CN105199039A - Nano-silver/graphene/polymer composite antibacterial emulsion and preparation method thereof - Google Patents
Nano-silver/graphene/polymer composite antibacterial emulsion and preparation method thereof Download PDFInfo
- Publication number
- CN105199039A CN105199039A CN201510598120.0A CN201510598120A CN105199039A CN 105199039 A CN105199039 A CN 105199039A CN 201510598120 A CN201510598120 A CN 201510598120A CN 105199039 A CN105199039 A CN 105199039A
- Authority
- CN
- China
- Prior art keywords
- graphene
- solution
- water
- preparation
- silver
- 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.)
- Granted
Links
Abstract
The invention discloses a nano-silver/graphene/polymer composite antibacterial emulsion and a preparation method thereof. The preparation method comprises the steps that graphene oxide is ultrasonically dispersed in water to obtain a solution A; a polyoxyethylene-polyoxypropylene-polyoxyethylene segmented copolymer and AgNO3 dissolve in water to obtain a solution B; the polyoxyethylene-polyoxypropylene-polyoxyethylene segmented copolymer dissolves in water and then acrylate is added to obtain a solution C; The solution A and the solution B are mixed to obtain a nano silver/graphene compound water solution, and a nano silver/graphene compound is obtained through treatment; then, the nano silver/graphene compound is mixed with the solution C, an initiator is added to perform polymerization reaction so as to obtain the nano-silver/graphene/polymer composite antibacterial emulsion. By means of the preparation method, nano-silver particles can be evenly supported on graphene, the nano silver/graphene compound is evenly dispersed in a polymer emulsion to form the stable nano-silver/graphene/polymer composite antibacterial emulsion, and the prepared composite antibacterial emulsion has good antibacterial performance.
Description
Technical field
The invention belongs to nano composite material and antimicrobial technology neck city, be specifically related to the preparation method of a kind of nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion.
Background technology
Nano silver particles has high-specific surface area, unique physico-chemical property, efficiently anti-microbial activity, has been widely used in the coating of medicine equipment, medical dressing, water body filtration, yarn fabric and other Healthy relevant products.Nano silver particles is with in the building-up process of water medium, and tensio-active agent has solubilising and stable effect.Meanwhile, when medicine and human body interact, tensio-active agent has auxiliary function, and it can be included into cytolemma, and inserts to cell interior, thus improves the pharmacologically active of antiseptic-germicide.
Graphene is with sp
2the single carbon atom lamella of hydridization forms a kind of Novel Carbon Nanomaterials.There is oxy radical at its lamella edge to graphene oxide, as carboxylic acid group and carbonyl, base plane has epoxide group and hydroxyl, and therefore graphene oxide can be dispersed in polar solvent well.Graphene also has certain anti-microbial effect, and when contacting with bacterium, the cytolemma of bacterium can cut by the two-dimension plane structure of Graphene, draws the phospholipid molecule on cytolemma simultaneously, makes inactivation of bacteria.Nano silver particles, because easily reunite, makes its Application Areas be restricted.Utilize the specific surface area of Graphene superelevation and unique physico-chemical property, by the growth in situ of nano silver particles on Graphene, effectively can prevent the nano silver particles of load on Graphene from reuniting, strengthen its anti-microbial property.
Application number be 201210322739.5 Chinese invention patent application document disclose and adopt LBL electrostatic self-assembled technique, graphene sheet layer and Ag nano particles compound is made by electrostatic adsorption, prepare the nanometer Ag/graphene composite film of biomimetic features, this film has excellent anti-microbial property and stronger film-substrate cohesion, can play antibacterial effect for a long time.
Application number be 201410173113.1 Chinese invention patent application document disclose a kind of graphene oxide/silver-colored complexing anti-biotic material and preparation method thereof, step is as follows: (1) graphene oxide powder dispersion in deionized water, graphene oxide dispersion is obtained through ultrasonic abundant stripping, add the water soluble organic substance with large π key more wherein, then through ultrasonic abundant mixing; (2) Silver Nitrate is water-soluble, then add S-WAT or Trisodium Citrate wherein, be obtained by reacting silver complex; (3) silver complex that graphene oxide water solution step (1) obtained and step (2) obtain mixes, and after reaction terminates, filters out precipitation.Silver and organic or inorganic complex compound are formed small molecules and strengthens its stability in conjunction with graphene oxide again, and extend anti-microbial property by its slow-releasing.
Application number be 201210054952.2 Chinese invention patent application document disclose the method for a kind of Liquid preparation methods Graphene/silver nano particle composite material.Adopt DMF as reductive agent, graphene powder as carrier, under the reaction conditions of gentleness, silver on graphene layer forming core, grow up, obtain Graphene/silver nano particle composite material.
