CN105199039B - A kind of Nano Silver/Graphene/polymer composite antibacterial emulsion and preparation method thereof - Google Patents
A kind of Nano Silver/Graphene/polymer composite antibacterial emulsion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Nano Silver/Graphene/polymer composite antibacterial emulsion and preparation method thereof, including：Graphene oxide ultrasonic disperse is obtained into solution A in water；By polyoxyethylene polyoxypropylene polyoxyethylene block copolymer and AgNO3Be dissolved in the water to obtain solution B；Polyoxyethylene polyoxypropylene polyoxyethylene block copolymer is dissolved in the water, acrylate is added and is obtained solution C；Solution A is mixed into obtain Nano Silver/graphene complex aqueous solution with solution B, Nano Silver/graphene complex is processed to obtain；Mix with solution C again, add initiator, polymerisation obtains Nano Silver/Graphene/polymer composite antibacterial emulsion.The inventive method can make that nano silver particles are more uniform to be supported on Graphene, and Nano Silver/graphene complex is dispersed in polymer emulsion, Nano Silver/Graphene/polymer composite antibacterial the emulsion of stabilization is formed, and obtained composite antibacterial emulsion has good anti-microbial property.
Description
Technical field
The invention belongs to nano composite material and antimicrobial technology neck city, and in particular to a kind of Nano Silver/Graphene/polymer
The preparation method of composite antibacterial emulsion.
Background technology
Nano silver particles have high-specific surface area, unique physico-chemical property, efficient antibacterial activity, are widely used to doctor
Treat the coating of apparatus, medical dressing, water body filtration, yarn fabric and other Healthy relevant products.Nano silver particles are with aqueous medium
Building-up process in, surfactant have solubilising and stabilization effect.Meanwhile, when medicine and human body interact, surface
Activating agent has the function of auxiliary, and it can be included into cell membrane, and indexing to cell interior, so as to improve the pharmacology of antiseptic
Activity.
Graphene is with sp2The single carbon atom lamella of hydridization constitutes a kind of Novel Carbon Nanomaterials.Graphene oxide its piece
Layer has oxy radical, such as carboxylic acid group and carbonyl on edge, there is epoxide group and hydroxyl, therefore graphene oxide energy on base plane
It is well dispersed into polar solvent.Graphene also has certain antibacterial action, the two dimensional surface of Graphene when being contacted with bacterium
Structure can cut the cell membrane of bacterium, while drawing the phospholipid molecule on cell membrane, make inactivation of bacteria.Nano silver particles because
Easily reunite, its application field is restricted.Using the specific surface area and the physico-chemical property of uniqueness of Graphene superelevation, by receiving
Growth in situ of the rice silver particles on Graphene, can effectively prevent the nano silver particles being supported on Graphene from reuniting, enhancing
Its anti-microbial property.
The Chinese invention patent application document of Application No. 201210322739.5 is disclosed using LBL electrostatic self-assembled works
Skill, by electrostatic adsorption so that graphene sheet layer is combined with Ag nano particles, prepares the nanometer Ag/graphite of biomimetic features
Alkene laminated film, the film has excellent anti-microbial property and stronger film-substrate cohesion, can for a long time play antibacterial
Effect.
The Chinese invention patent application document of Application No. 201410173113.1 discloses a kind of graphene oxide/silver network
Anti-biotic material and preparation method thereof is closed, step is as follows：(1) graphene oxide powder dispersion is in deionized water, abundant through ultrasound
Stripping obtains graphene oxide dispersion, then is added thereto to the water soluble organic substance with big π keys, then through ultrasonic fully mixed
Close；(2) silver nitrate is dissolved in water, then is added thereto to sodium sulfite or sodium citrate, reaction obtains silver complex；(3) will step
Suddenly the silver complex that the graphene oxide water solution that (1) obtains is obtained with step (2) mixes, and after reaction terminates, filters out precipitation.
