A kind of water-based two-component epoxy anticorrosive paint and preparation method thereof

Abstract

The invention relates to the field of anti-corrosion coatings, and in particular to a water-based two-component epoxy anti-corrosion paint and a preparation method thereof, which are used to solve the problem of poor corrosion resistance of existing water-based epoxy anti-corrosion paints; the water-based two-component epoxy anti-corrosion paint uses fluorine-containing organosilicon epoxy resin as a main raw material, imparts excellent corrosion resistance to the paint film, and can further enhance the corrosion resistance of the paint film after adding glutamic acid-modified graphene oxide, and the paint film is firmly combined with the metal surface and is not easy to fall off, and can still maintain good performance in a humid and highly corrosive environment, and is harmless to the environment and human health, and has broad application prospects.

Description

Technical Field

[0001] The invention relates to the field of anti-corrosion coatings, and in particular to a water-based two-component epoxy anti-corrosion paint and a preparation method thereof. Background Art

[0002] Metal materials have excellent mechanical properties and are widely used in the industrial field. The corrosion problem of metal structures has always been a severe challenge. With the development of industry, the anti-corrosion requirements for metal structures are getting higher and higher. However, metal corrosion often leads to safety accidents and causes huge economic losses. Applying organic coatings on metal surfaces can avoid and slow down metal corrosion. It has the advantages of low cost, convenient construction and good protective effect. Epoxy resin paint is a commonly used anti-corrosion coating. It has high mechanical strength, chemical resistance and good anti-corrosion performance. Water-based epoxy anti-corrosion paint has attracted widespread attention for its environmental protection and safety. However, the water-based epoxy anti-corrosion paint on the market currently evaporates water during the curing process, which is easy to produce a large number of micropores and defects, causing the corrosive medium to penetrate through the coating to the metal surface, affecting the firmness and corrosion resistance of the coating, causing metal corrosion, and it is difficult to meet the needs of practical applications.

[0003] Therefore, it is of great significance and practical value to develop an environmentally friendly water-based two-component epoxy anti-corrosion paint with excellent performance and a preparation method thereof. Summary of the invention

[0004] In order to overcome the above technical problems, the purpose of the present invention is to provide a water-based two-component epoxy anti-corrosion paint and a preparation method thereof, which solves the problem that the existing water-based epoxy anti-corrosion paint has poor anti-corrosion performance.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] A water-based two-component epoxy anticorrosive paint, comprising component A and component B;

[0007] The mass ratio of component A to component B is 1:0.3-0.6;

[0008] Wherein, the component A comprises the following components in parts by weight:

[0009] 35-45 parts of fluorinated silicone epoxy resin, 18-24 parts of deionized water, 1.1-2.3 parts of glutamic acid modified graphene oxide, 0.5-1.5 parts of dispersant, 0.2-0.6 parts of defoamer and 0.1-0.5 parts of wetting agent;

[0010] Wherein, the component B comprises the following components in parts by weight:

[0011] 25-33 parts of amine curing agent and 11-15 parts of deionized water.

[0012] As a further solution of the present invention: the fluorine-containing silicone epoxy resin is prepared by the following steps:

[0013] Step A1: trifluoropropylmethylcyclotrisiloxane and tetramethyldisiloxane are added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen is introduced for protection. The mixture is stirred and reacted for 30-40 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min. Trifluoromethanesulfonic acid is then added and stirred and reacted for 5-10 minutes. The mixture is then heated to 50-55° C. and stirred and reacted for 20-25 hours. After the reaction is completed, the reaction product is cooled to room temperature, added to n-heptane, dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then small molecular low-boiling substances are distilled off at a temperature of 180-185° C. to obtain hydrogen-containing fluoropolysiloxane;

[0014] Step A2: Add hydrogen-containing fluoropolysiloxane, eugenol, KARSTEDT catalyst and anhydrous toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 25-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then heat to 80-85° C. and continue to stir and react for 8-10 hours, then heat to 90-95° C. and continue to stir and react for 2-3 hours, after the reaction is completed, cool the reaction product to room temperature, and then rotary evaporate to remove the solvent to obtain terminal hydroxyl fluoropolysiloxane;

[0015] Step A3: Add terminal hydroxyl fluorinated polysiloxane, benzyltriethylammonium chloride and epichlorohydrin to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 80-85°C and continue to stir and react for 3-5 hours, then add sodium hydroxide solution dropwise while stirring, control the dropping rate to 1-2 drops / s, and continue to stir and react for 1-2 hours after the addition is completed. After the reaction is completed, the reaction product is cooled to room temperature, then added to distilled water, then allowed to stand for stratification, the organic phase is dried over anhydrous magnesium sulfate, then vacuum filtered, the filtrate is rotary evaporated to remove the solvent, then placed in a vacuum drying oven, and dried at a temperature of 80-85°C for 6-8 hours to obtain a fluorinated silicone epoxy resin.

[0016] As a further solution of the present invention: the trifluoropropylmethylcyclotrisiloxane, tetramethyldisiloxane and trifluoromethanesulfonic acid 15-20g: 0.3-1.3g: 0.3-0.5mL in step A1.

