CN110791178A - Hyperbranched polyether functionalized graphene/epoxy resin nano composite coating and preparation method and application thereof - Google Patents

Abstract

The invention relates to a hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating, a preparation method and application thereof. The nanocomposite coating is composed of A component and B component. Rust pigment, inorganic pigment, mineral powder, organic solvent, component B is epoxy resin curing agent, the mixed resin is composed of epoxy resin and hyperbranched polyether functionalized graphene, and the hyperbranched polyether functionalized The mass percentage of graphene in the epoxy resin is 2% to 10%. The coating prepared by the hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating of the present invention can effectively shield corrosive substances and show more excellent corrosion resistance, especially the acid resistance of the nanocomposite coating is obvious Improve, up to 50% higher than pure epoxy coating.

Description

A kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating and its Preparation method and application

technical field

The invention relates to the technical field of coatings, in particular to a hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating and a preparation method and application thereof.

Background technique

Epoxy resin coatings are widely used in various occasions due to their excellent adhesion, low shrinkage, good corrosion resistance and chemical resistance. However, its wide application is limited due to its poor corrosion resistance. Therefore, great efforts have been devoted to improving the corrosion resistance of epoxy coatings. Epoxy coatings are chemically or physically modified with thermoplastics, silicone modifiers, liquid rubbers, hyperbranched polymers. Thermoplastics can increase the viscosity of the coating system, which is not conducive to processing; siloxanes and liquid rubbers can react to induce phase separation and are sensitive to processing, which affects the flexibility of resin curing and processing conditions. Despite the above-mentioned progress, the existing improvement methods do not achieve the expected corrosion resistance. Therefore, the development of efficient epoxy resin modifiers is a top priority.

Graphene oxide (GO) exhibits excellent properties such as gas permeability resistance, chemical (acid/alkali/salt) resistance, thermal properties, and mechanical strength. Therefore, graphene-based materials have been extensively studied in the coatings industry in recent years. However, GO is a hydrophilic nanoparticle with serious agglomeration. Conventional silane coupling agents cannot modify it well, so that it cannot be uniformly dispersed in water or coatings. The decentralization problem limits its wide application. In recent years, hyperbranched polymers have attracted extensive attention due to their unique structures and excellent properties. Its unique structure makes it have the excellent properties of low melt, low solution viscosity and high solubility. When graphene oxide and hyperbranched polymers are combined, a hyperbranched polymer functionalized with graphene oxide is obtained. However, most of these reports focus on the improvement of mechanical properties and functional preparation methods, and most of the functionalization methods include multiple preparation steps, which are time-consuming and inefficient.

SUMMARY OF THE INVENTION

In order to solve the technical problems of complex graphene oxide functionalized preparation method, poor dispersibility and poor anticorrosion performance of epoxy resin, a hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating and preparation method and application thereof are provided, The nanocomposite material of the present invention has excellent anticorrosion performance.

In order to achieve the above object, the present invention realizes through the following technical solutions:

A hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating is composed of A component and B component, and the A component includes the following components in parts by weight: 30-40 parts of mixed resin, antirust pigment 10-15 parts, inorganic pigments 15-25 parts, mineral powder 10-15 parts, organic solvent 10-30 parts, the B component is epoxy resin curing agent 38-55 parts;

The mixed resin is composed of epoxy resin and hyperbranched polyether functionalized graphene. Ether-functionalized graphene is prepared by one-step reaction of graphene oxide and hyperbranched polyether epoxy resin under the action of catalyst.

Further, M _n of the hyperbranched polyether epoxy resin is 1200g/mol～2500g/mol, and the hyperbranched polyether epoxy resin is resorcinol, trimethylolpropane triglycidyl ether Under the action of catalyst tetrabutylammonium bromide, it is obtained by reacting at 100 °C;

The preparation method of the hyperbranched polyether functionalized graphene is as follows: at room temperature, graphene oxide and hyperbranched polyether epoxy resin are added to a DMF solvent in a mass ratio of 1:100, ultrasonically treated, and then a catalyst is added The amount of tetrabutylammonium bromide was heated to 80 °C for 10 h under stirring. After the reaction, the temperature was lowered to room temperature, washed with water, centrifuged and filtered to obtain hyperbranched polyether-functionalized graphene.

