Lanthanum oxide rare earth modified waterborne epoxy static conductive coating as well as preparation method and application thereof

Abstract

The invention relates to the technical field of coatings, in particular to a lanthanum oxide rare earth modified waterborne epoxy static conductive coating and a preparation method and application thereof.The lanthanum oxide rare earth modified waterborne epoxy static conductive coating is prepared from, by mass, a component A: 16-18 parts of deionized water; 0.1 to 0.2 part of a defoaming agent; 0.9 to 1.2 parts of a dispersant; 1-2 parts of propylene glycol monomethyl ether; 0.6 to 0.8 part of a water-based anti-settling agent; 0.5 to 1 part of rutile type titanium dioxide; 15 to 20 parts of sericite powder; 1.0 to 1.5 parts of strontium chrome yellow; 10 to 15 parts of lanthanum oxide rare earth; 40 to 45 parts of waterborne epoxy emulsion; 0.3 to 0.4 part of a water-based base material wetting agent; 0.6 to 0.8 part of a water-based thickening agent; the component B comprises the following components in parts by weight: 60-80 parts of a waterborne epoxy curing agent; 20 to 30 parts of propylene glycol monomethyl ether; 10 to 20 parts of deionized water; and 10-15 parts of a water-based flash rust inhibitor. The conductive paint has excellent and long-acting conductive stability and corrosion resistance, and is light in color and not easy to diffuse to pollute oil products.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and more specifically, to a method for preparing a water-based electrostatic conductive coating using a water-based epoxy emulsion as a film-forming substance and lanthanum oxide as a conductive medium. Background Art

[0002] For various oil products in oil storage tanks, such as ethanol, methanol, gasoline, etc., when there is relative movement between the oil products and the tank body, the release rate of static electricity is lower than the accumulation rate of static electricity, which will increase the static voltage of the inner wall of the oil tank. When the accumulated static electricity energy is greater than the explosion limit of the combustible material, combustion or even explosion will occur. Therefore, when protecting oil tanks, the design institute generally requires the coating to have static electricity conductivity to prevent the accumulation of static electricity energy and promote the release of static electricity, thereby preventing the increase of static electricity on the surface of the coated object and avoiding the occurrence of combustion and explosion. According to the national standards "Safety Regulations for Electrostatics of Liquid Petroleum Products GB13348-92" and "Method for Determination of Resistivity of Conductive Coatings for Petroleum Tanks GB16906-1996", the volume resistivity of the conductive anti-corrosion coating on the inner wall of the oil tank should be less than 10 8 Ω.

[0003] Water-based paint is an important branch of the world's paint development towards greening, and has developed rapidly in recent years under the support of national policies. Compared with oil-based paint, water-based paint has the advantages of low VOC emissions, low odor, non-flammability, and non-explosion. The safety of use, transportation, and storage is greatly improved, and it is accepted by the market and the country. Water-based epoxy paint has extremely high adhesion to various substrates, low shrinkage, good wear resistance, high hardness, and excellent acid, alkali, and salt resistance. It is widely used in primers or areas where sunlight is not seen. Therefore, it is a future development trend for water-based epoxy conductive static paint to replace oil-based epoxy conductive static paint, and it will have broad application prospects in the steel structure of oil storage tanks.

[0004] In the prior art, oil tank coating is mainly based on adding black conductive graphite or dark gray conductive mica powder to oily epoxy and polyurethane resins. Its advantages are low price and short validity period, while its disadvantages are poor oil resistance, dark color, and the possibility of diffusion into the oil and contaminating the oil. Summary of the invention

[0005] The invention provides a lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating and a preparation method and application thereof. The prepared lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating has excellent and long-lasting conductive stability and anti-corrosion performance, and is light in color and not easy to spread and pollute oil products.

[0006] In a first aspect, the present invention provides a lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating, comprising raw materials of the following mass components: Component A: 16-18 parts of deionized water; Defoaming agent 0.1-0.2 parts; Dispersant 0.9-1.2 parts; Propylene glycol methyl ether 1-2 parts; 0.6-0.8 parts of water-based anti-settling agent; 0.5-1 part of rutile titanium dioxide; Sericite powder 15-20 parts; Strontium chrome yellow 1.0-1.5 parts; Lanthanum oxide rare earth 10-15 parts; 40-45 parts of water-based epoxy emulsion; 0.3-0.4 parts of water-based substrate wetting agent; 0.6-0.8 parts of water-based thickener; Component B: 60-80 parts of waterborne epoxy curing agent; Propylene glycol methyl ether 20-30 parts; 10-20 parts of deionized water; 10-15 parts of water-based flash rust inhibitor.

[0007] Adding lanthanum oxide rare earth to waterborne epoxy electrostatic conductive coating can significantly improve the coating's reactivity, stability, anti-corrosion performance, mechanical properties and environmental protection characteristics. These improvements are mainly due to the unique chemical and physical properties of rare earth elements, high reactivity, strong reducibility and effective filling ability for coating defects.

[0008] Adding rutile titanium dioxide to waterborne epoxy electrostatic conductive coatings is an effective strategy that can significantly improve the hiding power, weather resistance and stability of the coating. By optimizing the particle size distribution and surface treatment of titanium dioxide, the rheological properties of the coating can be improved, making it more uniform and stable during construction.

[0009] Sericite powder has good dispersibility and suspension, which can improve the storage stability and brush resistance of the coating. Its flaky structure helps to improve the anti-penetration of the coating and the mechanical properties of the coating. After adding sericite powder to water-based epoxy electrostatic conductive coating, the water resistance of the coating can be significantly improved. Using sericite powder to replace part of titanium dioxide pigment not only reduces the cost, but also improves the corrosion resistance of the coating.

