A composition containing fluorine oxazole amide and chlorpyrifos, and preparation method and application thereof

Abstract

The present application relates to the field of pesticide technology, and in particular to a composition containing fluorine oxazolidinone and chlorpyrifos, and a preparation method and application thereof. A composition containing fluorine oxazolidinone and chlorpyrifos, by mass, includes the following raw materials: 10-12 parts of active ingredients, 4-6 parts of composite surfactants, 2-3 parts of ethylene glycol, 4-5 parts of bio-based thickening adsorbents, 0.3-0.5 parts of defoamers, 4-5 parts of synergists, 2-3 parts of dispersants, 0.5-0.8 parts of preservatives, 5-6 parts of propylene glycol methyl ether acetate, and 65-70 parts of water; wherein the active ingredient is prepared by mixing fluorine oxazolidinone and chlorpyrifos with a mass ratio of (6-8): (4-6), and the synergist is a modified siloxane surfactant. The present application provides a composition containing fluorine oxazolidinone and chlorpyrifos, which has the advantages of synergistic enhancement, high selectivity, environmental compatibility, reduced environmental pollution, and cost savings in the prevention and control of beet armyworms, and is a safe, efficient, and environmentally friendly new pesticide.

Description

Technical Field

[0001] The present application relates to the technical field of pesticides, and in particular to a composition containing fluorine-containing oxazolidinone and chlorpyrifos, and a preparation method and application thereof. Background Art

[0002] Cabbage is a biennial herbaceous plant of the cruciferous family and the genus Brassica, also known as cabbage, Chinese cabbage, cauliflower, etc. Cabbage can also be divided into spring cabbage, summer cabbage, autumn and winter cabbage, and large late-maturing cabbage that matures once a year. It is a multi-seasonal cabbage. Cabbage is rich in vitamins, minerals, and dietary fiber. Regular consumption can enhance human vitality, promote digestion, enhance immunity, and maintain physical health. It has gradually become one of the main vegetable varieties on my country's dining table. Cabbage in my country is mainly planted in the four major advantageous areas of the north, the middle and lower reaches of the Yangtze River, the southwest, and the south of China. In recent years, the domestic cabbage area is about 14 million mu, 65% of which is concentrated in the north and the middle and lower reaches of the Yangtze River.

[0003] The beet armyworm is a omnivorous pest of the family Noctuidae in the order Lepidoptera. In Shandong Province, there are generally five generations a year, especially between July and August, when the third and fourth generations of larvae occur in large numbers and cause serious damage. The adults are phototactic and are active at night. They hide in dark places such as the back of leaves, grass, and soil cracks during the day and become active in the evening. The eggs are mostly laid on the back of leaves, laid flat in one or more overlapping layers, and the egg masses are covered with white scales. The beet armyworm can harm vegetables such as cabbage, Chinese cabbage, celery, cauliflower, carrots, asparagus, water spinach, amaranth, and peppers. In recent years, it has developed into an important pest, and often breaks out, causing serious losses to vegetable growers and poor vegetable quality, resulting in low market prices, low yields, and reduced income. Therefore, the technical problems of beet armyworm control need to be solved urgently.

[0004] At present, most of the commonly used pesticide dosage forms for controlling cabbage pests are emulsions, wettable powders and other dosage forms with relatively high environmental risks. The failure of the pesticide to penetrate into the cells or wet and spread in time will lead to excessive local concentration on the leaf surface, thus causing leaf burn. The decrease in surface tension caused by traditional surfactants will increase the instability of droplets hitting the leaf surface after spraying, thereby increasing the possibility of droplets sliding off, further affecting the effective deposition of the pesticide, causing residues, which are unsafe for crops and the environment. Summary of the invention

[0005] The purpose of this application is to provide a composition containing fluorine oxazole amide and chlorpyrifos and its preparation method and application in view of the deficiencies of the current technology. The composition containing fluorine oxazole amide and chlorpyrifos prepared in this application has the advantages of synergistic synergy, high selectivity, environmental compatibility, reduced environmental pollution, cost savings, etc. in controlling beet armyworm. At the same time, the added composite surfactant has hydrophilic and lipophilic properties, low viscosity, good spreadability, and can make the agent better adhere to the leaf surface and penetrate into the leaf tissue, avoiding the phenomenon of leaf burning caused by excessive accumulation of the agent on the leaf surface, preventing the agent particles from clogging the leaf surface stomata, water pores or cell gaps, and reducing the occurrence of pesticide damage.

[0006] In a first aspect, the present application provides a composition containing fluorine oxazole amide and chlorpyrifos, using the following technical solution:

[0007] A composition containing fluorooxazolidinone and chlorpyrifos, comprising the following raw materials by weight: 10-12 parts of active ingredients, 4-6 parts of composite surfactants, 2-3 parts of ethylene glycol, 4-5 parts of bio-based thickening adsorbents, 0.3-0.5 parts of defoamers, 4-5 parts of synergists, 2-3 parts of dispersants, 0.5-0.8 parts of preservatives, 5-6 parts of propylene glycol methyl ether acetate, and 65-70 parts of water; wherein the active ingredient is prepared by mixing fluorooxazolidinone and chlorpyrifos at a weight ratio of (6-8):(4-6), and the synergist is a modified silicone surfactant.

