WO2024131338A1 - 防治水果类病害的纳米悬浮剂 - Google Patents

防治水果类病害的纳米悬浮剂 Download PDF

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Publication number
WO2024131338A1
WO2024131338A1 PCT/CN2023/129216 CN2023129216W WO2024131338A1 WO 2024131338 A1 WO2024131338 A1 WO 2024131338A1 CN 2023129216 W CN2023129216 W CN 2023129216W WO 2024131338 A1 WO2024131338 A1 WO 2024131338A1
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component
water
mancozeb
manganese
zinc
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PCT/CN2023/129216
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English (en)
French (fr)
Inventor
张子勇
梁冰
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张子勇
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Priority to CN202380012350.7A priority Critical patent/CN117794366A/zh
Publication of WO2024131338A1 publication Critical patent/WO2024131338A1/zh

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    • C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides

Definitions

  • the invention belongs to the field of nano pesticides, and particularly relates to the preparation of a ternary composite nano suspension with particle sizes less than 100 nanometers.
  • Nanopesticides refer to pesticide preparations whose particle size is at the nanometer level. From the perspective of application effect and stability, the particle size of nanopesticides is preferably below 100nm, and the smaller the better. At present, the particle size of mainstream pesticide preparations is at the micrometer level, that is, more than a few micrometers. If it can be reduced to the corresponding nanometer level, that is, the size is reduced by 1,000 times, then the same mass of active ingredients, while maintaining the particle shape unchanged, theoretically the number of particles can be increased by 1 billion times, and the surface area can be increased by 1,000 times.
  • Mancozeb has been used internationally for more than 50 years. It has always been used in large quantities and is a protective organic sulfur fungicide with good effects. It is characterized by low toxicity, long lasting effect, ability to kill multiple groups of pathogens, low resistance, and good control effect, so it is highly valued.
  • Mancozeb is a broad-spectrum, non-systemic fungicide with protective effects. It is used for a variety of crops such as fruit trees, ornamental vegetables, and tobacco. It can also prevent and treat a variety of important leaf fungal diseases. It is used to prevent and treat early blight and late blight of potatoes and tomatoes; grape downy mildew and black rot; net spot, stripe, and large spot of wheat and corn; damping-off and seedling spot of cotton and peanuts, vegetable downy mildew, anthracnose, and blight, and has a good control effect.
  • Mancozeb can be compounded with a variety of pesticides to form a variety of compound preparations. However, whether used alone or in combination, due to its physical properties - it is neither soluble in water nor in organic solvents - its main dosage forms are traditional powders, wettable powders, water-dispersible granules, and suspensions. According to the existing level of pesticide preparation processing technology, the minimum size of pesticide particles in its preparations is usually more than a few microns, and the largest ones are more than ten microns or even tens of microns. The large size of mancozeb pesticide particles is not conducive to the efficacy of the drug.
  • the preparation process of several existing mancozeb dosage forms is to first synthesize the technical drug and then process various dosage forms.
  • the specific steps include: (1) Technical drug synthesis . It is divided into two steps: the first step is to synthesize mancozeb or mancozeb sodium, and the second step is to synthesize mancozeb.
  • the synthesized mancozeb or mancozeb sodium is water-soluble and can be dissolved in water. Then, it is subjected to salt formation and complexation reaction with manganese salt and zinc salt respectively to obtain block precipitated mancozeb.
  • the precipitated mancozeb is neither soluble in water nor in organic solvents, and needs to be separated, washed and dried to obtain mancozeb technical drug.
  • (2) Preparation processing .
  • the solid mancozeb technical drug is used as the raw material for preparation processing. Usually, crushing, grinding, mixing and other processing are required to obtain mancozeb preparations.
  • the above preparation process after mancozeb or mancozeb sodium needs to add corresponding production equipment and workshops, such as filters, dryers, crushers, grinders, mixers, and corresponding production processes and processing techniques. It can be found that the process from synthesizing water-soluble mancozeb or mancozeb to processing it into different solid dosage forms of mancozeb is long and energy-consuming.
  • Chinese invention patent CN201711490378.4 discloses a nano mancozeb powder dosage form.
  • One of the purposes of the above invention is to overcome the shortcomings of the prior art and provide a new idea and method for preparing a mancozeb powder dosage form that is different from the prior art.
  • mancozeb or mancozeb, mancozeb potassium
  • manganese salt and zinc salt is achieved to generate mancozeb, thereby providing a mancozeb nano suspension that is apparently water-soluble and transparent in appearance, and is directly used for spraying.
  • mancozeb nano suspension described in the above invention can be loaded into a pesticide spraying device for spraying.
  • Mancozeb is a water-soluble ammonium salt, which is a single molecule dispersed in water as one component.
  • the manganese salt and zinc salt that react with it are also single molecules and metal ion dispersed in water as another component. When the two meet, the reaction between the ions can easily form a mancozeb and zinc salt structure. Since manganese ions and zinc ions are both multivalent metal ions, in addition to salt formation, they may also form a complex structure. Whether it is salt formation or complexation, when mixing, by controlling the amount of a certain component added, mancozeb nanoparticles can be generated.
  • an aqueous solution of one component such as manganese salt or zinc salt
  • another component such as mancozeb
  • the generated mancozeb nanoparticles can be temporarily and stably dispersed in the water system when the particle size is very small and the number is small. Due to the continuous generation of nanocrystals, collisions, growth and aggregation between the grains will occur. When the size of the mancozeb nanoparticles is close to the wavelength of visible light, the system begins to show opalescence, and when it exceeds, it gradually becomes opaque. Coupled with the effect of its own gravity, large-sized grains will precipitate. To prevent this phenomenon, polymer additives must be added to the system. Polymer additives are water-soluble polymers, usually non-crystalline polymers, which exist in the form of random coils after dissolving in water. Random coils are water-soluble polymers.
  • the loose spherical structure formed by the spontaneous curling of the chain has a collection of lipophilic and hydrophobic molecular main chains inside and hydrophilic polar groups outside.
  • the random coils are evenly dispersed in the water phase, and the nanoparticles diffused into the interior of the random coils are also evenly dispersed in the water phase.
  • the grain size is below 100 nanometers, the system is clear and transparent, and the apparent water-soluble, and the "Tyndall phenomenon" will occur.
  • the addition rate of components and the stirring rate of the components entering the system involve the amount added per unit time and the degree of uniformity of dispersion, which are important factors affecting the size of the generated nanocrystals.
  • the target size of the generated nanocrystals is less than 100 nanometers
  • the clarity and transparency of the system is the criterion. Its theoretical basis is that when the particle size is less than one-fourth of the lower limit of the visible light wavelength (400-760 nanometers), no serious refraction and reflection will be formed, so the system is transparent. On the contrary, if the system is opalescent or opaque, it indicates that the particle size is greater than 100 nanometers.
  • the mixing speed of the two-component solution i.e. the speed of adding one of the components
  • the mixing speed of the two-component solution cannot be too fast. If the two components are added too quickly, the two components will be unevenly dispersed, and the local concentration will be too high, which will lead to a fast and large number of crystals. Aggregation between nanocrystals may occur, thus increasing the size of the crystals. If the system has opalescence, it means that the crystal size is already several hundred nanometers. Therefore, the speed of adding one of the components should be based on keeping the system transparent.
  • the stirring speed of the system should be appropriately increased.
  • the stirring speed of the system is related to the generation and dispersion speed of nano-crystals in the water phase. Sufficient stirring and fast diffusion are conducive to the rapid formation and dispersion of nano-crystals, maintaining small-sized crystals and avoiding aggregation between crystals.
  • the stirring speed should be coordinated with the speed of adding components, and should also be based on keeping the system transparent at all times.
  • Tyndall phenomenon refers to the phenomenon that when a beam of light passes through a colloid, a bright "path” can be observed in the colloid from the direction perpendicular to the incident light. This phenomenon is also called the Tyndall effect.
  • the essence of the Tyndall effect is a scattering phenomenon when light propagates in a colloid. The reason for this phenomenon is mainly because the particle size of the colloid particles is between 1 and 100 nm. When visible light passes through the colloid, it will produce a more obvious scattering effect, while the scattering effect of the true solution on light is very weak.
  • Colloids have obvious Tyndall phenomenon, while true solutions with dispersed molecules have almost no Tyndall phenomenon, so it is often used to distinguish between colloidal solutions and true solutions.
  • the particles are smaller than the wavelength of the incident light, light scattering occurs, and the light waves surround the particles and radiate around them, which is called scattered light or opalescence.
  • the Tyndall effect is essentially a scattering phenomenon of light or opalescence.
  • the scattering effect of the true solution on light is very weak.
  • the intensity of scattered light also increases with the increase of particle concentration in the dispersed system. Therefore, when the observed solution is clear and transparent, it indicates that the particle size in the solution is less than 100nm, and the Tyndall phenomenon may occur.
  • the particle is larger than the wavelength of the incident light (400nm to 740nm), light reflection will occur obviously.
  • the solution shows increasingly heavy opalescence, turbidity or even opacity, the particle size has increased to near micrometers or above.
  • the so-called system refers to the suspension system formed by mixing two components under the premise of controlling the addition speed and stirring when preparing the mancozeb nano suspension in the present invention.
  • the system is the target product - suspension - generated by mixing water, precursor, manganese salt, zinc salt and water-soluble polymer additive.
  • a component refers to a composition containing one or more ingredients.
  • any ingredient used in the present invention can form a component alone, but considering the convenience of packaging, transportation and use, the components should be combined and simplified.
  • the principles are: 1 The components do not react with each other; 2 The number of components formed by the components should not be too large.
  • ingredients refer to the raw materials used in the present invention, including water-soluble mancozeb, manganese salt, zinc salt, water-soluble polymer additives and water.
  • the so-called precursor refers to the parent substance used in the production reaction of the target product mancozeb, that is, water-soluble mancozeb salts, including mancozeb, mancozeb sodium and mancozeb potassium.
  • Water-soluble polymer additives refers to polymer substances that can be dissolved in water with hydrophilic polar groups in the macromolecules, also known as polymer surfactants and active agents. Water-soluble polymer additives can play a role in dispersion, suspension, emulsification and stabilization. According to the nature of the group, they can be divided into anionic, cationic, zwitterionic and non-ionic polymer additives.
  • Particle size also known as particle size; refers to the size of the mancozeb crystals formed by the interaction of the precursor with zinc salts and manganese salts under the dispersion of water-soluble polymer additives in the system. It also includes the particle size formed by other pesticide varieties compounded with it, and does not specifically refer to the microscopic morphological structure of the crystals.
  • nano suspension below 100 nanometers It is a statistical classification of the size of pesticide particles in the system.
  • the sizes of all pesticide particles in the suspension present a statistical distribution.
  • the nano suspension below 100 nanometers described in the present invention refers to the peak value on the particle size distribution curve of the mass fraction of each fraction of the particle classification and its corresponding size is less than 100 nanometers. It can be detected by the British Malvern laser nanoparticle size analyzer and processed by the Number statistical method.
  • Stable period refers to the stable time that the nanosuspension can maintain a transparent state after preparation. In order to ensure the completion of the spraying operation, the stable period should be no less than 1 hour.
  • the hour-level stable period proposed in the present invention refers to a stable time between 1 and 5 hours.
  • Effective stirring speed refers to the fact that when one component is added to another component in a certain way, the nano-crystals generated in the system can be dispersed in time through stirring at a speed not less than the effective stirring speed, without the growth and aggregation of the grains, and the grain size does not increase to the level of several hundred nanometers.
  • the transparent state of the generated liquid in the system is a sign of effective stirring.
  • the addition of components and the stirring method and speed have an important impact on the system liquid.
  • the stirring methods include mechanical stirring, multi-point mechanical stirring, manual stirring, and multi-point manual stirring. Fast stirring speed is conducive to producing good results. If the system liquid is transparent, it is considered to be effectively stirred. Otherwise, it is considered to be ineffective stirring.
  • Addition method includes adding component A to component B, component B to component A, or adding component A and component B to the system at the same time, and also includes continuous addition, intermittent addition, trickle addition, drop addition, spray addition, and addition at a fixed position or a moving position, etc.
  • the best addition method is to mix and disperse the two components as quickly as possible.
  • Addition speed After determining the addition method, control the amount of components added with the goal of achieving effective stirring.
  • Nanoemulsion also known as nanoemulsion. It refers to a dispersion system of nano-sized latex particles formed by a solution of the active ingredients of pesticides under the action of adjuvants dispersed in water. The appearance of nanoemulsion is clear and transparent, the particle size is usually below 100nm, and it has thermodynamic stability.
  • Fluazinam/pyraclostrobin nanoemulsion also known as fluazinam and pyraclostrobin composite nanoemulsion
  • Mancozeb is a broad-spectrum multi-site protective fungicide, and its main function is to prevent the occurrence of fungal diseases. In order to achieve the best control effect, it should be used in advance and preferably mixed with other agents, especially systemic fungicides. Therefore, in order to improve the control effect of crop diseases, mancozeb is often compounded with other fungicides. In order to improve the disease control effect of mancozeb and obtain multi-target control effects in one plant protection, the present invention proposes to further obtain a binary, ternary or multi-component nanosuspension of mancozeb and different fungicides on the basis of the technology of obtaining mancozeb nanosuspension. The method and scheme proposed in the present invention can make the mancozeb compounded nanosuspension more widely used.
