A modified water-based cold-dip galvanizing anti-corrosion coating and preparation method thereof

Abstract

The present invention relates to the technical field of anti-corrosion coatings, and specifically to a modified water-based cold-galvanized anti-corrosion coating and a preparation method thereof, wherein the anti-corrosion coating comprises the following raw materials in parts by weight: 30 to 35 parts of water-based acrylic resin, 8 to 14 parts of functional additives based on endurance and stability adjustment, 7 to 11 parts of modified nano zinc oxide, 6 to 9 parts of curing agent, 2 to 4 parts of film-forming aid, 1 to 3 parts of defoaming agent, 4 to 7 parts of silane coupling agent KH560, and 25 to 30 parts of deionized water. The cold-galvanized anti-corrosion coating of the present invention adopts water-based acrylic resin as a matrix, and adds functional additives based on endurance and stability adjustment and modified nano zinc oxide as blending raw materials. Through the coordination and matching of the two, the product has a significant pulling adhesion performance effect, and enhances the anti-corrosion, anti-freezing and heat resistance and scratch stability performance of the coating product, thereby improving the performance stability of the product.

Description

Technical Field

[0001] The invention relates to the technical field of anti-corrosion coatings, and in particular to a modified water-based cold-dip galvanizing anti-corrosion coating and a preparation method thereof. Background Art

[0002] As a new type of zinc-rich coating, cold-dip galvanizing coating has a unique cathodic protection effect and excellent anti-corrosion performance. It can replace hot-dip galvanizing and can be coated on metal surfaces alone or used in conjunction with other coatings. The inorganic zinc powder added to the existing cold-dip galvanizing coating has poor interface properties with the organic matrix of the coating, and the zinc powder is easy to agglomerate, which leads to poor anti-corrosion, anti-freezing and anti-heat, and scratch stability performance of the product, limiting the use efficiency of the product. Based on this, the present invention further improves the product. Summary of the invention

[0003] In view of the defects of the prior art, the purpose of the present invention is to provide a modified water-based cold-dip galvanizing anti-corrosion coating and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0004] The present invention solves the technical problem by adopting the following technical solution:

[0005] The present invention provides a modified water-based cold-dip galvanizing anti-corrosion coating, which comprises the following raw materials in parts by weight:

[0006] 30-35 parts of water-based acrylic resin, 8-14 parts of functional additives based on stability adjustment, 7-11 parts of modified nano zinc oxide, 6-9 parts of curing agent, 2-4 parts of film-forming aid, 1-3 parts of defoaming agent, 4-7 parts of silane coupling agent KH560, and 25-30 parts of deionized water.

[0007] Preferably, the modified water-based cold-dip galvanizing anti-corrosion coating comprises the following raw materials in parts by weight:

[0008] 32.5 parts of water-based acrylic resin, 11 parts of functional additives based on stability adjustment, 9 parts of modified nano zinc oxide, 7.5 parts of curing agent, 3 parts of film-forming aid, 2 parts of defoaming agent, 5.5 parts of silane coupling agent KH560, and 27.5 parts of deionized water.

[0009] Preferably, the curing agent is an isocyanate curing agent; the defoaming agent is polysiloxane; and the film-forming aid is dipropylene glycol butyl ether.

[0010] Preferably, the preparation method of the functional additive based on stability regulation is:

[0011] S01: heat-treating the nano-mica powder at 155-165°C for 5-10 minutes, and then air-cooling to room temperature;

[0012] S02: Prepare a sodium lignin sulfonate solution with a mass fraction of 4-7%; a sodium alginate solution with a mass fraction of 2-5%;

[0013] 5 to 8 parts of nano-mica powder cooled to room temperature, 2 to 5 parts of sodium lignin sulfonate solution, 1 to 3 parts of silicon carbide whiskers and 3 to 6 parts of sodium alginate solution are fully mixed, then washed with water and dried to obtain a stabilizer;

[0014] S03: The modified liquid and the stabilizer are adjusted to a weight ratio of 3:(5-7), mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball milling is completed, the mixture is washed with water and dried to obtain a functional additive based on stabilizer adjustment.

[0015] Preferably, the preparation method of the adjustment and modification liquid is:

[0016] 3-5 parts of silicon micropowder, 2-5 parts of chitosan solution and 1-3 parts of lanthanum nitrate solution are mixed and ball-milled at a speed of 1500 r / min for 1 hour to obtain a modified silicon micropowder solution;

[0017] The zirconium dioxide is first pretreated in a sufficient amount of a 6% by mass potassium permanganate solution, and after the treatment, it is washed with water and dried to obtain the pretreated zirconium dioxide; then 1 to 3 parts of dopamine hydrochloride and 2 to 4 parts of the pretreated zirconium dioxide are added to 5 to 8 parts of modified silicon micropowder liquid, and then 2 to 3 parts of sodium citrate are added and stirred to obtain a regulated modified liquid.

[0018] Preferably, the mass fraction of the chitosan solution is 2-5%; the mass fraction of the lanthanum nitrate solution is 4%.

