Prochloraz manganese salt / kasugamycin NANO suspension dispersion liquid

Abstract

The present invention relates to the field of nanopesticides, in particular to preparation of a nano suspension dispersion liquid which belongs to a pesticide variety insoluble in water and a solvent, and has the particle size smaller than 100 nanometers, especially smaller than 50 nanometers. A prochloraz manganese salt / kasugamycin nano suspension dispersion liquid having the particle size of 100 nanometers or less of the present invention is formed by mixing and diluting three components with water.

Description

Prochloraz manganese salt / Kasugamycin nanosuspension dispersion

Technical field

[0001] The present invention belongs to the field of nano pesticides, and particularly relates to the preparation of suspension dispersions of water- and solvent-insoluble pesticides with particle sizes less than 100 nanometers, especially less than 50 nanometers. [Background Technology]

[0002] Modern agricultural production requires the use of pesticides. Improving the formulation performance of existing pesticides, increasing their efficacy, reducing their dosage, and mitigating their impact on the environment are of great significance to the sustainable development of agriculture.

[0003] An effective way to achieve pesticide reduction is to effectively reduce the particle size of the active ingredients in pesticide formulations. For water-insoluble pesticides, the minimum size is a few nanometers. Nanopesticides refer to formulations in which the pesticide particles are at the nanometer scale (1 to 100 nm). The particle size of traditional pesticide formulations is on the micrometer scale, ranging from a few microns to tens of microns or even larger. If the particle size is reduced to nanometers, the size is reduced by a thousand times. Theoretically, the number of particles can increase by a billion times, and the surface area can increase by a thousand times. The dramatic increase in the number and surface area of ​​pesticide particles allows for more even dispersion on the leaves, more extensive contact with the target, and full and enhanced efficacy.

[0004] On April 1, 2019, the International Union of Pure and Applied Chemistry (IUPAC), celebrating its 100th anniversary, announced its "Top 10 Chemical Inventions That Will Change the World," with nanopesticides topping the list. This is due to the growing global population, projected to approach 10 billion by 2050. Feeding this large population requires a significant increase in agricultural output while minimizing the environmental impact of land use, including reducing pesticide pollution and water consumption. Nanopesticides, with their small particle size and improved target absorption, offer a promising tool for addressing the key challenges of traditional pesticides: environmental pollution, pesticide accumulation in organisms, and the significant increase in pest and disease resistance. While nanopesticides are by no means the only path to sustainable agricultural development, they certainly offer a lower impact on the environment and human health, contributing to a more sustainable future for the planet.

[0005] Prochloraz, chemically known as N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide, is a white crystal with a melting point of 46.5-49.3°C. It is non-volatile, non-corrosive, and non-explosive, with a vapor pressure of 0.48 mPa (20°C). Its solubility in water at 25°C is 34.4 mg / L. It is soluble in most organic solvents and relatively stable under normal storage conditions, but unstable under alkaline and acidic conditions. Prochloraz, originally developed and produced by the German company Agfr, is a highly effective, broad-spectrum, low-toxic imidazole fungicide. It has both protective and eradicative properties, as well as systemic and conductive properties. It primarily inhibits sterol biosynthesis and is particularly effective against various plant diseases caused by ascomycetes. It also controls rice blast, seedling blight, mushroom brown spot, rapeseed sclerotinia rot, and anthracnose on various crops.

[0006] Prochloraz manganese salt is a complex of prochloraz and manganese chloride, with prochloraz and manganese ions as its active ingredients. Compared to prochloraz, prochloraz manganese salt is safer because the manganese ions in it inhibit spore germination and mycelial growth of pathogens. This makes prochloraz manganese salt more effective and safer, and it can more effectively protect crops from pathogens.

[0007] Prochloraz manganese salt, chemical name is N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazole-1-carboxamide-manganese chloride, chemical formula is [C 15 H 16 Cl₃N₃O₂]4·MnCl₂, with a molecular weight of 1635.51 and a CAS number of 278-301-3. The technical product is a white to brown, granular powder with a slightly aromatic odor, a melting point of 141-142.5°C, a solubility of 40 mg / L in water and 7 g / L in acetone, and a vapor pressure of 0.02 Pa (20°C). This complex rapidly separates in aqueous solutions or suspensions, achieving a resolution of 55% within 4 hours at 25°C.

[0008] Since the 1990s, my country has conducted extensive field trials on the efficacy of prochloraz manganese salt, which have shown that it has significant efficacy against rapeseed sclerotinia rot, rice panicle neck disease, stripe leaf blight and seedling blight, banana leaf spot, peanut brown spot, watermelon vine blight, citrus storage and preservation, tulip bulb rot, grape gray mold and black bean disease, tobacco brown spot, etc., and the dosage is relatively low. It was found that it has significant control effects on mango anthracnose, and has been used to control citrus black spot disease. 50 It is 0.186μg, and it was found that the prevention and control effect on garlic leaf blight can reach 47.9% to 63.4%, and it is safe for crops. At the same time, it has a certain effect of increasing and maintaining the yield of garlic bulbs.

[0009] It should be noted that the addition of manganese salts alters the original physical properties of prochloraz, making it insoluble in both water and organic solvents, limiting its processing to wettable powders. Currently, pesticide formulations processed through mechanical pulverization typically produce particle sizes ranging from a few microns to tens of microns or even larger. These large pesticide particles hinder pesticide efficacy, leading to increased pesticide usage and increased resistance in target species. Improving the formulation and enhancing the efficacy of pesticides containing polyvalent metal ions is a global challenge.

[0010] The existing process for synthesizing the technical of prochloraz manganese salt and processing the wettable powder formulation is as follows: (1) Technical synthesis. Prochloraz manganese salt is dissolved in toluene, and manganese chloride is added to carry out a complexation reaction to obtain a block precipitate of prochloraz manganese salt. After separation, washing, and drying, the technical of prochloraz manganese salt is obtained. (2) Preparation processing. The solid technical of prochloraz manganese salt is used as the raw material, and a multi-step process of crushing, grinding, mixing, etc. is carried out to obtain the prochloraz manganese salt preparation. The above preparation process requires corresponding workshops and production equipment, such as filters, dryers, crushers, grinders, and mixers. The process is both lengthy and energy-consuming.

[0011] [Summary of the invention]

[0012] One of the objectives of the present invention is to overcome the shortcomings of the prior art and provide a novel approach and method for preparing a wettable powder formulation of prochloraz manganese salt, which differs from the prior art. By diluting the formulation with water before spraying, prochloraz and manganese chloride react to form nanoparticles of prochloraz manganese salt, thereby providing a water-soluble, transparent nano-suspension dispersion of prochloraz manganese salt that can be directly used for spraying.

