Preparation method of environment-friendly quick-drying water-based matte oil

Abstract

The invention relates to the field of matt oil, in particular to a preparation method of environment-friendly quick-drying water-based matt oil, which is used for solving the problems that the existing water-based matt oil is poor in film forming effect, a formed matt coating is not high in compactness, and the existing water-based matt oil is poor in wear resistance and water resistance and is easy to wear and damage and is damaged by water erosion. According to the manufacturing method, the first water-based emulsion and the second water-based emulsion serve as main raw materials, advantages of the first water-based emulsion and the second water-based emulsion are combined, defects of the first water-based emulsion and the second water-based emulsion are mutually compensated, the water-based matt oil is endowed with good film-forming property and quick-drying property, an interpenetrating network structure is formed, the film-forming compactness is improved, and a coating is endowed with excellent weather resistance and water resistance; the modified nano silicon dioxide is added, so that the cross-linking reaction among the components is promoted, a compact structure is formed on the surface of the coating, the hardness and the wear resistance of the coating are remarkably improved, a good matte effect is achieved, and the coating has wide application prospects in multiple fields.

Description

Technical Field

[0001] The present invention relates to the field of matte oil, and particularly to a method for preparing an environmentally friendly and fast-drying waterborne matte oil. Background Art

[0002] Matte oil is a low-gloss coating. The paint film has no strong gloss, the matte coating is very soft, and the texture is very strong, making it more and more popular and valued in the printing industry. However, most of the current matte oils use a large amount of highly toxic ester and ketone solvents, which may produce harmful substances during production and use, causing negative impacts on the environment. Therefore, developing and using environmentally friendly alternative materials has become a trend.

[0003] Waterborne matte oil has received extensive attention and use because it uses water as a diluent, reducing the use of organic solvents and reducing environmental pollution and harm to human health. However, the existing waterborne matte oils have poor film-forming effects, the formed matte coatings have low density, and they perform poorly in terms of abrasion resistance and water resistance, being easily worn and damaged by water, affecting the user experience and the market competitiveness of products, and restricting the widespread application of waterborne matte oils. Therefore, developing a method for preparing an environmentally friendly and fast-drying waterborne matte oil is of great significance. Summary of the Invention

[0004] In order to overcome the above technical problems, the purpose of the present invention is to provide a method for preparing an environmentally friendly and fast-drying waterborne matte oil, which solves the problems that the existing waterborne matte oils have poor film-forming effects, the formed matte coatings have low density, and they perform poorly in terms of abrasion resistance and water resistance, being easily worn and damaged by water.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A method for preparing an environmentally friendly and fast-drying waterborne matte oil, comprising the following steps: Step 1: Weigh 17 - 23 parts of a first aqueous emulsion, 30 - 36 parts of a second aqueous emulsion, 3 - 11 parts of modified nano-silica, 0.2 - 0.3 parts of N,N-dimethylethanolamine, 0.5 - 0.9 parts of a wetting agent, 0.2 - 0.3 parts of an antifoaming agent, 0.5 - 0.7 parts of a leveling agent, 4 - 6 parts of a film-forming auxiliary, 1.3 - 2.5 parts of an anti-settling agent, and 13 - 15 parts of deionized water by weight; Step 2: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent and deionized water into a mixer, stir and mix for 5 - 10 min under the condition that the stirring rate is 1000 - 1200 r / min, then add modified nano-silica and stir and mix for 15 - 20 min under the condition that the stirring rate is 2500 - 3000 r / min, then add the first aqueous emulsion, the second aqueous emulsion, film-forming aid and anti-settling agent and stir and mix for 30 - 50 min under the condition that the stirring rate is 1000 - 1200 r / min to obtain an environmentally friendly and fast-drying water-based matte oil.

[0006] As a further scheme of the present invention: the wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming aid is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax paste 6900-20X.

[0007] As a further scheme of the present invention: the second aqueous emulsion is prepared by the following steps: Step a1: Add melamine, triethylamine and N,N-dimethylformamide into a three-necked flask equipped with a stirrer, thermometer and constant pressure dropping funnel, stir and react for 20 - 30 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, then dropwise add perfluorobutanesulfonyl fluoride drop by drop while stirring, control the dropping rate to be 1 - 2 drops / s, after dropping, raise the temperature to 40 - 45 °C and continue to stir and react for 10 - 15 h, after the reaction is completed, cool the reaction product to room temperature, then rotate and evaporate to remove the solvent, then wash with anhydrous acetone 2 - 3 times, and then place it in a vacuum drying oven and dry for 3 - 4 h under the condition of a temperature of 60 - 65 °C to obtain a fluorine-containing modifier; Step a2: Add polycarbonate diol, isophorone diisocyanate, dibutyltin dilaurate and anhydrous acetone into a three-necked flask equipped with a stirrer, thermometer and gas guide tube, introduce nitrogen for protection, stir and react for 30 - 50 min under the conditions of a temperature of 25 - 30 °C and a stirring rate of 200 - 300 r / min, then raise the temperature to 70 - 80 °C and continue to stir and react for 3 - 5 h, then add the fluorine-containing modifier and continue to stir and react for 2 - 3 h, after the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 7 with triethylamine, then rotate and evaporate to remove the solvent, and then add it to deionized water for emulsification to obtain a second aqueous emulsion with a solid content of 35 - 40%.

