CN115521701A - Corrosion-resistant anti-aging coating and preparation method thereof - Google Patents
Corrosion-resistant anti-aging coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a corrosion-resistant anti-aging coating and a preparation method thereof, and relates to the technical field of coatings. When the corrosion-resistant anti-aging coating is prepared, ethyl orthosilicate is hydrolyzed and polymerized, ammonium bicarbonate is used for pore-forming to prepare porous silicon dioxide, and silane coupling agent is used for pretreating the porous silicon dioxide; pretreating graphene oxide by using glycerol triglycidyl ether; reacting the pretreated silicon dioxide with the pretreated graphene oxide, and then reacting with ethylenediamine and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in sequence to obtain modified silicon dioxide; reacting isophorone diisocyanate with dimethylolbutyric acid to prepare a prepolymer, and reacting the prepolymer, polyethylene glycol and epoxy resin to prepare modified epoxy resin; and sequentially adding triethylamine, pure water, modified silicon dioxide and ethylenediamine into the modified epoxy resin, mixing and stirring to prepare the corrosion-resistant anti-aging coating. The corrosion-resistant anti-aging coating prepared by the invention has excellent corrosion resistance and aging resistance.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a corrosion-resistant anti-aging coating and a preparation method thereof.
Background
The paint is generally composed of a primary film-forming material, a secondary film-forming material, an auxiliary film-forming material and other auxiliary materials. The resin and grease in the coating can form a firm paint film attached to the surface of an object; the pigment and filler provide the color or hiding power required by the coating and play a role of auxiliary shielding, and the most commonly used pigment and filler are extender pigments, commonly called fillers. In general, various additives are added to the formulation for the purpose of stability of the coating itself during the production process, and the properties of the additives affect the properties of the coating, particularly the corrosion resistance. The epoxy resin and the curing system thereof have a series of excellent performances, and the active epoxy group can be crosslinked with various curing agents to meet various application requirements and has good alkali resistance; the inherent polar hydroxyl group and ether bond in the structure of the adhesive make the adhesive property of the adhesive to various foreign matters very outstanding; part of epoxy resin contains aromatic ring, which makes it have outstanding mechanical property, so that the epoxy resin is widely used as adhesive, paint, composite material, etc., especially in the field of anticorrosive paint research.
Currently, there are two major trends in the future development of epoxy anticorrosive coatings: the first is high-performance research. The epoxy anticorrosive paint has inherent defects, so that the performance of the epoxy anticorrosive paint is limited, and the improvement of the anticorrosive performance depends on modification. The anticorrosive paint with high performance value is developed, and not only has scientific research value, but also has very high application value. Therefore, the development of high-performance anticorrosive coatings to replace low-performance anticorrosive coatings and heavy anticorrosive coatings to replace common anticorrosive coatings is the trend of researching the future development of epoxy anticorrosive coatings, and is the demand of the times. The second is the hydration study. The water-based anticorrosive paint takes water as a solvent, the content of organic compounds in the components of the water-based anticorrosive paint is greatly reduced even can reach zero, and the water-based anticorrosive paint is very beneficial to environmental protection and human health, but the performance of the water-based anticorrosive paint is different from that of a solvent-based anticorrosive paint at present. Therefore, the wide-range use of the water-based epoxy anticorrosive paint instead of solvent-based epoxy paint and the improvement of the anticorrosive performance of the water-based epoxy paint are development directions of future epoxy anticorrosive paints, are a technical difficulty needing breakthrough, and have great research and development potential.
Disclosure of Invention
The invention aims to provide a corrosion-resistant anti-aging coating and a preparation method thereof, and aims to solve the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
the preparation method of the corrosion-resistant anti-aging coating is characterized by mainly comprising the following preparation steps:
(1) Pretreatment: hydrolyzing tetraethoxysilane for self polymerization, performing pore-forming by using ammonium bicarbonate to prepare porous silicon dioxide, and pretreating the porous silicon dioxide by using a silane coupling agent; pretreating graphene oxide by using glycerol triglycidyl ether;
(2) Preparation of modified silica: reacting the pretreated silicon dioxide with the pretreated graphene oxide, and then reacting with ethylenediamine and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in sequence to obtain modified silicon dioxide;
(3) Preparation of modified epoxy resin: reacting isophorone diisocyanate with dimethylolbutyric acid to prepare a prepolymer, and reacting the prepolymer, polyethylene glycol and epoxy resin to prepare modified epoxy resin;
(4) Preparing a coating: and sequentially adding triethylamine, pure water, modified silicon dioxide and ethylenediamine into the modified epoxy resin, mixing and stirring to prepare the corrosion-resistant anti-aging coating.
