Weeding composition containing phenoxy carboxylic acid and preparation method

Abstract

The invention belongs to the technical field of weeding compositions, and particularly relates to a weeding composition containing phenoxy carboxylic acid and a preparation method of the weeding composition. The weeding composition comprises at least one of an effective component A, an effective component B, an effective component C and a pesticide adjuvant, the effective component A comprises at least one of 2, 4-D acid, 2, 4-D salt and 2, 4-D ester; the effective component B comprises at least one of 2-methyl-4-chloro-phenoxyacetic acid, 2-methyl-4-chloro-phenoxyacetic acid salt and 2-methyl-4-chloro-phenoxyacetic acid ester; the effective component C comprises at least one of dicamba, dicamba salt and dicamba ester; the pesticide auxiliary agent comprises at least one of an effective component D, a biological source component, a solvent, a surfactant and other auxiliary agents. The weeding composition in the form of microemulsion / water aqua / soluble granules / missible oil / wettable powder / water dispersible granules is respectively prepared by different preparation methods. By combining different types of effective components, the weeding effect is enhanced, and the drug resistance is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of herbicidal compositions, and in particular relates to a herbicidal composition containing phenoxycarboxylic acids and a preparation method thereof. Background Art

[0002] Phenoxycarboxylic acid herbicides are widely used in agriculture and have attracted much attention due to their good control effect on a variety of broadleaf weeds. However, the use of a single phenoxycarboxylic acid herbicide can easily lead to problems such as increased weed resistance and decreased efficacy. Therefore, how to enhance the weed control effect and reduce resistance by combining different types of active ingredients is a hot topic in current research. Summary of the invention

[0003] The purpose of the present invention is to provide a herbicidal composition containing phenoxycarboxylic acids and a preparation method thereof. The present invention enhances the herbicidal effect and reduces drug resistance by combining different types of active ingredients.

[0004] In order to achieve the above-mentioned object and other related objects, the present invention provides the following technical solutions:

[0005] In a first aspect, the present invention provides a herbicidal composition containing phenoxycarboxylic acids, the herbicidal composition comprising at least one of an active ingredient A, an active ingredient B, an active ingredient C, and a pesticide adjuvant;

[0006] The active ingredient A comprises at least one of 2,4-D acid, 2,4-D salt, 2,4-D ester, and a salt or ester of 2,4-D acid;

[0007] The active ingredient B comprises at least one of 2-methyl-4-chloro-1-acid, 2-methyl-4-chloro-1-acid salt, 2-methyl-4-chloro-1-acid ester, and salt or ester of 2-methyl-4-chloro-1-acid;

[0008] The active ingredient C includes at least one of dicamba, dicamba salt, and dicamba ester;

[0009] The pesticide adjuvant includes at least one of an active ingredient D, a biogenic component, a solvent, a surfactant, and other adjuvants; the other adjuvants include at least one of nonylphenol polyoxyethylene ether, dimethylamine, sodium sulfate of fatty alcohol polyoxyethylene ether, polydimethylsiloxane, castor oil polyoxyethylene ether, ammonium sulfate, glucose, No. 150 solvent oil, styrene phenol polyoxyethylene ether, calcium dodecylbenzene sulfonate, sodium methylene bisnaphthalene sulfonate, pull open powder, diatomaceous earth, ammonia water, white carbon black, ammonium sulfate, calcium dodecylbenzene sulfonate, and sodium lignin sulfonate; the active ingredient D includes at least one of gentianine and sodium acetate.

[0010] In one embodiment, the biogenic component includes at least one of tea saponin and lotus seed extract; the solvent includes at least one of water and isopropyl alcohol; and the surfactant includes a silicone surfactant.

[0011] In one embodiment, the 2,4-D acid includes at least one of 2,4-D, 2,4-D propionic acid, and 2,4-D butyric acid; the salt of 2,4-D acid or the salt in the 2,4-D salt includes at least one of ammonium salt, dimethylamine salt, triethylamine salt, isopropylamine salt, sodium salt, and potassium salt; the ester of 2,4-D acid or the ester in the 2,4-D ester includes at least one of ethyl ester, butyl ester, isobutyl ester, and isooctyl ester.

[0012] In one embodiment, the 2-methyl-4-chloro-1-ol acid includes at least one of 2-methyl-4-chloro-1-ol, 2-methyl-4-chloro-propionic acid, and 2-methyl-4-chloro-butyric acid; the salt of 2-methyl-4-chloro-1-ol or the salt in the salt of 2-methyl-4-chloro-1-ol includes at least one of ammonium salt, dimethylamine salt, triethylamine salt, isopropylamine salt, sodium salt, and potassium salt; the ester of 2-methyl-4-chloro-1-ol or the ester in the ester of 2-methyl-4-chloro-1-ol includes at least one of ethyl ester, butyl ester, isobutyl ester, and isooctyl ester.

[0013] In one embodiment, the salt in the dicamba salt includes at least one of ammonium salt, dimethylamine salt, triethylamine salt, isopropylamine salt, sodium salt, and potassium salt; the ester in the dicamba ester includes at least one of ethyl ester, butyl ester, isobutyl ester, and isooctyl ester.

[0014] In one embodiment, the formulation of the herbicidal composition includes at least one of microemulsion, aqueous solution, soluble granules, emulsifiable concentrate, wettable powder, water dispersible granules, aqueous suspension, oil suspension, microcapsule granules, microcapsule suspension, and spray.

[0015] It should be noted that in the present application, different dosage forms have different preparation methods, and the preparation methods of different dosage forms are provided below.

[0016] In a second aspect, a method for preparing the herbicidal composition containing phenoxycarboxylic acids is provided, comprising the following steps:

[0017] Dissolving PLGA in dichloromethane, adding active ingredient A, active ingredient B, and active ingredient C to obtain an active ingredient solution;

[0018] While heating and stirring, inject the active ingredient solution into the aqueous solution of polyvinyl alcohol, stir and emulsify, let stand, and after the solvent evaporates completely, centrifuge, collect the particles, wash, and dry to obtain the core;

[0019] The core is dispersed in a solvent, acrylamide monomer and initiator are added, protective gas is introduced, and the reaction is carried out in a water bath. After the reaction is completed, the reaction is centrifuged, washed, and dried to obtain particles coated with the intermediate layer;

[0020] The particles coated with the middle layer are dispersed in a solvent, acrylic acid monomer and a cross-linking agent are added, the pH is adjusted, and the mixture is stirred under heating for reaction. After the reaction is completed, the mixture is centrifuged, washed, and dried to obtain particles coated with the outer layer;

[0021] Add at least one of the active ingredient D, the biogenic ingredient and the surfactant to the solvent, stir until completely dissolved to form a uniform solution, add the outer-layer coated particles and other adjuvants, stir to obtain an emulsion, add the solvent to the emulsion, stir, and homogenize to obtain a herbicidal composition in the form of a microemulsion.

[0022] It should be noted that PLGA can be used as a drug carrier to control drug release.

[0023] In a third aspect, a method for preparing the herbicidal composition containing phenoxycarboxylic acids is provided, comprising the following steps:

[0024] The active ingredient A, the active ingredient B, the active ingredient C, the solvent and other adjuvants are mixed and stirred, heated, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered, and then other adjuvants, the active ingredient D and at least one of the biological source ingredients are added, and stirred evenly to prepare an aqueous herbicidal composition.