[0008] As a further solution of the present invention: the dosage ratio of the melamine, triethylamine, N, N-dimethylformamide, and perfluorobutanesulfonyl fluoride in step a1 is 0.1 mol: 0.1 mol: 80-100 mL: 0.1 mol.

[0009] As a further solution of the present invention: the dosage ratio of the polycarbonate diol, isophorone diisocyanate, dibutyltin dilaurate, anhydrous acetone, and fluorine-containing modifier in step a2 is 11-15 mmol: 20 mmol: 1.5-2.1 g: 40-50 mL: 3-6 mmol.

[0010] As a further solution of the present invention: the polycarbonate diol in step a2 is PCDL-1000.

[0011] As a further solution of the present invention: the first aqueous emulsion is prepared by the following steps: Add 1 / 5 of the mixed monomers, sodium dodecyl sulfate, and deionized water into a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and constant pressure dropping funnel, and stir and react for 20-30 min under the conditions of a temperature of 25-30 °C and a stirring rate of 200-300 r / min. Then, while stirring, gradually add dropwise the remaining 4 / 5 of the mixed monomers and ammonium persulfate solution under the condition of heating to 80-85 °C, control the dropping rate to be 1-2 drops / s. After the dropping is completed, continue to stir and react for 2-3 h. Then, cool to 35-40 °C and adjust the pH to 7.5-8 with ammonia water, and then adjust the solid content to 35-40% with distilled water to obtain the first aqueous emulsion.

[0012] As a further solution of the present invention: the dosage ratio of the mixed monomers, sodium dodecyl sulfate, deionized water, and ammonium persulfate solution is 40-50 g: 1.2-1.8 g: 30-35 mL: 10-15 mL.

[0013] As a further solution of the present invention: the mixed monomers are a mixture of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid in a mass ratio of 0.8-1.0: 0.4-0.6: 0.4-0.6: 0.3-0.5; the mass fraction of the ammonium persulfate solution is 2-3%; the mass fraction of the ammonia water is 20%.

[0014] As a further solution of the present invention: the modified nano-silica is prepared by the following steps: Step b1: Add nano-silica, 3-aminopropyltriethoxysilane, ethanol solution and ammonia water into a three-necked flask equipped with a stirrer and a thermometer. Under the condition of ultrasonic frequency of 30 - 40 kHz, ultrasonically disperse for 20 - 30 min. Then, under the conditions of temperature of 25 - 30 °C and stirring rate of 200 - 300 r / min, stir and react for 10 - 15 min. After that, raise the temperature to 60 - 65 °C and continue to stir and react for 4 - 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with absolute ethanol 2 - 3 times, and then place it in a vacuum drying oven. Dry it at a temperature of 60 - 65 °C for 2 - 3 h to obtain pre-modified nano-silica; Step b2: Add pre-modified nano-silica, boric acid, glycerol and absolute ethanol into a three-necked flask equipped with a stirrer and a thermometer. Under the condition of ultrasonic frequency of 30 - 40 kHz, ultrasonically disperse for 20 - 30 min. Then, under the conditions of temperature of 25 - 30 °C and stirring rate of 200 - 300 r / min, stir and react for 10 - 15 min. After that, raise the temperature to 80 - 85 °C and continue to stir and react for 3 - 4 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge. Wash the precipitate with absolute methanol 2 - 3 times, and then place it in a vacuum drying oven. Dry it at a temperature of 40 - 45 °C for 4 - 5 h to obtain modified nano-silica.

[0015] As a further scheme of the present invention: The dosage ratio of the nano-silica, 3-aminopropyltriethoxysilane, ethanol solution and ammonia water in step b1 is 5 g: 3 - 6 g: 25 - 30 mL: 3 - 5 mL.

[0016] As a further scheme of the present invention: The volume fraction of the ethanol solution in step b1 is 85 - 90%; the mass fraction of the ammonia water is 20 - 25%.

[0017] As a further scheme of the present invention: The dosage ratio of the pre-modified nano-silica, boric acid, glycerol and absolute ethanol in step b2 is 5 g: 2 - 8 g: 40 - 45 mL: 20 - 25 mL.

[0018] The beneficial effects of the present invention: A method for preparing an environmentally friendly, fast-drying waterborne matte oil of the present invention comprises adding N,N-dimethylethanolamine, a wetting agent, an antifoaming agent, a leveling agent, and deionized water to a mixer for stirring and mixing. Then, modified nano-silica is added and stirring and mixing continue. Subsequently, a first waterborne emulsion, a second waterborne emulsion, a film-forming aid, and an anti-settling agent are added and stirring and mixing continue to obtain the environmentally friendly, fast-drying waterborne matte oil. In this preparation method, by using the first waterborne emulsion and the second waterborne emulsion as the main raw materials, combining their advantages and compensating for their disadvantages, the waterborne matte oil is given good film-forming properties and fast-drying properties, and an interpenetrating network structure is formed to improve the film-forming density, and the coating is given excellent weather resistance and water resistance. Adding modified nano-silica not only promotes the cross-linking reaction between the components, forming a dense structure on the coating surface, but also significantly improves the hardness and wear resistance of the coating and achieves a good matte effect. Moreover, this waterborne matte oil uses deionized water as the main solvent, endowing it with excellent environmental performance, and with its fast-drying characteristics, good matte effect, wear resistance, and water resistance, it has a wide range of application prospects in many fields.

