CN110506753B - Preparation method of modified nano-silver antibacterial composite material - Google Patents
Preparation method of modified nano-silver antibacterial composite material Download PDFInfo
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- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a preparation method of a modified nano-silver antibacterial composite material, which comprises the following steps: adding SBA-15 molecular sieve, nano zinc oxide, nano copper oxide, nano titanium dioxide and water into a reaction device, stirring uniformly, performing microwave treatment, cooling, filtering and drying to obtain a material A; mixing the material A, a silane coupling agent KH-540 and dimethylformamide, stirring under the protection of nitrogen, centrifuging, washing and drying to obtain a material B; uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, mixing with the material B after stirring, stirring at room temperature, centrifuging, washing and drying to obtain a material C; adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D; mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, stirring uniformly, and removing water to obtain the product.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a preparation method of a modified nano-silver antibacterial composite material.
Background
The antibacterial material is a novel material with bacteriostatic and bactericidal functions and is prepared by adding one or more specific antibacterial agents. The invasion of microorganisms is ubiquitous, and the development and application of the antibacterial material have important significance for improving the living environment of human beings, reducing diseases and protecting the health of the whole people. The antibacterial materials are roughly classified into three categories, inorganic antibacterial materials, organic antibacterial materials and natural antibacterial materials, according to their chemical compositions.
The nano silver is widely used due to the strong antibacterial and broad-spectrum antibacterial effects, but the pure nano silver without any modification has very high surface activity, is easy to agglomerate, has active property and is easy to oxidize, the penetrating effect on a biological film is not very good, the antibacterial effect of the nano silver taken as an antibacterial material alone is not very ideal, the application of the nano silver in certain antibacterial fields is limited, and the nano silver needs to be modified in order to obtain the good antibacterial effect.
Disclosure of Invention
In order to solve the technical problems in the background art, the invention provides a preparation method of a modified nano-silver antibacterial composite material, the process is simple, the obtained composite material has good heat resistance, is not easy to discolor, has broad sterilization spectrum and lasting antibacterial effect, and can be widely applied to the fields of rubber and plastic, chemical fibers, coatings, adhesives and the like.
The invention provides a preparation method of a modified nano-silver antibacterial composite material, which comprises the following steps:
s1, adding the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and water into a reaction device, uniformly stirring, placing the mixture into microwave equipment for microwave treatment, and cooling, filtering and drying to obtain a material A;
s2, mixing the material A, the silane coupling agent KH-540 and dimethylformamide, stirring for 10-15h at 85-95 ℃ by taking nitrogen as protective gas, centrifuging, washing and drying to obtain a material B;
s3, uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, stirring for 40-60min, mixing with the material B, stirring at room temperature for 180min, centrifuging, washing and drying to obtain a material C;
s4, adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D;
s5, mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, uniformly stirring, and removing water to obtain the modified nano-silver antibacterial composite material; wherein the 8-hydroxyquinoline complex is prepared according to the following process: uniformly mixing ethanol and water to obtain a solvent, adding 8-hydroxyquinoline, pimelic acid and cerium nitrate into the solvent to be uniformly dispersed, then placing the mixture into a hydrothermal reaction kettle to carry out hydrothermal reaction, and filtering, washing and drying the mixture after the reaction is finished to obtain the 8-hydroxyquinoline complex.
Preferably, in S1, the weight ratio of SBA-15 molecular sieve, nano zinc oxide, nano copper oxide, nano titanium dioxide and water is 35-55: 1-3: 0.5-2: 1-2.5: 250-300.
Preferably, in S1, the average particle size of the nano zinc oxide, the average particle size of the nano copper oxide and the average particle size of the nano titanium dioxide are all 25 to 40 nm.
Preferably, in S1, the power of the microwave treatment is 550-700W, and the time of the microwave treatment is 35-60 min.
Preferably, in S2, the weight ratio of the material A, the silane coupling agent KH-540 and the dimethylformamide is 4-6: 9-13: 40-60.
Preferably, in S3, the weight ratio of graphene oxide to material B is 1: 15-20.
Preferably, in S4, the nano-silver sol is an electrolytic nano-silver sol, and the weight content of nano-silver is 0.4 wt%; the weight volume ratio of the material C to the nano silver sol is 85-95: 160-220 mg/ml; the ultrasonic treatment time is 180-240min, the temperature is 45-55 ℃, and the frequency is 25-32 kHz.
