CN115353763A - Preparation method of corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder - Google Patents
Preparation method of corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 238000003756 stirring Methods 0.000 claims abstract description 17
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- 238000000227 grinding Methods 0.000 claims abstract description 11
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- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-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
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular 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
- 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
Abstract
The invention relates to a preparation technology of a metal anticorrosive coating material, and aims to provide a preparation method of a corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder. The method comprises the following steps: fully grinding and uniformly mixing sodium hydroxide, potassium hydroxide and a hexagonal boron nitride two-dimensional material, rinsing with deionized water, and transferring to a reaction kettle; reacting for 2 hours at 180 ℃; centrifuging and taking supernatant to obtain a hydroxylated boron nitride two-dimensional material BN-OH dispersion liquid; adding zinc nitrate hexahydrate and deionized water, and uniformly stirring; then adding 2-methylimidazole, benzotriazole and absolute ethyl alcohol, and reacting for 12 hours in a water bath at 25 ℃ under the stirring condition; separating, washing and drying the precipitate to obtain the composite powder. According to the method, the BTA load and the preparation of the load structure are realized on the surface of the boron nitride two-dimensional material in a one-step in-situ self-assembly mode, additional load steps such as vacuum impregnation and the like are not needed, and the load process is simplified. The composite powder has good dispersibility, is not easy to agglomerate and is easier to store, and the application range of the corrosion inhibitor BTA is expanded.
Description
Technical Field
The invention relates to a preparation technology of a metal anticorrosive coating material, in particular to a preparation method of a corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder.
Background
The benzotriazole BTA is used as a corrosion inhibitor and widely applied to metal anticorrosive coatings. The coating can protect the metal surface when the coating generates crack defects, slow down the corrosion of metal materials and greatly prolong the service life of the anticorrosive coating.
BTA corrosion inhibitor can only be added into the metal anticorrosive coating in a small amount of 0.1-1 percent, because the defects of the coating are increased easily and the corrosion resistance is deteriorated if a large amount of corrosion inhibitor is introduced into the coating, thereby limiting the long-term application of the BTA corrosion inhibitor in the anticorrosive coating.
Therefore, it is necessary to provide a new technique for loading the corrosion inhibitor BTA to solve the above problems.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder comprises the following steps:
(1) Taking 1-4 parts by mass of sodium hydroxide and 1.4-5.6 parts by mass of potassium hydroxide, fully grinding and uniformly mixing; then adding 0.2-0.8 mass part of hexagonal boron nitride two-dimensional material (h-BN), fully grinding and uniformly mixing;
(2) Rinsing the mixed powder obtained in the step (1) with 20-80 ml of deionized water, transferring the rinsed mixed powder into a high-pressure hydrothermal reaction kettle, and reacting for 2 hours at 180 ℃; centrifuging and taking supernatant to obtain a hydroxylated boron nitride two-dimensional material BN-OH dispersion liquid;
(3) Adding 0.75-3.00 parts by mass of zinc nitrate hexahydrate and 25-100 ml of deionized water into the BN-OH dispersion liquid obtained in the step (2), and uniformly stirring;
(4) Mixing and stirring 0.415-1.66 parts by mass of 2-methylimidazole, 0.015-0.06 part by mass of benzotriazole BTA and 25-100 ml of absolute ethanol until the materials are completely dissolved; then adding the mixture into the mixed solution obtained in the step (3), and reacting for 12 hours in a water bath at 25 ℃ under the stirring condition;
(5) Centrifugally separating the reaction solution obtained in the step (4), centrifugally washing and precipitating by using deionized water, and then drying at 50-60 ℃ to prepare the BTA @ ZIF-8/BN-OH composite powder loaded with the corrosion inhibitor.
In a preferred embodiment of the present invention, in the step (1), the purity of the sodium hydroxide is at least 99%, and the purity of the potassium hydroxide is at least 99%; the purity of the hexagonal boron nitride is at least 99.9 percent, and the granularity is less than or equal to 10 mu m;
in a preferred embodiment of the present invention, in the step (3), the purity of zinc nitrate hexahydrate is at least 99%.
As a preferable scheme of the invention, in the step (4), the purity of the 2-methylimidazole is at least 98%, the purity of the benzotriazole is at least 99%, and the purity of the absolute ethyl alcohol is at least 99.7%.
In a preferred embodiment of the present invention, in the step (4), the stirring speed during the reaction is 400rpm.
