Nano emamectin benzoate chlorantraniliprole suspending agent and preparation method and application thereof

Abstract

The invention belongs to the technical field of pesticides, and particularly relates to a nano emamectin benzoate chlorantraniliprole suspending agent as well as a preparation method and application thereof. The nano emamectin benzoate and chlorantraniliprole suspending agent is prepared from the following components in percentage by weight: 1 to 30 percent of emamectin benzoate, 1 to 30 percent of chlorantraniliprole, 0 to 3 percent of wetting agent or wetting dispersant, 3 to 10 percent of solvent, 0.1 to 4 percent of thickening agent, 0.1 to 1.5 percent of stabilizer, 0.1 to 0.5 percent of defoaming agent, 0.01 to 0.3 percent of preservative, 0.1 to 10 percent of anti-freezing agent and the balance of water, the solvent is DMF (Dimethyl Formamide) or a mixture containing DMF; the particle size D90 of the nano emamectin benzoate and chlorantraniliprole suspending agent is less than or equal to 100nm. The nano emamectin benzoate and chlorantraniliprole suspending agent is low in production cost and fine in particle size, the nano suspending agent with the same mass contains more pesticide nanoparticles, and the nano suspending agent is wide in target coverage, excellent in permeability, high in pesticide effect, low in viscosity, good in pouring property, capable of diffusing in a cloud mist shape after entering water, free of layering and precipitation and excellent in stability.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and particularly relates to a nano chloranil sulfoxide suspension and a preparation method and application thereof. Background Art

[0002] Emamectin benzoate, full name avermectin benzoate, is a white or light yellow crystalline powder, soluble in acetone and methanol, slightly soluble in water, and insoluble in hexane. It is a new type of highly effective semi-synthetic antibiotic insecticide synthesized from the fermentation product avermectin B1. It has the characteristics of ultra-high efficiency, low toxicity (the preparation is nearly non-toxic), low residue, and pollution-free biological pesticides. It is widely used in the prevention and control of various pests on crops such as vegetables, fruit trees, and cotton.

[0003] Chlorantraniliprole is used to control major pests of rice and other crops, protecting the growth of rice and other crops. It is especially effective against pests that have already developed resistance to other rice insecticides, such as rice leaf roller, striped stem borer, yellow stem borer, and rice borer. It also has a good control effect on rice gall midge, rice weevil and rice water weevil. The pesticide is slightly toxic and very safe for the pesticide applicators, as well as for beneficial insects, fish and shrimp in rice fields. The effective period can reach more than 15 days, with no residual effect on agricultural products, and good mixing performance with other pesticides.

[0004] In practical applications, in order to treat multiple diseases and pests, improve prevention effects or delay resistance, multiple active ingredients are generally processed into compound preparations for use. When a compound of emamectin benzoate and chlorantraniliprole is used as an insecticide, it can make up for the defects of emamectin benzoate that is easily photolyzed and has poor sustainability; it can also make up for the defect that long-term use of chlorantraniliprole easily causes pests to develop resistance to the drug. Therefore, the existing technology often uses emamectin benzoate and chlorantraniliprole in combination.

[0005] Nanopesticides have been one of the research hotspots in the field of nano-agriculture at home and abroad in recent years, and have good application prospects in alleviating food residues and environmental pollution caused by pesticide abuse. Nano-sizing can improve the dispersibility and dissolution rate of poorly soluble pesticide particles, and can also reduce the amount of organic solvents used in pesticide formulations, thereby reducing the pollution caused by harmful solvents and adjuvants flowing into the environment. The development history of pesticide suspensions is relatively short, and it is a new formulation that is being continuously improved. The emergence of this formulation has raised the pesticide formulation processing technology to a new level, creating broad development prospects and new opportunities for the production and application of many pesticides that are neither hydrophilic nor lipophilic.

[0006] The patent document with publication number CN117918366A discloses a method for preparing a suspension concentrate by compounding emamectin benzoate and chlorantraniliprole, wherein emamectin benzoate, chlorantraniliprole and other auxiliary agents are dissolved in water and ground to obtain the suspension concentrate. However, due to the original drug characteristics of emamectin benzoate, it will agglomerate in water, and it is very difficult to grind it into nanometer-scale particle size, and some special polymer dispersants need to be added, which greatly increases the production cost. Therefore, the particle size of the suspension concentrate obtained in CN117918366A is only 1 to 5 μm.

