CN113881327A - Preparation method of oil-resistant static-conductive anticorrosive paint added with modified graphene - Google Patents

Preparation method of oil-resistant static-conductive anticorrosive paint added with modified graphene Download PDF

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CN113881327A
CN113881327A CN202111324725.2A CN202111324725A CN113881327A CN 113881327 A CN113881327 A CN 113881327A CN 202111324725 A CN202111324725 A CN 202111324725A CN 113881327 A CN113881327 A CN 113881327A
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oil
water
phenoxy resin
modified graphene
graphene oxide
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王保军
拾振洪
李海洋
金传亮
回留柱
王家振
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Anhui Xindalu Special Paint Co ltd
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Anhui Xindalu Special Paint Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09D171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/025—Preservatives, e.g. antimicrobial agents
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints

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Abstract

The invention discloses a preparation method of an oil-resistant static-conducting anticorrosive coating added with modified graphene, belonging to the technical field of anticorrosive coatings. F-doped low-conductivity and flaky fluorinated graphene oxide, and is added into the phenoxy resin coating to improve the corrosion resistance of the coating. The fluorinated graphene oxide nanosheet not only has impermeability, but also has constant electrical insulation property and long-term anticorrosion effect, enhances the physical barrier of the coating and prolongs the anticorrosion time, and the fluorinated graphene oxide nanosheet is difficult to permeate and has good dispersion of the electrical insulation property.

Description

Preparation method of oil-resistant static-conductive anticorrosive paint added with modified graphene
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a preparation method of an oil-resistant static-conducting anticorrosive coating added with modified graphene.
Background
With the rapid development of the petroleum industry and the start of strategic petroleum reserves, oil resistance, static conduction and corrosion prevention are increasingly emphasized. For example, if the electrostatic hazard of a base material such as an oil tank is not eliminated in time, the potential explosion is likely to occur, and therefore, the coating layer must have excellent antistatic properties while considering the anti-corrosion protection of the oil tank. In the past, people adopt black oil-resistant conductive electrostatic coatings such as graphite, which are inconvenient to find hidden troubles during maintenance and have the defect that graphite seeps out to pollute oil products. On the other hand, in the selection of the paint variety of the oil-resistant static conductive paint, the epoxy resin paint is regarded as the best variety of the oil tank inner wall anticorrosive paint by virtue of excellent oil resistance and anticorrosive performance, but the traditional epoxy resin paint is difficult to cure at the temperature below 10 ℃, which seriously affects the adoption of the phenoxy resin paint in winter. The low-temperature cured light-color oil tank static-conducting oil-resistant phenoxy resin anticorrosive finish paint is developed. The imported sulfur-containing crude oil at present has high sulfide and acidic corrosive medium, the average sulfur content is over 1.107%, the acidic medium content is high, for example, high sulfur, hydrogen sulfide, mercaptan and other sulfides with high activity cause the corrosion degree of an oil storage container system to be intensified in the storage and transportation process, and partial sulfur corrosion products also have certain flammability, which brings great potential risks to the safe operation of an oil storage container and a refinery production system, is very easy to cause safety accidents such as fire, explosion and the like, and brings new difficulties to the maintenance of a newly-built oil storage container and an old oil storage container, so that a main corrosion mechanism needs to be understood urgently and effective anticorrosion measures are taken. As for the internal corrosion phenomenon of the prior oil storage container in China, the corrosion mainly comes from liquid corrosion and gas corrosion, and the corrosion parts are mainly distributed at a gas phase part, an oil storage part and the bottom of the oil storage container. The corrosion phenomenon of the gas phase part and the bottom of the oil storage container is serious, because for the gas phase part, a layer of liquid film can be formed on the tank top and the upper tank wall after the acid gases such as sulfur dioxide, hydrogen sulfide and the like volatilized by the oil product, oxygen and water undergo temperature rise and fall, under the action of the