  • Fluazinam has a molecular formula of C 13 H 4 Cl 2 F 6 N 4 O 4 and a chemical name of 3-chloro-N-(3-chloro-5-trifluoromethyl-2-pyridyl)- ⁇ , ⁇ , ⁇ -trifluoro-2,6-dinitro-p-toluidine. It is a type of pyridinamine derivative that has a broad fungicide spectrum, fast prevention effect, and is not prone to cross-resistance. It is the most active agent among the current broad-spectrum fungicides and is often used as a protective fungicide. Fluazinam is not systemic, so it cannot be absorbed by plants after use.
  • Fluazinam has a good control effect on both higher and lower fungi, and can effectively control downy mildew, gray mold, anthracnose, sclerotinia, clubroot, damping-off, and scab and black spot on fruit trees, among which it has special effects on gray mold, blight, and clubroot.
  • the molecular formula of pyraclostrobin is C 19 H 18 ClN 3 O 4 , and its chemical name is N-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-N-methoxycarbamic acid methyl ester or ⁇ 2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl ⁇ methoxycarbamic acid methyl ester. It is a broad-spectrum methoxyacrylate fungicide, mainly used to prevent various diseases caused by fungi on crops. Pyraclostrobin has been widely used in the global agricultural field due to its broad fungicide spectrum, high efficiency, low toxicity, odorlessness, low resistance to drug resistance, promotion of crop growth, and improvement of crop stress resistance.
  • Mancozeb and fluazinam are compounded in a certain proportion to form a broad-spectrum, low-toxic composite fungicide, which has a protective effect as the main function and a therapeutic effect as the auxiliary function. If used in advance, it can effectively prevent the occurrence of various diseases, is not easy to develop drug resistance, and has a long lasting effect.
  • mancozeb and fluazinam are compounded, they are suitable for a variety of crops and can effectively prevent diseases caused by Alternaria, Phytophthora, Monoparaceta, Sclerotinia and Venturia. It also has a good effect on Botrytis cinerea, which is resistant to benzimidazole and dicarboximide fungicides.
  • a compound preparation of mancozeb and fluazinam can be used for effective protection first, which can reduce the risk of recurrence of the disease in the later stage.
  • Mancozeb can also be compounded with pyraclostrobin in a certain proportion to form a broad-spectrum, low-toxic composite fungicide with dual protective and therapeutic effects.
  • the two fungicide mechanisms make it difficult for pathogens to develop drug resistance, and it is convenient and safe to use, with a long lasting effect.
  • Mancozeb/pyraclostrobin compound preparations are suitable for a variety of crops, and have good control effects on many higher fungal diseases, especially on black spot, powdery mildew, and leaf spot.
  • the crops and diseases currently used for prevention and control include: apple leaf spot disease; banana leaf spot disease, black spot disease; citrus scab, sand bark disease, anthracnose; melon downy mildew; strawberry brown spot disease, strawberry anthracnose; cowpea rust, etc.
  • the existing compounding ratio of mancozeb/pyraclostrobin is 100/5 to 100/25.
  • the dosage forms are mainly suspension concentrate, wettable powder, water dispersible granules and dispersible oil suspension concentrate.
  • pyraclostrobin can be added to the compound of mancozeb and fluazinam to prepare a ternary compound preparation of mancozeb/fluazinam/pyraclostrobin.
  • other fungicides can also be added.
  • the dosage range of the combined preparation of mancozeb/fluazinam/pyraclostrobin is: 100/10 ⁇ 30/5 ⁇ 25.
  • the mancozeb/fluazinam/pyraclostrobin nano suspension of the present invention refers to a nano suspension of less than 100 nanometers; the mancozeb/fluazinam/pyraclostrobin nano suspension of less than 100 nanometers is formed by diluting and mixing at least two components with water:
  • fluazinam/pyraclostrobin is added to further form a nanosuspension of ternary pesticides.
  • Fluazinam/pyraclostrobin is added to component A in the form of a nanoemulsion.
  • the form of the particles of fluazinam/pyraclostrobin depends on the amount of dilution water and the amount of polymer adjuvant in the system. When the amount of water is small, the amount of diluted polymer adjuvant can continue to maintain the existence of nanomicelles.
  • mancozeb nanoparticles and fluazinam/pyraclostrobin nanomicelles coexist. If the amount of water added is not enough to maintain the minimum concentration of polymer adjuvant required for the nanomicelles, the micelles will disappear, and fluazinam/pyraclostrobin will precipitate in the water in the form of nanocrystals, becoming a mixture of nanocrystals of the three pesticide active ingredients, or a mixture of nanocrystals generated by mixing the three pesticide active ingredients, coexisting in the nanosuspension.
  • the two-component regimen is as follows:
  • Component A water-soluble mancozeb or water-soluble mancozeb aqueous solution, water-soluble polymer additive and water;
  • the water-soluble mancozeb is one of mancozeb, sodium mancozeb, potassium mancozeb, or a mixture of at least two of them;
  • the water-soluble polymer additive is a composite additive composed of at least one nonionic surfactant or its aqueous solution;
  • component A is added with a nanoemulsion of fluazinam/pyraclostrobin
  • Component B a mixture of manganese salt and zinc salt in a certain proportion; the manganese salt and zinc salt are respectively composed of at least one salt;
  • the component B may be a solid mixture of manganese salt and zinc salt, or may be an aqueous solution formed by adding water, and a water-soluble polymer auxiliary agent may be further added.
  • the water-soluble polymer auxiliary agent is at least one nonionic surfactant.
  • the manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate;
  • the zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.
  • the amount of the water-soluble polymer additive includes the sum of the amounts of the polymer additives in component A and component B, and the ratio of the water-soluble polymer additive to the amount of dilution water is not greater than 1:1500.
  • the amount of dilution water includes all the water in the system.
  • Nonionic surfactants may be selected from water-soluble starch and its derivatives, water-soluble guar gum and its derivatives, polyoxypropylene-polyoxyethylene block copolymers, fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene ethers, fatty amine polyoxyethylene ethers, alkyl aryl polyoxypropylene polyoxyethylene ethers, arylphenol polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkyl polysaccharides, tween, polyvinyl alcohol, polyvinyl pyrrolidone, etc.
  • the degradation products of nonylphenol polyoxyethylene ether have estrogenizing toxicity and should be refused for use.
  • polyoxypropylene-polyoxyethylene block copolymers fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene ethers, fatty amine polyoxyethylene ethers, alkyl aryl polyoxypropylene polyoxyethylene ethers, PO-10, castor oil polyoxyethylene ethers, alkyl polysaccharides, tween, etc.
  • the mancozeb nanosuspension with a size below 100 nanometers has a stable period of hours.
  • the mancozeb/fluazinam/pyraclostrobin nano suspension prepared by the present invention is a type of transparent, water-soluble solution, but it is not a thermodynamically stable solution. Therefore, the time for the nano suspension to maintain a transparent state is not infinite, but there is a stable period. Considering the characteristics of the spraying operation, after the nano suspension is prepared, the required operating time should be at least more than 1 hour, so that the length of the stable period can be described in hours. Thus, the present invention proposes that the nano suspension below 100nm has the concept of "stable period". That is, the nano suspension below 100nm prepared by the present invention completes the spraying operation during the period when the solution remains transparent, and the stable period should reach at least 1 hour.
  • the stable period can be further divided into four time periods: less than 1 hour, 1 to 2 hours, 2 to 5 hours, and more than 5 hours.
  • the nanoscale suspension remains transparent, which ensures that the particle size remains less than 100 nm.
  • the stabilization time is about 1 hour, which is not enough for the spraying operation; it is difficult to achieve a multi-component nanosuspension with a stabilization period of more than 5 hours.
  • the stabilization time is between 2 and 5 hours, and the spraying operation of most pesticide equipment can be completed easily within this time.
  • the hour-level stabilization period mentioned in the present invention refers to a stabilization time between 1 and 5 hours.
  • the basic period for spraying operation is 1 to 2 hours; in most cases, the spraying equipment can complete the operation.
  • the traditional pesticide preparations of mancozeb, fluazinam and pyraclostrobin can be single agents of three components or two components, mancozeb/fluazinam is a compound component, and pyraclostrobin is another component. Most of these components are water dispersible granules. When the three are used together, they need to be "bucket mixed” and diluted with water before spraying, but the size of the pesticide particles is above micrometer level. In order to obtain a nano-scale suspension, the present invention adopts at least two-component mode, and dilutes with water according to a certain method to obtain a mancozeb/fluazinam/pyraclostrobin/nano suspension below 100 nanometers.
  • Mancozeb suspension with a size below 100 nanometers has a stable period of hours and is a system generated by the mixed reaction of two components. They are:
  • Component A It is composed of mancozeb (or sodium mancozeb, potassium mancozeb), fluazinam/pyraclostrobin nanoemulsion and water to form a transparent aqueous solution.
  • mancozeb or sodium mancozeb, potassium mancozeb
  • fluazinam/pyraclostrobin nanoemulsion and water to form a transparent aqueous solution.
  • the precursor of mancozeb, the water-soluble polymer surfactant and water that play the role of dispersion, suspension and stabilization are the basic components of component A.
  • the nanoemulsion of the active ingredient can be added.
  • the fluazinam and pyraclostrobin nanoemulsions contain a certain amount of water-soluble polymer additives. As required, further water-soluble polymer additives may be added.
  • Component B is a system of a mixture of inorganic manganese salt and zinc salt in a certain proportion.
  • the system has three forms: solid inorganic manganese salt and zinc salt (component B1 ), aqueous solution of inorganic manganese salt and zinc salt (component B2 ), and aqueous solution of inorganic manganese salt and zinc salt and water-soluble polymer additive (component B3 ).
  • the manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate;
  • the zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.
  • inorganic manganese salts and zinc salts have limited solubility in water
  • the amount of water used needs to be limited in order to minimize the capacity of component B.
  • the solubility of inorganic salts is also affected by the amount of additives, which also limits the amount of water-soluble polymer additives added to component B.
  • B3 is an improved solution, which is to distribute the water-soluble polymer additive to both component A and component B.
  • component B there is an upper limit to the proportion of the water-soluble polymer additive in component B, unless the limitation of component B to a certain capacity is not considered.
  • the two-component regimen includes three active ingredients: mancozeb, fluazinam, and pyraclostrobin.
  • Component A use maneb (or sodium maneb, potassium maneb), or an aqueous solution of a mixture of at least two thereof, fluazinam/pyraclostrobin nanoemulsion, and then continue to add adjuvants.
  • Component B manganese sulfate (or manganese acetate, manganese chloride, manganese nitrate) and zinc sulfate (or zinc acetate, zinc chloride, zinc nitrate) are dissolved in water in a certain proportion; auxiliary agents may also be added.
  • the dosage of the active ingredients is the basis for determining the composition of the two components.
  • Mancozeb or sodium mancozeb, potassium mancozeb in component A is the precursor for the formation of nano mancozeb and is the basis for determining the composition of component B.
  • the present invention takes the case that 1/15 hectare of field needs 70 grams of mancozeb and sprays according to the ratio of mancozeb/fluazinam/pyraclostrobin of (70/24/12) grams as an example. Based on generating (70+24+12) grams of mancozeb/fluazinam/pyraclostrobin nano suspension of less than 100 nm, a two-component design is performed.
  • Component A requires maneb or sodium maneb, potassium maneb, preferably maneb as a precursor, about 63 grams; 100 grams of fluazinam/pyraclostrobin (24%+12%) nanoemulsion (containing 24 grams of fluazinam and 12 grams of pyraclostrobin, and a certain amount of adjuvants). According to the aforementioned distribution principle of adjuvants in component A and component B, most of the adjuvants will be distributed in component A. If both component A and component B are packaged in 500 grams of mass, the amount of water used is the amount after deducting maneb, fluazinam/pyraclostrobin nanoemulsion, and polymer adjuvant.
  • Component B first determine the amount of inorganic manganese salt and zinc salt required for the reaction with maneb.
  • Manganese sulfate and zinc sulfate are preferred in the present invention. It is generally believed that manganese ions react with maneb to replace ammonium ions to form salts, generating a ring structure or linear polymer structure of maneb, while zinc ions are complexed with sulfur atoms on maneb salt molecules to form a complex structure.
  • Mass ratio of mancozeb manganese sulfate: zinc sulfate
  • the present invention adopts a ratio lower than it for the following reasons: 1 large amount of manganese and zinc ions are used, and the concentration is high, which is not conducive to the formation and stability of small-sized grains; 2 low amounts of manganese salts and zinc salts are used, and even if the reaction is not sufficient, all of their components are independently usable bactericides; 3 the preparation process of the nanosuspension does not require industrial production of mancozeb washing, separation and drying, and no components are lost.
  • the molecular ratio and mass ratio between the three are as follows:
  • the additives are mainly in component A.
  • Component A mainly contains mancozeb (or sodium mancozeb, potassium mancozeb) and fluazinam/pyraclostrobin nanoemulsion.
