Composite barrier coating and method of making and use thereof

Abstract

The present application relates to the field of oil tank anti-infiltration coating, discloses a kind of composite anti-infiltration coating and its preparation method and application, the preparation method of the coating of the present application includes:1) in the presence of solvent, graphene oxide is contacted with silane coupling agent and is carried out contact reaction, and is dried to obtain solid product;2) under acidic conditions, the solution containing solid product is contacted with titanium dioxide solution and is carried out contact reaction, and the contact reaction product is dried to obtain solid product;3) using polyaniline oligomer, the second solid product obtained in step 2) is dispersed, dried, to obtain re-dispersible composite powder;4) the re-dispersible composite powder obtained and film-forming resin are mixed.According to the present application, a new titanium dioxide modified graphene oxide composite anti-infiltration coating can be provided, so that the coating has better oil medium corrosion resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of oil storage tank anti-permeation coating, in particular to a titanium dioxide modified graphene oxide composite anti-permeation coating, a preparation method and application thereof. BACKGROUND

[0002] With the increase of crude oil import and transportation, more and more vertical storage tanks are put into use, however, there are inevitably corrosive media such as chloride salt, sulfate, anaerobic bacteria in these oil products, which leads to the phenomenon of oil leakage caused by tank wall perforation. However, with the increase of service time, the storage tank often causes soil and groundwater pollution due to corrosion leakage. Therefore, how to effectively and long-term protect the crude oil storage tank and prevent the negative effects of medium penetration is a problem that researchers need to solve.

[0003] Nowadays, surface coating protection technology is one of the most commonly used anti-permeation measures for storage tanks. This method is simple, widely applicable, low in cost, easy to maintain, and can directly shield the penetration and diffusion path of corrosive media. However, due to the continuous deterioration of the quality of crude oil, the existing traditional anti-permeation coating has been difficult to meet the safety needs of actual oil storage and transportation, production. Graphene oxide with two-dimensional sheet structure as a derivative of graphene, on the basis of having similar physicochemical properties as graphene, also exhibits higher mechanical strength and matrix dispersion performance than graphene. Therefore, graphene oxide plays an important role in improving the barrier performance of anti-permeation coating. However, graphene oxide also has a large specific surface area and strong van der Waals force, which still cannot achieve satisfactory dispersion effect, and the surface of graphene oxide is grafted with various oxygen-containing functional groups, which may cause nanostructure defects, and the compactness is slightly lower than that of graphene barrier material. Therefore, nano titanium dioxide particles are used to modify and couple graphene oxide, which can enhance the dispersion of graphene oxide on one hand, and compensate for the nanostructure defects of graphene oxide by plugging micropores on the other hand, becoming a practical means for optimizing and modifying graphene oxide. CN105802452A discloses a preparation method of graphene insulation coating, which synthesizes a corrosion-resistant coating by dispersing graphene in resin. CN106010091A discloses a corrosion-resistant and static-conductive coating and a preparation method thereof, which mainly disperses graphene and carbon nanotubes into epoxy resin by using a dispersing agent to prepare a static-conductive and corrosion-resistant coating. CN114958151A discloses a composite corrosion-resistant material containing modified graphene oxide and a preparation method thereof, which improves the ability of the coating to resist acidic and alkaline media. The graphene-based coatings prepared by the above three schemes are mainly used in external corrosion-resistant fields such as marine chemical industry and electrical equipment, and are not suitable for crude oil storage tanks. SUMMARY

[0004] The present application aims to overcome the problem that the existing graphene coating technology cannot meet the anti-permeation requirements of the complex corrosive environment inside the crude oil storage tank, and to solve the problems of graphene oxide structure defects and easy agglomeration, and to provide a new titanium dioxide modified graphene oxide composite anti-permeation coating, so that the coating has better oil medium corrosion resistance.

[0005] The modified graphene oxide preparation method has the advantages of simple process and controllable process, can better combine the graphene oxide filler with the coating resin matrix, and realize uniform dispersion of the graphene oxide. The new titanium dioxide modified graphene oxide composite anti-permeation coating provided by the present application can produce good barrier effect on corrosive media such as crude oil and tank bottom deposited water, solves the problem that the traditional anti-permeation coating cannot meet the internal protection requirements of the oil storage tank, and is conducive to the application and development of graphene-based high-performance anti-permeation coating.

[0006] In order to achieve the above-mentioned purpose, the present application provides a preparation method of a composite anti-permeation coating, wherein the method comprises:

[0007] 1) In the presence of a solvent, graphene oxide is subjected to a first contact reaction with a silane coupling agent, and the first contact reaction product is subjected to a first drying to obtain a first solid product;

[0008] 2) Under acidic conditions, a solution containing the first solid product is subjected to a second contact reaction with a titanium dioxide solution, and the second contact reaction product is subjected to a second drying to obtain a second solid product;

[0009] 3) The second solid product obtained in step 2) is dispersed using polyaniline oligomers as a dispersant, and is subjected to a third drying to obtain a redispersible graphene oxide-nano titanium dioxide composite powder;

[0010] 4) The redispersible graphene oxide-nano titanium dioxide composite powder obtained in step 3) is mixed with a film-forming resin.

[0011] The weight ratio of the graphene oxide to the solvent in step 1) is 1:8-20, preferably 1:10-15.

[0012] Preferably, the weight ratio of the graphene oxide to the silane coupling agent is 1:3-18, preferably 1:5-15.

[0013] The first contact reaction is carried out in an inert atmosphere.

[0014] Preferably, the first contact reaction conditions include a temperature of 10-35℃ and a reaction time of 0.2-2h.

[0015] Preferably, the first contact reaction conditions include a temperature of 25-30℃, 0.5-1h,

[0016] Preferably, the first drying condition comprises: temperature of 70-150℃, time of 4-15h,

[0017] Preferably, the first drying condition comprises: temperature of 90-110℃, time of 6-10h.

[0018] Preferably, the solvent used in step 1) is selected from one or more of N’N-dimethylformamide, N’N-dimethylacetamide and N’N-dimethylpropionamide, preferably N’N-dimethylformamide.

[0019] Preferably, the silane coupling agent comprises one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, preferably 3-aminopropyltriethoxysilane.

[0020] Preferably, the method further comprises: before performing the first drying, performing the steps of first drying and washing the first contact reaction product.

[0021] Preferably, the solvent used in the solution containing the first solid product in step 2) is selected from one or more of N’N-dimethylformamide, N’N-dimethylacetamide and N’N-dimethylpropionamide.

[0022] Preferably, the content of the first solid product in the solution containing the first solid product is 5-10wt%,

[0023] Preferably, the acidic condition is pH value of 3.5-5.5, preferably pH value of 4-5.

