CN112335681A - Preparation method of layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral agent - Google Patents
Preparation method of layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral agent Download PDFInfo
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Abstract
The invention relates to a preparation method of a layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral material. Weighing silver salt, zinc salt, copper salt, a modifier, a complexing agent and a solvent, and modifying and complexing metal ions by adopting ultrasonic-assisted high-speed shearing and stirring to prepare metastable-state complexing silver-zinc-copper composite ions; then stirring and dispersing, adsorbing the mixture to the interlayer of the two-dimensional nano layered material through unsaturation, adding the mixture into a supercritical reaction kettle, and pumping carbon dioxide into the reaction kettle from a high-pressure pump; and controlling the pressure and the temperature, quickly decompressing the supercritical fluid through a nozzle, centrifuging, drying and crushing to obtain the layered unsaturated load silver-zinc-copper composite antibacterial and antiviral material. The composite antibacterial and antiviral material prepared by the method has the advantages of good heat resistance, high safety and the like, can be used for preparing fibers such as antibacterial and antiviral terylene, nylon and the like, can be blended with tencel, combed cotton and the like, can be widely used in the fields of underwear, sports coats, home textiles and the like, and has comfortable fabric hand feeling and strong antibacterial and antiviral functions.
Description
Technical Field
The invention belongs to the field of nano preparation, and particularly relates to a preparation method of a layered material unsaturated load silver-zinc-copper composite antibacterial and antiviral material.
Background
With the development of modern society, the quality requirements of people on life are higher and higher, which also leads the attention of the masses to ubiquitous bacteria and viruses in life. Particularly, in 2020, new coronary pneumonia has abused worldwide, and people have increasingly demanded antibacterial and antiviral effects. In daily life, besides new coronavirus, bacterial viruses such as influenza virus, escherichia coli, staphylococcus aureus and the like also have great threat to the life health of people, so that the development of broad-spectrum and efficient antibacterial and antiviral materials which can be applied to a plurality of fields becomes a problem which needs to be solved urgently.
The commonly used antibacterial materials at present comprise inorganic antibacterial materials and organic antibacterial materials, the inorganic antibacterial materials are commonly used metal ion type antibacterial agents taking silver ions and the like as active components and photocatalytic type antibacterial agents taking titanium dioxide as a representative component, but the antibacterial effect of the silver ions is greatly influenced by light and heat, the titanium dioxide can play the antibacterial effect under the irradiation of near ultraviolet light, and the titanium dioxide is difficult to settle and recover and is limited in application. Quaternary ammonium salt, halogen amine and chitosan antibacterial agents are commonly used as organic antibacterial materials, but the quaternary ammonium salt antibacterial agent is a low-molecular antibacterial agent with poor heat resistance and high toxicity; the halamine antibacterial agent is a high-molecular antibacterial agent, has poor compatibility and limited application range; the chitosan antibacterial agent is a natural antibacterial agent, has poor water solubility and is difficult to be used as an additive. In view of the disadvantages of the conventional antibacterial materials, a new antibacterial and antiviral material with stability, safety and broad spectrum is needed.
The two-dimensional nanosheet layers are combined through Van der Waals force, and metal ions such as silver, zinc, copper and the like are absorbed in the two-dimensional nanosheet layers, so that the stability of the antibacterial agent can be improved. However, the interlayer spacing is often too small, and silver, zinc and copper ions are generally difficult to enter the two-dimensional nanosheet layers due to various reasons such as the surface tension of the solution, and the loading rate is affected.
The invention adsorbs specially prepared metastable silver-zinc-copper ions to the interlayer of the layered substance through unsaturation by utilizing the supercritical fluid. On one hand, the supercritical fluid has extremely low surface tension, and can introduce metastable complex silver, zinc and copper ions into the two-dimensional nanosheet layer; on the other hand, the supercritical fluid rapid expansion method can be used for increasing the interlayer spacing of the two-dimensional nanosheets and reducing the difficulty of metastable silver, zinc and copper ions entering the interlayer.
The layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material prepared by the method can quickly adsorb bacteria and viruses to enter the interlayer when in use, and then utilize the complex silver-zinc-copper ions to kill the bacteria and the viruses; on the other hand, the problem that the common silver ion antibacterial material is easy to oxidize and discolor to generate black spots can be solved, and compared with the common silver ion antibacterial material, the silver ion antibacterial material has less dissolved substances and longer service life. Even, the layered composite antibacterial and antiviral material is formed by composite processing with a weak light photocatalysis material and high-temperature firing, so that the broad spectrum of antibacterial and antiviral can be further enhanced. The composite antibacterial and antiviral material prepared by the method has the advantages of good heat resistance, high safety and the like, can be used for preparing antibacterial polyester, Nylon and Rayon fibers, blended yarns and fabrics with tencel, combed cotton, long stapled cotton, polyester, viscose, modal and the like, can be widely used for a plurality of fields of underwear, sports and leisure coats, shirts, home textiles and the like, and has comfortable hand feeling, antibacterial and antiviral properties and strong health care functions.
