阅读说明：本技术 一种水性环保涂料及其制备方法 (Water-based environment-friendly coating and preparation method thereof ) 是由 黄向阳 唐志龙 于 2021-08-02 设计创作，主要内容包括：本发明公开了一种水性环保涂料及其制备方法,该涂料包括如下重量份原料：水性聚氨酯乳液80-100份、增强树脂复合物15-30份、自修复微囊10-15份、固化微囊10-15份、消泡剂0.5-1份、水30-50份；该增强树脂复合物主链为环氧树脂,使得制备出的水性环保涂料具有很好耐冲击强度,同时石墨烯的存在,使得涂膜的耐冲击强度进一步的提升,在涂膜受到外力作用出现划伤时,自修复微囊和固化微囊破损,外力挤压大孔径介孔二氧化硅释放苯乙烯,固化微囊释放过氧化二苯甲酰,苯乙烯接触过氧化二苯甲酰发生自体聚合反应,使得涂膜表面划痕修复,保证涂膜能够正常使用。(The invention discloses a water-based environment-friendly coating and a preparation method thereof, wherein the coating comprises the following raw materials in parts by weight: 80-100 parts of aqueous polyurethane emulsion, 15-30 parts of reinforced resin compound, 10-15 parts of self-repairing microcapsule, 10-15 parts of cured microcapsule, 0.5-1 part of defoaming agent and 30-50 parts of water; the main chain of the reinforced resin compound is epoxy resin, so that the prepared water-based environment-friendly coating has good impact strength, and graphene exists, so that the impact strength of the coating is further improved, when the coating is scratched under the action of external force, the self-repairing microcapsule and the curing microcapsule are damaged, the external force extrudes the large-aperture mesoporous silica to release styrene, the curing microcapsule releases dibenzoyl peroxide, the styrene contacts the dibenzoyl peroxide to generate autopolymerization, the scratch on the surface of the coating is repaired, and the coating can be normally used.)

1. The water-based environment-friendly coating is characterized in that: the feed comprises the following raw materials in parts by weight: 80-100 parts of aqueous polyurethane emulsion, 15-30 parts of reinforced resin compound, 10-15 parts of self-repairing microcapsule, 10-15 parts of cured microcapsule, 0.5-1 part of defoaming agent and 30-50 parts of water;

the reinforced resin compound is prepared by the following steps;

step A1: adding phosphorus oxychloride into a reaction kettle, stirring, adding benzyltrimethylammonium chloride and molten phenol, reacting, adding p-hydroxybenzoic acid, and continuing to react to obtain an intermediate 1;

step A2: adding epoxy resin E-44 into a reaction kettle, stirring, adding polyethylene glycol 4000, adding potassium persulfate, reacting to obtain an intermediate 2, adding the intermediate 2 and deionized water into the reaction kettle, stirring, adding the intermediate 1 and triphenylphosphine, and performing reflux reaction to obtain an intermediate 3;

step A3: adding phloroglucinol, sodium carbonate, tetrahydrofuran, the intermediate 3 and dibromoethane into a reaction kettle, reacting, adding epoxy chloropropane, continuing to react to obtain an intermediate 4, adding the intermediate 4, triphenylphosphine, gallic acid and tetrahydrofuran into the reaction kettle, performing reflux reaction, adding graphene oxide, continuing to reflux, adding self-repairing microcapsules and 1-hydroxybenzotriazole, reacting, filtering to remove filtrate, drying a filter cake, and reinforcing a resin compound.

2. The aqueous environment-friendly coating material as claimed in claim 1, wherein: the molar ratio of the phosphorus oxychloride, the benzyltrimethylammonium chloride, the phenol and the p-hydroxybenzoic acid in the step A1 is 2.5: 0.08: 1.8: 1.2.

3. the aqueous environment-friendly coating material as claimed in claim 1, wherein: the mass ratio of the epoxy resin E-44, the polyethylene glycol 4000 and the potassium persulfate in the step A2 is 10: 5: 0.01, wherein the dosage mass ratio of the intermediate 1, the intermediate 2 and the triphenylphosphine is 10: 3: 1.5.

