CN106192214A - A kind of preparation method of antibacterial composite fibers film - Google Patents
A kind of preparation method of antibacterial composite fibers film Download PDFInfo
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- CN106192214A CN106192214A CN201610748681.9A CN201610748681A CN106192214A CN 106192214 A CN106192214 A CN 106192214A CN 201610748681 A CN201610748681 A CN 201610748681A CN 106192214 A CN106192214 A CN 106192214A
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- quantum dot
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- graphene
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- 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
Abstract
The invention discloses the preparation method of a kind of antibacterial composite fibers film, it comprises the following steps: the preparation of (1) antibacterial spinning solution: weigh appropriate PEG400 in tool plug conical flask, it is warming up to 50 DEG C, adding dichloromethane, wherein dichloromethane is 7: 2 with the volume ratio of PEG400；Add molecular weight 100,000 PLLA, at room temperature magnetic agitation 2h；The lower dropping concentration of 100 ~ 300rpm stirring is the antibiotic complex dispersion liquid of 0.01 ~ 0.1mol/l；Continue stirring 30 ~ 40min, make antibacterial spinning solution；(2) electrostatic spinning prepares antibacterial composite nano-fiber membrane.By in special antibiotic complex application to polylactic acid fiber membrane so that it is have the most effective antibacterial activity, good permeability, stability height, broad-spectrum antiseptic, biodegradable characteristic.
Description
Technical field
The present invention relates to composite fibre technology field, particularly relate to the preparation side of a kind of antibacterial composite fibers film
Method.
Background technology
It is big that nano fibrous membrane has surface area, and porosity is high, short texture, it is possible to function as required is pre-designed group
Become, analog cell epimatrix, the advantages such as preparation method is simple and have huge application potential in a lot of fields, at food
The fields such as product, medicine, daily use chemicals have had and have been widely applied very much.The nanofiber especially prepared with natural high polymer for spinning liquid
Film, in addition to having above feature, also has the biocompatibility of excellence, biodegradability and recyclability etc..Static Spinning
Silk is the simplest, the method for high-efficiency production of nano fibrous membrane.
Silver-carrying nano granule/composite cellulosic membrane poor biocompatibility, preparation process that prior art prepares have by-product produce
Coin into fiber membrane structure and be corrupted such that the application of anti-bacterial fibre film is limited.And owing to nanometer silver is in granular form, granularity is for receiving
Meter level is other, often can only be gathered in the specific part of fibrous membrane, it is impossible to be evenly distributed on surface, thus the antibacterial effect affected；
On the other hand, nanometer silver and fibrous membrane cannot be combined closely and (particularly when nano-Ag particles content increases, be susceptible to reunite
Phenomenon), the most easily come off, thus affect service life and antibacterial effect.
Summary of the invention
The technical problem to be solved there is provided the preparation method of a kind of antibacterial composite fibers film.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of antibacterial composite fibers film, it comprises the following steps:
(1) preparation of antibacterial spinning solution: weigh appropriate PEG400 in tool plug conical flask in, be warming up to 50 DEG C, add
Entering dichloromethane, wherein dichloromethane is 7: 2 with the volume ratio of PEG400；Add molecular weight 100,000 PLLA, in room temperature
Lower magnetic agitation 2h；The lower dropping concentration of 100 ~ 300rpm stirring is the antibiotic complex dispersion liquid of 0.01 ~ 0.1mol/l；Continue to stir
Mix 30 ~ 40min, make antibacterial spinning solution；(2) electrostatic spinning prepares antibacterial composite nano-fiber membrane.Electrospinning device by
High pressure digital display DC power supply, micro-injection pump, solution storage device, capillary tube, collection device forms, and the present invention uses the gold of ground connection
Belong to aluminium foil as collection device.Particularly as follows: the solution configured is poured into solution storage device, (20mL injects described electrostatic spinning
Device) in and be fixed on micro-injection pump, use the syringe needle that polishes as the capillary tube of injection thread, just connecting high voltage power supply
Pole, metal aluminum foil connects the negative pole of high voltage power supply, and the agent output of solution is by micro-injection pump control.Static Spinning procedure parameter is for executing
Making alive 22 ± 2kV, receiving range 12cm, fltting speed is 1mL/h, and air humidity is 10%, and temperature is room temperature, spinning institute
With syringe needle internal diameter 0.6mm, the most thoroughly it is dried after receiving fiber with aluminium foil.
