Zinc thiazole / tebuconazole suspended nano-emulsion dispersion

Abstract

The present invention belongs to the field of nano-pesticides, and particularly relates to a pesticide variety which is insoluble in water and a solvent, and the preparation of a suspended emulsion dispersion having a particle size of 100 nm or less. The zinc thiazole / tebuconazole suspended nano-emulsion dispersion at the scale of under 100 nm of the present invention is formed by means of diluting two or three components with water and mixing same.

Description

Thiazole zinc / tebuconazole nanoemulsion dispersion

Technical field

[0001] The present invention belongs to the field of nano pesticides, and particularly relates to a pesticide variety insoluble in water and solvent and a compounding system thereof, and the preparation of a suspension dispersion liquid with a particle size of less than 100 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 reduce pesticide use 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 on 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 extensive contact with the target, allowing the efficacy to be fully exerted and improved.

[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] Thiazole zinc, chemical name is 2-amino-5-mercapto-1,3,4-thiadiazole zinc, chemical formula is C4H4N6S4Zn, relative molecular mass is 329.8, off-white powder, melting point >300℃. It is insoluble in water and organic solvents, decomposes when exposed to alkali, and is stable under neutral and weak alkaline conditions. Thiazole zinc is a zinc-containing heterocyclic fungicide developed in China. It is effective against bacterial diseases and highly effective against a variety of fungal diseases. It can be used to prevent and control crop diseases. The molecular structure of thiazole zinc is composed of two groups. One is the thiazole group, which has no inhibitory effect on bacteria outside the plant body, but is an efficient therapeutic agent in the plant body. The drug causes serious damage to the bacteria in the plant's pore vessels, and its cell wall becomes thinner and then disintegrates, leading to the death of the bacteria. Second, zinc ions have both fungicidal and bactericidal effects. The zinc ions in the agent react with the cations (H + , K + The zinc ions exchange with the zinc ions (e.g., zinc ions in the cell membrane) to cause protein coagulation, thereby killing the bacteria. Some zinc ions penetrate into the pathogen's cells and bind to certain enzymes, affecting their activity, leading to dysfunction, exhaustion, and death. Therefore, the combined action of these two groups in zinc thiazole is highly effective in preventing and controlling pathogens, and its target is wide.

[0006] Thiazole zinc can control the following crops and targets: Cabbage: soft rot bacterial diseases, black spot, anthracnose, rust, powdery mildew, and zinc deficiency aging. Peanuts: bacterial wilt, dead stem and root rot, and leaf spot. Rice: stunted seedlings, yellowing and rotting seedlings, bacterial leaf streak, bacterial leaf blight, sheath blight, blast, and zinc deficiency seedling burn. Cucumbers: bacterial angular leaf spot, canker, downy mildew, yellow spot, and zinc deficiency yellowing. Tomatoes: bacterial canker, late blight, brown spot, anthracnose, and zinc deficiency leaflet.

[0007] The zinc ion in zinc thiazole has coordination properties, so the zinc thiazole molecule exhibits the physical characteristics of being insoluble in both water and organic solvents. For this type of pesticide, improving the dosage form and enhancing the performance of the formulation are both very difficult.

[0008] The existing process for synthesizing the technical substance and preparing the dosage form of zinc thiazole is as follows: (1) Technical substance synthesis. First, a 2-amino-5-mercapto-1,3,4-thiadiazole precursor is synthesized, and then reacted with a zinc salt to form a zinc thiazole precipitate. After separation, washing, and drying, a solid zinc thiazole technical substance is obtained. (2) Formulation processing. Using the solid technical substance of zinc thiazole as the raw material, crushing, grinding, mixing, and other processes are carried out to obtain a zinc thiazole suspension. The above technical substance synthesis and formulation processing process requires corresponding production workshops and equipment, such as filters, dryers, crushers, grinders, and mixers. The entire process is both lengthy and energy-consuming.

[0009] Prior Art 1: Chinese invention patent CN114073250A, "A Suspension Concentrate Containing Nano-Zinc Thiazole and Its Preparation Method," discloses a technology for preparing a nano-scale zinc thiazole suspension concentrate. However, this technology uses a traditional suspension concentrate preparation process, where the zinc thiazole technical and one or more of a surfactant, thickener, preservative, defoamer, and antifreeze agent are combined with water and subjected to a cyclic or multi-stage sanding process to produce the nano-suspension concentrate.

[0010] The obvious shortcomings of this technology are:

[0011] ① The current state of the art indicates that it is difficult to completely crush pesticide technical materials into nano-sized particles using traditional mechanical equipment and mechanical force. In particular, using traditional production equipment and processes, it is essentially impossible to produce a suspension concentrate with particle sizes all below 100 nanometers. This is also confirmed by the data in the patent specification. This is one of the obvious technical shortcomings of this technology.

[0012] ② The "surfactants" used in this technology are all anionic surfactants. Considering the type of surfactant, anionic surfactants are usually monovalent metal salts or their ammonium salts. When anionic surfactants in an aqueous solution encounter polyvalent metal ions, such as zinc ions, they will be replaced by the polyvalent metal ions, thereby losing water solubility and precipitating in the water. If cationic and zwitterionic surfactants are used, during the reaction between thiadiazole salts and zinc sulfate, their basic groups can react with the acidic groups of thiadiazole, disrupting the formation of thiadiazole zinc. Therefore, from the technical perspective of preparing thiadiazole zinc suspensions less than 100 nanometers, the use of anionic surfactants should be avoided. This is another obvious technical defect of this technology.

[0013] Prior Art 2: Chinese invention patent CN107047573A, "Method for Preparing Nano-thiazole Zinc," discloses a method for first producing nano-thiazole zinc technical and then producing thiazole zinc single-dose or compounded formulations. This method for producing nano-thiazole zinc technical involves dissolving a zinc salt and an adjuvant in water, adding a thiadiazole salt solution, and uniformly stirring until a suspension forms. Alternatively, the adjuvant is added to a thiadiazole salt solution, followed by an aqueous zinc salt solution, uniformly stirring until a suspension forms, and finally separating and drying to obtain powdered thiazole zinc. This method for producing nano-thiazole zinc compounded compositions involves combining the aforementioned powdered thiazole zinc with agriculturally acceptable excipients and a fungicide to obtain a wettable powder, water-dispersible granules, suspension, or granules.

[0014] The obvious shortcomings of this technology are:

[0015] ① The technical production process still follows the traditional reaction process and production model. The resulting reaction product is a suspension, which is then dried to obtain a powdered zinc thiazole. Common physics tells us that a liquid product with a "suspension" appearance indicates that its particles are already in the submicron and micron range, as only particles that appear as a transparent liquid are smaller than 100 nanometers. Furthermore, the subsequent drying process inevitably leads to particle aggregation and crystal growth. Therefore, the powdered technical described in this technology cannot fully achieve nanometer dimensions. This is common knowledge in nanofabrication technology.

[0016] ② Using this original drug as raw material and the traditional preparation production process, whether it is a single dose of thiazole zinc or a compound preparation, the particle size of the preparation cannot achieve a true nano size, and is far from achieving a level below 100 nanometers.

[0017] [Summary of the invention]

[0018] One of the objectives of the present invention is to overcome the shortcomings of the existing technology and provide a novel approach and method for preparing traditional zinc thiazole technical and suspension concentrates, which differ from existing technologies. The present invention proposes a dilution process to react a pesticide precursor with a zinc salt in an aqueous solution to produce zinc thiazole. The resulting zinc thiazole nanoparticle suspension dispersion is water-soluble and transparent.

[0019] Another object of the present invention is to compound zinc thiazole with tebuconazole, a fungicide with excellent control effects against fungal diseases, in order to enhance the control effect of zinc thiazole and expand its fungicidal spectrum, thereby achieving a synergistic effect and reducing the dosage of a single species. This method provides a zinc thiazole nanosuspension dispersion and a tebuconazole nanoemulsion dispersion, i.e., a zinc thiazole / tebuconazole nanosuspension dispersion.

[0020] The zinc thiazole / tebuconazole nano-suspension dispersion of the present invention can be directly sprayed after being loaded into a pesticide spraying device.

