Prochloraz-manganese chloride complex / triazole bactericide nano-suspoemulsion dispersion

Abstract

The present invention relates to the field of nano-pesticides, and in particular to preparation of a suspension dispersion having a particle size smaller than 100 nanometers, especially smaller than 50 nanometers, of a pesticide variety insoluble in water and a solvent. A prochloraz-manganese chloride complex / triazole bactericide nano-suspoemulsion dispersion having a particle size at most 100 nanometers in the present invention is formed by diluting three components with water and mixing same.

Description

Prochloraz manganese salt / triazole fungicide nano-emulsion 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. This means that the original pesticide can only be processed primarily into a wettable powder formulation. Currently, pesticide formulations processed through mechanical pulverization 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 the manganese salt of prochloraz with triazole fungicides such as difenoconazole, tebuconazole, hexaconazole, and epoxiconazole, which have excellent fungal disease control effects, in order to improve the control effect of the manganese salt of prochloraz and expand the fungicidal spectrum, so that it has a synergistic effect and reduce the amount of a single variety used. When a nano-suspension dispersion of the manganese salt of prochloraz is obtained, nano-emulsion dispersions of difenoconazole, tebuconazole, hexaconazole, and epoxiconazole are also obtained, that is, nano-suspension dispersions of the manganese salt of prochloraz / triazole fungicides are obtained at the same time.

[0014] The nano-suspension dispersion of prochloraz manganese salt / triazole fungicide of the present invention can be directly sprayed by loading it into a pesticide spraying device.

[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, stably existing as one component in nanoemulsions with water as the dispersion medium. Manganese chloride, which reacts with it, dissociates into manganese ions and chloride ions in water, 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] Triazole fungicides are a class of organic compounds containing a 1,2,4-triazole structure. They primarily inhibit ergosterol biosynthesis in fungal cells, disrupting their structure and function, preventing their growth and reproduction, and thus achieving their bactericidal effect. These fungicides have the following characteristics: They are highly systemic; most are absorbed by plant roots or leaves and carried throughout the plant's body. They have a broad spectrum of activity and are effective against a variety of fungal diseases, such as rust and powdery mildew in wheat crops, large and small leaf spot in corn, and anthracnose and scab in fruit trees. Their systemic nature means they are absorbed and carried throughout the plant's body, killing pathogens within the plant, achieving both protective and therapeutic effects. They typically have a long-lasting effect, maintaining their efficacy within the plant after a single application, reducing the number of applications and labor costs.

[0018] The combination of prochloraz manganese salt and triazole fungicides (difenoconazole, tebuconazole, hexaconazole, fluphenazine, etc.) has the following significant advantages:

[0019] Expanding the fungicide spectrum. Prochloraz manganese itself has a broad fungicide spectrum and can control a variety of fungal diseases. Triazole fungicides such as difenoconazole and tebuconazole are also effective against different types of fungal diseases. When combined, they can cover a wider range of pathogens, including those caused by ascomycetes, basidiomycetes, and deuteromycetes. This broadens the overall fungicide spectrum and avoids missing certain pathogens due to the limited fungicidal range of a single agent, thereby more comprehensively controlling a variety of fungal diseases that may occur on crops.

[0020] Enhanced bactericidal efficacy. Prochloraz manganese kills bacteria primarily by interfering with bacterial respiration, while triazole fungicides such as difenoconazole and tebuconazole inhibit the biosynthesis of ergosterol in bacterial cell membranes. The two have different mechanisms of action. When combined, they produce a synergistic effect, complementing and reinforcing each other. This creates multiple barriers within the pathogen, interfering with its metabolism and growth. This kills bacteria more quickly and effectively than using either agent alone, significantly improving disease prevention and control, and effectively controlling the occurrence and development of diseases within a short period of time.

[0021] Delaying the development of drug resistance in pathogens. Long-term use of a single fungicide alone can cause pathogens to gradually develop resistance, reducing the control effectiveness of the agent. Due to differences in their mechanisms of action, the combination of prochloraz manganese and triazole fungicides makes it difficult for pathogens to develop resistance to two agents with different mechanisms of action simultaneously. This slows the development of drug resistance, extends the lifespan of the agent, and maintains effective control over a longer period of time, reducing the frequency and dosage of drug use, and lowering production costs and environmental pollution risks.

[0022] Improves the conductivity of the agent within the plant. Triazole fungicides typically have good systemic conductivity, allowing them to conduct upward and downward within the plant, delivering the agent to all parts of the plant. When combined with a triazole fungicide, prochloraz manganese leverages the triazole fungicide's conductivity to more evenly distribute prochloraz manganese throughout the plant's roots, stems, leaves, and fruit, ensuring that every part of the plant is adequately protected and treated. This enhances the overall protective and therapeutic effects of the agent and improves the crop's overall resistance to disease.

[0023] The combination of prochloraz manganese salt and triazole fungicides can prevent and control the following crop diseases:

[0024] Grain crops. Wheat: Rust (divided into stripe rust, leaf rust, and stem rust); Fusarium head blight: damages the wheat ear, causing ear rot, shrunken grains, and reduced quality. Rice: Blast (divided into leaf blast and neck blast) and sheath blight: primarily damage rice stems, causing cloud-like spots on the stems and, in severe cases, causing plant lodging.

