CN110791167A

CN110791167A - Graphene heavy-duty anticorrosive coating, preparation method thereof and heavy-duty anticorrosive coating

Info

Publication number: CN110791167A
Application number: CN201910525847.4A
Authority: CN
Inventors: 温世峰; 马嘉呈; 冯涛; 元辛; 张子濛; 岳珠峰
Original assignee: Northwestern Polytechnical University
Current assignee: Northwestern Polytechnical University
Priority date: 2019-06-18
Filing date: 2019-06-18
Publication date: 2020-02-14

Abstract

The invention provides a graphene heavy anti-corrosion coating, a preparation method thereof and a heavy anti-corrosion coating, and belongs to the technical field of corrosion prevention. The graphene heavy anti-corrosion coating comprises a resin system and a curing agent system, and is characterized in that the resin system comprises, by mass, 0.82-1.5 parts of modified graphene, 70-80 parts of epoxy resin, 13-28 parts of a first organic solvent, 1-2 parts of an adhesive and 5-7 parts of a leveling agent; wherein the mass ratio of the curing agent system to the resin system is 3.5-4.5: 1. the heavy anti-corrosion coating formed by the graphene heavy anti-corrosion coating has good anti-corrosion performance and mechanical property.

Description

Graphene heavy-duty anticorrosive coating, preparation method thereof and heavy-duty anticorrosive coating

Technical Field

The disclosure relates to the technical field of corrosion prevention, and in particular relates to a graphene heavy-duty anticorrosive coating, a preparation method thereof and a heavy-duty anticorrosive coating.

Background

Metal structures are often subjected to various corrosion factors in exposed environments, and without proper protection, the metal structures may corrode and their function may be affected. Epoxy coatings are widely used as an important means of metal corrosion protection. However, when an epoxy resin coating is prepared from an epoxy resin coating, the volatilization of the organic solvent can cause micro-pores invisible to the naked eye on the epoxy resin coating, and the corrosion resistance of the epoxy resin coating is reduced.

The above information disclosed in the background section is only for enhancement of understanding of the background of the present disclosure and therefore it may contain information that does not constitute prior art that is known to a person of ordinary skill in the art.

Disclosure of Invention

The invention aims to provide a graphene heavy-duty anticorrosive coating, a preparation method thereof and a heavy-duty anticorrosive coating, and the anticorrosive property and the mechanical property of the heavy-duty anticorrosive coating formed by the graphene heavy-duty anticorrosive coating are improved.

In order to achieve the purpose, the technical scheme adopted by the disclosure is as follows:

according to a first aspect of the present disclosure, there is provided a graphene heavy duty anticorrosive coating comprising a resin system and a curing agent system; the resin system comprises, by mass, 0.82-1.5 parts of modified graphene, 70-80 parts of epoxy resin, 13-28 parts of a first organic solvent, 1-2 parts of an adhesive and 5-7 parts of a leveling agent; wherein the mass ratio of the curing agent system to the resin system is 3.5-4.5: 1.

in an exemplary embodiment of the present disclosure, the modified graphene is a polymer surface-modified graphene, and the polymer includes one or more of polyvinylpyrrolidone, polypyrrole, polythiophene, and polyaniline.

In an exemplary embodiment of the present disclosure, in the graphene surface-modified by the polymer, a mass ratio of the polymer to the graphene is 0.5-0.64: 1.

In an exemplary embodiment of the present disclosure, the epoxy resin includes one or more of a bisphenol F type epoxy resin, a silicone epoxy resin, a novolac epoxy resin, and a glycerin epoxy resin.

In one exemplary embodiment of the present disclosure, the binder is gamma- (2, 3-glycidoxy) propyl trimethoxysilane.

In an exemplary embodiment of the present disclosure, the curing agent system includes gamma-aminopropyltriethoxysilane and a second organic solvent, and a mass ratio of the gamma-aminopropyltriethoxysilane to the second organic solvent is 1.2-1.9: 1.