Further, the epoxy resin is a bisphenol A epoxy resin.

Further, the anti-rust pigment is zinc molybdate and/or zinc sulfate, and the particle size of the anti-rust pigment is 800 mesh.

Further, the inorganic pigment is one or more of ferric oxide, zinc oxide and titanium dioxide, and the particle size of the inorganic pigment is 800 mesh to 2000 mesh.

Further, the mineral powder is mica and/or talc powder, and the particle size of the mineral powder is 800 mesh to 1250 mesh.

Further, the organic solvent is that xylene and butanone are mixed in a ratio of 7:3 by volume.

Further, the epoxy resin curing agent is LITE3000.

Another aspect of the present invention provides a preparation method of the above-mentioned hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating, comprising the following steps:

(1) Weigh the raw materials of component A and component B according to the formula; the mixed resin composed of epoxy resin and hyperbranched polyether-functionalized graphene and a part of organic solvent are stirred and mixed to uniform and transparent, and then added under stirring Antirust pigments, inorganic pigments and mineral powders are pre-mixed and transferred to a cone mill for grinding to form a uniformly dispersed color paste;

(2) the epoxy resin curing agent, the remaining part of the organic solvent and the color paste are stirred until uniform and transparent to obtain a hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating, which is coated on the surface of the substrate, and is After curing at room temperature for 2-7 days, the coating of the nanocomposite coating can be obtained.

The last aspect of the present invention provides the anticorrosion of the above-mentioned hyperbranched polyether-functionalized graphene/epoxy resin nanocomposite coating applied to the surface of a metal substrate. The anti-corrosion performance of the nano-composite coating of the invention is particularly manifested in that its anti-acid corrosion ability is improved by 50% compared with that of pure epoxy resin, and has excellent anti-corrosion performance.

Beneficial technical effects:

In the present invention, hyperbranched polyether epoxy resin and graphene oxide are grafted to form hyperbranched polyether functionalized graphene, which is added to the epoxy resin as a modifier. The hyperbranched polyether epoxy resin is branched, so that its dispersibility in the epoxy resin matrix is better than that of graphene oxide modified by other general modification means such as silane coupling agent, so that each component is better. The compatibility of graphene oxide is better, so that the network structure in the coating formed during curing is more uniform. Because graphene oxide itself has good impermeability, it can be uniformly dispersed in the network structure to play its role more effectively. On the other hand, the hyperbranched polymer at one end of the hyperbranched polyether-functionalized graphene contains multiple terminal active groups, which increases the crosslinking points for forming the epoxy resin network and increases the crosslinking density. This makes the epoxy resin network in the prepared nanocomposite coating have smaller micropores, so the diffusion path is narrower, so that the nanocomposite coating of the present invention can be used in graphene oxide and hyperbranched polyether epoxy resins. It has better corrosion resistance under the synergistic effect of 1+1>2.

The coating prepared by the hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating of the present invention has a narrower diffusion path, can effectively shield corrosive substances, has a lower corrosion rate, and exhibits more excellent performance. The corrosion resistance, especially the acid resistance of the nanocomposite coating, is significantly improved, which is 50% higher than that of the pure epoxy resin coating.

Description of drawings

Figure 1 is a schematic diagram of the reaction process of hyperbranched polyether-functionalized graphene.

