CN110964403A - Paint film of static conductive anticorrosive paint, high-solid-content graphene static conductive anticorrosive paint and preparation method thereof - Google Patents
Paint film of static conductive anticorrosive paint, high-solid-content graphene static conductive anticorrosive paint and preparation method thereof Download PDFInfo
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Abstract
The invention provides a paint film of a static conductive anticorrosive paint, wherein graphene sheets are uniformly distributed in the paint film structure to form a graphene layer; the thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure. According to the invention, a paint film with a special structure is obtained, in the paint film, graphene sheets are uniformly distributed in the paint film structure to form a graphene layer; the thickness direction of the graphene layer is the same as or similar to that of the paint film structure, the shielding and blocking effects of the coating are effectively improved by utilizing the extremely high specific surface area, the extremely high ground-to-thickness ratio, the excellent conductive performance and the excellent blocking performance of the two-dimensional material of the graphene, the corrosion resistance of the coating is improved, and meanwhile, the static electricity conducting performance of the coating is greatly improved by the paint film structure, so that the paint film structure has a great application prospect in the field of corrosion-resistant static electricity conducting paint.
Description
Technical Field
The invention belongs to the technical field of static conductive anticorrosive coatings, and relates to a paint film of a static conductive anticorrosive coating, the static conductive anticorrosive coating and a preparation method thereof, in particular to the paint film of the static conductive anticorrosive coating, the high-solid-content graphene static conductive anticorrosive coating and the preparation method thereof.
Background
Static electricity is a static charge, and the generation of the static charge is inevitable in industrial production and has many hazards, which can be mainly attributed to two mechanisms, namely, the hazard caused by static discharge, such as causing the failure or malfunction of electronic equipment and causing electromagnetic interference; breakdown of integrated circuits and precision electronic components, or aging of components, lowering production yield; high-voltage electrostatic discharge causes electric shock, endangers personal safety, and is extremely easy to cause explosion, fire and the like in production places of various flammable and explosive articles or dust and oil mist. Another is the damage caused by electrostatic attraction, such as the electronics industry, the film and plastic industry, the paper and printing industry, the textile industry, and so on. As a result, various industries have long begun implementing various levels of antistatic measures and engineering.
The static conductive coating is one of common anti-static measures, and the static conductive coating takes epoxy resin with excellent oil resistance and corrosion resistance as a main film forming agent, and additives such as a modifier, a conductive pigment, a filler, a conductive additive, a solvent and the like are added, so that the static conductive coating has the functions of static conductivity and corrosion resistance. At present, the static conductive coating plays a very important role in the anticorrosion and antistatic protection of the inner and outer walls of oil storage tanks, oil pipelines, oil tank cars, oil tankers and other oil storage and transmission equipment in the industries of petroleum, chemical engineering, railways, traffic and the like, the anticorrosion and antistatic protection of gas tanks, water gates, underground pipelines and the like, and the anticorrosion and antistatic protection of equipment and facilities in the industries of coal mines, aviation, textiles, grains and the like.
However, as the petrochemical industry gradually becomes an indispensable part of national production and life, the problems of corrosion prevention and safety of the petroleum storage tank always trouble the chemical workers. The oil pipe and the oil tank are easy to generate electrostatic enrichment, when the discharge capacity of the enriched charges is larger than the minimum ignition energy of combustible materials, explosion is easy to occur, and great potential safety hazards also exist in the corrosion prevention problem of chemical equipment such as the oil tank. However, the metal powder is generally used as the static conductive medium in the current static conductive coating, but the color of the coating is not only limited by the color of the metal powder, but also the metal powder is easily oxidized to form oxide, thereby reducing the conductive performance of the paint film. In addition, there are a number of limitations. If metal powder with electrode potential higher than that of steel is used as a conductive medium, electrochemical corrosion can be formed when the metal powder is directly contacted with a base material, and the metal powder has a protection effect when the metal powder has lower potential; conductive carbon black and graphite powder are used as static conductive media, but the color of the conductive carbon black and graphite powder is limited, the conductive carbon black and graphite powder can only be made into dark colored paint, the electrode potential is higher, electrochemical corrosion can be formed, the oil absorption value is higher, and when the conductive performance requirement is higher, the addition amount is larger, the paint film performance can be reduced. In addition, the existing coating has high VOC content, is not environment-friendly and does not accord with the current strategic direction of green environment-friendly sustainable development.
Therefore, how to prepare an electrostatic conductive anticorrosive coating has better electrostatic conductive performance and anticorrosive performance, and can solve the above problems, which has become a problem to be solved by many application manufacturers and front-line research and development personnel.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a paint film of a static conductive anticorrosive paint, a static conductive anticorrosive paint and a preparation method thereof, and particularly to a high solid content graphene static conductive anticorrosive paint, in which graphene sheets can be uniformly and orderly distributed in a paint film structure to form a graphene layer with a specific barrier effect, and the graphene sheets in the graphene layer have a labyrinth structure and effect, so that the anticorrosive performance of an epoxy coating is greatly improved, and the static conductive performance of the coating can be greatly improved.
The invention provides a paint film of a static conductive anticorrosive paint, wherein graphene sheets are uniformly distributed in the paint film structure to form a graphene layer;
the thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure.
Preferably, viewed from the section of the paint film structure, along the thickness direction of the graphene layer, adjacent or similar graphene sheets in the graphene layer are distributed in a staggered manner;
viewed from the section of the paint film structure, a graphene layer with a labyrinth effect is formed between the graphene sheets along the thickness direction of the graphene layer;
the similarity is that the included angle between the thickness direction of the graphene layer and the thickness direction of the paint film structure is less than or equal to 60 degrees;
the thickness of the graphene sheet is 0.8-1.6 nm;
the number of the graphene sheets is 1-5;
the thickness of the paint film is 80-100 mu m.
The invention also provides a static conductive anticorrosive paint which comprises a component A and a component B;
the component A comprises the following components in percentage by mass:
the component B comprises a curing agent.
Preferably, the epoxy resin comprises bisphenol a type epoxy resin;
the mass ratio of the component A to the component B is (8-15): 1;
the curing agent comprises an epoxy curing agent;
the surfactant dispersant comprises a sulfonate surfactant and/or a Tween surfactant.
