CN107114407A - The preparation method and application of Nanometer Copper zinc composite antibacterial material - Google Patents
The preparation method and application of Nanometer Copper zinc composite antibacterial material Download PDFInfo
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Abstract
The invention provides a kind of preparation method and application of Nanometer Copper zinc composite antibacterial material, belong to field of environment engineering, more particularly to anti-biotic material field, the Nanometer Copper zinc composite antibacterial material bactericidal effect prepared is good, can prepare antibiotic paint.The preparation method of the Nanometer Copper zinc composite antibacterial material, specifically includes following steps：Zinc salt and mantoquita are dissolved in the water to form copper zinc solution, added and the isometric absolute ethyl alcohol of copper zinc solution, it is ultrasonically treated, obtain solution I；It is 5.5 6.7 to adjust solution I pH, adds monohydrate potassium, stirring, it is ultrasonically treated into solution without flocculation, obtain solution II；By the heating water bath of solution II, stirring, centrifuging to precipitate, washing of precipitate, dry, and calcine, and cooling obtains copper zinc complex；Above-mentioned copper zinc complex and graphene are mixed in N, N dimethylacetamide solutions, it is ultrasonically treated, obtain solution III；Solution III, which is centrifuged, to be precipitated, washing of precipitate, dried, produced Nanometer Copper zinc composite antibacterial material.
Description
Technical field
The present invention relates to field of environment engineering, more particularly to anti-biotic material, and in particular to a kind of Nanometer Copper zinc composite antibacterial
The preparation method and application of material.
Background technology
The features such as industrial circulating cooling water has proper temperature (30~40 DEG C), dissolved oxygen content is high, easily causes micro- life
Thing amount reproduction in cooling water system, so as to cause quality of water conveyance to deteriorate, forms biological clay, cause heat transfer efficiency to decline,
Corrosive pipeline, the increase of aqueduct energy consumption, blocking cooling device and aqueduct etc., make the normal operation of industrial enterprise by prestige
The side of body.
For control microbiologic(al) corrosion and the formation of biological clay, conventional method is chemical antimicrobial technology at present, that is, is being followed
Chemical antiseptic is added in ring cooling water system, such as contains chloro, quaternary alkylphosphonium salt antiseptic.Its effect seems obvious, still
Its larger, operating cost of investment is high, management difficulty is big, while changing the chemical composition in water and easily causing secondary to environment
Pollution, especially adds the recirculating cooling water system of phosphorus system water treatment agent, can cause body eutrophication with the discharge of phosphorus, sternly
Weight influence ecological environment.At present, the recirculating cooling water system antiseptic of green non-pollution needs research badly.
In the nano material with antibacterial potentiality, metal nanoparticle be most development potentiality nano anti-biotic material it
One.But, the complex metal particle of nano metal is single, and germicidal efficiency is low, it is impossible to reach at lower levels higher
Bactericidal effect, during cooling water system, cost is higher and bactericidal effect is unsatisfactory.
The content of the invention
It is an object of the invention to provide a kind of preparation method and application of Nanometer Copper zinc composite antibacterial material, bactericidal effect
Good, can prepare antibiotic paint is used for recirculating cooling water system, is applied to after recirculating cooling water system tube wall, can be effective
The microorganism in recirculated water is killed, consumption is few, sterilizing rate is high and cost is relatively low.
An aspect of of the present present invention provides the preparation method of Nanometer Copper zinc composite antibacterial material, specifically includes following steps：
Zinc salt and mantoquita are dissolved in the water to form copper zinc solution, added and the isometric absolute ethyl alcohol of copper zinc solution, is surpassed
Sonication, obtains solution I；
It is 5.5-6.7 to adjust solution I pH, adds monohydrate potassium, stirring, it is ultrasonically treated into solution without flocculation, obtain
To solution II；
By the heating water bath of solution II, stirring, centrifuging to precipitate, washing of precipitate, dry, and calcine, cooling, obtain the complexing of copper zinc
Thing；
Above-mentioned copper zinc complex and graphene are mixed in DMA solution, it is ultrasonically treated, obtain molten
Liquid III；
Solution III, which is centrifuged, to be precipitated, washing of precipitate, dried, produced Nanometer Copper zinc composite antibacterial material.
