CN113736343A

CN113736343A - Synthesis method of corrosion-resistant cathode electrophoretic coating

Info

Publication number: CN113736343A
Application number: CN202111119320.5A
Authority: CN
Inventors: 王洪涛
Original assignee: Zaoyang Wangqian Electrophoretic Coating Co ltd
Current assignee: Zaoyang Wangqian Electrophoretic Coating Co ltd
Priority date: 2021-09-23
Filing date: 2021-09-23
Publication date: 2021-12-03

Abstract

The invention provides a synthesis method of a corrosion-resistant cathode electrophoretic coating, belonging to the technical field of electrophoretic coatings. The synthesis method of the corrosion-resistant cathode electrophoretic coating comprises the following raw materials in percentage by mass: 31.5-40.5% of modified epoxy resin, 3.5-4.4% of carboxyl-terminated nitrile rubber, 1-2% of catalyst slurry, 3-5% of color paste, 7-10% of mixed solvent, 2-4% of thickening agent and 35-55% of diluent, wherein the modified epoxy resin, the carboxyl-terminated nitrile rubber and acrylate resin form main resin.

Description

Synthesis method of corrosion-resistant cathode electrophoretic coating

Technical Field

The application relates to the field of coatings, in particular to a synthesis method of a corrosion-resistant cathode electrophoretic coating.

Background

The anticorrosive cathodic electrophoretic paint is a double component, one component is white uniform emulsion liquid, and the other component is gray (or black) pigment slurry.

The corrosion-resistant cathode electrophoretic coating in the related technology is mainly produced by high-temperature mixing reaction of epoxy resin, deionized water, corresponding pigment and mixed auxiliary agent, only the epoxy resin is adopted as main resin, the weather resistance, the aging resistance and the gloss retention are poor, the mixed auxiliary agent in the related technology usually only contains a shrinkage-proof agent, a neutralizing agent, an antifoaming agent, a mildew preventive, an anti-wrinkling agent, an anti-settling agent, an antirust agent and a catalyst with low toxicity, so that the advection performance and the corrosion resistance after the coating is produced are difficult to improve, the appearance of a workpiece with the coating on the surface is rough, the service life of the workpiece is shortened, the environmental protection performance of the coating during the whole use can not be improved, and the experience feeling of the coating in use is greatly reduced.

How to invent a synthesis method of a corrosion-resistant cathode electrophoretic coating to improve the problems becomes a problem to be solved by the technical personnel in the field.

Disclosure of Invention

In order to make up for the above deficiencies, the application provides a method for synthesizing a corrosion-resistant cathode electrophoretic coating, aiming at solving the problems that the advection performance and the corrosion resistance of the corrosion-resistant cathode electrophoretic coating in the related art after the coating is produced are difficult to improve, and the environmental protection performance of the coating in use can not be improved.

In order to achieve the purpose, the invention provides the following technical scheme: a synthesis method of a corrosion-resistant cathode electrophoresis paint comprises the following raw materials by mass percent: 31.5 to 40.5 percent of modified epoxy resin, 3.5 to 4.4 percent of carboxyl-terminated nitrile rubber, 1 to 2 percent of catalyst slurry, 3 to 5 percent of color paste, 7 to 10 percent of mixed solvent, 2 to 4 percent of thickening agent and 35 to 55 percent of diluent.

In a specific embodiment, the modified epoxy resin, the carboxyl-terminated nitrile rubber and the acrylate resin form a main resin, and the main resin is synthesized by a method comprising the following steps:

s1: taking materials, namely mixing the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber acrylate resin according to the weight ratio of 7.2: 0.8: 2, putting the mixture into two barrels with the same weight for weighing and proportioning for later use;

s2: mixing, taking a mixing tank with a stirrer, pouring the solution in the two barrels into the mixing tank from a feeding port on the mixing tank, starting the stirrer to mix and stir the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber in the tank at a rotating speed of 40-60 minutes for 10 minutes to obtain a mixed solution A, namely a main resin solution.

In a specific embodiment, the catalyst slurry comprises the following raw materials in percentage by mass: 17-19% of an auxiliary agent I, 3-5% of an acid solution, 3-5% of a binder, 35-40% of deionized water, 1-2% of alumina powder, 1-2% of zirconium dioxide, 17-19% of an auxiliary agent II, 17-19% of an auxiliary agent III and 4-5% of an active component agent, wherein the auxiliary agent I is one or more of alkali metal salts and alkali metal oxides, and the alkali metal comprises any one or more of Li, Na, K, Rb and Cs.

In a specific embodiment, the acid solution comprises any one or more of nitric acid, hydrochloric acid and citric acid, the binder is MS modified silane, the auxiliary agent II comprises any one or more of lanthanide metals and oxides thereof, and the lanthanide metals comprise any one or more of La, Ce and Nd and Lu; the auxiliary agent III comprises one or more of polyvinyl alcohol, polyethylene glycol, polyurethane, acrylate, modified acrylate, polyacrylate and cellulose, the active component agent comprises one or more of noble metal, noble metal salt and noble metal oxide, and the noble metal comprises one or more of Pd, Pt and Ru and Rh.

In a specific embodiment, the method for synthesizing the catalyst slurry comprises the following steps:

s1: taking materials, namely weighing and proportioning an auxiliary agent I, an acid solution, a binder, deionized water, alumina powder, zirconium dioxide, an auxiliary agent II, an auxiliary agent III and an active component agent by using an external electronic scale according to mass percentage for later use;

s2: grinding and mixing, namely firstly putting the auxiliary agent I, a certain amount of acid solution, deionized water and a binding agent into a stirring tank for mixing, adjusting the rotating speed of a servo motor arranged in the stirring tank to 40-60 revolutions, stirring into a viscous state to obtain a mixed solution A, then adding alumina powder and zirconium dioxide into the mixed solution A, continuously stirring at the same rotating speed for 10-15 minutes to obtain a mixed solution B, then pouring the auxiliary agent II, the auxiliary agent III and the mixed solution B into a ball mill for grinding and stirring, stirring for 10-15 minutes to obtain a mixed solution C, then adding an active component agent, continuously stirring, stirring for 5-8 minutes to obtain a mixed solution D, testing the pH value of the mixed solution D according to a pH value tester arranged in the ball mill, and obtaining a catalyst slurry after the test is qualified, and after the test is unqualified, adding a proper amount of acid solution and deionized water for pH value debugging until qualified catalyst slurry is obtained.

