Preparation method of water-based bi-component epoxy primer

Abstract

The preparation method comprises the following steps: weighing raw materials in parts by weight: firstly weighing raw materials of a component A: 35-45 parts of epoxy resin, 10-15 parts of a modified functional agent, 5-8 parts of a carbon nanotube regulator, 4-7 parts of a flame retardant, 4-6 parts of a silane coupling agent, 2-5 parts of a wetting dispersant and 20-30 parts of water; the waterborne two-component epoxy primer is prepared by mixing the component A and the component B, the component A is prepared by blending the epoxy resin with the flame retardant, the silane coupling agent and the wetting dispersant, and meanwhile, the modified functional agent and the carbon nanotube regulator are added for cooperation and synergism, so that the flame-retardant and flame-retardant waterborne two-component epoxy primer is prepared through co-cooperation and synergism of the raw materials; the flame retardance, adhesive force and impact resistance balance coordination of the product are optimized, and meanwhile, the corrosion resistance and weather resistance durability effect of the product is remarkable.

Description

Technical Field

[0001] The invention relates to the technical field of epoxy primers, and in particular to a preparation method of a water-based two-component epoxy primer. Background Art

[0002] As the foundation of the coating system, primers play a key role in substrate adhesion, corrosion and rust prevention, and improving topcoat adhesion. They are widely used for surface protection of metal components such as bridges, machinery, ships, and automobiles. Existing epoxy primers utilize an epoxy matrix combined with a curing agent. To optimize the primer's flame retardancy, flame retardants and inorganic raw materials are often added to enhance the product's functionality. However, this can lead to poor interfacial properties between the raw materials, making it difficult to balance the product's flame retardancy, adhesion, and impact resistance. Furthermore, the product's corrosion resistance and weathering durability are poorly maintained, limiting its effectiveness. Summary of the Invention

[0003] In view of the defects of the prior art, the purpose of the present invention is to provide a method for preparing a water-based two-component epoxy primer to solve the problems raised in the above background technology.

[0004] The present invention solves the technical problem by adopting the following technical solutions: The present invention provides a method for preparing a water-based two-component epoxy primer, comprising the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 35-45 parts of epoxy resin, 10-15 parts of modifying functional agent, 5-8 parts of carbon nanotube regulator, 4-7 parts of flame retardant, 4-6 parts of silane coupling agent, 2-5 parts of wetting and dispersing agent and 20-30 parts of water; Then weigh the raw materials of component B: 35-40 parts of polyamide curing agent, 2-4 parts of epoxy catalyst and 20-30 parts of cosolvent; Step 2, preparation of component A: uniformly mix the raw materials of component A to prepare component A; preparation of component B: uniformly mix the raw materials of component B to prepare component B; Step 3: Component A and component B are evenly mixed in a weight ratio of (6-8):1 to prepare a two-component epoxy primer.

[0005] Preferably, the wetting and dispersing agent is Digo 760w, the flame retardant is magnesium hydroxide; the epoxy resin is a mixture of bisphenol A epoxy resin and aliphatic flexible epoxy resin in a weight ratio of 9:2; The epoxy equivalent weight of the bisphenol A epoxy resin is 480-500 g / mol; the aliphatic flexible epoxy resin is a polyglycol diglycidyl ether resin, with an epoxy equivalent weight of 320-330 g / mol, a solid content of ≥99%, and a viscosity of 70-80 mPa·s; The polyamide curing agent is 200 low molecular weight polyamide, solid content ≥99%, amine value 250-260 mgKOH / g; the epoxy drier is 2,4,6-tris(dimethylaminomethyl)phenol; the cosolvent is xylene; and the silane coupling agent is silane coupling agent KH560.

[0006] Preferably, the preparation method of the modified functional agent is: S01: 5-8 parts of mesoporous silica, 2-4 parts of β-cyclodextrin, 1-3 parts of sodium dodecylbenzenesulfonate and 5-8 parts of phosphate buffer solution are uniformly mixed to obtain a mesoporous silica solution; Stir calcium sulfate whiskers thoroughly in a sufficient amount of 8-12% sulfuric acid solution, then wash with water, filter and dry; The dried calcium sulfate whiskers and mesoporous silica liquid were mixed and stirred uniformly in a weight ratio of 4:7 to obtain a whisker-mesoporous silica functional liquid; S02: Preparation of modified titanium oxide agent: S021: Thoroughly blend 2-4 parts of tetrabutyl titanate, 5-8 parts of acetone solvent, 2-3 parts of sodium alginate, and 2-3 parts of formic acid solution to obtain a modifier; S022: impregnating the titanium oxide into a modifier in an amount 3-5 times the total amount of the titanium oxide, filtering and drying after the impregnation is completed to obtain a modified titanium oxide agent; S03: The modified titanium oxide agent and whisker-mesoporous silica functional liquid are mixed and ball-milled in a weight ratio of 7:(3-5) at a ball-milling speed of 1500-1700 r / min for 2 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the modified functional agent.

[0007] Preferably, the particle size of the mesoporous silica is 70-100 nm, and the pore size is 15-20 nm; the pH value of the phosphate buffer solution is 5.5-6.0.

[0008] Preferably, the mass fraction of the formic acid solution is 4-7%.