4. the aqueous environment-friendly coating material as claimed in claim 1, wherein: the using amount mass ratio of the phloroglucinol, the sodium carbonate, the intermediate 3, the dibromoethane and the epichlorohydrin in the step A3 is 3: 30: 10: 9: 9.25, the dosage mass ratio of the intermediate 4, triphenylphosphine, gallic acid, graphene oxide, the self-repairing microcapsule to the 1-hydroxybenzotriazole is 5: 8.2: 3.5: 10: 3: 5.5.

5. the aqueous environment-friendly coating material as claimed in claim 1, wherein: the self-repairing microcapsule is prepared by the following steps:

step B1: dissolving sodium acetate in deionized water to prepare a sodium acetate solution, mixing acetic acid and deionized water to prepare an acetic acid solution, mixing the sodium acetate solution and the acetic acid solution to prepare a buffer solution, adding gelatin and the buffer solution into a reaction kettle, stirring, adding gamma-aminopropyltriethoxysilane, reacting, and preparing a coating solution;

step B2: adding P123, potassium chloride and hydrochloric acid solution into a reaction kettle, stirring, adding 3, 3', 5, 5' -tetramethylbenzidine, continuing stirring, adding tetraethoxysilane, after heat preservation reaction, heating and continuing heat preservation, and filtering to remove filtrate to obtain the large-aperture mesoporous silica;

step B3: soaking the large-aperture mesoporous silica in styrene, carrying out ultrasonic treatment, filtering to obtain a core material, adding the core material, a coating solution and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring, adding a sodium sulfate solution, continuously stirring under the condition of ice-water bath, adding glutaraldehyde, continuously stirring and standing to obtain the self-repairing microcapsule.

6. The aqueous environment-friendly paint as claimed in claim 5, wherein: the dosage ratio of the sodium acetate to the deionized water in the step B1 is 2.74 g: 100mL, and the volume ratio of the acetic acid to the deionized water is 1.6: 50, the volume ratio of the sodium acetate solution to the acetic acid solution is 9: 1, the dosage ratio of gelatin, buffer solution and gamma-aminopropyltriethoxysilane is 5 g: 50mL of: 4g of the total weight.

7. The aqueous environment-friendly paint as claimed in claim 5, wherein: the dosage ratio of the P123, the potassium chloride, the hydrochloric acid solution, the 3, 3', 5, 5' -tetramethyl benzidine and the ethyl orthosilicate in the step B2 is 4.2 g: 3 g: 120mL of: 3 g: 8.6g, the concentration of the hydrochloric acid solution is 2 mol/L.

8. The aqueous environment-friendly paint as claimed in claim 5, wherein: the using amount ratio of the core material, the coating solution, the fatty alcohol-polyoxyethylene ether, the sodium sulfate solution and the glutaraldehyde in the step B3 is 15 g: 80mL of: 0.3 mL: 15mL of: 10mL, and the mass fraction of the sodium sulfate solution is 40%.

9. The preparation method of the water-based environment-friendly paint as claimed in claim 1, characterized in that: the method specifically comprises the following steps:

step S1: weighing aqueous polyurethane emulsion, a reinforced resin compound, a self-repairing microcapsule, a curing microcapsule, a defoaming agent and water;

step S2: the raw materials are mixed and stirred evenly under the condition that the rotating speed is 1000-1200r/min, and the water-based environment-friendly coating is prepared.

Technical Field

The invention relates to the technical field of paint preparation, in particular to a water-based environment-friendly paint and a preparation method thereof.

