Acaricidal composition containing acequinocyl as well as preparation method and application thereof

Abstract

The invention relates to an acequinocyl-containing acaricidal composition as well as a preparation method and application thereof, and relates to the field of pesticides, the active ingredients of the acequinocyl-containing acaricidal composition comprise acequinocyl and fluralan, and the weight ratio of acequinocyl to fluralan is (99: 1)-(1: 99), optionally (70-1: 1-70), optionally (50-1: 1-50), optionally (30-1: 1-30), optionally (0.2-50): 1, optionally (0.1-20): 1, optionally (0.1-10): 1, optionally (5-10): 1 and optionally (0.1-5): 1. The acaricidal composition (acequinocyl and fluralan) selected by the invention shows activity superior to that of a single agent in a certain ratio range, and particularly has higher prevention and control advantages on populations which are easy to generate resistance, such as panonychus citri and tetranychus urticae.

Description

[0001] Cross-referencing

[0002] This invention claims priority to Chinese Patent Application No. 202411707326.8, filed on November 26, 2024, entitled "An acaricidal composition containing acaricide quinone and its preparation method and application", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of pesticides, and in particular to an acaricidal composition containing miticide quinone, its preparation method, and its application. Background Technology

[0004] The information disclosed in this background section is intended only to enhance the understanding of the overall background of the invention and should not be construed as an admission or in any way implying that the information constitutes prior art known to those skilled in the art.

[0005] Agricultural mites belong to the phylum Arthropoda, class Arachnida, and order Arachnoidea. They are diverse, and mites that harm plants and their products are called phytophagous mites. Most cultivated plants suffer from mite damage during their growth. Mites are characterized by their small size, wide distribution, strong adaptability, rapid reproduction, short growth cycle, and highly variable overwintering sites. All life stages (eggs, larvae, nymphs, and adults) can exist within a single colony, making them difficult to control and prone to developing pesticide resistance. Currently, mites have become the second most resistant species among arthropods.

[0006] Acequinocyl, chemically known as 2-(acetoxy)-3-dodecyl-1,4-naphthoquinone, is a naphthoquinone derivative. Within mites, it hydrolyzes to 2-dodecyl-3-hydroxy-1,4-naphthoquinone, which binds to the Qo point of cytochrome b, thereby inhibiting electron transport. Therefore, acequinocyl is a class III acaricide of the mitochondrial complex, exhibiting both stomach poison and contact action against mites. It is effective against citrus parvum mites, spider mites, leaf miners, broad mites, and apple spider mites, among others. It is effective against mite eggs and highly effective against larvae, nymphs, and adults.

[0007] Fluralaner, chemically known as 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-[2-oxo-2-[(2,2,2-trifluoro-2-ethyl)amino]ethane]benzamide, is an isoxazoline insecticide and acaricide. It is a non-competitive antagonist of the γ-aminobutyric acid (GABA) receptor, blocking the ligand-gated chloride ion pathway of the GABA receptor. Fluralaner primarily mediates rapid inhibitory synaptic transmission by inhibiting chloride ion permeability of the postsynaptic membrane, ultimately leading to paralysis and death of target insects. Summary of the Invention

[0008] Purpose of the invention

[0009] The purpose of this invention is to provide an acaricidal composition containing miticide quinone, its preparation method, and its application. The acaricidal composition selected in this invention (miticide quinone and flena) combines the acaricidal advantages of the two components. By combining a highly effective acaricide for killing mite eggs with a highly effective acaricide for killing adult mites, it is possible to achieve complete elimination of all mite stages with a single application, reducing the number of manual applications and saving costs.

[0010] Solution

[0011] To achieve the objective of this invention, embodiments of this invention provide an acaricidal composition containing acaricide quinone, wherein the active ingredients include acaricide quinone and flenarine, and the weight ratio of acaricide quinone to flenarine is 99:1 to 1:99, optionally 70 to 1:1 to 70, optionally 50 to 1:1 to 50, optionally 30 to 1:1 to 30, optionally 20 to 1:1 to 20, optionally (0.1 to 70):1, optionally (0.2 to 50):1, optionally (0.1 to 20):1, optionally (0.1 to 10):1, optionally (5 to 10):1, optionally (0.1 to 5):1.

[0012] Optionally, synergistic effects are observed in the range of 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 15:1, 16:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, or any two of these values.

[0013] Optionally, synergistic effects are observed in the range of 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 15:1, 16:1, 18:1, 19:1, 20:1, or any two of these values.

[0014] Optionally, the ratios can be 0.01:1, 0.05:1, 0.08:1, 1:10 (0.1:1), 1:9, 1:8 (0.125:1), 1:7, 1:6, 1:5 (0.2:1), 1:4 (0.25:1), 1:3, 1:2 (0.5:1), 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12: The range of 1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, or any two of these ranges, all exhibit synergistic effects.