[0007] Therefore, how to prepare a nano-scale chloranil sulfamethoxam suspension has become a technical problem that needs to be solved urgently. Summary of the invention

[0008] In order to solve the drawbacks of the above-mentioned prior art, the present invention provides a nano chloranil sulfoxide suspension and a preparation method and application thereof, which specifically adopts the following technical means.

[0009] A nano chloranil sulfamethoxazole suspension, comprising the following components by weight:

[0010] 1-30% of emamectin benzoate, 1-30% of chlorantraniliprole, 0-3% of a wetting agent or a wetting dispersant, 3-10% of a solvent, 0.1-4% of a thickener, 0.1-1.5% of a stabilizer, 0.1-0.5% of a defoaming agent, 0.01-0.3% of a preservative and 0.1-10% of an antifreeze agent, and the balance is water; the solvent is DMF or a mixture containing DMF;

[0011] The particle size of the nano chloranil sulfoxide suspension is D90≤100nm.

[0012] Furthermore, based on the weight fraction of the nano-emamectin methyl sulfoxide suspension as 100%, in the mixture containing DMF, the weight fraction of the DMF is at least 3%;

[0013] The mixture containing DMF is a mixture of DMF and any one of alcohols, benzenes, cyclohexanone and pyrrolidone.

[0014] Furthermore, the weight percentage of the total weight of emamectin benzoate and chlorantraniliprole in the nano emamectin benzoate suspension is 5 to 36%.

[0015] Furthermore, the nano-emamectin methyl sulfoxide suspension comprises the following components by weight:

[0016] 1-5% of avermectin benzoate, 1-10% of chlorantraniliprole, 0-1.5% of wetting agent or wetting dispersant, 3-10% of solvent, 0.5-2.5% of thickener, 0.5-1.5% of stabilizer, 0.1-0.5% of defoaming agent, 0.01-0.2% of preservative and 2-5% of antifreeze agent, and the balance is water.

[0017] Further, the wetting and dispersing agent is one or a combination of fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, sorbitan polyoxyethylene ether, phenol ether phosphate salt, high molecular weight block copolymer, phenethylphenol polyether phosphate salt, alkyl sulfonate, naphthalene sulfonate, sulfate, carboxylate, lignin sulfonate, betaine, dodecyl cocamide betaine, polycarboxylate and dioctyl sodium sulfosuccinate;

[0018] Further, the thickener is one or a combination of xanthan gum, magnesium aluminum silicate, guar gum, polyvinyl alcohol, carboxymethyl cellulose and organic bentonite;

[0019] Further, the stabilizer is one or a combination of BHT, BIT, disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, epoxidized vegetable oil, kaolin, bentonite, attapulgite, white carbon black, talc, montmorillonite and starch;

[0020] Further, the defoaming agent is one or a combination of C10-C20 saturated fatty acid compounds, silicone oil, silicone compounds and C8-C10 fatty alcohols;

[0021] Further, the preservative is one or a combination of isothiazolinone, benzisothiazolinone, dibromocyanopropionamide, sodium benzoate and sodium benzoate;

[0022] Further, the antifreeze agent is one or a combination of alcohols, alcohol ethers, chlorinated hydrocarbons and inorganic salts;

[0023] Further, the wetting and dispersing agent is one or a combination of fatty alcohol polyoxyethylene ether, alkyl sulfonate, phenethylphenol polyether phosphate salt, carboxylate, and lignin sulfonate;

[0024] Further, the thickener is a mixture of xanthan gum and magnesium aluminum silicate;

[0025] Further, the stabilizer is BHT;

[0026] Furthermore, the defoamer is a silicone defoamer;

[0027] Further, the preservative is sodium benzoate;

[0028] Furthermore, the antifreeze agent is ethylene glycol.

