A nano-rust-inhibiting filler and a tank exterior wall coating containing the nano-rust-inhibiting filler

Abstract

This invention discloses a nano-rust-inhibiting filler and a tank exterior wall coating containing the nano-rust-inhibiting filler. The invention uses a liquid-phase precipitation method to prepare cerium-doped zirconium phosphate nano-rust-inhibiting filler. Cerium salt and zirconium salt are reacted and aged in an acid solution, then filtered, washed, dried, and ground. The mixture is then sieved through a 48-125 μm filter to obtain a cerium ion to zirconium ion molar ratio of 1:(4-7). The tank exterior wall coating containing the nano-rust-inhibiting filler disclosed in this invention is formed by thoroughly mixing component A (18-25 parts deionized water, 0.8-1.2 parts dispersant, 30-45 parts pigments and fillers, 4-10 parts auxiliary rust-inhibiting filler, 25-35 parts self-emulsifying waterborne epoxy curing agent) with component B (55-95 parts liquid epoxy resin, 3-6 parts reactive diluent, 4-10 parts co-solvent, 10-35 parts nano-rust-inhibiting filler). This invention improves the corrosion resistance and physical properties of the coating film on the substrate surface, while reducing pollution to human health and the environment.

Description

Technical Field

[0001] This invention relates to the field of coating technology, specifically to a nano-rust-inhibiting filler and a tank exterior wall coating containing the nano-rust-inhibiting filler. Background Technology

[0002] Currently, most exterior wall coatings for oil storage tanks on the market are solvent-based epoxy coatings, which have problems such as high toxicity, high pollution, and greenhouse gas emissions. Long-term use will have serious impacts on human health and the environment. At the same time, in order to respond to the national policy of reducing carbon emissions, the use of water-based coatings to replace solvent-based coatings has become an inevitable trend.

[0003] In patent application CN202211740673.1, an anti-corrosion coating using epoxy emulsion combined with water-based polyamide and zinc phosphate is described, which can be used for storage tank corrosion protection. However, the polyamide curing agent itself has limited performance in acid resistance tests, and the zinc phosphate used is not inherently acid-resistant, therefore the chemical resistance of this formulation is insufficient. In patent application CN201711047869.1, an anti-corrosion coating using acrylic emulsion is described, which can be used for storage tank corrosion protection. Because the curing process of acrylic emulsion involves the extension and entanglement of long-chain molecules, with molecules linked by van der Waals forces, its anti-corrosion performance is not as good as that of epoxy coatings, which are linked by chemical bonds. Summary of the Invention

[0004] The technical problem solved by this invention is how to improve the anti-corrosion and physical properties of the coating film on the substrate surface, while reducing pollution to human body and environment.

[0005] To address the above technical problems, the first objective of this invention is to provide a nano-rust-preventive filler, wherein the nano-rust-preventive filler is a cerium-doped zirconium phosphate nano-rust-preventive filler prepared by liquid-phase precipitation.

[0006] Preferably, the step of preparing nano-rust inhibitory fillers by liquid-phase precipitation includes,

[0007] Step A): Dissolve zirconium salt and cerium salt in deionized water at certain concentrations to obtain zirconium salt aqueous solution and cerium salt aqueous solution; mix the two aqueous solutions according to a molar ratio of cerium ion to zirconium ion of 1: (4~7) to obtain a mixed ionic solution;

[0008] Step B): Weigh a mixed acid solution of a certain concentration; the mass ratio of the mixed acid solution to the mixed ion solution in Step A) is 1:(8~10).

[0009] Step C): Under a certain stirring speed, add the mixed acid solution from step B) dropwise to the mixed ionic solution from step A). ​​After the addition is complete, stir and let it age.

[0010] Step D) The aged solution from step C) is filtered, and then washed with deionized water. After vacuum drying, it is ground and sieved through a filter screen to obtain cerium-doped zirconium phosphate nano-rust inhibitory filler.

[0011] Preferably, in step A), the concentration of the zirconium salt aqueous solution is 0.1~0.3 mol / L, and the concentration of the cerium salt aqueous solution is 0.1~0.3 mol / L;

[0012] In step C), the stirring speed is 300-400 rpm, the dropping rate of the mixed acid solution is 1.5-3 ml / min, the stirring time is 20-30 min, and the mixture is left to age for 16-24 h.

[0013] In step D), a polytetrafluoroethylene filter membrane with a filter diameter of 0.1-0.2 μm is used for vacuum filtration. The filter is washed and vacuum filtered 2-6 times. The vacuum drying temperature is 55-75℃ and the drying time is 24-72h. The pore size of the filter screen is 48-125 μm.