FIG. 2 is an electrochemical impedance spectroscopy diagram of coated steel sheets obtained by coating the coatings of Examples 2 to 5 and Comparative Example 1 after curing in a 3.5 wt % NaCl solution for 5 days. Among them, 0% EHBPE-GO represents the coated steel plate obtained by curing the pure epoxy resin coating in Comparative Example 1, 3% EHBPE-GO represents the coated steel plate obtained by curing the nanocomposite coating in Example 2, and 5% EHBPE-GO represents the example 3 The coated steel plate obtained by curing the nanocomposite coating, 8% EHBPE-GO represents the coated steel plate obtained by curing the nanocomposite coating in Example 4, and 10% EHBPE-GO represents the coated steel plate obtained by curing the nanocomposite coating in Example 4.

Figure 3 is the electrochemical Bode diagram of the coated steel plate obtained by curing the nanocomposite coating of Example 4 (8wt% EHBPE-GO) immersed in 3.5wt% NaCl solution for different times, wherein (a) is the Bode modulus diagram, (b) ) Bode phase diagram.

FIG. 4 is a graph showing the relationship between the soaking time and the corrosion depth of the coated steel plate obtained by curing the nanocomposite coating of Example 4 (8wt% EHBPE-GO) in a 3.5wt% NaCl solution.

Detailed ways

The present invention is further described below with reference to the accompanying drawings and specific embodiments, but does not limit the scope of the present invention.

The preparation method of the hyperbranched polyether epoxy resin of the present invention is as follows: adding resorcinol (4.40 g, 0.04 mol) and trimethylolpropane triglycidyl ether (36.28 g, 0.12 mol) to a container containing The three-necked flask with mechanical stirring, thermometer and nitrogen inlet and outlet was heated to 100°C under nitrogen protection, and then the catalyst tetrabutylammonium bromide (1.93 g, 0.006 mmol) was added to react for 48 hours; after the reaction was completed, it was cooled to room temperature and added 100ml THF dissolves the product, then pour the solution into a large amount of hot water and stir well, and then remove the upper layer liquid after standing, this step is repeated 3 times, the purpose is to remove the catalyst; add a small amount of THF to the remaining lower layer liquid to dissolve, add MgSO ₄ After drying, suction filtration, the obtained filtrate is subjected to rotary evaporation to remove part of THF, then the liquid is immersed in diethyl ether for 3 times, and the upper layer liquid is fully stirred to remove the polymer with low molecular weight; The yellow transparent viscous liquid is hyperbranched polyether epoxy resin, hereinafter abbreviated as EHBPE, and Mn=2000g/mol of hyperbranched polyether epoxy resin is obtained by GPC detection and calculation.

Example 1

The preparation method of the hyperbranched polyether-functionalized graphene of the present invention is as follows: at room temperature of 25° C., adding 10.2 mg of graphene oxide and 1.019 g of EHBPE prepared by the above method into 40 mL of DMF, and treating with ultrasound (frequency is 5000 Hz) for 30 minutes , then add 0.05g of tetrabutylammonium bromide, heat to 80°C under the condition of magnetic stirring speed of 300rpm, after 10h of reaction, the reaction system is lowered to room temperature, washed with water, centrifuged and filtered to obtain graphene oxide modified hyperbranched Polyether epoxy resin, hereinafter abbreviated as EHBPE-GO.

The reaction process is shown in Figure 1.

The obtained EHBPE-GO was tested by Fourier transform infrared spectroscopy, and the results showed that there was a carbonyl peak on the surface of graphene oxide at 1750cm- ¹ , and aliphatic-CH stretching vibration peak at 2960cm ^{- 1} ～2880cm ^-1 was at 1231cm-1. ¹ and 1100 cm ^-1 belong to the stretch vibration peaks of Ph-OC and COC, respectively, and the characteristic absorption peaks of epoxy group at 908 cm ^-1 and 843 cm ^-1 , which indicated that EHBPE was successfully grafted on the end of GO.

