A pesticide composition and preparation method thereof

Abstract

The present invention discloses an insecticide composition and a preparation method thereof, relating to the technical field of pesticide compounding. The composition compounds oxazolidinone with highly effective cypermethrin, using a multifunctional modified silica composite carrier as a carrier, and achieves synergistic efficacy through micelle-slow-release technology. The insecticide composition exhibits both rapid and long-lasting control effects against beet armyworm, corn borer, gray leafhopper, and wheat aphid, significantly outperforming a single agent and delaying the development of resistance. The preparation process of the present invention is simple, and the composition can be processed into various dosage forms, such as suspension concentrates and aqueous emulsions, showing promising application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticide compounding, and in particular to an insecticide composition and a preparation method thereof. Background Art

[0002] In recent years, changes in farming and cultivation systems have led to an increasing incidence of pests, severely impacting crop yield and quality. Chemical insecticides are the most economical and effective means of pest control. Their application plays a vital role in recovering crop yield losses and improving the marketability and quality of agricultural products.

[0003] Oxazosulfyl is the first new benzoxazole insecticide containing an ethylsulfonylpyridine structural fragment, recently developed by Sumitomo Chemical Co., Ltd. With its novel structure and novel mechanism of action, it is a broad-spectrum insecticide with excellent control effects against a wide range of pests, including Hemiptera, Coleoptera, and Lepidoptera. It is used to control rice pests and maintains good control effects against brown planthoppers and diamondback moths at low concentrations. It also exhibits good insecticidal effects against planthoppers resistant to fipronil and neonicotinoids.

[0004] Beta-cypermethrin is a representative pyrethroid insecticide and a highly effective isomer of cypermethrin. This compound targets neural sodium ion channels and acts on the peripheral and central nervous systems of insects, causing insects to lose their ability to move by stimulating repeated discharges of nerve cells. Compared with other insecticides, it has relatively low toxicity to humans, has a broad spectrum, stronger insecticidal activity, higher persistence, and exhibits good stability. It is widely used in the control of agricultural pests, sanitary pests, and grain storage.

[0005] When using pesticides for pest control, the long-term, continuous, high-dose use of a single chemical insecticide or one with a single mode of action can easily lead to problems such as insect resistance and the evolution of resistance. Rational compounding or blending of insecticide compounds offers advantages such as reducing pesticide usage, improving control effectiveness, and delaying the onset and development of insect resistance and tolerance, making it one of the most effective approaches to addressing these issues.

[0006] At present, there are no reports on the combined use of Oxazosulfyl and the pyrethroid insecticide cypermethrin for the prevention and control of chewing mouthparts pests such as cotton bollworm, beet armyworm, armyworm, fall armyworm, corn borer, peach borer, striped suppressalis, rice leaf roller, and wheat aphid, cotton aphid, corn aphid, bean aphid, potato aphid, apple aphid, tomato whitefly, gray planthopper, brown planthopper, false-eyed green leafhopper, thrips and other piercing-sucking and rasping-sucking mouthparts pests. Summary of the Invention

[0007] In order to solve the above technical problems, the present invention provides a group of insecticide compositions comprising Oxazosulfyl and the pyrethroid insecticide cypermethrin, which can effectively control chewing mouthparts pests such as cotton bollworm, beet armyworm, armyworm, fall armyworm, corn borer, peach borer, striped suppressalis, and rice leaf roller, and piercing-sucking and rasping-sucking mouthparts pests such as wheat aphid, cotton aphid, corn aphid, bean aphid, potato aphid, apple aphid, tomato whitefly, gray leafhopper, brown planthopper, false-eyed green leafhopper, and thrips, thereby reducing the amount of pesticide applied, improving crop safety, and solving the problem of pest resistance.

[0008] In order to solve the above problems existing in the prior art, the present invention is achieved through the following technical solutions:

[0009] In a first aspect, the present invention provides an insecticide composition comprising an active ingredient A of oxazosulfyl and an active ingredient B of highly effective cypermethrin.

[0010] The mass ratio of the active ingredient A to the active ingredient B is 1-100:1-100.

[0011] Preferably, the mass ratio of the active ingredient A to the active ingredient B is 1-40:1-20.

[0012] More preferably, the mass ratio of the active ingredient A to the active ingredient B is 1-2:1-2.

[0013] The total mass percentage of the active ingredient A and the active ingredient B in the insecticide composition accounts for 1%-95% of the total mass of the insecticide composition.

[0014] Preferably, the total mass percentage of active ingredient A and active ingredient B in the insecticide composition accounts for 3%-9% of the total mass of the insecticide composition. Generally, the insecticide composition of the present invention contains 3%-9% of active ingredients and 91%-97% by weight of pesticide adjuvants.

