O-vanillin-based ZIFs in-situ coated MXene nano material as well as preparation method and application thereof

Abstract

The invention discloses an o-vanillin-based ZIFs in-situ coated MXene nano material as well as a preparation method and application thereof. The o-vanillin-based ZIFs in-situ coated MXene nano material is prepared by carrying out coordination reaction on raw materials including a bio-based organic precursor oVBZMI, a multi-layer MXene nano sheet and zinc nitrate hexahydrate, wherein the bio-based organic precursor oVBZMI is prepared by mixing and reacting o-vanillin, ammonium acetate, absolute ethyl alcohol and 1, 2-diaminobenzene. Nitrogen and oxygen atoms in oVBZMI have very strong chelating ability, and are adsorbed on the surface of a metal substrate to form a layer of protective film after being combined with Fe < 2 + >, so that the anti-corrosion process of metal is slowed down.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanocomposites, and particularly relates to an o-vanillin-based ZIFs in-situ coated MXene nanomaterial, a preparation method thereof, and an application thereof. Background Art

[0002] The phenomenon of metal corrosion cannot be ignored. It will seriously damage the performance and service life of metal materials, and thus cause huge losses to human society. Among various metal anti-corrosion methods, organic coating anti-corrosion is a widely used and effective method. Among various organic coatings, epoxy resin is widely used due to its excellent adhesion, chemical resistance, corrosion resistance, and excellent mechanical properties. However, during the actual application process, internal defects are likely to occur in the epoxy resin coating due to reasons such as solvent volatilization, resulting in a weakened shielding effect of the coating, allowing corrosive media to enter the substrate, thereby affecting the anti-corrosion performance of the coating. Therefore, it is crucial to introduce corrosion inhibitors to improve the long-term anti-corrosion performance of the coating.

[0003] O-vanillin (also known as o-vanillin) is one of the most widely sourced and applied biomass raw materials at present. It can be used to construct nitrogen-containing aromatic heterocyclic compounds, and then be used to prepare corrosion inhibitors and flame retardants. However, due to the limitation of flame retardant elements, the flame retardant efficiency of the flame retardant prepared from o-vanillin as a raw material is not high. The two-dimensional layered nanomaterial MXene has been widely applied in various fields due to its excellent physical barrier properties, thermal stability, and mechanical properties. However, the compatibility between inorganic fillers and the epoxy resin matrix is poor, and the fillers are unevenly dispersed in the resin and prone to agglomeration, which will introduce more defects in the matrix, thereby leading to a decrease in anti-corrosion performance.

[0004] Therefore, how to combine the above two materials, simultaneously exert their unique advantages, and prepare a multifunctional epoxy resin composite material has become an urgent problem to be solved. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects of the prior art and provide an o-vanillin-based ZIFs in-situ coated MXene nanomaterial.

[0006] Another purpose of the present invention is to provide a preparation method of the above o-vanillin-based ZIFs in-situ coated MXene nanomaterial.

[0007] Another purpose of the present invention is to provide an application of the above o-vanillin-based ZIFs in-situ coated MXene nanomaterial.

[0008] The technical solution of the present invention is as follows:

[0009] An o-vanillin-based ZIFs in-situ coated MXene nanomaterial is prepared by a coordination reaction of raw materials including a bio-based organic precursor oVBZMI, multilayer MXene nanosheets and zinc nitrate hexahydrate;

[0010] Among them, the bio-based organic precursor oVBZMI is made by the mixed reaction of o-vanillin, ammonium acetate, anhydrous ethanol and 1,2-diaminobenzene.

[0011] In a preferred embodiment of the present invention, the mass ratio of the bio-based organic precursor oVBZMI, the multilayer MXene nanosheets and the zinc nitrate hexahydrate is 2-2.5:0.3-0.4:1.5-2.

[0012] In a preferred embodiment of the present invention, the ratio of o-vanillin, ammonium acetate, anhydrous ethanol and 1,2-diaminobenzene is 12-18 g: 0.3-0.8 g: 100-200 mL: 11-12 g.