Preferably, in S5, the weight ratio of the material D, the boron oxide, the copper chlorophyllin acid and the 8-hydroxyquinoline complex is 5-9: 0.5-1.5: 0.3-1.2: 2-4.5.
Preferably, in S5, the volume ratio of ethanol to water in the preparation process of the 8-hydroxyquinoline complex is 1-3: 1-5; the mol ratio of 8-hydroxyquinoline to pimelic acid to cerium nitrate is 1: 1: 0.5-1.5.
Preferably, in S5, the hydrothermal reaction temperature is 105-130 ℃ and the time is 24-40h during the preparation of the 8-hydroxyquinoline complex.
According to the preparation method of the modified nano-silver antibacterial composite material, firstly, the SBA-15 molecular sieve, the nano-zinc oxide, the nano-copper oxide, the nano-titanium dioxide and water are used as raw materials to be subjected to microwave treatment, the nano-zinc oxide, the nano-copper oxide and the nano-titanium dioxide are assembled in pore channels of the SBA-15 molecular sieve, and meanwhile, the framework structure of the SBA-15 molecular sieve is kept, so that a material A is obtained; then, the silane coupling agent KH-540 is used as a modifier to carry out surface modification on the material A, and amino is introduced to the surface of the material A to obtain a material B; then mixing the material B with the activated graphene oxide, stirring to enable amino on the surface of the material B to react with carboxyl on the surface of the graphene oxide, further combining the graphene oxide with the material B into a whole to obtain a material C, mixing with nano-silver sol, increasing the motion frequency and speed of the material C and the nano-silver in a solvent under the action of ultrasound to enable the material C and the nano-silver to be fully contacted and combined, enabling the nano-silver to be adsorbed on the surface of the graphene oxide, simultaneously enabling part of the nano-silver to enter a pore channel of an SBA-15 molecular sieve, forming a small amount of silver ions to obtain a material D, matching the material D with boron oxide, copper chlorophyllin and 8-hydroxyquinoline complex to serve as an antibacterial material, wherein the SBA-15 molecular sieve and the graphene oxide can play a role in stabilizing and protecting the nano-silver, and avoiding the agglomeration of the nano-silver, the obtained composite material can play the performance of various antibacterial materials, has broad antibacterial spectrum, has effects on Candida albicans, Staphylococcus aureus, Escherichia coli, etc., has slow release effect, can control the release of the antibacterial materials, and has lasting antibacterial effect; the 8-hydroxyquinoline, pimelic acid and cerium nitrate are selected as main materials to prepare the complex, and the complex is added into a system to be matched with boron oxide and nano titanium dioxide, so that the antibacterial material has good heat resistance and excellent high temperature resistance; the added copper chlorophyllin acid can convert the absorbed visible light energy into chemical energy to be transferred to the nano zinc oxide and the nano titanium dioxide, so that the light energy utilization rate is improved, and the antibacterial efficiency of the composite material is obviously improved; the antibacterial composite material prepared by the preparation method disclosed by the invention is wide in application and can be used in the fields of rubber and plastic, chemical fibers, coatings, adhesives and the like.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a modified nano-silver antibacterial composite material comprises the following steps:
s1, adding the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and water into a reaction device, uniformly stirring, placing the mixture into microwave equipment for microwave treatment, and cooling, filtering and drying to obtain a material A;
s2, mixing the material A, the silane coupling agent KH-540 and dimethylformamide, stirring for 10 hours at 95 ℃ by taking nitrogen as protective gas, centrifuging, washing and drying to obtain a material B;
s3, uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, stirring for 60min, mixing with the material B, stirring at room temperature for 120min, centrifuging, washing and drying to obtain a material C;
s4, adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D;
s5, mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, uniformly stirring, and removing water to obtain the modified nano-silver antibacterial composite material; wherein the 8-hydroxyquinoline complex is prepared according to the following process: uniformly mixing ethanol and water to obtain a solvent, adding 8-hydroxyquinoline, pimelic acid and cerium nitrate into the solvent to be uniformly dispersed, then placing the mixture into a hydrothermal reaction kettle to carry out hydrothermal reaction, and filtering, washing and drying the mixture after the reaction is finished to obtain the 8-hydroxyquinoline complex.
