Acaricidal composition containing cyenopyrafen and etoxazole as well as preparation method and application of acaricidal composition

Abstract

The invention relates to the technical field of pesticides, in particular to an acaricidal composition containing cyenopyrafen and etoxazole and a preparation method and application of the acaricidal composition, the acaricidal composition comprises the active ingredients of cyenopyrafen and etoxazole, and the mass ratio of cyenopyrafen to etoxazole is (2.5-3.5): 1. A compounding system of cyenopyrafen and etoxazole is selected and combined with the block polyether dispersing agent and the carboxylic ester dispersing agent according to the mass ratio of (2-5): (2-5) to form a stable dispersing system, so that the prepared acaricidal composition has a remarkable prevention and control effect on citrus red mites, and meanwhile, the heat storage stability of the acaricidal composition can be remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and in particular to an acaricidal composition containing cypermethrin and etoxazole, and a preparation method and application thereof. Background Art

[0002] Mites are one of the most serious pest groups in global agricultural production. They have strong reproductive capacity and rapidly develop resistance to pesticides, especially on economic crops such as citrus, apples, and cotton. The long-term use of traditional single acaricides such as organophosphates and pyrethroids has led to a significant increase in the resistance of mites to pesticides, and the control effect has declined year by year. For example, etoxazole, a spirocyclazole acaricide, works by inhibiting the synthesis of chitin in mite eggs and larvae. However, after long-term use, mites in some areas have developed a 10-20-fold resistance to it. Cyclopyraclostrobin, a new pyridineamide acaricide, has dual effects of contact and stomach poisoning, but when used alone, it is not fast-acting on adult mites and is prone to decomposition under high temperature or long-term storage conditions, affecting the stability of the efficacy. However, existing rice field herbicides have exposed many shortcomings in actual application.

[0003] To address the limitations of single agents, compound acaricides have become a research and development hotspot. For example, Chinese patent application CN104542618A provides a synergistic acaricidal composition containing cypermethrin and etoxazole, which has excellent control effects on various mite pests on crops such as fruit trees, vegetables, cotton, and tea trees, as well as flowers. However, in actual use, cypermethrin and etoxazole have high decomposition rates and poor stability under conditions such as high-temperature storage. Summary of the Invention

[0004] In order to solve the problems in the prior art, the first aspect of the present invention provides a miticide composition containing cypermethrin and etoxazole. The active ingredients in the miticide composition include cypermethrin and etoxazole, and the mass ratio of cypermethrin to etoxazole is (2.5-3.5):1. Examples include 2.5:1, 28.9:9.7, 3:1, and 3.5:1.

[0005] In one embodiment, the active ingredient content in the acaricidal composition is 35-40 wt %, which can be exemplified by 35 wt %, 36 wt %, 37 wt %, 38 wt %, 38.6 wt %, 39 wt %, or 40 wt %.

[0006] In one embodiment, the cypermethrin and etoxazole are both from Xingnong Pharmaceutical (China) Co., Ltd., and the purities of cypermethrin and etoxazole are 98% and 97%, respectively.

[0007] In one embodiment, the acaricidal composition further comprises a dispersant, a thickener, a defoaming agent, a suspension thixotropic agent, a pH regulator, an antifreeze agent, a preservative, and a solvent.

[0008] In one embodiment, the acaricidal composition comprises, by weight percentage, 35-40% active ingredient, 5-7% dispersant, 5-7% antifreeze, 0.1-0.3% preservative, 0.05-0.2% thickener, 1-2.3% pH regulator, 0.1-0.2% defoaming agent, 1-2% suspension thixotropic agent, and the balance is made up of solvent.

[0009] In one embodiment, the dispersant includes a block polyether dispersant and a carboxylate dispersant.

[0010] In one embodiment, the mass ratio of the block polyether dispersant to the carboxylate dispersant is (2-5):(2-5), which can be exemplified as 2:3, 2:5, 3:2, or 3:5.

[0011] In one embodiment, the block polyether dispersant includes a brand name of featdis 894D, which is from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0012] In one embodiment, the carboxylate dispersant includes a brand of featdis SC800, which is from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0013] In one embodiment, the pH adjuster comprises sodium citrate.

[0014] In one embodiment, the antifreeze agent comprises propylene glycol.

[0015] In one embodiment, the preservative comprises a benzisothiazolinone.

[0016] In one embodiment, the antifoaming agent comprises polydimethylsiloxane.

[0017] In one embodiment, the suspending thixotropic agent comprises magnesium aluminum silicate.