As optimization, the preparation method of the corrosion-resistant anti-aging coating comprises the following preparation steps:
(1) Pretreatment: mixing a silane coupling agent and ethanol according to a mass ratio of 1:150 to 1:200, uniformly mixing, dripping pure water with the mass of 16-20 times that of the silane coupling agent at a constant speed within 10-15 min under the stirring conditions of 10-30 ℃ and 200-400 r/min, continuously stirring for 30-40 min, adding porous silicon dioxide with the mass of 10-14 times that of the silane coupling agent, continuously stirring for 80-100 min, centrifugally separating, washing for 3-5 times by using pure water and absolute ethyl alcohol respectively, and drying for 4-5 h at the temperature of 60-70 ℃ to prepare pretreated silicon dioxide; mixing graphene oxide, glycerol triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide according to a mass ratio of 10:8:1:20 to 10:10:1:25, uniformly mixing, stirring and reacting for 2-3 h at 80-90 ℃ at 800-1000 r/min in a nitrogen atmosphere, centrifugally separating, washing for 3-5 times by using pure water and absolute ethyl alcohol respectively, and standing for 8-10 h at 40-50 ℃ under 1-2 kPa to obtain pretreated graphene oxide;
(2) Preparation of modified silica: mixing pretreated silicon dioxide, pretreated graphene oxide and ammonia water with the mass fraction of 5-8% according to the mass ratio of 1:0.6: 10-1: 1.2:15, uniformly mixing, stirring and reacting for 2-3 h at 30-40 ℃ at 600-800 r/min, then adding ethylenediamine with the mass of 2-3 times that of the pre-modified silicon dioxide, continuously stirring and reacting for 1-2 h, filtering, washing 3-5 times by using pure water and absolute ethyl alcohol respectively, and drying for 6-8 h at 30-40 ℃ under 1-2 kPa to obtain pre-modified silicon dioxide; pre-modified silicon dioxide, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine, 4-dimethylaminopyridine and dichloromethane are mixed according to the mass ratio of 1:0.3:0.1:0.1:20 to 1:0.4:0.2:0.2:30, stirring for 1-2 h at 1-10 ℃ and 300-500 r/min, drying for 6-8 h at 20-30 ℃ and 100-500 Pa, centrifugally separating, washing for 3-5 times by using pure water and absolute ethyl alcohol respectively, and standing for 8-10 h at 40-50 ℃ and 1-2 kPa to prepare modified silicon dioxide;
(3) Preparation of modified epoxy resin: and (2) mixing the prepolymer, polyethylene glycol and epoxy resin according to a mass ratio of 1:0.2:4 to 1:0.3:6, uniformly mixing, stirring for 1-2 h at 60-70 ℃ at 300-500 r/min, heating to 80-90 ℃ for reaction for 3-4 h, and cooling to room temperature to obtain modified epoxy resin;
(4) Preparing a coating: preparing modified epoxy resin into epoxy resin emulsion, and adding modified epoxy resin emulsion with the mass 0.04-0.06 times that of the epoxy resin emulsionSilicon is continuously stirred for 10-15 min, and reduced pressure distillation is carried out to adjust the viscosity to 150-300 mm 2 And/s, adding ethylenediamine with the mass of 0.02-0.04 time of that of the epoxy resin emulsion, and continuously stirring for 8-10 min to obtain the corrosion-resistant anti-aging coating.
Preferably, the preparation method of the epoxy polyhedral silicone in the step (1) comprises the following steps: mixing vinyl trimethoxy silane, hydrochloric acid with the mass fraction of 25-30% and absolute ethyl alcohol according to the mass ratio of 1:1: 10-1: 2:15, uniformly mixing, stirring and reacting for 4-6 h at the temperature of 20-30 ℃ and at the speed of 1500-2000 r/min, cooling to 1-5 ℃, filtering, washing for 3-5 times by using pure water and absolute ethyl alcohol respectively, drying for 6-8 h at the temperature of 60-70 ℃ and under the pressure of 5-10 Pa to prepare the vinyl polyhedral organic silicon, mixing the vinyl polyhedral organic silicon with hydrogen peroxide with the mass fraction of 25-30% according to the mass ratio of 1:4 to 1:6, uniformly mixing, stirring and reacting for 3-4 h at 30-40 ℃ and 800-1000 r/min, and drying for 6-8 h at-10 to-1 ℃ and 5-10 Pa to prepare the catalyst.
As optimization, the preparation method of the porous silica in the step (1) comprises the following steps: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:5 to 1:8, after uniformly mixing, titrating the mixture into ammonia water with the mass fraction of 20-30% 30-40 times of the mass of tetraethoxysilane by 0.1-0.2 mL/s under the stirring condition of 10-30 ℃ and 100-500 r/min, after the titration is finished, continuously stirring for 30-40 min, filtering and washing for 3-5 times by using absolute ethyl alcohol, putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, adding the absolute ethyl alcohol into the reaction kettle to form 70% of the total volume, adding ammonium bicarbonate with the mass of 0.5-0.8 time of the mass of tetraethoxysilane into the reaction kettle, uniformly mixing, sealing the reaction kettle, heating for 6-8 h at the constant temperature of 50-60 ℃, cooling to room temperature, performing centrifugal separation, sequentially washing for 3-5 times by using pure water and absolute ethyl alcohol respectively, and drying for 4-6 h at the temperature of 60-70 ℃ to prepare the catalyst.
And (3) optimally, the model of the silane coupling agent in the step (1) is KH550.
As an optimization, the preparation method of the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in the step (2) comprises the following steps: 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, thionyl chloride and tetrahydrofuran are mixed according to the mass ratio of 20:100:1 to 30:200:1, uniformly mixing, stirring and reacting for 2-3 h at 40-50 ℃ at 300-500 r/min, heating to 60-70 ℃, continuously stirring and reacting for 2-3 h, and drying for 2-3 h at 10-30 ℃ under 100-500 Pa to prepare the nano-composite material.
As optimization, the preparation method of the prepolymer in the step (3) comprises the following steps: mixing isophorone diisocyanate and dimethylolbutyric acid according to a mass ratio of 1:0.6 to 1:0.8, adding a catalyst with the mass of 0.01 to 0.03 time of that of isophorone diisocyanate, and stirring and reacting for 2 to 3 hours at the temperature of between 70 and 80 ℃ at the speed of between 200 and 300r/min in the nitrogen atmosphere to prepare the isophorone diisocyanate.
Preferably, the catalyst is one or a mixture of more of bis-dimethylamino ethyl ether, pentamethyl diethylenetriamine, dimethyl cyclohexylamine and dibutyltin dilaurate.
Preferably, the molecular weight of the polyethylene glycol in the step (3) is 2000-3000.
Preferably, the epoxy resin in the step (3) is bisphenol A type epoxy resin.
And (3) optimally, the epoxy resin emulsion in the step (4) is prepared by heating the modified epoxy resin to 60-70 ℃, adding triethylamine to adjust the pH value to 7-7.5, dropwise adding pure water with the mass of 4-6 times of that of the modified epoxy resin at a constant speed within 20-30 min, and stirring at 400-600 r/min.
Compared with the prior art, the invention has the following beneficial effects:
when the corrosion-resistant anti-aging coating is prepared, firstly, a silane coupling agent is used for pretreating porous silicon dioxide; pretreating graphene oxide by glycerol triglycidyl ether, reacting pretreated silicon dioxide with the pretreated graphene oxide, and then reacting with ethylenediamine and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in sequence to obtain modified silicon dioxide; reacting isophorone diisocyanate with dimethylolbutyric acid to prepare a prepolymer, and reacting the prepolymer, polyethylene glycol and epoxy resin to prepare modified epoxy resin; and sequentially adding triethylamine, pure water, modified silicon dioxide and ethylenediamine into the modified epoxy resin, mixing and stirring to prepare the corrosion-resistant and anti-aging coating.
