Composite anti-seepage paint, preparation method thereof and composite anti-seepage paint coating

Abstract

The invention relates to the field of anti-seepage coatings, and discloses a composite anti-seepage coating, a preparation method thereof and a composite anti-seepage coating coating. The preparation method of the composite anti-seepage coating comprises the following steps: 1) in the presence of a solvent, carrying out contact reaction on graphene oxide and a silane coupling agent to obtain a contact reaction product; 2) dispersing the contact reaction product and glass fibers to obtain a dispersed product; and (3) the dispersion product and epoxy resin are mixed, the composite anti-seepage coating is obtained, and the weight ratio of the glass fibers to the graphene oxide is (0.5-3): 3. A composite anti-seepage paint coating formed by using the composite anti-seepage paint is high in mechanical strength and better in physical barrier property, especially in anti-seepage property on small molecule media, and meanwhile, the composite anti-seepage paint has an extremely excellent anti-corrosion effect.

Description

Technical Field

[0001] The invention relates to the field of anti-seepage coatings, and in particular to a composite anti-seepage coating and a preparation method thereof, and a composite anti-seepage coating coating. Background Art

[0002] Graphene oxide is similar to the nanomaterial graphene and has a single-layer flaky structure. The difference is that graphene oxide has functional groups such as hydroxyl, carboxyl and epoxy groups grafted on its surface, and can be covalently or non-covalently combined with various active groups to obtain different functions. In addition, compared with graphene, graphene oxide has better mechanical properties and shielding barrier capabilities, and shows great application potential in the field of anti-seepage of small molecule permeable media. It can be used as a reinforcing filler for polymer anti-seepage coatings. In actual application, the strong interaction between graphene oxide flakes leads to its easy agglomeration during the synthesis, preparation and processing of composite coatings, which greatly reduces the physical barrier properties of the composite coatings, especially the anti-seepage properties, and often leads to failure problems.

[0003] CN105802452A discloses a method for preparing a graphene coating, which mainly comprises dispersing graphene in a resin to prepare an anti-corrosion coating with a partial anti-seepage function.

[0004] CN102807812A discloses a novel polyurethane latent curing agent, and discloses a one-component polyurethane waterproof coating using the novel latent curing agent and a preparation method thereof. The waterproof coating prepared by the method has relatively good anti-seepage performance. However, the coating disclosed in the patent has the problem of too fast storage viscosity growth and poor storage performance.

[0005] CN109929426B discloses a latent curing agent type one-component polyurethane waterproof coating and a preparation method thereof, which mainly enhances the waterproof performance and storage performance of the finished coating by adding polyisocyanate, but there are also problems such as low mechanical strength of the coating formed by the coating.

[0006] These three solutions only strengthen the anti-corrosion performance, anti-seepage performance or storage performance of the coating, but fail to take into account all the performances. Therefore, it is of great significance and necessity to develop a coating with high mechanical strength, excellent anti-seepage performance and anti-corrosion performance. Summary of the invention

[0007] The purpose of the present invention is to overcome the problem that the coatings in the prior art cannot have high mechanical strength, excellent impermeability and high anti-corrosion performance, and to provide a composite anti-seepage coating and a preparation method thereof and a composite anti-seepage coating coating. The composite anti-seepage coating coating formed by the composite anti-seepage coating of the present invention has high mechanical strength, better physical barrier properties, especially better anti-penetration properties for small molecule media, and at the same time has extremely excellent anti-corrosion effect.

[0008] In order to achieve the above object, the present invention provides a method for preparing a composite anti-seepage coating, which comprises the following steps:

[0009] 1) contacting graphene oxide with a silane coupling agent in the presence of a solvent to obtain a contact reaction product;

[0010] 2) dispersing the contact reaction product with glass fibers to obtain a dispersed product;

[0011] 3) mixing the dispersed product with epoxy resin to obtain a composite anti-seepage coating,

[0012] Wherein, the weight ratio of the glass fiber to the graphene oxide is 0.5-3:3.

[0013] Preferably, the method further comprises: in step 1), a step of dispersing the graphene oxide and the solvent.

[0014] Preferably, the weight ratio of the graphene oxide to the solvent is 1:600-1000.

[0015] Preferably, the solvent is selected from one or more of acetone, methanol and DMF, preferably acetone.

[0016] The method for dispersing the graphene oxide and the solvent is ultrasonic dispersion.