[0015] Further, the content of the active ingredient accounts for 1% to 90% of the total composition, optionally 1% to 40%, optionally 10% to 40%, optionally 10% to 30%, optionally 10% to 22%, and the balance is an adjuvant acceptable for pesticides;

[0016] And / or, the active ingredient may also contain one or more other agricultural active ingredients.

[0017] Furthermore, the additive is one or more of the following: emulsifier, wetting agent, dispersant, solvent, stabilizer, preservative, thickener, defoamer, antifreeze agent, or filler.

[0018] Further, the emulsifier includes nonionic emulsifiers and anionic emulsifiers; optionally, the nonionic emulsifier is selected from one or more of sorbitan monooleate polyoxyethylene ether, fatty alcohol polyoxyethylene ether, tristyrene-phenol polyoxyethylene ether, styrene-phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrene-phenol formaldehyde resin polyoxyethylene polyoxypropylene ether, or castor oil polyoxyethylene ether; the anionic emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, triphenylethylphenol polyoxyethylene ether phosphate amine salt, nonylphenol polyoxyethylene ether phosphate amine salt, or castor oil polyoxyethylene ether phosphate amine salt, agricultural emulsion 0201B, and agricultural emulsion 600.

[0019] Further, the dispersant is selected from one or more of the following: comb-grafted acrylic acid copolymer, sodium salt of acrylic acid homopolymer, sodium salt of maleic olefin polymer, sodium salt of naphthalene sulfonate formaldehyde condensate (including sodium alkyl naphthaldehyde condensate), lignin sulfonate, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenylethylphenol polyoxyethylene ether phosphate, styrenephenol polyoxyethylene ether phosphate ammonium salt, fatty alcohol polyoxyethylene ether phosphate, sodium p-hydroxyphenyl lignin sulfonate, or alkyl naphthaldehyde condensate sulfonate;

[0020] Optionally, the wetting agent is selected from one or more of fatty alcohol polyoxyethylene ether, naphthalene sulfonate, sodium dodecyl sulfate or alkylphenol resin polyoxyethylene ether sulfate;

[0021] Optionally, the solvent is selected from one or more of water, trimethylbenzene, tetramethylbenzene, N,N-dimethyloctylamide, tributyl phosphate, N-octylpyrrolidone, methyl oleate, and solvent oil;

[0022] Optionally, the thickener is selected from one or more of xanthan gum, magnesium aluminum silicate, sodium alginate, sodium carboxymethyl cellulose, gum arabic, gelatin, polyvinyl alcohol, or methyl cellulose;

[0023] Optionally, the defoamer is selected from one or more of alcohols, fatty acids and fatty acid esters, amides, phosphoric acids, and polyethers;

[0024] Optionally, the antifreeze is selected from one or more of carbonates, ethanol, ethylene glycol, glycerol, ethylene glycol butyl ether acetate, and urea;

[0025] Optionally, the filler is selected from one or more of carbonates, sulfates, sodium chloride, kaolin, diatomaceous earth, pearl clay, vermiculite, talc, and silica; optionally, the carbonates include one or more of precipitated calcium carbonate hydrate and precipitated calcium carbonate; optionally, the sulfates include one or more of sodium sulfate or calcium sulfate.

[0026] Optionally, the preservative includes Kathon.

[0027] The pesticide formulation of the present invention is applicable to any formulation in the agricultural field. Optionally, the formulation of the acaricide composition is a wettable powder, emulsifiable concentrate, suspension concentrate, dispersible oil suspension, suspension emulsion, microemulsion, water emulsion or water dispersible granules.

[0028] Furthermore, the formulation of the acaricide composition is an aqueous emulsion, and optionally, the adjuvants include organic solvents, emulsifiers, dispersants, thickeners, and water;

[0029] Optionally, the additives constitute the following percentages by mass in the composition: 10-50% organic solvent, 1-20% emulsifier, 0-10% dispersant, 0.1-2% thickener, and water to make up to 100%.

[0030] Optionally, the additives constitute the following percentages by mass in the composition: 20-30% organic solvent, 5-20% emulsifier, 5-10% dispersant, 0.1-2% thickener, and water to make up to 100%.

[0031] Optionally, the organic solvent includes one or more of methyl oleate and solvent oil; optionally, the weight ratio of methyl oleate to solvent oil is 1:(1-3), or optionally 1:2.

[0032] Further, the formulation of the acaricide composition is an emulsifiable concentrate. Optionally, the adjuvants include solvents, emulsifiers, and dispersants. Optionally, the adjuvants account for the following mass fractions of the composition: solvent 30-75%, emulsifier 1-20%, and dispersant 1-10%. Optionally, the solvent includes one or more of N,N-dimethyloctylamide, tributyl phosphate, and solvent oil.

