CN116622272B - Modified basalt flake @ ZIF-8-epoxy resin composite coating and preparation method thereof - Google Patents
Modified basalt flake @ ZIF-8-epoxy resin composite coating and preparation method thereof Download PDFInfo
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- CN116622272B CN116622272B CN202310600685.2A CN202310600685A CN116622272B CN 116622272 B CN116622272 B CN 116622272B CN 202310600685 A CN202310600685 A CN 202310600685A CN 116622272 B CN116622272 B CN 116622272B
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- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000003751 zinc Chemical class 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 26
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- 238000001035 drying Methods 0.000 claims abstract description 18
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- 239000002904 solvent Substances 0.000 claims description 14
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
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- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
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- 230000003993 interaction Effects 0.000 abstract description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 40
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 40
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Abstract
The invention provides a preparation method of a modified basalt flake @ ZIF-8-epoxy resin composite coating, which comprises the following steps: a) Alkylating and modifying basalt flakes to obtain modified basalt flakes; b) Mixing the modified basalt flakes obtained in the step a) with zinc salt solution, adding 2-methylimidazole, reacting, and sequentially filtering, washing and drying the obtained mixture to obtain modified basalt flakes @ ZIF-8; c) Dispersing the modified basalt flake @ ZIF-8 obtained in the step b) in an organic solvent, mixing with an epoxy resin solution and a polyamide curing agent, and sequentially coating and curing after ultrasonic defoaming to obtain the modified basalt flake @ ZIF-8-epoxy resin composite coating. The preparation method adopts specific process steps to realize better overall interaction, and the prepared modified basalt flake@ZIF-8-epoxy resin composite coating has excellent anti-corrosion performance and antibacterial performance, and can effectively solve the problems of marine corrosion and marine biofouling.
Description
Technical Field
The invention relates to the technical field of composite coatings, in particular to a modified basalt flake@ZIF-8-epoxy resin composite coating and a preparation method thereof.
Background
Corrosion can severely reduce the useful life of the metal. Metal surfaces are often coated with corrosion-resistant coatings to extend their useful life. However, in severe marine environments, microorganisms in the marine environment affect the corrosion protection coating, they can aggregate to form microbial communities on the surface of the coating, and form biofilms on the surface of the coating, which affects the corrosion protection performance of the coating. Therefore, a good corrosion-resistant coating should possess certain antimicrobial properties to resist attachment and growth of marine fouling organisms. At present, the effective means for protecting marine organisms from fouling is mainly to use the low surface energy of the paint or add bactericides to perform antibiosis, but the traditional toxic bactericides are not the mainstream application of the paint any more, and the development of an environment-friendly long-acting antibiosis material is the key point of research.
Basalt flake is a low-cost and environment-friendly material. The addition of basalt flakes to the coating can create a special "maze effect". The basalt flakes have good weather resistance, the working temperature of the basalt flakes can be as low as minus 200 ℃ and as high as 1000 ℃, and the basalt flakes can be suitable for working environments with large temperature difference and severe conditions. The basalt flakes are added into the organic resin to improve the corrosion resistance of the coating, but the basalt flakes are used as inorganic pigment filler, are hydrophilic and oleophobic and have high density, the surface of the basalt flakes is chemically inert to organic polymers, the dispersion stability in the epoxy resin is poor, and the basalt flakes are easy to sink, so that the improvement of the uniform dispersion and interface compatibility of the basalt flakes in the organic resin is a key for improving the performance of the basalt flakes-organic coating.
There are researches and reports that a super-hydrophobic composite coating is prepared by preparing basalt flakes with hydrophobic property and assembling the basalt flakes on an epoxy resin matrix on the surface of a metal matrix; the method comprises the steps of etching basalt flakes by alkali, sequentially depositing polydopamine and AgNPs on the etched basalt flakes, and then modifying the basalt material with low surface energy to prepare the super-hydrophobic coating material. However, the common basalt flakes are added into the coating as a filler, only have single anti-corrosion performance, have poor dispersion stability in epoxy resin, and are easy to sink.