[0008] By adopting the above technical scheme, the active ingredients (fluoxazolidinone and chlorpyrifos): they are mixed in a specific ratio, have a synergistic effect, and can improve the control effect of cabbage beet armyworm. Composite surfactant: This surfactant has hydrophilic and lipophilic properties, low viscosity, and good spreadability. It can make the agent better adhere to the surface of the leaves and penetrate into the inner part of the leaf tissue, avoid the phenomenon of leaf burning caused by excessive accumulation of the agent on the surface of the leaves, prevent the agent particles from blocking the stomata, water pores or cell gaps on the leaf surface, and reduce the occurrence of pesticide damage. Ethylene glycol as an antifreeze: maintain the stability of the composition under low temperature conditions to prevent stratification or crystallization caused by temperature changes. Bio-based thickening adsorbent: not only efficiently adsorbs the active ingredients, but also promotes the slow dissolution of chitosan when it meets water by adding citric acid, thereby accelerating the release of the active ingredients, further improving the control effect and duration of the beet armyworm. Defoamer: used to eliminate foam in the product to ensure the quality and use effect of the product. Synergist (modified siloxane surfactant): effectively reduces the surface tension of the product, so that the agent can be fully spread on the crop, so that the contact area between the agent and the crop is larger, the residence time of the liquid on the plant surface can be enhanced, the loss of effective ingredients is reduced, and the efficacy is more significant. Dispersant: helps the active ingredients to be evenly dispersed in the product and improves the use effect of the product. Preservative: prevents the product from deteriorating during storage and use, and ensures the quality and safety of the product. Propylene glycol methyl ether acetate: as a harmless solvent, it has a strong solubility and has a variety of functional groups. It has a better compounding effect with other materials, making the overall performance of the product more stable. Water: as a solvent, it helps to mix and dissolve the components. In summary, the components in the present application cooperate with each other and play a synergistic role together, so that the composition containing fluorine oxazolidinone and chlorpyrifos has the advantages of synergistic enhancement, high selectivity, environmental compatibility, reduced environmental pollution, and cost savings in the prevention and control of beet armyworms.

[0009] Preferably, the active ingredient is prepared by mixing fluazifopamide and chlorpyrifos at a mass ratio of 6:5.

[0010] By adopting the above technical scheme, firstly, fluazifop-doxazolidinone is a broad-spectrum insecticide with good control effect on various pests. It inhibits the activity of acetylcholinesterase in the insect nervous system, causing the neurotransmitter acetylcholine to accumulate in the synaptic cleft, thereby causing overexcitement and death of the insect. Secondly, fluazifop-doxazolidinone is a benzoylurea insecticide with the characteristics of high efficiency, low toxicity and low residue. It inhibits the formation of the insect cuticle, making it impossible for the insect to molt normally, thereby causing the death of the insect. When these two active ingredients are mixed in an appropriate proportion, a synergistic effect will be generated between them. This means that their control effects will enhance each other and improve the control effect on beet armyworm. At the same time, this composition also has high selectivity, which can prevent and control beet armyworm in a targeted manner and reduce the impact on other organisms.

[0011] Preferably, the composite surfactant comprises the following raw materials, measured by mass: 15 parts of lauramide propyl hydroxysulfobetaine, 15 parts of tristyrylphenol polyoxyethylene ether phosphate, 25 parts of ester-based glycyrrhetinic acid pyridinium bromide, 32 parts of cyclohexanone, and 18 parts of deionized water.

[0012] By adopting the above technical scheme, firstly, lauramide propyl hydroxysulfo betaine is a hydrophilic surfactant with good emulsification, dispersion and wetting properties. It can reduce the surface tension of water, make the agent easier to spread on the surface of crops, and help the penetration and absorption of the agent. Secondly, tristyrylphenol polyoxyethylene ether phosphate is a lipophilic surfactant, which also has good emulsification, dispersion and wetting properties. It works together with lauramide propyl hydroxysulfo betaine to further enhance the emulsification, dispersion and wetting properties of the composition, and improve the stability and adhesion of the agent on the surface of crops. Ester-based glycyrrhetinic acid bromopyridinium, which is hydrophilic and lipophilic, has low viscosity and good spreadability, so that the pesticide can be well transferred and penetrated when applied, so as not to cause burning leaves due to excessive local concentration and drug damage caused by drug particles blocking the stomata and water pores on the leaf surface or blocking the intercellular space after entering the tissue. Finally, cyclohexanone is an organic solvent that can increase the solubility and stability of the composition. Deionized water is used to adjust the concentration and viscosity of the composition to make it easier to use. In summary, the components in the composite surfactant act synergistically with each other to improve the performance of the composition. The composite surfactant has hydrophilic and lipophilic properties, low viscosity, and good spreadability, which can make the agent better adhere to the leaf surface and penetrate into the leaf tissue, avoiding the phenomenon of leaf burning caused by excessive accumulation of the agent on the leaf surface, preventing the agent particles from blocking the stomata, water pores or cell gaps on the leaf surface, and reducing the occurrence of drug damage.

