Ionically catalyzed agrochemical composition, process for its preparation and use

Abstract

The application discloses an ion catalytic type agricultural insecticide and fungicide composition and a preparation method and application thereof, and belongs to the technical field of agricultural chemicals. The composition is composed of the following components in percentage by mass: tetradecyl dimethyl benzyl ammonium chloride 1.8%-2.2%, fatty alcohol polyoxyethylene ether 1.5%-2.0%, propylene glycol 1.0%, zinc chloride 20.0%, the sum of potassium chloride and sodium chloride ≤2.0%, citric acid 1.2%-1.5%, and the balance is deionized water. The composition solves the problems of poor solubility, easy stratification, insufficient stability, and unstable insecticide and fungicide effect of 1427 in the existing formula, and the ion catalytic activity cannot be fully exerted. After electrocatalysis, the composition has excellent insecticide and fungicide effect, and has the advantages of low cost and green environmental protection compared with traditional chemical agents.

Description

Technical Field

[0001] This application belongs to the field of agricultural chemical technology, specifically relating to ion-catalyzed agricultural insecticide and fungicide compositions, their preparation methods, and applications. Background Technology

[0002] Tetradecyl dimethyl benzyl ammonium chloride (trade name 1427, CAS No.: 139-08-2) is a typical quaternary ammonium salt cationic surfactant. Due to its excellent bactericidal, algicidal, and emulsifying properties, it is considered a fungicide with broad application potential in agricultural disease control. This compound can effectively disrupt the cell membrane structure of microorganisms and also possesses good surface activity, thus promising to provide a solution for agricultural fungicides that combines interfacial activity and biocidal function.

[0003] Currently, agricultural fungicide formulations containing tetradecyl dimethyl benzyl ammonium chloride (1427) generally enhance the wetting, spreading, and film-breaking penetration capabilities of the solution on plant target surfaces by increasing the amount of 1427 added, with the dosage often exceeding 3%. To broaden the fungicidal spectrum and improve the integrated pest management effect, existing formulations typically combine 1427 with zinc salt components, hoping to utilize the synergistic fungicidal effect of zinc ions and quaternary ammonium salts. In addition, inorganic salts such as potassium chloride and sodium chloride are often introduced into the formulation as ionic strength regulators or filler additives, and conventional acid-base regulators are used to perform preliminary pH adjustments to meet the general requirements of formulation processing and basic storage.

[0004] However, the existing formulations exhibit several limitations in application, primarily: In high-salt environments, the solubility of 1427 decreases sharply, easily leading to stratification and precipitation. The stability of the formulation deteriorates significantly during low-temperature storage, failing to meet the reliability requirements for long-term storage in agricultural formulations. Increasing the dosage of 1427 to over 3% in pursuit of excellent spreading and film-breaking effects not only exceeds the actual needs of agricultural scenarios and increases usage costs, but the high concentration of quaternary ammonium salt itself becomes a key factor inducing phase separation in the system. Furthermore, existing zinc-containing formulations contain large amounts of non-core salts such as potassium chloride and sodium chloride, resulting in excessively high total salt content in the system. This severely inhibits the dissolution of 1427 and hinders the full catalytic activity of zinc ions, preventing effective synergistic effects between quaternary ammonium salts and zinc ions. Simultaneously, the biological activity and chemical stability of 1427 are highly sensitive to pH, and existing formulations lack precise pH control methods. Excessive or insufficient acidity easily triggers 1427 degradation and activity reduction, leading to fluctuations and poor reproducibility in the insecticidal and fungicidal effects of the formulation.

[0005] The aforementioned defects severely restrict the practical application of 1427 in the field of agricultural fungicide. There is an urgent need in this field to develop an ion-catalyzed agricultural insecticide and fungicide composition that combines high stability, high insecticidal and fungicidal activity, and low cost. Summary of the Invention

[0006] In view of this, the primary objective of this application is to provide an ion-catalyzed pesticide insecticidal and fungicide composition to solve the problems of poor solubility, easy layering, insufficient stability, and inability to fully exert ion catalytic activity and unstable insecticidal and fungicide effects of 1427 in existing formulations.

[0007] To achieve the above objectives, this application adopts the following technical solution: One aspect of this application discloses an ion-catalyzed agricultural insecticide and fungicide composition, which, by weight percentage, comprises the following components: Tetradecyl dimethyl benzyl ammonium chloride 1.8% ~ 2.2%, fatty alcohol polyoxyethylene ether 1.5% ~ 2.0%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride and sodium chloride ≤2.0%, citric acid 1.2% ~ 1.5%, balance deionized water.

