CN109463380A - A kind of high activity composite antibacterial spray and preparation method thereof - Google Patents
A kind of high activity composite antibacterial spray and preparation method thereof Download PDFInfo
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- CN109463380A CN109463380A CN201811220398.4A CN201811220398A CN109463380A CN 109463380 A CN109463380 A CN 109463380A CN 201811220398 A CN201811220398 A CN 201811220398A CN 109463380 A CN109463380 A CN 109463380A
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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
- A01N25/02—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 liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
-
- 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
-
- 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
Abstract
The invention discloses a kind of high activity composite antibacterial sprays and preparation method thereof, the antimicrobial spray is made of following raw material, and zinc ion, silver ion including one step hydro thermal method synthesis are co-doped with bismuth tungstate nano particle, waterglass, coalescing agent, age resister, emulsifier, ethyl alcohol, deionized water.The present invention carries out the bismuth tungstate nano particle that impurity synthesizes zinc ion, silver ion codope by one step hydro thermal method, and it is blended with waterglass ball milling, antibacterial ion is uniform and stable in obtained antimicrobial spray is scattered in bismuth tungstate lattice, antibacterial ion gradually discharges in use process, the Strong oxdiative reducing power for utilizing bismuth tungstate electron-hole pair simultaneously generates synergetic antibacterial effect with antibacterial ion.The present invention has sustained release, long-acting, wide spectrum, stable antibacterial, sterilization, antimildew function, and is used for a long time non-discolouring.
Description
Technical field
The present invention relates to anti-biotic material technical field more particularly to a kind of high activity composite antibacterial spray and its preparation sides
Method.
Background technique
Raising with people to modern life quality, people more and more pay close attention to air quality and living environment, especially
It is the indoor air quality and living environment that itself lives.It among these include that the households such as indoor wall, glass and sofa are raw
Product are applied flexibly, they are extremely easy the unwanted particles such as dust, bacterium, the virus of absorption, if such particle long-term accumulation will endanger
Evil people's health.How to inhibit or kill the nocuousness such as bacterium, the virus in the home life supplieshome life supplies such as wall, glass and sofa
Particle becomes an important issue concerning life and health.
Common anti-biotic material can be summarized as organic, inorganic and natural class etc..There are non-wide for traditional organic antibacterial agent
Compose that antibacterial, chemical stability is poor, heat resistance is poor, the deadly defects such as easy to aging；Natural antibacterial agent usually at 150-180 DEG C just
Start charing to decompose, application range is narrow；Inorganic antiseptic has many advantages, such as broad-spectrum antiseptic, heat-resist.However, common at present
Inorganic antiseptic is mainly using the oxide containing antibacterial ions such as silver, copper, zinc or simple substance particle and zeolite, phosphate, hydroxyl
The carriers such as apatite or soluble glass mix, and make it through certain slow releasing function to improve antimicrobial long-acting, but its
Antibacterial ion dispersion is uneven, and antibacterial ion rate of release is too fast and random uncontrollable, and the slow releasing function sustainable time is short, antibacterial
Performance long-time stability are poor, these carriers and antibacterial ion do not have synergetic antibacterial effect.The antibacterial ions such as silver, copper are chemically
Matter is active, is easily changed into the silver oxide of brown, the copper oxide of black or redox at the elemental silver of black, in white and light color
Material product can not be applied, and the discoloration problem for solving inorganic antiseptic is global problem.
Summary of the invention
Technical problem: the present invention is to solve above-mentioned inorganic antiseptic to disperse uneven, antibacterial ion release speed in the carrier
Spend it is fast and it is random it is uncontrollable, the slow releasing function sustainable time is short, anti-microbial property long-time stability are poor, carrier and antibacterial ion
The problems such as do not have to change colour after synergetic antibacterial effect, long-time service, provides a kind of high activity composite antibacterial spray and its preparation side
Method.