[0018] In one embodiment, the thickening agent comprises xanthan gum.

[0019] In one embodiment, the solvent is demineralized water.

[0020] In one embodiment, the acaricidal composition is in the form of a suspension.

[0021] The second aspect of the present invention provides a method for preparing a miticide composition containing cypermethrin and etoxazole, comprising the following steps:

[0022] Add solvent, dispersant, antifreeze, suspension thixotropic agent, preservative, and defoamer into the homogenizing kettle in sequence, start stirring, add active ingredients, and stir to form a uniform slurry;

[0023] The slurry is sand-milled and then a thickener and a pH regulator are added to obtain the acaricidal composition containing cypermethrin and etoxazole.

[0024] In one embodiment, the particle size of the slurry after sanding is controlled to be D[4,3]<2 μm. In this application, D[4,3] is the volume average particle size.

[0025] In one embodiment, the viscosity (25° C.) of the acaricidal composition containing cypermethrin and etoxazole is 1800-2200 cP.

[0026] A third aspect of the present invention provides an application of an acaricidal composition containing cypermethrin and etoxazole, which is applied to the prevention and treatment of citrus red spider mites.

[0027] Beneficial effects

[0028] 1. This application uses a compound system of cypermethrin and etoxazole, and controls the mass ratio of the two to (2.5-3.5):1. The prepared acaricidal composition has a significant control effect on citrus red spider mites.

[0029] 2. This application forms a stable dispersion system by combining a block polyether dispersant and a carboxylate dispersant in a mass ratio of (2-5):(2-5), which can significantly improve the thermal storage stability of the acaricidal composition. Possible reasons are: on the one hand, the polyether segments in the dispersion system can interact with the layered structure of magnesium aluminum silicate through van der Waals forces, forming a three-dimensional network structure. This structure imparts thixotropy to the system and improves stability; on the other hand, at this mass ratio, the block polyether dispersant adsorbs on the particle surface through the long-chain hydrophobic block, and the hydrophilic block extends outward to form steric hindrance, preventing particle aggregation; the carboxylate groups in the carboxylate dispersant stabilize the particles through electrostatic repulsion, and at the same time, cooperate with the block polyether to form a composite adsorption layer, enhancing the dynamic equilibrium of the dispersion system.

[0030] 3. This application adds 1-2.3 wt% of a pH regulator, and the synergistic emulsifier is completely ionized (RCOO-) under neutral to weakly alkaline conditions, generating strong electrostatic repulsion, which synergizes with the steric hindrance of the block polyether to form a stable double-layer structure, thereby solving the problem of high thermal storage decomposition rate of traditional suspension formulations.

[0031] 4. The preparation method of the pesticide formulation provided by the present invention has a simple process and is applicable to industrial production. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the examples. It should be understood that the specific examples described herein are only used to explain the present invention and are not intended to limit the present invention. The experimental methods in the examples where specific conditions are not specified are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used where the manufacturer is not specified are conventional products that can be purchased commercially.

[0033] Example 1

[0034] In a first aspect, the present embodiment provides a miticide composition containing cypermethrin and etoxazole, wherein the active ingredients in the miticide composition are cypermethrin and etoxazole, and the mass ratio of cypermethrin to etoxazole is 28.9:9.7.

[0035] The active ingredient content of the acaricide composition is 38.6 wt %. Both cypermethrin and etoxazole are from Xingnong Pharmaceutical (China) Co., Ltd., and the purities of cypermethrin and etoxazole are 98% and 97%, respectively.

[0036] Calculated by weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 5% dispersant, 6% antifreeze, 0.2% preservative, 0.1% thickener, 1.5% pH regulator, 0.1% defoamer, 1% suspension thixotropic agent, and the balance is made up of solvent.

[0037] The dispersants are block polyether dispersants and carboxylate dispersants, and the mass ratio of the block polyether dispersants to the carboxylate dispersants is 3:2.

[0038] The block polyether dispersant is of the brand name featdis 894D, which is from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0039] The carboxylate dispersant is of the brand Featdis SC800, which is from Shanghai Xuezhuo Fine Chemical Co., Ltd.

[0040] The pH regulator is sodium citrate.

[0041] The antifreeze agent is propylene glycol.

[0042] The preservative is benzisothiazolinone.

[0043] The defoaming agent is polydimethylsiloxane.

[0044] The suspension thixotropic agent is magnesium aluminum silicate.

[0045] The thickener is xanthan gum.

[0046] The solvent is soft water.

