CN114875497A - Metal nano self-assembly fiber material, and preparation method and application thereof - Google Patents
Metal nano self-assembly fiber material, and preparation method and application thereof Download PDFInfo
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- CN114875497A CN114875497A CN202210477807.9A CN202210477807A CN114875497A CN 114875497 A CN114875497 A CN 114875497A CN 202210477807 A CN202210477807 A CN 202210477807A CN 114875497 A CN114875497 A CN 114875497A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
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- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000001338 self-assembly Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 24
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- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002033 PVDF binder Substances 0.000 claims description 44
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 44
- 238000009987 spinning Methods 0.000 claims description 36
- 239000002082 metal nanoparticle Substances 0.000 claims description 34
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 31
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- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 238000005516 engineering process Methods 0.000 claims description 6
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- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
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- 239000000243 solution Substances 0.000 description 32
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 25
- 239000002105 nanoparticle Substances 0.000 description 20
- 229910052709 silver Inorganic materials 0.000 description 20
- 239000004332 silver Substances 0.000 description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 18
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 2
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- 230000000845 anti-microbial effect Effects 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
- A41D13/1192—Protective face masks, e.g. for surgical use, or for use in foul atmospheres with antimicrobial agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/04—Organic material, e.g. cellulose, cotton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/02—Loose filtering material, e.g. loose fibres
- B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/10—Filtering material manufacturing
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention provides a metal nanoparticle-doped high-molecular polymer electrostatic spinning nanofiber medical material prepared by a one-step method. The medical material prepared by the method has the performances of electrostatic regeneration, antibiosis and radiation protection, and is used for the mask core filter material. The prepared mask has the advantages that the antibacterial effect is guaranteed, meanwhile, long-time static adsorption is unchanged, the service life of the mask is prolonged, and meanwhile, the mask is endowed with the radiation-proof function. The pressure of the waste mask on the environment is effectively relieved, and the harm of electromagnetic radiation on a human body in production and life is reduced.
Description
Technical Field
The invention belongs to the field of medical protective materials, and particularly relates to an electrostatic spinning micro-nanofiber medical protective material with long-acting filtering, antibacterial and radiation-proof properties and a preparation method thereof.
Background
Masks typically consist of a three layer structure including outer spunbond, interlayer meltblown, inner spunbond, where the interlayer meltblown plays a critical role in filtration. Melt-blown cloth has unique advantage in the aspect of the mechanical guarantee, direct interception, brown diffusion, gravity subsides and the electrostatic action to the particle, polymer solution or fuse-element are through the extrusion to traditional preparation melt-blown cloth, pile up fast under the thermal current effect, produce the superfine fiber of micron or micron order, there is an easy problem of weing in the gauze mask use, filtration efficiency is along with breathing the moist air that produces constantly reduces, the life of the greatly reduced gauze mask, the indirect or direct increase of remaining bacterium and virus on the gauze mask has propagated and the risk of infecting. The service life of the mask is prolonged, the pressure of the waste mask to the environment can be fundamentally reduced, and meanwhile, higher requirements on the antibacterial performance of the mask are provided.
With the rapid development of the electronic industry and the popularization of electronic products such as televisions, computers, mobile phones and the like, people are invisibly damaged by electromagnetic wave radiation, and a multifunctional mask which can meet the requirements of people on bacteriostasis and radiation protection in work, study and life is urgently needed.
Electrostatic spinning uses an electric field to convert polymer solution into continuous polymer fibers, a woven fiber membrane can be well used as a protective material of a mask, and compared with the traditional melt-blown manufacturing process, the nanofiber consisting of superfine fibers and continuous fibers has high porosity, variable pore size distribution, high surface area and volume ratio and is paid much attention to.
