Ethiprole and flonicamid composition and preparation method and water dispersible granule thereof

Abstract

The invention provides an ethiprole and flonicamid composition and a dispersible granule containing the ethiprole and flonicamid composition. In the composition provided by the invention, the effective active components ethiprole and flonicamid belong to two insecticides with different action mechanisms, and when the ethiprole and flonicamid are mutually mixed, antagonism cannot be generated, a good synergistic interaction effect is achieved, and the control effect is higher than that of a single agent; the insecticidal efficiency is high, the dosage is small, the drug resistance is delayed, the lasting period of the drug is prolonged, and sustainable development of the environment is facilitated. The composition provided by the invention can be used for preventing and treating pests with chewing mouthparts and / or piercing-sucking mouthparts. Particularly, thrips, phylloxera, greenhouse whiteflies, brown planthoppers, miridae, snout beetles, citrus leaf miners, aphids, leafhoppers, locusts and the like can be effectively prevented and treated. The insecticidal spectrum is wide. The water dispersible granule has a good application prospect in preventing and treating water plant bugs, aphids and whiteflies.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and in particular to an ethiprole and flonicamid composition, a preparation method thereof, and a water-dispersible granule thereof. Background Art

[0002] Ethiprole, chemical name: 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-ethylsulfinyl-5-aminopyrazole. Molecular formula: C 13 H9C 12 F3N4OS. Ethiopromide is an insecticide and acaricide discovered by Rhone-Poulenc and developed by Bayer. It belongs to the second generation of insecticides that act on GABA. It is effective against a variety of chewing and sucking pests at low dosages. Its insecticidal mechanism is to hinder the chloride metabolism controlled by insect γ-aminobutyric acid (GABA), interfere with chloride ion channels, thereby disrupting the normal activity of the central nervous system (CNS) and killing insects. It can be used for seed treatment and foliar spraying, with a lasting effect of up to 21-28 days. It is mainly used to control thrips, stink bugs, weevils, beet aphids, planthoppers and locusts, and also shows activity against some whiteflies, especially against the extremely difficult to control rice pest green stink bug.

[0003] Flunicamid (Flonicamid, Flunicotamid), chemical name: N-cyanomethyl-(trifluoromethyl) nicotinamide. Flunicamid is a low-toxic insecticide variety and a pyridine amide insecticide. It has a new mechanism of action on the target, has no effect on acetylcholinesterase and nicotinyl acetylcholine receptors, has good neural effects and rapid antifeedant activity on aphids, has strong systemicity and good conduction activity, small dosage, high activity, long lasting effect, no cross-resistance with organophosphate, carbamate and pyrethroid pesticides, and has good ecological compatibility. It is mainly used to control piercing-sucking mouthparts pests such as aphids, leafhoppers, whiteflies, etc. At the recommended dose, it is effective against both larvae and adults of aphids, and can also control greenhouse whiteflies, tea yellow thrips, tea green leafhoppers and brown planthoppers. It has no activity against coleoptera, diptera and lepidoptera insects and mites. It is safe for most beneficial arthropods, such as silkworms, bees, Harmonia axyridis and Amblyseius punctatus. It is safe for crops, humans, animals and the environment when used at the recommended dose.

[0004] Under the current long-term use of pesticides, the resistance of Hemiptera pests such as rice planthoppers and aphids is gradually increasing, the effectiveness of single-dose pesticides in controlling pests is gradually decreasing, and there is no effective preparation for the control of Hemiptera pests. Summary of the invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an ethiprole and flonicamid composition, a preparation method thereof and a water-dispersible granule, wherein the prepared ethiprole and flonicamid composition has a synergistic effect.

[0006] To achieve the above-mentioned purpose, the present invention provides an ethiprole and flonicamid composition, wherein the active ingredients include ethiprole and flonicamid.

[0007] The invention expands the control spectrum of ethidium bromide and flonicamid by compounding them, and has an obvious synergistic effect on controlling hemiptera pests.

