CN110607112A - Water-based epoxy heavy-duty anticorrosive paint and preparation method thereof - Google Patents

Abstract

The invention relates to a water-based epoxy heavy-duty anticorrosive paint and a preparation method thereof, belonging to the technical field of anticorrosive paint, and the water-based epoxy heavy-duty anticorrosive paint comprises a first component and a second component, wherein the first component comprises the following components in parts by weight: 1 part of modified water-based epoxy emulsion, 0.1-0.3 part of deionized water, 0.005-0.01 part of modified graphene, 1.15-1.56 parts of pigment and filler, 0.02-0.03 part of defoaming agent, 0.01-0.02 part of dispersing agent, 0.01-0.02 part of flatting agent, 0.03-0.05 part of flash rust inhibitor, 0.03-0.05 part of bactericide and 0.01-0.05 part of thickening agent; has good physical and chemical properties, no crack of a 1-degree bending resistant coating, 50cm of impact resistance, more than or equal to 10MPa of adhesive force, and resistance to 5 percent of NaOH solution and 5 percent of H under the normal temperature condition₂SO₄The solution and 5% NaCl coating layer has no bubbling, cracking and falling off after 30 days.

Description

Water-based epoxy heavy-duty anticorrosive paint and preparation method thereof

Technical Field

The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a water-based epoxy heavy-duty anticorrosive coating and a preparation method thereof.

Background

Along with the continuous enhancement of environmental protection consciousness of people, the research and development and the use of the environmental protection coating are more and more paid attention. The water-based anticorrosion paint is a great trend in the development of the current paint industry, and the development of the water-based paint is also greatly promoted in China. Compared with solvent-based coatings, the waterborne coatings greatly reduce the VOC content, even reduce the VOC content to zero, and are real "green" coatings.

Waterborne epoxy coatings have been used in large quantities because of their advantages of good handling properties, good adhesion to most substrates, and ability to cure at room temperature and in humid environments, but they also have their own drawbacks. First, the water-based epoxy coating has poor wettability to steel due to high surface tension of water, and is likely to cause problems of shrinkage and poor adhesion. Secondly, in the process of preparing the water-based epoxy emulsion, a large number of hydrophilic groups are usually introduced into a resin chain segment, so that the crosslinking density of the water-based epoxy coating is greatly reduced, and the adhesive force between the coating and a base material is influenced. Meanwhile, the corrosion resistance of the coating is reduced due to the introduction of a large number of hydrophilic groups and the reduction of crosslinking density. Therefore, the development of a water-based epoxy coating having good adhesion and excellent corrosion resistance has been the focus of research on water-based coatings.

Disclosure of Invention

In view of the above problems, the present invention has been made to provide a water-based epoxy heavy duty paint and a method for preparing the same, which overcome or at least partially solve the above problems.

The embodiment of the invention provides a water-based epoxy heavy-duty anticorrosive paint which comprises a first component and a second component, wherein the first component comprises the following components in parts by weight:

1 part of modified water-based epoxy emulsion

0.1 to 0.3 portion of deionized water

0.005-0.01 part of modified graphene

1.15 to 1.56 portions of pigment and filler

0.02-0.03 portion of defoaming agent

0.01 to 0.02 portion of dispersant

0.01-0.02 part of flatting agent

0.03-0.05 part of flash rust inhibitor

0.03-0.05 part of bactericide

0.01 to 0.05 portion of thickening agent,

the preparation method of the modified water-based epoxy emulsion comprises the following steps:

mixing maleic anhydride and allyl alcohol, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with epoxy resin, hydroquinone and phenol, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with a piperidine catalyst, and carrying out three reactions to obtain a third reactant;

cooling the third reactant, mixing and dissolving the cooled third reactant and a styrene solution to obtain unsaturated epoxy fumaric acid resin;

uniformly mixing the unsaturated epoxy fumaric resin with the waterborne epoxy emulsion to obtain a modified waterborne epoxy emulsion;

the epoxy equivalent of the modified waterborne epoxy emulsion is 240-300 g/eq.

Further, the first component comprises the following components in parts by weight:

1 part of modified water-based epoxy emulsion

0.2 part of deionized water

0.006 part of modified graphene

1.404 parts of pigment and filler

0.025 portions of antifoaming agent

0.015 part of dispersant

0.015 part of flatting agent

0.05 part of flash rust inhibitor

0.05 part of bactericide

0.03 part of thickening agent.