  • component A and component B must be packaged separately. If a two-component method is used, the fluazinam/pyraclostrobin nanoemulsion in component A contains an adjuvant, and an adjuvant must be added separately, unless a third component of a separate adjuvant is added. This makes the component and dilution process complicated.
  • the condition for adding adjuvants to component A is that both mancozeb and the adjuvant are soluble in water and can be miscible without precipitation and other unstable phenomena. However, considering that the content of mancozeb and the adjuvant is high and the viscosity itself is large, it is not easy to operate. Therefore, a certain amount of water should be added to dissolve and dilute it, reduce the viscosity, and facilitate operation. After achieving the above purpose, the amount of water added should reduce the total mass of component A as much as possible to reduce the production, packaging and transportation costs.
  • Component B is mainly a mixture of manganese salt and zinc salt, or an aqueous solution thereof, or an aqueous solution of a polymer auxiliary agent thereof.
  • Component B can be a solid mixture of manganese salt and zinc salt. It needs to be dissolved in water before mixing with component A. For convenience, their aqueous solutions can be used. Their solubility is not high and a large amount of water is required. Depending on the dissolution of the mixed salt, you can choose to add or not add an adjuvant.
  • component B If the amount of adjuvant in component A is not enough to support the dispersion and suspension of nanoparticles, appropriate adjuvants should be added to component B.
  • the premise is that in the mixed aqueous solution of manganese salt and zinc salt, the amount of adjuvant added should make component B still transparent and no condensation and film formation occurs on the surface of the mixed solution.
  • the mass concentration of the additive added to component B of the mixed solution of dissolved manganese salt and zinc salt is generally not higher than 5%.
  • both component A and component B can solve the above difficulties by expanding their capacity, the increase in the dosage of the two components will undoubtedly increase the production, packaging and transportation costs. Taking these factors into consideration, it is important to balance the relationship between the dosage of each component and the product specifications and use as little adjuvant and water as possible under the premise of generating unit mass of mancozeb compound pesticide nanoparticles.
  • the water-soluble polymer auxiliary agent with dispersing and suspending effects is an important component substance related to the size of the mancozeb/fluazinam/pyraclostrobin nanoparticles generated when two or three components are diluted and mixed in the present invention, as well as whether they can be stably dispersed and suspended.
  • Water-soluble polymer additives are polymer surfactants with properties such as dispersion, suspension, and viscosity improvement, which are derived from the hydrophobic chain structure and hydrophilic functional groups. These groups distributed in the end groups and side groups include hydroxyl, carboxyl, carboxymethyl, sulfonic acid, sulfate, phosphoric acid, amino, quaternary ammonium salt, etc. According to the source, they are divided into natural and synthetic polymers, and according to the nature of the hydrophilic group, they are divided into anionic, cationic, nonionic and zwitterionic polymers.
  • the principles for selecting water-soluble polymer additives in the present invention are: 1 being able to stably disperse and suspend the generated pesticide nanoparticles; 2 being unaffected by the reaction of multivalent metal ions with water-soluble mancozeb; 3 being as environmentally friendly as possible. Therefore, the present invention selects non-ionic polymer additives derived from natural substances. Such as polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymers, various polyoxyethylene ethers with fatty alcohols, fatty acids, fatty amines, alkyl aromatic phenols, oil groups, etc.
  • hydrophobic groups such as Peregram series, OP series, Tween series, polyol series, ricinoleic acid series, alkyl polysaccharides, etc.
  • Peregram series OP series
  • Tween series polyol series
  • ricinoleic acid series alkyl polysaccharides
  • alkyl polysaccharides etc.
  • nonylphenol polyoxyethylene ethers with estrogenic toxicity should be abandoned.
  • the mancozeb/fluazinam/pyraclostrobin nano suspension is generated by the reaction of water-soluble mancozeb (or sodium) with manganese salt and zinc salt during the dilution and mixing process, and the fluazinam/pyraclostrobin nanoemulsion generates latex particles or nanocrystal particles.
  • the content of the active ingredient is at a spraying concentration of about 0.35/0.12/0.06 g/kg water (for example, the dosage of contemporary mancozeb/fluazinam/pyraclostrobin is 70/24/12 g/mu, respectively, and the sprayer uses 200 liters/mu of water. Mu is 1/15 hectare, the same below).
  • the amount of polymer additives is related to the amount of mancozeb/fluazinam/pyraclostrobin generated by the system and the amount of water used for dilution.
  • mancozeb/fluazinam/pyraclostrobin are 70/24/12 g/mu respectively. If the amount of water used for dilution is 200 kg or 300 kg respectively, the percentage concentration of the active ingredient is 0.035%/0.012%/0.006% or 0.023%/0.008%/0.004% respectively.
  • the concentration of polymer additives is at least in the range of 0.1% to 0.2%.
  • the particle size of the mancozeb/fluazinam/pyraclostrobin nanosuspension is about 40-80nm. This nanosuspension can be in a stable state within 2-5 hours without precipitation or settling, and can be directly used in the spraying operation of various pesticide spraying equipment.
  • the mancozeb/fluazinam/pyraclostrobin nano suspension is mainly mancozeb nanoparticles, which are formed by reaction during the dilution and mixing process. Not only does it save the synthesis and purification process of preparing mancozeb original medicine from mancozeb or mancozeb in the pesticide original medicine factory, but it also saves the multi-step physical processing process of processing mancozeb and other original medicines into wettable powders in the pesticide preparation factory.
  • the solution proposed by the present invention can be directly applied to the plant protection link of agricultural production. The process is obviously energy-saving and environmentally friendly, and the production cost can be significantly reduced.
  • a nano suspension dispersion with a mancozeb particle size of less than 100nm is obtained.
  • the small-sized nanoparticles of the present invention can give full play to the efficacy of the medicine, significantly reduce the amount of pesticides used, and play a role of reducing the amount and increasing the efficiency in agricultural production.
  • FIG2 is a flow chart of preparing the mancozeb/fluazinam/pyraclostrobin nanosuspension by diluting with water in the present invention.
  • the invention innovatively proposes a new mode and method for preparing nano suspensions from mancozeb, a pesticide variety containing polyvalent metal ions that is insoluble in water and organic solvents, and a new method for preparing nano suspensions by compounding with other pesticides and fungicides.
  • the precursor of the target product is mixed with the corresponding metal salt, and the mixing and stirring speed of the reactants are controlled by utilizing the rapid nature of ion reaction, so as to obtain a nano suspension with a particle size of less than 100 nanometers for direct use.
  • the method of the invention saves the chemical synthesis and purification process of preparing mancozeb technical from water-soluble mancozeb salt by the pesticide raw material factory, and also saves the multi-step physical processing process of mixing mancozeb technical with other technical materials into wettable powder with larger particle size by the pesticide formulation factory.
  • This innovative research idea, preparation mode and method are the most important key technologies of the invention.
  • This key technology is also suitable for the process of preparing nano suspensions by compounding mancozeb with other pesticides.
  • the dilution water amount is one of the key technologies for controlling the dilution concentration of the two components, thereby obtaining mancozeb/fluazinam/pyraclostrobin nano suspension.
  • the dilution water amount determines the concentration of component A and component B in the dilution. If the amount of water is too little, such as 20 kg, the concentration of component A and component B in the dilution is large, the concentration of nanoparticles generated is high, and the stable time of the particle size below 100nm is short.
  • the amount of water exceeds 300 kg, although a transparent dilution can still be obtained, the concentration of the auxiliary agent contained in the component is significantly reduced, and the stability of the nano suspension will also deteriorate, unless the amount of the auxiliary agent is increased.
  • the appropriate dilution water amount for example, a water amount range greater than 20 kg and less than 300 kg, is one of the key technologies for controlling the concentration of the two components and generating a stable mancozeb/fluazinam/pyraclostrobin nano suspension.
  • auxiliary agents is another key technology for obtaining nano suspensions of mancozeb and its compound active ingredients.
  • water-soluble mancozeb and manganese and zinc salts generate mancozeb nanoparticles in water
  • the dispersion effect of a large amount of water and stirring alone cannot stabilize the size of the generated mancozeb nanoparticles. This is because the particles are not stationary, but are constantly moving and colliding with each other. As a result of effective collision, the particles merge, crystallize and grow, and finally precipitate.
  • auxiliary agent also called dispersant
  • This type of dispersant is first of all a water-soluble polymer that can be dissolved in water.
  • the microscopic state of water-soluble polymers in water usually exists in the form of random coils.
  • the size of the random coils is much larger than the size of the newly generated mancozeb particles and fluazinam/pyraclostrobin particles, depending on the molecular weight and concentration, and the largest can be more than 1 micron.
  • nanoparticles of mancozeb and its compound active ingredients are smaller than 100nm, they can enter the interior of the random coils, preventing and slowing down the collisions between the particles, thereby improving the stability of the generated nanoparticles. This is the role of dispersion, suspension and stabilization played by the addition of additives.
  • the present invention has tested various types of water-soluble polymers.
  • nonionic polymer additives can achieve the desired effect, such as polyoxyethylene ethers of fatty alcohols, acids and amines, polyoxypropylene polyoxyethylene ethers of alkyl aromatic groups, Tween-80, alkyl polysaccharides, castor oil polyoxyethylene ethers, etc.
  • Anionic surfactants The agent can react with manganese and zinc ions to form a water-insoluble precipitate, which loses the dispersing effect.
  • the present invention does not exclude the special case that an individual cationic surfactant is optimized in combination with an appropriate anionic or nonionic surfactant and is soluble in water without precipitation.
  • the type and amount of the water-soluble polymer additive used in the present invention can be determined by experiments. The judgment conditions are as follows: first, the generated mancozeb sodium/fluazinam/pyraclostrobin nano suspension must be transparent in appearance, water-soluble in appearance, and ensure that the particle size is below 100nm; second, the stability time of this transparent nano suspension is in the range of 2 to 5 hours.
  • the amount of adjuvant can be allocated to component A and component B.
  • the proportion of adjuvants in component A and component B can be arbitrarily allocated.
  • component A and component B are specified to be 500 grams each.
  • the amount of water used to dissolve manganese and zinc salts in component B is large, and the solubility of this inorganic salt solution in adjuvants is poor, the amount of adjuvant added to component B will be greatly limited. In this way, the amount of adjuvants allocated to the two components can be determined by the following formula:
  • Amount of additive (component B) total amount of additive - amount of additive (component A) - amount of additive (nanoemulsion)
  • the amount of the auxiliary agent used in the present invention is affected by the amount of dilution water.
  • the amount of the auxiliary agent used will be appropriately increased when the amount of dilution water is large.
  • the ratio of the amount of the auxiliary agent used to the amount of dilution water is at least within 1:1500, preferably within 1:1200, and more preferably within 1:1000.
  • the feeding method is also one of the important factors affecting the performance of mancozeb/fluazinam/pyraclostrobin nanosuspension. Once the amount of water used for dilution and the proportion of components A and B are determined, how to operate during the mixing process will affect the size and stability of the generated particles. For example, the feeding method will involve the following issues:
  • the stirring method will also be involved.
  • the stirring method is closely related to the stirring speed.
  • the present invention adopts the following technical solution:
  • the component A dilution is added to the component B dilution, or the component B dilution is added to the component A dilution; a nano suspension of mancozeb/fluazinam/pyraclostrobin is generated.
  • Component A diluent and component B diluent are aqueous solutions formed by diluting component A and component B with water respectively;
  • Component A composed of water-soluble manebrite or water-soluble manebrite aqueous solution and water-soluble polymer additives; the water-soluble manebrite
  • the salt is one of maneb, maneb, maneb, or a mixture of at least two of them;
  • component A is added with fluazinam/pyraclostrobin nanoemulsion
  • Component B a mixture of manganese salt and zinc salt in a certain proportion, or an aqueous solution thereof.
  • the adding method, adding speed and stirring speed are controlled so that 100 nanometer-level mancozeb/fluazinam/pyraclostrobin nanoparticles are generated in the suspension, and the final suspension is a 100 nanometer-level mancozeb/fluazinam/pyraclostrobin nanosuspension.
  • the stirring speed can be adjusted to the operating speed that is consistent with the physiological functions of the human body.
  • the material addition speed can be appropriately reduced, and the material addition speed can be determined by observing the transparent state of the product in the system.
  • one component can be added to another component in a continuous, intermittent or dropwise manner.
  • dropwise addition method you can use the artificial sprayer commonly available in rural areas to spray and add, which has the best effect.
  • the speed of addition is still determined by observing the transparent state of the product in the system to determine the speed of material addition.
  • the pesticide preparation For existing pesticide preparations, water is used as a dispersion medium for spraying. Usually, the pesticide preparation needs to be diluted with water before spraying, or the pesticide preparations used together need to be mixed together. This process is commonly known as “tank mixing”.
  • the present invention utilizes the “tank mixing” process to mix component A and component B according to a certain concentration, a certain addition method and an addition speed under the action of a specific adjuvant, a dispersant, so as to directly obtain a "tank mixed” transparent mancozeb/fluazinam/pyraclostrobin nanosuspension that can be sprayed on site.
  • the purpose of the present invention is to obtain a mancozeb/fluazinam/pyraclostrobin nano suspension with a transparent stability period of 2 to 5 hours at a level below 100 nm.