Background

The coating is a continuous film which is coated on the surface of a protected or decorated object and can form firm adhesion with the coated object, and is a viscous liquid which is prepared by taking resin, oil or emulsion as a main material, adding or not adding pigments and fillers, adding corresponding auxiliaries and using an organic solvent or water;

the inner wall coating is the emulsion paint for general decoration, the emulsion paint is an emulsion material and is divided into two categories of polyvinyl acetate emulsion and acrylic emulsion according to the difference of base materials, the emulsion paint takes water as a diluent, and is a material with convenient construction, safety, water washing resistance and good air permeability, and different colors can be prepared according to different color matching schemes;

however, a paint film formed by coating the existing water-based environment-friendly paint has low impact strength, and after the paint film is soaked in water for a long time, the paint film can bubble or fall off, part of the paint is used for protecting a metal piece, the metal piece can rust due to falling off, and the paint film is easy to scratch under the action of external force in the process of protecting the paint film, so that the integrity of the paint film is influenced, and the using effect of the paint is further influenced;

a solution is now proposed to address the technical drawback in this respect.

Disclosure of Invention

The invention aims to provide a water-based environment-friendly coating and a preparation method thereof.

The purpose of the invention can be realized by the following technical scheme:

the water-based environment-friendly coating comprises the following raw materials in parts by weight: 80-100 parts of aqueous polyurethane emulsion, 15-30 parts of reinforced resin compound, 10-15 parts of self-repairing microcapsule, 10-15 parts of cured microcapsule, 0.5-1 part of defoaming agent and 30-50 parts of water;

the environment-friendly coating is prepared by uniformly blending the raw materials.

Furthermore, the defoaming agent is one or a mixture of more of polydimethylsiloxane, dimethyl polysiloxane and dimethyl silicone oil in any proportion.

Further, the reinforced resin composite is prepared by the following steps;

step A1: adding phosphorus oxychloride into a reaction kettle, stirring for 20-30min under the conditions that the rotating speed is 150-;

the reaction process is as follows:

step A2: adding epoxy resin E-44 into a reaction kettle, stirring and adding polyethylene glycol 4000 under the conditions that the rotating speed is 120-plus-150 r/min and the temperature is 50-60 ℃, heating to the temperature of 100-plus-110 ℃, adding potassium persulfate, continuously heating to the temperature of 180-plus-190 ℃, reacting for 2-3h to obtain an intermediate 2, adding the intermediate 2 and deionized water into the reaction kettle, stirring and adding the intermediate 1 and triphenylphosphine under the conditions that the rotating speed is 150-plus-200 r/min and the temperature is 55-65 ℃, heating to the temperature of 100-plus-120 ℃, and performing reflux reaction for 1-1.5h to obtain an intermediate 3;

the reaction process is as follows:

step A3: adding phloroglucinol, sodium carbonate, tetrahydrofuran, an intermediate 3 and dibromoethane into a reaction kettle, reacting for 5-8h at the rotation speed of 120-60 ℃ for 5-8h, adding epichlorohydrin, continuing to react for 8-10h to obtain an intermediate 4, adding the intermediate 4, triphenylphosphine, gallic acid and tetrahydrofuran into the reaction kettle, performing reflux reaction for 3-5h at the temperature of 110-60 ℃ for 3-5h, adding graphene oxide, continuing to reflux for 3-5h, adding self-repairing microcapsules and 1-hydroxybenzotriazole, reacting for 2-4h at the temperature of 50-60 ℃, filtering to remove filtrate, drying filter cakes and reinforcing resin compounds.

The reaction process is as follows:

further, the molar ratio of the phosphorus oxychloride, the benzyltrimethylammonium chloride, the phenol and the p-hydroxybenzoic acid in the step a1 is 2.5: 0.08: 1.8: 1.2.

further, the dosage mass ratio of the epoxy resin E-44, the polyethylene glycol 4000 and the potassium persulfate in the step A2 is 10: 5: 0.01, wherein the dosage mass ratio of the intermediate 1, the intermediate 2 and the triphenylphosphine is 10: 3: 1.5.

further, the amount mass ratio of the phloroglucinol, the sodium carbonate, the intermediate 3, the dibromoethane and the epichlorohydrin in the step A3 is 3: 30: 10: 9: 9.25, the dosage mass ratio of the intermediate 4, triphenylphosphine, gallic acid, graphene oxide, the self-repairing microcapsule to the 1-hydroxybenzotriazole is 5: 8.2: 3.5: 10: 3: 5.5.