According to a second aspect of the present disclosure, a preparation method of a graphene heavy anti-corrosion coating is provided, and the preparation method of the graphene heavy anti-corrosion coating comprises a step of preparing a resin system and a step of preparing a curing agent system, wherein the mass ratio of the curing agent system to the resin system is 3.5-4.5: 1; wherein, preparing the resin system comprises:

preparing modified graphene;

uniformly mixing 0.82-1.5 parts by mass of modified graphene, 70-80 parts by mass of epoxy resin and 13-28 parts by mass of a first organic solvent to obtain a first mixture;

uniformly mixing the first mixture, 1-2 parts by mass of an adhesive and 5-7 parts by mass of a flatting agent to obtain a second mixture;

and carrying out ultrasonic treatment on the second mixture to obtain a resin system.

In one exemplary embodiment of the present disclosure, the modified graphene is a polymer surface-modified graphene; the preparation of the modified graphene comprises:

uniformly mixing graphene and a dispersing solvent, and then carrying out ultrasonic treatment to obtain a graphene dispersion liquid;

dissolving a polymer in a dispersion solvent to obtain a polymer solution;

uniformly mixing the graphene dispersion liquid and the polymer solution to obtain a third mixture;

and removing the dispersion solvent in the third mixture to obtain the polymer surface modified graphene.

In an exemplary embodiment of the present disclosure, when the graphene and the dispersing solvent are uniformly mixed and then subjected to ultrasonic treatment, the ultrasonic frequency is 1 to 2MHz, and the ultrasonic time is 10 to 40 min.

According to a third aspect of the present disclosure, a heavy-duty anticorrosion coating is provided, which is formed from the graphene heavy-duty anticorrosion paint described above.

According to the graphene heavy-duty anticorrosive coating, the preparation method thereof and the heavy-duty anticorrosive coating, when the heavy-duty anticorrosive coating is formed, due to the fact that graphene has a large specific surface area, the defect of micro holes in the heavy-duty anticorrosive coating can be repaired, corrosion factors are prevented from permeating, and compactness and anticorrosive capacity of the heavy-duty anticorrosive coating are improved. Moreover, the graphene has excellent conductivity, so that the graphene is beneficial to forming a compact passivation layer on the surface of the metal substrate, and the corrosion resistance of the metal is further improved. Experiments prove that compared with an epoxy resin coating without modified graphene, a heavy anti-corrosion coating formed by the graphene heavy anti-corrosion coating provided by the disclosure has stronger adhesive force, stronger flexibility, stronger impact resistance and salt spray resistance, and the anti-corrosion performance and the mechanical property of the heavy anti-corrosion coating are obviously improved.

Detailed Description

The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.

The present disclosure provides a graphene heavy duty anticorrosive coating comprising a resin system and a curing agent system. The resin system comprises, by mass, 0.82-1.5 parts of modified graphene, 70-80 parts of epoxy resin, 13-28 parts of a first organic solvent, 1-2 parts of an adhesive and 5-7 parts of a leveling agent; wherein the mass ratio of the curing agent system to the resin system is 3.5-4.5: 1.

when the graphene heavy-duty anticorrosive coating is formed, due to the fact that graphene has a large specific surface area, the defect of a micro hole in the heavy-duty anticorrosive coating can be repaired, corrosion factors are prevented from permeating, and compactness and anticorrosive capacity of the heavy-duty anticorrosive coating are improved. Moreover, the graphene has excellent conductivity, so that the graphene is beneficial to forming a compact passivation layer on the surface of the metal substrate, and the corrosion resistance of the metal is further improved. Experiments prove that compared with an epoxy resin coating without modified graphene, a heavy anti-corrosion coating formed by the graphene heavy anti-corrosion coating provided by the disclosure has stronger adhesive force, stronger flexibility, stronger impact resistance and salt spray resistance, and the anti-corrosion performance and the mechanical property of the heavy anti-corrosion coating are obviously improved.

The modified graphene can be polymer surface modified graphene. The graphene with the modified polymer surface avoids modifying the graphene surface by using a grafting method, so that the complete structure of the graphene is retained to the maximum extent, the excellent performance of the graphene is retained, and the performance of the graphene heavy anti-corrosion coating can be effectively improved. When the graphene is modified by the polymer, the mass ratio of the polymer to the graphene can be 0.5-0.64: 1.

In an embodiment, in the polymer surface-modified graphene, the polymer may include one or more of polyvinylpyrrolidone, polypyrrole, polythiophene, and polyaniline.