[0013] Another object of the present invention is to compound prochloraz manganese salt with kasugamycin, an antibiotic bactericide with good control effects against various bacterial diseases, in order to enhance the control effect of prochloraz manganese salt and expand its bactericidal spectrum, thereby achieving a synergistic effect and reducing the dosage of a single variety. While obtaining a nano-suspension dispersion of prochloraz manganese salt, an aqueous solution of kasugamycin is also obtained, i.e., a nano-suspension dispersion of prochloraz manganese salt / kasugamycin is obtained.

[0014] The prochloraz manganese salt / kasugamycin nano suspension dispersion of the present invention can be directly loaded into a pesticide spraying device for spraying.

[0015] The innovative ideas of the present invention are as follows:

[0016] The precursor of prochloraz manganese salt is prochloraz. Although insoluble in water, prochloraz is soluble in organic solvents and has a high solubility. Prochloraz dissolves in organic solvents as a monomolecular dispersion, allowing it to be stably present as one component in nanoemulsions with water as the dispersion medium. Manganese chloride, which reacts with it, dissociates in water into manganese ions and chloride ions, forming an ionically dispersed component. When the two interact under stirring, a coordination reaction readily occurs between the manganese ions and prochloraz molecules, forming a prochloraz manganese salt complex. By controlling the reaction conditions, the nucleation and crystallization growth of the prochloraz manganese salt molecules generated by the reaction can be controlled, thereby obtaining a nanosuspension dispersion of prochloraz manganese salt.

[0017] Kasugamycin, whose chemical name is (5-amino-2-methyl-6-(2,3,4,5,6-pentahydroxycyclohexyloxy)tetrahydropyran-3-yl)amino-α-iminoacetic acid, has a molecular formula of C 14 H 25 N3O9. Kasugamycin is an agricultural antibiotic fungicide. Its characteristics: It has strong systemic properties, allowing it to be rapidly absorbed by plants and transported throughout the body, exerting its bactericidal effects. It has excellent control effects on a variety of bacterial and fungal diseases, especially rice blast. Kasugamycin acts on the amino acid metabolic esterase system of pathogens, disrupting protein biosynthesis and normal function of this system. This inhibits mycelial growth and causes cell granulation, rendering the pathogen incapable of reproduction and infection, thereby achieving the goal of disease control. Through the synergistic effects of these multiple mechanisms, it interferes with the normal physiological metabolism of pathogens, effectively inhibiting their growth and reproduction, thus achieving disease control. Pure kasugamycin appears as white crystals, while the hydrochloride salt appears as white needle-shaped or flaky crystals. The pure product is poorly soluble in organic solvents, dissolving 12.5% ​​(w / v) in water at 25°C. The hydrochloride salt is readily soluble in water but insoluble in organic solvents such as methanol, ethanol, acetone, and benzene. It is relatively stable under acidic and neutral conditions. It is easily destroyed and ineffective when encountering alkaline solution.

[0018] Kasugamycin's properties: It has a broad fungicidal spectrum and is effective against a wide range of bacterial diseases, including bacterial wilt, soft rot, bacterial angular leaf spot, gummosis, rice blast, scab, leaf spot, and canker, among over 30 others. It also has some control effects against some fungal diseases, such as early blight, anthracnose, and gray mold. It has strong systemic penetration. After application, it is rapidly absorbed by plants and penetrates through the leaves to the underside, dispersing throughout the plant to rapidly kill pathogens. It is highly safe, with very low toxicity and low environmental residues, meeting modern environmental standards and making it suitable for the production of green and organic agricultural products. It also has a long-lasting effect: It resists rainwater erosion, adheres well to plants after application, is not easily washed away by rain, and maintains its fungicidal effect. It also has excellent compatibility with various fungicides, achieving significant synergistic effects. It has a certain regulatory effect on crop growth. While preventing and controlling a variety of diseases, it can also stimulate crop growth, induce plant resistance responses, and enhance plant immunity.

[0019] Kasugamycin's shortcomings include: relatively weak killing ability. It's not very effective in killing pathogens directly, but rather acts as an inhibitor. Its protective properties are weak. While effective as a curative fungicide, its protective effect is relatively weak when used as a protective agent before disease outbreaks occur. Some crops, such as legumes, are sensitive to kasugamycin and are prone to developing resistance.

[0020] The combination of prochloraz manganese salt and kasugamycin can complement and improve the performance:

[0021] Prochloraz manganese salt has a broader fungicidal spectrum. It is highly effective against a variety of fungal diseases, such as anthracnose and leaf spot. Kasugamycin is particularly effective against bacterial diseases, with particular efficacy against canker, angular leaf spot, and soft rot. When combined, the two can simultaneously control both fungal and bacterial diseases, covering a wider range of disease types.

[0022] Enhanced control effectiveness. Fungicides with different mechanisms of action work synergistically, enhancing pathogen killing and providing a more comprehensive attack on pathogens, effectively improving control effectiveness. This can reduce the amount of a single agent used, reduce the risk of a single pathogen developing resistance to a specific agent, and extend the lifespan of the agent.

[0023] Improved stability. After compounding, the stability of the drug under different environmental conditions can be enhanced to a certain extent, ensuring the continued effectiveness of the drug and prolonging its duration. This reduces the impact of environmental factors (such as temperature and humidity) on the drug's effects.

[0024] Wider applicability. It can adapt to different crop growth stages and environments, providing more comprehensive crop protection. For areas with high incidence of both fungal and bacterial infections, the use of compound pesticides is more efficient and convenient.

[0025] The combination of prochloraz manganese salt and kasugamycin can prevent and control diseases of various crops

[0026] Fruit trees: citrus canker, anthracnose; apple anthracnose, ring rot, etc.

[0027] Vegetables: bacterial angular spot and downy mildew of cucumber; leaf mold and canker of tomato, etc.

[0028] Rice: rice blast, sheath blight, bacterial leaf streak, etc.

[0029] When combining prochloraz manganese salt and kasugamycin, the mass ratio of prochloraz manganese salt to the active ingredient of kasugamycin varies depending on factors such as the specific application scenario, the target pest, and the formulation. The typical ratio is between 1:7:1, preferably between 1:3:1. The formulation is primarily a traditional wettable powder. No other nanoformulations, let alone nanosuspensions or dispersions, have been reported.

[0030] The compounding of prochloraz manganese salt and kasugamycin is achieved through a dilution process with water. A prochloraz nanoemulsion and a kasugamycin aqueous solution are used as one component, while the manganese salt is the other. When the diluted manganese salt solution is added to the diluted solution of the nanoemulsion and kasugamycin aqueous solution, the manganese ions react with prochloraz to form prochloraz manganese salt molecules, while kasugamycin remains dispersed as a single molecule in the dilution solution. The resulting prochloraz manganese salt molecules are insoluble in the original solvent and precipitate from the solubilizing micelles to form prochloraz manganese salt nanocrystals. The water-soluble polymer additive added to the system exists not only in the form of micelles and flocs, but also in the larger form of random coils. Random coils are loose spherical structures formed by the spontaneous coiling of water-soluble polymer chains. When the prochloraz manganese salt nanocrystals formed in the system are less than 100 nm, especially less than 50 nm in size, they diffuse into the interior of the random coils under the shear force of mechanical agitation. The random coils isolate and prevent the effective collision, aggregation, growth, and precipitation of the crystallites. Therefore, the water-soluble polymer additive disperses, suspends, stabilizes, and protects the nanocrystals of prochloraz manganese salt, hence the name "prochloraz manganese salt / kasugamycin nanosuspension dispersion." At this point, the system appears clear and transparent, appears water-soluble, and exhibits the "Tyndall phenomenon."

