CN106942274B - A kind of high-effective broad-spectrum fungicide of low content Nano silver solution - Google Patents
A kind of high-effective broad-spectrum fungicide of low content Nano silver solution Download PDFInfo
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- CN106942274B CN106942274B CN201710200973.3A CN201710200973A CN106942274B CN 106942274 B CN106942274 B CN 106942274B CN 201710200973 A CN201710200973 A CN 201710200973A CN 106942274 B CN106942274 B CN 106942274B
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 235000021186 dishes Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012533 medium component Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000006916 nutrient agar Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- UPDATVKGFTVGQJ-UHFFFAOYSA-N sodium;azane Chemical compound N.[Na+] UPDATVKGFTVGQJ-UHFFFAOYSA-N 0.000 description 1
- MENHWGVPQSXCBC-UHFFFAOYSA-N sodium;n-methylmethanamine Chemical compound [Na+].CNC MENHWGVPQSXCBC-UHFFFAOYSA-N 0.000 description 1
- WSWCOQWTEOXDQX-MQQKCMAXSA-N sorbic acid group Chemical group C(\C=C\C=C\C)(=O)O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- RTKIYNMVFMVABJ-UHFFFAOYSA-L thimerosal Chemical compound [Na+].CC[Hg]SC1=CC=CC=C1C([O-])=O RTKIYNMVFMVABJ-UHFFFAOYSA-L 0.000 description 1
- 229940033663 thimerosal Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- A01N25/26—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 in coated particulate form
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Agronomy & Crop Science (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides a kind of high-effective broad-spectrum fungicide of low content Nano silver solution, and by weight, its preparing raw material includes：0.1 0.5 parts of nano-ag composite；5 10 parts of surfactant；1000 parts of deionized water；5 30 parts of auxiliary agent.
Description
Technical field
The present invention relates to a kind of bactericide, and in particular to a kind of high-effective broad-spectrum fungicide containing Nano Silver.
Technical background
Nano anti-biotic material is a kind of novel antibacterial sterilization material developed in recent years, is nanosecond science and technology and antibacterial skill
The emphasis of art research.It is excellent that there is nano anti-biotic material ageing-resistant, high temperature resistant, high comprehensive performance, antibiotic property stabilization, length to wait so long
Point, expands application, improves application level.With the reduction of agent particle size, specific surface area greatly increases, huge ratio
Surface and less particle number, make key state severe mismatch, many activated centres occur, so that nano material has extremely strong suction
Attached ability so that nano-particle is to promoting oxygen atom, the oxygen radical of material corruption, and hydrocarbon molecules of other peculiar smell etc. are equal
Prisoner's ability is grabbed with very strong, therefore nano anti-biotic material has irreplaceable superiority compared to common anti-biotic material.
The antimicrobial spectrum of silver ion is extremely wide, and it is to staphylococcus aureus, Pseudomonas aeruginosa, pseudomonad, gonococcus, hemolytic
Streptococcus, ETEC, fungi etc. kill effect, while under anaerobic also can bacteria growing inhibiting.Meanwhile
Nano-Ag particles have superpower permeability, subcutaneous 2mm sterilizations can be rapidly permeated into, to common bacteria, stubborn bacteria, drug-resistant bacteria
And the tissue infection of fungus-caused higher depth has good bactericidal action.
The reason for Nano Silver can work one is that nano-Ag particles have superpower permeability, can penetrate into bacterium
It is interior, and then further influence the physiologically active of bacterium；Reason two is that silver ion has electropositive, and bacterium surface has elecrtonegativity,
Between the two because positive and negative attraction, the physiologically active of bacterium is further influenceed；Reason three be Nano Silver under the irradiation of light, can and
Either water generation superoxide radical or hydroxyl radical free radical, this two classes material have extremely strong chemical property, can destroyed air
The multiplication capacity of biological cell, suppress or kill bacterium.
But this requires that Nano Silver has several characteristics, first, the particle diameter of Nano Silver can not be too big, because particle diameter is in 25nm
Following nano silver particles can be just directly entered inside bacterium with penetration cell wall, but existing nano silver particles can be rolled into a ball
It is poly-；Second, silver ion be by Nano Silver dissociate Lai, therefore in solution silver ion concentration be well below actual Nano Silver
Concentration, this have impact on the sterilizing actual performance of silver ion.
For this case, the present invention provides a kind of high-effective broad-spectrum fungicide of low content Nano silver solution, and it is in content
Less than the performance still under 0.0004ppm with efficient quick sterilization, and to definitely several greatly bacteriums there is certain sterilization to press down
Equal performance, and used solution is reusable, still with excellent bactericidal property.
The content of the invention
The present invention provides a kind of high-effective broad-spectrum fungicide of low content Nano silver solution, by weight, its preparing raw material
Comprising：
As one embodiment of the present invention, a kind of high-effective broad-spectrum fungicide of described low content Nano silver solution,
By weight, its preparing raw material includes：
As one embodiment of the present invention, the auxiliary agent is selected from dispersant, stabilizer, preservative, thickener, wetting
One or more in agent.
As one embodiment of the present invention, the dispersant be selected from calcium lignosulfonate, sodium methylene bis-naphthalene sulfonate,
At least one of naphthalenesulfonate formaldehyde condensation compound, polycarboxylate and polyoxyethylene polyoxypropylene base ether block copolymers.
As one embodiment of the present invention, the stabilizer is selected from 2,6- di-t-butyl -4- methyl-phenols, butyl
At least one of BHA, phosphoric acid, acetic acid, triethylamine, ammonium chloride and sodium carbonate；The preservative include benzoic acid,
At least one of sorbic acid, benzoate and sorbate.
As one embodiment of the present invention, the wetting agent is selected from lauryl sodium sulfate, sldium lauryl sulfate, ten
At least one of dialkyl benzene sulfonic acids sodium, AEO and APES.
As one embodiment of the present invention, in the preservative benzoic acid, sorbic acid, benzoate and sorbate
At least one.
As one embodiment of the present invention, the thickener includes sodium alginate, Magnesiumaluminumsilicate, xanthans, poly- second
At least one of glycol, polyvinyl alcohol, carboxymethyl cellulose and phenolic resin.
As one embodiment of the present invention, the nano-ag composite is Nano silver piece, water-based chitosan and oxidation
Cuprous compound.
As one embodiment of the present invention, the preparing raw material is primary raw material also comprising formula (1) material, is prepared into
The release membranes arrived；The structure of the formula (1) is as follows：
Beneficial effect：
1st, the high-effective broad-spectrum fungicide provided by the invention, the content of its Nano Silver is extremely low, in 0.0004ppm or so,
Imponderable influence will not be caused on environment and the mankind；
2nd, the present invention has efficient, quick broad-spectrum sterilization performance, and the used aqueous solution may be reused, and repetition makes
With still having excellent bactericidal property.
Brief description of the drawings
Fig. 1：The X-ray diffraction spectrogram of Nano silver grain.
Fig. 2：The spectrogram of the SEM of Nano silver piece.
Embodiment
Participate in the election of the detailed description of the invention below for being preferable to carry out method and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with art of the present invention
The identical implication that technical staff is generally understood that.When contradiction be present, the definition in this specification is defined.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover including for non-exclusionism.For example, the combination comprising listed elements
Thing, step, method, product or device are not necessarily limited to those key elements, but can include not expressly listed other key elements or
Such a composition, step, method, product or the intrinsic key element of device.
Conjunction " Consists of " excludes any key element do not pointed out, step or component.If be used in claim, this
Phrase will make claim be closed, it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following in the clause that phrase " Consists of " appears in claim main body after theme,
It is only limited to the key element described in the clause；Other key elements are not excluded outside the claim as entirety.