Disclosure of Invention
The invention aims to provide a preparation method of a layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material aiming at the defects of insufficient antiviral performance, poor stability and the like of the existing antibacterial and antiviral material.
The method for preparing the layered material unsaturated silver-zinc-copper ion loaded composite antibacterial and antiviral material provided by the invention comprises the following steps: weighing inorganic silver salt, zinc salt, copper salt, a modifier and a solvent, firstly adding the silver salt, the zinc salt, the copper salt, a complexing agent and the modifier into the solvent, and modifying and complexing metal ions by adopting ultrasonic-assisted high-speed shearing and stirring to prepare a modified metal silver zinc copper ion solution; adding the two-dimensional nano-layered material into the solution, stirring and dispersing, then adding into a supercritical reaction kettle, opening a carbon dioxide steel cylinder, cooling carbon dioxide gas into liquid through a cold machine, pressurizing by a high-pressure pump, and then entering into the reaction kettle. Controlling certain pressure and temperature, and maintaining the pressure for a certain time under an ultrasonic environment. And (3) rapidly decompressing the supercritical fluid through a nozzle, centrifuging, drying and crushing the residual mixed solution to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material.
The method comprises the following specific steps:
1) according to the formula, inorganic silver salt, zinc salt, copper salt, a modifier, a complexing agent and a solvent are accurately weighed, firstly, the silver salt, the zinc salt, the copper salt, the complexing agent and the modifier are added into the solvent, metal ions are modified and complexed in an ultrasonic-assisted high-speed shearing and stirring mode, and metastable complex silver-zinc-copper composite ions are prepared and can enter between two-dimensional nanosheet layers more easily.
2) Adding a two-dimensional nano layered material into the metastable state complexing silver-zinc-copper composite ion solution prepared in the step 1), stirring and dispersing, and adsorbing the metastable state complexing silver-zinc-copper composite ion to the interlayer of the two-dimensional nano layered material through unsaturated adsorption.
3) Adding the mixed solution prepared in the step 2) into a supercritical reaction kettle, opening a carbon dioxide steel cylinder, cooling carbon dioxide gas into liquid through a cold machine, pressurizing by a high-pressure pump, and then feeding into the reaction kettle. Controlling certain pressure and temperature, and maintaining the pressure for a certain time under an ultrasonic environment.
4) And (3) rapidly decompressing the supercritical fluid in the reaction kettle in the step 3) through a nozzle, centrifuging, drying and crushing the residual mixed solution to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material.
Preferably, the silver salt in the step (1) is any one or a mixture of several of silver nitrate, silver fluoride, silver chlorate, silver perchlorate and silver bicarbonate; the zinc salt is any one or a mixture of zinc chloride, zinc bromide, zinc nitrate, zinc carbonate, zinc acetate and zinc sulfate; the copper salt is any one or a mixture of more of copper chloride, copper sulfate and copper nitrate;
preferably, the complexing agent in the step (1) is one or a mixture of more of ethylenediamine tetraacetic acid, citric acid, dibenzo-18-crown-6, diethylenetriamine pentaacetic acid, benzo-15-crown-5, inositol phosphate, ethylene glycol-bis- (2-aminoethyl) tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, beta-mercaptoethylamine hydrochloride, sodium hydroxyethylidene diphosphonate, PN sodium hydroxymethyl sulfonate and diethylenetriamine pentaethanol; the solvent is one or more of deionized water, ethanol, isopropanol, acetone, ethylene glycol and dimethylformamide; the modifier is one or a mixture of more of ethylenediamine, 2-bipyridine, 1, 10-diazophenanthrene, nitrilotriacetic acid, ethylenediamine tetraacetic acid, dithizone, 8-hydroxyquinoline, phenanthroline, potassium sodium tartrate, ammonium citrate and polyphosphate;
preferably, the mass ratio of the silver salt to the solvent in the step (1) is 1: 1-1000; the mass ratio of the silver salt to the zinc salt is 1: 0.01-100; the mass ratio of the silver salt to the copper salt is 1: 0.01-100; the mass ratio of the silver salt to the complexing agent to the modifier is 1: 0.01-100;
preferably, the ultrasonic power in the step (1) is 1000-8000W; the high-speed shearing dispersion adopts a Fluke FA25 high-shear dispersion emulsifying machine, the rotating speed is 5000-30000 r/min, and the processing time is 0.5-10 hours.
