CN114934356B - Degradable nanofiber mask filter core with renewable antibacterial property and preparation method thereof - Google Patents
Degradable nanofiber mask filter core with renewable antibacterial property and preparation method thereof Download PDFInfo
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- CN114934356B CN114934356B CN202210636821.9A CN202210636821A CN114934356B CN 114934356 B CN114934356 B CN 114934356B CN 202210636821 A CN202210636821 A CN 202210636821A CN 114934356 B CN114934356 B CN 114934356B
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- graphene oxide
- nanofiber
- polylactic acid
- halamine
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 143
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 90
- 239000004626 polylactic acid Substances 0.000 claims abstract description 58
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 57
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 46
- 239000002243 precursor Substances 0.000 claims abstract description 44
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 98
- 239000000243 solution Substances 0.000 claims description 81
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 80
- 239000012528 membrane Substances 0.000 claims description 75
- 239000002131 composite material Substances 0.000 claims description 54
- 239000003242 anti bacterial agent Substances 0.000 claims description 53
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- 238000009987 spinning Methods 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 37
- 239000004593 Epoxy Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- UAZRLZKBADJCKK-UHFFFAOYSA-N imidazolidine-2,4-dione;sodium Chemical compound [Na].O=C1CNC(=O)N1 UAZRLZKBADJCKK-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 claims description 17
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 16
- 239000004745 nonwoven fabric Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 230000000845 anti-microbial effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000001523 electrospinning Methods 0.000 claims 2
- 238000013329 compounding Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 28
- 229910052736 halogen Inorganic materials 0.000 description 13
- 239000004744 fabric Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 239000004594 Masterbatch (MB) Substances 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000005119 centrifugation Methods 0.000 description 10
- 238000011049 filling Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000000835 fiber Substances 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000000527 sonication Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 241000711573 Coronaviridae Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000005713 exacerbation Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2055—Carbonaceous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
-
- 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
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- 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
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
-
- 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
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4374—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece using different kinds of webs, e.g. by layering webs
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D2500/00—Materials for garments
- A41D2500/30—Non-woven
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geology (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
- Filtering Materials (AREA)
- Artificial Filaments (AREA)
Abstract
The invention provides a degradable nanofiber mask filter core with renewable antibacterial property and a preparation method thereof, which are used for solving the technical problems that a traditional mask is difficult to degrade, the antibacterial property is not renewable, the filtering property is poor and is not durable. According to the invention, 5-dimethyl hydantoin and epichlorohydrin are used as raw materials to prepare the halamine precursor, and the halamine precursor is grafted on the surface of graphene oxide through a covalent grafting technology, so that the graphene oxide-halamine nanocomposite with high-efficiency renewable antibacterial performance is prepared. Secondly, the polylactic acid which is a green bio-based degradable material is selected, based on extremely thin solution theory, superfine nanofibers which are 10 times finer than the conventional nanofiber in diameter are successfully prepared through an electrostatic spinning technology, and the multi-scale three-dimensional space structure of stacking of the thick nanofiber and the thin nanofiber is successfully constructed through regulating and controlling the ratio of the thick nanofiber to the thin nanofiber. The degradable nanofiber mask filter core prepared by the invention has the characteristics of biodegradability, renewable antibacterial performance, excellent filtering performance and durability and stability.
Description
Technical Field
The invention belongs to the technical field of air filtration, and particularly relates to a degradable nanofiber mask filter core with renewable antibacterial performance and a preparation method thereof.
Background
First, the exacerbation of air pollution and the global outbreak of new coronaviruses have increased the demands and usage of masks. However, the large amount of plastic garbage is caused by the large amount of disposable masks and incorrect treatment, so that the pollution of white plastic is further aggravated, and the environment is greatly harmed. Recent reports issued by ocean Asia, the marine protection organization, show that a total of about 520 million masks are produced worldwide in 2020, at least 15.6 million of which are lost into the ocean, severely threatening the marine environment. Because the main raw material of the mask is polypropylene (PP) and the like at present, the degradation in the environment can take 400-500 years, and the decomposed plastic fragments can cause continuous harm to the environment.
Secondly, the outbreak of new crown epidemic situation leads the personal hygiene protection consciousness to be unprecedented and the demands of people on biological safety protection mask products to be increased sharply. However, the traditional mask on the market at present does not have the problems of unstable antibacterial function or antibacterial effect, poor durability and the like. According to the different antibacterial agents and antibacterial mechanisms, the antibacterial textiles mainly comprise three systems of metal ion type, organic cation type and photocatalyst type. Most of the antibacterial textiles on the market at present use silver ions as antibacterial agents, and the products are easy to oxidize and have poor antibacterial durability. In addition, the problems of environmental pollution and bacterial drug resistance caused by the dissolution of the antibacterial agent are also a great difficulty in the development of antibacterial textiles. Haloamine compounds are receiving attention because of their broad-spectrum and high-efficiency sterilization, easy degradation, low toxicity, good storage stability and the like. And after killing bacteria and viruses and losing activity, the halogen amine compound can regain the sterilization function after being rinsed by a hypochlorite solution with low concentration, and has excellent long-acting renewable characteristics. However, the active chlorine release performance of the single small molecule halamine compound is unstable and cannot be directly combined with various textiles which need to achieve the antibacterial effect, so that the application of the single small molecule halamine compound in antibacterial textiles is limited.
In addition, the mask industry in China at present mainly focuses on the repeated manufacturing with low technical content, and the traditional single melt-blown fiber filter material is unstable in filtering performance, short in service life and the like due to the filtering mechanism of electrostatic adsorption. Compared with the traditional mask filter element in the market, the electrostatic spinning nanofiber material is widely applied in the air filtering field due to the fact that the fiber fineness is in the nanometer level, the specific surface area is large, the pore diameter is small, the porosity is high, the functionalization modification is easy, and the like. However, the conventional electrospun fiber has a fiber diameter of more than 100nm, is difficult to refine, severely limits the great improvement of the filtering performance of the material, and still has the bottleneck problem of insufficient filtering efficiency for the particles with the most penetrable particle size (-0.3 μm). Therefore, the development of the mask filter element which has the advantages of biodegradability, reproducible antibacterial performance, excellent filtering performance and durability and stability is of great significance.
