CN115353763B - 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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- 238000005260 corrosion Methods 0.000 title claims abstract description 58
- 230000007797 corrosion Effects 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 title claims abstract description 40
- 239000003112 inhibitor Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 49
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 229910052582 BN Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000012964 benzotriazole Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000006228 supernatant Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 239000003973 paint Substances 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 239000002184 metal Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000001453 impedance spectrum Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- -1 zeolite imidazole ester Chemical class 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002539 nanocarrier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005316 response function Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a preparation technology of a metal anti-corrosion coating material, and aims to provide a preparation method of a corrosion inhibitor loaded BTA@ZIF-8/BN-OH composite powder. Comprising the following steps: fully grinding and uniformly mixing sodium hydroxide, potassium hydroxide and hexagonal boron nitride two-dimensional materials, rinsing with deionized water, and transferring to a reaction kettle; reacting for 2h at 180 ℃; centrifuging to obtain supernatant to obtain a BN-OH dispersion of the hydroxylated boron nitride two-dimensional material; adding zinc nitrate hexahydrate and deionized water, and uniformly stirring; adding 2-methylimidazole, benzotriazole and absolute ethyl alcohol, and reacting for 12 hours in a water bath at 25 ℃ under stirring; separating, washing and drying the precipitate to obtain the composite powder. The invention adopts a one-step method in-situ self-assembly mode to realize the load of BTA and the preparation of a load structure on the surface of the boron nitride two-dimensional material, does not need additional load steps such as vacuum impregnation and the like, and simplifies the load process. The composite powder has good dispersibility, is not easy to agglomerate, is easier to store, and expands the application range of the corrosion inhibitor BTA.
Description
Technical Field
The invention relates to a preparation technology of a metal anti-corrosion coating material, in particular to a preparation method of a corrosion inhibitor loaded BTA@ZIF-8/BN-OH composite powder.
Background
Benzotriazole BTA is used as a corrosion inhibitor and widely applied to metal anticorrosive paint. The anti-corrosion coating can protect the metal surface when crack defects are generated on the coating, slow down the corrosion of metal materials and greatly improve the service life of the anti-corrosion coating.
The BTA corrosion inhibitor can only be added into the metal anti-corrosion coating in a small amount of 0.1-1%, because the corrosion inhibitor is introduced into the coating in a large amount to easily cause the increase of coating defects, the corrosion resistance is poor, and the long-acting application of the BTA corrosion inhibitor in the anti-corrosion coating is limited.
Accordingly, there is a need to provide a new technique for loading 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 providing a preparation method of corrosion inhibitor-loaded BTA@ZIF-8/BN-OH composite powder.
In order to solve the technical problems, the invention adopts the following solutions:
the preparation method of the corrosion inhibitor loaded BTA@ZIF-8/BN-OH composite powder comprises the following steps:
(1) Taking 1 to 4 parts by mass of sodium hydroxide and 1.4 to 5.6 parts by mass of potassium hydroxide, and fully grinding and uniformly mixing; then adding 0.2 to 0.8 mass part of hexagonal boron nitride two-dimensional material (h-BN), and fully grinding and uniformly mixing;
(2) Washing the mixed powder obtained in the step (1) with 20-80 ml of deionized water, transferring the washed mixed powder into a high-pressure hydrothermal reaction kettle, and reacting for 2 hours at 180 ℃; centrifuging to obtain supernatant to obtain a BN-OH dispersion of the hydroxylated boron nitride two-dimensional material;
(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 parts by mass of benzotriazole BTA and 25-100 ml of absolute ethyl alcohol until the materials are completely dissolved; then adding the mixture obtained in the step (3) into the mixture, and reacting for 12 hours under the conditions of water bath and stirring at 25 ℃;
(5) And (3) centrifugally separating the reaction solution obtained in the step (4), centrifugally washing the precipitate by using deionized water, and then drying at 50-60 ℃ to obtain the corrosion inhibitor-loaded BTA@ZIF-8/BN-OH composite powder.