Firstly, hydrolyzing tetraethoxysilane for self-polymerization, and performing pore-forming by using ammonium bicarbonate to prepare porous silicon dioxide, wherein the modification degree of a porous structure is higher, and other components are wound and solidified in porous gaps, so that the bonding degree of the material is increased; the porous silicon dioxide is pretreated, so that the dispersibility of the porous silicon dioxide is improved, and meanwhile, the porous silicon dioxide reacts with the pretreated graphene oxide, so that the overall combination degree is improved; the method has the advantages that graphene oxide is pretreated, so that the surface of the pretreated graphene oxide has more epoxy groups, the reaction degree with pretreated silicon dioxide and ethylenediamine is improved, the subsequent reaction effect is improved, and meanwhile, a good blocking effect is provided in the main body, so that the ageing resistance and the corrosion resistance are improved.
Secondly, modifying the pre-modified silicon dioxide by using 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, so that the 3, 5-di-tert-butyl-4-hydroxyphenyl is grafted on the modified silicon dioxide and is not easy to run off, when the modified silicon dioxide is aged by oxygen, an organic matter generates an alkyl peroxy radical and an alkyl free radical, the 3, 5-di-tert-butyl-4-hydroxyphenyl easily provides proton hydrogen to terminate the alkyl peroxy radical and generate hydroperoxide, the proton hydrogen is provided to form a stable aryl oxygen radical, and the aryl oxygen radical can be directly coupled with an active free radical to terminate the free radical, so that the ageing resistance is improved; the epoxy resin is modified, the introduced polyethylene glycol chain segment improves the hydrophilicity, the polyethylene glycol has low surface energy and a defoaming effect, the coating is easy to infiltrate into a coating matrix, the bonding effect is improved, and meanwhile, the introduced prepolymer contains carboxyl which can be bonded with amino and imino on the modified silicon dioxide through electrostatic adsorption and can be used as an acid-base buffer layer when in use, so that the corrosion resistance is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are used for detailed description, and the test methods of the indexes of the corrosion-resistant anti-aging coating prepared in the following examples are as follows:
preparation of a sample: the corrosion-resistant anti-aging coating obtained in each example and the comparative example material are sprayed on a glass plate according to the GB 9271 standard and cured into a coating film with the same size and shape, so as to obtain a test plate, and the test plate is subjected to an experiment.
Aging resistance: and (3) measuring the tear strength of the coating film on the test board according to an ASTM D624 standard method, placing the test board in an ozone environment with the same concentration and the same temperature for the same time, measuring the tear strength again, and calculating the aging retention rate = the tear strength after aging/the initial tear strength.
Water resistance: reference is made to paint film water resistance assay GB T1733. Adding deionized water into a glass tank, adjusting the water temperature to 40 ℃, keeping the temperature in the whole process, putting three test panels into the glass tank, soaking 2/3 of the length of the test panels in water for 240h, taking out the test panels, sucking water by using filter paper, observing and recording whether phenomena such as light loss, color change, air bubbles, wrinkling and falling exist.
Salt resistance: reference is made to the paint film resistance to chemical reagents assay GB 1763. And (3) coating a film on the tinplate, sealing the edge by using paraffin, and drying for 48 hours under the conditions of constant temperature and constant humidity. Preparing sodium chloride into a solution with the mass fraction of 3% by using distilled water, immersing two-thirds area of a coating sample plate into a saline solution with the temperature of 25 ℃, taking out the sample plate after 240h, washing off salt traces by using water, and sucking water by using filter paper. The appearance was observed for peeling, wrinkling, bubbling, rusting, discoloration, and loss of gloss.
Acid resistance: drying the cured test plate for 5 days at room temperature, then drying the test plate in a vacuum drying oven at 100 ℃ for 3 hours, cooling the test plate to the room temperature, sealing the edge by using paraffin, immersing two thirds of the coating sample plate in a 5% hydrochloric acid solution for 48 hours, then taking out the sample plate, washing the sample plate by using water, and then sucking water by using filter paper. The appearance of the film was observed for loss of gloss, discoloration, bubbling, spotting, and peeling.
Alkali resistance: drying the cured test plate for 5 days at room temperature, then drying the test plate in a vacuum drying oven at 100 ℃ for 3 hours, cooling the test plate to the room temperature, sealing the edge by using paraffin, immersing two thirds of the coating sample plate in a 5% sodium hydroxide solution for 48 hours, then taking out the sample plate, washing the sample plate by using water, and then absorbing the water by using filter paper. The appearance of the film was observed for loss of gloss, discoloration, bubbling, spotting, and peeling.
