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WO2020135600A1 - Formulation de nano-pesticide et procédé de préparation - Google Patents

Formulation de nano-pesticide et procédé de préparation Download PDF

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WO2020135600A1
WO2020135600A1 PCT/CN2019/128757 CN2019128757W WO2020135600A1 WO 2020135600 A1 WO2020135600 A1 WO 2020135600A1 CN 2019128757 W CN2019128757 W CN 2019128757W WO 2020135600 A1 WO2020135600 A1 WO 2020135600A1
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Prior art keywords
pesticide
water
nano
preparation
miscible
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PCT/CN2019/128757
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English (en)
Chinese (zh)
Inventor
张子勇
梁冰
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南京善思生物科技有限公司
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Priority claimed from CN201811618803.8A external-priority patent/CN109673631A/zh
Priority claimed from CN201811618804.2A external-priority patent/CN109744245A/zh
Priority claimed from CN201811618956.2A external-priority patent/CN109645014A/zh
Priority claimed from CN201811618802.3A external-priority patent/CN109757487A/zh
Priority claimed from CN201811618805.7A external-priority patent/CN109673649A/zh
Priority claimed from CN201811632002.7A external-priority patent/CN109757509A/zh
Priority claimed from CN201811632136.9A external-priority patent/CN109757499A/zh
Priority claimed from CN201811632004.6A external-priority patent/CN109744239A/zh
Priority claimed from CN201811632005.0A external-priority patent/CN109673633A/zh
Priority claimed from CN201811632003.1A external-priority patent/CN109673632A/zh
Priority claimed from PCT/IB2019/057429 external-priority patent/WO2020136451A1/fr
Application filed by 南京善思生物科技有限公司 filed Critical 南京善思生物科技有限公司
Priority to CN201980086511.0A priority Critical patent/CN113260257B/zh
Publication of WO2020135600A1 publication Critical patent/WO2020135600A1/fr

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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
    • 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
    • A01N25/12—Powders or granules

Definitions

  • the invention belongs to the technical field of pesticides, and relates to a nano pesticide preparation and a preparation method thereof, in particular to a preparation method of a miscible nano pesticide suspension agent, a nano pesticide suspension agent, and a nano pesticide solid powder.
  • Nanopesticides have been selected as the top of emerging technologies based on the growing population of the world. It is predicted that the world’s population will be close to 10 billion by 2050. In order to feed a large number of people, it is necessary to greatly increase agricultural output and minimize the environmental impact on land use, including reducing pesticide pollution, reducing water consumption, and reducing the number of people. Nano pesticides and their delivery systems will be a good tool to solve the main problems of traditional pesticides. These problems include environmental pollution, the accumulation of pesticides in organisms and the substantial increase in resistance to diseases and insect pests. Nano pesticide particles are small in size, and the target has better absorption. Although it cannot be said that it is the only path for sustainable development of agriculture, it is certain that it has less impact on the ecological environment and human health.
  • Nanometer also known as nanometer, is a unit of length. 1nm is one billionth of a meter (10 -9 m) or one millionth of a millimeter (10 -6 mm).
  • nano pesticides refer to pesticide preparations whose particle size of pesticide active ingredients is in the nanometer order. The order of nanometers usually includes a few to several hundred nanometers.
  • nanopesticide can be used to describe any pesticide formulation including the following: 1
  • the active ingredient particles of the formulation are in the nanometer size range, generally a few to several hundred nanometers; 2
  • the formulation is formed with the specified "nano" as a prefix Substances, such as nano-grains, nano-hybrids, nano-composites, nano-microspheres, nano-capsules, etc.; 3 preparations with novel characteristics related to small-size particles, such as huge surface area and excellent control effect
  • pesticides can be roughly divided into three categories according to their solubility in water: one is water-soluble pesticides, and the number of these types of pesticides is not large, accounting for about 8%; the second category is pesticides that are hardly soluble in water or insoluble in water, but can be dissolved in a certain type of organic solvent, this type of pesticide accounts for about 50%; the third category is both insoluble in water and insoluble in organic solvents The pesticide is close to 20%. The remaining pesticides are of unclear nature, or biological or gaseous pesticides.
  • Pesticides soluble in water are monomolecularly dispersed in water and belong to true solutions. Since most pesticides are small molecule organic compounds, the molecular size is generally less than 1 nanometer. Because the molecular size is smaller than the nano size, this part of water-soluble pesticide need not be prepared as a nano pesticide. It can be seen that nano pesticides are for water-insoluble pesticides. Since they cannot be dissolved in water, they can only aggregate. Therefore, it is hoped that the aggregates in water can be dispersed in the smallest possible size, that is, the nano size, from several nanometers. , To tens or hundreds of nanometers, this is nano pesticides.
  • nano-pesticides Compared with traditional pesticide preparations, nano-pesticides have four obvious advantages: One is the improvement of drug efficacy. Due to the small size of the active ingredient particles, the same quality of drugs, the number of particles is greater, and the area contacting the crop target is larger, so under the same plant protection effect, the amount of pesticides can be significantly reduced. Second, the preparation is stable. The smaller the size of the nano pesticide particles dispersed in water, the better the transparency of the preparation, achieving apparent water solubility and thermodynamic stability. Through performance control, it can be diluted with water without precipitation or precipitation of pesticides, which makes the use of pesticides more efficient and convenient. The third is green.
  • nano pesticides can be developed into green and environmentally friendly formulations that use water as a dispersion medium, natural substances or their derivatives as additives, and do not use highly toxic benzene solvents and additives, thus fundamentally solving Agricultural non-point source pollution caused by pesticide application.
  • the fourth is manufacturing safety.
  • the original intention of studying nano-pesticides is to improve the efficacy of pesticides and reduce the amount of pesticides. In this process, high-toxic organic solvents and additives are not used. Organic solvents are replaced or partially replaced with water. All these measures not only mark nano Pesticides are highly efficient and environmentally friendly, and also show that they are safer than traditional pesticide formulations such as emulsifiable concentrates in production, storage, transportation, and operation. Because of this, nano-pesticides have become a hotspot in which countries around the world are competing in research and development.
  • the first category is nano pesticides that improve the apparent solubility of pesticides.
  • the purpose of this type of nano pesticide formulation is to increase the apparent solubility of the water-insoluble pesticide active ingredient.
  • the size of pesticide particles dispersed in water is less than one-quarter of the visible light wavelength (400-760nm)
  • the incident light does not cause serious refraction and reflection, and the solution exhibits the properties of apparent water solubility and transparent appearance, thereby improving the Apparent solubility in water.
  • Such nano pesticides include: microemulsion, nanoemulsion, nanodispersant, etc.
  • the second category is nano-pesticides that protect nano-pesticide particles and impart slow-release or controlled-release properties.
  • the original intention of developing slow-release or controlled-release preparations was mainly to address the problem of premature degradation or deviation from targeting of pesticide active ingredients, and also to the case of active ingredients with low water solubility. It is recognized that after spraying, most of the active ingredients of pesticides will be degraded or decomposed by environmental factors (ultraviolet light, oxygen, heat), which will affect the effectiveness of the drug. In order to achieve slow or controlled release of pesticides, it is necessary to protect the active ingredients from premature decomposition. The way to protect is to use carrier substances.
  • the carrier material is divided into a soft carrier (polymer, solid liposome) and a hard carrier (porous hollow nano-SiO 2 , layered double metal hydroxide (LDH) and clay).
  • these types of nano pesticides include nano pesticide microspheres, nano pesticide gels, nano pesticide fibers, nano pesticide liposomes, nano pesticide hollow porous SiO 2 , nano pesticide LDH, nano pesticide clay, etc. .
  • Nano-metals such as silver (Ag) and nano-oxides such as titanium dioxide (TiO 2 ) are typical inorganic substances, each with its own special properties. They can be used alone or in combination with pesticide nanoparticles to form nanometal or nanometal oxide pesticide formulations.
  • Ag has well-known antibacterial properties. Nano Nano Ag can significantly inhibit the growth of plant pathogens in a dose-dependent manner. Nano-TiO 2 is called a photocatalyst, and it can catalyze and decompose organic substances under the action of ultraviolet light.
  • This type of nano pesticide formulation includes two types: one is nano metal and nano metal oxide used alone; the other is nano pesticide used in combination with nano metal or nano metal oxide.
  • nano-pesticides for application in agricultural production, specifically, to improve the efficacy, reduce the amount of pesticides, and reduce the impact on the ecological environment.
  • problems in the research and development of nano pesticides including: (1) The lack of common technology research. Most research and development are isolated and divergent research and exploration, usually for the preparation and characterization of nano pesticides for a certain pesticide variety; (2) Lack of directionality and overall thinking and design for the development of nano pesticide research, the research is not systematic and in-depth. (3) Lack of knowledge of relevant cross-disciplines, and some studies are biased without knowing it. (4) Lack of practicality. The vast majority of research is limited to laboratory results, and it is difficult to realize the industrialization and commercialization of nano pesticides. For the latter, it is mainly related to the difficulty of the preparation method of nano pesticides, the control of process operation flow, the performance control of nano pesticides, and the availability and cost performance of additives.
  • nano-pesticide does not mean that it is inherently environmentally friendly. Only by establishing the concept of green environmental protection in the research and development process, without using highly toxic benzene solvents and toxic auxiliary agents, such as nonylphenol polyoxyethylene ether feminizing agents, can we obtain green environmentally friendly nano pesticides.
  • the present invention relates to some specific terms. Among these specialized terms, some of which are well-known to those skilled in the art, and others are for the convenience of the description of the present invention, some components and intermediate products obtained are specifically labeled, and only represent the prescribed meanings. Some terms are described in Table-1.
  • the primary purpose of the present invention is to overcome the shortcomings of the prior art, and to provide new green and environmentally friendly nano pesticide preparations, especially miscible nano pesticide suspension agents, nano pesticide suspension agents and nano pesticide solid powders.
  • the miscible nano-suspending agent, nano-suspending agent and nano-powder described in the present invention have the characteristics of being better than existing emulsifiable concentrates, suspending agents, water emulsions, wettable powders, dispersible granules, water-dispersible granules and other dosage forms: (1) pesticides
  • the nanometer size of the particles is dispersed, which is 2 to 3 orders of magnitude smaller than the micrometer size of the existing pesticide formulation particles.
  • the same quality of the pesticide active ingredient has more particles and a larger specific surface area, which is more conducive to improving the efficacy .
  • (3) The performance of miscible nano-suspending agent, nano-suspending agent and nano-powder is stable, and the performance index conforms to relevant national regulations.
  • the technology of the present invention is relatively uncomplicated, which is beneficial to the industrialization of nano pesticides.
  • Another object of the present invention is to provide a method for preparing green and environmentally friendly nano pesticide preparations, especially miscible nano suspending agents, nano suspending agents and nano solid powders.
  • the preparation process is also different.
