CN113234342B - Amino acid grafted graphene oxide filler, preparation method thereof and application of filler in water-based epoxy zinc-rich coating - Google Patents
Amino acid grafted graphene oxide filler, preparation method thereof and application of filler in water-based epoxy zinc-rich coating Download PDFInfo
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- CN113234342B CN113234342B CN202110654765.7A CN202110654765A CN113234342B CN 113234342 B CN113234342 B CN 113234342B CN 202110654765 A CN202110654765 A CN 202110654765A CN 113234342 B CN113234342 B CN 113234342B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000004593 Epoxy Substances 0.000 title claims abstract description 74
- 239000011701 zinc Substances 0.000 title claims abstract description 63
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 63
- 239000000945 filler Substances 0.000 title claims abstract description 58
- 238000000576 coating method Methods 0.000 title claims abstract description 52
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- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims abstract description 36
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 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 abstract description 11
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- IFGCUJZIWBUILZ-UHFFFAOYSA-N sodium 2-[[2-[[hydroxy-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyphosphoryl]amino]-4-methylpentanoyl]amino]-3-(1H-indol-3-yl)propanoic acid Chemical compound [Na+].C=1NC2=CC=CC=C2C=1CC(C(O)=O)NC(=O)C(CC(C)C)NP(O)(=O)OC1OC(C)C(O)C(O)C1O IFGCUJZIWBUILZ-UHFFFAOYSA-N 0.000 claims description 10
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
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- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 17
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- 239000002904 solvent Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- 238000000967 suction filtration Methods 0.000 description 3
- 125000001176 L-lysyl group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C([H])([H])C([H])([H])C([H])([H])C(N([H])[H])([H])[H] 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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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
- 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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- 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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- 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)
- Paints Or Removers (AREA)
Abstract
The invention relates to an amino acid grafted graphene oxide filler, a preparation method thereof and application thereof in a water-based epoxy zinc-rich coating, wherein the preparation raw materials of the amino acid grafted graphene oxide filler comprise: l-lysine, L-tryptophan and graphene oxide. The water-based epoxy zinc-rich paint comprises: zinc powder, water-based epoxy resin, a water-based epoxy curing agent, propylene glycol methyl ether, talcum powder, an amino acid grafted graphene oxide filler, a modifier, an auxiliary agent and water. The water-based epoxy zinc-rich paint has the advantages of simple preparation process, environmental protection, good stability, strong adhesive force, long-acting corrosion resistance and suitability for the field of heavy corrosion resistance.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to an amino acid grafted graphene oxide filler, a preparation method thereof and application thereof in a water-based epoxy zinc-rich coating.
Background
Corrosion is a phenomenon whereby metal and the surrounding environment are destroyed, and a direct economic loss of around $ 2.5 trillion per year worldwide is due to corrosion, corresponding to 3.4% of the world's GDP. In current metal corrosion protection technology, applying protective coatings is the more common method of preventing corrosion. Among different coatings, the zinc-rich anticorrosive coating is widely concerned, has wide application in infrastructure construction of ships, offshore oil platforms, storage tanks, pipelines, bridges and the like, and also has good development prospect in the fields of newly-built urban rail transit and the like.
The current research on the zinc-rich coating is mainly based on a solvent type, and although the zinc-rich coating has good anti-corrosion performance, the zinc-rich coating contains volatile organic substances, so that the zinc-rich coating is harmful to the environment and the health of people, and the development of the zinc-rich coating in the solvent type is limited. The waterborne epoxy zinc-rich anticorrosive paint is more and more popular among people due to the concepts of safety, no toxicity, environmental protection and green, has a good development prospect, but has an anticorrosive performance which is difficult to meet the market requirement, and is still not applied on a large scale at present, so that the key is to ensure that the waterborne epoxy zinc-rich anticorrosive paint is applied on a large-scale market and improve the anticorrosive performance.
CN106833271A discloses a graphene type waterborne epoxy zinc-rich anticorrosive paint, which consists of a component A and a component B, wherein the component A is prepared from the following raw materials in percentage by weight: 8-16% of a water-based epoxy resin curing agent; 0.1 to 1 percent of defoaming agent; 0.3 to 1 percent of dispersant; 0.5 to 3 percent of thixotropic agent; 3-10% of deionized water; 60-70% of zinc powder; 1-10% of graphene. The component B is prepared from the following raw materials in percentage by weight: 20-40% of water-based epoxy emulsion. According to the invention, the graphene is added to increase the adhesive force and flexibility of a paint film and increase the corrosion resistance of a base material. However, the compatibility of graphene in the coating and the water-based epoxy emulsion is relatively poor, and the graphene is easy to aggregate, so that the stability of the product is relatively poor, and the corrosion resistance is limited.