In a specific embodiment, the color paste comprises the following raw materials in percentage by mass: 3-5.5% of catalyst slurry, 35-45% of main resin, 40-55% of deionized water, 5-9% of pigment and 1-1.5% of cosolvent.

In a specific embodiment, the method for synthesizing the color paste comprises the following steps:

s1: taking materials, weighing and proportioning the catalyst slurry, the main resin, the deionized water, the pigment and the cosolvent by using an external electronic scale according to mass percent for later use;

s2: grinding and mixing, pouring the main resin and deionized water into a mixing tank for mixing, adding catalyst slurry for dispersion catalysis, wherein the mixing time is 10-15 minutes to obtain a solution A, pouring the pigment and the catalyzed solution A into a ball mill for grinding and mixing, controlling the rotating speed of the ball mill at 40-60 rpm, grinding and mixing for 5-8 minutes to obtain a solution B, diluting the cosolvent by adding deionized water, adding the diluted cosolvent into the solution B for continuous stirring, and stirring for 3-5 minutes to obtain the color paste.

In a specific embodiment, the thickener is specifically an acrylate copolymer thickener that is a milky white liquid with a viscosity of 2500-.

In a specific embodiment, the mixed solvent comprises an organic bismuth catalyst, an anti-cratering agent, an aqueous adhesion promoter, a neutralizer, a mildew preventive, an anti-wrinkling agent, an anti-settling agent, an anti-rust agent and a defoaming agent, wherein the anti-cratering agent is any one or all of polyethylene wax or polyamide wax, the anti-cratering agent is one of polyacrylic acid and cellulose acetate butyrate, the anti-cratering agent is ethylene glycol monobutyl ether, the neutralizer is one or more of glacial acetic acid and formic acid, and the defoaming agent is any one or more of emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.

The invention also provides a synthesis method of the corrosion-resistant cathode electrophoretic coating, which comprises the following steps:

s1: taking materials, namely weighing and proportioning modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber, catalyst slurry, color slurry, a mixed solvent, a thickening agent and a diluting agent according to mass percent by using an external electronic scale for later use;

s2: mixing, namely adding a diluent into a reaction kettle, adding main resin into the reaction kettle through a feed inlet at the upper part of the reaction kettle for dissolving, wherein the reaction kettle is a stainless steel reaction kettle, the temperature in the reaction kettle is adjusted to 165-169.5 ℃, starting a servo motor at the top of the reaction kettle to stir the solution in the reaction kettle at the speed of 40-60 revolutions per minute for 10-20 minutes, and obtaining a mixed solution A after complete dissolution;

s3: adding materials, namely adding color paste, mixed solvent and thickening agent into the mixed solution A obtained in the step S2 through a feeding port at the upper part of the reaction kettle in sequence, keeping the temperature in the reaction kettle and the rotating speed of a servo motor at the top of the reaction kettle unchanged, and continuously stirring for 20-25 minutes to obtain the corrosion-resistant cathode electrophoretic coating emulsion;

s4: and (5) packaging, namely quantitatively filling the corrosion-resistant cathode electrophoretic coating emulsion obtained in the step S3 by using a full-automatic liquid filling machine, and merging the emulsion into a warehouse for storage.

Compared with the prior art, the invention has the beneficial effects that: the application adopts modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber and acrylate resin to form main body resin, promotes the determination of poor weather resistance, aging resistance and light retention property which are generated only by adopting epoxy resin as primer in the past, and also promotes the anti-embrittlement performance of cathode electrophoretic paint, the application adopts MS modified silane as a binder in catalyst slurry, the storage stability and the curing speed are better, the temperature resistance, antifouling performance and mechanical strength are higher, the cohesive effect with a workpiece is also better, the using effect of the catalyst slurry is effectively promoted, the application comprises an organic bismuth catalyst, a shrinkage-proof agent, a water-based adhesion promoter, a neutralizer, a mildew preventive, a crease-proof agent, an anti-settling agent, an antirust agent and a defoaming agent in a mixed solvent, and the organic bismuth catalyst belongs to an environment-friendly polyurethane catalyst, the toxicity is lower, the radioactivity is lower, the environment is protected, the anti-shrinkage agent can reduce irregular small depressions formed on the surface of a wet coating after being dried, the smoothness of the formed coating is improved, the adhesive force of the coating on the surface of a metal workpiece body can be improved through the water-based adhesive force promoter, the probability of stripping or paint falling after the workpiece body is long-term is reduced, the neutralizing agent is one or more of glacial acetic acid and formic acid in the application, the resin and color paste filler in a paint liquid can be mixed more uniformly through the neutralizing agent, so that the precipitation is not easy to generate, the leveling property is improved, the mildew preventive is selected as a composite mildew preventive, one or more organic acids are combined with a certain carrier, the original mildew inhibiting function of the organic acids is maintained and even improved, the corrosivity and the irritation of the organic acids are avoided or reduced, and the manufacturing effect of the electrophoretic coating is improved, the anti-wrinkling agent is ethylene glycol monobutyl ether, so that the glossiness and the fluidity of the coating are improved, the anti-wrinkling phenomenon of a coating film is reduced, the anti-settling agent is a rheological control agent of the coating, the coating has thixotropy, the viscosity is greatly improved, the adhesive force of the coating on the surface of a workpiece is further improved, the peeling phenomenon generated after the coating is used for a long time is reduced, the rust inhibitor can reduce the corrosion caused by the mixing reaction of oxygen and water on the metal surface and increase the stability of the coating in use, the defoaming agent can reduce the surface tension of the coating, prevent the formation of foam and improve the production quality of the coating, and in conclusion, the anti-wrinkling performance, the leveling performance, the mildew-proof, anti-corrosion and anti-rust performance and the stability of the coating can be improved when the wear-resistant cathode electrophoretic coating is prepared, the weather resistance and the aging resistance of the coating can also be improved, and better glossiness can be kept, meanwhile, the adhesive force between the coating and a workpiece can be increased, the coating is high in environmental friendliness and low in irritation in use, the curing speed of the coating is increased, and the preparation efficiency of the coating is indirectly improved.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