[0025] Fruit tree crops. Apple, leaf spot disease, the pathogen infects the leaves, causing brown spots on the leaves that gradually expand, and in severe cases, lead to early leaf fall. Anthracnose, harms the fruit, causing brown sunken lesions on the fruit surface, seriously affecting the fruit quality and yield. Citrus, anthracnose, mainly harms leaves, branches and fruits. Brown spots appear after the leaves are infected, and sunken lesions appear after the fruits are infected, which can easily lead to fruit rot. Scab, causes tumor-like protrusions to appear on the surface of leaves and fruits, affecting the appearance and quality of the fruit. Mango, anthracnose, black streaks appear after the young shoots are infected, and round or oval lesions appear after the fruits are infected, which can cause fruit rot in severe cases. Powdery mildew: mainly harms the inflorescence and young leaves of mangoes, causing the inflorescence to be deformed, the flowers to wilt, and the young leaves to curl and deform.

[0026] Vegetable crops. Powdery mildew in cucumbers: A white, powdery mildew layer appears on the leaf surface, and in severe cases, the leaves turn yellow and dry. Anthracnose: Circular lesions appear on the leaves, and sunken lesions appear on the fruit. Leaf mold in tomatoes: Yellow lesions appear on the front of the leaves, and a gray-brown mildew layer forms on the back. Early blight: Brown, circular lesions appear on the leaves, and black, sunken lesions appear on the fruit. Anthracnose in peppers: Brown lesions appear on the fruit, and in severe cases, the fruit rots. Blight causes plant wilt, leaf rot, and fruit soft rot.

[0027] The dosage of manganese salts of prochloraz and triazole fungicides in combination varies depending on the specific crop, disease, and formulation. Commonly reported ratios include 2.5-4:1 manganese salts of prochloraz / difenoconazole; 1-5:1 manganese salts of prochloraz / tebuconazole; 12:1 manganese salts of prochloraz / hexaconazole; and 3-4:1 manganese salts of prochloraz / epoxiconazole. Traditional formulations are primarily wettable powders, with some being water-dispersible granules and suspension concentrates. No other nanoformulations, let alone nanoemulsion dispersions, have been reported.

[0028] Unlike the process of forming prochloraz manganese salt nanocrystals independently, the dilution process utilizes water. Prochloraz manganese salt and triazole fungicide are formulated using a prochloraz / triazole fungicide nanoemulsion as one component and a manganese salt as the other. When the salt solution is added to the diluted composite nanoemulsion, the manganese ions react exclusively with prochloraz to form a prochloraz manganese complex. This prochloraz manganese salt is insoluble in the original solvent and precipitates from the solubilizing micelles or flocs, forming prochloraz manganese salt nanocrystals. The addition of a water-soluble polymer additive with emulsifying properties allows the system to exist not only in micelles and flocs but also in larger random coil structures. Random coils are loose, spherical structures formed by the spontaneous coiling of water-soluble polymer chains. When the nanocrystals of prochloraz manganese salt 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 settling of the crystals. Therefore, the water-soluble polymer additive disperses, suspends, stabilizes, and protects the nanocrystals of prochloraz manganese salt. When the crystal size is 100nm, the system appears clear and transparent, and appears water-soluble, exhibiting the "Tyndall phenomenon." The compounded triazole fungicide remains in the original solubilized micelles or flocs, as long as the additive dosage in the diluted dispersion is sufficient to exceed the critical micelle concentration. At this point, the aqueous dispersion of the system contains both prochloraz manganese salt nanocrystals and triazole fungicide nano-solubilized micelles, resulting in the solubilization of the nanoemulsion dispersion.

[0029] What needs attention is that in the process of generating nanocrystals of prochloraz manganese salt, the addition rate of components 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. These are all important factors affecting the size of the generated nanocrystals. Regarding the addition rate, the goal is to generate nanocrystals with a size of less than 100 nanometers, and the clarity of the system is the judgment standard. 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), no serious 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.

[0030] To achieve this goal, the following points must be focused on:

[0031] 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.

[0032] 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.

[0033] Explanation of terms

[0034] 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).

[0035] 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.

[0036] 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.

[0037] Nano-suspension dispersion: This refers to a system in which two dispersion mechanisms coexist: nanoparticle suspension dispersion and nano-solubilized micelle dispersion. These two dispersion mechanisms differ. Nano-suspension dispersion refers to the dispersion and stabilization of nano-sized particles of a substance by the action of a polymer additive, resulting in a kinetically stable state. Nano-solubilized micelle dispersion, on the other hand, refers to the solubilization of a substance or solution into micelles formed by emulsifier molecules. Under the right conditions, this can be a thermodynamically stable system. Because the system exhibits both suspension dispersion and emulsion dispersion, it is called a suspension dispersion.

[0038] 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.

[0039] 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.

[0040] System: The so-called system refers to the suspension and emulsion dispersion system formed by mixing the two components of the prochloraz manganese salt / triazole fungicide nanosuspension dispersion in the present invention, while controlling the addition rate and stirring. The system is composed of water, a nanoemulsion of the precursor and triazole fungicide, a water-soluble polymer adjuvant and a manganese salt, and the resulting prochloraz manganese salt, to form the target product—the prochloraz manganese salt / triazole fungicide nanosuspension dispersion.

