Suspending agent containing emamectin benzoate and preparation method thereof

Abstract

The invention discloses a suspending agent containing emamectin benzoate and a preparation method of the suspending agent. The suspending agent is prepared from an active component A, an active component B, an agriculturally acceptable dispersing agent, a wetting agent, a defoaming agent, an anti-freezing agent, a thickening agent, a preservative and water, the active ingredient A is methylamino abamectin benzoate, and the mass percentage content of the active ingredient A is 5-15%; the active ingredient B is chlorantraniliprole or lufenuron, and the mass percentage content of the active ingredient B is 5-30%; the dispersing agent is a weak cationic surfactant containing an amide group; and the wetting agent is an anionic surfactant. According to the suspending agent disclosed by the invention, the performance of a single agent is improved, the control effect on resistant plutella xylostella is improved, and the problems that a suspending agent containing emamectin benzoate is easy to paste after being ground, poor in compatibility with xanthan gum, easy to flocculate after being diluted with water and easy to paste after being stored in heat are solved.

Description

TECHNICAL FIELD

[0001] The present application relates to a suspension containing emamectin benzoate and a preparation method thereof, and belongs to the technical field of pesticide preparation. BACKGROUND

[0002] Emamectin benzoate is a low-toxicity insecticide and acaricide of microbial origin, which is a highly effective biological agent synthesized on the basis of avermectin. It has the characteristics of high activity, wide insecticidal spectrum, good miscibility, long persistence, and safety in use. Its action mode is mainly stomach toxicity, with a certain contact action. Its insecticidal mechanism is to hinder the movement of the nervous system of pests.

[0003] Chlorantraniliprole is a new type of diacyl amide insecticide with a new action mechanism, which is a highly effective insecticide for preventing and treating different Coleoptera, Lepidoptera, Diptera and Hemiptera pests. Lufenuron is a new generation of substituted urea insecticide developed by the United States Novartis Company. It can inhibit the chitin synthesis of insect larvae, interfere with the deposition of chitin on the cuticle, and cause the insect to die due to abnormal molting. It is a highly effective and broad-spectrum low-toxicity insecticide that mainly acts on the stomach, with a certain contact action, no systemic action, and good ovicidal effect. It is mainly used for preventing and treating rice leaf roller, Spodoptera exigua, Spodoptera littoralis, Plutella xylostella, Agrotis segetum, Pieris rapae, and Tetranychus urticae, etc.

[0004] Mixing different single agents together for use to improve the performance of single agents has become a technology widely used in plant protection at home and abroad. Emamectin benzoate, chlorantraniliprole or lufenuron can be prepared into a complex preparation to achieve better control effect on Plutella xylostella, delay the problem of resistance to single agents, and reduce the control cost.

[0005] Combinations of emamectin benzoate with chlorfenapyr or lufenuron are generally prepared as suspension concentrates, offering the advantages of being environmentally friendly and low-cost. However, emamectin is a new, highly effective antibiotic insecticide and acaricide synthesized from the fermentation product avermectin B1. Because it is synthesized from a fermentation product, its technical component is relatively complex, especially low-content technical components. Currently, approved technical components registered in my country have content levels of 79.1%, 81.5%, 83.5%, 83.6%, 84.4%, 90%, 95%, and 96%. Because high-content technical components (above 95%) are technically difficult to prepare and expensive, low-content technical components remain the mainstream product on the market. This results in significant difficulty in preparing single-dose emamectin benzoate suspension concentrates and combined formulations containing emamectin benzoate. These formulations tend to become paste-like during grinding and hot storage (at 54°C for two weeks), especially when the emamectin benzoate content in the formulation is above 3%. Chinese patent application CN102754643 A discloses a suspension concentrate of emamectin benzoate. The preparation of emamectin benzoate suspension concentrates, particularly those with a weight percentage of emamectin benzoate greater than 3%, and particularly greater than 5%, presents significant technical challenges. Problems often arise, such as difficulty grinding the original drug, easy paste formation during sand-grinding, poor adaptability, and flocculation upon dilution with water. Suspensions formulated with emamectin benzoate and chlorfenapyr or lufenuron still present similar problems. These problems are not only related to the low content of the original drug and the complex composition, but also to the properties of emamectin benzoate itself and the thickening system used. The amino group in emamectin benzoate can be protonated, typically carrying a positive charge, while the benzoate group is generally neutral, resulting in a positive overall molecule under certain conditions. However, the primary structure of xanthan gum, a commonly used thickener, consists of a cellulose backbone and trisaccharide side chains composed of mannose, glucuronic acid, and mannose (attached to the C-3 position of alternating glucose residues on the backbone). The mannose residues within the side chains are partially O-acetylated at the C-6 position, and approximately 50% of the terminal mannose residues have a pyruvate ketal at the C-4 and C-6 positions. The number of substituents depends on the growth conditions and strain. Generally, the dissolved oxygen rate is low, and the pyruvate content is low. The glucuronic acid and pyruvic acid on the side chains impart a negative charge to the xanthan gum. Emamectin benzoate is easily attracted to the charge of the xanthan gum in the thickener. This characteristic makes the addition of xanthan gum more susceptible to deterioration of physical properties, such as flocculation and creaming. This is why the present invention was developed. Summary of the Invention

