CN106192214B - A kind of preparation method of antibacterial composite fibers film - Google Patents
A kind of preparation method of antibacterial composite fibers film Download PDFInfo
- Publication number
- CN106192214B CN106192214B CN201610748681.9A CN201610748681A CN106192214B CN 106192214 B CN106192214 B CN 106192214B CN 201610748681 A CN201610748681 A CN 201610748681A CN 106192214 B CN106192214 B CN 106192214B
- Authority
- CN
- China
- Prior art keywords
- graphene quantum
- stirring
- silver
- quantum dots
- antibacterial
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000000835 fiber Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 151
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 239000012528 membrane Substances 0.000 claims abstract description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 13
- 238000009987 spinning Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 12
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims abstract description 6
- 229920001432 poly(L-lactide) Polymers 0.000 claims abstract description 6
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 105
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 101
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 100
- 229910021389 graphene Inorganic materials 0.000 claims description 89
- 229910052709 silver Inorganic materials 0.000 claims description 88
- 239000004332 silver Substances 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 52
- 238000001035 drying Methods 0.000 claims description 47
- 239000002096 quantum dot Substances 0.000 claims description 47
- 239000000725 suspension Substances 0.000 claims description 47
- 238000005303 weighing Methods 0.000 claims description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 42
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 36
- 238000004140 cleaning Methods 0.000 claims description 29
- 239000005457 ice water Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 21
- -1 polytetrafluoroethylene Polymers 0.000 claims description 21
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 21
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 21
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 21
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000012286 potassium permanganate Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 238000004381 surface treatment Methods 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- 229910052681 coesite Inorganic materials 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 15
- 229910052682 stishovite Inorganic materials 0.000 claims description 15
- 229910052905 tridymite Inorganic materials 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000502 dialysis Methods 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 238000000520 microinjection Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000002121 nanofiber Substances 0.000 abstract description 7
- 229920000747 poly(lactic acid) Polymers 0.000 abstract description 3
- 239000004626 polylactic acid Substances 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 230000003115 biocidal effect Effects 0.000 abstract 2
- 238000013019 agitation Methods 0.000 abstract 1
- 230000002421 anti-septic effect Effects 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 24
- 239000004408 titanium dioxide Substances 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 229910001923 silver oxide Inorganic materials 0.000 description 11
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 description 4
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
- D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
-
- 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
- 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
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/005—Synthetic yarns or filaments
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/13—Physical properties anti-allergenic or anti-bacterial
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of antibacterial composite fibers film comprising following steps：（1）The preparation of antibacterial spinning solution：Suitable polyethylene glycol 400 is weighed in conical flask with cover, is warming up to 50 DEG C, dichloromethane is added, the wherein volume ratio of dichloromethane and polyethylene glycol 400 is 7: 2；100,000 PLLA of molecular weight is added, at room temperature magnetic agitation 2h；The lower antibiotic complex dispersion liquid that a concentration of 0.01 ~ 0.1mol/l is added dropwise of 100 ~ 300rpm stirrings；Continue 30 ~ 40min of stirring, antibacterial spinning solution is made；（2）Electrostatic spinning prepares antibacterial composite nano-fiber membrane.Special antibiotic complex is applied in polylactic acid fiber membrane, lasting effective antibacterial activity, good permeability, stability height, broad-spectrum antiseptic, biodegradable characteristic are made it have.
Description
Technical Field
The invention relates to the technical field of composite fibers, in particular to a preparation method of an antibacterial composite fiber membrane.
Background
The nanofiber membrane has the advantages of large surface area, high porosity, loose structure, capability of being designed and formed in advance according to required functions, simulation of extracellular matrix, simple preparation method and the like, has huge application potential in many fields, and is widely applied in the fields of food, medicine, daily chemicals and the like. Especially, the nanofiber membrane prepared by using natural high polymer as spinning solution has the characteristics of excellent biocompatibility, biodegradability, renewability and the like. Electrospinning is the simplest and most efficient method for preparing nanofiber membranes.
The silver-loaded nano-particle/composite fiber membrane prepared by the prior art has poor biocompatibility, and the fiber membrane structure is damaged due to the generation of byproducts in the preparation process, so that the application of the antibacterial fiber membrane is limited. Moreover, because the nano silver is granular and the granularity is nano-grade, the nano silver can only be gathered at a specific part of the fiber membrane and cannot be uniformly distributed on the surface, thereby influencing the antibacterial effect; on the other hand, the nano silver cannot be tightly combined with the fiber membrane (particularly, when the content of nano silver particles is increased, agglomeration phenomenon is easy to occur), and the nano silver is easy to fall off in the using process, so that the service life and the antibacterial effect are influenced.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of an antibacterial composite fiber membrane.
