WO2016145908A1 - 一种农药纳米固体分散体及其制备方法 - Google Patents

一种农药纳米固体分散体及其制备方法 Download PDF

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WO2016145908A1
WO2016145908A1 PCT/CN2015/095771 CN2015095771W WO2016145908A1 WO 2016145908 A1 WO2016145908 A1 WO 2016145908A1 CN 2015095771 W CN2015095771 W CN 2015095771W WO 2016145908 A1 WO2016145908 A1 WO 2016145908A1
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Prior art keywords
pesticide
dispersion
weight
nanosolid
parts
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PCT/CN2015/095771
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English (en)
French (fr)
Inventor
崔海信
崔博
冯磊
刘国强
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中国农业科学院农业环境与可持续发展研究所
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Priority to US15/313,199 priority Critical patent/US20170188575A1/en
Priority to DK15885277.2T priority patent/DK3269243T3/da
Priority to ES15885277T priority patent/ES2781674T3/es
Priority to PL15885277T priority patent/PL3269243T3/pl
Priority to EP15885277.2A priority patent/EP3269243B9/en
Publication of WO2016145908A1 publication Critical patent/WO2016145908A1/zh

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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
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N25/30—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 characterised by the surfactants
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/02—Acyclic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A—HUMAN NECESSITIES
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A—HUMAN NECESSITIES
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    • A01N43/22—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom rings with more than six members
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
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    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A—HUMAN NECESSITIES
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    • 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
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    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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    • 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
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    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
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    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
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    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur

Definitions

  • the invention belongs to the technical field of pesticides. More specifically, the present invention relates to a pesticide nanosolid dispersion, and to a process for preparing the pesticide nanosolid dispersion.
  • Pesticides are an important material basis for safeguarding major biological disasters, ensuring food security, and promoting sustained and steady growth of agricultural output. According to the statistics of the Food and Agriculture Organization of the United Nations (FAO), the loss of agricultural products recovered by pesticides and pests worldwide is about 30% of total production. Except for a few varieties, the original pesticides can not be directly applied, and must be processed or prepared into a specific form according to the characteristics of the original drug and the specific requirements of use, and processed or prepared into a specific form.
  • the pesticide form is a pesticide dosage form.
  • Nanomicroemulsions are one of the water-based pesticide formulations and are one of the new formulations for replacing emulsifiable concentrates and reducing organic solvent contamination.
  • CN 1656893A discloses a method for producing pesticide microemulsions. Nanomicroemulsion is thermodynamically stable composed of liquid pesticides, surfactants, water, stabilizers, etc. Decentralized system.
  • microemulsions have some drawbacks and limitations. Common problems are unstable emulsion, easy crystallization, narrow transparent temperature zone, low preparation content, and the stability of the preparation is easily damaged by external environment.
  • CN 102499236A discloses solid microemulsions containing pyrethroid insecticides and a process for their preparation.
  • the original drug is mixed with a surfactant and/or an organic solvent to form an oil phase, and then mixed with a solid phase and/or an aqueous phase containing a carrier to form a solid oil mixture or a water-solid oil mixture.
  • the solid microemulsion can be dispersed in water into a colorless, transparent or translucent microemulsion, which is the same as the emulsion formed by the conventional microemulsion diluted with water, can inherit the advantages of the microemulsion, and overcome the stability of the liquid preparation and is vulnerable to the external environment. Disadvantages and damage, inconveniences such as long-term preservation and transportation, but still can not solve the environmental pollution and food safety problems caused by the use of a large number of surfactants.
  • Pesticide nanosuspension is another new water-based pesticide formulation. It is a submicron colloidal dispersion system formed by dispersing the "pure" pesticide active ingredient in water through the stabilization of surfactant.
  • the active ingredient of the pesticide in the dosage form has a small particle size, a large specific surface area, an increased dissolution rate of the drug and an increase in target adhesion, thereby contributing to an improvement in effective utilization rate.
  • the main drawback is that the stability of the liquid preparation is poor, and it is usually necessary to add more stabilizers and suspending agents.
  • the invention has created a nanoparticle with a solid form in a highly soluble form, which is highly dispersed in a carrier and a surface by a long-term innovation and exploration.
  • a solid preparation in a sex agent and a preparation method thereof can eliminate organic solvents and greatly reduce the use of surfactants and auxiliaries, can not only take advantage of the many advantages of pesticide nano-formulations, but also overcome the main limitations of existing dosage forms.
  • As a solid preparation it is less affected by the external environment, and the stability and shelf life are significantly improved, which is convenient for packaging, storage and transportation.
  • the preparation can be directly diluted with water to form a water-based nanodispersion system with excellent comprehensive performance.
  • Another object of the present invention is to provide a process for the preparation of the pesticide nanosolid dispersion.
  • the present invention has been achieved by the following technical solutions.
  • the present invention relates to a pesticide nanosolid dispersion characterized in that it is a pesticide nanosolid dispersion formed by uniformly dispersing poorly soluble pesticide nanoparticles in a surfactant and a water-soluble carrier, in parts by weight thereof.
  • the composition is as follows:
  • the pesticide is one or more pesticides selected from the group consisting of poorly soluble insecticides, fungicides, herbicides or plant growth regulators;
  • the pesticide nanoparticles have an average particle diameter of from 1 to 1000 nm, preferably an average particle diameter of less than 500 nm, and more preferably an average particle diameter of less than 100 nm.
  • the poor solubility of the insecticide, bactericide, herbicide or plant growth regulator is understood to be a solubility in water of less than or equal to 0.1 g/L.
  • the insecticide should be understood to be a medicine which can be used for controlling agricultural pests encountered in the application of the product of the present invention. It is well known that almost all pesticides have an impact on the ecosystem, most of which are harmful to the human body, and others are concentrated in the food chain. Therefore, a balance must be struck between agricultural development and the environment and health.
  • the insecticide is selected from the group consisting of pyrethroids, carbamates, organophosphorus, organic sulfur, organic choline, silkworm toxin, neonicotinoid, phenyl acyl urea, Avermectin , ⁇ , ⁇ , phenylpyrazole, indoxacarb or butyl ether urea insecticide, but not limited to this range;
  • insecticides used in the present invention are all currently marketed products.
  • the bactericide is understood to be an effective control or killing of microorganisms encountered in the application of the product of the present invention, including bacteria, fungi and algae chemicals.
  • the bactericide is selected from the group consisting of anilinopyridine, antibiotics, aromatic hydrocarbons, dinitroaniline, allylamine, benzenesulfonamide, benzimidazole, benzisothiazole, benzophenone, benzoyl Pyrimidine, benzotriazine, benzyl carbamate, carbamate, carboxamide, carboxylic acid diamide, chloronitrile, cyanoimidazole, cyclopropanecarboxamide, ethylaminothiazole carboxamide, imidazole, hydroxyanilide , imidazolinone, isobenzofuranone, methoxy acrylate, methoxy carbamate, morpholine, N-phenyl carbamate, oxazolidinedione, phenylacetamide, phenyl Amide, phenylpyrrole, phenylurea, phosphorothioate, o-carbam
  • the bactericides used in the present invention are all currently marketed products.
  • the herbicide is understood to be an agent which allows the farmland weed to be completely or selectively killed to eliminate or inhibit plant growth.
  • the herbicide is selected from the group consisting of an amide, an aryloxyphenoxypropionate, a phenoxycarboxylic acid, an organophosphorus, a benzamide, a benzofuran, a benzoic acid, a benzothiadiazinone, an amino group.
  • the herbicides used in the present invention are all currently marketed products.
  • the plant growth regulator is understood to be a chemical substance which has a regulating effect on the growth and development of plants.
  • the plant growth regulator is selected from the group consisting of chlorophyll, methyl naphthaleneacetate, 6-benzylaminopurine, brassinolide, aminooxyethylglycine or paclobutraz growth regulation Agent, but not limited to this range.
  • the plant growth regulators used in the present invention are all currently marketed products.
  • the surfactant is understood to be a substance which causes a significant change in the state of the interface of the solution system.
  • the molecular structure of the surfactant is amphiphilic: one end is a hydrophilic group and the other end is a hydrophobic group; the hydrophilic group is often a polar group such as a carboxylic acid, a sulfonic acid, a sulfuric acid, an amino group, a hydroxyl group, Amido groups and the like; and hydrophobic groups are often non-polar hydrocarbon chains.
  • the surfactant is one or more surfactants selected from the group consisting of cationic surfactants, anionic surfactants, nonionic surfactants or amphoteric surfactants.
  • the cationic surfactant is selected from the group consisting of fatty amine salts, ethanolamine salts, polyethylene polyamine salts or quaternary ammonium salt cationic surfactants;
  • the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, maleic rosin polyoxyethylene-oxypropylene ether sulfonate, alkylphenol poly Oxyethylene ether phosphate salt, monododecyl ether phosphate salt, dodecyl ether phosphate salt, octyl ether phosphate, fatty alcohol polyoxyethylene phosphinate, fatty alcohol polyoxyethylene ether carboxylic acid a salt, a polycarboxylate or a lignosulfonate anionic surfactant;
  • the nonionic surfactant is selected from the group consisting of alkylphenol polyoxyethylene ether formaldehyde condensate, styrylphenol polyoxyethylene ether formaldehyde condensate, polystyrene phenol polyoxyethylene ether, cumene phenol polyoxyethylene ether Formaldehyde condensate, benzylphenol polyoxyethylene ether formaldehyde condensate, castor oil polyoxyethylene ether, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, sorbitan oleate, polyoxyethylene polyoxygen a propylene block copolymer or a sucrose monooleate nonionic surfactant;
  • amphoteric surfactant is selected from the group consisting of dodecyl hydroxypropyl sulfobetaine, dodecyl betaine, octadecyl dihydroxyethyl amine oxide, octadecyl urea or oil-based biuret. Surfactant.
  • the cationic surfactant, anionic surfactant, nonionic surfactant or amphoteric surfactant used in the present invention are all currently marketed products.
  • the water-soluble carrier is selected from the group consisting of urea, sodium sulfate, magnesium sulfate, sodium benzoate, sucrose, lactose, soluble starch, hydroxypropylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose.
  • urea sodium sulfate, magnesium sulfate, sodium benzoate
  • sucrose lactose
  • soluble starch hydroxypropylmethylcellulose
  • hydroxyethyl- ⁇ -cyclodextrin hydroxypropyl- ⁇ -cyclodextrin
  • sulfonate- ⁇ -cyclodextrin polyvinyl alcohol, polyethylene glycol, xanthan gum, magnesium aluminum silicate, Acacia gum, sodium acrylate or polyvinylpyrrolidone carrier.
  • the dosage form of the pesticide nanosolid dispersion is a powder, a tablet, a granule or a microcapsule.
  • the powders, tablets, granules and microcapsules are all prepared according to the composition of the pesticide nanosolid dispersion of the present invention by a corresponding conventional method.
  • the invention also relates to a process for the preparation of the pesticide nanosolid dispersion. See Figure 1 for the specific preparation process.
  • the "nano-dispersion liquid” and the “nano-solid dispersion” mean a dispersion liquid and a dispersion having an average particle diameter of the pesticide particles of 1 ⁇ m or less, preferably having an average particle diameter of less than 500 nm. Preferably the average particle size is less than 100 nm.