CN109554073A discloses an oil-resistant high-efficiency anticorrosive water-based epoxy zinc-rich primer, which comprises the following components in parts by weight: 130-190 parts of water-based resin, 20-60 parts of environment-friendly cosolvent, 5-10 parts of ferrophosphorus powder, 700-750 parts of zinc powder, 5-10 parts of dispersant, 1-2 parts of defoamer, 2-3 parts of flash rust prevention auxiliary agent and 60-80 parts of curing agent. The invention aims to provide an oil-resistant, efficient and anticorrosive water-based epoxy zinc-rich primer which is used for replacing solvent-based coatings of radiating oil tanks of transformer boxes, reduces the cost, greatly reduces the usage amount of solvents, does not contain heavy metals, is more beneficial to the health of human bodies, and achieves the performance of the solvent-based coatings on the indexes of salt mist, adhesion, hardness, water resistance, solvent resistance and the like. The corrosion protection properties of the primer are relatively weak.
Therefore, the water-based epoxy zinc-rich paint which is simple in preparation process, green, environment-friendly, good in stability, excellent in corrosion resistance and mechanical property is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the amino acid grafted graphene oxide filler which is energy-saving, environment-friendly, good in stability, excellent in corrosion resistance and mechanical properties and especially suitable for the water-based epoxy zinc-rich paint.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an amino acid-grafted graphene oxide filler, where the raw materials for preparing the amino acid-grafted graphene oxide filler include: l-lysine, L-tryptophan and graphene oxide.
The amino acid grafted graphene oxide filler is creatively grafted and modified with L-lysine and L-tryptophan, and has better mechanical property and corrosion resistance than the single L-lysine or L-tryptophan grafted and modified graphene oxide when being applied to a coating. The invention finds that when L-lysine and L-tryptophan are used for grafting and modifying graphene oxide simultaneously, the effect of improving the mechanical property and the corrosion resistance of the coating is better than that when the graphene oxide is modified by single L-lysine or L-tryptophan, and the two have synergistic interaction.
The graphene oxide is used as a single-layer material stripped from the graphite oxide, can stably exist in an aqueous solution and a polar solvent due to the introduction of a large number of oxygen-containing groups on the surface and the edge, can still maintain the layered structure of the graphite after oxidation treatment, can be orderly and densely stacked in a coating to form a powerful protective layer, and has an ultra-large specific surface area, so that the path of an external corrosive medium penetrating to the surface of a steel structure is complicated, and the impermeability of the coating is improved. A plurality of oxygen-based functional groups are introduced into the graphene single sheet by the graphene oxide, so that the compatibility with the water-based paint is improved, and the stability of the paint is further improved.
The L-lysine and the L-tryptophan both contain amino and carboxyl functional groups, wherein the amino can react with rich epoxy groups and carboxyl groups on the surface of graphene oxide, so that the graphene can be uniformly dispersed in water, and the defect that the graphene oxide is prone to surface aggregation after being applied to a water-based epoxy zinc-rich coating, so that the self-corrosion resistance cannot be exerted is overcome.
Preferably, the mass ratio of the L-lysine to the L-tryptophan to the graphene oxide is (1-5): (1-5): 3, and preferably, (2-4): (2-4): 3.
When the mass ratio of the L-lysine to the L-tryptophan to the graphene oxide is specifically selected to be within the range of the above ratio, the coating has more remarkable mechanical property and corrosion resistance when being used for preparing a coating, and the range of (2-4): 3 is the range with the best effect.
The term (1-5) means that specific values can be selected from 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 or 5, and other specific values in the range of values can be selected, and are not described herein again.
Preferably, the sheet diameter of the graphene oxide is 3-16 μm, such as 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, and the like, and other specific values in the numerical range can be selected, which is not described herein again.