[0025] In a fourth aspect, a method for preparing the herbicidal composition containing phenoxycarboxylic acids is provided, comprising the following steps:

[0026] The active ingredient A, the active ingredient B, the active ingredient C, the solvent and other adjuvants are mixed and stirred, heated, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered, and then other adjuvants, the active ingredient D, and at least one of the biological source components are added, stirred evenly, and the evenly mixed solution is extruded into granules and dried to obtain a herbicidal composition in the form of soluble granules.

[0027] In a fifth aspect, a method for preparing the herbicidal composition containing phenoxycarboxylic acids is provided, comprising the following steps:

[0028] Active ingredient A, active ingredient B and active ingredient C are added into a reaction container, and then other adjuvants, active ingredient D and at least one of the biological source ingredients are added, and stirred evenly to obtain a herbicidal composition in the form of emulsifiable concentrate.

[0029] In a sixth aspect, a method for preparing the herbicidal composition containing phenoxycarboxylic acids is provided, comprising the following steps:

[0030] Active ingredient A, active ingredient B and active ingredient C are added into a reaction container, and then other adjuvants, active ingredient D and at least one of biological source ingredients are added, mixed evenly, and crushed to less than 44 microns to obtain a wettable powder herbicidal composition.

[0031] In a seventh aspect, a method for preparing the herbicidal composition containing phenoxycarboxylic acids is provided, comprising the following steps:

[0032] Active ingredient A, active ingredient B, active ingredient C and other adjuvants are added into a reaction container and mixed, and then other adjuvants, active ingredient D and at least one of the biological source ingredients are added, mixed evenly, crushed to less than 44 microns, extruded into granules, and dried to obtain a herbicidal composition of water dispersible granules.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. The components of the herbicidal composition of the present application include: active ingredient A, active ingredient B, active ingredient C, and pesticide adjuvants, and the pesticide adjuvants include active ingredient D, biological source ingredients, solvents, surfactants, and other adjuvants. Specifically:

[0035] (1) Selecting a multi-component compound can improve the broad-spectrum of the herbicidal composition. The selected active ingredients are easily decomposed under natural conditions, reducing pollution to the environment. The herbicidal composition has low environmental toxicity. Through the combination of multiple action mechanisms, the risk of weed resistance is reduced.

[0036] (2) The three herbicides, active ingredient A, active ingredient B, and active ingredient C, act on different targets respectively. Their combined use enhances the comprehensive herbicidal effect on various weeds, while also reducing the drug resistance that may be caused by a single ingredient.

[0037] (3) Active ingredient D includes gentianine and sodium acetate. On the basis of active ingredients A, B, and C, the present application further introduces a fourth active ingredient D, which can increase the broad spectrum of the weed control effect. The multi-level composition design can provide more efficient solutions for different types of weeds, including stubborn weeds that are difficult to control. Gentianine, as an alkaloid, can inhibit the germination and early growth of weed seeds and reduce the reproductive capacity of weeds. Sodium acetate can change the pH value inside weed cells, disrupt cell metabolism, and cause cell death. With the synergistic effect of other active ingredients and pesticide adjuvants, gentianine and sodium acetate improve the penetration and conduction effect of the agent in the weed body, thereby enhancing the overall weed control efficacy.

[0038] (4) Biosource ingredients include tea saponin and lotus seed extract. Tea saponin is a natural plant extract that can destroy the wax layer on the epidermis of weeds, making weeds more sensitive to the external environment and enhancing the effects of other chemical ingredients. Lotus seed extract contains a variety of bioactive substances that can inhibit weed growth, enhance soil health, and reduce weed recurrence. The synergistic effect of tea saponin and lotus seed extract with active ingredients and pesticide adjuvants improves the overall permeability and utilization rate of the pesticide, reduces the amount of pesticide used, and improves the weed control effect.

[0039] (5) Surfactants can enhance the wettability and permeability of the pesticide solution on the surface of weed leaves. Solvents help dissolve and evenly distribute the active ingredients, ensuring the stability of the pesticide. Other adjuvants can increase the activity of the pesticide in the weeds, making the efficacy appear faster; they can also enhance the permeability of the pesticide, allowing other active ingredients to enter the weeds more quickly, thus playing a synergistic role.

[0040] 2. The present application provides methods for preparing herbicidal compositions of various dosage forms, thereby improving the specificity, specificity and pertinence of the preparation methods.

[0041] (1) Herbicidal compositions in the form of microemulsions:

[0042] 1) The core part is composed of PLGA coated particles. The particles are obtained by dissolving active ingredients A, B and C in dichloromethane and then emulsifying. PLGA effectively loads or encapsulates these three herbicidal active ingredients. The high shear force and appropriate stirring speed during the emulsification process ensure that the particle size is uniform and a stable core structure is formed. By utilizing the biodegradability and controlled release of PLGA, the release rate of the herbicidal active ingredients in the environment can be effectively controlled, the efficacy time can be extended, and the potential toxicity to crops and the environment can be reduced.

[0043] 2) The middle layer uses N-isopropylacrylamide monomer, which exhibits reversible sol-gel transition characteristics at a specific temperature. By performing a polymerization reaction at a suitable temperature, PNIPAM is coated on the outer layer of the inner core, forming a layer of thermosensitive polymer shell on the surface of the inner core, forming a temperature-responsive middle layer. This coating can respond to temperature changes and control the release of active ingredients. Under high temperature conditions, the polymer shell undergoes a phase change, opening the release channel and releasing the active ingredients faster; under low temperature conditions, the shell closes, slowing down the release rate of the active ingredients.

[0044] 3) The outer layer uses a copolymer of acrylic acid and N,N'-methylenebisacrylamide, which exhibits good stability and sustained release properties under low pH conditions. The coating process of the outer layer further enhances the physical stability of the particles and provides an additional regulatory mechanism for drug release. The multi-layer controlled release mechanism effectively combines the regulation of sustained release, temperature and pH, making the herbicide have better adaptability and release control under different environmental conditions.

[0045] 4) The coated nanoparticles are dispersed in silicone surfactant and isopropanol, and then stirred and homogenized at high pressure to obtain a microemulsion. Stirring and high pressure homogenization make the nanoparticles in the microemulsion more evenly distributed and smaller in particle size, thereby improving the permeability and stability of the agent and enhancing the overall weed control effect. It can also be said that the microemulsion has good stability and dispersibility, can effectively cover the surface of weeds when applying the agent, and achieves a sustained and long-lasting weed control effect by gradually releasing the active ingredients in the kernel.

[0046] (2) Herbicidal compositions in aqueous form

[0047] As an alkaline solvent, dimethylamine can not only effectively improve the solubility of the active ingredient, but also adjust the pH value of the solution and stabilize the aqueous solution of the herbicide. The improvement of solubility reduces the crystallization or precipitation of the components in the solution and improves the stability of the solution. By adding a variety of pesticide adjuvants, a multifunctional adjuvant composite system is formed. Each adjuvant plays its unique role and synergistic effect in the formula. For example: the synergistic effect of fatty alcohol polyoxyethylene ether sodium sulfate and polydimethylsiloxane can not only improve the wettability of the agent, but also form a stable drug film on the surface of the plant, which can improve the penetration efficiency of the herbicide and prolong the duration of the drug effect. The combination of the two makes the herbicide more uniform during the application process, reduces the loss of the agent, and improves the use efficiency. There is also the synergistic effect of tea saponin and lotus seed extract described above, and the synergistic effect between the active ingredients.

