CN111648138B - Super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material and environment-friendly mask - Google Patents
Super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material and environment-friendly mask Download PDFInfo
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- CN111648138B CN111648138B CN202010527479.XA CN202010527479A CN111648138B CN 111648138 B CN111648138 B CN 111648138B CN 202010527479 A CN202010527479 A CN 202010527479A CN 111648138 B CN111648138 B CN 111648138B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 65
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002346 layers by function Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 14
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 13
- 239000000741 silica gel Substances 0.000 claims abstract description 12
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 101710134784 Agnoprotein Proteins 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- -1 titanium ions Chemical class 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 8
- 241000700605 Viruses Species 0.000 abstract description 5
- 239000007921 spray Substances 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 4
- 230000029058 respiratory gaseous exchange Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000000903 blocking effect Effects 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 7
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- 239000002344 surface layer Substances 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000711573 Coronaviridae Species 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000241 respiratory effect Effects 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 208000035473 Communicable disease Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241001543506 Hazeus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000002979 Influenza in Birds Diseases 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- 201000003176 Severe Acute Respiratory Syndrome Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 206010064097 avian influenza Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
-
- 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
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/02—Layered materials
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/30—Antimicrobial, e.g. antibacterial
- A41D31/305—Antimicrobial, e.g. antibacterial using layered materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
- D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2400/00—Functions or special features of garments
- A41D2400/70—Removability
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/14—Properties of the materials having chemical properties
- D06N2209/142—Hydrophobic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1671—Resistance to bacteria, mildew, mould, fungi
Abstract
The invention discloses a super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material and environment-friendly mask, which take chitosan as raw material, polyvinyl alcohol as flexible agent, silica gel as pore-forming agent, ag@AgCl-TiO 2 As functional particles by hydrophobic nano SiO 2 Sol post-treatment to form super-hydrophobic porous chitosan/Ag@AgCl-TiO with crisscrossed micro-nano pore channels on sterile medical gauze skeleton 2 A composite material. The mask provided by the invention uses the composite material as an independent disassembly and assembly functional layer, is convenient to clean and replace, can effectively resist the inhalation of haze particles, effectively prevent the propagation of spray such as bacteria and viruses, has a self-cleaning function under the illumination of sunlight, ultraviolet light and the like, has super-hydrophobic property, and can prevent the mask from swelling in exhaled weak acidic water vapor, blocking pore channels and affecting breathing. Therefore, the mask can be repeatedly used, and is suitable for haze and new crown epidemic low and medium risk areas.
Description
Technical Field
The invention belongs to the technical field of articles for daily use, and particularly relates to super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material and environment-friendly mask with haze-preventing and antibacterial functions and repeated use。
Background
The mask is one of the articles which are often used in life, and particularly in places with serious urban air pollution, the haze must be prevented by the mask. In recent years, diseases such as SARS, middle Eastern Respiratory Syndrome (MERS), avian influenza, etc. have become more contagious and have a higher mortality rate. Especially, the new coronavirus pneumonia exploded at the end of 2019 brings serious threat to the lives and health of people worldwide. The spray transmission is a main transmission way of the novel coronavirus, and the mask not only can prevent patients from spraying the spray, but also can prevent the virus-containing spray nuclei from being inhaled by the wearer, thus being an important defense line for preventing respiratory infectious diseases. When masks used in low and medium risk areas are mostly disposable medical protective masks, the consumption is huge, a large amount of material resources, manpower resources and the like are needed for preparing the masks, and the treatment of waste masks is also a huge difficult problem. In particular, most of melt-blown layer materials of medical protective masks are plastics such as polypropylene, tetrafluoroethylene and the like which are difficult to degrade, and huge pressure is brought to the environment.
Disclosure of Invention
The invention aims to solve the technical problems that a mask in the prior art cannot be used repeatedly and can not prevent haze and bacteria, and the environment is polluted by a waste mask, and provides a super-hydrophobic porous chitosan/Ag@AgCl-TiO with the functions of preventing haze and bacteria 2 The composite material and the environment-friendly mask which adopts the composite material as the functional layer and has the haze-preventing and antibacterial functions and can be repeatedly used.