[0013] Preferably, the preparation method of the composite surfactant comprises the following steps:

[0014] S41, according to the mass fractions, the ester-based glycyrrhetinic acid pyridinium bromide, tristyrylphenol polyoxyethylene ether phosphate and cyclohexanone are fully mixed to obtain a mixed solution A;

[0015] S42. According to the mass fractions, lauramide propyl hydroxysulfobetaine and deionized water are added to the mixed solution A, stirred and heated to 60° C., then stirred for 30 min, and cooled to room temperature to obtain a composite surfactant.

[0016] Preferably, the preparation method of the ester-based glycyrrhetinic acid pyridinium bromide comprises the following steps:

[0017] S51. Dissolve 110 parts of glycyrrhetinic acid in 3000 parts of methanol according to mass fractions, add 1500 parts of 1 mol / L hydrochloric acid at 0°C, stir at 72°C for 26 hours, and concentrate to dryness at 5°C and 0.05 MPa to obtain a white solid A;

[0018] S52, according to the mass fraction, dissolve 120 parts of white solid A in 4000 parts of dichloromethane, add 35 parts of potassium carbonate, add 74 parts of bromoacetyl bromide at 0°C, stir at 10°C for 16 hours, filter, and concentrate the filter cake to dryness at 48°C and 0.05MPa to obtain a white solid B;

[0019] S53. Dissolve 120 parts of white solid B in 65 parts of pyridine according to mass fractions, stir at 20°C for 6 hours, and concentrate to dryness at 48°C and 0.05 MPa to obtain ester glycyrrhetinic acid bromopyridine.

[0020] By adopting the above technical scheme, the prepared ester-based glycyrrhetinic acid pyridinium bromide is hydrophilic and lipophilic, has low viscosity and good spreadability, so that the pesticide can be well transmitted and penetrated when applied, thereby preventing leaf burning due to excessive local concentration and pesticide damage caused by the drug particles blocking the stomata and water pores on the leaf surface or blocking the intercellular spaces after entering the tissue.

[0021] Preferably, the method for preparing the bio-based thickening adsorbent comprises the following steps:

[0022] S61, according to the mass parts, add 80 parts of chitosan, 2 parts of citric acid, 6 parts of xanthan gum and 12 parts of white carbon black into an ultrafine grinder, mix and grind evenly to obtain chitosan mother powder;

[0023] S62. According to the mass proportions, 100 parts of chitosan mother powder and 60 parts of magnesium aluminum silicate are added into an ultrafine grinder for pulverization and mixing, and 23 parts of purified water are added into an extrusion granulator for granulation and grinding to obtain a bio-based thickening adsorbent with a particle size of 0.02-0.05 mm.

[0024] By adopting the above technical scheme, the bio-based thickening adsorbent is prepared by mixing and grinding chitosan, citric acid, xanthan gum and white carbon black to obtain a mother powder, which is then granulated and ground together with magnesium aluminum silicate to obtain a bio-based thickening adsorbent with a particle size of 0.02-0.05 mm. The bio-based thickening adsorbent not only efficiently absorbs the active ingredients, but also promotes the slow dissolution of chitosan when it meets water by adding citric acid, thereby accelerating the release of the active ingredients, further improving the protective effect and duration against beet armyworm.

[0025] Preferably, the preparation method of the modified siloxane surfactant is: under nitrogen protection, 4 mmol methyl stearate, 2 mmol 1,1,1,3,5,5,5-heptamethyltrisiloxane, 0.1 mmol catalyst nano Au / TiO2 and 5 mL toluene are added to a reactor equipped with a stirrer, the mixture is stirred evenly, the temperature is raised to 135°C, the reaction is carried out for 12 hours, and the modified siloxane surfactant is obtained by distillation under reduced pressure, wherein the mass content of Au in the catalyst nano Au / TiO2 is 5%.

[0026] By adopting the above technical scheme, the prepared modified siloxane surfactant can effectively reduce the surface tension of the product, so that the agent can be fully spread on the crop, the contact area between the agent and the crop is larger, the residence time of the drug solution on the plant surface is enhanced, the loss of active ingredients is reduced, and the drug effect is more significant.

[0027] Preferably, the dispersant is polyoxyethylene fatty acid ester; the preservative is potassium sorbate; and the defoaming agent is a silicone defoaming agent.

[0028] In a second aspect, the present application provides a method for preparing a composition containing fluorine-containing oxazole amide and chlorpyrifos, using the following technical solution:

[0029] As a general technical concept, the present application also provides a method for preparing the above-mentioned composition containing fluorine oxazole amide and chlorpyrifos, comprising the following steps:

[0030] S91. Mix the active ingredient, composite surfactant, ethylene glycol, bio-based thickening adsorbent, defoamer, synergist, dispersant, preservative, propylene glycol methyl ether acetate and water according to their weight fractions, and pre-disperse and shear at a speed of 3500 rpm for 30 minutes to obtain a mixed solution;

[0031] S92, subjecting the mixed solution to ultrafine grinding, grinding at a rotation speed of 2500 rpm for 3 hours, detecting the particle size D90 ≤ 0.8 μm and filtering to obtain a composition containing fluorooxazole amide and chlorpyrifos.