Example 2

A hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating is composed of A component and B component, and the A component includes the following components by weight: 33.4 parts of mixed resin, antirust pigment: molybdenum 6 parts of zinc acid and 8 parts of zinc phosphate, inorganic pigment: 20 parts of ferric oxide, mineral powder: 4.8 parts of mica and 7.8 parts of talcum powder, organic solvent: xylene and methyl ethyl ketone mixed in a volume ratio of 7:3 to prepare 20 share,

The B component is 43.6 parts of epoxy resin curing agent LITE3000;

The mixed resin is composed of the hyperbranched polyether-functionalized graphene obtained in Example 1 and a bisphenol A-type epoxy resin, and the weight of the hyperbranched polyether-functionalized graphene accounts for about the bisphenol A-type ring. 3% of the weight of the oxygen resin, that is, 1 part of hyperbranched polyether-functionalized graphene, and 32.4 parts of bisphenol A epoxy resin.

Example 3

The hyperbranched polyether-functionalized graphene/epoxy resin nanocomposite coating of this embodiment is the same as that of embodiment 2, the difference is that the weight of hyperbranched polyether-functionalized graphene accounts for about 30% of the bisphenol A-type ring. 5% by weight of the oxygen resin, namely 1.6 parts of hyperbranched polyether-functionalized graphene and 31.8 parts of bisphenol A epoxy resin.

Example 4

The hyperbranched polyether-functionalized graphene/epoxy resin nanocomposite coating of this embodiment is the same as that of embodiment 2, the difference is that the weight of hyperbranched polyether-functionalized graphene accounts for about 30% of the bisphenol A-type ring. 8% by weight of the oxygen resin, namely 2.5 parts of hyperbranched polyether-functionalized graphene and 30.9 parts of bisphenol A epoxy resin.

Example 5

The hyperbranched polyether-functionalized graphene/epoxy resin nanocomposite coating of this embodiment is the same as that of embodiment 2, the difference is that the weight of hyperbranched polyether-functionalized graphene accounts for about 30% of the bisphenol A-type ring. 10% by weight of the oxygen resin, namely 3.1 parts of hyperbranched polyether-functionalized graphene and 30.3 parts of bisphenol A epoxy resin.

Example 6

A hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating is composed of component A and component B, the component A includes the following components by weight: 40 parts of mixed resin, antirust pigment: molybdenum 4 parts of zinc acid and 6 parts of zinc phosphate, inorganic pigment: 25 parts of ferric oxide, mineral powder: 6 parts of mica and 9 parts of talc powder, organic solvent: xylene and methyl ethyl ketone mixed in a volume ratio of 7:3 to prepare 30 share,

The B component is 53 parts of epoxy resin curing agent LITE3000;

The mixed resin is composed of the hyperbranched polyether-functionalized graphene obtained in Example 1 and a bisphenol A-type epoxy resin, and the weight of the hyperbranched polyether-functionalized graphene accounts for about the bisphenol A-type ring. 8.1% by weight of the oxygen resin, namely 3 parts of hyperbranched polyether-functionalized graphene and 37 parts of bisphenol A epoxy resin.

Example 7

A hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating is composed of A component and B component, and the A component includes the following components in parts by weight: 30 parts of mixed resin, antirust pigment: molybdenum 5 parts of zinc acid and 7 parts of zinc phosphate, inorganic pigment: 15 parts of ferric oxide, mineral powder: 3 parts of mica and 7 parts of talcum powder, organic solvent: xylene and methyl ethyl ketone mixed in a volume ratio of 7:3 to prepare 12 share,

The B component is 39.2 parts of epoxy resin curing agent LITE3000;

The mixed resin is composed of the hyperbranched polyether-functionalized graphene obtained in Example 1 and a bisphenol A-type epoxy resin, and the weight of the hyperbranched polyether-functionalized graphene accounts for the bisphenol A-type epoxy resin. 7.9% by weight of the resin, namely 2.2 parts of hyperbranched polyether-functionalized graphene and 27.8 parts of bisphenol A epoxy resin.