Example 1

A synthesis method of a corrosion-resistant cathode electrophoretic coating comprises the following raw materials by mass percent: 37.52% of modified epoxy resin, 3.5% of carboxyl-terminated nitrile rubber, 1% of catalyst slurry, 3% of color paste, 7% of mixed solvent, 2% of thickening agent and 42% of diluent, wherein the thickening agent is specifically acrylate copolymer thickening agent, the appearance is milky white liquid, the viscosity is 6000mpa.S, the stability is high, the advection performance of the electrophoretic paint can be improved, the biological stability is high, the service life of the electrophoretic paint can be effectively prolonged, and the diluent is specifically deionized water.

The modified epoxy resin, the carboxyl-terminated nitrile rubber and the acrylate resin form a main body resin, and the synthesis method of the main body resin comprises the following steps:

s1: taking materials, namely mixing the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber acrylate resin according to the weight ratio of 7.2: 0.8: 2, putting the mixture into two barrels with the same weight for weighing and proportioning for later use; according to the cathode electrophoretic paint, the modified epoxy resin, the carboxyl-terminated butadiene-acrylonitrile rubber and the acrylate resin are adopted to form the main body resin, so that the determination of poor weather resistance, aging resistance and gloss retention caused by only adopting the epoxy resin as a primer in the past is improved, and the embrittlement resistance of the cathode electrophoretic paint is also improved.

S2: and mixing, namely taking a mixing tank with a stirrer, pouring the solution in the two barrels into the mixing tank from a feeding port on the mixing tank, starting the stirrer to mix and stir the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber in the mixing tank at the rotating speed of 40 minutes per minute, and stirring for 10 minutes to obtain a mixed solution A, namely a main resin solution.

The catalyst slurry comprises the following raw materials in percentage by mass: 17% of an auxiliary agent I, 3% of an acid solution, 3% of a binder, 37% of deionized water, 1% of alumina powder, 1% of zirconium dioxide, 17% of an auxiliary agent II, 17% of an auxiliary agent III and 4% of an active component agent, wherein the auxiliary agent I is one or more of alkali metal salts and alkali metal oxides, the alkali metals include one or more of Li, Na, K, Rb and Cs, in the embodiment, the auxiliary agent I selects a metal salt, the acid solution includes one or more of nitric acid, hydrochloric acid and citric acid, in the embodiment, the acid solution adopts nitric acid, the binder is MS modified silane, the catalyst slurry adopts MS modified silane as the binder, the storage stability and the curing speed are good, the temperature resistance, the antifouling performance and the mechanical strength are high, and the auxiliary agent II includes one or more of lanthanide metals and oxides thereof, the lanthanide metal comprises one or more of La, Ce, Nd and Lu, in the embodiment, the auxiliary agent II adopts a mixture of La, Ce and Nd; the auxiliary agent III comprises one or more of polyvinyl alcohol, polyethylene glycol, polyurethane, acrylate, modified acrylate, polyacrylate and cellulose, in the embodiment, the auxiliary agent III is polyvinyl alcohol, the active component agent comprises one or more of noble metals, noble metal salts and noble metal oxides, the noble metals comprise one or more of Pd, Pt, Ru and Rh, and in the embodiment, the active component agent is noble metal salts.

Specifically, the synthesis method of the catalyst slurry comprises the following steps:

s2: grinding and mixing, namely firstly putting an auxiliary agent I, a certain amount of acid solution, deionized water and a binding agent into a stirring tank for mixing, regulating the rotating speed of a servo motor arranged in the stirring tank to 40 revolutions, stirring the mixture into a viscous state to obtain a mixed solution A, then adding aluminum oxide powder and zirconium dioxide into the mixed solution A, continuously stirring the mixture A at the rotating speed in the same range for 10 minutes to obtain a mixed solution B, then pouring an auxiliary agent II, an auxiliary agent III and the mixed solution B into a ball mill for grinding and stirring, stirring the mixture B for 10 minutes to obtain a mixed solution C, adding an active component agent, continuously stirring the mixture C for 5 minutes to obtain a mixed solution D, testing the pH value of the mixed solution D according to a pH value tester arranged in the ball mill, obtaining catalyst slurry after the test is qualified, then adding a proper amount of acid solution and deionized water for pH value debugging after the test is unqualified, until qualified catalyst slurry is obtained.

The color paste comprises the following raw materials in percentage by mass: 3% of catalyst slurry, 40% of main resin, 51% of deionized water, 5% of pigment and 1% of cosolvent.

