Chlorantraniliprole nano suspending agent taking hectorite as stabilizer as well as preparation method and application of chlorantraniliprole nano suspending agent

Abstract

The invention discloses a chlorantraniliprole nano suspending agent taking hectorite as a stabilizer as well as a preparation method and application of the chlorantraniliprole nano suspending agent, and relates to the technical field of pesticide preparations. Comprising the following steps: dispersing artificially synthesized hectorite (the purity is 100%) in water to obtain a colloidal suspension, adding a surfactant for intercalation reaction, then dispersing superfine crushed chlorantraniliprole powder in a reaction solution, stirring at a high speed to form a uniform suspension, and performing ball milling on the suspension to obtain the nano pesticide suspending agent. According to the preparation method disclosed by the invention, the defects of addition of a dispersing aid, a thickening agent and the like in a traditional process are overcome, and the problems of poor batch stability, inconsistent performance and the like of a clay-based product in an industrial production process are solved. In addition, the nano pesticide water suspending agent prepared by the invention has an obvious prevention and treatment effect on diseases and insect pests.

Description

Technical Field

[0001] This invention relates to a nano-pesticide suspension, specifically to a chlorantraniliprole nano-suspension with lithium saponite as a stabilizer, its preparation method, and its application, belonging to the field of nano-pesticide application technology. Background Technology

[0002] Clay minerals have been widely reported and applied as pesticide nanocarriers due to their diverse morphologies (such as rod-shaped, tubular, and lamellar structures), small size, large specific surface area, controllable structure, easy chemical modification of the surface, abundant resources, low price, and non-toxicity. Chemical Engineering Journal, 2018, 349: 101-110; Applied Clay Science, 2018,161: 194-202 Simultaneously, based on the electronegativity, viscosity, and surface -OH / Si-O-Si groups of clay minerals, the suspension stability of pesticide suspension concentrates and the adhesion of pesticides to leaf surfaces can be significantly improved. Chemical Engineering Journal, 2025, 503: 158168 Therefore, in recent years there have been reports of clay minerals being used in the preparation of pesticide suspensions. CN202411423925.7, CN202411424056.X, Chemical Engineering Journal, 2025, 503: 158168 However, most clay minerals cannot be synthesized artificially. Clay minerals derived from nature have significant differences in composition due to different geological formations, and their associated minerals cannot be completely separated using existing purification technologies. Therefore, clay-based products often experience problems such as poor batch stability and inconsistent performance during industrial production.

[0003] Lithium saponite is a synthetic trioctahedral layered silicate clay mineral with a purity of up to 100%. Its layered structure consists of nanoscale sheets, but due to electrostatic interactions, these sheets tend to aggregate, limiting their nanoscale properties. Depending on the synthesis method, its thickness varies from a few nanometers to hundreds of nanometers. Its surface and edges exhibit double-charge characteristics, allowing for the intercalation of cations between the layers to achieve sheet exfoliation. Lithium saponite can form a three-dimensional network structure in water, exhibiting strong gelling, thixotropic, dispersible, suspending, and thickening properties, making it suitable as a pesticide carrier, suspension stabilizer, and dispersant. Therefore, this invention aims to introduce lithium saponite, utilizing its multifunctionality as a nanomaterial to efficiently solve the current problems associated with water-insoluble pesticide suspensions. Summary of the Invention

[0004] The purpose of this invention is to provide a chlorantraniliprole nano-suspension with lithium saponite as a stabilizer, its preparation method and application, in order to solve the problems of existing chlorantraniliprole aqueous suspensions, such as the large number of additives, large particle size, complex preparation process, poor storage stability and low bioavailability, as well as the problems of poor batch stability and inconsistent performance of clay-based pesticide suspensions in industrial production.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: A chlorantraniliprole nano-suspension agent with lithium saponite as a stabilizer is prepared through the following steps: (1) Disperse lithium saponite in water to form a colloidal suspension; (2) Add a surfactant to the colloidal suspension to carry out an intercalation reaction, thereby achieving the exfoliation and functionalization of lithium saponite sheets; (3) The ultra-fine chlorantraniliprole powder is added to the solution after the intercalation reaction, and a uniform suspension is formed under high-speed stirring conditions; (4) The suspension is ball-milled to obtain a nano-pesticide suspension with uniform particle size distribution and high stability.