[0017] As a further solution of the present invention: the usage ratio of the hydrogen-containing fluoropolysiloxane, eugenol, KARSTEDT catalyst and anhydrous toluene in step A2 is 30-40 g: 2.5-3.5 g: 0.5-0.9 g: 40-50 mL.

[0018] As a further solution of the present invention: the terminal hydroxyl fluorinated polysiloxane, benzyltriethylammonium chloride, epichlorohydrin and sodium hydroxide solution in step A3 20-30 g: 0.6-1.2 g: 60-80 mL.

[0019] As a further solution of the present invention: the mass fraction of the sodium hydroxide solution in step A3 is 35-40%.

[0020] As a further solution of the present invention: the glutamic acid modified graphene oxide is prepared by the following steps:

[0021] Step B1: Graphite powder, concentrated sulfuric acid, phosphoric acid and sodium nitrate are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 0-5°C and a stirring rate of 300-400r / min for 20-30min, and then potassium permanganate is added and the mixture is heated to 45-50°C and stirred for reaction for 1-1.5h, and then heated to 95-100°C and stirred for reaction for 1-1.5h. After the reaction is completed, the reaction product is poured into ice water, and then a hydrogen peroxide solution is added, and then the mixture is allowed to stand for 8-10h, and then centrifuged. The precipitate is washed with hydrochloric acid solution and distilled water for 3-5 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 90-100°C for 5-6h to obtain graphene oxide;

[0022] Step B2: Add graphene oxide, deionized water, L-glutamic acid and sodium hydroxide solution to a three-necked flask equipped with a stirrer and a thermometer, perform ultrasonic treatment at an ultrasonic frequency of 40-50kHz for 30-40min, then stir the reaction at a temperature of 40-45°C and a stirring rate of 300-400r / min for 8-10h. After the reaction, cool the reaction product to room temperature and then centrifuge it. Wash the precipitate with anhydrous ethanol and distilled water for 3-5 times in turn, then place it in a vacuum drying oven and dry it at a temperature of 50-55°C for 2-3h to obtain glutamic acid modified graphene oxide.

[0023] As a further solution of the present invention: the usage ratio of the graphite powder, concentrated sulfuric acid, phosphoric acid, sodium nitrate, potassium permanganate and hydrogen peroxide solution in step B1 is 5g:90-100mL:13-15mL:2.5-3.5g:15-20g:15-20mL.

[0024] As a further solution of the present invention: the mass fraction of the concentrated sulfuric acid in step B1 is 98%, the mass fraction of the hydrogen peroxide solution is 30%, and the mass fraction of the hydrochloric acid solution is 8-10%.

[0025] As a further solution of the present invention: the usage ratio of the graphene oxide, deionized water, L-glutamic acid and sodium hydroxide solution in step B2 is 1 g: 100-120 mL: 2.5-4.5 g: 40-50 mL.

[0026] As a further solution of the present invention: the mass fraction of the sodium hydroxide solution in step B2 is 30-40%.

[0027] As a further solution of the present invention: a method for preparing a water-based two-component epoxy anticorrosive paint comprises the following steps:

[0028] Step 1: Weigh 35-45 parts of fluorinated silicone epoxy resin, 18-24 parts of deionized water, 1.1-2.3 parts of glutamic acid modified graphene oxide, 0.5-1.5 parts of dispersant, 0.2-0.6 parts of defoamer, 0.1-0.5 parts of wetting agent, 25-33 parts of amine curing agent and 11-15 parts of deionized water according to weight parts;

[0029] Step 2: adding fluorinated organosilicon epoxy resin, deionized water, glutamic acid-modified graphene oxide, dispersant, defoamer and wetting agent into a mixer and mixing evenly to obtain component A;

[0030] Step 3: Add the amine curing agent and deionized water into a mixer and mix them evenly to obtain component B;

[0031] Step 4: Evenly mix component A and component B in a mass ratio of 1:0.3-0.6 to obtain a water-based two-component epoxy anticorrosive paint.

[0032] As a further solution of the present invention: the dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; and the amine curing agent is polyetheramine curing agent T5000.

[0033] Beneficial effects of the present invention:

[0034] The invention discloses a water-based two-component epoxy anticorrosive paint and a preparation method thereof. The method comprises the following steps: adding fluorinated organosilicon epoxy resin, deionized water, glutamic acid modified graphene oxide, a dispersant, a defoamer and a wetting agent into a mixer and mixing them evenly to obtain a component A; adding an amine curing agent and deionized water into the mixer and mixing them evenly to obtain a component B; and mixing the components A and B evenly to obtain the water-based two-component epoxy anticorrosive paint. The water-based two-component epoxy anticorrosive paint uses the fluorinated organosilicon epoxy resin as a main raw material, and imparts excellent corrosion resistance to the paint film. After adding glutamic acid modified graphene oxide, the anticorrosive performance of the paint film can be further enhanced. The paint film is firmly combined with the metal surface and is not easy to fall off. The paint film can still maintain good performance in a humid and highly corrosive environment, and is harmless to the environment and human health, and has broad application prospects.

