Prochloraz manganese salt / propineb NANO suspension dispersion

Abstract

The present invention belongs to the field of nanopesticides, and in particular relates to the preparation of a suspension dispersion of a water-insoluble and solvent-insoluble pesticide, the particle size of which is less than 100 nanometers, especially less than 50 nanometers. The less than 100 nanometer-level prochloraz manganese salt / propineb nano suspension dispersion of the present invention is formed by diluting three components with water and mixing.

Description

Prochloraz manganese salt / Propineb nano-suspension 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 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 a highly effective, low-toxic, broad-spectrum carbamate protective organosulfur fungicide, propineb, 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. This method provides a nano-suspension dispersion of prochloraz manganese salt and a nano-suspension dispersion of propineb, i.e., a nano-suspension dispersion of prochloraz manganese salt / propineb, simultaneously obtaining.

[0014] The prochloraz manganese salt / propineb 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] Propineb is a highly effective, low-toxic, broad-spectrum, protective organosulfur fungicide from the carbamate class. Its bactericidal mechanism primarily inhibits the oxidation of pyruvate within pathogens, a crucial process in their energy metabolism. By interfering with this process, propineb prevents the pathogens from obtaining energy, thereby impacting their growth, reproduction, and infectivity, and inhibiting mycelial growth, ultimately achieving its bactericidal effect. Because propineb primarily acts before pathogens infect crops, forming a protective film on the crop surface to prevent pathogen invasion, it is a protective fungicide. Therefore, spraying before or at the onset of disease can achieve effective control. Propineb's key performance attributes include its broad spectrum of activity, including high efficacy against a variety of diseases, including downy mildew, early blight, late blight, leaf spots (black and brown spot), anthracnose, scab, and ring rot. It can be used to control a variety of crop diseases, including apple leaf spot, Chinese cabbage downy mildew, cucumber downy mildew, tomato early blight, tomato late blight, and grape downy mildew. Outstanding protective effect: It forms a protective film on the crop surface, preventing the invasion of pathogens, achieving excellent protection and preventive effects. Fast-acting and long-lasting efficacy: It quickly exerts its fungicidal effect, controlling the development of diseases in a short period of time, while also maintaining its effectiveness for a long time, reducing the frequency and cost of application. High safety: Propineb is a low-toxic fungicide that is non-toxic to bees and relatively safe for users. It acts as a micro-fertilizer: Propineb releases zinc ions to supplement the zinc required for crop growth. While preventing and controlling diseases, it also promotes crop growth, improves the quality of fruits and vegetables, and enhances color. High compatibility: It can be combined with a variety of fungicides to expand its fungicidal spectrum, enhance control effectiveness, and delay the development of drug resistance in pathogens.

[0018] The combination of prochloraz manganese salt and propineb has the following significant advantages:

[0019] Broad fungicidal spectrum. Myclobutanil manganese salt has preventive and therapeutic effects on various diseases such as anthrax and leaf spot. Propineb is effective against diseases such as downy mildew and blight. When the two are combined, the fungicidal range is expanded and a variety of fungal diseases can be prevented and treated at the same time. Enhanced efficacy. After combination, they have a synergistic effect, which improves the prevention and control effect of diseases, reduces the amount of a single agent used, and reduces the risk of drug resistance. Delaying drug resistance. Due to different mechanisms of action, combined use can delay the speed at which pathogens develop resistance to a single agent. Both protective and therapeutic. Myclobutanil manganese salt has a certain therapeutic effect, while propineb mainly plays a protective role. The combination of the two, when used before and in the early stages of the disease, can play a preventive and protective role; when used after the disease occurs, it can inhibit the further development of the disease.

[0020] The combination of prochloraz manganese salt and propineb can prevent and control diseases of various crops

[0021] Fruit trees: Citrus, can effectively prevent and control citrus anthracnose, sand bark disease, etc. Anthracnose is a common disease of citrus, which harms the leaves, branches, and fruits of citrus, causing leaf fall, flower drop, fruit drop, and branch dieback. Sand bark disease can occur on the branches, new shoots, leaves, young fruits, and ripe fruits of citrus, causing symptoms such as lesions and gummosis on various parts of the tree. Pear, has a good prevention and control effect on pear anthracnose. Pear anthracnose can harm the fruits, leaves and other parts of the pear tree, affecting the quality and yield of the fruit. Grape, can prevent and control grape anthracnose. Grape anthracnose mainly harms grape fruits, and begins to cause the disease when the fruit is basically grown to size. The risk of disease is higher for unbagged grapes, which can cause lesions, rot, etc.