  • the mass of the precursor per unit mass and the metal salt (manganese sulfate, zinc sulfate) reacting therewith are fixed, and the mass of fluazinam and pyraclostrobin is also fixed, the factors that can affect the nanometer size and stability of the particles also include: the amount of dilution water, the amount of auxiliary agent and the preparation method.
  • the amount of water used for dilution can affect the size of the generated nano-mancozeb crystals and the length of the stable period.
  • the reason is that the amount of water used as a dispersion medium will affect the concentration of the mancozeb solution and the manganese sulfate and zinc sulfate solutions at the moment of contact reaction, as well as the uniformity of dispersion, and thus will also affect the size of the generated crystals, the effect of crystal dispersion, and the chances of crystal aggregation and growth.
  • the amount of additives used affects the concentration of its aqueous solution in different water amounts, as well as its effect on the generated nano-crystals. The dispersion, suspension and stabilization effect and the length of stabilization time of the suspension.
  • the amount of water is too little, there will be a limit.
  • the stabilization time of the transparent mancozeb/fluazinam/pyraclostrobin nanosuspension is about 1 hour, which cannot fully guarantee the spraying operation time. Therefore, it is necessary to increase the dilution water amount.
  • the invention selects the dilution water amount between 30 and 300 kilograms, preferably between 50 and 200 kilograms, for generating 100 grams of the target product, i.e., a mancozeb suspension with a transparent stable period of 2 to 5 hours at a level below 100 nm.
  • the basic scheme of the 100 nanometer-level or less mancozeb/fluazinam/pyraclostrobin nanosuspension of the present invention is a system formed by three components. They are:
  • Component A' It is composed of solid or aqueous solution of mancozeb, sodium mancozeb or potassium mancozeb, which is the precursor for generating mancozeb nanoparticles.
  • Component A' can be mancozeb or sodium mancozeb, potassium mancozeb, or a mixture thereof.
  • the single component or a mixture of two or three components can be solid, which is easy to package, small in size, and can be dissolved in water before use and dissolve quickly. However, its aqueous solution can also be used, which can be directly diluted to a certain volume with water before use. A certain amount of water-soluble polymer additives can be added to component A' or not.
  • Component B' It is composed of a certain proportion of manganese salt and zinc salt solids or their aqueous solutions, which are multivalent metal ions required for generating mancozeb nanoparticles.
  • Component B' is a mixture of inorganic manganese salt and zinc salt in a certain proportion.
  • the manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate;
  • the zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.
  • Component B' can be solid, so that the packaging volume is small, or its aqueous solution can be used. Due to the limitation of their solubility, the solution volume is large, which is not conducive to storage and transportation, but convenient to use. A certain amount of water-soluble polymer additives may or may not be added to component B'.
  • Component C Fluazinam/pyraclostrobin nanoemulsion
  • Fluazinam/pyraclostrobin nanoemulsion is used as component C.
  • Fluazinam/pyraclostrobin nanoemulsion contains a certain amount of water-soluble polymer additives. As required, the water-soluble polymer additives may be added to component C or not.
  • the total mass of the water-soluble polymer adjuvant required for the three-component solution is distributed among component A', component B' and component C, and is also contained in the fluazinam/pyraclostrobin nanoemulsion in component C.
  • the basic scheme of the 100 nanometer-level or less mancozeb/fluazinam/pyraclostrobin nanosuspension of the present invention is a system formed by four components. They are:
  • Component A' It is composed of solid or aqueous solution of mancozeb, sodium mancozeb or potassium mancozeb, which is the precursor for generating mancozeb nanoparticles.
  • Component A' can be mancozeb or mancozeb, mancozeb, or a mixture thereof.
  • the single component or a mixture of two or three thereof can be a solid substance, which is easy to pack, small in volume, soluble in water before use, and dissolves quickly, but it can also be used
  • the aqueous solution can be directly diluted to a certain volume with water before use.
  • a certain amount of water-soluble polymer additives may or may not be added to component A'.
  • Component B i It is composed of a certain proportion of manganese salt solid or its aqueous solution, which is the manganese metal ion required for the production of mancozeb nanoparticles.
  • the manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate.
  • Component B i can be used in solid form with a small packaging volume; it can also be its aqueous solution. Due to its solubility, the solution volume is large, which is not conducive to storage and transportation, but is convenient to use.
  • a certain amount of water-soluble polymer additive can be further added to component Bi .
  • Component B ii It is composed of zinc salt solid or its aqueous solution in a certain proportion, which is the zinc metal ion required for generating mancozeb nanoparticles.
  • the zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.
  • Component B ii can be in solid form with a small packaging volume; it can also be in aqueous solution, which, due to its solubility, has a large solution volume and is not conducive to storage and transportation, but is convenient to use.
  • a certain amount of water-soluble polymer additive may be further added to component B ii .
  • Component C Fluazinam/pyraclostrobin nanoemulsion
  • Fluazinam/pyraclostrobin nanoemulsion is used as component C.
  • Fluazinam/pyraclostrobin nanoemulsion contains a certain amount of water-soluble polymer additives. As required, the water-soluble polymer additives may be added to component C or not.
  • the total mass of the water-soluble polymer auxiliary agent required for the four-component solution is distributed among component A', component B i , component B ii and component C, and is also contained in the fluazinam/pyraclostrobin nanoemulsion in component C.
  • the four-component solution can also be composed of four components: the precursor as component A, the manganese salt and the zinc salt as component B, the nanoemulsion as component C and the adjuvant as component D.
  • Figure 1 a process flow chart of the traditional preparation of mancozeb technical and processing into wettable powder formulations
  • Figure 2 Schematic diagram of the process for preparing mancozeb/fluazinam/pyraclostrobin nanosuspension (two components)
  • Figure 3 Schematic diagram of the process for preparing mancozeb/fluazinam/pyraclostrobin nanosuspension (three components)
  • the method for preparing a transparent mancozeb/fluazinam/pyraclostrobin nano suspension of less than 100 nm in size comprises the following steps:
  • component A and component B are diluted respectively according to different water amounts and different dilution ratios to form component A dilution liquid and component B dilution liquid.
  • the second step is to uniformly add the component A dilution to the component B dilution in a certain adding method (continuous or intermittent pouring, dropping, spraying, etc.) under mechanical stirring (preferably) or manual stirring conditions at a stirring speed not less than the effective stirring speed; or add in the reverse order.
  • a certain adding method continuous or intermittent pouring, dropping, spraying, etc.
  • mechanical stirring preferably or manual stirring conditions at a stirring speed not less than the effective stirring speed; or add in the reverse order.
  • component A' and component B' are diluted respectively according to different water amounts and different dilution ratios to form component A' dilution liquid and component B' dilution liquid.
  • the second step is to add component C into the diluted solution of component A’ and stir to disperse evenly.
  • the third step is to uniformly add the component A' and component C dilutions to the component B' dilution in a certain adding method (continuous or intermittent pouring, dropping, spraying, etc.) under mechanical stirring (preferred) or manual stirring conditions at a stirring speed not less than the effective stirring speed; or add in the reverse order.
  • Mancozeb/fluazinam/pyraclostrobin nanosuspension can be used to prevent and treat citrus scab and anthracnose.
  • the dosage of its active ingredients is 70/20/12 g/mu respectively, and the dilution water dosage for spraying citrus is about 200 kg/mu.
  • the precursor mancozeb required to produce 70 g of mancozeb is about 63 g.
  • Component ratio The component ratio, dilution water volume, water volume distribution, addition sequence and method, and test results of each component are listed in the following table:
  • Component A and component B were diluted and dissolved in the ratio of 2/3 and 1/3 of 200 kg of water, respectively. Under manual stirring, the component B dilution was added to the component A dilution in a continuous stream to obtain a transparent mancozeb/fluazinam/pyraclostrobin nanosuspension. The stability time was 4.5 hours.
  • Mancozeb/fluazinam/pyraclostrobin nanosuspension can be used to control banana scab and leaf spot.
  • the dosage of its active ingredients is 120/20/8 g/mu respectively, and the dilution water dosage for spraying bananas is 300 kg/mu.
  • the precursor mancozeb required to produce 120 g of mancozeb is about 108 g.
  • Component ratio The component ratio, dilution water volume, water volume distribution, addition sequence and method, and test results of each component are listed in the following table:
  • Component A' and component B' were diluted and dissolved in a ratio of 4/5 and 1/5 of 300 kg of water, respectively, and then component C was added to the dilution of component A' and dispersed evenly to form a mixed dilution of component A' and component C. Under stirring, the dilution of component B' was added to the mixed dilution of component A' and component C in a continuous spraying manner to obtain a transparent nano suspension of mancozeb/fluazinam/pyraclostrobin, which had a stable time of 4.5 hours.
  • Mancozeb/fluazinam/pyraclostrobin nanosuspension can be used to control downy mildew of melons.
  • the dosage of active ingredients is 55/10/5 g/mu respectively, and the dilution water dosage for spraying melons is 60 kg/mu.
  • the precursor mancozeb required to generate 55 g of mancozeb is about 50 g.
  • Component ratio The component ratio, dilution water volume, water volume distribution, addition sequence and method, and test results of each component are listed in the following table:
  • Component A' and component B' were diluted and dissolved in a ratio of 2/3 and 1/3 of 60 kg of water, respectively, and then component C was added to the dilution of component A' and dispersed evenly to form a mixed dilution of component A' and component C. Under stirring, the dilution of component B' was added to the dilutions of component A' and component C in a continuous spraying manner to obtain a transparent nano suspension of mancozeb/fluazinam/pyraclostrobin. The stability time was 8 hours.
  • Mancozeb/fluazinam/pyraclostrobin nanosuspension can be used to control potato late blight.
  • the dosage of its active ingredients is 50/8/5 g/mu respectively, and the dilution water dosage for spraying potatoes is 50 kg/mu.
  • the precursor mancozeb required to produce 50 g of mancozeb is about 45 g.
  • Component ratio The component ratio, dilution water volume, water volume distribution, addition sequence and method, and test results of each component are listed in the following table:
  • Component A and component B were diluted and dissolved in a ratio of 2/3 and 1/3 of 50 kg of water, respectively. Under manual stirring, the component B dilution was added to the component A dilution in a continuous dropwise manner to obtain a transparent mancozeb/fluazinam/pyraclostrobin nanosuspension. The stability time was 4 hours.