Silver and organic or inorganic complex compound are formed small molecule in conjunction with graphene oxide to strengthen its stability, and by its slow release
To extend anti-microbial property.
The Chinese invention patent application document of Application No. 201210054952.2 discloses a kind of liquid phase method and prepares graphite
The method of alkene/silver nano particle composite material.Using DMF as reducing agent, graphene powder is used as load
Body, under gentle reaction condition, silver on graphene layer forming core, grow up, obtain Graphene/silver nano particle composite material.
The Chinese invention patent application document of Application No. 201410508312.3 discloses a kind of polyphenol compound and repaiies
The preparation method of decorations silver-colored Graphene antibiosis hydrogel also published originally.Graphene oxide, polyphenol compound are added to deionized water
In, ultrasonic disperse is got a uniform mixture, and 80~100 DEG C is heated to afterwards and is reacted 4~20 hours, and polyphenol is obtained after cooling
The grapheme modified hydrogel of class.Then the grapheme modified hydrogel of Polyphenols that will be obtained is immersed in certain density silver nitrate water
In solution, question response obtains anti-bacterial hydrogel afterwards completely.
The Chinese invention patent application document of Application No. 201110003784.X discloses a kind of silver/graphite alkene antibacterial and answers
The preparation method of condensation material, including：A) aqueous solution of reduced form graphene oxide-polystyrene sulphuric acid sodium compound is provided；b)
50 DEG C~70 DEG C are heated to the aqueous solution of the compound of the step a)；The aqueous solution of the compound after c) being heated to step b)
Silver/graphene antimicrobial composite material is obtained after middle addition silver nitrate solution reaction.
The Chinese invention patent application document of Application No. 201510159459.0 is related to a kind of heat-resistance antibacterial PLA material
Material and preparation method thereof, the material includes PLA matrix material and the nanometer being dispersed in the PLA matrix material
Silver/stannic oxide/graphene nano composite.Nano Silver/stannic oxide/graphene nano composite is by graphene oxide solution
Situ reduces silver nitrate and forms nano-Ag particles in surface of graphene oxide and obtain.The poly- breast of heat-resistance antibacterial of the present invention
Sour material has excellent heat-resisting and anti-microbial property than common poly-lactic acid material.
The Chinese invention patent application document of Application No. 201410686251.X discloses a kind of amino polyethylene glycol
Functional graphene oxide loading nano silvery anti-biotic material and preparation method.The method is comprised the following steps：By the poly- second of amination
Glycol is added in the aqueous solution of graphene oxide, adds 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate
And N-hydroxy-succinamide, stirring reaction after regulation pH, obtain the polyethyleneglycol modified graphene oxide of amination；Matched somebody with somebody
Into the aqueous solution, add silver nitrate, it is to be dissolved after be heated to boiling, add sodium citrate or the NaBH4 aqueous solution, reaction, cooling is obtained
To amino polyethylene glycol functional graphene oxide loading nano silvery anti-biotic material.
The Chinese invention patent application document of Application No. 201410129503.9 is related to a kind of graphene oxide/silver/change
The preparation method and application of property titanium dioxide compound.First, with crystalline flake graphite as raw material, oxidation stone is prepared using Hummer methods
Black alkene, and graphene oxide solution is made into, then have the nano titanium oxide of polyacrylate with surface grafting, and silver salt is common
Mix, boil, super filter tube wash-out obtains composite slow-release anti-biotic material.Above-mentioned anti-biotic material and thermoplastic resin are squeezed
Go out, blown film, the plastics prepared have long duration high-efficiency antimicrobial act on.
The Chinese invention patent application document 5 of Application No. 201410337717. provides one kind and efficiently prepares nano grain of silver
The method of son-Graphene three dimensional composite structure, the method is comprised the following steps：1. glucose is passed through under conditions of ammoniacal liquor is added
Reduction silver nitrate obtains Nano silver grain, it is deposited in graphene oxide layer by charge effect；2. in reaction under high pressure
The oxygen-containing functional group of removal surface of graphene oxide is reduced in kettle by hydro-thermal method, Nano silver grain-Graphene is obtained three-dimensional multiple
Close structure hydrogel；3. resulting three dimensional composite structure hydrogel is carried out into freeze-drying, removes moisture removal, obtain intensity it is high,
Well conducting, compound uniform Nano silver grain-Graphene three dimensional composite structure.
