CN115960511A - Graphene-containing heavy-duty anticorrosive coating and preparation method and application thereof - Google Patents
Graphene-containing heavy-duty anticorrosive coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heavy-duty anticorrosive paint containing graphene and a preparation method and application thereof. The heavy anti-corrosion coating containing graphene comprises a component A and a component B; the component A comprises 1-6 parts of graphene, 10-50 parts of epoxy resin, 0.5-3 parts of hydroxy triazine, 0.5-3 parts of glycidyl ether silane, 10-25 parts of first solvent and 30-65 parts of filler in parts by weight; the component B comprises 38-80 parts of a second solvent, 19-60 parts of a curing agent and 0.5-2 parts of aminophenol by weight. The graphene-containing heavy-duty anticorrosive paint provided by the invention has the characteristics of good acid/alkali corrosion resistance, strong hydrogen sulfide corrosion resistance, high adhesion, good ultraviolet aging resistance, strong salt mist/humidity resistance and the like, and can meet the corrosion resistance of various metal substrates.
Description
Technical Field
The invention relates to the field of corrosion prevention, and particularly relates to a heavy-duty anticorrosive coating containing graphene as well as a preparation method and application thereof.
Background
The heavy anti-corrosion coating is used as a coating which can provide long-acting protection for a metal substrate in a severe corrosion environment, and is widely applied to engineering equipment and facilities which are in contact with corrosive media such as seawater, high-sulfur-content crude oil, acid/alkali liquid and the like. The economic loss caused by metal corrosion reaches thousands of billions of dollars every year around the world, and the development of heavy anticorrosive coatings, especially anticorrosive coatings which are resistant to corrosion of special chemicals such as acid, alkali and hydrogen sulfide, has great significance for the rapid development of national economy and industry.
At present, commercially available heavy-duty anticorrosive paint systems mainly comprise epoxy resin systems, acrylic acid systems, polyurethane systems, fluorocarbon systems, organosilicon systems, chlorinated rubber systems and the like, and play irreplaceable roles in railways, highway bridges, automobiles, metallurgical industries and the like. However, with the continuous development of industrial technology, the market demand for heavy-duty anticorrosive coatings is continuously upgraded, and high adhesion, chemical corrosion resistance, low film thickness and environmental protection (without zinc and lead) become the future development trend of heavy-duty anticorrosive coatings.
Graphene as a host sp 2 The carbon material with a single-layer two-dimensional honeycomb lattice structure formed by connecting hybridized carbon atoms has extremely strong impermeability, can effectively block the contact of oxygen and water molecules when being used as an additive in the anticorrosive paint, and improves the anticorrosive performance of the paint. CN103897556B discloses a zinc-containing graphene anticorrosive paint, which utilizes the synergistic effect of a small amount of graphene (less than 2%) and a small amount of zinc powder (less than 30%) to improve the comprehensive performance of the paint, but the product has the adhesion, salt spray resistance and ultraviolet light aging resistanceThere is a need for improvement and no chemical resistance is reported.
CN106189719B discloses a graphene anticorrosive paint, wherein the component A adopts 1-3% of graphene, 10-20% of zinc powder and 1-5% of aluminum paste to improve the anticorrosive performance of the paint, and the component B adopts 30-50% of cashew nut shell oil phenolic amide and 10-30% of polyamide as curing agents. However, the graphene anticorrosive paint is added with zinc powder and aluminum paste, so that the cost is high, certain environmental pollution risks exist, a large amount of non-renewable resources are consumed, and the weather resistance of the resin is partially reduced.
Therefore, the development of the graphene heavy-duty anticorrosive coating which is resistant to acid/alkali corrosion, resistant to hydrogen sulfide corrosion, high in adhesive force (more than or equal to 10 MPa), excellent in ageing resistance and free of heavy metal belongs to the technical problem in the field.
Disclosure of Invention
The invention aims to solve the problems that a graphene heavy-duty anticorrosive coating in the prior art is not resistant to hydrogen sulfide corrosion, poor in acid/alkali resistance, low in adhesive force, poor in ageing resistance and the like, and provides a heavy-duty graphene-containing heavy-duty anticorrosive coating which is excellent in comprehensive performance and does not contain heavy metal, and a preparation method and application thereof. The heavy-duty anticorrosive coating containing graphene has the characteristics of strong hydrogen sulfide corrosion resistance, good acid/alkali resistance, strong salt spray/damp-heat resistance, strong adhesive force, good ageing resistance and the like.
The invention provides a heavy-duty anticorrosive paint containing graphene, wherein the heavy-duty anticorrosive paint containing graphene comprises a component A and a component B; the component A comprises 1-6 parts of graphene, 10-50 parts of epoxy resin, 0.5-3 parts of hydroxy triazine, 0.5-3 parts of glycidyl ether silane, 10-25 parts of first solvent and 30-65 parts of filler in parts by weight; the component B comprises 38-80 parts of a second solvent, 19-60 parts of a curing agent and 0.5-2 parts of aminophenol by weight.
Further, in the heavy anti-corrosive paint containing graphene, the mass ratio of the component A to the component B is 10:1-4:1.
further, preferably, in the graphene-containing heavy duty anticorrosive coating, the component a comprises, by weight, 1 to 3 parts of graphene, 12 to 35 parts of epoxy resin, 0.5 to 2 parts of hydroxy triazine, 0.5 to 2 parts of glycidyl ether silane, 10 to 25 parts of first solvent, and 33 to 65 parts of filler.