Equivalent, concentration or other values or parameter are excellent with scope, preferred scope or a series of upper limit preferred values and lower limit
During the Range Representation that choosing value limits, this, which is appreciated that, specifically discloses by any range limit or preferred value and any scope
All scopes that any pairing of lower limit or preferred value is formed, regardless of whether the scope separately discloses.For example, when open
During scope " 1 to 5 ", described scope should be interpreted as including scope " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When number range is described herein, unless otherwise indicated, otherwise the scope is intended to include its end
Value and all integers and fraction within the range.
Singulative includes plural number and object is discussed, unless the context clearly dictates otherwise." optional " or it is " any
It is a kind of " refer to that the item that describes thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to represent that the present invention is not limited to this
Quantity, include the part of the amendment of the acceptable change without cause related basic function close to the quantity.Phase
Answer, modify a numerical value with " about ", " about " etc., mean that the invention is not restricted to the exact numerical.It is approximate in some examples
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, scope limits can be with
Combine and/or exchange, these scopes include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article " one kind " before key element of the present invention or component and "one" to key element or the quantitative requirement of component
(i.e. occurrence number) unrestriction.Therefore "one" or " one kind " should be read as including one or at least one, and odd number
The key element or component of form also include plural form, unless the obvious purport of the quantity refers to singulative.
" polymer " means by the polymerizable compound prepared by the monomer that polymerize identical or different type.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " EVA ".
" EVA " means the polymer prepared by polymerizeing at least two different monomers.Generic term " EVA " includes
(its is general with term " terpolymer " for term " copolymer " (its typically to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymerization for planting monomer by polymerization four or more to manufacture
Thing." blend " means that two or more polymer mixes the polymerization to be formed by physics or chemical method jointly
Thing.
The present invention provides a kind of high-effective broad-spectrum fungicide of low content Nano silver solution, by weight, its preparing raw material
Comprising：
Nano-ag composite
Heretofore described nano-ag composite is the compound of Nano silver piece, water-based chitosan and Nano silver grain, is made
Standby mode prepares Nano silver piece, the composite water soluble chitosan particle on Nano silver piece；Then Nano silver piece and water-based shell are gathered
The compound of sugared particulate carries out mineral acid treatment, then to the compound of the Nano silver piece after processing and water-based chitosan particle and
Nano silver grain it is compound, nano-ag composite is finally prepared.
Nano silver piece
The preparation process of heretofore described Nano silver piece is as follows：
It is standby with 100 milliliters of preparing ethylene glycol and dimethylformamide mixed solvent by 1: 1 volume ratio；1 gram is weighed again to gather
After vinylpyrrolidone (mean molecule quantity 33000) is added to 50 milliliters of above-mentioned in the mixed solvent ultrasonic dissolutions, 6 millis are added
Gram KBr and 6 milligrams of copper chlorides, ultrasonic dissolution it is uniform solution A, it is standby；Mixed solvent is prepared again and silver nitrate mixing is molten
Liquid：Weigh 1 gram of silver nitrate and be added to the solution B that 50 milliliters of above-mentioned in the mixed solvents are uniformly dissolved, it is standby.
Solution A and solution B is 1: 1 well mixed and be transferred in reaction vessel by volume, it is heated to and seethes with excitement back
Flow and kept for 3 hours, then stop heating.After reaction stops, with water and ethanol, each 100 milliliters are cleaned and centrifuged, finally by institute
The Nano silver piece for being dried and can obtain that the dry powder-shaped length of side is 40 nanometers, thickness is 10~15 nanometers must be precipitated.
Water-based chitosan particle
The preparation method of heretofore described water-based chitosan particle is as follows：
1st, the preparation of carboxymethyl chitosan：
(1) 10g chitosans (160kDa DD 79.01%) are weighed in 500mL beakers, add 80mL isopropanols, 13.5g
NaOH solids, 100mL water, stirring swelling 1h, reaction temperature is 50 DEG C.
(2) 15g monoxones are dissolved in 20mL isopropanols, are slowly dropped into above-mentioned solution, be added dropwise (be added dropwise in 0.5h while stirring
It is complete), 60 DEG C are maintained the temperature at during dropwise addition.Continue to react 7h at 60 DEG C after being added dropwise.
(3) question response is completed, and after cooling down at room temperature, with filtered on buchner funnel, filter residue is transferred in 500mL beakers, added
Enter 70% ethanol solution except desalt, the impurity such as alkali 3 times, each duration 2h；95% ethanol dehydration 3 times is added, when each
Long 2h, freeze-drying, obtains carboxymethyl chitosan crude product.
(4) by obtained carboxymethyl chitosan (1g), it is put into 100mL 80% ethanol, adds concentrated hydrochloric acid 5mL, at 60 DEG C
Filtered after stirring reaction 30min, gained filter residue with 75% ethanol depickling and desalination 3 times, each duration 2h,；Again with 95%
Ethanol dehydration 3 times, each duration 2h.It is freeze-dried and produces carboxymethyl chitosan.
2nd, the preparation of water-based chitosan particle：
(1) carboxymethyl chitosan sample is dissolved in distilled water, it is molten obtains the carboxymethyl chitosan that concentration is 0.5mg/mL
Liquid.
(2) CaCl that 2mL concentration is 1.0mg/mL is taken2Solution is added in the above-mentioned carboxymethyl chitosan solutions of 5mL, room temperature
Stir 30min.Solution is changed into milky emulsion and can obtain carboxymethyl chitosan nano particle.
(3) gained emulsion 20000rpm is centrifuged, removes supernatant, added distilled water and precipitation is blown to outstanding, freeze-drying.
Nano silver grain
The preparation method of heretofore described Nano silver grain is as follows：
1g dodecyl acid silver is dissolved in 20mL solvent toluenes, to abundant dissolving；Secondly, 6g lauryl amines are taken to be dissolved in
In 30mL toluene, stir to being completely dissolved, be added in the silver-colored solution of above-mentioned dodecyl acid；Then, by the 1g acyl of decanedioic acid two
Hydrazine is added in 20mL toluene, is stirred well to abundant dissolving.The amount of final solvent toluene is controlled in 70mL.In normal temperature and simultaneously
Under stirring, the solution constant current of the sebacic dihydrazide prepared is added drop-wise to the mixed of above-mentioned configuration dodecyl acid silver and lauryl amine
Close in solution.Stop after reacting 60 minutes at normal temperatures, obtain the colloid of monodispersed Nano silver grain, be prepared above-mentioned
The colloid of monodispersed Nano silver grain carry out centrifugation, sediment using acetone and butanol mixed solvent (volume ratio
For 2：1) clean at least 3 times.Then, in 50 DEG C of drying, nano-silver powder is obtained.The particle diameter of the nano-silver powder be 9.0 ±
3.1nm。
In the present invention, the Nano silver grain is based on { 200 } crystal face.
The compound of Nano silver piece and water-based chitosan particle
The preparation method of the compound of heretofore described Nano silver piece and water-based chitosan particle is as follows：
1st, by the above-mentioned Nano silver piece being prepared be dispersed in ethanol it is easy in, it is quiet under ultrasound after ultrasonic 1-3 hours
Put, take out；
2nd, the Nano silver piece after ultrasound in step 1 and carboxymethyl chitosan sample dispersion are obtained into carboxylic first in distilled water
Base enclosure glycan and Nano silver piece mixed solution.
(2) CaCl is taken2Solution is added in above-mentioned carboxymethyl chitosan and Nano silver piece mixed solution, is stirred at room temperature
30min.Solution is changed into milky emulsion and can obtain carboxymethyl chitosan nano particle.