[0006] The present invention aims to provide a composite suspension concentrate containing emamectin benzoate for controlling resistant diamondback moth, wherein another active ingredient may be chlorfenapyr or lufenuron. The present invention adopts a suitable dispersant and a wetting agent, wherein the dispersant contains an amide group in its molecular structure and is a weak cationic surfactant, and the wetting agent is an anionic surfactant, thereby reducing the influence of charge, thereby solving the problems of low content of the original drug and the mutual influence of the charges of emamectin benzoate and xanthan gum.

[0007] The suspension concentrate containing emamectin benzoate provided by the present invention is prepared from active ingredient A, active ingredient B, an agriculturally acceptable dispersant, a wetting agent, a defoaming agent, an antifreeze agent, a thickener, a preservative and water;

[0008] The active ingredient A is emamectin benzoate, with a mass percentage of 5-15%;

[0009] The active ingredient B is chlorantraniliprole or lufenuron, with a mass percentage of 5-30%;

[0010] The dispersant is a weak cationic surfactant containing an amide group, which shields the positive charge of emamectin benzoate;

[0011] The wetting agent is an anionic surfactant that balances the electrical properties of the system.

[0012] In the suspension concentrate of the present invention, the total mass percentage of the active ingredient A and the active ingredient B is 10-45%.

[0013] In the suspending agent of the present invention, the dispersant is selected from one or more of fatty acid alkanolamide surfactants and lauric acid monoethanolamide;

[0014] The fatty acid alkanolamide surfactants include coconut diethanolamide, ethylene bisstearamide, and AG902.

[0015] In the suspension concentrate of the present invention, the wetting agent is a sulfonate surfactant, including YC 7007F, sodium dodecylbenzenesulfonate, and α-olefin sulfonate.

[0016] In the suspending agent of the present invention, the defoaming agent is an organosilicon defoaming agent, such as Sag 622.

[0017] In the suspension concentrate of the present invention, the antifreeze agent is selected from propylene glycol, glycerol or a mixture thereof.

[0018] In the suspension concentrate of the present invention, the preservative is selected from sodium benzoate and isothiazolinone.

[0019] In the suspending agent of the present invention, the thickener is xanthan gum.

[0020] The present invention also provides a method for preparing the suspension concentrate, comprising the following steps:

[0021] S1. Mixing emamectin benzoate, chlorantraniliprole or lufenuron, a dispersant, a wetting agent, a defoaming agent, an antifreeze agent and water to prepare a base material;

[0022] S2. Grind the base material with a sand mill to an average particle size of 2 μm-4 μm to ensure suspension stability and control the grinding temperature to 10-30° C.;

[0023] S3, mixing xanthan gum, preservatives and water to prepare a thickener solution;

[0024] S4. Mixing the base material ground in step S2 with the thickener solution obtained in step S3 to obtain the suspending agent.

