CN111286258B - Water-based graphene conductive anticorrosive paint and preparation method thereof - Google Patents
Water-based graphene conductive anticorrosive paint and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 178
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003973 paint Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000006185 dispersion Substances 0.000 claims abstract description 75
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- 239000011787 zinc oxide Substances 0.000 claims abstract description 44
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 27
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000000945 filler Substances 0.000 claims abstract description 23
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 13
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 13
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 13
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000010008 shearing Methods 0.000 claims abstract description 11
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000000440 bentonite Substances 0.000 claims description 11
- 229910000278 bentonite Inorganic materials 0.000 claims description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 8
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- 239000002904 solvent Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 238000005536 corrosion prevention Methods 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 30
- 239000011248 coating agent Substances 0.000 description 27
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
Abstract
The invention relates to a water-based graphene conductive anticorrosive paint and a preparation method thereof, wherein the raw materials comprise a component A and a component B; the component A is mainly prepared from the following raw materials in parts by weight: 40-60 parts of waterborne epoxy resin, 20-60 parts of filler, 2-4 parts of assistant and 10-20 parts of water; the component B is mainly prepared from the following raw materials in parts by weight: 5-10 parts of graphene water dispersion, 10-20 parts of zinc oxide and 40-60 parts of water-based epoxy curing agent; the preparation method of the graphene aqueous dispersion comprises the following steps: mixing graphene, carboxymethyl cellulose and water, and shearing and dispersing for 1-2 hours to obtain a mixture; and carrying out ultrasonic treatment on the mixture for 3-4 h. The solvent of the aqueous graphene conductive anticorrosive paint is water, the paint is energy-saving and environment-friendly, the conductive fillers, namely graphene and zinc oxide, are small in addition amount, the paint is well dispersed in water, a conductive network can be formed, the paint has an excellent conductive anticorrosive effect, and the paint is particularly suitable for corrosion prevention of storage tanks, pipelines, underground power grids and the like.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a water-based graphene conductive anticorrosive coating and a preparation method thereof.
Background
The anticorrosive paint is a paint which is widely applied in modern industry, traffic, energy, ocean engineering and other departments. With the rapid development of the petroleum industry, railways, highway bridges, metallurgical industry, electric power and energy industry, machinery and textile industry, industrial product field, automobiles, ships, containers and other industries in China, continuous innovation of the technology of the anti-corrosive coating field is urgently needed. In some special fields such as electric power transportation, storage tanks and pipelines, on one hand, metal materials are required to have corrosion resistance, and on the other hand, the conductive properties of the materials are required to be maintained.
By electrically conductive is meant that the coating has the ability to conduct electrical current and dissipate accumulated static charge. Besides protecting the base material from corrosion, the conductive anticorrosive paint also has conductivity so as to eliminate the accumulation of static charges of an oil tank and the like, and when the finish paint of the pipeline is damaged, the cathodic protection system of the coating can immediately protect the pipeline through the conductive primer so as to ensure the safe and economic operation of equipment and the pipeline.
The conductive filler is an additive material composed of a conductive material, is an important component of the conductive coating, has a large influence on the conductive coating, and is a metal filler, a carbon filler, a conductive fiber material and the like which are commonly used at present. Various conductive fillers each have advantages and disadvantages. Carbon black has a stable structure and is not easily oxidized, but the addition amount of the carbon black is large, so that the adhesion and appearance of a coating are affected, and cracks and peeling are easily caused. The noble metal silver has good conductivity, but has high cost, and is easy to migrate to cause the conductivity of the coating to be reduced, so that the conductivity is unstable. The common metal is easy to increase the resistance due to the surface oxidation, which brings inconvenience to the use.