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Abstract

本发明属于纳米农药领域，涉及微粒尺寸小于100纳米的代森锰锌复配纳米悬浮液及其制备方法。本发明采用两种或三种组分兑水稀释混合形成100纳米以下级代森锰锌复配纳米悬浮液。制备方法：在搅拌速度不小于有效搅拌速度的条件下，将组分一稀释液加入到组分二稀释液中，或将组分二稀释液加入到组分一稀释液中；形成代森锰锌复配纳米悬浮液。

Description

防治水果类病害的纳米悬浮剂 【技术领域】
本发明属于纳米农药领域，特别涉及微粒尺寸小于100纳米的三元复配纳米悬浮液的制备。
【背景技术】
纳米农药是指农药微粒尺寸处于纳米量级的农药制剂。从应用效果和稳定性看，纳米农药的微粒尺寸最好在100nm以下，且越小越好。目前，主流农药制剂的微粒尺寸在微米量级，即在几个微米以上。如能减小至相应的纳米量级，即尺寸缩小1000倍，则相同质量的有效成分，在保持微粒形态不变的前提下，理论上微粒数量可增加10亿倍，表面积可增加1000倍。农药微粒数量和表面积的剧增，将使农药有可能分散得更加均匀，与防治靶标接触得更为广泛，药效就能充分发挥和提高。这就是为什么要发展纳米农药的根本原因。
代森锰锌(mancozeb)在国际上已有超过五十年的使用历史。它的用量一直是大吨位产品，是一种效果很好的保护性有机硫杀菌剂。其特点是毒性低、持效期长、能杀灭多组病菌、不易产生抗性、防治效果较好，因此受到重视。
代森锰锌属于具有保护作用的广谱、非内吸性杀菌剂。用于果树、蔬菜观赏植物、烟草等多种作物。同时还可防治多种重要的叶部真菌病害。用于防治马铃薯、番茄的早疫病、晚疫病；葡萄霜霉病、黑腐病；小麦、玉米的网斑病、条斑病、大斑病；棉花、花生的立枯病、苗斑病、蔬菜霜霉病、炭疽病、疫病等，都有很好的防治效果。
代森锰锌可以和多种农药复配，形成多种复配制剂。但无论是单独使用，还是复配使用，由于受其物理性能——既不溶于水，也不溶于有机溶剂——的影响，其主要剂型为传统的粉剂、可湿性粉剂、水分散粒剂，以及悬浮剂。按照现有的农药制剂加工技术水平，其制剂中农药微粒的最小尺寸通常也在几个微米以上，大的十几微米甚至几十微米。代森锰锌农药微粒尺寸大，不利于药效的发挥，加上多年来大量使用产生的一定抗药性，目前单位面积的使用量大，通常为有效成分750克～2250克/hm2。这样，如何提高它的药效，减少它的单位面积用量？就成为该农药品种的制剂类型研究的一项重要内容。
需要明确的是，现有的几种代森锰锌剂型的制备，其过程是在先合成原药的基础上，再进行各种剂型的加工。具体步骤包括：(1)原药合成。分为两步：第一步是合成代森铵或代森钠，第二步是合成代森锰锌。合成的代森铵或代森钠是水溶性的，可溶解在水中，再分别与锰盐、锌盐进行成盐及络合反应，得到块状沉淀的代森锰锌。沉淀的代森锰锌既不溶于水，也不溶于有机溶剂，需要进行分离、洗涤、干燥，得到代森锰锌原药。(2)制剂加工。以固体代森锰锌原药为原料，进行制剂的加工。通常需要进行粉碎、研磨、混合等加工，才能得到代森锰锌制剂。上述从代森铵或代森钠之后的制备过程，需要添加相应的生产设备与车间，如过滤机、干燥机、粉碎机、研磨机、混合机，还需要相应的生产过程和加工工艺。可以发现，从合成出水溶性的代森铵或代森钠，到加工成代森锰锌不同固体剂型，工艺长又耗能。
传统制备代森锰锌原药和加工成最普遍的粉剂、可湿性粉剂的工艺流程如图1所示。
现有技术：以代森锰锌为原药制备纳米代森锰锌的技术方案。
中国发明专利CN201711490378.4公开了一种纳米代森锰锌粉剂剂型。
该发明专利公布的技术方案，不能获得严格意义上的“纳米代森锰锌”，尤其是微粒尺寸在100nm以下的代森锰锌。必须指出的是，在体系中加入了水溶性高分子作为分散剂，其水溶液应呈现透明状态。而滤饼的水分散液则呈现“悬浊”状态，表明了该技术方案不能得到真正意义上的纳米悬浮液，尤其是微粒尺寸小于100nm的代森锰锌纳米制剂。
对比技术(CN201711490378.4)声称在合成代森锰锌的反应中，通过加入分散剂和缓冲液来生成纳米尺寸的代森锰锌。但按照科学常识分析，分散剂的选择是错误的，加之使用酸性的缓冲液，使分散剂的作用丧失。本发明通过试验发现，只有在生成代森锰锌的浓度极低的情况下，才可能生成代森锰锌微粒纳米尺寸。因此认为对比技术无法实现工业生产“纳米代森锰锌”。
鉴于国内外农药公司在中国登记的各种剂型的代森锰锌产品，其微粒都是微米尺寸，以及上述纳米代森锰锌技术方案中存在的不足，这也反映出，创新纳米代森锰锌，尤其是尺寸小于100nm的纳米代森锰锌产品，存在很大的技术难度。这也提示我们，要获得代森锰锌纳米悬浮液，必须创新思路和另辟蹊径。
【发明内容】
在先申请：PCT/CN2022/139831；PCT/CN2022/139832；PCT/CN2022/139833
上述发明的目的之一在于克服现有技术的不足，提供一种有别于现有技术制备代森锰锌粉剂剂型的新思路与方法，通过兑水稀释过程，实现代森铵(或代森纳、代森钾)和锰盐、锌盐的反应，生成代森锰锌，从而提供一种表观水溶、外观透明的代森锰锌纳米悬浮液，并直接用于喷洒。
上述发明所述代森锰锌纳米悬浮液，装入农药喷施器械，即可进行喷施作业。
本发明的创新思路如下：
代森铵是水溶性铵盐，在水中是单分子分散，作为一种组分。与之反应的锰盐、锌盐，在水中也是单分子及金属离子的分散，作为另一组分。当二者相遇时，离子之间的反应，很容易形成代森锰盐和锌盐结构。由于锰离子、锌离子都是多价金属离子，除认为成盐外，还可能形成配合物结构。无论是成盐或络合，在混合时，通过控制某一组分加入量，可生成代森锰锌的纳米晶粒。
在搅拌速度可控的条件下，将一组分(例如锰盐、锌盐)水溶液加到另一组分(例如代森铵)水溶液中。控制滴加速度和搅拌速度，可以生成代森锰锌的纳米晶粒及其悬浮液。
生成的代森锰锌纳米晶粒，当微粒尺寸很小数量很少时，是可暂时稳定地分散在水体系中。由于纳米晶粒的不断生成，就会发生晶粒之间的碰撞、长大和聚集。当代森锰锌纳米晶粒的尺寸接近可见光波长，体系就开始出现乳光，当超过时，逐渐不透明。加上自身重力的作用，将以大尺寸的晶粒沉淀析出。为防止这一现象，体系中须加入高分子助剂。高分子助剂是水溶性高分子，通常都是非结晶性聚合物，在水中溶解后是以无规线团形态结构存在。无规线团是水溶性高分子 链自发卷曲形成的疏松的球形结构，内部聚集的是亲油疏水的分子主链，外部是亲水的极性基团。此时，体系生成的代森锰锌纳米晶粒，当尺寸小于100纳米时，在机械搅拌剪切力作用下，这些不溶于水的纳米晶粒，就会扩散进入到无规线团内部并被负载，隔离和阻止了晶粒的有效碰撞、长大、析出和沉淀。因此，水溶性高分子助剂形成的无规线团，对代森锰锌纳米晶粒起到了分散、悬浮、稳定和保护作用。无规线团是均匀分散在水相，扩散进入无规线团内部的纳米晶粒也均匀分散在水相。当晶粒尺寸在100纳米以下，体系清澈透明，表观水溶，会出现“丁达尔现象”。
需要指出的是，在生成纳米晶粒的过程中，组分的加入速度和进入体系的搅拌速度，涉及到在单位时间内加入的量和分散均匀程度，是影响生成纳米晶粒大小的重要因素。对于加入速度，如果以生成的纳米晶粒尺寸小于100纳米为目标，则体系是否清澈透明就是判断标准。它的理论基础是，当微粒尺寸小于可见光波长(400～760纳米)下限的四分之一时，不形成严重的折射和反射，因此体系是透明的。反之，如果体系有乳光或不透明，表明晶粒尺寸大于100纳米。
要实现这一目标，必须关注以下几点：
①两组分溶液的混合速度(即其中一组分的加入速度)不能太快。加入太快，两组分分散不均，局部浓度过高，则生成晶粒的速度也快，生成的晶粒数量也多，有可能发生纳米晶粒之间的聚集，从而使晶粒尺寸变大。如果体系出现乳光，就说明晶粒尺寸已经在几百纳米。因此，其中一组分的加入速度以保持体系始终透明为准。
②体系的搅拌速度要适当加快。体系的搅拌速度涉及到水相中纳米晶粒的生成速度和分散速度。搅拌充分，扩散快，有利于纳米晶粒的快速形成和分散，保持小尺寸晶粒，避免发生晶粒之间的聚集。搅拌速度应与组分加入速度配合，也以保持体系始终透明为准。
术语解释
丁达尔现象：所谓丁达尔现象，是指当一束光线透过胶体，从垂直入射光方向可以观察到胶体里出现的一条光亮的“通路”，这一现象也叫丁达尔效应(Tyndall effect)。丁达尔效应的实质，是光在胶体中传播时的一种散射现象。之所以会发生这种现象，主要是因为胶体粒子的粒径在1～100nm，可见光透过胶体时会产生较为明显的散射作用，而真溶液对光的散射作用则非常微弱。胶体有明显的丁达尔现象，而分子分散的真溶液几乎没有，因此常被用来区分胶体溶液和真溶液。如果粒子小于入射光波长，则发生光的散射，是光波环绕微粒而向其四周放射，被称为散射光或乳光。丁达尔效应本质上是光的散射现象或称乳光现象。真溶液对光的散射作用很微弱。散射光的强度还随分散体系中粒子浓度增大而增强。由此，当观察的溶液清澈透明时，表明溶液中的微粒尺寸小于100nm，可出现丁达尔现象。如果粒子大于入射光波长(400nm～740nm)，则明显发生光的反射。溶液显示乳光越来越重、浑浊液甚至不透明时，微粒尺寸已增至接近微米或以上。
体系：所谓体系，是指本发明在制备代森锰锌纳米悬浮液时，在控制加入速度方式和搅拌的前提下，两组分混合而形成的悬浮液系统。体系是由水、前驱体、锰盐锌盐和水溶性高分子助剂等物质混合生成的目标产物——悬浮液。
组分：所谓组分，是指包含一种或多种成份的组合物。原则上，本发明使用的任何一种成分，都可以单独形成一种组分，但考虑到包装运输和使用方便，应对成分进行组合简化。其原则是：①成分之间不发生反应；②成分形成的组分数量不宜过多。
成分：所谓成分，是指本发明使用的原料物质，包括水溶性代森盐、锰盐、锌盐、水溶性高分子助剂和水。
前驱体：所谓前驱体，是指目标产物代森锰锌的生成反应所使用的母体物质，即指水溶性的代森盐，包括代森铵、代森钠、代森钾。
水溶性高分子助剂：是指大分子中含有亲水的极性基团能够溶于的高分子物质，也称为高分子表面活性剂、活性剂。水溶性高分子助剂可以起到分散、悬浮、乳化及稳定作用。根据基团性质，可以分为阴离子、阳离子、两性离子和非离子高分子助剂。
微粒粒径：又称微粒尺寸；是指体系中前驱体在水溶性高分子助剂的分散下，与锌盐、锰盐相互作用形成的代森锰锌晶粒尺寸的大小，也包括与之复配的其它农药品种形成的微粒尺寸，并不特指晶粒的微观形态结构。
100纳米以下级：是对体系中农药微粒尺寸的统计学意义上的分类。悬浮液中所有农药微粒尺寸呈现一种统计学分布。本发明所述的100纳米以下级纳米悬浮液，是指在微粒分级的各级分的质量分数与其对应尺寸的粒径分布曲线上的峰值小于100纳米。可用英国马尔文激光纳米粒度测定仪进行检测，采用Number统计方法进行处理。
稳定期：是指纳米悬浮液在制备完成后能够保持透明状态的稳定时间。为保障喷施作业的完成，稳定期应当不小于1小时。本发明提出小时级稳定期，是指稳定时间在1～5小时之间。
有效搅拌速度：所谓有效搅拌速度，是指在一定的加入方式下，一组分在加入到另一组分时，通过不小于有效搅拌速度的搅拌，使得体系中生成的纳米晶粒能够及时分散开来，不发生晶粒的长大和聚集，晶粒尺寸不增大到几百纳米级别。体系生成液呈现透明状态是有效搅拌的标志。
有效搅拌：加入组分和搅拌的方式、速度对体系生成液产生重要影响。搅拌方式包括机械搅拌、多点机械搅拌、人工搅拌、多点人工搅拌。搅拌速度快，有利于产生好的效果。若体系生成液呈现透明状态，则视为有效搅拌。反之，视为无效搅拌。
加入方式：所谓加入方式，包括组分A加入组分B、组分B加入组分A，或组分A和组分B同时加入体系中，还包括连续加入、间断加入、细流加入、滴加、喷雾加入，以及固定位置或移动位置加入等。加入方式以两组分尽快混合与分散为宜。
加入速度：在确定加入方式后，以实现有效搅拌为目标，控制组分的加入量。
纳米乳剂：又称纳米乳液。是指农药有效成分形成的溶液在分散于水中助剂的作用下，形成纳米尺寸乳胶粒的分散体系。纳米乳液的外观清澈透明，微粒尺寸通常在100nm以下，具有热力学稳定性。
氟啶胺/吡唑醚菌酯纳米乳液：也称为氟啶胺和吡唑醚菌酯复配纳米乳液
代森锰锌/氟啶胺/吡唑醚菌酯的多元复配
代森锰锌是一种广谱性多位点的保护性杀菌剂，主要作用是预防真菌性病害的发生，要想它发挥最佳防治效果，在使用时一是要提前使用，二是最好与其他药剂、特别是内吸性的杀菌剂混配使用。因此，为了提高对作物病害的防治效果，往往将代森锰锌与其他杀菌剂进行复配。本发明为了提高代森锰锌防治病害效果，一次植保获得多靶标防治效果，提出在获得代森锰锌纳米悬浮液技术的基础上，进一步获得代森锰锌与不同杀菌剂的二元、三元或多元复配的纳米悬浮液。本发明提出方法和方案可使代森锰锌复配纳米悬浮液应用得更为广泛。
