A waterborne epoxy zinc-rich coating containing lepidolite slag and its preparation method

Abstract

The present invention discloses a waterborne epoxy zinc-rich coating containing lepidolite slag and a preparation method thereof, which relates to the technical field of coatings and includes: preparing a Ti3C2T X -silica composite nanomaterial; mixing the lithium slag, zinc powder and the talc powder intercalation complex to prepare a lithium slag / zinc powder / talc powder intercalation complex; stirring the waterborne epoxy emulsion, Ti3C2T X -silica composite nanomaterial, deionized water, dispersant, defoamer, wetting agent, deionized water, and lithium slag / zinc powder / talc powder intercalation complex evenly to prepare component A; stirring the waterborne epoxy curing agent, defoamer, leveling agent, and film-forming auxiliary evenly to prepare component B; mixing component A and component B to obtain the product. The beneficial effects of the present invention are that the coating has good storage stability, is safe and convenient for construction, has a fast drying speed of the coating, strong film adhesion, and excellent anti-corrosion performance.

Description

Technical Field

[0001] The present invention particularly relates to a waterborne epoxy zinc-rich coating containing lepidolite slag and a preparation method thereof, belonging to the technical field of coatings. Background Art

[0002] The corrosion of steel not only causes economic losses, but most importantly, it will seriously weaken the life and safety of steel structures. Epoxy zinc-rich coatings are one of the heavy-duty anti-corrosion coatings and are widely used due to their excellent physical and mechanical properties and anti-corrosion properties. Generally, 70% - 80% by mass of zinc powder needs to be added to this coating as a sacrificial anode. However, if the amount of zinc powder used is too high, the coating is prone to be porous, the adhesion decreases, and the bonding force with the intermediate paint will also be reduced, affecting the overall anti-corrosion performance of the coating. Moreover, when the zinc powder content is too high, a large amount of zinc oxide will be generated during welding, which is extremely harmful to the health of construction workers. At the same time, zinc powder is expensive and the coating cost is relatively high. Therefore, the research on reducing the amount of zinc powder used and improving the anti-corrosion level of waterborne zinc-rich epoxy coatings has attracted wide attention from anti-corrosion workers. Summary of the Invention

[0003] The purpose of the present invention is to solve at least one of the technical problems existing in the prior art, and to provide a waterborne epoxy zinc-rich coating containing lepidolite slag and a preparation method thereof.

[0004] The technical solution of the present invention is as follows:

[0005] The first aspect of the present invention provides a preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag, comprising the following steps:

[0006] Mix nano-silica with toluene and perform ultrasonic dispersion for 2 - 3 h. Add KH-560 to a flask and react at 80 - 90 °C for 4 - 8 h. After cooling to room temperature, perform suction filtration, wash with water and ethanol, and dry under vacuum to prepare nano-silica with epoxy groups introduced on the surface;

[0007] Mix the nano-silica with epoxy groups introduced on the surface with water and perform ultrasonic dispersion for 2 - 5 h. Then continue to add Ti3C2T X , react at 60 - 90 °C for 6 - 8 h, then add a 70 - 80 wt% hydrazine hydrate solution, react at 90 - 95 °C for 10 - 12 h. After cooling to room temperature, perform suction filtration, wash with water and ethanol, and dry under vacuum to prepare Ti3C2T X -silica composite nanomaterials;

[0008] Put the lepidolite slag into a ball mill for ball milling until its specific surface area is 1000 - 1500 m 2Particles of / kg are obtained to get lithium slag; Talc powder and ethylene glycol are mixed and ultrasonically treated at room temperature for 2 - 5 h, then an aqueous urea solution is added and stirred for reaction, followed by suction filtration, washing with water and ethanol, and vacuum drying to prepare a talc powder intercalation complex; Then, the lithium slag, zinc powder and the talc powder intercalation complex are ultrasonically treated at room temperature for 0.5 - 2 h, and then ground in a ball mill at a rotation speed of 300 - 600 r / min for 0.4 - 1 h to prepare a lithium slag / zinc powder / talc powder intercalation complex;

[0009] In a stirring kettle, aqueous epoxy emulsion, the Ti3C2T X -silica composite nanomaterial, deionized water, dispersant, defoamer, wetting agent, deionized water, and lithium slag / zinc powder / talc powder intercalation complex are stirred evenly at a rotation speed of 100 - 500 r / min for 0.5 - 1 h to prepare component A;

[0010] In a stirring kettle, aqueous epoxy curing agent, defoamer, leveling agent, and film-forming auxiliary agent are stirred evenly to prepare component B;

[0011] In a stirring kettle, component A and component B are added in sequence and stirred and dispersed at a rotation speed of 200 - 500 r / min for 0.5 - 1 h to prepare a waterborne epoxy zinc-rich coating containing lithium mica slag.