[0022] Vegetables: Cucumbers, watermelons, cantaloupes, and other melons can be treated for anthracnose. Black spots appear on leaves and fruit, severely impacting quality and yield. Tomatoes also benefit from the treatment. Anthracnose primarily harms the fruit. Initially, small, water-soaked, transparent spots appear on the surface, expanding into circular or nearly circular spots that are dark and slightly sunken, impacting the marketability of the tomatoes.

[0023] Food crops: Rice, can be used to prevent and control rice blast. Rice blast is one of the most important rice diseases, including leaf blast, panicle blast and other types, which seriously affect rice yield and quality.

[0024] When combining prochloraz manganese salt and propineb, the mass ratio of prochloraz manganese salt to the active ingredient propineb is generally 1:1-5. The specific dosage and ratio need to be determined based on the specific crop and disease. The formulation used is primarily a traditional wettable powder. No other nanoformulations, let alone nanosuspension dispersions, have been reported.

[0025] The dilution process, unlike the process of forming prochloraz manganese salt nanocrystals independently, utilizes a mixture of prochloraz manganese salt and propineb, using a prochloraz nanoemulsion and a propineb aqueous solution as one component, and manganese and zinc salts as the other. When the salt solution is added to the diluted nanoemulsion and propineb aqueous solution, the manganese and zinc ions react with prochloraz and propineb to form prochloraz manganese salt and propineb. It should be noted that in the aqueous dispersion, manganese and zinc ions can interact with prochloraz and propineb to form prochloraz manganese and propineb, as well as various possible morphological structures, such as prochloraz zinc, propineb manganese, and propineb manganese. When the prochloraz manganese salt / propineb nanosuspension dispersion is sprayed on crops, it still provides the sterilizing, protective, and micro-fertilizer effects of the prochloraz manganese salt / propineb matrix, along with the corresponding manganese and zinc ions.

[0026] The formation mechanism of prochloraz / propineb is that manganese ions react with prochloraz to form manganese salt molecules, which are insoluble in the original solvent and precipitate from the solubilized micelles or flocs, forming prochloraz manganese salt nanocrystals. Zinc ions react with propineb in water to form propineb molecules, which also form propineb nanocrystals. The water-soluble polymer additives added to the system exist 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 and propineb nanocrystals generated in the system are less than 100nm, especially less than 50nm, they diffuse into the interior of the random coils under the shear force of mechanical stirring, isolating and preventing the effective collision, aggregation, growth, precipitation, and precipitation of the crystallites. Therefore, the water-soluble polymer additive disperses, suspends, stabilizes, and protects the nanoparticles of prochloraz manganese salt and propineb, resulting in the name of the nano-suspension dispersion of prochloraz manganese salt / propineb. At this point, the system appears clear and transparent, appears water-soluble, and exhibits the "Tyndall phenomenon."

[0027] It is important to note that during the generation of nanoparticles of prochloraz manganese salt and propineb, the rate of salt addition and the stirring speed of the system affect the amount of reactants and products added per unit time, as well as the uniformity of product dispersion. These are all important factors affecting the size of the resulting nanoparticles. Regarding the addition rate, the goal is to generate nanoparticles less than 100 nanometers in size, and the clarity of the system is the criterion. This is based on the theory that when the particle size is less than one-quarter of the lower limit of the visible light wavelength (400-760 nanometers), no significant refraction or reflection occurs, 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.

[0028] To achieve this goal, the following points must be focused on:

[0029] 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, leading to localized excessive concentrations. This will also accelerate the formation of product crystals, resulting in a large number of crystals. This may lead to aggregation between nanocrystals, resulting in larger grain sizes. If the system exhibits opalescence, this indicates that the grain size is already several hundred nanometers. Therefore, the speed at which one component is added should be such that the system remains transparent.

[0030] 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.

[0031] Explanation of terms

[0032] 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).

