CN109251661B - Ultrahigh-performance epoxy primer and preparation method thereof - Google Patents

Ultrahigh-performance epoxy primer and preparation method thereof Download PDF

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CN109251661B
CN109251661B CN201810994776.8A CN201810994776A CN109251661B CN 109251661 B CN109251661 B CN 109251661B CN 201810994776 A CN201810994776 A CN 201810994776A CN 109251661 B CN109251661 B CN 109251661B
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modified
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elastomer
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CN109251661A (en
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冯兆均
江瀚
施沃成
陈忠
李新
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Yatu High Tech Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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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    • 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
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Abstract

The invention belongs to the technical field of coatings, and particularly relates to an ultrahigh-performance epoxy primer and a preparation method thereof. The invention provides an ultrahigh-performance epoxy primer which comprises a component A and a component B, wherein the component A consists of elastomer modified epoxy resin, dimethylbenzene, butanol, a dispersing agent, an activated siloxane-based coupling agent, a zinc molybdate modified pigment, activated siloxane modified nano mica powder, organic modified mica iron oxide, superfine talcum powder, superfine barium sulfate, titanium dioxide, organic soil and carbon black; the component B consists of modified fatty amine, an epoxy curing accelerator K54, xylene and isopropanol; the weight ratio of the component A to the component B is 5: 1. The ultrahigh-performance epoxy primer disclosed by the invention has excellent corrosion resistance and rust resistance, water resistance, salt spray resistance and aging resistance; the drying is quick, and the construction performance is good; the coating is uniform and compact; good mechanical stability and strong adhesive force.

Description

Ultrahigh-performance epoxy primer and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an ultrahigh-performance epoxy primer and a preparation method thereof.
Background
Painting is a main anti-corrosion process and also a key means for obtaining good appearance of products, and paint is an important raw material for painting. The coating comprises a primer, a middle coat and a finish coat according to the coating components. The adhesion and corrosion resistance of the paint film mainly depend on the primer layer. The epoxy primer is a common industrial anticorrosive paint with excellent anticorrosive performance. The salt spray resistance time was 120 hours, as specified in the national standard HG/T4566-2013 epoxy primer. In the HG/T4566-2013 epoxy resin primer standard, epoxy primers are divided into two types of products for metal substrates and products for concrete substrates. The products for the metal substrate are divided into two types of universal primer and seal primer, and only the universal primer has the requirement of salt spray resistance. This is specified in HG/T4566-2013: the salt spray resistance of the epoxy primer is 120h, the index requires that the unidirectional corrosion at the scribed position is less than or equal to 2.0mm, and the unscored area has no phenomena of bubbling, rusting, cracking, peeling and the like. The salt spray resistance time of the epoxy primer is at least 120 h. The salt spray test simulates the condition that marine atmosphere containing a large amount of salt has strong corrosivity to metal materials and protective layers thereof, examines the corrosion resistance of a paint film in a severe environment, is started to be used in 1939, is improved to be improved continuously, and is generally used as a method for testing the corrosion resistance of the paint film at present.
Chinese patent application 201310517893.2A discloses a modified epoxy primer, which comprises the following components in parts by weight: epoxy resin: 25-65 parts of nano silicon oxide: 1-10 parts of a thixotropic agent: 2-5 parts of a dispersant: 1-3 parts of anticorrosive filler: 10-20 parts of pigment and filler, 10-20 parts of defoaming agent: 0.1-1 part; polyamide-based curing agent: 20-40 parts of a solvent; the epoxy resin has an epoxy equivalent of 250-400 EE. Although the modified epoxy primer provided by the invention can be directly coated on the surface of the aluminum material and has good adhesion with the surface of the aluminum material, the salt spray resistance and the water resistance of the modified epoxy primer are still not ideal.
At present, the existing epoxy primer on the market has the problems of unsatisfactory salt spray resistance, poor adhesion, unsatisfactory water resistance and the like. Therefore, it is highly desirable to develop an epoxy primer with excellent properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an ultrahigh-performance epoxy primer and a preparation method thereof. The ultrahigh-performance epoxy primer provided by the invention has excellent corrosion resistance and rust resistance, water resistance and salt spray resistance; the drying is quick, and the construction performance is good; the coating is uniform and compact; good mechanical stability and strong adhesive force. In addition, the ultra-high performance epoxy primer provided by the invention has excellent aging resistance.
The ultrahigh-performance epoxy primer comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 15-30 parts of elastomer modified epoxy resin, 5-10 parts of dimethylbenzene, 5-10 parts of butanol, 0.1-0.6 part of dispersing agent, 1-3 parts of activated siloxane-based coupling agent, 5-15 parts of zinc molybdate modified pigment, 3-12 parts of activated siloxane modified nano mica powder, 5-15 parts of organic modified mica iron oxide, 5-15 parts of superfine talcum powder, 3-12 parts of superfine barium sulfate, 5-15 parts of titanium dioxide, 0.2-0.8 part of organic soil and 0.2-0.5 part of carbon black;
the component B comprises the following components in parts by weight: 30-60 parts of modified fatty amine, 541-3 parts of epoxy curing accelerator K, 15-30 parts of dimethylbenzene and 10-20 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
Further, the ultrahigh-performance epoxy primer comprises a component A and a component B, wherein the component A comprises the following components in parts by weight: 20 parts of elastomer modified epoxy resin, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, 1.5 parts of activated siloxane-based coupling agent, 12 parts of zinc molybdate modified pigment, 11 parts of activated siloxane modified nano mica powder, 10 parts of organic modified mica iron oxide, 9 parts of superfine talcum powder, 4 parts of superfine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organic soil and 0.2 part of carbon black;
the component B comprises the following components in parts by weight: 54 parts of modified aliphatic amine, 541.2 parts of epoxy curing accelerator K, 26.8 parts of xylene and 18 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
Further, the preparation method of the elastomer modified epoxy resin comprises the following steps:
(1) adding epoxy resin, cyclohexanone and butyl acetate into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding polymethylhydrosiloxane after the epoxy resin is completely melted, heating to 160 ℃, uniformly dropwise adding dibutyltin dilaurate for 30min, and continuously reacting for 1.5h after dropwise adding is completed to obtain a modifier, wherein the weight ratio of the epoxy resin, the cyclohexanone, the butyl acetate, the polymethylhydrosiloxane and the dibutyltin dilaurate is 50:10:15:6: 1;
(2) and (2) cooling the modified substance obtained in the step (1) to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the modified substance obtained in the step (1), the addition amount of the tetrabutylammonium chloride is 1% of that of the modified substance obtained in the step (1), heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the modified substance.