[0012] Preferably, the Ti3C2T X is a single-layer or multi-layer structure.

[0013] Preferably, the aqueous epoxy emulsion is a bisphenol A type epoxy resin emulsion with a solid content of 40% - 60%.

[0014] Preferably, the preparation method of the aqueous epoxy curing agent includes:

[0015] 1) Weigh diethylenetriamine and butanediol diglycidyl ether according to a molar ratio of 8:1 respectively for reaction, heat to 60 - 70 °C, and the reaction time is 3 - 5 h to prepare a polyamine adduct intermediate;

[0016] 2) Evaporate the residual small molecule diethylenetriamine in the polyamine adduct intermediate completely with diethylene glycol monoethyl ether;

[0017] 3) Weigh bisphenol A type epoxy resin and polyamine adduct intermediate according to a molar ratio of 0.2:1 respectively for addition reaction, heat to 80 - 90 °C, and the reaction time is 3 - 5 h to prepare the aqueous epoxy curing agent.

[0018] Preferably, the mass ratio of the silica:KH-560 is 5 - 20:1.

[0019] Preferably, the silica:Ti3C2TX The mass ratio is 2 - 5:1.

[0020] Preferably, the mass ratio of talcum powder: ethylene glycol: urea is 10 - 15:1:0.5.

[0021] Preferably, the mass ratio of lithium slag: zinc powder: talcum powder intercalation complex is 1:30 - 150:5 - 20.

[0022] Preferably, in the component A, the mass ratio of waterborne epoxy emulsion: Ti3C2T X - silicon dioxide nanomaterial: defoamer: dispersant: wetting agent: deionized water: lithium slag / zinc powder / talcum powder intercalation complex = 50 - 100:2 - 6:0.1 - 0.5:0.5 - 1:0.1 - 0.5:20 - 80:30 - 100.

[0023] Preferably, in the component B, the mass ratio of waterborne epoxy curing agent: defoamer: leveling agent: film - forming auxiliary = 50 - 100:0.1 - 0.5:0.1 - 0.5:0.1 - 0.5; the mass ratio of the waterborne epoxy emulsion: component B = 0.5 - 2:1

[0024] The second aspect of the present invention provides a water - borne epoxy zinc - rich coating containing lithium mica slag, which is prepared by the above - mentioned method.

[0025] The present invention has at least one of the following beneficial effects:

[0026] Ti3C2T X has good structural stability and chemical inertness. Due to its small size, two - dimensional sheet structure, excellent electrical conductivity and high electron mobility, theoretically it is a material similar to graphene oxide, which can not only enhance the anti - corrosion performance of the epoxy zinc - rich coating, but also replace part of the zinc powder to play a conductive role. Especially, Ti3C2T X has high dispersibility and stability in the water - solvent system. The silanol groups on the surface of silicon dioxide can interact with adjacent fumed silica particles to form hydrogen bonds, and the hydrogen - bond interaction makes it form a thixotropic structure. Fumed silica is a good anti - settling agent. However, the particle size of nano - silica is small, the specific surface area is large, and the interaction between particles is not easy to be completely dispersed. When added into the resin, it is easy to agglomerate, affecting its anti - settling effect and the performance of the product.

[0027] The present invention uses the coupling agent method to introduce epoxy groups on the surface of silicon dioxide, and then chemically connects the nano - silica with Ti3C2T X due to Ti3C2T XSurface grafted nano-silica, with an isolation effect between the two, better overcomes the agglomeration between nano-silica particles, and effectively improves the dispersion of silica in the resin. In epoxy zinc-rich coatings, well-dispersed Ti3C2T X -silica forms a dense conductive network and an efficient anti-settling system. On the one hand, due to the conductivity of Ti3C2T X , it replaces most of the conductive and barrier functions of zinc powder. On the other hand, due to the efficient anti-settling effect of nano-silica, it greatly improves the dispersion of zinc powder in epoxy resin, increases the conductivity and electrochemical corrosion efficiency of zinc powder in the coating. At the same time, nano-silica itself has a positive promoting effect on the corrosion resistance of epoxy coatings. Therefore, the addition of Ti3C2T X -silica to prepare waterborne epoxy zinc-rich coatings greatly reduces the zinc powder consumption and realizes zero emission of organic solvents. At the same time, waterborne epoxy anti-corrosion coatings greatly reduce the environmental pollution caused by organic solvents and zinc powder, reduce product costs, and eliminate fire and safety hazards.