As a preferred embodiment of the present invention, in the step (1), the purity of sodium hydroxide is at least 99%, and the purity of 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;
as 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%.
As a preferable mode of the present invention, in the step (4), the stirring speed at the time of the reaction is 400rpm.
As a preferable mode of the invention, in the step (5), the speed during centrifugal separation is at least 8000rpm and the time is at least 20min; the speed during centrifugal washing is at least 8000rpm and the time is at least 20min.
The invention further provides an application method of the corrosion inhibitor loaded BTA@ZIF-8/BN-OH composite powder prepared by the method, wherein the composite powder and the dispersion liquid are added into the sol-gel ceramic anticorrosive paint according to the mass percentage of 0.5%, and the mixture is stirred uniformly; then the evenly mixed paint is covered on the surface of the base material in a spraying or coating mode; curing for 1 hour at 170 ℃ to obtain the coating with slow-release and anti-corrosion functions.
Description of the inventive principles:
1. the zeolite imidazole ester framework material (ZIF-8) is used as a metal organic framework Material (MOFs) with a zeolite-like structure and is made of Zn 2+ And imidazolyl ligands, is a porous material with a topology that is typically represented in zeolitic imidazolate metal organic frameworks (ZIFs). The ZIF-8 skeleton structure has permanent pores and high heightThe metal corrosion inhibitor has the characteristics of surface area, hydrophobicity, open metal sites, excellent water stability and heat stability, pH response release, high chemical stability, simple preparation method and the like, so that the metal corrosion inhibitor has wide application prospect in the aspect of nano carrier materials of the metal corrosion inhibitor. However, currently ZIF-8 is mainly applied to organic resin-based metal anti-corrosion coatings such as epoxy, polyurethane and the like, and the problems of compatibility and the like are less concerned in inorganic coating systems or organic/inorganic composite coating systems.
The hexagonal boron nitride two-dimensional material (h-BN) is a two-dimensional nano boron nitride material with a hexagonal crystal structure, is one kind of hexagonal boron nitride, and is analogous 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 physical and chemical properties of the hexagonal boron nitride two-dimensional material and the graphite are relatively similar, so that the hexagonal boron nitride two-dimensional material is also called 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 anti-corrosion coating to improve the physical shielding performance and 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 adjacent interlayer B and N atoms of the hexagonal boron nitride two-dimensional material causes the hexagonal boron nitride two-dimensional material to be relatively easy to agglomerate, so that the hexagonal boron nitride two-dimensional material has poor dispersibility in the metal anticorrosive paint.
Based on the reasons, the composite material of 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 capacity and the corrosion resistance of an inorganic coating system or an organic/inorganic composite corrosion-resistant coating, and related research work in the aspect belongs to the difficult problem in the industry, and related research results are not reported all the time.
2. The invention creatively proposes that the surface of the hexagonal boron nitride two-dimensional material h-BN is subjected to hydroxylation treatment by adopting a hydrothermal method to obtain the hydroxylated boron nitride two-dimensional material BN-OH so as to improve the dispersibility of the hydroxylated boron nitride two-dimensional material in a solution. Then, a one-step method in-situ self-assembly mode is adopted to load BTA in the ZIF-8 zeolite structure, and diamond dodecahedron nano particles are formed by BN-OH growth.
Compared with other similar material preparation processes in the prior art, the invention 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 proposes that the corrosion inhibitor BTA is loaded in situ in the ZIF-8 structure of the organic metal framework, so that the corrosion inhibitor with the pH response function can be controllably released, and the problem of reduced coating performance caused by directly introducing the corrosion inhibitor into the anti-corrosion coating is avoided. Meanwhile, the surface of the ZIF-8 microsphere is modified with the hydroxylated boron nitride two-dimensional material, so that the compatibility of the powder and the anti-corrosion coating can be improved, and the generation of microcracks and defects in the coating caused by the introduction of the powder can be reduced.
