Acrylic marker ink and preparation method thereof

Abstract

The present application discloses an acrylic marker ink and a preparation method thereof, relating to the technical field of pen inks. The acrylic marker ink comprises the following raw materials by weight: 10-20 parts of a MOF-modified acrylic resin emulsion, 15-40 parts of a pigment, 1-3 parts of a leveling agent, 2-4 parts of a moisturizer, and 50-160 parts of deionized water. The raw materials of the MOF-modified acrylic resin emulsion include acrylic acid and a vinyl-MOF material, with the mass ratio of acrylic acid to vinyl-MOF material being (3-5):1. By adding the vinyl-MOF material to the preparation of the acrylic resin emulsion, a small amount of the MOF material can be connected to the long chain of the acrylic resin. Due to the porous adsorption properties of the MOF material, the adsorption performance of the acrylic resin emulsion on the pigment can be improved after the ink dries, allowing the ink to be preserved for a longer period of time and preventing it from falling off or fading.

Description

Technical Field

[0001] The present application relates to the technical field of pen ink, and in particular to an acrylic marker ink and a preparation method thereof. Background Art

[0002] Acrylic markers, as an important drawing tool, are widely used in art creation, design, and other fields. The quality of their ink directly impacts the expressiveness and durability of the work. With technological advancements, acrylic marker inks have evolved from single-ingredient to multifunctional components to meet user performance requirements. This shift not only improves the performance of the ink but also enhances its display quality and shelf life. Prior art methods for enhancing the performance of acrylic marker inks typically involve introducing modifiers to improve the properties of acrylic resin emulsions.

[0003] Patent publication number CN118185382A discloses an acrylic marker ink and its preparation method. The acrylic marker ink comprises, by weight: 15-25 parts of a water-based acrylic resin, 25-40 parts of a pigment paste, 1-5 parts of a crosslinker, 3-5 parts of a humectant, 0.1-6 parts of a surfactant with wetting and defoaming properties, 0.1-1 parts of a leveling agent, 0.1-6 parts of a dispersant, 0.1-1 parts of an ink pH adjuster, 0.05-0.2 parts of a preservative, and the remainder being deionized water. Patent publication number CN118185381A discloses a marker ink and its preparation method. The marker ink comprises the following components, by weight: 5-20 parts of an azo metal complex dye, 2-10 parts of a film-forming resin, 25-80 parts of alcohol, 0.5-2 parts of a leveling agent, 15-50 parts of a cosolvent, 0.5-1 parts of a defoamer, and 2-5 parts of a humectant. The ink contains no ketone or benzene-based irritating solvents, making it safe and non-toxic to the human body. The inks in the aforementioned solutions are all made by bonding pigments and other components with acrylic resin. While the water solubility and adhesive properties of acrylic resin ensure the ink's writing performance under water-based conditions, water-based inks have poorer adhesive properties than oil-based inks, making the ink easily detachable and discolored after writing, resulting in the ink not remaining legible for a long time. Summary of the Invention

[0004] The purpose of the present application is to provide an acrylic marker ink and a preparation method thereof, so as to solve the problem that the ink marks written with water-based ink cannot be preserved intact for a long time.

[0005] In the first aspect, the present application provides an acrylic marker ink using the following technical solution:

[0006] An acrylic marker ink comprises the following raw materials by weight:

[0007] 10-20 parts of MOF modified acrylic resin emulsion, 15-40 parts of pigment, 1-3 parts of leveling agent, 2-4 parts of moisturizing agent and 50-160 parts of deionized water;

[0008] The raw materials of the MOF-modified acrylic resin emulsion include: acrylic acid and vinyl MOF material, and the mass ratio of the acrylic acid to the vinyl MOF material is (3-5):1.

[0009] By adopting the above technical solution, by adding a vinyl MOF material to the preparation of an acrylic resin emulsion, a small amount of MOF material can be connected to the long acrylic resin chain. Due to the porous adsorption properties of the MOF material, the acrylic resin emulsion's adsorption of pigments can be improved after the ink dries, allowing the ink to be preserved for a longer period of time without shedding or fading. Compared to the vinyl MOF material, acrylic acid has a smaller relative atomic mass. Therefore, controlling the mass ratio of the two to (3-4):1 can effectively form an impurity with the vinyl MOF material, preventing the vinyl MOF material from affecting the performance of the acrylic acid.