Piezoelectric materials are regarded by people, piezoelectricity refers to the ability of a material to generate electric charges when mechanically deformed in a proper direction, and mechanical energy generated by people in daily activities can be converted into electric energy by the piezoelectric materials. Mechanical deformation results in a displacement of the charge centers, resulting in an electrical polarization of the non-centrosymmetric unit cell. Piezoelectric effects can be observed in both organic and inorganic materials, and the most widely studied piezoelectric materials are barium titanate, potassium sodium niobate, zinc oxide, polyvinylidene fluoride, and the like. Nanostructured piezoelectric polymers exhibit significantly higher piezoelectric performance than bulk and thin film counterparts, and the piezoelectric response is observed in certain directions only when the material is synthesized as nanofibers. Therefore, through proper nano engineering and process control, the piezoelectric performance of the polymer can be obviously enhanced, the static attenuation of the fiber surface caused by breathing is effectively reduced, and the filtering efficiency of the filter material is kept, so that the service life of the mask is prolonged; the antibacterial material comprises synthetic organic matters, inorganic particles and natural antibacterial materials. Inorganic antibacterial materials tend to have stability and durability, which makes them have broad application prospects. As the particle size is reduced to the nanometer scale, the higher specific surface area and volume ratio makes these particles have different physical and chemical properties compared to common materials. Electrospun fibers can readily immobilize inorganic nanoparticles, providing unique catalytic, optical, and antimicrobial properties. Therefore, inorganic antibacterial materials currently used for electrospinning are mainly nanoscale metals, metal oxides, and carbon materials. The metal nano particles are widely researched antibacterial materials, have excellent antibacterial activity on staphylococcus aureus and escherichia coli, have excellent shielding efficiency on electromagnetic waves while having good antibacterial performance, and can reduce the harm of electromagnetic radiation on human bodies. For conventional electromagnetic interference (EMI) shielding materials, metals such as aluminum, copper, and stainless steel are typically coated around electrical equipment to block the transmission of electromagnetic radiation. But the wide application of the electromagnetic shielding material in the electromagnetic shielding field is limited by the large weight, the easy corrosion, the large processing difficulty and the like. The preparation of metal nanoparticles generally utilizes chemical methods and physical methods, but has high requirements on instruments and equipment and expensive manufacturing cost, and limits the large-scale production of the metal nanoparticles. The metal nano particles prepared by the electrostatic spinning process have the advantages of small size and large specific surface area, and also have good mechanical stability and good fiber continuity.
Disclosure of Invention
The invention provides a metal nanoparticle-doped high-molecular polymer electrostatic spinning nanofiber medical material prepared by a one-step method, which is used for solving the technical problems that the conventional preparation process for preparing metal nanoparticles is complex, agglomeration is easy to occur, the metal nanoparticles cannot be uniformly dispersed on fibers, and the production efficiency is influenced. The prepared mask has the advantages that the antibacterial effect is guaranteed, meanwhile, long-time static adsorption is unchanged, the service life of the mask is prolonged, and meanwhile, the mask is endowed with the radiation-proof function. The pressure of the waste mask on the environment is effectively relieved, and the harm of electromagnetic radiation on a human body in production and life is reduced.
The invention provides a preparation method of a metal nano self-assembly fiber material, which comprises the following steps:
firstly, reducing metal salt by a one-step method to prepare metal nanoparticles;
secondly, preparing a metal nanoparticle doped high-molecular polymer precursor spinning solution;
and thirdly, electrostatic spinning is carried out to prepare the metal nano self-assembly fiber material.
The first step is to add a stabilizer into an organic solvent, perform a constant-temperature water bath reaction, add metal salt after cooling, and perform magnetic stirring to obtain metal nanoparticles.
Wherein the metal salt is silver nitrate, copper sulfate, zinc sulfate or chloroauric acid.
Wherein the stabilizer is polyvinylpyrrolidone.
And the second step is to weigh a certain amount of organic matter macromolecules, add the organic matter macromolecules into an organic solvent, stir in a constant-temperature water bath, cool to room temperature, add the metal nanoparticles prepared in the first step, and continue stirring to obtain the metal nanoparticle doped high-molecular polymer spinning solution precursor.
Wherein the high molecular polymer is polyvinylidene fluoride.
And the third step specifically comprises the steps of collecting the precursor spinning solution prepared in the second step on melt-blown fabric on the surface of a receiving device through an electrostatic spinning technology, collecting to obtain a metal nano particle self-assembly fiber layer, and taking the obtained composite material off the receiving device.
The metal nano self-assembly fiber material prepared by the preparation method.
Wherein the self-assembled fibrous material has a spider-web structure.
The metal nano self-assembly fiber material is applied to medical protective articles and labor protection articles.
The invention has the advantages of
According to the piezoelectric antibacterial radiation-proof multifunctional mask, the non-woven fabric is protected outside the mask to have dustproof and antistatic properties, and the metal nano particles are self-assembled to prepare the high polymer-metal nano fiber layer. Mechanical energy generated along with human body movement is converted into electric energy by a piezoelectric material, the piezoelectric efficiency reaches 49.5V, the high-efficiency electrostatic adsorption performance of the filter material is kept, the influence of moisture gas generated by breathing on the filtering efficiency is effectively reduced, the service life of the mask is prolonged, the circulating filtering performance reaches 24 times, high efficiency and low resistance are still kept, (under the condition of 85L/min airflow, continuous filtering is carried out for 144 minutes), high-activity antibacterial metal ions are released durably at the same time, bacteria and viruses can be inhibited and killed, the filtering efficiency of the bacteria is detected to reach more than 95%, high-efficiency protection is kept, human body health is protected, metal nano particles are uniformly dispersed in fibers, electromagnetic waves can be shielded under specific electromagnetic wave frequency, and the harm to human bodies caused by electromagnetic radiation in production and life is reduced. Under 30-100HZ, the shielding effectiveness reaches 20dB, and the shielding effectiveness is good. The multifunctional mask has a four-layer structure, has more excellent filtering efficiency compared with the traditional mask, prolongs the service life of the mask, fundamentally relieves the pressure of a large amount of waste masks on the environment, changes the current situation of single function of the traditional mask, realizes the multifunction of piezoelectricity, antibiosis and radiation protection, and simultaneously can well improve the pain feeling of ears when people wear the mask for a long time by the design of wide ear bands.
