CN107306942A - The preparation method of control release type nano-pesticide formulation - Google Patents

The preparation method of control release type nano-pesticide formulation Download PDF

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Publication number
CN107306942A
CN107306942A CN201710486028.4A CN201710486028A CN107306942A CN 107306942 A CN107306942 A CN 107306942A CN 201710486028 A CN201710486028 A CN 201710486028A CN 107306942 A CN107306942 A CN 107306942A
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pesticide
nano
parts
preparation
miniemulsion
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CN107306942B (en
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崔海信
王琰
王安琪
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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Institute of Environment and Sustainable Development in Agriculturem of CAAS
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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
    • 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
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention provides a kind of preparation method of nano-pesticide formulation, and methods described includes：The component of nano-pesticide formulation is formed into colostric fluid through emulsification, the nano-pesticide formulation of wall material parcel is then made through high-pressure homogeneous formation miniemulsion.The preparation method for the nano-pesticide formulation that the present invention is provided is simple, easy to operate, reproducible, and the nano-pesticide formulation particle diameter prepared is small, particle dispersion is good and sustained release performance is excellent.

Description

The preparation method of control release type nano-pesticide formulation
Technical field
The invention belongs to technical field of pesticide.In particular it relates to a kind of preparation method of nano-pesticide formulation.
Background technology
Agricultural chemicals is the important substance basis for ensureing national food security.Traditional formulations of pesticide are generally open system, from From the point of view of formulations of pesticide registration situation, the agricultural chemicals conventional dosage forms based on missible oil, wettable powder, microemulsion etc. account for domestic city More than 70% share of field, these conventional dosage forms belong to open system, there is medicine drop to some extent in use mostly Tumble, drift, the loss such as spring and dust drift, eventually arrive at the effective rate of utilization of crop target less than 30%, reach insect It is internal by dose less than 0.1%, the effective rate of utilization of agricultural chemicals is relatively low.
The differences such as globulate, hollow scrotiform are prepared by being wrapped up, being coupled using high polymer material by agricultural chemicals, inlayed etc. During the formulation of structure, wall material can provide physical barrier effect, thus can block ultraviolet light, and the illumination for significantly improving agricultural chemicals is stable Property, the absorption of soil is reduced, delays degraded caused by illumination or other undesirable elements, decompose and be lost in, while poison can be reduced Property, pollution abatement improves the prevention effect of product.Such formulation also has the effect of control release, according to dispenser scene not Together, spacetabs type and quick releasing type can be divided into.Spacetabs type is mainly used in soil treatment and seed treatment, and quick releasing type is mainly used in cauline leaf Spraying, ground surface blockage are administered and Aerial spraying.However, from the point of view of the registration situation of the current formulations of pesticide, relative to other formulations, The formulation proportions such as agricultural chemicals is spherical, scrotiform are less, and it is also relative complex that it researches and develops technique.
The traditional preparation methods of agricultural chemicals microballoon/microcapsule formulation mainly include situ aggregation method, interfacial polymerization, coacervation, Spray drying process etc..Wherein situ aggregation method need to be heated certain time when forming cyst wall, not only have certain to process equipment It is required that, and have an impact to the repeatability of product.Easily occur when preparing high concentration microballoon/microcapsule formulation using interfacial polymerization Crystalline polamer, the irregular crystal crystallized out can destroy cyst wall to lead to not play drug effect.Spray drying process is a kind of thing Preparation method is managed, the particle diameter of the agricultural chemicals microballoon/microcapsule formulation prepared using this method is larger, and particle diameter is difficult to realize nanometer scale. There is following defect in the agricultural chemicals microballoon/microcapsule formulation prepared at present using conventional method：In configuration aspects, presently commercially available agricultural chemicals The particle diameter of microballoon/microcapsule formulation is universal in 5 microns, not up to nanoscale, and thick particle diameter easily causes drop to tumble, powder Dirt drift so that the tack, permeability and bioavilability in use to crop target are poor, at the same activity also compared with It is low；In terms of particle dispersion, the monodispersity of the agricultural chemicals microballoon/microcapsule formulation prepared at present is poor, serious and particle diameter point of reuniting Cloth is uneven, and its surface nature and structure and morphology are not also regulated and controled effectively；It is existing in terms of the controllable sustained-release of agricultural chemicals Agricultural chemicals microballoon/microcapsule formulation can only be realized mostly simply, qualitatively slowly to be discharged, and rate of release is unstable controllable；In technique stream In terms of journey, using techniques, complex process, more difficult control and poor repeatability such as heating and thermal insulation, gas shields more than conventional method.
Therefore, how a kind of preparation side of simple, easy to operate, the reproducible agricultural chemicals microballoon/microcapsule formulation of technique is provided Method, so that it is urgently to be resolved hurrily as this area to prepare the nano-pesticide formulation that particle diameter is small, particle dispersion is good and sustained release performance is excellent Problem.
The content of the invention
In view of the above-mentioned problems, it is an object of the invention to provide a kind of preparation method of nano-pesticide formulation, the preparation side Method is simple, easy to operate, reproducible, and the nano-pesticide formulation particle diameter prepared is small, particle dispersion good and slow release Can be excellent.
To reach above-mentioned purpose, the present invention provides a kind of preparation method of nano-pesticide formulation, and methods described includes：It will receive The component of rice pesticidal preparations forms colostric fluid through emulsification, and nano-pesticide formulation then is made through high-pressure homogeneous formation miniemulsion.
In some embodiments, the preparation method comprises the following steps：
Step a：Pesticide activity component, organic solvent, cyst material, emulsifying dispersant and water are mixed, breast is then carried out Change, obtain colostric fluid；
Step b：By the colostric fluid obtained in step a by high-pressure homogeneous carry out fine crankshaft, miniemulsion is obtained；
Step c：By the miniemulsion obtained in step b stirring, organic solvent is volatilized, obtain nano pesticide mother liquor；
Step d：The nano pesticide mother liquor obtained in step c is mixed with excipient and adjuvant, nano pesticide system is obtained Agent.
In some embodiments, the nano-pesticide formulation is spherical, and the step a includes：By pesticide activity component It is dissolved in organic solvent, adds cyst material, obtain oil phase, emulsifying dispersant is dissolved in the water and obtains aqueous phase, by oil phase It is mixed with water after conjunction, is emulsified, obtains O/W (oil-in-water) type colostric fluid.
In some embodiments, the nano-pesticide formulation is nano pesticide aqueous suspension agent, and the excipient is thickening Agent, the step d includes：Thickener and adjuvant are directly added into the nano pesticide mother liquor obtained in step c, mixing is equal It is even, obtain nano pesticide aqueous suspension agent.
In some embodiments, the nano-pesticide formulation is nano pesticide solid powder, and the excipient is solid Filler, the step d includes：The nano pesticide mother liquor obtained in step c is obtained into solid powder after centrifugation and drying, added Solid packing and adjuvant, are well mixed, obtain nano pesticide solid powder.
In some embodiments, the emulsification in the step a is one in ultrasonic emulsification, emulsification pretreatment and grinding emulsification Plant or a variety of, preferably the one or more in emulsification pretreatment and grinding emulsification；The particle diameter of the drop of the colostric fluid is 100- 900nm, preferably 100-500nm.
Wherein described ultrasonic emulsification is carried out using ultrasonic grinder, and the power of the ultrasonic grinder is 65-650W, It is preferred that 325-637W, more preferably 585W；The time of ultrasonic emulsification is 2-30min, more preferably preferably 5-25min, 15min.
Wherein described emulsification pretreatment is carried out using high-speed shearing machine, and the shearing rotating speed of the high-speed shearing machine is 10000- 28000rmp, preferably 22000-28000rmp, more preferably 28000rmp；Shear time is 3-40min, preferably 3-30min, more excellent Select 15min.
Wherein described grinding emulsification is carried out using grinding distribution machine, and the frequency of grinding emulsification is 30-50Hz, preferably 40- 50Hz, more preferably 50Hz；Milling time is 5-60min, preferably 5-40min, more preferably 15min.
In some embodiments, the high-pressure homogeneous use high pressure homogenizer in the step b is carried out, high-pressure homogeneous pressure Power is 100-1200Pa, preferably 600-1000Pa, more preferably 900Pa；The high-pressure homogeneous time is 10min-2h, preferably 10min- 1h, more preferably 15min；The particle diameter of the drop of the miniemulsion is 10-600nm, preferably 10-100nm.
In some embodiments, it is stirred in the step c using electric mixer, mixing speed is 500- 1500rpm, preferably 1000-1500rpm, more preferably 1500rpm；Mixing time is 5-24h, preferably 10-20h, more preferably 12h.
In some embodiments, when the nano-pesticide formulation is nano pesticide solid powder, in the step d, 10-30min is centrifuged under rotating speed 4000-15000rpm using high speed freezing centrifuge；Preferably, using high speed freezing centrifuge 20-30min is centrifuged under rotating speed 4000-15000rpm；It is highly preferred that using high speed freezing centrifuge under rotating speed 15000rpm Centrifuge 20min.