[0006] Preferably, in step (1), the thickness of the lithium saponite lamellae is less than 10 nm and the mass percentage concentration is 0.5%~5.0%.

[0007] Preferably, the surfactant in step (2) has a carbon chain length of C4~C6. 18 At least one or two quaternary ammonium salts are used, with a mass percentage concentration of 0.1% to 2%, and the reaction is carried out at room temperature for 4 to 12 hours.

[0008] Preferably, the chlorantraniliprole powder ultra-finely pulverized in step (3) is pulverized using an ultra-fine pulverizer at a speed of 5000~10000 rpm for 2~10 min, with a mass percentage concentration of 5%~40%.

[0009] Preferably, in step (3), the high-speed stirring is performed at a speed of 4000~8000 rpm for 10 min.

[0010] Preferably, in step (4), the ball-to-material ratio is 10:1 to 50:1, and the ball is milled at 100 rpm for 0.5 to 4 hours.

[0011] The nano-suspension prepared by the above method has an average particle size of less than 200 nm and exhibits excellent physical and storage stability.

[0012] This invention also provides the application of the nano-suspension agent in the prevention and control of crop diseases and pests, including but not limited to cabbage caterpillars, aphids, diamondback moths, thrips, etc.

[0013] The principle of the method of this invention is as follows: based on the layered structure characteristics of lithium saponite itself, the effective peeling of lithium saponite flakes is achieved by adding surfactants, and then a "carrying house" structure is formed by high-speed stirring to attach water-insoluble pesticides to the surface of lithium saponite flakes. Then, the particle size of the pesticides is further reduced by grinding. By utilizing the high suspension and high viscosity of lithium saponite itself, the effective preparation of water-based nano-pesticide suspension is achieved.

[0014] Structural characterization of the product of this invention: Figure 1 Infrared spectra of chlorantraniliprole (a), lithium saponite (b), and the suspension obtained in Example 2 (c) are presented. Figure 1 c can be seen in the range of 3400~2800 cm. -1 and 1700~450 cm -1 The characteristic infrared absorption peak of chlorantraniliprole was observed (see...) Figure 1 a), at 1640 cm -1 1005 cm -1 and 449 cm -1 The characteristic infrared absorption peak of lithium saponite appeared at (see) Figure 1 (b) Among them, the infrared absorption peak of lithium saponite is slightly shifted, indicating that lithium saponite mainly achieves complexation with chlorantraniliprole through weak interactions such as hydrogen bonds and van der Waals forces. Figure 2 XRD patterns of chlorantraniliprole (a), lithium saponite (b), and the suspension obtained in Example 2 (c) are presented. Figure 2 As can be seen from c, the characteristic X-ray diffraction peaks of chlorantraniliprole appeared in the range of 8.5° to 32.5° at 2θ (see Figure 2 a), characteristic X-ray diffraction peaks of lithium saponite appeared at 34.9° and 60.9° (see a). Figure 2 (b) The above results further corroborate that the two components achieved effective compounding without any chemical reaction.

[0015] Stability testing of the product of this invention: Figure 3 The changes in particle size of the suspension obtained in Example 2 before and after hot and cold storage are shown. From... Figure 3 It can be seen that, after testing according to the conditions specified in GB / T 19136—2021 and GB / T 19137—2003 national standards, the average particle size (D) of the suspension after hot and cold storage is [data missing]. 50 It is still less than 200 nm. Figure 4 Digital photographs of the stability of the suspensions obtained in the comparative and example studies after high and low temperature storage are provided. Figure 4 It is evident that the suspension obtained in the examples did not exhibit water separation, stratification, or precipitation after high and low temperature storage, which is significantly superior to the comparative example.

[0016] Application performance test of the product of this invention: The nano-suspension obtained in the example was diluted 200 times and sprayed onto plant leaves. The mortality rate of cabbage caterpillars was measured within 24 hours, and the results are as follows. Figure 5 As shown. From Figure 5 It can be seen that the suspension obtained in the example has a kill rate of more than 95% against cabbage caterpillars within 24 hours.