[0028] In the present invention, ethylene glycol and urea are used to intercalate talc powder. Talc powder is a magnesium silicate mineral of the talc family, and its main component is hydrous magnesium silicate. By intercalating talc powder, ethylene glycol and urea can enter the interlayer of the layered compound by inserting and embedding, etc., without destroying its layered structure, thereby increasing the interlayer spacing and improving the interlayer microenvironment. Then, lithium slag, zinc powder and the talc powder intercalation complex are subjected to ultrasonic and ball milling treatments. The main components of lithium slag include a mixture of silicon oxide, aluminum oxide and calcium oxide. Through the above method, not only can the dispersion of zinc powder be effectively improved and the conductive efficiency of zinc powder be increased, but also it can play a filling role, enhance the density of the system, improve the mechanical properties of the paint film, and also play a medium barrier role, indirectly enhancing the corrosion resistance, thereby improving the anti-corrosion effect of the coating.

[0029] In summary, through the above method, the present invention not only reduces the zinc powder consumption, but also improves the anti-corrosion effect of waterborne zinc-rich epoxy coatings. The coatings have good storage stability, are safe and convenient for construction, have fast drying of the coating, strong adhesion of the paint film, and excellent anti-corrosion performance. Specific Embodiments

[0030] In order to make the technical problems, technical solutions and beneficial effects solved by the present invention clearer, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0031] The following uses specific embodiments to further describe the present invention in detail, but the present invention is not limited to the following specific embodiments.

[0032] In the following examples and comparative examples, the defoamer used was AF-706, the dispersant was HH2800, the wetting agent was 9440; the leveling agent was BYK-333, the film-forming auxiliary was lauryl alcohol ester film-forming auxiliary, the model of butanediol diglycidyl ether was 2425-79-8, the waterborne epoxy emulsion was 2164 (solid content 50%), and the model of bisphenol A type epoxy resin was E44 (Balin Petrochemical).

[0033] The preparation method of the waterborne epoxy curing agent used in the examples and comparative examples is as follows:

[0034] 1) Weigh diethylenetriamine (DETA) and butanediol diglycidyl ether into a round-bottom flask according to a molar ratio of 8:1 for reaction, heat to 65 °C, and react for 4 h to prepare a polyamine adduct intermediate;

[0035] 2) Evaporate the residual small molecule DETA in the polyamine adduct intermediate completely with diethylene glycol monoethyl ether with a slightly higher boiling point;

[0036] 3) Weigh bisphenol A type epoxy resin (model E44, Balin Petrochemical) and polyamine adduct intermediate into a round-bottom flask according to a molar ratio of 0.2:1 for addition reaction, heat to 85 °C, and react for 4 h to prepare a waterborne epoxy curing agent.

[0037] Example 1

[0038] (1) Take 10 g of nano-silica into a 500 mL flask, add 100 mL of toluene and ultrasonically disperse for 3 h, add 1 g of KH-560 (γ-(2,3-epoxypropoxy)propyltrimethoxysilane), react at 80 °C for 5 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare nano-silica with epoxy groups introduced on the surface.

[0039] (2) Take 9 g of nano-silica with epoxy groups introduced on the surface into a 500 ml beaker, add 50 ml of water to the beaker, and ultrasonically disperse the water solution for 3 h. Then take 3 g of Ti3C2T X into a 500 ml beaker, react at 60 °C for 6 h, then add 80 wt% hydrazine hydrate solution, react at 90 °C for 10 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare Ti3C2T X -silica composite nanomaterial.

[0040] (3)Put 100 g of lepidolite slag into a ball mill for ball milling until its specific surface area is 1200 m 2Particles of / kg are reserved. Mix 10 g of talcum powder with 1 g of ethylene glycol and conduct ultrasonic treatment at room temperature for 3 h in proportion. Then continue to add 3 g of urea aqueous solution (0.5 g of urea and 2.5 g of water), stir and react, then filter by suction, wash with water and ethanol, and dry in vacuum to prepare a talcum powder intercalation complex; then conduct ultrasonic treatment at room temperature for 1 h on 0.5 g of lithium slag, 60 g of zinc powder and 4.5 g of talcum powder intercalation complex in proportion, and then grind for 0.5 h with a ball mill under the condition of a rotation speed of 500 r / min to prepare a lithium slag / zinc powder / talcum powder intercalation complex.