[0017] Preferably, the ultrasonic dispersion conditions include: ultrasonic power of 100-400 W, ultrasonic temperature of 20-30° C., and ultrasonic time of 1-2 h.

[0018] Preferably, the thickness of the graphene oxide is 1-3 nm; more preferably, the thickness of the graphene oxide is 2 nm.

[0019] Preferably, the diameter of the graphene oxide is 0.2-10 μm; more preferably, the diameter of the graphene oxide is 4-8 μm.

[0020] The silane coupling agent is one or more of N-aminoethyl-3-aminopropylmethyldimethoxysilane, methyltrichlorosilane and methyltriethoxysilane, preferably N-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0021] Preferably, the usage ratio of the graphene oxide to the silane coupling agent is 1:150-200; more preferably, the usage ratio of the graphene oxide to the silane coupling agent is 1:160-170.

[0022] Preferably, the contact reaction conditions include: temperature of 70-90° C. and time of 4-8 hours.

[0023] Preferably, the weight ratio of the glass fiber to the graphene oxide is 0.5-3:3.

[0024] Preferably, the dispersion method is to ultrasonically disperse the mixture of the contact reaction product and the glass fiber.

[0025] Preferably, the conditions for ultrasonic dispersion include: ultrasonic power of 200-2600 W, ultrasonic temperature of 25-30° C., and ultrasonic time of 2-3 h.

[0026] The weight ratio of the graphene oxide to the epoxy resin is 1:150-180, preferably 1:160-170.

[0027] The mixing conditions include: temperature of 10-35° C. and time of 6-8 h.

[0028] Step 3) also includes the step of adding an auxiliary agent during the mixing process. Preferably, the auxiliary agent is a pigment.

[0029] According to a second aspect of the present invention, a composite anti-seepage coating prepared by the preparation method of the composite anti-seepage coating of the present invention is provided.

[0030] According to a third aspect of the present invention, a composite anti-seepage coating is provided, wherein the composite anti-seepage coating is prepared using the composite anti-seepage coating prepared by the preparation method of the composite anti-seepage coating described in the present invention or is prepared by the composite anti-seepage coating described in the present invention.

[0031] Through the above technical solution, the present invention modifies graphene oxide by using a silane coupling agent, thereby improving the dispersion performance of graphene oxide in the coating, thereby extending the diffusion path of the permeable medium inside the coating, and making the composite anti-seepage coating have better physical barrier performance. At the same time, glass fiber is added to the modified graphene oxide filler to enhance the mechanical strength of the coating, form a double-layer physical barrier inside the coating, further optimize the anti-penetration ability of the coating, and also make up for the structural defects caused by local graphene oxide agglomeration. DETAILED DESCRIPTION

[0032] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0033] According to a first aspect of the present invention, a method for preparing a composite anti-seepage coating is provided, wherein the method comprises:

[0034] 1) contacting graphene oxide with a silane coupling agent in the presence of a solvent to obtain a contact reaction product;

[0035] 2) dispersing the contact reaction product with glass fibers to obtain a dispersed product;

[0036] 3) mixing the dispersed product with epoxy resin to obtain a composite anti-seepage coating,

[0037] Wherein, the weight ratio of the glass fiber to the graphene oxide is 0.5-3:3.

[0038] According to the present invention, in order to make the graphene oxide evenly dispersed in the solvent, step 1) also includes a step of dispersing the graphene oxide and the solvent.

[0039] Preferably, the dispersion is ultrasonic dispersion.

[0040] Preferably, the ultrasonic dispersion conditions include: ultrasonic power of 100-400W, ultrasonic temperature of -2-5°C, and ultrasonic time of 1-3h; more preferably, the ultrasonic dispersion conditions include: ultrasonic power of 100-400W, ultrasonic temperature of 0°C, and ultrasonic time of 1-2h.

[0041] In a preferred embodiment of the present invention, the ultrasonic dispersion needs to be performed in an ice water bath environment (temperature is 0° C.).

[0042] According to the present invention, the amount of the solvent can be selected according to the amount of the graphene oxide. In order to save the solvent cost, preferably, the weight ratio of the graphene oxide to the solvent in step 1) is 1:600-1000; more preferably, the weight ratio of the graphene oxide to the solvent is 1:750-850.

[0043] In the present invention, in order to make the graphene oxide uniformly dispersed, the solvent contained in step 1) is preferably selected from one or more of acetone, methanol and DMF; more preferably, the solvent is acetone.

