Mesotrione soluble liquid as well as preparation method and application thereof

Abstract

The invention relates to the technical field of pesticides, in particular to mesotrione soluble liquid as well as a preparation method and application thereof. The mesotrione suspending agent comprises the following components in percentage by mass: 5-40% of mesotrione technical, 5-30% of a solvent, 3-20% of a surfactant, 1-10% of an antifreeze agent, 0.3-3% of a pH regulator and the balance of deionized water. According to the invention, the solubility of mesotrione is improved by selecting proper solvent, antifreezing agent and surfactant and reasonable proportion, so that the soluble liquid with high stability and high drug effect is prepared. The mesotrione soluble liquid can be applied to prevention and removal of weeds in uncultivated land and cultivated land, and does not cause phytotoxicity to crops. The herbicide is an agricultural herbicide which is good in weeding effect, simple in production process and free of environmental pollution.

Description

Technical Field

[0001] This application relates to the field of pesticide technology, and more specifically, to a soluble liquid formulation of nicosulfuron, its preparation method, and its application. Background Technology

[0002] Mesotrione, a triketone herbicide developed by Syngenta, was first registered and marketed in 2001. Its mechanism of action involves inhibiting p-hydroxyphenylpyruvate dioxygenase (HPPD) in weeds, blocking the biosynthesis of plastoquinones and tocopherols, leading to bleaching and death of susceptible weeds. Its broad-spectrum, low-toxicity, and environmentally compatible characteristics make it one of the core herbicides for post-emergence control of broadleaf weeds and some grassy weeds in cornfields. As of 2023, global annual sales of mesotrione exceeded $500 million, accounting for more than 20% of the cornfield herbicide market.

[0003] Currently, the available formulations of mesotrione on the market are suspension concentrates (SC) and water-dispersible granules (WDG). However, their physical stability is insufficient, and they are prone to stratification or clumping during long-term storage. Uneven particle size distribution leads to low leaf deposition efficiency and large fluctuations in efficacy (±15%). Furthermore, the processing is complex, requiring the addition of large amounts of dispersants and wetting agents, resulting in high costs. Secondary dilution is required during application, making the process cumbersome, and the dispersibility decreases at low temperatures. Summary of the Invention

[0004] As pesticide formulations evolve towards higher efficiency and environmental friendliness, soluble liquid formulations, due to their low toxicity and low residue characteristics, have become a key focus for upgrading nicosulfuron formulations. The purpose of this invention is to address the shortcomings of existing technologies and provide a soluble nicosulfuron liquid formulation that effectively controls weeds. By optimizing the solvent ratio and introducing functional adjuvants (such as antifreeze agents and surfactants), the formulation's weather resistance and duration of action can be further improved, meeting the needs of field operations under complex climatic conditions.

[0005] Another objective of this invention is to provide a method for preparing the soluble nicosulfuron liquid and its application in the prevention and control of crop diseases.

[0006] To achieve the above objectives, the technical content disclosed in this invention is as follows: The soluble liquid formulation of nicosulfuron provided by this invention is made from the following raw materials in weight percentage: 5%-40% nicosulfuron technical grade, 5%-30% solvent, 3-20% surfactant, 1-10% antifreeze agent, 0.3-3% pH adjuster, and the balance is made up with deionized water.

[0007] Preferably, the soluble liquid containing nicosulfuron comprises the following components in weight percentage: 10%-25% nicosulfuron technical grade, 20%-30% solvent, 7-15% surfactant, 5-8% antifreeze agent, 0.5-1% pH adjuster, with the remainder being deionized water.

[0008] The solvent is selected from one or more of methylated soybean oil, PEG-400, α-terpineol, glucamide, sorbitol, and deionized water.

[0009] Preferably, the solvent is selected from a combination of deionized water + PEG-400 + glucamide or deionized water + sorbitol.

[0010] The surfactant is selected from polyoxyethylene lauryl ether, castor oil polyoxyethylene ether, octadecyl carboxylate betaine, sodium fatty alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, long-chain carboxylic acid ester polyoxyethylene-18, oleic acid polyoxyethylene ester, oleyl alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene sulfate, polyethylene glycol sulfate, fatty alcohol polyoxyethylene carboxylate, fatty alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ether, polyoxyethylene-polyoxypropylene copolymer, and polyoxyethylene... Alkylphenol ethers, polyoxyethylene castor oil derivatives, polyoxyethylene glycerol esters, cocamidopropyl betaine, sodium dodecylbenzene sulfonate, dodecyl hydroxypropyl sulfobetaine, dodecyl hydroxypropyl sulfobetaine, dodecyl hydroxypropyl sulfobetaine, lauramide propyl hydroxysulfobetaine, decylamide propyl betaine, decylamide propyl betaine, erucamide propyl betaine, erucamide propyl betaine, erucamide propyl betaine, C12-C15 alkyl glycosides, APG-1214, APG-0814, and sodium oleoyl methyl taurate salt, one or more of these.

[0011] Preferably, the surfactant is selected from the following combinations: polyoxyethylene lauryl ether + sodium oleoyl methyl taurate, alkylphenol polyoxyethylene ether + C12-C15 alkyl glycoside, polyoxyethylene fatty acid ether + lauryl alcohol polyoxyethylene ether, castor oil polyoxyethylene ether + C12-C15 alkyl glycoside. The weight ratio of the two selected surfactants is (1~6.5):(1~4.5).

[0012] The antifreeze agent is selected from one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, inorganic salts, polyethylene glycol, sorbitol, and isopropanol.

[0013] The pH adjuster is selected from one or more of sodium hydroxide, ammonia, glacial acetic acid, citric acid, phosphoric acid, sodium citrate, and sodium lactate.

[0014] Preferably, the pH adjuster is selected from citric acid-phosphate and citric acid-sodium citrate.

[0015] Another objective of this invention is to provide a method for preparing the above-mentioned nitrosulfuron-methyl soluble liquid, the steps of which are as follows: S1. Add the prescribed amount of deionized water to the reaction vessel, and slowly add the nicosulfuron technical and solvent under stirring conditions. Control the stirring speed at 200-400 rpm and continue stirring for 10-20 minutes to form a suspension. S2. Add pH adjuster to adjust pH to 6-9, stir to form a transparent solution; then add surfactant and antifreeze in sequence. S3. Heat the solution obtained in S2 to 30-50℃ and stir continuously for 20-40 minutes. Mix thoroughly and let stand for 2 to 5 hours until the system is clear and transparent. After passing quality inspection, it can be bottled.

[0016] The soluble liquid form of nicosulfuron provided by this invention can be used for the control of weeds in cultivated and non-cultivated land, such as broadleaf weeds and grass weeds, such as cocklebur, velvetleaf, spiny amaranth, lambsquarters weeds, knotweed weeds (such as sorrel knotweed and willow-leaf knotweed), black nightshade, purslane, kochia, ragweed, dayflower, barnyard grass, crabgrass, foxtail grass, and arm-shaped grass.

[0017] By adopting the above technical solution, the present invention has the following beneficial effects: 1. This invention achieves complete water solubility of nicosulfuron, with no particulate residue and good stability; 2. The adjuvant system of the present invention can improve the wettability and permeability of the drug solution; 3. No grinding or granulation is required, reducing energy consumption and production costs.

[0018] 4. This invention contains no organic solvents and is environmentally and crop-friendly. Detailed Implementation

[0019] The present invention will be further described below with reference to embodiments, but the present invention is not limited thereto.

[0020] All reagents used in the following embodiments of the present invention can be obtained commercially or in-house. The 97% nicosulfuron technical grade used in the embodiments was purchased from Changqing (Hubei) Biotechnology Co., Ltd. Unless otherwise specified, all percentages mentioned in the following embodiments are mass percentages.

[0021] Example 1: 10% nicosulfuron-methyl soluble liquid S1. Add the prescribed amount of deionized water and 20% PEG-400 + 5% glucamide to the reaction vessel. Slowly add 10% nicosulfuron technical grade under stirring conditions, control the stirring speed at 200-400 rpm, and continue stirring for 10-20 minutes to form a suspension. S2. Add 0.6% citric acid-sodium citrate solution, adjust the pH to 6-7.5, and stir to form a transparent solution; then add 10% surfactant (polyoxyethylene lauryl ether + sodium oleoyl methyl taurate (3:2)) and 4.5% ethylene glycol in sequence. S3. Heat the solution obtained in S2 to 35℃ and stir continuously for 20-40 minutes. Mix thoroughly and let stand for 2 to 5 hours until the system is clear and transparent. After passing quality inspection, it can be bottled.

[0022] Example 2: 15% nicosulfuron-methyl soluble liquid S1. Add the prescribed amount of deionized water + 21.5% sorbitol to the reaction vessel, and slowly add 15% mesotrione technical grade under stirring conditions. Control the stirring speed at 200-400 rpm and continue stirring for 10-20 minutes to form a suspension. S2. Add 0.5% citric acid-phosphate, adjust the pH to 6-7.5, and stir to form a transparent solution; then add 14.5% surfactant (alkylphenol polyoxyethylene ether + C12-C15 alkyl glycoside (1:1)) and 7% ethylene glycol in sequence. S3. Heat the solution obtained in S2 to 40℃ and stir continuously for 20-40 minutes. Mix thoroughly and let stand for 2 to 5 hours until the system is clear and transparent. After passing quality inspection, it can be bottled.

[0023] Example 3: 20% nicosulfuron-methyl soluble liquid S1. Add the prescribed amount of deionized water + 21.5% sorbitol to the reaction vessel, and slowly add 20% mesotrione technical grade under stirring conditions. Control the stirring speed at 200-400 rpm and continue stirring for 10-20 minutes to form a suspension. S2. Add 0.5% citric acid-sodium citrate solution, adjust the pH to 6-7.5, and stir to form a transparent solution; then add 13% surfactant (polyoxyethylene fatty acid ether + lauryl alcohol polyoxyethylene ether (5.5:4.5)) and 7.5% polyethylene glycol in sequence. S3. Heat the solution obtained in S2 to 40℃ and stir continuously for 20-40 minutes. Mix thoroughly and let stand for 2 to 5 hours until the system is clear and transparent. After passing quality inspection, it can be bottled.

[0024] Example 4: 25% nicosulfuron-methyl soluble liquid S1. Add the prescribed amount of deionized water and 20% PEG-400 + 5% glucamide to the reaction vessel. Slowly add 25% nicosulfuron technical grade under stirring conditions, control the stirring speed at 200-400 rpm, and continue stirring for 10-20 minutes to form a suspension. S2. Add 0.6% citric acid-sodium citrate solution, adjust the pH to 6-7.5, and stir to form a transparent solution; then add 13% (castor oil polyoxyethylene ether + C12-C15 alkyl glycoside (6.5:4.5)) and 7% isopropanol in sequence. S3. Heat the solution obtained in S2 to 35℃ and stir continuously for 20-40 minutes. Mix thoroughly and let stand for 2 to 5 hours until the system is clear and transparent. After passing quality inspection, it can be bottled.

[0025] Comparative Example 1: 20% nicosulfuron-methyl soluble liquid S1. Weigh 20% nicosulfuron technical grade, add it to deionized water + 15% sorbitol under stirring conditions, and after forming a uniform suspension, add 0.5% citric acid to adjust the pH to 6.0-7.5 to dissolve the technical grade. S2, add 13% sodium dodecylbenzenesulfonate and 8% polyethylene glycol in sequence; S3. Heat the solution obtained in S2 to 40℃ and stir continuously for 20-40 minutes. Mix thoroughly, let stand for 2 to 5 hours, and filter and fill after passing the test.

[0026] Comparative Example 2: 25% nicosulfuron-methyl soluble liquid S1. Weigh 25% nicosulfuron technical grade, add it to deionized + 25% xylene under stirring conditions, and after forming a uniform suspension, add 0.6% citrate-sodium citrate buffer solution to adjust the pH to 6.0-7.5 to dissolve the technical grade. S2, add 13% sodium dodecylbenzenesulfonate and 7% isopropanol in sequence; S3. Heat the solution obtained in S2 to 40℃ and stir continuously for 20-40 minutes. Mix thoroughly, let stand for 2 to 5 hours, and filter and fill after passing the test.