Example 2
A preparation method of a modified nano-silver antibacterial composite material comprises the following steps:
s1, adding the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and water into a reaction device, uniformly stirring, placing the mixture into microwave equipment for microwave treatment, and cooling, filtering and drying to obtain a material A;
s2, mixing the material A, the silane coupling agent KH-540 and dimethylformamide, stirring for 12 hours at 88 ℃ by taking nitrogen as protective gas, centrifuging, washing and drying to obtain a material B;
s3, uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, stirring for 40min, mixing with the material B, stirring for 180min at room temperature, centrifuging, washing and drying to obtain a material C;
s4, adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D;
s5, mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, uniformly stirring, and removing water to obtain the modified nano-silver antibacterial composite material; wherein the 8-hydroxyquinoline complex is prepared according to the following process: uniformly mixing ethanol and water to obtain a solvent, adding 8-hydroxyquinoline, pimelic acid and cerium nitrate into the solvent to be uniformly dispersed, then placing the mixture into a hydrothermal reaction kettle to carry out hydrothermal reaction, and filtering, washing and drying the mixture after the reaction is finished to obtain the 8-hydroxyquinoline complex.
Example 3
A preparation method of a modified nano-silver antibacterial composite material comprises the following steps:
s1, adding the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and water into a reaction device, wherein the weight ratio of the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and the water is 35: 2: 0.5: 1.5: 250, uniformly stirring the nano zinc oxide with the average particle size of 25nm, the nano copper oxide with the average particle size of 550W, placing the mixture in microwave equipment for microwave treatment for 60min, and cooling, filtering and drying the mixture to obtain a material A;
s2, mixing the material A, the silane coupling agent KH-540 and dimethylformamide, wherein the weight ratio of the material A to the silane coupling agent KH-540 to dimethylformamide is 4: 13: 40, stirring for 15 hours at 85 ℃ by taking nitrogen as protective gas, centrifuging, washing and drying to obtain a material B;
s3, uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, stirring for 50min, and mixing with a material B, wherein the weight ratio of the graphene oxide to the material B is 1: 20, stirring for 150min at room temperature, centrifuging, washing and drying to obtain a material C;
s4, adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D; the nano silver sol is electrolytic nano silver sol, and the weight content of the nano silver is 0.4 wt%; the weight volume ratio of the material C to the nano silver sol is 85: 220 mg/ml; the ultrasonic treatment time is 180min, the temperature is 55 ℃, and the frequency is 25 kHz;
s5, mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, uniformly stirring, and removing water to obtain the modified nano-silver antibacterial composite material; wherein the weight ratio of the material D, the boron oxide, the copper chlorophyllin acid and the 8-hydroxyquinoline complex is 9: 0.5: 1.2: 2; the 8-hydroxyquinoline complex is prepared according to the following process: uniformly mixing ethanol and water to obtain a solvent, wherein the volume ratio of the ethanol to the water is 1: adding 8-hydroxyquinoline, pimelic acid and cerium nitrate into a solvent, and uniformly dispersing, wherein the molar ratio of the 8-hydroxyquinoline to the pimelic acid to the cerium nitrate is 1: 1: 0.5, then placing the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 40 hours at 105 ℃, and filtering, washing and drying the mixture after the reaction is finished to obtain the 8-hydroxyquinoline complex.
Example 4
A preparation method of a modified nano-silver antibacterial composite material comprises the following steps:
s1, adding the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and water into a reaction device, wherein the weight ratio of the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide and the nano titanium dioxide to the water is 55: 3: 2: 2.5: 300, uniformly stirring, placing in microwave equipment, carrying out microwave treatment for 35min under the power of 700W, cooling, filtering and drying to obtain a material A; wherein the average particle size of the nano zinc oxide, the average particle size of the nano copper oxide and the average particle size of the nano titanium dioxide are all 30 nm;
s2, mixing the material A, the silane coupling agent KH-540 and dimethylformamide, wherein the weight ratio of the material A to the silane coupling agent KH-540 to dimethylformamide is 5: 9: stirring for 11 hours at the temperature of 92 ℃ by taking nitrogen as protective gas, centrifuging, washing and drying to obtain a material B;
s3, uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, stirring for 45min, and mixing with a material B, wherein the weight ratio of the graphene oxide to the material B is 1: 15, stirring for 160min at room temperature, centrifuging, washing and drying to obtain a material C;
s4, adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D; wherein the nano silver sol is electrolytic nano silver sol, and the weight content of the nano silver is 0.4 wt%; the weight volume ratio of the material C to the nano silver sol is 95: 160 mg/ml; the ultrasonic treatment time is 240min, the temperature is 45 ℃, and the frequency is 32 kHz;
s5, mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, uniformly stirring, and removing water to obtain the modified nano-silver antibacterial composite material; wherein the weight ratio of the material D, the boron oxide, the copper chlorophyllin acid and the 8-hydroxyquinoline complex is 7: 1.5: 0.3: 4.5; the 8-hydroxyquinoline complex is prepared according to the following process: uniformly mixing ethanol and water to obtain a solvent, wherein the volume ratio of the ethanol to the water is 3: 1, adding 8-hydroxyquinoline, pimelic acid and cerium nitrate into a solvent, and uniformly dispersing, wherein the molar ratio of the 8-hydroxyquinoline to the pimelic acid to the cerium nitrate is 1: 1: 1.5, then placing the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for 24 hours at the temperature of 130 ℃, and filtering, washing and drying the mixture after the reaction is finished to obtain the 8-hydroxyquinoline complex.