  • the preparation of the traditional suspending agent requires the use of a high-speed shearing machine for initial crushing, and then it is transferred to a continuous sand mill for grinding with additives. Therefore, the preparation of traditional suspending agents requires the purchase of corresponding high-speed pulverizers, grinders and other mechanical equipment, and the preparation operations go through different processes. In addition, the performance of the formulation is different.
  • the method and process for preparing the miscible nano-suspending agent and the nano-suspending agent of the present invention have the following significant advantages: (1) The equipment used is simple. The required equipment is only a stirring kettle with a controllable stirring speed, a reflux condenser, and a vacuum distillation operation under heating conditions.
  • the operation is not complicated, including controlling the drop acceleration, heating and decompressing the solvent recovery.
  • (3) The manufacturing process is green and energy-saving. During the preparation process, although a certain amount of organic solvent is used, the low-toxic organic solvent is selected, and the solvent can be recovered through subsequent operations.
  • the invention provides a universal and effective method for preparing miscible nano-suspending agents, nano-suspending agents and nano-solid powders for many kinds of pesticides.
  • a nano pesticide preparation the raw and auxiliary materials of the preparation contain an effective amount of pesticide active ingredient or pesticide original drug, and an appropriate amount of solvent, high molecular adjuvant, small molecule adjuvant and dispersant.
  • the raw and auxiliary materials of the preparation contain the following mass percentage substances:
  • the raw and auxiliary materials of the preparation contain the following mass percentage substances:
  • the raw and auxiliary materials of the preparation contain the following mass percentage substances:
  • the raw and auxiliary materials of the preparation contain the following mass percentage substances:
  • the said nano pesticide preparation wherein the pesticide active ingredient or pesticide original drug is mainly a kind of pesticide that is insoluble in water but soluble in organic solvents; the solvent is one or more of organic solvents that can dissolve the pesticide active ingredient or pesticide original drug
  • Polymer additives are water-soluble natural polymers, water-soluble natural polymer derivatives, or water-soluble synthetic polymer materials; small molecular additives are mixed additives composed of anionic additives and nonionic additives, anionic additives
  • the mass percentage of the agent in the small molecule adjuvant is 1 to 99%, and the balance is non-ionic adjuvant, the total of the two is 100%, wherein the anionic adjuvant is a linear or branched hydrocarbon group of 8 to 18 carbon atoms or/ And aryl carboxylates, sulfonates, sulfates or phosphates, non-ionic additives are polyoxyethylene ether surfactants, polyol surfactants, or polyoxyethylene-polyoxypropy
  • the solvent includes a mixed solvent composed of at least one water-soluble solvent and at least one water-insoluble solvent, and the ratio between the two is pre-tested according to the pesticide and the type of solvent to determine the optimal ratio.
  • the mass ratio between the two is about 1:2.
  • the nano pesticide preparation wherein the polymer adjuvant is selected from starch and its derivatives (water-soluble starch, oxidized starch, carboxymethyl starch, modified starch, dextrin, cyclodextrin), cellulose and its derivatives (Carboxymethyl cellulose, hydroxyethyl hydroxypropyl cellulose), carboxymethyl chitosan, modified guar gum, tea saponin, water-soluble humic acid, sodium lignosulfonate, polyvinyl alcohol, poly Acrylic acid, polyacrylamide, polystyrene-maleic anhydride copolymer, one or more of water-soluble species in polyvinylpyrrolidone, the water-soluble species include salts of the above substances; the anionic auxiliary agent is selected from twelve Sodium alkyl sulfate, sodium dodecyl sulfonate, sodium dodecyl ether sulfate, sodium dodecyl monophosphate, sodium ⁇ -alkenyl s
  • the dosage form of the preparation is all dosage forms suitable for nano pesticides, preferably a miscible nano pesticide suspension agent, a nano pesticide suspension agent, a nano pesticide solid powder.
  • the nano pesticide preparation wherein the miscible nano pesticide suspension agent is an aqueous dispersion liquid in which nano crystal grains and sol-enriched beam coexist are formed by dropping the miscible prodrug solution into the aqueous solution of the composite auxiliary; the mixture
  • the lyotropic drug solution is a solution formed by dissolving pesticide pesticides in a mixed solvent
  • the composite auxiliary aqueous solution is an aqueous solution formed by separately dissolving a polymer auxiliary and a small molecule auxiliary in water
  • the mixed solvent is composed of At least two solvents are mixed according to a certain ratio;
  • the mixed solvent includes at least one water-soluble solvent and at least one water-insoluble solvent; each solvent must be able to dissolve the pesticide pesticide.
  • the miscible nano pesticide suspension agent wherein in the miscible nano pesticide suspension agent, the mass percentage of the miscible original drug solution and the composite auxiliary aqueous solution is 100%; the miscible original drug solution and the composite auxiliary aqueous solution
  • the mass percentage ranges are: 35% ⁇ 5%, 65% ⁇ 5%; preferably, the mass percentage ranges of the miscible original drug solution and the composite auxiliary solution are: 35% ⁇ 3%, 65% ⁇ 3% .
  • miscible nano pesticide suspension agent wherein in the miscible original drug solution, the mass percentage of the pesticide pesticide and the mixed solvent in the miscible nano pesticide suspension agent are respectively: 3% to 18 %, 17% to 32%; preferably, the mass percentages of the pesticide original drug and the mixed solvent in the miscible nano pesticide suspension are: 3% to 12% and 23% to 32%, respectively.
  • the miscible nano pesticide suspension agent wherein the small molecule auxiliary agent and the high molecular auxiliary agent together form a composite auxiliary agent; in the aqueous solution of the composite auxiliary agent, the composite auxiliary agent and water account for the miscibility
  • the range of the mass percentage of the nano pesticide suspension agent is: 22% to 28%, 35% to 45%; preferably, the range of the mass percentage of the composite auxiliary agent and water to the miscible nano pesticide suspension agent is: 23 % ⁇ 27%, 38% ⁇ 42%.
  • miscible nano pesticide suspension agent wherein the small molecule adjuvant and the polymer adjuvant account for the mass percentage of the miscible nano pesticide suspension agent are respectively: 12% to 22%, 2% to 7 %; preferably, the mass percentages of the small molecule adjuvant and the polymer adjuvant to the miscible nano pesticide suspension agent are respectively: 16% to 21%, 3% to 6%.
  • miscible nano pesticide suspension agent wherein the HLB value of the small molecule adjuvant is at least 13; preferably 14 or more.
  • miscible nano pesticide suspension agent wherein the small molecule auxiliary agent includes an anionic auxiliary agent and a non-ionic auxiliary agent.
  • miscible nano pesticide suspension agent wherein the anionic auxiliary agent is a carboxylate, sulfonate, sulfate or phosphate of a linear or branched hydrocarbon group or/and aryl group with 8 to 18 carbon atoms.
  • the anionic auxiliary agent is a sodium, potassium, or ammonium salt of a linear alkyl carboxylic acid having 8 to 18 carbon atoms, sulfonic acid, sulfuric acid, or phosphoric acid.
  • the miscible nano pesticide suspension agent wherein the non-ionic auxiliary agent is a polyoxyethylene ether surfactant, a polyol surfactant, or a polyoxyethylene-polyoxypropylene polyether surfactant;
  • the polyoxyethylene ether surfactants do not include nonylphenol polyoxyethylene ether surfactants.
  • the polymer aid is a water-soluble natural polymer, a water-soluble natural polymer derivative, or a water-soluble synthetic polymer substance.
  • the water-soluble natural polymer, the water-soluble natural polymer derivative, and the water-soluble synthetic polymer are easily biodegradable.
  • the miscible nano pesticide suspension agent wherein the pesticide original drug and the mixed solvent thereof are water-soluble and water-insoluble solvents from the following table:
  • the preparation method of the nano pesticide preparation includes the following steps:
  • the preparation method of the nano pesticide preparation wherein the other preparations include a nano pesticide suspension agent and a nano pesticide solid powder.
  • the method for preparing the nano pesticide preparation wherein the miscible nano pesticide suspension agent is formed by dropping a miscible original drug solution made of a certain pesticide original drug into an aqueous solution of a composite auxiliary agent, which has nano crystal grains and An aqueous dispersion in which sol beams coexist;
  • the preparation method of the miscible nano pesticide suspension agent includes the following steps:
  • miscible original drug solution add the pesticide original drug to the mixed solvent and dissolve by stirring to obtain a miscible original drug solution;
  • aqueous solution of compound additives First, one or several polymer additives are added to water under stirring, and if necessary, static swelling; after the polymer additives are fully swelled, stirring is started until completely dissolved, Generate a transparent polymer aqueous solution; then add one or more small molecule additives to the polymer aqueous solution, stir and dissolve to obtain a composite auxiliary solution;
  • miscible nano pesticide suspension agent Under the condition of controllable agitation speed, the miscible prodrug solution is added dropwise to the aqueous solution of the composite auxiliary; the drop acceleration and the agitation speed are controlled to produce a uniformly dispersed The nano pesticide grains finally complete the preparation of the miscible nano pesticide suspension agent.
  • the system by controlling the drop acceleration and/or stirring speed, the system is always kept in a transparent state.
  • the method of dropping includes single point dropping, multiple point dropping or spray dropping.
  • the preferred range of the stirring speed is 100-200 rpm.
  • the preparation method wherein, in the miscible nano pesticide suspension agent, the sum of the mass percentage of the miscible original drug solution and the composite auxiliary aqueous solution is 100%; the mass percentage of the miscible original drug solution and the composite auxiliary aqueous solution
  • the ranges are: 35% ⁇ 5%, 65% ⁇ 5%; preferably, the mass percentage ranges of the miscible original drug solution and the composite auxiliary aqueous solution are: 35% ⁇ 3%, 65% ⁇ 3%, respectively.
  • the preparation method wherein, in the miscible original drug solution, the mass percentage of the pesticide original drug and the mixed solvent in the miscible nano pesticide suspension agent are respectively: 3% to 18%, 17 % To 32%; preferably, the mass percentages of the pesticide original drug and the mixed solvent in the miscible nano pesticide suspension agent are respectively: 3% to 12%, 23% to 32%.
  • the preparation method wherein the small molecule auxiliary agent and the polymer auxiliary agent together constitute a composite auxiliary agent; in the aqueous solution of the composite auxiliary agent, the composite auxiliary agent and water account for the suspension of the miscible nano pesticide
  • the mass percentage range of the agent is: 22% ⁇ 28%, 35% ⁇ 45%; preferably, the mass percentage range of the composite auxiliary agent and water in the miscible nano pesticide suspension agent is: 23% ⁇ 27 %, 38% ⁇ 42%.
  • the preparation method wherein the mass percentages of the small molecule adjuvant and the polymer adjuvant to the miscible nano pesticide suspension agent are respectively: 12%-22%, 2%-7%; preferably The mass percentages of the small molecule adjuvant and the polymer adjuvant to the miscible nano pesticide suspension agent are respectively: 16%-21%, 3%-6%.
  • the HLB value of the small molecule adjuvant is at least 12; preferably 14 or more.
  • the preparation method wherein the preparation of the mixed solvent is carried out in a vessel equipped with a reflux condenser.