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] System: The so-called system refers to the suspension dispersion system formed by mixing the two components of the prochloraz manganese salt / propineb nanosuspension dispersion in the present invention under controlled addition rate and stirring. The system is a mixture of water, a precursor nanoemulsion, a precursor solution, a water-soluble polymer auxiliary agent, a manganese salt, a zinc salt, the generated prochloraz manganese salt, and propineb to form the target product, the prochloraz manganese salt / propineb nanosuspension dispersion.

[0038] 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.

[0039] Ingredients: The so-called ingredients refer to the raw materials used in the present invention, including prochloraz, propisonium, manganese chloride, zinc chloride, water-soluble polymer additives and water.

[0040] Precursor: The so-called precursor refers to the parent substance used to generate the target product. Here, the target products are prochloraz manganese salt and propineb, and the precursors are prochloraz and propineb.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] Addition speed: After determining the addition method, control the amount of components added with the goal of achieving effective stirring.

[0049] The prochloraz manganese salt / propineb nano-suspension dispersion of the present invention refers to a prochloraz manganese salt / propineb nano-suspension dispersion of less than 100 nanometers; the prochloraz manganese salt / propineb nano-suspension dispersion of less than 100 nanometers is formed by diluting and mixing three components with water:

[0050] Component A: It is composed of prochloraz nanoemulsion, propison ammonium (or propison sodium, propison potassium), a water-soluble polymer additive and water.

[0051] Component B: solid manganese salt, zinc salt, or a combination of solid manganese salt, zinc salt and water to form a transparent aqueous solution.

[0052] 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.

[0053] The water-soluble polymer auxiliary agent is a nonionic surfactant.

[0054] The nonionic surfactant may be selected from (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-based polyoxyethylene ether, arylphenol-based 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-based polyoxyethylene ether, arylphenol-based polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polyglycoside, Tween.

[0055] Furthermore, the nano-suspension dispersion of prochloraz manganese salt / propineb below 100 nanometers has a stable period of hours.

[0056] Stable period

[0057] The prochloraz manganese salt / propineb nano-suspension dispersion liquid prepared by the present invention is a class transparent appearance, apparent water-soluble dispersion liquid, but itself is not a thermodynamically stable solution. Therefore, the time that the nano-suspension dispersion liquid keeps the transparent state of appearance is not infinitely long, but has a plateau. Consider from the characteristics of spraying operation, after the nano-suspension dispersion liquid prepares, the operating time needed should be at least more than 1 hour, can like this describe the length of the plateau time in hours. Thus, the present invention proposes that the following nano-suspension of 100nm has the concept of "plateau". That is, the following level nano-suspension dispersion liquid of 100nm prepared by the present invention finishes the spraying operation during solution keeps transparency, and plateau should reach 1 hour at least.

[0058] 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.

[0059] During the stabilization period, the nano-scale suspension dispersion remains transparent, which ensures that the particle size remains less than 100 nm.

[0060] Hourly stability period

[0061] From the perspective of spraying operations:

[0062] 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.

[0063] The hour-level stabilization period mentioned in the present invention refers to a stabilization time between 1 and 5 hours.

[0064] For the hourly stable period, further detailed division can be carried out.

[0065] The basic period for spraying operation is 1 to 2 hours; in most cases, the spraying equipment can complete the operation.

[0066] 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.

[0067] Composition and additives of prochloraz manganese salt / propineb nano-suspension dispersion

[0068] Traditional prochloraz / propineb 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. 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 / propineb with particles smaller than 100 nanometers.

[0069] Three-component solution

[0070] The nano-suspension dispersion of prochloraz manganese salt / propineb below 100 nanometers has a stable period of hours and is a system generated by the mixed reaction of three components. They are:

[0071] Component A: It consists of prochloraz nanoemulsion, precursor of propineb (propineb ammonium or propine sodium or propine potassium), water-soluble polymer additive and water.

[0072] Component B: composed of solid manganese salt, zinc salt or a combination of manganese salt and water.

[0073] 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 may be a solid, which reduces packaging volume; or an aqueous solution thereof may be used, but this solution is limited by solubility and requires a certain volume specification.

[0074] 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.