further, the self-repairing microcapsule is prepared by the following steps:

step B1: dissolving sodium acetate in deionized water to prepare a sodium acetate solution, mixing acetic acid with the deionized water to prepare an acetic acid solution, mixing the sodium acetate solution with the acetic acid solution to prepare a buffer solution, adding gelatin and the buffer solution into a reaction kettle, stirring and adding gamma-aminopropyltriethoxysilane at the rotation speed of 120-150r/min and the temperature of 35-40 ℃ to react for 7-9h to prepare a coating solution;

step B2: adding P123, potassium chloride and hydrochloric acid solution into a reaction kettle, stirring for 10-15min under the conditions that the rotation speed is 200-plus-energy 300r/min and the temperature is 50-60 ℃, cooling to the temperature of 25-30 ℃, adding 3, 3', 5, 5' -tetramethylbenzidine, stirring for 10-15h, adding tetraethoxysilane, keeping the temperature for 20-25h under the condition that the temperature is 40-50 ℃, heating to the temperature of 100 ℃, continuing to keep the temperature for 20-25h, filtering to remove filtrate, and drying a filter cake to obtain the large-aperture mesoporous silica;

step B3: soaking large-aperture mesoporous silica in styrene, carrying out ultrasonic treatment for 1-1.5h under the condition of 40-50KHz frequency, filtering to obtain a core material, adding the core material, coating liquid and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 3-5min at the rotation speed of 400-500r/min and the temperature of 40-50 ℃, adding a sodium sulfate solution, continuously stirring for 30-40min under the condition of ice-water bath, adding glutaraldehyde, continuously stirring for 3-5min, standing for 10-15min, filtering and drying to obtain the self-repairing microcapsule.

Further, the ratio of the sodium acetate to the deionized water in the step B1 is 2.74 g: 100mL, and the volume ratio of the acetic acid to the deionized water is 1.6: 50, the volume ratio of the sodium acetate solution to the acetic acid solution is 9: 1, the dosage ratio of gelatin, buffer solution and gamma-aminopropyltriethoxysilane is 5 g: 50mL of: 4g of the total weight.

Further, the dosage ratio of the P123, the potassium chloride, the hydrochloric acid solution, the 3, 3', 5, 5' -tetramethylbenzidine and the ethyl orthosilicate in the step B2 is 4.2 g: 3 g: 120mL of: 3 g: 8.6g, the concentration of the hydrochloric acid solution is 2 mol/L.

Further, the usage ratio of the core material, the coating solution, the fatty alcohol-polyoxyethylene ether, the sodium sulfate solution and the glutaraldehyde in the step B3 is 15 g: 80mL of: 0.3 mL: 15mL of: 10mL, and the mass fraction of the sodium sulfate solution is 40%.

Further, the cured microcapsule is prepared by the following steps:

step C1: adding the gelatin solution, dibenzoyl peroxide and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 3-5min at the rotation speed of 400-500r/min and at the temperature of 40-50 ℃, adding a sodium sulfate solution, continuously stirring for 30-40min under the ice-water bath condition, adding glutaraldehyde, continuously stirring for 3-5min, standing for 10-15min, filtering and drying to obtain the cured microcapsule.

Further, the using amount ratio of the gelatin solution, dibenzoyl peroxide, fatty alcohol-polyoxyethylene ether, sodium sulfate solution and glutaraldehyde is 80 mL: 20 g: : 0.3 mL: 15mL of: 10mL, sodium sulfate solution was the same as described in step B3.