  • the preparation of the aqueous solution of the composite auxiliary agent is carried out in a vessel equipped with stirring, a reflux condenser, and a vessel capable of heating and vacuum distillation.
  • the preparation method of the nano-pesticide preparation wherein the preparation method of the nano-pesticide suspension agent, after completing the preparation of the miscible nano-pesticide suspension agent by the above method, further adopts one of the following two distillation recovery solvent methods to complete the nano-pesticide suspension Preparation of agent:
  • the heating temperature must be below the cloud point temperature of the nonionic surfactant.
  • the preparation method of the nano pesticide preparation wherein the preparation method of the nano solid powder is the miscible nano pesticide suspension prepared by the above method or the nano pesticide suspension prepared by the above method is spray dried to recover part or all After the solvent, a nanometer pesticide powder solid preparation is formed.
  • Macro precipitation refers to solid particles with a particle size greater than 1 micron.
  • the first step of the present invention is to select a mixed solvent that is miscible with pesticides.
  • the mixed solvent is formed by mixing at least two solvents in a certain ratio.
  • the selection principles include: (1) The solubility of the pesticide should be as good as possible so that the amount of solvent used is not too large; (2) The boiling point of the solvent should not be too high to facilitate recovery; (3) The toxicity should be as small as possible. When choosing, choose a solvent with low toxicity; (4) In the mixed solvent, each solvent must be able to dissolve the pesticide pesticide; divided into two categories: one is a solvent soluble in water; the other is a solvent insoluble in water . (5) The mixed solvent should include at least a solvent soluble in water and a solvent insoluble in water.
  • organic solvents There are many types of organic solvents. According to different structure types, they are mainly divided into: benzene solvents, alkane solvents, ketone solvents, ester solvents, alcohol solvents, and oil solvents.
  • the pesticides targeted by the present invention are mainly pesticide varieties that are insoluble in water but soluble in organic solvents.
  • the physical properties of pesticide varieties are generally listed, including the solubility of some solvents, but the information is not complete.
  • the dissolution properties of these solvents can be used as the choice of the solvent and mixed solvent used in the present invention.
  • Table-2 lists some important pesticide active ingredients, including fungicides, insecticides and herbicides.
  • the solvents that can be used are selected.
  • the data unit in parentheses is g/L, which is the grams of soluble pesticide active ingredient per liter.
  • the number of solvents without parentheses is not clear, which is used as a reference for the selection of composite solvents.
  • the method of the present invention is only used as an example, but is not limited to the types of pesticides listed in this table and the tables and the types of solvents that dissolve it.
  • solubility performance data of pesticide active ingredients provided in Table 2 above, the following empirical rules still exist for the selection of mixed solvents:
  • acetone soluble in water
  • water-insoluble ketone solvents formulated with it include cyclohexanone, methyl ethyl ketone, acetophenone, and their derivatives It has similar solubility to acetone.
  • water-soluble solvents for methanol, ethanol, isopropanol, acetonitrile, and tetrahydrofuran
  • the water-insoluble solvent compounded with it except ketone solvents, ethyl acetate insoluble in water is less toxic, The boiling point is not high, it is an alternative ester solvent, its homologues propyl acetate, isopropyl acetate, etc., have similar solubility.
  • Table-2 Compound solvents that can be selected for some different types of important pesticide varieties
  • the miscible nano pesticide suspension agent and the nano pesticide suspension agent prepared by the present invention need a compound auxiliary agent (system) in addition to the mixed solvent.
  • Compound additives include small molecule additives and polymer additives. Their components and functions are described below.
  • Small molecule additives are all surfactants, mainly including anionic surfactants and nonionic surfactants.
  • Anionic surfactant molecules are composed of hydrophilic polar groups and hydrophobic hydrocarbon groups. It dissociates into an ionic state in aqueous solution, with negatively charged acid radicals and positively charged metal ions around it. From the chemical structure, it can be a carboxylate, sulfonate, sulfate or phosphate of 8 to 18 carbon atoms of a linear or branched hydrocarbon group (including alkanes and alkenes), or of 8 to 18 carbon atoms Carboxylates, sulfonates, sulfates or phosphates composed of linear or branched hydrocarbon groups (including alkanes and alkenes) and aryl groups. Considering environmentally friendly performance, the order of environmentally friendly performance from good to poor is: various salts of linear hydrocarbon groups>various salts of branched hydrocarbon groups>various salts of aryl groups.
  • anionic surfactants have the properties of reducing surface tension, emulsifying and solubilizing.
  • CMC critical micelle concentration
  • the so-called micelle means that the anionic surfactant is below the CMC concentration and is dissolved in water in a single-molecule dispersed state. When the concentration exceeds the CMC, the molecules aggregate, and several anionic surfactant molecules aggregate in a state with the lowest energy.
  • Hydrophilic polar groups face the water phase, while hydrophobic non-polar groups (lipophilic groups) gather together to form a spherical micelle with a diameter of a few nanometers.
  • the morphological structure is shown in Figure -1.
  • rod-shaped micelles may be formed in addition to spherical micelles.
  • the outside is a hydrophilic group such as carboxylate, sulfonate, sulfate or phosphate
  • the inside is a lipophilic hydrocarbon group, a hydrophobic and lipophilic environment
  • it can accommodate solutions of water-insoluble pesticides or its hydrophobic solvents.
  • the CMC of an anionic surfactant generally the smaller the value, the higher the activity.
  • the second is the Krafft temperature, which is the temperature when the anionic surfactant forms micelles, and is also the temperature when the molecules are dissolved, the micelles, and the gel are in three-phase equilibrium.
  • HLB hydrophilic-lipophilic balance
  • non-ionic surfactants are required for small molecule additives.
  • This surfactant does not dissociate into an ionic state in an aqueous solution, but exists in the solution in the state of molecules or micelles, so it is called a nonionic surfactant.
  • Its lipophilic group is generally a hydrocarbon chain or a polyoxypropylene chain, and the hydrophilic part is a polyoxyethylene, hydroxyl or ether group, amide group, etc.
  • Most non-ionic surfactant products are liquid or slurry, which is different from anionic surfactants.
  • Nonionic surfactants differ in their hydrophilic group structure and mainly include polyoxyethylene-type nonionic surfactants, polyol-type ionic surfactants, and alkyl alcohol amide-type nonionic surfactants. Among them, the former is the most important type of nonionic surfactant, especially polyoxyethylene ethers of fatty alcohols have many varieties and large output. The performance of this type of nonionic surfactant not only depends on the hydrophobic group, but also has a great relationship with the length of the polyoxyethylene ether chain.
  • Several nonionic surfactant molecules in water form spherical micelles above the CMC. The morphology and structure of the micelles are similar to micelles.
  • the hydrophilic polyoxyethylene chain is on the outside, towards the water phase, and the lipophilic hydrocarbon-based structure is Inside, the size is slightly larger than the micelle, see Figure-3.
  • the biodegradation of nonionic surfactants includes two parts: hydrocarbon chain and polyoxyethylene chain.
  • the part of the hydrocarbon chain is still straight chain which is easier to degrade than branched chain, and the degradation of aromatic group is more difficult than the degradation of fatty group.
  • the longer the polyoxyethylene chain the worse the degradability.
  • alkylphenol polyoxyethylene ether especially degradation of nonylphenol polyoxyethylene ether occurs on phenolic ether, and nonylphenol is generated.
  • Nonylphenol has proved to be a feminine toxic substance, and entering the environment, especially into the water, will feminize aquatic organisms. Humans eat feminized aquatic organisms, and they also have infertility. Therefore, although such nonionic surfactants have good emulsifying properties, they have been banned.
  • the nonionic surfactants are characterized by cloud point and HLB value. Slowly heating the transparent aqueous solution of the non-ionic surfactant, after reaching a certain temperature, the solution will become cloudy, indicating that the surfactant begins to precipitate. The lowest temperature at which a solution appears cloudy is called the “cloud point", which is the temperature at which the aqueous solution separates as the temperature increases. In the homologous series of nonionic surfactants with the same lipophilic group, the longer the polyoxyethylene chain, the stronger the hydrophilicity and the higher the cloud point. From the practical point of view, if a system requires a heating process, then the cloud point of the nonionic surfactant used must be considered, otherwise the stability of the system will be destroyed due to the cloud point.
  • the HLB value of nonionic surfactants is the same as the description of anionic surfactants, and it is a qualitative characterization of the hydrophilic and lipophilic properties.
  • the HLB value of the surfactant can be obtained by various methods of analytical determination and calculation, and can also be found in the manual and literature. According to the dissolution state of the surfactant in water, the range of the HLB value can be roughly estimated. For example, Table-4 lists a quick method for estimating the range of surfactant HLB values.
  • the small molecule adjuvant selected for use in the present invention is composed of at least one anion and at least one nonionic surfactant, and its purpose is to form micelles and micelles with solubilizing properties in aqueous solution. Therefore, the principle for selecting small molecular compound additives is: first, considering the stability of the system, the krafft temperature of the anionic surfactant should be as low as possible, preferably close to 0 °C; second, the non-ionic surfactant The cloud point temperature should be higher than 60°C as much as possible, so as not to heat the temperature above the cloud point temperature when the solvent is recovered under reduced pressure; third, the miscible prodrug solution of the mixed solvent in which the pesticide active ingredient is dissolved must be realized in micelles and micelles For the solubilization of nanometer size, the HLB value of the small molecule compound additive should be above 13 and preferably above 14. Because the solution is transparent at this time, and transparent means that the size of the pesticide particles is less than a quarter of the wavelength of visible
  • Polymer additives are also polymer surfactants, usually referring to substances with a relative molecular mass greater than 10,000 and having surface activity. Compared with small molecule surfactants, macromolecular surfactants have less ability to reduce surface tension, but have some other special properties, such as dispersion, suspension, and viscosity enhancement. Polymer surfactants can be divided into natural polymers and their derivatives and synthetic polymers according to their source. Polymer surfactants have a hydrophobic main chain and suspended hydrophilic functional groups, such as hydroxyl, carboxyl, carboxymethyl, sulfonate, sulfate, phosphate, and amino groups, so they are all water-soluble polymers.
  • Water-soluble natural polymer and its derivatives including starch, dextrin and various derivatives, water-soluble starch, oxidized starch, carboxymethyl starch, modified starch, cellulose and its derivatives, carboxymethyl cellulose, Hydroxyethyl hydroxypropyl cellulose; carboxymethyl chitosan, modified guar gum, tea saponin, water-soluble humic acid, sodium lignosulfonate, etc.
  • Synthetic water-soluble polymers including polyvinyl alcohol, polyacrylic acid, polyacrylamide, polystyrene-maleic anhydride copolymer, polyvinylpyrrolidone, etc. Since the main chain of water-soluble synthetic polymers is mostly carbon chains, it is not easy to biodegrade. From the consideration of environmental friendliness, water-soluble natural polymers and their derivatives should be selected as much as possible to minimize the impact on the ecological environment.