In some embodiments, when the nano-pesticide formulation is nano pesticide solid powder, in the step d Dry as spray drying or be freeze-dried, wherein the spray drying is carried out using spray dryer, the condition of spray drying is 30-300 DEG C of EAT, 30-140 DEG C of leaving air temp, drying time 1-1.5s；The freeze-drying is entered using freeze drier OK, the condition of freeze-drying is the precooling 4h at -50 DEG C, keeps 12-24h at -60 DEG C；It is preferred that at -50 DEG C precooling 4h, keeps 12h at -60 DEG C.
In some embodiments, the particle diameter of the nano-pesticide formulation is 20-500nm, preferably smaller than equal to 100nm, More preferably less than 50nm；Preferably, the drugloading rate of the nano pesticide solid powder is 0.1-90%, and the nano pesticide water hangs The drugloading rate of floating agent is 0.1-20%.
In some embodiments, by weight, the nano-pesticide formulation is made up of following components：
Pesticide activity component：0.1-40 parts
Cyst material：0.1-40 parts
Emulsifying dispersant：0.2-30 parts
Organic solvent：10-300 parts
Water：20-500 parts
Excipient：0.1-400 parts
Adjuvant：0-20 parts,
Wherein, the ratio of the pesticide activity component and cyst material is 0.1:1-10:1.
In some embodiments, the nano-pesticide formulation is nano pesticide solid powder, wherein the excipient is Solid packing, by weight, the nano pesticide solid powder are made up of following components：
Pesticide activity component：0.1-40 parts
Cyst material：0.1-40 parts
Emulsifying dispersant：0.2-30 parts
Organic solvent：10-300 parts
Water：20-500 parts
Solid packing：0.1-400 parts
Adjuvant：0-20 parts,
Wherein, the ratio of the pesticide activity component and cyst material is 0.1:1-10:1；
Preferably, by weight, the nano pesticide solid powder is made up of following components：
Pesticide activity component：0.5-30 parts
Cyst material：0.5-30 parts
Emulsifying dispersant：0.5-20 parts
Organic solvent：10-100 parts
Water：50-200 parts
Solid packing：10-400 parts
Adjuvant：0-15 parts；
It is highly preferred that by weight, the nano pesticide solid powder is made up of following components：
Pesticide activity component：1-20 parts
Cyst material：1-20 parts
Emulsifying dispersant：0.5-10 parts
Organic solvent：20-100 parts
Water：50-200 parts
Solid packing：10-200 parts
Adjuvant：0-15 parts.
Or, the nano-pesticide formulation is nano pesticide aqueous suspension agent, wherein the excipient is thickener, by weight Meter, the nano pesticide aqueous suspension agent is made up of following components：
Pesticide activity component：0.1-40 parts
Cyst material：0.1-40 parts
Emulsifying dispersant：0.2-30 parts
Organic solvent：10-300 parts
Water：20-500 parts
Thickener：0.1-20 parts
Adjuvant：0-20 parts,
Wherein, the ratio of the pesticide activity component and cyst material is 0.1:1-10:1；
Preferably, by weight, the nano pesticide aqueous suspension agent is made up of following components：
Pesticide activity component：0.5-30 parts
Cyst material：0.5-30 parts
Emulsifying dispersant：0.5-20 parts
Organic solvent：10-100 parts
Water：50-200 parts
Thickener：1-15 parts
Adjuvant：0-15 parts；
It is highly preferred that by weight, the nano pesticide aqueous suspension agent is made up of following components：
Pesticide activity component：1-20 parts
Cyst material：1-20 parts
Emulsifying dispersant：0.5-10 parts
Organic solvent：20-100 parts
Water：50-200 parts
Thickener：1-10 parts
Adjuvant：0-15 parts.
In some embodiments, the pesticide activity component is selected from insecticide, bactericide, herbicide and plant growth and adjusted Save the one or more in agent；
The cyst material is degradable high polymer material.
In some embodiments, the insecticide is selected from following one or more：AVM, methylamino Avermectin Plain benzoate, gamma cyhalothrin, Rynaxypyr, pleocidin, indoxacarb, clothianidin, carbosulfan, triazole Phosphorus, diazinon, many mite prestige, chlopyrifos, Biphenthrin, cyphenothrin, ethofenprox, decis, fenvalerate, cyfluthrin, Tefluthrin, lythidathion, phoxim, imidacloprid and Diacloden, preferably Diacloden, pleocidin, Rynaxypyr, Avermectin One or more in element, emamectin-benzoate and gamma cyhalothrin.
In some embodiments, the bactericide is selected from following one or more：Fluoxastrobin, pyraclostrobin, thiophene Ofurace, metconazole, 2-cyano-3-amino-3-phenylancryic acetate, fluazinam, cymoxanil, Boscalid, ethofenprox, cyflumetofen, Fenpropathrin, benzene thiophene bacterium Ester, pefurazoate, Prochloraz, propiconazole, Difenoconazoles, Metalaxyl-M, Flusilazole, epoxiconazole, trifloxystrobin and pyraclostrobin, preferably thiophene One kind or many in ofurace, metconazole, 2-cyano-3-amino-3-phenylancryic acetate, fluazinam, Fluoxastrobin, pyraclostrobin, cymoxanil and Boscalid Kind.
In some embodiments, the herbicide is selected from following one or more：Pendimethalin, tri-allate, 2,4-D Different monooctyl ester, benthiocarb, molinate, cover grass energy, clomazone, butralin, S-metolachlor, trefanocide and prometryn, preferably two One or more in the spirit of first penta and S-metolachlor.
In some embodiments, the plant growth regulator is selected from following one or more：Brassinosteroid, ammonia Oxygen ethyl vinyl glycine and multiple-effect azole plant growth regulator, preferably multiple-effect azole plant growth regulator.
In some embodiments, the cyst material is selected from following one or more：Polyester acrylate and its spread out Biology, polyvinyl acetate resin, polyacrylonitrile resin, polystyrene resin, PLA, gelatin, modified starch, cellulose and its One kind in derivative, chitosan and Arabic gum, preferred cellulose and its derivative, chitosan, PLA and modified starch Or it is a variety of.
In some embodiments, the emulsifying dispersant is the one or more in agricultural emulsifier and dispersant, excellent Selection of land, the agricultural emulsifier is selected from the serial (Nonyl pheno of OP serial (OPEO, such as OP-10), NP Ether), EL serial (castor oil polyoxyethylene ether, such as EL 40), Tween series (tween, such as Tween 80, Tween 60, Tween 20), Span serial (sapn, such as Span 60, Span 80), AEO serial (AEO, such as AEO-9), agriculture breast system One or more in row, polyvinyl alcohol, cithrol, polyvinylpyrrolidone and polyethylene glycol (PEG) oleate；It is excellent Select the one or more in Tween series, polyvinyl alcohol and the serial emulsifying agent of agriculture breast；More preferably polyvinyl alcohol, agriculture breast 300 are One in row, the series of agriculture breast 500, the series of agriculture breast 600, Nongru-700 series and serial (such as agriculture breast 1601) emulsifying agent of agriculture breast 1600 Plant or a variety of.
In some embodiments, the dispersant is selected from carboxylate, sulfate, sulfonate, phosphate ester salt and alkyl phenol One or more in APEO, it is preferable that the dispersant is selected from aliphatic alcohol polyethenoxy ether carboxylate, dodecyl Sodium sulphate, lignosulfonates, dodecyl sodium sulfate, maleated rosin polyethenoxy-oxypropylene ether sulfonate and dodecyl In one or more in ether phosphate salt, more preferably lignosulfonates, lauryl sodium sulfate and dodecyl sodium sulfate One or more.
In some embodiments, the adjuvant is selected from preservative, defoamer, antifreeze, pH adjusting agent and wetting point One or more in powder, preferably antifreeze, defoamer and one kind in wetting dispersing agent (such as TERSPERSE 2020) or It is a variety of.
In some embodiments, the antifreeze is in ethylene glycol, propane diols, glycerine, isopropanol and urea One or more, preferably ethylene glycol.
In some embodiments, one or more of the defoamer in organic silicon and low-carbon alcohols defoamer, It is preferred that organic silicon defoamer.
In some embodiments, the thickener be selected from xanthans, Arabic gum, gelatin, cellulose and its derivates, It is one or more in diatomite, polyvinyl alcohol, Sodium Polyacrylate, dextrin, aluminium-magnesium silicate and Silica hydrogel, preferably xanthans, bright One or more in glue, aluminium-magnesium silicate, cellulose and its derivates and polyvinyl alcohol.
In some embodiments, the organic solvent is selected from dichloromethane, chloroform, vegetable oil, petroleum ether and fat One or more in fat hydrocarbon solvent oil, preferably dichloromethane.