[0015] Preferably, the pesticide adjuvant consists of a surfactant, a carrier, an emulsifier, a wetting agent, a thickener, an antifreeze agent and a solvent.

[0016] Preferably, the active ingredient, multifunctional modified silica composite carrier, surfactant, thickener, emulsifier, wetting agent, antifreeze agent and solvent are calculated in percentage by weight as follows: active ingredient 3%-9%, carrier 20%-30%, surfactant 3%-7%, emulsifier 3%-8%, wetting agent 1%-3%, thickener 1%-3%, antifreeze agent 2%-4%, and the solvent is supplemented to 100%.

[0017] Preferably, the emulsifier is any one of styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, and fatty alcohol polyoxyethylene ether.

[0018] Preferably, the wetting agent is any one of sodium methylene bisnaphthalene sulfonate, fatty alcohol polyoxyethylene ether and taurine alkyl ester.

[0019] Preferably, the thickener is any one or more of xanthan gum, sodium alginate, sodium carboxymethyl cellulose, and magnesium aluminum silicate.

[0020] Preferably, the antifreeze agent is any one or more of propylene glycol, glycerol, sorbitol and dipropylene glycol monomethyl ether.

[0021] Preferably, the solvent is cyclohexane and / or deionized water.

[0022] Preferably, the carrier is a multifunctional modified silica composite carrier, and the preparation method of the multifunctional modified silica composite carrier comprises the following preparation steps:

[0023] A1: Add silica to ammonium oxalate solution and stir to react. After the reaction is complete, filter and wash until neutral, and dry to obtain ammonium oxalate-etched silica.

[0024] A2: Add ammonium oxalate-etched silica to a citric acid ethanol solution, heat and stir, and blend with a plant-derived synergist and a light protectant in steps. After the reaction is completed, filter and wash to neutrality, and dry to obtain a multifunctional modified silica composite carrier.

[0025] Preferably, the specific steps of A1 are: adding white carbon black to ammonium oxalate solution, stirring and reacting at 80°C-90°C for 4h-6h, filtering and washing to neutrality after the reaction, and drying at 80°C-90°C for 8h-12h to obtain ammonium oxalate-etched white carbon black.

[0026] Preferably, the specific steps of A2 are: adding the ammonium oxalate-etched white carbon black obtained in A1 to a citric acid ethanol solution, stirring the reaction at 76°C-82°C for 3h-6h, adding a plant-derived synergist, stirring at 55°C-65°C for 50min-80min, adding a light protectant, stirring at 70°C-75°C for 30min-40min, filtering and washing until neutral, and drying at 80°C-90°C for 12h-15h to obtain a multifunctional modified white carbon black composite carrier.

[0027] Preferably, the mass parts of the white carbon black, ammonium oxalate solution, citric acid ethanol solution, plant-derived synergist and light protectant are respectively 20-30 parts of white carbon black, 60-80 parts of ammonium oxalate solution, 50-70 parts of citric acid ethanol solution, 1.5-2.1 parts of plant-derived synergist and 1.5-2 parts of light protectant.

[0028] Preferably, the mass percentage of the ammonium oxalate solution is 10%.

[0029] Preferably, the plant-derived synergist is rosinic acid.

[0030] Preferably, the mass ratio of citric acid to anhydrous ethanol in the citric acid ethanol solution is 2:8.

[0031] Preferably, the light protectant is nano zinc oxide and stearic acid, and the mass ratio of nano zinc oxide to stearic acid is 3:1-2.

[0032] Preferably, the average particle size of the nano zinc oxide is 30 nm.

[0033] Preferably, the insecticide composition may also contain various other components, such as protective colloids, binders, thixotropic agents, penetrants, stabilizers, chelating agents, film formers, dyes, colorants and polymers.

[0034] Preferably, the insecticide composition can be diluted or used directly by the user before use.

[0035] Preferably, the specific formulation of the insecticide composition is a wettable powder, a dispersible oil suspension, a suspension concentrate, a suspension seed coating, an emulsifiable concentrate, a water-dispersible granule (dry suspension concentrate), an aqueous emulsion, or a microemulsion.

[0036] In short, the compositions of the present invention can be mixed with solid and liquid additives conventionally used in prior art formulations.

[0037] The insecticide composition of the present invention can be applied to the leaves and seeds of plants to be treated by spraying or seed treatment. Experimental investigations have revealed significant synergistic effects between active ingredients A and B in the insecticide composition of the present invention. This synergistic effect manifests as a reduced application dosage, faster insecticidal action, and longer-lasting results.

