Cyflufenamid-fluopyram composition as well as preparation method and application thereof

Abstract

The invention discloses a cyflufenamid-fluopyram composition, the preparation raw materials at least comprise an active compound, the active compound comprises cyflufenamid and fluopyram, and the weight ratio of the cyflufenamid to the fluopyram is 1: (1-5). According to the microemulsion dosage form prepared by the invention, the particle size of the microemulsion is close to nanoscale, the microemulsion can be absorbed by crops more easily, the surface tension of contact with plant leaves is small, the microemulsion is easy to spread on the surfaces of the leaves, and liquid medicine is not easy to lose; the prepared missible oil dosage form and liquid medicine have stronger adhesion, can be mixed with a fertilizer for use, have good compatibility, and do not generate the problems of layering and flocculation; the prepared soluble concentrate can form a true solution after being diluted, and is convenient to apply and good in cold and hot storage stability. The nematicide provided by the invention is a broad-spectrum bactericide, can prevent and control alternaria leaf spot, leaf spot, gray mold, powdery mildew and the like on fruits, vegetables and field crops, is an efficient, green and low-toxicity nematicide, and has unique mobility and low toxicity.

Description

Technical Field

[0001] The invention relates to a cyfluanid-fluopyram microemulsion and a preparation method and application thereof, and relates to A01N, and in particular to the field of pesticides or herbicides. Background Art

[0002] Cyfluanid has a good control effect on various powdery mildews. Powdery mildews mainly occur on plant leaves. However, since leaves have a certain degree of hydrophobicity, the drug is easy to roll off the surface of the leaves after application, causing the loss of the drug. Therefore, making the drug into a microemulsion can improve the stability of the drug and increase its efficacy. The microemulsion particle size of the microemulsion is close to the nanometer level, and the drug is more easily absorbed by plants. The drug solution diluted with the emulsifiable concentrate has stronger adhesion, is resistant to rain erosion, and can be mixed with fertilizers. It has good compatibility and will not cause stratification and flocculation problems; the soluble concentrate can form a true solution after dilution, which is more convenient to apply and has good cold and hot storage stability. Microemulsions and soluble concentrates have small particle sizes and are easy to aggregate in different environments, especially in high and low temperature environments, or after the drug is diluted with water for use, the aggregation of drug particles affects the actual efficacy of the drug. After the emulsifiable concentrate is diluted, it is easy to produce emulsifiable concentrate or precipitation. Therefore, it is very important to develop a dilution-stable, high and low temperature storage-stable microemulsion, emulsifiable concentrate, and soluble concentrate.

[0003] Chinese invention patent CN201410362664.2 discloses a fungicide composition containing cyfluthrin and amide fungicides. Cyfluthrin and fluopyram are used in a weight ratio of 1:10 to 8:1, and are prepared into suspension, water-dispersible granules, wettable powders, dispersible oil suspensions or water-emulsion formulations, which have good control effects on wheat powdery mildew, cucumber powdery mildew, and strawberry powdery mildew. However, it is easy to crystallize under low temperature conditions, and the low-temperature storage stability effect is not good. Chinese invention patent CN201410621645.7 discloses a fungicide composition containing copper oxalate diacetonamine and amide fungicides. The active ingredients are copper oxalate diacetonamine and amide fungicides, which are prepared into water-dispersible granules, wettable powders or dispersible oil suspensions, and have good control effects on cucumber downy mildew, cucumber powdery mildew, potato late blight, rice blast, and rice sheath blight. However, it has not been prepared into a microemulsion formulation, and the actual efficacy is poor. Summary of the invention

[0004] In order to improve the efficacy of pesticides and optimize the stability of microemulsions, the first aspect of the present invention provides a cyfluanid-fluopyram composition, wherein the preparation raw materials include at least the technical drug, the technical drug includes cyfluanid and fluopyram, and the weight ratio of cyfluanid to fluopyram is 1:(1-5).

[0005] As a preferred embodiment, the technical drug includes cyfluanid and fluopyram, and the weight ratio of cyfluanid to fluopyram is 1:3.

[0006] As a preferred embodiment, the dosage form prepared from the composition is selected from one or a combination of powders, emulsifiable concentrates, microemulsions, suspensions, water dispersible granules, and soluble solutions.

[0007] As a preferred embodiment, the raw materials for preparing the microemulsion include, by weight percentage: 5-10% original drug, 25-35% emulsifier, 50-60% solvent, 5-10% cosolvent, 0.01-0.05% defoamer, and deionized water supplemented to 100%.

[0008] As a preferred embodiment, the emulsifier comprises a combination of a nonionic emulsifier and an anionic emulsifier, and the weight ratio of the nonionic emulsifier to the anionic emulsifier is (20-28): (1-5).

[0009] As a preferred embodiment, the weight ratio of the nonionic emulsifier to the anionic emulsifier is 24:4.

[0010] As a preferred embodiment, the nonionic emulsifier includes a polyoxyethylene ether emulsifier and a block emulsifier, and the weight ratio of the polyoxyethylene ether emulsifier to the block emulsifier is (3-6):1.