The metal nano particle doped high molecular polymer fiber layer is prepared by the one-step method, the preparation method is simple and novel, the electrostatic spinning technology is adopted, metal salt is added into an organic solvent, metal particles are reduced by utilizing the reducibility of the organic solvent, the reduced metal particles are added into a high molecular polymer spinning solution to obtain a metal nano particle doped high molecular polymer precursor spinning solution, the metal nano particles are self-assembled along with the ejection of the spinning solution to prepare the fiber membrane with the cobweb structure, the fiber has high porosity, high specific surface area, high mechanical stability and high continuity, meanwhile, mechanical energy generated by human motion is converted into electric energy, the high-efficiency electrostatic adsorption capacity is kept, the released antibacterial metal ions also achieve the lasting antibacterial and bacteriostatic effects, and meanwhile, the harm of electromagnetic waves to human bodies is reduced. The melt-blown fabric is directly used as a receiving base material during spinning, processing steps are reduced, production efficiency is improved, the ear band is a wider soft ear band, pain of ears when the mask is worn for a long time is reduced, and the mask has great potential value.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 and FIG. 2 are scanning electron micrographs of the polymer-metal nanofibers according to the present invention;
FIG. 3 is a schematic structural view of a piezoelectric antibacterial radiation-proof multifunctional mask of the present invention;
fig. 4 is a schematic view of the layered structure of the multifunctional mask body according to the present invention.
1. A mask body; 2. seamless edge pressing; 3. the nose bridge strip can be adjusted; 4. a wide elastic ear band; 5. horizontal pleating; 11. an outer protective non-woven fabric layer; 12. a high molecular polymer-metal nanolayer; 13. spraying and melting the filter layer; 14. a soft skin-friendly inner layer.
Detailed Description
The invention provides a metal nanoparticle doped high molecular polymer electrostatic spinning nanofiber medical material, which has a spider-web structure, is prepared by adopting an electrostatic spinning technology, has an air slip effect, has a fiber diameter of 200nm-700nm, and has a large specific surface area, high porosity, high efficiency and low resistance.
The metal nanoparticles are prepared by reducing metal salts, including silver nitrate, copper sulfate, zinc sulfate or chloroauric acid.
The high molecular polymer polyvinylidene fluoride.
The invention provides a process for preparing metal nanoparticle doped high molecular polymer electrostatic spinning nanofibers by a one-step method, which comprises the following steps:
firstly, reducing metal salt to prepare metal nanoparticles;
secondly, preparing a metal nanoparticle doped high-molecular polymer precursor spinning solution;
and spinning the nanofiber membrane.
The first step is specifically to add a stabilizer into an organic solvent to prevent metal particles from agglomerating, stir and dissolve the metal particles in a water bath at a constant temperature of 80 ℃, cool the metal particles to room temperature, add metal salt into the water bath, and magnetically stir the metal particles for 12 hours in a dark environment to obtain metal salt nanoparticles. The concentration of the added metal salt is 3-5 Wt%, the metal salt is silver nitrate, copper sulfate, zinc sulfate or chloroauric acid, the organic solvent is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone, the stabilizer is polyvinylpyrrolidone, the concentration is 2 Wt%,
preferably, the metal salt is silver nitrate and the metal salt concentration is 5 Wt%.
The second step is specifically as follows:
weighing a certain amount of organic matter macromolecules, adding the organic matter macromolecules into an organic solvent, stirring for 4 hours at a constant temperature of 80 ℃, swelling and decomposing the macromolecular organic matter, uniformly dissolving the macromolecular organic matter in the organic solvent, cooling to room temperature, adding the metal nanoparticles prepared in the first step, and stirring for 1 hour at a dark environment of 80 ℃ to obtain a metal nanoparticle doped macromolecular polymer spinning solution precursor. The concentration of the added high molecular polymer is 13-15 Wt%, the high molecular polymer is polyvinylidene fluoride, and the organic solvent is N, N-dimethylformamide, N-dimethylacetamide or N-methylpyrrolidone.
Preferably, the concentration of the high molecular polymer is 14 Wt%, and the solvent is N, N-dimethylformamide.