Further, preferably, in the graphene-containing heavy duty anticorrosive coating, the component B comprises 38 to 77 parts by weight of the second solvent, 22 to 60 parts by weight of the curing agent, and 0.5 to 2 parts by weight of aminophenol.
Further, in the heavy-duty anticorrosive coating containing graphene, the graphene in the component a is few-layer graphene (generally, graphene with less than five layers), and the median particle size of the graphene is 5 μm to 15 μm.
Further, in the graphene-containing heavy anti-corrosive paint, the epoxy value of the epoxy resin is 0.2-0.6, and preferably, two or three epoxy resins with different epoxy values are adopted as the epoxy resin.
Further, in the heavy duty anticorrosive coating containing graphene, the glycidyl ether silane is selected from at least one of glycidyl ether oxypropyltriethoxysilane, glycidyl ether oxypropyltrimethoxysilane and glycidyl ether oxypropylmethyldimethoxysilane.
Further, in the graphene-containing heavy anti-corrosive paint, the filler in the component A is selected from one or more of titanium dioxide, barium sulfate, zinc oxide, bentonite, aluminium dihydrogen tripolyphosphate, talcum powder, carbon black, mica powder and calcium carbonate. The first solvent in the component A is selected from one or more of toluene, xylene, N-butyl acetate, propylene glycol methyl ether acetate, butanone, methyl isobutyl ketone, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol methyl ether, diethylene glycol ethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, ethyl acetate and N-methyl pyrrolidone, preferably at least 2 solvents are adopted for compound use, and more preferably at least 3 solvents are adopted for compound use.
Further, in the heavy-duty anticorrosive coating containing graphene, the component a may further include an auxiliary agent, and the auxiliary agent is one or more selected from a leveling agent, a defoaming agent, a dispersing agent, a dehydrating agent, and the like. The component A contains 0.5-5 parts of auxiliary agent by weight. The auxiliary agent can be selected from leveling agents, antifoaming agents, dispersing agents, dehydrating agents and the like which are commonly used in the field.
Further, in the graphene-containing heavy anti-corrosion coating, the curing agent in the component B is selected from one or more of phenolic aldehyde amine, phenolic aldehyde amide and polyamide, preferably one or more of cashew nut shell oil phenolic aldehyde amine, cashew nut shell oil phenolic aldehyde amide and polyamide, preferably, the hydrogen equivalent of the curing agent is 100-300, the viscosity (25 ℃) is 500cps-3000cps, such as NX-6654, LITE 3060, NT-1545, NX-5110 and NX-5445.
Further, in the graphene-containing heavy-duty anticorrosive paint, the aminophenol in the component B is at least one selected from 2-aminophenol, bis [ - (dimethylamino) -methyl ] phenol, and 2, 4, 6-tris (dimethylaminomethyl) phenol.
In the graphene-containing heavy duty anticorrosive coating, the second solvent in the component B is selected from one or more of toluene, xylene, N-butyl acetate, propylene glycol methyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol methyl ether, diethylene glycol ethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, ethyl acetate, and N-methylpyrrolidone, preferably at least 2 or more solvents are used in combination, and more preferably at least 3 or more solvents are used in combination. The second solvent may be the same as or different from the first solvent.
Furthermore, the adhesion force of the heavy anti-corrosive paint containing the graphene is more than or equal to 10MPa, and is preferably 12-16MPa.
Furthermore, the heavy anti-corrosion coating containing graphene does not contain fluorine.
Furthermore, the heavy-duty anticorrosive coating containing graphene does not contain metal zinc powder.
The second aspect of the invention provides a preparation method of the graphene-containing heavy-duty anticorrosive paint, which comprises the following steps:
(1) Mixing graphene, a filler, a first solvent and an optional auxiliary agent, and shearing at a high speed;
(2) Mixing epoxy resin with the mixture obtained in the step (1), and then grinding;
(3) Mixing the mixture obtained in the step (2) with glycidyl ether silane and hydroxy triazine, and shearing at a high speed to obtain a component A;
(4) Mixing a curing agent, aminophenol and a second solvent, and shearing at a high speed to obtain a component B;
(5) And mixing the component A and the component B to prepare the graphene-containing heavy anti-corrosion coating.
Further, the high-speed shearing conditions in the step (1) are as follows: the time is 30-40min, and the rotating speed is 1000-2000 rpm. The temperature is controlled to be 30-50 ℃ in the high-speed shearing process in the step (1).
Further, the grinding in the step (2) can adopt a sand mill, and the grinding is carried out until the fineness is less than or equal to 25 μm. Preferably, the grinding media of the sand mill are zirconium beads of 1.5mm to 3 mm.
Further, the high-speed shearing conditions in the step (3) are as follows: the time is 20min-30min, and the rotating speed is 800rpm-1300rpm.
Further, the high-speed shearing conditions in the step (4) are as follows: the time is 10min-20min, and the rotating speed is 800rpm-1200rpm.
The third aspect of the invention provides application of the graphene-containing heavy-duty anticorrosive paint in crude oil storage tanks, ships, offshore platforms and offshore wind power devices.
Further, the film thickness of the heavy anti-corrosive paint containing graphene is preferably 80-120 μm.
Compared with the prior art, the invention has the beneficial effects that:
1. the heavy-duty anticorrosive coating formula containing graphene is formed by utilizing the mutual matching of a plurality of components in the component A and the component B, has the characteristics of strong adhesive force, good acid/alkali corrosion resistance, strong hydrogen sulfide corrosion resistance, no zinc, tin, aluminum and other metal substances, strong neutral salt spray resistance, good ultraviolet light aging resistance, small neutral film thickness (80-120 mu m), good brushing performance (no bubbling and peeling), simple construction process (spraying and brushing), can meet the construction requirements of various metal base materials, and can provide comprehensive anticorrosive protection for the metal base materials.