(3) gained emulsion 20000rpm is centrifuged, removes supernatant, added distilled water and precipitation is blown to outstanding, freeze-drying, you can
Obtain the compound crude product of Nano silver piece and water-based chitosan particle.
(4) Nano silver piece and the compound crude product of water-based chitosan particle obtained step (3) is dispersed in distilled water,
3% hydrogen peroxide is added, lucifuge stirring 0.1-0.5 hours, then adds Na2SO3Terminating reaction, 89% ethanol solution is added,
Stir 0.5 hour at room temperature, centrifuge 20min, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying, produce product.
Nano-ag composite
In the present invention, the preparation method of the nano-ag composite is as follows：By the above-mentioned Nano silver piece and water being prepared
Property chitosan particle the silver-colored common distribution of compound and dodecyl acid in toluene solvant；Secondly, lauryl amine is taken to be dissolved in first
In benzene, stir to being completely dissolved, in the solution for the compound for being added to the silver-colored and water-based chitosan particle of above-mentioned dodecyl acid；So
Afterwards, sebacic dihydrazide is added in toluene, is stirred well to abundant dissolving.Under stirring in normal temperature and simultaneously, it will prepare
The solution constant current of sebacic dihydrazide be added drop-wise to above-mentioned configuration dodecyl acid silver, Nano silver piece and water-based chitosan particle
In the mixed solution of compound and lauryl amine.After reacting a period of time at normal temperatures, the colloid of nano-ag composite is obtained, will be upper
State the colloid being prepared and carry out centrifugation, sediment utilizes the mixed solvent (volume ratio 2 of acetone and butanol：1) clean
At least 3 times.Then, in 50 DEG C of drying, nano-ag composite is obtained.
As one embodiment of the present invention, the parts by weight of the Nano silver piece, water-based chitosan and Nano silver grain
Than for 1：(10-50)：(20-80).
As one embodiment of the present invention, the parts by weight of the Nano silver piece, water-based chitosan and Nano silver grain
Than for 1：30：50.
As one embodiment of the present invention, the Nano silver grain is based on { 200 } crystal face.
Surfactant
Surfactant, refer to add the material that can make the interface state of its solution system that significant change occur on a small quantity.Tool
There is fixed hydrophilic lipophilic group, aligned in the surface energy of solution.The molecular structure of surfactant has amphipathic：One
It is hydrophobic grouping to hold as hydrophilic radical, the other end；Hydrophilic radical is often polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amine
Base and its salt, hydroxyl, amide groups, ehter bond etc. can also be used as polar hydrophilic group；And hydrophobic grouping is often nonpolar hydrocarbon chain, such as 8
Individual carbon atom above hydrocarbon chain.
In the present invention, the surfactant is selected from nonionic surfactant and/or cationic surfactant.
Conventional cationic surfactant has amine salt cationic surfactant and quaternary ammonium salt cationic surface to live
Property agent；
Suitable cationic surfactant includes：Alkyl trimethyl ammonium sodium, dialkyl dimethyl ammonium sodium and alkyl two
Methyl-benzyl ammonium sodium.Quaternary ammonium salt cationic surfactant have low-corrosiveness and gentle smell and to heat, pH and have
Machine thing has high stability.
The advantages of cationic surface active agent, is that cationic surface active agent has for all kinds plant
Affinity, there is low-down toxicity, or even wherein using in the case of very small amount of cationic surface active agent
It is very effective, and is tasteless and odorless.In addition, cationic surface active agent at smooth and soft aspect better than other
Surfactant.
Conventional nonionic surface active agent：Polyethylene glycol type nonionic surfactant, polyol type nonionic table
Face activating agent；
Suitable nonionic surface active agent include polyoxyethylene ether, polyoxyethylene propylidene alkyl ether,
Polyoxyethylene phenyl ether and polyoxyethylene fatty acid ester.Particularly with for stability be preferably polyoxyethylene
Alkyl ether, polyoxyethylene propylidene alkyl ether and polyoxyethylene phenyl ether.Suitable example includes polyoxyethylene
Octyl Ether, polyoxyethylene nonyl ethers, polyoxyethylene certain herbaceous plants with big flowers base ether, polyoxyethylene propylidene certain herbaceous plants with big flowers base ether, the polyoxyethylene moon
Osmanthus base ether, polyoxyethylene propylidene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene propylidene tridecyl
Ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl group
Phenyl ether, polyoxyethylene nonylplenyl ether and polyoxyethylene styrenated phenyl ether.
In one embodiment of the invention, the surfactant is selected from alkyl trimethyl ammonium sodium, dialkyl group diformazan
Base ammonium sodium, polyoxyethylene ether, polyoxyethylene nonyl ethers, polyoxyethylene myristyl ether, polyoxyethylene are stearic
One or more in base ether.
In the present invention, the parts by weight of the surfactant are 5-10 parts, more preferably 8 parts.
Deionized water
In the present invention, the deionized water is redistilled water, is bought from Shanghai joint-trial chemical reagent Co., Ltd.
Auxiliary agent
In the present invention, the one kind or more of the auxiliary agent in dispersant, stabilizer, preservative, thickener, wetting agent
Kind.
As one embodiment of the present invention, the dispersant be selected from calcium lignosulfonate, sodium methylene bis-naphthalene sulfonate,
At least one of naphthalenesulfonate formaldehyde condensation compound, polycarboxylate and polyoxyethylene polyoxypropylene base ether block copolymers.
As one embodiment of the present invention, the stabilizer is selected from 2,6- di-t-butyl -4- methyl-phenols, butyl
At least one of BHA, phosphoric acid, acetic acid, triethylamine, ammonium chloride and sodium carbonate；The preservative include benzoic acid,
At least one of sorbic acid, benzoate and sorbate.
As one embodiment of the present invention, the wetting agent is selected from lauryl sodium sulfate, sldium lauryl sulfate, ten
At least one of dialkyl benzene sulfonic acids sodium, AEO and APES.
As one embodiment of the present invention, in the preservative benzoic acid, sorbic acid, benzoate and sorbate
At least one.
As one embodiment of the present invention, the thickener includes sodium alginate, Magnesiumaluminumsilicate, xanthans, poly- second
At least one of glycol, polyvinyl alcohol, carboxymethyl cellulose and phenolic resin.
Release membranes
In the present invention, the release membranes refer to using formula (1) material as primary raw material, and the structure of the formula (1) is as follows：
The preparation method of the release membranes is as follows：
Formula (1) material and 1- hexenes are squeezed into by tank field be added dropwise it is stand-by in kettle.Into polymerization reaction kettle, vacuum is pumped into through water
Emulsifier sodium lauryl sulfate solution after dissolving, then appropriate deionized water is added by head tank, stirring is opened, passes through drop
Add addition formula (1) material and 1- hexenes in kettle, heated up by steam, by temperature control at 43-45 DEG C, filled after stable using nitrogen
Divide air and keeping temperature stable 20-40 minutes in purging kettle, close nitrogen, add appropriate initiator potassium peroxydisulfate and carry out instead
Should, and it is warming up to 80 DEG C of insulation reactions 1 hour, then it is spray-dried, produces product.
In above-mentioned preparation process, the parts by weight of formula (1) material are that the parts by weight of 1,1- hexenes are 1.3, the emulsifying agent
Parts by weight are 0.1-0.2 parts, and the parts by weight of the deionized water are 50 parts, and the parts by weight of the initiator are 0.002 part.
The above-mentioned release membranes being prepared and nano-ag composite are quickly stirred into 1-3 hours in ethanol solution, then
It is static, it is dried in vacuo at 50 DEG C.