The third step specifically comprises:
injecting the precursor spinning solution prepared in the second step into an injection pump, selecting a 17G needle, controlling the high-voltage direct current output voltage at 25ky, controlling the distance between the needle and a receiving device at 15cm, the speed of the injection pump at 0.05mL/min, the moving speed of a horizontal sliding table at 80mm/s, the moving width at 18cm, the relative humidity at 50% RH, the temperature at 25 ℃, and controlling the surface density of a fiber membrane at 5G/m 2 And collecting the high molecular polymer-metal nano fiber on the melt-blown cloth on the surface of the receiving device to obtain a metal nano particle self-assembled fiber layer, and taking the obtained composite material off the receiving device.
Preferably, the drying treatment method is drying treatment in a vacuum drying oven at 35 ℃.
The invention can be applied to the field of medical protection.
The invention provides electrostatic spinning equipment which comprises a high-voltage power supply, an injection pump, a liquid storage device, a flat-plate type and roller type receiving device, a movable sliding table, a temperature and humidity regulating and controlling device and ventilation equipment.
The invention provides a preparation method of a piezoelectric antibacterial radiation-proof multifunctional mask, which comprises the following steps:
the mask body is provided with seamless edge pressing around and is formed by hot pressing a soft skin-friendly inner layer, an organic polymer-metal nanofiber layer, a melt-blown filter layer and an outer protective non-woven fabric layer from inside to outside in sequence.
Preferably, the preparation method is to compound another layer of non-woven fabric on the high molecular polymer-metal nanofiber layer and the base material melt-blown fabric dried in the third step to form an external protection non-woven fabric layer, a high molecular polymer-metal nanofiber layer and a base material melt-blown fabric composite structure. Sequentially overlapping an outer protection non-woven fabric layer, a high polymer-metal nanofiber layer, a melt-blown filter layer and a soft skin-friendly inner layer in sequence, adhering the peripheries of the layers by hot pressing to obtain a mask body, pressing a plurality of folds in the horizontal direction, mounting a nose support on the upper part of the mask body, mounting an adjustable nose bridge strip on the lower side of the nose support, and symmetrically mounting wide and high-elastic ear bands on two sides of the outer protection non-woven fabric layer by hot pressing to obtain the multifunctional mask.
Preferably, the mask adopts a four-layer structure, the non-woven fabric is compounded on the metal nano particle doped polyvinylidene fluoride nano fiber layer and the base material melt-blown fabric, and the outer protective non-woven fabric layer, the metal nano particle doped high molecular polymer nano fiber layer, the melt-blown filter layer and the soft skin-friendly inner layer are sequentially overlapped to obtain the mask body.
The outer protective layer is made of antistatic dustproof non-woven material; the inner layer is non-irritant to skin and is a textile material of grade B or above; the width of the elastic ear band is 0.5-1.5cm, so that the pain feeling of ears when the mask is worn for a long time is reduced.
The invention provides a high-elasticity wide ear band which is used for fixing a multifunctional mask on the face and can reduce the pain feeling of ears when the multifunctional mask is worn for a long time.
The mask is subjected to particle circulating filtration for 24 times, still keeps high efficiency and low resistance, has the bacteriostatic rate on staphylococcus aureus and escherichia coli of more than 90 percent, has the shielding efficiency of 20dB under the frequency of 30-100MHz, and has good piezoelectric antibacterial and radiation-proof functions.
The technical solution of the present invention will be fully and clearly described below by describing in detail embodiments of the present invention with examples and the accompanying drawings, wherein the described examples are only a part of the embodiments of the present invention, and not all of the embodiments.
Example one
Weighing 1g of stabilizer polyvinylpyrrolidone, adding the stabilizer polyvinylpyrrolidone into a 20g N, N-dimethylformamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding 1.5g of silver nitrate in a dark environment, stirring for dissolution at room temperature for 12h to obtain silver nanoparticles, and standing the solution for defoaming. Weighing 7g of polyvinylidene fluoride, adding the polyvinylidene fluoride into a 20.5g N N-dimethylformamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding silver nanoparticles in a dark environment, stirring for 1h at 80 ℃ to prepare a silver nanoparticle doped polyvinylidene fluoride precursor spinning solution, and standing for defoaming. The mass fraction of the polyvinylpyrrolidone is 2%, the mass fraction of the polyvinylidene fluoride is 14%, and the mass fraction of the silver nitrate is 3%.