Example 1
The preparation method of the corrosion-resistant anti-aging coating mainly comprises the following preparation steps:
(1) Pretreatment: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:5, after uniformly mixing, titrating the mixture into ammonia water with the mass fraction of 20 percent, 30 times that of tetraethoxysilane, in a ratio of 0.1mL/s under the stirring condition of 10 ℃ and 100r/min, continuously stirring for 40min after the titration is finished, filtering and washing the mixture for 3 times by using absolute ethyl alcohol, putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, adding the absolute ethyl alcohol into the reaction kettle with the total volume of 70 percent, then adding ammonium bicarbonate with the mass of 0.5 time that of tetraethoxysilane into the mixture, uniformly mixing the mixture, sealing the reaction kettle, heating the mixture at the constant temperature of 50 ℃ for 8h, cooling the mixture to the room temperature, performing centrifugal separation, sequentially washing the mixture for 3 times by using pure water and the absolute ethyl alcohol respectively, and drying the mixture for 6h at the temperature of 60 ℃ to prepare porous silicon dioxide; mixing a silane coupling agent KH550 and ethanol according to a mass ratio of 1:150, uniformly mixing, dripping pure water with the mass of 16 times of that of the silane coupling agent KH550 at a constant speed within 15min under the stirring condition of 200r/min at 10 ℃, continuously stirring for 40min, adding porous silicon dioxide with the mass of 10 times of that of the silane coupling agent KH550, continuously stirring for 100min, centrifugally separating, washing for 3 times by using pure water and absolute ethyl alcohol respectively, and drying for 5h at 60 ℃ to obtain pretreated silicon dioxide; graphene oxide, glycerol triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10:8:1:20, uniformly mixing, stirring and reacting for 3 hours at 80 ℃ and 800r/min in a nitrogen atmosphere, centrifugally separating, washing for 3 times by using pure water and absolute ethyl alcohol respectively, and standing for 10 hours at 40 ℃ and 1kPa to obtain pretreated graphene oxide;
(2) Preparation of modified silica: mixing pretreated silicon dioxide, pretreated graphene oxide and ammonia water with the mass fraction of 5-8% according to the mass ratio of 1:0.6:10, uniformly mixing, stirring and reacting for 3 hours at 30 ℃ at 600r/min, then adding ethylenediamine with the mass 2 times that of the pre-modified silicon dioxide, continuously stirring and reacting for 2 hours, filtering, washing for 3 times by using pure water and absolute ethyl alcohol respectively, and drying for 8 hours at 30 ℃ under 1kPa to obtain pre-modified silicon dioxide; mixing 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, thionyl chloride and tetrahydrofuran in a mass ratio of 20:100:1, uniformly mixing, stirring and reacting for 3h at 40 ℃ and 300r/min, heating to 60 ℃, continuing stirring and reacting for 3h, and drying for 3h at 10 ℃ and 100Pa to obtain 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride; pre-modified silicon dioxide, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine, 4-dimethylaminopyridine and dichloromethane are mixed according to the mass ratio of 1:0.3:0.1:0.1:20, uniformly mixing, stirring at 1 ℃ and 300r/min for 2h, drying at 20 ℃ and 100Pa for 8h, centrifugally separating, washing with pure water and absolute ethyl alcohol for 3 times respectively, and standing at 40 ℃ and 1kPa for 10h to prepare modified silicon dioxide;
(3) Preparation of modified epoxy resin: mixing isophorone diisocyanate and dimethylolbutyric acid according to a mass ratio of 1:0.6, adding dibutyltin dilaurate with the mass of 0.01 time of that of isophorone diisocyanate, and stirring and reacting for 3 hours at 70 ℃ at 200r/min in a nitrogen atmosphere to obtain a prepolymer; the prepolymer, polyethylene glycol with molecular weight of 2000 and bisphenol A epoxy resin are mixed according to a mass ratio of 1:0.2:4, uniformly mixing, stirring for 2 hours at 60 ℃ at 300r/min, heating to 80 ℃ for reaction for 4 hours, and cooling to room temperature to obtain modified epoxy resin;
(4) Preparing a coating: heating modified epoxy resin to 60 ℃, adding triethylamine to adjust the pH value to 7, dripping pure water 4 times of the modified epoxy resin in mass at a constant speed within 20min, stirring at 400r/min to form epoxy resin emulsion, adding modified silicon dioxide 0.04 times of the epoxy resin emulsion in mass, continuously stirring for 10min, and carrying out reduced pressure distillation to adjust the viscosity to 150mm 2 And/s, adding ethylenediamine with the mass of 0.02 time of that of the epoxy resin emulsion, and continuously stirring for 8min to obtain the corrosion-resistant anti-aging coating.
Example 2
The preparation method of the corrosion-resistant anti-aging coating mainly comprises the following preparation steps:
(1) Pretreatment: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:6, after uniformly mixing, titrating the mixture into 25 mass percent ammonia water with the mass of 35 times of that of ethyl orthosilicate by 0.15mL/s under the stirring condition of 20 ℃ and 300r/min, continuing to stir for 35min after titration is finished, filtering and washing the mixture for 4 times by absolute ethyl alcohol, putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, adding the absolute ethyl alcohol into the reaction kettle with 70 percent of the total volume, adding ammonium bicarbonate with the mass of 0.6 time of that of the ethyl orthosilicate, uniformly mixing, sealing the reaction kettle, heating the mixture at the constant temperature of 55 ℃ for 7h, cooling the mixture to room temperature, performing centrifugal separation, sequentially washing the mixture for 4 times by pure water and absolute ethyl alcohol respectively, and drying the mixture for 5h at the temperature of 65 ℃ to obtain porous silicon dioxide; mixing a silane coupling agent KH550 and ethanol according to a mass ratio of 1:180, uniformly dripping pure water with the mass of 18 times of that of the silane coupling agent KH550 into the mixture at a constant speed within 12min under the stirring condition of 300r/min at the temperature of 20 ℃, continuously stirring the mixture for 35min, adding porous silicon dioxide with the mass of 12 times of that of the silane coupling agent KH550 into the mixture, continuously stirring the mixture for 90min, centrifugally separating the mixture, washing the mixture for 4 times by using pure water and absolute ethyl alcohol respectively, and drying the mixture for 4.5h at the temperature of 65 ℃ to prepare pretreated silicon dioxide; graphene oxide, glycerol triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10:9:1:22, uniformly mixing, stirring and reacting for 2.5 hours at 85 ℃ and 900r/min in a nitrogen atmosphere, centrifugally separating, washing for 4 times by using pure water and absolute ethyl alcohol respectively, and standing for 9 hours at 45 ℃ and 1.5kPa to prepare pretreated graphene oxide;