[0008] Another aspect of this application discloses the application of the ion-catalyzed agricultural insecticide and fungicide composition described in this application in insecticidal and fungicide applications; This application has at least the following beneficial effects: This application utilizes a compound solubilizing system of AEO-9 and propylene glycol, which exhibits excellent compatibility with tetradecyl dimethyl benzyl ammonium chloride. This significantly improves its solubility under high salt and low temperature conditions, solving the problems of easy layering and precipitation in existing formulations. After a long-term storage test at 20-25°C in the dark for 12 months, the composition disclosed in the examples of this application showed no layering, precipitation, or turbidity throughout the process, demonstrating excellent long-term storage stability.

[0009] In this application, the amount of tetradecyl dimethyl benzyl ammonium chloride is reduced from 3.2% to 1.8% to 2.2%, which significantly reduces the raw material cost while ensuring the spreading and film breaking effect, and avoids the system stratification problem caused by high concentration.

[0010] This application retains the core zinc chloride ion catalytic component, significantly reduces the amount of non-core potassium chloride and sodium chloride, reduces the inhibition of solubility of tetradecyl dimethyl benzyl ammonium chloride by high salt environment, and at the same time, the catalytic effect of zinc ions can significantly improve the insecticidal and bactericidal activity of tetradecyl dimethyl benzyl ammonium chloride, achieving a synergistic effect of 1 + 1>2. This application precisely controls the pH of the system to a slightly acidic environment of 4.5 to 5.5 using citric acid. Under this environment, tetradecyl dimethyl benzyl ammonium chloride exhibits optimal stability, while zinc ions show the highest catalytic activity. This avoids degradation of active components caused by excessive acidity and provides excellent control effects against thin-walled leaf bacteria, superficial fungal diseases, and small piercing-sucking pests with soft skin, thin waxy layers, and tiny size.

[0011] Furthermore, the preparation method of the composition in this application does not require special conditions such as high temperature and high pressure. All steps are carried out at room temperature. The process is simple, energy consumption is low, and it is easy to scale up production, making it suitable for large-scale promotion and application in agricultural scenarios. Attached Figure Description

[0012] Figure 1 Commercially available standardized agricultural liquid-phase bipolar plate electrocatalytic devices were showcased.

[0013] Figure 2 The image shows the insecticidal and fungicidal effects of the composition of this application in the field after electrocatalysis. Detailed Implementation

[0014] The embodiments of this application will be clearly and completely described below. The technical solutions in the embodiments described below are exemplary and only possible technical implementations of this application, not all possible implementations. Those skilled in the art can combine the embodiments of this application to obtain other embodiments without creative effort, and these embodiments are also within the protection scope of this application.

[0015] This application first discloses an ion-catalyzed agricultural insecticide and fungicide composition, with tetradecyl dimethyl benzyl ammonium chloride as the core component. By optimizing the formulation and ratio, a synergistic system is obtained that can efficiently generate active oxygen species with insecticidal and fungicidal activities under electrocatalytic conditions. This composition has long-term storage stability and has a significant killing effect on target pests and pathogens. Compared with traditional chemical agents, it has significant advantages in being green and environmentally friendly.

[0016] In this application, the ion-catalyzed agricultural insecticide and fungicide composition comprises the following components in the following mass percentages: Tetradecyl dimethyl benzyl ammonium chloride 1.8% ~ 2.2%, fatty alcohol polyoxyethylene ether 1.5% ~ 2.0%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride and sodium chloride ≤2.0%, citric acid 1.2% ~ 1.5%, balance deionized water.

[0017] Tetradecyl dimethyl benzyl ammonium chloride (1427, CAS No. 139-08-2) belongs to the quaternary ammonium salt cationic surfactant class. Its molecular structure contains a hydrophilic quaternary ammonium cationic head group and hydrophobic long-chain alkyl and benzyl groups, exhibiting typical amphiphilic properties. In this application, it serves as the core insecticidal and bactericidal active ingredient in the composition. Specifically, the positively charged quaternary ammonium cations electrostatically adsorb onto the negatively charged cell walls and membranes of microorganisms, thereby penetrating the cell membrane, disrupting its semi-permeable barrier, and causing leakage of small molecule metabolites such as potassium ions and nucleotides, ultimately leading to metabolic disorder and cell death. Simultaneously, its hydrophobic long chains can insert into the phospholipid bilayer of the cell membrane, altering membrane fluidity and permeability, further accelerating the bactericidal process. The mass percentage of tetradecyl dimethyl benzyl ammonium chloride is 1.8% to 2.2%. Within this mass percentage range, while ensuring spreading and membrane-breaking effects, it significantly reduces raw material costs and avoids system stratification problems caused by high concentrations. As a specific example, the mass percentage of this component can be any value from 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, or a range between any two values. In some preferred embodiments, the mass percentage of tetradecyl dimethyl benzyl ammonium chloride is 2.0%. It should be understood that in practical applications, the amount of this component added can fluctuate appropriately within the above range depending on the purity of different batches of the active ingredient or the specific application requirements, and this application does not impose excessive restrictions on it.

