Sustained-release granule containing clothianidin and chlorantraniliprole as well as preparation method and application thereof

Abstract

The invention discloses sustained-release granules containing clothianidin and chlorantraniliprole as well as a preparation method and application of the sustained-release granules, and relates to the field of pesticides, the sustained-release granules comprise clothianidin mother liquor and chlorantraniliprole mother powder; wherein the granules are prepared by mixing chlorantraniliprole mother powder and clothianidin mother liquor according to the weight ratio of 1: (0.1-0.25), and the clothianidin mother liquor comprises the following components in parts by weight: 0.1-10 parts of clothianidin, 0.1-10 parts of an organic solvent, 0.1-10 parts of urea resin and the like; the chlorantraniliprole mother powder comprises the following components in parts by weight: 0.1-10 parts of chlorantraniliprole, 1-20 parts of humic acid fertilizer and the like. According to the clothianidin-chlorantraniliprole sustained-release granules prepared by combining specific types of urea-formaldehyde resin and the acid solution, the problems that clothianidin is easily dissolved in water in soil and runs away along with the water body, and the long-acting effect and the control effect are greatly reduced are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and particularly relates to a slow-release granule containing clothianidin and chlorantraniliprole, a preparation method thereof, and an application thereof. Background Art

[0002] Clothianidin, chemical name: (E)-1-(2-chloro-1,3-thiazol-5-ylmethyl)-3-methyl-2-nitroguanidine; chemical formula: C6H8ClN5O2S; clothianidin is an insecticide in the neonicotinoid class, a class of highly efficient, safe, and highly selective new insecticides. Its action is similar to that of the nicotinic acetylcholine receptor, with contact, stomach toxicity, and systemic activity. Solubility: 0.327 g / L in water, 15.2 g / L in acetone, 6.26 g / L in methanol, 2.03 g / L in ethyl acetate, 1.32 g / L in dichloromethane, 0.0128 g / L in xylene, <0.00104 g / L in n-heptane, 0.938 g / L in n-octanol (measurement temperature: 25°C for water, 20°C for organic solvents). Clothianidin is the second-generation neonicotinoid insecticide developed after imidacloprid. Compared with imidacloprid, it has better water solubility, higher insecticidal activity, and stronger systemicity. It has contact and stomach toxicity effects and can be used to control a variety of pests. It can be used for spraying, soil treatment, and seed dressing, but it is not a universal insecticide, and appropriate control methods and dosages need to be selected according to the pest species and damage situation. It shows good quick-acting properties, and the residual effect period is about 7 days. It is mainly used for rice, vegetables, fruit trees, and other crops to control pests of Hemiptera, Coleoptera, Diptera, and certain Lepidoptera.

[0003] Chlorantraniliprole belongs to the class of benzamide compounds, and its chemical name is 3-bromo-N-[4-chloro-2-methyl-6-[(methylcarbamoyl)phenyl]-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide, chemical formula:

[0004] C 18 H 14 N5O2BrCl2; Chlorantraniliprole belongs to the class of o-formylaminobenzamide insecticides. Chlorantraniliprole is highly efficient and broad-spectrum, and has good control effects on Noctuidae, Pyralidae, Carposinidae, Tortricidae, Plutellidae, Plutellidae, Gelechiidae, Gracillariidae, etc. of Lepidoptera, and can also control Curculionidae and Chrysomelidae of Coleoptera; Agromyzidae of Diptera; Bemisia tabaci and other non-Lepidoptera pests. It is low-toxic to mammals, birds, fish, and bees, and is safe for the environment, humans, and livestock, and is suitable for integrated pest control. Chlorantraniliprole also has some disadvantages: slow insecticidal speed: The mechanism of action of chlorantraniliprole results in a relatively slow insecticidal speed, and it takes 48 to 72 hours to see obvious dead insects, which may not be ideal for rapid control in emergency situations.

[0005] In the production of granule agents, the production method is to mix the active ingredient with a filler and carry out air pulverization, then add an appropriate amount of water and obtain the product through spray adsorption, fluidized bed drying, and screening; in terms of application, although granule agent products have the advantages of good sedimentation, small drift, light environmental pollution, convenient application, and labor and time saving, and can be used as a soil treatment agent for centralized area release, due to the leaching effect of rainwater or groundwater and / or the influence of soil pH, the active ingredient of pesticides is likely to be lost or degraded, and the effective period is relatively short. Therefore, it is necessary to increase the number of pesticide applications and the dosage, resulting in an increase in the cost of using pesticides and environmental pollution.

[0006] In the main sugarcane production areas of China, rainfall is frequent. During the planting process, the sugarcane borer, a subterranean pest in sugarcane fields, is the main pest. In actual use, clothianidin and chlorantraniliprole mixed formulation is usually selected as a soil treatment agent for control, and the effect is excellent. Although there are also granule agents of chlorantraniliprole and clothianidin in the prior art, there are still a series of problems, such as:

[0007] 1) The conventional method is to mix and pulverize chlorantraniliprole, clothianidin, wetting agent, binder, etc., add water and knead to granulate, such as patent applications CN 109006830 A, CN 111226920 A, CN 103621535 A, and CN 116730763 A, etc. However, the inventors have found through research that the traditional method often ignores the high water solubility of clothianidin, resulting in poor resistance to rain leaching, easy dispersion into the soil and water bodies, and short effective period.

[0008] 2) Some researchers have also prepared a suspension by grinding chlorantraniliprole, clothianidin and other materials through a sand mill, and then adopted the spray coating method to spray and coat on fertilizer particles, such as CN 116178070 A. However, for the granule agent prepared by the spray coating method, the suspension coating of chlorantraniliprole and clothianidin is extremely easy to fall off due to groundwater flow and internal fertilizer dissolution, also resulting in a short effective period.

[0009] 3) Some researchers have also prepared granule agents with a slow-release effect, such as CN 112273379 A, which is a granule agent prepared by adhering chlorantraniliprole and clothianidin together with vinyl acetate and adding other materials. However, it shows poor quick-acting property. At the same time, after being adhered by vinyl acetate, the release performance is further reduced, which will lead to a further decline in the quick-acting property after pesticide application. The inventors have found in applied research that factors such as microorganisms and pH in soil or sludge will also accelerate the degradation of vinyl acetate. Compared with the pure water phase, its slow-release and long-acting effects are not obvious. Multiple pesticide applications are required in actual application, which is time-consuming and laborious, greatly increasing the cost of pest control and also harming the natural environment.

[0010] In summary, there is an urgent need to provide a granule of chlorantraniliprole and clothianidin with controlled release that has good stability, quick-acting property, long-acting property and can be actually applied in the field, as well as a preparation method thereof, to change this situation. Summary of the Invention

[0011] Object of the Invention

[0012] To overcome the above deficiencies, the purpose of the present invention is to provide a sustained-release granule containing clothianidin and chlorantraniliprole, a preparation method and an application thereof. The clothianidin·chlorantraniliprole sustained-release granule prepared by combining a specific type of urea-formaldehyde resin and an acidic solution solves the problem that clothianidin is easily dissolved in water in the soil and lost with the water body, resulting in a significant reduction in long-acting property and control efficacy.

[0013] Solution

[0014] To achieve the purpose of the present invention, the technical solutions adopted by the present invention are as follows:

[0015] In the first aspect, the present invention provides a sustained-release granule containing clothianidin and chlorantraniliprole, which is a granule prepared by mixing chlorantraniliprole mother powder and clothianidin mother liquid according to a weight ratio of 1:(0.1-0.25), wherein:

[0016] The clothianidin mother liquid comprises the following raw materials in parts by weight: 0.1-10 parts by weight of clothianidin, 0.1-10 parts by weight of organic solvent, 0.1-10 parts by weight of urea-formaldehyde resin, 0.5-5 parts by weight of emulsifier, 2-15 parts by weight of water, 0.1-2 parts by weight of acidic solution;

[0017] The chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.1-10 parts by weight of chlorantraniliprole, 1-20 parts by weight of humic acid fertilizer, 0-10 parts by weight of dispersant, 0-10 parts by weight of wetting agent, 50-75 parts by weight of solid carrier, 0-10 parts by weight of warning color.

