MOFs-based blood perfusion adsorption material and preparation method thereof

Abstract

The invention discloses an MOFs-based blood perfusion adsorption material and a preparation method thereof, and relates to the technical field of blood perfusion, the adsorption material takes a melt-blown non-woven fabric as a matrix, in-situ growth of an adsorbent MOFs and heparin connected with an MOFs organic ligand in a covalent bond mode is carried out on the surface of the melt-blown non-woven fabric, the gram weight of the melt-blown non-woven fabric is 30-200g / m < 2 >, and the fiber diameter is 0.3-7.5 [mu] m. The hemolysis rate of the MOFs-based blood perfusion adsorption material is kept within 10%, the MOFs-based blood perfusion adsorption material has good biocompatibility, the selected melt-blown cloth base body has good biocompatibility and high porosity, part of protein binding elements with large particle sizes can be preliminarily screened out, the MOFs-based blood perfusion adsorption material shows excellent adsorption performance for various toxins in blood, and the MOFs-based blood perfusion adsorption material is suitable for being applied to various toxins in blood. The excellent anticoagulation effect is realized.

Description

Technical Field

[0001] This invention relates to the field of hemoperfusion technology, and in particular to a MOFs-based hemoperfusion adsorbent material and its preparation method. Background Technology

[0002] Hemoperfusion is a medical treatment method that has been widely used to treat liver failure, uremia, drug poisoning, autoimmune diseases, and other conditions. The core material in hemoperfusion is an adsorbent, which removes toxins, waste products, and metabolic waste from the blood drawn out of the body before returning the blood to the body.

[0003] Commonly used adsorbent materials for hemoperfusion include activated carbon, chitosan microspheres, and adsorbent resins, with adsorbent resins being the most widely used. For example, Chinese invention patent CN114288997A discloses an adsorbent resin with self-anticoagulant properties and its preparation method. This patent uses polystyrene-based macroporous resin as a carrier, introducing a large amount of chloromethyl groups onto the primary cross-linked resin carrier through a chloromethylation reaction. The chloromethyl groups undergo an epoxy modification reaction with 1-hydroxy-1,3-epoxypropane, and heparin-like molecules are then grafted onto the highly cross-linked macroporous adsorbent resin using the activity of the epoxy groups. This patent achieves good anticoagulant effects while maintaining resin adsorption, reducing the amount of heparin used in subsequent treatments. However, these methods all use highly toxic chloromethyl ether as a chloromethylation agent in their preparation processes, and the residues of these highly toxic organic reagents pose serious safety hazards. Furthermore, most existing adsorbent materials have relatively simple adsorption modes, only targeting specific toxins or cytokines, thus failing to achieve good therapeutic effects. For example, Chinese patent CN109046282B discloses a method for preparing an adsorbent material for removing endotoxins. By grafting a large number of hydroxyl or epoxy groups onto the surface of nonwoven fibers using ultraviolet irradiation grafting technology, and then fixing polyvinylimine onto the hydroxyl or epoxy groups through chemical covalent bonds, an adsorbent material with good endotoxin adsorption performance is prepared. However, this adsorbent material cannot remove multiple pathogenic factors from the body of sepsis patients.

[0004] Therefore, it is of great significance to develop a blood perfusion adsorption material that can simultaneously remove multiple blood toxins such as endotoxins, creatinine, and bilirubin, and can effectively avoid the residue of toxic organic solvents during the preparation process. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a MOFs-based hemoperfusion adsorbent material and its preparation method, which enables the hemoperfusion adsorbent material to remove multiple pathogenic factors. It not only has excellent blood compatibility and toxin removal ability as well as anticoagulant effect, but also avoids the use of highly toxic chloromethyl ether in the preparation process, effectively reducing the risk of clinical application.

[0006] In a first aspect, the present invention provides a MOF-based blood perfusion adsorbent material, wherein the adsorbent material uses meltblown nonwoven fabric as a matrix, and adsorbent MOFs are grown in situ on the surface of the meltblown nonwoven fabric, and heparin is covalently linked to the MOFs organic ligands, wherein the basis weight of the meltblown nonwoven fabric is 30-200 g / m³. 2 The fiber diameter is 0.3-7.5um.

