Polyurea material containing modified MOFs and preparation method thereof

Abstract

The invention belongs to the field of composite materials, and particularly relates to a polyurea material containing modified MOFs and a preparation method of the polyurea material. The polyurea material is prepared from polyurea resin and a modified MOFs (Metal-Organic Frameworks) material, wherein the polyurea resin is prepared from double-component polyurea, single-component polyurea and water-based polyurea; the modified MOFs material is prepared by adopting a'one-pot method ', graphene oxide is ultrasonically dispersed into a precursor solution required for synthesizing MOFs, and a hydrothermal reaction is performed under the same reaction conditions as pure MOFs preparation, so that the modified MOFs material is obtained. The MOFs material is an MOFs material of which the surface is modified by-NH2; the modified MOFs material has the advantages of high porosity and large specific surface area, and can be used as a container for packaging functional aids. The modified MOFs-containing polyurea material has excellent corrosion resistance, adhesive force, impact resistance, water resistance and thermal stability, the preparation method is simple, the characteristics of organic and inorganic composite materials are exerted, and the application range of polyurea is widened.

Description

Technical Field

[0001] This invention belongs to the field of composite materials, specifically relating to a polyurea material containing modified MOFs and its preparation method. Background Technology

[0002] Metal-organic frameworks (MOFs) are porous crystalline materials formed by the self-assembly of organic ligands and metal ions. They have the characteristics of large specific surface area, low framework density, open metal sites, and regular and ordered crystal structure. They are inorganic nanomaterials that have been developed rapidly in the field of coordination chemistry in recent decades. However, due to their structural instability, easy aggregation, and easy structural collapse when exposed to moisture, the application of MOF materials is limited.

[0003] Graphene oxide (GO) is a representative two-dimensional nanosheet material, characterized by its large specific surface area, abundant oxygen-containing functional groups, good solvent dispersibility, and highly tunable physicochemical properties. The GO surface has numerous oxygen-containing groups, including strongly conjugated structures and negatively charged functional groups, making GO readily interact with MOFs to form hybrid composites. Furthermore, MOFs modified with -NH2 provide more binding sites, further increasing the porosity and stability of the modified MOFs. The stable two-dimensional planar structure of GO enhances the structural stability of MOFs, while GO's strong hydrophilicity facilitates the dispersion of MOFs in solvents.

[0004] GO, with its ultra-thin single-atom thickness, excellent conductivity, high chemical inertness, and perfect barrier properties against gases and ions, has become one of the most promising corrosion-resistant nanofillers. MOFs (Metal-Organic Facility) materials contain organic molecules with electron donor atoms (such as nitrogen, phosphorus, sulfur, and oxygen) and electron acceptor centers (such as transition metal ions like zinc). They are effective metal corrosion inhibitors in both solution and coated phases. Furthermore, MOFs possess abundant microporous structures, huge specific surface areas, and high porosity, making them suitable containers for encapsulating corrosion inhibitors. Therefore, the combination of GO and MOFs can not only improve upon the shortcomings of MOFs but also serve as an excellent corrosion-resistant filler.

[0005] Polyurea is a novel, solvent-free, and pollution-free green material. Due to the significant polarity difference and strong intermolecular forces between the soft and hard segments in polyurea, a unique microphase separation morphology emerges in its structure, resulting in excellent thermal and mechanical properties, as well as weather resistance. However, its corrosion resistance is insufficient. Therefore, it is necessary to combine MOF materials with polyurea resin to develop a polyurea material with superior corrosion resistance, mechanical properties, and weather resistance. Summary of the Invention

[0006] The purpose of this invention is to provide a polyurea material containing modified MOFs and its preparation method, so as to solve the problems of insufficient anti-corrosion performance and process.

[0007] The technical solution of the present invention is a polyurea material containing the following components in parts by weight: Polyurea resin: 50-85 parts by weight, preferably 75-85 parts by weight, more preferably 83.4 parts by weight or 50 parts by weight; Modified MOFs material: 0.5 to 5 parts by weight, preferably 0.5 to 2 parts by weight, more preferably 1 part by weight or 3 parts by weight; Dispersant: 0.2 to 1 part by weight, preferably 0.3 to 0.5 parts by weight, more preferably 0.4 parts by weight or 1 part by weight; Defoamer: 0.2 to 1 part by weight, preferably 0.2 to 0.4 parts by weight, more preferably 0.2 parts by weight or 1 part by weight; Solvent: 10-45 parts by weight, preferably 14-23 parts by weight, more preferably 15 parts by weight or 45 parts by weight.