[0031] What needs attention is that in the process of generating nanocrystals of manganese salt of prochloraz, the addition rate of the manganese salt dilution and the stirring speed of the system involve the amount of reactants and products added per unit time, as well as the uniformity of product dispersion, which are all important factors affecting the size of the resulting nanocrystals. Regarding the addition rate, with the goal of generating nanocrystals with a size less than 100 nanometers, the clarity and transparency of the system can be used as a criterion. Its theoretical basis is that when the particle size is less than one-quarter of the lower limit of the visible light wavelength (400-760 nanometers), that is, less than 100 nm, no severe refraction and reflection will occur, and therefore the system is transparent. Conversely, if the system is opalescent or opaque, it indicates that the particle size is greater than 100 nanometers.

[0032] To achieve this goal, the following points must be focused on:

[0033] ① The mixing speed of the two-component solution (i.e., the speed at which one component is added) should not be too fast. If added too quickly, the two components will be unevenly dispersed, and the local concentration of the reactant will be too high. This will accelerate the formation of products and crystals, resulting in a large number of crystals. This may cause aggregation between nanocrystals, resulting in larger grain sizes. If the system exhibits opalescence, it indicates that the grain size is already several hundred nanometers. Therefore, the addition speed of one component should be based on maintaining the system's transparency.

[0034] ② The stirring speed of the system should be appropriately increased. The stirring speed of the system is related to the formation and dispersion rate of the product nanoparticles in the aqueous phase. Adequate stirring and rapid diffusion promote the rapid formation and dispersion of nanoparticles, maintain small particle size, and avoid aggregation of particles. The stirring speed should be coordinated with the addition rate of the components and should also be based on maintaining the transparency of the system.

[0035] Explanation of terms

[0036] Dispersed system: A dispersed system is formed when one or more substances are dispersed in another. The dispersed substance in a dispersed system is called the dispersed phase, and the other substance is called the dispersion medium. Based on the size of the dispersed phase particles, dispersed systems are categorized as: molecular (ionic) dispersed systems (particle size < 1 nm) and colloidal dispersed systems (particle size < 100 nm).

[0037] Colloids and Sols: A colloid is a state in which matter exists at a certain degree of dispersion, rather than being an inherent state of a particular type of substance. Many normally insoluble substances can, under appropriate conditions, disperse in a medium to form a seemingly uniform solution. While superficially indistinguishable from a true solution, their diffusion rate and permeability, among other factors, place them within the realm of colloidal substances and are referred to as sols.

[0038] Classification of colloidal solutions: Based on their stability and the structure of their colloidal particles, they are divided into the following categories: 1. Lyophobic sols, formed by insoluble substances dispersed in a dispersion medium, are referred to as sols. These particles consist of varying numbers of molecules, exhibiting large interphases and apparent free energies. These sols are highly unstable and easily disrupted, leading to aggregation and irreversible return to their original state. 2. Solutions of polymer compounds, whose molecular size reaches the colloid range and exhibits colloidal properties, are true solutions of dispersed molecules, making them thermodynamically stable and reversible systems. These sols are also known as lyophilic sols.

[0039] Tyndall effect: When a beam of light passes through a colloid, a bright "pathway" can be observed in the colloid perpendicular to the incident light. This phenomenon, also known as the Tyndall effect, is essentially the scattering of light when propagating through a colloid. This phenomenon occurs primarily because the particle size of colloidal particles ranges from 1 to 100 nm, resulting in a significant scattering effect of visible light passing through the colloid, while true solutions scatter very little light. Colloids exhibit a pronounced Tyndall effect, while true solutions with dispersed molecules exhibit virtually no light scattering. Therefore, it is often used to distinguish colloidal solutions from true solutions.

[0040] If the particles are smaller than the wavelength of the incident light, light scattering occurs, with the light waves radiating outward around the particles, a phenomenon known as scattered light or opalescence. The Tyndall effect is essentially a phenomenon of light scattering, also known as opalescence. True solutions scatter light very weakly. The intensity of scattered light also increases with increasing 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 100 nm, and the Tyndall effect may occur. If the particles approach or exceed the wavelength of the incident light (400-740 nm), significant light reflection occurs. When the solution displays increasing opalescence, turbidity, or even opacity, the particle size has increased to near micrometers or above.

[0041] System: The so-called system refers to the suspension dispersion system formed by mixing the two components of the prochloraz manganese salt / kasugamycin nanosuspension dispersion in the present invention while controlling the addition rate and stirring. The system is composed of water, the precursor nanoemulsion, kasugamycin, a water-soluble polymer auxiliary, the added manganese salt, and the generated prochloraz manganese salt, to form the target product—the prochloraz manganese salt / kasugamycin nanosuspension dispersion.

[0042] Component: A component is a composition comprising one or more ingredients. In principle, any ingredient used in this invention can constitute a component on its own. However, for ease of packaging, transportation, and use, the components should be simplified. The principles are: 1) the ingredients should not react with each other; 2) the number of components should not be too large.

[0043] Ingredients: The so-called ingredients refer to the raw materials used in the present invention, including prochloraz, manganese chloride, kasugamycin, a water-soluble polymer auxiliary agent and water.

[0044] Precursor: The so-called precursor refers to the parent substance used to generate the target product. Here, the target product is prochloraz manganese salt, and the precursor is prochloraz.

[0045] Water-soluble polymer additives are macromolecular substances containing hydrophilic polar groups that are soluble in water. They are also called polymer surfactants or active agents. Water-soluble polymer additives can provide dispersion, suspension, emulsification, and stabilization. Based on the nature of the groups, they can be categorized as anionic, cationic, zwitterionic, and nonionic polymer additives.

[0046] Particle size: also known as particle size; refers to the size of the crystals of prochloraz manganese salt formed by the interaction of the precursor in the system with the manganese salt under the dispersion of water-soluble polymer additives. It also includes the size of the particles formed by other pesticide varieties compounded with it, and does not specifically refer to the microscopic morphological structure of the crystals.

[0047] Sub-100 nanometers is a statistical classification of pesticide particle sizes within a system. All pesticide particle sizes within a suspension exhibit a statistical distribution. The sub-100 nanometer nanosuspension described herein means that at least 80% of the pesticide particles are smaller than 100 nanometers. Thus, particles larger than 100 nanometers constitute only a small fraction.