Described antibiotic complex prepares by the following method:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 60 ~
120min；Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load silver, continues ultrasonic agitation 10 ~ 30min, moves to the microwave hydrothermal that liner is politef
In reactor (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, at 200 ~ 240 DEG C
Reaction 60 ~ 90min；Cooling, filter, dry surface process SiO2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and be configured to the graphite that concentration is 0.2 ~ 0.8mg/ml
Alkene dispersion soln, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W ultrasonic power, 600 ~ 800rpm stirs ultrasonic agitation
Mix speed) 80 ~ 100ml graphene dispersion solution, add the SiO that step (4) prepares2Cladding carries silver graphene quantum dot, ultrasonic
Stirring 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal,
Clean, dry to obtain antimicrobial composite material.
Described antibiotic complex prepares by the following method:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 60 ~
120min；Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(4) 0.1 ~ 0.3mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (3) prepares2Cladding carries silver graphene quantum dot, heats up
To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after be aged 6 hours, clean, be dried, obtain carrying silver-colored/
Titanium dioxide graphene quantum dot.
(5) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and be configured to the graphite that concentration is 0.2 ~ 0.8mg/ml
Alkene dispersion soln, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W ultrasonic power, 600 ~ 800rpm stirs ultrasonic agitation
Mix speed) 80 ~ 100ml graphene dispersion solution, add the load silver/titanium dioxide graphene quantum dot that step (5) prepares, ultrasonic
Stirring 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal,
Clean, dry to obtain antimicrobial composite material.
Described antibiotic complex prepares by the following method:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is
Water；Ultrasonic agitation (500 ~ 1000W ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, dropping step
Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature
Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 M sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis-
Titanium oxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and be configured to the graphite that concentration is 0.2 ~ 0.8mg/ml
Alkene dispersion soln, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000W ultrasonic power, 600 ~ 800rpm stirs ultrasonic agitation
Mix speed) 80 ~ 100ml graphene dispersion solution, add graphene quantum dot and the step of the load zinc oxide that step (3) prepares
(7) load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation 10 ~ 30min prepared, then moves
To the reactor of politef, at 80 ~ 120 DEG C, it is incubated 15 ~ 30min；Cooling, centrifugal, clean, dry antibacterial compound
Material.
There is advantages that
Antibiotic complex method of the present invention uses the graphene quantum dot after laser irradiation as the carrier of silver, is then coated with dioxy
SiClx thin layer, surface processes, is finally attached on porous graphene, can preferably load and fix Nano silver grain, prevent
It is reunited, and significantly improves the stability of Nano silver grain, makes Nano silver grain have more efficient antibacterial activity；This is antibacterial multiple
Compound is applied to polylactic acid fiber membrane so that it is have the most effective antibacterial activity, and good permeability, stability are high, wide spectrum resists
Bacterium, biodegradable characteristic.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g C60 powder, measure the dense sulfur that 50ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 0.5g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
Bath temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then saturating with the bag filter that molecular cut off is 1000
Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation
30min, laser irradiation power is 1W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.08mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:2.