In a preferable embodiment of the present invention, in the step (5), the speed of centrifugation is at least 8000rpm, and the time is at least 20min; the speed of centrifugal washing is at least 8000rpm, and the time is at least 20min.
Further, the invention also provides an application method of the corrosion inhibitor load BTA @ ZIF-8/BN-OH composite powder prepared by the method, which is characterized in that the composite powder and dispersion liquid are added into the sol-gel type ceramic anticorrosive paint according to the mass percentage of 0.5 percent and are stirred uniformly; then the evenly mixed coating is coated on the surface of the base material in a spraying or coating mode; curing for 1 hour at 170 ℃ to obtain the coating with the slow-release and anti-corrosion functions.
Description of the inventive concept:
1. zeolite imidazolate framework material (ZIF-8) as gold having a zeolite-like structureBelongs to organic framework Materials (MOFs), and is formed by Zn 2+ And imidazole-based ligands are typical representatives of zeolitic imidazolate metal organic frameworks (ZIFs). The ZIF-8 skeleton structure has permanent pores, high surface area, hydrophobicity, open metal sites, excellent water stability and thermal stability, and has wide application prospect in the aspect of metal corrosion inhibitor nano carrier materials due to the characteristics of pH response release, high chemical stability, simple preparation method and the like. However, ZIF-8 is mainly applied to organic resin based metal anticorrosive coatings such as epoxy and polyurethane, and the inorganic coating system or organic/inorganic composite coating system is less concerned due to problems such as compatibility.
The hexagonal boron nitride two-dimensional material (h-BN) refers to a two-dimensional nano boron nitride material with a hexagonal crystal structure, is one of hexagonal boron nitrides and is similar to the relationship between graphite and graphene. The hexagonal boron nitride two-dimensional material (h-BN) is white powder, the crystal structure of the hexagonal boron nitride two-dimensional material is very similar to that of graphite, and the two materials have similar physical and chemical properties, so the hexagonal boron nitride is also called as 'white graphite', and has important application in the fields of heat conduction, lubrication, hydrogen storage, battery diaphragm materials, high-temperature oxidation resistant coatings, catalysis and the like. The hexagonal boron nitride two-dimensional material h-BN can be used as a nano filling material in an anticorrosive coating to improve the physical shielding performance and the mechanical performance of the coating due to the unique nano lamellar structure and excellent thermal stability, chemical stability and mechanical performance. However, the interaction force between B and N atoms between adjacent layers of the hexagonal boron nitride two-dimensional material leads the hexagonal boron nitride two-dimensional material to be easy to agglomerate, so that the dispersibility in the metal anticorrosive paint is poor.
Based on the reasons, the composite material of the ZIF-8 nano particles loaded with the organic corrosion inhibitor and the hexagonal boron nitride two-dimensional material is used for enhancing the physical shielding capability and the corrosion resistance of an inorganic coating system or an organic/inorganic composite anticorrosive coating, and related research work in the aspect belongs to the problems in the industry and is not reported in related research results all the time.
2. The invention creatively provides that a hydrothermal method is adopted to carry out hydroxylation treatment on the h-BN surface of the hexagonal boron nitride two-dimensional material to obtain a hydroxylated boron nitride two-dimensional material BN-OH so as to improve the dispersibility of the hydroxylated boron nitride two-dimensional material BN-OH in the solution. And then, BTA is loaded in a ZIF-8 zeolite structure in a one-step in-situ self-assembly mode, and grows in BN-OH to form rhombic dodecahedron nanoparticles.
Compared with other similar material preparation processes in the prior art, the method also needs additional loading steps such as vacuum impregnation and the like, greatly simplifies the loading process, and simultaneously reduces the material cost.
3. The invention creatively provides that the corrosion inhibitor BTA is loaded in situ in the organic metal framework ZIF-8 structure, so that the controllable release of the corrosion inhibitor with the pH response function can be realized, and the problem of coating performance reduction caused by the direct introduction of the corrosion inhibitor into the anticorrosive coating is avoided. Meanwhile, the surface of the ZIF-8 microsphere is modified with a hydroxylated boron nitride two-dimensional material, so that the compatibility of the powder and an anticorrosive coating can be improved, and microcracks and defects in the coating caused by the introduction of the powder are reduced.