2. The heavy-duty anticorrosive coating containing graphene provided by the invention has the advantages that the adhesive force can reach 13MPa, further can reach 15MPa, and the hydrogen sulfide resistance (5 percent of NaCl +5 percent) 3 COOH+H 2 S saturated solution) has a corrosion resistance of 850h, more preferably 1000h or more, and is acid resistant (5% H) 2 SO 4 ) And alkali (5 percent of NaOH) for more than 3600h, further more than 5000h, the ultraviolet aging resistant time can reach 800-1000 h, and the neutral salt spray resistance can reach 2600-3000 h.
3. In the heavy-duty anticorrosive coating containing graphene, due to the coordination of the added glycidyl ether silane and the hydroxy triazine, the graphene can be better dispersed in the coating, the shielding effect and the labyrinth effect of the graphene can be fully exerted, in addition, due to the coordination of the glycidyl ether silane and the hydroxy triazine, an anticorrosive coating with good comprehensive performance is formed on the surface of a base material by the coating, the ultraviolet aging resistance (weather resistance) of the anticorrosive coating is improved, and the service life of the base material used in high-temperature, high-humidity, high-salt, high-acid/alkali and other strong corrosive environments can be greatly prolonged.
Drawings
Fig. 1 is a schematic view of an anticorrosion mechanism of a conventional anticorrosion paint and a graphene-containing heavy anticorrosion paint of the present invention;
FIG. 2 is a photo of the graphene-containing heavy duty anticorrosive coating obtained in example 1 after a hydrogen sulfide corrosion test experiment;
fig. 3 is a photo of the graphene-containing heavy duty anticorrosive coating obtained in example 1 after a neutral salt spray experiment (3000 h).
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The hydrogen sulfide corrosion resistance test of the graphene-containing heavy-duty anticorrosive coating is carried out according to GB/T4157-2006, the salt spray test is carried out according to GB/T1771-2007, and the paint film adhesion test is carried out according to GB/T1720-1979. And cleaning treatment is carried out according to GB/T8923.1-2011 before the paint film is coated.
In the following examples and application examples, the room temperature is 25 ℃.
The anticorrosion mechanism of the conventional anticorrosive paint and the graphene-containing heavy anticorrosive paint of the present invention is briefly described below with reference to fig. 1. The circles in the left picture of fig. 1 represent zinc powder, and the traditional anticorrosive paint has the problems of large zinc powder consumption, low utilization rate, large film thickness, easy cracking, chemical corrosion resistance and the like according to the cathode protection principle of the zinc powder, and water, oxygen molecules and the like are easy to contact with a substrate through gaps among zinc powder particles to cause corrosion. The circles in the right diagram of fig. 1 represent solid fillers, and the short lines represent graphene, and the heavy anti-corrosive coating containing graphene of the present invention utilizes the coordination of the components, so as to sufficiently exert the shielding effect (atomic impermeability) and the labyrinth effect (prolonging the transmission path of corrosive media) of graphene, and greatly improve the comprehensive anti-corrosive performance of the coating.
Example 1
(1) Taking 2 parts of powder graphene (3 layers of graphene, the median particle size is 8 mu m), 0.5 part of defoaming agent (brand Deform 6500), 0.5 part of dispersing agent (brand Disponer 9850), 1 part of bentonite, 3 parts of titanium dioxide, 6 parts of talcum powder, 3 parts of aluminium dihydrogen tripolyphosphate, 17 parts of barium sulfate, 29 parts of calcium carbonate, 0.5 part of flatting agent (brand BYK-310), 22 parts of solvent (a mixed solvent of toluene, xylene, n-butyl acetate, propylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether, the volume ratio is 1: 0.5), sequentially adding the mixture into a high-speed shearing stirrer, adjusting the rotating speed to 1200rpm, shearing and dispersing for 30min, and controlling the shearing temperature to be 40 ℃ until all solids are uniformly dispersed and no layering occurs.
(2) And (2) adding 14 parts of bisphenol A type epoxy resin (with the epoxy value of 0.22) into the mixture obtained in the step (1), mechanically stirring, and then transferring into a sand mill, and grinding for 30min at the rotation speed of 700rpm, wherein the fineness is less than or equal to 25 mu m.
(3) And (3) adding 1 part of glycidyl ether silane (KH-560) and 0.5 part of hydroxy triazine into the mixture obtained in the step (2), and shearing and dispersing at the rotating speed of 1200rpm for 20min to obtain the component A of the graphene-containing heavy-duty anticorrosive coating.
(4) Taking 50 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent (NX-6654), 1 part of aminophenol (2-aminophenol) and 49 parts of solvent (mixed solvent of toluene, xylene, n-butyl acetate, propylene glycol monomethyl ether acetate and diethylene glycol monobutyl ether, wherein the volume ratio is 1: 0.5), and shearing and stirring at 1000rpm for 15min to obtain the graphene-containing heavy anticorrosive paint B component.
(5) Uniformly mixing the component A and the component B of the heavy-duty anticorrosive coating containing graphene according to the mass ratio of 5: 1 to obtain the heavy-duty anticorrosive coating containing graphene, namely spraying the heavy-duty anticorrosive coating on the pretreated carbon steel substrate by adopting a spraying mode (the spraying pressure is 0.3 MPa). The paint film in all the embodiments of the invention adopts a two-time spraying process, the two-time spraying interval is 2 hours, and the thickness of the paint film is 90 mu m.