The Chinese invention patent application document of Application No. 201310549749.7 discloses a kind of with anti-microbial property
The preparation method of flexible and transparent conductive thin polymer film, belongs to nano composite material technical field.The present invention is used first
Hummers methods prepare the graphene oxide colloid of stable dispersion, then using the electrostatic of diallyl dimethyl ammoniumchloride
Suction-operated carries out surface modification to graphene oxide, and silver nanoparticle is prepared by the method for original position induction silver nanowire growth
Line/graphene nano hybrid material, further prepares nano silver wire/Graphene/polyvinyl alcohol film using solution-casting method, should
Film has the characteristics such as antibacterial, high conductivity, high transmission rate, softness.
The content of the invention
It is an object of the invention to provide a kind of Nano Silver/Graphene/polymer composite antibacterial emulsion preparation method, this hair
Bright method can make that nano silver particles are more uniform to be supported on Graphene, and Nano Silver/graphene complex is dispersed in polymerization
In thing emulsion, the Nano Silver/Graphene/polymer composite antibacterial emulsion of stabilization, and obtained composite antibacterial emulsion tool are formed
There is good anti-microbial property.
A kind of preparation method of Nano Silver/Graphene/polymer composite antibacterial emulsion, comprises the following steps：
(1) graphene oxide ultrasonic disperse is obtained into solution A in water；By polyoxyethylene-poly-oxypropylene polyoxyethylene block
Copolymer is dissolved in the water, and adds AgNO3Obtain solution B；Polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer is molten
In Xie Yushui, add acrylate and obtain solution C；
(2) solution A is well mixed to obtain Nano Silver/graphene complex aqueous solution with solution B, by gained Nano Silver/stone
Black alkene compound water solution carries out post-processing to obtain Nano Silver/graphene complex；
(3) solution C is mixed with Nano Silver/graphene complex, adds initiator, carry out being polymerized instead in water bath with thermostatic control
Deserved Nano Silver/Graphene/polymer composite antibacterial emulsion.
Preferably, the water is pure water, more preferably ultra-pure water.Graphene as nano silver particles excellent load
Body, obtained nano silver particles/graphene composite material has synergetic antibacterial effect.And using amphiphilic block copolymer as reduction
Agent and stabilizer prepare Nano Silver/graphene complex, and then using amphiphilic block copolymer as surfactant, prepare with poly-
Compound emulsion important is ground for decentralized medium is one of current nanometer Ag antiseptic comprising nano silver particles/graphene complex
Study carefully direction.
The inventive method is first with AgNO3It is presoma, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer is
Reducing agent and nano-particle dispersion stabilizer, Nano Silver/graphene complex is prepared by ultrasonic wave added hydrothermal synthesis method.Then
With acrylate as function monomer, Nano Silver/graphene complex is filler, and polyoxyethylene-poly-oxypropylene polyoxyethylene is embedding
Section copolymer is surfactant and dispersion stabilizer, and Nano Silver/Graphene/polymer Composite Milk is prepared by emulsion polymerization
Liquid.The present invention takes full advantage of polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer has reducing agent, nano-particle point
The characteristics such as dispersion stabilizer, surfactant, Nano Silver/Graphene/poly- is prepared by a kind of environmental protection, fast and convenient method
Compound complex emulsions, obtained Nano Silver/Graphene/polymer complex emulsions have preferable anti-microbial property, to Escherichia coli
Antibiotic rate reach more than 96%.