[0035] In the process of preparing the water-based two-component epoxy anticorrosive paint, a fluorine-containing silicone epoxy resin is first prepared, and trifluoropropylmethylcyclotrisiloxane and tetramethyldisiloxane are first used as raw materials for polymerization to form a hydrogen-containing fluorine polysiloxane, and then the hydrogen-containing fluorine polysiloxane and eugenol react, and the Si-H on the hydrogen-containing fluorine polysiloxane reacts with the alkenyl on the eugenol to obtain a terminal hydroxyl-containing fluorine polysiloxane, and then the terminal hydroxyl-containing fluorine polysiloxane and epichlorohydrin react to obtain the hydroxyl on the terminal hydroxyl-containing fluorine polysiloxane. After the ring-opening-ring-closing reaction with epichlorohydrin, epoxy groups are introduced to obtain a fluorine-containing silicone epoxy resin; the molecular structure of the fluorine-containing silicone epoxy resin contains a large number of fluorine atoms and silicon atoms, which give it extremely strong electronegativity and low surface energy, so that the surface energy of the paint film formed by the water-based two-component epoxy anti-corrosion paint is significantly reduced, thereby improving the paint film's ability to repel moisture, oxygen and corrosive ions, and the presence of fluorine atoms can also enhance the chemical stability of the paint film and resist corrosion by corrosive media such as acids, alkalis, and salts;

[0036] In the process of preparing the water-based two-component epoxy anti-corrosion paint, a glutamic acid-modified graphene oxide is also prepared. First, graphite powder is used as a raw material to prepare graphene oxide, and then L-glutamic acid is used to modify the graphene oxide, and a large number of carboxyl groups and amino groups are introduced into the surface of the graphene oxide to obtain glutamic acid-modified graphene oxide. After the modification, the dispersibility of the glutamic acid-modified graphene oxide is greatly improved, so that it is evenly distributed in the water-based two-component epoxy anti-corrosion paint. Graphene oxide has a unique two-dimensional layered structure and a high specific surface area, can be tightly attached to the surface of the paint film, and can fill the micropores in the paint film, hinder the invasion of corrosive media, and form a physical barrier. Moreover, the large number of carboxyl groups and amino groups introduced can form complexes with metal ions, reduce the activity of metal ions, and play a role in inhibiting corrosion of metals, so that it can better synergize with the fluorine-containing silicone epoxy resin and enhance the overall anti-corrosion performance of the paint film. DETAILED DESCRIPTION

[0037] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example

[0038] This embodiment is a method for preparing a water-based two-component epoxy anticorrosive paint, comprising the following steps:

[0039] Step S1: 15 g of trifluoropropylmethylcyclotrisiloxane and 0.3 g of tetramethyldisiloxane are added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen is introduced for protection. The mixture is stirred and reacted for 30 min at a temperature of 25° C. and a stirring rate of 300 r / min. Then, 0.3 mL of trifluoromethanesulfonic acid is added and the stirring reaction is continued for 5 min. Then, the mixture is heated to 50° C. and the stirring reaction is continued for 20 h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to n-heptane, and then dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then small molecular low-boiling substances are distilled off at a temperature of 180° C. to obtain hydrogen-containing fluoropolysiloxane;

[0040] Step S2: 30 g of hydrogen-containing fluoropolysiloxane, 2.5 g of eugenol, 0.5 g of KARSTEDT catalyst and 40 mL of anhydrous toluene were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred for reaction at 25° C. and a stirring rate of 300 r / min for 25 min, and then the mixture was heated to 80° C. and stirred for reaction for 8 h, and then heated to 90° C. and stirred for reaction for 2 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain terminal hydroxyl fluoropolysiloxane;

[0041] Step S3: 20 g of terminal hydroxyl fluorinated polysiloxane, 0.6 g of benzyltriethylammonium chloride and 60 mL of epichlorohydrin are added to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred for reaction at a temperature of 25° C. and a stirring rate of 300 r / min for 20 min, then heated to 80° C. and continued to stir for reaction for 3 h, then added dropwise with stirring a 35% sodium hydroxide solution, and the dropping rate was controlled to be 1 drop / s. After the dropwise addition, the stirring reaction was continued for 1 h. After the reaction was completed, the reaction product was cooled to room temperature, and then added to distilled water, and then allowed to stand for stratification, the organic phase was dried over anhydrous magnesium sulfate, and then vacuum filtered, the filtrate was rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 80° C. for 6 h to obtain a fluorinated organosilicon epoxy resin;

[0042] Step S4: 5g of graphite powder, 90mL of 98% concentrated sulfuric acid, 13mL of phosphoric acid and 2.5g of sodium nitrate are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, and nitrogen is introduced for protection. The reaction is stirred for 20min at a temperature of 0°C and a stirring rate of 300r / min, and then 15g of potassium permanganate is added and the temperature is raised to 45°C and the stirring reaction is continued for 1h, and then the temperature is raised to 95°C and the stirring reaction is continued for 1h. After the reaction is completed, the reaction product is poured into ice water, and then 15mL of 30% hydrogen peroxide solution is added, and then it is allowed to stand for 8h, and then centrifuged. The precipitate is washed 3 times with 8% hydrochloric acid solution and distilled water in sequence, and then placed in a vacuum drying oven and dried at a temperature of 90°C for 5h to obtain graphene oxide;