[0021] The innovative ideas of the present invention are as follows:

[0022] The precursor of zinc thiazole is 2-amino-5-mercapto-1,3,4-thiadiazole (abbreviated as thiadiazole). To maintain its stability, it can be salified with a monovalent metal or ammonia to form its sodium, potassium, or ammonium salts. These salts are highly water-soluble and exist as a single molecular dispersion in water, serving as one component. The zinc salt that reacts with it is also soluble in water and is also dispersed as molecules and metal ions in water, serving as another component. When the two meet under stirring, a substitution reaction between the ions occurs rapidly, easily forming zinc thiazole. By controlling the reaction conditions, the amount of zinc thiazole produced, as well as its nucleation and crystallization growth processes, a nano-suspension dispersion of zinc thiazole can be obtained.

[0023] Tebuconazole, chemically known as (RS)-1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol. Tebuconazole is a highly effective, broad-spectrum, systemic triazole fungicide. Tebuconazole appears as white crystals with a molecular formula of C 16 H 22 ClN3O has a melting point of 102.4°C and a vapor pressure of 0.0133 MPa (20°C). Its solubility in water at 20°C is 32 mg / L, and in toluene it is 50-100 g / L. It is a low-toxic fungicide. Its mechanism of action is to inhibit the demethylation of ergosterol in pathogenic fungi, hindering biofilm formation and achieving a bactericidal effect. Tebuconazole has three functions: protection, treatment, and eradication, with a broad spectrum of activity and a long-lasting effect. It can be used before pathogen infection to prevent invasion and provide protection; after infection to inhibit its growth and reproduction and provide treatment; and it can also kill already infected pathogens and provide eradication. It can be used to prevent and control fungal diseases of various crops, such as powdery mildew, root rot, smut and various rusts of wheat; sheath blight and false smut of rice; leaf spot of peanuts; powdery mildew, anthracnose and leaf spot of vegetables; leaf spot of bananas; powdery mildew, rust, black spot and anthracnose of fruit trees such as apples and pears.

[0024] The performance of zinc thiazole and tebuconazole is improved after compounding:

[0025] Broader bactericidal spectrum. Thiazole zinc is primarily effective against bacterial diseases, such as rice bacterial leaf streak and cabbage soft rot. Tebuconazole is significantly effective against a variety of fungal diseases, such as wheat rust, rice blast, and fruit anthracnose. When combined, the two can simultaneously control bacterial and fungal diseases, greatly broadening the control spectrum and addressing the diverse threats crops may face during growth. For example, in vegetable cultivation, it can effectively control bacterial leaf spot and canker diseases, while also effectively controlling fungal diseases such as downy mildew and gray mold, providing comprehensive protection for the healthy growth of vegetables.

[0026] Enhanced prevention and control effects. Thiazole zinc and tebuconazole have different mechanisms of action, and can produce a synergistic effect when combined. Thiazole zinc kills pathogens by inhibiting the cellular respiration and energy metabolism of pathogens, while tebuconazole mainly inhibits the ergosterol biosynthesis of fungi. The two work together to attack pathogens from different angles, significantly improving the bactericidal effect. For some stubborn diseases, a single agent may have limited prevention and control effects, while compound agents can more effectively control the occurrence and development of diseases. For example, in the prevention and control of fruit tree diseases, the prevention and control effects of anthracnose, black spot, etc. are significantly better than using thiazole zinc or tebuconazole alone.

[0027] Delaying the development of drug resistance. Long-term use of a single fungicide can easily lead to pathogen resistance, reducing control effectiveness. Due to the diverse mechanisms of action, the combination of zinc thiazole and tebuconazole makes it difficult for pathogens to develop resistance to two agents with different mechanisms of action simultaneously, thereby delaying the development of drug resistance and extending the lifespan of the agents. In practical applications, this can reduce the frequency and dosage of drug applications, lowering agricultural production costs while also minimizing environmental pollution.

[0028] Improved crop safety. Well-formulated pesticides typically undergo rigorous safety testing and, when used correctly, are highly safe for crops. Zinc thiazole and tebuconazole, when combined, generally do not cause phytotoxicity to crops and have no adverse effects on their growth and development. For example, when used on grain crops like rice and wheat, they do not affect key growth stages such as heading and grain filling, ensuring crop yield and quality. This also reduces economic losses caused by pesticide damage.

[0029] Thiazole zinc and tebuconazole can be used in combination to prevent and control diseases of the following crops:

[0030] Grain crops: Rice: Bacterial leaf streak, bacterial leaf blight, blast, sheath blight, etc. Wheat: Rust, powdery mildew, head blight, take-all disease, etc. Corn: Large leaf spot, small leaf spot, rust, stem base rot, etc.

[0031] Cash crops: Cotton: Damping off, anthracnose, wilt, and Verticillium wilt. Rapeseed: Sclerotinia rot, downy mildew, and black spot. Soybean: Root rot, gray spot, and rust.

[0032] Vegetable crops: Cucumbers: Downy mildew, bacterial angular leaf spot, target leaf spot, etc. Tomatoes: Early blight, late blight, leaf mold, canker, etc. Cabbage: Soft rot, downy mildew, black spot, etc. Peppers: Blight, anthracnose, scab, etc.

[0033] Fruit crops: Citrus: canker, anthracnose, scab, and black spot. Apple: ring rot, anthracnose, and leaf spot. Pear: black spot, rust, and ring rot. Grape: downy mildew, white rot, and anthracnose.

[0034] The dosage of zinc thiazole and tebuconazole in a compound formulation varies depending on factors such as the specific crop, the disease, and the formulation. Generally speaking: Zinc thiazole: In compound formulations, the typical dosage of zinc thiazole is approximately 10 to 50 grams per mu (approximately 10 to 50 grams per acre). However, this dosage may be adjusted based on actual conditions. In the early stages of some diseases or when they are mild, the dosage can be appropriately reduced. Tebuconazole: The typical dosage per acre is approximately 4 to 7 grams. A reported zinc thiazole / tebuconazole formulation has a 3 / 1 ratio, using a traditional suspension concentrate. No other nanoformulations, let alone nanoemulsion dispersions, have been reported.

[0035] The preparation of the zinc thiazole / tebuconazole nano-suspension emulsion involves stirring one component (e.g., an ammonium salt, sodium salt, or potassium salt of thiadiazole) before the two-component reaction begins. An aqueous solution of a component (e.g., zinc sulfate) is then added to the auxiliary agent aqueous solution of the other component under a controlled stirring speed. By controlling the addition rate and stirring speed, nano-crystals of zinc thiazole and a suspension dispersion thereof can be generated. If a nano-emulsion of tebuconazole is also present in one component, a diluted dispersion of the nano-emulsion of tebuconazole can also be formed while generating the zinc thiazole nano-suspension dispersion, provided that the system contains a sufficient amount of polymer additives. At this point, the system is a mixed dispersion of a nano-suspension and a nano-emulsion, i.e., a nano-suspension dispersion.

[0036] Formation Mechanism of Thiazole Zinc / Tebuconazole Nanoemulsion Dispersion

[0037] In the system, thiadiazole salts and zinc ions meet to form zinc thiazolium molecules, which then aggregate to form zinc thiazolium nanocrystals. When the particles are small and few in number, they can be temporarily and stably dispersed in the aqueous system. As the nanocrystals continue to form, they collide, aggregate, and grow. When the size of the zinc thiazolium nanocrystals approaches the wavelength of visible light, the system begins to exhibit an opalescent sheen. Beyond this, the system gradually becomes opaque. Combined with the force of gravity, the system precipitates as crystals. To prevent this, a water-soluble polymer additive must be present in the system. When dissolved in water, the water-soluble polymer additive forms a random coil structure. A random coil is a loose, spherical structure formed by the spontaneous coiling of water-soluble polymer chains. The interior is composed of lipophilic and hydrophobic molecular chains, while the exterior is composed of hydrophilic polar groups. Numerous random coils aggregate to form micelles. At this point, when the zinc thiazole nanoparticles generated by the system are less than 100nm in size, they diffuse into the interior of the random coils and micelles under the action of stirring shear forces. The random coils and micelles isolate and prevent effective collisions between the grains, thereby preventing further growth, aggregation, precipitation, and settling of the grains. Therefore, the water-soluble polymer additive disperses, suspends, stabilizes, and protects the zinc thiazole nanoparticles. When the grain size is below 100nm, especially below 50nm, the system appears clear and transparent, and appears water-soluble, exhibiting the "Tyndall phenomenon."