[0041] 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.

[0042] Ingredients: The so-called ingredients refer to the raw materials used in the present invention, including prochloraz, triazole fungicide, manganese chloride, water-soluble polymer additives and water.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] Addition speed: After determining the addition method, control the amount of components added with the goal of achieving effective stirring.

[0052] Nanoemulsion compounded with triazole fungicides (difenoconazole or tebuconazole or hexaconazole or fluepoxiconazole)

[0053] The precursor of prochloraz manganese salt is prochloraz. Its combination with triazole fungicides includes the following four forms:

[0054] 1) Prochloraz / Denofoconazole Nanoemulsion

[0055] 2) Prochloraz / Tebuconazole Nanoemulsion

[0056] 3) Prochloraz / hexaconazole nanoemulsion

[0057] 4) Prochloraz / epoxiconazole nanoemulsion

[0058] Effects of binary combination of prochloraz manganese salt and triazole fungicides

[0059] Prochloraz manganese salt has both protective and therapeutic effects. To improve its effectiveness against crop diseases, it is often compounded with triazole fungicides, which have strong systemic properties, a broad spectrum, and a long-lasting effect. Therefore, the combination of prochloraz manganese salt and triazole fungicides offers four key advantages: a broadened antibacterial spectrum, enhanced antibacterial efficacy, delayed development of bacterial resistance, and improved conductivity within plants. To enhance the disease control effectiveness of prochloraz manganese salt, the present invention proposes compounding prochloraz and triazole fungicides into a nanoemulsion. Using a dilution process, the diluted manganese salt solution is added to the diluted prochloraz / triazole fungicide nanoemulsion, simultaneously producing a suspension dispersion of prochloraz manganese salt nanocrystals and a nanoemulsion dispersion of the triazole fungicide, i.e., a prochloraz manganese salt / triazole fungicide nanoemulsion dispersion. The present invention provides a method and scheme, which can reduce the particle size of the compounded prochloraz manganese salt / triazole fungicide nano-suspension dispersion to below 100 nm, thereby improving the efficacy and reducing the dosage, so that the compounded prochloraz manganese salt / triazole fungicide nano-suspension dispersion can play a greater role and be more widely used.

[0060] Performance and application of binary combination of prochloraz manganese salt / triazole fungicide (difenoconazole or tebuconazole or hexaconazole or epoxiconazole)

[0061] Prochloraz manganese salt combined with difenoconazole

[0062] Triazole fungicides are sterol demethylation inhibitors characterized by high efficacy, broad spectrum, low toxicity, and low dosage. Difenoconazole is a superior triazole fungicide with strong systemic properties and a unique mechanism of action. It is primarily used to control sheath blight, rust, early blight, leaf spot, scab, and powdery mildew on crops such as fruit trees, vegetables, wheat, potatoes, beans, and melons, achieving excellent control. It also offers excellent protection and treatment against a variety of fungal diseases in vegetables, fruits, and melons, with a long-lasting effect and no cross-resistance with other fungicides. Furthermore, it possesses three characteristics: no environmental pollution, no contamination of agricultural products, and no harm to natural enemies. It is currently an ideal fungicide for controlling crop resistance diseases such as apple leaf spot and citrus scab in countries around the world.

[0063] Prochloraz manganese salt is combined with difenoconazole to enhance performance, providing systemic and protective properties with a longer duration of action. This broadens the fungicide spectrum, leveraging the strengths of different fungicides to enhance control effectiveness. It is widely used in crops such as fruit trees and vegetables. It can control a variety of fungal diseases, including anthracnose, leaf spot, powdery mildew, and scab.

[0064] Prochloraz manganese salt combined with tebuconazole

[0065] Tebuconazole has three functions: protection, treatment, and eradication. It has a broad spectrum of activity and a long-lasting effect. Its mechanism of action is to inhibit the biosynthesis of ergosterol in fungi. Tebuconazole can be used for seed treatment or foliar spraying of important economic crops. It is effective in controlling various diseases of cereals, including rust, powdery mildew, web blotch, root rot, fusarium head blight, smut, seed-borne ring spot, and early rice sheath blight.

[0066] The combination of prochloraz manganese and tebuconazole broadens the fungicide spectrum. Prochloraz manganese has good control effects against a variety of diseases, including anthrax and leaf spot, while tebuconazole is particularly effective against rust, powdery mildew, and scab. This combination simultaneously targets a wider range of fungal diseases, expanding the scope of control. Tebuconazole is highly systemic and can be transported throughout the plant, and prochloraz manganese also has some systemic transport. The synergistic effect of the two compounds significantly enhances their fungicidal efficacy, enabling more effective pathogen control. The combination exhibits even stronger fungicidal activity against difficult-to-control diseases, such as stubborn anthrax and severe powdery mildew. It also extends the duration of action. When used alone, prochloraz manganese or tebuconazole may have limited effectiveness. However, when combined, the different mechanisms of action of the two components complement each other in the plant, extending the duration of the agent's effect. It delays drug resistance and, through the synergistic effect of different mechanisms of action, can reduce the risk of pathogens developing resistance to a single agent, thus ensuring the long-term effectiveness of the agent.