In a second aspect, the present invention provides a method for preparing an amino acid-grafted graphene oxide filler according to the first aspect, wherein the method comprises the following steps:
(1) Mixing L-lysine, L-tryptophan, sodium hydroxide and water, stirring for dispersion, and performing ultrasonic water bath to obtain a compound amino acid solution;
(2) Mixing the composite amino acid solution obtained in the step (1) with graphene oxide, stirring and dispersing, performing ultrasonic water bath, and stirring and dispersing again to obtain a graphene oxide dispersion liquid;
(3) And (3) filtering, washing and drying the graphene oxide dispersion liquid obtained in the step (2) to obtain the amino acid grafted graphene oxide filler.
The preparation process of the amino acid grafted graphene oxide filler is relatively simple and easy to operate, and is very suitable for large-scale industrial production.
Preferably, in step (1), the mass ratio of L-lysine, sodium hydroxide to water is (2-10): (1-5): 5, such as 2.
Preferably, the stirring dispersion of step (1) is carried out at 15-30 deg.C (e.g., 15 deg.C, 18 deg.C, 20 deg.C, 22 deg.C, 25 deg.C, 28 deg.C, 30 deg.C, etc.) for 0.5-2h (e.g., 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, 2h, etc.).
Preferably, the ultrasonic water bath of step (1) is carried out at 15-30 ℃ (e.g., 15 ℃, 18 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃, etc.) for 0.5-2h (e.g., 0.5h, 0.8h, 1h, 1.2h, 1.5h, 1.8h, 2h, etc.).
Preferably, the stirring dispersion of step (2) is carried out at 50-70 deg.C (e.g., 50 deg.C, 55 deg.C, 60 deg.C, 62 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, etc.) for 1-3h (e.g., 1h, 1.5h, 2h, 2.5h, 3h, etc.).
Preferably, the ultrasonic water bath of step (2) is carried out at 50-70 deg.C (e.g., 50 deg.C, 55 deg.C, 60 deg.C, 62 deg.C, 65 deg.C, 68 deg.C, 70 deg.C, etc.) for 1-3h (e.g., 1h, 1.5h, 2h, 2.5h, 3h, etc.).
Preferably, the further stirring and dispersing of step (2) is carried out at 20-30 deg.C (e.g. 20 deg.C, 22 deg.C, 25 deg.C, 28 deg.C, 30 deg.C, etc.) for 20-30h (e.g. 20h, 22h, 25h, 28h, 30h, etc.).
Other specific point values within the above numerical ranges can be selected, and are not described in detail herein.
The stirring dispersion or ultrasonic water bath in the steps needs to meet specific temperature and time conditions, and the advantages of the product in mechanical property and corrosion resistance can be maximized under the organic cooperation of the process parameters.
Preferably, the filtration in step (3) is performed by using a 0.22 μm polytetrafluoroethylene membrane filter.
Preferably, the washing in step (3) is performed by using water and absolute ethyl alcohol in sequence.
Preferably, the drying in the freeze drying oven in the step (3) is performed for 25 to 50 hours, for example, 25 hours, 28 hours, 30 hours, 32 hours, 35 hours, 38 hours, 40 hours, 45 hours, 50 hours, and the like, and other specific values in the value range can be selected, which is not described in detail herein.
In a third aspect, the present invention provides a waterborne epoxy zinc-rich coating, comprising: zinc powder, water-based epoxy resin, a water-based epoxy curing agent, propylene glycol methyl ether, talcum powder, the amino acid grafted graphene oxide filler, a modifier, an auxiliary agent and water, wherein the amino acid grafted graphene oxide filler is prepared from the following raw materials; the modifier is any one or the combination of at least two of polyvinyl alcohol, carboxymethyl cellulose, polyanion cellulose or hydroxymethyl cellulose.
The amino acid grafted graphene oxide filler is added into the water-based epoxy zinc-rich paint, and is modified together with a modifier, so that the amino acid grafted graphene oxide filler and the modifier have a remarkable synergistic effect in the aspects of improving the mechanical property and the corrosion resistance of the paint.
Preferably, the water-based epoxy zinc-rich paint comprises the following components in percentage by mass: 30-60% of zinc powder, 20-30% of water-based epoxy resin, 8-12% of water-based epoxy curing agent, 3-6% of propylene glycol methyl ether, 1-5% of talcum powder, 0.4-8% of amino acid grafted graphene oxide filler, 0.1-2% of modifier, 0.6-6% of assistant and 5-30% of water.