liquid film, the depolarization reaction of the oxygen can be stronger, and the corrosion of the storage key can be serious. The corrosion to the bottom of the oil storage container is mainly caused by that water is continuously deposited in the oil storage container in the long-term use process, and in addition, various impurities in oil products are settled or dissolved in the oil storage container, the substances are fused together to have high corrosivity, the bottom of the oil storage container is seriously corroded over time, and the corrosion puddle of the oil storage part is mainly from the oil products and belongs to liquid corrosion. In the past, people use carbon black to conduct static electricity, spherical carbon black filler which is mostly applied in the past cannot be uniformly dispersed and is not tightly isolated enough, corrosive electrolyte solution can permeate through a coating to form a plurality of tiny primary batteries between carbon black and a metal substrate to form galvanic corrosion, so that the coating generates a bubbling phenomenon, and finally the coating falls off and is protected to lose efficacy. For example, CN109233406A, a preparation method of static conductive paint, has shown a significant advantage over traditional corrosion protection materials in that graphene coating maintains its protective properties for a short period of time, but during long-term soaking, graphene promotes metal corrosion at coating defects. The uniform dispersibility of the graphene is crucial to the performance of the anticorrosive coating, and the graphene with good dispersibility can obviously improve the anticorrosive performance of the anticorrosive coating, and otherwise, the comprehensive performance of the anticorrosive coating can be rapidly reduced. The nano graphene powder has unbalanced surface charges, and is easy to agglomerate, even to cause bulk accumulation. The technical personnel in the field need to develop a preparation method of the oil-resistant static-conductive anticorrosive coating added with the modified graphene so as to meet the existing use requirements and performance requirements.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of an oil-resistant static-conducting anticorrosive coating added with modified graphene.
The invention is realized by the following technical scheme:
a preparation method of an oil-resistant static-conducting anticorrosive coating added with modified graphene comprises the following steps:
firstly, preparing phenoxy resin emulsion: the phenoxy resin emulsion is prepared by emulsifying and mixing 7-9% of water-soluble organic silicon, 0.2-0.5% of defoaming agent, 45-50% of phenoxy resin slurry and the balance of water, wherein the sum of the components is one hundred percent; the specific emulsification and mixing method comprises the following steps: adding water-soluble organic silicon, a defoaming agent and water into an emulsifier, stirring, adding the preheated phenoxy resin slurry in a fine line shape, and fully stirring to obtain phenoxy resin emulsion;
the water emulsion type phenoxy resin is prepared by mixing, milling, granulating and dissolving. Preparing phenoxy resin slurry, adding water-soluble sodium silicate, emulsifier and part of water into an emulsifier, stirring, adding preheated phenoxy resin thick slurry coating in a fine line shape, and fully stirring to obtain phenoxy resin emulsion.
Phenoxy resins are thermoplastic resins and not epoxy resins. Phenoxy resins have good adhesion to adherends such as copper, brass, steel, aluminum, wood, and other non-metals.
Secondly, preparing a crosslinking solution: uniformly mixing 0.1-0.2 part of sodium fluosilicate, 1-2 parts of a cross-linking agent, 12-14 parts of modified graphene and 78-84 parts of water in parts by weight, heating to 60-65 ℃, uniformly stirring and dispersing for 10-20 min to obtain a cross-linking solution; mixing the coating before use: uniformly mixing the phenoxy resin emulsion and the crosslinking liquid obtained in the step one according to the mass ratio of 6-7: 1.3-1.5 to obtain the oil-resistant static-conducting anticorrosive coating added with the modified graphene.
Further, the water-soluble organic silicon is a sodium methyl silanol water solution, the pH value of the water-soluble organic silicon is 12-13, and the solid content of the water-soluble organic silicon is 27-29%.
Further, the step two crosslinking agent is one or more of Epilink701, Anquamine670, Anquamine156, Anquamine419 and 2-sulfoterephthalic acid anhydride.
Further, the modified graphene is fluorinated graphene oxide, the fluorinated graphene oxide is directly fluorinated graphene containing oxygen functional groups and fluorine atoms, preferably, the fluorinated graphene oxide has a sheet diameter of 0.5-5 μm and a sheet thickness of 0.8-1.2 nm; preferably, the fluorinated graphene oxide F/C is 0.47; preferably, the fluorinated graphene oxide sheet layer is modified with a secondary amine group.