The mechanism of the invention at the microscopic level is as follows: with the increase of the service time of the metal anticorrosion coating, the aging phenomenon of the coating material can cause the surface defects of microcracks, micropores and the like on the surface of the coating, and accelerates the corrosion media of moisture, salt and the like to invade into the matrix of the coating and reach the surface of the metal to cause the local corrosion of the metal. The electrochemical reaction caused by corrosion can cause the local pH value change of a corrosion area, the decomposition of a ZIF-8 skeleton structure is caused, BTA molecules serving as a corrosion inhibitor are released, and a layer of corrosion inhibitor film is adsorbed on the surface of metal to prevent a corrosion medium from further corroding the surface of the metal material. Meanwhile, a large number of hydroxyl functional groups exist in the hydroxylated boron nitride lamellar structure, so that the dispersibility of the boron nitride lamellar structure in the coating can be increased, a net-shaped cross-linking structure is formed with the coating in the sol-gel coating film forming process, the compatibility of the ZIF-8 microspheres in the sol-gel coating is improved, and the generation of microcracks and defects in the coating caused by the introduction of the microspheres is reduced.
The concrete implementation formula in the practical application scene is as follows: BTA @ ZIF-8/BN-OH composite powder or dispersion liquid is added into the primer coating, and after spraying, the BTA @ ZIF-8/BN-OH nano filler is uniformly dispersed in a coating matrix, so that the active protection function of the coating is realized.
Therefore, the technical realization process breaks through the conventional thought of application research on the metal corrosion inhibitor coating material and the zeolite imidazolate framework material in the prior work.
4. The existing preparation method of ZIF-8 generally uses methanol as a solvent, has higher cost and is harmful to human bodies. In the process of self-assembly of the organic metal framework ZIF-8, the invention innovatively adopts water/ethanol mixed liquor as a liquid phase solvent in the synthesis process. In this way replacing the traditional methanol solvent; not only reduces the preparation cost, but also avoids the harm to human body caused by methanol volatilization in the production process.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts a one-step method in-situ self-assembly mode to realize BTA loading and load structure preparation on the surface of the boron nitride two-dimensional material, does not need additional loading steps such as vacuum impregnation and the like, and simplifies the loading process.
2. The composite powder prepared by the invention has good dispersibility, is not easy to agglomerate, is easier to store, and widens the application range of the corrosion inhibitor BTA.
3. The hydroxylation repulsion force on the surface of the boron nitride two-dimensional material improves the dispersibility of the powder in the coating and the compatibility with an inorganic coating or an organic/inorganic composite coating.
Drawings
FIG. 1 is a scanning electron microscope image (500 times) of a hydroxylated boron nitride two-dimensional material BN-OH.
FIG. 2 is a scanning electron micrograph of BTA @ ZIF-8/BN-OH composite powder (20000 times).
FIG. 3 is a nitrogen adsorption curve of BTA @ ZIF-8/BN-OH composite powder.
FIG. 4 is a pore size distribution diagram of BTA @ ZIF-8/BN-OH composite powder.
FIG. 5 is an electrochemical impedance spectrum of sol-gel ceramic anticorrosive coating without BTA @ ZIF-8/BN-OH composite powder for different soaking times.
FIG. 6 is an electrochemical impedance spectrum of a sol-gel ceramic anticorrosive coating added with 0.5% BTA @ ZIF-8/BN-OH composite powder for various immersion times.
Detailed Description
The invention is further illustrated below with reference to specific embodiments and the accompanying drawings.
In each example, hexagonal boron nitride, benzotriazole BTA, and 2-methylimidazole are products of the Arlatin industries, and anhydrous ethanol and zinc nitrate hexahydrate are products of the chemical reagents of the national pharmaceutical group, inc. The purity of the sodium hydroxide is at least 99 percent, and the purity of the potassium hydroxide is at least 99 percent; the purity of the BTA is at least 99 percent, the purity of the 2-methylimidazole is at least 98 percent, the purity of the absolute ethyl alcohol is at least 99.7 percent, and the purity of the zinc nitrate hexahydrate is at least 99 percent. The purity of the hexagonal boron nitride is at least 99.9 percent, and the granularity is less than or equal to 10 mu m.
Unless otherwise specified, the following percentages are percentages by mass, and the parts are parts by mass.
