Stain-resistant acrylic resin, paint and preparation method thereof

Abstract

The invention relates to the technical field of acrylic resin, and discloses a smudginess-resistant polyethylene glycol-graphene grafted acrylic resin coating, which is characterized in that graphene of TEMPO-polyethylene glycol modified graphene is used as a polymerization carrier, TEMPO free radicals are used as initiation sites to initiate in-situ chemical graft polymerization of monomers such as n-butyl acrylate, acrylic acid and the like on the surface of graphene so as to prepare the smudginess-resistant polyethylene glycol-graphene grafted acrylic resin coating. The graphene is connected with the acrylic resin through a polyethylene glycol molecular chain, so that the graphene is organically combined with the acrylic resin, the dispersity of the graphene is improved, the agglomeration in the acrylic resin is overcome, and the graphene-graphene-grafted acrylic resin is prepared. The graphene obviously improves the tensile strength and other mechanical properties of the acrylic resin, and meanwhile, the grafted polar polyethylene glycol molecular chain can improve the hydrophilicity and smudginess resistance of the acrylic resin.

Description

Technical Field

[0001] The invention relates to the technical field of acrylic resins, and in particular to a stain-resistant polyethylene glycol-graphene grafted acrylic resin, a coating and a preparation method thereof. Background Art

[0002] Acrylic resin coating is a polymer material obtained by polymerizing monomers such as n-butyl acrylate and acrylic acid. Traditional acrylic resin polymerization methods mainly include emulsion polymerization, suspension polymerization, in-situ polymerization and other methods. Acrylic resin coating has good film-forming properties, gloss retention, color retention, water resistance and chemical resistance, and is widely used in automobiles, consumer electronics, etc. However, it is not resistant to dirt, which makes it difficult to clean once it is stained with oil and dust. In order to expand the practical application of acrylic resin coating, it is necessary to modify the acrylic resin to improve its mechanical strength and dirt resistance.

[0003] Graphene has excellent mechanical properties, thermodynamic stability and oleophobicity, and is an ideal nanofiller for polymer materials. It has broad application prospects in polymers such as polyurea resins and acrylic resins, and can enhance the thermal stability, mechanical strength and oil resistance of materials. However, graphene has an obvious defect, that is, it has poor compatibility with acrylic resins and is easy to form agglomerates. The in-situ polymerization method is to chemically graft monomers such as acrylic acid on the graphene surface, which is an effective way to solve the dispersion and agglomeration problems of graphene.

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies in the prior art, the present invention provides a dirt-resistant polyethylene glycol-graphene grafted acrylic resin, a coating and a preparation method thereof, wherein the coating has better mechanical strength and oil resistance.

[0006] (II) Technical solution

[0007] To achieve the above object, the present invention provides the following technical solution: a stain-resistant polyethylene glycol-graphene grafted acrylic resin, and the preparation method of the stain-resistant polyethylene glycol-graphene grafted acrylic resin is as follows: (1) Succinic anhydride and polyethylene glycol are reacted to obtain double-terminal carboxyl polyethylene glycol, which is then reacted with thionyl chloride to obtain double-terminal acyl chloride polyethylene glycol.

[0008] (2) Adding graphene oxide to toluene solvent, adding double-ended acyl chloride polyethylene glycol after ultrasonic homogenization to carry out modification reaction, removing the solvent by centrifugation, and washing the product with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0009] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO), and reaction promoter triethylamine to toluene solvent for esterification reaction. Centrifuge to separate and remove the solvent, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene.

[0010] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate, and TEMPO-polyethylene glycol modified graphene to distilled water. Treat it by liquid nitrogen cooling - vacuum pumping - nitrogen cycling, then ultrasonically homogenize it, and carry out in-situ polymerization reaction in a nitrogen atmosphere. Add distilled water for centrifugation to obtain polyethylene glycol-graphene grafted acrylic resin.

[0011] Add polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, and film-forming aid alcohol ester twelve to distilled water solvent, and obtain a stain-resistant polyethylene glycol-graphene grafted acrylic resin coating after high-speed emulsification. The mass ratio of the polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, and film-forming aid alcohol ester twelve is: 100:50 - 100:60 - 150:30 - 80.