[0067] The combination of myclobutanil manganese salt and tebuconazole can be used to prevent and control a variety of crop diseases. Fruit trees: Apple, it can prevent and control anthracnose, ring rot, leaf spot, etc. Pear trees, it has a good control effect on black spot, rust, ring rot, etc. Citrus, it can effectively prevent and control anthracnose, scab, black spot, etc. Field crops: Wheat, it mainly prevents and controls ergot, powdery mildew, rust, etc. Rice, it can be used to prevent and control rice blast, sheath blight, rice false smut, etc. Vegetables: Cucumber, it has a certain control effect on anthracnose, powdery mildew, etc. Tomato, it can prevent and control leaf mold, early blight, gray mold, etc. Pepper, it can prevent and control anthracnose, blight, etc.

[0068] Prochloraz manganese salt mixed with hexaconazole

[0069] Hexaconazole is also a sterol demethylation inhibitor, capable of disrupting and preventing the biosynthesis of ergosterol, a key component of pathogenic cell membranes. This prevents cell membrane formation and leads to the death of the pathogen. It has a broad spectrum of systemic, protective, and therapeutic effects against fungal diseases, particularly those caused by Basidiomycetes and Ascomycetes. It effectively controls diseases caused by Ascomycetes, Basidiomycetes, and Deuteromycetes, and has an excellent protective and eradicative effect against diseases caused by Basidiomycetes and Ascomycetes, such as powdery mildew, rust, scab, brown spot, and anthracnose.

[0070] The performance of prochloraz manganese salt is enhanced when combined with hexaconazole. This broadens the fungicidal spectrum, allowing it to simultaneously target multiple fungal diseases and improve control effectiveness. The enhanced fungicidal activity and synergistic effect enhance the fungicidal capacity, enabling more effective disease control. This product is widely applicable to fruit trees such as apples, pears, and citrus, as well as grain crops and vegetables such as wheat, rice, and corn. It controls fruit tree diseases such as anthracnose, leaf spot, and scab; grain crop diseases such as sheath blight, powdery mildew, and rust; and vegetable diseases such as downy mildew, gray mold, and leaf mold.

[0071] Prochloraz manganese salt combined with epoxiconazole

[0072] Fluoxetine is a broad-spectrum, systemic triazole fungicide with a strong affinity for a fungal enzyme. Compared to currently known fungicides, it is more effective in inhibiting pathogenic fungi. The combined performance advantage is its broad spectrum of activity, effectively controlling over ten diseases of cereal crops, including damping-off, powdery mildew, and eye stripe. It also controls diseases of sugar beets, peanuts, rapeseed, turfgrass, coffee, rice, and fruit trees. It is also effective against vegetable crops such as bananas, onions, garlic, celery, beans, melons, and asparagus, as well as against anthracnose and white rot in grapes. Its strong systemic properties allow it to be rapidly absorbed by the plant and transported to susceptible areas, immediately halting infection. Even localized application provides complete control. Its long-lasting effect on cereals can last for over 40 days, reducing the frequency of drug applications and labor costs. It can enhance the disease resistance of crops, regulate the activity of enzymes to improve the biochemical disease resistance of crops, enhance the disease resistance of crops, make the leaves greener, ensure the maximization of crop photosynthesis, and thus increase yield and improve quality.

[0073] When combined with epoxiconazole, manganese salt of prochloraz complements its fungicidal spectrum, providing effective control of wheat fusarium head blight. Prochloraz manganese salt exhibits both protective and eradicative properties, with systemic conductivity, providing some protection against wheat fusarium head blight. Epoxiconazole is a highly systemic triazole fungicide with excellent control effects against a variety of fungal diseases. It strongly inhibits the growth and reproduction of wheat fusarium head blight pathogens. The combination of the two broadens the fungicidal spectrum, effectively controlling wheat fusarium head blight at different stages and different pathogen types. The combination of prochloraz manganese salt and epoxiconazole exhibits synergistic effects, enhancing fungicidal efficacy and reducing the risk of pathogen resistance to a single agent. Epoxiconazole also exhibits a long-lasting effect, demonstrating strong protection, with disease protection lasting for over 40 days after application to wheat. When combined with manganese salt of prochloraz, the long-lasting effect of the fungus can be extended, reducing the number of applications and lowering control costs.

[0074] The nano-emulsion dispersion of prochloraz manganese salt / triazole fungicide of the present invention refers to a nano-emulsion dispersion of prochloraz manganese salt / triazole fungicide with a size of less than 100 nanometers. The nano-emulsion dispersion of prochloraz manganese salt / triazole fungicide with a size of less than 100 nanometers is formed by diluting and mixing three components with water:

[0075] Component A: Prochloraz / triazole fungicide (difenoconazole, tebuconazole, hexaconazole, or epoxiconazole) nanoemulsion. It consists of a nanoemulsion formed by prochloraz (a precursor of prochloraz manganese salt) and a triazole fungicide, a water-soluble polymer additive, and water.

[0076] Component B: Manganese chloride solid or combined with water to form a transparent aqueous solution.

[0077] 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.

[0078] The water-soluble polymer auxiliary agent is a nonionic surfactant.

[0079] 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, etc.

[0080] Furthermore, the nano-suspension dispersion of prochloraz manganese salt / triazole fungicide with a size below 100 nanometers has a stability period of hours.