[0010] The addition of strontium chrome yellow to water-based epoxy electrostatic conductive coatings is mainly to take advantage of its anti-rust properties. Strontium chrome yellow can provide chromate ions, which can form a protective film on the metal surface, thereby playing an anti-rust role.

[0011] Preferably, the dispersant is an acrylic block copolymer dispersant, which is synthesized by a solvent polymerization method using azobisisobutyronitrile as an initiator, allyl polyoxyethylene ether, α-methylstyrene and methacrylic acid as main monomers.

[0012] Preferably, the preparation method of the acrylic block copolymer dispersant is as follows: add isopropanol and n-dodecyl mercaptan to a four-necked flask equipped with a thermometer and a nitrogen-protected reflux device, heat to reflux, start dripping a measured mixture of an initiator and a mixed monomer and complete the dripping within 120-180 minutes, continue to keep warm for a period of time after the dripping is completed, continue to drip the initiator azobisisobutyronitrile solution, keep warm for 3 hours after the dripping is completed, cool to room temperature and add ammonia water for neutralization, add measured water, and then perform reduced pressure distillation to remove the solvent in the product, and finally obtain an aqueous acrylic block copolymer dispersant.

[0013] Preferably, the waterborne epoxy curing agent is synthesized by using 4,4'-diaminodicyclohexylmethane as a base amine, 1,3-propylenediamine as a hydrophilic modifier, liquid epoxy resin and polyethylene glycol diglycidyl ether.

[0014] Preferably, the preparation method of the water-based epoxy curing agent is as follows: a certain mass of dicyclic alicyclic amine 4,4'-diaminodicyclohexylmethane, hydrophilic amine, polyethylene glycol diglycidyl ether and auxiliary agent are put into a reaction bottle, stirred and heated to 60°C, and reacted for 1 hour; then a mixed solution of liquid epoxy resin and polyethylene glycol diglycidyl ether is added dropwise, the dropping time is not less than 3 hours, and the temperature in the kettle is maintained at (60±2)°C during the dropping process; after the dropping is completed, the temperature is raised to (70±2)°C and kept warm until the epoxy value is almost 0, then the stirring speed is increased, pure water is added to dilute to 50% (mass fraction), and the temperature is lowered to 50°C, and stirring is continued for 30 minutes to obtain a water-based epoxy curing agent.

[0015] Preferably, the aqueous substrate wetting agent is prepared by mixing allyloxy polyoxyethylene ether and polyoxyethylene polyoxypropylene ether in proportion, adding a platinum catalyst for temperature activation, adding silicone oil for hydrosilylation reaction to obtain a dipolyether co-modified trisiloxane, and reacting the dipolyether co-modified trisiloxane with a polyether precursor to connect the polyether chain to the siloxane main chain to obtain a polyether-modified siloxane wetting agent.

[0016] Preferably, the preparation method of the polyether-modified siloxane wetting agent is as follows: allyloxy polyoxyethylene ether and polyoxyethylene polyoxypropylene ether are mixed in a certain proportion, and then 0.002% of a platinum catalyst is added, the temperature is raised to 80° C. for activation for 0.5 h, the temperature is continuously raised to 105° C., and heptamethyl trisiloxane is added dropwise using a constant pressure funnel. After the addition is completed, the mixture is stirred and reacted at 105° C. for 5 h. After the reaction is completed, low-boiling substances are removed by vacuum distillation to obtain a dipolyether co-modified trisiloxane. The dipolyether co-modified trisiloxane is reacted with a polyether precursor under nitrogen protection and the temperature is controlled at 100° C., so that the polyether chain is connected to the siloxane main chain to obtain a polyether-modified siloxane wetting agent.

[0017] Preferably, the aqueous epoxy emulsion comprises the following raw materials in mass ratio: Liquid epoxy resin 54-58 parts; Emulsifier 5-10 parts; 30-55 parts of deionized water; The liquid epoxy resin is prepared by secondary modification of polyamine and γ-aminopropyltriethoxysilane.

[0018] Preferably, the mass ratio of the polyamine to γ-aminopropyltriethoxysilane is 1-2:3-5.

[0019] Preferably, the preparation method of the liquid epoxy resin is: using diethylenetriamine to react with epoxy resin to generate a modified epoxy resin having an amino group; mixing the modified epoxy resin with γ-aminopropyltriethoxysilane, stirring and reacting at 60° C. to allow the silane coupling agent to fully react with the epoxy group to obtain the liquid epoxy resin.

[0020] Preferably, the defoaming agent is TEGO810, TEGO901, TEGO902, the water-based anti-settling agent is the water-based anti-settling agent LT, DE, 140W of Zhejiang Fenghong New Materials Co., Ltd., the water-based thickener is RHEOLATE299, RHEOLATE175, RM2020, the water-based anti-flash rust agent is Halox 150, Hemmings FA179, Raybo57, and the emulsifier is CZY, OP-10, TX of Changzhiyou New Materials Co., Ltd.

[0021] Preferably, the mass ratio of component A to component B is 10:1.

[0022] Preferably, the aqueous epoxy emulsion comprises the following raw materials in mass ratio: Liquid epoxy resin 55-56 parts; Emulsifier 8-10 parts; 45-55 parts of deionized water.