[0033] Alternatively, the formulation of the acaricide composition is a microemulsion; optionally, the adjuvants include organic solvents, emulsifiers, dispersants, and water; optionally, the adjuvants account for the following mass fractions of the composition: 10-25% organic solvent, 5-30% emulsifier, 1-10% dispersant, and water to make up to 100%; optionally, the organic solvents include one or more of thiol, tetramethylbenzene, N,N-dimethyloctylamide, tributyl phosphate, N-octylpyrrolidone, methyl oleate, and solvent oil.

[0034] Furthermore, the formulation of the acaricide composition is a suspension, and optionally, the adjuvants include water, wetting agent, dispersant, thickener, antifreeze agent and defoamer;

[0035] Optionally, the additives constitute the following percentages by mass in the composition: wetting agent 0-20%, dispersant 0.3-15%, thickener 0.1-3%, antifreeze agent 2-5%, defoamer 0.1-3%, and water to 100%.

[0036] In a second aspect, a method for preparing the acaricidal composition described in the first aspect is provided, wherein acaricide quinone and fluranal are mixed evenly with adjuvants in appropriate proportions to prepare the acaricidal composition.

[0037] Thirdly, the application of the acaricidal composition described in the first aspect in the control of plant pests is provided; optionally, the pest is a mite, optionally a phytophagous mite, wherein the mite is selected from at least one of the following: Citrus citrus rust mite, apple red spider mite, cotton red spider mite, carmine spider mite, two-spotted spider mite, hawthorn spider mite, or broad mite.

[0038] The equipment used in the processing of the formulations of this invention is all publicly known.

[0039] Beneficial effects

[0040] 1) The two components of the acaricide composition selected in this invention have different mechanisms of action and have a good control effect on resistant populations with single-site mutations, which is conducive to improving acaricide efficiency and delaying the development of resistance in mites.

[0041] 2) The acaricide composition selected in this invention combines the acaricide advantages of two components. By combining a highly effective acaricide for killing mite eggs with a highly effective acaricide for killing adult mites, it is possible to eliminate all mite stages with a single application, reducing the number of manual applications and saving costs.

[0042] 3) The acaricide composition selected in this invention exhibits superior activity compared to single agents within the set ratio range, especially showing a higher control advantage against populations that are prone to developing resistance, such as citrus psyllid and two-spotted spider mite.

[0043] 4) The present invention also provides a formulation of an acaricidal composition, which is easy to implement, and the resulting product is stable, practical and easy to use.

[0044] 5) The acaricide composition selected in this invention combines old chemical components with new chemical components, protecting the efficacy of the new chemical components while extending the service life of the old chemical components, greatly maximizing the commercial value of both, and providing ideas and cases for more novel combinations of agents.

[0045] 6) The acaricide quinone aqueous suspension of the present invention, by introducing or combining a functional dispersant—comb-grafted acrylic acid copolymer, can make the formulation uniform and stable in appearance after being stored at 54°C for 14 days, without clumping, paste formation or precipitation, and all quality indicators meet national standards, actual transportation, storage and use requirements. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprising of," etc., will be understood to include the stated elements or components, and does not exclude other elements or other components.

[0047] Furthermore, to better illustrate the present invention, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In some embodiments, raw materials, elements, methods, and means well-known to those skilled in the art are not described in detail, in order to highlight the main points of the present invention. All percentages in all formulations of the present invention are by weight.

[0048] The acaricide quinone and flurana technical grade (TC) of the present invention can be obtained commercially.

[0049] (I) Indoor biological testing

[0050] Experimental Example 1: The synergistic effect of acaricide quinone and flenazone on eggs of *Paecilomyces citrus* was determined using the Bliss method.

[0051] Test subject: Panonychus citri, genetically independent, kept in an indoor constant temperature incubator, without exposure to any drugs, culture conditions were 26±1℃, relative humidity (RH) 70±5%, and light intensity 14L:10D.

[0052] Test reagents: acaricide TC, flurana TC, acetone, 0.1% Tween 80.

[0053] Drug solution preparation: Set up a series of experimental concentration gradients, dissolve the original drug in acetone to prepare a stock solution, and then dilute the stock solution to the required concentration with 0.1% Tween 80 according to the experimental requirements.

