A dirt-resistant acrylic resin, a paint, and a method for producing the same

Abstract

This invention relates to the field of acrylic resin technology and discloses a stain-resistant polyethylene glycol-graphene-grafted acrylic resin coating. TEMPO-modified graphene is used as a polymerization carrier, and TEMPO free radicals serve as initiation sites to initiate in-situ chemical grafting polymerization of monomers such as n-butyl acrylate and acrylic acid on the graphene surface, resulting in a polyethylene glycol-graphene-grafted acrylic resin. The graphene is linked to the acrylic resin through polyethylene glycol molecular chains, organically combining the graphene and acrylic resin. This improves the dispersibility of graphene, overcomes its agglomeration in the acrylic resin, and significantly enhances the tensile strength and other mechanical properties of the acrylic resin. Simultaneously, the grafted polar polyethylene glycol molecular chains improve the hydrophilicity and stain resistance of the acrylic resin.

Description

Technical Field

[0001] This invention relates to the field of acrylic resin technology, specifically to a dirt-resistant polyethylene glycol-graphene grafted acrylic resin, a coating, and a method for preparing the same. Background Technology

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

[0003] Graphene possesses excellent mechanical properties, thermodynamic stability, and oleophobicity, making it an ideal nanofiller for polymer materials. It has broad application prospects in polymers such as polyurea resin and acrylic resin, enhancing the thermal stability, mechanical strength, and oil resistance of these materials. However, graphene has a significant drawback: poor compatibility with acrylic resin, leading to agglomeration. In-situ polymerization, which involves the in-situ chemical grafting of monomers such as acrylic acid onto the graphene surface, is an effective method to address the dispersibility and agglomeration issues of graphene.

[0004] (a) Technical problems to be solved

[0005] To address the shortcomings of existing technologies, this invention provides a stain-resistant polyethylene glycol-graphene-grafted acrylic resin, a coating, and a method for preparing the same. The coating exhibits improved mechanical strength and oil resistance.

[0006] (II) Technical Solution

[0007] To achieve the above objectives, the present invention provides the following technical solution: a dirt-resistant polyethylene glycol-graphene-grafted acrylic resin, wherein the preparation method of the dirt-resistant polyethylene glycol-graphene-grafted acrylic resin is as follows:

[0008] (1) Succinic anhydride and polyethylene glycol are reacted to obtain bicarboxyl-terminated polyethylene glycol, which is then reacted with thionyl chloride to obtain biacyl chloride-terminated polyethylene glycol.

[0009] (2) Add graphene oxide to toluene solvent, sonicate to homogenize, add bis-terminated acyl chloride polyethylene glycol to carry out the modification reaction, centrifuge to remove the solvent, wash the product with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0010] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical (TEMPO) and reaction promoter triethylamine to toluene solvent to carry out esterification reaction, remove the solvent by centrifugation, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene.

[0011] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water, cool with liquid nitrogen, vacuum and circulate nitrogen, then homogenize by ultrasonication, carry out in-situ polymerization reaction in nitrogen atmosphere, add distilled water and centrifuge to obtain polyethylene glycol-graphene grafted acrylic resin.

[0012] Polyethylene glycol-graphene-grafted acrylic resin, sodium dodecyl sulfate emulsifier, polyether-modified silicone defoamer, and film-forming aid alcohol ester dodecyl are added to distilled water solvent. After high-speed emulsification, a dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating is obtained. The mass ratio of the polyethylene glycol-graphene-grafted acrylic resin, sodium dodecyl sulfate emulsifier, polyether-modified silicone defoamer, and film-forming aid alcohol ester dodecyl is 100:50-100:60-150:30-80.

[0013] Preferably, the molecular weight of polyethylene glycol in step (1) is 200 or 400.

[0014] Preferably, in step (2), the mass ratio of graphene oxide to dichloroethylene glycol is 10:250-450.

[0015] Preferably, the temperature of the modification reaction in step (2) is 60-90 °C and the reaction time is 12-24 h.

[0016] Preferably, in step (3), the mass ratio of acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and triethylamine is 100:60-110:150-280.

[0017] Preferably, the temperature of the esterification reaction in step (3) is 50-75 °C and the reaction time is 24-48 h.

[0018] Preferably, in step (4), 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.

[0019] Preferably, the temperature of the in-situ polymerization reaction in step (4) is 80-110 °C and the reaction time is 24-48 h.

[0020] (iii) Beneficial technical effects

[0021] Compared with the prior art, the present invention has the following beneficial technical effects:

[0022] This is a stain-resistant polyethylene glycol-graphene grafted acrylic resin coating. One acyl chloride group of the double-terminated polyethylene glycol reacts with the surface hydroxyl groups of graphene oxide to obtain acyl chloride-modified graphene. Then, in a triethylamine-promoting system, the terminal acyl chloride group undergoes an esterification reaction with the hydroxyl groups that generate 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radicals to obtain TEMPO-modified graphene, thereby introducing polar polyethylene glycol molecular chains and active TEMPO radicals onto the graphene surface.