氟啶胺(fluazinam)分子式为C13H4Cl2F6N4O4，化学名称为3-氯-N-(3-氯-5-三氟甲基-2-吡啶基)-α，α,α-三氟-2,6-二硝基-对甲苯胺，是一类吡啶胺衍生物，具有杀菌谱广、防效快且不易产生交互抗性的特点，是目前广谱性杀菌剂中活性最高的药剂，常被用作保护性的杀菌剂。氟啶胺不具有内吸性，因此使用后无法被植物吸收。氟啶胺对高等真菌和低等真菌都有较好的防治效果，可有效防治霜霉病、灰霉病、炭疽病、菌核病、根肿病、猝倒病及果树上的疮痂病、黑星病等，其中对灰霉病、疫病、根肿病有特效。
吡唑醚菌酯(pyraclostrobin)分子式为C19H18ClN3O4，化学名称为N-[2-[[1-(4-氯苯基)吡唑-3-基]氧甲基]苯基]-N-甲氧基氨基甲酸甲酯或{2-[1-(4-氯苯基)-1H-吡唑-3-基氧甲基]苯基}甲氧基氨基甲酸甲酯，是一种甲氧基丙烯酸酯类广谱杀菌剂，主要用于防冶作物上由真菌引起的多种病害。吡唑醚菌酯由于其具有杀菌谱广、高效、低毒、无味、不易发生抗药性、促进作物生长、提升作物抗逆性等特点，在全球农业领域得到了广泛应用。
代森锰锌与氟啶胺按一定比例复配形成一种广谱低毒复合杀菌剂，以保护作用为主，治疗作用为辅。提前使用，可有效预防多种病害的发生，且不易产生抗药性，持效期长。代森锰锌与氟啶胺复配后，适用于多种作物，能有效预防由交链孢属、疫霉属、单轴霉属、核盘菌属和黑星菌属等引起的病害，对抗苯并咪唑和二羧酰亚胺类杀菌剂的灰葡萄孢也有很好的效果。如在大棚番茄发病初期，可先用代森锰锌和氟啶胺的复配制剂进行有效保护，可降低后期病害重发的风险。
代森锰锌与氟啶胺的复配制剂，目前未见有登记，生产上常见两种有效成分的复配比例范围为：100/10～100/30。
代森锰锌也可与吡唑醚菌酯按一定比例复配形成一种广谱低毒复合杀菌剂，具有保护和治疗双重作用。两种杀菌机理，使得病菌不宜产生抗药性，使用方便安全，持效期较长。代森锰锌/吡唑醚菌酯复配制剂适用于多种作物，对许多高等真菌性病害都有较好的防治效果，对黑星病、白粉病、叶斑病效果突出。目前已用于防治的作物和病害有：苹果斑点落叶病；香蕉叶斑病、黑星病；柑橘疮痂病、砂皮病、炭疽病；甜瓜霜霉病；草莓褐斑病、草莓炭疽病；豇豆锈病等。
代森锰锌/吡唑醚菌酯的复配制剂，两种有效成分的现有的复配比例范围为：100/5～100/25。剂型主要为悬浮剂、可湿性粉剂、水分散粒剂、可分散油悬浮剂。
由于作物病害的发生，需要杀菌剂在保护的同时，能兼具治疗作用。因此，可在代森锰锌与氟啶胺复配的基础上，再加入吡唑醚菌酯，制备成代森锰锌/氟啶胺/吡唑醚菌酯三元复配制剂。除吡唑醚菌酯外，也可加入其它一些杀菌剂品种。
代森锰锌/氟啶胺/吡唑醚菌酯的复配制剂，三者的用量范围为：100/10～30/5～25。
本发明所述代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液是指100纳米以下级的纳米悬浮液；所述100纳米以下级代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液由至少两种组分兑水稀释混合形成：
代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液
在先申请(PCT/CN2022/139831)已对代森锰锌纳米悬浮液的形成机制进行了描述。在此基础上，加入氟啶胺/吡唑醚菌酯，进一步形成三元农药的纳米悬浮液。氟啶胺/吡唑醚菌酯是以纳米乳液的形式加入到组分A中，当按照一定条件进行两组分混合时，氟啶胺/吡唑醚菌酯的微粒存在形式取决于稀释水量和体系中高分子助剂的量。当水量较少时，被稀释的高分子助剂的量能够继续维持纳米胶束的存在，此时，代森锰锌纳米晶粒、氟啶胺/吡唑醚菌酯纳米胶粒共存。若水加入量多到不足以维持纳米胶粒所需最低高分子助剂的浓度，胶束就会消失，氟啶胺/吡唑醚菌酯会以纳米晶粒的形态在水中析出，成为三种农药有效成分的纳米晶粒混合物，或三种农药有效成分混合生成的纳米晶粒的混合物，共存于纳米悬浮液中。
两组分的方案如下：
组分A：水溶性代森盐或水溶性代森盐水溶液，水溶性高分子助剂和水；所述水溶性代森盐为代森铵、代森钠、代森钾之一，或至少两种的混合物；所述水溶性高分子助剂为至少一种非离子表面活性剂的组成复合助剂或其水溶液；
同时，组分A添加氟啶胺/吡唑醚菌酯复配的纳米乳液；
组分B：是由按照一定比例组成的锰盐和锌盐混合物；锰盐锌盐分别为至少一种盐类的组成物质；
所述组分B，可以是锰盐和锌盐的固体混合物，也可以是加水形成水溶液，还可以进一步添加水溶性高分子助剂。
所述水溶性高分子助剂为至少一种非离子表面活性剂。
所述锰盐选自硫酸锰、醋酸锰、氯化锰、硝酸锰中的至少一种；所述锌盐选自硫酸锌、醋酸锌、氯化锌、硝酸锌中的至少一种。
所述水溶性高分子助剂的用量包括组分A和组分B中的高分子助剂用量之和，其与稀释用水量之比，不大于1∶1500。所述稀释用水量包含体系中的所有水。
非离子表面活性剂，可选水溶性淀粉及其衍生物、水溶性瓜尔胶及其衍生物，聚氧丙烯-聚氧乙烯嵌段共聚物、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚、脂肪胺聚氧乙烯醚、烷基芳基聚氧丙烯聚氧乙烯醚、芳基酚聚氧乙烯醚、蓖麻油聚氧乙烯醚、烷基多糖苷、吐温、聚乙烯醇、聚乙烯吡咯烷酮等。其中，壬基酚聚氧乙烯醚的降解产物具有雌性化毒性，应拒绝使用。优选的，聚氧丙烯-聚氧乙烯嵌段共聚物、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚、脂肪胺聚氧乙烯醚、烷基芳基聚氧丙烯聚氧乙烯醚、PO-10、蓖麻油聚氧乙烯醚、烷基多糖苷、吐温等。
进一步的，所述100纳米以下级代森锰锌纳米悬浮液，具备小时级稳定期。
对于代森盐、锰盐、锌盐分别为代森铵、硫酸锰、硫酸锌时，其质量比的范围为：
代森铵∶硫酸锰∶硫酸锌＝90∶35～55∶6～17
优选的，代森铵∶硫酸锰∶硫酸锌＝90∶41～45∶7～9
进一步的，代森铵∶硫酸锰∶硫酸锌＝90∶41∶7
当三者质量比代森铵(生成100代森锰锌)∶硫酸锰∶硫酸锌＝90∶41∶7时，在以尽可能少的水溶解锰盐锌盐的组分B中，加入水溶性高分子助剂的质量以不出现浑浊状态为宜，通常不高于5％。
稳定期
本发明制备的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液是一类外观透明、表观水溶的溶液，但本身并不是热力学稳定的溶液。因此，纳米悬浮液保持外观透明状态的时间并不是无限长，而是存在一个稳定期。从喷施作业的特点考虑，在纳米悬浮液配制好后，需要的操作时间至少应在1小时以上，这样可以以小时计，描述稳定期时间的长短。由此，本发明提出100nm以下纳米悬浮液存在“稳定期”的概念。即，本发明制备的100nm以下级纳米悬浮液，在溶液保持透明期间内完成喷施作业，稳定期至少应达到1小时。
从应用的角度，稳定期可以进一步区分为4个时间段：1小时以内，1～2小时，2～5小时，5小时以上。
在稳定期内，纳米级悬浮液仍保持透明状态，即保证微粒尺寸仍然小于100nm。
小时级稳定期
从喷施作业的角度来分析：
稳定时间在1小时左右，对于喷施作业的操作时间并不充裕；稳定期超过5小时以上多元复配的纳米悬浮液很难实现。
稳定时间在2～5小时之间，大部分农药器械的喷施作业都能够在这个时间内从容完成。
本发明所述小时级稳定期，是指稳定时间在1～5小时之间。
对于小时级稳定期，还可以再进行细化分期。
1～2小时为喷施作业的基本期；大多数情况下喷施器械都能完成作业。
2～5小时为喷施作业的充分期；可以适应于遇到特殊情况被耽搁的喷施作业。
代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的成分和助剂
使用传统代森锰锌、氟啶胺、吡唑醚菌酯农药制剂，可以分别是三个组分的单剂，也可以是两个组分，代森锰锌/氟啶胺是复配组分，吡唑醚菌酯则是另一组分。这些组分多为水分散粒剂，三者一起使用时，需要进行“桶混”，用水稀释后才可喷施作业，但农药微粒尺寸都在微米级以上。本发明为了获得纳米级悬浮液，采取至少两组分模式，按照一定方法，进行兑水稀释，可以获得100纳米以下级代森锰锌/氟啶胺/吡唑醚菌酯/纳米悬浮液。
两组分方案
100纳米以下级代森锰锌悬浮液，具备小时级稳定期，是由两种组分混合反应生成的体系。它们分别是：
组分A：由代森铵(或代森钠、代森钾)、氟啶胺/吡唑醚菌酯纳米乳液、水组合而成，形成一种透明的水溶液。其中，生成代森锰锌的前驱体，起到分散、悬浮和稳定作用的水溶性高分子表面活性剂和水，是组分A的基本成分。在此基础上，可加入有效成分的纳米乳剂。
在组分A中，氟啶胺和吡唑醚菌酯纳米乳液中含有一定量的水溶性高分子助剂。根据需要，可继续另外添加水溶性高分子助剂。
组分B，是由按照一定比例组成的无机锰盐和锌盐混合物的体系，该体系有三种形态：固体的无机锰盐和锌盐(组分B1)、无机锰盐和锌盐的水溶液(组分B2)、无机锰盐和锌盐与水溶性高分子助剂组成的水溶液(组分B3)。
所述锰盐选自硫酸锰、醋酸锰、氯化锰、硝酸锰中的至少一种；所述锌盐选自硫酸锌、醋酸锌、氯化锌、硝酸锌中的至少一种。
由于无机锰盐和锌盐在水中的溶解度有限，为了尽可能减少组分B的容量，需要限制使用水的用量。加之无机盐的溶解性能也受到助剂用量的影响，从而也限制了水溶性高分子助剂在组分B中的加入量。
B3属于改进方案，在于将水溶性高分子助剂既分配到组分A中，又分配到组分B中。鉴于组分B的几种限制，水溶性高分子助剂在组分B中的比例存在一上限，除非不考虑组分B对一定容量的限制。
生成代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的成分配比
两组分方案包括三种有效成分：代森锰锌、氟啶胺、吡唑醚菌酯。
组分A：使用代森铵(或代森钠、代森钾)，或其至少两种混合物的水溶液，氟啶胺/吡唑醚菌酯纳米乳液，然后可继续加入助剂。
组分B：以硫酸锰(或醋酸锰、氯化锰、硝酸锰)、和硫酸锌(或醋酸锌、氯化锌、硝酸锌)按照一定比例溶于水；也可以加入助剂。
在组分A和组分B中，有效成分的用量是决定两组分构成的基础。组分A中的代森铵(或代森钠、代森钾)，是生成纳米代森锰锌的前驱体，是决定组分B构成的基础。
本发明以1/15公顷田地假若需要70克代森锰锌，按照代森锰锌/氟啶胺/吡唑醚菌酯三者之比为(70/24/12)克喷施为例。以生成(70+24+12)克100nm以下级代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液为基础，进行两组分的设计。
组分A，需要代森铵或代森钠、代森钾，优选代森铵作为前驱体，大约63克；氟啶胺/吡唑醚菌酯(24％+12％)纳米乳液100克(含氟啶胺24克和吡唑醚菌酯12克，及一定量的助剂)，根据前述助剂在组分A和组分B中的分配原则，绝大部分助剂将分配在组分A中。如果组分A和组分B都以500克质量包装规格计，水的用量就是减去代森铵、氟啶胺/吡唑醚菌酯纳米乳液、高分子助剂后的量。
组分B，先确定与代森铵反应所需要的无机锰盐和锌盐的量。本发明优选硫酸锰、硫酸锌。一般倾向于认为，锰离子与代森铵反应，取代铵离子而成盐，生成一种代森锰的环状结构或线性聚合物结构，而锌离子则和代森锰盐分子上的硫原子发生络合，形成络合物结构。
代森铵∶硫酸锰∶硫酸锌质量比
代森铵与锰离子、锌离子与之间并无严格的配比，工业生产为保证反应完全，使用的三者比例大，是其上限。本发明采用低于它的比例，原因：①锰、锌离子用量大，浓度高，不利于小尺寸晶粒的形成和稳定；②使用低用量的锰盐、锌盐，即使反应不充分，其所有成分都是可独立使用的杀菌剂；③纳米悬浮液的制备过程，无需工业生产对代森锰锌的水洗、分离和干燥，不损失成分。三者之间的分子比与质量比如下所示：
代森铵∶硫酸锰∶硫酸锌＝1∶0.8∶0.15(分子比)；90∶55∶17(质量比)(理论上限)
优选的，代森铵∶硫酸锰∶硫酸锌＝1∶0.64∶0.08(分子比)；90∶43∶9(质量比)(工业 生产比例)
更优选的，代森铵∶硫酸锰∶硫酸锌＝1∶0.6∶0.06(分子比)；90∶41∶7(质量比)(实际 应用)
组分A和组分B的助剂分配
助剂主要在组分A中。
组分A主要含有代森铵(或代森钠、代森钾)、氟啶胺/吡唑醚菌酯纳米乳液。
