Hydrogen permeation resistant composite coating as well as preparation method and application thereof

Abstract

The invention relates to the field of composite materials, and discloses an anti-hydrogen permeation composite coating as well as a preparation method and application thereof. The hydrogen permeation resistant composite coating is prepared from the following raw materials: epoxy resin, carboxyl-terminated liquid nitrile rubber, polyhedral oligomeric silsesquioxane and an ionic liquid modified layered nano composite material. Wherein the layered nano composite material is graphite phase carbon nitride and / or cobalt-aluminum double metal hydroxide; and the thickness of the layered nano composite material is 2 to 100 nm. According to the present invention, the coating material with characteristics of excellent internal resistance reducing effect and hydrogen permeation resistance is prepared mainly through the design of the polymer matrix material and the compounding of the functional filler, and can be used in all devices and pipelines in the hydrogen environment, such that the intrinsic safety performance is improved, and the service life is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of composite materials, in particular to an anti-hydrogen permeation composite coating and a preparation method and application thereof. BACKGROUND

[0002] The drag-reducing coating in the gas pipeline can greatly reduce the gas transmission friction coefficient, increase the transmission capacity and improve the transmission efficiency. The drag-reducing coating in the gas pipeline has many advantages in economy, technology, management, environmental protection and other aspects. The internal drag-reducing technology is widely used in long-distance natural gas pipelines at home and abroad. However, hydrogen energy, as an ideal carrier to promote the large-scale development of renewable energy, plays an important role in the future energy structure. The hydrogen-doped pipeline natural gas transportation technology is to mix hydrogen into natural gas according to a certain volume ratio and transport it through the existing natural gas pipeline. Research has shown that hydrogen embrittlement can cause failure of metal materials. Therefore, for natural gas pipelines doped with hydrogen or pure hydrogen, the coupling of hydrogen embrittlement and drag resistance of metal can further reduce the service life of the pipeline. Therefore, improving the long-term safety and reliability of long-distance hydrogen-doped pipelines is a serious challenge.

[0003] Coating a layer of internal drag-reducing coating on the surface of the metal is a key means to improve the transmission efficiency and the service life of the gas pipeline. Coating a layer of coating with hydrogen permeation resistance on the surface of the metal is one of the key means to improve the hydrogen embrittlement resistance of the metal.

[0004] At present, the common anti-hydrogen permeation coating with delayed hydrogen permeation on the surface of the metal is one of the means to solve the problem of metal hydrogen embrittlement. The common anti-hydrogen permeation coating is mostly metal oxide coating, silicide coating, aluminide coating, etc.; the preparation processes are also different, such as chemical / physical vapor deposition, plasma spraying, sol-gel method and micro-arc oxidation method, etc. The above preparation processes and conditions are relatively complex and high in cost, which cannot meet the requirements of large-scale use, and the above coatings are non-polymer-based coatings, which have poor designability. In addition, the existing polymer-based hydrogen-resistant coating (patent application CN107916045A) only has improved hydrogen resistance, but does not have the drag-reducing function. Therefore, designing and preparing a dual-functional coating with hydrogen resistance and internal drag-reducing function can solve the above problems and promote the rapid development of hydrogen energy technology in China.

[0005] Patent application CN103820005B provides a two-component solvent-free epoxy internal drag-reducing coating applied in the internal drag reduction of pipelines. The coating overcomes the problem of poor flexibility of the coating by selecting a toughening agent in component A and a curing agent in component B, reduces the viscosity of the coating, and reduces the requirements for the production process and construction conditions of the coating. Due to the excellent performance of the coating, combined with the convenience, safety and environmental protection of production and construction, the coating will be widely used in the field of internal drag reduction of pipelines. However, the patent does not involve anti-hydrogen permeation, and is not suitable for hydrogen pipelines.

[0006] Patent application CN108300147B discloses a solvent-free internal drag reduction coating and its preparation method. It can simultaneously meet the requirements of thin coating, flexibility, short-term heat resistance and salt spray resistance of internal drag reduction coating. However, this patent does not involve hydrogen permeation resistance and is not suitable for hydrogen transport pipelines.

[0007] Patent application CN110724435B discloses a water-based pipeline internal drag reduction epoxy coating and its preparation method, anticorrosive coating and application. However, this patent does not involve hydrogen permeation resistance and is not suitable for hydrogen transport pipelines. SUMMARY

[0008] The purpose of the present application is to overcome the current lack of a dual functional coating with hydrogen resistance and internal drag reduction for hydrogen transport pipelines and hydrogen mixed pipelines. The present application provides an anti-hydrogen permeation composite coating, its preparation method and application. The anti-hydrogen permeation composite coating has excellent internal drag reduction effect and hydrogen permeation resistance.

[0009] To achieve the above purpose, the present application provides an anti-hydrogen permeation composite coating. The raw materials for preparing the anti-hydrogen permeation composite coating contain epoxy resin, carboxyl-terminated liquid nitrile rubber, polyhedral oligomeric silsesquioxane and ion liquid modified layered nanocomposite.

[0010] The layered nanocomposite is graphite phase carbon nitride and / or cobalt-aluminum double metal hydroxide. The thickness of the layered nanocomposite is 2-100 nm.

[0011] Preferably, the weight ratio of the amounts of the epoxy resin, carboxyl-terminated liquid nitrile rubber, polyhedral oligomeric silsesquioxane and ion liquid modified layered nanocomposite is 1:0.05-0.5:0.05-0.3:0.01-0.5.

[0012] Preferably, the epoxy resin is E51 and / or E44.

[0013] Preferably, the carboxyl content of the carboxyl-terminated liquid nitrile rubber is 0.24-0.65 mol / kg.

[0014] Preferably, the number of layers of the graphite phase carbon nitride is 5-50 layers.

[0015] Preferably, the aspect ratio of the cobalt-aluminum double metal hydroxide is 20-80:1.

[0016] Preferably, the ion liquid is 1-butyl-3-methylimidazolium hexafluorophosphate and / or 1-butyl-3-methylimidazolium tetrafluoroborate.

[0017] Preferably, the raw materials for preparing the anti-hydrogen permeation composite coating further contain diluent, curing agent, leveling agent and defoaming agent.

[0018] Preferably, the diluent is one or more of glycidyl neodecanoate, glycidyl neoundecanoate, glycidyl valerate and glycidyl monocarboxylic acid;

[0019] Preferably, the curing agent is amidoamine and / or triethylenetetramine;

[0020] Preferably, the leveling agent is one or more of fluorine-modified acrylate, polyether polyester-modified organosiloxane and melamine formaldehyde resin;

[0021] Preferably, the defoaming agent is polyether type organosilicon polymer and / or polyethylene glycol fatty acid.

