Quizalofop-p-ethyl and imazamox compound missible oil preparation

Abstract

The invention provides a quizalofop-p-ethyl and imazamox compound missible oil preparation, which successfully solves the problem of crystallization of imazamox, and ensures the emulsifying dispersity at the same time. Compared with the prior art, the preparation disclosed by the invention has remarkable advantages in the aspects of storage stability, volatility resistance and field applicability. The quizalofop-p-ethyl and imazamox compound missible oil preparation disclosed by the invention is mainly applied to fields of crops such as soybeans and corns, and can be used for preventing and removing gramineous weeds and broadleaf weeds at the same time and delaying the development of drug resistance of the weeds.

Description

Technical Field

[0001] This invention relates to the field of pesticide formulations, and more specifically, to a compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide. Background Technology

[0002] Emulsifiable concentrates (ECs) are homogeneous, transparent, oily liquids made by dissolving pesticide technical in an organic solvent and adding emulsifiers and other adjuvants. Before use, they are diluted with water to form a stable emulsion, which is then applied by spraying. Due to their mature technology and outstanding efficacy, ECs remain the mainstream pesticide formulation.

[0003] Quizalofop-P-ethyl is a phenoxycarboxylic acid herbicide with the molecular formula C19H17ClN2O4 and the chemical name (R)-2-[4-(6-chloroquinoxaloline-2-yloxy)phenoxy]propionate ethyl ester. The technical grade is a pale yellow solid, sparingly soluble in water (solubility 0.61 mg / L at pH=7), but readily soluble in organic solvents such as acetone and xylene. Quizalofop-P-ethyl is absorbed through the stems and leaves of weeds, inhibiting fatty acid synthesis in cells and causing necrosis of meristematic tissues. It is suitable for use on cash crops, vegetables, and fruit trees, such as soybeans, rapeseed, peanuts, cotton, tobacco, potatoes, peppers, watermelons, sugar beets, cabbage, cucumbers, strawberries, citrus, and grapes. It is effective in controlling a variety of annual and perennial grasses, including crabgrass, barnyard grass, goosegrass, wild oats, foxtail grass, reeds, bermudagrass, and cogongrass. Common dosage forms include emulsifiable concentrates, microemulsions, and water-dispersible granules.

[0004] Imazamox is an imidazolinone herbicide with the molecular formula C15H19N3O4 and the chemical name (RS)-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-5-methoxymethylnicotinic acid. It is a white, odorless solid with a melting point of 166-167℃, readily soluble in water, and easily hydrolyzed under alkaline conditions. Imazamox inhibits acetolactate synthase (ALS), blocks the synthesis of branched-chain amino acids (valine and leucine), and interferes with protein metabolism. It is suitable for economic crops such as soybeans, sunflowers, rapeseed, peanuts, and alfalfa, and can effectively control various gramineous and broadleaf weeds, including wild oats, barnyard grass, foxtail grass, crabgrass, velvetleaf, amaranth, black nightshade, cocklebur, and dayflower. Common formulations include aqueous solutions and water-dispersible granules.

[0005] Methimidine has low solubility in common organic solvents (such as xylene and 150# solvent oil), and usually requires the use of polar solvents (such as DMF and methanol) or salt-forming techniques (such as triethylamine) to improve its solubility. However, existing studies have shown that triethylamine is volatile, causing methimidine to crystallize after exposure to open containers, and DMF or xylene alone cannot completely inhibit crystallization. Therefore, existing methimidine formulations suffer from problems such as crystallization, insufficient emulsification properties, and a single solvent system. Summary of the Invention

[0006] In view of the above-mentioned technical problems, the formulation of the present invention faces the following technical difficulties during development: (1) Stability issues: Triethylamine is volatile, which leads to the precipitation of methoxymethylene smoke, so more stable adjuvants need to be used.

[0007] (2) Emulsification performance issues: It is necessary to select an emulsifier that is compatible with the two active ingredients to ensure the stability of the emulsion after dilution.

[0008] (3) Solvent selection: The solubility of the two active ingredients in solvents is quite different. Methimidine has low solubility in non-polar solvents (such as xylene, 150#), while quizalofop-p-ethyl is easily soluble in non-polar solvents. Therefore, the solvent system needs to be optimized.

[0009] This invention effectively solves the problems of active ingredient crystallization and storage stability by optimizing the solvent and emulsifier system and replacing triethylamine with triethanolamine, thereby providing a stable emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide.

[0010] Unless otherwise specified, "%" in this invention refers to mass percentage content.

[0011] This invention provides a compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide, comprising, by weight percentage: 2-5% quizalofop-P-ethyl, 2-5% methoxyfenozide, 20-30% emulsifier, 2%-6% triethanolamine, 10-20% N,N-dimethylformamide (DMF), with organic solvent to make up to 100%.

[0012] Preferably, the triethanolamine content is 2%-2.5%.

[0013] Preferably, the emulsifier is selected from one or more of alkylphenol polyoxyethylene ethers (OP-10, OP-15), phenethylphenol polyoxyethylene ethers (agricultural emulsion 600, agricultural emulsion 1601), castor oil polyoxyethylene ethers (EL-40, EL-60), fatty alcohol polyoxyethylene ethers (AEO-9, AEO-15), and polyol fatty acid esters (Span-80, Tween-80).

[0014] Preferably, the organic solvent is selected from one or more of cyclohexanone, toluene, xylene, ethanol, N-methylpyrrolidone, ethyl acetate, 150# solvent oil, and 200# solvent oil.

[0015] Preferably, the compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide of the present invention comprises: 3.5% quizalofop-P-ethyl, 3.5% methoxyfenozide, 25% emulsifier Nong Emulsifier 600, 2.5% triethanolamine, 15% N,N-dimethylformamide, and 150# solvent oil to make up to 100%.

[0016] This invention also provides a method for preparing a compound emulsifiable concentrate formulation of quizalofop-p-ethyl and methoxyfenozide, comprising the following steps: (1) Salt formation reaction: Methoxymethylene nicotine and triethanolamine are stirred in DMF (40-50℃, 30min) to form a soluble salt; (2) Dissolve quizalofop-P-ethyl: Add quizalofop-P-ethyl and stir until completely dissolved; (3) Add emulsifier: Add emulsifier and mix well; (4) Replenish solvent: Adjust to the target volume with organic solvent and stir until homogeneous and transparent.

[0017] By adopting the above technical solution, the present invention has the following beneficial effects: (1) This invention successfully solved the crystallization problem of methoxymethylene by using triethanolamine instead of triethylamine and combining it with an optimized solvent system of 15% DMF + 150# solvent oil, while ensuring emulsification and dispersibility. Compared with existing technologies, this solution has significant advantages in terms of storage stability, volatility resistance and field applicability.

[0018] (2) The compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide of the present invention is mainly used in fields of crops such as soybeans and corn. It can control both grass and broadleaf weeds at the same time and delay the development of herbicide resistance in weeds.

[0019] (3) The formulation of the present invention uses an environmentally friendly solvent formula, which is in line with the green development trend of pesticides. The formula can be adjusted according to different application scenarios, which has good market application prospects and technology expansion space, and provides a more efficient weed control solution for agricultural production. Detailed Implementation

[0020] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] I. Optimization process of adjuvants 1. Based on the experience of developers, Formulation 1 was initially obtained, which, by mass percentage, contains: 3.5% quizalofop-p-ethyl, 3.5% imazamox, 10% N,N-dimethylformamide (DMF), 25% emulsifier Nongru 600, 1.6% triethylamine, and the balance is xylene.

[0022] After the cold and heat storage stability test, the properties of this composition were normal, but under the condition of open exposure, crystals precipitated at the bottom of the sample.

[0023] 2. Based on the crystallization problem of Formulation 1, the formulation was adjusted to: 3.5% quizalofop-p-ethyl, 3.5% imazamox, 10% DMF, 10% methanol, 25% emulsifier Nongru 600, 1.6% triethylamine, and the balance is xylene.

[0024] The cold and heat storage stability of this composition was qualified, but crystals still precipitated at the bottom after open exposure.

[0025] 3. The solvent was adjusted to obtain Formulation 3, which contains: 3.5% quizalofop-p-ethyl, 3.5% imazamox, 10% DMF, 25% emulsifier Nongru 600, 1.6% triethylamine, and the solvent was replaced with 150# solvent oil.

[0026] The cold and heat storage stability of this composition was good, but crystals precipitated after open exposure.

[0027] 4. The solvent ratio was optimized to obtain Formulation 4, which contains: 3.5% quizalofop-p-ethyl, 3.5% imazamox, 15% DMF, 25% emulsifier Nongru 600, 1.6% triethylamine, and the balance is 150# solvent oil.

[0028] The cold and heat storage stability met the standard, but there was still a crystallization problem after open exposure.

[0029] 5. Through analysis, it was determined that the crystallization was caused by the volatilization of triethylamine. To solve this problem, triethanolamine was used to replace triethylamine to obtain the preferred formulation, which contains: 3.5% quizalofop-p-ethyl, 3.5% imazamox, 25% emulsifier Nongru 600, 2.5% triethanolamine, 15% DMF, and 150# solvent oil was made up to 100%.