Disclosure of Invention
In view of the above, the invention aims to provide a modified basalt flake @ ZIF-8-epoxy resin composite coating and a preparation method thereof, wherein ZIF-8 is grown on modified basalt flakes in situ to prepare modified basalt flake functional filler with antibacterial property, and then the modified basalt flake functional filler is compounded with epoxy resin to prepare the composite coating with antiseptic and antibacterial properties; the modified basalt flake@ZIF-8-epoxy resin composite coating prepared by the preparation method provided by the invention can effectively solve the practical problem that a ship needs bacteriostasis and corrosion prevention, has excellent wear resistance, can resist bacterial fouling and corrosion in high-salinity, weak alkaline and high-low-temperature marine environments, and achieves the bacteriostasis and corrosion prevention effects.
The invention provides a preparation method of a modified basalt flake @ ZIF-8-epoxy resin composite coating, which comprises the following steps:
a) Alkylating and modifying basalt flakes to obtain modified basalt flakes;
b) Mixing the modified basalt flakes obtained in the step a) with zinc salt solution, adding 2-methylimidazole, reacting, and sequentially filtering, washing and drying the obtained mixture to obtain modified basalt flakes @ ZIF-8;
c) Dispersing the modified basalt flake @ ZIF-8 obtained in the step b) in an organic solvent, mixing with an epoxy resin solution and a polyamide curing agent, and sequentially coating and curing after ultrasonic defoaming to obtain the modified basalt flake @ ZIF-8-epoxy resin composite coating.
Preferably, the mesh number of the basalt flakes in the step a) is 200-500 mesh.
Preferably, the alkylation modification in step a) is specifically performed by:
a1 Stirring basalt flakes in ethanol for 0.5-1.5 h, and then carrying out suction filtration, separation and drying to remove surface dirt for later use;
a2 0.5M-1.5 MHCl is used as a catalyst to prepare KH-550 solution with the volume percentage of 1-3 percent in ethanol, wherein the mass ratio of KH-550 to basalt flake is (1-2): 10;
a3 Adding the basalt flakes of the step a 1) into the solution of the step a 2), stirring for 3-5 hours, filtering, separating, and drying at room temperature to obtain the modified basalt flakes.
Preferably, the zinc salt in step b) is selected from zinc nitrate and/or zinc acetate; the solvent of the zinc salt solution is selected from one or more of methanol, ethanol and water.
Preferably, the mass ratio of the zinc salt to the modified basalt flake in the step b) is (0.5-2.5): 1, a step of; the molar ratio of Zn 2+ to 2-methylimidazole in the zinc salt is 1: (2-8).
Preferably, the reaction in step b) is performed by:
stirring at 20-30 deg.c and 100-300 r/min for 0.5-1.5 hr, and setting for 20-30 hr to obtain the mixture.
Preferably, the organic solvent in step c) is selected from one or more of acetone, butanone, toluene, xylene, methyl ethyl ketone, cyclohexanone, n-butanol, dioctyl phthalate, dibutyl phthalate and triethyl phosphate;
The mass ratio of the organic solvent to the modified basalt flake @ ZIF-8 is (0.5-1.5): 1.
Preferably, in the step c), the mass ratio of the modified basalt flake @ ZIF-8 to the epoxy resin solution and the polyamide curing agent is 1: (5-15): (5-15).
Preferably, the time of ultrasonic bubble removal in the step c) is 20-40 min.
The invention also provides a modified basalt flake@ZIF-8-epoxy resin composite coating, which is prepared by adopting the preparation method of the technical scheme.