The adhesive force of the heavy anti-corrosion coating containing graphene is 15MPa.
Fig. 2 is a photograph of a sample immersed in the hydrogen sulfide test solution of the graphene-containing heavy duty anticorrosive coating obtained in example 1. As can be seen from the figure, the surface of the substrate soaked for 1000 hours has no bubbling or peeling phenomenon. Fig. 3 is a real photograph of the heavy anti-corrosion coating containing graphene after neutral salt spray experiment, and it can be seen from the picture that after 3000 hours, only a scribing part has a corrosion trace, and the line is not expanded to two sides due to corrosion, so that the requirements of GB/T1771-2007 are met. After 1000 hours in the ultraviolet aging box, the phenomenon of yellowing and cracking begins to occur. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5 percent of NaOH, placing the substrate sprayed with the graphene heavy anti-corrosion coating prepared in example 1 into the solution, observing the surface paint film condition of the sample plate at intervals of 48 hours, and observing that the two substrates respectively have paint film bubbling phenomenon at 5880 hours and 5040 hours.
Example 2
(1) Taking 4 parts of powder graphene (3 layers of graphene, the median particle size of which is 8 microns), 0.5 part of defoaming agent (brand Deform 6500), 0.5 part of dispersing agent (brand Disponer 9850), 1 part of bentonite, 3 parts of titanium dioxide, 6 parts of talcum powder, 3 parts of aluminium dihydrogen tripolyphosphate, 4 parts of carbon black, 17 parts of barium sulfate, 27 parts of calcium carbonate, 0.5 part of flatting agent (brand BYK-310), and 22 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, n-butyl acetate, propylene glycol methyl ether and diethylene glycol monobutyl ether, the volume ratio of which is 1: 0.5), sequentially adding the mixture into a high-speed shearing stirrer, adjusting the rotating speed to 1200rpm, shearing and dispersing for 30min, and controlling the shearing temperature to be 40 ℃ until all solids are uniformly dispersed and no layering occurs.
(2) And (2) adding 10 parts of bisphenol A type epoxy resin (the epoxy value is 0.22) into the mixture obtained in the step (1), mechanically stirring, transferring into a sand mill, and grinding for 30min at the rotating speed of 700rpm, wherein the fineness is less than or equal to 25 microns.
(3) And (3) adding 1 part of glycidyl ether silane (KH-560) and 0.5 part of hydroxy triazine into the mixture obtained in the step (2), and shearing and dispersing for 20min at the rotating speed of 1200rpm to obtain the component A of the graphene-containing heavy anti-corrosion coating.
(4) Taking 50 parts of cashew nut shell oil modified phenolic amide curing agent (LITE 3060), 1 part of aminophenol (2, 4, 6-tri (dimethylaminomethyl) phenol) and 49 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, n-butyl acetate, propylene glycol methyl ether and diethylene glycol monobutyl ether, wherein the volume ratio is 1: 0.5), and shearing and stirring at 1000rpm for 15min to obtain the component B of the graphene-containing heavy anti-corrosion coating.
(5) Uniformly mixing the component A and the component B of the heavy-duty anticorrosive coating containing graphene according to the mass ratio of 5: 1 to obtain the heavy-duty anticorrosive coating containing graphene, namely spraying the heavy-duty anticorrosive coating on the pretreated carbon steel substrate by adopting a spraying mode (the spraying pressure is 0.3 MPa). The paint film in all the embodiments of the invention adopts a two-time spraying process, the two-time spraying interval is 2 hours, and the thickness of the paint film is 90 mu m.
The adhesion force of the heavy anti-corrosive paint containing the graphene is 12.5MPa.
The panels sprayed with the graphene-containing heavy duty coating from example 2 were then subjected to hydrogen sulfide corrosion testing and neutral salt spray testing as described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 700 hours. For carrying out neutral salt spray experimentsAfter 2472 hours, the expanding erosion distance of the template at the scribing position is more than or equal to 1.5mm, and the requirement of GB/T1771-2007 cannot be met. After 1000 hours in the ultraviolet aging box, the phenomenon of yellowing and cracking begins to occur. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5% of a test solution of NaOH, and the substrate sprayed with the graphene heavy anti-corrosive coating prepared in example 2 was placed in the above solution, and the paint film condition of the surface of the sample was observed every 48 hours, and the above two substrates were observed to show the paint film bubbling phenomenon at 2880 hours and 2160 hours, respectively.
Example 3
(1) Taking 2 parts of powder graphene (3 layers of graphene, the median particle size of which is 8 mu m), 0.5 part of defoaming agent (brand Deform 6500), 0.5 part of dispersing agent (brand Disponer 9850), 1 part of bentonite, 3 parts of titanium dioxide, 6 parts of talcum powder, 3 parts of aluminium dihydrogen tripolyphosphate, 17 parts of barium sulfate, 29 parts of calcium carbonate, 0.5 part of flatting agent (brand BYK-310), 22 parts of solvent (mixed solvent of toluene, methyl isobutyl ketone, ethylene glycol, ethyl acetate and diethylene glycol monobutyl ether, the volume ratio is 1: 0.5), sequentially adding the mixture into a high-speed shearing stirrer, adjusting the rotating speed to 1200rpm, shearing and dispersing for 30min, and controlling the shearing temperature to be 40 ℃ until all solids are uniformly dispersed and no layering occurs.
(2) And (2) adding 14 parts of bisphenol A type epoxy resin (with the epoxy value of 0.22) into the mixture obtained in the step (1), mechanically stirring, and then transferring into a sand mill, and grinding for 30min at the rotation speed of 700rpm, wherein the fineness is less than or equal to 25 mu m.