[0014] Preferably, in step B), the mixed acid solution is a mixture of a hydrochloric acid solution with a mass concentration of 15-36% and a phosphoric acid solution with a mass concentration of 55-85% at a mass ratio of 1:(3-4).

[0015] Preferably, the zirconium salt is one or more of zirconium oxychloride octahydrate, zirconium chloride, and zirconium acetate.

[0016] Preferably, the cerium salt is one or more of cerium chloride heptahydrate, cerium chloride hexahydrate, cerium chloride trihydrate, cerium chloride, cerium bromide, and cerium iodide.

[0017] The second objective of this invention is to provide a tank exterior wall coating containing nano-rust-inhibiting fillers, which is composed of a uniform mixture of component A and component B. The raw material composition of each component includes, by weight,

[0018] Component A: 18-25 parts deionized water, 0.8-1.2 parts dispersant, 30-45 parts pigments and fillers, 4-10 parts auxiliary rust-inhibiting fillers, and 25-35 parts self-emulsifying waterborne epoxy curing agent;

[0019] Component B: 55-95 parts liquid epoxy resin, 3-6 parts reactive diluent, 4-10 parts cosolvent, and 10-35 parts nano-rust-inhibiting filler.

[0020] Preferably, the auxiliary rust-preventive filler in component A is one or more of the following: zinc phosphate, aluminum phosphate, zinc aluminum phosphate, aluminum tripolyphosphate, calcium phosphate, calcium strontium phosphosilicate, zinc strontium phosphosilicate, barium phosphosilicate, calcium phosphosilicate, strontium phosphosilicate, barium metaborate, magnesium metaborate, and calcium metaborate.

[0021] Preferably, the dispersant in component A is one or more of ammonium polyacrylate, sodium polyacrylate, sodium polycarboxylate, and Additol VXW 6208 / 60.

[0022] Preferably, the pigments and fillers in component A are one or more of titanium dioxide, barium sulfate, mica powder, talc powder, glass flakes, and mica iron oxide.

[0023] Preferably, the self-emulsifying waterborne epoxy curing agent in component A is one or more of the following: WSCM-6460 from Zhejiang Wansheng, Aradur 3986 from Huntsman, Banco 920 from LianGu Chemical, and EPIKURE 8545-W-52 from Hansen.

[0024] Preferably, the liquid epoxy resin in component B is one or more of bisphenol F type epoxy resin or bisphenol A type epoxy resin.

[0025] Preferably, the active diluent in component B is cashew phenol glycidyl ether or neopentyl glycol diglycidyl ether.

[0026] Preferably, the co-solvent in component B is one or more of alcohol esters, ethers, alcohol ethers, and alcohols.

[0027] Preferably, the raw material components of component A and component B further include, by weight,

[0028] Component A: 0.3-0.6 parts thixotropic agent, 0.2-0.4 parts defoamer, 0.2-0.5 parts flash rust inhibitor, 0.3-0.7 parts corrosion inhibitor, 0.2-0.4 parts leveling agent, and 0.3-0.6 parts adhesion promoter;

[0029] Component B: 0.5~1.2 parts of dispersant.

[0030] Preferably, the thixotropic agent in component A is one or more of bentonite, fumed silica, and attapulgite; the defoamer is a compound of polyether siloxane copolymer and fumed silica, which is an emulsion-type organosilicon-modified defoamer; the flash rust inhibitor is one or more of Nalzin FA~179, Halox Flash X-150, and 15% sodium nitrite aqueous solution; the corrosion inhibitor is Halox 550WF or Halox 515; the leveling agent is one or more of organosilicon, polyacrylate, acetylacetonate, and fluorocarbon-modified polyacrylate; the adhesion promoter is one or more of glycidyl etheroxypropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, and epoxy-functionalized oligomeric siloxane; and the dispersant in component B is one or more of ammonium polyacrylate, sodium polyacrylate, sodium polycarboxylate, and Additol VXW6208 / 60.

[0031] Preferably, the preparation method is as shown in the following steps.

[0032] To prepare component A, the appropriate mass of deionized water, dispersant, and defoamer were dispersed at 800-1000 rpm for 10-15 min. Then, the appropriate mass of pigments, fillers, auxiliary rust inhibitors, and thixotropic agents were added and dispersed at 1500-2000 rpm until the fineness was less than 50 μm. Next, the appropriate weight of self-emulsifying waterborne epoxy curing agent, flash rust inhibitor, corrosion inhibitor, leveling agent, adhesion promoter, and the remaining deionized water were added and dispersed at 1000-1500 rpm for 10-15 min to obtain component A.