[0019] Preferably, the pretreatment temperature is 50-55° C., the treatment time is 10-20 min, and the treatment speed is 550-650 r / min.

[0020] Preferably, the preparation method of the modified nano zinc oxide is:

[0021] S11: treating the nano zinc oxide powder in a plasma box for 10 to 15 minutes, with a plasma power of 350 to 400 W, and then the treatment is completed;

[0022] 5 to 8 parts of plasma-treated nano zinc oxide powder, 4 to 6 parts of sodium silicate solution, and 1 to 3 parts of silane coupling agent KH550 are uniformly mixed to obtain nano zinc oxide liquid;

[0023] S12: Preparation of modified treatment agent:

[0024] S121: Stirring titanium carbide in a sufficient amount of nitric acid aqueous solution with a mass concentration of 15-20%, then washing and drying to obtain acid-treated titanium carbide;

[0025] S122: 3 to 6 parts of flaky aluminum oxide and 1 to 3 parts of nano-silica sol are added to 5 to 8 parts of lanthanum chloride solution, and then 2 to 4 parts of carboxymethyl cellulose are added, and stirred thoroughly to obtain a flaky aluminum oxide agent;

[0026] S123: Acid-treated titanium carbide and flaky aluminum oxide are stirred in a weight ratio of 3:(5-7) to obtain a modified treatment agent;

[0027] S13: mixing the nano zinc oxide liquid and the modifying agent in a weight ratio of 5:(2-3) and subjecting them to ball milling at a ball milling speed of 1000-1500 r / min for 1 hour. After the ball milling is completed, washing with water and drying are performed to obtain modified nano zinc oxide.

[0028] Preferably, the diameter of the flaky aluminum oxide is 150-200 nm, and the thickness is 10-15 nm; the particle size of the nano zinc oxide powder is 50-60 nm;

[0029] The mass fraction of the sodium silicate solution is 2-5%; the mass fraction of the lanthanum chloride solution is 3-6%.

[0030] The present invention also provides a method for preparing a modified water-based cold-dip galvanizing anti-corrosion coating, comprising the following steps:

[0031] The functional additive based on resistance and stability adjustment, modified nano zinc oxide, and silane coupling agent KH560 are first mixed to obtain a mixture; then the mixture, water-based acrylic resin, film-forming aid and defoaming agent are added to deionized water in sequence, and then a curing agent is added, and the mixture is stirred at 550-750r / min for 1h. After the stirring is completed, a modified water-based cold-dip galvanizing anti-corrosion coating can be obtained.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The cold-dip galvanizing anti-corrosion coating of the present invention adopts water-based acrylic resin as a matrix, adds a curing agent, a film-forming aid, a defoaming agent and a silane coupling agent KH560 as functional additives, and simultaneously adds functional additives based on resistance and stability adjustment and modified nano zinc oxide as blending raw materials. Through the coordination and coordination of the two, the pulling adhesion performance of the product is remarkable, and the anti-corrosion, frost resistance and scratch stability performance of the coating product are enhanced, and the performance stability of the product is improved; the modified nano zinc oxide adopts nano zinc oxide that is treated with plasma to stimulate its active efficiency, and then is blended and blended uniformly with a sodium silicate solution and a silane coupling agent KH550 to optimize the dispersion stability of the nano zinc oxide, and titanium carbide is treated with a nitric acid solution to improve its activity, and flaky aluminum oxide, nano silica sol, lanthanum chloride solution and carboxymethyl cellulose are fully stirred to obtain a flaky aluminum oxide agent, and the flaky aluminum oxide with a flaky structure is used to blend the lanthanum chloride solution, etc. Raw materials, and then coordinated with titanium carbide to optimize the bearing stability of nano zinc oxide, thereby improving the dispersion stability of nano zinc oxide, and then improving the performance of the system; based on the functional additive of stability regulation, nano mica powder is heat treated at 155-165°C for 5-10min, and at the same time, sodium lignin sulfonate solution, silicon carbide whisker and sodium alginate solution are blended and coordinated, and the whisker-like structure is blended with the nano-layered structure in the system to enhance the interface of the system and improve the performance stability of the system, and the modified liquid is adjusted to use silicon micropowder, chitosan solution and lanthanum nitrate solution for ball milling treatment, and then zirconium dioxide is pretreated in a sufficient amount of potassium permanganate solution with a mass fraction of 6% to optimize the activity of zirconium dioxide, and dopamine hydrochloride, pretreated zirconium dioxide, modified silicon micropowder liquid and sodium citrate are coordinated. Through the synergistic effect between the raw materials, the performance stability of the product is further improved. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. 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.

[0035] A modified water-based cold-dip galvanizing anti-corrosion coating according to the present embodiment comprises the following raw materials in parts by weight:

[0036] 30-35 parts of water-based acrylic resin, 8-14 parts of functional additives based on stability adjustment, 7-11 parts of modified nano zinc oxide, 6-9 parts of curing agent, 2-4 parts of film-forming aid, 1-3 parts of defoaming agent, 4-7 parts of silane coupling agent KH560, and 25-30 parts of deionized water.