[0024] Preferably, the acidic condition is adjusted by adding acetic acid.

[0025] Preferably, the concentration of the nanometer titanium dioxide solution in step 2) is 0.5-7wt%, preferably 2-5wt%,

[0026] Preferably, the weight ratio of the amount of nanometer titanium dioxide to the amount of graphene oxide is 1:1-4, preferably 1:1.5-2.5.

[0027] Preferably, the second contact reaction condition in step 2) comprises: temperature of 60-90℃, time of 5-12h,

[0028] Preferably, the second contact reaction condition comprises: temperature of 80℃, time of 6-10h,

[0029] Preferably, the second drying condition comprises: temperature of 45-100℃, time of 18-64h,

[0030] Preferably, the second drying condition comprises: temperature of 50-90℃, time of 24-48h.

[0031] Preferably, the method further comprises: before performing the second drying, performing the steps of second drying and washing on the second contact reaction product,

[0032] Preferably, the weight ratio of the graphene oxide to the polyaniline oligomer is 1:20-60, preferably 1:30-40.

[0033] In step 3), the average molecular weight of the polyaniline oligomer is 6000-10000, preferably 7000-8000,

[0034] In step 3), the dispersion is ultrasonic dispersion.

[0035] Preferably, the ultrasonic dispersion condition comprises: ultrasonic power of 100-500W, ultrasonic time of 0.2-5h.

[0036] Preferably, the ultrasonic dispersion condition comprises: ultrasonic power of 200-400W, ultrasonic time of 0.5-3h.

[0037] In step 3), the third drying condition comprises: temperature of 50-95℃, time of 6-30h.

[0038] Preferably, the third drying condition comprises: temperature of 70-90℃, time of 10-20h.

[0039] In step 4), the redispersible graphene oxide-nano titanium dioxide composite powder obtained in step 3) and part of the film-forming resin are ground, and then mixed with another part of the film-forming resin.

[0040] Preferably, the redispersible graphene oxide-nano titanium dioxide composite powder is ground with 5-20wt% of the total amount of the film-forming resin.

[0041] Preferably, the redispersible graphene oxide-nano titanium dioxide composite powder is ground with 10-15wt% of the total amount of the film-forming resin.

[0042] Preferably, the content of the redispersible graphene oxide-nano titanium dioxide composite powder is 0.1-5wt%, preferably 0.2-3wt%, based on the composite impermeable coating.

[0043] In step 4), the step of adding an additive,

[0044] Preferably, the additive is a pigment.

[0045] Preferably, the content of the auxiliary is 0.5-2% by weight based on the composite impermeable coating.

[0046] In step 4), the film-forming resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, polyurea resin, polyurethane resin, silicone resin and carbon resin, preferably phenolic epoxy resin.

[0047] According to the second aspect of the present application, the composite impermeable coating prepared by the preparation method of the composite impermeable coating of the present application is provided.

[0048] According to the third aspect of the present application, the composite impermeable coating prepared by the preparation method of the composite impermeable coating of the present application is applied in the internal impermeable of oil storage.

[0049] The preparation method of the composite impermeable coating of the present application obtains the composite impermeable coating, which has the advantages of simple process and controllable process, can produce good barrier effect on corrosive media such as crude oil and tank bottom deposited water, solves the problem that the traditional impermeable coating is difficult to meet the internal protection of oil storage tank, and is conducive to the application and development of graphene-based high-performance impermeable coating. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 The water vapor permeability of the impermeable material of test example 1 is shown.

[0051] Figure 2 The surface morphology of the impermeable material of test example 3 after immersion in crude oil for 30 days is shown.

[0052] Figure 3 The hardness of the impermeable material of test example 4 changes with the immersion time. DETAILED DESCRIPTION

[0053] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The exact numerical values of the endpoints of the ranges and any values are approximations that allow for a little variation either ways without resulting in a change in the basic function of the compositions or methods, or methods described. In this context, each numerical value should be construed in light of the number of significant figures chosen for that value and by applying normal rounding techniques to enable practical, in addition to theoretical, construal of the value.

[0054] According to the first aspect of the present application, a preparation method of a composite impermeable coating is provided, wherein the method comprises:

[0055] 1) In the presence of a solvent, graphene oxide is subjected to a first contact reaction with a silane coupling agent, and the first contact reaction product is subjected to a first drying to obtain a first solid product;

[0056] 2) under acidic conditions, subjecting a solution containing the first solid product to a second contact reaction with a titanium dioxide solution, and subjecting the second contact reaction product to a second drying to obtain a second solid product;

[0057] 3) dispersing the second solid product obtained in step 2) using polyaniline oligomer as dispersant, third drying to obtain a redispersible graphene oxide-nano titanium dioxide composite powder;

[0058] 4) mixing the redispersible graphene oxide-nano titanium dioxide composite powder obtained in step 3) with a film-forming resin.

[0059] According to the present application, the amount of the solvent can be selected according to the amount of the graphene oxide, and preferably, the weight ratio of the graphene oxide to the solvent in step 1) is 1:8-20, more preferably, the weight ratio of the graphene oxide to the solvent in step 1) is 1:10-15, in consideration of improving the dispersing performance of graphene oxide in organic solvents.

[0060] According to the present application, the amount of the silane coupling agent can be selected according to the amount of the graphene oxide, and preferably, the weight ratio of the graphene oxide to the silane coupling agent is 1:3-18, more preferably, the weight ratio of the graphene oxide to the silane coupling agent is 1:5-15, in consideration of improving the interlayer spacing of graphene oxide.

[0061] According to the present application, preferably, the first contact reaction in step 1) is carried out under an inert atmosphere. The inert atmosphere can be implemented by introducing an inert gas, and as the inert gas, for example, nitrogen, argon, etc. can be mentioned. In a specific embodiment of the present application, the inert gas can be introduced into the reaction system for bubbling. According to the present application, preferably, the first contact reaction conditions include a temperature of 10-35°C and a reaction time of 0.2-2h, more preferably, the first contact reaction conditions include a temperature of 25-30°C and a reaction time of 0.5-1h.

[0062] According to the present application, preferably, the first drying conditions include a temperature of 70-150°C and a time of 4-15h, more preferably, the first drying conditions include a temperature of 90-110°C and a time of 6-10h.

[0063] According to the present application, in order to uniformly disperse graphene oxide, as the solvent contained in the first contact reaction, preferably, the solvent is selected from one or more of N’N-dimethylformamide, N’N-dimethylacetamide and N’N-dimethylpropionamide, more preferably, the solvent is N’N-dimethylformamide.