In the present invention, the parts by weight of the release membranes are 0.05-0.3 parts.
The second aspect of the present invention provides a kind of high-effective broad-spectrum fungicide for preparing described low content Nano silver solution
Preparation technology, comprise the following steps for：
According to the parts by weight meter, by nano-ag composite, surfactant, auxiliary agent and deionized water, 2-4 is mixed
Hour, 30-50 DEG C is warming up to, and 3-4h is maintained, cool down, filtering, stand 2-3 hours, produce.
Mechanism is explained：The antimicrobial spectrum of silver ion is extremely wide, and it is to staphylococcus aureus, Pseudomonas aeruginosa, pseudomonad, leaching ball
Bacterium, hemolytic streptococcus, ETEC, fungi etc. kill effect, while can also suppress bacterium under anaerobic
Growth.Meanwhile nano-Ag particles have superpower permeability, subcutaneous 2mm sterilizations can be rapidly permeated into, it is thin to common bacteria, stubbornness
The tissue infection of bacterium, drug-resistant bacteria and fungus-caused higher depth has good bactericidal action.But conventional Nano Silver
Particle is easily reunited, while Nano Silver easily aoxidizes, and influence of the Nano Silver for the mankind is not yet clear and definite, therefore Nano Silver contains
Amount needs to control in certain scope, avoids causing the mankind imponderable influence；But when the content of Nano Silver reduces
When, its sterilizing performance needs to reappraise again, may be unable to reach complete sterilizing performance.It is provided by the invention
A kind of high-effective broad-spectrum fungicide of low content Nano silver solution, it still has efficiently quick in the case where content is less than 0.0004ppm
The performance of sterilization, and used solution is reusable, still with excellent sterilizing performance.The reason for its is possible
It is that Nano silver piece is because with the presence of sheet form, its phenomenon reunited can be far smaller than the situation of silver nano-grain, while its
Exist in the form of nanometer sheet so that it produces hydroxyl radical free radical within the unit interval or the speed of superoxide radical is much high
Nano-Ag particles after reunion；Secondly water-based chitosan with Nano silver piece it is compound after, after peroxide degradation, its table
There is hole in face so that later stage Nano silver grain can be dispersed in the hole on water-based chitosan surface, effectively prevent Yin Na
The reunion of rice corpuscles, while improve the dissociation of silver ion.Meanwhile after adding release membranes, nano-ag composite is embedded
Processing, the consumption process of nano-ag composite can be alleviated so that the bactericide being prepared, stability is high, and repeatable makes
With, and the group in release membranes has cooperative effect with nano-ag composite.
Embodiment 1：Present embodiment provides a kind of high-effective broad-spectrum fungicide of low content Nano silver solution, by weight
Meter, its preparing raw material include：
Embodiment 2：The high-effective broad-spectrum fungicide of a kind of low content Nano silver solution as tdescribed in embodiment 1, by weight
Part meter is measured, its preparing raw material includes：
Embodiment 3：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as tdescribed in embodiment 1, it is described
One or more of the auxiliary agent in dispersant, stabilizer, preservative, thickener, wetting agent.
Embodiment 4：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as described in embodiment 3, it is described
Dispersant is selected from calcium lignosulfonate, sodium methylene bis-naphthalene sulfonate, naphthalenesulfonate formaldehyde condensation compound, polycarboxylate and polyoxyethylene
At least one of polyoxypropylene base ether block copolymers.
Embodiment 5：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as described in embodiment 3, it is described
Stabilizer is selected from 2,6- di-t-butyl -4- methyl-phenols, butylated hydroxy anisole, phosphoric acid, acetic acid, triethylamine, ammonium chloride and carbon
At least one of sour sodium；The preservative includes at least one of benzoic acid, sorbic acid, benzoate and sorbate.
Embodiment 6：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as described in embodiment 3, it is described
Wetting agent is selected from lauryl sodium sulfate, sldium lauryl sulfate, neopelex, AEO and alkyl
At least one of phenol polyethenoxy ether.
Embodiment 7：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as described in embodiment 3, it is described
At least one of preservative benzoic acid, sorbic acid, benzoate and sorbate.
Embodiment 8：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as described in embodiment 3, it is described
Thickener is included in sodium alginate, Magnesiumaluminumsilicate, xanthans, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and phenolic resin
At least one.
Embodiment 9：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as tdescribed in embodiment 1, it is described
Nano-ag composite is the compound of Nano silver piece, water-based chitosan and cuprous oxide.
Embodiment 10：A kind of high-effective broad-spectrum fungicide of low content Nano silver solution as tdescribed in embodiment 1, it is described
Preparing raw material is the release membranes that primary raw material is prepared also comprising formula (1) material；The structure of the formula (1) is as follows：
The present invention is specifically described below by embodiment.It is necessarily pointed out that following examples are only used
In the invention will be further described, it is impossible to be interpreted as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of the invention described above, still fall within protection scope of the present invention.
In addition, if without other explanations, raw materials used is all commercially available, and number used in following material is weight
Part.
Embodiment 1：
The present embodiment provides a kind of high-effective broad-spectrum fungicide of low content Nano silver solution, and by weight, it prepares former
Material includes：
Wherein, the preparation method of the nano-ag composite is as follows：
First, Nano silver piece：It is standby with 100 milliliters of preparing ethylene glycol and dimethylformamide mixed solvent by 1: 1 volume ratio；
1 gram of polyvinylpyrrolidone (mean molecule quantity 33000) is weighed again is added to 50 milliliters of above-mentioned in the mixed solvent ultrasonic dissolutions
Afterwards, add 6 milligrams of KBrs and 6 milligrams of copper chlorides, ultrasonic dissolution it is uniform solution A, it is standby；Mixed solvent and nitre are prepared again
The silver-colored mixed solution of acid：Weigh 1 gram of silver nitrate and be added to the solution B that 50 milliliters of above-mentioned in the mixed solvents are uniformly dissolved, it is standby.
Solution A and solution B is 1: 1 well mixed and be transferred in reaction vessel by volume, it is heated to and seethes with excitement back
Flow and kept for 3 hours, then stop heating.After reaction stops, with water and ethanol, each 100 milliliters are cleaned and centrifuged, finally by institute
The Nano silver piece for being dried and can obtain that the dry powder-shaped length of side is 40 nanometers, thickness is 10~15 nanometers must be precipitated.
2nd, the compound of Nano silver piece and water-based chitosan particle：
1st, the preparation of carboxymethyl chitosan：
(1) 10g chitosans (160kDa DD 79.01%) are weighed in 500mL beakers, add 80mL isopropanols, 13.5g
NaOH solids, 100mL water, stirring swelling 1h, reaction temperature is 50 DEG C.
(2) 15g monoxones are dissolved in 20mL isopropanols, are slowly dropped into above-mentioned solution, be added dropwise (be added dropwise in 0.5h while stirring
It is complete), 60 DEG C are maintained the temperature at during dropwise addition.Continue to react 7h at 60 DEG C after being added dropwise.
(3) question response is completed, and after cooling down at room temperature, with filtered on buchner funnel, filter residue is transferred in 500mL beakers, added
Enter 70% ethanol solution except desalt, the impurity such as alkali 3 times, each duration 2h；95% ethanol dehydration 3 times is added, when each
Long 2h, freeze-drying, obtains carboxymethyl chitosan crude product.
(4) by obtained carboxymethyl chitosan (1g), it is put into 100mL 80% ethanol, adds concentrated hydrochloric acid 5mL, at 60 DEG C
Filtered after stirring reaction 30min, gained filter residue with 75% ethanol depickling and desalination 3 times, each duration 2h,；Again with 95%
Ethanol dehydration 3 times, each duration 2h.It is freeze-dried and produces carboxymethyl chitosan.