Disclosure of Invention
Aiming at the technical problems that the traditional mask is difficult to degrade, the antibacterial property is not renewable, the filtering property is poor and is not durable, the invention provides the degradable nanofiber mask filter core with the renewable antibacterial property and the preparation method thereof.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a preparation method of a degradable nanofiber mask filter core with renewable antibacterial performance comprises the following steps:
(1) Adding 5, 5-dimethyl hydantoin and sodium hydroxide into acetone, stirring until the mixture is completely dissolved, and then removing an acetone solvent to prepare hydantoin sodium salt; dissolving hydantoin sodium salt into N, N-dimethylformamide, then adding epoxy chloropropane to react, and after the reaction is finished, carrying out suction filtration and distillation to obtain an epoxy haloamine precursor;
(2) Dissolving graphene oxide and the epoxy haloamine precursor prepared in the step (1) in a mixed solvent composed of water and ethanol for reaction, and separating and purifying reactants after the reaction is finished to prepare a grafting product of the graphene oxide-based epoxy haloamine precursor;
(3) Sequentially dissolving the grafting product of the graphene oxide-based epoxy halogen amine precursor prepared in the step (2), tetrabutylammonium chloride and polylactic acid in a mixed solution solvent consisting of N, N-dimethylformamide and dimethyl carbonate to prepare polylactic acid mixed spinning solution;
(4) Sequentially dissolving tetrabutyl ammonium chloride and polylactic acid in a mixed solution solvent consisting of N, N-dimethylformamide and dimethyl carbonate to prepare polylactic acid ultra-dilute spinning solution;
(5) Carrying out electrostatic spinning on the polylactic acid mixed spinning solution prepared in the step (3) to prepare a graphene oxide-halamine composite antibacterial agent nanofiber membrane;
(6) Carrying out electrostatic spinning on the polylactic acid ultra-dilute spinning solution prepared in the step (4), spraying a layer of ultra-fine nanofiber membrane on a receiving substrate, wherein the receiving substrate is the graphene oxide-halamine composite antibacterial agent nanofiber membrane prepared in the step (5), and thus a multi-scale nanofiber membrane is prepared;
(7) And fixing the nanofiber membrane with the multi-scale structure through an ultrasonic composite process to prepare the degradable nanofiber mask filter core.
The molar ratio of the 5, 5-dimethyl hydantoin to the sodium hydroxide particles in the step (1) is 1: (1-2) the concentration of 5, 5-dimethylhydantoin in acetone is 3-8wt%; the molar ratio of hydantoin sodium salt to epichlorohydrin is 1: (1-2) the concentration of hydantoin sodium salt in N, N-dimethylformamide is 5-15wt%; the reaction temperature of the hydantoin sodium salt and the epichlorohydrin is 80-100 ℃ and the reaction time is 10-15h.
In the step (2), the mass ratio of the graphene oxide to the epoxy haloamine precursor is 1: (2-5), the volume ratio of the water to the ethanol in the mixed solvent consisting of the water and the ethanol is (1-2): 1, the concentration of graphene oxide in a mixed solvent consisting of water and ethanol is 0.5-2wt%, the reaction temperature of the graphene oxide and the epoxy haloamine precursor is 70-90 ℃, and the reaction time is 6-12 h.
The method comprises the steps that in a mixed solvent consisting of N, N-dimethylformamide and dimethyl carbonate, the volume ratio of the N, N-dimethylformamide to the dimethyl carbonate is (3:7) - (1:1), a graphene oxide-halogen amine compound antibacterial agent solution is prepared after a grafting product of a graphene oxide-halogen amine precursor is dissolved, the dissolving temperature of the grafting product of the graphene oxide-halogen amine precursor is 35-55 ℃, and the concentration of the grafting product of the graphene oxide-halogen amine precursor in the graphene oxide-halogen amine compound antibacterial agent solution is 0.3-1.0wt%; the tetrabutylammonium chloride is dissolved to prepare a tetrabutylammonium chloride mixed solution, the dissolution temperature of the tetrabutylammonium chloride is 35-55 ℃, and the concentration of the tetrabutylammonium chloride in the tetrabutylammonium chloride mixed solution is 0.3-0.9wt%; the dissolution temperature of the polylactic acid is 60-80 ℃, and the concentration of the polylactic acid in the polylactic acid mixed spinning solution is 10-15 wt%.
The mixed solvent composed of N, N-dimethylformamide and dimethyl carbonate in the step (4) has the volume ratio of N, N-dimethylformamide to dimethyl carbonate of (3:7) - (1:1), tetrabutylammonium chloride is dissolved to prepare tetrabutylammonium chloride solution, the dissolution temperature of tetrabutylammonium chloride is 35-55 ℃, the concentration of tetrabutylammonium chloride in the tetrabutylammonium chloride solution is 3-7wt%, the dissolution temperature of polylactic acid is 60-80 ℃, and the concentration of polylactic acid in the polylactic acid ultra-dilute spinning solution is 1-7wt%.
The electrostatic spinning process parameters in the step (5) are as follows: the voltage of the high-voltage generator is 20-30 KV, the distance from the nozzle to the receiving substrate is 15-18 cm, the caliber of the nozzle is 0.1-0.2 cm, the flow rate of the electrostatic spinning solution is 0.5-3.0mL/h, the receiving time is 10-60 min, and the receiving substrate is polylactic acid non-woven fabric.