[0048] (3) Herbicidal compositions in the form of soluble granules:

[0049] 1) The mixed solution is made into particles by extrusion granulation, and these particles contain multiple active ingredients and multiple adjuvants. This composite particle structure can ensure that each component is released synchronously during use, thereby ensuring the effectiveness and durability of the herbicide. On the surface of the particles, due to the presence of different adjuvants, a multi-level microstructure can be formed. These adjuvants work simultaneously inside and on the surface of the particles, so that the particles dissolve quickly after contact with water, and can quickly release the active ingredients of the herbicide. This multi-level structure not only improves the stability of the agent, but also effectively controls the release rate of the agent, preventing excessive active ingredients from being released at one time, resulting in drug damage or environmental pollution.

[0050] 2) By dissolving multiple active ingredients together with ammonia and water in a reactor, this method utilizes the alkaline conditions of ammonia to help dissolve the active ingredients, increase their solubility in water, and ensure uniformity in the solution. This control based on solubility and chemical environment can effectively optimize the preparation process of the herbicide. In the cooling process after dissolution, different pesticide adjuvants are gradually added to play their respective different roles. For example, castor oil polyoxyethylene ether can increase the adhesion of the herbicide on the plant surface, ammonium sulfate helps to inhibit the growth of weeds, glucose can be used as a stabilizer and / or nutrient enhancer, and tea saponin and lotus seed extract can be used as bio-source synergists. The composite use of these adjuvants is based on their chemical properties and biological activities to enhance the weed control effect through synergistic effects. The synergistic effect includes: castor oil polyoxyethylene ether synergizes with tea saponin and lotus seed extract to enhance the absorption and penetration capacity of the herbicide, ensuring that the herbicide can be absorbed by weeds faster and more evenly, thereby improving the efficacy. The combination of tea saponin and lotus seed extract, two bio-source components, and chemical adjuvants can provide a composite synergistic mechanism. Biogenic ingredients can not only increase the sensitivity of plants to herbicides, but also reduce the amount of chemical ingredients used, achieving better weed control effects while reducing toxicity to the environment. Through extrusion granulation and fluidized bed drying processes, the granules produced have high stability and good release control characteristics during application. The design of this granule can ensure that the drug effect is evenly released in the soil, avoiding local over-concentration or over-diluted, and improving the efficiency of herbicide use.

[0051] (4) Herbicidal composition in emulsifiable concentrate form

[0052] 1) No. 150 solvent oil is used as an organic solvent to effectively dissolve a variety of active ingredients. By selecting an appropriate solvent, the good solubility of the herbicide in the emulsifiable concentrate is ensured, and precipitation or stratification of the agent during storage or use is avoided. This solvent system not only improves the stability of the agent, but also increases its diffusivity and permeability during use. Styrylphenol polyoxyethylene ether and calcium dodecylbenzene sulfonate can reduce the surface tension of the system and promote the dispersion and emulsification of the components in water. Through emulsification, the oil phase can form a stable emulsion in the aqueous phase, which not only increases the stability of the herbicidal composition, but also improves the spraying uniformity of the agent. 2) By adding active ingredient D, tea saponin and lotus seed extract, a functional complex structure is formed. These synergists not only enhance the efficacy of the herbicidal composition, but also further improve the permeability and absorbability of the agent through the synergistic effect of the biologically active ingredients, ensuring that the herbicidal composition can act more effectively on weeds.

[0053] (5) Wettable powder herbicidal composition

[0054] 1) By combining the active ingredient in the form of sodium salt with the pesticide adjuvant, a multifunctional wettable powder structure is formed. This structure ensures the uniform distribution, stability and solubility of the herbicide, allowing the herbicide to quickly dissolve and disperse in water after application to exert its maximum effectiveness.

[0055] 2) The sodium salt forms of 2,4-D, 2-Methyl-4-chloro-1-4-chloride and dicamba are used as active ingredients. These sodium salt forms are more soluble in water than their corresponding acidic forms, making them easy to evenly distribute in the powder and dissolve quickly after application. The high water solubility of sodium salts ensures that the herbicide is quickly released in water and effectively acts on weeds. Sodium methylene bisnaphthalene sulfonate can help sodium salt herbicides to be evenly dispersed in water and prevent particles from agglomerating in water; the pull-opening powder not only enhances the dispersion effect, but also improves the adsorption capacity of the agent on weed leaves by reducing the surface tension of the solution. Diatomaceous earth can be used as a carrier to adsorb active ingredients and prevent powders from agglomerating during storage. The mixed materials are crushed into fine particles below 44 microns by a jet mill. This micronization process can significantly increase the surface area of ​​the powder, ensure that it dissolves faster in water, and improve the bioavailability and permeability of the herbicide. This micronized powder structure ensures the high efficiency and rapid action of the agent.

[0056] 3) Synergistic effect: The dispersing effect of sodium methylene bisnaphthalene sulfonate and the powder, combined with the adsorption effect of diatomaceous earth, ensures the uniform distribution of the herbicide in the powder and its rapid dispersion in water. Diatomaceous earth not only acts as a carrier, but also improves the fluidity of the powder, enhances the uniformity of application, and ensures uniform coverage of the agent on the soil and plant surface.

[0057] (6) Herbicidal composition of water dispersible granules

[0058] 1) By fully mixing multiple active ingredients with white carbon black, adding pesticide adjuvants, and then through air flow crushing and extrusion granulation, micron-sized composite particles are formed. This structure ensures the stability and uniform distribution of the herbicide ingredients, while improving its dispersibility in water. The particle structure of the composite particles can quickly disperse after contact with water to form a uniform suspension, ensuring uniform distribution and effective release of the agent. The granulated particles have a high density and good fluidity, which is easy to apply.

[0059] 2) As the main carrier material, white carbon black has a very high specific surface area and good adsorption capacity, and it can evenly distribute a variety of effective ingredients in the powder. The porous structure of white carbon black ensures the dispersibility of the agent in water, avoids agglomeration, and enables the water-dispersible granules to dissolve quickly and be evenly distributed when used. As a fertilizer component, ammonium sulfate has a certain auxiliary weed control effect in the composite composition of the present application, which can enhance the absorption of weeds to the herbicide. Calcium dodecylbenzene sulfonate can reduce the surface tension of water, enhance the adhesion and permeability of the agent on plant leaves, and ensure that the efficacy is fully exerted.

[0060] 3. The present application has found that there is a synergistic effect between gentianine, sodium acetate, tea saponin, and lotus seed extract by setting multiple embodiments: 1) The combination of tea saponin and lotus seed extract makes the herbicide more evenly distributed on the plant surface and more permeable. The two ingredients work together to destroy the protective layer of the plant epidermis, making the active ingredients of gentianine and herbicides more easily absorbed by the plant, thereby improving the efficacy. 2) The polyphenol compounds and tea saponin in the lotus seed extract work together, not only enhancing the permeability of the agent, but also providing a sustained release effect, so that the active ingredients can remain active for a longer time and extend the shelf life of the agent. This sustained release effect can reduce the need for multiple spraying, reduce the cost of pesticide use and the environmental burden. 3) The combination of gentianine and sodium acetate improves the chemical stability of the herbicide on the one hand, preventing the active ingredients from decomposing rapidly in the environment; on the other hand, the synergistic effect of gentianine can directly enhance the biological activity of the herbicide, by increasing the sensitivity of the plant to the herbicide, reducing the amount of the agent used, and achieving a higher weed control efficiency. 4) Tea saponin and lotus seed extract, as biosource ingredients, together with gentianine and sodium acetate, can enhance the efficacy of the drug at different levels. Tea saponin and lotus seed extract improve the permeability and absorption rate of the drug, while gentianine and sodium acetate enhance the overall effect by stabilizing and prolonging the efficacy of the drug. This multi-level synergistic effect ensures that the herbicidal combination can take effect more quickly after application and maintain its effectiveness for a longer period of time. DETAILED DESCRIPTION

[0061] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0062] Unless otherwise specified, the equipment and materials used in the examples can be easily obtained from commercial companies.

