Pesticide composition containing fluazifop-propyl and glufosinate-ammonium, preparation method and application thereof

Abstract

The present application relates to the field of pesticides, and specifically discloses a pesticide composition containing fluazifop-butyl and glufosinate-ammonium, and a preparation method and application thereof. The pesticide composition comprises the following raw materials: fluazifop-butyl, glufosinate-ammonium, a dispersant, an emulsifier, an anti-settling agent and vegetable oil; wherein the emulsifier is a mixture of sodium salt of sulfonated styrene-maleic anhydride copolymer and hydroxylated lecithin; and the preparation method comprises the following steps: mixing and stirring the vegetable oil, the emulsifier and the anti-settling agent to obtain an oil phase, then adding fluazifop-butyl and glufosinate-ammonium, mixing and stirring, adding the dispersant, and then performing homogenization and grinding to obtain a dispersible oil suspension type pesticide composition; the present application also discloses the use of the above pesticide composition for weeding. The present application has the characteristics of a pesticide reagent containing fluazifop-butyl and glufosinate-ammonium at the same time, which can be directly diluted with water when used without the need for fresh preparation, while ensuring its efficacy and being simpler and more convenient to operate.

Description

Technical Field

[0001] The present application relates to the field of pesticide products, and more specifically, to a pesticide composition containing fluazifop-butyl and glufosinate-ammonium, and a preparation method and application thereof. Background Art

[0002] In recent years, with the development of modern agriculture, chemical herbicides have become an important tool for field weed management due to their high efficiency and rapidity. In particular, orchard weeding mainly relies on chemical pesticides. However, the long-term use of single-ingredient pesticides has led to increased resistance, causing traditional single-dose herbicides to gradually lose their original effectiveness, while causing environmental pollution and destruction of the ecological balance.

[0003] In order to solve the above problems, new strategies for compounding multiple active ingredients have been studied. Through reasonable drug combinations, the weed control effect can be improved and the incidence of drug resistance can be reduced. One of the methods is: single-dose rotation application method, that is, using different single herbicides alternately in different seasons. Although this method delays the occurrence of drug resistance to a certain extent, it cannot completely solve the problem. Therefore, it is more widely used to mix two or more different types of herbicides with complementary properties and use them together, which can effectively overcome the problem that a single herbicide is difficult to control multiple types of weeds.

[0004] Fluazifop-butyl is a highly effective herbicide belonging to the N-phenylphthalimide herbicide class. It has the characteristics of high efficiency, low toxicity and strong selectivity. Fluazifop-butyl is mainly used in orchards, non-arable land and crops such as soybeans, sugarcane and cotton to control grass weeds and broad-leaved weeds. It has a fast effect, a long weed control period, and can effectively control a variety of difficult-to-control malignant weeds.

[0005] Glufosinate is a broad-spectrum contact herbicide with systemic conductivity. It can be transmitted through the stems and leaves to the underground part, killing the weeds with their roots. Glufosinate has a strong destructive power on the underground tissues of perennial deep-rooted weeds and can reach depths that ordinary agricultural machinery cannot reach.

[0006] The combination of glufosinate and fluazifop-butyl has a significant effect on a variety of malignant weeds. However, due to the different properties of the two, the fluazifop-butyl currently available on the market is generally a wettable powder, while glufosinate is in liquid form. Therefore, the current method of using the two in combination is to mix and use them immediately, specifically, first dissolve one in half water, then dissolve the other in the other half of water and then mix them. However, the above-mentioned method of mixing and using immediately is relatively cumbersome.

[0007] Therefore, a pesticide product containing fluazifop-butyl and glufosinate-ammonium is provided, which can be directly diluted with water when used, thereby greatly reducing the operation steps and making it more convenient to use. At the same time, ensuring its efficacy is of great significance for meeting current agricultural needs. Summary of the invention

[0008] In order to prepare a pesticide reagent containing both fluazifop-butyl and glufosinate-ammonium, which can be directly diluted with water before use without fresh preparation, while ensuring its efficacy and making the operation simpler and more convenient, the present application provides a pesticide composition containing fluazifop-butyl and glufosinate-ammonium, and a preparation method and application thereof.

[0009] In a first aspect, the present application provides a pesticide composition containing fluazifop-butyl and glufosinate-ammonium, which adopts the following technical solution:

[0010] A pesticide composition containing fluazifop-butyl and glufosinate-ammonium comprises the following raw materials in parts by weight:

[0011] 2-8 parts of fluazifop-butyl, 15-25 parts of glufosinate-ammonium, 3-8 parts of dispersant, 18-30 parts of emulsifier, 1-3 parts of anti-settling agent and 60-75 parts of vegetable oil;

[0012] The emulsifier is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin.

[0013] By adopting the above technical scheme, in the present application, fluazifop-butyl and glufosinate-ammonium are combined with a dispersant, an emulsifier and a vegetable oil as an oil-based medium to prepare a dispersible oil suspension, and the insolubility or slight solubility of fluazifop-butyl and glufosinate-ammonium in the oil-based medium is utilized to form a tiny particle suspension system, and the addition of the emulsifier utilizes the hydrophilicity at one end and the lipophilicity at the other end to form an interface film between the oil droplets and the water phase to stabilize the emulsion, and more importantly, utilizes the hydrophilicity and lipophilicity balance adjustment of the particles in the suspension, so that when the dispersible oil suspension is used, the oil suspension is diluted with water. The floating agent quickly disperses in the water and forms a uniform suspension. Compared with the current ready-made use, it only needs to add water to evenly cover the plant leaves, which is more convenient. What's more important is that when the suspension is sprayed on the plant leaves, the oil-based medium will form an oil film on the surface of the leaves. This oil film can not only increase the contact area between the agent and the leaves, but also promote the penetration of the agent into the leaves. Because the oil film has the characteristics of strong penetration conduction, good adhesion and long retention time, it can ensure that the agent maintains an effective concentration on the leaves for a long time, thereby improving the prevention and control effect.

[0014] At present, there is a small amount of 66% fluazifop-butyl and 60% glufosinate wettable powder on the market, which is a compound herbicide of fluazifop-butyl and glufosinate ammonium. Although the active ingredients in the wettable powder are directly dispersed when the recommended dosage is added to water for application, the water solubility of fluazifop-butyl is poor, resulting in poor dispersion uniformity of the above two active ingredients, affecting the efficacy, and compared with the dispersible oil suspension in the present application, the wettable powder has poor adhesion and spreadability on plant leaves, resulting in reduced utilization rate and control effect of the agent, and the wettable powder may generate dust pollution during use, causing certain harm to the environment and users. Moreover, the compounding of fluazifop-butyl and glufosinate ammonium into a dispersible oil suspension in the present application can be combined with drone application, overcoming the shortcomings of easy evaporation and drift of water-based formulations when using drones for application, making drone application more efficient.

[0015] In addition, the emulsifier in the present application is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin. The sulfonated styrene-maleic anhydride copolymer sodium salt contains styrene and maleic anhydride units. The styrene unit gives it hydrophobicity, and the sulfonic acid group introduced by sulfonation modification in maleic anhydride increases its hydrophilicity and dispersibility. In this way, the hydrophobic segment interacts with the oil phase and the active molecules of the pesticide, thereby achieving stable dispersion of the oil-water system. As an emulsifier, it has better emulsification and dispersibility when finally diluted with water. Hydroxylated lecithin, as a natural non-ionic emulsifier, can play a good emulsifying role when combined with sulfonated styrene-maleic anhydride copolymer sodium salt.

[0016] More importantly, the presence of the benzene ring structure in the styrene unit in the sodium salt of the sulfonated styrene-maleic anhydride copolymer can form a stable adsorption with the aromatic rings in fluazifop-propyl and glufosinate-ammonium through π-π stacking, and adsorb on the surface of solid particles in combination with the dispersant to form a charged protective film, thereby preventing particle aggregation, significantly reducing the sedimentation of the active particle components of the pesticide, and improving the suspension stability. Finally, when the pesticide composition of the dispersible oil suspension of the present application uses the above-mentioned emulsifier, not only a stable emulsified system can be formed, but also the obtained suspension has excellent stability. Compared with the traditional polyoxyethylene ether emulsifier, which is affected by temperature during storage and causes sedimentation and bottoming, the suspension in the present application has no stratification, oil separation and bottoming after long-term storage, and has excellent storage stability.

[0017] Optionally, the anti-settling agent is selected from organic bentonite and modified fumed silica in a mass ratio of 1: (1.2-1.5), and the modified fumed silica is prepared by soaking the fumed silica in an immersion aqueous solution prepared from 2-hydroxy-N, N, N,-trimethylethylamine chloride and 3-aminopropyltriethoxysilane and then drying.

[0018] By adopting the above technical scheme, the anti-settling agent in the present application is a composite of organic bentonite and modified fumed silica. Compared with commonly used xanthan gum and carboxymethyl cellulose, it is difficult to expand in an oil-based medium to form a three-dimensional network structure and it is difficult to play its role. The organic bentonite in the present application is a complex of inorganic minerals and organic cations obtained by exchanging the interlayer cations of bentonite with organic cations. In the oil phase, oil molecules can enter the gaps in the layered structure of bentonite, causing the bentonite to swell into a sol state, thereby increasing the viscosity of the system. The extremely high specific surface area of ​​fumed silica adsorbs vegetable oil, and the silicon hydroxyl groups on its surface form hydrogen bonds with the vegetable oil, thereby increasing the viscosity of the system, playing a thickening and anti-settling role in the oil-based system, providing good stability for the pesticide composition containing fluazifop-butyl and glufosinate-ammonium, and maintaining uniform dispersion during storage and use, thereby giving full play to its weed control effect.

[0019] Moreover, the fumed silica in the present application is modified by soaking in an aqueous solution of 2-hydroxy-N, N, N,-trimethylethylamine chloride and 3-aminopropyltriethoxysilane before application. The addition of 3-aminopropyltriethoxysilane introduces amino groups into the surface of silica, and the addition of 2-hydroxy-N, N, N,-trimethylethylamine chloride also introduces amino groups into the surface of fumed silica through the action of hydroxyl groups with silane groups in fumed silica. The amino groups on the surface of fumed silica form hydrogen bonds with functional groups such as carboxyl groups and amide groups in the molecular structures of fluazifop and glufosinate ammonium, thereby improving the adsorption of the fumed silica on the above-mentioned active ingredients of pesticides, further improving its anti-sedimentation effect, and ultimately improving the stability of the dispersible oil suspension concentrate.