Example 5
A preparation method of a modified nano-silver antibacterial composite material comprises the following steps:
s1, adding the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and water into a reaction device, uniformly stirring, placing the mixture into microwave equipment for microwave treatment, and cooling, filtering and drying to obtain a material A; wherein the weight ratio of SBA-15 molecular sieve, nano zinc oxide, nano copper oxide, nano titanium dioxide and water is 50: 1: 1: 1: 280 parts of; the average particle size of the nano zinc oxide, the average particle size of the nano copper oxide and the average particle size of the nano titanium dioxide are all 40 nm; the power of the microwave treatment is 620W, and the time of the microwave treatment is 40 min;
s2, mixing the material A, the silane coupling agent KH-540 and dimethylformamide, wherein the weight ratio of the material A to the silane coupling agent KH-540 to dimethylformamide is 6: 11: 45, stirring for 13 hours at 90 ℃ by taking nitrogen as protective gas, centrifuging, washing and drying to obtain a material B;
s3, uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, stirring for 55min, and mixing with a material B, wherein the weight ratio of the graphene oxide to the material B is 1: 18, stirring at room temperature for 125min, centrifuging, washing and drying to obtain a material C;
s4, adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D; wherein the nano silver sol is electrolytic nano silver sol, and the weight content of the nano silver is 0.4 wt%; the weight volume ratio of the material C to the nano silver sol is 90: 200 mg/ml; the ultrasonic treatment time is 210min, the temperature is 50 ℃, and the frequency is 29 kHz;
s5, mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, uniformly stirring, and removing water to obtain the modified nano-silver antibacterial composite material; wherein the weight ratio of the material D, the boron oxide, the copper chlorophyllin acid and the 8-hydroxyquinoline complex is 5: 1: 0.5: 3; the 8-hydroxyquinoline complex is prepared according to the following process: uniformly mixing ethanol and water to obtain a solvent, adding 8-hydroxyquinoline, pimelic acid and cerium nitrate into the solvent to be uniformly dispersed, then placing the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 35 hours, and filtering, washing and drying the mixture after the reaction is finished to obtain the 8-hydroxyquinoline complex; wherein the volume ratio of ethanol to water is 2: 3; the mol ratio of 8-hydroxyquinoline to pimelic acid to cerium nitrate is 1: 1: 1.
comparative example 1
The blend of SBA-15 molecular sieve, nano zinc oxide, nano copper oxide, nano titanium dioxide, graphene oxide, nano silver sol, boron oxide, copper chlorophyllin and 8-hydroxyquinoline complex which is equal to that in example 5 is used as the antibacterial composite material.
Comparative example 2
The only difference from example 5 is that: the preparation method does not include S1, and in S2, SBA-15 molecular sieve, silane coupling agent KH-540 and dimethylformamide are directly mixed.
Comparative example 3
The only difference from example 5 is that: in S5, copper chlorophyllin was not contained.
Comparative example 4
The only difference from example 5 is that: in S5, the 8-hydroxyquinoline complex is not contained.
