CN115627094A - Functional anticorrosive filler capable of being stably dispersed in water phase and preparation method and application thereof - Google Patents
Functional anticorrosive filler capable of being stably dispersed in water phase and preparation method and application thereof Download PDFInfo
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- CN115627094A CN115627094A CN202211177672.0A CN202211177672A CN115627094A CN 115627094 A CN115627094 A CN 115627094A CN 202211177672 A CN202211177672 A CN 202211177672A CN 115627094 A CN115627094 A CN 115627094A
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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
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- 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
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
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Abstract
The invention discloses a functional anticorrosive filler capable of being stably dispersed in a water phase, and a preparation method and application thereof, wherein the functional anticorrosive filler consists of thiazole grafted graphene oxide, carboxylated aniline trimer, naOH and deionized water in a mass ratio of 18-22: 8-12: 2-4: 95-105. The functional anticorrosive filler can be stored for a long time without sedimentation, water is used as a dispersing agent, the graphene content in the slurry can be adjusted according to different conditions, the whole process is green and environment-friendly and pollution-free, and the resin and the slurry are weighed according to the addition amount in proportion during use, so that the functional anticorrosive filler is efficient and convenient.
Description
Technical Field
The invention belongs to the technical field of water-based anticorrosive materials, and particularly relates to a functional anticorrosive filler capable of being stably dispersed in a water phase, and a preparation method and application thereof.
Background
Organic resin is widely applied to the field of metal corrosion prevention due to excellent mechanical properties, higher compactness and certain acid and alkali resistance. The traditional anticorrosive paint mainly takes oleoresin as matrix resin, and can generate a plurality of Volatile Organic Compounds (VOCs) in the preparation and construction processes, thereby not only polluting the natural environment, but also seriously harming the health of human beings.
In recent years, with the advent of national environmental protection policies and the increasing awareness of environmental protection, there is an increasing call for replacing conventional oil-based coatings with water-based coatings. The water-based paint is a paint taking water as a solvent or a dispersion medium, and compared with the traditional oil-based paint, the water-based paint hardly involves the use of an organic solvent in the preparation and construction processes, so that the water-based paint is very green and environment-friendly. However, when the water-based paint is applied to the anticorrosion field, the anticorrosion performance cannot reach the effect of the same type of oil-based paint. The problem can be well improved by adding some functional anticorrosion additives, and the commonly used functional anticorrosion additives mainly comprise some two-dimensional materials, corrosion inhibitors, conductive polymers and the like.
Graphene as a two-dimensional material has excellent physical shielding performance and is the best choice as a functional anticorrosive additive. However, the dispersibility problem of the graphene material in the aqueous resin limits the use thereof. How to modify graphene so as to realize stable dispersion in an aqueous resin is an urgent problem to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a functional anticorrosive filler capable of being stably dispersed in a water phase.
Another object of the present invention is to provide a method for preparing the above functional corrosion inhibiting filler which can be stably dispersed in an aqueous phase.
It is still another object of the present invention to provide the use of the above functional corrosion inhibiting filler which is stably dispersible in an aqueous phase.
The technical scheme of the invention is as follows:
a functional anticorrosion filler capable of being stably dispersed in a water phase is composed of thiazole grafted graphene oxide, carboxylated aniline tripolymer, naOH and deionized water in a mass ratio of 18-22: 8-12: 2-4: 95-105, wherein,
the thiazole grafted graphene oxide is prepared by reacting graphene oxide, 2-aminothiazole, dicyclohexylcarbodiimide, 1-hydroxybenzotriazole and DMF (dimethyl formamide);
the carboxylated aniline trimer is prepared by reacting aniline trimer, succinic anhydride and tetrahydrofuran.
In a preferred embodiment of the present invention, the mass ratio of the graphene oxide, the 2-aminothiazole, the dicyclohexylcarbodiimide and the 1-hydroxybenzotriazole is 8-12: 15-17.
Further preferably, the mass ratio of the graphene oxide, the 2-aminothiazole, the dicyclohexylcarbodiimide and the 1-hydroxybenzotriazole is 10: 16.
In a preferred embodiment of the invention, the molar ratio of aniline trimer to succinic anhydride is 1: 2.1-2.3.
Further preferably, the molar ratio of aniline trimer to succinic anhydride is 1: 2.2.
In a preferred embodiment of the present invention, the thiazole-grafted graphene oxide, the carboxylated aniline trimer, naOH and deionized water are in a ratio of 20: 10: 3: 100.