Technical solution: a kind of high activity composite antibacterial spray of the invention, by weight, the antimicrobial spray is by a step hydro-thermal
Method synthesis zinc ion, silver ion codope bismuth tungstate nano particle 0.01%-5%, silica and sodium oxide molybdena molar ratio be
Waterglass 0.5%-20%, coalescing agent 0.5%-2%, age resister 0.5%-5%, the emulsifier 0.5%- of 0.8:1-2:1
2%, ethyl alcohol 5%-25%, remaining is deionized water composition.
Wherein:
The coalescing agent is diisobutyl adipate, diisopropanol adipate ester, acrylic acid double cyclopentenyl oxygen ethyl
Ester, Lauryl Alcohol ester, propylene-glycol ethyl ether, propandiol butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol list
Butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenylate, the one or two of hexylene glycol monobutyl ether acetate, 3- ethoxyl ethyl propionate
It is used in mixed way above.
The age resister is 2-hydroxy-4-n-octoxybenzophenone, 2'- (2'- hydroxyl -3'- tert-butyl -5'- methyl
Phenyl)-5- chlorobenzotriazole, 2- (2H- benzotriazole-2- base)-4,6- two (1- methyl-1-phenylethyl) phenol, three (2,4- bis-
Tert-butyl-phenyl) one or two or more of phosphite ester are used in mixed way.
The emulsifier is polyoxyethylene sorbitan carboxylic ester, cetyl trimethylammonium bromide, phthalic acid
Dimethyl ester, dimethyl acetamide, dodecyl trimethyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride, dodecyl two
Methyl oxidation amine, monoalkyl phosphoric acid esters, one or two of dimethyl acetamide or more are used in mixed way.
The silver ion codope bismuth tungstate nano particle diameter is 2nm-100nm, zinc ion doping weight percent
For 0.01%-5%, silver ion doping weight percent is 0.01%-5%.
High activity composite antibacterial spray of the invention and preparation method thereof the following steps are included:
1) one step hydro thermal method synthesis zinc ion, silver ion are co-doped with bismuth tungstate nano particle: by enuatrol and Bi (NO3)3·
5H2O is add to deionized water, stirring, then by Zn (NO3)2And AgNO3It is added in above-mentioned mixed liquor, magnetic agitation, then
By Na2WO4·2H2O is added in above-mentioned solution, then obtained mixed liquor is added to polytetrafluoroethylene (PTFE) by magnetic agitation hour
Reactor tank in, hydro-thermal is cooled to room temperature, obtained precipitating n-hexane and ethyl alcohol is cleaned for several times, the powder obtained after dry
The bismuth tungstate nano particle that body is zinc ion, silver ion is co-doped with；
2) it the sodium silicate gel preparation containing zinc ion, silver ion codope bismuth tungstate nano particle: prepared by step 1)
Zinc ion, silver ion be co-doped with bismuth tungstate nano particle and be blended with waterglass powder by mechanical ball mill, after evenly mixing, be added
Deionized water, after magnetic agitation, further ultrasonic disperse, forms sodium silicate gel；
3) step 2) preparation the preparation of antimicrobial spray: is contained into zinc ion, silver ion codope bismuth tungstate nano particle
Sodium silicate gel mixed with coalescing agent, age resister, emulsifier, ethyl alcohol, after magnetic agitation, further ultrasonic disperse,
Obtain high activity composite antibacterial spray.
Wherein:
The enuatrol and Bi (NO3)3·5H2The molar ratio of O is (1-5): (0.1-2)；Zn(NO3)2、AgNO3With
Na2WO4·2H2The molar ratio of O is (0.01-2): (0.01-0.2): (0.1-2)；
The magnetic agitation be the time be 0.5-2 hours.
In the step 1), the temperature of hydro-thermal is 160-220 DEG C；Dry temperature is 50-80 DEG C.
The antimicrobial spray is sprayable directly to be used in different furniture, household electrical appliances, glass surface, or in macromolecule, metal, glass
Behind the different material appliances such as glass, ceramics surface or internal spray film forming, it is heat-treated using 50-600 DEG C, further increases antibacterial
The binding force of film and substrate, with sustained release, long-acting, broad-spectrum antiseptic, sterilization, except mould and other effects.