[0032] In a third aspect, the present application provides an application of a composition containing fluorine-containing oxazole amide and chlorpyrifos, using the following technical solution:

[0033] As a general technical concept, the present application also provides the above-mentioned composition containing fluorooxazolidinone and chlorpyrifos for controlling cabbage beet armyworm, corn beet armyworm and cabbage beet armyworm.

[0034] In summary, the beneficial technical effects of this application are:

[0035] 1. Synergistic effect: By mixing fluazifop and fluazifop in a specific ratio, the synergistic effect of the two active ingredients is achieved, significantly enhancing the control effect on beet armyworm. This combination not only improves the insecticidal efficiency, but also may delay the development of pest resistance to a single ingredient.

[0036] 2. Environmental friendliness and safety: Auxiliary ingredients such as added composite surfactants and bio-based thickening adsorbents are designed to improve the environmental compatibility of the agent and reduce the impact on non-target organisms. These ingredients help reduce the residue and migration of the agent in the environment and mitigate potential negative impacts on the ecosystem.

[0037] 3. Improve application performance: The use of modified siloxane surfactants reduces the surface tension of the product, allowing the liquid medicine to better adhere to and penetrate into the leaves of crops, increasing the contact area and prolonging the residence time, thereby improving the efficacy and reducing the loss of active ingredients. In addition, propylene glycol methyl ether acetate is used as a solvent, and its good solubility and compounding effect ensure the stability and efficiency of the product.

[0038] 4. Reduce the risk of pesticide damage: Through carefully selected formula components, such as ester-based glycyrrhetinic acid pyridinium bromide, and optimized formulation process, the risk of pesticide accumulation on the leaf surface and particles clogging stomata is reduced, thereby reducing the possibility of pesticide damage.

[0039] 5. Cost-effectiveness: By improving the efficacy and selectivity of pesticides, the amount of pesticides used is reduced, which indirectly reduces the cost of agricultural production. At the same time, due to the reduction of environmental pollution and the risk of pesticide damage, it may also save farmers the additional costs incurred by remedial measures.

[0040] 6. Extended duration of effect: The application of bio-based thickening adsorbents, especially the design of combining citric acid to promote the slow dissolution of chitosan, helps to control the release rate of active ingredients, prolong the effective action time of the agent, reduce the frequency of application, further reduce costs and improve the durability of the protective effect.

[0041] 7. Adding composite surfactants: Composite surfactants have hydrophilic and lipophilic properties, low viscosity and good spreadability. They can make the pesticide adhere better to the leaf surface and penetrate into the leaf tissue, avoiding leaf burning caused by excessive accumulation of pesticide on the leaf surface, preventing pesticide particles from clogging the stomata, water pores or cell gaps on the leaf surface, and reducing the occurrence of pesticide damage. DETAILED DESCRIPTION

[0042] The embodiments of the present application will be described in detail below in conjunction with the examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. In the examples, if specific conditions are not specified, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0043] In the following examples, preparation examples and comparative preparation examples, 1 part means 10 g.

[0044] Preparation Example 1 Preparation of modified siloxane surfactant

[0045] The preparation method of the modified siloxane surfactant is as follows: under nitrogen protection, 4 mmol methyl stearate, 2 mmol 1,1,1,3,5,5,5-heptamethyltrisiloxane, 0.1 mmol catalyst nano Au / TiO2 and 5 mL toluene are added into a reactor equipped with a stirrer, the mixture is stirred evenly, the temperature is raised to 135° C., and after reacting for 12 hours, the modified siloxane surfactant is obtained by distillation under reduced pressure, wherein the mass content of Au in the catalyst nano Au / TiO2 is 5%.

[0046] Preparation Example 2 Preparation of bio-based thickening adsorbent

[0047] The preparation method of the bio-based thickening adsorbent comprises the following steps:

[0048] S61, according to the mass parts, add 80 parts of chitosan, 2 parts of citric acid, 6 parts of xanthan gum and 12 parts of white carbon black into an ultrafine grinder, mix and grind evenly to obtain chitosan mother powder;

[0049] S62. According to the mass proportions, 100 parts of chitosan mother powder and 60 parts of magnesium aluminum silicate are added into an ultrafine grinder for pulverization and mixing, and 23 parts of purified water are added into an extrusion granulator for granulation and grinding to obtain a bio-based thickening adsorbent with a particle size of 0.02-0.05 mm.

