CN110506753A - A kind of preparation method of modified Nano silver antimicrobial composite material - Google Patents
A kind of preparation method of modified Nano silver antimicrobial composite material Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/14—Boron; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of preparation methods of modified Nano silver antimicrobial composite material, it include: that SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water are added in reaction unit, carry out microwave treatment after stirring evenly, cooling, filtering, dry material A；Material A, silane coupling agent KH-540 are mixed with dimethylformamide, is stirred under the protection of nitrogen, is centrifuged, washs, drying and to obtain material B；1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide and water is mixed into obtain activator；Graphene oxide and water are mixed, activator is added, mixes, is stirred at room temperature with material B after stirring, be centrifuged, wash, drying and to obtain material C；Material C and nano silver colloidal sol are added in ethyl alcohol, dry material D after ultrasonic treatment；It stirs evenly after material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex are mixed with water, is obtained after water removal.
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to a kind of preparation side of modified Nano silver antimicrobial composite material
Method.
Background technique
Anti-biotic material is that one kind has antibacterial and sterilizing function new material, is specifically resisted by the way that addition is one or more of
Microbial inoculum and be made.The invasion of microorganism are ubiquitous, and the development and application of anti-biotic material is for improving human habitat, reducing
Disease, protection fitness-for-all have a very important significance.According to its chemical composition, anti-biotic material is broadly divided into inorganic antibacterial
Material, organic anti-bacterial material and natural antibacterial material three categories.
Nano silver is widely used because it has the function of potent antibacterial and broad-spectrum antiseptic, however without being repaired by any
Its surface-active of the simple nano silver of decorations is very high, easily reunites, and its property is active, is easily oxidized, to biomembrane
Penetrability effect is not very good, and exclusive use nano silver is less desirable as the antibacterial effect of anti-biotic material, limits it
Application in certain antibacterial fields must be modified nano silver to obtain good antibacterial effect.
Summary of the invention
In order to solve the technical problems in background technology, the invention proposes a kind of modified Nano silver antibacterial composite woods
The preparation method of material, process is simple, and obtained composite material is heat-resist, not easy to change, and broad-spectrum, antibacterial effect are held
Long, the fields such as rubber and plastic, chemical fibre, coating, adhesive can be widely used in.
A kind of preparation method of modified Nano silver antimicrobial composite material proposed by the present invention, comprising the following steps:
S1, reaction unit is added in SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water
In, it stirs evenly to be placed in microwave equipment and carries out microwave treatment, cool down, filter, be dried to obtain material A；
S2, material A, silane coupling agent KH-540 are mixed with dimethylformamide, is protection gas with nitrogen, in 85-95
10-15h is stirred at DEG C, obtains material B after centrifugation, washing, drying；
S3,1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide are mixed with water
Uniformly obtain activator；Graphene oxide is uniformly mixed with water, is then added activator, stir after 40-60min with material B
Mixing, is stirred at room temperature 120-180min, is centrifuged, washs, being dried to obtain material C；
S4, material C and nano silver colloidal sol are added in ethyl alcohol, material D is dried to obtain after ultrasonic treatment；
S5, it stirs evenly, removes after mixing material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex with water
The modified Nano silver antimicrobial composite material is obtained after water；Wherein, the 8-hydroxyquinoline complex is carried out according to following technique
Preparation: ethyl alcohol being uniformly mixed to obtain solvent with water, and 8-hydroxyquinoline, pimelic acid, cerous nitrate are added in solvent and are uniformly dispersed,
It is subsequently placed in hydrothermal reaction kettle and carries out hydro-thermal reaction, be filtered, washed after reaction, be dried to obtain the 8-hydroxyquinoline and match
Close object.
Preferably, in S1, SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water weight
Amount is than being 35-55:1-3:0.5-2:1-2.5:250-300.
Preferably, in S1, average grain diameter, the average grain diameter of nano cupric oxide, nano-silica of the nano zine oxide
The average grain diameter for changing titanium is 25-40nm.
Preferably, in S1, the power of the microwave treatment is 550-700W, and the time of microwave treatment is 35-60min.
Preferably, in S2, material A, silane coupling agent KH-540, dimethylformamide weight ratio be 4-6:9-13:
40-60。
Preferably, in S3, graphene oxide, material B weight ratio be 1:15-20.
Preferably, in S4, the nano silver colloidal sol is electrolysis nano silver colloidal sol, and the weight content of nano silver is
0.4wt%；The w/v of material C and nano silver colloidal sol is 85-95:160-220mg/ml；The time of the ultrasonic treatment
For 180-240min, temperature is 45-55 DEG C, frequency 25-32kHz.
