CN110760239A - Composite nano material reinforced water-based epoxy primer and preparation method thereof - Google Patents
Composite nano material reinforced water-based epoxy primer and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a composite nano material reinforced water-based epoxy primer, wherein the weight ratio of a component A to a component B in raw materials is 3-5: 1; the component A comprises, by weight, 30-65 parts of an aqueous epoxy resin emulsion, 2-5 parts of a first solvent, 0.2-1 part of a suspending agent, 2-10 parts of an anti-rust pigment, 0.5-1.5 parts of an anti-flash rust agent, 20-60 parts of a pigment and filler, 0.2-2.5 parts of an auxiliary agent, 0.05-4 parts of a zero-dimensional nano material, 0.05-1 part of a two-dimensional nano material and 0.1-5 parts of a siloxane compound; the component B comprises 40-85 parts of a water-based epoxy curing agent and 0-10 parts of a second solvent. Wherein the weight part of the zero-dimensional nano material is not less than that of the two-dimensional nano material. The zero-dimensional nano material and the two-dimensional nano material with specific sizes in the raw materials of the water-based epoxy primer can be connected with the siloxane compound through chemical bonds, so that a complete three-dimensional network structure is formed in a paint film, and the paint film is endowed with excellent flexibility, mechanical properties, water resistance and salt spray resistance.
Description
Technical Field
The invention relates to the technical field of epoxy coatings. More particularly, relates to a composite nano material reinforced water-based epoxy primer and a preparation method thereof.
Background
The epoxy resin has stable chemical structure and is not easy to decompose in electrochemical corrosion environment, so that the coating taking the epoxy resin as a matrix is widely applied to the anticorrosion primer. The traditional solvent-based epoxy primer contains a large amount of harmful solvents, and the environment is harmed inevitably in the using process. With the increasing awareness of environmental protection, the traditional solvent-based epoxy primer is gradually replaced by high-solid, water-based and solvent-free epoxy primer. Among them, the water-based epoxy primer uses water as a diluent, has a small construction odor, and is favored by more and more factories. Similar to the traditional solvent-based epoxy primer, the water-based epoxy primer has the advantages of high adhesion to metal substrates, good barrier property, stable chemical structure, high mechanical strength and the like. However, the water-borne epoxy primer has a lot of hydrophilic groups and components, so that the water resistance of the water-borne epoxy primer is obviously inferior to that of the traditional solvent-borne epoxy primer, and the salt spray resistance of the water-borne epoxy primer is affected. In addition, the water-based epoxy primer also has some defects of a solvent-based epoxy primer, including the problems of easy cracking, poor impact strength, remarkably lower wet adhesion than dry adhesion and the like.
Modification with nanomaterials is one of the effective means to solve these problems. Chinese patent 'a nanometer modified high solid epoxy primer' (publication number is CN 106867357B), discloses a nanometer modified epoxy primer, and the addition of zero-dimensional inorganic nanoparticles improves the wet adhesion, flexibility and salt spray resistance of a paint film. Chinese patent 'a graphene modified anti-rust pigment anti-corrosion primer and a preparation method thereof' (publication number is CN 108329793A) discloses a graphene modified epoxy primer, and the addition of two-dimensional graphene improves the salt spray resistance of a paint film. However, only one nano material or several nano materials with the same dimension are adopted in the prior art to improve the epoxy primer, and the effect of the epoxy primer on improving the anticorrosion effect, the hardness and the wet adhesion of the primer is limited.
Therefore, how to improve the prior art, exert the function of the nano material and provide the water-based epoxy primer with excellent mechanical property, high adhesive force and excellent corrosion resistance is very important.
Disclosure of Invention
The invention aims to provide a composite nano-material reinforced water-based epoxy primer, which simultaneously comprises a zero-dimensional nano material, a two-dimensional nano material and a siloxane compound, and can form a three-dimensional network structure in the curing process of the primer, thereby improving the mechanical property and the corrosion resistance of a paint film.