[0022] Preferably, the weight ratio of the amounts of the epoxy resin, the diluent, the curing agent, the leveling agent and the defoaming agent is 1:0.1-0.5:0.1-0.2:0.01-0.06:0.01-0.03.

[0023] The second aspect of the present application provides a method for preparing the above-mentioned anti-hydrogen permeation composite coating, the method comprising the following steps:

[0024] (1) mixing the epoxy resin, the diluent and the carboxyl-terminated liquid butyl nitrile rubber and stirring to obtain solution A;

[0025] (2) mixing the solution A and the polyhedral oligomeric silsesquioxane and stirring to obtain solution B;

[0026] (3) mixing the solution B and the ionic liquid-modified layered nanocomposite and stirring to obtain solution C;

[0027] (4) mixing the solution C and the curing agent, the leveling agent and the defoaming agent and stirring.

[0028] Preferably, in step (1), the stirring conditions include a time of 10-100 min and a speed of 3000-12000 rmp.

[0029] Preferably, in step (2), the stirring conditions include a time of 10-60 min and a speed of 3000-10000 rmp.

[0030] Preferably, in step (3), the stirring conditions include a time of 20-160 min and a speed of 2000-5000 rmp.

[0031] Preferably, in step (4), the stirring conditions include a time of 10-30 min and a speed of 1000-5000 rmp.

[0032] The third aspect of the present application provides application of the above hydrogen permeation resistant composite coating in preparation of an inner drag reduction hydrogen resistant coating.

[0033] The fourth aspect of the present application provides an inner drag reduction hydrogen resistant coating, which is prepared by coating and curing the above hydrogen permeation resistant composite coating.

[0034] The fifth aspect of the present application provides application of the inner drag reduction hydrogen resistant coating in protection of a hydrogen-containing fuel conveying pipeline.

[0035] The present application mainly prepares a coating with excellent inner drag reduction effect and hydrogen permeation resistance through design of a polymer matrix material and compounding of functional fillers, which can be used in all hydrogen environments of equipment and pipelines to improve intrinsic safety performance and prolong service life. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is a scanning electron microscope image of the ionic liquid modified cobalt-aluminum double metal hydroxide obtained in Example 2;

[0037] Figure 2 is a transmission electron microscope image of the ionic liquid modified graphite phase carbon nitride obtained in Example 1. DETAILED DESCRIPTION

[0038] The specific embodiments of the present application are described in detail below. It should be understood that the specific embodiments described herein are merely intended to illustrate and explain the present application, and are not intended to limit the present application.

[0039] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges or values should be construed to be approximations that allow for significant variation. Various ranges of values that are stated herein are considered to be approximate values that can vary by a small amount. Endpoints of various ranges, endpoints of various ranges and individual point values, and individual point values can be combined with each other to form one or more new ranges of values, which should be considered to be specifically disclosed herein.

[0040] The present application provides a hydrogen permeation resistant composite coating, which is prepared from raw materials containing an epoxy resin, a carboxyl-terminated liquid nitrile rubber, a polyhedral oligomeric silsesquioxane, and an ionic liquid modified layered nanocomposite material.

[0041] The layered nanocomposite material is graphite phase carbon nitride and / or cobalt-aluminum double metal hydroxide, and the thickness of the layered nanocomposite material is 2-100 nm.

[0042] In the present application, the thickness of the layered nanocomposite material is not affected before and after modification by the ionic liquid, so the thickness of the layered nanocomposite material is the thickness of the ionic liquid modified layered nanocomposite material.

[0043] In the present application, in order to obtain an anti-hydrogen permeation composite coating with suitable performance, the amount of each raw material needs to be further controlled, preferably, the weight ratio of the amount of the epoxy resin, the carboxyl-terminated liquid nitrile rubber, the polyhedral oligomeric silsesquioxane and the ionic liquid modified layered nanocomposite is 1:0.05-0.5:0.05-0.3:0.01-0.5.

[0044] In a specific embodiment, the weight ratio of the amount of the epoxy resin and the carboxyl-terminated liquid nitrile rubber can be 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4 or 1:0.5, the weight ratio of the amount of the epoxy resin and the polyhedral oligomeric silsesquioxane is 1:0.05, 1:0.1, 1:0.2 or 1:0.3, and the weight ratio of the amount of the epoxy resin and the ionic liquid modified layered nanocomposite is 1:0.01, 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4 or 1:0.5.

[0045] Preferably, the epoxy resin is E51 and / or E44.

[0046] Preferably, the carboxyl content of the carboxyl-terminated liquid nitrile rubber is 0.24-0.65 mol / kg, and in a specific embodiment, the carboxyl content of the carboxyl-terminated liquid nitrile rubber can be 0.24-0.30 mol / kg, 0.37-0.45 mol / kg or 0.53-0.65 mol / kg.

[0047] In the present application, the number of layers of the graphite phase carbon nitride will affect the hydrogen resistance performance of the final product material, and preferably, the number of layers of the graphite phase carbon nitride is 5-50 layers.

[0048] In the present application, the aspect ratio of the cobalt-aluminum double metal hydroxide will affect the dispersibility and material density of the final product material, and therefore, preferably, the aspect ratio of the cobalt-aluminum double metal hydroxide is 20-80:1, and specifically can be 20:1, 30:1, 40:1, 50:1, 60:1, 70:1 or 80:1.

[0049] In the present application, the ionic liquid modified layered nanocomposite is obtained by self-preparation, wherein the cobalt-aluminum double metal hydroxide in the ionic liquid modified cobalt-aluminum double metal hydroxide can be commercially available or self-prepared.

[0050] When the cobalt-aluminum double metal hydroxide is commercially available, the preparation method of the ion liquid modified cobalt-aluminum double metal hydroxide comprises: mixing the cobalt-aluminum double metal hydroxide with ethanol to obtain a cobalt-aluminum double metal hydroxide solution, then mixing the cobalt-aluminum double metal hydroxide solution with an ion liquid, stirring for 1-3 h, and then filtering and drying; wherein the molar ratio of the amount of the ion liquid to the amount of the cobalt-aluminum double metal hydroxide is 0.1-0.8:1.

[0051] In the above preparation method, ethanol plays a role in dissolving the cobalt-aluminum double metal hydroxide, and the amount of ethanol can be used to completely dissolve the cobalt-aluminum double metal hydroxide.

[0052] In a specific embodiment, the stirring time can be 1 h, 2 h or 3 h.