[0009] Preferably, the preparation method of the carbon nanotube regulator is: S11: stirring the carbon nanotubes uniformly in a sufficient amount of 8% by mass potassium permanganate solution, then washing with water, filtering, and drying, and then stirring the carbon nanotubes uniformly in a sufficient amount of 5% by mass sulfuric acid solution, then washing with water, filtering, and drying to obtain pretreated carbon nanotubes; S12: Preparation of AB compound solution: S12a: Preparation of Solution A: Tannic acid, water, and sodium carbonate are uniformly blended in a weight ratio of 3:7:1, and then nanocellulose is added thereto in an amount of 45-55% of the total amount of tannic acid. The mixture is then stirred thoroughly, filtered, and dried to obtain tannin-modified nanocellulose. Tannin-modified nanocellulose and silane coupling liquid were stirred thoroughly in a weight ratio of 5:8 to obtain liquid A; the silane coupling liquid was prepared by stirring silane coupling agent KH550, ethanol and water in a weight ratio of 4:7:5; S12b: Preparation of Agent B: 3-5 parts of strontium titanate, 2-3 parts of aluminum silicate fiber and 5-8 parts of modified lanthanum oxide are uniformly blended to obtain agent B; solution A and agent B are blended in a weight ratio of 7:5 and ball-milled at a speed of 1000-1500 r / min for 2 hours to obtain AB polyhydric solution; S13: adding the pretreated carbon nanotubes to the AB reconstitution solution in an amount of 4-7 times the total amount of the pretreated carbon nanotubes and stirring; after stirring, filtering and drying to obtain a carbon nanotube regulator.

[0010] Preferably, the stirring speed of the stirring treatment in S13 is 350-400 r / min, the stirring is for 1 hour, and the stirring temperature is 50-55°C.

[0011] Preferably, the modification method of the modified lanthanum oxide is: Preheat lanthanum oxide at 55-60°C for 1 hour, keep the temperature, and mix the kept lanthanum oxide and the modified solution in a weight ratio of 7:(3-4) and ball mill at a ball milling speed of 1000-1200 r / min for 2 hours. After the ball milling is completed, filter and dry to obtain the modified lanthanum oxide; The preparation method of the modified liquid is as follows: 3-5 parts of flaky boron nitride, 2-4 parts of α-aluminum oxide, 5-8 parts of sodium silicate solution, 1-2 parts of diethanolamine and 0.5-0.7 parts of sodium acrylate are mixed.

[0012] Preferably, the mass fraction of the sodium silicate solution is 2-5%; and the diameter of the flaky boron nitride is 1-2 μm.

[0013] Compared with the prior art, the present invention has the following beneficial effects: 1. The water-based two-component epoxy primer of the present invention is prepared by mixing component A and component B. Component A is prepared by mixing epoxy resin with flame retardant, silane coupling agent and wetting dispersant, and functional modifying agent and carbon nanotube regulator are added for synergistic effect. The performance of the product is optimized by the synergistic effect of the co-mixing of raw materials. Meanwhile, component B is prepared by mixing and optimizing polyamide curing agent, epoxy catalyst and cosolvent. The co-mixing and co-helping of raw materials further enhance the interface between raw materials in the epoxy primer, optimize the balance and coordination of flame retardancy, adhesion and impact resistance of the product, and at the same time, the corrosion resistance and weather resistance of the product are significantly improved. 2. The functional modification agent is treated by impregnating titanium oxide into the modifier. The tetrabutyl titanate, acetone solvent, sodium alginate and formic acid solution in the modifier are optimized and blended together. Through the co-coordination and coordination between the raw materials, the coordination effect between titanium oxide and the whisker-mesoporous silica functional liquid is enhanced, and the interface connectivity of the functional modification agent in the system is optimized, while improving the performance efficiency of the product. 3. The whisker-mesoporous silica functional liquid is optimized by using calcium sulfate whiskers activated by acid solution, and then optimized by blending with mesoporous silica liquid. The mesoporous silica in the mesoporous silica liquid is used as the matrix, and is blended with β-cyclodextrin, sodium dodecylbenzenesulfonate and phosphate buffer solution. The calcium sulfate whiskers are blended with mesoporous silica. Through the co-matching improvement between the raw materials, the bearing interface capacity of the whisker-mesoporous silica is enhanced, thereby better matching and connecting the raw materials. Combined with the modified titanium oxide agent, the performance of the product is further improved. 4. The carbon nanotube regulator uses carbon nanotubes that have been improved and optimized by potassium permanganate solution and sulfuric acid solution to improve the activity of the carbon nanotubes. At the same time, nanocellulose is optimized and improved with tannic acid, water and sodium carbonate to produce tannin-modified nanocellulose, which is then blended with silane coupling liquid to enhance the interfacial activity of the nanocellulose and the stability of its connection with other raw materials. Strontium titanate, aluminum silicate fiber and modified lanthanum oxide are blended to form agent B. The needle-like structure of the aluminum silicate fiber in agent B is combined with strontium titanate and modified lanthanum oxide to be distributed in the liquid A system. By improving the matching of the raw materials, the AB compound liquid prepared is combined with the improved carbon nanotubes. The high specific surface area of ​​the carbon nanotubes supports the AB compound liquid system, and the resulting carbon nanotube regulator further enhances the performance of the product in the system. 5. Modified lanthanum oxide is prepared by preheating lanthanum oxide and then improving it by ball milling with a modifying liquid. The modifying liquid is based on flaky boron nitride. Sodium silicate solution, diethanolamine and sodium acrylate are blended with α-alumina. The flaky boron nitride is adjusted into the system with α-alumina, and further combined with sodium silicate solution, diethanolamine and sodium acrylate. The modified lanthanum oxide prepared by the co-combination improvement of the raw materials is added into the system to further optimize the performance of the product. DETAILED DESCRIPTION

[0014] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0015] The preparation method of a water-based two-component epoxy primer of this embodiment comprises the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 35-45 parts of epoxy resin, 10-15 parts of modifying functional agent, 5-8 parts of carbon nanotube regulator, 4-7 parts of flame retardant, 4-6 parts of silane coupling agent, 2-5 parts of wetting and dispersing agent and 20-30 parts of water; Then weigh the raw materials of component B: 35-40 parts of polyamide curing agent, 2-4 parts of epoxy catalyst and 20-30 parts of cosolvent; Step 2, preparation of component A: uniformly mix the raw materials of component A to prepare component A; preparation of component B: uniformly mix the raw materials of component B to prepare component B; Step 3: Component A and component B are evenly mixed in a weight ratio of (6-8):1 to prepare a two-component epoxy primer.