[0043] Step S5: 1 g of graphene oxide, 100 mL of deionized water, 2.5 g of L-glutamic acid and 40 mL of a 30 mL sodium hydroxide solution were added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 30 min at an ultrasonic frequency of 40 kHz, and then stirred for 8 h at a temperature of 40° C. and a stirring rate of 300 r / min. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with anhydrous ethanol and distilled water for 3 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 50° C. for 2 h to obtain glutamic acid-modified graphene oxide;

[0044] Step S6: weighing 35 parts of fluorine-containing silicone epoxy resin, 18 parts of deionized water, 1.1 parts of glutamic acid-modified graphene oxide, 0.5 parts of dispersant, 0.2 parts of defoamer, 0.1 parts of wetting agent, 25 parts of amine curing agent and 11 parts of deionized water according to weight; the dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; the amine curing agent is polyetheramine curing agent T5000;

[0045] Step S7: adding fluorinated organosilicon epoxy resin, deionized water, glutamic acid-modified graphene oxide, dispersant, defoamer and wetting agent into a mixer and mixing them evenly to obtain component A;

[0046] Step S8: adding an amine curing agent and deionized water into a mixer and mixing them evenly to obtain component B;

[0047] Step S9: Evenly mix component A and component B in a mass ratio of 1:0.3 to obtain a water-based two-component epoxy anticorrosive paint. Example

[0048] This embodiment is a method for preparing a water-based two-component epoxy anticorrosive paint, comprising the following steps:

[0049] Step S1: 18 g of trifluoropropylmethylcyclotrisiloxane and 0.8 g of tetramethyldisiloxane are added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen is introduced for protection. The mixture is stirred for reaction at 28° C. and a stirring rate of 350 r / min for 35 min, and then 0.4 mL of trifluoromethanesulfonic acid is added for continued stirring for reaction for 8 min. The mixture is then heated to 52° C. and continued to stir for reaction for 22 h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to n-heptane, and then dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then small molecular weight low-boiling substances are distilled off at a temperature of 182° C. to obtain hydrogen-containing fluoropolysiloxane;

[0050] Step S2: 35 g of hydrogen-containing fluoropolysiloxane, 3 g of eugenol, 0.7 g of KARSTEDT catalyst and 45 mL of anhydrous toluene were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred at 28° C. and a stirring rate of 350 r / min for 28 min, and then the mixture was heated to 82° C. and stirred for 9 h, and then heated to 92° C. and stirred for 2.5 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain terminal hydroxyl fluoropolysiloxane;

[0051] Step S3: 25g of terminal hydroxyl fluorinated polysiloxane, 0.9g of benzyltriethylammonium chloride and 70mL of epichlorohydrin are added to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and stirred for reaction at a temperature of 28°C and a stirring rate of 350r / min for 25min, then heated to 82°C and continued to stir for reaction for 4h, then added dropwise with stirring a 38% sodium hydroxide solution, and the dropping rate was controlled to be 1 drop / s. After the dropwise addition, the stirring reaction was continued for 1.5h. After the reaction was completed, the reaction product was cooled to room temperature, then added to distilled water, then allowed to stand for stratification, the organic phase was dried with anhydrous magnesium sulfate, then vacuum filtered, the filtrate was rotary evaporated to remove the solvent, then placed in a vacuum drying oven, and dried at a temperature of 82°C for 7h to obtain a fluorinated organosilicon epoxy resin;

[0052] Step S4: 5g of graphite powder, 95mL of 98% concentrated sulfuric acid, 14mL of phosphoric acid and 3g of sodium nitrate are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 3°C and a stirring rate of 350r / min for 25min, and then 18g of potassium permanganate is added and the mixture is stirred for reaction for 1h at a temperature of 48°C, and then the mixture is stirred for reaction for 1h at a temperature of 98°C. After the reaction is completed, the reaction product is poured into ice water, and then 18mL of 30% hydrogen peroxide solution is added, and then the mixture is allowed to stand for 9h, and then centrifuged. The precipitate is washed 4 times with a 9% hydrochloric acid solution and distilled water, and then placed in a vacuum drying oven and dried at a temperature of 95°C for 5.5h to obtain graphene oxide;

[0053] Step S5: 1 g of graphene oxide, 110 mL of deionized water, 3.5 g of L-glutamic acid and 45 mL of a sodium hydroxide solution with a mass fraction of 35 mL were added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 35 min at an ultrasonic frequency of 45 kHz, and then stirred for 9 h at a temperature of 42 ° C and a stirring rate of 350 r / min. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with anhydrous ethanol and distilled water for 4 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 52 ° C for 2.5 h to obtain glutamic acid modified graphene oxide;

