by using the above-mentioned preparation method of the super hydrophobic, oleophobic, anti-seepage fluorine-containing coating.

[0016] The super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating provided by the present invention may also have the following characteristics: wherein, the super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating is composed of a double-layer structure of a low surface energy fluorine-containing copolymer surface layer and a dense organic silicone layer; the fluorine-containing copolymer surface layer has hydrophobic and oleophobic properties, which can prevent aqueous or oily substances from adhering to and wetting the coating; the organic silicone layer can prevent the solution from penetrating the coating, and can also play a bonding role between the substrate and the fluorine-containing copolymer surface layer.

[0017] Functions and Effects of the Invention

[0018] According to the super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating and its preparation method involved in the present invention, and super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating and its preparation method, because the preparation method of super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating includes: according to a specific ratio, fluorine-containing monomers and non-fluorine monomers are dispersed in an emulsifier aqueous solution, and then AIBA is added, and polymerization reaction is performed at a specific temperature to obtain a fluorine-containing copolymer emulsion, and the fluorine-containing copolymer emulsion is demulsified with alcohol, filtered, and washed and then vacuum dried, ground into powder, and sieved to obtain a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating. The coating is a low surface energy polymer, relative to low surface energy compounds of small molecules (long-chain alkanes, fluoroalkane, silane, fluorosilane, etc.), it has excellent hydrophobic and oleophobic properties of fluorine-containing compounds, and at the same time, the cost is lower, the stability is better, and it is less likely to be lost during service.

[0019] In addition, the preparation method of the super-hydrophobic, oleophobic and anti-seepage fluorine-containing coating is simple in method, easy to operate and suitable for large-scale production.

[0020] Further, the super hydrophobic and oleophobic anti-seepage fluorine-containing coating of the present invention is composed of a low surface energy fluorine-containing copolymer surface layer and a dense organic silicone layer double-layer structure. The fluorine-containing copolymer surface layer has a hydrophobic and oleophobic property, which can prevent the adhesion and wetting of aqueous or oily substances to the coating. The organic silicone layer can prevent the solution from penetrating the coating, and can also play a good bonding effect between the substrate and the fluorine-containing copolymer surface layer. Therefore, the super hydrophobic and oleophobic anti-seepage fluorine-containing coating of the present invention has excellent waterproof, oil-proof and anti-seepage capabilities. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is a flowchart of a method for preparing a super-hydrophobic, oleophobic and anti-seepage fluorine-containing coating according to Example 1 of the present invention;

[0022] Figure 2 This is a hydrophobic and oleophobic photograph of the fluorine-containing copolymer powder (super-hydrophobic and oleophobic anti-seepage fluorine-containing coating) in Example 2 of the present invention (blue is water droplets dyed with methylene blue, and red is dyed mineral oil droplets). DETAILED DESCRIPTION

[0023] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the following embodiments and drawings are combined to specifically describe the super-hydrophobic, oleophobic, anti-seepage fluorine-containing coating and its preparation method, as well as the super-hydrophobic, oleophobic, anti-seepage fluorine-containing coating and its preparation method of the present invention.

[0024] Example 1

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

[0026] Figure 1 It is a flowchart of the method for preparing the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating of Example 1 of the present invention.

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

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

[0029] In this step, the fluorine-containing monomer is selected from any one or any combination 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; the non-fluorine-containing monomer is selected from any one or any combination of alkyl acrylates having a carbon chain number of 1 to 18 and alkyl methacrylates having a carbon chain number of 1 to 18; and the emulsifier is composed of a nonionic surfactant and / or an anionic surfactant.

[0030] Step S20, mixing the alcohol and the fluorine-containing copolymer emulsion in a mass ratio of (2-10):1 to demulsify, filtering after demulsification to obtain a demulsified precipitate.

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

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

[0033] Step S40, vacuum drying the washed precipitate at 40°C for 72 hours, grinding it into powder, and passing it through a 400-mesh sieve to obtain a fluorine-containing copolymer powder (ie, a super-hydrophobic, oleophobic, and anti-seepage fluorine-containing coating).

[0034] Step S50: Add the adhesive at a rate of (0.2-1) L / m 2 The amount of the adhesive is brushed on the surface of the substrate and cured at room temperature for 0.5h, which is recorded as the bottom layer. In this step, the adhesive is K-704 silicone sealant.

[0035] Step S60, fluorine-containing copolymer powder is prepared at a concentration of (100-500) g / m 2 The amount of the coating was sprayed on the base layer and cured at room temperature for 24 hours to obtain a super hydrophobic, oleophobic and anti-permeable fluorine-containing coating.

[0036] Example 2

[0037] This embodiment provides a super hydrophobic, oleophobic and anti-seepage fluorine-containing coating, which is prepared by the preparation method of the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating of Example 1.