Preferably, the sulfonate surfactant comprises one or more of alkyl benzene sulfonate, α -olefin sulfonate, alkyl sulfonate, α -sulfo monocarboxylic acid ester, fatty acid sulfoalkyl ester, succinate sulfonate, alkyl naphthalene sulfonate, petroleum sulfonate, lignosulfonate, and alkyl glyceryl ether sulfonate;
the Tween surfactant comprises one or more of Tween-80, Tween-20, Tween-60 and Tween-40;
the filler comprises one or more of titanium dioxide, calcium carbonate, kaolin, montmorillonite, talcum powder, barium sulfate, mica powder, aluminum tripolyphosphate, zinc phosphate, modified zinc orthophosphate and superfine calcite powder;
the anti-settling agent comprises one or more of an anti-settling agent 3300, organic bentonite, organic clay, organic argil, fumed silica, wax slurry, polyethylene wax and cellulose ether;
the organic solvent comprises one or more of acetone, methyl isobutyl ketone, ethanol, isopropanol, butanone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate and butyl acetate;
the second dispersant comprises one or more of caprolactone polyol-polyethyleneimine segmented copolymer, acrylate high molecular dispersant, polyurethane dispersant, polyester dispersant and phosphate high molecular polymer;
the curing agent comprises one or more of polyamide, ethylenediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamine and polyether diamine.
The invention also provides a preparation method of the static conductive anticorrosive paint, which comprises the following steps:
1) dispersing graphene dry powder, an organic solvent, epoxy resin and a surfactant dispersant to obtain graphene resin dispersion liquid;
2) re-dispersing the graphene resin dispersion liquid and the second dispersing agent obtained in the previous step to obtain a mixed liquid;
3) and mixing and grinding the mixed solution, the filler and the anti-settling agent obtained in the step to obtain the component A of the static conductive anticorrosive paint.
Preferably, the dispersing comprises ultrasonic dispersing;
the dispersing time is 30-60 min;
the graphene dry powder is obtained by spray drying a graphene solution;
the mass concentration of the graphene solution is 0.1-6%;
the time of spray drying is 0.5-3 h;
the pressure of the spray drying is 0.6-5 MPa;
the temperature of the spray drying is 30-70 ℃;
the static conductive anticorrosive paint also comprises a component B.
Preferably, said redispersion comprises ultrasonic dispersion;
the re-dispersing time is 30-60 min;
the grinding time is 30-180 min;
the fineness of the ground slurry is 10-60 mu m;
the solid content of the static conductive anticorrosive paint is 88-98 percent;
the component A and the component B can be used after final mixing and uniform mixing.
Preferably, the step 1) is specifically:
1A) stirring and mixing graphene and an organic solvent to obtain a graphene mixed solution;
1B) stirring and mixing the graphene mixed solution obtained in the step and the surfactant dispersant again to obtain a graphene dispersion solution;
1C) and adding epoxy resin into the graphene dispersion liquid obtained in the step, stirring and mixing for the third time, and grinding to obtain the graphene epoxy resin dispersion liquid.
Preferably, the surfactant dispersant comprises a sulfonate surfactant and a tween surfactant;
the stirring and mixing time is 15-30 min;
the stirring and mixing speed is 300-600 r/min;
the time for stirring and mixing again is 15-40 min;
the speed of stirring and mixing again is 300-600 r/min;
the third stirring and mixing time is 20-60 min;
the third stirring and mixing speed is 400-1000 r/min;
the addition is slow;
the grinding time is 5-20 min;
the stirring and mixing comprises magnetic stirring and/or mechanical stirring;
the secondary stirring and mixing comprises magnetic stirring and/or mechanical stirring;
the third stirring and mixing comprises magnetic stirring and/or mechanical stirring;
the mass ratio of the graphene to the sulfonate surfactant is 1: (0.2 to 12);
the mass ratio of the graphene to the Tween surfactant is 1: (0.7 to 20);
the mass ratio of the graphene to the surfactant dispersant is 1: (1-30).
The invention provides a paint film of a static conductive anticorrosive paint, wherein graphene sheets are uniformly distributed in the paint film structure to form a graphene layer; the thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure. Compared with the prior art, the invention aims at the problems that the color of the existing static conductive anticorrosive paint is limited by the color of metal powder, the metal powder is easy to oxidize to form oxide, and further the electric conductivity of a paint film is reduced, the material selection is limited and the like, and the defect of high VOC content exists.
The invention selects the static electricity conducting anticorrosive material, takes the graphene as the static electricity conducting anticorrosive material, and aims at solving the problems that the existing graphene composite anticorrosive paint has the defects of obvious agglomeration and winding phenomena, unstable dispersion, uneven and disordered distribution in a paint film, poor anticorrosive performance, accelerated corrosion of a metal substrate, difficult achievement of an expected metal protection function and the like. Starting from an electrochemical mechanism, the self-assembly of the coating is realized after the coating is sprayed on a substrate by combining a physical shielding direction and through formula adjustment and preparation of the coating, a paint film with a special structure is creatively obtained, and graphene sheets in the paint film are uniformly distributed in the paint film structure to form a graphene layer; the thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure, the graphene layer formed by the graphene sheet is uniformly distributed between the upper surface and the lower surface of the paint film, the high specific surface area, the high ground-to-thickness ratio, the excellent conductivity and the excellent barrier property of a two-dimensional material of the graphene are utilized, the shielding barrier effect of the coating is effectively improved, the corrosion resistance of the coating is improved, meanwhile, the graphene layer with the labyrinth effect is formed between the graphene sheet and the graphene sheet along the thickness direction of the graphene layer from the section of the paint film structure, the static electricity conducting performance of the coating is greatly improved, and the graphene layer has a great application prospect in the field of corrosion-resistant static electricity conducting paint.
According to the high-solid-content environment-friendly novel coating for the heavy-duty anti-corrosion static conductive coating field, due to the fact that the ultrahigh diameter-thickness ratio of graphene and the special barrier effect of a two-dimensional material are utilized, and the sheet structure of the two-dimensional material of graphene forms a labyrinth effect through ordered arrangement, the shielding barrier effect of a coating is effectively improved, the anti-corrosion performance of an epoxy coating is improved, and the durability of the coating is prolonged; meanwhile, the ultrahigh conductivity of the graphene is utilized, and the specific labyrinth arrangement mode of graphene sheet layers is combined, so that the resistance of the coating is reduced, the static electricity conducting effect is achieved, and the static electricity conducting performance of the coating can be greatly improved with extremely small addition amount. The high-solid-content environment-friendly novel coating provided by the invention only needs to use few solvents, fundamentally reduces the main source of VOC in use, has extremely low VOC, meets the requirements of green environment-friendly coatings at present, and is an environment-friendly coating. And the preparation process is simple, strong in controllability and suitable for industrial mass production and popularization and application.
Experimental results show that the high-solid-content graphene anti-corrosion static-conducting coating is prepared in a relatively simple mode, and the graphene and resin compounding degreeThe graphene is distributed in a staggered labyrinth type layer by layer in the coating, the anti-corrosion performance and the electrostatic conduction performance of the coating are greatly improved, and the surface resistance of the coating can reach 108Omega, and the mass solid content can reach 93 percent.