[0048] Effective stirring speed: The so-called effective stirring speed refers to the ability, under a certain addition method, to disperse the nanocrystals generated in the system promptly when one component is added to another, by stirring at a speed no less than the effective stirring speed, preventing grain growth and aggregation, and preventing the grain size from increasing to several hundred nanometers. Transparency of the resulting solution is a sign of effective stirring.

[0049] Effective stirring: The addition of components and the stirring method and speed have a significant impact on the resulting liquid. Stirring methods include mechanical stirring, multi-point mechanical stirring, manual stirring, and multi-point manual stirring. Fast stirring speeds are associated with optimal results. If the resulting liquid is transparent, the stirring is considered effective. Otherwise, the stirring is considered ineffective.

[0050] Pre-stirring: When one component (the additive) is added to another (the matrix), the relative speed at which the two components contact each other affects whether the nanocrystals generated in the system can be dispersed in a timely manner. Pre-stirring the matrix component before adding the additive, i.e., stirring the matrix component in advance so that the matrix component rotates at a certain speed, can achieve a good dispersion effect. Generally, the pre-stirring speed should reach or be close to the effective stirring speed.

[0051] Addition method: The so-called addition method includes the order in which the different components are mixed with water to form two components. The two components can be added one after the other, or vice versa. Addition methods include continuous addition, intermittent addition, trickle addition, dropwise addition, spray addition, and addition at a fixed or mobile position. The addition method is preferably to achieve rapid mixing and dispersion.

[0052] Addition speed: After determining the addition method, control the amount of components added with the goal of achieving effective stirring.

[0053] The prochloraz manganese salt / kasugamycin nano-suspension dispersion of the present invention refers to a prochloraz manganese salt / kasugamycin nano-suspension dispersion of less than 100 nanometers; the prochloraz manganese salt / kasugamycin nano-suspension dispersion of less than 100 nanometers is formed by diluting and mixing three components with water:

[0054] Component A: It is composed of prochloraz nanoemulsion, kasugamycin, water-soluble polymer additives and water. Kasugamycin needs to be dissolved in water. In order to maintain the stability of the dilution system, polymer additives need to be added.

[0055] Component B: a manganese salt solid or a (transparent) aqueous solution formed by dissolving a manganese salt solid in water.

[0056] Component C: A mixture of one or more water-soluble polymer additives, or a transparent solution formed by adding an appropriate amount of water to reduce the viscosity.

[0057] The water-soluble polymer auxiliary agent is a nonionic surfactant.

[0058] The nonionic surfactant may be (at least one) water-soluble starch, cellulose and its derivatives, water-soluble guar gum and its derivatives, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, aliphatic polyoxyethylene ether, aliphatic aryl polyoxyethylene ether, aliphatic phenol polyoxyethylene ether, arylphenol polyoxypropylene polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polyglycoside, Tween, polyvinyl alcohol, etc. Preferably, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, aliphatic polyoxyethylene ether, aliphatic aryl polyoxyethylene ether, aliphatic phenol polyoxyethylene ether, arylphenol polyoxypropylene polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polyglycoside, Tween.

[0059] Furthermore, the nano-suspension dispersion of prochloraz manganese salt / kasugamycin with a size below 100 nanometers has a stable period of hours.

[0060] Stable period

[0061] The prochloraz manganese salt / kasugamycin nano-suspension dispersion prepared by the present invention is a type of transparent, apparently water-soluble dispersion, but is not itself a thermodynamically stable solution. Therefore, the time for the nano-suspension dispersion to maintain a transparent appearance is not infinitely long, but rather a plateau. Considering the characteristics of the spraying operation, after the nano-suspension dispersion is prepared, the required operating time should be at least more than 1 hour, so that the length of the plateau time can be described in hours. Thus, the present invention proposes that the concept of "plateau" exists in nano-suspensions below 100nm. That is, the nano-suspension dispersions below 100nm prepared by the present invention complete the spraying operation while the solution remains transparent, and the plateau should reach at least 1 hour.

[0062] From the application perspective, 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.

[0063] During the stabilization period, the nano-scale suspension dispersion remains transparent, which ensures that the particle size remains less than 100 nm.

[0064] Hourly stability period

[0065] From the perspective of spraying operations:

[0066] The stabilization time is about 1 hour, which is not sufficient for spraying operations. It is difficult to achieve a stable period of more than 5 hours for multi-component nano-suspension dispersions. The stabilization time is between 2 and 5 hours, which is sufficient for most pesticide spraying equipment.

[0067] The hour-level stabilization period mentioned in the present invention refers to a stabilization time between 1 and 5 hours.

[0068] For the hourly stable period, further detailed division can be carried out.

[0069] The basic period for spraying operation is 1 to 2 hours; in most cases, the spraying equipment can complete the operation.

[0070] 2 to 5 hours is a sufficient period for spraying operations; it can be used to accommodate spraying operations that are delayed due to special circumstances.

[0071] Compositions and additives of prochloraz manganese salt / kasugamycin nanosuspension dispersion

[0072] Traditional prochloraz manganese salt / kasugamycin formulations, such as wettable powders, are typically single-component and can be sprayed after dilution with water. However, the pesticide particles are typically larger than microns in size. The present invention, in order to obtain a suspension dispersion with nanometer-sized particles, employs a three-component formulation and, following a specific method, dilutes the suspension dispersion with water to produce a nano-sized suspension dispersion of prochloraz manganese salt / kasugamycin with particles smaller than 100 nanometers.

[0073] Three-component solution

[0074] The nano-suspension dispersion of prochloraz manganese salt / kasugamycin with a size below 100 nanometers has a stable period of hours and is a system generated by the reaction of three components. They are:

[0075] Component A: consists of prochloraz nanoemulsion, kasugamycin, a water-soluble polymer additive and water.

[0076] Component B: composed of manganese salt solid or in combination with water.

[0077] The manganese salt is selected from at least one of manganese sulfate, manganese acetate, manganese chloride and manganese nitrate; component B can be used in solid form, so that the packaging volume is small; or its aqueous solution can be used, which is limited by certain solubility and needs to have a certain capacity specification.

[0078] Component C: A mixture of one or more water-soluble polymer additives, or a transparent solution formed by adding an appropriate amount of water to reduce the viscosity.

[0079] Proportion of ingredients for generating prochloraz manganese salt / kasugamycin nanosuspension dispersion

[0080] In component A, the amount of the precursor is the basis for determining the composition of components A and B. Prochloraz in component A is the precursor for the formation of nano-prochloraz manganese salt and is also the basis for determining the composition of component B.

[0081] The above shows that the mass ratio of prochloraz manganese salt to kasugamycin is generally 1 to 3 / 1, preferably 3 / 1. The present invention uses the example of spraying Y times the amount of prochloraz manganese salt per mu (1 / 15 hectare, the same below) of field as an example. A three-component design is based on generating Y (3 / 1) grams of a 100 nm or less nanosuspension dispersion of prochloraz manganese salt / kasugamycin.