Preferably, in S5, material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex weight ratio be 5-9:
0.5-1.5:0.3-1.2:2-4.5.
Preferably, in S5, in the preparation process of 8-hydroxyquinoline complex, the volume ratio of ethyl alcohol and water is 1-3:1-5；
8-hydroxyquinoline, pimelic acid, cerous nitrate molar ratio be 1:1:0.5-1.5.
Preferably, in S5, in the preparation process of 8-hydroxyquinoline complex, the temperature of hydro-thermal reaction is 105-130 DEG C,
Time is 24-40h.
In the preparation method of modified Nano silver antimicrobial composite material of the present invention, first with SBA-15 molecular sieve, nanometer
Zinc oxide, nano cupric oxide, nano-titanium dioxide and water are that raw material has carried out microwave treatment, the group in SBA-15 molecular sieve pore passage
Nano zine oxide, nano cupric oxide, nano-titanium dioxide have been filled, the skeleton structure of SBA-15 molecular sieve has been maintained, obtains
Material A；Surface has been carried out to material A as modifying agent using silane coupling agent KH-540 later to be modified, and amino has been introduced into object
The surface of material A has obtained material B；It is stirred after material B is mixed with the graphene oxide after activation later, makes material B surface
Amino and the carboxyl of surface of graphene oxide are acted on, and further graphene oxide and material B are combined as a whole, obtain
Material C after mixing with nano silver colloidal sol, under the action of ultrasound, increases the movement frequency of material C and nano silver in a solvent
Rate and speed make nano silver be adsorbed on the surface of graphene oxide, while part enters so that the two comes into full contact with and combines
In the duct of SBA-15 molecular sieve, and a small amount of silver ion is formd, has obtained material D, by material D and boron oxide, Ye Lv
Plain copper acid, the cooperation of 8-hydroxyquinoline complex are used as anti-biotic material, and SBA-15 molecular sieve therein and graphene oxide can be to receiving
Meter Yin plays stable and protective effect, avoids the reunion of nano silver, gained composite material can play the property of a variety of anti-biotic materials
Can, make antibacterial wide spectrum, Candida albicans, staphylococcus aureus, Escherichia coli etc. are functioned both on, while there is sustained release to make
With can control the release of anti-biotic material, make durable antibacterial effect；8-hydroxyquinoline, pimelic acid have been specifically chosen it, based on cerous nitrate
Material is prepared for complex, is added into system, cooperates with boron oxide, nano-titanium dioxide, makes the heat-resist of anti-biotic material,
High temperature resistance is excellent；The chlorophyll cupric acid of addition can convert the visible light luminous energy of absorption to chemical energy pass to it is nano oxidized
Zinc and nano-titanium dioxide improve its efficiency of light energy utilization, significantly improve the antimicrobial efficiency of composite material；Preparation method of the present invention
The antimicrobial composite material of preparation is widely used, and can be used for the fields such as rubber and plastic, chemical fibre, coating and adhesive.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of modified Nano silver antimicrobial composite material, comprising the following steps:
S1, reaction unit is added in SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water
In, it stirs evenly to be placed in microwave equipment and carries out microwave treatment, cool down, filter, be dried to obtain material A；
S2, material A, silane coupling agent KH-540 are mixed with dimethylformamide, is protection gas with nitrogen, at 95 DEG C
10h is stirred, obtains material B after centrifugation, washing, drying；
S3,1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide are mixed with water
Uniformly obtain activator；Graphene oxide is uniformly mixed with water, activator is then added, is mixed after stirring 60min with material B
It closes, 120min is stirred at room temperature, is centrifuged, washs, being dried to obtain material C；
S4, material C and nano silver colloidal sol are added in ethyl alcohol, material D is dried to obtain after ultrasonic treatment；
S5, it stirs evenly, removes after mixing material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex with water
The modified Nano silver antimicrobial composite material is obtained after water；Wherein, the 8-hydroxyquinoline complex is carried out according to following technique
Preparation: ethyl alcohol being uniformly mixed to obtain solvent with water, and 8-hydroxyquinoline, pimelic acid, cerous nitrate are added in solvent and are uniformly dispersed,
It is subsequently placed in hydrothermal reaction kettle and carries out hydro-thermal reaction, be filtered, washed after reaction, be dried to obtain the 8-hydroxyquinoline and match
Close object.
