High-weather-resistance anticorrosive epoxy resin paint and preparation method thereof

Abstract

The application discloses a kind of high weather-resistant anticorrosive epoxy resin paint and preparation method thereof, it is related to paint field, the high weather-resistant anticorrosive epoxy resin paint includes following weight parts raw materials: modified epoxy resin 50-55 parts, amino resin 30-35 parts, urea-formaldehyde resin 15-17 parts, modified polysulfide rubber 10-12 parts, titanium white 8-10 parts, kaolin 3-5 parts, dispersing agent 0.5-1.0 parts, leveling agent 0.6-0.8 parts, defoaming agent 0.2-0.4 parts, drying agent 0.8-1.0 parts and solvent 15-20 parts.The modified epoxy resin is obtained by introducing diazene fluorene structure into epoxy resin molecular chain, glass flake;The modified polysulfide rubber is obtained by introducing POSS, hydroxyl and alkane long chain into polysulfide rubber molecular chain.The epoxy resin paint of the application has excellent corrosion resistance, mechanical strength, weather resistance in high temperature and high humidity environment, and is worth popularizing and using.

Description

Technical Field

[0001] The present invention relates to the field of coatings, and in particular to a highly weather-resistant and anti-corrosion epoxy resin coating and a preparation method thereof. Background Art

[0002] Epoxy resins are widely used in coatings, adhesives, composite materials, and other fields due to their low shrinkage during the curing reaction, as well as the excellent adhesion, heat resistance, chemical resistance, mechanical properties, and electrical properties of the cured products. However, due to their molecular structure, epoxy resin cured products have high internal stress, brittleness, poor impact resistance, and easy cracking. To improve these shortcomings, epoxy resins need to be toughened and modified. Because the main chain structure of polysulfide rubber molecules is connected by single bonds and contains a large number of ether bonds, the molecular chain is extremely flexible and highly compatible with epoxy resins. Therefore, it is often used to toughen epoxy resins. However, the heat resistance of polysulfide rubber does not meet the requirements of epoxy resin coatings with higher heat resistance requirements.

[0003] Furthermore, epoxy resins are limited in their development as long-lasting anti-corrosion coatings due to their poor water resistance, low toughness, and reduced adhesion after long-term use. The corrosion resistance of epoxy resin coatings does not meet current usage requirements. Furthermore, epoxy coatings can age to varying degrees due to factors such as high temperature, humidity, and rain, resulting in a reduced lifespan, increased operating costs, and waste of resources. Therefore, the weather resistance of epoxy resin coatings urgently needs to be improved.

[0004] In summary, a suitable modification method is needed to apply polysulfide rubber with improved heat resistance to epoxy resin coatings, while improving the corrosion resistance and water resistance of epoxy resin coatings, so as to obtain epoxy resin coatings with excellent performance such as corrosion resistance and weather resistance in high temperature and high humidity environments. Summary of the Invention

[0005] In order to solve the above technical problems, the present invention provides a highly weather-resistant and anti-corrosion epoxy resin coating and a preparation method thereof.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A highly weather-resistant and anti-corrosion epoxy resin coating, comprising the following raw materials in parts by weight: 50-55 parts of a modified epoxy resin, 30-35 parts of an amino resin, 15-17 parts of a urea-formaldehyde resin, 10-12 parts of a modified polysulfide rubber, 8-10 parts of titanium dioxide, 3-5 parts of kaolin, 0.5-1.0 parts of a dispersant, 0.6-0.8 parts of a leveling agent, 0.2-0.4 parts of a defoaming agent, 0.8-1.0 parts of a drying agent, and 15-20 parts of a solvent;

[0008] Furthermore, the dispersant is BYK-2070, the leveling agent is BYK-306, the defoaming agent is BYK-A530, the drying agent is potassium isooctanoate, and the solvent is ethyl acetate;

[0009] The highly weather-resistant and anti-corrosion epoxy resin coating is prepared by the following steps: stirring and mixing a modified epoxy resin, a urea-formaldehyde resin, and a modified polysulfide rubber at 80-90° C. for 2-2.5 hours, adding an amino resin and stirring at 60-70° C. for 1-1.5 hours, then adding titanium dioxide, kaolin, a dispersant, a leveling agent, a defoamer, a drying agent, and a solvent, and continuing stirring at 60-70° C. for 1.5-2.0 hours to obtain the highly weather-resistant and anti-corrosion epoxy resin coating;

[0010] The modified epoxy resin is prepared by the following steps:

[0011] Step A1, adding 1,10-phenanthroline-2-carboxylic acid methyl ester and potassium hydroxide to deionized water and stirring at 75-80° C. for 20-30 minutes, then adding potassium permanganate aqueous solution dropwise within 4.5-5 hours, continuing to stir and react for 3-3.5 hours, then hot filtering, concentrating, recrystallizing in water, and vacuum drying at 70-80° C. overnight to obtain reaction product 1;

[0012] Furthermore, the usage ratio of 1,10-phenanthroline-2-carboxylic acid methyl ester, potassium hydroxide, deionized water, and potassium permanganate aqueous solution is 3.8-4.0 g: 2.6-2.8 g: 170-175 mL: 111-115 mL; the potassium permanganate aqueous solution is prepared by adding 6.5-6.7 g of potassium permanganate to 105-110 mL of deionized water and stirring;

[0013] During the reaction of step A1, 1,10-phenanthroline-2-carboxylic acid methyl ester is oxidized by potassium permanganate to obtain a reaction product 1 containing an ester group and fluorenone;

[0014] Step A2, adding the dried glass flakes to an ethanol-water solution and stirring for 15-20 minutes, then adding an ethanol solution of a silane coupling agent, stirring at 80-85° C. for 4-4.5 hours, vacuum filtering, washing with deionized water and ethanol three times each, and vacuum drying at 40-45° C. to obtain NH2-glass flakes; in a protective gas atmosphere, reflux stirring the reaction product 1 at 100-105° C. for 1-1.2 hours, cooling to 50-55° C., adding methanol and NH2-glass flakes, and then adding sodium methoxide, stirring and reacting for 24-25 hours to obtain reaction product 2;