[0038] In another aspect, the present invention provides a method for preparing an insecticide composition, comprising the following steps:

[0039] S1: After adding the surfactant and active ingredient B into the solvent and stirring to dissolve, the active ingredient A is added and stirred to obtain an active ingredient micellar solution;

[0040] S2: After uniformly mixing the active ingredient micelle solution with the carrier, a thickener, an emulsifier, a wetting agent and an antifreeze agent are added in sequence, and the mixture is fully mixed and ball-milled to obtain an insecticide composition.

[0041] Preferably, the specific steps of S1 are: adding the surfactant and active ingredient B to a solvent at 45° C.-50° C., stirring to dissolve, adding active ingredient A, stirring for 40 min-50 min, to obtain an active ingredient micellar solution.

[0042] Preferably, the surfactant is polyether-modified heptamethyltrisiloxane.

[0043] Preferably, the specific steps of S2 are: mixing the active ingredient micellar solution and the carrier, stirring at 40°C-50°C for 40min-60min, cooling to 20°C-30°C, adding a thickener, stirring for 20min-30min, adding an emulsifier, a wetting agent and an antifreeze agent, mixing evenly to obtain a mixture, adding the mixture to a zirconium oxide grinding jar, wherein the diameter of the zirconium balls is 3mm-5mm, the ball-to-material ratio is 3:1-3, the rotation speed is controlled at 300rpm-600rpm, ball milling is carried out for 20min-30min, and the amount of grinding aid added is 5% (v / w) of the mixture to obtain an insecticide composition.

[0044] Preferably, the grinding aid is any one or more of ethanol, diethanolamine, and triethanolamine.

[0045] Beneficial effects of the present invention:

[0046] When Oxazosulfyl is combined with highly effective cypermethrin, it exhibits significant synergistic effects against a variety of pests (such as beet armyworm, corn borer, gray leafhopper, and wheat aphid), reducing the amount of medicine used and improving the prevention effect.

[0047] The present invention can effectively delay the development of pest resistance to a single agent and extend the service life of the agent by compounding two active ingredients with different action mechanisms.

[0048] The insecticide composition prepared by the present invention has good control effects on both chewing mouthparts pests (such as corn borer and beet armyworm) and piercing-sucking mouthparts pests (such as gray leafhopper and aphid), and has a wide range of applications.

[0049] This invention uses a two-step ammonium oxalate-citric acid process to etch silica into a high-specific-surface-area, carboxylated porous carrier. Rosinic acid and a photoprotectant are then chemically fixed to the surface, creating a stable composite system. Oxazosulfyl and beta-cypermethrin are then encapsulated in polyether-modified heptamethyltrisiloxane micelles, achieving both physical and chemical fixation between the micelles and the carrier pores, resulting in sustained release. This system utilizes ZnO to shield UV rays and rosinic acid to promote penetration, reducing photolysis and overapplication. By minimizing the risk of rainwater washout and sudden release, the pesticide's residence time on the crop surface is prolonged, significantly reducing exposure to beneficial insects and aquatic organisms, and enhancing overall safety. DETAILED DESCRIPTION

[0050] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0051] Study on the control effect of active ingredient A (Oxazosulfyl) and active ingredient B (Cypermethrin) on pests:

[0052] 1. Test agents: Oxazosulfyl and cypermethrin technical. Dissolve oxazolidinone and cypermethrin technical in acetone to a 10,000 μg / kg stock solution. Store in a refrigerator at 4°C until use.

[0053] 2. Test insects: beet armyworm, corn borer, small brown planthopper, and cereal aphid.

[0054] 3. Determination method:

[0055] 1. Artificial feed mixture method: The 3rd instar larvae of beet armyworm and corn borer were used as test materials, and the toxicity of active ingredient A, active ingredient B and their mixed preparations were determined by the artificial feed mixture method.

[0056] Single-dose toxicity assay method:

[0057] The artificial feed mixing method was used. The test agent (including active ingredient A and active ingredient B) was first prepared into a 10,000 mg / kg stock solution with acetone, and then serially diluted to 5 treatment concentrations of 10 mg / kg, 5 mg / kg, 2.5 mg / kg, 1.25 mg / kg, and 0.625 mg / kg in a geometrically decreasing series. 1 mL of each concentration solution was evenly mixed into 20 g of feed and stirred to prepare 5 concentration gradient mixed feeds. After cooling, the different treatment feeds were cut into 1 cm square pieces and placed in 24-well insect culture plates. 3rd-instar beet armyworm and corn borer larvae of uniform size and growth were selected and then placed in 24-well insect culture plates. The larvae were placed in a 27°C light incubator and the number of live insects was investigated after 48 hours. Each treatment was repeated 3 times, and DSP was used to calculate the toxicity regression equation and the median lethal concentration (LC) of the larvae. 50 ) and 95% confidence intervals.