  • One of the preparation methods of the present invention first obtains a nanoparticle dispersion of a suitable concentration.
  • the poorly soluble solid drug is dispersed in the solution in nanometer-sized particles.
  • the small size, large specific surface area of the drug-loaded particles and the functional modification of the hydrophilic group on its surface in the auxiliary component significantly improve the solubility, dispersibility and stability of the poorly soluble drug in solution, and ensure the nanosolid dispersion. Good dispersibility, suspension and uniformity of drug concentration can be maintained during water spray application.
  • nanosolid dispersions For pesticides having a melting point below 100 ° C, water can be used as a solvent for the preparation of nanosolid dispersions. For pesticides having a melting point above 100 ° C, a poor dispersion of the original drug is selected to prepare a nanosolid dispersion.
  • the steps of the preparation method of the pesticide nanosolid dispersion are as follows:
  • the pesticide has been described above and will not be described herein.
  • This step uses a method of dispersing the original drug in a molten state, so that the drug is dispersed into nanoparticles in a liquid state, on the one hand, the hardness of the raw material during shearing or homogenization can be reduced, the energy consumption can be reduced, and the wear of the instrument can be prevented; Improve the uniformity of dispersion and minimize the particle size after dispersion.
  • the cooling operation is to rapidly convert the dispersed small droplets of the original drug into a solid state, reducing the dissolution.
  • the viscosity of the liquid and the interaction between the drugs stabilize the drug particles at the nanometer scale in a short time.
  • the particle size and dispersion uniformity of the pesticide solid nanoparticle dispersion obtained in this step greatly affect the particle size and solubility of the final nanosolid dispersion. Therefore, the particle size and the particle size of the nanoparticle dispersion obtained in this step are large. The smaller the dispersion index, the better.
  • the high-speed shear emulsifier used in the present invention is a product currently on the market, such as a product sold by ATS under the trade name C25, and its rotational speed is 1000-30000 rpm.
  • the high-pressure homogenizer used in the present invention is a product currently on the market, such as a product sold by ATS under the trade name AH-100D, and its pressure is 50-1500 bar.
  • the agitator used in the present invention is a product currently on the market, such as a product sold by Guohua Instrument Company under the trade name 78-2, and its speed is 50-5000 rpm.
  • the pesticide solid nanoparticle dispersion obtained in the step A stirring uniformly, and then drying by heating, evaporation under reduced pressure, vacuum drying or freezing The drying method removes moisture, and thus the pesticide nanosolid dispersion is prepared.
  • an auxiliary component such as a surfactant or a water-soluble carrier is added to the solid nanoparticle dispersion obtained in the step A, and the drug particles are coated and surface-modified to obtain drug-loaded particles.
  • the drug-loaded particles are prevented from coalescence, flocculation and precipitation by electrostatic action or steric hindrance, so that they are stably dispersed in the solution.
  • the solvent is removed, the drug-loaded particles are converted into a stable nano-solid dispersion, which improves the convenience and safety during storage and transportation while maintaining its nano-particle size.
  • the water can be removed by heating, drying under reduced pressure, vacuum drying, and freeze drying.
  • heating and drying use Shanghai Yiheng DHG-9070A and other drying equipment, vacuum evaporation using EYELA N-2100 rotary evaporator and other equipment, vacuum drying using Jinghong XMTD-8222 and other equipment, freeze drying using EYELA FD-81 and other equipment .
  • the heating, drying, vacuum evaporation, vacuum drying or freeze drying are carried out in a conventional manner in accordance with the operating instructions of the equipment.
  • the steps of the preparation method of the pesticide nanosolid dispersion are as follows:
  • the poor solvent of the pesticide should be understood to be a solvent having a solubility of the pesticide of less than or equal to 5%; for example, n-hexane, octane, ethylene glycol monomethyl ether, ethylene glycol or hexamethylphosphinic triamide, which are all Products currently on the market.
  • the high speed shear emulsifier has a rotational speed of 1000 to 30,000 rpm
  • the high pressure homogenizer has a pressure of 50 to 1500 bar
  • the agitation speed is 50 to 5000 rpm.
  • the device used in this step is the device as described above, and will not be described here.
  • Freeze drying, spray drying, centrifugation and distillation are conventional techniques in the art, and the equipment involved is also currently on the market.
  • step A and the step B of this preparation method are the same as those described above, and therefore, the description thereof will not be repeated here.
  • Another preparation method of the present invention is to dissolve 0.001-90 parts by weight of the pesticide with the good pesticide solvent, and then add 0.001-50 parts by weight of the surfactant, 5-99.9 parts by weight of the water-soluble carrier and 0-50 parts by weight of water.
  • the mixture is uniformly mixed, and then dispersed by using a high-speed shear emulsifier or a high-pressure homogenizer, followed by distillation, vacuum evaporation, spray drying, freeze drying or drying to remove the solvent, thereby preparing the above-mentioned pesticide nanosolid dispersion.
  • the preparation method firstly dissolves the pesticide in a molecular state into a good solvent, and then, in the process of adding water or removing the solvent, the solubility of the drug is lowered, the drug is precipitated, and is coated with an auxiliary component such as a surfactant and a water-soluble carrier. Forming stable nanoparticles.
  • a good solvent for the pesticide should be understood as a solvent having a solubility of the pesticide of 5% or more; for example, C Ketones, ethyl acetate, dichloromethane, ethanol, methanol, which are currently on the market.
  • the agent is heated and blended in one step and then cooled to a microemulsion. Due to the spontaneous milk forming properties of the surfactant in the microemulsion formulation and the lack of external energy input, the amount of surfactant is greater.
  • CN 102499236A discloses solid microemulsions containing pyrethroid insecticides and their preparation.
  • the solid preparation obtained by the invention is less affected by the external environment than the nano microemulsion and the nanosuspension, the preparation is more stable, the packaging, storage and transportation are more convenient, and the shelf life is longer.
  • the present invention is a method in which the original drug is melt-sheared or melt-homogenized in the presence of water or a solvent, and a pesticide solid nanoparticle dispersion liquid is first obtained, and an auxiliary component such as a surfactant is added thereto, and the drug obtained in this manner is obtained.
  • the dispersed particle size is smaller and more uniform, and the effect of the surfactant on the coating is also better.
  • the preparation method of the invention can control the particle diameter of the final drug particle at the nanometer scale and maintain good dispersibility by controlling the temperature of the drug dispersion, combined with the means of shearing, homogenization and the like, and the method is suitable for most of the difficulties.
  • Soluble pesticides such as insecticides, herbicides, fungicides and plant growth regulators.
  • the surfactant in the nanosolid dispersion of the present invention may have a content of less than 1%, or even less than 0.1%, and maintain good dispersibility and stability as compared with the existing microemulsion and solid microemulsion technology. Sexuality, significantly saving production costs, reducing pesticide residue pollution, and ensuring food, food and ecological security.
  • nano-type pesticides are generally obtained by grinding method.
  • This method not only consumes a large amount of energy, but also obtains uneven particle size distribution, and also causes problems such as corrosion and shedding of grinding beads, polluting the system and affecting the final quality of the product.
  • the preparation method of the invention does not need to use high energy-consuming equipment such as a grinder, has simple preparation process, is easy to control, has stable product quality and good reproducibility, and not only improves production efficiency but also saves production cost.
  • the beneficial effects of the invention are: compared with the prior art, the pesticide dispersion particle size of the invention is smaller and more uniform, and the surfactant has better effect on coating, and the surfactant content can be less than 1%. Even below 0.1%, and maintaining good dispersibility and stability, the organic solvent can be completely eliminated, and the production cost is remarkably saved. Not only can the use of pesticides be saved by increasing the effective utilization rate, but also the agricultural residues and environmental pollution of residual pesticides, harmful solvents and additives can be significantly reduced, and food, food and ecological safety can be ensured.
  • the preparation method of the invention does not need to use high energy-consuming equipment such as a grinder, has simple preparation process, is easy to control, has stable product quality, good reproducibility, and improves health. Productivity also saves production costs.
  • Figure 1 is a flow chart showing the preparation process of the pesticide nanosolid dispersion of the present invention.
  • Example 1 Preparation of the pesticide nanosolid dispersion of the present invention
  • 0.001 parts by weight of the lambda-cypermethrin insecticide is heated to a temperature of 49.2 ° C above the melting point of about 10 ° C, poured into water, and then used in a high-speed shear emulsifier sold by ATS under the trade name C25 at a speed of 10,000 rpm After shearing for 20 min, the lambda-cyhalothrin was uniformly dispersed in water, and then cooled to room temperature to obtain a dispersion of the solid lambda-cyhalothrin nanoparticles;
  • the nano-solid dispersion of the lambda-cypermethrin insecticide prepared in the present example was dispersed in distilled water, and the average particle diameter was 65 nm, and the suspension ratio was 99.2, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. %, the wetting time is 25s.
  • nitenpyram insecticide 10 parts by weight of the nitenpyram insecticide is heated to a temperature of about 10 ° C above its melting point of 83 ° C, poured into water, and then sheared at a speed of 20000 rpm using a high-speed shear emulsifier sold by ATS under the trade name C25. After cutting for 20 min, the nitenpyram was uniformly dispersed in water and cooled to room temperature to obtain a nitenpyram solid nanoparticle dispersion;
  • the nitenpyram nanosolid dispersion was prepared by evaporation of a rotary evaporation apparatus sold by BUCHI under the trade name R-210 under reduced pressure in a 40-degree water bath and a vacuum pressure of 10 mbar.
  • the nanosolid dispersion of nitenpyram insecticide prepared in the present example was dispersed in distilled water, and the average particle diameter was 45 nm and the suspension ratio was 99%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 35 s.
  • Example 3 Preparation of the pesticide nanosolid dispersion of the present invention
  • spinosyn insecticide 30 parts by weight of the spinosyn insecticide was heated to a temperature of about 10 ° C above its melting point of 84 ° C, poured into water, and then used in a high pressure homogenizer sold by ATS under the trade name AH-100D at a pressure of 600 bar. After 20 min, the spinosyn is uniformly dispersed in water and cooled to room temperature to obtain a spinosyn solid nanoparticle dispersion;
  • the spinosad insecticide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 210 nm, and the suspension ratio was 98%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wet time is 40s.
  • trifluralin herbicide 25 parts by weight of trifluralin herbicide is heated to a temperature of about 10 ° C above its melting point of 49 ° C, poured into water Then, using a high-speed shear emulsifier sold by ATS Company under the trade name C25, the product was sheared at a speed of 6000 rpm for 12 min, and the trifluralin was uniformly dispersed in water and cooled to room temperature to obtain a trifluralin solid nanoparticle. Dispersion; then
  • the liquid dispersion of the trifluralin herbicide prepared in the present example was dispersed in distilled water, and the average particle diameter was 256 nm and the suspension ratio was 98%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The time is 47s.
  • Example 5 Preparation of the pesticide nanosolid dispersion of the present invention
  • step A Adding 12 parts by weight of cumene phenol polyoxyethylene ether formaldehyde condensate nonionic surfactant, 64 parts by weight of urea and sodium sulfate mixture to the frosty ground hydrochloride solid nanoparticle dispersion obtained in step A (weight ratio 1:1), 6 parts by weight of a mixture of polyethylene glycol and xanthan gum (weight ratio 1:2) auxiliary ingredients, stirred at a speed of 1000 rpm, and then used equipment sold by Shanghai Yiheng Company under the trade name DHG-9070A The water was dried by heating at 60 ° C to remove water, and thus the hypoallridin hydrochloride nanosolid dispersion was prepared.