(2) Preparation of modified silica: mixing pretreated silicon dioxide, pretreated graphene oxide and ammonia water with the mass fraction of 6% according to the mass ratio of 1:0.8:12, uniformly mixing, stirring and reacting for 2.5h at 35 ℃ and 700r/min, adding ethylenediamine with the mass of 2.5 times that of the pre-modified silicon dioxide, continuing stirring and reacting for 1.5h, filtering, washing for 4 times by using pure water and absolute ethyl alcohol respectively, and drying for 7h at 35 ℃ and 1.5kPa to obtain pre-modified silicon dioxide; mixing 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, thionyl chloride and tetrahydrofuran according to a mass ratio of 25:150:1, uniformly mixing, stirring and reacting for 2.5h at 45 ℃ and 400r/min, then heating to 65 ℃, continuing stirring and reacting for 2.5h, and drying for 2.5h at 20 ℃ and 300Pa to obtain 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride; pre-modified silicon dioxide, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine, 4-dimethylaminopyridine and dichloromethane are mixed according to the mass ratio of 1:0.35:0.15:0.15:25, uniformly mixing, stirring at 5 ℃ and 400r/min for 1.5h, drying at 25 ℃ and 300Pa for 7h, centrifugally separating, washing with pure water and absolute ethyl alcohol for 4 times respectively, and standing at 45 ℃ and 1.5kPa for 9h to prepare modified silicon dioxide;
(3) Preparation of modified epoxy resin: mixing isophorone diisocyanate and dimethylolbutyric acid according to a mass ratio of 1:0.7, adding dibutyltin dilaurate with the mass of 0.02 times of that of isophorone diisocyanate, and stirring and reacting at 75 ℃ and 250r/min for 2.5 hours in a nitrogen atmosphere to obtain a prepolymer; the prepolymer, polyethylene glycol with the molecular weight of 2500 and bisphenol A epoxy resin are mixed according to the mass ratio of 1:0.25:5, uniformly mixing, stirring at 65 ℃ for 1.5h at 400r/min, heating to 85 ℃, reacting for 3.5h, and cooling to room temperature to obtain modified epoxy resin;
(4) Preparing a coating: heating modified epoxy resin to 65 ℃, adding triethylamine to adjust the pH value to 7.2, dripping pure water 5 times of the modified epoxy resin in mass at a constant speed within 25min, stirring at 500r/min to form epoxy resin emulsion, adding modified silicon dioxide 0.05 times of the epoxy resin emulsion in mass, continuing stirring for 12min, carrying out reduced pressure distillation to adjust the viscosity to 220mm 2 And/s, adding ethylenediamine with the mass of 0.03 time of that of the epoxy resin emulsion, and continuously stirring for 9min to obtain the corrosion-resistant anti-aging coating.
Example 3
The preparation method of the corrosion-resistant anti-aging coating mainly comprises the following preparation steps:
(1) Pretreatment: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:8, after uniformly mixing, titrating into 30 mass percent ammonia water with 40 times of the mass of tetraethoxysilane by 0.2mL/s under the stirring condition of 30 ℃ and 500r/min, continuously stirring for 40min after titration, filtering, washing for 5 times by using absolute ethyl alcohol, putting into a reaction kettle with a polytetrafluoroethylene lining, adding the absolute ethyl alcohol into 70 percent of the total volume, adding ammonium bicarbonate with 0.8 time of the mass of tetraethoxysilane, uniformly mixing, sealing the reaction kettle, heating at the constant temperature of 60 ℃ for 7h, cooling to room temperature, performing centrifugal separation, sequentially washing for 5 times by using pure water and the absolute ethyl alcohol respectively, and drying at the temperature of 70 ℃ for 6h to obtain porous silicon dioxide; mixing a silane coupling agent KH550 and ethanol according to a mass ratio of 1:200, uniformly dripping pure water with the mass of 20 times of that of a silane coupling agent KH550 at a constant speed within 15min under the stirring condition of 400r/min at the temperature of 30 ℃, continuously stirring for 40min, adding porous silicon dioxide with the mass of 14 times of that of the silane coupling agent KH550, continuously stirring for 100min, centrifugally separating, washing for 5 times by using pure water and absolute ethyl alcohol respectively, and drying for 4h at the temperature of 70 ℃ to obtain pretreated silicon dioxide; graphene oxide, glycerol triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10:10:1:25, uniformly mixing, stirring and reacting for 2 hours at 90 ℃ and 1000r/min in a nitrogen atmosphere, centrifugally separating, washing for 5 times by using pure water and absolute ethyl alcohol respectively, and standing for 8 hours at 50 ℃ and 2kPa to obtain pretreated graphene oxide;
(2) Preparation of modified silica: mixing pretreated silicon dioxide, pretreated graphene oxide and 8% ammonia water by mass percent according to a mass ratio of 1:1.2:15, uniformly mixing, stirring and reacting for 3 hours at 40 ℃ at 800r/min, then adding ethylenediamine with the mass of 3 times that of the pre-modified silicon dioxide, continuously stirring and reacting for 1 hour, filtering, washing for 5 times by using pure water and absolute ethyl alcohol respectively, and drying for 6 hours at 40 ℃ under 2kPa to obtain pre-modified silicon dioxide; mixing 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, thionyl chloride and tetrahydrofuran in a mass ratio of 30:200:1, uniformly mixing, stirring and reacting for 3h at 50 ℃ and 500r/min, heating to 70 ℃, continuing stirring and reacting for 2h, and drying for 2h at 30 ℃ and 500Pa to obtain 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride; pre-modified silicon dioxide, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine, 4-dimethylaminopyridine and dichloromethane are mixed according to a mass ratio of 1:0.4:0.2:0.2:30, uniformly mixing, stirring for 2 hours at 10 ℃ and 500r/min, drying for 6 hours at 30 ℃ and 500Pa, centrifugally separating, washing for 5 times by using pure water and absolute ethyl alcohol respectively, and standing for 8 hours at 50 ℃ and 2kPa to prepare modified silicon dioxide;
(3) Preparation of modified epoxy resin: mixing isophorone diisocyanate and dimethylolbutyric acid according to a mass ratio of 1:0.8, adding dibutyltin dilaurate with the mass of 0.03 time of that of isophorone diisocyanate, and stirring and reacting for 2 hours at 80 ℃ and 300r/min in a nitrogen atmosphere to obtain a prepolymer; the prepolymer, polyethylene glycol with the molecular weight of 3000 and bisphenol A epoxy resin are mixed according to the mass ratio of 1:0.3:6, uniformly mixing, stirring for 1h at 70 ℃ at 500r/min, heating to 90 ℃ for reaction for 3h, and cooling to room temperature to obtain modified epoxy resin;
(4) Preparing a coating: heating modified epoxy resin to 70 ℃, adding triethylamine to adjust the pH value to 7.5, dripping pure water with the mass 6 times of that of the modified epoxy resin at a constant speed within 30min, stirring at 600r/min to form epoxy resin emulsion, adding modified silicon dioxide with the mass 0.06 time of that of the epoxy resin emulsion, continuing stirring for 15min, and carrying out reduced pressure distillation to adjust the viscosity to 300mm 2 And/s, adding ethylenediamine with the mass of 0.04 time of that of the epoxy resin emulsion, and continuously stirring for 10min to obtain the corrosion-resistant anti-aging coating.