The graphene is functionalized by ethanolamine, the obtained ethanolamine functionalized graphene shows a stripped state in DMF and can be stably dispersed in solvents such as water, ethanol, acetone and the like, AFM tests show that the average thickness of the obtained functionalized graphene is 3-4 nm, and the introduction of the ethanolamine enables the thermal stability of the functionalized graphene to be improved compared with that of graphene oxide, but lower than that of reduced graphene oxide, and the functionalized graphene can further participate in a crosslinking reaction due to good redispersibility and active primary hydroxyl and secondary amine groups.
Further, the defoaming agent is one or more of FoamasterMO2157 and FoamaStarST 2410.
Further, the mixed using method comprises the following steps:
(1) pretreatment: carrying out acid washing, grinding and polishing treatment on a metal base material, and then washing and drying the metal base material to ensure that the surface of the metal base material is clean and rough;
(2) spraying the paint: preheating the treated metal substrate to 35-40 ℃, and spraying the oil-resistant static-conducting anticorrosive paint of the modified graphene on the metal substrate;
(3) and (3) thermal radiation curing: and (3) performing thermal radiation crosslinking treatment on the sprayed metal base material for 30-50 min by an infrared baking lamp at a lamp distance of 40-48 cm.
The invention has the beneficial effects that:
the invention discloses a preparation method of an oil-resistant static-conductive anticorrosive coating added with modified graphene, which is characterized in that phenoxy resin is dissolved in a solvent to prepare high-concentration oxygen resin slurry, and then a proper amount of anionic surfactant, stabilizer, water and the like are added. The modified fluorinated graphene oxide shows excellent dispersibility in phenoxy resin emulsion, can effectively fill pores in a polymer matrix, obviously inhibits the permeation of corrosion-related media through a coating, greatly improves the oil-resistant and corrosion-resistant performance of the coating, reduces the oxygen transmission rate, and has the advantages of physical barrier effect, inhibition of corrosion promotion activity, high compatibility between the fluorinated graphene oxide and the phenoxy resin, effective inhibition of galvanic corrosion of the conventional directly added graphene, and good dispersion in the phenoxy resin matrix. The fluorinated graphene oxide has low conductivity and flake shape, and is added into the phenoxy resin coating to improve the corrosion resistance of the coating and endow electrostatic conduction effect. F atom doping can change the electron conduction path of fluorinated graphene oxide, continuous pi-pi bonds are converted into isolated pi-pi bonds, and the conductivity can reach static electricity and avoid galvanic corrosion along with the F doping degree, and meanwhile, the fluorinated graphene oxide is used for preparing the material for the surface of the material for the surface for the material for the surface for the material for the. Therefore, the added modified graphene can inhibit the corrosion promoting activity of the simply added graphene, the obtained ethanolamine-functionalized graphene shows a state of being peeled off, can be stably dispersed in water and a solvent, can further promote crosslinking due to the secondary amine group, and the fluorinated graphene oxide has impermeability and certain electrical insulation. Open circuit potential-time curve and salt spray tests show that the coating added with the modified graphene has a long-term anticorrosion effect, and the fluorinated graphene oxide nanosheets which are difficult to permeate and have good electrical insulation performance and good dispersion enhance the physical barrier of phenoxy resin and prolong the anticorrosion time. FG has less surface energy and better hydrophobic properties than graphene, and thus the corrosion resistance of the coating is improved. On the other hand, phenoxy resin has-0H group, and is crosslinked with acid anhydride, amino group and the like at normal temperature to be cured, and the phenoxy resin can be uniformly coated on the surface of an object even if a curing agent is not used, can achieve the strength of the plastic after being cooled, and can be used for bonding metal, wood, glass, ceramic and the like. If the crosslinking agent is used to react with hydroxyl in the molecule, a thermosetting coating with higher glossiness can be generated. The graphene oxide is prepared into the fluorinated graphene in a hydrothermal mode, although the cost is low, the reaction speed is high, the obtained product can be dissolved in water again, the fluorination degree is low, and oxygen-containing functional groups exist on the surface of the fluorinated graphene, so that the ethanolamine can be conveniently functionalized, and secondary amino groups are endowed.