(3) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；It is centrifuged
And clean acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2The load of cladding
The graphene quantum dot of silver.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.005g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.3g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 90min at 240 DEG C；Cooling, filters, dries to obtain surface
The SiO of reason2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) to be configured to the Graphene that concentration is 0.2mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml stone
Ink alkene dispersion soln, adds the SiO that step (4) prepares2Cladding carries silver graphene quantum dot, ultrasonic agitation 30min, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.6g C60 powder, measure the dense sulfur that 80ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 40min, swash
Photoirradiation power is 1.3W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.05mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (800W ultrasonic power, 500rpm mixing speed) point of 0.3g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of ink alkene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1.2 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.008g graphite oxide joins the dispersion of 8mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.2g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, and dries to obtain surface process
SiO2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) to be configured to the Graphene that concentration is 0.5mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml stone
Ink alkene dispersion soln, adds the SiO that step (4) prepares2Cladding carries silver graphene quantum dot, ultrasonic agitation 30min, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g C60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 5h；Rapidly join 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash
Photoirradiation power is 2W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.01mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:3:2.
(3) by the graphene quantum dot ultrasonic agitation (500W ultrasonic power, 500rpm mixing speed) point of 0.5g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of ink alkene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged
And clean acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2The load of cladding
The graphene quantum dot of silver.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.01g graphite oxide joins the dispersion of 10mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.1g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 90min at 200 DEG C；Cooling, filters, and dries to obtain surface process
SiO2Cladding carries silver graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) to be configured to the Graphene that concentration is 0.8mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml stone
Ink alkene dispersion soln, adds the SiO that step (4) prepares2Cladding carries silver graphene quantum dot, ultrasonic agitation 30min, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 1
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps: weigh porous graphene (2 ~
5 layers, hole size about 3 ~ 6nm) it is configured to the graphene dispersion solution that concentration is 0.8mg/ml, solvent is water, acetone or dimethyl
Sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, dropping concentration is
0.001mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/L bis-citric acid monohydrate trisodium,
Continue ultrasonic agitation 90min；Ageing, cleans, dries to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) compound concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/L
Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, the volume ratio of silver nitrate solution and two citric acid monohydrate trisodiums is 3:2；Afterwards
Add water and the ammonia of volume ratio 3:1, be stirring evenly and then adding into the tetraethyl orthosilicate (quality with the graphene quantum dot of load silver
Ratio is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged and successively with acetone and going
Ionized water cleans and obtains precipitation；This is deposited in 90o3h it is dried, to obtain Ag/SiO under C2。
(2) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) to be configured to the Graphene that concentration is 0.8mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml stone
Ink alkene dispersion soln, adds the Ag/SiO that step (2) prepares2, ultrasonic agitation 30min, then move to the reaction of politef
In still, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Detailed process and step that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated are as follows:
The antibacterial of test is respectively staphylococcus aureus and escherichia coli；With reference to minimal inhibitory concentration (minimal
Inhibitory concentration, MIC) method of testing (Xiang Cai, Shaozao Tan, Aili Yu,
Jinglin Zhang, Jiahao Liu, Wenjie Mai, Zhenyou Jiang. Sodium1-
naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver
nanoparticles with lower cytotoxicity and long-term antibacterial
Activity.Chemistry-An Asian Journal. 2012,7 (7): 1664-1670.), first weigh with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material MH meat soup to the most serial dilute
Release variable concentrations, be added separately in the MH culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/mL,
Then shaken cultivation 24h at 37 DEG C, observes its result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, nothing
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of the longest tube.