[0044] According to the present invention, from the aspect of improving the dispersibility of the graphene oxide powder in the anti-seepage coating, preferably, the thickness of the graphene oxide is 1-3 nm; more preferably, the thickness of the graphene oxide is 2 nm.

[0045] In addition, the length of the graphene oxide may be 0.2-10 μm, and preferably, the length of the graphene oxide is 4-8 μm.

[0046] In the present invention, the length of the graphene oxide refers to the longest distance between two points on the graphene oxide.

[0047] The graphene oxide may be obtained by the Hummers method and / or may be a commercially available graphene oxide product.

[0048] In the present invention, in order to improve the dispersion performance of graphene oxide in the polymer coating and extend the diffusion path of the permeable medium inside the coating, and have better physical barrier performance, the silane coupling agent is selected from one or more of N-aminoethyl-3-aminopropylmethyldimethoxysilane, methyltrichlorosilane and methyltriethoxysilane; more preferably, the silane coupling agent is N-aminoethyl-3-aminopropylmethyldimethoxysilane.

[0049] According to the present invention, the amount of the silane coupling agent can be selected according to the amount of the graphene oxide. Considering the rational use of the binding sites on the graphene oxide, preferably, the weight ratio of the graphene oxide to the silane coupling agent is 1:150-200; more preferably, the weight ratio of the graphene oxide to the silane coupling agent is 1:160-170.

[0050] According to the present invention, in order to modify graphene oxide with a silane coupling agent and improve the dispersion performance and physical properties of graphene oxide, in step 1), preferably, the contact reaction conditions include: temperature of 70-90°C and time of 4-8h; more preferably, the contact reaction conditions include: temperature of 75-85°C and time of 5-7h.

[0051] In the present invention, preferably, the weight ratio of the graphene oxide to the glass fiber is 3:0.5-3; more preferably, the weight ratio of the graphene oxide to the glass fiber is 3:1-2.

[0052] According to the present invention, the diameter of the glass fiber may be 4-12 μm, preferably 6-8 μm.

[0053] In addition, the length of the glass fiber may be 2-6 mm, preferably 2-3 mm.

[0054] According to the present invention, in order to make the glass fiber uniformly dispersed in the contact reaction product of step 1), in step 2), the contact reaction product and the glass fiber are dispersed, and the dispersion is preferably ultrasonic dispersion. The ultrasonic dispersion can be performed once or multiple times. When multiple ultrasonic dispersions are performed, it is preferred that after the previous ultrasonic dispersion, the dispersion is subjected to stillness and solid-liquid separation to obtain a dispersion, and then the dispersion is subjected to ultrasonic separation.

[0055] According to the present invention, the ultrasonic dispersion conditions may be existing conditions that can be used for dispersion. Preferably, the ultrasonic dispersion conditions include: ultrasonic power of 200-2600W, ultrasonic temperature of 20-30°C, and ultrasonic time of 2-3h.

[0056] According to the present invention, in order to make the dispersion product obtained in step 2) disperse more uniformly and to fully exert the barrier properties of the filler, in step 3), the dispersion product obtained is mixed with an epoxy resin.

[0057] Preferably, the epoxy resin is selected from various existing resins that can be used for film formation. Preferably, the epoxy resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, polyurea resin, polyurethane resin, silicone resin and fluorocarbon resin; more preferably, the epoxy resin is novolac epoxy resin.

[0058] According to the present invention, the weight ratio of the graphene oxide to the epoxy resin in step 1) is 1:150-180; more preferably, the weight ratio of the graphene oxide to the epoxy resin in step 1) is 1:160-170.

[0059] According to the present invention, in step 3), preferably, the conditions for mixing the dispersed product with the epoxy resin include: temperature of 10-35°C, time of 4-10h; more preferably, the conditions for mixing the dispersed product with the epoxy resin include: temperature of 20-30°C, time of 6-8h.

[0060] According to the present invention, preferably, the method further comprises: a step of adding a pigment during the mixing of the dispersed product with the epoxy resin. The pigment may be any existing pigment that can be used in coatings, preferably, the pigment is one or more of titanium dioxide, zinc oxide and red iron oxide.

[0061] According to the present invention, preferably, the amount of the pigment is such that the content of the pigment in the composite anti-seepage coating is 0-1.5 wt %; more preferably, the amount of the pigment is such that the content of the pigment in the composite anti-seepage coating is 0.8-1.0 wt %.