[0082] Component A, prochloraz as a precursor, according to the (3 / 1) ratio, requires 3Y grams of prochloraz and 1 gram of kasuminomycin, 3Y grams of prochloraz are formulated into a nanoemulsion, and 1 gram of kasuminomycin is dissolved in the water of component A.

[0083] Component B, determine the amount of manganese salt (e.g., manganese chloride) required to react with prochloraz. It is generally believed that prochloraz and manganese ions form a 4:1 molecular complex structure, and the amount of manganese chloride can be calculated based on this.

[0084] Component C, determine the type and amount of water-soluble polymer additives, based on the appearance of a transparent state, which is affected by the amount of water used for dilution.

[0085] The ratio of the amount of the auxiliary agent to the amount of water used for dilution is at least within 1:1000, preferably within 1:800, and more preferably within 1:600.

[0086] Mass ratio of prochloraz: manganese chloride

[0087] There is no strict ratio between prochloraz and manganese ions. To ensure a complete reaction in industrial production, the ratio of the two is large, which is the upper limit. The present invention adopts a ratio lower than this for the following reasons: ① The large amount of manganese ions and high concentration are not conducive to the formation and stability of small-sized grains; ② Using a low amount of manganese salt means that even if the reaction is not complete, all its components are independently usable fungicides; ③ The preparation process of the composite nano-suspension dispersion does not require industrial production of water washing, separation and drying of prochloraz manganese salt, and no components are lost. The molecular ratio and mass ratio between the two are as follows:

[0088] Prochloraz: manganese chloride = 1:0.3 (molecular ratio); 100:10 (mass ratio) (theoretical upper limit)

[0089] Preferably, prochloraz: manganese chloride = 1:0.275 (molecular ratio); 100:9 (mass ratio) (industrial production ratio)

[0090] More preferably, prochloraz: manganese chloride = 1:0.25 (molecular ratio); 100:8 (mass ratio) (practical application)

[0091] Water-soluble polymer additives

[0092] (1) The prochloraz manganese salt / kasugamycin nanosuspension dispersion is prepared by a tank-mixing process involving dilution with water to obtain a directly usable composite nanosuspension dispersion. The precursor prochloraz is present in component A as a nanoemulsion, while kasugamycin is dissolved in the water of component A as a single molecule dispersion. The water-soluble polymer additive can be present in component C or partially added to component A. The water-soluble polymer additive has emulsifying, suspending, and dispersing properties, which are the basis for stably suspending and dispersing the generated prochloraz manganese salt nanoparticles in water. When the total particle size is less than 100 nanometers, the system becomes a transparent, apparently water-soluble prochloraz manganese salt / kasugamycin nanosuspension dispersion.

[0093] (2) Water-soluble polymer additives are polymer surfactants that disperse, suspend, stabilize, and increase solution viscosity for nanoparticles. This is due to their hydrophobic chain structure and hydrophilic groups. These hydrophilic groups are distributed on the side and end groups of the macromolecular chain and include hydroxyl, carboxyl, carboxymethyl, sulfonic acid, sulfate, phosphate, amino, and quaternary ammonium groups. Based on their source, they are classified as natural and synthetic polymers. Based on the nature of their hydrophilic groups, they are classified as anionic, cationic, nonionic, and zwitterionic polymers.

[0094] (3) The principles for selecting water-soluble polymer adjuvants in the present invention are: 1. They can suspend, disperse, and stabilize the pesticide nanoparticles generated in the system; 2. They are not affected by the reaction between polyvalent metal ions and prochloraz; and 3. They are as environmentally friendly as possible. Therefore, the present invention selects non-ionic polymer adjuvants from natural substances and their derivatives, such as various polyoxyethylene ethers with hydrophobic groups such as aliphatic, aliphatic aromatic, aliphatic phenolic, arylphenolic, and oleyl groups, such as the Peregal series, OP series, Tween series, polyol series, ricinoleic acid series, and alkyl polyglycosides. However, nonylphenol polyoxyethylene ethers, which are known to have estrogenic toxicity, should be discarded.

[0095] (4) The prochloraz manganese salt / kasugamycin nanosuspension dispersion is formed during the dilution process by the reaction of the precursor prochloraz with manganese chloride to form prochloraz manganese nanoparticles. Kasugamycin is dissolved as a single molecule in the diluted water. Due to its low active ingredient content, it is at a sprayable concentration and can be used directly for spraying. The size and stability of the prochloraz manganese salt nanoparticles can be adjusted by controlling the amount of polymer adjuvant. The amount of polymer adjuvant used is related to the amount of prochloraz manganese salt produced in the system and the amount of dilution water used. For example, when using prochloraz manganese salt / kasugamycin to control gray leaf spot on vegetables, the active ingredient dosage is 15 / 5g / mu. If the dilution water consumption is 20kg, the active ingredient concentrations are 0.075% and 0.025%, respectively. The polymer adjuvant concentration is at least 0.2% to 0.5%. Testing has shown that the active ingredient particles in the prochloraz manganese salt / kasugamycin nanosuspension dispersion are approximately 10 to 50 nm in size. This nanosuspension can remain in a stable state within 2 to 8 hours without precipitation or settling, and can be directly used in the spraying operations of various pesticide spraying equipment.

[0096] (5) The nanoparticles of the manganese salt of prochloraz / kasugamycin nanosuspension dispersion are formed by reaction during the dilution and mixing of the components. This not only eliminates the need for the synthesis and purification process of the manganese salt of prochloraz from prochloraz in the pesticide technical plant, but also eliminates the need for the multi-step physical processing process of the manganese salt of prochloraz, kasugamycin, and other adjuvants into a wettable powder in the pesticide formulation plant, as well as the corresponding plant equipment. More importantly, the formulation performance is greatly improved. The solution proposed by the present invention integrates the synthesis of the technical product and the manufacture of the formulation. Using the technical product precursor, the nanoparticle of prochloraz / kasugamycin suspension dispersion can be obtained through simple operations in the field and directly used for crop protection. The process is simple, energy-saving and environmentally friendly, significantly reduces production costs, and improves formulation performance. The particle size of the manganese salt of prochloraz / kasugamycin nanosuspension dispersion obtained by the present invention is less than 100 nm, and the number of particles is greatly increased, which can significantly improve the efficacy of the pesticide, reduce the amount of pesticide used, and achieve the effect of reducing the amount of pesticide and increasing the efficiency.