[0007] Secondly, this invention provides a method for preparing MOFs-based blood perfusion adsorbent materials, comprising the following steps:

[0008] S1. Select meltblown nonwoven fabric;

[0009] S2. Dissolve the water-soluble metal salt in an organic solvent and stir magnetically at 30-120℃ for 0.5-6 hours to prepare a metal salt solution A with a concentration of 0.25-2.5 mol / L.

[0010] S3. Immerse the meltblown nonwoven fabric selected in step S1 in the metal salt solution prepared in step S2 for 1-12 hours to ensure that the metal ions are firmly loaded onto the fiber surface.

[0011] S4. Dissolve 2-aminoterephthalic acid in an organic solvent and stir magnetically at 30-120℃ for 0.5-6 hours to prepare an organic ligand solution B with a concentration of 0.25-2.5 mol / L.

[0012] S5. Add the organic ligand solution prepared in step S4 to the metal salt solution used to impregnate the nonwoven fabric in step S3, and then seal it in a hydrothermal reactor. React under static conditions of 30-120℃ for 0.5-36h. After the reaction is completed, take it out and dry it to obtain a nonwoven fabric with MOFs loaded on the surface, wherein the molar ratio of metal salt to organic ligand is 1:1-10.

[0013] S6. Prepare a sodium heparin solution with a volume fraction of 2-10%, and then add 0.25-1 times the mass of activator to activate the sodium heparin solution to obtain solution C.

[0014] S7. Add the nonwoven fabric with MOFs loaded on its surface obtained in step S5 to the solution C obtained in step S6, react at 30-120℃ for 0.5-24h, then wash with deionized water 3-5 times, and dry to obtain MOFs-based blood perfusion adsorption material.

[0015] In conjunction with the second aspect, in some embodiments, the meltblown nonwoven fabric mentioned in S1 is one of polypropylene meltblown nonwoven fabric, polyethylene terephthalate nonwoven fabric, and polybutylene terephthalate nonwoven fabric.

[0016] In conjunction with the second aspect, in some embodiments, the meltblown nonwoven fabric described in S1 is a polybutylene terephthalate nonwoven fabric.

[0017] In conjunction with the second aspect, in some embodiments, the basis weight of the meltblown nonwoven fabric described in S1 is 60-150 g / m². 2 The fiber diameter is 0.3-2.5um.

[0018] In conjunction with the second aspect, in some embodiments, the basis weight of the meltblown nonwoven fabric described in S1 is 90-110 g / m². 2 The fiber diameter is 0.3-1.0um.

[0019] In conjunction with the second aspect, in some embodiments, the metal salt mentioned in S3 is one of cobalt nitrate hexahydrate, ferric nitrate nonahydrate, zirconium tetrachloride, zinc acetate dihydrate, and nickel nitrate hexahydrate; the organic solvent mentioned in S3 is one of deionized water, anhydrous methanol, anhydrous ethanol, DMF, and DMAc.

[0020] In conjunction with the second aspect, in some embodiments, the organic solvent mentioned in S4 is one of deionized water, anhydrous methanol, anhydrous ethanol, DMF, and DMAc.

[0021] In conjunction with the second aspect, in some embodiments, the organic solvents mentioned in S3 and S4 are all one of deionized water, anhydrous methanol, and anhydrous ethanol.

[0022] In conjunction with the second aspect, in some embodiments, the activator in S6 is one or more of N-hydroxysuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

[0023] The beneficial effects of this invention are:

[0024] 1. The hemolysis rate of the MOFs-based blood perfusion adsorbent material of the present invention is kept below 10%, which has good biocompatibility. The selected meltblown fabric matrix has good biocompatibility and high porosity, which can initially screen out some protein-binding proteins with larger particle sizes.

[0025] 2. This invention uses meltblown nonwoven fabric as a matrix to produce MOFs-based adsorbent materials in situ, which can improve the mechanical strength and stability of the adsorbent materials during use, making them less prone to pulverization and shedding, and improving the safety of clinical use.

[0026] 3. The MOFs-based adsorbent material prepared by this invention has a high specific surface area and exhibits excellent adsorption performance for various toxins in the blood.

[0027] 4. The preferred 2-aminoterephthalic acid organic ligand of the present invention can covalently solidify heparin, resulting in a clotting time greater than 150 min, thereby improving the anticoagulant efficacy of the adsorbent material.

