CN106364124B - A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane - Google Patents
A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane Download PDFInfo
- Publication number
- CN106364124B CN106364124B CN201610748813.8A CN201610748813A CN106364124B CN 106364124 B CN106364124 B CN 106364124B CN 201610748813 A CN201610748813 A CN 201610748813A CN 106364124 B CN106364124 B CN 106364124B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- silver
- graphene quantum
- added
- polymer
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Mechanical Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses the preparation methods that a kind of antibacterial removes aldehyde composite cellulosic membrane comprising following steps：（1）It is prepared by polymer anti-bacterial fibre layer：10 ~ 20 parts of polymer A are dissolved with 80 ~ 90 parts of small molecule solvents；The antibiotic complex dispersion liquid of a concentration of 0.01 ~ 0.1mol/l is added dropwise under 100 ~ 300rpm stirrings, the antibiotic complex dispersion liquid is 8 ~ 10 with polymer solution A volume ratio:1~2；Continue 30 ~ 40min of stirring, prepares antibacterial nano fiber；（2）Polymer removes the preparation of formaldehyde fibers film layer：3 ~ 8 parts of diatomite/porous carbons and 70 ~ 80 parts of polymer Bs, 0.5 ~ 2 part of antioxidant, 10 ~ 15 parts of plasticizer are sufficiently mixed, is made and removes formaldehyde composite fibre；（3）By step（1）And step（2）The fibrous layer composite membrane-forming prepared.The present invention makes anti-bacterial fibre and removes formaldehyde fibers, then composite membrane-forming respectively, passes through the synergistic effect of antibiotic complex and diatomite/porous carbon.So that composite cellulosic membrane has excellent antibacterial and removes formaldehyde performance, meets the needs of multifunctional fibre film, further widen its application.
Description
Technical field
The present invention relates to composite fibre technical field of membrane, and the system of aldehyde composite cellulosic membrane is removed more particularly to a kind of antibacterial
Preparation Method.
Background technology
Nano fibrous membrane has surface area big, and porosity is high, and short texture, function that can be as required is pre-designed group
At, simulate extracellular matrix, the advantages that preparation method is simple and have huge application potential in many fields, eating
The fields such as product, medicine, daily use chemicals have to be widely applied very much.The nanofiber especially prepared as spinning solution using natural high polymer
Film, in addition to have the characteristics that it is above other than, also have excellent biocompatibility, biodegradability and recyclability etc..
Silver-carrying nano particle/composite cellulosic membrane poor biocompatibility, preparation process made from the prior art have by-product produce
It coins into fiber membrane structure and is corrupted such that the application of anti-bacterial fibre film is limited.And since nano silver is in granular form, granularity is to receive
Meter level is other, can only often be gathered in the privileged site of graphene, can not be evenly distributed on surface, to the antibacterial effect influenced；
On the other hand, nano silver can not combine closely with graphene（Especially when nano-Ag particles content increases, it is easy to happen reunion
Phenomenon）, it is easy to fall off in use, to influence service life and antibacterial effect.Meanwhile existing tunica fibrosa function compared with
Single, a kind of tunica fibrosa cannot be satisfied a variety of demands, often by the fiber film material of superposition multiple functions, but be relatively inaccessible to
Desired effect.
Invention content
Technical problem to be solved by the invention is to provide the preparation methods that a kind of antibacterial removes aldehyde composite cellulosic membrane.
The technical problems to be solved by the invention are achieved by the following technical programs：
A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane comprising following steps：
（1）It is prepared by polymer anti-bacterial fibre layer：10 ~ 20 parts of polymer A are dissolved with 80 ~ 90 parts of small molecule solvents；100
The lower antibiotic complex dispersion liquid that a concentration of 0.01 ~ 0.1mol/l is added dropwise of ~ 300rpm stirrings, the antibiotic complex dispersion liquid with
Polymer solution A volume ratio is 8 ~ 10:1~2；Continue 30 ~ 40min of stirring, antibacterial spinning solution is made, using solution electrostatic spinning
Method prepares antibacterial nano fiber.Solution electrospinning parameters are arranged：Spinning distance 12cm, voltage 20KV, feed flow rate
3ml/h.The antibiotic complex is pre-processed by coupling agent, and specially antibiotic complex is added in absolute ethyl alcohol, 500 ~
800rpm stirs 1 ~ 2h；The coupling agent for accounting for antibiotic complex mass fraction 2% is added dropwise dropwise, continues 1 ~ 2h of stirring, is dried after filtering
It is dry.
（2）Polymer removes the preparation of formaldehyde fibers film layer：Diatomite/porous carbon is added in absolute ethyl alcohol, 500 ~
800rpm stirs 1 ~ 2h；The coupling agent for accounting for diatomite/porous carbon mass fraction 2% is added dropwise dropwise, continues 1 ~ 2h of stirring, after filtering
Drying.Again by through above-mentioned processing 3 ~ 8 parts of diatomite/porous carbons and 70 ~ 80 parts of polymer Bs, 0.5 ~ 2 part of antioxidant, 10 ~ 15 parts
Plasticizer is sufficiently mixed, and using melt electrostatic spinning technology spinning, is made and is removed formaldehyde composite fibre.The parameter of melt electrostatic spinning
Setting：Spinning temperature is 50 DEG C of polymer B melting temperature or more, spinning distance 12cm, spinning voltage 30kV.
（3）By step（1）And step（2）The fibrous layer composite membrane-forming prepared.Complex method be pressure sintering, gluing,
One kind in blended method.
Small molecule solvent is water, methanol, ethyl alcohol, ethylene glycol, isopropanol, formic acid, acetic acid, acetone, dimethylformamide, four
The mixture of one kind or more persons in hydrogen furans.