[0033] To prepare component B, the appropriate weights of liquid epoxy resin, reactive diluent, dispersant, cosolvent, and nano-rust inhibitory filler were dispersed by sand milling at 1000~1500 rpm for 15~30 min to achieve a fineness of less than 50 μm, thus obtaining component B.

[0034] Mix components A and B in a ratio of (2~6):1 to obtain a tank exterior wall coating containing nano-rust-preventive fillers.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] The cerium-doped zirconium phosphate nano-rust inhibitor provided in this invention utilizes zirconium phosphate, which has a lamellar structure. This structure not only passivates the substrate and fills small gaps but also creates a labyrinth effect and exhibits good acid and alkali resistance. The cerium phosphate doped with it not only participates in substrate passivation but also reacts with alkaline substances or water to form insoluble substances, acting as a barrier. Due to the small size effect of the nanoparticles, the cerium-doped zirconium phosphate nano-rust inhibitor also significantly improves the mechanical properties of the paint film. A synergistic effect is achieved between the nano-rust inhibitor and auxiliary rust inhibitors (such as barium metaborate). The first type of rust inhibitor acts as an acid buffer, slowing down the rate of acid corrosion and also forming insoluble substances with some acids, thus providing a barrier. Simultaneously, the use of a self-emulsifying epoxy curing agent allows for direct emulsification of liquid epoxy resin, reducing the amount of highly toxic and polluting organic solvents used while maintaining good anti-corrosion performance.

[0037] The rust-preventive mechanism of cerium phosphate is as follows:

[0038] .

[0039] The passivation mechanism of cerium-doped zirconium phosphate nanofiller for rust prevention is as follows:

[0040] .

[0041] The reaction mechanism of barium metaborate with sulfuric acid is as follows:

[0042] .

[0043] Specifically: (1) The paint film is obtained by curing epoxy resin and curing agent. The curing speed is fast and the cured paint film has good anti-corrosion performance. (2) Nanoparticles are used as fillers. Due to the small size effect, the mechanical properties of the paint film will be significantly improved. (3) Cerium-doped zirconium phosphate nanoparticles are used as anti-rust pigments. While passivating the substrate, they can form insoluble substances to play a barrier effect. (4) Barium metaborate and other materials are used as auxiliary anti-rust fillers and acid buffers. Under acidic conditions, they will react with acid to slow down the corrosion rate. At the same time, they will also form insoluble substances with some acid to play a better barrier role. (5) Using 1200 mesh barium sulfate, 800 mesh mica powder and barium metaborate and cerium-doped zirconium phosphate nanoparticle anti-rust fillers of three different finenesses can make the paint film denser and stronger infiltration resistance.

[0044] The coating of this invention has the characteristics of low toxicity, fast curing speed, environmental protection, good salt spray resistance, and good resistance to corrosive media. Attached Figure Description

[0045] Figure 1 Blue light phenomenon of nano-rust inhibitory filler suspension

[0046] Figure 2 A diagram illustrating the maze effect.

[0047] Table 1 shows the specific technical specifications of the coating.

[0048] Table 2 shows the preparation requirements for the test samples.

[0049] Table 3 shows the results of the physical performance tests.

[0050] Table 4 shows the results of the 1000h salt spray test.

[0051] Table 5 shows the results of the hot water resistance test at 90~100℃.

[0052] Table 6 shows the test results for resistance to liquid chemicals. Detailed Implementation

[0053] To further illustrate the present invention, the following embodiments are provided, but the present invention is not limited to these embodiments, and those skilled in the art can make appropriate modifications.

[0054] Examples 1 to 3 are examples of the preparation of cerium-doped zirconium phosphate nano-rust inhibitors.

[0055] Example 1

[0056] ① Take 33.7 parts of zirconium oxychloride octahydrate and 7.8 parts of cerium chloride heptahydrate by mass, dissolve them in 488.7 parts and 96.7 parts of deionized water respectively, and mix them.

[0057] ② Take 53.01 parts of 85% phosphoric acid solution and 16.69 parts of 36% hydrochloric acid solution by mass and mix them.

[0058] ③ Add a mixture of phosphoric acid and hydrochloric acid dropwise to the zirconium oxychloride and cerium chloride solution at a stirring speed of 300~400 rpm at a rate of 1.5~3 ml / min. After the addition is complete, stir for 20 min and let it age for 16 h.

[0059] ④ The filter was filtered using a polytetrafluoroethylene membrane with a filter diameter of 0.1 μm, and washed with deionized water four times. After vacuum drying at 65℃ for 48 hours, the filter was ground and sieved through a 200-mesh (approximately 75 micrometers in pore size) screen to finally obtain cerium-doped zirconium phosphate nano-rust inhibitor filler.