[0038] It should be noted that during the production of zinc thiazole nanoparticles, the addition rate of a component and the stirring speed of the system affect the amount of reactants added per unit time and the uniformity of the product dispersion. These factors influence the concentration of reactants in the microscopic reaction zone and are crucial factors influencing the rate of product formation and the size of the resulting nanoparticles. Regarding the addition rate, the goal is to produce nanoparticles with a size of less than 100 nm, and the clarity and transparency of the system are used as the criterion. The theoretical basis for this is that when the particle size is less than one-quarter of the lower limit of the visible light wavelength (400-760 nm), that is, less than 100 nm, there is no significant refraction or reflection, only slight scattering, and the system is transparent, exhibiting the "light pillar" phenomenon known as the Tyndall effect. Conversely, if the system exhibits opalescence or opacity, it indicates a particle size greater than 100 nm. The "suspension" described in the aforementioned comparative art demonstrates particle sizes above the micrometer level.

[0039] Tebuconazole is added to one component in the form of a transparent nanoemulsion. When the two components are mixed, the form of the tebuconazole particles depends on the amount of dilution water and the amount of polymeric additive in the system. When the amount of polymeric additive is sufficient to maintain the presence of nanosolubilized micelles, zinc thiazole nanoparticles and tebuconazole nanoemulsion particles coexist. If the amount of polymeric additive is insufficient to maintain the minimum emulsifier concentration required for the nanoemulsion particles, the micelles disintegrate, and tebuconazole precipitates in the water as nanoparticles. If the tebuconazole is stabilized and suspended by the water-soluble polymeric additive in the system, it forms a mixture of nanoparticles of the two pesticide active ingredients, coexisting in the nanosuspension dispersion.

[0040] To achieve the above goals, we must pay attention to the following points:

[0041] 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 the two components are added too quickly, the two components will be unevenly dispersed, and the local concentration will be too high. This will also accelerate the formation of product crystals, which may cause aggregation between the resulting crystals, resulting in larger grain sizes. If the system exhibits opalescence, it indicates that the grain size is already several hundred nanometers. Therefore, the speed of adding one component should be based on maintaining the system's transparency.

[0042] 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 to ensure that the system remains transparent.

[0043] Explanation of terms

[0044] 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).

[0045] 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.

[0046] 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 the dispersion of insoluble substances in a dispersing medium, are referred to as sols. These particles consist of varying numbers of molecules, exhibiting large interphases and apparent free energies. These sols are unstable, easily disrupted and subject to aggregation, and cannot be restored to their original state, making them thermodynamically unstable and irreversible systems. 2. Solutions of polymer compounds, whose molecular size reaches the colloid range and possesses colloidal properties, are true solutions of dispersed molecules, resulting in thermodynamically stable and reversible systems. These sols are also known as lyophilic sols.

[0047] 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 both suspension dispersion and emulsion dispersion exist within the system, it is called a suspension dispersion.

[0048] 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.

[0049] 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.

[0050] System: The term "system" refers to the suspension dispersion system formed by mixing two components under controlled addition rate and stirring during the preparation of the zinc thiazole nanosuspension in the present invention. The system is the target product—a nanosuspension dispersion—formed by mixing water, a precursor solution, a water-soluble polymer additive, and the generated zinc thiazole.

[0051] 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.

[0052] Ingredients: The so-called ingredients refer to the raw materials used in the present invention, including ammonium salt (or sodium salt, potassium salt) of thiadiazole, zinc salt, water-soluble polymer auxiliary agent, tebuconazole nanoemulsion and water.

[0053] Precursor: The so-called precursor refers to the parent substance used to generate the target product zinc thiazole, namely 2-amino-5-mercapto-1,3,4-thiadiazole ammonium salt (or sodium salt, potassium salt).

[0054] Water-soluble polymer additives are water-soluble polymers containing hydrophilic polar groups within their macromolecules. They are also known as polymer surfactants or polymer additives. 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.

[0055] Particle size: also known as particle size; refers to the size of the thiazole zinc crystals formed by the interaction of the precursor with the zinc salt under the dispersion of the water-soluble polymer additive in the system, and does not specifically refer to the microscopic morphology of the crystals.

[0056] Sub-100 nanometers: This is a statistical classification of the pesticide particle size in a system. Pesticide particle sizes in a suspension exhibit a statistical distribution. The sub-100 nanometer nanosuspension described herein means that at least 90% of the pesticide particles are smaller than 100 nanometers. Thus, particles larger than 100 nanometers constitute only a small fraction.

[0057] Effective stirring speed: The so-called effective stirring speed refers to the ability, under a specific 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 liquid in the system is a sign of achieving an effective stirring speed.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Addition speed: After determining the addition method, control the amount of components added with the goal of achieving effective stirring.

[0062] The zinc thiazole / tebuconazole nano-emulsion dispersion of the present invention refers to a zinc thiazole / tebuconazole nano-emulsion dispersion with a size of less than 100 nm. The zinc thiazole / tebuconazole nano-emulsion dispersion with a size of less than 100 nm is formed by diluting and mixing two components with water:

[0063] Component A: a water-soluble thiadiazole salt aqueous solution, comprising a water-soluble polymer auxiliary agent and a tebuconazole nanoemulsion; the water-soluble thiadiazole salt is one of ammonium thiadiazole, sodium thiadiazole, potassium thiadiazole, or a mixture of at least two of the three.

[0064] Component B: zinc salt or aqueous solution of zinc salt.

[0065] The component B may be further added with a water-soluble polymer auxiliary agent to form an aqueous solution.

[0066] The water-soluble polymer auxiliary agent is a nonionic surfactant.

[0067] The ratio of the amount of the water-soluble polymer additive to the amount of water used for dilution is at least within 1:1000, preferably within 1:800, and more preferably within 1:600.

[0068] The nonionic surfactant may be (at least one) water-soluble starch and its derivatives, water-soluble cellulose and its derivatives, water-soluble guar gum and its derivatives, water-soluble chitosan and its derivatives, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, aliphatic polyoxyethylene ether, aliphatic aromatic polyoxyethylene ether, aliphatic phenolic polyoxyethylene ether, aliphatic aromatic polyoxypropylene polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polyglycoside, etc.

[0069] Preferred are polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymers, aliphatic polyoxyethylene ethers, aliphatic aryl polyoxyethylene ethers, aliphatic phenolic polyoxyethylene ethers, aliphatic aryl polyoxypropylene polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkyl polyglycosides, and the like.

[0070] The zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.

[0071] Furthermore, the zinc thiazole / tebuconazole nano-emulsion dispersion with a size below 100 nm has a stable period of hours.

[0072] For thiadiazole salts and zinc salts, when they are thiadiazole ammonium and zinc sulfate respectively, the range of their mass ratio is:

[0073] Thiadiazole ammonium (the mass of thiazolidine zinc is 100): zinc sulfate = 90: 45-55

[0074] Preferably, thiadiazole ammonium: zinc sulfate = 90: 47-53

[0075] Furthermore, thiadiazole ammonium: zinc sulfate = 90: 48-50

[0076] When the mass ratio of thiadiazole ammonium (the mass of the generated thiadiazole zinc is 100): zinc sulfate = 90:48-50, the mass of the water-soluble polymer additive added to component B, which dissolves the zinc salt in as little water as possible, is preferably such that no turbidity occurs, and is usually not more than 10%.

[0077] In order to achieve better preparation results, the two components should be pre-stirred before mixing. That is to say:

[0078] The zinc thiazole / tebuconazole nano-suspension dispersion liquid with a size of less than 100 nm is prepared by diluting two components with water and mixing them under pre-stirring conditions.

[0079] Thiazole zinc / tebuconazole suspension dispersion below 100nm

[0080] In order to improve the efficacy of the nano-scale zinc thiazole / tebuconazole suspension dispersion, the present invention needs to reduce its particle size as much as possible. The original intention of studying nanopesticides is to improve the efficacy of pesticides and reduce the amount of pesticides used. The particle size of traditional pesticide preparations is usually several microns or above. Reducing it to a corresponding few nanometers spans three orders of magnitude. When the size is reduced to different orders of magnitude, the number of increased particles is also different. For example, if the usual particle size of the traditional preparation is reduced from 2μm to 200nm, 20nm, and 2nm, respectively, theoretically, the number of particles will increase by 1000 (10 3 ), 1 million (10 6 ), 1 billion (10 9 ) times. Therefore, it can be seen that different reductions in particle size and increases in particle number lead to different effects on drug efficacy. Therefore, in order to improve drug efficacy, the particle size should be reduced as much as possible.