(3) And (3) adding 1 part of glycidyl ether silane (KH-560) and 0.5 part of hydroxy triazine into the mixture obtained in the step (2), and shearing and dispersing for 20min at the rotating speed of 1200rpm to obtain the component A of the graphene-containing heavy anti-corrosion coating.
(4) Taking 20 parts of polyamide curing agent (NT-1545), 0.5 part of aminophenol (2-aminophenol) and 79.5 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, ethylene glycol, ethyl acetate and diethylene glycol monobutyl ether, wherein the volume ratio is 1: 0.5), and shearing and stirring at 1000rpm for 15min to obtain the graphene-containing heavy-duty anticorrosive coating B component.
(5) The component A and the component B of the graphene-containing heavy anti-corrosion coating are uniformly mixed according to the mass ratio of 5: 1 to obtain the graphene-containing heavy anti-corrosion coating, and the graphene-containing heavy anti-corrosion coating can be sprayed on a pretreated carbon steel substrate by adopting a spraying mode (the spraying pressure is 0.3 MPa). The paint film in the embodiment adopts a two-time spraying process, the curing time is prolonged due to the adjustment of the proportion of the curing agent, the two-time spraying interval is adjusted to be 5 hours, and the thickness of the paint film is 90 mu m.
The adhesion force of the heavy anti-corrosion coating containing graphene is 10MPa.
The panels sprayed with the graphene-containing heavy duty coating from example 3 were then subjected to hydrogen sulfide corrosion testing and neutral salt spray testing as described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 300 hours. After 1200h, the extended erosion distance of the marking line is more than or equal to 1.5mm, and the requirement of GB/T1771-2007 cannot be met. After 1000 hours in the ultraviolet aging box, the phenomenon of yellowing and cracking begins to occur. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5 percent of NaOH, placing the substrate sprayed with the graphene heavy-duty anticorrosive coating prepared in example 3 into the solution, observing the surface paint film condition of the sample plate at intervals of 48 hours, and observing the two substrates to generate paint film bubbling at 1080h and 720h respectively.
Example 4
(1) Taking 2.5 parts of powder graphene (3 layers of graphene, the median particle size is 8 μm), 0.5 part of defoaming agent (brand Deform 6500), 0.5 part of dispersing agent (brand Disponer 9850), 1 part of bentonite, 2 parts of titanium dioxide, 3.1 parts of zinc oxide, 3 parts of aluminium dihydrogen tripolyphosphate, 9 parts of barium sulfate, 20 parts of mica powder, 0.5 part of flatting agent (brand BYK-310), 21.5 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, propylene glycol methyl ether, ethyl acetate and N-methyl pyrrolidone, the volume ratio of 1.
(2) And (2) adding 34 parts of bisphenol A type epoxy resin (containing 10 parts of epoxy resin with the epoxy value of 0.22 and 24 parts of epoxy resin with the epoxy value of 0.55) into the mixture obtained in the step (1), mechanically stirring, transferring into a sand mill, and grinding for 30min at the rotating speed of 700rpm, wherein the fineness is less than or equal to 25 mu m.
(3) And (3) adding 0.6 part of glycidyl ether silane (KH-561) and 1.8 parts of hydroxy triazine into the mixture obtained in the step (2), and shearing and dispersing at the rotating speed of 1000rpm for 30min to obtain the component A of the graphene-containing heavy-duty anticorrosive coating.
(4) Taking 23 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent (NX-5110), 0.5 part of aminophenol (2-aminophenol) and 76.5 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, propylene glycol methyl ether, ethyl acetate and N-methyl pyrrolidone, wherein the volume ratio is 1.
(5) Uniformly mixing the component A and the component B of the heavy anti-corrosion coating containing the graphene according to the mass ratio of 4. The paint film in the embodiment adopts a two-time spraying process, the curing time is prolonged due to the adjustment of the proportion of the curing agent, the two-time spraying interval is adjusted to be 5h, and the thickness of the paint film is 90 mu m.
The adhesion force of the heavy anti-corrosion coating containing graphene is 13MPa.
The panels sprayed with the graphene-containing heavy duty coating from example 4 were then subjected to hydrogen sulfide corrosion testing and neutral salt spray testing as described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 850 hours. After 2600 hours, the expanding erosion distance of the marking line of the sample plate for developing the neutral salt spray experiment is more than or equal to 1.5mm, and the requirement of GB/T1771-2007 cannot be met. After 1000 hours, the yellowing and cracking phenomena begin to occur in the ultraviolet aging box. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5% of a test solution of NaOH, and the substrate sprayed with the graphene heavy anti-corrosive coating prepared in example 4 was placed in the above solution, and the varnish appearance of the sample surface was observed every 48 hours, and the varnish bubbling phenomenon was observed in 4680h and 4080h for the above two substrates, respectively.
Example 5
(1) Taking 2.5 parts of powder graphene (3 layers of graphene, the median particle size of which is 8 microns), 0.5 part of a defoaming agent (brand Deform 6500), 0.5 part of a dispersing agent (brand Disponer 9850), 1 part of carbon black, 2 parts of titanium dioxide, 2.5 parts of talcum powder, 3 parts of aluminium dihydrogen tripolyphosphate, 9 parts of barium sulfate, 20 parts of calcium carbonate, 0.5 part of a flatting agent (brand BYK-310), 21.5 parts of a solvent (a mixed solvent of toluene, methyl isobutyl ketone, ethanol, ethyl acetate and N-methyl pyrrolidone, the volume ratio of 1.