[0060] Example 2

[0061] ① Take 32.5 parts of zirconium oxychloride octahydrate and 9.4 parts of cerium chloride heptahydrate by mass, dissolve them in 471.8 parts and 116.7 parts of deionized water respectively, and mix them.

[0062] ② Take 53.01 parts of 85% phosphoric acid solution and 16.69 parts of 36% hydrochloric acid solution by mass and mix them.

[0063] ③ Add a mixture of phosphoric acid and hydrochloric acid dropwise to the zirconium oxychloride and cerium chloride solution at a stirring speed of 300~400 rpm at a rate of 1.5~3 ml / min. After the addition is complete, stir for 20 min and let it age for 16 h.

[0064] ④ The filter was filtered using a polytetrafluoroethylene membrane with a filter diameter of 0.1 μm, and washed with deionized water four times. After vacuum drying at 65℃ for 48 hours, the filter was ground and sieved through a 200-mesh screen to finally obtain cerium-doped zirconium phosphate nano-rust inhibitory filler.

[0065] Example 3

[0066] ① Take 34.5 parts of zirconium oxychloride octahydrate and 7.75 parts of cerium chloride heptahydrate by mass, dissolve them in 500.6 parts and 96.3 parts of deionized water respectively, and mix them.

[0067] ② Take 53.01 parts of 75% phosphoric acid solution and 16.69 parts of 25% hydrochloric acid solution by mass and mix them.

[0068] ③ Add a mixture of phosphoric acid and hydrochloric acid dropwise to the zirconium oxychloride and cerium chloride solution at a stirring speed of 300~400 rpm at a rate of 1.5~3 ml / min. After the addition is complete, stir for 20 min and let it age for 16 h.

[0069] ④ The filter was filtered using a polytetrafluoroethylene membrane with a filter diameter of 0.1 μm, and washed with deionized water four times. After vacuum drying at 75℃ for 48 hours, the filter was ground and sieved through a 200-mesh screen to finally obtain cerium-doped zirconium phosphate nano-rust inhibitory filler.

[0070] Examples 4 to 6 are examples of preparation of tank exterior wall coatings containing cerium-doped zirconium phosphate nano-rust inhibitory fillers.

[0071] Example 4

[0072] Preparation of component A:

[0073] ① Take 19 parts by weight of deionized water, 0.9 parts of dispersant OROTAN 1124, and 0.2 parts of defoamer TEGO Airex810W and add them to the dispersion tank. Control the rotation speed at 800 rpm and disperse for 10 minutes.

[0074] ② Take 7 parts titanium dioxide, 16 parts barium sulfate, 17 parts mica powder, 4 parts barium metaborate, 0.2 parts fumed silica Aerosil R972, and 0.2 parts bentonite BP-188B by mass ratio, add them to the dispersion tank, and gradually increase the rotation speed to 2500 rpm while adding the materials. Disperse for 3 hours until the fineness reaches 20~30μm.

[0075] ③ Reduce the rotation speed to 1500 rpm, and take the following materials by weight: 28 parts of water-based epoxy curing agent WSCM-6460, 0.2 parts of defoamer TEGO Airex 902W, 0.3 parts of anti-flash rust agent Halox Flash X-150, 0.5 parts of corrosion inhibitor Halox 550W, 0.4 parts of adhesion promoter Coatosil MP200, 0.2 parts of leveling agent TEGO TWIN 4100, and 5.9 parts of deionized water. After adding all of them, disperse for 30 minutes.

[0076] ④ After dispersion is complete, the material is discharged to obtain component A.

[0077] Preparation of component B:

[0078] ① Take 66.5 parts by weight of liquid epoxy resin YD~170, 1 part of dispersant Additol VXW 6208 / 60, 9 parts of cosolvent PM, 4 parts of reactive diluent WSCM-5110, and 19.5 parts of nano-cerium phosphate doped zirconium phosphate and add them to the dispersion tank. Use a sand mill to maintain the speed at 2000 rpm and disperse for 3 hours until the fineness reaches 0 μm.

[0079] ② After dispersion is complete, component B is obtained by discharging the material;

[0080] Mix components A and B in a ratio of 4.73:1 to obtain a water-based epoxy coating.

[0081] Example 5

[0082] Preparation of component A:

[0083] ① Take 19 parts by weight of deionized water, 0.9 parts of dispersant OROTAN 1124, and 0.2 parts of defoamer TEGO Airex810W and add them to the dispersion tank. Control the rotation speed at 800 rpm and disperse for 10 minutes.