In some embodiments, the solid packing be selected from diatomite, kaolin, talcum powder, montmorillonite, white carbon, One or more in one or more in cornstarch and sepiolite, preferably kaolin, cornstarch and white carbon.
By using the method for the present invention, nano level spherical pesticidal preparations are can obtain, nano-pesticide formulation is small due to its Size, bigger serface and modifiability, the effective rate of utilization for raising agricultural chemicals provide a new approach.Carried using nanometer Body material unique skin effect and small-size effect, by the mode carrying medicament such as adsorbing, being coupled, wrap up or inlay, both may be used To realize the high-efficient carrier of medicine, by adjusting the fine structure of nano-carrier medicine can also be realized in time, space and agent Intellectuality precisely release in amount, minimum effective target activity is maintained in a period of setting, medicine is significantly increased Validity and security.Pass through the work(such as the carrier loaded of nano medicament carrying system, water baseization scattered, targeting delivery, controlled release Can, the dispersiveness, stability and utilization rate of agricultural chemicals can be improved, extends the lasting period, residual contamination is reduced.In addition, relative to micro- Microballoon/encapsulated form of metrical scale, the granularity of nano-pesticide formulation reaches nanometer scale, and its small-size effect can spray in field Increase ductility, wetability, the target adsorptivity of pesticide droplet during applying, with advantage more efficiently with environmental protection, and Nanometer formulation is easier to be deposited on plant leaf blade, and its bigger serface characteristic adds the adhesiveness to target, and then reduces The loss of agricultural chemicals.
High pressure homogenization method refers to liquid material under super-pressure effect, special homogeneous chamber generation is flowed through at a high speed tiny Drop.High pressure homogenization method can produce the particle of micro/nano level, effectively prevent particle from caking.The present invention uses new preparation Technique prepares nano-pesticide formulation, specifically, and the present invention prepares nano-pesticide formulation using emulsifying method.In the system of the present invention In Preparation Method, colostric fluid is prepared using the one or more in ultrasonic emulsification, emulsification pretreatment and grinding emulsification first, is then used High pressure homogenization method prepares miniemulsion, finally adds excipient and adjuvant obtains the nano-pesticide formulation of favorable dispersibility.
The present invention prepares nano-pesticide formulation using emulsifying method, and by adjusting component formula, technological process and step In rapid each parameter etc. prepared be uniformly dispersed, the nano-pesticide formulation of function admirable.
Compared with prior art, the preparation method for the nano-pesticide formulation that the present invention is provided has the advantage that：
1. in terms of particle diameter, nano-pesticide formulation of the invention has Nano Particle, particle diameter is smaller than 50nm so that receive The specific surface area increase of rice pesticidal preparations, improves the contact area of agricultural chemicals and crop surface, adds agricultural chemicals on crop blade face Adhesiveness and permeability, be conducive to agricultural chemicals to be embedded into the micro-nano structure on crop blade face, strengthen blade face retention rate, reduce stream Lose, so as to improve the effective rate of utilization and drug effect of agricultural chemicals, reduce spray dosage and number of times；In addition, the nano pesticide of the present invention The particle diameter of preparation is smaller, the contact area increase with insect target, can increase the insecticidal activity to insect target；
2. in terms of particle diameter, the nano-pesticide formulation prepared using the inventive method has Nano Particle, particle diameter can be small In 50nm so that the specific surface area increase of nano-pesticide formulation, the contact area of agricultural chemicals and crop surface is improved, increases agricultural chemicals Adhesiveness and permeability on crop blade face, strengthen blade face retention rate, are conducive to being embedded into the micro-nano structure on crop blade face, subtract It is few to be lost in, so as to improve the effective rate of utilization and drug effect of agricultural chemicals；In addition, the nano-pesticide formulation prepared using the inventive method Particle diameter it is smaller, with the increase of the contact area of insect target, the insecticidal activity to insect target can be increased；
3. in terms of particle dispersion, the monodispersity of the nano-pesticide formulation prepared using the inventive method is good, grain Footpath is small and is evenly distributed；
4. in terms of the controllable sustained-release of agricultural chemicals, the slow release speed of the nano-pesticide formulation prepared using the inventive method is accurate It is adjustable, can be by adjusting one in constituent content, particle size, appearance structure, cavernous structure, total pore volume, duct quantity etc. Plant or a variety of, to realize the control accurate of pesticide slow-release speed；The pesticide slow-release formulation prepared at present using conventional method Sustained release preventing and treating period regulation be limited, and use the inventive method prepare nano-pesticide formulation the sustained release phase in -3 months 3 days, can Regulated and controled according to specific dispenser scene demand, effectively extend the sustained release phase of pesticidal preparations, so as to be conducive to improving agriculture The activity and reduction spray number of times and dosage of medicine；
5. in terms of material, the wall material of the nano-pesticide formulation prepared using the inventive method using safety, low cost and Degradable high polymer material is made, and advantageously reduces the pollution to environment；
6. in terms of drugloading rate, the drugloading rate of the nano-pesticide formulation prepared using the inventive method can 0.1-90% it Between adjust, application is wider；
7. in terms of ultraviolet light degradation property, the anti-purple of nano-pesticide formulation can be effectively improved using the inventive method Outer light degradation property, so as to drastically increase effective rate of utilization and bioavilability, reduces spraying times and dosage, is conducive to Environmental protection and ecological safety.
Brief description of the drawings
Fig. 1 is the transmission electron micrograph of gamma cyhalothrin nano-pesticide formulation prepared by the embodiment of the present invention And grain size distribution；
Fig. 2 is the scanning electron microscope diagram piece of avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention；
Fig. 3 is that the scanning electron of emamectin-benzoate nano-pesticide formulation prepared by the embodiment of the present invention shows Micro mirror picture；
Fig. 4 is the electron microscope picture of avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention；
Fig. 5 is the particle diameter and grain size distribution of avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention；
Fig. 6 shows the emamectin-benzoate nano-pesticide formulation of preparation of the embodiment of the present invention in cucumber leaf Distribution on piece；
Fig. 7 is the elution profiles of avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention；
Fig. 8 is the ultraviolet photolysis figure of avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention.
Embodiment
Illustrate the present invention referring to specific embodiment.It will be appreciated by those skilled in the art that these embodiments are only For illustrating the present invention, it does not limit the scope of the present invention in any way.
Experimental method in following embodiments, is conventional method unless otherwise specified.Medicine used in following embodiments Agent raw material, reagent material etc., unless otherwise specified, are commercially available products.
Instrument
Ultrasonic grinder (SCIENTZ, JY92-IIN)
High-speed shearing machine (FLUKO, FA25)
Grinding distribution machine (SGN, GMSD2000/4)
High pressure homogenizer (ATS, AH-100D)
Electric mixer (IKA, EUROSTAR 60)
High speed freezing centrifuge (Thermo SCIENTIFIC, ST 16R)
Freeze drier (BIOCOOL, Pilot2-4M)
SEM (Hitachi, SU8010)
Transmission electron microscope (HITACHI, HT7700)
Environmental scanning electron microscope (FEI, Quanta FEG 250)
Nanometer laser particle size analyzer (Malvern, Nano ZS90)
Ultraviolet-uisible spectrophotometer (Shimadzu, TU901)
Agricultural chemicals photo-stability testing case (Xutemp, XT5409-XPC80)
The preparation of the nano pesticide solid powder 1 of embodiment 1
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials are added fine Dimension element, obtains oil phase, 2g emulsifying dispersants (1g polyvinyl alcohol and 1g agriculture breasts 1601) is dissolved in 200ml water and obtain aqueous phase, Oil phase is mixed with water after conjunction, using ultrasonic grinder under 585W ultrasonic emulsification 15min, obtain O/W type colostric fluids, wherein The particle diameter of the drop of colostric fluid is 600nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 400nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 0.5g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 1.
The preparation of the nano pesticide aqueous suspension agent 2 of embodiment 2
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials are added fine Dimension element, obtains oil phase, 2g emulsifying dispersants (1g polyvinyl alcohol and 1g agriculture breasts 1601) is dissolved in 200ml water and obtain aqueous phase, Oil phase is mixed with water after conjunction, using ultrasonic grinder under 585W ultrasonic emulsification 15min, obtain O/W type colostric fluids, wherein The particle diameter of the drop of colostric fluid is 600nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 400nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 2.
The preparation of the nano pesticide solid powder 3 of embodiment 3
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 1g emulsifying dispersants (0.5g polyvinyl alcohol and 0.5g agriculture breasts 1601) are dissolved in 200ml water and obtain water Phase, oil phase is mixed with water after conjunction, is emulsified 15min in 28000rmp down cuts using high-speed shearing machine, is obtained O/W type colostrums The particle diameter of the drop of liquid, wherein colostric fluid is 300nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 0.5g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 3.