The invention provides a modified basalt flake@ZIF-8-epoxy resin composite coating and a preparation method thereof; the preparation method comprises the following steps: a) Alkylating and modifying basalt flakes to obtain modified basalt flakes; b) Mixing the modified basalt flakes obtained in the step a) with zinc salt solution, adding 2-methylimidazole, reacting, and sequentially filtering, washing and drying the obtained mixture to obtain modified basalt flakes @ ZIF-8; c) Dispersing the modified basalt flake @ ZIF-8 obtained in the step b) in an organic solvent, mixing with an epoxy resin solution and a polyamide curing agent, and sequentially coating and curing after ultrasonic defoaming to obtain the modified basalt flake @ ZIF-8-epoxy resin composite coating. Compared with the prior art, the preparation method provided by the invention adopts specific process steps to realize better overall interaction, the basalt flakes are alkylated and modified by a simple method, ZIF-8 is grown on the modified basalt flakes in situ to obtain modified basalt flakes@ZIF8 functional filler with antibacterial and hydrophobic properties, and finally the functional filler is compounded with epoxy resin to obtain the coating with excellent corrosion resistance and antibacterial properties; the modified basalt flake@ZIF-8-epoxy resin composite coating provided by the invention has excellent anti-corrosion performance and antibacterial performance, and can effectively solve the problems of marine corrosion and marine biofouling.
Drawings
FIG. 1 is a scanning electron microscope image obtained under examination of different solvents in an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image obtained under examination of different mole ratios of Zn 2+ and 2-methylimidazole in the examples of the present invention;
FIG. 3 is an XRD pattern of modified basalt flake@ZIF-8, raw basalt flake and ZIF-8 obtained in the embodiment of the invention;
FIG. 4 shows salt spray test results of modified basalt flake@ZIF-8-epoxy resin composite coating, epoxy resin coating, modified basalt flake-added coating, ZIF-8-added coating 0d, 5d, 10d, 20d, 30d and 45d obtained in the embodiment of the invention;
FIG. 5 is a panel count test result of antibacterial activity of modified basalt flake@ZIF-8, blank control group, modified basalt flake, ZIF-8 against Staphylococcus aureus and Escherichia coli obtained in the example of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a modified basalt flake @ ZIF-8-epoxy resin composite coating, which comprises the following steps:
a) Alkylating and modifying basalt flakes to obtain modified basalt flakes;
b) Mixing the modified basalt flakes obtained in the step a) with zinc salt solution, adding 2-methylimidazole, reacting, and sequentially filtering, washing and drying the obtained mixture to obtain modified basalt flakes @ ZIF-8;
c) Dispersing the modified basalt flake @ ZIF-8 obtained in the step b) in an organic solvent, mixing with an epoxy resin solution and a polyamide curing agent, and sequentially coating and curing after ultrasonic defoaming to obtain the modified basalt flake @ ZIF-8-epoxy resin composite coating.
According to the invention, firstly, the basalt flakes are subjected to alkylation modification to obtain modified basalt flakes.
The source of the basalt flakes is not particularly limited, and commercially available products known to those skilled in the art may be used. In the present invention, the mesh number of the basalt flakes is preferably 200 mesh to 500 mesh.
In the present invention, the alkylation modification process is preferably specifically:
a1 Stirring basalt flakes in ethanol for 0.5-1.5 h, and then carrying out suction filtration, separation and drying to remove surface dirt for later use;
a2 Using 0.5M-1.5M HCl as a catalyst to prepare KH-550 solution with the volume percentage of 1-3% in ethanol, wherein the mass ratio of KH-550 to basalt flakes is (1-2): 10;
a3 Adding the basalt flakes of the step a 1) into the solution of the step a 2), stirring for 3-5 hours, filtering, separating, and drying at room temperature to obtain modified basalt flakes;
More preferably:
a1 Stirring basalt flakes in ethanol for 1h, and then carrying out suction filtration, separation and drying to remove surface dirt for later use;
a2 Using 1M HCl as a catalyst, a 2% by volume KH-550 solution was prepared in ethanol, wherein the mass ratio of KH-550 to basalt flake was 1.5:10;
a3 Adding the basalt flakes of the step a 1) into the solution of the step a 2), stirring for 4 hours, filtering, separating, and drying at room temperature to obtain modified basalt flakes.