Comparative example 1
The preparation method of the corrosion-resistant anti-aging coating of the comparative example 1 is different from that of the example 2 only in the difference of the step (1), and the step (1) is modified as follows: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:6, after uniformly mixing, titrating the mixture into ammonia water with the mass fraction of 25 percent, 35 times of the mass of tetraethoxysilane, in a 0.15mL/s manner under the stirring condition of 20 ℃ and 300r/min, continuing to stir for 35min after the titration is finished, filtering and washing the mixture for 4 times by using absolute ethyl alcohol, putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, adding the absolute ethyl alcohol into the reaction kettle with the total volume of 70 percent, sealing the reaction kettle, heating the reaction kettle at the constant temperature of 55 ℃ for 7h, cooling the mixture to the room temperature, performing centrifugal separation, washing the mixture for 4 times by using pure water and absolute ethyl alcohol in sequence, and drying the mixture for 5h at the temperature of 65 ℃ to obtain nano silicon dioxide; mixing a silane coupling agent KH550 and ethanol according to a mass ratio of 1:180, uniformly dripping pure water with the mass of 18 times of that of the silane coupling agent KH550 into the mixture at a constant speed within 12min under the stirring condition of 300r/min at the temperature of 20 ℃, continuously stirring the mixture for 35min, adding nano-silica with the mass of 12 times of that of the silane coupling agent KH550 into the mixture, continuously stirring the mixture for 90min, centrifugally separating the mixture, washing the mixture for 4 times by using pure water and absolute ethyl alcohol respectively, and drying the mixture for 4.5h at the temperature of 65 ℃ to prepare pretreated silica; graphene oxide, glycerol triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10:9:1:22, stirring and reacting for 2.5h at the temperature of 85 ℃ and 900r/min in the nitrogen atmosphere, centrifugally separating, washing for 4 times by using pure water and absolute ethyl alcohol respectively, and standing for 9h at the temperature of 45 ℃ and 1.5kPa to prepare the pretreated graphene oxide. The remaining steps were performed in the same manner as in example 2.
Comparative example 2
The preparation method of the corrosion-resistant anti-aging coating of comparative example 2 is different from that of example 2 in the difference of step (1), and the step (1) is modified as follows: (1) pretreatment: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:6, after uniformly mixing, titrating the mixture into 25 mass percent ammonia water with the mass of 35 times of that of ethyl orthosilicate by 0.15mL/s under the stirring condition of 20 ℃ and 300r/min, continuing to stir for 35min after titration is finished, filtering and washing the mixture for 4 times by absolute ethyl alcohol, putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, adding the absolute ethyl alcohol into the reaction kettle with 70 percent of the total volume, adding ammonium bicarbonate with the mass of 0.6 time of that of the ethyl orthosilicate, uniformly mixing, sealing the reaction kettle, heating the mixture at the constant temperature of 55 ℃ for 7h, cooling the mixture to room temperature, performing centrifugal separation, sequentially washing the mixture for 4 times by pure water and absolute ethyl alcohol respectively, and drying the mixture for 5h at the temperature of 65 ℃ to obtain porous silicon dioxide; graphene oxide, glycerol triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10:9:1:22, uniformly mixing, stirring and reacting for 2.5h at the temperature of 85 ℃ and 900r/min in the nitrogen atmosphere, centrifugally separating, washing for 4 times by using pure water and absolute ethyl alcohol respectively, and standing for 9h at the temperature of 45 ℃ and 1.5kPa to obtain the pretreated graphene oxide. And replacing the "pretreated silica" in step (2) with "porous silica".
Comparative example 3
The preparation method of the corrosion-resistant anti-aging coating of the comparative example 3 is different from that of the example 2 in the difference of the step (1), and the step (1) is modified as follows: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:6, after uniformly mixing, titrating the mixture into 25 mass percent ammonia water with the mass of 35 times of that of ethyl orthosilicate by 0.15mL/s under the stirring condition of 20 ℃ and 300r/min, continuing to stir for 35min after titration is finished, filtering and washing the mixture for 4 times by absolute ethyl alcohol, putting the mixture into a reaction kettle with a polytetrafluoroethylene lining, adding the absolute ethyl alcohol into the reaction kettle with 70 percent of the total volume, adding ammonium bicarbonate with the mass of 0.6 time of that of the ethyl orthosilicate, uniformly mixing, sealing the reaction kettle, heating the mixture at the constant temperature of 55 ℃ for 7h, cooling the mixture to room temperature, performing centrifugal separation, sequentially washing the mixture for 4 times by pure water and absolute ethyl alcohol respectively, and drying the mixture for 5h at the temperature of 65 ℃ to obtain porous silicon dioxide; mixing a silane coupling agent KH550 and ethanol according to a mass ratio of 1:180, uniformly dripping pure water with the mass being 18 times of that of the KH550 silane coupling agent into the mixture at a constant speed within 12min under the stirring conditions of 20 ℃ and 300r/min, continuously stirring the mixture for 35min, adding porous silicon dioxide with the mass being 12 times of that of the KH550 silane coupling agent into the mixture, continuously stirring the mixture for 90min, centrifugally separating the mixture, washing the mixture for 4 times by using pure water and absolute ethyl alcohol respectively, and drying the mixture for 4.5h at 65 ℃ to obtain the pretreated silicon dioxide. And replacing the pretreated graphene oxide in the step (2) with graphene oxide.