The zinc powder can be 30%, 40%, 45%, 50%, 55%, 60% and the like in percentage by mass.
The mass percentage of the water-based epoxy resin can be 20%, 22%, 23%, 25%, 26%, 28%, 29%, 30% and the like.
The mass percentage of the water-based epoxy curing agent can be 8%, 9%, 10%, 11%, 12% and the like.
The propylene glycol methyl ether can be 3%, 4%, 5%, 5.5%, 6% and the like in percentage by mass.
The mass percentage of the talcum powder can be 1%, 2%, 3%, 4%, 5% and the like.
The mass percentage of the amino acid-grafted graphene oxide filler according to the first aspect may be 0.4%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 3%, 4%, 5%, 8%, etc.
The mass percentage of the modifier can be 0.1%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2% and the like.
The mass percentage of the auxiliary agent can be 0.6%, 1%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6% and the like.
The water may be present in an amount of 5%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, etc. by mass.
Other specific point values within the above numerical ranges can be selected, and are not described in detail herein.
Preferably, the auxiliary agent comprises any one or a combination of at least two of a thixotropic agent, a film forming auxiliary agent, a dispersing agent, an antifoaming agent, an anti-flash rust agent or a wetting agent; the combination of at least two of the thixotropic agent and the film-forming assistant, the combination of the dispersant and the defoamer, the combination of the flash rust inhibitor and the wetting agent, and the like can be selected in any combination mode, and the details are not repeated.
Preferably, the epoxy equivalent of the aqueous epoxy resin is 400-800, such as 400, 450, 500, 550, 600, 650, 700, 750, 800, etc., and other specific values within the value range can be selected, which is not described herein again.
Preferably, the active hydrogen equivalent weight of the aqueous epoxy curing agent is 200-320, such as 200, 220, 250, 270, 300, 310, 320, etc., and other specific values within the value range can be selected, which is not repeated herein.
Preferably, the zinc powder has a particle size of 3 to 7 μm, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, etc., and is spherical or flaky in morphology.
In a fourth aspect, the present invention provides a method for preparing the water-based epoxy zinc-rich paint according to the third aspect, wherein the method comprises the following steps:
(1) Mixing and stirring the waterborne epoxy resin and the waterborne epoxy curing agent to obtain a mixture A;
(2) Mixing and stirring the mixture A and propylene glycol methyl ether to obtain a mixture B;
(3) Mixing and stirring the mixture B with an auxiliary agent, zinc powder, talcum powder and a modifier to obtain a mixture C;
(4) And mixing and stirring the mixture C, the amino acid grafted graphene oxide filler and water, and adjusting the viscosity of the coating to obtain the waterborne epoxy zinc-rich coating.
The preparation process of the waterborne epoxy zinc-rich coating is relatively simple and easy to operate, and is very suitable for large-scale industrial production.
Preferably, the mixing and stirring of step (1) is carried out at 500-600r/min (e.g., 500r/min, 520r/min, 550r/min, 580r/min, 600r/min, etc.) for 5-15min (e.g., 5min, 8min, 10min, 12min, 15min, etc.).
Preferably, the mixing and stirring of step (2) is carried out at 500-600r/min (e.g., 500r/min, 520r/min, 550r/min, 580r/min, 600r/min, etc.) for 10-20min (e.g., 10min, 12min, 15min, 18min, 20min, etc.).
Preferably, the mixing and stirring in step (3) is carried out at 850-900r/min (e.g., 850r/min, 860r/min, 870r/min, 880r/min, 900r/min, etc.) for 30-40min (e.g., 30min, 32min, 35min, 38min, 40min, etc.).
Preferably, the mixing and stirring of step (4) is carried out at 500-600r/min (e.g., 500r/min, 520r/min, 550r/min, 580r/min, 600r/min, etc.) for 15-25min (e.g., 15min, 17min, 20min, 22min, 25min, etc.).
In a fifth aspect, the invention provides an application of the amino acid grafted graphene oxide filler according to the first aspect and the waterborne epoxy zinc-rich coating according to the third aspect in preparing an anticorrosive coating.