  • the reason for selecting the polymer adjuvant in the present invention is to utilize the functions of dispersion and suspension of the water-soluble polymer in the aqueous solution.
  • a water-soluble polymer with a relative molecular mass of tens of thousands, hundreds of thousands, or hundreds of thousands is usually a linear polymer chain structure that can be dissolved in water.
  • the linear polymer is dissolved in water, the length-to-diameter ratio of the linear polymer is very large, but it is not presented in a straight linear state, but due to the flexibility of the molecular chain, it exhibits a curled state, that is The morphological structure of "random coil" is shown in Figure-5.
  • the hydrophilic groups in the random coil are oriented towards the water phase as much as possible, while the lipophilic chain structure is curled inside the random coil.
  • the size of the random coil depends on the relative molecular mass of the polymer additives, the concentration level, and the aggregation state structure of the polymer. The larger the molecular weight, the larger the volume of random coils formed by a single molecule; when the concentration of water-soluble polymer is higher, the random coils formed by different molecules will gather together, so the volume is also larger. Generally, when the molecular weight of the water-soluble polymer is tens of thousands to hundreds of thousands, the size of the formed random coil is usually tens to hundreds of nanometers.
  • the oleophilic nanocrystals tend to enter the oleophilic random coil and dope in different parts of the random coil.
  • the size of the pesticide nanocrystals is small, several nanocrystals can be dispersed inside the random coil.
  • the water-soluble polymer additives can act as a dispersant and stabilizer for the generated nano-grains.
  • Traditional pesticide suspending agents also use this principle, but their pesticide particles are in the micron size. Because the size of the micron particles is large and at the same time has a large gravitational effect, there is a large uncertainty in the stability of the suspending agent. When the size of pesticide particles is reduced by 2 to 3 orders of magnitude, the gravitational force of the particles is much smaller.
  • the same water-soluble polymer surfactant can obtain a more stable suspension and dispersion system to achieve apparent water solubility and transparent appearance.
  • the components of the miscible nano pesticide suspension agent and the nano pesticide suspension agent of the present invention include: pesticide active ingredients, solvents (including water-soluble solvents and water-insoluble solvents), auxiliary agents (including small molecule anionic auxiliary agents) Agents, small molecule non-ionic additives and polymer additives) and water.
  • pesticide active ingredients include: pesticide active ingredients, solvents (including water-soluble solvents and water-insoluble solvents), auxiliary agents (including small molecule anionic auxiliary agents) Agents, small molecule non-ionic additives and polymer additives) and water.
  • solvents including water-soluble solvents and water-insoluble solvents
  • auxiliary agents including small molecule anionic auxiliary agents
  • Agents small molecule non-ionic additives and polymer additives
  • water water.
  • the mass ratio between the three components is:
  • miscible original drug solution compound adjuvant: water ⁇ 35%:25%:40% ⁇ 0.875:0.625:1.
  • miscible drug solution and the compound auxiliary agent are about 0.875 and 0.625 times the mass of water, respectively.
  • Miscible original drug solution aqueous solution of compound additives ⁇ 35%:65% ⁇ 7:13
  • the miscible drug solution includes the quality of the active ingredient of the drug and the quality of the mixed solvent.
  • the former is often used, and the present invention is also expressed as a mass percentage when referring to the mass of components.
  • traditional pesticide formulations although the pesticides have different activities and different usage levels, manufacturers often like to pursue high levels of active ingredients in pesticides when preparing pesticide formulations.
  • the high content can reduce the volume and transportation cost of the packaging, due to the relatively small amount of additives, it will affect the dispersion performance of the pesticide solution diluted with water and the prevention and control effect on diseases and insect pests.
  • each different pesticide variety should have different content of active ingredients suitable for itself according to the level of pesticide activity and physical solubility.
  • the present invention prepares its miscible nano pesticide suspension agent and nano pesticide suspension agent (nano dispersant) according to the solubility (St 1 , St 2 ... St i ) of a pesticide in a certain type of solvent system. Taking into account that the amount of solvent has a rough upper limit, such as 30%, it also determines the final content of pesticide active ingredients in the formulation.
  • the fungicide with serial number 4, phenoxyquinoline, its solubility in acetone is 116g/L. That is, 10g of acetone (a solvent that is soluble in water) can dissolve about 1.16g of the active ingredient of the pesticide, and similar solvents that are insoluble in water, such as methyl ethyl ketone and cyclohexanone, have similar solubility. In this way, if a 30 g mass of solvent is used, 3.48 g of active ingredient can be dissolved. Considering that the saturated solution easily precipitates solute, the miscible drug solution cannot be prepared into a saturated state, so in the miscible drug solution, the mass percentage of the active ingredient of the drug can be set to 3.3%.
  • the miscible original drug solution is 3.3%, and the remaining components are compound additives and water.
  • the solvent was recovered by distillation under reduced pressure. Assuming that all the solvents used are recovered, and water is distilled as part of the azeotrope composition, the final active ingredient content can reach about 5%. Although it is possible to increase the amount of solvent used to dissolve more pesticide active ingredients, this will inevitably reduce the ratio of the amount of compounding aid and water, which may affect the uniformity and stability of the pesticide nano-grains. Therefore, the upper limit of the miscible drug solution is set to 35%. Although it can be prepared slightly beyond this content, if it exceeds too much, it will obviously affect the proportion of other components.
  • the upper limit of the mass ratio of the mixed solvent is about 30%, which in turn can check the solubility of the original drug, and thus select the type of original drug, mixed solvent .
  • the above example is the case where the solubility of the original drug is about 100 g/L.
  • the solubility of the original drug in a mixed solvent is greater than 100g/L, the mass of the solvent used can be less than 30%, and the mass percentage of the active ingredient of the original drug can be appropriately increased, between 3% and 12%, so that the mixed solvent and the original
  • the sum of the two drugs (that is, the miscible drug solution) is approximately 35%, and the proportion of other components in the system is selected from the remaining mass percentages.
  • the solubility of the original drug in a mixed solvent is less than 100g/L, only the target product with a lower active ingredient content can be obtained.
  • the mass percentage of the active ingredient, W ai % is set in the range of 3% to 12%. In theory, it is equal to the mass percentage S 1 % of the solvent S 1 times the solubility of the original drug in this solvent St 1 , plus the mass percentage S 2 % of the solvent S 2 times the solubility of the pesticide in this solvent St 2 , as shown in the following formula:
  • W ai % S 1 % ⁇ St 1 +S 2 % ⁇ St 2 + ⁇
  • Compound additives include small molecule additives and polymer additives.
  • Small molecule adjuvants include anionic surfactants and nonionic surfactants.
  • anionic surfactants factors to be considered include: chemical structure, critical micelle concentration (CMC), three-phase equilibrium point (krafft) temperature, and affinity-phobic balance value (HLB) value; for nonionic surfactants, need to be considered
  • CMC critical micelle concentration
  • HLB affinity-phobic balance value
  • nonionic surfactants need to be considered
  • the factors include: chemical structure, CMC value, cloud point temperature, HLB value. The two have in common: 1 chemical structure.
  • biodegradable surfactant chooses the type of biodegradable surfactant; 2 CMC value. Considering the activity of the surfactant, choosing a variety with a low CMC value can reduce the dosage. 3 HLB value. Considering the characteristics of the surfactant and generating a transparent solution (transparency or not involves whether the particles are nano-sized), choose a surfactant variety with an HLB value greater than 13. The difference between the two is that the krafft temperature of the anionic surfactant is the temperature at which the molecule dissolves, the micelles, and the gel equilibrate in three phases.
  • the cloud point temperature of a nonionic surfactant is the temperature at which the aqueous solution separates as the temperature increases. Considering the need to raise the temperature for vacuum distillation at a later stage of the preparation process to recover the solvent. The temperature of vacuum distillation must be lower than the cloud point temperature of the non-ionic surfactant, otherwise the non-ionic surfactant will condense out from the water and the stability of the system will be destroyed. Therefore, cloud point temperature should be higher, the best temperature ⁇ 60 °C.
  • small molecule additives include anionic and nonionic surfactants, and when they are dissolved in water, they form micelles or micelles in water, see Figure -1 and figure -3.
  • miscible prodrug solutions When the miscible prodrug solutions are dropped into the aqueous solution of small molecule adjuvants, they function to disperse, solubilize, and stabilize the pesticide solution droplets.
  • the droplets of the miscible prodrug solution contain water-soluble and water-insoluble organic solvents. After entering the aqueous solution of the small molecule adjuvant, the water-soluble solvent is immediately miscible with water and enters the aqueous phase, where it dissolves.
  • a part of the pesticide will be precipitated from the water.
  • the rate of precipitation of the pesticide grains is also controllable.
  • the system solution is controlled to be transparent, the size of the pesticide particles is controlled below 100 nm.
  • the remaining water-insoluble pesticide solution belongs to the oil phase in the system and is not miscible with water, but according to the principle of similar miscibility, the oil-soluble pesticide solution can enter the micelles and micelles formed by small molecule additives In it, it becomes a sol-enhancing beam (see Figure-2) and a sol-enhancing cluster ( Figure-4).
  • the system When the volume of the sol-enhancing beam and sol-enhancing mass is small enough, less than 100 nm, the system is clear and transparent. Because of the small size of the sol-enhancing beam and sol-enhancing mass formed by this part of the original drug solution, it is thermodynamically stable. To achieve this goal, a large number of micelles and micelles are required, and the formation of a large number of micelles and micelles requires a large amount of small molecule surfactants.
  • the mass percentage of small molecule additives to meet this demand should be 20% or more.
  • Polymer additives must be soluble in water, including natural polymers and synthetic polymers.
  • the selection principles include: 1 performance should be environmentally friendly. From the standpoint of being beneficial to biodegradation and the safety of degradation products, natural water-soluble polymers and their derivatives are preferred. Synthetic water-soluble polymers can also be used as a choice if they have good performance and little impact on the environment. 2The dissolution performance is better. The dissolution of macromolecules is different from the dissolution of small molecules. The dissolution process often goes through the swelling stage, which is more difficult than the dissolution of small molecules, and some takes longer time. Their solubility is affected by the variety of polymers, the aggregate structure of the polymers, and the relative molecular mass.
  • the precipitated pesticide grains are oleophilic (hydrophobic) and will diffuse into the hydrophobic internal formation of random coils formed by polymer additives. Due to the small grain size (keeping the system transparent, indicating less than 100 nm), Disperse into the random coil formed by the polymer additives suspended in water, see Figure 6. Therefore, the polymer additives actually play a role in suspending, dispersing and stabilizing the generated nano pesticide grains. Because the relative molecular mass of a water-soluble polymer is large, the viscosity of its aqueous solution is much higher than that of small molecules of the same concentration. This is the basic feature of polymer solutions. In order to not only suspend nanocrystalline grains, but also maintain a slightly higher viscosity of the system than the microemulsion, for example 300-500 mPas, the mass percentage of this component should be controlled at about 5%.