The implementation mechanism of the invention at the microscopic level is as follows: along with the increase of the service time of the metal anti-corrosion coating, the aging phenomenon of the coating material can cause surface defects such as microcracks, micropores and the like on the surface of the coating, so that the invasion of corrosive media such as moisture, salt and the like into the coating matrix is accelerated, the corrosive media reach the surface of the metal, and the local corrosion of the metal is caused. The electrochemical reaction initiated by corrosion can cause the local pH value change of the corrosion area, trigger the decomposition of the ZIF-8 framework structure, release corrosion inhibitor BTA molecules, adsorb on the metal surface to form a corrosion inhibitor film, and prevent the corrosion medium from further corroding the metal material surface. Meanwhile, a large number of hydroxyl functional groups exist in the hydroxylated boron nitride lamellar structure, so that the dispersibility of the hydroxylated boron nitride lamellar structure in the coating can be improved, a reticular cross-linked structure is formed between the hydroxylated boron nitride lamellar structure and the coating in the film forming process of the sol-gel coating, the compatibility of ZIF-8 microspheres in the sol-gel coating is improved, and the generation of microcracks and defects in the coating caused by introduction of the microspheres is reduced.
The specific implementation formula in the actual application scene is as follows: and adding BTA@ZIF-8/BN-OH composite powder or dispersion liquid into the primer coating, and uniformly dispersing BTA@ZIF-8/BN-OH nano filler into a coating matrix after spraying to realize the active protection function of the coating.
Therefore, the technology of the invention realizes the process, and breaks through the conventional thought of application research on the metal corrosion inhibitor coating material and the zeolite imidazole ester framework material in the existing work.
4. The existing ZIF-8 preparation method generally uses methanol as a solvent, has high cost and is harmful to human bodies. In the self-assembly process of the organometallic framework ZIF-8, the invention innovatively adopts water/ethanol mixed solution 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 invention adopts a one-step method in-situ self-assembly mode to realize the load of BTA and the preparation of a load structure on the surface of the boron nitride two-dimensional material, does not need additional load steps such as vacuum impregnation and the like, and simplifies the load process.
2. The composite powder prepared by the invention has good dispersibility, is not easy to agglomerate, is easier to store, and expands the application range of the corrosion inhibitor BTA.
3. The hydroxylation repulsive force of the surface of the boron nitride two-dimensional material improves the dispersibility of the powder in the coating and the compatibility of the powder with the inorganic coating or the 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 microscope (20000 times) of BTA@ZIF-8/BN-OH composite powder.
FIG. 3 is a nitrogen adsorption curve of BTA@ZIF-8/BN-OH composite powder.
FIG. 4 is a graph showing pore size distribution of BTA@ZIF-8/BN-OH composite powder.
FIG. 5 is an electrochemical impedance spectrum of a sol-gel ceramic corrosion protection coating without BTA@ZIF-8/BN-OH composite powder added for different soaking times.
FIG. 6 is an electrochemical impedance spectrum of a sol-gel ceramic corrosion protection coating added with 0.5% BTA@ZIF-8/BN-OH composite powder for different soaking times.
Detailed Description
The invention is further described below with reference to specific embodiments and figures.
In each example, hexagonal boron nitride, benzotriazole BTA and 2-methylimidazole are products of Allatin industry company, and absolute ethyl alcohol and zinc nitrate hexahydrate are products of national pharmaceutical group chemical reagent company. 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 BTA is at least 99%, the purity of 2-methylimidazole is at least 98%, the purity of absolute ethyl alcohol is at least 99.7%, and the purity of zinc nitrate hexahydrate 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.
The following percentages are mass percentages unless otherwise indicated, and the parts are mass parts.
