Pesticide suspending agent containing clothianidin and chlorfenapyr

Abstract

The invention discloses a pesticide suspending agent containing clothianidin and chlorfenapyr, which comprises the following components in percentage by mass: 10-30% of clothianidin, 10-30% of chlorfenapyr, 10-30% of chlorfenapyr, 10- 5%-25% of chlorfenapyr; 10%-35% of a thickening agent; 2%-15% of a dispersant; and the balance of water. The thickening agent is a mixture of magnesium aluminum silicate, precipitated white carbon black and a 1 wt% xanthan gum aqueous solution; the dispersing agent is a high-molecular polymer aqueous solution or a mixed aqueous solution of a high-molecular polymer and DETA. The pesticide suspending agent containing clothianidin and chlorfenapyr disclosed by the invention can still keep relatively thin appearance property and texture, is free from layering and creaming after being stored for 14 days at normal temperature in a heat storage manner, a cold storage manner and a freeze thawing manner, and has good flowability.

Description

Technical Field

[0001] The present invention belongs to the field of pesticide suspension concentrates, and particularly relates to a pesticide suspension concentrate containing clothianidin and chlorfenapyr. Background Art

[0002] Pesticides are the material basis for ensuring national food security. China is the largest producer and user of pesticides in the world. In order to ensure the insecticidal effect and grain yield, pesticides are often over-applied, resulting in low utilization rate and posing a serious threat to the environment and human health. Some pesticides remain in agricultural products or escape into the soil and water, causing serious ecological and environmental problems such as pesticide residues in food, soil degradation, water eutrophication, and biodiversity degradation. Traditional pesticide formulations urgently need to develop towards environmentally friendly formulations to promote the sustainable development of agriculture.

[0003] Pesticide suspension concentrate (SC) is a new water-based formulation. Its basic characteristic is that the solid pesticide technical is uniformly dispersed in water in the form of fine particles to form a stable suspension system. This formulation has no problem of dust flying, is not flammable or explosive, has small particle size, high biological activity, large specific gravity, small packaging volume, and is safer and more environmentally friendly than other pesticide formulations. In addition, the main components of the suspension concentrate are water and surfactants, which have little impact on the environment and less phytotoxicity. Pesticide suspension concentrates have significant advantages in terms of efficacy, safety, environmental friendliness, and economy, and have become a pesticide variety with a large tonnage in the new water-based pesticide formulations.

[0004] At the same time, pesticide suspension concentrates also have some disadvantages, including easy precipitation and poor storage stability. The suspension concentrate is prone to poor physical stability during long-term storage, mainly manifested as phenomena such as pasting, delamination, bottom sedimentation, and water separation. Since the suspension concentrate contains a relatively large amount of pesticide technical, the suspension of the drug components is poor and easy to precipitate. Therefore, it is necessary to improve its stability by controlling the production method, adjusting the drug formula, etc.

[0005] CN118511873A discloses a bactericidal preparation containing a particle size growth inhibitor and its preparation process. The bactericidal preparation containing a particle size growth inhibitor includes compound A (substituted pyrazole compound), compound B, agriculturally acceptable auxiliaries, and water; the particle size growth inhibitor is polyvinyl acetate, polyvinylpyrrolidone, sodium polyphosphate, or acrylic acid copolymer. After using this particle size growth inhibitor to prepare a solid-liquid dispersion system product, the problems of excessive particle size growth (particle size D50 / 90 growth > 50%) and a decrease in effective suspension rate (effective suspension rate < 95%) after heat storage test (54°C, 14d) compared with the sample stored at room temperature are solved.

[0006] CN117918366A discloses a pesticide preparation with high adhesiveness to plant leaves. The pesticide preparation comprises the following components: chlorantraniliprole, emamectin benzoate, dispersant, synergist, stabilizer, defoamer, preservative, antifreeze, thickener, deionized water. The pesticide preparation solves the problems of high resistance of chlorantraniliprole, easy decomposition of emamectin benzoate in the natural environment, poor retention of the liquid medicine on plant leaves, and low drug utilization rate through a specific synergist combination and stabilizer combination. It can also effectively solve the problem of uneven dispersion of the active ingredient in the preparation caused by the increase in the particle size of the active ingredient, which makes it difficult to mix evenly during field use and results in excessive drug concentration on the surface of some plants, causing phytotoxicity.