[0075] The composition ratio of prochloraz manganese salt / propineb nano-suspension dispersion

[0076] In Component A, the amount of precursors determines the composition of the two components. Prochloraz in Component A is the precursor for nano-prochloraz manganese salt, while propinephrine (or propinephrine sodium or propinephrine potassium) is the precursor for propineb. The ratio and amount of these two precursors determine the composition of Component B.

[0077] The above indicates that the mass ratio of prochloraz / propineb is 1 / 1 to 5, preferably 1 / 2. The present invention uses the example of spraying Y times the amount of prochloraz / propineb required on 1 / 15 hectare of land. A three-component design is based on generating Y(1 / 2) grams of a nano-suspension dispersion of prochloraz / propineb with a particle size of less than 100 nm.

[0078] Component A, prochloraz and propionate, serves as precursors, each with a specific ratio to its product. Based on a 1 / 2 ratio, approximately Y grams of prochloraz and 2Y grams of propionate are required. Y grams of prochloraz are formulated into a nanoemulsion, and 2Y grams of propionate are dissolved in the solution of component A.

[0079] For component B, determine the amount of manganese salt (e.g., manganese chloride) required to react with prochloraz and the amount of zinc salt (e.g., zinc sulfate) required to react with propionate. It is generally assumed that prochloraz and manganese ions form a 4:1 molecular complex, which allows the calculation of the amount of manganese chloride. Prochloraz and zinc ions bind in a 1:1 ratio, which allows the calculation of the amount of zinc sulfate.

[0080] 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.

[0081] 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.

[0082] Mass ratio of prochloraz: manganese chloride

[0083] There is no strict ratio between prochloraz and manganese ions. To ensure a complete reaction in industrial production, a large ratio of the two is used, 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 the prochloraz manganese salt solid, and no components are lost. The molecular ratio and mass ratio between the two are as follows:

[0084] Prochloraz: manganese chloride = 1:0.3 (molecular ratio); 100:10 (mass ratio) (theoretical upper limit)

[0085] Preferably, prochloraz: manganese chloride = 1:0.275 (molecular ratio); 100:9 (mass ratio) (industrial production ratio)

[0086] More preferably, prochloraz: manganese chloride = 1:0.25 (molecular ratio); 100:8 (mass ratio) (practical application)

[0087] Mass ratio of propinephrine: zinc sulfate

[0088] Existing literature indicates that in the synthesis of propineb, the molecular (molar) ratio of propineb to zinc ion is 1:1.00 to 1.05. Propineb has two ammonium groups, and zinc ion is a divalent metal ion, so the molecular molar ratio should be 1:1, with a slight excess to ensure complete reaction. Although zinc ion also has tetravalent coordination properties, elemental analysis of propineb samples revealed a zinc content close to the theoretical value of 22.8%, indicating that propineb (propylene bisdithiocarbamate) and zinc sulfate are bound in a 1:1 ratio.

[0089] In the present invention, when propineb is used as a precursor, the mass of the precursor is 90 g (0.346 mole, generating 100 g of propineb), and the zinc salt used is zinc sulfate (anhydrate), the mass of the same mole is 56.5 g, and a mass slightly lower than this can also be used.

[0090] Water-soluble polymer additives

[0091] (1) The prochloraz manganese salt / propineb nano-suspension dispersion is prepared by a tank-mixing process involving dilution with water to obtain a ready-to-use composite nano-suspension dispersion. The precursor prochloraz manganese salt is present in component A as a nanoemulsion, while the precursor propineb is dissolved as a monomolecular dispersion in the water of component A. The water-soluble polymer additive can be present in component C or added to component A. The water-soluble polymer additive has emulsifying, suspending, and dispersing properties, which are essential for the formation of prochloraz manganese salt and propineb nanoparticles and their stable suspension and dispersion in water. When the total particle size is less than 100 nanometers, the system becomes a transparent, apparently water-soluble prochloraz manganese salt / propineb nano-suspension dispersion.

[0092] (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.

[0093] (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 by the system, and stabilize the solubilized micelles or flocs; 2. They are not affected by the reaction of polyvalent metal ions with prochloraz or propineb; and 3. They are as environmentally friendly as possible. Therefore, the present invention selects non-ionic polymer adjuvants based on natural substances and their derivatives, such as various polyoxyethylene ethers with aliphatic, aliphatic aromatic, aliphatic phenolic, arylphenolic, or oleyl groups as hydrophobic groups, such as the Peregal series, OP series, Tween series, polyol series, ricinoleic acid series, and alkyl polyglycosides. However, nonylphenol polyoxyethylene ethers, which have estrogenic toxicity, should be discarded.