[0008] Preferably, the mass ratio of ethiprole to flonicamid is 20:40 to 60:10, more preferably 30:20 to 50:30.

[0009] The present invention has no particular limitation on the dosage form of the ethiprole and flonicamid composition, and may be any suitable dosage form familiar to those skilled in the art, including but not limited to water dispersible granules, wettable powders, suspensions, dispersible oil suspensions, and the like.

[0010] Water-dispersible granules can be dissolved or evenly dispersed in water. Since they do not use organic solvents, they avoid unfavorable factors such as flammability, explosion and environmental damage; and have the following advantages: high content of active ingredients, high relative density and small volume; good fluidity, easy packaging and measurement, easy handling of packaging materials, and low toxicity of highly toxic pesticides; good physical and chemical stability, good dispersibility in water, high suspension rate; no dust flying, safe for operators, and reduced pollution to the environment.

[0011] Based on this, the present invention provides a water-dispersible granule formulation of ethiprole and flonicamid. However, due to the difference in the performance of ethiprole and flonicamid, the two are prone to problems of difficulty in suspension, easy agglomeration and sedimentation, and difficulty in disintegration of particles after compounding. The present invention overcomes the above problems by screening the auxiliary agent.

[0012] Based on this, the present invention provides a water dispersible granule of ethiprole and flonicamid, which comprises, by mass content:

[0013] Ethiopromide 1% to 80%, flonicamid 1% to 80%, dispersant 4% to 15%, wetting agent 2% to 10%, disintegrant 5% to 40%, and the balance is filler.

[0014] The above-mentioned water-dispersible granules overcome the shortcomings of being difficult to suspend and easy to settle by combining a dispersant and a filler; the shortcomings of being difficult to disintegrate of the particles are overcome by combining a wetting agent and a disintegrant; and the shortcomings of easy agglomeration of suspended particles are overcome by selecting different types of dispersants for combination and screening out the best dispersant combination, thereby improving the insecticidal effect.

[0015] The mass content of ethiprole is preferably 20% to 60%, more preferably 30% to 50%.

[0016] The mass content of flonicamid is preferably 10% to 40%, more preferably 20% to 30%.

[0017] The mass content of the dispersant is preferably 6% to 15%, more preferably 8% to 15%, specifically 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.

[0018] Specifically, the dispersant is preferably one or more of calcium lignin sulfonate, sodium lignin sulfonate, maleic acid-acrylic acid copolymer salt, polyoxyethylene-polyoxypropylene block copolymer, sodium alkylphenol sulfonate, alkylnaphthalenesulfonic acid formaldehyde condensate sodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, ethylene oxide-propylene oxide block copolymer and polycarboxylic acid sodium salt, more preferably two or more thereof, and further preferably three or more thereof.

[0019] Further preferably, the dispersant is selected from a mixed dispersant of sodium polycarboxylate, sodium lignin sulfonate and calcium lignin sulfonate.

[0020] The mass ratio of the sodium polycarboxylate salt, sodium lignin sulfonate and calcium lignin sulfonate is preferably 1-5:2-8:1-4, more preferably 1:2-4:1.

[0021] The mass content of the sodium polycarboxylate in the water dispersible granules is preferably 1% to 5%. In some specific embodiments of the present invention, the mass content of the sodium polycarboxylate in the water dispersible granules is 1%, 2%, 3%, 4% or 5%.

[0022] The mass content of the sodium lignin sulfonate in the water dispersible granules is preferably 2% to 8%. In some specific embodiments of the present invention, the mass content of the sodium lignin sulfonate in the water dispersible granules is 2%, 4%, 6% or 8%.

[0023] The mass content of the calcium lignin sulfonate in the water dispersible granules is preferably 1% to 4%. In some specific embodiments of the present invention, the mass content of the calcium lignin sulfonate in the water dispersible granules is 1%, 2%, 3% or 4%.