[0007] The pesticide preparation prepared by the above patent does not belong to a water-soluble pesticide suspension, does not have a very excellent performance in maintaining the stability of the pesticide suspension before and after heat storage, cold storage, and freeze-thaw storage, and has a relatively complex formula composition, high cost, and relatively cumbersome preparation process steps. Summary of the Invention

[0008] The purpose of the present invention is to provide a pesticide suspension containing clothianidin and chlorfenapyr. By compounding a thickener and a dispersant, and through the synergistic effect of the thickener and the dispersant, the storage stability of the clothianidin and chlorfenapyr pesticide suspension is improved.

[0009] The present invention discloses the following technical solutions:

[0010] A pesticide suspension containing clothianidin and chlorfenapyr, the components and mass percentage contents are as follows:

[0011] Clothianidin, 10% - 30%;

[0012] Chlorfenapyr, 5% - 25%;

[0013] Thickener, 10% - 35%;

[0014] Dispersant, 2% - 15%;

[0015] The balance is water;

[0016] The thickener is a mixture of magnesium aluminum silicate, precipitated silica, and a 1wt% xanthan gum aqueous solution;

[0017] The dispersant is an aqueous solution of a polymer or a mixed aqueous solution of a polymer and DETA, and the polymer is:

[0018]

[0019] Further, the molar ratio of the DETA to the high molecular polymer is 0.01:1 to 1:0.05. Preferably, it is 0.05:1 to 1:0.1. The concentration of the high molecular polymer in the aqueous solution is 0.5 wt% to 12 wt%.

[0020] Further, the aluminum magnesium silicate accounts for 0.1% to 2% of the total mass of the suspending agent, the precipitated silica accounts for 0.5% to 3% of the total mass of the suspending agent, and the 1 wt% xanthan gum aqueous solution accounts for 10% to 30% of the total mass of the suspending agent.

[0021] Further, it further includes an antifreeze agent, and the antifreeze agent is one or both of ethylene glycol and propylene glycol, and the dosage is 1% to 8% of the total mass of the pesticide suspending agent. Preferably, the antifreeze agent is ethylene glycol, and the dosage is 4% of the total mass of the pesticide suspending agent.

[0022] Further, it further includes an antifoaming agent, and the antifoaming agent is one or both of AF1501 and AFE2010; the dosage is 0.05% to 1% of the total mass of the pesticide suspending agent. Preferably, the antifoaming agent is AF1501, and the dosage is 0.3% of the total mass of the pesticide suspending agent.

[0023] Further, it further includes a pH stabilizer, and the pH stabilizer is one or more of citric acid, sorbic acid, and tartaric acid, and the dosage is 0.04% to 1% of the total mass of the pesticide suspending agent. Preferably, the pH stabilizer is citric acid, and the dosage is 0.2% of the total mass of the pesticide suspending agent.

[0024] When the high molecular polymer dispersant and the thickener coexist in the suspending agent system, the high molecular polymer dispersant forms an adsorption layer on the surface of the pesticide particles, increasing the number of charges on the particle surface and the repulsive force between the particles. Due to its high molecular weight and many adsorption sites, it prevents the aggregation and precipitation of particles through electrostatic and steric repulsion effects, thereby maintaining the uniform dispersion state of the pesticide suspending agent; when the thickener is added to the solvent, the thickener molecules will curl and entangle with each other, and there will be an association effect between the thickener molecules, so that the overall viscosity of the suspending agent system is controlled within a reasonable range. Therefore, the synergistic effect of the high molecular polymer dispersant and the thickener promotes the stability, uniformity, and viscosity of the suspending agent to be maintained in the best state, and they work together to improve the storage stability of the suspending agent.