[0084] ② Take 7 parts titanium dioxide, 16 parts barium sulfate, 17 parts mica powder, 4.1 parts barium metaborate, 0.2 parts fumed silica Aerosil R972, and 0.2 parts bentonite BP-188B by mass ratio, add them to the dispersion tank, and gradually increase the rotation speed to 2500 rpm while adding the materials. Disperse for 3 hours until the fineness reaches 20~30μm.

[0085] ③ Reduce the rotation speed to 1500 rpm, and take the following materials by weight: 29 parts of water-based epoxy curing agent WSCM-6460, 0.2 parts of defoamer TEGO Airex 902W, 0.3 parts of anti-flash rust agent Halox Flash X-150, 0.5 parts of corrosion inhibitor Halox 550W, 0.4 parts of adhesion promoter Coatosil MP200, 0.2 parts of leveling agent TEGO TWIN 4100, and 4.8 parts of deionized water. After adding all of them, disperse for 30 minutes.

[0086] ④ After dispersion is complete, the material is discharged to obtain component A;

[0087] Preparation of component B:

[0088] ① Take 60.5 parts by weight of liquid epoxy resin YD~170, 1 part of dispersant Additol VXW 6208 / 60, 9 parts of cosolvent PM, 3.5 parts of reactive diluent WSCM-5110, and 26 parts of cerium-doped zirconium phosphate nano-rust inhibitor filler and add them to a dispersion tank. Use a sand mill to maintain a speed of 2000 rpm and disperse for 3 hours until the fineness reaches 0 μm.

[0089] ② After dispersion is complete, component B is obtained by discharging the material;

[0090] Mix components A and B evenly in a ratio of 4.15:1 to obtain a water-based epoxy coating.

[0091] Example 6

[0092] Preparation of component A:

[0093] ① Take 19 parts by weight of deionized water, 0.9 parts of dispersant OROTAN 1124, and 0.2 parts of defoamer TEGO Airex810W and add them to the dispersion tank. Control the rotation speed at 800 rpm and disperse for 10 minutes.

[0094] ② Take 7 parts titanium dioxide, 16 parts barium sulfate, 17 parts mica powder, 4.2 parts barium metaborate, 0.2 parts fumed silica Aerosil R972, and 0.2 parts bentonite BP-188B by mass ratio, add them to the dispersion tank, and gradually increase the rotation speed to 2500 rpm while adding the materials, and disperse for 3 hours until the fineness reaches 20~30μm;

[0095] ③ Reduce the rotation speed to 1500 rpm, and take the following materials by weight: 30 parts of water-based epoxy curing agent WSCM-6460, 0.2 parts of defoamer TEGO Airex 902W, 0.3 parts of anti-flash rust agent Halox Flash X-150, 0.5 parts of corrosion inhibitor Halox 550W, 0.4 parts of adhesion promoter Coatosil MP200, 0.2 parts of leveling agent TEGO TWIN 4100, and 3.7 parts of deionized water. After adding all of them, disperse for 30 minutes.

[0096] ④ After dispersion is complete, the material is discharged to obtain component A;

[0097] Preparation of component B:

[0098] ① Take 58 parts by weight of liquid epoxy resin YD-170, 1 part of dispersant Additol VXW 6208 / 60, 6 parts of cosolvent PM, 3.5 parts of reactive diluent WSCM-5110, and 31.5 parts of cerium-doped zirconium phosphate nano-rust inhibitor filler and add them to a dispersion tank. Use a sand mill to maintain a speed of 2000 rpm and disperse for 3 hours until the fineness reaches 0 μm.

[0099] ② After dispersion is complete, component B is obtained by discharging the material;

[0100] Mix components A and B evenly in a ratio of 3.85:1 to obtain a water-based epoxy coating.

[0101] Comparative Example 1

[0102] Preparation of component A:

[0103] ① Take 19 parts by weight of deionized water, 1 part of dispersant OROTAN 1124, and 0.2 parts of defoamer TEGO Airex810W and add them to the dispersion tank. Control the speed at 800 rpm and disperse for 10 minutes.

[0104] ② Take 7 parts titanium dioxide, 13 parts barium sulfate, 16 parts mica powder, 8 parts calcium strontium phosphosilicate, 4 parts barium metaborate, 0.2 parts fumed silica Aerosil R972, and 0.2 parts bentonite BP-188B by mass ratio, add them to the dispersion tank, and gradually increase the rotation speed to 2500 rpm while adding the materials, and disperse for 3 hours until the fineness reaches 20~30μm;

[0105] ③ Reduce the rotation speed to 1500 rpm, and take the following materials by weight: 29.5 parts of water-based epoxy curing agent WSCM-6460, 0.2 parts of defoamer TEGO Airex 902W, 0.3 parts of anti-flash rust agent Halox Flash X-150, 0.5 parts of corrosion inhibitor Halox 550W, 0.4 parts of adhesion promoter Coatosil MP200, 0.2 parts of leveling agent TEGO TWIN 4100, and 0.3 parts of deionized water. After adding all of them, disperse for 30 minutes.