Table 1: embodiment 1 ~ 3 and the anti-microbial property of comparative example 1,2 antimicrobial composite material
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, adds prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200mL saline (0.9mass%), and in water, soak 6 respectively, 24, sample after 72h, measure it
Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite material
Embodiment 4
A kind of preparation method of antibacterial composite fibers film, it comprises the following steps:
(1) preparation of antibacterial spinning solution: weigh 4mL PEG400 in tool plug conical flask in, be warming up to 50 DEG C, add
14mL dichloromethane；The mass fraction adding molecular weight 100,000 PLLA, PLLA is 10%, at room temperature magnetic agitation 2h；
The lower dropping 3mL concentration of 200rpm stirring is the embodiment 2 antibiotic complex dispersion liquid of 0.04mol/l；Continue stirring 40min, system
Become antibacterial spinning solution；
(2) electrostatic spinning prepares antibacterial composite nano-fiber membrane.Electrospinning device is by high pressure digital display DC power supply, micro-injection
Pump, solution storage device, capillary tube, collection device forms, and the present invention uses the metal aluminum foil of ground connection as collection device.Described quiet
Electrospun particularly as follows: the solution configured poured in solution storage device (20mL syringe) and be fixed on micro-injection pump,
Using the syringe needle polished as the capillary tube of injection thread, connect the positive pole of high voltage power supply, metal aluminum foil connects high voltage power supply
Negative pole, the agent output of solution is by micro-injection pump control.Static Spinning procedure parameter is for applying voltage 22 ± 2kV, receiving range
12cm, fltting speed is 1mL/h, and air humidity is 10%, and temperature is room temperature, and used by spinning, syringe needle internal diameter 0.6mm, uses aluminium foil
The most thoroughly it is dried after receiving fiber.
Embodiment 5
Preparation method based on embodiment 4, difference is: described antibiotic complex prepares by the following method:
(1) prepare graphene quantum dot suspension: weigh 0.6g C60 powder, measure 50 ~ 100ml mass fraction be 98% dense
Sulphuric acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously,
Mixed liquor；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
Bath temperature 30 ~ 40 DEG C, reacts 7h；Rapidly join 200ml pure water, filter, then saturating with the bag filter that molecular cut off is 1000
Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation
45min, laser irradiation power is 1.2W.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.05mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(4) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (3) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(5) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face processes.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) to be configured to the Graphene that concentration is 0.5mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml stone
Ink alkene dispersion soln, adds the load silver/titanium dioxide graphene quantum dot that step (5) prepares, ultrasonic agitation 30min, then moves
To the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Embodiment 6
Preparation method based on embodiment 4, difference is: described antibiotic complex prepares by the following method:
(1) prepare graphene quantum dot suspension: weigh 0.7g C60 powder, measure the dense sulfur that 80ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash
Photoirradiation power is 1.5W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, dropping step (1) prepares
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) to be configured to the Graphene that concentration is 0.5mg/ml and divide
Dissipating solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml stone
Ink alkene dispersion soln, adds the graphene quantum dot of the load zinc oxide that step (3) prepares and load silver/bis-that step (7) is prepared
Titanium oxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min, then moves to the reactor of politef
In, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 3
Preparation method based on embodiment 4, difference is: described antibiotic complex is TCC.
Comparative example 4
Preparation method based on embodiment 4, difference is: described antimicrobial compound is nano silver antimicrobials.
Made nanometer film uses the anti-microbial property of the shake flasks method detection nano fibrous membrane of improvement.According to GB-15979-
2002 " Disposable Sanitary Accessory sanitary standard " evaluates antibiotic rate.
Antibacterial Evaluation for Uniformity: choose 100 regions on same fibrous membrane and carry out sterilizing test, the data recorded are entered
Row Uniformity Analysis, by the uniformity=100* (1-standard deviation/meansigma methods).When the uniformity is more than 97%, then be labeled as ▲；When
The uniformity more than 90% and less than 97%, is then labeled as ☆；When the uniformity is less than 90%, then it is labeled as.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not
Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained
Art scheme, all should fall within the scope and spirit of the invention.