Further, the elastomer in the step (2) is prepared from the following components in parts by weight:
10-13 parts of methyl methacrylate, 3-5 parts of butyl acrylate, 0.5-1 part of acrylic acid, 0.2-0.5 part of azobisisobutyronitrile, 0.8-1.5 parts of thioglycolic acid and 40-45 parts of n-butyl alcohol.
Further, the elastomer in the step (2) is prepared from the following components in parts by weight:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azobisisobutyronitrile, 1.2 parts of thioglycolic acid and 42 parts of n-butanol.
Further, the preparation method of the elastomer comprises the following steps:
(a) uniformly mixing methyl methacrylate, butyl acrylate, acrylic acid and azodiisobutyronitrile to obtain a mixture;
(b) adding n-butanol into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adding thioglycollic acid and 1/2 amounts of the mixture obtained in the step (a), heating to a reflux temperature, continuously dropwise adding the rest amount of the mixture obtained in the step (a) by using the dropping funnel after 30min, wherein the dropwise adding time is 2h, and after the dropwise adding is finished, keeping the temperature at 120 ℃ and reacting for 1.5h to obtain a mixed system;
(c) and (c) distilling the mixed system obtained in the step (b) under reduced pressure to remove the solvent and unreacted monomers, thus obtaining the compound.
Further, the organic matter modified mica iron oxide is prepared from the following components in parts by weight:
12-15 parts of mica iron oxide, 0.5-1 part of nano zinc oxide, 1.8-3.5 parts of oleic acid, 0.5-1 part of oleic acid diethanolamide, 0.4-0.6 part of polydimethylsiloxane, 0.4-0.7 part of sodium dodecyl benzene sulfonate and 40-50 parts of absolute ethyl alcohol.
Furthermore, the organic matter modified mica iron oxide is prepared from the following components in parts by weight:
13 parts of mica iron oxide, 0.6 part of nano zinc oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethanolamide, 0.5 part of polydimethylsiloxane, 0.6 part of sodium dodecyl benzene sulfonate and 46 parts of absolute ethyl alcohol.
Further, the preparation method of the organic matter modified mica iron oxide comprises the following steps:
adding oleic acid, oleic acid diethanolamide and absolute ethyl alcohol into nano zinc oxide, wherein the addition amount of the absolute ethyl alcohol is 8 times of the weight of the nano zinc oxide, and performing ultrasonic reaction for 25min at the temperature of 60 ℃, the ultrasonic power of 100W and the ultrasonic frequency of 60Hz to obtain slurry;
(II) adding sodium dodecyl benzene sulfonate into absolute ethyl alcohol to ensure that the mass concentration of the sodium dodecyl benzene sulfonate in the absolute ethyl alcohol is 6 percent to obtain an alcohol solution;
and (III) adding the slurry obtained in the step (I) and the residual amount of absolute ethyl alcohol into mica iron oxide, performing ultrasonic treatment with ultrasonic power of 100W, ultrasonic frequency of 50Hz and ultrasonic time of 6min, stirring in a constant-temperature water bath at 55 ℃ for 20min, adding polydimethylsiloxane, uniformly stirring, adding the alcohol solution obtained in the step (II), stirring at constant temperature for reaction for 1.5h, performing vacuum filtration, drying the obtained solid in a vacuum drying oven at 60 ℃ for 12h, and crushing to obtain the mica iron oxide.
Further, the preparation method of the activated siloxane modified nano mica powder comprises the following steps:
① adding the nano mica powder into absolute ethyl alcohol to make the mass concentration of the nano mica powder in the absolute ethyl alcohol 20%, uniformly dispersing by ultrasonic with the ultrasonic power of 100W, the ultrasonic frequency of 60Hz and the ultrasonic time of 15min to obtain slurry;
② adding 95 vol% ethanol water solution to get 20 vol% of active siloxane-based coupling agent (12 wt% of ①) based on the weight of the mica powder, adjusting pH to 5 with acetic acid, and stirring for 40min to get hydrolysate;
③ heating the slurry obtained in step ① to 80 ℃, adding the hydrolysate obtained in step ②, reacting for 1.5h, and performing suction filtration, washing, drying and grinding on the reaction product to obtain the catalyst.
Further, the dispersing agent consists of a high molecular weight polyurethane dispersing agent EFKA-4010 and a wetting dispersing agent CT-3050 in a weight ratio of 6-8: 1-3.
Further, the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 7: 2.
Further, the organic soil is organic bentonite.
In addition, the invention also provides a preparation method of the ultrahigh-performance epoxy primer, which comprises the following steps:
s1 sequentially adding elastomer modified epoxy resin, xylene, butanol and a dispersing agent according to the formula amount, stirring for 5-10min at the speed of 600r/min for 300-10 min to obtain a mixture A, adding an activated siloxane-based coupling agent according to the formula amount into the mixture A, stirring for 5-10min at the speed of 600r/min for 300-10 min to obtain a mixture B, sequentially adding zinc molybdate modified pigment, activated siloxane modified nano mica powder, organic matter modified mica iron oxide, superfine talcum powder, superfine barium sulfate, titanium dioxide, organic soil and carbon black according to the formula amount into the mixture B, sanding at the rotating speed of 1200r/min for 900-1200r/min until the fineness is below 35 mu m, and at the temperature of below 60 ℃, and at the flow rate of 10-15L/min to obtain a component A;
s2, mixing the dimethylbenzene and the isopropanol with the formula amount, adding the modified aliphatic amine and the epoxy curing accelerator K54 with the formula amount at the rotating speed of 300-600r/min, and then stirring for 20min at the rotating speed of 600-900r/min to obtain a component B;
s3, mixing the component A obtained in the step S1 and the component B obtained in the step S2 uniformly to obtain the product.