The electrostatic spinning process parameters in the step (6) are as follows: the voltage of the high-voltage generator is 20-30 KV, the distance from the nozzle to the receiving base cloth is 15-18 cm, the caliber of the nozzle is 0.1-0.2 cm, and the flow rate of the electrostatic spinning solution is 0.3-1.0 mL/h; the receiving time is 10-60 min.
Comprises a polylactic acid non-woven fabric, a graphene oxide-halamine composite antibacterial agent nanofiber membrane and an ultrafine nanofiber membrane which are sequentially arranged.
The average diameter of the nanofiber in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 100-400 nm, and the average pore diameter of the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 1-10um.
The average diameter of the nano fibers in the superfine nano fiber membrane is 25-100nm, and the average pore diameter of the superfine nano fiber membrane is 0.05-10 um.
Firstly, 5-dimethyl hydantoin and epichlorohydrin are used as raw materials to prepare a halamine precursor, the halamine precursor is grafted on the surface of graphene oxide through a covalent grafting technology, and epoxy groups on the epichlorohydrin can react with hydroxyl and other active groups in the graphene oxide to prepare the graphene oxide-halamine nanocomposite with high-efficiency renewable antibacterial performance. Secondly, the green bio-based degradable material polylactic acid (PLA) is selected, and based on the extremely dilute solution theory, the superfine nanofiber with the diameter 10 times smaller than that of the conventional nanofiber is successfully prepared by an electrostatic spinning technology, and the diameter of the superfine nanofiber is distributed between 35 and 45 and nm. The multi-scale three-dimensional space structure with stacked coarse and fine nano fibers is successfully constructed by regulating the ratio of the coarse and fine fibers, so that the high-efficiency low-resistance filtration of the nano-scale aperture is realized, and the high-efficiency filtration performance of PM10, PM5, PM2.5 and even harmful particulate matters with the highest penetrability and PM0.3 level is realized. The constructed multi-scale three-dimensional space filtering structure can capture particulate matters through physical interception instead of electrostatic adsorption, and the filtering stability and durability of the mask are greatly improved. Finally, the in-situ doped fiber modification technology is utilized to introduce the synthesized graphene oxide-halamine composite antibacterial agent with renewable antibacterial performance into the nanofiber membrane, and the nanofiber membrane is subjected to renewable antibacterial functional modification.
The technical scheme for realizing the degradable nanofiber mask filter core with the renewable antibacterial performance is as follows: based on the extremely dilute solution spinning theory, the graphene oxide-halamine composite antibacterial agent is obtained through an electrostatic spinning method and an ultrasonic composite process, and consists of graphene oxide-halamine composite antibacterial agent, polylactic acid non-woven fabrics and PLA nanofibers. The preparation method comprises the steps of preparing an epoxy haloamine precursor by taking 5, 5-dimethyl hydantoin and epichlorohydrin as raw materials, and covalently grafting a haloamine small molecular compound on the surface of graphene oxide to synthesize the graphene oxide-haloamine (GO-Halamine) composite antibacterial agent.
The invention has the beneficial effects that:
(1) The invention utilizes the high reactivity and good dispersibility of the graphene oxide with high specific area to effectively improve the load and stability of haloamine molecules, and meanwhile, the probability of contact of the antibacterial agent with bacteria is improved by virtue of the high specific surface area of the nanofiber, so that the antibacterial activity is greatly improved.
(2) The graphene oxide-halamine doped nanofiber filter element prepared by the invention has reproducible antibacterial performance, and the antibacterial performance is hardly changed after ten chlorine bleaching cycles.
(3) The invention prepares the superfine nanofiber based on the extremely dilute solution of the high-salt content and high-molecular weight polymer, and compared with the conventional electrostatic spinning nanofiber, the superfine nanofiber has the characteristics of small diameter (about 20-30 nm) and small pore diameter (about 300-500 nm).
(4) The invention constructs the air filter material with multi-scale and multi-dimension (two-dimension and three-dimension combined) of thick and thin nano fibers based on the electrostatic spinning multi-scale nano fiber membrane technology, the initial filter efficiency is up to 98.67 percent, the filter resistance is only 78Pa, the filter efficiency is still 95.76 percent after 12 hours of use, and the filter resistance is 84Pa. Realizing high-efficiency low-resistance durable and stable filtering performance.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an electron microscope image of a graphene oxide-halamine composite antibacterial agent nanofiber membrane
Fig. 2 is a multi-scale nanofiber membrane electron microscopy image.
Fig. 3 is a physical diagram of a degradable nanofiber mask filter cartridge.
Fig. 4 is an antimicrobial efficiency graph of a degradable nanofiber mask filter.
Fig. 5 is a graph of the filtration performance of the degradable nanofiber mask filter cartridge.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a degradable nanofiber mask filter core with renewable antibacterial performance comprises the following steps:
1) Equal molar amounts (0.1 mol) of 5, 5-dimethylhydantoin and sodium hydroxide particles were weighed, added to acetone, stirred at room temperature until completely dissolved, and a 5, 5-dimethylhydantoin concentration of 5wt% in acetone was prepared. And (3) removing the acetone solvent by rotary evaporation, and placing the obtained hydantoin sodium salt in a vacuum drying oven to be dried at 45 ℃ for 1 day, thereby finally obtaining the hydantoin sodium salt.
2) 0.1mol of hydantoin sodium salt obtained in the step 1) is weighed, dissolved into N, N-Dimethylformamide (DMF), added with 0.1mol of epichlorohydrin, prepared into DMF solution with the hydantoin sodium salt concentration of 10wt%, and kept at the temperature of 90 ℃ for reaction of 12 h. And after the reaction is finished, removing a byproduct NaCl through suction filtration. And (3) removing the solvent by reduced pressure distillation to finally obtain the milky epoxy haloamine precursor product.