To achieve the aim, the invention adopts the super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 The composite material takes sterile medical gauze as a framework and chitosan/Ag@AgCl-TiO 2 The composite is a casting material, nano silica gel is used as a pore-forming agent, and hydrophobic nano SiO is used 2 The sol is the super-hydrophobic treatment agent and is prepared by the following steps:
1. preparation of Ag@AgCl-TiO 2 Composite material
Mixing isopropyl titanate or butyl titanate with 6mol/L hydrochloric acid to make titanium ions and H in the mixed solution + The molar ratio of (3) to (5) is 1, and the room temperature is the room temperatureStirring for 2-4 hours, stirring for 2-5 hours in a constant temperature water bath at 60-80 ℃, ageing for 20-30 hours at room temperature, filtering, washing with deionized water, drying, calcining the dried solid at 600-700 ℃ for 3-4 hours to obtain TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the TiO is mixed with 2 Dispersing in deionized water, and adding 0.1mol/L AgNO 3 Aqueous solution in which TiO 2 Mass of (2) and AgNO 3 The molar ratio of the components is 1 g:0.5-1.5 mmol, stirring for 20-30 min at room temperature, adding 0.1mol/L hydrochloric acid, stirring for 20-30 min, filtering, washing with deionized water, drying, dispersing the obtained solid product in 40% ethanol water solution by volume fraction, and using wavelength lambda>Visible light irradiation at 400nm for 20 to 30 minutes to reduce part of Ag + Forming Ag simple substance, filtering and drying to obtain Ag@AgCl-TiO 2 A complex; or adding 0.1mol/L hydrochloric acid into the mixture, stirring the mixture for 20 to 30 minutes, and then adding Ag in a glucose reduction part + Forming Ag simple substance, filtering and drying to obtain Ag@AgCl-TiO 2 A complex.
2. Preparation of Chitosan/Ag@AgCl-TiO 2 Composite material
Dissolving chitosan and polyvinyl alcohol in 2% acetic acid aqueous solution to prepare 1% -5% chitosan solution (1); ag@AgCl-TiO 2 Adding the compound into distilled water, and uniformly dispersing by ultrasonic to obtain Ag@AgCl-TiO with the mass fraction of 1% -5% 2 Adding glycerol into the composite suspension, continuing ultrasonic treatment for 20-30 minutes, then dropwise adding the solution (1) under the ultrasonic condition, reacting for 2-3 hours at 50-60 ℃, adding nano silica gel particles, and continuing stirring for 20-30 minutes to obtain chitosan/Ag@AgCl-TiO 2 A complex.
3. Preparation of superhydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material
chitosan/Ag@AgCl-TiO 2 The compound is arranged on the sterile medical gauze at the concentration of 2.0-2.5 mL/m 2 Casting at a speed, drying at 50-60 ℃ to form a film, soaking in 8-12% sodium hydroxide aqueous solution for 40-80 min, washing with water, drying, and then placing the film in hydrophobic nano SiO 2 Soaking in sol for 40-80 min to perform superhydrophobic treatment, washing with water, and drying to obtainTo the super-hydrophobic porous chitosan/Ag@AgCl-TiO taking medical gauze as a framework 2 A composite material.
In the step 2, the addition amount of the polyvinyl alcohol is preferably 10 to 20 percent of the mass of the chitosan, the addition amount of the nano silica gel particles is preferably 20 to 50 percent of the mass of the chitosan, and the chitosan and Ag@AgCl-TiO are preferably added 2 The mass ratio of the compound to the glycerol is 1:0.02-0.10:0.5-1.5.
In the above step 3, hydrophobic nano SiO is preferable 2 Nano SiO in sol 2 The mass concentration of the hydrophobic nano SiO is 2.5-3.0 percent 2 Sol is described in documents Liu Tao, zhang Jipeng, dong Wenying, zhang Weigong preparation and characterization of silica superhydrophobic sols suitable for textiles [ J ]]Guangzhou chemical industry, 2017, 45 (22): 34-36", are prepared by the methods disclosed in" a.
The environment-friendly mask of the invention comprises: the super-hydrophobic porous chitosan/Ag@AgCl-TiO composite material comprises a surface layer, a bag Bian Songjin belt, a nose bridge strip, hanging lugs, a first layer lining, a functional layer and a second layer lining, wherein the functional layer is an independent dismounting structure layer and adopts the super-hydrophobic porous chitosan/Ag@AgCl-TiO composite material 2 A composite material.