[0015] Furthermore, the amount ratio of dried glass flakes, ethanol aqueous solution, and ethanol solution of silane coupling agent is 5.0-5.5g:50-55mL:700-750mL, the silane coupling agent is KH550, the dried glass flakes are obtained by drying the glass flakes at 105-110°C for 24-25h, the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 4:1; the ethanol solution of silane coupling agent is obtained by adding silane coupling agent to ethanol and stirring and mixing, and the concentration is 0.1-0.15mol / L; the volume fraction of ethanol is 95%; the amount ratio of reaction product 1, methanol, NH2-glass flakes, and sodium methoxide is 25-27g:200-250mL:10-11g:0.2-0.4g;

[0016] During the reaction of step A2, KH550 modifies the surface of the glass flakes to obtain NH2-glass flakes; the amino groups of the NH2-glass flakes react with the ester groups in the reaction product 1 to obtain the reaction product 2 containing fluorenone;

[0017] Step A3, adding the reaction product 2, phenol, and zinc chloride to concentrated hydrochloric acid, stirring and reacting at 45-50° C. for 12-13 hours, then pouring into ice water, adjusting the pH to 7.5-8, filtering, washing, recrystallizing from ethanol, and vacuum drying at 55-60° C. to obtain a bisphenol product;

[0018] Furthermore, the ratio of reaction product 2, phenol, zinc chloride, concentrated hydrochloric acid and ice water is 13-15 g: 48-50 g: 5.2-5.5 g: 330-350 mL: 3200-3300 mL;

[0019] During the reaction of step A3, the fluorenone of reaction product 2 reacts with phenol to obtain a bisphenol product containing a diazafluorene structure and glass flakes;

[0020] Step A4: In a protective gas atmosphere, heating bisphenol A, the bisphenol product, epichlorohydrin, and the catalyst to 75-80° C. with stirring, stirring for 3.5-4.0 hours, adding alkali solution and continuing stirring for 1-1.5 hours, extracting with toluene, washing with deionized water until neutral, separating the liquids, drying, distilling under reduced pressure, and drying at 70-75° C. to obtain a modified epoxy resin;

[0021] Furthermore, the usage ratio of bisphenol A, bisphenol product, epichlorohydrin, catalyst, and alkali solution is 21-23 g: 3.9-4.1 g: 188-192 g: 3.3-3.5 g: 20-22 g; the catalyst is tetrabutylammonium bromide, and the alkali solution is a sodium hydroxide solution with a mass fraction of 40-45%;

[0022] During the reaction of step A4, bisphenol A, the bisphenol product, and epichlorohydrin react under the action of a catalyst to obtain a modified epoxy resin.

[0023] The modified polysulfide rubber is prepared by the following steps:

[0024] Step B1, after mixing polysulfide rubber and 1,2-dichloroethane, add an ethanol solution of sodium hydroxide dropwise thereto, stir and react at 55-60° C. for 3-3.5 hours, and distill under reduced pressure to obtain a chlorinated polysulfide rubber; in a protective gas atmosphere, add the chlorinated polysulfide rubber to a mixed solvent, stir for 10-15 minutes, and then add dropwise to oleylamine, stir and react at 75-80° C. for 4.5-5 hours, cool, add sodium hydroxide, continue stirring for 30-35 minutes, filter, and distill under reduced pressure to obtain a double bond product;

[0025] Furthermore, the usage ratio of polysulfide rubber, 1,2-dichloroethane, and sodium hydroxide ethanol solution is 1-1.5 g: 4-6 g: 200-210 mL, and the concentration of the sodium hydroxide ethanol solution is 1 g / L; the usage ratio of chlorinated polysulfide rubber, mixed solvent, oleylamine, and sodium hydroxide is 2-2.5 g: 40-50 mL: 9-11 g: 0.16-1.18 g, and the mixed solvent is a mixture of isopropyl alcohol and toluene in a volume ratio of 2:1;

[0026] During the reaction of step B1, the polysulfide rubber undergoes a nucleophilic substitution reaction with ethylene dichloride in an ethanol solution of sodium hydroxide to produce a chlorine-terminated polysulfide rubber; the chlorine-terminated polysulfide rubber undergoes a nucleophilic substitution reaction with the amino group of oleylamine to produce a polysulfide rubber containing a long alkane chain and a carbon-carbon double bond, i.e., a double bond product;

[0027] Step B2, adding the double bond product to dichloromethane, stirring for 30-35 minutes, then adding m-chloroperbenzoic acid, stirring and reacting at room temperature for 8-9 hours to obtain an epoxy product;

[0028] Furthermore, the ratio of the double bond product, dichloromethane, and m-chloroperbenzoic acid is 5-6 g:75-85 mL:19-21 g;

[0029] During the reaction of step B2, the carbon-carbon double bonds in the double bond product are oxidized into epoxy groups to obtain a polysulfide rubber containing epoxy groups, i.e., an epoxy product;

[0030] Step B3, stirring the epoxy product, aminopropylheptyl POSS, and dimethyl sulfoxide at 50-60° C. for 24-25 hours, filtering, and drying to obtain a modified polysulfide rubber;

[0031] Furthermore, the usage ratio of the epoxy product, aminopropylheptyl POSS, and dimethyl sulfoxide is 8-9 g: 18-20 g: 90-100 mL;

[0032] During the reaction of step B3, the epoxy group of the epoxy product reacts with the amino group of the aminopropylheptyl POSS to obtain a polysulfide rubber containing hydroxyl groups, POSS, etc., namely, a modified polysulfide rubber.