[0050] Preparation Example 3 Preparation of Ester-Based Glycyrrhetinic Acid Bromopyridinium

[0051] The preparation method of ester-based glycyrrhetinic acid pyridinium bromide comprises the following steps:

[0052] S51. Dissolve 110 parts of glycyrrhetinic acid in 3000 parts of methanol according to mass fractions, add 1500 parts of 1 mol / L hydrochloric acid at 0°C, stir at 72°C for 26 hours, and concentrate to dryness at 5°C and 0.05 MPa to obtain a white solid A;

[0053] S52, according to the mass fraction, dissolve 120 parts of white solid A in 4000 parts of dichloromethane, add 35 parts of potassium carbonate, add 74 parts of bromoacetyl bromide at 0°C, stir at 10°C for 16 hours, filter, and concentrate the filter cake to dryness at 48°C and 0.05MPa to obtain a white solid B;

[0054] S53. Dissolve 120 parts of white solid B in 65 parts of pyridine according to mass fractions, stir at 20°C for 6 hours, and concentrate to dryness at 48°C and 0.05 MPa to obtain ester glycyrrhetinic acid bromopyridine.

[0055] Preparation Example 4 Preparation of composite surfactant

[0056] The preparation method of the composite surfactant comprises the following steps:

[0057] S41, according to the mass parts, 25 parts of ester-based glycyrrhetinic acid bromide pyridinium (ester-based glycyrrhetinic acid bromide pyridinium prepared in Preparation Example 3), 15 parts of tristyrylphenol polyoxyethylene ether phosphate and 32 parts of cyclohexanone are fully mixed to obtain a mixed solution A;

[0058] S42. According to their weight proportions, 15 parts of lauramide propyl hydroxysulfobetaine and 18 parts of deionized water were added to the mixed solution A, stirred and heated to 60° C., then stirred for 30 minutes, and cooled to room temperature to obtain a composite surfactant.

[0059] Preparation Comparative Example 1 Preparation of surfactant

[0060] The preparation method of a surfactant comprises the following steps: 55 parts of tristyrylphenol polyoxyethylene ether phosphate and 32 parts of cyclohexanone are fully mixed according to their weight parts, 18 parts of deionized water are added thereto, the mixture is stirred and heated to 60°C, the mixture is stirred for 30 minutes, and the mixture is cooled to room temperature to obtain a surfactant.

[0061] Preparation Comparative Example 2 Preparation of surfactant

[0062] The preparation method of a surfactant comprises the following steps: fully mixing 55 parts of lauramide propyl hydroxysulfobetaine and 32 parts of cyclohexanone according to their weight parts, adding 18 parts of deionized water thereto, stirring and heating to 60°C, stirring for 30 minutes, and cooling to room temperature to obtain a surfactant.

[0063] Preparation Comparative Example 3 Preparation of Surfactant

[0064] The preparation method of a surfactant comprises the following steps: 55 parts of ester-glycyrrhetinic acid bromopyridinium (ester-glycyrrhetinic acid bromopyridinium prepared in Preparation Example 3) and 32 parts of cyclohexanone are fully mixed according to their weight parts, and then 18 parts of deionized water are added thereto, and the mixture is stirred and heated to 60° C., and then stirred for 30 minutes, and cooled to room temperature to obtain a surfactant. Example 1

[0065] A composition containing fluorooxazolidinone and chlorfluazuron, comprising the following raw materials by mass: 10 parts of active ingredient, 4 parts of composite surfactant, 2 parts of ethylene glycol, 4 parts of bio-based thickening adsorbent, 0.3 parts of organosilicon defoamer, 4 parts of modified siloxane surfactant, 2 parts of fatty acid polyoxyethylene ester, 0.5 parts of potassium sorbate, 5 parts of propylene glycol methyl ether acetate, and 65 parts of water; wherein the active ingredient is prepared by mixing fluorooxazolidinone and chlorfluazuron in a mass ratio of 6:4;

[0066] The preparation method of the above-mentioned composition containing fluorine oxazole amide and chlorpyrifos comprises the following steps:

[0067] S91. Mix the active ingredient, composite surfactant, ethylene glycol, bio-based thickening adsorbent, silicone defoamer, modified siloxane surfactant, fatty acid polyoxyethylene ester, potassium sorbate, propylene glycol methyl ether acetate and water according to their weight fractions, and pre-disperse and shear at a speed of 3500 rpm for 30 minutes to obtain a mixed solution;

[0068] S92, subjecting the mixed solution to ultrafine grinding at a rotation speed of 2500 rpm for 3 hours, filtering after the particle size D90 is detected to be 0.7 μm, to obtain a composition containing fluorooxazole amide and chlorpyrifos. Example 2

[0069] A composition containing fluorooxazolidinone and chlorfluazuron, comprising the following raw materials by mass: 12 parts of active ingredient, 6 parts of composite surfactant, 3 parts of ethylene glycol, 5 parts of bio-based thickening adsorbent, 0.5 parts of organosilicon defoamer, 5 parts of modified siloxane surfactant, 3 parts of fatty acid polyoxyethylene ester, 0.8 parts of potassium sorbate, 6 parts of propylene glycol methyl ether acetate, and 70 parts of water; wherein the active ingredient is prepared by mixing fluorooxazolidinone and chlorfluazuron in a mass ratio of 8:5;

[0070] The preparation method of the above-mentioned composition containing fluorine oxazole amide and chlorpyrifos comprises the following steps:

[0071] S91. Mix the active ingredient, composite surfactant, ethylene glycol, bio-based thickening adsorbent, silicone defoamer, modified siloxane surfactant, fatty acid polyoxyethylene ester, potassium sorbate, propylene glycol methyl ether acetate and water according to their weight fractions, and pre-disperse and shear at a speed of 3500 rpm for 30 minutes to obtain a mixed solution;