[0037] The modified water-based cold-dip galvanizing anti-corrosion coating of this embodiment includes the following raw materials in parts by weight:

[0038] 32.5 parts of water-based acrylic resin, 11 parts of functional additives based on stability adjustment, 9 parts of modified nano zinc oxide, 7.5 parts of curing agent, 3 parts of film-forming aid, 2 parts of defoaming agent, 5.5 parts of silane coupling agent KH560, and 27.5 parts of deionized water.

[0039] The curing agent in this embodiment is an isocyanate curing agent; the defoaming agent is polysiloxane; and the film-forming aid is dipropylene glycol butyl ether.

[0040] The preparation method of the functional additive based on the stability regulation of this embodiment is:

[0041] S01: heat-treating the nano-mica powder at 155-165°C for 5-10 minutes, and then air-cooling to room temperature;

[0042] S02: Prepare a sodium lignin sulfonate solution with a mass fraction of 4-7%; a sodium alginate solution with a mass fraction of 2-5%;

[0043] 5 to 8 parts of nano-mica powder cooled to room temperature, 2 to 5 parts of sodium lignin sulfonate solution, 1 to 3 parts of silicon carbide whiskers and 3 to 6 parts of sodium alginate solution are fully mixed, then washed with water and dried to obtain a stabilizer;

[0044] S03: The modified liquid and the stabilizer are adjusted to a weight ratio of 3:(5-7), mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball milling is completed, the mixture is washed with water and dried to obtain a functional additive based on stabilizer adjustment.

[0045] The preparation method of the modified liquid of this embodiment is:

[0046] 3-5 parts of silicon micropowder, 2-5 parts of chitosan solution and 1-3 parts of lanthanum nitrate solution are mixed and ball-milled at a speed of 1500 r / min for 1 hour to obtain a modified silicon micropowder solution;

[0047] The zirconium dioxide is first pretreated in a sufficient amount of a 6% by mass potassium permanganate solution, and after the treatment, it is washed with water and dried to obtain the pretreated zirconium dioxide; then 1 to 3 parts of dopamine hydrochloride and 2 to 4 parts of the pretreated zirconium dioxide are added to 5 to 8 parts of modified silicon micropowder liquid, and then 2 to 3 parts of sodium citrate are added and stirred to obtain a regulated modified liquid.

[0048] The mass fraction of the chitosan solution in this embodiment is 2-5%; the mass fraction of the lanthanum nitrate solution is 4%.

[0049] The pretreatment temperature of the present embodiment is 50-55° C., the treatment time is 10-20 min, and the treatment speed is 550-650 r / min.

[0050] The preparation method of the modified nano zinc oxide of this embodiment is:

[0051] S11: treating the nano zinc oxide powder in a plasma box for 10 to 15 minutes, with a plasma power of 350 to 400 W, and then the treatment is completed;

[0052] 5 to 8 parts of plasma-treated nano zinc oxide powder, 4 to 6 parts of sodium silicate solution, and 1 to 3 parts of silane coupling agent KH550 are uniformly mixed to obtain nano zinc oxide liquid;

[0053] S12: Preparation of modified treatment agent:

[0054] S121: Stirring titanium carbide in a sufficient amount of nitric acid aqueous solution with a mass concentration of 15-20%, then washing and drying to obtain acid-treated titanium carbide;

[0055] S122: 3 to 6 parts of flaky aluminum oxide and 1 to 3 parts of nano-silica sol are added to 5 to 8 parts of lanthanum chloride solution, and then 2 to 4 parts of carboxymethyl cellulose are added, and stirred thoroughly to obtain a flaky aluminum oxide agent;

[0056] S123: Acid-treated titanium carbide and flaky aluminum oxide are stirred in a weight ratio of 3:(5-7) to obtain a modified treatment agent;

[0057] S13: mixing the nano zinc oxide liquid and the modifying agent in a weight ratio of 5:(2-3) and subjecting them to ball milling at a ball milling speed of 1000-1500 r / min for 1 hour. After the ball milling is completed, washing with water and drying are performed to obtain modified nano zinc oxide.

[0058] The diameter of the flaky aluminum oxide in this embodiment is 150-200 nm, and the thickness is 10-15 nm; the particle size of the nano zinc oxide powder is 50-60 nm;

[0059] The mass fraction of the sodium silicate solution is 2-5%; the mass fraction of the lanthanum chloride solution is 3-6%.

[0060] The preparation method of the modified water-based cold-dip galvanizing anti-corrosion coating of this embodiment comprises the following steps:

[0061] The functional additive based on resistance and stability adjustment, modified nano zinc oxide, and silane coupling agent KH560 are first mixed to obtain a mixture; then the mixture, water-based acrylic resin, film-forming aid and defoaming agent are added to deionized water in sequence, and then a curing agent is added, and the mixture is stirred at 550-750r / min for 1h. After the stirring is completed, a modified water-based cold-dip galvanizing anti-corrosion coating can be obtained.

[0062] Example 1.