  • the nanosolid dispersion of the downyzil hydrochloride bactericide prepared in the present example was dispersed in distilled water, and the average particle diameter was 324 nm and the suspension ratio was 99% as measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 42s.
  • fluconazole bactericide 5.9 parts by weight of fluconazole bactericide was heated to a temperature higher than 63.5 ° C of about 10 ° C, poured into water, and then sheared at 10,000 rpm for 18 min using a high speed shear emulsifier sold by ATS under the trade name C25. Dissolving fluconazole uniformly in water and cooling to room temperature to obtain a fluconazole solid nanoparticle dispersion;
  • the fluconazole bactericide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 67 nm, and the suspension ratio was 99.4%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The time is 31s.
  • alachlor herbicide 90.0 parts by weight of alachlor herbicide was heated to a temperature of 41.5 ° C above its melting point of about 10 ° C, poured into water, and then homogenized under a pressure of 800 bar using a high pressure homogenizer sold by ATS under the trade name AH-100D. 12 min, the alachlor was uniformly dispersed in water and cooled to room temperature to obtain a alachlor solid nanoparticle dispersion;
  • the alachlor herbicide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 263 nm and the suspension ratio was 98.7%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The time is 37s.
  • n-triacontanol plant growth regulator 20.0 parts by weight of n-triacontanol plant growth regulator was heated to a temperature of 87 ° C higher than its melting point of about 5 ° C, poured into water, and then used in a high-speed shear emulsifier sold by ATS under the trade name C25 at a rotational speed of 18000 rpm After shearing for 15 min, the n-triacontanol was uniformly dispersed in water and cooled to room temperature to obtain a n-triacontanol solid nanoparticle dispersion;
  • n-tricadecanol solid nanoparticle dispersion obtained in the step A 8.0 parts by weight of dodecyl betaine and 72 parts by weight of a sodium sulfate water-soluble carrier were added, and the mixture was stirred at a rotation speed of 2,600 rpm, and then used by the EYELA company under the trade name.
  • the equipment sold by FD-81 was freeze-dried under 10 Pa conditions to remove moisture, and thus the n-triacontanol nanosolid dispersion was prepared.
  • the n-tricadecanol plant growth regulator nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 430 nm and the suspension ratio was 98 using a Nano ZS90 laser particle size analyzer manufactured by Malvern. %, the wetting time is 42s.
  • Example 9 Preparation of the pesticide nanosolid dispersion of the present invention
  • deltamethrin insecticide 0.001 parts by weight of deltamethrin insecticide is heated to about 5 ° C above its melting point of 101 ° C, then deltamethrin is poured into ethylene glycol solvent, and then used by ATS company under the trade name C25 high-speed shears The emulsifier was sheared at a speed of 25,000 rpm for 18 min, and the deltamethrin was uniformly dispersed in ethylene glycol, followed by cooling to room temperature to obtain a deltamethrin solid nanoparticle dispersion;
  • the deltamethrin insecticide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 85 nm and the suspension ratio was 99%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 42 s.
  • Example 10 Preparation of the pesticide nanosolid dispersion of the present invention
  • 29.0 parts by weight of the buprofezin insecticide was heated to a temperature of 105 ° C, followed by pouring the buprozin into dimethylformamide, and then using a high speed shear emulsifier sold by ATS under the trade name C25 at a rotational speed of 16,000 rpm. Under the conditions of shearing for 14 min, the buprofezin was uniformly dispersed in dimethylformamide, and cooled to room temperature to obtain a buprofezin solid nanoparticle dispersion;
  • An aqueous solution of a lactose-soluble carrier was uniformly stirred at a number of revolutions of 2,200 rpm, and the solvent was removed by lyophilization at 5 Pa using an apparatus sold by EYELA Corporation under the trade name of FD-81, whereby the buprofezin nanosolid dispersion was prepared.
  • the pyrazinone insecticide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 342 nm and the suspension ratio was 97.5%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The wet time is 48s.
  • Example 11 Preparation of the pesticide nanosolid dispersion of the present invention
  • biphenyl triazole alcohol bactericide 90.0 parts by weight of the biphenyl triazole alcohol bactericide is heated to a temperature of about 5 ° C above its melting point of 125 ° C, then the biphenyl triazole alcohol is poured into dimethylformamide, and then used by the ATS company under the trade name AH-100D
  • the high-pressure homogenizer sold is homogenized for 18 min under the pressure of 800 bar, and the joint will be
  • the benzotriazole alcohol is uniformly dispersed in dimethylformamide and cooled to room temperature to obtain a biphenyl triazole alcohol solid nanoparticle dispersion;
  • an aqueous solution containing 0.001 part by weight of a fatty alcohol polyoxyethylene phosphatidylate anionic surfactant and 9.999 parts by weight of a water-soluble carrier of hydroxypropylmethylcellulose is added.
  • the mixture was stirred at a rotation speed of 2,200 rpm, and the solvent was removed at 40 ° C using a vacuum drying apparatus sold by Jinghong under the trade name XMTD-822, thereby preparing the biphenyl triazole alcohol nanosolid dispersion.
  • the biphenyl triazole alcohol bactericide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 560 nm and the suspension ratio was 96.5%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 50 s.
  • Example 12 Preparation of the pesticide nanosolid dispersion of the present invention
  • 50.0 parts by weight of the flufenazole bactericide is heated to a temperature of 118.5 ° C above its melting point of about 5 ° C, followed by pouring the flurazol into ethylene glycol, and then using a high-speed shear emulsifier sold by ATS under the trade name C25 After shearing for 14 min at a rotational speed of 16,000 rpm, the silicoazole was uniformly dispersed in ethylene glycol, and cooled to room temperature to obtain a dispersion of a solid silicone nanoparticle;
  • aqueous solution containing 45.0 parts by weight of a polyvinylpyrrolidone nonionic surfactant and 5.0 parts by weight of a hydroxyethylcellulose water-soluble carrier was added to the dispersion of the silicon fluoroazole solid nanoparticle obtained in the step A, stirring at a rotation speed of 3,500 rpm, and then using The apparatus sold by EYELA Corporation under the trade name FD-81 was freeze-dried to remove the solvent under 5 Pa conditions, thereby preparing the silicofluoride nanosolid dispersion.
  • the nano-solid dispersion of the silicone-containing azole fungicide prepared in the present example was dispersed in distilled water, and the average particle diameter was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern, and the suspension ratio was 98%. The time is 33s.
  • Example 13 Preparation of the pesticide nanosolid dispersion of the present invention
  • pyrazosulfuron-methyl herbicide 0.05 parts by weight was heated to a melting point of 178 ° C, then pyrazosulfuron was poured into ethylene glycol, and a high-pressure homogenizer sold by ATS under the trade name AH-100D was used at a pressure of 1200 bar. Under the condition of homogenization for 10 min, the pyrazosulfuron-methyl is uniformly dispersed in ethylene glycol, and cooled to room temperature to obtain a pyrimidosulfuron solid nanoparticle dispersion;
  • An aqueous solution of a mixture of ethylene glycol and xanthan gum (weight ratio 1:2) was uniformly stirred at a rotational speed of 3200 rpm, and then lyophilized to remove the solvent at 5 Pa using a device sold by EYELA under the trade name FD-81, thereby preparing The pyrazosulfuron-methyl nanosolid dispersion is obtained.
  • the pyrazosulfuron-methyl herbicide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 482 nm and the suspension rate was 98%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The wet time is 35s.
  • Example 14 Preparation of the pesticide nanosolid dispersion of the present invention
  • step A Adding 8.0 parts by weight of sorbitan oleate nonionic surfactant, 70 parts by weight of hydroxyethyl- ⁇ -cyclodextrin, and 5 parts by weight of polyethyl bromide to the butylated hydrazide solid nanoparticle dispersion obtained in step A
  • An aqueous solution of a mixture of a diol and a magnesium aluminum silicate (weight ratio of 3:1) was uniformly stirred at a rotational speed of 1800 rpm, and then a solvent was removed at 5 Pa using a freeze-drying apparatus sold by EYELA under the trade name FD-81, thereby preparing The butyrylhydrazine nanosolid dispersion is obtained.
  • the butadiene hydrazide plant growth regulator nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 490 nm and the suspension ratio was 98.5%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 40 s.
  • Example 15 Preparation of the pesticide nanosolid dispersion of the present invention
  • avermectin insecticide 25 parts by weight of the avermectin insecticide was dissolved in acetone, and then 25 parts by weight of an aqueous solution of a fatty alcohol polyoxyethylene ether carboxylate anionic surfactant and 50 parts by weight of a lactose water-soluble carrier were added thereto, and the mixture was uniformly stirred.
  • a high-speed shear emulsifier sold by ATS Corporation under the trade name C25
  • shearing at a rotational speed of 18,000 rpm for 12 min shearing at a rotational speed of 18,000 rpm for 12 min, and then removing the solvent at 45 ° C using a rotary evaporation apparatus sold by EYELA under the trade name N-2100.
  • the avermectin nanosolid dispersion is then prepared.
  • the avermectin insecticide nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 95 nm and the suspension ratio was 99%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 25 s.
  • Example 16 Preparation of the pesticide nanosolid dispersion of the present invention
  • emamectin benzoate insecticide 45 parts by weight of emamectin benzoate insecticide was dissolved in ethyl acetate, and then 25 parts by weight of maleic rosin polyoxyethylene-oxypropylene ether sulfonate and 15 parts by weight of 12 were added thereto.
  • An aqueous solution of an alkyl benzene sulfonate anionic surfactant and 15 parts by weight of a urea water-soluble carrier is uniformly stirred, and then homogenized at a pressure of 800 bar for 12 minutes using a high-pressure homogenizer sold by ATS under the trade name AH-100D.
  • the methylamino group was prepared by using a spray drying apparatus sold by EYELA under the trade name SD-1000 at an inlet air temperature of 120 ° C, an outlet air temperature of 95 ° C, a spray pressure of 20 kPa, and an injection speed of 0.09 L/h.
  • Abamectin benzoate nanosolid dispersion was prepared by using a spray drying apparatus sold by EYELA under the trade name SD-1000 at an inlet air temperature of 120 ° C, an outlet air temperature of 95 ° C, a spray pressure of 20 kPa, and an injection speed of 0.09 L/h.
  • the nanosolid dispersion of the amifostatin benzoate insecticide prepared in the present example was dispersed in distilled water, and the average particle diameter was 87 nm as measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The suspension rate was 99% and the wetting time was 23 s.
  • Example 17 Preparation of the pesticide nanosolid dispersion of the present invention
  • the nanosolid dispersion of the prochlorazicide sterilizing agent prepared in the present example was dispersed in distilled water, and the average particle diameter was 550 nm and the suspension ratio was 97.5%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The time is 42s.
  • Example 18 Preparation of the pesticide nanosolid dispersion of the present invention
  • 0.05 part by weight of a thiofuramide bactericide was dissolved in chloroform, and then 0.05 part by weight of an oil-based biuret amphoteric surfactant, 99.9 parts by weight of a mixture of urea and sodium sulfate (weight ratio of 3:1), a water-soluble carrier, was added thereto.