[0081] To further enhance the efficacy of the nanoscale zinc thiazole / tebuconazole suspension dispersion, the present invention aims to reduce its particle size to below 100 nm. This is based on two factors. First, the 1-100 nm scale defines the size that nanomaterials and nanoproducts must possess in any one dimension. Second, pesticide particles in the 1-100 nm range form colloidal solutions, appearing water-soluble and transparent. When a beam of light is shone upon the solution, the boundaries of the light beam are visible, consistent with the description of the Tyndall phenomenon. The less pronounced the light beam, the smaller the particle size.

[0082] Concentration of suspension emulsion

[0083] In suspensions with low active ingredient concentrations, the number of particles below 100 nm is relatively high, which has little effect on transparency. This is the case when the zinc thiazole dosage is 10 g / mu (1 mu = 1 / 15 hectare, the same below) and the system is diluted with more than 5 kg of water.

[0084] Suspensions with high active ingredient concentrations have fewer particles smaller than 100nm, significantly impacting transparency. Similarly, for a system with 100g / mu of zinc thiazole diluted with 20kg of water, while the suspension may briefly become transparent, the high active ingredient concentration makes the particles more likely to collide with each other, leading to crystal growth and aggregation, significantly affecting the suspension's transparency and stability.

[0085] The dosage of active ingredient, water and adjuvant, the adaptation and balance among them, and the control of the water dilution process are important factors affecting the acquisition of transparent zinc thiazole / tebuconazole suspension dispersion.

[0086] Stable period

[0087] The zinc thiazole / tebuconazole nano-suspension dispersion liquid prepared by the present invention is a class of transparent appearance, apparent water-soluble dispersion liquid, but the whole is not a thermodynamically stable system. Therefore, the time that the suspension emulsion keeps the transparent appearance state is not infinitely long, but has a plateau. Consider from the operating characteristics of the spraying operation, after the zinc thiazole / tebuconazole 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-level zinc thiazole / tebuconazole nano-suspension dispersion liquid of 100nm has the concept of " plateau". That is, the following level zinc thiazole / tebuconazole nano-suspension dispersion liquid of 100nm prepared by the present invention finishes the spraying operation under the interior that dispersion liquid keeps transparent, and plateau should reach 1 hour at least.

[0088] From the application perspective, the stable period can be further divided into four time periods: less than 1 hour, 1 to 5 hours, 5 to 10 hours, and more than 10 hours.

[0089] The spraying operation was achieved within 1 hour, indicating that the zinc thiazole / tebuconazole nano-emulsion dispersion remained transparent, that is, the particle size was ensured to be still less than 100 nm.

[0090] Direct observation can be used to determine changes in the transparency and particle size of nano-scale zinc thiazole / tebuconazole nanoemulsion dispersions. During the stable period, the suspension remains transparent, with particle sizes less than 100 nm. When the suspension becomes unstable, opalescence first appears, indicating that the particle size is beginning to increase. A faint opalescence indicates that the particle size within the suspension is beginning to exceed 100 nm. Gradually increasing opalescence indicates that the particle size has increased to several hundred nanometers. Further turbidity or even opacity indicates that the particle size has increased to the micrometer level or above. Crystallization or precipitation indicates that the particle size has increased to the millimeter level.

[0091] The present invention observes the phenomenon of the stable period of the zinc thiazole / tebuconazole nano-suspension dispersion liquid with a size below 100 nm, and is applicable to stable periods of different hour levels.

[0092] Hourly stability period

[0093] From the perspective of spraying operations: the stabilization time is about 1 hour, which is not enough for the operation time of spraying operations; if the stabilization period exceeds 10 hours, it is not meaningful to use the spray liquid as a pesticide formulation, because even if the liquid is very stable, it is not conducive to storage and transportation due to the low content of active ingredients and large volume capacity.

[0094] Therefore, the stabilization time is between 1 and 10 hours, and the spraying operations of most pesticide equipment can be completed easily within this time.

[0095] The hour-level stabilization period mentioned in the present invention refers to a stabilization time between 1 and 10 hours.

[0096] For the hourly stable period, further detailed division can be carried out.

[0097] The basic period for spraying operation is 1 to 5 hours; in most cases, the spraying equipment can complete the operation.

[0098] 5 to 10 hours is a sufficient period for spraying operations; it can be used to accommodate spraying operations that are delayed due to special circumstances.

[0099] Components and additives of zinc thiazole / tebuconazole nanoemulsion dispersion

[0100] Traditional zinc thiazole single-ingredient and binary compound formulations typically consist of only one component and can be sprayed after dilution with water. However, most pesticide particles are larger than micrometers in size. To obtain a nanoscale zinc thiazole / tebuconazole nano-emulsion dispersion, the present invention employs at least two components and, through dilution with water according to a specific method, produces a zinc thiazole / tebuconazole nano-emulsion dispersion with a particle size of less than 100 nm.

[0101] Taking the three-component model as an example, the following explanation is given.

[0102] Three-component basic scheme

[0103] The basic scheme of the 100nm-scale zinc thiazole / tebuconazole nanoemulsion dispersion of the present invention is a system generated by the mixing reaction of three components. They are:

[0104] Component A: It is composed of solids of ammonium thiadiazole, sodium thiadiazole or potassium thiadiazole or their aqueous solutions, which are the precursors for generating zinc thiadiazole nanoparticles.

[0105] Component A can be ammonium thiadiazole, sodium thiadiazole, potassium thiadiazole, or a mixture thereof. A single component or a mixture of two or more of the three components can be used. It can be a solid form, which facilitates packaging, minimizes packaging volume, and dissolves quickly in water before use. Alternatively, an aqueous solution can be used, simply diluting to a desired volume with water before use. However, considering the significant amount of water-soluble polymeric additives used, to reduce the number of components, component A typically also contains a certain amount of water-soluble polymeric additives.

[0106] Component B: zinc salt solid or its aqueous solution, which is the multivalent metal ion required to generate zinc thiazole nanoparticles.

[0107] Component B, the zinc salt, is selected from at least one of zinc sulfate, zinc acetate, zinc chloride, and zinc nitrate. Component B can be a solid, which reduces packaging volume, or an aqueous solution, which requires a certain volume specification. Component B may also contain a certain amount of a water-soluble polymer additive.

[0108] Component C: Tebuconazole Nanoemulsion

[0109] Tebuconazole nanoemulsion is used as component C. Tebuconazole nanoemulsion itself contains a certain amount of water-soluble polymer auxiliary agent that plays an emulsifying role. As needed, the water-soluble polymer auxiliary agent can be added or not added to component C.

[0110] The ratio of the total mass of the water-soluble polymer additives in the three components to the amount of dilution water is preferably within 1:800.

[0111] The polymer surfactant selected in the present invention cannot use anionic surfactants. Considering the type of surfactant, commonly used anionic surfactants are usually monovalent metal salts or ammonium salts thereof. When anionic surfactants in aqueous solution encounter polyvalent metal ions, they will be replaced by the polyvalent metal ions, thereby losing water solubility and precipitating in water. Therefore, the present invention selects nonionic surfactants as water-soluble polymer additives to suspend, disperse and stabilize the zinc thiazole nanoparticles generated in the system.

[0112] The water-soluble polymer additive described in the present invention is selected from nonionic surfactants. Preferred are triblock copolymers of polyoxyethylene and polyoxypropylene, fatty acid polyoxyethylene ethers, vegetable oil polyoxyethylene ethers, and alkyl polyglycosides. It can also be selected from natural products and their derivatives, such as water-soluble starch, water-soluble cellulose, water-soluble chitosan, and water-soluble guar gum nonionic derivatives. The water-soluble polymer additive described in the present invention is one or more of the above-mentioned nonionic surfactants. For environmental reasons, natural substances and their derivatives are preferred.

[0113] In order to simplify the components and make the packaging, storage, transportation and dilution with water operation simpler, the above three-component system can be combined into two components.

[0114] Two-component improvement plan

[0115] One of the improvements of the present invention is a zinc thiazole / tebuconazole nanosuspension with a size of less than 100 nm, which has a stability period of hours and is a system generated by the reaction of two components. They are:

[0116] Component A: A dispersion consisting of ammonium thiadiazole (or sodium thiadiazole, potassium thiadiazole), a water-soluble polymer additive, a tebuconazole nanoemulsion, and water. The dispersion contains a precursor for zinc thiazolyl oxide particles smaller than 100 nm, a water-soluble polymer additive for dispersing, suspending, and stabilizing the particles, and the tebuconazole nanoemulsion containing an emulsifier and solvent, along with water.

[0117] Here, component A in the two-component solution can be considered equivalent to "component A + component C" in the three-component solution.