Comparative Example 1

The difference between this comparative example and Example 2 is that no EHBPE-GO is added, and it is a pure epoxy resin coating (abbreviated as DGEBA).

Example 8

The preparation method of embodiment 2 coating, comprises the steps:

(1) Weigh the raw materials of component A and component B according to the formula; stir and mix mixed resin and epoxy resin with a part of organic solvent until uniform and transparent, and then add antirust pigment, inorganic pigment, mineral The material powder is premixed and transferred to a cone mill for grinding to form a uniformly dispersed color paste;

(2) the epoxy resin curing agent, the remaining organic solvent and the color paste are stirred until uniform and transparent, coated on the surface of the substrate, and cured at room temperature for 7 days to obtain the hyperbranched polyether-functionalized graphene of Example 2 / Coating of epoxy nanocomposite coatings.

The coating preparation methods of the coatings of Examples 3 to 7 and Comparative Example 1 are the same as the coating preparation methods of Example 2.

Example 9

Taking Q235 low carbon steel plate (100mm×50mm×1mm) as the metal matrix, first grind the steel plate with No. 400 sandpaper to remove the abrasive dust, then wash with acetone and ethanol, and then according to the preparation method of the coating in Example 8, the embodiment The coatings of 2-5 and Comparative Example 1 were applied to the front and back surfaces of the Q235 steel plate, and cured for one week at room temperature to obtain a coated steel plate with a coating thickness of about 30 μm.

Anti-corrosion performance test

In order to accelerate the failure process of the coating, 10wt% _H2SO4 solution, 5wt% _NaOH solution, and deionized water were selected as the corrosion medium for electrochemical corrosion test. The coated steel plates obtained by coating the coatings of Examples 2 to 5 and Comparative Example 1 on Q235 were immersed in 10wt% H ₂ SO ₄ solution, 5wt% NaOH solution and deionized water respectively, and the coated steel plate was separated from the surface of the solution. 7cm deep, the test time for immersion is up to 80 days.

The electrochemical impedance spectra of the coated steel sheets obtained by coating the coatings of Examples 2 to 5 and Comparative Example 1 after being immersed in 3.5wt% NaCl solution for 5 days are shown in Figure 2, and 0% EHBPE-GO in Figure 2 represents Comparative Example 1 The coated steel plate obtained by curing the pure epoxy resin coating, 3% EHBPE-GO represents the coated steel plate obtained by curing the nanocomposite coating in Example 2, and 5% EHBPE-GO represents the coating obtained by curing the nanocomposite coating in Example 3. Layer steel plate, 8% EHBPE-GO represents the coated steel plate obtained by curing the nanocomposite coating in Example 4, and 10% EHBPE-GO represents the coated steel plate obtained by curing the nanocomposite coating in Example 4. It can be seen from Figure 2 that the higher the impedance value, the better the corrosion resistance, that is, the corrosion resistance of the hyperbranched polyether functionalized graphene/epoxy nanocomposite coating is obviously better than that of the pure epoxy coating. , which indicates that EHBPE-GO can significantly improve the corrosion resistance of epoxy resin coatings. In addition, when the amount of EHBPE-GO was 8 wt%, the corrosion resistance of the nanocomposite coating was the best.

The results obtained at shorter test times were insufficient to reveal the protective properties of the nanocomposite coatings. Therefore, the electrochemical corrosion under longer immersion time was tested, as shown in Figure 3, which shows the coated steel plate obtained by curing the nanocomposite coating of Example 4 (8wt% EHBPE-GO) in 3.5wt% NaCl solution Electrochemical Bode diagrams of different immersion time, in which (a) is the Bode modulus diagram, (b) the Bode phase diagram, the test time is 1 day, 2 days, 5 days, 15 days, 30 days, 50 days and 80 days, respectively . It can be seen from Figure 3 that after 80 days of immersion in (a), the impedance at 0.1 Hz is greater than 107Ω·cm ² , and the nanocomposite coating still has good corrosion resistance and can protect the metal well. But with the immersion test carried out at low frequency, the impedance value of the nanocomposite coating does not decrease but increases, which is inconsistent with the traditional phenomenon. The main reason is that during the corrosion process, no matter how dense the coating is, the corrosive ions in the solution can penetrate the substrate for a long time. Once the corrosive ions in the solution contact the metal, a corrosion reaction occurs, and the corrosion produces a corrosion product film. And the film can function as a protective layer.