Another object of the present invention is to provide a method for preparing a composite nanomaterial-reinforced waterborne epoxy primer.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a composite nano-material reinforced water-based epoxy primer, wherein the weight ratio of a component A to a component B in raw materials is 3-5: 1; based on the weight portion, the weight portion of the material,
the component A comprises 30-65 parts of water-based epoxy resin emulsion, 2-5 parts of a first solvent, 0.2-1 part of a suspending agent, 2-10 parts of an anti-rust pigment, 0.5-1.5 parts of an anti-flash rust agent, 20-60 parts of pigment and filler, 0.2-2.5 parts of an auxiliary agent, 0.05-4 parts of a zero-dimensional nano material, 0.05-1 part of a two-dimensional nano material and 0.1-5 parts of a siloxane compound;
the component B comprises 40-85 parts of a water-based epoxy curing agent and 0-10 parts of a second solvent;
wherein the weight part of the zero-dimensional nano material is not less than that of the two-dimensional nano material.
Optionally, the particle size of the zero-dimensional nano material is 2-100nm, and the radial extension size of the two-dimensional nano material is 0.1-50 μm.
Optionally, the zero-dimensional nanomaterial includes one or more of silicon oxide nanoparticles, titanium oxide nanoparticles, and zinc oxide nanoparticles, the surfaces of which are not modified or are modified with epoxy groups, amino groups, or carboxyl groups.
Optionally, the two-dimensional nanomaterial comprises graphene oxide or/and graphene; preferably, the number of graphene oxide layers is 1 to 10, and the number of graphene layers is 1 to 10.
Alternatively, the silicone compound is selected from the winning Dynasylan series.
Optionally, the first solvent is propylene glycol methyl ether, and the second solvent is an alcohol ether solvent;
optionally, the second solvent comprises at least one of propylene glycol methyl ether, propylene glycol phenyl ether, diethylene glycol butyl ether.
Optionally, the suspending agent is an organobentonite.
Optionally, the auxiliary agent comprises one or more of a base material wetting agent, a defoaming agent and a dispersing agent.
Optionally, the substrate wetting agent is a silicon-based or non-silicon-based substrate wetting agent;
optionally, the defoamer is a silicon-based or non-silicon-based defoamer;
optionally, the dispersant is a non-ionic or ionic dispersant.
In a second aspect, the present invention provides a method for preparing a composite nanomaterial-reinforced waterborne epoxy primer, comprising the following steps:
s1: adding deionized water and a first solvent into the aqueous epoxy resin emulsion, and uniformly stirring; adding a suspending agent under stirring, then adding a dispersing agent, a pigment filler and an anti-rust pigment, stirring uniformly, grinding and diluting; adding deionized water, a base material wetting agent, a defoaming agent, an anti-flash rust agent, two-dimensional nano material dispersion slurry and zero-dimensional nano material dispersion slurry containing siloxane compounds, stirring and uniformly mixing, and discharging to obtain a component A;
s2: adding a waterborne epoxy curing agent into deionized water, uniformly mixing, adding a second solvent, filtering and discharging to obtain a component B;
s3: and uniformly mixing the component A and the component B to obtain the water-based epoxy primer.
The invention has the following beneficial effects:
according to the water-based epoxy primer provided by the invention, the zero-dimensional nano material and the two-dimensional nano material with specific sizes in the raw materials can be connected with the siloxane compound through chemical bonds, a complete three-dimensional network structure is formed in a paint film, the three-dimensional network structure is tightly combined with the paint film, the whole paint film can be anchored on the surface of a base material, and the paint film is endowed with excellent mechanical properties, water resistance and salt spray resistance, and meanwhile, the paint film is ensured to have excellent flexibility. The water-based epoxy primer can be applied to the fields of locomotives, engineering machinery, agricultural machinery and the like.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to specific embodiments.
One specific embodiment of the invention provides a composite nano-material reinforced water-based epoxy primer, which is prepared from the following raw materials, wherein the weight ratio of a component A to a component B is 3-5: 1; according to the weight portion of the raw materials,
the component A comprises 30-65 parts of water-based epoxy resin emulsion, 2-5 parts of a first solvent, 0.2-1 part of a suspending agent, 2-10 parts of an anti-rust pigment, 0.5-1.5 parts of an anti-flash rust agent, 20-60 parts of pigment and filler, 0.2-2.5 parts of an auxiliary agent, 0.05-4 parts of a zero-dimensional nano material, 0.05-1 part of a two-dimensional nano material and 0.1-5 parts of a siloxane compound;
the component B comprises 40-85 parts of a water-based epoxy curing agent and 0-10 parts of a second solvent;
wherein the weight part of the zero-dimensional nano material is not less than that of the two-dimensional nano material.