Example 1
(1) Fully grinding and uniformly mixing 1 part by mass of sodium hydroxide and 1.4 parts by mass of potassium hydroxide, adding 0.2 part by mass of hexagonal boron nitride two-dimensional material h-BN, and fully grinding and uniformly mixing;
(2) Rinsing the mixed powder obtained in the step (1) with 20ml of deionized water, transferring the rinsed mixed powder into a high-pressure hydrothermal reaction kettle, reacting at the high temperature of 180 ℃ for 2 hours, centrifuging and taking supernatant to obtain hydroxylated boron nitride two-dimensional material BN-OH dispersion liquid;
(3) Adding 3.00 parts by mass of zinc nitrate hexahydrate and 100ml of deionized water into the BN-OH dispersion liquid obtained in the step (2) and uniformly stirring;
(4) 1.66 parts by mass of 2-methylimidazole, 0.06 part by mass of benzotriazole BTA and 100ml of absolute ethyl alcohol are stirred to be completely dissolved, added into the mixed dispersion liquid obtained in the step (3), and reacted for 12 hours under the conditions of water bath at 25 ℃ and stirring;
(5) And (5) separating the mixed solution obtained in the step (4) by using a centrifugal separator, centrifugally washing the obtained precipitate by using deionized water, and drying in a 50 ℃ oven to obtain the corrosion inhibitor supported BTA @ ZIF-8/BN-OH composite powder.
In the step (4), the stirring speed during the reaction is 400rpm; in the step (5), the speed of centrifugal separation is at least 8000rpm, and the time is at least 20min; the speed of the centrifugal washing was at least 8000rpm, and the time was at least 20min (the same applies to examples 2 and 3 below).
Example 2
(1) Fully grinding and uniformly mixing 4 parts by mass of sodium hydroxide and 5.6 parts by mass of potassium hydroxide, adding 0.8 part by mass of hexagonal boron nitride two-dimensional material h-BN, and fully grinding and uniformly mixing;
(2) Rinsing the mixed powder obtained in the step (1) with 80ml of deionized water, transferring the rinsed mixed powder into a high-pressure hydrothermal reaction kettle, reacting at 180 ℃ for 2 hours, centrifuging, and taking supernatant to obtain hydroxylated boron nitride two-dimensional material BN-OH dispersion liquid;
(3) Adding 0.75 mass part of zinc nitrate hexahydrate and 25-100 ml of deionized water into the BN-OH dispersion liquid obtained in the step (2) and uniformly stirring;
(4) 0.415 parts by mass of 2-methylimidazole, 0.015 parts by mass of benzotriazole BTA and 25ml of absolute ethanol are stirred until the materials are completely dissolved, added into the mixed dispersion liquid obtained in the step (3), and reacted for 12 hours under the conditions of water bath at 25 ℃ and stirring;
(5) And (4) separating the mixed solution obtained in the step (4) by using a centrifugal separator, centrifugally washing the obtained precipitate by using deionized water, and drying in an oven at 60 ℃ to obtain the corrosion inhibitor supported BTA @ ZIF-8/BN-OH composite powder.
Example 3
(1) Fully grinding and uniformly mixing 2 parts by mass of sodium hydroxide and 2.8 parts by mass of potassium hydroxide, adding 0.4 part by mass of hexagonal boron nitride two-dimensional material h-BN, and fully grinding and uniformly mixing;
(2) Rinsing the mixed powder obtained in the step (1) with 40ml of deionized water, transferring the rinsed mixed powder into a high-pressure hydrothermal reaction kettle, reacting at the high temperature of 180 ℃ for 2 hours, centrifuging and taking supernatant to obtain hydroxylated boron nitride two-dimensional material BN-OH dispersion liquid;
(3) Adding 1.5 parts by mass of zinc nitrate hexahydrate and 50ml of deionized water into the BN-OH dispersion liquid obtained in the step (2) and uniformly stirring;
(4) 0.83 mass part of 2-methylimidazole, 0.03 mass part of benzotriazole BTA and 50ml of absolute ethyl alcohol are stirred until the materials are completely dissolved, added into the mixed dispersion liquid obtained in the step (3), and reacted for 12 hours under the conditions of water bath at 25 ℃ and stirring;
(5) And (4) separating the mixed solution obtained in the step (4) by using a centrifugal separator, centrifugally washing the obtained precipitate by using deionized water, and drying in an oven at 55 ℃ to obtain the corrosion inhibitor supported BTA @ ZIF-8/BN-OH composite powder.
The application method comprises the following steps:
the application method of the corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder prepared in the embodiments 1 to 3 is as follows: adding the composite powder and the dispersion liquid into a commercially available sol-gel type ceramic anticorrosive coating according to the mass percent of 0.5%, and uniformly stirring; then covering the uniformly mixed coating on the surface of the base material in a spraying or coating mode; curing for 1 hour at 170 ℃ to obtain the coating with the slow-release and anti-corrosion functions.