Polymer A is polyacrylonitrile, polyamide, polycarbonate, pet resin, polyether sulfone tree
It is one or more in fat, poly (L-lactic acid), polymethyl methacrylate, polyvinylpyrrolidone, polyethylene glycol oxide.
Coupling agent is or mixtures thereof silane coupling agent, titanate coupling agent.
Polymer B is polyamide, polybutylene terephthalate (PBT), pet resin, poly- carbonic acid
It is one or more in fat, polyethylene, polypropylene, poly (L-lactic acid), polymethyl methacrylate, polyethersulfone resin.
Antioxidant is or mixtures thereof antioxidant 1010, irgasfos 168.
Plasticizer is or mixtures thereof polyesters plasticizer, polyalcohol ester plasticizer.
The diatomite/porous carbon preparation method is as follows：By 5g celluloses, 12mg polystyrolsulfon acids potassium and 30ml water add
Enter into 100ml water heating kettles, sealing reaction 10h, after cleaned drying, is forged under 900 DEG C of air atmosphere in 180 DEG C of baking ovens
1h is burnt, porous carbon is obtained；Nano diatomite is dispersed in the aqueous solution of 120ml, porous carbon 2h is immersed, makes nano material abundant
Into in duct, cleaning is repeatedly filtered, the weight ratio of dry diatomite/porous carbon, diatomite and porous carbon is 5:1.
In the present invention, a kind of preparation method of antimicrobial composite material includes the following steps：
（1）Prepare graphene quantum dot suspension：0.5 ~ 0.8g C60 powder is weighed, measuring 50 ~ 100ml mass fractions is
98% concentrated sulfuric acid mixes C60 powder and the concentrated sulfuric acid in beaker, and beaker is placed in ice-water bath, while with 300 ~ 500rpm
Speed stirring, obtain mixed liquor；0.5 ~ 3g potassium permanganate powders are weighed, are slowly added in above-mentioned mixed liquor；Remove ice water
Bath changes water-bath into, keeps 30 ~ 40 DEG C of bath temperature, reacts 5 ~ 8h；100 ~ 200ml pure water is rapidly joined, is filtered, then uses and cuts
It stays the bag filter that molecular weight is 1000 to dialyse 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot
Suspension, while laser irradiates 30 ~ 60min, laser irradiation power is 1 ~ 2W.
（2）Prepare the graphene quantum dot of load silver：Ultrasonic agitation（300 ~ 500W ultrasonic powers, 200 ~ 300rpm stirrings
Speed）A concentration of 0.001 ~ 0.005mol/L silver nitrate solutions, control reaction is added dropwise in 50 ~ 60ml graphene quantum dot suspension
Temperature is 45 ~ 60 DEG C, and a concentration of 0.01~0.08mol/L two citric acid monohydrate trisodiums are added dropwise, continue ultrasonic agitation 60 ~
120min；The silver-colored graphene quantum dot of load is dried to obtain in ageing, cleaning；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 the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver（500 ~ 1000W ultrasonic powers, 300 ~
500rpm mixing speeds）It is scattered in ethyl alcohol；Volume ratio 3 ~ 5 is added later:1 water and ammonium hydroxide, is stirring evenly and then adding into positive silicon
Acetoacetic ester（Mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1, it is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25
DEG C, it reacts 1 ~ 3 hour；Centrifuge and cleaned with acetone and deionized water successively being precipitated；This is deposited in 90oIt is done under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
（4）By 0.1 ~ 0.3mol/L titanium sources（Titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride）Add
Enter into 1 mol/L sulfuric acid solutions, is uniformly mixed；Step is added（3）SiO obtained2Cladding carries silver-colored graphene quantum dot, heating
To 100 ~ 110 DEG C, after reacting 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, after ageing 6 hours, clean, it is dry, obtain carrying silver/
Titanium dioxide graphene quantum dot.
（5）Carry the surface treatment of silver/titanium dioxide graphene quantum dot：0.005 ~ 0.01g graphite oxides are added to 5 ~
The dispersant of 10mL（DMSO）In, ultrasonic agitation（300 ~ 500W ultrasonic powers, 200 ~ 300rpm mixing speeds）And addition 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues 10 ~ 30min of ultrasonic agitation, moves to the microwave that liner is polytetrafluoroethylene (PTFE)
Hydrothermal reaction kettle（50 mL）In, sealing be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；It is cooling, filtering, the load silver/titanium dioxide graphene quantum dot for drying to be surface-treated.
（6）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm）It is configured to the graphite of a concentration of 0.2 ~ 0.8mg/ml
Alkene disperses solution, and solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（500 ~ 1000W ultrasonic powers, 600 ~ 800rpm are stirred
Mix speed）Step is added in 80 ~ 100ml graphene dispersion solution（5）Load silver/titanium dioxide graphene quantum dot obtained, ultrasound
10 ~ 30min is stirred, is then moved in the reaction kettle of polytetrafluoroethylene (PTFE), 15 ~ 30min is kept the temperature at 80 ~ 120 DEG C；It is cooling, centrifugation,
Cleaning, dries to obtain antimicrobial composite material.
The present invention has the advantages that：
Nano diatomite is pre-dispersed in porous carbon again with polymer reaction by the present invention, has both improved diatomaceous dispersion
Property but also polymer fiber have anti-formaldehyde characteristic；Graphene quantum dot and the load of load zinc oxide are first prepared respectively
The graphene quantum dot of silver/titanium dioxide, is then surface-treated, and is finally attached on porous graphene, can preferably load
And Nano silver grain and titanium dioxide are fixed, its reunion is prevented, the stability of Nano silver grain and titanium dioxide is significantly improved, makes
Nano silver grain and titanium dioxide have more efficient antibacterial activity；It is compounded with silver particles, titanium dioxide antibiotic performance, phase simultaneously
Than having better antibacterial effect, antibacterial lasting in single silver nano antibacterial agent；Anti-bacterial fibre is made respectively and except formaldehyde is fine
Dimension, then composite membrane-forming, by the synergistic effect of antibiotic complex and diatomite/porous carbon so that composite cellulosic membrane has excellent
Antibacterial and remove formaldehyde performance, meet the needs of multifunctional fibre film, further widen its application.