[0058] Combined toxicity test of mixed agents:

[0059] On the basis of the single-dose toxicity determination, preliminary experiments were conducted to set the active ingredient A (Oxazosulfyl) and active ingredient B (Cypermethrin) to be mixed into 9 ratios of 20:1, 10:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:10 and 1:20 respectively. Five geometrically decreasing mass concentrations were prepared according to different ratios: 10 mg / kg, 5 mg / kg, 2.5 mg / kg, 1.25 mg / kg and 0.625 mg / kg. Three replicates were set for each gradient. The lethal median concentration (LC) of the mixed pesticides to Spodoptera exigua and Corn borer was determined by linear regression analysis between insect mortality and the logarithm of pesticide concentration. 50 value and CTC value.

[0060] 2. Seedling immersion method: Using Laodelphax striatellus and Rhizophora graminearum as test materials, the toxicity of active ingredient A, active ingredient B and their mixed preparations were determined according to the seedling immersion method of Wang Lihua (2008).

[0061] The seedling immersion method was used. The test agent (including active ingredient A and active ingredient B) was first prepared into a 10,000 mg / kg stock solution with acetone. Then, 0.1% Tween-80 solution was used as a solvent to serially dilute the solution into five treatment concentrations of 10 mg / kg, 5 mg / kg, 2.5 mg / kg, 1.25 mg / kg, and 0.625 mg / kg. Wheat seedlings were collected, the roots were washed and wrapped with moistened absorbent cotton. The wheat seedlings were immersed in the series of concentration solutions for 10 seconds and then removed. The blank seedlings were immersed in 0.1% Tween-80 aqueous solution and the excess solution was absorbed with filter paper. After 20 minutes of treatment, the gray leafhopper was inoculated and placed in a large test tube, and the tube mouth was sealed with gauze. In the test of cereal aphid, wheat seedlings with aphids were inoculated in advance and immersed in the test seedlings. A brush was used to select wingless adult aphids of the same size and body shape for the test. Each treatment was repeated 3 times, and the toxicity regression equation and the median lethal concentration (LC) were calculated using DSP. 50 ) and 95% confidence intervals.

[0062] Combined toxicity test of mixed agents:

[0063] Based on the single-dose toxicity test, a preliminary experiment was conducted to set the active ingredient A (Oxazosulfyl) and active ingredient B (Cypermethrin) in a mass ratio of 40:1, 20:1, 10:1, 5:1, 2:1, 1:1, 1:2, 1:5, and 1:10, respectively, for a total of 9 ratios. Five geometrically decreasing mass concentrations were prepared according to different ratios: 10 mg / kg, 5 mg / kg, 2.5 mg / kg, 1.25 mg / kg, and 0.625 mg / kg, with 3 replicates for each gradient. The lethal concentration (LC) of the mixed agent for Laodelphax striatellus and Grain Stalk Aphid was determined by linear regression analysis between insect mortality and the logarithm of the agent concentration. 50 value and CTC value.

[0064] (2) Data statistical analysis

[0065] The experimental data were statistically analyzed using Microsoft Excel 2016 and DPS data processing platform to calculate the LC of each agent. 50 The co-toxicity coefficient of the mixed agents was calculated using the Sun Yunpei method (1960), and the synergistic effect of the mixed agents was evaluated based on the size of the co-toxicity coefficient.

[0066] The inhibition rate of each drug was calculated according to the following formula:

[0067] ;

[0068] ;

[0069] ;

[0070] ;

[0071] ;

[0072] In the theoretical toxicity index (TTI) of the mixture, PA and PB are the percentages of the active ingredients in the mixture, respectively).

[0073] ;

[0074] Judgment of synergistic effect: CTC ≥ 120, synergistic effect; 80 < CTC < 120, additive effect; CTC ≤ 80, antagonistic effect.

[0075] Results and analysis: as shown in Tables 1 to 4.

[0076] Table 1 Toxicity test results of oxazolidinone, beta-cypermethrin and their mixture to Spodoptera exigua

[0077]

[0078] Table 2 Toxicity test results of Oxazosulfyl, cypermethrin and their mixture to corn borer

[0079]

[0080] Table 3 Toxicity test results of Oxazosulfyl, Beta-cypermethrin and their mixture to Laodelphax striatellus

[0081]

[0082] Table 4 Toxicity test results of Oxazosulfyl, cypermethrin and their mixtures against Psoralea graminearum

[0083]

[0084] As shown in Table 1, Oxazosulfyl, highly effective cypermethrin and their mixtures have high indoor toxicity to Spodoptera exigua. When the ratio of Oxazosulfyl to highly effective cypermethrin is between 10:1 and 1:2, the co-toxicity coefficient to Spodoptera exigua is above 120, indicating that the two insecticides have a good synergistic effect at this ratio.

[0085] As shown in Table 2, Oxazosulfyl, highly effective cypermethrin and their mixtures have high indoor toxicity to corn borer. When the ratio of Oxazosulfyl to highly effective cypermethrin is between 2:1 and 1:2, the co-toxicity coefficient to corn borer is above 120, indicating that the two insecticides have a good synergistic effect at this ratio.

[0086] As shown in Table 3, Oxazosulfyl, highly effective cypermethrin and their mixtures have high indoor toxicity to Laodelphax striatellus. When the ratio of Oxazosulfyl to highly effective cypermethrin is between 20:1 and 1:2, the co-toxicity coefficient to Laodelphax striatellus is above 120, indicating that the two insecticides have a good synergistic effect at this ratio.

[0087] As can be seen from Table 4, Oxazosulfyl, highly effective cypermethrin and their mixtures have high indoor toxicity to Psoralea graminicola. When the ratio of Oxazosulfyl to highly effective cypermethrin is between 20:1 and 1:1, the co-toxicity coefficient to Psoralea graminicola is above 120, indicating that the two insecticides have a good synergistic effect at this ratio.

[0088] Example 1

[0089] An insecticide composition is composed of the following components in percentage by weight:

[0090] Oxazosulfyl 2%, highly effective cypermethrin 1%, multifunctional modified silica composite carrier 20%, polyether modified heptamethyl trisiloxane 3%, styrylphenol polyoxyethylene ether 3%, sodium methylene bisnaphthalene sulfonate 1%, xanthan gum 1%, sodium alginate 1%, magnesium aluminum silicate 1%, propylene glycol 1%, sorbitol 1%, deionized water 65%.

[0091] A method for preparing a multifunctional modified silica composite carrier comprises the following steps:

[0092] A1: Add 20 parts of silica to 60 parts of 10% by mass ammonium oxalate solution, stir at 80°C for 6 hours, filter and wash until neutral, and dry at 80°C for 12 hours to obtain ammonium oxalate-etched silica.

[0093] A2: Add the ammonium oxalate-etched silica obtained in A1 to 50 parts of a citric acid-ethanol solution with a mass ratio of citric acid to anhydrous ethanol of 2:8, stir at 76°C for 6 hours, add 1.5 parts of rosinic acid, stir at 55°C for 80 minutes, add 1.5 parts of nano-zinc oxide and 0.5 parts of stearic acid, stir at 70°C for 40 minutes, filter and wash until neutral, and dry at 80°C for 15 hours to obtain a multifunctional modified silica composite carrier.

[0094] A method for preparing an insecticide composition is as follows:

[0095] S1: Dissolve polyether-modified heptamethyltrisiloxane and beta-cypermethrin in deionized water at 45°C, stir to dissolve, add oxazolidinone, and stir for 50 minutes to obtain an active ingredient micelle solution.

[0096] S2: Mix the active ingredient micellar solution and the multifunctional modified silica composite carrier, stir at 40°C for 60 minutes, cool to 20°C, add xanthan gum, sodium alginate, and magnesium aluminum silicate, stir for 30 minutes, add lactostyrene phenol polyoxyethylene ether, sodium methylene bisnaphthalene sulfonate, propylene glycol, and sorbitol, mix well to obtain a mixture, add the mixture to a zirconium oxide grinding jar, wherein the zirconium balls have a diameter of 3 mm, the ball-to-material ratio is 3:3, the rotation speed is controlled at 600 rpm, ball milling is carried out for 20 minutes, and the amount of ethanol added is 5% (v / w) of the mixture to obtain an insecticide composition.

[0097] Example 2

[0098] An insecticide composition is composed of the following components in percentage by weight:

[0099] Oxazosulfyl 3%, highly effective cypermethrin 3%, multifunctional modified silica composite carrier 25%, polyether modified heptamethyl trisiloxane 5%, castor oil polyoxyethylene ether 5%, fatty alcohol polyoxyethylene ether 2%, sodium carboxymethyl cellulose 1%, sodium alginate 1%, glycerol 2%, dipropylene glycol monomethyl ether 1%, cyclohexane 20%, deionized water 32%.

[0100] A method for preparing a multifunctional modified silica composite carrier comprises the following steps:

[0101] A1: Add 25 parts of silica to 70 parts of 10% by mass ammonium oxalate solution, stir at 86°C for 5 hours, filter and wash until neutral, and dry at 85°C for 10 hours to obtain ammonium oxalate-etched silica.

[0102] A2: The ammonium oxalate-etched silica obtained in A1 was added to 60 parts of a citric acid-ethanol solution having a mass ratio of citric acid to anhydrous ethanol of 2:8, and the mixture was stirred at 79°C for 4 hours. 1.8 parts of rosinic acid were added, and the mixture was stirred at 60°C for 67 minutes. 1 part of nano-zinc oxide and 0.5 parts of stearic acid were added, and the mixture was stirred at 70°C for 35 minutes. The mixture was filtered and washed until neutral, and dried at 85°C for 13 hours to obtain a multifunctional modified silica composite carrier.