[0010] Optionally, the preparation method of the vinyl MOF material comprises the following steps:

[0011] S001, preparing MOF front-end;

[0012] S002. Dissolve vinyl imidazole in an organic solvent, add the MOF precursor prepared in step S001, react at 80-150° C. for 5-10 hours, and obtain a vinyl MOF material after filtering and washing.

[0013] By adopting the above technical solution, since the vinyl MOF material needs to maintain its performance in both the ink state and the ink state after drying, the performance of the vinyl MOF material is improved by preparing a MOF front end. The vinyl MOF material is prepared by using vinyl imidazole as a ligand. On the one hand, it can form a stable complex structure with the MOF front end, and on the other hand, it can introduce unsaturated bonds, thereby participating in the polymerization reaction of acrylic resin.

[0014] Optionally, the organic solvent is selected from one or more of methanol, ethanol and DMF.

[0015] By adopting the above technical solution, the above organic solvents can dissolve vinyl imidazole well and do not react with the MOF front end and vinyl imidazole, thereby ensuring the stability of the reaction during the synthesis process. Moreover, the above organic solvents will not dissolve and corrode the reaction products, and the reaction products can be quickly separated by filtration.

[0016] Optionally, the preparation of the MOF front end comprises the following steps:

[0017] S011, acidifying the carbon source;

[0018] S012, adding the treated carbon source to deionized water, then adding the metal ion source and the ligand source, keeping stirring, reacting at 40-70° C. for 10-15 hours, filtering and drying to obtain an intermediate product;

[0019] S013. Under a nitrogen atmosphere, the intermediate product obtained in step S012 is heated to 500-700° C., and hydrogen is introduced for 50-100 min. After the hydrogen introduction is stopped, the temperature is further raised to 700-900° C., carbonized for 90-120 min, and then cooled to room temperature to obtain a MOF front end.

[0020] By adopting the above technical solution, acidification can increase the surface activity of the carbon source, allowing metal ions to complex on the carbon source surface. By stirring the reaction in deionized water, the metal ions and ligand source are loaded on the carbon source. The ligand source allows the carbon source and metal ions to be stably complexed. Then, through high-temperature carbonization, a MOF precursor composed of metal ions and carbon nanomaterials is formed. Due to the porous adsorption properties of MOF materials, MOF materials easily aggregate in water-based inks, thereby destroying the material's performance. Therefore, by loading the carbon nanomaterials and using the hydrophobic carbon nanomaterials, the MOF materials can remain dispersed in the water-based ink, improving the material's performance.

[0021] Optionally, the carbon source is selected from one of graphene or carbon nanotubes, the metal ion source is selected from one of zinc nitrate, zinc chloride, cobalt nitrate and cobalt chloride, and the ligand source is selected from one or more of pyridine compounds, imidazole compounds, carboxylic acid compounds and porphyrin compounds.

[0022] By employing this technical solution, the smaller size of graphene and carbon nanotubes allows the vinyl MOF material to be easily incorporated into the ink, preventing it from affecting ink performance. Zinc ions, cobalt ions, and various ligand compounds contribute to a stable framework structure. Optimizing the specific types of carbon, metal ion, and ligand sources results in a MOF precursor with a more optimized structure and properties. This, in turn, results in a superior modified vinyl MOF material, enhancing the performance stability and usability of acrylic marker inks.

[0023] Optionally, the molar ratio of the metal ion source, the ligand source and the vinyl imidazole is 1:(2.5-3.7):(3.2-4.6).

[0024] By adopting the above technical solution, since the ligand source and vinyl imidazole are both common ligands in the MOF material, the ratio of the ligand source to the metal ion source is relatively reduced in the preparation of the MOF front end, and the coordination space is released for the vinyl imidazole to be complexed. By complexing the vinyl imidazole on the MOF front end after the composite carbon nanomaterial, the vinyl imidazole can have a double bond while loading the hydrophobic carbon nanomaterial, which can be polymerized with acrylic acid to form a modified resin material.