[0118] Component B is a zinc salt solid, or an aqueous solution thereof with water, or an aqueous solution thereof with a water-soluble polymer additive and water. The zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride, and zinc nitrate.

[0119] Since the aqueous solution of zinc salt is affected by the amount of additive added, the amount of water-soluble polymer additive added to component B is limited.

[0120] This improvement plan is to distribute the water-soluble polymer additive used into component A and component B. In view of the fact that the stability of component B will be affected by the amount of water and the amount of water-soluble polymer additive, there is an upper limit to the proportion in component B, unless the limitation of component B to a certain capacity is not considered.

[0121] The present invention takes the example of spraying 1 / 15 hectare (1 mu) of land with 10 grams of zinc thiazole and 3.5 grams of tebuconazole (the ratio of the two is about 3 / 1) as an example, and designs the two components based on the generation of a (10+3.5) grams of zinc thiazole / tebuconazole nanosuspension with a size of less than 100 nm.

[0122] Component A requires approximately 9 grams of thiadiazole ammonium, sodium thiadiazole, or potassium thiadiazole, preferably thiadiazole ammonium, as a precursor, and a tebuconazole nanoemulsion containing 3.5 grams of the active ingredient. Based on the aforementioned principle of distributing the adjuvants between components A and B, the vast majority of the water-soluble polymer adjuvant will be distributed in component A. If component A is packaged in a 250-gram mass, the amount of water used is the amount after subtracting the thiadiazole ammonium, tebuconazole nanoemulsion, and water-soluble polymer adjuvant.

[0123] For component B, first determine the amount of inorganic zinc salt required to react with thiadiazole ammonium. Zinc sulfate is preferred in this invention. It is generally believed that the zinc ion undergoes a displacement reaction with thiadiazole ammonium, but it has a stronger tetravalent coordination ability, coordinating with the sulfur atom on the thiadiazole molecule to form a complex structure.

[0124] In the present invention, when the precursor ammonium thiadiazole is used at a mass of 9 grams (10 grams of zinc thiazolidine produced), the zinc salt is anhydrous zinc sulfate at a mass of 4.8 to 5 grams. If the amount of water-soluble polymer additive in component A is sufficient to suspend and disperse the generated nano-zinc thiazolidine particles, then the water-soluble polymer additive is not required in component B.

[0125] Components A and B must be packaged separately because they react when mixed. If a two-component formulation is used, component A must contain an adjuvant; otherwise, there's nowhere to place the adjuvant, unless a separate adjuvant is added as a dedicated third component. This complicates the packaging and dilution process. In addition to the water-soluble polymer adjuvant, component A also contains a tebuconazole nanoemulsion. The addition of the adjuvant to component A requires that both thiadiazole and the water-soluble polymer adjuvant are water-soluble and miscible. However, given the high total amount of thiadiazole, adjuvant, and tebuconazole nanoemulsion, the dispersion has a high viscosity. For ease of handling, a certain amount of water must be added to dilute and reduce the viscosity. The amount of water added should minimize the overall mass of component A, achieving the aforementioned objectives, thereby reducing the resulting production, packaging, and transportation costs.

[0126] Component B can be a solid zinc salt, which should be dissolved in water before use. For convenience, aqueous solutions of these salts can be used, requiring a certain amount of water. Adding or omitting additives is optional for two reasons: First, a large amount of additive in Component B may form a film on the surface of the zinc salt, additive, and water mixture, hindering the subsequent dilution process. Second, if the amount of additive in Component A is sufficient to suspend and disperse the resulting zinc thiazole nanoparticles, additives can be omitted from Component B. However, if zinc thiazole is used for disease control in orchards, where the tree canopy is large and the water volume required for spraying is high, water consumption can often reach 200 kg / mu or more. If the amount of additive in Component A is insufficient to support the dispersion and suspension of the resulting zinc thiazole nanoparticles in such a large dilution solution, an appropriate additive should be added to Component B to compensate for the additive deficiency in the dilution solution. However, the additive must be added to the aqueous zinc salt solution in an amount that maintains transparency and prevents condensation on the surface of the solution during storage. The mass concentration of the added additive is generally not higher than 10%.

[0127] Although both component A and component B can be increased in mass to address the above difficulties, increasing the dosage of the two components will undoubtedly increase production, packaging, and transportation costs. Taking all these factors into consideration, balancing the dosage of other components and product specifications to minimize the use of other ingredients (adjuvants, water) while maintaining the desired unit mass of zinc thiazole is an important factor to consider.

[0128] Water-soluble polymer additives

[0129] (1) The zinc thiazole / tebuconazole dispersion is obtained by "tank mixing," i.e., a directly usable nano-emulsion dispersion of zinc thiazole and tebuconazole. A water-soluble polymeric additive with a dispersing effect is added to this solution, resulting in the zinc thiazole being dispersed and suspended in the polymeric additive solution in nanometer-sized particles, while the tebuconazole exists as solubilized latex particles. Because the particle size is less than 100 nanometers, the resulting nano-emulsion dispersion of zinc thiazole / tebuconazole is transparent and apparently water-soluble.

[0130] (2) The water-soluble polymer auxiliary agent with dispersing effect is an important component that affects the size of the zinc thiazole nanoparticles generated when the two components are diluted and mixed, as well as whether they can be evenly dispersed and stably suspended.

[0131] ⑶Polymer additives are also called polymer surfactants. They usually refer to substances with large relative molecular mass and surface activity. Compared with small molecule surfactants, polymer surfactants not only reduce surface tension but also have other special properties, such as dispersion, suspension, and viscosity increase. Polymer surfactants can be classified into natural polymers and their derivatives and synthetic polymers according to their source. Polymer surfactants have a hydrophobic chain structure and hydrophilic groups distributed in the side groups and end groups of the chain, such as hydroxyl, carboxyl, carboxymethyl, sulfonic acid, sulfate, phosphoric acid, amino, etc., and are therefore water-soluble. Water-soluble natural polymers and their derivatives include starch and various derivatives (such as oxidized starch, carboxymethyl starch, modified starch), cellulose and its derivatives (carboxymethyl cellulose, hydroxyethyl hydroxypropyl cellulose), guar gum and its derivatives, chitosan and its derivatives, tea saponin, water-soluble humic acid, sodium lignin sulfonate, derivatives of natural substances and polyethylene oxide, etc. Synthetic water-soluble polymers include polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate, polyacrylamide, polystyrene-maleic anhydride copolymer, and polyoxyethylene-polyoxypropylene-polyoxyethylene. Water-soluble synthetic polymers with carbon chains as their backbone are not easily biodegradable. For environmental reasons, biodegradable heterochain polymers and their derivatives should be selected to minimize their impact on the ecological environment.

[0132] (4) The reason for selecting polymeric additives in the present invention is to utilize the dispersing and suspending functions of water-soluble polymers in aqueous solutions. A water-soluble polymer with a relative molecular mass of tens of thousands, hundreds of thousands, or even hundreds of thousands typically has a linear polymer chain structure and can be dissolved in water. When a linear polymer is dissolved in water, its aspect ratio is very large, but it does not appear as a straight chain. Instead, due to the flexibility of the molecular chain, it exhibits a curled state, i.e., a "random coil" morphology. The hydrophilic groups in the random coil tend to face the aqueous phase, while the lipophilic hydrocarbon chains curl within the random coil. The size of the random coil depends on the relative molecular mass of the polymeric additive, its concentration, and the polymer chain structure. The larger the molecular weight, the larger the volume of the random coil formed by a single molecule. The more flexible the polymer chain, the easier it is to rotate internally, and the more stretched it is in the solvent, the larger the volume of the random coil. When the concentration of water-soluble polymers is high, random coils formed by different molecules aggregate to form micelles, resulting in a larger volume. Generally, when the molecular weight of a water-soluble polymer is in the tens of thousands or hundreds of thousands, the size of the resulting random coils ranges from a few nanometers to tens of nanometers or larger. If pesticide nanoparticles form in the system, based on the principle that like dissolves like, the lipophilic nanoparticles tend to enter the interior of the lipophilic random coils and become intercalated in different locations within the random coils. When the pesticide nanoparticles are smaller, more nanoparticles can be dispersed within the random coils. Therefore, water-soluble polymer adjuvants can disperse and stabilize the generated nanoparticles. Traditional pesticide suspension concentrates also utilize this principle, but their pesticide particles are micron-sized. Because the micron particles are larger than the random coils and micelles, suspension concentrates are typically opaque. Furthermore, the greater gravity affects their stability. When the size of pesticide particles is reduced by 2 to 3 orders of magnitude, the gravitational effect on the particles is much smaller. Using the same water-soluble polymer surfactant, a more stable suspension and dispersion system can be obtained, making the suspension and dispersion liquid appear water-soluble and transparent in appearance.