The method for synthesizing the color paste comprises the following steps:

s1: taking materials, weighing and proportioning the catalyst slurry, the main resin, the deionized water, the pigment and the cosolvent according to mass percent by using an external electronic scale for later use;

s2: grinding and mixing, pouring the main resin and deionized water into a mixing tank for mixing, adding catalyst slurry for dispersion catalysis, wherein the mixing time is 10 minutes to obtain a solution A, then pouring the pigment and the catalyzed solution A into a ball mill for grinding and mixing, controlling the rotating speed of the ball mill at 40 revolutions per minute, grinding and mixing for 5 minutes to obtain a solution B, diluting the cosolvent with deionized water, adding the diluted cosolvent into the solution B for continuous stirring, and stirring for 3 minutes to obtain the color slurry.

The mixed solvent comprises an organic bismuth catalyst, a shrinkage-proof agent, a water-based adhesion promoter, a neutralizing agent, a mildew-proof agent, a crease-resist agent, an anti-settling agent, an antirust agent and a defoaming agent, wherein the organic bismuth catalyst belongs to an environment-friendly polyurethane catalyst, has low toxicity and low radioactivity and is environment-friendly, the water-based adhesion promoter can improve the adhesion of the coating on the surface of a metal workpiece body and reduce the probability of stripping or paint dropping of the workpiece body after a long time, the mildew-proof agent is selected to be a composite mildew-proof agent and is formed by combining one or more organic acids with a certain carrier, the original mildew-proof function of the organic acids is maintained or even improved, the corrosivity and the irritation of the organic acids are avoided or reduced, the manufacturing effect of the electrophoretic coating is improved, the anti-settling agent is any one or all of polyethylene wax or polyamide wax, the anti-settling agent is a rheological control agent of the coating, and enables the coating to have thixotropy, greatly improve viscosity, further improve adhesion of the coating on the surface of a workpiece, and reduce the peeling phenomenon generated after the coating is used for a long time.

The anti-shrinkage agent is one of polyacrylic acid and cellulose acetate butyrate, in the embodiment, the anti-shrinkage agent is polyacrylic acid, the anti-shrinkage agent can reduce irregular small depressions formed on the surface of a wet coating after being dried, the smoothness of the formed film is increased, the anti-wrinkling agent is ethylene glycol monobutyl ether, the glossiness and the fluidity of the coating are improved, and the anti-wrinkle phenomenon of the formed film of the coating is reduced, the neutralizing agent is one or more of glacial acetic acid and formic acid, in the embodiment, the neutralizing agent is glacial acetic acid, the resin and the color paste filler in the paint liquid can be uniformly mixed by using the neutralizing agent, so that the resin and the color paste filler are not easy to precipitate, the leveling performance is increased, the defoaming agent is one or more of emulsified silicone oil, a high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glyceryl ether and polydimethylsiloxane, in this embodiment, the defoaming agent is silicone emulsion, and the defoaming agent can reduce the surface tension of coating, prevents the foam formation, promotes coating production quality, and the rust inhibitor can reduce the corrosion that oxygen and water brought at metal surface mixing reaction, increases the stability of coating use.

In this embodiment, the present invention further provides a method for synthesizing a corrosion-resistant cathode electrophoretic coating, which specifically includes the following steps:

s1: taking materials, namely weighing and proportioning modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber, catalyst slurry, color slurry, mixed solvent, thickening agent and diluent by using an external electronic scale according to mass percent for later use;

s2: mixing, namely adding a diluent into a reaction kettle, adding main body resin into the reaction kettle through a feeding port at the upper part of the reaction kettle for dissolving, wherein the reaction kettle is a stainless steel reaction kettle, the temperature in the reaction kettle is adjusted to 165 ℃, a servo motor at the top of the reaction kettle is started to stir the solution in the reaction kettle at the speed of 40 revolutions per minute, the stirring time is 10 minutes, and after complete dissolution, a mixed solution A is obtained;

s3: adding materials, namely adding color paste, mixed solvent and thickening agent into the mixed solution A obtained in the step S2 through a feeding port at the upper part of the reaction kettle in sequence, keeping the temperature in the reaction kettle and the rotating speed of a servo motor at the top of the reaction kettle unchanged, and continuously stirring for 20 minutes to obtain corrosion-resistant cathode electrophoretic coating emulsion;

s4: and (5) packaging, namely quantitatively filling the corrosion-resistant cathode electrophoretic coating emulsion obtained in the step S3 by using a liquid filling machine, and merging into a warehouse for sealing.

Example 2

A synthesis method of a corrosion-resistant cathode electrophoretic coating comprises the following raw materials by mass percent: 40.5% of modified epoxy resin, 4.4% of carboxyl-terminated nitrile rubber, 2% of catalyst slurry, 5% of color paste, 10% of mixed solvent, 4% of thickening agent and 39.1% of diluent, wherein the thickening agent is specifically acrylate copolymer thickening agent, the appearance of the thickening agent is milky white liquid, the viscosity of the thickening agent is 5000mpa.S, the advection performance of the electrophoretic paint can be improved, the biological stability is high, the service life of the electrophoretic paint is prolonged, and the diluent is deionized water.

The modified epoxy resin, the carboxyl-terminated nitrile rubber and the acrylate resin form a main body resin, and the synthesis method of the main body resin comprises the following steps: s1: taking materials, namely mixing the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber acrylate resin according to the weight ratio of 7.2: 0.8: 2, putting the mixture into two barrels with the same weight for weighing and proportioning for later use; according to the cathode electrophoretic paint, the modified epoxy resin, the carboxyl-terminated butadiene-acrylonitrile rubber and the acrylate resin are adopted to form the main body resin, so that the determination of poor weather resistance, aging resistance and gloss retention caused by only adopting the epoxy resin as a primer in the past is improved, and the embrittlement resistance of the cathode electrophoretic paint is also improved. S2: mixing, taking a mixing tank with a stirrer, pouring the solution in the two barrels into the mixing tank from a feeding port on the mixing tank, starting the stirrer to mix and stir the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber in the mixing tank at the rotating speed of 60 minutes per minute, and stirring for 10 minutes to obtain a mixed solution A, namely a main resin solution.