The graphene has the characteristics of good toughness, strong adhesive force, good stability, high hardness and the like. Firstly, a physical barrier layer can be formed between metal and an active medium due to a stable sp2 hybrid structure of graphene, so that diffusion and permeation are prevented; secondly, graphene has good thermal and chemical stability, and can be stable under high temperature conditions (up to 1500 ℃), and in corrosive or oxidative gas and liquid environments. In addition, the good conductivity of graphene is suitable for being used as an excellent conductive filler. The metal oxide has the characteristics of excellent conductivity, light color and strong oxidation resistance. However, graphene and metal oxide are difficult to wet and disperse in an aqueous solution, and graphene is easy to agglomerate in a coating, thereby affecting the performance of the coating. Patent 201610813904.5 reports that the conductive paint using graphene oxide and tin oxide nanoparticles as fillers has poor stability and general corrosion resistance; patent 201611154411.1 reports a conductive anticorrosive paint using metallic and non-metallic conductive material particles as conductive fillers, but the resistivity of the paint is still high; patent 201811076130.8 reports an anticorrosive paint using hydroxy acrylic resin and epoxy resin as film forming substances and modified graphene and carbon nanotubes as conductive fillers, but the paint contains a large amount of organic solvents and is easy to cause environmental pollution. Therefore, in conclusion, the development of the conductive anticorrosive paint with good dispersion effect and environmental protection has important application value.
Disclosure of Invention
Based on the above, the invention provides the water-based graphene conductive anticorrosive paint, the solvent is water, the paint is energy-saving and environment-friendly, the conductive fillers, namely graphene and zinc oxide, are small in addition amount, the conductive fillers are well dispersed in water, a conductive network can be formed, the paint has an excellent conductive anticorrosive effect, and the paint is particularly suitable for corrosion prevention of storage tanks, pipelines, underground power grids and the like.
The specific technical scheme is as follows:
the raw materials of the water-based graphene conductive anticorrosive paint comprise a component A and a component B;
the component A is mainly prepared from the following raw materials in parts by weight:
40-60 parts of waterborne epoxy resin,
20-60 parts of filler,
2-4 parts of auxiliary agent,
10-20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
5-10 parts of graphene aqueous dispersion,
10-20 parts of zinc oxide,
40-60 parts of a water-based epoxy curing agent;
the preparation method of the graphene aqueous dispersion comprises the following steps:
mixing graphene, carboxymethyl cellulose and water, and shearing and dispersing for 1-2 hours to obtain a mixture;
and carrying out ultrasonic treatment on the mixture for 3-4 h.
In some preferred embodiments, the component a of the aqueous graphene conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight:
50-60 parts of waterborne epoxy resin,
25-50 parts of filler,
2-4 parts of auxiliary agent,
10-20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
8-10 parts of graphene water dispersion,
15-20 parts of zinc oxide,
50-60 parts of a water-based epoxy curing agent.
In some preferred embodiments, the component a of the aqueous graphene conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight:
50 parts of waterborne epoxy resin,
30 portions of filler,
3 portions of auxiliary agent,
20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
10 parts of graphene water dispersion,
20 portions of zinc oxide,
50 parts of a water-based epoxy curing agent.
In some preferred embodiments, the graphene aqueous dispersion has a mass fraction of graphene of 3-10%.
In some preferred embodiments, the graphene aqueous dispersion has a mass fraction of graphene of 5%.
In some preferred embodiments, the weight ratio of the graphene aqueous dispersion to the zinc oxide is 1 (1.5-2).
In some preferred embodiments, the weight ratio of the graphene aqueous dispersion to the zinc oxide is 1: 2.
In some preferred embodiments, the filler is selected from one or more of organic bentonite, silica micropowder and barium sulfate.
In some preferred embodiments, the filler is present in a mass ratio of 1: (1-3): (1-3) a mixture of organobentonite, fine silica powder and barium sulfate.
In some preferred embodiments, the filler is present in a mass ratio of 1: 1: 1 of organobentonite, silica micropowder and barium sulfate.
In some preferred embodiments, the aqueous epoxy resin is a bisphenol a type epoxy resin.
In some preferred embodiments, the aqueous epoxy curing agent is an amine curing agent.
In some preferred embodiments, the auxiliary agent is selected from one or more of a dispersing agent, a leveling agent and an antifoaming agent.
In some preferred embodiments, the dispersant is PE 100.
In some preferred embodiments, the leveling agent is BYK 346.
In some preferred embodiments, the anti-foaming agent is BYK-028.