Embodiment 2
A kind of preparation method of modified Nano silver antimicrobial composite material, comprising the following steps:
S1, reaction unit is added in SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water
In, it stirs evenly to be placed in microwave equipment and carries out microwave treatment, cool down, filter, be dried to obtain material A；
S2, material A, silane coupling agent KH-540 are mixed with dimethylformamide, is protection gas with nitrogen, at 88 DEG C
12h is stirred, obtains material B after centrifugation, washing, drying；
S3,1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide are mixed with water
Uniformly obtain activator；Graphene oxide is uniformly mixed with water, activator is then added, is mixed after stirring 40min with material B
It closes, 180min is stirred at room temperature, is centrifuged, washs, being dried to obtain material C；
S4, material C and nano silver colloidal sol are added in ethyl alcohol, material D is dried to obtain after ultrasonic treatment；
S5, it stirs evenly, removes after mixing material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex with water
The modified Nano silver antimicrobial composite material is obtained after water；Wherein, the 8-hydroxyquinoline complex is carried out according to following technique
Preparation: ethyl alcohol being uniformly mixed to obtain solvent with water, and 8-hydroxyquinoline, pimelic acid, cerous nitrate are added in solvent and are uniformly dispersed,
It is subsequently placed in hydrothermal reaction kettle and carries out hydro-thermal reaction, be filtered, washed after reaction, be dried to obtain the 8-hydroxyquinoline and match
Close object.
Embodiment 3
A kind of preparation method of modified Nano silver antimicrobial composite material, comprising the following steps:
S1, reaction unit is added in SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water
In, wherein SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water weight ratio be 35:2:
0.5:1.5:250, the average grain diameter of the nano zine oxide, the average grain diameter of nano cupric oxide, nano-titanium dioxide are averaged
Partial size is 25nm, stirs evenly and is placed in microwave equipment progress microwave treatment 60min, and the power of the microwave treatment is
550W is cooled down, filters, is dried to obtain material A；
S2, material A, silane coupling agent KH-540 are mixed with dimethylformamide, wherein material A, silane coupling agent
KH-540, dimethylformamide weight ratio be 4:13:40, with nitrogen be protection gas, stir 15h at 85 DEG C, be centrifuged, wash
Wash, dry after obtain material B；
S3,1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide are mixed with water
Uniformly obtain activator；Graphene oxide is uniformly mixed with water, activator is then added, is mixed after stirring 50min with material B
Close, wherein graphene oxide, material B weight ratio be 1:20,150min is stirred at room temperature, is centrifuged, washs, is dried to obtain
Material C；
S4, material C and nano silver colloidal sol are added in ethyl alcohol, material D is dried to obtain after ultrasonic treatment；The nano silver is molten
Glue is electrolysis nano silver colloidal sol, and the weight content of nano silver is 0.4wt%；The w/v of material C and nano silver colloidal sol
For 85:220mg/ml；The time of the ultrasonic treatment is 180min, and temperature is 55 DEG C, frequency 25kHz；
S5, it stirs evenly, removes after mixing material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex with water
The modified Nano silver antimicrobial composite material is obtained after water；Wherein, material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline are matched
The weight ratio for closing object is 9:0.5:1.2:2；The 8-hydroxyquinoline complex is prepared according to following technique: by ethyl alcohol and water
It is uniformly mixed and obtains solvent, the volume ratio of ethyl alcohol and water is 1:5, and 8-hydroxyquinoline, pimelic acid, cerous nitrate are added in solvent and divided
Dissipate uniformly, 8-hydroxyquinoline, pimelic acid, cerous nitrate molar ratio be 1:1:0.5, be subsequently placed in hydrothermal reaction kettle, at 105 DEG C
Lower progress hydro-thermal reaction 40h, is filtered, washed after reaction, is dried to obtain the 8-hydroxyquinoline complex.