[0063] A modified water-based cold-dip galvanizing anti-corrosion coating according to the present embodiment comprises the following raw materials in parts by weight:

[0064] 30 parts of water-based acrylic resin, 8 parts of functional additives based on stability adjustment, 7 parts of modified nano zinc oxide, 6 parts of curing agent, 2 parts of film-forming aid, 1 part of defoaming agent, 4 parts of silane coupling agent KH560, and 25 parts of deionized water.

[0065] The curing agent in this embodiment is an isocyanate curing agent; the defoaming agent is polysiloxane; and the film-forming aid is dipropylene glycol butyl ether.

[0066] The preparation method of the functional additive based on the stability regulation of this embodiment is:

[0067] S01: heat-treat the nano-mica powder at 155°C for 5 min, and then air-cool to room temperature;

[0068] S02: Prepare 4% sodium lignin sulfonate solution and 2% sodium alginate solution;

[0069] 5 parts of nano-mica powder cooled to room temperature, 2 parts of sodium lignin sulfonate solution, 1 part of silicon carbide whisker and 3 parts of sodium alginate solution are fully mixed, then washed with water and dried to obtain a stabilizer;

[0070] S03: The modified liquid and the stabilizer are adjusted to a weight ratio of 3:5, mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball milling is completed, the mixture is washed with water and dried to obtain a functional additive based on stabilizer adjustment.

[0071] The preparation method of the modified liquid of this embodiment is:

[0072] 3 parts of silicon micropowder, 2 parts of chitosan solution and 1 part of lanthanum nitrate solution were mixed and ball-milled at a speed of 1500 r / min for 1 h to obtain a modified silicon micropowder solution;

[0073] The zirconium dioxide is first pretreated in a sufficient amount of 6% by mass potassium permanganate solution. After the treatment, it is washed with water and dried to obtain pretreated zirconium dioxide; then 1 part of dopamine hydrochloride and 2 parts of pretreated zirconium dioxide are added to 5 parts of modified silicon micropowder liquid, and then 2 parts of sodium citrate are added and stirred sufficiently to obtain an adjusted modified liquid.

[0074] The mass fraction of the chitosan solution in this embodiment is 2%; the mass fraction of the lanthanum nitrate solution is 4%.

[0075] The pretreatment temperature of this embodiment is 50° C., the treatment time is 10 min, and the treatment speed is 550 r / min.

[0076] The preparation method of the modified nano zinc oxide of this embodiment is:

[0077] S11: The nano zinc oxide powder is first treated in a plasma box for 10 minutes, the plasma power is 350W, and the treatment is completed;

[0078] 5 parts of plasma treated nano zinc oxide powder, 4 parts of sodium silicate solution and 1 part of silane coupling agent KH550 are uniformly mixed to obtain nano zinc oxide liquid;

[0079] S12: Preparation of modified treatment agent:

[0080] S121: Stirring titanium carbide in a sufficient amount of 15% by mass nitric acid aqueous solution, then washing with water and drying to obtain acid-treated titanium carbide;

[0081] S122: 3 parts of flaky aluminum oxide and 1 part of nano-silica sol are added to 5 parts of lanthanum chloride solution, and then 2 parts of carboxymethyl cellulose are added and stirred thoroughly to obtain a flaky aluminum oxide agent;

[0082] S123: Acid-treated titanium carbide and flaky aluminum oxide are stirred in a weight ratio of 3:5 to obtain a modified treatment agent;

[0083] S13: mixing the nano zinc oxide liquid and the modifying agent in a weight ratio of 5:2, and ball milling the mixture at a speed of 1000 r / min for 1 h. After the ball milling is completed, washing and drying are performed to obtain modified nano zinc oxide.

[0084] The diameter of the flaky aluminum oxide in this embodiment is 150 nm, and the thickness is 10 nm; the particle size of the nano zinc oxide powder is 50 nm;

[0085] The mass fraction of the sodium silicate solution is 2%; the mass fraction of the lanthanum chloride solution is 3%.

[0086] The preparation method of the modified water-based cold-dip galvanizing anti-corrosion coating of this embodiment comprises the following steps:

[0087] The functional additive based on resistance and stability adjustment, modified nano zinc oxide, and silane coupling agent KH560 are first mixed to obtain a mixture; then the mixture, water-based acrylic resin, film-forming aid and defoaming agent are added to deionized water in sequence, and then a curing agent is added, and the mixture is stirred at 550 r / min for 1 hour. After the stirring is completed, a modified water-based cold-dip galvanizing anti-corrosion coating can be obtained.

[0088] Example 2.

[0089] A modified water-based cold-dip galvanizing anti-corrosion coating according to the present embodiment comprises the following raw materials in parts by weight:

[0090] 35 parts of water-based acrylic resin, 14 parts of functional additives based on stability adjustment, 11 parts of modified nano zinc oxide, 9 parts of curing agent, 4 parts of film-forming aid, 3 parts of defoaming agent, 7 parts of silane coupling agent KH560, and 30 parts of deionized water.

[0091] The curing agent in this embodiment is an isocyanate curing agent; the defoaming agent is polysiloxane; and the film-forming aid is dipropylene glycol butyl ether.