[0018] Furthermore, this application selects fatty alcohol polyoxyethylene ether and propylene glycol as a solubilizing system. Specifically, the fatty alcohol polyoxyethylene ether is AEO-9. AEO-9 and propylene glycol are combined as solubilizing stabilizers, forming a synergistic solubilizing system. AEO-9, a nonionic surfactant, can form stable mixed micelles with tetradecyl dimethyl benzyl ammonium chloride, effectively weakening the salting-out effect caused by high concentrations of inorganic salts and preventing the active ingredient from precipitating out. Propylene glycol, as a polar polyol co-solvent, can enhance the hydration ability of water molecules, lower the freezing point of the system, and significantly improve the low-temperature stability of the product. This combination is highly compatible with the cationic active ingredients, zinc chloride ion catalytic components, and the weakly acidic environment within the system, and will not reduce insecticidal and fungicidal activity or ion catalytic efficiency. It also has the advantages of good agricultural safety and low raw material cost.

[0019] In this application, the mass percentage of AEO-9 is 1.5% to 2.0%. As a specific example, the mass percentage of this component can be any value from 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, or a range between any two values. In some preferred embodiments, the mass percentage of AEO-9 is 1.8%, at which concentration it can form a stable mixed micelle system with 1.8% to 2.2% tetradecyl dimethyl benzyl ammonium chloride, resulting in better transparency and stability of the composition. Meanwhile, the mass percentage of propylene glycol is preferably 1.0%.

[0020] Furthermore, the composition of this application uses zinc chloride (ZnCl2) as the ion-catalyzing component, with a mass percentage of 20.0%. This significantly reduces the amount of potassium chloride and sodium chloride used, minimizing the inhibition of solubility of tetradecyl dimethyl benzyl ammonium chloride by high-salt environments. Simultaneously, the catalytic effect of zinc ions significantly enhances the insecticidal and bactericidal activity of tetradecyl dimethyl benzyl ammonium chloride. Specifically, zinc chloride completely ionizes into zinc ions (Zn²⁺) in aqueous solution. + ) and chloride ions (Cl - Zinc ions, as transition metal ions, exhibit excellent electrochemical activity. When the composition undergoes electrocatalytic activation treatment during subsequent applications, zinc ions can participate in redox cycles on the electrode surface, mediating the electrochemical conversion of water molecules and dissolved oxygen, and efficiently catalyzing the generation of highly oxidizing reactive oxygen species, such as hydroxyl radicals (·OH) and superoxide anion radicals (O2). - • and hydrogen peroxide (H2O2), etc. These reactive oxygen species are the actual effectors that exert rapid insecticidal and bactericidal effects. They can indiscriminately oxidize and decompose biomolecules such as proteins, nucleic acids, and unsaturated fatty acids in pests and pathogens, causing them to quickly become inactive. Secondly, zinc ions themselves also have excellent antibacterial effects and essential micronutrient functions for plants. While killing pathogens, they can supplement crops with zinc, promoting crop growth. Thirdly, high concentrations of zinc chloride form a weakly acidic environment in aqueous solution (due to Zn²⁺). + Hydrolysis reaction of Zn² + + H2O [Zn(OH)] + + H + Together with the citric acid added to the composition of this application, it maintains the acidic pH range of the system, which is beneficial to the chemical stability of each active component.