The beneficial effects of the invention are as follows:
1. the invention takes chitosan as raw material, polyvinyl alcohol as flexible agent, nano silica gel particles as pore-forming agent, ag@AgCl-TiO 2 As functional particles with the functions of resisting bacteria and degrading pollutants by photocatalysis, the porous chitosan/Ag@AgCl-TiO with crisscrossed micro-nano pore channels is formed on a sterile medical gauze framework 2 Composite material and through hydrophobic nano SiO 2 And (3) performing sol post-treatment to ensure that the composite material has superhydrophobicity.
2. The invention uses super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 The composite material is used as the functional layer of the mask, the functional layer is an independent disassembly and assembly structural layer, the cleaning and replacement of the functional layer are convenient, and the functional layer is provided with micro-nano pore channels which are criss-cross, so that not only can the passage of pollutants such as haze particles be effectively prevented, but also the propagation of the spray of bacteria and viruses can be effectively prevented, and especially the functional layer contains a photocatalyst Ag@AgCl-TiO 2 Has antibacterial and photocatalytic decomposition effectsThe pollutant has self-cleaning effect under the illumination of sunlight, ultraviolet light and the like, and can be repeatedly used. Meanwhile, the functional layer has super-hydrophobic performance, and can prevent the functional layer from swelling in weak acidic water vapor exhaled by a person, blocking pore channels and affecting breathing. The mask is suitable for haze and new crown epidemic situation low and medium risk areas.
Drawings
Fig. 1 is a schematic view of the structure of the mask of the present invention.
Fig. 2 is a cross-sectional view of the mask of the present invention.
FIG. 3 is a super hydrophobic porous chitosan/Ag@AgCl-TiO 2 Scanning electron microscopy of composite material (magnification 50000).
FIG. 4 is a super hydrophobic porous chitosan/Ag@AgCl-TiO 2 Transmission electron microscopy of the composite (magnification 100000).
FIG. 5 is a super hydrophobic porous chitosan/Ag@AgCl-TiO 2 Ultraviolet absorption spectrum of the composite material.
FIG. 6 is a super hydrophobic porous chitosan/Ag@AgCl-TiO 2 Photographs of the contact angle of the composite with water.
The elements in fig. 1 are illustrated: 1-a surface layer; 2-edge-wrapping elastic bands; 3-a nose bridge bar; 4-hanging lugs; 5-a first liner; 6-a functional layer; 7-a second liner.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Hydrophobic nano SiO with mass concentration of 2.6% used in the following examples 2 The preparation method of the sol comprises the following steps: taking 30 mL ammonia water and adding the ammonia water into 300 mL absolute ethyl alcohol, uniformly mixing, pouring the mixture into a 1000 mL round bottom flask, and magnetically stirring the mixture at room temperature, wherein the solution is denoted as A solution; and taking 16 mL ethyl orthosilicate, adding the ethyl orthosilicate into 300 mL absolute ethyl alcohol, uniformly stirring, and marking the mixture as solution B. Under the condition of rapid stirring, the solution B is rapidly poured into a flask where the solution A is positioned, and the mixture is stirred and reacted for 12 hours at room temperature to obtain light blue nano silica sol. Adding 200 mL absolute ethanol into the obtained sol, evaporating ammonia, concentrating to obtain final solutionThe total gel volume was 500 mL. Taking 100 mL sol, regulating the pH value to 8.5 by glacial acetic acid or ammonia water, transferring 1.5 mL dodecyl trimethoxy silane by a pipette, adding the mixture into a single-neck flask after uniform stirring, placing the flask into an oil bath at 80 ℃ for stirring and refluxing reaction for 3 hours to obtain the hydrophobic nano SiO with the mass concentration of 2.6 percent 2 And (3) sol.
Example 1
As shown in fig. 1 and 2, the environment-friendly mask of the present embodiment includes a face layer 1, a bag Bian Songjin belt 2, nose bridge strips 3, an ear hook 4, a first layer lining 5, a functional layer 6, and a second layer lining 7.
The surface layer 1 is linen or cotton linen or all cotton or blended cloth, the first lining 5 and the second lining 7 are all cotton cloth, the cloth is natural, the wearing is comfortable, and the cleaning can be performed. The functional layer 6 is placed between the first lining 5 and the second lining 7, and the functional layer 6 is an independent dismounting structure layer, so that the functional layer 6 is convenient to clean and replace. The number of the functional layers 6 can be set to be 1-3 layers (the number of the functional layers is determined according to the haze and epidemic situation), so that the mask can prevent haze, bacteria and viruses from being inhaled into a human body. The surface layer 1, the first lining 5 and the second lining 7 are covered by a bag Bian Songjin belt 2 with the width of about 1 cm and are naturally processed into an ear hook 4 by a bag Bian Songjin belt 2 on the left side and the right side, and a nose bridge strip 3 is arranged on the inner side of the surface layer 1.