In some preferred embodiments, the mass ratio of component A to component B is (1-3): 1.
In some preferred embodiments, the mass ratio of component a to component B is 2: 1.
The invention also provides a preparation method of the water-based graphene conductive anticorrosive paint.
The specific technical scheme is as follows:
a preparation method of a water-based graphene conductive anticorrosive paint comprises the following steps:
mixing the waterborne epoxy resin, the filler, the auxiliary agent and water, and stirring for 1-2 h at the rotating speed of 1000-1500 rpm;
and mixing the graphene aqueous dispersion, the zinc oxide and the water-based epoxy curing agent, and stirring at 1500-2000 rpm for 1-2 h.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, graphene, carboxymethyl cellulose and water are mixed, and are subjected to ultrasonic treatment after being sheared and dispersed to obtain a graphene aqueous solution with good dispersion and stability, and then the graphene aqueous dispersion, zinc oxide and a water-based epoxy curing agent are mixed to obtain a component B, wherein the graphene and the zinc oxide have small addition amount and can be stably dispersed in the component B. Meanwhile, a conductive network is formed by the graphene and the zinc oxide, and the conductive network still has excellent conductive and anticorrosion effects under the condition that the graphene and the zinc oxide have small addition amount, so that the finally prepared coating has the adhesive force of 8Mpa, the salt spray resistance of more than 3000H, the humidity and heat resistance of more than 2000H, the flexibility of 2mm and the 10% H resistance2SO41000h, 10% NaOH resistance for 1000h, 3% NaCl resistance for 720h, 93# gasoline resistance for 600 h, and surface resistivity of 1.8 x 102Omega. Meanwhile, the solvent of the aqueous graphene conductive anticorrosive paint is water, volatile organic compounds are not generated, and the aqueous graphene conductive anticorrosive paint is very environment-friendly. No VOC and is environment-friendly. The method is particularly suitable for corrosion prevention of storage tanks, pipelines, underground power grids and the like, and is suitable for large-scale production.
Drawings
FIG. 1 is a schematic surface view of a coating obtained using the dope of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The graphene has the characteristics of good toughness, strong adhesive force, good stability, high hardness and the like. Firstly, a physical barrier layer can be formed between metal and an active medium due to a stable sp2 hybrid structure of graphene, so that diffusion and permeation are prevented; secondly, graphene has good thermal and chemical stability, and can be stable under high temperature conditions (up to 1500 ℃), and in corrosive or oxidative gas and liquid environments. In addition, the good conductivity of graphene is suitable for being used as an excellent conductive filler. However, graphene is poorly dispersed in an aqueous solution, which hinders the application of graphene as a conductive filler in a water-based paint, and at present, a considerable portion of conductive anticorrosive paint containing graphene is solvent-based, which is high in cost, pollutes the environment, and is not beneficial to sustainable development of social economy, so how to prepare an environment-friendly water-based conductive anticorrosive paint containing graphene is an important research topic in the field.
The invention provides a water-based graphene conductive anticorrosive paint which comprises a component A and a component B as raw materials;
the component A is mainly prepared from the following raw materials in parts by weight:
40-60 parts of waterborne epoxy resin,
20-60 parts of filler,
2-4 parts of auxiliary agent,
10-20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
5-10 parts of graphene aqueous dispersion,
10-20 parts of zinc oxide,
40-60 parts of a water-based epoxy curing agent;
the preparation method of the graphene aqueous dispersion comprises the following steps:
mixing graphene, carboxymethyl cellulose and water, and shearing and dispersing for 1-2 hours to obtain a mixture;
and carrying out ultrasonic treatment on the mixture for 3-4 h.
According to the invention, graphene, carboxymethyl cellulose and water are mixed, and are subjected to ultrasonic treatment after being sheared and dispersed to obtain a graphene aqueous solution with good dispersion and stability, and then the graphene aqueous dispersion, zinc oxide and a water-based epoxy curing agent are mixed to obtain a component B, wherein the graphene and the zinc oxide have small addition amount and can be stably dispersed in the component B. Meanwhile, a conductive network is formed by the graphene and the zinc oxide, and the graphene and the zinc oxide still have excellent conductive and anticorrosion effects under the condition that the graphene and the zinc oxide have small addition amount.