[0013] The preparation method of the above-mentioned o-vanillin-based ZIFs in-situ coated MXene nanomaterial comprises the following steps:

[0014] (1) After mixing o-vanillin, ammonium acetate and anhydrous ethanol, the mixture is heated to 60-70° C. while stirring, and then 1,2-diaminobenzene is added. After the mixture is stirred at the same temperature, the product is filtered and washed, and then filtered by suction, and then washed with anhydrous ethanol and deionized water, and then dried in an oven to obtain a bio-based organic precursor oVBZMI;

[0015] (2) stirring and mixing the multilayer MXene nanosheets and deionized water, and performing ultrasonic dispersion to obtain a mixture A;

[0016] (3) stirring and mixing zinc nitrate hexahydrate and deionized water to obtain a clear solution B;

[0017] (4) adding the clear solution B obtained in step (3) dropwise to the mixture A obtained in step (2), and performing ultrasonic dispersion treatment after the addition is complete to obtain a mixture C;

[0018] (5) mixing the oVBZMI obtained in step (1) with anhydrous ethanol, and after the oVBZMI is completely dissolved and naturally cooled, a clear orange liquid D is obtained;

[0019] (6) stirring and mixing the mixture C obtained in step (4) and the clear orange liquid D obtained in step (5) to uniformly carry out coordination reaction, followed by vacuum filtration, washing with anhydrous ethanol, washing with deionized water and vacuum drying in sequence to obtain the o-vanillin-based ZIFs in-situ coated MXene nanomaterial;

[0020] Use of the above o - vanillin - based ZIFs in - situ coated MXene nanomaterials in the preparation of epoxy resin composites.

[0021] An epoxy resin composite, the raw materials of which include the above o - vanillin - based ZIFs in - situ coated MXene nanomaterials.

[0022] In a preferred embodiment of the present invention, the raw materials further include E - 51 epoxy resin.

[0023] Use of the above o - vanillin - based ZIFs in - situ coated MXene nanomaterials in the preparation of epoxy resin anti - corrosion coatings.

[0024] An epoxy resin anti - corrosion coating, the raw materials of which include the above o - vanillin - based ZIFs in - situ coated MXene nanomaterials.

[0025] In a preferred embodiment of the present invention, the raw materials further include 901 epoxy resin.

[0026] The beneficial effects of the present invention are as follows:

[0027] 1. The present invention synthesizes a new biomass corrosion inhibitor, abbreviated as oVBZMI, using the biomass raw material o - vanillin. The nitrogen and oxygen atoms therein have strong chelating abilities and adsorb on the surface of the metal substrate after binding with Fe 2+ to form a protective film and slow down the corrosion process of the metal.

[0028] 2. The present invention uses MXene as a template and in - situ coats MXene nanosheets with the biomass precursor oVBZMI.

[0029] 3. The nanorods in the present invention are directly grown on the surface of MXene from the biomass organic precursor oVBZMI.

[0030] 4. The physical barrier of MXene and the corrosion inhibition effect of oVBZMI in the present invention greatly delay the corrosion of metals and endow the epoxy resin composite with long - term anti - corrosion performance.

[0031] 5. The present invention directly uses epoxy resin to infiltrate and exfoliate MXene sheets, maximizing the role of MXene while reducing the pollution and raw material waste caused by etching single - layer MXene.

[0032] 6. The modification with o - vanillin - based ZIFs in the present invention improves the compatibility between MXene and epoxy resin, and successfully improves the defects such as easy oxidation and easy folding of MXene, and improves the mechanical properties of the epoxy resin composite.

[0033] 7. In the MXene@ZIF nanomaterial of the present invention, the synergistic effect of flame retardant elements such as N, Zn, and Ti in the gas phase and condensed phase greatly improves the flame retardant efficiency of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 It is the technical principle diagram of the present invention.