[0028] 5. The preparation process described in this invention uses green solvents to avoid the harm to human body and environment caused by a large number of toxic reagents. Attached Figure Description

[0029] Figure 1 SEM image of the MOFs-based blood perfusion adsorption material prepared for this invention. Detailed Implementation

[0030] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the test data. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0031] Unless otherwise specified in the following examples, the conditions are as per standard conditions or the manufacturer's recommendations. Raw materials, equipment, or instruments whose manufacturers are not specified are all commercially available products.

[0032] This invention proposes a MOFs-based blood perfusion adsorbent material and its preparation method. MOFs with high adsorption capacity are grown in situ on the surface of meltblown nonwoven fabric to remove various pathogenic toxins in the blood. Then, heparin is covalently linked to the organic ligands of MOFs to improve the anticoagulant effect of the adsorbent material and reduce the use of heparin in clinical applications.

[0033] A method for preparing a MOF-based hemoperfusion adsorbent material according to the present invention includes the following steps:

[0034] Step 1: Select a meltblown nonwoven fabric with a basis weight of 30-200 g / m². 2 Preferred concentration: 60-15g / m 2 Further optimization is needed for 90-120g / m 2 The nonwoven fabric with a preferred weight can maintain better support strength; the fiber diameter is 0.3-7.5um, preferably 0.3-2.5um, and even more preferably 0.3-1.0um. The nonwoven fabric with the preferred fiber diameter can remove some protein-bound toxins; the nonwoven fabric is one of polypropylene meltblown nonwoven fabric, polyethylene terephthalate nonwoven fabric, and polybutylene terephthalate nonwoven fabric, preferably polybutylene terephthalate.

[0035] Step 2: Dissolve a certain mass of metal salt in an organic solvent and magnetically stir at 30-120℃ for 0.5-6 hours to obtain a metal salt solution A with a concentration of 0.25-2.5 mol / L. Then, immerse the meltblown nonwoven fabric selected in Step 1 in the metal salt solution for 1-12 hours to firmly load the metal ions onto the fiber surface. The metal salt mentioned in this step is one of a variety of water-soluble metal salts such as cobalt nitrate hexahydrate, ferric nitrate nonahydrate, zirconium tetrachloride, zinc acetate dihydrate, and nickel nitrate hexahydrate. The organic solvent is one of deionized water, anhydrous methanol, anhydrous ethanol, DMF, and DMAc, preferably green solvents such as deionized water, anhydrous methanol, and anhydrous ethanol.

[0036] Step 3: Dissolve a certain mass fraction of 2-aminoterephthalic acid in an organic solvent and stir magnetically at 30-120℃ for 0.5-6 hours to obtain a 0.25-2.5 mol / L organic ligand solution B. The organic solvent used in this step is one of deionized water, anhydrous methanol, anhydrous ethanol, DMF, and DMAc, preferably green solvents such as deionized water, anhydrous methanol, and anhydrous ethanol.

[0037] Step 4: Add the organic ligand solution obtained in Step 3 to the metal salt solution impregnated with the nonwoven fabric in Step 2 in an equal proportion, then seal it in a hydrothermal reactor, and react it under static conditions of 30-120℃ for 0.5-36h. After the reaction is completed, take it out and dry it to obtain the MOFs adsorbent material loaded on the nonwoven fabric.

[0038] Step 5: To improve the anticoagulant efficacy of the adsorbent material, heparin is covalently grafted onto the surface of the adsorbent material. Specifically, sodium heparate is prepared into a 2-10% (v / v) aqueous solution, and then 0.25-1 times the mass of activator is added to activate it, resulting in solution C. Finally, the adsorbent material prepared in Step 4 is added, and the reaction is carried out at 30-120℃ for 0.5-24 hours. After washing with deionized water 3-5 times, the solution is dried to obtain a blood perfusion adsorbent material with the ability to clear multiple pathogenic factors. The activator mentioned in this step is one or more of N-hydroxysuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

[0039] The following examples 1-3 provide a detailed description of a MOFs-based blood perfusion adsorbent material and its preparation method according to the present invention.

[0040] Example 1

[0041] This embodiment provides a method for preparing MOFs-based blood perfusion adsorbent materials. The specific preparation steps are as follows:

[0042] Step 1: A polybutylene terephthalate meltblown nonwoven fabric with a basis weight of 100 g / m² was selected. 2The fiber diameter distribution is concentrated at 0.75 μm.