Comparative example 4
The preparation method of the corrosion-resistant anti-aging coating of comparative example 4 is different from that of example 2 only in the difference of step (2), and the step (2) is modified as follows: mixing pretreated silicon dioxide, pretreated graphene oxide and ammonia water with the mass fraction of 6% according to the mass ratio of 1:0.8:12, uniformly mixing, stirring and reacting for 2.5h at 35 ℃ and 700r/min, adding ethylenediamine with the mass of 2.5 times of that of the pre-modified silicon dioxide, continuing stirring and reacting for 1.5h, filtering, washing for 4 times by using pure water and absolute ethyl alcohol respectively, and drying for 7h at 35 ℃ and 1.5kPa to obtain the modified silicon dioxide.
Comparative example 5
The preparation method of the corrosion-resistant anti-aging coating material of comparative example 5 is different from that of example 2 only in that step (3) is not performed, and the "modified epoxy resin" in step (4) is replaced with the "bisphenol A type epoxy resin"
Examples of effects
The following table 1 shows the performance analysis results of the corrosion resistance and aging resistance of the corrosion-resistant and aging-resistant coatings of examples 1 to 3 and comparative examples 1 to 5 using the present invention.
TABLE 1
As can be seen from the comparison of the experimental data of examples 1-3 and comparative examples 1-5 in Table 1, the corrosion-resistant anti-aging coating prepared by the invention has good corrosion resistance and aging resistance.
Compared with the experimental data of examples 1, 2 and 3 and comparative example 1, the aging retention rate of examples 1, 2 and 3 is higher than that of comparative example 1, which shows that the modification degree of the porous structure is higher, and other components can be wound and cured in the porous gaps, so that the bonding degree of the materials is increased, and the aging resistance of the corrosion-resistant and aging-resistant coating is improved; compared with the experimental data of the examples 1, 2 and 3 and the comparative example 2, the experimental data of the examples 1, 2 and 3 show that the aging retention rate of the examples 1, 2 and 3 is higher than that of the comparative example 2, and the phenomena of light loss, color change, bubbles, spots, falling off and the like exist, so that the porous silicon dioxide is pretreated, the dispersity of the porous silicon dioxide is improved, and meanwhile, the porous silicon dioxide can react with the pretreated graphene oxide, the overall combination degree is improved, and the aging resistance and the corrosion resistance of the corrosion-resistant and anti-aging coating are improved; the experimental data comparison of the examples 1, 2 and 3 and the comparative example 3 shows that the aging retention rate of the examples 1, 2 and 3 is high compared with the comparative example 3, and the phenomena of light loss, color change, bubbles, spots, falling off and the like exist, which indicates that the pretreatment of the graphene oxide enables the surface of the pretreated graphene oxide to have more epoxy groups, the reaction degree with pretreated silicon dioxide and ethylenediamine is improved, the subsequent reaction effect is improved, and the aging resistance and the corrosion resistance of the corrosion-resistant and anti-aging coating are improved; the experimental data of examples 1, 2 and 3 and comparative example 4 show that the aging retention of examples 1, 2 and 3 is high compared with comparative example 4, which illustrates that the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is used for modifying pre-modified silica, so that the 3, 5-di-tert-butyl-4-hydroxyphenyl is grafted on the modified silica and is not easy to run off, when the pre-modified silica is aged by oxygen, organic matters generate alkyl peroxy radicals and alkyl free radicals, the 3, 5-di-tert-butyl-4-hydroxyphenyl is easy to provide proton hydrogen to terminate the alkyl peroxy radicals and generate hydroperoxides, and stable aryl oxygen radicals are formed after providing proton hydrogen, and the aryl oxygen radicals can be directly coupled with active free radicals to terminate the free radicals, so that the aging resistance of the corrosion-resistant and aging-resistant coating is improved; compared with the experimental data of the examples 1, 2 and 3 and the comparative example 5, the experimental data shows that the phenomena of light loss, color change, bubbles, spots, falling off and the like of the examples 1, 2 and 3 compared with the comparative example 5 illustrate that the epoxy resin is modified, the introduced polyethylene glycol chain segment improves the hydrophilicity, the surface energy of the polyethylene glycol is low, the polyethylene glycol has the defoaming effect, the coating is easy to infiltrate into a coating matrix, the bonding effect is improved, and meanwhile, the introduced prepolymer contains carboxyl groups, can be combined with amino groups and imino groups on the modified silicon dioxide through electrostatic adsorption and can be used as an acid-base buffer layer when in use, so that the corrosion resistance and the aging resistance of the corrosion-resistant coating are improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. The preparation method of the corrosion-resistant anti-aging coating is characterized by mainly comprising the following preparation steps:
(1) Pretreatment: hydrolyzing tetraethoxysilane for self polymerization, performing pore-forming by using ammonium bicarbonate to prepare porous silicon dioxide, and pretreating the porous silicon dioxide by using a silane coupling agent; pretreating graphene oxide by using glycerol triglycidyl ether;
(2) Preparation of modified silica: reacting the pretreated silicon dioxide with the pretreated graphene oxide, and then reacting with ethylenediamine and 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride in sequence to obtain modified silicon dioxide;
(3) Preparation of modified epoxy resin: reacting isophorone diisocyanate with dimethylolbutyric acid to prepare a prepolymer, and reacting the prepolymer, polyethylene glycol and epoxy resin to prepare modified epoxy resin;
(4) Preparing a coating: and sequentially adding triethylamine, pure water, modified silicon dioxide and ethylenediamine into the modified epoxy resin, mixing and stirring to prepare the corrosion-resistant anti-aging coating.