[0018] Further, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquid is 1:(0.11-0.25), and optionally 1:(0.13-0.18);

[0019] Further, the weight ratio of chlorantraniliprole to clothianidin is (0.1-4):(0.6-6), and optionally 1:

[0020] (1.2-3), and optionally 1:3;

[0021] Further, the sustained-release granule is prepared by mixing, kneading, drying and screening the clothianidin mother liquid and the chlorantraniliprole mother powder in proportion.

[0022] Further, the clothianidin mother liquor comprises raw materials in the following parts by weight: 0.3-6 parts by weight of clothianidin, 0.5-6 parts by weight of organic solvent, 0.3-3 parts by weight of urea-formaldehyde resin, 0.6-3.2 parts by weight of emulsifier, 2.5-11 parts by weight of water, and 0.2-1.6 parts by weight of acidic solution; optionally, the acidic solution is used to adjust the pH of the mixed material of the clothianidin mother liquor to 4.9-6.7.

[0023] Further, the clothianidin mother liquor comprises raw materials in the following parts by weight: 1.2-2.5 parts by weight of clothianidin, 1.4-3.8 parts by weight of organic solvent, 0.42-0.75 parts by weight of urea-formaldehyde resin, 0.65-2 parts by weight of emulsifier, 3.5-9.5 parts by weight of water, and 0.2-1.6 parts by weight of acidic solution; optionally, the acidic solution is used to adjust the pH of the mixed material of the clothianidin mother liquor to 5.2-6.1.

[0024] Optionally, the clothianidin mother liquor comprises raw materials in the following parts by weight: 1.2-2.5 parts by weight of clothianidin, 1.4-2.0 parts by weight of organic solvent, 0.42-0.66 parts by weight of urea-formaldehyde resin, 1.55-2 parts by weight of emulsifier, 9-9.5 parts by weight of water, and 0.5-0.53 parts by weight of acidic solution; optionally, the acidic solution is used to adjust the pH of the mixed material of the clothianidin mother liquor to 5.5-5.9.

[0025] Optionally, the weight ratio of clothianidin to urea-formaldehyde resin is 1:(0.1-1), optionally 1:(0.35-0.55).

[0026] Optionally, the weight ratio of urea-formaldehyde resin to acidic solution is 1:(0.6-1.5), optionally 1:(0.8-1.2).

[0027] Optionally, the clothianidin mother liquor accounts for 10-20% of the total weight of the slow-release granule, optionally 12-18%, optionally 12-15%.

[0028] Further, in the clothianidin mother liquor, the emulsifier is selected from one or more of styrene-maleic anhydride copolymer, magnesium salt of alkyl biphenyl ether disulfonic acid, calcium alkyl benzene sulfonate, nonylphenol polyoxyethylene ether phosphate, ammonium salt of styrene polyoxyethylene ether sulfate, benzyl dimethylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol formaldehyde resin polyoxyethylene ether, ethylene oxide-propylene oxide block copolymer, castor oil polyoxyethylene ether, Span series sorbitan monostearate, and fatty alcohol polyoxyethylene ether; optionally, the weight ratio of the emulsifier to water is 1:(1.5-5.9), optionally 1:(1.75-5.9);

[0029] And / or, in the clothianidin mother liquor, the organic solvent is selected from one or more of palm oil, soybean oil, methyl oleate or vegetable oil; optionally, the weight ratio of clothianidin technical and the organic solvent is 1:(1 - 2), optionally 1:(1 - 1.7);

[0030] And / or, in the clothianidin mother liquor, the acidic solution is a weak acid solution, optionally the acidic solution is selected from one or several of citric acid solution, phosphoric acid solution, acetic acid solution.

[0031] Furthermore, the chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.1 - 4 parts by weight of chlorantraniliprole, 2 - 15 parts by weight of humic acid fertilizer, 0 - 10 parts by weight of dispersant, 0 - 10 parts by weight of wetting agent, 52 - 71 parts by weight of solid carrier, 0 - 10 parts by weight of warning color;

[0032] Furthermore, the chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.1 - 4 parts by weight of chlorantraniliprole, 5 - 15 parts by weight of humic acid fertilizer, 1 - 10 parts by weight of dispersant, 1 - 10 parts by weight of wetting agent, 52.5 - 70.6 parts by weight of solid carrier, 0 - 10 parts by weight of warning color;

[0033] Optionally, the chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.1 - 4 parts by weight of chlorantraniliprole, 5 - 15 parts by weight of humic acid fertilizer, 2.5 - 6 parts by weight of dispersant, 1 - 6 parts by weight of wetting agent, 52.5 - 70.6 parts by weight of solid carrier, 0 - 10 parts by weight of warning color;

[0034] Optionally, the chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.4 - 2 parts by weight of chlorantraniliprole, 7 - 12 parts by weight of humic acid fertilizer, 3 - 5 parts by weight of dispersant, 3 - 6 parts by weight of wetting agent, 61.6 - 68.1 parts by weight of solid carrier, 0 - 10 parts by weight of warning color;

[0035] Optionally, the weight of the warning color is 0.2 - 7 parts by weight, optionally 1 - 7 parts by weight, optionally 0.2 - 3.2 parts by weight, optionally 0.2 - 0.5 parts by weight;

[0036] Optionally, the chlorantraniliprole mother powder accounts for 80 - 90% of the total weight of the slow - release granule, optionally 82 - 88%, optionally 85 - 88%.

[0037] Furthermore, the humic acid fertilizer comprises one or more of humic acid, nitro - humic acid, water - soluble salts of humic acid and water - soluble salts of nitro - humic acid;

[0038] And / or, the dispersant is selected from one or more of carboxylate, naphthalene sulfonate formaldehyde condensate, calcium lignosulfonate, polycarboxylate, sodium lauryl polyoxyethylene ether sulfate, de-sugared sodium lignosulfonate, de-sugared condensed sodium lignosulfonate, sodium lignosulfonate, alkyl naphthalene formaldehyde condensate sulfonate;

[0039] And / or, the wetting agent is selected from one or more of calcium dodecylbenzenesulfonate, wetting penetrant T, EFW, Nekal, alkylphenol polyoxyethylene ether nonylphenol polyoxyethylene ether;

[0040] And / or, the solid carrier is selected from one or more of carboxymethyl cellulose, kaolin, montmorillonite, sepiolite, pyrophyllite, xylitol, montmorillonite, pottery clay, bentonite, white carbon black, diatomite, talcum powder and light calcium carbonate;

[0041] And / or, the warning color is selected from one or more of metal phthalocyanine, iron oxide, azo dye, triphenylmethane dye.

[0042] In a second aspect, there is provided a preparation method of the sustained-release granule agent including the sustained-release granule agent described in the first aspect, comprising the following steps:

[0043] S1. Mix the solid chlorantraniliprole technical in the chlorantraniliprole mother powder with each auxiliary agent in proportion, and carry out air-flow pulverization to obtain the chlorantraniliprole mother powder;

[0044] S2. Liquefy the solid clothianidin technical, and wrap it with urea formaldehyde resin to prepare a controlled-release clothianidin mother liquid;

[0045] S3. Add the prepared clothianidin mother liquid to the chlorantraniliprole mother powder, adsorb and knead, granulate, dry and screen to obtain the clothianidin·chlorantraniliprole sustained-release granule agent.