[0021] Furthermore, in this application, potassium chloride (KCl) and sodium chloride (NaCl), as alkali metal chloride salts, are controlled to have a total mass percentage of no more than 2.0% in the composition, and their mass ratio is preferably 5:1. Potassium chloride and sodium chloride mainly function to regulate conductivity in this system. During electrocatalytic activation, the aqueous solution needs to have a certain ionic strength to reduce the internal resistance of the solution, allowing current to be efficiently conducted between the electrodes, thereby ensuring the efficiency of the electrocatalytic reaction. The addition of appropriate amounts of potassium chloride and sodium chloride can significantly improve the conductivity of the solution, reduce ohmic polarization during the electrocatalytic process, and enable electrical energy to be more efficiently converted into chemical energy for the generation of reactive oxygen species. Furthermore, potassium ions (KCl... + ) and sodium ions (Na + Both potassium chloride and sodium chloride are inert cations and will not participate in the Faraday reaction on the electrode surface, thus not interfering with the target catalytic process. Furthermore, potassium chloride has high solubility in water and potassium ions have a large hydrated ionic radius, effectively increasing the conductivity of the solution without significantly affecting the diffusion and mass transfer of zinc ions. The addition of a small amount of sodium chloride helps stabilize the conductivity fluctuations of the solution under different temperature conditions. Therefore, in this application, the total mass percentage of both is strictly controlled within the range of ≤2.0%, ensuring sufficient conductivity while avoiding excessive inert salt ions from having an adverse competitive effect on the electrochemical activity of zinc ions and the generation efficiency of reactive oxygen species. As specific examples, the total mass percentage of potassium chloride and sodium chloride can be 0.5%, 1.0%, 1.5%, 2.0%, etc., and in some preferred embodiments, the mass ratio is 5:1. It should be understood that in practical applications, this ratio can be adjusted and optimized according to the specific parameters of the target electrocatalytic device (such as electrode material, electrode spacing, etc.), and this application does not impose any restrictions on this.

[0022] In this application, the mass percentage of citric acid (C6H8O7) is 1.2% to 1.5%, for example, any value among 1.2%, 1.3%, 1.4%, and 1.5%, or a range between these values. The appropriate amount can be selected based on the target pH range. Firstly, citric acid, as an organic acid pH adjuster, can regulate and stabilize the pH of the composition within a weakly acidic range of 4.5 to 5.5. Secondly, the three carboxyl and hydroxyl groups in the citric acid molecule can form stable five- or six-membered ring chelates with zinc ions. This chelation effect inhibits the hydrolysis and polymerization of zinc ions during storage, preventing the formation of zinc hydroxide or basic zinc salt precipitates, significantly improving the long-term storage stability of the composition. Thirdly, the chelated zinc ions retain electrochemical activity under electrocatalytic conditions, effectively reducing or oxidizing them on the electrode surface to participate in the catalytic cycle. Furthermore, citric acid itself is an environmentally friendly organic acid, readily biodegradable in soil, with no residual risk.

[0023] Under the formulation system of this application, the composition exhibits excellent storage stability, remaining clear and transparent without precipitation or stratification for 12 months at room temperature. It also maintains a state free of stratification and precipitation under both low-temperature (-5°C for 7 days) and high-temperature (54°C for 14 days) conditions.

[0024] The second aspect of this application discloses a method for preparing the above-mentioned ion-catalyzed agricultural insecticide and fungicide composition. This method adopts a stepwise mixing and dissolution strategy, and designs a specific order of addition according to the physicochemical properties and solubility characteristics of each component to ensure that a uniform, stable, and transparent solution can be obtained at room temperature. The entire process does not require heating or high-pressure treatment, and the process is simple, energy-efficient, and easy to scale up for industrial production.

[0025] In some specific embodiments, the preparation method mainly includes the following steps: (1) Preparation of premix A - solubilizing and stabilizing premix Under room temperature conditions (i.e., ambient temperature without additional heating, typically 15°C to 30°C, preferably 20°C to 25°C), accurately weigh AEO-9 and propylene glycol according to the aforementioned ratio, and mix them thoroughly until a premixed solution A is formed.

[0026] (2) Preparation of premixed solution B—active component premixed solution While maintaining stirring, add an accurate amount of tetradecyl dimethyl benzyl ammonium chloride to the premix A obtained in step (1). Continue stirring at room temperature until the tetradecyl dimethyl benzyl ammonium chloride is completely dissolved to obtain premix B. The specific stirring time can be determined as needed, based on the complete dissolution of the tetradecyl dimethyl benzyl ammonium chloride.

[0027] (3) Preparation of premixed C-ion catalytic system premix Add accurately weighed zinc chloride, potassium chloride, and sodium chloride sequentially or simultaneously to the premixed solution B obtained in step (2) while continuously stirring. Continue stirring at room temperature until all inorganic salts are completely dissolved to obtain premixed solution C.