[0025] The present invention adopts an amide dispersant, and a weak cationic surfactant containing an amide group can shield the positive charge of emamectin benzoate; the present invention adopts a sulfonate anionic surfactant, which can balance the electrical properties of the system, thereby ensuring that the suspension system has a balanced charge after adding a xanthan gum (weak anion) thickener, avoiding the mutual combination of emamectin benzoate and xanthan gum through electrostatic interaction, and maintaining good fluidity after heat storage.

[0026] The suspension concentrate of the invention improves the performance of a single agent, enhances the control effect on resistant diamondback moth, and solves the problems that the suspension concentrate containing emamectin benzoate is easy to paste after grinding, has poor compatibility with xanthan gum, is easy to flocculate when diluted with water, and is easy to paste during hot storage.

[0027] The present invention has the following beneficial technical effects:

[0028] 1. The present invention is beneficial to protecting the agricultural ecological environment, does not contain organic solvents, and reduces environmental pollution;

[0029] 2. The composite suspension concentrate of the present invention improves the control effect on resistant diamondback moth. The two single agents have different mechanisms of action and can delay the development of drug resistance.

[0030] 3. The content of emamectin benzoate in the suspension concentrate of the present invention is relatively high, reaching 5%-15%, which is helpful for preparing high-content products and reducing transportation costs;

[0031] 4. The suspending agent of the present invention improves the compatibility of emamectin benzoate and xanthan gum, has a simple preparation method, and reduces product cost;

[0032] 5. The suspension concentrate of the present invention has a wide range of adaptability to the emamectin benzoate technical drug, and qualified suspension concentrates can be prepared from the technical drug content of 79.1% to 96%. DETAILED DESCRIPTION

[0033] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0034] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0035] Example 1: 10% Emamectin-Chlorantraniliprole Suspension Concentrate

[0036]

[0037] According to the above formula, emamectin benzoate technical, chlorantraniliprole technical, dispersant, wetting agent, defoamer, and antifreeze were weighed and mixed with water to obtain a base. The base was ground in a horizontal sand mill at a temperature of 25°C until the average particle size reached 2.5 μm, and then filtered. A thickener solution was prepared by mixing xanthan gum, a preservative, and water. The ground base and the pre-prepared thickener solution were then mixed to obtain a 10% emamectin / chlorantraniliprole suspension concentrate.

[0038] The physical and chemical properties of the prepared suspension concentrate were measured according to the following methods: 1. Mass fraction of active ingredient. The mass fraction of emamectin benzoate was determined with reference to the national standard for emamectin emulsifiable concentrate (GB 20694-2006), and the mass fraction of chlorantraniliprole was determined using liquid chromatography; 2. pH was determined according to the method of CIPAC MT 75.3; 3. Suspension rate. The suspension rate test method was carried out in accordance with CIPAC MT 184, and the physical suspension rate was determined by the gravimetric method; 4. Wet sieve test. The wet sieve test was carried out in accordance with CIPAC MT 185; 5. Persistent foaming property. Persistent foaming property was determined in accordance with CIPAC MT 47.2; 6. Thermal storage stability. Thermal storage stability was determined in accordance with 2.3 of GB / T 19136-2003; 7. Pourability. Pourability was determined in accordance with CIPAC MT 148.1.

[0039] The quality and technical indicators of Example 1 are shown in Table 1.

[0040] Table 1 Quality specifications of 10% emamectin benzoate·chlorantraniliprole suspension concentrate

[0041]

[0042]

[0043] The emamectin technical content used in this example was 79.1%. The preparation did not cream during the grinding process, and no flocculation or creaming occurred after the addition of xanthan gum. It did not cream or agglomerate after storage at 54° C. for 14 days, and maintained good fluidity. No flocculation occurred when the preparation was diluted with water.

[0044] Example 2: 35% emamectin benzoate·chlorantraniliprole suspension concentrate

[0045]

[0046] The preparation method of Example 1 was used, and the grinding temperature was controlled at 23°C to obtain a 35% emamectin benzoate·chlorantraniliprole suspension concentrate with an average particle size of 3.1 μm. The suspension concentrate was tested according to the test method of Example 1. The test results are shown in Table 2.