[0008] The polyurea resin is selected from at least one of two-component polyurea, one-component polyurea, and waterborne polyurea, preferably any one of two-component polyurea, one-component polyurea, and waterborne polyurea, and more preferably one-component polyurea or waterborne polyurea.

[0009] The defoamer is selected from at least one of polysiloxane, polyether polysiloxane, and mineral oil, preferably BYK-024 or polyether polysiloxane.

[0010] The dispersant is selected from at least one of sodium dodecyl sulfate, polyacrylamide, methylpentanol, and cellulose derivatives, preferably sodium dodecyl sulfate or polyacrylamide.

[0011] The solvent is selected from at least one of water, anhydrous methanol, acetone, methyl ethyl ketone, ethyl acetate, toluene, dichloromethane, tetrahydrofuran, and N,N-dimethylformamide, preferably water or anhydrous methanol.

[0012] The modified MOF material is a modified MOF material loaded with functional additives, and its preparation includes: S1, graphene oxide is uniformly dispersed in a precursor solution for MOF synthesis, and a one-pot hydrothermal reaction is performed to obtain graphene oxide-modified MOF materials; the precursor solution for MOF synthesis is an organic solvent uniformly dispersed with organic ligands and metal ions; the amount of graphene oxide incorporated accounts for 0.5 wt%-5 wt% of the mass of the precursor solution for MOF synthesis, preferably 0.5 wt%-2 wt%, more preferably 1 wt%; the purity of the graphene oxide is greater than 95 wt%, preferably 99 wt%; the thickness is 1 nm ~ The nanometer diameter is 20 nm, preferably 3 nm; the lateral dimension of the planar structure is 1 μm-100 μm, preferably 10 μm; in the precursor solution for synthesizing MOFs, the molar ratio of organic ligand to metal ion is 1:2-3, preferably 1:2-2.5, more preferably 1:2; the molar ratio of organic ligand to organic solvent is 0.01-0.08 mol:1 L, preferably 0.04-0.05 mol:1 L; the organic ligand is selected from at least one of 2-aminoterephthalic acid, 3-aminophthalic acid, and 4-aminophthalic acid, preferably 2-aminoterephthalic acid; the metal ion includes all metal ions, such as main group element metal ions, transition element metal ions, lanthanide metal ions, etc., preferably Zn ions; the organic solvent is selected from N, At least one of N-dimethylformamide (DMF), 1-methyl-2-pyrrolidone (NMP), methanol, and ethanol, preferably DMF; the temperature of the one-pot hydrothermal reaction is 80℃-130℃, preferably 100℃, and the reaction time is 12-24 h, preferably 24 h; the synthesized MOF material belongs to at least one of the IRMOF series, ZIF series, CPL series, MIL series, PCN series, and UIO series, preferably the IRMOF series.

[0013] The graphene oxide-modified MOFs material has the advantages of high porosity and large specific surface area, and can be used as a container for encapsulating functional additives.

[0014] S2, the graphene oxide-modified MOF material is uniformly dispersed in a solvent containing functional additives and stirred to obtain a modified MOF material loaded with functional additives; the solvent is selected from at least one of anhydrous ethanol, anhydrous methanol, dichloromethane, and acetone, preferably anhydrous ethanol; the functional additives include at least one of many additives such as self-healing agents, corrosion inhibitors, flame retardants, antistatic agents, and antioxidants, preferably corrosion inhibitors; the corrosion inhibitors include at least one of benzotriazole, phosphonic acid, and sulfonated lignin, preferably benzotriazole.

[0015] This invention provides a method for preparing modified MOFs materials with functional additives, comprising the following steps: S1, graphene oxide is uniformly dispersed in a precursor solution for synthesizing MOFs, and a one-pot hydrothermal reaction is carried out to obtain graphene oxide modified MOFs materials; the precursor solution for synthesizing MOFs is an organic solvent in which organic ligands and metal ions are uniformly dispersed. S2, the graphene oxide modified MOF material is uniformly dispersed in a solvent containing functional additives, and stirred to obtain the modified MOF material loaded with functional additives.