[0064] In the present application, in order to uniformly disperse the graphene oxide, ultrasonic dispersion is performed in the solvent, and the ultrasonic dispersion conditions can be the existing conditions that can be used for dispersion. Specifically, the ultrasonic dispersion conditions can include: ultrasonic power of 200-500 W, ultrasonic temperature of 20-35℃, and ultrasonic time of 0.5-4 h.

[0065] According to the present application, from the dispersibility of the composite filler in the anti-permeation coating, preferably, the particle size of the graphene oxide is 20-50 μm; more preferably, the particle size of the graphene oxide is 30-40 μm. The graphene oxide can be obtained by Hummers method and / or using commercially available graphene oxide products.

[0066] According to the present application, in order to graft and modify the nano-titanium dioxide on the surface of the graphene oxide, the silane coupling agent is contained in the first contact reaction, preferably, the silane coupling agent is selected from one or more of 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, and N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane; more preferably, the silane coupling agent is 3-aminopropyl triethoxysilane.

[0067] In the present application, in order to remove the excess silane coupling agent and other impurities in the first contact reaction product, the method further comprises the steps of first drying, washing the first contact reaction product before performing the first drying. Preferably, the first drying conditions include: temperature of 80-120℃, and time of 6-15 h; more preferably, the first drying conditions include: temperature of 100℃, and time of 8-10 h.

[0068] According to the present application, as the washing solution for washing the first contact reaction product to remove the excess silane coupling agent and other impurities in the first contact reaction product, preferably, the washing solution is selected from one or more of ethanol, ethyl acetate, and tetrahydrofuran; more preferably, the washing solution is anhydrous ethanol. The number of washing times can be one or more, preferably 3-5 times.

[0069] According to the present application, in step 2), in order to achieve the modification of the titanium dioxide on the graphene oxide, the first solid product is mixed with a solvent to obtain the solution containing the first solid product. The solvent used in the solution containing the first solid product is selected from one or more of N’N-dimethylformamide, N’N-dimethylacetamide, and N’N-dimethylpropionamide; more preferably, the solvent used in the solution containing the first solid product is N’N-dimethylformamide.

[0070] In addition, the solution containing the first solid product can have a concentration of 3-17 wt%; preferably, the solution containing the first solid product has a concentration of 5-10 wt%.

[0071] According to the present application, in order to ensure that the second contact reaction is carried out sufficiently, in step 2), the system is adjusted to an acidic environment, preferably, the acidic system can be adjusted by adding acetic acid and / or citric acid; more preferably, the acidic system can be adjusted by adding acetic acid. According to the present application, preferably, the pH value is adjusted to be between 3.5-5.5; more preferably, the pH value is adjusted to be between 4-5.

[0072] According to the present application, in order to produce a good barrier effect on corrosive media and solve the problem that traditional impermeable coatings are difficult to meet the internal protection of oil storage tanks, in the second contact reaction, the solution containing the first solid product is subjected to a second contact reaction with titanium dioxide.

[0073] According to the present application, in step 2), the titanium dioxide is preferably used in the form of a solution, for example, which can be obtained by slowly centrifuging nano-titanium dioxide in deionized water and removing large particles in the supernatant. Preferably, the concentration of the nano-titanium dioxide solution is 0.5-7 wt%; more preferably, the concentration of the nano-titanium dioxide solution is 2-5 wt%.

[0074] According to the present application, preferably, the weight ratio of the amount of nano-titanium dioxide to the amount of graphene oxide is 1:1-4; more preferably, the weight ratio of the amount of nano-titanium dioxide to the amount of graphene oxide is 1:1.5-2.5.

[0075] According to the present application, preferably, the second contact reaction conditions include a temperature of 60-90℃ and a time of 5-12h; more preferably, the second contact reaction conditions include a temperature of 80℃ and a time of 6-10h.

[0076] According to the present application, preferably, the second drying conditions include a temperature of 45-100℃ and a time of 18-64h; more preferably, the second drying conditions include a temperature of 50-90℃ and a time of 24-48h.

[0077] In the present application, in order to remove excess N’N-dimethylformamide in the second contact reaction product, the method further comprises the steps of performing a second drying and washing of the second contact reaction product before performing the second drying. Preferably, the second drying conditions include a temperature of 80-100℃ and a time of 6-15h; more preferably, the second drying conditions include a temperature of 90℃ and a time of 8-10h.

[0078] The washing solution comprises one or more of ethanol, ethyl acetate, tetrahydrofuran, and preferably anhydrous ethanol. The washing can be performed once or multiple times, and preferably 3-5 times.

[0079] According to the present application, in order to improve the structural defects of graphene oxide and the dispersion performance of the material, the second solid product is dispersed and dried by using polyaniline oligomers as a dispersant.

[0080] According to the present application, preferably, the average molecular weight of the polyaniline oligomers is 6000-10000; more preferably, the average molecular weight of the polyaniline oligomers is 7000-8000.

[0081] According to the present application, preferably, the weight ratio of the graphene oxide to the polyaniline oligomers is 1:20-60; more preferably, the weight ratio of the graphene oxide to the polyaniline oligomers is 1:30-40.

[0082] According to the present application, the dispersion method can be ultrasonic dispersion, and preferably, the ultrasonic dispersion conditions include an ultrasonic power of 100-500W, an ultrasonic temperature of 20-35℃, and an ultrasonic time of 0.5-5h; more preferably, the ultrasonic dispersion conditions include an ultrasonic power of 200-400W, an ultrasonic temperature of 25-30℃, and an ultrasonic time of 1-3h.

[0083] According to the present application, the ultrasonic dispersion can be performed once or multiple times. When the ultrasonic dispersion is performed multiple times, preferably, after the previous ultrasonic dispersion, the dispersion liquid is obtained after standing and solid-liquid separation, and then the dispersion liquid is subjected to ultrasonic separation. The standing conditions can be performed using the conditions commonly used in the art, for example, a standing temperature of 10-35℃ and a standing time of 0.5-3h. The solid-liquid separation can be performed using various means of solid-liquid separation commonly used in the art, for example, a rotation speed of 10000-13000r / min, a temperature of 25℃, and a time of 1.5-2h.

[0084] According to the present application, the third drying conditions include a temperature of 50-95℃ and a time of 6-30h; more preferably, the third drying conditions include a temperature of 70-90℃ and a time of 10-20h.

[0085] According to the present application, in order to further improve the anticorrosion performance, preferably, the total amount of the redispersible graphene oxide-nano titanium dioxide composite powder is such that the total content of the redispersible graphene oxide-nano titanium dioxide composite powder in the composite anti-permeation coating is 0.1-5 wt%, more preferably, the total amount of the redispersible graphene oxide-nano titanium dioxide composite powder is such that the total content of the redispersible graphene oxide-nano titanium dioxide composite powder in the composite anti-permeation coating is 0.2-3 wt%.