[0081] The prochloraz manganese salt / triazole fungicide nano-suspension dispersion liquid of the present invention's preparation is a class transparent appearance, apparent water-soluble liquid, but itself is not a thermodynamically stable solution.Therefore, it is not infinitely long that the nano-suspension dispersion liquid keeps the time of transparent appearance state, but has a stable period. Consider from the characteristics of spraying operation, after the nano-suspension dispersion liquid prepares, the operating time needed should be more than 1 hour at least, can like this describe the length of the stable period time in hours.Thus, the present invention proposes that there is the concept of " stable period" in the following nano-suspension of 100nm.That is, the following level nano-suspension dispersion liquid of the 100nm of the present invention's preparation finishes spraying operation during solution keeps transparency, and the stable period should reach 1 hour at least.

[0082] 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.

[0083] During the stable period, the nano-scale suspension emulsion dispersion remains transparent, which means that the particle size is still less than 100nm.

[0084] Hourly stability period

[0085] From the perspective of spraying operations:

[0086] 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-emulsion dispersions. The stabilization time is between 2 and 5 hours, which is sufficient for most pesticide spraying equipment.

[0087] The hour-level stabilization period mentioned in the present invention refers to a stabilization time between 1 and 5 hours.

[0088] For the hourly stable period, further detailed division can be carried out.

[0089] The basic period for spraying operation is 1 to 2 hours; in most cases, the spraying equipment can complete the operation.

[0090] 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.

[0091] Composition and additives of prochloraz manganese salt / triazole fungicide nano-emulsion dispersion

[0092] Traditional prochloraz manganese salt pesticide 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 nanoscale suspension dispersion, employs a three-component formulation and, following a specific method, dilutes the suspension with water to produce a nanoscale suspension dispersion of prochloraz manganese salt / triazole fungicide with particles smaller than 100 nanometers.

[0093] Three-component solution

[0094] The nano-emulsion dispersion of prochloraz manganese salt / triazole fungicide with a size below 100 nanometers has a stable period of hours and is a system generated by the mixed reaction of three components. They are:

[0095] Component A: Nanoemulsion prepared from prochloraz / triazole fungicide.

[0096] Component B: Manganese chloride solid or dissolved in water.

[0097] 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.

[0098] Proportion of ingredients for forming prochloraz manganese salt / triazole fungicide nano-suspension dispersion

[0099] In component A and component B, the amount of the precursor is the basis for determining the composition of the two components. Prochloraz in component A is the precursor for the formation of nano-prochloraz manganese salt and is the basis for determining the composition of component B.

[0100] The above indicates that the ratio of prochloraz manganese salt to triazole fungicide is X / 1. The ratio (X / 1) varies depending on the triazole fungicide used. The present invention uses the example of spraying Y times the amount of prochloraz manganese salt per 1 / 15 hectare of field. A three-component design is based on generating Y (X / 1) grams of a nano-emulsion dispersion of prochloraz manganese salt / triazole fungicide with a particle size of less than 100 nm.

[0101] Component A, prochloraz as a precursor, requires XY grams of prochloraz and Y grams of triazole fungicide according to the ratio (X / 1), which are formulated into a nanoemulsion.

[0102] Component B, determine the amount of manganese chloride required to react with prochloraz. It is generally believed that prochloraz and manganese ions form a 4:1 molecular complex structure, based on which the amount of manganese chloride can be calculated.

[0103] 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.

[0104] 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.

[0105] Prochloraz: manganese chloride mass ratio

[0106] There is no strict ratio between prochloraz and manganese ions. In industrial production, to ensure complete reaction, 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, 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:

[0107] Prochloraz: manganese chloride = 1:0.3 (molecular ratio); 100:10 (mass ratio) (theoretical upper limit)

[0108] Preferably, prochloraz: manganese chloride = 1:0.275 (molecular ratio); 100:9 (mass ratio) (industrial production ratio)

[0109] More preferably, prochloraz: manganese chloride = 1:0.25 (molecular ratio); 100:8 (mass ratio) (practical application)

[0110] Water-soluble polymer additives

[0111] (1) The prochloraz manganese salt / triazole fungicide nanoemulsion dispersion is prepared by a tank-mixing process involving dilution with water to obtain a ready-to-use composite nanoemulsion dispersion. The precursor prochloraz and the triazole fungicide are present in component A as a nanoemulsion. A water-soluble polymeric additive can be present in component C or added to component A. The water-soluble polymeric additive has emulsifying, suspending, and dispersing properties, which are the basis for the formation of prochloraz manganese salt nanoparticles and their stable suspension and dispersion in water. The nanoemulsion particles containing the triazole fungicide are stably dispersed in the dilution solution, with all particles having a size of less than 100 nanometers. This results in a transparent, apparently water-soluble prochloraz manganese salt / triazole fungicide nanoemulsion dispersion.

[0112] (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.

[0113] (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 floccules; 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 phenolic, aliphatic arylphenolic, and oily 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.