Specific implementation mode
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material comprising following steps：
（1）Prepare graphene quantum dot suspension：0.5g C60 powder is weighed, it is 98% to measure 100ml mass fractions
The concentrated sulfuric acid mixes C60 powder and the concentrated sulfuric acid in beaker, and beaker is placed in ice-water bath, while being stirred with the speed of 500rpm,
Obtain mixed liquor；3g potassium permanganate powders are weighed, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is kept
30 ~ 40 DEG C of bath temperature reacts 5h；200ml pure water is rapidly joined, is filtered, it is 1000 bag filter then to use molecular cut off
Dialysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, while laser irradiates
30min, laser irradiation power are 2W.
（2）Prepare the graphene quantum dot of load silver：Ultrasonic agitation（500W ultrasonic powers, 300rpm mixing speeds）50ml
A concentration of 0.005mol/L silver nitrate solutions are added dropwise in graphene quantum dot suspension, and controlling reaction temperature is 50 DEG C, and concentration is added dropwise
For 0.08mol/L two citric acid monohydrate trisodiums, continue that 90min is stirred by ultrasonic；The silver-colored graphene of load is dried to obtain in ageing, cleaning
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
（3）By the graphene quantum dot ultrasonic agitation of 0.1g load silver（1000W ultrasonic powers, 500rpm mixing speeds）
It is scattered in ethyl alcohol；Volume ratio 5 is added later:1 water and ammonium hydroxide, is stirring evenly and then adding into ethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, it is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, is reacted 2 hours；Carry out from
The heart and being cleaned successively with acetone and deionized water is precipitated；This is deposited in 90oDry 3h under C, to obtain SiO2Cladding is born
Carry the graphene quantum dot of silver.
（4）By 0.3mol/L titanium sources（Titanium source is potassium fluotitanate）It is added in 1 mol/L sulfuric acid solutions, is uniformly mixed；Add
Enter step（3）SiO obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reacting 2h, with concentrated ammonia solution tune pH
Value is to 7, after being aged 6 hours, cleans, dry, obtains carrying silver/titanium dioxide graphene quantum dot.
（5）Carry the surface treatment of silver/titanium dioxide graphene quantum dot：0.005g graphite oxides are added to point of 10mL
Powder（DMSO）In, ultrasonic agitation（500W ultrasonic powers, 300rpm mixing speeds）And 0.3g is added and carries silver/titanium dioxide graphite
Alkene quantum dot continues that 30min is stirred by ultrasonic, and moves to the microwave hydrothermal reaction kettle that liner is polytetrafluoroethylene (PTFE)（50 mL）In, sealing
It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power 200W, reacts 60min at 240 DEG C；Cooling, filtering is dried
The load silver/titanium dioxide graphene quantum dot of surface treatment.
（6）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, 100 ~ 500nm of layer size）It is configured to a concentration of
The graphene dispersion solution of 0.2mg/ml, solvent are water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（1000W ultrasonic powers,
800rpm mixing speeds）Step is added in 100ml graphene dispersion solution（5）Load silver/titanium dioxide graphene quantum obtained
Point is stirred by ultrasonic 30min, then moves in the reaction kettle of polytetrafluoroethylene (PTFE), 30min is kept the temperature at 100 DEG C；It is cooling, centrifugation, clearly
It washes, dries to obtain antimicrobial composite material.
Embodiment 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material comprising following steps：
（1）Prepare graphene quantum dot suspension：0.6g C60 powder is weighed, it is 98% to measure 50 ~ 100ml mass fractions
The concentrated sulfuric acid, C60 powder and the concentrated sulfuric acid are mixed in beaker, beaker is placed in ice-water bath, while being stirred with the speed of 500rpm
It mixes, obtains mixed liquor；1g potassium permanganate powders are weighed, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is protected
30 ~ 40 DEG C of water holding bath temperature reacts 7h；200ml pure water is rapidly joined, is filtered, it is 1000 dialysis then to use molecular cut off
Bag dialysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, while laser irradiates
45min, laser irradiation power are 1.2W.
（2）Prepare the graphene quantum dot of load silver：Ultrasonic agitation（500W ultrasonic powers, 300rpm mixing speeds）60ml
A concentration of 0.003mol/L silver nitrate solutions are added dropwise in graphene quantum dot suspension, and controlling reaction temperature is 50 DEG C, and concentration is added dropwise
For 0.05mol/L two citric acid monohydrate trisodiums, continue that 90min is stirred by ultrasonic；The silver-colored graphene of load is dried to obtain in ageing, cleaning
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 of 0.3g load silver（1000W ultrasonic powers, 500rpm mixing speeds）
It is scattered in ethyl alcohol；Volume ratio 4 is added later:1 water and ammonium hydroxide, is stirring evenly and then adding into ethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, it is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, is reacted 1 hour；Carry out from
The heart and being cleaned successively with acetone and deionized water is precipitated；This is deposited in 90oDry 3h under C, to obtain SiO2Cladding is born
Carry the graphene quantum dot of silver.
（4）By 0.2mol/L titanium sources（Titanium source is ammonium titanium fluoride）It is added in 1 mol/L sulfuric acid solutions, is uniformly mixed；Add
Enter step（3）SiO obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reacting 3h, with concentrated ammonia solution tune pH
Value is to 7, after being aged 6 hours, cleans, dry, obtains carrying silver/titanium dioxide graphene quantum dot.