[0086] According to the present application, in order to make the redispersible graphene oxide-nano titanium dioxide composite powder more uniformly dispersed, the redispersible graphene oxide-nano titanium dioxide composite powder is ground with part of the film-forming resin, and the grinding can be carried out under conditions commonly used in the art, for example, the temperature of the grinding can be 10-25℃, and the time of the grinding can be 0.5-2h, preferably 1-1.5h.

[0087] According to the present application, preferably, the redispersible graphene oxide-nano titanium dioxide composite powder is ground with 5-20 wt% of the total amount of the film-forming resin; more preferably, the redispersible graphene oxide-nano titanium dioxide composite powder is ground with 10-15 wt% of the total amount of the film-forming resin.

[0088] In the present application, after the grinding, the redispersible graphene oxide-nano titanium dioxide composite powder is mixed with another part of the film-forming resin, and preferably, the conditions for mixing the redispersible graphene oxide-nano titanium dioxide composite powder with another part of the film-forming resin include a temperature of 10-30℃ and a time of 20-80min; more preferably, the conditions for mixing the redispersible graphene oxide-nano titanium dioxide composite powder with another part of the film-forming resin include a temperature of 20-25℃ and a time of 30-60min.

[0089] In the present application, preferably, the amount of the film-forming resin is such that the content of the film-forming resin in the composite anti-permeation coating is 70-95 wt%; more preferably, the amount of the film-forming resin is such that the content of the film-forming resin in the composite anti-permeation coating is 80-90 wt%. For example, the amount of the film-forming resin can be 70 wt%, 75 wt% and 85 wt%.

[0090] According to the present application, preferably, the film-forming resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, polyurea resin, polyurethane resin, silicone resin and carbon resin; more preferably, the film-forming resin is phenolic epoxy resin.

[0091] According to the present application, preferably, the content of the redispersible graphene oxide-nano titanium dioxide composite powder in the composite anti-permeation coating is 0.1-5 wt% based on the composite anti-permeation coating; more preferably, the content of the redispersible graphene oxide-nano titanium dioxide composite powder is 0.2-3 wt%.

[0092] According to the present application, when the redispersible graphene oxide-nano titanium dioxide composite powder is ground with the film-forming resin, a step of adding a pigment is further included, which can be various pigments that can be used in coatings, preferably, the pigment is aniline black and / or yellow iron oxide. According to the present application, preferably, the content of the pigment in the composite impermeable coating is 0.5-2% by weight; more preferably, the content of the pigment in the composite impermeable coating is 1-1.5% by weight.

[0093] According to the present application, when the redispersible graphene oxide-nano titanium dioxide composite powder is mixed with another part of the film-forming resin, a step of adding an additive is further included, which can be various functional additives that can be used in coatings, preferably, the additive is one or more of wetting dispersants, leveling agents, anti-settling agents, defoaming agents, matting agents and thickening agents. The amount of the additive can be selected according to the conventional amount in the art, and the skilled person in the art can select according to the actual needs.

[0094] Preferably, the amount of the wetting dispersant is such that the content of the wetting dispersant in the composite impermeable coating is 1-5% by weight, more preferably 3-4% by weight.

[0095] Preferably, the amount of the leveling agent is such that the content of the leveling agent in the composite impermeable coating is 1-2% by weight, more preferably 1.4-1.6% by weight.

[0096] Preferably, the amount of the anti-settling agent is such that the content of the anti-settling agent in the composite impermeable coating is 1-7% by weight, more preferably 3-4% by weight.

[0097] Preferably, the amount of the defoaming agent is such that the content of the defoaming agent in the composite impermeable coating is 1-4% by weight, more preferably 2-3% by weight.

[0098] Preferably, the amount of the matting agent is such that the content of the matting agent in the composite impermeable coating is 1-6% by weight, more preferably 1.5-3% by weight.

[0099] Preferably, the amount of the thickening agent is such that the content of the thickening agent in the composite impermeable coating is 1-3% by weight, more preferably 1.5-2% by weight.

[0100] Preferably, the wetting dispersant is a polyester polyamide and / or a polymethyl aralkyl siloxane.

[0101] Preferably, the leveling agent is a polyether siloxane copolymer.

[0102] Preferably, the anti-settling agent is one or more of fumed silica, thixotropic resin and organically modified bentonite.

[0103] Preferably, the defoaming agent is polyether modified silicon and / or polyether.

[0104] Preferably, the matting agent is diatomite and / or silicon dioxide.

[0105] Preferably, the thickening agent is polyethylene glycol and / or magnesium aluminum silicate.

[0106] According to the present application, the composite anti-permeation coating is particularly suitable for oil storage tanks.

[0107] According to the second aspect of the present application, the composite anti-permeation coating prepared by the preparation method of the composite anti-permeation coating of the present application.

[0108] According to the third aspect of the present application, the composite anti-permeation coating prepared by the preparation method of the composite anti-permeation coating of the present application is applied in the internal anti-permeation of oil storage.

[0109] The present application will be described in detail below through examples, but the present application is not limited to the following examples.

[0110] Example 1

[0111] 1) Preparation of graphene oxide-nano titanium dioxide composite material

[0112] 1 part by weight of graphene oxide (purchased from Qingdao Laixi Colloidal Graphite Products Co., Ltd., particle size 30-38 μm) was mixed with 12 parts by weight of N’N-dimethylformamide (purchased from Beijing Chemical Industry Group Co., Ltd., analytical pure) and ultrasonic dispersion was performed (dispersion power 500 W, dispersion temperature 25℃, dispersion time 1 h). 10 parts by weight of 3-aminopropyl triethoxysilane (purchased from Beijing Bailingwei Technology Co., Ltd.) was added to the solution, nitrogen was continuously bubbled into the solution at room temperature (25℃) for 0.5 h, then the solution was heated to 100℃ and stirred for 8 h for first drying, then washed with anhydrous ethanol (purchased from Shanghai Sigma-Aldrich Trading Co., Ltd., analytical pure) for 5 times, and then first drying was performed (drying temperature 90℃, drying time 6 h) to obtain a first solid product. The first solid product was dissolved in N’N-dimethylformamide to obtain a solution containing the first solid product (the content of the first solid product was 8% by weight), the solution containing the first solid product was mixed with 3% by weight of a nano titanium dioxide solution (purchased from Nanjing Reagent, analytical pure), and acetic acid was added to adjust the pH value of the solution to 4, then heated to 90℃ and stirred for 8 h for second drying, wherein the weight ratio of nano titanium dioxide to graphene oxide was 1:2, then washed with anhydrous ethanol for 5 times, and second drying was performed at 60℃ for 24 h to obtain a graphene oxide-nano titanium dioxide composite material A1.