[0023] This invention relates to a stain-resistant polyethylene glycol-graphene-grafted acrylic resin coating. TEMPO-modified graphene serves as the polymerization carrier, and TEMPO radicals act as initiation sites, initiating in-situ chemical grafting polymerization of monomers such as n-butyl acrylate and acrylic acid on the graphene surface. This yields a polyethylene glycol-graphene-grafted acrylic resin. The graphene is linked to the acrylic resin via polyethylene glycol molecular chains, resulting in an organic combination of graphene and acrylic resin. This improves the dispersibility of graphene and overcomes its agglomeration properties in the acrylic resin. Graphene significantly enhances the tensile strength and other mechanical properties of the acrylic resin, as well as its oil resistance. Simultaneously, the grafted polar polyethylene glycol molecular chains improve the hydrophilicity and organic solvent resistance of the acrylic resin, further enhancing the coating's oil resistance. Attached Figure Description

[0024] Figure 1 This is a reaction diagram of graphene oxide and polyethylene glycol with diterminated acyl chloride;

[0025] Figure 2 This is a schematic diagram illustrating the reaction mechanism of acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical, and the reaction promoter triethylamine. Detailed Implementation

[0026] To achieve the above objectives, the present invention provides the following specific embodiments and examples: A dirt-resistant polyethylene glycol-graphene grafted acrylic resin and a method for preparing coatings using this resin are shown below:

[0027] (1) Succinic anhydride and polyethylene glycol are reacted, wherein the molecular weight of polyethylene glycol is 200 or 400, to obtain bi-carboxyl-terminated polyethylene glycol, which is then reacted with thionyl chloride to obtain bi-acyl chloride-terminated polyethylene glycol.

[0028] (2) Add graphene oxide to toluene solvent, sonicate to homogenize, and then add bis-terminated acyl chloride polyethylene glycol in a mass ratio of 10:250-450. Carry out the modification reaction at 60-90 °C for 12-24 h, centrifuge to remove the solvent, and wash the product with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0029] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and reaction promoter triethylamine to toluene solvent in a mass ratio of 100:60-110:150-280, and carry out esterification reaction at 50-75 °C for 24-48 h. Remove the solvent by centrifugation, wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene;

[0030] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water in a mass ratio of 100:35-50:4-10:3-7:1.5-4. The mixture is cooled by liquid nitrogen, vacuumed and circulated with nitrogen, then ultrasonically homogenized. In an atmosphere of nitrogen, the mixture is subjected to in-situ polymerization at 80-110 °C for 24-48 h. Distilled water is added and the mixture is centrifuged to obtain polyethylene glycol-graphene grafted acrylic resin.

[0031] Polyethylene glycol-graphene-grafted acrylic resin, sodium dodecyl sulfonate emulsifier, polyether-modified silicone defoamer, and dodecyl alcohol ester film-forming aid are added to distilled water solvent and emulsified at high speed to obtain a dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating.

[0032] Example 1

[0033] (1) Succinic anhydride and polyethylene glycol 200 were reacted to obtain bicarboxyl-terminated polyethylene glycol, which was then reacted with thionyl chloride to obtain biacyl chloride-terminated polyethylene glycol.

[0034] (2) Add graphene oxide to toluene solvent, sonicate to homogenize, and then add bis-terminated acyl chloride polyethylene glycol in a mass ratio of 10:250. The modification reaction is carried out at 60 °C for 12 h. The solvent is removed by centrifugation, and the product is washed with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0035] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and reaction promoter triethylamine to toluene solvent in a mass ratio of 100:60:150, and carry out esterification reaction at 50 °C for 24-48 h. Remove the solvent by centrifugation, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene.

[0036] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water in a mass ratio of 100:35:4:3:1.5. The mixture is cooled by liquid nitrogen, vacuumed and circulated with nitrogen, then ultrasonically homogenized. In situ polymerization is carried out at 80 °C for 24 h in a nitrogen atmosphere. Distilled water is added and centrifuged to obtain polyethylene glycol-graphene grafted acrylic resin.

[0037] Polyethylene glycol-graphene-grafted acrylic resin, sodium dodecyl sulfonate emulsifier, polyether-modified silicone defoamer, and dodecyl alcohol ester film-forming aid are added to distilled water solvent and emulsified at high speed to obtain a dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating.

[0038] Example 2

[0039] (1) Succinic anhydride and polyethylene glycol 400 were reacted to obtain bicarboxyl-terminated polyethylene glycol, which was then reacted with thionyl chloride to obtain biacyl chloride-terminated polyethylene glycol.