3) Weighing 0.1g of GO and 0.2g of the epihalohydrin precursor obtained in step 2), and dissolving in a mixed solvent of water and ethanol (v/v, 2: 1) A mixed solution having a graphene oxide concentration of 0.5wt% was prepared. After 30 min of sonication, transfer to an oil bath and reaction at 80℃for 6 h. Centrifugation (10000 rpm,15 min) and removal of supernatant, repeated washing with ethanol and centrifugation. And (3) drying in a vacuum drying oven at 45 ℃ for 2 days to obtain black solid, namely the final graphene oxide based epoxy haloamine precursor grafted product (graphene oxide-haloamine composite antibacterial agent).
4) The grafting product of the graphene oxide-based epihalohydrin precursor obtained in step 3) was weighed and slowly added to a solution containing 150ml of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) And (3) in a mixed solution flask, under the conditions of 45 ℃ and 400 r/min, stirring vigorously for 2h to prepare the graphene oxide-halogen amine composite antibacterial agent solution with the grafting product concentration of the graphene oxide-epoxy halogen amine precursor of 0.3 wt%.
5) Tetrabutylammonium chloride was added to the solution obtained in the step 4), and the mixture was vigorously stirred at 45℃and 400 r/min for 2h to prepare a mixed solution having a tetrabutylammonium chloride concentration of 0.3% by weight. Polylactic acid master batch (M) W =200000) was added to the mixed solution and vigorously stirred at 65 ℃, 400 r/min for 6 h to prepare a spinning solution having a polylactic acid concentration of 10 wt%.
6) The tetrabutylammonium chloride was weighed and added to a mixture containing only a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) In the mixed solution, the mixture was vigorously stirred at 45℃and 400 r/min for 2h to prepare a mixed solution having a tetrabutylammonium chloride concentration of 3 wt%. Adding polylactic acid master batch with certain mass, and vigorously stirring for 6 h at 65 ℃ and 400 r/min to prepare the ultra-dilute spinning solution with the polylactic acid concentration of 3 wt%.
7) Filling the spinning solution obtained in the step 5) into a needle tube, carrying out electrostatic spinning, and spinning the needle tube on the surface of polylactic acid non-woven fabric (the gram weight of the non-woven fabric is 50 g/m) 2 ) The graphene oxide-halamine composite antibacterial agent nanofiber membrane is prepared (figure 1).Electrostatic spinning conditions: the voltage of the high voltage generator is 25 KV; the distance from the nozzle to the receiving base cloth is 18 cm, and the caliber of the nozzle is 0.15 cm; the flow rate of the sprayed electrostatic spinning solution is 0.8 mL/h; the reception time was 20 min.
8) Filling the spinning solution obtained in the step 6) into a needle tube, carrying out electrostatic spinning, and preparing a layer of superfine nanofiber membrane on the surface of the graphene oxide-halamine composite antibacterial agent nanofiber membrane obtained in the step 7) to obtain the multi-scale nanofiber membrane (figure 2). Electrostatic spinning conditions: the voltage of the high voltage generator is 25 KV; the distance from the nozzle to the receiving base cloth is 18 cm, and the caliber of the nozzle is 0.15 cm; the flow rate of the sprayed electrostatic spinning solution is 0.5 mL/h; the reception time was 20 min.
9) Ultrasonic wave composite processing is carried out on the multi-scale nanofiber membrane, and the degradable nanofiber mask filter core is manufactured, as shown in figure 3.
As shown by testing the degradable nanofiber mask filter core, the diameter of the nanofiber in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 210 nm, and the pore diameter in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 4um. The diameter of the nanofiber in the superfine nanofiber membrane is 61nm, and the pore diameter of the multi-scale nanofiber membrane is 3um.
Example 2
A preparation method of a degradable nanofiber mask filter core with renewable antibacterial performance comprises the following steps:
1) Equal molar amounts (0.1 mol) of 5, 5-dimethylhydantoin and sodium hydroxide particles were weighed, added to acetone, stirred at room temperature until completely dissolved, and an acetone solution with a concentration of 3% of 5, 5-dimethylhydantoin was prepared. And (3) removing the acetone solvent by rotary evaporation, and placing the obtained hydantoin sodium salt in a vacuum drying oven to be dried at 45 ℃ for 1 day, thereby finally obtaining the hydantoin sodium salt.
2) 0.1mol of hydantoin sodium salt obtained in the step 1) is weighed, dissolved into N, N-Dimethylformamide (DMF), added with 0.1mol of epichlorohydrin, prepared into DMF solution with the hydantoin sodium salt concentration of 5 weight percent, and kept at the temperature of 90 ℃ for reaction of 12 h. And after the reaction is finished, removing a byproduct NaCl through suction filtration. And (3) removing the solvent by reduced pressure distillation to finally obtain the milky epoxy haloamine precursor product.
3) Weighing 0.1g of GO and 0.2g of the epihalohydrin precursor obtained in step 2), and dissolving in a mixed solvent of water and ethanol (v/v, 2: 1) A mixed solution having a graphene oxide concentration of 1wt% was prepared. After 30 min of sonication, transfer to an oil bath and reaction at 80℃for 6 h. Centrifugation (10000 rpm,15 min) and removal of supernatant, repeated washing with ethanol and centrifugation. And (3) drying in a vacuum drying oven at 45 ℃ for 2 days to obtain black solid, namely the final graphene oxide based epoxy haloamine precursor grafted product (graphene oxide-haloamine composite antibacterial agent).
4) Weighing a certain mass of the grafting product of the graphene oxide-based epoxy halamine precursor obtained in the step 3), and slowly adding the grafting product into a mixture containing a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) And (3) in a mixed solution flask, stirring vigorously at 45 ℃ and 400 r/min for 2h to prepare the graphene oxide-halogen amine composite antibacterial agent solution with the grafting product concentration of the graphene oxide-epoxy halogen amine precursor of 0.5 wt%.
