CN105200663B - The preparation method of antibacterial nanofiber membrane - Google Patents
The preparation method of antibacterial nanofiber membrane Download PDFInfo
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- CN105200663B CN105200663B CN201510737628.4A CN201510737628A CN105200663B CN 105200663 B CN105200663 B CN 105200663B CN 201510737628 A CN201510737628 A CN 201510737628A CN 105200663 B CN105200663 B CN 105200663B
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- 239000012528 membrane Substances 0.000 title claims abstract description 88
- 239000002121 nanofiber Substances 0.000 title claims abstract description 75
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 85
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 230000003641 microbiacidal effect Effects 0.000 claims abstract description 28
- 229940124561 microbicide Drugs 0.000 claims abstract description 28
- 239000002855 microbicide agent Substances 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229920002521 macromolecule Polymers 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 7
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 4
- 239000000417 fungicide Substances 0.000 claims abstract description 4
- 238000009987 spinning Methods 0.000 claims description 38
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 22
- 239000002105 nanoparticle Substances 0.000 claims description 20
- 229920002101 Chitin Polymers 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 229960003638 dopamine Drugs 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004132 cross linking Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000009938 salting Methods 0.000 claims description 7
- 229920003169 water-soluble polymer Polymers 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 230000000845 anti-microbial effect Effects 0.000 claims description 6
- 238000005352 clarification Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229920005615 natural polymer Polymers 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 239000011032 tourmaline Substances 0.000 claims description 4
- 229910052613 tourmaline Inorganic materials 0.000 claims description 4
- 229940070527 tourmaline Drugs 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 claims description 3
- 239000001856 Ethyl cellulose Substances 0.000 claims description 3
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000003899 bactericide agent Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000009396 hybridization Methods 0.000 claims description 3
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002068 microbial inoculum Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000002657 fibrous material Substances 0.000 claims 1
- 239000004745 nonwoven fabric Substances 0.000 claims 1
- 229920000915 polyvinyl chloride Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 239000013557 residual solvent Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229960001296 zinc oxide Drugs 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 239000013528 metallic particle Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 229940108928 copper Drugs 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- YVZZXWOQIYDEHO-UHFFFAOYSA-N NCCC1=CC(O)=C(O)C=C1.[Ag] Chemical compound NCCC1=CC(O)=C(O)C=C1.[Ag] YVZZXWOQIYDEHO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007937 eating Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229940043774 zirconium oxide Drugs 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention is a kind of preparation method of antibacterial nanofiber membrane, including the preparation of nano fibrous membrane, the preparation of microbicide solution and microbicide solution modification nano fibrous membrane, it is characterised in that：The antibacterial nanofiber membrane is to be immersed in nano fibrous membrane in the microbicide solution of various concentrations to be made, described nano fibrous membrane passes through polymerisation film forming in organic monomer or organic monomer and inorganic fungicide solution, or film forming is directly soaked in the microbicide solution of Polymer Solution or macromolecule and inorganic mixed solution, described preparation method comprises the following steps：Step（1）Prepare microbicide solution；Step（2）Prepared polymer electrostatic spinning solution and prepare nano fibrous membrane；Step（3）Microbicide solution modifies nano fibrous membrane, and the multi-stage porous nanofiber cross-linked structure film of obtained core shell structure is antibacterial nanofiber membrane finished product.
Description
Technical field
The present invention relates to a kind of preparation method of tunica fibrosa, particularly discloses a kind of preparation side of antibacterial nanofiber membrane
Method, apply the field that antibacterial functions are needed to have in medical science, air filtration, water process etc..
Background technology
Today of 21 century, scientific and technical development are made that the contribution of brilliance, but people to the survival and development of the mankind
Class have ignored the synergy of development in science and technology and environmental problem.For the ecological environment of nature by serious destruction, the mankind's is strong
Health is greatly threatened.Hang Seng makes facing mankind wantonly for the SARS of 2003, the various bird flus in later stage and bacterial virus
Unprecedented disaster.Therefore people start there is antibacterial on row of eating and drinking, antibacterial fabric etc. it is high will
Ask.