It is to be understood that, in the preparation of the resin system, the modified graphene used may be modified graphene obtained by purifying or completely removing a solvent, or may be modified graphene mixed with a component such as a solvent, and the like, and the disclosure is not particularly limited thereto. When the resin system is prepared by using the mixture containing the modified graphene, the charged mass parts of the mixture may be calculated from the mass parts of the modified graphene and the content of the modified graphene in the mixture, and the resin system may be prepared by using the mixture in accordance with the charged mass parts.

In one embodiment, the epoxy resin may include one or more of an epoxy resin including bisphenol F type epoxy resin, silicone epoxy resin, novolac epoxy resin, and glycerin epoxy resin.

In one embodiment, the first organic solvent may be a single solvent or a mixture of a plurality of different solvents. It is to be understood that, when the first solvent is a mixture of a plurality of different solvents, in preparing the resin system, the plurality of different solvents may be previously mixed to be the first solvent and then the first solvent may be added to the preparation system; it is also possible to add a plurality of different solvents to the preparation system separately, and the disclosure is not limited thereto.

For example, the first solvent may include n-butanol and butyl acetate. Wherein, when 13-28 parts by mass of the first organic solvent is obtained, the mass part of the n-butyl alcohol can be 4-8 parts, and the mass part of the butyl acetate can be 9-20 parts.

In one embodiment, the adhesive can be KH-560, namely gamma- (2, 3-glycidoxy) propyl trimethoxy silane, and is used for enhancing the adhesive capacity of epoxy resin, improving the performance of the graphene heavy-duty anticorrosive coating and improving the anticorrosive performance and mechanical property of an anticorrosive coating prepared from the graphene heavy-duty anticorrosive coating.

In one embodiment, the leveling agent can be BYK-3700 or other leveling agents.

The curing agent system can comprise a curing agent and a second organic solvent, wherein the mass ratio of the curing agent to the second organic solvent can be 1.2-1.9: 1.

In one embodiment, the curing agent may be gamma-Aminopropyltriethoxysilane (AMEO), such as Dynasylan AMEO.

In an embodiment, the second organic solvent may include one or more of n-butanol, butyl acetate, and ethylene glycol.

In one embodiment, the mass ratio of the curing agent system to the resin system may be 4: 1.

The preparation method comprises the steps of preparing a resin system and preparing a curing agent system, wherein the mass ratio of the curing agent system to the resin system is 3.5-4.5: 1;

wherein preparing the resin system may comprise:

preparing modified graphene;

According to the preparation method of the graphene heavy anti-corrosion coating provided by the disclosure, the prepared graphene heavy anti-corrosion coating is the same as the graphene heavy anti-corrosion coating described in the embodiment of the graphene heavy anti-corrosion coating, and therefore, the graphene heavy anti-corrosion coating has the same or similar beneficial effects, and the details of the disclosure are not repeated.

In one embodiment, the modified graphene is a polymer surface modified graphene; the preparation of the modified graphene comprises:

dissolving a polymer in a dispersion solvent to obtain a polymer solution;

The preparation method of the modified graphene avoids the damage of the grafting method to the surface of the graphene, retains the complete structure of the graphene to the maximum extent, retains the excellent performance of the graphene, and can more effectively improve the performance of the graphene heavy anti-corrosion coating.

In one embodiment, when the graphene and the dispersing solvent are uniformly mixed and then subjected to ultrasonic treatment, the ultrasonic frequency is 1-2 MHz, and the ultrasonic time is 10-40 min. Therefore, the graphene can be fully dispersed, a thinner flaky material can be formed as far as possible, the specific surface area of the material is increased, and subsequent polymer surface modification is facilitated.

In one embodiment, when graphene and the dispersing solvent are uniformly mixed, the ratio of graphene to the dispersing solvent may be 1g (40-50) mL. Therefore, agglomeration caused by too high concentration of graphene can be avoided, and low surface modification rate and long evaporation drying time caused by too low concentration of graphene can also be avoided.

In one embodiment, the dispersion solvent may be one or more of DMF (N, N-dimethylacetamide) and THF (tetrahydrofuran).