[0043] Step 2: Dissolve 4.66g (20mmol) of zirconium tetrachloride in 100ml of anhydrous ethanol and stir magnetically at 80℃ for 6h to obtain a 0.2mol / L zirconium tetrachloride ethanol solution A. Immerse the meltblown PBT nonwoven fabric selected in Step 1 in solution A for 6h.

[0044] Step 3: Dissolve 3.623g of 2-aminoterephthalic acid in 100ml of anhydrous ethanol and stir magnetically at 80℃ for 6h to obtain 0.2mol / L 2-aminoterephthalic acid ethanol solution B.

[0045] Step 4: Add solution B obtained in step 3 to solution A that impregnates the nonwoven fabric in step 2 in equal proportion, then seal it in a hydrothermal reactor, and react it at 120℃ under static conditions for 24 hours. After the reaction is completed, take it out and dry it to obtain MOFs adsorbent material loaded on nonwoven fabric.

[0046] Step 5: Take 20g of sodium heparinate to prepare a 5% sodium heparinate aqueous solution, then add 5g of N-hydroxysuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride to obtain solution C; finally, add the adsorbent material prepared in step 4, react at 60℃ for 12h, wash with deionized water 5 times and dry to obtain a blood perfusion adsorbent material with the function of clearing multiple pathogenic factors.

[0047] Example 2

[0048] This embodiment provides a method for preparing MOFs-based blood perfusion adsorbent materials. The specific preparation steps are as follows:

[0049] Step 1: A polyethylene terephthalate meltblown nonwoven fabric with a basis weight of 100 g / m² was selected. 2 The fiber diameter distribution is concentrated at 0.75 μm.

[0050] Step 2: Dissolve 4.39g (20mmol) of zinc acetate dihydrate in 100ml of anhydrous ethanol and stir magnetically at 80℃ for 6h to obtain a 0.2mol / L zinc acetate ethanol solution A. Immerse the meltblown PET nonwoven fabric selected in Step 1 in solution A for 6h.

[0051] Step 3: Dissolve 3.623g of 2-aminoterephthalic acid in 100ml of anhydrous ethanol and stir magnetically at 80℃ for 6h to obtain 0.2mol / L 2-aminoterephthalic acid ethanol solution B.

[0052] Step 4: Add solution B obtained in step 3 to solution A that impregnates the nonwoven fabric in step 2 in equal proportion, then seal it in a hydrothermal reactor, and react it at 120℃ under static conditions for 24 hours. After the reaction is completed, take it out and dry it to obtain MOFs adsorbent material loaded on nonwoven fabric.

[0053] Step 5: Take 20g of sodium heparinate to prepare a 5% sodium heparinate aqueous solution, then add 10g of N-hydroxysuccinimide to obtain solution C; finally add the adsorbent material prepared in step 4, react at 60℃ for 12h, wash with deionized water 5 times and dry to obtain a blood perfusion adsorbent material with multiple pathogenic factors removal effects.

[0054] Example 3

[0055] This embodiment provides a method for preparing MOFs-based blood perfusion adsorbent materials. The specific preparation steps are as follows:

[0056] Step 1: A polypropylene meltblown nonwoven fabric with a basis weight of 100 g / m² was selected. 2 The fiber diameter distribution is concentrated at 0.75 μm.

[0057] Step 2: Dissolve 5.82g (20mmol) of cobalt nitrate hexahydrate in 100ml of anhydrous ethanol and stir magnetically at 80℃ for 6h to obtain a 0.2mol / L cobalt nitrate ethanol solution A. Immerse the meltblown PP nonwoven fabric selected in Step 1 in solution A for 6h.

[0058] Step 3: Dissolve 3.623g of 2-aminoterephthalic acid in 100ml of anhydrous ethanol and stir magnetically at 80℃ for 6h to obtain 0.2mol / L 2-aminoterephthalic acid ethanol solution B.

[0059] Step 4: Add solution B obtained in step 3 to solution A that impregnates the nonwoven fabric in step 2 in equal proportion, then seal it in a hydrothermal reactor, and react it at 120℃ under static conditions for 24 hours. After the reaction is completed, take it out and dry it to obtain MOFs adsorbent material loaded on nonwoven fabric.