According to the invention, firstly, polymethylhydrosiloxane is adopted to modify epoxy resin, so that active groups in the polymethylhydrosiloxane react with hydroxyl groups in the epoxy resin under the action of a catalyst to prepare a modified substance, and then an elastomer is used to modify the modified substance for the second time, so that carboxyl groups in the elastomer react with epoxy groups in the modified substance to prepare the elastomer modified epoxy resin, the crosslinking density of a system is greatly improved, and the absorption of a paint film to cations is also hindered, so that not only can the corrosion resistance of the paint film be enhanced, but also the water resistance of the prepared paint film can be improved, and the salt fog resistance of the paint film can be further enhanced. Meanwhile, the stability, toughness and impact resistance of the paint film can be enhanced.
The oleic acid diethanolamide added in the preparation of the organic matter modified mica iron oxide can improve the dispersing performance of the nano zinc oxide, enables the nano zinc oxide to be uniformly dispersed and to participate in the reaction more fully, enhances the stability of the nano zinc oxide in a coating system, can also enhance the adhesion performance of the product, and improves the adhesive force, the aging resistance and the corrosion resistance.
According to the invention, the elastomer prepared from methyl methacrylate, butyl acrylate, acrylic acid, thioglycollic acid and the like is used for preparing the elastomer modified epoxy resin, so that the adhesive force and flexibility of a paint film can be enhanced, the film forming effect is better, and the elastomer modified epoxy resin has good water resistance, oil resistance, solvent resistance and other properties.
The ultrahigh-performance epoxy primer provided by the invention is prepared from elastomer modified epoxy resin, zinc molybdate modified pigment, activated siloxane modified nano mica powder, organic modified mica iron oxide and the like. The ultrahigh-performance epoxy primer provided by the invention has excellent corrosion resistance and rust resistance, water resistance and salt spray resistance; the drying is quick, and the construction performance is good; the coating is uniform and compact; the mechanical stability is good; also has excellent adhesive force and aging resistance.
Compared with the prior art, the invention has the following advantages:
(1) the ultra-high performance epoxy primer provided by the invention has ultra-high tolerance, salt spray resistance can reach more than 1000 hours (dry film is 40-50 mu m), and the adhesive force is 0-1 grade when the adhesive force is measured by cross; the salt spray resistance of the existing epoxy primer on the market is 700 hours (dry film is 40-50 mu m), and the adhesive force is more than or equal to grade 2 when the adhesive force is measured by dividing grids.
(2) The ultra-high performance epoxy primer provided by the invention can be polished after being sprayed for 12 hours at room temperature, does not stick sand, and can be scraped with putty after being polished without bottom biting.
(3) The ultra-high performance epoxy primer provided by the invention has excellent water resistance, the water resistance is more than 30 days, and the cross-cut adhesion is 0-1 grade.
(4) The modified fatty amine is used as a curing agent, and has excellent adhesive force and corrosion resistance; the epoxy resin is modified by combining elastic resin, so that the adhesive force can be greatly improved.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
According to the invention, the ultrafine talcum powder can be purchased from Guangyin Guangyuan Guangyi super-fine powder limited company with the specification of 5000 meshes, the ultrafine barium sulfate can be purchased from Fushan Guangyi super-fine powder limited company with the specification of 1000 meshes, the carbon black can be purchased from Shanghai Qingli industry development limited company with the brand of Cambet with the model of M800, the epoxy resin can be purchased from Kyoho chemical industry limited company with the brand of E-128 with the model of 0002516, the titanium dioxide can be purchased from Dongguan Waishi trade limited company with the model of R-996, the high molecular weight polyurethane dispersant EFKA-4010 can be purchased from Qianshan Qiancai chemical industry limited company with the model of EFKA 0810, the wetting dispersant CT-3050 can be purchased from Jinan Changtai chemical industry limited company with the model of CT-3050, the zinc molybdate modified pigment can be purchased from Zhengzhou Huamai chemical industry product limited company with the model of No. of CT-20180226, the polymethylhydrosiloxane can be purchased from Wuhanhanhan far-synthetic co-created from Wuhan Co-created company with the model of Wuhan, the model of nanometer zinc oxide 46305, the nanometer silicone oxide modified pigment can be purchased from Xianhua Yonghua Kanghua industrial product with the model of AS 54, the model of Xhoya product with the model of Xhoid product of Xhoff, the model of Xhoya product of Xhoff, the model of Xhoya product of Xhoff-3669, the model of Xhoff, the model of Xhoya product of X.
Example 1 an ultra high Performance epoxy primer
The ultrahigh-performance epoxy primer consists of a component A and a component B, wherein the component A consists of the following components in parts by weight: 20 parts of elastomer modified epoxy resin, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, 1.5 parts of activated siloxane-based coupling agent, 12 parts of zinc molybdate modified pigment, 11 parts of activated siloxane modified nano mica powder, 10 parts of organic modified mica iron oxide, 9 parts of superfine talcum powder, 4 parts of superfine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organic soil and 0.2 part of carbon black; the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 7: 2; the organic soil is organic bentonite;
the component B comprises the following components in parts by weight: 54 parts of modified aliphatic amine, 541.2 parts of epoxy curing accelerator K, 26.8 parts of xylene and 18 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
The preparation method of the elastomer modified epoxy resin comprises the following steps:
(1) adding epoxy resin, cyclohexanone and butyl acetate into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding polymethylhydrosiloxane after the epoxy resin is completely melted, heating to 160 ℃, uniformly dropwise adding dibutyltin dilaurate for 30min, and continuously reacting for 1.5h after dropwise adding is completed to obtain a modifier, wherein the weight ratio of the epoxy resin, the cyclohexanone, the butyl acetate, the polymethylhydrosiloxane and the dibutyltin dilaurate is 50:10:15:6: 1;
(2) and (2) cooling the modified substance obtained in the step (1) to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the modified substance obtained in the step (1), the addition amount of the tetrabutylammonium chloride is 1% of that of the modified substance obtained in the step (1), heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the modified substance.
The preparation method of the elastomer modified epoxy resin comprises the following steps of (2) preparing the elastomer from the following components in parts by weight:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azobisisobutyronitrile, 1.2 parts of thioglycolic acid and 42 parts of n-butanol.