In one embodiment, the dissolution of the polymer may be accelerated by stirring, sonication, or the like, when the polymer is dissolved in the dispersion solvent. When necessary, it is possible to ensure complete dissolution of the polymer by increasing the amount of the dispersion solvent, and to obtain a polymer solution by concentration after complete dissolution of the polymer.

In an embodiment, the polymer may include one or more of polyvinylpyrrolidone, polypyrrole, polythiophene, and polyaniline.

In one embodiment, the volume of the polymer solution may be 1/4 of the volume of the graphene dispersion liquid, so as to maximize the concentration of the polymer in the polymer solution, so as to increase the concentration of the graphene and the polymer in the third mixture, and accelerate the modification of the graphene surface by the polymer.

In one embodiment, the mass ratio of the polymer to the graphene in the third mixture may be 0.5-0.64: 1, so as to achieve an optimal surface modification effect on the graphene and inhibit the graphene from agglomerating.

In an embodiment, when the graphene dispersion and the polymer solution are uniformly mixed, the graphene dispersion and the polymer solution may be mixed and stirred first, and then graphene and the polymer in the third mixture are uniformly distributed by ultrasound. It is understood that when the third mixture is subjected to ultrasonic treatment, the ultrasonic treatment can accelerate the surface modification of the graphene.

In one embodiment, the third mixture may be cooled to ambient temperature to allow sufficient bonding of the graphene to the polymer. It will be appreciated that the heat in the third mixture may be derived from the ultrasound waves that sonicate the third mixture.

In one embodiment, the dispersion solvent in the third mixture may be removed by drying under reduced pressure. For example, the third mixture may be placed in a vacuum drying oven and dried at 30-60 ℃ to remove the dispersing solvent. The vacuum drying time may be 36 hours or until the dispersion solvent is removed.

In one embodiment, the first organic solvent may include n-butanol and butyl acetate. When the first mixture is prepared, 0.82-1.5 parts by mass of modified graphene can be added into 70-80 parts by mass of epoxy resin and 4-8 parts by mass of n-butyl alcohol, and then 9-20 parts by mass of butyl acetate is added to adjust the concentration, so that the first mixture is obtained.

In one embodiment, the binder may be KH-560, i.e., gamma- (2, 3-glycidoxy) propyltrimethoxysilane.

In one embodiment, the leveling agent may be BYK-3700 or other leveling agents.

In one embodiment, the adhesive may be added to the second mixture, and the leveling agent may be added after the mixture is uniformly stirred. Experiments prove that the method can improve the performance of the prepared graphene heavy-duty anticorrosive coating and improve the performance of a heavy-duty anticorrosive coating formed by the graphene heavy-duty anticorrosive coating.

In one embodiment, when the second mixture is subjected to ultrasonic treatment, the ultrasonic treatment time is 10-50 min, so as to ensure that the modified graphene is uniformly dispersed.

In one embodiment, the curing agent system may include a curing agent and a second organic solvent, wherein the mass ratio of the curing agent to the second organic solvent may be 1.2-1.9: 1.

The disclosure also provides a heavy-duty anticorrosion coating which is formed by the graphene heavy-duty anticorrosive paint.

It can be understood that when the heavy-duty anticorrosion coating is formed, the resin system and the curing agent system need to be stirred uniformly and then coated on the metal structure to realize the anticorrosion of the metal structure.

The graphene heavy duty anticorrosive coating and the preparation method thereof according to the present disclosure will be further explained and illustrated below in various examples.

The first embodiment is as follows:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. The resin system comprises modified graphene, 77g of organic silicon epoxy resin, 5g of n-butanol, 9g of butyl acetate, KH-5601.5 g and BYK-37007 g; the modified graphene is a product obtained by surface-modifying 0.5g of graphene with 0.32g of polypyrrole. The curing agent system included Dynasylan AMEO240g and n-butanol 160 g.

When the graphene heavy anti-corrosion coating is prepared, a resin system and a curing agent system can be respectively prepared. The preparation method of the resin system comprises the following steps:

step 1), adding 0.5g of graphene into 20mL of DMF, uniformly stirring, and carrying out ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 1MHz, and the ultrasonic treatment time is 10 min.

Step 2), adding 0.32g of polypyrrole into DMF, and completely dissolving the polypyrrole by stirring or ultrasonic methods; the solution was concentrated to 5mL to obtain a polypyrrole solution.