The functional layer 6 is super-hydrophobic porous chitosan/Ag@AgCl-TiO taking medical gauze as a framework 2 A composite material prepared according to the following method:
1. preparation of Ag@AgCl-TiO 2 Composite material
Mixing 14 mL (51.31 mmol) isopropyl titanate and 36 mL 6mol/L hydrochloric acid, stirring at room temperature for 3 hours, stirring at constant temperature water bath at 70deg.C for 3 hours, aging at room temperature for 24 hours, filtering, washing with deionized water, drying, and calcining the dried solid in a muffle furnace at 650deg.C for 3 hours to obtain TiO 2 .5 g of TiO 2 Uniformly dispersing in 150 mL deionized water, and adding 50 mL of 0.1mol/L AgNO 3 The aqueous solution was stirred at room temperature for 20 minutes, and then 50 mL of 0.1 mol.L was added -1 Continuously stirring for 30 min, filtering and removingWashing with ionized water, drying, dispersing the obtained solid product in 150 mL volume fraction 40% ethanol water solution, irradiating with 90W sodium lamp (average wavelength of 589.3 nm) for 20 min at a lamp distance of 10 cm, filtering, and drying to obtain Ag@AgCl-TiO 2 A complex.
2. Preparation of Chitosan/Ag@AgCl-TiO 2 Composite material
1, g chitosan (molecular weight Mw: 100.0-200.0 kDa) and 0.1g of polyvinyl alcohol (alcoholysis degree is more than 99%) are dissolved in 2% acetic acid aqueous solution with the mass fraction of 32.33-g, so as to prepare a chitosan solution (1) with the mass fraction of 3%; 0.05 g of Ag@AgCl-TiO 2 Adding the compound into distilled water of 1.62 and g, and performing ultrasonic dispersion to obtain Ag@AgCl-TiO with the mass fraction of 3 percent 2 Adding 1g glycerol into the composite suspension, continuing to carry out ultrasonic treatment for 20 minutes, then dropwise adding the solution (1) under the ultrasonic condition, reacting for 2 hours at 60 ℃, adding 0.3 g nano silica gel particles, and continuing to stir for 20 minutes to obtain chitosan/Ag@AgCl-TiO 2 A complex.
3. Preparation of superhydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material
chitosan/Ag@AgCl-TiO 2 The complex was applied to sterile medical gauze at a rate of 2.4. 2.4 mL/m 2 Casting at a speed, drying at 60 ℃ to form a film, soaking in 10% sodium hydroxide aqueous solution for 60 minutes, and fully dissolving silica gel to form crisscross pore channels; then washing and drying, and finally putting the membrane into a hydrophobic nano SiO with the mass concentration of 2.6% 2 Soaking in sol for 60 min to perform superhydrophobic treatment, washing with water, and drying to obtain superhydrophobic porous chitosan/Ag@AgCl-TiO with medical gauze as skeleton 2 A composite material.
To facilitate the preparation of the super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 The morphology of the composite material is characterized, and the inventor directly uses chitosan/Ag@AgCl-TiO according to the method of the step 3 2 The compound is cast on transparent glass, soaked in sodium hydroxide aqueous solution and subjected to superhydrophobic treatment. The morphology of the resulting composite was then analyzed using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), see fig. 3 and 4. As can be seen from FIG. 3, the resulting composite material has a distribution of crisscrossThe wrong micro-nano pore canal can ensure normal respiration of people and can effectively block haze and viruses. In FIG. 4, the off-white color is a matrix of chitosan and polyvinyl alcohol, and the black particles are nano silver particles and Ag@AgCl-TiO 2 And (3) nanoparticles. Chitosan is a cationic polysaccharide, has excellent adsorption and antibacterial functions, and nano silver particles can generate strong punctiform positive charges to quickly destroy cell membranes of bacteria, so that the bacteria die, and are commonly used as medical materials. Ag@AgCl-TiO 2 Surface plasmon resonance effect of noble metal Ag and semiconductor TiO are combined 2 The advantage of the photocatalytic activity can improve the utilization rate of visible light and the photocatalytic activity, and can decompose pollutants under the irradiation of ultraviolet and visible light, which is also reflected on the ultraviolet-visible light absorption spectrum of the composite material in fig. 5. As can be seen from FIG. 5, the obtained composite material has high light absorption intensity in the ultraviolet light region with the wavelength of 225-275 nm and also has obvious light absorption in the visible light region of 340-550 nm, which indicates that the composite material has photocatalytic activity under the irradiation of sunlight, ultraviolet light and the like. As can be seen from fig. 6, the contact angle of the obtained composite material with water is about 121.5 °, which is far greater than 90 °, indicating that it is a superhydrophobic material.