[0017] In summary, the present invention has the following advantages compared with the prior art: (1) The lithium saponite clay mineral introduced in this invention is artificially synthesized and has stable properties, which can ensure the batch stability and performance consistency of the product during the production process. At the same time, its own stability can significantly improve the high / low temperature storage stability of the nano-pesticide suspension.

[0018] (2) Lithium saponite combines gelling, thixotropic, dispersing and suspending properties. Compared with traditional processes, lithium saponite can replace dispersants and thickeners, greatly reducing production costs. Attached Figure Description

[0019] Figure 1 Infrared spectra of (a) chlorantraniliprole, (b) lithium saponite and (c) the suspension obtained in Example 2.

[0020] Figure 2 XRD of (a) chlorantraniliprole, (b) lithium saponite and (c) the suspension obtained in Example 2.

[0021] Figure 3 The change in particle size of the suspending agent obtained in Example 2 before and after high and low temperature storage.

[0022] Figure 4 Digital photographs of the stability of the suspensions obtained in (a) comparative examples, (b) Example 1, (c) Example 2, (c) Example 3 and (c) Example 4 after high-temperature storage (A) and low-temperature storage (B).

[0023] Figure 5 The insecticidal performance of the suspension obtained in the example is shown. Detailed Implementation

[0024] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention. It should be noted that the lithium saponite used in the present invention was purchased from Jiangsu Haimings New Material Technology Co., Ltd.

[0025] Comparative example (traditional method without adding lithium soapstone) 0.15 g of octadecyltrimethylammonium chloride was dissolved in 100 mL of deionized water under stirring at 300 rpm. 10.00 g of chlorantraniliprole technical (pre-crushed at 8000 rpm for 10 min using an ultrafine grinder) was added to this solution. After stirring for 4 h, the mixture was sheared at 8000 rpm for 10 min. The slurry was then transferred to a ball mill and ball-milled for 4 h at a ball-to-particle ratio of 20:1 and a rotation speed of 100 rpm. The resulting suspension had an average particle size of 1305 nm and a pesticide suspension rate of 83.48%. After high-temperature storage (54±2°C, 14 days) and low-temperature storage (0±2°C, 7 days) tests according to GB / T 19136-2021 and GB / T 19137-2003 standards, the system showed obvious water separation, stratification, and precipitation (see GB / T 19136-2021 and GB / T 19137-2003). Figure 4 (Sample a in A and 4B).

[0026] Example 1 0.5 g of lithium saponite was dispersed in 100 mL of deionized water under stirring at 300 rpm to form a homogeneous colloidal suspension. 2.0 g of tetraalkyltrimethylammonium chloride was added, and the mixture was reacted at room temperature (approximately 25°C) for 12 h to complete intercalation and exfoliation. Then, 40.00 g of chlorantraniliprole technical (pre-crushed at 5000 rpm for 2 min using an ultrafine pulverizer) was added. The mixture was then subjected to high-speed shear stirring at 4000 rpm for 10 min to form a preliminary suspension. Finally, the suspension was ball-milled in a ball mill at a ball-to-particle ratio of 10:1 and a rotation speed of 100 rpm for 0.5 h to obtain the target nano-suspension. The average particle size (D) of the obtained suspension was... 50 The nanometer diameter (nm) was 142 nm, and the pesticide suspension rate was 90.59%. No water separation, stratification, or precipitation was observed after hot and cold storage (see [reference]). Figure 4 It exhibits excellent physical stability. When the suspension was diluted 200 times and sprayed onto cabbage leaves infected with cabbage caterpillars, the corrected mortality rate was higher than 95% after 24 hours (see [link to relevant documentation]). Figure 5 ).