[0016] The wetting and dispersing agent in this embodiment is Digo 760w, the flame retardant is magnesium hydroxide; the epoxy resin is a mixture of bisphenol A epoxy resin and aliphatic flexible epoxy resin in a weight ratio of 9:2; The epoxy equivalent weight of the bisphenol A epoxy resin is 480-500 g / mol; the aliphatic flexible epoxy resin is a polyglycol diglycidyl ether resin, with an epoxy equivalent weight of 320-330 g / mol, a solid content of ≥99%, and a viscosity of 70-80 mPa·s; The polyamide curing agent is 200 low molecular weight polyamide, solid content ≥99%, amine value 250-260 mgKOH / g; the epoxy drier is 2,4,6-tris(dimethylaminomethyl)phenol; the cosolvent is xylene; and the silane coupling agent is silane coupling agent KH560.

[0017] The preparation method of the modified functional agent of this embodiment is: S01: 5-8 parts of mesoporous silica, 2-4 parts of β-cyclodextrin, 1-3 parts of sodium dodecylbenzenesulfonate and 5-8 parts of phosphate buffer solution are uniformly mixed to obtain a mesoporous silica solution; Stir calcium sulfate whiskers thoroughly in a sufficient amount of 8-12% sulfuric acid solution, then wash with water, filter and dry; The dried calcium sulfate whiskers and mesoporous silica liquid were mixed and stirred uniformly in a weight ratio of 4:7 to obtain a whisker-mesoporous silica functional liquid; S02: Preparation of modified titanium oxide agent: S021: Thoroughly blend 2-4 parts of tetrabutyl titanate, 5-8 parts of acetone solvent, 2-3 parts of sodium alginate, and 2-3 parts of formic acid solution to obtain a modifier; S022: impregnating the titanium oxide into a modifier in an amount 3-5 times the total amount of the titanium oxide, filtering and drying after the impregnation is completed to obtain a modified titanium oxide agent; S03: The modified titanium oxide agent and whisker-mesoporous silica functional liquid are mixed and ball-milled in a weight ratio of 7:(3-5) at a ball-milling speed of 1500-1700 r / min for 2 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the modified functional agent.

[0018] The particle size of the mesoporous silica in this embodiment is 70-100 nm, and the pore size is 15-20 nm; the pH value of the phosphate buffer solution is 5.5-6.0.

[0019] The mass fraction of the formic acid solution in this embodiment is 4-7%.

[0020] The preparation method of the carbon nanotube regulator of this embodiment is: S11: stirring the carbon nanotubes uniformly in a sufficient amount of 8% by mass potassium permanganate solution, then washing with water, filtering, and drying, and then stirring the carbon nanotubes uniformly in a sufficient amount of 5% by mass sulfuric acid solution, then washing with water, filtering, and drying to obtain pretreated carbon nanotubes; S12: Preparation of AB compound solution: S12a: Preparation of Solution A: Tannic acid, water, and sodium carbonate are uniformly blended in a weight ratio of 3:7:1, and then nanocellulose is added thereto in an amount of 45-55% of the total amount of tannic acid. The mixture is then stirred thoroughly, filtered, and dried to obtain tannin-modified nanocellulose. Tannin-modified nanocellulose and silane coupling liquid were stirred thoroughly in a weight ratio of 5:8 to obtain liquid A; the silane coupling liquid was prepared by stirring silane coupling agent KH550, ethanol and water in a weight ratio of 4:7:5; S12b: Preparation of Agent B: 3-5 parts of strontium titanate, 2-3 parts of aluminum silicate fiber and 5-8 parts of modified lanthanum oxide are uniformly blended to obtain agent B; solution A and agent B are blended in a weight ratio of 7:5 and ball-milled at a speed of 1000-1500 r / min for 2 hours to obtain AB polyhydric solution; S13: adding the pretreated carbon nanotubes to the AB reconstitution solution in an amount of 4-7 times the total amount of the pretreated carbon nanotubes and stirring; after stirring, filtering and drying to obtain a carbon nanotube regulator.

[0021] The stirring process in S13 of this embodiment has a stirring speed of 350-400 r / min, stirring for 1 hour, and a stirring temperature of 50-55°C.

[0022] The modification method of the modified lanthanum oxide of this embodiment is: Preheat lanthanum oxide at 55-60°C for 1 hour, keep the temperature, and mix the kept lanthanum oxide and the modified solution in a weight ratio of 7:(3-4) and ball mill at a ball milling speed of 1000-1200 r / min for 2 hours. After the ball milling is completed, filter and dry to obtain the modified lanthanum oxide; The preparation method of the modified liquid is as follows: 3-5 parts of flaky boron nitride, 2-4 parts of α-aluminum oxide, 5-8 parts of sodium silicate solution, 1-2 parts of diethanolamine and 0.5-0.7 parts of sodium acrylate are mixed.

[0023] The mass fraction of the sodium silicate solution in this embodiment is 2-5%; the diameter of the flake boron nitride is 1-2 μm.

[0024] Example 1. The preparation method of a water-based two-component epoxy primer of this embodiment comprises the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 35 parts of epoxy resin, 10 parts of modifying functional agent, 5 parts of carbon nanotube regulator, 4 parts of flame retardant, 4 parts of silane coupling agent, 2 parts of wetting and dispersing agent and 20 parts of water; Then weigh the raw materials of component B: 35 parts of polyamide curing agent, 2 parts of epoxy catalyst and 20 parts of cosolvent; Step 2, preparation of component A: uniformly mix the raw materials of component A to prepare component A; preparation of component B: uniformly mix the raw materials of component B to prepare component B; Step 3: Component A and component B are evenly mixed in a weight ratio of 6:1 to prepare a two-component epoxy primer.