[0040] (2) Add graphene oxide to toluene solvent, sonicate to homogenize, and then add bis-terminated acyl chloride polyethylene glycol in a mass ratio of 10:320. The modification reaction is carried out at 80 °C for 18 h. The solvent is removed by centrifugation, and the product is washed with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0041] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and reaction promoter triethylamine to toluene solvent in a mass ratio of 100:75:190, and carry out esterification reaction at 65 °C for 36 h. Remove the solvent by centrifugation, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene.

[0042] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water in a mass ratio of 100:40:6:4.5:2.2. Then, cool with liquid nitrogen, vacuum and circulate nitrogen, and then homogenize by ultrasonication. In situ polymerization reaction is carried out at 100 °C for 36 h in a nitrogen atmosphere. Distilled water is added and centrifuged to obtain polyethylene glycol-graphene grafted acrylic resin.

[0043] Polyethylene glycol-graphene-grafted acrylic resin, sodium dodecyl sulfonate emulsifier, polyether-modified silicone defoamer, and dodecyl alcohol ester film-forming aid are added to distilled water solvent and emulsified at high speed to obtain a dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating.

[0044] Example 3

[0045] (1) Succinic anhydride and polyethylene glycol 200 were reacted to obtain bicarboxyl-terminated polyethylene glycol, which was then reacted with thionyl chloride to obtain biacyl chloride-terminated polyethylene glycol.

[0046] (2) Add graphene oxide to toluene solvent, sonicate to homogenize, and then add bis-terminated acyl chloride polyethylene glycol in a mass ratio of 10:380. The modification reaction was carried out at 75 °C for 18 h. The solvent was removed by centrifugation, and the product was washed with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0047] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and reaction promoter triethylamine to toluene solvent in a mass ratio of 100:95:240, and carry out esterification reaction at 60 °C for 36 h. Remove the solvent by centrifugation, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene.

[0048] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water in a mass ratio of 100:45:8:5.5:3.2. The mixture is cooled by liquid nitrogen, vacuumed and circulated with nitrogen, then ultrasonically homogenized. In situ polymerization is carried out at 100 °C for 36 h in a nitrogen atmosphere. Distilled water is added and centrifuged to obtain polyethylene glycol-graphene grafted acrylic resin.

[0049] Polyethylene glycol-graphene-grafted acrylic resin, sodium dodecyl sulfonate emulsifier, polyether-modified silicone defoamer, and dodecyl alcohol ester film-forming aid are added to distilled water solvent and emulsified at high speed to obtain a dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating.

[0050] Example 4

[0051] (1) Succinic anhydride and polyethylene glycol were reacted at 400°C to obtain bicarboxyl-terminated polyethylene glycol, which was then reacted with thionyl chloride to obtain biacyl chloride-terminated polyethylene glycol.

[0052] (2) Add graphene oxide to toluene solvent, sonicate to homogenize, and then add bis-terminated acyl chloride polyethylene glycol in a mass ratio of 10:450. The modification reaction is carried out at 90 °C for 24 h. The solvent is removed by centrifugation, and the product is washed with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0053] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and reaction promoter triethylamine to toluene solvent in a mass ratio of 100:110:280, and carry out esterification reaction at 75 °C for 48 h. Remove the solvent by centrifugation, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene.

[0054] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene to distilled water in a mass ratio of 100:50:10:7:4. The mixture is cooled by liquid nitrogen, vacuumed and circulated with nitrogen. Then it is ultrasonically homogenized and in situ polymerized at 110 °C for 48 h in a nitrogen atmosphere. Distilled water is added and centrifuged to obtain polyethylene glycol-graphene grafted acrylic resin.

[0055] Polyethylene glycol-graphene-grafted acrylic resin, sodium dodecyl sulfonate emulsifier, polyether-modified silicone defoamer, and dodecyl alcohol ester film-forming aid are added to distilled water solvent and emulsified at high speed to obtain a dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating.

[0056] Comparative Example 1

[0057] Polyethylene glycol, graphene, acrylic resin, sodium dodecyl sulfonate emulsifier, polyether-modified silicone defoamer, and dodecyl alcohol ester film-forming aid are added to distilled water solvent, and acrylic resin coating is obtained after high-speed emulsification.

[0058] Comparative Example 2

[0059] (1) Succinic anhydride and polyethylene glycol 400 were reacted to obtain bicarboxyl-terminated polyethylene glycol, which was then reacted with thionyl chloride to obtain biacyl chloride-terminated polyethylene glycol.

[0060] (2) Add graphene oxide to toluene solvent, sonicate to homogenize, and then add bis-terminated acyl chloride polyethylene glycol in a mass ratio of 10:520. The modification reaction is carried out at 90 °C for 24 h. The solvent is removed by centrifugation, and the product is washed with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene.