Further, the weight ratio of the maleic anhydride to the allyl alcohol is 5: 2;

the weight ratio of the first reactant, the epoxy resin, the hydroquinone and the phenol is 80-100: 0.02-0.03: 0.4-0.6;

the weight ratio of the second reactant to the piperidine catalyst is 80-100: 0.5-0.6;

the weight ratio of the third reactant to the styrene solution is 3: 2, and the weight percentage of the styrene solution is 60%;

the weight ratio of the unsaturated epoxy fumaric resin to the aqueous epoxy emulsion is 1: 9.

Further, in the primary reaction, the temperature is 80-85 ℃, and the time is 4 hours;

in the secondary reaction, after reacting for 2 hours at the temperature of 80-85 ℃, heating to 120 ℃ at the speed of 8-10 ℃/h, and finishing the secondary reaction;

in the third reaction, the temperature is 160-165 ℃, and the time is 4 hours; the cooling is carried out to a temperature of 105-110 ℃.

Further, the preparation method of the modified graphene comprises the following steps:

mixing the flake graphite with concentrated sulfuric acid, slowly adding potassium permanganate under the stirring condition, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with deionized water, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with hydrogen peroxide, standing, and carrying out three reactions to obtain a third reactant;

carrying out primary filtration, primary washing and primary drying treatment on the third reactant to obtain a graphene sample;

mixing the graphene sample with DMF (dimethyl formamide), and carrying out primary ultrasonic treatment to obtain a suspension;

mixing the suspension with ethylenediamine and dicyclohexylcarbodiimide, and carrying out four-time reaction after secondary ultrasonic treatment to obtain a fourth reactant;

mixing the fourth reactant with an anhydrous solvent, standing and layering to obtain a supernatant and a lower precipitate;

and removing the supernatant, and carrying out secondary filtration, secondary washing and secondary drying treatment on the lower-layer precipitate to obtain the modified graphene.

Further, the weight volume ratio of the crystalline flake graphite to concentrated sulfuric acid is 1 g: 20-25 mL;

in the primary reaction, the temperature is 0-5 ℃ and the time is 90-100 h; the volume ratio of the first reactant to the deionized water is 1-1.5: 2-3;

in the secondary reaction, after the reaction is carried out for 1.5 to 2 hours at the temperature of 30 to 35 ℃, the temperature is increased to 90 to 95 ℃ and the reaction is carried out for 1 to 2 hours; the volume ratio of the second reactant to the hydrogen peroxide is 20-25: 1-1.2, and the weight concentration of the hydrogen peroxide is 30%;

in the third reaction, the temperature is room temperature, and the time is 10-15 h;

in the washing, firstly, hydrochloric acid is used for washing, and then deionized water is used for washing until sulfate ions do not exist, wherein the weight concentration of the hydrochloric acid is 5%; the primary drying temperature is 65-70 ℃;

the weight-volume ratio of the graphene sample to DMF is 1 g: 1000-1500 mL; the primary ultrasonic treatment time is 2.5-3h, and the secondary ultrasonic treatment time is 5-10 min;

the weight-volume ratio of the suspension to the ethylenediamine and the dicyclohexylcarbodiimide is 150-200 mL: 6 g: 1 g;

in the fourth reaction, the temperature is 120 ℃, and the time is 45-50 h; the volume ratio of the fourth reactant to the absolute ethyl alcohol is 3-5: 0.8-1.2.

The standing and layering time is more than or equal to 12 hours, the secondary filtration is carried out by adopting a polytetrafluoroethylene membrane, and the secondary drying temperature is 65-70 ℃.

Further, the pigment and filler comprises the following components in parts by weight:

0.45 to 0.6 portion of barium sulfate

0.3-0.55 part of talcum powder

0.25-0.3 part of iron oxide red

0.1-0.25 part of aluminum tripolyphosphate

0.003 to 0.005 part of fumed silica.

Further, the pigment and filler comprises the following components in parts by weight:

0.5 portion of barium sulfate

0.4 part of talcum powder

0.3 portion of iron oxide red

0.2 part of aluminum tripolyphosphate

0.004 portion of fumed silica.

Further, the weight ratio of the first component to the second component is 1: 0.09-0.1.

Further, the second component includes:

1 part of waterborne epoxy amine curing agent

0.2 part of film-forming assistant.

Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the water-based epoxy heavy-duty anticorrosive paint, which comprises the following steps:

preparing a first component, and preparing raw materials of the first component according to the weight part of the first component;

heating the pigment filler for dewatering to obtain dewatered pigment filler, wherein the heating temperature is 120-180 ℃, and the dewatering time is 10-15 h;

mixing deionized water, a defoaming agent, a dispersing agent, a leveling agent, an anti-flash rust agent and a bactericide, stirring for the first time, adding modified graphene and the pigment and filler for removing water under the condition of the first stirring, continuing the first stirring until the modified graphene and the pigment and filler are uniformly mixed, and grinding to obtain water slurry;

mixing the water slurry with the modified water-based epoxy emulsion, stirring for the second time, and slowly adding a thickening agent under the condition of the second stirring to obtain a first component, wherein the rotation speed of the second stirring is less than or equal to 1000r/min, and the temperature of the second stirring is less than or equal to 60 ℃;

preparing a second component, and preparing raw materials of the second component according to the weight part of the second component;

uniformly mixing the waterborne epoxy amine curing agent with the film-forming additive to obtain a second component;

and uniformly mixing the first component and the second component according to the weight ratio of the first component to the second component to obtain the water-based epoxy heavy anti-corrosion coating.

Based on the same invention concept, the embodiment of the invention also provides application of the water-based epoxy heavy-duty anticorrosive paint, which is applied to corrosion prevention of inner and outer tank bodies of the steel petroleum storage tank.

One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:

(1) the water-based epoxy heavy-duty anticorrosive paint provided by the embodiment of the invention is prepared by blending water-based epoxy resin emulsion and unsaturated epoxy fumaric acid resin. The existence of carboxyl in the epoxy fumaric acid resin increases the polarity of the resin emulsion and improves the adhesive force of the coating to the metal surface. The introduced unsaturated bond participates in the crosslinking reaction of the water-based epoxy coating, and the crosslinking density of the coating is improved. The improvement of the crosslinking density is beneficial to improving the adhesive force of the coating to the matrix and the corrosion resistance of the coating. Finally, the blending unsaturated epoxy fumaric resin can improve the glass transition temperature Tg of the water-based epoxy coating, thereby improving the hardness and corrosion resistance of the coating.

(2) The water-based epoxy heavy-duty anticorrosive coating provided by the embodiment of the invention uses the graphene which is prepared and modified by self, and the problem that the graphene is difficult to disperse in the coating is well solved. The graphene has the advantages of good thermal stability, chemical medium resistance, good thermal conductivity, high hardness and the like, and the heat resistance, the shock resistance and the wear resistance of the coating can be improved by adding the graphene into the coating. Meanwhile, the flaky graphene can be arranged in an oriented manner in the coating drying process and overlapped with each other, so that H is effectively shielded₂O、CO₂、Cl^-1And the like, so that the coating cannot directly permeate the scales and only can be permeated in a roundabout manner, the permeation path is prolonged, a labyrinth effect is realized, capillary micro-channels in the coating are cut off, the permeability is reduced, and the corrosion resistance and the cathode stripping resistance of the coating are improved.

(3) The water-based epoxy heavy-duty coating provided by the embodiment of the invention uses the anticorrosion filler aluminum triphosphate. The aluminum tripolyphosphate has a double anti-rust mechanism, and the tripolyphosphate ions (P) obtained by depolymerization reaction₃O₁₀ ^5-) For Fe³⁺The ions have strong chelating force, can form a passive film on the surface and have strong inhibiting effect on the corrosion of metal.

(4) The water-based epoxy heavy-duty anticorrosive coating provided by the embodiment of the invention has good physical and chemical properties, a 1-degree bending resistant coating has no crack, the impact resistance is 50cm, the adhesive force is more than or equal to 10MPa, and the coating can resist 5% NaOH solution and 5% H solution at normal temperature₂SO₄The solution and 5% NaCl coating layer has no bubbling, cracking and falling off after 30 days.

(5) The water-based epoxy heavy-duty anticorrosive paint provided by the embodiment of the invention can be used for internal and external corrosion prevention of a steel petroleum storage tank.

Detailed Description

The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.

Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, 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. If there is a conflict, the present specification will control.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

The following will describe the waterborne epoxy heavy-duty anticorrosive coating and the preparation method thereof in detail with reference to specific examples.