Application number be 201410508312.3 Chinese invention patent application document disclose a kind of polyphenolic compound and modify the preparation method of silver-colored Graphene antibiosis hydrogel of also publishing originally.Join in deionized water by graphene oxide, polyphenolic compound, ultrasonic disperse gets a uniform mixture, and is heated to 80 ~ 100 DEG C of reactions 4 ~ 20 hours afterwards, namely obtains the grapheme modified hydrogel of Polyphenols after cooling.Then grapheme modified for the Polyphenols obtained hydrogel is immersed in certain density silver nitrate aqueous solution, after question response is complete, namely obtains anti-bacterial hydrogel.
Application number is the preparation method that the Chinese invention patent application document of 201110003784.X discloses a kind of silver/graphene antimicrobial composite material, comprising: aqueous solution a) providing reduced form graphene oxide-polystyrene sulphuric acid sodium mixture; B) aqueous solution to described step mixture a) is heated to 50 DEG C ~ 70 DEG C; C) to step b) heating after mixture the aqueous solution in add silver nitrate solution reaction after obtain silver/graphene antimicrobial composite material.
Application number be 201510159459.0 Chinese invention patent application document relate to a kind of heat-resistance antibacterial poly-lactic acid material and preparation method thereof, this material comprises poly(lactic acid) body material and is dispersed in nanometer silver/stannic oxide/graphene nano matrix material in this poly(lactic acid) body material.Nanometer silver/stannic oxide/graphene nano matrix material obtains by forming nano-Ag particles at graphene oxide solution situ reduction Silver Nitrate in surface of graphene oxide.Heat-resistance antibacterial poly-lactic acid material of the present invention has excellent heat-resisting and anti-microbial property than common poly-lactic acid material.
Application number is that the Chinese invention patent application document of 201410686251.X discloses a kind of amination polyoxyethylene glycol functional graphene oxide loading nano silvery anti-biotic material and preparation method.The method comprises the following steps: add in the aqueous solution of graphene oxide by amination polyoxyethylene glycol, add 1-ethyl-(3-dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate and N-hydroxy-succinamide again, stirring reaction after adjustment pH, obtains the graphene oxide that amination is polyethyleneglycol modified; Be made into the aqueous solution, add Silver Nitrate, post-heating to be dissolved, to boiling, adds Trisodium Citrate or the NaBH4 aqueous solution, reaction, and cooling, obtains amination polyoxyethylene glycol functional graphene oxide loading nano silvery anti-biotic material.
Application number be 201410129503.9 Chinese invention patent application document relate to a kind of preparation method and application of graphene oxide/silver/modifying titanium dioxide mixture.First, take crystalline flake graphite as raw material, adopt Hummer legal system for graphene oxide, and be made into graphene oxide solution, then have the nano titanium oxide of polyacrylic ester with surface grafting, and silver salt jointly mixes, boils, super filter tube wash-out, obtains composite slow-release anti-biotic material.Above-mentioned anti-biotic material and thermoplastic resin are extruded, blown film, the plastics prepared have the high-efficiency antimicrobial effect of long duration.
The Chinese invention patent application document 5 that application number is 201410337717. provides a kind of method efficiently preparing Nano silver grain-Graphene three dimensional composite structure, the method comprises the following steps: 1. under the condition of adding ammoniacal liquor, obtain Nano silver grain by Reduction of Glucose Silver Nitrate, make it be deposited on graphene oxide lamella by charge effect; 2. in autoclave, removed the oxygen-containing functional group of surface of graphene oxide by hydrothermal method reduction, obtain Nano silver grain-Graphene three dimensional composite structure hydrogel; 3. obtained three dimensional composite structure hydrogel is carried out lyophilize, remove moisture, obtain that intensity is high, conduction is good, compound uniform Nano silver grain-Graphene three dimensional composite structure.
Application number be 201310549749.7 Chinese invention patent application document disclose a kind of preparation method with the flexible and transparent conductive polymeric film of anti-microbial property, belong to nano composite material technical field.First the present invention adopts Hummers method to prepare the graphene oxide colloid of stable dispersion, then the electrostatic adsorption of diallyl dimethyl ammoniumchloride is utilized to carry out finishing to graphene oxide, nano silver wire/graphene nano hybrid material is prepared by the method for original position induction silver nanowire growth, further employing solution-casting method prepares nano silver wire/Graphene/PVA (PVOH) FILM, and this film has antibacterial, the characteristic such as high conductivity, high transmission rate, softness.
Summary of the invention
The object of the present invention is to provide a kind of nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion preparation method, the inventive method can make nano silver particles comparatively uniform loading on Graphene, and nanometer silver/graphene complex is dispersed in polymer emulsion, form stable nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion, and obtained composite antibacterial emulsion has good antimicrobial property.
A preparation method for nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion, comprises the steps:
(1) graphene oxide ultrasonic disperse is obtained solution A in water; Polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is dissolved in the water, then adds AgNO
3obtain solution B; Polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is dissolved in the water, then adds acrylate and obtain solution C;
(2) solution A is mixed to obtain nanometer silver/graphene complex aqueous solution with solution B, gained nanometer silver/graphene complex aqueous solution is carried out aftertreatment and obtains nanometer silver/graphene complex;
(3) solution C is mixed with nanometer silver/graphene complex, then add initiator, carry out polyreaction in water bath with thermostatic control and obtain nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion.