[0029] Furthermore, the mass ratio of xanthan gum to magnesium aluminum silicate in the thickener is 1:5.

[0030] The present invention also discloses a method for preparing any of the above-mentioned nano-emamectin methyl chloranil suspensions, comprising the following steps:

[0031] After measuring each raw material according to weight percentage, chlorantraniliprole is mixed with a wetting agent or a wetting dispersant, a stabilizer, a defoaming agent, a preservative, an antifreeze agent and water, graded and ground until the material particle size D90 is less than or equal to 100 nm, a thickener is added, and the mixture is mixed to obtain a chlorantraniliprole nano suspension;

[0032] Emamectin benzoate is dissolved in a solvent and then mixed with chlorfenapyr nano suspension to obtain nano emamectin benzoate suspension.

[0033] The nano suspension formulation contains no or a trace amount of wetting agent and defoamer, which can eliminate the adverse effects of the two on grinding efficiency. The foam during grinding is significantly reduced, and the adverse effects of the defoamer on the friction shear force of the grinding medium (such as zirconium beads) surface are no longer present, so the grinding efficiency is greatly improved, so that the particle size of the prepared chlorantraniliprole suspension can reach 50 to 100 nanometers.

[0034] Conventional nano suspension production process is just to repeatedly sand-grind the material to make it reach nanometer particle size. This process is simple and rough, and is suitable for some original drugs that are easy to sand-grind. However, due to the original drug characteristics of emamectin benzoate, it will reunite in water, and it is more difficult to sand-grind it to nanometer particle size, and some special polymer dispersants need to be added, and the production cost will be greatly increased. The present invention is prepared by dissolving emamectin benzoate with a solvent to prepare an oil phase, and then mixing it with the chlorantraniliprole suspension agent that is sand-grinded to nanometer particle size. The emamectin benzoate suspension agent finally prepared can reach nanometer level, and greatly reduces the production cost. At the same time, the present invention avoids the destruction of the stability of the nano suspension system by the solvent by selecting a specific solvent. After emamectin benzoate is dissolved by the solvent of the present invention, the stability of the nano suspension agent obtained by mixing with the chlorantraniliprole suspension agent is better.

[0035] Furthermore, the grinding media used during grinding is one or a combination of glass beads, zirconium oxide beads, polystyrene beads and aluminum oxide grinding beads.

[0036] The invention also discloses the application of any of the above-mentioned nano chloranil sulfoxide suspensions as a herbicide.

[0037] Compared with the prior art, the invention has the following beneficial effects: the particle size D90 of the nano-emamectin benzoate suspension of the invention is less than or equal to 100 nm, the nanoparticles in the system have strong non-directional Brownian motion, and the system has dynamic stability; since the particle size of the nano-emamectin benzoate suspension of the invention is relatively fine, the nano-suspension of the same mass has a larger number of pesticide nanoparticles, has a wide coverage of the target, has an increased specific surface area, has enhanced leaf surface adhesion and penetration properties, and has high drug efficacy; the nano-emamectin benzoate suspension prepared by the invention has low viscosity, good pourability, diffuses in a cloud-like manner into water, does not stratify or precipitate, and has excellent stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1a This is a photo of a corn field without the application of nano-chloranil suspension. Figure 1b This is a photo of a corn field where nano-chlorpyrifos suspension was applied;

[0039] Figure 2a This is a photo of a cotton field without the application of nano-chloranil suspension. Figure 2b This is a photo of a cotton field where nano-chlorpyrifos suspension was applied. DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings.

[0041] It should be noted that the experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents described are commercially available unless otherwise specified.

[0042] Example 1

[0043] A preparation method of nano chloranil sulfamethoxazole suspension:

[0044] Formula composition: 1.5% of emamectin benzoate, 4.5% of chlorfenapyr, 2% of fatty alcohol polyoxyethylene ether, 1% of magnesium aluminum silicate, 0.2% of xanthan gum, 0.5% of BHT, 0.2% of organic silicon defoamer, 0.02% of sodium benzoate, 4% of ethylene glycol and 7% of DMF, and the balance is water;

[0045] Preparation method: chlorantraniliprole is mixed with a wetting dispersant, a stabilizer, a defoamer, a preservative, an antifreeze agent and deionized water, and then wet-grinded. The sand-grinding medium is zirconium oxide beads, and the particle sizes of the zirconium oxide beads are 1.0-1.2 mm, 0.6-0.8 mm and 0.2-0.3 mm. The product particle size is sand-milled to D90≤100 nm, the material is discharged, a thickener is added, and the mixture is homogeneously mixed to obtain a chlorantraniliprole nano suspension, which is then set aside.