It should be noted that the zero-dimensional nanomaterial content and the two-dimensional nanomaterial content of the a component are both measured on a dry basis. Because during the preparation process, commercial nano-material dispersion slurry, which is made by itself or purchased, is added.
The water-based epoxy primer provided by the invention contains a certain amount of zero-dimensional nano material, two-dimensional nano material and siloxane compound. In the curing process, the zero-dimensional nano material and the two-dimensional nano material can be connected with the siloxane compound through chemical bonds, so that a complete three-dimensional network structure is formed in the paint film, the three-dimensional network structure is tightly combined with the paint film, the whole paint film can be anchored on the surface of a base material, and the paint film has excellent adhesive force and barrier property. The nano materials with different sizes have a synergistic effect, so that the advantages of the zero-dimensional nano material in improving the stability, wear resistance and flexibility of the coating are exerted, the effect of the two-dimensional nano material in corrosion resistance is also exerted, and the three-dimensional network structure formed by the zero-dimensional nano material and the two-dimensional nano material together with the siloxane compound has the greater advantages in improving the hardness, flexibility, adhesive force, barrier property and corrosion resistance of the paint film.
In some preferred examples, the zero-dimensional nanomaterial has a particle size of 2 to 100nm and the two-dimensional nanomaterial has a radial extension dimension of 0.1 to 50 μm. The smaller the particle size of the zero-dimensional nanoparticles, the more favorable is their uniform distribution in the paint film and thus the formation of a three-dimensional network. However, the too small particle size can lead to the absorption of a large amount of wetting dispersant, and influence on the dispersion of the pigment and filler. The larger the radial size of the two-dimensional nano material is, the more the three-dimensional network structure can be built, and the barrier property of the coating can be improved. However, the graphene obtained by the existing graphene preparation technology is larger in radial size and larger in thickness. A large thickness corresponds to a reduction in the number of effective sheets for the same amount of addition, and is therefore detrimental to the effect of the graphene. In summary, the sizes of both zero-dimensional nanomaterials and two-dimensional nanomaterials need to be optimized.
The surface of the zero-dimensional nano material can be unmodified or modified. After the surface of the zero-dimensional nano material is modified with epoxy groups, amino groups or carboxyl groups, the epoxy groups, the amino groups or the carboxyl groups can form chemical bonds with active groups on the surfaces of resin and siloxane compounds in the epoxy primer, so that the thermal stability and the chemical stability of the epoxy primer are improved; particularly, a three-dimensional network structure formed by the graphene, a siloxane compound and graphene plays an important role in optimizing the performance of a paint film. In some preferred examples of the present invention, the zero-dimensional nanomaterial includes one or more of silicon oxide nanoparticles, titanium oxide nanoparticles, and zinc oxide nanoparticles, which are surface-unmodified or surface-modified with epoxy groups, amino groups, or carboxyl groups.
The two-dimensional nano material in the invention extends in a sheet shape, and the size of the two-dimensional nano material in the radial extension direction is far larger than that in the thickness direction. In some preferred examples, the two-dimensional nanomaterial comprises graphene oxide or/and graphene; the number of layers of the graphene oxide is 1-10, and the number of layers of the graphene is 1-10. The graphite layer with the lamellar conjugated structure can form a compact super-hydrophobic isolation layer, the salt spray resistance of the paint film is improved, and the three-dimensional network structure formed by the graphite layer, the siloxane compound and the zero-dimensional nano material improves the wet adhesion of the paint film.
The siloxane compound in the present invention is a compound capable of chemically reacting with a hydroxyl group, an epoxy group, an amino group or a carboxyl group, or itself capable of undergoing a crosslinking reaction; in some preferred examples, the silicone compound includes, but is not limited to, the winning Dynasylan series.
In some preferred examples, the first solvent is propylene glycol methyl ether and the second solvent is an alcohol ether-based solvent; the second solvent includes, but is not limited to, at least one of propylene glycol methyl ether, propylene glycol phenyl ether, diethylene glycol butyl ether.
In some preferred examples, the suspending agent is an organobentonite.