[0046] Further, in step S2, the preparation method of the clothianidin mother liquid includes:

[0047] (1) Dissolve the solid clothianidin technical in an organic solvent to liquefy it, and mix it with urea formaldehyde resin to form a first material;

[0048] (2) Mix water with an emulsifier to form a second material;

[0049] (3) Mix the first material with the second material and shear to form a third material;

[0050] (4) Mix the third material with an acidic solution, heat up and cure to wrap clothianidin therein to obtain a controlled-release clothianidin microcapsule mother liquid; optionally, when heating up and curing, the temperature is 50-65°C and the heat preservation time is 2-3 h.

[0051] In a third aspect, there is provided an application of the sustained-release granule agent described in the first aspect or the sustained-release granule agent prepared by the preparation method described in the second aspect in controlling underground pests. Optionally, the underground pest is sugarcane borer, and optionally the application method is broadcasting.

[0052] Advantageous Effects

[0053] (1) The present invention has conducted extensive research on the encapsulation performance of the controlled-release clothianidin mother liquor. The clothianidin·chlorantraniliprole sustained-release granule agent prepared by combining a specific type of urea-formaldehyde resin and an acidic solution solves the problem that clothianidin is easily dissolved in water in the soil and lost with the water body, resulting in a significant reduction in long-term effectiveness and control efficacy.

[0054] (2) The present invention has made extensive selections on the ratio of chlorantraniliprole mother powder and clothianidin mother liquor, and found that by using the ratio within the range provided by the present invention, the clothianidin microcapsule mother liquor can be used to replace water for kneading and granulation, minimizing the moisture content of the prepared product without increasing the complexity of the granulation process. Furthermore, the drying speed of the granule moisture is fast, reducing production energy consumption and suggesting production costs, creating greater benefits for enterprises. Detailed Embodiments

[0055] 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. Apparently, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0056] In addition, for better illustration of the present invention, numerous specific details are given in the following detailed embodiments. Those skilled in the art should understand that the present invention can be implemented without some specific details. In some embodiments, the raw materials, schemes, methods, means, etc. well-known to those skilled in the art are not described in detail to highlight the gist of the present invention.

[0057] Unless otherwise clearly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "having" etc. will be understood to include the stated elements or components, without excluding other elements or other components.

[0058] The above bactericidal composition provides a new option for controlling pests. The following examples are used to further illustrate the present disclosure, but the present disclosure is not limited thereby.

[0059] In the following examples, chlorantraniliprole mother powder and clothianidin can be obtained commercially, and other auxiliaries are also commercially available products.

[0060] The present invention will be further described in detail by way of examples below.

[0061] Example 1

[0062] A preparation method of a clothianidin·chlorantraniliprole sustained-release granule, the preparation method comprising the following steps:

[0063] S1. Prepare the chlorantraniliprole mother powder: Mix 0.4 g of chlorantraniliprole, 10 g of sodium humate, 3 g of sodium lignosulfonate, 3 g of Nekal, 68.1 g of light calcium carbonate, and 0.5 g of azo dye, and then perform air flow pulverization to form a chlorantraniliprole mother powder with an average particle size of 5 μm;

[0064] S2. Prepare the clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.44 g of methyl oleate, then add 0.42 g of urea-formaldehyde resin to form a first material;

[0065] Then mix 2 g of calcium alkylbenzene sulfonate with 9.44 g of water to form a second material, and then mix and shear the second material with the first material to form a third material;

[0066] Finally, mix 0.5 g of citric acid solution with the third material evenly, adjust the pH to 5.5, heat up to 56 °C and keep warm for 2.7 h. By heating and curing, the clothianidin is wrapped therein to obtain a controllable-release clothianidin microcapsule mother liquor;

[0067] S3. Drop 15 g of the clothianidin mother liquor obtained in step S2 into 85 g of the chlorantraniliprole mother powder obtained in step S1, perform adsorption kneading, granulation, drying, and screening to obtain the clothianidin·chlorantraniliprole sustained-release granule.

[0068] In the clothianidin·chlorantraniliprole sustained-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.176; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.35, and the weight ratio of urea-formaldehyde resin to acidic solution is 1:1.2.

[0069] Example 2

[0070] A preparation method of a clothianidin·chlorantraniliprole sustained-release granule, the preparation method comprising the following steps:

[0071] S1. Prepare the chlorantraniliprole mother powder: Mix 0.4 g of chlorantraniliprole, 10 g of nitrohumic acid, 3.5 g of sodium lignosulfonate, 3 g of Nekal, 67.9 g of light calcium carbonate, and 0.2 g of azo dye, and then perform air flow pulverization to form a chlorantraniliprole mother powder with an average particle size of 5 μm;

[0072] S2. Preparation of clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.92 g of methyl oleate, then add 0.66 g of urea-formaldehyde resin to form the first material;

[0073] Mix 1.55 g of calcium alkylbenzene sulfonate with 9.14 g of water to form the second material, and then mix and shear it with the first material to form the third material;

[0074] Finally, mix 0.53 g of citric acid solution evenly with the third material, adjust the pH to 5.9, raise the temperature to 62 °C and keep it warm for 2.2 h. Through heating and curing, wrap the clothianidin in it to obtain the controlled-release clothianidin mother liquor;

[0075] S3. Drop 15 g of the clothianidin mother liquor obtained in step S2 into 85 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry and screen to obtain the clothianidin·chlorantraniliprole slow-release granule.

[0076] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.176; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.55, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:0.8;

[0077] Example 3

[0078] A preparation method of clothianidin·chlorantraniliprole slow-release granule, the preparation method includes the following steps:

[0079] S1. Preparation of chlorantraniliprole mother powder: Mix 0.4 g of chlorantraniliprole, 12 g of nitrohumic acid, 5 g of sodium lignosulfonate, 5 g of Nekal, 61.6 g of light calcium carbonate, and 1 g of azo dye, and then carry out air flow pulverization to form chlorantraniliprole mother powder with an average particle size of 5 μm;

[0080] S2. Preparation of clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.68 g of methyl oleate, then add 0.48 g of urea-formaldehyde resin to form the first material;

[0081] Mix 1.86 g of calcium alkylbenzene sulfonate with 9.3 g of water to form the second material, and then mix and shear it with the first material to form the third material;

[0082] Finally, mix 0.48 g of citric acid solution evenly with the third material, adjust the pH to 5.95, raise the temperature to 58 °C and keep it warm for 2.5 h. Through heating and curing, wrap the clothianidin in it to obtain the controlled-release clothianidin mother liquor;

[0083] S3. Drop 15 g of the clothianidin mother liquor obtained in step S2 into 85 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry and screen to obtain the clothianidin·chlorantraniliprole slow-release granule.

[0084] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.176; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.4, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:1.

[0085] Example 4

[0086] A preparation method of clothianidin·chlorantraniliprole slow-release granule, the preparation method includes the following steps:

[0087] S1. Prepare chlorantraniliprole mother powder: Mix 2 g of chlorantraniliprole, 7 g of nitrohumic acid, 3.5 g of lignosulfonate, 6 g of calcium dodecylbenzenesulfonate, 66.3 g of light calcium carbonate, and 3.2 g of azo dye, and then carry out air-flow pulverization to form chlorantraniliprole mother powder with an average particle size of 5 μm;

[0088] S2. Prepare clothianidin mother liquor: Dissolve 2.5 g of clothianidin in 3.75 g of methyl oleate, and then add 0.75 g of urea-formaldehyde resin to form the first material;

[0089] Then mix 0.65 g of ethylene oxide-propylene oxide block copolymer with 3.52 g of water to form the second material, and then mix and shear the second material with the first material to form the third material;

[0090] Finally, mix 0.83 g of citric acid solution evenly with the third material, adjust the pH to 5.73, raise the temperature to 57 °C and keep it warm for 2.6 h. Through heating and curing, wrap clothianidin in it to obtain a controllable-release clothianidin mother liquor;

[0091] S3. Drop 12 g of the clothianidin mother liquor obtained in step S2 into 88 g of the chlorantraniliprole mother powder obtained in step S1, carry out adsorption kneading, granulation, drying and screening to obtain clothianidin·chlorantraniliprole slow-release granule.