Drawings
FIG. 1 is an SEM micrograph of a cross-section of a paint film prepared according to example 1 of the present invention;
FIG. 2 is a high magnification SEM micrograph of a cross section of a paint film prepared according to example 1 of the invention;
FIG. 3 is a high magnification SEM micrograph of a cross section of a paint film prepared according to example 1 of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably adopts the purity of analytical grade or the purity conventionally used in the field of resin coating.
All the raw materials of the invention have the same trade marks as the conventional trade marks in the field, each trade mark is clear and definite in the field of related application, and the raw materials can be purchased from the market by the technicians in the field according to the trade marks and the corresponding application.
The invention provides a paint film of a static conductive anticorrosive paint, wherein graphene sheets are uniformly distributed in the paint film structure to form a graphene layer;
the thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure.
The definition of the paint film is not particularly limited by the present invention, and the paint film produced by the anticorrosive paint known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the paint film of the present invention is a coating produced by the static electricity conducting anticorrosive paint, more preferably a coating produced by the static electricity conducting anticorrosive paint aiming at the corrosion prevention of the metal substrate, and more preferably a static electricity conducting anticorrosive coating obtained after the static electricity conducting anticorrosive paint is coated.
In the paint film structure, graphene sheets are flatly and uniformly distributed in the paint film structure to form a graphene layer. The parameters of the graphene layer are not particularly limited, and the parameters of the graphene layer known by a person skilled in the art can be used, and the person skilled in the art can select and adjust the parameters according to the actual application situation, the product requirement and the quality requirement, and in order to ensure the performance of the anticorrosive coating, the thickness of the graphene layer is preferably 80-100 μm, more preferably 82-98 μm, more preferably 85-95 μm, and more preferably 87-92 μm. In the invention, the graphene layers are uniformly distributed in the paint film from the upper surface of the paint film to the lower surface of the paint film, namely the thickness of the graphene layers is the same as or similar to that of the paint film.
In the present invention. The thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure, and more preferably the thickness direction of the graphene layer is the same as the thickness direction of the paint film structure. In the plane of the paint film, the plane close to the substrate is the lower surface, and the plane far away from the substrate is the upper surface, i.e. the plane of the graphene layer is basically the same as the plane of the paint film. In the present invention, the effect can also be achieved when the thickness direction of the graphene layer is similar to the thickness direction of the paint film structure, and to ensure the technical effect, specifically, the angle between the thickness direction of the graphene layer and the thickness direction of the paint film structure is less than or equal to 60 °, more preferably less than or equal to 50 °, more preferably less than or equal to 40 °, more preferably less than or equal to 30 °, more preferably less than or equal to 20 °, and more preferably less than or equal to 10 °.
The definition of the graphene layer in the present invention is not particularly limited, and may be a graphene layer known to those skilled in the art, and those skilled in the art can understand based on the basic general knowledge that, in the present invention, the graphene layer is not a layer containing only graphene, but is a graphene layer in which graphene is uniformly and intensively distributed, and the entire paint film is epoxy resin, so that the graphene layer is a mixed layer composed of graphene and a resin material, or a mixed layer composed of graphene, a resin and other materials. The graphene layer contains graphene sheets, and the microscopic two-dimensional lamellar structure of the graphene is combined with the graphene layer formed macroscopically, so that a better physical shielding effect is achieved, and the performance of the anticorrosive paint is improved.
In order to ensure that the graphene material has a physical shielding effect and also has better electrostatic conduction performance, adjacent or similar graphene sheets in the graphene layer are distributed in a staggered manner along the thickness direction of the graphene layer from the section of a paint film structure. The definition of the section of the paint film structure is not particularly limited by the present invention, and the positional relationship of the section of the conventional coating, which is well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and those skilled in the art can understand that the section, i.e., the section or the cross section in the thickness direction of the coating, of the coating is produced after the anticorrosive paint is sprayed on the substrate. Furthermore, in the paint film of the invention, when viewed from the section (section) of the paint film structure, graphene layers with labyrinth effect are formed between the graphene sheets (or the paint film) along the thickness direction of the graphene layers, namely, the graphene layers are distributed in a staggered way to form a labyrinth-like graphene layer.
The parameters of the graphene are not particularly limited, and the parameters of the graphene materials known by the skilled in the art can be selected and adjusted by the skilled in the art according to the actual application situation, the composite situation and the product performance, and in order to ensure the performance of the anticorrosive coating, the thickness of the graphene sheet is preferably 0.8-1.6 nm, more preferably 0.9-1.5 nm, more preferably 1.0-1.4 nm, and more preferably 1.1-1.3 nm. The graphene of the invention preferably comprises one or more of single-layer graphene, few-layer graphene, multi-layer graphene and reduced graphene oxide, and more preferably comprises single-layer grapheneGraphene, few-layer graphene, multi-layer graphene, or reduced graphene oxide. The number of graphene sheets is preferably 1 to 5, 2 to 4, 1 to 3, and the like, and specifically, the ratio of graphene sheets having 5 or less sheets is preferably 80% or more, more preferably 85% or more, and more preferably 90% or more. The sheet diameter of the graphene sheet layer is preferably 7-20 μm, more preferably 10-18 μm, and more preferably 12-15 μm. The specific surface area of the graphene is preferably 400-600 m2(ii)/g, more preferably 420 to 580m2(iv)/g, more preferably 450 to 550m2/g。
The thickness of the paint film is not particularly limited, the thickness of the paint film generated by the conventional anticorrosive paint known by the skilled in the art can be selected and adjusted by the skilled in the art according to the actual application condition, the compounding condition and the product performance, the thickness of the paint film can be effectively reduced by the anticorrosive paint containing the graphene material due to the addition of the graphene under the condition of ensuring the corrosion resistance requirement, and the thickness of the paint film is preferably 80-100 μm, more preferably 82-98 μm, more preferably 85-95 μm, and more preferably 87-92 μm.
The invention also provides a static conductive anticorrosive paint which comprises a component A and a component B;
the component A comprises the following components in percentage by mass:
the component B comprises a curing agent.
The selection and composition of the raw materials required in the static conductive anticorrosive paint, and the corresponding preferred principle, and the selection and composition of the raw materials corresponding to the paint film, and the corresponding preferred principle can all correspond to each other, and are not described in detail herein.
In the invention, the mass ratio of the materials in the component A refers to the mass ratio of the materials in the component A to the whole component A, but not to the whole static conductive anticorrosive paint; similarly, the mass ratio of the materials in the component B refers to the mass ratio of the materials in the component B to the whole component B, not to the whole static conductive anticorrosive paint.
In the component A, the addition amount of the epoxy resin is preferably 20 to 30 parts by weight, more preferably 22 to 28 parts by weight, and still more preferably 24 to 26 parts by weight. The selection of the epoxy resin is not particularly limited in the present invention, and may be a common epoxy resin known to those skilled in the art, and those skilled in the art can select and adjust the epoxy resin according to the actual application, the product requirement and the quality requirement, and the epoxy resin of the present invention preferably includes bisphenol a type epoxy resin.