5) Adding tetrabutylammonium chloride with a certain mass into the solution obtained in the step 4), and vigorously stirring for 2h at 45 ℃ and 400 r/min to prepare a mixed solution with the tetrabutylammonium chloride concentration of 0.5 wt%. Weighing polylactic acid master batch (M) with certain mass W 200000), under 65 ℃, 400 r/min conditions, stirring vigorously for 6 h, and preparing a spinning solution having a polylactic acid concentration of 11 wt%.
6) The tetrabutylammonium chloride was weighed and added to a mixture containing only a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) In the mixed solution, the mixture was vigorously stirred at 45℃and 400 r/min for 2h to prepare a mixed solution having a tetrabutylammonium chloride concentration of 5wt%. Adding polylactic acid master batch with certain mass, and vigorously stirring for 6 h at 65 ℃ and 400 r/min to prepare the ultra-dilute spinning solution with the polylactic acid concentration of 3 wt%.
7) Filling the spinning solution obtained in the step 5) into a needle tube, carrying out electrostatic spinning, and spinning the needle tube on the surface of polylactic acid non-woven fabric (the gram weight of the non-woven fabric is 50 g/m) 2 ) And preparing the graphene oxide-halamine composite antibacterial agent nanofiber membrane. Electrostatic spinning conditions: the voltage of the high-voltage generator is 20 KV, the distance from the nozzle to the receiving base cloth is 18 cm, the caliber of the nozzle is 0.15 cm, the flow rate of the sprayed electrostatic spinning solution is 0.8 mL/h, and the receiving time is 30 min.
8) Filling the spinning solution obtained in the step 6) into a needle tube, carrying out electrostatic spinning, and preparing a layer of superfine nanofiber membrane on the surface of the graphene oxide-halamine composite antibacterial agent nanofiber membrane obtained in the step 7) to obtain the multi-scale nanofiber membrane. Electrostatic spinning conditions: the voltage of the high-voltage generator is 20 KV, the distance from the nozzle to the receiving base cloth is 18 cm, the caliber of the nozzle is 0.15 cm, the flow rate of the sprayed electrostatic spinning solution is 0.6 mL/h, and the receiving time is 10 min.
9) And carrying out ultrasonic composite processing on the multi-scale nanofiber membrane to obtain the degradable nanofiber mask filter core.
As shown by testing the degradable nanofiber mask filter core, the diameter of the nanofiber in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 156 nm, and the pore diameter in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 2.5um. The diameter of the nanofiber in the superfine nanofiber membrane is 41 nm, and the pore diameter of the multi-scale nanofiber membrane is 1.3um.
Example 3
A preparation method of a degradable nanofiber mask filter core with renewable antibacterial performance comprises the following steps:
1) Equal molar amounts (0.1 mol) of 5, 5-dimethylhydantoin and sodium hydroxide particles were weighed, added to acetone, stirred at room temperature until completely dissolved, and an acetone solution with a 5, 5-dimethylhydantoin concentration of 8% was prepared. And (3) removing the acetone solvent by rotary evaporation, and placing the obtained hydantoin sodium salt in a vacuum drying oven to be dried at 45 ℃ for 1 day, thereby finally obtaining the hydantoin sodium salt.
2) 0.1mol of hydantoin sodium salt obtained in the step 1) is weighed, dissolved into N, N-Dimethylformamide (DMF), added with 0.1mol of epichlorohydrin, prepared into DMF solution with the concentration of hydantoin sodium salt of 15 weight percent, and kept at the temperature of 80 ℃ for reaction of 15h. And after the reaction is finished, removing a byproduct NaCl through suction filtration. And (3) removing the solvent by reduced pressure distillation to finally obtain the milky epoxy haloamine precursor product.
3) Weighing 0.1g of GO and 0.5g of the epihalohydrin precursor obtained in step 2), and dissolving in a mixed solvent of water and ethanol (v/v, 2: 1) A mixed solution having a graphene oxide concentration of 2wt% was prepared. After 30 min of sonication, transfer to an oil bath and reaction at 90℃was carried out for 8 h. Centrifugation (10000 rpm,15 min) and removal of supernatant, repeated washing with ethanol and centrifugation. And (3) drying in a vacuum drying oven at 45 ℃ for 2 days to obtain black solid, namely the final graphene oxide based epoxy haloamine precursor grafted product (graphene oxide-haloamine composite antibacterial agent).
4) Weighing a certain mass of the grafting product of the graphene oxide-based epoxy halamine precursor obtained in the step 3), and slowly adding the grafting product into a mixture containing a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) In a mixed solution flask, the mixed solution is vigorously stirred at 45 ℃ and 400 r/min for 2h, and a graphene oxide-haloamine composite antibacterial agent solution with the concentration of 0.7wt% is prepared.
5) Adding tetrabutylammonium chloride with a certain mass into the solution obtained in the step 4), and vigorously stirring for 4 h at 35 ℃ and 400 r/min to prepare a mixed solution with the tetrabutylammonium chloride concentration of 0.5 wt%. Weighing polylactic acid master batch (M) with certain mass W =200000), under 80 ℃, 400 r/min conditions, stirring vigorously for 6 h, and preparing a spinning solution having a polylactic acid concentration of 13 wt%.
6) The tetrabutylammonium chloride was weighed and added to a mixture containing only a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) In the mixed solution, the mixture was vigorously stirred at 45℃and 400 r/min for 2h to prepare a mixed solution having a tetrabutylammonium chloride concentration of 7wt%. Adding polylactic acid master batch with certain mass, and vigorously stirring for 6 h at 65 ℃ and 400 r/min to prepare the ultra-dilute spinning solution with the polylactic acid concentration of 5wt%.
7) Filling the spinning solution obtained in the step 5) into a needle tube, carrying out electrostatic spinning, and spinning the needle tube on the surface of polylactic acid non-woven fabric (the gram weight of the non-woven fabric is 50 g/m) 2 ) And preparing the graphene oxide-halamine composite antibacterial agent nanofiber membrane. Electrostatic spinning conditions: the voltage of the high voltage generator is 25 KV; the distance from the nozzle to the receiving base cloth is 18 cm, and the caliber of the nozzle is 0.15 cm; the flow rate of the sprayed electrostatic spinning solution is 0.8 mL/h; the receiving time is 50 min.