Compared with the prior art, the invention has the following beneficial effects:
the amino acid grafted graphene oxide filler is creatively grafted and modified with L-lysine and L-tryptophan, and has better mechanical property and corrosion resistance than the single L-lysine or single L-tryptophan grafted and modified graphene oxide when being applied to the coating. The invention finds that when L-lysine and L-tryptophan are used for grafting and modifying graphene oxide simultaneously, the effect of improving the mechanical property and the corrosion resistance of the coating is better than that when the graphene oxide is modified by single L-lysine or L-tryptophan, and the two have synergistic interaction.
The graphene oxide is used as a single-layer material stripped from the graphite oxide, can stably exist in an aqueous solution and a polar solvent due to the introduction of a large number of oxygen-containing groups on the surface and the edge, can still maintain the layered structure of the graphite after oxidation treatment, can be orderly and densely stacked in a coating to form a powerful protective layer, and has an ultra-large specific surface area, so that the path of an external corrosive medium penetrating to the surface of a steel structure is complicated, and the impermeability of the coating is improved. A plurality of oxygen-based functional groups are introduced into the graphene single sheet by the graphene oxide, so that the compatibility with the water-based paint is improved, and the stability of the paint is further improved.
The L-lysine and the L-tryptophan both contain amino and carboxyl functional groups, wherein the amino can react with rich epoxy groups and carboxyl groups on the surface of the graphene oxide, so that the graphene can be uniformly dispersed in water, and the defect that the graphene oxide is prone to surface aggregation after being applied to a water-based epoxy zinc-rich coating and cannot exert the self-corrosion resistance is overcome.
Drawings
FIG. 1 is an electron micrograph (12000X) of the amino acid-grafted graphene oxide filler obtained in example 1.
FIG. 2 is an electron micrograph (6000X) of the amino acid-grafted graphene oxide filler prepared in example 1.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
The information on the raw materials involved in the following examples, comparative examples, application examples or comparative application examples is as follows:
graphene oxide dispersion, purchased from Nanjing Xiancheng nanomaterial science and technology Limited;
waterborne epoxy resin, F0704, available from Jitian chemical Co., ltd, shenzhen city;
the waterborne epoxy curing agent F0704 is purchased from Jitian chemical industry Co., ltd, shenzhen city;
thixotropic agent, PAMID D770, available from core chemistry;
the film-forming aid, J1901, is purchased from Jitian chemical Co., ltd, shenzhen city;
a dispersant, J1803, available from Jitian chemical Co., ltd, shenzhen city;
defoamer, J0401, available from shenzhen ji tian chemical ltd;
anti-flash rust agent, FA179, available from Yongfeng chemical Co., ltd, zhongshan City;
a wetting agent, J1701, available from Jitian chemical Co., ltd, shenzhen;
propylene glycol methyl ether, available from Shanghai Aladdin Biotechnology, inc.;
talcum powder of 1250 meshes, purchased from Yongfeng chemical Co., ltd, zhongshan City;
l-tryptophan, national pharmaceutical group chemical reagents, inc.;
l-lysine, national chemical group chemical reagents, inc.;
sodium hydroxide, national chemical group chemical agents ltd;
polyvinyl alcohol, model number cx336, san dong, jun xin chemical ltd.
Example 1
The embodiment provides an amino acid grafted graphene oxide filler, and a preparation method thereof is as follows:
(1) Mixing 3g of L-lysine, 3g of L-tryptophan, 2g of sodium hydroxide and 82g of water, stirring and dispersing at 25 ℃ for 1h, and performing ultrasonic water bath at 25 ℃ for 1.5h to obtain a compound amino acid solution;
(2) Mixing the composite amino acid solution obtained in the step (1) with 3g of graphene oxide powder, stirring and dispersing at 60 ℃ for 2h, then carrying out ultrasonic water bath at 60 ℃ for 1.5h, and stirring and dispersing at 25 ℃ for 24h again to obtain a graphene oxide dispersion liquid;
(3) And (3) filtering the graphene oxide dispersion liquid obtained in the step (2) by using a polytetrafluoroethylene suction filtration membrane with the diameter of 0.22 mu m, washing by using water and absolute ethyl alcohol in sequence, and drying in a freeze drying oven for 30h to obtain the amino acid grafted graphene oxide filler, wherein electron micrographs of the graphene oxide filler are shown in FIG. 1 (12000X) and FIG. 2 (6000X).