The preparation method of the elastomer comprises the following steps:
(a) uniformly mixing methyl methacrylate, butyl acrylate, acrylic acid and azodiisobutyronitrile to obtain a mixture;
(b) adding n-butanol into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adding thioglycollic acid and 1/2 amounts of the mixture obtained in the step (a), heating to a reflux temperature, continuously dropwise adding the rest amount of the mixture obtained in the step (a) by using the dropping funnel after 30min, wherein the dropwise adding time is 2h, and after the dropwise adding is finished, keeping the temperature at 120 ℃ and reacting for 1.5h to obtain a mixed system;
(c) and (c) distilling the mixed system obtained in the step (b) under reduced pressure to remove the solvent and unreacted monomers, thus obtaining the compound.
The organic matter modified mica iron oxide is prepared from the following components in parts by weight:
13 parts of mica iron oxide, 0.6 part of nano zinc oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethanolamide, 0.5 part of polydimethylsiloxane, 0.6 part of sodium dodecyl benzene sulfonate and 46 parts of absolute ethyl alcohol.
The preparation method of the organic matter modified mica iron oxide comprises the following steps:
adding oleic acid, oleic acid diethanolamide and absolute ethyl alcohol into nano zinc oxide, wherein the addition amount of the absolute ethyl alcohol is 8 times of the weight of the nano zinc oxide, and performing ultrasonic reaction for 25min at the temperature of 60 ℃, the ultrasonic power of 100W and the ultrasonic frequency of 60Hz to obtain slurry;
(II) adding sodium dodecyl benzene sulfonate into absolute ethyl alcohol to ensure that the mass concentration of the sodium dodecyl benzene sulfonate in the absolute ethyl alcohol is 6 percent to obtain an alcohol solution;
and (III) adding the slurry obtained in the step (I) and the residual amount of absolute ethyl alcohol into mica iron oxide, performing ultrasonic treatment with ultrasonic power of 100W, ultrasonic frequency of 50Hz and ultrasonic time of 6min, stirring in a constant-temperature water bath at 55 ℃ for 20min, adding polydimethylsiloxane, uniformly stirring, adding the alcohol solution obtained in the step (II), stirring at constant temperature for reaction for 1.5h, performing vacuum filtration, drying the obtained solid in a vacuum drying oven at 60 ℃ for 12h, and crushing to obtain the mica iron oxide.
The preparation method of the activated siloxane modified nano mica powder comprises the following steps:
① adding the nano mica powder into absolute ethyl alcohol to make the mass concentration of the nano mica powder in the absolute ethyl alcohol 20%, uniformly dispersing by ultrasonic with the ultrasonic power of 100W, the ultrasonic frequency of 60Hz and the ultrasonic time of 15min to obtain slurry;
② adding 95 vol% ethanol water solution to get 20 vol% of active siloxane-based coupling agent (12 wt% of ①) based on the weight of the mica powder, adjusting pH to 5 with acetic acid, and stirring for 40min to get hydrolysate;
③ heating the slurry obtained in step ① to 80 ℃, adding the hydrolysate obtained in step ②, reacting for 1.5h, and performing suction filtration, washing, drying and grinding on the reaction product to obtain the catalyst.
The preparation method of the ultrahigh-performance epoxy primer comprises the following steps:
s1, sequentially adding elastomer modified epoxy resin, xylene, butanol and a dispersing agent according to the formula amount, stirring for 7min at the speed of 500r/min to obtain a mixture A, adding an activated siloxane-based coupling agent according to the formula amount to the mixture A, stirring for 7min at the speed of 500r/min to obtain a mixture B, sequentially adding zinc molybdate modified pigment, activated siloxane modified nano mica powder, organic modified mica iron oxide, superfine talcum powder, superfine barium sulfate, titanium dioxide, organic soil and carbon black according to the formula amount to the mixture B, sanding at the rotating speed of 1100r/min until the fineness is below 35 mu m, keeping the temperature below 60 ℃, and obtaining a component A at the flow rate of 13L/min;
s2, mixing dimethylbenzene and isopropanol according to the formula amount, adding modified aliphatic amine and an epoxy curing accelerator K54 according to the formula amount at the rotating speed of 400r/min, and stirring for 20min at the rotating speed of 400r/min to obtain a component B;
s3, mixing the component A obtained in the step S1 and the component B obtained in the step S2 uniformly to obtain the product.
Example 2 an ultra high Performance epoxy primer
The ultrahigh-performance epoxy primer consists of a component A and a component B, wherein the component A consists of the following components in parts by weight: 15 parts of elastomer modified epoxy resin, 5 parts of dimethylbenzene, 5 parts of butanol, 0.1 part of dispersing agent, 1 part of activated siloxane-based coupling agent, 5 parts of zinc molybdate modified pigment, 3 parts of activated siloxane modified nano mica powder, 5 parts of organic modified mica iron oxide, 5 parts of superfine talcum powder, 3 parts of superfine barium sulfate, 5 parts of titanium dioxide, 0.2 part of organic soil and 0.2 part of carbon black; the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 6: 3; the organic soil is organic bentonite.
The component B comprises the following components in parts by weight: 30 parts of modified aliphatic amine, 541 parts of epoxy curing accelerator K, 15 parts of dimethylbenzene and 10 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
The preparation method of the elastomer modified epoxy resin comprises the following steps:
(1) adding epoxy resin, cyclohexanone and butyl acetate into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding polymethylhydrosiloxane after the epoxy resin is completely melted, heating to 160 ℃, uniformly dropwise adding dibutyltin dilaurate for 30min, and continuously reacting for 1.5h after dropwise adding is completed to obtain a modifier, wherein the weight ratio of the epoxy resin, the cyclohexanone, the butyl acetate, the polymethylhydrosiloxane and the dibutyltin dilaurate is 50:10:15:6: 1;
(2) and (2) cooling the modified substance obtained in the step (1) to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the modified substance obtained in the step (1), the addition amount of the tetrabutylammonium chloride is 1% of that of the modified substance obtained in the step (1), heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the modified substance.
