CN112940275B - Preparation method of metal organic framework compound material - Google Patents
Preparation method of metal organic framework compound material Download PDFInfo
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- CN112940275B CN112940275B CN202110181793.1A CN202110181793A CN112940275B CN 112940275 B CN112940275 B CN 112940275B CN 202110181793 A CN202110181793 A CN 202110181793A CN 112940275 B CN112940275 B CN 112940275B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
The invention discloses a preparation method of a metal organic framework compound material, which comprises the steps of firstly dissolving zinc nitrate, 2-methylimidazole and 8-hydroxyquinoline as a corrosion response agent in methanol according to a certain proportion, mixing and crystallizing for 1-24 hours at room temperature to obtain white turbid liquid; centrifuging the obtained white suspension at a centrifugal speed of 10000r/min for 10 minutes, and then centrifuging and cleaning for 3 times by using ethanol; and (3) putting the cleaned product into a drying oven, and drying for 6-9 hours at the temperature of 60-90 ℃ to obtain the metal organic framework compound loaded with the corrosion response agent 8-hydroxyquinoline. The method can effectively coat and release the corrosion response agent to make the corrosion response agent timely respond to corrosion, thereby monitoring and early warning the corrosion of the coating, prolonging the service life of the metal material and improving the service safety.
Description
Technical Field
The invention relates to the technical field of metal corrosion and protection, in particular to a preparation method of a metal organic framework compound material.
Background
The intelligent self-repairing anticorrosive coating developed in recent years can automatically repair the damaged part of the coating according to environmental changes, enhance the protective capability of the coating and prolong the service life of a metal substrate, however, the limited self-repairing capability of the coating is still in the face of a new corrosion risk problem after being consumed along with the passage of the service time of the coating, so that the corrosion control and monitoring of the metal are particularly important, the corrosion detection in the prior art mainly depends on expensive equipment such as an electrochemical instrument, and the detection personnel are required to have higher professional knowledge capability for test analysis, the method is inconvenient to operate, and the result is easily interfered by the external environment.
The addition of a corrosion-responsive agent to the coating is a simple method of corrosion monitoring, such as doping the coating itself directly with a corrosion-responsive agent that precipitates during penetration of the coating by the environmental medium and responds to corrosion. However, the direct addition has many problems, such as that the release behavior of the corrosion response agent is difficult to regulate, the corrosion response agent is rapidly consumed in a short period, and the corrosion response agent may react with a coating substrate, so that the corrosion response agent fails or the coating degrades, and the like, so that how to realize the coating and release of the corrosion response agent can timely respond to corrosion when the corrosion occurs has important significance for the safe service of metal materials.
Disclosure of Invention
The invention aims to provide a preparation method of a metal organic framework compound material, which can effectively coat and release a corrosion response agent to make the corrosion response agent respond to corrosion in time, so that monitoring and early warning are carried out on coating corrosion, the service life of a metal material is prolonged, and the service safety is improved.
The purpose of the invention is realized by the following technical scheme:
a method of preparing a metal-organic framework compound material, the method comprising:
and 3, putting the product cleaned in the step 2 into an oven, and drying for 6-9 hours at the temperature of 60-90 ℃ to obtain the metal organic framework compound loaded with the corrosion response agent 8-hydroxyquinoline.
According to the technical scheme provided by the invention, the corrosion response agent can be effectively coated and released by the method, so that the corrosion response agent can timely respond to corrosion, the corrosion of the coating is monitored and early-warned, the service life of the metal material is prolonged, and the service safety is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 is a schematic flow chart of a preparation method of a metal-organic framework compound material according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
The following will describe embodiments of the present invention in further detail with reference to the accompanying drawings, and as shown in fig. 1, a schematic flow chart of a method for preparing a metal organic framework compound material provided by the embodiments of the present invention is shown, where the method includes:
in the step, the molar ratio of the zinc nitrate to the 2-methylimidazole is 1: 6-1: 12;
wherein the concentration of the 2-methylimidazole is 0.5-1 mol/L;
the addition amount of the corrosion response agent 8-hydroxyquinoline is 0.0025-0.1 mol/L.
and 3, putting the product cleaned in the step 2 into an oven, and drying for 6-9 hours at the temperature of 60-90 ℃ to obtain the metal organic framework compound loaded with the corrosion response agent 8-hydroxyquinoline.
The finally obtained metal organic framework compound carrying the corrosion response agent 8-hydroxyquinoline is white powder, and the particle size is 200-500 nm.