[0053] In the present application, the amount of the ion liquid and the cobalt-aluminum double metal hydroxide will affect the performance of the finished product, so the amount of the ion liquid and the cobalt-aluminum double metal hydroxide needs to be reasonably controlled within the above range, specifically, the molar ratio of the amount of the ion liquid to the amount of the cobalt-aluminum double metal hydroxide can be 0.1:1, 0.3:1, 0.5:1 or 0.8:1.

[0054] When the cobalt-aluminum double metal hydroxide is prepared by oneself, preferably, the ion liquid is added during the preparation of the cobalt-aluminum double metal hydroxide, and the ion liquid modified cobalt-aluminum double metal hydroxide is directly prepared by a co-precipitation method, and the specific method comprises:

[0055] (a) mixing Co(NO3)2, Al(OH)3 and deionized water to prepare a mixed salt solution; wherein the molar ratio of the amount of Co(NO3)2 to the amount of Al(OH)3 is 0.5-2:1, the concentration of Co element in the mixed salt solution is 0.05-0.8 mol / L, and the concentration of Al element is 0.2-0.8 mol / L;

[0056] (b) mixing the ion liquid, the mixed salt solution and deionized water to obtain a mixed solution; wherein the molar ratio of the amount of Al(OH)3 to the amount of the ion liquid is 2:0.1-1, the concentration of Al(OH)3 in the mixed solution is 0.01-0.5 mol / L, and the concentration of the ion liquid is 0.005-0.3 mol / L;

[0057] (c) mixing the mixed solution with a sodium hydroxide solution, crystallizing at 110-130℃ for 8-18 h, then precipitating, and the precipitation conditions comprise: the pH value of the system is 8-10, and then filtering.

[0058] In step (a), the amount and concentration of Co(NO3)2 and Al(OH)3 in the mixed salt solution affect the performance of the material. To obtain the ionic liquid-modified cobalt-aluminum double metal hydroxide required by the present application, the amount of Co(NO3)2, Al(OH)3 and deionized water is controlled within the above range.

[0059] In a specific embodiment of step (a), the molar ratio of the amount of Co(NO3)2 to Al(OH)3 can be 0.5:1, 1:1, 1.5:1 or 2:1.

[0060] In a specific embodiment of step (a), the concentration of Co in the mixed salt solution can be 0.05 mol / L, 0.1 mol / L, 0.3 mol / L, 0.5 mol / L or 0.8 mol / L, and the concentration of Al can be 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L or 0.8 mol / L.

[0061] In a specific embodiment of step (b), the molar ratio of the amount of Al(OH)3 to ionic liquid can be 2:0.1, 2:0.5 or 2:1.

[0062] In a specific embodiment of step (b), the concentration of Al(OH)3 in the mixed solution can be 0.01 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L or 0.5 mol / L, and the concentration of ionic liquid can be 0.005 mol / L, 0.1 mol / L, 0.2 mol / L or 0.3 mol / L.

[0063] In step (c), the temperature of the crystallization can be 110°C, 120°C or 130°C, and the time of the crystallization can be 8h, 10h, 12h, 15h or 18h.

[0064] In the present application, the preparation method of the ionic liquid-modified graphite phase carbon nitride comprises:

[0065] S1, mixing dicyandiamide, ammonium chloride and deionized water and stirring, then heating to remove water, and annealing the obtained material at 500-600°C for 1-3h to obtain graphite phase carbon nitride; wherein the weight ratio of dicyandiamide to ammonium chloride is 1:5-10;

[0066] S2, mixing and stirring the graphite phase carbon nitride with deionized water, the solid-liquid ratio of the graphite phase carbon nitride and the deionized water being 10 g:100-1000 mL, then heat preservation at 150-300℃ for 10-15 h, then taking the supernatant and mixing with the ionic liquid, the volume ratio of the supernatant and the ionic liquid being 10:0.1-1, ultrasonic treatment for 20-40 min.

[0067] In step S1, the deionized water plays a role of dissolving raw materials, and the amount of the deionized water can be used as long as the raw materials can be completely dissolved.

[0068] In the specific embodiment of step S1, the weight ratio of dicyandiamide and ammonium chloride can be 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0069] In step S2, because the graphite phase carbon nitride obtained in step S1 has different layers, leading to different weights of the graphite phase carbon nitride, in order to further obtain the graphite phase carbon nitride with a limited number of layers defined in the present application, the graphite phase carbon nitride is mixed and stirred with deionized water in step S2, the graphite phase carbon nitride with more layers, i.e. heavier, will precipitate, and the graphite phase carbon nitride with fewer layers, i.e. lighter, will remain in the supernatant, facilitating screening.

[0070] In the specific embodiment of step S2, the solid-liquid ratio of the graphite phase carbon nitride and the deionized water can be 10 g:100 mL, 10 g:300 mL, 10 g:500 mL, 10 g:700 mL or 10 g:100 mL.

[0071] In the specific embodiment of step S2, the temperature of heat preservation can be 150℃, 180℃, 200℃, 250℃ or 300℃, and the time of heat preservation can be 10 h, 11 h, 12 h, 13 h, 14 h or 15 h.

[0072] In the specific embodiment of step S2, the volume ratio of the supernatant and the ionic liquid can be 10:0.1, 10:0.3, 10:0.5, 10:0.7 or 10:1.

[0073] In the present application, the ionic liquid is 1-butyl-3-methylimidazolium hexafluorophosphate and / or 1-butyl-3-methylimidazolium tetrafluoroborate.

[0074] Preferably, the raw materials for preparing the anti-hydrogen permeation composite coating also contain a diluent, a curing agent, a leveling agent and a defoaming agent.

[0075] Preferably, the diluent is glycidyl ester of monocarboxylic acid;

[0076] Preferably, the curing agent is amidoamine and / or triethylenetetramine;

[0077] Preferably, the leveling agent is one or more of fluorine-modified acrylate, polyether polyester-modified organosiloxane and melamine formaldehyde resin.

[0078] Preferably, the defoaming agent is polyether type silicone polymer and / or polyethylene glycol fatty acid.

[0079] In the present application, the diluent helps to improve the dispersibility of the filler; the leveling agent and the defoaming agent can avoid the occurrence of bubbles in the coating and the coating forming process, and help to reduce the mechanical properties and hydrogen barrier properties of the coating; the curing agent can promote the material forming.

[0080] In the present application, the weight ratio of the epoxy resin, the diluent, the curing agent, the leveling agent and the defoaming agent is 1:0.1-0.5:0.1-0.2:0.01-0.06:0.01-0.03.