[0025] The wetting and dispersing agent in this embodiment is Digo 760w, the flame retardant is magnesium hydroxide; the epoxy resin is a mixture of bisphenol A epoxy resin and aliphatic flexible epoxy resin in a weight ratio of 9:2; The epoxy equivalent weight of the bisphenol A epoxy resin is 480 g / mol; the aliphatic flexible epoxy resin is a polyglycol diglycidyl ether resin with an epoxy equivalent weight of 320 g / mol, a solid content of ≥99%, and a viscosity of 70 mPa·s; The polyamide curing agent is 200 low molecular weight polyamide, with a solid content of ≥99% and an amine value of 250 mgKOH / g; the epoxy drier is 2,4,6-tris(dimethylaminomethyl)phenol; the cosolvent is xylene; and the silane coupling agent is silane coupling agent KH560.

[0026] The preparation method of the modified functional agent of this embodiment is: S01: 5 parts of mesoporous silica, 2 parts of β-cyclodextrin, 1 part of sodium dodecylbenzenesulfonate and 5 parts of phosphate buffer solution are mixed evenly to obtain a mesoporous silica solution; Stir calcium sulfate whiskers thoroughly in a sufficient amount of 8% sulfuric acid solution, then wash with water, filter and dry; The dried calcium sulfate whiskers and mesoporous silica liquid were mixed and stirred uniformly in a weight ratio of 4:7 to obtain a whisker-mesoporous silica functional liquid; S02: Preparation of modified titanium oxide agent: S021: 2 parts of tetrabutyl titanate, 5 parts of acetone solvent, 2 parts of sodium alginate and 2 parts of formic acid solution are thoroughly mixed to obtain a modifier; S022: impregnating the titanium oxide into a modifier in an amount three times the total amount of the titanium oxide, filtering and drying after the impregnation is completed to obtain a modified titanium oxide agent; S03: The modified titanium oxide agent and whisker-mesoporous silica functional liquid are mixed and ball-milled in a weight ratio of 7:3 at a ball-milling speed of 1500 r / min for 2 h. After the ball-milling is completed, the mixture is filtered and dried to obtain a modified functional agent.

[0027] The particle size of the mesoporous silica in this embodiment is 70 nm, and the pore size is 15 nm; the pH value of the phosphate buffer solution is 5.5.

[0028] The mass fraction of the formic acid solution in this embodiment is 4%.

[0029] The preparation method of the carbon nanotube regulator of this embodiment is: S11: stirring the carbon nanotubes uniformly in a sufficient amount of 8% by mass potassium permanganate solution, then washing with water, filtering, and drying, and then stirring the carbon nanotubes uniformly in a sufficient amount of 5% by mass sulfuric acid solution, then washing with water, filtering, and drying to obtain pretreated carbon nanotubes; S12: Preparation of AB compound solution: S12a: Preparation of Solution A: Tannic acid, water, and sodium carbonate are uniformly blended in a weight ratio of 3:7:1, and then nanocellulose is added thereto in an amount of 45% of the total amount of tannic acid. The mixture is then stirred thoroughly, filtered, and dried to obtain tannin-modified nanocellulose. Tannin-modified nanocellulose and silane coupling liquid were stirred thoroughly in a weight ratio of 5:8 to obtain liquid A; the silane coupling liquid was prepared by stirring silane coupling agent KH550, ethanol and water in a weight ratio of 4:7:5; S12b: Preparation of Agent B: 3 parts of strontium titanate, 2 parts of aluminum silicate fiber and 5 parts of modified lanthanum oxide were uniformly blended to obtain agent B; solution A and agent B were blended in a weight ratio of 7:5 and ball-milled at a ball-milling speed of 1000 r / min for 2 hours to obtain AB polyadjusted solution; S13: adding the pretreated carbon nanotubes to the AB reconstitution solution in an amount of 4 times the total amount of the pretreated carbon nanotubes and stirring; after stirring, filtering and drying to obtain a carbon nanotube regulator.

[0030] The stirring process in S13 of this embodiment has a stirring speed of 350 r / min, stirring for 1 hour, and a stirring temperature of 50°C.

[0031] The modification method of the modified lanthanum oxide of this embodiment is: Lanthanum oxide was preheated at 55°C for 1 hour and kept warm. The kept warm lanthanum oxide and the modified solution were mixed and ball-milled at a weight ratio of 7:3 at a ball-milling speed of 1000 r / min for 2 hours. After the ball-milling was completed, the mixture was filtered and dried to obtain the modified lanthanum oxide. The preparation method of the modified liquid is as follows: 3 parts of flaky boron nitride, 2 parts of α-alumina, 5 parts of sodium silicate solution, 1 part of diethanolamine and 0.5 parts of sodium acrylate are mixed.

[0032] The mass fraction of the sodium silicate solution in this embodiment is 2%; the diameter of the flake boron nitride is 1 μm.

[0033] Example 2. The preparation method of a water-based two-component epoxy primer of this embodiment comprises the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 45 parts of epoxy resin, 15 parts of functional modifying agent, 8 parts of carbon nanotube regulator, 7 parts of flame retardant, 6 parts of silane coupling agent, 5 parts of wetting and dispersing agent and 30 parts of water; Then weigh the raw materials of component B: 40 parts of polyamide curing agent, 4 parts of epoxy catalyst and 30 parts of cosolvent; Step 2, preparation of component A: uniformly mix the raw materials of component A to prepare component A; preparation of component B: uniformly mix the raw materials of component B to prepare component B; Step 3: Component A and component B are evenly mixed in a weight ratio of 8:1 to prepare a two-component epoxy primer.