[0041] (4)In a stirring kettle A, add 50 g of waterborne epoxy emulsion, 2 g of Ti3C2T X -silica, 0.1 g of defoamer, 0.4 g of dispersant, 0.1 g of wetting agent, 30 g of deionized water, and 65 g of lithium slag / zinc powder / talcum powder intercalation complex, and conduct stirring and dispersion at a rotation speed of 1000 r / min for 0.5 h to prepare 147.6 g of component A.

[0042] (5)In a stirring kettle B, add 50 g of waterborne epoxy curing agent, 0.1 g of defoamer, 0.1 g of leveling agent, and 0.1 g of film-forming aid, and stir evenly to prepare component B

[0043] (6)In a stirring kettle, add 147.6 g of component A and 50.3 g of component B in sequence, conduct stirring and dispersion at a rotation speed of 300 r / min for 0.5 h to prepare a waterborne epoxy zinc-rich coating containing lithium mica slag.

[0044] Example 2

[0045] (1)Take 10 g of nano-silica in a 500 mL flask, add 100 mL of toluene and conduct ultrasonic dispersion for 3 h, add 1 g of KH-560 (γ-(2,3-epoxypropoxy)propyltrimethoxysilane), react at 80 °C for 5 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare nano-silica with epoxy groups introduced on the surface.

[0046] (2)Take 9 g of nano-silica with epoxy groups introduced on the surface in a 500 ml beaker, add 50 ml of water to the beaker, and conduct ultrasonic dispersion on the water solution for 3 h. Then take 3 g of Ti3C2T X in a 500 ml beaker, react at 60 °C for 6 h, then add 80 wt% hydrazine hydrate solution, react at 90 °C for 10 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare Ti3C2T X -silica composite nano-material.

[0047] (3)Put 100 g of lithium mica slag into a ball mill for ball milling until its specific surface area is 1200 m 2Particles of / kg are reserved. Mix 10 g of talcum powder with 1 g of ethylene glycol, perform ultrasonic treatment at room temperature for 3 h in proportion, then add 3 g of urea aqueous solution (0.5 g of urea and 2.5 g of water) and stir to react. After that, filter by suction, wash with water and ethanol, and dry in vacuum to prepare the talcum powder intercalation complex; then perform ultrasonic treatment at room temperature for 1 h on 0.5 g of lithium slag, 50 g of zinc powder and 4.5 g of talcum powder intercalation complex in proportion, and then grind with a ball mill at a rotation speed of 500 r / min for 0.5 h to prepare the lithium slag / zinc powder / talcum powder intercalation complex.

[0048] (4)In a stirring kettle A, add 50 g of waterborne epoxy emulsion, 2 g of Ti3C2T X -silica, 0.1 g of defoamer, 0.4 g of dispersant, 0.1 g of wetting agent, 25 g of deionized water, 55 g of lithium slag / zinc powder / talcum powder intercalation complex, and perform stirring and dispersion at a rotation speed of 1000 r / min for 0.5 h to prepare 132.6 g of component A.

[0049] (5)In a stirring kettle B, add 50 g of waterborne epoxy curing agent, 0.1 g of defoamer, 0.1 g of leveling agent, 0.1 g of film-forming auxiliary agent and stir evenly to prepare component B

[0050] (6)In a stirring kettle, add 132.6 g of component A and 50.3 g of component B in sequence, perform stirring and dispersion at a rotation speed of 300 r / min for 0.5 h to prepare the waterborne epoxy zinc-rich coating containing lepidolite slag.

[0051] Example 3

[0052] (1)Take 10 g of nano-silica in a 500 mL flask, add 100 mL of toluene and perform ultrasonic dispersion for 3 h, add 1 g of KH-560 (γ-(2,3-epoxypropoxy)propyltrimethoxysilane), react at 80 °C for 5 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare nano-silica with epoxy groups introduced on the surface.

[0053] (2)Take 9 g of nano-silica with epoxy groups introduced on the surface in a 500 ml beaker, add 50 ml of water to the beaker, and perform ultrasonic dispersion on the water solution for 3 h. Then take 3 g of Ti3C2T X in a 500 ml beaker, react at 60 °C for 6 h, then add 80 wt% hydrazine hydrate solution, react at 90 °C for 10 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare Ti3C2T X -silica composite nano-material.