[0023] Preferably, the method for preparing the waterborne epoxy emulsion comprises the following steps: S1: Weigh 54-58 parts of liquid epoxy resin according to the mass ratio, slowly add 5-10 parts of emulsifier under stirring at 500-600r / min, and control the dropping time to 10-12min; S2: Continue dispersing for another 8-10 minutes, increase the speed to 1200-1500 r / min, and slowly add 30-55 parts of deionized water, with the addition time controlled at 30-35 minutes; S3: Continue dispersing for another 120-150 minutes, increase the speed to 800-1000r / min, and filter and package.

[0024] In a second aspect, the present invention provides a method for preparing a lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating, comprising the following steps: (1) Preparation of component A: Weigh 16-18 parts of deionized water according to the mass ratio, slowly add 0.1-0.2 parts of defoamer and 0.9-1.2 parts of dispersant in sequence under stirring at 600-800 r / min, disperse for 8-10 minutes until uniform, slowly add 1-2 parts of propylene glycol methyl ether and 0.6-0.8 parts of water-based anti-settling agent in sequence under stirring at 600-800 r / min, disperse again for 8-10 minutes until uniform without agglomeration ..., Add 0.5-1 part of rutile titanium dioxide, 15-20 parts of sericite powder, 1.0-1.5 parts of strontium chrome yellow, and 15-20 parts of lanthanum oxide rare earth, disperse for 8-10 minutes to form a uniform slurry, then grind the slurry with a sand mill, take the ground slurry according to the mass ratio, slowly add 40-45 parts of water-based epoxy emulsion, 0.3-0.4 parts of water-based substrate wetting agent, and 0.6-0.8 parts of water-based thickener in sequence under stirring at 600-800r / min, disperse for 50-60 minutes, filter and package for use; (2) Preparation of component B: Weigh 60-80 parts of water-based epoxy curing agent according to the mass ratio, slowly add 20-300 parts of propylene glycol methyl ether and 10-20 parts of deionized water in sequence under stirring at 500-600 r / min, continue to disperse for 8-10 minutes until uniform, slowly add 10-15 parts of water-based flash rust inhibitor in sequence under stirring at 500-600 r / min, and continue to disperse for 30-35 minutes until uniform; (3) Component A obtained in step (1) and component B obtained in step (2) are mixed in a mass ratio of 10-12:1 to obtain a lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

[0025] Preferably, in step (1), the sand mill grinds the powder to a fineness of ≤50 μm.

[0026] In a third aspect, the present invention provides an application of a lanthanum oxide rare earth modified waterborne epoxy antistatic coating, wherein the lanthanum oxide rare earth modified waterborne epoxy antistatic coating is used on the steel structure of a petroleum storage tank.

[0027] In summary, the present invention has the following beneficial effects: The coating prepared by the present invention is mainly composed of water-based epoxy emulsion, water-based substrate wetting agent, lanthanum oxide rare earth, rutile titanium dioxide and sericite powder. It has the advantages of low price and short aging. Lanthanum oxide rare earth is a wide-bandgap p-type semiconductor (bandgap of about 4.3-5.8 eV) with a low surface work function (about 2.0 eV), which is conducive to electron emission and charge migration. This characteristic can effectively reduce the surface resistance of the coating, promote the rapid dissipation of static electricity, and avoid safety hazards caused by charge accumulation, which is particularly important in flammable and explosive environments. The introduction of lanthanum oxide achieves a performance leap of water-based epoxy electrostatic conductive coatings through multi-scale effects (electronic conduction, structural densification, and interface strengthening), especially showing irreplaceable advantages in high-corrosion and high-static risk environments.

[0028] 2. The present invention aims at the defects of existing electrostatic conductive coatings and uses white powdered lanthanum oxide rare earth as the conductive medium. This rare earth raw material has a larger specific surface area and more active conductive properties. Its internal electrons will form Coulomb pairs, thereby producing zero resistance and perfect conductivity. It can also optimize the charge transfer path and maximize the conductive performance. The most important thing is that the local materials are easy to obtain and the price is low. The coating prepared by the present invention has excellent and long-lasting conductive stability and anti-corrosion performance, and is light in color and not easy to spread and pollute oil products.

[0029] 3. The lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating prepared by the present invention is prepared by using a homemade waterborne epoxy emulsion and using lanthanum oxide rare earth as an electrostatic conductive medium to obtain a conductivity volume resistivity of less than 10 8 Ω's water-based epoxy electrostatic conductive coating meets the requirements of low VOC emission, low odor, non-flammable, non-explosive, etc. It is safe to use, transport and store. It also has extremely high adhesion, small shrinkage, good wear resistance, high hardness, good neutral salt spray resistance, excellent oil resistance, and most importantly, light color that is not easy to spread into oil and pollute the oil. Therefore, it has great economic and environmental value.

[0030] It should be understood that the foregoing general description and the following detailed description are exemplary and explanatory only and are not intended to limit the scope of protection of the present invention. DETAILED DESCRIPTION

[0031] The present invention is further described in detail below in conjunction with the examples. It is particularly noted that if no specific conditions are specified in the following examples, the reactions are carried out according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following examples can be obtained from common commercial sources.

[0032] Preparation Example 1: A water-based epoxy emulsion comprising the following raw materials in the following mass ratios: Liquid epoxy resin 54 parts; Emulsifier CZY 5 parts; 30 parts of deionized water; The liquid epoxy resin is obtained by secondary modification of polyamine and γ-aminopropyltriethoxysilane; the mass ratio of diethylenetriamine and γ-aminopropyltriethoxysilane is 1:3.