The technical problem to be solved by the invention is realized by the following technical scheme:
a preparation method of an antibacterial composite fiber membrane comprises the following steps:
(1) preparing an antibacterial spinning solution: weighing a proper amount of polyethylene glycol 400 in a conical flask with a plug, heating to 50 ℃, and adding dichloromethane, wherein the volume ratio of the dichloromethane to the polyethylene glycol 400 is 7: 2; adding PLLA with molecular weight of 10 ten thousand, and magnetically stirring at room temperature for 2 h; dripping 0.01-0.1 mol/l antibacterial compound dispersion liquid under stirring at 100-300 rpm; continuously stirring for 30-40 min to prepare an antibacterial spinning solution; (2) and (3) preparing the antibacterial composite nanofiber membrane by electrostatic spinning. The electrostatic spinning equipment consists of a high-voltage digital display direct-current power supply, a micro-injection pump, a solution storage, a capillary tube and a collecting device, and the invention adopts a grounded metal aluminum foil as the collecting device. The electrostatic spinning specifically comprises the following steps: the prepared solution is poured into a solution storage (20 mL syringe) and fixed on a micro-injection pump, a ground needle head is used as a capillary for jetting a trickle, the capillary is connected with the anode of a high-voltage power supply, a metal aluminum foil is connected with the cathode of the high-voltage power supply, and the dosage of the solution is controlled by the micro-injection pump. The parameters of the electrostatic spinning process are that the applied voltage is 22 +/-2 kV, the receiving distance is 12cm, the advancing speed is 1mL/h, the air humidity is 10 percent, the temperature is room temperature, the inner diameter of a needle used for spinning is 0.6mm, and the needle is completely dried in the air after receiving fibers by using aluminum foil.
The antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.5-0.8 g C60 powder, weighing 50-100 ml of 98 mass percent concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 300-500 rpm to obtain a mixed solution; weighing 0.5-3 g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5-8 h; quickly adding 100-200 ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30-60 min, wherein the laser irradiation power is 1-2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (300-500W ultrasonic power, stirring speed of 200-300 rpm) 50-60 ml of graphene quantum dot suspension, dropwise adding 0.001-0.005 mol/L silver nitrate solution, controlling the reaction temperature to be 45-60 ℃, dropwise adding 0.01-0.08 mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3-4: 2-3: 1-2.
(3) Dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (500-1000W of ultrasonic power and stirring speed of 300-500 rpm); then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1-2: 1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1-3 hours, centrifuging, sequentially washing with acetone and deionized water to obtain a precipitate, and placing the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent (DMSO), carrying out ultrasonic stirring (300-500W of ultrasonic power and stirring speed of 200-300 rpm) and adding 0.1-0.3 g of silver-loaded graphene quantum dots, continuing to carry out ultrasonic stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, carrying out reaction for 60-90 min at 200-240 ℃ and with the microwave power of 200-400W; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 10-30 min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 15-30 min at 80-120 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.5-0.8 g C60 powder, weighing 50-100 ml of 98 mass percent concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 300-500 rpm to obtain a mixed solution; weighing 0.5-3 g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5-8 h; quickly adding 100-200 ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30-60 min, wherein the laser irradiation power is 1-2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (300-500W ultrasonic power, stirring speed of 200-300 rpm) 50-60 ml of graphene quantum dot suspension, dropwise adding 0.001-0.005 mol/L silver nitrate solution, controlling the reaction temperature to be 45-60 ℃, dropwise adding 0.01-0.08 mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3-4: 2-3: 1-2.
(3) Dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (500-1000W of ultrasonic power and stirring speed of 300-500 rpm); then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1-2: 1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1-3 hours, centrifuging, sequentially washing with acetone and deionized water to obtain a precipitate, and placing the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(4) Adding 0.1-0.3 mol/L titanium source (the titanium source is potassium fluotitanate, ammonium fluotitanate, isopropyl titanate or titanium tetrachloride) into 1mol/L sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (3)2Coating the silver-loaded graphene quantum dots, heating to 100-110 ℃, reacting for 2-4 h, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6h, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(5) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent (DMSO), carrying out ultrasonic stirring (300-500W of ultrasonic power and stirring speed of 200-300 rpm) and adding 0.1-0.3 g of silver-loaded/titanium dioxide graphene quantum dots, continuing to carry out ultrasonic stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, carrying out reaction for 60-90 min at 200-240 ℃ and with the microwave power of 200-400W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(6) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of graphene dispersion solution, adding the silver-loaded/titanium dioxide graphene quantum dots prepared in the step (5), ultrasonically stirring for 10-30 min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 15-30 min at 80-120 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.5-0.8 g C60 powder, weighing 50-100 ml of 98 mass percent concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 300-500 rpm to obtain a mixed solution; weighing 0.5-3 g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5-8 h; quickly adding 100-200 ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30-60 min, wherein the laser irradiation power is 1-2W.
(2) Weighing zinc oxide quantum dots (with the particle size of about 2-5 nm) to prepare a dispersion liquid with the concentration of 0.5-1 mg/ml, wherein the solvent is water; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of zinc oxide dispersion liquid, dropwise adding half of the graphene quantum dot suspension liquid prepared in the step (1), and continuously ultrasonically stirring for 30-60 min; centrifuging, cleaning and drying to obtain the graphene quantum dots loaded with zinc oxide.