[0062] According to the present invention, preferably, the method further comprises: a step of adding an auxiliary agent during the mixing of the dispersed product with the epoxy resin. The auxiliary agent may be any existing functional auxiliary agent that can be used for coatings, preferably, the auxiliary agent is one or more of a wetting and dispersing agent, a leveling agent, an anti-settling agent, a defoaming agent, a matting agent and a thickener.

[0063] In addition, the dosage of the auxiliary agent can be selected according to the conventional dosage in the art, and those skilled in the art can select it according to actual needs.

[0064] Preferably, the amount of the wetting and dispersing agent used is such that the content of the wetting and dispersing agent in the composite anti-seepage coating is 2-3% by weight, more preferably 2.5% by weight.

[0065] Preferably, the amount of the leveling agent is such that the content of the leveling agent in the composite anti-seepage coating is 1-2% by weight, more preferably 1.5% by weight.

[0066] Preferably, the amount of the anti-settling agent is such that the content of the anti-settling agent in the composite anti-seepage coating is 1-7% by weight, more preferably 4% by weight.

[0067] Preferably, the defoaming agent is used in an amount such that the content of the defoaming agent in the composite anti-seepage coating is 1-4% by weight, more preferably 3% by weight.

[0068] Preferably, the amount of the matting agent is such that the content of the matting agent in the composite anti-seepage coating is 1-4% by weight, more preferably 2% by weight.

[0069] Preferably, the amount of the thickener is such that the content of the thickener in the composite anti-seepage coating is 1-3% by weight, more preferably 2% by weight.

[0070] Preferably, the wetting and dispersing agent is lecithin.

[0071] Preferably, the leveling agent is ethylene glycol butyl ether and / or polyacrylate.

[0072] Preferably, the anti-settling agent is one or more of fumed silica, thixotropic resin and organic modified bentonite.

[0073] Preferably, the defoaming agent is silicone oil and / or polyacrylate.

[0074] Preferably, the matting agent is one or more of silica aerogel, micro powder wax and talcum powder.

[0075] Preferably, the thickener is polyurethane and / or bentonite.

[0076] According to a second aspect of the present invention, a composite anti-seepage coating prepared by the preparation method of the composite anti-seepage coating of the present invention is provided.

[0077] According to a third aspect of the present invention, a composite anti-seepage coating is provided, wherein the composite anti-seepage coating is prepared using the composite anti-seepage coating prepared by the preparation method of the composite anti-seepage coating described in the present invention or is prepared by the composite anti-seepage coating described in the present invention.

[0078] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0079] Example 1

[0080] 3 parts by weight of graphene oxide (purchased from Shanghai Aladdin Chemical Co., Ltd., with a thickness of 2 nm and a length of 6 μm) were mixed with 2400 parts by weight of acetone (purchased from Shanghai Titan Technology Co., Ltd., analytical grade) and ultrasonically dispersed in an ice-water bath (ultrasonic power of 250 W, ultrasonic temperature of 0° C., and ultrasonic time of 1.5 h). After uniform ultrasonic dispersion, 500 parts by weight of N-aminoethyl-3-aminopropylmethyldimethoxysilane (purchased from Sinopharm Chemical Reagent Company, analytical grade) were added to the suspension and stirred at 80° C. for 6 hours. 1 part by weight of glass fiber (purchased from Jiangsu Lihua New Materials Co., Ltd., 200 g / m 2 Model, length is 2mm, diameter is 8μm), and ultrasonic dispersion is carried out (ultrasonic power is 400W, ultrasonic temperature is 25℃, ultrasonic time is 2.5h), and pigment (titanium dioxide), wetting dispersant (lecithin, purchased from Jiangsu Maiqi Chemical Co., Ltd. egg phosphatidylcholine model), leveling agent (ethylene glycol butyl ether), anti-settling agent (organic modified bentonite, purchased from Ningbo Xindong Mining Industry and Trade Co., Ltd. Organoclay 935 model, the same below), defoaming agent (silicone oil, purchased from Shanghai Pucheng Chemical Co., Ltd. PDMS100 model), matting agent (talcum powder, purchased from Anhui Shiguang (Group) Co., Ltd. 325 mesh model), thickener (polyurethane, purchased from Hunan Hengda Paint Co., Ltd. 1K model) and epoxy resin (bisphenol A type epoxy resin, purchased from Shanghai Aladdin Chemical Co., Ltd. E44 model, the same below) 80g are added to the obtained solution, and stirred at 25℃ for 7 hours to obtain a composite anti-seepage coating S1, whose component ratio is shown in Table 1;