The preparation method of the elastomer modified epoxy resin comprises the following steps of (2) preparing the elastomer from the following components in parts by weight:
10 parts of methyl methacrylate, 3 parts of butyl acrylate, 0.5 part of acrylic acid, 0.2 part of azobisisobutyronitrile, 0.8 part of thioglycolic acid and 40 parts of n-butyl alcohol.
The elastomer was prepared analogously to example 1.
The organic matter modified mica iron oxide is prepared from the following components in parts by weight:
12 parts of mica iron oxide, 0.5 part of nano zinc oxide, 1.8 parts of oleic acid, 0.5 part of oleic acid diethanolamide, 0.4 part of polydimethylsiloxane, 0.4 part of sodium dodecyl benzene sulfonate and 40 parts of absolute ethyl alcohol.
The preparation of the organic modified micaceous iron oxide was similar to that of example 1.
The preparation method of the activated siloxane modified nano mica powder is similar to that of the example 1.
The preparation method of the ultrahigh-performance epoxy primer comprises the following steps:
s1, sequentially adding elastomer modified epoxy resin, xylene, butanol and a dispersing agent according to the formula amount, stirring for 5min at the speed of 300r/min to obtain a mixture A, adding an activated siloxane-based coupling agent according to the formula amount to the mixture A, stirring for 5min at the speed of 300r/min to obtain a mixture B, sequentially adding zinc molybdate modified pigment, activated siloxane modified nano mica powder, organic modified mica iron oxide, superfine talcum powder, superfine barium sulfate, titanium dioxide, organic soil and carbon black according to the formula amount to the mixture B, sanding at the rotating speed of 900r/min until the fineness is below 35 mu m, the temperature is below 60 ℃, and the flow rate is 10L/min to obtain a component A;
s2, mixing dimethylbenzene and isopropanol according to the formula amount, adding modified aliphatic amine and an epoxy curing accelerator K54 according to the formula amount at the rotating speed of 300r/min, and then stirring for 20min at the rotating speed of 600r/min to obtain a component B;
s3, mixing the component A obtained in the step S1 and the component B obtained in the step S2 uniformly to obtain the product.
Example 3 an ultra high Performance epoxy primer
The ultrahigh-performance epoxy primer consists of a component A and a component B, wherein the component A consists of the following components in parts by weight: 30 parts of elastomer modified epoxy resin, 10 parts of dimethylbenzene, 10 parts of butanol, 0.6 part of dispersing agent, 3 parts of activated siloxane-based coupling agent, 15 parts of zinc molybdate modified pigment, 12 parts of activated siloxane modified nano mica powder, 15 parts of organic modified mica iron oxide, 15 parts of superfine talcum powder, 12 parts of superfine barium sulfate, 15 parts of titanium dioxide, 0.8 part of organic soil and 0.5 part of carbon black; the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 8: 1; the organic soil is organic bentonite.
The component B comprises the following components in parts by weight: 60 parts of modified aliphatic amine, 543 parts of epoxy curing accelerator K, 30 parts of dimethylbenzene and 20 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
The preparation method of the elastomer modified epoxy resin comprises the following steps:
(1) adding epoxy resin, cyclohexanone and butyl acetate into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding polymethylhydrosiloxane after the epoxy resin is completely melted, heating to 160 ℃, uniformly dropwise adding dibutyltin dilaurate for 30min, and continuously reacting for 1.5h after dropwise adding is completed to obtain a modifier, wherein the weight ratio of the epoxy resin, the cyclohexanone, the butyl acetate, the polymethylhydrosiloxane and the dibutyltin dilaurate is 50:10:15:6: 1;
(2) and (2) cooling the modified substance obtained in the step (1) to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the modified substance obtained in the step (1), the addition amount of the tetrabutylammonium chloride is 1% of that of the modified substance obtained in the step (1), heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the modified substance.
The preparation method of the elastomer modified epoxy resin comprises the following steps of (2) preparing the elastomer from the following components in parts by weight:
13 parts of methyl methacrylate, 5 parts of butyl acrylate, 1 part of acrylic acid, 0.5 part of azobisisobutyronitrile, 1.5 parts of thioglycolic acid and 45 parts of n-butyl alcohol.
The elastomer was prepared analogously to example 1.
The organic matter modified mica iron oxide is prepared from the following components in parts by weight:
15 parts of mica iron oxide, 1 part of nano zinc oxide, 3.5 parts of oleic acid, 1 part of oleic acid diethanolamide, 0.6 part of polydimethylsiloxane, 0.7 part of sodium dodecyl benzene sulfonate and 50 parts of absolute ethyl alcohol.
The preparation of the organic modified micaceous iron oxide was similar to that of example 1.
The preparation method of the activated siloxane modified nano mica powder is similar to that of the example 1.
The preparation method of the ultrahigh-performance epoxy primer comprises the following steps:
s1, sequentially adding elastomer modified epoxy resin, xylene, butanol and a dispersing agent according to the formula amount, stirring for 10min at the speed of 600r/min to obtain a mixture A, adding an activated siloxane-based coupling agent according to the formula amount to the mixture A, stirring for 10min at the speed of 600r/min to obtain a mixture B, sequentially adding zinc molybdate modified pigment, activated siloxane modified nano mica powder, organic modified mica iron oxide, superfine talcum powder, superfine barium sulfate, titanium dioxide, organic soil and carbon black according to the formula amount to the mixture B, sanding at the rotating speed of 1200r/min until the fineness is below 35 mu m, the temperature is below 60 ℃, and the flow rate is 15L/min to obtain a component A;
s2, mixing dimethylbenzene and isopropanol according to the formula amount, adding modified aliphatic amine and an epoxy curing accelerator K54 according to the formula amount at the rotating speed of 600r/min, and then stirring for 20min at the rotating speed of 900r/min to obtain a component B;
s3, mixing the component A obtained in the step S1 and the component B obtained in the step S2 uniformly to obtain the product.