In the component A, the organic solvent is used as a high-solid-content static conductive anticorrosive coating, and the addition amount of the organic solvent is only 3-7 parts by weight, more preferably 3.5-6.5 parts by weight, more preferably 4-6 parts by weight, and more preferably 4.5-5.5 parts by weight. The organic solvent is not particularly limited, and may be selected and adjusted by those skilled in the art according to practical application, product requirements and quality requirements, and preferably includes one or more of acetone, methyl isobutyl ketone, ethanol, isopropanol, butanone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate and butyl acetate, more preferably acetone, methyl isobutyl ketone, ethanol, isopropanol, butanone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate or butyl acetate, and more preferably acetone, methyl isobutyl ketone, ethanol, isopropanol, butanone, 2-pyrrolidone, toluene, xylene, butyl acetate, Two or more of n-butanol, propylene glycol methyl ether, propylene carbonate and butyl acetate, specifically xylene and n-butanol.
In the component a of the present invention, the surfactant dispersant of the present invention is preferably added in an amount of 0.1 to 1.5 parts by weight, more preferably 0.3 to 1.3 parts by weight, more preferably 0.5 to 1.0 part by weight, the selection of the surfactant dispersant of the present invention is not particularly limited in principle, and a person skilled in the art can select and adjust the surfactant dispersant according to actual application conditions, product requirements and quality requirements, in order to ensure that graphene can be uniformly distributed in a paint film, the surfactant dispersant of the present invention particularly preferably includes a sulfonate surfactant and/or a tween surfactant, more preferably a sulfonate surfactant and a tween surfactant, the sulfonate surfactant of the present invention preferably includes one or more of an alkylbenzene sulfonate, α -olefin sulfonate, an alkyl sulfonate, α -sulfo monocarboxylate, a fatty acid sulfoalkyl ester, a succinate sulfonate, an alkyl naphthalene sulfonate, a petroleum sulfonate, a sulfonate and an alkyl glyceryl ether sulfonate, more preferably includes one or more of an alkylbenzene sulfonate, a α -olefin sulfonate, an alkyl sulfonate, a α -sulfo monocarboxylate, a fatty acid alkyl ester, a succinate, a naphthalene sulfonate, a petroleum sulfonate, a tween 80-20-tween-20-or a tween-20-tween-surfactant.
In the component A, the addition amount of the graphene-based material is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 1 part by weight, more preferably 0.3 to 0.8 part by weight, and more preferably 0.5 to 0.6 part by weight.
In the component A, the filler is preferably added in an amount of 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, more preferably 30 to 60 parts by weight, and more preferably 40 to 50 parts by weight. The filler is not particularly limited, and may be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and preferably includes one or more of titanium dioxide, calcium carbonate, kaolin, montmorillonite, talcum powder, barium sulfate, mica powder, aluminum tripolyphosphate, zinc phosphate, modified zinc orthophosphate and ultrafine calcite powder, and more preferably includes two or more of titanium dioxide, calcium carbonate, kaolin, montmorillonite, talcum powder, barium sulfate, mica powder, aluminum tripolyphosphate, zinc phosphate, modified zinc orthophosphate and ultrafine calcite powder.
In the component A, the addition amount of the anti-settling agent is preferably 0.5-10 parts by weight, more preferably 1-9 parts by weight, more preferably 2-8 parts by weight, more preferably 3-7 parts by weight, and more preferably 4-6 parts by weight. The selection of the anti-settling agent is not particularly limited, and can be a common anti-settling agent for epoxy resin coatings, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and the anti-settling agent of the present invention preferably includes one or more of an anti-settling agent 3300, organobentonite, organoclay, fumed silica, wax slurry, polyethylene wax and cellulose ether, and more preferably an anti-settling agent 3300, organobentonite, organoclay, fumed silica, wax slurry, polyethylene wax or cellulose ether.
In the component A, the addition amount of the second dispersant is preferably 0.3 to 0.6 part by weight, more preferably 0.35 to 0.55 part by weight, and still more preferably 0.4 to 0.5 part by weight. The selection of the second dispersant is not particularly limited in the present invention, and may be a commonly used dispersant for epoxy resin coating materials well known to those skilled in the art, and those skilled in the art may select and adjust the dispersant according to the actual application, product requirements and quality requirements, and the second dispersant preferably includes one or more of caprolactone polyol-polyethyleneimine block copolymer, acrylate polymer dispersant, polyurethane dispersant, polyester dispersant and phosphate ester salt polymer, and more preferably caprolactone polyol-polyethyleneimine block copolymer, acrylate polymer dispersant, polyurethane dispersant, polyester dispersant or phosphate ester salt polymer.
In the component B of the present invention, there is no particular limitation on the selection of the curing agent, and the curing agent may be a commonly used curing agent for aqueous resin, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, the product requirements and the quality requirements, and the curing agent of the present invention preferably includes an epoxy curing agent, more preferably one or more of polyamide, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethylenepolyamine and polyetherdiamine, and more preferably polyamide, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethylenepolyamine or polyetherdiamine.
The specific dosage ratio of the component A and the component B is not particularly limited, and can be a conventional ratio in the use of conventional epoxy resin well known to those skilled in the art, and the selection and adjustment can be performed by those skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the component A and the component B is preferably (8-15): 1, more preferably (9-14): 1, more preferably (10 to 13): 1, more preferably (11-12): 1. in the invention, when the component A and the component B are mixed according to the proportion, an organic solvent can be added for viscosity adjustment according to the use requirement.
The invention also provides a preparation method of the static conductive anticorrosive paint, which comprises the following steps:
1) dispersing graphene dry powder, an organic solvent, epoxy resin and a surfactant dispersant to obtain graphene resin dispersion liquid;
2) re-dispersing the graphene resin dispersion liquid and the second dispersing agent obtained in the previous step to obtain a mixed liquid;
3) and mixing and grinding the mixed solution, the filler and the anti-settling agent obtained in the step to obtain the component A of the static conductive anticorrosive paint.
The selection and composition of the raw materials required in the preparation process and the corresponding preferred principle can be corresponding to the selection and composition of the raw materials corresponding to the static conductive anticorrosive paint and the corresponding preferred principle, and are not described in detail herein.
Firstly, dispersing graphene dry powder, an organic solvent, epoxy resin and a surfactant dispersant to obtain a graphene resin dispersion liquid.
The source of the graphene dry powder is not particularly limited, and a person skilled in the art can select and adjust the graphene dry powder according to the actual production condition, the product requirement and the quality requirement, and the graphene dry powder is preferably obtained by spray drying a graphene solution. The mass concentration of the graphene solution is preferably 0.1-6%, more preferably 0.5-5%, more preferably 1-4%, and more preferably 2-3%.