The invention has the following beneficial effects:

the invention prepares a reinforced resin compound, a self-repairing microcapsule and a curing microcapsule in the process of preparing a water-based environment-friendly coating, the reinforced resin compound takes phosphorus oxychloride as a raw material to react with phenol and p-hydroxybenzoic acid in sequence to prepare an intermediate 1, epoxy resin E-44 and polyethylene glycol 4000 are subjected to chain extension reaction to prepare an intermediate 2, the intermediate 1 and the intermediate 2 are reacted to ensure that epoxy groups on the intermediate 2 are subjected to ring opening reaction with carboxyl groups of the intermediate 1 to prepare an intermediate 3, the intermediate 3 and phloroglucinol are treated with sodium carbonate and dibromoethane to ensure that the phloroglucinol is grafted on the intermediate 3 and then reacted with epichlorohydrin to prepare an intermediate 4, the intermediate 4 is connected with gallic acid and graphene oxide to ensure that epoxy groups on the intermediate 4 are subjected to ring opening reaction respectively with carboxyl groups on the gallic acid and the graphene oxide, the self-repairing microcapsule is added, the surface of the self-repairing microcapsule contains a large amount of amino, and the amino and the unreacted carboxyl on the surface of graphene oxide are subjected to dehydration condensation under the action of 1-hydroxybenzotriazole to prepare a reinforced resin compound, the main chain of the reinforced resin compound is epoxy resin, so that the prepared water-based environment-friendly coating has good impact strength, meanwhile, the existence of graphene further improves the impact strength of a coating film, the coating film is not easy to scratch, a molecular chain of the reinforced resin compound contains a large amount of o-phenolic hydroxyl, the o-phenolic hydroxyl reacts with ferrous ions and ferric ions in iron rust to form a complex, a protective film is further formed on a metal surface, the coating has a good antirust effect, the two ends of the molecular chain contain oxyacids of phosphorus, and can catalyze a hydroxyl-containing compound to dehydrate into carbon during combustion, so that a coke layer is generated on the surface of the material, the coating has a flame retardant effect, when the coating is scratched under the action of external force, the self-repairing microcapsule and the curing microcapsule are damaged, the external force extrudes the large-aperture mesoporous silica to release styrene, the curing microcapsule releases dibenzoyl peroxide, and the styrene contacts the dibenzoyl peroxide to generate autopolymerization reaction, so that scratches on the surface of the coating are repaired, and the coating can be normally used.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the water-based environment-friendly coating comprises the following raw materials in parts by weight: 80 parts of aqueous polyurethane emulsion, 15 parts of reinforced resin compound, 10 parts of self-repairing microcapsule, 10 parts of curing microcapsule, 0.5 part of defoaming agent and 30 parts of water;

the environment-friendly coating is prepared by uniformly blending the raw materials.

The reinforced resin composite is produced by the following steps;

step A1: adding phosphorus oxychloride into a reaction kettle, stirring for 20min under the conditions that the rotating speed is 150r/min and the temperature is 80 ℃, adding benzyltrimethylammonium chloride and molten phenol, reacting for 3h, adding p-hydroxybenzoic acid, and continuing to react for 1h to obtain an intermediate 1;

step A2: adding epoxy resin E-44 into a reaction kettle, stirring and adding polyethylene glycol 4000 under the conditions of the rotating speed of 120r/min and the temperature of 50 ℃, heating to 100 ℃, adding potassium persulfate, continuously heating to 180 ℃, reacting for 2 hours to obtain an intermediate 2, adding the intermediate 2 and deionized water into the reaction kettle, stirring and adding the intermediate 1 and triphenylphosphine under the conditions of the rotating speed of 150r/min and the temperature of 55 ℃, heating to 100 ℃, and performing reflux reaction for 1 hour to obtain an intermediate 3;

step A3: adding phloroglucinol, sodium carbonate, tetrahydrofuran, an intermediate 3 and dibromoethane into a reaction kettle, reacting for 5 hours at the rotation speed of 120r/min and the temperature of 50 ℃, adding epichlorohydrin, continuing to react for 8 hours to prepare an intermediate 4, adding the intermediate 4, triphenylphosphine, gallic acid and tetrahydrofuran into the reaction kettle, performing reflux reaction for 3 hours at the temperature of 110 ℃, adding graphene oxide, continuing to reflux for 3 hours, adding self-repairing microcapsules and 1-hydroxybenzotriazole, reacting for 2 hours at the temperature of 50 ℃, filtering to remove filtrate, drying a filter cake, and reinforcing a resin compound.