After the modified basalt flakes are obtained, the obtained modified basalt flakes are mixed with zinc salt solution, then 2-methylimidazole is added for reaction, and the obtained mixture is filtered, washed and dried in sequence to obtain the modified basalt flakes@ZIF-8.
ZIF-8 is a typical zinc-based material in ZIFs, and is a nano material with a regular pore structure, which is formed by metal ions Zn 2+ and organic ligand 2-methylimidazole through N-Zn bonds, and ZIF-8 has certain water stability and alkali resistance, so that the ZIF-8 can exist in seawater more stably; ZIF-8 also has excellent sterilization performance, the excellent sterilization performance is mainly derived from active oxygen free radicals generated by photocatalysis, ZIF-8 generates LMCT by photo-generated electrons under the action of solar catalysis, and O 2 can be effectively activated to form O 2- and H 2O2, so that bacteria are oxidized and killed, and meanwhile Zn 2+ can be released from ZIF-8 crystals, so that the ZIF-8 has certain antibacterial activity; ZIF-8 is a metal organic frame material with excellent water resistance and alkali resistance, can realize high-efficiency long-term antibacterial performance in seawater, and meanwhile, imidazole organic ligands in ZIF-8 can interact with polymer matrixes such as epoxy resin and the like, and can also effectively improve the crosslinking density of the epoxy resin. Based on the above, ZIF-8 is probably a good anti-corrosion pigment, and can effectively improve the anti-corrosion performance of the polymer coating.
In the present invention, the zinc salt is preferably selected from zinc nitrate and/or zinc acetate, more preferably zinc nitrate; the source of the zinc salt is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the solvent of the zinc salt solution is preferably selected from one or more of methanol, ethanol and water, more preferably methanol. The source of the solvent of the zinc salt solution is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the mass ratio of the zinc salt to the modified basalt flakes is preferably (0.5-2.5): 1, more preferably (1 to 2): 1, a step of; the molar ratio of Zn 2+ to 2-methylimidazole in the zinc salt is preferably 1: (2 to 8), more preferably 1: (2-4).
In the present invention, the process of adding 2-methylimidazole is preferably carried out by dissolving 2-methylimidazole in a solvent of the above zinc salt solution and then mixing.
In the present invention, the process of the reaction is preferably specifically:
Stirring for 0.5 to 1.5 hours at the temperature of between 20 and 30 ℃ and the rotating speed of between 100 and 300r/min, and standing for 20 to 30 hours to obtain a mixture;
More preferably:
Stirring at 25deg.C and 200r/min for 1 hr, and standing for 24 hr to obtain mixture.
The obtained mixture is sequentially filtered, washed (preferably by ethanol for a plurality of times) and dried (preferably by oven drying at 60-80 ℃) to obtain the modified basalt flake@ZIF-8.
The modified basalt flake @ ZIF-8 prepared by the invention is used as a functional filler, has certain hydrophobic property, and meanwhile, the antibacterial property of the coating is endowed by the ZIF-8; meanwhile, the amino group of ZIF-8 reacts with epoxy to improve the crosslinking density, so that the chemical barrier is achieved, and the problem that basalt flakes are easy to sink in epoxy resin and poor in dispersion stability is effectively solved.
After the modified basalt flake@ZIF-8 is obtained, the obtained modified basalt flake@ZIF-8 is dispersed in an organic solvent, then mixed with an epoxy resin solution and a polyamide curing agent, and after ultrasonic defoaming, the modified basalt flake@ZIF-8-epoxy resin composite coating is obtained through coating and curing in sequence.
In the present invention, the organic solvent is preferably one or more selected from the group consisting of acetone, butanone, toluene, xylene, methyl ethyl ketone, cyclohexanone, n-butanol, dioctyl phthalate, dibutyl phthalate and triethyl phosphate, more preferably xylene and n-butanol; in a preferred embodiment of the present invention, the organic solvent has a mass ratio of 7:3 xylene and n-butanol. The source of the organic solvent is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the invention, the mass ratio of the organic solvent to the modified basalt flake @ ZIF-8 is preferably (0.5-1.5): 1, more preferably 1:1.