[0046] Emamectin benzoate is dissolved in a solvent and then mixed with chlorfenapyr nano suspension to obtain nano emamectin benzoate suspension.

[0047] Example 2

[0048] The difference between this embodiment and embodiment 1 is that the solvent is replaced with 4% DMF plus 3% xylene;

[0049] Example 3

[0050] The difference between this embodiment and embodiment 1 is that the solvent is replaced with 3% DMF plus 4% cyclohexanone;

[0051] Example 4

[0052] A preparation method of nano chloranil sulfamethoxazole suspension:

[0053] Formula composition: 2% of emamectin benzoate, 8% of chlorfenapyr, 0.5% of phenethylphenol polyether phosphate salt, 2% of lignin sulfonate, 1% of magnesium aluminum silicate, 0.2% of xanthan gum, 0.5% of BHT, 0.2% of organosilicon defoamer, 0.02% of sodium benzoate, 4% of ethylene glycol and 7% of DMF, and the balance is water;

[0054] The preparation method is the same as Example 1.

[0055] Example 5

[0056] A preparation method of nano chloranil sulfamethoxazole suspension:

[0057] Formula composition: 1% avermectin benzoate, 30% chlorantraniliprole, 1% fatty alcohol polyoxyethylene ether, 1.5% guar gum, 1% disodium hydrogen phosphate, 0.5% organosilicon defoamer, 0.3% isothiazolinone, 0.1% ethylene glycol and 3% DMF, the balance is water;

[0058] The preparation method is the same as Example 1.

[0059] Example 6

[0060] A preparation method of nano chloranil sulfamethoxazole suspension:

[0061] Formula composition: 30% of emamectin benzoate, 1% of chlorantraniliprole, 4% of organic bentonite, 0.1% of white carbon black, 0.1% of organic silicon defoamer, 0.1% of dibromocyanopropionamide, 10% of ethylene glycol and 10% of DMF, and the balance is water;

[0062] Example 7

[0063] The difference between this embodiment and embodiment 1 is that the formula composition contains 10% of emamectin benzoate and 10% of chlorantraniliprole, and the rest is exactly the same as that of embodiment 1.

[0064] Example 8

[0065] The difference between this embodiment and embodiment 1 is that the formula composition contains 20% avermectin benzoate and 10% chlorantraniliprole. The rest is exactly the same as embodiment 1.

[0066] Comparative Example 1

[0067] The difference between this comparative example and Example 1 is that the solvent in the formula composition is 7% methanol. The rest is exactly the same as Example 1.

[0068] Comparative Example 2

[0069] The difference between this comparative example and Example 1 is that the solvent in the formula composition is 7% xylene. The rest is exactly the same as Example 1.

[0070] Comparative Example 3

[0071] The difference between this comparative example and Example 1 is that the solvent in the formula composition is 7% cyclohexanone. The rest is exactly the same as Example 1.

[0072] Comparative Example 4

[0073] The formulation of this comparative example does not contain a solvent, and the rest of the formulation is exactly the same as that of Example 1.

[0074] Preparation method: chlorantraniliprole, emamectin benzoate, a wetting dispersant, a stabilizer, a defoaming agent, a preservative, an antifreeze agent, and deionized water are mixed evenly, and then wet sand milled. The selected sand milling medium is zirconium oxide beads, and the particle size of the zirconium oxide beads is 1.0-1.2 mm, 0.6-0.8 mm, and 0.2-0.3 mm. The mixed solution is obtained by graded sand milling, and the grinding time is the same as that in Example 1 to obtain a mixed solution, a thickener is added, and the mixture is mixed to obtain a chlorantraniliprole suspension.