[0081] Example 2

[0082] 3 parts by weight of graphene oxide (purchased from Shanghai Aladdin Chemical Co., Ltd., with a thickness of 2 nm and a length of 6 μm) and 2400 parts by weight of acetone (purchased from Shanghai Titan Technology Co., Ltd., analytical grade) were mixed and uniformly dispersed in an ice-water bath ultrasonic manner (ultrasonic power of 250 W, ultrasonic temperature of 0 ° C, and ultrasonic time of 1.5 h). After uniform ultrasonic dispersion, 500 parts by weight of N-aminoethyl-3-aminopropylmethyldimethoxysilane (purchased from Sinopharm Chemical Reagent Company, analytical grade) were added to the suspension and stirred at 80 ° C for 5 hours. 1.5 parts by weight of glass fiber (purchased from Jiangsu Lihua New Materials Co., Ltd. 200 g / m 2Model, length 2mm, diameter 8μm), and ultrasonic dispersion (ultrasonic power 400W, ultrasonic temperature 25℃, ultrasonic time 2.5h), and add pigment (titanium dioxide), wetting dispersant (lecithin), leveling agent (ethylene glycol butyl ether), anti-settling agent (organic modified bentonite), defoaming agent (silicone oil), matting agent (talc), thickener (polyurethane) and epoxy resin (bisphenol A type epoxy resin) 81g to the obtained solution, stir at 25℃ for 7 hours to obtain a composite anti-seepage coating S2, whose component ratio is shown in Table 1.

[0083] Example 3

[0084] 3 parts by weight of graphene oxide (purchased from Shanghai Aladdin Chemical Co., Ltd., with a thickness of 2 nm and a length of 6 μm) and 2400 parts by weight of acetone (purchased from Shanghai Titan Technology Co., Ltd., analytical grade) were mixed and uniformly dispersed in an ice-water bath by ultrasonication (ultrasonic power of 250 W, ultrasonic temperature of 0 ° C, and ultrasonic time of 1.5 h). After uniform ultrasonication, 500 parts by weight of N-aminoethyl-3-aminopropylmethyldimethoxysilane (purchased from Sinopharm Chemical Reagent Company, analytical grade) were added to the suspension and stirred at 80 ° C for 5 hours. 2 parts of glass fiber (purchased from Jiangsu Lihua New Materials Co., Ltd. 200 g / m 2 Model, length 2mm, diameter 8μm), and ultrasonic dispersion (ultrasonic power 400W, ultrasonic temperature 25℃, ultrasonic time 2.5h), and add pigment (titanium dioxide), wetting dispersant (lecithin), leveling agent (ethylene glycol butyl ether), anti-settling agent (organic modified bentonite), defoaming agent (silicone oil), matting agent (talc), thickener (polyurethane) and epoxy resin (bisphenol A type epoxy resin) 80g to the obtained solution, stir at 25℃ for 7 hours to obtain a composite anti-seepage coating S3, whose component ratio is shown in Table 1.

[0085] Example 4

[0086] The method of Example 1 was followed, except that the amount of glass fiber used was 0.5 parts by weight. A composite anti-seepage coating S4 was obtained in the same manner, and its composition ratio is shown in Table 1.

[0087] Example 5

[0088] The method of Example 1 was followed, except that the amount of glass fiber used was 2.5 parts by weight. A composite anti-seepage coating S5 was obtained in the same manner, and its composition ratio is shown in Table 1.

[0089] Example 6

[0090] The method of Example 1 is followed, except that the glass fiber has a diameter of 10 μm and a length of 6 mm (purchased from Guangdong Chaoying New Material Technology Co., Ltd., model number E-Glass Fiber). The composite anti-seepage coating S6 is obtained in the same manner, and its component ratio is shown in Table 1.

[0091] Example 7

[0092] The method of Example 1 was followed, except that N-aminoethyl-3-aminopropylmethyldimethoxysilane was replaced with the same amount of methyltrichlorosilane to obtain a composite anti-seepage coating S7, the composition ratio of which is shown in Table 1.