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

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

[0040] In the process of preparing the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating, step S40 also prepares a super hydrophobic, oleophobic and anti-seepage fluorine-containing coating, and the hydrophobic and oleophobic properties of the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating are tested, and the results are as follows:

[0041] Figure 2 This is a hydrophobic and oleophobic photograph of the fluorine-containing copolymer powder (super-hydrophobic and oleophobic anti-seepage fluorine-containing coating) in Example 2 of the present invention (blue is water droplets dyed with methylene blue, and red is dyed mineral oil droplets).

[0042] like Figure 2 As shown, the surface fluorinated copolymer powder of the super hydrophobic and oleophobic anti-seepage fluorinated coating provided in this embodiment has significant hydrophobic and oleophobic properties.

[0043] Example 3

[0044] This example uses the method for preparing the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating in Example 1 to prepare 35 super hydrophobic, oleophobic and anti-seepage fluorine-containing coatings, and the 35 super hydrophobic, oleophobic and anti-seepage fluorine-containing coatings are respectively recorded as samples 1 to 35. The specific parameters in the preparation process of the 35 samples are shown in Table 1.

[0045] Table 1 (Specific parameters during the preparation of samples 1-35)

[0046]

[0047]

[0048]

[0049]

[0050] This embodiment also refers to the prior art Chinese patents CN104245802B, CN105694682A, and CN109504239B to prepare three coatings, which are respectively recorded as sample 36, sample 37, and sample 38.

[0051] This example also performs the following performance characterization on the prepared samples 1-38:

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

[0053] (2) Apply the coating sample on the concrete surface and test the water absorption rate and mineral oil absorption rate of the coating concrete according to the standard JC474-2008 "Mortar and Concrete Waterproofing Agent";

[0054] (3) The coating sample was coated on the concrete surface, and the surface of the super hydrophobic, oleophobic and anti-permeable fluorine-containing coating was rubbed 50 times with 1500-grit sandpaper. The water contact angle (WCA) and mineral oil contact angle (OCA) of the coating surface were tested.

[0055] The above 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 Table 1 and Table 2, combined with the performance characterization test of samples 1-35, the super-hydrophobic and oleophobic anti-seepage fluorine-containing coating of the present invention has a hydrophobicity greater than 150°, and an oleophobicity of about 150°, and has super-hydrophobic and strong oleophobic properties, which can prevent the adhesion and wetting of aqueous or oily substances to the coating. After 50 frictions with 1500-mesh sandpaper, the super-hydrophobic and oleophobic anti-seepage fluorine-containing coating of the present invention is still super-hydrophobic and strong oleophobic, and has good wear resistance.

[0060] As shown in Table 1 and Table 2, samples 1-35 in this embodiment have very low water absorption and oil absorption compared to samples 36-38 prepared under the prior art, indicating that the super hydrophobic, oleophobic and anti-permeability fluorine-containing coating of the present invention has excellent anti-penetration performance.

[0061] Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached 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 of (1.5-5) wt% at a ratio of (2-30) wt%: (2-30) wt%, adding (0.5-3) wt% of azobisisobutylamidine hydrochloride AIBA, and polymerizing at a temperature of 50° C.-90° C. for 1-12 hours to obtain a fluorine-containing copolymer emulsion; Step S20, demulsifying the fluorine-containing copolymer emulsion with alcohol, filtering with 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-seepage fluorine-containing coating.

2. The method for preparing the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating according to claim 1, characterized in that: 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 the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating according to claim 1, characterized in that: 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 the 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 the 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 washing times with deionized water and alcohol are both no less than 3 times.

6. A super hydrophobic, oleophobic, and anti-seepage fluorine-containing coating, characterized in that: The super hydrophobic, oleophobic, anti-seepage fluorine-containing coating is prepared by the preparation method of any one of claims 1 to 5.

7. A method for preparing a super hydrophobic, oleophobic and anti-seepage fluorine-containing coating, characterized in that: The following steps are involved: S50, applying the adhesive to the surface of the cement-based material by brushing and waiting for it to be semi-dry, which is recorded as semi-dry coating; S60, spraying the super hydrophobic, oil-repellent and anti-seepage fluorine-containing coating according to claim 6 onto the semi-dried coating and curing the coating to obtain a super hydrophobic, oil-repellent and anti-seepage fluorine-containing coating.

8. The method for preparing the super hydrophobic, oleophobic and anti-seepage fluorine-containing coating according to claim 7, characterized in that: 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.

9. A super hydrophobic, oleophobic, and anti-seepage fluorine-containing coating, characterized in that: The super hydrophobic, oleophobic and anti-seepage fluorine-containing coating is prepared by the preparation method of claim 7 or 8.

10. The super hydrophobic, oleophobic and anti-seepage fluorine-containing coating according to claim 9, characterized in that: in, The super hydrophobic, oleophobic and anti-seepage fluorine-containing coating is composed of a double-layer structure of a low surface energy fluorine-containing copolymer surface layer and a dense organic silicone layer. The fluorine-containing copolymer surface layer has hydrophobic and oleophobic properties, which can prevent aqueous or oily substances from adhering to and wetting the coating. The organic silicone layer can prevent the solution from penetrating the coating, and can also play a bonding role between the substrate and the fluorine-containing copolymer surface layer.

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