CN115011202A - Water-based epoxy resin coating based on modified graphite and preparation method thereof - Google Patents
Water-based epoxy resin coating based on modified graphite and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 121
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 239000011248 coating agent Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 58
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 21
- 239000010439 graphite Substances 0.000 claims abstract description 21
- -1 polydimethylsiloxane Polymers 0.000 claims abstract description 19
- 239000000839 emulsion Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 16
- HVOBSBRYQIYZNY-UHFFFAOYSA-N 2-[2-(2-aminoethylamino)ethylamino]ethanol Chemical compound NCCNCCNCCO HVOBSBRYQIYZNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims abstract description 11
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims abstract description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 11
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims abstract description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000007792 addition Methods 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 235000010344 sodium nitrate Nutrition 0.000 claims description 6
- 239000004317 sodium nitrate Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000009849 vacuum degassing Methods 0.000 description 2
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified graphite-based waterborne epoxy resin coating and a preparation method thereof, belonging to the technical field of waterborne coatings, wherein the coating comprises the following raw materials in parts by weight: 38-45 parts of waterborne epoxy resin emulsion, 3-4 parts of modified graphite, 25-29 parts of filler, 1.5-1.9 parts of surfactant, 0.1-0.2 part of polydimethylsiloxane, 0.2-0.3 part of hydroxyethyl cellulose and 20-30 parts of deionized water. According to the invention, graphite is subjected to oxidation treatment and then modified by hydroxyethyl diethylenetriamine, so that the problems of nonuniform dispersion of graphene powder, difficulty in direct action with a coating matrix and the like are solved, and the prepared water-based epoxy resin coating has the characteristics of high stability, low cost, safety, environmental protection and no toxicity, and meets the corrosion resistance requirements of the water-based environment-friendly coating.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a modified graphite-based waterborne epoxy resin coating and a preparation method thereof.
Background
In the water paint, the epoxy resin paint has high adhesion and corrosion resistance and relatively good safety, so the epoxy resin paint is widely applied. At present, the coating prepared from the water-based epoxy resin is widely applied to the field of automobile coating, but because automobiles are exposed in natural environment for a long time, and the corrosion resistance of the automobiles is poor due to the influence of ultraviolet radiation, rainwater, high and low temperature and the like in sunlight, the improvement of the corrosion resistance of the water-based epoxy resin coating is very critical. The performances of corrosion resistance, high temperature resistance and the like of the coating can be improved under the condition of a very small adding amount of the graphene and the derivatives thereof, but the graphene and the graphene oxide are not easy to disperse, so that the anticorrosive performance of the coating after the addition is still relatively low.
For example, chinese patent application No. 201710894372.7 discloses a graphene-containing aqueous epoxy resin emulsion and a preparation method thereof, and the preparation method of the aqueous epoxy resin emulsion specifically comprises the following steps: preparing a polyethylene glycol/graphene composite material, preparing a water-based epoxy resin emulsifier, and preparing a water-based epoxy resin emulsion. The polyethylene glycol/graphene composite material is prepared through an in-situ polymerization method, graphene can be uniformly dispersed and anchored in a polyethylene glycol matrix, hydroxyl on the surface of the polyethylene glycol reacts with epoxy resin under the action of a catalyst during preparation of an emulsifier, connection among the polyethylene glycol, the graphene and the epoxy resin is achieved, in the process of preparing an emulsion, the graphene enters the emulsion along with the emulsifier, the problems that the graphene is difficult to disperse in the emulsion, the compatibility is poor and the like are solved, and the uniformly dispersed graphene-containing aqueous epoxy resin emulsion is obtained. Although the patent can improve the dispersion problem of graphene in epoxy resin to a certain extent, in the polymerization process of polyethylene glycol, the oxygen-containing groups on the surface of graphene are difficult to specifically react with a polymer, so that the interaction between graphene and polyethylene glycol is not strong, and the dispersion of graphene in the water-based epoxy coating is further influenced. Therefore, the interaction of graphene with the epoxy matrix needs to be further strengthened.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a modified graphite-based waterborne epoxy resin coating and a preparation method thereof.