Compared with the prior art, the invention has the following advantages:
the fluorinated graphene oxide with low surface energy endows the phenoxy resin coating with excellent super-hydrophobicity and corrosion resistance, and meanwhile, the fluorinated graphene oxide with low surface energy endows the phenoxy resin coating with excellent super-hydrophobicity due to the self-cleaning function, mechanical wear resistance and chemical stability in acidic and alkaline aqueous solutions, and has excellent protection performance due to the self-cleaning function, mechanical wear resistance and chemical stability in acidic and alkaline aqueous solutions. The flexible fluorinated graphene oxide sheet structure shows outstanding isolation, well blocks the spread and corrosion of corrosive media, can strengthen the corrosion resistance of the phenoxy resin coating, and has better physical isolation performance than the traditional carbon conductive filler. In unit longitudinal thickness, the number of layers that graphene can be stacked is more, the path that a corrosive medium reaches a metal matrix is prolonged, the shielding performance of the coating on the corrosive medium is enhanced, and therefore the protective performance of the coating is improved. The graphene is used as a static conductive filler, the addition amount of the graphene is greatly lower than that of conductive fillers such as metals and carbon black, and meanwhile, the fluorinated graphene oxide is easy to disperse, is not easy to settle and oxidize in a phenoxy resin coating, and has the characteristic of stable conductive capacity. Due to the small size effect, the two-dimensional lamellar structure, the hydrophobicity and the electrical conductivity of the graphene, the graphene can be used as a filler for improving the anticorrosion performance of a coating in an anticorrosive coating. The small-size graphene can be filled into the holes of the coating, and meanwhile, the two-dimensional lamellar structure is stacked in the coating layer by layer to form a compact physical isolation layer. The hydrophobicity prevents and lightens the action that water molecules penetrate through the coating to reach the metal surface to corrode, so that the probability and degree of corrosion are reduced, and meanwhile, the coating has rigidity and toughness, has excellent performance as engineering plastics, particularly gas transmittance, oxygen is 1/40 of PE, and the water vapor transmittance is the same as that of PVC. The phenoxy resin has excellent performances of weather resistance, biodegradation resistance, inorganic acid resistance, alkali resistance, alcohol resistance, salt mist resistance, cold water resistance and aliphatic hydrocarbon resistance. The phenoxy resin swells in aromatic hydrocarbon and ketone solvents. The heat stability is good, and the cold flow resistance and the creep resistance are good even at 80 ℃ with the use temperature of-62-82 ℃. The oil-resistant static-conducting anticorrosive coating added with the modified graphene has proper static-conducting performance, excellent oil resistance and good corrosion resistance, and avoids the hidden danger of explosion and combustion if static hazard is not eliminated in time.
Drawings
FIG. 1 is a graph of open circuit potential (Eocp) versus time (t) at 20 ℃ in a sodium chloride solution with a mass fraction of 3.5% using an electrochemical workstation (Chenghua CHI 660C) coated with a strip of 10mm × 50mm coated with comparative examples 1-2 and examples 1-2, and a platinum sheet as a counter electrode to form a three-electrode electrolytic cell, wherein 1 is comparative example 1, 2 is comparative example 2, 3 is examples 1, 4 is example 2, 5 is example 2, and 6 is example 2, and the open circuit potential (Eocp) is measured at 20 ℃; FIG. 2 is a Tafel plot of a sodium chloride solution with a mass fraction of 3.5% for a three-electrode cell coated with a 10mm x 50mm Q-235 carbon steel sheet with a thickness of 2mm as a working electrode and a platinum sheet as a counter electrode in comparative examples 1-2 and examples 1-2, wherein 7 is comparative example 1, 8 is comparative example 2, 9 is example 1, 10 is example 2, 11 is example 2 for 10 days of immersion, and 12 is example 2 for 20 days of immersion; .
Detailed Description
The invention is illustrated by the following specific examples, which are not intended to be limiting.