[0024] In some specific embodiments of the present invention, the dispersant is selected from:

[0025] Polycarboxylate sodium salt 2%, sodium lignin sulfonate 4%, calcium lignin sulfonate 2%;

[0026] Or selected from sodium polycarboxylate 1%, sodium lignin sulfonate 4%, calcium lignin sulfonate 1%;

[0027] Or selected from sodium polycarboxylate 4%, sodium lignin sulfonate 8%, calcium lignin sulfonate 3%;

[0028] Or selected from sodium polycarboxylate 1%, sodium lignin sulfonate 2%, calcium lignin sulfonate 4%;

[0029] Or selected from sodium polycarboxylate 3%, sodium lignin sulfonate 6%, calcium lignin sulfonate 2%;

[0030] Or selected from sodium polycarboxylate 2%, sodium lignin sulfonate 8%, calcium lignin sulfonate 2%;

[0031] Or selected from sodium polycarboxylate 5%, sodium lignin sulfonate 2%, calcium lignin sulfonate 2%.

[0032] The selection of the above dispersant improves the suspension rate of ethiprole in the dispersible granules.

[0033] The wetting agent is preferably one or more of sodium dodecyl sulfate, α-sulfo fatty acid methyl ester, sodium tetradecyl sulfate, sodium dodecylbenzene sulfonate, sodium alkylnaphthalene sulfonate, sodium α-olefin sulfonate, sodium alkylphenol polyoxyethylene ether sulfate, sodium lignin sulfonate, pull-opening powder BX, fatty acid sulfate and fatty acid ester sulfate, and sodium sulfonated dioctyl succinate. Sodium dodecyl sulfate is further preferred.

[0034] The mass content of the wetting agent is preferably 2% to 8%, more preferably 2% to 6%, specifically 2%, 3%, 4%, 5%, 6%, 7% or 8%.

[0035] The disintegrant is preferably one or more of potassium sulfate, sodium hydroxymethylcellulose, potassium chloride, diammonium phosphate, urea, sodium sulfate, ammonium sulfate, ammonium nitrate, sodium carbonate, magnesium chloride, magnesium sulfate, calcium chloride and sodium chloride; more preferably ammonium sulfate.

[0036] The mass content of the disintegrant is preferably 10% to 30%, more preferably 15% to 25%, specifically 10%, 15%, 20%, 25%, or 30%.

[0037] The filler is preferably one or more of calcined kaolin, kaolin, bentonite, talc, attapulgite, diatomaceous earth, white carbon black, starch, and light calcium carbonate, and more preferably two or more thereof.

[0038] Further preferably, the filler is selected from white carbon black and calcined kaolin.

[0039] The mass content of the white carbon black in the water-dispersible granules is preferably 1% to 4%, specifically 1%, 2%, 3% or 4%.

[0040] The calcined kaolin makes up 100% of the total amount of the water dispersible granule components.

[0041] The invention improves the fluidity of the material and the hardness of the particles by adding white carbon black into the filler, thereby improving the manufacturability of the product.

[0042] The present invention determines the system with the best matching degree between the components through a large amount of screening work on the auxiliary agents of each component. Among them, the selection of dispersants and wetting agents is particularly critical: the preferred dispersant can ensure the dispersion effect; the preferred wetting agent can ensure the disintegration and dispersion effect of the active ingredients. The water-dispersible granules prepared by the above preferred auxiliary agents have higher thermal stability, and the disintegration performance, suspension rate and dispersion performance are all improved. And the amount of auxiliary agents used and the cost of the product are greatly reduced.

[0043] The present invention provides a method for preparing the above-mentioned ethiprole and flonicamid water dispersible granules, comprising the following steps:

[0044] S1) mixing ethiprole, flonicamid, a dispersant, a wetting agent, a disintegrant and a filler uniformly, crushing to a particle size D98 of 15 to 25 μm, and then mixing uniformly to obtain a dry material;

[0045] S2) adding water to the above dry materials for extrusion granulation, and drying to obtain ethiprole and flonicamid water dispersible granules.