组分A和组分B必须分装的原因是，两者混合在一起就会发生反应。如果采用两组分方式，组分A中氟啶胺/吡唑醚菌酯纳米乳液含有助剂，还须另加助剂，除非增加单独助剂的第三组分。这样将组分和稀释过程变得繁杂。组分A加助剂的条件在于：代森铵和助剂都溶于水，可以混溶，而不会出现沉淀等不稳定现象。但考虑到代森铵和助剂的含量高、本身粘度较大，不易操作，因此要加入一定量的水使其溶解稀释，降低粘度，便于操作。加入的水量，在实现上述目的后，应尽可能减少组分A的总质量，降低生产、包装和运输成本。
组分B主要是锰盐和锌盐混合物，或其水溶液，或其高分子助剂的水溶液。
组分B可以是锰盐和锌盐的固体混合物。与组分A混合前需溶于水，为方便，可使用他们的水溶液。它们的溶解度不高，需要的水量较大。根据混合盐溶解情况，可选择加入或不加助剂。原因有二：一是组分B中加入助剂量多，在锰盐、锌盐、助剂和水的混合溶液表面会出现凝结成膜现象，影响下一步操作；二是如果组分A中助剂量能够悬浮和分散生成的代森锰锌/氟啶胺/吡唑醚菌酯纳米晶粒，组分B中就可以不加助剂。但考虑到这类农药主要用于果园的病害防治，喷施用水量大，通常多达300千克/亩。如果组分A中的助剂量并不足以支撑纳米晶粒的分散和悬浮，故在组分B中应加入适当助剂。其前提是，在锰盐和锌盐的混合水溶液中，加入助剂的量，应使组分B依然保持透明，不发生混合溶液表面凝结成膜的情况。
当质量比代森铵(生成100代森锰锌)∶硫酸锰∶硫酸锌＝90∶41∶7时，在溶解锰盐、锌盐的混合溶液的组分B中，加入助剂的质量浓度一般不高于5％。
虽然组分A和组分B都可以通过扩大容量的方法来解决上述难点，但两组分用量规格的加大，无疑会增大生产、包装和运输成本。综合考虑这些因素，在生成单位质量代森锰锌复配农药纳米微粒的前提下，平衡各成分用量和产品规格之间的关系，尽可能少使用助剂和水，是考虑的重要因素。
水溶性高分子助剂
⑴具有分散悬浮作用的水溶性高分子助剂，是关系到本发明在两组分或三组分稀释混合时生成的代森锰锌/氟啶胺/吡唑醚菌酯纳米晶粒尺寸大小，以及能否稳定分散、悬浮的重要成分物质。
⑵水溶性高分子助剂属于高分子表面活性剂，具有分散、悬浮、提高粘度等性能，源于具有疏水的链结构和亲水性官能团。这些分布在端基和侧基的基团有，羟基、羧基、羧甲基、磺酸基、硫酸基、磷酸基、氨基、季铵盐基等。按照来源分为天然和合成高分子，按照亲水基团的性质分为阴离子、阳离子、非离子和两性离子高分子。
⑶本发明选择水溶性高分子助剂的原则是，①能够稳定分散、悬浮生成的农药纳米晶粒；②不受多价金属离子与水溶性代森盐反应的影响；③尽可能环境友好。因此本发明选择天然物质衍生物的非离子高分子助剂。如聚氧乙烯-聚氧丙烯-聚氧乙烯嵌段共聚物，各种以脂肪醇、脂肪酸、脂肪胺、烷基芳基酚、油基等为疏水基团的聚氧乙烯醚，如平平加(Pere克al)系列、OP系列、吐温(Tween)系列、多元醇系列、蓖麻油酸系列、烷基多糖苷等。但对具有雌性化毒性的壬基酚聚氧乙烯醚类，应该摒弃使用。
⑷所述代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液，是利用兑水稀释混合过程中，由水溶性代森铵(或钠)与锰盐、锌盐反应生成，由氟啶胺/吡唑醚菌酯纳米乳剂生成乳胶粒或纳米晶粒。有效成分含量处于喷施浓度，约0.35/0.12/0.06克/千克水(例如，当代森锰锌/氟啶胺/吡唑醚菌酯用量分别为70/24/12克/亩，喷雾机用水200升/亩。亩为1/15公顷，以下同)。控制高分子助剂用量，可获得分散稳定的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液。
高分子助剂用量与体系生成的代森锰锌/氟啶胺/吡唑醚菌酯的用量和稀释用水量相关。比如，代森锰锌/氟啶胺/吡唑醚菌酯分别为70/24/12克/亩，如果稀释用水量分别是200千克或300千克，则有效成分的百分浓度分别是0.035％/0.012％/0.006％，或0.023％/0.008％/0.004％。高分子助剂的浓度至少为0.1％～0.2％的范围。
经检测，代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液中微粒尺寸约为40～80nm。这种纳米悬浮液可在2～5h以内处于稳定状态，不发生析出或沉淀，并直接应用于多种农药喷施器械的喷洒作业。
⑸所述代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液，主要是代森锰锌纳米微粒，是在稀释混合过程中经反应形成的。不仅省掉了农药原药厂从代森铵或代森钠制备代森锰锌原药的合成与纯化过程，而且也省掉了农药制剂厂将代森锰锌和其它原药加工成可湿性粉剂的多步物理加工过程。本发明提出的解决方案，可直接应用于农业生产的植保环节，过程明显节能环保，可显著降低生产成本，并获得代森锰锌微粒尺寸小于100nm的纳米悬浮分散液。本发明的小尺寸纳米微粒可充分发挥药效，明显减少农药用量，在农业生产中起到减量增效的作用。
本发明通过兑水稀释制备代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的流程图如图2。
本发明的关键技术在于以下几个方面：
1.纳米悬浮液的生成过程
创新提出了将不溶于水和有机溶剂的含多价金属离子的农药品种代森锰锌制备纳米悬浮剂的新模式和新方法，以及与其它农药杀菌剂复配制备纳米悬浮剂的新方法。利用农药需要兑水稀释的过程，将目标产物的前驱体与相应金属盐混合，利用离子反应快速性质，控制反应物的混合与搅拌速度，从而获得直接使用的粒径小于100纳米的纳米悬浮液。本发明方法省掉了农药原药厂从水溶性代森盐制备代森锰锌原药的化学合成与纯化过程，也省掉了农药制剂厂将代森锰锌原药和其它原药混合加工成微粒尺寸较大的可湿性粉剂的多步物理加工过程。这一创新研究思路、制备模式和方法是本发明最重要的关键技术。这一关键技术也适合于代森锰锌与其它农药复配制备纳米悬浮剂的过程。
2.稀释用水量
当组分A和组分B的用量固定后，稀释用水量是控制两组分的稀释浓度，从而获得代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的关键技术之一。稀释用水量决定了组分A和组分B在稀释液中的浓度。若用水量太少，如20千克，则组分A和组分B在稀释液中的浓度大，生成纳米微粒的浓度高，形成100nm以下的微粒尺寸的稳定时间短。如果用水量超过300千克，虽仍可获得透明稀释液，但组分中含有的助剂浓度明显降低，纳米悬浮液的稳定性也会变差，除非增大助剂的用量。由此，当组分A和组分B的用量固定后，例如，每组分为500克，合适的稀释用水量，例如，大于20千克而小于300千克的用水量范围，是控制两组分的浓度和生成稳定的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的关键技术之一。
3.助剂的种类和用量
选择和使用合适的助剂的种类和用量，是获得代森锰锌及其复配有效成分纳米悬浮液的又一关键技术。但当水溶性代森盐与锰盐锌盐在水中生成代森锰锌纳米微粒时，仅靠大量水和搅拌的分散作用，并不能使生成的代森锰锌纳米微粒尺寸稳定。这是因为微粒不是静止不动的，都在不停的运动，相互发生碰撞，有效碰撞的结果，就使微粒合并，结晶长大，最终沉淀出来。阻止已生成的微粒尺寸变大的有效方法，就是选择合适的助剂(也叫分散剂)类型，并确定其合适的用量，使生成纳米微粒均匀分散在分散剂形成的水溶液中。这类分散剂首先是水溶性高分子，可以溶于水中。水溶性高分子在水中的微观状态，通常是以无规线团的方式存在。无规线团的尺寸远大于新生成的代森锰锌微粒、氟啶胺/吡唑醚菌酯微粒的尺寸，取决于分子量和浓度的大小，大的可在1个微米以上。如果此时生成的代森锰锌及其复配有效成分纳米微粒小于100nm，这些微粒就可进入无规线团的内部，使微粒之间的相互碰撞受到阻止和减缓，从而使生成的纳米微粒稳定性提高。这就是加入助剂起到的分散、悬浮和稳定作用。
本发明对多种不同水溶性高分子的类型进行了试验。在众多的阴离子、阳离子、非离子表面活性剂中，目前只有非离子高分子助剂才能起到希望的效果，如脂肪醇、酸、胺的聚氧乙烯醚、烷基芳基的聚氧丙烯聚氧乙烯醚、吐温-80、烷基多糖苷、蓖麻油聚氧乙烯醚等。阴离子表面活性 剂能与锰锌离子起反应从而生成不溶于水的沉淀析出，失去分散作用。本发明并不排除个别阳离子表面活性剂与适当的阴离子或非离子表面活性剂实现优化组合而溶于水并不出现沉淀的特殊情况。
本发明使用的水溶性高分子助剂的种类和用量可以通过试验加以确定。判断条件如下：一是生成的代森锰锌纳/氟啶胺/吡唑醚菌酯纳米悬浮液必须是外观透明，表观水溶，保证微粒尺寸在100nm以下；二是这种透明的纳米悬浮液的稳定时间在2～5小时范围。
对于两种组分体系，助剂用量可以分配到组分A和组分B中。原则上，若两组分并无容量限制，可任意分配助剂在组分A和组分B中的比例。如果对两组分有包装容量的限制，例如对于在1/15公顷田地用药(生成100克代森锰锌)，组分A和组分B规定各为500克的情况，考虑到组分B中溶解锰盐、锌盐的用水量较多，以及这一无机盐溶液对助剂的溶解性较差，则助剂加入组分B的量会受到大的限制。这样，两组分的助剂分配量可以下式确定：
助剂量(组分B)＝助剂总量―助剂量(组分A)―助剂量(纳米乳剂)
本发明的助剂用量受稀释用水量的影响。稀释用水量大，助剂的用量将适当增大。助剂用量与稀释用水量之比，至少在1∶1500以内，优选的1∶1200以内，更优选的1∶1000以内。
4.加入方式和搅拌方式
加料方式也是影响代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液性能的重要因素之一。当稀释用水量和分配于组分A和组分B的比例确定后，在混合过程中如何操作？都会影响到生成的微粒大小和稳定性。例如，加入方式会涉及到如下问题：
一是组分A的稀释液向组分B的稀释液添加，还是组分B的稀释液向组分A的稀释液添加？
二是如何添加？是倒入添加，细流添加，还是滴加？还是喷雾添加？是单点添加，还是多点添加？是连续添加，还是间歇添加？等等。
实际上，在加入方式确定后，还会涉及到搅拌方式问题。同样，搅拌也有不同的方式，是人工搅拌，还是机械搅拌？是单点搅拌，还是多点搅拌？是连续搅拌，还是间歇搅拌？等等。搅拌方式与搅拌速度紧密相关。
无论加料方式还是搅拌方式、搅拌速度，实质上都涉及到两组分稀释液混合瞬间形成的反应区域中反应物浓度的大小和生成物能否迅速分散问题。判断这两种方式和搅拌速度的标准，最直接的方法就是观察体系中的生成物是否呈现透明状态。如果生成的纳米悬浮液清澈透明，且稳定时间长，就表明加入方式合适，搅拌方式和搅拌速度属于有效搅拌。
代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的制备方法
对于两组分方案，本发明采用了如下的技术方案：
在搅拌速度不小于有效搅拌速度的条件下，将组分A稀释液加入到组分B稀释液中，或将组分B稀释液加入到组分A稀释液中；生成代森锰锌/氟啶胺/吡唑醚菌酯的纳米悬浮液。
组分A稀释液和组分B稀释液，分别为组分A和组分B兑水稀释形成的水溶液；
组分A：由水溶性代森盐或水溶性代森盐水溶液和水溶性高分子助剂组成；所述水溶性代森
盐为代森铵、代森钠、代森钾之一，或至少两种的混合物；
同时，组分A加有氟啶胺/吡唑醚菌酯纳米乳液；
组分B：是由按照一定比例组成的锰盐和锌盐混合物，或其水溶液。
控制加入的方式、加入速度和搅拌速度，使得悬浮液中生成100纳米级代森锰锌/氟啶胺/吡唑醚菌酯的纳米晶粒，最终的悬浮液也就是100纳米级代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液。
搅拌方式
人工搅拌：这个比较符合大多数应用场景；这种情形下，搅拌速度必须符合人工搅拌的生理要求，不可能太快。
机械搅拌：在田间，具备带有搅拌装置的大型容器困难。如果能够具备这样的条件，大型搅拌设备的转速一般不超过100转/分钟。以接近这样的转速搅拌即可。
对于人工搅拌方式，搅拌速度以符合人体生理功能的操作速度搅拌即可。为了获得稳定的目标产物，可适当降低物料的加入速度，通过观察生成物在体系内呈现透明状态，决定物料的加入速度。
加入方式和加入速度
为了使加入的物料更加均匀细小，进入体系后迅速被分散，一组分加入另一组分的方式，可以是连续加入，也可以是断续分量加入，或是滴加。对于滴加方式，可以使用农村普遍具有的人工喷雾器，进行喷雾加入，这种加入方式的效果最佳。加入速度，仍以观察生成物在体系内呈现的透明状态，决定物料的加入快慢。