[0113] 2) Preparation of redispersible graphene oxide-nano titanium dioxide composite powder

[0114] The obtained graphene oxide-nano titanium dioxide composite material A1 was mixed with polyaniline oligomer (purchased from Hubei Watson Chemical Technology Co., Ltd.) with an average molecular weight of 7500 for ultrasonic dispersion, wherein the weight ratio of graphene oxide to polyaniline oligomer was 1:30. After ultrasonic dispersion, the filtrate was obtained by filtering after standing at 25°C for 1 h, and the filtrate was again subjected to ultrasonic dispersion and centrifugal separation, and the uniformly dispersed graphene oxide-nano titanium dioxide composite material dispersion liquid was obtained by taking the upper layer liquid of the centrifugal separation. Among them, the conditions of ultrasonic dispersion were: power 300 W, temperature 25°C, time 2 h. The conditions of centrifugal separation were: speed 12000 r / min, temperature 25°C, time 1.5 h; the graphene oxide-nano titanium dioxide composite material dispersion liquid was subjected to a third drying at 80°C for 10 h to remove the solvent, and redispersible graphene oxide-nano titanium dioxide composite powder B1 was obtained.

[0115] 3) Preparation of composite impermeable coating

[0116] The redispersible graphene oxide-nano titanium dioxide composite powder B1, pigment (aniline black, purchased from DuPont Company, USA) and part of the film-forming resin (phenolic epoxy resin, 12% by weight of the total amount of film-forming resin, purchased from Nan Ya Plastics Corporation) were mixed and milled at 20°C for 1 h to obtain the color paste finished product. Another part of the film-forming resin and the auxiliary agent were added to the obtained color paste finished product, and the mixture was stirred in a stirrer for 30 min (temperature 20°C) to obtain the impermeable coating S1. In addition, the amounts of the components are shown in Table 1.

[0117] Example 2

[0118] 1) Preparation of graphene oxide-nano titanium dioxide composite material

[0119] 1 part by weight of graphene oxide (purchased from Ningbo Gaolene Technology Co., Ltd., particle size 32-40 μm) was mixed with 10 parts by weight of N,N-dimethylformamide (purchased from Beijing Chemical Industry Group Co., Ltd., analytical pure), and ultrasonic dispersion was performed (dispersion power 400 W, dispersion temperature 25°C, dispersion time 2 h). 5 parts by weight of 3-aminopropyltriethoxysilane (purchased from Shanghai McLean Biochemical Technology Co., Ltd.) was added to the solution, nitrogen was continuously bubbled into the solution at room temperature (25°C) for 1 h, then the solution was warmed to 100°C, and first drying was performed by stirring for 10 h, then the solution was washed with anhydrous ethanol (purchased from Beijing Chemical Industry Group Co., Ltd., analytical pure) 5 times, and second drying was performed (drying temperature 110°C, drying time 8 h) to obtain a first solid product. The first solid product was dissolved in N,N-dimethylformamide to obtain a solution containing the first solid product (the content of the first solid product was 10% by weight), the solution containing the first solid product was mixed with 2% by weight of a nanometer titanium dioxide solution (purchased from Nanjing Reagent, analytical pure), and acetic acid was added to adjust the pH value of the solution to 4.5, then the solution was heated to 90°C, and second drying was performed by stirring for 9 h, wherein the weight ratio of nanometer titanium dioxide to graphene oxide was 1:2.5, then the solution was washed with anhydrous ethanol 4 times, and third drying was performed at 50°C for 36 h to obtain a graphene oxide-nanometer titanium dioxide composite material A2.

[0120] 2) Preparation of redispersible graphene oxide-nanometer titanium dioxide composite powder

[0121] The obtained graphene oxide-nanometer titanium dioxide composite material A2 was mixed with polyaniline oligomers (purchased from Hubei Watson Chemical Technology Co., Ltd.) with an average molecular weight of 7000, and ultrasonic dispersion was performed, wherein the weight ratio of graphene oxide to polyaniline oligomers was 1:35. After ultrasonic dispersion, the solution was filtered after standing at 25°C for 1 h to obtain a filtrate, the filtrate was again subjected to ultrasonic dispersion and centrifugal separation, and the upper layer of the centrifugal separation was taken to obtain a uniformly dispersed graphene oxide-nanometer titanium dioxide composite material dispersion liquid, wherein the ultrasonic dispersion conditions were: power 400 W, temperature 25°C, and time 1.5 h, and the centrifugal separation conditions were: rotation speed 11000 r / min, temperature 25°C, and time 1.5 h; the graphene oxide-nanometer titanium dioxide composite material dispersion liquid was subjected to third drying at 70°C for 15 h to remove the solvent, and redispersible graphene oxide-nanometer titanium dioxide composite powder B2 was obtained.

[0122] 3) Preparation of composite impermeable coating

[0123] The dispersible graphene oxide-nano titanium dioxide composite powder B2, pigment (aniline black, purchased from DuPont Company, USA) and part of the film-forming resin (phenolic epoxy resin, 10 wt% of the total amount of film-forming resin, purchased from Chongqing Yonghua Chemical Group Co., Ltd.) were mixed, milled at 25℃ for 1.5h to obtain the ink product. In the obtained ink product, the remaining film-forming resin and additives were added and stirred in a stirrer for 60min (temperature 25℃) to obtain the anti-permeation coating S2. In addition, the amount of each component is shown in Table 1.

[0124] Example 3

[0125] 1) Preparation of graphene oxide-nano titanium dioxide composite material

[0126] 1 part by weight of graphene oxide (purchased from Qingdao Laixi Colloidal Graphite Products Co., Ltd., particle size 30-38μm) was mixed with 15 parts by weight of N'N-dimethylformamide (purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd., analytical pure) and uniformly dispersed by ultrasonic dispersion (dispersion power 500W, dispersion temperature 30℃, dispersion time 1h). Then 6 parts by weight of 3-aminopropyl triethoxysilane (purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.) was added to the solution, and nitrogen was continuously bubbled into the solution at 30℃ for 1h. Then the solution was heated to 100℃ and stirred for 9h for first drying, then washed with anhydrous ethanol (purchased from Shanghai Sigma-Aldrich Trading Co., Ltd.) for 4 times, and then first dried (drying temperature 100℃, drying time 6h) to obtain a first solid product. The first solid product was dissolved in N'N-dimethylformamide to obtain a solution containing the first solid product (the content of the first solid product was 9 wt%). The solution containing the first solid product was mixed with 2 wt% of nano titanium dioxide solution (purchased from Nanjing Reagent, analytical pure), and citric acid was added to adjust the pH value of the solution to 5, then heated to 90℃ and stirred for 10h for second drying, wherein the weight ratio of nano titanium dioxide to graphene oxide was 1:2. Then washed with anhydrous ethanol for 5 times, and then second dried at 60℃ for 48h to obtain the graphene oxide-nano titanium dioxide composite material A3.