[0054] Experimental Methods: The leaf immersion method was used for biological testing. Referring to the guidelines for indoor bioassay of insecticides (Agricultural Industry Standard NY / T1154.7-2006) and the standard operating procedures for pesticide bioactivity testing (Insecticides), the specific operating procedures are as follows:

[0055] Mite oviposition assay procedure: Select a 10cm diameter petri dish as the container. Place an absorbent sponge, filter paper, and soybean leaves (2cm×2cm; back side down) in the petri dish from bottom to top. Select several female adult mites to lay eggs on the leaves for 24 hours. Remove the female adult mites from the leaves, fixing 30 eggs on each leaf. Immerse the soybean leaves in the prepared drug solution for 5 seconds, then remove them and place them on a leaf dish for culture. After all eggs in the CK water treatment group have hatched (egg hatching takes about 7 days), record the egg mortality rate on each leaf. Each concentration is repeated three times, and the mortality rate in the blank control group should not exceed 10% for the data to be considered valid.

[0056] Evaluation method: The Bliss method was adopted. Based on his concept of independent combined action, Bliss believed that the theoretical mortality rate P when insecticides and acaricides are mixed can be calculated using the following formula:

[0057] P = Pm + Pn(1 - Pm)

[0058] Wherein, Pm is the target mortality rate (%) when the active ingredient miticide quinone is used at a concentration of m; Pn is the target mortality rate (%) when the second active ingredient is used at a concentration of n.

[0059] If the measured actual mortality rate is greater than the theoretical mortality rate, it indicates that the combination of the two has a synergistic effect; otherwise, it has an antagonistic effect. The results are shown in Table 1.

[0060] Table 1. Synergistic effect determination of miticide and fluranal on eggs of *Paecilomyces citrus*.

[0061]

[0062] According to the results in Table 1, both acaricide and flurranal showed synergistic effects at ratios of (0.2–50):1. Specifically, synergistic effects were observed at ratios of 0.2:1, 1:4 (0.25:1), 1:3, 1:2 (0.5:1), 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, 30:1, 35:1, 40:1, 45:1, 50:1, or any two of these ratios.

[0063] Experimental Example 2: The synergistic effect of acaricide quinone and flenazone on adult female citrus parvovirus was determined using the Sun yp method.

[0064] Test subject: Citrus panonychus citri (female adult mite), genetically independent, kept in an indoor constant temperature incubator, without exposure to any drugs, culture conditions were 26±1℃, RH 70±5%, light 14L:10D.

[0065] Test reagents: acaricide TC, flurana TC, acetone, 0.1% Tween 80.

[0066] Drug solution preparation: Set up a series of experimental concentration gradients, dissolve the original drug in acetone to prepare a stock solution, and then dilute the stock solution to the required concentration with 0.1% Tween 80 according to the experimental requirements.

[0067] Experimental method: Biological testing was conducted using the immersion method.

[0068] Principle: The pesticide solution is applied directly to the surface of the test insect, and the contact toxicity of the insecticide / acaricide, which penetrates the epidermis and causes death, is measured. The Food and Agriculture Organization of the United Nations recommends the slide immersion method as a standard method for determining mite resistance, and it is suitable for testing adult female mites.

[0069] Operating steps:

[0070] ① Cut double-sided tape into 2-3cm lengths, stick it to one end of the glass slide, and use tweezers to peel off the paper off the tape;

[0071] ② Select healthy female adult mites that are 3-5 days old and stick their backs onto double-sided tape (Note: Do not stick the mite legs, antennae and mouthparts. Stick 4 rows per tape, and stick 10 mites per row).

[0072] ③ After placing the animals under normal feeding conditions for 4 hours, observe them with a stereomicroscope and remove any dead or inactive individuals.

[0073] ④ Prepare a stock solution of the original drug using an organic solvent (acetone, dimethyl sulfoxide, methanol, etc.), and then prepare 5-7 series of gradient concentrations using a 0.05%–0.1% Triton X-100 (or 0.1% Tween 80) aqueous solution. Immerse one end of a glass slide with the mite attached into the drug solution, gently shake for 5 seconds, then remove it and quickly blot the mite and excess drug solution around it with absorbent paper. Repeat each concentration 3 times, with a control prepared by immersing the slide in 0.1% Tween 80 water.

[0074] ⑤ After being placed under normal feeding conditions for 24 hours, the survival and mortality of citrus paronychia were observed and counted using a stereomicroscope.

[0075] Data analysis method: First, the Bliss method was used to screen the ratio range of miticide quinone and fluranal that increased the activity of female adult mites. Then, the Sun yp method was used to obtain the optimal synergistic ratio range in detail.

[0076] Sun Yunpei's method:

[0077] Formula for the co-toxicity coefficient (CTC value) of a mixture:

[0078] Relative toxicity index (TI) = (LC50 of standard reagent / LC50 of test reagent) × 100;

[0079] Actual Toxicity Index (ATI) of Mixture = (LC50 of Standard Agent / LC50 of Mixture) × 100;

[0080] Theoretical toxicity index (TTI) of a mixture = TI(A) × percentage content of agent A in the mixture + TI(B) × percentage content of agent B in the mixture;

[0081] Co-toxicity coefficient (CTC) = (Actual toxicity index ATI of the mixture / Theoretical toxicity index TTI of the mixture) × 100. A CTC greater than 120 indicates a synergistic effect; 80 to 120 indicates an additive effect; and less than 80 indicates an antagonistic effect.