[0034] The wetting and dispersing agent in this embodiment is Digo 760w, the flame retardant is magnesium hydroxide; the epoxy resin is a mixture of bisphenol A epoxy resin and aliphatic flexible epoxy resin in a weight ratio of 9:2; The epoxy equivalent weight of the bisphenol A epoxy resin is 500 g / mol; the aliphatic flexible epoxy resin is a polyglycol diglycidyl ether resin, which has an epoxy equivalent weight of 330 g / mol, a solid content of ≥99%, and a viscosity of 80 mPa·s; The polyamide curing agent is 200 low molecular weight polyamide, with a solid content of ≥99% and an amine value of 260 mgKOH / g; the epoxy drier is 2,4,6-tris(dimethylaminomethyl)phenol; the cosolvent is xylene; and the silane coupling agent is silane coupling agent KH560.

[0035] The preparation method of the modified functional agent of this embodiment is: S01: 8 parts of mesoporous silica, 4 parts of β-cyclodextrin, 3 parts of sodium dodecylbenzenesulfonate and 8 parts of phosphate buffer solution are mixed evenly to obtain a mesoporous silica solution; Stir calcium sulfate whiskers thoroughly in a sufficient amount of 12% sulfuric acid solution, then wash with water, filter and dry; The dried calcium sulfate whiskers and mesoporous silica liquid were mixed and stirred uniformly in a weight ratio of 4:7 to obtain a whisker-mesoporous silica functional liquid; S02: Preparation of modified titanium oxide agent: S021: 4 parts of tetrabutyl titanate, 8 parts of acetone solvent, 3 parts of sodium alginate and 3 parts of formic acid solution are thoroughly mixed to obtain a modifier; S022: impregnating the titanium oxide into a modifier in an amount 5 times the total amount of the titanium oxide, filtering and drying after the impregnation is completed to obtain a modified titanium oxide agent; S03: The modified titanium oxide agent and whisker-mesoporous silica functional liquid are mixed and ball-milled in a weight ratio of 7:5 at a ball-milling speed of 1700 r / min for 2 h. After the ball-milling is completed, the mixture is filtered and dried to obtain a modified functional agent.

[0036] The particle size of the mesoporous silica in this embodiment is 100 nm, and the pore size is 20 nm; the pH value of the phosphate buffer solution is 6.0.

[0037] The mass fraction of the formic acid solution in this embodiment is 7%.

[0038] The preparation method of the carbon nanotube regulator of this embodiment is: S11: stirring the carbon nanotubes uniformly in a sufficient amount of 8% by mass potassium permanganate solution, then washing with water, filtering, and drying, and then stirring the carbon nanotubes uniformly in a sufficient amount of 5% by mass sulfuric acid solution, then washing with water, filtering, and drying to obtain pretreated carbon nanotubes; S12: Preparation of AB compound solution: S12a: Preparation of Solution A: Tannic acid, water, and sodium carbonate are uniformly blended in a weight ratio of 3:7:1, and then nanocellulose is added thereto in an amount of 55% of the total amount of tannic acid. The mixture is then stirred thoroughly, filtered, and dried to obtain tannin-modified nanocellulose. Tannin-modified nanocellulose and silane coupling liquid were stirred thoroughly in a weight ratio of 5:8 to obtain liquid A; the silane coupling liquid was prepared by stirring silane coupling agent KH550, ethanol and water in a weight ratio of 4:7:5; S12b: Preparation of Agent B: 5 parts of strontium titanate, 3 parts of aluminum silicate fiber and 8 parts of modified lanthanum oxide were uniformly blended to obtain agent B; solution A and agent B were blended in a weight ratio of 7:5 and ball-milled at a ball-milling speed of 1500 r / min for 2 hours to obtain AB polyadjusted solution; S13: adding the pretreated carbon nanotubes to the AB reconstitution solution in an amount of 7 times the total amount of the pretreated carbon nanotubes and stirring; after stirring, filtering and drying to obtain a carbon nanotube regulator.

[0039] The stirring process in S13 of this embodiment has a stirring speed of 400 r / min, stirring for 1 hour, and a stirring temperature of 55°C.

[0040] The modification method of the modified lanthanum oxide of this embodiment is: Lanthanum oxide was preheated at 60°C for 1 hour and kept warm. The kept warm lanthanum oxide and the modified solution were mixed in a weight ratio of 7:4 and ball-milled at a speed of 1200 r / min for 2 hours. After the ball milling was completed, the mixture was filtered and dried to obtain the modified lanthanum oxide. The preparation method of the modified liquid is as follows: 5 parts of flaky boron nitride, 4 parts of α-alumina, 8 parts of sodium silicate solution, 2 parts of diethanolamine and 0.7 parts of sodium acrylate are mixed.

[0041] The mass fraction of the sodium silicate solution in this embodiment is 5%; the diameter of the flake boron nitride is 2 μm.

[0042] Example 3. The preparation method of a water-based two-component epoxy primer of this embodiment comprises the following steps: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 37.5 parts of epoxy resin, 12.5 parts of functional modifying agent, 6.5 parts of carbon nanotube regulator, 5.5 parts of flame retardant, 5 parts of silane coupling agent, 3.5 parts of wetting and dispersing agent and 25 parts of water; Then weigh the raw materials of component B: 37.5 parts of polyamide curing agent, 3 parts of epoxy catalyst and 25 parts of cosolvent; Step 2, preparation of component A: uniformly mix the raw materials of component A to prepare component A; preparation of component B: uniformly mix the raw materials of component B to prepare component B; Step 3: Component A and component B are evenly mixed in a weight ratio of 7:1 to prepare a two-component epoxy primer.