Injecting the spinning solution into an injection pump, selecting a 17G needle, adjusting the distance from a spinning needle point to a receiving device to be 15cm, setting the output voltage of high-voltage direct current to be 25kv, setting the speed of the injection pump to be 0.05mL/min, setting the moving speed of a horizontal sliding table to be 80mm/s and the width to be 18cm, flatly paving a non-woven fabric base material on a metal receiving device, preparing fibers at the temperature of 25 ℃ and the relative humidity of 50% RH, collecting polyvinylidene fluoride-silver nano fibers on melt-blown cloth on the surface of the receiving device, collecting to obtain a silver nano particle self-assembled fiber layer, taking the obtained composite material off from the receiving device, placing the composite material in a vacuum drying box at 35 ℃, and drying.
Compounding another layer of non-woven fabric 11 on the dried silver nanoparticle-doped polyvinylidene fluoride nanofiber layer 12 and the base material melt-blown fabric 13, sequentially laminating the outer protective non-woven fabric layer 11, the silver nanoparticle-doped polyvinylidene fluoride nanofiber layer 12, the melt-blown filter layer 13 and the soft skin-friendly inner layer 14 in sequence to prepare the mask body 1, bonding the periphery 2 by hot pressing, pressing a plurality of folds 3 in the horizontal direction, installing a nose support on the upper part of the mask body, installing an adjustable nose bridge strip 4 on the lower side of the nose support, and symmetrically installing wide high-elastic ear bands 5 on two sides of the outer protective non-woven fabric layer by hot pressing to prepare the multifunctional mask.
Example II
Weighing 1g of stabilizer polyvinylpyrrolidone, adding the stabilizer polyvinylpyrrolidone into a 20g N, N-dimethylformamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding 2g of silver nitrate in a dark environment, stirring for dissolution at room temperature for 12h to obtain silver nanoparticles, and standing the solution for defoaming. Weighing 7g of polyvinylidene fluoride, adding the polyvinylidene fluoride into a 20g N N-dimethylformamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding silver nanoparticles in a dark environment, stirring for 1h at 80 ℃ to prepare a silver nanoparticle doped polyvinylidene fluoride precursor spinning solution, and standing for defoaming. The mass fraction of the polyvinylpyrrolidone is 2%, the mass fraction of the polyvinylidene fluoride is 14%, and the mass fraction of the silver nitrate is 4%.
Injecting the spinning solution into an injection pump, selecting a 17G needle, adjusting the distance from a spinning needle point to a receiving device to be 15cm, setting the output voltage of high-voltage direct current to be 25kv, setting the speed of the injection pump to be 0.05mL/min, setting the moving speed of a horizontal sliding table to be 80mm/s and the width to be 18cm, flatly paving a non-woven fabric base material on a metal receiving device, preparing fibers at the temperature of 25 ℃ and the relative humidity of 50% RH, collecting polyvinylidene fluoride-silver nano fibers on melt-blown cloth on the surface of the receiving device, collecting to obtain a silver nano particle self-assembled fiber layer, taking the obtained composite material off from the receiving device, placing the composite material in a vacuum drying box at 35 ℃, and drying.
Compounding another layer of non-woven fabric 11 on the dried silver nanoparticle-doped polyvinylidene fluoride nanofiber layer 12 and the base material melt-blown fabric 13, sequentially laminating the outer protective non-woven fabric layer 11, the silver nanoparticle-doped polyvinylidene fluoride nanofiber layer 12, the melt-blown filter layer 13 and the soft skin-friendly inner layer 14 in sequence to prepare the mask body 1, bonding the periphery 2 by hot pressing, pressing a plurality of folds 3 in the horizontal direction, installing a nose support on the upper part of the mask body, installing an adjustable nose bridge strip 4 on the lower side of the nose support, and symmetrically installing wide high-elastic ear bands 5 on two sides of the outer protective non-woven fabric layer by hot pressing to prepare the multifunctional mask.
Example three
Weighing 1g of stabilizer polyvinylpyrrolidone, adding the stabilizer polyvinylpyrrolidone into a 20g N, N-dimethylformamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding 2.5g of silver nitrate in a dark environment, stirring for dissolution at room temperature for 12h to obtain silver nanoparticles, and standing the solution for defoaming. Weighing 7g of polyvinylidene fluoride, adding the polyvinylidene fluoride into a 19.5g N N-dimethylformamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding silver nanoparticles in a dark environment, stirring for 1h at 80 ℃ to prepare a silver nanoparticle doped polyvinylidene fluoride precursor spinning solution, and standing for defoaming. The mass fraction of the polyvinylpyrrolidone is 2%, the mass fraction of the polyvinylidene fluoride is 14%, and the mass fraction of the silver nitrate is 5%.