[0063] Among them, the information of some materials is shown in Table 1:

[0064] Table 1

[0065]

[0066]

[0067]

[0068] Example 1

[0069] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0070] By weight:

[0071] 1. Preparation of the kernel:

[0072] (1) 70 parts of PLGA were dissolved in 100 parts of dichloromethane, and 5 parts of active ingredient A (2,4-D), 5 parts of active ingredient B (2-Methyl-4-chlorobenzene), and 5 parts of active ingredient C (dicamba) were added successively to obtain an active ingredient solution.

[0073] (2) Add 4 parts of polyvinyl alcohol to 200 parts of deionized water and stir until completely dissolved to obtain an aqueous solution; continue stirring the aqueous solution at 30°C, preheat it in advance, and then slowly inject 50 parts of the active ingredient solution, stir it using a 10,000 rpm high-speed shear agitator. After emulsification, let it stand at room temperature for 30 minutes. After the solvent is completely evaporated, centrifuge it at 10,000 rpm for 10 minutes to collect the particles. Wash the obtained nanoparticles three times with ultrapure water, and then vacuum dry them at 40°C for 24 hours to obtain the inner core.

[0074] 2. The middle layer covers the core:

[0075] Disperse 10 parts of the core in 100 parts of water, add 20 parts of N-isopropylacrylamide monomer and 1 part of ammonium persulfate, introduce nitrogen, and keep in a 70°C water bath for 2 hours. After the reaction is completed, centrifuge at 10,000 rpm for 10 minutes, wash three times with deionized water, and then vacuum dry at 40°C for 24 hours to obtain particles coated with the intermediate layer.

[0076] 3. Outer coating particles:

[0077] 10 parts of the particles coated with the middle layer were dispersed in 100 parts of water, 15 parts of acrylic acid monomer and 1 part of N,N'-methylenebisacrylamide were added, and the mixture was stirred and reacted at 40°C for 4 hours at pH 4-5. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes, washed three times with deionized water, and then vacuum dried at 40°C for 24 hours to obtain particles coated with the outer layer.

[0078] 4. Preparation of Microemulsion

[0079] In a reaction kettle, 1 part of silicone surfactant was added to 100 parts of isopropanol, and stirred until completely dissolved to form a uniform solution. 50 parts of outer-layer coated particles and 1 part of nonylphenol polyoxyethylene ether were added, and stirred at a low speed of 300-500 rpm for 10-15 minutes to obtain an emulsion. 100 parts of water was added to the emulsion, and stirred at a high speed of 5000 rpm for 5 minutes at room temperature, and then homogenized by a high-pressure homogenizer at 500 bar for 3 times to obtain a microemulsion.

[0080] Example 2

[0081] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0082] By weight:

[0083] 1. Preparation of the kernel:

[0084] (1) 70 parts of PLGA were dissolved in 100 parts of dichloromethane, and 5 parts of active ingredient A (2,4-D), 5 parts of active ingredient B (2-Methyl-4-chlorobenzene), and 5 parts of active ingredient C (dicamba) were added successively to obtain an active ingredient solution.

[0085] (2) Add 4 parts of polyvinyl alcohol to 200 parts of deionized water and stir until completely dissolved to obtain an aqueous solution; continue stirring the aqueous solution at 30°C, preheat it in advance, and then slowly inject 50 parts of the active ingredient solution, stir it using a 10,000 rpm high-speed shear agitator. After emulsification, let it stand at room temperature for 30 minutes. After the solvent is completely evaporated, centrifuge it at 10,000 rpm for 10 minutes to collect the particles. Wash the obtained nanoparticles three times with ultrapure water, and then vacuum dry them at 40°C for 24 hours to obtain the inner core.

[0086] 2. The middle layer covers the core:

[0087] Disperse 10 parts of the core in 100 parts of water, add 20 parts of N-isopropylacrylamide monomer and 1 part of ammonium persulfate, introduce nitrogen, and keep in a 70°C water bath for 2 hours. After the reaction is completed, centrifuge at 10,000 rpm for 10 minutes, wash three times with deionized water, and then vacuum dry at 40°C for 24 hours to obtain particles coated with the intermediate layer.

[0088] 3. Outer coating particles:

[0089] 10 parts of the particles coated with the middle layer were dispersed in 100 parts of water, 15 parts of acrylic acid monomer and 1 part of N,N'-methylenebisacrylamide were added, and the mixture was stirred and reacted at 40°C for 4 hours at pH 4-5. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes, washed three times with deionized water, and then vacuum dried at 40°C for 24 hours to obtain particles coated with the outer layer.

[0090] 4. Preparation of Microemulsion

[0091] In a reaction kettle, 2 parts of gentianine are added to 100 parts of isopropanol, and stirred until completely dissolved to form a uniform solution. 1 part of silicone surfactant is added and stirring is continued. 50 parts of outer-layer coated particles and 1 part of nonylphenol polyoxyethylene ether are added, and stirring is carried out at a low speed of 300-500 rpm for 10-15 minutes to obtain an emulsion. 100 parts of water are added to the emulsion, and high-speed stirring is carried out at 5000 rpm for 5 minutes at room temperature, and then homogenized by a high-pressure homogenizer at 500 bar for 3 times to obtain a microemulsion.

[0092] Example 3

[0093] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0094] By weight:

[0095] 1. Preparation of the kernel:

[0096] (1) 70 parts of PLGA were dissolved in 100 parts of dichloromethane, and 5 parts of active ingredient A (2,4-D), 5 parts of active ingredient B (2-Methyl-4-chlorobenzene), and 5 parts of active ingredient C (dicamba) were added successively to obtain an active ingredient solution.

[0097] (2) Add 4 parts of polyvinyl alcohol to 200 parts of deionized water and stir until completely dissolved to obtain an aqueous solution; continue stirring the aqueous solution at 30°C, preheat it in advance, and then slowly inject 50 parts of the active ingredient solution, stir it using a 10,000 rpm high-speed shear agitator. After emulsification, let it stand at room temperature for 30 minutes. After the solvent is completely evaporated, centrifuge it at 10,000 rpm for 10 minutes to collect the particles. Wash the obtained nanoparticles three times with ultrapure water, and then vacuum dry them at 40°C for 24 hours to obtain the inner core.

[0098] 2. The middle layer covers the core:

[0099] Disperse 10 parts of the core in 100 parts of water, add 20 parts of N-isopropylacrylamide monomer and 1 part of ammonium persulfate, introduce nitrogen, and keep in a 70°C water bath for 2 hours. After the reaction is completed, centrifuge at 10,000 rpm for 10 minutes, wash three times with deionized water, and then vacuum dry at 40°C for 24 hours to obtain particles coated with the intermediate layer.

[0100] 3. Outer coating particles:

[0101] 10 parts of the particles coated with the middle layer were dispersed in 100 parts of water, 15 parts of acrylic acid monomer and 1 part of N,N'-methylenebisacrylamide were added, and the mixture was stirred and reacted at 40°C for 4 hours at pH 4-5. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes, washed three times with deionized water, and then vacuum dried at 40°C for 24 hours to obtain particles coated with the outer layer.

[0102] 4. Preparation of Microemulsion

[0103] In a reaction kettle, 2 parts of gentianine and 1 part of sodium acetate are added to 100 parts of isopropanol, and stirred until completely dissolved to form a uniform solution. 1 part of silicone surfactant is added and stirring is continued. 50 parts of outer-layer coated particles and 1 part of nonylphenol polyoxyethylene ether are added, and stirring is carried out at a low speed of 300-500 rpm for 10-15 minutes to obtain an emulsion. 100 parts of water are added to the emulsion, and high-speed stirring is carried out at 5000 rpm for 5 minutes at room temperature, and then homogenized by a high-pressure homogenizer at 500 bar for 3 times to obtain a microemulsion.

[0104] Example 4

[0105] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0106] By weight:

[0107] 1. Preparation of the kernel:

[0108] (1) 70 parts of PLGA were dissolved in 100 parts of dichloromethane, and 5 parts of active ingredient A (2,4-D), 5 parts of active ingredient B (2-Methyl-4-chlorobenzene), and 5 parts of active ingredient C (dicamba) were added successively to obtain an active ingredient solution.

[0109] (2) Add 4 parts of polyvinyl alcohol to 200 parts of deionized water and stir until completely dissolved to obtain an aqueous solution; continue stirring the aqueous solution at 30°C, preheat it in advance, and then slowly inject 50 parts of the active ingredient solution, stir it using a 10,000 rpm high-speed shear agitator. After emulsification, let it stand at room temperature for 30 minutes. After the solvent is completely evaporated, centrifuge it at 10,000 rpm for 10 minutes to collect the particles. Wash the obtained nanoparticles three times with ultrapure water, and then vacuum dry them at 40°C for 24 hours to obtain the inner core.

[0110] 2. The middle layer covers the core:

[0111] Disperse 10 parts of the core in 100 parts of water, add 20 parts of N-isopropylacrylamide monomer and 1 part of ammonium persulfate, introduce nitrogen, and keep in a 70°C water bath for 2 hours. After the reaction is completed, centrifuge at 10,000 rpm for 10 minutes, wash three times with deionized water, and then vacuum dry at 40°C for 24 hours to obtain particles coated with the intermediate layer.

[0112] 3. Outer coating particles:

[0113] 10 parts of the particles coated with the middle layer were dispersed in 100 parts of water, 15 parts of acrylic acid monomer and 1 part of N,N'-methylenebisacrylamide were added, and the mixture was stirred and reacted at 40°C for 4 hours at pH 4-5. After the reaction was completed, the mixture was centrifuged at 10000 rpm for 10 minutes, washed three times with deionized water, and then vacuum dried at 40°C for 24 hours to obtain particles coated with the outer layer.

[0114] 4. Preparation of Microemulsion

[0115] In a reaction kettle, 2 parts of gentianine and 1 part of sodium acetate are added to 100 parts of isopropanol, and stirred until completely dissolved to form a uniform solution. 0.5 parts of tea saponin and 0.5 parts of lotus seed extract are gradually added to the solution, and stirring is continued. 1 part of silicone surfactant is added, and stirring is continued. 50 parts of outer-layer coated particles and 1 part of nonylphenol polyoxyethylene ether are added, and stirring is carried out at a low speed of 300-500rpm for 10-15 minutes to obtain an emulsion. 100 parts of water are added to the emulsion, and high-speed stirring is carried out at 5000rpm for 5 minutes at room temperature, and then homogenization is carried out 3 times by a high-pressure homogenizer at 500bar to obtain a microemulsion.

[0116] Example 5

[0117] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0118] By weight:

[0119] Add 8 parts of 2,4-D, 30 parts of 2-Methyl-4-chloro-4-yl chloride, 4 parts of dicamba, 30 parts of water and 23 parts of dimethylamine (40%) into a reaction kettle respectively, turn on the stirring device, slowly heat up to 50-60°C, dissolve until transparent, gradually cool down to 30-40°C during the dissolution process, then add 8 parts of fatty alcohol polyoxyethylene ether sodium sulfate and 1 part of polydimethylsiloxane, stir evenly, and prepare an aqueous solution.

[0120] Example 6

[0121] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0122] By weight:

[0123] Add 8 parts of 2,4-D, 30 parts of 2-Methyl-4-chloro-4-yl chloride, 4 parts of dicamba, 30 parts of water and 23 parts of dimethylamine (40%) into a reaction kettle respectively, turn on the stirring device, slowly heat up to 50-60°C, and dissolve until transparent. During the dissolution process, gradually cool down to 30-40°C, then add 8 parts of fatty alcohol polyoxyethylene ether sodium sulfate, 1 part of polydimethylsiloxane, and 1 part of gentianine, stir evenly to prepare an aqueous solution.

[0124] Example 7

[0125] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0126] By weight:

[0127] Add 8 parts of 2,4-D, 30 parts of 2-Methyl-4-chloro-4-yl chloride, 4 parts of dicamba, 30 parts of water and 23 parts of dimethylamine (40%) into a reaction kettle respectively, turn on the stirring device, slowly heat up to 50-60°C, dissolve until transparent, gradually cool down to 30-40°C during the dissolution process, then add 8 parts of fatty alcohol polyoxyethylene ether sodium sulfate, 1 part of polydimethylsiloxane, 1 part of gentianine, and 0.5 part of sodium acetate, stir evenly to prepare an aqueous solution.

[0128] Example 8

[0129] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0130] By weight:

[0131] Add 8 parts of 2,4-D, 30 parts of 2-Methyl-4-chloro-4-yl chloride, 4 parts of dicamba, 30 parts of water and 23 parts of dimethylamine (40%) into a reaction kettle respectively, turn on the stirring device, slowly heat up to 50-60°C, dissolve until transparent, gradually cool down to 30-40°C during the dissolution process, then add 8 parts of fatty alcohol polyoxyethylene ether sodium sulfate, 1 part of polydimethylsiloxane, 1 part of gentianine, 0.5 part of sodium acetate, continue stirring, add 0.5 part of tea saponin and 0.5 part of lotus seed extract, stir evenly to obtain an aqueous solution.

[0132] Example 9

[0133] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0134] By weight:

[0135] 10 parts of 2,4-D, 40 parts of 2-Methyl-4-chloro-4-yl chloride, 5 parts of dicamba, 50 parts of water and 27 parts of ammonia water (17%) are added into a reaction kettle respectively, a stirring device is turned on, the temperature is slowly raised to 50-60°C, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered to 30-40°C, and then 6 parts of castor oil polyoxyethylene ether, 8 parts of ammonium sulfate and 4 parts of glucose are added, and the mixture is stirred evenly. The mixed solution is granulated by an extrusion granulator at a temperature of 50-60°C and a pressure of 5-10MPa to prepare 1-3 mm granular materials. The granulated granular materials are placed in a fluidized bed dryer, the drying temperature is set to 50-60°C and the wind speed is set to 1-2m / s, and the drying treatment is carried out for 30-60 minutes to prepare soluble granules.

[0136] Example 10

[0137] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0138] By weight:

[0139] 10 parts of 2,4-D, 40 parts of 2-Methyl-4-chloro-4-yl chloride, 5 parts of dicamba, 50 parts of water and 27 parts of ammonia water (17%) are added to a reaction kettle respectively, a stirring device is turned on, the temperature is slowly raised to 50-60°C, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered to 30-40°C, and then 6 parts of castor oil polyoxyethylene ether, 8 parts of ammonium sulfate, 4 parts of glucose and 1 part of gentianine are added, and the mixture is stirred evenly. The mixed solution is granulated by an extrusion granulator at a temperature of 50-60°C and a pressure of 5-10MPa to prepare 1-3 mm granular materials. The granulated granular materials are placed in a fluidized bed dryer, the drying temperature is set to 50-60°C and the wind speed is set to 1-2m / s, and the drying treatment is carried out for 30-60 minutes to prepare soluble granules.