As optimal technical scheme, the zinc salt and mantoquita and mol ratio are 2-5:1, the molal volume of copper zinc total amount and water
Than for 1:750-1250mol/ml.
As optimal technical scheme, the mol ratio of zinc salt and the mantoquita sum and monohydrate potassium is 1:1-1.5.
As optimal technical scheme, the mass ratio of the copper zinc complex and graphene is 3-10：1, the copper zinc complexing
The mass volume ratio of thing and DMAC N,N' dimethyl acetamide solution is：1：50-100g/ml.
As optimal technical scheme, the bath temperature is 70-90 DEG C, and the washing of precipitate is to wash 3- with absolute ethyl alcohol
5 times, the drying of the copper zinc complex is dries 24-48h in 80 DEG C of baking ovens, grind into powder after drying, and powder is in Muffle furnace
Middle 480-520 DEG C of calcining 1-3h, cooling.
As optional technical scheme, obtained after the sonicated 0.2-0.6h of the solution I；The solution II is through 30-
Obtained after the ultrasonically treated 0.5-1h of 50kHz；Obtained after the sonicated 5-7h of the solution III.
As optional technical scheme, the solution III is centrifuged and must precipitated, and is placed in after washing of precipitate in baking oven in 60 DEG C of baking ovens
Dry 24-48h.
Another aspect provides receiving that the preparation method of above-mentioned Nanometer Copper zinc composite antibacterial material is prepared
Rice copper zinc composite antibacterial material.
Another aspect of the invention provides the method for preparing antibiotic paint using above-mentioned Nanometer Copper zinc composite antibacterial material,
Comprise the following steps：Nanometer Copper zinc composite antibacterial material is added in aqueous polyurethane, stirred；Auxiliary agent is added, it is ultrasonically treated,
Produce antibiotic paint.
As optimal technical scheme, the mass ratio of the Nanometer Copper zinc composite antibacterial material and aqueous polyurethane is 1：
37.5-100；The auxiliary agent is the one or more in water, wetting agent, defoamer, wax emulsion；The ultrasonication is：
Solution is stirred into 5min, ultrasonic temperature≤35 DEG C every 30min during ultrasound.
It is yet another aspect of the present invention to provide application of the above-mentioned antibiotic paint in recirculating cooling water system.
As optimal technical scheme, the antibiotic paint is coated on circulating cooling as the antiseptic of recirculating cooling water system
The tube wall of water system.
Compared with prior art, advantages and positive effects of the present invention are：
1st, with stone after mantoquita and zinc salt being fully complexed in the preparation process of Nanometer Copper zinc composite antibacterial material of the invention
Black alkene composite Nano, obtained Nanometer Copper zinc composite antibacterial material anti-microbial property is good, and sterilizing rate is high under low concentration, significantly carries
The high anti-microbial property of material；
2nd, the composite antibacterial coating that Nanometer Copper zinc composite antibacterial material of the invention is prepared, with conventional antimicrobial coating phase
Than preparation method is easy, nontoxic pollution-free, belongs to environment-friendly antibiosis coating；
3rd, the composite antibacterial coating that Nanometer Copper zinc composite antibacterial material of the invention is prepared is applied to circulating cooling water system
After wall under the overall leadership, carbon steel tube wall can be significantly slowed and corroded by recirculated cooling water, the antibacterial cycle is long, stability is good.
Brief description of the drawings
Fig. 1 compares Nanometer Copper zinc composite antibacterial material for the Mole percent that the copper acetate of the embodiment of the present invention accounts for copper zinc salt summation
Expect sterilizing rate influence figure；
Fig. 2 kills for the mass percent that graphene accounts for Nanometer Copper zinc composite antibacterial material to Nanometer Copper zinc composite antibacterial material
Bacterium rate influence figure；
Fig. 3 is the nanometer that nano zine oxide, bar-shaped cuprous oxide, graphene, copper zinc complex and embodiment 1 are prepared
Copper zinc composite antibacterial material sterilizing rate comparison diagram；
Fig. 4 is that Nanometer Copper zinc composite antibacterial material preparation process different solvents influence to scheme on sterilizing rate；
Fig. 5 is that addition of the Nanometer Copper zinc composite antibacterial material in antibiotic paint influences to scheme on antibiotic paint sterilizing rate.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
One embodiment of the invention provides a kind of preparation method of Nanometer Copper zinc composite antibacterial material, specifically includes as follows
Step：
S1：Zinc salt and mantoquita are dissolved in the water to form copper zinc solution, added and the isometric absolute ethyl alcohol of copper zinc solution,
It is ultrasonically treated, obtain solution I.