[0054] (3)Put 100 g of lepidolite slag into a ball mill for ball milling until its specific surface area is 1200 m 2Particles of / kg are reserved. Mix 10 g of talcum powder with 1 g of ethylene glycol and perform ultrasonic treatment at room temperature for 3 h according to a certain ratio. Then continue to add 3 g of urea aqueous solution (0.5 g of urea and 2.5 g of water), stir and react, then filter, wash with water and ethanol, and dry in vacuum to prepare a talcum powder intercalation complex; then perform ultrasonic treatment at room temperature for 1 h on 0.5 g of lithium slag, 40 g of zinc powder and 4.5 g of talcum powder intercalation complex according to a certain ratio, and then grind with a ball mill at a rotation speed of 500 r / min for 0.5 h to prepare a lithium slag / zinc powder / talcum powder intercalation complex.

[0055] (4)In a stirring kettle A, add 50 g of waterborne epoxy emulsion, 2 g of Ti3C2T X -silica, 0.1 g of defoamer, 0.4 g of dispersant, 0.1 g of wetting agent, 20 g of deionized water, and 45 g of lithium slag / zinc powder / talcum powder intercalation complex, and perform stirring and dispersion at a rotation speed of 1000 r / min for 0.5 h to prepare 117.1 g of component A.

[0056] (5)In a stirring kettle B, add 50 g of waterborne epoxy curing agent, 0.1 g of defoamer, 0.1 g of leveling agent, and 0.1 g of film-forming auxiliary agent, and stir evenly to prepare component B

[0057] (6)In a stirring kettle, add 117.1 g of component A and 50.3 g of component B in sequence, and perform stirring and dispersion at a rotation speed of 300 r / min for 0.5 h to prepare a waterborne epoxy zinc-rich coating containing lepidolite slag.

[0058] Example 4

[0059] (1)Take 10 g of nano-silica in a 500 mL flask, add 100 mL of toluene and perform ultrasonic dispersion for 3 h, add 1 g of KH-560 (γ-(2,3-epoxypropoxy)propyltrimethoxysilane), react at 80 °C for 5 h, filter after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare nano-silica with epoxy groups introduced on the surface.

[0060] (2)Take 9 g of nano-silica with epoxy groups introduced on the surface in a 500 ml beaker, add 50 ml of water to the beaker, and perform ultrasonic dispersion on the water solution for 3 h. Then take 6 g of Ti3C2T X in a 500 ml beaker, react at 60 °C for 6 h, then add 80 wt% hydrazine hydrate solution, react at 90 °C for 10 h, filter after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare Ti3C2T X -silica composite nano-material.

[0061] (3)Put 100 g of lepidolite slag into a ball mill for ball milling until its specific surface area is 1200 m2 Particles of / kg, reserved. Mix 10 g of talcum powder with 1 g of ethylene glycol and perform ultrasonic treatment at room temperature for 3 h according to the ratio. Then continue to add 3 g of urea aqueous solution (0.5 g of urea and 2.5 g of water), stir and react, then filter by suction, wash with water and ethanol, and dry in vacuum to prepare a talcum powder intercalation complex; then perform ultrasonic treatment at room temperature for 1 h on 0.5 g of lithium slag, 40 g of zinc powder and 4.5 g of talcum powder intercalation complex according to the ratio, and then grind for 0.5 h with a ball mill at a rotation speed of 500 r / min to prepare a lithium slag / zinc powder / talcum powder intercalation complex.

[0062] (4)Add 50 g of waterborne epoxy emulsion, 2.5 g of Ti3C2T X -silica, 0.1 g of defoamer, 0.4 g of dispersant, 0.1 g of wetting agent, 20 g of deionized water, and 45 g of lithium slag / zinc powder / talcum powder intercalation complex to a stirring kettle A, stir and disperse at a rotation speed of 1000 r / min for 0.5 h to prepare 118.1 g of component A.

[0063] (5)Add 50 g of waterborne epoxy curing agent, 0.1 g of defoamer, 0.1 g of leveling agent, and 0.1 g of film-forming auxiliary agent to a stirring kettle B and stir evenly to prepare component B.

[0064] (6)Add 118.1 g of component A and 50.3 g of component B to a stirring kettle in sequence, stir and disperse at a rotation speed of 300 r / min for 0.5 h to prepare a waterborne epoxy zinc-rich coating containing lepidolite slag.