Preferably, described water is pure water, more preferably ultrapure water.Graphene is as the excellent carrier of nano silver particles, and obtained nano silver particles/graphene composite material has synergetic antibacterial effect.And nanometer silver/graphene complex is prepared using amphiphilic block copolymer as reductive agent and stablizer, and then using amphiphilic block copolymer as tensio-active agent, prepare with polymer emulsion be dispersion medium comprise the important research direction that nano silver particles/graphene complex is current nanometer Ag antiseptic-germicide.
The inventive method is first with AgNO
3for presoma, polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is reductive agent and nanoparticle dispersion stablizer, prepares nanometer silver/graphene complex by ultrasonic wave added hydrothermal synthesis method.Then be function monomer with acrylate, nanometer silver/graphene complex is weighting material, polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is tensio-active agent and dispersion stabilizer, prepares nanometer silver/Graphene/polymkeric substance composite emulsion by letex polymerization.The present invention takes full advantage of polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer and has the characteristics such as reductive agent, nanoparticle dispersion stablizer, tensio-active agent, nanometer silver/Graphene/polymkeric substance composite emulsion is prepared by a kind of environmental protection, fast and convenient method, obtained nanometer silver/Graphene/polymkeric substance composite emulsion has good anti-microbial property, reaches more than 96% to colibacillary antibiotic rate.
Nanometer silver/Graphene of the present invention/polymkeric substance composite antibacterial emulsion can be widely used in the aspects such as architectural lighting body, road lighting lampshade, automobile lamp and sanitary ware by coating method.The present invention adopts hydrothermal synthesis method to prepare nanometer silver/graphene complex, selects amphiphilic block copolymer as reductive agent and dispersion agent, meanwhile, prepares amphiphilic block copolymer in the process of antimicrobial emulsion use as tensio-active agent again in polymerization.Graphene, as the excellent carrier of nano silver particles, improves the dispersiveness of nano silver particles, indirectly also just improves antibacterial effect; In addition, due to the very good mechanical properties of Graphene self, will make the object such as glass, plastic plate, pottery of coated nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion while having good antibacterial effect, its shock resistance improves.
Preferably, in solution A, graphene oxide quality and pure water volume ratio are 1 ~ 5mg/ml.Further preferably, in solution A, graphene oxide quality and pure water volume ratio are 2.5 ~ 4mg/ml.
The oxygen level of described graphene oxide is 10 ~ 25wt%, preferably, graphene oxide can select the 800 order Graphite Powder 99s of AladdinIndustrialCooperation to obtain (Zhao Li by the self-control of Hummers method, Chen Yufei, Wang Ting, Wu Liguang. the in-situ polymerization of graphene oxide/polyurethane hybrid film builds and gas permeability. matrix material journal, 2015,32,673-682).
Preferably, in solution B, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and pure water volume ratio are 10 ~ 50mg/ml, AgNO
3quality and pure water volume ratio are 50 ~ 100mg/ml.
Further preferably, in solution B, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and pure water volume ratio are 20 ~ 50mg/ml, AgNO
3quality and pure water volume ratio are 60 ~ 90mg/ml.
Preferably, in solution C, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and water volume ratio are 10 ~ 50mg/ml, and acrylate quality is 30 ~ 60mg/ml with the ratio of volume of water.
Further preferably, in solution C, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and water volume ratio are 20 ~ 50mg/ml, and acrylate quality is 40 ~ 55mg/ml with the ratio of volume of water.
Most preferably, in solution A, graphene oxide quality and pure water volume ratio are 2.6mg/ml; In solution B, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and pure water volume ratio are 20mg/ml, AgNO
3quality and pure water volume ratio are 60mg/ml; In solution C, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and water volume ratio are 20mg/ml, and acrylate quality is 40mg/ml with the ratio of volume of water.
Acrylate is any one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate or butyl methacrylate, is preferably methyl methacrylate.
Polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is the one in commercially available Pluronic series product, preferred F108, F98, F88, F68 product.
Preferably, in step (2), solution A mixes with solution B equal-volume.
Preferably, in step (3), nanometer silver/graphene complex add-on is 0.1 ~ 0.5wt% of acrylate quality in solution C; Initiator add-on is the 0.5wt% of acrylate quality in solution C.
Preferably, described initiator is Diisopropyl azodicarboxylate.
Preferably, solution A, solution B and solution C are all obtained at 25 ~ 35 DEG C.Preferred obtained at 30 DEG C further.
Preferably, after solution A mixes with solution B in step (2), then at 25 ~ 35 DEG C supersound process 2.5 ~ 3.5 hours.Further, after solution A mixes with solution B in step (2), then at 30 DEG C supersound process 3 hours.
Described in step (2), aftertreatment is: after obtained nanometer silver/graphene complex aqueous solution is left standstill 3 hours, topple over supernatant liquor, then use pure water, ethanol repetitive scrubbing respectively, until do not have Ag in washings
+detect; Vacuum-drying 24 hours at 60 DEG C again.