[0046] Preferably, the powder is crushed and then tested with a laser particle size distribution analyzer until the particle size D98 is between 15 and 25 μm.

[0047] The drying temperature is preferably 45 to 55°C.

[0048] The amount of water added is preferably 13 wt% to 18 wt% of the dry material.

[0049] The preparation method provided by the present invention is simple and easy to operate, the preparation process is environmentally friendly and safe, no pollution problems occur, the cost is low, and it is easy to industrialize production.

[0050] Compared with the prior art, the present invention provides a composition of ethiprole and flonicamid and dispersible granules. In the composition provided by the present invention, the effective active ingredients ethiprole and flonicamid are two insecticides with different action mechanisms, and the two are mixed with each other without antagonism, and have a good synergistic effect, and the prevention effect is higher than that of a single agent; the insecticidal efficiency is high, the dosage is small, the drug resistance is delayed, the drug lasting period is extended, and it is conducive to environmental sustainable development.

[0051] The composition provided by the present invention can be used to control pests with chewing mouthparts and / or piercing-sucking mouthparts. In particular, it can effectively control thrips, psyllids, greenhouse whiteflies, brown planthoppers, blind bugs, weevils, citrus leafminers, aphids, leafhoppers and locusts. The insecticide spectrum is wide. The water-dispersible granules show good application prospects in controlling water blind bugs, aphids and whiteflies. DETAILED DESCRIPTION

[0052] To further illustrate the present invention, the ethiprole and flonicamid composition provided by the present invention, its preparation method and water dispersible granules are described in detail below with reference to the examples.

[0053] Unless otherwise specified, the percentages in the following embodiments are all by weight.

[0054] Examples 1-10

[0055] First, ethiprole, flonicamid, dispersant, wetting agent, disintegrant and filler are mixed evenly in a mixer, crushed to a particle size D98 between 15-25 μm by a jet mill, and then mixed evenly to obtain a dry material; the dry material is extruded and granulated with water, the amount of water added is 12wt%-20wt% of the dry material, and then dried at 40-55° C. to obtain water-dispersible granules containing ethiprole and flonicamid. The crushing pressure of the jet mill is 0.7 Mpa.

[0056] The raw material proportions of each embodiment are shown in Table 1.

[0057] Comparative Examples 1-5

[0058] The preparation method is the same as in Examples 1 to 10, and the raw material ratio is shown in Table 1.

[0059] Table 1 Ratios of raw materials in Examples 1-10 and Comparative Examples 1-5

[0060]

[0061]

[0062] The properties of the water dispersible granules prepared in the above examples and comparative examples were tested, and the results are shown in Table 2.

[0063] Among them, the suspension rate is tested according to the pesticide suspension rate determination method GB / T14825-2006, the wet screening is carried out according to the fineness determination method of the wet screening method (applicable to wettable powders) in Section 2.2 of GB / T16150-1995 Pesticide Powders, and the hot storage stability is tested according to the pesticide hot storage stability determination method GB / T19136-2003.

[0064] Table 2 Performance test results of water dispersible granules prepared in Examples 1 to 10 and Comparative Examples 1 to 5

[0065]

[0066]

[0067] As can be seen from Table 2, Examples 1-9 have obtained better stability by screening the adjuvants. Among them, the products of Example 1, Example 3, and Examples 6 to 8 have relatively stable quality before and after heat storage, maintaining a high suspension rate and good wet screening, indicating that the adjuvant formulations of Example 1, Example 3, and Examples 6 to 8 are excellent, while the heat storage stability of the products of Examples 2, 4, 5, and 9 is slightly worse than that of Example 1, Example 3, and Examples 6 to 8, but the performance is also relatively excellent. Due to improper selection of dispersants, wetting agents, and disintegrants, Example 10 has poor dispersion stability of the preparation, low suspension rate, and greatly reduced stability after heat storage. Screening has more fine powder and large particles. Due to appropriate selection of adjuvants, Examples 1, 3, and 6 to 8 have a higher suspension rate and better heat storage stability. It shows that the type and ratio of adjuvants play a key role in product quality.