[0060] Step 5: Take 20g of sodium heparinate to prepare a 5% sodium heparinate aqueous solution, then add 3g of N-hydroxysuccinimide and 7g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride to obtain solution C; finally, add the adsorbent material prepared in step 4, react at 60℃ for 12h, wash with deionized water 5 times and dry to obtain a blood perfusion adsorbent material with the function of clearing multiple pathogenic factors.

[0061] To characterize the microstructure of the MOFs-based blood perfusion adsorbent materials prepared in this invention, the MOFs-based blood perfusion adsorbent materials prepared in Examples 1 to 3 were characterized by SEM, and the results are as follows: Figure 1 As shown. By Figure 1 It can be seen that many particles with specific morphologies have grown on the meltblown nonwoven fabric fibers, indicating that MOFs have been successfully grown on the surface of the meltblown nonwoven fabric fibers. The surface of the particles with specific morphologies has smaller particle structures, which are heparin covalently linked to the organic ligands of MOFs.

[0062] Performance testing

[0063] 1. Adsorption performance test

[0064] blood toxin adsorption q t The calculation formula is as follows:

[0065] q t =(C0―C t )×V / m

[0066] Adsorption scavenging rate = (C0 - C) t ) / C0*100%

[0067] Among them, q t (mg / g) represents the mass of blood toxins adsorbed by a unit mass of adsorbent material at time t; C0 (mg / L) represents the initial blood toxin concentration; C t (mg / L) represents the residual blood toxin concentration at time t; V(L) represents the solution volume; and m(g) represents the mass of the adsorbent material.

[0068] (1) Testing the bilirubin scavenging rate: A bilirubin solution with a concentration of 200 mg / L was prepared, and 10 mg of the adsorbent materials prepared in Examples 1, 2, and 3 were added to it respectively. The adsorption process was carried out in a constant temperature shaker (37℃, 150 rpm / min). The absorbance value of the bilirubin solution at 438 nm after 3 h of adsorption was measured using a UV spectrophotometer. The concentrations of bilirubin solution before and after adsorption were obtained based on the absorbance value and the standard curve.

[0069] (2) Test the scavenging rate of methylene blue: Similarly, a methylene blue solution with a concentration of 200 mg / L was prepared, and 10 mg of the adsorbent material prepared in Examples 1, 2 and 3 was added to it respectively. The adsorption process was carried out in a constant temperature shaker (37℃, 150 rpm / min). The light absorption value at 290 nm after 3 h of adsorption was measured using a UV spectrophotometer.

[0070] (3) Test the endotoxin clearance rate: Similarly, prepare a methylene blue solution with a concentration of 200 mg / L, and add 10 mg of the adsorbent material prepared in Examples 1, 2 and 3 respectively. The adsorption process is carried out in a constant temperature shaker (37℃, 150 rpm / min). The light absorption value at 405 nm after 3 h of adsorption is measured using a UV spectrophotometer.

[0071] (4) Test the scavenging rate of creatinine: Similarly, prepare a methylene blue solution with a concentration of 200 mg / L, and add 10 mg of the adsorbent material prepared in Examples 1, 2 and 3 respectively. The adsorption process is carried out in a constant temperature shaker (37℃, 150 rpm / min). The light absorption value at 248 nm after 3 h of adsorption is measured using a UV spectrophotometer.

[0072] The test results are shown in Table 1. The adsorbent material prepared by the present invention exhibits excellent removal efficiency for a variety of toxins in the blood.

[0073] Table 1

[0074]

[0075] 2. Clotting Time Test

[0076] The adsorbent materials prepared in Examples 1 to 3 were added to 2 mL of freshly collected blood and incubated at 37°C. The blood clotting time was recorded. The test results are shown in Table 2. The clotting time of all three groups of samples was greater than 150 min, demonstrating excellent anticoagulant efficacy.

[0077] Table 2

[0078] sample Whole blood clotting time (min) Example 1 157 Example 2 170 Example 3 163

[0079] 3. Hemolysis rate test

[0080] Take 1 mL of red blood cell solution and centrifuge at 8000 rpm for 10 min to obtain red blood cells. Dilute the red blood cells with 1 mL of deionized water and 1 mL of PBS respectively to obtain red blood cell suspensions (PBS is a negative control, and deionized water is a positive control). Add 5 mg of the adsorbent material prepared in Examples 1-3 to 1 mL of red blood cell suspension (PBS) of each group and incubate at 37°C for 3 h. Then centrifuge the suspension at 8000 rpm for 3 min and collect the supernatant. Measure the maximum absorption peak of the supernatant at 540 nm using a UV spectrophotometer. The hemolysis rate can be calculated using the following formula:

[0081] Hemolysis rate (%) = (As – An) / (Ap – An) × 100

[0082] In the formula, As is the absorbance of the suspension, and Ap and An are the absorbances of the positive control and negative control, respectively.