2nd, the compound of Nano silver piece and water-based chitosan particle：
(1) by the above-mentioned Nano silver piece being prepared be dispersed in ethanol it is easy in, it is quiet under ultrasound after ultrasonic 1-3 hours
Put, take out；
(2) Nano silver piece after ultrasound in step (1) and carboxymethyl chitosan sample dispersion are obtained into carboxylic in distilled water
Methyl chitosan and Nano silver piece mixed solution, the wherein concentration of carboxymethyl chitosan are 0.5mg/mL.
(3) CaCl that 2mL concentration is 1.0mg/mL is taken2Solution is added to the above-mentioned carboxymethyl chitosans of 5mL and Nano silver piece
In mixed solution, 30min is stirred at room temperature.Solution is changed into milky emulsion, you can obtains Nano silver piece and water-based chitosan particle
Compound.
(4) gained emulsion 20000rpm is centrifuged, removes supernatant, added distilled water and precipitation is blown to outstanding, freeze-drying, you can
Obtain the compound crude product of Nano silver piece and water-based chitosan particle.
(5) Nano silver piece and the compound crude product of water-based chitosan particle obtained step (4) is dispersed in distilled water,
3% hydrogen peroxide is added, lucifuge stirring 0.1-0.5 hours, then adds Na2SO3Terminating reaction, 89% ethanol solution is added,
Stir 0.5 hour at room temperature, centrifuge 20min, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying, produce product.
3rd, nano-ag composite
The compound of the above-mentioned Nano silver piece being prepared and water-based chitosan particle and 1g dodecyls acid silver is common
It is dispersed in 20mL toluene solvants；Secondly, take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added to
In the solution for stating the compound of dodecyl acid silver, Nano silver piece and water-based chitosan particle；Then, by 1g sebacic dihydrazides
It is added in 20mL toluene, is stirred well to abundant dissolving, the amount of final solvent toluene is in 70mL.Stir in normal temperature and simultaneously
Under, the solution constant current of the sebacic dihydrazide prepared is added drop-wise to above-mentioned configuration dodecyl acid silver, Nano silver piece and water-based
In the compound of chitosan particle and the mixed solution of lauryl amine.After reacting 60min at normal temperatures, nano-ag composite is obtained
Colloid, the above-mentioned colloid that is prepared is subjected to centrifugation, (volume ratio is sediment using the mixed solvent of acetone and butanol
2：1) clean at least 3 times.Then, in 50 DEG C of drying, nano-ag composite is obtained.
In the present embodiment, the Nano silver grain is based on { 200 } crystal face.
In the present embodiment, the weight part ratio of the Nano silver piece, water-based chitosan and Nano silver grain is 1：30：50.
The preparation method of the release membranes is as follows：Formula (1) material and 1- hexenes are squeezed into by tank field be added dropwise it is stand-by in kettle.To
Vacuum is pumped into the emulsifier sodium lauryl sulfate solution after water dissolves in polymerization reaction kettle, then is added in right amount by head tank
Deionized water, stirring is opened, add formula (1) material and 1- hexenes by being added dropwise in kettle, heated up by steam, temperature control is existed
43-45 DEG C, air and keeping temperature stable 20-40 minutes in kettle are fully purged using nitrogen after stablizing, nitrogen is closed, adds
Appropriate initiator potassium peroxydisulfate is reacted, and is warming up to 80 DEG C of insulation reactions 1 hour, is then spray-dried, produces production
Product.
In above-mentioned preparation process, the parts by weight of formula (1) material are that the parts by weight of 1,1- hexenes are 1.3, the emulsifying agent
Parts by weight are 0.1 part, and the parts by weight of the deionized water are 50 parts, and the parts by weight of the initiator are 0.002 part.
The above-mentioned release membranes being prepared and nano-ag composite are quickly stirred 2 hours in ethanol solution, Ran Houjing
Only, it is dried in vacuo at 50 DEG C, obtains the compound of release membranes and nano-ag composite.
Surfactant：Surfactant described in the present embodiment is trimethyl ammonium iodide and polyoxyethylene
Myristyl ether is 1 according to weight ratio：1 mixture, the trimethyl ammonium iodide purchase are scientific and technological from the huge victory in Hubei
Co., Ltd, the polyoxyethylene myristyl ether are bought from Guangzhou Rui Yang surfactants Co., Ltd.
Deionized water is redistilled water, is bought from Shanghai joint-trial chemical reagent Co., Ltd.
The dispersant is calcium lignosulfonate, is bought from the general new material Co., Ltd of Qingzhou City.
The stabilizer is sodium carbonate, is bought from Chemical Reagent Co., Ltd., Sinopharm Group.
The wetting agent is lauryl sodium sulfate, is bought from Chemical Reagent Co., Ltd., Sinopharm Group.
The preservative is sorbic acid, is bought from Chemical Reagent Co., Ltd., Sinopharm Group.
The thickener is sodium alginate, is bought from Chemical Reagent Co., Ltd., Sinopharm Group.
In the present embodiment, the dispersant, stabilizer, wetting agent, the weight ratio of preservative and thickener are 1：1：1：1：
1。
The second aspect of the present embodiment provides a kind of high-effective broad-spectrum fungicide for preparing described low content Nano silver solution
Preparation technology, comprise the following steps for：
According to the parts by weight meter, by the compound of release membranes and nano-ag composite, surfactant, auxiliary agent and go from
Sub- water, 2-4 hours are mixed, are warming up to 30-50 DEG C, and maintain 3-4h, cooled down, filtering, stood 2-3 hours, produce.
The content that the nano-ag composite is measured in thimerosal is approximately equal to 0.0004ppm.
Embodiment 2：The present embodiment and the difference of embodiment 1 be, the nano-ag composite is Nano silver piece, the silver
The preparation method of nanometer sheet is the same as embodiment 1.
Embodiment 3：The present embodiment and the difference of embodiment 1 are that the nano-ag composite is silver nano-grain, described
The preparation method of Nano silver grain is as follows：1g dodecyl acid silver is dissolved in 20mL solvent toluenes, to abundant dissolving；Its
It is secondary, take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added in the silver-colored solution of above-mentioned dodecyl acid；So
Afterwards, 1g sebacic dihydrazide is added in 20mL toluene, is stirred well to abundant dissolving.Control the amount of final solvent toluene
In 70mL.Under stirring in normal temperature and simultaneously, the solution constant current of the sebacic dihydrazide prepared is added drop-wise to above-mentioned configuration 12
In the mixed solution of alkyl acid silver and lauryl amine.Stop after reacting 60 minutes at normal temperatures, obtain monodispersed Nano silver grain
Colloid, the colloid of the above-mentioned monodispersed Nano silver grain being prepared is subjected to centrifugation, sediment using acetone with
Mixed solvent (the volume ratio 2 of butanol：1) clean at least 3 times.Then, in 50 DEG C of drying, nano-silver powder is obtained.The nanometer
The particle diameter of silver powder is 9.0 ± 3.1nm.