[0019] Among them, the first waterborne emulsion is a polyacrylate emulsion formed by polymerizing methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid as polymerization monomers, providing excellent initial film-forming properties and good flexibility. The second waterborne emulsion is a fluorinated polyurethane emulsion formed by using a fluorinated modifier formed by reacting an amino group on melamine with a sulfonyl fluoride group on perfluorobutanesulfonyl fluoride as a chain extender and polymerizing polycarbonate diol and isophorone diisocyanate as polymerization monomers. A large number of fluorine atoms can form closely arranged fluorocarbon chain segments, endowing the matte oil with a unique matte effect. At the same time, it endows the coating with excellent weather resistance and water resistance, significantly enhancing the ability of the coating to resist the erosion of corrosive media. The modified nano-silica is obtained by hydrolyzing 3-aminopropyltriethoxysilane and grafting it onto the surface of nano-silica particles, introducing a large number of amino groups at the same time, and further treating it with boric acid to form B-N and introducing a large number of boric acid groups at the same time, significantly improving the dispersibility of nano-silica, enabling it to be evenly distributed in the coating, significantly improving the hardness and wear resistance of the coating, and further enhancing the matte effect of the matte oil. Moreover, a large number of boric acid groups can react with the hydroxyl groups in the first waterborne emulsion and the amino groups in the second waterborne emulsion, enhancing the cross-linking degree between the components, further enhancing the density between the coatings, and significantly improving the comprehensive performance of the coating. Specific embodiments

[0020] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0021] Example 1: This example is a method for preparing an environmentally friendly and fast-drying water-based matte oil, including the following steps: Step S1: Add 8 g of mixed monomers, 1.2 g of sodium dodecyl sulfate, and 30 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant pressure dropping funnel. Stir and react for 20 min at a temperature of 25 °C and a stirring rate of 200 r / min. Then, while stirring, gradually add dropwise the remaining 32 g of mixed monomers and 10 mL of a 2% ammonium persulfate solution at 80 °C, control the dropping rate at 1 drop / s. After the dropping is completed, continue to stir and react for 2 h. Then, cool to 35 °C and adjust the pH to 7.5 with 20% ammonia water, and then adjust to a solid content of 35% with distilled water to obtain the first water-based emulsion; the mixed monomers are composed of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid mixed in a mass ratio of 0.8:0.4:0.4:0.3; Step S2: Add 0.1 mol of melamine, 0.1 mol of triethylamine, and 80 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a constant pressure dropping funnel. Stir and react for 20 min at a temperature of 25 °C and a stirring rate of 200 r / min. Then, while stirring, gradually add dropwise 0.1 mol of perfluorobutanesulfonyl fluoride, control the dropping rate at 1 drop / s. After the dropping is completed, continue to stir and react for 10 h at 40 °C. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, wash twice with anhydrous acetone, and then place it in a vacuum drying oven and dry at 60 °C for 3 h to obtain a fluorine-containing modifier; Step S3: Add 11 mmol of polycarbonate diol PCDL-1000, 20 mmol of isophorone diisocyanate, 1.5 g of dibutyltin dilaurate, and 40 mL of anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection, and stir and react for 30 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, continue to stir and react for 3 h under the condition of raising the temperature to 70°C. After that, add 3 mmol of fluorine-containing modifier and continue to stir and react for 2 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 7 with triethylamine, then remove the solvent by rotary evaporation, and then add it to deionized water for emulsification to obtain a second aqueous emulsion with a solid content of 35%; Step S4: Add 5 g of nano-silica, 3 g of 3-aminopropyltriethoxysilane, 25 mL of an ethanol solution with a volume fraction of 85%, and 3 mL of an ammonia water with a mass fraction of 20% into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 20 min under the condition of an ultrasonic frequency of 30 kHz. Then, stir and react for 10 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, continue to stir and react for 4 h under the condition of raising the temperature to 60°C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate twice with anhydrous ethanol, and then place it in a vacuum drying oven and dry for 2 h under the condition of a temperature of 60°C to obtain pre-modified nano-silica; Step S5: Add 5 g of pre-modified nano-silica, 2 g of boric acid, 40 mL of glycerol, and 20 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 20 min under the condition of an ultrasonic frequency of 30 kHz. Then, stir and react for 10 min under the conditions of a temperature of 25°C and a stirring rate of 200 r / min. Then, continue to stir and react for 3 h under the condition of raising the temperature to 80°C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate twice with anhydrous methanol, and then place it in a vacuum drying oven and dry for 4 h under the condition of a temperature of 40°C to obtain modified nano-silica; Step S6: Weigh 17 parts of the first aqueous emulsion, 30 parts of the second aqueous emulsion, 3 parts of modified nano-silica, 0.2 part of N,N-dimethylethanolamine, 0.5 part of wetting agent, 0.2 part of defoaming agent, 0.5 part of leveling agent, 4 parts of film-forming auxiliary, 1.3 parts of anti-settling agent, and 13 parts of deionized water by weight; the wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming auxiliary is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax slurry 6900-20X; Step S7: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent and deionized water into a mixer, stir and mix for 5 min under the condition that the stirring rate is 1000 r / min, then add modified nano-silica and stir and mix for 15 min under the condition that the stirring rate is 2500 r / min, and then add the first aqueous emulsion, the second aqueous emulsion, film-forming aid and anti-settling agent and stir and mix for 30 min under the condition that the stirring rate is 1000 r / min to obtain an environmentally friendly and fast-drying waterborne matte oil.