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 into the mixture, and fully grinding and uniformly mixing the mixture;
(2) Washing the mixed powder obtained in the step (1) with 20ml of deionized water, transferring to a high-pressure hydrothermal reaction kettle, reacting for 2 hours at a high temperature of 180 ℃, and centrifuging to obtain supernatant to obtain hydroxylated boron nitride two-dimensional material BN-OH dispersion;
(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 until being completely dissolved, and are added into the mixed dispersion liquid obtained in the step (3) to react for 12 hours under the water bath and stirring conditions at 25 ℃;
(5) And (3) separating the mixed solution obtained in the step (4) by using a centrifugal separator, centrifugally washing the obtained precipitate by using deionized water, and then placing the precipitate in a 50 ℃ oven for drying to obtain the corrosion inhibitor-loaded BTA@ZIF-8/BN-OH composite powder.
In the step (4), the stirring speed at the time of the reaction was 400rpm; in step (5), the speed during centrifugation is at least 8000rpm and the time is at least 20min; the speed during the centrifugal washing was at least 8000rpm and the time was at least 20min (the same as in 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 into the mixture, and fully grinding and uniformly mixing the mixture;
(2) Washing the mixed powder obtained in the step (1) with 80ml of deionized water, transferring the mixed powder into a high-pressure hydrothermal reaction kettle, reacting for 2 hours at a high temperature of 180 ℃, and centrifuging to obtain supernatant fluid to obtain hydroxylated boron nitride two-dimensional material BN-OH dispersion;
(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) Stirring 0.415 parts by mass of 2-methylimidazole, 0.015 parts by mass of benzotriazole BTA and 25ml of absolute ethyl alcohol until the benzotriazole BTA and the absolute ethyl alcohol are completely dissolved, adding the mixture into the mixed dispersion liquid obtained in the step (3), and reacting for 12 hours under the conditions of water bath at 25 ℃ and stirring;
(5) And (3) separating the mixed solution obtained in the step (4) by using a centrifugal separator, centrifugally washing the obtained precipitate by using deionized water, and then placing the precipitate in a 60 ℃ oven for drying to obtain the corrosion inhibitor-loaded 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 into the mixture, and fully grinding and uniformly mixing the mixture;
(2) Washing the mixed powder obtained in the step (1) with 40ml of deionized water, transferring the mixed powder into a high-pressure hydrothermal reaction kettle, reacting for 2 hours at a high temperature of 180 ℃, and centrifuging to obtain supernatant fluid to obtain hydroxylated boron nitride two-dimensional material BN-OH dispersion;
(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) Stirring 0.83 part by mass of 2-methylimidazole, 0.03 part by mass of benzotriazole BTA and 50ml of absolute ethyl alcohol until the benzotriazole BTA and the absolute ethyl alcohol are completely dissolved, adding the mixture into the mixed dispersion liquid obtained in the step (3), and reacting for 12 hours under the conditions of water bath at 25 ℃ and stirring;
(5) And (3) separating the mixed solution obtained in the step (4) by using a centrifugal separator, centrifugally washing the obtained precipitate by using deionized water, and then placing the precipitate in a 55 ℃ oven for drying to obtain the corrosion inhibitor-loaded BTA@ZIF-8/BN-OH composite powder.
The application method comprises the following steps:
the corrosion inhibitor load BTA@ZIF-8/BN-OH composite powder prepared in examples 1-3 is prepared by the following application method: adding the composite powder and the dispersion liquid into the commercial sol-gel ceramic anticorrosive paint according to the mass percentage of 0.5%, and uniformly stirring; then the evenly mixed paint is covered on the surface of the base material in a spraying or coating mode; curing for 1 hour at 170 ℃ to obtain the coating with slow-release and anti-corrosion functions.
Comparison experiment:
1. the sol-gel ceramic anticorrosive paint without BTA@ZIF-8/BN-OH composite powder is sprayed on a substrate by using a 5052 aluminum alloy plate after 100-mesh silicon carbide sand blasting as a substrate, and is cured for 1 hour at 170 ℃, and electrochemical impedance maps (soaked in 5% neutral sodium chloride solution) of different soaking times of the coating are acquired, as shown in figure 5.