[0133] 5. Water-soluble polymer additives are divided into different types according to the properties of the active groups contained in the macromolecular chain, just like small molecule surfactants. They include anionic polymer additives, cationic polymer additives, zwitterionic polymer additives and non-ionic polymer additives. These polymer additives carry active groups of different properties on the side groups or main chains. For example, anionic polymer additives carry acidic groups such as carboxyl groups, sulfonic acid groups, sulfate groups and monovalent metal salts. Such as carboxymethyl starch, carboxymethyl cellulose, lignin sulfonate, humate, sodium polyacrylate, polystyrene-sodium maleate, etc. Cationic polymer additives carry basic groups or salts formed with acidic groups, such as chitosan (hydrochloride), polyacrylamide, and polymers containing pyridine groups on the side groups and being quaternized. Amphoteric polymer additives are polymers that contain both anionic and cationic groups in their molecular structure, such as carboxymethyl chitosan. Non-ionic polymer additives, such as polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymers, and various polyoxyethylene ethers with aliphatic, aliphatic aromatic, alkylphenol, aromatic phenol, oily, etc. as hydrophobic groups, such as Peregal series, OP series, Tween series, polyol series, ricinoleic acid series, alkyl polyglycosides, etc.

[0134] (6) Among the first three types of polymeric additives, anions, cations, and zwitterions all contain acidic groups, as well as corresponding metal ions and basic groups. The presence of these groups causes the anionic polymeric additives to react with the zinc sulfate metal ions during the reaction between thiadiazole ammonium and zinc sulfate, forming a water-insoluble structure that precipitates. Meanwhile, the basic groups of cationic polymeric additives can react with the acidic groups of thiadiazole, potentially disrupting the formation of zinc thiadiazole. Therefore, generally speaking, anionic, cationic, and zwitterionic polymeric additives are not suitable for use as water-soluble polymeric additives in the present invention.

[0135] (7) The aforementioned water-soluble polymeric additives with dispersing properties are limited to nonionic polymeric additives. The hydrophilic groups of nonionic polymeric additives are mostly random coils formed from polyoxyethylene ethers. These random coils aggregate to form "micelles," with the outer sides of the micelles being hydrophilic and the inner sides being hydrophobic. The generated zinc thiazole nanoparticles enter these micelles, achieving dispersion and stabilization. Furthermore, nonionic polymeric additives also have an emulsifying and dispersing effect, dispersing and stabilizing the diluted tebuconazole latex particles.

[0136] (8) The zinc thiazole / tebuconazole nanoemulsion dispersion is directly formed by the reaction of the precursor ammonium thiazole (or sodium thiazole or potassium thiazole) with a zinc salt during the dilution process before use. During this process, the tebuconazole nanoemulsion particles are not affected and remain stable.

[0137] (9) Testing has shown that the active ingredient particles in the zinc thiazole / tebuconazole nanoemulsion 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 spraying equipment.

[0138] ⑽ In the zinc thiazole / tebuconazole nano-suspension dispersion, zinc thiazole nanoparticles are directly formed during the dilution process with water before spraying. This solution not only eliminates the synthesis and purification process of zinc thiazole from thiadiazoles in the pesticide raw material factory, but also eliminates the multi-step physical processing process of the pesticide formulation factory to process the zinc thiazole raw material and tebuconazole into the existing traditional suspension concentrate. The solution proposed by the present invention can be directly applied to the plant protection link of agricultural production. The process is significantly energy-saving and environmentally friendly, significantly reducing production costs, and the particle size of the obtained zinc thiazole / tebuconazole suspension dispersion is less than 100 nm. Because the particle size is thousands of times smaller than that of existing zinc thiazole / tebuconazole suspension concentrates, the nano-suspension emulsion of the present invention can significantly improve the efficacy of the pesticide, achieving a reduction in pesticide dosage and increased efficiency.

[0139] FIG2 is a flow chart of the present invention for preparing the zinc thiazole / tebuconazole nano-suspension dispersion by diluting with water.

[0140] The key technologies of the present invention lie in the following aspects:

[0141] 1. Synthesis of zinc thiazole and simultaneous formation of zinc thiazole / tebuconazole nanosuspension emulsion

[0142] This invention innovatively proposes a new model and method for preparing nanosuspensions from water- and organic solvent-insoluble pesticides containing polyvalent metal ions, as well as from their combination with water-insoluble pesticides. By utilizing the need for dilution of pesticides with water, the precursor of the target product is mixed with the corresponding metal salt. By leveraging the rapid reaction of metal ions and controlling the mixing and stirring speeds of the reactants, a nanosuspension of zinc thiazole with a particle size of less than 100 nm is obtained, which can be directly used. A nanoemulsion dispersion of tebuconazole is also obtained. This method eliminates both the synthesis and purification steps required by pesticide technical manufacturers to prepare zinc thiazole technical from thiadiazoles, and the multi-step processing required by pesticide formulation manufacturers to convert zinc thiazole technical into the traditional zinc thiazole / tebuconazole suspension concentrate. This innovative research approach, preparation model, and method are the key technologies of this invention. This key technology is applicable not only to zinc thiazole / tebuconazole but also to the preparation of nanosuspensions from similar pesticides and their combined formulations.

[0143] 2. Concentration of zinc thiazole

[0144] The concentration of zinc thiazole in the diluted water can be controlled by controlling the concentration of thiadiazole ammonium in component A and the zinc salt in component B, as well as the amount of dilution water. Specifically, if the dosage of the zinc thiazole active ingredient is fixed (e.g., 10 g / mu), the concentration of zinc thiazole produced by the reaction of thiadiazole ammonium with zinc sulfate is affected by the amount of dilution water. For example, the concentration of thiadiazole ammonium should be controlled within the range of 0.1-0.05 g / kg, and the concentration of zinc sulfate should be controlled within the range of 0.05-0.025 g / kg, corresponding to a water dosage of 10-20 kg. If the water dosage is too low, the resulting particles are large and the transparency of the dilution solution is reduced. This is because the high concentration of particles increases the probability of collisions to form larger particles, which reduces stability and is not conducive to the formation of particles smaller than 100 nm. If the water dosage exceeds 20 kg, while a transparent dilution solution can still be obtained, the concentration of the dispersant in the components is significantly reduced, potentially affecting the stability of the dilution solution. Therefore, controlling the concentration of the final zinc thiazole / tebuconazole, that is, controlling the amount of water used for dilution, is another key technology for obtaining a transparent zinc thiazole / tebuconazole nano-emulsion dispersion of a certain concentration.

[0145] 3. Type and dosage of dispersant

[0146] Selecting the appropriate type and dosage of dispersant is another key technology for obtaining zinc thiazole / tebuconazole nanoemulsion dispersions. However, when ammonium thiazolamide and zinc salts are combined in water to form zinc thiazole particles, the dispersion effect of large amounts of water and stirring alone cannot maintain the size of the newly formed zinc thiazole nanoparticles. This is because the nanoparticles dispersed in water are not static; they are constantly undergoing Brownian motion and colliding with each other. These collisions result in particle fusion, crystallization, and eventual precipitation. An effective method to prevent the size of the formed particles from increasing is to select the appropriate type and dosage of dispersant to uniformly disperse the nanoparticles of the active ingredient in the aqueous solution. These dispersants are soluble in water and exist in the form of random coils and micelles. If the resulting zinc thiazole nanoparticles are smaller than 100 nm, for example, a few nanometers or more than ten nanometers, they can enter the interior of the random coils and micelles. In this case, the random coils and micelles prevent and mitigate collisions between the particles, thereby improving the stability of the zinc thiazole nanoparticles. This is the important role played by polymer dispersants.