In this steps, water-soluble zinc salt and mantoquita formation copper zinc mixed solution are selected, polar solvent dissolving is added,
It is that next step complex reaction is prepared beneficial to the high degree of dispersion of copper zinc in a solvent.
S2：It is 5.5-6.7 to adjust solution I pH, adds monohydrate potassium, stirring, it is ultrasonically treated into solution without flocculation,
Obtain solution II.
In this step, monohydrate potassium is have selected as complexing agent, and effectively zinc ion and copper ion can be carried out
Complexing, so that zinc ion and copper ion activity are higher, beneficial to the bactericidal activity that height is kept with the compound tense of graphene.
S3：By the heating water bath of solution II, stirring, centrifuging to precipitate, washing of precipitate, dry, and calcine, and cooling obtains copper zinc network
Compound.
This step can be separated copper zinc complex, washed dried calcination processing and obtained more stable copper
Zinc complex.
S4：Above-mentioned copper zinc complex and graphene are mixed in DMA solution, it is ultrasonically treated, obtain
Solution III.
In this step, the copper zinc complex of functionalization is combined in a solvent with graphene, ultrasonically treated to be beneficial to nano-antibacterial
The formation of material, ensure that the bactericidal activity of material.
S5：Solution III, which is centrifuged, to be precipitated, washing of precipitate, dried, produced Nanometer Copper zinc composite antibacterial material.
After this step removes unnecessary solvent, washing drying can obtain the Nanometer Copper zinc composite antibacterial material of purifying.
In the preferred embodiment of the present invention, zinc salt and mantoquita and mol ratio are 2-5:1, mole of copper zinc total amount and water
Volume ratio is 1:750-1250mol/ml.Zinc salt and the mol ratio of mantoquita are given in the present embodiment and the two is integrated and water
Ratio.It is understood that in a particular embodiment, zinc salt and mantoquita can be the metal salt for being dissolved in water, such as second
Sour zinc, copper acetate etc..To ensure sufficient bactericidal effect, zinc salt and mantoquita and mol ratio are 2-5:1, any within the range
Ratio, such as 2.5:1,3:1,3.5:Isosorbide-5-Nitrae:Isosorbide-5-Nitrae .5:1 etc., within the range, the two coordinates sterilizing rate high, bactericidal property
It is stable.For the consumption of water, it can dissolve mantoquita and zinc salt, and consumption excessively causes copper zinc ion concentration height too low, no
Beneficial to the progress of subsequent reactions, the copper zinc total amount and the molal volume ratio of water provided in the present embodiment is 1:750-1250mol/
Ml, any proportion within the range, such as 1:850,1:950,1:1050,1:1150 etc..
In the preferred embodiment of the present invention, zinc salt and mantoquita sum and the mol ratio of monohydrate potassium are 1:1-
1.5.For complexing agent, it is to be understood that complexing agent species commonly used in the art can be used in above-mentioned steps such as EDTA
In, complexing agent preferably is monohydrate potassium；Monohydrate potassium is as chelating agent, if consumption is very little, can cause mantoquita
It is incomplete with zinc salt complexing, it is unfavorable for subsequently compound with graphene, consumption excessively causes complexing agent to cause while waste
And solution property changes, and is unfavorable for the output of copper zinc complex, therefore, mole of zinc salt and mantoquita sum and monohydrate potassium
Than for 1:1-1.5, within the above range can arbitrarily value, such as 1:1.1,1:1.2,1:1.3,1:1.4 wait.
In the preferred embodiment of the present invention, the mass ratio of copper zinc complex and graphene is 3-10：1, the copper zinc
The mass volume ratio of complex compound and DMAC N,N' dimethyl acetamide solution is：1：50-100g/ml.In the present embodiment, copper zinc complex
The load of graphene can be ensured with the aforementioned proportion of graphene, it is ensured that the material after load possesses bactericidal activity, specifically, copper
The ratio of zinc complex and graphene can be any proportion in above range, such as 4:1,5:1,6:1,7:1,8:1,9:1
Deng.For DMA as solvent, to avoid very few influence load-reaction, cost, the complexing of copper zinc are excessively improved
The volume ratio of thing and DMAC N,N' dimethyl acetamide solution is：1：50-100g/mL, specifically, above-mentioned mass volume ratio can be 1:
50,1:55,1:60,1:65,1:70,1:75,1:80,1:85,1:90,1:95,1:100 etc..