According to the invention, the modified graphite is obtained by carrying out oxidation treatment and hydroxyethyl diethylenetriamine grafting modification on graphite, the modified graphite not only retains the structure of a graphene lamellar layer, but also grafts an organic molecular chain on the surface, so that the uniform dispersion of graphene in a coating can be promoted, the acting force of the graphene and an epoxy resin matrix is improved, and the graphene can continuously and stably play a role; the lamellar graphene is uniformly dispersed, a compact isolation layer which is difficult to pass by micromolecule corrosive media such as water molecules and chloride ions can be formed, the shielding performance of the coating is greatly improved, and in addition, the graphene also has excellent heat-conducting performance, so that the corrosion resistance and the heat dissipation performance of the epoxy resin coating are improved.
The purpose of the invention can be realized by the following technical scheme:
the modified graphite-based waterborne epoxy resin coating comprises the following raw materials in parts by weight: 38-45 parts of waterborne epoxy resin emulsion, 3-4 parts of modified graphite, 25-29 parts of filler, 1.5-1.9 parts of surfactant, 0.1-0.2 part of polydimethylsiloxane, 0.2-0.3 part of hydroxyethyl cellulose and 20-30 parts of deionized water;
when in use, a water-based curing agent is required to be added, and the addition amount of the curing agent is 20 percent of the mass of the water-based epoxy resin coating.
Further, the filler is a mixture of talcum powder and mica powder according to the mass ratio of 1: 1.
Further, the surfactant is one of alkylphenol polyoxyethylene, high-carbon fatty alcohol polyoxyethylene, fatty acid polyoxyethylene ester and alkylolamide.
Further, the modified graphite is prepared by the following steps:
s1, sequentially adding flake graphite, potassium permanganate and sodium nitrate into a hydrothermal reaction kettle, then pouring concentrated sulfuric acid (mass fraction is 75%), covering a kettle cover, refrigerating the reaction kettle at 2 ℃ for 80-90min, and then placing the reaction kettle in an oven at 80 ℃ for heating for 2 h; taking out the reaction kettle, cooling to room temperature, pouring the product into a beaker filled with deionized water for dilution, then dropwise adding hydrogen peroxide, standing for 24 hours to obtain a lower-layer precipitate, carrying out acid washing for 3 times by using a dilute hydrochloric acid solution (the mass fraction is 5%), then carrying out water washing for 5 times to obtain a concentrated solution of graphene oxide, centrifuging, and carrying out freeze drying for 24 hours to obtain the graphene oxide; the dosage ratio of the crystalline flake graphite to the potassium permanganate to the sodium nitrate to the concentrated sulfuric acid to the deionized water to the hydrogen peroxide is 1g:5g:5g:50mL:250mL:10 mL;
oxidizing the flake graphite into graphene oxide under the strong oxidation effect of potassium permanganate, concentrated sulfuric acid and hydrogen peroxide;
s2, putting graphene oxide into a flask, adding deionized water into the flask, starting magnetic stirring, stirring for 12 hours, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours, dropwise adding hydroxyethyl diethylenetriamine into the mixture, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours after the addition is finished, performing suction filtration, washing for 3-5 times by using deionized water, finally drying in a vacuum drying oven at 60 ℃ to obtain modified graphite, and sealing for later use; the dosage ratio of the graphene oxide, the deionized water and the hydroxyethyl diethylenetriamine is 0.2mg to 150mL to 3.2 mL;
oxidizing the flake graphite in the step S1 to obtain graphene oxide, wherein the surface of a sheet layer of the graphene oxide contains more oxygen-containing groups such as epoxy groups, hydroxyl groups and carboxyl groups, and-NH on the molecule of hydroxyethyl diethylenetriamine is utilized 2 Chemically reacting with-COOH on the surface of graphene oxide to graft 4-aminostyrene on the surface of the graphene oxide through-CO-NH-, -NH 2 The reaction activity with-COOH is high, the reaction condition is simple and mild, and the specific reaction equation is as follows:
after the graphene oxide is modified by hydroxyethyl diethylenetriamine, a molecular chain of the hydroxyethyl diethylenetriamine is bonded through a precise chemical reaction, so that an active-OH group is introduced to the surface of the graphene oxide, the introduced-OH can react with an epoxy resin matrix under the action of a catalyst, the epoxy resin is subjected to ring opening, the direct connection between the graphene and the epoxy resin is realized, the uniform dispersion of the graphene oxide in the coating is promoted, the interaction force between the graphene and the resin matrix is improved, the migration resistance of the graphene in the coating is further improved, and the graphene is enabled to play a role stably and continuously.