[0072] S92, subjecting the mixed solution to ultrafine grinding, grinding at a rotation speed of 2500 rpm for 3 hours, filtering after detecting the particle size D90 to be 0.8 μm, to obtain a composition containing fluorooxazole amide and chlorpyrifos. Example 3

[0073] A composition containing fluorine oxazolidinone and chlorpyrifos, comprising the following raw materials by mass: 11 parts of active ingredient, 5 parts of composite surfactant, 2.5 parts of ethylene glycol, 4.5 parts of bio-based thickening adsorbent, 0.4 parts of organosilicon defoamer, 4.5 parts of modified siloxane surfactant, 2.5 parts of fatty acid polyoxyethylene ester, 0.7 parts of potassium sorbate, 5.5 parts of propylene glycol methyl ether acetate, and 68 parts of water; wherein the active ingredient is prepared by mixing fluorine oxazolidinone and chlorpyrifos at a mass ratio of 7:5;

[0074] The preparation method of the above-mentioned composition containing fluorine oxazole amide and chlorpyrifos comprises the following steps:

[0075] S91. Mix the active ingredient, composite surfactant, ethylene glycol, bio-based thickening adsorbent, silicone defoamer, modified siloxane surfactant, fatty acid polyoxyethylene ester, potassium sorbate, propylene glycol methyl ether acetate and water according to their weight fractions, and pre-disperse and shear at a speed of 3500 rpm for 30 minutes to obtain a mixed solution;

[0076] S92, subjecting the mixed solution to ultrafine grinding, grinding at a rotation speed of 2500 rpm for 3 hours, filtering after detecting the particle size D90 to be 0.8 μm, to obtain a composition containing fluorooxazole amide and chlorpyrifos. Example 4

[0077] The same as Example 3, except that the active ingredient is prepared by mixing fluoxetine amide and chlorpyrifos amide in a mass ratio of 6:5.

[0078] Comparative Example 1

[0079] The same as Example 4, except that an equal amount of magnesium aluminum silicate with a particle size of 0.02-0.05 mm is used instead of the bio-based thickening adsorbent.

[0080] Comparative Example 2

[0081] The same as Example 4, except that an equal amount of the surfactant prepared in Comparative Preparation Example 1 is used instead of the composite surfactant.

[0082] Comparative Example 3

[0083] The same as Example 4, except that an equal amount of the surfactant prepared in Comparative Preparation Example 2 is used instead of the composite surfactant.

[0084] Comparative Example 4

[0085] The same as Example 4, except that an equal amount of the surfactant prepared in Comparative Preparation Example 3 is used instead of the composite surfactant.

[0086] Comparative Example 5

[0087] Same as Example 4, except that an equal amount of water is used instead of the modified siloxane surfactant.

[0088] Test Example 1

[0089] 1. Field trial on the control of cabbage beet armyworm

[0090] The efficacy experiment of the composition containing fluorine oxazolidinone and chlorpyrifos prepared in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 5 was carried out. The experiment set 10 treatments (Table 1), each treatment was repeated 4 times, a total of 40 areas, each area was about 20m 2 , each treatment was randomly arranged. The experimental field was flat, the cabbage was in the early stage of rosette, and the growth was good. It was cloudy on the day of application, the temperature was 22-29℃, and the northerly wind was 3-4. From the application of the pesticide to the end of the investigation, there were 6 cloudy days, 1 cloudy day, and no precipitation. The front and back of the cabbage leaves were evenly sprayed, and the same amount of clean water was sprayed as a blank control CK. Only one pesticide was applied during the experiment, the dosage was 20mL / mu, and the dilution multiple was 500 times. 18 days before the application of the pesticide, the experimental field used highly effective cypermethrin to control the diamondback moth once. The survey method adopted the five-point sampling method. 10 cabbages were randomly selected in each area. The insect population density was investigated before and 1, 3, and 7 days after the application of the pesticide, and the data was recorded. The insect population reduction rate and the corrected control effect were calculated. During the experiment, it was observed whether the agent caused phytotoxicity to the cabbage and had an effect on the beet armyworm pest. The formula for calculating the insect population reduction rate and control effect is as follows:

[0091] Insect population reduction rate = (insect population base - number of live insects after application) / insect population base × 100%;

[0092] Corrected control effect = (insect population reduction rate in the pesticide treatment area - insect population reduction rate in the blank control area) / (100 - insect population reduction rate in the blank control area) * 100%;

[0093] The test results are shown in Table 1.

[0094] Table 1 Field test results of controlling cabbage beet armyworm

[0095]

[0096] Different lowercase letters after the data indicate significant differences (P < 0.05).