[0027] Example 2 2.5 g of lithium saponite was dispersed in 100 mL of deionized water under stirring at 300 rpm. 0.15 g of octadecyltrimethylammonium chloride was added, and the mixture was reacted at room temperature for 4 h. Then, 10.00 g of chlorantraniliprole technical (pre-crushed at 8000 rpm for 10 min using an ultrafine pulverizer) was added. After high-speed shear stirring at 8000 rpm for 10 min, the suspension was ball-milled in a ball mill at a ball-to-particle ratio of 20:1 and a rotation speed of 100 rpm for 4 h. The resulting suspension had an average particle size of 139 nm and a pesticide suspension rate as high as 96.67%. After hot and cold storage tests, the particle size remained below 200 nm (see [link to relevant documentation]). Figure 3 Furthermore, its appearance is uniform and stable, with no phase separation phenomena (see...). Figure 4 Infrared spectroscopy ( Figure 1 c) and X-ray diffraction pattern ( Figure 2 c) indicates that chlorantraniliprole and lithium saponite achieve an effective combination through physical action. Bioactivity testing shows that its 24-hour control efficacy against cabbage caterpillars exceeds 95% (see [link to relevant documentation]). Figure 5 ).

[0028] Example 3 5.0 g of lithium saponite was dispersed in 100 mL of deionized water under stirring at 300 rpm. A mixed surfactant of 0.05 g of hexadecyltrimethylammonium chloride and 0.05 g of octadecyltrimethylammonium chloride was added, and the mixture was reacted at room temperature for 6 h. Subsequently, 20.00 g of chlorantraniliprole technical (pre-crushed at 10000 rpm for 5 min using an ultrafine grinder) was added. After high-speed shearing and stirring at 5000 rpm for 10 min, the mixture was ball-milled at a ball-to-particle ratio of 50:1 and a rotation speed of 100 rpm for 2 h. The resulting suspension had an average particle size of 145 nm and a pesticide suspension rate of 92.13%. It exhibited good stability after hot and cold storage (see [reference]). Figure 4 ), with excellent insecticidal activity (see Figure 5 ).

[0029] Example 4 2.0 g of lithium saponite was dispersed in 100 mL of deionized water under stirring at 300 rpm. 1.00 g of dodecyltrimethylammonium chloride was added, and the reaction was carried out at room temperature for 3 h. Then, 20.00 g of chlorantraniliprole technical (pre-crushed at 6000 rpm for 5 min using an ultrafine pulverizer) was added. After high-speed shear stirring at 6000 rpm for 10 min, the mixture was ball-milled for 2 h at a ball-to-particle ratio of 30:1 and a rotation speed of 100 rpm. The resulting suspension had an average particle size of 125 nm and a pesticide suspension rate of 90.72%. After high and low temperature storage, the system remained homogeneous and stable (see [reference]). Figure 4 ), and exhibits highly effective insecticidal properties (see Figure 5）。

Claims

1. A method for preparing chlorantraniliprole nano-suspending agent using lithium saponite as a stabilizer, characterized in that, Includes the following steps: S1. Preparation of stabilizer: Lithium saponite with a sheet thickness of less than 10 nm is dispersed in water at a mass percentage concentration of 0.5% to 5.0% to form a colloidal suspension; then, a quaternary ammonium salt surfactant with a carbon chain length of C4 to C18 is added to the colloidal suspension, the amount of the surfactant added is 0.1% to 2.0% of the total mass of the colloidal suspension, and the mixture is stirred at room temperature for 4 to 12 hours to complete the intercalation and exfoliation, and an activated lithium saponite nanosheet dispersion is obtained; S2. Preparation of nano-suspension: The chlorantraniliprole technical material is ultra-finely pulverized, and then added to the activated lithium saponite nanosheet dispersion obtained in step S1 at a final mass percentage concentration of 5%~40%. The mixture is stirred at high speed at 4000~8000 rpm for 10~15 min to form a primary suspension. The primary suspension is then ball-milled at a ball-to-material mass ratio of 10:1~50:1 and a speed of 100 rpm for 0.5~4 hours to obtain the chlorantraniliprole nano-suspension with lithium saponite as a stabilizer.

2. The method as described in claim 1, characterized in that, The ultrafine pulverization is carried out at a rotation speed of 5000~10000 rpm for 2~10 minutes.

3. The method as described in claim 1, characterized in that, The chlorantraniliprole nano-suspension with lithium saponite as a stabilizer has a particle size of less than 200 nm.

4. The use of the chlorantraniliprole nano-suspension according to any one of claims 1-3 in the preparation of pesticide formulations for controlling Lepidoptera, Hemiptera or Thysanoptera pests.

5. The application according to claim 4, characterized in that, The pests mentioned are cabbage caterpillars, aphids, diamondback moths, or thrips.

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