[0022] Example 2: This example is a method for preparing an environmentally friendly and fast-drying waterborne matte oil, which includes the following steps: Step S1: Add 9 g of mixed monomers, 1.5 g of sodium dodecyl sulfate and 32 mL of deionized water into a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel, stir and react for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min, then raise the temperature to 82 °C and simultaneously add the remaining 36 g of mixed monomers and 12 mL of ammonium persulfate solution with a mass fraction of 2.5% drop by drop while stirring, control the dropping rate at 1 drop / s, continue to stir and react for 2.5 h after the dropping is completed, then cool to 38 °C and adjust the pH to 7.5 with 20% ammonia water, and then adjust to a solid content of 38% with distilled water to obtain the first aqueous emulsion; the mixed monomers are methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate and acrylic acid mixed in a mass ratio of 0.9:0.5:0.5:0.4; Step S2: Add 0.1 mol of melamine, 0.1 mol of triethylamine and 90 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, thermometer and constant pressure dropping funnel, stir and react for 25 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min, then add 0.1 mol of perfluorobutanesulfonyl fluoride drop by drop while stirring, control the dropping rate at 1 drop / s, continue to stir and react for 12 h after the dropping is completed under the condition of raising the temperature to 42 °C, cool the reaction product to room temperature after the reaction is completed, then rotate and evaporate to remove the solvent, then wash twice with anhydrous acetone, and then place it in a vacuum drying oven and dry for 3.5 h under the condition of a temperature of 62 °C to obtain a fluorine-containing modifier; Step S3: Add 13 mmol of polycarbonate diol PCDL-1000, 20 mmol of isophorone diisocyanate, 1.8 g of dibutyltin dilaurate, and 45 mL of anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer, and a gas pipe. Introduce nitrogen for protection. Stir and react for 40 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 4 h under the condition of raising the temperature to 75 °C. After that, add 4.5 mmol of fluorine-containing modifier and continue to stir and react for 2.5 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 7 with triethylamine. Then, remove the solvent by rotary evaporation, and then add it to deionized water for emulsification to obtain a second aqueous emulsion with a solid content of 38%; Step S4: Add 5 g of nano-silica, 4.5 g of 3-aminopropyltriethoxysilane, 28 mL of an ethanol solution with a volume fraction of 88%, and 4 mL of ammonia water with a mass fraction of 22% into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 25 min under the condition of an ultrasonic frequency of 35 kHz. Then, stir and react for 12 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 4.5 h under the condition of raising the temperature to 62 °C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate twice with anhydrous ethanol, and then place it in a vacuum drying oven and dry for 2.5 h under the condition of a temperature of 62 °C to obtain pre-modified nano-silica; Step S5: Add 5 g of pre-modified nano-silica, 5 g of boric acid, 42 mL of glycerol, and 22 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 25 min under the condition of an ultrasonic frequency of 35 kHz. Then, stir and react for 12 min under the conditions of a temperature of 28 °C and a stirring rate of 250 r / min. Then, continue to stir and react for 3.5 h under the condition of raising the temperature to 82 °C. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate twice with anhydrous methanol, and then place it in a vacuum drying oven and dry for 4.5 h under the condition of a temperature of 42 °C to obtain modified nano-silica; Step S6: Weigh 20 parts of the first aqueous emulsion, 33 parts of the second aqueous emulsion, 7 parts of modified nano-silica, 0.25 part of N,N-dimethylethanolamine, 0.7 part of wetting agent, 0.25 part of defoaming agent, 0.6 part of leveling agent, 5 parts of film-forming auxiliary, 1.9 parts of anti-settling agent, and 14 parts of deionized water according to weight; the wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming auxiliary is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax slurry 6900-20X; Step S7: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent and deionized water into a mixer, stir and mix for 8 min under the condition that the stirring rate is 1100 r / min, then add modified nano-silica and stir and mix for 18 min under the condition that the stirring rate is 2800 r / min, and then add the first aqueous emulsion, the second aqueous emulsion, film-forming aid and anti-settling agent and stir and mix for 40 min under the condition that the stirring rate is 1100 r / min to obtain an environmentally friendly and fast-drying water-based matte oil.