[0033] The preparation method of liquid epoxy resin is as follows: diethylenetriamine is used to react with epoxy resin to generate modified epoxy resin with amino groups; the modified epoxy resin is mixed with γ-aminopropyltriethoxysilane, and stirred to react at 60°C to make the silane coupling agent and epoxy group fully react to obtain liquid epoxy resin.

[0034] The preparation method of water-based epoxy emulsion comprises the following steps: Take liquid epoxy resin according to the mass ratio and place it in a three-necked flask. Slowly add emulsifier CZY under stirring at 500r / min. The dripping time is controlled within 10min. Continue to disperse for 8min at 45℃ for co-reaction. Increase the speed to 1200r / min and slowly drip deionized water. The dripping time is controlled within 30min. Continue to disperse for 120min and increase the speed to 800r / min. After cooling to room temperature, filter and package.

[0035] Preparation Example 2: A water-based epoxy emulsion comprising the following raw materials in the following mass ratios: Liquid epoxy resin 56 parts; Emulsifier CZY 8 parts; 45 parts of deionized water; The liquid epoxy resin is obtained by secondary modification of polyamine and γ-aminopropyltriethoxysilane; the mass ratio of diethylenetriamine and γ-aminopropyltriethoxysilane is 2:3.

[0036] The preparation method of liquid epoxy resin is as follows: diethylenetriamine is used to react with epoxy resin to generate modified epoxy resin with amino groups; the modified epoxy resin is mixed with γ-aminopropyltriethoxysilane, and stirred to react at 60°C to make the silane coupling agent and epoxy group fully react to obtain liquid epoxy resin.

[0037] The preparation method of water-based epoxy emulsion comprises the following steps: Take liquid epoxy resin according to the mass ratio and place it in a three-necked flask. Slowly add emulsifier CZY under stirring at 600r / min. The dripping time is controlled within 10min. Continue to disperse for 10min at 45℃ for co-reaction. Increase the speed to 1200r / min and slowly add deionized water. The dripping time is controlled within 30min. Continue to disperse for 120min and increase the speed to 1000r / min. After cooling to room temperature, filter and package.

[0038] Preparation Example 3: A water-based epoxy emulsion comprising the following raw materials in the following mass ratios: Liquid epoxy resin 58 parts; Emulsifier CZY 10 parts; 55 parts of deionized water; The liquid epoxy resin is obtained by secondary modification of polyamine and γ-aminopropyltriethoxysilane; the mass ratio of diethylenetriamine and γ-aminopropyltriethoxysilane is 1:5.

[0039] The preparation method of liquid epoxy resin is as follows: diethylenetriamine is used to react with epoxy resin to generate modified epoxy resin with amino groups; the modified epoxy resin is mixed with γ-aminopropyltriethoxysilane, and stirred to react at 60°C to make the silane coupling agent and epoxy group fully react to obtain liquid epoxy resin.

[0040] The preparation method of water-based epoxy emulsion comprises the following steps: Take 23 parts of liquid epoxy resin by mass ratio and put them in a three-necked flask. Slowly add emulsifier CZY under stirring at 600r / min. The dripping time is controlled within 12min. Continue to disperse for 10min and react at 50℃. Increase the speed to 1500r / min and slowly drip deionized water. The dripping time is controlled within 35min. Continue to disperse for 150min and increase the speed to 1000r / min. After cooling to room temperature, filter and package.

[0041] Preparation Example 4: A preparation method for an acrylic block copolymer dispersant is as follows: 10 mL of isopropanol and 15 mL of n-dodecyl mercaptan are added to a four-necked flask equipped with a thermometer and a nitrogen-protected reflux device, the temperature is raised to 150°C to reflux, 50 mL of a mixture of initiator azobisisobutyronitrile and mixed monomers is started to be added dropwise and the mixture is completed within 120 min. After the addition is completed, the mixture is kept warm for a period of time, and the initiator azobisisobutyronitrile solution is continued to be added dropwise. After the addition is completed, the mixture is kept warm for 3 h, the mixture is cooled to room temperature, ammonia water is added to neutralize the mixture, 200 mL of water is added, and the solvent in the product is removed by reduced pressure distillation to obtain a water-based acrylic block copolymer dispersant.

[0042] Preparation Example 5: A preparation method for an acrylic block copolymer dispersant is as follows: 20 mL of isopropanol and 20 mL of n-dodecyl mercaptan are added to a four-necked flask equipped with a thermometer and a nitrogen-protected reflux device, the temperature is raised to reflux, 70 mL of a mixture of initiator azobisisobutyronitrile and mixed monomers are started to be added dropwise and the mixture is completed within 180 min. After the addition is completed, the mixture is kept warm for a period of time, and the initiator azobisisobutyronitrile solution is continued to be added dropwise. After the addition is completed, the mixture is kept warm for 3 h, the temperature is lowered to room temperature, ammonia water is added to neutralize the mixture, 200 mL of ammonia water is added, and the solvent in the product is removed by reduced pressure distillation to obtain a water-based acrylic block copolymer dispersant.

[0043] Preparation Example 6: A method for preparing a water-based epoxy curing agent is as follows: 12 g of dicyclic alicyclic amine 4,4'-diaminodicyclohexylmethane, 8 g of hydrophilic amine, 21 g of polyethylene glycol diglycidyl ether and an auxiliary agent are put into a reaction bottle, stirred and heated to 60°C, and reacted for 1 hour; then a mixture of liquid epoxy resin and polyethylene glycol diglycidyl ether is added dropwise, and the addition time is not less than 3 hours. During the addition, the temperature in the kettle is maintained at 60°C; after the addition is completed, the temperature is raised to 70°C and kept warm until the epoxy value is almost 0, then the stirring speed is increased, pure water is added to dilute it to 50% (mass fraction), and the temperature is lowered to 50°C, and stirring is continued for 30 minutes to obtain a water-based epoxy curing agent.