[0075] Comparative Example 5

[0076] The formulation of this comparative example does not contain a solvent, and the rest of the formulation is exactly the same as that of Example 4.

[0077] Preparation method: chlorantraniliprole, emamectin benzoate, a wetting dispersant, a stabilizer, a defoaming agent, a preservative, an antifreeze agent, and deionized water are mixed evenly, and then wet sand milled. The selected sand milling medium is zirconium oxide beads, and the particle size of the zirconium oxide beads is 1.0-1.2 mm, 0.6-0.8 mm, and 0.2-0.3 mm. The sand milling is graded, and the sand milling time is the same as that in Example 4 to obtain a mixed solution, and a thickener is added. The mixture is mixed to obtain a chlorantraniliprole suspension.

[0078] The chloranil sulfamethoxam suspension prepared in Examples 1 to 8 and Comparative Examples 1 to 5 were tested as follows:

[0079] ①Particle size test

[0080] 100 g of each sample from Examples 1 to 8 and Comparative Examples 1 to 5 was placed at room temperature (25° C.), frozen (-15° C.), and hot storage (54° C.) for 14 days, and then the particle size was measured using a laser particle size analyzer (BT-9300S, Dandong Better Instrument Co., Ltd.). The test results are shown in Table 1:

[0081] Table 1 Particle size test experimental data table (D90 / nm)

[0082]

[0083]

[0084] ② Effect of solvent on physical stability of preparations

[0085] 100 g of each sample from Examples 1 to 8 and Comparative Examples 1 to 5 was taken and placed at room temperature (25°C), frozen (-15°C), and hot storage (54°C) for 14 days, respectively. The cold and hot storage samples were then restored to room temperature and the appearance changes of each sample were observed. The appearance of each sample is shown in Table 2:

[0086]

[0087] ③ The samples of Examples 1 to 8 were subjected to a dumping test using the method of GB / T 31737-2015. The test results are shown in Table 3.

[0088] Table 3 Pourability of Examples 1-8 Samples

[0089]

[0090] According to the test results in Tables 1 to 3, the particle size of the chloranil benzoate suspension prepared in Examples 1 to 8 of the present invention is D90≤100 nm, and they are all nano suspensions, which have the advantages of wide coverage of the target and excellent permeability, and the prepared nano chloranil benzoate suspension has better stability and better pouring performance.

[0091] According to the comparison of the test results of Example 1, Example 4 and Comparative Examples 4 to 5 in Table 1, it can be known that the emamectin phenylate is dissolved in a solvent to prepare an oil phase, and then mixed with the chlorantraniliprole suspension agent that is sand-ground into a nanometer particle size, and finally a nanoscale suspension agent with D90≤100nm can be obtained. Under the same conditions, after the emamectin phenylate is mixed with chlorantraniliprole and ground together, the particle size of the suspension agent obtained is larger and D90≤100nm cannot be reached. The particle size of the nanometer emamectin phenylate suspension agent prepared by the present invention is finer, and the nanometer suspension agent of the same mass has a larger number of pesticide nanoparticles, a wide coverage of the target, excellent permeability, and high efficacy.

[0092] According to the comparison of the test results of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1 and Table 2, the nano chloranil methyl sulfoxide suspension prepared by using the solvent of the present invention does not delaminate or precipitate after 14 days of storage at room temperature, freezing or heat storage, and has excellent stability.

[0093] Figure 1a , Figure 2a These are photos of corn fields and cotton fields without pesticides. Figure 1b , Figure 2b The following are photos of the nano-emamectin chlorfenapyr suspension prepared in Example 1, wherein Figure 1a , Figure 1b For the same corn variety in the same corn field at the same growth period, Figure 2a , Figure 2b The photos are of the same cotton variety in the same cotton field at the same growth period. It can be seen from the photos that the application of the nano-emamectin chlorfenapyr suspension prepared by the present invention greatly reduces the occurrence of plant diseases and insect pests.