[0114] (4) The prochloraz manganese salt / triazole fungicide nano-suspension dispersion is directly produced by the reaction of the precursor prochloraz with manganese chloride during the dilution process prior to use. Since the active ingredient content is at the spraying concentration, it is relatively low, approximately 0.1-0.2 g / kg water (for example, if the active ingredient dosage of prochloraz manganese salt is 10 g / mu, the sprayer uses 50-100 kg / mu of water, with an acre being 1 / 15 of a hectare, and the same applies hereinafter). The size and stability of the prochloraz manganese salt nanoparticles are adjusted by controlling the dosage of the polymer additive. The dosage of the polymer additive is related to the amount of prochloraz manganese salt produced in the system and the amount of water used for dilution. For example, if the prochloraz manganese salt is 10 g / mu and the dilution water dosage is 50, 100, and 150 kg, respectively, the active ingredient concentrations are 0.02%, 0.01%, and 0.0067%, respectively. The concentration of the polymer additive is at least in the range of 0.1% to 0.2%. Testing has shown that the active ingredient particles in the prochloraz manganese salt / triazole fungicide nanoemulsion dispersion are approximately 10 to 50 nm in size. This nanosuspension remains stable for less than 8 hours without precipitation or settling, and can be directly applied to various pesticide sprayers.

[0115] (5) In the prochloraz manganese salt / triazole fungicide nano-suspension dispersion, the prochloraz manganese salt nanoparticles are formed by reaction during the dilution and mixing process. This not only eliminates the need for the synthesis and purification process of the prochloraz manganese salt technical drug prepared from prochloraz in the pesticide raw material factory, but also eliminates the need for the multi-step physical processing process of the prochloraz manganese salt, triazole fungicide, and other adjuvants in the pesticide formulation factory to form a wettable powder. The solution proposed by the present invention eliminates the manufacturing process of the technical drug and formulation, and the nano-suspension dispersion can be obtained in the field and directly applied to the plant protection of crops. The operation process is simple, energy-saving and environmentally friendly, and production costs are significantly reduced. The particle size of the prochloraz manganese salt / triazole fungicide nano-suspension dispersion obtained by the present invention is less than 100 nm, which can significantly increase the number of particles, improve the efficacy of the pesticide, reduce the amount of pesticide used, and play a significant role in reducing the amount of pesticide and increasing its efficiency.

[0116] The key technologies of the present invention lie in the following aspects:

[0117] 1. Nano-emulsion dispersion generation technology

[0118] This invention innovatively proposes a new model and method for preparing nanoemulsion dispersions by compounding a water- and organic solvent-insoluble pesticide, prochloraz manganese salt, containing polyvalent metal ions, with a triazole fungicide. Utilizing the dilution process required for pesticide spraying, prochloraz manganese salt precursor prochloraz and a compounded triazole fungicide are prepared as nanoemulsions, with the corresponding metal manganese salt as the other component. These two components are diluted and mixed in a specific manner, with controlled reactant concentrations and stirring speeds. By leveraging the rapid nature of ionic reactions, the resulting nanoemulsion dispersions, i.e., nanosuspension dispersions of prochloraz manganese salt and diluted nanoemulsion dispersions of triazole fungicide, are obtained. This method eliminates both the synthesis and purification steps required by prochloraz manganese salt manufacturers to prepare prochloraz manganese salt from prochloraz, as well as the multi-step processing steps required by pesticide formulation manufacturers to compound prochloraz manganese salt technical with a triazole fungicide into a wettable powder, as well as the associated expensive equipment. 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 dispersants by compounding prochloraz manganese salt with other pesticides.

[0119] 2. Dilution water volume

[0120] After the amount of component A and component B is 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 / triazole fungicide suspension dispersion. The dilution water amount determines the concentration of the reactants in the dilution and the product. If the water amount is too little, such as 2 kg, the concentration of the reactants in the dilution is relatively large, the concentration of the generated nanoparticles is high, and the stability time of the particle size below 100 nm is short. If the water amount exceeds 300 kg, although a transparent dilution can still be obtained, the concentration of the auxiliary agent contained in the component is significantly reduced, and the stability of the nano suspension will also deteriorate unless the amount of the auxiliary agent is increased. Thus, after the amount of component A and component B is fixed, the appropriate dilution water amount, for example, a water amount range greater than 5 kg and less than 300 kg, is one of the key technologies for controlling the concentration of the two components and generating a stable prochloraz manganese salt nano suspension dispersion.

[0121] 3. Types and dosage of additives

[0122] Selecting and using the appropriate type and dosage of additives is another key technology for producing nano-suspension dispersions of prochloraz manganese salt / triazole fungicide. However, when prochloraz and manganese salt are combined in water to form prochloraz manganese salt nanoparticles, 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 collisions, the particles merge, grow, and eventually precipitate. An effective way 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 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 random coils. The size of these random coils is generally larger than the newly formed prochloraz manganese salt particles, depending on the molecular weight and concentration of the polymer additive. If the nanoparticles of prochloraz manganese salt generated at this time are smaller than 100nm or even smaller 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 additives.

[0123] The present invention has tested a variety of different types of water-soluble polymers. Among the numerous anionic, cationic, and nonionic surfactants, only nonionic polymer additives can currently achieve the desired effect, such as fatty polyoxyethylene ethers, aryl polyoxyethylene ethers, fatty phenol-based polyoxyethylene ethers, fatty aryl polyoxypropylene polyoxyethylene ethers, oil-based polyoxyethylene ethers, and alkyl polyglycosides. In most cases, anionic surfactants react with manganese ions to form a water-insoluble precipitate, which loses the 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.