[0103] A method for preparing an insecticide composition is as follows:

[0104] S1: Dissolve polyether-modified heptamethyltrisiloxane and beta-cypermethrin in a mixed solvent of cyclohexane and deionized water at 48°C, stir to dissolve, add oxazolidinone, and stir for 45 minutes to obtain an active ingredient micelle solution.

[0105] S2: Mix the active ingredient micellar solution and the multifunctional modified silica composite carrier, stir at 45°C for 50 minutes, cool to 25°C, add sodium carboxymethyl cellulose and sodium alginate, stir for 24 minutes, add castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, glycerol and dipropylene glycol monomethyl ether, mix well to obtain a mixture, add the mixture to a zirconium oxide grinding jar, wherein the zirconium ball has a diameter of 5 mm, the ball-to-material ratio is 3:2, the rotation speed is controlled at 500 rpm, ball milling is carried out for 25 minutes, and the amount of diethanolamine added is 5% (v / w) of the mixture to obtain an insecticide composition.

[0106] Example 3

[0107] An insecticide composition is composed of the following components in percentage by weight:

[0108] Oxazosulfyl 3%, highly effective cypermethrin 6%, multifunctional modified silica composite carrier 30%, polyether modified heptamethyl trisiloxane 7%, styrylphenol polyoxyethylene ether 8%, sodium methylene bisnaphthalene sulfonate 3%, xanthan gum 0.5%, sodium alginate 0.5%, propylene glycol 2%, dipropylene glycol monomethyl ether 2%, deionized water 38%.

[0109] A method for preparing a multifunctional modified silica composite carrier comprises the following steps:

[0110] A1: Add 30 parts of silica to 80 parts of 10% by mass ammonium oxalate solution, stir at 90°C for 4 hours, filter and wash until neutral, and dry at 90°C for 8 hours to obtain ammonium oxalate-etched silica.

[0111] A2: Add the ammonium oxalate-etched silica obtained in A1 to 70 parts of a citric acid-ethanol solution with a mass ratio of citric acid to anhydrous ethanol of 2:8, stir at 82°C for 3 hours, add 2.1 parts of rosinic acid, stir at 65°C for 50 minutes, add 1.2 parts of nano-zinc oxide and 0.8 parts of stearic acid, stir at 75°C for 30 minutes, filter and wash until neutral, and dry at 90°C for 12 hours to obtain a multifunctional modified silica composite carrier.

[0112] A method for preparing an insecticide composition is as follows:

[0113] S1: Dissolve polyether-modified heptamethyltrisiloxane and beta-cypermethrin in deionized water at 50°C, stir to dissolve, add oxazolidinone, and stir for 40 minutes to obtain an active ingredient micelle solution.

[0114] S2: Mix the active ingredient micellar solution and the multifunctional modified silica composite carrier, stir at 50°C for 40 minutes, cool to 30°C, add xanthan gum and sodium alginate, stir for 20 minutes, add styrylphenol polyoxyethylene ether, sodium methylene bisnaphthalene sulfonate, propylene glycol and dipropylene glycol monomethyl ether, mix well to obtain a mixture, add the mixture to a zirconium oxide grinding jar, wherein the diameter of the zirconium balls is 5 mm, the ball-to-material ratio is 1:1, the rotation speed is controlled at 300 rpm, ball milling is carried out for 20 minutes, and the amount of triethanolamine added is 5% (v / w) of the mixture to obtain an insecticide composition.

[0115] Comparative Example 1

[0116] Compared with Example 1, this comparative example kept the amount of active ingredient unchanged, only selected the active ingredient AOxazosulfyl, and the remaining steps and parameters were the same, which will not be repeated in this comparative example. Finally, an insecticide composition was obtained.

[0117] Comparative Example 2

[0118] Compared with Example 1, this comparative example controls the amount of active ingredient to remain unchanged, selects only active ingredient B, highly effective cypermethrin, and the remaining steps and parameters are the same, which will not be repeated in this comparative example. Finally, an insecticide composition is obtained.

[0119] Comparative Example 3

[0120] Compared with Example 1, this comparative example replaces the "multifunctional modified silica composite carrier" with "silica" of equal mass. The remaining steps and parameters are the same and will not be repeated in this comparative example. Finally, an insecticide composition is obtained.

[0121] Comparative Example 4

[0122] Compared with Example 1, the preparation method of the multifunctional modified silica composite carrier in this comparative example is different, and the remaining steps and parameters are the same, which will not be repeated in this comparative example. Finally, an insecticide composition is obtained.