[0011] As a preferred embodiment, the weight ratio of the polyoxyethylene ether emulsifier to the block emulsifier is 5:1.

[0012] As a preferred embodiment, the cloud point of the polyoxyethylene ether emulsifier is 60-65° C., and the pH value of a 1 wt % aqueous solution is 5-7. Preferably, the polyoxyethylene ether emulsifier is triphenyl phenol polyoxyethylene ether.

[0013] As a preferred embodiment, the block emulsifier is a hydroxy polyethylene oxide block copolymer, the molar ratio of EO:PO is 1:(1.7-2), and the pH value of the hydroxy polyethylene oxide block copolymer is 6.5-7.5.

[0014] As a preferred embodiment, the anionic emulsifier is calcium dodecylbenzenesulfonate.

[0015] The applicant found in the experiment that the combination of triphenylethylphenol polyoxyethylene ether, hydroxy polyethylene oxide, and calcium dodecylbenzene sulfonate as an emulsifier combination can improve the high temperature stability of the pesticide and avoid the turbidity of the pesticide as the temperature rises. The possible reason is speculated to be: the combination of non-ionic surfactants and anionic surfactants can transform some non-soluble substances at high temperatures into completely soluble substances, and the introduction of non-ionic block copolymer hydroxy polyethylene oxide can adjust the hydrophilic and lipophilic values ​​of the system, increase the cloud point of the system, and improve the high temperature stability of the pesticide.

[0016] As a preferred embodiment, the solvent is selected from one or a combination of naphtha, amide solvents, cyclohexanone, alkanes, and ether solvents.

[0017] As a preferred embodiment, the solvent is a combination of S-150 light aromatic solvent naphtha and dimethylacetamide. Preferably, the weight ratio of S-150 light aromatic solvent naphtha to dimethylacetamide is (25-30): (23-28). More preferably, the weight ratio of S-150 light aromatic solvent naphtha to dimethylacetamide is 29:25.

[0018] During the experiment, the applicant found that the original drugs fluopyram and cyfluthrin have poor solubility in water. When used with water, the microemulsion particles will aggregate, increasing the particle size distribution range of the microemulsion particles, causing the microemulsion to precipitate and block the pesticide spray nozzle. The applicant found that the use of a combination of dimethylacetamide and s-150 light aromatic solvent naphtha as a mixed solvent can improve the stability of the emulsion and effectively slow down the generation of precipitation. The possible reason is speculated to be: when the combination of dimethylacetamide and s-150 light aromatic solvent naphtha is used as a solvent, the interface film of the microemulsion becomes thinner after being diluted with water, dimethylacetamide can be dissolved in water, and the oil-water miscibility of the microemulsion is improved. In addition, the use of the low water-soluble s-150 light aromatic solvent naphtha further slows down the precipitation of the original drug, thereby maintaining the stability of the microemulsion.

[0019] As a preferred embodiment, the weight ratio of the solvent to the co-solvent is (50-55):(8-12).

[0020] As a preferred embodiment, the weight ratio of the solvent to the co-solvent is 54:10.

[0021] As a preferred embodiment, the co-solvent is selected from one or a combination of ethanol, isobutanol, isooctyl alcohol, propylene carbonate, and cyclohexanone.

[0022] As a preferred embodiment, the co-solvent is isooctyl alcohol.

[0023] As a preferred embodiment, the defoaming agent is polyoxypropylene glyceryl ether.

[0024] The applicant discovered during the experiment that the use of isooctyl alcohol as a cosolvent and the weight ratio of the solvent to the cosolvent (50-55): (8-12) can improve the low-temperature stability of the pesticide microemulsion, allowing it to be stored for a long time in a low-temperature environment without crystallization or precipitation. The possible reason is speculated to be: the introduction of isooctyl alcohol can lower the freezing point of the microemulsion pesticide and reduce the separation of the solvent and the original drug, and the weight ratio of the solvent to the cosolvent (50-55): (8-12) makes the original drug more soluble in the solvent and less likely to crystallize and precipitate in a low-temperature environment, thereby improving the low-temperature stability of the pesticide microemulsion.

[0025] As a preferred embodiment, the raw materials for preparing the emulsifiable concentrate include, by weight percentage: 5-10% of the original drug, 5-15% of the emulsifier, 5-15% of the cosolvent, and the organic solvent is supplemented to 100%.

[0026] As a preferred embodiment, the original drug in the emulsifiable concentrate includes cyfluanid and fluopyram, and the weight ratio of cyfluanid to fluopyram is 1:3.

[0027] As a preferred embodiment, the emulsifier in the emulsifiable concentrate includes a combination of triphenylethylphenol polyoxyethylene ether, calcium dodecylbenzene sulfonate, and fatty alcohol polyoxyethylene ether in a weight ratio of (3-5):1:(1-5).

[0028] As a preferred embodiment, the weight ratio of triphenylphenol polyoxyethylene ether, calcium dodecylbenzene sulfonate, and fatty alcohol polyoxyethylene ether is 4:1:3.