Example 1

The preparation method of the water-based epoxy heavy-duty anticorrosive paint comprises the following steps of:

step (1), 0.6 part of barium sulfate, 0.5 part of talcum powder, 0.25 part of iron oxide red, 0.2 part of aluminum tripolyphosphate and 0.003 part of fumed silica are placed in a high-temperature box at 150 ℃ to be heated and dehydrated for 12 hours, and the pigment and filler of the coating is obtained;

step (2), mixing 0.2 part of deionized water, 0.02 part of defoaming agent, 0.015 part of dispersing agent, 0.015 part of flatting agent, 0.05 part of anti-flash rust agent and 0.05 part of bactericide, stirring at normal temperature, adding coating pigment and filler and 0.005 part of modified graphene under the stirring condition, continuing stirring at high speed for 30-40min to uniformly disperse the components, and then grinding for 0.5-1 hour by using a grinding machine to obtain water slurry;

step (3), mixing 1 part of modified waterborne epoxy resin emulsion and the obtained water slurry, uniformly stirring, and slowly adding 0.03 part of thickening agent in the stirring process to obtain a first component of the waterborne epoxy heavy-duty anticorrosive paint;

step (4), mixing 1 part of waterborne epoxy amine curing agent and 0.2 part of film-forming assistant, and uniformly stirring to obtain a second component of the waterborne epoxy heavy-duty anticorrosive paint;

and (5) uniformly mixing the first component and the second component in a weight ratio of 1: 0.1 to obtain the water-based epoxy heavy-duty anticorrosive paint.

The properties of the waterborne epoxy heavy-duty anticorrosive coating prepared in example 1 were tested, and the properties of the coating and the coating thereof are shown in table 1.

Table 1 example 1 properties of the waterborne epoxy heavy duty coating prepared in example 1

Example 2

The preparation method of the water-based epoxy heavy-duty anticorrosive paint comprises the following steps of:

step (1), 0.6 part of barium sulfate, 0.4 part of talcum powder, 0.3 part of iron oxide red, 0.2 part of aluminum tripolyphosphate and 0.004 part of fumed silica are placed in a high-temperature box at 150 ℃ to be heated and dewatered for 12 hours to obtain a coating pigment and filler;

step (2), mixing 0.2 part of deionized water, 0.02 part of defoaming agent, 0.015 part of dispersing agent, 0.015 part of flatting agent, 0.05 part of anti-flash rust agent and 0.05 part of bactericide, stirring at normal temperature, adding coating pigment and filler and 0.005 part of modified graphene under the stirring condition, continuing stirring at high speed for 30-40min to uniformly disperse the components, and then grinding for 0.5-1 hour by using a grinding machine to obtain water slurry;

step (3), mixing 1 part of modified waterborne epoxy resin emulsion and the obtained water slurry, uniformly stirring, and slowly adding 0.03 part of thickening agent in the stirring process to obtain a first component of the waterborne epoxy heavy-duty anticorrosive paint;

step (4), mixing 1 part of waterborne epoxy amine curing agent and 0.2 part of film-forming assistant, and uniformly stirring to obtain a second component of the waterborne epoxy heavy-duty anticorrosive paint;

and (5) uniformly mixing the first component and the second component in a weight ratio of 1:0.09 to obtain the water-based epoxy heavy-duty anticorrosive paint.

The properties of the waterborne epoxy heavy-duty anticorrosive coating prepared in example 2 were tested, and the properties of the coating and the coating thereof are shown in table 2.

Table 2 example 2 properties of the waterborne epoxy heavy duty coating prepared in example 2

Example 3

The water-based epoxy heavy-duty anticorrosive paint comprises a first component and a second component, wherein the first component comprises the following components in parts by weight:

1 part of modified water-based epoxy emulsion

0.1 part of deionized water

0.005 part of modified graphene

0.45 portion of barium sulfate

0.3 part of talcum powder

0.25 portion of iron oxide red

0.1 part of aluminum tripolyphosphate

Fumed silica 0.003 part.

0.02 portion of defoaming agent

0.01 part of dispersant

0.01 part of flatting agent

0.03 part of flash rust inhibitor

0.03 portion of bactericide

0.01 part of a thickening agent, namely,

the second component includes:

1 part of waterborne epoxy amine curing agent

0.2 part of a film-forming auxiliary agent,

the weight ratio of the first component to the second component is 1:0.09,

the preparation method of the modified water-based epoxy emulsion comprises the following steps:

mixing maleic anhydride and allyl alcohol, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with epoxy resin, hydroquinone and phenol, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with a piperidine catalyst, and carrying out three reactions to obtain a third reactant;

cooling the third reactant, mixing and dissolving the cooled third reactant and a styrene solution to obtain unsaturated epoxy fumaric acid resin;

uniformly mixing the unsaturated epoxy fumaric resin with the waterborne epoxy emulsion to obtain a modified waterborne epoxy emulsion;

the epoxy equivalent of the modified waterborne epoxy emulsion is 240 g/eq.