In the preferred embodiment of the present invention, bath temperature is 70-90 DEG C, and washing of precipitate is to wash 3- with absolute ethyl alcohol
5 times, the drying of copper zinc complex is dries 24-48h in 80 DEG C of baking ovens, grind into powder after drying, and powder is in Muffle furnace
480-520 DEG C of calcining 1-3h, cooling.In above-mentioned parameter, the temperature of water-bath is the temperature that suitable complex compound is separated out, it is possible to understand that
It is that the number of times of washing and time, temperature for drying etc. can be adjusted correspondingly according to the purifying and degree of drying of product.Tool
The calcining vessel of body can be adjusted, and the temperature of calcining is the temperature for being adapted to the calcining of copper zinc complex, and the time of calcining is according to specific
Calcining situation be adjustable.
In the alternative embodiment of the present invention, obtained after the sonicated 0.2-0.6h of solution I；The solution II is passed through
Obtained after the ultrasonically treated 0.5-1h of 30-50kHz；Obtained after the sonicated 5-7h of the solution III.When above-mentioned ultrasonically treated
Between ensure that the abundant progress of reaction, but it is understood that, the above-mentioned ultrasonically treated time can be according to the shape of reaction
State is adjusted.
In the alternative embodiment of the present invention, solution III, which is centrifuged, to be precipitated, and 60 DEG C of bakings in baking oven are placed in after washing of precipitate
24-48h is dried in case.Obtained material dries the bactericidal property that ensure that material, in specific operating process, drying at 60 DEG C
Temperature and time can fluctuate.
Another embodiment of the present invention provides the Nanometer Copper zinc composite antibacterial material that above-mentioned preparation method is prepared, should
Anti-biotic material being capable of efficient sterilizing.
One more embodiment of the present invention provides the side that antibiotic paint is prepared using above-mentioned Nanometer Copper zinc composite antibacterial material
Method, comprises the following steps：Nanometer Copper zinc composite antibacterial material is added in aqueous polyurethane, stirred；Add at auxiliary agent, ultrasound
Reason, produces antibiotic paint.In the present embodiment, Nanometer Copper zinc composite antibacterial material is sufficiently mixed with aqueous polyurethane, and ultrasound is uniform
Processing, enables to anti-biotic material effectively to disperse, and aqueous polyurethane can be carried and beneficial to performance antibiotic paint as carrier
Antibacterial action.
In the preferred embodiment of the present invention, the mass ratio of Nanometer Copper zinc composite antibacterial material and aqueous polyurethane is 1：
37.5-100；Auxiliary agent is the one or more in water, wetting agent, defoamer, wax emulsion；Ultrasonication is：During ultrasound
Solution is stirred into 5min, ultrasonic temperature≤35 DEG C every 30min.In the present embodiment, the too high levels of polyurethane, anti-biotic material
Anti-microbial property do not play well, the content of polyurethane is very few, causes the performance of coating not meet the requirement of coating, it is preferred that to receive
The ratio of rice copper zinc composite antibacterial material and aqueous polyurethane can be any number in above range, for example, can be 1:
40,1:50,1:60,1:70,1:80,1:90 etc..It is understood that above-mentioned auxiliary agent is preferred coating additive, but other
The auxiliary agent for constituting coating can also be used in the preparation of above-mentioned coating.Ultrasonically treated interval stirring can ensure coating in the present embodiment
The anti-microbial property that ensure that coating is prepared under the degree of scatter of middle anti-biotic material, low temperature.
Another embodiment of the present invention provides application of the above-mentioned antibiotic paint in recirculating cooling water system.In this implementation
In example, antibiotic paint is coated on the tube wall of recirculating cooling water system as the antiseptic of recirculating cooling water system, so as to circulation
Cooling water system is sterilized, but it is understood that, the present embodiment is not limited thereto, it is other can be to recirculated cooling water
The embodiment that system is sterilized is also feasible.
In order to become apparent from introducing Nanometer Copper zinc composite antibacterial material and the antibacterial that the embodiment of the present invention is provided in detail
The preparation method of coating, is illustrated below with reference to specific embodiment.