[0094] (4) The prochloraz manganese salt / propineb nanoparticle suspension dispersion is produced during the dilution process by the reaction of the precursor prochloraz with manganese chloride to form prochloraz manganese nanoparticles, and by the reaction of zinc sulfate with the precursor propineb to form propineb nanoparticles, forming a mixed suspension dispersion. Because the active ingredient content is low and at a sprayable concentration, it can be directly used for spraying. The size and stability of the prochloraz manganese salt and propineb nanoparticles are regulated by controlling the amount of polymer additives used. The amount of polymer additives used is related to the amount of prochloraz manganese salt produced in the system and the amount of dilution water used. For example, when the prochloraz manganese salt / propineb nanoparticle suspension is used to control anthracnose in cucumbers, the active ingredient dosage is 8 / 16 g / mu. If the dilution water used is 50 kg, the active ingredient concentrations are 0.016% and 0.032%, respectively. The concentration of the polymer additive is at least 0.1% to 0.2%. Testing has shown that the active ingredient particles in the prochloraz manganese salt / propineb nanosuspension dispersion are approximately 10 to 50 nm in size. This nanosuspension remains stable for 2 to 8 hours without precipitation or settling, and can be directly applied to various pesticide sprayers.

[0095] (5) The prochloraz manganese salt / propineb nano-suspension dispersion comprises prochloraz manganese salt and propineb nanoparticles formed by reaction during the dilution and mixing of the components. This not only eliminates the synthesis and purification steps required by the pesticide manufacturer to prepare the prochloraz manganese salt technical from prochloraz and the propineb technical from propineb sodium, but also eliminates the multi-step physical processing required by the pesticide formulation manufacturer to convert prochloraz manganese salt, propineb, and other adjuvants into a wettable powder. The solution proposed by the present invention shortens the formulation manufacturing process, allowing the resulting composite nano-suspension dispersion to be obtained in the field and directly applied to crop protection. This process is energy-efficient and environmentally friendly, significantly reducing production costs. The prochloraz manganese salt / propineb nano-suspension dispersion obtained by the present invention has a particle size of less than 100 nm, significantly increasing the number of particles, thereby improving efficacy and reducing pesticide usage, thereby achieving a reduced dosage and increased efficiency.

[0096] The key technologies of the present invention lie in the following aspects:

[0097] 1. Nanosuspension dispersion generation process

[0098] This invention innovatively proposes a new model and method for preparing a nano-suspension dispersion by compounding the water- and organic solvent-insoluble pesticides prochloraz manganese salt and propineb. Taking advantage of the dilution process required for pesticide spraying, prochloraz, a precursor of prochloraz manganese salt, is prepared in the form of a nanoemulsion, along with water-soluble propinebium, a precursor of propineb, as one component, and the corresponding metal manganese and zinc salts as the other components. The two components are diluted and mixed in a specific manner, and the concentration and stirring speed of the reactants are controlled. By leveraging the rapid nature of ionic reactions, a nano-suspension dispersion of prochloraz manganese salt / propineb with crystal sizes less than 100 nanometers is obtained. This method eliminates the chemical synthesis and purification steps required by the original pharmaceutical manufacturer to prepare prochloraz manganese salt from prochloraz and propineb from sodium propineb. It also eliminates the multi-step processing steps required by the pesticide formulation manufacturer to compound prochloraz manganese salt and propineb into a wettable powder formulation. This model and method are the most important key technologies of the invention. This key technology is also suitable for the process of preparing nano-suspension dispersions by compounding myclobutanil manganese salt with other pesticides.