[0061] (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and reaction promoter triethylamine to toluene solvent in a mass ratio of 100:120:330, and carry out esterification reaction at 75 °C for 48 h. Remove the solvent by centrifugation, and wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene.

[0062] (4) Add n-butyl acrylate, methyl methacrylate, acrylic acid, hydroxyethyl acrylate and TEMPO-polyethylene glycol modified graphene in a mass ratio of 100:55:12:8.5:5 to distilled water, treat it by liquid nitrogen cooling-vacuuming-nitrogen circulation, then sonicate it, and carry out in-situ polymerization reaction at 110 °C for 48 h in a nitrogen atmosphere. Add distilled water and centrifuge to obtain polyethylene glycol-graphene grafted acrylic resin.

[0063] TEMPO-polyethylene glycol modified graphene, acrylic resin, sodium dodecyl sulfonate emulsifier, polyether-modified silicone defoamer, and dodecyl alcohol ester film-forming aid are added to distilled water solvent, and acrylic resin coating is obtained after high-speed emulsification.

[0064] An acrylic resin coating was applied to the surface of tinplate, cured into a film, and then immersed in toluene solvent. The surface condition of the acrylic resin coating was then observed.

[0065]

[0066] An acrylic resin coating is applied to the surface of a tinplate, cured into a film, then immersed in vegetable oil, and finally rinsed with water. The surface condition of the acrylic resin coating is then observed.

[0067]

[0068] A dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating was applied to the surface of tinplate, cured into a film, then immersed in ink, and finally rinsed with water. The surface condition of the acrylic resin coating was then observed.

[0069]

[0070] A dirt-resistant polyethylene glycol-graphene-grafted acrylic resin coating was poured into a mold and cured into a film. The tensile strength and compressive strength of the acrylic resin film were tested using a WD-P3 electronic testing machine.

[0071]

Claims

1. A stain-resistant acrylic resin, characterized in that, This resin uses TEMPO-polyethylene glycol-modified graphene as a polymerization carrier and TEMPO radicals as initiation sites to initiate in-situ chemical graft polymerization of n-butyl acrylate and acrylic monomers on the graphene surface, yielding the resin. The graphene is linked to the acrylic resin via polyethylene glycol molecular chains. The TEMPO-polyethylene glycol-modified graphene is obtained by introducing polar polyethylene glycol molecular chains and active TEMPO radicals onto the graphene surface. The preparation method of the dirt-resistant acrylic resin is as follows: (1) Succinic anhydride and polyethylene glycol are reacted to obtain bicarboxyl-terminated polyethylene glycol, which is then reacted with thionyl chloride to obtain biacyl chloride-terminated polyethylene glycol, wherein the molecular weight of the polyethylene glycol is 200 or 400. (2) Add graphene oxide to toluene solvent, sonicate to homogenize, add bi-terminated acyl chloride polyethylene glycol, carry out modification reaction, centrifuge to remove solvent, wash product with toluene and ethanol to obtain acyl chloride polyethylene glycol modified graphene, wherein the mass ratio of graphene oxide to bi-terminated acyl chloride polyethylene glycol is 10:250-450. (3) Add acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical and reaction promoter triethylamine to toluene solvent to carry out esterification reaction, remove the solvent by centrifugation, wash the product with chloroform and distilled water to obtain TEMPO-polyethylene glycol modified graphene, wherein the mass ratio of acyl chloride polyethylene glycol modified graphene, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide 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, cool with liquid nitrogen, vacuum and circulate nitrogen, then homogenize by ultrasonication, and carry out in-situ polymerization reaction in a nitrogen atmosphere. Add distilled water and centrifuge to obtain dirt-resistant 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. The temperature of the modification reaction in step (2) is 60-90 ℃ and the reaction time is 12-24 h. The temperature of the esterification reaction in step (3) is 50-75 ℃ and the reaction time is 24-48 h. The temperature of the in-situ polymerization reaction in step (4) is 80-110 ℃ and the reaction time is 24-48 h.

2. A stain-resistant acrylic coating, characterized in that, The stain-resistant acrylic coating comprises the stain-resistant acrylic resin as described in claim 1, sodium dodecyl sulfonate as emulsifier, polyether-modified silicone defoamer, and film-forming aid alcohol ester dodecyl, wherein the mass ratio of the stain-resistant acrylic resin, sodium dodecyl sulfonate as emulsifier, polyether-modified silicone defoamer, and film-forming aid alcohol ester dodecyl is 100:50-100:60-150:30-80; the preparation method of the stain-resistant acrylic coating is as follows: Add the stain-resistant acrylic resin as described in claim 1, the emulsifier sodium dodecyl sulfonate, the polyether-modified silicone defoamer, and the film-forming aid alcohol ester dodecyl to a distilled water solvent, and emulsify at high speed to obtain a stain-resistant acrylic coating.

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