[0035] Figure 2 It is the XPS energy spectrum diagram and the fine spectrum diagram of the elements contained in MXene@ZIF prepared in Example 1 of the present invention, ZIF-oV prepared in Comparative Example 1, and MXene prepared in Comparative Example 2.

[0036] Figure 3 It is the scanning electron microscope diagram of MXene@ZIF prepared in Example 1 of the present invention, ZIF-oV prepared in Comparative Example 1, and MXene prepared in Comparative Example 2.

[0037] Figure 4 It is the XRD diagram of MXene@ZIF prepared in Example 1 of the present invention, ZIF-oV prepared in Comparative Example 1, and MXene prepared in Comparative Example 2.

[0038] Figure 5 It is the comparison diagram of the tensile test of the EP / MX@ZIF, EP / ZIFs, and EP / MXene resin splines prepared in Example 1, Comparative Example 1, and Comparative Example 2 of the present invention.

[0039] Figure 6 It is the heat release curve diagram of the EP / MX@ZIF, EP / ZIFs, and EP / MXene resin splines prepared in Example 1, Comparative Example 1, and Comparative Example 2 of the present invention tested by a cone calorimeter.

[0040] Figure 7 It is the electrochemical impedance spectroscopy test diagram of the EP / MX@ZIF, EP / ZIFs, and EP / MXene resin coatings prepared in Example 1, Comparative Example 1, and Comparative Example 2 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0041] The technical solutions of the present invention will be further described and described below through specific embodiments in conjunction with the drawings.

[0042] Example 1

[0043] The specific principle of the present invention is as Figure 1 shown. Specifically in this embodiment, it includes the following steps:

[0044] (1) Add 15 g of o-vanillin, 0.4 g of ammonium acetate, and 100 mL of absolute ethanol into a three-necked flask equipped with a magnetic stirrer and under nitrogen protection. After heating to 60 °C, add 11 g of 1,2-diaminobenzene thereto, keep the temperature and continue stirring for a period of time. Filter and wash the product, and then after suction filtration, wash it twice with absolute ethanol and deionized water respectively, and then dry it in a vacuum oven at 55 °C to obtain the bio-based organic precursor oVBZMI;

[0045] (2) Add 0.38 g of multi-layer MXene nanosheets into a beaker, then add 150 mL of deionized water, stir evenly, and place it in an ultrasonic cleaner to disperse the multi-layer MXene nanosheets evenly to obtain mixture A;

[0046] (3) Add 2 g of Zn(NO3)2·6H2O into a beaker, then add 100 mL of deionized water, stir evenly to obtain a clear solution B;

[0047] (4) Drop the clear solution B obtained in step (3) into the mixture A obtained in step (2). After dropping, place it in an ultrasonic cleaner for ultrasonic dispersion treatment to obtain mixture C;

[0048] (5) Place a single-necked flask in an oil bath equipped with a magnetic stirrer, put in a magnetic stir bar, then add 2 g of oVBZMI prepared in step (1) and 400 mL of absolute ethanol and stir. After oVBZMI is completely dissolved and naturally cooled, a clear orange liquid D is obtained;

[0049] (6) Place the mixture C prepared in step (4) on a stirring table and stir. Then quickly pour the clear orange liquid D prepared in step (5) into it, stir for 2 h for the coordination reaction. After the reaction ends, pour the reaction product into a Buchner funnel for vacuum filtration, wash it three times with absolute ethanol and deionized water respectively, and then place the product in a vacuum drying at 55 °C for 48 h to obtain ZIF-oV coated multi-MXene nanosheets (MXene@ZIF);

[0050] (7) Mix the MXene@ZIF prepared in step (6) with E-51 epoxy resin (mass ratio 1:20), cure it at 130 °C and 170 °C for 1 h respectively, and then cure it at 200 °C for 1 h to obtain an epoxy resin composite spline EP / MX@ZIF; Mix the MXene@ZIF prepared in step (6) with 901 epoxy resin (mass ratio 1:20), coat the paint on the polished steel plate, then let the coated coating stand at room temperature for 24 h, and then place it in a forced-air oven at 70 °C for further curing for 1 h, and then cure it at room temperature for 3 days to obtain an anti-corrosion coating.