A preparation method of a modified graphite-based waterborne epoxy resin coating comprises the following steps:
firstly, ultrasonically dispersing modified graphite in deionized water with half volume, and adding half of surfactant to obtain a graphite water dispersion;
and secondly, mixing the epoxy resin emulsion, the graphite aqueous dispersion, the filler, the rest half of the surfactant, the polydimethylsiloxane, the hydroxyethyl cellulose and the rest half of the deionized water, and performing ultrasonic dispersion for 2-3 hours to obtain the water-based epoxy resin coating.
When in use, the curing agent is added into the water-based epoxy resin coating, the mixture is mechanically stirred uniformly, and the spraying or coating operation can be carried out after vacuum degassing is carried out for 30-40min at room temperature.
The invention has the beneficial effects that:
according to the invention, the modified graphite is obtained by carrying out oxidation treatment and hydroxyethyl diethylenetriamine grafting modification on graphite, the modified graphite not only retains the structure of a graphene lamellar layer, but also grafts an organic molecular chain on the surface, so that the uniform dispersion of graphene in a coating can be promoted, the acting force of the graphene and an epoxy resin matrix is improved, and the graphene can continuously and stably play a role; the lamellar graphene is uniformly dispersed, a compact isolation layer which is difficult for micromolecular corrosive media such as water molecules and chloride ions to pass through can be formed, the shielding performance of the coating is greatly improved, and in addition, the graphene also has excellent heat-conducting performance, so that the corrosion resistance and the heat dissipation performance of the epoxy resin coating are improved;
the invention not only overcomes the problems that the graphene powder is not uniformly dispersed and is difficult to directly act with the coating matrix, but also has the characteristics of high stability, low cost, safety, environmental protection and no toxicity, and meets the corrosion resistance requirement of the water-based environment-friendly coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing modified graphite:
s1, sequentially adding 1g of crystalline flake graphite, 5g of potassium permanganate and 5g of sodium nitrate into a hydrothermal reaction kettle, then pouring 50mL of concentrated sulfuric acid (mass fraction is 75%), covering a kettle cover, refrigerating the reaction kettle at 2 ℃ for 80min, and then placing the reaction kettle in an oven at 80 ℃ to heat for 2 h; taking out the reaction kettle, cooling to room temperature, pouring the product into a beaker filled with 250mL of deionized water for dilution, then dropwise adding 10mL of hydrogen peroxide, standing for 24 hours to obtain a lower-layer precipitate, carrying out acid washing for 3 times by using a dilute hydrochloric acid solution (the mass fraction is 5%), then carrying out water washing for 5 times to obtain a concentrated solution of graphene oxide, centrifuging, and carrying out freeze drying for 24 hours to obtain the graphene oxide;
s2, putting 2mg of graphene oxide into a flask, adding 1500mL of deionized water into the flask, starting magnetic stirring, stirring for 12 hours, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours, dropwise adding 32mL of hydroxyethyl diethylenetriamine into the solution, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours after the addition is finished, performing suction filtration, washing for 3 times by using deionized water, finally drying in a vacuum drying oven at 60 ℃ to obtain modified graphite, and sealing for later use.