[0123] Specifically, the preparation method of the multifunctional modified silica composite carrier is as follows:

[0124] A1: Add 20 parts of silica to 60 parts of a 10% by mass ammonium oxalate solution and 1.5 parts of rosinic acid, and stir at 80°C for 6 hours. After the reaction is complete, filter and wash until neutral, and dry at 80°C for 12 hours to obtain ammonium oxalate-etched silica.

[0125] A2: The ammonium oxalate-etched silica obtained in A1 was added to 50 parts of a citric acid-ethanol solution having a mass ratio of citric acid to anhydrous ethanol of 2:8, and the mixture was stirred at 76°C for 6 hours. 1.5 parts of nano-zinc oxide and 0.5 parts of stearic acid were added, and the mixture was stirred at 65°C for 40 minutes. The mixture was filtered and washed until neutral, and dried at 80°C for 15 hours to obtain a multifunctional modified silica composite carrier.

[0126] Comparative Example 5

[0127] Compared with Example 1, this comparative example replaced the "polyether-modified heptamethyltrisiloxane" with "sodium rosin acid" of equal mass. The remaining steps and parameters were the same and will not be repeated in this comparative example. Finally, an insecticide composition was obtained.

[0128] Experiment on Control of Cabbage Beet Armyworm

[0129] Test criteria: Refer to "Guidelines for Pesticide Field Efficacy Tests (I) GB / T 17980.13-2000".

[0130] Application period: Peak period of 2nd to 3rd instar beet armyworm larvae.

[0131] Survey method: The plot area was set at 25 m², repeated 4 times, and randomized block arrangement was adopted. 1 m wide isolation rows were set between the plots. Sampling was carried out at 5 points on the diagonal of each plot, and 5 cabbages were checked at each point. The number of live insects on the 3rd and 7th days after the application of the medicine was recorded.

[0132] Experimental treatment: The insecticide compositions prepared in Examples 1-3 and Comparative Examples 1-5 were used for field efficacy testing, and a clear water control group CK was set up.

[0133] Calculation of drug efficacy:

[0134] .

[0135] .

[0136] The results of the control test are recorded in Table 5.

[0137] Table 5

[0138]

[0139] Corn borer control experiment

[0140] Test criteria: Refer to "Guidelines for Field Efficacy Tests of Pesticides (I) GB / T17980.6-2000".

[0141] Application period: the initial peak period of corn borer pests.

[0142] Survey Methodology:

[0143] Experimental treatment: The insecticide compositions prepared in Examples 1-3 and Comparative Examples 1-5 were used for field efficacy testing, and a clear water control group CK was set up.

[0144] Efficacy calculation: The plot area was set at 18 m², repeated 4 times, and arranged in random blocks. A 1 m wide isolation zone was set between the plots. A chessboard 5-point sampling method was used in each plot. 10 corn plants were fixedly surveyed at each point, for a total of 50 corn plants. The insect population base was recorded in detail before application of the pesticide, and the number of live insects was surveyed on the 3rd and 7th days after application.

[0145] .

[0146] .

[0147] The results of the corn borer control test are recorded in Table 6.

[0148] Table 6

[0149]

[0150] Experiment on Control of Corn Laodelphax striatellus

[0151] Test criteria: Refer to "Guidelines for Field Efficacy Tests of Pesticides (I) GB / T 17980.4-2000".

[0152] Application period: the initial peak period of corn gray leafhopper pest.

[0153] Survey method: The plot area was set at 25m², repeated 4 times, and random block arrangement was adopted. 1m wide isolation rows were set between the plots. Parallel line 5-point sampling method was adopted in each plot, and 5 corn plants were surveyed at each point, for a total of 25 corn plants. The insect population base was accurately recorded before pesticide application. The number of live insects was surveyed on the 3rd and 7th days after pesticide application to evaluate the control effect of the pesticide.

[0154] Experimental treatment: The insecticide compositions prepared in Examples 1-3 and Comparative Examples 1-5 were used for field efficacy testing, and a clear water control group CK was set up.

[0155] Calculation of drug efficacy:

[0156] .

[0157] .

[0158] The results of the corn Laodelphax striatellus control test are recorded in Table 7.

[0159] Table 7

[0160]

[0161] Wheat aphid control experiment

[0162] Test criteria: Refer to "Guidelines for Field Efficacy Tests of Pesticides (I) GB / T 17980.15-2000".

[0163] Application period: the initial peak period of wheat aphid infestation.

[0164] Survey method: The plot area was set at 25m², repeated 4 times, and random block arrangement was adopted. 1m wide isolation rows were set between the plots. Sampling was carried out at 5 points on the diagonal of each plot. Each plot adopted the 5-point diagonal sampling method. 10 wheat plants were surveyed at each point, and a total of 50 wheat plants were surveyed. The insect population base was accurately recorded before the application of the pesticide. The number of live insects was surveyed on the 3rd and 7th days after the application of the pesticide to analyze the changes in the control effect of the pesticide.