[0016] In S1, the amount of graphene oxide incorporated accounts for 0.5 wt%-5 wt% of the precursor solution for synthesizing MOFs, preferably 0.5 wt%-2 wt%, more preferably 1 wt%; the purity of the graphene oxide is greater than 95 wt%, preferably 99 wt%; the thickness is 1 nm to 20 nm, preferably 3 nm; the lateral dimension of the planar surface is 1 μm to 100 μm, preferably 10 μm.

[0017] In S1, the molar ratio of organic ligand to metal ion in the precursor solution for synthesizing MOFs is 1:2-3, preferably 1:2-2.5, and more preferably 1:2; the molar ratio of organic ligand to organic solvent is 0.01-0.08 mol:1 L, preferably 0.04-0.05 mol:1 L; the organic ligand is selected from at least one of 2-aminoterephthalic acid, 3-aminophthalic acid, and 4-aminophthalic acid, preferably 2-aminoterephthalic acid; the metal ion includes all metal ions, such as main group element metal ions, transition element metal ions, lanthanide metal ions, etc., preferably Zn ions; the organic solvent is selected from at least one of N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidone (NMP), methanol, and ethanol, preferably DMF.

[0018] In S1, the temperature of the hydrothermal reaction is 80℃-130℃, preferably 100℃; the reaction time is 12-24 h, preferably 24 h.

[0019] In S1, the synthesized MOFs material belongs to at least one of the IRMOF series, ZIF series, CPL series, MIL series, PCN series, and UIO series, preferably belonging to the IRMOF series.

[0020] In S2, the solvent is selected from at least one of anhydrous ethanol, anhydrous methanol, dichloromethane, and acetone, with anhydrous ethanol being preferred.

[0021] In S2, the functional additives include at least one of many additives such as self-healing agents, corrosion inhibitors, flame retardants, antistatic agents, and antioxidants, preferably corrosion inhibitors; the corrosion inhibitors include at least one of benzotriazole, phosphonic acid, and sulfonated lignin, preferably benzotriazole.

[0022] The present invention also provides a modified MOF material with functional additives, which is prepared by the above-described preparation method of a modified MOF material with functional additives.

[0023] This invention provides a method for preparing a polyurea material containing modified MOFs, comprising the steps of: incorporating a modified MOF material carrying functional additives into a polyurea resin to obtain the polyurea material. The amount of polyurea resin incorporated is 50-85 parts by weight, preferably 75-85 parts by weight, and more preferably 83.4 parts by weight; the polyurea resin is selected from at least one of two-component polyurea, one-component polyurea, and waterborne polyurea, preferably two-component polyurea. The amount of the modified MOF material carrying functional additives incorporated is 0.5-5 parts by weight, preferably 0.5-2 parts by weight, and more preferably 1 part by weight.

[0024] Furthermore, a dispersant, an antifoaming agent, and a solvent are also incorporated. The dispersant is incorporated in an amount of 0.2 to 1 part by weight, preferably 0.3 to 0.5 parts by weight, more preferably 0.4 parts by weight; the antifoaming agent is incorporated in an amount of 0.2 to 1 part by weight, preferably 0.2 to 0.4 parts by weight, more preferably 0.2 parts by weight; the solvent is incorporated in an amount of 10 to 45 parts by weight, preferably 14 to 23 parts by weight, more preferably 15 parts by weight. The antifoaming agent is selected from at least one of polysiloxane, polyether polysiloxane, and mineral oil, preferably BYK-024. The dispersant is selected from at least one of sodium dodecyl sulfate, polyacrylamide, methylpentanol, and cellulose derivatives, preferably sodium dodecyl sulfate. The solvent is selected from at least one of water, acetone, methyl ethyl ketone, ethyl acetate, toluene, dichloromethane, tetrahydrofuran, and N,N-dimethylformamide, preferably water.

[0025] The polyurea materials and modified MOFs materials with functional additives provided by the present invention can be used to prepare electrochemical components, including but not limited to batteries, sensors, and electrolyzers.

[0026] This invention provides an electrochemical component containing the polyurea material provided by this invention or a modified MOF material with functional additives. The electrochemical component includes, but is not limited to, batteries, sensors, and electrolyzers.

[0027] Compared with the prior art, the present invention has the following significant advantages: This invention discloses a method for preparing polyurea materials containing modified MOFs. By modifying MOFs with graphene oxide to form a multi-component composite material, the method not only increases the dispersion force within the MOFs, thus preventing aggregation, but also provides strong support for the MOF framework due to its stable planar structure, enhancing the structural stability of the MOFs. Furthermore, the high chemical inertness and perfect barrier properties of graphene oxide, combined with the metal slow-release properties of the MOFs themselves, can fully leverage their synergistic anti-corrosion effect. The polyurea material containing modified MOFs exhibits excellent adhesion, impact resistance, water resistance, corrosion resistance, and thermal stability. It not only provides a new approach to combining inorganic materials with polyurea resins but also broadens the application range of polyurea coatings, demonstrating significant progress and unexpected effects compared to existing technologies.