[0044] Preparation Example 7: A method for preparing a water-based epoxy curing agent is as follows: 5 g of dicyclic alicyclic amine 4,4'-diaminodicyclohexylmethane, 10 g of hydrophilic amine, 30 g of polyethylene glycol diglycidyl ether and an auxiliary agent are put into a reaction bottle, stirred and heated to 60°C, and reacted for 1 hour; then a mixed solution of liquid epoxy resin and polyethylene glycol diglycidyl ether is added dropwise, and the addition time is not less than 3 hours. During the addition, the temperature in the kettle is maintained at 60°C; after the addition is completed, the temperature is raised to 70°C and kept warm until the epoxy value is almost 0, then the stirring speed is increased, pure water is added to dilute it to 50% (mass fraction), and the temperature is lowered to 50°C, and stirring is continued for 30 minutes to obtain a water-based epoxy curing agent.

[0045] Preparation Example 8: A method for preparing a polyether-modified siloxane wetting agent is as follows: allyloxypolyoxyethylene ether and polyoxyethylenepolyoxypropylene ether are mixed in a mass ratio of 2:5, followed by adding 0.002% of a platinum catalyst, heating to 80°C for activation for 0.5h, continuously heating to 105°C, and adding heptamethyltrisiloxane dropwise using a constant pressure funnel. After the addition is completed, stirring and reacting at 105°C for 5h. After the reaction is completed, vacuum distillation is performed to remove low-boiling substances to obtain a dipolyether co-modified trisiloxane. The dipolyether co-modified trisiloxane is reacted with 50mL of a polyether precursor under nitrogen protection and the temperature is controlled at 100°C to connect the polyether chain to the siloxane main chain to obtain a polyether-modified siloxane wetting agent.

[0046] Preparation Example 9: A method for preparing a polyether-modified siloxane wetting agent is as follows: allyloxypolyoxyethylene ether and polyoxyethylenepolyoxypropylene ether are mixed in a mass ratio of 3:8, followed by adding 0.002% of a platinum catalyst, heating to 80°C for activation for 0.5h, continuously heating to 105°C, adding heptamethyltrisiloxane dropwise using a constant pressure funnel, and after the addition is completed, stirring and reacting at 105°C for 5h. After the reaction is completed, vacuum distillation is performed to remove low-boiling substances to obtain a dipolyether co-modified trisiloxane, and the dipolyether co-modified trisiloxane is reacted with 50mL of a polyether precursor under nitrogen protection and the temperature is controlled at 100°C to connect the polyether chain to the siloxane main chain to obtain a polyether-modified siloxane wetting agent.

[0047] Embodiment 1: A method for preparing a lanthanum oxide modified waterborne epoxy electrostatic conductive coating, comprising the following steps: (1) Preparation of component A: Weigh 16 parts of deionized water according to the mass ratio, slowly add 0.1 parts of defoamer TEGO810 and 0.9 parts of water-based acrylic block copolymer dispersant obtained in Preparation Example 4 in sequence under 600r / min stirring, and disperse for 8min until uniform. Slowly add 1 part of propylene glycol methyl ether and 0.6 parts of water-based anti-settling agent LT in sequence under 600r / min stirring, and disperse again for 8min until uniform without agglomeration. Slowly add 0.5 parts of rutile titanium dioxide, 15 parts of sericite powder, 1.0 parts of strontium chrome yellow, and 15 parts of lanthanum oxide rare earth in sequence under 600r / min stirring, and disperse for 10min into a uniform slurry. Then the above slurry is ground to a fineness of ≤50μm using a sand mill, and filtered and packaged for standby after grinding to a fineness. Take the above-mentioned slurry ground to a fineness according to the mass ratio, slowly add 40 parts of the water-based epoxy emulsion prepared in Preparation Example 1, 0.3 parts of the polyether-modified siloxane wetting agent prepared in Preparation Example 8, and 0.6 parts of the water-based thickener RHEOLATE299 in sequence under stirring at 600r / min, disperse for 50 minutes, filter and package for use, this is the main paint of the lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

[0048] (2) Preparation of component B: Weigh 60 parts of the waterborne epoxy curing agent prepared in Preparation Example 6 according to the mass ratio, slowly add 20 parts of propylene glycol methyl ether and 10 parts of deionized water in sequence under 500r / min stirring, and continue to disperse for 10min until uniform. Slowly add 10 parts of waterborne flash rust preventer Halox150 in sequence under 500r / min stirring, and continue to disperse for 30min until uniform. Filter and package, this is a curing agent for lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating.

[0049] (3) Preparation of lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating and board testing: Weigh the main paint of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating and the curing agent of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating in the ratio of 10:1, disperse them at 600r / min stirring for 5-10min, and add 10 parts of deionized water after they are completely dispersed, disperse them at 600r / min stirring for 5-10min, mix them evenly, and start making boards. Mainly test the pull-off adhesion, color, appearance, volume resistivity, neutral salt spray resistance, abrasion resistance (500g / 500r), (3.5%NaCL), methanol resistance, ethanol resistance, gasoline resistance, milk diesel resistance, and whether there is color bleeding.