[0083] The test results are shown in Table 3. The hemolysis rate of the three groups of samples remained below 10%, indicating good biocompatibility.

[0084] Table 3

[0085] sample hemolysis rate Example 1 3.2％ Example 2 5.6％ Example 3 4.9％

[0086] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention. Technologies not described in detail in this invention are known technologies.

Claims

1. A MOF-based blood perfusion adsorbent material, characterized in that, The adsorbent material uses meltblown nonwoven fabric as a matrix, and adsorbent MOFs are grown in situ on the surface of the meltblown nonwoven fabric, along with heparin covalently linked to the MOFs organic ligands. The basis weight of the meltblown nonwoven fabric is 30-200 g / m³. 2 The fiber diameter is 0.3-7.5um.

2. A method for preparing a MOF-based blood perfusion adsorbent, characterized in that, Includes the following steps: S1. Select meltblown nonwoven fabric; S2. Dissolve the water-soluble metal salt in an organic solvent and stir magnetically at 30-120℃ for 0.5-6 hours to prepare a metal salt solution A with a concentration of 0.25-2.5 mol / L. S3. Immerse the meltblown nonwoven fabric selected in step S1 in the metal salt solution prepared in step S2 for 1-12 hours to ensure that the metal ions are firmly loaded onto the fiber surface. S4. Dissolve 2-aminoterephthalic acid in an organic solvent and stir magnetically at 30-120℃ for 0.5-6 hours to prepare an organic ligand solution B with a concentration of 0.25-2.5 mol / L. S5. Add the organic ligand solution B prepared in step S4 to the metal salt solution used to impregnate the nonwoven fabric in step S3, then seal it in a hydrothermal reactor and react it under static conditions of 30-120℃ for 0.5-36h. After the reaction is completed, take it out and dry it to obtain a nonwoven fabric with MOFs loaded on the surface. S6. Prepare a sodium heparin solution with a volume fraction of 2-10%, and then add 0.25-1 times the mass of activator to activate the sodium heparin solution to obtain solution C. S7. Add the nonwoven fabric with MOFs loaded on its surface obtained in step S5 to solution C obtained in step S6, react at 30-120℃ for 0.5-24h, then wash with deionized water 3-5 times, and dry to obtain MOFs-based blood perfusion adsorption material.

3. The preparation method according to claim 2, characterized in that, The meltblown nonwoven fabric mentioned in S1 is one of polypropylene meltblown nonwoven fabric, polyethylene terephthalate nonwoven fabric, and polybutylene terephthalate nonwoven fabric.

4. The preparation method according to claim 3, characterized in that, The meltblown nonwoven fabric mentioned in S1 is polybutylene terephthalate nonwoven fabric.

5. The preparation method according to claim 4, characterized in that, The basis weight of the meltblown nonwoven fabric mentioned in S1 is 60-150 g / m². 2 The fiber diameter is 0.3-2.5um.

6. The preparation method according to claim 5, characterized in that, The basis weight of the meltblown nonwoven fabric mentioned in S1 is 90-110 g / m². 2 The fiber diameter is 0.3-1.0um.

7. The preparation method according to claim 6, characterized in that, The metal salt mentioned in S3 is one of cobalt nitrate hexahydrate, ferric nitrate nonahydrate, zirconium tetrachloride, zinc acetate dihydrate, and nickel nitrate hexahydrate; the organic solvent mentioned in S3 is one of deionized water, anhydrous methanol, anhydrous ethanol, DMF, and DMAc.

8. The preparation method according to claim 7, characterized in that, The organic solvent mentioned in S4 is one of deionized water, anhydrous methanol, anhydrous ethanol, DMF, and DMAc.

9. The preparation method according to claim 7 or 8, characterized in that, The organic solvents mentioned in S3 and S4 are all one of deionized water, anhydrous methanol, and anhydrous ethanol.

10. The preparation method according to claim 9, characterized in that, The activator mentioned in S6 is one or more of N-hydroxysuccinimide and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

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