Specifically, the weight ratio of the maleic anhydride to the allyl alcohol is 5: 2;

the weight ratio of the first reactant, the epoxy resin, the hydroquinone and the phenol is 80: 0.02: 0.4;

the weight ratio of the second reactant to the piperidine catalyst is 80: 0.5;

the weight ratio of the third reactant to the styrene solution is 3: 2, and the weight percentage of the styrene solution is 60%;

the weight ratio of the unsaturated epoxy fumaric resin to the aqueous epoxy emulsion is 1: 9.

Specifically, in the primary reaction, the temperature is 80 ℃, and the time is 4 hours;

in the secondary reaction, after reacting for 2 hours at the temperature of 80 ℃, heating to 120 ℃ at the speed of 8 ℃/h, and finishing the secondary reaction;

in the third reaction, the temperature is 160 ℃, and the time is 4 hours; the cooling was carried out to a temperature of 105 ℃.

Specifically, the preparation method of the modified graphene comprises the following steps:

mixing the flake graphite with concentrated sulfuric acid, slowly adding potassium permanganate under the stirring condition, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with deionized water, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with hydrogen peroxide, standing, and carrying out three reactions to obtain a third reactant;

carrying out primary filtration, primary washing and primary drying treatment on the third reactant to obtain a graphene sample;

mixing the graphene sample with DMF (dimethyl formamide), and carrying out primary ultrasonic treatment to obtain a suspension;

mixing the suspension with ethylenediamine and dicyclohexylcarbodiimide, and carrying out four-time reaction after secondary ultrasonic treatment to obtain a fourth reactant;

mixing the fourth reactant with an anhydrous solvent, standing and layering to obtain a supernatant and a lower precipitate;

and removing the supernatant, and carrying out secondary filtration, secondary washing and secondary drying treatment on the lower-layer precipitate to obtain the modified graphene.

Specifically, the weight volume ratio of the crystalline flake graphite to concentrated sulfuric acid is 1 g: 20 mL;

in the primary reaction, the temperature is 0 ℃ and the time is 90 hours; the volume ratio of the first reactant to the deionized water is 1: 2;

in the secondary reaction, after the reaction is carried out for 1.5h at the temperature of 30 ℃, the temperature is raised to 90 ℃ for reaction for 1 h; the volume ratio of the second reactant to the hydrogen peroxide is 20: 1, and the weight concentration of the hydrogen peroxide is 30%;

in the third reaction, the temperature is room temperature, and the time is 10 hours;

in the washing, firstly, hydrochloric acid is used for washing, and then deionized water is used for washing until sulfate ions do not exist, wherein the weight concentration of the hydrochloric acid is 5%; the primary drying temperature is 65 ℃;

the weight-volume ratio of the graphene sample to DMF is 1 g: 1000 mL; the primary ultrasonic treatment time is 2.5h, and the secondary ultrasonic treatment time is 5 min;

the weight volume ratio of the suspension to the ethylenediamine to the dicyclohexylcarbodiimide is 150mL to 6g to 1 g;

in the fourth reaction, the temperature is 120 ℃, and the time is 45 h; the volume ratio of the fourth reactant to the absolute ethyl alcohol is 3: 0.8.

The standing and layering time is more than or equal to 12 hours, the secondary filtration is carried out by adopting a polytetrafluoroethylene membrane, and the secondary drying temperature is 65 ℃.

Example 4

The water-based epoxy heavy-duty anticorrosive paint comprises a first component and a second component, wherein the first component comprises the following components in parts by weight:

1 part of modified water-based epoxy emulsion

0.3 portion of deionized water

0.01 part of modified graphene

0.6 portion of barium sulfate

0.55 part of talcum powder

0.3 portion of iron oxide red

0.25 part of aluminum tripolyphosphate

Fumed silica 0.005 part

0.03 portion of defoaming agent

0.02 portion of dispersant

0.02 part of flatting agent

0.05 part of flash rust inhibitor

0.05 part of bactericide

0.05 part of a thickening agent, namely,

the second component includes:

1 part of waterborne epoxy amine curing agent

0.2 part of a film-forming auxiliary agent,

the weight ratio of the first component to the second component is 1:0.09-0.1,

the preparation method of the modified water-based epoxy emulsion comprises the following steps:

mixing maleic anhydride and allyl alcohol, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with epoxy resin, hydroquinone and phenol, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with a piperidine catalyst, and carrying out three reactions to obtain a third reactant;

cooling the third reactant, mixing and dissolving the cooled third reactant and a styrene solution to obtain unsaturated epoxy fumaric acid resin;

uniformly mixing the unsaturated epoxy fumaric resin with the waterborne epoxy emulsion to obtain a modified waterborne epoxy emulsion;

the epoxy equivalent of the modified waterborne epoxy emulsion is 300 g/eq.