  • the silufamide nanosolid dispersion was prepared by stirring at a rotational speed of 4,200 rpm and then removing the solvent at 30 ° C using a rotary evaporation apparatus sold by the company EELLA under the trade name N-2100.
  • the nanosolid dispersion of the thiafuramide bactericide prepared in the present example was dispersed in distilled water, and the average particle diameter was 620 nm and the suspension ratio was 97%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The time is 48s.
  • the herbicide nanosolid dispersion prepared in this example was dispersed in distilled water, and the average particle diameter was 190 nm, the suspension ratio was 98%, and the wetting was measured using a Nano ZS90 laser particle size analyzer manufactured by Malvern. The time is 38s.
  • sulfasulfuron-methyl herbicide 20 parts by weight of the sulfasulfuron-methyl herbicide was dissolved in methanol, and then 50 parts by weight of an oil-based biuret amphoteric surfactant, 25 parts by weight of a mixture of urea and sodium sulfate (weight ratio of 3:1), and 5 weights were added thereto.
  • An aqueous solution of a mixture of polyethylene glycol and magnesium aluminum silicate (3:5 by weight) was sheared at 10,000 rpm for 8 min using a high speed shear emulsifier sold by ATS under the trade name C25, and then used by EYELA.
  • the solvent sold by the company under the trade name FD-81 was freeze-dried at 10 Pa to remove the solvent to prepare the sulfimsulfuron nanosolid dispersion.
  • the cyazosulfuron herbicide nanosolid dispersion prepared in this example was dispersed in distilled water, and the average particle diameter was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern Co., Ltd., and the suspension ratio was 98%.
  • the wet time is 33s.
  • 0.001 parts by weight of a benzylaminopurine plant growth regulator was dissolved in methanol, followed by the addition of 25 parts by weight of castor oil polyoxyethylene ether nonionic surfactant, 25 parts by weight of dodecyl betaine amphoteric surfactant, 30
  • An aqueous solution of a mixture of urea and sucrose (weight ratio of 1:1) and 19.999 parts by weight of a polyethylene glycol water-soluble carrier was uniformly stirred at a rotation speed of 4,200 rpm, and then spray-drying equipment sold by EYELA under the trade name SD-1000 was used.
  • the benzylaminoguanidine nanosolid dispersion was prepared by removing the solvent under the conditions of an inlet air temperature of 120 ° C, an outlet temperature of 95 ° C, a spray pressure of 20 kPa, and an injection rate of 0.1 L/h.
  • the benzylaminoguanidine plant growth regulator nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 85 nm, and the suspension ratio was 99%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 22 s.
  • a pyridyl alcohol plant growth regulator 42.0 parts by weight of a pyridyl alcohol plant growth regulator was dissolved in chloroform, followed by adding 0.001 part by weight of a fatty alcohol polyoxyethylene ether carboxylate anionic surfactant, 57.999 parts by weight of an aqueous solution of a sucrose water-soluble carrier, using ATS
  • the pyridyl alcohol nanosolid was prepared by shearing under high speed shear emulsifier sold under the trade name C25 at a rotation speed of 10,000 rpm for 15 min. Dispersions.
  • the pyridyl plant growth regulator nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern Co., Ltd., and the suspension ratio was 98%.
  • the wet time is 32s.
  • the nano-dispersion of the cyhalothrin-spinhin insecticide prepared in the present example was dispersed in distilled water, and the average particle diameter was 175 nm measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. The suspension rate was 99% and the wetting time was 35 s.
  • Example 24 Preparation of the pesticide nanosolid dispersion of the present invention
  • spinosyn insecticide and 30 parts by weight of trifluralin herbicide were heated to 90 ° C, poured into water, and then used in a high pressure homogenizer sold by ATS under the trade name AH-100D at a pressure of 1200 bar. After homogenization for 20 min, the spinosyn and trifluralin were uniformly dispersed in water, followed by cooling to room temperature to obtain a solid nanoparticle dispersion containing spinosyn and trifluralin;
  • the spinosad-trifluralin nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 320 nm and the suspension ratio was 98.7%, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 43 s.
  • Example 25 Preparation of the pesticide nanosolid dispersion of the invention
  • the propionate hydrochloride- alachlor nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 255 nm and the suspension ratio was measured using a Nano ZS90 laser particle size analyzer manufactured by Malvern. 98.2%, the wetting time is 29s.
  • Example 26 Preparation of the pesticide nanosolid dispersion of the invention
  • the deltamethrin-silicofluorazole nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 172 nm and the suspension ratio was 98.5% as measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern.
  • the wetting time is 34s.
  • Surfactant 15 parts by weight of cumene phenol polyoxyethylene ether formaldehyde condensate nonionic surfactant, 34 parts by weight aqueous solution of sucrose water-soluble carrier, using a high-speed shear emulsifier sold by ATS under the trade name C25 The mixture was sheared at a speed of 10,000 rpm for 15 minutes, and then lyophilized to remove the solvent under the condition of 5 Pa using the equipment sold by EYELA under the trade name FD-81 to prepare a lambda-cypermethrin avermectin nanosolid dispersion. body.