[0099] 2. Dilution water volume

[0100] Once the dosages of components A and B are fixed, the dilution water dosage is one of the key techniques for controlling the dilution concentrations of the two components, thereby producing a nanoscale prochloraz / propineb suspension dispersion. The dilution water dosage determines the reaction of the reactants and the concentration of the products in the dilution. For example, if the dosage of the active ingredients of prochloraz / propineb is 8 / 16 g / mu, using too little water, such as 2 kg, results in a relatively high concentration of the reactants in the dilution, resulting in a 0.4% to 0.8% higher concentration of the resulting nanoparticles and a shorter stability time for particles smaller than 100 nm. If the water dosage exceeds 300 kg, a transparent dilution can still be obtained, but the concentration of the additives in the components is significantly reduced, and the stability of the nanosuspension will also deteriorate unless the additive dosage is increased. Therefore, once the dosages of components A and B are fixed, maintaining an appropriate dilution water dosage, for example, within a range of greater than 5 kg and less than 300 kg, is one of the key techniques for controlling the concentrations of the two components and producing a stable prochloraz / propineb nanosuspension dispersion.

[0101] 3. Types and dosage of additives

[0102] Selecting and using the appropriate type and dosage of additives is another key technology for producing nano-sized suspensions of prochloraz manganese salt / propineb. However, when prochloraz reacts with manganese salts to form nano-sized prochloraz manganese salt particles, and propineb reacts with zinc salts to form nano-sized propineb particles, the dispersion effect of large amounts of water and stirring alone cannot stabilize the resulting nano-sized particles of prochloraz manganese salt and propineb. This is because the particles are not static; they are constantly undergoing Brownian motion and colliding with each other. As a result of these collisions, the particles merge, 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 dosage to ensure that the resulting nano-sized particles are evenly dispersed in the aqueous solution of the polymer dispersant. These dispersants are primarily water-soluble polymers that are soluble in water. Water-soluble polymers typically exist in the form of random coils in water. The size of random coils is typically larger than newly formed prochloraz manganese salt and propineb particles, depending on the molecular weight and concentration of the polymer additive. If the resulting nanoparticles of prochloraz manganese salt and propineb are smaller than 100nm or even 50nm, they can enter the interior of the random coils, preventing and slowing collisions between the particles, thereby improving the stability of the resulting nanoparticles. This is the dispersing, suspending, and stabilizing effect of the water-soluble polymer additive.

[0103] The present invention has tested a variety of different water-soluble polymer types. Among the numerous anionic, cationic, and nonionic surfactants, only nonionic polymer additives currently achieve the desired effect, such as polyoxyethylene-polyoxypropylene-polyoxypropylene triblock polyethers, fatty polyoxyethylene ethers, aryl polyoxyethylene ethers, fatty aryl polyoxypropylene polyoxyethylene ethers, oil-based polyoxyethylene ethers, and alkyl polyglycosides. In most cases, anionic surfactants react with manganese and zinc ions to form water-insoluble precipitates, which lose their dispersing effect. However, the present invention does not exclude the special case where appropriate anionic and cationic surfactants, or nonionic surfactants, are optimized in combination to achieve water solubility without precipitation.

[0104] The type and amount of the water-soluble polymer additive used in the present invention can be determined through experimentation. The criteria for determining this are as follows: first, the resulting prochloraz manganese salt / propineb nanosuspension dispersion must be transparent and water-soluble, ensuring a particle size of less than 100 nm; and second, the stability of this transparent nanosuspension dispersion must be at least 2 to 5 hours.

[0105] 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.

[0106] 4. Adding method and stirring method

[0107] The method of adding ingredients is also a key factor influencing the performance of the prochloraz / propineb nanosuspension dispersion. Once the dilution water volume and the ratio between components A and 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:

[0108] 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? And then how should the two be mixed?

[0109] 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.

[0110] 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.

[0111] Whether it's the addition method, stirring method, or stirring speed, these all ultimately impact 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 remains stable for a long time, this indicates an appropriate addition method and an effective stirring method and speed.

[0112] Preparation method of prochloraz manganese salt / propineb nano suspension dispersion

[0113] Three-component technical solution

[0114] The present invention adopts a three-component technical solution: a nano-suspension dispersion of prochloraz manganese salt / propineb below 100 nm, which has a stable period of hours. The system is formed by diluting and mixing the three components to form two dilutions, which are then reacted.

[0115] Component A: consists of prochloraz nanoemulsion, propisonium and water.

[0116] Component B: solid manganese salt, zinc salt, or an aqueous solution of solid manganese salt, zinc salt and water.

[0117] Component C: water-soluble polymer additive, or an aqueous solution consisting of a water-soluble polymer additive and water.