[0097] 2. Contact angle test

[0098] The contact angle is an important indicator for evaluating the wettability of a solution at the target interface. In this experiment, cabbage leaves were used as the interface to study the leaf surface wetting effect of the prepared composition. The contact angle reflects the wetting and spreading characteristics of a liquid on the target surface, and a smaller contact angle means better wetting and spreading performance. Better wettability on the leaf surface is conducive to the attachment and distribution of poorly soluble drug particles on the leaf surface, improving their adhesion to the target and the control effect. The prepared composition was formulated into a 0.1 g / mL aqueous solution, 1 μL was dropped on the surface of the cabbage leaf, and the contact angle on its surface was calculated. Each group was tested three times, and the results were averaged. The test results are shown in Table 2.

[0099] Table 2 Contact angle

[0100]

[0101] 3. Pesticide resistance test

[0102] The compositions containing oxazolidinone and chlorpyrifos prepared in Examples 1 to 4 and Comparative Examples 1 to 5 were tested for their resistance to pesticide damage. The test was conducted with 10 treatments, 4 replicates per treatment, and a total of 40 areas, each area of ​​about 20 m 2 , each treatment was randomly arranged. The experimental field was flat, the cabbage was in the early stage of rosette, and the growth was good. It was cloudy on the day of application, the temperature was 20-27℃, and the northerly wind was 3-4. From the application of the pesticide to the end of the investigation, the weather was mainly cloudy with no precipitation. The front and back of the cabbage leaves were evenly sprayed, and the same amount of water was sprayed as a blank control CK. During the experiment, only one pesticide was applied, the dosage was 20mL / mu, and the dilution multiple was 500 times. The cabbage leaves were observed and registered on the 7d, 14d, and 28d of the application of the drug, and the resistance to pesticide damage was recorded. The resistance to pesticide damage is divided into the following types: Level 0, the leaves are yellowed or even dead; Level I, 3 / 4 of the leaves are yellowed; Level II, 1 / 2 of the leaves are yellowed; Level III, 1 / 4 of the leaves are yellowed; Level IV plants grow normally; the specific test results are shown in Table 3.

[0103] Table 3 Resistance to pesticide damage

[0104]

[0105] Analyzing the data in Table 1, Table 2 and Table 3, we can see that:

[0106] 1) The compositions containing fluorine-containing oxazolidinone and chlorpyrifos prepared in Examples 1 to 4 have the advantages of synergistic effect, high selectivity, environmental compatibility, reduced environmental pollution, cost savings, etc. in controlling beet armyworm. At the same time, the added composite surfactant has hydrophilic and lipophilic properties, low viscosity, and good spreadability, which can make the agent better adhere to the leaf surface and penetrate into the leaf tissue, avoiding the phenomenon of leaf burning caused by excessive accumulation of the agent on the leaf surface, preventing the agent particles from clogging the leaf surface stomata, water pores or cell gaps, and reducing the occurrence of pesticide damage.

[0107] 2) The performance comparison analysis of the composition containing fluorine oxazolidinone and chlorpyrifos prepared in Example 4 and Example 3 shows that the active ingredient is prepared by mixing fluorine oxazolidinone and chlorpyrifos in a mass ratio of 6:5. When these two active ingredients are mixed in a specific ratio, a synergistic effect will be generated between them. This means that their control effects will enhance each other and improve the control effect on beet armyworm. At the same time, this composition also has a high selectivity, which can prevent and control beet armyworm in a targeted manner and reduce the impact on other organisms.

[0108] 3) The comparative analysis of the performance of the composition containing fluorine-containing oxazolidinone and chlorpyrifos prepared in Example 4 and Comparative Example 1 shows that the bio-based thickening adsorbent prepared in the present application not only efficiently adsorbs the active ingredients, but also promotes the slow dissolution of chitosan when it comes into contact with water by adding citric acid, thereby accelerating the release of the active ingredients, further improving the control effect and duration of the effect on beet armyworm.

[0109] 4) The performance comparison analysis of the composition containing fluorine-containing oxazolidinone and chlorpyrifos prepared in Example 4 and Comparative Examples 2-4 shows that the composite surfactant prepared in the present application, the components of which act synergistically with each other, jointly improve the performance of the composition, and the composite surfactant has hydrophilic and lipophilic properties, low viscosity, and good spreadability, which enables the agent to better adhere to the leaf surface and penetrate into the leaf tissue, avoiding the phenomenon of leaf burning caused by excessive accumulation of the agent on the leaf surface, preventing the agent particles from clogging the stomata, water pores or cell gaps on the leaf surface, and reducing the occurrence of pesticide damage.

[0110] 5) The comparative analysis of the performance of the composition containing fluorine-containing oxazolidinone and chlorpyrifos prepared in Example 4 and Comparative Example 5 shows that the modified siloxane surfactant prepared in the present application can effectively reduce the surface tension of the product, so that the agent can be fully spread on the crop, so that the contact area between the agent and the crop is larger, and the residence time of the drug solution on the plant surface can be enhanced, and the loss of active ingredients is reduced, so that the drug effect is more significant.

[0111] The above embodiments are only used to explain the technical solutions of the present application rather than to limit them. Although the above embodiments provide a specific description of the present application, relevant technical personnel should understand that the specific implementation modes of the present invention can still be modified or replaced by equivalents, and any modifications and equivalent replacements that do not depart from the spirit and scope of the present application should be included in the scope of protection of the present application.