[0051] Comparative Example 1

[0052] (1) Add 12 g of o-vanillin, 0.32 g of ammonium acetate, and 100 mL of absolute ethanol into a three-necked flask equipped with a magnetic stirrer and under nitrogen protection. After heating to 60 °C, add 11 g of 1,2-diaminobenzene thereto, keep the temperature and continue stirring for a period of time. Filter and wash the product, and then after suction filtration, wash it twice with absolute ethanol and deionized water respectively, and then dry it in a vacuum oven at 55 °C to obtain the bio-based organic precursor oVBZMI;

[0053] (2) Add 1.5 g of Zn(NO3)2·6H2O into a beaker, and then add 100 mL of deionized water and stir evenly to obtain a clear solution B;

[0054] (3) Add the bio-based organic precursor oVBZMI obtained in step (1) to the clear solution B obtained in (2). After dropping, place it in an ultrasonic cleaner for ultrasonic dispersion treatment to obtain biomass ZIFs (ZIF-oV);

[0055] (4) Mix the ZIF-oV prepared in step (3) with E-51 epoxy resin (mass ratio 1:20), cure it at 130 °C and 170 °C for 2 h respectively, and then cure it at 200 °C for 2 h to obtain an epoxy resin composite spline EP / ZIFs; Mix the ZIF-oV prepared in step (3) with 901 epoxy resin (mass ratio 1:20), coat the paint on the polished steel plate, then let the coated coating stand at room temperature for 12 h, and then place it in a forced-air oven at 70 °C for further curing for 1 h, and then cure it at room temperature for 3 days to obtain an anti-corrosion coating.

[0056] Comparative Example 2

[0057] (1) Add 0.38 g of multi-layer MXene nanosheets into a beaker, then add 150 mL of deionized water, stir evenly, and place it in an ultrasonic cleaner to disperse the multi-layer MXene nanosheets evenly to obtain multi-layer MXene nanosheets (MXene);

[0058] (2) Mix the multi-layer MXene nanosheets prepared in step (1) with E-51 epoxy resin (mass ratio 1:20), cure it at 130 °C and 170 °C for 2 h respectively, and then cure it at 200 °C for 2 h to obtain an epoxy resin composite spline EP / MXene; Mix the multi-layer MXene nanosheets prepared in step (1) with 901 epoxy resin (mass ratio 1:20), coat the paint on the polished steel plate, then let the coated coating stand at room temperature for 12 h, and then place it in a forced-air oven at 70 °C for further curing for 1 h, and then cure it at room temperature for 3 days to obtain an anti-corrosion coating.

[0059] Figures 2 to 4All of them prove that the synthesized MXene@ZIF has the characteristic structures of MXene and vanillin ZIFs, indicating that the MXene@ZIF nanomaterial has been successfully prepared.

[0060] Figure 6 It is concluded that the MXene@ZIF flame-retardant epoxy resin nanomaterial prepared by the present invention has the best flame-retardant performance. Through comparison by a cone calorimeter test, compared with pure epoxy resin, when the mass fraction of MXene@ZIF is only 3%, the flame-retardant performance of the epoxy resin composite has been significantly improved, and its total heat release and total smoke production are reduced by about 32.2% and about 16.2% respectively, and the heat release rate, smoke production rate, and the release amounts of CO and CO2 are also reduced. By tensile test comparison,

[0061] From Figure 5 it can be seen that compared with pure epoxy resin, when the mass fraction of MXene@ZIF is only 3%, the tensile strength and Young's modulus of the epoxy resin composite spline are increased by 13.8% and 20% respectively. The corrosion protection performance test is carried out for comparison.