[0092] The preparation method of the functional additive based on the stability regulation of this embodiment is:

[0093] S01: heat-treat the nano-mica powder at 165°C for 10 min, and then air-cool to room temperature;

[0094] S02: Prepare 7% sodium lignin sulfonate solution and 5% sodium alginate solution;

[0095] 8 parts of nano-mica powder cooled to room temperature, 5 parts of sodium lignin sulfonate solution, 3 parts of silicon carbide whiskers and 6 parts of sodium alginate solution are fully mixed, then washed with water and dried to obtain a stabilizer;

[0096] S03: The modified liquid and the stabilizer are adjusted to a weight ratio of 3:7, mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball milling is completed, the mixture is washed with water and dried to obtain a functional additive based on stabilizer adjustment.

[0097] The preparation method of the modified liquid of this embodiment is:

[0098] 5 parts of silicon micropowder, 5 parts of chitosan solution and 3 parts of lanthanum nitrate solution were mixed and ball-milled at a speed of 1500 r / min for 1 h to obtain a modified silicon micropowder solution;

[0099] The zirconium dioxide is first pretreated in a sufficient amount of 6% by mass potassium permanganate solution. After the treatment, it is washed with water and dried to obtain the pretreated zirconium dioxide; then 3 parts of dopamine hydrochloride and 4 parts of the pretreated zirconium dioxide are added to 8 parts of modified silicon micropowder liquid, and then 3 parts of sodium citrate are added and stirred sufficiently to obtain an adjusted modified liquid.

[0100] The mass fraction of the chitosan solution in this embodiment is 5%; the mass fraction of the lanthanum nitrate solution is 4%.

[0101] The pretreatment temperature of this embodiment is 55° C., the treatment time is 20 min, and the treatment speed is 650 r / min.

[0102] The preparation method of the modified nano zinc oxide of this embodiment is:

[0103] S11: The nano zinc oxide powder is first treated in a plasma box for 15 minutes, the plasma power is 400W, and the treatment is completed;

[0104] 8 parts of plasma treated nano zinc oxide powder, 6 parts of sodium silicate solution and 3 parts of silane coupling agent KH550 are uniformly mixed to obtain nano zinc oxide liquid;

[0105] S12: Preparation of modified treatment agent:

[0106] S121: Stirring titanium carbide in a sufficient amount of 20% by mass concentration nitric acid aqueous solution, then washing with water and drying to obtain acid-treated titanium carbide;

[0107] S122: 6 parts of flaky aluminum oxide and 3 parts of nano-silica sol are added to 8 parts of lanthanum chloride solution, and then 4 parts of carboxymethyl cellulose are added and stirred to obtain a flaky aluminum oxide agent;

[0108] S123: Acid-treated titanium carbide and flaky aluminum oxide are stirred in a weight ratio of 3:7 to obtain a modified treatment agent;

[0109] S13: The nano zinc oxide liquid and the modifying agent are mixed in a weight ratio of 5:3, and the mixture is ball-milled at a speed of 1500 r / min for 1 h. After the ball-milling is completed, the mixture is washed with water and dried to obtain modified nano zinc oxide.

[0110] The diameter of the flaky aluminum oxide in this embodiment is 200 nm, and the thickness is 15 nm; the particle size of the nano zinc oxide powder is 60 nm;

[0111] The mass fraction of the sodium silicate solution is 5%; the mass fraction of the lanthanum chloride solution is 6%.

[0112] The preparation method of the modified water-based cold-dip galvanizing anti-corrosion coating of this embodiment comprises the following steps:

[0113] The functional additive based on resistance and stability adjustment, modified nano zinc oxide, and silane coupling agent KH560 are first mixed to obtain a mixture; then the mixture, water-based acrylic resin, film-forming aid and defoaming agent are added to deionized water in sequence, and then a curing agent is added, and the mixture is stirred at 750r / min for 1h. After the stirring is completed, a modified water-based cold-dip galvanizing anti-corrosion coating can be obtained.

[0114] Example 3.

[0115] A modified water-based cold-dip galvanizing anti-corrosion coating according to the present embodiment comprises the following raw materials in parts by weight:

[0116] 32.5 parts of water-based acrylic resin, 11 parts of functional additives based on stability adjustment, 9 parts of modified nano zinc oxide, 7.5 parts of curing agent, 3 parts of film-forming aid, 2 parts of defoaming agent, 5.5 parts of silane coupling agent KH560, and 27.5 parts of deionized water.

[0117] The curing agent in this embodiment is an isocyanate curing agent; the defoaming agent is polysiloxane; and the film-forming aid is dipropylene glycol butyl ether.

[0118] The preparation method of the functional additive based on the stability regulation of this embodiment is:

[0119] S01: heat-treat the nano-mica powder at 160°C for 7.5 min, and then air-cool to room temperature;

[0120] S02: Prepare 5.5% sodium lignin sulfonate solution and 3.5% sodium alginate solution;

[0121] 6.5 parts of nano-mica powder cooled to room temperature, 3.5 parts of sodium lignin sulfonate solution, 2 parts of silicon carbide whiskers and 4.5 parts of sodium alginate solution were fully mixed, then washed with water and dried to obtain a stabilizer;

[0122] S03: The modified liquid and the stabilizer are adjusted to a weight ratio of 1:2, mixed and ball-milled at a speed of 1500 r / min for 1 hour. After the ball milling is completed, the mixture is washed with water and dried to obtain a functional additive based on stabilizer adjustment.