[0092] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.136; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.3, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:1.1.

[0093] Example 5

[0094] A preparation method of clothianidin·chlorantraniliprole slow-release granule, the preparation method includes the following steps:

[0095] S1. Preparation of chlorantraniliprole mother powder: Mix 1.5 g of chlorantraniliprole, 12 g of nitrohumic acid sodium salt, 2.5 g of alkylnaphthalene formaldehyde condensate sulfonate, 4 g of wetting and penetrating agent T, 58 g of diatomaceous earth, and 4 g of azo dye, and then perform air flow pulverization to form chlorantraniliprole mother powder with an average particle size of 5 μm;

[0096] S2. Preparation of clothianidin mother liquid: Dissolve 4 g of clothianidin in 4.4 g of soybean oil, and then add 1.8 g of urea-formaldehyde resin to form the first material;

[0097] Then mix 1 g of castor oil polyoxyethylene ether with 5.54 g of water to form the second material, and then mix and shear the second material with the first material to form the third material;

[0098] Finally, mix 1.26 g of phosphoric acid solution evenly with the third material, adjust the pH to 5.86, heat up to 61 °C and keep warm for 2.5 h. Through heating and curing, wrap clothianidin in it to obtain a controlled-release clothianidin mother liquid;

[0099] S3. Drop 12 g of the clothianidin mother liquid obtained in step S2 into 88 g of the chlorantraniliprole mother powder obtained in step S1, perform adsorption kneading, granulation, drying, and screening to obtain clothianidin·chlorantraniliprole slow-release granules.

[0100] In the clothianidin·chlorantraniliprole slow-release granules prepared by the above method, the weight ratio of chlorantraniliprole mother powder to clothianidin mother liquid is 1:0.22; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.45, and the weight ratio of urea-formaldehyde resin to acidic solution is 1:0.7.

[0101] Example 6

[0102] A preparation method of clothianidin·chlorantraniliprole slow-release granules, the preparation method includes the following steps:

[0103] S1. Preparation of chlorantraniliprole mother powder: Mix 1 g of chlorantraniliprole, 13 g of nitrohumic acid potassium salt, 5 g of lignosulfonic acid sodium salt, 5 g of EFW, 55.5 g of silica white, and 1.5 g of azo dye, and then perform air flow pulverization to form chlorantraniliprole mother powder with an average particle size of 5 μm;

[0104] S2. Preparation of clothianidin mother liquid: Dissolve 2 g of clothianidin in 3 g of palm oil, and then add 0.4 g of urea-formaldehyde resin to form the first material;

[0105] Then mix 2.2 g of calcium alkylbenzene sulfonate with 11 g of water to form the second material, and then mix and shear the second material with the first material to form the third material;

[0106] Finally, mix 0.4 g of acetic acid solution with the third material evenly, adjust the pH to 5.2, heat up to 60 °C and keep warm for 2.7 h. Through heating and curing, clothianidin is wrapped in it to obtain a controlled-release clothianidin mother liquor;

[0107] S3. Drop 19 g of the clothianidin mother liquor obtained in step S2 into 81 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry and screen to obtain the clothianidin·chlorantraniliprole slow-release granule.

[0108] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.235; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.2, and the weight ratio of urea-formaldehyde resin to acidic solution is 1:1.

[0109] Example 7

[0110] A preparation method of clothianidin·chlorantraniliprole slow-release granule, the preparation method includes the following steps:

[0111] S1. Prepare chlorantraniliprole mother powder: Mix 0.5 g of chlorantraniliprole, 5 g of nitrohumic acid, 6 g of sodium lignosulfonate, 3 g of Nekal, 68.5 g of diatomite, and 6 g of azo dye, and then carry out air flow pulverization to form a chlorantraniliprole mother powder with an average particle size of 5 μm;

[0112] S2. Prepare clothianidin microcapsule mother liquor: Dissolve 1 g of clothianidin with 1.4 g of methyl oleate, and then add 0.4 g of urea-formaldehyde resin to form the first material;

[0113] Then mix 3.2 g of calcium alkylbenzene sulfonate with 4.8 g of water to form the second material, and then mix and shear it with the first material to form the third material;

[0114] Finally, mix 0.5 g of citric acid solution with the third material evenly, adjust the pH to 5.63, heat up to 63 °C and keep warm for 2.2 h. Through heating and curing, clothianidin is wrapped in it to obtain a controlled-release clothianidin microcapsule mother liquor;

[0115] S3. Drop 11 g of the clothianidin mother liquor obtained in step S2 into 89 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry and screen to obtain the clothianidin·chlorantraniliprole slow-release granule.

[0116] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.124; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.4, and the weight ratio of urea-formaldehyde resin to acidic solution is 1:0.5.

[0117] Example 8

[0118] A preparation method of clothianidin·chlorantraniliprole sustained-release granules, the preparation method comprising the following steps:

[0119] S1. Prepare the chlorantraniliprole mother powder: Mix 4 g of chlorantraniliprole, 15 g of nitrohumic acid, 3.5 g of sodium lignosulfonate, 3 g of Nekal, 52.5 g of diatomite, and 2 g of azo dye, and then carry out air-flow pulverization to form chlorantraniliprole mother powder with an average particle size of 5 μm;

[0120] S2. Prepare the clothianidin mother liquor: Dissolve 6 g of clothianidin in 6 g of methyl oleate, and then add 0.6 g of urea-formaldehyde resin to form the first material;

[0121] Then mix 1.1 g of calcium alkylbenzene sulfonate with 5.7 g of water to form the second material, and then mix and shear the second material with the first material to form the third material;

[0122] Finally, mix 0.6 g of citric acid solution evenly with the third material, adjust the pH to 6.1, heat up to 55 °C and keep warm for 2.7 h. Through heating and curing, wrap the clothianidin therein to obtain a controllable-release clothianidin microcapsule mother liquor with a weight percentage of 20%;

[0123] S3. Drop 20 g of the clothianidin mother liquor obtained in step S2 into 80 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry, and screen to obtain clothianidin·chlorantraniliprole sustained-release granules.

[0124] In the clothianidin·chlorantraniliprole sustained-release granules prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.25; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.1, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:1.

[0125] Example 9

[0126] A preparation method of clothianidin·chlorantraniliprole sustained-release granules, the preparation method comprising the following steps:

[0127] S1. Prepare the chlorantraniliprole mother powder: Mix 0.1 g of chlorantraniliprole, 10 g of nitrohumic acid, 6 g of sodium lignosulfonate, 7 g of alkylphenol polyoxyethylene nonylphenol polyoxyethylene ether, 62.9 g of kaolin, and 4 g of metal phthalocyanine, and then carry out air-flow pulverization to form chlorantraniliprole mother powder with an average particle size of 5 μm;

[0128] S2. Prepare the clothianidin mother liquor: Dissolve 0.3 g of clothianidin in 0.51 g of methyl oleate, and then add 0.3 g of urea-formaldehyde resin to form the first material;

[0129] Then mix 2 g of calcium alkylbenzene sulfonate with 6.62 g of water to form the second material, and then mix and shear the second material with the first material to form the third material;

[0130] Finally, 0.27 g of citric acid solution was mixed evenly with the third material, the pH was adjusted to 6.71, the temperature was raised to 52 °C and kept warm for 2.9 h. Through heating and curing, clothianidin was encapsulated therein to obtain a controlled-release clothianidin microcapsule mother liquor;

[0131] S3. 10 g of the clothianidin mother liquor obtained in step S2 was dropped into 90 g of the chlorantraniliprole mother powder obtained in step S1, adsorbed and kneaded, granulated, dried and sieved to obtain a clothianidin·chlorantraniliprole slow-release granule.

