CN106280578B - A kind of limbic function graphite alkene, preparation method and the purposes for being used to prepare anticorrosive paint - Google Patents

Abstract

The invention belongs to the functionalization of graphene and application field, it is related to a kind of limbic function graphite alkene, preparation method and the purposes for being used to prepare anticorrosive paint.The present invention method be using chlorate, the concentrated sulfuric acid and hydrogen peroxide system to graphene carry out functionalization, obtain carboxylic group selective modification the lamella edge of complete structure limbic function graphite alkene；Gained limbic function graphite alkene individually film forming and/or with anticorrosion paint formulation component composite membrane-forming, limbic function graphite alkene anticorrosive paint can be made.The method and process that the present invention prepares limbic function graphite alkene is simple, efficient, graphene is not only overcome to be difficult to handle, be easy the problem of accumulation, impart graphene solution machinability and handlability, simultaneously, avoid to graphene sheet layer structural damage, realize the holding of graphene sheet layer structure and characteristic, the anticorrosion ability of limbic function graphite alkene anticorrosive paint obtained is good, applied widely.

Description

A kind of edge functionalized graphene, its preparation method and its preparation method for anti-corrosion coating use

technical field

The invention belongs to the field of functionalization and application of graphene, relates to a kind of edge functionalized graphene, its preparation method and the application for preparing anti-corrosion coating, especially relates to a kind of carboxyl group selective modification in complete graphene sheet Edge-functionalized graphene on the edge of , a preparation method thereof and use for preparing an edge-functionalized graphene anticorrosion coating.

Background technique

Since its discovery in 2004, graphene has attracted much attention as a new type of carbon material. Graphene materials can be widely used in high-performance nanoelectronic devices, optoelectronic devices, gas sensors, composite materials, field emission materials, and energy storage. In view of the difficult dispersion of graphene and the difficulty of stacking between sheets, the functional modification of graphene has broadened the industrial application potential of graphene. Graphene oxide (GO) is the most typical edge-functionalized graphene that has been extensively tested. There are a large number of functional groups such as carboxyl, epoxy, hydroxyl, and carbonyl on the sheet, which can make graphene oxide have a relatively high density in solution. Good dispersion. However, when the oxygen-containing functional groups are introduced, the conjugated structure of the graphene sheet itself is greatly destroyed. Even though various reduction methods can remove the oxygen-containing groups on the sheet to a certain extent, the obtained reduced Graphene oxide (RGO) sheets still have a large number of irreparable defects or holes (Kris Erickson, RolfErni, Zonghoon Lee, Nasim Alem, Will Gannett, Alex Zettl, Determination of the Local Chemical Structure of Graphene Oxide and Reduced Graphene Oxide, Adv. Mater.2010,22,4467-4472), so that the characteristics of graphene oxide and/or reduced graphene oxide have a large gap with many excellent physical and chemical properties of graphene.

Coating anticorrosion is widely used in the field of surface protection because of its simplicity, economy, applicability, freedom from equipment shape constraints, and decorative effects. Because graphene has a unique two-dimensional honeycomb structure composed of sp ² hybridized carbon atoms and excellent thermal and chemical stability, graphene can form a physical barrier between the surface interface of metals and other materials and active materials, It can effectively prevent the diffusion and penetration of gas or liquid molecules, and has the potential to become an excellent protective coating material. At present, graphene has been applied to some aspects of coating anticorrosion, mainly divided into two methods: (1) directly using graphene in the coating formulation preparation process, however, the graphene used is difficult to disperse, making the coating preparation method cumbersome , time-consuming, and lead to poor uniformity and stability of the prepared coating; (2) use solution-processable graphene oxide or its derivatives in the coating formulation preparation process, however, because graphene oxide or its derivatives have a large amount of Irreparable holes greatly reduce the effectiveness of graphene as an anti-corrosion coating, and the scope of use of coatings is limited. For example, some cannot be used in marine environments, and some cannot be used in high-temperature environments.