[0065] Example 5

[0066] (1)Take 10 g of nano-silica in a 500 mL flask, add 100 mL of toluene and disperse ultrasonically for 3 h, add 1 g of KH-560 (γ-(2,3-epoxypropoxy)propyltrimethoxysilane), react at 80 °C for 5 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare nano-silica with epoxy groups introduced on the surface.

[0067] (2)Take 9 g of nano-silica with epoxy groups introduced on the surface in a 500 ml beaker, add 50 ml of water to the beaker, and disperse the water solution ultrasonically for 3 h. Then take 3 g of Ti3C2T X in a 500 ml beaker, react at 60 °C for 6 h, then add 80 wt% hydrazine hydrate solution, react at 90 °C for 10 h, filter by suction after cooling to room temperature, wash with water and ethanol, and dry in vacuum to prepare Ti3C2T X -silica composite nanomaterial.

[0068] (3) Put 100 g of lepidolite slag into a ball mill for ball milling until the particle has a specific surface area of 1,200 m 2 / kg, and set aside. Mix 10 g of talc powder with 1 g of ethylene glycol and perform ultrasonic treatment at room temperature for 3 h in proportion. Then continue to add 3 g of urea aqueous solution (0.5 g of urea and 2.5 g of water), stir and react, then filter by suction, wash with water and ethanol, and dry in vacuum to prepare a talc powder intercalation complex; then perform ultrasonic treatment at room temperature for 1 h on 0.5 g of lithium slag, 40 g of zinc powder and 4.5 g of talc powder intercalation complex in proportion, and then grind with a ball mill at a rotation speed of 500 r / min for 0.5 h to prepare a lithium slag / zinc powder / talc powder intercalation complex.

[0069] (4) Add 50 g of waterborne epoxy emulsion, 1 g of Ti3C2T X -silica, 0.1 g of defoamer, 0.4 g of dispersant, 0.1 g of wetting agent, 20 g of deionized water, and 45 g of lithium slag / zinc powder / talc powder intercalation complex to a stirring kettle A, and perform stirring and dispersion at a rotation speed of 1,000 r / min for 0.5 h to prepare 116.6 g of component A.

[0070] (5) Add 50 g of waterborne epoxy curing agent, 0.1 g of defoamer, 0.1 g of leveling agent, and 0.1 g of film-forming auxiliary agent to a stirring kettle B and stir evenly to prepare component B.

[0071] (6) Add 116.6 g of component A and 50.3 g of component B to a stirring kettle in sequence, perform stirring and dispersion at a rotation speed of 300 r / min for 0.5 h to prepare a waterborne epoxy zinc-rich coating containing lepidolite slag.

[0072] Comparative Example 1

[0073] (1) Put 100 g of lepidolite slag into a ball mill for ball milling until the particle has a specific surface area of 1,200 m 2 / kg, and set aside. Mix 10 g of talc powder with 1 g of ethylene glycol and perform ultrasonic treatment at room temperature for 3 h in proportion. Then continue to add 3 g of urea aqueous solution (0.5 g of urea and 2.5 g of water), stir and react, then filter by suction, wash with water and ethanol, and dry in vacuum to prepare a talc powder intercalation complex; then perform ultrasonic treatment at room temperature for 1 h on 0.5 g of lithium slag, 80 g of zinc powder and 4.5 g of talc powder intercalation complex in proportion, and then grind with a ball mill at a rotation speed of 500 r / min for 0.5 h to prepare a lithium slag / zinc powder / talc powder intercalation complex.

[0074] (2) 50 g of waterborne epoxy emulsion, 1.5 g of silica, 0.1 g of defoamer, 0.4 g of dispersant, 0.1 g of wetting agent, 40 g of deionized water, and 85 g of lithium slag / zinc powder / talcum powder intercalation complex were successively added to a stirring kettle A for stirring and dispersion at a rotation speed of 1000 r / min for 0.5 h to prepare 177.1 g of component A.

[0075] (3) 50 g of waterborne epoxy curing agent, 0.1 g of defoamer, 0.1 g of leveling agent, and 0.1 g of film-forming auxiliary agent were added to a stirring kettle B and stirred evenly to prepare component B.

[0076] (4) 177.1 g of component A and 50.3 g of component B were successively added to a stirring kettle for stirring and dispersion at a rotation speed of 300 r / min for 0.5 h to prepare a waterborne epoxy zinc-rich coating containing lithium mica slag.

[0077] Comparative Example 2

[0078] The difference from Example 1 is that "1 g of KH-560 (γ-(2,3-epoxypropoxy)propyltrimethoxysilane)" was not added in step (1), and the other steps were the same as those in Example 1.