[0029] As a preferred embodiment, the co-solvent is isooctyl alcohol, and the organic solvent is a combination of dimethylacetamide and light aromatic solvent naphtha (s-150). The weight ratio of dimethylacetamide to light aromatic solvent naphtha is (20-30): (50-60). Preferably, the weight ratio of dimethylacetamide to light aromatic solvent naphtha is 25:51.

[0030] As a preferred embodiment, the raw materials for preparing the soluble solution include, by weight percentage: 5-10% of the original drug, 10-20% of the emulsifier, 5-15% of the cosolvent, and the organic solvent is supplemented to 100%.

[0031] As a preferred embodiment, the original drug in the soluble solution includes cyfluanid and fluopyram, and the weight ratio of cyfluanid to fluopyram is 1:3.

[0032] As a preferred embodiment, the emulsifier in the soluble solution includes a combination of an anionic nonionic mixed emulsifier and a fatty alcohol polyoxyethylene ether, with a weight ratio of (5-10):10.

[0033] As a preferred embodiment, the anionic nonionic mixed emulsifier is alkoxylated alkylphenol + 4-C 10-14 -alkyl derivative benzenesulfonic acid calcium salt; the fatty alcohol polyoxyethylene ether is AEO-9.

[0034] As a preferred embodiment, the cosolvent is decanoic acid amide, and the organic solvent is a combination of dimethylpropionamide and tetrahydrofurfuryl alcohol. Preferably, the weight ratio of dimethylpropionamide to tetrahydrofurfuryl alcohol is (20-30): (40-50).

[0035] As a preferred embodiment, the weight ratio of dimethylpropionamide to tetrahydrofurfuryl alcohol is 25:41.

[0036] The second aspect of the present invention provides a method for preparing a cyfluthrin-fluopyram microemulsion, comprising the following steps:

[0037] S1: Add the solvent and co-solvent into the preparation kettle, turn on the agitator, add the original drug, stir, dissolve, and mix for 30-60 minutes;

[0038] S2: accurately weigh the emulsifier and defoamer according to the feeding ratio and add them into the preparation kettle in sequence, turn on the stirrer and mix for 30-60 minutes;

[0039] S3: Add deionized water into the preparation kettle and mix for 30-60 minutes.

[0040] As a preferred embodiment, the method for preparing the cyfluthrin-fluopyram emulsifiable concentrate comprises the following steps:

[0041] S1: Add the organic solvent and co-solvent into the preparation kettle, turn on the agitator, add the original drug, stir and dissolve for 30-60 minutes;

[0042] S2: accurately weigh the emulsifier according to the feeding ratio and add it into the preparation kettle in sequence, turn on the stirrer and mix for 30-60 minutes.

[0043] As a preferred embodiment, the method for preparing a soluble solution of cyfluthrin and fluopyram comprises the following steps:

[0044] S1: Add the organic solvent and co-solvent into the preparation kettle, turn on the agitator, add the original drug, stir and dissolve for 30-60 minutes;

[0045] S2: accurately weigh the emulsifier according to the feeding ratio and add it into the preparation kettle in sequence, turn on the stirrer and mix for 30-60 minutes.

[0046] The third aspect of the present invention provides an application of a cyfluthrin-fluopyram combination, which is applied to leaf spot, leaf spot, gray mold, powdery mildew, sclerotinia, and early blight on fruit trees, vegetables, and field crops; and is applied to the prevention and control of nematodes.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] (1) The cyfluanid / fluopyram composition of the present invention uses a combination of dimethylacetamide and S-150 light aromatic solvent naphtha as solvent, so that the prepared pesticide microemulsion system is stable and is not easy to become turbid after being diluted with water or hard water. The particle size distribution of the microemulsion is uniform, the microemulsion particles are not easy to precipitate, the microemulsion system is stable, and crystals are not easy to precipitate.

[0049] (2) The cyfluanid / fluopyram composition of the present invention uses a combination of triphenyl phenol polyoxyethylene ether, hydroxy polyethylene oxide, and calcium dodecylbenzene sulfonate as an emulsifier in the microemulsion, which can improve the high temperature stability of the pesticide and prevent the pesticide from becoming turbid as the temperature rises.

[0050] (3) The cyfluanid-fluopyram composition of the present invention uses isooctyl alcohol as a cosolvent in the microemulsion, and the weight ratio of the solvent to the cosolvent is (50-55):(8-12), which can improve the low-temperature stability of the pesticide microemulsion, and can be stored in a low-temperature environment for a long time without crystallization or precipitation, and can be stably stored at -10°C for 14 days without crystallization or precipitation.

[0051] (4) The cyfluanid / fluopyram composition of the present invention is used to prepare a microemulsion formulation. The particle size of the microemulsion is close to the nanometer level, which is easier for crops to absorb. In addition, when in contact with plant leaves, the surface tension is small and it is easy to spread on the leaf surface, and the liquid is not easy to lose. At the same time, when mixed with fertilizers, it has good compatibility and will not cause stratification and flocculation problems.