Preferably, in the step (2), the two-dimensional nano layered material is any one or a mixture of several of nickel cobalt lithium manganate, boron nitride, molybdenum sulfide, zirconium hydrogen phosphate, mica, vermiculite, graphite, black phosphorus and graphite-like phase carbon nitride. The mass ratio of the silver salt to the two-dimensional nano layered material is 1: 1-10000;
preferably, the ultrasonic power in the step (3) is 1000-8000W; the pressure is 10-40 MPa; the temperature is 323-383K; the pressure maintaining time is 10-90 min.
Preferably, the diameter of the nozzle in the step (4) is 100-500 μm.
Compared with the prior art, the method for preparing the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material, on one hand, utilizes the specific extremely low surface tension of the supercritical fluid to guide the silver-zinc-copper ions into the two-dimensional nanosheet layers; on the other hand, the supercritical fluid rapid expansion method is utilized to increase the interlayer spacing of the two-dimensional nanosheets, reduce the difficulty of metastable silver, zinc and copper ions entering the interlayer and improve the loading capacity; meanwhile, the unsaturated silver-zinc-copper ions are loaded, so that the adsorption and promotion killing effect on viruses is achieved, and meanwhile, the silver-zinc-copper ions can be more easily dissolved out to kill bacteria and viruses.
Compared with the prior art, the unsaturated silver-zinc-copper ion-loaded layered material composite antibacterial and antiviral material prepared by the method can quickly adsorb bacteria and viruses to enter the interlayer when in use, and then kill the bacteria and the viruses by using the silver-zinc-copper ions; on the other hand, the problem that the common silver ion antibacterial material is easy to oxidize and discolor to generate black spots can be solved, and compared with the common silver ion antibacterial material, the silver ion antibacterial material has less dissolved substances and longer service life. Even, the broad spectrum of the antibacterial and antiviral materials can be further enhanced by processing the materials in a compounding way with a weak light photocatalysis material and firing the materials at high temperature to form the layered composite antibacterial and antiviral material.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a comparison of the killing efficiency of the first, second and third products of the invention and the commercial antibacterial and antiviral material against H1N1 influenza virus
FIG. 2 is a comparison of specific surface areas of the first, second and third products of the present invention and commercially available antibacterial and antiviral materials
FIG. 3 is a diagram illustrating a particle size distribution of a powder according to an embodiment of the present invention
FIG. 4 is an SEM photograph of three powders in the example of the invention
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The first embodiment is as follows:
weighing inorganic silver salt, zinc salt, copper salt, a modifier, a complexing agent and a solvent (silver salt is silver nitrate, zinc salt is zinc chloride, copper salt is copper sulfate, the solvent is deionized water, the mass ratio of the silver salt to the solvent is 1:1, the mass ratio of the silver salt to the zinc salt is 1:0.01, the mass ratio of the silver salt to the copper salt is 1:0.01, the modifier is nitrilotriacetic acid, the complexing agent is benzo-15-crown-5, and the mass ratio of the silver salt to the complexing agent to the modifier is 1:0.01:0.01), firstly adding the silver salt, the zinc salt, the copper salt, the complexing agent and the modifier into the solvent, and modifying metal ions by adopting an ultrasonic (power of 1000W) assisted high-speed shearing (the rotating speed is 5000 r/min, and the processing time is 0.5h) stirring mode to obtain a modified metastable silver-zinc-copper ion complexing solution; adding a two-dimensional nano-layered material (the two-dimensional nano-layered material is zirconium hydrogen phosphate, the mass ratio of silver salt to the two-dimensional nano-layered material is 1:1) into the solution, stirring and dispersing, then adding into a supercritical reaction kettle, opening a carbon dioxide steel cylinder, cooling carbon dioxide gas into liquid by a cold machine, pressurizing by a high-pressure pump, and then entering into the reaction kettle. Controlling certain pressure (pressure is 10MPa) and temperature (temperature is 323K), and maintaining the pressure for a certain time (pressure maintaining time is 10min) in an ultrasonic environment (ultrasonic power is 1000W); and (3) rapidly decompressing the supercritical fluid through a nozzle (the diameter of the nozzle is 100 mu m), centrifuging, drying and crushing the residual mixed solution to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material.