Injecting the spinning solution into an injection pump, selecting a 17G needle, adjusting the distance from a spinning needle point to a receiving device to be 15cm, setting the output voltage of high-voltage direct current to be 25kv, setting the speed of the injection pump to be 0.05mL/min, setting the moving speed of a horizontal sliding table to be 80mm/s and the width to be 18cm, flatly paving a non-woven fabric base material on a metal receiving device, preparing fibers at the temperature of 25 ℃ and the relative humidity of 50% RH, collecting polyvinylidene fluoride-silver nano fibers on melt-blown cloth on the surface of the receiving device, collecting to obtain a silver nano particle self-assembled fiber layer, taking the obtained composite material off from the receiving device, placing the composite material in a vacuum drying box at 35 ℃, and drying.
Compounding another layer of non-woven fabric 11 on the dried silver nanoparticle-doped polyvinylidene fluoride nanofiber layer 12 and the base material melt-blown fabric 13, sequentially laminating the outer protective non-woven fabric layer 11, the silver nanoparticle-doped polyvinylidene fluoride nanofiber layer 12, the melt-blown filter layer 13 and the soft skin-friendly inner layer 14 in sequence to prepare the mask body 1, bonding the periphery 2 by hot pressing, pressing a plurality of horizontal folds 3, installing a nose support on the upper part of the mask body, installing an adjustable nose bridge strip 4 on the lower side of the nose support, and symmetrically installing wide high-elastic ear bands 5 on two sides of the outer protective non-woven fabric layer by hot pressing to prepare the multifunctional mask.
Example four
Weighing 1g of stabilizer polyvinylpyrrolidone, adding the stabilizer polyvinylpyrrolidone into 20g N, N-dimethylacetamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding 1.5g of copper sulfate in a dark environment, stirring for dissolution at room temperature for 12h to obtain copper nanoparticles, and standing the solution for defoaming. Weighing 7g of polyvinylidene fluoride, adding the polyvinylidene fluoride into a 20.5g N N-dimethylacetamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding copper nanoparticles in a dark environment, stirring for 1h at 80 ℃ to obtain a copper nanoparticle doped polyvinylidene fluoride precursor spinning solution, and standing for defoaming. The mass fraction of the polyvinylpyrrolidone is 2%, the mass fraction of the polyvinylidene fluoride is 14%, and the mass fraction of the copper sulfate is 3%.
Injecting the spinning solution into an injection pump, selecting a 17G needle, adjusting the distance from a spinning needle point to a receiving device to be 15cm, setting the output voltage of high-voltage direct current to be 25kv, setting the speed of the injection pump to be 0.05mL/min, setting the moving speed of a horizontal sliding table to be 80mm/s and the width to be 18cm, flatly paving a non-woven fabric base material on a metal receiving device, preparing fibers at the temperature of 25 ℃ and the relative humidity of 50% RH, collecting polyvinylidene fluoride-copper nanofibers on melt-blown fabric on the surface of the receiving device, collecting to obtain a copper nanoparticle self-assembled fiber layer, taking the obtained composite material off the receiving device, placing the composite material in a vacuum drying box at 35 ℃, and drying.
Compounding another layer of non-woven fabric 11 on the dried copper nanoparticle-doped polyvinylidene fluoride nanofiber layer 12 and the base material melt-blown fabric 13, sequentially laminating the outer protective non-woven fabric layer 11, the copper nanoparticle-doped polyvinylidene fluoride nanofiber layer 12, the melt-blown filter layer 13 and the soft skin-friendly inner layer 14 in sequence to prepare the mask body 1, bonding the periphery 2 by hot pressing, pressing a plurality of folds 3 in the horizontal direction, installing a nose support on the upper part of the mask body, installing an adjustable nose bridge strip 4 on the lower side of the nose support, and symmetrically installing wide high-elastic ear bands 5 on two sides of the outer protective non-woven fabric layer by hot pressing to prepare the multifunctional mask.
Example five
Weighing 1g of stabilizer polyvinylpyrrolidone, adding the stabilizer polyvinylpyrrolidone into a 20g N-methyl pyrrolidone solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding 1.5g of zinc sulfate in a dark environment, stirring for dissolution at room temperature for 12h to obtain zinc nanoparticles, and standing the solution for defoaming. Weighing 7g of polyvinylidene fluoride, adding the polyvinylidene fluoride into a 20.5g N-methyl pyrrolidone solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding zinc nanoparticles in a dark environment, stirring for 1h at 80 ℃ to prepare a zinc nanoparticle doped polyvinylidene fluoride precursor spinning solution, and standing for defoaming. The mass fraction of the polyvinylpyrrolidone is 2%, the mass fraction of the polyvinylidene fluoride is 14%, and the mass fraction of the zinc sulfate is 3%.