[0079] Comparative Example 3

[0080] The difference from Example 1 is that step (3) was not carried out, that is, component A did not contain "lithium slag / zinc powder / talcum powder intercalation complex", and the other steps were the same as those in Example 1.

[0081] Comparative Example 4

[0082] The difference from Example 1 is that step (3) was changed to:

[0083] 4.5 g of talcum powder, 0.5 g of lithium slag, and 40 g of zinc powder were subjected to normal temperature ultrasonic treatment for 1 h in proportion, and then ground in a ball mill at a rotation speed of 350 r / min for 6 h to prepare a lithium slag / zinc powder / talcum powder mixture.

[0084] The other steps were the same as those in Example 1.

[0085] Comparative Example 5

[0086] The difference from Example 1 is that zinc powder was not added in step (3), that is, a lithium slag / talcum powder intercalation complex was prepared in step (3); and 60 g of zinc powder was added simultaneously in step (4).

[0087] The other steps were the same as those in Example 1.

[0088] Comparative Example 6

[0089] The difference from Example 1 is that: zinc powder is not added in step (3), that is, the lithium slag / talcum powder intercalation composite is prepared in step (3);

[0090] The other steps are the same as those in Example 1.

[0091] Table 1 Formulas of coatings prepared in Examples 1-5 and Comparative Examples 1-5

[0092]

[0093] The performance tests of the waterborne epoxy zinc-rich coatings containing lithium mica slag prepared in Examples 1 to 6 and the coatings prepared in Comparative Examples 1 to 5 were carried out. The performance tests were conducted according to the following standards: (1) The drying time of the coating was tested in accordance with GB / T 1728-2020 "Determination of drying time of paint film and putty film"; (2) The impact resistance of the coating was tested in accordance with GB / T 1732-1993 "Determination of impact resistance of paint film" with a 1 kg hammer; (3) The adhesion of the coating was tested in accordance with GB / T 9286-1998 "Scratch test for paint and varnish film" and GB / T 5210-2006 "Adhesion test for paint and varnish by pull-off method"; (4) The freeze-thaw stability of the coating was tested in accordance with GB / T 9268-2008 "Determination of freeze-thaw resistance of latex paint"; (5) The coating was cured for 10 days under the conditions specified in GB / T 9278-2008 "Temperature and humidity for condition adjustment and testing of paint specimens" After 14 days, the salt spray resistance of the paint film was tested in accordance with GB / T 1771-2007 “Determination of resistance of paints and varnishes to neutral salt spray”, and the test was conducted after the paint film sample was scratched.

[0094] Table 2 Performance test results of coatings prepared in Examples 1-5 and Comparative Examples 1-6

[0095]

[0096] As can be seen from Table 2, the water-based epoxy zinc-rich coating containing lithium mica slag prepared in Examples 1-6 has no lumps after stirring and mixing, is in a uniform state, has no obstacles in application, has a normal coating appearance, a surface drying time of 2h, a practical drying time of 12h, an impact resistance of 50-55, an adhesion of level 1, and a salt spray resistance of 480-960h.

[0097] Comparing Example 1 with Comparative Examples 1-2, it can be seen that Comparative Example 1 does not add KH-560 and Ti3C2T X Comparative Example 2 does not add KH-560. The impact resistance and salt spray resistance of Comparative Example 1-2 are significantly lower than those of Example 1. This shows that whether KH-560 and Ti3C2T are added X Will affect impact resistance and salt spray resistance.

[0098] Comparing Example 1 with Comparative Examples 3-6, it can be seen that in Comparative Example 3, "lithium slag / zinc powder / talcum powder intercalation complex" was not added; in Comparative Example 4, "lithium slag / zinc powder / talcum powder mixture" was added; in Comparative Example 5, lithium slag / talcum powder intercalation complex was prepared and zinc powder was added separately; in Comparative Example 6, zinc powder was not added. The salt spray resistance of Comparative Examples 3-6 decreased significantly compared with that of Example 1. Therefore, whether to add "lithium slag / zinc powder / talcum powder intercalation complex", whether to add "zinc powder", and the preparation method of "lithium slag / zinc powder / talcum powder intercalation complex" will affect the salt spray resistance of the coating.