Antimicrobial spray obtained is subjected to antibiotic property test to more plants of test strains, antimicrobial spectrum measurement result shows antibacterial
Spray has broad spectrum antibacterial, and antibiotic rate is 99% or more.
The utility model has the advantages that the advantageous effect of the invention is as follows:
1, one step hydro thermal method carries out impurity synthesis zinc ion through the invention, silver ion is co-doped with bismuth tungstate nanometer
Grain, zinc ion in obtained antimicrobial spray, silver ion is uniform and stable is scattered in bismuth tungstate lattice, on this basis, in conjunction with
Zinc ion, silver ion are co-doped with bismuth tungstate nano particle even dispersion and are distributed in waterglass colloid and itself consolidated by ball milling blending technology
Having in micropore, further sustained release effect of collaboration enhancing antibacterial ion, antibacterial ion rate of release is stably and controllable in use process,
Its slow releasing function sustainable time is long, and anti-microbial property long-time stability are good.
2, there is synergetic antibacterial effect between antibacterial ion and bismuth tungstate nanoparticle vector.Bismuth tungstate itself has relatively narrow
Forbidden bandwidth, under the irradiation of visible light, valence-band electrons are easy to be excited to form photo-generated carrier, then its by oxygen molecule also
Original shape is at the O with strong oxidizing property2 -Free radical.Meanwhile valence band hole and hydrone occur oxidation reaction and form strong oxidizing property
OH-Free radical, this O with strong oxidizing property2 -Free radical and OH-Free radical with virus, bacterium contacts to occur
Redox reaction, and then virus and bacterium are killed, and the O of strong oxidizing property2 -Free radical and OH-Free radical can be by bismuth tungstate
The monovalence silver ion adulterated in lattice, which further aoxidizes, forms the stronger trivalent silver iron of sterilizing ability, and collaboration enhancing silver ion is certainly
The antibacterial effect of body；Meanwhile zinc ion, silver ion are incorporated into altogether in bismuth tungstate lattice, can form more crystal defects, are increased
Add the excitation probability of electron-hole pair, increases the quantity of electron-hole pair and the O with strong oxidizing property indirectly2 -Freely
Base and OH-Free radical quantity, and then the trivalent silver iron of more strong sterilizing ability is caused to generate, have significant collaboration anti-
Bacterium effect.
3, the discoloration problem of inorganic antiseptic is efficiently solved.Silver ion is uniform and stable in antimicrobial spray of the present invention is scattered in
In bismuth tungstate lattice, it is not easy to be changed into the elemental silver of the silver oxide of brown or black, this may refrain from and solve inorganic antiseptic
Metachroic problem is used for a long time.
Specific embodiment
A kind of high activity composite antibacterial spray of the present invention, by weight, the zinc which is synthesized by one step hydro thermal method
Ion, silver ion codope bismuth tungstate nano particle 0.01%-5%, silica and sodium oxide molybdena molar ratio are the water of 0.8:1-2:1
Glass 0.5%-20%, coalescing agent 0.5%-2%, age resister 0.5%-5%, emulsifier 0.5%-2%, ethyl alcohol 5%-
25%, remaining is deionized water composition.
Wherein:
The coalescing agent is diisobutyl adipate, diisopropanol adipate ester, acrylic acid double cyclopentenyl oxygen ethyl
Ester, Lauryl Alcohol ester, propylene-glycol ethyl ether, propandiol butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol list
Butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenylate, the one or two of hexylene glycol monobutyl ether acetate, 3- ethoxyl ethyl propionate
It is used in mixed way above.
The age resister is 2-hydroxy-4-n-octoxybenzophenone, 2'- (2'- hydroxyl -3'- tert-butyl -5'- methyl
Phenyl)-5- chlorobenzotriazole, 2- (2H- benzotriazole-2- base)-4,6- two (1- methyl-1-phenylethyl) phenol, three (2,4- bis-
Tert-butyl-phenyl) one or two or more of phosphite ester are used in mixed way.