The preparation of the nano pesticide aqueous suspension agent 4 of embodiment 4
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 1g emulsifying dispersants (0.5g polyvinyl alcohol and 0.5g agriculture breasts 1601) are dissolved in 200ml water and obtain water Phase, oil phase is mixed with water after conjunction, is emulsified 15min in 28000rmp down cuts using high-speed shearing machine, is obtained O/W type colostrums The particle diameter of the drop of liquid, wherein colostric fluid is 300nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 4.
The preparation of the nano pesticide solid powder 5 of embodiment 5
4g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 2g emulsifying dispersants (1g polyvinyl alcohol and 1g agriculture breasts 1601) are dissolved in 200ml water and obtain aqueous phase, Oil phase is mixed with water after conjunction, emulsification 15min is ground using grinding distribution machine at 50 hz, O/W type colostric fluids are obtained, wherein just The particle diameter of the drop of emulsion is 250nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 90nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 1g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 5.
The preparation of the nano pesticide aqueous suspension agent 6 of embodiment 6
4g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 2g emulsifying dispersants (1g polyvinyl alcohol and 1g agriculture breasts 1601) are dissolved in 200ml water and obtain aqueous phase, Oil phase is mixed with water after conjunction, emulsification 15min is ground using grinding distribution machine at 50 hz, O/W type colostric fluids are obtained, wherein just The particle diameter of the drop of emulsion is 250nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 90nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 6.
The preparation of the nano pesticide solid powder 7 of embodiment 7
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 3g emulsifying dispersants (2g polyvinyl alcohol and 1g gelatin) are dissolved in 200ml water and obtain aqueous phase, by oil Mutually it is mixed with water after conjunction, 15min is emulsified in 28000rmp down cuts using high-speed shearing machine, O/W type colostric fluids are obtained, wherein just The particle diameter of the drop of emulsion is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 300nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 0.5g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 7.
The preparation of the nano pesticide solid powder 8 of embodiment 8
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 2.5g emulsifying dispersants (1.5g polyvinyl alcohol and 1g gelatin) are dissolved in 200ml water and obtain aqueous phase, Oil phase is mixed with water after conjunction, 15min is emulsified in 28000rmp down cuts using high-speed shearing machine, O/W type colostric fluids are obtained, its The particle diameter of the drop of middle colostric fluid is 500nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 400nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 0.5g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 8.
The preparation of the nano pesticide solid powder 9 of embodiment 9
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 2g emulsifying dispersants (1g polyvinyl alcohol and 1g gelatin) are dissolved in 200ml water and obtain aqueous phase, by oil Mutually it is mixed with water after conjunction, 15min is emulsified in 28000rmp down cuts using high-speed shearing machine, O/W type colostric fluids are obtained, wherein just The particle diameter of the drop of emulsion is 650nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 600nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 0.5g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 9.
The preparation of the nano pesticide solid powder 10 of embodiment 10
2g pesticide activity component AVMs are dissolved in 50ml organic solvent dichloromethanes, 2g cyst materials is added and gathers Lactic acid, obtains oil phase, and 1.5g emulsifying dispersants (0.5g polyvinyl alcohol and 1g gelatin) are dissolved in 200ml water and obtain aqueous phase, Oil phase is mixed with water after conjunction, 15min is emulsified in 28000rmp down cuts using high-speed shearing machine, O/W type colostric fluids are obtained, its The particle diameter of the drop of middle colostric fluid is 900nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 800nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 0.5g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 10.
The preparation of the nano pesticide solid powder 11 of embodiment 11
2g pesticide activity component emamectin-benzoates are dissolved in 50ml organic solvent dichloromethanes, plus Enter 2g cyst material celluloses, obtain oil phase, 2.5g emulsifying dispersants (1g polyvinyl alcohol and 1.5g EL 40) are dissolved in Obtain aqueous phase in 200ml water, oil phase be mixed with water after conjunction, using ultrasonic grinder under 585W ultrasonic emulsification 15min, obtain To O/W type colostric fluids, the wherein particle diameter of the drop of colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 100g solid packing kaolinites Soil and 0.5g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 11.
The preparation of the nano pesticide aqueous suspension agent 12 of embodiment 12
2g pesticide activity component emamectin-benzoates are dissolved in 50ml organic solvent dichloromethanes, plus Enter 2g cyst material celluloses, obtain oil phase, 2.5g emulsifying dispersants (1g polyvinyl alcohol and 1.5g EL 40) are dissolved in Obtain aqueous phase in 200ml water, oil phase be mixed with water after conjunction, using ultrasonic grinder under 585W ultrasonic emulsification 15min, obtain To O/W type colostric fluids, the wherein particle diameter of the drop of colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 12.
The preparation of the nano pesticide solid powder 13 of embodiment 13
2g pesticide activity component emamectin-benzoates are dissolved in 50ml organic solvent dichloromethanes, plus Enter 2g cyst material celluloses, obtain oil phase, 0.5g emulsifying dispersant polyvinyl alcohol is dissolved in 200ml water and obtains aqueous phase, Oil phase is mixed with water after conjunction, 15min is emulsified in 28000rmp down cuts using high-speed shearing machine, O/W type colostric fluids are obtained, its The particle diameter of the drop of middle colostric fluid is 600nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 400nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 80g solid packing kaolin With 0.3g adjuvants TERSPERSE 2020, it is well mixed, obtains nano pesticide solid powder 13.
The preparation of the nano pesticide aqueous suspension agent 14 of embodiment 14
2g pesticide activity component emamectin-benzoates are dissolved in 50ml organic solvent dichloromethanes, plus Enter 2g cyst material celluloses, obtain oil phase, 0.5g emulsifying dispersant polyvinyl alcohol is dissolved in 200ml water and obtains aqueous phase, Oil phase is mixed with water after conjunction, 15min is emulsified in 28000rmp down cuts using high-speed shearing machine, O/W type colostric fluids are obtained, its The particle diameter of the drop of middle colostric fluid is 600nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 400nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 14.
The preparation of the nano pesticide solid powder 15 of embodiment 15
2g pesticide activity component emamectin-benzoates are dissolved in 50ml organic solvent dichloromethanes, plus Enter 2g cyst material celluloses, obtain oil phase, 2.5g emulsifying dispersants (1g polyvinyl alcohol and 1.5g EL 40) are dissolved in Aqueous phase is obtained in 200ml water, oil phase is mixed with water after conjunction, emulsification 15min is ground using grinding distribution machine at 50 hz, obtained O/W type colostric fluids, the wherein particle diameter of the drop of colostric fluid are 250nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 90nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 80g solid packing kaolin With 0.5g adjuvants TERSPERSE 2020, it is well mixed, obtains nano pesticide solid powder 15.
The preparation of the nano pesticide aqueous suspension agent 16 of embodiment 16
2g pesticide activity component emamectin-benzoates are dissolved in 50ml organic solvent dichloromethanes, plus Enter 2g cyst material celluloses, obtain oil phase, 2.5g emulsifying dispersants (1g polyvinyl alcohol and 1.5g EL 40) are dissolved in Aqueous phase is obtained in 200ml water, oil phase is mixed with water after conjunction, emulsification 15min is ground using grinding distribution machine at 50 hz, obtained O/W type colostric fluids, the wherein particle diameter of the drop of colostric fluid are 250nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 90nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 16.
The preparation of the nano pesticide solid powder 17 of embodiment 17
2g pesticide activity component gamma cyhalothrins are dissolved in 100ml organic solvent dichloromethanes, 2g capsules are added Wall material PLA, obtains oil phase, and 6g emulsifying dispersant dodecyl sodium sulfates are dissolved in 200ml water and obtain aqueous phase, will Oil phase is mixed with water after conjunction, is emulsified 6min in 28000rmp down cuts using high-speed shearing machine, is obtained O/W type colostric fluids, wherein The particle diameter of the drop of colostric fluid is 150nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 15min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 50nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 150g solid packing kaolinites Soil and 0.2g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 17.
The preparation of the nano pesticide aqueous suspension agent 18 of embodiment 18
2g pesticide activity component gamma cyhalothrins are dissolved in 100ml organic solvent dichloromethanes, 2g capsules are added Wall material PLA, obtains oil phase, and 6g emulsifying dispersant dodecyl sodium sulfates are dissolved in 200ml water and obtain aqueous phase, will Oil phase is mixed with water after conjunction, is emulsified 6min in 28000rmp down cuts using high-speed shearing machine, is obtained O/W type colostric fluids, wherein The particle diameter of the drop of colostric fluid is 150nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 15min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 50nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 18.
The preparation of the nano pesticide solid powder 19 of embodiment 19
2g pesticide activity component gamma cyhalothrins are dissolved in 50ml organic solvent dichloromethanes, 2g cyst walls are added Material PLA, obtains oil phase, and 3g emulsifying dispersant polyvinyl alcohol is dissolved in 200ml water and obtains aqueous phase, by oil phase and water After mixing, using ultrasonic grinder under 585W ultrasonic emulsification 15min, obtain O/W type colostric fluids, the wherein liquid of colostric fluid The particle diameter of drop is 200nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 70nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 120g solid packing kaolinites Soil and 0.2g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 19.