Suitable rust inhibiting pigments, flash rust inhibitors with the waterborne epoxy primers are known to those skilled in the art and may vary depending on the desired appearance of the waterborne epoxy primer. In some preferred examples, the rust inhibitive pigment includes, but is not limited to, at least one of phosphate, molybdate based rust inhibitive pigments; the flash rust inhibitor includes but is not limited to at least one of nitrite, borate and phosphate.
The pigment and filler are added to increase the volume of the paint, play a role in filling, reduce the cost of the paint and simultaneously enable the epoxy primer to have certain functions of covering, coloring, protecting and the like. In some preferred examples, the pigment and filler include, but are not limited to, at least one of talc, barium sulfate, black iron oxide, titanium dioxide, and carbon black.
In a specific embodiment, the aqueous epoxy resin emulsion is 703A aqueous epoxy resin emulsion from shanghai xinhua resin factory or EP384 aqueous epoxy resin emulsion from new resins shanghai ltd.
In another specific embodiment, the waterborne epoxy curing agent is one or more of VEH2188 waterborne epoxy curing agent from Shanghai Co., Ltd, Linde gas (Nanjing) Co., Ltd, WH900 waterborne epoxy curing agent from Linde gas (Nanjing) Co., Ltd, and 419 waterborne epoxy curing agent.
In a preferred example, the auxiliary agent comprises one or more of a base material wetting agent, a defoaming agent and a dispersing agent; the substrate wetting agent is a silicon or non-silicon substrate wetting agent, preferably a BYK346 substrate wetting agent; the defoaming agent is a silicon defoaming agent or a non-silicon defoaming agent, and is preferably a tego904 defoaming agent; the dispersant is nonionic or ionic, preferably BYK190 dispersant.
In another embodiment, the present invention provides a method for preparing the water-based epoxy primer as described above, comprising the steps of:
s1: adding deionized water and a first solvent into the aqueous epoxy resin emulsion, and uniformly stirring; adding a suspending agent under stirring, then adding a dispersing agent, a pigment filler and an anti-rust pigment, stirring uniformly, grinding and diluting; adding deionized water, a base material wetting agent, a defoaming agent, an anti-flash rust agent, two-dimensional nano material dispersion slurry and zero-dimensional nano material dispersion slurry containing siloxane compounds, stirring and uniformly mixing, and discharging to obtain a component A;
s2: adding a waterborne epoxy curing agent into deionized water, uniformly mixing, adding a second solvent, filtering and discharging to obtain a component B;
s3: and uniformly mixing the component A and the component B to obtain the water-based epoxy primer.
In the preparation process, the raw materials are added according to a specific ratio.
In S1, the two-dimensional nanomaterial slurry to be added may be an aqueous slurry that is either self-made or commercially available. For example, the preparation process of the graphene dispersion slurry is as follows: uniformly mixing the graphene, deionized water and a dispersing agent according to the ratio of 1:8:1, and then transferring the mixture to a grinding machine or an ultrasonic dispersion machine for grinding or dispersing for 4 hours. Discharging and filtering to obtain the graphene dispersion slurry. The zero-dimensional nanoparticle dispersion slurry in S1 can be self-made or commercially available water-based dispersion slurry or water-miscible solvent-based dispersion slurry, and during use, a proper amount of siloxane compound needs to be added, and then mechanical stirring is carried out for 24 hours at normal temperature.
The technical solution of the present invention is described below with reference to some specific examples:
the weights of the two-dimensional nanomaterials and the zero-dimensional nanomaterials in the following example formulations are both referred to as dry weights.
Example 1
The preparation method of the composite nano material reinforced water-based epoxy primer comprises the following steps:
preparing raw materials:
uniformly mixing the graphene, deionized water and a dispersing agent according to the ratio of 1:8:1, and then transferring the mixture to a grinding machine or an ultrasonic dispersion machine for grinding or dispersing for 4 hours. Discharging and filtering to obtain the graphene dispersion slurry.
A water dispersion slurry of graphene oxide was purchased.
Adding a proper amount of siloxane compound into the purchased or self-made zero-dimensional nano-particle aqueous dispersion slurry, and mechanically stirring for 24 hours at normal temperature.