The emulsifier is polyoxyethylene sorbitan carboxylic ester, cetyl trimethylammonium bromide, phthalic acid
Dimethyl ester, dimethyl acetamide, dodecyl trimethyl ammonium bromide, stearyl dimethyl benzyl ammonium chloride, dodecyl two
Methyl oxidation amine, monoalkyl phosphoric acid esters, one or two of dimethyl acetamide or more are used in mixed way.
The silver ion codope bismuth tungstate nano particle diameter is 2nm-100nm, and zinc ion doping is 0.01%-
5%, silver ion doping is 0.01%-5%.
High activity composite antibacterial spray of the invention and preparation method thereof, the preparation method of the antimicrobial spray, including with
Lower step:
1) one step hydro thermal method synthesis zinc ion, silver ion are co-doped with bismuth tungstate nano particle: by 1-5mmol enuatrol and 0.1-
2mmol Bi(NO3)3·5H2O is add to deionized water, and is stirred 0.2-2 hours, then by 0.01-2mmol Zn (NO3)2With
0.01-0.2mmol AgNO3It is added in above-mentioned mixed liquor, magnetic agitation 0.5-2 hours, then by 0.1-2mmol Na2WO4·
2H2O is added in above-mentioned solution, and magnetic agitation 0.5-2 hours, obtained mixed liquor is then added to the anti-of polytetrafluoroethylene (PTFE)
Answer in tank, 160-220 DEG C hydro-thermal 18-32 hours.It is cooled to room temperature, obtained precipitating is cleaned into 3-6 with n-hexane and ethyl alcohol
Secondary, the powder obtained after dry 5-10 hours at 50-80 DEG C is the bismuth tungstate nano particle that zinc ion, silver ion are co-doped with；
2) it the sodium silicate gel preparation containing zinc ion, silver ion codope bismuth tungstate nano particle: prepared by step 1)
Zinc ion, silver ion be co-doped with bismuth tungstate nano particle and be blended 1-10 hours with waterglass powder by mechanical ball mill, it is uniformly mixed
After conjunction, deionized water is added, after magnetic agitation 0.5-2 hours, further ultrasonic disperse 0.5-2 hours, it is solidifying to form waterglass
Glue；
3) step 2) preparation the preparation of antimicrobial spray: is contained into zinc ion, silver ion codope bismuth tungstate nano particle
Sodium silicate gel mixed in proportion with coalescing agent, age resister, emulsifier, ethyl alcohol, after magnetic agitation 0.5-2 hours, then
Further ultrasonic disperse 0.5-2 hours, obtain high activity composite antibacterial spray.
Combined with specific embodiments below, present invention is further described in detail.The following examples are intended to illustrate the invention,
But it is not intended to limit the scope of the invention.
Embodiment 1
By 2.2mmol enuatrol and 0.4mmol Bi (NO3)3·5H2O is added in 40ml deionized water, and stirring 0.3 is small
When, then by 0.01mmol Zn (NO3)2With 0.01mol AgNO3It is added in above-mentioned mixed liquor, stirs 0.5 hour, then will
0.4mmol Na2WO4·2H2O is added in above-mentioned solution, magnetic agitation 2 hours, is then added to obtained mixed liquor
In the reactor tank of 50ml polytetrafluoroethylene (PTFE), 180 DEG C hydro-thermal 18 hours.Be cooled to room temperature, by obtained precipitating n-hexane and
Ethyl alcohol cleans 3 times, and the powder obtained after 5 hours dry at 60 DEG C is zinc ion, silver ion is co-doped with bismuth tungstate nano particle.