Embodiment 4：The present embodiment and the difference of embodiment 1 are that the silver nano-grain is directly loaded in Nano silver piece
On, the preparation method of the Nano silver piece is as follows with embodiment 1, the preparation method of the silver nano-grain load Nano silver piece：
By the above-mentioned Nano silver piece being prepared and the silver-colored common distribution of 1g dodecyls acid in 20mL toluene solvants；Its
It is secondary, take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added to above-mentioned dodecyl acid silver and Nano silver piece
Solution in；Then, 1g sebacic dihydrazides are added in 20mL toluene, are stirred well to abundant dissolving, final solvent first
The amount of benzene is in 70mL.Under stirring in normal temperature and simultaneously, the solution constant current of the sebacic dihydrazide prepared is added drop-wise to above-mentioned match somebody with somebody
In the mixed solution for putting dodecyl acid silver, Nano silver piece and lauryl amine.After reacting 60min at normal temperatures, colloid is obtained, will be upper
State the colloid being prepared and carry out centrifugation, sediment utilizes the mixed solvent (volume ratio 2 of acetone and butanol：1) clean
At least 3 times.Then, in 50 DEG C of drying, silver nano-grain load Nano silver piece is obtained.
Embodiment 5：The present embodiment and the difference of embodiment 1 are that the nano-ag composite is Argent grain and water-based shell
The compound of glycan, specific preparation process is as follows,
1st, the preparation of carboxymethyl chitosan：
(1) 10g chitosans (160kDa DD 79.01%) are weighed in 500mL beakers, add 80mL isopropanols, 13.5g
NaOH solids, 100mL water, stirring swelling 1h, reaction temperature is 50 DEG C.
(2) 15g monoxones are dissolved in 20mL isopropanols, are slowly dropped into above-mentioned solution, be added dropwise (be added dropwise in 0.5h while stirring
It is complete), 60 DEG C are maintained the temperature at during dropwise addition.Continue to react 7h at 60 DEG C after being added dropwise.
(3) question response is completed, and after cooling down at room temperature, with filtered on buchner funnel, filter residue is transferred in 500mL beakers, added
Enter 70% ethanol solution except desalt, the impurity such as alkali 3 times, each duration 2h；95% ethanol dehydration 3 times is added, when each
Long 2h, freeze-drying, obtains carboxymethyl chitosan crude product.
(4) by obtained carboxymethyl chitosan (1g), it is put into 100mL 80% ethanol, adds concentrated hydrochloric acid 5mL, at 60 DEG C
Filtered after stirring reaction 30min, gained filter residue with 75% ethanol depickling and desalination 3 times, each duration 2h,；Again with 95%
Ethanol dehydration 3 times, each duration 2h.It is freeze-dried and produces carboxymethyl chitosan.
2nd, the preparation of water-based chitosan particle：
(1) carboxymethyl chitosan sample is dissolved in distilled water, it is molten obtains the carboxymethyl chitosan that concentration is 0.5mg/mL
Liquid.
(2) CaCl that 2mL concentration is 1.0mg/mL is taken2Solution is added in the above-mentioned carboxymethyl chitosan solutions of 5mL, room temperature
Stir 30min.Solution is changed into milky emulsion and can obtain carboxymethyl chitosan nano particle.
(3) by gained emulsion 20000rpm centrifuge, remove supernatant, add distilled water precipitation is blown it is outstanding, freeze-drying, obtain
Water-based chitosan particle crude product；
(4) water-based chitosan particle crude product is dispersed in distilled water, adds 3% hydrogen peroxide, lucifuge stirring 0.1-0.5
Hour, then add Na2SO3Terminating reaction, 89% ethanol solution is added, stirred 0.5 hour at room temperature, centrifuged 20min, go
Except supernatant, it is repeated 3 times, 50 DEG C of vacuum drying, produces water-based chitosan particle.
3rd, the compound of Argent grain and water-based chitosan：
Water-based chitosan particle and 1g dodecyl acid silver are dissolved in 20mL solvent toluenes, to abundant dissolving；Secondly,
Take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added in the silver-colored solution of above-mentioned dodecyl acid；Then,
1g sebacic dihydrazide is added in 20mL toluene, is stirred well to abundant dissolving.The amount of final solvent toluene is controlled to exist
70mL.Under stirring in normal temperature and simultaneously, the solution constant current of the sebacic dihydrazide prepared is added drop-wise to above-mentioned configuration dodecane
In the mixed solution of base acid silver and lauryl amine.Stop after reacting 60 minutes at normal temperatures, obtain monodispersed Nano silver grain
Colloid, the colloid of the above-mentioned monodispersed Nano silver grain being prepared is subjected to centrifugation, sediment utilizes acetone and fourth
Mixed solvent (the volume ratio 2 of alcohol：1) clean at least 3 times.Then, in 50 DEG C of drying, Argent grain and water-based chitosan are obtained
Compound.
The weight part ratio of the water-based chitosan and Nano silver grain is 30：50.
Embodiment 6：The present embodiment and the difference of embodiment 1 are that the nano-ag composite is Argent grain and water-based shell
The compound of glycan, specific preparation process is as follows,
1st, the preparation of carboxymethyl chitosan：
(1) 10g chitosans (160kDa DD 79.01%) are weighed in 500mL beakers, add 80mL isopropanols, 13.5g
NaOH solids, 100mL water, stirring swelling 1h, reaction temperature is 50 DEG C.
(2) 15g monoxones are dissolved in 20mL isopropanols, are slowly dropped into above-mentioned solution, be added dropwise (be added dropwise in 0.5h while stirring
It is complete), 60 DEG C are maintained the temperature at during dropwise addition.Continue to react 7h at 60 DEG C after being added dropwise.
(3) question response is completed, and after cooling down at room temperature, with filtered on buchner funnel, filter residue is transferred in 500mL beakers, added
Enter 70% ethanol solution except desalt, the impurity such as alkali 3 times, each duration 2h；95% ethanol dehydration 3 times is added, when each
Long 2h, freeze-drying, obtains carboxymethyl chitosan crude product.
(4) by obtained carboxymethyl chitosan (1g), it is put into 100mL 80% ethanol, adds concentrated hydrochloric acid 5mL, at 60 DEG C
Filtered after stirring reaction 30min, gained filter residue with 75% ethanol depickling and desalination 3 times, each duration 2h,；Again with 95%
Ethanol dehydration 3 times, each duration 2h.It is freeze-dried and produces carboxymethyl chitosan.
2nd, the preparation of water-based chitosan particle：
(1) carboxymethyl chitosan sample is dissolved in distilled water, it is molten obtains the carboxymethyl chitosan that concentration is 0.5mg/mL
Liquid.
(2) CaCl that 2mL concentration is 1.0mg/mL is taken2Solution is added in the above-mentioned carboxymethyl chitosan solutions of 5mL, room temperature
Stir 30min.Solution is changed into milky emulsion and can obtain carboxymethyl chitosan nano particle.
(3) by gained emulsion 20000rpm centrifuge, remove supernatant, add distilled water precipitation is blown it is outstanding, freeze-drying, obtain
Water-based chitosan particle.
3rd, the compound of Argent grain and water-based chitosan：
Water-based chitosan particle and 1g dodecyl acid silver are dissolved in 20mL solvent toluenes, to abundant dissolving；Secondly,
Take 6g lauryl amines to be dissolved in 30mL toluene, stir to being completely dissolved, be added in the silver-colored solution of above-mentioned dodecyl acid；Then,
1g sebacic dihydrazide is added in 20mL toluene, is stirred well to abundant dissolving.The amount of final solvent toluene is controlled to exist
70mL.Under stirring in normal temperature and simultaneously, the solution constant current of the sebacic dihydrazide prepared is added drop-wise to above-mentioned configuration dodecane
In the mixed solution of base acid silver and lauryl amine.Stop after reacting 60 minutes at normal temperatures, obtain monodispersed Nano silver grain
Colloid, the colloid of the above-mentioned monodispersed Nano silver grain being prepared is subjected to centrifugation, sediment utilizes acetone and fourth
Mixed solvent (the volume ratio 2 of alcohol：1) clean at least 3 times.Then, in 50 DEG C of drying, Argent grain and water-based chitosan are obtained
Compound.