Example 2
Preparing modified graphite:
s1, sequentially adding 1g of crystalline flake graphite, 5g of potassium permanganate and 5g of sodium nitrate into a hydrothermal reaction kettle, then pouring 50mL of concentrated sulfuric acid (mass fraction of 75%), covering a kettle cover, refrigerating the reaction kettle at 2 ℃ for 90min, and then placing the reaction kettle in an oven at 80 ℃ to heat for 2 h; taking out the reaction kettle, cooling to room temperature, pouring the product into a beaker filled with 250mL of deionized water for dilution, then dropwise adding 10mL of hydrogen peroxide, standing for 24 hours to obtain a lower-layer precipitate, carrying out acid washing for 3 times by using a dilute hydrochloric acid solution (the mass fraction is 5%), then carrying out water washing for 5 times to obtain a concentrated solution of graphene oxide, centrifuging, and carrying out freeze drying for 24 hours to obtain the graphene oxide;
s2, putting 1mg of graphene oxide into a flask, adding 750mL of deionized water into the flask, starting magnetic stirring, stirring for 12 hours, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours, dropwise adding 16mL of hydroxyethyl diethylenetriamine into the solution, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours after the addition is finished, performing suction filtration, washing for 5 times by using deionized water, finally drying in a vacuum drying oven at 60 ℃ to obtain modified graphite, and sealing for later use.
Example 3
A modified graphite-based waterborne epoxy resin coating comprises the following raw materials: 38g of aqueous epoxy resin emulsion, 3g of modified graphite prepared in example 1, 25g of filler, 1.5g of alkylphenol polyoxyethylene, 0.1g of polydimethylsiloxane, 0.2g of hydroxyethyl cellulose and 20g of deionized water;
the filler is a mixture of talcum powder and mica powder according to the mass ratio of 1: 1.
The water-based epoxy resin coating is prepared by the following steps:
firstly, ultrasonically dispersing modified graphite in deionized water with half volume, and adding half alkylphenol ethoxylates to obtain a graphite water dispersion;
and secondly, mixing the epoxy resin emulsion, the graphite aqueous dispersion, the filler, the rest half alkylphenol ethoxylates, the polydimethylsiloxane, the hydroxyethyl cellulose and the rest half deionized water, and performing ultrasonic dispersion for 2 hours to obtain the water-based epoxy resin coating.
Example 4
A modified graphite-based waterborne epoxy resin coating comprises the following raw materials: 41g of aqueous epoxy resin emulsion, 3.5g of modified graphite prepared in example 2, 27g of filler, 1.7g of high-carbon fatty alcohol polyoxyethylene ether, 0.15g of polydimethylsiloxane, 0.25g of hydroxyethyl cellulose and 25g of deionized water;
the filler is a mixture of talcum powder and mica powder according to the mass ratio of 1: 1.
The water-based epoxy resin coating is prepared by the following steps:
firstly, ultrasonically dispersing modified graphite in deionized water with half volume, and adding half of high-carbon fatty alcohol polyoxyethylene ether to obtain a graphite water dispersion;
and secondly, mixing the epoxy resin emulsion, the graphite aqueous dispersion, the filler, the rest half of high-carbon fatty alcohol polyoxyethylene ether, polydimethylsiloxane, hydroxyethyl cellulose and the rest half of deionized water, and performing ultrasonic dispersion for 2.5 hours to obtain the water-based epoxy resin coating.
Example 5
A modified graphite-based waterborne epoxy resin coating comprises the following raw materials: 45g of aqueous epoxy resin emulsion, 4g of modified graphite prepared in example 1, 29g of filler, 1.9g of fatty acid polyoxyethylene ester, 0.2g of polydimethylsiloxane, 0.3g of hydroxyethyl cellulose and 30g of deionized water;
the filler is a mixture of talcum powder and mica powder according to the mass ratio of 1: 1.
The water-based epoxy resin coating is prepared by the following steps:
the method comprises the following steps of firstly, ultrasonically dispersing modified graphite in deionized water with half volume, and adding half fatty acid polyoxyethylene ester to obtain a graphite water dispersion;
and secondly, mixing the epoxy resin emulsion, the graphite aqueous dispersion, the filler, the rest half of fatty acid polyoxyethylene ester, polydimethylsiloxane, hydroxyethyl cellulose and the rest half of deionized water, and performing ultrasonic dispersion for 3 hours to obtain the water-based epoxy resin coating.
Comparative example
The modified graphite in example 3 was replaced with ordinary graphene oxide, and the remaining raw materials and preparation process were unchanged.
When in use, the curing agent (the addition amount is 20 percent of the mass of the waterborne epoxy resin coating) is added into the waterborne epoxy resin coatings obtained in the examples 3-5 and the comparative example, the mixture is mechanically stirred uniformly, and performance test is carried out after vacuum degassing is carried out for 30-40min at room temperature.