[0123] The preparation method of the modified liquid of this embodiment is:

[0124] 4 parts of silicon micropowder, 3.5 parts of chitosan solution and 2 parts of lanthanum nitrate solution were mixed and ball-milled at a speed of 1500 r / min for 1 h to obtain a modified silicon micropowder solution;

[0125] The zirconium dioxide is first pretreated in a sufficient amount of 6% by mass potassium permanganate solution. After the treatment, it is washed with water and dried to obtain pretreated zirconium dioxide; then 2 parts of dopamine hydrochloride and 3 parts of pretreated zirconium dioxide are added to 6.5 parts of modified silicon micropowder liquid, and then 2.5 parts of sodium citrate are added and stirred sufficiently to obtain an adjusted modified liquid.

[0126] The mass fraction of the chitosan solution in this embodiment is 3.5%; the mass fraction of the lanthanum nitrate solution is 4%.

[0127] The pretreatment temperature of this embodiment is 52.5° C., the treatment time is 15 min, and the treatment speed is 600 r / min.

[0128] The preparation method of the modified nano zinc oxide of this embodiment is:

[0129] S11: The nano zinc oxide powder is first treated in a plasma box for 12.5 minutes, the plasma power is 370W, and the treatment is completed;

[0130] 6.5 parts of plasma treated nano zinc oxide powder, 5 parts of sodium silicate solution and 2 parts of silane coupling agent KH550 were uniformly mixed to obtain nano zinc oxide liquid;

[0131] S12: Preparation of modified treatment agent:

[0132] S121: Stirring titanium carbide in a sufficient amount of 17.5% mass concentration nitric acid aqueous solution, then washing with water and drying to obtain acid-treated titanium carbide;

[0133] S122: 4.5 parts of flaky aluminum oxide and 2 parts of nano-silica sol are added to 6.5 parts of lanthanum chloride solution, and then 3 parts of carboxymethyl cellulose are added, and stirred thoroughly to obtain a flaky aluminum oxide agent;

[0134] S123: Acid-treated titanium carbide and flaky aluminum oxide are stirred in a weight ratio of 1:2 to obtain a modified treatment agent;

[0135] S13: The nano zinc oxide liquid and the modifying agent are mixed in a weight ratio of 2:1 and subjected to ball milling at a ball milling speed of 1250 r / min for 1 h. After the ball milling is completed, the mixture is washed with water and dried to obtain modified nano zinc oxide.

[0136] The diameter of the flaky aluminum oxide in this embodiment is 175 nm, and the thickness is 12.5 nm; the particle size of the nano zinc oxide powder is 55 nm;

[0137] The mass fraction of the sodium silicate solution is 3.5%; the mass fraction of the lanthanum chloride solution is 4.5%.

[0138] The preparation method of the modified water-based cold-dip galvanizing anti-corrosion coating of this embodiment comprises the following steps:

[0139] The functional additive based on resistance and stability adjustment, modified nano zinc oxide, and silane coupling agent KH560 are first mixed to obtain a mixture; then the mixture, water-based acrylic resin, film-forming aid and defoaming agent are added to deionized water in sequence, and then a curing agent is added, and the mixture is stirred at 600r / min for 1h. After the stirring is completed, a modified water-based cold-dip galvanizing anti-corrosion coating can be obtained.

[0140] Comparative Example 1.

[0141] The difference from Example 3 is that no functional additive based on stability regulation is added.

[0142] Comparative Example 2.

[0143] The difference from Example 3 is that no stabilizer is added in the preparation of the functional additive based on the stability regulation.

[0144] Comparative Example 3.

[0145] The difference from Example 3 is that the nano-mica powder air-cooled to room temperature is not added to the stabilizer.

[0146] Comparative Example 4.

[0147] The difference from Example 3 is that no sodium lignin sulfonate solution or silicon carbide whisker is added to the stabilizer.

[0148] Comparative Example 5.

[0149] The difference from Example 3 is that no regulating and modifying liquid is added in the preparation of the functional additive based on the stability regulation.

[0150] Comparative Example 6.

[0151] The difference from Example 3 is that the modified nano zinc oxide is replaced by nano zinc oxide.

[0152] Comparative Example 7.

[0153] The difference from Example 3 is that in the preparation of modified nano-zinc oxide, nano-zinc oxide liquid is replaced by nano-zinc oxide.

[0154] Comparative Example 8.

[0155] The difference from Example 3 is that no modifying agent is added in the preparation of the modified nano zinc oxide.

[0156] Comparative Example 9.

[0157] The difference from Example 3 is that no acid-treated titanium carbide is added in the preparation of the modifying agent.

[0158] Comparative Example 10.