[0127] 2) Preparation of dispersible graphene oxide-nano titanium dioxide composite powder

[0128] The obtained graphene oxide-nano titanium dioxide composite material A3 was mixed with polyaniline oligomer with an average molecular weight of 8000 (purchased from Shanghai Haohong Biomedical Technology Co., Ltd.) for ultrasonic dispersion, wherein the weight ratio of graphene oxide to polyaniline oligomer was 1:32. After ultrasonic dispersion, the filtrate was obtained by filtering after standing at 30°C for 2h, and the uniform dispersion of graphene oxide-nano titanium dioxide composite material dispersion liquid was obtained by centrifugal separation after ultrasonic dispersion again. Among them, the conditions of ultrasonic dispersion were: power 350W, temperature 27°C, time 3h, and the conditions of centrifugal separation were: speed 10000r / min, temperature 25°C, time 2h. The graphene oxide-nano titanium dioxide composite material dispersion liquid was dried at 90°C for 20h to remove the solvent, and the redispersible graphene oxide-nano titanium dioxide composite powder B3 was obtained.

[0129] 3) Preparation of composite impermeable coating

[0130] The redispersible graphene oxide-nano titanium dioxide composite powder B3, pigment (yellow iron oxide, purchased from Tianjin Jifa Pigment Co., Ltd.) and part of the film-forming resin (phenolic epoxy resin, 11% by weight of the total amount of film-forming resin, purchased from Nantong Xingchen Synthetic Material Co., Ltd.) were mixed and milled at 25°C for 2h to obtain the color paste product. The remaining film-forming resin and auxiliary agents were added to the obtained color paste product, and stirred in a stirrer for 45min (temperature 25°C) to obtain the impermeable coating S3. In addition, the amounts of each component are shown in Table 1.

[0131] Example 4

[0132] 1) Preparation of graphene oxide-nano titanium dioxide composite material

[0133] The graphene oxide (purchased from Changzhou Sixth Element Material Technology Co., Ltd., particle size 35-40 μm) was mixed with 14 parts by weight of N'N-dimethylformamide (purchased from Shanghai Macklin Biochemical Technology Co., Ltd., analytical pure) and uniformly dispersed by ultrasonic dispersion (power 400 W, temperature 25℃, time 1.5 h). Then, 12 parts by weight of 3-aminopropyl triethoxysilane (purchased from Sinopharm Chemical Reagent Co., Ltd.) was added to the solution. Nitrogen was continuously bubbled into the solution at room temperature (25℃) for 0.5 h. Then, the solution was heated to 100℃ and stirred for 10 h for first drying. The first solid product was obtained. The first solid product was dissolved in N'N-dimethylformamide to obtain a solution containing the first solid product (the content of the first solid product was 10% by weight). The solution containing the first solid product was mixed with 5% by weight of nano-titanium dioxide solution (purchased from Nanjing Reagent, analytical pure) and adjusted to pH 4.5 by adding acetic acid. Then, the solution was heated to 90℃ and stirred for 10 h for second drying. The weight ratio of nano-titanium dioxide to graphene oxide was 1:1.5. After washing with anhydrous ethanol for 5 times, the graphene oxide-nano-titanium dioxide composite material A4 was obtained by second drying at 70℃ for 24 h.

[0134] 2) Preparation of redispersible graphene oxide-nano-titanium dioxide composite powder

[0135] The obtained graphene oxide-nano-titanium dioxide composite material A4 was mixed with polyaniline oligomer (purchased from Hubei Watson Chemical Technology Co., Ltd.) with an average molecular weight of 7000. The weight ratio of graphene oxide to polyaniline oligomer was 1:35. After ultrasonic dispersion, the mixture was placed at 25℃ for 2.5 h and then filtered to obtain a filtrate. The filtrate was ultrasonically dispersed again and then centrifuged. The upper layer of the centrifuged solution was taken to obtain a uniformly dispersed graphene oxide-nano-titanium dioxide composite material dispersion. The ultrasonic dispersion conditions were as follows: power 400 W, temperature 25℃, time 1.5 h. The centrifugation conditions were as follows: speed 13000 r / min, temperature 25℃, time 1.5 h. The graphene oxide-nano-titanium dioxide composite material dispersion was dried at 75℃ for 12 h to remove the solvent, thereby obtaining the redispersible graphene oxide-nano-titanium dioxide composite powder B4.

[0136] 3) Preparation of composite impermeable coating

[0137] The dispersible graphene oxide-nano titanium dioxide composite powder B4, pigment (yellow iron oxide, purchased from Tianjin Jifa Pigment Co., Ltd.) and part of the film-forming resin (phenolic epoxy resin, 15 wt% of the total amount of film-forming resin, purchased from BASF SE, Germany) were mixed and milled at 25°C for 2h to obtain the color paste product. The remaining film-forming resin and additives were added to the obtained color paste product and stirred in a stirrer for 30min (temperature 25°C) to obtain the anti-permeation coating S4. In addition, the amounts of the components are shown in Table 1.

[0138] Example 5

[0139] 1) Preparation of graphene oxide-nano titanium dioxide composite material

[0140] 1 part by weight of graphene oxide (purchased from Changzhou Sixth Element Material Technology Co., Ltd., particle size 35-40 μm) was mixed with 16 parts by weight of N’N-dimethylformamide (purchased from Shanghai Macklin Biochemical Technology Co., Ltd., analytical pure) and uniformly ultrasonically dispersed (dispersion power 300W, dispersion temperature 25°C, dispersion time 3h), then 18 parts by weight of 3-aminopropyl triethoxysilane (purchased from National Pharmaceutical Group Chemical Reagent Co., Ltd.) was added to the solution, nitrogen was continuously bubbled into the solution at room temperature (25°C) for 1.5h, then the solution was heated to 90°C and stirred for 7h for first drying, then washed with anhydrous ethanol (purchased from Shanghai Macklin Biochemical Technology Co., Ltd., analytical pure) for 5 times, then first drying (drying temperature 90°C, drying time 7h) was carried out to obtain a first solid product. The first solid product was dissolved in N’N-dimethylformamide to obtain a solution containing the first solid product (the content of the first solid product was 12 wt%), the solution containing the first solid product was mixed with 5 wt% of a nano titanium dioxide solution (purchased from Nanjing Reagent, analytical pure), and acetic acid was added to adjust the pH value of the solution to 5.5, then heated to 80°C and stirred for 10h for second drying, wherein the weight ratio of nano titanium dioxide to graphene oxide was 1:3, then washed with anhydrous ethanol for 5 times and second dried at 70°C for 18h to obtain the graphene oxide-nano titanium dioxide composite material A5;