[0147] However, there is a problem here. Water-soluble polymers come in different types. Can all water-soluble polymers be used? The present invention has tested a variety of different types of water-soluble polymers and concluded that they are not. Among the numerous anionic surfactants, cationic surfactants, and nonionic surfactants, only nonionic polymer additives can currently achieve the desired effect, such as fatty polyoxyethylene ethers, fatty aryl polyoxyethylene ethers, fatty phenol polyoxyethylene ethers, fatty aryl polyoxypropylene polyoxyethylene ethers, castor oil polyoxyethylene ethers, OP-10, alkyl polyglycosides, etc., and only a few combinations have the best effect. The reason why anionic surfactants cannot be used is that the reaction mechanism of zinc thiazole formed during the dilution process is essentially a process in which polyvalent metal ions replace ammonium ions or sodium ions to form zinc salts or complexes. When anionic surfactants are used, zinc ions will replace the sodium ions of the water-soluble polymer, making it insoluble in water and precipitating the generated zinc thiazole nanoparticles from the water-soluble state, thus playing a flocculating role. However, the present invention does not exclude the special case where an individual cationic surfactant is optimally combined with an appropriate anionic or nonionic surfactant to dissolve in water without precipitation.

[0148] The important role of the water-soluble polymer auxiliary agent used in the present invention is thus apparent. The present invention utilizes a method of mixing water-soluble ammonium thiadiazole, sodium thiadiazole, or potassium thiadiazole with a zinc salt, such as zinc sulfate, that provides zinc ions during a dilution process. During the mixing process, the zinc ions react with the ammonium thiadiazole, sodium thiadiazole, or potassium thiadiazole to generate a zinc thiadiazole suspension dispersion of less than 100 nm. In the system, if no surfactant, particularly no nonionic surfactant, is present, the generated nanocrystals will continuously collide with each other, causing crystal growth and aggregation, until macroscopic precipitation occurs.

[0149] The type and amount of the water-soluble polymer adjuvant used in the present invention can be determined through experiments. The type of water-soluble polymer adjuvant can be determined by conducting stability tests on different adjuvants under fixed conditions and observing the effects. The adjuvant type test includes a single dose of a water-soluble polymer adjuvant or a compounded adjuvant of two or more. The present invention will give examples of different types of water-soluble polymer adjuvants in the test examples. The determination of the amount of the water-soluble polymer adjuvant will be based on meeting the following two conditions: First, the generated zinc thiazole / tebuconazole nanosuspension dispersion must be transparent in appearance and water-soluble in appearance, so as to ensure that the particle size is below 100nm; second, the stability time of this transparent nanosuspension is between 1 and 10 hours, at least between 1 and 5 hours.

[0150] The amount of water-soluble polymer used in this invention is relative to the amount of water used for dilution. The amount of additive used will increase appropriately as the amount of dilution water used increases. The ratio of additive to dilution water should be at least 1:1000, preferably within 1:800.

[0151] 4. Feeding method

[0152] The method of addition is also a key factor influencing the performance of zinc thiazole / tebuconazole nanoemulsion dispersions. Determining the active ingredient content or concentration in the dilution solution effectively determines the water dosage. How is the dilution water distributed? How much is used in Component A and Component B? How is the dilution process performed? These factors all affect the size and stability of the zinc thiazole / tebuconazole particles in the resulting dilution solution. For example, if the water dosage is 100 kg, two issues arise:

[0153] First, how to distribute the amount of water used into the two components to form component A dilution and component B dilution?

[0154] Second, how is it added? Is the component A diluent added to the component B diluent, or vice versa?

[0155] These issues all involve the concentration of reactants at the moment the two components are mixed. Furthermore, the presence or absence of stirring also affects the dispersion of the resulting product. The general principle is that a high concentration of water-soluble polymers in the precursor component is beneficial for the dispersion and stability of the nanoparticles. Stirring should be performed effectively, and after the system has begun to stir and stabilize, the addition method (spraying, dripping, or trickling) should be used to promote uniform dispersion and stability of the resulting nanoparticles.

[0156] Preparation method of zinc thiazole / tebuconazole nano-suspension dispersion

[0157] The present invention adopts the following technical solutions:

[0158] The component A dilution is pre-stirred first, and then the component B dilution is added to the component A dilution at a stirring speed not less than an effective stirring speed to form a zinc thiazole / tebuconazole nano-emulsion dispersion.

[0159] If the addition is done in the opposite way, that is, adding the diluted solution of component A to the diluted solution of component B, precipitation may occur due to the high concentration of zinc salt.

[0160] The component A diluent and the component B diluent are aqueous solutions formed by diluting the following components A and B with water respectively;

[0161] Component A: a water-soluble thiadiazole salt or its aqueous solution, containing a water-soluble polymer auxiliary agent and a tebuconazole nanoemulsion; the water-soluble thiadiazole salt is one of ammonium thiadiazole, sodium thiadiazole, potassium thiadiazole, or a mixture of at least two of the three;

[0162] Component B: solid zinc salt or its aqueous solution, which may or may not contain a water-soluble polymer auxiliary agent.

[0163] The addition method, addition speed and stirring speed are controlled so that nano-crystals of zinc thiazole with a size of less than 100 nm are generated in the suspension, that is, a zinc thiazole / tebuconazole nano-suspension dispersion with a size of less than 100 nm.

[0164] Effective stirring speed

[0165] The so-called effective stirring speed refers to the situation where when component B is added to component A, under a certain adding method and adding speed, the nanopesticide crystals generated in the mixed liquid can be dispersed in time through stirring at a speed not less than the effective stirring speed, and no significant crystal aggregation will occur, thus preventing the size of these crystals from increasing to hundreds of nanometers or micrometers, thereby causing precipitation in the system.

[0166] Stirring method

[0167] 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.

[0168] 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.

[0169] 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.

[0170] Joining method and joining speed

[0171] 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.

[0172] Traditional pesticide formulations sprayed with water as the dispersion medium 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 and B at specific concentrations, addition methods, and speeds in an aqueous solution containing specific polymeric adjuvants, thereby directly producing a transparent, tank-mixed zinc thiazole / tebuconazole nanoemulsion dispersion suitable for on-site spraying.

[0173] Dilution water consumption

[0174] Current experimental data indicates that a reasonable starting point is 10 kg or more, depending on the dosage and concentration of the active ingredients of zinc thiazole and tebuconazole. This dilution volume is strongly correlated with our target stabilization period.

[0175] This is a multivariable problem, and the additives (composition, content) in the components will also affect the stability of the zinc thiazole nanosuspension dispersion.

[0176] The present invention aims to produce a zinc thiazole suspension dispersion with a transparency below 100 nm and a stability period of 1 to 10 hours. When the unit mass of the precursor (e.g., 9 grams of ammonium thiazole) and the metal salt (zinc sulfate) reacting with it are fixed, factors that can affect the nanometer size and stability of the particles include the amount of dilution water, the amount of additives used, and the preparation method.

[0177] The amount of water used for dilution can have an impact on the size of the nano-zinc thiazole crystal grains and the length of the stable period generated. The reason is that the amount of water as a dispersion medium will affect the size of the concentrations of the ammonium thiazole solution and the zinc sulfate solution when they react at the moment of contact, as well as the uniformity of the dispersion, and therefore will also affect the grain size and the effect of the grain dispersion, the aggregation and the growth of the particles. The amount of auxiliary agent used will affect its concentration in different water consumptions, as well as the size and the length of the stable period of the dispersion, suspension and stabilization of the nano-crystals generated. Too little water consumption will produce a limit. For example, when the dilution water consumption is 10 kilograms (if the zinc thiazole / tebuconazole consumption is 10 / 3.5 grams / mu), the concentration of the zinc thiazole generated is 1 gram / kilogram, and the concentration of tebuconazole is 0.35 grams / kilogram. If the zinc thiazole / tebuconazole nano-suspension dispersion is unstable, it is necessary to increase the amount of water for dilution.

[0178]

Brief description of the attached drawings

[0179] Figure 1: Flowchart for preparing zinc thiazole / tebuconazole nanoemulsion dispersion

[0180] [Implementation Method]

[0181] The method of the present invention for preparing a transparent zinc thiazole / tebuconazole nano-suspension dispersion of less than 100 nm in size comprises the following steps:

[0182] In the first step, component A and component B are diluted separately according to different water amounts and different dilution ratios to form component A dilution liquid and component B dilution liquid.

[0183] In the second step, under mechanical stirring (preferably) or manual stirring conditions, the stirring speed is not less than the effective stirring speed, and the component B dilution is evenly added to the component A dilution according to a certain addition method (continuous or intermittent pouring, dropwise addition, spraying, etc.).

[0184] Here are some examples:

[0185] Example 1.

[0186] A zinc thiazole / tebuconazole nanoemulsion dispersion can be used to control rice sheath blight. The dosage of the active ingredient in conventional suspension concentrates ranges from 18.6 to 21.7 grams per mu (approximately 1.8 to 2.1 acre). Considering the high efficacy of the nanopesticide, the dosage in this example is 12.4 grams per mu (approximately 1.2 to 0.4 acre). The dilution water used is 10 kilograms (approximately 100 kg), resulting in a zinc thiazole / tebuconazole nanoemulsion dispersion with a concentration of 1.2 to 0.4 grams per liter (approximately 1.2 to 0.4 acre).