The self-repairing microcapsule is prepared by the following steps:

step B1: dissolving sodium acetate in deionized water to prepare a sodium acetate solution, mixing acetic acid with the deionized water to prepare an acetic acid solution, mixing the sodium acetate solution with the acetic acid solution to prepare a buffer solution, adding gelatin and the buffer solution into a reaction kettle, stirring and adding gamma-aminopropyltriethoxysilane at the rotation speed of 120r/min and the temperature of 35 ℃ to react for 7 hours to prepare a coating solution;

step B2: adding a P123 solution, potassium chloride solution and hydrochloric acid solution into a reaction kettle, stirring for 10min at a rotation speed of 200r/min and a temperature of 50 ℃, cooling to a temperature of 25 ℃, adding 3, 3', 5, 5' -tetramethylbenzidine, stirring for 10h, adding tetraethoxysilane, keeping the temperature at 40 ℃ for 20h, heating to a temperature of 100 ℃, continuing to keep the temperature for 20h, filtering to remove filtrate, and drying a filter cake to obtain the large-aperture mesoporous silica;

step B3: soaking large-aperture mesoporous silica in styrene, carrying out ultrasonic treatment for 1h under the condition of 40KHz frequency, filtering to obtain a core material, adding the core material, coating liquid and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 3min under the conditions of 400r/min of rotation speed and 40 ℃, adding a sodium sulfate solution, continuously stirring for 30min under the condition of ice-water bath, adding glutaraldehyde, continuously stirring for 3min, standing for 10min, filtering and drying to obtain the self-repairing microcapsule.

The cured microcapsule is prepared by the following steps:

step C1: adding the gelatin solution, dibenzoyl peroxide and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 3min at the rotation speed of 400r/min and the temperature of 40 ℃, adding a sodium sulfate solution, continuously stirring for 30min under the condition of ice-water bath, adding glutaraldehyde, continuously stirring for 3min, standing for 10min, filtering and drying to obtain the cured microcapsule.

Example 2:

the water-based environment-friendly coating comprises the following raw materials in parts by weight: 90 parts of aqueous polyurethane emulsion, 20 parts of reinforced resin compound, 13 parts of self-repairing microcapsule, 13 parts of curing microcapsule, 0.8 part of defoaming agent and 40 parts of water;

the environment-friendly coating is prepared by uniformly blending the raw materials.

The reinforced resin composite is produced by the following steps;

step A1: adding phosphorus oxychloride into a reaction kettle, stirring for 20min under the conditions that the rotating speed is 150r/min and the temperature is 90 ℃, adding benzyltrimethylammonium chloride and molten phenol, reacting for 5h, adding p-hydroxybenzoic acid, and continuing to react for 1h to obtain an intermediate 1;

step A2: adding epoxy resin E-44 into a reaction kettle, stirring and adding polyethylene glycol 4000 under the conditions of the rotation speed of 150r/min and the temperature of 50 ℃, heating to the temperature of 110 ℃, adding potassium persulfate, continuing heating to the temperature of 180 ℃, reacting for 3 hours to obtain an intermediate 2, adding the intermediate 2 and deionized water into the reaction kettle, stirring and adding the intermediate 1 and triphenylphosphine under the conditions of the rotation speed of 150r/min and the temperature of 65 ℃, heating to the temperature of 100 ℃, and performing reflux reaction for 1.5 hours to obtain an intermediate 3;

step A3: adding phloroglucinol, sodium carbonate, tetrahydrofuran, an intermediate 3 and dibromoethane into a reaction kettle, reacting for 5 hours at the rotation speed of 120r/min and the temperature of 60 ℃, adding epoxy chloropropane, continuing to react for 10 hours to prepare an intermediate 4, adding the intermediate 4, triphenylphosphine, gallic acid and tetrahydrofuran into the reaction kettle, performing reflux reaction for 5 hours at the temperature of 110 ℃, adding graphene oxide, continuing to reflux for 3 hours, adding a self-repairing microcapsule and 1-hydroxybenzotriazole, reacting for 2 hours at the temperature of 60 ℃, filtering to remove filtrate, drying a filter cake, and reinforcing a resin compound.