[0062] From Figure 7 it can be seen that compared with pure epoxy resin, EP / ZIFs composite and EP / MXene composite, the EP / MX@ZIF composite has excellent corrosion protection performance, which can effectively slow down the penetration rate of the corrosive medium into the steel plate, making the epoxy resin composite have excellent long-term corrosion protection performance.

[0063] As mentioned above, it is only a preferred embodiment of the present invention, so the scope of implementation of the present invention cannot be limited thereby. That is, equivalent changes and modifications made according to the scope of the present invention patent and the content of the specification should still fall within the scope covered by the present invention.

Claims

1. A o-vanillin-based ZIFs in-situ coated MXene nanomaterial, characterized in that: It is made by coordination reaction of raw materials including bio-based organic precursor oVBZMI, multilayer MXene nanosheets and zinc nitrate hexahydrate; Among them, the bio-based organic precursor oVBZMI is made by the mixed reaction of o-vanillin, ammonium acetate, anhydrous ethanol and 1,2-diaminobenzene.

2. The o - vanillin - based ZIFs in - situ coated MXene nanomaterial according to claim 1, wherein: The mass ratio of the bio-based organic precursor oVBZMI, the multilayer MXene nanosheets and the hexahydrate zinc nitrate is 2-2.5:0.3-0.4:1.5-2.

3. The o - vanillin - based ZIFs in - situ coated MXene nanomaterial according to claim 1 or 2, characterized in that: The ratio of o-vanillin, ammonium acetate, anhydrous ethanol and 1,2-diaminobenzene is 12-18 g: 0.3-0.8 g: 100-200 mL: 11-12 g.

4. The preparation method of a vanillin-based ZIFs in-situ coated MXene nanomaterial according to any one of claims 1 to 3, characterized in that: The steps include: (1) After mixing o-vanillin, ammonium acetate and anhydrous ethanol, the mixture is heated to 60-70° C. while stirring, and then 1,2-diaminobenzene is added. After the mixture is stirred at the same temperature, the product is filtered and washed, and then filtered by suction, and then washed with anhydrous ethanol and deionized water, and then dried in an oven to obtain a bio-based organic precursor oVBZMI; (2) stirring and mixing the multilayer MXene nanosheets and deionized water, and performing ultrasonic dispersion to obtain a mixture A; (3) stirring and mixing zinc nitrate hexahydrate and deionized water to obtain a clear solution B; (4) adding the clear solution B obtained in step (3) dropwise to the mixture A obtained in step (2), and performing ultrasonic dispersion treatment after the addition is complete to obtain a mixture C; (5) mixing the oVBZMI obtained in step (1) with anhydrous ethanol, and after the oVBZMI is completely dissolved and naturally cooled, a clear orange liquid D is obtained; (6) The mixture C obtained in step (4) and the clear orange liquid D obtained in step (5) are stirred and mixed uniformly to carry out coordination reaction, followed by vacuum filtration, washing with anhydrous ethanol, washing with deionized water and vacuum drying to obtain the o-vanillin-based ZIFs in-situ coated MXene nanomaterial.

5. Use of the o-vanillin-based ZIFs in-situ coated with MXene nanomaterials according to any one of claims 1 to 3 in the preparation of epoxy resin composites.

6. An epoxy resin composite material, characterized in that: The raw materials include the o-vanillin-based ZIFs in-situ coated MXene nanomaterials described in any one of claims 1 to 3.

7. An epoxy resin composite according to claim 6, characterized in that: Its raw materials also include E-51 epoxy resin.

8. Use of the o-vanillin-based ZIFs in-situ coated with MXene nanomaterials according to any one of claims 1 to 3 in the preparation of epoxy resin anti-corrosion coatings.

9. An epoxy resin anti-corrosion coating, characterized in that: The raw materials include the o-vanillin-based ZIFs in-situ coated MXene nanomaterials described in any one of claims 1 to 3.

10. An epoxy resin anti-corrosion coating according to claim 9, characterized in that: Its raw materials also include 901 epoxy resin.

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