[0025] Optionally, the preparation method of the MOF-modified acrylic resin emulsion comprises the following steps:

[0026] Add acrylic acid, vinyl MOF material and chain transfer agent to deionized water, increase the temperature to 70-90°C, add initiator, keep stirring, react for 2-4 hours, and cool to room temperature to obtain MOF-modified acrylic resin emulsion.

[0027] By adopting the above technical solution, the initiator can trigger the polymerization reaction, while the chain transfer agent can control the molecular size of the polymerization reaction product. Through the combined action of the two, the vinyl MOF material can be polymerized with acrylic acid to obtain a MOF-modified acrylic resin emulsion with moderate molecular weight and balanced performance.

[0028] Optionally, the initiator is selected from one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptanenitrile, and the chain transfer agent is selected from one of dodecyl mercaptan, toluene, trichloroethylene and tetrachloromethane.

[0029] By adopting the above technical solution and selecting specific initiators and chain transfer agents, the polymerization reaction rate and product molecular weight distribution can be effectively controlled, thereby improving the performance stability of MOF-modified acrylic resin emulsion and the overall performance of acrylic marker ink.

[0030] Optionally, the pigment is selected from one of titanium dioxide, iron oxide, ultramarine blue, carbon black, phthalocyanine and carbon black, the leveling agent is selected from one of polydimethylsiloxane and polymethylalkylsiloxane, and the moisturizer is selected from one of sodium lauryl sulfate, lecithin and sucrose fatty acid ester.

[0031] By adopting the above technical solution, different types of pigments can make the ink present different colors, the leveling agent improves the fluidity of the ink, so that the ink can be used normally, and the moisturizing agent can ensure that the solvent will not evaporate quickly when the ink is not in use, ensuring that the ink can be used normally for a long time.

[0032] In a second aspect, the present application provides a method for preparing acrylic marker ink using the following technical solution:

[0033] A method for preparing acrylic marker ink, based on the above-mentioned acrylic marker ink, comprises the following steps:

[0034] S021, adding pigment, moisturizing agent and part of deionized water into a grinder, and grinding for 10-30 hours to obtain a pre-processed pigment;

[0035] S022, mixing the MOF-modified acrylic resin emulsion and the remaining deionized water, stirring evenly to obtain a resin solution;

[0036] S023. Mix the pre-processed pigment obtained in step S021 and the resin solution obtained in step S022, add a leveling agent, and stir evenly to obtain acrylic marker ink.

[0037] By adopting the above technical solution, grinding the pigment can reduce the pigment particles, so that it can be better dispersed in the ink, and MOF modified acrylic resin

[0038] In summary, this application includes at least one of the following beneficial technical effects:

[0039] 1. By adding vinyl MOF materials to the preparation of acrylic resin emulsion, a small amount of MOF materials can be connected to the long chain of acrylic resin. Due to the porous adsorption characteristics of MOF materials, the adsorption performance of acrylic resin emulsion to pigment can be improved after the ink dries, so that the ink can be preserved for a longer time and avoid shedding or fading;

[0040] 2. Vinyl MOF materials are prepared by using vinyl imidazole as a ligand. On the one hand, it can form a stable complex structure with the MOF front end, and on the other hand, it can introduce unsaturated bonds, thereby participating in the polymerization reaction of acrylic resin;

[0041] 3. Acidification can increase the surface activity of the carbon source, allowing metal ions to complex on the carbon source surface. By stirring the reaction in deionized water, the metal ions and ligand source are loaded on the carbon source. The ligand source allows the carbon source and metal ions to be stably complexed. Then, through high-temperature carbonization, a MOF precursor composed of metal ions and carbon nanomaterials is formed. Due to the porous adsorption properties of MOF materials, MOF materials easily aggregate in water-based inks, thereby destroying the material's performance. Therefore, by loading carbon nanomaterials and using hydrophobic carbon nanomaterials, the MOF material can remain dispersed in water-based inks, improving the material's performance. DETAILED DESCRIPTION

[0042] The present application is further described in detail below with reference to the following embodiments and comparative examples.