Injecting the spinning solution into an injection pump, selecting a 17G needle, adjusting the distance from a spinning needle point to a receiving device to be 15cm, setting the output voltage of high-voltage direct current to be 25kv, setting the speed of the injection pump to be 0.05mL/min, setting the moving speed of a horizontal sliding table to be 80mm/s and the width to be 18cm, flatly paving a non-woven fabric base material on a metal receiving device, preparing fibers at the temperature of 25 ℃ and the relative humidity of 50% RH, collecting polyvinylidene fluoride-zinc nanofibers on melt-blown fabric on the surface of the receiving device, collecting to obtain a zinc nanoparticle self-assembled fiber layer, taking the obtained composite material off the receiving device, placing the composite material in a vacuum drying box at 35 ℃, and drying.
Compounding another layer of non-woven fabric 11 on the zinc nanoparticle-doped polyvinylidene fluoride nanofiber layer 12 and the base material melt-blown fabric 13 dried in the third step, sequentially laminating an outer protection non-woven fabric layer 11, a copper nanoparticle-doped polyvinylidene fluoride nanofiber layer 12, a melt-blown filter layer 13 and a soft skin-friendly inner layer 14 in sequence to prepare the mask body 1, bonding the periphery 2 by hot pressing, pressing a plurality of folds 3 in the horizontal direction, mounting a nose support on the upper part of the mask body, mounting an adjustable nose bridge strip 4 on the lower side of the nose support, and symmetrically mounting wide high-elasticity ear bands 5 on two sides of the outer protection non-woven fabric layer by hot pressing to prepare the multifunctional mask.
Comparative example one:
directly adding 1.5g of silver nitrate into 21g of N, N-dimethylformamide solvent in a dark environment, stirring and dissolving for 12 hours at room temperature to obtain silver nanoparticles, and standing and defoaming the solution. Weighing 7g of polyvinylidene fluoride, adding the polyvinylidene fluoride into a 20.5g N N-dimethylformamide solvent, stirring for 4h at 80 ℃ for dissolution, then cooling to room temperature, adding silver nanoparticles in a dark environment, stirring for 1h at 80 ℃ to prepare a silver nanoparticle doped polyvinylidene fluoride precursor spinning solution, and standing for defoaming. The mass fraction of the polyvinylidene fluoride is 14%, and the mass fraction of the silver nitrate is 3%.
Comparative example two:
7g of polyvinylidene fluoride is weighed, added into 43g N, N-dimethylacetamide solvent, stirred for 4 hours at 80 ℃ to be dissolved, then cooled to room temperature, and kept stand for defoaming. And adding the spinning solution into an injection pump, spinning, putting the obtained nano-fiber membrane into a solution with silver nitrate as a silver source, glucose as a reducing agent and polyvinylpyrrolidone as a stabilizing agent, and reacting for 1h in a dark place to obtain the silver nano-particle polyvinylidene fluoride composite fiber membrane subjected to later reduction. The mass fraction of the polyvinylidene fluoride is 14%, and the mass fraction of the silver nitrate is 3%.
Comparative example three:
preparing a silver ammonia solution with the mass fraction of 3% by taking silver nitrate as a silver source, taking glucose as a reducing agent, immersing the activated and sensitized non-woven fabric into the silver ammonia solution, dropwise adding the glucose reducing agent, and reacting for 1 hour in a dark place at normal temperature to obtain the post-reduced non-woven fabric nano silver antibacterial layer. The volume ratio of the reducing agent glucose to the silver nitrate is 1: 1.
The multifunctional masks prepared in the examples and the comparative examples were subjected to performance tests, and the results are as follows:
the bacterial filtration efficiency is tested according to YY0469-2011 requirement of medical surgical masks; referring to technical requirements of GB 19083-; reference is made to GB/T20944.3-2008 < evaluation of antibacterial properties of textiles section 3: the oscillation method evaluates the antibacterial performance of the material, and takes staphylococcus aureus (gram-positive pathogenic bacteria) and escherichia coli (gram-negative pathogenic bacteria) as test strains; GB/T30142 and 2013, planar electromagnetic shielding material shielding effectiveness test method, tests the shielding effectiveness of the sample.
The fifth embodiment has the advantages that the piezoelectric efficiency reaches 49V, the electrostatic adsorption capacity of the mask is maintained, the mask has good antibacterial property, the bacteriostatic rate of staphylococcus aureus and escherichia coli reaches more than 90%, the bacterial filtering efficiency reaches more than 95%, and the mask still maintains high efficiency and low resistance and has certain shielding efficiency after being subjected to particle circulating filtering for 24 times.