Comparative experiment:
1. a5052 aluminum alloy plate subjected to sand blasting by using 100-mesh carborundum is taken as a base material, a sol-gel type ceramic anticorrosive paint without BTA @ ZIF-8/BN-OH composite powder is sprayed on the base material to be about 25 micrometers, the base material is cured for 1 hour at 170 ℃, and electrochemical impedance spectrums (soaked in a 5% neutral sodium chloride solution) of different soaking times of the coating are collected, as shown in figure 5.
2. A5052 aluminum alloy plate subjected to sand blasting by using 100-mesh carborundum is taken as a base material, 0.5% of the sol-gel type ceramic anticorrosive coating of BTA @ ZIF-8/BN-OH composite powder in example 1 is added to the base material, the sol-gel type ceramic anticorrosive coating is sprayed on the base material by about 25 micrometers, the sol-gel type ceramic anticorrosive coating is cured for 1 hour at 170 ℃, and electrochemical impedance spectrums (soaked in a 5% neutral sodium chloride solution) of the coating at different soaking times are collected, as shown in figure 6.
3. Comparing the electrochemical impedance maps of the surfaces of the samples soaked in the sodium chloride solution for different time periods, see fig. 5 and 6 in detail. The comparison result shows that the electrochemical impedance value of the anticorrosive coating added with the composite powder after 1-day soaking is obviously higher than that of the anticorrosive coating not added with BTA @ ZIF-8/BN-OH composite powder, and the electrochemical impedance value reduction rate of the anticorrosive coating added with the composite powder after 2-day and 3-day soaking is obviously lower than that of the anticorrosive coating not added with BTA @ ZIF-8/BN-OH composite powder. It can be seen that the composite powder can obviously improve the corrosion resistance of the anticorrosive coating.
FIGS. 3 and 4 are graphs showing the nitrogen adsorption curve and pore size distribution of BTA @ ZIF-8/BN-OH composite powder, which has a high specific surface area of 2046m 2 The/g, the average pore diameter is about 1nm, and is the typical ZIF-8 characteristic.
Claims (7)
1. A preparation method of corrosion inhibitor supported BTA @ ZIF-8/BN-OH composite powder is characterized by comprising the following steps:
(1) Taking 1-4 parts by mass of sodium hydroxide and 1.4-5.6 parts by mass of potassium hydroxide, fully grinding and uniformly mixing; then adding 0.2-0.8 part by mass of hexagonal boron nitride two-dimensional material h-BN, fully grinding and uniformly mixing;
(2) Rinsing the mixed powder obtained in the step (1) with 20-80 ml of deionized water, transferring the rinsed mixed powder into a high-pressure hydrothermal reaction kettle, and reacting for 2 hours at 180 ℃; centrifuging and taking supernatant to obtain a hydroxylated boron nitride two-dimensional material BN-OH dispersion liquid;
(3) 0.75-3.00 parts by mass of zinc nitrate hexahydrate and 25-100 ml of deionized water are added into the BN-OH dispersion liquid obtained in the step (2) and are stirred uniformly;
(4) Taking 0.415-1.66 parts by mass of 2-methylimidazole, 0.015-0.06 part by mass of benzotriazole BTA and 25-100 ml of absolute ethyl alcohol, mixing and stirring until the materials are completely dissolved; then adding the mixture into the mixed solution obtained in the step (3), and reacting for 12 hours in a water bath at 25 ℃ under the stirring condition;
(5) Centrifugally separating the reaction solution obtained in the step (4), centrifugally washing and precipitating by using deionized water, and then drying at 50-60 ℃ to prepare the corrosion inhibitor loaded BTA @ ZIF-8/BN-OH composite powder.
2. The method according to claim 1, wherein in the step (1), the purity of the sodium hydroxide is at least 99%, and the purity of the potassium hydroxide is at least 99%; the purity of the hexagonal boron nitride two-dimensional material is at least 99.9 percent, and the granularity is less than or equal to 10 mu m.
3. The method of claim 1, wherein in step (3), the zinc nitrate hexahydrate has a purity of at least 99%.
4. The method as claimed in claim 1, wherein in step (4), the purity of 2-methylimidazole is at least 98%, the purity of benzotriazole is at least 99%, and the purity of anhydrous ethanol is at least 99.7%.