[0132] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.111; the weight ratio of clothianidin to urea-formaldehyde resin is 1:1, and the weight ratio of urea-formaldehyde resin to acidic solution is 1:0.9.

[0133] Example 10

[0134] A preparation method of a clothianidin·chlorantraniliprole slow-release granule, the preparation method comprising the following steps:

[0135] S1. Preparation of chlorantraniliprole mother powder: 3.5 g of chlorantraniliprole, 10 g of humic acid, 5 g of sodium lignosulfonate, 4 g of Nekal, 55 g of sepiolite, and 4 g of triphenylmethane dye were mixed and then subjected to air flow pulverization to form a chlorantraniliprole mother powder with an average particle size of 5 μm;

[0136] S2. Preparation of clothianidin mother liquor: 5 g of clothianidin was dissolved in 6 g of methyl oleate and then 2.6 g of urea-formaldehyde resin was added to form a first material;

[0137] Then 0.8 g of calcium alkylbenzene sulfonate was mixed with 2.54 g of water to form a second material, which was then mixed and sheared with the first material to form a third material;

[0138] Finally, 1.56 g of citric acid solution was mixed evenly with the third material, the pH was adjusted to 4.9, the temperature was raised to 60 °C and kept warm for 3 h. Through heating and curing, clothianidin was encapsulated therein to obtain a controlled-release clothianidin microcapsule mother liquor with a weight percentage of 18.5%;

[0139] S3. The clothianidin mother liquor obtained in step S2 was dropped into the chlorantraniliprole mother powder obtained in step S1, adsorbed and kneaded, granulated, dried and sieved to obtain a clothianidin·chlorantraniliprole slow-release granule.

[0140] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.227; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.52, and the weight ratio of urea-formaldehyde resin to acidic solution is 1:0.6.

[0141] Example 11

[0142] A preparation method of a clothianidin·chlorantraniliprole sustained-release granule, the preparation method comprising the following steps:

[0143] S1. Prepare the chlorantraniliprole mother powder: Mix 1.2 g of chlorantraniliprole, 11 g of nitrohumic acid, 3.5 g of sodium lignosulfonate, 1 g of Nekal, 70.6 g of kaolin, and 2.5 g of azo dye, and then carry out air flow pulverization to form a chlorantraniliprole mother powder with an average particle size of 5 μm;

[0144] S2. Prepare the clothianidin mother liquor: Dissolve 0.6 g of clothianidin in 0.78 g of methyl oleate, and then add 0.23 g of urea-formaldehyde resin to form a first material;

[0145] Then mix 3 g of calcium alkylbenzenesulfonate with 5.25 g of water to form a second material, and then mix and shear the second material with the first material to form a third material;

[0146] Finally, mix 0.34 g of citric acid solution with the third material evenly, adjust the pH to 6.55, heat up to 65 °C and keep warm for 2 h. Through heating and curing, wrap the clothianidin therein to obtain a controllable-release clothianidin microcapsule mother liquor with a weight percentage of 10.2%;

[0147] S3. Drop 10.2 g of the clothianidin mother liquor obtained in step S2 into 89.8 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry, and screen to obtain the clothianidin·chlorantraniliprole sustained-release granule.

[0148] In the clothianidin·chlorantraniliprole sustained-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.114; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.38, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:1.5.

[0149] Comparative Example 1

[0150] The difference from Example 1 lies in the different composition of the clothianidin mother liquor:

[0151] S1. Refer to step S1 of Example 1;

[0152] S2. Prepare the clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.44 g of methyl oleate, and then add 1.44 g of urea-formaldehyde resin to form a first material;

[0153] Then mix 2 g of calcium alkylbenzenesulfonate with 8.49 g of water to form a second material, and then mix and shear the second material with the first material to form a third material;

[0154] Finally, mix 0.43 g of citric acid solution with the third material evenly, adjust the pH to 5.5, heat up to 56 °C and keep warm for 2.7 h. Through heating and curing, the clothianidin is encapsulated therein to obtain a controlled-release clothianidin microcapsule mother liquor;

[0155] S3. Drop 15 g of the clothianidin mother liquor obtained in step S2 into 85 g of the chlorantraniliprole mother powder obtained in step S1, perform adsorption kneading, granulation, drying and screening to obtain a clothianidin·chlorantraniliprole slow-release granule.

[0156] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.176; the weight ratio of clothianidin to urea formaldehyde resin is 1:1.2, and the weight ratio of urea formaldehyde resin to the acidic solution is 1:0.3.

[0157] Comparative Example 2

[0158] The difference from Example 1 lies in the different composition of the clothianidin mother liquor:

[0159] S1. Refer to step S1 of Example 1;

[0160] S2. Prepare the clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.44 g of methyl oleate, then add 0.42 g of urea formaldehyde resin to form the first material;

[0161] Then mix 2 g of calcium alkylbenzene sulfonate with 9.23 g of water to form the second material, and then mix and shear it with the first material to form the third material;

[0162] Finally, mix 0.71 g of citric acid solution with the third material evenly, adjust the pH to 5.3, heat up to 56 °C and keep warm for 2.7 h. Through heating and curing, the clothianidin is encapsulated therein to obtain a controlled-release clothianidin microcapsule mother liquor;

[0163] S3. Drop 15 g of the clothianidin mother liquor obtained in step S2 into 85 g of the chlorantraniliprole mother powder obtained in step S1, perform adsorption kneading, granulation, drying and screening to obtain a clothianidin·chlorantraniliprole slow-release granule.

[0164] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.176; the weight ratio of clothianidin to urea formaldehyde resin is 1:0.35, and the weight ratio of urea formaldehyde resin to the acidic solution is 1:1.7.

[0165] Comparative Example 3

[0166] The difference from Example 1 lies in the different composition of the clothianidin mother liquor:

[0167] S1. Refer to step S1 of Example 1;

[0168] S2. Preparation of clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.44 g of methyl oleate, then add 0.1 g of urea-formaldehyde resin to form the first material;

[0169] Mix 2 g of calcium alkylbenzenesulfonate with 10.15 g of water to form the second material, and then mix and shear it with the first material to form the third material;

[0170] Finally, mix 0.12 g of citric acid solution evenly with the third material, adjust the pH to 7.1, heat up to 56 °C and keep warm for 2.7 h. Through heating and curing, wrap the clothianidin in it to obtain a controlled-release clothianidin microcapsule mother liquor;

[0171] S3. Drop 15 g of the clothianidin mother liquor obtained in step S2 into 85 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry and screen to obtain the clothianidin·chlorantraniliprole slow-release granule.

[0172] In the clothianidin·chlorantraniliprole slow-release granule prepared by the above method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.176; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.08, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:1.2.

[0173] Comparative Example 4

[0174] The difference from Example 1 lies in the different compositions of the chlorantraniliprole mother powder and the clothianidin mother liquor:

[0175] S1. Chlorantraniliprole mother powder: Mix 0.4 g of chlorantraniliprole, 10 g of sodium humate, 3 g of sodium lignosulfonate, 3 g of Nekal, 61.1 g of light calcium carbonate, and 0.5 g of azo dye, and then perform air-flow pulverization to form a chlorantraniliprole mother powder with an average particle size of 5 μm;

[0176] S2. Preparation of clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.44 g of methyl oleate, then add 0.42 g of urea-formaldehyde resin to form the first material;

[0177] Mix 2 g of calcium alkylbenzenesulfonate with 16.44 g of water to form the second material, and then mix and shear it with the first material to form the third material;

[0178] Finally, mix 0.5 g of citric acid solution evenly with the third material, adjust the pH to 5.2, heat up to 56 °C and keep warm for 2.7 h. Through heating and curing, wrap the clothianidin in it to obtain a controlled-release clothianidin microcapsule mother liquor;

[0179] S3. Drop 22 g of the clothianidin mother liquor obtained in step S2 into 78 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry and screen to obtain the clothianidin·chlorantraniliprole slow-release granule.