[0033] Beneficial effects of the invention: The invention discloses a highly weather-resistant and anti-corrosion epoxy resin coating and a preparation method thereof. The highly weather-resistant and anti-corrosion epoxy resin coating comprises raw materials such as modified epoxy resin, amino resin, urea-formaldehyde resin, and modified polysulfide rubber.

[0034] The synthesized modified epoxy resin is obtained by introducing a diazafluorene structure and glass flakes into the epoxy resin molecular chain. The diazafluorene structure is a nitrogen-containing polycyclic heterocycle, in which the non-coordinating electrons of the nitrogen and the π electrons of the benzene ring can adsorb on metal surfaces to form a corrosion protection film. The glass flakes in the modified epoxy resin can be arranged in parallel, preventing corrosive media from approaching the substrate. This not only synergizes with the diazafluorene structure to enhance the corrosion resistance of the coating, but also improves the mechanical strength and heat resistance of the epoxy resin. The diazafluorene structure has strong rigidity, which can effectively reduce the free volume of the epoxy resin cured product, hinder the movement of polymer chain segments, and increase the polymer packing density, which is beneficial to improving the heat resistance of the coating, thereby synergizing with the glass flakes to enhance the weather resistance of the coating in high-temperature environments.

[0035] The synthesized modified polysulfide rubber is obtained by introducing POSS, hydroxyl groups, and long alkane chains into the polysulfide rubber molecular chain. The hydroxyl groups enable the modified polysulfide rubber to form a denser hydrogen-bonded cross-linked network with modified epoxy resins, preventing water molecules from penetrating into the epoxy resin coating in humid environments. The long alkane chains are hydrophobic and form an intramolecular synergistic effect with the hydroxyl groups, improving the weather resistance of the epoxy resin coating in high-humidity environments. The POSS has extremely high thermal and structural stability, which not only improves the heat resistance of the modified polysulfide rubber, making it more suitable for epoxy resin coatings with high heat resistance requirements, but also synergizes with the rigid diazine structure and glass flakes in the modified epoxy resin to improve the weather resistance of the epoxy resin coating in high-temperature environments.

[0036] In summary, the epoxy resin coating of the present invention has excellent corrosion resistance, mechanical strength, and weather resistance under high temperature and high humidity environments, and is worthy of promotion and use. DETAILED DESCRIPTION

[0037] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention. Example 1

[0038] A modified epoxy resin, the preparation of which comprises the following steps:

[0039] Step A1, 1,10-phenanthroline-2-carboxylic acid methyl ester and potassium hydroxide were added to deionized water and stirred at 75° C. for 20 minutes, and then potassium permanganate aqueous solution was added dropwise thereto. The addition was completed within 4.5 hours, and the reaction was continued with stirring for 3 hours. Then, hot filtration, concentration, recrystallization in water, and vacuum drying at 70° C. overnight to obtain reaction product 1; the amount ratio of 1,10-phenanthroline-2-carboxylic acid methyl ester, potassium hydroxide, deionized water, and potassium permanganate aqueous solution was 3.8 g:2.6 g:170 mL:111 mL; the potassium permanganate aqueous solution was obtained by adding 6.5 g of potassium permanganate to 105 mL of deionized water and stirring;

[0040] Step A2, add the dried glass flakes to the ethanol-water solution and stir for 15 minutes, then add the ethanol solution of the silane coupling agent, stir at 80°C for 4 hours, vacuum filter, wash three times with deionized water and ethanol respectively, and vacuum dry at 40°C to obtain NH2-glass flakes; in a nitrogen atmosphere, reflux the reaction product 1 at 100°C for 1 hour, cool to 50°C, add methanol and NH2-glass flakes, and then add sodium methoxide, stir and react for 24 hours to obtain reaction product 2; the amount ratio of dried glass flakes, ethanol-water solution, and silane coupling agent ethanol solution is 5.0 g: 50mL: 700mL, the silane coupling agent is KH550, the dried glass flakes are obtained by drying glass flakes (supplier: Lingshou County Hengxin Mineral Products Processing Plant, 200 mesh) at 105°C for 24h, the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 4:1; the ethanol solution of the silane coupling agent is obtained by adding the silane coupling agent to ethanol and stirring and mixing, and the concentration is 0.1mol / L; the volume fraction of the ethanol is 95%; the amount ratio of the reaction product 1, methanol, NH2-glass flakes and sodium methoxide is 25g: 200mL: 10g: 0.2g;

[0041] Step A3: Add reaction product 2, phenol, and zinc chloride to concentrated hydrochloric acid, stir and react at 45°C for 12 hours, then pour into ice water, adjust the pH to 8, filter, wash, recrystallize from ethanol, and vacuum dry at 55°C to obtain a bisphenol product; the amount ratio of reaction product 2, phenol, zinc chloride, concentrated hydrochloric acid, and ice water is 13 g:48 g:5.2 g:330 mL:3200 mL;

[0042] Step A4. In a nitrogen atmosphere, bisphenol A (supplier: Shandong Baiyao Chemical Co., Ltd.), bisphenol product, epichlorohydrin, and a catalyst were heated to 75°C with stirring, stirred for 3.5 hours, and then an alkali solution was added and stirred for 1 hour. The mixture was extracted with toluene, washed with deionized water until neutral, separated, dried, distilled under reduced pressure, and dried at 70°C to obtain a modified epoxy resin. The ratio of bisphenol A, bisphenol product, epichlorohydrin, catalyst, and alkali solution was 21 g:3.9 g:188 g:3.3 g:20 g. The catalyst was tetrabutylammonium bromide, and the alkali solution was a 40% by mass sodium hydroxide solution. Example 2

[0043] A modified epoxy resin, the preparation of which comprises the following steps:

[0044] Step A1, 1,10-phenanthroline-2-carboxylic acid methyl ester and potassium hydroxide were added to deionized water and stirred at 80° C. for 25 minutes, and then potassium permanganate aqueous solution was added dropwise thereto. The addition was completed within 4.7 hours, and the reaction was continued with stirring for 3.3 hours. Then, the mixture was hot filtered, concentrated, recrystallized in water, and vacuum dried at 75° C. overnight to obtain reaction product 1; the amount ratio of 1,10-phenanthroline-2-carboxylic acid methyl ester, potassium hydroxide, deionized water, and potassium permanganate aqueous solution was 3.9 g:2.7 g:173 mL:113 mL; the potassium permanganate aqueous solution was obtained by adding 6.6 g of potassium permanganate to 108 mL of deionized water and stirring;

[0045] Step A2: Add dried glass flakes to an ethanol-water solution and stir for 17 minutes, then add an ethanol solution of a silane coupling agent, stir at 83°C for 4.3 hours, vacuum filter, wash three times with deionized water and ethanol, and vacuum dry at 43°C to obtain NH2-glass flakes; in a nitrogen atmosphere, reflux the reaction product 1 at 100°C for 1.1 hours, cool to 53°C, add methanol and NH2-glass flakes, and then add sodium methoxide, and stir for 24 hours to obtain reaction product 2; the ratio of dried glass flakes, ethanol-water solution, and silane coupling agent ethanol solution is 5. 3g:53mL:730mL, the silane coupling agent is KH550, the dried glass flakes are obtained by drying glass flakes (supplier: Lingshou County Hengxin Mineral Products Processing Plant, 200 mesh) at 105°C for 24h, the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 4:1; the ethanol solution of the silane coupling agent is obtained by adding the silane coupling agent to ethanol and stirring and mixing, and the concentration is 0.1mol / L; the volume fraction of the ethanol is 95%; the amount ratio of the reaction product 1, methanol, NH2-glass flakes and sodium methoxide is 26g:230mL:10.5g:0.3g;

[0046] Step A3: Add reaction product 2, phenol, and zinc chloride to concentrated hydrochloric acid, stir and react at 48°C for 12.5 hours, then pour into ice water, adjust the pH to 8, filter, wash, recrystallize from ethanol, and vacuum dry at 58°C to obtain a bisphenol product; the amount ratio of reaction product 2, phenol, zinc chloride, concentrated hydrochloric acid, and ice water is 14 g:49 g:5.3 g:340 mL:3250 mL;

[0047] Step A4. In a protective gas atmosphere, bisphenol A (supplier: Shandong Baiyao Chemical Co., Ltd.), bisphenol product, epichlorohydrin, and a catalyst were heated to 80°C with stirring, stirred for 3.7 hours, and then alkali solution was added and stirred for 1.3 hours. The mixture was extracted with toluene, washed with deionized water until neutral, separated, dried, distilled under reduced pressure, and dried at 70°C to obtain a modified epoxy resin. The ratio of bisphenol A, bisphenol product, epichlorohydrin, catalyst, and alkali solution was 22 g:4.0 g:190 g:3.4 g:21 g. The catalyst was tetrabutylammonium bromide, and the alkali solution was a 43% by mass sodium hydroxide solution. Example 3

[0048] A modified epoxy resin, the preparation of which comprises the following steps:

[0049] Step A1, 1,10-phenanthroline-2-carboxylic acid methyl ester and potassium hydroxide were added to deionized water and stirred at 80° C. for 30 minutes, and then potassium permanganate aqueous solution was added dropwise thereto. The addition was completed within 5 hours, and the reaction was continued with stirring for 3.5 hours. Then, hot filtration, concentration, recrystallization in water, and vacuum drying at 80° C. overnight to obtain reaction product 1; the amount ratio of 1,10-phenanthroline-2-carboxylic acid methyl ester, potassium hydroxide, deionized water, and potassium permanganate aqueous solution was 4.0 g:2.8 g:175 mL:115 mL; the potassium permanganate aqueous solution was obtained by adding 6.7 g of potassium permanganate to 110 mL of deionized water and stirring;

[0050] Step A2, add the dried glass flakes to the ethanol-water solution and stir for 20 minutes, then add the ethanol solution of the silane coupling agent, stir at 85 ° C for 4.5 hours, vacuum filter, wash with deionized water and ethanol three times each, and vacuum dry at 45 ° C to obtain NH2-glass flakes; in a nitrogen atmosphere, reflux the reaction product 1 at 105 ° C for 1.2 hours, cool to 55 ° C, add methanol and NH2-glass flakes, and then add sodium methoxide, stir and react for 25 hours to obtain reaction product 2; the amount ratio of dried glass flakes, ethanol-water solution, and silane coupling agent ethanol solution is 5 0.5g:55mL:750mL, the silane coupling agent is KH550, the dried glass flakes are obtained by drying glass flakes (supplier: Lingshou County Hengxin Mineral Products Processing Plant, 200 mesh) at 110°C for 25h, the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 4:1; the ethanol solution of the silane coupling agent is obtained by adding the silane coupling agent to ethanol and stirring and mixing, and the concentration is 0.1mol / L; the volume fraction of the ethanol is 95%; the amount ratio of reaction product 1, methanol, NH2-glass flakes and sodium methoxide is 27g:250mL:11g:0.4g;

[0051] Step A3: Add reaction product 2, phenol, and zinc chloride to concentrated hydrochloric acid, stir and react at 50°C for 13 hours, then pour into ice water, adjust the pH to 8, filter, wash, recrystallize from ethanol, and vacuum dry at 60°C to obtain a bisphenol product; the amount ratio of reaction product 2, phenol, zinc chloride, concentrated hydrochloric acid, and ice water is 15 g:50 g:5.5 g:350 mL:3300 mL;