[0052] (5) The cyfluanid-fluopyram composition of the present invention is a broad-spectrum fungicide, seed treatment agent, and agricultural product storage preservative. It can prevent and control leaf spot disease, leaf spot disease, gray mold, powdery mildew, sclerotinia disease, early blight, etc. on fruits and vegetables such as grapes, pears, bananas, apples, cucumbers, tomatoes, and field crops. It can also prevent and control various nematodes. It is a highly effective, green, low-toxic nematicide with unique mobility and low toxicity. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is a photograph of the crystallization of the microemulsion prepared in Comparative Example 1 under fluorescent light; Figure 2 This is a stability photograph of the microemulsion prepared in Comparative Example 1 after being diluted and stored for 30min-120min and then diluted with water; Figure 3 This is a photo of the microemulsion prepared in Comparative Example 2 after cold storage at 0°C for 7 days; Figure 4 This is a photo of the microemulsion prepared in Comparative Example 2 being diluted in water after being stored at 0°C for 7 days; Figure 5 This is a photo of the microemulsion prepared in Comparative Example 3 that was heat stored at 54°C for 1-4 days; Figure 6 The microemulsions prepared in Example 1, Comparative Examples 1-3 and commercially available competitive microemulsions are photographed on trees; Figure 7 The test results of the contact angles of the microemulsions prepared in Example 1 and Comparative Examples 1-3; Figure 8 This is Example 1, the leaf spreading performance test of the competitor's microemulsion, left: competitor; right: Example 1; Fig. 9 The dilution stability of the microemulsion of Example 1 using potassium dihydrogen phosphate solution; Fig.10 The dilution stability of the microemulsions prepared in Example 1 and Comparative Examples 1-3 was diluted 3 times with hard water and then diluted 20 times with deionized water.

[0054] Fig.11 The stability photos of Comparative Examples 4 and 5 after being stored at -10°C for 14 days, with Comparative Example 4 on the left and Comparative Example 5 on the right; Fig.12 The stability photos of Example 2 and Comparative Example 6 after being stored at 54°C for 14 days, with Example 2 on the left and Comparative Example 6 on the right; Fig.13 The emulsified dispersibility photos of Example 2, Comparative Examples 7, 8, and 9 are shown from left to right: Example 2, Comparative Examples 7, 8, and 9; Fig.14 For Example 2, Comparative Examples 7, 8, and 9, the emulsifiable concentrate was dripped into the measuring cylinder, the stopper was covered, and the measuring cylinder was turned over 15 times. From left to right, they are Example 2, Comparative Examples 7, 8, and 9; Fig.15 The pictures are after 200 times dilution of hard water, from left to right are Example 2, Comparative Example 10, Comparative Example 11, Comparative Example 12; Fig.16 Dynamic surface tension image for testing spreadability.

[0055] Fig.17 This is a stability photo of Comparative Example 10 after storage at -10°C for 14 days; Fig.18 The stability photos of Example 3 and Comparative Example 11 after being stored at 54°C for 14 days, with Comparative Example 11 on the left and Example 3 on the right; Fig.19 The pictures are after 200 times dilution of hard water, left: Example 3, right: Comparative Example 15; Fig. 20 Dynamic surface tension pictures for testing spreadability, No. 1. Example 3; No. 2. Comparative Example 16. DETAILED DESCRIPTION

[0056] Embodiment 1

[0057] A cyfluanid·fluopyram microemulsion, the preparation raw materials of which are calculated by weight percentage and include the following preparation raw materials as shown in Table 1 below.

[0058] Table 1

[0059]

[0060] The triphenyl phenol polyoxyethylene ether is Nongru 600#, purchased from Kaiyuan, with a turbidity point of 60-65°C and a pH value of 1wt% aqueous solution of 5-7; the hydroxy polyethylene oxide is purchased from Nouryon, model Ethylan NS 500LQ, the molar ratio of EO:PO is 1:1.71, and the pH value is 6.5-7.5; the s-150 light aromatic solvent naphtha is purchased from Sentai Chemical; the polyoxypropylene glycerol ether is purchased from Gutian, model P-3114. The polyoxyethylene alkylphenol ether is purchased from Jiangsu Kaiyuan, model OP-10; the alkylphenol polyoxyethylene ether formaldehyde condensate is purchased from Jiangsu Kaiyuan, model 700#.

[0061] A method for preparing a cyfluanid / fluopyram microemulsion comprises the following steps:

[0062] S1: Add the solvent and co-solvent into the preparation kettle, turn on the agitator, add the original drug, stir, dissolve, and mix for 50 minutes;

[0063] S2: accurately weigh the emulsifier and defoamer according to the feeding ratio and add them into the preparation kettle in sequence, turn on the stirrer and mix for 50 minutes;

[0064] S3: Add deionized water into the preparation kettle and mix for 50 minutes.

[0065] Embodiment 2

[0066] A cyfluanid-fluopyram emulsifiable concentrate, the preparation raw materials of which are calculated by weight percentage and include the following preparation raw materials as shown in Table 2 below.

[0067] Table 2

[0068]

[0069]

[0070] A method for preparing cyfluthrin-fluopyram emulsifiable concentrate comprises the following steps:

[0071] S1: add the solvent and co-solvent into the preparation kettle, turn on the stirrer, add the original drug, stir and dissolve for 60 minutes; S2: accurately weigh the emulsifier according to the feeding ratio and add it into the preparation kettle in sequence, turn on the stirrer and mix for 60 minutes.