In the first comparative example, no polyvinylpyrrolidone as a stabilizer was added to the spinning solution, which resulted in agglomeration of silver nanoparticles and blockage of the spinning needle during spinning, resulting in severe decrease in production efficiency. In the second comparative example, the silver nanoparticle polyvinylidene fluoride composite fiber membrane prepared by the post-reduction method has the advantages that the silver nanoparticles prepared by the electrospinning technology are not uniformly distributed, the agglomeration phenomenon occurs, and the taylor cone whip can form uniformly distributed silver nanoparticles when the electrospinning technology is used for spinning. The nanofiber membrane has a large specific surface area and excellent fiber continuity, and the nanofiber membrane is used as a base material to prepare the nanoparticle antibacterial layer so as to provide more reaction sites, so that more excellent antibacterial property and filtering efficiency can be obtained compared with the traditional base material. In the third comparative example, the non-woven fabric antibacterial layer was prepared by post-reduction, the metal nanoparticles were not uniformly distributed on the substrate, the metal particles agglomerated, the substrate provided reaction sites were few, the antibacterial property and filtration efficiency were inferior to those of the nanofiber membrane antibacterial layer, the reaction was mild and not severe when the metal salt was reduced by using an organic solvent as a reducing agent, and the reaction was fast and the agglomeration of the metal particles was easily caused when using a reducing agent such as glucose.
Claims (10)
1. A preparation method of a metal nano self-assembly fiber material is characterized by comprising the following steps:
firstly, reducing metal salt by a one-step method to prepare metal nanoparticles;
secondly, preparing a metal nanoparticle doped high-molecular polymer precursor spinning solution;
and step three, electrostatic spinning is carried out to prepare the metal nano self-assembly fiber material.
2. The method for preparing the metal nano self-assembled fiber material according to claim 1, wherein the method comprises the following steps:
the first step is to add the stabilizer into the organic solvent, perform a constant temperature water bath reaction, add the metal salt after cooling, and perform magnetic stirring to obtain the metal nanoparticles.
3. The method for preparing the metal nano self-assembled fiber material according to claim 2, wherein the method comprises the following steps:
the metal salt is silver nitrate, copper sulfate, zinc sulfate or chloroauric acid.
4. The method for preparing the metal nano self-assembled fiber material according to claim 2, wherein the method comprises the following steps:
the stabilizer is polyvinylpyrrolidone.
5. The method for preparing the metal nano self-assembled fiber material according to claim 1, wherein the method comprises the following steps:
and the second step is to weigh a certain amount of organic matter macromolecules, add the organic matter macromolecules into an organic solvent, stir in a constant temperature water bath, cool to room temperature, add the metal nanoparticles prepared in the first step, and continue stirring to obtain the metal nanoparticle doped high molecular polymer spinning solution precursor.
6. The method for preparing the metal nano self-assembled fiber material according to claim 5, wherein the method comprises the following steps:
the high molecular polymer is polyvinylidene fluoride.
7. The method for preparing the metal nano self-assembled fiber material according to claim 1, wherein the method comprises the following steps: the third step specifically comprises:
collecting the precursor spinning solution prepared in the second step on melt-blown fabric on the surface of a receiving device through an electrostatic spinning technology, collecting to obtain a metal nano particle self-assembled fiber layer, and taking the obtained composite material off the receiving device.
8. A metallic nano self-assembled fiber material produced by the production method according to any one of claims 1 to 7.
9. The metallic nano self-assembled fiber material of claim 8, wherein: the self-assembled fibrous material has a spider-web structure.
10. The metal nano self-assembled fiber material of claim 8 or 9 is applied to medical protective articles and labor protection articles.
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| CN1584135A (en) * | 2004-05-31 | 2005-02-23 | 吉林大学 | Electrical spinning method for making metal nanometer particles in order in high-polymer nanometer fibre |
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| CN103643347A (en) * | 2013-12-09 | 2014-03-19 | 北京化工大学常州先进材料研究院 | Core-shell structure metal/polymer nanofiber and preparation method thereof |
| CN104392847A (en) * | 2014-09-24 | 2015-03-04 | 黑龙江大学 | Preparation method of morphology controllable metal oxide/active carbon fiber combination electrode material |
| CN111068406A (en) * | 2019-12-26 | 2020-04-28 | 浙江理工大学 | Antibacterial nanofiber filtering material and preparation method thereof |
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| CN1584135A (en) * | 2004-05-31 | 2005-02-23 | 吉林大学 | Electrical spinning method for making metal nanometer particles in order in high-polymer nanometer fibre |
| US20110121227A1 (en) * | 2004-12-22 | 2011-05-26 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Carbon nanotube fibers/filaments formulated from metal nanoparticle catalyst and carbon source |
| CN103643347A (en) * | 2013-12-09 | 2014-03-19 | 北京化工大学常州先进材料研究院 | Core-shell structure metal/polymer nanofiber and preparation method thereof |
| CN104392847A (en) * | 2014-09-24 | 2015-03-04 | 黑龙江大学 | Preparation method of morphology controllable metal oxide/active carbon fiber combination electrode material |
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