[0097] The key technologies of the present invention lie in the following aspects:

[0098] 1. Nanosuspension dispersion generation process

[0099] This invention innovatively proposes a new model and method for preparing a nanosuspension dispersion by compounding a water- and organic solvent-insoluble pesticide, prochloraz manganese salt, containing polyvalent metal ions, with kasugamycin. Utilizing the dilution process required for pesticide spraying, prochloraz, the precursor of prochloraz manganese salt, is prepared in the form of a nanoemulsion with water-soluble kasugamycin as one component and the corresponding metal manganese salt as the other component. The two components are diluted and mixed in a specific manner. By controlling the concentration and stirring speed of the reactants and leveraging the rapid nature of ionic reactions, a nanosuspension dispersion of prochloraz manganese salt / kasugamycin with a crystal size of less than 100 nanometers is obtained. This method eliminates both the chemical synthesis and purification steps required by the original manufacturer to prepare prochloraz manganese salt from prochloraz, as well as the multi-step processing steps required by the pesticide formulation manufacturer to compound prochloraz manganese salt with kasugamycin to form a wettable powder formulation. This model and method are the most important key technologies of the invention and are also suitable for compounding prochloraz manganese salt with other pesticides to prepare nanosuspension dispersions.

[0100] 2. Dilution water volume

[0101] When the amounts of component A and component B are fixed, the dilution water amount is one of the key technologies for controlling the dilution concentration of the two components to obtain a nanoscale prochloraz manganese salt / kasugamycin suspension dispersion. The dilution water amount determines the reaction of the reactants in the dilution and the concentration of the product. For example, if the amount of prochloraz manganese salt / kasugamycin active ingredient is 15 / 5 grams per mu, if the water amount is too little, such as 2kg, the concentration of the reactants in the dilution is relatively high, the concentration of the generated nanoparticles is 0.75% higher, and the stability time for forming particles with a size of less than 100nm is short. If the water amount exceeds 200kg, although a transparent dilution can still be obtained, the concentration of the auxiliary agent contained in the components is significantly reduced, and the stability of the nanosuspension will also deteriorate unless the amount of auxiliary agent is increased. Therefore, when the amounts of component A and component B are fixed, the appropriate dilution water amount, for example, a water amount range of greater than 5kg and less than 200kg, is one of the key technologies for generating a stable prochloraz manganese salt nanosuspension dispersion.

[0102] 3. Types and dosage of additives

[0103] Selecting and using the appropriate type and dosage of additives is another key technology for obtaining a nano-suspension dispersion of prochloraz manganese salt / kasugamycin. However, when prochloraz and manganese salt form prochloraz manganese salt nanoparticles in water, the dispersion effect of large amounts of water and stirring alone cannot stabilize the resulting nano-sized prochloraz manganese salt particles. This is because the particles are not static; they are constantly undergoing Brownian motion and colliding with each other. As a result of these effective collisions, the particles merge, crystallize, grow, and eventually precipitate. An effective method to prevent the size of the generated particles from increasing is to select the appropriate type of water-soluble polymer additive (also called a dispersant) and determine its appropriate dosage to ensure that the resulting nanoparticles are evenly dispersed in the aqueous solution of the polymer dispersant. This type of dispersant is primarily a water-soluble polymer that is soluble in water. The microscopic state of water-soluble polymers in water is typically the form of random coils. The size of the random coils is usually larger than that of the newly formed prochloraz manganese salt, depending on the molecular weight and concentration of the polymer additive. If the size of the generated prochloraz manganese salt nanoparticles is less than 100nm or even less than 50nm, these particles can enter the interior of the random coils, preventing and slowing the mutual collisions between the particles, thereby improving the stability of the generated nanoparticles. This is the dispersing, suspending and stabilizing effect of adding water-soluble polymer additives.

[0104] The present invention has been tested on a variety of different water-soluble polymer types. Among the numerous anionic, cationic, and nonionic surfactants, only nonionic polymer additives can currently achieve the desired effect, such as polyoxyethylene-polyoxypropylene-polyoxypropylene triblock polyethers, aliphatic polyoxyethylene ethers, aliphatic aryl polyoxyethylene ethers, aliphatic phenol-based polyoxyethylene ethers, aliphatic aryl polyoxyethylene ethers, arylphenol-based polyoxypropylene polyoxyethylene ethers, oil-based polyoxyethylene ethers, alkyl polyglycosides, etc. In most cases, anionic surfactants can react with manganese ions and zinc ions to generate water-insoluble precipitation, thus losing their dispersing effect. However, the present invention does not exclude the special case where appropriate anionic and cationic surfactants are optimized in combination with each other or with nonionic surfactants to achieve a water-soluble and non-precipitated state.

[0105] The type and amount of the water-soluble polymer additive used in the present invention can be determined through experimentation. The criteria for determining the effect are as follows: first, the resulting prochloraz manganese salt / kasugamycin nanosuspension dispersion must be transparent, water-soluble, and have a particle size of less than 100 nm; second, the stability of this transparent nanosuspension dispersion must be at least 2 to 5 hours.

[0106] The amount of the adjuvant used in the present invention is affected by the amount of dilution water. A larger amount of dilution water is used, the amount of the adjuvant used will be appropriately increased. The ratio of the adjuvant to the dilution water should be at least 1:1200, preferably within 1:800, and more preferably within 1:600.

[0107] 4. Adding method and stirring method

[0108] The method of adding ingredients is also a key factor influencing the performance of the prochloraz manganese salt / kasugamycin nanosuspension dispersion. Once the dilution water volume and the ratio between component A and component B are determined, how the mixing process is performed will affect the resulting particle size and stability. For example, the method of adding the three components raises the following questions:

[0109] First, during the dilution process, how and in what order should the three components be diluted? Should component A be added first or component C first? How should the two be mixed?

[0110] Second, should the mixed dilution of components A and C be added to the dilution of component B, or vice versa? Is the addition method pouring, trickling, dripping, or spraying? Is it a single-point addition or multiple-point addition? Is it continuous addition or intermittent addition? And so on.

[0111] In reality, once the addition method is determined, the question of stirring method also arises. Similarly, there are different stirring methods, such as pre-stirring or post-addition mixing? Manual or mechanical stirring? Single-point stirring or multi-point stirring? Continuous stirring or intermittent stirring? The stirring method is closely related to the stirring speed.

[0112] Whether it's the method of addition, stirring, or speed, these factors all hinge on the concentration of the reactants in the reaction zone formed instantly upon mixing the two dilute components, and the ability to rapidly disperse the products. The most direct way to assess the effectiveness of these two methods and stirring speeds is to observe the transparency of the resulting product. If the resulting nanosuspension is clear and transparent, and exhibits a prolonged stability, this indicates an appropriate method of addition and an effective stirring method and speed.

[0113] Preparation method of prochloraz manganese salt / kasugamycin nano-suspension dispersion

[0114] Three-component technical solution

[0115] The present invention adopts a three-component technical solution: a 100nm-level prochloraz manganese salt / kasugamycin nano-suspension dispersion with a stable period of hours. The system is formed by diluting and mixing the three components to form two dilutions, which are then reacted.

[0116] Component A: It is composed of prochloraz nanoemulsion, kasugamycin, a water-soluble polymer additive, and water. Whether the water-soluble polymer additive is added is determined by the stability of component A.

[0117] Component B: solid manganese salt, or its aqueous solution with water.

[0118] Component C: a water-soluble polymer, or an aqueous solution thereof and water.