（5）Carry the surface treatment of silver/titanium dioxide graphene quantum dot：0.008g graphite oxides are added to point of 8mL
Powder（DMSO）In, ultrasonic agitation（500W ultrasonic powers, 300rpm mixing speeds）And 0.2g is added and carries silver/titanium dioxide graphite
Alkene quantum dot continues that 30min is stirred by ultrasonic, and moves to the microwave hydrothermal reaction kettle that liner is polytetrafluoroethylene (PTFE)（50 mL）In, sealing
It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power 300W, reacts 60min at 220 DEG C；Cooling, table is dried to obtain in filtering
The load silver/titanium dioxide graphene quantum dot of surface treatment.
（6）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, 100 ~ 500nm of layer size）It is configured to a concentration of
The graphene dispersion solution of 0.5mg/ml, solvent are water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（1000W ultrasonic powers,
800rpm mixing speeds）Step is added in 80ml graphene dispersion solution（5）Load silver/titanium dioxide graphene quantum dot obtained,
30min is stirred by ultrasonic, then moves in the reaction kettle of polytetrafluoroethylene (PTFE), 30min is kept the temperature at 100 DEG C；It is cooling, it centrifuges, cleaning,
Dry to obtain antimicrobial composite material.
Embodiment 3
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material comprising following steps：
（1）Prepare graphene quantum dot suspension：0.8g C60 powder is weighed, it is 98% to measure 100ml mass fractions
The concentrated sulfuric acid mixes C60 powder and the concentrated sulfuric acid in beaker, and beaker is placed in ice-water bath, while being stirred with the speed of 500rpm,
Obtain mixed liquor；0.5g potassium permanganate powders are weighed, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, is protected
30 ~ 40 DEG C of water holding bath temperature reacts 8h；100ml pure water is rapidly joined, is filtered, it is 1000 dialysis then to use molecular cut off
Bag dialysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, while laser irradiates
60min, laser irradiation power are 1W.
（2）Prepare the graphene quantum dot of load silver：Ultrasonic agitation（500W ultrasonic powers, 300rpm mixing speeds）50ml
A concentration of 0.001mol/L silver nitrate solutions are added dropwise in graphene quantum dot suspension, and controlling reaction temperature is 50 DEG C, and concentration is added dropwise
For 0.01mol/L two citric acid monohydrate trisodiums, continue that 90min is stirred by ultrasonic；The silver-colored graphene of load is dried to obtain in ageing, cleaning
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
（3）By the graphene quantum dot ultrasonic agitation of 0.5g load silver（1000W ultrasonic powers, 500rpm mixing speeds）
It is scattered in ethyl alcohol；Volume ratio 3 is added later:1 water and ammonium hydroxide, is stirring evenly and then adding into ethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 1:1, it is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, is reacted 3 hours；Carry out from
The heart and being cleaned successively with acetone and deionized water is precipitated；This is deposited in 90oDry 3h under C, to obtain SiO2Cladding is born
Carry the graphene quantum dot of silver.
（4）By 0.1mol/L titanium sources（Titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride）It is added to
In 1 mol/L sulfuric acid solutions, it is uniformly mixed；Step is added（3）SiO obtained2Cladding carries silver-colored graphene quantum dot, is warming up to
It 110 DEG C, after reacting 4h, with concentrated ammonia solution tune pH value to 7, after being aged 6 hours, cleans, it is dry, it obtains carrying silver/titanium dioxide
Graphene quantum dot.
（5）Carry the surface treatment of silver/titanium dioxide graphene quantum dot：0.01g graphite oxides are added to the dispersion of 5mL
Agent（DMSO）In, ultrasonic agitation（500W ultrasonic powers, 300rpm mixing speeds）And 0.1g is added and carries silver/titanium dioxide graphene
Quantum dot continues that 30min is stirred by ultrasonic, and moves to the microwave hydrothermal reaction kettle that liner is polytetrafluoroethylene (PTFE)（50 mL）In, after sealing
It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power 400W, reacts 60min at 200 DEG C；Cooling, surface is dried to obtain in filtering
The load silver/titanium dioxide graphene quantum dot of processing.
（6）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, 100 ~ 500nm of layer size）It is configured to a concentration of
The graphene dispersion solution of 0.8mg/ml, solvent are water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（1000W ultrasonic powers,
800rpm mixing speeds）Step is added in 100ml graphene dispersion solution（5）Load silver/titanium dioxide graphene quantum obtained
Point is stirred by ultrasonic 30min, then moves in the reaction kettle of polytetrafluoroethylene (PTFE), 30min is kept the temperature at 100 DEG C；It is cooling, centrifugation, clearly
It washes, dries to obtain antimicrobial composite material.
Comparative example 1
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material comprising following steps：It weighs
Porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, 100 ~ 500nm of layer size）It is configured to the graphene point of a concentration of 0.8mg/ml
Solution is dissipated, solvent is water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（1000W ultrasonic powers, 800rpm mixing speeds）80ml stones
Black alkene disperses solution, and a concentration of 0.001mol/L silver nitrate solutions are added dropwise, and controlling reaction temperature is 50 DEG C, is added dropwise a concentration of
0.01mol/L two citric acid monohydrate trisodiums continue that 90min is stirred by ultrasonic；Ageing, cleaning, dries to obtain antimicrobial composite material.