[0093] Example 8

[0094] The method of Example 1 was followed, except that N-aminoethyl-3-aminopropylmethyldimethoxysilane was replaced with the same amount of methyltriethoxysilane to obtain a composite anti-seepage coating S8, the composition ratio of which is shown in Table 1.

[0095] Comparative Example 1

[0096] The method of Example 1 was followed, except that the step of adding glass fiber was not included.

[0097] 3 parts by weight of graphene oxide (purchased from Shanghai Aladdin Chemical Co., Ltd., with a thickness of 2 nm and a length of 6 μm) were mixed with 2400 parts by weight of acetone (purchased from Shanghai Titan Technology Co., Ltd., analytical grade) and uniformly dispersed by ultrasonication in an ice-water bath (ultrasonic power of 250 W, ultrasonic temperature of 0°C, and ultrasonic time of 1.5 h). After uniform ultrasonic dispersion, 500 parts by weight of N-aminoethyl-3-aminopropylmethyldimethoxysilane (purchased from Sinopharm Chemical Reagent Company, analytical grade) were added to the suspension and stirred continuously at 80°C for 6 hours. Without adding glass fiber, ultrasonic dispersion (ultrasonic power of 400 W, ultrasonic temperature of 25° C., and ultrasonic time of 2.5 h) was performed, and pigment (titanium dioxide), wetting dispersant (lecithin), leveling agent (ethylene glycol butyl ether), anti-settling agent (organically modified bentonite), defoaming agent (silicone oil), matting agent (talc), thickener (polyurethane) and epoxy resin (bisphenol A type epoxy resin) were added to the obtained solution, and stirred at room temperature for 7 hours to obtain an anti-seepage composite coating D1.

[0098] The group distribution ratio is shown in Table 1.

[0099] Comparative Example 2

[0100] The method of Example 1 was followed, except that the amount of glass fiber used was 0.2 parts by weight. A composite anti-seepage coating D2 was obtained in the same manner, and its composition ratio is shown in Table 1.

[0101] Comparative Example 3

[0102] The method of Example 1 was followed, except that the amount of glass fiber used was 4 parts by weight. A composite anti-seepage coating D3 was obtained in the same manner, and its composition ratio was as shown in Table 1.

[0103] Comparative Example 4

[0104] The method of Example 1 was followed, except that the modification with N-aminoethyl-3-aminopropylmethyldimethoxysilane was not performed.

[0105] 3 parts by weight of graphene oxide (purchased from Shanghai Aladdin Chemical Co., Ltd., with a thickness of 2 nm and a length of 6 μm) and 2400 parts by weight of acetone (purchased from Shanghai Titan Technology Co., Ltd., analytical grade) were mixed and uniformly dispersed by ultrasonication in an ice-water bath (ultrasonic power of 250 W, ultrasonic temperature of 0° C., and ultrasonic time of 1.5 h). After uniform ultrasonic dispersion, 2 parts by weight of glass fiber (purchased from Jiangsu Lihua New Materials Co., Ltd., 200 g / m 2 Model, length 2mm, diameter 8μm), and ultrasonic dispersion (ultrasonic power 400W, ultrasonic temperature 25℃, ultrasonic time 2.5h), and pigment (titanium dioxide), wetting dispersant (lecithin), leveling agent (ethylene glycol butyl ether), anti-settling agent (organic modified bentonite), defoaming agent (silicone oil), matting agent (talc), thickener (polyurethane) and epoxy resin (bisphenol A type epoxy resin) were added to the obtained solution, and stirred at 25℃ for 7 hours to obtain a composite anti-seepage coating D4, whose component ratio is shown in Table 1.

[0106] Comparative Example 5

[0107] 1.0g aniline trimer and 1.0g graphene (purchased from Ningbo Moxi Technology Co., Ltd.) are dispersed in 1.0L toluene solution, and ultrasonic dispersion is performed for 1 hour to obtain a graphene dispersion. The content of graphene in toluene after modification by aniline trimer reaches 1g / L. The graphene dispersion is added to 45g epoxy resin (model E44, purchased from Jiangsu Wujiang Heli Resin Factory), and a mixture A is obtained after mixing. 2g leveling agent (ethylene glycol butyl ether), 4g defoamer (silicone oil), 2g anti-settling agent (organically modified bentonite) and 45g polyamide curing agent are added successively to the mixture A, and stirred evenly to obtain a graphene composite coating D5.