The weight part ratio of the water-based chitosan and Nano silver grain is 30：50.
Embodiment 7：The present embodiment and the difference of embodiment 1 be, the nano-ag composite is Nano silver piece and water-based
The compound of chitosan, its preparation process is the same as the compound of Nano silver piece and water-based chitosan particle in embodiment 1.
Embodiment 8：The present embodiment and the difference of embodiment 1 be, the nano-ag composite is Nano silver piece and water-based
The compound of chitosan, its preparation process are as follows：1st, the preparation of carboxymethyl chitosan：
(1) 10g chitosans (160kDa DD 79.01%) are weighed in 500mL beakers, add 80mL isopropanols, 13.5g
NaOH solids, 100mL water, stirring swelling 1h, reaction temperature is 50 DEG C.
(2) 15g monoxones are dissolved in 20mL isopropanols, are slowly dropped into above-mentioned solution, be added dropwise (be added dropwise in 0.5h while stirring
It is complete), 60 DEG C are maintained the temperature at during dropwise addition.Continue to react 7h at 60 DEG C after being added dropwise.
(3) question response is completed, and after cooling down at room temperature, with filtered on buchner funnel, filter residue is transferred in 500mL beakers, added
Enter 70% ethanol solution except desalt, the impurity such as alkali 3 times, each duration 2h；95% ethanol dehydration 3 times is added, when each
Long 2h, freeze-drying, obtains carboxymethyl chitosan crude product.
(4) by obtained carboxymethyl chitosan (1g), it is put into 100mL 80% ethanol, adds concentrated hydrochloric acid 5mL, at 60 DEG C
Filtered after stirring reaction 30min, gained filter residue with 75% ethanol depickling and desalination 3 times, each duration 2h,；Again with 95%
Ethanol dehydration 3 times, each duration 2h.It is freeze-dried and produces carboxymethyl chitosan.
2nd, the compound of Nano silver piece and water-based chitosan particle：
(1) by the above-mentioned Nano silver piece being prepared be dispersed in ethanol it is easy in, it is quiet under ultrasound after ultrasonic 1-3 hours
Put, take out；
(2) Nano silver piece after ultrasound in step (1) and carboxymethyl chitosan sample dispersion are obtained into carboxylic in distilled water
Methyl chitosan and Nano silver piece mixed solution, the wherein concentration of carboxymethyl chitosan are 0.5mg/mL.
(3) CaCl that 2mL concentration is 1.0mg/mL is taken2Solution is added to the above-mentioned carboxymethyl chitosans of 5mL and Nano silver piece
In mixed solution, 30min is stirred at room temperature.Solution is changed into milky emulsion, you can obtains Nano silver piece and water-based chitosan particle
Compound.
(4) gained emulsion 20000rpm is centrifuged, removes supernatant, added distilled water and precipitation is blown to outstanding, freeze-drying, you can
Obtain the compound of Nano silver piece and water-based chitosan particle.
Embodiment 9：The present embodiment and the difference of embodiment 1 be, the nano-ag composite is but described with embodiment 1
The compound of Nano silver piece and water-based chitosan particle is handled without peroxide degradation in nano-ag composite, and without following
Step process：" Nano silver piece and the compound crude product of water-based chitosan particle that (5) obtain step (4) are dispersed in distilled water
In, 3% hydrogen peroxide is added, lucifuge stirring 0.1-0.5 hours, Na2SO3 terminating reactions is then added, adds 89% ethanol
Solution, stir 0.5 hour at room temperature, centrifuge 20min, remove supernatant, be repeated 3 times, 50 DEG C of vacuum drying, produce product.”
Embodiment 10：The present embodiment and the difference of embodiment 1 be, the Nano silver grain based on { 111 } crystal face,
Its preparation method is as follows：By 90mg silver nitrates, 110mg PVP, 20mL ethylene glycol and 0.05mg NaCl are placed in 50mL polytetrafluoros
In ethylene reaction container, dissolving is sufficiently stirred.It is placed in micro-wave oven and heating response is carried out under 320W, in reaction 3 minutes
Take out afterwards and obtain product, reacted product after natural cooling, is carried out clearly with acetone, ethanol and ultra-pure water successively at room temperature
Wash：Cleaning agent, the dispersion product under ul-trasonic irradiation are added, then 20 minutes are centrifuged with precipitated nanocrystals solid with 4500rpm rotating speeds,
Altogether in triplicate.After product cleaning, preserved after being disperseed with ultra-pure water.
Embodiment 11：The present embodiment and the difference of embodiment 1 be, the Nano silver piece, water-based chitosan and silver nanoparticle
The weight part ratio of particle is 1：5：10.
Embodiment 12：The present embodiment and the difference of embodiment 1 are that the high-effective broad-spectrum fungicide is free of release membranes.
Performance test：
1st, antibacterial ring size determines：Anti-microbial property detection using staphylococcus aureus and Escherichia coli as gram-positive bacteria with
The representative of Gram-negative bacteria, around-France the anti-microbial property of material is evaluated using antibacterial.
The preparation of 1.1 culture mediums
The preparation of PBS：Disodium hydrogen phosphate 2.83g is weighed respectively, and phosphoric acid dioxy potassium L36g is placed in the big of 1000mL
In sesame seed cake, add distilled water to stir to 1000mL, until completely dissolved, pH to 7.2-7.4 is adjusted with sodium hydroxide solution, in
121 DEG C of pressuresteam sterilization 20min are standby.
Escherichia coli, staphylococcus aureus solid medium (LB)：Tryptone 10g, beef extract 5g, NaCl 5g, fine jade
Cosmetics 20g, distilled water 1000mL.Prepare：Mentioned component is taken, is added in 1000mL distilled water, adjusts pH to 7.2-7.4, is heated molten
Solution, is dispensed in rearmounted high-pressure steam sterilizing pan, and sterilize 30min in 121 DEG C.This medium component prepare be suitable for Escherichia coli and
Staphylococcus aureus solid medium.
1.2 antibacterial ring sizes are tested
(1) preparation of bacteria inhibition tablet
To liquid bacteriostatic agent, filter paper that is sterile and drying is taken.Every is added dropwise the antibacterial μ L of agent solution 20, afterwards by filter paper
Lie against in the sterilized petri dishes of cleaning, put dried in incubator (37 DEG C) it is rear standby.
(2) preparation of print is compareed
Sterile dry filter paper piece is taken, the μ L of starch solution 20 are added dropwise, it is standby after drying.
(3) inoculation of test organisms
Concentration is dipped as 5 × 10 with sterile cotton swab5Cfu/mL~5 × 106Cfu/mL tests bacteria suspension, in nutrient agar
Uniformly smear 3 times on culture medium flat plate surface.Often smear 1 time, flat board should rotate 60 °, finally smear cotton swab around plate edge
One week.Plate is covered, puts drying at room temperature 5min.
(4) bacteriostatic agent print is placed with
Feared subsample piece with sterile and be placed with planar surface.At a distance of more than 25mm between each print center, the week with flat board
Edge is at a distance of more than 15rmn.After being placed with, with the light pressure-like piece of aseptic nipper, it is set to be close to planar surface.Glass dish is covered, is put
In 37 DEG C of insulating boxs, result is observed after cultivating 24h.With the diameter and record of vernier caliper measurement antibacterial ring size.
Experiment is repeated 3 times.The diameter of the diametrically-sample of antibacterial ring size=outside.Measure antibacterial ring size when, should select uniformly and entirely without
The antibacterial ring size of bacteria growing is carried out.Measuring its diameter should be using antibacterial ring size outer as boundary.Inhibition zone diameter is more than 7nim, has been judged to antibacterial
Effect；Inhibition zone diameter is less than or equal to 7mm, is judged to no bacteriostasis.