[0043] In the following preparation examples, embodiments and comparative examples, the pigment is selected from carbon black, the leveling agent is selected from polydimethylsiloxane, the moisturizing agent is selected from sodium lauryl sulfate, the initiator is selected from benzoyl peroxide, the chain transfer agent is selected from dodecyl mercaptan, the carbon source is selected from graphene, the ion source is selected from zinc nitrate and cobalt nitrate, the ligand source is selected from 2,2'-bipyridine among pyridine compounds, and the organic solvent is selected from DMF.

[0044] Preparation Example 1

[0045] The preparation of vinyl MOF materials includes the following steps:

[0046] S031. Take 200 ml of 1 mol / L nitric acid solution and add 50 g of graphene. After ultrasonic dispersion, keep in a constant temperature water bath at 70°C for 4 hours, filter, wash until neutral, and dry to obtain an acidified carbon source.

[0047] S032. Add 20 g of the acidified carbon source prepared in step S031, 18.9 ml of a zinc nitrate solution with a mass concentration of 1 g / ml, and 48.4 g of 2,2'-bipyridine to 50 ml of deionized water, stir and disperse evenly, and keep stirring at 55°C in a constant temperature water bath for 12 hours. After filtering and drying, an intermediate product is obtained.

[0048] S033. Add the intermediate product prepared in step S032 into a quartz tube, introduce a nitrogen atmosphere, heat the tube to 600°C at a heating rate of 8°C / min, and start to introduce hydrogen. After maintaining the reaction for 75 minutes, stop introducing hydrogen, continue to heat the tube to 800°C at a heating rate of 10°C / min, react for 100 minutes, and then cool naturally to obtain a MOF front end.

[0049] S034. Add 35.8 g of vinyl imidazole to 200 ml of DMF and stir until dissolved. Then add all the MOF precursor prepared in step S033 and stir evenly. Keep stirring and react at 120°C for 8 hours. After the reaction is completed, filter, wash and dry the product to obtain a vinyl MOF material.

[0050] Preparation Example 2

[0051] The preparation of vinyl MOF materials includes the following steps:

[0052] S031. Take 200 ml of 1 mol / L nitric acid solution and add 50 g of graphene. After ultrasonic dispersion, keep in a constant temperature water bath at 70°C for 4 hours, filter, wash until neutral, and dry to obtain an acidified carbon source.

[0053] S032. Add 20 g of the acidified carbon source prepared in step S031, 18.9 ml of a zinc nitrate solution with a mass concentration of 1.0 g / ml, and 39.0 g of 2,2'-bipyridine to 50 ml of deionized water, stir and disperse evenly, and keep stirring at 40°C in a constant temperature water bath for 10 hours. After filtering and drying, an intermediate product is obtained.

[0054] S033. Add the intermediate product prepared in step S032 into a quartz tube, introduce a nitrogen atmosphere, heat the tube to 500°C at a heating rate of 6°C / min, and start to introduce hydrogen. After maintaining the reaction for 50 minutes, stop introducing hydrogen, continue to heat the tube to 700°C at a heating rate of 10°C / min, react for 90 minutes, and then cool naturally to obtain a MOF front end.

[0055] S034. Add 30.1 g of vinyl imidazole to 200 ml of DMF and stir until dissolved. Then add all the MOF precursor prepared in step S033 and stir evenly. Keep stirring and react at 80°C for 5 hours. After the reaction is completed, filter, wash and dry the product to obtain a vinyl MOF material.

[0056] Preparation Example 3

[0057] The preparation of vinyl MOF materials includes the following steps:

[0058] S031. Take 200 ml of 1 mol / L nitric acid solution and add 50 g of graphene. After ultrasonic dispersion, keep in a constant temperature water bath at 70°C for 4 hours, filter, wash until neutral, and dry to obtain an acidified carbon source.