The self-repairing microcapsule is prepared by the following steps:

step B1: dissolving sodium acetate in deionized water to prepare a sodium acetate solution, mixing acetic acid with the deionized water to prepare an acetic acid solution, mixing the sodium acetate solution with the acetic acid solution to prepare a buffer solution, adding gelatin and the buffer solution into a reaction kettle, stirring and adding gamma-aminopropyltriethoxysilane at the rotation speed of 150r/min and the temperature of 35 ℃ to react for 9 hours to prepare a coating solution;

step B2: adding a P123 solution, potassium chloride solution and a hydrochloric acid solution into a reaction kettle, stirring for 10min at a rotation speed of 200r/min and a temperature of 60 ℃, cooling to a temperature of 30 ℃, adding 3, 3', 5, 5' -tetramethylbenzidine, stirring for 10h, adding tetraethoxysilane, keeping the temperature at 50 ℃ for 20h, heating to a temperature of 100 ℃, keeping the temperature for 25h, filtering to remove filtrate, and drying a filter cake to obtain the large-aperture mesoporous silica;

step B3: soaking large-aperture mesoporous silica in styrene, carrying out ultrasonic treatment for 1.5h under the condition of 40KHz frequency, filtering to obtain a core material, adding the core material, coating liquid and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 3min under the conditions of 400r/min of rotation speed and 50 ℃, adding a sodium sulfate solution, continuing to stir for 40min under the condition of ice-water bath, adding glutaraldehyde, continuing to stir for 3min, standing for 15min, filtering and drying to obtain the self-repairing microcapsule.

The cured microcapsule is prepared by the following steps:

step C1: adding the gelatin solution, dibenzoyl peroxide and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 3min at the rotation speed of 400r/min and the temperature of 50 ℃, adding a sodium sulfate solution, continuously stirring for 40min under the condition of ice-water bath, adding glutaraldehyde, continuously stirring for 3min, standing for 15min, filtering and drying to obtain the cured microcapsule.

Example 3:

the water-based environment-friendly coating comprises the following raw materials in parts by weight: 100 parts of aqueous polyurethane emulsion, 30 parts of reinforced resin compound, 15 parts of self-repairing microcapsule, 15 parts of curing microcapsule, 1 part of defoaming agent and 50 parts of water;

the environment-friendly coating is prepared by uniformly blending the raw materials.

The reinforced resin composite is produced by the following steps;

step A1: adding phosphorus oxychloride into a reaction kettle, stirring for 30min under the conditions that the rotating speed is 200r/min and the temperature is 90 ℃, adding benzyltrimethylammonium chloride and molten phenol, reacting for 3-5h, adding p-hydroxybenzoic acid, and continuing to react for 2h to obtain an intermediate 1;

step A2: adding epoxy resin E-44 into a reaction kettle, stirring and adding polyethylene glycol 4000 under the conditions that the rotating speed is 150r/min and the temperature is 60 ℃, heating to the temperature of 110 ℃, adding potassium persulfate, continuing heating to the temperature of 190 ℃, reacting for 3 hours to obtain an intermediate 2, adding the intermediate 2 and deionized water into the reaction kettle, stirring and adding the intermediate 1 and triphenylphosphine under the conditions that the rotating speed is 200r/min and the temperature is 65 ℃, heating to the temperature of 120 ℃, and performing reflux reaction for 1.5 hours to obtain an intermediate 3;

step A3: adding phloroglucinol, sodium carbonate, tetrahydrofuran, an intermediate 3 and dibromoethane into a reaction kettle, reacting for 8 hours at the rotation speed of 150r/min and the temperature of 60 ℃, adding epoxy chloropropane, continuing to react for 10 hours to prepare an intermediate 4, adding the intermediate 4, triphenylphosphine, gallic acid and tetrahydrofuran into the reaction kettle, performing reflux reaction for 5 hours at the temperature of 120 ℃, adding graphene oxide, continuing to reflux for 5 hours, adding self-repairing microcapsules and 1-hydroxybenzotriazole, reacting for 4 hours at the temperature of 60 ℃, filtering to remove filtrate, drying a filter cake, and reinforcing a resin compound.