The features such as traditional nano fibrous membrane because its fibre diameter is small, aperture is small, and porosity is high, and specific surface area is big, makes
It has a wide range of applications in air filtration, water process, catalysis, medicine and other fields.It is but various by being added in spinning solution
Small molecule nano particle not only increase only the difficulty of spinning technique, while be greatly reduced the active site of functional material, its
Cost greatly increases.It is thin that traditional nano fibrous membrane by the porous nano-fibre of its surface modification makes it be shaped as core-shell structure
Film, and some other nano particles can be fixed simultaneously, metallic particles such as argent, copper, zinc, metal salt solution such as nitric acid
Silver, copper nitrate, zinc nitrate, metal oxide such as cupric oxide, zinc oxide, iron oxide, zirconium oxide etc., inorganic nanoparticles such as dioxy
Change one or more therein, the nano fibrous membranes such as titanium, tourmaline, boehmite and secure nanometer while there is antibacterial effect
Particle, its surface area and the scope contacted with bacterium are added, and there is the characteristics of difficult for drop-off, so as to strengthen antibacterial effect
Fruit.Nano fibrous membrane not only has excellent anti-microbial property, also has the characteristics that acidproof, water-fastness, nontoxic, and therefore, preparation has
Modification of the machine inorganic hybrid nano antiseptic to functional nano fibrous membrane has great Practical significance.
The content of the invention
The invention aims to strengthen the anti-microbial property of existing nano fibrous membrane, its nanofiber mechanical property is overcome
Can be poor, intolerant to stranding and antifouling property difference the shortcomings of, a kind of preparation method of antibacterial nanofiber membrane is disclosed.
What the present invention was realized in：A kind of preparation method of antibacterial nanofiber membrane, including nano fibrous membrane preparation,
The preparation of microbicide solution and microbicide solution modification nano fibrous membrane, it is characterised in that：The antibacterial nanofiber membrane be by
Nano fibrous membrane is immersed in the microbicide solution of various concentrations and is made, and described nano fibrous membrane is in organic monomer or organic list
By polymerisation film forming in body and inorganic fungicide solution, or killing in Polymer Solution or macromolecule and inorganic mixed solution
Film forming is directly soaked in microbial inoculum solution, described preparation method comprises the following steps：
A, step（1）Prepare microbicide solution：
（a）The bactericide powder or microbicide solution of 0.1~20 parts by weight are dissolved or dispersed in water, temperature control exists
20~50 DEG C, stir 1~3 hour；
（b）Under the conditions of 20~50 DEG C of bath temperatures, antimicrobial nano particle or salting liquid are added, then using ultrasonic wave
Concussion or magnetic stir bar stir 10~60 minutes；
B, step（2）Prepared polymer electrostatic spinning solution and prepare nano fibrous membrane：
（a）By polymer or using polymer as template inorganic salts and mixed with polymers solution magnetic stir bar effect
Lower dissolving in a solvent, is stirred 10~24 hours, until being rendered as the polymer dope of homogeneous clarification；
（b）The polymer dope configured loads spinning head, in nonwoven at humidity 20~50%, 20~50 DEG C of temperature
Spinning is carried out in cloth substrate, spinning technology parameter is：Spinning 10~30cm of distance, 0.1~5ml/h of spinning speed, obtains nanometer
Tunica fibrosa, then it is placed in vacuum drying oven, in the case where temperature is 50~100 DEG C, the time is 2~12 hours, removes residual
Organic solvent；
C, step（3）Microbicide solution modifies nano fibrous membrane：By step（2）The nano fibrous membrane of middle preparation is immersed in matter
Measure in the microbicide solution that fraction is 0.1~20wt%, stirred 1 minute to 24 hours in the presence of magnetic stir bar, stand 10
Be positioned over baking oven after~30 seconds, drying temperature is 50~100 DEG C, and the time is 120~600 minutes, obtained core shell structure it is more
Level hole nanofiber cross-linked structure film is antibacterial nanofiber membrane finished product.