[0108] Table 1

[0109]

[0110] Note: The contents of the above ingredients are all based on the total weight of the anti-seepage coating as 100% by weight.

[0111] Test Example 1

[0112] The obtained anti-seepage coatings S1-S8 and D1-D5 were coated on Q235 steel plates with a thickness of 100 μm after curing. The water penetration time of the coatings formed by the coatings was tested under the test conditions of GB / T16777-2008. The results are shown in Table 2.

[0113] Table 2

[0114] Water seepage time / h S1 1070 S2 1200 S3 1100 S4 920 S5 970 S6 1010 S7 950 S8 920 D1 700 D2 810 D3 890 D4 770 D5 700

[0115] Test Example 2

[0116] The obtained anti-seepage coatings S1-S8 and D1-D5 were coated on Q235 steel plates with a thickness of 100 μm after curing, and the salt spray corrosion resistance was tested under the test conditions of GB / T 1771-2017. The results are shown in Table 3.

[0117] Table 3

[0118] Salt spray resistance time S1 3700 S2 3920 S3 3840 S4 3430 S5 3500 S6 3610 S7 3670 S8 3640 D1 2300 D2 3230 D3 3310 D4 2980 D5 2200

[0119] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing a composite anti-seepage coating, It is characterized in that The Method The following steps are included: 1) contacting graphene oxide with a silane coupling agent in the presence of a solvent to obtain a contact reaction product; 2) dispersing the contact reaction product with glass fibers to obtain a dispersed product; 3) mixing the dispersed product with epoxy resin to obtain a composite anti-seepage coating, Wherein, the weight ratio of the graphene oxide to the glass fiber is 3:0.5-3.

2. The method according to claim 1, in, The method further comprises: in step 1), a step of dispersing the graphene oxide and the solvent; Preferably, the weight ratio of the graphene oxide to the solvent is 1:600-800; Preferably, the solvent is selected from one or more of acetone, methanol and DMF, preferably acetone.

3. The method according to claim 2, in, In step 1), the method of dispersing the graphene oxide and the solvent is ultrasonic dispersion; Preferably, the ultrasonic dispersion conditions include: ultrasonic power of 100-400 W, ultrasonic temperature of 20-30° C., and ultrasonic time of 1-2 h.

4. The method according to claim 1, in, The thickness of the graphene oxide is 1-3 nm, preferably 2 nm; Preferably, the length of the graphene oxide is 0.2-10 μm, preferably 4-8 μm.

5. The method according to claim 1, in, In step 1), the silane coupling agent is selected from one or more of N-aminoethyl-3-aminopropylmethyldimethoxysilane, methyltrichlorosilane and methyltriethoxysilane, preferably N-aminoethyl-3-aminopropylmethyldimethoxysilane.

6. The method according to claim 1, in, In step 1), the ratio of the graphene oxide to the silane coupling agent is 1:150-200; preferably 1:160-170; Preferably, the contact reaction conditions include: temperature of 70-90° C. and time of 4-8 h.

7. The method according to claim 1, in, The weight ratio of the graphene oxide to the glass fiber is 1:0.3-1.

8. The method according to claim 1, in, In step 2), preferably, the dispersion method is to ultrasonically disperse the mixture of the contact reaction product and the glass fiber; Preferably, the conditions for ultrasonic dispersion include: ultrasonic power of 200-2600 W, ultrasonic temperature of 20-30° C., and ultrasonic time of 2-3 h.

9. The method according to claim 1, in, The weight ratio of the graphene oxide to the epoxy resin is 1:150-180, preferably 1:160-170.

10. The method according to claim 1, in, In step 3), the mixing conditions include: temperature of 10-35° C. and time of 6-8 h.

11. The method according to claim 1, in, The method further comprises: the step of adding an auxiliary agent during the mixing process of step 3); Preferably, the auxiliary agent is a pigment.

12. The composite anti-seepage coating prepared by the preparation method of the composite anti-seepage coating according to any one of claims 1 to 11.

13. A composite anti-seepage coating, It is characterized in that The composite anti-seepage coating is prepared by using the composite anti-seepage coating prepared by the preparation method of the composite anti-seepage coating described in any one of claims 1 to 11 or the composite anti-seepage coating described in claim 12.

14. The composite anti-seepage coating according to claim 13, in, The composite anti-seepage coating is obtained by coating the composite anti-seepage coating on the surface of a substrate and then curing the coating.

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