[0141] 2) Preparation of dispersible graphene oxide-nano titanium dioxide composite powder

[0142] The obtained graphene oxide-nano titanium dioxide composite material A4 was mixed with polyaniline oligomer with an average molecular weight of 8500 (purchased from Shanghai Haohong Biomedical Technology Co., Ltd.) for ultrasonic dispersion, wherein the weight ratio of graphene oxide to polyaniline oligomer was 1:45. After ultrasonic dispersion, the filtrate was obtained by filtering after standing at 25°C for 2 h, and the uniformly dispersed graphene oxide-nano titanium dioxide composite material dispersion was obtained by centrifugal separation after ultrasonic dispersion of the filtrate again. The conditions for ultrasonic dispersion were all as follows: power 500 W, temperature 25°C, time 1.5 h, and the conditions for centrifugal separation were as follows: speed 13000 r / min, temperature 25°C, and time 2 h. The graphene oxide-nano titanium dioxide composite material dispersion was dried at 60°C for 12 h to remove the solvent, and the redispersible graphene oxide-nano titanium dioxide composite powder B5 was obtained.

[0143] 3) Preparation of composite impermeable coating

[0144] The redispersible graphene oxide-nano titanium dioxide composite powder B5, pigment (yellow iron oxide, purchased from Tianjin Jifa Pigment Co., Ltd.), and part of the film-forming resin (phenolic epoxy resin, 18% by weight of the total amount of film-forming resin, purchased from BASF SE, Germany) were mixed and milled at 25°C for 2 h to obtain the color paste product. The remaining film-forming resin and additives were added to the obtained color paste product, and stirring was performed in a stirrer for 40 min (temperature 25°C) to obtain the impermeable coating S5. In addition, the amounts of the components are shown in Table 1.

[0145] Table 1

[0146]

[0147] In Table 1, the content of each component is based on 100% by weight of the total weight of the impermeable coating. The “composite powder” is the redispersible graphene oxide-nano titanium dioxide composite powder obtained in the respective examples; the wetting dispersant is polyester polyamide (purchased from BASF SE, Germany); the leveling agent is polyether siloxane copolymer (purchased from Hubei Longsheng Sihai New Material Co., Ltd.); the anti-settling agent is fumed silica (purchased from Wacker Chemie AG, Germany); the defoaming agent is polyether modified silicon (purchased from Yantai Hengxin Chemical Technology Co., Ltd.); the matting agent is diatomite (purchased from Hebei Hengyue Mineral Products Co., Ltd.); and the thickening agent is polyethylene glycol (purchased from BASF SE, Germany).

[0148] Comparative Example 1

[0149] The method of Example 1 was followed, except that step 1) was not included, and graphene was directly used instead of graphene oxide-nano titanium dioxide composite material A1, to obtain the impermeable coating D1.

[0150] Comparative Example 2

[0151] The method of Example 1 was followed except that step 1) was not included and graphene oxide-nano titanium dioxide composite material Al was directly used instead of graphene oxide-nano titanium dioxide composite material Al, and the same way to obtain the anti-permeable coating D2.

[0152] Comparative Example 3

[0153] The method of Example 1 was followed except that step 2) was not included and graphene oxide-nano titanium dioxide composite material Al was directly used instead of re-dispersible graphene oxide-nano titanium dioxide composite powder Bl, and the same way to obtain the anti-permeable coating D3.

[0154] Test Example 1

[0155] The obtained anti-permeable coatings S1, S2, S3, S4, S5, D1, D2, D3 were coated on polytetrafluoroethylene sample plates with an automatic coater (TBJ-A1-DJ4, Shandong Zhongyi Instrument Co., Ltd.) and the film thickness was controlled at 20 μm. After complete curing and room temperature curing for 5 days, the water vapor permeability of the anti-permeable coating was tested according to the cup method of standard ASTM E96 / E96M, and the results are shown in Table 1. Figure 1

[0156] Test Example 2

[0157] The obtained anti-permeable coatings S1, S2, S3, S4, S5, D1, D2, D3 were coated on copper foil with a thickness of 100 μm after curing, and after curing, the samples were tested for corrosion resistance according to the method for determining the neutral salt spray resistance of paint and varnish GB / T1771, and the results are shown in Table 2.

[0158] Table 2

[0159] Type Salt fog resistance length / h S1 5800 S2 5400 S3 6000 S4 5800 S5 4800 D1 2000 D2 2600 D3 4000

[0160] Test Example 3

[0161] The obtained anti-permeable coatings S1, S2, S3, S4, S5, D1, D2, D3 were cast in a mold of 8 x 1.5 x 0.3 cm, and after complete curing and room temperature curing for 5 days, the cast body material was immersed in crude oil (sampled from Shengli Oilfield Crude Oil Depot of Sinopec) at room temperature 25°C for 30 days. The surface morphology was observed as shown in Table 3. Figure 2

[0162] Table 3

[0163] Type Material state after immersion S1 No abnormalities S2 No abnormalities S3 No abnormalities S4 No abnormalities S5 No abnormalities D1 Fracture, blistering D2 Blistering D3 Blistering

[0164] Test Example 4 ​​

[0165] The obtained anti-permeation coatings S1, S2, S3, S4, S5, D1, D2, D3 were cast in a mold of 8x1.5x0.3cm, and after complete solidification and curing at room temperature for 5 days, the cast body material was immersed in the crude oil tank bottom deposit water (sampled from the crude oil tank of Shengli Oilfield) at room temperature 25℃ for 30 days, and the change of Shore hardness with time was tested according to the standard GB / T2411-2008, as shown in Figure 3 .

[0166] Comprehensive Figure 1 , Table 2, Figure 2 , Table 3 and Figure 3 The test results show that the redispersible graphene oxide-nano titanium dioxide composite powder filler used in the titanium dioxide modified graphene oxide composite anti-permeation coating has more excellent water vapor barrier performance, salt mist resistance, and resistance to crude oil and crude oil tank bottom deposit water than graphene, graphene oxide, and graphene oxide-nano titanium dioxide composite material filler dispersed by polyaniline oligomer auxiliary dispersion. This is because the coupling modification of graphene oxide with nano titanium dioxide particles can enhance the dispersibility of graphene oxide, and can compensate for the structural defects of graphene oxide by plugging micropores. In addition, the use of polyaniline oligomer for filler auxiliary dispersion can further improve the dispersion ability of the filler in the resin matrix, thereby prolonging the penetration and diffusion path of corrosive media and producing better medium shielding effect.