[0082] The results of the Bliss method are shown in Table 2, and the results of the Sun yp method are shown in Table 3.

[0083] Table 2. Synergistic effect determination of mixed acaricides and fleraclods on adult female pseudococcus citrus.

[0084]

[0085] According to the results in Table 2, both miticides (0.1–70):1 showed good control efficacy against adult *Pachycarpus citrinum*. A synergistic effect was observed at ratios of (0.1–70):1, (0.1–20):1, and (0.1–10):1. The synergistic effect was even more significant at ratios of 0.1:1, 1:9, and 1:8. The ranges of 0.125:1, 1:7, 1:6, 1:5 (0.2:1), 1:4 (0.25:1), 1:3, 1:2 (0.5:1), 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, or any two of these values ​​all showed synergistic effects.

[0086] Table 3. Results of indoor combined virulence assay of miticide quinone and fleraclod mixed with adult female pseudococcus citrus.

[0087]

[0088] According to the results in Table 3, both miticide quinone and flenazone showed a synergistic effect on adult female citrus paronychia at ratios of (0.1–10):1 (co-toxicity coefficients were all greater than 120). The synergistic effect was more significant at ratios of (0.1–5):1, specifically (0.2–5):1. Alternatively, ratios of 1:10 (0.1:1), 1:9, 1:8 (0.125:1), 1:7, 1:6, and 1:5 (…) were also effective. The range of values ​​between any two of the following 0:1, 1:4 (0.25:1), 1:3, 1:2 (0.5:1), 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, or any two of these values ​​all showed synergistic effects.

[0089] Tables 2 and 3 show that the combination of abamectin and fluranal has a synergistic effect within a certain range (e.g., (0.1–70):1, (0.1–50):1, (0.2–50):1, (0.1–20):1, (5–10):1, (0.1–10):1, (0.1–5):1). Therefore, when achieving the same control effect, the amount of the combination used is lower than the total amount used by the single agent, thereby reducing the amount of pesticide used, reducing costs, and also reducing the risk of pesticide residue pollution in the environment.

[0090] Optionally, the ratios can be 0.01:1, 0.05:1, 0.08:1, 1:10 (0.1:1), 1:9, 1:8 (0.125:1), 1:7, 1:6, 1:5 (0.2:1), 1:4 (0.25:1), 1:3, 1:2 (0.5:1), 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, or 12:1. The following ratios may exhibit synergistic effects: 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, or any two of these ratios.

[0091] (II) Formulation Examples

[0092] Example 1: Preparation of 22% acaricide·flurane water-based emulsion (acaricide·flurane weight ratio 20:2)

[0093] A 22% miticide-flurane water emulsion was prepared by mixing the following ingredients according to the water emulsion processing technology: 20% miticide-flurane, 2% flurane, 10% methyl oleate, 20% 150# solvent oil, 5% tristyrene phenol polyoxyethylene ether, 0.1% xanthan gum, 5% sorbitan monooleate polyoxyethylene ether, and water to make up to 100%.

[0094] Example 2: Preparation of 20% miticide·flurane emulsifiable concentrate (miticide·flurane weight ratio 10:10)

[0095] Add 10% miticide quinone, 10% flurana, 5% agricultural emulsion 0201B, 2% sodium dodecylbenzenesulfonate, 2% agricultural emulsion 600, 10% N,N-dimethyloctylamide, 5% tributyl phosphate, and solvent oil S-150 to a mixing vessel to a final volume of 100%. Stir and mix thoroughly. If necessary, dissolve by heating in a hot water bath to obtain 20% miticide quinone·flurana emulsifiable concentrate.

[0096] Example 3: Preparation of 15% acaricide·flurane suspension (acaricide·flurane weight ratio 10:5)

[0097] The following ingredients are added sequentially to a mixing tank: 10% miticide quinone, 5% fluranal, 2% magnesium aluminum silicate, 5% sodium alkylnaphthalene formaldehyde condensate sulfonate, 2% sodium maleic olefin polymer, 0.3% xanthan gum, 5% ethylene glycol, 0.2% Kathon, and 0.5% defoamer SAG1522. Water is added to bring the total volume to 100%. The mixture is first coarsely pulverized and homogenized using high shear, and then fed into a sand mill for fine grinding. The particle size of the ground material is measured using a particle size analyzer. Once the particle size meets the standard requirements, the mixture is filtered to obtain a 15% miticide quinone·fluranal suspension.

[0098] Example 4: Preparation of 20% miticide·flurane suspension (miticide·flurane weight ratio 10:10)

[0099] The following ingredients are added sequentially to a mixing tank: 10% miticide quinone, 10% flurana, 2.5% methylcellulose, 3% comb-grafted acrylic acid copolymer, 0.5% silica, 0.2% xanthan gum, 5% ethylene glycol, and 0.5% defoamer SAG1522, with the remainder water to make up to 100 parts. The mixture is first coarsely pulverized and homogenized using high shear, and then pumped into a sand mill for fine grinding. The particle size of the sand-ground material is measured using a particle size analyzer. Once the particle size meets the standard requirements, the mixture is filtered to obtain a 20% miticide quinone·flurana suspension.

[0100] Example 5: Preparation of 10% acaricide·flurane wettable powder (acaricide·flurane weight ratio 5:5)

[0101] A 10% acaricide·flurane wettable powder is prepared by pulverizing the following ingredients: 5% miticide quinone, 5% flurana, 2% sodium dodecylbenzene sulfonate, 5% sodium lignosulfonate, 4% silica, and the remainder kaolin to make up 100%.

[0102] Example 6: Preparation of 20% acaricide·flurane microemulsion (acaricide·flurane weight ratio 15:5)

[0103] A 20% acaricide-flurane microemulsion was prepared by mixing 15% miticide quinone, 5% flurana, 6% N-octylpyrrolidone, 15% solvent oil S-150, 2% tristyrene-phenol polyoxyethylene ether phosphate ammonium salt, 15% alkylphenol formaldehyde resin polyoxyethylene ether, and water to make up the remainder to 100%, according to the microemulsion preparation method.

[0104] Comparative Example 1: 15% Acaricide Suspension

[0105] The following ingredients are added sequentially to a mixing tank: 15% miticide quinone, 0.5% methylcellulose, 2% comb-grafted acrylic acid copolymer, 0.5% silica, 0.2% xanthan gum, 5% ethylene glycol, and 0.5% defoamer SAG1522. The remaining water is added to make up to 100 parts. The mixture is first coarsely pulverized and homogenized under high shear, and then pumped into a sand mill for fine grinding. The particle size of the sand-ground material is measured by a particle size analyzer. Once the particle size meets the standard requirements, the mixture is filtered to obtain a 15% miticide quinone suspension.

[0106] Comparative Example 2, 5% Freranar Suspension

[0107] The following ingredients are added sequentially to a mixing tank: 5% Freranal, 0.5% methylcellulose, 3% comb-grafted acrylic acid copolymer, 0.5% silica, 0.4% xanthan gum, 5% ethylene glycol, and 1% defoamer SAG1522. The remaining water is added to make up to 100 parts. The mixture is first coarsely pulverized and homogenized under high shear, and then pumped into a sand mill for fine grinding. The particle size of the sand-ground material is detected by a particle size analyzer. Once the particle size meets the standard requirements, the mixture is filtered to obtain a 5% Freranal suspension.

[0108] Comparative Example 3: 10% Fipronil Suspension

[0109] The following ingredients are added sequentially to a mixing tank: 10% fipronil, 2% alkyl naphthalene sulfonate condensate, 5% comb-grafted acrylic acid copolymer, 0.5% silica, 0.2% xanthan gum, 5% ethylene glycol, and 0.5% defoamer SAG1522. The remaining water is added to make up to 100 parts. The mixture is first coarsely pulverized and homogenized under high shear, and then pumped into a sand mill for fine grinding. The particle size of the sand-ground material is measured by a particle size analyzer. Once the particle size meets the standard requirements, the mixture is filtered to obtain a 10% fipronil suspension.

[0110] In the above embodiments, the raw materials are all commercially available materials. For example, the comb-grafted acrylic acid copolymer was purchased from Croda (4913), or it can be purchased from Jierun (755) or Fangzhong (DS809).

[0111] Test Example 1: Field Efficacy Verification Example

[0112] Field efficacy trial of citrus parchomitid

[0113] Experimental objective: Field efficacy trials are conducted to evaluate the efficacy of tested pesticides against target organisms in complex field environments, in order to verify the practical application value of pesticides in agricultural production. Through field efficacy trials, the combined product of miticide quinone and flenafil can be verified for its effectiveness in controlling citrus psyllids in the field.

[0114] Experimental Methods: According to the National Efficacy Testing Guidelines (GB / T 17980.11-2000), after delineating the plots, the citrus trees within each plot need to be tagged. Two citrus trees are used in each plot. Branches in five directions (east, south, west, north, and center) of each tree are tagged. Five leaves are selected from each branch, ideally with at least two live mites on each leaf. A total of 25 leaves are counted per tree, and the number of live mites on 50 leaves is counted for each plot. The initial mites population in each plot needs to be counted before application. The number of live mites in each plot needs to be counted 1 day, 3 days, and 10 days after application.