2. The sol-gel ceramic anticorrosive paint added with 0.5% of BTA@ZIF-8/BN-OH composite powder in example 1 is sprayed on a substrate by using a 5052 aluminum alloy plate subjected to 100-mesh silicon carbide sand blasting as a substrate, and is cured for 1 hour at 170 ℃, and an electrochemical impedance spectrum (soaked in 5% neutral sodium chloride solution) of the coating at different soaking times is acquired, as shown in FIG. 6.
3. The electrochemical impedance spectra of the surfaces of the samples after being soaked in sodium chloride solution at different times are compared, and particularly, the electrochemical impedance spectra are shown in fig. 5 and 6. The comparison result shows that the electrochemical impedance value of the anticorrosive coating added with the composite powder is obviously higher than that of the anticorrosive coating without BTA@ZIF-8/BN-OH composite powder after 1 day of soaking, and the electrochemical impedance value reduction rate of the anticorrosive coating added with the composite powder after 2 days and 3 days of soaking is obviously lower than that of the anticorrosive coating without BTA@ZIF-8/BN-OH composite powder. It can be seen that the composite powder of the invention can obviously improve the corrosion resistance of the anti-corrosion coating.
In addition, FIGS. 3 and 4 show BTA@ZIF-8/BN-OH composite powderAs can be seen from the graph, the composite powder has a relatively high specific surface area of 2046m 2 The average pore diameter per gram is about 1nm, which is typical of ZIF-8.
Claims (3)
1. The preparation method of the corrosion inhibitor loaded BTA@ZIF-8/BN-OH composite powder is characterized by comprising the following steps of:
(1) Taking 1-4 parts by mass of sodium hydroxide and 1.4-5.6 parts by mass of potassium hydroxide, and fully grinding and uniformly mixing; then adding 0.2-0.8 part by mass of hexagonal boron nitride two-dimensional material h-BN, and fully grinding and uniformly mixing; 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 hexagonal boron nitride two-dimensional material is at least 99.9%, and the granularity is less than or equal to 10 mu m;
(2) Washing the mixed powder obtained in the step (1) with 20-80 mL of deionized water, transferring the washed mixed powder into a high-pressure hydrothermal reaction kettle, and reacting for 2h at 180 ℃; centrifuging to obtain supernatant to obtain a BN-OH dispersion of the hydroxylated boron nitride two-dimensional material;
(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; the zinc nitrate hexahydrate has a purity of at least 99%;
(4) Mixing and stirring 0.415-1.66 parts by mass of 2-methylimidazole, 0.015-0.06 parts by mass of benzotriazole BTA and 25-100 mL of absolute ethyl alcohol until the materials are completely dissolved; 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%; then adding the mixture obtained in the step (3) into the mixture to react under the conditions of water bath at 25 ℃ and stirring at the speed of 400rpm for 12h;
(5) And (3) centrifugally separating the reaction liquid obtained in the step (4), centrifugally washing the precipitate by using deionized water, and then drying at 50-60 ℃ to obtain the corrosion inhibitor-loaded BTA@ZIF-8/BN-OH composite powder.
2. The method according to claim 1, wherein in step (5), the speed at which the centrifugal separation is performed is at least 8000rpm for at least 20min; the speed during centrifugal washing is at least 8000rpm and the time is at least 20min.
3. The application method of the corrosion inhibitor-loaded BTA@ZIF-8/BN-OH composite powder prepared by the method of claim 1 is characterized in that the composite powder is added into sol-gel ceramic anticorrosive paint according to the mass percentage of 0.5%, and the mixture is stirred uniformly; then the evenly mixed paint is covered on the surface of the base material in a spraying mode; curing for 1 hour at 170 ℃ to obtain the coating with slow-release and anti-corrosion functions.
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