According to the national standard GB/T20944.2-2008 textile antibacterial performance evaluation method, the antibacterial performance of the functional layer is tested, staphylococcus aureus and escherichia coli are used as indicator bacteria, and the antibacterial rate of the material is more than 99%.
Example 2
The mask structure of this example is the same as that of example 1, wherein the functional layer 6 is super-hydrophobic porous chitosan/Ag@AgCl-TiO with medical gauze as skeleton 2 A composite material prepared according to the following method:
1. preparation of Ag@AgCl-TiO 2 Composite material
14 mL (39.74 mmol) butyl titanate and 36 mL 6mol/L hydrochloric acid are mixed, stirred at room temperature for 3 hours, stirred in a constant-temperature water bath at 70 ℃ for 3 hours, aged at room temperature for 24 hours, filtered, washed by deionized water, dried, and the dried solid is put into a muffle furnace for calcination at 650 ℃ for 3 hours to obtain TiO 2 .5 g of TiO 2 Evenly divideDispersing in 150 mL deionized water, adding 50 mL of 0.1mol/L AgNO 3 The aqueous solution was stirred at room temperature for 20 minutes, and then 40 mL of 0.1 mol.L was added -1 Stirring for 30 min, and adding 10 mL of mol.L -1 Continuously stirring for 30 min, filtering, washing with deionized water, and drying to obtain Ag@AgCl-TiO 2 A complex.
2. Preparation of Chitosan/Ag@AgCl-TiO 2 Composite material
1, g chitosan (molecular weight Mw: 100.0-200.0 kDa) and 0.2g of polyvinyl alcohol (alcoholysis degree is more than 99%) are dissolved in 2% acetic acid aqueous solution with the mass fraction of 32.33-g, so as to prepare a chitosan solution (1) with the mass fraction of 3%; 0.1g of Ag@AgCl-TiO 2 Adding the compound into 3.3 g distilled water, and performing ultrasonic dispersion to obtain Ag@AgCl-TiO with the mass fraction of 3% 2 Adding 1g glycerol into the composite suspension, continuing to carry out ultrasonic treatment for 20 minutes, then dropwise adding the solution (1) under the ultrasonic condition, reacting for 2 hours at 60 ℃, adding 0.3 g nano silica gel particles, and continuing to stir for 20 minutes to obtain chitosan/Ag@AgCl-TiO 2 A complex.
3. Preparation of superhydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material
chitosan/Ag@AgCl-TiO 2 The complex was applied to sterile medical gauze at a rate of 2.4. 2.4 mL/m 2 Casting at a speed, drying at 60 ℃ to form a film, soaking in 10% sodium hydroxide aqueous solution for 60 minutes, and fully dissolving silica gel to form crisscross pore channels; then washing with water, drying, and finally putting the membrane into a hydrophobic nano SiO with the mass concentration of 2.6% 2 Soaking in sol for 60 min to perform superhydrophobic treatment, washing with water, and drying to obtain superhydrophobic porous chitosan/Ag@AgCl-TiO with medical gauze as skeleton 2 A composite material.