  • the cyhalothrin-averager nanosolid dispersion prepared in the present example was dispersed in distilled water, and the average particle diameter was 67 nm, which was measured by a Nano ZS90 laser particle size analyzer manufactured by Malvern. It is 99.5% and the wetting time is 21s.

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Abstract

本发明涉及一种农药纳米固体分散体及其制备方法，所述的农药纳米固体分散体由0.001-90重量份农药、0.001-50份表面活性剂与5-99.9份水溶性载体组成，所述的农药选自一种或多种难溶性的杀虫剂、杀菌剂、除草剂或植物生长调节剂；所述固体分散体粒径是1μm以下。与现有技术相比，本发明的农药分散粒径更小、更均匀，表面活性剂对其包覆的效果更好，表面活性剂含量可以低于1％，甚至低于0.1％，且保持了良好的分散性和稳定性，可以完全杜绝有机溶剂，显著节约生产成本。不仅可以通过提高有效利用率来节约农药使用量，而且可以显著降低残留农药、有害溶剂与助剂的农产品残留与环境污染，确保粮食、食品和生态安全。

Description

一种农药纳米固体分散体及其制备方法
本申请要求申请日为2015年3月13日、为申请号为CN 2015101098872的中国发明专利申请为优先权。
【技术领域】
本发明属于农药技术领域。更具体地，本发明涉及一种农药纳米固体分散体，还涉及所述农药纳米固体分散体的制备方法。
【背景技术】
农药是防御重大生物灾害、保障粮食安全、促进农产品产量持续稳定增长的重要物质基础。根据***粮农组织(FAO)统计，全世界使用农药防治病虫害挽回的农产品损失约占总产量的30％。除少数品种外，农药原药一般不能直接施用，必须根据原药特性和使用的具体要求与一种或多种农药助剂配合使用，加工或制备成某种特定的形式，这种加工后的农药形式就是农药剂型。
目前我国生产和使用的高效与环保型农药比重不高，仍以乳油、可湿性粉剂等传统剂型为主，存在大量使用有机溶剂、粉尘飘移、分散性差、药效不稳定等局限性，有效利用率普遍偏低。提高农药有效利用率和生物利用度的常用药剂学方法有：助溶剂法、减小粒径、改变晶型、表面活性剂助溶法和把药物加载到水溶性载体上等。
纳米科技的迅猛发展，为现代农业科学提供了新的理论与技术方法。利用纳米材料与技术对原有农药进行剂型加工、改造及创新，使许多新型、高效剂型大量出现。
纳米微乳剂是水基化农药剂型中的一种，是替代乳油、减少有机溶剂污染的新剂型之一，例如CN 1656893A公开了一种生产农药微乳剂的方法。纳米微乳剂是由液态农药、表面活性剂、水、稳定剂等组成的热力学稳定 的分散体系。其特点是以水为介质，不含或少含有机溶剂，因而不燃不爆，生产操作、贮运安全，环境污染少，大量节省有机溶剂；农药在水中分散度极高，粒径一般为10～100nm，外观近似于透明或微透明液；具有优异的增溶作用、更高的传递效率、更易润湿展布以及更强的渗透能力等，可获得更高的生物利用度。尽管如此，微乳剂也存在着一些缺点和局限性。常见问题为乳液不稳定、容易结晶析出、透明温区窄、制剂含量不高、制剂的稳定性易受外界环境干扰而被破坏，在储存和运输过程中存在安全隐患，尤其是为了维持其稳定性和分散性，需要大量使用表面活性剂，通常是农药含量的3-4倍以上。各种表面活性剂和助剂的大量使用，也导致了新的环境污染与食品安全性问题，特别是在新鲜食用的蔬菜和水果等作物保护上应用受到了很大限制。
CN 102499236A公开了含拟除虫菊酯杀虫剂的固体微乳剂及其制备方法。该方法是将原药与表面活性剂和/或有机溶剂混合形成油相，再与含有载体的固相和/或水相混合，形成固油混合物或水固油混合物。此固体微乳剂能在水中分散成无色、透明或半透明微乳液，与常规微乳剂用水稀释后形成的乳状液相同，可继承微乳剂的优点，同时克服了液态制剂稳定性易受外界环境干扰与破坏、不便于长期保存和运输等缺陷，但仍然不能解决大量使用表面活性剂所引发的环境污染与食品安全性问题。
农药纳米混悬剂是另一种水基化农药新剂型，它是通过表面活性剂的稳定作用将“纯”农药有效成分分散在水中而形成的一种亚微米胶体分散体系。该剂型中的农药有效成分的粒径小，比表面积大，药物的溶出速率和靶标粘着性增大增强，从而有利于提高有效利用率。但其主要缺陷是液体制剂的稳定性差，通常需要加入较多的稳定剂及助悬剂。
此外，将难溶性农药制备成纳米尺度的超精细粉体制剂的研究也取得了一定进展，但是，农药纳米粉体颗粒在兑水分散过程中因静电引力和范德华力等相互作用所导致的团聚、絮凝、沉降等问题一直未能得到有效克服和解决，使其难以发挥理想的施用效果。
本发明在既存技术的基础上，通过长时间的锐意创新和探索研究，创造了一种能使难溶性药物以固体形态的纳米粒子高度分散于载体与表面活 性剂中的固体制剂及其制备方法。它可以杜绝有机溶剂和大幅度减少表面活性剂与助剂的使用，既能发挥农药纳米制剂的许多优越性，又能克服现有剂型的主要局限性。作为一种固体制剂，它受外界环境影响小，稳定性和货架期显著改善，便于包装、储存和运输。该制剂直接兑水稀释后可形成综合性能优良的水基化纳米分散体系，对作物喷洒使用后，有利于提高难溶性药物的分散度与溶出速率，增加药物在叶面的粘附性和渗透性，从而提高其生物利用度，节约农药使用量，减少残留污染。
【发明内容】
[要解决的技术问题]
本发明的目的是提供一种农药纳米固体分散体。
本发明的另一个目的是提供所述农药纳米固体分散体的制备方法。
[技术方案]
本发明是通过下述技术方案实现的。
本发明涉及一种农药纳米固体分散体，其特征在于它是由难溶性农药纳米粒子均匀地分散在表面活性剂和水溶性载体中所形成的农药纳米固体分散体，以重量份计，它的组成如下：
农药             0.001-90；
表面活性剂       0.001-50；
水溶性载体       5-99.9；
所述的农药是一种或多种选自难溶性的杀虫剂、杀菌剂、除草剂或植物生长调节剂的农药；
所述的农药纳米粒子的平均粒径为1-1000nm，优选平均粒径小于500nm，更优选平均粒径小于100nm。
根据本发明，所述杀虫剂、杀菌剂、除草剂或植物生长调节剂的难溶性应该理解是在水中的溶解度小于或等于0.1g/L。
在本发明中，所述的杀虫剂应该理解是能用于防治在应用本发明产品时所遇到农业害虫的药品。众所周知，几乎所有杀虫剂都会对生态***造成影响，大部分对人体有害，其它的会被集中在食物链中。因此，必须在农业发展与环境及健康中取得平衡。
根据本发明，所述的杀虫剂选自拟选自拟除虫菊酯、氨基甲酸酯、有机磷、有机硫、有机胆碱、沙蚕毒素、新烟碱、苯基酰尿、阿维菌素、哒螨灵、灭螨醌、苯基吡唑、茚虫威或丁醚脲类杀虫剂，但不限于此范围；
本发明使用的杀虫剂都是目前市场上销售的产品。
在本发明中，所述的杀菌剂应该理解是能有效地控制或杀死在应用本发明产品时所遇到微生物，其中包括细菌、真菌和藻类的化学制剂。
根据本发明，所述的杀菌剂选自苯胺基吡啶、抗生素、芳族烃、二硝基苯胺、烯丙胺、苯磺酰胺、苯并咪唑、苯并异噻唑、二苯甲酮、苯并基嘧啶、苯并三嗪、氨基甲酸苄酯、氨基甲酸酯、羧酰胺、羧酸二酰胺、氯腈、氰基咪唑、环丙烷羧酰胺、乙基氨基噻唑羧酰胺、咪唑、羟基酰替苯胺、咪唑啉酮、异苯并呋喃酮、甲氧基丙烯酸酯、甲氧基氨基甲酸酯、吗啉、N-苯基氨基甲酸酯、噁唑烷二酮、苯基乙酰胺、苯基酰胺、苯基吡咯、苯脲、硫代磷酸酯、邻氨甲酰苯甲酸、邻苯二甲酰亚胺、哌嗪、哌啶、丙酰胺、吡啶、吡啶基甲基酰胺、甲苯酰胺、三嗪或***类杀菌剂，但不限于此范围；
本发明使用的杀菌剂都是目前市场上销售的产品。
在本发明中，所述的除草剂应该理解是可使农田杂草彻底地或选择地发生枯死的药剂，用以消灭或抑制植物生长。
根据本发明，所述的除草剂选自酰胺、芳氧基苯氧基丙酸酯、苯氧羧酸、有机磷、苯甲酰胺、苯并呋喃、苯甲酸、苯并噻二嗪酮、氨基甲酸酯、氯乙酰胺、吡啶羧酸、氯羧酸、环已二酮、二硝基苯胺、二苯醚、异恶唑、异恶唑烷酮、N-苯基邻苯二甲酰亚胺、噁二唑、噁唑烷二酮、氧基乙酰胺、苯基氨基甲酸酯、苯基哒嗪、磺基氨基羧基***啉酮、磺酰***并羧酰胺、***并嘧啶、三酮、尿嘧啶或脲类除草剂，但不限于此范围；
本发明使用的除草剂都是目前市场上销售的产品。
在本发明中，所述的植物生长调节剂应该理解是对植物的生长发育具有调节作用的化学物质。
根据本发明，所述的植物生长调节剂选自青鲜素、萘乙酸甲酯、6-苄基氨基嘌呤，油菜素内酯、氨氧乙基乙烯基甘氨酸或多效唑类植物生长调节 剂，但不限于此范围。
本发明使用的植物生长调节剂都是目前市场上销售的产品。
在本发明中，所述的表面活性剂应该理解是能使其溶液体系界面状态发生明显改变的物质。表面活性剂的分子结构具有两亲性：一端为亲水基团，另一端为憎水基团；亲水基团常为极性基团，如羧酸、磺酸、硫酸、氨基、羟基、酰胺基等；而憎水基团常为非极性烃链。所述的表面活性剂是一种或多种选自阳离子表面活性剂、阴离子表面活性剂、非离子表面活性剂或两性表面活性剂的表面活性剂。
根据本发明，所述阳离子表面活性剂选自脂肪胺盐、乙醇胺盐、聚乙烯多胺盐或季铵盐阳离子表面活性剂；
所述阴离子表面活性剂选自十二烷基磺酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、马来松香聚氧乙烯-氧丙烯醚磺酸盐、烷基酚聚氧乙烯醚磷酸酯盐、单十二烷基醚磷酸酯盐、双十二烷基醚磷酸酯盐、辛基醚磷酸酯、脂肪醇聚氧乙烯磷脂酸盐、脂肪醇聚氧乙烯醚羧酸盐、聚羧酸盐或木质素磺酸盐阴离子表面活性剂；
所述非离子表面活性剂选自烷基酚聚氧乙烯醚甲醛缩合物、苯乙烯基酚聚氧乙烯醚甲醛缩合物、多苯乙烯苯酚聚氧乙烯醚、异丙苯基酚聚氧乙烯醚甲醛缩合物、苄基酚聚氧乙烯醚甲醛缩合物、蓖麻油聚氧乙烯醚、聚乙烯吡咯烷酮、聚氧乙烯脱水山梨醇单油酸酯、山梨糖醇酐油酸酯、聚氧乙烯聚氧丙烯嵌段共聚物或蔗糖单油酸酯非离子表面活性剂；
所述两性表面活性剂选自十二烷基羟丙基磺基甜菜碱、十二烷基甜菜碱、十八烷基二羟乙基氧化胺、十八烷基脲或油基缩二脲两性表面活性剂。
本发明使用的阳离子表面活性剂、阴离子表面活性剂、非离子表面活性剂或两性表面活性剂都是目前市场上销售的产品。
在本发明中，所述的水溶性载体选自尿素、硫酸钠、硫酸镁、苯甲酸钠、蔗糖、乳糖、可溶性淀粉、羟丙基甲基纤维素、羟乙基纤维素、羧甲基纤维素钠、羟乙基-β-环糊精、羟丙基-β-环糊精、磺酸基-β-环糊精、聚乙烯醇、聚乙二醇、黄原胶、硅酸镁铝、***胶、丙烯酸钠或聚乙烯吡咯烷酮载体。
所述农药纳米固体分散体的剂型是粉剂、片剂、颗粒剂或微胶囊剂。
所述的粉剂、片剂、颗粒剂与微胶囊剂都是按照本发明农药纳米固体分散体的组成采用相应的常规方法制备的。
本发明还涉及所述农药纳米固体分散体的制备方法。具体制备工艺流程参见附图1。
在本发明中，所述的“纳米分散液”和“纳米固体分散体”是指其含有的农药粒子的平均粒径为1μm以下的分散液和分散体，优选地平均粒径小于500nm，更优选地平均粒径小于100nm。
本发明的制备方法之一首先得到合适浓度的纳米粒子分散液。在分散液中，难溶性的固体药物以纳米尺寸的颗粒分散于溶液中。载药粒子的小尺寸、大比表面积及其辅助成分中亲水基团对其表面的功能修饰，显著提高了难溶性药物在溶液中的溶解度、分散性和稳定性，保证了纳米固体分散体在兑水喷洒使用过程中，可以维持良好的分散性、悬浮性及药物浓度的均一性。
对于熔点在100℃以下的农药，可以水为溶剂进行纳米固体分散体的制备。对于熔点在100℃以上的农药，选取不溶解原药的不良溶剂制备纳米固体分散体。
对于熔点在100℃以下的农药，所述农药纳米固体分散体制备方法的步骤如下：
B、制备纳米分散液
将0.001-90重量份农药加热达到高于所述农药熔点，但低于其分解与变性温度的温度，接着把所述农药倒入水中，再使用高速剪切乳化机或高压均质机将所述农药均匀分散在水中，冷却至常温，得到一种农药固体纳米粒子分散液；
所述的农药已在前面描述，在此不再赘述。
这个步骤采用熔化状态下分散原药的方法，使药物在液态下被分散为纳米颗粒，一方面可以减小剪切或均质时的原料硬度，降低能耗，防止仪器磨损；另一方面可以提高分散的均匀度，最大程度地削减分散后的粒径。
随后，冷却操作是为了将分散的原药小液滴迅速转变成固态，减低溶 液黏度和药物间的相互作用，将药物颗粒短时间内稳定在纳米尺度。
这个步骤获得的农药固体纳米粒子分散液的粒径及分散均匀度会对最终纳米固体分散体的粒径及溶解性产生很大影响，因此，这个步骤得到的纳米粒子分散液的粒径和多分散指数越小越好。
本发明使用的高速剪切乳化机是目前市场上销售的产品，例如由ATS公司以商品名C25销售的产品，它的转速是1000-30000rpm。本发明使用的高压均质机是目前市场上销售的产品，例如由ATS公司以商品名AH-100D销售的产品，它的压力是50-1500bar。本发明使用的搅拌机是目前市场上销售的产品，例如由国华仪器公司以商品名78-2销售的产品，它的速度是50-5000rpm。
B、制备纳米固体分散体
往步骤A得到的农药固体纳米粒子分散液中添加0.001-50重量份表面活性剂和5-99.9重量份水溶性载体辅助成分，搅拌均匀，再采用加热烘干、减压蒸发、真空干燥或冷冻干燥方法去除水分，于是制备得到所述农药纳米固体分散体。