In the invention, the mass ratio of the modified basalt flake @ ZIF-8 to the epoxy resin solution to the polyamide curing agent is preferably 1: (5-15): (5 to 15), more preferably 1:10:10.
In the present invention, the time for ultrasonic bubble removal is preferably 20 to 40 minutes, more preferably 30 minutes.
Microorganisms in the marine environment often gather on the surface of the coating to form a microbial community, and marine biofouling seriously affects the application and service life of the anticorrosive paint in the severe marine environment; according to the invention, the ZIF-8 is grown on the modified basalt flakes in situ to obtain the modified basalt flakes@ZIF-8 antibacterial functional filler, and then the modified basalt flakes@ZIF-8 are compounded with the epoxy resin to prepare the epoxy coating with excellent corrosion resistance and antibacterial property, so that the modified basalt flakes@ZIF-8 antibacterial functional filler can effectively work in a marine environment.
The invention also provides a modified basalt flake@ZIF-8-epoxy resin composite coating, which is prepared by adopting the preparation method of the technical scheme. The modified basalt flake@ZIF-8-epoxy resin composite coating provided by the invention has excellent anti-corrosion performance and antibacterial performance, and can effectively solve the problems of marine corrosion and marine biofouling. The experimental results show that: the modified basalt flake @ ZIF-8-epoxy resin composite coating with antibacterial and anti-corrosion properties, which is prepared by the invention, is used for antifouling substrate materials in static or dynamic environments required for ships, offshore infrastructures and the like.
The invention provides a modified basalt flake@ZIF-8-epoxy resin composite coating and a preparation method thereof; the preparation method comprises the following steps: a) Alkylating and modifying basalt flakes to obtain modified basalt flakes; b) Mixing the modified basalt flakes obtained in the step a) with zinc salt solution, adding 2-methylimidazole, reacting, and sequentially filtering, washing and drying the obtained mixture to obtain modified basalt flakes @ ZIF-8; c) Dispersing the modified basalt flake @ ZIF-8 obtained in the step b) in an organic solvent, mixing with an epoxy resin solution and a polyamide curing agent, and sequentially coating and curing after ultrasonic defoaming to obtain the modified basalt flake @ ZIF-8-epoxy resin composite coating. Compared with the prior art, the preparation method provided by the invention adopts specific process steps to realize better overall interaction, the basalt flakes are alkylated and modified by a simple method, ZIF-8 is grown on the modified basalt flakes in situ to obtain modified basalt flakes@ZIF8 functional filler with antibacterial and hydrophobic properties, and finally the functional filler is compounded with epoxy resin to obtain the coating with excellent corrosion resistance and antibacterial properties; the modified basalt flake@ZIF-8-epoxy resin composite coating provided by the invention has excellent anti-corrosion performance and antibacterial performance, and can effectively solve the problems of marine corrosion and marine biofouling.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the invention are all commercially available, wherein basalt flakes are basalt flakes of 325 meshes, zinc salt is zinc nitrate hexahydrate, epoxy resin solution is provided by Jiangsu Sanmu chemical Co., ltd., model E51, polyamide curing agent is provided by Jiangsu Sanmu chemical Co., ltd., model 650; pretreated carbon steel sheet: using 150mm×75mm×3mm low carbon steel as substrate, sand blasting the substrate with sand blaster, cleaning with deionized water and acetone, and standing by. The performance characterization of the following examples of the invention includes:
Surface morphology characterization: the surface morphology of the samples was analyzed using a scanning electron microscope (FE-SEM).
X-ray powder diffraction (XRD): analyzing the crystal structure, lattice parameter, crystal defect, content of different crystal phases and internal stress of the material by utilizing diffraction phenomenon of X-rays in the crystal; x-ray generator power: 2.2kW, a Cu target ceramic X-ray tube, a scanning mode: θ/2θ goniometer, scan range: 3-80 degrees, angle measurement precision: 0.0001 °, scan speed: 1000 DEG/min.
Antibacterial performance test: the invention adopts a plate counting method and a real sea hanging plate to explore the antifouling property of the sample and the coating.
And (3) testing the corrosion resistance of the coating: adopting an electrochemical test and a salt spray test to test the corrosion resistance of the coating; AUTOLAB testing and analyzing instruments such as an electrochemical workstation and the like are used for carrying out impedance spectroscopy (ELS) testing and polarization curve testing on basalt flake/graphene oxide composite sheets; salt spray resistance test chamber according to ISO 7253:1996 standard test for corrosion resistance.
Paint film hardness test of the antifouling coating in the invention: the adhesion of the paint film was tested according to national standard [ GB/T6739-1996 ].
Examples
(1) Preparing modified basalt flakes:
step one: firstly, weighing 10g basalt flakes, stirring in ethanol for 1h, and then carrying out suction filtration, separation and drying to remove surface dirt for later use;
step two: subsequently, a 2% (v/v) KH-550 solution (wherein KH-550 has a mass of 1.5 g) was prepared in ethanol using 1MHCl as a catalyst;
Step three: and then adding 10g of dried basalt flakes into the solution, continuously stirring for 4 hours, filtering, separating, and drying at room temperature to obtain the functionalized modified basalt flakes (MBS).
(2) Preparing modified basalt flake @ ZIF-8:
Step one: 1.485g of zinc salt is weighed and dissolved in 50mL of solvent and stirred uniformly to obtain zinc salt solution;
step two: adding 1g of the modified basalt flakes prepared in the step (1) into the zinc salt solution, and stirring for 12h;
Step three: weighing 0.819g of 2-methylimidazole, dissolving in 50mL of solvent, and uniformly stirring;
step four: adding the solution obtained in the second step and the solution obtained in the third step together, stirring for 1h to be uniform at the rotating speed of 200r/min, and standing for 24h to completely react to obtain a mixture;
Step five: filtering the mixture, washing the mixture with ethanol for a plurality of times, and placing the mixture in a 70 ℃ oven for drying to obtain the modified basalt flake@ZIF-8.
(3) Preparing a modified basalt flake @ ZIF-8-epoxy resin composite coating:
step one: weighing 1g of modified basalt flake@ZIF-8 functional filler, and dispersing in 1g of organic solvent (dimethylbenzene and n-butanol with the mass ratio of 7:3) to obtain an organic solvent of dispersed filler;
step two: weighing 10g of epoxy resin solution, adding an organic solvent for dispersing filler and 10g of polyamide curing agent into the epoxy resin solution, stirring the mixture to be uniform, performing ultrasonic treatment for 30 minutes to remove bubbles, then coating the dispersed coating on the pretreated carbon steel sheet, controlling the coating thickness to be 130+/-10 mu m, and naturally drying and curing the coating at room temperature (25 ℃) for 7 days to obtain the modified basalt flake@ZIF-8-epoxy resin composite coating.
Aiming at the modified basalt flake@ZIF-8 prepared in the step (2), the solvent (step one and step three) is respectively selected from DMF, methanol, ethanol and water, and the reaction is carried out under the experimental condition of a greenhouse, so that a scanning electron microscope image is obtained as shown in figure 1.
Observing the growth condition of the modified basalt flake @ ZIF-8 prepared in different solvents at room temperature through a scanning electron microscope; the crystal morphology of the ZIF-8 prepared in the methanol solvent is most regular under the condition of room temperature, and the grain size is uniform; therefore, the modified basalt flake @ ZIF-8 prepared by the methanol solvent has the optimal effect.
Aiming at the modified basalt flake @ ZIF-8,0.819g of 2-methylimidazole and 1.485g of zinc salt (zinc nitrate hexahydrate) prepared in the step (2), the corresponding molar ratio of Zn 2+ to 2-methylimidazole is 1:2, further looking at the molar ratio of Zn 2+ to 2-methylimidazole as 2: 1. 1: 1. 1: 3. 1: 4. 1: 6. 1: 8. 1:10, the solvent is methanol, and the experimental conditions are reaction under the greenhouse conditions, and a scanning electron microscope chart is shown in fig. 2.
The growth condition of ZIF-8 is explored by changing the proportion of metal Zn 2+ to 2-methylimidazole; it can be seen that, in Zn 2+: the proportion of 2-methylimidazole is 1: 1. 1:2 and 1:3, the crystal form of the grown ZIF-8 crystal is more regular, wherein Zn 2+: 2-methylimidazole = 1:2, the crystal form of the grown ZIF-8 crystal is most regular, and the grain size is uniform; thus, the examples employ Zn 2+: 2-methylimidazole = 1:2 (molar ratio) to prepare modified basalt flake @ ZIF-8 with optimal effect.
Aiming at the modified basalt flake @ ZIF-8 prepared in the step (2), methanol and Zn 2+ are selected as solvents: 2-methylimidazole = 1:2 (molar ratio), and the experimental condition is that the modified basalt flake@ZIF-8 (recorded as MBS@ZIF-8) is reacted under the greenhouse condition, and the XRD patterns of the modified basalt flake@ZIF-8, the basalt flake (BS) and the ZIF-8 are shown in figure 3.
According to the invention, crystal structures of ZIF-8, BS and MBS@ZIF-8 fillers are respectively determined through XRD tests; the crystal structure of the ZIF-8 in-situ growth modified basalt flake (MBS@ZIF-8) filler is similar to that of a BS material, but the typical characteristic peak of the ZIF-8 can be observed in the range of 5-20 degrees 2 theta by amplifying an XRD spectrogram, so that the ZIF-8 in-situ growth modified basalt flake composite material is proved to be successfully prepared.
Aiming at the modified basalt flake@ZIF-8 prepared in the step (2), the invention uses a blank control group, modified basalt flake (MBS) and ZIF-8 as comparison, and performs a plate count test of antibacterial activity of staphylococcus aureus and escherichia coli, and the result is shown in figure 5.
The antibacterial performance of ZIF-8, MBS and MBS@ZIF-8 functional filler on escherichia coli and staphylococcus aureus is explored by a plate counting method; as shown in FIG. 5, a large number of bacterial colonies can be seen in the medium of the blank and MBS groups; due to the introduction of the ZIF-8, bacteria are fewer in a culture medium of the ZIF-8 and ZIF-8 in-situ growth modified basalt flakes (MBS@ZIF-8), wherein bacterial colonies in the ZIF-8 culture medium can only be observed at the edge of the culture medium, which indicates that the introduction of the ZIF-8 effectively improves the antibacterial property of the filler; therefore, the prepared ZIF-8 and MBS@ZIF-8 have excellent bactericidal effect on escherichia coli and staphylococcus aureus.
Salt spray tests of 0d, 5d, 10d, 20d, 30d and 45d were performed on the modified basalt flake @ ZIF-8-epoxy composite coating (denoted as MBS@ZIF-8/EP) prepared in the step (3) by using an epoxy resin coating (EP), a modified basalt flake coating (MBS/EP) and a ZIF-8 coating (ZIF-8/EP) as controls, and the results are shown in FIG. 4.
The corrosion resistance of the coating is characterized by a neutral salt spray test (NSS); it can be seen that in the salt spray test 5d, no obvious corrosion phenomena such as pitting and the like are observed on the surfaces of all the coatings; at 10d, the epoxy coating (EP) began to show significant pitting products, with greater corrosion areas of the epoxy coating (EP) occurring with prolonged exposure time; the epoxy coating (MBS/EP) added with the basalt flake filler modified by silane has pitting corrosion when exposed for 20d, and the corrosion resistance of the epoxy coating is improved relative to that of the epoxy coating; the ZIF-8 in-situ growth modified basalt flake functional filler is added into the epoxy coating, and no obvious corrosion is observed in the whole salt spray test process; the introduction of the surface ZIF-8 in-situ growth modified basalt flakes effectively improves the corrosion resistance of the epoxy coating.
The powder prepared by the preparation method of the invention is subjected to field emission scanning electron microscope and X-ray powder diffraction analysis to obtain the modified basalt flake functional filler with ZIF-8 uniform growth; carrying out mechanical property, antibacterial property test, electrochemical test and salt spray test on the antifouling coating to obtain a modified basalt flake @ ZIF-8-epoxy resin composite coating with excellent antibacterial and antiseptic properties; the coating prepared by the preparation scheme has excellent antibacterial salt spray resistance and meets the requirements of antifouling and anticorrosion under the current marine environment conditions; the salt spray resistance time of the coating material is 1080H, the chemical resistance after 216H soaking is 7.75X106 Ω & cm 2, the coating hardness is up to 6H, and the antibacterial performance is up to more than 98%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The preparation method of the modified basalt flake @ ZIF-8-epoxy resin composite coating is characterized by comprising the following steps of:
a) Alkylating and modifying basalt flakes to obtain modified basalt flakes; the alkylation modification process specifically comprises the following steps:
a1 Stirring basalt flakes in ethanol for 0.5-1.5 h, and then carrying out suction filtration, separation and drying to remove surface dirt for later use;
a2 0.5-1.5M HCl is used as a catalyst to prepare KH-550 solution with the volume percentage of 1-3% in ethanol, wherein the mass ratio of KH-550 to basalt flakes is (1-2): 10;
a3 Adding the basalt flakes in the step a 1) into the solution in the step a 2), stirring for 3-5 hours, filtering, separating, and drying at room temperature to obtain modified basalt flakes;
b) Mixing the modified basalt flakes obtained in the step a) with zinc salt solution, adding 2-methylimidazole, reacting, and sequentially filtering, washing and drying the obtained mixture to obtain modified basalt flakes @ ZIF-8; the mass ratio of the zinc salt to the modified basalt flakes is (0.5-2.5): 1, a step of; the molar ratio of Zn 2+ to 2-methylimidazole in the zinc salt is 1: (2-8); the reaction process specifically comprises the following steps:
Stirring at the temperature of 20-30 ℃ and the rotating speed of 100-300 r/min for 0.5-1.5 h, and standing for 20-30 h to obtain a mixture;
c) Dispersing the modified basalt flake @ ZIF-8 obtained in the step b) in an organic solvent, mixing with an epoxy resin solution and a polyamide curing agent, and sequentially coating and curing after ultrasonic defoaming to obtain the modified basalt flake @ ZIF-8-epoxy resin composite coating.
2. The method according to claim 1, wherein the basalt flakes in step a) have a mesh number of 200 mesh to 500 mesh.
3. The preparation method according to claim 1, characterized in that in step b) the zinc salt is selected from zinc nitrate and/or zinc acetate; the solvent of the zinc salt solution is selected from one or more of methanol, ethanol and water.
4. The preparation method according to claim 1, wherein the organic solvent in step c) is selected from one or more of acetone, butanone, toluene, xylene, methyl ethyl ketone, cyclohexanone, n-butanol, dioctyl phthalate, dibutyl phthalate and triethyl phosphate;
The mass ratio of the organic solvent to the modified basalt flake @ ZIF-8 is (0.5-1.5): 1.
5. The method according to claim 1, wherein the mass ratio of the modified basalt flake @ ZIF-8 to the epoxy resin solution and the polyamide curing agent in the step c) is 1: (5-15): (5-15).
6. The method according to claim 1, wherein the ultrasonic defoaming time in step c) is 20min to 40min.
7. The modified basalt flake@ZIF-8-epoxy resin composite coating is characterized by being prepared by the preparation method of any one of claims 1-6.
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