In principle, the conditions of the spray drying are not particularly limited, and the conditions of the spray drying known to those skilled in the art may be used, and the selection and adjustment may be performed by those skilled in the art according to the actual production situation, the product requirement, and the quality requirement, and in order to ensure the quality of the graphene dry powder, the time of the spray drying is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and more preferably 1.5 to 2 hours. The pressure of the spray drying is preferably 0.6-5 MPa, more preferably 1-4.5 MPa, more preferably 1.5-4 MPa, more preferably 2-3.5 MPa, and more preferably 2.5-3 MPa. The temperature of the spray drying is preferably 30-70 ℃, more preferably 35-65 ℃, more preferably 40-60 ℃, and more preferably 45-55 ℃.
The method and conditions for the dispersion are not particularly limited in the present invention, and the dispersion method and conditions known to those skilled in the art can be selected and adjusted according to the actual production situation, the product requirements and the quality requirements, and the dispersion method of the present invention preferably includes ultrasonic dispersion. The dispersing time is preferably 30-60 min, more preferably 35-55 min, and more preferably 40-50 min.
In order to ensure the uniform dispersion and specific dispersion mode of graphene in a paint film, complete and refined preparation process, the step 1) is preferably as follows:
1A) stirring and mixing graphene and an organic solvent to obtain a graphene mixed solution;
1B) stirring and mixing the graphene mixed solution obtained in the step and the surfactant dispersant again to obtain a graphene dispersion solution;
1C) and adding epoxy resin into the graphene dispersion liquid obtained in the step, stirring and mixing for the third time, and grinding to obtain the graphene epoxy resin dispersion liquid.
According to the invention, graphene and an organic solvent are stirred and mixed to obtain a graphene mixed solution.
The addition amount of the organic solvent is not particularly limited in the present invention, and may be the addition amount of a conventional organic solvent well known to those skilled in the art, and those skilled in the art may select and adjust the addition amount according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the graphene to the organic solvent in the present invention is preferably 1: (5-30), more preferably 1: (10-25), more preferably 1: (15-20).
The concrete mode of stirring and mixing is not particularly limited by the invention, and the stirring and mixing mode known by the person skilled in the art can be selected and adjusted by the person skilled in the art according to the actual production situation, the product requirement and the quality control, and the process route is optimized for further improving the uniformity and the performance of the dispersion liquid and the subsequent coating product, and the stirring and mixing preferably comprises magnetic stirring and/or mechanical stirring, more preferably magnetic stirring or mechanical stirring, and more preferably magnetic stirring.
The stirring and mixing time is not particularly limited, and the stirring and mixing time known by a person skilled in the art can be selected and adjusted by the person skilled in the art according to the actual production condition, the product requirement and the quality control, and in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route, the stirring and mixing time is preferably 15-30 min, more preferably 17-28 min, and more preferably 20-25 min.
The stirring and mixing speed is not particularly limited, and can be selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality control, and is preferably 300-600 r/min, more preferably 350-550 r/min, and more preferably 400-500 r/min, in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route.
According to the invention, the graphene mixed solution obtained in the above step and the surfactant dispersant are stirred and mixed again to obtain the graphene dispersion solution.
The addition amount of the surfactant dispersant is not particularly limited, and may be a conventional addition amount well known to those skilled in the art, and those skilled in the art may select and adjust the addition amount according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the graphene to the surfactant dispersant in the present invention is preferably 1: (1 to 30), more preferably 1: (5-25), more preferably 1: (10-20). The surfactant dispersant of the present invention preferably comprises a sulfonate surfactant and a tween surfactant.
The addition amount of the sulfonate surfactant is not particularly limited, and may be a conventional addition amount well known to those skilled in the art, and those skilled in the art may select and adjust the addition amount according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the graphene to the sulfonate surfactant in the present invention is preferably 1: (0.2 to 12), more preferably 1: (1-10), more preferably 1: (3-8), more preferably 1: (5-6).
The addition amount of the tween surfactant is not particularly limited, and the tween surfactant can be added in a conventional amount well known to those skilled in the art, and those skilled in the art can select and adjust the addition amount according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the graphene to the tween surfactant is preferably 1: (0.7-20), more preferably 1: (2-18), more preferably 1: (5-15), more preferably 1: (8-12).
The specific manner of the re-stirring and mixing is not particularly limited in the present invention, and may be any stirring and mixing manner known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality control, and the present invention optimizes the process route for further improving the uniformity and performance of the dispersion and the subsequent coating product, and the re-stirring and mixing preferably includes magnetic stirring and/or mechanical stirring, more preferably magnetic stirring or mechanical stirring, and still more preferably magnetic stirring.
The time for stirring and mixing again is not particularly limited, and the time for stirring and mixing which is well known by the skilled in the art can be selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality control, and in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route, the time for stirring and mixing again is preferably 15-40 min, more preferably 20-35 min, and more preferably 25-30 min.
The speed of the secondary stirring and mixing is not particularly limited by the invention, and the speed of the secondary stirring and mixing is selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality control, and the speed of the secondary stirring and mixing is preferably 300-600 r/min, more preferably 350-550 r/min, and more preferably 400-500 r/min, in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route.
Finally, adding epoxy resin into the graphene dispersion liquid obtained in the step, stirring and mixing for the third time, and grinding to obtain the graphene epoxy resin dispersion liquid.
The epoxy resin is not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality control, and the epoxy resin of the present invention preferably includes bisphenol a type epoxy resin, more preferably E-51 bisphenol a type epoxy resin and/or 601 bisphenol a type epoxy resin, and most preferably E-51 bisphenol a type epoxy resin or 601 bisphenol a type epoxy resin. The present invention is not limited to other parameters of the epoxy resin, and the parameters of the conventional epoxy resin known to those skilled in the art can be selected and adjusted according to the actual application, the product requirements and the quality requirements.
The addition amount of the epoxy resin is not particularly limited, and may be a conventional addition amount well known to those skilled in the art, and those skilled in the art may select and adjust the addition amount according to the actual application situation, the product requirement and the quality requirement, and the mass ratio of the epoxy resin to the graphene in the present invention is preferably 100: (0.5 to 3), more preferably 100: (1.0 to 2.5), more preferably 100: (1.5-2.0).
The addition mode of the epoxy resin is not particularly limited by the invention, and the epoxy resin can be added in a conventional manner well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production condition, the product requirement and the quality control, and the addition is preferably slowly added in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route.
The third mixing method is not particularly limited, and may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality control, and the third mixing method preferably includes magnetic stirring and/or mechanical stirring, more preferably magnetic stirring or mechanical stirring, and even more preferably mechanical stirring, to further improve the uniformity and performance of the dispersion and the subsequent coating product and optimize the process route.
The time for stirring and mixing for the third time is not particularly limited, and the time for stirring and mixing known by the skilled in the art can be selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality control, and in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route, the time for stirring and mixing again is preferably 20-60 min, more preferably 25-55 min, more preferably 30-50 min, and more preferably 35-45 min.