[0028] The graphene oxide modified MOFs material of this invention adopts a "one-pot method", in which graphene oxide is ultrasonically dispersed into a precursor solution containing the precursor solution required for the synthesis of MOFs, and then subjected to a hydrothermal reaction under the same reaction conditions as the preparation of pure MOFs. Attached Figure Description

[0029] Figure 1 The Nyquist plots show the polyurea coatings prepared in Examples 1-4 and Comparative Example 1.

[0030] Figure 2 The potential dynamics polarization curves are for the polyurea coatings prepared in Examples 1-4 and Comparative Example 1. Detailed Implementation

[0031] To make the technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. However, the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention.

[0032] Example 1 Preparation of polyurea materials containing modified MOFs: (1) Weigh 1 wt% of graphene oxide, which accounts for the total mass of DMF, Zn(NO3)2•6H2O and 2-aminoterephthalic acid, and add it to 40 mL of DMF solution. Use sonication to disperse the graphene oxide evenly. Then add 1.662 g of Zn(NO3)2•6H2O and 0.356 g of 2-aminoterephthalic acid in sequence. After stirring evenly with magnetic force, pour the solution into a hydrothermal synthesis reactor equipped with polytetrafluoroethylene. After reacting at 100 °C for 24 hours, filter the solution. After washing the product repeatedly, dry it at 100 °C for 24 hours to obtain modified MOFs. (2) Modified MOFs were mixed with 1.0 wt% of single-component polyurea resin, 0.4 wt% of BYK-024, 0.2 wt% of sodium dodecyl sulfate and 15 wt% of water to prepare a composite material.

[0033] Electrochemical experiments were conducted on polyurea materials containing modified MOFs, and the results are as follows: Figure 1 and Figure 2 As shown.

[0034] Example 2 Preparation of modified MOFs polyurea materials containing corrosion inhibitors: (1) Weigh 1 wt% of graphene oxide, which accounts for the total mass of DMF, Zn(NO3)2•6H2O and 2-aminoterephthalic acid, and add it to 40 mL of DMF solution. Use sonication to disperse the graphene oxide evenly. Then add 1.662 g of Zn(NO3)2•6H2O and 0.356 g of 2-aminoterephthalic acid in sequence. After stirring evenly with magnetic force, pour the solution into a hydrothermal synthesis reactor equipped with polytetrafluoroethylene. After reacting at 100 °C for 24 hours, filter the solution. After washing the product repeatedly, dry it at 100 °C for 24 hours to obtain the modified MOFs material. (2) The modified MOFs material was ultrasonically dispersed in anhydrous ethanol containing benzotriazole, and after magnetic stirring for 24 hours, it was centrifuged and washed to obtain the modified MOFs material loaded with corrosion inhibitor.

[0035] (3) A composite coating was prepared by uniformly mixing modified MOFs with corrosion inhibitors at a doping amount of 3.0 wt% with 50.0 wt% aqueous polyurea, 1.0 wt% polyether polysiloxane, 1.0 wt% polyacrylamide, and 45.0 wt% anhydrous methanol. Electrochemical experiments were conducted on the polyurea coating containing the modified MOFs material, and the results are as follows: Figure 1 and Figure 2 As shown.

[0036] Example 3 Preparation of polyurea coatings containing graphene oxide: Weigh out the same amount of graphene oxide as in Example 1, and mix it thoroughly with polyurea resin to prepare a composite coating. The polyurea resin used in Example 1 was also prepared using the same material. Electrochemical experiments were performed on the polyurea coating containing graphene oxide, and the results are as follows: Figure 1 and Figure 2 As shown.

[0037] Example 4 Preparation of polyurea coatings containing MOFs materials: (1) Weigh 1.662 g Zn(NO3)2•6H2O and 0.356 g 2-aminoterephthalic acid into 40 mL DMF solution, stir magnetically until homogeneous, pour the solution into a hydrothermal synthesis reactor with a polytetrafluoroethylene liner, react at 100 °C for 24 hours, filter, wash the product repeatedly, and dry at 100 °C for 24 hours to obtain MOFs material; (2) The above MOFs material was mixed with 65.8 wt% of two-component polyurea resin, 0.6 wt% of polysiloxane, 0.5 wt% of methyl pentanol and 29.6 wt% of dichloromethane to obtain a composite coating.