The results obtained are shown in the following table:
the data in the table show that the epoxy resin coating prepared by the invention has higher coating impact resistance, better coating stability, excellent water resistance and salt spray resistance; according to the data of the comparative example, the graphene oxide can obviously improve the acting force with the epoxy resin matrix after being modified, promote dispersion and further improve various performances of the coating.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (8)
1. The modified graphite-based waterborne epoxy resin coating comprises the following raw materials in parts by weight: 38-45 parts of waterborne epoxy resin emulsion, 3-4 parts of modified graphite, 25-29 parts of filler, 1.5-1.9 parts of surfactant, 0.1-0.2 part of polydimethylsiloxane, 0.2-0.3 part of hydroxyethyl cellulose and 20-30 parts of deionized water, and is characterized in that the modified graphite is prepared by the following steps:
s1, sequentially adding flake graphite, potassium permanganate and sodium nitrate into a hydrothermal reaction kettle, then pouring concentrated sulfuric acid, covering a kettle cover, refrigerating the reaction kettle at 2 ℃ for 80-90min, and then placing the reaction kettle in an oven at 80 ℃ for heating for 2 h; taking out the reaction kettle, cooling to room temperature, pouring the product into a beaker filled with deionized water for dilution, then dropwise adding hydrogen peroxide, standing for 24 hours to obtain a lower-layer precipitate, carrying out acid washing for 3 times by using a dilute hydrochloric acid solution, then carrying out water washing for 5 times to obtain a concentrated solution of graphene oxide, centrifuging, and carrying out freeze drying for 24 hours to obtain graphene oxide;
s2, placing graphene oxide into a flask, adding deionized water into the flask, starting magnetic stirring, stirring for 12 hours, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours, then dropwise adding hydroxyethyl diethylenetriamine into the solution, continuing to perform ultrasonic treatment at 30 ℃ for 2 hours after the addition is finished, performing suction filtration, washing with deionized water for 3-5 times, and finally placing the solution in a vacuum drying oven at 60 ℃ for drying to obtain modified graphite.
2. The modified graphite-based waterborne epoxy resin coating as claimed in claim 1, wherein the mass fraction of the concentrated sulfuric acid in the step S1 is 75%; the mass fraction of the dilute hydrochloric acid solution is 5%.
3. The modified graphite-based waterborne epoxy resin coating of claim 1, wherein the amount of the flake graphite, the potassium permanganate, the sodium nitrate, the concentrated sulfuric acid, the deionized water, and the hydrogen peroxide in step S1 is 1g:5g:5g:50mL:250mL:10 mL.
4. The modified graphite-based waterborne epoxy resin coating of claim 1, wherein the amount ratio of graphene oxide to deionized water to hydroxyethyl diethylenetriamine in step S2 is 0.2mg:150mL:3.2 mL.
5. The modified graphite-based waterborne epoxy resin coating as claimed in claim 1, wherein a waterborne curing agent is added to the waterborne epoxy resin coating during use, and the addition amount of the curing agent is 20% of the mass of the waterborne epoxy resin coating.
6. The modified graphite-based waterborne epoxy resin coating as claimed in claim 1, wherein the filler is a mixture of talc powder and mica powder in a mass ratio of 1: 1.
7. The modified graphite-based waterborne epoxy resin coating as claimed in claim 1, wherein the surfactant is one of alkylphenol ethoxylates, higher fatty alcohol ethoxylates, fatty acid polyoxyethylene esters and alkylolamides.
8. The preparation method of the modified graphite-based waterborne epoxy resin coating as claimed in claim 1, wherein the method comprises the following steps:
firstly, ultrasonically dispersing modified graphite in deionized water with half volume, and adding half of surfactant to obtain a graphite water dispersion;
and secondly, mixing the epoxy resin emulsion, the graphite water dispersion, the filler, the rest half of the surfactant, the polydimethylsiloxane, the hydroxyethyl cellulose and the rest half of the deionized water, and performing ultrasonic dispersion for 2-3 hours to obtain the water-based epoxy resin coating.
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