Preferably, in step (3), polymeric reaction temperature is 55 ~ 65 DEG C.Preferably 60 DEG C further
The present invention also provide a kind of as described in nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion of preparing of preparation method.
Compared with prior art, the present invention has following beneficial effect:
The inventive method can make nano silver particles comparatively uniform loading on Graphene, and nanometer silver/graphene complex is dispersed in polymer emulsion, form stable nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion, and obtained composite antibacterial emulsion has good antimicrobial property.
Embodiment
Further illustrating below by way of specific embodiment utilizes the present invention how to prepare nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion, and the anti-microbial property of prepared composite emulsion.
Raw materials usedly in following examples except specified otherwise, all commercial goods can be adopted.
Embodiment 1
1. the graphene oxide (oxygen level is 22.4wt%) ultrasonic (frequency 100Hz) of 2.0g is scattered in the pure water of 500ml at 30 DEG C.
2. the F108 of 25g is dissolved in 500ml pure water at 30 DEG C, then adds the AgNO of 45g
3, stirring and dissolving.
What 2. the graphene oxide water solution 3. step 1. prepared and step were prepared contains F108 and AgNO
3the mixing of aqueous solution equal-volume, ultrasonic at 30 DEG C (frequency 100Hz) processes 3 hours, obtained containing nanometer silver/graphene complex aqueous solution.Leave standstill 3 hours, topple over supernatant liquor, throw out uses pure water, dehydrated alcohol repetitive scrubbing more respectively, until do not have Ag in washings
+detect, finally product is placed in 60 DEG C of vacuum drying ovens dry 24 hours, obtains nanometer silver/graphene complex.
4. the F108 of 25g is dissolved in 500ml pure water at 30 DEG C, add the methyl methacrylate of 27.5g again, after stirring and dissolving, add nanometer silver/graphene complex 75mg that 3. step obtains, add the Diisopropyl azodicarboxylate of 137.5mg again, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain the polymkeric substance composite emulsion including nanometer silver/Graphene.
Comparative example 1-1
At 30 DEG C, the F108 of 25g is dissolved in 500ml pure water, then adds the AgNO of 45g
3, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 27.5g again, the Diisopropyl azodicarboxylate of 137.5mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 1-2
Be dissolved in 500ml pure water by the F108 of 25g at 30 DEG C, then add the graphene oxide (oxygen level is 22.4wt%) of 2.0g, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 27.5g again, the Diisopropyl azodicarboxylate of 137.5mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 1-3
At 30 DEG C, the F108 of 25g is dissolved in 500ml pure water, then adds the methyl methacrylate of 27.5g, be uniformly mixed.Add the Diisopropyl azodicarboxylate of 137.5mg, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Embodiment 2
1. ultrasonic for the graphene oxide of 1.7g (oxygen level is 19.2wt%) (frequency 100Hz) is scattered in the pure water of 500ml at 30 DEG C.
2. the F98 of 20g is dissolved in 500ml pure water at 30 DEG C, then adds the AgNO of 40g
3, stirring and dissolving.
What 2. the graphene oxide water solution 3. step 1. prepared and step were prepared contains F98 and AgNO
3the mixing of aqueous solution equal-volume, ultrasonic at 30 DEG C (frequency 100Hz) processes 3 hours, obtained containing nanometer silver/graphene complex aqueous solution.Leave standstill 3 hours, topple over supernatant liquor, throw out uses pure water, dehydrated alcohol repetitive scrubbing more respectively, until do not have Ag in washings
+detect, finally product is placed in 60 DEG C of vacuum drying ovens dry 24 hours, obtains nanometer silver/graphene complex.
4. the F98 of 20g is dissolved in 500ml pure water at 30 DEG C, add the methyl methacrylate of 25g again, after stirring and dissolving, add nanometer silver/graphene complex 60mg that 3. step obtains, add the Diisopropyl azodicarboxylate of 125mg again, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain the polymkeric substance composite emulsion including nanometer silver/Graphene.
Comparative example 2-1
At 30 DEG C, the F98 of 20g is dissolved in 500ml pure water, then adds the AgNO of 40g
3, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 25g again, the Diisopropyl azodicarboxylate of 125mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 2-2
Be dissolved in 500ml pure water by the F98 of 20g at 30 DEG C, then add the graphene oxide (oxygen level is 19.2wt%) of 1.7g, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 25g again, the Diisopropyl azodicarboxylate of 125mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 2-3
At 30 DEG C, the F98 of 20g is dissolved in 500ml pure water, then adds the methyl methacrylate of 25g, be uniformly mixed.Add the Diisopropyl azodicarboxylate of 125mg, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Embodiment 3
1. the graphene oxide (oxygen level is 16.3wt%) ultrasonic (frequency 100Hz) of 1.5g is scattered in the pure water of 500ml at 30 DEG C.