[0023] Example 3: This example is a method for preparing an environmentally friendly and fast-drying water-based matte oil, including the following steps: Step S1: Add 10 g of mixed monomers, 1.8 g of sodium dodecyl sulfate and 35 mL of deionized water into a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel, stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then while stirring, gradually add dropwise the remaining 40 g of mixed monomers and 15 mL of ammonium persulfate solution with a mass fraction of 3% under the condition of heating to 85 °C, control the dropping rate to be 2 drops / s, continue to stir and react for 3 h after the dropping is completed, then cool to 40 °C and adjust to pH 8 with 20% ammonia water, and then adjust to a solid content of 40% with distilled water to obtain the first aqueous emulsion; the mixed monomers are methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate and acrylic acid mixed in a mass ratio of 1.0:0.6:0.6:0.5; Step S2: Add 0.1 mol of melamine, 0.1 mol of triethylamine and 100 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, thermometer and constant pressure dropping funnel, stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then gradually add dropwise 0.1 mol of perfluorobutanesulfonyl fluoride while stirring, control the dropping rate to be 2 drops / s, continue to stir and react for 15 h under the condition of heating to 45 °C after the dropping is completed, cool the reaction product to room temperature after the reaction ends, then remove the solvent by rotary evaporation, then wash 3 times with anhydrous acetone, and then place it in a vacuum drying oven and dry for 4 h under the condition of a temperature of 65 °C to obtain a fluorine-containing modifier; Step S3: Add 15 mmol of polycarbonate diol PCDL-1000, 20 mmol of isophorone diisocyanate, 2.1 g of dibutyltin dilaurate, and 50 mL of anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection. Stir and react at a temperature of 30 °C and a stirring rate of 300 r / min for 50 min. Then, raise the temperature to 80 °C and continue to stir and react for 5 h. After that, add 6 mmol of fluorine-containing modifier and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 7 with triethylamine. Then, remove the solvent by rotary evaporation, and then add it to deionized water for emulsification to obtain a second aqueous emulsion with a solid content of 40%; Step S4: Add 5 g of nano-silica, 6 g of 3-aminopropyltriethoxysilane, 30 mL of an ethanol solution with a volume fraction of 90%, and 5 mL of ammonia water with a mass fraction of 25% into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 30 min under the condition of an ultrasonic frequency of 40 kHz. Then, stir and react at a temperature of 30 °C and a stirring rate of 300 r / min for 15 min. Then, raise the temperature to 65 °C and continue to stir and react for 5 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with anhydrous ethanol 3 times, and then place it in a vacuum drying oven and dry at a temperature of 65 °C for 3 h to obtain pre-modified nano-silica; Step S5: Add 5 g of pre-modified nano-silica, 8 g of boric acid, 45 mL of glycerol, and 25 mL of anhydrous ethanol into a three-necked flask equipped with a stirrer and a thermometer. Ultrasonically disperse for 30 min under the condition of an ultrasonic frequency of 40 kHz. Then, stir and react at a temperature of 30 °C and a stirring rate of 300 r / min for 15 min. Then, raise the temperature to 85 °C and continue to stir and react for 4 h. After the reaction is completed, cool the reaction product to room temperature, then centrifuge, wash the precipitate with anhydrous methanol 3 times, and then place it in a vacuum drying oven and dry at a temperature of 45 °C for 5 h to obtain modified nano-silica; Step S6: Weigh 23 parts of the first aqueous emulsion, 36 parts of the second aqueous emulsion, 11 parts of modified nano-silica, 0.3 part of N,N-dimethylethanolamine, 0.9 part of wetting agent, 0.3 part of defoaming agent, 0.7 part of leveling agent, 6 parts of film-forming aid, 2.5 parts of anti-settling agent, and 15 parts of deionized water by weight; the wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming aid is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax paste 6900-20X; Step S7: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent and deionized water into a mixer, stir and mix for 10 min under the condition that the stirring rate is 1200 r / min, then add modified nano-silica and stir and mix for 20 min under the condition that the stirring rate is 3000 r / min, and then add the first aqueous emulsion, the second aqueous emulsion, film-forming aid and anti-settling agent and stir and mix for 50 min under the condition that the stirring rate is 1200 r / min to obtain an environmentally friendly and fast-drying waterborne matte oil.

[0024] Comparative Example 1: This comparative example is a method for preparing an environmentally friendly and fast-drying waterborne matte oil, including the following steps: Step S1: Add 10 g of mixed monomers, 1.8 g of sodium dodecyl sulfate and 35 mL of deionized water into a four-necked flask equipped with a stirrer, thermometer, reflux condenser and constant pressure dropping funnel, stir and react for 30 min under the conditions of a temperature of 30 °C and a stirring rate of 300 r / min, then raise the temperature to 85 °C and simultaneously dropwise add the remaining 40 g of mixed monomers and 15 mL of 3% ammonium persulfate solution drop by drop while stirring, control the dropping rate to be 2 drops / s, continue to stir and react for 3 h after dropping, then cool down to 40 °C and adjust to pH 8 with 20% ammonia water, and then adjust to a solid content of 40% with distilled water to obtain the first aqueous emulsion; the mixed monomers are a mixture of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate and acrylic acid in a mass ratio of 1.0:0.6:0.6:0.5; Step S2: Weigh 23 parts of the first aqueous emulsion, 0.3 part of N,N-dimethylethanolamine, 0.9 part of wetting agent, 0.3 part of defoaming agent, 0.7 part of leveling agent, 6 parts of film-forming aid, 2.5 parts of anti-settling agent and 15 parts of deionized water by weight; the wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming aid is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax paste 6900-20X; Step S3: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent and deionized water into a mixer, stir and mix for 10 min under the condition that the stirring rate is 1200 r / min, then stir and mix for 20 min under the condition that the stirring rate is 3000 r / min, and then add the first aqueous emulsion, film-forming aid and anti-settling agent and stir and mix for 50 min under the condition that the stirring rate is 1200 r / min to obtain an environmentally friendly and fast-drying waterborne matte oil.