[0052] Step A4. In a nitrogen atmosphere, bisphenol A (supplier: Shandong Baiyao Chemical Co., Ltd.), bisphenol product, epichlorohydrin, and a catalyst were heated to 80°C with stirring, stirred for 4.0 hours, and then an alkali solution was added and stirred for 1.5 hours. The mixture was extracted with toluene, washed with deionized water until neutral, separated, dried, distilled under reduced pressure, and dried at 75°C to obtain a modified epoxy resin. The ratio of bisphenol A, bisphenol product, epichlorohydrin, catalyst, and alkali solution was 23 g:4.1 g:192 g:3.5 g:22 g. The catalyst was tetrabutylammonium bromide, and the alkali solution was a 45% by mass sodium hydroxide solution. Example 4

[0053] A modified polysulfide rubber, the preparation of which comprises the following steps:

[0054] Step B1: After mixing polysulfide rubber (supplier: Hubei Maidehao Biotechnology Co., Ltd.) and 1,2-dichloroethane, an ethanol solution of sodium hydroxide was added dropwise thereto, and the mixture was stirred at 55° C. for 3 hours, and the chlorinated polysulfide rubber was obtained by distillation under reduced pressure. In a nitrogen atmosphere, the chlorinated polysulfide rubber was added to a mixed solvent, stirred for 10 minutes, and then added dropwise to oleylamine, stirred at 75° C. for 4.5 hours. After cooling, sodium hydroxide was added and stirring was continued for 30 minutes. The product was filtered and distilled under reduced pressure to obtain a double bond product. The amount ratio of polysulfide rubber, 1,2-dichloroethane, and the ethanol solution of sodium hydroxide was 1g:4g:200mL, and the concentration of the ethanol solution of sodium hydroxide was 1g / L. The amount ratio of the chlorinated polysulfide rubber, mixed solvent, oleylamine, and sodium hydroxide was 2g:40mL:9g:0.16g, and the mixed solvent was a mixture of isopropanol and toluene in a volume ratio of 2:1.

[0055] Step B2, adding the double bond product to dichloromethane, stirring for 30 minutes, then adding m-chloroperbenzoic acid, stirring and reacting at room temperature for 8 hours to obtain an epoxy product; the amount ratio of the double bond product, dichloromethane, and m-chloroperbenzoic acid is 5g:75mL:19g;

[0056] Step B3: Stir the epoxy product, aminopropylheptyl POSS, and dimethyl sulfoxide at 50° C. for 24 h, filter, and dry to obtain a modified polysulfide rubber; the epoxy product, aminopropylheptyl POSS, and dimethyl sulfoxide are used in a ratio of 8 g:18 g:90 mL. Example 5

[0057] A modified polysulfide rubber, the preparation of which comprises the following steps:

[0058] Step B1: After mixing polysulfide rubber (supplier: Hubei Maidehao Biotechnology Co., Ltd.) and 1,2-dichloroethane, an ethanol solution of sodium hydroxide was added dropwise thereto, and the mixture was stirred at 55° C. for 3.3 hours, and the chlorinated polysulfide rubber was obtained by distillation under reduced pressure. In a nitrogen atmosphere, the chlorinated polysulfide rubber was added to a mixed solvent, stirred for 13 minutes, and then added dropwise to oleylamine, stirred at 75° C. for 4.7 hours. After cooling, sodium hydroxide was added and stirring was continued for 33 minutes. The product was filtered and distilled under reduced pressure to obtain a double bond product. The amount ratio of polysulfide rubber, 1,2-dichloroethane, and the ethanol solution of sodium hydroxide was 1.3 g: 5 g: 205 mL, and the concentration of the ethanol solution of sodium hydroxide was 1 g / L. The amount ratio of chlorinated polysulfide rubber, mixed solvent, oleylamine, and sodium hydroxide was 2.3 g: 45 mL: 10 g: 0.17 g, and the mixed solvent was a mixture of isopropanol and toluene in a volume ratio of 2: 1.

[0059] Step B2, the double bond product was added into dichloromethane, and after stirring for 33 min, m-chloroperoxybenzoic acid was added, and the reaction was stirred at room temperature for 8.5 h to obtain the epoxy product; the amount ratio of the double bond product, dichloromethane and m-chloroperoxybenzoic acid was 5.5 g:80 mL:20 g;

[0060] Step B3, the epoxy product, aminopropylheptyl POSS and dimethyl sulfoxide were stirred at 55 ℃ for 24.5 h, and then filtered and dried to obtain the modified polysulfide rubber; the amount ratio of the epoxy product, aminopropylheptyl POSS and dimethyl sulfoxide was 8.5 g:19 g:95 mL. Example 6

[0061] A modified polysulfide rubber, the preparation comprising the following steps:

[0062] Step B1, the polysulfide rubber (supplier: Hubei Maidehao Biotechnology Co., Ltd.) was mixed with 1,2-dichloroethane, and then sodium hydroxide ethanol solution was added dropwise, and the reaction was stirred at 60 ℃ for 3.5 h, and then distilled under reduced pressure to obtain a terminal chloro polysulfide rubber; the terminal chloro polysulfide rubber was added into a mixed solvent, stirred for 15 min, and then added dropwise into oleylamine, and the reaction was stirred at 80 ℃ for 5 h, and then sodium hydroxide was added after cooling, and the stirring was continued for 35 min, and then filtered and distilled under reduced pressure to obtain a double bond product; the amount ratio of the polysulfide rubber, 1,2-dichloroethane and sodium hydroxide ethanol solution was 1.5 g:6 g:210 mL, and the concentration of the sodium hydroxide ethanol solution was 1 g / L; the amount ratio of the terminal chloro polysulfide rubber, mixed solvent, oleylamine and sodium hydroxide was 2.5 g:50 mL:11 g:1.18 g, and the mixed solvent was obtained by mixing isopropyl alcohol and toluene in a volume ratio of 2:1;