Comparative example 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material comprising following steps：
（1）Compound concentration is 0.001mol/L silver nitrate solutions, and controlling reaction temperature is 50 DEG C, is added dropwise a concentration of
90min, the volume ratio of silver nitrate solution and two citric acid monohydrate trisodiums is stirred by ultrasonic in 0.01mol/L two citric acid monohydrate trisodiums
It is 2:1；Volume ratio 3 is added later:1 water and ammonium hydroxide, is stirring evenly and then adding into ethyl orthosilicate, the graphene amount with load silver
The mass ratio of son point is 1:1, it is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, is reacted 3 hours；Centrifuge and successively
It is cleaned and is precipitated with acetone and deionized water；This is deposited in 90oDry 3h under C, to obtain Ag/SiO2；
（2）By 0.1mol/L titanium sources（Titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride）It is added to
In 1 mol/L sulfuric acid solutions, it is uniformly mixed；Step is added（1）Ag/SiO obtained2, 110 DEG C are warming up to, after reacting 4h, use is dense
Ammonia spirit tune pH value is to 7, after being aged 6 hours, cleans, dry, obtains Ag/SiO2/ titanium dioxide；
（3）Weigh porous graphene（2 ~ 5 layers, hole size about 3 ~ 6nm, 100 ~ 500nm of layer size）It is configured to a concentration of
The graphene dispersion solution of 0.8mg/ml, solvent are water, acetone or dimethyl sulfoxide (DMSO)；Ultrasonic agitation（1000W ultrasonic powers,
800rpm mixing speeds）Step is added in 100ml graphene dispersion solution（3）Ag/SiO obtained2/ titanium dioxide, ultrasonic agitation
Then 30min is moved in the reaction kettle of polytetrafluoroethylene (PTFE), 30min is kept the temperature at 100 DEG C；It is cooling, it centrifuges, cleaning is dried anti-
Bacterium composite material.
The detailed process and steps are as follows that the antibacterial activity of antimicrobial composite material prepared by the present invention is evaluated：
The bacterium of test is respectively staphylococcus aureus and Escherichia coli；With reference to minimal inhibitory concentration（minimal
inhibitory concentration, MIC）Test method（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 weighed with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with MH meat soups to serial dilute again
Various concentration is released, is added separately in the MH culture solutions containing certain bacterium amount, it is about 10 to make the concentration of final bacterium solution6A/mL,
Then for 24 hours, observation is as a result, as shown in table 1 for shaken cultivation at 37 DEG C.The test tube for being not added with antimicrobial sample is managed as a contrast, nothing
The experiment tube liquid-transparent of bacterium growth, the antiseptic metering with not long tube are the minimum inhibitory concentration (MIC) of the antiseptic.
Table 1：The anti-microbial property of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Long-term effect is tested：A conical flask is put in 40 DEG C of thermostatic water baths, it is made that each embodiment and comparative examples of 1g are added in bottle
Standby antimicrobial composite material sample and 200mL brine（0.9mass%）, and impregnate 6 in water respectively, 24, sample after 72h, measure
Its minimum inhibitory concentration, as shown in table 2.
Table 2：Embodiment 1 ~ 3 and comparative example 1, the long acting antibiotic activity of 2 antimicrobial composite materials
Embodiment 4
A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane comprising following steps：
（1）It is prepared by polymer anti-bacterial fibre layer：20 parts of poly (L-lactic acid) are dissolved with 80 parts of ethyl alcohol；Under 200rpm stirrings
The 2 antibiotic complex dispersion liquid of embodiment of a concentration of 0.04mol/l, the antibiotic complex dispersion liquid and poly (L-lactic acid) is added dropwise
Liquor capacity ratio is 8:1；Continue to stir 40min, antibacterial spinning solution is made, antimicrobial nano is prepared using solution electrospinning process
Fiber；Solution electrospinning parameters are arranged：Spinning distance 12cm, voltage 20KV, feed flow rate 3ml/h.The antibiotic complex passes through
Coupling agent pretreatment is crossed, specially antibiotic complex is added in absolute ethyl alcohol, 800rpm stirs 2h；Dropwise addition accounts for anti-dropwise
The silane coupling agent of bacterium compound mass fraction 2% continues to stir 2h, be dried after filtering.
（2）Polymer removes the preparation of formaldehyde fibers film layer：Diatomite/porous carbon is added in absolute ethyl alcohol, 800rpm
Stir 2h；The silane coupling agent for accounting for diatomite/porous carbon mass fraction 2% is added dropwise dropwise, continues to stir 2h, be dried after filtering；
Again by 3 parts of diatomite/porous carbons and 40 parts of polyethylene, 40 parts of polypropylene, 1 part of irgasfos 168,12 parts of polyester through above-mentioned processing
Class plasticizer is sufficiently mixed, and using melt electrostatic spinning technology spinning, is made and is removed formaldehyde composite fibre；The ginseng of melt electrostatic spinning
Number setting：Spinning temperature is 50 DEG C of polymer B melting temperature or more, spinning distance 12cm, spinning voltage 30kV.The diatom
Soil/porous carbon preparation method is as follows：By 5g celluloses, 12mg polystyrolsulfon acids potassium and 30ml water are added to 100ml water heating kettles
In, sealing reaction 10h, after cleaned drying, 1h is calcined under 900 DEG C of air atmosphere, is obtained porous in 180 DEG C of baking ovens
Carbon；Nano diatomite is dispersed in the aqueous solution of 120ml, porous carbon 2h is immersed, allows nano material well into duct, it is more
The weight ratio of the cleaning of secondary suction filtration, dry diatomite/porous carbon, diatomite and porous carbon is 5:1.
（3）Pressure sintering step will be passed through（1）And step（2）The fibrous layer composite membrane-forming prepared.
Embodiment 5
A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane comprising following steps：
（1）It is prepared by polymer anti-bacterial fibre layer：20 parts of poly (L-lactic acid) are dissolved with 80 parts of ethyl alcohol；Under 200rpm stirrings
The 2 antibiotic complex dispersion liquid of embodiment of a concentration of 0.04mol/l, the antibiotic complex dispersion liquid and poly (L-lactic acid) is added dropwise
Liquor capacity ratio is 10:2；Continue to stir 40min, antibacterial spinning solution is made, preparing antibacterial using solution electrospinning process receives
Rice fiber；Solution electrospinning parameters are arranged：Spinning distance 12cm, voltage 20KV, feed flow rate 3ml/h.The antibiotic complex
It pre-processes by coupling agent, specially antibiotic complex is added in absolute ethyl alcohol, 800rpm stirs 2h；It is added dropwise and accounts for dropwise
The silane coupling agent of antibiotic complex mass fraction 2% continues to stir 2h, be dried after filtering.