The preparation method of the functional anticorrosive filler comprises the following steps:
(1) Mixing graphene oxide, 2-aminothiazole, dicyclohexylcarbodiimide, 1-hydroxybenzotriazole and DMF, performing ultrasonic dispersion for 1h, stirring at room temperature for reaction for 24h, and performing centrifugal washing to obtain the thiazole grafted graphene oxide;
(2) Mixing aniline trimer, succinic anhydride and tetrahydrofuran, reacting at 45 ℃ for 4 hours, and performing precipitation and filtration by using petroleum ether to obtain carboxylated aniline trimer;
(3) And mixing the thiazole grafted graphene oxide, the carboxylated aniline trimer, naOH and deionized water, and performing ultrasonic treatment for 1h at room temperature to obtain the functional anticorrosive filler.
The functional anticorrosive filler is applied to the preparation of the aqueous anticorrosive organic resin coating composition.
An aqueous anticorrosion organic resin coating composition contains an aqueous organic resin material and the functional anticorrosion filler.
In a preferred embodiment of the present invention, the aqueous organic resin material includes an aqueous epoxy resin, a one-part aqueous polyurethane, and an aqueous polyester resin.
The invention has the beneficial effects that:
1. the functional anticorrosive filler has good water dispersibility, can be stably dispersed in most of water-based resins, and has a very wide application prospect.
2. The functional anticorrosive filler can be stored for a long time without sedimentation, the content of graphene in the slurry can be adjusted according to different conditions by using water as a dispersing agent, the whole process is green and environment-friendly, and is free from pollution, and the resin and the slurry are weighed according to the addition amount in proportion when the functional anticorrosive filler is used, so that the functional anticorrosive filler is efficient and convenient.
3. The functional anticorrosive filler has the shielding effect of graphene and the corrosion inhibition capability of a corrosion inhibitor, the graphene has the effect shown in figure 5, the graphene serving as a two-dimensional thin-layer material can be tiled on the surface of a substrate to form a physical protective layer, so that the corrosion medium can be prevented from permeating, the corrosion can be slowed down, and compared with a pure resin coating, the anticorrosive coating prepared by the functional anticorrosive filler has the advantages that the anticorrosive performance is greatly improved, and the service life is longer.
Drawings
FIG. 1 is a graph of the infrared spectra of thiazole before (GO) and after (GO-TZ) grafting, as well as Aniline Trimer (AT) and Carboxylated Aniline Trimer (CAT) in example 1 of the present invention.
FIG. 2 is a 1H Nuclear Magnetic (NMR) spectrum of Aniline Trimer (AT) and Carboxylated Aniline Trimer (CAT) in example 1 of the present invention.
FIG. 3 is a graph of the results of the dispersion of GO-TZ-CAT prepared in example 2 of the present invention in water, wherein GO (a, a 1); GO-TZ (b, b 1); optical photos of the GO-TZ-CAT (c, c 1) dispersion liquid after ultrasonic standing for 0h and 48h (the key of the modified graphene composite material in the water-based epoxy resin for exerting excellent performance lies in good dispersibility in water, so that the water dispersibility of the graphene composite material before and after modification is respectively researched, a small amount of GO, GO-TZ and GO-TZ-CAT are respectively dispersed in deionized water after ultrasonic standing for 48h, and whether the GO-TZ and GO-TZ-CAT precipitate or not is observed.
FIG. 4 is a graph showing the corrosion prevention effect of a waterborne epoxy coating prepared from a functional anticorrosive filler (GO-TZ-CAT) in example 3 of the present invention.
FIG. 5 is an electrochemical diagram of shielding effect of graphene and corrosion inhibition ability of corrosion inhibitor.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1 preparation of thiazole-grafted graphene oxide and carboxylated aniline trimer
The formulation of this example is as follows:
(1) 0.1g of graphene oxide was dispersed in 10mL of DMF, and after 2h of sonication at room temperature, 0.1g of NaOH was added, and stirred at room temperature for 1h, and NaOH was added to open the carboxylic acid groups on GO. Subsequently, 0.1g of 2-Aminothiazole (ATZ), 0.16g of HOBt and 0.2g of DCC were weighed out separately and added to the mixture, and stirring was continued at room temperature for 24 hours. After the reaction is finished, the mixed system is diluted and centrifuged by DMF, DMF and ethanol are sequentially used for washing for 2 times respectively, and finally deionized water is used for washing for 1 time. And (3) freeze-drying the obtained precipitate for 24 hours to obtain the thiazole grafted graphene oxide (GO-TZ, as shown in figures 1 to 2).