Claims

1. A nano chloranil sulfamethoxazole suspension, characterized in that: By weight, it contains the following components: 1-30% of emamectin benzoate, 1-30% of chlorantraniliprole, 0-3% of wetting agent or wetting dispersant, 3-10% of solvent, 0.1-4% of thickener, 0.1-1.5% of stabilizer, 0.1-0.5% of defoamer, 0.01-0.3% of preservative and 0.1-10% of antifreeze, and the balance is water; The solvent is DMF or a mixture containing DMF; The particle size of the nano chloranil sulfoxide suspension is D90≤100nm.

2. Nano chloranil sulfoxide suspension according to claim 1, characterized in that, Taking the weight fraction of the nano-emamectin methyl sulfoxide suspension as 100%, the weight fraction of DMF in the mixture containing DMF is at least 3%; The mixture containing DMF is a mixture of DMF and any one of alcohols, benzenes, cyclohexanone and pyrrolidone.

3. Nano chloranil sulfoxide suspension according to claim 1, characterized in that, By weight, it contains the following components: 1-5% of avermectin benzoate, 1-10% of chlorantraniliprole, 0-1.5% of wetting agent or wetting dispersant, 3-10% of solvent, 0.5-2.5% of thickener, 0.5-1.5% of stabilizer, 0.1-0.5% of defoaming agent, 0.01-0.2% of preservative and 2-5% of antifreeze agent, and the balance is water.

4. The nano chloranil sulfoxide suspension according to claim 1, characterized in that The wetting and dispersing agent is one or a combination of fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, sorbitan polyoxyethylene ether, phenol ether phosphate salt, high molecular weight block copolymer, phenethylphenol polyether phosphate salt, alkyl sulfonate, naphthalene sulfonate, sulfate, carboxylate, lignin sulfonate, betaine, dodecyl cocamide betaine, polycarboxylate and dioctyl sodium sulfosuccinate; The thickener is one or a combination of xanthan gum, magnesium aluminum silicate, guar gum, polyvinyl alcohol, carboxymethyl cellulose and organic bentonite; The stabilizer is one or a combination of BHT, BIT, disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, epoxidized vegetable oil, kaolin, bentonite, attapulgite, white carbon black, talc, montmorillonite and starch; The defoaming agent is one or a combination of C10-C20 saturated fatty acid compounds, silicone oil, silicone compounds and C8-C10 fatty alcohols; The preservative is one or a combination of isothiazolinone, benzisothiazolinone, dibromocyanopropionamide and sodium benzoate; The antifreeze agent is one or a combination of alcohols, alcohol ethers, chlorinated hydrocarbons and inorganic salts.

5. The nano chloranil sulfoxide suspension according to claim 1, characterized in that The wetting and dispersing agent is one or a combination of fatty alcohol polyoxyethylene ether, alkyl sulfonate, phenethylphenol polyether phosphate salt, carboxylate, and lignin sulfonate; The thickener is a mixture of xanthan gum and magnesium aluminum silicate; The stabilizer is BHT; The defoamer is an organosilicon defoamer; The preservative is sodium benzoate; The antifreeze agent is ethylene glycol.

6. The nano emamectin methyl sulfoxide suspension according to claim 5, characterized in that, The mass ratio of xanthan gum to magnesium aluminum silicate in the thickener is 1:

5.

7. A method for preparing the nano-emamectin methyl sulfoxide suspension according to any one of claims 1 to 6, characterized in that: The steps include: After measuring each raw material according to weight percentage, chlorantraniliprole is mixed with a wetting and dispersing agent, a stabilizer, a defoaming agent, a preservative, an antifreeze agent and water, graded and ground until the material particle size D90 is less than or equal to 100 nm, a thickener is added, and the mixture is mixed to obtain a chlorantraniliprole nano suspension; Emamectin benzoate is dissolved in a solvent and then mixed with chlorfenapyr nano suspension to obtain nano emamectin benzoate suspension.

8. The preparation method according to claim 7, characterized in that: The grinding media used during grinding are one or a combination of glass beads, zirconium oxide beads, polystyrene beads and aluminum oxide grinding beads.

9. An application of the nano-emamectin methyl suspension according to any one of claims 1 to 6, characterized in that: Used as a herbicide.

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