（2）Polymer removes the preparation of formaldehyde fibers film layer：Diatomite/porous carbon is added in absolute ethyl alcohol, 800rpm
Stir 2h；The silane coupling agent for accounting for diatomite/porous carbon mass fraction 2% is added dropwise dropwise, continues to stir 2h, be dried after filtering；
Again by 5 parts of diatomite/porous carbons and 40 parts of polyethylene, 40 parts of polypropylene, 1 part of irgasfos 168,12 parts of polyester through above-mentioned processing
Class plasticizer is sufficiently mixed, and using melt electrostatic spinning technology spinning, is made and is removed formaldehyde composite fibre；The ginseng of melt electrostatic spinning
Number setting：Spinning temperature is 50 DEG C of polymer B melting temperature or more, spinning distance 12cm, spinning voltage 30kV.The diatom
Soil/porous carbon preparation method is as follows：By 5g celluloses, 12mg polystyrolsulfon acids potassium and 30ml water are added to 100ml water heating kettles
In, sealing reaction 10h, after cleaned drying, 1h is calcined under 900 DEG C of air atmosphere, is obtained porous in 180 DEG C of baking ovens
Carbon；Nano diatomite is dispersed in the aqueous solution of 120ml, porous carbon 2h is immersed, allows nano material well into duct, it is more
The weight ratio of the cleaning of secondary suction filtration, dry diatomite/porous carbon, diatomite and porous carbon is 5:1.
（3）Pressure sintering step will be passed through（1）And step（2）The fibrous layer composite membrane-forming prepared.
Embodiment 6
A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane comprising following steps：
（1）It is prepared by polymer anti-bacterial fibre layer：20 parts of poly (L-lactic acid) are dissolved with 80 parts of ethyl alcohol；Under 200rpm stirrings
The 2 antibiotic complex dispersion liquid of embodiment of a concentration of 0.04mol/l, the antibiotic complex dispersion liquid and poly (L-lactic acid) is added dropwise
Liquor capacity ratio is 8:2；Continue to stir 40min, antibacterial spinning solution is made, antimicrobial nano is prepared using solution electrospinning process
Fiber；Solution electrospinning parameters are arranged：Spinning distance 12cm, voltage 20KV, feed flow rate 3ml/h.The antibiotic complex passes through
Coupling agent pretreatment is crossed, specially antibiotic complex is added in absolute ethyl alcohol, 800rpm stirs 2h；Dropwise addition accounts for anti-dropwise
The silane coupling agent of bacterium compound mass fraction 2% continues to stir 2h, be dried after filtering.
（2）Polymer removes the preparation of formaldehyde fibers film layer：Diatomite/porous carbon is added in absolute ethyl alcohol, 800rpm
Stir 2h；The silane coupling agent for accounting for diatomite/porous carbon mass fraction 2% is added dropwise dropwise, continues to stir 2h, be dried after filtering；
Again by 8 parts of diatomite/porous carbons and 40 parts of polyethylene, 40 parts of polypropylene, 1 part of irgasfos 168,12 parts of polyester through above-mentioned processing
Class plasticizer is sufficiently mixed, and using melt electrostatic spinning technology spinning, is made and is removed formaldehyde composite fibre；The ginseng of melt electrostatic spinning
Number setting：Spinning temperature is 50 DEG C of polymer B melting temperature or more, spinning distance 12cm, spinning voltage 30kV.The diatom
Soil/porous carbon preparation method is as follows：By 5g celluloses, 12mg polystyrolsulfon acids potassium and 30ml water are added to 100ml water heating kettles
In, sealing reaction 10h, after cleaned drying, 1h is calcined under 900 DEG C of air atmosphere, is obtained porous in 180 DEG C of baking ovens
Carbon；Nano diatomite is dispersed in the aqueous solution of 120ml, porous carbon 2h is immersed, allows nano material well into duct, it is more
The weight ratio of the cleaning of secondary suction filtration, dry diatomite/porous carbon, diatomite and porous carbon is 5:1.
（3）Pressure sintering step will be passed through（1）And step（2）The fibrous layer composite membrane-forming prepared.
Comparative example 3
Based on the preparation method of embodiment 6, the difference is that：It is not added with antibiotic complex.
Comparative example 4
Based on the preparation method of embodiment 6, the difference is that：It is not added with diatomite/porous carbon.
Comparative example 5
Based on the preparation method of embodiment 6, the difference is that：The antibiotic complex is nano silver antimicrobials.
Comparative example 6
Based on the preparation method of embodiment 6, the difference is that：Diatomite/the porous carbon replaces with diatomite.