这个步骤是往步骤A得到的固体纳米粒子分散液中加入表面活性剂、水溶性载体等辅助成分，对药物粒子进行包覆和表面修饰，进而获得载药粒子。载药粒子间通过静电作用或空间位阻，阻止药物聚结、絮凝和沉淀，使其稳定地分散在溶液中。溶剂去除后，载药粒子被转化为稳定的纳米固体分散体，在保持其纳米粒径的同时，提高了储存和运输过程中的便捷性和安全性。
去除水分可采用加热烘干、减压蒸发、真空干燥及冷冻干燥等方法。例如加热烘干使用上海一恒DHG-9070A等烘干设备、减压蒸发使用EYELA N-2100旋转蒸发仪等设备，真空干燥使用精宏XMTD-8222等设备，冷冻干燥使用EYELA FD-81等设备。
在进行加热烘干、减压蒸发、真空干燥或冷冻干燥时都是按照其设备说明书操作规程以常规方式进行的。
对于熔点在100℃以上的农药，所述农药纳米固体分散体的制备方法的步骤如下：
B、制备纳米分散液
将0.001-90重量份农药加热达到高于所述农药熔点的温度，接着把它倒入所述农药的不良溶剂中，再使用高速剪切乳化机或高压均质机将所述农药均匀分散在不良溶剂中，冷却至常温，得到一种农药固体纳米粒子分散液。
所述农药的不良溶剂应该理解是农药的溶解度小于或等于5％的溶剂；例如正己烷、辛烷、乙二醇单甲醚、乙二醇或六甲基亚膦酰三胺，它们都是目前市场上销售的产品。
所述高速剪切乳化机的转速是1000-30000rpm，所述高压均质机的压力是50-1500bar；所述搅拌速度是50-5000rpm。这个步骤使用的设备是如前面所述的设备，这里不再赘述。
B、制备纳米固体分散体
往步骤A得到的农药固体纳米粒子分散液中添加含有0.001-50重量份表面活性剂和5-99.9重量份水溶性载体辅助成分的水溶液，搅拌均匀，再采用冷冻干燥、喷雾干燥、离心及蒸馏去除不良溶剂，于是制备得到所述的农药纳米固体分散体。
冷冻干燥、喷雾干燥、离心及蒸馏都是本技术领域里常规技术，所涉及的设备也是目前市场上销售的产品。
这个制备方法的步骤A与步骤B的情况如前面所述的相同，因此，在此不再赘述。
本发明的另一制备方法为将0.001-90重量份农药用所述农药良溶剂溶解，然后加入0.001-50重量份表面活性剂、5-99.9重量份水溶性载体与0-50重量份水，混合均匀，再使用高速剪切乳化机或高压均质机进行分散，接着进行蒸馏、减压蒸发、喷雾干燥、冷冻干燥或烘干，除去溶剂，于是制备得到所述的农药纳米固体分散体。该制备方法首先是将农药以分子状态溶解到良溶剂中，随后在加入水或去除溶剂的过程中，使药物溶解度下降，药物析出，并被表面活性剂和水溶性载体等辅助成分包覆，形成稳定的纳米颗粒。
所述农药的良溶剂应该理解是农药的溶解度在5％以上的溶剂；例如丙 酮、乙酸乙酯、二氯甲烷、乙醇、甲醇，它们都是目前市场上销售的产品。
剂一步加热共混，再冷却成微乳液。由于微乳剂剂型中表面活性剂的自发成乳特性和缺少外界能量输入，表面活性剂的用量较大。
CN 102499236A公开了含拟除虫菊酯杀虫剂的固体微乳剂及其制备。
本发明得到的固体制剂较纳米微乳液和纳米混悬剂受外界环境影响小，制剂更加稳定，包装、储存和运输更为方便，货架寿命更长。另外，本发明是在水或溶剂存在的条件下对原药进行熔融剪切或熔融均质，先得到农药固体纳米粒子分散液，再加入表面活性剂等辅助成分，以这种方式得到的药物分散粒径更小，更均匀，表面活性剂对其包覆的效果也更好。本发明制备方法通过控制药物分散时的温度，结合剪切、均质等分散手段，可以将最终药物粒子粒径控制在纳米尺度，并保持了良好的分散性，该方法适用于绝大多数难溶性农药，如杀虫剂、除草剂、杀菌剂和植物生长调节剂等。此外，与现有微乳剂及固体微乳剂技术相比，本发明中纳米固体分散体中的表面活性剂的含量可以低于1％，甚至可以低于0.1％，且保持良好的分散性和稳定性，显著节约了生产成本，降低了农药残留污染，保证了粮食、食品和生态安全。
目前，纳米剂型农药普遍采用研磨方式获得，此方法不仅能耗大，获得的粒径分布不均，还会因研磨珠溶蚀和脱落等问题，污染体系，影响产品的最终质量。本发明的制备方法无需使用研磨机等高能耗设备，制备工艺简单，易于控制，产品质量稳定，重现性好，既提高了生产效率，又节约了生产成本。
[有益效果]
本发明的有益效果是：与现有技术相比，本发明的农药分散粒径更小、更均匀，表面活性剂对其包覆的效果也更好，表面活性剂含量可以低于1％，甚至低于0.1％，且保持了良好的分散性和稳定性，可以完全杜绝有机溶剂，显著地节约了生产成本。不仅可以通过提高有效利用率来节约农药使用量，而且可以显著降低残留农药、有害溶剂与助剂的农产品残留与环境污染，确保粮食、食品和生态安全。本发明的制备方法无需使用研磨机等高能耗设备，制备工艺简单，易于控制，产品质量稳定，重现性好，既提高了生 产效率，又节约了生产成本。
【附图说明】
图1是本发明农药纳米固体分散体的制备工艺流程图。
【具体实施方式】
通过下述实施例将能够更好地理解本发明。
实施例1：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将0.001重量份高效氯氟氰菊酯杀虫剂加热达到高于其熔点49.2℃约10℃，倒入水中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速10000rpm的条件下剪切20min，将所述高效氯氟氰菊酯均匀分散在水中，接着冷却至常温，得到一种高效氯氟氰菊酯固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的高效氯氟氰菊酯固体纳米粒子分散液中添加0.099重量份十二烷基磺酸钠阴离子表面活性剂和99.9重量份尿素，以转速1000rpm搅拌均匀，再使用由上海一恒公司以商品名DHG-9070A销售的烘干设备在80℃条件下进行加热烘干去除水分，于是制备得到所述高效氯氟氰菊酯纳米固体分散体。
将本实施例制备得到的高效氯氟氰菊酯杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为65nm，悬浮率为99.2％，润湿时间为25s。
实施例2：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将10重量份烯啶虫胺杀虫剂加热达到高于其熔点83℃约10℃，倒入水中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速20000rpm的条件下剪切20min，将烯啶虫胺均匀分散在水中，冷却至常温，得到一种烯啶虫胺固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的烯啶虫胺固体纳米粒子分散液中添加50重量份单十二烷基醚磷酸酯盐阴离子表面活性剂和40重量份硫酸钠水溶性载体，以转速1800rpm搅拌均匀，再使用由BUCHI公司以商品名R-210销售的旋转蒸发设备在40度水浴和10mbar的真空压力条件下进行减压蒸发去除水分，于是制备得到所述烯啶虫胺纳米固体分散体。
将本实施例制备得到的烯啶虫胺杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为45nm，悬浮率为99％，润湿时间为35s。
实施例3：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将30重量份多杀菌素杀虫剂加热达到高于其熔点84℃约10℃，倒入水中，再使用由ATS公司以商品名AH-100D销售的高压均质机在压力600bar的条件下均质20min，将多杀菌素均匀分散在水中，冷却至常温，得到一种多杀菌素固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的多杀菌素固体纳米粒子分散液中添加0.03重量份辛基醚磷酸酯阴离子表面活性剂和69.97重量份硫酸镁水溶性载体，以转速1200rpm搅拌均匀，再使用由精宏公司以商品名XMTD-822销售的设备在40℃条件下进行真空干燥去除水分，于是制备得到所述多杀菌素纳米固体分散体。
将本实施例制备得到的多杀菌素杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为210nm,悬浮率为98％，润湿时间为40s。
实施例4：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将25重量份氟乐灵除草剂加热达到高于其熔点49℃约10℃，倒入水 中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速6000rpm的条件下剪切12min，将氟乐灵均匀分散在水中，冷却至常温，得到一种氟乐灵固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的氟乐灵固体纳米粒子分散液中添加17重量份多苯乙烯苯酚聚氧乙烯醚非离子表面活性剂和58重量份尿素水溶性载体，以转速5000rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的设备在10pa条件下进行冷冻干燥去除水分，于是制备得到所述氟乐灵纳米固体分散体。
将本实施例制备得到的氟乐灵除草剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为256nm，悬浮率为98％，润湿时间为47s。
实施例5：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将18重量份霜霉威盐酸盐杀菌剂加热达到高于其熔点55℃约10℃，倒入水中，再使用由ATS公司以商品名AH-100D销售的高压均质机在压力800bar的条件下均质10min，将霜霉威盐酸盐均匀分散在水中，冷却至常温，得到一种霜霉威盐酸盐固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的霜霉威盐酸盐固体纳米粒子分散液中添加12重量份异丙苯基酚聚氧乙烯醚甲醛缩合物非离子表面活性剂、64重量份尿素与硫酸钠混合物(重量比1:1)、6重量份聚乙二醇与黄原胶混合物(重量比1:2)辅助成分，以转速1000rpm搅拌均匀，再使用由上海一恒公司以商品名DHG-9070A销售的设备在60℃条件下进行加热烘干去除水分，于是制备得到所述霜霉威盐酸盐纳米固体分散体。
将本实施例制备得到的霜霉威盐酸盐杀菌剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为324nm，悬浮率为99％，润湿时间为42s。
实施例6：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将5.9重量份氟菌唑杀菌剂加热达到高于其熔点63.5℃约10℃，倒入水中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速10000rpm的条件下剪切18min，将氟菌唑均匀分散在水中，冷却至常温，得到一种氟菌唑固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的氟菌唑固体纳米粒子分散液中添加0.001重量份苄基酚聚氧乙烯醚甲醛缩合物非离子表面活性剂、70重量份硫酸钠与硫酸镁混合物(重量比2:3)、24.099重量份聚乙二醇与硅酸镁铝混合物(重量比3:1)水溶性载体辅助成分，以转速3000rpm搅拌均匀，再使用由BUCHI公司以商品名R-210销售的设备在35℃水浴和12mbar的条件下进行减压蒸发去除水分，于是制备得到所述氟菌唑纳米固体分散体。
将本实施例制备得到的氟菌唑杀菌剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为67nm，悬浮率为99.4％，润湿时间为31s。
实施例7：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将90.0重量份甲草胺除草剂加热达到高于其熔点41.5℃约10℃，倒入水中，再使用由ATS公司以商品名AH-100D销售的高压均质机在压力800bar的条件下均质12min，将甲草胺均匀分散在水中，冷却至常温，得到一种甲草胺固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的甲草胺固体纳米粒子分散液中添加5.0重量份十二烷基羟丙基磺基甜菜碱两性表面活性剂、5.0重量份尿素水溶性载体，以转速2000rpm搅拌均匀，再使用由精宏公司以商品名XMTD-822销售的设备在40℃条件下进行真空干燥去除水分，于是制备得到所述甲草胺纳米固体分 散体。
将本实施例制备得到的甲草胺除草剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为263nm，悬浮率为98.7％，润湿时间为37s。