[0063] Step B2, the double bond product was added into dichloromethane, and after stirring for 33 min, m-chloroperoxybenzoic acid was added, and the reaction was stirred at room temperature for 8.5 h to obtain the epoxy product; the amount ratio of the double bond product, dichloromethane and m-chloroperoxybenzoic acid was 5.5 g:80 mL:20 g;

[0064] Step B3, the epoxy product, aminopropylheptyl POSS and dimethyl sulfoxide were stirred at 55 ℃ for 24.5 h, and then filtered and dried to obtain the modified polysulfide rubber; the amount ratio of the epoxy product, aminopropylheptyl POSS and dimethyl sulfoxide was 8.5 g:19 g:95 mL. Example 7

[0065] A high weather-resistant anticorrosive epoxy resin paint comprises the following raw materials by weight: modified epoxy resin 50 parts, amino resin 30 parts, urea-formaldehyde resin 15 parts, modified polysulfide rubber 10 parts, titanium white 8 parts, kaolin 3 parts, dispersing agent 0.5 parts, leveling agent 0.6 parts, defoaming agent 0.2 parts, drying agent 0.8 parts and solvent 15 parts; the dispersing agent is BYK-2070, the leveling agent is BYK-306, the defoaming agent is BYK-A530, the drying agent is potassium isooctanoate, and the solvent is ethyl acetate.

[0066] The high weather-resistant anticorrosive epoxy resin paint is prepared by the following steps: mixing the modified epoxy resin obtained in Example 1, the urea-formaldehyde resin (supplier: Shandong Haoyao New Material Co., Ltd.) and the modified polysulfide rubber obtained in Example 4 at 80℃ for 2h, then adding the amino resin (supplier: Shandong Wangtong Chemical Co., Ltd.) and stirring at 60℃ for 1h, and then adding the titanium white, kaolin, dispersing agent, leveling agent, defoaming agent, drying agent and solvent and continuing to stir at 60℃ for 1.5h to obtain the high weather-resistant anticorrosive epoxy resin paint. Example 8

[0067] A high weather-resistant anticorrosive epoxy resin paint comprises the following raw materials by weight: modified epoxy resin 53 parts, amino resin 33 parts, urea-formaldehyde resin 16 parts, modified polysulfide rubber 11 parts, titanium white 9 parts, kaolin 4 parts, dispersing agent 0.8 parts, leveling agent 0.7 parts, defoaming agent 0.3 parts, drying agent 0.9 parts and solvent 17 parts; the dispersing agent is BYK-2070, the leveling agent is BYK-306, the defoaming agent is BYK-A530, the drying agent is potassium isooctanoate, and the solvent is ethyl acetate.

[0068] The high weather-resistant anticorrosive epoxy resin paint is prepared by the following steps: mixing the modified epoxy resin obtained in Example 2, the urea-formaldehyde resin (supplier: Shandong Haoyao New Material Co., Ltd.) and the modified polysulfide rubber obtained in Example 5 at 85℃ for 2.3h, then adding the amino resin (supplier: Shandong Wangtong Chemical Co., Ltd.) and stirring at 65℃ for 1.3h, and then adding the titanium white, kaolin, dispersing agent, leveling agent, defoaming agent, drying agent and solvent and continuing to stir at 65℃ for 1.7h to obtain the high weather-resistant anticorrosive epoxy resin paint. Example 9

[0069] A high weather-resistant anticorrosive epoxy resin paint comprises the following raw materials by weight: modified epoxy resin 55 parts, amino resin 35 parts, urea-formaldehyde resin 17 parts, modified polysulfide rubber 12 parts, titanium white 10 parts, kaolin 5 parts, dispersing agent 1.0 parts, leveling agent 0.8 parts, defoaming agent 0.4 parts, drying agent 1.0 parts and solvent 20 parts; the dispersing agent is BYK-2070, the leveling agent is BYK-306, the defoaming agent is BYK-A530, the drying agent is potassium isooctanoate, and the solvent is ethyl acetate.

[0070] The preparation of the highly weather-resistant and anti-corrosion epoxy resin coating comprises the following steps: the modified epoxy resin obtained in Example 3, the urea-formaldehyde resin (supplier: Shandong Haoyao New Materials Co., Ltd.) and the modified polysulfide rubber obtained in Example 6 are stirred and mixed at 90° C. for 2.5 hours, and then an amino resin (supplier: Shandong Wangtong Chemical Co., Ltd.) is added and stirred at 70° C. for 1.5 hours. Titanium dioxide, kaolin, dispersant, leveling agent, defoaming agent, drying agent and solvent are then added and stirred at 70° C. for 2.0 hours to obtain the highly weather-resistant and anti-corrosion epoxy resin coating.

[0071] Comparative Example 1

[0072] Compared with Example 9, the NH2-glass flakes in the preparation process of the modified epoxy resin were replaced with 1-aminopentane, and the rest were exactly the same as in Example 9 to prepare the epoxy resin coating.

[0073] Comparative Example 2

[0074] Compared with Example 9, the reaction product 1 in the preparation process of the modified epoxy resin was replaced with 9-fluorenone-2,7-dicarboxylic acid methyl ester, and the rest was exactly the same as Example 9 to prepare the epoxy resin coating.

[0075] Comparative Example 3

[0076] Compared with Example 9, the bisphenol product in the preparation process of the modified epoxy resin was replaced with methyl 2,2-bis(4-hydroxyphenyl)acetate, and the rest was exactly the same as Example 9 to prepare the epoxy resin coating.

[0077] Comparative Example 4

[0078] Compared with Example 9, the epoxy resin coating was prepared by replacing oleylamine in the preparation process of the modified polysulfide rubber with N-methylallylamine and proceeding in the same manner as in Example 9.

[0079] Comparative Example 5

[0080] Compared with Example 9, the modified polysulfide rubber used was replaced with a double-bond product, and the rest was exactly the same as Example 9 to prepare an epoxy resin coating.