(2) 145mg of AT and 123mg of succinic anhydride were weighed out and dissolved in 40mL of Tetrahydrofuran (THF), respectively, and the reaction was stirred AT 45 ℃ under reflux for 5 hours. After the reaction is finished, the mixed system is slowly added into 200mL of petroleum ether while stirring, and after precipitation, suction filtration is carried out by using a Buchner funnel. Dissolving the obtained precipitate with tetrahydrofuran and petroleum ether, precipitating again, and vacuum filtering until the filtrate is clear and transparent. And drying the filter cake in a vacuum oven at 60 ℃ for 24h, and grinding to obtain purple black powder, namely carboxylated aniline trimer (CAT, as shown in figures 1 to 2).
Example 2 preparation of functional anti-corrosive Filler
The formulation of this example is as follows:
weighing 20mg of GO-TZ into a container, adding 100mL of deionized water, performing ultrasonic dispersion, adding 10mg of CAT, and continuing performing ultrasonic treatment for 1h to obtain the functional anticorrosive filler (GO-TZ-CAT) shown in figure 3, which can be stored for a long time without sedimentation. In FIG. 3, (a, a 1), (b, b 1), (c, c 1) show optical photographs of dispersions of GO, GO-TZ-CAT after ultrasonic standing for 0h and 48h, respectively.
Example 3:
the formulation of this example is as follows:
weighing 20g of waterborne epoxy resin, adding 10mL of functional anticorrosive filler, a proper amount of waterborne auxiliary agent and 6g of titanium dioxide into a container, stirring and dispersing at a high speed for 20min, adjusting the viscosity to be proper by using water to obtain a component A of the functional anticorrosive paint, adding 20g of a component B curing agent, continuing stirring and dispersing for 15min to obtain the final functional anticorrosive paint, coating a steel plate (the specification is 150 x 70 x 1 mm), and testing the mechanical property and the anticorrosive property of an anticorrosive coating after curing.
In order to explore the mechanical properties of the modified composite epoxy system, the adhesion, flexibility, impact resistance, hardness and bending resistance of the composite water-based epoxy coating are respectively tested, and the specific results are shown in table 1.
TABLE 1 physical Properties of epoxy composite anticorrosion coatings
The coated steel sheets were tested according to GB 6458-86. The experiment was performed using the salt spray test item model Q-Lab. The concentration of the sodium chloride solution used in the test is 5%, and the test pressure is determined by a salt spray sedimentation amount test. For preventing among the test process corrosion medium from leading to the fact the influence to the experimental result from the back of test model and inside the side infiltration coating, need carry out the banding to the model before the test, concrete operation is: and sealing the back and the side of the sample plate by using a wide adhesive tape, further sealing the test steel plate by using paraffin and rosin or room temperature curing silicone rubber, and fully curing and drying the test steel plate to be subjected to edge sealing at room temperature. And (3) scratching a part of the test steel plate on the surface of the coating until the part of the test steel plate is in contact with the surface of the steel plate, and placing the test steel plate and the scratched steel plate in a salt spray test box at an inclination angle of 5 degrees with the vertical line. And (3) evaluating the corrosion resistance of the coating by using a timing method, and observing and evaluating the sample plate after 500 hours of salt spray test. Fig. 4 shows the optical morphology of a GO-TZ-CAT composite coating (modified epoxy coating) prepared from a pure water epoxy coating and the functional anticorrosive coating prepared in this example after a neutral salt spray test for 500 hours and a coating with cross damage after a neutral salt spray test for 300 hours. For the undamaged coating, black rust spots appeared on all coating surfaces after 500h neutral salt spray test, since over time the corrosive medium continuously penetrated into the metal interface through defects in the coating surface. The pure water-borne epoxy coating has the largest number of rusts, because the surfactant remaining on the surface of the pure water-borne epoxy resin when cured provides a diffusion path for corrosive media. Compared with the GO-TZ-CAT composite coating, the surface rusty spot of the GO-TZ-CAT composite coating is obviously reduced, and the GO-TZ-CAT is uniformly dispersed in the coating to fill up the defects left when the coating is cured. For the coating after the damage, all coatings showed a noticeable rust mark at the scratch after the 500h salt spray test. But, in contrast, corrosion is more severe near the scratch by the purely aqueous epoxy coating due to penetration of corrosive agents from the scratch into the near-scratch area. For the GO-TZ-CAT composite coating, obvious corrosion does not occur near the scratches of the coating, and the scratches are covered by dense rust, because the GO-TZ-CAT filler is uniformly dispersed in the coating, thiazole groups and carboxylated aniline trimer on the filler have corrosion inhibition capacity, and can be complexed with iron ions to form dense rust to cover a damaged area, thereby slowing down the corrosion rate.