[0059] S032. Add 20 g of the acidified carbon source prepared in step S031, 18.9 ml of a zinc nitrate solution with a mass concentration of 1 g / ml, and 57.7 g of 2,2'-bipyridine to 50 ml of deionized water, stir and disperse evenly, and keep stirring at 70°C in a constant temperature water bath for 15 hours. After filtering and drying, an intermediate product is obtained.

[0060] S033. Add the intermediate product prepared in step S032 into a quartz tube, introduce a nitrogen atmosphere, heat the tube to 700°C at a heating rate of 10°C / min, and start to introduce hydrogen. After maintaining the reaction for 75 minutes, stop introducing hydrogen, continue to heat the tube to 800°C at a heating rate of 10°C / min, react for 100 minutes, and then cool naturally to obtain a MOF front end.

[0061] S034. Add 43.3 g of vinyl imidazole to 200 ml of DMF and stir until dissolved. Then add all the MOF precursor prepared in step S033 and stir evenly. Keep stirring and react at 150°C for 10 hours. After the reaction is completed, filter, wash and dry the product to obtain a vinyl MOF material.

[0062] Preparation Example 4

[0063] The preparation of vinyl MOF materials includes the following steps:

[0064] S031. Take 200 ml of 1 mol / L nitric acid solution and add 50 g of graphene. After ultrasonic dispersion, keep in a constant temperature water bath at 70°C for 4 hours, filter, wash until neutral, and dry to obtain an acidified carbon source.

[0065] S032. Add 20 g of the acidified carbon source prepared in step S031, 29.1 ml of a cobalt nitrate solution with a mass concentration of 1 g / ml, and 48.4 g of 2,2'-bipyridine to 50 ml of deionized water, stir and disperse evenly, and keep stirring at 55°C in a constant temperature water bath for 12 hours. After filtering and drying, an intermediate product is obtained.

[0066] S033. Add the intermediate product prepared in step S032 into a quartz tube, introduce a nitrogen atmosphere, heat the tube to 600°C at a heating rate of 8°C / min, and start to introduce hydrogen. After maintaining the reaction for 75 minutes, stop introducing hydrogen, continue to heat the tube to 800°C at a heating rate of 10°C / min, react for 100 minutes, and then cool naturally to obtain a MOF front end.

[0067] S034. Add 36.7 g of vinyl imidazole to 200 ml of DMF and stir until dissolved. Then add all the MOF front end prepared in step S033 and stir evenly. Keep stirring and react at 120°C for 8 hours. After the reaction is completed, filter, wash and dry the product to obtain a vinyl MOF material.

[0068] Example 1

[0069] The preparation method of acrylic marker ink comprises the following steps:

[0070] S041. Add 120 g of acrylic acid, 30 g of the vinyl MOF material prepared in Preparation Example 1, and 10 g of dodecyl mercaptan to 500 ml of deionized water, raise the temperature to 80°C, keep stirring, add 8 g of benzoyl peroxide, react for 3 hours, and cool to room temperature to obtain a MOF-modified acrylic resin emulsion.

[0071] S042, adding 50g of carbon black, 6g of sodium lauryl sulfate and 150g of deionized water to a grinder, and grinding for 20h to obtain a pre-processed pigment;

[0072] S043, mix 30g of MOF-modified acrylic resin emulsion and 60g of deionized water, stir well to obtain a resin solution;

[0073] S044. Mix the pre-processed pigment prepared in step S042 and the resin solution prepared in step S043, keep stirring, and add 4 g of polydimethylsiloxane to obtain acrylic marker ink.

[0074] Example 2

[0075] The preparation method of acrylic marker ink comprises the following steps:

[0076] S041. Add 120 g of acrylic acid, 30 g of the vinyl MOF material prepared in Preparation Example 1, and 10 g of dodecyl mercaptan to 500 ml of deionized water, raise the temperature to 80°C, keep stirring, add 8 g of benzoyl peroxide, react for 3 hours, and cool to room temperature to obtain a MOF-modified acrylic resin emulsion.