[0012] Preferably, the molecular weight of the polyethylene glycol in step (1) is 200 or 400.

[0013] Preferably, the mass ratio of graphene oxide and bis-terminal acyl chloride polyethylene glycol in step (2) is 10:250 - 450.

[0014] Preferably, the temperature of the modification reaction in step (2) is 60 - 90 °C, and the reaction time is 12 - 24 h.

[0015] Preferably, the mass ratio of acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and triethylamine in step (3) is 100:60 - 110:150 - 280.

[0016] Preferably, the temperature of the esterification reaction in step (3) is 50 - 75 °C, and the reaction time is 24 - 48 h.

[0017] Preferably, the mass ratio of n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate, and TEMPO-polyethylene glycol modified graphene in step (4) is 100:35 - 50:4 - 10:3 - 7:1.5 - 4.

[0018] Preferably, the temperature of the in-situ polymerization reaction in step (4) is 80 - 110 °C, and the reaction time is 24 - 48 h.

[0019] (III) Beneficial technical effects

[0020] Compared with the prior art, the present invention has the following beneficial technical effects: For the stain-resistant polyethylene glycol-graphene grafted acrylic resin coating, one acyl chloride group of the bis-terminal acyl chloride polyethylene glycol reacts with the surface hydroxyl group of graphene oxide to obtain acyl chloride polyethylene glycol modified graphene. Then, in the promotion system of triethylamine, the terminal acyl chloride group further undergoes an esterification reaction with the hydroxyl group of 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide to obtain TEMPO-polyethylene glycol modified graphene, thereby introducing polar polyethylene glycol molecular chains and active TEMPO free radicals on the surface of graphene.

[0021] For the stain-resistant polyethylene glycol-graphene grafted acrylic resin coating, the graphene of the TEMPO-polyethylene glycol modified graphene serves as a polymerization carrier, and the TEMPO free radical serves as an initiation site to initiate the in-situ chemical graft polymerization of monomers such as n-butyl acrylate and acrylic acid on the surface of graphene, obtaining polyethylene glycol-graphene grafted acrylic resin. Graphene is connected to the acrylic resin through the polyethylene glycol molecular chain, enabling the organic combination of graphene and the acrylic resin, improving the dispersibility of graphene, overcoming the agglomeration in the acrylic resin. Graphene significantly enhances the mechanical properties such as the tensile strength of the acrylic resin and the oil resistance performance. At the same time, the grafted polar polyethylene glycol molecular chain can improve the hydrophilicity and organic solvent resistance of the acrylic resin, further enhancing the oil resistance performance of the coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a reaction diagram of graphene oxide and bis-terminal acyl chloride polyethylene glycol; Figure 2 is a reaction schematic diagram of acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide and the reaction promoter triethylamine. DETAILED DESCRIPTION OF THE INVENTION

[0023] To achieve the above object, the present invention provides the following specific embodiments and examples: A stain-resistant polyethylene glycol-graphene grafted acrylic resin and a method for preparing a coating using the resin are as follows: (1) React succinic anhydride with polyethylene glycol, where the molecular weight of polyethylene glycol is 200 or 400, to obtain bis-terminal carboxyl polyethylene glycol, and then react with thionyl chloride to obtain bis-terminal acyl chloride polyethylene glycol; (2) Graphene oxide was added to toluene solvent. After ultrasonic homogenization, bis - terminal acyl chloride polyethylene glycol was added, and the mass ratio of the two was 10:250 - 450. The modification reaction was carried out at 60 - 90 °C for 12 - 24 h. The solvent was removed by centrifugation, and the product was washed with toluene and ethanol to obtain acyl chloride polyethylene glycol - modified graphene; (3) Acyl chloride polyethylene glycol - modified graphene, 4 - hydroxy - 2,2,6,6 - tetramethylpiperidine nitroxide and the reaction promoter triethylamine with a mass ratio of 100:60 - 110:150 - 280 were added to toluene solvent. The esterification reaction was carried out at 50 - 75 °C for 24 - 48 h. The solvent was removed by centrifugation, and the product was washed with chloroform and distilled water to obtain TEMPO - polyethylene glycol - modified graphene; (4) n - butyl acrylate, methyl methacrylate, acrylic acid, 2 - hydroxyethyl acrylate and TEMPO - polyethylene glycol - modified graphene with a mass ratio of 100:35 - 50:4 - 10:3 - 7:1.5 - 4 were added to distilled water. Through liquid nitrogen cooling - vacuum pumping - nitrogen circulation treatment, and then ultrasonic homogenization, in a nitrogen atmosphere, the in - situ polymerization reaction was carried out at 80 - 110 °C for 24 - 48 h. Distilled water was added for centrifugation to obtain polyethylene glycol - graphene grafted acrylic resin.