对于现有农药制剂，以水为分散介质喷施，通常在喷施前需要将农药制剂兑水稀释，或者需要将共同使用的农药制剂混配在一起，这一过程俗称为“桶混”。本发明就是利用“桶混”过程，将组分A和组分B按照一定的浓度、一定的加入方式和加入速度，在特定的助剂——分散剂的作用下进行混合，从而直接获得可现场喷施作业的“桶混”透明的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液。
稀释用水量
目前的实验数据显示：50公斤上下是一个比较合理的起步范围。这个稀释用水量和我们的目标稳定期有强关联。这是一个多变量的问题，组分中的助剂含量、助剂组成，也是影响因素。
本发明的目的是为了获得在100nm以下级透明稳定期在2～5小时的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液。当单位质量的前驱体和与之反应的金属盐(硫酸锰、硫酸锌)质量固定，以及氟啶胺和吡唑醚菌酯的质量也固定时，能够影响微粒纳米尺寸和稳定性能的因素还包括：稀释用水量、助剂用量和制备方法。
稀释用水量可以对生成的纳米代森锰锌晶粒尺寸大小和稳定期长短产生影响。原因在于水作为分散介质的多少，会影响到代森铵溶液和硫酸锰、硫酸锌溶液在接触反应瞬间两者浓度的大小，以及分散的均匀性，因此也会影响到生成的晶粒大小、晶粒分散效果，以及结晶聚集和长大的机会。使用的助剂的多少，影响到它在不同用水量中水溶液的浓度，以及它对生成的纳米晶粒起到 的分散、悬浮和稳定作用的大小和稳定时间的长短。用水量太少，将会产生一个极限，例如稀释用水量在20公斤时，生成透明的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的稳定时间在1个小时左右，不能充分保证喷施作业时间。因此，需要增大稀释用水量。
本发明对于生成100克目标产物，即在100nm以下级透明稳定期在2～5小时的代森锰锌悬浮液，选择的稀释用水量在30～300公斤之间，优选的在50～200公斤范围。
三组分基本方案
本发明所述的100纳米以下级代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的基本方案，是由三种组分形成的体系。它们分别是：
组分A’：由代森铵、代森钠或代森钾固体或其水溶液组成，这是生成代森锰锌纳米晶粒的前驱体。
组分A’，可以是代森铵或代森钠、代森钾，或是其混合物。使用的单一成分或两者或三者的混合物，可以是固体物，这样包装简便，体积小，在使用前溶于水，且溶解迅速，但也可使用它的水溶液，在使用前直接兑水稀释到一定容量即可。组分A’中可加入或不加入一定质量的水溶性高分子助剂。
组分B’：由一定比例的锰盐和锌盐固体或其水溶液组成，这是生成代森锰锌纳米晶粒所需的多价金属离子。
组分B’，是由无机的锰盐和锌盐按照一定比例组成的混合物。所述锰盐选自硫酸锰、醋酸锰、氯化锰、硝酸锰中至少一种；所述锌盐选自硫酸锌、醋酸锌、氯化锌、硝酸锌中至少一种。组分B’可以使用固体物，这样包装体积小,也可以使用其水溶液。由于受它们溶解度的限制，形成溶液容量较大，虽不利于储存运输，但使用方便。组分B’中可加入或不加入一定质量的水溶性高分子助剂。
组分C：氟啶胺/吡唑醚菌酯纳米乳液
氟啶胺/吡唑醚菌酯纳米乳液作为组分C。氟啶胺/吡唑醚菌酯纳米乳液含有一定质量的水溶性高分子助剂。按照需要，在组分C中也可加入或不加入水溶性高分子助剂。
三组分方案所需要的水溶性高分子助剂的总质量，分配在组分A’，组分B’和组分C中，也包含在组分C中的氟啶胺/吡唑醚菌酯纳米乳液之中。
四组分基本方案
本发明所述的100纳米以下级代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的基本方案，是由四种组分形成的体系。它们分别是：
组分A’：由代森铵、代森钠或代森钾固体或其水溶液组成，这是生成代森锰锌纳米晶粒的前驱体。
组分A’，可以是代森铵或代森钠、代森钾，或是其混合物。使用的单一成分或两者或三者的混合物，可以是固体物，这样包装简便，体积小，在使用前溶于水，且溶解迅速，但也可使用它 的水溶液，在使用前直接兑水稀释到一定容量即可。组分A’中可加入或不加入一定质量的水溶性高分子助剂。
组分Bi：由按照一定比例的锰盐固体或其水溶液组成，这是生成代森锰锌纳米晶粒所需的锰金属离子。
所述锰盐选自硫酸锰、醋酸锰、氯化锰、硝酸锰中至少一种。
组分Bi可以使用固体物，包装体积小；也可是其水溶液。受其溶解度的限制，溶液容量较大，不利于储存运输，但使用方便。
组分Bi中可进一步加入一定质量的水溶性高分子助剂。
组分Bii：由按照一定比例的锌盐固体或其水溶液组成，这是生成代森锰锌纳米晶粒所需的锌金属离子。
所述锌盐选自硫酸锌、醋酸锌、氯化锌、硝酸锌中至少一种。
组分Bii可以使用固体物，包装体积小；也可是其水溶液，受其溶解度的限制，溶液容量较大，不利于储存运输，但使用方便。
组分Bii中可进一步加入一定质量的水溶性高分子助剂。
组分C：氟啶胺/吡唑醚菌酯纳米乳液
氟啶胺/吡唑醚菌酯纳米乳液作为组分C。氟啶胺/吡唑醚菌酯纳米乳液含有一定质量的水溶性高分子助剂。按照需要，在组分C中也可加入或不加入水溶性高分子助剂。
四组分方案所需要的水溶性高分子助剂的总质量，分配在组分A’，组分Bi，组分Bii和组分C中，也包含在组分C中的氟啶胺/吡唑醚菌酯纳米乳液之中。
四组分方案也可以按照前驱体为组分A、锰盐和锌盐为组分B、纳米乳剂为组分C和助剂为组分D四种组分组成。
【附图简要说明】
附图1:传统制备代森锰锌原药和加工成可湿性粉剂制剂的工艺流程图；
附图2:制备代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的流程示意图(两组分)
附图3:制备代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的流程示意图(三组分)
【实施方式】
本发明制备100nm以下级透明代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液的方法，以两组分方案的操作步骤为：
第一步，按照不同用水量、不同的稀释比例，将组分A和组分B分别进行稀释，形成组分A稀释液和组分B稀释液。
第二步，在机械搅拌(优选)或人工搅拌条件下，搅拌速度不小于有效搅拌速度，按照一定的加入方式(连续或间歇倒入、滴加、喷雾等)，将组分A稀释液均匀加入组分B稀释液中；或者是以相反的顺序加入。
三组分方案的操作步骤如下：
第一步，按照不同用水量、不同的稀释比例，将组分A’和组分B’分别进行稀释，形成组分A’稀释液和组分B’稀释液。
第二步，将组分C加入到组分A’稀释液中，搅拌分散均匀。
第三步，在机械搅拌(优选)或人工搅拌条件下，搅拌速度不小于有效搅拌速度，按照一定的加入方式(连续或间歇倒入、滴加、喷雾等)，将组分A’和组分C稀释液均匀加入组分B’稀释液中；或者是以相反的顺序加入。
现举例如下：
实施例1
代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液，可用于防治柑橘砂皮病、炭疽病，其有效成分用量分别为70/20/12克/亩，喷洒柑橘的稀释用水量约为200公斤/亩。生成70克代森锰锌所需要的前驱体代森胺约为63克。
组分配比：各组分配比、稀释水量、水量分配、加入顺序与方式，及试验结果列于下表：
操作方法：
将组分A和组分B分别按照200千克用水量的2/3和1/3的比例稀释溶解。在人工搅拌下，将组分B稀释液以连续细流加入方式加入到组分A稀释液中，得到外观透明的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液。稳定时间4.5小时。
实施例2
代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液，可用于防治香蕉黑星病、叶斑病，其有效成分用量分别为120/20/8克/亩，喷洒香蕉的稀释用水量为300公斤/亩。生成120克代森锰锌所需要的前驱体代森胺约为108克。
组分配比：各组分配比、稀释水量、水量分配、加入顺序与方式，及试验结果列于下表：
操作方法：
将组分A’、组分B’分别按照300千克用水量的4/5和1/5比例稀释溶解，然后将组分C加入组分A’的稀释液中，分散均匀，形成组分A’和组分C的混合稀释液。在搅拌下，将组分B’稀释液以连续喷雾方式加入到组分A’和组分C的混合稀释液中，得到外观透明的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液，稳定时间4.5小时。
实施例3
代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液，可用于防治甜瓜的霜霉病，其有效成分用量分别为55/10/5克/亩，喷施甜瓜的稀释用水量为60公斤/亩。生成55克代森锰锌所需要的前驱体代森胺约为50克。
组分配比：各组分配比、稀释水量、水量分配、加入顺序与方式，及试验结果列于下表：

操作方法：
将组分A’、组分B’分别按照60千克用水量的2/3和1/3比例稀释溶解，然后将组分C加入组分A’的稀释液中，分散均匀，形成组分A’和组分C的混合稀释液。在搅拌下，将组分B’稀释液以连续喷雾方式加入到组分A’和组分C的稀释液中，得到外观透明的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液。稳定时间8小时。
实施例4
代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液，可用于防治马铃薯晚疫病，其有效成分用量分别为50/8/5克/亩，喷洒马铃薯的稀释用水量为50千克/亩。生成50克代森锰锌所需要的前驱体代森胺约为45克。
组分配比：各组分配比、稀释水量、水量分配、加入顺序与方式，及试验结果列于下表：
操作方法：
将组分A和组分B分别按照50千克用水量的2/3和1/3的比例稀释溶解。在人工搅拌下，将组分B稀释液以连续滴加方式加入到组分A稀释液中，得到外观透明的代森锰锌/氟啶胺/吡唑醚菌酯纳米悬浮液。稳定时间4小时。

Claims (10)

  1. 一种防治水果类病害的纳米悬浮液，其特征在于，所述纳米悬浮液是指100纳米以下级纳米悬浮液；所述纳米悬浮液由两种组分兑水稀释混合形成：
    组分A：水溶性代森盐或水溶性代森盐水溶液，水溶性高分子助剂和水；所述水溶性代森盐为代森铵、代森钠、代森钾之一，或至少两种的混合物；
    同时，组分A添加氟啶胺/吡唑醚菌酯纳米乳液；
    组分B：是由按照一定比例组成的锰盐和锌盐混合物；锰盐锌盐分别为至少一种盐类的组成物质。
  2. 如权利要求1所述的纳米悬浮液，其特征在于，所述100纳米以下级纳米悬浮液，具备小时级稳定期。
  3. 如权利要求1所述的纳米悬浮液，其特征在于，所述组分B，添加水溶性高分子助剂和水形成水溶液。
  4. 如权利要求1所述的纳米悬浮液，其特征在于，所述水溶性高分子助剂为非离子表面活性剂。
  5. 如权利要求1所述的纳米悬浮液，其特征在于，所述水溶性高分子助剂用量与稀释用水量之比，不大于1∶1200。
  6. 如权利要求1所述的纳米悬浮液，其特征在于，当代森盐、锰盐、锌盐分别为代森铵、硫酸锰、硫酸锌时，其质量比的范围为：
    代森铵∶硫酸锰∶硫酸锌＝90∶41～55∶7～17
    优选的，代森铵∶硫酸锰∶硫酸锌＝90∶41～43∶7～9。
  7. 如权利要求4所述的纳米悬浮液，其特征在于，所述非离子表面活性剂，为下列选项中至少一种：水溶性淀粉及其衍生物、水溶性瓜尔胶及其衍生物，聚氧丙烯-聚氧乙烯嵌段共聚物、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚、脂肪胺聚氧乙烯醚、烷基芳基聚氧丙烯聚氧乙烯醚、芳基酚聚氧乙烯醚、蓖麻油聚氧乙烯醚、OP-10、烷基多糖苷、吐温、聚乙烯醇、聚乙烯吡咯烷酮。
  8. 如权利要求1至7之一所述的纳米悬浮液，其特征在于，所述锰盐选自硫酸锰、醋酸锰、氯化锰、硝酸锰中至少一种；所述锌盐选自硫酸锌、醋酸锌、氯化锌、硝酸锌中至少一种。
  9. 一种如权利要求1至8之一所述的防治水果类病害的纳米悬浮液的制备方法；在搅拌速度不小于有效搅拌速度的条件下，将组分A稀释液加入到组分B稀释液中；或者将组分B稀释液加入到组分A稀释液中，形成三元复配纳米悬浮液。
  10. 如权利要求9所述的制备方法，其特征在于，一组分加入另一组分的方式，为如下四种方式之一：连续加入，断续分量加入，滴加，喷雾加入。
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