[0050] Embodiment 2: A method for preparing a lanthanum oxide modified waterborne epoxy electrostatic conductive coating, comprising the following steps: (1) Preparation of component A: Weigh 17 parts of deionized water according to the mass ratio, slowly add 0.2 parts of defoamer TEGO810 and 1.0 parts of water-based acrylic block copolymer dispersant obtained in Preparation Example 5 in sequence under 600r / min stirring, and disperse for 10min until uniform. Slowly add 2 parts of propylene glycol methyl ether and 0.8 parts of water-based anti-settling agent LT in sequence under 600r / min stirring, and disperse again for 10min until uniform without agglomeration. Slowly add 1 part of rutile titanium dioxide, 18 parts of sericite powder, 1.5 parts of strontium chrome yellow, and 16 parts of lanthanum oxide rare earth in sequence under 600r / min stirring, and disperse for 10min into a uniform slurry. Then the above slurry is ground to a fineness of ≤50μm using a sand mill, and filtered and packaged for standby after grinding to a fineness. Take the above-mentioned slurry ground to a fineness according to the mass ratio, slowly add 42 parts of the water-based epoxy emulsion prepared in Preparation Example 2, 0.4 parts of the polyether-modified siloxane wetting agent prepared in Preparation Example 9, and 0.8 parts of the water-based thickener RHEOLATE299 in sequence under stirring at 600r / min. After dispersing for 60 minutes, filter and package for later use. This is the main paint of the lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

[0051] (2) Preparation of component B: Weigh 70 parts of the waterborne epoxy curing agent prepared in Preparation Example 7 according to the mass ratio, slowly add 25 parts of propylene glycol methyl ether and 10 parts of deionized water in sequence under 600r / min stirring, and continue to disperse for 10min until uniform. Slowly add 10 parts of waterborne flash rust preventer Halox150 in sequence under 600r / min stirring, and continue to disperse for 30min until uniform. Filter and package, this is a curing agent for lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating.

[0052] (3) Preparation of lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating and board testing Weigh the main paint of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating and the curing agent of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating in the ratio of 10:1, disperse them at 600r / min stirring for 10min, add 10 parts of deionized water after they are completely dispersed, disperse them at 600r / min stirring for 10min, mix them evenly and start making boards. Mainly test the pull-off adhesion, color, appearance, volume resistivity, neutral salt spray resistance, abrasion resistance (500g / 500r), (3.5%NaCL), methanol resistance, ethanol resistance, gasoline resistance, milk diesel resistance, and whether there is color bleeding.

[0053] Embodiment 3: A method for preparing a lanthanum oxide modified waterborne epoxy electrostatic conductive coating, comprising the following steps: (1) Preparation of component A: Weigh 18 parts of deionized water according to the mass ratio, slowly add 0.2 parts of defoamer TEGO810 and 1.2 parts of water-based acrylic block copolymer dispersant obtained in Preparation Example 4 in sequence under 600r / min stirring, and disperse for 10min until uniform. Slowly add 2 parts of propylene glycol methyl ether and 0.8 parts of water-based anti-settling agent LT in sequence under 600r / min stirring, and disperse again for 10min until uniform without agglomeration. Slowly add 0.8 parts of rutile titanium dioxide, 18 parts of sericite powder, 1.2 parts of strontium chrome yellow, and 16 parts of lanthanum oxide rare earth in sequence under 600r / min stirring, and disperse for 10min into a uniform slurry. Then the above slurry is ground to a fineness of ≤50μm using a sand mill, and filtered and packaged for standby after grinding to a fineness. Take the above-mentioned slurry ground to a fineness according to the mass ratio, slowly add 42 parts of the water-based epoxy emulsion prepared in Preparation Example 3, 0.4 parts of the polyether-modified siloxane wetting agent prepared in Preparation Example 8, and 0.8 parts of the water-based thickener RHEOLATE299 in sequence under stirring at 600r / min. After dispersing for 60 minutes, filter and package for later use. This is the main paint of the lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

[0054] (2) Preparation of component B: Weigh 60 parts of the water-based epoxy curing agent prepared in Preparation Example 6 according to the mass ratio, slowly add 20 parts of propylene glycol methyl ether and 10 parts of deionized water in sequence under 600r / min stirring, and continue to disperse for 10min until uniform. Slowly add 10 parts of water-based flash rust preventer Halox150 in sequence under 600r / min stirring, and continue to disperse for 35min until uniform. Filter and package, this is a curing agent for lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

[0055] (3) Preparation of lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating and board testing Weigh the main paint of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating and the curing agent of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating in the ratio of 10:1, disperse them at 600r / min stirring for 10min, add 10 parts of deionized water after they are completely dispersed, disperse them at 600r / min stirring for 10min, mix them evenly and start making boards. Mainly test the pull-off adhesion, color, appearance, volume resistivity, neutral salt spray resistance, abrasion resistance (500g / 500r), (3.5%NaCL), methanol resistance, ethanol resistance, gasoline resistance, milk diesel resistance, and whether there is color bleeding.