[0124] 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 use of the nano-suspension dispersion are as follows: first, the resulting prochloraz manganese salt / triazole fungicide nano-suspension dispersion must be transparent, water-soluble, and have a particle size of less than 100 nm; and second, the stability of the transparent nano-suspension dispersion must be at least 2 to 5 hours.

[0125] 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 amount of dilution water is at least within 1:1200, preferably within 1:1000, and more preferably within 1:800.

[0126] 4. Adding method and stirring method

[0127] The method of adding ingredients is also a key factor influencing the performance of a prochloraz manganese salt / triazole fungicide nanoemulsion 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:

[0128] 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?

[0129] 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.

[0130] 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.

[0131] 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.

[0132] Preparation method of prochloraz manganese salt / triazole fungicide nano-suspension dispersion

[0133] Three-component technical solution

[0134] The three-component technical solution adopted by the present invention: a nano-suspension dispersion of prochloraz manganese salt / triazole fungicide with a size below 100 nm, which has a stable period of hours, is a system formed by diluting and mixing the three components to form two dilutions, which are then reacted.

[0135] Component A: composed of prochloraz / triazole fungicide nanoemulsion.

[0136] Component B: solid manganese salt, or its aqueous solution dissolved in water.

[0137] Component C: a water-soluble polymer, or an aqueous solution thereof dissolved in water.

[0138] Under the conditions that the stirring speed is not less than the effective stirring speed and pre-stirring:

[0139] 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 to disperse, to form a transparent mixed diluted aqueous solution of "component A + component C"; component B is added to the allocated amount of dilution water, stirred to dissolve, to form a transparent diluted aqueous solution of component B.

[0140] 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.

[0141] The addition method, addition speed and stirring speed are controlled to generate nanocrystalline particles of prochloraz manganese salt and nano latex particles of triazole fungicide below 100 nm in the system, that is, nano suspension dispersion of prochloraz manganese salt / triazole fungicide below 100 nm.

[0142] Two-component improvement plan

[0143] One of the improved solutions of the present invention is: a nano-suspension dispersion of prochloraz manganese salt / triazole fungicide with a size below 100 nm, which has a stable period of hours and is a system generated by a mixing reaction of two components.

[0144] Component A: A dispersion consisting of a prochloraz / triazole fungicide nanoemulsion, a water-soluble polymer additive, and water. The dispersion contains prochloraz (a precursor to prochloraz manganese salt), a triazole fungicide, a water-soluble polymer additive that acts as a suspending, dispersing, and emulsifying agent, and water.

[0145] Here, component A in the two-component solution can be considered equivalent to "component A + component C" in the three-component solution.

[0146] Component B is a manganese salt solid, or an aqueous solution of the manganese salt dissolved in water, or an aqueous solution of the manganese salt, a water-soluble polymer additive and water.

[0147] 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.

[0148] Effective stirring speed

[0149] 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.

[0150] Stirring method

[0151] 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.

[0152] 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.

[0153] 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.

[0154] Joining method and joining speed

[0155] 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.

[0156] 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 process to mix components A, B, and C according to a specific addition method and rate in the presence of a specific water-soluble polymer adjuvant, thereby directly producing a transparent, tank-mixed nanoemulsion dispersion of prochloraz manganese salt / triazole fungicide suitable for on-site spraying.

[0157] Dilution water consumption

[0158] Current experimental data indicates that around 5 kg is a reasonable starting range. This dilution water consumption is strongly correlated with our target stabilization period. This is a multivariate issue, and the additive content and composition of the components also play a role.

[0159] The present invention aims to produce a nano-suspension dispersion of a manganese salt of prochloraz / triazole fungicide with a transparent stability period of 2 to 5 hours at a level below 100 nm. When the unit mass of the precursor and the mass of manganese chloride reacted with it 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.

[0160] The amount of water used for dilution can affect 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 solution and manganese chloride solution in the reaction zone at the moment of contact, the concentration of the product, and the uniformity of dispersion. This influences the number of generated nuclei, grain size, grain dispersion, and the chances of crystal aggregation and growth. The amount of additive used affects its concentration in aqueous solution at different water dosages, as well as the extent and duration of its dispersion, suspension, and stabilization of the resulting nano-particles. Using too little water will reach a limit. For example, when the dilution water dosage is less than 2 kg (drone spraying), the resulting transparent manganese salt of prochloraz suspension emulsion has a short stability time, necessitating an increase in the dilution water dosage.

[0161] The present invention produces 20 grams of the target product, i.e., a prochloraz manganese salt suspension 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 30 to 200 kilograms.

[0162]

Brief description of the attached drawings

[0163] Figure 1: Flowchart for the preparation of prochloraz manganese salt / triazole fungicide nanoemulsion dispersion (three components)

[0164] [Implementation Method]

[0165] 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:

[0166] In the first step, prochloraz manganese salt, triazole fungicide nanoemulsion and water-soluble polymer additive (as component A) are added to a distribution ratio of water, stirred and diluted to form a transparent diluted aqueous solution of component A.