8) Filling the spinning solution obtained in the step 6) into a needle tube, carrying out electrostatic spinning, and preparing a layer of superfine nanofiber membrane on the surface of the graphene oxide-halamine composite antibacterial agent nanofiber membrane obtained in the step 7) to obtain the multi-scale nanofiber membrane. Electrostatic spinning conditions: the voltage of the high voltage generator is 25 KV; the distance from the nozzle to the receiving base cloth is 18 cm, and the caliber of the nozzle is 0.15 cm; the flow rate of the sprayed electrostatic spinning solution is 0.5 mL/h; the reception time was 20 min.
9) And carrying out ultrasonic composite processing on the multi-scale nanofiber membrane to obtain the degradable nanofiber mask filter core.
As shown by testing the degradable nanofiber mask filter core, the diameter of the nanofiber in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 397. 397 nm, and the pore diameter in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 9.5um. The diameter of the nanofiber in the superfine nanofiber membrane is 98 nm, and the pore diameter of the multi-scale nanofiber membrane is 9.3 um.
Example 4
A preparation method of a degradable nanofiber mask filter core with renewable antibacterial performance comprises the following steps:
1) 0.1mol of 5, 5-dimethyl hydantoin and 0.2mol of sodium hydroxide particles are weighed into acetone, stirred at room temperature until the mixture is completely dissolved, and an acetone solution with the concentration of 5, 5-dimethyl hydantoin of 3% is prepared. And (3) removing the acetone solvent by rotary evaporation, and placing the obtained hydantoin sodium salt in a vacuum drying oven to be dried at 45 ℃ for 1 day, thereby finally obtaining the hydantoin sodium salt.
2) 0.1mol of hydantoin sodium salt obtained in the step 1) is weighed, dissolved in N, N-Dimethylformamide (DMF), and 0.2mol of epichlorohydrin is added to prepare a DMF solution with the hydantoin sodium salt concentration of 10 weight percent. Reaction 12h was carried out at a temperature of 100 ℃. And after the reaction is finished, removing a byproduct NaCl through suction filtration. And (3) removing the solvent by reduced pressure distillation to finally obtain the milky epoxy haloamine precursor product.
3) Weighing 0.1g of GO and 0.3g of the epihalohydrin precursor obtained in step 2), and dissolving in a mixed solvent of water and ethanol (v/v, 2: 1) A mixed solution having a graphene oxide concentration of 0.5wt% was prepared. After 30 min of sonication, transfer to an oil bath and react at 70 ℃ for 12 h. Centrifugation (10000 rpm,15 min) and removal of supernatant, repeated washing with ethanol and centrifugation. And (3) drying in a vacuum drying oven at 45 ℃ for 2 days to obtain black solid, namely the final graphene oxide based epoxy haloamine precursor grafted product (graphene oxide-haloamine composite antibacterial agent).
4) Weighing a certain mass of the grafting product of the graphene oxide-based epoxy halamine precursor obtained in the step 3), and slowly adding the grafting product into a mixture containing a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) In a mixed solution flask, under the conditions of 35 ℃ and 400 r/min, the mixed solution is vigorously stirred for 4 h, and the graphene oxide-haloamine composite antibacterial agent solution with the concentration of 1 weight percent is prepared.
5) Adding tetrabutylammonium chloride with a certain mass into the solution obtained in the step 4), and vigorously stirring for 2h at 55 ℃ and 400 r/min to prepare a mixed solution with the tetrabutylammonium chloride concentration of 0.3 wt%. Weighing polylactic acid master batch (M) with certain mass W =200000) was added to the above solution and vigorously stirred at 60 ℃, 400 r/min for 6 h to prepare a spinning solution having a polylactic acid concentration of 15wt%.
6) The tetrabutylammonium chloride was weighed and added to a mixture containing only a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 3: 7) In the mixed solution, the mixture was vigorously stirred at 45℃and 400 r/min for 2h to prepare a mixed solution having a tetrabutylammonium chloride concentration of 7wt%. Adding polylactic acid master batch with certain mass, and vigorously stirring for 6 h at 65 ℃ and 400 r/min to prepare the ultra-dilute spinning solution with the polylactic acid concentration of 3 wt%.
7) Filling the spinning solution obtained in the step 5) into a needle tube, carrying out electrostatic spinning, and spinning the needle tube on the surface of polylactic acid non-woven fabric (the gram weight of the non-woven fabric is 50 g/m) 2 ) Is made intoObtaining the graphene oxide-halamine composite antibacterial agent nanofiber membrane. Electrostatic spinning conditions: the voltage of the high voltage generator is 25 KV; the distance from the nozzle to the receiving base cloth is 18 cm, and the caliber of the nozzle is 0.15 cm; the flow rate of the sprayed electrostatic spinning solution is 0.8 mL/h; the reception time was 30 min.
8) Filling the spinning solution obtained in the step 6) into a needle tube, carrying out electrostatic spinning, and preparing a layer of superfine nanofiber membrane on the surface of the graphene oxide-halamine composite antibacterial agent nanofiber membrane obtained in the step 7) to obtain the multi-scale nanofiber membrane. Electrostatic spinning conditions: the voltage of the high-voltage generator is 25 KV, the distance from the nozzle to the receiving base cloth is 16 cm, the caliber of the nozzle is 0.15 cm, the flow rate of the sprayed electrostatic spinning solution is 0.8 mL/h, and the receiving time is 30 min.
9) And carrying out ultrasonic composite processing on the multi-scale nanofiber membrane to obtain the degradable nanofiber mask filter core.