Comparative example 1 an epoxy primer
The epoxy primer consists of a component A and a component B, wherein the component A consists of the following components in parts by weight: 20 parts of elastomer modified epoxy resin, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, 1.5 parts of activated siloxane-based coupling agent, 12 parts of zinc molybdate modified pigment, 11 parts of activated siloxane modified nano mica powder, 10 parts of organic modified mica iron oxide, 9 parts of superfine talcum powder, 4 parts of superfine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organic soil and 0.2 part of carbon black; the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 7: 2; the organic soil is organic bentonite;
the component B comprises the following components in parts by weight: 54 parts of modified aliphatic amine, 541.2 parts of epoxy curing accelerator K, 26.8 parts of xylene and 18 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
The preparation method of the elastomer modified epoxy resin comprises the following steps:
heating the epoxy resin to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the epoxy resin, the addition amount of the tetrabutylammonium chloride is 1% of that of the epoxy resin, heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the epoxy resin.
The elastomer is prepared from the following components in parts by weight:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azobisisobutyronitrile, 1.2 parts of thioglycolic acid and 42 parts of n-butanol.
The elastomer was prepared analogously to example 1.
The organic matter modified mica iron oxide is prepared from the following components in parts by weight:
13 parts of mica iron oxide, 0.6 part of nano zinc oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethanolamide, 0.5 part of polydimethylsiloxane, 0.6 part of sodium dodecyl benzene sulfonate and 46 parts of absolute ethyl alcohol.
The preparation of the organic modified micaceous iron oxide was similar to that of example 1.
The preparation method of the activated siloxane modified nano mica powder is similar to that of the example 1.
The preparation method of the ultra-high performance epoxy primer is similar to that of example 1.
The difference from example 1 is that the epoxy resin is modified only once.
Comparative example 2 an epoxy primer
The epoxy primer consists of a component A and a component B, wherein the component A consists of the following components in parts by weight: 20 parts of elastomer modified epoxy resin, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, 1.5 parts of activated siloxane-based coupling agent, 12 parts of zinc molybdate modified pigment, 11 parts of activated siloxane modified nano mica powder, 10 parts of organic modified mica iron oxide, 9 parts of superfine talcum powder, 4 parts of superfine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organic soil and 0.2 part of carbon black; the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 7: 2; the organic soil is organic bentonite;
the component B comprises the following components in parts by weight: 54 parts of modified aliphatic amine, 541.2 parts of epoxy curing accelerator K, 26.8 parts of xylene and 18 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
The elastomer-modified epoxy resin was prepared in a similar manner to example 1.
The organic matter modified mica iron oxide is prepared from the following components in parts by weight:
13 parts of mica iron oxide, 0.6 part of nano zinc oxide, 2.8 parts of oleic acid, 0.5 part of polydimethylsiloxane, 0.6 part of sodium dodecyl benzene sulfonate and 46 parts of absolute ethyl alcohol.
The preparation of the organic modified micaceous iron oxide was similar to that of example 1.
The preparation method of the activated siloxane modified nano mica powder is similar to that of the example 1.
The preparation method of the ultra-high performance epoxy primer is similar to that of example 1.
The difference from example 1 is that oleic acid diethanolamide is not added to the organic modified mica iron oxide, and the weight part of oleic acid is increased.
Comparative example 3 an epoxy primer
The epoxy primer consists of a component A and a component B, wherein the component A consists of the following components in parts by weight: 20 parts of elastomer modified epoxy resin, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, 1.5 parts of activated siloxane-based coupling agent, 12 parts of zinc molybdate modified pigment, 11 parts of activated siloxane modified nano mica powder, 10 parts of organic modified mica iron oxide, 9 parts of superfine talcum powder, 4 parts of superfine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organic soil and 0.2 part of carbon black; the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 7: 2; the organic soil is organic bentonite;
the component B comprises the following components in parts by weight: 54 parts of modified aliphatic amine, 541.2 parts of epoxy curing accelerator K, 26.8 parts of xylene and 18 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
The preparation method of the elastomer modified epoxy resin comprises the following steps:
(1) adding epoxy resin, cyclohexanone and butyl acetate into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding polymethylhydrosiloxane after the epoxy resin is completely melted, heating to 160 ℃, uniformly dropwise adding dibutyltin dilaurate for 30min, and continuously reacting for 1.5h after dropwise adding is completed to obtain a modifier, wherein the weight ratio of the epoxy resin, the cyclohexanone, the butyl acetate, the polymethylhydrosiloxane and the dibutyltin dilaurate is 50:10:15:6: 1;
(2) and (2) cooling the modified substance obtained in the step (1) to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the modified substance obtained in the step (1), the addition amount of the tetrabutylammonium chloride is 1% of that of the modified substance obtained in the step (1), heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the modified substance.
The preparation method of the elastomer modified epoxy resin comprises the following steps of (2) preparing the elastomer from the following components in parts by weight:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azobisisobutyronitrile, 1.2 parts of mercaptoethanol and 42 parts of n-butanol.
The elastomer was prepared analogously to example 1.
The organic matter modified mica iron oxide is prepared from the following components in parts by weight:
13 parts of mica iron oxide, 0.6 part of nano zinc oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethanolamide, 0.5 part of polydimethylsiloxane, 0.6 part of sodium dodecyl benzene sulfonate and 46 parts of absolute ethyl alcohol.
The preparation of the organic modified micaceous iron oxide was similar to that of example 1.
The preparation method of the activated siloxane modified nano mica powder is similar to that of the example 1.
The preparation method of the ultra-high performance epoxy primer is similar to that of example 1.
The difference from example 1 is that the elastomer has mercaptoacetic acid replaced by mercaptoethanol.
Comparative example 4 an epoxy primer
The epoxy primer consists of a component A and a component B, wherein the component A consists of the following components in parts by weight: 20 parts of elastomer modified epoxy resin, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, 1.5 parts of activated siloxane-based coupling agent, 12 parts of zinc molybdate modified pigment, 11 parts of activated siloxane modified nano mica powder, 10 parts of organic modified mica iron oxide, 9 parts of superfine talcum powder, 4 parts of superfine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organic soil and 0.2 part of carbon black; the dispersant consists of a high molecular weight polyurethane dispersant EFKA-4010 and a wetting dispersant CT-3050 in a weight ratio of 7: 2; the organic soil is organic bentonite;
the component B comprises the following components in parts by weight: 54 parts of modified aliphatic amine, 541.2 parts of epoxy curing accelerator K, 26.8 parts of xylene and 18 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
The preparation method of the elastomer modified epoxy resin comprises the following steps:
(1) adding epoxy resin, cyclohexanone and butyl acetate into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding polymethylhydrosiloxane after the epoxy resin is completely melted, heating to 160 ℃, uniformly dropwise adding dibutyltin dilaurate for 30min, and continuously reacting for 1.5h after dropwise adding is completed to obtain a modifier, wherein the weight ratio of the epoxy resin, the cyclohexanone, the butyl acetate, the polymethylhydrosiloxane and the dibutyltin dilaurate is 50:10:15:6: 1;
(2) and (2) cooling the modified substance obtained in the step (1) to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the modified substance obtained in the step (1), the addition amount of the tetrabutylammonium chloride is 1% of that of the modified substance obtained in the step (1), heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the modified substance.