2nd, MIC experimentations
(1) sterilize：The glass apparatus (beaker, glass bar, pipette and culture dish) that will be used in antiseptic and experiment
It is placed on progress high-temperature sterilization processing in digital display Constant Temp. Oven.
(2) bacterium solution prepares：With taking collarium to be inoculated into the strain of preservation on LB bases (staphylococcus aureus) with method of scoring,
24h is cultivated in 37 DEG C of incubators, takes typical bacterium colony to move on in the conical flask equipped with culture medium, is rocked under the conditions of 37 DEG C
24h is cultivated, a series of dilution is carried out to culture medium by PBS, makes bacteria suspension concentration 1 × 107-2×107μg/
ML, it is standby.
(3) then the antimicrobial for weighing 2mL with pipette is resisted in beaker with the PBS for weighing 38mL
Microbial inoculum is diluted, and is stirred, and forms the PBS dilutions that antimicrobial agent concentration is 5.0% (volume fraction).Take the sample of the concentration
Product 10mL, then using double dilution method, obtain a series of sample of concentration：500,250,125,62.5,31.25 μ g/mL
(ppm)。
(4) above-mentioned concentration sample and blank sample 1mL are taken, is mixed with 1mL bacteria suspensions, by each pipe bacterium transferred species LB flat board cultures
On base, after being cultivated 24 hours at 37 DEG C, culture dish observation is taken out, photographs to record experiment clump count.
3rd, security test：With reference to the cytotoxicity experiments of GB/T 16886.5, the cytotoxicity of all embodiments is 0
Level.
The antibacterial ring size experimental results of table 1
Table 2MIC test results
Note：" ++ " represents to have grown a large amount of bacteriums on culture medium, shows that pressing down (anti-) microbial inoculum does not press down (anti-) bacterium work to bacterium
With；"+" represents to show that pressing down (anti-) microbial inoculum has bacterium the effect of certain suppression (anti-) bacterium with the presence of a small amount of bacterium on culture medium；
" ± ", represents there is few bacterium in culture medium, shows that pressing down (anti-) microbial inoculum has the effect of larger suppression (anti-) bacterium to bacterium；"-" represents
Without bacteria living in culture medium, show that pressing down (anti-) microbial inoculum has complete suppression (anti-) bacterium effect to bacterium.
Meanwhile by heretofore described high-effective broad-spectrum fungicide according to《QB/T 2738-2005》To Escherichia coli, gold
Staphylococcus aureus and Candida albicans carry out sterilization test, and the formula of embodiment 1 reaches 100% to the sterilizing rate of three,
Remaining embodiment has a weak tendency.
Foregoing example is merely illustrative, some features of the feature for explaining the disclosure.Appended claim
It is intended to require the scope as wide as possible being contemplated that, and embodiments as presented herein is only according to all possible embodiment
Combination selection embodiment explanation.Therefore, the purpose of applicant is appended claim not by the explanation present invention
Feature example selectional restriction.And the progress in science and technology will not formed due to the inaccuracy of language performance and not
The possible equivalent or son being presently considered are replaced, and these changes should also be interpreted by appended in the conceived case
Claim covers.
Claims (1)
- A kind of 1. high-effective broad-spectrum fungicide of low content Nano silver solution, it is characterised in that by weight, its preparing raw material bag Contain：One or more of the auxiliary agent in dispersant, stabilizer, preservative, thickener, wetting agent；The dispersant be selected from calcium lignosulfonate, sodium methylene bis-naphthalene sulfonate, naphthalenesulfonate formaldehyde condensation compound, polycarboxylate and At least one of polyoxyethylene polyoxypropylene base ether block copolymers；The stabilizer is selected from 2,6- di-t-butyl -4- methyl-phenols, butylated hydroxy anisole, phosphoric acid, acetic acid, triethylamine, chlorine Change at least one of ammonium and sodium carbonate；The preservative is included in benzoic acid, sorbic acid, benzoate and sorbate extremely Few one kind；The wetting agent is selected from lauryl sodium sulfate, sldium lauryl sulfate, neopelex, aliphatic alcohol polyethenoxy At least one of ether and APES；At least one of the preservative benzoic acid, sorbic acid, benzoate and sorbate；The thickener includes sodium alginate, Magnesiumaluminumsilicate, xanthans, polyethylene glycol, polyvinyl alcohol, carboxymethyl cellulose and phenol At least one of urea formaldehyde；The nano-ag composite is the compound of Nano silver piece, water-based chitosan and Nano silver grain；The Nano silver grain is based on { 200 } crystal face；The weight of the Nano silver piece, water-based chitosan and Nano silver grain Part is than being 1：30：50；The preparing raw material of the high-effective broad-spectrum fungicide also includes release membranes, and the preparing raw material of the release membranes includes formula (1) thing Matter, the structure of the formula (1) are as follows：
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| CN108392591B (en) * | 2018-05-29 | 2021-08-06 | 安徽省银锂子生物科技发展有限公司 | Nano-silver female bacteriostatic balance gel capable of preventing vaginitis |
| CN108907231B (en) * | 2018-07-26 | 2020-02-28 | 湖南大学 | Method for improving antibacterial property of nano-silver |
| CN109221104B (en) * | 2018-10-18 | 2022-03-22 | 河南师范大学 | Silver-containing carbon dots, preparation method and application thereof |
| TWI698507B (en) | 2018-12-06 | 2020-07-11 | 財團法人工業技術研究院 | Modified metal nanoplate and conductive paste comprising the same |
| CN109362801A (en) * | 2018-12-12 | 2019-02-22 | 薛双 | A kind of nanometer of animal and veterinary thimerosal and preparation method thereof |
| EP4093203A1 (en) * | 2020-01-23 | 2022-11-30 | Clearleaf Inc. | Methods of using a colloidal silver-based composition in reducing or preventing microbial contamination in plants or explants in tissue culture processes |
| CN111449086A (en) * | 2020-05-11 | 2020-07-28 | 武汉工程大学 | Colloidal silver/polymer mixed disinfectant and preparation method and application thereof |
| CN112021340A (en) * | 2020-07-28 | 2020-12-04 | 北京工业大学 | Preparation and application of nano composite bactericidal antiviral material |
| CN112143583A (en) * | 2020-10-10 | 2020-12-29 | 苏州特密达新材料有限公司 | Semi-aqueous cleaning agent containing nano silver |
| CN115885986A (en) * | 2021-10-28 | 2023-04-04 | 郝文杰 | Preparation method and application of multifunctional metal salt composite membrane composition |
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| CN101050315A (en) * | 2006-04-07 | 2007-10-10 | 中国科学院上海应用物理研究所 | Method for preparing Nano silver grain, and prepared Nano silver grain |
| CN101204158A (en) * | 2007-12-13 | 2008-06-25 | 沈阳大学 | Nanometer compound fungicide and preparation method thereof |
| CN104145993A (en) * | 2014-08-04 | 2014-11-19 | 太原理工大学 | Method for preparing complex antimicrobial agent by blending chitosan and silver copper |
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| CN101050315A (en) * | 2006-04-07 | 2007-10-10 | 中国科学院上海应用物理研究所 | Method for preparing Nano silver grain, and prepared Nano silver grain |
| CN101204158A (en) * | 2007-12-13 | 2008-06-25 | 沈阳大学 | Nanometer compound fungicide and preparation method thereof |
| CN104145993A (en) * | 2014-08-04 | 2014-11-19 | 太原理工大学 | Method for preparing complex antimicrobial agent by blending chitosan and silver copper |
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