[0180] When prepared by the above method, the content of the clothianidin mother liquor is too high, and the chlorantraniliprole mother powder cannot be completely adsorbed. The particles are in a liquid state and cannot form granules, so the clothianidin·chlorantraniliprole sustained-release granule cannot be prepared. When preparing the granule by this method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.282; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.35, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:1.2.

[0181] Comparative Example 5

[0182] The difference from Example 1 lies in the different compositions of the chlorantraniliprole mother powder and the clothianidin mother liquor:

[0183] S1. Chlorantraniliprole mother powder: Mix 0.4 g of chlorantraniliprole, 10 g of sodium humate, 3 g of sodium lignosulfonate, 3 g of Nekal, 75.1 g of light calcium carbonate, and 0.5 g of azo dye, and then carry out air flow pulverization to form a chlorantraniliprole mother powder with an average particle size of 5 μm;

[0184] S2. Preparation of clothianidin mother liquor: Dissolve 1.2 g of clothianidin in 1.44 g of methyl oleate, then add 0.42 g of urea-formaldehyde resin to form the first material;

[0185] Mix 2 g of calcium alkylbenzenesulfonate with 2.44 g of water to form the second material, and then mix and shear it with the first material to form the third material;

[0186] Finally, mix 0.5 g of citric acid solution with the third material evenly, adjust the pH to 5.5, heat up to 56 °C and keep it warm for 2.7 h. Through heating and curing, wrap the clothianidin in it to obtain a controlled-release clothianidin microcapsule mother liquor;

[0187] S3. Drop 8 g of the clothianidin mother liquor obtained in step S2 into 92 g of the chlorantraniliprole mother powder obtained in step S1, adsorb and knead, granulate, dry, and screen to obtain the clothianidin·chlorantraniliprole sustained-release granule.

[0188] When prepared by the above method, the content of the clothianidin microcapsule mother liquor is too low. After the chlorantraniliprole mother powder is completely adsorbed, it is still in a powdery state and cannot form granules, so the clothianidin·chlorantraniliprole sustained-release granule cannot be prepared. When preparing the granule by this method, the weight ratio of the chlorantraniliprole mother powder to the clothianidin mother liquor is 1:0.087; the weight ratio of clothianidin to urea-formaldehyde resin is 1:0.35, and the weight ratio of urea-formaldehyde resin to the acidic solution is 1:1.2.

[0189] Comparative Example 6

[0190] Prepare a slow-release fertilizer granule of chlorantraniliprole and clothianidin with a weight percentage of 13.5% according to Example 1 in the publication No. CN 112273379 A.

[0191] Comparative Example 7

[0192] Prepare a granular medicated fertilizer of a composition of chlorantraniliprole and clothianidin with a weight percentage of 1.3% according to Example 1 in the publication No. CN 116178070 A.

[0193] Comparative Example 8

[0194] Refer to the method of Example 1 described in the publication No. CN 109006830 A, the method of Example 4 described in the publication No. CN 111226920 A, and the method of Example 12 described in the publication No. CN 103621535 A; for the disclosed methods, they are prepared by using the conventional granule preparation method, which is to mix and pulverize chlorantraniliprole, clothianidin, wetting agent, binder, etc., and add water and knead to granulate; the specific preparation method of this comparative example is as follows: Mix 0.4 g of chlorantraniliprole, 1.2 g of clothianidin, 10 g of sodium humate, 3 g of sodium lignosulfonate, 3 g of Nekal, 81.9 g of light calcium carbonate, and 0.5 g of azo dye, and then perform air-flow pulverization to form a mother powder of clothianidin·chlorantraniliprole with a weight percentage of 100%; add 15 g of deionized water dropwise to the mother powder, perform adsorption kneading, granulation, drying, and screening to obtain the clothianidin·chlorantraniliprole granule.

[0195] Comparative Example 9

[0196] Prepare a medicated fertilizer granule of chlorantraniliprole and clothianidin with a weight percentage of 0.16% according to Example 3 (Table 4 - Formula 4) in the publication No. CN 116730763 A.

[0197] Test Example 1

[0198] Indoor determination of the release rate of clothianidin·chlorantraniliprole slow-release granules in soil

[0199] Soil preparation:

[0200] Soil without baking treatment: Take the soil from the sugarcane planting area in Long'an County, Nanning City. This soil has not been applied with other pesticide components in the past two years. Take the cultivated soil from the surface to a depth of 10 cm, pulverize it evenly, sieve it through a 40-mesh sieve, adjust the humidity to 75 - 85%, and load it into a flower pot (diameter 20 cm) without holes at the bottom, with a thickness of 15 cm for standby.

[0201] Soil baked at high temperature: Another portion of the soil passed through a 40-mesh sieve was placed in a high-temperature oven at 500 °C and baked for 9 h to fully burn the organic matter into inorganic matter. After taking it out and cooling, the humidity was adjusted to 75 - 85%, and it was filled into a flower pot without holes at the bottom (diameter 20 cm) with a thickness of 15 cm for standby.

[0202] Treatment method of the medicament in the soil without baking treatment: 2 grams of the treatment medicament were placed in each flower pot. The clothianidin·chlorantraniliprole slow-release granules of Examples 1, 3, 5, 7, 9, 11 and Comparative Examples 1 - 3 and Comparative Examples 6 - 9 were put into a mesh cloth bag with a pore size of 200 meshes, so that the medicament could be spread flat in the mesh cloth bag. After tying the mouth, it was placed into the above flower pot, covered with 10 cm of soil without high-temperature baking treatment. After dripping 500 mL of water in the center, the mouth of the flower pot was covered with a plastic film to keep moisture. There were 12 replicates for each medicament, and a total of 13 experimental groups.

[0203] Treatment method of the medicament in the soil with high-temperature baking treatment: Another portion of the clothianidin·chlorantraniliprole granules of Example 1 and Comparative Examples 1, 6 and 9 were put into a mesh cloth bag with a pore size of 200 meshes, so that the medicament could be spread flat in the mesh cloth bag. After tying the mouth, it was placed into the above flower pot, covered with 10 cm of soil after high-temperature baking treatment. After dripping 500 mL of water in the center, the mouth of the flower pot was covered with a plastic film to keep moisture. There were 12 replicates for each medicament, and a total of 4 experimental groups.

[0204] Detection: After placing it at 25 °C for 14 days, 30 days, 45 days, and 60 days, 3 flower pots were randomly selected each time. The mesh cloth bag containing the medicament was taken out, and the contents of clothianidin and chlorantraniliprole in the soil were detected by high-performance liquid chromatography, and the weight was measured. The release rate of the clothianidin·chlorantraniliprole slow-release granules in the soil was calculated, and the average value of the data measured from 3 groups of samples was taken. The results are shown in Table 1 below.

[0205] Release rate of the active ingredient of the granule in the soil % = (actual measured weight of the active ingredient in the soil / initial theoretical weight of the active ingredient) * 100%

[0206] Table 1 Release rate of clothianidin·chlorantraniliprole slow-release granules in the soil

[0207]

[0208]

[0209] As can be seen from Table 1, the thiamethoxam·chlorantraniliprole slow-release granules of Examples 1, 3, 5, 7, 9, and 11 of the present invention are slowly released in the soil over time, the released drug amount is relatively uniform, and the drug release time can reach 60 days, achieving the purpose of controlled release; in Comparative Example 1 and Comparative Example 2, the release is relatively fast, especially when the release has reached more than 85% at the 45th day; in Comparative Example 6, the release is relatively slow in the initial 14 days, the release rate increases significantly on the 30th day, and reaches 100% on the 45th day, and all have been released; in Comparative Examples 7-9, the release of the conventional thiamethoxam·chlorantraniliprole slow-release granules in the soil is relatively fast, the release reaches more than 95% on the 14th day, and is basically completely released at 30 days. In addition, the results show that the initial release rate of Comparative Example 7 is the fastest and all have been released on the 14th day, and the release effect of Comparative Example 3 is the slowest, and the release rate reaches 40% at 60 days.