[0081] In a specific embodiment, the weight ratio of the epoxy resin and the diluent can be 1:0.1, 1:0.2, 1:0.3, 1:0.4 or 1:0.5, the weight ratio of the epoxy resin and the curing agent can be 1:0.1, 1:0.12, 1:0.14, 1:0.15, 1:0.16, 1:0.18 or 1:0.2, the weight ratio of the epoxy resin and the leveling agent can be 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05 or 1:0.06, and the weight ratio of the epoxy resin and the defoaming agent can be 1:0.01, 1:0.02 or 1:0.03.

[0082] In the present application, the molecular chain amino group of the polyhedral oligomeric silsesquioxane reacts chemically with the end carboxyl liquid butyl nitrile rubber, forms hydrogen bonds with the molecular chain hydroxyl of the epoxy resin, and forms hydrogen bonds with the hydroxyl or ionic liquid modified cobalt aluminum bimetallic hydroxide interlayer OH - of the ionic liquid modified graphite phase carbon nitride, thereby improving the crosslinking density of the high-temperature-resistant polyimide, and greatly improving the mechanical properties of the material and effectively reducing the hydrogen permeability.

[0083] In addition, the ionic liquid modified graphite phase carbon nitride in the present application has stable physical and chemical properties, and the layered structure can extend the hydrogen transmission path and delay the diffusion of hydrogen; the ionic liquid modified cobalt aluminum bimetallic hydroxide in situ forms Al2O3 particles with hydrogen barrier function due to the frictional resistance effect in the gas transport process, thereby playing a role in resisting hydrogen permeation. Further, the ionic liquid modified graphite phase carbon nitride and the ionic liquid modified cobalt aluminum layered double hydroxide have excellent wear resistance, which can improve the cavitation effect of the pipeline.

[0084] And the ionic liquid can form a protective film, play a role in inhibiting corrosion; layered graphite phase carbon nitride and cobalt aluminum double metal hydroxide due to its multi-layer structure has "labyrinth effect" to play a role in corrosion protection.

[0085] The second aspect of the present application provides a method for preparing the above-mentioned anti-hydrogen permeation composite coating, the method comprising the following steps:

[0086] (1) mixing epoxy resin, diluent and carboxyl-terminated liquid nitrile rubber, and stirring to obtain solution A;

[0087] (2) mixing the solution A with polyhedral oligomeric silsesquioxane and stirring to obtain solution B;

[0088] (3) mixing the solution B with ionic liquid modified layered nanocomposite and stirring to obtain solution C;

[0089] (4) mixing the solution C with curing agent, leveling agent and defoaming agent and stirring.

[0090] In step (1) of the present application, in order to ensure sufficient stirring uniformity, the stirring conditions are controlled to include a time of 10-100 min and a speed of 3000-12000 rmp.

[0091] In a specific embodiment of step (1), the stirring time can be 10 min, 30 min, 50 min, 70 min or 100 min, and the stirring speed can be 3000 rmp, 5000 rmp, 7000 rmp, 10000 rmp or 12000 rmp.

[0092] Preferably, in step (2), in order to ensure sufficient stirring uniformity, the stirring conditions are controlled to include a time of 10-60 min and a speed of 3000-10000 rmp.

[0093] In a specific embodiment of step (2), the stirring time can be 10 min, 20 min, 30 min, 40 min, 50 min or 60 min, and the stirring speed can be 3000 rmp, 4000 rmp, 5000 rmp, 6000 rmp, 7000 rmp, 8000 rmp, 9000 rmp or 10000 rmp.

[0094] Preferably, in step (3), in order to ensure uniform stirring, the stirring conditions are controlled to include a time of 20-160 min and a speed of 2000-5000 rmp.

[0095] In the specific embodiment of step (3), the stirring time can be 20 min, 60 min, 100 min, 140 min, 150 min or 160 min, and the stirring speed can be 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm or 5000 rpm.

[0096] In step (4), in order to ensure uniform mixing of the materials, the curing agent, the leveling agent and the defoaming agent are preferably mixed uniformly to obtain a curing composite solution, and then the solution C is mixed with the solution to perform stirring.

[0097] Preferably, in step (4), the stirring conditions include a time of 10-30 min and a speed of 1000-5000 rpm.

[0098] In the specific embodiment of step (4), the stirring time can be 10 min, 15 min, 20 min, 25 min or 30 min, and the stirring speed can be 1000 rpm, 1500 rpm, 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm, 4000 rpm, 4500 rpm or 5000 rpm.

[0099] The third aspect of the present application provides a use of the above-mentioned hydrogen permeation resistant composite coating in the preparation of an internal drag reduction hydrogen resistant coating.

[0100] The fourth aspect of the present application provides an internal drag reduction hydrogen resistant coating, which is prepared by coating and curing the above-mentioned hydrogen permeation resistant composite coating.

[0101] The fifth aspect of the present application provides a use of the internal drag reduction hydrogen resistant coating in the protection of a hydrogen-containing fuel conveying pipeline.

[0102] The present application prepares a coating with drag reduction and hydrogen permeation resistance by using an epoxy resin, a liquid carboxyl-terminated butyl nitrile rubber, a polyhedral oligomeric silsesquioxane and an ionic liquid modified layered nanocomposite material, etc. The coating can slow down the occurrence of hydrogen embrittlement of metal by significantly inhibiting hydrogen permeation, can improve the service life and reliability of metal parts of hydrogen-containing equipment, and has a broad application prospect in the above-mentioned fields and related fields.

[0103] The present application will be described in detail below through examples, but the protection scope of the present application is not limited thereto.

[0104] In the following examples, the carboxyl-terminated liquid nitrile rubber was purchased from Jingjiang Tonggao Chemical Co., Ltd., the polyhedral oligomeric silsesquioxane was purchased from Aladdin, the glycidyl ester of mono carboxylic acid was purchased from Wuhan Kemik Biological Medicine Technology Co., Ltd., the fluorine-modified acrylate was purchased from Weifang Fule New Material, the amidoamine was purchased from Yingchuang, and the polyether type silicone polymer was purchased from Hubei Chengfeng Chemical Co., Ltd.