[0072] Comparative Example 10

[0073] A cyfluanid-fluopyram emulsifiable concentrate, the specific implementation manner is the same as that of Example 2, except that the emulsifier is a combination of dimethicone copolyol, 500# (calcium dodecylbenzene sulfonate), and benzylphenol polyoxyethylene polypropylene ether, with a weight ratio of 4:1:3.

[0074] Comparative Example 11

[0075] A cyfluanid-fluopyram emulsifiable concentrate, the specific implementation manner is the same as that of Example 2, except that the emulsifier is a combination of 603# (triphenol polyoxyethylene ether), 500# (calcium dodecylbenzene sulfonate), and alkylphenol polyoxyethylene polyoxypropylene ether, with a weight ratio of 4:1:3.

[0076] Comparative Example 12

[0077] A cyfluanid / fluopyram emulsifiable concentrate, the specific implementation manner is the same as that of Example 2, except that the emulsifier is a combination of dimethicone copolyol, 500# (calcium dodecylbenzene sulfonate), and fatty amide taurate, with a weight ratio of 4:1:3.

[0078] Embodiment 3

[0079] A soluble solution of cyfluthamidopyram, the preparation raw materials of which are calculated by weight percentage and include the following raw materials:

[0080] Table 3

[0081]

[0082]

[0083] The method for preparing a soluble solution of cyfluthrin and fluopyram comprises the following steps:

[0084] S1: Add the solvent and co-solvent into the preparation kettle, turn on the agitator, add the original drug, stir and dissolve for 60 minutes;

[0085] S2: accurately weigh the emulsifier according to the feeding ratio and add it into the preparation kettle in sequence, turn on the stirrer and mix for 60 minutes to obtain the product.

[0086] Comparative Example 15

[0087] A soluble preparation of cyfluthamidoanilide / fluopyram, the specific implementation manner is the same as that of Example 3, except that the emulsifier is a combination of alkylphenol polyoxyethylene polyoxypropylene ether and AEO-9 (fatty alcohol polyoxyethylene ether), with a weight ratio of 8:10.

[0088] Comparative Example 16

[0089] A soluble solution of cyfluthrin and fluopyram, the specific implementation method is the same as that of Example 3, except that the emulsifier is Termul 5030 (alkoxylated alkylphenol + 4-C 10-14 -alkyl derivative benzenesulfonic acid calcium salt) and dimethicone copolyol in a weight ratio of 8:10.

[0090] Performance Testing

[0091] 1. The cyfluanid·fluopyram microemulsion of Example 1 was tested for physical and chemical properties, and the test results are shown in Tables 4 and 5 below. The cyfluanid·fluopyram emulsifiable concentrate of Example 2 was tested for physical and chemical properties, and the test results are shown in Table 5 below. The cyfluanid·fluopyram emulsifiable concentrate of Example 3 was tested for physical and chemical properties, and the test results are shown in Table 5 below.

[0092] Table 4

[0093]

[0094] Table 5

[0095]

[0096]

[0097] 2. The cyflufenamid·fluopyram microemulsion of Comparative Example 1 was placed under light for observation. A large amount of crystals were precipitated in Comparative Example 1. The test results are shown in Figure 1 After being diluted with water, the system of comparative example 1-3 was turbid, and the test results were shown in Figure 2 , Figure 2 From left to right in the figure are Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3.

[0098] 3. The cyflufenamid·fluopyram microemulsion of Comparative Example 2 was stored at 0°C for 7 days, and crystals precipitated at the bottom. The test results are shown in Figure 3 The cyfluthrin-fluopyram microemulsion of Comparative Example 1-3 was stored at 0°C for 7 days and then diluted with water. The system was turbid. The test results were shown in Figure 4 , Figure 4 From left to right in the figure are Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3.

[0099] 5. The cyflufenamid·fluopyram microemulsion of Comparative Example 3 was stored at 54°C for 1-4 days, and the system became turbid. The test results are shown in Figure 5 , from left to right are heat storage for 1 day, 4 days, 3 days, and 2 days.

[0100] 6. Wood climbing: The microemulsions prepared in Example 1, Comparative Examples 1-3, and the commercially available competitor's microemulsions with pigment added were placed in a watch glass. Five identical wooden sticks were placed in the watch glass liquid. The liquid height was consistent. The wood climbing was observed. The test results are shown in Figure 6 The higher the climbing height, the better, indicating that the absorbability of the agent is stronger, and the agent absorption effect of Example 1 is the best.

[0101] 7. Contact angle test: Test the contact angles of the microemulsions prepared in Example 1 and Comparative Examples 1-3. The test results are shown in Figure 7 The surface tension of Example 1 is lower and the spreading is faster.

[0102] 8. Leaf spreading performance test: The microemulsion of Example 1 and the commercial competitor was tested for spreading effect on leaves. The test results are shown in Figure 8 , the left is the partial spreading of the hanging leaf liquid (competitor's product), and the right is the complete spreading of the liquid (Example 1), which reduces the loss of the liquid and can achieve a moisturizing effect.