5. The method according to claim 1, wherein in the step (4), the stirring speed during the reaction is 400rpm.
6. The method according to claim 1, wherein in the step (5), the speed of centrifugation is at least 8000rpm, and the time is at least 20min; the speed of centrifugal washing is at least 8000rpm, and the time is at least 20min.
7. The application method of the corrosion inhibitor supported BTA @ ZIF-8/BN-OH composite powder prepared by the method of claim 1 is characterized in that the composite powder and the dispersion are added into the sol-gel type ceramic anticorrosive coating according to the mass percentage of 0.5 percent and are stirred uniformly; then covering the uniformly mixed coating on the surface of the base material in a spraying or coating mode; curing for 1 hour at 170 ℃ to obtain the coating with the slow-release and anti-corrosion functions.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150291870A1 (en) * | 2012-08-15 | 2015-10-15 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| KR101703814B1 (en) * | 2015-09-16 | 2017-02-08 | 한국과학기술연구원 | Method for controlling thickness of two dimensional material thin film using seeding promoter and solvent |
| CN109592653A (en) * | 2018-11-29 | 2019-04-09 | 盐城师范学院 | A kind of preparation method of two dimension hydroxylating boron nitride |
| CN110079140A (en) * | 2019-04-30 | 2019-08-02 | 中山大学 | A kind of intelligent response selfreparing anticorrosion coating material and preparation method |
| CN111085275A (en) * | 2019-12-31 | 2020-05-01 | 华南理工大学 | Reductive graphene oxide/metal organic framework composite material and preparation method and application thereof |
| CN112266530A (en) * | 2020-10-28 | 2021-01-26 | 苏州特聚新材料科技有限公司 | Antirust film and preparation method thereof |
| CN113058633A (en) * | 2021-03-29 | 2021-07-02 | 浙江理工大学 | Boron nitride hollow composite material and preparation method and application thereof |
| CN114163860A (en) * | 2021-11-30 | 2022-03-11 | 上海应用技术大学 | ZIF-8 structure-based nano container and sol-gel coating and preparation method thereof |
| CN114836035A (en) * | 2022-05-30 | 2022-08-02 | 兰州中科聚润新材料有限公司 | Modified polyphenylene sulfide and preparation method thereof |
-
2022
- 2022-08-22 CN CN202211007079.1A patent/CN115353763B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150291870A1 (en) * | 2012-08-15 | 2015-10-15 | Arkema Inc. | Adsorption systems using metal-organic frameworks |
| KR101703814B1 (en) * | 2015-09-16 | 2017-02-08 | 한국과학기술연구원 | Method for controlling thickness of two dimensional material thin film using seeding promoter and solvent |
| CN109592653A (en) * | 2018-11-29 | 2019-04-09 | 盐城师范学院 | A kind of preparation method of two dimension hydroxylating boron nitride |
| CN110079140A (en) * | 2019-04-30 | 2019-08-02 | 中山大学 | A kind of intelligent response selfreparing anticorrosion coating material and preparation method |
| CN111085275A (en) * | 2019-12-31 | 2020-05-01 | 华南理工大学 | Reductive graphene oxide/metal organic framework composite material and preparation method and application thereof |
| CN112266530A (en) * | 2020-10-28 | 2021-01-26 | 苏州特聚新材料科技有限公司 | Antirust film and preparation method thereof |
| CN113058633A (en) * | 2021-03-29 | 2021-07-02 | 浙江理工大学 | Boron nitride hollow composite material and preparation method and application thereof |
| CN114163860A (en) * | 2021-11-30 | 2022-03-11 | 上海应用技术大学 | ZIF-8 structure-based nano container and sol-gel coating and preparation method thereof |
| CN114836035A (en) * | 2022-05-30 | 2022-08-02 | 兰州中科聚润新材料有限公司 | Modified polyphenylene sulfide and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CONG YANG ET AL: "A pH-responsive hydrophilic controlled release system based on ZIF-8 for self-healing anticorrosion application", vol. 415, pages 3 * |
| RAM KUMAR ET AL: "Functionality preservation with enhanced mechanical integrity in the nanocomposites of the metal–organic framework, ZIF-8, with BN nanosheets", no. 5, pages 514 * |
| 陈汇凯: "功能化氮化硼纳米片改性水性环氧涂层的防腐蚀性能研究", 中国优秀硕士学位论文全文数据库, pages 1 - 77 * |
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