[0106] ④ After dispersion is complete, the material is discharged to obtain component A;

[0107] Preparation of component B:

[0108] ① Take 91 parts of liquid epoxy resin YD~170, 5 parts of cosolvent PM, and 4 parts of reactive diluent WSCM-5110 according to the mass ratio and add them to the dispersion tank. Keep the rotation speed at 1500 rpm and disperse for 20 min.

[0109] ② After dispersion is complete, component B is obtained by discharging the material;

[0110] Mix components A and B in a ratio of 6.11:1 to obtain a water-based epoxy coating.

[0111] Comparative Example 2

[0112] Preparation of component A:

[0113] ① Take 19 parts by weight of deionized water, 0.9 parts of dispersant OROTAN 1124, and 0.2 parts of defoamer TEGO Airex810W and add them to the dispersion tank. Control the rotation speed at 800 rpm and disperse for 10 minutes.

[0114] ② Take 7 parts titanium dioxide, 16 parts barium sulfate, 17 parts mica powder, 4.2 parts barium metaborate, 0.2 parts fumed silica Aerosil R972, and 0.2 parts bentonite BP-188B by mass ratio, add them to the dispersion tank, and gradually increase the rotation speed to 2500 rpm while adding the materials, and disperse for 3 hours until the fineness reaches 20~30μm;

[0115] ③ Reduce the rotation speed to 1500 rpm, and take the following materials by weight: 30.5 parts of water-based epoxy curing agent WSCM-6460, 0.2 parts of defoamer TEGO Airex 902W, 0.3 parts of anti-flash rust agent Halox Flash X-150, 0.5 parts of corrosion inhibitor Halox 550W, 0.4 parts of adhesion promoter Coatosil MP200, 0.2 parts of leveling agent TEGO TWIN 4100, and 3.2 parts of deionized water. After adding all of them, disperse for 30 minutes.

[0116] ④ After dispersion is complete, the material is discharged to obtain component A;

[0117] Preparation of component B:

[0118] ① Take 58 parts by weight of liquid epoxy resin YD~170, 1 part of dispersant Additol VXW 6208 / 60, 6 parts of cosolvent PM, 3.5 parts of reactive diluent WSCM-5110, and 31.5 parts of zinc phosphate and add them to the dispersion tank. Keep the rotation speed at 2000 rpm and disperse for 2 hours until the fineness reaches 30~40μm.

[0119] ② After dispersion is complete, component B is obtained by discharging the material;

[0120] Mix components A and B in a ratio of 3.79:1 to obtain a water-based epoxy coating.

[0121] The liquid epoxy resin is YD-170; the reactive diluent is WSCM-5110 from Zhejiang Wansheng; the dispersant is one or more of OROTAN 1124, SN-5040, LX-5040, and Additol VXW 6208 / 60; the defoamer is one or more of 902W and 810W; the flash rust inhibitor is one or more of FA-179 and Halox Flash X-150; the corrosion inhibitor is Halox 550WF; the adhesion promoter is Coatosil MP200 and ADP~452; the leveling agent is one or more of TWIN 4100, Surfynol 440, and BYK~333; and the thixotropic agent is BP-188B, Bentone DE, and Aerosil. One or more of R972; the co-solvent is one or more of PM and Texanol; the water-based epoxy curing agent is WSCM-6460 from Zhejiang Wansheng.

[0122] Performance testing

[0123] The waterborne epoxy coatings prepared in Comparative Examples 1-2 and Examples 4-6 were subjected to performance tests. The specific indicators are shown in Tables 1 and 2, and the test results are shown in Tables 3, 4, and 5.

[0124] The adhesion test of waterborne epoxy coatings is based on the standard GB 5210~2006; the flexibility test of waterborne epoxy coatings is based on the standard GB / T 1731~2020; the impact resistance test of waterborne epoxy coatings is based on the standard GB 1732~2020; the salt spray resistance test of waterborne epoxy coatings is based on the standard GB / T 1771~2007; and the chemical resistance, hot water resistance test, and all test requirements of waterborne epoxy coatings are based on the standard GB / T 50393~2017.