Example 2
The embodiment provides an amino acid grafted graphene oxide filler, and a preparation method thereof is as follows:
(1) Mixing 2g of L-lysine, 4g of L-tryptophan, 3g of sodium hydroxide and 79g of water, stirring and dispersing at 15 ℃ for 2h, and performing ultrasonic water bath at 15 ℃ for 2h to obtain a compound amino acid solution;
(2) Mixing the composite amino acid solution obtained in the step (1) with 3g of graphene oxide powder, stirring and dispersing at 50 ℃ for 3h, then carrying out ultrasonic water bath at 50 ℃ for 3h, and stirring and dispersing at 20 ℃ for 30h again to obtain a graphene oxide dispersion liquid;
(3) And (3) filtering the graphene oxide dispersion liquid obtained in the step (2) by using a polytetrafluoroethylene suction filtration membrane with the diameter of 0.22 mu m, washing by using water and absolute ethyl alcohol in sequence, and drying in a freeze drying oven for 30h to obtain the amino acid grafted graphene oxide filler.
Example 3
The embodiment provides an amino acid grafted graphene oxide filler, and a preparation method thereof is as follows:
(1) Mixing 4g of L-lysine, 2g of L-tryptophan, 4g of sodium hydroxide and 76g of water, stirring and dispersing for 0.5h at 30 ℃, and then carrying out ultrasonic water bath for 0.5h at 30 ℃ to obtain a compound amino acid solution;
(2) Mixing the composite amino acid solution obtained in the step (1) with 3g of graphene oxide powder, stirring and dispersing at 70 ℃ for 1h, then carrying out ultrasonic water bath at 70 ℃ for 1h, and stirring and dispersing at 30 ℃ for 20h again to obtain a graphene oxide dispersion liquid;
(3) And (3) filtering the graphene oxide dispersion liquid obtained in the step (2) by using a polytetrafluoroethylene suction filtration membrane with the diameter of 0.22 mu m, washing by using water and absolute ethyl alcohol in sequence, and drying in a freeze drying oven for 30h to obtain the amino acid grafted graphene oxide filler.
Example 4
This example provides an amino acid-grafted graphene oxide filler, and the preparation method thereof is different from that of example 1 only in that the mass of L-lysine in step (1) is 5g, the mass of L-tryptophan is 1g, and other conditions are kept unchanged.
Example 5
This example provides an amino acid-grafted graphene oxide filler, and the preparation method thereof is different from that of example 1 only in that the mass of L-lysine in step (1) is 1g, the mass of L-tryptophan is 5g, and other conditions are kept unchanged.
Comparative example 1
The comparative example provides an amino acid-grafted graphene oxide filler, and the preparation method of the filler is different from that of example 1 only in that L-lysine is not contained in step (1), the mass of L-tryptophan is 6g, and other conditions are kept unchanged.
Comparative example 2
The present comparative example provides an amino acid-grafted graphene oxide filler, and the preparation method thereof is different from example 1 only in that L-tryptophan is not contained in step (1), the mass of L-lysine is 6g, and other conditions are maintained.
Comparative example 3
The present comparative example provides a graphene oxide filler without graft modification.
Application example 1
The application example provides a water-based epoxy zinc-rich paint which comprises the following components in percentage by mass: 60g of zinc powder, 44g of water-based epoxy resin, 20g of water-based epoxy curing agent, 10g of propylene glycol methyl ether, 5g of talcum powder, 5g of amino acid grafted graphene oxide filler prepared in example 1, 3g of polyvinyl alcohol, 1.5g of thixotropic agent, 1.5g of dispersing agent, 1.5g of film-forming additive, 1.5g of defoaming agent, 0.5g of flash rust inhibitor, 0.75g of wetting agent and 20g of water.
The preparation method comprises the following steps:
(1) Mixing and stirring the waterborne epoxy resin and the waterborne epoxy curing agent at 550r/min for 10min to obtain a mixture A;
(2) Mixing the mixture A and propylene glycol methyl ether at 550r/min, and stirring for 15min to obtain a mixture B;
(3) Mixing and stirring the mixture B, various additives, zinc powder, talcum powder and polyvinyl alcohol for 35min at 850r/min to obtain a mixture C;
(4) And mixing and stirring the mixture C and the aqueous dispersion of the amino acid grafted graphene oxide filler at 550r/min for 20min, and adjusting the viscosity of the coating to three cups for 12 seconds to obtain the water-based epoxy zinc-rich coating.