[0081] The epoxy resin coating prepared by the present invention is further tested for its effect, and the test results are as follows.

[0082] Corrosion inhibition efficiency: The epoxy resin coating was scraped onto the surface of a standard test steel plate cleaned and dried with anhydrous ethanol to obtain a test sample. The dry film thickness of the coating was (50±5) μm. After curing at 60°C for 3 days, an electrochemical impedance spectroscopy test was performed. Electrochemical impedance spectroscopy: A three-electrode system was used, with the working electrode being the coating / standard test steel plate, the reference electrode being a saturated calomel electrode, and the counter electrode being a graphite electrode. The test sample was immersed in a 3.5% NaCl solution for 7 days before testing. The test frequency range was 10 5 -10 -2 Hz, the test sine wave signal amplitude was 50mV, the test was carried out at open circuit potential and room temperature, and the instrument used was a CS310H electrochemical workstation; the surface charge transfer resistance R1 (of the test sample) and R0 (of the standard steel plate without coating protection) were recorded, and the corrosion inhibition efficiency was calculated, corrosion inhibition efficiency = (R1-R0) / R1×100%, and the results are recorded in Table 1;

[0083] Tensile strength: The tensile strength was tested using a universal tensile testing machine according to the method specified in GB / T 528-2009. The moving speed of the clamp was set at 10 mm / min. The results are recorded in Table 1.

[0084] Weather resistance (high temperature environment): Place the test sample in a 160°C oven for 12 hours, measure and calculate the tensile strength retention rate according to the above method, and record the results in Table 1;

[0085] Weather resistance (high humidity environment): Soak the test sample in water for 12 hours, measure and calculate the tensile strength retention rate according to the above method, and record the results in Table 1;

[0086] Table 1: Test results

[0087] Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Corrosion inhibition efficiency (%) 92.85 93.02 93.18 86.62 85.28 85.42 93.15 93.16 Tensile strength (MPa) 15.3 15.5 16.1 12.7 15.9 15.6 15.9 15.6 Tensile strength retention after high temperature treatment (%) 96.2 96.4 96.9 92.7 96.8 92.6 96.8 92.4 Tensile strength retention after high humidity treatment (%) 95.6 95.8 96.1 96.0 96.1 96.0 91.1 91.5

[0088] According to the data in Table 1, the epoxy resin coating of the present invention has excellent corrosion resistance, mechanical strength and weather resistance in high temperature and high humidity environments. As shown in Example 9 compared with Comparative Example 1, the NH2-glass flakes in the modified epoxy resin preparation process are replaced with 1-aminopentane, and glass flakes are not introduced into the epoxy resin molecular chain. It can neither synergize with the diazafluorene structure to enhance the corrosion resistance of the coating, nor enhance the mechanical strength and heat resistance of the epoxy resin, resulting in a decrease in the corrosion inhibition efficiency, tensile strength and tensile strength retention rate of the coating in a high temperature environment. As shown in Example 9 compared with Comparative Example 2, the reaction product 1 in the modified epoxy resin preparation process is replaced with 9-fluorenone-2,7-dicarboxylic acid methyl ester, and a nitrogen-free rigid fluorene structure is introduced into the epoxy resin molecular chain. A corrosion protection film cannot be formed, and thus the corrosion resistance of the coating cannot be enhanced in synergy with the glass flakes, resulting in a decrease in the corrosion inhibition efficiency of the coating. As can be seen from Example 9 compared with Comparative Example 3, the bisphenol product in the modified epoxy resin preparation process is replaced with methyl 2,2-bis(4-hydroxyphenyl)methyl acetate, and the diazafluorene structure is not introduced into the epoxy resin molecular chain. It can neither cooperate with the glass flakes to enhance the corrosion resistance of the coating, nor cooperate with the glass flakes and POSS to enhance the weather resistance of the coating in a high-temperature environment, resulting in a decrease in the corrosion inhibition efficiency of the coating and the tensile strength retention rate in a high-temperature environment. As can be seen from Example 9 compared with Comparative Example 4, the oleylamine in the modified polysulfide rubber preparation process is replaced with N-methylallylamine, and no long alkane chain is introduced. It is impossible to produce intramolecular synergy with the hydroxyl group, which reduces the weather resistance of the epoxy resin coating in a high-humidity environment and causes a decrease in the tensile strength retention rate of the coating in a high-humidity environment. Comparison of Example 9 with Comparative Example 5 shows that by replacing the modified polysulfide rubber with a double bond product without introducing POSS and hydroxyl groups, it can neither synergize with the diazafluorene structure and glass flakes to improve the weather resistance of the coating in a high-temperature environment, nor produce an intramolecular synergistic effect with the long chain of alkanes, which reduces the weather resistance of the epoxy resin coating in a high-humidity environment and causes a decrease in the tensile strength retention rate of the coating in a high-temperature, high-humidity environment.