Embodiment 4
A kind of preparation method of modified Nano silver antimicrobial composite material, comprising the following steps:
S1, reaction unit is added in SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water
In, wherein SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water weight ratio be 55:3:2:
2.5:300 is stirred evenly and is placed in microwave equipment, and microwave treatment 35min is carried out under the power of 700W, and cooling, filtering is done
It is dry to obtain material A；Wherein, the average grain diameter of the nano zine oxide, the average grain diameter of nano cupric oxide, nano-titanium dioxide
Average grain diameter is 30nm；
S2, material A, silane coupling agent KH-540 are mixed with dimethylformamide, wherein material A, silane coupling agent
KH-540, dimethylformamide weight ratio be 5:9:60, be protection gas with nitrogen, stir 11h at 92 DEG C, centrifugation, washing,
Material B is obtained after drying；
S3,1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide are mixed with water
Uniformly obtain activator；Graphene oxide is uniformly mixed with water, activator is then added, is mixed after stirring 45min with material B
Close, wherein graphene oxide, material B weight ratio be 1:15,160min is stirred at room temperature, is centrifuged, washs, is dried to obtain
Material C；
S4, material C and nano silver colloidal sol are added in ethyl alcohol, material D is dried to obtain after ultrasonic treatment；Wherein, described to receive
Rice silver sol is electrolysis nano silver colloidal sol, and the weight content of nano silver is 0.4wt%；The weight of material C and nano silver colloidal sol
Volume ratio is 95:160mg/ml；The time of the ultrasonic treatment is 240min, and temperature is 45 DEG C, frequency 32kHz；
S5, it stirs evenly, removes after mixing material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex with water
The modified Nano silver antimicrobial composite material is obtained after water；Wherein, material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline are matched
The weight ratio for closing object is 7:1.5:0.3:4.5；The 8-hydroxyquinoline complex is prepared according to following technique: by ethyl alcohol with
Water, which is uniformly mixed, obtains solvent, and the volume ratio of ethyl alcohol and water is 3:1, and 8-hydroxyquinoline, pimelic acid, cerous nitrate are added in solvent
Be uniformly dispersed, 8-hydroxyquinoline, pimelic acid, cerous nitrate molar ratio be 1:1:1.5, be subsequently placed in hydrothermal reaction kettle, 130
Hydro-thermal reaction is carried out for 24 hours at DEG C, is filtered, washed after reaction, is dried to obtain the 8-hydroxyquinoline complex.
Embodiment 5
A kind of preparation method of modified Nano silver antimicrobial composite material, comprising the following steps:
S1, reaction unit is added in SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water
In, it stirs evenly to be placed in microwave equipment and carries out microwave treatment, cool down, filter, be dried to obtain material A；Wherein, SBA-15 points
Sub sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water weight ratio be 50:1:1:1:280；The nano oxygen
Average grain diameter, the average grain diameter of nano cupric oxide, the average grain diameter of nano-titanium dioxide for changing zinc are 40nm；At the microwave
The power of reason is 620W, and the time of microwave treatment is 40min；
S2, material A, silane coupling agent KH-540 are mixed with dimethylformamide, wherein material A, silane coupling agent
KH-540, dimethylformamide weight ratio be 6:11:45, with nitrogen be protection gas, stir 13h at 90 DEG C, be centrifuged, wash
Wash, dry after obtain material B；
S3,1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide are mixed with water
Uniformly obtain activator；Graphene oxide is uniformly mixed with water, activator is then added, is mixed after stirring 55min with material B
Close, wherein graphene oxide, material B weight ratio be 1:18,125min is stirred at room temperature, is centrifuged, washs, is dried to obtain
Material C；
S4, material C and nano silver colloidal sol are added in ethyl alcohol, material D is dried to obtain after ultrasonic treatment；Wherein, described to receive
Rice silver sol is electrolysis nano silver colloidal sol, and the weight content of nano silver is 0.4wt%；The weight of material C and nano silver colloidal sol
Volume ratio is 90:200mg/ml；The time of the ultrasonic treatment is 210min, and temperature is 50 DEG C, frequency 29kHz；
S5, it stirs evenly, removes after mixing material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex with water
The modified Nano silver antimicrobial composite material is obtained after water；Wherein, material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline are matched
The weight ratio for closing object is 5:1:0.5:3；The 8-hydroxyquinoline complex is prepared according to following technique: ethyl alcohol and water are mixed
Conjunction uniformly obtains solvent, and 8-hydroxyquinoline, pimelic acid, cerous nitrate are added in solvent and are uniformly dispersed, is subsequently placed in hydro-thermal reaction
In kettle, hydro-thermal reaction 35h is carried out at 120 DEG C, is filtered, washed after reaction, is dried to obtain the 8-hydroxyquinoline cooperation
Object；Wherein, the volume ratio of ethyl alcohol and water is 2:3；8-hydroxyquinoline, pimelic acid, cerous nitrate molar ratio be 1:1:1.
Comparative example 1
With SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, the nano-titanium dioxide, oxidation with 5 equivalent of embodiment
Graphene, nano silver colloidal sol, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex blend as antimicrobial composite material.
Comparative example 2
With being different only in that for embodiment 5: its preparation step does not include S1, in S2, directly by SBA-15 molecular sieve, silicon
Alkane coupling agent KH-540 is mixed with dimethylformamide.