[0047] The formulation of the acaricidal composition is a suspension.

[0048] A second aspect of this embodiment provides a method for preparing a miticide composition containing cypermethrin and etoxazole, comprising the following steps:

[0049] Add solvent, dispersant, antifreeze, suspension thixotropic agent, preservative, and defoamer into the homogenizing kettle in sequence, start stirring, add active ingredients, and stir to form a uniform slurry;

[0050] The slurry is sand-milled and then a thickener and a pH regulator are added to obtain the acaricidal composition containing cypermethrin and etoxazole.

[0051] The particle size D[4,3] of the slurry after sanding was 1.43 μm.

[0052] The viscosity (25° C.) of the acaricidal composition containing cypermethrin and etoxazole is 1800 cP.

[0053] A third aspect of this embodiment provides an application of a miticide composition containing cypermethrin and etoxazole, which is applied to the prevention and treatment of citrus red spider mites.

[0054] Example 2

[0055] The specific implementation of this embodiment is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 5% dispersant, 6% antifreeze agent, 0.2% preservative, 0.1% thickener, 1% pH regulator, 0.1% defoamer, 1% suspension thixotropic agent, and the balance is made up of solvent.

[0056] The mass ratio of the block polyether dispersant to the carboxylate dispersant is 2:3.

[0057] Example 3

[0058] The specific implementation of this embodiment is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 7% dispersant, 6% antifreeze agent, 0.2% preservative, 0.1% thickener, 1.8% pH adjuster, 0.1% defoamer, 2% suspension thixotropic agent, and the balance is made up of solvent.

[0059] The mass ratio of the block polyether dispersant to the carboxylate dispersant is 2:5.

[0060] Example 4

[0061] The specific implementation of this embodiment is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 7% dispersant, 6% antifreeze agent, 0.2% preservative, 0.1% thickener, 2.3% pH regulator, 0.1% defoamer, 1.5% suspension thixotropic agent, and the balance is made up of solvent.

[0062] The mass ratio of the block polyether dispersant to the carboxylate dispersant is 5:2.

[0063] Comparative Example 1

[0064] The specific implementation of this comparative example is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 4% dispersant, 6% antifreeze agent, 0.2% preservative, 0.1% thickener, 0.4% pH regulator, 0.1% defoamer, 1% suspension thixotropic agent, and the balance is made up of solvent.

[0065] The dispersants are alkyl sulfonic acid dispersants and liquid sodium polycarboxylate dispersants.

[0066] The brands of the dispersants are SP-SC29 and SP-27001, and both SP-SC29 and SP-27001 are from Jiangsu Qingyu Chemical Technology Co., Ltd.

[0067] The mass ratio of SP-SC29 to SP-27001 is 1:1.

[0068] The pH regulator is aqueous ammonia.

[0069] Comparative Example 2

[0070] The specific implementation of this comparative example is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 5% dispersant, 6% antifreeze, 0.2% preservative, 0.1% thickener, 0.1% defoaming agent, 1% suspension thixotropic agent, and the balance is made up of solvent.

[0071] Comparative Example 3

[0072] The specific implementation of this comparative example is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 5% dispersant, 6% antifreeze agent, 0.2% preservative, 0.1% thickener, 0.1% pH regulator, 0.1% defoamer, 1% suspension thixotropic agent, and the balance is made up of solvent.

[0073] The pH adjuster is citric acid.

[0074] Comparative Example 4

[0075] The specific implementation of this comparative example is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 6% dispersant, 6% antifreeze agent, 0.2% preservative, 0.1% thickener, 0.1% pH regulator, 0.1% defoamer, 1% suspension thixotropic agent, and the balance is made up of solvent.

[0076] The dispersants are phosphate dispersants and liquid sodium carboxylate dispersants.

[0077] The dispersants are Ultrasurf 1010 and SP-SC3275. SP-SC3275 is from Jiangsu Qingyu Chemical Technology Co., Ltd., and Ultrasurf 1010 is from Wuxi Yijingfeng Technology Co., Ltd.

[0078] The mass ratio of SP-SC29 to SP-27001 is 1:1.

[0079] Comparative Example 5

[0080] The specific implementation of this comparative example is the same as that of Example 1, except that, based on weight percentage, the acaricidal composition comprises: 38.6% active ingredient, 5% dispersant, 6% antifreeze agent, 0.2% preservative, 0.1% thickener, 0.4% pH regulator, 0.1% defoamer, 1% suspension thixotropic agent, and the balance is made up of solvent.