[0105] Example 1

[0106] (1) After adding the diluent glycidyl ester of mono carboxylic acid to the epoxy resin E51, the carboxyl-terminated liquid nitrile rubber was added and mixed, and then stirred at a speed of 3000 rmp for 10 min to obtain solution A; wherein the carboxyl content of the carboxyl-terminated liquid nitrile rubber was in the range of 0.24-0.30 mol / kg;

[0107] (2) After adding the polyhedral oligomeric silsesquioxane to the solution A, it was mixed and stirred at a speed of 3000 rmp for 10 min to obtain solution B;

[0108] (3) After adding the ionic liquid modified layered nanocomposite (ionic liquid modified graphite phase carbon nitride, the number of layers of the graphite phase carbon nitride was 5 layers, and the ionic liquid was 1-butyl-3-methylimidazolium hexafluorophosphate) to the solution B, it was mixed and stirred at a speed of 2000 rmp for 20 min to obtain solution C;

[0109] (4) After mixing the curing agent amidoamine, the leveling agent fluorine-modified acrylate, and the defoaming agent polyether type silicone polymer uniformly, a curing composite solution was obtained, and then the curing composite solution was added to the solution C, mixed and stirred at a speed of 1000 rmp for 10 min to obtain the hydrogen permeation resistant composite coating A1;

[0110] The weight ratio of the epoxy resin, the carboxyl-terminated liquid nitrile rubber, the polyhedral oligomeric silsesquioxane, and the ionic liquid modified layered nanocomposite was 1:0.05:0.05:0.01;

[0111] The weight ratio of the epoxy resin, the diluent, the curing agent, the leveling agent, and the defoaming agent was 1:0.1:0.1:0.01:0.01;

[0112] The preparation method of the ionic liquid modified graphite phase carbon nitride was as follows:

[0113] S1, 2g dicyandiamide and 10g ammonium chloride were dissolved in 50mL deionized water, mixed and magnetically stirred until the solution was clear, then heated at 100℃ to remove water, and the obtained material was placed in a muffle furnace at a temperature of 550℃ for 2h to obtain graphite phase carbon nitride;

[0114] S2, 1g graphite phase carbon nitride was placed in 50ml deionized water and mixed and ultrasonically stirred, then the mixture was transferred to a stainless steel autoclave, and kept at a temperature of 200℃ for 12h, then 40ml supernatant was mixed with 4ml ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate), ultrasonically treated for 30min and filtered, and the obtained solid was dried to obtain ionic liquid modified graphite phase carbon nitride.

[0115] Example 2

[0116] (1) After adding diluent monobasic carboxylic acid glycidyl ester to epoxy resin E51, adding carboxyl-terminated liquid butadiene-acrylonitrile rubber, mixing and stirring, the stirring time was 100min and the stirring speed was 12000rmp, and after uniform stirring, solution A was obtained; wherein the carboxyl content of the carboxyl-terminated liquid butadiene-acrylonitrile rubber was in the range of 0.43-0.65mol / kg;

[0117] (2) After adding polyhedral oligomeric silsesquioxane to solution A, mixing and stirring, the stirring time was 60min and the stirring speed was 10000rmp, and after uniform stirring, solution B was obtained;

[0118] (3) After adding ionic liquid modified layered nanocomposite (ionic liquid modified cobalt-aluminum double metal hydroxide, the aspect ratio of the cobalt-aluminum double metal hydroxide was 20:1, and the ionic liquid was 1-butyl-3-methylimidazolium hexafluorophosphate) to solution B, mixing and stirring, the stirring time was 160min and the stirring speed was 1800rmp, and after uniform stirring, solution C was obtained;

[0119] (4) After mixing the curing agent amidoamine, the leveling agent fluorine-modified acrylate and the defoaming agent polyether-type organosilicon polymer uniformly, a curing composite solution was obtained, then the curing composite solution was added to solution C, mixed and stirred, the stirring time was 30min and the stirring speed was 5000rmp, and after uniform stirring, hydrogen permeation resistant composite coating A2 was obtained;

[0120] The weight ratio of the amounts of the epoxy resin, the carboxyl-terminated liquid butadiene-acrylonitrile rubber, the polyhedral oligomeric silsesquioxane and the ionic liquid modified layered nanocomposite was 1:0.5:0.3:0.01;

[0121] The weight ratio of the amounts of the epoxy resin, the diluent, the curing agent, the leveling agent and the defoaming agent was 1:0.5:0.2:0.06:0.03;

[0122] The preparation method of the ion liquid modified cobalt-aluminum double metal hydroxide is as follows:

[0123] (a) Co(NO3)2 and Al(OH)3 are dissolved in 50 mL of deionized water to prepare a mixed salt solution; wherein the molar ratio of the use amount of Co(NO3)2 to Al(OH)3 is 2:1, the concentration of Co element in the mixed salt solution is 0.05 mol / L, and the concentration of Al element is 0.2 mol / L;

[0124] (b) The ion liquid (1-butyl-3-methylimidazolium hexafluorophosphate), the mixed salt solution and deionized water are mixed to obtain a mixed solution; wherein the molar ratio of the use amount of Al(OH)3 to the ion liquid is 2:1, the concentration of Al(OH)3 in the mixed solution is 0.01 mol / L, and the concentration of the ion liquid is 0.005 mol / L;

[0125] (c) The mixed solution is mixed with a 2 mol / L sodium hydroxide solution, then crystallized at 120°C for 10 h, and then precipitated; the precipitation conditions include that the pH value of the system is 9, followed by filtration, washing the obtained solid by deionized water, and finally filtering and drying.

[0126] Example 3

[0127] (1) After adding a diluent monobasic carboxylic acid glycidyl ester to the epoxy resin E51, adding a carboxyl-terminated liquid butyl nitrile rubber, mixing and stirring, the stirring time is 10 min, the stirring speed is 3000 rmp, and after uniform stirring, solution A is obtained; wherein the carboxyl content of the carboxyl-terminated liquid butyl nitrile rubber ranges from 0.43 to 0.50 mol / kg;

[0128] (2) After adding a polyhedral oligomeric silsesquioxane to solution A, mixing and stirring, the stirring time is 10 min, the stirring speed is 3000 rmp, and after uniform stirring, solution B is obtained;

[0129] (3) After adding an ion liquid modified layered nanocomposite (ion liquid modified cobalt-aluminum double metal hydroxide and ion liquid modified graphite phase carbon nitride, the number of layers of the graphite phase carbon nitride is 50 layers, the aspect ratio of the cobalt-aluminum double metal hydroxide is 80:1, and the ion liquid is 1-butyl-3-methylimidazolium hexafluorophosphate) to solution B, mixing and stirring, the stirring time is 20 min, the stirring speed is 2000 rmp, and after uniform stirring, solution C is obtained;