The catalyst slurry comprises the following raw materials in percentage by mass: 17% of an auxiliary agent I, 4% of an acid solution, 4% of a binder, 37% of deionized water, 2% of alumina powder, 2% of zirconium dioxide, 17% of an auxiliary agent II, 17% of an auxiliary agent III and 5% of an active component agent, wherein the auxiliary agent I is one or more of alkali metal salts and alkali metal oxides, the alkali metals comprise one or more of Li, Na, K, Rb and Cs, in the embodiment, the auxiliary agent I is an alkali metal oxide, the acid solution comprises one or more of nitric acid, hydrochloric acid and citric acid, in the embodiment, the acid solution is hydrochloric acid, the binder is MS modified silane, the MS modified silane is adopted as the binder in the catalyst slurry, the storage stability and the curing speed are good, the temperature resistance, the antifouling performance and the mechanical strength are high, and the auxiliary agent II comprises one or more of lanthanide metals and oxides thereof, the lanthanide metal comprises one or more of La, Ce, Nd and Lu, in the embodiment, the auxiliary agent II is a mixture of La, Ce, Nd and Lu; the auxiliary agent III comprises one or more of polyvinyl alcohol, polyethylene glycol, polyurethane, acrylate, modified acrylate, polyacrylate and cellulose, in the embodiment, the auxiliary agent III is a mixture of polyacrylate and cellulose, the active component agent comprises one or more of noble metal, noble metal salt and noble metal oxide, the noble metal comprises one or more of Pd, Pt and Ru and Rh, and in the embodiment, the active component agent is a mixture of Pd, Pt and Ru.

The synthesis method of the catalyst slurry comprises the following steps: s1: taking materials, namely weighing and proportioning an auxiliary agent I, an acid solution, a binder, deionized water, alumina powder, zirconium dioxide, an auxiliary agent II, an auxiliary agent III and an active component agent by using an external electronic scale according to mass percentage for later use; s2: grinding and mixing, namely firstly adding the auxiliary agent I, a certain amount of acid solution, deionized water and a binder into a stirring tank for mixing, adjusting the rotating speed of a servo motor arranged in the stirring tank to 45 revolutions, stirring the mixture into a viscous state to obtain a mixed solution A, then adding alumina powder and zirconium dioxide into the mixed solution A, continuously stirring the mixture A at the rotating speed in the same range for 11 minutes to obtain a mixed solution B, then pouring the auxiliary agent II, the auxiliary agent III and the mixed solution B into a ball mill for grinding and stirring, stirring the mixture B for 11 minutes to obtain a mixed solution C, adding an active component agent, continuously stirring the mixture C for 6 minutes to obtain a mixed solution D, testing the pH value of the mixed solution D according to a pH value tester arranged in the ball mill, obtaining a catalyst slurry after the test is qualified, adding a proper amount of acid solution and deionized water for pH value debugging after the test is unqualified, until qualified catalyst slurry is obtained.

The color paste comprises the following raw materials in percentage by mass: 4% of catalyst slurry, 43% of main resin, 45% of deionized water, 7% of pigment and 1% of cosolvent. Wherein, 1 percent of cosolvent is beneficial to the faster decomposition and fusion of the pigment with deionized water and main resin, and the synthesis method of the color paste comprises the following steps: s1: taking materials, weighing and proportioning the catalyst slurry, the main resin, the deionized water, the pigment and the cosolvent according to mass percent by using an external electronic scale for later use;

s2: grinding and mixing, pouring the main resin and deionized water into a mixing tank for mixing, adding catalyst slurry for dispersion catalysis, wherein the mixing time is 15 minutes to obtain a solution A, then pouring the pigment and the catalyzed solution A into a ball mill for grinding and mixing, controlling the rotating speed of the ball mill at 60 revolutions per minute, grinding and mixing for 8 minutes to obtain a solution B, diluting the cosolvent with deionized water, adding the diluted cosolvent into the solution B for continuous stirring, and stirring for 5 minutes to obtain the color slurry.

In the application, the mixed solvent comprises an organic bismuth catalyst, a shrinkage-proof agent, a water-based adhesion promoter, a neutralizing agent, a mildew-proof agent, a crease-resist agent, an anti-settling agent, an antirust agent and a defoaming agent, wherein the organic bismuth catalyst belongs to an environment-friendly polyurethane catalyst, the toxicity is lower, the radioactivity is lower, the environment is protected, the water-based adhesion promoter can promote the adhesive force of the coating on the surface of a metal workpiece body, the probability of demoulding or paint dropping generated after the workpiece body is used for a long time is reduced, the mildew-proof agent is selected to be a composite mildew-proof agent, one or more organic acids are combined with a certain carrier, the original mildew-proof function of the organic acids is kept or even promoted, the corrosivity and the irritation of the organic acids are avoided or reduced, the manufacturing effect of the electrophoretic coating is promoted, the anti-settling agent is any one or all of polyethylene wax or polyamide wax, the anti-settling agent is a rheological control agent of the coating, and enables the coating to have thixotropy, greatly improve the viscosity, further improve the adhesive force of the coating on the surface of a workpiece, and reduce the peeling phenomenon generated after the coating is used for a long time.