[0119] Under the conditions that the stirring speed is not less than the effective stirring speed and pre-stirring:

[0120] Preferably, first add component C to the allocated amount of dilution water and stir to dissolve, then add component A to the diluted solution of component C and stir to disperse to form a transparent mixed diluted aqueous solution of "component A + component C". Separately, add component B to the allocated amount of dilution water and stir to dissolve to form a transparent diluted aqueous solution of component B. The dilution water ratio of component B should be much smaller than the dilution water ratio of "component A + component C".

[0121] Preferably, the diluted aqueous solution of component B is added to the mixed diluted aqueous solution of "component A + component C" according to a certain adding method.

[0122] The addition method, addition speed and stirring speed are controlled to generate nanoparticles of prochloraz manganese salt with a size of less than 100 nm in the system, i.e., a nano-suspension dispersion of prochloraz manganese salt / kasugamycin with a size of less than 100 nm, wherein kasugamycin is dispersed and dissolved in the diluent as a single molecule.

[0123] Two-component improvement plan

[0124] One of the improved solutions of the present invention is that the nano-suspension dispersion of prochloraz manganese salt / kasugamycin with a size below 100 nm has a stable period of hours and is a system generated by a mixing reaction of two components.

[0125] Component A: It is composed of nanoemulsion of prochloraz, a precursor of prochloraz manganese salt, kasugamycin, a water-soluble polymer auxiliary agent and water.

[0126] Here, component A in the two-component solution can be considered equivalent to "component A + component C" in the three-component solution.

[0127] Component B is a manganese salt solid, or an aqueous solution of the manganese salt and water, or an aqueous solution of the manganese salt, a water-soluble polymer additive and water.

[0128] This improved solution involves distributing the water-soluble polymer additive between components A and B. If the amount of water-soluble polymer additive in component A is excessive, it can be appropriately added to component B. Considering that the stability of component B is affected by the amount of water and the amount of water-soluble polymer additive, there is an upper limit to the proportion of water-soluble polymer additive in component B, unless the capacity restriction of component B is not considered.

[0129] Effective stirring speed

[0130] The so-called effective stirring speed refers to the process in which when one component is added to another component, the nanopesticide crystals generated in the mixed liquid can be dispersed in time by stirring at a speed not less than the effective stirring speed, without significant crystal aggregation, thus preventing the size of these crystals from increasing to hundreds of nanometers or micrometers.

[0131] Stirring method

[0132] Mechanical stirring: In the field, such conditions are ideal. Large stirring equipment generally does not exceed 100 rpm, and the specific stirring speed can be adjusted within this stirring rate. However, obtaining large containers with stirring devices in the field is often difficult.

[0133] Manual stirring: This is more suitable for most application scenarios. In this case, the stirring speed must meet the physiological requirements of manual stirring and cannot be too fast.

[0134] For manual stirring, the stirring speed should be consistent with the human body's physiological function. To obtain a stable target product, the material addition rate can be appropriately reduced. The material addition rate can be determined by observing the product's transparent state in the system.

[0135] Joining method and joining speed

[0136] In order to make the added materials more uniform and fine, and to disperse them quickly after entering the system, there are three different ways of adding: stirring first and then adding (pre-stirring), stirring and adding at the same time (synchronous stirring), and adding first and then stirring. The present invention gives priority to the first method of stirring first and then adding. In addition, there can be multiple ways of adding, which can be continuous addition, continuous trickle addition, intermittent addition, or dropwise addition, spray addition. For the dropwise addition method, you can use the manual sprayer commonly available in rural areas to spray addition, and this method of adding has the best effect. The speed of addition is still determined by observing the transparent state of the product in the system to determine how fast the material is added.

[0137] Existing pesticide formulations, which use water as a dispersion medium for spraying, typically require dilution or mixing of co-used pesticide formulations before spraying, a process commonly known as "tank mixing." The present invention utilizes this "tank mixing" process, mixing components A and B according to a specific addition method and rate in the presence of a specific water-soluble polymer adjuvant to produce a transparent, tank-mixed nano-suspension dispersion of prochloraz manganese salt / kasugamycin that can be sprayed on-site.

[0138] Dilution water consumption

[0139] Based on the dosage of prochloraz manganese salt, current experimental data indicates that 2 kg or above is a reasonable starting point. This dilution water volume is strongly correlated with the active ingredient dosage and the target stability period. This is a multivariate issue, and the additive content and composition of the components also play a role.

[0140] The present invention aims to produce a nano-suspension dispersion of prochloraz manganese salt / kasugamycin with a transparent stability period of 2 to 5 hours at a level below 100 nm. When the unit masses of the two precursors and the manganese salt and zinc salt reacting therewith are fixed, factors that can affect the nano-size and stability of the particles include the amount of dilution water, the amount of additives used, and the preparation method.

[0141] The amount of water used for dilution can affect the size of the resulting nano-manganese salt of prochloraz crystals and the duration of their stability. This is because the amount of water used as the dispersion medium affects the concentration of the prochloraz and manganese salt solutions at the moment of contact, the concentration of the product in the reaction zone, the uniformity of the product dispersion, and, consequently, the number of generated crystal nuclei, grain size, grain dispersion, and the chances of crystal aggregation and growth. The amount of additive used affects its concentration in aqueous solutions at different water dosages, as well as the extent and duration of its dispersion, suspension, and stabilization effects on the resulting nano-particles. Using too little water will reach a limit. For example, when the dilution water dosage is below 2 kg (drone spraying), the resulting transparent manganese salt of prochloraz / kasugamycin nanosuspension has a short stability time, necessitating an increase in the amount of dilution water.

[0142] The present invention produces more than 10 grams of the target product, i.e., a prochloraz manganese salt / kasugamycin nano-suspension dispersion with a transparent stability period of 2 to 5 hours at a level below 100 nm. Depending on the type of crops to be sprayed, the amount of water used for dilution is selected to be between 5 and 200 kilograms, preferably in the range of 10 to 150 kilograms.

[0143]

Brief description of the attached drawings

[0144] Figure 1: Flowchart for the preparation of prochloraz manganese salt / kasugamycin nanoemulsion dispersion (three components)

[0145] [Implementation Method]

[0146] The method for preparing a nano-suspension dispersion of prochloraz manganese salt with a size of less than 100 nm according to the present invention, taking two components as an example, comprises the following steps:

[0147] In the first step, component A containing prochloraz, kasugamycin, a water-soluble polymer additive and water is added to a proportion of water, stirred and dispersed to form a transparent diluted dispersion of component A.

[0148] In the second step, component B containing manganese chloride solid or its aqueous solution is added to a proportion of water, stirred and dissolved to form a transparent diluted aqueous solution of component B.

[0149] The third step is to uniformly add the diluted aqueous solution of component B to the diluted dispersed aqueous solution of component A in a certain addition method (continuous or intermittent pouring, dropwise addition, spraying, etc.) under mechanical stirring (preferably) or manual stirring conditions and with pre-stirring at a stirring speed not less than the effective stirring speed.