2. the F88 of 15g is dissolved in 500ml pure water at 30 DEG C, then adds the AgNO of 35g
3, stirring and dissolving.
What 2. the graphene oxide water solution 3. step 1. prepared and step were prepared contains F88 and AgNO
3the mixing of aqueous solution equal-volume, ultrasonic at 30 DEG C (frequency 100Hz) processes 3 hours, obtained containing nanometer silver/graphene complex aqueous solution.Leave standstill 3 hours, topple over supernatant liquor, throw out uses pure water, dehydrated alcohol repetitive scrubbing more respectively, until do not have Ag in washings
+detect, finally product is placed in 60 DEG C of vacuum drying ovens dry 24 hours, obtains nanometer silver/graphene complex.
4. the F88 of 15g is dissolved in 500ml pure water at 30 DEG C, add the methyl methacrylate of 22.5g again, after stirring and dissolving, add nanometer silver/graphene complex 45mg that 3. step obtains, add the Diisopropyl azodicarboxylate of 112.5mg again, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain the polymkeric substance composite emulsion including nanometer silver/Graphene.
Comparative example 3-1
At 30 DEG C, the F88 of 15g is dissolved in 500ml pure water, then adds the AgNO of 35g
3, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 22.5g again, the Diisopropyl azodicarboxylate of 112.5mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 3-2
Be dissolved in 500ml pure water by the F88 of 15g at 30 DEG C, then add the graphene oxide (oxygen level is 16.3wt%) of 1.5g, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 22.5g again, the Diisopropyl azodicarboxylate of 112.5mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 3-3
At 30 DEG C, the F88 of 15g is dissolved in 500ml pure water, then adds the methyl methacrylate of 22.5g, be uniformly mixed.Add the Diisopropyl azodicarboxylate of 112.5mg, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Embodiment 4
1. the graphene oxide (oxygen level is 14.4wt%) ultrasonic (frequency 100Hz) of 1.3g is scattered in the pure water of 500ml at 30 DEG C.
2. the F68 of 10g is dissolved in 500ml pure water at 30 DEG C, then adds the AgNO of 30g
3, stirring and dissolving.
What 2. the graphene oxide water solution 3. step 1. prepared and step were prepared contains F68 and AgNO
3the mixing of aqueous solution equal-volume, ultrasonic at 30 DEG C (frequency 100Hz) processes 3 hours, obtained containing nanometer silver/graphene complex aqueous solution.Leave standstill 3 hours, topple over supernatant liquor, throw out uses pure water, dehydrated alcohol repetitive scrubbing more respectively, until do not have Ag in washings
+detect, finally product is placed in 60 DEG C of vacuum drying ovens dry 24 hours, obtains nanometer silver/graphene complex.
4. the F68 of 10g is dissolved in 500ml pure water at 30 DEG C, add the methyl methacrylate of 20g again, after stirring and dissolving, add nanometer silver/graphene complex 30mg that 3. step obtains, add the Diisopropyl azodicarboxylate of 100mg again, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain the polymkeric substance composite emulsion including nanometer silver/Graphene.
Comparative example 4-1
At 30 DEG C, the F68 of 10g is dissolved in 500ml pure water, then adds the AgNO of 30g
3, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 20g again, the Diisopropyl azodicarboxylate of 100mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 4-2
Be dissolved in 500ml pure water by the F68 of 10g at 30 DEG C, then add the graphene oxide (oxygen level is 14.4wt%) of 1.3g, ultrasonic (frequency 100Hz) processes 3 hours.Add the methyl methacrylate of 20g again, the Diisopropyl azodicarboxylate of 100mg, is uniformly mixed.In the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Comparative example 4-3
At 30 DEG C, the F68 of 10g is dissolved in 500ml pure water, then adds the methyl methacrylate of 20g, be uniformly mixed.Add the Diisopropyl azodicarboxylate of 100mg, in the water-bath of 60 DEG C, carry out polyreaction, react after reaching 100mPa to emulsion viscosity and stop heating, obtain polymer emulsion.
Adopt the method for plate culture count, testing example and the emulsion prepared by comparative example are to colibacillary antibacterial effect.
Concrete operation step is as follows:
(1) by extractum carnis 4.5g, peptone 15g, NaCl7.5g, agar 35g, water 2000mL are configured to LB nutrient solution (pH7.0 ~ 7.2).
(2) get 18 Erlenmeyer flasks, be labeled as 1 ~ No. 18, in every Erlenmeyer flask, add the LB nutrient solution of 100mL respectively; Then be placed in high-pressure sterilizing pot together with the test tube bandaged with some by 18 Erlenmeyer flasks, liquid-transfering gun rifle are first-class, 121 DEG C of moist heat sterilization 20min.
(3) Erlenmeyer flask getting No. 1 sterilizing is placed on aseptic, ultra-clean worktable, accesses the Escherichia coli bacteria liquid 1mL activated in bottle, mixing of suitably vibrating, and puts into constant temperature oscillator (30 DEG C, 150r/min) and cultivates 16 hours.