[0103] 9. Brine dilution performance: 20 times the concentration of the microemulsion of Example 1 was added to a 20 wt% potassium dihydrogen phosphate solution. The test results are shown in Fig. 9 , no crystal precipitation. (Simulating the effect of mixing with fertilizer)

[0104] 10. Dilution performance of different water qualities: The microemulsions prepared in Example 1 and Comparative Examples 1-3 were diluted with 3 times hard water and then diluted 20 times with deionized water. The test results are shown in Fig.10 , from left to right are Comparative Example 2, Comparative Example 1, Example 1, and Comparative Example 3. The results show that the system of Example 1 is clearer.

[0105] 11. Toxicity test:

[0106] Test method: This test was conducted in accordance with the Agricultural Industry Standard of the People's Republic of China (NY / T 1156.11-2008 and NY / T1156.6-2006) "Guidelines for Indoor Bioassay Tests of Pesticides - Fungicides" Part 11: Pot Plant Method for Control of Powdery Mildew of Cucurbits and Part 6: Determination of Combined Effects of Mixtures.

[0107] The test results are shown in Table 6.

[0108] Table 6

[0109]

[0110] 12. Field trial data: The trial was conducted in a farmer's greenhouse in Xianggu Village, Fancun Town, Taigu District, Jinzhong City, Shanxi Province from September to October 2023. The test site has suffered from severe powdery mildew of cucumbers in previous years.

[0111] The test agents and dosages are detailed in Table 1. The test set up 1 treatment, each treatment had 4 plots, and the plots were randomly arranged, with a total of 28 plots, with a plot area of ​​11.2m 2 , 4 replicates per treatment. Use a backpack electric sprayer, start at the early stage of cucumber powdery mildew, follow the instructions for each treatment, and spray with water. Apply the pesticide twice, 7 days apart, and set up a clean water treatment as a blank control. Investigate the disease base before applying the pesticide, and investigate the control effect before the second application and 10 days after the second application. The test results are shown in Table 5 below.

[0112] Table 7

[0113]

[0114] Anhui field trial: In accordance with the Quality Management Standards for Pesticide Registration Tests, Quality Management Standards for Pesticide Registration Field Efficacy Tests, test plans and relevant SOPs of the test institutions, quality assurance personnel reviewed the test plans, original data and final reports, checked the test operations, and the report results truly reflected the original data.

[0115] Test reagents:

[0116]

[0117] Application method and water consumption:

[0118] Use a backpack electric sprayer (3WBD-18) and add 50 liters of water per mu for spraying.

[0119] Test results:

[0120] Suitable application period and dosage: Apply the first time at the early stage of powdery mildew of cucumber, apply 6% fluopyram·cyfluthrin microemulsion, the preparation dosage is 40 ml / mu to 60 ml / mu (active ingredient dosage is 36 g / hectare to 54 g / hectare), and continue to apply the pesticide every 7 to 10 days, for a total of 3 applications.

[0121] How to use: Use a backpack electric sprayer to spray, disperse and dilute twice, and add water at 50 liters per mu. If rainfall is expected within 2 hours, do not apply pesticides.

[0122] Safety: The test agent is safe for the mid- and late-stage growth of cucumbers (plants) within the test dosage range (40 ml / mu to 60 ml / mu), and no phytotoxicity occurs.

[0123] The test results are shown in Table 6.

[0124] Table 8

[0125]

[0126] Shanxi field trial: Comply with the "Quality Management Standards for Pesticide Registration Tests" and the agricultural industry standard "Quality Management Standards for Pesticide Registration Field Efficacy Tests" (NY / T2885-2016), refer to the "Pesticide Field Efficacy Test Guidelines (I): Fungicide Control of Cucumber Powdery Mildew" (GB / T 17980.30-2000), and follow the relevant requirements of the SOP "Fungicide Control of Cucumber Powdery Mildew" (SXAU-SOP-F-002) of this test unit.

[0127] Test reagents:

[0128]

[0129] Start applying the pesticide at the early stage of cucumber powdery mildew. Weigh the pesticide according to the dosage required for each treatment, add water and spray normally. The spray should be uniform and consistent, without repeated spraying or missing spraying. The blank control is sprayed with clean water.

[0130] Use backpack electric sprayer, UIV-5 model, Weifang Motong Machinery Manufacturing Co., Ltd. The liquid volume is 50 liters / mu.

[0131] Refer to "Guidelines for Field Efficacy Tests of Pesticides (I): Control of Cucumber Powdery Mildew with Fungicides" (GB / T17980.30-2000) and proceed in accordance with the relevant requirements of this test unit's SOP "Control of Cucumber Powdery Mildew with Fungicides" (SXAU-SOP-F-002).

[0132] First survey: The first application of pesticide was carried out on September 5, 2023. Sporadic lesions appeared in the field and the disease index was recorded as zero.

[0133] Second investigation: The prevention efficacy will be investigated 10 days after the last application of pesticides on September 22, 2023, and the disease incidence will be recorded according to the grading standards.

[0134] Four random survey points were selected in each plot, and all leaves of two plants were surveyed at each point. The results were graded and recorded according to the percentage of lesions to leaf area.