[0068] Field efficacy experiment 1:

[0069] The efficacy test of ethiprole and flonicamid water dispersible granules prepared in the above example for controlling soybean green stink bug was carried out. The experiment was arranged to be carried out in Brazil, and the control agent was a suspension concentrate of (imidacloprid 250 g / L + bioresmethrin 50 g / L).

[0070] Experimental location and dates: The experiment was carried out under field conditions at the Palmital Farm-Plantec Laboratorios Experimental Station, in the municipality of Santa Mariana, between March 16 and May 3, 2022. Geographical coordinates: 23°08'37.72"S; 50°29'30.59"W, 360 m above sea level.

[0071] Experimental variety: soybean variety TMG7063IPRO, planted on January 11, 2022, with a row spacing of 0.45 meters and a plant spacing of 0.08 meters.

[0072] Test method: Use a carbon dioxide backpack sprayer to spray the stems and leaves. The test plots are randomly arranged. The test has 5 treatments, including the drug control, blank control, and drug treatment, and each treatment is repeated 4 times.

[0073] The spray volume of WG (37.5% ethiprole + 22.5% flonicamid) was 150 liters / ha, and the spray volume of suspension (250 g / L imidacloprid + 50 g / L bioresmethrin) was 200 liters / ha, and the solution was prepared by adding water. The data were investigated 3 and 7 days after the first application of the drug, and the data were investigated 3, 10, 15 and 20 days after the second application of the drug, and the control effect was calculated.

[0074] The calculation method of protection effect is:

[0075]

[0076] The control area described above is a blank control area and no pesticide is sprayed.

[0077] During the test period, the compound preparation of the present invention had no adverse effects on soybean within the test medication range. The experimental results are shown in Table 3 below:

[0078] Table 3 Efficacy test of (ethyprole 37.5% + flonicamid 22.5%) WG against soybean green stink bug

[0079]

[0080]

[0081] As can be seen from Table 3, (ethiprole 37.5% + flonicamid 22.5%) WG can effectively control soybean green stink bug, with an active ingredient dosage of 200-400 g / ha, and the control effect is better than the control agent.

[0082] Field efficacy experiment 2

[0083] The efficacy of the ethiprole and flonicamid water dispersible granules prepared in the above example for controlling soybean stink bugs was tested. The experiment was arranged to be carried out in Brazil, and the control agent was ethiprole 200 g / L suspension.

[0084] Experimental location and dates: The experiment was carried out under field conditions at the GOPalmital Farm-Plantec Laboratorios Experimental Station in the municipality of Anapolis between February 18 and March 25, 2022. Geographical coordinates: 16°17'17.75"S; 48°47'23.54"W, 981 m above sea level.

[0085] Experimental variety: soybean variety TMG7067 IPRO, planted on December 1, 2021, with a row spacing of 0.45 meters and a plant spacing of 0.06 meters.

[0086] Test method: Use a Sider sprayer with compressed air to spray the stems and leaves. The test plots are randomly arranged. The test has 5 treatments, including the drug control, blank control, and drug treatment, and each treatment is repeated 4 times.

[0087] The spray volume of (ethycloprid 37.5% + flonicamid 22.5%) WG is 150L / ha, and the spray volume of (imidacloprid 250g / L + bioresmethrin 50g / L) suspension is 150L / ha, and the solution is prepared by adding water. The data are investigated 3 and 7 days after the first application of the drug, and the data are investigated before and 3, 7, 10 and 21 days after the second application of the drug, and the control effect is calculated.

[0088] The calculation method of protection effect is:

[0089]

[0090] The control area described above is a blank control area and no pesticide is sprayed.