[0125] Table 1. Specific technical specifications of Comparative Examples 1-2 and Examples 4-6

[0126]

[0127] Conclusion: Except for the content of VOC and rust-inhibiting filler, the specific technical indicators of Comparative Examples 1-2 and Examples 4-6 are not significantly different.

[0128] Table 2 Requirements for Test Sample Preparation

[0129]

[0130] Table 3 Physical Performance Test Results

[0131]

[0132] Conclusion: With the increase of cerium-doped zirconium phosphate nano-rust inhibitory filler, the flexibility and impact resistance are significantly improved. The flexibility of Example 6 is better than that of Comparative Examples 1 and 2 and Examples 4 and 5, and the impact resistance of Examples 5 and 6 is better than that of Comparative Examples 1 and 2 and Example 1.

[0133] Table 4 Results of 1000h Salt Spray Resistance Test in the Laboratory

[0134]

[0135] Conclusion: Comparative Example 2 and Example 6 showed the best salt spray resistance. The results show that as the amount of cerium-doped zirconium phosphate nano-rust inhibitory filler increased, the corrosion width decreased significantly.

[0136] Table 5 Results of laboratory tests for resistance to 90-100℃ hot water for 2 days

[0137]

[0138] Conclusion: The results of Examples 4-6 are significantly better than those of Comparative Examples 1 and 2, and Examples 5 and 6 are better than Example 4. This is because as the amount of cerium-doped zirconium phosphate nano-rust inhibitory filler increases, more gaps between particles are filled, the maze effect is enhanced, and the density of the paint film is increased, resulting in better impermeability.

[0139] Table 6 Results of 7-day chemical resistance test in the laboratory

[0140]

[0141] Conclusion: In the sulfuric acid resistance test, Examples 4-5 were superior to Comparative Examples 1 and 2, and Example 6 was superior to Examples 4 and 5. This is because zinc phosphate has good rust prevention performance but poor acid resistance, calcium strontium phosphosilicate has good acid resistance but insufficient rust prevention performance, and cerium-doped zirconium phosphate nano-rust inhibitory filler has both good acid resistance and rust prevention performance.

[0142] The above description represents several preferred embodiments of a water-based epoxy primer disclosed in this invention. For those skilled in the art, any modifications or improvements made without departing from the concept of this invention are within the scope of protection of this invention.

Claims

1. A nano-rust-inhibiting filler, characterized in that, The nano-rust-inhibiting filler is a cerium-doped zirconium phosphate nano-rust-inhibiting filler prepared by liquid-phase precipitation. The steps of preparing the nano-rust-inhibiting filler by liquid-phase precipitation include: Step A): Dissolve zirconium salt and cerium salt in deionized water at certain concentrations to obtain zirconium salt aqueous solution and cerium salt aqueous solution; mix the two aqueous solutions according to a molar ratio of cerium ion to zirconium ion of 1: (4~7) to obtain a mixed ionic solution; Step B): Weigh a mixed acid solution of a certain concentration; the mass ratio of the mixed acid solution to the mixed ion solution in Step A) is 1:(8~10). Step C): Under a certain stirring speed, add the mixed acid solution from step B) dropwise to the mixed ionic solution from step A). ​​After the addition is complete, stir and let it age. Step D) The aged solution from step C) is filtered, and then washed with deionized water. After vacuum drying, it is ground and sieved through a filter screen to obtain cerium-doped zirconium phosphate nano-rust inhibitory filler. In step A), the concentration of the zirconium salt aqueous solution is 0.1~0.3 mol / L, and the concentration of the cerium salt aqueous solution is 0.1~0.3 mol / L; In step C), the stirring speed is 300-400 rpm, the dropping rate of the mixed acid solution is 1.5-3 ml / min, the stirring time is 20-30 min, and the mixture is left to age for 16-24 h. In step D), a polytetrafluoroethylene filter membrane with a filter diameter of 0.1-0.2 μm is used for vacuum filtration, and the filter is washed 2-6 times. The vacuum drying temperature is 55-75℃, the drying time is 24-72h, and the pore size of the filter screen is 48-125 μm. In step B), the mixed acid solution is a mixture of a hydrochloric acid solution with a mass concentration of 15-36% and a phosphoric acid solution with a mass concentration of 55-85% at a mass ratio of 1:(3-4). The zirconium salt is one or more of zirconium oxychloride octahydrate, zirconium chloride, and zirconium acetate; The cerium salt is one or more of cerium chloride heptahydrate, cerium chloride hexahydrate, cerium chloride trihydrate, cerium chloride, cerium bromide, and cerium iodide.