Embodiment 1
The preparation of Nanometer Copper zinc composite antibacterial material：
0.35mol zinc acetates and 0.15mol copper acetates are dissolved in 500ml water and form copper zinc solution, plus 50ml anhydrous
Ethanol, ultrasonically treated 0.5h obtains solution I；
It is 6.0 to adjust the pH of solution I, adds 0.6mol monohydrate potassiums, stirring, the ultrasonically treated 0.75h of 40kHz to solution
It is middle without flocculation, obtain solution II；
By II 80 DEG C of heating water baths of solution, stirring, centrifuging to precipitate, 80 DEG C of bakings after precipitation is washed 3-5 times with absolute ethyl alcohol
24-48h is dried in case, grind into powder after drying, powder 500 DEG C of calcining 2h, cooling in Muffle furnace obtain copper zinc complex；
0.85g copper zinc complex is taken to be mixed in 0.15g graphenes in 80mlN, N- dimethylacetamide solutions, at ultrasound
6h is managed, solution III is obtained；
Solution III, which is centrifuged, to be precipitated, and dried 24-48h after precipitation is washed 3-5 times with absolute ethyl alcohol in 60 DEG C of baking ovens, produced
Nanometer Copper zinc composite antibacterial material.
The preparation of antibiotic paint：
The above-mentioned Nanometer Copper zinc composite antibacterial materials of 1g are added in 50g aqueous polyurethanes, stirred；Add proper quantity of defoaming agent
And wax emulsion, ultrasonically treated 6h, solution is stirred vigorously 5min every 30min during ultrasound, ultrasonic temperature≤35 DEG C are produced anti-
Bacterium coating.
Embodiment 2
The preparation of Nanometer Copper zinc composite antibacterial material：
0.67mol zinc acetates and 0.33mol copper acetates are dissolved in 750ml water and form copper zinc solution, plus 75ml anhydrous
Ethanol, ultrasonically treated 0.2h obtains solution I；
It is 5.5 to adjust the pH of solution I, adds 1mol monohydrate potassiums, is stirred, the ultrasonically treated 0.5h of 30kHz are into solution
Without flocculation, solution II is obtained；
By II 70 DEG C of heating water baths of solution, stirring, centrifuging to precipitate, 80 DEG C of bakings after precipitation is washed 3-5 times with absolute ethyl alcohol
24-48h is dried in case, grind into powder after drying, powder 480 DEG C of calcining 3h, cooling in Muffle furnace obtain copper zinc complex；
0.6g copper zinc complex is taken to be mixed in 0.2g graphenes in 40mlN, N- dimethylacetamide solutions, it is ultrasonically treated
5h, obtains solution III；
Solution III, which is centrifuged, to be precipitated, and dried 24-48h after precipitation is washed 3-5 times with absolute ethyl alcohol in 60 DEG C of baking ovens, produced
Nanometer Copper zinc composite antibacterial material.
The preparation of antibiotic paint：
The above-mentioned Nanometer Copper zinc composite antibacterial materials of 1g are added in 100g aqueous polyurethanes, stirred；Add appropriate froth breaking
Solution is stirred vigorously 5min every 30min during agent and wax emulsion, ultrasonically treated 6h, ultrasound, ultrasonic temperature≤35 DEG C are produced
Antibiotic paint.
Embodiment 3
The preparation of Nanometer Copper zinc composite antibacterial material：
0.75mol zinc acetates and 0.15mol copper acetates are dissolved in formation copper zinc solution in 1125ml water, plus 112.5ml
Absolute ethyl alcohol, ultrasonically treated 0.6h obtains solution I；
It is 6.7 to adjust the pH of solution I, adds 1.35mol monohydrate potassiums, is stirred, the ultrasonically treated 1h of 50kHz are into solution
Without flocculation, solution II is obtained；
By II 80 DEG C of heating water baths of solution, stirring, centrifuging to precipitate, 80 DEG C of bakings after precipitation is washed 3-5 times with absolute ethyl alcohol
24-48h is dried in case, grind into powder after drying, powder 520 DEG C of calcining 1h, cooling in Muffle furnace obtain copper zinc complex；
1g copper zinc complex is taken to be mixed in 0.1g graphenes in 110mlN, N- dimethylacetamide solutions, it is ultrasonically treated
7h, obtains solution III；
Solution III, which is centrifuged, to be precipitated, and dried 24-48h after precipitation is washed 3-5 times with absolute ethyl alcohol in 60 DEG C of baking ovens, produced
Nanometer Copper zinc composite antibacterial material.