[0028] (4) pH adjustment Under continuous stirring, accurately weighed citric acid was slowly added to the premixed solution C obtained in step (3). After the citric acid was added, stirring was continued until homogeneous. The citric acid rapidly ionized in the solution and underwent a complexation reaction with zinc ions, while releasing hydrogen ions to lower the pH value of the system. After the addition was complete, the pH value of the system was measured using a precision pH meter, and fine-tuned by adding appropriate amounts of citric acid or very dilute sodium citrate solution to stabilize the final pH value of the system within the target range of 4.5 to 5.5. This pH range is a key parameter to ensure the long-term stability of the composition and its subsequent electrocatalytic activity. Specifically, within this pH range, the composition maintains good solubility and stability under both low and high temperature conditions, and the degradation degree of tetradecyl dimethyl benzyl ammonium chloride and the catalytic activity of zinc chloride ions both reach excellent levels, exhibiting excellent comprehensive insecticidal and bactericidal effects. If the pH is below 4.5, the system is too acidic, which will accelerate the degradation and deactivation of tetradecyl dimethyl benzyl ammonium chloride, weaken the synergistic effect of zinc ions, and gradually reduce the efficacy. If the pH is above 5.5, the system is too alkaline, and zinc ions are easily converted into zinc hydroxide precipitate, causing the loss of catalytic components, the liquid phase system is destroyed, and problems of stratification and precipitation occur. The higher the pH, the more serious the precipitation phenomenon, and the activity of cationic bactericidal components continues to decrease.

[0029] (5) Volume adjustment and filtration—add solvent and remove mechanical impurities After pH adjustment, add deionized water to the system until the total mass reaches 100%, and continue stirring until the solution is completely homogeneous. Then, filter the resulting solution through a filtration device to remove trace mechanical impurities or insoluble particles that may have been introduced during the preparation process, obtaining a final clear and transparent product. A 200-mesh filter can be used for filtration. The filtered product is the ion-catalyzed agricultural insecticide and fungicide composition described in this application, which can be directly filled into suitable containers and sealed for storage at room temperature.

[0030] The third aspect of this application discloses the application of the aforementioned ion-catalyzed agricultural insecticide and fungicide composition in insecticidal and fungicidal applications. The composition requires electrocatalytic activation treatment before use. Specifically, electrocatalytic activation treatment refers to placing the composition in an electrocatalytic reactor, where, under the action of an applied DC electric field, zinc ions in the composition mediate the generation of reactive oxygen species through an electrochemical reaction at the electrode-solution interface. The composition generates a large number of highly oxidizing species such as hydroxyl radicals, superoxide anion radicals, and hydrogen peroxide. These species possess extremely high reactivity and can indiscriminately oxidize and destroy the cell membranes, proteins, and nucleic acids of target organisms within seconds to minutes, thereby achieving a rapid and efficient killing effect.

[0031] In some specific embodiments, the above-mentioned electrocatalytic activation treatment is carried out using commercially available standardized agricultural liquid-phase bipolar plate electrocatalytic equipment commonly used in the art. Typical examples include, but are not limited to, the Zhongjie Sifang EOW series (EOW-150 laboratory type / EOW-1500 field type) or the Wuhan Luoge Purun PRS-BP series (PRS-BP50 / PRS-BP1000).

[0032] In some specific examples, the preferred electrocatalytic process parameters are: DC voltage 18 ~ 24 V, DC current 2.5 ~ 4.0 A, electrode spacing 8 ~ 12 mm, and activation treatment at room temperature (i.e., without additional heating, typically 15℃ ~ 30℃) for 40 to 90 seconds. The pH of the system is maintained at 4.5 ~ 5.5 throughout the process.

[0033] The composition in this application exhibits significantly enhanced catalytic activity of free zinc ions after electrocatalytic activation. Combined with the epidermal penetration effect of low-concentration tetradecyl dimethyl benzyl ammonium chloride, it achieves significant insecticidal and fungicidal effects. It is particularly effective against small, piercing-sucking pests with soft skin, thin waxy layers, and tiny size, as well as thin-walled bacterial foliar diseases and superficial, high-humidity fungal leaf spot diseases. Typical examples include, but are not limited to: various aphids, phytophagous mites such as red / white spider mites, young nymphs of whiteflies / tobacco whiteflies, thrips nymphs, psyllid nymphs, as well as bacterial angular leaf spot of cucumber, scab of tomato, bacterial shot-hole disease of peach, wildfire disease of tobacco, bacterial leaf blight of vegetables, and powdery mildew, small leaf spot diseases (Cercospora, Stigmocystis), and early-stage gray mold in various crops.

[0034] Because the mechanism of action of this composition is the rapid oxidative damage of target biological cells by reactive oxygen species, it is not easy to develop drug resistance. It can be used as an alternative or supplement to chemically synthesized pesticides in green organic agricultural production, which has significant advantages.

[0035] The present application will be further illustrated below with reference to specific embodiments. It should be noted that the specific embodiments below are for illustrative purposes only and do not limit the scope of the present application in any way.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application.

[0037] In addition, unless otherwise specified, methods without detailed conditions or steps are conventional methods, and the reagents and materials used are commercially available.

[0038] Example 1: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this embodiment consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8%, AEO-9 1.5%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride 1.5%, sodium chloride 0.3%, citric acid 1.2%, balance deionized water.