(3) Surface treatment of graphene quantum dots loaded with zinc oxide: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent (DMSO), carrying out ultrasonic stirring (300-500W of ultrasonic power and stirring speed of 200-300 rpm) and adding 0.1-0.3 g of graphene quantum dots loaded with zinc oxide, continuing to carry out ultrasonic stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, carrying out reaction for 60-90 min at 200-240 ℃ and with the microwave power of 200-400W; and cooling, filtering and drying to obtain the surface-treated graphene quantum dots loaded with zinc oxide.
(4) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (300-500W ultrasonic power, stirring speed of 200-300 rpm) the other half of the graphene quantum dot suspension, dropwise adding a silver nitrate solution with the concentration of 0.001-0.005 mol/L, controlling the reaction temperature to be 45-60 ℃, dropwise adding trisodium citrate dihydrate with the concentration of 0.01-0.08 mol/L, and continuously ultrasonically stirring for 60-120 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3-4: 2-3: 1-2.
(5) Dispersing 0.1-0.5 g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (500-1000W of ultrasonic power and stirring speed of 300-500 rpm); then adding water and ammonia water in a volume ratio of 3-5: 1, uniformly stirring, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1-2: 1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1-3 hours, centrifuging, sequentially washing with acetone and deionized water to obtain a precipitate, and placing the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(6) 0.1 to 0.3mol/L of a titanium source(the titanium source is potassium fluotitanate, ammonium fluotitanate, isopropyl titanate or titanium tetrachloride) is added into 1M sulfuric acid solution and mixed evenly; adding the SiO prepared in the step (5)2Coating the silver-loaded graphene quantum dots, heating to 100-110 ℃, reacting for 2-4 h, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6h, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(7) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.005-0.01 g of graphite oxide into 5-10 mL of dispersing agent (DMSO), carrying out ultrasonic stirring (300-500W of ultrasonic power and stirring speed of 200-300 rpm) and adding 0.1-0.3 g of silver-loaded/titanium dioxide graphene quantum dots, continuing to carry out ultrasonic stirring for 10-30 min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer, carrying out reaction for 60-90 min at 200-240 ℃ and with the microwave power of 200-400W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(8) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.2-0.8 mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (500-1000W ultrasonic power, stirring speed of 600-800 rpm) 80-100 ml of graphene dispersion solution, adding the zinc oxide-loaded graphene quantum dots prepared in the step (3) and the silver/titanium dioxide-loaded graphene quantum dots prepared in the step (7) (the mass ratio of the two is 2: 1-3) and ultrasonically stirring for 10-30 min, then moving the mixture into a polytetrafluoroethylene reaction kettle, and keeping the temperature at 80-120 ℃ for 15-30 min; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The invention has the following beneficial effects:
according to the antibacterial compound method, the graphene quantum dots subjected to laser irradiation are used as carriers of silver, then the carriers are coated with the silicon dioxide thin layer, the surface treatment is carried out, and finally the silicon dioxide thin layer is attached to the porous graphene, so that the silver nano particles can be better loaded and fixed, the agglomeration of the silver nano particles is prevented, the stability of the silver nano particles is remarkably improved, and the silver nano particles have longer-acting antibacterial activity; the antibacterial compound is applied to the polylactic acid fiber membrane, so that the polylactic acid fiber membrane has the characteristics of lasting and effective antibacterial activity, good air permeability, high stability, broad-spectrum antibacterial property and biodegradability.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Example 1
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.5g C60 powder, weighing 50ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 0.5g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, replacing the ice water bath with a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 8 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30min, wherein the laser irradiation power is 1W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 60ml of graphene quantum dot suspension, dropwise adding 0.005mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.08mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:2: 2.
(3) Carrying out ultrasonic treatment on 0.5g of silver-loaded graphene quantum dotsStirring (1000W ultrasonic power, 500rpm stirring speed) and dispersing in ethanol; then adding water and ammonia water in a volume ratio of 5:1, uniformly stirring, adding ethyl orthosilicate in a mass ratio of 2:1 to the silver-loaded graphene quantum dots, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃ for 3 hours; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: adding 0.005g of graphite oxide into 5mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.3g of silver-loaded graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer with microwave power of 400W, and reacting at 240 ℃ for 90 min; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, with the pore size of about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.2mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 30min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Example 2
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.6g C60 powder, weighing 80ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 1g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice-water bath, changing the ice-water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 6 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 40min, wherein the laser irradiation power is 1.3W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 50ml of graphene quantum dot suspension, dropwise adding 0.003mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.05mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:3: 2.