The preparation of the nano pesticide aqueous suspension agent 20 of embodiment 20
2g pesticide activity component gamma cyhalothrins are dissolved in 50ml organic solvent dichloromethanes, 2g cyst walls are added Material PLA, obtains oil phase, and 3g emulsifying dispersant polyvinyl alcohol is dissolved in 200ml water and obtains aqueous phase, by oil phase and water After mixing, using ultrasonic grinder under 585W ultrasonic emulsification 15min, obtain O/W type colostric fluids, the wherein liquid of colostric fluid The particle diameter of drop is 200nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 70nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
2g thickeners (1g xanthans and 1g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, is well mixed, obtains Nano pesticide aqueous suspension agent 20.
The preparation of the nano pesticide solid powder 21 of embodiment 21
4g pesticide activity component gamma cyhalothrins are dissolved in 50ml organic solvent dichloromethanes, 2g cyst walls are added Material PLA, obtains oil phase, and 4g emulsifying dispersants (2g EL 40 and 2g agriculture breasts 500) are dissolved in 200ml water and obtain water Phase, oil phase is mixed with water after conjunction, is ground emulsification 15min at 50 hz using grinding distribution machine, is obtained O/W type colostric fluids, its The particle diameter of the drop of middle colostric fluid is 200nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 40nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 200g solid packing kaolinites Soil and 1g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 21.
The preparation of the nano pesticide aqueous suspension agent 22 of embodiment 22
4g pesticide activity component gamma cyhalothrins are dissolved in 50ml organic solvent dichloromethanes, 2g cyst walls are added Material PLA, obtains oil phase, and 4g emulsifying dispersants (2g EL 40 and 2g agriculture breasts 500) are dissolved in 200ml water and obtain water Phase, oil phase is mixed with water after conjunction, is ground emulsification 15min at 50 hz using grinding distribution machine, is obtained O/W type colostric fluids, its The particle diameter of the drop of middle colostric fluid is 200nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 40nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickeners (0.5g xanthans and 0.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, are well mixed, Obtain nano pesticide aqueous suspension agent 22.
The preparation of the nano pesticide solid powder 23 of embodiment 23
0.1g pesticide activity component AVMs are dissolved in 10ml organic solvent dichloromethanes, 1g cyst materials are added PLA, obtains oil phase, and 0.2g emulsifying dispersants (0.1g polyvinyl alcohol and 0.1g lignosulfonates) are dissolved in into 20ml water In obtain aqueous phase, oil phase is mixed with water after conjunction, using ultrasonic grinder under 65W ultrasonic emulsification 30min, obtain O/W types The particle diameter of the drop of colostric fluid, wherein colostric fluid is 300nm.
Using high pressure homogenizer under 1200Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 2h, obtain miniemulsion, wherein The particle diameter of the drop of miniemulsion is 50nm.
Above-mentioned miniemulsion is stirred under 1300rpm by 20h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 30min using high speed freezing centrifuge under 4000rpm, then using spraying Drying machine is spray-dried 1s at 100 DEG C of EAT, 140 DEG C of leaving air temp, obtains solid powder, adds 0.1g solid packings Diatomite, is well mixed, obtains nano pesticide solid powder 23.
The preparation of the nano pesticide aqueous suspension agent 24 of embodiment 24
0.1g pesticide activity component AVMs are dissolved in 10ml organic solvent dichloromethanes, 1g cyst materials are added PLA, obtains oil phase, and 0.2g emulsifying dispersants (0.1g polyvinyl alcohol and 0.1g lignosulfonates) are dissolved in into 20ml water In obtain aqueous phase, oil phase is mixed with water after conjunction, using ultrasonic grinder under 325W ultrasonic emulsification 15min, obtain O/W types The particle diameter of the drop of colostric fluid, wherein colostric fluid is 300nm.
Using high pressure homogenizer under 1000Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 1h, obtain miniemulsion, wherein The particle diameter of the drop of miniemulsion is 50nm.
Above-mentioned miniemulsion is stirred under 1000rpm by 22h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
0.1g thickener xanthans is added in above-mentioned nano pesticide mother liquor, is well mixed, obtains nano pesticide aqueous suspension Agent 24.
The preparation of the nano pesticide solid powder 25 of embodiment 25
1g pesticide activity component emamectin-benzoates are dissolved in 10ml organic solvent dichloromethanes, plus Enter 0.1g cyst material PLAs, obtain oil phase, by 0.2g emulsifying dispersants (0.1g polyvinyl alcohol and 0.1g lignin sulfonic acids Salt) be dissolved in 20ml water and obtain aqueous phase, oil phase is mixed with water after conjunction, using ultrasonic grinder under 585W ultrasonic emulsification 5min, obtains O/W type colostric fluids, the wherein particle diameter of the drop of colostric fluid is 500nm.
Using high pressure homogenizer under 600Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 50min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 50nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 5h using electric mixer, organic solvent is volatilized, obtains a nanometer agriculture Medicine mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using spray Mist drying machine is spray-dried 1.2s at 300 DEG C of EAT, 100 DEG C of leaving air temp, obtains solid powder, adds 0.1g solids Filler diatomite and 0.05g adjuvant propane diols, are well mixed, obtain nano pesticide solid powder 25.
The preparation of the nano pesticide aqueous suspension agent 26 of embodiment 26
1g pesticide activity component emamectin-benzoates are dissolved in 10ml organic solvent dichloromethanes, plus Enter 0.1g cyst material celluloses, obtain oil phase, 0.2g emulsifying dispersants agriculture breast 1601 is dissolved in 20ml water and obtains aqueous phase, Oil phase is mixed with water after conjunction, using ultrasonic grinder under 585W ultrasonic emulsification 2min, obtain O/W type colostric fluids, wherein The particle diameter of the drop of colostric fluid is 500nm.
Using high pressure homogenizer under 600Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 40min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 50nm.
Above-mentioned miniemulsion is stirred at 500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains a nanometer agriculture Medicine mother liquor.
0.1g thickeners (0.05g xanthans and 0.05g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, mixing is equal It is even, obtain nano pesticide aqueous suspension agent 26.
The preparation of the nano pesticide solid powder 27 of embodiment 27
30g pesticide activity component gamma cyhalothrins are dissolved in 260ml organic solvent dichloromethanes, 20g is added Cyst material cellulose, obtains oil phase, and 13g emulsifying dispersants (6.5g polyvinyl alcohol and 6.5g agriculture breasts 1601) are dissolved in Aqueous phase is obtained in 400ml water, oil phase is mixed with water after conjunction, 30min is emulsified in 22000rmp down cuts using high-speed shearing machine, O/W type colostric fluids are obtained, the wherein particle diameter of the drop of colostric fluid is 900nm.
Using high pressure homogenizer under 100Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 2h, obtain miniemulsion, wherein The particle diameter of the drop of miniemulsion is 500nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 10h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 10min using high speed freezing centrifuge under 15000rpm, then using spray Mist drying machine is spray-dried 1.5s at 30 DEG C of EAT, 30 DEG C of leaving air temp, obtains solid powder, adds 350g solids and fills out Expect diatomite and 15g adjuvants TERSPERSE 2020, be well mixed, obtain nano pesticide solid powder 27.
The preparation of the nano pesticide aqueous suspension agent 28 of embodiment 28
30g pesticide activity component gamma cyhalothrins are dissolved in 260ml organic solvent dichloromethanes, 20g is added Cyst material cellulose, obtains oil phase, and 13g emulsifying dispersant polyvinyl alcohol is dissolved in 400ml water and obtains aqueous phase, by oil phase It is mixed with water after conjunction, 20min is emulsified in 25000rmp down cuts using high-speed shearing machine, O/W type colostric fluids, wherein colostrum is obtained The particle diameter of the drop of liquid is 900nm.
Using high pressure homogenizer under 100Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 2h, obtain miniemulsion, wherein The particle diameter of the drop of miniemulsion is 500nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
15g thickeners (7.5g gelatin and 7.5g aluminium-magnesium silicates) and 15g adjuvants are added in above-mentioned nano pesticide mother liquor TERSPERSE 2020, is well mixed, obtains nano pesticide aqueous suspension agent 28.
The preparation of the nano pesticide solid powder 29 of embodiment 29
15g pesticide activity component AVMs are dissolved in 200ml organic solvent dichloromethanes, 15g cyst wall materials are added Expect PLA, obtain oil phase, 10g emulsifying dispersants (5g polyvinyl alcohol and 5g agriculture breasts 1601) are dissolved in 300ml water and obtained Aqueous phase, oil phase is mixed with water after conjunction, is emulsified 3min in 28000rmp down cuts using high-speed shearing machine, is obtained O/W type colostrums The particle diameter of the drop of liquid, wherein colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 24h is kept at -60 DEG C, obtains solid powder, adds 250g solid packing kaolinites Soil, is well mixed, obtains nano pesticide solid powder 29.