Specifically, the weight ratio of the maleic anhydride to the allyl alcohol is 5: 2;

the weight ratio of the first reactant, the epoxy resin, the hydroquinone and the phenol is 100: 0.03: 0.6;

the weight ratio of the second reactant to the piperidine catalyst is 100: 0.6;

the weight ratio of the third reactant to the styrene solution is 3: 2, and the weight percentage of the styrene solution is 60%;

the weight ratio of the unsaturated epoxy fumaric resin to the aqueous epoxy emulsion is 1: 9.

Specifically, in the primary reaction, the temperature is 85 ℃ and the time is 4 hours;

in the secondary reaction, after reacting for 2 hours at the temperature of 85 ℃, heating to 120 ℃ at the speed of 10 ℃/h, and finishing the secondary reaction;

in the third reaction, the temperature is 165 ℃ and the time is 4 hours; the cooling was carried out to a temperature of 110 ℃.

Specifically, the preparation method of the modified graphene comprises the following steps:

mixing the flake graphite with concentrated sulfuric acid, slowly adding potassium permanganate under the stirring condition, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with deionized water, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with hydrogen peroxide, standing, and carrying out three reactions to obtain a third reactant;

carrying out primary filtration, primary washing and primary drying treatment on the third reactant to obtain a graphene sample;

mixing the graphene sample with DMF (dimethyl formamide), and carrying out primary ultrasonic treatment to obtain a suspension;

mixing the suspension with ethylenediamine and dicyclohexylcarbodiimide, and carrying out four-time reaction after secondary ultrasonic treatment to obtain a fourth reactant;

mixing the fourth reactant with an anhydrous solvent, standing and layering to obtain a supernatant and a lower precipitate;

and removing the supernatant, and carrying out secondary filtration, secondary washing and secondary drying treatment on the lower-layer precipitate to obtain the modified graphene.

Specifically, the weight volume ratio of the crystalline flake graphite to concentrated sulfuric acid is 1 g: 25 mL;

in the primary reaction, the temperature is 5 ℃ and the time is 100 hours; the volume ratio of the first reactant to the deionized water is 1: 2;

in the secondary reaction, after reacting for 2 hours at the temperature of 35 ℃, heating to 95 ℃ and reacting for 2 hours; the volume ratio of the second reactant to the hydrogen peroxide is 25: 1.2, and the weight concentration of the hydrogen peroxide is 30%;

in the third reaction, the temperature is room temperature, and the time is 15 hours;

in the washing, firstly, hydrochloric acid is used for washing, and then deionized water is used for washing until sulfate ions do not exist, wherein the weight concentration of the hydrochloric acid is 5%; the primary drying temperature is 70 ℃;

the weight-volume ratio of the graphene sample to DMF is 1 g: 1500 mL; the primary ultrasonic treatment time is 3 hours, and the secondary ultrasonic treatment time is 10 min;

the weight volume ratio of the suspension to the ethylenediamine to the dicyclohexylcarbodiimide is 200mL to 6g to 1 g;

in the fourth reaction, the temperature is 120 ℃, and the time is 50 h; the volume ratio of the fourth reactant to the absolute ethyl alcohol is 5: 1.2.

The standing and layering time is more than or equal to 12 hours, the secondary filtration is carried out by adopting a polytetrafluoroethylene membrane, and the secondary drying temperature is 70 ℃.

Example 5

A preparation method of a water-based epoxy heavy-duty anticorrosive paint comprises the following steps:

preparing a first component, and preparing raw materials of the first component according to the weight part of the first component;

heating the pigment filler for dewatering to obtain dewatered pigment filler, wherein the heating temperature is 120 ℃, and the dewatering time is 10 hours;

mixing deionized water, a defoaming agent, a dispersing agent, a leveling agent, an anti-flash rust agent and a bactericide, stirring for the first time, adding modified graphene and the pigment and filler for removing water under the condition of the first stirring, continuing the first stirring until the modified graphene and the pigment and filler are uniformly mixed, and grinding to obtain water slurry;

mixing the water slurry with the modified water-based epoxy emulsion, stirring for the second time, and slowly adding a thickening agent under the condition of the second stirring to obtain a first component, wherein the rotation speed of the second stirring is 1000r/min, and the temperature of the second stirring is 60 ℃;

preparing a second component, and preparing raw materials of the second component according to the weight part of the second component;

uniformly mixing the waterborne epoxy amine curing agent with the film-forming additive to obtain a second component;

and uniformly mixing the first component and the second component according to the weight ratio of the first component to the second component to obtain the water-based epoxy heavy anti-corrosion coating.