Preparation of component A:
1. firstly, adding the waterborne epoxy resin emulsion into a stirring kettle, and then adding deionized water and propylene glycol methyl ether for slow stirring.
2. LT organobentonite is weighed, slowly added into a stirring kettle while stirring, and then stirred at a high speed of 1000 rpm for 30 min.
3. Adding BYK190 dispersant into a stirring kettle, slowly adding weighed pigment filler (325-mesh talcum powder, 760 iron oxide black, precipitated barium sulfate, R-996 titanium pigment) and anti-rust pigment (409 zinc phosphate) into the kettle after 10min, and simultaneously adjusting the stirring speed to 600 revolutions per minute.
4. And then increasing the stirring speed, continuing stirring for 30min, controlling the temperature to be lower than 40 ℃, and controlling the stirring speed to be 800 revolutions per minute.
5. After being stirred evenly, the mixture is transferred to a grinder, and the mixture can enter a dilution tank for dilution after being ground to specified fineness, wherein the grinding speed is 1000 r/min. The temperature was controlled below 40 ℃.
6. Adding deionized water, graphene or graphene oxide dispersion slurry, nano particle dispersion slurry, an auxiliary agent (TEGO904 antifoaming agent, BYK346 base material wetting agent) and FA179, stirring for 30min, and filtering and discharging.
And B component:
1. propylene glycol methyl ether was weighed into a stirred tank.
2. The stirring speed was set at 400 rpm, and then VEH2188 aqueous epoxy hardener was added thereto and stirred for 20 min.
3. Slowly adding deionized water into the stirring kettle in the stirring process, and then continuously stirring for 30min to filter and discharge.
The construction process comprises the following steps:
the amounts of the respective raw materials added in the preparation of the A-component and the B-component are shown in Table 1. Wherein the radial extension size of the graphene is 5 μm, and the thickness is 5 layers; the graphene oxide has a radial extension size of 5 μm and a thickness of 5 layers; the particle size of the silicon oxide nanoparticles is 10nm, the particle size of the zinc oxide nanoparticles is 10nm, and the particle size of the titanium oxide nanoparticles is 10 nm.
The component A and the component B are mixed and mixed uniformly according to the proportion of 5:1, deionized water accounting for 10-20% of the total amount of the A, B components is added for dilution after the components are fully stirred, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup.
TABLE 1 compositions of formulations 1-4 of example 1
Example 2
The waterborne epoxy primer of example 2 was prepared according to formulations 5-8 of Table 2 and was prepared in the same manner as in example 1.
The construction process comprises the following steps:
the amounts of the respective raw materials added in the preparation of the A-component and the B-component are shown in Table 2. Wherein the radial extension size of the graphene is 5 μm, and the thickness of the graphene is 10 layers; the radial extension size of the graphene oxide is 0.1 mu m, and the thickness of the graphene oxide is 1 layer; the particle size of the silicon oxide nano particles is 2nm and 100 nm.
The component A and the component B are mixed and mixed uniformly according to the proportion of 5:1, deionized water accounting for 10-20% of the total amount of the A, B components is added for dilution after the components are fully stirred, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup.
TABLE 2 compositions of formulations 5-8 of example 2
Example 3
The waterborne epoxy primer of example 3 was prepared according to formulations 9-15 of Table 3 and was prepared in the same manner as in example 1.
The construction process comprises the following steps:
the amounts of the respective raw materials added in the preparation of the A-component and the B-component are shown in Table 3. Wherein the radial extension size of the graphene is 5 μm, and the thickness is 5 layers; the particle size of the silicon oxide nano particles is 10 nm.
The component A and the component B are uniformly mixed according to the proportion, and are fully stirred, deionized water with the mass accounting for 10-20% of the total mass of the A, B component is added for dilution, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup. Wherein, the ratio of the component A to the component B is 4:1 for formula 9, 3.5:1 for formula 10, 5:1 for formula 11, 5:1 for formula 12, 5:1 for formula 13, 4:1 for formula 14 and 4.3:1 for formula 15.
TABLE 3 compositions of formulations 9-15 of example 3
Comparative example 1
The waterborne epoxy primer of comparative example 1 was prepared according to formulation 16 shown in table 4, and the preparation method was the same as example 1, but formulation 16 of comparative example 1 did not include zero-dimensional nanoparticles, two-dimensional nanoparticles, and siloxane compound.