It is 2% that the zinc ion of preparation, silver ion, which are co-doped with bismuth tungstate nano particle by mass fraction 1% and mass fraction,
Waterglass powder (silica and sodium oxide molybdena molar ratio be 0.8:1) was by mechanical ball mill 2 hours, after evenly mixing, addition go from
Sub- water presses mass fraction 88%, and after magnetic agitation 1 hour, further ultrasonic disperse 1 hour, forms sodium silicate gel.It will system
The standby sodium silicate gel containing bismuth tungstate nano particle is by mass fraction respectively by 1% diisobutyl adipate, 2% 2-
Hydroxyl -4- oxy-octyl benzophenone, 1% polyoxyethylene sorbitan carboxylic ester, the mixing of 5% ethyl alcohol, magnetic agitation 1
After hour, further ultrasonic disperse 1 hour, obtains antimicrobial spray.
Embodiment 2
By 4.4mmol enuatrol and 0.8mmol Bi (NO3)3·5H2O is added in 40ml deionized water, and stirring 0.2 is small
When, then by 0.01mmol Zn (NO3)2With 0.02mol AgNO3It is added in above-mentioned mixed liquor, stirs 1 hour, then will
0.8mmol Na2WO4·2H2O is added in above-mentioned solution, magnetic agitation 1 hour, is then added to obtained mixed liquor
In the reactor tank of 50ml polytetrafluoroethylene (PTFE), 200 DEG C hydro-thermal 24 hours.Be cooled to room temperature, by obtained precipitating n-hexane and
Ethyl alcohol cleans 6 times, and the powder obtained after dry after 8 hours dry at 70 DEG C is zinc ion, silver ion is co-doped with bismuth tungstate nanometer
Grain.
The bismuth tungstate nano particle that the zinc ion of preparation, silver ion are co-doped with is 5% by mass fraction 2% and mass fraction
Waterglass powder (silica and sodium oxide molybdena molar ratio be 1:1) by mechanical ball mill 1 hour, after evenly mixing, addition go from
Sub- water presses mass fraction 80%, and after magnetic agitation 1 hour, further ultrasonic disperse 0.5 hour, forms sodium silicate gel.It will
The sodium silicate gel containing bismuth tungstate nano particle of preparation is by mass fraction respectively by 1% own acrylic acid double cyclopentenyl oxygen
Ethyl ester, 1% 2'- (2'- hydroxyl -3'- tert-butyl -5'- aminomethyl phenyl) -5- chlorobenzotriazole, 1% hexadecyldimethylamine
Base benzyl ammonium chloride, 10% ethyl alcohol mixing, after magnetic agitation 1 hour, further ultrasonic disperse 1 hour obtains antibacterial spray
Agent.
Embodiment 3
By 1mmol enuatrol and 0.1mmol Bi (NO3)3·5H2O is added in 40ml deionized water, is stirred 0.2 hour,
Then by 0.01mmol Zn (NO3)2With 0.01mmol AgNO3It is added in above-mentioned mixed liquor, stirs 0.5 hour, then will
0.1mmol Na2WO4·2H2O is added in above-mentioned solution, magnetic agitation 0.5 hour, is then added to obtained mixed liquor
In the reactor tank of 50ml polytetrafluoroethylene (PTFE), 160 DEG C hydro-thermal 18 hours.Be cooled to room temperature, by obtained precipitating n-hexane and
Ethyl alcohol cleans 3 times, and the powder obtained after dry after 5 hours dry at 50 DEG C is zinc ion, silver ion is co-doped with bismuth tungstate nanometer
Grain.
The zinc ion of preparation, silver ion, which are co-doped with bismuth tungstate nano particle by mass fraction 0.01% and mass fraction, is
(silica and sodium oxide molybdena molar ratio pass through mechanical ball mill 1 hour 0.5% waterglass powder for 0.8:1), after evenly mixing, add
Enter deionized water by mass fraction 92.99%, after magnetic agitation 0.5 hour, further ultrasonic disperse 0.5 hour, forms water
Glass gels.By the sodium silicate gel containing bismuth tungstate nano particle of preparation by mass fraction respectively by 0.5% own propylene
Sour double cyclopentenyl oxygen ethyl ester, 0.5% 2'- (2'- hydroxyl -3'- tert-butyl -5'- aminomethyl phenyl) -5- chlorobenzotriazole,
0.5% dodecyldimethylamine oxide, 5% ethyl alcohol mixing, after magnetic agitation 0.5 hour, further ultrasonic disperse
0.5 hour, obtain antimicrobial spray.