The step（2）In prepare nano fibrous membrane include using solvent based polymer, water solubility or environmentally friendly
Polymer, natural polymerses and the inorganic salt solution using macromolecule as template prepare inorganic nano-fiber material；It is described
Solvent based polymer include solvent-borne type PEI, polyurethane, polyimides, polysulfones, polyacrylonitrile, polystyrene, gather
Vinyl chloride, one or more of mixtures in polyvinylidene fluoride, described water-soluble or environmentally friendly polymer include
High molecular polymer using ethanol or water as solvent, including polyvinyl alcohol, PEO, polyacrylic acid, polyvinylpyrrolidine
Ketone, polyethyleneimine, polyacrylamide, one or more of mixtures in PLA, described natural polymerses
Including cellulose, cellulose acetate, ethyl cellulose, one or more of mixtures in chitin are described with macromolecule
Inorganic salt solution for template is the inorganic salt solution using polyvinyl alcohol as template, and prepared inorganic nano-fiber includes dioxy
SiClx, zirconium oxide, aluminum oxide or titanium oxide.Handled first by glutaraldehyde using nano fibrous membrane made from water-soluble polymer
Or pyroreaction carries out cross-linking reaction, after treatment as water-insoluble nano fibrous membrane.The step（2）In solvent be
Water, tetrahydrofuran, trifluoroacetic acid, chloroform, 1-METHYLPYRROLIDONE, the one or more of of DMF appoint
The mixture of meaning ratio.It is described that nano fibrous membrane is immersed directly in organic solution film forming or is dispersed in nano particle
Into composite hybridization film in organic mixed solution, wherein described nano particle is metal nanoparticle or inorganic nanoparticles,
For grain diameter at 5~200 nanometers, described metallic particles is the one or more in argent, copper, zinc, cupric oxide and zinc oxide,
Described inorganic nanoparticles are the one or more in titanium dioxide, tourmaline and boehmite.It is described to enter with nano fibrous membrane
It is that three (methylol) aminomethane hydrochlorides are molten in water-bath that the organic monomer of row polymerisation, which is included using water as the dopamine of solvent,
Film forming in liquid, described three（Methylol）Aminomethane hydrochloride solution is 5~50 mM, pH value 8.0~9.0；It is described to receive
Rice tunica fibrosa directly soak film forming Polymer Solution include using water and ethanol as the organosilicon quaternary ammonium salt of solvent and using acetic acid as
One or both of chitin of solvent.The nano particle is dispersed in dopamine solution or organosilicon quaternary ammonium salt
In one or more solution in alcoholic solution or the aqueous solution and chitin acetum, then nano fibrous membrane is immersed in inorganic
In mixed solution, the concentration of the inorganic mixed solution is 0.1~10wt%, and the reaction time controls at 120~600 minutes, soaked
Soak nano fibrous membrane to be placed in vacuum drying oven after film and dry, its temperature is at 50~100 DEG C.By in the inorganic mixed solution
Particle scattered 10 minutes to 1 hour by ultrasonic oscillation, it is scattered after inorganic mixed solution mass fraction to be crosslinked
React 0.1~10wt% of the high molecular weight water soluble polymer solution of film.Described step（3）Obtained antibacterial nano fiber
The grammes per square metre of film is 1~100 g/m2, fibre diameter is between 0.05~10 micron.Received using water-insoluble made from cross-linking reaction
The mechanical property of rice tunica fibrosa greatly improves, and its intensity is in 10~30MPa.