[0024] Polyethylene glycol - graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether - modified silicone defoamer, film - forming auxiliary alcohol ester twelve were added to distilled water solvent. After high - speed emulsification, a dirt - resistant polyethylene glycol - graphene grafted acrylic resin coating was obtained.

[0025] Example 1

[0026] (1) Succinic anhydride was reacted with polyethylene glycol 200 to obtain bis - terminal carboxyl polyethylene glycol, and then reacted with thionyl chloride to obtain bis - terminal acyl chloride polyethylene glycol; (2) Graphene oxide was added to toluene solvent. After ultrasonic homogenization, bis - terminal acyl chloride polyethylene glycol was added, and the mass ratio of the two was 10:250. The modification reaction was carried out at 60 °C for 12 h. The solvent was removed by centrifugation, and the product was washed with toluene and ethanol to obtain acyl chloride polyethylene glycol - modified graphene; (3) Acyl chloride polyethylene glycol - modified graphene, 4 - hydroxy - 2,2,6,6 - tetramethylpiperidine nitroxide and the reaction promoter triethylamine with a mass ratio of 100:60:150 were added to toluene solvent. The esterification reaction was carried out at 50 °C for 24 - 48 h. The solvent was removed by centrifugation, and the product was washed with chloroform and distilled water to obtain TEMPO - polyethylene glycol - modified graphene; (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate, and TEMPO-polyethylene glycol modified graphene with a mass ratio of 100:35:4:3:1.5 to distilled water. Through liquid nitrogen cooling-vacuum pumping-nitrogen cycling treatment, and then ultrasonic homogenization, in a nitrogen atmosphere, carry out in-situ polymerization reaction at 80 °C for 24 h, add distilled water for centrifugal separation to obtain polyethylene glycol-graphene grafted acrylic resin.

[0027] Add polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, and film-forming aid 2,2,4-trimethyl-1,3-pentanediol isobutyrate to distilled water solvent, and obtain stain-resistant polyethylene glycol-graphene grafted acrylic resin coating after high-speed emulsification.

[0028] Example 2

[0029] (1) React succinic anhydride with polyethylene glycol 400 to obtain double-terminal carboxyl polyethylene glycol, and then react with thionyl chloride to obtain double-terminal acyl chloride polyethylene glycol; (2) Add graphene oxide to toluene solvent, after ultrasonic homogenization, add double-terminal acyl chloride polyethylene glycol, with a mass ratio of 10:320 between the two, carry out modification reaction at 80 °C for 18 h, centrifugally separate to remove the solvent, and wash the product with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene; (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and reaction promoter triethylamine with a mass ratio of 100:75:190 to toluene solvent, carry out esterification reaction at 65 °C for 36 h, centrifugally separate to remove the solvent, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene; (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate, and TEMPO-polyethylene glycol modified graphene with a mass ratio of 100:40:6:4.5:2.2 to distilled water. Through liquid nitrogen cooling-vacuum pumping-nitrogen cycling treatment, and then ultrasonic homogenization, in a nitrogen atmosphere, carry out in-situ polymerization reaction at 100 °C for 36 h, add distilled water for centrifugal separation to obtain polyethylene glycol-graphene grafted acrylic resin.