Embodiment 4
By 5mmol enuatrol and 2mmol Bi (NO3)3·5H2O is added in 40ml deionized water, stirring 2 hours, then
By 0.2mmol Zn (NO3)2With 0.2mmol AgNO3It is added in above-mentioned mixed liquor, stirs 2 hours, then by 0.8mmol
Na2WO4·2H2O is added in above-mentioned solution, and magnetic agitation 2 hours, obtained mixed liquor is then added to 50ml polytetrafluoro
In the reactor tank of ethylene, 220 DEG C hydro-thermal 32 hours.It is cooled to room temperature, obtained precipitating is cleaned 6 with n-hexane and ethyl alcohol
Secondary, the powder obtained after dry after 10 hours dry at 80 DEG C is zinc ion, silver ion is co-doped with bismuth tungstate nano particle.
It is 20% that the zinc ion of preparation, silver ion, which are co-doped with bismuth tungstate nano particle by mass fraction 5% and mass fraction,
Waterglass powder (silica and sodium oxide molybdena molar ratio be 2:1) by mechanical ball mill 1 hour, after evenly mixing, addition go from
Sub- water presses mass fraction 80%, and after magnetic agitation 2 hours, further ultrasonic disperse 2 hours, form sodium silicate gel.It will system
The standby sodium silicate gel containing bismuth tungstate nano particle is by mass fraction respectively by 2% own acrylic acid double cyclopentenyl oxygen second
Base ester, 5% 2- (2H- benzotriazole-2- base)-4,6- two (1- methyl-1-phenylethyl) phenol, 2% hexadecyldimethylamine
Base benzyl ammonium chloride, 25% ethyl alcohol mixing, after magnetic agitation 2 hours, further ultrasonic disperse 2 hours obtain antibacterial spray
Agent.
The antimicrobial spray as made from embodiment is to staphylococcus aureus, bacillus subtilis, Candida albicans, large intestine
Bacillus carries out antibiotic property test, their antibiotic rate is respectively 99.3%, 99.6%, 99.1%, 99.7%.
Claims (9)
1. a kind of high activity composite antibacterial spray, it is characterised in that: by weight, what which was synthesized by one step hydro thermal method
Zinc ion, silver ion codope bismuth tungstate nano particle 0.01%-5%, silica and sodium oxide molybdena molar ratio are 0.8:1-2:1's
Waterglass 0.5%-20%, coalescing agent 0.5%-2%, age resister 0.5%-5%, emulsifier 0.5%-2%, ethyl alcohol 5%-
25%, remaining is deionized water composition.
2. a kind of high activity composite antibacterial spray according to claim 1, it is characterised in that: the coalescing agent be oneself two
Sour diisobutyl ester, diisopropanol adipate ester, acrylic acid double cyclopentenyl oxygen ethyl ester, Lauryl Alcohol ester, propylene-glycol ethyl ether, third
Glycol butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol mono-n-butyl Ether, tripropylene glycol n-butyl ether, propylene glycol phenyl
Ether, hexylene glycol monobutyl ether acetate, one or two of 3- ethoxyl ethyl propionate or more are used in mixed way.
3. a kind of high activity composite antibacterial spray according to claim 1, it is characterised in that: the age resister is 2- hydroxyl
Base -4- oxy-octyl benzophenone, 2'- (2'- hydroxyl -3'- tert-butyl -5'- aminomethyl phenyl) -5- chlorobenzotriazole, 2- (2H-
Benzotriazole-2- base)-4,6- two (1- methyl-1-phenylethyl) phenol, three (2,4- di-tert-butyl-phenyl) phosphite esters one kind
Or two kinds or more be used in mixed way.