[0081] The pH regulator is aqueous ammonia.

[0082] Performance Testing

[0083] 1. Thermal storage decomposition rate test

[0084] Test sample: the acaricidal composition prepared in each example and comparative example.

[0085] Test method: High performance liquid chromatography was used to detect the contents of cypermethrin and etoxazole at room temperature (25°C) and hot storage (54°C), referring to the general standard GB / T 19136-2021 Pesticide Hot Storage Stability Determination Method.

[0086] Decomposition rate calculation: (normal temperature content - thermal storage content) / normal temperature content * 100%. Test results are shown in Table 1-2.

[0087] In the table, / indicates that the test was not performed. The acaricidal composition prepared in Comparative Example 1 thickened after heat storage, so no subsequent test was performed.

[0088] Table 1

[0089]

[0090] Table 2

[0091]

[0092]

[0093] As can be seen from Tables 1 and 2, the decomposition rates of the active ingredients cypermethrin and etoxazole in the acaricidal composition prepared in the present application at 54°C were both less than 5%, demonstrating that the acaricidal composition prepared in the present application has good thermal storage stability. In contrast, the cypermethrin and etoxazole contents in Comparative Examples 2-5 at 54°C decreased to varying degrees compared to the technical solution of the present application. In Comparative Example 5, the decomposition rates of cypermethrin and etoxazole reached 77% and 22.7%, respectively, significantly reducing thermal storage stability.

[0094] 2. Field efficacy test

[0095] 1) Field efficacy test 1:

[0096] Crop and target: The crop is citrus trees; the target is spider mite [Panonychus citri];

[0097] Experimental Conditions: The experiment was conducted from April 8 to May 8, 2020, in Commune 7, Wenshu Village, Fengming Town, Pengshan District, Meishan City, Sichuan Province. Citrus trees were planted in the Jinkuai (Golden Knot) variety, with approximately 56 trees per mu (approximately 56 trees per acre) and a row spacing of 3 x 4 m. The trees were four years old and grew during the spring shoot emergence period, when spider mites are common. No pesticides were applied after the winter opening, and weeding was performed. The soil in the field was sandy loam with a pH of 6.8 and an organic matter content of 1.70%, indicating medium fertility.

[0098] Experimental design and arrangement:

[0099] Plot size and replication: 4 replications, 2 trees per plot, with guard rows between plots.

[0100] Application method:

[0101] Time and frequency of application: On April 8, 2020, spray once during the spring shoots of citrus trees and the period when red spider mites occur.

[0102] Equipment used and application method: The solution was prepared by the secondary dilution method. The main preparation tools included a balance, a measuring cylinder, a pipette, a glass rod, etc. The solution was sprayed with a Linong HD400 manual sprayer. The spray pressure was 0.2-0.4 MPa, the nozzle diameter was 1 mm, and the water consumption per tree was about 2 liters.

[0103] Soil data: Sandy loam, pH 6.8, organic matter content 1.70%, medium fertility level.

[0104] Control of non-target organisms: No other pesticides were used during the trial.

[0105] Investigation and Results:

[0106] Survey Method: Mark tender shoots on each tree in five locations (east, west, south, north, and center) in each plot and count the number of active mites on 25 leaves. Count the mites by directly observing the leaf surface with a handheld magnifying glass.

[0107] Survey time and frequency: One survey every 10 days after medication. Specific time: April 18, 2020. Test results are shown in Table 3.

[0108] Table 3

[0109] Name of test drug Preventive effect 10 days after medication (%) Significance of difference Example 1 92.7 <![CDATA[ a A]]> Example 2 84.3 <![CDATA[b c BC]]> Example 3 90.3 <![CDATA[ a A]]> Example 4 82.90 oeLh Blank control 60.5 dD

[0110] 2) Field efficacy test 2:

[0111] The trial site is located at the Mawang Village Demonstration Base in Wuling Town, Binyang County, Guangxi. The citrus variety tested was the Wogan (Wogan). At the time of the trial, the trees were approximately 1.6 meters tall and had a crown diameter of approximately 1.4 meters. The citrus trees were planted in a continuous area covering approximately 50 mu (approximately 16 acres), with approximately 100 trees per mu. Consistent fertilization and watering ensured uniform growth, in accordance with local Good Agricultural Practices (GAP).

[0112] Test target situation: The test object was citrus red spider. The pesticide was applied at the early stage of the occurrence of citrus red spider nymphs, and the insect population was average.