Example 1
Firstly, according to parts by weight, phenoxy resin 48, trioctyl trimellitate 16, epoxidized soybean oil 6, stearoylbenzoylmethane 1 and OP-10 surfactant 2 are selected, wherein Gabriel PKHH is selected as the phenoxy resin, and the solvent: 73 parts of mixed solvent of methyl ethyl ketone and glycol ether in a volume ratio of 1: 1, wherein the drying temperature of the phenoxy resin is 90 ℃, and the drying time is 24 hours. The extruder is provided with a screw with the diameter of 40mm, a gradual compression type, the compression ratio of 3:1, the rotating speed of 20rpm, the length-diameter ratio of 18:1, the number of die holes of 2, furnace wire heating, pressure regulator temperature regulation, a feeding port and water cooling, a filter plate and a filter screen are arranged on a machine head, the machine head at the front section of the middle section of the material section is provided with 110 ℃, 190 ℃, 220 ℃ and 200 ℃, and the water cooling of a feeding area is carried out. The ingredients are respectively weighed according to the prescription, and the phenoxy resin and other raw materials are fully mixed. And (4) granulation, namely adopting a strand extrusion and granulation method. The solvent was added to a stirred tank equipped with a jacket heating device, and then the pellets were added with stirring while the temperature was raised to maintain the temperature at 60 ℃. The rotating speed of the stirrer is 300 revolutions per minute, the mixture can be completely dissolved within 5 hours and then filtered by a copper wire sieve of 100 meshes to remove impurities and coarse materials, and the phenoxy resin slurry is obtained. Preparing phenoxy resin emulsion: the phenoxy resin emulsion is prepared by emulsifying and mixing 7% of water-soluble organic silicon, 0.2% of defoaming agent, 45% of phenoxy resin slurry and the balance of water, wherein the sum of the components is one hundred percent; the specific emulsification and mixing method comprises the following steps: adding sodium methyl silanol water solution with the pH value of 13 and the solid content of 29 percent, a defoaming agent FoamasterMO2157 and water into an emulsifier, stirring, adding the preheated phenoxy resin slurry in a fine line shape, and fully stirring to obtain phenoxy resin emulsion; secondly, preparing a crosslinking solution: uniformly mixing 0.2 part of sodium fluosilicate, 2 parts of cross-linking agent, 14 parts of modified graphene and 84 parts of water in parts by weight, heating to 65 ℃, uniformly stirring and dispersing for 20min to obtain a cross-linking solution; mixing the coating before use: and (3) uniformly mixing the phenoxy resin emulsion and the crosslinking liquid obtained in the step one according to the mass ratio of 7: 1.5 to obtain the oil-resistant static-conducting anticorrosive coating added with the modified graphene. The water-soluble organic silicon is. The step two cross-linking agent is a mixture of Anquamine670, Anquamine156 and Anquamine419 according to the mass ratio of 1: 1. The modified graphene is amino-modified fluorinated graphene oxide, 2 parts of graphene oxide (Nanjing pioneer nano XF 002-1) are weighed and added into 100 parts of dichloromethane according to parts by weight, and the mixture is placed in an ultrasonic oscillation cleaner for ultrasonic treatment for 30min to obtain a uniform graphene oxide dispersion liquid. Adding the dispersion into a hydrothermal kettle with a polytetrafluoroethylene lining, adding 3.5 parts of diethylaminosulfur trifluoride, screwing the hydrothermal kettle tightly to seal the hydrothermal kettle, then placing the hydrothermal kettle into an oven, preserving heat for 24 hours at 120 ℃, and naturally cooling the hydrothermal kettle to room temperature after the reaction is finished. The reaction solution was filtered, and the filter cake was washed with ultrapure water several times until the pH value reached neutrality. And drying the obtained solid product to obtain fluorinated graphene oxide, dissolving 100mg of fluorinated graphene oxide in 100mL of deionized water, performing ultrasonic treatment for 30min to form a uniform dispersion liquid, adding dilute hydrochloric acid to adjust the pH value to 2, stirring at room temperature, slowly dropwise adding 0.5g of ethanolamine, reacting for 24h to obtain a pasty product, namely, a modified graphene oxide, washing the modified graphene oxide to be neutral by using absolute ethyl alcohol and deionized water, and finally drying in a vacuum drying oven at 60 ℃ for 48h, wherein the sheet diameter size is 0.5-5 mu m, the sheet thickness is 0.8-1.2nm, the F/C is 0.47, and secondary amine groups are modified. The use method of the oil-resistant static-conducting anticorrosive coating added with the modified graphene comprises the following steps: (1) pretreatment: carrying out acid washing, grinding and polishing treatment on a metal base material, and then washing and drying the metal base material to ensure that the surface of the metal base material is clean and rough; (2) spraying the paint: preheating the treated metal substrate to 35 ℃, and spraying the oil-resistant static-conductive anticorrosive paint of the modified graphene on the metal substrate; (3) and (3) thermal radiation curing: subjecting the sprayed metal base material to DP-KQD1100W medium wave infrared lamp with lamp distance of 48cm, cross-linking treatment at 99 deg.C for 30min, and cooling.