The third stirring and mixing speed is not particularly limited, and the third stirring and mixing speed is selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality control, and in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route, the second stirring and mixing speed is preferably 400-1000 r/min, more preferably 500-900 r/min, and more preferably 600-800 r/min.
The grinding mode is not particularly limited by the invention, and the grinding mode is a conventional grinding mode well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality control, and the grinding mode is preferably wet grinding, in order to further improve the uniformity and the performance of the dispersion liquid and the subsequent coating product and optimize the process route.
The grinding time is not particularly limited by the invention, and the grinding time known by the technicians in the field can be selected and adjusted by the technicians in the field according to the actual production condition, the product requirement and the quality control, the process route is optimized for further improving the uniformity and the performance of the dispersion and the subsequent coating product, and the grinding time is preferably 5-20 min, more preferably 7-18 min, and more preferably 10-15 min.
In the process of preparing the graphene resin dispersion liquid, a specific adding sequence is further preferably adopted, so that the graphene is better and uniformly dispersed in the epoxy resin, the problem of non-uniform dispersion of the graphene can be effectively solved, the excellent performance of the graphene can be better exerted, a resin mixture of uniformly dispersed graphene materials can be obtained, and the performance of the resin anticorrosive paint can be further improved subsequently. Moreover, the invention particularly carries out the operation without the existence of protective gas, thereby simplifying the production flow and production equipment and reducing the production consumption. The composite method provided by the invention has the advantages of simple process, mild conditions, safety and environmental protection, and is more suitable for industrialized production.
The graphene epoxy resin dispersion liquid is prepared by grinding, stirring and adding a surfactant dispersant. The preparation process is carried out at normal temperature, the traditional ultrasonic dispersion method is changed, the noise pollution and energy consumption are reduced, and the harm of noise to human bodies is avoided; the used solvents are all required for preparing the anticorrosive paint, and no additional solvent is used, so that the problems of environmental pollution and the like caused by the preparation process are solved. The problem that graphene is not uniformly dispersed in the anticorrosive paint and is easy to agglomerate is solved, the graphene is effectively added in a lamellar form to form a structure stacked layer by layer, the problem that the corrosion resistance of the graphene anticorrosive paint cannot be improved due to the fact that graphene does not exist in a lamellar structure in resin in the prior art is effectively solved, and the coating has a good application prospect in the anticorrosive field of paints.
According to the invention, the graphene resin dispersion liquid and the second dispersing agent obtained in the above steps are dispersed again to obtain a mixed liquid.
The invention is not limited to the mode and parameters of re-dispersion, and the mixing mode and parameters for the anticorrosive paint are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality requirement, and the re-dispersion is preferably ultrasonic dispersion. The re-dispersing time is preferably 30-60 min, more preferably 35-55 min, and more preferably 40-50 min.
The component A of the static conductive anticorrosive paint is obtained by mixing and grinding the mixed solution, the filler and the anti-settling agent obtained in the step.
The grinding time is preferably 30-180 min, more preferably 60-120 min, and even more preferably 80-100 min, in order to further ensure that the filler can be uniformly dispersed. The fineness of the grinding, namely the fineness of the ground slurry, is preferably 10-60 μm, more preferably 20-50 μm, and more preferably 30-40 μm.
The component A of the static conductive anticorrosive paint is obtained through the steps. The static conductive anticorrosive paint of the invention preferably further comprises a component B. In order to ensure that the performance of the product can be fully exerted, optimized and integrated in the use process, the component A of the resin anticorrosive paint can be obtained, and the following steps can be carried out:
the component A and the component B can be used after being regulated, finally mixed and kept stand.
Whether the above-mentioned steps are continued with the preparation steps of the A component and the B component is not particularly limited in the present invention, and those skilled in the art will know based on the common knowledge that the steps may be performed before the anticorrosive coating is used, that is, after the steps, the static conductive anticorrosive coating may be used. Therefore, this step may not be included in the preparation of the resin anticorrosive coating.
The final mixing method and parameters are not particularly limited in the present invention, and can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality requirement, and the final mixing method and parameters are preferably stirring mixing. The final mixing time of the invention is preferably 10-20 min, more preferably 12-18 min, and more preferably 14-16 min. The final mixing of the invention can be manually stirred and mixed, and can also be stirred and mixed by a machine, and the rotating speed can be 400-800 rpm, or 500-700 rpm.
The parameter of the standing is not particularly limited, and the parameter of the standing defoaming step in the application of the anticorrosive paint, which is well known to those skilled in the art, can be selected and adjusted by those skilled in the art according to the actual production condition, the product requirement and the quality requirement, and the standing time in the invention is preferably 10-30 min, more preferably 12-28 min, and more preferably 15-25 min.
Based on the sheet structure, excellent corrosion resistance and electrostatic conductivity of graphene, and good chemical stability and electrostatic conductivity of graphene, the novel composite coating with good electrostatic conductivity, long service life and good corrosion resistance is prepared by adopting a specific coating formula and combining a specific preparation process. In order to further ensure the corrosion resistance of the final coating, complete and detailed preparation process, the preparation steps can be as follows:
carrying out spray drying on the graphene solution to obtain graphene dry powder, and carrying out ultrasonic dispersion on the dry powder, organic solvents such as benzene ethers or ketones, epoxy resin and a surfactant dispersant according to a certain proportion to obtain a graphene resin dispersion liquid.
Adding the graphene resin dispersion liquid and a second dispersing agent into a production cylinder, and fully dispersing in a stirring and mixing mode;
and 3, adding the filler and the anti-settling agent while stirring, and grinding the mixture by using a blue grinding machine after the filler and the anti-settling agent are added and stirred for a certain time.
And 4, adding an anti-settling agent into the slurry obtained in the step 3, and further diluting by adopting an organic solvent to adjust the viscosity and the solid content.
5 ] sample implementation: uniformly mixing A and B in a ratio of 6:1, adding a certain amount of diluent to adjust the spraying viscosity to be 30-40S (T-4 cup, 25 ℃), spraying 90 +/-10 mu m on a 3mm carbon steel plate, and naturally curing for 7 days at room temperature to test the chemical resistance, the salt spray resistance and the cold-hot cycle resistance.