[0025] Comparative Example 2: This comparative example is a method for preparing an environmentally friendly, quick-drying water-based matte oil, comprising the following steps: Step S1: Add 0.1 mol of melamine, 0.1 mol of triethylamine, and 100 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 30 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 0.1 mol of perfluorobutanesulfonyl fluoride dropwise, controlling the dropping rate at 2 drops / s. After the addition is complete, continue to stir and react at 45 °C for 15 h. After the reaction ends, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, wash it 3 times with anhydrous acetone, and then place it in a vacuum drying oven and dry it at 65 °C for 4 h to obtain a fluorine-containing modifier; Step S2: Add 15 mmol of polycarbonate diol PCDL-1000, 20 mmol of isophorone diisocyanate, 2.1 g of dibutyltin dilaurate, and 50 mL of anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Pass in nitrogen for protection and stir and react at 30 °C and a stirring rate of 300 r / min for 50 min. Then, continue to stir and react at 80 °C for 5 h. Then, add 6 mmol of the fluorine-containing modifier and continue to stir and react for 3 h. After the reaction ends, cool the reaction product to room temperature, then adjust the pH to 7 with triethylamine, then remove the solvent by rotary evaporation, and then add it to deionized water for emulsification to obtain a second water-based emulsion with a solid content of 40%; Step S3: Weigh 36 parts of the second water-based emulsion, 0.3 part of N,N-dimethylethanolamine, 0.9 part of wetting agent, 0.3 part of defoaming agent, 0.7 part of leveling agent, 6 parts of film-forming auxiliary, 2.5 parts of anti-settling agent, and 15 parts of deionized water by weight; the wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming auxiliary is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax paste 6900-20X; Step S4: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent, and deionized water into a mixer and stir and mix at a stirring rate of 1200 r / min for 10 min. Then, stir and mix at a stirring rate of 3000 r / min for 20 min. Then, add the second water-based emulsion, film-forming auxiliary, and anti-settling agent and stir and mix at a stirring rate of 1200 r / min for 50 min to obtain an environmentally friendly, quick-drying water-based matte oil.

[0026] Comparative Example 3: This comparative example is a method for preparing an environmentally friendly, quick-drying water-based matte oil, comprising the following steps: Step S1: Add 10 g of the mixed monomers, 1.8 g of sodium dodecyl sulfate, and 35 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant-pressure dropping funnel. Stir and react for 30 min at a temperature of 30°C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise the remaining 40 g of the mixed monomers and 15 mL of an ammonium persulfate solution with a mass fraction of 3% at a temperature of 85°C, controlling the dropping rate to be 2 drops / s. After the dropping is completed, continue to stir and react for 3 h. Then, cool to 40°C and adjust the pH to 8 with ammonia water with a mass fraction of 20%. Then, adjust to a solid content of 40% with distilled water to obtain the first aqueous emulsion; the mixed monomers are composed of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid mixed in a mass ratio of 1.0:0.6:0.6:0.5; Step S2: Add 0.1 mol of melamine, 0.1 mol of triethylamine, and 100 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 30 min at a temperature of 30°C and a stirring rate of 300 r / min. Then, while stirring, gradually add dropwise 0.1 mol of perfluorobutanesulfonyl fluoride, controlling the dropping rate to be 2 drops / s. After the dropping is completed, continue to stir and react for 15 h at a temperature of 45°C. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, then wash 3 times with anhydrous acetone, and then place it in a vacuum drying oven and dry at a temperature of 65°C for 4 h to obtain the fluorine-containing modifier; Step S3: Add 15 mmol of polycarbonate diol PCDL-1000, 20 mmol of isophorone diisocyanate, 2.1 g of dibutyltin dilaurate, and 50 mL of anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection and stir and react for 50 min at a temperature of 30°C and a stirring rate of 300 r / min. Then, continue to stir and react for 5 h at a temperature of 80°C. Then, add 6 mmol of the fluorine-containing modifier and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 7 with triethylamine, then remove the solvent by rotary evaporation, and then add it to deionized water for emulsification to obtain the second aqueous emulsion with a solid content of 40%; Step S4: Weigh 23 parts by weight of the first aqueous emulsion, 36 parts of the second aqueous emulsion, 0.3 part of N,N-dimethylethanolamine, 0.9 part of wetting agent, 0.3 part of defoaming agent, 0.7 part of leveling agent, 6 parts of film-forming aid, 2.5 parts of anti-settling agent, and 15 parts of deionized water; the wetting agent is Tego 245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming aid is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax paste 6900-20X; Step S5: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent, and deionized water into a mixer, stir and mix for 10 min under the condition of a stirring rate of 1200 r / min, then stir and mix for 20 min under the condition of a stirring rate of 3000 r / min, then add the first aqueous emulsion, the second aqueous emulsion, the film-forming aid, and the anti-settling agent and stir and mix for 50 min under the condition of a stirring rate of 1200 r / min to obtain an environmentally friendly and fast-drying water-based matte oil.