The relationship between the soaking time and the corrosion depth of the coated steel plate obtained by curing the nanocomposite coating of Example 4 (8wt% EHBPE-GO) in 3.5wt% NaCl solution is shown in Figure 4. It can be seen from Figure 4 that for DGEBA (pure Epoxy) coating, the corrosion depth increases with the increase of immersion time; while the corrosion depth of the nanocomposite coating containing 8wt% EHBPE-GO is significantly lower than that of the pure epoxy coating, and the corrosion depth increases with the increase of time. The depth has not increased. For the nanocomposite coating containing 8 wt% EHBPE-GO, the corrosion depth remained basically unchanged with the prolongation of immersion time, indicating that it has excellent corrosion resistance during the 80-day immersion time. The electrochemical performance parameters of the nanocomposite coating of Example 4 (8wt% EHBPE-GO) and the pure epoxy resin coating of Comparative Example 1 after being soaked in 3.5wt% NaCl solution for 80 days are shown in Table 1.

Table 1 Electrochemical performance parameters of coatings after soaking in 3.5wt% NaCl solution for 80 days

Electrochemical performance parameters of the nanocomposite coating of Example 4 (8wt% EHBPE-GO) and the pure epoxy resin coating of Comparative Example 1 after soaking in 10wt% H2SO4 solution, 5wt% NaOH solution and deionized water solution for 80 days, respectively , In addition, a salt spray test was also carried out, and the data are shown in Table 2.

Table 2 Electrochemical performance parameters of coatings after soaking in 10wt% H2SO4 solution, 5wt% NaOH solution and deionized water solution for 80 days, respectively

From Table 2, it can be seen that both the DGEBA (pure epoxy resin) coating and the 8wt% EHBPE-GO/DGEBA (nanocomposite coating) showed better resistance to deionized water and 5wt% NaOH solution . But there is a significant difference in resistance to 10wt _{% H2SO4} solution. The results show that the acid resistance of the nanocomposite coating is significantly improved, which is 50% higher than that of the pure epoxy resin coating.

Even in a highly cross-linked network, there are some micropores. When the coated steel sheet is immersed in a corrosive solution, the channels formed by the larger pores provide channels for the diffusion of corrosive substances. The weaker the corrosion resistance of the material, the wider its diffusion path, which means that the micropores in the material are larger. Therefore, the diffusion path in the pure epoxy coating is wider than that in the nanocomposite coating. Once the pure epoxy coating is penetrated by the electrolyte solution, the corrosion process is accelerated sharply and the corrosion rate increases. In the present invention, the hyperbranched polyether epoxy resin and graphene oxide are grafted to form hyperbranched polyether functionalized graphene, which is added to the epoxy resin as a modifier. The hyperbranched polyether epoxy resin is grafted on the olefin, so that its dispersibility in the epoxy resin matrix is better than that of graphene oxide modified by other general modification means such as silane coupling agent, so that the The compatibility of each component is better, so that the network structure in the coating formed during curing is more uniform. Because graphene oxide itself has good impermeability, it can be uniformly dispersed in the network structure to play a role. Its more effective impermeability; on the other hand, because the hyperbranched polymer at one end of the hyperbranched polyether-functionalized graphene contains multiple terminal active groups, the crosslinking points for forming the epoxy resin network are increased, making the crosslinking The density increases, which makes the epoxy resin network in the prepared nanocomposite coating have smaller micropores, so the diffusion path is narrower, so that the nanocomposite coating of the present invention can be used in graphene oxide and hyperbranched polyethers. Under the synergistic effect of epoxy resin, it has better corrosion resistance and achieves the effect of 1+1>2.