(2) Adding 34 parts of bisphenol A type epoxy resin (containing 10 parts of epoxy resin with the epoxy value of 0.22, 20 parts of epoxy resin with the epoxy value of 0.55 and 4 parts of epoxy resin with the epoxy value of 0.4) into the mixture obtained in the step (1), mechanically stirring, transferring into a sand mill, grinding at the rotating speed of 900rpm for 30min, and grinding the mixture to obtain the product with the fineness of less than or equal to 25 microns.
(3) And (3) adding 2 parts of glycidyl ether silane (Z-6044) and 1 part of hydroxy triazine into the mixture obtained in the step (2), and shearing and dispersing for 30min at the rotating speed of 1200rpm to obtain the component A of the graphene-containing heavy anti-corrosion coating.
(4) Taking 58 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent (NX-5445), 2 parts of aminophenol (2-aminophenol) and 40 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, ethanol, ethyl acetate and N-methyl pyrrolidone, wherein the volume ratio is 1.
(5) Uniformly mixing the component A and the component B of the heavy anti-corrosion coating containing the graphene according to the mass ratio of 6. The paint film in the embodiment adopts a two-time spraying process, the curing time is prolonged due to the adjustment of the proportion of the curing agent, the two-time spraying interval is adjusted to be 5h, and the thickness of the paint film is 90 mu m.
The adhesive force of the heavy anti-corrosion coating containing graphene is 15MPa.
Then the mixture obtained in example 5 is sprayed withSamples of graphene heavy duty coatings were tested for hydrogen sulfide corrosion and neutral salt spray in the manner described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 950 hours. After 2880 hours, the expanding erosion distance of the marking line is more than or equal to 1.5mm, and the requirement of GB/T1771-2007 cannot be met. After 900 hours in the ultraviolet aging box, the phenomenon of yellowing and cracking begins to occur. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5 percent of NaOH, and a substrate sprayed with the graphene heavy anti-corrosion coating prepared in example 5 was placed in the solution, and the surface paint film condition of the sample plate was observed every 48 hours, and the two substrates were observed to have paint film bubbling phenomenon at 4800 hours and 4560 hours, respectively.
Example 6
(1) Taking 2.5 parts of powder graphene (3 layers of graphene, the median particle size is 8 microns), 0.5 part of a defoaming agent (brand Deform 6500), 0.5 part of a dispersing agent (brand Disponer 9850), 1 part of bentonite, 2 parts of titanium dioxide, 2.5 parts of talcum powder, 3 parts of aluminium dihydrogen tripolyphosphate, 9 parts of barium sulfate, 20 parts of calcium carbonate, 0.5 part of a flatting agent (brand BYK-310), 21.5 parts of a solvent (a mixed solvent of toluene, methyl isobutyl ketone, ethanol, diethylene glycol monobutyl ether and N-methyl pyrrolidone, the volume ratio of 1.
(2) And (2) adding 34 parts of bisphenol A type epoxy resin (with the epoxy value of 0.22) into the mixture obtained in the step (1), mechanically stirring, transferring into a sand mill, and grinding for 30min at the rotating speed of 700rpm, wherein the fineness is less than or equal to 25 microns.
(3) And (3) adding 2 parts of glycidyl ether silane (KH-560) and 1 part of hydroxy triazine into the mixture obtained in the step (2), and shearing and dispersing at the rotating speed of 1300rpm for 20min to obtain the component A of the graphene-containing heavy-duty anticorrosive coating.
(4) Taking 35 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent (NX-6654), 2 parts of aminophenol (di [ - (dimethylamino) -methyl ] phenol) and 63 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, ethanol, diethylene glycol monobutyl ether and N-methyl pyrrolidone, wherein the volume ratio is 1: 0.5), and shearing and stirring at 1000rpm for 15min to obtain the component B of the graphene-containing heavy anti-corrosion coating.
(5) The component A and the component B of the graphene-containing heavy anti-corrosion coating are uniformly mixed according to the mass ratio of 4:1 to obtain the graphene-containing heavy anti-corrosion coating, and the graphene-containing heavy anti-corrosion coating can be sprayed on a pretreated carbon steel substrate by adopting a spraying mode (the spraying pressure is 0.3 MPa). The paint film in the embodiment adopts a two-time spraying process, the curing time is prolonged due to the adjustment of the proportion of the curing agent, the two-time spraying interval is adjusted to be 5 hours, and the thickness of the paint film is 90 mu m.
The adhesion force of the heavy anti-corrosion coating containing graphene is 13MPa.
The panels sprayed with the graphene-containing heavy duty coating from example 6 were then subjected to hydrogen sulfide corrosion testing and neutral salt spray testing as described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 850 hours. After 2700 hours, the extended erosion distance of the marking line is more than or equal to 1.5mm, which can not meet the requirement of GB/T1771-2007. After 850h in the ultraviolet aging box, the phenomenon of yellowing and cracking begins to occur. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5 percent of NaOH, placing the substrate sprayed with the graphene heavy anti-corrosion coating prepared in example 6 into the solution, observing the surface paint film condition of the sample plate at intervals of 48 hours, and observing the paint film bubbling phenomenon of the two substrates respectively at 3840 hours and 3600 hours.