[0027] Comparative Example 4: This comparative example is a method for preparing an environmentally friendly and fast-drying water-based matte oil, including the following steps: Step S1: Add 10 g of mixed monomers, 1.8 g of sodium dodecyl sulfate, and 35 mL of deionized water into a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a constant-pressure dropping funnel, stir and react for 30 min under the conditions of a temperature of 30°C and a stirring rate of 300 r / min, then raise the temperature to 85°C and simultaneously add the remaining 40 g of mixed monomers and 15 mL of 3% ammonium persulfate solution dropwise while stirring, control the dropping rate at 2 drops / s, continue to stir and react for 3 h after dropping, then cool down to 40°C and adjust the pH to 8 with 20% ammonia water, and then adjust to a solid content of 40% with distilled water to obtain the first aqueous emulsion; the mixed monomers are a mixture of methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate, and acrylic acid in a mass ratio of 1.0:0.6:0.6:0.5; Step S2: Add 0.1 mol of melamine, 0.1 mol of triethylamine, and 100 mL of N,N-dimethylformamide into a three-necked flask equipped with a stirrer, a thermometer, and a constant-pressure dropping funnel. Stir and react for 30 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, while stirring, gradually add 0.1 mol of perfluorobutanesulfonyl fluoride dropwise, controlling the dropping rate at 2 drops / s. After the addition is complete, continue to stir and react at 45 °C for 15 h. After the reaction is completed, cool the reaction product to room temperature, then remove the solvent by rotary evaporation, wash it 3 times with anhydrous acetone, and then place it in a vacuum drying oven and dry it at 65 °C for 4 h to obtain a fluorine-containing modifier; Step S3: Add 15 mmol of polycarbonate diol PCDL-1000, 20 mmol of isophorone diisocyanate, 2.1 g of dibutyltin dilaurate, and 50 mL of anhydrous acetone into a three-necked flask equipped with a stirrer, a thermometer, and a gas guide tube. Introduce nitrogen for protection and stir and react for 50 min at a temperature of 30 °C and a stirring rate of 300 r / min. Then, continue to stir and react at 80 °C for 5 h. Then, add 6 mmol of the fluorine-containing modifier and continue to stir and react for 3 h. After the reaction is completed, cool the reaction product to room temperature, then adjust the pH to 7 with triethylamine, then remove the solvent by rotary evaporation, and then add it to deionized water for emulsification to obtain a second aqueous emulsion with a solid content of 40%; Step S4: Weigh 23 parts of the first aqueous emulsion, 36 parts of the second aqueous emulsion, 11 parts of nano-silica, 0.3 part of N,N-dimethylethanolamine, 0.9 part of wetting agent, 0.3 part of defoaming agent, 0.7 part of leveling agent, 6 parts of film-forming aid, 2.5 parts of anti-settling agent, and 15 parts of deionized water by weight; the wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming aid is propylene glycol methyl ether acetate; the anti-settling agent is polyamide wax anti-settling wax slurry 6900-20X; Step S5: Add N,N-dimethylethanolamine, wetting agent, defoaming agent, leveling agent, and deionized water into a mixer, stir and mix for 10 min at a stirring rate of 1200 r / min, then add nano-silica and stir and mix for 20 min at a stirring rate of 3000 r / min, and then add the first aqueous emulsion, the second aqueous emulsion, film-forming aid, and anti-settling agent and stir and mix for 50 min at a stirring rate of 1200 r / min to obtain an environmentally friendly, fast-drying, water-based matte oil.

[0028] The environment-friendly fast-drying water-based matte oil of Examples 1-3 and Comparative Examples 1-4 was evenly coated on a 25-μm-thick PET plastic film with a 1.5-μm wire bar, and then dried and cured at 90°C for 30 s, after which the coating properties were tested. The test results are shown in the following table:

[0029] Referring to the data in the above table, by comparing Examples 1-3 and Comparative Examples 1-4, it can be known that the environment-friendly fast-drying water-based matte oil of the present application has excellent wear resistance and water resistance.

[0030] Among them, the wear resistance test method is as follows: under the conditions of a friction pressure of 20±0.2 N, a friction speed of 43 times / min, and a friction area of 155 mm (L)×50 mm (W), friction is carried out 100 times, and the surface state of the coating is observed.

[0031] Among them, the water resistance test method is as follows: the sample is immersed in distilled water at 25°C for 7 d, and the surface state of the coating is observed.

[0032] Among them, the damp heat resistance test method is as follows: the sample is placed in a constant temperature and humidity chamber at 65°C and 90% humidity for 3 d, and the surface state of the coating is observed.

