Composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl and preparation method and application thereof

Abstract

The invention relates to the field of pesticides and herbicides, in particular to a composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl as well as a preparation method and application of the composition. The composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl is prepared from the following preparation raw materials in parts by mass: 23 to 26 parts of an active component, 4 to 6 parts of a composite surfactant, 1 to 3 parts of an anti-freezing agent, 1 to 2 parts of a bio-based thickening agent, 4 to 5 parts of a synergist, 1 to 5 parts of a dispersing agent, 10 to 15 parts of an emulsifying agent and 50 to 55 parts of methyl oleate. The pesticide composition disclosed by the invention has the advantages of low toxicity, environment friendliness, cost saving and the like while improving the weeding effect, and is an efficient, safe and environment-friendly pesticide product.

Description

Technical Field

[0001] This application relates to the field of pesticide herbicides, and particularly relates to a composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, and a preparation method and application thereof. Background Art

[0002] Wheat is one of the most important food crops in the world, and its yield and sown area account for about 1 / 3 of the world's food. In crop production, weeds compete with crops for nutrients, light, water and space, seriously affecting crop yield and quality. Due to the long-term unreasonable use of herbicides, weeds have developed resistance, and the effect of controlling weeds in the field has gradually declined. In order to pursue a better control effect, usually, methods such as increasing the number of pesticide applications and increasing the dosage of pesticides are adopted, forming a vicious cycle. The mixture of herbicides can improve the application level of herbicides, improve the control effect, expand the weed control spectrum, extend the suitable application period of pesticides, reduce the dosage of pesticides and reduce phytotoxicity, which is an effective measure to promote the reduction of pesticide use and increase efficiency and delay the occurrence and development of weed resistance.

[0003] Carfentrazone-ethyl is a contact-type selective herbicide. Under the condition of light, during the process of chlorophyll biosynthesis, it inhibits protoporphyrinogen oxidase, resulting in the accumulation of toxic intermediates, thereby destroying the cell membrane of weeds and causing the leaves to dry and die quickly.

[0004] Tribenuron-methyl is a sulfonylurea post-emergence selective herbicide for wheat fields with systemic conduction. It is an inhibitor of acetolactate synthase (ALS). After foliar treatment, it can be directly absorbed by the roots, stems and leaves of weeds and conduct in vivo. It acts by inhibiting the activity of acetolactate synthase. After being damaged, the weeds show growth point necrosis, vein chlorosis, serious inhibition of plant growth, dwarfing, and finally the whole plant dies.

[0005] Fluroxypyr is a systemic post-emergence herbicide. It is quickly absorbed by plants after application, causing sensitive plants to show typical responses of hormonal herbicides, such as plant deformity and distortion. In resistant plants such as wheat, fluroxypyr can be conjugated to lose toxicity, thus having selectivity. Temperature has no effect on the final herbicidal effect, but affects the speed of its efficacy. Generally, at low temperatures, the efficacy is exerted slowly, which can cause plants to stop growing after being poisoned, but not die immediately; after the temperature rises, the plants die quickly. Its leaching in the soil is not significant, and most of it is distributed in the 0-10 cm surface soil layer. Under aerobic conditions, it is quickly degraded into non-toxic substances such as 2-pyridinol by soil microorganisms, and has a short half-life in the soil, and will not affect the next crop of broad-leaved crops.

[0006] At present, chemical herbicides are still one of the important measures for weed control. Herbicide varieties containing a single active ingredient have defects in weed control to varying degrees. After continuous use, weeds are prone to develop resistance, narrowing the weed control spectrum, and environmental pollution. Reasonable compounding of herbicides is an effective way to improve the control effect, expand the weed control spectrum, delay weed resistance, reduce environmental pollution, reduce the cost of use, and reduce herbicide residues. After experiments, the applicant found that after compounding bensulfuron-methyl, clofopyralid and mesotrione, it not only significantly improved the control effect of weeds in wheat fields, expanded the weed control spectrum, reduced the amount of medicine used, and reduced the cost of control; it also improved the safety of crops and solved a series of problems caused by the long-term use of single-component herbicides. Summary of the invention

[0007] The purpose of this application is to provide a composition containing bensulfuron-methyl, clofopyralid and mesotrione and its preparation method and application in view of the shortcomings of the current technology. The composition containing bensulfuron-methyl, clofopyralid and mesotrione prepared in this application has the advantages of synergistic effect, high prevention effect, low toxicity, reduced environmental pollution, low dosage, high stability, cost saving, etc. in preventing and controlling weeds in wheat fields. At the same time, the added composite surfactant has hydrophilic and lipophilic properties, low viscosity, good spreadability, and can make the agent better adhere to the surface of the leaves, penetrate into the inner part of the leaf tissue, and improve the weed control effect.

[0008] In the first aspect, the present application provides a composition containing bensulfuron-methyl, clofopyralid and mesotrione, using the following technical solution: A composition containing bensulfuron-methyl, flupyralid and mesotrione comprises the following raw materials by weight: 23-26 parts of active ingredients, 4-6 parts of composite surfactants, 1-3 parts of antifreeze agents, 1-2 parts of bio-based thickeners, 4-5 parts of synergists, 1-5 parts of dispersants, 10-15 parts of emulsifiers and 50-55 parts of methyl oleate; wherein the active ingredient is prepared by mixing bensulfuron-methyl, flupyralid and mesotrione in a weight ratio of 1:20:2, and the synergist is an organosilicon emulsion.

[0009] By adopting the above technical scheme, the active ingredients: bensulfuron-methyl, clofopyralid and mesotrione are the main herbicidal active ingredients. They are mixed and used in a specific mass ratio to achieve the best herbicidal effect and synergistic effect. Composite surfactant: It has hydrophilic and lipophilic properties, which can make the agent better adhere to the surface of the leaves and penetrate into the inner part of the leaf tissue, thereby improving the herbicidal effect. Antifreeze: It is used to prevent the pesticide from freezing in a low temperature environment and maintain its stability and effectiveness. Bio-based thickener: By adsorbing active ingredients and promoting their slow release, it improves the weed control effect and duration. At the same time, it can also improve the suspension rate, dispersibility and pesticide adhesion rate of the pesticide composition. Synergist: As a synergist, silicone emulsion can improve the utilization rate of the pesticide composition and the efficacy of the unit pesticide active ingredient, reduce surface tension, increase the contact area between the agent and the crop, and reduce the loss of active ingredients. Dispersant: Helps the active ingredients of the pesticide to be evenly distributed in the water, prevents precipitation or stratification, and ensures that the pesticide can maintain a stable efficacy during use. Emulsifier: It works synergistically with surfactants to improve the suspension rate, dispersibility and pesticide adhesion rate of the pesticide composition, thereby significantly improving the efficacy. Methyl oleate: As a solvent and carrier, it helps dissolve and disperse the active ingredients while providing a stable environment. The result of the joint action of these components is the formation of a highly efficient, low-toxic and environmentally friendly pesticide composition. It not only has the advantages of synergistic enhancement, high prevention effect, low toxicity, reduced environmental pollution, and low dosage, but also ensures the stability and effectiveness of the pesticide during use. By precisely controlling the proportion and quality of each component, its synergistic effect can be maximized to achieve the best weed control effect and economic benefits.

[0010] Preferably, the preparation method of the silicone emulsion is as follows: 23 parts of hydroxy silicone oil and 18 parts of amino polyether block silicone oil are mixed according to their mass fractions, stirred for 30-40 minutes, then 4 parts of XL-50 and 3 parts of XL-70 are added, the temperature is raised to 43-45°C, and the mixture is fully stirred for 18-20 minutes. 1 part of acetic acid is added, and the mixture is stirred for 20-25 minutes. Then, water is slowly dripped in while stirring, 40 parts of water are added at a dripping speed of 0.01 parts / 10s, then 1 part of acetic acid is added, and 0.5 parts of silicone defoamer are added, and the mixture is stirred for 5 minutes to obtain the silicone emulsion.

[0011] By adopting the above technical solution, the preparation method of the silicone emulsion involves multiple steps and components. The following are the specific functions of these steps and components and their combined effects in the preparation process: Mixing of hydroxy silicone oil and amino polyether block silicone oil: These two components are the main active ingredients in the preparation of the silicone emulsion. They form a stable emulsion matrix through mixing. The hydroxy silicone oil provides the stability and flexibility of the emulsion, while the amino polyether block silicone oil provides good wettability and dispersibility. Adding XL-50 and XL-70: These two isomeric alcohol ethers are used to adjust the stability, spreadability and efficacy of the emulsion. They help to adjust the viscosity and surface tension of the emulsion, making it more suitable for the application of pesticide compositions. Heating and stirring: After adding XL-50 and XL-70, the mixture is heated and stirred thoroughly. This step helps to ensure that all components are evenly mixed and promotes the occurrence of chemical reactions, thus forming a stable emulsion. Adding acetic acid and water: Acetic acid, as a neutralizing agent, helps to adjust the pH value of the emulsion to keep it within an appropriate range. At the same time, the addition of water helps to dilute the mixture and promote the formation of the emulsion. The dropping rate and addition method of water are also crucial and need to be added slowly to avoid the destruction of the emulsion. Adding silicone defoamer: Adding silicone defoamer at the final stage of emulsion preparation helps to eliminate the possible foam and ensure the stability of the emulsion. The combined effect of these steps and components is the formation of a silicone emulsion with good stability and spreadability. This emulsion can improve the utilization rate and efficacy of pesticide compositions, reduce the surface tension, increase the contact area between the agent and the crop, and reduce the loss of active ingredients. At the same time, it can form a stable oil-in-water emulsion, improve the suspension rate, dispersibility and adhesion rate of pesticide compositions, thus significantly enhancing the efficacy.

[0012] Preferably, the composite surfactant is composed of triphenylvinylphenol polyoxyethylene ether phosphate ester and an amphoteric surfactant in a mass ratio of 3:2-4.

[0013] By adopting the above technical solutions, the amphoteric surfactant has good hydrophilicity and lipophilicity, enabling the medicament to better adhere to the leaf surface and penetrate into the leaf tissue. Meanwhile, triphenylvinylphenol polyoxyethylene ether phosphate can achieve good wetting effect on the hydrophobic surface, further enhancing the permeability and spreading property of the medicament. The synergistic effect of the amphoteric surfactant and triphenylvinylphenol polyoxyethylene ether phosphate can improve the suspension rate and dispersibility of the composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, ensuring that the medicament can be evenly distributed during use and preventing precipitation or stratification. The synergistic effect of the amphoteric surfactant and triphenylvinylphenol polyoxyethylene ether phosphate can reduce the surface tension of the medicament, increase the contact area between the medicament and the crop, prolong the residence time of the liquid medicine on the plant surface, reduce the loss of the active ingredient, and thus improve the efficacy. The amphoteric surfactant can adsorb both anions and cations simultaneously, contributing to the formation of a stable water-in-oil emulsion system and ensuring the stability of the medicament during use. In summary, the composite surfactant, which is a composition composed of triphenylvinylphenol polyoxyethylene ether phosphate and amphoteric surfactant in a mass ratio of 3:2 - 4, plays a role in improving the spreading property, permeability, suspension rate, dispersibility and efficacy, and also helps to form a stable medicament system.

[0014] Preferably, the preparation method of the amphoteric surfactant includes the following steps: S41. Under nitrogen protection, add 21.34 g of dodecyl dimethyl tertiary amine into the reactor, then add 30 mL of isopropanol as a solvent. After stirring at 25 °C for 4 - 5 min, add 6.46 g of 1,3 - dichloro - 2 - propanol. After mixing evenly, heat the reaction system to 70 °C and react for 8 - 10 h. After the reaction is completed, remove the solvent by rotary evaporation and recrystallize 3 times with a mixed solvent of ethyl acetate / absolute ethanol, where the volume ratio of ethyl acetate to absolute ethanol in the mixed solvent is 15:2, to obtain a white solid. S42. Under nitrogen protection, mix 22.24 g of the white solid with 30 mL of dichloromethane at 25 °C and add it into the reactor. Then mix 5.60 g of chlorosulfonic acid with 20 mL of dichloromethane evenly and slowly add it into the reactor. After reacting for 4 - 5 h, slowly add the saturated aqueous solution of NaOH to adjust the pH to 9 - 10. After neutralization, remove the solvent by rotary evaporation, reflux in ethanol for 0.5 - 1 h, filter to remove inorganic salts, and recrystallize 3 times with acetone to obtain the amphoteric surfactant.

[0015] By adopting the above technical solution, an amphoteric surfactant with a sulfate group on the linking group was synthesized using docosyl dimethyl tertiary amine, 1,3-dichloro-2-propanol, and chlorosulfonic acid as raw materials. It can achieve wetting on the hydrophobic surface of weeds and has a high deposition efficiency, which enables the pesticide composition to be well transmitted and penetrate during application, killing weeds efficiently. The surfactant has amphoteric groups and can adsorb anions and cations simultaneously, making the emulsion in water form a stable system. Through the synergistic effect of the amphoteric surfactant and the emulsifier, the suspension rate, dispersibility, and pesticide adhesion rate of the composition containing tribenuron-methyl, fluroxypyr, and carfentrazone-ethyl are improved, thereby significantly enhancing the pesticidal efficacy.

[0016] Preferably, the preparation method of the bio-based thickener includes the following steps: S51. According to the mass parts, 80 - 85 parts of chitosan, 2 parts of citric acid, 6 parts of xanthan gum, and 12 parts of silica white are added to an ultrafine pulverizer and mixed and pulverized evenly to obtain a chitosan mother powder. S52. According to the mass parts, 100 parts of the chitosan mother powder and 20 parts of organic bentonite are added to an ultrafine pulverizer for pulverization and mixing, 15 parts of pure water are added, and granulation is carried out in an extrusion granulator, followed by grinding to obtain a bio-based thickener with a particle size of 0.02 - 0.04 mm.

[0017] By adopting the above technical solution, the bio-based thickener is obtained by mixing and pulverizing chitosan, citric acid, xanthan gum, and silica white to obtain a mother powder, and then granulating and grinding it together with organic bentonite to obtain a bio-based thickener with a particle size of 0.02 - 0.04 mm. The bio-based thickening adsorbent not only efficiently adsorbs the active ingredient but also promotes the slow dissolution of chitosan when encountering water by adding citric acid, thereby accelerating the release of the active ingredient, further improving the control effect on weeds and the persistence time. At the same time, it can also improve the suspension rate, dispersibility, and pesticide adhesion rate of the pesticide composition.

[0018] The dispersant consists of modified acrylate and fatty acid polyoxyethylene ester in a mass part ratio of 3:1 - 3.

[0019] By adopting the above technical solution, the modified acrylate has good biocompatibility and biodegradability, can form stable liposomes in water, thereby increasing the viscosity of the pesticide composition. This viscosity helps the active ingredient of the pesticide to be evenly distributed in the liquid, prevents its precipitation or stratification, and ensures that the pesticide can maintain a stable efficacy during use. At the same time, fatty acid polyoxyethylene ester, as a commonly used dispersant, can effectively reduce the surface tension, improve the suspension and dispersibility of the pesticide composition. The combined use of the modified acrylate and fatty acid polyoxyethylene ester can achieve the synergistic effect of the two. The biocompatibility and biodegradability provided by the modified acrylate help to reduce environmental pollution, and its stability in water helps to maintain the uniformity of the pesticide composition. The fatty acid polyoxyethylene ester further enhances the suspension and dispersibility of the pesticide composition through its dispersing effect, ensuring that the pesticide components can be evenly distributed in the liquid. This combined dispersant can improve the suspension rate and dispersibility of the pesticide composition, thereby increasing the pesticide adhesion rate. This means that the pesticide components are more likely to adhere to the surface of crops or weeds, thus improving the effectiveness and use efficiency of the pesticide. In summary, the combined action of the modified acrylate and fatty acid polyoxyethylene ester as dispersants in the pesticide composition is mainly reflected in improving suspension and dispersibility, achieving synergistic effects, and increasing the pesticide adhesion rate. This combined use can not only improve the performance of the pesticide composition, but also reduce environmental pollution, and is an environmentally friendly and efficient pesticide formulation design.

[0020] Preferably, the preparation method of the modified acrylate includes the following steps: S71. By mass, take 10 parts of polyethylene glycol, heat it up to 130 °C, dropwise add 1 part of octyl polyoxyethylene ether and stir for reaction for 45 - 50 min, the stirring speed is 270 r / min. After the dropping is completed, continue to keep the temperature at 110 °C for heat preservation reaction for 25 - 30 min to obtain a polyethylene glycol emulsion; S72. By mass, take 0.75 part of octyl polyoxyethylene ether and mix it with 1 part of deionized water, stir and dissolve it, then add 5 parts of methyl acrylate and 0.3 part of potassium persulfate and stir for emulsification for 40 min. Add the polyethylene glycol emulsion and heat up to 120 °C, continue to stir and react for 2 - 2.5 h. After the reaction is completed, when the reaction temperature drops to 90 °C, carry out vacuum distillation to obtain the modified acrylate.

[0021] By adopting the above technical solution, the prepared modified acrylate has good biocompatibility and biodegradability due to the introduction of polyethylene glycol. This makes the pesticide composition have less impact on the environment during use and is beneficial to environmental protection. The modified acrylate can form stable liposomes in water, thereby increasing the viscosity of the pesticide composition. This helps the active ingredient of the pesticide to be evenly distributed in the liquid, prevents it from precipitating or stratifying, and ensures that the pesticide can maintain a stable efficacy during use. It can significantly improve the suspension rate, dispersibility and pesticide adhesion rate of the pesticide composition.

[0022] Preferably, the emulsifier is composed of calcium dodecylbenzenesulfonate and alkylphenol formaldehyde resin polyoxyethylene ether in a mass ratio of 4:1 - 2.

[0023] By adopting the above technical solution, calcium dodecylbenzenesulfonate is a common anionic surfactant with good emulsifying and dispersing properties. It can form a stable emulsion in water, which helps to improve the suspension rate and dispersibility of the pesticide composition. At the same time, calcium dodecylbenzenesulfonate can also increase the viscosity of the pesticide composition, enabling it to better adhere to the leaf surface and penetrate into the leaf tissue during application. Alkylphenol formaldehyde resin polyoxyethylene ether is a non-ionic surfactant with good emulsifying and dispersing properties. It can act together with calcium dodecylbenzenesulfonate to form a stable emulsion. Alkylphenol formaldehyde resin polyoxyethylene ether can also improve the stability of the pesticide composition, preventing the active ingredient from precipitating or stratifying. The combined action between calcium dodecylbenzenesulfonate and alkylphenol formaldehyde resin polyoxyethylene ether can significantly improve the suspension rate, dispersibility and pesticide adhesion rate of the pesticide composition. This synergistic effect helps to enhance the efficacy, making the pesticide composition more efficient and environmentally friendly in controlling weeds in wheat fields. At the same time, this combination can also reduce the amount of pesticide used and reduce the impact on the environment.

[0024] Preferably, the antifreeze is ethylene glycol.

[0025] In the second aspect, the present application provides a preparation method of a composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, adopting the following technical solution: As a general technical concept, the present application also provides a preparation method of the above composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, including the following steps: S91. According to the mass parts, mix the active ingredient, composite surfactant, antifreeze, bio-based thickener, synergist, dispersant, emulsifier and methyl oleate, and pre-disperse and shear at a speed of 3000 - 3500 rpm for 30 - 40 min to obtain a mixed liquid; S92. Ultra-finely grind and pulverize the mixture, grind at a speed of 3000 rpm for 3 - 3.5 h, filter after detecting that the particle size D90 ≤ 0.7 μm to obtain a composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl.

[0026] In a third aspect, the present application provides an application of a composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, and adopts the following technical solutions: As a general technical concept, the present application also provides the above composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl for controlling weeds in corn fields, wheat fields and Cyperaceae weeds.

[0027] In summary, the beneficial technical effects of the present application are as follows: 1. Synergistic effect: Through the mixing of active ingredients in a specific ratio, the synergistic effect between tribenuron-methyl, fluroxypyr and carfentrazone-ethyl is achieved, improving the herbicidal effect.

[0028] 2. High efficiency in control: The added composite surfactant and emulsifier can make the medicament better adhere to the leaf surface and penetrate into the leaf tissue, enhancing the herbicidal control effect.

[0029] 3. Low toxicity: The modified acrylate has good biocompatibility and biodegradability, reducing environmental pollution.

[0030] 4. Cost saving: By optimizing the formula and process, the usage amount of pesticides is reduced, lowering the cost.

[0031] 5. High stability: By adding specific thickeners and emulsifiers, the stability and suspension rate of the pesticide composition are improved.

[0032] 6. Environmentally friendly: The use of silicone emulsion reduces the surface tension of the product, improves the spreading property and contact area of the medicament, reduces the loss of active ingredients, and at the same time, the use of modified acrylate also contributes to environmental protection.

[0033] 7. Improving the drug effect: Through the synergistic effect of specific surfactants and emulsifiers, the suspension rate, dispersibility and pesticide adhesion rate of the pesticide composition are improved, thus significantly enhancing the drug effect. Specific embodiments

[0034] The following will describe the implementation solutions of the present application in detail in combination with examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present application and should not be regarded as limiting the scope of the present application. For those not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. For the reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase. XL-50 and XL-70 are isomeric alcohol ether products of BASF.

[0035] In the following Examples and Preparation Examples, 1 part means 100 g.

[0036] Preparation Example 1 Preparation of silicone emulsion The preparation method of the silicone emulsion is as follows: According to the mass parts, 23 parts of hydroxyl silicone oil and 18 parts of amino polyether block silicone oil are mixed, and after stirring for 35 min, 4 parts of XL-50 and 3 parts of XL-70 are added, the temperature is raised to 44 °C, and after stirring thoroughly for 120 min, 1 part of acetic acid is added. After stirring for 23 min, water is slowly added dropwise while stirring, and 40 parts of water are added at a dropping rate of 0.01 part / 10 s. Then 1 part of acetic acid is added, and 0.5 part of silicone defoamer is added, and stirring is carried out for 5 min to obtain the silicone emulsion.