The elastomer in the step (2) is prepared from the following components in parts by weight:
5.6 parts of methyl methacrylate, 5.6 parts of butyl acrylate, 5.6 parts of acrylic acid, 0.4 part of azobisisobutyronitrile, 1.2 parts of thioglycolic acid and 42 parts of n-butanol.
The elastomer was prepared analogously to example 1.
The organic matter modified mica iron oxide is prepared from the following components in parts by weight:
13 parts of mica iron oxide, 0.6 part of nano zinc oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethanolamide, 0.5 part of polydimethylsiloxane, 0.6 part of sodium dodecyl benzene sulfonate and 46 parts of absolute ethyl alcohol.
The preparation of the organic modified micaceous iron oxide was similar to that of example 1.
The preparation method of the activated siloxane modified nano mica powder is similar to that of the example 1.
The preparation method of the ultra-high performance epoxy primer is similar to that of example 1.
The difference from the embodiment 1 is that the elastomer is prepared by modifying 12 parts by mass of methyl methacrylate to 5.6 parts by mass, modifying 4 parts by mass of butyl acrylate to 5.6 parts by mass and modifying 0.8 part by mass of acrylic acid to 5.6 parts by mass.
Test example I, Performance test
1. Test materials: examples 1, 2, 3, 1, 2, 3 and 4.
2. The test method comprises the following steps: the epoxy primer was tested for water resistance, salt spray resistance, and the like with reference to relevant standards.
3. And (3) test results: the test results are shown in Table 1.
Table 1: results of Performance testing
Figure BDA0001781618910000161
As can be seen from table 1, the epoxy primer prepared by the present invention has excellent salt spray corrosion resistance and strong water resistance, wherein, after the epoxy primer prepared in example 3 has salt spray corrosion resistance for 1000 hours, the adhesion is 0 grade, and after a water resistance test is performed at 40 ℃ for 30 days, the adhesion is 0 grade, and the salt spray corrosion resistance and the water resistance of example 3 are the best examples of the present invention; compared with comparative examples 1-4, the epoxy primer prepared by the invention has better performance.
Test example two, adhesion test
1. Test materials: epoxy primers prepared in example 1, example 2, example 3, comparative example 2, comparative example 3 and comparative example 4.
2. The test method comprises the following steps: adhesion was evaluated on folding (1 best, 5 worst) after 30 minutes of putty (2mm thickness) application, and tested against putty adhesion. The adhesion of primed zinc, steel and aluminium plates (without substrate grinding) was tested with reference to GB/T9286.
3. And (3) test results: the test results are shown in tables 2 and 3.
Table 2: test results of adhesion to putty
Figure BDA0001781618910000171
As can be seen from Table 2, the ultra-high performance epoxy primer prepared by the invention has excellent adhesion with putty. Example 3 has stronger adhesion to atomic ash than comparative examples 2-4.
Table 3: test results of adhesion to zinc plate, steel plate and aluminum plate
Figure BDA0001781618910000172
As can be seen from Table 3, the ultra-high performance epoxy primer prepared by the invention has stronger adhesive force to zinc plates, steel plates and aluminum plates, wherein the adhesive force of the embodiment 3 is strongest, and is the best embodiment of the invention; example 3 of the present invention has stronger adhesion compared to comparative examples 2-4.

Claims (9)

1. The ultrahigh-performance epoxy primer is characterized by comprising a component A and a component B, wherein the component A comprises the following components in parts by weight: 15-30 parts of elastomer modified epoxy resin, 5-10 parts of dimethylbenzene, 5-10 parts of butanol, 0.1-0.6 part of dispersing agent, 1-3 parts of activated siloxane-based coupling agent, 5-15 parts of zinc molybdate modified pigment, 3-12 parts of activated siloxane modified nano mica powder, 5-15 parts of organic modified mica iron oxide, 5-15 parts of superfine talcum powder, 3-12 parts of superfine barium sulfate, 5-15 parts of titanium dioxide, 0.2-0.8 part of organic soil and 0.2-0.5 part of carbon black;
the component B comprises the following components in parts by weight: 30-60 parts of modified fatty amine, 541-3 parts of epoxy curing accelerator K, 15-30 parts of dimethylbenzene and 10-20 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1;
the preparation method of the elastomer modified epoxy resin comprises the following steps:
(1) adding epoxy resin, cyclohexanone and butyl acetate into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, heating to 70 ℃, adding polymethylhydrosiloxane after the epoxy resin is completely melted, heating to 160 ℃, uniformly dropwise adding dibutyltin dilaurate for 30min, and continuously reacting for 1.5h after dropwise adding is completed to obtain a modifier, wherein the weight ratio of the epoxy resin, the cyclohexanone, the butyl acetate, the polymethylhydrosiloxane and the dibutyltin dilaurate is 50:10:15:6: 1;
(2) and (2) cooling the modified substance obtained in the step (1) to 90 ℃, adding an elastomer and tetrabutylammonium chloride, wherein the weight of the elastomer is 15% of that of the modified substance obtained in the step (1), the addition amount of the tetrabutylammonium chloride is 1% of that of the modified substance obtained in the step (1), heating to 110 ℃ after the tetrabutylammonium chloride is completely melted, and reacting for 2 hours to obtain the modified substance.