The preparation of the nano pesticide aqueous suspension agent 30 of embodiment 30
15g pesticide activity component AVMs are dissolved in 200ml organic solvent dichloromethanes, 15g cyst wall materials are added Expect PLA, obtain oil phase, 10g emulsifying dispersants (5g polyvinyl alcohol and 5g agriculture breasts 1601) are dissolved in 300ml water and obtained Aqueous phase, oil phase is mixed with water after conjunction, is emulsified 40min in 10000rmp down cuts using high-speed shearing machine, is obtained O/W type colostrums The particle diameter of the drop of liquid, wherein colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
15g thickeners (7.5g gelatin and 7.5g aluminium-magnesium silicates) are added in above-mentioned nano pesticide mother liquor, is well mixed, obtains To nano pesticide aqueous suspension agent 30.
The preparation of the nano pesticide solid powder 31 of embodiment 31
20g pesticide activity component AVMs are dissolved in 220ml organic solvent dichloromethanes, 30g cyst wall materials are added Expect PLA, obtain oil phase, 20g emulsifying dispersants (10g polyvinyl alcohol and 10g agriculture breasts 1601) are dissolved in 350ml water and obtained To aqueous phase, oil phase is mixed with water after conjunction, emulsification 60min is ground under 30Hz using grinding distribution machine, obtains O/W type colostrums The particle diameter of the drop of liquid, wherein colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 18h is kept at -60 DEG C, obtains solid powder, adds 300g solid packing kaolinites Soil and 10g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 31.
The preparation of the nano pesticide aqueous suspension agent 32 of embodiment 32
20g pesticide activity component AVMs are dissolved in 220ml organic solvent dichloromethanes, 30g cyst wall materials are added Expect PLA, obtain oil phase, 20g emulsifying dispersants (10g polyvinyl alcohol and 10g agriculture breasts 1601) are dissolved in 350ml water and obtained To aqueous phase, oil phase is mixed with water after conjunction, emulsification 40min is ground under 40Hz using grinding distribution machine, obtains O/W type colostrums The particle diameter of the drop of liquid, wherein colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
10g thickeners (5g xanthans and 5g aluminium-magnesium silicates) and 10g adjuvants are added in above-mentioned nano pesticide mother liquor TERSPERSE 2020, is well mixed, obtains nano pesticide aqueous suspension agent 32.
The preparation of the nano pesticide solid powder 33 of embodiment 33
40g pesticide activity component AVMs are dissolved in 300ml organic solvent dichloromethanes, 40g cyst wall materials are added Expect PLA, obtain oil phase, 30g emulsifying dispersants (15g polyvinyl alcohol and 15g agriculture breasts 1601) are dissolved in 500ml water and obtained To aqueous phase, oil phase is mixed with water after conjunction, emulsification 20min is ground under 45Hz using grinding distribution machine, obtains O/W type colostrums The particle diameter of the drop of liquid, wherein colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 20min using high speed freezing centrifuge under 10000rpm, then using cold Lyophilizer precooling 4h at -50 DEG C, 12h is kept at -60 DEG C, obtains solid powder, adds 400g solid packing kaolinites Soil and 20g adjuvants TERSPERSE 2020, are well mixed, obtain nano pesticide solid powder 33.
The preparation of the nano pesticide aqueous suspension agent 34 of embodiment 34
40g pesticide activity component AVMs are dissolved in 300ml organic solvent dichloromethanes, 40g cyst wall materials are added Expect PLA, obtain oil phase, 30g emulsifying dispersants (15g polyvinyl alcohol and 15g agriculture breasts 1601) are dissolved in 500ml water and obtained To aqueous phase, oil phase is mixed with water after conjunction, emulsification 5min is ground using grinding distribution machine at 50 hz, O/W type colostric fluids are obtained, Wherein the particle diameter of the drop of colostric fluid is 400nm.
Using high pressure homogenizer under 900Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 10min, obtain miniemulsion, its The particle diameter of the drop of middle miniemulsion is 100nm.
Above-mentioned miniemulsion is stirred at 1500 rpm by 24h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
20g thickeners (10g xanthans and 10g aluminium-magnesium silicates) and 20g adjuvants are added in above-mentioned nano pesticide mother liquor TERSPERSE 2020, is well mixed, obtains nano pesticide aqueous suspension agent 34.
The preparation of the nano pesticide solid powder 35 of embodiment 35
0.5g pesticide activity component AVMs are dissolved in 20ml organic solvent dichloromethanes, 0.5g cyst wall materials are added Expect PLA, obtain oil phase, 0.5g emulsifying dispersants (0.25g polyvinyl alcohol and 0.25g lignosulfonates) are dissolved in Obtain aqueous phase in 50ml water, oil phase be mixed with water after conjunction, using ultrasonic grinder under 650W ultrasonic emulsification 20min, obtain To O/W type colostric fluids, the wherein particle diameter of the drop of colostric fluid is 100nm.
Using high pressure homogenizer under 1200Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 2h, obtain miniemulsion, wherein The particle diameter of the drop of miniemulsion is 10nm.
Above-mentioned miniemulsion is stirred under 1300rpm by 20h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
Above-mentioned nano pesticide mother liquor is centrifuged into 30min using high speed freezing centrifuge under 4000rpm, then using spraying Drying machine is spray-dried 1s at 100 DEG C of EAT, 140 DEG C of leaving air temp, obtains solid powder, adds 10g solid packings Diatomite, is well mixed, obtains nano pesticide solid powder 35.
The preparation of the nano pesticide aqueous suspension agent 36 of embodiment 36
0.5g pesticide activity component AVMs are dissolved in 20ml organic solvent dichloromethanes, 0.5g cyst wall materials are added Expect PLA, obtain oil phase, 0.5g emulsifying dispersants (0.25g polyvinyl alcohol and 0.25g lignosulfonates) are dissolved in Obtain aqueous phase in 50ml water, oil phase be mixed with water after conjunction, using ultrasonic grinder under 637W ultrasonic emulsification 25min, obtain To O/W type colostric fluids, the wherein particle diameter of the drop of colostric fluid is 100nm.
Using high pressure homogenizer under 1000Pa by above-mentioned O/W types colostric fluid high pressure homogenizing 1h, obtain miniemulsion, wherein The particle diameter of the drop of miniemulsion is 10nm.
Above-mentioned miniemulsion is stirred under 1000rpm by 22h using electric mixer, organic solvent is volatilized, obtains nanometer Pesticide mother liquor.
1g thickener xanthans is added in above-mentioned nano pesticide mother liquor, is well mixed, obtains nano pesticide aqueous suspension agent 36。
The optimum choice of the emulsifying dispersant of embodiment emamectin-benzoate nano-pesticide formulation
The step of according to colostric fluid is prepared in embodiment 11, using polyvinyl alcohol and a kind of following material：EL 40、 Span 60, Tween 80, Span 80, Tween 60, agriculture breast 500#, agriculture breast 600#, Nongru-700#, agriculture breast 1601#And AEO-9 Emamectin-benzoate nano-pesticide formulation colostric fluid is prepared as emulsifying dispersant, using nanometer laser particle size analyzer The particle size and dispersion index (PDI) of the nano-particle of the primary emulsifying stage formation of test, compare using different emulsion dispersions The particle size and dispersion index of the nano-particle formed during agent in primary emulsifying stage, select optimal emulsifying dispersant.
Table 1 shows that the emamectin-benzoate nano-pesticide formulation prepared using different emulsifying dispersants is existed The average grain diameter and dispersion index of the nano-particle of primary emulsifying stage formation, from table 1 it follows that using the conducts of EL 40 During emulsifying dispersant, in emamectin-benzoate nano-pesticide formulation colostric fluid the average grain diameter of nano-particle and point Scattered index is smaller (dispersiveness is preferably), and emulsification degree is best, therefore the present invention preferably EL 40 is used as emulsifying dispersant.
In emamectin-benzoate nano-pesticide formulation colostric fluid of the table 1 using the preparation of different emulsifying dispersants The average grain diameter and dispersion index of nano-particle
Note：S.D. standard deviation is represented.
Pattern, particle diameter and the particle diameter distribution test of the nano-pesticide formulation of test case 1
The nano-pesticide formulation that transmission electron microscope, SEM observe above-described embodiment preparation is respectively adopted Pattern and its particle diameter and particle diameter distribution are tested using nanometer laser particle size analyzer.
Fig. 1 is the transmission electron microscope figure of gamma cyhalothrin nano-pesticide formulation prepared by the embodiment of the present invention 17 Piece and grain size distribution.It is seen in fig. 1, that gamma cyhalothrin nano-pesticide formulation prepared by the embodiment of the present invention is in ball Shape, average grain diameter is 98.18nm (shown in (a) and (b) in such as Fig. 1).