Claims

1. A composition containing fluorine oxazole amide and chlorpyrifos, characterized in that: The preparation material is composed of the following raw materials by weight: 10-12 parts of active ingredients, 4-6 parts of composite surfactants, 2-3 parts of ethylene glycol, 4-5 parts of bio-based thickening adsorbents, 0.3-0.5 parts of defoamers, 4-5 parts of synergists, 2-3 parts of dispersants, 0.5-0.8 parts of preservatives, 5-6 parts of propylene glycol methyl ether acetate, and 65-70 parts of water; wherein the active ingredient is prepared by mixing fluoxetine amide and chlorpyrifos amide in a weight ratio of (6-8):(4-6), and the synergist is a modified siloxane surfactant; The composite surfactant is composed of the following raw materials by weight: 15 parts of lauramide propyl hydroxysulfobetaine, 15 parts of tristyrylphenol polyoxyethylene ether phosphate, 25 parts of ester-based glycyrrhetinic acid pyridinium bromide, 32 parts of cyclohexanone, and 18 parts of deionized water; The preparation method of the composite surfactant comprises the following steps: S41, according to the mass fractions, the ester-based glycyrrhetinic acid pyridinium bromide, tristyrylphenol polyoxyethylene ether phosphate and cyclohexanone are fully mixed to obtain a mixed solution A; S42, according to the mass fractions, lauramide propyl hydroxysulfobetaine and deionized water were added to the mixed solution A, stirred and heated to 60° C., stirred for 30 min, and cooled to room temperature to obtain a composite surfactant; The preparation method of the ester-based glycyrrhetinic acid pyridinium bromide comprises the following steps: S51. Dissolve 110 parts of glycyrrhetinic acid in 3000 parts of methanol according to mass fractions, add 1500 parts of 1 mol / L hydrochloric acid at 0°C, stir at 72°C for 26 hours, and concentrate to dryness at 5°C and 0.05 MPa to obtain a white solid A; S52, according to the mass fraction, dissolve 120 parts of white solid A in 4000 parts of dichloromethane, add 35 parts of potassium carbonate, add 74 parts of bromoacetyl bromide at 0°C, stir at 10°C for 16 hours, filter, and concentrate the filter cake to dryness at 48°C and 0.05MPa to obtain a white solid B; S53, according to the mass fraction, dissolve 120 parts of white solid B in 65 parts of pyridine, stir at 20°C for 6 hours, and concentrate to dryness at 48°C and 0.05 MPa to obtain ester glycyrrhetinic acid pyridine bromide; The preparation method of the bio-based thickening adsorbent comprises the following steps: S61, according to the mass parts, add 80 parts of chitosan, 2 parts of citric acid, 6 parts of xanthan gum and 12 parts of white carbon black into an ultrafine grinder, mix and grind evenly to obtain chitosan mother powder; S62, according to the mass fractions, 100 parts of chitosan mother powder and 60 parts of magnesium aluminum silicate were added into an ultrafine grinder for pulverization and mixing, and 23 parts of purified water were added into an extrusion granulator for granulation, and ground to obtain a bio-based thickening adsorbent with a particle size of 0.02-0.05 mm; The preparation method of the modified siloxane surfactant is as follows: under nitrogen protection, 4mmol methyl stearate, 2mmol 1,1,1,3,5,5,5-heptamethyltrisiloxane, 0.1mmol catalyst nano Au / TiO2 and 5mL toluene are added into a reactor equipped with a stirrer, the mixture is stirred evenly, the temperature is raised to 135°C, and after reacting for 12h, the mixture is distilled under reduced pressure to obtain the modified siloxane surfactant, wherein the mass content of Au in the catalyst nano Au / TiO2 is 5%.

2. A composition containing fluorine-containing oxazole amide and chlorpyrifos according to claim 1, characterized in that: The active ingredient is prepared by mixing fluoxetine amide and chlorpyrifos amide in a mass ratio of 6:

5.

3. A composition containing fluorine-containing oxazole amide and chlorpyrifos according to claim 1, characterized in that: The dispersant is fatty acid polyoxyethylene ester; the preservative is potassium sorbate; and the defoaming agent is an organosilicon defoaming agent.

4. A method for preparing a composition containing fluorine-containing oxazole amide and chlorpyrifos according to any one of claims 1 to 3, characterized in that: The following steps are involved: S91. Mix the active ingredient, composite surfactant, ethylene glycol, bio-based thickening adsorbent, defoamer, synergist, dispersant, preservative, propylene glycol methyl ether acetate and water according to their weight fractions, and pre-disperse and shear at a speed of 3500 rpm for 30 minutes to obtain a mixed solution; S92, subjecting the mixed solution to ultrafine grinding, grinding at a rotation speed of 2500 rpm for 3 hours, detecting the particle size D90 ≤ 0.8 μm and filtering to obtain a composition containing fluorooxazole amide and chlorpyrifos.

5. Use of a composition containing fluorooxazolidinone and chlorpyrifos according to any one of claims 1 to 3 for controlling cabbage beet armyworm, corn beet armyworm and cabbage beet armyworm.

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