The anti-shrinkage agent is one of polyacrylic acid and cellulose acetate butyrate, in the embodiment, the anti-shrinkage agent is cellulose acetate butyrate, the anti-shrinkage agent can reduce irregular small depressions formed on the surface of a wet coating after being dried, smoothness after film forming is improved, the anti-wrinkling agent is ethylene glycol monobutyl ether, glossiness and fluidity of the coating are improved, and anti-wrinkle phenomenon of film forming of the coating is reduced, the neutralizing agent is one or more of glacial acetic acid and formic acid, in the embodiment, the neutralizing agent is formic acid, corrosion resistance is strong, resin and color paste filler in a paint liquid can be uniformly mixed by using the neutralizing agent, so that the paint liquid is not easy to precipitate, and leveling performance is improved, and the defoaming agent is emulsified silicon oil, a high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene ether, polyoxypropylene glycerol ether, In the embodiment, the defoaming agent is a mixture of polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane, the defoaming agent can reduce the surface tension of the coating, prevent foam formation and improve the production quality of the coating, and the rust inhibitor can reduce rust caused by mixing reaction of oxygen and water on a metal surface and increase the use stability of the coating.

The invention also provides a synthesis method of the corrosion-resistant cathode electrophoretic coating, which comprises the following steps: s1: taking materials, namely weighing and proportioning modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber, catalyst slurry, color slurry, a mixed solvent, a thickening agent and a diluting agent according to mass percent by using an external electronic scale for later use; s2: mixing, namely adding a diluent into a reaction kettle, adding a main body resin into the reaction kettle through a feeding port at the upper part of the reaction kettle for dissolving, wherein the reaction kettle is a stainless steel reaction kettle, the temperature in the reaction kettle is adjusted to 166 ℃, a servo motor at the top of the reaction kettle is started to stir the solution in the reaction kettle at the speed of 45 revolutions per minute for 16 minutes, and after complete dissolution, a mixed solution A is obtained;

s3: adding materials, namely adding color paste, mixed solvent and thickening agent into the mixed solution A obtained in the step S2 through a feeding port at the upper part of the reaction kettle in sequence, keeping the temperature in the reaction kettle and the rotating speed of a servo motor at the top of the reaction kettle unchanged, and continuously stirring for 24 minutes to obtain corrosion-resistant cathode electrophoretic coating emulsion; s4: and (5) packaging, namely quantitatively filling the corrosion-resistant cathode electrophoretic coating emulsion obtained in the step S3 by using a full-automatic liquid filling machine, and merging the emulsion into a warehouse for storage.

Example 3

A synthesis method of a corrosion-resistant cathode electrophoretic coating comprises the following raw materials by mass percent: 40.5% of modified epoxy resin, 4.4% of carboxyl-terminated nitrile rubber, 2% of catalyst slurry, 5% of color paste, 7% of mixed solvent, 3% of thickening agent and 38.1% of diluent, wherein the thickening agent is specifically acrylate copolymer thickening agent, the appearance of the thickening agent is milky white liquid, the viscosity of the thickening agent is 5500mpa.S, the advection performance of the electrophoretic paint can be improved, the biological stability is high, the service life of the electrophoretic paint is prolonged, and the diluent is deionized water.

In this embodiment, the modified epoxy resin, the carboxyl-terminated nitrile rubber, and the acrylate resin constitute a main resin, and the main resin synthesis method includes the following steps:

s1: taking materials, namely mixing the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber acrylate resin according to the weight ratio of 7.2: 0.8: 2, putting the mixture into two barrels with the same weight for weighing and proportioning for later use; according to the cathode electrophoretic paint, the modified epoxy resin, the carboxyl-terminated butadiene-acrylonitrile rubber and the acrylate resin are adopted to form the main body resin, so that the determination of poor weather resistance, aging resistance and gloss retention caused by only adopting the epoxy resin as a primer in the past is improved, and the embrittlement resistance of the cathode electrophoretic paint is also improved;

s2: mixing, taking a mixing tank with a stirrer, pouring the solution in the two barrels into the mixing tank from a feeding port on the mixing tank, starting the stirrer to mix and stir the modified epoxy resin and the carboxyl-terminated butadiene-acrylonitrile rubber in the mixing tank at a rotating speed of 50 minutes per minute, and stirring for 10 minutes to obtain a mixed solution A, namely a main resin solution.

The catalyst slurry comprises the following raw materials in percentage by mass: the catalyst comprises an auxiliary agent I17%, an acid solution 3%, a binder 3%, deionized water 36%, alumina powder 1%, zirconium dioxide 1%, an auxiliary agent II 18%, an auxiliary agent III 17% and an active component agent 4%, wherein the auxiliary agent I is one or more of alkali metal salt and alkali metal oxide, the alkali metal comprises one or more of Li, Na, K, Rb and Cs, the auxiliary agent I is alkali metal salt, the acid solution comprises one or more of nitric acid, hydrochloric acid and citric acid, the acid solution is hydrochloric acid, the binder is MS modified silane, MS modified silane is adopted as the binder in catalyst slurry, the storage stability and the curing speed are good, the temperature resistance and the antifouling performance are high, the mechanical strength is high, the auxiliary agent II comprises one or more of lanthanide metal and oxide thereof, the lanthanide metal comprises one or more of La, Ce, Nd and Lu, wherein the auxiliary agent II is Nd; the auxiliary agent III comprises one or more of polyvinyl alcohol, polyethylene glycol, polyurethane, acrylate, modified acrylate, polyacrylate and cellulose, wherein the auxiliary agent III is cellulose, the active component agent comprises one or more of noble metals, noble metal salts and noble metal oxides, the noble metals comprise one or more of Pd, Pt, Ru and Rh, and the active component agent is Pd.