  • the compound auxiliary is composed of small molecule auxiliary (20%) and high molecular auxiliary (5%), so the mass percentage of the sum of the two is about 25%.
  • the remaining component is water.
  • the mass percentage of water is about 40%.
  • Water is a dispersion medium, which plays a role in maintaining the dispersion and stabilization of each component in the system, and its proportion of components is also very important.
  • the proportion of water is too large, and the proportion of active ingredients and components in the system is relatively small, which is not conducive to obtaining nano pesticides with high content of active ingredients.
  • the proportion of water is small and the viscosity of the system is large, which is not conducive to the formation, dispersion and stability of nano pesticide grains. Proper water ratio is necessary to prepare nano pesticide suspension.
  • the mass percentage of water should be around 40%.
  • the components of the miscible nano pesticide suspension agent of the present invention and the mass percentages of the combined three components and two components are shown in Table-8 and Table-9.
  • the pesticide species choose a solvent system that can dissolve it, including water-soluble/water-insoluble mixed solvent systems, including at least one water-soluble solvent and at least one water-insoluble solvent.
  • a solvent system that can dissolve it, including water-soluble/water-insoluble mixed solvent systems, including at least one water-soluble solvent and at least one water-insoluble solvent.
  • solubility in Table-2 determine the amount of pesticide active ingredient and the amount of mixed solvent (in terms of mass percentage). This method is not limited to the types of pesticides and solvents collected in Table-2.
  • a container equipped with a reflux condenser add a certain mass percentage of solvent, including water-soluble and water-insoluble solvents, and mix them into a mixed solvent after proper stirring.
  • a certain mass percentage of the pesticide active ingredient is added, and after proper stirring and dissolution, a miscible pesticide active ingredient miscible original drug solution is obtained.
  • the pesticide active ingredient is a single molecule dispersed in it, resulting in a true solution, transparent and stable.
  • Adjuvants include small molecular adjuvants and high molecular adjuvants, and small molecular adjuvants include anionic surfactants and nonionic surfactants. Considering that it is difficult to dissolve the polymer additives, the preparation of the aqueous solution of the compound additives should first dissolve the polymer additives, then the small molecule additives, and finally obtain the aqueous solution of the compound additives. The preparation process is as follows:
  • the solution of the miscible prodrug is added dropwise to the aqueous solution of the compound auxiliary agent under conditions of controllable stirring speed. Control the drop acceleration and stirring speed to generate nano pesticide grains, which is also a miscible nano pesticide suspension agent. If solvent recovery is not considered, this miscible nano pesticide suspension can also be used as a nano pesticide.
  • the miscible prodrug solution contains a solvent that is miscible with water.
  • the available solvents include acetone, methanol, tetrahydrofuran, and acetonitrile.
  • the solvent soluble in water quickly dissolves with water and enters the aqueous phase, leaving only the original drug solution insoluble in water in the aqueous solution. Since the amount of solvent to dissolve the original drug in the solution is reduced, it is not enough to dissolve the original drug, so a part of the original drug will precipitate out in water.
  • the particle size of the drug uniformly precipitated can be controlled.
  • the addition of water-insoluble solvents and proportions plays an important role in controlling the rate of precipitation of the original drug, not to mention the formation of large-sized crystal aggregates due to the excessive precipitation of the original drug. Therefore, the ratio of water-soluble/water-insoluble solvents is also an important influencing factor for controlling the precipitation speed of pesticide nanocrystals.
  • the chemical structure of each original drug is different, the physical properties and dissolution properties are different, the mixing ratio between the two or more selected solvents is different, generally the mass ratio between the two is 1: 2 ⁇ 5, but it is best to experiment and carry out appropriate Adjustment can be determined.
  • the generated nano crystal grains cannot be stably stored in water. Due to its own gravity, when it is at rest, the aggregation and growth of grains will occur, so that large-sized grains will precipitate out. In order to prevent this phenomenon, the polymer additives added to the system play a role of dispersion and stability.
  • Water-soluble polymers exist in the form of random coils. Random coils are loose spherical structures formed spontaneously by water-soluble polymer chains. The inner part is a main chain of lipophilic and hydrophobic molecules, and the outside is a hydrophilic polar group.
  • miscible solvents remain in the miscible drug solution.
  • the droplets of this original drug solution are also oleophilic, they are much larger than micelles, micelles, and random coils. Their best places are micelles and micelles. According to the principle of "similar miscibility", they can quickly and spontaneously enter the inside of micelles and micelles and become sol-enhancing sols (see Figure-2) and sol-enhancing lumps. As long as the number of micelles and micelles is sufficient, the remaining miscible prodrug solution can be solubilized, and the size below 100 nm can be maintained, so the system still looks clear and transparent.
  • the dripping acceleration of the miscible drug solution and the stirring speed of the aqueous solution of the composite additive are related to the amount of the aqueous phase added and the uniformity of dispersion in a unit time , Is an important factor that affects the grain size of the nano pesticides produced.
  • the particle size of the precipitated nano pesticides is less than 100 nanometers, whether the system is clear and transparent is the criterion. Its theoretical basis is that when the particle size is less than a quarter of the wavelength of visible light, it does not produce severe refraction and reflection, so the system is transparent. The wavelength of visible light is 400 to 760 nanometers, less than a quarter is less than 100 nanometers. Conversely, if the system for generating nano pesticide grains is clear and transparent, it indicates that the size of the generated grains is less than 100 nanometers.
  • the drop acceleration of the miscible drug solution should not be too fast. If it is too fast, the speed of generating pesticide grains is also fast. If too many nano pesticide grains are produced in the water phase at the same time, there is a possibility of aggregation between the nano grains, thereby increasing the grain size. If the system has opalescence, it means that the grain size is already in the hundreds of nanometers, and the opalescence becomes more and more serious or even opaque, which means that the grain size is close to or more than one micrometer. Therefore, the drop acceleration is subject to keeping the system always transparent. 2 The method of dropping the solution may also affect the grain size.
  • the stirring speed of the system should be properly accelerated.
  • the stirring speed of the system involves the generation and dispersion speed of the nano-pesticide grains generated by the aqueous phase. The faster the stirring, the faster the dispersion, the less likely the aggregation and collision between the grains, and the more beneficial it is to keep the grains of a smaller size Of dispersion.
  • the stirring speed of the system is greater than the stirring speed of the original drug dissolved in the mixed solvent, and also higher than the stirring speed of the polymer auxiliary and small molecule auxiliary dissolved in water. Only by matching with the dripping acceleration of the miscible prodrug solution, can the nanometer pesticide grains with smaller size and uniformity be obtained. When the dropping of the miscible prodrug solution is completed, the miscible nano pesticide suspension agent has been obtained at this time, and it can also be used as a nano pesticide formulation.
  • the miscible nano pesticide suspension agent obtained above also contains a certain mass percentage of organic solvent.
  • the pesticide active ingredient dissolved in this part of solvent does not exist in the form of nano-grain. To this end, this transition needs to be completed through the latter process.
  • the latter preparation process of the present invention is vacuum distillation.
  • the purpose of vacuum distillation is as follows: 1Complete the transformation of all pesticide active ingredients into nano pesticide grains, and convert all or most of the pesticide active ingredients in the system into nano grains. 2Recover the organic solvent in the system to further improve the environmentally friendly performance of the nano pesticide suspension agent. 3 The organic solvent is recovered by vacuum distillation, which plays the role of concentrating and miscible nano pesticide suspension agent, and can increase the active ingredient content of the nano pesticide suspension agent.
  • the miscible nano pesticide suspension agent obtained above contains organic solvents, including water-soluble solvents and water-insoluble solvents.
  • the organic solvent soluble in water is miscible in the aqueous phase.
  • a solution in which the water-insoluble solvent dissolves the active ingredient is solubilized in micelles or micelles.
  • the lower boiling point is distilled first.
  • acetone is miscible with water and has a low boiling point.
  • the first one to be distilled off is acetone with a boiling point of 56.12°C.
  • methyl ethyl ketone-water (composition ratio 88.7/11.3) azeotrope began to be distilled off, with a boiling point of 73.41°C. Since methyl ethyl ketone also dissolves pesticide active ingredients and exists inside the micelles or micelles, during the decompression process, as the methyl ethyl ketone solvent is distilled off and gradually reduced, the pesticide active ingredients dissolved in the solvent are continuously precipitated to form pesticides Nanocrystalline. Pesticide nanocrystals may either remain inside the micelles or micelles, or they may be precipitated from the micelles or micelles and transferred into the random coils formed by the polymer additives. Until most or all of the methyl ethyl ketone solvent is distilled off.
  • the method of solvent evaporation depends on the boiling point of the solvent and the cloud point temperature of the nonionic surfactant.
  • the cloud point temperature of commonly used non-ionic surfactants is usually around 60 °C, the boiling point of acetone is less than 60 °C, can be distilled at atmospheric pressure; and the azeotropic point of methyl ethyl ketone-water is 74 °C, exceeding the cloud point temperature, must be reduced Distill under pressure.
  • the vacuum distillation of the organic solvent in the system will involve the type and boiling point of the organic solvent, and whether it forms an azeotrope with water, including the composition, boiling point, and the relationship between boiling point and pressure of the azeotrope. In order to speed up the distillation of the azeotrope, the system can be heated. There are a few points to pay attention to:
  • the boiling point of the azeotrope composed of different solvents and water is different.
  • the azeotropes and compositions of some solvents involved in the present invention can form azeotropes are collected in Table-10.
  • the solvent with a low azeotropic point is distilled off first, and then the solvent with a high azeotropic point is distilled off.
  • the mass of water carried by the solvent with different percentages of mass can be roughly calculated. From this, the mass percentage of the pesticide active ingredient in the final miscible nano pesticide suspension is further calculated. It should be pointed out that not all organic solvents can be completely distilled off. When the boiling point of a certain solvent is high, the solvent is difficult to be distilled off, such as dimethylformamide, dimethylsulfoxide, etc., so choose this type Be careful when using solvents.
  • 2Different solvents may form ternary azeotrope with water.
  • the maximum temperature of system heating is limited.
  • the heating temperature of the system must be below the cloud point temperature of the nonionic surfactant. Otherwise, as the nonionic surfactant in the system rises to the cloud point temperature or above, turbidity and aggregation will occur, and the stability of the system will be destroyed.
  • Equation (2) is an expression for the mass percentage of the pesticide active ingredient before vacuum distillation
  • Equation (3) is an expression for the mass percentage of the pesticide active ingredient after vacuum distillation.
  • W ai1 and W ai2 are the mass percentages of pesticide active ingredients before and after vacuum distillation, W ai1 ⁇ W ai2 ; W w1 and W w2 are the masses of water before and after vacuum distillation, W w1 >W w2
  • the nano-pesticide solid powder is based on the miscible nano-suspending agent (nano-suspending agent) or nano-suspending agent, and finally forms a nano-pesticide powdery solid preparation after spray drying to recover part or all of the solvent. Other methods for preparing powders can also be used.