2. The preparation method of the corrosion-resistant anti-aging coating according to claim 1, characterized in that the preparation method mainly comprises the following preparation steps:
(1) Pretreatment: mixing a silane coupling agent and ethanol according to a mass ratio of 1:150 to 1:200, uniformly mixing, dripping pure water with the mass of 16 to 20 times of that of the silane coupling agent at a constant speed within 10 to 15min under the stirring condition of 200 to 400r/min at 10 to 30 ℃, continuously stirring for 30 to 40min, adding porous silicon dioxide with the mass of 10 to 14 times of that of the silane coupling agent, continuously stirring for 80 to 100min, centrifugally separating, washing for 3 to 5 times by using pure water and absolute ethyl alcohol respectively, and drying for 4 to 5h at 60 to 70 ℃ to prepare pretreated silicon dioxide; graphene oxide, glycerol triglycidyl ether, tetrabutylammonium bromide and N, N-dimethylformamide are mixed according to the mass ratio of 10:8:1:20 to 10:10:1:25, uniformly mixing, stirring and reacting for 2 to 3 hours at 80 to 90 ℃ and 800 to 1000r/min in a nitrogen atmosphere, centrifugally separating, washing for 3 to 5 times by using pure water and absolute ethyl alcohol respectively, and standing for 8 to 10 hours at 40 to 50 ℃ and 1 to 2kPa to prepare pretreated graphene oxide;
(2) Preparation of modified silica: mixing pretreated silicon dioxide, pretreated graphene oxide and ammonia water with the mass fraction of 5-8% according to the mass ratio of 1:0.6:10 to 1:1.2:15, uniformly mixing, stirring and reacting for 2-3h at 30-40 ℃ and 600-800r/min, adding ethylenediamine with the mass of 2-3 times that of the pre-modified silicon dioxide, continuing stirring and reacting for 1-2h, filtering, washing for 3-5 times by using pure water and absolute ethyl alcohol respectively, and drying for 6-8h at 30-40 ℃ and 1-2kPa to obtain the pre-modified silicon dioxide; pre-modified silicon dioxide, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride, triethylamine, 4-dimethylaminopyridine and dichloromethane are mixed according to a mass ratio of 1:0.3:0.1:0.1:20 to 1:0.4:0.2:0.2:30, uniformly mixing, stirring for 1 to 2h at 1 to 10 ℃ and 300 to 500r/min, drying for 6 to 8h at 20 to 30 ℃ and 100 to 500Pa, centrifugally separating, washing for 3 to 5 times by using pure water and absolute ethyl alcohol respectively, and standing for 8 to 10h at 40 to 50 ℃ and 1 to 2kPa to prepare modified silicon dioxide;
(3) Preparation of modified epoxy resin: and (2) mixing the prepolymer, polyethylene glycol and epoxy resin according to a mass ratio of 1:0.2:4 to 1:0.3:6, uniformly mixing, stirring for 1 to 2h at the temperature of 60 to 70 ℃ and at the speed of 300 to 500r/min, heating to the temperature of 80 to 90 ℃ for reaction for 3 to 4h, and cooling to the room temperature to prepare modified epoxy resin;
(4) Preparing a coating: preparing epoxy resin emulsion from the modified epoxy resin, adding modified silicon dioxide with the mass of 0.04-0.06 time of that of the epoxy resin emulsion, continuously stirring for 10-15min, and carrying out reduced pressure distillation to adjust the viscosity to 150-300mm 2 And/s, adding ethylene diamine with the mass of 0.02-0.04 times of that of the epoxy resin emulsion, and continuously stirring for 8-10min to prepare the corrosion-resistant anti-aging coating.
3. The method for preparing the corrosion-resistant anti-aging coating according to claim 2, wherein the porous silica prepared in the step (1) is prepared by: ethyl orthosilicate and absolute ethyl alcohol are mixed according to a mass ratio of 1:5 to 1:8, uniformly mixing, titrating into ammonia water with the mass fraction of 20-30% and the mass of 30-40 times of that of ethyl orthosilicate by 0.1-0.2mL/s under the stirring condition of 10-30 ℃ and 100-500r/min, continuously stirring for 30-40min after titration, filtering, washing for 3-5 times by using absolute ethyl alcohol, putting into a reaction kettle with a polytetrafluoroethylene lining, adding absolute ethyl alcohol into the reaction kettle, adding ammonium bicarbonate with the mass of 0.5-0.8 time of that of ethyl orthosilicate, uniformly mixing, sealing the reaction kettle, heating for 6-8h at the constant temperature of 50-60 ℃, cooling to room temperature, performing centrifugal separation, sequentially washing for 3-5 times by using pure water and absolute ethyl alcohol, and drying for 4-6h at the temperature of 60-70 ℃ to prepare the water-based organic silicon dioxide.
4. The method for preparing the corrosion-resistant anti-aging coating according to claim 2, wherein the silane coupling agent in the step (1) is KH550.
5. The method for preparing the corrosion-resistant anti-aging coating according to claim 2, wherein the 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride prepared in step (2) is prepared by: 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, thionyl chloride and tetrahydrofuran are mixed according to the mass ratio of 20:100:1 to 30:200:1, uniformly mixing, reacting for 2 to 3 hours at the temperature of 40 to 50 ℃ and under stirring at the speed of 300 to 500r/min, heating to the temperature of 60 to 70 ℃, continuing to react for 2 to 3 hours under stirring, and drying for 2 to 3 hours at the temperature of 10 to 30 ℃ and under 100 to 500Pa to prepare the nano-composite material.
6. The preparation method of the corrosion-resistant anti-aging coating as claimed in claim 2, wherein the preparation method of the prepolymer in the step (3) comprises the following steps: mixing isophorone diisocyanate and dimethylolbutyric acid according to a mass ratio of 1:0.6 to 1:0.8, adding a catalyst with the mass of 0.01 to 0.03 times that of isophorone diisocyanate, and stirring and reacting for 2 to 3h at the temperature of 200 to 300r/min in a nitrogen atmosphere to prepare the isophorone diisocyanate.
7. The method for preparing the corrosion-resistant anti-aging coating according to claim 6, wherein the catalyst is one or more of bis-dimethylaminoethyl ether, pentamethyldiethylenetriamine, dimethylcyclohexylamine and dibutyltin dilaurate.
8. The preparation method of the corrosion-resistant anti-aging coating as claimed in claim 2, wherein the molecular weight of the polyethylene glycol in the step (3) is 2000 to 3000.
9. The method for preparing the corrosion-resistant anti-aging coating according to claim 2, wherein the epoxy resin in the step (3) is bisphenol A epoxy resin.
10. The preparation method of the corrosion-resistant and anti-aging coating as claimed in claim 2, wherein the epoxy resin emulsion in the step (4) is prepared by heating the modified epoxy resin to 60 to 70 ℃, adding triethylamine to adjust the pH to 7 to 7.5, dripping pure water with the mass of 4 to 6 times of that of the modified epoxy resin at a constant speed within 20 to 30min, and stirring at 400 to 600r/min.
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