[0037] Preparation Example 2 Preparation of amphoteric surfactant The preparation method of the amphoteric surfactant includes the following steps: S41. Under nitrogen protection, 21.34 g of dodecyl dimethyl tertiary amine is added to the reactor, and then 30 mL of isopropanol is added as a solvent. After stirring at 25 °C for 5 min, 6.46 g of 1,3-dichloro-2-propanol is added. After mixing evenly, the reaction system is heated to 70 °C and reacted for 9 h. After the reaction is completed, the solvent is removed by rotary evaporation, and recrystallization is carried out 3 times with a mixed solvent of ethyl acetate / absolute ethanol, and the mixed solvent of ethyl acetate / absolute ethanol is ethyl acetate and absolute ethanol in a volume ratio of 15:2 to obtain a white solid; S42. Under nitrogen protection, 22.24 g of the white solid is mixed with 30 mL of dichloromethane at 25 °C and added to the reactor. Then 5.60 g of chlorosulfonic acid is mixed evenly with 20 mL of dichloromethane and slowly added to the reactor. After reacting for 4.5 h, a saturated aqueous solution of NaOH is slowly added to adjust the pH to 9.5. After neutralization, the solvent is removed by rotary evaporation, refluxed in ethanol for 0.7 h, the inorganic salts are removed by filtration, and recrystallization is carried out 3 times with acetone to obtain the amphoteric surfactant.

[0038] Preparation Example 3 Preparation of bio-based thickener The preparation method of the bio-based thickener includes the following steps: S51. According to the mass parts, 83 parts of chitosan, 2 parts of citric acid, 6 parts of xanthan gum and 12 parts of white carbon black are added to an ultrafine pulverizer and mixed and pulverized evenly to obtain a chitosan master powder; S52. According to the mass parts, 100 parts of the chitosan master powder and 20 parts of organic bentonite are added to an ultrafine pulverizer for pulverization and mixing, and 15 parts of pure water are added to an extrusion granulator for granulation and grinding to obtain a bio-based thickener with a particle size of 0.02 - 0.04 mm.

[0039] Preparation Example 4 Preparation method of modified acrylate, comprising the following steps: S71. By mass fraction, take 10 parts of polyethylene glycol, heat it up to 130 °C, dropwise add 1 part of octyl polyoxyethylene ether and stir for reaction for 48 min, with a stirring speed of 270 r / min. After the dropping is completed, continue to keep the temperature for reaction at 110 °C for 28 min to obtain a polyethylene glycol emulsion; S72. By mass fraction, take 0.75 part of octyl polyoxyethylene ether and mix it with 1 part of deionized water. After stirring and dissolving, add 5 parts of methyl acrylate and 0.3 part of potassium persulfate and stir for emulsification for 40 min. Add the polyethylene glycol emulsion and heat up to 120 °C, and continue to stir for reaction for 2.2 h. After the reaction is completed, when the reaction temperature drops to 90 °C, carry out vacuum distillation to obtain the modified acrylate. Example 1

[0040] A composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, by mass fraction, comprising the following preparation raw materials: 23 parts of active ingredient, 4 parts of composite surfactant, 1 part of antifreeze, 1 part of bio-based thickener, 4 parts of silicone emulsion, 1 part of dispersant, 10 parts of emulsifier, 50 parts of methyl oleate; wherein, the active ingredient is prepared by mixing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl in a mass ratio of 1:20:2, the composite surfactant is composed of triphenylvinylphenol polyoxyethylene ether phosphate and amphoteric surfactant in a mass ratio of 3:2, the dispersant is composed of modified acrylate and fatty acid polyoxyethylene ester in a mass ratio of 3:1, and the emulsifier is composed of calcium dodecylbenzenesulfonate and alkylphenol formaldehyde resin polyoxyethylene ether in a mass ratio of 4:1; The preparation method of the above composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, comprising the following steps: S91. By mass fraction, mix the active ingredient, composite surfactant, antifreeze, bio-based thickener, silicone emulsion, dispersant, emulsifier and methyl oleate, and pre-disperse and shear at a speed of 3000 rpm for 40 min to obtain a mixed solution; S92. Carry out ultrafine grinding and pulverization on the mixed solution, grind at a speed of 3000 rpm for 3 h, filter after detecting that the particle size D90 is 0.7 μm to obtain the composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl. Example 2

[0041] A composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, by mass, comprises the following preparation raw materials: 26 parts of active ingredients, 6 parts of composite surfactant, 3 parts of antifreeze, 2 parts of bio-based thickener, 5 parts of silicone emulsion, 5 parts of dispersant, 15 parts of emulsifier, 55 parts of methyl oleate; wherein, the active ingredients are prepared by mixing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl in a mass ratio of 1:20:2, the composite surfactant is composed of triphenylvinylphenol polyoxyethylene ether phosphate and amphoteric surfactant in a mass ratio of 3:4, the dispersant is composed of modified acrylate and fatty acid polyoxyethylene ester in a mass ratio of 3:3, and the emulsifier is composed of calcium dodecylbenzenesulfonate and alkylphenol formaldehyde resin polyoxyethylene ether in a mass ratio of 4:2; The preparation method of the above composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl comprises the following steps: S91. According to the mass parts, mix the active ingredients, composite surfactant, antifreeze, bio-based thickener, silicone emulsion, dispersant, emulsifier and methyl oleate, and pre-disperse and shear at a speed of 3500 rpm for 30 min to obtain a mixed solution; S92. Ultrafinely grind and crush the mixed solution, grind at a speed of 3000 rpm for 3.5 h, filter after detecting that the particle size D90 is 0.6 μm to obtain the composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl. Example 3

[0042] A composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, by mass, comprises the following preparation raw materials: 25 parts of active ingredients, 5 parts of composite surfactant, 2 parts of antifreeze, 1.5 parts of bio-based thickener, 4.5 parts of silicone emulsion, 3 parts of dispersant, 12 parts of emulsifier, 53 parts of methyl oleate; wherein, the active ingredients are prepared by mixing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl in a mass ratio of 1:20:2, the composite surfactant is composed of triphenylvinylphenol polyoxyethylene ether phosphate and amphoteric surfactant in a mass ratio of 3:3, the dispersant is composed of modified acrylate and fatty acid polyoxyethylene ester in a mass ratio of 3:2, and the emulsifier is composed of calcium dodecylbenzenesulfonate and alkylphenol formaldehyde resin polyoxyethylene ether in a mass ratio of 4:1.5; The preparation method of the above composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl comprises the following steps: S91. According to the mass parts, mix the active ingredients, composite surfactant, antifreeze, bio-based thickener, silicone emulsion, dispersant, emulsifier and methyl oleate, and pre-disperse and shear at a speed of 3300 rpm for 35 min to obtain a mixed solution; S92. The mixed solution was subjected to ultrafine grinding and pulverization, ground at a speed of 3000 rpm for 3.2 h, filtered after detecting that the particle size D90 was 0.6 μm, and a composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl was obtained.

[0043] Comparative Example 1 Same as Example 3, except that an equal amount of organic bentonite with a particle size of 0.02 - 0.04 mm was used instead of the bio-based thickener.

[0044] Comparative Example 2 Same as Example 3, except that the composite surfactant was triphenylvinylphenol polyoxyethylene ether phosphate.

[0045] Comparative Example 3 Same as Example 3, except that the composite surfactant was an amphoteric surfactant.

[0046] Comparative Example 4 Same as Example 3, except that the dispersant was a modified acrylate.

[0047] Comparative Example 5 Same as Example 3, except that the dispersant was fatty acid polyoxyethylene ester.

[0048] Comparative Example 6 Same as Example 3, except that the emulsifier was calcium dodecylbenzenesulfonate.

[0049] Comparative Example 7 Same as Example 3, except that the emulsifier was alkylphenol formaldehyde resin polyoxyethylene ether.

[0050] 1. Performance Testing Samples were taken from the compositions containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl prepared in Examples 1 - 3 and Comparative Examples 1 - 7 respectively, and the following tests were carried out. The test results are shown in Table 1.

[0051] Suspension rate detection: Detection was carried out according to the pesticide suspension rate determination method of GB / T14825 - 2006; Pesticide adhesion rate detection: A cover glass (2 cm × 2 cm) was vertically immersed in the compositions containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl prepared in Examples 1 - 3 and Comparative Examples 1 - 7 for 1 minute, taken out vertically and tilted at 50° and left standing for 2 minutes, and then the amount of pesticide on the cover glass was measured to calculate the pesticide adhesion rate; Low-temperature stability: The low-temperature stability test was carried out with reference to the standard of GB / T19137 - 2003, and the appearance change of the sample was observed for 3 hours; Extended area test: Add a composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl into a droplet generator to generate single pesticide droplets with a diameter of 340 - 360 μm and release them onto the leaves of Capsella bursa-pastoris, then observe under a microscope (16x focal length); use Image-proplu6.0 image processing software to measure the area of the droplets in the captured pictures.

[0052] Table 1 Performance test

[0053] 2. Field efficacy test: Field efficacy tests of the compositions containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl prepared in Examples 1 - 3 and Comparative Examples 1 - 7, and the results are shown in Table 2.

[0054] Test reference: "Guidelines for field efficacy trials of pesticides" (GB / T17980.42 - 2004); Test time and location: Xuchang, Henan, March 2024; The test crop is wheat, the control object is common weeds in wheat fields, and the medicine is applied at the 2 - 4 leaf stage of the weeds; The test field is flat, the soil is loam, with medium fertility and a pH value of 7.3. A blank control is set, with 4 replicates for each treatment and 20 m for each plot 2 , and the different treatment plots of the test are randomly arranged in blocks. The conventional spraying method is used, and the dosage of the composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl is 10 g.a.i / hm 2 , and it is sprayed after dilution with water.

[0055] Investigation method: On the day of treatment, record the weed species, growth stage of the main weeds, growth stage and coverage of wheat, etc. in each plot; 7 days after treatment, visually observe the control situation; conduct a fresh weight investigation of the weeds 21 days after application of the medicine.

[0056] Efficacy calculation method: Control effect of fresh matter weight (%) = (fresh weight of weeds in the blank control area - fresh weight of weeds in the treatment area) × 100 / fresh weight of weeds in the blank control area; Crop safety investigation: Observe whether there is phytotoxicity of the medicine to wheat, record the type and degree of phytotoxicity, and grade the phytotoxicity of each plot according to the method of phytotoxicity grading; Grading standard: Grade 1: Wheat grows normally without any damage symptoms; Grade 2: Slight phytotoxicity to wheat, with less than 10% phytotoxicity; Grade 3: Moderate phytotoxicity to wheat, which can recover later without affecting the yield; Grade 4: Severe phytotoxicity to wheat, difficult to recover, resulting in yield reduction; Grade 5: Severe phytotoxicity to wheat, unable to recover, resulting in obvious yield reduction or complete crop failure. At the same time, accurately describe the phytotoxicity symptoms of wheat and record the growth status of wheat in all cases.

[0057] Results and Analysis Field investigations found that the main dicotyledonous weeds in wheat fields were Descurainia sophia, Capsella bursa-pastoris, Galium aparine, Stellaria media, Portulaca oleracea, and Cirsium setosum.

[0058] Table 2 Field efficacy test results of the composition containing tribenuron-methyl, fluroxypyr, and carfentrazone

[0059] Analyzing the data in Table 1 and Table 2, it can be seen that: 1) The compositions containing tribenuron-methyl, fluroxypyr, and carfentrazone prepared in Examples 1 - 3 have the advantages of synergistic effect, high control efficacy, low toxicity, reduced environmental pollution, low dosage, high stability, and cost savings in controlling weeds in wheat fields. They also have excellent suspension rate, dispersibility, pesticide adhesion rate, and weed control efficacy.

[0060] 2) Through the performance comparison and analysis of the compositions containing tribenuron-methyl, fluroxypyr, and carfentrazone prepared in Example 3 and Comparative Example 1, it is shown that the bio-based thickener prepared in this application is obtained by mixing and pulverizing chitosan, citric acid, xanthan gum, and silica white to obtain a mother powder, and then granulating and grinding it with organic bentonite to obtain a bio-based thickener with a particle size of 0.02 - 0.04 mm. The bio-based thickening adsorbent not only efficiently adsorbs the active ingredients, but also promotes the slow dissolution of chitosan when encountering water by adding citric acid, thereby accelerating the release of the active ingredients, further improving the control efficacy and persistence time against weeds. At the same time, it can also improve the suspension rate, dispersibility, and pesticide adhesion rate of the pesticide composition.

[0061] 3) Comparative analysis of the performance of the compositions containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl prepared in Example 3 and Comparative Examples 2-3 shows that the composite surfactant consists of triphenylvinylphenol polyoxyethylene ether phosphate and an amphoteric surfactant in a mass ratio of 3:3. The amphoteric surfactant has good hydrophilicity and lipophilicity, enabling the medicament to better adhere to the leaf surface and penetrate into the leaf tissue. At the same time, triphenylvinylphenol polyoxyethylene ether phosphate can achieve good wetting on the hydrophobic surface, further enhancing the permeability and spreading property of the medicament. The synergistic effect of the amphoteric surfactant and triphenylvinylphenol polyoxyethylene ether phosphate can improve the suspension rate and dispersibility of the composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, ensuring that the medicament can be evenly distributed during use and preventing precipitation or stratification. The synergistic effect of the amphoteric surfactant and triphenylvinylphenol polyoxyethylene ether phosphate can reduce the surface tension of the medicament, increase the contact area between the medicament and the crop, prolong the residence time of the liquid medicine on the plant surface, reduce the loss of active ingredients, and thus improve the drug efficacy. In summary, the composition in which the composite surfactant consists of triphenylvinylphenol polyoxyethylene ether phosphate and an amphoteric surfactant in a mass ratio of 3:3 plays a role in improving the spreading property, permeability, suspension rate, dispersibility and drug efficacy, and also helps to form a stable medicament system.

[0062] 4) Comparative analysis of the performance of the compositions containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl prepared by combining Example 3 with Comparative Examples 4 - 5 shows that the dispersant consists of a modified acrylate and a fatty acid polyoxyethylene ester in a mass ratio of 3:2. The modified acrylate has good biocompatibility and biodegradability and can form stable liposomes in water, thereby increasing the viscosity of the pesticide composition. This viscosity helps the active ingredients of the pesticide to be evenly distributed in the liquid, preventing precipitation or stratification and ensuring stable efficacy during pesticide use. At the same time, as a commonly used dispersant, the fatty acid polyoxyethylene ester can effectively reduce the surface tension and improve the suspension and dispersibility of the pesticide composition. The combined use of the modified acrylate and the fatty acid polyoxyethylene ester can achieve their synergistic effect. The biocompatibility and biodegradability provided by the modified acrylate help reduce environmental pollution, and its stability in water helps maintain the uniformity of the pesticide composition. The fatty acid polyoxyethylene ester further enhances the suspension and dispersibility of the pesticide composition through its dispersing effect, ensuring that the pesticide ingredients can be evenly distributed in the liquid. This combined dispersant can improve the suspension rate and dispersibility of the pesticide composition, thereby increasing the pesticide adhesion rate. This means that the pesticide ingredients are more likely to adhere to the surface of crops or weeds, thus improving the effectiveness and usage efficiency of the pesticide. In summary, the combined effects of the modified acrylate and the fatty acid polyoxyethylene ester as dispersants in the pesticide composition are mainly reflected in improving suspension and dispersibility, achieving synergistic effects and increasing the pesticide adhesion rate, etc.

[0063] 5) Comparative analysis of the performance of the compositions containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl prepared by combining Example 3 with Comparative Examples 6 - 7 shows that the emulsifier consists of calcium dodecylbenzenesulfonate and an alkylphenol formaldehyde resin polyoxyethylene ether in a mass ratio of 4:1.5. By virtue of their combined effects, it can significantly improve the suspension rate, dispersibility and pesticide adhesion rate of the pesticide composition. This synergistic effect helps to enhance the efficacy, making the pesticide composition more efficient and environmentally friendly in controlling weeds in wheat fields. At the same time, this combination can also reduce the amount of pesticide used and reduce the impact on the environment.

[0064] The above examples are only used to explain the technical solutions of the present application rather than limit them. Although the above examples have specifically described the present application, those skilled in the art should understand that modifications or equivalent replacements can still be made to the specific embodiments of the present invention. Any modification and equivalent replacement without departing from the spirit and scope of the present application shall be covered by the protection scope of the present application.

Claims

1. A composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl, characterized in that, By mass parts, it includes the following preparation raw materials: 23-26 parts of active ingredient, 4-6 parts of composite surfactant, 1-3 parts of antifreeze, 1-2 parts of bio-based thickener, 4-5 parts of synergist, 1-5 parts of dispersant, 10-15 parts of emulsifier, and 50-55 parts of methyl oleate; wherein, the active ingredient is prepared by mixing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl in a mass ratio of 1:20:2, and the synergist is an organosilicon emulsion; The preparation method of the organosilicon emulsion is as follows: According to mass parts, 23 parts of hydroxy silicone oil and 18 parts of amino polyether block silicone oil are mixed, stirred for 30-40 min, then 4 parts of XL-50 and 3 parts of XL-70 are added, the temperature is raised to 43-45 °C, stirred thoroughly for 18-20 min, 1 part of acetic acid is added, stirred for 20-25 min, then water is slowly dropped in while stirring, 40 parts of water are added at a dropping rate of 0.01 part / 10 s, 1 part of acetic acid is added again, and 0.5 part of organosilicon defoamer is added, stirred for 5 min to obtain the organosilicon emulsion.

2. The composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl according to claim 1, characterized in that, The composite surfactant consists of triphenylvinylphenol polyoxyethylene ether phosphate and an amphoteric surfactant in a mass ratio of 3:2-4.

3. The composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl according to claim 2, characterized in that, The preparation method of the amphoteric surfactant includes the following steps: S41. Under nitrogen protection, 21.34 g of dodecyl dimethyl tertiary amine is added to the reactor, then 30 mL of isopropanol is added as a solvent, stirred at 25 °C for 4-5 min, 6.46 g of 1,3-dichloro-2-propanol is added, after mixing evenly, the reaction system is heated to 70 °C and reacted for 8-10 h. After the reaction is completed, the solvent is removed by rotary evaporation, and recrystallized 3 times with a mixed solvent of ethyl acetate / absolute ethanol, and the volume ratio of ethyl acetate to absolute ethanol in the mixed solvent of ethyl acetate / absolute ethanol is 15:2 to obtain a white solid; S42. Under nitrogen protection, 22.24 g of the white solid is mixed with 30 mL of dichloromethane at 25 °C and added to the reactor. Then, 5.60 g of chlorosulfonic acid is mixed evenly with 20 mL of dichloromethane and slowly added to the reactor. After reacting for 4-5 h, a saturated aqueous solution of NaOH is slowly added to adjust the pH to 9-10. After neutralization, the solvent is removed by rotary evaporation, refluxed in ethanol for 0.5-1 h, the inorganic salts are removed by filtration, and recrystallized 3 times with acetone to obtain the amphoteric surfactant.

4. A composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl according to claim 1, characterized in that The preparation method of the bio-based thickener includes the following steps: S51. According to mass parts, 80-85 parts of chitosan, 2 parts of citric acid, 6 parts of xanthan gum and 12 parts of white carbon black are added to a superfine pulverizer and mixed and pulverized evenly to obtain a chitosan master powder; S52. According to mass parts, 100 parts of the chitosan master powder and 20 parts of organic bentonite are added to a superfine pulverizer for pulverization and mixing, 15 parts of pure water are added to an extrusion granulator for granulation and grinding to obtain a bio-based thickener with a particle size of 0.02-0.04 mm.

5. The composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl according to claim 1, characterized in that, The dispersant consists of modified acrylate and fatty acid polyoxyethylene ester in a mass ratio of 3:1-3.

6. The composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl according to claim 5, characterized in that, The preparation method of the modified acrylate includes the following steps: S71. By mass fraction, take 10 parts of polyethylene glycol, heat it up to 130 °C, dropwise add 1 part of octyl polyoxyethylene ether, stir and react for 45 - 50 min, with a stirring speed of 270 r / min. After the dropping is completed, continue to keep the temperature at 110 °C and react for 25 - 30 min to obtain a polyethylene glycol emulsion; S72. By mass fraction, take 0.75 part of octyl polyoxyethylene ether and mix it with 1 part of deionized water. After stirring and dissolving, add 5 parts of methyl acrylate and 0.3 part of potassium persulfate, stir and emulsify for 40 min, add the polyethylene glycol emulsion, heat up to 120 °C, and continue to stir and react for 2 - 2.5 h. After the reaction is completed, when the reaction temperature drops to 90 °C, carry out vacuum distillation to obtain a modified acrylate.

7. The composition containing tribenuron-methyl, fluroxypyr and carfentrazone-ethyl according to claim 1, characterized in that, The emulsifier consists of calcium dodecylbenzenesulfonate and alkylphenol formaldehyde resin polyoxyethylene ether in a mass fraction ratio of 4:1 - 2; the antifreeze agent is ethylene glycol.

8. A method for preparing a composition comprising tribenuron-methyl, fluroxypyr and carfentrazone-ethyl according to any one of claims 1-7, characterized in that, It includes the following steps: S91. By mass fraction, mix the active ingredient, composite surfactant, antifreeze agent, bio - based thickener, synergist, dispersant, emulsifier and methyl oleate, and pre - disperse and shear at a speed of 3000 - 3500 rpm for 30 - 40 min to obtain a mixed solution; S92. Ultra - micro grind and crush the mixed solution, grind it at a speed of 3000 rpm for 3 - 3.5 h, filter it after detecting that the particle size D90 ≤ 0.7 μm to obtain a composition containing tribenuron - methyl, fluroxypyr and carfentrazone - ethyl.

9. A composition containing tribenuron - methyl, fluroxypyr and carfentrazone - ethyl according to any one of claims 1 - 7 is used for controlling weeds in corn fields, wheat fields and Cyperaceae weeds.

Images