[0039] The preparation method steps are as follows: (1) At room temperature, AEO-9 (15 g) and propylene glycol (10 g) were mixed and stirred until homogeneous to obtain a premixed solution A of solubilizing stabilizer; (2) Add tetradecyl dimethyl benzyl ammonium chloride (18 g) to premix A, stir for 30 min until completely dissolved, and obtain premix B of active component; (3) Add zinc chloride (200 g), potassium chloride (15 g), and sodium chloride (3 g) to the premixed solution B, stir for 20 min until completely dissolved, and obtain the premixed solution C of the ion catalysis system; (4) Slowly add citric acid (12 g) to premixed solution C, stir evenly, and then finely adjust the pH of the system to 4.5; (5) Add deionized water to a total mass of 1000 g, stir well, and then filter with a 200-mesh filter to obtain the finished product.

[0040] Example 2: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this embodiment consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8%, AEO-9 1.8%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride 1.7%, sodium chloride 0.3%, citric acid 1.35%, balance deionized water.

[0041] The preparation method is the same as in Example 1, except that the pH value of the system is finely adjusted to 5.0 in step (4).

[0042] Example 3: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this embodiment consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 2.2%, AEO-9 2.0%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride 1.8%, sodium chloride 0.2%, citric acid 1.5%, balance deionized water.

[0043] The preparation method is the same as in Example 1, except that the pH value of the system is finely adjusted to 5.5 in step (4).

[0044] Example 4: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this embodiment consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 2.0%, AEO-9 1.8%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride 1.67%, sodium chloride 0.33%, citric acid 1.35%, balance deionized water.

[0045] The preparation method is the same as in Example 1, except that the pH value of the system is finely adjusted to 5.0 in step (4).

[0046] Comparative Example 1: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this comparative example consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 3.2%, zinc chloride 20.0%, potassium chloride 2.5%, sodium chloride 0.5%, citric acid 1.8%, balance deionized water.

[0047] Comparative Example 2: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this comparative example consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8%, AEO-9 1.8%, zinc chloride 20.0%, potassium chloride 1.7%, sodium chloride 0.3%, citric acid 1.35%, balance deionized water.

[0048] Comparative Example 3: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this comparative example consists of the following components by mass percentage: The composition is: tetradecyl dimethyl benzyl ammonium chloride 1.8%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride 1.7%, sodium chloride 0.3%, citric acid 1.35%, with the remainder being deionized water.

[0049] Comparative Example 4: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this comparative example consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8%, Tween-80 1.8%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride 1.7%, sodium chloride 0.3%, citric acid 1.35%, balance deionized water.

[0050] Comparative Example 5: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this comparative example consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8%, AEO-9 1.8%, glycerol 1.0%, zinc chloride 20.0%, potassium chloride 1.7%, sodium chloride 0.3%, citric acid 1.35%, balance deionized water.

[0051] Comparative Example 6: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this comparative example consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8%, LAS 1.8%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride 1.7%, sodium chloride 0.3%, citric acid 1.35%, balance deionized water.

[0052] Comparative Example 7: Ion-catalyzed agricultural insecticide and fungicide composition The ion-catalyzed agricultural insecticide and fungicide composition in this comparative example consists of the following components by mass percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8%, AEO-9 1.8%, ethanol 1.0%, zinc chloride 20.0%, potassium chloride 1.7%, sodium chloride 0.3%, citric acid 1.35%, balance deionized water.

[0053] Performance testing (1) Stability test The compositions of Example 2 and Comparative Examples 1-7 were stored at -5°C for 7 days and at 54°C for 14 days, respectively. The state of the compositions was observed, and the results are shown in Table 1. Table 1. High and low temperature storage stability of different compositions

[0054] As shown in Table 1, without the addition of solubilizing stabilizers, the system exhibits severe stratification and produces a large amount of precipitation under accelerated storage conditions at both -5℃ and 54℃. AEO-9 alone can only slightly improve the high-temperature storage condition, while fine impurities and turbidity still precipitate under low-temperature storage. Propylene glycol alone cannot resist the salting-out effect of the high-salt system, and the stratification and precipitation problems remain prominent under both low-temperature and high-temperature conditions. Replacing propylene glycol with glycerol and AEO-9 with Tween-80 in the AEO-9 and propylene glycol compound system resulted in no obvious stratification during short-term accelerated storage at high and low temperatures, but long-term storage led to increased viscosity and turbidity, simultaneously reducing the insecticidal and fungicidal effects. When using LAS anionic surfactants to compound with propylene glycol, the anions would undergo charge association flocculation with cationic tetradecyl dimethyl benzyl ammonium chloride, directly precipitating large amounts of flocculent precipitate under high and low temperatures, rendering the product completely ineffective. Using ethanol instead of propylene glycol in the compound system resulted in stable appearance during short-term storage at high and low temperatures, but ethanol is volatile, flammable, and explosive, and its application in the field can easily cause crop damage, which does not comply with the regulations for the production, storage, transportation, and use of agricultural formulations.