[0165] Experimental treatment: The insecticide compositions prepared in Examples 1-3 and Comparative Examples 1-5 were used for field efficacy testing, and a clear water control group CK was set up.

[0166] Calculation of drug efficacy:

[0167] .

[0168] .

[0169] The results of the wheat aphid control test are recorded in Table 8.

[0170] Table 8

[0171]

[0172] According to the data in Table 5, Table 6, Table 7 and Table 8, the synergistic effect of Oxazosulfyl and cypermethrin in the insecticide composition of the present invention is outstanding, and the control effect is significantly improved compared with a single agent.

[0173] Comparison between Example 1 and Comparative Example 3 shows that since the silica in Comparative Example 3 has not been etched with ammonium oxalate, carboxylated, and bonded with a synergist, the silica has fewer active sites and voids, which affects the combination with the stable micelles formed with the polyether-modified heptamethyltrisiloxane, resulting in no sustained release and synergistic effects, and the pest control effect is weakened.

[0174] Comparison between Example 1 and Comparative Example 4 shows that in Comparative Example 4, the synergist rosinic acid is not bonded to the carrier, which results in easy loss of rosinic acid, thereby weakening the control effect.

[0175] Comparison between Example 1 and Comparative Example 5 shows that in Comparative Example 5, the polyether-modified heptamethyl trisiloxane is replaced with sodium rosinate. The polyether-modified heptamethyl trisiloxane can form stable micelles to adsorb oxazolidinyl and beta-cypermethrin, which are then adsorbed and bonded by the multifunctional modified silica composite carrier, thereby protecting and slowly releasing oxazolidinyl and beta-cypermethrin. The polyether-modified heptamethyl trisiloxane can form stable micelles to combine oxazolidinyl, beta-cypermethrin, and the synergist rosinic acid, thereby stabilizing and synergizing the micelles and improving the pest control effect.

[0176] The above content is merely an example and explanation of the concept of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the scope of protection of the present invention.

Claims

1. An insecticide composition, characterized in that The insecticide composition comprises an active ingredient A and an active ingredient B, wherein the active ingredient A is Oxazosulfyl and the active ingredient B is highly effective cypermethrin, and the mass ratio of the active ingredient A to the active ingredient B is 1-2:1-2.

2. The insecticide composition according to claim 1, characterized in that The insecticide composition further comprises a pesticide adjuvant, which consists of a surfactant, a carrier, an emulsifier, a wetting agent, a thickener, an antifreeze agent and a solvent. The surfactant is polyether-modified heptamethyltrisiloxane, the emulsifier is any one of styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether and fatty alcohol polyoxyethylene ether, and the wetting agent is any one of sodium methylene bisnaphthalene sulfonate, fatty alcohol polyoxyethylene ether and taurine alkyl ester.

3. An insecticide composition according to claim 2, characterized in that: The carrier is a multifunctional modified silica composite carrier, and the preparation method of the multifunctional modified silica composite carrier comprises the following preparation steps: A1: Add silica to ammonium oxalate solution and stir to react. After the reaction is complete, filter and wash until neutral, and dry to obtain ammonium oxalate-etched silica. A2: Add ammonium oxalate-etched silica to a citric acid ethanol solution, heat and stir, and blend with a plant-derived synergist and a light protectant in steps. After the reaction is completed, filter and wash to neutrality, and dry to obtain a multifunctional modified silica composite carrier.

4. The insecticide composition according to claim 3, characterized in that The plant-derived synergist is rosinic acid, the light protectant is nano zinc oxide and stearic acid, and the mass ratio of nano zinc oxide to stearic acid is 3:1-2.

5. The insecticide composition according to claim 2, characterized in that: The thickener is any one or more of xanthan gum, sodium alginate, sodium carboxymethyl cellulose, and magnesium aluminum silicate.

6. The insecticide composition according to claim 2, characterized in that: The antifreeze agent is any one or more of propylene glycol, glycerol, sorbitol and dipropylene glycol monomethyl ether.

7. A method for preparing the insecticide composition according to any one of claims 1 to 6, characterized in that: The method comprises the following preparation steps: S1: After adding the surfactant and active ingredient B into the solvent and stirring to dissolve, the active ingredient A is added and stirred to obtain an active ingredient micellar solution; S2: After uniformly mixing the active ingredient micelle solution with the carrier, a thickener, an emulsifier, a wetting agent and an antifreeze agent are added in sequence, and the mixture is fully mixed and ball-milled to obtain an insecticide composition.

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