(4) Erlenmeyer flask getting 2 ~ No. 18 sterilizings is placed on aseptic, clean worktable, adds the nanometer silver/Graphene/each 0.45ml of polymkeric substance composite antibacterial emulsion of embodiment 1, embodiment 2, embodiment 3, embodiment 4 preparation in 2 ~ No. 5 Erlenmeyer flasks respectively; In 6 ~ No. 9 Erlenmeyer flasks, add comparative example 1-1, comparative example 2-1 respectively, each 0.45ml of emulsion prepared by comparative example 3-1, comparative example 4-1 organizes 1 as a comparison; In 10 ~ No. 13 Erlenmeyer flasks, add comparative example 1-2, comparative example 2-2 respectively, each 0.45ml of emulsion prepared by comparative example 3-2, comparative example 4-2 organizes 2 as a comparison; In 14 ~ No. 17 Erlenmeyer flasks, add comparative example 1-3, comparative example 2-3 respectively, each 0.45ml of emulsion prepared by comparative example 3-3, comparative example 4-3 organizes 3 as a comparison; Do not add any material (blank) in No. 18 Erlenmeyer flasks and organize 4 as a comparison.
(5) Escherichia coli bacteria liquid cultivated 16 hours in No. 1 Erlenmeyer flask is respectively got 0.10mL to access respectively in 2 ~ No. 18 Erlenmeyer flask nutrient solutions, carry out constant-temperature table cultivation (150r/min, 30 DEG C).
(6) constant-temperature table cultivates live bacterial count after 24 hours, calculates antibiotic rate.
Embodiment and the emulsion prepared by comparative example to colibacillary anti-bacteria test result in table 1.
Table 1
As seen from the results in Table 1, the antimicrobial emulsion antibacterial effect that the present invention prepares can reach more than 96%, higher than nano silver/polymer composite emulsion, far above Graphene/polymkeric substance composite emulsion.
Claims (10)
1. a preparation method for nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion, is characterized in that, comprise the steps:
(1) graphene oxide ultrasonic disperse is obtained solution A in water; Polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is dissolved in the water, then adds AgNO
3obtain solution B; Polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer is dissolved in the water, then adds acrylate and obtain solution C;
(2) solution A is mixed to obtain nanometer silver/graphene complex aqueous solution with solution B, gained nanometer silver/graphene complex aqueous solution is carried out aftertreatment and obtains nanometer silver/graphene complex;
(3) solution C is mixed with nanometer silver/graphene complex, then add initiator, carry out polyreaction in water bath with thermostatic control and obtain nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion.
2. preparation method according to claim 1, it is characterized in that, described water is pure water.
3. preparation method according to claim 1, it is characterized in that, in solution A, graphene oxide quality and water volume ratio are 1 ~ 5mg/ml.
4. preparation method according to claim 1, it is characterized in that, in solution B, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and water volume ratio are 10 ~ 50mg/ml, AgNO
3quality and water volume ratio are 50 ~ 100mg/ml.
5. preparation method according to claim 1, it is characterized in that, in solution C, polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymerization amount and water volume ratio are 10 ~ 50mg/ml, and acrylate quality is 30 ~ 60mg/ml with the ratio of volume of water.
6. preparation method according to claim 1, is characterized in that, in step (2), solution A mixes with solution B equal-volume.
7. preparation method according to claim 1, is characterized in that, in step (3), nanometer silver/graphene complex add-on is 0.1 ~ 0.5wt% of acrylate quality in solution C; Initiator add-on is the 0.5wt% of acrylate quality in solution C.
8. preparation method according to claim 1, it is characterized in that, described initiator is Diisopropyl azodicarboxylate.
9. preparation method according to claim 1, is characterized in that, in step (3), polymeric reaction temperature is 55 ~ 65 DEG C.