[0167] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A method for preparing a composite waterproof coating, characterized in that, This method Includes the following steps, 1) In the presence of a solvent, graphene oxide is subjected to a first contact reaction with a silane coupling agent, and the product of the first contact reaction is subjected to a first drying process to obtain a first solid product; 2) Under acidic conditions, the solution containing the first solid product is subjected to a second contact reaction with a titanium dioxide solution, and the product of the second contact reaction is subjected to a second drying to obtain a second solid product; 3) The second solid product obtained in step 2) is dispersed and dried using polyaniline oligomer as a dispersant to obtain redispersible graphene oxide-nano titanium dioxide composite powder; 4) Mix the redispersible graphene oxide-nano titanium dioxide composite powder obtained in step 3) with the film-forming resin; the silane coupling agent includes one or more selected from 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane; In step 2), the solvent used in the solution containing the first solid product is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylpropionamide; The first contact reaction conditions include: a temperature of 10-35℃ and a reaction time of 0.2-2h.

2. The method according to claim 1, wherein, The weight ratio of graphene oxide to solvent in step 1) is 1:8-20; And / or, the weight ratio of the graphene oxide to the silane coupling agent is 1:3-18.

3. The method according to claim 2, wherein, The weight ratio of graphene oxide to solvent in step 1) is 1:10-15; And / or, the weight ratio of the graphene oxide to the silane coupling agent is 1:5-15.

4. The method according to claim 1, wherein, In step 1), the first contact reaction is carried out under an inert atmosphere.

5. The method according to claim 1, wherein, The first contact reaction conditions include: a temperature of 25-30℃ and a reaction time of 0.5-1h.

6. The method according to claim 1, wherein, The first drying conditions include: a temperature of 70-150℃ and a time of 4-15h.

7. The method according to claim 6, wherein, The first drying conditions are: temperature 90-110℃ and time 6-10h.

8. The method according to claim 1, wherein, In step 1), the solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and N,N-dimethylpropionamide; And / or, the silane coupling agent is 3-aminopropyltriethoxysilane.

9. The method according to claim 1, wherein, In step 1), the solvent is N,N-dimethylformamide.

10. The method according to claim 1, wherein, The method further includes the steps of first drying and washing the first contact reaction product before performing the first drying.

11. The method according to claim 1, wherein, The content of the first solid product in the solution containing the first solid product is 5-10% by weight.

12. The method according to claim 1, wherein, The acidic conditions are defined as a pH value between 3.5 and 5.

5.

13. The method according to claim 12, wherein, The acidic conditions are defined as a pH value of 4-5.

14. The method according to claim 1, wherein, The acidic conditions are adjusted by adding acetic acid.

15. The method according to claim 1, wherein, In step 2), the concentration of the nano-titanium dioxide solution is 0.5-7% by weight. And / or, the weight ratio of the amount of nano-titanium dioxide to the amount of graphene oxide is 1:1-4.

16. The method according to claim 15, wherein, In step 2), the concentration of the nano-titanium dioxide solution is 2-5% by weight. And / or, the weight ratio of the amount of nano-titanium dioxide to the amount of graphene oxide is 1:1.5-2.

5.

17. The method according to claim 1, wherein, In step 2), the second contact reaction conditions include: a temperature of 60-90℃ and a time of 5-12h.

18. The method according to claim 17, wherein, The second contact reaction conditions include: a temperature of 80°C and a time of 6-10 hours.

19. The method according to claim 1, wherein, The second drying conditions include a temperature of 45-100℃ and a time of 18-64h.

20. The method according to claim 19, wherein, The second drying conditions include a temperature of 50-90℃ and a time of 24-48h.

21. The method according to claim 1, wherein, The method further includes the steps of subjecting the second contact reaction product to a second drying and washing process prior to the second drying.

22. The method according to claim 1, wherein, In step 3), the average molecular weight of the polyaniline oligomer is 6000-10000; And / or, the weight ratio of the graphene oxide to the polyaniline oligomer is 1:20-60.

23. The method according to claim 22, wherein, In step 3), the average molecular weight of the polyaniline oligomer is 7000-8000; And / or, the weight ratio of the graphene oxide to the polyaniline oligomer is 1:30-40.

24. The method according to claim 1, wherein, In step 3), the dispersion is ultrasonic dispersion.

25. The method according to claim 24, wherein, The conditions for ultrasonic dispersion include: ultrasonic power of 100-500W and ultrasonic time of 0.2-5h.

26. The method according to claim 25, wherein, The conditions for ultrasonic dispersion include: ultrasonic power of 200-400W and ultrasonic time of 0.5-3h.

27. The method according to claim 1, wherein, In step 3), the conditions for the third drying process include: a temperature of 50-95℃ and a time of 6-30h.

28. The method according to claim 27, wherein, The conditions for the third drying process include: a temperature of 70-90℃ and a time of 10-20 hours.

29. The method according to claim 1, wherein, In step 4), the redispersible graphene oxide-nano titanium dioxide composite powder obtained in step 3) and part of the film-forming resin are ground and then mixed with another part of the film-forming resin.

30. The method according to claim 29, wherein, The redispersible graphene oxide-nano titanium dioxide composite powder is ground with 5-20% by weight of the total amount of film-forming resin.

31. The method according to claim 30, wherein, The redispersible graphene oxide-nano titanium dioxide composite powder is ground with 10-15% by weight of the total amount of film-forming resin.

32. The method according to claim 1, wherein, Based on the composite anti-seepage coating, the content of the redispersed graphene oxide-nano titanium dioxide composite powder is 0.1-5% by weight.

33. The method according to claim 32, wherein, Based on the composite anti-seepage coating, the content of the redispersed graphene oxide-nano titanium dioxide composite powder is 0.2-3% by weight.

34. The method according to claim 1, wherein, The method also includes the step of adding an adjuvant in step 4).

35. The method according to claim 34, wherein, The additive is a pigment.

36. The method according to claim 34, wherein, Based on the composite waterproof coating, the content of the additive is 0.5-2% by weight.

37. The method according to claim 1, wherein, In step 4), the film-forming resin is selected from one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, polyurea resin, polyurethane resin, and organosilicon resin.

38. The method according to claim 37, wherein, In step 4), the film-forming resin is phenolic epoxy resin.

39. The composite anti-seepage coating prepared by the method of any one of claims 1-38.

40. The composite anti-seepage coating prepared by the method of any one of claims 1-38 or the composite anti-seepage coating of claim 39 is used for internal anti-seepage in oil storage.

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