[0054] Step S6: weighing 40 parts of fluorine-containing silicone epoxy resin, 21 parts of deionized water, 1.7 parts of glutamic acid-modified graphene oxide, 1 part of dispersant, 0.4 parts of defoamer, 0.3 parts of wetting agent, 29 parts of amine curing agent and 13 parts of deionized water according to weight; the dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; the amine curing agent is polyetheramine curing agent T5000;

[0055] Step S7: adding fluorinated organosilicon epoxy resin, deionized water, glutamic acid-modified graphene oxide, dispersant, defoamer and wetting agent into a mixer and mixing them evenly to obtain component A;

[0056] Step S8: adding an amine curing agent and deionized water into a mixer and mixing them evenly to obtain component B;

[0057] Step S9: Evenly mix component A and component B in a mass ratio of 1:0.5 to obtain a water-based two-component epoxy anticorrosive paint. Example

[0058] This embodiment is a method for preparing a water-based two-component epoxy anticorrosive paint, comprising the following steps:

[0059] Step S1: 20 g of trifluoropropylmethylcyclotrisiloxane and 1.3 g of tetramethyldisiloxane are added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen is introduced for protection. The mixture is stirred and reacted for 40 min at a temperature of 30° C. and a stirring rate of 400 r / min, and then 0.5 mL of trifluoromethanesulfonic acid is added to continue stirring and reacting for 10 min. The mixture is then heated to 55° C. and continued to stir and react for 25 h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to n-heptane, and then dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then small molecular low-boiling substances are distilled off at a temperature of 185° C. to obtain hydrogen-containing fluoropolysiloxane;

[0060] Step S2: 40 g of hydrogen-containing fluoropolysiloxane, 3.5 g of eugenol, 0.9 g of KARSTEDT catalyst and 50 mL of anhydrous toluene were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then the temperature was raised to 85° C. and the stirring reaction was continued for 10 h. The temperature was then raised to 95° C. and the stirring reaction was continued for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain terminal hydroxyl fluoropolysiloxane;

[0061] Step S3: 30 g of terminal hydroxyl fluorinated polysiloxane, 1.2 g of benzyltriethylammonium chloride and 80 mL of epichlorohydrin are added to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and the mixture is stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then the mixture is heated to 85° C. and the stirring reaction is continued for 5 h, and then a sodium hydroxide solution with a mass fraction of 40% is added dropwise while stirring, and the dropping rate is controlled to be 2 drops / s. After the dropwise addition is completed, the stirring reaction is continued for 2 h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to distilled water, and then allowed to stand for stratification, the organic phase is dried over anhydrous magnesium sulfate, and then vacuum filtered, the filtrate is rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 85° C. for 8 h to obtain a fluorinated organosilicon epoxy resin;

[0062] Step S4: 5g of graphite powder, 100mL of 98% concentrated sulfuric acid, 15mL of phosphoric acid and 3.5g of sodium nitrate are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 5°C and a stirring rate of 400r / min for 30min, and then 20g of potassium permanganate is added and the mixture is heated to 50°C and stirred for reaction for 1.5h, and then heated to 100°C and stirred for reaction for 1.5h. After the reaction is completed, the reaction product is poured into ice water, and then 20mL of 30% hydrogen peroxide solution is added, and then the mixture is allowed to stand for 10h, and then centrifuged. The precipitate is washed 5 times with 10% hydrochloric acid solution and distilled water in sequence, and then placed in a vacuum drying oven and dried at a temperature of 100°C for 6h to obtain graphene oxide;

[0063] Step S5: 1 g of graphene oxide, 120 mL of deionized water, 4.5 g of L-glutamic acid and 50 mL of a 40% sodium hydroxide solution were added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 40 min at an ultrasonic frequency of 50 kHz, and then stirred for 10 h at a temperature of 45° C. and a stirring rate of 400 r / min. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with anhydrous ethanol and distilled water for 5 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 55° C. for 3 h to obtain glutamic acid-modified graphene oxide;

[0064] Step S6: weighing 45 parts of fluorine-containing silicone epoxy resin, 24 parts of deionized water, 2.3 parts of glutamic acid-modified graphene oxide, 1.5 parts of dispersant, 0.6 parts of defoamer, 0.5 parts of wetting agent, 33 parts of amine curing agent and 15 parts of deionized water according to weight; the dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; the amine curing agent is polyetheramine curing agent T5000;

[0065] Step S7: adding fluorinated organosilicon epoxy resin, deionized water, glutamic acid-modified graphene oxide, dispersant, defoamer and wetting agent into a mixer and mixing them evenly to obtain component A;

[0066] Step S8: adding an amine curing agent and deionized water into a mixer and mixing them evenly to obtain component B;

[0067] Step S9: Evenly mix component A and component B in a mass ratio of 1:0.6 to obtain a water-based two-component epoxy anticorrosive paint.