Example 6

A preparation method of a water-based epoxy heavy-duty anticorrosive paint comprises the following steps:

preparing a first component, and preparing raw materials of the first component according to the weight part of the first component;

heating the pigment filler for dewatering to obtain dewatered pigment filler, wherein the heating temperature is 180 ℃, and the dewatering time is 15 hours;

mixing deionized water, a defoaming agent, a dispersing agent, a leveling agent, an anti-flash rust agent and a bactericide, stirring for the first time, adding modified graphene and the pigment and filler for removing water under the condition of the first stirring, continuing the first stirring until the modified graphene and the pigment and filler are uniformly mixed, and grinding to obtain water slurry;

mixing the water slurry with the modified water-based epoxy emulsion,

carrying out secondary stirring, and slowly adding a thickening agent under the secondary stirring condition to obtain a first component, wherein the secondary stirring speed is 800r/min, and the secondary stirring temperature is 50 ℃;

preparing a second component, and preparing raw materials of the second component according to the weight part of the second component;

uniformly mixing the waterborne epoxy amine curing agent with the film-forming additive to obtain a second component;

and uniformly mixing the first component and the second component according to the weight ratio of the first component to the second component to obtain the water-based epoxy heavy anti-corrosion coating.

Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.

It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The water-based epoxy heavy-duty anticorrosive paint is characterized by comprising a first component and a second component, wherein the first component comprises the following components in parts by weight:

1 part of modified water-based epoxy emulsion

0.1 to 0.3 portion of deionized water

0.005-0.01 part of modified graphene

1.15 to 1.56 portions of pigment and filler

0.02-0.03 portion of defoaming agent

0.01 to 0.02 portion of dispersant

0.01-0.02 part of flatting agent

0.03-0.05 part of flash rust inhibitor

0.03-0.05 part of bactericide

0.01 to 0.05 portion of thickening agent,

the preparation method of the modified water-based epoxy emulsion comprises the following steps:

mixing maleic anhydride and allyl alcohol, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with epoxy resin, hydroquinone and phenol, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with a piperidine catalyst, and carrying out three reactions to obtain a third reactant;

cooling the third reactant, mixing and dissolving the cooled third reactant and a styrene solution to obtain unsaturated epoxy fumaric acid resin;

uniformly mixing the unsaturated epoxy fumaric resin with the waterborne epoxy emulsion to obtain a modified waterborne epoxy emulsion;

the epoxy equivalent of the modified waterborne epoxy emulsion is 240-300 g/eq.

2. The water-based epoxy heavy-duty anticorrosive coating according to claim 1, wherein the first component comprises, in parts by weight:

1 part of modified water-based epoxy emulsion

0.2 part of deionized water

0.006 part of modified graphene

1.404 parts of pigment and filler

0.025 portions of antifoaming agent

0.015 part of dispersant

0.015 part of flatting agent

0.05 part of flash rust inhibitor

0.05 part of bactericide

0.03 part of thickening agent.

3. The water-based epoxy heavy-duty coating according to claim 1 or 2, wherein the weight ratio of maleic anhydride and allyl alcohol is 5: 2;

the weight ratio of the first reactant to the epoxy resin to the hydroquinone to the phenol is 80-100: 80-100: 0.02-0.03: 0.4-0.6;

the weight ratio of the second reactant to the piperidine catalyst is 80-100: 0.5-0.6;

the weight ratio of the third reactant to the styrene solution is 3: 2, the weight percentage of the styrene solution is 60 percent;

the weight ratio of the unsaturated epoxy fumaric resin to the aqueous epoxy emulsion is 1: 9.

4. The water-based epoxy heavy-duty anticorrosive paint according to claim 1 or 2, characterized in that in the first reaction, the temperature is 80-85 ℃ and the time is 4 h;

in the secondary reaction, after reacting for 2 hours at the temperature of 80-85 ℃, heating to 120 ℃ at the speed of 8-10 ℃/h, and finishing the secondary reaction;

in the third reaction, the temperature is 160-165 ℃, and the time is 4 hours; the cooling is carried out to a temperature of 105-110 ℃.