[0135] Grading method (based on leaves):

[0136] Level 0: no lesions;

[0137] Level 1: The lesion area accounts for less than 5% of the entire leaf area;

[0138] Level 3: The lesion area accounts for 6% to 10% of the entire leaf area;

[0139] Level 5: The lesion area accounts for 11% to 20% of the entire leaf area;

[0140] Level 7: The lesion area accounts for 21% to 40% of the entire leaf area;

[0141] Level 9: The lesion area accounts for more than 40% of the total leaf area.

[0142] The efficacy calculation method and formula used are as follows: calculate the disease index and control effect of each plot, calculate the average control effect of each treatment, and use SPSS17.0 software Duncan's new multiple range method to analyze the significance of differences among treatments.

[0143]

[0144] One day, two days, and three days after each application, it was observed that the pesticide did not cause any damage to the cucumber plants and fruits. The test results are shown in Table 7.

[0145] Table 9

[0146]

[0147] Shenyang field trial:

[0148] Refer to "Quality Management Specifications for Field Efficacy Tests for Pesticide Registration"; GB / T 17980.30-2000 "Guidelines for Field Efficacy Tests of Pesticides (I)": Fungicides for Controlling Cucumber Powdery Mildew. Comply with the SOP of the Institute of Biology and Medicine of Shenyang Research Institute of Chemical Industry Co., Ltd.: SOP-G-010 "Field Efficacy Tests of Fungicides for Controlling Cucumber Powdery Mildew". Test agents:

[0149]

[0150] Test method: Spray, spraying liquid volume 60 liters / mu.

[0151] The test results are shown in Table 8:

[0152] Table 10

[0153]

[0154]

[0155] Sichuan field trial:

[0156] Comply with the "Quality Management Standards for Pesticide Registration Tests", the "Guidelines for Pesticide Field Efficacy Tests" GB / T17980.30-2000, and SOP-TM-F-017a "Powdery Mildew Test on Cucurbitaceae Vegetables".

[0157] Test reagents:

[0158]

[0159] Application method and water consumption: Spray. The water consumption per hectare is about 600 liters for the first application and about 675 liters for the second and third applications.

[0160] The test results are shown in Table 9:

[0161] Table 11

[0162]

[0163] Conclusion: 6% fluopyram·cyfluthrin microemulsion has a good control effect on cucumber powdery mildew. During the trial, the cucumbers grew normally and no phytotoxicity symptoms were observed.

[0164] 13. Low temperature stability of emulsifiable concentrates / soluble concentrates: According to the low temperature stability requirements of GB / T 19137-2003, pesticide formulations need to be stored at 0°C for 7 days without crystallization or separation. In order to enhance the antifreeze effect of the product and adapt it to the storage conditions in northern winter, we increased the intensity of destructive experiments during development. According to the verification conditions after the formulation was stored at -10°C for 14 days, by adjusting the solvent and co-solvent and their ratio, it can be achieved that after storage at -10°C for 14 days, it is stable without crystal precipitation. Example 2 was stable without crystal precipitation after storage at -10°C for 14 days. After storage at -10°C for 14 days, crystals precipitated in Comparative Example 4. After storage at -10°C for 14 days, stratification occurred in Comparative Example 5. Results are shown in the table below. Fig.11 After storage at -10°C for 14 days, Example 3 was stable without crystal precipitation. After storage at -10°C for 14 days, crystal precipitation occurred in Comparative Example 10. Test results are shown in Fig.17 .

[0165] 14. Thermal storage stability of emulsifiable concentrates / soluble concentrates: To ensure that the microemulsion can maintain a transparent appearance in any season and any region, and to prevent it from becoming turbid at high temperatures and stratifying due to long-term storage, according to the thermal storage stability requirements of GB / T19136-2021 for pesticides, the sample will become turbid or even stratified after thermal storage at 54°C for 14 days. By adjusting the proportion of adjuvant types, Example 2 remained clear and stable after the thermal storage experiment. Comparative Example 6 was turbid after thermal storage. Results are shown in Fig.12 Example 3 remained clear and stable after the heat storage test. Comparative Example 11 was stratified after heat storage. Test results are shown in Fig.18 .

[0166] 15. Emulsification and dispersibility: Dispersibility refers to the automatic emulsification and dispersion of emulsifiable concentrate in water. The emulsifiable concentrate is required to automatically form a cloudy dispersion when poured into water, slowly diffuse into the water, and evenly disperse in the water as fine oil droplets after slight stirring, forming a uniform, stable, blue fluorescent emulsion to meet the spraying requirements. Adjust the type and ratio of the emulsifier to meet the dispersion requirements. Put 99.5mL of water into a 100mL measuring cylinder, and transfer 0.5mL of emulsifiable concentrate to observe its dispersion state. Example 2 is dispersed in a cloudy state, Comparative Example 7 is dispersed in a floating state, Comparative Example 8 is dispersed in a small amount of floating oil, and Comparative Example 9 is floating in the form of oil droplets. See the results. Fig.13; After the emulsifiable concentrate was dropped into the measuring cylinder, the stopper was covered, and the measuring cylinder was turned over 15 times to observe the colostrum state. The emulsion of Example 2 had a strong opalescence, while the emulsion of Comparative Example 7 was in an emulsified state without opalescence, and the emulsified state of Comparative Example 8 had opalescence at the bottom, and Comparative Example 9 had visible particles. Fig.14 .