[0099] As mentioned above, the above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

Claims

1. A preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag, characterized in that, It includes the following steps: Mix nano-silica with toluene and carry out ultrasonic dispersion for 2 - 3 h. Add KH-560 into a flask and react at 80 - 90 °C for 4 - 8 h. After cooling to room temperature, perform suction filtration, wash with water and ethanol, and dry under vacuum to prepare nano-silica with epoxy groups introduced on the surface; Mix the nano-silica with epoxy groups introduced on the surface with water and carry out ultrasonic dispersion for 2 - 5 h. Then continue to add Ti3C2T X , react at 60 - 90 °C for 6 - 8 h, add 70 - 80 wt% hydrazine hydrate solution, react at 90 - 95 °C for 10 - 12 h. After cooling to room temperature, perform suction filtration, wash with water and ethanol, and dry under vacuum to prepare Ti3C2T X -silica composite nanomaterials; Put the lepidolite slag into a ball mill for ball milling until the specific surface area of the particles is 1000 - 1500 m 2 / kg to obtain lithium slag; mix talcum powder and ethylene glycol and perform ultrasonic treatment at room temperature for 2 - 5 h, then continue to add an aqueous urea solution and stir to react, followed by suction filtration, washing with water and ethanol, and vacuum drying to prepare a talcum powder intercalation complex; then perform ultrasonic treatment on the lithium slag, zinc powder and the talcum powder intercalation complex at room temperature for 0.5 - 2 h, and then grind with a ball mill at a rotational speed of 300 - 600 r / min for 0.4 - 1 h to prepare a lithium slag / zinc powder / talcum powder intercalation complex; Add the waterborne epoxy emulsion, the Ti3C2T X -silica composite nanomaterial, deionized water, dispersant, defoamer, wetting agent, deionized water, and lithium slag / zinc powder / talc powder intercalation complex into the stirring kettle in sequence, stir evenly at a rotation speed of 100-500 r / min for 0.5-1 h to prepare Component A; Add a waterborne epoxy curing agent, an antifoaming agent, a leveling agent, and a film-forming auxiliary agent into a stirring kettle and stir evenly to prepare Component B; Add Component A and Component B into a stirring kettle in sequence and carry out stirring and dispersion at a rotation speed of 200 - 500 r / min for 0.5 - 1 h to prepare a waterborne epoxy zinc-rich coating containing lepidolite slag.

2. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, characterized in that, The described Ti3C2T X is a single-layer or multi-layer structure.

3. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, characterized in that, The waterborne epoxy emulsion is a bisphenol A type epoxy resin emulsion with a solid content of 40% - 60%.

4. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, characterized in that, The preparation method of the waterborne epoxy curing agent includes: 1) Weigh diethylenetriamine and butanediol diglycidyl ether according to a molar ratio of 8:1 respectively for reaction, heat to 60 - 70 °C, and the reaction time is 3 - 5 h to prepare a polyamine adduct intermediate; 2) Evaporate the residual small molecule diethylenetriamine in the polyamine adduct intermediate completely with diethylene glycol monoethyl ether; 3) Weigh bisphenol A type epoxy resin and polyamine adduct intermediate according to a molar ratio of 0.2:1 respectively for addition reaction, heat to 80 - 90 °C, and the reaction time is 3 - 5 h to prepare a waterborne epoxy curing agent.

5. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, characterized in that, The mass ratio of the silicon dioxide to KH-560 is 5 - 20:

1.

6. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, wherein, The described silica:Ti3C2T X has a mass ratio of 2-5:1; the described talcum powder:ethylene glycol:urea has a mass ratio of 10-15:1:0.

5.

7. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, characterized in that, The mass ratio of the lithium slag to the zinc powder to the talc powder intercalation complex is 1:30 - 150:5 - 20.

8. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, characterized in that, In the described Component A, the mass ratio of the aqueous epoxy emulsion: Ti3C2T X - silica nanomaterial: defoamer: dispersant: wetting agent: deionized water: lithium slag / zinc powder / talc powder intercalation complex is 50-100: 2-6: 0.1-0.5: 0.5-1: 0.1-0.5: 20-80: 30-100.

9. The preparation method of a waterborne epoxy zinc-rich coating containing lepidolite slag according to claim 1, characterized in that, In Component B, the mass ratio of the waterborne epoxy curing agent to the antifoaming agent to the leveling agent to the film-forming auxiliary agent = 50 - 100:0.1 - 0.5:0.1 - 0.5:0.1 - 0.5; the mass ratio of the waterborne epoxy emulsion to Component B = 0.5 - 2:

1.

10. A waterborne epoxy zinc-rich coating containing lepidolite slag, characterized in that, It is prepared by using the method described in any one of Claims 1 - 9.

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