[0159] The difference from Example 3 is that no flaky alumina agent is added in the preparation of the modified treatment agent.

[0160] Comparative Example 11.

[0161] The difference from Example 3 is that no flaky alumina or nano-silica sol is added in the preparation of the flaky alumina agent.

[0162] Comparative Example 12.

[0163] The difference from Example 3 is that carboxymethyl cellulose was not added in the preparation of the flaky alumina agent, and deionized water was used instead of the lanthanum chloride solution.

[0164] Examples 1 to 3 and Comparative Examples 1 to 12 were coated on a substrate with a coating thickness of 2 mm. The products were subjected to a pull-off adhesion performance test, and the product anti-corrosion (the coating was placed under 2% hydrochloric acid mist for 24 hours, and then placed under 2% sodium hydroxide alkaline mist for 24 hours), frost resistance (the coating was placed at -5°C for 24 hours, and then at 65°C for 24 hours) and scratch stability (the coating was scratched 10 times with a load of 5N applied), and the performance test results are as follows;

[0165]

[0166]

[0167] It can be seen from Comparative Examples 1 to 12 and Examples 1 to 3 that;

[0168] The product of Example 3 has excellent pull-off adhesion, and the product has excellent performance stability under anti-corrosion conditions, freezing and heat resistance conditions, and scratch conditions;

[0169] From Comparative Examples 1 to 12 and Example 3, it can be seen that the performance of the product is significantly deteriorated when the functional additive based on the stability adjustment is not added and the modified nano zinc oxide is replaced by nano zinc oxide. The performance effect of the product is most significant when the modified nano zinc oxide and the functional additive based on the stability adjustment are coordinated and work together.

[0170] The performance of the products showed a trend of deterioration when no stabilizer was added in the preparation of the functional additive based on the stability adjustment, no nano-mica powder air-cooled to room temperature was added to the stabilizer, no sodium lignin sulfonate solution and silicon carbide whiskers were added to the stabilizer, and no adjusting and modifying liquid was added in the preparation of the functional additive based on the stability adjustment. The performance of the products showed a trend of deterioration when no adjusting and modifying liquid was added in the preparation of the functional additive based on the stability adjustment. The performance of the products showed a significant deterioration when the functional additive based on the stability adjustment was obtained by the specific method of the present invention.

[0171] No modifying agent was added in the preparation of modified nano zinc oxide, no acid-treated titanium carbide was added in the preparation of the modifying agent, no flaky alumina agent was added in the preparation of the modifying agent, no flaky alumina was added in the preparation of the flaky alumina agent, nano silica sol, no carboxymethyl cellulose was added in the preparation of the flaky alumina agent, and deionized water was used instead of lanthanum chloride solution, and the performance of the products showed a trend of deterioration to varying degrees;

[0172] The performance effect of the modified nano zinc oxide is most significant when the specific flaky alumina agent of the present invention is combined with the modification agent obtained by the process of the present invention. Other methods are not as obvious as the effect of the present invention.

[0173] Since adjusting the modifying liquid has a significant impact on the performance of the product, further research is conducted on this:

[0174] Experimental example 1.

[0175] The only difference from Example 3 is that no pretreated zirconium dioxide is added to the modified solution.

[0176] Experimental example 2.

[0177] The only difference from Example 3 is that dopamine hydrochloride and sodium citrate are not added to the modified solution.

[0178] Experimental Example 3.

[0179] The only difference from Example 3 is that no silicon powder is added to the modified silicon powder liquid.

[0180] Experimental Example 4.

[0181] The only difference from Example 3 is that no chitosan solution is added to the modified silicon micropowder solution.

[0182] Experimental Example 5.

[0183] The only difference from Example 3 is that no lanthanum nitrate solution is added to the modified silicon micropowder solution.

[0184]

[0185] It can be seen from Experimental Examples 1-5 that when no pretreated zirconium dioxide is added to the modified liquid, the performance of the product is most significantly affected by the modified liquid, followed by the modified silicon powder liquid without adding silicon powder, and at the same time, when no dopamine hydrochloride and sodium citrate are added to the modified liquid, and when no chitosan solution and lanthanum nitrate solution are added to the modified silicon powder liquid, the performance of the product has a tendency to deteriorate to varying degrees. The modified silicon powder liquid obtained by the specific method of the present invention is combined with pretreated zirconium dioxide, dopamine hydrochloride and sodium citrate, and the specific raw material components of the present invention are used. The modified liquid obtained by mutual coordination and synergy between the raw materials has the most significant effect on the product performance. The raw materials in the modified liquid are indispensable, and other methods are used instead, which are not as significant as the effect of the present invention.