[0047] Table 2 Quality specifications of 35% emamectin benzoate·chlorantraniliprole suspension concentrate

[0048]

[0049] The emamectin technical content used in this example was 83.5%. The preparation did not cream during the grinding process, and no flocculation or creaming occurred after the addition of xanthan gum. It did not cream or agglomerate after storage at 54° C. for 14 days, and maintained good fluidity. No flocculation occurred when the preparation was diluted with water.

[0050] Example 3: 30% emamectin benzoate and lufenuron suspension

[0051]

[0052]

[0053] Preparation was performed according to the preparation method of Example 1, with the grinding temperature controlled at 25°C, to obtain a 30% emamectin benzoate / lufenuron suspension concentrate with an average particle size of 2.3 μm. This suspension was assayed according to the testing method of Example 1, with the mass fraction of lufenuron determined by liquid chromatography. The test results are shown in Table 3.

[0054] Table 3 Quality specifications of 30% emamectin benzoate·lufenuron suspension concentrate

[0055]

[0056] The emamectin benzoate technical content used in this example was 79.1%. The preparation did not cream during the grinding process, and no flocculation or creaming occurred after the addition of xanthan gum. It did not cream or agglomerate after storage at 54° C. for 14 days, and maintained good fluidity. No flocculation occurred when the preparation was diluted with water.

[0057] Example 4: 20% emamectin benzoate-lufenuron suspension

[0058]

[0059] A 20% emamectin benzoate / lufenuron suspension concentrate with an average particle size of 3.1 μm was prepared according to the preparation method of Example 1, with a grinding temperature of 26°C. The suspension concentrate was tested according to the test method of Example 1, with the mass fraction of lufenuron determined by liquid chromatography. The test results are shown in Table 4.

[0060] Table 4 Quality specifications of 20% emamectin benzoate·lufenuron suspension concentrate

[0061]

[0062]

[0063] The emamectin technical content used in this example was 84.5%. The preparation did not cream during the grinding process, and no flocculation or creaming occurred after the addition of xanthan gum. It did not cream or agglomerate after storage at 54° C. for 14 days, and maintained good fluidity. No flocculation occurred when the preparation was diluted with water.

[0064] Example 5: 45% emamectin benzoate and lufenuron suspension

[0065]

[0066] A 45% emamectin benzoate / lufenuron suspension concentrate with an average particle size of 3.2 μm was prepared according to the preparation method of Example 1, with a grinding temperature of 30°C. The suspension concentrate was tested according to the test method of Example 1, with the mass fraction of lufenuron determined by liquid chromatography. The test results are shown in Table 5.

[0067] Table 5 Quality specifications of 45% emamectin benzoate·lufenuron suspension concentrate

[0068]

[0069]

[0070] The emamectin benzoate used in the embodiment has a content of 95.5%, and the preparation does not appear creaming during the grinding process, does not appear flocculation and creaming after the addition of xanthan gum, does not appear creaming and caking after storage at 54℃ for 14 days, and still has good fluidity. The preparation does not appear flocculation after dilution with water.

[0071] Comparative Example 1, 30% emamectin benzoate · lufenuron suspension agent

[0072]

[0073] The comparative examples are prepared by using emamectin benzoate of 79.1% and 95% content respectively according to the preparation method of Example 1, and the grinding temperature is controlled at 25℃. The sample creaming occurs during the grinding of the emamectin benzoate of 79.1% content, and the state is viscous during the grinding of the emamectin benzoate of 95% content. After the addition of xanthan gum, creaming occurs during the heat storage.

[0074] Example 6, field control effect of the compound preparation on resistant Plutella xylostella

[0075] In order to verify the control effect of the suspension agent of the present application on Plutella xylostella, field efficacy test was carried out in Xiangongshan village, Dongpu town, Shaoxing city, Zhejiang province. The cabbage was sowed on May 18, 2024, and the pesticide was applied on May 23. At this time, it was the occurrence period of Plutella xylostella, and the growth stage of cabbage was rosette stage. The test results are shown in Table 6. The test results show that the compound suspension agent of Example 1 and Example 3 has good control effect on Plutella xylostella, and the control effect reaches 91.94% and 90.93% respectively 10 days after the pesticide application.