[0130] (4)mixing the curing agent amidoamine, the leveling agent fluorine-modified acrylate and the defoaming agent polyether-type organosilicon polymer uniformly to obtain a curing composite solution, then adding the curing composite solution into the solution C, mixing and stirring, the stirring time is 10 min, the stirring speed is 1000 rmp, and the anti-hydrogen permeation composite coating A3 is obtained after uniform stirring;

[0131] The weight ratio of the amounts of the epoxy resin, the end carboxyl liquid nitrile rubber, the polyhedral oligomeric silsesquioxane and the ionic liquid modified layered nanocomposite is 1:0.05:0.05:0.02; the weight ratio of the amounts of the epoxy resin, the ionic liquid modified cobalt-aluminum double-metal hydroxide and the ionic liquid modified graphite phase carbon nitride is 1:0.01:0.01;

[0132] The weight ratio of the amounts of the epoxy resin, the diluent, the curing agent, the leveling agent and the defoaming agent is 1:0.1:0.1:0.01:0.01;

[0133] The preparation of the ionic liquid modified cobalt-aluminum double-metal hydroxide is carried out according to the method of Example 2, except that the molar ratio of the amounts of Al(OH)3 and the ionic liquid is 2:0.3, the concentration of Al(OH)3 in the mixed solution is 0.1 mol / L, the concentration of the ionic liquid is 0.015 mol / L, and the crystallization time is 8 h;

[0134] The preparation of the ionic liquid modified graphite phase carbon nitride is carried out according to the method of Example 1, except that the amount of ammonium chloride is 20 g.

[0135] Example 4

[0136] (1) After adding the diluent monobasic glycidyl ester into the epoxy resin E44, the end carboxyl liquid nitrile rubber is added and stirred, the stirring time is 60 min, the stirring speed is 5000 rmp, and the solution A is obtained after uniform stirring; wherein the carboxyl content of the end carboxyl liquid nitrile rubber ranges from 0.37 to 0.45 mol / kg;

[0137] (2) After adding the polyhedral oligomeric silsesquioxane into the solution A, stirring is carried out, the stirring time is 30 min, the stirring speed is 5000 rmp, and the solution B is obtained after uniform stirring;

[0138] (3) After adding the ionic liquid modified layered nanocomposite (the ionic liquid modified graphite phase carbon nitride, the number of layers of the graphite phase carbon nitride is 15 layers, and the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate) into the solution B, stirring is carried out, the stirring time is 100 min, the stirring speed is 3000 rmp, and the solution C is obtained after uniform stirring;

[0139] (4) the curing agent amidoamine, the leveling agent fluorine-modified acrylate, the defoaming agent polyether type organosilicon polymer are mixed uniformly to obtain a curing composite solution, then the curing composite solution is added into the solution C, mixed and stirred, the stirring time is 20 min, the stirring speed is 4000 rmp, and the anti-hydrogen permeation composite coating A4 is obtained after uniform stirring;

[0140] The weight ratio of the epoxy resin, the carboxyl-terminated liquid nitrile rubber, the polyhedral oligomeric silsesquioxane and the ionic liquid modified layered nanocomposite is 1:0.15:0.1:0.2;

[0141] The weight ratio of the epoxy resin, the diluent, the curing agent, the leveling agent and the defoaming agent is 1:0.5:0.15:0.03:0.03;

[0142] The preparation of the ionic liquid modified graphite phase carbon nitride is carried out according to the method of Example 1, and the difference is that the amount of ammonium chloride is 14 g.

[0143] Example 5

[0144] (1) The carboxyl-terminated liquid nitrile rubber is mixed and stirred after being added into the epoxy resin E44 and the diluent monocarboxylic acid glycidyl ester, the stirring time is 90 min, the stirring speed is 8000 rmp, and the solution A is obtained after uniform stirring; wherein the carboxyl content of the carboxyl-terminated liquid nitrile rubber ranges from 0.50 to 0.65 mol / kg;

[0145] (2) The polyhedral oligomeric silsesquioxane is mixed and stirred after being added into the solution A, the stirring time is 60 min, the stirring speed is 8000 rmp, and the solution B is obtained after uniform stirring;

[0146] (3) The ionic liquid modified layered nanocomposite (the ionic liquid modified cobalt-aluminum double metal hydroxide and the ionic liquid modified graphite phase carbon nitride, the number of layers of the graphite phase carbon nitride is 30, the aspect ratio of the cobalt-aluminum double metal hydroxide is 50:1, and the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate) is mixed and stirred after being added into the solution B, the stirring time is 80 min, the stirring speed is 4000 rmp, and the solution C is obtained after uniform stirring;

[0147] (4) The curing agent amidoamine, the leveling agent fluorine-modified acrylate, the defoaming agent polyether type organosilicon polymer are mixed uniformly to obtain a curing composite solution, then the curing composite solution is added into the solution C, mixed and stirred, the stirring time is 30 min, the stirring speed is 5000 rmp, and the anti-hydrogen permeation composite coating A5 is obtained after uniform stirring;

[0148] The weight ratio of the amounts of the epoxy resin, the carboxyl-terminated liquid butyl nitrile rubber, the polyhedral oligomeric silsesquioxane, and the ionic liquid modified layered nanocomposite is 1:0.15:0.18:0.16; the weight ratio of the amounts of the epoxy resin, the ionic liquid modified cobalt-aluminum double-metal hydroxide, and the ionic liquid modified graphite phase carbon nitride is 1:0.01:0.15;

[0149] The weight ratio of the amounts of the epoxy resin, the diluent, the curing agent, the leveling agent, and the defoaming agent is 1:0.5:0.16:0.05:0.018;

[0150] The preparation of the ionic liquid modified cobalt-aluminum double-metal hydroxide is carried out according to the method of Example 2, except that the molar ratio of the amounts of Al(OH)3 and the ionic liquid is 2:0.5, the concentration of Al(OH)3 in the mixed solution is 0.5 mol / L, the concentration of the ionic liquid is 0.125 mol / L, and the crystallization time is 18 h;

[0151] The preparation of the ionic liquid modified graphite phase carbon nitride is carried out according to the method of Example 1, except that the amount of ammonium chloride is 18 g.