The self-repairing microcapsule is prepared by the following steps:

step B1: dissolving sodium acetate in deionized water to prepare a sodium acetate solution, mixing acetic acid and the deionized water to prepare an acetic acid solution, mixing the sodium acetate solution and the acetic acid solution to prepare a buffer solution, adding gelatin and the buffer solution into a reaction kettle, stirring and adding gamma-aminopropyltriethoxysilane at the rotation speed of 150r/min and the temperature of 40 ℃ to react for 9 hours to prepare a coating solution;

step B2: adding a P123 solution, potassium chloride solution and hydrochloric acid solution into a reaction kettle, stirring for 15min at the rotation speed of 300r/min and the temperature of 60 ℃, cooling to the temperature of 30 ℃, adding 3, 3', 5, 5' -tetramethylbenzidine, stirring for 15h, adding tetraethoxysilane, keeping the temperature at 50 ℃ for 25h, heating to the temperature of 100 ℃, continuing to keep the temperature for 25h, filtering to remove filtrate, and drying a filter cake to obtain the large-aperture mesoporous silica;

step B3: soaking large-aperture mesoporous silica in styrene, carrying out ultrasonic treatment for 1.5h under the condition that the frequency is 50KHz, filtering to obtain a core material, adding the core material, coating liquid and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 5min under the conditions that the rotating speed is 500r/min and the temperature is 50 ℃, adding a sodium sulfate solution, continuously stirring for 40min under the condition of ice-water bath, adding glutaraldehyde, continuously stirring for 5min, standing for 15min, filtering and drying to obtain the self-repairing microcapsule.

The cured microcapsule is prepared by the following steps:

step C1: adding the gelatin solution, dibenzoyl peroxide and fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 5min at the rotation speed of 500r/min and the temperature of 50 ℃, adding a sodium sulfate solution, continuously stirring for 40min under the condition of ice-water bath, adding glutaraldehyde, continuously stirring for 5min, standing for 15min, filtering and drying to obtain the cured microcapsule.

Comparative example 1:

this comparative example compares to example 1 without the addition of a reinforcing resin composite and the rest of the procedure is the same.

Comparative example 2:

compared with the example 1, the self-repairing microcapsule and the curing microcapsule are not added in the comparative example, and the rest steps are the same.

Comparative example 3:

the comparative example is an environment-friendly coating disclosed in Chinese patent CN 109897521A.

An iron plate of 10cm × 10cm was cut, the coating materials prepared in examples 1 to 3 and comparative examples 1 to 3 were applied to the iron plate to a thickness of 40 μm to prepare a sample plate, and the results of the performance test were as shown in the following table;

determination of impact strength: refer to GB/T1732-93 ball falling method; the test was carried out at 23. + -. 2 ℃ and relative humidity 50%. + -. 5%.

And (3) water resistance measurement: testing according to a GB/T method; the test panels were visually inspected and recorded for blistering, wrinkling, flaking, rusting, etc.

Self-repairing performance: the paint film was quickly brushed with a 500g weight copper brush 10 times back and forth at 25 ℃ to see whether scratches on the surface of the paint film were recovered, and water resistance was measured again.

From the above table, it can be seen that the impact strength of the water-based paint prepared in examples 1-3 is 60-65N · cm, and after soaking in water for 960h, the paint film still has no bubbling, shedding, rusting, and has a repairing effect, which indicates that the present invention has good impact resistance, and at the same time, scratches can be automatically repaired under the action of external force.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.