Example 7
(1) Taking 2.5 parts of powder graphene (3 layers of graphene, the median particle size is 8 microns), 0.5 part of defoaming agent (brand Deform 6500), 0.5 part of dispersing agent (brand Disponer 9850), 2 parts of bentonite, 6 parts of titanium dioxide, 3.1 parts of zinc oxide, 2 parts of aluminium dihydrogen tripolyphosphate, 5 parts of barium sulfate, 20 parts of calcium carbonate, 0.5 part of flatting agent (brand BYK-310), 21.5 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, propylene glycol methyl ether, ethyl acetate and N-methyl pyrrolidone, the volume ratio is 1: 0.5), sequentially adding the mixture into a high-speed shearing stirrer, adjusting the rotating speed to be 1500rpm, shearing and dispersing for 30min, and controlling the shearing temperature to be 40 ℃ until all solids are uniformly dispersed and no layering occurs.
(2) And (2) adding 34 parts of bisphenol A type epoxy resin (containing 10 parts of epoxy resin with the epoxy value of 0.22 and 24 parts of epoxy resin with the epoxy value of 0.55) into the mixture obtained in the step (1), mechanically stirring, and then transferring into a sand mill for grinding for 30min at the rotating speed of 700rpm, wherein the fineness is less than or equal to 25 mu m.
(3) And (3) adding 1.5 parts of glycidyl ether silane (KH-561) and 0.9 part of hydroxy triazine into the mixture obtained in the step (2), and shearing and dispersing for 30min at the rotating speed of 1000rpm to obtain the component A of the graphene-containing heavy-duty anticorrosive coating.
(4) 55 parts of cashew nut shell oil modified phenolic aldehyde amine curing agent (NX-5110), 0.5 part of aminophenol (2-aminophenol) and 44.5 parts of solvent (a mixed solvent of toluene, methyl isobutyl ketone, propylene glycol methyl ether, ethyl acetate and N-methyl pyrrolidone with the volume ratio of 1: 0.5) are sheared and stirred at 1000rpm for 15min to obtain the component B of the graphene-containing heavy anti-corrosion coating.
(5) The component A and the component B of the graphene-containing heavy anti-corrosion coating are uniformly mixed according to the mass ratio of 4:1 to obtain the graphene-containing heavy anti-corrosion coating, and the graphene-containing heavy anti-corrosion coating can be sprayed on a pretreated carbon steel substrate by adopting a spraying mode (the spraying pressure is 0.3 MPa). The paint film in the embodiment adopts a two-time spraying process, the curing time is prolonged due to the adjustment of the proportion of the curing agent, the two-time spraying interval is adjusted to be 5 hours, and the thickness of the paint film is 90 mu m.
The adhesive force of the heavy anti-corrosion coating containing graphene is 15MPa.
The panels sprayed with the graphene-containing heavy duty coating from example 7 were then subjected to hydrogen sulfide corrosion testing and neutral salt spray testing as described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 1000 hours. After 3240h, the extended erosion distance of the marking line of the sample plate for developing the neutral salt spray experiment is more than or equal to 1.5mm, and the requirement of GB/T1771-2007 cannot be met. After 1000 hours in the ultraviolet aging box, the phenomenon of yellowing and cracking begins to occur. Reference GB/T1763-1979 to configuration5％H 2 SO 4 And 5 percent of NaOH, and the substrate sprayed with the graphene heavy anti-corrosion coating prepared in example 7 was placed in the solution, and the surface paint film condition of the sample plate was observed at intervals of 48 hours, and the paint film bubbling phenomenon was observed at 6000 hours and 5280 hours for the two substrates, respectively.
Comparative example 1
Comparative example 2 differs from example 1 only in that no glycidyl ether silane (KH-560) was added.
The adhesion force of the heavy anti-corrosive paint containing graphene is 8MPa.
The panels sprayed with the graphene-containing heavy duty paint obtained in comparative example 1 were then subjected to a hydrogen sulfide corrosion test and a neutral salt spray test in the manner described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 800 hours. After 1500h, the extended erosion distance of the marking line of the sample plate for developing the neutral salt spray experiment is more than or equal to 1.5mm, and the requirement of GB/T1771-2007 cannot be met. After 1000 hours, the yellowing and cracking phenomena begin to occur in the ultraviolet aging box. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5 percent of NaOH, placing the substrate sprayed with the graphene heavy anti-corrosion coating prepared in the comparative example 1 into the solution, observing the surface paint film condition of the sample every 48 hours, and observing that the two substrates respectively have paint film bubbling phenomenon at 720 hours and 400 hours.
Comparative example 2
Comparative example 2 differs from example 1 only in that no hydroxytriazine is added.
The adhesion force of the heavy anti-corrosion coating containing graphene is 12.5MPa.
The panels coated with the heavy duty graphene-containing anti-corrosive coating obtained in comparative example 2 were then subjected to a hydrogen sulfide corrosion test and a neutral salt spray test in the manner described in example 1. After comparison, the sample plate of the heavy anti-corrosion coating containing the graphene, which is immersed in the hydrogen sulfide solution, begins to peel and bubble after 1000 hours. After 3000 hours, the extended erosion distance of the marking line of the sample plate for developing the neutral salt spray experiment is more than or equal to 1.5mm, and the requirement of GB/T1771-2007 cannot be met. Ultraviolet aging boxAfter 600h, yellowing and cracking begin to occur. Acid corrosion resistance 5% according to GB/T1763-1979 arrangement 2 SO 4 And 5 percent of NaOH, placing the substrate sprayed with the graphene heavy anti-corrosion coating prepared in the comparative example 2 into the solution, observing the surface paint film condition of the sample plate at intervals of 48 hours, and observing that the paint film bubbling phenomenon occurs on the two substrates after 3600 hours and 3120 hours respectively.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. The graphene-containing heavy-duty anticorrosive paint is characterized by comprising a component A and a component B; the component A comprises 1-6 parts of graphene, 10-50 parts of epoxy resin, 0.5-3 parts of hydroxy triazine, 0.5-3 parts of glycidyl ether silane, 10-25 parts of first solvent and 30-65 parts of filler in parts by weight; the component B comprises 38-80 parts of a second solvent, 19-60 parts of a curing agent and 0.5-2 parts of aminophenol by weight.