[0027] Application Example 1 The effective component content and stability of the soluble liquid preparations obtained in four embodiments and two comparative examples of the present invention were tested. The specific test methods are as follows, and the results are shown in Table 1: Content of active ingredient: determined according to the method of HJ 850-2017 "Determination of nicosulfuron in water by liquid chromatography".

[0028] Cold storage stability: According to GB / T 19137-2003, the test method is to first place the sample in a refrigerator at (0±2)℃ for 1 hour and observe whether there is any change in appearance. Then, continue to store it in a refrigerator at (0±2)℃ for 7 days and test the specified items.

[0029] Thermal storage stability: According to the test method of GB / T 28138-2011, the sample was sealed and stored in a constant temperature chamber at (54±2)℃ for 14 days, then taken out and cooled to room temperature, and the specified items were tested.

[0030] Persistent foaming property: Determination method according to GB / T 28137-2011.

[0031] The test results show that the stability and active ingredient content of all formulations in the examples are qualified after cold and hot storage. Comparative Examples 1 and 2, however, failed the stability test after cold and hot storage, indicating a risk of stratification and deterioration.

[0032] Table 1. Test results of the physicochemical properties of nitrosulfuron-methyl soluble liquid.

[0033] Application Example 2 Efficacy test of nicosulfuron-methyl soluble liquid for controlling weeds in corn fields: Test agents: Examples 1-4, Comparative Examples 1-2, and commercially available 40% nicosulfuron suspension, commercially available 75% nicosulfuron water-dispersible granules, and blank control were sprayed with the same weight of water (30 kg / mu).

[0034] In 2021, a demonstration and promotion trial was conducted at the experimental base in Nong'an County, Changchun City, Jilin Province. The main weeds that occurred in the field included: barnyard grass, crabgrass, velvetleaf, goosegrass, amaranth retroflexus, and lambsquarters.

[0035] Experimental method: When weeds are at the 2-3 leaf stage and corn seedlings are at the 3-6 leaf stage, use a manual sprayer with a water concentration of 35 kg / 667 m². 2 Foliar spraying was used. Each treatment was repeated four times in a 50-square-meter plot. Weeds were identified and counted in the planting area 20 and 45 days after application. The plant control efficacy was calculated using the following formula. While investigating the efficacy, the presence of any phytotoxicity to the maize plants was observed. Specific experimental agents, dosages, and results are shown in Table 2.

[0036]

[0037] The results of the weed control efficacy survey (Table 2) show that 21 days after application, Examples 1-4 all demonstrated good control effects against barnyard grass, crabgrass, velvetleaf, goosegrass, amaranth, and lambsquarters in cornfields, with a total control efficacy of 87.5-90.3%, significantly better than the comparative example and commercially available herbicides. 42 days after application, the control efficacy further improved, with the total control efficacy of Examples 1-4 against weeds in cornfields increasing to 90.7-92.0%. Furthermore, no phytotoxicity was observed during the spraying process in Examples 1-4.

[0038] Table 2. Control efficacy of nicosulfuron-methyl soluble liquid against weeds in corn fields

[0039] Field trial results of nicosulfuron-methyl soluble liquid for controlling weeds in non-cultivated land: Test agents: Example 3 and commercially available 40% nicosulfuron suspension, with the blank control being sprayed with the same weight of water (30 kg / mu).

[0040] In 2021, a control trial was conducted at the National Grass Variety Regional Experiment Station in Xikou Village, Jianyang District, Nanping City, Fujian Province. The weeds occurring in the field included broadleaf weeds and grass weeds, such as cocklebur, velvetleaf, spiny amaranth, lambsquarters weeds, knotweed weeds (such as sorrel-leaved knotweed and willow-leaved knotweed), black nightshade, purslane, kochia scoparia, ragweed, dayflower, barnyard grass, crabgrass, foxtail grass, and arm-shaped grass.

[0041] The experimental methods and efficacy calculation methods are described in the Corn Field Herb Efficacy Test.