[0118] Under the conditions that the stirring speed is not less than the effective stirring speed and pre-stirring:

[0119] Preferably, component C is first added to the allocated amount of dilution water, stirred to dissolve, and then component A is added to the diluted solution of component C, stirred and dispersed to form a transparent mixed diluted aqueous solution of components A and C; component B is added to the allocated amount of dilution water, stirred and dissolved to form a transparent diluted aqueous solution of component B.

[0120] Preferably, the diluted aqueous solution of component B is added to the mixed diluted aqueous solution of component A and component C according to a certain adding method.

[0121] The addition method, addition speed and stirring speed are controlled so that nano-crystals of prochloraz manganese salt and propineb below 100 nm are generated in the system, that is, nano-suspension dispersion of prochloraz manganese salt / propineb below 100 nm.

[0122] Two-component improvement plan

[0123] One of the improved solutions of the present invention is a nano-suspension dispersion of prochloraz manganese salt / propineb below 100 nm, which has a stable period of hours and is a system generated by a mixing reaction of two components.

[0124] Component A: It is composed of a nano-emulsion of prochloraz, a precursor of prochloraz manganese salt, a precursor of propineb (or propineb sodium or propineb potassium), a water-soluble polymer auxiliary agent and water.

[0125] Here, component A in the two-component solution can be considered equivalent to "component A + component C" in the three-component solution.

[0126] Component B is a manganese salt or zinc salt solid, or an aqueous solution of the manganese salt or zinc salt with water, or an aqueous solution of the manganese salt or zinc salt with a water-soluble polymer additive and water.

[0127] 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.

[0128] In order to achieve better preparation results, the two components should be pre-stirred before mixing. That is to say:

[0129] The nano-suspension dispersion of prochloraz manganese salt / propineb below 100 nm of the present invention is prepared by diluting components A and B with water and mixing them under pre-stirring conditions.

[0130] Effective stirring speed

[0131] 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.

[0132] Stirring method

[0133] 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.

[0134] 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.

[0135] 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.

[0136] Joining method and joining speed

[0137] 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.

[0138] 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 and propineb, suitable for on-site spraying.

[0139] Dilution water consumption

[0140] Current experimental data indicates that a reasonable starting range is around 5 kg. This dilution water usage is strongly correlated with the active ingredient dosage and our target stability period. This is a multivariate issue, and the additive content and composition of the components also play a role.

[0141] The present invention aims to produce a nano-suspension dispersion of prochloraz manganese salt / propineb 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.

[0142] The amount of water used in the dilution process can influence the size and stability of the resulting nano-manganese salt of prochloraz. This is because the amount of water used as the dispersion medium affects the concentration of the prochloraz, propineb, and manganese and zinc salt solutions at the moment of contact, the concentration of the product in the reaction zone, and the uniformity of its dispersion. This, in turn, influences the number of resulting crystal nuclei, grain size, grain dispersion, and the chances of crystal aggregation and growth. The amount of additive used influences its concentration in the aqueous solution at different water dosages, as well as the extent and duration of its dispersion, suspension, and stabilization of the resulting nano-particles. Excessive water usage reaches a limit. For example, when the dilution water dosage is 2 kg or less (drone spraying), the resulting transparent nano-suspension of prochloraz / propineb has a short stability period, necessitating an increase in the dilution water dosage.

[0143] The present invention produces more than 20 grams of the target product, i.e., a prochloraz manganese salt / propineb 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 300 kilograms, preferably in the range of 10 to 200 kilograms.

[0144]

Brief description of the attached drawings

[0145] Figure 1: Flowchart for the preparation of prochloraz manganese salt / propineb nanosuspension dispersion (three components)

[0146] [Implementation Method]

[0147] 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:

[0148] In the first step, component A containing prochloraz manganese salt nanoemulsion, propison ammonium and water-soluble polymer additives is added to a distributed amount of water, stirred and diluted to form a transparent diluted aqueous solution of component A.

[0149] In the second step, component B containing manganese chloride, zinc sulfate 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.

[0150] The third step is to uniformly add the diluted aqueous solution of component B to the diluted 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.

[0151] Here are some examples:

[0152] Example 1.

[0153] A nano-suspension dispersion of prochloraz / propineb can be used to control anthrax in cucumbers. The active ingredient dosage of a conventional wettable powder of prochloraz / propineb is 8-10 / 16-20 g / mu, respectively. Considering the high efficacy of nanopesticides, this example uses a minimum dosage of 8 / 16 g / mu of prochloraz / propineb, with 30 kg of water used for dilution. The amount of propineb required to produce 16 g of propineb is 14.5 g, and the amount of zinc sulfate is 8.8 g.

[0154] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0155] How to do it:

[0156] ⑴ In an appropriate container, add dilution water in a distribution ratio of 9 / 10 (27 kg), add component A, stir and disperse to obtain a transparent diluted aqueous solution of component A.

[0157] ⑵In another container, add 1 / 10 (3 kg) of dilution water in the distribution ratio, add component B, stir and dissolve to obtain a transparent diluted aqueous solution of component B.

[0158] (3) While stirring, add the diluted aqueous solution of component B to the diluted aqueous solution of component A in a continuous stream. Control the addition speed and stirring speed to keep the system transparent until the solution is completely added.

[0159] A transparent prochloraz manganese salt / propineb nano-suspension dispersion was obtained, which can be directly used for spraying cucumbers. The stability time of the prochloraz manganese salt / propineb nano-suspension dispersion was observed and the stability time was 4 hours.

[0160] Example 2.

[0161] A nano-suspension dispersion of prochloraz / propineb can be used to control anthracnose in apple trees. The active ingredient dosage of a conventional wettable powder of prochloraz / propineb is 40-80 / 50-100 g / mu, respectively. Considering the high efficacy of nanopesticides, this example uses a minimum dosage of 40 / 50 g / mu for prochloraz / propineb, with a dilution water consumption of 200 kg. The amount of propineb required to produce 50 g of propineb is 45 g and the amount of zinc sulfate is 27 g.

[0162] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0163] How to do it:

[0164] (1) In an appropriate container, add dilution water in a distribution ratio of 19 / 20 (190 kg), add component C, stir and dissolve to obtain a transparent diluted aqueous solution of component C.

[0165] 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".

[0166] ⑶ In another container, add dilution water in a distribution ratio of 1 / 20 (10 kg), add component B, stir and dissolve to obtain a transparent diluted aqueous solution of component B.

[0167] (4) While pre-stirring, add the diluted aqueous solution of component B to the mixed diluted solution of "component A + component C" by continuous spraying. Control the addition speed and stirring speed to keep the system transparent until it is completely added.

[0168] A transparent prochloraz manganese salt / propineb nano-suspension dispersion was obtained, which can be directly used for spraying apple trees. The stability time of the prochloraz manganese salt / propineb nano-suspension dispersion was observed and the stability time was 5 hours.

Claims

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

2. The prochloraz manganese salt / propineb 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 / propineb 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 / propineb 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 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 polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkyl polyglycosides, and Tween.

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

6. The prochloraz manganese salt / propineb 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 / propineb nano-suspension dispersion according to any one of claims 1 to 6, characterized in that: The mass ratio of prochloraz manganese salt to propineb in the prochloraz manganese salt / propineb nano-suspension dispersion is in the range of: Prochloraz manganese salt: propineb = 1: 1-5; Preferably, the ratio of prochloraz manganese salt: propineb = 1:

2.

8. The prochloraz manganese salt / propineb nano-suspension dispersion according to any one of claims 1 to 6, characterized in that: When the manganese salt is manganese chloride, the mass ratio of the manganese salt of prochloraz to the manganese chloride in the prochloraz manganese salt / propineb nano-suspension dispersion is in the range of: Prochloraz: manganese chloride = 100: 8-10; Preferably, prochloraz:manganese chloride=100:

8.

9. A method for preparing a nano-suspension dispersion of prochloraz manganese salt / propineb, comprising: first adding component C to a distributed dilution water volume, stirring and dissolving, and then adding component A to a dilution solution 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, propionate and water; Component B: solid manganese salt, zinc salt, or an aqueous solution consisting of solid manganese salt, zinc salt and water; Component C: a water-soluble polymer additive, or an aqueous solution consisting of a water-soluble polymer additive and water.

10. The preparation method according to claim 9, 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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