10. nanometer silver/Graphene/polymkeric substance composite antibacterial emulsion that as described in a claim as arbitrary in claim 1 ~ 9, preparation method prepares.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510598120.0A CN105199039B (en) | 2015-09-18 | 2015-09-18 | A kind of Nano Silver/Graphene/polymer composite antibacterial emulsion and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510598120.0A CN105199039B (en) | 2015-09-18 | 2015-09-18 | A kind of Nano Silver/Graphene/polymer composite antibacterial emulsion and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105199039A true CN105199039A (en) | 2015-12-30 |
| CN105199039B CN105199039B (en) | 2017-06-27 |
Family
ID=54947021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510598120.0A Active CN105199039B (en) | 2015-09-18 | 2015-09-18 | A kind of Nano Silver/Graphene/polymer composite antibacterial emulsion and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105199039B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106893012A (en) * | 2017-04-17 | 2017-06-27 | 山东本源晶体科技有限公司 | A kind of Nano Silver modified graphene crystal composite material and preparation method thereof |
| CN106905454A (en) * | 2017-04-17 | 2017-06-30 | 山东本源晶体科技有限公司 | A kind of Graphene crystal composite polrvinyl chloride anti-biotic material and preparation method thereof |
| CN108083252A (en) * | 2017-12-21 | 2018-05-29 | 上海应用技术大学 | A kind of method for the carbon material that uniform pore diameter is prepared using block polymer as template |
| CN110638359A (en) * | 2019-11-11 | 2020-01-03 | 苏州宝丽洁日化有限公司 | Preparation method of wet tissue without antibacterial agent residue on skin after use |
| CN111617103A (en) * | 2020-04-15 | 2020-09-04 | 温军海 | Silver ion graphene oxide-containing antibacterial and disinfectant protective cleaning solution |
| CN112962324A (en) * | 2021-02-01 | 2021-06-15 | 苏州大学 | Preparation method of graphene oxide/nano-silver composite coating non-woven material |
| CN113068903A (en) * | 2021-03-26 | 2021-07-06 | 莆田市协诚鞋业有限公司 | Antifouling and antibacterial upper material and preparation method thereof |
| CN113402964A (en) * | 2021-07-15 | 2021-09-17 | 桂林清研皓隆复合材料研究院有限公司 | Antibacterial coating material, preparation method thereof, antibacterial coating and product |
| CN113637232A (en) * | 2021-09-11 | 2021-11-12 | 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 |
| CN114606596A (en) * | 2022-04-13 | 2022-06-10 | 东莞市艾尔佳过滤器制造有限公司 | Graphene filter element material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637183A (en) * | 2021-08-17 | 2021-11-12 | 安徽大学 | Modified graphene-loaded nano-silver/polyvinyl alcohol antibacterial hydrogel and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544718A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | Method for preparing antibacterial composite material with nano silver particles evenly dispersed in polymeric matrix |
| 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 |
| CN103172775A (en) * | 2013-03-19 | 2013-06-26 | 浙江工商大学 | Preparation method and application of antibiosis composite emulsion containing nano silver particles |
| US20150065601A1 (en) * | 2013-09-04 | 2015-03-05 | Alfaisal University | Novel antimicrobial polymer -graphene-silver nanocomposite |
-
2015
- 2015-09-18 CN CN201510598120.0A patent/CN105199039B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544718A (en) * | 2009-05-06 | 2009-09-30 | 河北科技大学 | Method for preparing antibacterial composite material with nano silver particles evenly dispersed in polymeric matrix |
| 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 |
| CN103172775A (en) * | 2013-03-19 | 2013-06-26 | 浙江工商大学 | Preparation method and application of antibiosis composite emulsion containing nano silver particles |
| US20150065601A1 (en) * | 2013-09-04 | 2015-03-05 | Alfaisal University | Novel antimicrobial polymer -graphene-silver nanocomposite |
Non-Patent Citations (2)
| Title |
|---|
| 何光裕等: "纳米银@石墨烯复合材料的绿色制备及其抑菌性能", 《精细化工》 * |
| 张凯等: "粒子表面处理对纳米Ag/PMMA复合粒子的影响", 《塑料工业》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905454A (en) * | 2017-04-17 | 2017-06-30 | 山东本源晶体科技有限公司 | A kind of Graphene crystal composite polrvinyl chloride anti-biotic material and preparation method thereof |
| CN106893012B (en) * | 2017-04-17 | 2018-07-20 | 山东宜建新材料技术有限公司 | A kind of nano silver modified graphene crystal composite material and preparation method thereof |
| CN106905454B (en) * | 2017-04-17 | 2018-07-20 | 山东宜建新材料技术有限公司 | A kind of graphene crystal composite polrvinyl chloride anti-biotic material and preparation method thereof |
| CN106893012A (en) * | 2017-04-17 | 2017-06-27 | 山东本源晶体科技有限公司 | A kind of Nano Silver modified graphene crystal composite material and preparation method thereof |
| CN108083252A (en) * | 2017-12-21 | 2018-05-29 | 上海应用技术大学 | A kind of method for the carbon material that uniform pore diameter is prepared using block polymer as template |
| CN110638359A (en) * | 2019-11-11 | 2020-01-03 | 苏州宝丽洁日化有限公司 | Preparation method of wet tissue without antibacterial agent residue on skin after use |
| CN111617103A (en) * | 2020-04-15 | 2020-09-04 | 温军海 | Silver ion graphene oxide-containing antibacterial and disinfectant protective cleaning solution |
| CN112962324B (en) * | 2021-02-01 | 2022-04-08 | 苏州大学 | Preparation method of graphene oxide/nano-silver composite coating non-woven material |