[0042] As shown in Table 3, the dosage of nicosulfuron soluble concentrate used in Example 3 was 80 g ai / hm. 2 ~140g ai / hm 2 In comparison, the 15-day visual control efficacy and the 15-day measured control efficacy were both superior to 40% nicosulfuron suspension. The application rate of nicosulfuron soluble concentrate was 140 g ai / hm. 2 At the same time, the control efficacy against broadleaf weeds and grass weeds is higher than 95%.

[0043] Table 3. Field trial results of nicosulfuron-methyl soluble liquid for controlling weeds in non-cultivated land.

[0044] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0045] 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. A soluble liquid formulation comprising mesotrione, characterized in that, By mass percent, it contains the following components: mesotrione technical 5%-40%, solvent 5%-30%, surfactant 3-20%, antifreeze 1-10%, pH regulator 0.3-3%, the rest is deionized water.

2. A soluble liquid formulation comprising mesotrione according to claim 1, characterized in that, By mass percent, it contains the following components: mesotrione technical 5%-40%, solvent 5%-30%, surfactant 3-20%, antifreeze 1-10%, pH regulator 0.3-3%, the rest is deionized water.

3. The soluble liquid formulation of mesotrione according to claim 2, characterized in that, The solvent is selected from one or more of methylated soybean oil, PEG-400, alpha-terpineol, glucose amide, sorbitol, deionized water; The antifreeze is selected from one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, inorganic salt, polyethylene glycol, sorbitol, isopropyl alcohol; The pH regulator is selected from one or more of sodium hydroxide, ammonia, glacial acetic acid, citric acid, phosphoric acid, sodium citrate, sodium lactate; The surfactant is selected from one or more of polyoxyethylene lauryl ether, castor oil polyoxyethylene ether, octadecyl betaine, fatty alcohol polyoxyethylene ether sodium sulfate, fatty alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, long-chain carboxylic acid ester polyoxyethylene-18, polyoxyethylene oleate, oleyl polyoxyethylene ether, fatty alcohol polyoxyethylene sulfate, polyethylene glycol sulfate, fatty alcohol polyoxyethylene carboxylate, fatty alcohol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, alkyl phenol polyoxyethylene ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid ether, polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene alkyl phenol ether, polyoxyethylene castor oil derivative, polyoxyethylene glycerol ester, cocamide propyl betaine, sodium dodecyl benzene sulfonate, dodecyl hydroxypropyl sulfobetaine, dodecyl hydroxypropyl sulfobetaine, dodecyl hydroxypropyl sulfobetaine, lauryl amide propyl hydroxy sulfobetaine, decyl amide propyl betaine, decyl amide propyl betaine, erucamide propyl betaine, erucamide propyl betaine, erucamide propyl betaine, C12-C15 alkyl glycoside, APG-1214, APG-0814, sodium oleoyl methyl taurate.

4. The soluble liquid formulation of mesotrione according to claim 3, characterized in that, The solvent is selected from one or more of deionized water + PEG-400 + glucose amide or deionized water + sorbitol; The surfactant is selected from one or more of polyoxyethylene lauryl ether + sodium oleoyl methyl taurate, alkyl phenol polyoxyethylene ether + C12-C15 alkyl glycoside, polyoxyethylene fatty acid ether + lauryl alcohol polyoxyethylene ether, castor oil polyoxyethylene ether + C12-C15 alkyl glycoside.

5. The solubility liquid of mesotrione according to claim 4, characterized by, The weight ratio of the two selected surfactants is (1~6.5):(1~4.5).

6. A process for the preparation of the soluble liquid formulation of mesotrione according to any one of claims 1 to 5, characterized in that, The preparation method comprises the following steps: S1, add the formula amount of deionized water to the reaction container, slowly add mesotrione technical and solvent under stirring, control the stirring speed to be 200-400 rpm, and continuously stir for 10-20 minutes to form a suspension; S2, add the pH regulator and adjust the pH to 6-9 to form a transparent solution; then add the surfactant, antifreeze in sequence; S3, the solution obtained in S2 is warmed to 30-50℃, and stirring is continued for 20-40 minutes. The mixture is mixed evenly, and left to stand for 2-5 hours until the system appears clear and transparent. After quality testing, it is filled into containers.

7. Use of the soluble liquid formulation of mesotrione as defined in any one of claims 1 to 5 for controlling weeds.

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