[0187] The dosage of each component, the amount of dilution water and its distribution, and the preparation of the solution are listed in the following table:

[0188] How to do it:

[0189] ⑴ In an appropriate container, add water in a distribution ratio of 4 / 5 (8 kg), add component A, stir and dissolve to obtain a transparent diluted aqueous solution of component A.

[0190] ⑵In another container, add water in a distribution ratio of 1 / 5 (2 kg), add component B, stir and dissolve to obtain a transparent diluted aqueous solution of component B.

[0191] ⑶ Under pre-stirring, add the diluted 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.

[0192] A transparent zinc thiazole / tebuconazole nanosuspension dispersion was obtained, which can be directly used for spraying rice. The stability time of the zinc thiazole / tebuconazole nanosuspension dispersion was observed. The stability time was 4 hours.

[0193] Example 2.

[0194] A zinc thiazole / tebuconazole nanoemulsion dispersion can be used to control bacterial puncture of peach trees. When the dilution water consumption is 200 kg, the dosage of the active ingredient in a conventional zinc thiazole / tebuconazole suspension concentrate is approximately 50 / 15 to 75 / 25 g / mu. The dosage used in this embodiment is 50 / 15 g / mu. The resulting zinc thiazole / tebuconazole nanoemulsion dispersion has a concentration of 0.25 / 0.075 g / L.

[0195] The dosage of each component, the amount of dilution water and its distribution, and the preparation of the solution are listed in the following table:

[0196] How to do it:

[0197] (1) In an appropriate container, add water in a distribution ratio of 9 / 10 (180 kg), add component A, stir and dissolve to obtain a transparent diluted aqueous solution of component A.

[0198] ⑵ Add component C to the diluted aqueous solution of component A, stir and disperse to obtain a transparent "component A + component C" mixed dilution solution.

[0199] ⑶ In another container, add water in a distribution ratio of 1 / 10 (20 kg), add component B, stir and dissolve to obtain a transparent diluted aqueous solution of component B.

[0200] (4) While pre-stirring, add the diluted solution of component B to the diluted solution of "component A + component C" by continuous spraying. Control the addition speed and stirring speed to keep the system transparent until the addition of component B is complete.

[0201] A transparent zinc thiazole / tebuconazole nanosuspension dispersion was obtained, which can be directly used for spraying peach trees. The stability time of the zinc thiazole / tebuconazole nanosuspension dispersion was observed. The stability time was 5 hours.

Claims

1. A zinc thiazole / tebuconazole nano-suspension dispersion, characterized in that: The zinc thiazole / tebuconazole nano-suspension dispersion refers to a zinc thiazole / tebuconazole nano-suspension dispersion of less than 100 nanometers; the zinc thiazole / tebuconazole nano-suspension dispersion of less than 100 nanometers is formed by diluting and mixing two components with water: Component A: a water-soluble thiadiazole salt aqueous solution, comprising a water-soluble polymer auxiliary agent and a tebuconazole nanoemulsion; the water-soluble thiadiazole salt is one of ammonium thiadiazole, sodium thiadiazole, potassium thiadiazole, or a mixture of at least two of the three; Component B: zinc salt or aqueous solution of zinc salt.

2. The zinc thiazole / tebuconazole nano-emulsion dispersion according to claim 1, characterized in that: The zinc thiazole / tebuconazole nano-suspension dispersion liquid with a size below 100 nanometers has a stable period of hours.

3. The zinc thiazole / tebuconazole nano-emulsion dispersion according to claim 1, characterized in that: The component B is added with a water-soluble polymer auxiliary agent to form an aqueous solution; the water-soluble polymer auxiliary agent is a non-ionic surfactant.

4. The zinc thiazole / tebuconazole 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; Preferably, it is not greater than 1:

800.

5. The zinc thiazole / tebuconazole nano-emulsion dispersion according to claim 4, characterized in that: The nonionic surfactant is at least one of the following options: Water-soluble starch and its derivatives, water-soluble cellulose and its derivatives, water-soluble guar gum and its derivatives, water-soluble chitosan and its derivatives, polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, aliphatic polyoxyethylene ether, aliphatic aryl polyoxyethylene ether, aliphatic phenol polyoxyethylene ether, aliphatic aryl polyoxypropylene polyoxyethylene ether, castor oil polyoxyethylene ether, alkyl polyglycoside; Preferred are polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymers, aliphatic polyoxyethylene ethers, aliphatic aryl polyoxyethylene ethers, aliphatic phenolic polyoxyethylene ethers, aliphatic aryl polyoxypropylene polyoxyethylene ethers, castor oil polyoxyethylene ethers, and alkyl polyglycosides.

6. The zinc thiazole / tebuconazole nano-emulsion dispersion according to any one of claims 1 to 5, characterized in that: The zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.

7. The zinc thiazole / tebuconazole nano-emulsion dispersion according to claim 6, characterized in that: When the thiadiazole salt and zinc salt are ammonium thiadiazole and zinc sulfate, respectively, and the mass of the generated thiadiazole zinc is 100, the range of their mass ratio is: Thiadiazole ammonium: zinc sulfate = 90: 45-55 Preferably, thiadiazole ammonium: zinc sulfate = 90: 47-53 Furthermore, thiadiazole ammonium: zinc sulfate = 90: 48-50.

8. A zinc thiazole / tebuconazole nano-suspension dispersion, characterized in that: The zinc thiazole / tebuconazole nano-suspension dispersion refers to a zinc thiazole / tebuconazole nano-suspension dispersion of less than 100 nanometers; the zinc thiazole / tebuconazole nano-suspension dispersion of less than 100 nanometers is formed by diluting and mixing three components with water: Component A: composed of solid or aqueous solution of ammonium thiadiazole, sodium thiadiazole or potassium thiadiazole; Component B: zinc salt solid or its aqueous solution; Component C: Tebuconazole nanoemulsion; it contains a water-soluble polymer auxiliary agent that plays an emulsifying role.

9. The zinc thiazole / tebuconazole nano-suspension dispersion according to claim 8, characterized in that: The ratio of the amount of the water-soluble surfactant to the amount of dilution water is not greater than 1:

800.

10. The zinc thiazole / tebuconazole nano-emulsion dispersion according to claim 8, characterized in that: The zinc thiazole / tebuconazole nano-suspension dispersion liquid with a size below 100 nanometers has a stable period of hours.

11. The zinc thiazole / tebuconazole nano-suspension dispersion according to claim 8, characterized in that: The zinc salt is selected from at least one of zinc sulfate, zinc acetate, zinc chloride and zinc nitrate.

12. The zinc thiazole / tebuconazole nano-emulsion dispersion according to claim 8, characterized in that: The water-soluble surfactant is selected from nonionic surfactants.

13. The zinc thiazole / tebuconazole nano-emulsion dispersion according to claim 12, characterized in that: The nonionic surfactant is selected from: Triblock copolymers of polyoxyethylene and polyoxypropylene, aliphatic polyoxyethylene ethers, aliphatic aryl polyoxyethylene ethers, aliphatic phenolic polyoxyethylene ethers, aliphatic aryl polyoxypropylene polyoxyethylene ethers, vegetable oil polyoxyethylene ethers, alkyl polysaccharides; and can also be selected from natural products and their derivatives such as water-soluble starch, water-soluble cellulose, water-soluble chitosan, and water-soluble guar gum nonionic derivatives.

14. A method for preparing a zinc thiazole / tebuconazole nano-emulsion dispersion; the component A dilution is pre-stirred, and then the component B dilution is added to the component A dilution under the condition that the stirring speed is not less than the effective stirring speed to form the zinc thiazole / tebuconazole nano-emulsion dispersion; The component A diluent and the component B diluent are aqueous solutions formed by diluting component A and component B with water respectively; Component A: a water-soluble thiadiazole salt or its aqueous solution, containing a water-soluble polymer auxiliary agent and a tebuconazole nanoemulsion; the water-soluble thiadiazole salt is one of ammonium thiadiazole, sodium thiadiazole and potassium thiadiazole, or a mixture of at least two of the three; Component B: is a zinc salt solid or its aqueous solution, and the aqueous solution may or may not contain a water-soluble polymer auxiliary agent.

15. The preparation method according to claim 14, 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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