In the graphene aqueous dispersion, the mass fraction of graphene also has an influence on the dispersion stability of graphene in a dispersion system. In some preferred embodiments, the graphene aqueous dispersion has a mass fraction of graphene of 3-10%. In some more preferred embodiments, the graphene aqueous dispersion has a mass fraction of graphene of 5%.
In the component B, the graphene aqueous dispersion, the zinc oxide and the aqueous epoxy curing agent are mixed, the combined system is more stable, and compared with the method that the graphene aqueous dispersion and the zinc oxide are directly added into the component A, the paint film is more uniform in particle size and better in flexibility.
Compared with the graphene mixed with other metal oxides, the graphene and the zinc oxide coexist in the coating system, a conductive grid is more favorably formed, and the excellent conductive anticorrosion effect is still achieved under the condition of less adding amount of the graphene and the zinc oxide, and in some preferred embodiments, the weight ratio of the graphene aqueous dispersion to the zinc oxide is 1 (1.5-2). In some more preferred embodiments, the weight ratio of the aqueous graphene dispersion to zinc oxide is 1: 2.
In some preferred embodiments, the aqueous epoxy curing agent is a bisphenol a type epoxy resin.
In some preferred embodiments, the aqueous epoxy curing agent is an amine curing agent.
Preferably, the component A of the aqueous graphene conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight:
50-60 parts of waterborne epoxy resin,
25-50 parts of filler,
2-4 parts of auxiliary agent,
10-20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
8-10 parts of graphene water dispersion,
15-20 parts of zinc oxide,
50-60 parts of a water-based epoxy curing agent.
More preferably, the component a of the aqueous graphene conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight:
50 parts of waterborne epoxy resin,
30 portions of filler,
3 portions of auxiliary agent,
20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
10 parts of graphene water dispersion,
20 portions of zinc oxide,
50 parts of a water-based epoxy curing agent.
In some preferred embodiments, the filler is selected from one or more of organic bentonite, silica micropowder and barium sulfate. In some more preferred embodiments, the filler is present in a mass ratio of 1: (1-3): (1-3) a mixture of organobentonite, fine silica powder and barium sulfate. In some most preferred embodiments, the filler is present in a mass ratio of 1: 1: 1 of organobentonite, silica micropowder and barium sulfate.
It is understood that the auxiliary agent is selected from one or more of a dispersant, a leveling agent and an antifoaming agent.
In some preferred embodiments, the dispersant is PE 100.
In some preferred embodiments, the leveling agent is BYK 346.
In some preferred embodiments, the anti-foaming agent is BYK-028.
It should be noted that the auxiliary agents described in the present invention can be selected from the auxiliary agents conventional in the art, and the present invention is not further described herein.
When in use, the component A and the component B are mixed according to the mass ratio of (1-3) to 1.
In some preferred embodiments, the component a is mixed with the component B in a mass ratio of 2: 1.
The invention also provides a preparation method of the water-based graphene conductive anticorrosive paint.
The specific technical scheme is as follows:
a preparation method of a water-based graphene conductive anticorrosive paint comprises the following steps:
mixing the waterborne epoxy resin, the filler, the auxiliary agent and water, and stirring for 1-2 h at the rotating speed of 1000-1500 rpm;
and mixing the graphene aqueous dispersion, the zinc oxide and the water-based epoxy curing agent, and stirring at 1500-2000 rpm for 1-2 h.
The following is a further description with reference to specific examples.
In the following examples, all the starting materials are commercially available unless otherwise specified.
The model number of the waterborne epoxy resin is F0707, and the waterborne epoxy resin can be purchased from Shenzhen Jitian chemical industry.
The model of the waterborne epoxy curing agent is F0704, and can be purchased from Shenzhen Jitian chemical industry.
Example 1
The embodiment provides a water-based graphene conductive anticorrosive paint and a preparation method thereof, and the preparation method comprises the following steps:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5h to obtain a mixture.
And carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 5%.