[0076] Table 6 Field efficacy test of Plutella xylostella

[0077]

[0078] In summary, the compound suspension agent containing emamectin benzoate of the present application can achieve the following beneficial effects:

[0079] 1. The present application is beneficial to the protection of agricultural ecological environment, does not contain organic solvent, and reduces the pollution to the environment;

[0080] 2. The compound suspension agent provided by the present application improves the control effect on resistant Plutella xylostella, and the two single agents have different action mechanisms, which can delay the generation of drug resistance;

[0081] 3. The content of emamectin benzoate in the compound suspension agent prepared by the present application can reach 5% to 15%, which is helpful for the preparation of high content products and reduces the transportation cost;

[0082] 4. The suspension concentrate containing emamectin benzoate prepared by the present invention improves the compatibility of emamectin benzoate and xanthan gum, has a simple preparation method, and reduces product cost;

[0083] 5. The suspension concentrate containing emamectin benzoate prepared by the present invention has a wide range of adaptability to the emamectin benzoate technical drug, and qualified suspension concentrates can be prepared from technical drugs with a content of 79.1% to 96%;

[0084] 6. The raw materials used in the present invention are all available on the market and are very practical. Among them, AG 902 was purchased from Xiaoxiong (Shanghai) Chemical Technology Co., Ltd., YC 7007F was purchased from Yancheng Xingtai Yancheng Chemical Additive Co., Ltd., coconut acid diethanolamide was purchased from Guoli Chemical Co., Ltd., and sag 622 was purchased from Jierun Technology Co., Ltd.

[0085] The various embodiments provided herein may be combined in any manner as needed, and the resulting technical solutions are also within the scope of the present invention. Obviously, those skilled in the art may make various modifications and variations to the present invention without departing from the spirit and scope of the present invention. Thus, if such modifications and variations fall within the scope of the claims and their equivalents, the present invention also encompasses such modifications and variations.

Claims

1. A suspension concentrate containing emamectin benzoate, comprising active ingredient A, active ingredient B, an agriculturally acceptable dispersant, a wetting agent, a defoaming agent, an antifreeze agent, a thickener, a preservative, and water; The active ingredient A is emamectin benzoate, with a mass percentage of 5-15%; The active ingredient B is chlorantraniliprole or lufenuron, with a mass percentage of 5-30%; The dispersant is a weak cationic surfactant containing an amide group; The wetting agent is an anionic surfactant.

2. The suspending agent according to claim 1, wherein: In the suspension concentrate, the total mass percentage of the active ingredient A and the active ingredient B is 10-45%.

3. The suspending agent according to claim 1 or 2, characterized in that: The dispersant is selected from one or more of fatty acid alkanolamide surfactants and lauric acid monoethanolamide.

4. The suspending agent according to claim 1 or 2, characterized in that: The wetting agent is a sulfonate surfactant.

5. The suspending agent according to claim 4, wherein: The wetting agents include YC 7007F, sodium dodecylbenzene sulfonate and α-olefin sulfonate.

6. The suspending agent according to claim 1 or 2, characterized in that: The defoaming agent is an organosilicon defoaming agent.

7. The suspending agent according to claim 1 or 2, characterized in that: The antifreeze agent is selected from propylene glycol, glycerol or a mixture thereof.

8. The suspending agent according to claim 1 or 2, characterized in that: The preservative is selected from sodium benzoate and isothiazolinone; The thickener is xanthan gum.

9. A method for preparing the suspension concentrate according to any one of claims 1 to 8, comprising the steps of: S1. Mixing emamectin benzoate, chlorantraniliprole or lufenuron, a dispersant, a wetting agent, a defoaming agent, an antifreeze agent and water to prepare a base material; S2, grinding the base material with a sand mill to an average particle size of 2 μm-4 μm; S3, mixing xanthan gum, preservatives and water to prepare a thickener solution; S4. Mixing the base material ground in step S2 with the thickener solution obtained in step S3 to obtain the suspending agent.

10. Use of the suspension concentrate according to any one of claims 1 to 8 in controlling resistant diamondback moth.

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