[0140] Embodiment 11

[0141] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0142] By weight:

[0143] 10 parts of 2,4-D, 40 parts of 2-Methyl-4-chloro-4-yl chloride, 5 parts of dicamba, 50 parts of water and 27 parts of ammonia water (17%) are added to a reaction kettle respectively, a stirring device is turned on, the temperature is slowly raised to 50-60°C, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered to 30-40°C, and then 6 parts of castor oil polyoxyethylene ether, 8 parts of ammonium sulfate, 4 parts of glucose, 1 part of gentianine and 0.5 part of sodium acetate are added, and the mixture is stirred evenly. The mixed solution is granulated by an extrusion granulator at a temperature of 50-60°C and a pressure of 5-10MPa to prepare 1-3 mm granular materials. The granulated granular materials are placed in a fluidized bed dryer, the drying temperature is set to 50-60°C and the wind speed is set to 1-2m / s, and the drying treatment is carried out for 30-60 minutes to prepare soluble granules.

[0144] Example 12

[0145] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0146] By weight:

[0147] 10 parts of 2,4-D, 40 parts of 2-Methyl-4-chloro-4-yl, 5 parts of dicamba, 50 parts of water and 27 parts of ammonia water (17%) are added to a reaction kettle respectively, a stirring device is turned on, the temperature is slowly raised to 50-60°C, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered to 30-40°C, and then 6 parts of castor oil polyoxyethylene ether, 8 parts of ammonium sulfate, 4 parts of glucose, 1 part of gentianine, and 0.5 parts of sodium acetate are added, and stirring is continued. 0.5 parts of tea saponin and 0.5 parts of lotus seed extract are added and stirred evenly. The mixed solution is granulated by an extrusion granulator at a temperature of 50-60°C and a pressure of 5-10MPa to prepare 1-3 mm granular materials. The granulated granular materials are placed in a fluidized bed dryer, and the drying temperature is set to 50-60°C and the wind speed is set to 1-2m / s for drying. The drying time is 30-60 minutes to prepare soluble granules.

[0148] Embodiment 13

[0149] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0150] By weight:

[0151] 18 parts of 2,4-D isooctyl butyrate, 50 parts of 2-methyl-4-chlorobutyrate isooctyl butyrate and 12 parts of dicamba isooctyl butyrate were added into a reaction kettle respectively, and then 50 parts of No. 150 solvent oil, 6 parts of styrylphenol polyoxyethylene ether and 2 parts of calcium dodecylbenzenesulfonate were added in sequence, and stirred evenly at a stirring speed of 300-500 rpm for 30-60 minutes to obtain an emulsifiable concentrate.

[0152] Embodiment 14

[0153] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0154] By weight:

[0155] 18 parts of 2,4-D isooctyl butyrate, 50 parts of 2-methyl-4-chlorobutyrate isooctyl butyrate and 12 parts of dicamba isooctyl butyrate were added into a reaction kettle respectively, and then 50 parts of No. 150 solvent oil, 6 parts of styrylphenol polyoxyethylene ether, 2 parts of calcium dodecylbenzenesulfonate and 1 part of gentianine were added in sequence, and stirred evenly at a stirring speed of 300-500 rpm for 30-60 minutes to obtain an emulsifiable concentrate.

[0156] Embodiment 15

[0157] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0158] By weight:

[0159] 18 parts of 2,4-D isooctyl butyrate, 50 parts of 2-methyl-4-chlorobutyrate isooctyl butyrate and 12 parts of dicamba isooctyl butyrate were added into a reaction kettle respectively, and then 50 parts of No. 150 solvent oil, 6 parts of styrylphenol polyoxyethylene ether, 2 parts of calcium dodecylbenzenesulfonate, 1 part of gentianine and 0.5 part of sodium acetate were added in sequence, and stirred evenly at a stirring speed of 300-500 rpm for 30-60 minutes to obtain an emulsifiable concentrate.

[0160] Example 16

[0161] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0162] By weight:

[0163] 18 parts of 2,4-D isooctyl butyrate, 50 parts of 2-methyl-4-chlorobutyrate isooctyl butyrate and 12 parts of dicamba isooctyl butyrate are respectively added into a reaction kettle, and then 50 parts of No. 150 solvent oil, 6 parts of styrylphenol polyoxyethylene ether, 2 parts of calcium dodecylbenzenesulfonate, 1 part of gentianine and 0.5 part of sodium acetate are added in sequence, and stirred evenly at a stirring speed of 300-500rpm for 30-60 minutes. The stirring is continued, and 0.5 parts of tea saponin and 0.5 parts of lotus seed extract are added, and stirred evenly to obtain an emulsifiable concentrate.

[0164] Embodiment 17

[0165] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0166] By weight:

[0167] 11 parts of 2,4-dichloropropionic acid sodium salt, 51 parts of 2-methyl-4-chloropropionic acid sodium salt, 8 parts of dicamba sodium salt, 5 parts of sodium methylene bis-naphthalene sulfonate, 5 parts of lakai powder and 5 parts of diatomaceous earth were added into a reaction kettle, mixed evenly at 200-300 rpm, and crushed to less than 44 microns in a 20-30°C, 50-80m / s air flow mill to obtain a wettable powder.

[0168] Embodiment 18

[0169] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0170] By weight:

[0171] 11 parts of 2,4-dichloropropionic acid sodium salt, 51 parts of 2-methyl-4-chloropropionic acid sodium salt, 8 parts of dicamba sodium salt, 5 parts of sodium methylenebisnaphthalene sulfonate, 5 parts of lakai powder, 5 parts of diatomaceous earth and 1 part of gentianine were added into a reaction kettle, mixed evenly at 200-300 rpm, and crushed to less than 44 microns in a 20-30°C, 50-80m / s air flow mill to obtain a wettable powder.

[0172] Embodiment 19

[0173] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0174] By weight:

[0175] 11 parts of 2,4-dichloropropionic acid sodium salt, 51 parts of 2-methyl-4-chloropropionic acid sodium salt, 8 parts of dicamba sodium salt, 5 parts of sodium methylenebisnaphthalene sulfonate, 5 parts of lakai powder, 5 parts of diatomaceous earth, 1 part of gentianine and 0.5 part of sodium acetate were added into a reaction kettle, mixed evenly at 200-300 rpm, and crushed to less than 44 microns in a 20-30°C, 50-80m / s air flow mill to obtain a wettable powder.

[0176] Embodiment 20

[0177] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0178] By weight:

[0179] 11 parts of 2,4-D propionic acid sodium salt, 51 parts of 2-methyl-4-chloropropionic acid sodium salt, 8 parts of dicamba sodium salt, 5 parts of sodium methylenebisnaphthalene sulfonate, 5 parts of lakai powder, 5 parts of diatomaceous earth, 1 part of gentianine and 0.5 part of sodium acetate were added into a reaction kettle, mixed evenly at 200-300rpm, and then 0.5 parts of tea saponin and 0.5 parts of lotus seed extract were added, mixed evenly, and ground to less than 44 microns by a 20-30°C, 50-80m / s air flow mill to obtain a wettable powder.

[0180] Embodiment 21

[0181] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0182] By weight:

[0183] 8 parts of 2,4-D butyl, 36 parts of 2-methyl-4-chlorobutyl, 6 parts of dicamba butyl and 35 parts of white carbon black were fully mixed, and then 5 parts of ammonium sulfate, 5 parts of calcium dodecylbenzenesulfonate and 5 parts of sodium lignin sulfonate were added and mixed evenly. The mixture was crushed into 5 micron powder by a 20-30°C, 50-80m / s air flow mill, and extruded and granulated at 50-60°C, 5-10MPa and 0.5-1m / min. After granulation, the mixture was dried at 50-60°C, 1.5-3m / s fluidized bed to obtain water dispersible granules.

[0184] Embodiment 22

[0185] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0186] By weight:

[0187] 8 parts of 2,4-D butyl, 36 parts of 2-methyl-4-chlorobutyl, 6 parts of dicamba butyl and 35 parts of white carbon black were fully mixed, and then 5 parts of ammonium sulfate, 5 parts of calcium dodecylbenzenesulfonate, 5 parts of sodium lignin sulfonate and 1 part of gentianine were added and mixed evenly. The mixture was crushed into 5 micron powder by a 20-30°C, 50-80m / s air flow mill, and extruded and granulated at 50-60°C, 5-10MPa and 0.5-1m / min. After granulation, the mixture was dried at 50-60°C, 1.5-3m / s fluidized bed to obtain water dispersible granules.

[0188] Embodiment 23

[0189] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0190] By weight:

[0191] 8 parts of 2,4-D butyl, 36 parts of 2-methyl-4-chlorobutyl, 6 parts of butyl dicamba and 35 parts of white carbon black are fully mixed, and then 5 parts of ammonium sulfate, 5 parts of calcium dodecylbenzenesulfonate, 5 parts of sodium lignin sulfonate, 1 part of gentianine and 0.5 part of sodium acetate are added and mixed evenly, and the mixture is crushed into 5 micron powder by a 20-30°C, 50-80m / s air flow mill, and extruded and granulated at 50-60°C, 5-10MPa and 0.5-1m / min. After granulation, the mixture is dried at 50-60°C, 1.5-3m / s fluidized bed to obtain water dispersible granules.

[0192] Embodiment 24

[0193] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0194] By weight:

[0195] 8 parts of 2,4-D butyl, 36 parts of 2-methyl-4-chlorobutyl, 6 parts of dicamba butyl and 35 parts of white carbon black are fully mixed, and then 5 parts of ammonium sulfate, 5 parts of calcium dodecylbenzenesulfonate, 5 parts of sodium lignin sulfonate, 1 part of gentianine and 0.5 parts of sodium acetate are added, and stirring is continued. 0.5 parts of tea saponin and 0.5 parts of lotus seed extract are added, and the mixture is evenly mixed. The mixture is crushed into 5 micron powder by a 20-30°C, 50-80m / s air flow mill, and extruded and granulated at 50-60°C, 5-10MPa and 0.5-1m / min. After granulation, the mixture is dried at 50-60°C, 1.5-3m / s fluidized bed to obtain water dispersible granules.

[0196] Comparative Example 1

[0197] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0198] By weight:

[0199] Add 80 parts of 2,4-D isooctyl butyrate into the reaction kettle, then add 50 parts of No. 150 solvent oil, 6 parts of styrylphenol polyoxyethylene ether, and 2 parts of calcium dodecylbenzene sulfonate in sequence, stir evenly, the stirring speed is 300-500rpm, the stirring time is 30-60 minutes, continue stirring, add 0.5 parts of tea saponin and 0.5 parts of lotus seed extract, stir evenly, and prepare emulsifiable concentrate.

[0200] Comparative Example 2

[0201] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0202] By weight:

[0203] 80 parts of 2-methyl-4-chlorobutyrate isooctyl ester are added into the reaction kettle respectively, and then 50 parts of No. 150 solvent oil, 6 parts of styrylphenol polyoxyethylene ether and 2 parts of calcium dodecylbenzenesulfonate are added in sequence, and stirred evenly at a stirring speed of 300-500rpm for 30-60 minutes. The stirring is continued, and 0.5 parts of tea saponin and 0.5 parts of lotus seed extract are added, and stirred evenly to obtain an emulsifiable concentrate.

[0204] Comparative Example 3

[0205] A herbicidal composition containing phenoxycarboxylic acids, the specific steps of the preparation method are as follows:

[0206] By weight:

[0207] 80 parts of dicamba isooctyl ester were added into the reaction kettle respectively, and then 50 parts of No. 150 solvent oil, 6 parts of styrylphenol polyoxyethylene ether, and 2 parts of calcium dodecylbenzene sulfonate were added in sequence, and stirred evenly at a stirring speed of 300-500rpm for 30-60 minutes. The stirring was continued, and 0.5 parts of tea saponin and 0.5 parts of lotus seed extract were added, and stirred evenly to obtain an emulsifiable concentrate.

[0208] test:

[0209] Indoor test, test method: select several plastic pots with a diameter of 25 cm, add an appropriate amount of moist sterilized soil, use the bottom of the pot to completely moisten the soil, and evenly spread the pre-treated test weed seeds (horsegrass, foxtail grass, and goosegrass) on the soil surface, and cover with 1 cm of soil. After sowing, move to the greenhouse for routine cultivation and use the bottom of the pot to replenish water. When horsegrass, foxtail grass, and goosegrass are in the 3-4 leaf stage, keep 15 plants in each pot for testing. The agent is sprayed on the stems and leaves according to the designed amount. The test is set up for 4 repetitions, and the average value is taken. After treatment, the growth status of the test weeds is regularly observed and recorded. 21 days after treatment, the aboveground weeds are harvested and weighed for fresh weight. In addition, a control group that is not sprayed with the agent and not treated is also set up.

[0210] The actual protection effect is recorded as E, and the calculation formula is:

[0211] E=[(W C -W t ) / W C ]*100%,W C : Fresh weight of weeds in the control group; W t : Fresh weight of weeds in the treatment group. The results are shown in Table 2 below:

[0212] Table 2

[0213] Drug Name <![CDATA[Treatment rate (g a.i. / hm 2 )]]> Setaria E (%) Crabgrass E(%) Glechoma longituba E(%) Example 1 600 93.82 93.78 93.85 Example 2 600 94.63 94.59 94.61 Example 3 600 95.53 95.48 95.57 Example 4 600 98.62 98.58 98.65 Example 5 500 90.85 90.82 90.88 Example 6 500 92.14 92.12 92.19 Example 7 500 93.72 93.69 93.74 Example 8 500 96.53 96.49 96.55 Example 9 450 90.21 90.25 90.22 Example 10 450 92.61 92.58 92.64 Embodiment 11 450 96.24 96.23 96.28 Example 12 450 98.12 98.08 98.14 Embodiment 13 400 95.34 95.31 95.37 Embodiment 14 400 95.84 95.81 95.88 Embodiment 15 400 96.73 96.72 96.76 Example 16 400 98.34 98.35 98.37 Embodiment 17 390 92.52 92.49 92.54 Embodiment 18 390 93.86 93.82 93.89 Embodiment 19 390 96.94 96.91 96.98 Embodiment 20 390 98.54 98.51 98.57 Embodiment 21 550 92.21 92.18 92.24 Embodiment 22 550 95.42 95.38 95.45 Embodiment 23 550 96.14 96.11 96.18 Embodiment 24 550 96.63 96.68 96.66 Comparative Example 1 800 75.32 75.10 75.48 Comparative Example 2 800 74.85 74.52 75.01 Comparative Example 3 800 76.48 76.23 76.82

[0214] Comments: Referring to Table 2, (1) Examples 1 to 24 successfully prepared herbicidal compositions of different dosage forms. The present application selected a multi-component compound, which can improve the broad-spectrum of the herbicidal composition. The selected active ingredients are easily decomposed under natural conditions, reducing pollution to the environment. The herbicidal composition has low environmental toxicity. Through the combination of multiple action mechanisms, the risk of weed resistance is reduced. Synergistic effects and overall synergistic effects are also produced between different components; (2) Comparison between the examples found that in the method of the present application, the herbicidal composition in the form of a microemulsion has better performance; (3) Comparing Examples 1 to 24 with Comparative Examples 1 to 3, it is further demonstrated that the addition of multiple active ingredients can improve the herbicidal effect. Different active ingredients act on different targets. The combined use can enhance the comprehensive herbicidal effect on various weeds and reduce the possible drug resistance of a single ingredient.