[0030] The cold and heat storage stability of this composition was excellent, and when the addition amount of triethanolamine was 2.0% - 2.5%, the emulsification and dispersion performance met the standard. After a 48-hour open exposure test, no crystal precipitation was observed, and the product analysis was qualified, so it was determined as the optimal industrial production plan.

[0031] The preparation method of the above optimal formulation composition includes the following steps: (1) Salt formation reaction: Imazamox and triethanolamine are stirred and reacted in DMF (40 - 50 °C, 30 min) to form a soluble salt; (2) Dissolve quizalofop-P-ethyl: Add quizalofop-P-ethyl and stir until completely dissolved; (3) Add emulsifier: Add emulsifier agricultural emulsion 600 and mix well; (4) Replenish solvent: Adjust to the target volume with 150# solvent oil and stir until uniform and transparent.

[0032] The key performance tests were conducted on the above-mentioned optimal formulation composition, and the results are as follows:

[0033] II. Field efficacy trials 1. Experimental site conditions: rapeseed field in the middle and lower reaches of the Yangtze River (representative weeds: barnyard grass, barnyard grass, and chickweed); soil conditions: pH 5.5–6.5, organic matter content 15–20 g / kg, humidity 60%–70%; weed population: grass weed density 30–50 plants / m², broadleaf weed density 20–40 plants / m², evenly distributed.

[0034] The area of ​​each plot is 30 m² (6m×5m), with 0.8 m wide earthen ridges between plots, repeated 4 times, using a randomized block design, and a 1.5 m protective row reserved around the perimeter.

[0035] 2. Processing settings (5 processes in total, 4 repetitions): T1: Low-dose formulation (600 mL / ha) T2: The dosage in the formulation (900 mL / ha, recommended dose). T3: High-dose formulation (1200 mL / ha). CK1: Control agent (10.8% quizalofop-P-ethyl EC 450 mL / ha + 4% methoxyfenozide Aqueous solution 750 mL / ha). CK2: Water control.

[0036] Application plan: Backpack sprayer (nozzle diameter 0.3 mm), droplet diameter 100–150 μm, application period: rapeseed 4-5 leaf stage, weeds 3-5 leaf stage, weed sensitivity period, application weather: no wind or light wind (wind speed <3 m / s), temperature 15–25℃.

[0037] 3. Methods for investigating drug efficacy The efficacy of the drug was investigated 15 days after application using a five-point sampling method: five points were taken from each plot, with each point measuring 0.25 m² (0.5m × 0.5m).

[0038] Survey content: Number of weeds (recorded by species); Control efficacy (%) = [(Number of weeds in the control area - Number of residual weeds in the treatment area) / Number of weeds in the control area] × 100% 4. Experimental results (data 15 days after application)

[0039] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide, characterized in that, By weight percentage, it contains: 2-5% quizalofop-p-ethyl, 2-5% methoxyfenozide, 20-30% emulsifier, 2%-6% triethanolamine, 10-20% N,N-dimethylformamide, with organic solvents to be made up to 100%.

2. The emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide according to claim 1, characterized in that, The triethanolamine content is 2%-2.5%.

3. The emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide according to claim 1, characterized in that, The emulsifier is selected from one or more of alkylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, and polyol fatty acid ester.

4. The emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide according to claim 1, characterized in that, The organic solvent is selected from one or more of cyclohexanone, toluene, xylene, ethanol, N-methylpyrrolidone, ethyl acetate, 150# solvent oil, and 200# solvent oil.

5. The emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide according to claim 1, characterized in that, Contains: 3.5% quizalofop-P-ethyl, 3.5% methoxyfenozide, 25% emulsifier agricultural emulsion 600, 2.5% triethanolamine, 15% N,N-dimethylformamide, and 150# solvent oil to bring the total to 100%.

6. A method for preparing a compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide according to any one of claims 1-5, characterized in that, Includes the following steps: (1) Salt formation reaction: Methoxymethylene nicotine and triethanolamine are stirred in DMF to form a soluble salt; (2) Dissolve quizalofop-P-ethyl: Add quizalofop-P-ethyl and stir until completely dissolved; (3) Add emulsifier: Add emulsifier and mix well; (4) Replenish solvent: Adjust to the target volume with organic solvent and stir until homogeneous and transparent.

7. The method for preparing the compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide according to claim 6, characterized in that, In step (1), the reaction temperature is 40-50℃ and the mixture is stirred for 30 minutes.

8. The application of the compound emulsifiable concentrate formulation of quizalofop-P-ethyl and methoxyfenozide according to any one of claims 1-5 in the control of crop weeds.

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