The steps of the invention provide a paint film of the static conductive anticorrosive paint, the high-solid-content graphene static conductive anticorrosive paint and a preparation method thereof. Starting from an electrochemical mechanism, the self-assembly of the coating after the coating is sprayed on a substrate is realized by combining a physical shielding direction and through formula adjustment of the coating and preparation of graphene epoxy resin dispersion liquid, a paint film with a special structure is creatively obtained, and graphene sheets in the paint film are uniformly distributed in the paint film structure to form a graphene layer; the thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure, the graphene layers formed by the graphene sheets are uniformly distributed between the upper surface and the lower surface of the paint film, the shielding and blocking effects of the coating are effectively improved by utilizing the extremely high specific surface area, the extremely high ground thickness ratio, the excellent conductivity and the excellent blocking performance of a two-dimensional material of the graphene, the corrosion resistance of the coating is improved, and meanwhile, the graphene layers with the labyrinth effect are formed between the graphene sheets and the graphene sheets along the thickness direction of the graphene layers from the section of the paint film structure, so that the static electricity conducting performance of the coating is greatly improved, and the coating has a great application prospect in the field of anticorrosion static electricity conducting coatings.
According to the high-solid-content environment-friendly novel coating for the heavy-duty anti-corrosion static conductive coating field, the ordered arrangement of graphene is realized by utilizing the ultrahigh diameter-thickness ratio of graphene and the special barrier effect of a two-dimensional material through adjusting a formula and a preparation process, and the sheet structure of the graphene two-dimensional material can form a labyrinth effect, so that the shielding barrier effect of a coating is effectively improved, the anti-corrosion performance of an epoxy coating is improved, and the durability of the coating is prolonged; meanwhile, the ultrahigh conductivity of the graphene is utilized, and the specific labyrinth arrangement mode of graphene sheet layers is combined, so that the resistance of the coating is reduced, the static electricity conducting effect is achieved, and the static electricity conducting performance of the coating can be greatly improved with extremely small addition amount. The high-solid-content environment-friendly novel coating provided by the invention only needs to use few solvents, fundamentally reduces the main source of VOC in use, has extremely low VOC, meets the requirements of green environment-friendly coatings at present, and is an environment-friendly coating. And the preparation process is simple, strong in controllability and suitable for industrial mass production and popularization and application.
Experimental results show that the high-solid-content graphene anti-corrosion static-conducting coating is prepared in a simple mode, the compounding degree of graphene and resin is high, the graphene is distributed in the coating layer in a staggered labyrinth type layer by layer, the anti-corrosion performance and the static-conducting performance of the coating layer are greatly improved, and the surface resistance of the coating layer can reach 108Omega, and the mass solid content can reach 93 percent.
For further illustration of the present invention, the paint film of the electrostatic conductive anticorrosive paint, the electrostatic conductive anticorrosive paint and the preparation method thereof provided by the present invention are described in detail with reference to the following examples, but it should be understood that the examples are implemented on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Examples 1 to 4
The following raw materials were used:
epoxy resin (Tai plastic group)
Organic bentonite (Zhongsen perlite Co., Ltd.)
Epoxy diluent (Anhui Xinyuan)
Dispersing agent (Nantong break Thailand chemical Co., Ltd.)
Graphene (Shandong Europe platinum New Material Co., Ltd.)
Aluminium triphosphate (national city Co., Ltd.)
Modified zinc phosphate (HEUBACH)
Calcium carbonate (Jiangyin Jiyue Jie trade company)
Wax slurry (Shanghai Mingdian chemical trade company Limited)
Table 1 shows the formulation ratios of examples 1 to 4 of the present invention and comparative examples.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Epoxy resin | 21 | 25 | 20 | 27 | 22 |
| Graphene | 0.02 | 0.05 | 0.1 | 0.2 | 0 |
| Conductive mica powder | 0 | 0 | 0 | 0 | 25 |
| Organic solvent | 6 | 3.5 | 5.2 | 4.9 | 17 |
| Dispersing agent (watch) | 0.3 | 1.5 | 0.15 | 1 | 1 |
| Organic bentonite | 2 | 1.2 | 1 | 2 | 3 |
| Aluminium triphosphate | 21.68 | 43.65 | 19.45 | 22.4 | 20 |
| Calcium carbonate | 31 | 18 | 18 | 15 | 1.4 |
| Titanium white powder | 2 | 1 | 2 | 3 | 2 |
| Wax slurry | 0.9 | 2 | 1 | 3 | 3 |
| Modified zinc phosphate | 15 | 4 | 32.8 | 21 | 5 |
| A second dispersant | 0.1 | 0.1 | 0.3 | 0.5 | 0.6 |
| Total up to | 100 | 100 | 100 | 100 | 100 |
Carrying out ultrasonic dispersion on graphene produced by Shandong Europe platinum New Material Co., Ltd, an organic solvent, epoxy resin and a surfactant dispersant for 4 hours according to a proportion to obtain a graphene resin dispersion liquid.
Adding the graphene resin dispersion liquid, epoxy diluent and a second dispersing agent into a production cylinder, and fully dispersing for 5min at a speed of 600 r/min;
and 3, adding titanium dioxide, organic bentonite, modified zinc phosphate, aluminum tripolyphosphate and calcium carbonate into the mixture in the step 2 while stirring at 800r/min, and grinding the mixture to the fineness of 50 microns by using a blue grinding machine after the mixture is added and stirred for 5 min.
And 4, adding the slurry obtained in the step 3 into wax slurry, and adjusting the viscosity and the solid content by adopting an organic solvent.
5 ] sample implementation: uniformly mixing A and B in a ratio of 6:1, adding a certain amount of organic solvent for dilution, adjusting the spraying viscosity to be 30-40S (T-4 cup, 25 ℃), spraying 90 +/-10 mu m on a 3mm carbon steel plate, and naturally curing for 7 days at room temperature to test the chemical resistance, the salt spray resistance and the cold-hot cycle resistance.
The paint films obtained in example 1 of the invention were characterized.
Referring to FIG. 1, FIG. 1 is an SEM micrograph of a cross-section of a paint film prepared according to example 1 of the present invention.
As can be seen from fig. 1, the graphene sheets are uniformly and orderly arranged and inserted into the paint film structure, and extend over the whole paint film, the thickness direction of the graphene layer is substantially the same as the thickness direction of the paint film structure, and adjacent or similar graphene sheets are distributed in a staggered manner in the whole paint film along the thickness direction of the graphene layer, so that a graphene layer (paint film) with a labyrinth effect is formed between the graphene sheets.
Referring to FIG. 2, FIG. 2 is a high magnification SEM micrograph of a cross section of a paint film prepared according to example 1 of the present invention.
As can be seen from fig. 2, the graphene sheets are uniformly arranged and embedded in the resin paint film, and adjacent or similar graphene sheets are distributed in a staggered manner, so that the graphene paint film has a labyrinth effect.
Referring to FIG. 3, FIG. 3 is a high magnification SEM micrograph of a cross section of a paint film prepared according to example 1 of the present invention.
As can be seen from fig. 3, the graphene sheet has a small number of sheets and a small thickness, indicating that the graphene sheet is uniformly dispersed and does not agglomerate.
According to the national standard requirements, the paint films obtained in the embodiments 1-4 and the comparative example of the invention are detected.