[0152] Example 6

[0153] (1) After the epoxy resin E44 is added with the diluent monobasic carboxylic glycidyl ester, the carboxyl-terminated liquid butyl nitrile rubber is added and mixed, and then stirred for 90 min at a stirring speed of 8000 rpm to obtain a solution A; the carboxyl content of the carboxyl-terminated liquid butyl nitrile rubber is in the range of 0.50-0.65 mol / kg;

[0154] (2) The polyhedral oligomeric silsesquioxane is added to the solution A, mixed, and then stirred for 60 min at a stirring speed of 8000 rpm to obtain a solution B;

[0155] (3) The ionic liquid modified layered nanocomposite (the ionic liquid modified cobalt-aluminum double-metal hydroxide, the aspect ratio of the cobalt-aluminum double-metal hydroxide is 40:1, and the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate) is added to the solution B, mixed, and then stirred for 80 min at a stirring speed of 4000 rpm to obtain a solution C;

[0156] (4) The curing agent amidoamine, the leveling agent fluorine-modified acrylate, and the defoaming agent polyether type organosilicon polymer are mixed uniformly to obtain a curing composite solution, which is then added to the solution C, mixed, and then stirred for 30 min at a stirring speed of 5000 rpm to obtain a hydrogen permeation resistant composite coating A6;

[0157] The weight ratio of the epoxy resin, the carboxyl-terminated liquid butyl nitrile rubber, the polyhedral oligomeric silsesquioxane, and the ionic liquid modified layered nanocomposite is 1:0.3:0.18:0.16;

[0158] The weight ratio of the epoxy resin, the diluent, the curing agent, the leveling agent, and the defoaming agent is 1:0.4:0.16:0.05:0.018;

[0159] The preparation of the ionic liquid modified cobalt-aluminum double metal hydroxide is carried out according to the method of Example 2, except that the molar ratio of Al(OH)3 to ionic liquid is 2:0.1, the concentration of Al(OH)3 in the mixed solution is 0.3 mol / L, and the concentration of ionic liquid is 0.015 mol / L.

[0160] Example 7

[0161] (1) After adding the diluent monobasic carboxylic acid glycidyl ester to the epoxy resin E51, the carboxyl-terminated liquid butyl nitrile rubber is added and mixed, and then stirred for 60 min at a speed of 5000 rpm to obtain solution A; the carboxyl content of the carboxyl-terminated liquid butyl nitrile rubber is in the range of 0.37-0.45 mol / kg;

[0162] (2) After adding the polyhedral oligomeric silsesquioxane to solution A, it is mixed and stirred for 30 min at a speed of 5000 rpm to obtain solution B;

[0163] (3) After adding the ionic liquid modified layered nanocomposite (ionic liquid modified cobalt-aluminum double metal hydroxide and ionic liquid modified graphite phase carbon nitride, the number of layers of the graphite phase carbon nitride is 38, the aspect ratio of the cobalt-aluminum double metal hydroxide is 55:1, and the ionic liquid is 1-butyl-3-methylimidazolium tetrafluoroborate) to solution B, it is mixed and stirred for 100 min at a speed of 3000 rpm to obtain solution C;

[0164] (4) After mixing the curing agent amidoamine, the leveling agent fluorine-modified acrylate, and the defoaming agent polyether type organosilicon polymer uniformly, a curing composite solution is obtained, and then the curing composite solution is added to solution C, mixed and stirred for 20 min at a speed of 4000 rpm to obtain hydrogen permeation resistant composite coating A7;

[0165] The weight ratio of the amounts of the epoxy resin, the carboxyl-terminated liquid butyl nitrile rubber, the polyhedral oligomeric silsesquioxane and the ionic liquid modified layered nanocomposite is 1:0.35:0.25:0.37; the weight ratio of the amounts of the epoxy resin, the ionic liquid modified cobalt-aluminum double-metal hydroxide and the ionic liquid modified graphite phase carbon nitride is 1:0.21:0.16;

[0166] The weight ratio of the amounts of the epoxy resin, the diluent, the curing agent, the leveling agent and the defoaming agent is 1:0.4:0.15:0.03:0.03;

[0167] The ionic liquid modified cobalt-aluminum double-metal hydroxide is prepared according to the method of Example 2, except that the molar ratio of the amounts of Al(OH)3 and the ionic liquid is 2:0.4, the concentration of Al(OH)3 in the mixed solution is 0.4 mol / L, the concentration of the ionic liquid is 0.08 mol / L, and the crystallization time is 12 h;

[0168] The ionic liquid modified graphite phase carbon nitride is prepared according to the method of Example 1.

[0169] Comparative Example 1

[0170] The method of Example 1 is implemented, except that the polyhedral oligomeric silsesquioxane and the ionic liquid modified layered nanocomposite are not added, and the curing composite solution is directly added to solution A to obtain a composite coating D1.

[0171] Comparative Example 2

[0172] The method of Example 1 is implemented, except that the ionic liquid modified layered nanocomposite is not added, and the curing composite solution is directly added to solution B to obtain a composite coating D2.

[0173] Comparative Example 3

[0174] The method of Example 1 is implemented, except that the ionic liquid modified layered nanocomposite is not used, and the ionic liquid modified layered nanocomposite is replaced by the same weight of the graphite phase carbon nitride prepared in step S1 to obtain a composite coating D3.

[0175] Test Example 1

[0176] The ionic liquid modified cobalt-aluminum double-metal hydroxide and the ionic liquid modified graphite phase carbon nitride in Examples 1 and 2 are detected by scanning electron microscopy and transmission electron microscopy, respectively. The scanning electron microscopy image of the ionic liquid modified cobalt-aluminum double-metal hydroxide is shown in FIG. 1, and the transmission electron microscopy image of the ionic liquid modified graphite phase carbon nitride is shown in FIG. 2. Figure 1 The scanning electron microscopy image of the ionic liquid modified cobalt-aluminum double-metal hydroxide is shown in FIG. 1, and the transmission electron microscopy image of the ionic liquid modified graphite phase carbon nitride is shown in FIG. 2. Figure 2 ​

[0177] According to Figure 1 and Figure 2 It can be seen that the ion liquid modified cobalt-aluminum double metal hydroxide has a uniform, sub-micron microstructure, which is beneficial to improve its dispersion in the coating; the ion liquid modified graphite phase carbon nitride has a multi-layer structure, which is beneficial to build a dense maze structure in the coating, which can more effectively block hydrogen; and the thickness of the ion liquid modified cobalt-aluminum double metal hydroxide and the ion liquid modified graphite phase carbon nitride is within 2-100 nm.

[0178] Test Example 2

[0179] The hydrogen blocking performance and other related properties of A1-A7 and D1-D3 were detected respectively;

[0180] Hydrogen blocking performance test: evenly coat A1-A7 and D1-D3 prepared on a 316 steel sheet with a size of 3 cm x 3 cm, and place it at room temperature (25°C) to solidify and form a coating with the same thickness. The obtained coating was subjected to hydrogen diffusion experiment by using Devnathan-Stachurski double electrolytic cell to obtain hydrogen permeation current, and the maximum hydrogen permeation current density was obtained.