The beneficial effects of the invention are as follows：Compared with the preparation method of traditional nano fibrous membrane, the present invention has operation letter
Single, film forming homogeneity is good, cheap and the advantages that easily industrialize, and makes the functionalized nano-fiber film that it is modified in medical science, empty
Gas filters, and the field that water process etc. needs to have antibacterial functions has a wide range of applications.Invention enhances existing Nanowire
The anti-microbial property of film is tieed up, overcomes its nanofiber poor mechanical property, intolerant to rubbing with the hands and the shortcomings of antifouling property difference.
Embodiment
A kind of preparation method of antibacterial nanofiber membrane of the present invention includes the preparation of nano fibrous membrane, the system of microbicide solution
Standby and microbicide solution modification nano fibrous membrane, the antibacterial nanofiber membrane is that nano fibrous membrane is immersed in into various concentrations
It is made in microbicide solution, described nano fibrous membrane is in organic monomer or organic monomer and inorganic fungicide solution by poly-
Reaction film forming is closed, or film forming, institute are directly soaked in the microbicide solution of Polymer Solution or macromolecule and inorganic mixed solution
The preparation method stated comprises the following steps：
A, step（1）Prepare microbicide solution：
（a）The bactericide powder or microbicide solution of 0.1~20 parts by weight are dissolved or dispersed in water, temperature control exists
20~50 DEG C, stir 1~3 hour；
（b）Under the conditions of 20~50 DEG C of bath temperatures, antimicrobial nano particle or salting liquid are added, then using ultrasonic wave
Concussion or magnetic stir bar stir 10~60 minutes；
B, step（2）Prepared polymer electrostatic spinning solution and prepare nano fibrous membrane：
（a）By polymer or using polymer as template inorganic salts and mixed with polymers solution magnetic stir bar effect
Lower dissolving in a solvent, is stirred 10~24 hours, until being rendered as the polymer dope of homogeneous clarification；
（b）The polymer dope configured loads spinning head, in nonwoven at humidity 20~50%, 20~50 DEG C of temperature
Spinning is carried out in cloth substrate, spinning technology parameter is：Spinning 10~30cm of distance, 0.1~5ml/h of spinning speed, obtains nanometer
Tunica fibrosa, then it is placed in vacuum drying oven, in the case where temperature is 50~100 DEG C, the time is 2~12 hours, removes residual
Organic solvent；
C, step（3）Microbicide solution modifies nano fibrous membrane：By step（2）The nano fibrous membrane of middle preparation is immersed in matter
Measure in the microbicide solution that fraction is 0.1~20wt%, stirred 1 minute to 24 hours in the presence of magnetic stir bar, stand 10
Be positioned over baking oven after~30 seconds, drying temperature is 50~100 DEG C, and the time is 120~600 minutes, obtained core shell structure it is more
Level hole nanofiber cross-linked structure film is antibacterial nanofiber membrane finished product.
The step（2）In prepare nano fibrous membrane include using solvent based polymer, water solubility or environmentally friendly
Polymer, natural polymerses and the inorganic salt solution using macromolecule as template prepare inorganic nano-fiber material；It is described
Solvent based polymer include solvent-borne type PEI, polyurethane, polyimides, polysulfones, polyacrylonitrile, polystyrene, gather
Vinyl chloride, one or more of mixtures in polyvinylidene fluoride, described water-soluble or environmentally friendly polymer include
High molecular polymer using ethanol or water as solvent, including polyvinyl alcohol, PEO, polyacrylic acid, polyvinylpyrrolidine
Ketone, polyethyleneimine, polyacrylamide, one or more of mixtures in PLA, described natural polymerses
Including cellulose, cellulose acetate, ethyl cellulose, one or more of mixtures in chitin are described with macromolecule
Inorganic salt solution for template is the inorganic salt solution using polyvinyl alcohol as template, and prepared inorganic nano-fiber includes dioxy
SiClx, zirconium oxide, aluminum oxide or titanium oxide.
The step（2）In solvent for water, tetrahydrofuran, trifluoroacetic acid, chloroform, 1-METHYLPYRROLIDONE, N,
The mixture of one or more of arbitrary proportions of dinethylformamide.
Handled first by glutaraldehyde using nano fibrous membrane made from water-soluble polymer or high temperature carry out cross-linking reaction,
Turn into water-insoluble nano fibrous membrane after treatment.Using the mechanical property of water-insoluble nano fibrous membrane made from cross-linking reaction
It can greatly improve, its intensity is in 10~30MPa.
It is described that nano fibrous membrane is immersed directly in organic solution film forming or is dispersed in nano particle organic mixed
Close in solution into composite hybridization film, wherein described nano particle is metal nanoparticle or inorganic nanoparticles, particle diameter
At 5~200 nanometers, described metallic particles is the one or more in argent, copper, zinc, cupric oxide and zinc oxide, described
Nano particle is the one or more in titanium dioxide, tourmaline and boehmite.The nano particle is dispersed in DOPA
In one or more solution in the alcoholic solution or the aqueous solution and chitin acetum of amine aqueous solution or organosilicon quaternary ammonium salt, then
Nano fibrous membrane is immersed in inorganic mixed solution, the concentration of the inorganic mixed solution is 0.1~10wt%, the reaction time
Nano fibrous membrane was placed in vacuum drying oven and dried, its temperature is 50~100 at 120~600 minutes by control after film forming is soaked
℃.Particle in the inorganic mixed solution is scattered 10 minutes to 1 hour by ultrasonic oscillation, and inorganic mixing is molten after disperseing
The mass fraction of liquid is 0.1~10wt% of the high molecular weight water soluble polymer solution for carrying out cross-linking reaction film.
The dopamine that the organic monomer that polymerisation is carried out with nano fibrous membrane is included using water as solvent is in water-bath
Film forming in three (methylol) aminomethane hydrochloride solution, described three（Methylol）Aminomethane hydrochloride solution is 5~50
MM, pH value are 8.0~9.0；The Polymer Solution that nano fibrous membrane is directly soaked to film forming is included using water and ethanol to be molten
The organosilicon quaternary ammonium salt of agent and using acetic acid as one or both of chitin of solvent.
Described step（3）The grammes per square metre of obtained antibacterial nanofiber membrane is 1~100 g/m2, fibre diameter 0.05~
Between 10 microns.
With reference to specific embodiment, the present invention is further elaborated.
Embodiment 1：
A kind of preparation method of dopamine@polyacrylonitrile nanofiber films, comprises the following steps：
A, step（1）Prepare dopamine solution：
（a）0.394g Tris are dissolved in 250g water, Nano silver grain 5g are then added, then using ultrasonic oscillation
It is scattered 30 minutes；
（b）0.5g dopamines are added in the solution, are adjusted pH to 8.5, are stirred；
B, step（2）Prepare polyacrylonitrile electrostatic spinning solution and prepare polyacrylonitrile nanofiber film：
（a）Polyacrylonitrile is dissolved in DMF solvent in the presence of magnetic stir bar, stirring 10
~24 hours, until being rendered as the polyacryl-nitrile spinning fluid of homogeneous clarification；
（b）The polyacryl-nitrile spinning fluid configured loads spinning head, in nothing at humidity 20~50%, 20~50 DEG C of temperature
Spin and carry out spinning in cloth substrate, spinning technology parameter is：10~30 centimetres of spinning distance, 0.1~5ml/h of spinning speed, is obtained
Polyacrylonitrile nanofiber film；
（c）Polyacrylonitrile nanofiber film is placed in vacuum drying oven, dries and dries 3 hours at 100 DEG C, remove residual
Organic solvent；
C, step（3）Dopamine solution modifies polyacrylonitrile nanofiber film：
（a）The polyacrylonitrile nanofiber film of drying is immersed in the dopamine solution that mass fraction is 0.1~20wt%
In, stirred 24 hours in the presence of magnetic stir bar；
（b）After polypropylene nano fiber is film modified, cleaned with distilled water, at least three times；
（c）It will be placed in vacuum drying oven with the polyacrylonitrile nanofiber film of dopamine solution modified, dried at 60 DEG C
Dry 8 hours.Prepared dopamine@polyacrylonitrile nanofibers film reaches 95% to effective antibacterial effect of Escherichia coli, institute
The fibre strength of obtained silver-dopamine@polyacrylonitrile nanofiber films reaches 5~15MPa.
Embodiment 2：
A kind of preparation method for having zinc oxide-machine silicon quaternary ammonium salt polyacrylonitrile nanofiber film, comprises the following steps：
A, step（1）Prepare organosilicone quaternary ammonium salting liquid：5g zinc-oxide nano ions are dispersed in 100g alcohol solutions,
Then it is scattered 30 minutes using ultrasonic oscillation, add organosilicon quaternary ammonium salt 5g；
B, step（2）Prepare polyacrylonitrile electrostatic spinning solution and prepare polyacrylonitrile nanofiber film：
（a）Polyacrylonitrile is dissolved in DMF solvent in the presence of magnetic stir bar, stirring 10
~24 hours, until being rendered as the polyacryl-nitrile spinning fluid of homogeneous clarification；
（b）The polyacryl-nitrile spinning fluid configured loads spinning head, in nothing at humidity 20~50%, 20~50 DEG C of temperature
Spin and carry out spinning in cloth substrate, spinning technology parameter is：10~30 centimetres of spinning distance, 0.1~5ml/h of spinning speed, is obtained
Polyacrylonitrile nanofiber film；
（c）Polyacrylonitrile nanofiber film is placed in vacuum drying oven, dries and dries 4 hours at 100 DEG C；
C, step（3）Organosilicone quaternary ammonium salting liquid modifies polyacrylonitrile nanofiber film：
（a）The polyacrylonitrile nanofiber film of drying is immersed in the organosilicon quaternary ammonium salt that mass fraction is 0.1~20wt%
In solution, stirred 1 minute in the presence of magnetic stir bar；
（b）It will be placed in the polyacrylonitrile nanofiber film of organosilicone quaternary ammonium salting liquid modified in vacuum drying oven, 60 DEG C
Lower drying is dried 4 hours.
Prepared has zinc oxide-machine silicon quaternary ammonium salt polyacrylonitrile nanofiber film to imitate effective antibacterial of Escherichia coli
Fruit reaches 90%, and its fibre strength reaches 10~20MPa.
Embodiment 3：
A kind of preparation method of chitin@polyacrylonitrile nanofiber films, comprises the following steps：
A, step（1）Prepare chitin solution：
（a）Boehmite nano-particle 5g is dispersed in 100g acetic acid, then disperseed 30 minutes using ultrasonic oscillation；
（b）5g chitins are added, are stirred 24 hours, it is in homogeneous chitin solution to make it；
B, step（2）Prepare polyacrylonitrile electrostatic spinning solution and prepare polyacrylonitrile nanofiber film：
（a）Polyacrylonitrile is dissolved in DMF solvent in the presence of magnetic stir bar, stirring 10
~24 hours, until being rendered as the polyacryl-nitrile spinning fluid of homogeneous clarification；
（b）The polyacryl-nitrile spinning fluid configured loads spinning head, in nothing at humidity 20~50%, 20~50 DEG C of temperature
Spin and carry out spinning in cloth substrate, spinning technology parameter is：10~30 centimetres of spinning distance, 0.1~5ml/h of spinning speed, is obtained
Polyacrylonitrile nanofiber film；
（c）Polyacrylonitrile nanofiber film is placed in vacuum drying oven, dries and dries 4 hours at 100 DEG C；
C, step（3）Chitin solution modifies polyacrylonitrile nanofiber film：
（a）The polyacrylonitrile nanofiber film of drying is immersed in the chitin solution that mass fraction is 0.1~20wt%
In, stirred 1 minute in the presence of magnetic stir bar；
（b）It will be placed in vacuum drying oven with the polyacrylonitrile nanofiber film of chitin solution modified, dried at 60 DEG C
Dry 4 hours.