Comparative example 3
With being uniquely different only in that for embodiment 5: in S5, being free of chlorophyll cupric acid.
Comparative example 4
With being uniquely different only in that for embodiment 5: in S5, being free of 8-hydroxyquinoline complex.
The antibacterial activity of antimicrobial composite material in embodiment 5 and comparative example 1-4 is tested, the bacterium of test is
Staphylococcus aureus and Escherichia coli, minimum inhibitory concentration (MIC) are as shown in the table:
| Staphylococcus aureus MIC/mg/L | Escherichia coli MIC/mg/L | |
| Embodiment 5 | 72 | 86 |
| Comparative example 1 | 137 | 149 |
| Comparative example 2 | 118 | 126 |
| Comparative example 3 | 87 | 94 |
| Comparative example 4 | 97 | 102 |
Five conical flasks are put in 40 DEG C of thermostatic water baths, are separately added into prepared by 1g embodiment 5 and comparative example 1-4 in bottle
Antimicrobial composite material sample, and 200mL salt water (0.9wt%) is added in each bottle, and impregnate 6,24,72h in water respectively
After sample, measure its minimum inhibitory concentration, as a result as shown in the table:
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified Nano silver antimicrobial composite material, which comprises the following steps:
S1, SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water are added in reaction unit, are stirred
It mixes uniformly to be placed in microwave equipment and carries out microwave treatment, cool down, filter, be dried to obtain material A；
S2, material A, silane coupling agent KH-540 are mixed with dimethylformamide, is protection gas with nitrogen, at 85-95 DEG C
10-15h is stirred, obtains material B after centrifugation, washing, drying；
S3,1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, n-hydroxysuccinimide are uniformly mixed with water
Obtain activator；Graphene oxide is uniformly mixed with water, activator is then added, is mixed after stirring 40-60min with material B,
120-180min is stirred at room temperature, is centrifuged, washs, being dried to obtain material C；
S4, material C and nano silver colloidal sol are added in ethyl alcohol, material D is dried to obtain after ultrasonic treatment；
S5, it is stirred evenly after mixing material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex with water, after removing water
Obtain the modified Nano silver antimicrobial composite material；Wherein, the 8-hydroxyquinoline complex is prepared according to following technique:
Ethyl alcohol is uniformly mixed to obtain solvent with water, 8-hydroxyquinoline, pimelic acid, cerous nitrate are added in solvent and are uniformly dispersed, then
It is placed in hydrothermal reaction kettle and carries out hydro-thermal reaction, be filtered, washed after reaction, be dried to obtain the 8-hydroxyquinoline cooperation
Object.
2. the preparation method of modified Nano silver antimicrobial composite material according to claim 1, which is characterized in that in S1,
SBA-15 molecular sieve, nano zine oxide, nano cupric oxide, nano-titanium dioxide and water weight ratio be 35-55:1-3:0.5-2:
1-2.5:250-300.
3. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S1,
Average grain diameter, the average grain diameter of nano cupric oxide, the average grain diameter of nano-titanium dioxide of the nano zine oxide are 25-
40nm。
4. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S1,
The power of the microwave treatment is 550-700W, and the time of microwave treatment is 35-60min.
5. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S2,
Material A, silane coupling agent KH-540, dimethylformamide weight ratio be 4-6:9-13:40-60.
6. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S3,
Graphene oxide, material B weight ratio be 1:15-20.
7. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S4,
The nano silver colloidal sol is electrolysis nano silver colloidal sol, and the weight content of nano silver is 0.4wt%；Material C and nano silver colloidal sol
W/v be 85-95:160-220mg/ml；The time of the ultrasonic treatment is 180-240min, temperature 45-55
DEG C, frequency 25-32kHz.
8. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S5,
Material D, boron oxide, chlorophyll cupric acid, 8-hydroxyquinoline complex weight ratio be 5-9:0.5-1.5:0.3-1.2:2-4.5.
9. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S5, In
In the preparation process of 8-hydroxyquinoline complex, the volume ratio of ethyl alcohol and water is 1-3:1-5；8-hydroxyquinoline, pimelic acid, nitric acid
The molar ratio of cerium is 1:1:0.5-1.5.
10. the preparation method of modified Nano silver antimicrobial composite material according to claim 1 or claim 2, which is characterized in that in S5,
In the preparation process of 8-hydroxyquinoline complex, the temperature of hydro-thermal reaction is 105-130 DEG C, time 24-40h.
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