The preparation of antibiotic paint：
The above-mentioned Nanometer Copper zinc composite antibacterial materials of 1g are added in 37.5g aqueous polyurethanes, stirred；Add appropriate froth breaking
Solution is stirred vigorously 5min every 30min during agent and wax emulsion, ultrasonically treated 6h, ultrasound, ultrasonic temperature≤35 DEG C are produced
Antibiotic paint.
Comparative example 1
Conventionally prepare nano zinc oxide material.
Comparative example 2
Conventionally prepare bar-shaped cuprous oxide material.
Antibiotic rate contrast test
Enterprises cooling water is refined as target progress antibacterial experiment using certain petrochemical industry, through strain idenfication, determined in recirculated water
Dominant bacteria has pseudomonadaceae, Bacteroides, rotten spiral Cordycepps, Characters of Flexibacter Strains section, thermophilic hydrogen Cordycepps, shank Cordycepps, red bacillus
Section, Burkholderia section, micrococcaceae, Propionibacteriaceae etc..
For the measure of Nanometer Copper zinc composite antibacterial material anti-microbial property, by Nanometer Copper zinc composite antibacterial material according to
0.2mg/mL concentration is added in recirculated cooling water, is well mixed, and bacterial concentration is calculated using colony counting method after 2h.
For the measure of antimicrobial coating performance, cated test piece will be applied and be immersed in recirculated cooling water, using flat after 24h
Plate counting method calculates bacterial concentration.
Antibiotic rate calculation formula：
In formula：
η-sterilizing rate, %；n0- blank bacterium number；Bacterium number after n-added material.
Experiment 1：
According to the preparation method of the Nanometer Copper zinc composite antibacterial material of embodiment 1, the Nanometer Copper prepared is measured respectively
During zinc composite antibacterial material, copper acetate accounts for the molar percentage of copper zinc salt summation 10%, 15%, 20%, 25%, 30%,
Sterilizing rate when 35%, as a result referring to Fig. 1, as seen in Figure 1, Nanometer Copper zinc composite antibacterial material antibiotic property of the invention
Can be excellent, the molar percentage that copper acetate accounts for copper zinc salt summation can ensure higher sterilizing rate in 15-35%.
Experiment 2：
The Nanometer Copper zinc composite antibacterial that preparation method according to the Nanometer Copper zinc composite antibacterial material of embodiment 1 is prepared
Material, when the mass fraction of graphene is respectively 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%
When, sterilizing rate is measured respectively, as a result as shown in Fig. 2 as seen in Figure 2, the mass fraction of graphene in 10-30%,
Bactericidal effect is notable.
Experiment 3：
The Nanometer Copper zinc composite antibacterial that preparation method according to the Nanometer Copper zinc composite antibacterial material of embodiment 1 is prepared
The material and graphene and copper zinc complex that the preparation method of material and comparative example 1 and comparative example 2 is prepared are sterilized
Rate is contrasted, as a result as shown in figure 3, as seen in Figure 3, Nanometer Copper zinc composite antibacterial material anti-microbial property of the invention is better than
The anti-biotic material of single metal ion.
Experiment 4：
Preparation method according to embodiment 1 prepares Nanometer Copper zinc composite antibacterial material, by solvent DMA
(DMAC) solution replaces with 1:3 alcohol water are than solution, 1:2 alcohol water are than solution, 1:1 alcohol water is prepared than solution, absolute ethyl alcohol
Material determines sterilizing rate respectively, as a result as shown in figure 4, as seen in Figure 4, Nanometer Copper zinc composite antibacterial material of the invention
During preparation, DMA (DMAC) solution is preferred dissolving, the Nanometer Copper zinc composite antibacterial material prepared
Bactericidal property is notable.