In the specific implementation, after the metal organic framework compound loaded with the corrosion responder 8-hydroxyquinoline is obtained, the obtained metal organic framework compound loaded with the corrosion responder 8-hydroxyquinoline can be added into organosilane, epoxy paint or polyurethane paint in a mechanical stirring manner and stirred uniformly;
and then applying the organic coating added with the metal organic framework compound on the surface of a metal matrix by any one of dip coating, brush coating and spray coating, and curing to form the anticorrosive coating with the corrosion early warning function.
The addition amount of the metal organic framework compound in organosilane is 0.1-5 g/L; the addition amount of the epoxy resin in the epoxy paint or polyurethane paint is 2-20 g/L.
The preparation method and application of the metal organic framework compound material are described in detail by the following specific examples:
examples 1, 1,
1. Preparation of metal organic framework compound with corrosion response function:
adding 9mmol of Zn (NO)3)·6H2Dissolving O in 60ml of methanol, dissolving 90mmol of 2-methylimidazole and 0.5mmol of 8-hydroxyquinoline in 60ml of methanol, mixing the two solutions, stirring the mixture in a closed manner for 24 hours at room temperature (25 +/-1 ℃) and carrying out ultrasonic treatment for 10 minutes;
then, the mixture was centrifuged at a centrifugation speed of 10000r/min for 10 minutes to collect a white precipitate.
And centrifugally cleaning the obtained precipitates for 3 times by using ethanol respectively, and drying the precipitates for 6 hours in an oven at the temperature of 60 ℃ to obtain white powder with the average particle size of 200 nm.
2. Preparing a self-repairing and corrosion monitoring early warning dual-function coating:
taking the organosilane coating as an example: adding 0.1g/L of the powder material into sol of which the main film-forming agent is 3-glycidyloxypropyltrimethoxysilane and tetraethoxysilane, hermetically stirring for 30 minutes at room temperature, aging for one day, and dip-coating after the components are uniformly mixed. And coating the sol on the surface of the polished and pretreated aluminum alloy 2024 sample by adopting a dip-coating method, and drying for one day in a 60 ℃ blast drying oven to obtain a uniform, compact and transparent organosilane coating.
After the coating sample is scratched, the coating sample is soaked in 3.5 wt% NaCl solution for 1-3 days, the macroscopic morphology of the scratched sample and the fluorescence condition under a fluorescence microscope are observed, the coating sample can emit obvious blue fluorescence at the scratched corrosion part, and the blue fluorescence points at the scratched part are increased along with the prolonging of the soaking time, which means that the corrosion condition is aggravated.
In addition, after the metal organic framework compound nano powder with the corrosion response function is added into organic silane, compared with an electrochemical impedance spectrum and a polarization curve of an organic silane sample which is not added, the corrosion resistance of the metal organic framework compound nano powder is obviously improved, and the capability of prolonging the corrosion resistance life of a coating is shown.
Examples 2,
1. Preparation of metal organic framework compound with corrosion response function:
adding 9mmol of Zn (NO)3)·6H2Dissolving O in 60ml of methanol, dissolving 90mmol of 2-methylimidazole and 1mmol of 8-hydroxyquinoline in 60ml of methanol, mixing the two solutions, stirring the mixture in a closed manner for 24 hours at room temperature (25 +/-1 ℃) and carrying out ultrasonic treatment for 10 minutes;
then centrifuging for 10 minutes at the centrifugal speed of 10000r/min, and collecting white precipitate;
and centrifugally cleaning the obtained precipitate with ethanol for 3 times, and drying in an oven at 60 ℃ for 6 hours to obtain white powder.
2. Preparing a self-repairing and corrosion monitoring early warning dual-function coating:
the method for adding the epoxy primer to the steel for corrosion prevention and corrosion monitoring comprises the following steps:
1) adding 5g/L of the powder into the epoxy primer, and stirring for 30 minutes at room temperature until the powder is uniformly mixed;
2) and brushing the mixed epoxy primer on the surface of the polished Q235 carbon steel, and curing for 24 hours at room temperature to obtain the self-repairing and corrosion monitoring and early warning epoxy coating.