(3) Dispersing 0.3g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (800W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 4:1, stirring uniformly, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 2:1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1.2 hours, centrifuging, sequentially cleaning with acetone and deionized water to obtain a precipitate, and putting the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: adding 0.008g of graphite oxide into 8mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, 300rpm stirring speed) and adding 0.2g of silver-loaded graphene quantum dots, continuously ultrasonically stirring for 30min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer with the microwave power of 300W, and reacting at 220 ℃ for 60 min; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.5mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 30min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Example 3
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a graphene quantum dot suspension: weighing 0.8g C60 powder, weighing 100ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 3g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice-water bath, changing the ice-water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 5 hours; quickly adding 100ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 30min, wherein the laser irradiation power is 2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 60ml of graphene quantum dot suspension, dropwise adding 0.001mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.01mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 4:3: 2.
(3) 0.5g of silver-loaded graphene quantum dotsDispersing the mixture in ethanol by ultrasonic stirring (500W ultrasonic power, 500rpm stirring speed); then adding water and ammonia water in a volume ratio of 3:1, stirring uniformly, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1:1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1 hour, centrifuging, sequentially cleaning with acetone and deionized water to obtain a precipitate, and putting the precipitate at 90 DEG CoDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
（4）SiO2Surface treatment of the coated silver-loaded graphene quantum dots: adding 0.01g of graphite oxide into 10mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.1g of silver-loaded graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer, reacting at 200 ℃ for 90min under the microwave power of 200W; cooling, filtering and drying to obtain the SiO with surface treatment2And coating the silver-loaded graphene quantum dots.
(5) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.8mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the SiO prepared in the step (4)2Coating silver-loaded graphene quantum dots, ultrasonically stirring for 30min, then transferring into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Comparative example 1
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps: weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.8mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, dropwise adding 0.001mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.01mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; and aging, cleaning and drying to obtain the antibacterial composite material.
Comparative example 2
A preparation method of a porous graphene silver-loaded antibacterial composite material comprises the following steps:
(1) preparing a silver nitrate solution with the concentration of 0.001mol/L, controlling the reaction temperature to be 50 ℃, dropwise adding trisodium citrate dihydrate with the concentration of 0.01mol/L, and ultrasonically stirring for 90min, wherein the volume ratio of the silver nitrate solution to the trisodium citrate dihydrate is 3: 2; then adding water and ammonia water in a volume ratio of 3:1, stirring uniformly, adding ethyl orthosilicate (the mass ratio of the ethyl orthosilicate to the silver-loaded graphene quantum dots is 1:1, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃, reacting for 1 hour, centrifuging, sequentially cleaning with acetone and deionized water to obtain a precipitate, and putting the precipitate at 90 DEG CoDrying for 3h to obtain Ag/SiO2。
(2) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.8mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, and adding the Ag/SiO prepared in the step (2)2Ultrasonically stirring for 30min, then moving into a polytetrafluoroethylene reaction kettle, and preserving the temperature for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
The specific process and steps of the antibacterial activity evaluation of the antibacterial composite material prepared by the invention are as follows:
the bacteria tested were staphylococcus aureus and escherichia coli, respectively; test methods with reference to Minimum Inhibitory Concentration (MIC) (Xiaoaininghibitory concentration, Xiaohao Tan, Aili Yu, Jinglin Zhang, Jianhao Liu, Wenjie Mai, Zhenyou Jiang, Sodium 1-naphthanenesulfonate-functionalized reduced graphene oxide stabilize the silver nanoparticles with lower cytotoxicity and long-term antibacterial activity chemistryistry-An Asian journal, 2012, 7(7):1664-6pieces/mL, followed by shaking culture at 37 ℃ for 24 hours, the results were observed as shown in Table 1. The test tube without the antibacterial sample is used as a control tube, the liquid of the test tube with aseptic growth is transparent, and the antibacterial agent of the test tube without the antibacterial sample is measured as the Minimum Inhibitory Concentration (MIC) of the antibacterial agent.
Table 1: antibacterial performance of antibacterial composite materials of examples 1-3 and comparative examples 1 and 2
And (3) long-acting performance test: an erlenmeyer flask was placed in a constant temperature water bath at 40 ℃, 1g of the antibacterial composite material sample prepared in each example and comparative example and 200mL of saline (0.9 mass%) were added to the erlenmeyer flask, and samples were taken after soaking in water for 6, 24, and 72 hours, respectively, to determine the minimum inhibitory concentration, as shown in table 2.
Table 2: long-acting antibacterial activity of antibacterial composite materials of examples 1-3 and comparative examples 1 and 2
Example 4
A preparation method of an antibacterial composite fiber membrane comprises the following steps:
(1) preparing an antibacterial spinning solution: weighing 4mL of polyethylene glycol 400 in a conical flask with a plug, heating to 50 ℃, and adding 14mL of dichloromethane; adding PLLA with the molecular weight of 10 ten thousand, wherein the mass fraction of the PLLA is 10%, and magnetically stirring for 2h at room temperature; 3mL of the antibacterial compound dispersion liquid of the example 2 with the concentration of 0.04mol/l is dropwise added under the stirring of 200 rpm; continuously stirring for 40min to obtain antibacterial spinning solution;
(2) and (3) preparing the antibacterial composite nanofiber membrane by electrostatic spinning. The electrostatic spinning equipment consists of a high-voltage digital display direct-current power supply, a micro-injection pump, a solution storage, a capillary tube and a collecting device, and the invention adopts a grounded metal aluminum foil as the collecting device. The electrostatic spinning specifically comprises the following steps: the prepared solution is poured into a solution storage (20 mL syringe) and fixed on a micro-injection pump, a ground needle head is used as a capillary for jetting a trickle, the capillary is connected with the anode of a high-voltage power supply, a metal aluminum foil is connected with the cathode of the high-voltage power supply, and the dosage of the solution is controlled by the micro-injection pump. The parameters of the electrostatic spinning process are that the applied voltage is 22 +/-2 kV, the receiving distance is 12cm, the advancing speed is 1mL/h, the air humidity is 10 percent, the temperature is room temperature, the inner diameter of a needle used for spinning is 0.6mm, and the needle is completely dried in the air after receiving fibers by using aluminum foil.