Nano Silver/Graphene/polymer composite antibacterial emulsion of the invention can be widely applied to building by coating method
The aspects such as light collecting body, road lighting lampshade, automobile lamp and sanitary ware.The present invention using hydrothermal synthesis method prepare Nano Silver/
Graphene complex, from amphiphilic block copolymer as reducing agent and dispersant, meanwhile, prepare the mistake of antimicrobial emulsion in polymerization
Amphiphilic block copolymer is used as surfactant again in journey.Graphene improves as the excellent carrier of nano silver particles
The dispersiveness of nano silver particles, also just improves antibacterial effect indirectly；Further, since the excellent mechanical of Graphene itself
Can, the objects such as glass, plastic plate, the ceramics of coated Nano Silver/Graphene/polymer composite antibacterial emulsion will be made with good
While good antibacterial effect, its shock resistance improves.
Preferably, graphene oxide quality and pure water volume ratio are 1~5mg/ml in solution A.It is further preferred that molten
Graphene oxide quality and pure water volume ratio are 2.5~4mg/ml in liquid A.
The oxygen content of the graphene oxide is 10~25wt%, it is preferable that graphene oxide can select Aladdin
The 800 mesh graphite powders of Industrial Cooperation are made by oneself by Hummers methods and obtain (Zhao Li, Chen Yufei, Wang Ting, Wu
The in-situ polymerization of gift light graphene oxides/polyurethane hybrid film builds and gas permeability composite journals, and 2015,
32,673-682)。
Preferably, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount of substance and pure water volume ratio in solution B
It is 10~50mg/ml, AgNO3Quality is 50~100mg/ml with pure water volume ratio.
It is further preferred that polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount of substance and pure water in solution B
Volume ratio is 20~50mg/ml, AgNO3Quality is 60~90mg/ml with pure water volume ratio.
Preferably, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount of substance and water volume ratio are 10 in solution C
The ratio between~50mg/ml, acrylate quality and water volume are 30~60mg/ml.
It is further preferred that polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount of substance and water volume in solution C
Than being 20~50mg/ml, the ratio between acrylate quality and water volume are 40~55mg/ml.
Most preferably, graphene oxide quality and pure water volume ratio are 2.6mg/ml in solution A；Polyoxy second in solution B
Alkene-Pluronic L121 quality is 20mg/ml, AgNO with pure water volume ratio3Quality and pure water body
Product is than being 60mg/ml；Polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount of substance is with water volume ratio in solution C
The ratio between 20mg/ml, acrylate quality and water volume are 40mg/ml.
Acrylate is methyl methacrylate, EMA, propyl methacrylate or methacrylic acid fourth
Any one in ester, preferably methyl methacrylate.
Polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer is the one kind in commercially available Pluronic series of products,
It is preferred that F108, F98, F88, F68 product.
Preferably, solution A mixes in equal volume with solution B in step (2).
Preferably, in step (3) Nano Silver/graphene complex addition be solution C in acrylate quality 0.1~
0.5wt%；Initiator addition is the 0.5wt% of acrylate quality in solution C.
Preferably, the initiator is azodiisobutyronitrile.
Preferably, solution A, solution B and solution C are obtained at 25~35 DEG C.Further preferably it is obtained at 30 DEG C.
Preferably, after solution A mixes with solution B in step (2), then at 25~35 DEG C it is ultrasonically treated 2.5~3.5 small
When.Further, after solution A mixes with solution B in step (2), then ultrasonically treated 3 hours at 30 DEG C.
Post-processed described in step (2) and be：After obtained Nano Silver/graphene complex aqueous solution is stood into 3 hours, incline
Supernatant is removed, then uses pure water, ethanol cyclic washing respectively, until there is no Ag in cleaning solution+Detection；The vacuum at 60 DEG C again
Dry 24 hours.
Preferably, polymeric reaction temperature is 55~65 DEG C in step (3).Further preferred 60 DEG C
The present invention also provides Nano Silver/Graphene/polymer composite antibacterial that a kind of preparation method as described is prepared
Emulsion.
Compared with prior art, the present invention has the advantages that：
The inventive method can make that nano silver particles are more uniform to be supported on Graphene, and Nano Silver/graphene complex is equal
It is even to be dispersed in polymer emulsion, the Nano Silver/Graphene/polymer composite antibacterial emulsion of stabilization is formed, and obtained answer
Closing antimicrobial emulsion has good anti-microbial property.
Specific embodiment
Further illustrated below by way of specific embodiment using how the present invention prepares Nano Silver/Graphene/polymer
Composite antibacterial emulsion, and its prepared complex emulsions anti-microbial property.
It is raw materials used in following examples to use commercial goods unless otherwise specified.
Embodiment 1
1. the graphene oxide (oxygen content is 22.4wt%) ultrasound (frequency 100Hz) of 2.0g is scattered at 30 DEG C
In the pure water of 500ml.
2. the F108 of 25g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 45g3, stirring and dissolving.
What 2. the graphene oxide water solution and step that 3. 1. step is prepared prepared contains F108 and AgNO3The aqueous solution
Isometric mixing, ultrasonic (frequency 100Hz) is processed 3 hours at 30 DEG C, is obtained and is contained Nano Silver/graphene complex aqueous solution.It is quiet
Put 3 hours, topple over supernatant, sediment uses pure water, absolute ethyl alcohol cyclic washing respectively again, until not having Ag in cleaning solution+Detection, is finally placed in product 60 DEG C of vacuum drying chambers and dries 24 hours, obtains Nano Silver/graphene complex.
4. the F108 of 25g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 27.5g, stirred
After mixing dissolving, step 3. obtained Nano Silver/graphene complex 75mg is added, adds the azodiisobutyronitrile of 137.5mg,
Polymerisation is carried out in 60 DEG C of water-bath, reaction stops heating, obtains including nanometer after reaching 100mPa to emulsion viscosity
The polymer complex emulsions of silver/graphite alkene.
Comparative example 1-1
The F108 of 25g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 45g3, ultrasonic (frequency 100Hz)
Treatment 3 hours.Add the methyl methacrylate of 27.5g, the azodiisobutyronitrile of 137.5mg, stirring mixing.In 60 DEG C
Polymerisation is carried out in water-bath, reaction stops heating, obtains polymer emulsion after reaching 100mPa to emulsion viscosity.
Comparative example 1-2
The F108 of 25g is dissolved in 500ml pure water at 30 DEG C, (oxygen content is to add the graphene oxide of 2.0g
22.4wt%), ultrasonic (frequency 100Hz) is processed 3 hours.Add the methyl methacrylate of 27.5g, the azo of 137.5mg
Bis-isobutyronitrile, stirring mixing.Polymerisation is carried out in 60 DEG C of water-bath, reaction stops adding after reaching 100mPa to emulsion viscosity
Heat, obtains polymer emulsion.
Comparative example 1-3
The F108 of 25g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 27.5g, stirred
Mixing.The azodiisobutyronitrile of 137.5mg is added, polymerisation is carried out in 60 DEG C of water-bath, reaction to emulsion viscosity reaches
Stop heating after 100mPa, obtain polymer emulsion.
Embodiment 2
1. graphene oxide ultrasound (oxygen content is 19.2wt%) (frequency 100Hz) of 1.7g is scattered at 30 DEG C
In the pure water of 500ml.
2. the F98 of 20g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 40g3, stirring and dissolving.
What 2. the graphene oxide water solution and step that 3. 1. step is prepared prepared contains F98 and AgNO3The aqueous solution
Isometric mixing, ultrasonic (frequency 100Hz) is processed 3 hours at 30 DEG C, is obtained and is contained Nano Silver/graphene complex aqueous solution.It is quiet
Put 3 hours, topple over supernatant, sediment uses pure water, absolute ethyl alcohol cyclic washing respectively again, until not having Ag in cleaning solution+Detection, is finally placed in product 60 DEG C of vacuum drying chambers and dries 24 hours, obtains Nano Silver/graphene complex.
4. the F98 of 20g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 25g, stirred
After dissolving, step 3. obtained Nano Silver/graphene complex 60mg is added, the azodiisobutyronitrile of 125mg is added, in 60
DEG C water-bath in carry out polymerisation, reaction stops heating after reaching 100mPa to emulsion viscosity, obtains including Nano Silver/stone
The polymer complex emulsions of black alkene.
Comparative example 2-1
The F98 of 20g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 40g3, ultrasonic (frequency 100Hz)
Treatment 3 hours.Add the methyl methacrylate of 25g, the azodiisobutyronitrile of 125mg, stirring mixing.In 60 DEG C of water-bath
In carry out polymerisation, reaction stops heating after reaching 100mPa to emulsion viscosity, obtains polymer emulsion.
Comparative example 2-2
The F98 of 20g is dissolved in 500ml pure water at 30 DEG C, (oxygen content is to add the graphene oxide of 1.7g
19.2wt%), ultrasonic (frequency 100Hz) is processed 3 hours.The methyl methacrylate of 25g is added, the azo two of 125mg is different
Butyronitrile, stirring mixing.Polymerisation is carried out in 60 DEG C of water-bath, reaction stops heating after reaching 100mPa to emulsion viscosity,
Obtain polymer emulsion.
Comparative example 2-3
The F98 of 20g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 25g, stirring is mixed
Close.The azodiisobutyronitrile of 125mg is added, polymerisation is carried out in 60 DEG C of water-bath, reaction to emulsion viscosity reaches
Stop heating after 100mPa, obtain polymer emulsion.
Embodiment 3
1. the graphene oxide (oxygen content is 16.3wt%) ultrasound (frequency 100Hz) of 1.5g is scattered at 30 DEG C
In the pure water of 500ml.
2. the F88 of 15g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 35g3, stirring and dissolving.
What 2. the graphene oxide water solution and step that 3. 1. step is prepared prepared contains F88 and AgNO3The aqueous solution
Isometric mixing, ultrasonic (frequency 100Hz) is processed 3 hours at 30 DEG C, is obtained and is contained Nano Silver/graphene complex aqueous solution.It is quiet
Put 3 hours, topple over supernatant, sediment uses pure water, absolute ethyl alcohol cyclic washing respectively again, until not having Ag in cleaning solution+Detection, is finally placed in product 60 DEG C of vacuum drying chambers and dries 24 hours, obtains Nano Silver/graphene complex.
4. the F88 of 15g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 22.5g, stirred
After mixing dissolving, step 3. obtained Nano Silver/graphene complex 45mg is added, adds the azodiisobutyronitrile of 112.5mg,
Polymerisation is carried out in 60 DEG C of water-bath, reaction stops heating, obtains including nanometer after reaching 100mPa to emulsion viscosity
The polymer complex emulsions of silver/graphite alkene.
Comparative example 3-1
The F88 of 15g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 35g3, ultrasonic (frequency 100Hz)
Treatment 3 hours.Add the methyl methacrylate of 22.5g, the azodiisobutyronitrile of 112.5mg, stirring mixing.In 60 DEG C
Polymerisation is carried out in water-bath, reaction stops heating, obtains polymer emulsion after reaching 100mPa to emulsion viscosity.
Comparative example 3-2
The F88 of 15g is dissolved in 500ml pure water at 30 DEG C, (oxygen content is to add the graphene oxide of 1.5g
16.3wt%), ultrasonic (frequency 100Hz) is processed 3 hours.Add the methyl methacrylate of 22.5g, the azo of 112.5mg
Bis-isobutyronitrile, stirring mixing.Polymerisation is carried out in 60 DEG C of water-bath, reaction stops adding after reaching 100mPa to emulsion viscosity
Heat, obtains polymer emulsion.
Comparative example 3-3
The F88 of 15g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 22.5g, stirred
Mixing.The azodiisobutyronitrile of 112.5mg is added, polymerisation is carried out in 60 DEG C of water-bath, reaction to emulsion viscosity reaches
Stop heating after 100mPa, obtain polymer emulsion.
Embodiment 4
1. the graphene oxide (oxygen content is 14.4wt%) ultrasound (frequency 100Hz) of 1.3g is scattered at 30 DEG C
In the pure water of 500ml.
2. the F68 of 10g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 30g3, stirring and dissolving.
What 2. the graphene oxide water solution and step that 3. 1. step is prepared prepared contains F68 and AgNO3The aqueous solution
Isometric mixing, ultrasonic (frequency 100Hz) is processed 3 hours at 30 DEG C, is obtained and is contained Nano Silver/graphene complex aqueous solution.It is quiet
Put 3 hours, topple over supernatant, sediment uses pure water, absolute ethyl alcohol cyclic washing respectively again, until not having Ag in cleaning solution+Detection, is finally placed in product 60 DEG C of vacuum drying chambers and dries 24 hours, obtains Nano Silver/graphene complex.
4. the F68 of 10g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 20g, stirred
After dissolving, step 3. obtained Nano Silver/graphene complex 30mg is added, the azodiisobutyronitrile of 100mg is added, in 60
DEG C water-bath in carry out polymerisation, reaction stops heating after reaching 100mPa to emulsion viscosity, obtains including Nano Silver/stone
The polymer complex emulsions of black alkene.
Comparative example 4-1
The F68 of 10g is dissolved in 500ml pure water at 30 DEG C, adds the AgNO of 30g3, ultrasonic (frequency 100Hz)
Treatment 3 hours.Add the methyl methacrylate of 20g, the azodiisobutyronitrile of 100mg, stirring mixing.In 60 DEG C of water-bath
In carry out polymerisation, reaction stops heating after reaching 100mPa to emulsion viscosity, obtains polymer emulsion.
Comparative example 4-2
The F68 of 10g is dissolved in 500ml pure water at 30 DEG C, (oxygen content is to add the graphene oxide of 1.3g
14.4wt%), ultrasonic (frequency 100Hz) is processed 3 hours.The methyl methacrylate of 20g is added, the azo two of 100mg is different
Butyronitrile, stirring mixing.Polymerisation is carried out in 60 DEG C of water-bath, reaction stops heating after reaching 100mPa to emulsion viscosity,
Obtain polymer emulsion.
Comparative example 4-3
The F68 of 10g is dissolved in 500ml pure water at 30 DEG C, adds the methyl methacrylate of 20g, stirring is mixed
Close.The azodiisobutyronitrile of 100mg is added, polymerisation is carried out in 60 DEG C of water-bath, reaction to emulsion viscosity reaches
Stop heating after 100mPa, obtain polymer emulsion.
Using the method for plate culture count, the emulsion prepared by testing example and comparative example is imitated to the antibacterial of Escherichia coli
Really.
Concrete operation step is as follows：
(1) by beef extract 4.5g, peptone 15g, NaCl 7.5g, agar 35g, water 2000mL are configured to LB nutrient solutions
(pH7.0~7.2).
(2) 18 conical flasks are taken, labeled as 1~No. 18, the LB nutrient solutions of 100mL is separately added into every conical flask；So
18 conical flasks and some test tubes for bandaging, liquid-transfering gun pipette tips etc. are placed in high-pressure sterilizing pot together afterwards, 121 DEG C damp and hot to go out
Bacterium 20min.
(3) take No. 1 conical flask for sterilizing to be placed on aseptic, ultra-clean workbench, to accessing the large intestine that has activated in bottle
Bacillus bacterium solution 1mL, appropriate vibration is mixed, and (30 DEG C, 150r/min) is cultivated 16 hours in being put into constant temperature oscillator.