And 3) mixing the graphene dispersion liquid and the polypyrrole solution, uniformly stirring at 2000r/min, and performing ultrasonic dispersion.

And 4), cooling to room temperature to obtain the modified graphene dispersion liquid.

And 5), evaporating and drying the graphene dispersion liquid in a vacuum drying oven at 60 ℃ to obtain the modified graphene.

And 6), adding the modified graphene into organic silicon epoxy resin (77g) and n-butanol (5g), and uniformly stirring by using a dispersion stirrer.

Step 7), adding butyl acetate into the mixture obtained in the step 6) to adjust the concentration.

Step 8), adding KH-560 and BYK-3700 to the mixture obtained in step 7) in this order.

And 9) uniformly stirring the mixture obtained in the step 8), performing ultrasonic treatment for 10min, and cooling to room temperature to obtain a resin system.

The curing agent system was prepared by mixing Dynasylan AMEO240g and n-butanol 160g uniformly.

The graphene heavy-duty anticorrosive coating provided by the disclosure needs to be uniformly mixed with a resin system and a curing agent system during application. For example, the resin system can be added into the curing agent system, and the graphene heavy anti-corrosion coating can be obtained after the resin system is uniformly stirred at 1000 r/min.

Example two:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. The resin system comprises modified graphene, phenolic epoxy resin 70g, n-butyl alcohol 4g, butyl acetate 9g, KH-5601.1g and BYK-37007 g; the modified graphene is a product obtained by surface-modifying 1.0g of graphene with 0.6g of polypyrrole. The curing agent system included Dynasylamm EO 220g and n-butanol 145 g.

step 1), adding 1.0g of graphene into 35mL of THF, uniformly stirring, and performing ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 1.5MHz, and the ultrasonic treatment time is 20 min.

Step 2), adding 0.6g of polypyrrole into THF, and completely dissolving the polypyrrole by stirring or ultrasonic methods; the solution was concentrated to 9mL to obtain a polypyrrole solution.

And 5) evaporating and drying the graphene dispersion liquid in a vacuum drying oven at the temperature of 30 ℃ to obtain the modified graphene.

And 6), adding the modified graphene into phenolic epoxy resin (70g) and n-butyl alcohol (4g), and uniformly stirring by using a dispersion stirrer.

And 9) uniformly stirring the mixture obtained in the step 8), performing ultrasonic treatment for 40min, and cooling to room temperature to obtain a resin system.

The curing agent system was prepared by mixing Dynasylan AMEO 220g and n-butanol 145g uniformly.

The graphene heavy-duty anticorrosive coating provided by the disclosure needs to be uniformly mixed with a resin system and a curing agent system during application. For example, the resin system can be added into the curing agent system, and the graphene heavy anti-corrosion coating can be obtained after the resin system is uniformly stirred at 3000 r/min.

Example three:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. Wherein the resin system comprises modified graphene, 77g of bisphenol F epoxy resin, 5g of n-butanol, 9g of butyl acetate, KH-5601.4 g and BYK-37007 g; the modified graphene is a product obtained by surface-modifying 0.6g of graphene with 0.35g of polythiophene. The curing agent system included Dynasylan AMEO240g and n-butanol 160 g.

step 1), adding 0.6g of graphene into 30mL of DMF, uniformly stirring, and carrying out ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 1.5MHz, and the ultrasonic treatment time is 20 min.

Step 2), adding 0.35g of polythiophene into DMF, and completely dissolving the polythiophene by stirring or ultrasonic and other methods; the solution was concentrated to 7.5mL to obtain a polythiophene solution.

And 3) mixing the graphene dispersion liquid and the polythiophene solution, stirring uniformly at 2000r/min, and performing ultrasonic dispersion.

And 5) evaporating and drying the graphene dispersion liquid in a vacuum drying oven at 50 ℃ to obtain the modified graphene.

And 6), adding the modified graphene into bisphenol F epoxy resin (77g) and n-butanol (5g), and uniformly stirring by using a dispersing stirrer.

The graphene heavy-duty anticorrosive coating provided by the disclosure needs to be uniformly mixed with a resin system and a curing agent system during application. For example, the resin system can be added into the curing agent system, and the graphene heavy anti-corrosion coating can be obtained after the resin system is uniformly stirred at 2000 r/min.