[0068] Comparative Example 1: This comparative example is a method for preparing a water-based two-component epoxy anticorrosive paint, comprising the following steps:

[0069] Step S1: Weigh 45 parts of E-51 epoxy resin, 24 parts of deionized water, 1.5 parts of dispersant, 0.6 parts of defoamer, 0.5 parts of wetting agent, 33 parts of amine curing agent and 15 parts of deionized water according to weight; the dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; the amine curing agent is polyetheramine curing agent T5000;

[0070] Step S2: adding E-51 epoxy resin, deionized water, dispersant, defoamer and wetting agent into a mixer and mixing them evenly to obtain component A;

[0071] Step S3: adding an amine curing agent and deionized water into a mixer and mixing them evenly to obtain component B;

[0072] Step S4: Evenly mix component A and component B in a mass ratio of 1:0.6 to obtain a water-based two-component epoxy anticorrosive paint.

[0073] Comparative Example 2: This comparative example is a method for preparing a water-based two-component epoxy anticorrosive paint, comprising the following steps:

[0074] Step S1: 20 g of trifluoropropylmethylcyclotrisiloxane and 1.3 g of tetramethyldisiloxane are added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen is introduced for protection. The mixture is stirred and reacted for 40 min at a temperature of 30° C. and a stirring rate of 400 r / min, and then 0.5 mL of trifluoromethanesulfonic acid is added to continue stirring and reacting for 10 min. The mixture is then heated to 55° C. and continued to stir and react for 25 h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to n-heptane, and then dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then small molecular low-boiling substances are distilled off at a temperature of 185° C. to obtain hydrogen-containing fluoropolysiloxane;

[0075] Step S2: 40 g of hydrogen-containing fluoropolysiloxane, 3.5 g of eugenol, 0.9 g of KARSTEDT catalyst and 50 mL of anhydrous toluene were added to a three-necked flask equipped with a stirrer, a thermometer and an air duct, and nitrogen was introduced for protection. The mixture was stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then the temperature was raised to 85° C. and the stirring reaction was continued for 10 h. The temperature was then raised to 95° C. and the stirring reaction was continued for 3 h. After the reaction was completed, the reaction product was cooled to room temperature, and then the solvent was removed by rotary evaporation to obtain terminal hydroxyl fluoropolysiloxane;

[0076] Step S3: 30 g of terminal hydroxyl fluorinated polysiloxane, 1.2 g of benzyltriethylammonium chloride and 80 mL of epichlorohydrin are added to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, and the mixture is stirred for reaction at a temperature of 30° C. and a stirring rate of 400 r / min for 30 min, and then the mixture is heated to 85° C. and the stirring reaction is continued for 5 h, and then a sodium hydroxide solution with a mass fraction of 40% is added dropwise while stirring, and the dropping rate is controlled to be 2 drops / s. After the dropwise addition is completed, the stirring reaction is continued for 2 h. After the reaction is completed, the reaction product is cooled to room temperature, and then added to distilled water, and then allowed to stand for stratification, the organic phase is dried over anhydrous magnesium sulfate, and then vacuum filtered, the filtrate is rotary evaporated to remove the solvent, and then placed in a vacuum drying oven and dried at a temperature of 85° C. for 8 h to obtain a fluorinated organosilicon epoxy resin;

[0077] Step S4: Weigh 45 parts of fluorine-containing silicone epoxy resin, 24 parts of deionized water, 1.5 parts of dispersant, 0.6 parts of defoamer, 0.5 parts of wetting agent, 33 parts of amine curing agent and 15 parts of deionized water according to weight; the dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; the amine curing agent is polyetheramine curing agent T5000;

[0078] Step S5: adding fluorine-containing organosilicon epoxy resin, deionized water, dispersant, defoamer and wetting agent into a mixer and mixing them evenly to obtain component A;

[0079] Step S6: adding an amine curing agent and deionized water into a mixer and mixing them evenly to obtain component B;

[0080] Step S7: Evenly mix component A and component B in a mass ratio of 1:0.6 to obtain a water-based two-component epoxy anticorrosive paint.

[0081] Comparative Example 3: This comparative example is a method for preparing a water-based two-component epoxy anticorrosive paint, comprising the following steps:

[0082] Step S1: 5g of graphite powder, 100mL of concentrated sulfuric acid with a mass fraction of 98%, 15mL of phosphoric acid and 3.5g of sodium nitrate are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 5°C and a stirring rate of 400r / min for 30min, and then 20g of potassium permanganate is added and the mixture is heated to 50°C and stirred for reaction for 1.5h, and then heated to 100°C and stirred for reaction for 1.5h. After the reaction is completed, the reaction product is poured into ice water, and then 20mL of a hydrogen peroxide solution with a mass fraction of 30% is added, and then the mixture is allowed to stand for 10h, and then centrifuged. The precipitate is washed 5 times with a hydrochloric acid solution with a mass fraction and distilled water, and then placed in a vacuum drying oven and dried at a temperature of 100°C for 6h to obtain graphene oxide;