4. a kind of high activity composite antibacterial spray according to claim 1, it is characterised in that: the emulsifier is polyoxy second
Alkene sorbitan carboxylic esters, cetyl trimethylammonium bromide, repefral, dimethyl acetamide, dodecane
Base trimethylammonium bromide, stearyl dimethyl benzyl ammonium chloride, dodecyldimethylamine oxide, monoalkyl phosphoric acid esters, two
One or two of methylacetamide or more are used in mixed way.
5. a kind of high activity composite antibacterial spray according to claim 1, it is characterised in that: the silver ion codope tungsten
Sour bismuth nano particle diameter is 2nm-100nm, and zinc ion doping weight percent is 0.01%-5%, silver ion doping weight
Amount percentage is 0.01%-5%.
6. a kind of high activity composite antibacterial spray as described in claim 1 and preparation method thereof, it is characterised in that: the antibacterial
The preparation method of spray, comprising the following steps:
1) one step hydro thermal method synthesis zinc ion, silver ion are co-doped with bismuth tungstate nano particle: by enuatrol and Bi (NO3)3·5H2O adds
Enter into deionized water, stirs, then by Zn (NO3)2And AgNO3It is added in above-mentioned mixed liquor, magnetic agitation, then will
Na2WO4·2H2O is added in above-mentioned solution, then obtained mixed liquor is added to polytetrafluoroethylene (PTFE) by magnetic agitation hour
In reactor tank, hydro-thermal is cooled to room temperature, and obtained precipitating n-hexane and ethyl alcohol are cleaned for several times, the powder obtained after dry
The bismuth tungstate nano particle being co-doped with for zinc ion, silver ion；
2) the sodium silicate gel preparation containing zinc ion, silver ion codope bismuth tungstate nano particle: zinc prepared by step 1)
Ion, silver ion are co-doped with bismuth tungstate nano particle and are blended with waterglass powder by mechanical ball mill, after evenly mixing, addition go from
Sub- water, after magnetic agitation, further ultrasonic disperse, forms sodium silicate gel；
3) preparation of antimicrobial spray: the water containing zinc ion, silver ion codope bismuth tungstate nano particle prepared by step 2)
Glass gels are mixed with coalescing agent, age resister, emulsifier, ethyl alcohol, and after magnetic agitation, further ultrasonic disperse, is obtained
High activity composite antibacterial spray.
7. high activity composite antibacterial spray as claimed in claim 6 and preparation method thereof, it is characterised in that: the enuatrol with
Bi(NO3)3·5H2The molar ratio of O is (1-5): (0.1-2)；Zn(NO3)2、AgNO3With Na2WO4·2H2The molar ratio of O is
(0.01-2): (0.01-0.2): (0.1-2).
8. high activity composite antibacterial spray as claimed in claim 6 and preparation method thereof, it is characterised in that: the magnetic agitation
Being is 0.5-2 hours the time.
9. high activity composite antibacterial spray as claimed in claim 6 and preparation method thereof, it is characterised in that: the step 1)
In, the temperature of hydro-thermal is 160-220 DEG C；Dry temperature is 50-80 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336304A (en) * | 2021-05-06 | 2021-09-03 | 东南大学 | Preparation method and application of high-purity silver-doped bismuth tungstate nano antibacterial fiber membrane |
| CN113877452A (en) * | 2021-09-02 | 2022-01-04 | 华南理工大学 | Centrifugal dispersion instrument and method for preparing inorganic nano antibacterial mildew-proof spray by using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113336304A (en) * | 2021-05-06 | 2021-09-03 | 东南大学 | Preparation method and application of high-purity silver-doped bismuth tungstate nano antibacterial fiber membrane |
| CN113877452A (en) * | 2021-09-02 | 2022-01-04 | 华南理工大学 | Centrifugal dispersion instrument and method for preparing inorganic nano antibacterial mildew-proof spray by using same |
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