The antibacterial composite materials of example 5 and comparative examples 1 to 4 were tested for antibacterial activity against staphylococcus aureus and escherichia coli, and the Minimum Inhibitory Concentrations (MICs) were as shown in the following table:
| staphylococcus aureus MIC/mg/L | Escherichia coli MIC/mg/L | |
| Example 5 | 72 | 86 |
| Comparative example 1 | 137 | 149 |
| Comparative example 2 | 118 | 126 |
| Comparative example 3 | 87 | 94 |
| Comparative example 4 | 97 | 102 |
Five conical flasks were placed in a constant temperature water bath at 40 ℃, 1g of the antibacterial composite material samples prepared in example 5 and comparative examples 1 to 4 was added to each flask, 200mL of saline (0.9 wt%) was added to each flask, and samples were taken after soaking in water for 6, 24 and 72 hours, respectively, to determine the minimum inhibitory concentrations, and the results are shown in the following table:
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 person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (6)
1. A preparation method of a modified nano-silver antibacterial composite material is characterized by comprising the following steps:
s1, adding the SBA-15 molecular sieve, the nano zinc oxide, the nano copper oxide, the nano titanium dioxide and water into a reaction device, uniformly stirring, placing the mixture into microwave equipment for microwave treatment, and cooling, filtering and drying to obtain a material A;
s2, mixing the material A, the silane coupling agent KH-540 and dimethylformamide, stirring for 10-15h at 85-95 ℃ by taking nitrogen as protective gas, centrifuging, washing and drying to obtain a material B;
s3, uniformly mixing 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, N-hydroxysuccinimide and water to obtain an activating agent; uniformly mixing graphene oxide with water, adding an activating agent, stirring for 40-60min, mixing with the material B, stirring at room temperature for 180min, centrifuging, washing and drying to obtain a material C;
s4, adding the material C and the nano silver sol into ethanol, performing ultrasonic treatment, and drying to obtain a material D;
s5, mixing the material D, boron oxide, copper chlorophyllin acid, 8-hydroxyquinoline complex and water, uniformly stirring, and removing water to obtain the modified nano-silver antibacterial composite material; wherein the 8-hydroxyquinoline complex is prepared according to the following process: uniformly mixing ethanol and water to obtain a solvent, adding 8-hydroxyquinoline, pimelic acid and cerium nitrate into the solvent to be uniformly dispersed, then placing the mixture into a hydrothermal reaction kettle to carry out hydrothermal reaction, and filtering, washing and drying the mixture after the reaction is finished to obtain the 8-hydroxyquinoline complex;
in S1, the weight ratio of SBA-15 molecular sieve, nano zinc oxide, nano copper oxide, nano titanium dioxide and water is 35-55: 1-3: 0.5-2: 1-2.5: 250-300;
in S2, the weight ratio of the material A, the silane coupling agent KH-540 and the dimethylformamide is 4-6: 9-13: 40-60 parts;
in S3, the weight ratio of graphene oxide to material B is 1: 15-20 parts of;
in S4, the nano silver sol is an electrolytic nano silver sol, and the weight content of the nano silver is 0.4 wt%; the weight volume ratio of the material C to the nano silver sol is 85-95: 160-220 mg/ml;
in S5, the weight ratio of the material D, boron oxide, copper chlorophyllin acid and 8-hydroxyquinoline complex is 5-9: 0.5-1.5: 0.3-1.2: 2-4.5.
2. The method for preparing the modified nano-silver antibacterial composite material according to claim 1, wherein in S1, the average particle size of nano-zinc oxide, the average particle size of nano-copper oxide and the average particle size of nano-titanium dioxide are all 25-40 nm.
3. The method for preparing the modified nano-silver antibacterial composite material as claimed in claim 1 or 2, wherein in S1, the power of the microwave treatment is 550-700W, and the time of the microwave treatment is 35-60 min.
4. The preparation method of the modified nano-silver antibacterial composite material as claimed in claim 1 or 2, wherein in S4, the ultrasonic treatment time is 180-240min, the temperature is 45-55 ℃, and the frequency is 25-32 kHz.
5. The preparation method of the modified nano-silver antibacterial composite material according to claim 1 or 2, wherein in the S5, in the preparation process of the 8-hydroxyquinoline complex, the volume ratio of ethanol to water is 1-3: 1-5; the mol ratio of 8-hydroxyquinoline to pimelic acid to cerium nitrate is 1: 1: 0.5-1.5.
6. The preparation method of the modified nano-silver antibacterial composite material as claimed in claim 1 or 2, wherein in the step of preparing the 8-hydroxyquinoline complex, the hydrothermal reaction is carried out at a temperature of 105 ℃ to 130 ℃ for 24-40h in S5.
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