Example two:
weighing inorganic silver salt, zinc salt, copper salt, a modifier, a complexing agent and a solvent (silver salt is silver chlorate, zinc salt is zinc carbonate, copper salt is copper chloride, solvent is ethanol, the mass ratio of the silver salt to the solvent is 1:500, the mass ratio of the silver salt to the zinc salt is 1:20, the mass ratio of the silver salt to the copper salt is 1:30, the modifier is potassium sodium tartrate, the complexing agent is diethylenetriamine pentaacetic acid, and the mass ratio of the silver salt to the complexing agent to the modifier is 1:50:50), firstly adding the silver salt, the zinc salt, the copper salt, the complexing agent and the modifier into the solvent, and modifying metal ions by adopting an ultrasonic (power of 3000W) assisted high-speed shearing (rotating speed of 15000 r/min, and processing time of 3h) stirring mode to obtain a modified metastable state complexing silver zinc-copper ion solution; adding a two-dimensional nano-layered material (the two-dimensional nano-layered material is graphite-like carbon nitride, the mass ratio of silver salt to the two-dimensional nano-layered material is 1:80) into the solution, stirring and dispersing, then adding into a supercritical reaction kettle, opening a carbon dioxide steel cylinder, cooling carbon dioxide gas into liquid by a cold machine, pressurizing by a high-pressure pump, and then entering into the reaction kettle. Controlling certain pressure (30 MPa) and temperature (348K), and maintaining the pressure for a certain time (50 min) in an ultrasonic environment (3000W ultrasonic power); and (3) rapidly decompressing the supercritical fluid through a nozzle (the diameter of the nozzle is 300 mu m), centrifuging, drying and crushing the residual mixed solution to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial antiviral material.
Example three:
weighing inorganic silver salt, zinc salt, copper salt, a modifier, a complexing agent and a solvent (silver salt is silver bicarbonate, zinc salt is zinc acetate, copper salt is copper nitrate, solvent is isopropanol, the mass ratio of the silver salt to the solvent is 1:300, the mass ratio of the silver salt to the zinc salt is 1:5, the mass ratio of the silver salt to the copper salt is 1:2, the modifier is dithizone, the complexing agent is PN sodium hydroxymethyl sulfonate, and the mass ratio of the silver salt to the complexing agent to the modifier is 1:100:100), firstly adding the silver salt, the zinc salt, the copper salt, the complexing agent and the modifier into the solvent, and modifying metal ions by adopting an ultrasonic (power of 8000W) assisted high-speed shearing (rotating speed of 30000 r/min and processing time of 10h) stirring mode to obtain a modified metastable state complexing silver-zinc-copper ion solution; adding a two-dimensional nano layered material (the mass ratio of nickel cobalt lithium manganate, silver salt and the two-dimensional nano layered material is 1:10000) into the solution, stirring and dispersing, adding into a supercritical reaction kettle, opening a carbon dioxide steel cylinder, cooling carbon dioxide gas into liquid by a cold machine, pressurizing by a high-pressure pump, and then entering into the reaction kettle. Controlling certain pressure (40 MPa) and temperature (383K), and maintaining the pressure for certain time (90 min) in an ultrasonic environment (8000W of ultrasonic power); and (3) rapidly decompressing the supercritical fluid through a nozzle (the diameter of the nozzle is 500 mu m), centrifuging, drying and crushing the residual mixed solution to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material.
TABLE A commonly used commercial antibacterial and antiviral material and the influenza H1N1 virus killing rate of the sample of the patent examples of the present invention
| Sample numbering | Specific surface area g/m3 | Influenza virus killing rate |
| Commercially available antibacterial and antiviral materials | 78 | 79.2％ |
| Example A Material | 192 | 99.9％ |
| EXAMPLE two materials | 187 | 99.8％ |
| EXAMPLES three materials | 213 | 99.95％ |
Claims (8)
1. A preparation method of a layered unsaturated silver-zinc-copper loaded composite antibacterial and antiviral material is characterized by comprising the following specific steps:
1) accurately weighing inorganic silver salt, zinc salt, copper salt, a modifier, a complexing agent and a solvent according to a formula, firstly adding the silver salt, the zinc salt, the copper salt and the modifier into the solvent, and modifying and complexing metal ions by adopting an ultrasonic-assisted high-speed shearing and stirring mode to prepare metastable complex silver-zinc-copper composite ions, so that the metastable complex silver-zinc-copper composite ions can enter between two-dimensional nanosheet layers more easily;
2) adding a two-dimensional nano layered material into the metastable state complexing silver-zinc-copper composite ion solution prepared in the step 1), stirring and dispersing, and adsorbing the metastable state complexing silver-zinc-copper composite ion to the interlayer of the two-dimensional nano layered material through unsaturated adsorption;
3) adding the mixed solution prepared in the step 2) into a supercritical reaction kettle, opening a carbon dioxide steel cylinder, cooling carbon dioxide gas into liquid by a cold machine, pressurizing by a high-pressure pump, then feeding into the reaction kettle, controlling certain pressure and temperature, and maintaining the pressure for a certain time under an ultrasonic environment;
4) and (3) rapidly decompressing the supercritical fluid in the reaction kettle in the step 3) through a nozzle, centrifuging, drying and crushing the residual mixed solution to obtain the layered material unsaturated load silver-zinc-copper ion composite antibacterial and antiviral material.