[0043] The wetting and dispersing agent in this embodiment is Digo 760w, the flame retardant is magnesium hydroxide; the epoxy resin is a mixture of bisphenol A epoxy resin and aliphatic flexible epoxy resin in a weight ratio of 9:2; The epoxy equivalent weight of the bisphenol A epoxy resin is 490 g / mol; the aliphatic flexible epoxy resin is a polyglycol diglycidyl ether resin with an epoxy equivalent weight of 325 g / mol, a solid content of ≥99%, and a viscosity of 75 mPa·s; The polyamide curing agent is 200 low molecular weight polyamide, with a solid content of ≥99% and an amine value of 255 mgKOH / g; the epoxy drier is 2,4,6-tris(dimethylaminomethyl)phenol; the cosolvent is xylene; and the silane coupling agent is silane coupling agent KH560.

[0044] The preparation method of the modified functional agent of this embodiment is: S01: 6.5 parts of mesoporous silica, 3 parts of β-cyclodextrin, 2 parts of sodium dodecylbenzenesulfonate and 6.5 parts of phosphate buffer solution are mixed evenly to obtain a mesoporous silica solution; Stir calcium sulfate whiskers thoroughly in a sufficient amount of 10% sulfuric acid solution, then wash with water, filter and dry; The dried calcium sulfate whiskers and mesoporous silica liquid were mixed and stirred uniformly in a weight ratio of 4:7 to obtain a whisker-mesoporous silica functional liquid; S02: Preparation of modified titanium oxide agent: S021: 3 parts of tetrabutyl titanate, 6.5 parts of acetone solvent, 2.5 parts of sodium alginate and 2.5 parts of formic acid solution are thoroughly mixed to obtain a modifier; S022: impregnating the titanium oxide into a modifier in an amount that is 4 times the total amount of the titanium oxide, filtering and drying after the impregnation is completed to obtain a modified titanium oxide agent; S03: The modified titanium oxide agent and whisker-mesoporous silica functional liquid are mixed and ball-milled in a weight ratio of 7:4 at a ball-milling speed of 1600 r / min for 2 h. After the ball-milling is completed, the mixture is filtered and dried to obtain a modified functional agent.

[0045] The particle size of the mesoporous silica in this embodiment is 85 nm, and the pore size is 17.5 nm; the pH value of the phosphate buffer solution is 5.8.

[0046] The mass fraction of the formic acid solution in this embodiment is 5.5%.

[0047] The preparation method of the carbon nanotube regulator of this embodiment is: S11: stirring the carbon nanotubes uniformly in a sufficient amount of 8% by mass potassium permanganate solution, then washing with water, filtering, and drying, and then stirring the carbon nanotubes uniformly in a sufficient amount of 5% by mass sulfuric acid solution, then washing with water, filtering, and drying to obtain pretreated carbon nanotubes; S12: Preparation of AB compound solution: S12a: Preparation of Solution A: Tannic acid, water, and sodium carbonate are uniformly blended in a weight ratio of 3:7:1, and then nanocellulose is added thereto in an amount of 48% of the total amount of tannic acid. The mixture is then stirred thoroughly, filtered, and dried to obtain tannin-modified nanocellulose. Tannin-modified nanocellulose and silane coupling liquid were stirred thoroughly in a weight ratio of 5:8 to obtain liquid A; the silane coupling liquid was prepared by stirring silane coupling agent KH550, ethanol and water in a weight ratio of 4:7:5; S12b: Preparation of Agent B: 4 parts of strontium titanate, 2.5 parts of aluminum silicate fiber and 6.5 parts of modified lanthanum oxide were uniformly blended to obtain agent B; solution A and agent B were blended in a weight ratio of 7:5 and ball-milled at a ball-milling speed of 1250 r / min for 2 h to obtain AB polyadjusted solution; S13: adding the pretreated carbon nanotubes to the AB reconstitution solution in an amount of 5.5 times the total amount of the pretreated carbon nanotubes and stirring the solution. After stirring is completed, filtering and drying are performed to obtain a carbon nanotube regulator.

[0048] The stirring process in S13 of this embodiment has a stirring speed of 375 r / min, stirring for 1 hour, and a stirring temperature of 52°C.

[0049] The modification method of the modified lanthanum oxide of this embodiment is: Lanthanum oxide was preheated at 58°C for 1 hour and kept warm. The kept warm lanthanum oxide and the modified solution were mixed and ball-milled at a weight ratio of 7:3.5 at a ball-milling speed of 1100 r / min for 2 hours. After the ball-milling was completed, the modified lanthanum oxide was filtered and dried to obtain the modified lanthanum oxide. The preparation method of the modified liquid is as follows: 4 parts of flaky boron nitride, 3 parts of α-alumina, 6.5 parts of sodium silicate solution, 1.5 parts of diethanolamine and 0.6 parts of sodium acrylate are mixed.

[0050] The mass fraction of the sodium silicate solution in this embodiment is 3.5%; the diameter of the flake boron nitride is 1.5 μm.

[0051] Comparative Example 1. The difference from Example 3 is that no modifying functional agent is added.

[0052] Comparative Example 2. The difference from Example 3 is that no modified titanium oxide agent is added during the preparation of the modified functional agent.

[0053] Comparative Example 3. The difference from Example 3 is that no modifier is added during the preparation of the modified titanium oxide agent.

[0054] Comparative Example 4. The difference from Example 3 is that sodium alginate and tetrabutyl titanate are not added to the modifier.

[0055] Comparative Example 5. The difference from Example 3 is that no whisker-mesoporous silica functional liquid is added in the preparation of the modified functional agent.