Example 5
The preparation process is based on example 4, with the difference that: the antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.6g C60 powder, weighing 50-100 ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 1g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice water bath, changing the ice water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 7 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 45min, wherein the laser irradiation power is 1.2W.
(2) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) 60ml of graphene quantum dot suspension, dropwise adding 0.003mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.05mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:3: 2.
(3) Dispersing 0.3g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (1000W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 4:1, uniformly stirring, adding ethyl orthosilicate in a mass ratio of 2:1 to the silver-loaded graphene quantum dots, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃ for 1 hour; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(4) Adding 0.2mol/L titanium source (the titanium source is ammonium fluotitanate) into 1mol/L sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (3)2Coating the silver-loaded graphene quantum dots, heating to 100 ℃, reacting for 3 hours, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6 hours, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(5) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.008g of graphite oxide into 8mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.2g of silver-loaded/titanium dioxide graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer, reacting at 220 ℃ for 60min and with the microwave power of 300W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(6) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.5mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, adding the silver/titanium dioxide graphene quantum dots prepared in the step (5), ultrasonically stirring for 30min, then moving into a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Example 6
The preparation process is based on example 4, with the difference that: the antibacterial compound is prepared by the following method:
(1) preparing a graphene quantum dot suspension: weighing 0.7g C60 powder, weighing 80ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 2g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice-water bath, changing the ice-water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 6 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 45min, wherein the laser irradiation power is 1.5W.
(2) Weighing zinc oxide quantum dots (with the particle size of about 2-5 nm) to prepare a dispersion liquid with the concentration of 0.8mg/ml, wherein the solvent is water; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 100ml of zinc oxide dispersion liquid, dropwise adding half of the graphene quantum dot suspension liquid prepared in the step (1), and continuously ultrasonically stirring for 60 min; centrifuging, cleaning and drying to obtain the graphene quantum dots loaded with zinc oxide.
(3) Surface treatment of graphene quantum dots loaded with zinc oxide: adding 0.008g of graphite oxide into 10mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.1g of graphene quantum dots loaded with zinc oxide, continuously ultrasonically stirring for 20min, moving to a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing in a microwave-assisted hydrothermal synthesizer with microwave power of 300W, and reacting at 220 ℃ for 60 min; and cooling, filtering and drying to obtain the surface-treated graphene quantum dots loaded with zinc oxide.
(4) Preparing silver-loaded graphene quantum dots: ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) the other half of the graphene quantum dot suspension, dropwise adding a silver nitrate solution with the concentration of 0.003mol/L, controlling the reaction temperature to be 50 ℃, dropwise adding trisodium citrate dihydrate with the concentration of 0.05mol/L, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:3: 2.
(5) Dispersing 0.3g of silver-loaded graphene quantum dots in ethanol by ultrasonic stirring (1000W ultrasonic power, stirring speed of 500 rpm); then adding water and ammonia water in a volume ratio of 4:1, uniformly stirring, adding ethyl orthosilicate in a mass ratio of 2:1 to the silver-loaded graphene quantum dots, adjusting the pH value to 9-10, reacting at the temperature of 20-25 ℃ for 1 hour; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots.
(6) Adding 0.2mol/L titanium source (the titanium source is ammonium fluotitanate) into 1mol/L sulfuric acid solution, and uniformly mixing; adding the SiO prepared in the step (5)2Coating the silver-loaded graphene quantum dots, heating to 100 ℃, reacting for 3 hours, adjusting the pH value to 7 by using concentrated ammonia water solution, aging for 6 hours, cleaning, and drying to obtain the silver-loaded/titanium dioxide graphene quantum dots.
(7) Carrying out surface treatment on the silver/titanium dioxide graphene quantum dots: adding 0.008g of graphite oxide into 8mL of Dispersant (DMSO), ultrasonically stirring (500W ultrasonic power, stirring speed of 300 rpm) and adding 0.2g of silver-loaded/titanium dioxide graphene quantum dots, continuously ultrasonically stirring for 30min, moving into a microwave hydrothermal reaction kettle (50 mL) with a polytetrafluoroethylene lining, sealing, placing into a microwave-assisted hydrothermal synthesizer, reacting at 220 ℃ for 60min and with the microwave power of 300W; and cooling, filtering and drying to obtain the silver/titanium dioxide loaded graphene quantum dots with the surface treated.