Fig. 2 be the embodiment of the present invention 1 prepare avermectin nanometer pesticidal preparations 1000 times (a), 3000 times (b) and Scanning electron microscope diagram piece under 8000 times (c) amplification.As seen from Figure 2, the AVM that prepared by the embodiment of the present invention is received Rice pesticidal preparations are spherical in shape, and average grain diameter is 487nm (shown in (a), (b) and (c) in such as Fig. 2).
Fig. 3 is that emamectin-benzoate nano-pesticide formulation prepared by the embodiment of the present invention 11 is amplifying respectively Scanning electron microscope diagram piece under 8000 times (Fig. 3 (a)) and 20000 times (Fig. 3 (b)).As seen from Figure 3, the present invention is implemented Emamectin-benzoate nano-pesticide formulation prepared by example is spherical in shape, and average grain diameter is about 100nm.
Fig. 4 and Fig. 5 show the electronic display of avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention 7,8,9 and 10 Micro mirror picture and particle diameter distribution, as shown in figure 4, avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention are spherical in shape (shown in (a), (b) (c) and (d) in such as Fig. 4), its particle diameter is respectively 344nm (a), 460nm (b), 615nm (c) and 827nm (d) (as shown in Figure 5).Therefore, using the method for the present invention, different-grain diameter is can obtain by changing component proportion, process conditions Avermectin nanometer pesticidal preparations, so as to be entered according to specific application scenarios to the particle diameter of avermectin nanometer pesticidal preparations Row regulation.
The emamectin-benzoate nano-pesticide formulation distribution tests of test case 2
Emamectin-benzoate nano-pesticide formulation prepared by above-described embodiment 14 is sprayed, and is sprayed at It is to be dried that point of the nano-pesticide formulation on blade is observed using environmental scanning electron microscope afterwards on clean cucumber leaves Cloth.
Fig. 6 shows distribution of the emamectin-benzoate nano-pesticide formulation on cucumber leaves, from figure Find out that nano-pesticide formulation prepared by the embodiment of the present invention favorable dispersibility on cucumber leaves is evenly distributed.
The sustained release performance test of the avermectin nanometer pesticidal preparations of test case 3
Avermectin nanometer pesticidal preparations and the former medicine of AVM that respectively prepared by test above-described embodiment 7,8,9 and 10 Sustained release performance (uses ultraviolet-uisible spectrophotometer, in different release time using in dialysis test nano-pesticide formulation The AVM content of release), make cumulative release amount-time graph.
Fig. 7 is avermectin nanometer pesticidal preparations (A, B, C, D) and Avermectin prepared by the embodiment of the present invention 7,8,9 and 10 Elution profiles of the plain active compound (E) in 240 hours, as seen from the figure, avermectin nanometer agricultural chemicals prepared by the embodiment of the present invention Preparation is in first 24 hours, and cumulative release amount reaches about 0-19%, and subsequent rate of release slows down, at 240 hours, cumulative release amount Reach about 53-80%；And the former medicine of AVM, in first 24 hours, cumulative release amount reaches about 94%.Therefore, with AVM Active compound is compared, and the release time of avermectin nanometer pesticidal preparations prepared by the embodiment of the present invention significantly extends, with obvious Slow release characteristic.In addition, the embodiment of the present invention prepare avermectin nanometer pesticidal preparations particle diameter be respectively 344nm (A), 460nm (B), 615nm (C), 827nm (D) (as shown in Figure 4), as seen from Figure 7, AVM prepared by the embodiment of the present invention The slow-release time of nano-pesticide formulation slows down with the increase of particle diameter.Therefore, using the method for the present invention, by adjusting particle diameter Size, can obtain the nano-pesticide formulation of different slow release characteristics, to meet different dispenser scenes and pest and disease damage pests occurrence rule Need.
In addition, after tested, nano-pesticide formulation prepared by other embodiments of the invention also has preferably sustained release performance.
The anti-light solution performance test of the avermectin nanometer pesticidal preparations of test case 4
The avermectin nanometer pesticidal preparations respectively prepared by above-described embodiment 7 and commercially available AVM water dispersible granules (Beijing China army are biological, Kai Wei) irradiates 12h, 24h, 36h, 48h, 60h and 72h under 500W ultraviolet lamps, and uses agricultural chemicals light Avermectin nanometer pesticidal preparations and commercially available AVM water dispersible granules prepared by stability test case difference testing example 7 Ultraviolet light degradation property, make photodissociation rate-time graph.
As shown in figure 8, compared with traditional commercially available AVM water dispersible granules, Avermectin prepared by the embodiment of the present invention Light resolution ratio of the plain nano-pesticide formulation under ultraviolet light is significantly reduced, with good ultraviolet light degradation property.Need Will especially, it is emphasized that avermectin pesticides preparation for easily occur photodissociation environment sensitive type agricultural chemicals, can by the inventive method Effectively protect it from by light degradation, so as to be greatly enhanced effective rate of utilization and bioavilability, reduce spraying times and agent Amount, is conducive to environmental protection and ecological safety.
In addition, after tested, nano-pesticide formulation prepared by other embodiments of the invention also there is excellent ultraviolet light to drop Solve performance.
It is aobvious for those skilled in the art although the preferred embodiments of the invention have been shown and described herein And be clear to is that these embodiments are only provided in an illustrative manner.Those skilled in the art are without departing from the present invention A variety of changes are will now occur, changes and substitutes.It should be understood that the various alternative solutions of embodiment of the present invention specifically described herein It is of the invention available for implementing.Purpose be with the claims below limit the scope of the present invention, and thus cover these rights will Method and structure and its equivalent item in the range of asking.

Claims (12)

1. a kind of preparation method of nano-pesticide formulation, methods described includes：The component of nano-pesticide formulation is formed through emulsification Colostric fluid, is then made nano-pesticide formulation through high-pressure homogeneous formation miniemulsion.
2. preparation method according to claim 1, it is characterised in that the preparation method comprises the following steps：
Step a：Pesticide activity component, organic solvent, cyst material, emulsifying dispersant and water are mixed, is then emulsified, obtained To colostric fluid；
Step b：By the colostric fluid obtained in step a by high-pressure homogeneous carry out fine crankshaft, miniemulsion is obtained；
Step c：By the miniemulsion obtained in step b stirring, organic solvent is volatilized, obtain nano pesticide mother liquor；
Step d：The nano pesticide mother liquor obtained in step c is mixed with excipient and adjuvant, nano-pesticide formulation is obtained.
3. preparation method according to claim 2, it is characterised in that the nano-pesticide formulation is spherical, the step a Including：Pesticide activity component is dissolved in organic solvent, cyst material is added, obtains oil phase, emulsifying dispersant is dissolved in Aqueous phase is obtained in water, oil phase is mixed with water after conjunction, is emulsified, O/W type colostric fluids are obtained.
4. the preparation method according to Claims 2 or 3, it is characterised in that the nano-pesticide formulation is nano pesticide water Suspending agent, the excipient is thickener, and the step d includes：It is directly added into the nano pesticide mother liquor obtained in step c Thickener and adjuvant, are well mixed, obtain nano pesticide aqueous suspension agent.
5. the preparation method according to Claims 2 or 3, it is characterised in that the nano-pesticide formulation is solid for nano pesticide Body pulvis, the excipient is solid packing, and the step d includes：By the nano pesticide mother liquor obtained in step c through centrifugation and Solid powder is obtained after drying, solid packing and adjuvant is added, is well mixed, obtains nano pesticide solid powder.
6. the preparation method according to any one of claim 2-5, it is characterised in that the emulsification in the step a is super One or more in one or more in sound emulsification, emulsification pretreatment and grinding emulsification, preferably emulsification pretreatment and grinding emulsification； The particle diameter of the drop of the colostric fluid is 100-900nm, preferably 100-500nm；
Wherein described ultrasonic emulsification is carried out using ultrasonic grinder, and the power of the ultrasonic grinder is 65-650W, preferably 325-637W, more preferably 585W；The time of ultrasonic emulsification is 2-30min, more preferably preferably 5-25min, 15min；
Wherein described emulsification pretreatment is carried out using high-speed shearing machine, and the shearing rotating speed of the high-speed shearing machine is 10000- 28000rmp, preferably 22000-28000rmp, more preferably 28000rmp；Shear time is 3-40min, preferably 3-30min, more excellent Select 15min；
Wherein described grinding is emulsified to be carried out using grinding distribution machine, grinds the frequency of emulsification for 30-50Hz, preferably 40-50Hz, more It is preferred that 50Hz；Milling time is 5-60min, preferably 5-40min, more preferably 15min；
Preferably, the high-pressure homogeneous use high pressure homogenizer in the step b is carried out, and high-pressure homogeneous pressure is 100- 1200Pa, preferably 600-1000Pa, more preferably 900Pa；The high-pressure homogeneous time be 10min-2h, preferably 10min-1h, it is more excellent Select 15min；The particle diameter of the drop of the miniemulsion is 10-600nm, preferably 10-100nm；
Preferably, it is stirred in the step c using electric mixer, mixing speed is 500-1500rpm, preferably 1000- 1500rpm, more preferably 1500rpm；Mixing time is 5-24h, preferably 10-20h, more preferably 12h；
Preferably, when the nano-pesticide formulation is nano pesticide solid powder, in the step d, using high speed freeze from Scheming centrifuges 10-30min under rotating speed 4000-15000rpm；Preferably, using high speed freezing centrifuge in rotating speed 4000- 20-30min is centrifuged under 15000rpm；It is highly preferred that centrifuging 20min under rotating speed 15000rpm using high speed freezing centrifuge；
Preferably, when the nano-pesticide formulation is nano pesticide solid powder, the drying in the step d is spray drying Or freeze-drying, wherein the spray drying is carried out using spray dryer, the condition of spray drying is EAT 30-300 DEG C, 30-140 DEG C of leaving air temp, drying time 1-1.5s；The freeze-drying is carried out using freeze drier, freeze-drying Condition is the precooling 4h at -50 DEG C, keeps 12-24h at -60 DEG C；It is preferred that at -50 DEG C precooling 4h, keep at -60 DEG C 12h。
7. the preparation method according to any one of the claims, it is characterised in that the grain of the nano-pesticide formulation Footpath is 20-500nm, preferably smaller than equal to 100nm, more preferably less than 50nm；Preferably, the load of the nano pesticide solid powder Dose is 0.1-90%, and the drugloading rate of the nano pesticide aqueous suspension agent is 0.1-20%.