Claims (5)
1. a preparation method for antibacterial composite fibers film, it comprises the following steps: the preparation of (1) antibacterial spinning solution: weigh
Appropriate PEG400, in tool plug conical flask, is warming up to 50 DEG C, adds dichloromethane, wherein dichloromethane and poly-second two
The volume ratio of alcohol 400 is 7: 2；Add molecular weight 100,000 PLLA, at room temperature magnetic agitation 2h；100 ~ 300rpm stirs lower
Add the antibiotic complex dispersion liquid that concentration is 0.01 ~ 0.1mol/l；Continue stirring 30 ~ 40min, make antibacterial spinning solution；(2)
Electrostatic spinning prepares antibacterial composite nano-fiber membrane；Wherein,
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, drips silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry to load the graphene quantum dot of silver；
(2) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90o3h it is dried, to obtain under C
SiO2The graphene quantum dot of the load silver of cladding；
(3) SiO2Cladding carries the surface of silver graphene quantum dot and processes；
(4) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the SiO that step (3) prepares2Cladding carries silver Graphene
Quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C be incubated 15 ~
30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
2. a preparation method for antibacterial composite fibers film, it comprises the following steps: the preparation of (1) antibacterial spinning solution: weigh
Appropriate PEG400, in tool plug conical flask, is warming up to 50 DEG C, adds dichloromethane, wherein dichloromethane and poly-second two
The volume ratio of alcohol 400 is 7: 2；Add molecular weight 100,000 PLLA, at room temperature magnetic agitation 2h；100 ~ 300rpm stirs lower
Add the antibiotic complex dispersion liquid that concentration is 0.01 ~ 0.1mol/l；Continue stirring 30 ~ 40min, make antibacterial spinning solution；(2)
Electrostatic spinning prepares antibacterial composite nano-fiber membrane；Wherein,
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, drips silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, and dropping continues ultrasonic agitation 60 ~ 120min；Ageing, cleans, and dries to obtain load silver
Graphene quantum dot；
(2) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried, obtains SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(3) 0.1 ~ 0.3mol/L titanium source is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add what step (2) prepared
SiO2Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, old
Change, clean, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) surface carrying silver/titanium dioxide graphene quantum dot processes；
(5) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) prepares
Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C be incubated 15 ~
30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
3. a preparation method for antibacterial composite fibers film, it comprises the following steps: the preparation of (1) antibacterial spinning solution: weigh
Appropriate PEG400, in tool plug conical flask, is warming up to 50 DEG C, adds dichloromethane, wherein dichloromethane and poly-second two
The volume ratio of alcohol 400 is 7: 2；Add molecular weight 100,000 PLLA, at room temperature magnetic agitation 2h；100 ~ 300rpm stirs lower
Add the antibiotic complex dispersion liquid that concentration is 0.01 ~ 0.1mol/l；Continue stirring 30 ~ 40min, make antibacterial spinning solution；(2)
Electrostatic spinning prepares antibacterial composite nano-fiber membrane；Wherein,
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30
~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that dropping step (1) prepares, continue ultrasonic agitation 30 ~
60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry to load the graphene quantum dot of silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2
Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~ 10mL
Dispersant in, ultrasonic agitation also adds 0.1 ~ 0.3g and carries silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~
30min, moves in the microwave hydrothermal reaction kettle that liner is politef, seals and is placed in microwave assisted hydrothermal synthesis apparatus,
Microwave power is 200 ~ 400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load silver/bis-
Titanium oxide graphene quantum dot；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~
100ml graphene dispersion solution, the graphene quantum dot of the load zinc oxide that addition step (3) prepares and step (7) prepare
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
4. according to the preparation method of the arbitrary described antibacterial composite fibers film of claims 1 to 3, it is characterised in that described graphite
The volume ratio of alkene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3 ~ 4:2 ~ 3:1 ~ 2.
The preparation method of antibacterial composite fibers film the most according to claim 1 and 2, it is characterised in that described Graphene amount
Son point suspension manufacturing methods is as follows: weighs 0.5 ~ 0.8g C60 powder, measures the dense sulfur that 50 ~ 100ml mass fraction is 98%
Acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 300 ~ 500rpm simultaneously,
Obtain mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into,
Keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with molecular cut off be
The bag filter of 1000 is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, with
Shi Jiguang irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
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