[0020] Optionally, when the modified fumed silica is prepared, the soaking water solution is prepared by mixing 2-hydroxy-N, N, N,-trimethylethylamine chloride, 3-aminopropyltriethoxysilane and water in a mass ratio of 1: (4-5): (8-10), and the soaking water solution is 6-8 times the mass of the fumed silica.

[0021] Optionally, the chlorinated 2-hydroxy-N, N, N,-trimethylethylamine is prepared by an amination modification treatment, and the specific method is: after mixing the chlorinated 2-hydroxy-N, N, N,-trimethylethylamine with an alkaline solution, heating to 40-45° C., then adding hydroxyethylethylenediamine, reacting for 40-60 minutes and then cooling to obtain the aminated modified chlorinated 2-hydroxy-N, N, N,-trimethylethylamine.

[0022] By adopting the above technical scheme, hydroxyethylethylenediamine contains one hydroxyl group and two amino groups. Under acidic conditions, one of the amino groups in hydroxyethylethylenediamine reacts with the hydroxyl group in chlorinated 2-hydroxy-N, N, N,-trimethylethylamine to form amide, and at the same time, another amino group and hydroxyl group are introduced into its molecular structure. The introduced hydroxyl group reacts with the silane group of fumed silica to achieve the modification of fumed silica by aminated chlorinated 2-hydroxy-N, N, N,-trimethylethylamine, and the other amino group in aminated chlorinated 2-hydroxy-N, N, N,-trimethylethylamine forms a hydrogen bond or a chemical bond with fluazifop-propylamine and glufosinate-ammonium to achieve the adsorption of active ingredients of pesticides. In this way, one hydroxyl group in aminated chlorinated 2-hydroxy-N, N, N,-trimethylethylamine is bonded to fumed silica to achieve a better thickening effect, and the other amino group forms a hydrogen bond or a chemical bond with fluazifop-propylamine and glufosinate-ammonium, and the aminated chlorinated 2-hydroxy-N, N, N,-trimethylethylamine forms a hydrogen bond or a chemical bond with fluazifop-propylamine and glufosinate-ammonium. The nitrogen atom in the terminal group of the original molecular structure of N,-trimethylethylamine forms a steric hindrance effect with the three methyl groups. Therefore, when it forms hydrogen bonds or chemical bonds with fluazifop-butyl and glufosinate-ammonium, due to its steric hindrance effect, the mutual agglomeration and sedimentation of the above-mentioned pesticide active ingredients are further reduced, thereby improving the stability of the dispersible oil suspension.

[0023] Optionally, during the amination modification process of 2-hydroxy-N, N, N,-trimethylethylamine chloride, the alkaline solution is a sodium hydroxide solution with a mass ratio of 20-30wt%, and the amount of alkaline solution added is 5-10wt% of the amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride added, and the mass ratio of hydroxyethylethylenediamine to 2-hydroxy-N, N, N,-trimethylethylamine chloride is 1:(1.2-1.5).

[0024] Optionally, the sulfonated styrene-maleic anhydride copolymer sodium salt is prepared by the following method:

[0025] Styrene monomer and maleic anhydride monomer are mixed, added to a mixed solvent of xylene and acetone, and then lauroyl peroxide and n-butyl mercaptan are added, the temperature is raised to 65-75° C., reacted for 2-3 hours, and then tert-butyl carbonate is added to continue the reaction for 30-50 minutes, and then cooled to room temperature, filtered and washed with water to obtain a styrene-maleic anhydride copolymer;

[0026] The prepared styrene-maleic anhydride copolymer is mixed with dichloromethane solvent, and then concentrated sulfuric acid is added dropwise under stirring, the reaction temperature is controlled not to exceed 40°C, the reaction is carried out for 20-30 minutes, the temperature is raised to 60-65°C, the reaction is continued for 60-90 minutes, the mixture is cooled, mixed with water, allowed to stand and precipitate, filtered and washed, added to a sodium hydroxide solution, the pH value is adjusted to 7.5-8.5, and then evaporated and crystallized to obtain the sulfonated styrene-maleic anhydride copolymer sodium salt.

[0027] By adopting the above technical scheme, in the present application, lauroyl peroxide is used as an initiator, n-butyl mercaptan is used as a chain transfer agent, the initiator decomposes to generate free radicals to initiate styrene and maleic anhydride to alternately generate copolymers, and in the final stage, tert-butyl carbonate monomers are added, tert-butyl carbonate and styrene monomers are polymerized to introduce tert-butyl carbonate into the styrene unit, and since the terminal group of tert-butyl carbonate is a tert-carbon group, it has a great steric hindrance effect, and after the reaction is completed, the styrene-maleic anhydride copolymer containing tert-butyl carbonate is obtained and sulfonated to achieve sulfonated hydrophilic modification of the maleic anhydride unit, and the hydrophilic-lipophilic balance value of the substance is achieved, and then the conjugated stacking effect formed between the benzene ring structure and the active ingredient of the pesticide and its steric hindrance effect are utilized, so that the stability of the product and the final redispersibility are improved, and a better weed control and synergistic effect is achieved.

[0028] Optionally, in the preparation process of the sodium salt of sulfonated styrene-maleic anhydride copolymer, the mass ratio of styrene monomer to maleic anhydride monomer is 1:(0.7-0.8), the mass ratio of xylene to acetone is 1:(0.8-1.2), and the amount of xylene added is 3-4 times the mass of the styrene monomer, the amount of lauroyl peroxide added is 2-4wt% of the styrene monomer, the amount of n-butyl mercaptan added is 0.5-1wt% of the styrene monomer, and the amount of versatate added is 20-30wt% of the styrene monomer;

[0029] The mass ratio of styrene-maleic anhydride copolymer to dichloromethane is 1:(3-4), and the amount of concentrated sulfuric acid added is 3-5wt% of the styrene-maleic anhydride copolymer.

[0030] By adopting the above technical solution and selecting the above raw material addition amount, the comprehensive performance of the dispersible oil suspension obtained in the end is better.

[0031] Optionally, the emulsifier is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin in a mass ratio of 1:(0.6-0.8);

[0032] The dispersant is a polycarboxylate dispersant.

[0033] Optionally, the vegetable oil is selected from one or more of soybean oil, corn oil, rapeseed oil, castor oil and vegetable oil esters.

[0034] In a second aspect, the present application provides a method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium, using the following technical solution:

[0035] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium comprises the following steps:

[0036] The vegetable oil, emulsifier and anti-settling agent are mixed and stirred to obtain an oil phase, and then fluazifop-butyl and glufosinate-ammonium are added and mixed and stirred, and then a dispersant is added, and then a dispersible oil suspension type pesticide composition is obtained after homogenization and grinding.

[0037] By adopting the above technical scheme, the pesticide composition prepared by the method of the present application is a dispersible oil suspension, which can be used after being diluted with water, making the operation more convenient, and is more conducive to plant adhesion, and has a better weed control effect.

[0038] In a third aspect, the present application provides an application of a pesticide composition containing fluazifop-butyl and glufosinate-ammonium, using the following technical solution:

[0039] The pesticide composition containing fluazifop-butyl and glufosinate-ammonium is mixed with water in a mass ratio of 1:(150-200) and then used for weeding.

[0040] In summary, this application has the following beneficial effects:

[0041] 1. In the present application, fluazifop-butyl and glufosinate-ammonium are formulated into a dispersible oil suspension, which can be evenly covered on plant leaves by directly adding water when used, which is more convenient. More importantly, when the suspension is sprayed on plant leaves, the oil-based medium will form an oil film on the surface of the leaves. This oil film can not only increase the contact area between the agent and the leaves, but also promote the penetration of the agent into the inside of the leaves. Since the oil film has the characteristics of strong penetration conduction, good adhesion, and long retention time, it can ensure that the agent maintains an effective concentration on the leaves for a long time, thereby improving the control effect;

[0042] 2. The emulsifier in the present application is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin. The sulfonated styrene-maleic anhydride copolymer sodium salt contains styrene and maleic anhydride units. The styrene unit gives it hydrophobicity, while the sulfonic acid group introduced by sulfonation modification in maleic anhydride increases its hydrophilicity and dispersibility. In this way, the hydrophobic segment interacts with the oil phase and the pesticide active molecules, thereby achieving stable dispersion of the oil-water system. As an emulsifier, it has better emulsification and dispersibility when it is finally diluted with water. Hydroxylated lecithin, as a natural nonionic emulsifier, can play a good emulsifying role when combined with sulfonated styrene-maleic anhydride copolymer sodium salt;

[0043] 3. The presence of the benzene ring structure in the styrene unit in the sodium salt of the sulfonated styrene-maleic anhydride copolymer in the present application can form a stable adsorption with the aromatic rings in fluazifop-propyl and glufosinate-ammonium through π-π stacking, and is adsorbed on the surface of solid particles in combination with a polycarboxylate dispersant to form a charged protective film, thereby preventing particle aggregation, significantly reducing the sedimentation of active particle components of the pesticide, and improving suspension stability. Finally, when the pesticide composition of the dispersible oil suspension of the present application uses the above-mentioned emulsifier and dispersant, not only a stable emulsified system can be formed, but also the obtained suspension has excellent stability. Compared with the traditional polyoxyethylene ether emulsifier, which is affected by temperature during storage and causes sedimentation and bottoming, the suspension in the present application has no stratification, oil separation and bottoming after long-term storage, and has excellent storage stability. DETAILED DESCRIPTION

[0044] The present application is further described in detail below in conjunction with the examples. It is particularly noted that if no specific conditions are specified in the following examples, the experiments are carried out according to conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following examples can be obtained from common commercial sources.

[0045] In the following examples, the polycarboxylate dispersant is selected from dispersant 5040 of Jingzhou Yinjie Chemical;

[0046] The organic bentonite used is Hemmings organic bentonite BENTONE27, model B27.

[0047] The following preparation example is an example of the preparation of the sodium salt of sulfonated styrene-maleic anhydride copolymer.

[0048] Preparation Example 1

[0049] A method for preparing a sodium salt of sulfonated styrene-maleic anhydride copolymer comprises the following steps:

[0050] 1) Styrene monomer and maleic anhydride monomer were mixed in a mass ratio of 1:0.8, and added to a mixed solvent obtained by mixing xylene and acetone in a mass ratio of 1:1, and the amount of xylene added was 4 times the mass of the styrene monomer, and then initiators lauroyl peroxide and n-butyl mercaptan were added, the temperature was raised to 70°C, and after reacting for 2.5 hours, tert-butyl carbonate was added and the reaction was continued for 40 minutes, and then cooled to room temperature, filtered and washed with water to obtain a styrene-maleic anhydride copolymer, wherein the amount of lauroyl peroxide added was 3wt% of the styrene monomer, the amount of n-butyl mercaptan added was 0.8wt% of the styrene monomer, and the amount of tert-butyl carbonate added was 25wt% of the styrene monomer;

[0051] 2) The styrene-maleic anhydride copolymer prepared in step 1) is mixed with dichloromethane solvent in a mass ratio of 1:3, and then concentrated sulfuric acid with a mass fraction of 98% is added dropwise under stirring, the amount of concentrated sulfuric acid added is 4wt% of the styrene-maleic anhydride copolymer, and the reaction temperature is controlled not to exceed 40°C. After the addition, the temperature is raised to 60°C after reacting for 25 minutes, and the reaction is continued for 80 minutes. After cooling, the mixture is mixed with water and allowed to stand for precipitation, and then filtered and washed with water, added to a sodium hydroxide solution, the pH is adjusted to 8, and then evaporated and crystallized to obtain a sulfonated styrene-maleic anhydride copolymer sodium salt.

[0052] Preparation Example 2

[0053] A method for preparing a sodium salt of sulfonated styrene-maleic anhydride copolymer comprises the following steps:

[0054] 1) Styrene monomer and maleic anhydride monomer were mixed in a mass ratio of 1:0.7, and added to a mixed solvent obtained by mixing xylene and acetone in a mass ratio of 1:0.8, and the amount of xylene added was 3 times the mass of the styrene monomer, and then initiators lauroyl peroxide and n-butyl mercaptan were added, and the temperature was raised to 65°C, and after reacting for 3 hours, tert-butyl carbonate was added and continued to react for 30 minutes, and then cooled to room temperature, filtered and washed with water to obtain a styrene-maleic anhydride copolymer, wherein the amount of lauroyl peroxide added was 2wt% of the styrene monomer, the amount of n-butyl mercaptan added was 0.5wt% of the styrene monomer, and the amount of tert-butyl carbonate added was 20wt% of the styrene monomer;

[0055] 2) The styrene-maleic anhydride copolymer prepared in step 1) is mixed with dichloromethane solvent in a mass ratio of 1:3, and then concentrated sulfuric acid with a mass fraction of 98% is added dropwise under stirring, and the amount of concentrated sulfuric acid added is 3wt% of the styrene-maleic anhydride copolymer. The reaction temperature is controlled not to exceed 40°C, and the temperature is raised to 60°C after the addition for 20 minutes, and the reaction is continued for 90 minutes. After cooling, it is mixed with water and allowed to stand for precipitation, and then filtered and washed with water, and then added to a sodium hydroxide solution, the pH is adjusted to 7.5, and then evaporated and crystallized to obtain a sulfonated styrene-maleic anhydride copolymer sodium salt.

[0056] Preparation Example 3

[0057] A method for preparing a sodium salt of sulfonated styrene-maleic anhydride copolymer comprises the following steps:

[0058] 1) Styrene monomer and maleic anhydride monomer were mixed in a mass ratio of 1:0.8, and added to a mixed solvent obtained by mixing xylene and acetone in a mass ratio of 1:1.2, and the amount of xylene added was 4 times the mass of the styrene monomer, and then initiators lauroyl peroxide and n-butyl mercaptan were added, and the temperature was raised to 75°C. After reacting for 2 hours, tert-butyl carbonate was added and the reaction was continued for 50 minutes, and then cooled to room temperature, filtered and washed with water to obtain a styrene-maleic anhydride copolymer, wherein the amount of lauroyl peroxide added was 4wt% of the styrene monomer, the amount of n-butyl mercaptan added was 1wt% of the styrene monomer, and the amount of tert-butyl carbonate added was 30wt% of the styrene monomer;

[0059] 2) The styrene-maleic anhydride copolymer prepared in step 1) is mixed with dichloromethane solvent in a mass ratio of 1:4, and then concentrated sulfuric acid with a mass fraction of 98% is added dropwise under stirring, and the amount of concentrated sulfuric acid added is 5wt% of the styrene-maleic anhydride copolymer. The reaction temperature is controlled not to exceed 40°C, and the temperature is raised to 65°C after the addition for 30 minutes, and the reaction is continued for 60 minutes. After cooling, it is mixed with water and allowed to stand for precipitation, and then filtered and washed with water, and then added to a sodium hydroxide solution, the pH is adjusted to 8.5, and then evaporated and crystallized to obtain a sulfonated styrene-maleic anhydride copolymer sodium salt.

[0060] Preparation Example 4

[0061] A method for preparing sodium salt of sulfonated styrene-maleic anhydride copolymer is carried out according to the method in Preparation Example 1, except that versatate vinyl carbonate is not added in step 1). Example 1

[0062] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium comprises the following steps:

[0063] 68 kg of vegetable oil, 25 kg of emulsifier and 2 kg of anti-settling agent were mixed and stirred to obtain an oil phase, and then 5 kg of fluazifop-butyl and 20 kg of glufosinate-ammonium were added and mixed and stirred, and then 5 kg of polycarboxylate dispersant was added, and then homogenized and ground to obtain a dispersible oil suspension type pesticide composition.

[0064] The vegetable oil is soybean oil, the emulsifier is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin in a mass ratio of 1:0.7, and the sulfonated styrene-maleic anhydride copolymer sodium salt is the sulfonated styrene-maleic anhydride copolymer sodium salt prepared in Preparation Example 1;

[0065] The anti-settling agent is selected from organic bentonite and modified fumed silica in a mass ratio of 1:1.3, wherein the modified fumed silica is prepared by the following method:

[0066] 2-Hydroxy-N, N, N,-trimethylethylamine chloride, 3-aminopropyltriethoxysilane and water are mixed in a mass ratio of 1:4.5:9 to prepare a soaking water solution, and then fumed silica is added, and the mixture is soaked for 25 minutes under ultrasonic-assisted conditions and then dried to obtain modified fumed silica, wherein the soaking water solution is 7 times the mass of the fumed silica. Example 2

[0067] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium comprises the following steps:

[0068] 60 kg of vegetable oil, 18 kg of emulsifier and 1 kg of anti-settling agent were mixed and stirred to obtain an oil phase, and then 2 kg of fluazifop-butyl and 15 kg of glufosinate-ammonium were added and mixed and stirred, and then 3 kg of polycarboxylate dispersant was added, and then homogenized and ground to obtain a dispersible oil suspension type pesticide composition.

[0069] The vegetable oil is soybean oil, the emulsifier is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin in a mass ratio of 1:0.6, and the sulfonated styrene-maleic anhydride copolymer sodium salt is the sulfonated styrene-maleic anhydride copolymer sodium salt prepared in Preparation Example 2;

[0070] The anti-settling agent is selected from organic bentonite and modified fumed silica in a mass ratio of 1:1.2, wherein the modified fumed silica is prepared by the following method:

[0071] 2-Hydroxy-N, N, N,-trimethylethylamine chloride, 3-aminopropyltriethoxysilane and water are mixed in a mass ratio of 1:4:8 to prepare a soaking water solution, and then fumed silica is added, and the mixture is soaked for 20 minutes under ultrasonic-assisted conditions and then dried to obtain modified fumed silica, wherein the soaking water solution is 6 times the mass of the fumed silica. Example 3

[0072] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium comprises the following steps:

[0073] 75 kg of vegetable oil, 30 kg of emulsifier and 3 kg of anti-settling agent were mixed and stirred to obtain an oil phase, and then 8 kg of fluazifop-butyl and 25 kg of glufosinate-ammonium were added and mixed and stirred, and then 8 kg of polycarboxylate dispersant was added, and then homogenized and ground to obtain a dispersible oil suspension type pesticide composition.

[0074] The vegetable oil is soybean oil, the emulsifier is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin in a mass ratio of 1:0.8, and the sulfonated styrene-maleic anhydride copolymer sodium salt is the sulfonated styrene-maleic anhydride copolymer sodium salt prepared in Preparation Example 3;

[0075] The anti-settling agent is selected from organic bentonite and modified fumed silica in a mass ratio of 1:1.5, wherein the modified fumed silica is prepared by the following method:

[0076] 2-Hydroxy-N, N, N,-trimethylethylamine chloride, 3-aminopropyltriethoxysilane and water are mixed in a mass ratio of 1:5:10 to prepare a soaking water solution, and then fumed silica is added, and the mixture is soaked for 30 minutes under ultrasonic-assisted conditions and then dried to obtain modified fumed silica, wherein the soaking water solution is 8 times the mass of the fumed silica. Example 4

[0077] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that the sodium salt of sulfonated styrene-maleic anhydride copolymer is the sodium salt of sulfonated styrene-maleic anhydride copolymer prepared in Preparation Example 4. Example 5

[0078] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that 2-hydroxy-N, N, N,-trimethylethylamine chloride is added after being modified by amination, and the specific operation is as follows: 2-hydroxy-N, N, N,-trimethylethylamine chloride is mixed with a sodium hydroxide solution with a mass fraction of 25wt%, heated to 40°C, and then hydroxyethylethylenediamine is added. After reacting for 50 minutes, the mixture is cooled to obtain aminated-modified 2-hydroxy-N, N, N,-trimethylethylamine chloride, wherein the amount of sodium hydroxide solution added is 8wt% of the amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride added, and the mass ratio of hydroxyethylethylenediamine to 2-hydroxy-N, N, N,-trimethylethylamine chloride is 1:1.3. Example 6

[0079] A method for preparing a pesticide composition containing fluazifop-propyl and glufosinate-ammonium is carried out according to the method in Example 1, except that 2-hydroxy-N, N, N,-trimethylethylamine chloride is added after being modified by amination, and the specific operation is as follows: 2-hydroxy-N, N, N,-trimethylethylamine chloride is mixed with a sodium hydroxide solution with a mass fraction of 20wt%, heated to 40°C, and then hydroxyethylethylenediamine is added. After reacting for 40 minutes, the mixture is cooled to obtain aminated-modified 2-hydroxy-N, N, N,-trimethylethylamine chloride, wherein the amount of sodium hydroxide solution added is 5wt% of the amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride added, and the mass ratio of hydroxyethylethylenediamine to 2-hydroxy-N, N, N,-trimethylethylamine chloride is 1:1.2. Example 7

[0080] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that 2-hydroxy-N, N, N,-trimethylethylamine chloride is added after being modified by amination, and the specific operation is as follows: 2-hydroxy-N, N, N,-trimethylethylamine chloride is mixed with a sodium hydroxide solution with a mass fraction of 30wt%, heated to 45°C, and then hydroxyethylethylenediamine is added. After reacting for 60 minutes, the mixture is cooled to obtain aminated-modified 2-hydroxy-N, N, N,-trimethylethylamine chloride, wherein the amount of sodium hydroxide solution added is 10wt% of the amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride added, and the mass ratio of hydroxyethylethylenediamine to 2-hydroxy-N, N, N,-trimethylethylamine chloride is 1:1.5.

[0081] Comparative Example 1

[0082] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that an equal amount of sulfonated styrene-maleic anhydride copolymer sodium salt is replaced by octylphenol polyoxyethylene ether.

[0083] Comparative Example 2

[0084] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that an equal amount of sulfonated styrene-maleic anhydride copolymer sodium salt is replaced by fatty alcohol polyoxyethylene ether phosphate AEO-3P.

[0085] Comparative Example 3

[0086] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that an equal amount of modified fumed silica is replaced by fumed silica.

[0087] Comparative Example 4

[0088] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that an equal amount of modified fumed silica is replaced by magnesium aluminum silicate.

[0089] Comparative Example 5

[0090] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that when the modified fumed silica is modified, an equal amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride is replaced by 3-aminopropyltriethoxysilane.

[0091] Comparative Example 6

[0092] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that when modifying the fumed silica, an equal amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride is replaced by 1-hydroxyethyl-3-methylimidazole chloride.

[0093] Comparative Example 7

[0094] A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium is carried out according to the method in Example 1, except that when modifying the fumed silica, an equal amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride is replaced by 1-hydroxyethyl-3-methylimidazole tetrafluoroborate.

[0095] Performance Testing

[0096] The pesticide compositions prepared in the examples and comparative examples of the present application were tested for suspension stability, suspension rate and dispersibility in water. Specifically, for suspension stability, the prepared pesticide composition was first placed at room temperature for 2 hours, then at 0°C for 2 hours, then at room temperature for 2 hours, then at 54°C for 2 hours, and then at room temperature for 2 hours, with 8 hours as one cycle. The above cycles were used to perform treatment, and the time for the obtained suspension to bottom out, stratify or precipitate was counted. The statistical results are shown in Table 1 below.

[0097] The dispersibility in water is obtained by diluting the dispersible oil suspension prepared in the examples and comparative examples in water at a ratio of 1:50, and then leaving it to stand to observe the time for stratification and precipitation to occur. The statistical results are shown in Table 1 below.

[0098] Table 1:

[0099]

[0100] Table 1 continued:

[0101]

[0102] Referring to the test results in Table 1 above, the pesticide composition prepared in the examples of the present application has excellent suspension stability and water dispersibility. Combining the test results of Example 1 and Example 4, when preparing the sodium salt of sulfonated styrene-maleic anhydride copolymer, when no tert-butyl carbonate monomer is added, its suspension stability is reduced. The steric hindrance of tert-butyl carbonate in tert-butyl carbonate helps to reduce the precipitation and bottoming of the pesticide active ingredient particles during subsequent storage. Combining the test results of Example 1 and Examples 5-7, the 2-hydroxy-N, N, N,-trimethylethylamine chloride in the fumed silica modifier is modified by ammoniation and then added to further improve its suspension stability and water dispersibility. Referring to the test results of Example 1 and Comparative Examples 1 and 2, when the emulsifier is a commonly used polyoxyethylene ether, although it has good dispersibility in water, its suspension stability is significantly reduced. Combined with the test results of Comparative Example 3, when the fumed silica is not modified and directly added, its anti-settling effect in the pesticide system of the present application is also significantly reduced. Combined with the test results of Comparative Example 4, when the modified fumed silica is replaced with a commonly used magnesium aluminum silicate anti-settling agent, its suspension stability is significantly reduced. Referring to the test results of Example 1 and Comparative Example 5, when only a silane coupling agent is used to modify the fumed silica, its water dispersibility and suspension stability are reduced. Combined with the test results of Comparative Examples 6 and 7, when the fumed silica is modified, when chlorinated 2-hydroxy-N, N, N,-trimethylethylamine is replaced with a hydroxyl group but does not contain a trimethylamine group, its suspension stability is significantly reduced.

[0103] In addition, the pesticide compositions prepared in the examples of the present application were tested for 14-day low-temperature stability in accordance with GB / T19137-2003, and all were qualified. They were then tested for 14-day hot storage stability in accordance with GB / T19136-2003, and the suspension rate at 54±2°C was greater than 99%, meeting the requirements.

[0104] Finally, the pesticide compositions prepared in Examples 1 and 5 of the present application were mixed with water at a mass ratio of 1:150, and a spraying weed control test was carried out in an orchard under sunny weather conditions. It can be seen that more than 70% of the weeds in the examples of the present application were withered 3 days after the pesticide composition was applied, more than 99% of the weeds were withered 5 days after the pesticide was applied, and the effective period was as long as 60 days. After 5 days of spraying with 66% fluazifop-glufosinate wettable powder as required, more than 50% of the weeds were withered, and more than 95% of the weeds were withered 7 days after the spraying, the dispersible oil suspension pesticide composition prepared in the present application is more convenient to use and has better efficacy.

[0105] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A pesticide composition containing fluazifop-butyl and glufosinate-ammonium, characterized in that: It includes the following raw materials in parts by weight: 2-8 parts of fluazifop-butyl, 15-25 parts of glufosinate-ammonium, 3-8 parts of dispersant, 18-30 parts of emulsifier, 1-3 parts of anti-settling agent and 60-75 parts of vegetable oil; Among them, the emulsifier is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin, the anti-settling agent is selected from an organic bentonite and modified fumed silica in a mass ratio of 1: (1.2-1.5), and the modified fumed silica is made by immersing fumed silica in an aqueous solution prepared by 2-hydroxy-N, N, N,-trimethylethylamine chloride and 3-aminopropyltriethoxysilane and then drying; The sulfonated styrene-maleic anhydride copolymer sodium salt is prepared by the following method: Styrene monomer and maleic anhydride monomer are mixed, added to a mixed solvent of xylene and acetone, and then lauroyl peroxide and n-butyl mercaptan are added, the temperature is raised to 65-75° C., reacted for 2-3 hours, and then tert-butyl carbonate is added to continue the reaction for 30-50 minutes, and then cooled to room temperature, filtered and washed with water to obtain a styrene-maleic anhydride copolymer; The prepared styrene-maleic anhydride copolymer is mixed with a dichloromethane solvent, and then concentrated sulfuric acid is added dropwise under stirring, the reaction temperature is controlled not to exceed 40° C., the reaction is continued for 20-30 minutes, and then the temperature is raised to 60-65° C., the reaction is continued for 60-90 minutes, and then cooled, mixed with water, allowed to stand and precipitate, and then filtered and washed with water, and then added to a sodium hydroxide solution, the pH is adjusted to 7.5-8.5, and then evaporated and crystallized to obtain a sulfonated styrene-maleic anhydride copolymer sodium salt; In the preparation process of sulfonated styrene-maleic anhydride copolymer sodium salt, the mass ratio of styrene monomer to maleic anhydride monomer is 1:(0.7-0.8), the mass ratio of xylene to acetone is 1:(0.8-1.2), and the added amount of xylene is 3-4 times the mass of the styrene monomer, the added amount of lauroyl peroxide is 2-4wt% of the styrene monomer, the added amount of n-butyl mercaptan is 0.5-1wt% of the styrene monomer, and the added amount of versatate is 20-30wt% of the styrene monomer; The mass ratio of styrene-maleic anhydride copolymer to dichloromethane is 1:(3-4), and the amount of concentrated sulfuric acid added is 3-5wt% of the styrene-maleic anhydride copolymer; The emulsifier is a mixture of sulfonated styrene-maleic anhydride copolymer sodium salt and hydroxylated lecithin in a mass ratio of 1: (0.6-0.8); The dispersant is a polycarboxylate dispersant; When the modified fumed silica is prepared, the soaking water solution is prepared by mixing 2-hydroxy-N, N, N,-trimethylethylamine chloride, 3-aminopropyltriethoxysilane and water in a mass ratio of 1: (4-5): (8-10), and the soaking water solution is 6-8 times the mass of the fumed silica.

2. The pesticide composition containing fluazifop-butyl and glufosinate-ammonium according to claim 1, characterized in that: The chlorinated 2-hydroxy-N, N, N,-trimethylethylamine is added after being modified by amination. The specific method is: after mixing the chlorinated 2-hydroxy-N, N, N,-trimethylethylamine with an alkaline solution, heating to 40-45° C., then adding hydroxyethylethylenediamine, reacting for 40-60 minutes and then cooling to obtain the aminated modified chlorinated 2-hydroxy-N, N, N,-trimethylethylamine.

3. A pesticide composition containing fluazifop-butyl and glufosinate-ammonium according to claim 2, characterized in that: In the amination modification process of 2-hydroxy-N, N, N,-trimethylethylamine chloride, the alkaline solution is a sodium hydroxide solution with a mass fraction of 20-30wt%, and the amount of the alkaline solution added is 5-10wt% of the amount of 2-hydroxy-N, N, N,-trimethylethylamine chloride added, and the mass ratio of hydroxyethylethylenediamine to 2-hydroxy-N, N, N,-trimethylethylamine chloride is 1: (1.2-1.5).

4. The pesticide composition containing fluazifop-butyl and glufosinate-ammonium according to claim 1, characterized in that: The vegetable oil is selected from one or more of soybean oil, corn oil, rapeseed oil, castor oil and vegetable oil esters.

5. A method for preparing a pesticide composition containing fluazifop-butyl and glufosinate-ammonium as claimed in any one of claims 1 to 4, characterized in that: The method comprises the following steps: mixing and stirring vegetable oil, an emulsifier and an anti-settling agent to obtain an oil phase, then adding fluazifop-butyl and glufosinate-ammonium, mixing and stirring, adding a dispersant, and then performing homogenization and grinding to obtain a dispersible oil suspension type pesticide composition.

6. Use of the pesticide composition containing fluazifop-butyl and glufosinate-ammonium as claimed in any one of claims 1 to 4, characterized in that: The pesticide composition containing fluazifop-butyl and glufosinate-ammonium is mixed with water in a mass ratio of 1:(150-200) and then used for weeding.

Images