Embodiment 4 to 6 and comparative example 3 to 6 are subjected to antibiotic rate and purifying formaldehyde rate test, it is as a result as follows：
Antibacterial Evaluation for Uniformity：Choose 100 regions on same tunica fibrosa and carry out sterilizing test, to the data that measure into
Row Uniformity Analysis passes through the uniformity=100* (1- standard deviations/average value).When the uniformity be more than 97%, then be labeled as ▲；When
The uniformity is more than 90% and is less than 97%, then is labeled as ☆；When the uniformity is less than 90%, then Biao Ji Wei ╳.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (1)
1. a kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane comprising following steps：
（1）It is prepared by polymer antibacterial nano fiber layer：20 parts of poly (L-lactic acid) are dissolved with 80 parts of ethyl alcohol；Under 200rpm stirrings
The antibiotic complex dispersion liquid of a concentration of 0.04mol/l, the antibiotic complex dispersion liquid and poly (L-lactic acid) solution body is added dropwise
Product is than being 8:1；Continue to stir 40min, antibacterial spinning solution is made, polymer antimicrobial nano is prepared using solution electrospinning process
Fibrous layer；Solution electrospinning parameters are arranged：Spinning distance 12cm, voltage 20KV, feed flow rate 3mL/h；The antibiotic complex
It pre-processes by coupling agent, specially antibiotic complex is added in absolute ethyl alcohol, 800rpm stirs 2h；It is added dropwise and accounts for dropwise
The silane coupling agent of antibiotic complex mass fraction 2% continues to stir 2h, be dried after filtering；
（2）Polymer removes the preparation of formaldehyde fibers layer：Diatomite/porous carbon is added in absolute ethyl alcohol, 800rpm stirrings
2h；The silane coupling agent for accounting for diatomite/porous carbon mass fraction 2% is added dropwise dropwise, continues to stir 2h, be dried after filtering；It again will be through
The 3 parts of diatomite/porous carbons and 40 parts of polyethylene of above-mentioned processing, 40 parts of polypropylene, 1 part of irgasfos 168,12 parts of polyesters plasticising
Agent is sufficiently mixed, and using melt electrostatic spinning technology spinning, polymer is made and removes formaldehyde fibers layer；The parameter of melt electrostatic spinning
Setting：Spinning temperature is 50 DEG C of polymer melting temperature or more, spinning distance 12cm, spinning voltage 30kV；The diatomite/
Porous carbon preparation method is as follows：By 5g celluloses, 12mg polystyrolsulfon acids potassium and 30mL water are added in 100mL water heating kettles,
Sealing reaction 10h, after cleaned drying, calcines 1h under 900 DEG C of air atmosphere, obtains porous carbon in 180 DEG C of baking ovens；It will
Nano diatomite is dispersed in the aqueous solution of 120mL, immerses porous carbon 2h, is allowed nano material well into duct, is repeatedly taken out
Filtering is washed, dry diatomite/porous carbon, and the weight ratio of diatomite and porous carbon is 5:1；
（3）By pressure sintering by step（1）The polymer antibacterial nano fiber layer and step of preparation（2）The polymer prepared removes
Formaldehyde fibers layer composite membrane-forming；Wherein,
The preparation method of antibiotic complex in the antibiotic complex dispersion liquid is as follows：
（A）Prepare graphene quantum dot suspension：Weigh 0.6g C60 powder, measure 50 ~ 100mL mass fractions be 98% it is dense
Sulfuric acid mixes C60 powder and the concentrated sulfuric acid in beaker, and beaker is placed in ice-water bath, while being stirred with the speed of 500rpm, obtains
Mixed liquor；1g potassium permanganate powders are weighed, are slowly added in above-mentioned mixed liquor；Ice-water bath is removed, changes water-bath into, keeps water
30 ~ 40 DEG C of bath temperature reacts 7h；200mL pure water is rapidly joined, is filtered, the bag filter for then molecular cut off being used to be 1000 is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, while laser irradiates
45min, laser irradiation power are 1.2W；
（B）Prepare the graphene quantum dot of load silver：60mL graphenes are stirred by ultrasonic in 500W ultrasonic powers, 300rpm mixing speeds
A concentration of 0.003mol/L silver nitrate solutions are added dropwise in quantum dot suspension, and controlling reaction temperature is 50 DEG C, is added dropwise a concentration of
0.05mol/L two citric acid monohydrate trisodiums continue that 90min is stirred by ultrasonic；The silver-colored graphene amount of load is dried to obtain in ageing, cleaning
Sub- point；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2；
（C）By the graphene quantum dot 1000W ultrasonic powers of 0.3g load silver, 500rpm mixing speeds ultrasonic agitation is scattered in second
In alcohol；Volume ratio 4 is added later:1 water and ammonium hydroxide is stirring evenly and then adding into ethyl orthosilicate, ethyl orthosilicate and load silver
Graphene quantum dot mass ratio be 2:1, it is 9 ~ 10 to adjust pH value, and reaction temperature is 20 ~ 25 DEG C, is reacted 1 hour；It carries out
It centrifuges and is cleaned successively with acetone and deionized water and precipitated；This is deposited in 90oDry 3h under C, to obtain SiO2Cladding
Load the graphene quantum dot of silver；
（D）0.2mol/L ammonium titanium fluorides are added in 1 mol/L sulfuric acid solutions, are uniformly mixed；Step is added（C）It is obtained
SiO2The graphene quantum dot of the load silver of cladding, is warming up to 100 DEG C, old with concentrated ammonia solution tune pH value to 7 after reacting 3h
After changing 6 hours, clean, it is dry, it obtains carrying silver/titanium dioxide graphene quantum dot；
（E）Carry the surface treatment of silver/titanium dioxide graphene quantum dot：0.008g graphite oxides are added to DMSO points of 8mL
In powder, 500W ultrasonic powers, 300rpm mixing speeds, which are stirred by ultrasonic and 0.2g is added, carries silver/titanium dioxide graphene quantum
Point continues that 30min is stirred by ultrasonic, and moves in the 50mL microwave hydrothermal reaction kettles that liner is polytetrafluoroethylene (PTFE), sealing is placed on micro-
In wave assisted hydrothermal synthesis apparatus, microwave power 300W reacts 60min at 220 DEG C；Cooling, filtering dries to be surface-treated
Carry silver/titanium dioxide graphene quantum dot；