[0030] Add polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, and film-forming aid 2,2,4-trimethyl-1,3-pentanediol isobutyrate to distilled water solvent, and obtain stain-resistant polyethylene glycol-graphene grafted acrylic resin coating after high-speed emulsification.

[0031] Example 3

[0032] (1) React succinic anhydride with polyethylene glycol 200 to obtain polyethylene glycol with carboxyl groups at both ends, and then react it with thionyl chloride to obtain polyethylene glycol with acyl chloride groups at both ends; (2) Add graphene oxide to toluene solvent. After ultrasonic homogenization, add polyethylene glycol with acyl chloride groups at both ends. The mass ratio of the two is 10:380. At 75 °C, carry out the modification reaction for 18 h. Centrifuge to separate and remove the solvent, and wash the product with toluene and ethanol to obtain graphene modified with polyethylene glycol acyl chloride; (3) Add graphene modified with polyethylene glycol acyl chloride, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide and the reaction promoter triethylamine with a mass ratio of 100:95:240 to toluene solvent. At 60 °C, carry out the esterification reaction for 36 h. Centrifuge to separate and remove the solvent, and wash the product with chloroform and distilled water to obtain graphene modified with TEMPO-polyethylene glycol; (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate and graphene modified with TEMPO-polyethylene glycol with a mass ratio of 100:45:8:5.5:3.2 to distilled water. Through liquid nitrogen cooling-vacuum pumping-nitrogen cycling treatment, and then ultrasonic homogenization. In a nitrogen atmosphere, carry out the in-situ polymerization reaction at 100 °C for 36 h, add distilled water and carry out centrifugation to obtain polyethylene glycol-graphene grafted acrylic resin.

[0033] Add polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, film-forming aid alcohol ester twelve to distilled water solvent, and obtain a stain-resistant polyethylene glycol-graphene grafted acrylic resin coating after high-speed emulsification.

[0034] Example 4

[0035] (1) React succinic anhydride with polyethylene glycol 400 to obtain polyethylene glycol with carboxyl groups at both ends, and then react it with thionyl chloride to obtain polyethylene glycol with acyl chloride groups at both ends; (2) Add graphene oxide to toluene solvent. After ultrasonic homogenization, add polyethylene glycol with acyl chloride groups at both ends. The mass ratio of the two is 10:450. At 90 °C, carry out the modification reaction for 24 h. Centrifuge to separate and remove the solvent, and wash the product with toluene and ethanol to obtain graphene modified with polyethylene glycol acyl chloride; (3) Add graphene modified with polyethylene glycol acyl chloride, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide and the reaction promoter triethylamine with a mass ratio of 100:110:280 to toluene solvent. At 75 °C, carry out the esterification reaction for 48 h. Centrifuge to separate and remove the solvent, and wash the product with chloroform and distilled water to obtain graphene modified with TEMPO-polyethylene glycol; (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate, and TEMPO-polyethylene glycol modified graphene with a mass ratio of 100:50:10:7:4 to distilled water. Through liquid nitrogen cooling-vacuum pumping-nitrogen cycling treatment, and then ultrasonic homogenization, carry out in-situ polymerization reaction at 110 °C for 48 h in a nitrogen atmosphere. Add distilled water for centrifugal separation to obtain polyethylene glycol-graphene grafted acrylic resin; Add polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, and film-forming auxiliary alcohol ester twelve to distilled water solvent. After high-speed emulsification, obtain a stain-resistant polyethylene glycol-graphene grafted acrylic resin coating.

[0036] Comparative Example 1 Add polyethylene glycol, graphene, acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, and film-forming auxiliary alcohol ester twelve to distilled water solvent. After high-speed emulsification, obtain an acrylic resin coating.