Prepared chitin@polyacrylonitrile nanofibers film reaches 90% to effective antibacterial effect of Escherichia coli, and it is fine
Dimension intensity reaches 10~20MPa.
Claims (10)
1. a kind of preparation method of antibacterial nanofiber membrane, including the preparation of nano fibrous membrane, the preparation of microbicide solution and kill
Microbial inoculum solution modifies nano fibrous membrane, it is characterised in that：The antibacterial nanofiber membrane is that nano fibrous membrane is immersed in into difference
It is made in the microbicide solution of concentration, described nano fibrous membrane is in organic monomer or organic monomer and inorganic fungicide solution
By polymerisation into antibacterial nanofiber membrane, or in Polymer Solution or macromolecule and the microbicide solution of inorganic mixed solution
In be directly soaked into antibacterial nanofiber membrane, described preparation method comprises the following steps：
A, step（1）Prepare microbicide solution：
（a）The bactericide powder or microbicide solution of 0.1~20 parts by weight are dissolved or dispersed in water, temperature control 20~
50 DEG C, stir 1~3 hour；
（b）Under the conditions of 20~50 DEG C of bath temperatures, antimicrobial nano particle or salting liquid are added, then using ultrasonic oscillation
Or magnetic stir bar stirs 10~60 minutes；
B, step（2）Prepared polymer electrostatic spinning solution and prepare nano fibrous membrane：
（a）By polymer or using polymer as inorganic salts and the mixed with polymers solution of template in the presence of magnetic stir bar it is molten
Solution in a solvent, stirs 10~24 hours, until being rendered as the polymer dope of homogeneous clarification；
（b）The polymer dope configured loads spinning head, in nonwoven fabric base at humidity 20~50%, 20~50 DEG C of temperature
Spinning is carried out on bottom, spinning technology parameter is：Spinning 10~30cm of distance, 0.1~5ml/h of spinning speed, obtains nanofiber
Film, then it is placed in vacuum drying oven, in the case where temperature is 50~100 DEG C, the time is 2~12 hours, removes the organic of residual
Solvent；
C, step（3）Microbicide solution modifies nano fibrous membrane：By step（2）The nano fibrous membrane of middle preparation is immersed in quality point
Number stands 10~30 in 0.1~20wt% microbicide solution, to be stirred 1 minute to 24 hours in the presence of magnetic stir bar
Baking oven is positioned over after second, drying temperature is 50~100 DEG C, and the time is 120~600 minutes, the multi-stage porous of obtained core shell structure
Nanofiber cross-linked structure film is antibacterial nanofiber membrane finished product；
The step（2）It is that template is to use the nothing using water-soluble polymer as template using polymer to prepare in nano fibrous membrane
Machine salting liquid prepares inorganic nano-fiber material；
Handled first by glutaraldehyde using nano fibrous membrane made from water-soluble polymer or high temperature carries out cross-linking reaction, located
Turn into water-insoluble nano fibrous membrane after reason.
2. the preparation method of the antibacterial nanofiber membrane according to claim 1, it is characterised in that：Described water-soluble poly
Compound includes the high molecular polymer using water as solvent, and described high molecular polymer includes polyvinyl alcohol, PEO, gathered
One or more of mixtures in acrylic acid, polyvinylpyrrolidone, polyethyleneimine or polyacrylamide, the preparation
Inorganic nano-fiber material includes silica, zirconium oxide, aluminum oxide or titanium oxide.