Example four:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. The resin system comprises modified graphene, 72g of novolac epoxy resin, 7g of n-butanol, 20g of butyl acetate, KH-5601.8 g and BYK-37007 g; the modified graphene is a product obtained by surface-modifying 0.7g of graphene with 0.4g of polyvinylpyrrolidone. The curing agent system included Dynasylan AMEO 235g, n-butanol 150g, and butyl acetate 45 g.

step 1), adding 0.7g of graphene into 35mL of THF, uniformly stirring, and performing ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 1.5MHz, and the ultrasonic treatment time is 20 min.

Step 2), adding 0.4g of polyvinylpyrrolidone into THF, and completely dissolving the polyvinylpyrrolidone by stirring or ultrasonic methods; the solution was concentrated to 9mL to obtain a polyvinylpyrrolidone solution.

And 3) mixing the graphene dispersion liquid and the polyvinylpyrrolidone solution, stirring uniformly at 2000r/min, and performing ultrasonic dispersion.

And 6), adding the modified graphene into novolac epoxy resin (72g) and n-butanol (7g), and uniformly stirring by using a dispersion stirrer.

And 9) uniformly stirring the mixture obtained in the step 8), performing ultrasonic treatment for 50min, and cooling to room temperature to obtain a resin system.

The curing agent system is prepared by uniformly mixing Dynasylan AMEO 235g, n-butanol 150g and butyl acetate 45 g.

Example five:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. The resin system comprises modified graphene, 77g of novolac epoxy resin, 5g of n-butanol, 9g of butyl acetate, KH-5601.4 g and BYK-37006.9 g; the modified graphene is a product obtained by surface-modifying 0.7g of graphene with 0.4g of polyvinylpyrrolidone. The curing agent system included Dynasylan AMEO240g and n-butanol 160 g.

step 1), adding 0.7g of graphene into 35mL of THF, uniformly stirring, and performing ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 1.5.0MHz, and the ultrasonic treatment time is 30 min.

And 6), adding the modified graphene into novolac epoxy resin (77g) and n-butanol (5g), and uniformly stirring by using a dispersion stirrer.

Example six:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. The resin system comprises modified graphene, 80g of novolac epoxy resin, 6g of n-butanol, 19g of butyl acetate, KH-5601.5 g and BYK-37006 g; the modified graphene is a product obtained by surface-modifying 0.7g of graphene with 0.4g of polyvinylpyrrolidone. The curing agent system comprises Dynasylan AMEO 270g, n-butanol 100g and butanediol 80 g.

step 1), adding 0.7g of graphene into 35mL of THF, uniformly stirring, and performing ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 1.5MHz, and the ultrasonic treatment time is 30 min.

And 6), adding the modified graphene into phenolic epoxy resin (80g) and n-butanol (6g), and uniformly stirring by using a dispersion stirrer.

And 9) uniformly stirring the mixture obtained in the step 8), performing ultrasonic treatment for 30min, and cooling to room temperature to obtain a resin system.

The curing agent system is prepared by uniformly mixing Dynasylan AMEO 270g, n-butanol 100g and butanediol 80 g.

Example seven:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. The resin system comprises modified graphene, 77g of glycerol epoxy resin, 5g of n-butanol, 9g of butyl acetate, KH-5601.3 g and BYK-37006.6 g; the modified graphene is a product obtained by surface-modifying 1g of graphene with 0.5g of polyaniline. The curing agent system included Dynasylamm EO240g and n-butanol 160 g.

step 1), adding 1g of graphene into 40mL of DMF, uniformly stirring, and carrying out ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 2.0MHz, and the ultrasonic treatment time is 40 min.

Step 2), adding 0.5g of polyaniline into DMF, and completely dissolving the polyaniline by stirring or ultrasonic and other methods; the solution was concentrated to 10mL to obtain a polyaniline solution.

And 3) mixing the graphene dispersion liquid and the polyaniline solution, uniformly stirring at 2000r/min, and performing ultrasonic dispersion.

And 5) evaporating and drying the graphene dispersion liquid in a vacuum drying oven at 40 ℃ to obtain the modified graphene.