（F）2 ~ 5 layers are weighed, the porous graphene of hole 3 ~ 6nm of size, 100 ~ 500nm of layer size are configured to a concentration of 0.5mg/mL
Graphene dispersion solution, solvent be water, acetone or dimethyl sulfoxide (DMSO)；1000W ultrasonic powers, 800rpm mixing speed ultrasounds are stirred
80mL graphene dispersion solution is mixed, step is added（E）Load silver/titanium dioxide graphene quantum dot obtained, ultrasonic agitation
Then 30min moves in the reaction kettle that liner is polytetrafluoroethylene (PTFE), 30min is kept the temperature at 100 DEG C；It is cooling, it centrifuges, cleans, dry
Do to obtain antibiotic complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748813.8A CN106364124B (en) | 2016-08-29 | 2016-08-29 | A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748813.8A CN106364124B (en) | 2016-08-29 | 2016-08-29 | A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106364124A CN106364124A (en) | 2017-02-01 |
| CN106364124B true CN106364124B (en) | 2018-07-17 |
Family
ID=57903737
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610748813.8A Active CN106364124B (en) | 2016-08-29 | 2016-08-29 | A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106364124B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108754778A (en) * | 2018-06-29 | 2018-11-06 | 安徽鼎鑫纺织品有限公司 | A kind for the treatment of process of silk, blend polyester fabric |
| CN109402745B (en) * | 2018-10-09 | 2021-04-20 | 保山恒丰纺织科技有限公司 | Micro-nano antibacterial fiber for yarn |
| CN109603206B (en) * | 2018-12-09 | 2021-07-30 | 英鸿纳米科技股份有限公司 | Nanofiber oil absorption material |
| CN114592592B (en) * | 2022-02-11 | 2024-04-26 | 瑞洲建设集团有限公司 | Assembled building construction process |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803527A (en) * | 2014-01-27 | 2014-05-21 | 浙江大学 | Preparation method of porous carbon and product thereof |
| CN104070751A (en) * | 2014-07-10 | 2014-10-01 | 北京化工大学 | Antibacterial composite fiber membrane for removing haze particles and formaldehyde and preparation method of Antibacterial composite fiber 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 |
| CN104472542A (en) * | 2014-12-18 | 2015-04-01 | 中山大学 | Method for preparing graphene/silver/titanium dioxide composite material |
| 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 |
| KR20160030696A (en) * | 2014-09-11 | 2016-03-21 | 전북대학교산학협력단 | Filter media having noxious substances reducing and antibacterial function and manufacturing method of the same |
| 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 |
| CN106120151A (en) * | 2016-08-29 | 2016-11-16 | 佛山市高明区尚润盈科技有限公司 | A kind of except the preparation method of formaldehyde composite cellulosic membrane |
-
2016
- 2016-08-29 CN CN201610748813.8A patent/CN106364124B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103803527A (en) * | 2014-01-27 | 2014-05-21 | 浙江大学 | Preparation method of porous carbon and product thereof |
| CN104070751A (en) * | 2014-07-10 | 2014-10-01 | 北京化工大学 | Antibacterial composite fiber membrane for removing haze particles and formaldehyde and preparation method of Antibacterial composite fiber 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 |
| KR20160030696A (en) * | 2014-09-11 | 2016-03-21 | 전북대학교산학협력단 | Filter media having noxious substances reducing and antibacterial function and manufacturing method of the same |
| CN104472542A (en) * | 2014-12-18 | 2015-04-01 | 中山大学 | Method for preparing graphene/silver/titanium dioxide composite material |
| 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 |
| CN106120151A (en) * | 2016-08-29 | 2016-11-16 | 佛山市高明区尚润盈科技有限公司 | A kind of except the preparation method of formaldehyde composite cellulosic membrane |
Non-Patent Citations (1)
| Title |
|---|
| 核壳结构纳米Ag@SiO2的制备及其杀菌、防腐和应用性能研究;张新生;《中国博士学位论文全文数据库 工程科技I辑》;20120415;第21-22页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106364124A (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106192214B (en) | A kind of preparation method of antibacterial composite fibers film | |
| CN106364124B (en) | A kind of antibacterial removes the preparation method of aldehyde composite cellulosic membrane | |
| CN106317386A (en) | Preparing method of antibacterial polylactic acid material | |
| CN106120151B (en) | It is a kind of except the preparation method of formaldehyde composite cellulosic membrane | |
| CN106085156A (en) | A kind of wash resistant anti static antibacterial coating and preparation method thereof | |
| CN106367837A (en) | Preparation method of photochromic composite fiber membrane | |
| CN106085139A (en) | A kind of preparation method of anticorrosive paint | |
| CN106349874A (en) | Anticorrosion coating preparing method | |
| CN106350893A (en) | Antibacterial and radiation resistant composite fiber membrane preparing method | |
| CN106221316A (en) | A kind of preparation method of waterborne antibacterial deodorization inorganic coating | |
| CN106172494A (en) | A kind of porous graphene Ag-carried antibacterial composite and preparation method thereof | |
| CN106220831A (en) | A kind of preparation method of poly-lactic acid material | |
| CN106283878A (en) | A kind of preparation method of antibiotic antistatic corrugated board | |
| CN106084704A (en) | A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch | |
| CN106221556A (en) | A kind of deodorization ultraviolet-curing paint and preparation method thereof | |
| CN106349663A (en) | Preparing method for polylactic acid antibacterial radiation-resistant masterbatch | |
| CN106243936A (en) | A kind of wash resistant coating and preparation method thereof | |
| CN106189400A (en) | A kind of preparation method of the photochromic inorganic coating of aqueous | |
| CN106182807A (en) | A kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates | |
| CN106084923A (en) | A kind of preparation method of aqueous deodorization inorganic coating | |
| CN106084921A (en) | A kind of preparation method of waterborne antibacterial inorganic coating | |
| CN106349622A (en) | Formaldehyde-removing resin composite material and preparation method thereof | |
| CN105256292B (en) | A kind of preparation method of cobalt nickel nano-fiber film | |
| CN106279645A (en) | A kind of preparation method of photochromic poly-lactic acid material | |
| CN106349627A (en) | Method for antibacterial resin composit and preparing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191210 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 |