  • the present invention provides an environmentally friendly prothioconazole nanopowder, including an active ingredient A, the active ingredient A is prothioconazole, and further includes a solvent 12 to 28% by weight, a small molecule adjuvant 10-25 wt%, polymer auxiliary less than 10-15 wt% and dispersant water 35-45 wt%.
  • the present invention provides an environmentally friendly pyrithapyr nanopowder, including active ingredient A, the active ingredient A is pyrithapyr, and further includes a solvent 15 to 35 wt%, a small molecule adjuvant 8-20wt%, polymer auxiliary less than 5-12wt% and dispersant water 40-50wt%.
  • the present invention provides an environmentally friendly benzoene fluconazole nanopowder, including an active ingredient A, the active ingredient A is benzoene fluconazole, and further includes a solvent 10-30 wt%, Small molecular additives 10-25 wt%, polymer additives less than 10 wt% and dispersant water 40-50 wt%.
  • the present invention provides an environmentally friendly fipronil nanopowder, including an active ingredient A, the active ingredient A is fipronil, and also includes a solvent 8 to 23% by weight, small molecules
  • the additive is 10-25 wt%, the polymer additive is less than 9-17 wt%, and the dispersant water is 35-52 wt%.
  • the present invention provides an environmentally friendly fipronil nanopowder, including an active ingredient A, the active ingredient A is fipronil, and further includes a solvent 14 to 32% by weight, a small molecule adjuvant 10-25wt%, polymer auxiliary less than 5-22wt% and dispersant water 25-40wt%.
  • the present invention provides an environmentally friendly snail acaride nanopowder, including an active ingredient A, the active ingredient A is a snail acaride, and also includes a solvent 12 to 21% by weight, a small molecule adjuvant 10 to 25 wt%, polymer additives less than 5 to 14 wt% and dispersant water 31 to 46 wt%.
  • the present invention provides an environmentally friendly dipropanate nanopowder, which includes an active ingredient A, the active ingredient A is dipropanate, and further includes a solvent 9 to 26% by weight, a small molecule
  • the additive is 10-25 wt%, the polymer additive is less than 8-16 wt%, and the dispersant water is 32-56 wt%.
  • the present invention provides an environmentally friendly valoxamide nanopowder, including an active ingredient A, the active ingredient A is valoxamide, and further includes a solvent 15-25 wt%, a small molecule adjuvant 10 ⁇ 25wt%, polymer additives less than 5-15wt% and dispersant water 40-50wt%.
  • the present invention provides an environmentally friendly nanometer powder of fine benzepine, including active ingredient A, the active ingredient A is fine benzepine, and also includes a solvent 13 to 27% by weight, a small molecule adjuvant 10-25 wt%, polymer auxiliary less than 8-15 wt% and dispersant water 33-48 wt%.
  • the present invention provides an environmentally friendly clotrifloxazole nanopowder, including an active ingredient A, the active ingredient A is clofluconazole, and also includes a solvent 8 to 26 wt%, small molecules
  • the additive is 10-25 wt%, the polymer additive is less than 11-18 wt% and the dispersant water is 37-52 wt%.
  • the solvent is one or two of acetone or cyclohexanone.
  • the small molecule adjuvant is selected from biodegradable small molecule adjuvants, including anionic surfactants or nonionic surfactants.
  • the ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the nonionic surfactants include linear chains composed of different carbon atoms Polyoxyethylene ethers of alkyl ethers, esters, and amides.
  • the biodegradable small molecule adjuvant is a mixture of at least two of the above surfactants.
  • the HLB value of the small molecule adjuvant is 12-15.
  • the dosage is 10-25%, 8-20%.
  • the polymer adjuvant is selected from water-soluble polymer adjuvants, including natural water-soluble polymers and their derivatives or synthetic polymers.
  • the natural water-soluble polymer and its derivatives include dextrin, cyclodextrin, water-soluble starch, oxidized starch, carboxymethyl starch, modified starch, carboxymethyl cellulose, hydroxyethyl hydroxypropyl Cellulose; carboxymethyl chitosan, modified guar gum, tea saponin, the synthetic polymer is selected from polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polypyrrolidone, polystyrene-maleic acid Sodium, one or more of the water-soluble polymer additives are selected.
  • the invention also discloses an environmentally friendly preparation method of prothioconazole nano powder, the preparation method comprises the following steps,
  • component A Dissolve a certain amount of pesticide pesticide in a solvent or mixed solvent to prepare a nearly saturated solution, called component A;
  • component B Dissolve a certain amount of polymer additives in water, stir, and prepare an aqueous solution of a certain concentration, called component B;
  • component C (2) Add a certain amount of small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • the pesticide pesticide in the step (1) includes an active ingredient A, and the active ingredient A is prothioconazole.
  • the polymer auxiliary in the step (2) is selected from dextrin, cyclodextrin, water-soluble starch, oxidized starch, carboxymethyl starch, modified starch, carboxymethyl cellulose, hydroxyethyl hydroxy Propyl cellulose, carboxymethyl chitosan, modified guar gum, tea saponin, the synthetic polymer is selected from polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polypyrrolidone, polystyrene-cis-butene One or more of sodium diacid.
  • the small molecule adjuvant in the step (3) is selected from the group consisting of carboxylates, sulfonates, sulfates, polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms At least two kinds, the HLB value of the small molecule adjuvant is 12-15, and the dosage is 10-25%, 8-20%.
  • the prothioconazole nano powder nano-level prepared by the present invention has the same quality of pesticides, more pesticide particles, a larger surface area, and a wider area of contact with the target. Even higher, it can be used as a special agent for aerial plant protection, without precipitation or clogging of the nozzle; choose environmentally friendly additives, do not choose highly toxic solvents (benzene, toluene, xylene, methanol) and additives (nonylphenol Polyoxyethylene ether), more efficient, more environmentally friendly and safer, changed the previous state where only high efficiency and low toxicity were the first choice, and required that the pharmaceuticals be environmentally safe as the primary condition.
  • the preparation method of other solid pesticide powders in the above embodiments is the same as the preparation method of prothioconazole nano powders, which will not be repeated here.
  • Existing document three (201310550703.7): relates to the preparation of a nanoemulsion. It is composed of a pesticide pesticide and an organic phase in which a synthetic polymer is dissolved in methylene chloride, and another aqueous phase in which a synthetic polymer is dissolved in water.
  • the formed milky (opaque) emulsion is prepared by dropping the organic phase into the aqueous phase, and the particle size is above 250 nm.
  • Existing document five (201810614177.9) relates to the preparation of a hydrophobic pesticide composition.
  • the organic phase is composed of a hydrophobic pesticide and a biodegradable polymer dissolved in an organic solvent, an aqueous phase composed of an emulsifier dissolved in water, the organic phase is poured into the aqueous phase to obtain an emulsion, and a precipitate (product) is obtained by distillation under reduced pressure.
  • the particle size is 220-250 nm.
  • the organic phase described in the present invention is a solution formed by pesticide pesticides in at least two miscible solvents.
  • the outstanding feature of the organic phase is that at least one solvent is a solvent that is soluble in water; and at least another solvent is a solvent that is insoluble in water. The two have a certain ratio.
  • the water phase described in the present invention is a solution formed by polymer additives and small molecule additives dissolved in water respectively.
  • the salient feature of the water phase is that 1 the polymer additives are dissolved in water first. Because the relative molecular mass of the polymer is large, it is relatively insoluble, and the dissolution process often goes through the swelling stage.
  • the best order is to dissolve the polymer additives first; Because small molecule additives are easily soluble in water, the best order of addition is to add the small molecule additives, and the small molecule additives are added to the aqueous solution generated by the polymer to quickly generate the aqueous solution of the additive; Phase, the preparation time is short, there is no polymer block insoluble matter, which is conducive to the formation of a homogeneous and transparent auxiliary aqueous solution.
  • the preparation method of the present invention is to gradually drop the organic phase into the aqueous phase. Its characteristics include: 1 Under room temperature and stirring, strictly control the drop acceleration of the organic phase to facilitate the control of the size of the nanocrystals; 2 The control index of the drop acceleration is that the system added to the water phase should always be kept transparent. In order to ensure that the particle size of the generated miscible nanosuspension (ie nanosuspension) is kept below 100 nanometers. 3Drip addition method can be one-drop addition, multi-drop addition, spray-drop addition, etc., by controlling the droplet size of the organic phase into the water phase, so as to achieve the control of the particle size of the suspoemulsion. 4Control the stirring speed to ensure that the organic phase droplets dropped into the water phase can diffuse quickly and evenly in the water phase, thereby generating uniform nano-grains.
  • nano pesticide suspension emulsion ⁇ 100 nm, especially ⁇ 10 nm can be obtained.
  • Nano-pesticide suspension emulsion is a mixture of nano-suspension and microemulsion. Its appearance is clear and transparent, which achieves the apparent water solubility of water-insoluble pesticides.
  • the outstanding feature of nano-suspension is the small particle size.
  • the particle size is below 100 nm, especially below 10 nm.
  • the size is reduced by three orders of magnitude.
  • the size of pesticide particles is reduced from several hundred nanometers to several nanometers, and unexpected effects are obtained.
  • nanosuspension is different from that of nanomedicines prepared in the prior art, and the generated microscopic morphology is also different.
  • the nano-dosage forms generated in the prior art are all single emulsions (microemulsions), or suspending agents, while the technology of the present invention generates both nano-suspensions and micro-emulsions at the same time.
  • the formation mechanism is as follows: when the organic phase solution is dropped into the aqueous phase, the water-soluble organic solvent in the organic phase solution quickly diffuses into the aqueous phase and is miscible with water.
  • the solvent of the organic phase solution decreases, and the pesticide solution becomes supersaturated, which causes the pesticide active ingredient to precipitate out of the organic phase solution and precipitate in the aqueous phase to form nano-grains.
  • the generated nano crystals diffuse in the water phase, and there are polymers dissolved in water everywhere around them, and the polymers exist in the form of random coils in the water. Because the volume of polymer random coils is significantly larger than the micelles formed by small molecule additives in the aqueous phase, pesticide grains are more likely to enter the polymer random coils and become a stable nano-grain suspension agent.
  • the pesticide solution after the precipitation of the pesticide will spontaneously enter the inside of a large number of micelles to become a sol-enriched beam, and become a thermodynamically stable microemulsion part.
  • the system is in the state of coexistence of two forms of nano-suspending agent and nano-microemulsion.
  • (4)Nano suspension emulsion has excellent performance.
  • the performance is as follows: 1
  • the particle size is small and the distribution is narrow.
  • the TEM photographs of the samples of the examples show that the particle size of the particles is less than 10 nm, and some are as small as 1 nm. This is far superior to the performance of existing technologies.
  • 2 The appearance of the preparation is a homogeneous transparent liquid, apparently water soluble, uniformly dispersed and thermodynamically stable. This sexual energy is better than the existing technology due to the small particle size.
  • the formulations described in the aforementioned patent documents are milk-like (opaque), should belong to aqueous emulsions, and have no thermodynamically stable properties.