3. the preparation method of the antibacterial nanofiber membrane according to claim 1, it is characterised in that：The step（2）In
Prepare nano fibrous membrane also include with solvent based polymer, environmentally friendly polymer, natural polymerses prepare receive
Rice fibrous material and the inorganic salt solution using macromolecule as template prepare inorganic nano-fiber material, described solvent based polymer
Including solvent-borne type PEI, polyurethane, polyimides, polysulfones, polyacrylonitrile, polystyrene, polyvinyl chloride or poly- inclined two
One or more of mixtures in PVF, described environmentally friendly polymer include the high score using ethanol or water as solvent
Sub- polymer, described high molecular polymer include polyvinyl alcohol, PEO, polyacrylic acid, polyvinylpyrrolidone, gathered
Aziridine, polyacrylamide, one or more of mixtures in PLA, described natural polymerses include fibre
Dimension is plain, cellulose acetate, ethyl cellulose, one or more of mixtures in chitin, described using macromolecule as template
Inorganic salt solution be inorganic salt solution using polyvinyl alcohol as template.
4. the preparation method of the antibacterial nanofiber membrane according to claim 1, it is characterised in that：The step（2）In
Solvent for water, tetrahydrofuran, trifluoroacetic acid, chloroform, 1-METHYLPYRROLIDONE, DMF one kind or
The mixture of several arbitrary proportions.
5. the preparation method of the antibacterial nanofiber membrane according to claim 1, it is characterised in that：It is described by nanofiber
Film is immersed directly in film forming in organic solution or nano particle is dispersed in organic mixed solution into composite hybridization film, its
Described in nano-particle diameter at 5~200 nanometers, described nano particle is argent, copper, zinc, cupric oxide and zinc oxide
In one or more, or one or more in titanium dioxide, tourmaline and boehmite.
6. the preparation method of the antibacterial nanofiber membrane according to claim 1, it is characterised in that：Described and nanofiber
Film carries out polymerisation includes the dopamine using water as solvent into the organic monomer in antibacterial nanofiber membrane, is three in water-bath
Progress polymerisation film forming in (methylol) aminomethane hydrochloride solution, described three（Methylol）Aminomethane hydrochloride is molten
Liquid is 5~50 mM, and pH value is 8.0~9.0；The Polymer Solution that nano fibrous membrane is directly soaked to film forming is included with water
With the organosilicon quaternary ammonium salt that ethanol is solvent, using acetic acid as one or both of chitin of solvent.
7. the preparation method of the antibacterial nanofiber membrane according to claim 1 or 5, it is characterised in that：By the nanometer
Even particulate dispersion in the alcoholic solution or the aqueous solution and chitin acetum of dopamine solution or organosilicon quaternary ammonium salt one
In kind or a variety of solution, then nano fibrous membrane is immersed in inorganic mixed solution, the concentration of the inorganic mixed solution is
0.1~10wt%, reaction time control at 120~600 minutes, nano fibrous membrane are placed in vacuum drying oven after film forming is soaked
Drying, its temperature is at 50~100 DEG C.
8. the preparation method of the antibacterial nanofiber membrane according to claim 5, it is characterised in that：By the inorganic mixing
Particle in solution is scattered 10 minutes to 1 hour by ultrasonic oscillation, it is scattered after inorganic mixed solution mass fraction be into
0.1~10wt% of the high molecular weight water soluble polymer solution of row cross-linking reaction film.
9. the preparation method of the antibacterial nanofiber membrane according to claim 1, it is characterised in that：Described step（3）
The grammes per square metre of obtained antibacterial nanofiber membrane is 1~100 g/m2, fibre diameter is between 0.05~10 micron.
10. the preparation method of antibacterial nanofiber membrane according to claim 1, it is characterised in that：Using cross-linking reaction system
The mechanical property of the water-insoluble nano fibrous membrane obtained greatly improves, and its intensity is in 10~30MPa.
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