[0091] During the test, the compound preparation of the present invention had no adverse effects on soybeans within the test medication range. The experimental results are as follows:

[0092] Table 4 Efficacy test of (ethyprole 37.5% + flonicamid 22.5%) WG against soybean stink bug

[0093]

[0094] As can be seen from Table 4, (ethiprole 37.5% + flonicamid 22.5%) WG can effectively control soybean stink bugs, with an active ingredient dosage of 200-400 g / ha, and the control effect is better than that of the control agent.

[0095] The above examples show that the combination of ethidium bromide and flonicamid can produce a high synergistic effect, kill insects quickly, overcome and delay pest resistance, expand the control spectrum, and reduce the cost of medication. Its effect is significantly higher than that of a single dose.

[0096] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A composition of ethiprole and flonicamid, characterized in that: The active ingredients include ethiprole and flonicamid.

2. The ethiprole and flonicamid composition according to claim 1, characterized in that The mass ratio of ethidium bromide to flonicamid is 20:40 to 60:

10.

3. A water dispersible granule of ethiprole and flonicamid, comprising, by mass content: Ethiopromide 1% to 80%, flonicamid 1% to 80%, dispersant 4% to 15%, wetting agent 2% to 10%, disintegrant 5% to 40%, and the balance is filler.

4. The ethiprole and flonicamid water dispersible granules according to claim 3, characterized in that: The dispersant is selected from one or more of calcium lignin sulfonate, sodium lignin sulfonate, maleic acid-acrylic acid copolymer salt, polyoxyethylene-polyoxypropylene block copolymer, sodium alkylphenol sulfonate, alkylnaphthalenesulfonic acid formaldehyde condensate sodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, ethylene oxide-propylene oxide block copolymer and polycarboxylic acid sodium salt.

5. The ethiprole and flonicamid water dispersible granules according to claim 4, characterized in that: The dispersant is selected from sodium polycarboxylate, sodium lignin sulfonate and calcium lignin sulfonate.

6. The ethiprole and flonicamid water dispersible granules according to claim 3, characterized in that: The wetting agent is selected from one or more of sodium dodecyl sulfate, α-sulfo fatty acid methyl ester, sodium tetradecyl sulfate, sodium dodecylbenzene sulfonate, sodium alkyl naphthalene sulfonate, sodium α-olefin sulfonate, sodium alkylphenol polyoxyethylene ether sulfate, sodium lignin sulfonate, pull-opening powder BX, fatty acid sulfate and fatty acid ester sulfate, and sodium sulfonated dioctyl succinate.

7. The ethiprole and flonicamid water dispersible granules according to claim 6, characterized in that: The wetting agent is selected from sodium lauryl sulfate.

8. The ethiprole and flonicamid water dispersible granules according to claim 3, characterized in that: The disintegrant is selected from one or more of potassium sulfate, sodium hydroxymethylcellulose, potassium chloride, diammonium phosphate, urea, sodium sulfate, ammonium sulfate, ammonium nitrate, sodium carbonate, magnesium chloride, magnesium sulfate, calcium chloride and sodium chloride; The filler is selected from one or more of calcined kaolin, kaolin, bentonite, talc, attapulgite, diatomaceous earth, white carbon black, starch, and light calcium carbonate.

9. The ethiprole and flonicamid water dispersible granules according to claim 8, characterized in that: The disintegrant is selected from ammonium sulfate; The filler is selected from white carbon black and calcined kaolin.

10. The method for preparing the ethiprole and flonicamid water dispersible granules according to any one of claims 1 to 9, comprising the following steps: S1) mixing ethiprole, flonicamid, a dispersant, a wetting agent, a disintegrant and a filler uniformly, crushing to a particle size D98 of 15 to 25 μm, and then mixing uniformly to obtain a dry material; S2) adding water to the above dry materials for extrusion granulation, and drying to obtain ethiprole and flonicamid water dispersible granules.

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