  • 3 The dilution performance of the preparation is stable. Whether it is diluted according to the amount of water used for manual spraying or drone spraying, the preparation will not accumulate in a short time.
  • Nano-suspension can also be used to prepare other nano pesticide preparations.
  • the organic solvent still exists in the nano-suspension, and the solvent can be further recovered in consideration of environmental friendliness.
  • the nano suspension emulsion is distilled under reduced pressure to control the temperature and vacuum degree, and the organic solvent can be recovered and prepared into a nano suspension emulsion.
  • the organic solvent in the system exists in two environments, one is the water-soluble solvent is miscible in water, and the other is the water-insoluble solvent is present inside the sol-enhancement beam. By distillation under reduced pressure, the solvent is recovered, thereby further obtaining a nano-suspending agent that does not contain an organic solvent. This is a more environmentally friendly nano pesticide formulation.
  • the difference between nano-suspension and nano-suspension is not only that the former does not contain organic solvents, but the former only has nano-crystal grains, and there is no sol-enriched beam containing pesticide solution.
  • nano-solid powder can be further prepared.
  • nano-solid powder can be prepared using the conventional spray drying equipment agent operation process, by adding water-soluble natural substances as solid dispersants, such as lignin sulfonate, xanthate, tea saponin, etc., nano pesticide solid powder can be prepared.
  • the nano-pesticide solid powder has the advantages of maintaining the nanometer size of the pesticide particles, no agglomeration, and stable storage and transportation.
  • Figure-7 Schematic diagram of the micro-morphology of small molecule additives and polymer additives in water
  • Figure-8 Schematic diagram of the microscopic distribution of pesticide nanocrystals and pesticide-insoluble aqueous solution beads
  • Figure-14 The particle size and distribution of the sample of the formulation of Example 1 measured by a laser nanoparticle size analyzer.
  • Figure-16 The particle size and distribution of the sample of the formulation of Example 2 as measured by a laser nanoparticle size analyzer.
  • Figure-18 The particle size and distribution of the sample of the formulation of Example 3 measured by a laser nanoparticle size analyzer.
  • Figure-20 The particle size and distribution of the sample of the formulation of Example 4 measured with a laser nanoparticle size analyzer.
  • Figure-22 The particle size and distribution of the sample of the formulation of Example 5 measured by a laser nanometer particle size analyzer.
  • the wt% in the present invention refers to the mass percentage of each raw material in the total mass of the raw material. Generally, the weight percentage and the mass percentage can be used equally, because commercially available raw materials are often measured by weight.
  • the results of the laser nanoparticle size analyzer show that the detection of 100% particles shows that the average particle size is 1.308nm and the standard deviation is 0.3337nm. Electron micrographs show that the particle size of the nanoparticles is very small, only a few nanometers, and the particles are evenly distributed.
  • a part or all of the solvent can be recovered by spray drying on the basis of E 1 or F 1 to prepare a nano-solid powder G 1 .
  • component D 2 Dissolve sodium dodecyl sulfonate, sodium linoleate, Tween-40, and AEO 20 in component C 2 to obtain an aqueous solution of a compound additive, which is referred to as component D 2 ;
  • the content of the active ingredient of cyclosporine was about 15%.
  • the appearance of the product is transparent, and the particle size of the active ingredient of the pesticide is judged to be below 100 nm according to the Tyndall phenomenon.
  • the test results of the instrument are shown in Figure-16 and Figure-17.
  • the results of the laser nanoparticle size analyzer show that the statistical results of the detection of 100% particles show that the average particle size is 4.858nm and the standard deviation is 0.7686nm. Electron micrographs show that the particle size of nanoparticles is very small, only a few nanometers, and the particles are evenly distributed.
  • a part or all of the solvent can be recovered by spray drying to prepare a nano-solid powder G 2 .
  • component D 3 Dissolve sodium lauryl ether sulfate, sodium linoleate, castor oil polyoxyethylene ether, and Tween-80 in component C 3 to obtain an aqueous solution of a composite additive, which is referred to as component D 3 ;
  • the content of the active ingredient of fenfluricide is determined, and the water is replenished until the active ingredient is 16%, to obtain a fenfluricide nano pesticide suspension agent of about 75 kg.
  • the appearance of the product is transparent, and the particle size of the pesticide active ingredient is judged to be below 100 nm according to the Tyndall phenomenon.
  • the test results of the instrument are shown in Figure -18 and Figure -19.
  • the results of the laser nanoparticle size analyzer show that the statistical results of the detection of 100% particles show that the average particle size is 1.282nm and the standard deviation is 0.3182nm. Electron micrographs show that the particle size of the nanoparticles is very small, only a few nanometers, and the particles are evenly distributed.
  • a part or all of the solvent can be recovered by spray drying on the basis of E 3 or F 3 to prepare a nano-solid powder G 3 .
  • Example 4 18% pyridoxamine nano-suspending agent
  • component D 4 Dissolve sodium dodecyl monophosphate, sodium linoleate, AEO 20 , and alkyl polyglycoside in component C 4 to obtain an aqueous solution of a compound additive, which is referred to as component D 4 ;
  • the content of the active ingredient of pyrimethanil was determined, and the water was replenished until the content of the active ingredient was 18%, to obtain a pyrithimide nano-suspension of about 77 kg.
  • the appearance of the product is transparent, and the particle size of the active ingredient of the pesticide is judged to be below 100 nm according to the Tyndall phenomenon.
  • the test results of the instrument are shown in Figure-20 and Figure-21.
  • the results of the laser nanoparticle size analyzer show that the statistical results of the detection of 100% particles show that the average particle size is 3.804nm and the standard deviation is 0.7440nm. Electron micrographs show that the particle size of nanoparticles is very small, only a few nanometers, and the particles are evenly distributed.
  • part or all of the solvent can be recovered by spray drying to prepare nano-solid powder G 4 .
  • component C 5 The styrene-maleic anhydride copolymer and sodium lignosulfonate are dissolved in water to obtain an aqueous solution of a polymer additive, which is referred to as component C 5 ;
  • the content of the active ingredient of cyanfluxate is determined, and the water is replenished until the content of the active ingredient is 10%, and the nanofluidate of cyanfluxate is obtained to be about 70 kg.
  • the appearance of the product is transparent, and the particle size of the active ingredient of the pesticide is judged to be below 100 nm according to the Tyndall phenomenon.
  • the test results of the instrument are shown in Figure-22 and Figure-23.
  • the results of the laser nanoparticle size analyzer show that the statistical results of the detection of 100% particles show that the average particle size is 6.826nm and the standard deviation is 1.248nm. Electron micrographs show that the particle size of the nanoparticles is very small, only a few nanometers, and the particles are evenly distributed.
  • Example 6-1 (corresponding application number is 201811618804.2)
  • An environmentally friendly prothioconazole nanopowder including active ingredient A, the active ingredient A is prothioconazole, the active ingredient is 18% by weight, further includes a solvent 12% by weight, a small molecule auxiliary agent 15% by weight, a polymer auxiliary agent 10wt%, dispersant water 45wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly prothioconazole nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly prothioconazole nanopowder including active ingredient A, the active ingredient A is prothioconazole, the mass fraction of the active ingredient is 15wt%, and also includes a solvent 18wt%, a small molecule adjuvant 12wt%, Polymer additives 15wt% and dispersant water 40wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms ,
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly prothioconazole nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly prothioconazole nanopowder including active ingredient A, the active ingredient A is prothioconazole, the active ingredient accounts for 10wt%, and also includes a solvent 25wt%, a small molecule adjuvant 16wt%, a polymer aid Agent 14wt% and dispersant water 35wt%.
  • the solvent is selected from acetone and cyclohexanone mixed in a volume ratio of 1:1.
  • small molecule additives are biodegradable small molecule additives, including nonionic surfactants, and nonionic surfactants include polyoxyethylene of linear alkyl ethers, esters, and amides composed of different carbon atoms
  • nonionic surfactants include polyoxyethylene of linear alkyl ethers, esters, and amides composed of different carbon atoms
  • the HLB value of ether and small molecule additives is 12-15.
  • water-soluble polymer additives are used as polymer additives, including synthetic polymers, and polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polypyrrolidone, and polystyrene-sodium maleate are selected as synthetic polymers.
  • the preparation method of the environmentally friendly prothioconazole nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 7-1 (corresponding application number is 201811618805.7)
  • An environmentally friendly pyrithapyr nanopowder including active ingredient A, the active ingredient A is pyrithapyr, the active ingredient 10wt%, also includes a solvent 35wt%, small molecule adjuvant 10wt%, polymer adjuvant 5wt%, dispersant water 40wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environment-friendly pyrithapyr nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly pyrithapyr nanopowder including an active ingredient A, the active ingredient A is pyrithapyr, the mass fraction of the active ingredient is 10wt%, also includes a solvent 15wt%, a small molecule adjuvant 20wt%, Polymer additives 10wt% and dispersant water 45wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 20%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environment-friendly pyrithapyr nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 8-1 (corresponding application number is 201811618956.2)
  • An environmentally friendly benzoene fluconazole nanopowder including an active ingredient A, the active ingredient A is benzoene fluconazole, the active ingredient is 8wt%, and also includes a solvent 30wt%, a small molecule adjuvant 10wt%, Polymer additives 2wt%, dispersant water 50wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include linear alkyl ethers, esters, amide polyoxyethylene ethers with different number of carbon atoms, small molecule additives with HLB value of 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly benzoene fluconazole nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly benzoene fluconazole nanopowder including an active ingredient A, the active ingredient A is benzoene fluconazole, the mass fraction of the active ingredient is 10wt%, and also includes a solvent 15wt%, small molecule auxiliary Agent 25wt%, polymer additives 5wt% and dispersant water 45%wt.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 25%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly benzoene fluconazole nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 9-1 (corresponding application number is 201811618803.8)
  • An environmentally friendly fipronil nanopowder including active ingredient A, the active ingredient A is fipronil, 10 wt% of the active ingredient, also includes 15 wt% of the solvent, 16 wt% of small molecule additives, polymer Auxiliary agent 14wt%, dispersant water 45%wt.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15.