[0037] Comparative Example 2 (1) React succinic anhydride with polyethylene glycol 400 to obtain double-terminal carboxyl polyethylene glycol, and then react with thionyl chloride to obtain double-terminal acyl chloride polyethylene glycol; (2) Add graphene oxide to toluene solvent. After ultrasonic homogenization, add double-terminal acyl chloride polyethylene glycol with a mass ratio of 10:520. Carry out modification reaction at 90 °C for 24 h. Centrifuge to separate and remove the solvent, and wash the product with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene; (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, and reaction promoter triethylamine with a mass ratio of 100:120:330 to toluene solvent. Carry out esterification reaction at 75 °C for 48 h. Centrifuge to separate and remove the solvent, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene; (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate, and TEMPO-polyethylene glycol modified graphene with a mass ratio of 100:55:12:8.5:5 to distilled water. Through liquid nitrogen cooling-vacuum pumping-nitrogen cycling treatment, and then ultrasonic homogenization, carry out in-situ polymerization reaction at 110 °C for 48 h in a nitrogen atmosphere. Add distilled water for centrifugal separation to obtain polyethylene glycol-graphene grafted acrylic resin.

[0038] Add TEMPO-polyethylene glycol modified graphene, acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, and film-forming auxiliary alcohol ester twelve to distilled water solvent. After high-speed emulsification, obtain an acrylic resin coating.

[0039] Coat the surface of the tinplate with acrylic resin paint, cure it to form a film, and then immerse it in toluene solvent, and observe the surface condition of the acrylic resin coating.

[0040]

[0041] Coat the surface of the tinplate with acrylic resin paint, cure it to form a film, then immerse it in vegetable oil, and then rinse it with clean water, and observe the surface condition of the acrylic resin coating.

[0042]

[0043] Coat the surface of the tinplate with stain-resistant polyethylene glycol-graphene grafted acrylic resin paint, cure it to form a film, then immerse it in ink, and then rinse it with clean water, and observe the surface condition of the acrylic resin coating.

[0044]

[0045] Introduce the stain-resistant polyethylene glycol-graphene grafted acrylic resin paint into a mold, cure it to form a rubber film, and use a WD-P3 electronic testing machine to test the tensile strength and compressive strength of the acrylic resin rubber film.

[0046]

Claims

1. A dirt-resistant acrylic resin, characterized in that, The resin uses graphene modified by TEMPO-polyethylene glycol as the polymerization carrier, and the TEMPO radical as the initiation site to initiate the in-situ chemical graft polymerization of monomers such as n-butyl acrylate and acrylic acid on the surface of graphene, obtaining the resin. Graphene is connected to the acrylic resin through the polyethylene glycol molecular chain. The TEMPO-polyethylene glycol modified graphene is obtained by introducing polar polyethylene glycol molecular chains and active TEMPO radicals on the surface of graphene.

2. A preparation method of a stain-resistant acrylic resin, characterized in that, The preparation method of the stain-resistant acrylic resin is as follows: (1) React succinic anhydride with polyethylene glycol to obtain polyethylene glycol with double-terminal carboxyl groups, and then react with thionyl chloride to obtain polyethylene glycol with double-terminal acyl chlorides. The molecular weight of the polyethylene glycol is 200 or 400; (2) Add graphene oxide to a toluene solvent, after ultrasonic homogenization, add polyethylene glycol with double-terminal acyl chlorides, carry out the modification reaction, centrifuge to separate and remove the solvent, and wash the product with toluene and ethanol to obtain graphene modified by acyl chloride polyethylene glycol. The mass ratio of graphene oxide to polyethylene glycol with double-terminal acyl chlorides is 10:250 - 450; (3) Add graphene modified by acyl chloride polyethylene glycol, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical and the reaction promoter triethylamine to a toluene solvent, carry out the esterification reaction, centrifuge to separate and remove the solvent, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene. The mass ratio of graphene modified by acyl chloride polyethylene glycol, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical and triethylamine is 100:60 - 110:150 - 280; (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water, perform the treatment of liquid nitrogen cooling - vacuum pumping - nitrogen circulation, then ultrasonic homogenization, carry out the in-situ polymerization reaction in a nitrogen atmosphere, add distilled water and carry out centrifugation to obtain polyethylene glycol-graphene grafted acrylic resin. The mass ratio of n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene is 100:35 - 50:4 - 10:3 - 7:1.5 - 4.