[0150] Here are some examples:

[0151] Example 1.

[0152] A nano-suspension dispersion of manganese prochloraz / kasugamycin can be used to control tobacco brown spot disease. A conventional wettable powder of manganese prochloraz / kasugamycin uses 5.6-6.4 g / mu and 1.4-1.6 g / mu of active ingredients, respectively. Considering the high efficacy of nanopesticides, this example uses a minimum dosage of 5.6 g / mu and 1.4 g / mu of manganese prochloraz / kasugamycin, with 2 kg of water used for dilution. The amount of manganese chloride required to produce 5.6 g of manganese prochloraz is 0.45 g.

[0153] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0154] How to do it:

[0155] (1) In an appropriate container, add water in a distribution ratio of 9 / 10 (1.8 kg), add component A, stir and disperse to obtain a transparent diluted aqueous solution of component A.

[0156] ⑵In another container, add water in a distribution ratio of 1 / 10 (0.2 kg), add component B, stir and dissolve to obtain a transparent diluted aqueous solution of component B.

[0157] ⑶ While stirring, add the diluted aqueous solution of component B to the diluted aqueous solution of component A by intermittent dropwise addition. Control the addition speed and stirring speed to keep the system transparent until the addition of component B is complete.

[0158] The resulting transparent prochloraz manganese salt / kasugamycin nanosuspension dispersion can be directly used for tobacco spraying using drones. The stability time of the prochloraz manganese salt / kasugamycin nanosuspension dispersion was observed to be 2.5 hours.

[0159] Example 2.

[0160] A nano-suspension dispersion of manganese prochloraz / kasugamycin can be used to control gray leaf spot on vegetables. A conventional wettable powder of manganese prochloraz / kasugamycin contains 15 g / mu of active ingredients and 3 g / mu of active ingredients, respectively. This example uses this ratio, with a dilution water consumption of 20 kg / mu. The amount of manganese chloride required to produce 15 g of manganese prochloraz is 1.2 g.

[0161] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0162] How to do it:

[0163] (1) In an appropriate container, add water in a distribution ratio of 19 / 20 (19 kg), add component C, stir and dissolve to obtain a transparent diluted aqueous solution of component C.

[0164] ⑵ Add component A to the diluted aqueous solution of component C, stir and disperse to obtain a transparent mixed dilution of "component A + component C".

[0165] ⑶ In another container, add water in a distribution ratio of 1 / 20 (1 kg), add component B, stir and dissolve to obtain a transparent diluted aqueous solution of component B.

[0166] (4) While stirring, add the diluted solution of component B to the mixed diluted solution of component A + component C by continuous dropwise addition. Control the addition speed and stirring speed to keep the system transparent until the addition of component B is complete.

[0167] A transparent prochloraz manganese salt / kasugamycin nanosuspension dispersion was obtained, which can be directly used for spraying vegetables. The stability time of the prochloraz manganese salt / kasugamycin nanosuspension dispersion was observed. The stability time was 4 hours.

Claims

1. A prochloraz manganese salt / kasugamycin nano-suspension dispersion, characterized in that: The prochloraz manganese salt / kasugamycin nano-suspension dispersion refers to a prochloraz manganese salt / kasugamycin nano-suspension dispersion of less than 100 nanometers; the prochloraz manganese salt / kasugamycin nano-suspension dispersion of less than 100 nanometers is formed by diluting and mixing three components with water: Component A: composed of prochloraz nanoemulsion, kasugamycin, water-soluble polymer additives and water; Component B: a manganese salt solid or an aqueous solution formed by a combination of a manganese salt solid and water; Component C: A mixture consisting of at least one water-soluble polymer auxiliary agent.

2. The prochloraz manganese salt / kasugamycin nano-suspension dispersion according to claim 1, characterized in that: The component C is added with diluting water to form a transparent aqueous solution.

3. The prochloraz manganese salt / kasugamycin nano-suspension dispersion according to claim 1, characterized in that: The water-soluble polymer auxiliary agent is a non-ionic surfactant.

4. The prochloraz manganese salt / kasugamycin nano-suspension dispersion according to claim 3, characterized in that: The nonionic surfactant is at least one of the following options: Water-soluble starch, cellulose and its derivatives, water-soluble guar gum and its derivatives, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, aliphatic polyoxyethylene ether, aliphatic aryl polyoxyethylene ether, aliphatic phenol polyoxyethylene ether, aryl phenol polyoxypropylene polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polysaccharide, Tween, polyvinyl alcohol; Preferred are polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymers, aliphatic polyoxyethylene ethers, aliphatic aryl polyoxyethylene ethers, aliphatic phenolic polyoxyethylene ethers, arylphenolic polyoxypropylene polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkyl polysaccharides, and Tweens.

5. The prochloraz manganese salt / kasugamycin nano-suspension dispersion according to claim 1, characterized in that: The nano-suspension dispersion of prochloraz manganese salt / kasugamycin with a size below 100 nanometers has a stable period of hours.

6. The prochloraz manganese salt / kasugamycin nano-suspension dispersion according to claim 1, characterized in that: The ratio of the amount of the water-soluble polymer additive to the amount of dilution water is not greater than 1:1000.

7. The prochloraz manganese salt / kasugamycin nano-suspension dispersion according to any one of claims 1 to 7, characterized in that: The mass ratio of prochloraz manganese salt to kasugamycin is in the range of: Prochloraz manganese salt: kasugamycin = 1-7:1; Preferably, the ratio of prochloraz manganese salt: kasugamycin is 1-3:

1.

8. The prochloraz manganese salt / kasugamycin nano-suspension dispersion according to any one of claims 1 to 7, characterized in that: When the manganese salt is manganese chloride, the mass ratio of prochloraz: manganese chloride is in the range of: Prochloraz: manganese chloride = 100: 8-10; Preferably, prochloraz:manganese chloride=100:8-9.

9. A method for preparing a prochloraz manganese salt / kasugamycin nano-suspension dispersion, comprising: first adding component C to a distributed dilution water volume, stirring and dissolving, and then adding component A to a dilution of component C, stirring and dispersing, to form a transparent mixed dilution aqueous solution of component A and component C; adding component B to a distributed dilution water volume, stirring and dissolving, to form a transparent dilution aqueous solution of component B; Then add the diluted aqueous solution of component B to the mixed diluted aqueous solution of component A and component C according to a certain adding method: Component A: composed of prochloraz nanoemulsion, kasugamycin, water-soluble polymer additives and water; Component B: a manganese salt solid or an aqueous solution formed by a combination of a manganese salt solid and water; Component C: A mixture consisting of at least one water-soluble polymer auxiliary agent.

10. The preparation method according to claim 10, characterized in that: The method of adding one component to another component is one of the following four methods: continuous addition, intermittent addition, dropwise addition, and spray addition.

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