(8) Weighing porous graphene (2-5 layers, the pore size is about 3-6 nm) to prepare a graphene dispersion solution with the concentration of 0.5mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring (1000W ultrasonic power, stirring speed of 800 rpm) 80ml of graphene dispersion solution, adding the zinc oxide-loaded graphene quantum dots prepared in the step (3) and the silver/titanium dioxide-loaded graphene quantum dots prepared in the step (7) (the mass ratio of the two is 2: 3), ultrasonically stirring for 30min, then moving to a polytetrafluoroethylene reaction kettle, and preserving heat for 30min at 100 ℃; and cooling, centrifuging, cleaning and drying to obtain the antibacterial composite material.
Comparative example 3
The preparation process is based on example 4, with the difference that: the antibacterial compound is TCC.
Comparative example 4
The preparation process is based on example 4, with the difference that: the antibacterial compound is a nano-silver antibacterial agent.
The prepared nano-film adopts an improved oscillating flask method to detect the antibacterial performance of the nano-fiber film. The antibacterial rate is evaluated according to GB-15979-2002 sanitation Standard for Disposable sanitary articles.
The uniformity of the antibacterial performance was evaluated by selecting 100 areas on the same fiber film and performing a sterilization test, and analyzing the uniformity of the measured data by uniformity =100 (1-standard deviation/average), wherein the mark was ▲ when the uniformity was greater than 97%, the mark was star when the uniformity was greater than 90% and less than 97%, and the mark was gamma when the uniformity was less than 90%.
The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should fall within the protection scope of the present invention.
Claims (1)
1. A preparation method of an antibacterial composite fiber membrane comprises the following steps:
(1) preparing an antibacterial spinning solution: weighing 4mL of polyethylene glycol 400 in a conical flask with a plug, heating to 50 ℃, and adding 14mL of dichloromethane; adding PLLA with the molecular weight of 10 ten thousand, wherein the mass fraction of the PLLA is 10%, and magnetically stirring for 2h at room temperature; dropwise adding 3mL of antibacterial compound dispersion liquid with the concentration of 0.04mol/l under the stirring of 200 rpm; continuously stirring for 40min to obtain antibacterial spinning solution;
(2) preparing an antibacterial composite fiber membrane by electrostatic spinning; the electrostatic spinning equipment consists of a high-voltage digital display direct-current power supply, a micro-injection pump, a solution storage device, a capillary tube and a collecting device, and a grounded metal aluminum foil is used as the collecting device; the electrostatic spinning specifically comprises the following steps: pouring the prepared antibacterial spinning solution into a solution storage device and fixing the solution on a micro-injection pump, adopting a flat-ground needle head as a capillary for jetting a trickle, connecting the flat-ground needle head with the anode of a high-voltage digital-display direct-current power supply, connecting a metal aluminum foil with the cathode of the high-voltage digital-display direct-current power supply, and controlling the ejection amount of the solution by using the micro-injection pump; the parameters of the electrostatic spinning process are that the applied voltage is 22 +/-2 kV, the receiving distance is 12cm, the advancing speed is 1mL/h, the air humidity is 10 percent, the temperature is room temperature, the inner diameter of a needle used for spinning is 0.6mm, and the fiber is completely dried in the air after being received by a metal aluminum foil; wherein,
the preparation method of the antibacterial compound in the antibacterial compound dispersion liquid comprises the following steps:
(A) preparing a graphene quantum dot suspension: weighing 0.6g C60 powder, weighing 80ml of 98% concentrated sulfuric acid, mixing the C60 powder and the concentrated sulfuric acid in a beaker, putting the beaker in an ice-water bath, and stirring at the speed of 500rpm to obtain a mixed solution; weighing 1g of potassium permanganate powder, and slowly adding the potassium permanganate powder into the mixed solution; removing the ice-water bath, changing the ice-water bath into a water bath, keeping the temperature of the water bath at 30-40 ℃, and reacting for 6 hours; rapidly adding 200ml of pure water, filtering, and dialyzing for 3 days by using a dialysis bag with the molecular weight cutoff of 1000 to obtain graphene quantum dot suspension; stirring the graphene quantum dot suspension at the speed of 100rpm, and simultaneously carrying out laser irradiation for 40min, wherein the laser irradiation power is 1.3W;