[0056] Comparative Example 6. The difference from Example 3 is that no dry calcium sulfate whiskers are added in the preparation of the whisker-mesoporous silica functional liquid.

[0057] Comparative Example 7. The difference from Example 3 is that no mesoporous silica liquid is added in the preparation of the whisker-mesoporous silica functional liquid.

[0058] Comparative Example 8. The difference from Example 3 is that no carbon nanotube regulator is added.

[0059] Comparative Example 9. The difference from Example 3 is that no AB rehydration solution is added during the preparation of the carbon nanotube regulator.

[0060] Comparative Example 10. The difference from Example 3 is that solution A is not added to the AB compounding solution.

[0061] Comparative Example 11. The difference from Example 3 is that tannin-modified nanocellulose is not added to liquid A.

[0062] Comparative Example 12. The difference from Example 3 is that no silane coupling liquid is added to liquid A.

[0063] Comparative Example 13. The difference from Example 3 is that no agent B is added to the AB compounding solution.

[0064] Comparative Example 14. The difference from Example 3 is that no strontium titanate or aluminum silicate fiber is added to Agent B.

[0065] Comparative Example 15. The difference from Example 3 is that modified lanthanum oxide is not added to Agent B.

[0066] Conventional tests, Examples 1 to 3 and Comparative Examples 1 to 15 were conducted to test flame retardancy, adhesion and impact resistance, and to test the corrosion resistance and weather resistance of the product (the product was tested under UV intensity of 500W / m The test results are as follows:

[0067] It can be seen from Comparative Examples 1 to 15 and Examples 1 to 3 that; The product of Example 3 has excellent flame retardancy, adhesion and impact resistance, and is also stable in corrosion-resistant and weather-resistant environments. From Comparative Examples 1 to 15 and Example 3, it can be seen that when neither the modifying functional agent nor the carbon nanotube regulator is added to the product, the performance of the product deteriorates significantly. When the two are blended and coordinated, the performance of the product is most significant. No modified titanium oxide agent was added in the preparation of the modified functional agent, no modifier was added in the preparation of the modified titanium oxide agent, no sodium alginate and tetrabutyl titanate were added to the modifier, no whisker-mesoporous silica functional liquid was added in the preparation of the modified functional agent, no dried calcium sulfate whiskers were added in the preparation of the whisker-mesoporous silica functional liquid, and no mesoporous silica liquid was added in the preparation of the whisker-mesoporous silica functional liquid. The performance of the products all showed a trend of deterioration to varying degrees. The whisker-mesoporous silica functional liquid obtained by the specific method of the present invention was combined with the modified titanium oxide agent to prepare a specific modified functional agent, and the performance effect of the product was the most significant. Using other methods instead was not as obvious as the effect of the present invention. No AB reconstitution liquid is added in the preparation of the carbon nanotube regulator, no A liquid is added to the AB reconstitution liquid, no tannin-modified nanocellulose is added to the A liquid, no silane coupling liquid is added to the A liquid, no B agent is added to the AB reconstitution liquid, no strontium titanate or aluminum silicate fiber is added to the B agent, and no modified lanthanum oxide is added to the B agent; the performance of the product also shows a trend of varying degrees of deterioration. The AB reconstitution liquid prepared by combining the A liquid and the B agent obtained by the specific method of the present invention to improve and optimize the pretreated carbon nanotubes, thereby obtaining a carbon nanotube regulator with the most significant effect on the performance of the product. In addition, no modified lanthanum oxide is added to the B agent, and the performance of the product also shows a relatively obvious trend of deterioration. The raw materials of the product of the present invention are unique.

[0068] Based on the above research, the present invention further explores the product performance through the preparation of modified lanthanum oxide; Experimental Example 1. The same as Example 3, the only difference is that no heat-insulated lanthanum oxide is added in the preparation of the modified lanthanum oxide.

[0069] Experimental Example 2. The same as Example 3, except that no modifying liquid was added during the preparation of the modified lanthanum oxide.

[0070] Experimental Example 3. The same as Example 3, the only difference is that diethanolamine and sodium acrylate are not added to the modification liquid.

[0071] Experimental Example 4. The same as Example 3, except that no flake boron nitride and α-alumina are added to the modified solution.

[0072] Experimental Example 5. The same as Example 3, the only difference is that the sodium silicate solution is replaced by water.

[0073] The performance test results of Experimental Examples 1-5 are as follows:

[0074] It can be seen from Experimental Examples 1-5 that when no heat-insulated lanthanum oxide is added to the preparation of the modified lanthanum oxide and no modifying liquid is added to the preparation of the modified lanthanum oxide, the performance of the product deteriorates significantly. At the same time, no diethanolamine and sodium acrylate are added to the modifying liquid, no flake boron nitride and α-alumina are added to the modifying liquid, and water is used instead of the sodium silicate solution. The performance of the product tends to deteriorate to varying degrees. The performance effect of the specific modified lanthanum oxide prepared by the modifying liquid obtained by the specific method of the present invention and the heat-insulated lanthanum oxide is the most significant. The effects of other methods are not as obvious as those of the present invention.

[0075] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0076] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing a water-based two-component epoxy primer, characterized in that: The following steps are involved: Step 1: weigh the raw materials according to weight: First weigh the raw materials of component A: 35-45 parts of epoxy resin, 10-15 parts of modifying functional agent, 5-8 parts of carbon nanotube regulator, 4-7 parts of flame retardant, 4-6 parts of silane coupling agent, 2-5 parts of wetting and dispersing agent and 20-30 parts of water; Then weigh the raw materials of component B: 35-40 parts of polyamide curing agent, 2-4 parts of epoxy catalyst and 20-30 parts of cosolvent; Step 2, preparation of component A: uniformly mix the raw materials of component A to prepare component A; preparation of component B: uniformly mix the raw materials of component B to prepare component B; Step 3: Component A and component B are evenly mixed in a weight ratio of (6-8):1 to prepare a two-component epoxy primer.