[0113] Test crops, varieties and growth conditions: The test crop was citrus (variety Wogan, 3 years old), the plants grew well and were in the fruit growth period when the pesticide was applied.

[0114] Soil type of the experimental site: The tobacco field is loam, with a soil pH of 6.8 and medium fertility.

[0115] Water and fertilizer management in the experimental site: conventional fertilizer and water management.

[0116] Meteorological data: On the day of application (September 5, 2020), the weather was cloudy with a southerly wind of 1-2. The temperature was 28°C when the application took place. Showers were the main rainfall during the entire test period, with a total precipitation of 76.9 mm, a maximum temperature of 34°C, and a minimum temperature of 20°C.

[0117] Information on pesticides used to control other diseases and pests: No insecticides or fungicides were used in the experimental field before the experiment, and no other pesticides were applied during the experiment.

[0118] Experimental design and arrangement:

[0119] Plot size: 2 trees / plot; number of repetitions: 4 times.

[0120] Application method:

[0121] Period and method of use: Apply the pesticide at the early stage of the occurrence of citrus red spider nymphs. Use the spray method to evenly spray each plot, so that the front and back of the citrus leaves are fully moistened without dripping. Spray the blank control with an equal amount of clean water.

[0122] Usage capacity: In this test, the agent prepared in each example was diluted 6000 times, and the water consumption per plot was 0.9 liter, that is, 0.45 liter per tree.

[0123] Application equipment: Toyota FT-18 backpack electric sprayer, serial number: P025.

[0124] Application time and number of times: This experiment only applied the pesticide once, and the application time was September 5, 2020.

[0125] Survey time:

[0126] The patients were surveyed once on the 10th day after taking the medicine.

[0127] The experimental results are shown in Table 4.

[0128] Table 4

[0129] Name of test drug Preventive effect 10 days after medication (%) Significance of difference Example 1 93.51 <![CDATA[ a A]]> Example 2 92.84 bB Example 3 91.36 <![CDATA[ a A]]> Example 4 88.92 <![CDATA[ c B]]> Blank control 67.3 dD

[0130] It can be seen from Tables 3 and 4 that the acaricidal composition prepared in the present application has a good killing effect on citrus red spider mites.

Claims

1. A mite-killing composition containing cypermethrin and etoxazole, characterized in that: The active ingredients in the acaricidal composition include cypermethrin and etoxazole, and the mass ratio of cypermethrin to etoxazole is (2.5-3.5):

1.

2. The acaricidal composition containing cypermethrin and etoxazole according to claim 1, characterized in that The active ingredient content of the acaricidal composition is 35-40 wt%.

3. The acaricidal composition containing cypermethrin and etoxazole according to claim 1, characterized in that The acaricidal composition further comprises a dispersant, a thickener, a defoaming agent, a suspension thixotropic agent, a pH regulator, an antifreeze agent, a preservative and a solvent.

4. The acaricidal composition containing cypermethrin and etoxazole according to claim 3, characterized in that: Calculated by weight percentage, the acaricidal composition comprises: 35-40% active ingredient, 5-7% dispersant, 5-7% antifreeze, 0.1-0.3% preservative, 0.05-0.2% thickener, 1-2.3% pH regulator, 0.1-0.2% defoamer, 1-2% suspension thixotropic agent, and the balance is made up of solvent.

5. The acaricidal composition containing cypermethrin and etoxazole according to claim 3, characterized in that: The dispersants include block polyether dispersants and carboxylate dispersants.

6. The acaricidal composition containing cypermethrin and etoxazole according to claim 5, characterized in that: The mass ratio of the block polyether dispersant to the carboxylate dispersant is (2-5): (2-5).

7. The acaricidal composition containing cypermethrin and etoxazole according to claim 3, characterized in that: The pH adjuster includes sodium citrate.

8. The acaricidal composition containing cypermethrin and etoxazole according to any one of claims 1 to 7, characterized in that: The formulation of the acaricidal composition is a suspension.

9. A method for preparing the acaricidal composition containing cypermethrin and etoxazole according to claim 8, characterized in that: The following steps are involved: Add solvent, dispersant, antifreeze, suspension thixotropic agent, preservative, and defoamer into the homogenizing kettle in sequence, start stirring, add active ingredients, and stir to form a uniform slurry; The slurry is sand-milled and then a thickener and a pH regulator are added to obtain the acaricidal composition containing cypermethrin and etoxazole.

10. Use of the acaricidal composition containing cypermethrin and etoxazole according to any one of claims 1 to 8, characterized in that: Used for the prevention and control of citrus red spider mites.

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