Preparation method of a clethodim solid preparation and the solid preparation thereof

Abstract

The application discloses a preparation method of an alkene oxime ketone solid preparation and the solid preparation. The alkene oxime ketone solid preparation is prepared by a one-pot method, that is, an auxiliary I (preferably selected from 1,4-diamine or 1,6-diamine) of alkene oxime ketone is complexed and solidified, and then a pesticide preparation auxiliary component is added. The preparation method does not use any organic solvent, is environment-friendly, greatly shortens a preparation technological process, causes less decomposition of raw material alkene oxime ketone, and in-situ obtains the alkene oxime ketone solid preparation, thereby avoiding the problems of storage decomposition of alkene oxime ketone amine salt and cost increase of low-temperature storage. Meanwhile, the alkene oxime ketone solid preparation prepared by the method has superior storage stability and good physical performance of the preparation, and has higher alkene oxime ketone content, which is beneficial to saving manufacturing and transportation costs. Meanwhile, the alkene oxime ketone solid preparation can fill the blank of alkene oxime ketone solid dosage forms, meet different medication scenes, and has better commercial prospects.

Description

Technical Field

[0001] This application relates to a method for preparing clethodim solid formulations and the solid formulation thereof, belonging to the field of agricultural herbicide technology. Background Technology

[0002] Clethodim, chemically known as 2-{1-[(3-chloro-2-allyl)oxy]iminopropyl}-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one, is a cyclohexanedione herbicide with excellent herbicidal activity. Currently, commercially available industrial clethodim products are liquids, typically containing 86-97% clethodim. The clethodim structure contains multiple non-adjacent carbon-carbon double bonds and oxime functional groups, resulting in poor stability, frequent configuration inversion, and sensitivity to ultraviolet light and heat. Therefore, it is prone to decomposition during long-term transportation and storage, leading to a decrease in clethodim content and reduced herbicidal efficacy in the product. Once clethodim decomposes, the content of active ingredients decreases, which seriously affects subsequent formulation processing and efficacy. Therefore, it is very important to reduce the decomposition rate of clethodim technical and formulations during storage, improve stability, and increase the content of active ingredients. At the same time, currently available clethodim formulations are all emulsifiable concentrates (EC), such as 240EC and 360EC formulations, and there are no solid formulations, such as water-dispersible granules (WG), soluble granules (SG), soluble powders (SP), or wettable powders (WP), which also limits the application scenarios and commercial use of clethodim.

[0003] Besides the formulation components, adjuvants, and adjuvant content of clethodim solid dosage forms, the preparation process of clethodim solid dosage forms is also crucial in affecting their performance. Different preparation processes for clethodim solid dosage forms will result in different production costs and will also affect their performance.

[0004] Patent CN102382023A discloses a method for improving the stability of clethodim, which discloses a variety of monoamine salts of clethodim, all of which are monoamine salts of clethodim. The amine compounds used in the examples are primary amines (such as ethylamine, n-butylamine) and secondary amines (such as isopropylamine), etc., but the composition of the solid formulation of clethodim monoamine salts and its preparation method are not disclosed.

[0005] Patent CN119390631A discloses clethodim tert-butylamine salt and its preparation method, but does not disclose the components of the solid formulation of clethodim tert-butylamine salt and its preparation method.

[0006] Patent CN120887818A discloses clethodim diamine salt and its preparation method, as well as the components and preparation method of solid formulations of clethodim diamine salt. The preparation method of solid formulations of clethodim diamine salt mainly includes the following two aspects:

[0007] 1. Preparation of clethodim diamine salt, the method includes the following steps: S1: Dissolve clethodim in a solvent to obtain mixture A; S2: Add a diamine compound or its solution to mixture A to carry out the reaction. After the reaction is completed, clethodim diamine salt is precipitated out of the reaction system. S3: Separate the precipitate to obtain clethodim diamine salt.

[0008] 2. Preparation of solid formulations of clethodim diamine salt, comprising the following steps: mixing clethodim diamine salt and various adjuvants in a certain proportion, stirring evenly in a stirred tank, and then passing through an air jet mill to obtain a wettable powder of clethodim diamine salt; or mixing clethodim diamine salt and various adjuvants in a certain proportion, pulverizing with an ultra-micro air jet mill, kneading, then adding to a fluidized bed dryer for drying, sieving, and sampling analysis to obtain a water-dispersible granule of clethodim diamine salt.

[0009] The preparation method of this solid formulation of clethodim diamine salt has the following problems: 1. The use of a large amount of organic solvent raises environmental and safety concerns; 2. The process involves dissolution, crystallization, filtration, and separation, resulting in a long preparation process, raw material loss, and increased production costs; 3. The preparation of clethodim diamine salt and the preparation of its solid formulation (wettable powder or water-dispersible granules) are completely separated into two independent steps, leading to issues related to the storage stability of clethodim diamine salt and the increased manufacturing costs due to the need for low-temperature storage; 4. The performance of the solid formulation of clethodim prepared by this method is not entirely satisfactory. For example, the clethodim content still needs further improvement, and the stability and physical properties need further enhancement.

[0010] Therefore, there is a need to develop manufacturing methods and solid formulations of clethodim that offer one or more improvements, such as simplified preparation processes, lower production costs, higher clethodim content in clethodim solid formulations, improved stability of clethodim solid formulations, and improved performance of clethodim solid formulations. Summary of the Invention

[0011] The purpose of this application is to address the technical problems of long preparation process and high production cost of clethodim solid dosage form, and how to further increase the clethodim content in clethodim solid dosage form, and further improve the physical properties and stability of clethodim solid dosage form. This application provides a method for preparing clethodim solid dosage form and the solid dosage form thereof.

[0012] To achieve the above objectives, this application adopts the following technical solution: A first aspect of this application provides a method for preparing clethodim solid dosage form, wherein the clethodim solid dosage form is a solid granule or a solid powder, and the preparation method includes the following steps: S1: Under solvent-free conditions, clethodim and adjuvant I are mixed to obtain solid mixture A; pesticide formulation auxiliary components are then added to solid mixture A in a certain proportion and mixed to obtain solid mixture B; S2: Solid mixture B is pulverized, then granulated, dried and sieved to obtain solid granules; or solid mixture B is uniformly stirred and pulverized to obtain solid powder. The auxiliary agent I is selected from at least one of 1,4-butanediamine, 1,5-pentanediamine and 1,6-hexanediamine.

[0013] Preferably, the solid granules are selected from water-dispersible granules and soluble granules; the solid powder is selected from wettable powder and soluble powder.

[0014] Preferably, the adjuvant I is selected from at least one of 1,4-butanediamine and 1,6-hexanediamine.

[0015] More preferably, the solid granules are selected from water-dispersible granules; the solid powder is selected from wettable powders.

[0016] More preferably, the preparation method of the clethodim solid dosage form includes the following steps: S1: Under solvent-free conditions, clethodim and adjuvant I are mixed to obtain solid mixture A; pesticide formulation auxiliary components are then added to solid mixture A in a certain proportion and mixed to obtain solid mixture B; S2: Solid mixture B, after being crushed, kneaded, granulated, dried and sieved, is used to obtain water-dispersible granules; or solid mixture B, after being uniformly stirred and crushed, is used to obtain wettable powder. The auxiliary agent I is selected from at least one of 1,4-butanediamine and 1,6-hexanediamine.

[0017] More preferably, the preparation method of the clethodim solid dosage form includes the following steps: S1: Under solvent-free conditions, clethodim and adjuvant I are mixed to obtain solid mixture A; pesticide formulation auxiliary components are then added to solid mixture A in a certain proportion and mixed to obtain solid mixture B; S2: Solid mixture B is pulverized by an ultra-fine airflow pulverizer to reduce the particle size (D90) of the material to below 20μm, kneaded, then granulated, dried to a moisture content of below 3%, and sieved to obtain water-dispersible granules; or solid mixture B is uniformly stirred and pulverized by an ultra-fine airflow pulverizer to reduce the particle size (D90) of the material to below 20μm to obtain wettable powder; Wherein, the adjuvant I is selected from at least one of 1,4-butanediamine and 1,6-hexanediamine; the molar ratio of clethodim to adjuvant I is (1:0.4) to (1:0.7).

[0018] By employing the above technical solution, the method for preparing clethodim solid formulations (water-dispersible granules or wettable powders) is simple. After clethodim is complexed and solidified with adjuvant I, it is immediately mixed with pesticide formulation auxiliary components to prepare the clethodim solid formulation. This method requires no solvents, has a short manufacturing process, short manufacturing time, and low production cost. Surprisingly, the clethodim solid formulation exhibits good physical properties, demonstrating better formulation storage stability and improved physical performance.

[0019] Preferably, the mixing temperature of clethodim and adjuvant I in S1 is 15-85°C; more preferably, the mixing temperature of clethodim and adjuvant I in S1 is 52°C to 65°C.

[0020] Preferably, the mixing time of clethodim and adjuvant I in S1 is 0.5 hours to 2.0 hours.

[0021] Preferably, the molar ratio of clethodim to adjuvant I in S1 is (1:0.5) to (1:0.6).

[0022] Preferably, the mixing method of clethodim and adjuvant I in S1 is shear-stirring mixing.

[0023] The pesticide formulation auxiliary ingredients described in this application are selected from one or more of the following: surfactants, diluents, dispersants, wetting agents, antioxidants, pH adjusters, defoamers, fillers, carriers, etc.

[0024] Preferably, the auxiliary components of the pesticide formulation include wetting agents, dispersants, defoamers, and fillers.

[0025] Preferably, the wetting agent is at least one of alkyl naphthalene sulfonates, naphthalene sulfonate condensates, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, phosphate esters, acetylacetonate, ethoxylated silicone, sodium dibutylnaphthalene sulfonate (spreading powder), soap powder, detergent LS (sodium p-methoxy fatty amide benzene sulfonate), alkyl-substituted naphthalene sulfonates, alkylphenol polyoxyethylene ethers, polyalkylene glycol ethers, and sodium alkyl hydroxysulfonates. More preferably, the wetting agent is selected from at least one of spreading powder, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonates, and sodium alkyl hydroxysulfonates.

[0026] Preferably, the dispersant is sodium salt of naphthalenesulfonate formaldehyde polymer, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, fatty acid polyoxyethylene ester and glycerol fatty acid polyoxyethylene ether, sodium salt, calcium salt and ammonium salt of lignin sulfonate, naphthalenesulfonate formaldehyde condensate, polyoxyethylene ether phosphate, or polycarboxylate. More preferably, the dispersant is selected from at least one of lignin sulfonate, sodium salt of naphthalenesulfonate formaldehyde polymer, polyoxyethylene ether phosphate, and polycarboxylate.

[0027] Defoamers encompass all substances commonly used for this purpose in agricultural chemical compositions. Suitable defoamers are known in the art and are commercially available. Preferably, the defoamer is one of polydimethylsiloxane, polyether-modified silicone, silicone compounds, C8-C10 fatty alcohols, dimethyl silicone oil, fatty acid salts, etc. More preferably, the defoamer is selected from at least one of polyether-modified silicone, dimethyl silicone oil, and fatty acid salts.

[0028] Preferably, the filler is one of the following: water, salts such as alkali metal phosphates (e.g., sodium dihydrogen phosphate), alkaline earth metal phosphates, sulfates of sodium, potassium, magnesium, and zinc, sodium chloride, potassium chloride, sodium acetate, sodium carbonate, lactose, sucrose, and mannitol, clay, synthetic silica and diatomaceous earth, kaolin, calcium silicate, titanium dioxide, alumina, precipitated silica, calcium oxide, and zinc oxide, and mixtures thereof. More preferably, the filler is selected from at least one of sodium sulfate, clay, diatomaceous earth, kaolin, and precipitated silica.

[0029] A second aspect of this application provides a clethodim water-dispersible granule formulation comprising the following components: Clethodim 5%-80%; Additive I2%-14%; Wetting agent 1%-9%; Dispersant 3%-12%; Defoamer 0.0%-2%; Filler content: 0.0% to 89%; Wherein, each percentage is a mass percentage, and the auxiliary agent I is selected from at least one of 1,4-butanediamine, 1,5-pentanediamine and 1,6-hexanediamine, and the wetting agent is selected from at least one of the following: pull-apart powder, disodium salt of alcohol ether sulfosuccinate monoester, alkyl naphthalene sulfonate, naphthalene sulfonate condensate, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonate, and sodium salt of alkyl hydroxy sulfonate.

[0030] Preferably, the content of each component is as follows: Clethodim 5%-65%; Additive I 2%-10%; Wetting agent 1%-9%; Dispersant 3%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 89%; Wherein, each percentage is a mass percentage, and the auxiliary agent I is selected from at least one of 1,4-butanediamine, 1,5-pentanediamine and 1,6-hexanediamine, and the wetting agent is selected from at least one of the following: pull-apart powder, disodium salt of alcohol ether sulfosuccinate monoester, alkyl naphthalene sulfonate, naphthalene sulfonate condensate, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonate, and sodium salt of alkyl hydroxy sulfonate.

[0031] More preferably, the content of each component is as follows: Clethodim 5%-65%; Additive I 4%-10%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 85%; Wherein, each percentage is a mass percentage, adjuvant I is selected from 1,4-butanediamine and / or 1,6-hexanediamine, wetting agent is selected from at least one of alkyl naphthalene sulfonates, naphthalene sulfonate condensates, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonate, sodium alkyl hydroxy sulfonate, and the molar ratio of clethodim technical to adjuvant I is (1:0.4) to (1:0.6).

[0032] More preferably, the content of each component is as follows: Clethodim 10%-65%; Additive I 5%-10%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 79%; Wherein, each percentage is a mass percentage, and the additive I is selected from one of 1,4-butanediamine and / or 1,6-hexanediamine; the wetting agent is selected from at least one of the following: dispersant, disodium salt of alcohol ether sulfosuccinate monoester, alkyl naphthalene sulfonate, naphthalene sulfonate condensate, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonate, and sodium salt of alkyl hydroxy sulfonate; the dispersant is selected from at least one of lignin sulfonate, sodium salt of naphthalene sulfonate formaldehyde polymer, polyoxyethylene ether phosphate, and polycarboxylate; the defoamer is selected from at least one of polyether modified organosilicon and dimethyl silicone oil; and the filler is selected from at least one of sodium sulfate, white carbon black, and kaolin.

[0033] The molar ratio of clethodim technical grade to adjuvant I is (1:0.4) to (1:0.6); Preferably, the mass ratio of wetting agent to dispersant is 1:0.1-10.0.

[0034] A third aspect of this application provides a clethodim solid formulation, wherein the clethodim solid formulation is a wettable powder comprising the following components: Clethodim 5%-80%; Additive I2%-14%; Wetting agent 1%-9%; Dispersant 3%-12%; Defoamer 0.0%-2%; Filler content: 0.0% to 89%; Wherein, each percentage is a mass percentage, and the auxiliary agent I is selected from one of 1,4-butanediamine, 1,5-pentanediamine or 1,6-hexanediamine, and the wetting agent is selected from at least one of the following: a separating powder, disodium salt of alcohol ether sulfosuccinate monoester, alkyl naphthalene sulfonates, naphthalene sulfonate condensates, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonates, and sodium salt of alkyl hydroxy sulfonates.

[0035] Preferably, the content of each component is as follows: Clethodim 5%-65%; Additive I 2%-10%; Wetting agent 1%-9%; Dispersant 3%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 89%; Wherein, each percentage is a mass percentage, and the auxiliary agent I is selected from one of 1,4-butanediamine, 1,5-pentanediamine or 1,6-hexanediamine, and the wetting agent is selected from at least one of the following: a separating powder, disodium salt of alcohol ether sulfosuccinate monoester, alkyl naphthalene sulfonates, naphthalene sulfonate condensates, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonates, and sodium salt of alkyl hydroxy sulfonates.

[0036] More preferably, the content of each component is as follows: Clethodim 5%-65%; Additive I 4%-10%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 85%; Wherein, each percentage is a mass percentage, adjuvant I is selected from at least one of 1,4-butanediamine and 1,6-hexanediamine, wetting agent is selected from at least one of the following: splitting powder, disodium salt of alcohol ether sulfosuccinate monoester, alkyl naphthalene sulfonate, naphthalene sulfonate condensate, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonate, sodium alkyl hydroxy sulfonate, and the molar ratio of clethodim technical to adjuvant I is (1:0.4) to (1:0.6).

[0037] More preferably, the content of each component is as follows: Clethodim 10%-65%; Additive I 5%-10%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 79%; Wherein, each percentage is a mass percentage, adjuvant I is selected from 1,4-butanediamine or 1,6-hexanediamine, wetting agent is selected from at least one of dispersant powder, disodium salt of alcohol ether sulfosuccinate monoester, alkyl naphthalene sulfonate, naphthalene sulfonate condensate, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonate, sodium alkyl hydroxy sulfonate; dispersant is selected from at least one of lignin sulfonate, sodium salt of naphthalene sulfonate formaldehyde polymer, polyoxyethylene ether phosphate, polycarboxylate; the defoamer is selected from at least one of polyether modified organosilicon and dimethyl silicone oil; the filler is selected from at least one of sodium sulfate, white carbon black, and kaolin; the molar ratio of clethodim technical to adjuvant I is (1:0.4) to (1:0.6).

[0038] Preferably, the mass ratio of wetting agent to dispersant is 1:0.1-10.0.

[0039] A fourth aspect of this application provides the use of clethodim water-dispersible granules according to the second aspect, or clethodim wettable powder according to the third aspect, in the control of harmful weeds.

[0040] The fifth aspect of this application provides a method for controlling weeds by applying a weed-repellent effective amount of clethodim water-dispersible granules according to the second aspect, or clethodim wettable powder according to the third aspect, to a plant, a part of a plant, or the environment surrounding the plant.

[0041] Preferably, the harmful weeds are selected from grass weeds and broadleaf weeds.

[0042] More preferably, the harmful weeds are selected from Alopecurus aequalis, Alopecurus aequalis, Cercis chinensis, Sedum aizoon, Forget-me-not, Chickweed, Ivy, Barnyardgrass, Crataegus pinnatifida, Veronica persica, Eleusine indica, Sophora flavescens, and Viola yedoensis.

[0043] Preferably, the clethodim solid formulation (water-dispersible granules or wettable powder) is used to control harmful weeds in ornamental plants, fruit trees, vegetables, legumes, and cereal crops.

[0044] Preferably, the clethodim solid formulation (water-dispersible granules or wettable powder) is used to control harmful weeds in winter wheat, potatoes, sunflowers, sugar beets, sugarcane, carrots, corn, and soybeans.

[0045] In this application, the clethodim in the solid formulation is present at a concentration sufficient to achieve the desired dosage when applied to the plant or its location, preferably at a concentration of about 1% to about 95% by weight of the total mixture, preferably at a concentration of about 2% to about 85% by weight of the total mixture, and more preferably at a concentration of about 10% to about 65% by weight of the total mixture.

[0046] The formulations prepared using the method described in this application, namely clethodim water-dispersible granules and wettable powders, exhibit better formulation storage stability and physical properties, and thus have better commercialization prospects.

[0047] As used herein, the term “about” when used in conjunction with a numerical quantity or range means slightly greater than or slightly less than the numerical quantity or range, and deviating from the endpoints of the numerical quantity or range by ±10%.

[0048] The term "room temperature" as used in this article refers to a temperature range of approximately 20°C to 25°C.

[0049] Compared with the prior art, this application has the following advantages: 1. This application provides a method for preparing clethodim solid dosage form. The method involves complexing and solidifying clethodim with an adjuvant I (preferably 1,4-butanediamine or 1,6-hexanediamine) in a "one-pot" process to obtain the clethodim solid dosage form. This method does not use any organic solvents, making it environmentally friendly and highly safe. Furthermore, the process does not include dissolution, crystallization, or filtration separation, significantly shortening the preparation process, reducing the decomposition and loss of clethodim, and lowering production costs. The "one-pot" process obtains the clethodim solid dosage form in situ, avoiding the decomposition problem of clethodim amine salts during storage and the increased cost of low-temperature storage of clethodim amine salts. 2. The clethodim solid dosage form prepared by the method of this application has superior storage stability and good formulation physical properties; the clethodim solid dosage form prepared by the method of this application has a lower degradation rate during high-temperature heat storage than other similar clethodim solid dosage forms currently disclosed, making it easier to store for a long time and beneficial to the shelf life stability of commercial products. 3. The clethodim solid dosage form prepared using the method of this application has a higher clethodim content, superior storage stability and good formulation physical properties, while also helping to save manufacturing and transportation costs; at the same time, the clethodim solid dosage form of this application can fill the gap in clethodim solid dosage forms, meet different medication scenarios, and has better commercial prospects. Attached Figure Description

[0050] Figure 1 This is a process flow diagram of the preferred method for preparing clethodim water-dispersible granules. Detailed Implementation

[0051] To make this application more apparent and understandable, preferred embodiments are described in detail below with reference to figures and tables.

[0052] Preparation Example 1 A method for preparing clethodim water-dispersible granules is as follows: S1: Under solvent-free conditions and at a mixing temperature of 55°C, 383g of clethodim technical (94%, 1.0mol) and 46.3g of 1,4-butanediamine (99%, 0.52mol) were added to shear stirrer No. 1 and stirred thoroughly for 1.0 hour to obtain solid mixture A; then, pesticide formulation adjuvants (14.4g of clethodim, 36.0g of sodium formaldehyde sulfoxylate polymer, 43.2g of sodium lignosulfonate, and 220.6g of sodium sulfate) were added to solid mixture A and stirred thoroughly in shear stirrer No. 1 for 0.5 hours to obtain solid mixture B; S2: Solid mixture B is pulverized by an ultra-fine airflow pulverizer to reduce the particle size (D90) of the material to 18-20μm (sampled and tested). The qualified material enters the No. 2 mixer and is stirred and mixed for 0.5 hours until uniform. The material is discharged and weighed to obtain 717.1g of dry powder. The dry powder is transferred to the extrusion granulation equipment, and 144.0g of deionized water is added for kneading. After kneading, the mixture is granulated, dried to a moisture content of 0.4%, sieved, and tested to be qualified. Approximately 720.0g of clethodim water-dispersible granules are obtained.

[0053] Formulation Example 1 Formulation Example 1: The clethodim water-dispersible granules described in this application were prepared by the preparation method described in Example 1, and their composition is as follows: Table 1. Components of Clethodim Water Dispersible Granules (WG) in Formulation Example 1

[0054] Preparation Examples 2-5 The preparation method of clethodim water-dispersible granules differs from that in Example 1 in that the process parameters and the amount of each adjuvant are different, while other conditions are completely the same. The specific differences are shown in Table 2.

[0055] Table 2. Preparation method parameters for Examples 1-5

[0056] Formulation Example 2 Formulation Example 2: The clethodim water-dispersible granules described in this application were prepared by the preparation method described in Example 2, and their composition is as follows: Table 3. Components of Clethodim Water Dispersible Granules (WG) in Formulation Example 2

[0057] Formulation Example 3 Formulation Example 3: The clethodim water-dispersible granules described in this application were prepared by the preparation method described in Example 3, and their composition is as follows: Table 4. Components of Clethodim Water Dispersible Granules (WG) in Formulation Example 3

[0058] Formulation Example 4 Formulation Example 4: The clethodim water-dispersible granules described in this application were prepared by the preparation method described in Example 4, and their composition is as follows: Table 5. Components of Clethodim Water Dispersible Granules (WG) in Formulation Example 4

[0059] Formulation Example 5 Formulation Example 5: The clethodim water-dispersible granules described in this application were prepared by the preparation method described in Example 5, and their composition is as follows: Table 6. Components of Clethodim Water Dispersible Granules (WG) in Formulation Example 5

[0060] Preparation Example 6 A method for preparing clethodim wettable powder is as follows: S1: Under solvent-free conditions and at a mixing temperature of 55°C, 459.6 g of clethodim technical grade (94%, 1.0 mol) and 53.4 g of 1,4-butanediamine (99%, 0.50 mol) were added to shear stirrer No. 1 and stirred thoroughly for 1.0 hour to obtain solid mixture A; pesticide formulation adjuvants (sodium dodecyl sulfate 8.6 g, sodium 2-naphthalenesulfonic acid formaldehyde polymer 28.8 g, polycarboxylate 14.4 g, dimethyl silicone oil 8.6 g, kaolin 174.2 g) were added to solid mixture A and stirred thoroughly in shear stirrer No. 1 for 0.5 hours to obtain solid mixture B; S2: Solid mixture B is pulverized by an ultra-micro airflow pulverizer to reduce the particle size (D90) of the material to 18-20μm (sampled and tested). The qualified material enters the No. 2 mixer and is stirred and mixed for 0.5 hours until it is uniformly mixed. The material is then discharged to obtain approximately 720.0 grams of clethodim wettable powder.

[0061] Formulation Example 6 Formulation Example 6: The clethodim wettable powder described in this application was prepared by the preparation method described in Example 6, and its composition is as follows: Table 7. Components of Clethodim Wettable Powder (WP) in Formulation Example 6

[0062] Preparation Examples 7-8 The preparation method of clethodim wettable powder differs from that of Preparation Example 6 in that the process parameters and the amount of each adjuvant are different, while other conditions are completely the same. The specific differences are shown in Table 8.

[0063] Table 8. Parameters of the preparation methods in Examples 6-8

[0064] Formulation Example 7 Formulation Example 7: The clethodim wettable powder described in this application was prepared by the preparation method described in Preparation Example 7, and its composition is as follows: Table 9. Components of Clethodim Wettable Powder (WP) in Formulation Example 7

[0065] Formulation Example 8 Formulation Example 8: The clethodim wettable powder described in this application was prepared by the preparation method described in Preparation Example 8, and its component table is as follows: Table 10. Components of Clethodim Wettable Powder (WP) in Formulation Example 8

[0066] Referring to Tables 1 to 10, and through the preparation examples 1 to 8, it can be seen that the preparation method of this application, when obtaining clethodim solid formulations, controls the mixing temperature within 52-65℃. Considering both production costs and final product quality indicators, the molar ratio of clethodim to adjuvant I is controlled at (1:0.5) to (1:0.6). By appropriately adjusting the type and amount of pesticide formulation auxiliary components, and controlling the particle size (D90) of the pulverized material to below 20μm, stable clethodim solid formulations can be obtained. This preparation method does not use any organic solvents, is environmentally friendly, and has high safety. Furthermore, the process does not include operations such as dissolution, crystallization, or filtration separation, significantly shortening the preparation process. The "one-pot" process obtains clethodim solid formulations in situ, avoiding the decomposition problem of clethodim amine salts during storage and the increased cost of low-temperature storage of clethodim amine salts.

[0067] Formulation Comparison Example 1 Using the preparation method of Example 5 in patent CN120887818A, and in conjunction with the method of Formulation Example 6 in patent CN120887818A, clethodim water-dispersible granules containing 1,4-butanediamine as adjuvant I were prepared. The composition table of the clethodim water-dispersible granules of Formulation Comparative Example 1 is as follows: Table 11. Components of Clethodim Water Dispersible Granules (WG) in Formulation Comparison 1

[0068] Formulation Comparison Example 2 Using the preparation method of Example 3 in patent CN120887818A, and in conjunction with the method of Formulation Example 2 in patent CN120887818A, clethodim water-dispersible granules containing 1,6-hexanediamine as adjuvant I were prepared. The composition table of the clethodim water-dispersible granules of Formulation Comparative Example 2 is as follows: Table 12. Components of Clethodim Water Dispersible Granules (WG) in Formulation Comparison Example 2

[0069] Formulation Comparison Example 3 Using the preparation method of Example 3 in patent CN120887818A, and in conjunction with the method of Formulation Example 1 in patent CN120887818A, a clethodim wettable powder containing adjuvant I as 1,6-hexanediamine was prepared. The composition table of the clethodim wettable powder of Formulation Comparative Example 3 is as follows: Table 13. Components of Clethodim Wettable Powder (WP) for Formulation Comparison 3

[0070] Formulation ratio 4-7 The preparation method of clethodim water-dispersible granules described in this application differs from that in Example 1 in that the process parameters and the amount of each additive are different, while other conditions are completely the same. The specific differences are shown in Table 14.

[0071] Table 14. Preparation method parameters for formulations (comparative examples 4-7)

[0072] The stability of the clethodim solid formulation samples from Formulation Examples 1-8 and Formulation Comparative Examples 1-7 was tested by accelerated storage testing.

[0073] According to the international method for the physicochemical determination of pesticide technicals and formulations—CIPAC method—CIPAC MT 46.4 Accelerated Storage procedure specifies that pesticide technicals and formulations have a shelf life of at least 2 years under standard operating conditions. The shelf life of pesticide technicals and formulations under standard operating conditions can be determined through accelerated storage testing. Accelerated storage testing is conducted according to the combination of storage temperature and storage period specified in CIPAC MT46.4 Accelerated Storage procedure. The test results for residual active ingredients in the sample can be considered as predictive values ​​for 2 years of storage. (1) 54±2℃, for 14 consecutive days; (2) 50±2℃, for 4 weeks; (3) 45±2℃, for 6 weeks; That is, storing at 54±2℃ for 14 days is equivalent to storing at 50±2℃ for 4 weeks, and so on.