[0210] At the same time, it was found that in the experimental groups where the soils used in Example 1, Comparative Example 1, Comparative Example 6, and Comparative Example 9 were treated by high-temperature baking, the release rates of thiamethoxam and chlorantraniliprole in Example 1, Comparative Example 1, and Comparative Example 9 were not much different from those in the experimental groups where the soil was not treated by high-temperature baking. The release rate difference of Comparative Example 6 was obvious. After the soil was treated by high-temperature baking, the release rate of the medicament was relatively uniform and could reach 85% at the 60th day. It can be seen that the organic matter in the soil significantly promoted the degradation of the vinyl acetate binder after the application of the medicament, resulting in rapid release of the medicament, and the controlled release effect decreased significantly in the soil not treated by high-temperature baking. Comparing the thiamethoxam·chlorantraniliprole slow-release granules of the present invention, they are slowly released in the soil in the same time, and the urea-formaldehyde resin is not affected by the degradation of organic matter, avoiding the effective components of the granules being completely exposed in the soil for a period of time.

[0211] Overall experimental comparison found that in Comparative Examples 1-3, the dosage ratios of urea-formaldehyde resin, acidic solution, mother liquor, and mother powder were different, and the slow-release effect decreased significantly compared with Example 1. Especially, the release of thiamethoxam was significantly accelerated. It was also significantly found that the release rate of thiamethoxam in the thiamethoxam·chlorantraniliprole granules of Comparative Examples 6-9 was significantly higher than that of chlorantraniliprole, indicating that thiamethoxam without special process treatment was more likely to dissolve and release into the water body after being leached by water.

[0212] Test Example 2

[0213] Test the long-term effectiveness of the control effect of thiamethoxam·chlorantraniliprole slow-release granules on sugarcane borers in sugarcane planting areas

[0214] The test area is a sugarcane planting area in Guangxi. The soil quality, fertility, irrigation, management, and growth of sugarcane plants in this plot are relatively consistent. It has been affected by sugarcane borer pests over the years and belongs to an area with serious losses.

[0215] In sugarcane plantations, the persistence of the clothianidin·chlorantraniliprole granule of Examples 1, 2, 4, 6, 8, 10 and Comparative Examples 1-3 and Comparative Examples 6-9 in controlling sugarcane borers was tested. The planting area of each sample was 1 mu. The specific steps were as follows: Fertilization was carried out by ditch application during the sowing period. According to the area of the experimental plot, 20 g of each granule agent was accurately weighed (the application amount was the application amount of the active ingredient of the granule per mu of land). The agent was scattered into the sugarcane ditch, covered with a thin layer of soil and covered with a film after application. The other materials after removing the active ingredients clothianidin and chlorantraniliprole in Example 1 were used to replace the granule as the CK blank treatment.

[0216] After applying the agent according to the above scheme, investigations were carried out on the 15th day, 30th day, 45th day, 60th day and 75th day respectively. The total number of seedlings and the dead heart seedlings in the plot were counted, and the dead heart rate and control effect were calculated.

[0217] Dead heart rate = number of dead heart seedlings / total number of seedlings × 100%;

[0218] Control effect = (control dead heart rate - treatment dead heart rate) / control dead heart rate × 100%. The test results are shown in Table 2.

[0219] Table 2 Field control effect of clothianidin·chlorantraniliprole granule on sugarcane borers

[0220]

[0221] It can be seen from the treatment results in Table 2 that after the clothianidin·chlorantraniliprole sustained-release granule of the present invention was applied during the sugarcane planting stage, both the dead heart rate and the control effect could reach an ideal state. Within 75 days, the dead heart rate was controlled below 3.5%, and the control effect could reach more than 84.2%. It could quickly and long-lastingly control the occurrence of sugarcane borers. The control effects of Comparative Example 3 and Comparative Example 6 were the worst at the initial stage of 15 days, and the corresponding emergence rate would also be greatly affected. Especially the test results of Comparative Examples 1-3 and Comparative Examples 6-9 showed that the control effect had dropped below 82% on the 45th day, and the long-term control effect on pests was not good, and it was necessary to apply the medicine again for further pest killing treatment.

[0222] From the treatment results in Table 2 and combined with the treatment results in Table 1, it was obvious that the clothianidin·chlorantraniliprole sustained-release granule of the present invention showed excellent long-acting controlled release effects. Especially, it effectively alleviated the problems of poor quick-acting property after applying the medicine and the problem that clothianidin was easily dissolved in running water in the soil and lost with the water body. The number of drug application times and the amount of drug used were less, saving costs and reducing environmental pollution.

[0223] The clothianidin·chlorantraniliprole granule of the present invention is easy to obtain materials and has a simple process. It creatively uses a clothianidin microcapsule mother liquor wrapped with urea-formaldehyde resin instead of water for kneading granulation. Without increasing the complexity of the granulation process, the prepared product has an obvious controlled release effect, achieving the purpose of long-term prevention and control of pests. Especially, without affecting the quick-acting property of chlorantraniliprole, it effectively alleviates the problem that clothianidin is easily dissolved in water in the soil and lost with the water body, resulting in a significant reduction in the control effect. The number of pesticide applications and the dosage are less, improving the utilization rate of pesticides and being safe for crops while reducing the pollution of environmental water bodies.

[0224] In summary, the clothianidin·chlorantraniliprole slow-release granule of the present invention has excellent control effect on sugarcane borers, has a longer sustained release period of up to 75 days without affecting the quick-acting property and control effect, basically meets the growth period of sugarcane during the jointing stage. Most importantly, it effectively alleviates the problem that clothianidin is easily dissolved in water in the soil and lost with the water body, resulting in a significant reduction in the control effect, solves the defects brought about when using the clothianidin·chlorantraniliprole granule, saves costs and reduces environmental pollution, and has broad application prospects and market promotion value.

[0225] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A sustained-release granule containing clothianidin and chlorantraniliprole, characterized in that: A granule prepared by mixing chlorantraniliprole mother powder and clothianidin mother solution in a weight ratio of 1: (0.1-0.25), wherein: The clothianidin mother solution comprises the following raw materials in parts by weight: 0.1 to 10 parts by weight of clothianidin, 0.1 to 10 parts by weight of an organic solvent, 0.1 to 10 parts by weight of a urea-formaldehyde resin, 0.5 to 5 parts by weight of an emulsifier, 2 to 15 parts by weight of water, and 0.1 to 2 parts by weight of an acidic solution; The chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.1 to 10 parts by weight of chlorantraniliprole, 1 to 20 parts by weight of humic acid fertilizer, 0 to 10 parts by weight of dispersant, 0 to 10 parts by weight of wetting agent, 50 to 75 parts by weight of solid carrier and 0 to 10 parts by weight of warning color.

2. The sustained-release granules according to claim 1, characterized in that The weight ratio of chlorantraniliprole mother powder to clothianidin mother solution is 1:(0.11-0.25), and optionally 1:(0.13-0.18); And / or, the weight ratio of chlorantraniliprole to clothianidin is (0.1-4):(0.6-6), optionally 1: (1.2~3), optionally 1:3; And / or, the sustained-release granules are prepared by mixing, kneading, drying and sieving clothianidin mother solution and chlorantraniliprole mother powder in proportion.