[0056] Embodiment 4: A method for preparing a lanthanum oxide modified waterborne epoxy electrostatic conductive coating, comprising the following steps: (1) Preparation of component A: Weigh 17 parts of deionized water according to the mass ratio, slowly add 0.2 parts of defoamer TEGO810 and 1.0 parts of water-based acrylic block copolymer dispersant obtained in Preparation Example 5 in sequence under 600r / min stirring, and disperse for 10min until uniform. Slowly add 2 parts of propylene glycol methyl ether and 0.8 parts of water-based anti-settling agent LT in sequence under 600r / min stirring, and disperse again for 10min until uniform without agglomeration. Slowly add 0.8 parts of rutile titanium dioxide, 19 parts of sericite powder, 1.4 parts of strontium chrome yellow, and 18 parts of lanthanum oxide rare earth in sequence under 600r / min stirring, and disperse for 10min into a uniform slurry. Then the above slurry is ground to a fineness of ≤50μm using a sand mill, and filtered and packaged for standby after grinding to a fineness. Take the above-mentioned slurry ground to a fineness according to the mass ratio, slowly add 42 parts of the water-based epoxy emulsion prepared in Preparation Example 1, 0.4 parts of the polyether-modified siloxane wetting agent prepared in Preparation Example 9, and 0.8 parts of the water-based thickener RHEOLATE299 in sequence under stirring at 600r / min. After dispersing for 60 minutes, filter and package for later use. This is the main paint of the lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

[0057] (2) Preparation of component B: Weigh 60 parts of the waterborne epoxy curing agent prepared in Preparation Example 7 according to the mass ratio, slowly add 20 parts of propylene glycol methyl ether and 10 parts of deionized water in sequence under 500r / min stirring, and continue to disperse for 10min until uniform. Slowly add 10 parts of waterborne flash rust preventer Halox150 in sequence under 500r / min stirring, and continue to disperse for 30min until uniform. Filter and package, this is the curing agent for lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating.

[0058] (3) Preparation of lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating and board testing Weigh the main paint of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating and the curing agent of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating in the ratio of 10:1, disperse them at 600r / min stirring for 10min, add 10 parts of deionized water after they are completely dispersed, disperse them at 600r / min stirring for 5min, mix them evenly and start making boards. Mainly test the pull-off adhesion, color, appearance, volume resistivity, neutral salt spray resistance, abrasion resistance (500g / 500r), (3.5%NaCL), methanol resistance, ethanol resistance, gasoline resistance, milk diesel resistance, and whether there is color bleeding.

[0059] Embodiment 5: A method for preparing a lanthanum oxide modified waterborne epoxy electrostatic conductive coating, comprising the following steps: (1) Preparation of component A: Weigh 18 parts of deionized water according to the mass ratio, slowly add 0.2 parts of defoamer TEGO810 and 1.1 parts of water-based acrylic block copolymer dispersant obtained in Preparation Example 4 in sequence under 600r / min stirring, and disperse for 10min until uniform. Slowly add 1 part of propylene glycol methyl ether and 0.8 parts of water-based anti-settling agent LT in sequence under 600r / min stirring, and disperse again for 10min until uniform without agglomeration. Slowly add 0.6 parts of rutile titanium dioxide, 18 parts of sericite powder, 1.2 parts of strontium chrome yellow, and 16 parts of lanthanum oxide rare earth in sequence under 600r / min stirring, and disperse for 10min into a uniform slurry. Then the above slurry is ground to a fineness of ≤50μm using a sand mill, and filtered and packaged for standby after grinding to a fineness. Take the above-mentioned slurry ground to a fineness according to the mass ratio, slowly add 40 parts of the water-based epoxy emulsion in Preparation Example 2, 0.4 parts of the polyether-modified siloxane wetting agent obtained in Preparation Example 8, and 0.8 parts of the water-based thickener RHEOLATE299 in sequence under stirring at 600r / min. After dispersing for 60 minutes, filter and package for later use. This is the main paint of the lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

[0060] (2) Preparation of component B: Weigh 60 parts of the waterborne epoxy curing agent prepared in Preparation Example 6 according to the mass ratio, slowly add 20 parts of propylene glycol methyl ether and 10 parts of deionized water in sequence under 600r / min stirring, and continue to disperse for 10min until uniform. Slowly add 10 parts of waterborne flash rust preventer Halox150 in sequence under 600r / min stirring, and continue to disperse for 35min until uniform. Filter and package, this is a curing agent for lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating.

[0061] (3) Preparation of lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating and board testing Weigh the main paint of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating and the curing agent of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating in the ratio of 10:1, disperse them at 600r / min stirring for 10min, add 10 parts of deionized water after they are completely dispersed, disperse them at 600r / min stirring for 10min, mix them evenly and start making boards. Mainly test the pull-off adhesion, color, appearance, volume resistivity, neutral salt spray resistance, abrasion resistance (500g / 500r), (3.5%NaCL), methanol resistance, ethanol resistance, gasoline resistance, milk diesel resistance, and whether there is color bleeding.

[0062] Comparative Example 1: The same preparation method as Example 1 was used to prepare the product, except that the aqueous epoxy emulsion was replaced by aqueous epoxy emulsion AQUAER3012 (Jiangsu Fuqisen New Materials Co., Ltd.).

[0063] Comparative Example 2: The same preparation method as Example 1 was used for preparation, except that no polyether-modified siloxane wetting agent was added.

[0064] Comparative Example 3: The same preparation method as Example 1 was used for preparation, except that no aqueous acrylic block copolymer dispersant was added.

[0065] Table 1 Performance test results of lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coatings prepared in Examples 1-5

[0066] As can be seen from the results in Table 1, the lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating prepared in Example 1 of the present invention has good pull-out adhesion, very light color, lowest volume resistivity, best wear resistance, high pull-out adhesion, good neutral salt spray resistance, good oil resistance, no color bleeding, color bleeding, and excellent volume resistivity of 1000h neutral salt spray resistant paint film. The use of conductive mica powder as a conductive medium or conductive graphite powder as a conductive medium improves the conductive performance. The waterborne epoxy emulsion has improved the pull-out adhesion, wear resistance, neutral salt spray resistance, and paint film resistivity after 1000h neutral salt spray; the addition amount of lanthanum oxide has improved the paint film resistivity and the paint film resistivity after 1000h neutral salt spray. At the same time, the waterborne product is safer to use, transport, and store, and the performance is more reliable. Therefore, the present invention has great economic value and environmental value, and is more suitable for promotion and application.