[0115] Application method: The dosage of pesticide is shown in Table 4. Place the prepared pesticide solution in the sprayer. After testing the uniformity of the pesticide spray, spray each plot according to the plan. Spray one liter of pesticide solution in each plot. Before spraying different treatments, rinse the sprayer with clean water three times to ensure the accuracy of the experiment. Only one spraying treatment is performed in the entire experiment.

[0116] Data processing methods: Based on the experimental design, the control effect was calculated using the following formula on the statistically analyzed data. The significance difference between each treatment was analyzed using SPSS analysis software (Duncan's new multiple range method) to compare the differences between the test drug and the control treatment. The data were analyzed and summarized.

[0117] Mite reduction rate = [(Number of live mites before application - Number of live mites after application) / Number of live mites before application] × 100%

[0118] Control efficacy = [(PT-CK) / (1-CK)] × 100%;

[0119] In the formula, CK represents the mite population reduction rate in the blank control area, and PT represents the mite population reduction rate in the drug-treated area. The results are shown in Table 4.

[0120] Table 4. Results of field efficacy trials of the combination of miticide quinone and fleraclod for controlling citrus parchomitid.

[0121]

[0122]

[0123] Note: The baseline values ​​for Chinese medicine in Table 4 are the average values ​​of four replicates.

[0124] As shown in Table 4, Examples 1-6 all exhibited good control effects against citrus parsnipus. The control rate reached over 80% 10 days after application, demonstrating faster efficacy than commercially available agents. This indicates a longer-lasting effect, achieving the goal of eliminating all mite stages with a single application. It significantly improved the activity in killing eggs and adults, and its duration of effect was also superior to the single-agent control.

[0125] In summary, the acaricidal composition selected in this invention combines the acaricidal advantages of two components. By combining a highly effective acaricide for killing mite eggs with a highly effective acaricide for killing adult mites, a single application can eliminate all mite stages, reducing the number of manual applications and saving costs. The two components of the acaricidal composition selected in this invention have different mechanisms of action and no interaction. It has a good control effect on resistant populations with single-site mutations that develop resistance to mitochondrial complex class III compounds, which is beneficial for improving acaricidal efficiency and delaying the development of mite resistance. The acaricidal composition selected in this invention combines old and new chemical components, protecting the efficacy of the new chemical component while extending the lifespan of the old chemical component, greatly maximizing the commercial value of both, and providing ideas and examples for more novel pesticide combinations.

[0126] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A mite-killing composition containing miticide quinone, characterized in that, The active ingredients include acaricide quinone and fleranal, wherein the weight ratio of acaricide quinone to fleranal is 99:1 to 1:

99.

2. The acaricide composition according to claim 1, characterized in that, The weight ratio of acaricide to fluranal is 70–1:1–70, optionally 50–1:1–50, optionally 30–1:1–30, optionally 20–1:1–20, optionally (0.1–70):1, optionally (0.1–50):1, optionally (0.2–50):1, optionally (0.1–20):1, optionally (0.1–10):1, optionally (5–10):1, optionally (0.1–5):

1.

3. The acaricide composition according to claim 1, characterized in that, The content of the active ingredient accounts for 1% to 90% of the total composition, optionally 1% to 40%, optionally 10% to 40%, optionally 10% to 30%, optionally 10% to 22%, and the balance is pesticide-acceptable adjuvants; And / or, the active ingredient may also contain one or more other agricultural active ingredients.