CN 104445163 A discloses a method for preparing carboxylated graphene, comprising the following steps: 1.1 preparing graphene oxide suspension; 1.2 reducing graphene oxide with reducing agent hydrazine hydrate to prepare graphene turbid liquid; 1.3 suspending graphene Cool the liquid to 70-80°C, add the alcohol solution of aminophenyl acid and isoamyl nitrite to adjust the content of each component, then add a strong base, condense and reflux in an oil bath at 70-80°C for 24-48 hours to obtain The precursor turbid solution of carboxylated graphene; 1.4 adjust the pH to 5～6 with strong acid to obtain the precursor turbid solution of acidic graphene; 1.5 the solid matter in the acidic carboxylated graphene turbid solution is rinsed and filtered with deionized water until When the pH reaches 6-7, water-containing carboxylated graphene is obtained; at 1.6 freeze-drying, carboxylated graphene powder is obtained. However, as mentioned above, even after various reduction treatments, the graphene oxide sheet itself has a large number of irreparable defects or holes, which greatly restricts the application of graphene in preventing the diffusion and penetration of gas or liquid molecules.

Contents of the invention

In order to overcome the defects of the prior art, the present invention provides a new graphene functionalization method with simple process and low cost, and simultaneously solves the problems of difficult dispersion, easy stacking and structure maintenance of graphene in the prior art, And it is applied to the field of graphene anti-corrosion coating, and the edge-functionalized graphene anti-corrosion coating is prepared, which has the characteristics of good anti-corrosion effect and wide application range.

For reaching above-mentioned object, the present invention adopts following technical scheme:

In a first aspect, the present invention provides an edge-functionalized graphene, in which the carboxyl group is selectively modified on the edge of a complete graphene sheet.

The edge-functionalized graphene of the present invention has a complete sheet structure, which greatly improves the efficiency of the graphene sheet in preventing gas or liquid diffusion. At the same time, the edge of the sheet is modified with carboxyl groups, which improves the dispersion of graphene sheets At the same time, it prevents the mutual stacking of the sheets, thereby effectively improving the utilization rate of the graphene sheets in preventing gas or liquid diffusion and penetration.

In a second aspect, the present invention provides a method for preparing edge-functionalized graphene as described in the first aspect, the method is as follows: graphene is dispersed in a mixed solution of chlorate, concentrated sulfuric acid and hydrogen peroxide to obtain a mixed solution, The reaction yields edge-functionalized graphene.

Preferably, the preparation method of graphene in the present invention can adopt the preparation method disclosed in the prior art, such as but not limited to mechanical exfoliation method, ball milling method, ultrasonic method, turbulent flow method or supercritical fluid method, etc.

Preferably, the chlorate includes any one or a mixture of at least two of sodium chlorate, potassium chlorate, magnesium chlorate or calcium chlorate, but is not limited to the chlorate listed above, other can achieve the same effect All chlorates can be used in the present invention.

Preferably, the mass concentration of concentrated sulfuric acid is 98%.

Preferably, the mass concentration of hydrogen peroxide is 30%.

Preferably, the mass ratio of graphene and chlorate is 1:(1～10), for example, it can be 1:1, 1:2, 1:3, 1:4, 1:4.5, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc., the preferred mass ratio is 1:(3-6).

Preferably, the concentration of graphene in the mixed solution is 0.1-50 mg/mL, such as 0.1 mg/mL, 0.5 mg/mL, 0.9 mg/mL, 1 mg/mL, 1.5 mg/mL, 2 mg/mL, 3mg/mL, 5mg/mL, 6.5mg/mL, 8mg/mL, 9mg/mL, 10mg/mL, 11mg/mL, 12mg/mL, 13mg/mL, 15mg/mL, 17mg/mL, 20mg/mL, 23mg /mL, 25mg/mL, 27.5mg/mL, 30mg/mL, 32.5mg/mL, 35mg/mL, 38mg/mL, 40mg/mL, 44mg/mL, 47mg/mL or 50mg/mL etc., the preferred concentration is 0.9～20mg/mL.