[0055] The above results demonstrate that the combination of AEO-9 and propylene glycol in this application serves as a solubilizer and stabilizer, with complementary advantages: AEO-9 weakens the salting-out effect of the high-salt system by relying on mixed micelles, while propylene glycol enhances the solvent's hydration ability and improves low-temperature stability. This combination exhibits excellent compatibility with the ion-catalyzing components and bactericidal active components within the system, maintains stable storage across the entire temperature range, and achieves optimal efficacy. Furthermore, it possesses the characteristics of readily available raw materials, suitable viscosity, safe use, and controllable cost, making it the optimal solubilization scheme for this high-salt agricultural composite catalyst.

[0056] (2) Long-term stability test at room temperature Test conditions: Ambient temperature 20 ~ 25℃, indoor storage in a dark, sealed container, and samples were taken at 3 months, 6 months, 9 months and 12 months of storage to observe the appearance and record the layering, sedimentation, turbidity and discoloration.

[0057] Test samples: Example 1, Example 2, Example 3, Comparative Examples 1 to 7.

[0058] Table 2. Results of long-term storage stability observation of each sample at room temperature

[0059] As can be seen from Table 2, Examples 1-3 of this application, which use a compound solubilizing system of AEO-9 and propylene glycol, maintained a clear and transparent liquid state for 12 months under sealed conditions at 20-25°C in the dark, without layering, precipitation, turbidity, or solute precipitation. This demonstrated excellent long-term storage stability and met the 12-month shelf-life requirements for conventional storage of agricultural formulations. Comparative Examples 1-3, which lacked a compound solubilizing system of AEO-9 and / or propylene glycol, exhibited layering, precipitation, and salting-out problems within 6 months of storage at room temperature, failing to meet the storage stability requirements. Furthermore, Comparative Examples 4-7, which replaced AEO-9 and propylene glycol with adjuvants such as Tween-80, glycerol, ethanol, and LAS, showed no obvious layering in the short term, but suffered from increased viscosity, turbidity, solute precipitation, and flocculation failure during long-term storage, failing to meet the 12-month long-term storage requirements.

[0060] (3) Insecticidal and bactericidal effect test Indoor bioactivity assays were used to simulate the actual field application effects. A water-based blank control was also included. Each treatment was repeated three times. The experimental environment was controlled at 25 ± 1℃ and 70% ± 5% relative humidity.

[0061] The test composition stock solution should be prepared and used immediately, and must be subjected to [a specific process] before use. Figure 1 The commercially available standardized agricultural liquid-phase bipolar plate electrocatalytic equipment shown is used for electrocatalytic activation, with a voltage of 20 V, a current of 3.0 A, a plate spacing of 10 mm, and an activation time of 60 s. After electrocatalytic activation, the solution is diluted 500 times with deionized water to prepare the test working solution.

[0062] A. Determination of wheat aphid toxicity (immersion method) Healthy, uniformly sized wingless adult wheat aphids were selected and starved for 2 hours before the experiment. Thirty aphids were selected from each group, and their bodies were completely immersed in the tested pesticide solution for 5 seconds. They were then removed and placed in petri dishes lined with moistened filter paper and containing fresh wheat leaves. After 24 hours of treatment, the number of live and dead aphids was counted. Aphids were considered dead when they showed no activity due to external stimuli. The mortality rate was calculated using the following formula:

[0063] B. Cucumber bacterial angular spot virus infectivity assay (plate punch inhibition zone method) The pathogen of bacterial angular leaf spot in cucumber, *Pseudomonas syringae* pv. *lachrymans* (Smith & Bryan) Young, Dye & Wilkie, was activated by incubation in LB broth at 25°C with shaking for 24 h. The culture was then diluted with sterile water to a concentration of 1×10⁻⁶. 6A bacterial suspension of CFU / mL was prepared. The bacterial suspension was mixed with melted and cooled LB solid medium to prepare bacterial plates. Using a Φ 6 mm sterile punch, equidistant wells were punched on the plates, and 20 μL of the tested drug solution was added to each well. The plates were allowed to stand for 30 min to allow the drug to penetrate. The plates were then inverted and incubated at 25℃ for 72 h. The diameter of the inhibition zone was measured, and the relative control effect of the drug on the pathogen was calculated using the following formula:

[0064] Table 3. Insecticidal and bactericidal effects of different solubilizing and stabilizing agent formulations

[0065] As can be seen from the results in Table 3, the ion-catalyzed agricultural insecticide and fungicide composition of this application has excellent insecticidal and fungicide effects.