[0083] Step S2: 1 g of graphene oxide, 120 mL of deionized water, 4.5 g of L-glutamic acid and 50 mL of a 40% sodium hydroxide solution were added to a three-necked flask equipped with a stirrer and a thermometer, and ultrasonically treated for 40 min at an ultrasonic frequency of 50 kHz, and then stirred for 10 h at a temperature of 45 ° C and a stirring rate of 400 r / min. After the reaction was completed, the reaction product was cooled to room temperature and then centrifuged. The precipitate was washed with anhydrous ethanol and distilled water for 5 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 55 ° C for 3 h to obtain glutamic acid modified graphene oxide;

[0084] Step S3: Weigh 45 parts of E-51 epoxy resin, 24 parts of deionized water, 2.3 parts of glutamic acid-modified graphene oxide, 1.5 parts of dispersant, 0.6 parts of defoamer, 0.5 parts of wetting agent, 33 parts of amine curing agent and 15 parts of deionized water according to weight; the dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; the amine curing agent is polyetheramine curing agent T5000;

[0085] Step S4: adding E-51 epoxy resin, deionized water, glutamic acid-modified graphene oxide, dispersant, defoamer and wetting agent into a mixer and mixing them evenly to obtain component A;

[0086] Step S5: adding an amine curing agent and deionized water into a mixer and mixing them evenly to obtain component B;

[0087] Step S6: Evenly mix component A and component B in a mass ratio of 1:0.6 to obtain a water-based two-component epoxy anticorrosive paint.

[0088] Performance test: The surface oil stains of Q235 low carbon steel sheet were removed by detergent, cleaned with anhydrous ethanol and deionized water, and dried at room temperature. Then, the water-based two-component epoxy anti-corrosion paints of Examples 1-3 and Comparative Examples 1-3 were applied to the Q235 low carbon steel sheet by an automatic coating machine. After drying at room temperature for 7 days and completely curing, a water-based two-component epoxy anti-corrosion paint coating with a coating thickness of 200±10μm was obtained. The salt water immersion resistance of the water-based two-component epoxy anti-corrosion paint coating was tested by GB / T 10834-2008, and the corrosion rate of the coating was calculated by the weight loss method. The acid and alkali resistance of the coating was analyzed according to GB / T 9274-1988.

[0089] The test results are shown in the following table:

[0090] .

[0091] Referring to the data in the above table, based on the comparison between Examples 1-3 and Comparative Examples 1-3, it can be seen that the water-based two-component epoxy anti-corrosion paint using fluorinated silicone epoxy resin and adding glutamic acid-modified graphene oxide has excellent corrosion resistance.

[0092] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0093] The above contents are merely examples and explanations of the present invention. Those skilled in the art may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the invention or exceed the scope defined by the claims, they shall all fall within the protection scope of the present invention.

Claims

1. A water-based two-component epoxy anticorrosive paint, It is characterized in that It includes component A and component B; The mass ratio of component A to component B is 1:0.3-0.6; Wherein, the component A comprises the following components in parts by weight: 35-45 parts of fluorinated silicone epoxy resin, 18-24 parts of deionized water, 1.1-2.3 parts of glutamic acid modified graphene oxide, 0.5-1.5 parts of dispersant, 0.2-0.6 parts of defoamer and 0.1-0.5 parts of wetting agent; Wherein, the component B comprises the following components in parts by weight: 25-33 parts of amine curing agent, 11-15 parts of deionized water; Wherein, the fluorine-containing silicone epoxy resin is prepared by the following steps: Step A1: trifluoropropylmethylcyclotrisiloxane and tetramethyldisiloxane are added to a three-necked flask equipped with a stirrer, a thermometer and an air guide tube, and nitrogen is introduced for protection. The mixture is stirred and reacted for 30-40 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min. Trifluoromethanesulfonic acid is then added and stirred and reacted for 5-10 minutes. The mixture is then heated to 50-55° C. and stirred and reacted for 20-25 hours. After the reaction is completed, the reaction product is cooled to room temperature, added to n-heptane, dried with anhydrous magnesium sulfate, and then vacuum filtered. The filtrate is rotary evaporated to remove the solvent, and then small molecular low-boiling substances are distilled off at a temperature of 180-185° C. to obtain hydrogen-containing fluoropolysiloxane; Step A2: Add hydrogen-containing fluoropolysiloxane, eugenol, KARSTEDT catalyst and anhydrous toluene into a three-necked flask equipped with a stirrer, a thermometer and an air duct, introduce nitrogen protection, stir and react for 25-30 minutes at a temperature of 25-30° C. and a stirring rate of 300-400 r / min, then heat to 80-85° C. and continue to stir and react for 8-10 hours, then heat to 90-95° C. and continue to stir and react for 2-3 hours, after the reaction is completed, cool the reaction product to room temperature, and then rotary evaporate to remove the solvent to obtain terminal hydroxyl fluoropolysiloxane; Step A3: Add terminal hydroxyl fluorinated polysiloxane, benzyltriethylammonium chloride and epichlorohydrin to a three-necked flask equipped with a stirrer, a thermometer and a constant pressure dropping funnel, stir and react for 20-30 minutes at a temperature of 25-30°C and a stirring rate of 300-400r / min, then heat to 80-85°C and continue to stir and react for 3-5 hours, then add sodium hydroxide solution dropwise while stirring, control the dropping rate to 1-2 drops / s, continue to stir and react for 1-2 hours after the dropwise addition is completed, and after the reaction is completed, cool the reaction product to room temperature, then add it to distilled water, then stand and stratify, dry the organic phase with anhydrous magnesium sulfate, then vacuum filter, rotary evaporate the filtrate to remove the solvent, then place it in a vacuum drying oven, and dry it at a temperature of 80-85°C for 6-8 hours to obtain a fluorinated organosilicon epoxy resin; The glutamic acid modified graphene oxide is prepared by the following steps: Step B1: Graphite powder, concentrated sulfuric acid, phosphoric acid and sodium nitrate are added to a three-necked flask equipped with a stirrer, a thermometer, an air guide tube and a reflux condenser, and nitrogen is introduced for protection. The mixture is stirred for reaction at a temperature of 0-5°C and a stirring rate of 300-400r / min for 20-30min, and then potassium permanganate is added and the mixture is heated to 45-50°C and stirred for reaction for 1-1.5h, and then heated to 95-100°C and stirred for reaction for 1-1.5h. After the reaction is completed, the reaction product is poured into ice water, and then a hydrogen peroxide solution is added, and then the mixture is allowed to stand for 8-10h, and then centrifuged. The precipitate is washed with hydrochloric acid solution and distilled water for 3-5 times in sequence, and then placed in a vacuum drying oven and dried at a temperature of 90-100°C for 5-6h to obtain graphene oxide; Step B2: Add graphene oxide, deionized water, L-glutamic acid and sodium hydroxide solution to a three-necked flask equipped with a stirrer and a thermometer, perform ultrasonic treatment at an ultrasonic frequency of 40-50kHz for 30-40min, then stir the reaction at a temperature of 40-45°C and a stirring rate of 300-400r / min for 8-10h. After the reaction, cool the reaction product to room temperature and then centrifuge it. Wash the precipitate with anhydrous ethanol and distilled water for 3-5 times in turn, then place it in a vacuum drying oven and dry it at a temperature of 50-55°C for 2-3h to obtain glutamic acid modified graphene oxide.