Preferably, the volume ratio of hydrogen peroxide to concentrated sulfuric acid is 1:(100-1:10000), for example, it can be 1:100, 1:150, 1:200, 1:300, 1:500, 1:600, 1:700, 1:800, 1:1000, 1:1200, 1:1500, 1:1800, 1:2000, 1:2350, 1:2600, 1:2800, 1:3000, 1:3200, 1: 3500, 1:3700, 1:4000, 1:4200, 1:4500, 1:4700 or 1:5000, etc., the preferred volume ratio is 1:(200-5000).

Preferably, the reaction time is 0.5 to 48 hours, such as 0.5 hours, 1 hour, 2 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 13 hours, 15 hours, 17.5 hours, 20 hours, 24 hours, 26 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 42 hours, 46 hours or 48 hours, preferably 2 to 10 hours;

Preferably, the reaction temperature is 0-90°C, for example, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 35°C, 40°C, 50°C, 60°C, 70°C, 80°C or 90°C, etc., the preferred temperature is 0 to 50°C.

Preferably, the method further includes the steps of separating and washing after the reaction is completed.

In a third aspect, the present invention provides an edge-functionalized graphene anti-corrosion coating, which contains the edge-functionalized graphene described in the first aspect.

The edge-functionalized graphene anti-corrosion coating of the present invention can be an edge-functionalized graphene single-component anti-corrosion coating, and can also be an edge-functionalized graphene composite anti-corrosion coating.

The edge-functionalized graphene single-component anti-corrosion coating in the present invention refers to: the anti-corrosion coating is composed of edge-functionalized graphene and a dispersant.

The edge-functionalized graphene composite anticorrosion coating in the present invention refers to: besides the edge-functionalized graphene and the dispersant, any one or two or more of film-forming agents, fillers, auxiliary agents or curing agents are also included The combination.

Preferably, the film-forming agent is an organic polymer, preferably any one or a combination of two or more of epoxy resin, acrylate, phenolic resin, polyurethane or alkyd resin, but is not limited to the above-mentioned composition Film agent, other commonly used film-forming agents for preparing anti-corrosion coatings in this field can also be used in the present invention. .

Preferably, based on the total mass of the anti-corrosion coating as 100%, the mass percentage of the film-forming agent is 0-80%, and does not include 0%, for example, it can be 0.01%, 0.1%, 0.2%, 0.5%, 1 %, 5%, 10%, 13%, 15%, 20%, 25%, 28%, 30%, 35%, 40%, 45%, 47.5%, 50%, 55%, 57%, 60%, 70%, 75% or 80%, etc.

Preferably, the filler is any one or a combination of two or more of silica, zinc oxide, titanium dioxide, aluminum oxide, magnesium silicate, aluminum silicate, calcium sulfate, and calcium carbonate, but is not limited to The fillers listed above and other fillers commonly used in the preparation of anti-corrosion coatings in this field can also be used in the present invention.

Magnesium silicate among the present invention can be commercially available magnesium silicate, also can be the mineral that contains magnesium silicate, such as talcum powder etc.; Aluminum silicate among the present invention can be commercially available aluminum silicate, also can be Minerals containing aluminum silicate, such as china clay and kaolin etc.; calcium sulfate in the present invention is also called gypsum powder; calcium carbonate in the present invention can be commercially available calcium carbonate, or minerals containing calcium carbonate, such as white clay .

Preferably, based on the total mass of the anti-corrosion coating as 100%, the mass percentage of the filler is 1-20%, for example, it can be 1%, 3%, 5%, 7%, 10%, 12.5%, 13.5%, 15%, 18%, or 20%, etc.

Preferably, the auxiliary agent is any one or a combination of two or more of organosiloxane, surfactant, polyacrylic acid, and carboxymethyl cellulose, but is not limited to the above-listed auxiliary agents. Others in the field Auxiliaries commonly used in the preparation of anti-corrosion coatings can also be used in the present invention.

Preferably, based on 100% of the total mass of the anti-corrosion coating, the mass percentage of the additive is 1-20%, such as 1%, 2%, 4%, 6.5%, 8.5%, 10%, 13% , 15%, 17% or 20%, etc.

Preferably, the curing agent is any one or a combination of two or more of amine curing agents, polyurethane curing agents, phenolic resin curing agents, acrylate curing agents or p-toluenesulfonic acid curing agents, but is not limited to the above Among the curing agents listed, other curing agents that can achieve the same effect can also be used in the present invention.

Preferably, based on the total mass of the anti-corrosion coating as 100%, the mass percentage of the curing agent is 1-20%, for example, it can be 1%, 3%, 6%, 8%, 10%, 12%, 14% , 16%, 18% or 20%, etc.

Preferably, based on the total mass of the anti-corrosion coating as 100%, the mass percentage of the edge-functionalized graphene is 0.1-70%, such as 0.1%, 0.6%, 1%, 2%, 3%, 5%. , 10%, 15%, 20%, 23%, 26%, 30%, 35%, 38%, 40%, 45%, 50%, 52.5%, 55%, 60%, 65% or 70%, etc.

Preferably, the dispersant is any one or a combination of two or more of water, N-methylpyrrolidone, N,N-dimethylformamide, acetone, ethanol, n-butanol or ethyl acetate.

Preferably, based on the total mass of the anti-corrosion coating as 100%, the mass percentage of the dispersant is 5-45%, such as 5%, 10%, 12%, 16%, 20%, 25%, 28% , 30%, 35%, 37%, 40%, 42.5% or 45%, etc.

The edge-functionalized graphene of the present invention is not only applicable to the above-mentioned edge-functionalized graphene single-component anti-corrosion coating and edge-functionalized graphene composite anti-corrosion coating, but also suitable for various preparation formulas of other anti-corrosion coatings.

In a fourth aspect, the present invention provides a method for preparing the edge-functionalized graphene anticorrosion coating as described in the third aspect.

Since the edge-functionalized graphene anti-corrosion coating in the present invention can specifically be an edge-functionalized graphene single-component anti-corrosion coating, or an edge-functionalized graphene composite anti-corrosion coating, there are differences in the preparation method. Specifically, the preparation methods of the edge-functionalized graphene single-component anti-corrosion coating and the edge-functionalized graphene composite anti-corrosion coating are as follows:

For edge-functionalized graphene one-component anti-corrosion coating, its preferred preparation method is: add edge-functionalized graphene in the dispersant, mechanically stir 1～24h, obtain edge-functionalized graphene anti-corrosion coating, this anti-corrosion coating is Edge-functionalized graphene one-component anti-corrosion coatings.

For the edge-functionalized graphene composite anticorrosion coating, its preferred preparation method is: add any one or two or more combinations of edge-functionalized graphene and film-forming agent, filler, auxiliary agent or curing agent to the dispersant , stirring for 1-24 hours, standing for defoaming, and obtaining an edge-functionalized graphene anti-corrosion coating, which is an edge-functionalized graphene composite anti-corrosion coating.

In summary, the prepared edge-functionalized graphene can be directly formed into a film to prepare a single-component edge-functionalized graphene anti-corrosion coating, or combined with film-forming agents, fillers and other auxiliary components to form a compound film to prepare an edge-functionalized graphene composite anti-corrosion coating. In addition, adding the edge-functionalized graphene to various currently known anti-corrosion coating formulations is within the protection scope of the present invention.

Compared with the prior art, the present invention has the following advantages:

(1) The present invention proposes a new graphene functionalization method, adopts the compound reaction system of chlorate, concentrated sulfuric acid and hydrogen peroxide, and realizes carboxyl group in graphene while keeping the structural integrity of graphene sheet Selective functionalization of edges; the process of the method of the invention is simple, efficient, low in cost, and easy to industrialized mass production.

(2) The edge-functionalized graphene of the present invention has the characteristics of complete lamellar structure, high lamellar quality, good solution processability, strong processability, and not easy to stack. The problem of difficult dispersibility, easy stacking and difficult structure maintenance of graphene in the prior art is solved.

(3) Based on the complete lamellar structure and excellent physicochemical properties of the edge functionalized graphene of the present invention, the edge functionalized graphene anticorrosion coating prepared by the edge functionalized graphene of the present invention has excellent anticorrosion properties, can It is widely used in the surface and interface corrosion protection involved in land, ocean and daily life. In addition, edge-functionalized graphene anti-corrosion coatings also have other physical, chemical and biological properties that other nanomaterials do not have, such as antibacterial, deodorizing, Anti-aging and anti-ultraviolet properties.

Description of drawings

Fig. 1 is a transmission electron micrograph of edge-functionalized graphene prepared in Example 1 of the present invention.

FIG. 2 is a Raman spectrum of edge-functionalized graphene prepared in Example 1 of the present invention.

Fig. 3 is an X-ray photoelectron spectrum diagram of edge-functionalized graphene prepared in Example 1 of the present invention.

Detailed ways

The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and through specific implementation methods.

Example 1

(1) Add 300 mg of graphene prepared by the turbulent flow method to a mixed system of 200 ml H ₂ SO ₄ (98%), 1.8 g NaClO ₃ and 1 ml _{H 2} O ₂ (30%), and stir for 8 h at room temperature (25° C.) , and then the product was repeatedly centrifuged and washed to obtain edge-functionalized graphene with carboxyl groups selectively modifying the edge of the sheet.

(2) Weigh 2.5mg of edge-functionalized graphene, 300mg of phenolic resin, 40mg of gypsum powder filler, 20mg of polyacrylic acid additive and 30mg of p-toluenesulfonic acid curing agent and disperse them in 100ml of water, and obtain edge-functionalized graphene after 5 hours of mechanical stirring Composite anti-corrosion coating.

It is applied to the surface of the substrate by spraying, and after drying, an edge-functionalized graphene composite anti-corrosion coating is obtained.

Figure 1 and Figure 2 are transmission electron micrographs and carbon Raman spectra of edge-functionalized graphene, indicating the integrity and high quality of its structure;

Figure 3 is the X-ray photoelectron spectrum of edge-functionalized graphene. After fitting the carbon peak, it shows that it mainly comes from the carboxyl group at the edge of the sheet;

Table 1 shows that the edge-functionalized graphene anticorrosion coating of the present embodiment has excellent corrosion resistance.

Example 2

(1) 1000 mg of graphene prepared by turbulent flow method was added to 200ml H ₂ SO ₄ (98%), 1.8g NaClO ₃ and 0.04ml H ₂ O ₂ (30%) in the mixed system, stirred at 15°C for 4h, Then the product was repeatedly centrifuged and washed with water to obtain edge-functionalized graphene with carboxyl groups selectively modifying the edge of the sheet.

(2) Weigh 5 mg of edge-functionalized graphene, 60 mg of epoxy resin, 8 mg of talc filler, 10 mg of tributyl phosphate additive and 5 mg of m-phenylenediamine curing agent and disperse them in 80 ml of N-methylpyrrolidone, and mechanically Stir to obtain edge functionalized graphene composite anticorrosion coating.

It is applied to the surface of the substrate by spraying, and after drying, an edge-functionalized graphene composite anti-corrosion coating is obtained.

Table 1 shows that the edge-functionalized graphene anticorrosion coating of the present embodiment has excellent corrosion resistance.

Example 3

(1) Add 200 mg of graphene prepared by mechanical exfoliation to a mixed system of 10 ml H ₂ SO ₄ (98%), 2 g KClO ₃ and 0.01 ml H ₂ O ₂ (30%), stir at 0° C. for 10 h, Then the product was repeatedly centrifuged and washed with water to obtain edge-functionalized graphene with carboxyl groups selectively modifying the edge of the sheet.

(2) Weigh 70 mg of edge-functionalized graphene and disperse it in 30 ml of water, and mechanically stir for 1 hour to obtain a single-component anti-corrosion coating with edge-functionalized graphene.

It is applied to the surface of the substrate by brushing, and after drying, an edge-functionalized graphene single-component anti-corrosion coating is obtained.

Table 1 shows that the edge-functionalized graphene anticorrosion coating of the present embodiment has excellent corrosion resistance.

Example 4

(1) Add 600 mg of graphene prepared by ball milling to 200 ml H ₂ SO ₄ (98%), 1.8 g NaClO ₃ and 0.04 ml H ₂ O ₂ (30%) in a mixed system, stir at 45° C. for 2 h, Then the product was repeatedly centrifuged and washed with water to obtain edge-functionalized graphene with carboxyl groups selectively modifying the edge of the sheet.

(2) Weigh 5mg of edge-functionalized graphene, 140mg of hydroxyacrylic resin, 10mg of fumed silica filler, 12mg of carboxymethylcellulose additives and 10mg of toluene diisocyanate curing agent and disperse them in a mixed dispersant of 100ml of n-butanol and water In the process, the edge-functionalized graphene composite anti-corrosion coating was obtained after 5 hours of mechanical stirring.

It is applied to the surface of the substrate by spraying, and after drying, an edge-functionalized graphene composite anti-corrosion coating is obtained.

Table 1 shows that the edge-functionalized graphene anticorrosion coating of the present embodiment has excellent corrosion resistance.

Comparative example 1

Weigh 2.5mg of graphene oxide (containing carboxyl, hydroxyl, carbonyl and other functional groups, and the sheet structure has a large number of irreparable defects or holes), 300mg of phenolic resin, 40mg of gypsum powder filler, 20mg of polyacrylic acid additives, 30mg of p-toluenesulfonate Add the acid curing agent in 100ml water and stir mechanically for 5 hours to obtain a graphene oxide-based anticorrosion coating.

It is applied to the surface of the substrate by spraying, and after drying, a graphene oxide-based anti-corrosion coating is obtained.

It is applied to the surface of the substrate by brushing, and after drying, an edge-functionalized graphene single-component anti-corrosion coating is obtained.

Comparative example 2

Except that step (1) is not carried out and the 2.5mg edge functionalized graphene used in step (2) is replaced by the graphene prepared by the turbulence method in the 2.5mg step (1), other preparation methods and conditions are the same as in Example 1 .

It is applied to the surface of the substrate by spraying, and after drying, a graphene-based anti-corrosion coating is obtained.

The graphene-based anticorrosion coating obtained in this comparative example is uneven, easy to precipitate, and has poor corrosion resistance.

Table 1 shows the performance of the graphene oxide-based anti-corrosion coating prepared by the edge functionalized graphene anti-corrosion coating prepared by the embodiment of the present invention 1-4, the graphene-based anti-corrosion coating prepared by the traditional method and the comparative example 2 , and its performance is tested according to GB/T 9755-2001.

Table 1

The applicant declares that the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims (31)

1. a kind of limbic function graphite alkene, which is characterized in that in the limbic function graphite alkene, carboxylic group is selectively It modifies at the edge of the graphene sheet layer of complete structure；

The limbic function graphite alkene is prepared via a method which to obtain：By graphene dispersion in chlorate, the concentrated sulfuric acid and double In the mixed solution of oxygen water, mixed solution is obtained, limbic function graphite alkene is obtained by the reaction；

The mass ratio of the graphene and chlorate is 1:(1~10), a concentration of the 0.1 of graphene in the mixed solution~ The volume ratio of 50mg/mL, the hydrogen peroxide and the concentrated sulfuric acid is 1:(100~10000).

2. the preparation method of limbic function graphite alkene as described in claim 1, which is characterized in that the method is：By stone Black alkene is dispersed in the mixed solution of chlorate, the concentrated sulfuric acid and hydrogen peroxide, obtains mixed solution, and limbic function fossil is obtained by the reaction Black alkene；

The mass ratio of the graphene and chlorate is 1:(1~10), a concentration of the 0.1 of graphene in the mixed solution~ The volume ratio of 50mg/mL, the hydrogen peroxide and the concentrated sulfuric acid is 1:(100~10000).

3. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the system of the graphene Preparation Method includes any one in mechanical stripping method, ball-milling method, ultrasonic method, turbulene method or supercritical fluid method.

4. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the chlorate includes In sodium chlorate, potassium chlorate, magron or calcium chlorate any one or at least two mixture.

5. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the quality of the concentrated sulfuric acid is dense Degree is 98%.

6. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the matter of the hydrogen peroxide Measure a concentration of 30%.

7. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the graphene and chlorine The mass ratio of hydrochlorate is 1:(3~6).

8. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that in the mixed solution A concentration of 0.9~20mg/mL of graphene.

9. the preparation method of limbic function graphite alkene according to claim 2, which is characterized in that the hydrogen peroxide and dense The volume ratio of sulfuric acid is 1:(200~5000).

10. according to the method described in claim 2, it is characterized in that, the time of the reaction is 0.5~48 hour.

11. according to the method described in claim 10, it is characterized in that, the time of the reaction is 2~10 hours.

12. according to the method described in claim 2, it is characterized in that, the temperature of the reaction is 0~90 DEG C.

13. according to the method for claim 12, which is characterized in that the temperature of the reaction is 0~50 DEG C.

14. according to the method described in claim 2, it is characterized in that, the method further includes after completion of the reaction, detached The step of with washing.

15. a kind of limbic function graphite alkene anticorrosive paint, which is characterized in that the anticorrosive paint contains described in claim 1 Limbic function graphite alkene.

16. anticorrosive paint according to claim 15, which is characterized in that the anticorrosive paint is by limbic function graphite alkene And dispersant composition.

17. anticorrosive paint according to claim 15, which is characterized in that further include film forming agent in the anticorrosive paint, fill out Material, auxiliary agent and curing agent.

18. anticorrosive paint according to claim 17, which is characterized in that the film forming agent is organic polymer.

19. anticorrosive paint according to claim 18, which is characterized in that the film forming agent be epoxy resin, acrylate, The combination of any one or two kinds or more in phenolic resin, polyurethane or alkyd resin.

20. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute The mass percent for stating film forming agent is 0~80%, and does not include 0%.

21. anticorrosive paint according to claim 17, which is characterized in that the filler is silica, zinc oxide, dioxy Change any one in titanium, alundum (Al2O3), magnesium silicate, alumina silicate, calcium sulfate, calcium carbonate or two or more combinations.

22. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute The mass percent for stating filler is 1~20%.

23. anticorrosive paint according to claim 17, which is characterized in that the auxiliary agent is organosiloxane, surface-active Any one in agent, polyacrylic acid, carboxymethyl cellulose or two or more combinations.

24. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute The mass percent for stating auxiliary agent is 1~20%.

25. anticorrosive paint according to claim 17, which is characterized in that the curing agent is amine curing agent, Polyurethane In curing agent, phenolic resin curing agent, acrylate cures agent or p-methyl benzenesulfonic acid curing agent any one or it is two or more Combination.

26. anticorrosive paint according to claim 17, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute The mass percent for stating curing agent is 1~20%.

27. anticorrosive paint according to claim 16, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute The mass percent for stating limbic function graphite alkene is 0.1~70%.

28. anticorrosive paint according to claim 16, which is characterized in that the dispersant be water, N-Methyl pyrrolidone, Any one in N,N-dimethylformamide, acetone, ethyl alcohol, n-butanol or ethyl acetate or two or more combinations.

29. anticorrosive paint according to claim 16, which is characterized in that by the gross mass of anticorrosive paint be 100% in terms of, institute The mass percent for stating dispersant is 5~45%.

30. the preparation method of the anticorrosive paint as described in claim 15 or 16, which is characterized in that the method includes following steps Suddenly：Limbic function graphite alkene is added in dispersant, mechanical agitation 1~for 24 hours, it obtains limbic function graphite alkene anti-corrosion and applies Material, the anticorrosive paint are limbic function graphite alkene one pack system anticorrosive paint.

31. the preparation method of the anticorrosive paint as described in claim 15 or 16, which is characterized in that the method includes following steps Suddenly：By any one or the two or more combinations in limbic function graphite alkene and film forming agent, filler, auxiliary agent or curing agent It is added in dispersant, stirring 1~for 24 hours, defoaming is stood, limbic function graphite alkene anticorrosive paint is obtained, which is Limbic function graphite alkene composite anticorrosion coating.