| CN112962324A (en) * | 2021-02-01 | 2021-06-15 | 苏州大学 | Preparation method of graphene oxide/nano-silver composite coating non-woven material |
| CN113068903A (en) * | 2021-03-26 | 2021-07-06 | 莆田市协诚鞋业有限公司 | Antifouling and antibacterial upper material and preparation method thereof |
| CN113068903B (en) * | 2021-03-26 | 2022-07-12 | 莆田市协诚鞋业有限公司 | Antifouling and antibacterial upper material and preparation method thereof |
| CN113402964A (en) * | 2021-07-15 | 2021-09-17 | 桂林清研皓隆复合材料研究院有限公司 | Antibacterial coating material, preparation method thereof, antibacterial coating and product |
| CN113637232A (en) * | 2021-09-11 | 2021-11-12 | 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 |
| 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 |
| CN114606596A (en) * | 2022-04-13 | 2022-06-10 | 东莞市艾尔佳过滤器制造有限公司 | Graphene filter element material and preparation method thereof |
| CN114606596B (en) * | 2022-04-13 | 2024-04-02 | 东莞市艾尔佳过滤器制造有限公司 | Graphene filter element material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105199039B (en) | 2017-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105199039A (en) | Nano-silver/graphene/polymer composite antibacterial emulsion and preparation method thereof | |
| Zhang et al. | Multilayer electrospun nanofibrous membranes with antibacterial property for air filtration | |
| Lee et al. | Electrospun chitosan nanofibers with controlled levels of silver nanoparticles. Preparation, characterization and antibacterial activity | |
| Zhao et al. | A facile method for electrospinning of Ag nanoparticles/poly (vinyl alcohol)/carboxymethyl-chitosan nanofibers | |
| Jayaramudu et al. | Chitosan-pluronic based Cu nanocomposite hydrogels for prototype antimicrobial applications | |
| Liu et al. | Fabrication and durable antibacterial properties of electrospun chitosan nanofibers with silver nanoparticles | |
| Spagnol et al. | Cellulose nanowhiskers decorated with silver nanoparticles as an additive to antibacterial polymers membranes fabricated by electrospinning | |
| Islam et al. | Electrospun pullulan/poly (vinyl alcohol)/silver hybrid nanofibers: Preparation and property characterization for antibacterial activity | |
| Shi et al. | Electrospun polyacrylonitrile nanofibers loaded with silver nanoparticles by silver mirror reaction | |
| Elbarbary et al. | Radiation synthesis and characterization of polyvinyl alcohol/chitosan/silver nanocomposite membranes: antimicrobial and blood compatibility studies | |
| Nguyen et al. | Synthesis and characterization of nanofiber webs of chitosan/poly (vinyl alcohol) blends incorporated with silver nanoparticles | |
| US20110129536A1 (en) | Nanocomposite materials based on metallic nanoparticles stabilized with branched polysaccharides | |
| Wei et al. | Controlled release of monodisperse silver nanoparticles via in situ cross-linked polyvinyl alcohol as benign and antibacterial electrospun nanofibers | |
| Yong et al. | Recyclable magnetite-silver heterodimer nanocomposites with durable antibacterial performance | |
| CN105478792A (en) | Environment-friendly preparing method for modified chitosan-nano-silver sol | |
| CN107652451B (en) | Silver nanoparticle hybrid supramolecular hydrogel based on cyclodextrin/PEG grafted polyacrylic acid, and preparation and application thereof | |
| Kong et al. | Antibacterial polyvinyl alcohol films incorporated with N-halamine grafted oxidized microcrystalline cellulose | |
| CN111407722B (en) | Silver nanoparticle composite hydrogel, preparation method and application thereof | |
| CN103665414A (en) | Method for preparing nano Ag/polymer antimicrobial film by utilizing irradiation method | |
| Abaza et al. | Incorporating silver nanoshell-coated mesoporous silica nanoparticles improves physicochemical and antimicrobial properties of chitosan films | |
| da Silva Jr et al. | Synthesis and characterization of highly conductive polypyrrole-coated electrospun fibers as antibacterial agents | |
| Jayaramudu et al. | Green synthesis of tea Ag nanocomposite hydrogels via mint leaf extraction for effective antibacterial activity | |
| Bandatang et al. | Antimicrobial electrospun nanofiber mats of NaOH-hydrolyzed chitosan (HCS)/PVP/PVA incorporated with in-situ synthesized AgNPs: Fabrication, characterization, and antibacterial activity | |
| CN108219066A (en) | A kind of nanometer of povidone-iodine antibacterial dyestuff and preparation method thereof | |
| An et al. | Preparation of chitosan‐graft‐(methyl methacrylate)/Ag nanocomposite with antimicrobial activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221124 Address after: Room 1011, 4 / F, building 5, No. 299, Hangfu Road, Chongfu Town, Tongxiang City, Jiaxing City, Zhejiang Province Patentee after: Tongxiang Beite Technology Co.,Ltd. Address before: 310018, No. 18 Jiao Tong Street, Xiasha Higher Education Park, Hangzhou, Zhejiang Patentee before: ZHEJIANG GONGSHANG University Effective date of registration: 20221124 Address after: 310,000 Rooms 411 and 412, East Area, Building A, 525 Xixi Road, Xihu District, Hangzhou, Zhejiang Patentee after: Hangzhou Weinaweikang New Material Co.,Ltd. Address before: Room 1011, 4 / F, building 5, No. 299, Hangfu Road, Chongfu Town, Tongxiang City, Jiaxing City, Zhejiang Province Patentee before: Tongxiang Beite Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |