A macrolide pesticide control effect improving organosilicon tank-mixing adjuvant

Abstract

The application discloses a kind of organic silicon tank-mixing adjuvant for improving macrolide pesticide control effect, by selecting specific drug and formula, it has the advantages such as strong wetting penetration, tank-mixing compatibility is good, high and low temperature stability is excellent, preparation process is simple, can significantly improve the control effect of insecticide on rice two-banded chaetodon, reduce pesticide usage, meet the demand of pesticide reduction and green agriculture development.

Description

Technical Field

[0001] This invention belongs to the field of pesticide adjuvant technology, specifically relating to an organosilicon barrel-mixed synergistic adjuvant, its preparation method, and its application in the control of rice pests. Background Technology

[0002] Tank-mixed organosilicon adjuvants are key supporting products for achieving reduced pesticide use and increased efficiency in the chemical control of pests and diseases in field crops such as rice. Abamectin, a typical macrolide insecticide, is widely used to control the rice stem borer. However, rice leaves and leaf sheaths are rich in wax, and when the stem borer larvae bore into the rice stems to feed, conventional abamectin solutions are blocked by the hydrophobic barrier of the wax, causing droplets to easily roll off the leaf surface and making it difficult for the pesticide to penetrate the insect's epidermis and crop tissue. This results in practical production problems such as insufficient wetting and spreading, slow systemic penetration, and low efficacy against older larvae. In actual field formulation, abamectin is often processed into various formulations such as emulsifiable concentrates, microemulsions, and suspensions. Different formulations have significant differences in solvent systems and ion content, making tank-mixing with conventional adjuvants difficult.

[0003] Currently, the mainstream performance-enhancing products on the market are mainly single polyether-modified trisiloxane organosilicon additives, which have long suffered from four common shortcomings in practical applications: 1. Limited penetration and efficacy enhancement, with a significant shortcoming in the control of older rice stem borers. Conventional single-component organosilicon relies solely on surface activity to reduce the surface tension of the pesticide solution for spreading. Lacking synergistic effects of cuticle penetration aids and oily penetration enhancers, it can only improve the spread of the pesticide solution on the crop surface, making it difficult to penetrate the thick waxy layer of rice and the body wall of the rice stem borer. The pesticide cannot reach the target site of the stem borer holes, generally showing acceptable efficacy for young larvae, but poor control effect for 3rd to 4th instar borer larvae, resulting in low pesticide utilization.

[0004] 2. Poor formulation compatibility, prone to stratification and flocculation during tank mixing. Commercially available general-purpose organosilicon adjuvants have a single emulsion system and weak resistance to hard water and electrolytes. When mixed with high-ionic formulations such as abamectin suspension, they are easily affected by the pH of the system, inorganic salts, and oily solvents, resulting in flocculation, stratification, oil separation, and precipitation. This not only significantly weakens the synergistic effect of the adjuvants but also easily clogs the spray nozzles, restricting the mixing of multiple pesticide formulations.

[0005] 3. Insufficient temperature stability limits storage, transportation, and cross-regional use. Ordinary organosilicon trisiloxane structures are prone to precipitating siloxane monomers at low temperatures, causing turbidity and stratification of the system. Long-term storage at high temperatures can easily lead to hydrolysis and chain breakage of silane-ether bonds, resulting in a rapid decline in surface activity and permeability. Furthermore, the large temperature differences between northern and southern China and the varying storage environments mean that existing products lack adequate low-temperature antifreeze and high-temperature hydrolysis resistance, resulting in short shelf lives and difficulty in ensuring stability during cross-seasonal and cross-regional storage and transportation.

[0006] 4. The components have a single function, making it difficult to achieve multi-dimensional synergistic effects. Most existing adjuvant formulations only focus on spreading and reducing surface tension, lacking composite functional components that promote penetration, aid solubility, stabilize liquid, and resist evaporation. They cannot take into account the multiple functions of leaf retention, cuticle penetration, and delaying water evaporation. After application, the liquid evaporates too quickly, resulting in insufficient retention of effective agents and further shortening the duration of effect.

[0007] In summary, existing organosilicon adjuvants cannot meet the field application requirements of abamectin for controlling rice stem borers. The industry urgently needs a composite organosilicon adjuvant that combines strong penetration, broad-spectrum compatibility in tank mixing, and stability at high and low temperatures to help reduce the amount and improve the quality of macrolide pesticides, which is in line with the policy guidance of green agriculture and pesticide reduction. Summary of the Invention

[0008] To achieve the above objectives, the technical content disclosed in this invention is as follows: An organosilicon adjuvant for improving the control efficacy of macrolide pesticides is made from the following raw materials in weight percentages: 20%–35% polyether-modified heptamethyltrisiloxane, 1%–10% lauryl azone, 1.0–5% hydrogenated palm oil fatty acid monoethanolamide, 10%–20% methylated soybean oil, 1%–10% fatty alcohol polyoxyethylene ether AEO-9, 1%–10% alkyl glycoside APG0810, 1%–8% propylene glycol, 1%–8% ethylene glycol, 0.05%–0.5% xanthan gum aqueous solution, 1–2% citric acid, and deionized water to 100%.

[0009] Preferably, the total amount of the mixture of polyether-modified heptamethyltrisiloxane, lauryl azone and hydrogenated palm oil fatty acid monoethanolamide is in a mass ratio of 7:3 to methylated soybean oil.

[0010] Preferably, the concentration of the xanthan gum aqueous solution is 0.5%.

[0011] This invention also provides a method for preparing an organosilicon synergist that is resistant to high and low temperatures, has strong wetting and penetrating properties, and is compatible with tank mixing. The specific steps are as follows: S1. At room temperature, polyether-modified heptamethyltrisiloxane, lauryl ketone, hydrogenated palm oil fatty acid monoethanolamide, and methylated soybean oil are added to the reaction vessel in sequence and stirred until uniform and transparent; S2. Add AEO-9 and APG0810, and continue stirring until completely mixed; S3. Add ethylene glycol, propylene glycol, and xanthan gum aqueous solution, and stir until well mixed; S4. Add deionized water, adjust the pH of the system to 6.5-7.0 with citric acid, and stir until the system is homogeneous and transparent.

[0012] This invention also provides a method for using an organosilicon synergist: the specific steps are as follows: I. Barrel Mixing Process (1) Add 2 / 3 of the rated water volume to the medicine mixing tank and stir; (2) Add all macrolide pesticide formulations and stir for 3 minutes until the pesticide is fully dispersed; (3) Add the additives in two parts: First, add 60% of the total amount of additives and stir for 2 minutes; then add the remaining 40% of the additives slowly after diluting with 5 times the amount of water and continue stirring for 3 minutes. (4) Add the remaining water, mix well, and then spray. Adding materials in stages avoids localized agglomeration of high-concentration additives and solves the potential problem of flocculation in high-electrolyte suspensions, making it an exclusive usage method suitable for this formula.

[0013] Preferably, the standard dosage of organosilicon synergist added during application is 0.025% to 0.04% of the total mass of the spray solution, and the standard dosage for 30 kg of standard spray solution (water consumption per acre) is 7.5 to 12 mL. 1. Control of rice stem borer: For older borer larvae (3rd-4th instar), apply a fixed amount of 8 mL per acre; reduce the dosage to 6 mL per acre for younger larvae; spray the solution directly onto the rice leaf sheaths and stem base. Utilizing the product's strong penetrability, the pesticide penetrates the leaf sheath gaps to reach the pest's habitat.

[0014] 2. Crops with thick waxy cuticles (citrus, cabbage): Due to the thick cuticle of leaves, the maximum dosage is 12 mL / acre; 3. Young leafy crops (leafy vegetables, seedlings): The cuticle is thin, so the lower limit is 7.5 mL / acre to avoid the pesticide solution penetrating too quickly and causing hidden phytotoxicity.

[0015] Preferably, this invention strictly prohibits immediate mixing with strongly alkaline pesticides with pH > 9. If it is necessary to mix with strongly alkaline agents such as lime sulfur, they must be applied separately with an interval of 3 days between applications. Preferably, the prepared medicine solution of the present invention should be stored at room temperature for ≤24 hours and should not be left to stand overnight for a long period of time; Preferably, when preparing medicine in a low-temperature and cold environment, the stirring time can be extended by 1 to 2 minutes to improve the dispersion efficiency.

[0016] By adopting the above technical solution, the present invention has the following beneficial effects: 1. Significantly improved wetting and penetration properties, with a prominent synergistic effect. This invention utilizes a synergistic ternary compound of polyether-modified heptamethyltrisiloxane, lauryl acetone, and methylated soybean oil to achieve a surface tension as low as 24 mN / m at a 0.1% dilution concentration. The average wetting and penetration time on standard canvas is only 20.9 s, representing a penetration rate increase of over 55% compared to conventional organosilicon adjuvants. This rapidly reduces the surface tension of the pesticide solution, enhances its spreading ability, and promotes penetration of the plant wax layer and the insect body wall, significantly improving pesticide absorption and utilization. It also demonstrates a marked improvement in control efficacy against rice stem borer (especially older larvae).

[0017] 2. Excellent compatibility with mixed containers, and wider range of applications. This invention employs a green non-ionic compound emulsification system of AEO-9 and APG 0810, which is reasonably compatible and has high ion resistance. When mixed with various pesticide formulations such as abamectin emulsifiable concentrate, microemulsion, and suspension, it shows no flocculation, precipitation, stratification, or demulsification within 24 hours. It has stable and reliable compatibility, can meet the needs of mixing various pesticides in the field, is not prone to clogging nozzles, and has high safety in use.

[0018] 3. Stable at high and low temperatures, with a longer shelf life. This invention employs a binary antifreeze system of propylene glycol and ethylene glycol, combined with a trace amount of xanthan gum for thickening and stabilization. This ensures that the additive remains clear and does not separate after 72 hours of refrigeration at 0°C, and does not decompose or deteriorate after 14 days of heat storage at 54°C, maintaining a homogeneous and stable system. This effectively solves the problems of traditional organosilicon additives, such as easy separation at low temperatures and easy hydrolysis and failure at high temperatures, significantly extending the product's shelf life and adaptability to cross-seasonal use, meeting the requirements of industrial production, storage, transportation, and long-term storage.

[0019] 4. The preparation process is simple and environmentally friendly, making it suitable for industrial production. This additive is prepared entirely at room temperature through stirring, requiring no heating, high-speed shearing, or complex pH adjustments. The process is simple, energy-efficient, requires minimal equipment, and exhibits high batch stability. All raw materials used are green and environmentally friendly additives, free of prohibited ingredients, making it environmentally friendly, with controllable production costs. It can be mass-produced industrially and possesses strong practicality and promotional value. Detailed Implementation

[0020] The present invention will be further described below with reference to embodiments, but the present invention is not limited thereto.

[0021] All reagents used in the following embodiments of the present invention can be obtained commercially available or prepared in-house. The following formulations are all prepared according to the preparation method described in the invention.

[0022] Example 1 Polyether-modified heptamethyltrisiloxane 24%, Laurozone 4%, Hydrogenated palm oil fatty acid monoethanolamide 3.5%, 13.5% methylated soybean oil Fatty alcohol polyoxyethylene ether AEO-9 8%, Alkyl glycoside APG0810 5%, Propylene glycol 3.5%, Ethylene glycol 3.5%, xanthan gum aqueous solution 2%, 1% citric acid Add deionized water to bring the total to 100%.

[0023] Preparation steps: S1. At room temperature, polyether-modified heptamethyltrisiloxane, lauryl ketone, hydrogenated palm oil fatty acid monoethanolamide, and methylated soybean oil are added to the reaction vessel in sequence and stirred until uniform and transparent; S2. Add AEO-9 and APG0810, and continue stirring until completely mixed; S3. Add ethylene glycol, propylene glycol, and xanthan gum aqueous solution, and stir until well mixed; S4. Add deionized water, adjust the pH of the system to 6.5-7.0 with citric acid, and stir until the system is homogeneous and transparent.

[0024] Example 2 Polyether-modified heptamethyltrisiloxane 33%, Laurozone 6%, Hydrogenated palm oil fatty acid monoethanolamide 3.0%, 18% methylated soybean oil AEO-9 9%, APG0810 5% Propylene glycol 4.0%, Ethylene glycol 4.0%, Xanthan gum aqueous solution 2.2%, 1% citric acid Add deionized water to bring the total to 100%.

[0025] The preparation method is the same as in Example 1.

[0026] Example 3 Polyether-modified heptamethyltrisiloxane 22%, Laurozone 4.0%, Hydrogenated palm oil fatty acid monoethanolamide 2.0%, 12% methylated soybean oil AEO-9 7%, APG0810 4.67% Propylene glycol 3.0%, Ethylene glycol 3.0%, Xanthan gum aqueous solution 1.8%, 1% citric acid Add deionized water to bring the total to 100%.

[0027] The preparation method is the same as in Example 1.

[0028] Comparative Example 1 Polyether-modified heptamethyltrisiloxane 31.5%, 13.5% methylated soybean oil Fatty alcohol polyoxyethylene ether AEO-9 8%, Alkyl glycoside APG0810 5%, Propylene glycol 3.5%, Ethylene glycol 3.5%, xanthan gum aqueous solution 2%, 1% citric acid Add deionized water to bring the total to 100%.

[0029] Comparative Example 2 Remove the methylated soybean oil, add deionized water to the remaining amount, and use the same raw materials and amounts as in Example 1.

[0030] Comparative Example 3 Polyether-modified heptamethyltrisiloxane + lauryl azone + hydrogenated palm oil fatty acid monoethanolamide, in a mass ratio of 1:1:1, totaling 31.5%. 13.5% methylated soybean oil Fatty alcohol polyoxyethylene ether AEO-9 8%, Alkyl glycoside APG0810 5%, Propylene glycol 3.5%, Ethylene glycol 3.5%, xanthan gum aqueous solution 2%, 1% citric acid Add deionized water to bring the total to 100%.

[0031] Comparative Example 4 Ethylene glycol was completely replaced with propylene glycol, and the remaining raw materials and amounts were the same as in Example 1.

[0032] Comparative Example 5 Remove APG0810 and add it to AEO-9. The remaining raw materials and amounts are the same as in Example 1.

[0033] Comparative Example 6 The formula ingredients and addition amounts are the same as in Example 1; the ingredients are added using a one-time addition method during drum mixing.

[0034] Application Example 1 The main performance indicators of the three embodiments and six comparative examples prepared by this invention were tested. The specific testing methods for the formulation design targets are as follows, and the results are shown in Table 1: Thermal storage stability test: This means that the sample is placed in an environment of (54±2)℃ for 14 days. The passing standard for the thermal storage stability test is that the sample should not be separated into layers and should be transparent.

[0035] Low temperature stability test: This means that the sample is placed in an environment of (0±2)℃ for 7 days. The passing standard for the low temperature stability test is that there should be no crystallization and the sample should be transparent.

[0036] Surface tension: The surface tension of the barrel-mixed spray additive to be tested was measured using a surface tension meter. After diluting it by different ratios, the surface tension of the additive at different dilution ratios was measured using the ring method.

[0037] Permeability: Using national standard pure cotton canvas sheets, prepare 0.1% mass concentration aqueous solutions of each test additive. Place the canvas sheet flat on the liquid surface and record the time for the canvas to be completely soaked and settled. Each group is tested in parallel 3 times and the average value is taken.

[0038] Barrel-mixed compatibility and stability: 5% abamectin emulsifiable concentrate, 1.8% abamectin microemulsion, 10% abamectin suspension concentrate, and each of the synergistic adjuvants prepared in this invention were diluted with 5 times the amount of hard water to prepare a barrel-mixed solution; the barrel-mixed solution was placed in a 100ml stoppered graduated cylinder with a pointed bottom and allowed to stand for 1 hour to observe whether there was any precipitate: those without precipitate were considered qualified, otherwise they were unqualified.

[0039] The embodiments of this invention with limited proportions exhibit excellent physicochemical properties: surface tension of 24.0–24.7 mN / m, canvas penetration time of 20.6–21.8 s, and the system remains transparent, stable, and free from layering and crystallization after 14 days of heat storage at 54°C and 72 hours of low temperature storage at 0°C. It can be mixed with various types of pesticide containers for long-term stability, and the compounding of the formulation components produces a synergistic effect. Comparative Example 1 lacked both lauryl azone and hydrogenated palm oil fatty acid monoethanolamide, resulting in the absence of the penetration-enhancing system. This led to a significant increase in surface tension and a substantial extension of penetration time, while the storage stability of the adjuvant itself remained unaffected. Comparative Example 2 lacked methyl ester soybean oil, resulting in a lack of solubilizing and stabilizing system components. This led to poorer cold and hot storage stability, and a slight decrease in surface tension and penetration. Comparative Example 3 altered the ratio of the three key active ingredients, disrupting the synergistic balance. This resulted in stratification at low temperatures and failure of flocculation in tank mixing. Comparative Example 4 used only propylene glycol without ethylene glycol formulation. This resulted in increased viscosity and decreased transparency in the system during long-term high-temperature storage, while maintaining normal performance at low temperatures. Comparative Example 5 eliminated the APG0810 compound emulsification system and used only AEO-9, which was insufficient for electrolyte resistance, leading to easy flocculation in tank mixing. Comparative Example 6 maintained the same formulation composition, but changed the tank mixing feeding process to a one-time addition. The physicochemical properties of the adjuvant itself remained unchanged, but trace amounts of flocculation appeared in the later stages of tank mixing.

[0040] Table 1. Key Performance Indicators Test

[0041] Application Example 2 Efficacy test of organosilicon barrel-mixed synergistic adjuvant: Experiment location: Rice-producing areas in the middle and lower reaches of the Yangtze River; Experimental subjects: Mixed larvae of rice stem borer (both young and old instars); Crop: Single-season medium-season rice; Application period: From the peak hatching period of rice stem borer eggs to the peak occurrence period of 2nd to 4th instar larvae.

[0042] Test reagents: Example 1, commercially available common organosilicon additive (Jiexiaoli), and control without additives (only an equal amount of water was added for preparation, without any synergistic additives).

[0043] Experimental treatments: 100 mL of 5% abamectin EC per acre was applied, and 8 mL of the corresponding adjuvant was added per acre to each adjuvant treatment group. The solution was diluted with 30 kg of water and sprayed evenly, focusing on the base of the rice stems and the inner side of the leaf sheaths. The blank control group was sprayed with only an equal amount of water. Each treatment was replicated three times in a randomized block design. The insect population reduction rate and control efficacy were investigated at 7 and 10 days after application.

[0044] The organosilicon barrel-mixing synergist of this invention is compatible with 5% abamectin emulsifiable concentrate barrel mixing, significantly improving the control efficacy of abamectin against rice stem borer, especially for older larvae.

[0045] Table 2 Results of field efficacy trials

[0046] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. Furthermore, various different embodiments of the present invention can also be arbitrarily combined, as long as they do not violate the spirit of the present invention, and should also be regarded as the content disclosed by the present invention.

Claims

1. An organosilicon tank-mixing adjuvant for improving the control efficacy of macrocyclic lactone pesticides, characterized in that, It is made from the following raw materials in weight percentages: 20%–35% polyether-modified heptamethyltrisiloxane, 1%–10% lauryl azone, 1.0–5% hydrogenated palm oil fatty acid monoethanolamide, 10%–20% methylated soybean oil, 1%–10% fatty alcohol polyoxyethylene ether AEO-9, 1%–10% alkyl glycoside APG0810, 1%–8% propylene glycol, 1%–8% ethylene glycol, 0.05%–0.5% xanthan gum aqueous solution, 1–2% citric acid, and deionized water to 100%. The total mass ratio of the mixture of polyether-modified heptamethyltrisiloxane, lauryl azone and hydrogenated palm oil fatty acid monoethanolamide to methylated soybean oil is 7:

3. The concentration of the xanthan gum aqueous solution is 0.5%.

2. The organosilicon tank-mixing adjuvant for improving the control effect of macrocyclic lactone pesticides according to claim 1, characterized in that, Composed of the following components by mass percentage: Polyether-modified heptamethyltrisiloxane 24%, Laurozone 4%, Hydrogenated palm oil fatty acid monoethanolamide 3.5%, 13.5% methylated soybean oil Fatty alcohol polyoxyethylene ether AEO-9 8%, Alkyl glycoside APG0810 5%, Propylene glycol 3.5%, Ethylene glycol 3.5%, xanthan gum aqueous solution 2%, 1% citric acid Add deionized water to bring the total to 100%.

3. The method for preparing an organosilicon adjuvant to improve the control effect of macrolide pesticides according to claim 1, characterized in that, Perform the following steps at room temperature: S1. Add polyether-modified heptamethyltrisiloxane, lauryl azone, hydrogenated palm oil fatty acid monoethanolamide, and methylated soybean oil to the reaction vessel in sequence, and stir until uniform and transparent; S2. Add AEO-9 and APG0810, and continue stirring until completely mixed; S3. Add ethylene glycol, propylene glycol, and xanthan gum aqueous solution, and stir until well mixed; S4. Add deionized water, adjust the pH of the system to 6.5-7.0 with citric acid, and stir until the system is homogeneous and transparent.

4. The organosilicon tank-mixing adjuvant for improving the control effect of macrocyclic lactone pesticides according to claim 1, characterized in that, It also includes a barrel mixing process, the specific steps of which are as follows: (1) Add 2 / 3 of the rated water volume to the medicine mixing tank and stir; (2) Add all macrolide pesticide formulations and stir for 3 minutes until the pesticide is fully dispersed; (3) Add the additives in two parts: First, add 60% of the total amount of additives and stir for 2 minutes; then add the remaining 40% of the additives slowly after diluting with 5 times the amount of water and continue stirring for 3 minutes. (4) Add the remaining water, mix well, and then spray. The amount of the adjuvant added is 0.025% to 0.04% of the total mass of the spray solution.

5. The application process of the organosilicon tank-mixed adjuvant for improving the control effect of macrocyclic lactone pesticides according to claim 4, characterized in that: At a standard water usage of 30 kg / mu, apply 8 mL of adjuvant per mu for the older larval stages of the rice stem borer and 6 mL per mu for the younger larval stages. For crops with thick wax coating, the maximum dosage is 12 mL / mu, and for crops with thin cuticle and tender leaves, the minimum dosage is 7.5 mL / mu. Adjuvants must not be mixed immediately with strong alkaline pesticides with pH > 9, and the prepared solution should be stored at room temperature for no more than 24 hours.

6. The application of an organosilicon adjuvant for improving the control efficacy of macrolide pesticides according to any one of claims 1-5 in the control of rice stem borer, characterized in that, The macrolide pesticide mentioned is abamectin.

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