Application examples 2 to 5
The present application example provides four waterborne epoxy zinc-rich coatings, the components of which are different from those of application example 1 only in that the amino acid-grafted graphene oxide filler prepared in example 1 is replaced by the amino acid-grafted graphene oxide filler prepared in examples 2 to 5, and other conditions are kept unchanged.
Comparative application examples 1 to 3
The present application example provides three aqueous epoxy zinc-rich coatings, the compositions of which differ from those of application example 1 only in that the amino acid-grafted graphene oxide filler prepared in example 1 was replaced with the graphene oxide fillers prepared in comparative examples 1 to 3, and the other conditions were kept the same.
Comparative application example 4
The application example provides a water-based epoxy zinc-rich paint, which is only different from the application example 1 in that polyvinyl alcohol is not contained in the components, 8g of the amino acid grafted graphene oxide filler prepared in the example 1 is contained, and other conditions are kept unchanged.
Comparative application example 5
The application example provides a water-based epoxy zinc-rich paint, which is only different from the application example 1 in that the paint does not contain the amino acid grafted graphene oxide filler prepared in the example 1, the polyvinyl alcohol is 8g, and other conditions are kept unchanged.
Comparative application example 6
The present application example provides a water-based epoxy zinc-rich paint, which has a composition different from that of application example 1 only in that the amino acid grafted graphene oxide filler prepared in example 1 is not contained, and other conditions are kept unchanged.
And (4) performance testing:
the waterborne epoxy zinc-rich paint prepared in the application examples 1-5 and the comparative application examples 1-6 is coated on the surface of a sandblasted steel plate substrate to obtain an anticorrosive coating with the thickness of 110 mu m. The following performance tests were carried out on the coatings according to the industry standard graphene zinc powder coatings (HG/T5573-2019):
the nonvolatile content is carried out according to the regulation of GB/T1725-2007.
Impact resistance was determined according to GB/T1732-2020.
The adhesion force is carried out according to the regulation of GB/T5210-2006.
The neutral salt spray test is carried out according to the regulations of GB/T1771-2007 and GB/T1766-2008.
The results are shown in table 1 (3 replicates for each group, averaged):
TABLE 1
As can be seen from the data in Table 1: when the amino acid grafted graphene oxide filler disclosed by the invention is applied to a coating, the mechanical property and the corrosion resistance of the amino acid grafted graphene oxide filler are better than those of single L-lysine or single L-tryptophan grafted modified graphene oxide, and when the amino acid grafted graphene oxide filler is used together with a modifier, the amino acid grafted graphene oxide filler and the modifier have a remarkable synergistic effect in the aspect of improving the mechanical property and the corrosion resistance of the coating.
The applicant states that the present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (25)
1. The waterborne epoxy zinc-rich paint is characterized by comprising the following components in parts by weight: zinc powder, water-based epoxy resin, a water-based epoxy curing agent, propylene glycol methyl ether, talcum powder, an amino acid grafted graphene oxide filler, a modifier, an auxiliary agent and water;
the modifier is any one or the combination of at least two of polyvinyl alcohol, carboxymethyl cellulose, polyanion cellulose or hydroxymethyl cellulose; the preparation raw materials of the amino acid grafted graphene oxide filler comprise: l-lysine, L-tryptophan and graphene oxide.
2. The aqueous epoxy zinc-rich paint of claim 1, wherein the mass ratio of the L-lysine, the L-tryptophan and the graphene oxide is (1-5): (1-5): 3.
3. The aqueous epoxy zinc-rich paint of claim 1, wherein the mass ratio of the L-lysine, the L-tryptophan and the graphene oxide is (2-4): (2-4): 3.
4. The aqueous epoxy zinc-rich paint according to claim 1, wherein the graphene oxide has a flake diameter of 3 to 16 μm.
5. The aqueous epoxy zinc-rich coating of claim 1, wherein the preparation method of the amino acid grafted graphene oxide filler comprises the following steps:
(1) Mixing L-lysine, L-tryptophan, sodium hydroxide and water, stirring for dispersion, and performing ultrasonic water bath to obtain a compound amino acid solution;
(2) Mixing the composite amino acid solution obtained in the step (1) with graphene oxide, stirring and dispersing, performing ultrasonic water bath, and stirring and dispersing again to obtain a graphene oxide dispersion liquid;
(3) And (3) filtering, washing and drying the graphene oxide dispersion liquid obtained in the step (2) to obtain the amino acid grafted graphene oxide filler.