[0038] Electrochemical experiments were conducted on polyurea coatings containing MOFs materials, and the results are as follows: Figure 1 and Figure 2 As shown.

[0039] Comparative Example 1 Preparation of blank polyurea coating: A blank polyurea coating was prepared under the process conditions of Example 1.

[0040] Electrochemical experiments were conducted on blank polyurea materials, and the results are as follows: Figure 1 and Figure 2 As shown.

[0041] As is widely known, the larger the diameter of the capacitive arc in the Nyquist diagram, the stronger the corrosion resistance of the coating. Figure 1 It can be seen that, under the same addition ratio, the order of capacitive arc diameter from smallest to largest is: Comparative Example 1 < Example 4 < Example 3 < Example 1 < Example 2, i.e., blank polyurea coating < polyurea coating containing MOFs material < polyurea coating containing graphene oxide < polyurea coating containing modified MOFs material < polyurea coating containing modified MOFs material with corrosion inhibitor. Figure 2 It can be seen that, under the same addition ratio, the polyurea coating containing the modified MOF material with corrosion inhibitor has a smaller corrosion current density, followed by the modified MOF material. This indicates that graphene oxide successfully modifies the MOF material, and the composite material is not only an excellent corrosion-resistant filler, but can also be used as a container for carrying functional additives such as corrosion inhibitors.

[0042] The above-described implementation scheme is the preferred one after a large number of experiments. It should be noted that those skilled in the art can make some improvements without departing from the principle of the present invention, and these improvements should also be considered within the scope of protection of the present invention.

Claims

1. A polyurea material containing modified MOFs, characterized in that, The following components are contained in parts by weight: Polyurea resin: 50-85 parts by weight; Modified MOF materials: 0.5 ~ 5 parts by weight; Dispersant: 0.2 ~ 1 part by weight; Defoamer: 0.2 ~ 1 part by weight; Solvent: 10-45 parts by weight.

2. The polyurea material according to claim 1, characterized in that, The polyurea resin is selected from any one or any combination of two-component polyurea resin, one-component polyurea resin, and waterborne polyurea.

3. The polyurea material according to claim 1, characterized in that, The modified MOF material is a modified MOF material loaded with functional additives, and its preparation includes: S1, graphene oxide is uniformly dispersed in a precursor solution for synthesizing MOFs, and a one-pot hydrothermal reaction is carried out to obtain graphene oxide modified MOFs materials; the precursor solution for synthesizing MOFs is an organic solvent in which organic ligands and metal ions are uniformly dispersed. S2, the graphene oxide modified MOF material is uniformly dispersed in a solvent containing functional additives, and stirred to obtain the modified MOF material loaded with functional additives.

4. A method for preparing a modified MOF material loaded with functional additives, characterized in that the steps include... include: S1, graphene oxide is uniformly dispersed in a precursor solution for synthesizing MOFs, and a one-pot hydrothermal reaction is carried out to obtain graphene oxide modified MOFs materials; the precursor solution for synthesizing MOFs is an organic solvent in which organic ligands and metal ions are uniformly dispersed. S2, the graphene oxide modified MOF material is uniformly dispersed in a solvent containing functional additives, and stirred to obtain the modified MOF material loaded with functional additives.

5. A modified MOF material incorporating functional additives, characterized in that, It was prepared by the method described in claim 4.

6. The method for preparing the polyurea material according to claim 1, characterized in that, The steps include: The modified MOFs material carrying functional additives, prepared by the method described in claim 4, is incorporated into polyurea resin to obtain a polyurea material.

7. The preparation method according to claim 6, characterized in that, It also contains dispersants, defoamers, and solvents.

8. The polyurea material according to any one of claims 1-3 or the modified MOF material with functional additives prepared by the preparation method according to claim 4 is used to prepare electrochemical components.

9. An electrochemical component, characterized in that, Modified MOFs containing the polyurea material according to any one of claims 1-3 or the preparation method according to claim 4, and loaded with functional additives.

10. The electrochemical component according to claim 9, characterized in that, The electrochemical component is selected from at least one of a battery, a sensor, and an electrolyzer.

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