2. The method for preparing a water-based two-component epoxy primer according to claim 1, wherein: The wetting and dispersing agent is Digo 760w, the flame retardant is magnesium hydroxide; the epoxy drier is 2,4,6-tris(dimethylaminomethyl)phenol; the cosolvent is xylene; and the silane coupling agent is silane coupling agent KH560.

3. The method for preparing a water-based two-component epoxy primer according to claim 1, wherein: The epoxy resin is prepared by mixing bisphenol A epoxy resin and aliphatic flexible epoxy resin in a weight ratio of 9:2; The epoxy equivalent weight of the bisphenol A epoxy resin is 480-500 g / mol; the aliphatic flexible epoxy resin is a polyglycol diglycidyl ether resin, with an epoxy equivalent weight of 320-330 g / mol, a solid content of ≥99%, and a viscosity of 70-80 mPa·s; The polyamide curing agent is a 200 low molecular weight polyamide with a solid content of ≥99% and an amine value of 250-260 mgKOH / g.

4. The method for preparing a water-based two-component epoxy primer according to claim 1, wherein: The preparation method of the modified functional agent is: S01: 5-8 parts of mesoporous silica, 2-4 parts of β-cyclodextrin, 1-3 parts of sodium dodecylbenzenesulfonate and 5-8 parts of phosphate buffer solution are uniformly mixed to obtain a mesoporous silica solution; Stir calcium sulfate whiskers thoroughly in a sufficient amount of 8-12% sulfuric acid solution, then wash with water, filter and dry; The dried calcium sulfate whiskers and mesoporous silica liquid were mixed and stirred uniformly in a weight ratio of 4:7 to obtain a whisker-mesoporous silica functional liquid; S02: Preparation of modified titanium oxide agent: S021: thoroughly mixing 2-4 parts of tetrabutyl titanate, 5-8 parts of acetone solvent, 2-3 parts of sodium alginate, and 2-3 parts of formic acid solution to obtain a modifier; S022: impregnating the titanium oxide into a modifier in an amount 3-5 times the total amount of the titanium oxide, filtering and drying after the impregnation is completed to obtain a modified titanium oxide agent; S03: The modified titanium oxide agent and whisker-mesoporous silica functional liquid are mixed and ball-milled in a weight ratio of 7:(3-5) at a ball-milling speed of 1500-1700 r / min for 2 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the modified functional agent.

5. The method for preparing a water-based two-component epoxy primer according to claim 4, wherein: The particle size of the mesoporous silica is 70-100 nm, and the pore size is 15-20 nm; the pH value of the phosphate buffer solution is 5.5-6.

0.

6. The method for preparing a water-based two-component epoxy primer according to claim 4, wherein: The mass fraction of the formic acid solution is 4-7%.

7. The method for preparing a water-based two-component epoxy primer according to claim 1, wherein: The preparation method of the carbon nanotube regulator is as follows: S11: stirring the carbon nanotubes uniformly in a sufficient amount of 8% by mass potassium permanganate solution, then washing with water, filtering, and drying, and then stirring the carbon nanotubes uniformly in a sufficient amount of 5% by mass sulfuric acid solution, then washing with water, filtering, and drying to obtain pretreated carbon nanotubes; S12: Preparation of AB compound solution: S12a: Preparation of Solution A: Tannic acid, water, and sodium carbonate are uniformly blended in a weight ratio of 3:7:1, and then nanocellulose is added thereto in an amount of 45-55% of the total amount of tannic acid. The mixture is then stirred thoroughly, filtered, and dried to obtain tannin-modified nanocellulose. Tannin-modified nanocellulose and silane coupling liquid were stirred thoroughly in a weight ratio of 5:8 to obtain liquid A; the silane coupling liquid was prepared by stirring silane coupling agent KH550, ethanol and water in a weight ratio of 4:7:5; S12b: Preparation of Agent B: 3-5 parts of strontium titanate, 2-3 parts of aluminum silicate fiber and 5-8 parts of modified lanthanum oxide are uniformly blended to obtain agent B; solution A and agent B are blended in a weight ratio of 7:5 and ball-milled at a speed of 1000-1500 r / min for 2 hours to obtain AB polyhydric solution; S13: adding the pretreated carbon nanotubes to the AB reconstitution solution in an amount of 4-7 times the total amount of the pretreated carbon nanotubes and stirring; after stirring, filtering and drying to obtain a carbon nanotube regulator.

8. The method for preparing a water-based two-component epoxy primer according to claim 7, wherein: The stirring speed of the stirring treatment in S13 is 350-400 r / min, stirring is 1 hour, and the stirring temperature is 50-55°C.

9. The method for preparing a water-based two-component epoxy primer according to claim 8, wherein: The modification method of the modified lanthanum oxide is: Preheat lanthanum oxide at 55-60°C for 1 hour, keep the temperature, and mix the kept lanthanum oxide and the modified solution in a weight ratio of 7:(3-4) and ball mill at a ball milling speed of 1000-1200 r / min for 2 hours. After the ball milling is completed, filter and dry to obtain the modified lanthanum oxide; The preparation method of the modified liquid is as follows: 3-5 parts of flaky boron nitride, 2-4 parts of α-aluminum oxide, 5-8 parts of sodium silicate solution, 1-2 parts of diethanolamine and 0.5-0.7 parts of sodium acrylate are mixed.

10. The method for preparing a water-based two-component epoxy primer according to claim 9, characterized in that: The mass fraction of the sodium silicate solution is 2-5%; the diameter of the flaky boron nitride is 1-2 μm.

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