And 6), adding the modified graphene into glycerol epoxy resin (77g) and n-butanol (5g), and uniformly stirring by using a dispersion stirrer.

Example eight:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. Wherein the resin system comprises 80g of modified graphene, 80g of glycerol epoxy resin, 4g of n-butanol, 12g of butyl acetate, KH-5601 g and BYK-37005.5 g; the modified graphene is a product obtained by surface-modifying 1g of graphene with 0.5g of polyvinylpyrrolidone. The curing agent system included Dynasylan AMEO 265g and n-butanol 145 g.

step 1), adding 1g of graphene into 40mL of THF, uniformly stirring, and performing ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 1.5MHz, and the ultrasonic treatment time is 40 min.

Step 2), adding 0.5g of polyvinylpyrrolidone into THF, and completely dissolving the polyvinylpyrrolidone by stirring or ultrasonic methods; the solution was concentrated to 10mL to obtain a polyvinylpyrrolidone solution.

And 3) mixing the graphene dispersion liquid and the polyvinylpyrrolidone solution, stirring uniformly under the condition of 1000r/min, and then performing ultrasonic dispersion.

And 6), adding the modified graphene into glycerol epoxy resin (80g) and n-butanol (4g), and uniformly stirring by using a dispersion stirrer.

The curing agent system was prepared by mixing Dynasylan AMEO 265g and n-butanol 145g uniformly.

Example nine:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. Wherein the resin system comprises modified graphene, 70g of glycerol epoxy resin, 6g of n-butanol, 16g of butyl acetate, KH-5602.0 g and BYK-37005.0 g; the modified graphene is a product obtained by surface-modifying 1g of graphene with 0.5g of polyaniline. The curative system included Dynasylan AMEO 225g and n-butanol 175 g.

And 3) mixing the graphene dispersion liquid and the polyaniline solution, stirring uniformly under the condition of 1000r/min, and then performing ultrasonic dispersion.

And 6), adding the modified graphene into glycerol epoxy resin (70g) and n-butanol (6g), and uniformly stirring by using a dispersion stirrer.

And 9) uniformly stirring the mixture obtained in the step 8), performing ultrasonic treatment for 20min, and cooling to room temperature to obtain a resin system.

The curing agent system was prepared by mixing Dynasylan AMEO 225g and n-butanol 175g uniformly.

Example ten:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. Wherein the resin system comprises modified graphene, 77g of glycerol epoxy resin, 5g of n-butanol, 8.1g of butyl acetate, KH-5601.3 g and BYK-37006.5 g; the modified graphene is a product obtained by surface-modifying 2g of graphene with 1g of polyaniline. The curing agent system included Dynasylamm EO240g and n-butanol 160 g.

step 1), adding 2g of graphene into 100mL of THF, uniformly stirring, and performing ultrasonic treatment to obtain a graphene dispersion liquid; wherein the ultrasonic treatment frequency is 2.0MHz, and the ultrasonic treatment time is 40 min.

Step 2), adding 1g of polyaniline into THF, and completely dissolving the polyaniline by stirring or ultrasonic methods; the solution was concentrated to 25mL to obtain a polyaniline solution.

The graphene heavy-duty anticorrosive coating provided by the disclosure needs to be uniformly mixed with a resin system and a curing agent system during application. For example, the resin system can be added into the curing agent system, and the graphene heavy anti-corrosion coating can be obtained after the resin system is uniformly stirred at 4000 r/min.

Example eleven:

a graphene heavy anti-corrosion coating comprises a resin system and a curing agent system. Wherein the resin system comprises 77g of organic silicon epoxy resin, 5g of n-butanol, 9g of butyl acetate, KH-5601.5 g and BYK-37007 g; the modified graphene is a product obtained by surface-modifying 0.5g of graphene with 0.32g of polypyrrole. The curative system included Dynasylan AMEO240g and 160g of n-butanol.

step 1), mixing the silicone epoxy resin (77g) and n-butanol (5g), and stirring uniformly with a dispersion stirrer.

Step 2), adding butyl acetate into the mixture obtained in the step 1) to adjust the concentration.

Step 3), adding KH-560 and BYK-3700 to the mixture obtained in step 2) in sequence.