Example 4:
the formulation of this example is as follows:
weighing 20g of single-component waterborne polyurethane, adding the single-component waterborne polyurethane into a container, adding 10mL of functional anticorrosive filler, a proper amount of water-based auxiliary agent and 6g of titanium dioxide, stirring and dispersing for 20min at a high speed, adjusting the viscosity to be proper by using water to obtain the functional anticorrosive coating, brushing a steel plate (the specification is 150 x 70 x 1 mm), and carrying out an anticorrosive performance test on an anticorrosive coating after curing (the same as example 3).
Example 5:
the formulation of this example is as follows:
weighing 20g of water-based polyester resin, adding 10mL of functional anticorrosive filler, a proper amount of water-based auxiliary agent and 6g of titanium dioxide into a container, stirring and dispersing for 20min at a high speed, adjusting the viscosity to be proper by using water to obtain the functional anticorrosive paint, brushing a steel plate (the specification is 150 x 70 x 1 mm), and carrying out an anticorrosive performance test on an anticorrosive coating after curing (the same as example 3).
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (10)
1. A functional anticorrosive filler capable of being stably dispersed in a water phase is characterized in that: consists of thiazole grafted graphene oxide, carboxylated aniline tripolymer, naOH and deionized water in a mass ratio of 18-22: 8-12: 2-4: 95-105, wherein,
the thiazole grafted graphene oxide is prepared by reacting graphene oxide, 2-aminothiazole, dicyclohexylcarbodiimide, 1-hydroxybenzotriazole and DMF (dimethyl formamide);
the carboxylated aniline trimer is prepared by reacting aniline trimer, succinic anhydride and tetrahydrofuran.
2. The functional corrosion inhibiting filler of claim 1, wherein: the mass ratio of the graphene oxide, the 2-aminothiazole, the dicyclohexylcarbodiimide and the 1-hydroxybenzotriazole is 8-12: 15-17.
3. The functional corrosion inhibiting filler of claim 2, wherein: the mass ratio of the graphene oxide to the 2-aminothiazole to the dicyclohexylcarbodiimide to the 1-hydroxybenzotriazole is 10: 16.
4. The functional corrosion inhibiting filler of claim 1, wherein: the molar ratio of the aniline tripolymer to the succinic anhydride is 1: 2.1-2.3.
5. The functional corrosion inhibiting filler of claim 4, wherein: the molar ratio of the aniline trimer to the succinic anhydride is 1: 2.2.
6. The functional anticorrosive filler according to any one of claims 1 to 5, characterized in that: the ratio of thiazole grafted graphene oxide to carboxylated aniline trimer to NaOH to deionized water is 20: 10: 3: 100.
7. The method for preparing a functional anticorrosive filler according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) Mixing graphene oxide, 2-aminothiazole, dicyclohexylcarbodiimide, 1-hydroxybenzotriazole and DMF, performing ultrasonic dispersion for 1h, stirring at room temperature for reaction for 24h, and performing centrifugal washing to obtain the thiazole grafted graphene oxide;
(2) Mixing aniline trimer, succinic anhydride and tetrahydrofuran, reacting at 45 ℃ for 4 hours, and performing precipitation and filtration by using petroleum ether to obtain carboxylated aniline trimer;
(3) And mixing the thiazole grafted graphene oxide, the carboxylated aniline trimer, naOH and deionized water, and performing ultrasonic treatment for 1h at room temperature to obtain the functional anticorrosive filler.
8. Use of the functional anticorrosive filler according to any one of claims 1 to 6 for the preparation of an aqueous anticorrosive organic resin coating composition.
9. An aqueous anticorrosion organic resin coating composition, which is characterized in that: containing an aqueous organic resin material and the functional anticorrosive filler according to any one of claims 1 to 6.
10. An aqueous anticorrosive organic resin coating composition according to claim 9, wherein: the water-based organic resin material comprises water-based epoxy resin, single-component water-based polyurethane and water-based polyester resin.
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| CN117820942A (en) * | 2024-03-04 | 2024-04-05 | 成都虹润制漆有限公司 | Bottom, middle and surface composite coating for railway bridge steel structure and preparation method thereof |
| CN117866470A (en) * | 2024-03-04 | 2024-04-12 | 成都虹润制漆有限公司 | Modified composite coating for railway bridge steel structure and preparation method thereof |
| CN117820942B (en) * | 2024-03-04 | 2024-05-10 | 成都虹润制漆有限公司 | Bottom, middle and surface composite coating for railway bridge steel structure and preparation method thereof |
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| CN117820942A (en) * | 2024-03-04 | 2024-04-05 | 成都虹润制漆有限公司 | Bottom, middle and surface composite coating for railway bridge steel structure and preparation method thereof |
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