(2) Preparation of component A
50g of water-based epoxy resin, 10g of organic bentonite, 10g of silicon micropowder, 10g of barium sulfate, 20g of water, 1g of dispersing agent PE100, 1g of flatting agent BYK346 and 1g of defoaming agent BYK-028 are mixed and stirred for 2 hours at the rotating speed of 1500rpm to obtain a component A.
(3) Preparation of component B
10g of the graphene aqueous dispersion, 20g of zinc oxide and 50g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2:1 to obtain the coating, and the coating effect is shown in figure 1.
Example 2
The embodiment provides a water-based graphene conductive anticorrosive paint and a preparation method thereof, the steps of which are basically the same as those of embodiment 1, the difference is that the raw material contents and preparation methods of the component A and the component B are different from those of embodiment 1, and the specific steps are as follows:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5h to obtain a mixture.
And carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 5%.
(2) Preparation of component A
60g of water-based epoxy resin, 10g of organic bentonite, 20g of silicon micropowder, 20g of barium sulfate, 15g of water, 1g of dispersing agent PE100, 2g of flatting agent BYK346 and 2g of defoaming agent BYK-028 are mixed and stirred at the rotating speed of 1000rpm for 1.5h to obtain the component A.
(3) Preparation of component B
8g of the graphene aqueous dispersion, 15g of zinc oxide and 60g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2: 1.
Example 3
The embodiment provides a water-based graphene conductive anticorrosive paint and a preparation method thereof, the steps of which are basically the same as those of embodiment 1, the difference is that the raw material contents and preparation methods of the component A and the component B are different from those of embodiment 1, and the specific steps are as follows:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5h to obtain a mixture.
And carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 5%.
(2) Preparation of component A
40g of water-based epoxy resin, 10g of organic bentonite, 15g of silicon micropowder, 30g of barium sulfate, 20g of water, 1g of dispersing agent PE100, 1g of flatting agent BYK346 and 2g of defoaming agent BYK-028 are mixed and stirred for 1h at the rotating speed of 1500rpm to obtain the component A.
(3) Preparation of component B
5g of the graphene aqueous dispersion, 10g of zinc oxide and 40g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2: 1.
Example 4
The embodiment provides an aqueous graphene conductive anticorrosive paint and a preparation method thereof, the steps of which are basically the same as those of embodiment 1, the difference is that the mass fraction of graphene in a graphene aqueous dispersion is different from that of embodiment 1, and the specific steps are as follows:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5h to obtain a mixture.
And carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 10%.
(2) Preparation of component A
50g of water-based epoxy resin, 10g of organic bentonite, 10g of silicon micropowder, 10g of barium sulfate, 20g of water, 1g of dispersing agent PE100, 1g of flatting agent BYK346 and 1g of defoaming agent BYK-028 are mixed and stirred for 2 hours at the rotating speed of 1500rpm to obtain a component A.
(3) Preparation of component B
10g of the graphene aqueous dispersion, 20g of zinc oxide and 50g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2:1 to obtain the coating.
Example 5
The embodiment provides an aqueous graphene conductive anticorrosive paint and a preparation method thereof, the steps of which are basically the same as those of embodiment 1, the difference is that the mass fraction of graphene in a graphene aqueous dispersion is different from that of embodiment 1, and the specific steps are as follows:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5h to obtain a mixture.
And carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 15%.
(2) Preparation of component A
50g of water-based epoxy resin, 10g of organic bentonite, 10g of silicon micropowder, 10g of barium sulfate, 20g of water, 1g of dispersing agent PE100, 1g of flatting agent BYK346 and 1g of defoaming agent BYK-028 are mixed and stirred for 2 hours at the rotating speed of 1500rpm to obtain a component A.
(3) Preparation of component B
10g of the graphene aqueous dispersion, 20g of zinc oxide and 50g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2:1 to obtain the coating.
Example 6
The embodiment provides an aqueous graphene conductive anticorrosive paint and a preparation method thereof, the steps of which are basically the same as those of embodiment 1, and the difference is that in the component B, the mass ratio of the graphene aqueous dispersion to the zinc oxide is different from that of embodiment 1, and the specific steps are as follows:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5h to obtain a mixture.
And carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 5%.
(2) Preparation of component A
50g of water-based epoxy resin, 10g of organic bentonite, 10g of silicon micropowder, 10g of barium sulfate, 20g of water, 1g of dispersing agent PE100, 1g of flatting agent BYK346 and 1g of defoaming agent BYK-028 are mixed and stirred for 2 hours at the rotating speed of 1500rpm to obtain a component A.
(3) Preparation of component B
10g of the graphene aqueous dispersion, 40g of zinc oxide and 50g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2:1 to obtain the coating.
Comparative example 1
The comparative example provides a water-based graphene conductive anticorrosive paint and a preparation method thereof, the steps of which are basically the same as those of example 1, and the difference is only that the preparation method of the graphene aqueous dispersion is different from that of example 1. The method comprises the following specific steps:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water, ethanol and polyvinyl alcohol, and mixing to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 5%.
(2) Preparation of component A
50g of water-based epoxy resin, 10g of organic bentonite, 10g of silicon micropowder, 10g of barium sulfate, 20g of water, 1g of dispersing agent PE100, 1g of flatting agent BYK346 and 1g of defoaming agent BYK-028 are mixed and stirred for 2 hours at the rotating speed of 1500rpm to obtain a component A.
(3) Preparation of component B
10g of the graphene aqueous dispersion, 20g of zinc oxide and 50g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2:1 to obtain the coating.
Comparative example 2
The comparative example provides a water-based graphene conductive anticorrosive paint and a preparation method thereof, the steps of the paint are basically the same as those of example 1, and the difference is only that zinc oxide in the component B is replaced by tin oxide, and the specific steps are as follows:
(1) preparation of graphene aqueous dispersion
Pouring the crystalline flake graphene (800 meshes) into a beaker, adding deionized water and carboxymethyl cellulose, and shearing and dispersing at a high speed for 1.5h to obtain a mixture.
And carrying out high-power ultrasonic treatment on the mixture for 3.5 hours to obtain a uniform graphene aqueous dispersion, wherein the mass fraction of graphene in the graphene aqueous dispersion is 5%.
(2) Preparation of component A
50g of water-based epoxy resin, 10g of organic bentonite, 10g of silicon micropowder, 10g of barium sulfate, 20g of water, 1g of dispersing agent PE100, 1g of flatting agent BYK346 and 1g of defoaming agent BYK-028 are mixed and stirred for 2 hours at the rotating speed of 1500rpm to obtain a component A.
(3) Preparation of component B
10g of the graphene aqueous dispersion, 20g of tin oxide and 50g of aqueous epoxy curing agent are mixed and stirred at the rotating speed of 1500rpm for 2 hours to obtain a component B.
When in use, the component A and the component B are mixed according to the mass ratio of 2:1 to obtain the coating.
Performance testing
1. The adhesion force is tested according to the GB/T1720-;
2. impact resistance was tested according to GB/T1732 + 1993 standard;
3. flexibility is tested according to GB/T1720-79 standard;
4. the salt water resistance is tested according to the GB/T1763-89 standard;
5. gasoline resistance was tested according to GB/T1734 + 1993 standard;
6. the salt spray resistance is tested according to the GB/T1771-91 standard;
7. the acid and alkali resistance is tested according to the GB/T1763 standard;
8. the humidity and heat resistance is tested according to the GB/T1740 standard;
9. the surface resistivity was measured according to the GB13348-92 standard.