2. A tank exterior wall coating containing nano-rust-inhibiting fillers, characterized in that, The tank exterior wall coating containing the nano-rust inhibitor filler as described in claim 1 is composed of a uniformly mixed component A and component B, wherein the raw material composition of each component includes, by weight, Component A: 18-25 parts deionized water, 0.8-1.2 parts dispersant, 30-45 parts pigments and fillers, 4-10 parts auxiliary rust-inhibiting fillers, and 25-35 parts self-emulsifying waterborne epoxy curing agent; Component B: 55-95 parts liquid epoxy resin, 3-6 parts reactive diluent, 4-10 parts cosolvent, and 10-35 parts nano-rust-inhibiting filler; The auxiliary rust-preventive filler in component A is one or more of the following: zinc phosphate, aluminum phosphate, zinc aluminum phosphate, aluminum tripolyphosphate, calcium phosphate, calcium strontium phosphosilicate, zinc strontium phosphosilicate, barium phosphosilicate, calcium phosphosilicate, strontium phosphosilicate, barium metaborate, magnesium metaborate, and calcium metaborate.

3. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 2, characterized in that, The dispersant in component A is one or more of the following: ammonium polyacrylate, sodium polyacrylate, sodium polycarboxylate, and Additol VXW 6208 / 60.

4. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 2, characterized in that, The pigments and fillers in component A are one or more of titanium dioxide, barium sulfate, mica powder, talc powder, glass flakes, and mica iron oxide.

5. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 2, characterized in that, The self-emulsifying waterborne epoxy curing agent in component A is one or more of the following: WSCM-6460 from Zhejiang Wansheng, Aradur 3986 from Huntsman, Banco 920 from LianGu Chemical, and EPIKURE 8545-W-52 from Hansen.

6. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 2, characterized in that, The liquid epoxy resin in component B is one or more of bisphenol F type epoxy resin or bisphenol A type epoxy resin.

7. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 2, characterized in that, The active diluent in component B is cashew phenol glycidyl ether or neopentyl glycol diglycidyl ether.

8. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 2, characterized in that, The co-solvent in component B is one or more of the following: alcohol esters, ethers, alcohol ethers, and alcohols.

9. The tank exterior wall coating containing nano-rust-inhibiting fillers according to any one of claims 2-8, characterized in that, The raw material components of component A and component B also include, by weight, Component A: 0.3-0.6 parts thixotropic agent, 0.2-0.4 parts defoamer, 0.2-0.5 parts flash rust inhibitor, 0.3-0.7 parts corrosion inhibitor, 0.2-0.4 parts leveling agent, and 0.3-0.6 parts adhesion promoter; Component B: 0.5~1.2 parts of dispersant.

10. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 9, characterized in that, The thixotropic agent in component A is one or more of bentonite, fumed silica, and attapulgite; the defoamer is a compound of polyether siloxane copolymer and fumed silica, which is an emulsion-type organosilicon-modified defoamer; the flash rust inhibitor is one or more of Nalzin FA~179, Halox Flash X-150, and 15% sodium nitrite aqueous solution; the corrosion inhibitor is Halox 550WF or Halox 515; the leveling agent is one or more of organosilicon, polyacrylate, acetylacetonate, and fluorocarbon-modified polyacrylate; the adhesion promoter is one or more of glycidyl etheroxypropyltrimethoxysilane, 3-piperazinylpropylmethyldimethoxysilane, and epoxy-functionalized oligomeric siloxane; the dispersant in component B is one or more of ammonium polyacrylate, sodium polyacrylate, sodium polycarboxylate, and Additol VXW 6208 / 60.

11. The tank exterior wall coating containing nano-rust-inhibiting fillers according to claim 9, characterized in that, The preparation method is as shown in the following steps. To prepare component A, the appropriate mass of deionized water, dispersant, and defoamer were dispersed at 800-1000 rpm for 10-15 min. Then, the appropriate mass of pigments, fillers, auxiliary rust inhibitors, and thixotropic agents were added and dispersed at 1500-2000 rpm until the fineness was less than 50 μm. Next, the appropriate weight of self-emulsifying waterborne epoxy curing agent, flash rust inhibitor, corrosion inhibitor, leveling agent, adhesion promoter, and the remaining deionized water were added and dispersed at 1000-1500 rpm for 10-15 min to obtain component A. To prepare component B, the appropriate weights of liquid epoxy resin, reactive diluent, dispersant, cosolvent, and nano-rust inhibitory filler were dispersed by sand milling at 1000~1500 rpm for 15~30 min to achieve a fineness of less than 50 μm, thus obtaining component B. Mix components A and B in a ratio of (2~6):1 to obtain a tank exterior wall coating containing nano-rust-preventive fillers.

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