[0215] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention is described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A herbicidal composition containing phenoxycarboxylic acids, characterized in that: The herbicidal composition comprises at least one of active ingredient A, active ingredient B, active ingredient C, and a pesticide adjuvant; The active ingredient A comprises at least one of 2,4-D acid, 2,4-D salt, 2,4-D ester, and a salt or ester of 2,4-D acid; The active ingredient B comprises at least one of 2-methyl-4-chloro-1-acid, 2-methyl-4-chloro-1-acid salt, 2-methyl-4-chloro-1-acid ester, and salt or ester of 2-methyl-4-chloro-1-acid; The active ingredient C includes at least one of dicamba, dicamba salt, and dicamba ester; The pesticide adjuvant includes at least one of an active ingredient D, a biogenic component, a solvent, a surfactant, and other adjuvants; the other adjuvants include at least one of nonylphenol polyoxyethylene ether, dimethylamine, sodium sulfate of fatty alcohol polyoxyethylene ether, polydimethylsiloxane, castor oil polyoxyethylene ether, ammonium sulfate, glucose, No. 150 solvent oil, styrene phenol polyoxyethylene ether, calcium dodecylbenzene sulfonate, sodium methylene bisnaphthalene sulfonate, pull open powder, diatomaceous earth, ammonia water, white carbon black, ammonium sulfate, calcium dodecylbenzene sulfonate, and sodium lignin sulfonate; the active ingredient D includes at least one of gentianine and sodium acetate.

2. The herbicidal composition containing phenoxycarboxylic acids according to claim 1, characterized in that: The biogenic component includes at least one of tea saponin and lotus seed extract; the solvent includes at least one of water and isopropanol; and the surfactant includes a silicone surfactant.

3. The herbicidal composition containing phenoxycarboxylic acids according to claim 1, characterized in that: The 2,4-D acid includes at least one of 2,4-D, 2,4-D propionic acid, and 2,4-D butyric acid; the salt of 2,4-D acid or the salt in the 2,4-D salt includes at least one of ammonium salt, dimethylamine salt, triethylamine salt, isopropylamine salt, sodium salt, and potassium salt; the ester of 2,4-D acid or the ester in the 2,4-D ester includes at least one of ethyl ester, butyl ester, isobutyl ester, and isooctyl ester; The 2-methyl-4-chloro-acid includes at least one of 2-methyl-4-chloro-acid, 2-methyl-4-chloro-propionic acid, and 2-methyl-4-chloro-butyric acid; the salt of 2-methyl-4-chloro-acid or the salt in the salt of 2-methyl-4-chloro-acid includes at least one of ammonium salt, dimethylamine salt, triethylamine salt, isopropylamine salt, sodium salt, and potassium salt; the ester of 2-methyl-4-chloro-acid or the ester in the ester of 2-methyl-4-chloro-acid includes at least one of ethyl ester, butyl ester, isobutyl ester, and isooctyl ester; The salt in the dicamba salt includes at least one of ammonium salt, dimethylamine salt, triethylamine salt, isopropylamine salt, sodium salt and potassium salt; the ester in the dicamba ester includes at least one of ethyl ester, butyl ester, isobutyl ester and isooctyl ester.

4. The herbicidal composition containing phenoxycarboxylic acids according to claim 1, characterized in that: The formulation of the herbicidal composition includes at least one of microemulsion, aqueous solution, soluble granules, emulsifiable concentrate, wettable powder, water-dispersible granules, water suspension, oil suspension, microcapsule granules, microcapsule suspension and spray.

5. A method for preparing a herbicidal composition containing phenoxycarboxylic acids according to any one of claims 1 to 4, characterized in that: The steps include: Dissolving PLGA in dichloromethane, adding active ingredient A, active ingredient B, and active ingredient C to obtain an active ingredient solution; While heating and stirring, inject the active ingredient solution into the aqueous solution of polyvinyl alcohol, stir and emulsify, let stand, and after the solvent evaporates completely, centrifuge, collect the particles, wash, and dry to obtain the core; The core is dispersed in a solvent, acrylamide monomer and initiator are added, protective gas is introduced, and the reaction is carried out in a water bath. After the reaction is completed, the reaction is centrifuged, washed, and dried to obtain particles coated with the intermediate layer; The particles coated with the middle layer are dispersed in a solvent, acrylic acid monomer and a cross-linking agent are added, the pH is adjusted, and the mixture is stirred under heating for reaction. After the reaction is completed, the mixture is centrifuged, washed, and dried to obtain particles coated with the outer layer; Add at least one of the active ingredient D, the biogenic ingredient and the surfactant to the solvent, stir until completely dissolved to form a uniform solution, add the outer-layer coated particles and other adjuvants, stir to obtain an emulsion, add the solvent to the emulsion, stir, and homogenize to obtain a herbicidal composition in the form of a microemulsion.

6. A method for preparing a herbicidal composition containing phenoxycarboxylic acids according to any one of claims 1 to 4, characterized in that: The steps include: The active ingredient A, the active ingredient B, the active ingredient C, the solvent and other adjuvants are mixed and stirred, heated, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered, and then other adjuvants, the active ingredient D and at least one of the biological source ingredients are added, and stirred evenly to prepare an aqueous herbicidal composition.

7. A method for preparing a herbicidal composition containing phenoxycarboxylic acids according to any one of claims 1 to 4, characterized in that: The steps include: The active ingredient A, the active ingredient B, the active ingredient C, the solvent and other adjuvants are mixed and stirred, heated, and dissolved until transparent. During the dissolution process, the temperature is gradually lowered, and then other adjuvants, the active ingredient D, and at least one of the biological source components are added, stirred evenly, and the evenly mixed solution is extruded into granules and dried to obtain a herbicidal composition in the form of soluble granules.

8. A method for preparing a herbicidal composition containing phenoxycarboxylic acids according to any one of claims 1 to 4, characterized in that: The steps include: Active ingredient A, active ingredient B and active ingredient C are added into a reaction container, and then other adjuvants, active ingredient D and at least one of the biological source ingredients are added, and stirred evenly to obtain a herbicidal composition in the form of emulsifiable concentrate.

9. A method for preparing a herbicidal composition containing phenoxycarboxylic acids according to any one of claims 1 to 4, characterized in that: The steps include: Active ingredient A, active ingredient B and active ingredient C are added into a reaction container, and then other adjuvants, active ingredient D and at least one of biological source ingredients are added, mixed evenly, and crushed to less than 44 microns to obtain a wettable powder herbicidal composition.

10. A method for preparing a herbicidal composition containing phenoxycarboxylic acids according to any one of claims 1 to 4, characterized in that: The steps include: Active ingredient A, active ingredient B, active ingredient C and other adjuvants are added into a reaction container and mixed, and then other adjuvants, active ingredient D and at least one of the biological source ingredients are added, mixed evenly, crushed to less than 44 microns, extruded into granules, and dried to obtain a herbicidal composition of water dispersible granules.

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