2. The heavy-duty anticorrosive paint according to claim 1, wherein in the heavy-duty anticorrosive paint containing graphene, the mass ratio of the component a to the component B is 10:1 to 4:1.
3. The heavy-duty anticorrosive paint according to claim 1, wherein in the graphene-containing heavy-duty anticorrosive paint, the component a comprises, in parts by weight, 1 to 3 parts of graphene, 12 to 35 parts of an epoxy resin, 0.5 to 2 parts of a hydroxytriazine, 0.5 to 2 parts of a glycidyl ether silane, 10 to 25 parts of a first solvent, and 33 to 65 parts of a filler;
and/or in the heavy anti-corrosion coating containing graphene, the component B comprises 38-77 parts of a second solvent, 22-60 parts of a curing agent and 0.5-2 parts of aminophenol in parts by weight.
4. The heavy-duty anticorrosive paint according to any one of claims 1 to 3, wherein the graphene in the A component is few-layer graphene, and the median particle diameter of the graphene is 5 μm to 15 μm.
5. The heavy-duty coating composition as claimed in claim 1, wherein said glycidyl ether silane is at least one member selected from the group consisting of glycidyl ether oxypropyltriethoxysilane, glycidyl ether oxypropyltrimethoxysilane, and glycidyl ether oxypropylmethyldimethoxysilane.
6. The heavy-duty anticorrosive paint according to claim 1, wherein the epoxy value of the epoxy resin in the a component is 0.2 to 0.6;
and/or the filler in the component A is selected from one or more of titanium dioxide, zinc oxide, barium sulfate, bentonite, aluminium dihydrogen tripolyphosphate, talcum powder, carbon black, mica powder and calcium carbonate;
and/or the first solvent in the component A is selected from one or more of toluene, xylene, N-butyl acetate, propylene glycol methyl ether acetate, butanone, methyl isobutyl ketone, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol methyl ether, diethylene glycol ethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, ethyl acetate and N-methylpyrrolidone.
7. The heavy-duty anticorrosive paint according to claim 1, wherein the component a further comprises an auxiliary agent, wherein the auxiliary agent is one or more selected from a leveling agent, a defoaming agent, a dispersing agent and a dehydrating agent; the component A contains 0.5 to 5 parts of auxiliary agent by weight.
8. The heavy-duty anticorrosive paint according to claim 1, wherein the curing agent in the component B is selected from one or more of phenolic aldehyde amine, phenolic amide and polyamide, preferably from one or more of cashew nut shell oil phenolic aldehyde amine, cashew nut shell oil phenolic amide and polyamide; preferably, the curing agent has a hydrogen equivalent weight of 100 to 300 and a viscosity of 500cps to 3000cps at 25 ℃;
and/or, the aminophenol in the component B is selected from at least one of 2-aminophenol, bis [ - (dimethylamino) -methyl ] phenol, 2, 4, 6-tris (dimethylaminomethyl) phenol;
and/or the second solvent in the component B is selected from one or more of toluene, xylene, N-butyl acetate, propylene glycol methyl ether acetate, butanone, methyl isobutyl ketone, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol methyl ether, diethylene glycol ethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol butyl ether acetate, ethyl acetate and N-methylpyrrolidone.
9. The heavy-duty anticorrosive coating according to claim 1, wherein the adhesion of the heavy-duty anticorrosive coating containing graphene is not less than 10MPa, preferably 12-16MPa.
10. The heavy-duty anticorrosive paint according to claim 1, wherein the graphene-containing heavy-duty anticorrosive paint does not contain fluorine; and/or the heavy anti-corrosion coating containing graphene does not contain metal zinc powder.
11. The preparation method of the heavy anti-corrosive paint containing graphene as claimed in any one of claims 1 to 10, which comprises the following steps:
(1) Mixing graphene, a filler, a first solvent and an optional auxiliary agent, and shearing at a high speed;
(2) Mixing epoxy resin with the mixture obtained in the step (1), and then grinding;
(3) Mixing the mixture obtained in the step (2) with glycidyl ether silane and hydroxy triazine, and shearing at a high speed to obtain a component A;
(4) Mixing a curing agent, aminophenol and a second solvent, and shearing at a high speed to obtain a component B;
(5) And mixing the component A and the component B to prepare the graphene-containing heavy anti-corrosion coating.
12. The method of claim 11, wherein the high shear conditions of step (1) are as follows: the time is 30-40min, and the rotating speed is 1000-2000 rpm; controlling the temperature to be 30-50 ℃ in the high-speed shearing process in the step (1);
and/or, grinding the mixture in the step (2) by a sand mill until the fineness is less than or equal to 25 mu m;
and/or, the high-speed shearing condition in the step (3) is as follows: the time is 20min-30min, and the rotating speed is 800rpm-1300rpm;
and/or, the high-speed shearing condition in the step (4) is as follows: the time is 10min-20min, and the rotating speed is 800rpm-1200rpm.
13. Use of the graphene-containing heavy duty coating of any one of claims 1 to 10 in crude oil storage tanks, ships, offshore platforms, offshore wind plants.
14. The use according to claim 13, wherein the graphene-containing heavy duty coating has a film thickness of 80 μm to 120 μm.
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