8. the preparation method according to any one of the claims, it is characterised in that by weight, the nano pesticide Preparation is made up of following components：
Pesticide activity component：0.1-40 parts
Cyst material：0.1-40 parts
Emulsifying dispersant：0.2-30 parts
Organic solvent：10-300 parts
Water：20-500 parts
Excipient：0.1-400 parts
Adjuvant：0-20 parts,
Wherein, the ratio of the pesticide activity component and cyst material is 0.1:1-10:1.
9. preparation method according to claim 8, it is characterised in that the nano-pesticide formulation is nano pesticide solid powder Agent, wherein the excipient is solid packing, by weight, the nano pesticide solid powder is made up of following components：
Pesticide activity component：0.1-40 parts
Cyst material：0.1-40 parts
Emulsifying dispersant：0.2-30 parts
Organic solvent：10-300 parts
Water：20-500 parts
Solid packing：0.1-400 parts
Adjuvant：0-20 parts,
Wherein, the ratio of the pesticide activity component and cyst material is 0.1:1-10:1；
Or, the nano-pesticide formulation is nano pesticide aqueous suspension agent, wherein the excipient is thickener, by weight, The nano pesticide aqueous suspension agent is made up of following components：
Pesticide activity component：0.1-40 parts
Cyst material：0.1-40 parts
Emulsifying dispersant：0.2-30 parts
Organic solvent：10-300 parts
Water：20-500 parts
Thickener：0.1-20 parts
Adjuvant：0-20 parts,
Wherein, the ratio of the pesticide activity component and cyst material is 0.1:1-10:1.
10. the preparation method according to any one of claim 2-9, it is characterised in that the pesticide activity component is selected from One or more in insecticide, bactericide, herbicide and plant growth regulator；
The cyst material is degradable high polymer material.
11. preparation method according to claim 10, it is characterised in that the insecticide is selected from following one kind or many Kind：AVM, emamectin-benzoate, gamma cyhalothrin, Rynaxypyr, pleocidin, indenes worm Prestige, clothianidin, carbosulfan, Hostathion, diazinon, many mite prestige, chlopyrifos, Biphenthrin, cyphenothrin, ethofenprox, bromine It is Cyano chrysanthemate, fenvalerate, cyfluthrin, Tefluthrin, lythidathion, phoxim, imidacloprid and Diacloden, preferably Diacloden, many One kind in bacteriocidin, Rynaxypyr, AVM, emamectin-benzoate and gamma cyhalothrin or It is a variety of；
The bactericide is selected from following one or more：Fluoxastrobin, pyraclostrobin, thifluzamide, metconazole, cyanogen alkene bacterium Ester, fluazinam, cymoxanil, Boscalid, ethofenprox, cyflumetofen, Fenpropathrin, benzothiostrobin, pefurazoate, Prochloraz, third Ring Zuo, Difenoconazoles, Metalaxyl-M, Flusilazole, epoxiconazole, trifloxystrobin and pyraclostrobin, preferably thifluzamide, metconazole, cyanogen alkene One or more in bacterium ester, fluazinam, Fluoxastrobin, pyraclostrobin, cymoxanil and Boscalid；
The herbicide is selected from following one or more：The different monooctyl ester of pendimethalin, tri-allate, 2,4-D, benthiocarb, molinate, In cover grass energy, clomazone, butralin, S-metolachlor, trefanocide and prometryn, preferably pendimethalin and S-metolachlor One or more；
The plant growth regulator is selected from following one or more：Brassinosteroid, ammonia oxygen ethyl vinyl glycine and Multiple-effect azole plant growth regulator, preferably multiple-effect azole plant growth regulator；
Preferably, the cyst material is selected from following one or more：Polyester acrylate and its derivative, polyvinyl acetate Resin, polyacrylonitrile resin, polystyrene resin, PLA, gelatin, modified starch, cellulose and its derivates, chitosan and One or more in Arabic gum, preferred cellulose and its derivative, chitosan, PLA and modified starch.
12. the preparation method according to any one of claim 2-11, it is characterised in that the emulsifying dispersant is agricultural One or more in emulsifying agent and dispersant, it is preferable that the agricultural emulsifier be selected from OP series, NP series, EL series, Tween series, Span series, AEO series, agriculture breast series, polyvinyl alcohol, cithrol, polyvinylpyrrolidone And the one or more in polyethylene glycol (PEG) oleate；It is preferred that Tween is serial, one kind in the serial emulsifying agent of polyvinyl alcohol and agriculture breast Or it is a variety of；More preferably polyvinyl alcohol, the series of agriculture breast 300, agriculture breast 500 are serial, agriculture breast 600 is serial, Nongru-700 is serial and agriculture breast One or more in 1600 serial emulsifying agents；
Preferably, the dispersant is in carboxylate, sulfate, sulfonate, phosphate ester salt and APES It is one or more, it is preferable that the dispersant is selected from aliphatic alcohol polyethenoxy ether carboxylate, lauryl sodium sulfate, lignin In sulfonate, dodecyl sodium sulfate, maleated rosin polyethenoxy-oxypropylene ether sulfonate and dodecyl ether phosphate salt One or more in one or more, more preferably lignosulfonates, lauryl sodium sulfate and dodecyl sodium sulfate.
Preferably, one kind in preservative, defoamer, antifreeze, pH adjusting agent and wetting dispersing agent of the adjuvant or It is a variety of, the one or more preferably in antifreeze, defoamer and wetting dispersing agent；
Preferably, one or more of the antifreeze in ethylene glycol, propane diols, glycerine, isopropanol and urea, preferably Ethylene glycol；
Preferably, one or more of the defoamer in organic silicon and low-carbon alcohols defoamer, preferably organic silicon disappears Infusion；
Preferably, the thickener is selected from xanthans, Arabic gum, gelatin, cellulose and its derivates, diatomite, polyethylene One or more in alcohol, Sodium Polyacrylate, dextrin, aluminium-magnesium silicate and Silica hydrogel, preferably xanthans, gelatin, aluminium-magnesium silicate, fibre One or more in dimension element and its derivative and polyvinyl alcohol；
Preferably, the organic solvent is in dichloromethane, chloroform, vegetable oil, petroleum ether and aliphatic solvent oil One or more, preferably dichloromethane；
Preferably, the solid packing is selected from diatomite, kaolin, talcum powder, montmorillonite, white carbon, cornstarch and Hai Pao One or more in one or more in stone, preferably kaolin, cornstarch and white carbon.
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CN108684688A (en) * 2018-06-14 2018-10-23 国家纳米科学中心 A kind of nano pesticide composition and preparation method thereof
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CN113854289A (en) * 2021-11-02 2021-12-31 中国农业科学院农业环境与可持续发展研究所 Double-carried nano pesticide capsule containing dinotefuran and abamectin and preparation method thereof
CN115812722A (en) * 2022-09-07 2023-03-21 深圳诺普信农化股份有限公司 Nano pesticide water suspending agent and preparation method and application thereof
CN118044507A (en) * 2024-04-16 2024-05-17 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) Drug-carrying system and preparation method and application thereof

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CN109792993A (en) * 2018-12-29 2019-05-24 南京善思生物科技有限公司 A kind of environmentally friendly Rynaxypyr nanometer pulvis and preparation method thereof
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CN110881462A (en) * 2019-11-25 2020-03-17 南京启佑生物科技有限公司 Nano pesticide composite preparation based on phosphate and metal ions and preparation method thereof
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