实施例8：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将20.0重量份正三十烷醇植物生长调节剂加热达到高于其熔点87℃约5℃，倒入水中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速18000rpm的条件下剪切15min，将正三十烷醇均匀分散在水中，冷却至常温，得到一种正三十烷醇固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的正三十烷醇固体纳米粒子分散液中添加8.0重量份十二烷基甜菜碱、72重量份硫酸钠水溶性载体，以转速2600rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的设备在10pa条件下进行冷冻干燥去除水分，于是制备得到所述正三十烷醇纳米固体分散体。
将本实施例制备得到的正三十烷醇植物生长调节剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为430nm，悬浮率为98％，润湿时间为42s。
实施例9：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将0.001重量份溴氰菊酯杀虫剂加热达到高于其熔点101℃约5℃，接着把溴氰菊酯倒入乙二醇溶剂中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速25000rpm的条件下剪切18min，将溴氰菊酯均匀分散在乙二醇中，接着冷却至常温，得到一种溴氰菊酯固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的溴氰菊酯固体纳米粒子分散液中添加含有50.0重量份 双十二烷基醚磷酸酯盐阴离子表面活性剂、49.999重量份蔗糖的水溶液，以转速1100rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的冷冻干燥设备在5pa条件下进行冷冻干燥去除溶剂，于是制备得到所述溴氰菊酯纳米固体分散体。
将本实施例制备得到的溴氰菊酯杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为85nm，悬浮率为99％，润湿时间为42s。
实施例10：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将29.0重量份噻嗪酮杀虫剂加热达到其熔点105℃，接着把噻嗪酮倒入二甲基甲酰胺中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速16000rpm的条件下剪切14min，将噻嗪酮均匀分散在二甲基甲酰胺中，冷却至常温，得到一种噻嗪酮固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的噻嗪酮固体纳米粒子分散液中添加含有10重量份辛基醚磷酸酯阴离子表面活性剂、10重量份十八烷基二羟乙基氧化胺两性表面活性剂、51重量份乳糖水溶性载体的水溶液，以转速2200rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的设备在5Pa条件下进行冷冻干燥去除溶剂，于是制备得到所述噻嗪酮纳米固体分散体。
将本实施例制备得到的噻嗪酮杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为342nm，悬浮率为97.5％，润湿时间为48s。
实施例11：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将90.0重量份联苯***醇杀菌剂加热达到高于其熔点125℃约5℃，接着把联苯***醇倒入二甲基甲酰胺中，再使用由ATS公司以商品名AH-100D销售的高压均质机在压力800bar的条件下均质18min，将所述联 苯***醇均匀分散在二甲基甲酰胺中，冷却至常温，得到一种联苯***醇固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的联苯***醇固体纳米粒子分散液中添加含有0.001重量份脂肪醇聚氧乙烯磷脂酸盐阴离子表面活性剂、9.999重量份羟丙基甲基纤维素水溶性载体的水溶液，以转速2200rpm搅拌均匀，再使用由精宏公司以商品名XMTD-822销售的真空干燥设备在40℃条件下去除溶剂，于是制备得到所述联苯***醇纳米固体分散体。
将本实施例制备得到的联苯***醇杀菌剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为560nm，悬浮率为96.5％，润湿时间为50s。
实施例12：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将50.0重量份硅氟唑杀菌剂加热达到高于其熔点118.5℃约5℃，接着把硅氟唑倒入乙二醇中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速16000rpm的条件下剪切14min，将所述硅氟唑均匀分散在乙二醇中，冷却至常温，得到一种硅氟唑固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的硅氟唑固体纳米粒子分散液中添加含有45.0重量份聚乙烯吡咯烷酮非离子表面活性剂、5.0重量份羟乙基纤维素水溶性载体的水溶液，以转速3500rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的设备在5Pa条件下进行冷冻干燥去除溶剂，于是制备得到所述硅氟唑纳米固体分散体。
将本实施例制备得到的硅氟唑杀菌剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为350nm，悬浮率为98％，润湿时间为33s。
实施例13：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将0.05重量份吡嘧磺隆除草剂加热达到其熔点178℃，接着把吡嘧磺隆倒入乙二醇中，再使用由ATS公司以商品名AH-100D销售的高压均质机在压力1200bar的条件下均质10min，将所述吡嘧磺隆均匀分散在乙二醇中，冷却至常温，得到一种吡嘧磺隆固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的吡嘧磺隆固体纳米粒子分散液中添加含有0.05重量份聚氧乙烯脱水山梨醇单油酸酯非离子表面活性剂、49.9重量份羧甲基纤维素钠、50重量份聚乙二醇与黄原胶混合物(重量比1:2)的水溶液，以转速3200rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的设备在5Pa条件下进行冷冻干燥去除溶剂，于是制备得到所述吡嘧磺隆纳米固体分散体。
将本实施例制备得到的吡嘧磺隆除草剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为482nm，悬浮率为98％，润湿时间为35s。
实施例14：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将17.0重量份丁酰肼植物生长调节剂加热达到高于其熔点157℃约5℃，接着把所述丁酰肼倒入乙二醇中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速15000rpm的条件下剪切15min，将所述丁酰肼均匀分散在乙二醇中，冷却至常温，得到一种丁酰肼固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的丁酰肼固体纳米粒子分散液中添加含有8.0重量份山梨糖醇酐油酸酯非离子表面活性剂、70重量份羟乙基-β-环糊精、5重量份聚乙二醇与硅酸镁铝混合物(重量比3:1)的水溶液，以转速1800rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的冷冻干燥设备在5Pa条件下进行去除溶剂，于是制备得到所述丁酰肼纳米固体分散体。
将本实施例制备得到的丁酰肼植物生长调节剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为490nm，悬浮率为98.5％，润湿时间为40s。
实施例15：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将25重量份阿维菌素杀虫剂溶于丙酮中，接着向其中加入25重量份脂肪醇聚氧乙烯醚羧酸盐阴离子表面活性剂和50重量份乳糖水溶性载体的水溶液，搅拌均匀后，使用由ATS公司以商品名C25销售的高速剪切乳化机在转速18000rpm的条件下剪切12min，再使用由EYELA公司以商品名N-2100销售的旋转蒸发设备在45℃条件下去除溶剂，于是制备得到所述阿维菌素纳米固体分散体。
将本实施例制备得到的阿维菌素杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为95nm，悬浮率为99％，润湿时间为25s。
实施例16：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将45重量份甲氨基阿维菌素苯甲酸盐杀虫剂溶于乙酸乙酯中，接着向其中加入25重量份马来松香聚氧乙烯-氧丙烯醚磺酸盐、15重量份十二烷基苯磺酸钠阴离子表面活性剂和15重量份尿素水溶性载体的水溶液，搅拌均匀后，使用由ATS公司以商品名AH-100D销售的高压均质机在压力800bar下均质12min，再使用由EYELA公司以商品名SD-1000销售的喷雾干燥设备在进风温度120℃，出风温度95℃，喷雾压力20kPa，进样速度0.09L/h条件下去除溶剂，制备得到所述甲氨基阿维菌素苯甲酸盐纳米固体分散体。
将本实施例制备得到的甲氨基阿维菌素苯甲酸盐杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为87nm，悬浮率为99％，润湿时间为23s。
实施例17：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将90.0重量份咪鲜胺杀菌剂溶于氯仿中，接着向其中加入3.5重量份双十二烷基醚磷酸酯盐、1.5重量份十二烷基苯磺酸钠阴离子表面活性剂和5.0重量份蔗糖水溶性载体的水溶液，搅拌均匀后，使用由ATS公司以商品名C25销售的高速剪切乳化机在转速10000rpm的条件下剪切18min，再使用由EYELA公司以商品名N-2100销售的旋转蒸发设备在30℃条件下去除溶剂，制备得到所述咪鲜胺纳米固体分散体。
将本实施例制备得到的咪鲜胺杀菌剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为550nm，悬浮率为97.5％，润湿时间为42s。
实施例18：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将0.05重量份噻呋酰胺杀菌剂溶于氯仿中，接着向其中加入0.05重量份油基缩二脲两性表面活性剂、99.9重量份尿素与硫酸钠混合物(重量比3:1)水溶性载体，以转速4200rpm搅拌均匀，再使用由EYELA公司以商品名N-2100销售的旋转蒸发设备在30℃条件下去除溶剂，制备得到所述噻呋酰胺纳米固体分散体。
将本实施例制备得到的噻呋酰胺杀菌剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为620nm，悬浮率为97％，润湿时间为48s。
实施例19：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将65重量份禾草灵除草剂溶于丙酮中，接着向其中加入11.0重量份十八烷基二羟乙基氧化胺两性表面活性剂、12.0重量份硫酸镁和12.0重量份硅酸镁铝水溶性载体,以转速5000rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的设备在10pa条件下进行冷冻干燥去除溶剂，制备得到所述禾草灵纳米固体分散体。
将本实施例制备得到的禾草灵除草剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为190nm，悬浮率为98％，润湿时间为38s。
实施例20：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将20重量份酰嘧磺隆除草剂溶于甲醇中，接着向其中加入50重量份油基缩二脲两性表面活性剂、25重量份尿素与硫酸钠混合物(重量比3:1)、5重量份聚乙二醇与硅酸镁铝混合物(重量比3:5)的水溶液,使用由ATS公司以商品名C25销售的高速剪切乳化机在转速10000rpm的条件下剪切8min，再使用由EYELA公司以商品名FD-81销售的设备在10pa条件下进行冷冻干燥去除溶剂，制备得到所述酰嘧磺隆纳米固体分散体。
将本实施例制备得到的酰嘧磺隆除草剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为220nm，悬浮率为98％，润湿时间为33s。