Claims (6)
1. Super-hydrophobic porous chitosan/Ag@AgCl-TiO 2 A composite material characterized in that: the composite material takes sterile medical gauze as a framework and chitosan/Ag@AgCl-TiO 2 The composite is a casting material, nano silica gel is used as a pore-forming agent, and hydrophobic nano SiO is used 2 The sol is super-hydrophobicThe treating agent is prepared by the following steps:
(1) Preparation of Ag@AgCl-TiO 2 Composite material
Mixing isopropyl titanate or butyl titanate with 6mol/L hydrochloric acid to make titanium ions and H in the mixed solution + The molar ratio of (3-5) is 1, (3-4) stirring for 2-4 hours at room temperature, stirring for 2-5 hours at the constant temperature of 60-80 ℃ in water bath, ageing for 20-30 hours at room temperature, filtering, washing with deionized water, drying, calcining the dried solid at 600-700 ℃ for 3-4 hours to obtain TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the TiO is mixed with 2 Dispersing in deionized water, and adding 0.1mol/L AgNO 3 Aqueous solution in which TiO 2 Mass of (2) and AgNO 3 The molar ratio of the components is 1 g:0.5-1.5 mmol, stirring for 20-30 min at room temperature, adding 0.1mol/L hydrochloric acid, stirring for 20-30 min, filtering, washing with deionized water, drying, dispersing the obtained solid product in 40% ethanol water solution by volume fraction, and using wavelength lambda>Visible light irradiation at 400nm for 20 to 30 minutes to reduce part of Ag + Forming Ag simple substance, filtering and drying to obtain Ag@AgCl-TiO 2 A complex;
or adding 0.1mol/L hydrochloric acid into the mixture, stirring the mixture for 20 to 30 minutes, and then adding Ag in a glucose reduction part + Forming Ag simple substance, filtering and drying to obtain Ag@AgCl-TiO 2 A complex;
(2) Preparation of Chitosan/Ag@AgCl-TiO 2 Composite material
Dissolving chitosan and polyvinyl alcohol in 2% acetic acid aqueous solution to prepare 1% -5% chitosan solution (1); ag@AgCl-TiO 2 Adding the compound into distilled water, and uniformly dispersing by ultrasonic to obtain Ag@AgCl-TiO with the mass fraction of 1% -5% 2 Adding glycerol into the composite suspension, continuing ultrasonic treatment for 20-30 minutes, then dropwise adding the solution (1) under the ultrasonic condition, reacting for 2-3 hours at 50-60 ℃, adding nano silica gel particles, and continuing stirring for 20-30 minutes to obtain chitosan/Ag@AgCl-TiO 2 A complex;
(3) Preparation of superhydrophobic porous chitosan/Ag@AgCl-TiO 2 Composite material
chitosan/Ag@AgCl-TiO 2 The compound is arranged on the sterile medical gauze at the concentration of 2.0-2.5 mL/m 2 Casting at a speed, drying at 50-60 ℃ to form a film, soaking in 8-12% sodium hydroxide aqueous solution for 40-80 min, washing with water, drying, and then placing the film in hydrophobic nano SiO 2 Soaking in sol for 40-80 min to perform superhydrophobic treatment, washing with water, and drying to obtain superhydrophobic porous chitosan/Ag@AgCl-TiO with medical gauze as skeleton 2 A composite material.
2. The superhydrophobic porous chitosan/ag@agcl-TiO according to claim 1 2 A composite material characterized in that: in the step (2), the addition amount of the polyvinyl alcohol is 10-20% of the mass of the chitosan.
3. The superhydrophobic porous chitosan/ag@agcl-TiO according to claim 1 2 A composite material characterized in that: in the step (2), the chitosan and Ag@AgCl-TiO 2 The mass ratio of the compound to the glycerol is 1:0.02-0.10:0.5-1.5.
4. The superhydrophobic porous chitosan/ag@agcl-TiO according to claim 1 2 A composite material characterized in that: in the step (2), the addition amount of the nano silica gel particles is 20-50% of the mass of the chitosan.
5. The superhydrophobic porous chitosan/ag@agcl-TiO according to claim 1 2 A composite material characterized in that: in step (3), the hydrophobic nano SiO 2 Nano SiO in sol 2 The mass concentration of (2.5-3.0%).
6. An environmental protection mask comprising: surface course (1), elastic webbing (2) bordure, bridge of the nose strip (3), hangers (4), first layer lining (5), functional layer (6), second floor lining (7), functional layer (6) are independent dismouting structural layer, its characterized in that: the functional layer (6) is the super-hydrophobic porous chitosan/Ag@AgCl-TiO according to any one of claims 1-5 2 A composite material.
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| WO2016156939A1 (en) * | 2015-03-27 | 2016-10-06 | Uniwersytet Jagielloński | Composite containing chitosan and zinc oxide nanoparticles and a process for its preparation |
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| CN106031530A (en) * | 2015-03-16 | 2016-10-19 | 华北电力大学（保定） | Anti-haze disinfecting mouth mask and preparation method |
| WO2016156939A1 (en) * | 2015-03-27 | 2016-10-06 | Uniwersytet Jagielloński | Composite containing chitosan and zinc oxide nanoparticles and a process for its preparation |
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