Examples 3,
1. Preparation of metal organic framework compound with corrosion response function:
adding 9mmol of Zn (NO)3)·6H2Dissolving O in 60ml of methanol, dissolving 90mmol of 2-methylimidazole and 3mmol of 8-hydroxyquinoline in 60ml of methanol, mixing the two solutions, stirring the mixture in a closed manner for 24 hours at room temperature (25 +/-1 ℃) and carrying out ultrasonic treatment for 10 minutes;
then centrifuging for 10 minutes at the centrifugal speed of 10000r/min, and collecting white precipitate;
and centrifugally cleaning the obtained precipitate with ethanol for 3 times, and drying in an oven at 60 ℃ for 6 hours to obtain white powder.
2. Preparing a self-repairing and corrosion monitoring early warning dual-function coating:
taking a polyurethane coating as an example, adding 3g/L of the powder into the polyurethane coating, and stirring for 30 minutes at room temperature until the powder is uniformly mixed;
and spraying the mixed polyurethane coating on the surface of the polished aluminum alloy 6063 sample, and curing at room temperature for 24 hours to obtain the polyurethane coating with the self-repairing and corrosion monitoring and early warning functions.
It is noted that those skilled in the art will recognize that embodiments of the present invention are not described in detail herein.
In summary, the metal organic framework compound material with the corrosion response function in the embodiment of the invention can be synthesized at room temperature, has the advantages of simple process, good repeatability, strong controllability, high yield and the like, can be widely applied to monitoring corrosion failure of metal in organic coating, can perform self-diagnosis and early warning on damaged sites of a coating in time without external interference, and prompts people to find damaged sites in time and perform manual repair, thereby ensuring the service safety of material equipment.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (3)
1. The application method of the metal organic framework compound material is characterized in that the preparation method of the metal organic framework compound material comprises the following steps:
step 1, dissolving zinc nitrate, 2-methylimidazole and 8-hydroxyquinoline serving as a corrosion response agent in a certain proportion in methanol, mixing at room temperature, and crystallizing for 1-24 hours to obtain a white suspension;
step 2, centrifuging the obtained white suspension for 10 minutes at a centrifugal speed of 10000r/min, and then centrifuging and cleaning for 3 times by using ethanol;
step 3, putting the product cleaned in the step 2 into an oven, and drying for 6-9 hours at the temperature of 60-90 ℃ to obtain a metal organic framework compound loaded with a corrosion response agent 8-hydroxyquinoline;
after the metal organic framework compound loaded with the corrosion responder 8-hydroxyquinoline is obtained in the step 3, adding the obtained metal organic framework compound loaded with the corrosion responder 8-hydroxyquinoline into organosilane, epoxy paint or polyurethane paint in a mechanical stirring manner, and uniformly stirring;
applying the organic coating added with the metal organic framework compound on the surface of a metal matrix by any one of dip coating, brush coating and spray coating, and curing to form the anticorrosive coating with a corrosion early warning function;
the addition amount of the metal organic framework compound in organosilane is 0.1-5 g/L;
the addition amount of the metal organic framework compound in the epoxy paint or the polyurethane paint is 2-20 g/L.
2. The application method of the metal-organic framework compound material as claimed in claim 1, wherein in the step 1, the molar ratio of the zinc nitrate to the 2-methylimidazole is 1: 6-1: 12;
wherein the concentration of the 2-methylimidazole is 0.5-1 mol/L;
the addition amount of the corrosion response agent 8-hydroxyquinoline is 0.0025-0.1 mol/L.
3. The application method of the metal organic framework compound material as claimed in claim 1, wherein the obtained metal organic framework compound carrying the corrosion-responsive agent 8-hydroxyquinoline is white powder with a particle size of 200-500 nm.
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| CN106892868A (en) * | 2017-02-28 | 2017-06-27 | 广东工业大学 | A kind of 8 oxyquinoline Zn complexes with one-dimensional catenary structure and preparation method thereof |
| CN110183569A (en) * | 2019-05-30 | 2019-08-30 | 江南大学 | A kind of metal erosion early warning polymer coating materials and preparation method thereof |
| CN111234566A (en) * | 2020-01-22 | 2020-06-05 | 湖南大学 | Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating |
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| CN106892868A (en) * | 2017-02-28 | 2017-06-27 | 广东工业大学 | A kind of 8 oxyquinoline Zn complexes with one-dimensional catenary structure and preparation method thereof |
| CN110183569A (en) * | 2019-05-30 | 2019-08-30 | 江南大学 | A kind of metal erosion early warning polymer coating materials and preparation method thereof |
| CN111234566A (en) * | 2020-01-22 | 2020-06-05 | 湖南大学 | Acid-base double-response hollow mesoporous silica composite nano container, self-repairing anticorrosive coating and preparation method of self-repairing anticorrosive coating |
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