2. The preparation method of the layered unsaturated silver-loaded zinc-copper composite antibacterial and antiviral material according to claim 1, wherein the silver salt in the step (1) is any one or a mixture of several of silver nitrate, silver fluoride, silver chlorate, silver perchlorate and silver bicarbonate; the zinc salt is any one or a mixture of zinc chloride, zinc bromide, zinc nitrate, zinc carbonate, zinc acetate and zinc sulfate; the copper salt is any one or a mixture of more of copper chloride, copper sulfate and copper nitrate.
3. The method for preparing the layered unsaturated silver-loaded zinc-copper composite antibacterial and antiviral material according to claim 1, wherein the complexing agent in the step (1) is any one or a mixture of more of ethylenediamine tetraacetic acid, citric acid, dibenzo-18-crown-6, diethylenetriamine pentaacetic acid, benzo-15-crown-5, inositol phosphate, ethylene glycol-bis- (2-aminoethyl) tetraacetic acid, nitrilotriacetic acid, diethylenetriamine pentaacetic acid, beta-mercaptoethylamine hydrochloride hydroxyethylidene diphosphonic acid sodium, PN hydroxymethyl sodium sulfonate, diethylenetriamine pentaethanol; the solvent is one or more of deionized water, ethanol, isopropanol, acetone, ethylene glycol and dimethylformamide; the modifier is one or more of ethylenediamine, 2-bipyridine, 1, 10-diazophenanthrene, nitrilotriacetic acid, ethylenediamine tetraacetic acid, dithizone, 8-hydroxyquinoline, phenanthroline, potassium sodium tartrate, ammonium citrate and polyphosphate.
4. The preparation method of the layered unsaturated silver-loaded zinc-copper composite antibacterial and antiviral material as claimed in claim 1, wherein the mass ratio of the silver salt to the solvent in the step (1) is 1: 1-1000; the mass ratio of the silver salt to the zinc salt is 1: 0.01-100; the mass ratio of the silver salt to the copper salt is 1: 0.01-100; the mass ratio of the silver salt to the complexing agent to the modifier is 1: 0.01-100.
5. The preparation method of the layered unsaturated silver-loaded zinc-copper composite antibacterial and antiviral material according to claim 1, wherein in the step (1), the ultrasonic power is 1000-8000W; the high-speed shearing dispersion adopts a Fluke FA25 high-shear dispersion emulsifying machine, the rotating speed is 5000-30000 r/min, and the processing time is 0.5-10 hours.
6. The method for preparing the layered unsaturated silver-loaded zinc-copper composite antibacterial and antiviral material according to claim 1, wherein the two-dimensional nano layered material in the step (2) is any one or a mixture of nickel-cobalt lithium manganate, boron nitride, molybdenum sulfide, zirconium hydrogen phosphate, mica, vermiculite, graphite, black phosphorus and graphite-like phase carbon nitride, and the mass ratio of the silver salt to the two-dimensional nano layered material is 1: 1-10000.
7. The preparation method of the layered unsaturated silver-loaded zinc-copper composite antibacterial and antiviral material as claimed in claim 1, wherein in the step (3), the ultrasonic power is 1000-8000W; the pressure is 10-40 MPa; the temperature is 323-383K; the pressure maintaining time is 10-90 min.
8. The method for preparing the layered unsaturated silver-loaded zinc-copper composite antibacterial and antiviral material as claimed in claim 1, wherein the diameter of the nozzle in the step (4) is 100-500 μm.
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| CN115517268B (en) * | 2022-09-05 | 2024-03-29 | 深圳市飞白科技有限公司 | Silver-loaded zinc-copper single-layer zirconium phosphate nano-sheet and preparation method thereof |
| CN115868485A (en) * | 2022-11-30 | 2023-03-31 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of silver-loaded copper layered zirconium phosphate composite antibacterial and antiviral nano material, product and application thereof |
| CN117285734A (en) * | 2023-10-16 | 2023-12-26 | 潍坊泰锋环保科技有限公司 | Environment-friendly degradable plastic and preparation method thereof |
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