2. The ultra-high performance epoxy primer of claim 1, wherein the component a comprises the following components in parts by weight: 20 parts of elastomer modified epoxy resin, 7 parts of dimethylbenzene, 5.5 parts of butanol, 0.3 part of dispersing agent, 1.5 parts of activated siloxane-based coupling agent, 12 parts of zinc molybdate modified pigment, 11 parts of activated siloxane modified nano mica powder, 10 parts of organic modified mica iron oxide, 9 parts of superfine talcum powder, 4 parts of superfine barium sulfate, 9.1 parts of titanium dioxide, 0.4 part of organic soil and 0.2 part of carbon black;
the component B comprises the following components in parts by weight: 54 parts of modified aliphatic amine, 541.2 parts of epoxy curing accelerator K, 26.8 parts of xylene and 18 parts of isopropanol;
the weight ratio of the component A to the component B is 5: 1.
3. The ultra-high performance epoxy primer of claim 1, wherein the elastomer of step (2) is prepared from the following components and parts by weight:
10-13 parts of methyl methacrylate, 3-5 parts of butyl acrylate, 0.5-1 part of acrylic acid, 0.2-0.5 part of azobisisobutyronitrile, 0.8-1.5 parts of thioglycolic acid and 40-45 parts of n-butyl alcohol.
4. The ultra-high performance epoxy primer of claim 3, wherein the elastomer is prepared from the following components in parts by weight:
12 parts of methyl methacrylate, 4 parts of butyl acrylate, 0.8 part of acrylic acid, 0.4 part of azobisisobutyronitrile, 1.2 parts of thioglycolic acid and 42 parts of n-butanol.
5. The ultra-high performance epoxy primer of claim 3, wherein the elastomer is prepared by a process comprising:
(a) uniformly mixing methyl methacrylate, butyl acrylate, acrylic acid and azodiisobutyronitrile to obtain a mixture;
(b) adding n-butanol into a four-necked bottle provided with a stirrer, a condenser pipe, a thermometer and a dropping funnel, adding thioglycollic acid and 1/2 amounts of the mixture obtained in the step (a), heating to a reflux temperature, continuously dropwise adding the rest amount of the mixture obtained in the step (a) by using the dropping funnel after 30min, wherein the dropwise adding time is 2h, and after the dropwise adding is finished, keeping the temperature at 120 ℃ and reacting for 1.5h to obtain a mixed system;
(c) and (c) distilling the mixed system obtained in the step (b) under reduced pressure to remove the solvent and unreacted monomers, thus obtaining the compound.
6. The ultra-high performance epoxy primer according to claim 1 or 2, wherein the organic modified mica iron oxide is prepared from the following components in parts by weight:
12-15 parts of mica iron oxide, 0.5-1 part of nano zinc oxide, 1.8-3.5 parts of oleic acid, 0.5-1 part of oleic acid diethanolamide, 0.4-0.6 part of polydimethylsiloxane, 0.4-0.7 part of sodium dodecyl benzene sulfonate and 40-50 parts of absolute ethyl alcohol.
7. The ultra-high performance epoxy primer according to claim 6, wherein the organic modified mica iron oxide is prepared from the following components in parts by weight:
13 parts of mica iron oxide, 0.6 part of nano zinc oxide, 2.2 parts of oleic acid, 0.6 part of oleic acid diethanolamide, 0.5 part of polydimethylsiloxane, 0.6 part of sodium dodecyl benzene sulfonate and 46 parts of absolute ethyl alcohol.
8. The ultra-high performance epoxy primer according to claim 6, wherein the organic modified mica iron oxide is prepared by the following steps:
adding oleic acid, oleic acid diethanolamide and absolute ethyl alcohol into nano zinc oxide, wherein the addition amount of the absolute ethyl alcohol is 8 times of the weight of the nano zinc oxide, and performing ultrasonic reaction for 25min at the temperature of 60 ℃, the ultrasonic power of 100W and the ultrasonic frequency of 60Hz to obtain slurry;
(II) adding sodium dodecyl benzene sulfonate into absolute ethyl alcohol to ensure that the mass concentration of the sodium dodecyl benzene sulfonate in the absolute ethyl alcohol is 6 percent to obtain an alcohol solution;
and (III) adding the slurry obtained in the step (I) and the residual amount of absolute ethyl alcohol into mica iron oxide, performing ultrasonic treatment with ultrasonic power of 100W, ultrasonic frequency of 50Hz and ultrasonic time of 6min, stirring in a constant-temperature water bath at 55 ℃ for 20min, adding polydimethylsiloxane, uniformly stirring, adding the alcohol solution obtained in the step (II), stirring at constant temperature for reaction for 1.5h, performing vacuum filtration, drying the obtained solid in a vacuum drying oven at 60 ℃ for 12h, and crushing to obtain the mica iron oxide.
9. The method of preparing an ultra high performance epoxy primer according to any one of claims 1 to 8, comprising the steps of:
s1 sequentially adding elastomer modified epoxy resin, xylene, butanol and a dispersing agent according to the formula amount, stirring for 5-10min at the speed of 600r/min for 300-10 min to obtain a mixture A, adding an activated siloxane-based coupling agent according to the formula amount into the mixture A, stirring for 5-10min at the speed of 600r/min for 300-10 min to obtain a mixture B, sequentially adding zinc molybdate modified pigment, activated siloxane modified nano mica powder, organic matter modified mica iron oxide, superfine talcum powder, superfine barium sulfate, titanium dioxide, organic soil and carbon black according to the formula amount into the mixture B, sanding at the rotating speed of 1200r/min for 900-1200r/min until the fineness is below 35 mu m, and at the temperature of below 60 ℃, and at the flow rate of 10-15L/min to obtain a component A;
s2, mixing the dimethylbenzene and the isopropanol with the formula amount, adding the modified aliphatic amine and the epoxy curing accelerator K54 with the formula amount at the rotating speed of 300-600r/min, and then stirring for 20min at the rotating speed of 600-900r/min to obtain a component B;
s3, mixing the component A obtained in the step S1 and the component B obtained in the step S2 uniformly to obtain the product.
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CN110256941A (en) * 2019-07-18 2019-09-20 江苏华云涂料有限公司 A kind of epoxy high-performance thick-slurry type priming paint
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CN112251108A (en) * 2020-10-26 2021-01-22 衡阳拓创聚合新材料有限公司 Solvent-free silicon modified elastic epoxy elastic floor coating
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