3. The stain-resistant polyethylene glycol-graphene grafted acrylic resin coating according to claim 2, characterized in that: The temperature of the modification reaction in step (2) is 60 - 90 °C, and the reaction time is 12 - 24 h.

4. The stain-resistant polyethylene glycol-graphene grafted acrylic resin coating according to claim 2, wherein: The temperature of the esterification reaction in step (3) is 50 - 75 °C, and the reaction time is 24 - 48 h.

5. The stain-resistant polyethylene glycol-graphene grafted acrylic resin coating according to claim 2, wherein: The temperature of the in-situ polymerization reaction in step (4) is 80 - 110 °C, and the reaction time is 24 - 48 h.

6. A dirt-resistant acrylic coating, characterized in that, The stain-resistant acrylic coating includes the acrylic resin as described in claim 1, the emulsifier sodium dodecyl sulfonate, the polyether-modified silicone defoamer, and the film-forming aid alcohol ester twelve. The mass ratio of the acrylic resin, the emulsifier sodium dodecyl sulfonate, the polyether-modified silicone defoamer, and the film-forming aid alcohol ester twelve is: 100:50 - 100:60 - 150:30 - 80.

7. A dirt-resistant acrylic coating, characterized in that, The preparation method of the acrylic coating is as follows: (1)React succinic anhydride with polyethylene glycol to obtain polyethylene glycol with carboxyl groups at both ends, and then react it with thionyl chloride to obtain polyethylene glycol with acyl chloride groups at both ends, where the molecular weight of the polyethylene glycol is 200 or 400; (2)Add graphene oxide to toluene solvent, after ultrasonic homogenization, add polyethylene glycol with acyl chloride groups at both ends, and carry out a modification reaction. Centrifuge to separate and remove the solvent, and wash the product with toluene and ethanol to obtain graphene modified with polyethylene glycol acyl chloride, where the mass ratio of graphene oxide to polyethylene glycol with acyl chloride groups at both ends is 10:250 - 450; (3)Add graphene modified with polyethylene glycol acyl chloride, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical and the reaction promoter triethylamine to toluene solvent, and carry out an esterification reaction. Centrifuge to separate and remove the solvent, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene, where the mass ratio of graphene modified with polyethylene glycol acyl chloride, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl radical and triethylamine is 100:60 - 110:150 - 280; (4)Add n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water, treat by liquid nitrogen cooling - vacuum pumping - nitrogen cycling, then ultrasonic homogenize, and carry out an in-situ polymerization reaction in a nitrogen atmosphere. Add distilled water and carry out centrifugation to obtain polyethylene glycol-graphene grafted acrylic resin, where the mass ratio of n-butyl acrylate, methyl methacrylate, acrylic acid, 2-hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene is 100:35 - 50:4 - 10:3 - 7:1.5 - 4; (5)Add polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, film-forming aid 2-ethylhexyl acetate to distilled water solvent, and obtain a stain-resistant polyethylene glycol-graphene grafted acrylic resin coating after high-speed emulsification, where the mass ratio of polyethylene glycol-graphene grafted acrylic resin, emulsifier sodium dodecyl sulfonate, polyether modified silicone defoamer, film-forming aid 2-ethylhexyl acetate is: 100:50 - 100:60 - 150:30 - 80.

8. The stain-resistant polyethylene glycol-graphene grafted acrylic resin coating according to claim 6, characterized in that: The temperature of the modification reaction in step (2) is 60 - 90 °C, and the reaction time is 12 - 24 h.

9. The stain-resistant polyethylene glycol-graphene grafted acrylic resin coating according to claim 6, wherein: The temperature of the esterification reaction in step (3) is 50 - 75 °C, and the reaction time is 24 - 48 h.

10. A stain-resistant polyethylene glycol-graphene grafted acrylic resin coating according to claim 6, wherein: The temperature of the in-situ polymerization reaction in step (4) is 80 - 110 °C, and the reaction time is 24 - 48 h.

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