Example 2
Phenoxy resin slurry and fluorinated graphene oxide were the same as in example 1. Firstly, preparing phenoxy resin emulsion: the phenoxy resin emulsion is prepared by emulsifying and mixing 9% of water-soluble organic silicon, 0.5% of defoaming agent, 50% of phenoxy resin slurry and the balance of water, wherein the sum of the components is one hundred percent; the specific emulsification and mixing method comprises the following steps: adding water-soluble organic silicon, a defoaming agent and water into an emulsifier, stirring, adding the preheated phenoxy resin slurry in a fine line shape, and fully stirring to obtain phenoxy resin emulsion; secondly, preparing a crosslinking solution: uniformly mixing 0.2 part of sodium fluosilicate, 2 parts of cross-linking agent, 14 parts of modified graphene and 84 parts of water in parts by weight, heating to 65 ℃, uniformly stirring and dispersing for 20min to obtain a cross-linking solution; then, mixing before using the coating: and (3) uniformly mixing the phenoxy resin emulsion and the crosslinking solution obtained in the step one according to the mass ratio of 6: 1.3 to obtain the oil-resistant static-conducting anticorrosive coating added with the modified graphene. The water-soluble organosilicon is a sodium methyl silanol aqueous solution, the pH value of the water-soluble organosilicon is 12, and the solid content of the water-soluble organosilicon is 27%. The step two crosslinking agent is a mixture of Epilink701 and 2-sulfoterephthalic acid anhydride according to the mass ratio of 1: 1. The use method of the oil-resistant static-conducting anticorrosive coating added with the modified graphene comprises the following steps: (1) pretreatment: carrying out acid washing, grinding and polishing treatment on a metal base material, and then washing and drying the metal base material to ensure that the surface of the metal base material is clean and rough; (2) spraying the paint: preheating the treated metal substrate to 40 ℃, and spraying the oil-resistant static-conductive anticorrosive paint of the modified graphene on the metal substrate; (3) and (3) thermal radiation curing: and (3) subjecting the sprayed metal base material to DP-KQD1100W medium wave infrared baking treatment with a lamp distance of 40cm for 50min, and cooling.
Comparative example 1
The present comparative example is an uncoated 235 steel surface, a blank control.
Comparative example 2
Compared with example 1, in the comparative example, the method of example 1 is adopted, and the modified graphene in the step (2) is omitted, except that the steps of the method are the same.