[0033] In the description of this specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0034] The above content is only an example and illustration of the present invention. Those skilled in the art of the present technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined by the present application, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an environmentally friendly quick-drying water-based matte oil, characterized in that: The following steps are involved: Step 1: Weigh 17-23 parts of the first aqueous emulsion, 30-36 parts of the second aqueous emulsion, 3-11 parts of modified nano-silica, 0.2-0.3 parts of N,N-dimethylethanolamine, 0.5-0.9 parts of wetting agent, 0.2-0.3 parts of defoaming agent, 0.5-0.7 parts of leveling agent, 4-6 parts of film-forming aid, 1.3-2.5 parts of anti-settling agent and 13-15 parts of deionized water according to weight parts; Step 2: Add N,N-dimethylethanolamine, a wetting agent, a defoaming agent, a leveling agent and deionized water into a mixer, stir and mix for 5-10 minutes at a stirring rate of 1000-1200 r / min, then add modified nano-silica and stir and mix for 15-20 minutes at a stirring rate of 2500-3000 r / min, then add the first aqueous emulsion, the second aqueous emulsion, a film-forming aid and an anti-settling agent and stir and mix for 30-50 minutes at a stirring rate of 1000-1200 r / min to obtain an environmentally friendly quick-drying aqueous matte oil; Wherein, the second aqueous emulsion is prepared by the following steps: Step a1: stirring melamine, triethylamine and N,N-dimethylformamide for reaction, then adding perfluorobutylsulfonyl fluoride dropwise while stirring, and continuing to stir the reaction after the addition is complete. After the reaction is completed, the reaction product is cooled, then rotary evaporated, and then washed and dried to obtain a fluorine-containing modifier; Step a2: Stirring polycarbonate diol, isophorone diisocyanate, dibutyltin dilaurate and anhydrous acetone for reaction, then adding a fluorine-containing modifier and continuing the stirring reaction. After the reaction is completed, the reaction product is cooled, the pH is adjusted, and then rotary evaporated, and then added to deionized water for emulsification to obtain a second aqueous emulsion with a solid content of 35-40%.

2. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 1, characterized in that: The wetting agent is Tego245 wetting agent; the defoaming agent is BYK-024 defoaming agent; the leveling agent is BYK-306 leveling agent; the film-forming aid is propylene glycol methyl ether acetate; and the anti-settling agent is polyamide wax anti-settling wax slurry 6900-20X.

3. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 1, characterized in that: The usage ratio of melamine, triethylamine, N,N-dimethylformamide and perfluorobutylsulfonyl fluoride in step a1 is 0.1 mol: 0.1 mol: 80-100 mL: 0.1 mol.

4. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 1, characterized in that: The usage ratio of the polycarbonate diol, isophorone diisocyanate, dibutyltin dilaurate, anhydrous acetone and fluorine-containing modifier in step a2 is 11-15mmol:20mmol:1.5-2.1g:40-50mL:3-6mmol; the polycarbonate diol is PCDL-1000.

5. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 1, characterized in that: The first aqueous emulsion is prepared by the following steps: 1 / 5 of the mixed monomer, sodium dodecyl sulfate and deionized water are stirred for reaction, and then the remaining 4 / 5 of the mixed monomer and ammonium persulfate solution are added dropwise while stirring. After the addition is completed, the stirring reaction is continued, and then the pH is adjusted, and then distilled water is used to adjust the solid content to 35-40% to obtain a first aqueous emulsion.

6. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 5, characterized in that: The usage ratio of the mixed monomer, sodium dodecyl sulfate, deionized water and ammonium persulfate solution is 40-50 g: 1.2-1.8 g: 30-35 mL: 10-15 mL.

7. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 5, characterized in that: The mixed monomer is methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate and acrylic acid in a mass ratio of 0.8-1.0: 0.4-0.6: 0.4-0.6: 0.3-0.5; the mass fraction of the ammonium persulfate solution is 2-3%.

8. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 1, characterized in that: The modified nano silicon dioxide is prepared by the following steps: Step b1: Ultrasonic dispersion of nano-silica, 3-aminopropyltriethoxysilane, ethanol solution and ammonia water, followed by stirring for reaction, cooling the reaction product after the reaction, centrifuging it, washing and drying the precipitate to obtain pre-modified nano-silica; Step b2: ultrasonically disperse the pre-modified nano-silica, boric acid, propylene glycol and anhydrous ethanol, and then stir to react. After the reaction is completed, cool the reaction product, centrifuge it, wash and dry the precipitate to obtain modified nano-silica.

9. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 8, characterized in that: The dosage ratio of the nano-silica, 3-aminopropyltriethoxysilane, ethanol solution and ammonia water in step b1 is 5g:3-6g:25-30mL:3-5mL; the volume fraction of the ethanol solution is 85-90%; and the mass fraction of the ammonia water is 20-25%.

10. The method for preparing an environmentally friendly quick-drying water-based matte oil according to claim 8, characterized in that: The dosage ratio of the pre-modified nano-silica, boric acid, glycerol and anhydrous ethanol in step b2 is 5g:2-8g:40-45mL:20-25mL.

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