[0167] In the second step, manganese chloride solid or its aqueous solution (as component B) is added to a proportion of water, stirred and dissolved to form a transparent diluted aqueous solution of component B.

[0168] 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.

[0169] Here are some examples:

[0170] Example 1.

[0171] A prochloraz manganese salt / difenoconazole nanoemulsion dispersion can be used to control rice sheath blight, false smut, and blast. A reported prochloraz manganese salt / difenoconazole wettable powder uses 8-24 / 3-6 g / mu of active ingredient, respectively. Considering the high efficiency of nanopesticides, this example uses a lower dosage of 8 / 4 g / mu, with a dilution water consumption of 2 kg.

[0172] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0173] How to do it:

[0174] ⑴ In an appropriate container, add water in a distribution ratio of 9 / 10 (1.8 kg), add component A, stir and dilute to obtain a transparent component A dilution solution.

[0175] 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.

[0176] ⑶ While stirring, add the diluted aqueous solution of component B to the diluted solution of component A in a discontinuous dropwise manner. Control the addition speed and stirring speed to keep the system transparent until the addition of component B is complete.

[0177] A transparent prochloraz manganese salt / difenoconazole nanoemulsion dispersion was obtained, which can be directly used for rice spraying using drones. The stability time of the prochloraz manganese salt / difenoconazole nanoemulsion dispersion was observed. The stability time was 2.5 hours.

[0178] Example 2.

[0179] A prochloraz manganese salt / tebuconazole nano-suspension dispersion can be used to control anthracnose and leaf spot disease in apple trees. A reported prochloraz manganese salt / tebuconazole wettable powder has an active ingredient dosage of 20-30 / 10-15 g / mu. Considering the high efficiency of nanopesticides, this embodiment uses a minimum dosage of 20 / 10 g / mu and a dilution water consumption of 200 kg.

[0180] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0181] How to do it:

[0182] (1) In an appropriate container, add 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.

[0183] ⑵Add component A to the diluent of component C, stir and disperse to obtain a transparent mixed diluent of "component A + component C".

[0184] ⑶ In another container, add 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.

[0185] (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 component B is added.

[0186] A transparent prochloraz manganese salt / tebuconazole nanoemulsion dispersion was obtained, which can be directly used for spraying apple trees. The stability time of the prochloraz manganese salt / tebuconazole nanoemulsion dispersion was observed. The stability time was 4 hours.

[0187] Example 3.

[0188] A nano-suspension dispersion of prochloraz manganese salt / hexaconazole can be used to control anthrax and powdery mildew on cucumbers. A reported dosage of the active ingredients of prochloraz manganese salt / hexaconazole is 20-40 g / mu and 1.5-3 g / mu, respectively. Considering the high efficiency of nanopesticides, this example uses a lower dosage of 18 g / mu and 2 g / mu, with a dilution water consumption of 20 kg / mu.

[0189] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0190] How to do it:

[0191] (1) In an appropriate container, add water in a distribution ratio of 9 / 10 (18 kg), add component C, stir and dissolve to obtain a transparent diluted aqueous solution of component C.

[0192] 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".

[0193] ⑶ In another container, add water in a distribution ratio of 1 / 10 (2 kg), add component B, stir and dissolve to obtain a transparent diluted aqueous solution of component B.

[0194] (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.

[0195] A transparent prochloraz manganese salt / hexaconazole nano-emulsion dispersion was obtained, which can be directly used for spraying cucumbers. The stability time of the prochloraz manganese salt / hexaconazole nano-emulsion dispersion was observed. The stability time was 4.5 hours.

[0196] Example 4.

[0197] A nanoemulsion dispersion of prochloraz manganese salt and epoxiconazole can be used to control wheat scab, powdery mildew, and rust. A reported dosage of the active ingredients, prochloraz manganese salt and epoxiconazole, alone is 8-18 g / mu and 6-7.5 g / mu, respectively. Considering the high efficacy of nanopesticides, this example reduces the dosage of the combined formulation to 7 / 3 g / mu, using 2 kg of water for dilution.

[0198] The dosage of each component, the amount of dilution water, and the preparation of the solution are listed in the table below:

[0199] How to do it:

[0200] ⑴ 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 component A dilution solution.

[0201] 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.

[0202] ⑶ While stirring, add the diluted aqueous solution of component B to the diluted solution of component A by continuous dropwise addition. Control the addition speed and stirring speed to keep the system transparent until the addition of component B is complete.

[0203] The resulting transparent prochloraz manganese salt / epoxiconazole nanoemulsion dispersion can be directly used for drone spraying of wheat. The stability time of the prochloraz manganese salt / epoxiconazole nanoemulsion dispersion was observed. The stability time was 2.5 hours.

Claims

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

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

6. The prochloraz manganese salt / triazole fungicide 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 / triazole fungicide nano-suspension dispersion according to claim 1, characterized in that: The triazole fungicide is difenoconazole, tebuconazole, hexaconazole or fluopicolide.

8. The prochloraz manganese salt / triazole fungicide nano-suspension dispersion according to any one of claims 1 to 7, characterized in that: 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 nano-suspension dispersion of prochloraz manganese salt / triazole fungicide, 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: prochloraz / triazole fungicide nanoemulsion; Component B: manganese chloride solid or manganese chloride aqueous solution; 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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