The application performance of the anticorrosive coatings of examples 1-2 and comparative example 2 was tested, and the test results are shown in table 1:
TABLE 1 results of performance test on application properties of anticorrosive coatings of examples 1-2 and comparative example 2
Item Example 1 Example 2 Comparative example 2
In the container state Uniform viscous liquid, no hard block after stirring and mixing Uniform viscous liquid, no hard block after stirring and mixing Uniform viscous liquid, no hard block after stirring and mixing
Adhesion force 1 1 1
Flexibility (mm) 2 2 1
NaOH with the mass fraction of 5 percent at 25 DEG C 2000h without change 2000h without change 1500h without change
Sulfuric acid with a mass fraction of 5% at 25 DEG C 2000h without change 2000h without change 1500h without change
1000h salt spray resistant 15% NaCl Grade 1, no red rust of coating Grade 1, no red rust of coating Grade 1, coating with slight red rust
Adhesion (lattice drawing method) Without change Without change Without change
Impact resistance/cm 42 43 40
Surface resistivity omega 3.2×108 4.9×108 5.7×1012
Resisting 120# solvent oil 50 DEG C 792h intact paint film 792h intact paint film Micro-wrinkling and micro-cracking for 480h
Resisting 95# gasoline at 50 DEG C 792h intact paint film 792h intact paint film 480h micro-foaming and micro-peeling
Diesel oil resistance 50 deg.C 792h intact paint film 792h intact paint film 480h wrinkling, cracking
Aviation oil resistance 50 DEG C 792h intact paint film 792h intact paint film Micro rusting and micro bubbling for 480h
Note: the test was carried out with reference to the following standards, sampling being carried out according to GB/T3186-2006 raw material sampling regulations for paints, varnishes and paints and varnishes; the test conditions are carried out according to the regulation of the state of the paint sample and the temperature and humidity regulation of the test of GB/T9278-2008; sample preparation is carried out according to the GB/T9271-2008 regulation; the state in the container was visually observed. The flexibility is determined according to the GB/T1731-2020 paint film and putty film flexibility determination method; the adhesive force (grid cutting method) is carried out according to the specification of a GB/T9286-2021 colored paint and varnish grid cutting test; the impact resistance is determined according to the GB/T1732-2020 paint film impact resistance determination method; the surface resistivity is determined according to the GB/T16972-1997 petroleum tank static conductive coating resistivity determination method; the oil resistance is determined according to the HG/T3343-1985 paint film oil resistance determination method; the salt spray resistance is determined according to the specification of GB/T1771-2007 color paint and varnish for neutral salt spray resistance. The reference electrode was a saturated calomel electrode, platinum was a counter electrode, the reference electrode was coated with the strips of comparative examples 1 to 2 and examples 1 to 2 cut into strips of 10mm × 50mm, a 2mm thick sheet of Q-235 carbon steel was used as the working electrode, and a platinum sheet was used as the counter electrode to form a three-electrode electrolytic cell, which was subjected to an open circuit potential (E) at 20 ℃ in a sodium chloride solution of 3.5% by mass fraction using an electrochemical workstation (Chenhua CHI 660C)ocp) Time (t) curve and Tafel diagram (potentiodynamic scanning mode, scanning speed 1 mV/s) to measure the corrosion protection properties of the coating. The control test area is the same in the test process and is 1cm2And (3) polishing by using water-milled sand paper, removing oil by using absolute ethyl alcohol, cleaning, coating, standing for 24 hours, and testing.
The Tafel curve electrochemical parameters in a sodium chloride solution with a mass fraction of 3.5% for a three-electrode electrolytic cell, in which 10mm X50 mm Q-235 carbon steel sheets with a thickness of 2mm as working electrodes and platinum sheets as counter electrodes were coated in comparative examples 1-2 and examples 1-2, are shown in Table 1
TABLE 1 coating Tafel Curve electrochemical parameters in comparative examples 1-2 and examples 1-2 test pieces 3.5wt% NaCl solution
Item Ecorr(V) icorr(A/cm2) bc(V/dec) ba(V/dec)
Comparative example 1 −0.593 2.327×10-6 10.226 11.405
Comparative example 2 −0.428 7.156×10-7 3.543 5.887
Example 1 −0.152 7.715×10-9 5.122 4.849
Example 2 −0.111 6.138×10-9 7.366 4.051
Example 2(10day) −0.441 1.938×10-7 2.886 7.613
Example 2(20day) −0.452 1.257×10-6 4.408 8.272
In summary, referring to the drawings and specific performance data, it can be shown that fluorinated graphene oxide in the coating of the present invention can reduce the diffusion of corrosive electrolyte on the metal surface to provide better barrier performance, and the oil-resistant static-conductive anticorrosive coating added with modified graphene has suitable static-conductive performance, excellent oil resistance and good corrosion resistance, and can avoid the static hazard from being eliminated in time and easily generating the hidden danger of explosion combustion.