  • water-soluble polymer additives are used for the polymer additives, including natural water-soluble polymers and their derivatives, and natural water-soluble polymers and their derivatives are selected for dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly fipronil nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly fipronil nanopowder including active ingredient A, the active ingredient A is fipronil, the mass fraction of the active ingredient is 9wt%, and also includes a solvent 21wt%, a small molecule adjuvant 13wt %, polymer additives 17wt% and dispersant water 40wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms ,
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly fipronil nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 10-1 (corresponding application number is 201811618802.3)
  • An environmentally friendly fipronil nanopowder including active ingredient A, the active ingredient A is fipronil, the active ingredient is 14% by weight, the solvent is 14% by weight, the small molecule auxiliary is 10% by weight, and the polymer auxiliary 22wt%, dispersant water 40wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly fipronil nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly fipronil nanopowder including active ingredient A, the active ingredient A is fipronil, the mass fraction of the active ingredient is 13wt%, and also includes a solvent 32wt%, a small molecule adjuvant 25wt%, Polymer additives 5wt% and dispersant water 25wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 25%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly fipronil nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 11-1 (corresponding application number is 201811632136.9)
  • An environmentally friendly snail mite diester nanopowder including active ingredient A, the active ingredient A is spirome diester, active ingredient 27wt%, also includes solvent 12wt%, small molecule additives 10wt%, polymer additives 5wt%, dispersant water 46wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly snail mite diester nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly snail mite diester nanopowder including active ingredient A, the active ingredient A is spirome diester, the mass fraction of the active ingredient is 9wt%, also includes a solvent 21wt%, small molecule adjuvant 25wt%, Polymer additives 14wt% and dispersant water 31wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 25%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly snail mite diester nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent, and prepare a nearly saturated solution (the content of the pesticide active ingredient will be smaller than that in the final nano-powder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 12-1 (corresponding application number is 201811632002.7)
  • An environmentally friendly dipropanate nanopowder including an active ingredient A, the active ingredient A is dipropanate, the active ingredient is 9wt%, and further includes a solvent 9wt%, a small molecule adjuvant 10wt%, a polymer Auxiliary agent 16wt%, dispersant water 56wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly dipropanate nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent, and prepare a nearly saturated solution (the content of the pesticide active ingredient will be smaller than that in the final nano-powder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly dipropanate nanopowder including an active ingredient A, the active ingredient A is dipropanate, the mass fraction of the active ingredient is 9wt%, and also includes a solvent 26wt%, a small molecule adjuvant 25wt %, polymer additives 8wt% and dispersant water 32wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 25%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly dipropanate nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent, and prepare a nearly saturated solution (the content of the pesticide active ingredient will be smaller than that in the final nano-powder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 14-1 (corresponding application number is 201811632003.1)
  • An environmentally friendly valoxamide nanopowder including active ingredient A, the active ingredient A is valoxamide, the active ingredient is 10% by weight, the solvent is 15% by weight, the small molecule auxiliary agent is 10% by weight, and the polymer auxiliary agent is 15% by weight. , 50wt% dispersant water.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly valoxamide nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent, and prepare a nearly saturated solution (the content of the pesticide active ingredient will be smaller than that in the final nano-powder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly valoxamide nanopowder including an active ingredient A, the active ingredient A is valoxamide, the mass fraction of the active ingredient is 5wt%, and also includes a solvent 25wt%, a small molecule adjuvant 25wt%, a polymer Auxiliaries 5wt% and dispersant water 40wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 25%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly valoxamide nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent, and prepare a nearly saturated solution (the content of the pesticide active ingredient will be smaller than that in the final nano-powder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 15-1 (corresponding application number is 201811632004.6)
  • An environment-friendly fine benxylamine nano powder including active ingredient A, the active ingredient A is fine benxylamine, active ingredient 14wt%, solvent 13wt%, small molecule adjuvant 10wt%, polymer adjuvant 15wt%, dispersant water 48wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly fine benxylamine nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly fine benxylamine nanopowder including active ingredient A, the active ingredient A is fine benxylamine, the mass fraction of the active ingredient is 7wt%, and also includes a solvent 27wt%, a small molecule auxiliary 25wt%, Polymer additives 8wt% and dispersant water 33wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 25%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly fine benxylamine nano powder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent and prepare a nearly saturated solution (the content of the pesticide active ingredient will be less than that in the final nanopowder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • Example 16-1 (corresponding application number is 201811632005.0)
  • An environmentally friendly clotrifloxazole nanopowder including active ingredient A, the active ingredient A is clotrifloxazole, the active ingredient is 12wt%, the solvent is also 8wt%, the small molecule adjuvant is 10wt%, the polymer Auxiliary agent 18wt%, dispersant water 52wt%.
  • the solvent is acetone.
  • the small molecule additives are biodegradable small molecule additives, including anionic surfactants or nonionic surfactants, and the ionic surfactants include carboxylates of linear alkyl groups composed of different carbon atoms Sulfonate, non-ionic surfactants include polyoxyethylene ethers of linear alkyl ethers, esters, and amides composed of different carbon atoms.
  • the HLB value of small molecule additives is 12-15, and the dosage is 10%.
  • the water-soluble polymer additives are used as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives are selected from dextrin, cyclodextrin and water-soluble starch.
  • the preparation method of the environmentally friendly clofluconazole nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent, and prepare a nearly saturated solution (the content of the pesticide active ingredient will be smaller than that in the final nano-powder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;
  • An environmentally friendly clotrifloxazole nanopowder including active ingredient A, the active ingredient A is clofluconazole, the mass fraction of the active ingredient is 11% by weight, and also includes 26% by weight of solvent and 25% by weight of small molecule additives %, polymer additives 11wt% and dispersant water 37wt%.
  • the solvent is cyclohexanone.
  • small molecule additives are biodegradable small molecule additives, including anionic surfactants, and ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • anionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • ionic surfactants include carboxylates, sulfonates, and sulfates of linear alkyl groups composed of different carbon atoms
  • the HLB value of small molecule additives is 12-15, and the dosage is 25%.
  • the water-soluble polymer additives are selected as the polymer additives, including natural water-soluble polymers and their derivatives, and the natural water-soluble polymers and their derivatives include carboxymethyl chitosan, modified guar gum and tea soap Prime.
  • the preparation method of the environmentally friendly clofluconazole nanopowder in this embodiment includes the following steps,
  • component A Dissolve the pesticide pesticide in a solvent or mixed solvent, and prepare a nearly saturated solution (the content of the pesticide active ingredient will be smaller than that in the final nano-powder preparation), which is called component A;
  • component B Dissolve the polymer adjuvant in water, stir to prepare an aqueous solution with a certain concentration, called component B;
  • component C (2) Add small molecule adjuvant to component B, stir, and prepare a compound adjuvant solution, called component C;

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
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  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
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Abstract

La présente invention concerne le domaine technique des pesticides La présente invention concerne une formulation de nano-pesticide et son procédé de préparation. Les matières premières et les matières auxiliaires de la préparation comportent une quantité efficace d'un principe actif pesticide ou d'un pesticide brut, ainsi qu'une quantité adéquate d'un solvant, d'un additif de haut poids moléculaire, d'un additif de faible poids moléculaire et d'un dispersant. La formulation a une petite taille nanométrique de particule. L'invention concerne également une nouvelle forme galénique. La formulation a un vaste potentiel d'application et peut connaître une grande popularité.
PCT/CN2019/128757 2018-12-28 2019-12-26 Formulation de nano-pesticide et procédé de préparation WO2020135600A1 (fr)

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CN201811618805.7 2018-12-28
CN201811618803.8 2018-12-28
CN201811618802.3A CN109757487A (zh) 2018-12-28 2018-12-28 一种环境友好型氟虫双酰胺纳米粉剂及其制备方法
CN201811618805.7A CN109673649A (zh) 2018-12-28 2018-12-28 一种环境友好型吡噻菌胺纳米粉剂及其制备方法
CN201811618804.2A CN109744245A (zh) 2018-12-28 2018-12-28 一种环境友好型丙硫菌唑纳米粉剂及其制备方法
CN201811618956.2 2018-12-28
CN201811618803.8A CN109673631A (zh) 2018-12-28 2018-12-28 一种环境友好型氟虫苯甲酰胺纳米粉剂及其制备方法
CN201811618956.2A CN109645014A (zh) 2018-12-28 2018-12-28 一种环境友好型苯并烯氟菌唑纳米粉剂及其制备方法
CN201811618804.2 2018-12-28
CN201811618802.3 2018-12-28
CN201811632136.9A CN109757499A (zh) 2018-12-29 2018-12-29 一种环境友好型螺螨双酯纳米粉剂及其制备方法
CN201811632002.7 2018-12-29
CN201811632004.6A CN109744239A (zh) 2018-12-29 2018-12-29 一种环境友好型精苯霜灵纳米粉剂及其制备方法
CN201811632136.9 2018-12-29
CN201811632004.6 2018-12-29
CN201811632005.0A CN109673633A (zh) 2018-12-29 2018-12-29 一种环境友好型氯氟醚菌唑纳米粉剂及其制备方法
CN201811632005.0 2018-12-29
CN201811632003.1A CN109673632A (zh) 2018-12-29 2018-12-29 一种环境友好型缬菌胺纳米粉剂及其制备方法
CN201811632002.7A CN109757509A (zh) 2018-12-29 2018-12-29 一种环境友好型双丙环虫酯纳米粉剂及其制备方法
CN201811632003.1 2018-12-29
PCT/IB2019/057429 WO2020136451A1 (fr) 2018-12-28 2019-09-04 Procédé de préparation d'une suspension de nano-pesticide miscible
PCT/IB2019/057428 WO2020136450A1 (fr) 2018-12-28 2019-09-04 Suspension de pesticide nanométrique miscible
IBPCT/IB2019/057429 2019-09-04
IBPCT/IB2019/057428 2019-09-04

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CN114342951A (zh) * 2021-12-09 2022-04-15 湖南农业大学 加速农药残留降解的复合纳米粒及其制备方法和应用
CN114342951B (zh) * 2021-12-09 2024-01-16 湖南农业大学 加速农药残留降解的复合纳米粒及其制备方法和应用
CN115141154A (zh) * 2022-06-29 2022-10-04 中国农业科学院植物保护研究所 一种丙硫菌唑铜盐纳米配合物及其制备方法和应用
CN115141154B (zh) * 2022-06-29 2023-11-10 中国农业科学院植物保护研究所 一种丙硫菌唑铜盐纳米配合物及其制备方法和应用
CN115812730A (zh) * 2022-11-23 2023-03-21 惠州市银农科技股份有限公司 一种含联苯肼酯的纳米悬浮剂及其制备方法
CN115812730B (zh) * 2022-11-23 2023-08-22 惠州市银农科技股份有限公司 一种含联苯肼酯的纳米悬浮剂及其制备方法
WO2024131339A1 (fr) * 2022-12-18 2024-06-27 张子勇 Nanosuspension pour lutter contre l'oïdium du concombre
WO2024131350A1 (fr) * 2022-12-18 2024-06-27 张子勇 Nanosuspension à composants multiples pour la prévention et le traitement de maladies d'arbres fruitiers et d'insectes nuisibles
WO2024130461A1 (fr) * 2022-12-18 2024-06-27 张子勇 Nanosuspension de mancozèbe contenant un fongicide triazole à large spectre, et son procédé de préparation
WO2024131347A3 (fr) * 2022-12-18 2024-08-02 张子勇 Nanosuspension de composé binaire de propineb et de triazole
WO2025091850A1 (fr) * 2022-12-18 2025-05-08 张子勇 Dispersion de nano-suspension de prochloraz manganèse
CN116889229A (zh) * 2023-07-11 2023-10-17 中国农业大学 一种提高飞防农药桶混稳定性喷雾助剂及其制备方法

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