5. The water-based epoxy heavy-duty anticorrosive coating as claimed in claim 1, wherein the preparation method of the modified graphene comprises:

mixing the flake graphite with concentrated sulfuric acid, slowly adding potassium permanganate under the stirring condition, and carrying out primary reaction to obtain a first reactant;

mixing the first reactant with deionized water, and carrying out secondary reaction to obtain a second reactant;

mixing the second reactant with hydrogen peroxide, standing, and carrying out three reactions to obtain a third reactant;

carrying out primary filtration, primary washing and primary drying treatment on the third reactant to obtain a graphene sample;

mixing the graphene sample with DMF (dimethyl formamide), and carrying out primary ultrasonic treatment to obtain a suspension;

mixing the suspension with ethylenediamine and dicyclohexylcarbodiimide, and carrying out four-time reaction after secondary ultrasonic treatment to obtain a fourth reactant;

mixing the fourth reactant with an anhydrous solvent, standing and layering to obtain a supernatant and a lower precipitate;

and removing the supernatant, and carrying out secondary filtration, secondary washing and secondary drying treatment on the lower-layer precipitate to obtain the modified graphene.

6. The water-based epoxy heavy-duty anticorrosive coating as claimed in claim 5, wherein the weight-to-volume ratio of the crystalline flake graphite to concentrated sulfuric acid is 1 g: 20-25 mL;

in the primary reaction, the temperature is 0-5 ℃ and the time is 90-100 h; the volume ratio of the first reactant to the deionized water is 1-1.5: 2-3;

in the secondary reaction, after the reaction is carried out for 1.5 to 2 hours at the temperature of 30 to 35 ℃, the temperature is increased to 90 to 95 ℃ and the reaction is carried out for 1 to 2 hours; the volume ratio of the second reactant to the hydrogen peroxide is 20-25: 1-1.2, wherein the weight concentration of the hydrogen peroxide is 30%;

in the third reaction, the temperature is room temperature, and the time is 10-15 h;

in the washing, firstly, hydrochloric acid is used for washing, and then deionized water is used for washing until sulfate ions do not exist, wherein the weight concentration of the hydrochloric acid is 5%; the primary drying temperature is 65-70 ℃;

the weight-volume ratio of the graphene sample to DMF is 1 g: 1000-; the primary ultrasonic treatment time is 2.5-3h, and the secondary ultrasonic treatment time is 5-10 min;

the weight-volume ratio of the suspension to the ethylenediamine and the dicyclohexylcarbodiimide was 150-200 mL: 6 g: 1g of a compound;

in the fourth reaction, the temperature is 120 ℃, and the time is 45-50 h; the volume ratio of the fourth reactant to the absolute ethyl alcohol is 3-5: 0.8-1.2;

the standing and layering time is more than or equal to 12 hours, the secondary filtration is carried out by adopting a polytetrafluoroethylene membrane, and the secondary drying temperature is 65-70 ℃.

7. The water-based epoxy heavy-duty paint as claimed in claim 1, wherein said pigment and filler comprises, in parts by weight:

0.45 to 0.6 portion of barium sulfate

0.3-0.55 part of talcum powder

0.25-0.3 part of iron oxide red

0.1-0.25 part of aluminum tripolyphosphate

0.003 to 0.005 part of fumed silica.

8. The water-based epoxy heavy-duty anticorrosive coating as claimed in claim 1, wherein the weight ratio of the first component to the second component is 1: 0.09-0.1.

9. The water-based epoxy heavy duty coating of claim 1, wherein said second component comprises:

1 part of waterborne epoxy amine curing agent

0.2 part of film-forming assistant.

10. A method for preparing a water-based epoxy heavy-duty coating, which is used for preparing the water-based epoxy heavy-duty coating as claimed in claims 1 to 9, and is characterized by comprising the following steps:

preparing a first component, and preparing raw materials of the first component according to the weight part of the first component;

heating the pigment filler for dewatering to obtain dewatered pigment filler, wherein the heating temperature is 120-180 ℃, and the dewatering time is 10-15 h;

mixing deionized water, a defoaming agent, a dispersing agent, a leveling agent, an anti-flash rust agent and a bactericide, stirring for the first time, adding modified graphene and the pigment and filler for removing water under the condition of the first stirring, continuing the first stirring until the modified graphene and the pigment and filler are uniformly mixed, and grinding to obtain water slurry;

mixing the water slurry with the modified water-based epoxy emulsion, stirring for the second time, and slowly adding a thickening agent under the condition of the second stirring to obtain a first component, wherein the rotation speed of the second stirring is less than or equal to 1000r/min, and the temperature of the second stirring is less than or equal to 60 ℃;

preparing a second component, and preparing raw materials of the second component according to the weight part of the second component;

uniformly mixing the waterborne epoxy amine curing agent with the film-forming additive to obtain a second component;

and uniformly mixing the first component and the second component according to the weight ratio of the first component to the second component to obtain the water-based epoxy heavy anti-corrosion coating.