(B) preparing silver-loaded graphene quantum dots: ultrasonically stirring 50ml of graphene quantum dot suspension, dropwise adding 0.003mol/L silver nitrate solution, controlling the reaction temperature to be 50 ℃, dropwise adding 0.05mol/L trisodium citrate dihydrate, and continuously ultrasonically stirring for 90 min; aging, cleaning and drying to obtain silver-loaded graphene quantum dots; the volume ratio of the graphene quantum dot suspension, the silver nitrate solution and the trisodium citrate dihydrate is 3:3: 2;
(C) ultrasonically stirring and dispersing 0.3g of silver-loaded graphene quantum dots in ethanol; then adding water and ammonia water in a volume ratio of 4:1, stirring uniformly, adding tetraethoxysilane and silicic acidThe mass ratio of the ethyl ester to the silver-loaded graphene quantum dots is 2:1, the pH value is adjusted to 9-10, the reaction temperature is 20-25 ℃, and the reaction time is 1.2 hours; centrifuging and washing with acetone and deionized water in sequence to obtain precipitate; the precipitate is taken up at 90oDrying for 3h under C to obtain SiO2Coated silver-loaded graphene quantum dots;
（D）SiO2surface treatment of the coated silver-loaded graphene quantum dots: 0.008g of graphite oxide is added to 8mL of dispersant, stirred with ultrasound and 0.2g of SiO is added2Continuously ultrasonically stirring the coated silver-loaded graphene quantum dots for 30min, transferring the coated silver-loaded graphene quantum dots into a microwave hydrothermal reaction kettle with a polytetrafluoroethylene lining, sealing the kettle, placing the kettle into a microwave-assisted hydrothermal synthesizer, and reacting the kettle for 60min at 220 ℃ with the microwave power of 300W; cooling, filtering and drying to obtain the SiO with surface treatment2Coated silver-loaded graphene quantum dots;
(E) weighing 2-5 layers of porous graphene with the pore size of 3-6 nm and the layer size of 100-500 nm to prepare a graphene dispersion solution with the concentration of 0.5mg/ml, wherein the solvent is water, acetone or dimethyl sulfoxide; ultrasonically stirring 80ml of graphene dispersion solution, and adding the SiO prepared in the step (D)2Ultrasonically stirring the coated silver-loaded graphene quantum dots for 30min, then transferring the coated silver-loaded graphene quantum dots into a reaction kettle with a polytetrafluoroethylene lining, and preserving the temperature for 30min at 100 ℃; cooling, centrifuging, cleaning and drying to obtain the antibacterial compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748681.9A CN106192214B (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of antibacterial composite fibers film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748681.9A CN106192214B (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of antibacterial composite fibers film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106192214A CN106192214A (en) | 2016-12-07 |
| CN106192214B true CN106192214B (en) | 2018-08-03 |
Family
ID=57527367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610748681.9A Active CN106192214B (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of antibacterial composite fibers film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106192214B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107083577A (en) * | 2017-05-19 | 2017-08-22 | 江苏华昌织物有限公司 | A kind of preparation method of composite high-molecular fiber for antibacterial screen cloth |
| CN107441545B (en) * | 2017-08-24 | 2020-04-28 | 陕西科技大学 | Preparation method of skin adhesion type nano silver ion antibacterial dressing |
| CN108130626A (en) * | 2017-12-22 | 2018-06-08 | 合肥洁诺无纺布制品有限公司 | A kind of moisture sorption effect good draping surgery acid fiber by polylactic preparation method |
| CN108854570A (en) * | 2018-07-11 | 2018-11-23 | 济南开发区星火科学技术研究院 | A kind of the fresh air system modified antibacterial water permeable membrane of graphene and preparation method |
| CN108823795A (en) * | 2018-07-13 | 2018-11-16 | 合肥洁诺医疗用品有限公司 | A kind of anti-radiation antibacterial nonwoven cloth |
| CN108914375A (en) * | 2018-09-21 | 2018-11-30 | 佛山市森昂生物科技有限公司 | A kind of preparation method of long acting antibiotic polylactic acid fiber membrane |
| CN112030352A (en) * | 2020-08-11 | 2020-12-04 | 太原理工大学 | Preparation method of novel antibacterial catheter outer-layer fiber membrane |
| CN118461326A (en) * | 2022-04-07 | 2024-08-09 | 施登娥 | Preparation method of high scratch-resistant fiber film |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1953286A1 (en) * | 2007-02-01 | 2008-08-06 | Nisshinbo Industries, Inc. | Fabric and mask |
| CN102086565A (en) * | 2010-12-08 | 2011-06-08 | 江南大学 | Polylactic acid antibacterial nanofiber membrane and preparation method thereof |
| CN102872889A (en) * | 2012-10-10 | 2013-01-16 | 江苏大学 | Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same |
| CN103252228A (en) * | 2013-06-08 | 2013-08-21 | 江苏悦达墨特瑞新材料科技有限公司 | Preparation method of composite nanomaterial of nano ZnO and graphene nanosheet |
| CN103480399A (en) * | 2013-09-22 | 2014-01-01 | 江苏大学 | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof |
| CN103774345A (en) * | 2014-01-24 | 2014-05-07 | 中国科学院重庆绿色智能技术研究院 | Preparation method for efficient low-impedance antibacterial air purification filter membrane |