4. The acaricide composition according to claim 3, characterized in that, The additives mentioned are one or more of the following: emulsifiers, wetting agents, dispersants, solvents, stabilizers, thickeners, defoamers, preservatives, antifreeze agents, or fillers; Optionally, the emulsifier includes nonionic emulsifiers and anionic emulsifiers; optionally, the nonionic emulsifier is selected from one or more of sorbitan monooleate polyoxyethylene ether, fatty alcohol polyoxyethylene ether, tristyrene-phenol polyoxyethylene ether, styrene-phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styrene-phenol formaldehyde resin polyoxyethylene polyoxypropylene ether, or castor oil polyoxyethylene ether; the anionic emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, triphenylethylphenol polyoxyethylene ether phosphate amine salt, nonylphenol polyoxyethylene ether phosphate amine salt, or castor oil polyoxyethylene ether phosphate amine salt, agricultural emulsion 0201B, and agricultural emulsion 600; Optionally, the dispersant is selected from one or more of the following: comb-grafted acrylic acid copolymer, sodium salt of acrylic acid homopolymer, sodium salt of maleic olefin polymer, sodium salt of naphthalene sulfonate formaldehyde condensate, lignin sulfonate, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenylethylphenol polyoxyethylene ether phosphate, tristyrenephenol polyoxyethylene ether phosphate ammonium salt, fatty alcohol polyoxyethylene ether phosphate, sodium salt of p-hydroxyphenyl lignin sulfonate, or alkyl naphthaldehyde condensate sulfonate. Optionally, the wetting agent is selected from one or more of fatty alcohol polyoxyethylene ether, naphthalene sulfonate, sodium dodecyl sulfate or alkylphenol resin polyoxyethylene ether sulfate; Optionally, the solvent is selected from one or more of water, trimethylbenzene, tetramethylbenzene, N,N-dimethyloctylamide, tributyl phosphate, N-octylpyrrolidone, methyl oleate, and solvent oil; Optionally, the thickener is selected from one or more of xanthan gum, magnesium aluminum silicate, sodium alginate, sodium carboxymethyl cellulose, gum arabic, gelatin, polyvinyl alcohol, or methyl cellulose; Optionally, the defoamer is selected from one or more of alcohols, fatty acids and fatty acid esters, amides, phosphoric acids, and polyethers; Optionally, the antifreeze is selected from one or more of carbonates, ethanol, ethylene glycol, glycerol, ethylene glycol butyl ether acetate, and urea; Optionally, the filler is selected from one or more of carbonates, sulfates, sodium chloride, kaolin, diatomaceous earth, pearl clay, vermiculite, talc, and silica; optionally, the carbonates include one or more of precipitated calcium carbonate hydrate and precipitated calcium carbonate; optionally, the sulfates include one or more of sodium sulfate or calcium sulfate.

5. The acaricide composition according to claim 4, characterized in that, The formulation of the acaricide composition is a wettable powder, emulsifiable concentrate, suspension concentrate, dispersible oil suspension, suspension emulsion, microemulsion, water emulsion, or water-dispersible granules.

6. The acaricide composition according to claim 5, characterized in that, The acaricide composition is in the form of an emulsion, and optionally, the adjuvants include organic solvents, emulsifiers, dispersants, thickeners and water; Optionally, the additives constitute the following percentages by mass in the composition: 10-50% organic solvent, 1-20% emulsifier, 0-10% dispersant, 0.1-2% thickener, and water to make up to 100%. Optionally, the additives constitute the following percentages by mass in the composition: 20-30% organic solvent, 5-20% emulsifier, 5-10% dispersant, 0.1-2% thickener, and water to make up to 100%. Optionally, the organic solvent includes one or more of methyl oleate and solvent oil; optionally, the weight ratio of methyl oleate to solvent oil is 1:(1-3), or optionally 1:

2.

7. The acaricide composition according to claim 5, characterized in that, The acaricide composition is in the form of an emulsifiable concentrate. Optionally, the adjuvants include a solvent, an emulsifier, and a dispersant. Optionally, the adjuvants account for the following mass fractions of the composition: 30-75% solvent, 1-20% emulsifier, and 1-10% dispersant. Optionally, the solvent includes one or more of N,N-dimethyloctylamide, tributyl phosphate, and solvent oil. Alternatively, the formulation of the acaricide composition is a microemulsion; optionally, the adjuvants include organic solvents, emulsifiers, dispersants, and water; optionally, the adjuvants account for the following mass fractions of the composition: 10-25% organic solvent, 5-30% emulsifier, 1-10% dispersant, and water to make up to 100%; optionally, the organic solvents include one or more of thiol, tetramethylbenzene, N,N-dimethyloctylamide, tributyl phosphate, N-octylpyrrolidone, methyl oleate, and solvent oil.

8. The acaricide composition according to claim 5, characterized in that, The acaricide composition is in the form of a suspension, and optionally, the adjuvants include water, wetting agent, dispersant, thickener, antifreeze agent and defoamer; Optionally, the additives constitute the following percentages by mass in the composition: wetting agent 0-20%, dispersant 0.3-15%, thickener 0.1-3%, antifreeze agent 2-5%, defoamer 0.1-3%, and water to 100%.

9. A method for preparing the acaricide composition according to any one of claims 1 to 8, characterized in that, Acaricide composition is prepared by mixing acaricide quinone and fleranal with adjuvants in appropriate proportions.

10. The use of the acaricidal composition according to any one of claims 1 to 8 in the control of plant pests; optionally, the pest is a mite, optionally a phytophagous mite, wherein the mite is selected from at least one of the following: Citrus pterocaryon, Citrus rust mite, apple red spider mite, cotton red spider mite, carmine spider mite, two-spotted spider mite, hawthorn spider mite, or broad mite.

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