[0074] In the combination of storage temperature and storage period, storage temperature has a significant impact on the accelerated storage testing of pesticide technicals and formulations, determining the accelerated storage testing cycle and reflecting the upper limit of extreme conditions that pesticide technicals and formulations can tolerate during storage.

[0075] This application uses "54±2℃ for 14 days" as the test parameter.

[0076] The specific testing method is as follows: the sample is sealed in an ampoule and stored in a constant temperature chamber at 54±2℃ for 14 days. Then, high performance liquid chromatography is used to analyze the change in purity of the active ingredient before and after heat storage. A commercially available clethodim sample (mass content of 94.0%) is used as a control example.

[0077] The test results are shown in Table 15: Table 15. Stability test results of formulation examples 1-8 and comparative examples 1-7

[0078] Note: The sample content refers to the content of the corresponding active ingredient (clethodim) in the sample after heat storage; the decomposition rate is calculated as follows: Decomposition rate (%) = heat storage sample content / (initial sample - heat storage sample content) × 100%.

[0079] As shown in Table 15, after 14 days of accelerated storage at 54±2℃, the samples of formulations 1-8 and the control examples all showed significant decomposition. The decomposition rate of formulations 1-8 was much lower than that of formulations 1-7 and the control examples, with formulations 1 and 3 showing decomposition rates below 2%. Therefore, the clethodim solid formulation prepared in this application exhibits superior stability, and it is reasonable to infer that the formulation is not prone to decomposition during long-term storage.

[0080] Solid formulation samples of clethodim from Formulation Examples 1-8 and Comparative Examples 1-7 were selected and their physical properties were compared and tested. The test results are shown in Table 16 below: Table 16. Physical property test results of formulation examples 1-8 and formulation comparative examples 1-7

[0081] Note: In Table 16, " / " indicates that it was not detected.

[0082] Based on the test results in Table 16, the water-dispersible granules (WG) and wettable powders (WP) of clethodim prepared using the process method of this application have better physical properties and meet the physical property requirements of commercial clethodim solid formulations, indicating better commercial prospects.

[0083] The data above show that different preparation methods or formulations lead to variations in the physicochemical properties of clethodim solid formulations, resulting in significant differences in their stability. The clethodim solid formulation prepared using the method and formulation described in this application exhibits better overall performance, superior physical properties, and broad commercial prospects.

[0084] The above description is merely a preferred embodiment of this application and is not intended to limit this application in any form or substance. It should be noted that those skilled in the art can make several improvements and additions without departing from this application, and these improvements and additions should also be considered within the scope of protection of this application.

Claims

1. A method for preparing a clethodim solid dosage form, characterized in that, Includes the following steps: S1: Under solvent-free conditions, clethodim and adjuvant I are mixed to obtain solid mixture A; pesticide formulation auxiliary components are then added to solid mixture A and mixed to obtain solid mixture B; S2: Solid mixture B is pulverized, then granulated, dried and sieved to obtain clethodim solid granules; or solid mixture B is uniformly stirred and pulverized to obtain clethodim solid powder. The auxiliary agent I is selected from 1,4-butanediamine and / or 1,6-hexanediamine.

2. The preparation method according to claim 1, characterized in that, Includes the following steps: S1: Under solvent-free conditions, clethodim and adjuvant I are mixed to obtain solid mixture A; pesticide formulation auxiliary components are then added to solid mixture A and mixed to obtain solid mixture B; S2: Solid mixture B is crushed, kneaded, granulated, dried and sieved to obtain water-dispersible granules; or solid mixture B is uniformly stirred and crushed to obtain wettable powder. The auxiliary agent I is selected from 1,4-butanediamine and / or 1,6-hexanediamine.

3. The preparation method according to claim 2, characterized in that, In S2, the solid mixture B is pulverized by an ultra-micro airflow pulverizer to reduce the particle size (D90) of the material to below 20 μm.

4. The preparation method according to claim 2, characterized in that, In S1, the molar ratio of clethodim to adjuvant I is 1:0.4~0.

7.

5. The preparation method according to claim 2, characterized in that, The preparation method of S2 clethodim water-dispersible granules, wherein the drying is performed until the moisture content is as low as 3% or less.

6. The method for preparing clethodim solid dosage form according to claim 2, characterized in that, The mixing temperature of clethodim and adjuvant I in S1 is 15℃ to 85℃; and / or, the mixing time of clethodim and adjuvant I in S1 is 0.5 hours to 2.0 hours; and / or, the molar ratio of clethodim to adjuvant I in S1 is (1:0.5) to (1:0.6); and / or, the mixing method of clethodim and adjuvant I in S1 is shear stirring.

7. The preparation method according to any one of claims 1-6, characterized in that, The pesticide formulation adjuvant in S1 includes the following components: Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content: 0.0% to 89%; The percentages represent the mass percentage of each component in the solid dosage form.