As shown by testing the degradable nanofiber mask filter core, the diameter of the nanofiber in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 163 nm, and the pore diameter in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 5.4um. The diameter of the nanofiber in the superfine nanofiber membrane is 63nm, and the pore diameter of the multi-scale nanofiber membrane is 5.6 um.
Example 5
A preparation method of a degradable nanofiber mask filter core with renewable antibacterial performance comprises the following steps:
1) 0.1mol of 5, 5-dimethyl hydantoin and 0.15mol of sodium hydroxide particles were weighed into acetone, stirred at room temperature until completely dissolved, and an acetone solution with a 5wt% concentration of 5, 5-dimethyl hydantoin was prepared. And (3) removing the acetone solvent by rotary evaporation, and placing the obtained hydantoin sodium salt in a vacuum drying oven to be dried at 45 ℃ for 1 day, thereby finally obtaining the hydantoin sodium salt.
2) 0.1mol of hydantoin sodium salt obtained in the step 1) is weighed, dissolved into N, N-Dimethylformamide (DMF), added with 0.15mol of epichlorohydrin, prepared into DMF solution with the hydantoin sodium salt concentration of 10wt%, and kept at the temperature of 80 ℃ for reaction of 15h. And after the reaction is finished, removing a byproduct NaCl through suction filtration. And (3) removing the solvent by reduced pressure distillation to finally obtain the milky epoxy haloamine precursor product.
3) Weighing 0.1g of GO and 0.5g of the epihalohydrin precursor obtained in step 2), and dissolving in a mixed solvent of water and ethanol (v/v, 1: 1) A mixed solution having a graphene oxide concentration of 0.5wt% was prepared. After 30 min of sonication, transfer to an oil bath and react at 80 ℃ for 12 h. Centrifugation (10000 rpm,15 min) and removal of supernatant, repeated washing with ethanol and centrifugation. And (3) drying in a vacuum drying oven at 45 ℃ for 2 days to obtain black solid, namely the final graphene oxide based epoxy haloamine precursor grafted product (graphene oxide-haloamine composite antibacterial agent).
4) The grafting product of the graphene oxide-based epihalohydrin precursor obtained in step 3) was weighed and slowly added to a solution containing 150ml of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 1: 1) And (3) in a mixed solution flask, vigorously stirring for 2h at the temperature of 55 ℃ and under the condition of 400 r/min, so as to prepare the graphene oxide-halogen amine composite antibacterial agent solution with the grafting product concentration of the graphene oxide-epoxy halogen amine precursor of 1 wt%.
5) Tetrabutylammonium chloride was added to the solution obtained in the step 4), and the mixture was vigorously stirred at 45℃and 400 r/min for 2h to prepare a mixed solution having a tetrabutylammonium chloride concentration of 0.9% by weight. Polylactic acid master batch (M) W =200000) was added to the mixed solution and vigorously stirred at 65 ℃, 400 r/min for 6 h to prepare a spinning solution having a polylactic acid concentration of 10 wt%.
6) The tetrabutylammonium chloride is weighed and added to a mixture containing only a certain volume of N, N-Dimethylformamide (DMF) and dimethyl carbonate (DMC) (v/v, 1: 1) In the mixed solution, the mixture was vigorously stirred at 45℃and 400 r/min for 2h to prepare a mixed solution having a tetrabutylammonium chloride concentration of 3 wt%. Adding polylactic acid master batch with certain mass, and vigorously stirring for 6 h at 65 ℃ and 400 r/min to prepare the ultra-dilute spinning solution with the polylactic acid concentration of 1 wt%.
7) Filling the spinning solution obtained in the step 5) into a needle tube, carrying out electrostatic spinning, and spinning the needle tube on the surface of polylactic acid non-woven fabric (the gram weight of the non-woven fabric is 50 g/m) 2 ) To obtainGraphene oxide-halamine composite antibacterial agent nanofiber membrane. Electrostatic spinning conditions: the voltage of the high voltage generator is 30 KV; the distance from the nozzle to the receiving base cloth is 15 cm, and the caliber of the nozzle is 0.1cm; the flow rate of the sprayed electrostatic spinning solution is 3 mL/h; the receiving time is 10 min.
8) Filling the spinning solution obtained in the step 6) into a needle tube, carrying out electrostatic spinning, and preparing a layer of superfine nanofiber membrane on the surface of the graphene oxide-halamine composite antibacterial agent nanofiber membrane obtained in the step 7) to obtain the multi-scale nanofiber membrane. Electrostatic spinning conditions: the voltage of the high voltage generator is 30 KV; the distance from the nozzle to the receiving base cloth is 15 cm, and the caliber of the nozzle is 0.1cm; the flow rate of the sprayed electrostatic spinning solution is 3 mL/h; the reception time was 60 min.
9) And carrying out ultrasonic composite processing on the multi-scale nanofiber membrane to obtain the degradable nanofiber mask filter core.
As shown by testing the degradable nanofiber mask filter core, the diameter of the nanofiber in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 105 nm, and the pore diameter in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 1.3um. The diameter of the nanofiber in the superfine nanofiber membrane is 26 nm, and the pore diameter of the multi-scale nanofiber membrane is 0.05 um.
Test case
In order to test the antibacterial property of the nanofiber membrane, the following steps are selectedE. coliAndS. aureusboth bacteria were tested. The experimental sample was a degradable nanofiber mask filter core prepared in example 1 and was designated as PLA- (N-hal). The comparative sample was PLA nanofiber membrane. As can be seen from FIG. 4, the PLA nanofiber membrane has almost no antibacterial property, and the haloamine-doped PLA- (N-hal) pairE.coli、S.aureusHas obvious inhibiting effect. PLA- (N-hal) pairE.coliThe antibacterial rate of (2) is 99.1%; for a pair ofS.aureusThe antibacterial rate of (2) is 99.2%. After ten chlorine bleaching cycles, the fiber membrane pairE. coliAndS. aureusthe antibacterial rate of the two bacteria is hardly changed.