Claims (6)

1. A preparation method of an oil-resistant static-conducting anticorrosive coating added with modified graphene is characterized by comprising the following steps:
firstly, preparing phenoxy resin emulsion: the phenoxy resin emulsion is prepared by emulsifying and mixing 7-9% of water-soluble organic silicon, 0.2-0.5% of defoaming agent, 45-50% of phenoxy resin slurry and the balance of water, wherein the sum of the components is one hundred percent; the specific emulsification and mixing method comprises the following steps: adding water-soluble organic silicon, a defoaming agent and water into an emulsifier, stirring, adding the preheated phenoxy resin slurry in a fine line shape, and fully stirring to obtain phenoxy resin emulsion; secondly, preparing a crosslinking solution: uniformly mixing 0.1-0.2 part of sodium fluosilicate, 1-2 parts of a cross-linking agent, 12-14 parts of modified graphene and 78-84 parts of water in parts by weight, heating to 60-65 ℃, uniformly stirring and dispersing for 10-20 min to obtain a cross-linking solution; mixing the coating before use: uniformly mixing the phenoxy resin emulsion and the crosslinking liquid obtained in the step one according to the mass ratio of 6-7: 1.3-1.5 to obtain the oil-resistant static-conducting anticorrosive coating added with the modified graphene.
2. The preparation method of the oil-resistant static-conductive anticorrosive coating added with the modified graphene according to claim 1, wherein the water-soluble organosilicon is a sodium methyl siliconate aqueous solution, the pH value of the water-soluble organosilicon is 12-13, and the solid content of the water-soluble organosilicon is 27-29%.
3. The preparation method of the oil-resistant, static-conductive and anticorrosive coating with high temperature resistance and added modified graphene according to claim 1, wherein the crosslinking agent in the second step is one of Epilink701, Anquamine670, Anquamine156, Anquamine419 and 2-sulfoterephthalic acid anhydride.
4. The preparation method of the oil-resistant static-conductive anticorrosive coating added with the modified graphene according to claim 1, wherein the modified graphene is fluorinated graphene oxide, the fluorinated graphene oxide is fluorinated graphene oxide modified by a functional group containing fluorine atoms, preferably, the fluorinated graphene oxide has a sheet diameter of 0.5-5 μm and a sheet thickness of 0.8-1.2 nm; preferably, the fluorinated graphene oxide F/C is 0.47; preferably, the fluorinated graphene oxide sheet layer is modified with a secondary amine group.
5. The preparation method of the oil-resistant static-conductive anticorrosive paint added with the modified graphene according to claim 1, wherein the defoaming agent is one of FoamasterMO2157 and FoamaStarST 2410.
6. The preparation method of the oil-resistant static-conductive anticorrosive paint added with the modified graphene in claim 1 is characterized in that the mixed using method comprises the following steps:
(1) pretreatment: carrying out acid washing, grinding and polishing treatment on a metal base material, and then washing and drying the metal base material to ensure that the surface of the metal base material is clean and rough; (2) spraying the paint: preheating the treated metal substrate to 35-40 ℃, and spraying the oil-resistant static-conducting anticorrosive paint of the modified graphene on the metal substrate; (3) and (3) thermal radiation curing: and (3) placing the sprayed metal base material in an infrared baking lamp, carrying out heat radiation crosslinking treatment for 30-50 min at a lamp distance of 40-48 cm, and cooling.
CN202111324725.2A 2021-11-10 2021-11-10 Preparation method of oil-resistant static-conductive anticorrosive paint added with modified graphene Pending CN113881327A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180061518A1 (en) * 2016-08-30 2018-03-01 The Boeing Company Electrically conductive materials
CN111635657A (en) * 2020-05-11 2020-09-08 兰州星河石化防腐有限公司 Titanium-based polymer alloy welding seam protection coating functional material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180061518A1 (en) * 2016-08-30 2018-03-01 The Boeing Company Electrically conductive materials
CN111635657A (en) * 2020-05-11 2020-09-08 兰州星河石化防腐有限公司 Titanium-based polymer alloy welding seam protection coating functional material and preparation method thereof

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