The results are shown in Table 2, where Table 2 shows the performance data of the paint films obtained in examples 1 to 4 of the present invention and comparative examples.
TABLE 2
Comparative example
Adding epoxy resin, an organic solvent and a second dispersing agent into a production cylinder, and fully dispersing for 5min at a speed of 600 r/min;
and 2, adding the conductive mica powder, the titanium dioxide, the organic bentonite, the modified zinc phosphate, the aluminum tripolyphosphate and the calcium carbonate into the mixture in the step 1 while stirring at 800r/min, and grinding the mixture to the fineness of 50 microns by using a blue grinding machine after the mixture is added and stirred for 5 min.
And 3, adding the slurry obtained in the step 2 into wax slurry, and adjusting the viscosity and the solid content by adopting an organic solvent.
5 ] sample implementation: mixing A and B at a ratio of 6:1, adding a certain amount of organic solvent for dilution, adjusting the spraying viscosity to 30-40S (T-4 cup, 25 ℃), spraying 90 +/-10 mu m on a 3mm carbon steel plate, and naturally curing at room temperature for 7 days to test the chemical resistance, the salt spray resistance and the cold-heat cycle resistance.
According to the national standard requirements, the paint films obtained in the embodiments 1-4 and the comparative example of the invention are detected.
The above detailed description of the paint film of the electrostatic conductive anticorrosive paint, the high-solid content graphene electrostatic conductive anticorrosive paint and the preparation method thereof according to the present invention is provided, and the principle and the embodiments of the present invention are described herein by using specific examples, which are only used to help understanding the method of the present invention and the core idea thereof, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any method in combination. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A paint film of a static conductive anticorrosive paint is characterized in that graphene sheets in the paint film are uniformly distributed in the paint film structure to form a graphene layer;
the thickness direction of the graphene layer is the same as or similar to the thickness direction of the paint film structure.
2. The paint film according to claim 1, wherein adjacent or similar graphene sheets in the graphene layer are distributed in a staggered manner in the thickness direction of the graphene layer as seen in a section of the paint film structure;
viewed from the section of the paint film structure, a graphene layer with a labyrinth effect is formed between the graphene sheets along the thickness direction of the graphene layer;
the similarity is that the included angle between the thickness direction of the graphene layer and the thickness direction of the paint film structure is less than or equal to 60 degrees;
the thickness of the graphene sheet is 0.8-1.6 nm;
the number of the graphene sheets is 1-5;
the thickness of the paint film is 80-100 mu m.
3. The static conductive anticorrosive paint is characterized by comprising a component A and a component B;
the component A comprises the following components in percentage by mass:
the component B comprises a curing agent.
4. The static conductive anticorrosive paint according to claim 3, wherein the epoxy resin comprises bisphenol A type epoxy resin;
the mass ratio of the component A to the component B is (8-15): 1;
the curing agent comprises an epoxy curing agent;
the surfactant dispersant comprises a sulfonate surfactant and/or a Tween surfactant.
5. The static conductive anticorrosive paint according to claim 4, wherein the sulfonate surfactant comprises one or more of alkyl benzene sulfonate, α -olefin sulfonate, alkyl sulfonate, α -sulfo monocarboxylic acid ester, fatty acid sulfoalkyl ester, succinate sulfonate, alkyl naphthalene sulfonate, petroleum sulfonate, lignin sulfonate, and alkyl glyceryl ether sulfonate;
the Tween surfactant comprises one or more of Tween-80, Tween-20, Tween-60 and Tween-40;
the filler comprises one or more of titanium dioxide, calcium carbonate, kaolin, montmorillonite, talcum powder, barium sulfate, mica powder, aluminum tripolyphosphate, zinc phosphate, modified zinc orthophosphate and superfine calcite powder;
the anti-settling agent comprises one or more of an anti-settling agent 3300, organic bentonite, organic clay, organic argil, fumed silica, wax slurry, polyethylene wax and cellulose ether;
the organic solvent comprises one or more of acetone, methyl isobutyl ketone, ethanol, isopropanol, butanone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate and butyl acetate;
the second dispersant comprises one or more of caprolactone polyol-polyethyleneimine segmented copolymer, acrylate high molecular dispersant, polyurethane dispersant, polyester dispersant and phosphate high molecular polymer;
the curing agent comprises one or more of polyamide, ethylenediamine, diethylenetriamine, triethylene tetramine, polyethylene polyamine and polyether diamine.
6. The preparation method of the static conductive anticorrosive paint is characterized by comprising the following steps of:
1) dispersing graphene dry powder, an organic solvent, epoxy resin and a surfactant dispersant to obtain graphene resin dispersion liquid;
2) re-dispersing the graphene resin dispersion liquid and the second dispersing agent obtained in the previous step to obtain a mixed liquid;
3) and mixing and grinding the mixed solution, the filler and the anti-settling agent obtained in the step to obtain the component A of the static conductive anticorrosive paint.
7. The method of manufacturing according to claim 6, wherein the dispersing includes ultrasonic dispersing;
the dispersing time is 30-60 min;
the graphene dry powder is obtained by spray drying a graphene solution;
the mass concentration of the graphene solution is 0.1-6%;
the time of spray drying is 0.5-3 h;
the pressure of the spray drying is 0.6-5 MPa;
the temperature of the spray drying is 30-70 ℃;
the static conductive anticorrosive paint also comprises a component B.
8. The method of manufacturing according to claim 7, wherein the re-dispersing includes ultrasonic dispersing;
the re-dispersing time is 30-60 min;
the grinding time is 30-180 min;
the fineness of the ground slurry is 10-60 mu m;
the solid content of the static conductive anticorrosive paint is 88-98 percent;
the component A and the component B can be used after final mixing and uniform mixing.
9. The preparation method according to any one of claims 6 to 8, wherein the step 1) is specifically:
1A) stirring and mixing graphene and an organic solvent to obtain a graphene mixed solution;
1B) stirring and mixing the graphene mixed solution obtained in the step and the surfactant dispersant again to obtain a graphene dispersion solution;
1C) and adding epoxy resin into the graphene dispersion liquid obtained in the step, stirring and mixing for the third time, and grinding to obtain the graphene epoxy resin dispersion liquid.
10. The method according to claim 9, wherein the surfactant dispersant comprises a sulfonate surfactant and a tween surfactant;
the stirring and mixing time is 15-30 min;
the stirring and mixing speed is 300-600 r/min;
the time for stirring and mixing again is 15-40 min;
the speed of stirring and mixing again is 300-600 r/min;
the third stirring and mixing time is 20-60 min;
the third stirring and mixing speed is 400-1000 r/min;
the addition is slow;
the grinding time is 5-20 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114075403A (en) * | 2020-08-19 | 2022-02-22 | 山东欧铂新材料有限公司 | Graphene static conductive floor coating film, graphene static conductive floor coating and preparation method thereof |
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