In this embodiment, the method for synthesizing the catalyst slurry includes the following steps:

s1: taking materials, namely weighing and proportioning an auxiliary agent I, an acid solution, a binder, deionized water, alumina powder, zirconium dioxide, an auxiliary agent II, an auxiliary agent III and an active component agent by using an external electronic scale according to mass percentage for later use; s2: grinding and mixing, namely firstly putting an auxiliary agent I, a certain amount of acid solution, deionized water and a binder into a stirring tank for mixing, adjusting the rotating speed of a servo motor arranged in the stirring tank to 45 revolutions, stirring the mixture into a viscous state, obtaining a mixed solution A after the stirring is finished, then adding alumina powder and zirconium dioxide into the mixed solution A, continuously stirring the mixture at the rotating speed in the same range for 13 minutes to obtain a mixed solution B, then pouring an auxiliary agent II, an auxiliary agent III and the mixed solution B into a ball mill for grinding and stirring, obtaining a mixed solution C after the stirring for 13 minutes, adding an active component agent, continuously stirring the mixture C for 7 minutes to obtain a mixed solution D, testing the pH value of the mixed solution D according to a pH value tester arranged in the ball mill, obtaining catalyst slurry after the test is qualified, adding a proper amount of acid solution and deionized water for pH value debugging after the test is unqualified, until qualified catalyst slurry is obtained.

In the embodiment, the color paste comprises the following raw materials in percentage by mass: 5.5% of catalyst slurry, 45% of main resin, 43.5% of deionized water, 5% of pigment and 1% of cosolvent.

In this embodiment, the method for synthesizing the color paste includes the following steps:

s1: taking materials, namely weighing and proportioning the catalyst slurry, the main resin, the deionized water, the pigment and the cosolvent according to mass percent by using an external electronic scale for later use;

s2: grinding and mixing, pouring the main resin and deionized water into a mixing tank for mixing, adding catalyst slurry for dispersion catalysis, wherein the mixing time is 14 minutes to obtain a solution A, then pouring the pigment and the catalyzed solution A into a ball mill for grinding and mixing, controlling the rotating speed of the ball mill at 60 revolutions per minute, grinding and mixing for 8 minutes to obtain a solution B, diluting the cosolvent with deionized water, adding the diluted cosolvent into the solution B for continuous stirring, and stirring for 3 minutes to obtain the color slurry.

In this embodiment, the mixed solvent includes an organic bismuth catalyst, a shrinkage-proof agent, a water-based adhesion promoter, a neutralizing agent, a mildew-proof agent, a wrinkle-proof agent, an anti-settling agent, an anti-rusting agent and a defoaming agent, the organic bismuth catalyst belongs to an environment-friendly polyurethane catalyst, the toxicity is low, the radioactivity is low, the environment is protected, the water-based adhesion promoter can improve the adhesion of the coating on the surface of the metal workpiece body and reduce the probability of demoulding or paint dropping of the workpiece body after a long time, the mildew-proof agent is selected as a composite mildew-proof agent, and is synthesized by combining one or more organic acids with a certain carrier, so that the original mildew-proof function of the organic acids is maintained or even improved, the corrosivity and the irritation of the organic acids are avoided or reduced, the manufacturing effect of the electrophoretic coating is improved, and the anti-settling agent is any one or all of polyethylene wax or polyamide wax, the anti-settling agent is a rheological control agent of the coating, and enables the coating to have thixotropy, greatly improve viscosity, further improve the adhesive force of the coating on the surface of a workpiece, and reduce the peeling phenomenon generated after the coating is used for a long time.

Then, the anti-shrinkage agent is one of polyacrylic acid and cellulose acetate butyrate, wherein the anti-shrinkage agent is cellulose acetate butyrate, the anti-shrinkage agent can reduce irregular small depressions formed on the surface of a wet coating after being dried, the smoothness of the formed film is improved, the anti-wrinkling agent is ethylene glycol monobutyl ether, the glossiness and the fluidity of the coating are improved, and the anti-wrinkle phenomenon of the formed film of the coating is reduced, the neutralizing agent is one or more of glacial acetic acid and formic acid, wherein the neutralizing agent is glacial acetic acid, the resin and the color paste filler in the coating liquid can be uniformly mixed by using the neutralizing agent, so that the resin and the color paste filler are not easy to generate precipitates and the leveling property is improved, the defoaming agent is any one or more of emulsified silicone oil, a high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene polyamine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane, the defoaming agent is polyoxypropylene polyoxyethylene glyceryl ether, the defoaming agent can reduce the surface tension of the coating, foam is prevented from being formed, the production quality of the coating is improved, the antirust agent can reduce the corrosion caused by the mixed reaction of oxygen and water on the metal surface, and the use stability of the coating is improved.

In this embodiment, the present invention further provides a method for synthesizing a corrosion-resistant cathode electrophoretic coating, including the following steps:

s1: taking materials, namely weighing and proportioning modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber, catalyst slurry, color slurry, a mixed solvent, a thickening agent and a diluting agent according to mass percent by using an external electronic scale for later use; s2: mixing, namely adding a diluent into a reaction kettle, adding a main body resin into the reaction kettle through a feeding port at the upper part of the reaction kettle for dissolving, wherein the reaction kettle is a stainless steel reaction kettle, the temperature in the reaction kettle is adjusted to 167 ℃, a servo motor at the top of the reaction kettle is started to stir the solution in the reaction kettle at the speed of 48 revolutions per minute for 14 minutes, and after complete dissolution, a mixed solution A is obtained; s3: adding materials, namely adding color paste, mixed solvent and thickening agent into the mixed solution A obtained in the step S2 through a feeding port at the upper part of the reaction kettle in sequence, keeping the temperature in the reaction kettle and the rotating speed of a servo motor at the top of the reaction kettle unchanged, and continuously stirring for 24 minutes to obtain corrosion-resistant cathode electrophoretic coating emulsion; s4: and (5) packaging, namely quantitatively filling the corrosion-resistant cathode electrophoretic coating emulsion obtained in the step S3 by using a full-automatic liquid filling machine, and merging the emulsion into a warehouse for storage.