The construction process comprises the following steps:
when in use, A, B components are uniformly mixed according to the proportion of 5:1, deionized water accounting for 10-20% of the total weight of A, B components is added for dilution after the mixture is fully stirred, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup.
Table 4 composition of formulation 16 of comparative example 1
Comparative example 2
The waterborne epoxy primer of comparative example 2 was prepared according to formulation 17 shown in table 5, and was prepared in the same manner as in example 1, except that formulation 17 of comparative example 2 did not include zero-dimensional nanoparticles and a siloxane compound.
The construction process comprises the following steps:
the amounts of the respective raw materials added in the preparation of the A-component and the B-component are shown in Table 5. Wherein the radial extension size of the graphene is 5 μm, and the thickness is 5 layers;
when in use, A, B components are uniformly mixed according to the proportion of 5:1, deionized water accounting for 10-20% of the total weight of A, B components is added for dilution after the mixture is fully stirred, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup.
TABLE 5 composition of formulation 17 of comparative example 2
Comparative example 3
The waterborne epoxy primer of comparative example 3 was prepared according to formulation 18 shown in Table 6, and was prepared in the same manner as in example 1, except that formulation 18 of comparative example 3 did not contain two-dimensional nanoparticles and a siloxane compound.
The construction process comprises the following steps:
the amounts of the respective raw materials added in the preparation of the A-component and the B-component are shown in Table 6. Wherein the particle size of the silicon oxide nano particles is 10 nm;
when in use, A, B components are uniformly mixed according to the proportion of 5:1, deionized water accounting for 10-20% of the total weight of A, B components is added for dilution after the mixture is fully stirred, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup.
TABLE 6 composition of formulation 18 of comparative example 3
Comparative example 4
The waterborne epoxy primer in comparative example 4 was prepared according to formulation 19 shown in Table 7, and was prepared in the same manner as in example 1, except that the silicone compound was not included in formulation 19 of comparative example 4.
The construction process comprises the following steps:
the amounts of the respective raw materials added in the preparation of the A-component and the B-component are shown in Table 7. Wherein the radial extension size of the graphene is 5 micrometers, the thickness of the graphene is 5 layers, and the particle size of the silicon oxide nano particles is 10 nm;
when in use, A, B components are uniformly mixed according to the proportion of 5:1, deionized water accounting for 10-20% of the total weight of A, B components is added for dilution after the mixture is fully stirred, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup.
TABLE 7 composition of formulation 19 of comparative example 4
Comparative example 5
The waterborne epoxy primer of comparative example 5 was prepared according to formulation 20 shown in table 8, and was prepared in the same manner as in example 1, except that formulation 20 of comparative example 5 did not include two-dimensional nanomaterials and zero-dimensional nanomaterials.
The construction process comprises the following steps:
the amounts of the respective raw materials added in the preparation of the A-component and the B-component are shown in Table 8.
When in use, A, B components are uniformly mixed according to the proportion of 5:1, deionized water accounting for 10-20% of the total weight of A, B components is added for dilution after the mixture is fully stirred, and the construction viscosity is between 11S and 21S of a No. Zahn-5 cup.
TABLE 8 composition of formulation 20 of comparative example 5
Test example
The performance tests were performed on the waterborne epoxy primers prepared in formulations 1-15 of examples 1-3 and the waterborne epoxy primers in formulations 16-20 of comparative examples 1-5, and the results are shown in Table 9.
TABLE 9 test results of the Performance of the waterborne epoxy primers in formulations 1-15 of examples 1-3 and formulations 16-20 of comparative examples 1-5
From the results obtained in table 9, it can be found that the waterborne epoxy primer of formulas 1 to 15, which simultaneously includes the zero-dimensional nanomaterial, the two-dimensional nanomaterial, and the siloxane compound, according to the present invention has more excellent properties in terms of hardness, drawing adhesion, normal temperature water resistance, and salt spray resistance. Compared with the common formula (formula 16) which does not contain the zero-dimensional nano material, the two-dimensional nano material and the siloxane compound, the formula (formula 17) only containing the two-dimensional nano material is only improved to a certain extent in the aspects of normal-temperature water resistance and salt spray resistance, the formula (formula 18) only containing the zero-dimensional nano material is far lower than the formulas 1 to 15 although the hardness, the drawing adhesion, the normal-temperature water resistance and the salt spray resistance are improved, meanwhile, the formula (formula 19) containing the zero-dimensional nano material and the two-dimensional nano material is improved in all aspects but still lower than the formulas 1 to 15, and the formula (formula 20) only containing the siloxane compound is basically the same as the formula (formula 16) in all aspects.