[0167] 16. According to the requirements for the stability of pesticide emulsions, the liquid preparation was diluted 200 times with standard hard water at 30°C and its emulsion stability was observed within 1 hour. Different adjuvants and different proportions resulted in different dilution states. The dilutions had emulsions, some had floccules, and some had crystals precipitated in the water. The most stable ratio after dilution was selected. Example 2 had blue fluorescence and was more transparent. Comparative Example 10 had no fluorescence and was turbid with floating oil. Comparative Example 11 had blue fluorescence and poor transparency. Comparative Example 12 had no fluorescence and was turbid with floating oil. See the results. Fig.15 Example 3 is clear and transparent, while Comparative Example 15 has floating oil. Fig.19 .

[0168] 17. Spreadability: To test the spreadability of emulsion, dilute the emulsion 200 times and test its dynamic surface tension. Fig.16 The curves in the figure are from top to bottom: Comparative Example 10, Comparative Example 12, Comparative Example 11, and Example 2. To test the spreading performance of the soluble agent, the soluble agent was diluted 200 times and its dynamic surface tension was tested. The results are shown in Fig. 20 The contact angle of Example 3 is smaller, the rolling time is longer, and the leaf surface adhesion is better (corresponding to No. 1). The surface tension result of Comparative Example 16 is inferior to that of Example 3 (corresponding to No. 2). Fig. 20 .

Claims

1. A cyfluanid / fluopyram composition, characterized in that: The preparation raw materials at least include the original drug, the original drug includes cyfluanid and fluopyram, and the weight ratio of cyfluanid to fluopyram is 1:(1-5).

2. The cyfluthrin-fluopyram composition according to claim 1, characterized in that: The dosage form prepared from the composition is selected from one or a combination of powders, emulsifiable concentrates, microemulsions, suspensions, water-dispersible granules, and soluble solutions.

3. The cyfluthrin-fluopyram composition according to claim 2, characterized in that: The raw materials for preparing the microemulsion include, by weight percentage, 5-10% of the original drug, 25-35% of the emulsifier, 50-60% of the solvent, 5-10% of the cosolvent, 0.01-0.05% of the defoamer, and deionized water supplemented to 100%; the raw materials for preparing the emulsifiable concentrate include, by weight percentage, 5-10% of the original drug, 5-15% of the emulsifier, 5-15% of the cosolvent, and the organic solvent supplemented to 100%; the raw materials for preparing the soluble solution include, by weight percentage, 5-10% of the original drug, 10-20% of the emulsifier, 5-15% of the cosolvent, and the organic solvent supplemented to 100%.

4. The cyfluthrin-fluopyram composition according to claim 3, characterized in that: The emulsifier in the microemulsion includes a combination of a nonionic emulsifier and an anionic emulsifier, and the weight ratio of the nonionic emulsifier to the anionic emulsifier is (20-28):(1-5); preferably, the nonionic emulsifier includes a polyoxyethylene ether emulsifier and a block emulsifier, and the weight ratio of the polyoxyethylene ether emulsifier to the block emulsifier is (3-6):

1.

5. The cyfluthrin-fluopyram composition according to claim 4, characterized in that: The cloud point of the polyoxyethylene ether emulsifier is 60-65° C., and the pH value of a 1 wt % aqueous solution is 5-7.

6. The cyfluthrin-fluopyram composition according to claim 4, characterized in that: The block emulsifier is a hydroxy polyethylene oxide block copolymer, the molar ratio of EO:PO is 1:(1.7-2), and the pH value of the hydroxy polyethylene oxide block copolymer is 6.5-7.

5.

7. The cyfluthrin-fluopyram composition according to claim 3, characterized in that: The solvent in the microemulsion is selected from one or a combination of naphtha, amide solvents, cyclohexanone, alkanes, and ether solvents.

8. The cyfluthrin-fluopyram composition according to claim 3, characterized in that: The weight ratio of the solvent to the co-solvent in the microemulsion is (50-55):(8-12).

9. A method for preparing a microemulsion from the cyflufenamid / fluopyram composition according to any one of claims 3 to 8, characterized in that: The following steps are involved: S1: Add the solvent and co-solvent into the preparation kettle, turn on the agitator, add the original drug, stir, dissolve, and mix for 30-60 minutes; S2: accurately weigh the emulsifier and defoamer according to the feeding ratio and add them into the preparation kettle in sequence, turn on the stirrer and mix for 30-60 minutes; S3: Add deionized water into the preparation kettle and mix for 30-60 minutes.

10. A use of the cyfluthrin-fluopyram composition according to any one of claims 1 to 8, characterized in that: It is used to prevent and control leaf spot, leaf spot, gray mold, powdery mildew, sclerotinia and early blight on fruit trees, vegetables and field crops; it is used to prevent and control nematodes.

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