[0089] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. A highly weather-resistant and anti-corrosion epoxy resin coating, characterized in that: The invention comprises the following raw materials in parts by weight: 50-55 parts of modified epoxy resin, 30-35 parts of amino resin, 15-17 parts of urea-formaldehyde resin, 10-12 parts of modified polysulfide rubber, 8-10 parts of titanium dioxide, 3-5 parts of kaolin, 0.5-1.0 parts of dispersant, 0.6-0.8 parts of leveling agent, 0.2-0.4 parts of defoaming agent, 0.8-1.0 parts of drying agent and 15-20 parts of solvent; The modified epoxy resin is prepared by the following steps: Step A1, adding 1,10-phenanthroline-2-carboxylic acid methyl ester and potassium hydroxide to deionized water, and then adding potassium permanganate aqueous solution dropwise thereto, and continuing to stir the reaction after the addition is complete to obtain reaction product 1; Step A2, adding dried glass flakes to an ethanol aqueous solution, then adding an ethanol solution of a silane coupling agent, stirring and reacting to obtain NH2-glass flakes; In a protective gas atmosphere, the reaction product 1 was refluxed with stirring, then cooled and methanol and NH2-glass flakes were added, followed by sodium methoxide, and the mixture was stirred to react to obtain the reaction product 2; Step A3, adding the reaction product 2, phenol and zinc chloride to concentrated hydrochloric acid, stirring for reaction, pouring into ice water, adjusting the pH and post-processing to obtain a bisphenol product; Step A4: In a protective gas atmosphere, bisphenol A, a bisphenol product, epichlorohydrin, a catalyst, and an alkaline solution are mixed and stirred to obtain a modified epoxy resin; The modified polysulfide rubber is prepared by the following steps: Step B1, after mixing polysulfide rubber and 1,2-dichloroethane, add an ethanol solution of sodium hydroxide dropwise thereto, stir and react at 55-60° C. for 3-3.5 hours, and distill under reduced pressure to obtain a chlorinated polysulfide rubber; in a protective gas atmosphere, add the chlorinated polysulfide rubber to a mixed solvent, stir for 10-15 minutes, and then add dropwise to oleylamine, stir and react at 75-80° C. for 4.5-5 hours, cool, add sodium hydroxide, continue stirring for 30-35 minutes, filter, and distill under reduced pressure to obtain a double bond product; Step B2, adding the double bond product to dichloromethane, stirring for 30-35 minutes, then adding m-chloroperbenzoic acid, stirring and reacting at room temperature for 8-9 hours to obtain an epoxy product; Step B3: Stir the epoxy product, aminopropylheptyl POSS, and dimethyl sulfoxide at 50-60° C. for 24-25 hours, filter, and dry to obtain the modified polysulfide rubber.

2. The highly weather-resistant and anti-corrosion epoxy resin coating according to claim 1, characterized in that: The dispersant is BYK-2070, the leveling agent is BYK-306, the defoaming agent is BYK-A530, the drying agent is potassium isooctanoate, and the solvent is ethyl acetate.

3. The highly weather-resistant and anti-corrosion epoxy resin coating according to claim 1, characterized in that: In step A1, the ratio of 1,10-phenanthroline-2-carboxylic acid methyl ester, potassium hydroxide, deionized water, and potassium permanganate aqueous solution is 3.8-4.0 g: 2.6-2.8 g: 170-175 mL: 111-115 mL; the potassium permanganate aqueous solution is prepared by adding 6.5-6.7 g of potassium permanganate to 105-110 mL of deionized water and stirring.

4. The highly weather-resistant and anti-corrosion epoxy resin coating according to claim 1, characterized in that: In step A2, the dosage ratio of dried glass flakes, ethanol aqueous solution, and ethanol solution of silane coupling agent is 5.0-5.5 g: 50-55 mL: 700-750 mL, the silane coupling agent is KH550, the dried glass flakes are obtained by drying the glass flakes at 105-110°C for 24-25 hours, and the volume ratio of ethanol to deionized water in the ethanol aqueous solution is 4:

1.

5. The highly weather-resistant and anti-corrosion epoxy resin coating according to claim 1, characterized in that: In step A2, the ethanol solution of the silane coupling agent is obtained by adding the silane coupling agent to ethanol and stirring, and the concentration is 0.1-0.15 mol / L; the volume fraction of the ethanol is 95%; and the amount ratio of the reaction product 1, methanol, NH2-glass flakes and sodium methoxide is 25-27 g: 200-250 mL: 10-11 g: 0.2-0.4 g.

6. The highly weather-resistant and anti-corrosion epoxy resin coating according to claim 1, characterized in that: In step A3, the ratio of reaction product 2, phenol, zinc chloride, concentrated hydrochloric acid, and ice water is 13-15 g: 48-50 g: 5.2-5.5 g: 330-350 mL: 3200-3300 mL; in step A4, the ratio of bisphenol A, bisphenol product, epichlorohydrin, catalyst, and alkali solution is 21-23 g: 3.9-4.1 g: 188-192 g: 3.3-3.5 g: 20-22 g; the catalyst is tetrabutylammonium bromide, and the alkali solution is a sodium hydroxide solution with a mass fraction of 40-45%.

7. The highly weather-resistant and anti-corrosion epoxy resin coating according to claim 1, characterized in that: In step B1, the amount ratio of polysulfide rubber, 1,2-dichloroethane, and sodium hydroxide ethanol solution is 1-1.5 g: 4-6 g: 200-210 mL, and the concentration of the sodium hydroxide ethanol solution is 1 g / L; the amount ratio of chlorinated polysulfide rubber, mixed solvent, oleylamine, and sodium hydroxide is 2-2.5 g: 40-50 mL: 9-11 g: 0.16-1.18 g, and the mixed solvent is isopropyl alcohol and toluene mixed in a volume ratio of 2:

1.

8. The highly weather-resistant and anti-corrosion epoxy resin coating according to claim 1, characterized in that: In step B2, the ratio of double bond product, dichloromethane, and m-chloroperbenzoic acid is 5-6 g:75-85 mL:19-21 g; In step B3, the usage ratio of the epoxy product, aminopropylheptyl POSS, and dimethyl sulfoxide is 8-9 g:18-20 g:90-100 mL.

9. A method for preparing the highly weather-resistant and anti-corrosion epoxy resin coating according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: stirring and mixing modified epoxy resin, urea-formaldehyde resin and modified polysulfide rubber at 80-90°C for 2-2.5 hours, adding amino resin and stirring at 60-70°C for 1-1.5 hours, then adding titanium dioxide, kaolin, dispersant, leveling agent, defoaming agent, drying agent and solvent and continuing stirring at 60-70°C for 1.5-2.0 hours to obtain a highly weather-resistant and anti-corrosion epoxy resin coating.