(4) take 2~No. 18 conical flasks for sterilizing to be placed on aseptic, clean workbench, in 2~No. 5 conical flasks points
Not Jia Ru embodiment 1, embodiment 2, embodiment 3, embodiment 4 prepare Nano Silver/Graphene/polymer composite antibacterial emulsion it is each
0.45ml；To be separately added into 6~No. 9 conical flasks comparative example 1-1, comparative example 2-1, comparative example 3-1, comparative example 4-1 prepare
Each 0.45ml of emulsion organizes 1 as a comparison；To being separately added into comparative example 1-2, comparative example 2-2, comparative example in 10~No. 13 conical flasks
Each 0.45ml of emulsion prepared by 3-2, comparative example 4-2 organizes 2 as a comparison；To being separately added into comparative example 1- in 14~No. 17 conical flasks
3rd, each 0.45ml of emulsion prepared by comparative example 2-3, comparative example 3-3, comparative example 4-3 organizes 3 as a comparison；It is not added with No. 18 conical flasks
Enter any material (blank) and organize 4 as a comparison.
(5) Escherichia coli bacteria liquid cultivated 16 hours in No. 1 conical flask is respectively taken into 0.10mL and is respectively connected to 2~No. 18 cones
In shape bottle nutrient solution, constant-temperature table culture (150r/min, 30 DEG C) is carried out.
(6) count plate after constant-temperature table culture 24 hours, calculates antibiotic rate.
Emulsion prepared by embodiment and comparative example is shown in Table 1 to the anti-bacteria test result of Escherichia coli.
Table 1
As seen from the results in Table 1, the antimicrobial emulsion antibacterial effect for preparing of the present invention is up to more than 96%, higher than nanometer
Silver/polymer complex emulsions, far above Graphene/polymer complex emulsions.
Claims (4)
1. the preparation method of a kind of Nano Silver/Graphene/polymer composite antibacterial emulsion, it is characterised in that comprise the following steps：
(1) graphene oxide ultrasonic disperse is obtained into solution A in water；By polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization
Thing is dissolved in the water, and adds AgNO3Obtain solution B；Polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer is dissolved in
In water, add acrylate and obtain solution C；The water is pure water；Graphene oxide quality and water volume ratio are 1 in solution A
~5mg/ml；Polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount of substance and water volume ratio are 10~50mg/ in solution B
Ml, AgNO3Quality is 50~100mg/ml with water volume ratio；Polyoxyethylene-poly-oxypropylene polyoxyethylene block is total in solution C
Polymers quality is 10~50mg/ml with water volume ratio, and the ratio between acrylate quality and water volume are 30~60mg/ml；
(2) solution A and solution B are well mixed to obtain Nano Silver/graphene complex aqueous solution in equal volume, by gained Nano Silver/
The graphene complex aqueous solution carries out post-processing to obtain Nano Silver/graphene complex；
(3) solution C is mixed with Nano Silver/graphene complex, adds initiator, polymerisation carried out in water bath with thermostatic control and is obtained
Nano Silver/Graphene/polymer composite antibacterial emulsion.
2. preparation method according to claim 1, it is characterised in that Nano Silver/graphene complex addition in step (3)
It is 0.1~0.5wt% of acrylate quality in solution C；Initiator addition is acrylate quality in solution C
0.5wt%.
3. preparation method according to claim 1, it is characterised in that the initiator is azodiisobutyronitrile.
4. preparation method according to claim 1, it is characterised in that polymeric reaction temperature is 55~65 DEG C in step (3).
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| CN113637232B (en) * | 2021-09-11 | 2022-04-15 | 深圳环能石墨烯科技有限公司 | Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof |
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| CN101564400A (en) * | 2009-05-31 | 2009-10-28 | 中山大学 | Antibacterial supermolecule aquogel and preparation method and application thereof |
| CN102224819A (en) * | 2011-04-02 | 2011-10-26 | 中国科学院海洋研究所 | Nano silver loaded graphene oxide composite bactericide, and its preparation and application |
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