By comparison, the improvement range of the performance of the epoxy primer simultaneously comprising the zero-dimensional nano material, the two-dimensional nano material and the siloxane compound is not the simple addition of the functions of the zero-dimensional nano material, the two-dimensional nano material or the siloxane compound, but the synergistic effect of the three. And even if other components in the formula are changed, the synergistic effect exists, and the universal primer has universality in the aspect of improving the performance of the water-based epoxy primer.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. The composite nano material reinforced water-based epoxy primer is characterized in that the weight ratio of a component A to a component B in raw materials is 3-5: 1; based on the weight portion, the weight portion of the material,
the component A comprises 30-65 parts of water-based epoxy resin emulsion, 2-5 parts of a first solvent, 0.2-1 part of a suspending agent, 2-10 parts of an anti-rust pigment, 0.5-1.5 parts of an anti-flash rust agent, 20-60 parts of pigment and filler, 0.2-2.5 parts of an auxiliary agent, 0.05-4 parts of a zero-dimensional nano material, 0.05-1 part of a two-dimensional nano material and 0.1-5 parts of a siloxane compound;
the component B comprises 40-85 parts of a water-based epoxy curing agent and 0-10 parts of a second solvent;
wherein the weight part of the zero-dimensional nano material is not less than that of the two-dimensional nano material.
2. The waterborne epoxy primer of claim 1, wherein the zero-dimensional nanomaterial has a particle size of 2-100nm and the two-dimensional nanomaterial has a radial extension of 0.1-50 μm.
3. The water-based epoxy primer according to claim 1, wherein the zero-dimensional nanomaterial comprises one or more of silica nanoparticles, titanium oxide nanoparticles, and zinc oxide nanoparticles, the surface of which is not modified or is modified with epoxy groups, amino groups, or carboxyl groups.
4. The water-based epoxy primer according to claim 1, wherein the two-dimensional nanomaterial comprises graphene oxide or/and graphene; preferably, the number of graphene oxide layers is 1 to 10, and the number of graphene layers is 1 to 10.
5. The waterborne epoxy primer according to claim 1, wherein the silicone compound is selected from the winning Dynasylan series.
6. The waterborne epoxy primer of claim 1, wherein the first solvent is propylene glycol methyl ether and the second solvent is an alcohol ether solvent; preferably, the second solvent comprises at least one of propylene glycol methyl ether, propylene glycol phenyl ether, diethylene glycol butyl ether.
7. The waterborne epoxy primer of claim 1, wherein the suspending agent is an organobentonite clay.
8. The water-based epoxy primer according to claim 1, wherein the auxiliary agent comprises one or more of a substrate wetting agent, a defoaming agent and a dispersing agent.
9. The waterborne epoxy primer of claim 8, wherein the substrate wetting agent is a silicon-based or non-silicon-based substrate wetting agent; preferably, the defoaming agent is a silicon-based or non-silicon-based defoaming agent; preferably, the dispersant is a non-ionic or ionic dispersant.
10. A method of preparing a composite nanomaterial-reinforced waterborne epoxy primer according to any of claims 8 or 9, comprising the steps of:
s1: adding deionized water and a first solvent into the aqueous epoxy resin emulsion, and uniformly stirring; adding a suspending agent under stirring, then adding a dispersing agent, a pigment filler and an anti-rust pigment, stirring uniformly, grinding and diluting; adding deionized water, a base material wetting agent, a defoaming agent, an anti-flash rust agent, two-dimensional nano material dispersion slurry and zero-dimensional nano material dispersion slurry containing siloxane compounds, stirring and uniformly mixing, and discharging to obtain a component A;
s2: adding a waterborne epoxy curing agent into deionized water, uniformly mixing, adding a second solvent, filtering and discharging to obtain a component B;
s3: and uniformly mixing the component A and the component B to obtain the water-based epoxy primer.
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