8. The preparation method according to claim 7, characterized in that, The pesticide formulation adjuvant in S1 includes the following components: Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 79%; The components of the pesticide formulation auxiliary ingredients are selected from the following group: i) The wetting agent is selected from at least one of the following: dispersant, disodium sulfosuccinate monoester, and sodium dodecyl sulfate; the dispersant is selected from at least one of the following: lignin sulfonate, sodium naphthalene sulfonate formaldehyde polymer, polyoxyethylene ether phosphate, and polycarboxylate; the amount of defoamer added is 0; the filler is selected from at least one of the following: sodium sulfate, white carbon black, and kaolin. ii) The wetting agent is selected from at least one of alkyl naphthalene sulfonates, naphthalene sulfonate condensates, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonates, and sodium salt of alkyl hydroxy sulfonates; the dispersant is selected from at least one of sodium lignin sulfonate, sodium salt of 2-naphthalene sulfonate formaldehyde polymer, sodium secondary alkyl sulfonate, and polycarboxylate; the amount of defoamer added is not 0, and the defoamer is selected from at least one of polyether modified organosilicon and dimethyl silicone oil; the filler is selected from at least one of sodium sulfate, white carbon black, and kaolin.

9. A clethodim water-dispersible granule, characterized in that, Includes the following components: Clethodim 5%-80%; Additive I 4%-14%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content: 0.0% to 89%; Wherein, each percentage is a mass percentage, the adjuvant I is selected from 1,4-butanediamine and / or 1,6-hexanediamine, and the molar ratio of clethodim to adjuvant I is 1:0.4~0.

6.

10. The clethodim water-dispersible granules according to claim 9, characterized in that, The clethodim water-dispersible granules comprise the following components: Clethodim 10%-65%; Additive I 5%-10%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 79%; The components of the clethodim water-dispersible granules are selected from the following group: i) The wetting agent is selected from at least one of the following: dispersant, disodium sulfosuccinate monoester, and sodium dodecyl sulfate; the dispersant is selected from at least one of the following: lignin sulfonate, sodium naphthalene sulfonate formaldehyde polymer, polyoxyethylene ether phosphate, and polycarboxylate; the amount of defoamer added is 0; the filler is selected from at least one of the following: sodium sulfate, white carbon black, and kaolin. ii) The wetting agent is selected from at least one of alkyl naphthalene sulfonates, naphthalene sulfonate condensates, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonates, and sodium salt of alkyl hydroxy sulfonates; the dispersant is selected from at least one of sodium lignin sulfonate, sodium salt of 2-naphthalene sulfonate formaldehyde polymer, sodium secondary alkyl sulfonate, and polycarboxylate; the amount of defoamer added is not 0, and the defoamer is selected from at least one of polyether modified organosilicon and dimethyl silicone oil; the filler is selected from at least one of sodium sulfate, white carbon black, and kaolin.

11. A clethodim wettable powder, characterized in that, Includes the following components: Clethodim 5%-80%; Additive I 4%-14%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content: 0.0% to 89%; Wherein, each percentage is a mass percentage, and the adjuvant I is selected from 1,4-butanediamine and / or 1,6-hexanediamine; the molar ratio of clethodim technical to adjuvant I is 1:0.4~0.

6.

12. The clethodim wettable powder according to claim 11, characterized in that, The clethodim wettable powder comprises the following components: Clethodim 10%-65%; Additive I 5%-10%; Wetting agent 1%-9%; Dispersant 5%-12%; Defoamer 0.0%-2%; Filler content ranges from 2% to 79%; The components of the clethodim wettable powder are selected from the following group; i) The wetting agent is selected from at least one of the following: dispersant powder, disodium sulfosuccinate monoester, and sodium dodecyl sulfate; the dispersant is selected from at least one of the following: lignin sulfonate, sodium naphthalene sulfonate formaldehyde polymer, polyoxyethylene ether phosphate, and polycarboxylate; the amount of defoamer added is 0; the filler is selected from at least one of the following: sodium sulfate, white carbon black, and kaolin. ii) The wetting agent is selected from at least one of alkyl naphthalene sulfonates, naphthalene sulfonate condensates, disodium salt of alcohol ether sulfosuccinate monoester, sodium dodecyl sulfate, alkyl-substituted naphthalene sulfonates, and sodium salt of alkyl hydroxy sulfonates; the dispersant is selected from at least one of sodium lignin sulfonate, sodium salt of 2-naphthalene sulfonate formaldehyde polymer, sodium secondary alkyl sulfonate, and polycarboxylate; the amount of defoamer added is not 0, and the defoamer is selected from at least one of polyether modified organosilicon and dimethyl silicone oil; the filler is selected from at least one of sodium sulfate, white carbon black, and kaolin.

13. The application of clethodim water-dispersible granules according to claim 9 or 10, or clethodim wettable powder according to claim 11 or 12, in the control of harmful weeds.

14. A method for controlling weeds, characterized in that, Apply an effective amount of clethodim water-dispersible granules according to claim 9 or 10, or clethodim wettable powder according to claim 11 or 12, to plants, plant parts, or the environment surrounding the plants for weed control.

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