And 4), uniformly stirring the mixture obtained in the step 3), performing ultrasonic treatment for 10min, and cooling to room temperature to obtain a resin system.

Example twelve

The performance of the heavy anti-corrosion coating formed by the graphene heavy anti-corrosion coatings of the first, third, fifth, seventh, tenth and eleventh examples is detected, and the detection results are shown in table 1:

table 1: performance detection results of heavy anti-corrosion coatings prepared from graphene heavy anti-corrosion coatings of different embodiments

Wherein, the salt spray experiment is a neutral salt spray experiment with the salt water concentration of 5 percent and the pH value of about 7, and the change of the test piece is observed by the spray experiment under the condition of 35 ℃.

As can be known from table 1, compared with the eleventh embodiment, the indexes of flexibility, adhesion, salt spray resistance, impact resistance and the like of the heavy anti-corrosion coating formed by the graphene heavy anti-corrosion coatings of the first, third, fifth and seventh embodiments are all improved to a greater extent, which indicates that the addition of the modified graphene significantly improves the corrosion resistance and mechanical properties of the epoxy resin coating, and eliminates or reduces micro defects in the epoxy resin coating.

Compared with the eleventh embodiment, the heavy anti-corrosion coating formed by the graphene heavy anti-corrosion coating of the tenth embodiment has a small reduction in the indexes such as flexibility, salt spray resistance and impact resistance, which indicates that an opposite effect is achieved when the addition amount of the modified graphene is too large, and the corrosion resistance and the mechanical property of the epoxy resin coating are reduced. This is because the modified graphene is easily agglomerated to form particles at a high content, resulting in an increase in defects on the epoxy resin coating and a decrease in its performance.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims

1. The graphene heavy-duty anticorrosive paint comprises a resin system and a curing agent system, and is characterized in that the resin system comprises, by mass, 0.82-1.5 parts of modified graphene, 70-80 parts of epoxy resin, 13-28 parts of a first organic solvent, 1-2 parts of an adhesive and 5-7 parts of a leveling agent; wherein the mass ratio of the curing agent system to the resin system is 3.5-4.5: 1.

2. The graphene heavy anti-corrosion coating according to claim 1, wherein the modified graphene is a polymer surface modified graphene, and the polymer comprises one or more of polyvinylpyrrolidone, polypyrrole, polythiophene and polyaniline.

3. The graphene heavy anti-corrosion coating according to claim 2, wherein the mass ratio of the polymer to the graphene in the polymer surface-modified graphene is 0.5-0.64: 1.

4. The graphene heavy-duty anticorrosive coating according to any one of claims 1 to 3, wherein the epoxy resin comprises one or more of bisphenol F type epoxy resin, silicone epoxy resin, novolac epoxy resin, and glycerol epoxy resin.

5. The graphene heavy-duty anticorrosive coating according to any one of claims 1 to 3, characterized in that the binder is γ - (2, 3-glycidoxy) propyltrimethoxysilane.

6. The graphene heavy-duty anticorrosive coating according to any one of claims 1 to 3, wherein the curing agent system comprises gamma-aminopropyltriethoxysilane and a second organic solvent, and the mass ratio of the gamma-aminopropyltriethoxysilane to the second organic solvent is 1.2 to 1.9: 1.

7. The preparation method of the graphene heavy anti-corrosion coating is characterized by comprising the steps of preparing a resin system and a curing agent system, wherein the mass ratio of the curing agent system to the resin system is 3.5-4.5: 1; wherein, preparing the resin system comprises:

preparing modified graphene;

8. The preparation method of the graphene heavy anti-corrosion coating according to claim 7, wherein the modified graphene is polymer surface-modified graphene; the preparation of the modified graphene comprises:

dissolving a polymer in a dispersion solvent to obtain a polymer solution;

9. The preparation method of the graphene heavy anti-corrosion coating according to claim 8, wherein when the graphene and the dispersing solvent are uniformly mixed and then subjected to ultrasonic treatment, the ultrasonic frequency is 1-2 MHz, and the ultrasonic time is 10-40 min.

10. A heavy-duty anticorrosive coating, characterized in that the heavy-duty anticorrosive coating is formed from the graphene heavy-duty anticorrosive coating according to any one of claims 1 to 6.