[0186] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0187] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A modified water-based cold-dip galvanizing anti-corrosion coating, characterized in that: The anticorrosive coating comprises the following raw materials in parts by weight: 30-35 parts of water-based acrylic resin, 8-14 parts of functional additives based on stability adjustment, 7-11 parts of modified nano zinc oxide, 6-9 parts of curing agent, 2-4 parts of film-forming aid, 1-3 parts of defoaming agent, 4-7 parts of silane coupling agent KH560, and 25-30 parts of deionized water; The preparation method of the functional additive based on stability regulation is: S01: heat-treat the nano-mica powder at 155-165°C for 5-10 min, and then air-cool to room temperature; S02: prepare a sodium lignin sulfonate solution with a mass fraction of 4-7%; 2~5% sodium alginate solution by mass; 5-8 parts of nano-mica powder cooled to room temperature, 2-5 parts of sodium lignin sulfonate solution, 1-3 parts of silicon carbide whiskers and 3-6 parts of sodium alginate solution are fully mixed, then washed with water and dried to obtain a stabilizer; S03: Adjust the modifying liquid and the stabilizer according to the weight ratio of 3: (5-7), mix and ball mill, the ball mill speed is 1500r / min, the ball milling is 1h, after the ball milling is completed, wash with water, and dry to obtain a functional additive based on stabilizer adjustment; The preparation method of the regulating and modifying liquid is: 3-5 parts of silicon micropowder, 2-5 parts of chitosan solution and 1-3 parts of lanthanum nitrate solution were mixed and ball-milled at a speed of 1500 r / min for 1 h to obtain a modified silicon micropowder solution; The zirconium dioxide is first pretreated in a sufficient amount of a 6% by mass potassium permanganate solution, and after the treatment, it is washed with water and dried to obtain the pretreated zirconium dioxide; Then, 1 to 3 parts of dopamine hydrochloride and 2 to 4 parts of pretreated zirconium dioxide are added to 5 to 8 parts of modified silicon micropowder solution, and then 2 to 3 parts of sodium citrate are added and stirred to obtain an adjusted modified solution; The preparation method of the modified nano zinc oxide is: S11: treating the nano zinc oxide powder in a plasma box for 10-15 minutes, with a plasma power of 350-400W, and then the treatment is completed; 5-8 parts of plasma-treated nano zinc oxide powder, 4-6 parts of sodium silicate solution, and 1-3 parts of silane coupling agent KH550 are uniformly mixed to obtain nano zinc oxide liquid; S12: Preparation of modified treatment agent: S121: Stirring titanium carbide in a sufficient amount of nitric acid aqueous solution with a mass concentration of 15-20%, then washing with water and drying to obtain acid-treated titanium carbide; S122: 3-6 parts of flaky aluminum oxide and 1-3 parts of nano-silica sol are added to 5-8 parts of lanthanum chloride solution, and then 2-4 parts of carboxymethyl cellulose are added, and stirred thoroughly to obtain a flaky aluminum oxide agent; S123: Acid-treated titanium carbide and flaky aluminum oxide are stirred in a weight ratio of 3:(5-7) to obtain a modified treatment agent; S13: Mix the nano zinc oxide liquid and the modifying agent in a weight ratio of 5:(2-3) and perform ball milling at a ball milling speed of 1000-1500 r / min for 1 hour. After the ball milling is completed, wash with water and dry to obtain modified nano zinc oxide.

2. A modified water-based cold-dip galvanizing anti-corrosion coating according to claim 1, characterized in that: The modified water-based cold-dip galvanizing anti-corrosion coating comprises the following raw materials in parts by weight: 32.5 parts of water-based acrylic resin, 11 parts of functional additives based on stability adjustment, 9 parts of modified nano zinc oxide, 7.5 parts of curing agent, 3 parts of film-forming aid, 2 parts of defoaming agent, 5.5 parts of silane coupling agent KH560, and 27.5 parts of deionized water.

3. A modified water-based cold-dip galvanizing anti-corrosion coating according to claim 1, characterized in that: The curing agent is an isocyanate curing agent; the defoaming agent is polysiloxane; and the film-forming aid is dipropylene glycol butyl ether.

4. A modified water-based cold-dip galvanizing anti-corrosion coating according to claim 1, characterized in that: The mass fraction of the chitosan solution is 2-5%; the mass fraction of the lanthanum nitrate solution is 4%.

5. The modified water-based cold-dip galvanizing anti-corrosion coating according to claim 1, characterized in that: The pretreatment temperature is 50-55° C., the treatment time is 10-20 min, and the treatment speed is 550-650 r / min.

6. The modified water-based cold-dip galvanizing anti-corrosion coating according to claim 1, characterized in that: The sheet diameter of the flaky aluminum oxide is 150-200 nm, and the sheet thickness is 10-15 nm; the particle size of the nano zinc oxide powder is 50-60 nm; The mass fraction of the sodium silicate solution is 2-5%; the mass fraction of the lanthanum chloride solution is 3-6%.

7. The method for preparing the modified water-based cold-dip galvanizing anticorrosive coating according to any one of claims 1 to 6, characterized in that: The following steps are involved: The functional additive based on resistance and stability adjustment, modified nano zinc oxide, and silane coupling agent KH560 are first mixed to obtain a mixture; then the mixture, water-based acrylic resin, film-forming aid and defoaming agent are added to deionized water in sequence, and then a curing agent is added, and the mixture is stirred at 550-750r / min for 1h. After the stirring is completed, a modified water-based cold-dip galvanizing anti-corrosion coating can be obtained.

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