The aqueous graphene conductive anticorrosive coatings prepared in the above examples and comparative examples were tested, and the results are shown in tables 1 and 2:
TABLE 1
TABLE 2
With reference to tables 1 and 2, it can be seen from the data of examples 1, 2 and 3 that the contents of the raw materials of component A and component B have a direct influence on the corrosion resistance and conductivity of the coating, and the overall performance of the coatings of examples 1 and 2 is better than that of example 3. It can be seen from the data of examples 1, 4 and 5 that the mass fraction of graphene in the graphene aqueous solution affects the dispersion stability of the graphene in the coating system, and further affects the corrosion resistance and conductivity of the coating, and the overall performance of the coating of example 1 is better than that of examples 4 and 5. From the data of example 1 and example 6, it can be seen that the mass ratio of the graphene aqueous solution to the zinc oxide also has an effect on the corrosion resistance and conductivity of the coating, and the overall performance of the coating of example 1 is better than that of example 6. Further combining with comparative example 1, in the graphene aqueous solution obtained by mixing graphene, deionized water, ethanol and polyvinyl alcohol, the graphene dispersion effect is inferior to that of example 1, and the corrosion resistance and the conductivity of the coating are relatively poor. As can be seen from the data of example 1 and comparative example 2, the matching effect of the graphene aqueous solution and the zinc oxide is better than the matching effect of the graphene aqueous solution and the tin oxide.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. The water-based graphene conductive anticorrosive paint is characterized in that raw materials comprise a component A and a component B;
the component A is mainly prepared from the following raw materials in parts by weight:
40-60 parts of waterborne epoxy resin,
20-60 parts of filler,
2-4 parts of auxiliary agent,
10-20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
5-10 parts of graphene aqueous dispersion,
10-20 parts of zinc oxide,
40-60 parts of a water-based epoxy curing agent;
the preparation method of the graphene aqueous dispersion comprises the following steps:
mixing graphene, carboxymethyl cellulose and water, and shearing and dispersing for 1-2 hours to obtain a mixture;
carrying out ultrasonic treatment on the mixture for 3-4 h;
the weight ratio of the graphene aqueous dispersion to the zinc oxide is 1 (1.5-2).
2. The aqueous graphene conductive anticorrosive paint according to claim 1, wherein the component A is prepared from the following raw materials in parts by weight:
50-60 parts of waterborne epoxy resin,
25-50 parts of filler,
2-4 parts of auxiliary agent,
10-20 parts of water;
the component B is mainly prepared from the following raw materials in parts by weight:
8-10 parts of graphene water dispersion,
15-20 parts of zinc oxide,
50-60 parts of a water-based epoxy curing agent.
3. The aqueous graphene conductive anticorrosive paint according to claim 2, wherein the graphene aqueous dispersion comprises 3-10% by mass of graphene.
4. The aqueous graphene conductive anticorrosive paint according to claim 2, wherein the weight ratio of the graphene aqueous dispersion to the zinc oxide is 1: 2.
5. The aqueous graphene conductive anticorrosive paint according to claim 2, wherein the filler is one or more selected from organic bentonite, silica micropowder and barium sulfate.
6. The aqueous graphene conductive anticorrosive paint according to claim 5, wherein the filler is a mixture of the following components in a mass ratio of 1: (1-3): (1-3) a mixture of organobentonite, fine silica powder and barium sulfate.
7. The aqueous graphene conductive anticorrosive paint according to any one of claims 1 to 6, wherein the aqueous epoxy resin is bisphenol A epoxy resin.
8. The aqueous graphene conductive anticorrosive paint according to any one of claims 1 to 6, wherein the aqueous epoxy curing agent is an amine curing agent.
9. The aqueous graphene conductive anticorrosive paint according to any one of claims 1 to 6, wherein the auxiliary agent is one or more selected from a dispersing agent, a leveling agent and an antifoaming agent.
10. The aqueous graphene conductive anticorrosive paint according to claim 9, wherein the dispersant is PE 100.
11. The aqueous graphene conductive anticorrosive paint according to claim 9, wherein the leveling agent is BYK 346.
12. The aqueous graphene conductive anticorrosive paint according to claim 9, wherein the defoaming agent is BYK-028.
13. The aqueous graphene conductive anticorrosive paint according to any one of claims 1 to 6, wherein the mass ratio of the component A to the component B is (1-3): 1.
14. The preparation method of the aqueous graphene conductive anticorrosive paint according to any one of claims 1 to 13, characterized by comprising the following steps:
mixing the waterborne epoxy resin, the filler, the auxiliary agent and water, and stirring for 1-2 h at the rotating speed of 1000-1500 rpm;
and mixing the graphene aqueous dispersion, the zinc oxide and the water-based epoxy curing agent, and stirring at 1500-2000 rpm for 1-2 h.
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