The above embodiments are merely examples of the present application and are not intended to limit the scope of the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

The above description is only for the specific embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present application, and all the changes or substitutions should be covered by the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A synthetic method of corrosion-resistant cathode electrophoretic paint is characterized by comprising the following steps: the raw materials are as follows by mass percent: 31.5 to 40.5 percent of modified epoxy resin, 3.5 to 4.4 percent of carboxyl-terminated nitrile rubber, 1 to 2 percent of catalyst slurry, 3 to 5 percent of color paste, 7 to 10 percent of mixed solvent, 2 to 4 percent of thickening agent and 35 to 55 percent of diluent.

2. The method for synthesizing the corrosion-resistant cathode electrophoretic coating according to claim 1, wherein the modified epoxy resin, the carboxyl-terminated nitrile rubber and the acrylate resin form a main resin, and the method for synthesizing the main resin comprises the following steps:

3. The method for synthesizing the corrosion-resistant cathode electrophoretic coating according to claim 1, wherein the catalyst slurry comprises the following raw materials in percentage by mass: 17-19% of an auxiliary agent I, 3-5% of an acid solution, 3-5% of a binder, 35-40% of deionized water, 1-2% of alumina powder, 1-2% of zirconium dioxide, 17-19% of an auxiliary agent II, 17-19% of an auxiliary agent III and 4-5% of an active component agent, wherein the auxiliary agent I is one or more of alkali metal salts and alkali metal oxides, and the alkali metal comprises any one or more of Li, Na, K, Rb and Cs.

4. The method for synthesizing the corrosion-resistant cathode electrophoretic coating according to claim 3, wherein the acid solution comprises one or more of nitric acid, hydrochloric acid and citric acid, the binder is MS modified silane, the auxiliary agent II comprises one or more of lanthanide metals and oxides thereof, and the lanthanide metals comprise one or more of La, Ce, Nd and Lu; the auxiliary agent III comprises one or more of polyvinyl alcohol, polyethylene glycol, polyurethane, acrylate, modified acrylate, polyacrylate and cellulose, the active component agent comprises one or more of noble metal, noble metal salt and noble metal oxide, and the noble metal comprises one or more of Pd, Pt, Ru and Rh.

5. The method for synthesizing the corrosion-resistant cathode electrophoretic coating according to claim 4, wherein the method for synthesizing the catalyst slurry comprises the following steps:

s2: grinding and mixing, namely firstly putting an auxiliary agent I, a certain amount of acid solution, deionized water and a binder into a stirring tank for mixing, adjusting the rotating speed of a servo motor arranged in the stirring tank to 40-60 revolutions, stirring into a viscous state to obtain a mixed solution A, then adding alumina powder and zirconium dioxide into the mixed solution A, continuously stirring at the rotating speed in the same range for 10-15 minutes to obtain a mixed solution B, then pouring an auxiliary agent II, an auxiliary agent III and the mixed solution B into a ball mill for grinding and stirring, stirring for 10-15 minutes to obtain a mixed solution C, then adding an active component agent, continuously stirring for 5-8 minutes to obtain a mixed solution D, testing the pH value of the mixed solution D according to a pH value tester arranged in the ball mill, and obtaining a catalyst slurry after the test is qualified, and after the test is unqualified, adding a proper amount of acid solution and deionized water for pH value debugging until qualified catalyst slurry is obtained.

6. The synthesis method of the corrosion-resistant cathode electrophoretic paint according to claim 1, wherein the color paste comprises the following raw materials by mass percent: 3-5.5% of catalyst slurry, 35-45% of main resin, 40-55% of deionized water, 5-9% of pigment and 1-1.5% of cosolvent.

7. The method for synthesizing the corrosion-resistant cathode electrophoretic paint as claimed in claim 6, wherein the method for synthesizing the color paste comprises the following steps:

s2: grinding and mixing, pouring the main resin and deionized water into a mixing tank for mixing, adding catalyst slurry for dispersion catalysis, wherein the mixing time is 10-15 minutes to obtain a solution A, pouring the pigment and the catalyzed solution A into a ball mill for grinding and mixing, controlling the rotating speed of the ball mill at 40-60 rpm, grinding and mixing for 5-8 minutes to obtain a solution B, adding deionized water into a cosolvent for dilution, adding the solution B, continuously stirring, and stirring for 3-5 minutes to obtain the color paste.

8. The method for synthesizing corrosion-resistant cathodic electrophoretic paint as defined in claim 1, wherein said thickener is acrylate copolymer thickener, the appearance is milky white liquid with viscosity of 2500-.

9. A method for synthesizing a corrosion-resistant cathodic electrophoretic coating according to claim 1, wherein: the mixed solvent comprises an organic bismuth catalyst, a shrinkage-proof agent, a water-based adhesion promoter, a neutralizing agent, a mildew-proof agent, a crease-resist agent, an anti-settling agent, an antirust agent and a defoaming agent, and the mixing ratio is 1: 1: 1: 1: 1: 1: 1: 1: the anti-settling agent is any one or all of polyethylene wax or polyamide wax, the anti-shrinkage agent is one of polyacrylic acid and cellulose acetate butyrate, the anti-wrinkling agent is ethylene glycol monobutyl ether, the neutralizing agent is one or more of glacial acetic acid and formic acid, and the defoaming agent is any one or more of emulsified silicone oil, a high-carbon alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.

10. The method for synthesizing the corrosion-resistant cathode electrophoretic coating according to claim 1, comprising the following steps:

s1: taking materials, namely weighing and proportioning modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber, catalyst slurry, color paste, a mixed solvent, a thickening agent and a diluent by using an external electronic scale according to mass percent for later use;

s2: mixing, namely adding a diluent into a reaction kettle, adding main resin into the reaction kettle through a feed inlet at the upper part of the reaction kettle for dissolving, adjusting the temperature in the reaction kettle to 165-169.5 ℃, starting a servo motor at the top of the reaction kettle to stir the solution in the reaction kettle at the speed of 40-60 revolutions per minute for 10-20 minutes, and obtaining a mixed solution A after complete dissolution;