实施例21：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将0.001重量份苄氨基嘌呤植物生长调节剂溶于甲醇中，接着向其中加入25重量份蓖麻油聚氧乙烯醚非离子表面活性剂、25重量份十二烷基甜菜碱两性表面活性剂、30重量份尿素与蔗糖混合物(重量比1:1)和19.999重量份聚乙二醇水溶性载体的水溶液,以转速4200rpm搅拌均匀，再使用由EYELA公司以商品名SD-1000销售的喷雾干燥设备在进风温度120℃，出风温度95℃，喷雾压力20kPa，进样速度0.1L/h条件下去除溶剂，制备得到所述苄氨基嘌呤纳米固体分散体。
将本实施例制备得到的苄氨基嘌呤植物生长调节剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为85nm，悬浮率为99％，润湿时间为22s。
实施例22：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将42.0重量份吡啶醇植物生长调节剂溶于氯仿中，接着向其中加入0.001重量份脂肪醇聚氧乙烯醚羧酸盐阴离子表面活性剂、57.999重量份蔗糖水溶性载体的水溶液，使用由ATS公司以商品名C25销售的高速剪切乳化机在转速10000rpm的条件下剪切15min，制备得到所述吡啶醇纳米固体 分散体。
将本实施例制备得到的吡啶醇植物生长调节剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为250nm，悬浮率为98％，润湿时间为32s。
实施例23：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将10重量份高效氯氟氰菊酯杀虫剂和5重量份多杀菌素杀虫剂加热到90℃，倒入水中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速10000rpm的条件下剪切20min，将所述高效氯氟氰菊酯和多杀菌素均匀分散在水中，接着冷却至常温，得到一种含有上述杀虫剂的固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的固体纳米粒子分散液中添加15.0重量份十二烷基磺酸钠、15.0重量份聚羧酸盐阴离子表面活性剂和45重量份尿素，以转速1000rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的设备在5pa条件下进行冷冻干燥去除水分，于是制备得到所述高效氯氟氰菊酯·多杀菌素纳米固体分散体。
将本实施例制备得到的高效氯氟氰菊酯·多杀菌素杀虫剂纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为175nm，悬浮率为99％，润湿时间为35s。
实施例24：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将30重量份多杀菌素杀虫剂和30重量份氟乐灵除草剂加热到90℃，倒入水中，再使用由ATS公司以商品名AH-100D销售的高压均质机在压力1200bar的条件下均质20min，将所述多杀菌素和氟乐灵均匀分散在水中，接着冷却至常温，得到一种含有多杀菌素和氟乐灵的固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的固体纳米粒子分散液中添加10.0重量份十二烷基磺酸钠、5.0重量份聚羧酸盐阴离子表面活性剂和22重量份尿素水溶性载体，以转速1200rpm搅拌均匀，再使用由EYELA公司以商品名SD-1000销售的喷雾干燥设备在进风温度120℃，出风温度95℃，喷雾压力20kPa，进样速度0.1L/h条件下去除水分，于是制备得到所述多杀菌素·氟乐灵纳米固体分散体。
将本实施例制备得到的多杀菌素·氟乐灵纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为320nm，悬浮率为98.7％，润湿时间为43s。
实施例25：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将6重量份霜霉威盐酸盐杀菌剂和24重量份甲草胺除草剂加热到65℃，倒入水中，再使用由ATS公司以商品名AH-100D销售的高压均质机在压力1000bar的条件下均质20min，将所述霜霉威盐酸盐和甲草胺均匀分散在水中，接着冷却至常温，得到一种含有上述杀菌剂和除草剂的固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的固体纳米粒子分散液中添加12.0重量份十二烷基磺酸钠阴离子表面活性剂、8.0重量份异丙苯基酚聚氧乙烯醚甲醛缩合物非离子表面活性剂和50重量份尿素与硫酸钠混合物(重量比1:1)，以转速1000rpm搅拌均匀，再使用由EYELA公司以商品名FD-81销售的冷冻干燥设备在5pa条件下进行冷冻干燥去除水分，于是制备得到所述霜霉威盐酸盐·甲草胺纳米固体分散体。
将本实施例制备得到的霜霉威盐酸盐·甲草胺纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为255nm，悬浮率为98.2％，润湿时间为29s。
实施例26：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
A、制备纳米分散液
将27.0重量份溴氰菊酯杀虫剂和20.0重量份硅氟唑杀菌剂加热达到120℃，接着把所述杀虫剂和杀菌剂倒入辛烷中，再使用由ATS公司以商品名C25销售的高速剪切乳化机在转速15000rpm的条件下剪切15min，将所述溴氰菊酯和硅氟唑均匀分散在辛烷中，冷却至常温，得到一种含有上述杀虫剂和杀菌剂的固体纳米粒子分散液；然后
B、制备纳米固体分散体
往步骤A得到的固体纳米粒子分散液中添加含有13.0重量份十八烷基二羟乙基氧化胺两性表面活性剂、32重量份硫酸镁、8重量份硅酸镁铝水溶性载体辅助成分，以转速4000rpm搅拌均匀，再使用由开封宏兴公司以商品名S212销售的蒸馏设备在150条件下进行蒸馏去除溶剂，于是制备得到所述溴氰菊酯·硅氟唑的纳米固体分散体。
将本实施例制备得到的溴氰菊酯·硅氟唑纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为172nm，悬浮率为98.5％，润湿时间为34s。
实施例27：制备本发明的农药纳米固体分散体
该实施例的实施步骤如下：
将18重量份高效氯氟氰菊酯杀虫剂和18重量份阿维菌素杀虫剂溶于丙酮中，接着向其中加入15重量份马来松香聚氧乙烯-氧丙烯醚磺酸盐阴离子表面活性剂、15重量份异丙苯基酚聚氧乙烯醚甲醛缩合物非离子表面活性剂、34重量份蔗糖水溶性载体的水溶液，使用由ATS公司以商品名C25销售的高速剪切乳化机在转速10000rpm的条件下剪切15min，再使用由EYELA公司以商品名FD-81销售的设备在5pa条件下进行冷冻干燥去除溶剂，制备得到高效氯氟氰菊酯·阿维菌素纳米固体分散体。
将本实施例制备得到的高效氯氟氰菊酯·阿维菌素纳米固体分散体用蒸馏水进行分散，再使用由Malvern公司生产的Nano ZS90激光粒度仪测得其平均粒径为67nm，悬浮率为99.5％，润湿时间为21s。

Claims (10)

  1. 一种农药纳米固体分散体，其特征在于它是由难溶性农药纳米粒子均匀地分散在表面活性剂和水溶性载体中所形成的农药纳米固体分散体，以重量份计，它的组成如下：
    农药          0.001-90；
    表面活性剂    0.001-50；
    水溶性载体    5-99.9；
    所述的农药是一种或多种选自难溶性的杀虫剂、杀菌剂、除草剂或植物生长调节剂的农药；
    所述的农药纳米粒子的平均粒径为1-1000nm；
    所述的农药纳米固体分散体的形态为粉剂、片剂、颗粒剂或微胶囊剂型。
  2. 根据权利要求1所述的农药纳米固体分散体，其特征在于所述的杀虫剂选自拟除虫菊酯、氨基甲酸酯、有机磷、有机硫、有机胆碱、沙蚕毒素、新烟碱、苯基酰尿、阿维菌素、哒螨灵、灭螨醌、苯基吡唑、茚虫威或丁醚脲类杀虫剂；
    所述的杀菌剂选自苯胺基吡啶、抗生素、芳族烃、二硝基苯胺、烯丙胺、苯磺酰胺、苯并咪唑、苯并异噻唑、二苯甲酮、苯并基嘧啶、苯并三嗪、氨基甲酸苄酯、氨基甲酸酯、羧酰胺、羧酸二酰胺、氯腈、氰基咪唑、环丙烷羧酰胺、乙基氨基噻唑羧酰胺、咪唑、羟基酰替苯胺、咪唑啉酮、异苯并呋喃酮、甲氧基丙烯酸酯、甲氧基氨基甲酸酯、吗啉、N-苯基氨基甲酸酯、噁唑烷二酮、苯基乙酰胺、苯基酰胺、苯基吡咯、苯脲、硫代磷酸酯、邻氨甲酰苯甲酸、邻苯二甲酰亚胺、哌嗪、哌啶、丙酰胺、吡啶、吡啶基甲基酰胺、甲苯酰胺、三嗪或***类杀菌剂；
    所述的除草剂选自酰胺、芳氧基苯氧基丙酸酯、苯氧羧酸、有机磷、苯甲酰胺、苯并呋喃、苯甲酸、苯并噻二嗪酮、氨基甲酸酯、氯乙酰胺、吡啶羧酸、氯羧酸、环已二酮、二硝基苯胺、二苯醚、异恶唑、异恶唑烷酮、N-苯基邻苯二甲酰亚胺、噁二唑、噁唑烷二酮、氧基乙酰胺、苯基氨 基甲酸酯、苯基哒嗪、磺基氨基羧基***啉酮、磺酰***并羧酰胺、***并嘧啶、三酮、尿嘧啶或脲类除草剂；
    所述的植物生长调节剂选自青鲜素、萘乙酸甲酯、6-苄基氨基嘌呤、油菜素内酯、氨氧乙基乙烯基甘氨酸或多效唑类植物生长调节剂。
  3. 根据权利要求1所述的农药纳米固体分散体，其特征在于所述的表面活性剂是一种或多种选自阳离子表面活性剂、阴离子表面活性剂、非离子表面活性剂或两性表面活性剂的表面活性剂；
    所述阳离子表面活性剂选自脂肪胺盐、乙醇胺盐、聚乙烯多胺盐或季铵盐阳离子表面活性剂；
    所述阴离子表面活性剂选自十二烷基磺酸钠、十二烷基硫酸钠、十二烷基苯磺酸钠、马来松香聚氧乙烯-氧丙烯醚磺酸盐、烷基酚聚氧乙烯醚磷酸酯盐、单十二烷基醚磷酸酯盐、双十二烷基醚磷酸酯盐、辛基醚磷酸酯、脂肪醇聚氧乙烯磷脂酸盐、脂肪醇聚氧乙烯醚羧酸盐、聚羧酸盐或木质素磺酸盐阴离子表面活性剂；
    所述非离子表面活性剂选自烷基酚聚氧乙烯醚甲醛缩合物、苯乙烯基酚聚氧乙烯醚甲醛缩合物、多苯乙烯苯酚聚氧乙烯醚、异丙苯基酚聚氧乙烯醚甲醛缩合物、苄基酚聚氧乙烯醚甲醛缩合物、蓖麻油聚氧乙烯醚、聚乙烯吡咯烷酮、聚氧乙烯脱水山梨醇单油酸酯、山梨糖醇酐油酸酯、聚氧乙烯聚氧丙烯嵌段共聚物或蔗糖单油酸酯非离子表面活性剂；
    所述两性表面活性剂选自十二烷基羟丙基磺基甜菜碱、十二烷基甜菜碱、十八烷基二羟乙基氧化胺、十八烷基脲或油基缩二脲两性表面活性剂。
  4. 根据权利要求1所述的农药纳米固体分散体，其特征在于所述的水溶性载体选自尿素、硫酸钠、硫酸镁、苯甲酸钠、蔗糖、乳糖、可溶性淀粉、羟丙基甲基纤维素、羟乙基纤维素、羧甲基纤维素钠、羟乙基-β-环糊精、羟丙基-β-环糊精、磺酸基-β-环糊精、聚乙烯醇、聚乙二醇、黄原胶、硅酸镁铝、***胶、丙烯酸钠或聚乙烯吡咯烷酮载体。
  5. 权利要求1-4中任一权利要求所述农药纳米固体分散体的制备方法，其特征在于所述制备方法的步骤如下：
    A、制备纳米分散液
    将0.001-90重量份农药加热达到高于所述农药熔点，但低于其分解与变性温度的温度，接着把所述农药倒入水中，再使用高速剪切乳化机或高压均质机将所述农药均匀分散在水中，冷却至常温，得到一种农药固体纳米粒子分散液；然后
    B、制备纳米固体分散体
    往步骤A得到的农药固体纳米粒子分散液中添加0.001-50重量份表面活性剂和5-99.9重量份水溶性载体辅助成分，搅拌均匀，再采用加热烘干、减压蒸发、真空干燥或冷冻干燥方法去除水分，于是制备得到所述农药纳米固体分散体。
  6. 根据权利要求5所述的制备方法，其特征在于所述高速剪切乳化机的转速是1000-30000rpm，所述高压均质机的压力是50-1500bar；所述搅拌速度是50-5000rpm。
  7. 权利要求1-4中任一项权利要求所述农药纳米固体分散体的制备方法，其特征在于所述制备方法的步骤如下：
    A、制备纳米分散液
    将0.001-90重量份农药加热达到高于所述农药熔点的温度，接着把它倒入所述农药的不良溶剂中，再使用高速剪切乳化机或高压均质机将所述农药均匀分散在不良溶剂中，冷却至常温，得到一种农药固体纳米粒子分散液；然后
    B、制备纳米固体分散体
    往步骤A得到的农药固体纳米粒子分散液中添加含有0.001-50重量份表面活性剂和5-99.9重量份水溶性载体辅助成分的水溶液，搅拌均匀，再采用冷冻干燥、喷雾干燥、离心及蒸馏去除不良溶剂和水，于是制备得到所述的农药纳米固体分散体。
  8. 根据权利要求7所述的制备方法，其特征在于所述高速剪切乳化机的转速是1000-30000rpm，所述高压均质机的压力是50-1500bar；所述搅拌速度是50-5000rpm。
  9. 权利要求1-4中任一项权利要求所述农药纳米固体分散体的制备方法，其特征在于所述制备方法的步骤如下：
    将0.001-90重量份农药用所述农药良溶剂溶解，然后加入0.001-50重量份表面活性剂、5-99.9重量份水溶性载体与0-50重量份水，混合均匀，再使用高速剪切乳化机或高压均质机进行分散，接着进行蒸馏、减压蒸发、喷雾干燥、冷冻干燥或烘干，除去溶剂，于是制备得到所述的农药纳米固体分散体。
  10. 根据权利要求9所述的制备方法，其特征在于所述高速剪切乳化机的转速是1000-30000rpm，所述高压均质机的压力是50-1500bar。
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