[0067] The above is only an exemplary embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating, characterized in that: Raw materials including the following quality components: Component A: 16-18 parts of deionized water; Defoaming agent 0.1-0.2 parts; Dispersant 0.9-1.2 parts; Propylene glycol methyl ether 1-2 parts; 0.6-0.8 parts of water-based anti-settling agent; 0.5-1 part of rutile titanium dioxide; Sericite powder 15-20 parts; Strontium chrome yellow 1.0-1.5 parts; Lanthanum oxide rare earth 10-15 parts; 40-45 parts of water-based epoxy emulsion; 0.3-0.4 parts of water-based substrate wetting agent; 0.6-0.8 parts of water-based thickener; Component B: 60-80 parts of waterborne epoxy curing agent; Propylene glycol methyl ether 20-30 parts; 10-20 parts of deionized water; 10-15 parts of water-based flash rust inhibitor.

2. The lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating according to claim 1, characterized in that: The dispersant is an acrylic acid block copolymer dispersant, which is synthesized by a solvent polymerization method using azobisisobutyronitrile as an initiator, allyl polyoxyethylene ether, alpha-methylstyrene and methacrylic acid as main monomers.

3. The lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating according to claim 1, characterized in that: The waterborne epoxy curing agent is synthesized by using 4,4'-diaminodicyclohexylmethane as the base amine, 1,3-propylenediamine as a hydrophilic modifier, liquid epoxy resin and polyethylene glycol diglycidyl ether.

4. The lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating according to claim 1, characterized in that: The water-based substrate wetting agent is prepared by mixing allyloxy polyoxyethylene ether and polyoxyethylene polyoxypropylene ether in proportion, adding a platinum catalyst for temperature activation, adding silicone oil for hydrosilylation reaction to obtain dipolyether co-modified trisiloxane, and reacting the dipolyether co-modified trisiloxane with a polyether precursor to connect the polyether chain to the siloxane main chain to obtain a polyether-modified siloxane wetting agent.

5. The lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating according to claim 1, characterized in that: The aqueous epoxy emulsion comprises the following raw materials in mass ratio: Liquid epoxy resin 54-58 parts; Emulsifier 5-10 parts; 30-55 parts of deionized water; The liquid epoxy resin is prepared by secondary modification of polyamine and γ-aminopropyltriethoxysilane.

6. The lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating according to claim 5, characterized in that: The mass ratio of the polyamine to γ-aminopropyltriethoxysilane is 1-2:3-5.

7. The lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating according to claim 5, characterized in that: The preparation method of the aqueous epoxy emulsion comprises the following steps: S1: Weigh 54-58 parts of liquid epoxy resin according to the mass ratio, slowly add 5-10 parts of emulsifier under stirring at 500-600r / min, and control the dropping time to 10-12min; S2: Continue dispersing for another 8-10 minutes, increase the speed to 1200-1500 r / min, and slowly add 30-55 parts of deionized water, with the addition time controlled at 30-35 minutes; S3: Continue dispersing for another 120-150 minutes, increase the speed to 800-1000r / min, and filter and package.

8. The method for preparing the lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating according to any one of claims 1 to 7, characterized in that: The following steps are involved: (1) Preparation of component A: Weigh 16-18 parts of deionized water according to the mass ratio, slowly add 0.1-0.2 parts of defoamer and 0.9-1.2 parts of dispersant in sequence under stirring at 600-800 r / min, disperse for 8-10 minutes until uniform, slowly add 1-2 parts of propylene glycol methyl ether and 0.6-0.8 parts of water-based anti-settling agent in sequence under stirring at 600-800 r / min, disperse again for 8-10 minutes until uniform without agglomeration ..., Add 0.5-1 part of rutile titanium dioxide, 15-20 parts of sericite powder, 1.0-1.5 parts of strontium chrome yellow, and 15-20 parts of lanthanum oxide rare earth, disperse for 8-10 minutes to form a uniform slurry, then grind the slurry with a sand mill, take the ground slurry according to the mass ratio, slowly add 40-45 parts of water-based epoxy emulsion, 0.3-0.4 parts of water-based substrate wetting agent, and 0.6-0.8 parts of water-based thickener in sequence under stirring at 600-800r / min, disperse for 50-60 minutes, filter and package for use; (2) Preparation of component B: Weigh 60-80 parts of water-based epoxy curing agent according to the mass ratio, slowly add 20-300 parts of propylene glycol methyl ether and 10-20 parts of deionized water in sequence under stirring at 500-600 r / min, continue to disperse for 8-10 minutes until uniform, slowly add 10-15 parts of water-based flash rust inhibitor in sequence under stirring at 500-600 r / min, and continue to disperse for 30-35 minutes until uniform; (3) Component A obtained in step (1) and component B obtained in step (2) are mixed in a mass ratio of 10-12:1 to obtain a lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating.

9. The use of the lanthanum oxide rare earth modified waterborne epoxy electrostatic conductive coating according to any one of claims 1 to 7, characterized in that: The lanthanum oxide rare earth modified water-based epoxy electrostatic conductive coating is used on the steel structure of the petroleum storage tank.

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