[0066] C. Field trials At the Wujiayao Experimental Base in Jungar Banner, field spraying tests were conducted using the composition formulation and electrocatalytic process described in Example 2 above. The test areas were apple orchards (powdery mildew and spider mite control test areas) and wheat fields (aphid control test areas). Before the experiment, the pesticide was electrocatalytically activated (DC voltage 20 V, current 3.0 A, electrode spacing 10 mm, activation at room temperature for 60 s), then diluted 500 times with deionized water to prepare a field spraying solution. A backpack electric high-pressure sprayer with a fan-shaped atomizing nozzle and a nozzle orifice diameter of 0.8 mm was used. Application was conducted on sunny mornings from 9:00 AM to 11:00 AM, with an ambient temperature of 20–28℃, relative humidity of 60%–75%, and no wind or a light breeze (wind speed ≤1.5 m / s), and no rainfall or strong sunlight exposure. 30 L of diluted pesticide solution was sprayed per acre, evenly on both sides of the plant, ensuring the leaves, branches, and fruits were thoroughly moistened until just before dripping. Special attention was paid to the undersides of leaves, tender buds, and crevices where pests and diseases might hide. The first application was made at the initial stage of disease or pest infestation, followed by a repeat application after 7 days, for a total of two applications. The control effects against powdery mildew, spider mites, and aphids were as follows: Figure 2 As shown in the figure, the ion-catalyzed agricultural insecticide and fungicide composition of this application exhibits excellent performance.

[0067] It should be noted that this application is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments with the same structure and effect as the technical concept within the scope of this application are included in the technical scope of this application. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of this application, are also included in the scope of this application.

Claims

1. An ion-catalyzed agricultural insecticide and fungicide composition, characterized in that, It consists of the following components by weight percentage: Tetradecyl dimethyl benzyl ammonium chloride 1.8% ~ 2.2%, fatty alcohol polyoxyethylene ether 1.5% ~ 2.0%, propylene glycol 1.0%, zinc chloride 20.0%, potassium chloride and sodium chloride ≤2.0%, citric acid 1.2% ~ 1.5%, balance deionized water.

2. The ion-catalyzed agricultural insecticide and fungicide composition as described in claim 1, characterized in that, The mass percentage of the tetradecyl dimethyl benzyl ammonium chloride is 2.0%.

3. The ion-catalyzed agricultural insecticide and fungicide composition as described in claim 1, characterized in that, The fatty alcohol polyoxyethylene ether is AEO-9.

4. The ion-catalyzed agricultural insecticide and fungicide composition as described in claim 1, characterized in that, The fatty alcohol polyoxyethylene ether has a mass percentage of 1.8%.

5. The ion-catalyzed agricultural insecticide and fungicide composition as described in claim 1, characterized in that, The mass ratio of potassium chloride to sodium chloride is 5:

1.

6. The ion-catalyzed agricultural insecticide and fungicide composition as described in claim 1, characterized in that, The pH of the composition is between 4.5 and 5.

5.

7. The method for preparing the ion-catalyzed agricultural insecticide and fungicide composition according to any one of claims 1-6, characterized in that, Includes the following steps: At room temperature, fatty alcohol polyoxyethylene ether and propylene glycol are mixed according to the formula and stirred evenly to obtain premix A; Add tetradecyl dimethyl benzyl ammonium chloride to premix A and stir until completely dissolved to obtain premix B; Add zinc chloride, potassium chloride and sodium chloride to premix B, and stir until completely dissolved to obtain premix C; Slowly add citric acid to premixed solution C, stir well, and then fine-tune the pH of the system to 4.5 ~ 5.5; Add deionized water, stir well, and filter to obtain the ion-catalyzed agricultural insecticide and bactericide composition.

8. The preparation method according to claim 7, characterized in that, All steps are performed at room temperature, without the need for high temperature and high pressure.

9. The use of the ion-catalyzed agricultural insecticide and fungicide composition according to any one of claims 1-6 in insecticidal and fungicide applications.

10. The application as described in claim 9, characterized in that, The ion-catalyzed agricultural insecticide and fungicide composition needs to undergo electrocatalytic activation treatment; Optionally, the electrocatalytic process parameters are: DC voltage 18 ~ 24 V, DC current 2.5 ~ 4.0 A, electrode spacing 8 ~ 12 mm, and room temperature activation 40 ~ 90 s.

Images