The filtration performance of the degradable nanofiber mask filter core was tested, and as shown in fig. 5, the initial filtration efficiency of the degradable nanofiber mask filter core (PLA filter core) was 98.67%, the filtration resistance was 78Pa, the filtration efficiency was reduced by 95.76% after 12 hours of use, and the filtration resistance was 84Pa.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (6)
1. The degradable nanofiber mask filter core with the renewable antibacterial performance is characterized by comprising a polylactic acid non-woven fabric, a graphene oxide-halamine composite antibacterial agent nanofiber membrane and an ultrafine nanofiber membrane which are sequentially arranged; the average diameter of the nanofiber in the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 105-163 nm, and the average pore diameter of the graphene oxide-halamine composite antibacterial agent nanofiber membrane is 1-10 um; the average diameter of the nano fibers in the superfine nano fiber membrane is 26-63nm, and the average pore diameter of the superfine nano fiber membrane is 0.05-10 um;
the preparation method comprises the following steps:
(1) Adding 5, 5-dimethyl hydantoin and sodium hydroxide into acetone, stirring until the mixture is completely dissolved, and then removing the acetone to obtain hydantoin sodium salt; dissolving hydantoin sodium salt into N, N-dimethylformamide, then adding epoxy chloropropane to react, and after the reaction is finished, carrying out suction filtration and distillation to obtain an epoxy haloamine precursor;
(2) Dissolving graphene oxide and the epoxy haloamine precursor prepared in the step (1) in a mixed solvent I for reaction, and separating and purifying reactants after the reaction is finished to prepare a grafting product of the graphene oxide-based epoxy haloamine precursor;
(3) Dissolving the grafting product of the graphene oxide-based epoxy halamine precursor prepared in the step (2) into a mixed solution solvent II to obtain a graphene oxide-halamine composite antibacterial agent solution, adding tetrabutyl ammonium chloride, dissolving to obtain a tetrabutyl ammonium chloride mixed solution, and finally adding polylactic acid, and dissolving to obtain a polylactic acid mixed spinning solution;
(4) Dissolving tetrabutyl ammonium chloride in a mixed solution solvent II to prepare tetrabutyl ammonium chloride solution, adding polylactic acid, and dissolving to prepare polylactic acid ultra-dilute spinning solution;
(5) Carrying out electrostatic spinning on the polylactic acid mixed spinning solution prepared in the step (3) to prepare a graphene oxide-halamine composite antibacterial agent nanofiber membrane;
(6) Carrying out electrostatic spinning on the polylactic acid ultra-thin spinning solution prepared in the step (4), spraying a layer of ultra-thin nanofiber membrane on a receiving substrate, preparing a multi-scale nanofiber membrane by using the graphene oxide-halamine composite antibacterial agent nanofiber membrane prepared in the step (5) as the receiving substrate, and preparing a degradable nanofiber mask filter element by ultrasonic compounding;
the concentration of a grafting product of the graphene oxide-epoxy halamine precursor in the graphene oxide-halamine composite antibacterial agent solution in the step (3) is 0.3-1.0wt%, the concentration of tetrabutylammonium chloride in the tetrabutylammonium chloride mixed solution is 0.3-0.9wt%, and the concentration of polylactic acid in the polylactic acid mixed spinning solution is 10-15 wt%;
the concentration of tetrabutyl ammonium chloride in the tetrabutyl ammonium chloride solution in the step (4) is 3-7wt% and the concentration of polylactic acid in the polylactic acid ultra-dilute spinning solution is 1-7wt%.
2. The degradable nanofiber mask filter cartridge with renewable antimicrobial properties of claim 1 wherein: the molar ratio of the 5, 5-dimethyl hydantoin to the sodium hydroxide particles in the step (1) is 1: (1-2) the concentration of 5, 5-dimethylhydantoin in acetone is 3-8wt%; the molar ratio of hydantoin sodium salt to epichlorohydrin is 1: (1-2) the concentration of hydantoin sodium salt in N, N-dimethylformamide is 5-15wt%; the reaction temperature of the hydantoin sodium salt and the epichlorohydrin is 80-100 ℃ and the reaction time is 10-15h.
3. The degradable nanofiber mask filter cartridge with renewable antimicrobial properties of claim 2, wherein: in the step (2), the mass ratio of the graphene oxide to the epoxy haloamine precursor is 1: (2-5), wherein the volume ratio of the mixed solvent I is (1-2): 1 water and ethanol, wherein the concentration of the graphene oxide in the mixed solvent I is 0.5-2wt%, the reaction temperature of the graphene oxide and the epoxy haloamine precursor is 70-90 ℃, and the reaction time is 6-12 h.
4. A degradable nanofiber mask filter cartridge having renewable antimicrobial properties according to any one of claims 1-3, wherein: the mixed solvent II in the step (3) or the step (4) is N, N-dimethylformamide and dimethyl carbonate with the volume ratio of (3:7) - (1:1).
5. The degradable nanofiber mask filter cartridge with renewable antibacterial properties according to claim 4, wherein the process parameters of electrospinning in step (5) are: the voltage of the high-voltage generator is 20-30 KV, the distance from the nozzle to the receiving substrate is 15-18 cm, the caliber of the nozzle is 0.1-0.2 cm, the flow rate of the electrostatic spinning solution is 0.5-3.0mL/h, the receiving time is 10-60 min, and the receiving substrate is polylactic acid non-woven fabric.
6. The degradable nanofiber mask filter cartridge with renewable antibacterial properties according to claim 5, wherein the process parameters of electrospinning in step (6) are: the voltage of the high-voltage generator is 20-30 KV, the distance from the nozzle to the receiving substrate is 15-18 cm, the caliber of the nozzle is 0.1-0.2 cm, and the flow rate of the electrostatic spinning solution is 0.3-1.0 mL/h; the receiving time is 10-60 min.
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