| CN104211050A (en) * | 2014-07-15 | 2014-12-17 | 中国科学技术大学 | Preparation method of suspension liquid and powder of graphene quantum dot |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| CN104941643A (en) * | 2015-06-16 | 2015-09-30 | 北京科技大学 | Preparation method of Ag-GQDs(Graphene Quantum Dots)/ZnO ternary photocatalyst |
| CN105839291A (en) * | 2016-04-25 | 2016-08-10 | 苏州宝丽洁纳米材料科技股份有限公司 | Antibacterial nano-fiber non-woven material and preparation method |
-
2016
- 2016-08-29 CN CN201610748681.9A patent/CN106192214B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1953286A1 (en) * | 2007-02-01 | 2008-08-06 | Nisshinbo Industries, Inc. | Fabric and mask |
| CN102086565A (en) * | 2010-12-08 | 2011-06-08 | 江南大学 | Polylactic acid antibacterial nanofiber membrane and preparation method thereof |
| CN102872889A (en) * | 2012-10-10 | 2013-01-16 | 江苏大学 | Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same |
| CN103252228A (en) * | 2013-06-08 | 2013-08-21 | 江苏悦达墨特瑞新材料科技有限公司 | Preparation method of composite nanomaterial of nano ZnO and graphene nanosheet |
| CN103480399A (en) * | 2013-09-22 | 2014-01-01 | 江苏大学 | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof |
| CN103774345A (en) * | 2014-01-24 | 2014-05-07 | 中国科学院重庆绿色智能技术研究院 | Preparation method for efficient low-impedance antibacterial air purification filter membrane |
| CN104211050A (en) * | 2014-07-15 | 2014-12-17 | 中国科学技术大学 | Preparation method of suspension liquid and powder of graphene quantum dot |
| CN104291321A (en) * | 2014-07-28 | 2015-01-21 | 长春工业大学 | Preparation method for graphene quantum dot film |
| CN104941643A (en) * | 2015-06-16 | 2015-09-30 | 北京科技大学 | Preparation method of Ag-GQDs(Graphene Quantum Dots)/ZnO ternary photocatalyst |
| CN105839291A (en) * | 2016-04-25 | 2016-08-10 | 苏州宝丽洁纳米材料科技股份有限公司 | Antibacterial nano-fiber non-woven material and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106192214A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106192214B (en) | A kind of preparation method of antibacterial composite fibers film | |
| Athauda et al. | Tuning physical and optical properties of ZnO nanowire arrays grown on cotton fibers | |
| CN103361885B (en) | A kind of preparation method of antibacterial fibroin fiber film | |
| CN106317386A (en) | Preparing method of antibacterial polylactic acid material | |
| CN102525827A (en) | Method for preparing medical titanium material with long-acting antibacterial property and good biocompatibility | |
| CN106364124B (en) | A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane | |
| CN115318291B (en) | Preparation method and application of copper nanoparticle-carbon nitride photocatalysis sterilization composite material | |
| CN102294052B (en) | Preparation method of medical high polymer based silver nano material | |
| CN106349874A (en) | Anticorrosion coating preparing method | |
| CN111034720A (en) | Preparation method of zinc oxide-metal organic framework composite antibacterial material | |
| CN106366590A (en) | Preparing method of polylactic acid photochromic master batch | |
| CN106221316A (en) | A kind of preparation method of waterborne antibacterial deodorization inorganic coating | |
| CN109675100A (en) | Polylactic acid-zinc oxide micrometer nanometer hierarchical structure composite micro-sphere material and application | |
| CN104194233B (en) | PAA-calcium carbonate composite Nano rod and its preparation method | |
| CN106350893A (en) | Antibacterial and radiation resistant composite fiber membrane preparing method | |
| CN106283878A (en) | A kind of preparation method of antibiotic antistatic corrugated board | |
| CN106120151B (en) | It is a kind of except the preparation method of formaldehyde composite cellulosic membrane | |
| CN104227017A (en) | Preparation method of silver nanoparticle with controllable particle size | |
| CN106366849A (en) | Preparation method of antibacterial, anti-radiation and anticorrosion paint | |
| CN106189717A (en) | A kind of preparation method of photochromic anticorrosive paint | |
| CN106221556A (en) | A kind of deodorization ultraviolet-curing paint and preparation method thereof | |
| CN106189400A (en) | A kind of preparation method of the photochromic inorganic coating of aqueous | |
| CN106349663A (en) | Preparing method for polylactic acid antibacterial radiation-resistant masterbatch | |
| CN106349627A (en) | Method for antibacterial resin composit and preparing method thereof | |
| CN114847302A (en) | Core/shell type nano silver-based composite material and preparation method and antibacterial application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191204 Address after: Taihu County, Anhui city of Anqing Province Jin Xi Zhen 246400 Patentee after: Taihu County market supervision and Inspection Institute (Taihu County functional membrane Testing Institute) Address before: Foshan City, Guangdong province 528500 city streets Gaoming District, Taixing Taixing street, Lane seven, No. 26, 8 Patentee before: Gaoming District of Foshan city is Runying Technology Co. Ltd. |
|
| TR01 | Transfer of patent right |