6. The waterborne epoxy zinc-rich paint of claim 5, wherein the mass ratio of L-lysine, sodium hydroxide and water in the step (1) is (6-15): (2-5): (75-90).
7. The waterborne epoxy zinc-rich paint of claim 5, wherein the stirring dispersion of step (1) is performed at 15-30 ℃ for 0.5-2h.
8. The waterborne epoxy zinc-rich paint of claim 5, wherein the ultrasonic water bath of step (1) is carried out at 15-30 ℃ for 0.5-2h.
9. The waterborne epoxy zinc-rich paint of claim 5, wherein the stirring dispersion of step (2) is performed at 50-70 ℃ for 1-3h.
10. The waterborne epoxy zinc-rich paint of claim 5, wherein the ultrasonic water bath of step (2) is performed at 50-70 ℃ for 1-3h.
11. The waterborne epoxy zinc-rich coating of claim 5, wherein the further stirring and dispersing of step (2) is performed at 20-30 ℃ for 20-30h.
12. The aqueous epoxy zinc-rich paint as claimed in claim 5, wherein the filtration in step (3) is performed by using a 0.22 μm polytetrafluoroethylene membrane filter.
13. The aqueous epoxy zinc-rich paint of claim 5, wherein the washing in step (3) is performed by using water and absolute ethyl alcohol in sequence.
14. The waterborne epoxy zinc-rich paint of claim 5, wherein the drying in step (3) is performed in a freeze drying oven for 25-50h.
15. The aqueous epoxy zinc-rich paint according to claim 1, wherein the aqueous epoxy zinc-rich paint comprises the following components in percentage by mass: 30-60% of zinc powder, 20-30% of water-based epoxy resin, 8-12% of water-based epoxy curing agent, 3-6% of propylene glycol methyl ether, 1-5% of talcum powder, 0.4-8% of amino acid grafted graphene oxide filler, 0.1-2% of modifier, 0.6-6% of assistant and 5-30% of water.
16. The aqueous epoxy zinc rich coating of claim 1 wherein the adjuvant comprises any one or a combination of at least two of a thixotropic agent, a film forming adjuvant, a dispersant, an anti-foaming agent, an anti-flash rust agent, or a wetting agent.
17. The aqueous epoxy zinc rich coating of claim 1 wherein the aqueous epoxy resin has an epoxy equivalent weight of 400 to 800.
18. The waterborne epoxy zinc rich coating of claim 1, wherein the waterborne epoxy curing agent has an active hydrogen equivalent weight of from 200 to 320.
19. The aqueous epoxy zinc-rich paint as claimed in claim 1, wherein the zinc powder has a particle size of 3-7 μm and a spherical or flaky morphology.
20. The method of preparing the aqueous epoxy zinc rich coating of any one of claims 1-19, comprising the steps of:
(1) Mixing and stirring the waterborne epoxy resin and the waterborne epoxy curing agent to obtain a mixture A;
(2) Mixing and stirring the mixture A and propylene glycol methyl ether to obtain a mixture B;
(3) Mixing and stirring the mixture B with an auxiliary agent, zinc powder, talcum powder and a modifier to obtain a mixture C;
(4) And mixing and stirring the mixture C, the amino acid grafted graphene oxide filler and water, and adjusting the viscosity of the coating to obtain the water-based epoxy zinc-rich coating.
21. The method for preparing the waterborne epoxy zinc-rich paint as claimed in claim 20, wherein the mixing and stirring in the step (1) are carried out at 500-600r/min for 5-15min.
22. The method for preparing the water-based epoxy zinc-rich paint as claimed in claim 20, wherein the mixing and stirring in the step (2) are carried out at 500-600r/min for 10-20min.
23. The method for preparing the waterborne epoxy zinc-rich paint as claimed in claim 20, wherein the mixing and stirring in the step (3) are carried out at 850-900r/min for 30-40min.
24. The method for preparing the waterborne epoxy zinc-rich paint as claimed in claim 20, wherein the mixing and stirring in the step (4) are carried out at 500-600r/min for 15-25min.
25. Use of the aqueous epoxy zinc-rich coating according to any one of claims 1 to 19 for the preparation of an anti-corrosive coating.
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