To sum up, the coating prepared with the hyperbranched polyether-functionalized graphene/epoxy resin nanocomposite coating of the present invention has a narrower diffusion path, which can effectively shield corrosive substances, so as to have a lower corrosion rate , showing more excellent corrosion resistance. The nanocomposite coating of the invention can be applied to the surface anticorrosion of metal substrates, and the formed nanocomposite coating has better anticorrosion effect.

Claims (10)

1. a hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating, is characterized in that, described nanocomposite coating is made up of A component and B component, and described A component comprises following parts by weight component : Mixed resin 30-40 parts, anti-rust pigment 10-15 parts, inorganic pigment 15-25 parts, mineral powder 10-15 parts, organic solvent 10-30 parts, the B component is epoxy resin curing agent 38 - 55 copies; The mixed resin is composed of epoxy resin and hyperbranched polyether functionalized graphene. Ether-functionalized graphene is prepared by one-step reaction of graphene oxide and hyperbranched polyether epoxy resin under the action of catalyst. 2. a kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to claim 1, is characterized in that, the M _n =1200g/mol～2500g of described hyperbranched polyether epoxy resin /mol, the hyperbranched polyether epoxy resin is obtained by reacting resorcinol and trimethylolpropane triglycidyl ether at 100°C under the action of catalyst tetrabutylammonium bromide; The preparation method of the hyperbranched polyether functionalized graphene is as follows: at room temperature, graphene oxide and hyperbranched polyether epoxy resin are added to a DMF solvent in a mass ratio of 1:100, ultrasonically treated, and then a catalyst is added The amount of tetrabutylammonium bromide was heated to 80 °C for 10 h under stirring. After the reaction, the temperature was lowered to room temperature, washed with water, centrifuged and filtered to obtain hyperbranched polyether-functionalized graphene. 3. a kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to claim 1, is characterized in that, described epoxy resin is bisphenol A type epoxy resin. 4. a kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to claim 1, is characterized in that, described antirust pigment is zinc molybdate and/or zinc sulfate, and described antirust pigment is zinc molybdate and/or zinc sulfate The particle size of the pigment is 800 mesh. 5. a kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to claim 1, is characterized in that, described inorganic pigment is a kind of in ferric oxide, zinc oxide, titanium dioxide or Several kinds, the particle size of the inorganic pigment is 800 mesh to 2000 mesh. 6. a kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to claim 1, is characterized in that, described mineral powder is mica and/or talcum powder, and described mineral powder is The particle size is 800 mesh to 1250 mesh. 7. a kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to claim 1, is characterized in that, described organic solvent is that xylene and methyl ethyl ketone are mixed in the ratio of volume ratio 7:3 . 8. a kind of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to claim 1, is characterized in that, described epoxy resin curing agent is LITE3000. 9. a preparation method of hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating according to any one of claims 1～8, is characterized in that, comprises the steps: (1) Weigh the raw materials of component A and component B according to the formula; the mixed resin composed of epoxy resin and hyperbranched polyether-functionalized graphene and a part of organic solvent are stirred and mixed to uniform and transparent, and then added under stirring Antirust pigments, inorganic pigments and mineral powders are pre-mixed and transferred to a cone mill for grinding to form a uniformly dispersed color paste; (2) the epoxy resin curing agent, the remaining part of the organic solvent and the color paste are stirred until uniform and transparent to obtain a hyperbranched polyether functionalized graphene/epoxy resin nanocomposite coating, which is coated on the surface of the substrate, and is After curing at room temperature for 2-7 days, the coating of the nanocomposite coating can be obtained. 10 . The hyperbranched polyether-functionalized graphene/epoxy resin nanocomposite coating according to any one of claims 1 to 8 is applied to the anticorrosion of the surface of a metal substrate. 11 .

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