[0181] The hydrogen blocking performance detection method is: first fix the coating sample, then configure the anode cell solution as 0.2 mol / L NaOH solution, and the cathode cell solution as 3.5% NaCl solution. The reference electrode type of the main channel is Hg / HgO (1M NaOH), and the reference electrode of the auxiliary channel is SCE (mercury / saturated KCL). The results are shown in Table 1.

[0182] Table 1

[0183] Number Maximum hydrogen permeation current density A1 0.29 μA / cm 2 ]] A2 0.25 μA / cm 2 ]] A3 0.23 μA / cm 2 ]] A4 0.27 μA / cm 2 ]] A5 0.25 μA / cm 2 ]] A6 0.27 μA / cm 2 ]] A7 0.24 μA / cm 2 ]] D1 0.54 μA / cm 2 ]] D2 0.48 μA / cm 2 ]] D3 0.50 μA / cm 2 ]]

[0184] The other related performance tests and detection standards and detection results are shown in Tables 2-4, respectively.

[0185] Table 2

[0186]

[0187]

[0188] Table 3

[0189]

[0190]

[0191] Table 4

[0192]

[0193]

[0194] It can be seen from the results of Tables 1-4 that, compared with Comparative Example 1, the hydrogen barrier property of the coating of Example 1 is greatly improved by 46% by adding polyhedral oligomeric silsesquioxane and ion liquid modified graphitic carbon nitride nanosheets, and other performances are better than those of Comparative Example 1; compared with Comparative Example 2, the hydrogen barrier property of the coating of Example 1 is improved by 40% by adding polyhedral oligomeric silsesquioxane, and other performances are better than those of Comparative Example 2. Compared with the coating obtained by adding unmodified layered graphitic carbon nitride nanosheets in Comparative Example 3, the hydrogen barrier property of the coating obtained by adding ion liquid modified layered graphitic carbon nitride nanosheets in Comparative Example 2 is improved by 4%, and other performances are better than those of Comparative Example 3.

[0195] According to the above results, the coating prepared by the anti-hydrogen permeation composite coating of the present application has good flexibility, corrosion resistance, solvent resistance, wear resistance and excellent anti-hydrogen permeation effect, and has a broad application prospect in hydrogen transmission pipelines.

[0196] The preferred embodiments of the present application are described in detail above, 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, and 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. An anti-hydrogen permeation composite coating, characterized by, The raw materials for preparing the anti-hydrogen permeation composite coating contain an epoxy resin, a carboxyl-terminated liquid butyl nitrile rubber, a polyhedral oligomeric silsesquioxane and an ionic liquid modified layered nanocomposite. The layered nanocomposite is graphitic carbon nitride and / or cobalt-aluminum double metal hydroxide, and the thickness of the layered nanocomposite is 2-100 nm.

2. The anti-hydrogen permeation composite coating of claim 1, wherein, The weight ratio of the epoxy resin, the carboxyl-terminated liquid butyl nitrile rubber, the polyhedral oligomeric silsesquioxane and the ionic liquid modified layered nanocomposite is 1:0.05-0.5:0.05-0.3:0.01-0.

5.

3. The anti-hydrogen permeation composite coating according to claim 1 or 2, characterized in that, The epoxy resin is E51 and / or E44.

4. The anti-hydrogen permeation composite coating according to claim 1 or 2, characterized in that, The carboxyl content of the carboxyl-terminated liquid butyl nitrile rubber is 0.24-0.65 mol / kg.

5. The anti-hydrogen permeation composite coating of claim 1, wherein, The number of layers of the graphitic carbon nitride is 5-50 layers. Preferably, the aspect ratio of the cobalt-aluminum double metal hydroxide is 20-80:

1. Preferably, the ionic liquid is 1-butyl-3-methylimidazolium hexafluorophosphate and / or 1-butyl-3-methylimidazolium tetrafluoroborate.

6. The hydrogen permeation resistant composite coating of claim 1, wherein, The raw materials for preparing the anti-hydrogen permeation composite coating further contain a diluent, a curing agent, a leveling agent and a defoaming agent.

7. The anti-hydrogen permeation composite coating of claim 6, wherein, The diluent is one or two or more of glycidyl neodecanoate, glycidyl neoundecanoate, glycidyl valerate and glycidyl monocarboxylic acid. Preferably, the curing agent is amidoamine and / or triethylenetetramine. Preferably, the leveling agent is one or two or more of fluorine-modified acrylate, polyether polyester-modified organosiloxane and melamine formaldehyde resin. Preferably, the defoaming agent is polyether type organosilicon polymer and / or polyethylene glycol fatty acid.

8. The anti-hydrogen permeation composite coating according to claim 6 or 7, characterized in that The weight ratio of the epoxy resin, the diluent, the curing agent, the leveling agent and the defoaming agent is 1:0.1-0.5:0.1-0.2:0.01-0.06:0.01-0.

03.

9. A method of preparing the anti-hydrogen permeation composite coating according to any one of claims 1 to 8, characterized in that, The method comprises the following steps: (1) mixing the epoxy resin, the diluent and the carboxyl-terminated liquid butyl nitrile rubber and stirring to obtain solution A; (2) mixing the solution A and the polyhedral oligomeric silsesquioxane and stirring to obtain solution B; (3) mixing the solution B and the ionic liquid modified layered nanocomposite and stirring to obtain solution C; (4) mixing the solution C and the curing agent, the leveling agent and the defoaming agent and stirring.

10. The method of claim 9, wherein, In step (1), the stirring conditions include a time of 10-100 min and a speed of 3000-12000 rpm.

11. The method according to claim 9 or 10, characterized in that, In step (2), the stirring conditions include a time of 10-60 min and a speed of 3000-10000 rpm.

12. The method of claim 9, wherein, In step (3), the stirring conditions include a time of 20-160 min and a speed of 2000-5000 rpm.

13. The method according to claim 9 or 12, characterized in that, In step (4), the stirring conditions include a time of 10-30 min and a speed of 1000-5000 rpm.

14. Use of the anti-hydrogen permeation composite coating according to any one of claims 1-8 in the preparation of an inner drag-reducing hydrogen-resistant coating.

15. An internal drag reducing hydrogen barrier coating, characterized by, The internal drag reducing hydrogen barrier coating is made by coating and curing the hydrogen permeation resistant composite coating according to any one of claims 1-8.

16. Use of the internal drag reducing hydrogen barrier coating according to claim 15 for protection of hydrogen containing fuel pipelines.

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