Experiment 5：
Preparation method according to embodiment 1 prepares antibiotic paint, and Nanometer Copper zinc composite antibacterial material is determined respectively and accounts for antibacterial
The mass percent of coating is respectively 0.33%, 0.67%, 1%, 1.33%, 1.67%, 2%, 2.33%, killing when 2.67%
Bacterium rate, as a result as shown in figure 5, as seen in Figure 5 when Nanometer Copper zinc composite antibacterial material accounts for the quality percentage of antibiotic paint
Than reaching when 2%, then increase Nanometer Copper zinc composite antibacterial material amount sterilizing rate increase not substantially, 2% can be defined as satisfying
And content.
To sum up, the present invention, can not only be in low copper Zinc supplementation by the way of being combined after first copper zinc is complexed with graphene
On the premise of improve compound ratio；Copper zinc is improved with the compound rear germicidal efficiency of graphene.According to obtained by the preparation method of the present invention
Copper zinc complex-graphene nanocomposite material, when composite concentration is 0.2mg/mL, effect 2h sterilizing rates are reachable
99.9%.The antibiotic paint bactericidal property prepared by the Nanometer Copper zinc composite antibacterial material of the present invention is excellent, nanometer in coating
Copper zinc composite antibacterial material addition is low, reduces cost, and stability is high.
Claims (10)
1. the preparation method of Nanometer Copper zinc composite antibacterial material, it is characterised in that specifically include following steps：
Zinc salt and mantoquita are dissolved in the water to form copper zinc solution, added and the isometric absolute ethyl alcohol of copper zinc solution, at ultrasound
Reason, obtains solution I；
It is 5.5-6.7 to adjust solution I pH, adds monohydrate potassium, stirring, it is ultrasonically treated into solution without flocculation, obtain molten
Liquid II；
By the heating water bath of solution II, stirring, centrifuging to precipitate, washing of precipitate, dry, and calcine, and cooling obtains copper zinc complex；
Above-mentioned copper zinc complex and graphene are mixed in DMA solution, it is ultrasonically treated, obtain solution III；
Solution III, which is centrifuged, to be precipitated, washing of precipitate, dried, produced Nanometer Copper zinc composite antibacterial material.
2. the preparation method of Nanometer Copper zinc composite antibacterial material according to claim 1, it is characterised in that the zinc salt and
Mantoquita and mol ratio are 2-5:1, the molal volume ratio of copper zinc total amount and water is 1:750-1250mol/ml.
3. the preparation method of Nanometer Copper zinc composite antibacterial material according to claim 1, it is characterised in that the zinc salt and
Mantoquita sum and the mol ratio of monohydrate potassium are 1:1-1.5.
4. the preparation method of Nanometer Copper zinc composite antibacterial material according to claim 1, it is characterised in that the copper zinc network
The mass ratio of compound and graphene is 3-10：1, the mass volume ratio of the copper zinc complex and DMA solution
For：1：50-100g/ml.
5. the preparation method of the Nanometer Copper zinc composite antibacterial material according to claim any one of 1-4, it is characterised in that institute
It is 70-90 DEG C to state bath temperature, and the washing of precipitate is washs 3-5 times with absolute ethyl alcohol, and the drying of the copper zinc complex is
24-48h is dried in 80 DEG C of baking ovens, grind into powder after drying, powder 480-520 DEG C of calcining 1-3h, cooling in Muffle furnace.
6. the Nanometer Copper zinc that the preparation method of the Nanometer Copper zinc composite antibacterial material described in claim any one of 1-5 is prepared
Composite antibacterial material.
7. the method for preparing antibiotic paint using the Nanometer Copper zinc composite antibacterial material described in claim 6, it is characterised in that bag
Include following steps：
Nanometer Copper zinc composite antibacterial material is added in aqueous polyurethane, stirred；
Auxiliary agent is added, it is ultrasonically treated, produce antibiotic paint.
8. the method according to claim 7 for preparing antibiotic paint, it is characterised in that
The mass ratio of the Nanometer Copper zinc composite antibacterial material and aqueous polyurethane is 1：37.5-100；
The auxiliary agent is the one or more in water, wetting agent, defoamer, wax emulsion；
The ultrasonication is：Solution is stirred into 5min, ultrasonic temperature≤35 DEG C every 30min during ultrasound.
9. the method according to claim 7 for preparing antibiotic paint, it is characterised in that above-mentioned antibiotic paint is cold for circulating
But in water system.
10. the method according to claim 9 for preparing antibiotic paint, it is characterised in that the antibiotic paint is used as circulation
The antiseptic of cooling water system is coated on the tube wall of recirculating cooling water system.
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