[0077] S042, add 30g of carbon black, 4g of sodium lauryl sulfate and 60g of deionized water into a grinder, and grind for 20h to obtain a pre-processed pigment;

[0078] S043, mixing 20 g of MOF-modified acrylic resin emulsion and 40 g of deionized water, stirring evenly to obtain a resin solution;

[0079] S044. Mix the pre-processed pigment prepared in step S042 and the resin solution prepared in step S043, keep stirring, and add 2 g of polydimethylsiloxane to obtain acrylic marker ink.

[0080] Example 3

[0081] The preparation method of acrylic marker ink comprises the following steps:

[0082] S041. Add 120 g of acrylic acid, 30 g of the vinyl MOF material prepared in Preparation Example 1, and 10 g of dodecyl mercaptan to 500 ml of deionized water, raise the temperature to 80°C, keep stirring, add 8 g of benzoyl peroxide, react for 3 hours, and cool to room temperature to obtain a MOF-modified acrylic resin emulsion.

[0083] S042, adding 80g of carbon black, 8g of sodium lauryl sulfate and 240g of deionized water into a grinder, and grinding for 20h to obtain a pre-processed pigment;

[0084] S043, mixing 40 g of MOF-modified acrylic resin emulsion and 80 g of deionized water, stirring evenly to obtain a resin solution;

[0085] S044. Mix the pre-processed pigment prepared in step S042 and the resin solution prepared in step S043, keep stirring, and add 4 g of polydimethylsiloxane to obtain acrylic marker ink.

[0086] Example 4

[0087] The difference from Example 1 is:

[0088] In step S041, the amount of acrylic acid used is 90 g.

[0089] Example 5

[0090] In step S041, the amount of acrylic acid used is 150 g.

[0091] Example 6

[0092] The difference from Example 1 is that the vinyl MOF material prepared in Preparation Example 2 of equal mass is used to replace the vinyl MOF material prepared in Preparation Example 1.

[0093] Example 7

[0094] The difference from Example 1 is that the vinyl MOF material prepared in Preparation Example 3 of equal mass is used to replace the vinyl MOF material prepared in Preparation Example 1.

[0095] Example 8

[0096] The difference from Example 1 is that the vinyl MOF material prepared in Preparation Example 4 is used in place of the vinyl MOF material prepared in Preparation Example 1 with the same mass.

[0097] Comparative Example 1

[0098] The difference from Example 1 is that in step S041, the vinyl MOF material prepared in Preparation Example 1 is not added.

[0099] Comparative Example 2

[0100] The difference from Example 1 is that in step S041, polyurethane of equal mass is used to replace the vinyl MOF material prepared in Preparation Example 1.

[0101] The performance tests were performed on the acrylic marker inks prepared in the examples and comparative examples:

[0102] Adhesion Test: According to the national standard QB / T 2777-2015 for the adhesion test of water-based marker inks, five consecutive circles with a diameter of 20mm-30mm are drawn on a glass plate with a pen. After 5 minutes, the traces are covered with two layers of medical gauze and pressed with a 500g special weight (bottom diameter 50mm). The traces are rubbed back and forth five times to test whether they have been erased. The adhesion strength of the ink to the substrate is graded from 0 to 5, with grade 0 indicating excellent adhesion with no signs of detachment, grade 1 indicating 5% detachment, grade 2 indicating 15% detachment, grade 3 indicating 35% detachment, grade 4 indicating 65% detachment, and grade 5 indicating complete detachment and no adhesion.

[0103] Color fading test: Draw five consecutive circles with a diameter of 20mm-30mm on a glass plate, place the glass vertically for 24 hours, and observe whether the ink falls off.

[0104] Table 1 Performance test results of acrylic marker inks prepared in Examples and Comparative Examples

[0105] Adhesion test Whether it fades Adhesion test Whether it fades Example 1 Level 0 no Example 6 Level 0 no Example 2 Level 0 no Example 7 Level 0 no Example 3 Level 0 no Example 8 Level 0 no Example 4 Level 0 no Comparative Example 1 Level 3 yes Example 5 Level 0 no Comparative Example 2 Level 4 yes

[0106] The properties of acrylic marker ink were investigated according to Table 1, Examples, and Preparation Examples.