2. A water-based two-component epoxy anticorrosive paint according to claim 1, It is characterized in that The usage ratio of the trifluoropropylmethylcyclotrisiloxane, tetramethyldisiloxane and trifluoromethanesulfonic acid in step A1 is 15-20 g: 0.3-1.3 g: 0.3-0.5 mL.

3. A water-based two-component epoxy anticorrosive paint according to claim 1, It is characterized in that The usage ratio of the hydrogen-containing fluoropolysiloxane, eugenol, KARSTEDT catalyst and anhydrous toluene in step A2 is 30-40 g: 2.5-3.5 g: 0.5-0.9 g: 40-50 mL.

4. A water-based two-component epoxy anticorrosive paint according to claim 1, It is characterized in that The amount ratio of the terminal hydroxyl fluorinated polysiloxane, benzyltriethylammonium chloride and epichlorohydrin in step A3 is 20-30 g: 0.6-1.2 g: 60-80 mL; the mass fraction of the sodium hydroxide solution is 35-40%.

5. A water-based two-component epoxy anticorrosive paint according to claim 1, It is characterized in that The amount ratio of the graphite powder, concentrated sulfuric acid, phosphoric acid, sodium nitrate, potassium permanganate and hydrogen peroxide solution in step B1 is 5g:90-100mL:13-15mL:2.5-3.5g:15-20g:15-20mL; the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide solution is 30%.

6. A water-based two-component epoxy anticorrosive paint according to claim 1, It is characterized in that The amount ratio of the graphene oxide, deionized water, L-glutamic acid and sodium hydroxide solution in step B2 is 1g:100-120mL:2.5-4.5g:40-50mL; the mass fraction of the sodium hydroxide solution is 30-40%.

7. A method for preparing a water-based two-component epoxy anticorrosive paint according to any one of claims 1 to 6, It is characterized in that The following steps are involved: Step 1: Weigh 35-45 parts of fluorinated silicone epoxy resin, 18-24 parts of deionized water, 1.1-2.3 parts of glutamic acid modified graphene oxide, 0.5-1.5 parts of dispersant, 0.2-0.6 parts of defoamer, 0.1-0.5 parts of wetting agent, 25-33 parts of amine curing agent and 11-15 parts of deionized water according to weight parts; Step 2: adding fluorinated organosilicon epoxy resin, deionized water, glutamic acid-modified graphene oxide, dispersant, defoamer and wetting agent into a mixer and mixing evenly to obtain component A; Step 3: Add the amine curing agent and deionized water into a mixer and mix them evenly to obtain component B; Step 4: Evenly mix component A and component B in a mass ratio of 1:0.3-0.6 to obtain a water-based two-component epoxy anticorrosive paint.

8. A method for preparing a water-based two-component epoxy anticorrosive paint according to claim 7, It is characterized in that The dispersant is CF-10 dispersant; the defoamer is HT-608 defoamer; the wetting agent is water-based system wetting agent RF-875; and the amine curing agent is polyetheramine curing agent T5000.