3. The sustained-release granules according to claim 1, characterized in that The clothianidin mother solution comprises the following raw materials in parts by weight: 0.3-6 parts by weight of clothianidin, 0.5-6 parts by weight of an organic solvent, 0.3-3 parts by weight of a urea-formaldehyde resin, 0.6-3.2 parts by weight of an emulsifier, 2.5-11 parts by weight of water, and 0.2-1.6 parts by weight of an acidic solution; the acidic solution is optionally used to adjust the pH of the mixture of the clothianidin mother solution to 4.9-6.71; Optionally, the clothianidin mother solution comprises the following raw materials in parts by weight: 1.2-2.5 parts by weight of clothianidin, 1.4-3.8 parts by weight of an organic solvent, 0.42-0.75 parts by weight of a urea-formaldehyde resin, 0.65-2 parts by weight of an emulsifier, 3.5-9.5 parts by weight of water, and 0.2-1.6 parts by weight of an acidic solution; optionally, the acidic solution is used to adjust the pH of the mixture of the clothianidin mother solution to 5.2-6.1; Optionally, the clothianidin mother solution comprises the following raw materials in parts by weight: 1.2-2.5 parts by weight of clothianidin, 1.4-2.0 parts by weight of an organic solvent, 0.42-0.66 parts by weight of a urea-formaldehyde resin, 1.55-2 parts by weight of an emulsifier, 9-9.5 parts by weight of water, and 0.5-0.53 parts by weight of an acidic solution; optionally, the acidic solution is used to adjust the pH of the mixture of the clothianidin mother solution to 5.5-5.9; Optionally, the weight ratio of clothianidin to urea-formaldehyde resin is 1:(0.1-1), optionally 1:(0.35-0.55); Optionally, the weight ratio of urea-formaldehyde resin to acid solution is 1:(0.6-1.5), optionally 1:(0.8-1.2); Optionally, the clothianidin mother solution accounts for 10-20% of the total weight of the sustained-release granules, optionally 12-18%, optionally 12-15%.

4. The sustained-release granules according to any one of claims 1 to 3, characterized in that: In the clothianidin mother solution, the emulsifier is selected from one or more of styrene-maleic anhydride copolymer, alkyl biphenyl ether disulfonic acid magnesium salt, alkyl benzene sulfonate calcium, nonylphenol polyoxyethylene ether phosphate, styrene polyoxyethylene ether ammonium sulfate, benzyl dimethylphenol polyoxyethyl ether, alkylphenol formaldehyde resin polyoxyethyl ether, phenethylphenol formaldehyde resin polyoxyethyl ether, ethylene oxide-propylene oxide block copolymer, castor oil polyoxyethylene ether, Span series sorbitan monostearate, and fatty alcohol polyoxyethylene ether; optionally, the weight ratio of the emulsifier to water is 1:(1.5-5.9), optionally 1:(1.75-5.9); And / or, in the clothianidin mother solution, the organic solvent is selected from one or more of palm oil, soybean oil, methyl oleate or vegetable oil; optionally, the weight ratio of clothianidin technical to the organic solvent is 1:(1-2), optionally 1:(1-1.7); And / or, in the clothianidin mother solution, the acidic solution is a weak acid solution, and optionally the acidic solution is selected from one or more of a citric acid solution, a phosphoric acid solution, and an acetic acid solution.

5. The sustained-release granules according to any one of claims 1 to 4, characterized in that: The chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.1 to 4 parts by weight of chlorantraniliprole, 2 to 15 parts by weight of humic acid fertilizer, 0 to 10 parts by weight of dispersant, 0 to 10 parts by weight of wetting agent, 52 to 71 parts by weight of solid carrier, and 0 to 10 parts by weight of warning color; Optionally, the chlorantraniliprole master powder comprises the following raw materials in parts by weight: 0.1 to 4 parts by weight of chlorantraniliprole, 5 to 15 parts by weight of humic acid fertilizer, 1 to 10 parts by weight of dispersant, 1 to 10 parts by weight of wetting agent, 52.5 to 70.6 parts by weight of solid carrier, and 0 to 10 parts by weight of warning color; Optionally, the chlorantraniliprole mother powder comprises the following raw materials in parts by weight: 0.1 to 4 parts by weight of chlorantraniliprole, 5 to 15 parts by weight of humic acid fertilizer, 2.5 to 6 parts by weight of dispersant, 1 to 6 parts by weight of wetting agent, 52.5 to 70.6 parts by weight of solid carrier, and 0 to 10 parts by weight of warning color; Optionally, the chlorantraniliprole master powder comprises the following raw materials in parts by weight: 0.4-2 parts by weight of chlorantraniliprole, 7-12 parts by weight of humic acid fertilizer, 3-5 parts by weight of dispersant, 3-6 parts by weight of wetting agent, 61.6-68.1 parts by weight of solid carrier, and 0-10 parts by weight of warning color; Optionally, the weight portion of the warning color is 0.2 to 7 weight portions, optionally 1 to 7 weight portions, optionally 0.2 to 3.2 weight portions, optionally 0.2 to 0.5 weight portions; Optionally, the chlorantraniliprole mother powder accounts for 80-90% of the total weight of the sustained-release granules, optionally 82-88%, optionally 85-88%; Optionally, the average particle size of the chlorantraniliprole mother powder is 1 to 10 μm, optionally 3 to 6 μm, optionally 4 to 6 μm, optionally 5 μm.

6. The sustained-release granules according to any one of claims 1 to 5, characterized in that: The humic acid fertilizer includes one or more of humic acid, nitrohumic acid, humic acid water-soluble salt and nitrohumic acid water-soluble salt; And / or, the dispersant is selected from one or more of carboxylates, sodium naphthalene sulfonate formaldehyde condensate, calcium lignin sulfonate, polycarboxylates, sodium lauryl alcohol polyoxyethylene ether sulfate, desugared sodium lignin sulfonate, desugared condensed sodium lignin sulfonate, sodium lignin sulfonate, and alkylnaphthalene formaldehyde condensate sulfonate; And / or, the wetting agent is selected from one or more of calcium dodecylbenzene sulfonate, wetting and penetrating agent T, EFW, pull-opening powder, alkylphenol polyoxyethylene ether nonylphenol polyoxyethylene ether; and / or, the solid carrier is selected from one or more of carboxymethyl cellulose, kaolin, montmorillonite, sepiolite, pyrophyllite, xylitol, montmorillonite, clay, bentonite, white carbon black, diatomaceous earth, talc and light calcium carbonate; And / or, the warning color is selected from one or more of metal phthalocyanine, iron oxide, azo dye, and triphenylmethane dye.

7. A method for preparing the sustained-release granules according to any one of claims 1 to 6, characterized in that: The steps include: S1, mixing the solid chlorantraniliprole original drug in the chlorantraniliprole mother powder with various adjuvants in proportion, and performing air flow milling to obtain the chlorantraniliprole mother powder; S2, liquefying the solid clothianidin technical, and wrapping it with urea-formaldehyde resin to prepare a controlled-release clothianidin mother solution; S3. Adding the prepared clothianidin mother solution into the chlorantraniliprole mother powder for adsorption, kneading, granulation, drying and sieving to obtain clothianidin / chlorantraniliprole sustained-release granules.

8. The preparation method according to claim 7, characterized in that: In step S2, the method for preparing clothianidin mother solution comprises: (1) dissolving solid clothianidin technical into a liquefied state in an organic solvent, and mixing the liquefied state with a urea-formaldehyde resin to form a first material; (2) mixing water and an emulsifier to form a second material; (3) mixing the first material and the second material, and shearing them to form a third material; (4) mixing the third material with the acidic solution, heating and curing, encapsulating the clothianidin therein, and obtaining a controlled-release clothianidin microcapsule mother solution; optionally, during the heating and curing, the temperature is 50 to 65° C., and the heat preservation time is 2 to 3 h.

9. Use of the slow-release granule according to any one of claims 1 to 6, or the slow-release granule prepared by the preparation method according to claim 7 or 8, in controlling underground pests.

10. The use according to claim 9, characterized in that: The underground pest is sugarcane borer, and the optional application method is broadcasting.

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