[0107] Comparing Examples 1-8, it can be seen that the acrylic marker inks prepared within the raw material ratio range of this application all have excellent adhesion, and the pigment can be maintained for a long time without falling off, which has good applicability in applications where long-term ink retention is required. Comparing the Examples and Comparative Examples, it can be seen that the inks prepared without the vinyl MOF material as a raw material have weaker adhesion and the ink will fall off after long-term storage, indicating that the vinyl MOF material is effective in improving ink retention.

[0108] The embodiments of this specific implementation are all preferred embodiments of this application and are not intended to limit the scope of protection of this application. Therefore, any equivalent changes made based on the structure, shape, and principle of this application should be included in the scope of protection of this application.

Claims

1. An acrylic marker ink, characterized in that: The raw materials include the following components by weight: 10-20 parts of MOF modified acrylic resin emulsion, 15-40 parts of pigment, 1-3 parts of leveling agent, 2-4 parts of moisturizing agent and 50-160 parts of deionized water; The raw materials of the MOF-modified acrylic resin emulsion include: acrylic acid and vinyl MOF material, and the mass ratio of the acrylic acid to the vinyl MOF material is (3-5):1; The preparation method of the vinyl MOF material comprises the following steps: S001, preparing MOF front-end; S002, dissolving vinyl imidazole in an organic solvent, and adding the MOF precursor prepared in step S001, reacting at 80-150° C. for 5-10 hours, and filtering and washing to obtain a vinyl MOF material; The preparation of the MOF front end comprises the following steps: S011, acidifying the carbon source; S012, adding the treated carbon source to deionized water, then adding the metal ion source and the ligand source, keeping stirring, reacting at 40-70° C. for 10-15 hours, filtering and drying to obtain an intermediate product; S013. Under a nitrogen atmosphere, the intermediate product obtained in step S012 was heated to 500-700° C., and hydrogen was introduced for 50-100 min. After the hydrogen introduction was stopped, the temperature was further raised to 700-900° C., carbonized for 90-120 min, and then cooled to room temperature to obtain a MOF front end. The molar ratio of the metal ion source, the ligand source and the vinyl imidazole is 1: (2.5-3.7): (3.2-4.6); The preparation method of the MOF-modified acrylic resin emulsion comprises the following steps: Add acrylic acid, vinyl MOF material and chain transfer agent to deionized water, increase the temperature to 70-90°C, add initiator, keep stirring, react for 2-4 hours, and cool to room temperature to obtain MOF-modified acrylic resin emulsion.

2. The acrylic marker ink according to claim 1, characterized in that The organic solvent is selected from one or more of methanol, ethanol and DMF.

3. The acrylic marker ink according to claim 1, wherein The carbon source is selected from one of graphene or carbon nanotubes, the metal ion source is selected from one of zinc nitrate, zinc chloride, cobalt nitrate and cobalt chloride, and the ligand source is selected from one or more of pyridine compounds, imidazole compounds, carboxylic acid compounds and porphyrin compounds.

4. The acrylic marker ink according to claim 1, wherein The initiator is selected from one of benzoyl peroxide, azobisisobutyronitrile and azobisisoheptanenitrile, and the chain transfer agent is selected from one of dodecyl mercaptan, toluene, trichloroethylene and tetrachloromethane.

5. The acrylic marker ink according to claim 1, wherein: The pigment is selected from one of titanium dioxide, iron oxide, ultramarine blue, phthalocyanine and carbon black; the leveling agent is selected from one of polydimethylsiloxane and polymethylalkylsiloxane; and the moisturizing agent is selected from one of sodium lauryl sulfate, lecithin and sucrose fatty acid ester.

6. A method for preparing an acrylic marker ink, based on the acrylic marker ink according to any one of claims 1 to 5, characterized in that: The steps include: S021, adding pigment, moisturizing agent and part of deionized water into a grinder, and grinding for 10-30 hours to obtain a pre-processed pigment; S022, mixing the MOF-modified acrylic resin emulsion and the remaining deionized water, stirring evenly to obtain a resin solution; S023. Mix the pre-processed pigment obtained in step S021 and the resin solution obtained in step S022, add a leveling agent, and stir evenly to obtain acrylic marker ink.