[0025] Advantages and beneficial effects of the present invention:

[0026] The pesticide suspending agent containing clothianidin and chlorfenapyr of the present invention can still maintain a relatively thin appearance texture, no stratification, no pasting, and good fluidity after being stored at normal temperature, hot storage, cold storage, and freeze-thaw storage for 14 days. Description of the drawings

[0027] Figure 1 Photographs of the 28% clothianidin·chlorfenapyr SC prepared in Examples 1-2 and Comparative Examples 1-3 after grinding (at room temperature).

[0028] Figure 2 Photographs of the 28% clothianidin·chlorfenapyr SC prepared in Examples 1-2 and Comparative Examples 1-3 after heat storage for 14 days.

[0029] Figure 3 Photographs of the 28% clothianidin·chlorfenapyr SC prepared in Examples 1-2 and Comparative Examples 1-3 after cold storage for 14 days.

[0030] Figure 4 Photographs of the 28% clothianidin·chlorfenapyr SC prepared in Examples 1-2 and Comparative Examples 1-3 after freeze-thaw storage for 14 days.

[0031] Figure 5 Particle size results of the 28% clothianidin·chlorfenapyr SC prepared in Examples 1-2 and Comparative Examples 1-3 before and after heat storage.

[0032] Figure 6 Particle size results of the 28% clothianidin·chlorfenapyr SC prepared in Examples 1-2 and Comparative Examples 1-3 before and after cold storage.

[0033] Figure 7 Particle size results of the 28% clothianidin·chlorfenapyr SC prepared in Examples 1-2 and Comparative Examples 1-3 before and after freeze-thaw storage. Detailed implementation mode

[0034] It should be noted that the following detailed description is exemplary and is intended to provide further illustration of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention pertains.

[0035] Example 1

[0036] The formulation and preparation process of the 28% clothianidin·chlorfenapyr SC. The preparation formulation of the 28% clothianidin·chlorfenapyr SC (100 g) is shown in Table 1. Among them, the pesticide technical clothianidin is a water-soluble pesticide. When the temperature is 20 °C, the solubility of clothianidin in water is 327 mg / L.

[0037] Table 1 Preparation formulation of 28% clothianidin·chlorfenapyr SC

[0038]

[0039] The thickener consists of magnesium aluminum silicate, precipitated silica, and 1 wt% xanthan gum aqueous solution, where magnesium aluminum silicate accounts for 0.8% of the total mass of the suspending agent, precipitated silica accounts for 1.3% of the total mass of the suspending agent, and 1 wt% xanthan gum aqueous solution accounts for 20% of the total mass of the suspending agent.

[0040] The dispersant is an aqueous solution mixture of a high molecular polymer and DETA, numbered g / D. The high molecular polymer is:

[0041]

[0042] The molar ratio of DETA to the high molecular polymer is 1:1. The concentration of the high molecular polymer in the aqueous solution is 3 wt%.

[0043] The specific steps of the preparation process of the suspending agent of the present invention are as follows:

[0044] Step 1: First, take a 250 mL beaker, add a magnetic stirrer, deionized water and ethylene glycol in sequence, then add the dispersant, and place it on a stirrer to stir until completely dissolved;

[0045] Step 2: Add a pH stabilizer, a thickener, clothianidin, chlorfenapyr and an antifoaming agent in sequence, and mix and stir evenly;

[0046] Step 3: Add it together with sand grinding zirconia beads to a sand grinding tank, and grind it on a vertical sand mill for 2 h;

[0047] Step 4: After grinding for 2 h, take it out from the sand grinding tank, filter it, and put it into a 150 mL sample bottle for storage and standby.

[0048] The test method for the storage stability of the above 28% clothianidin·chlorfenapyr SC is as follows:

[0049] Step 1: Observe the appearance properties, fluidity, and whether there is stratification, and then perform particle size analysis (at room temperature) using a laser particle size distribution analyzer respectively.

[0050] Step 2: Divide 28% clothianidin·chlorfenapyr SC into 3 portions and put them into 20 mL sample bottles, and store them in environments of 54 °C (hot storage), 0 °C (cold storage) and -18 °C (freeze-thaw storage) for 14 d. During the 14 d storage period of hot storage and cold storage, there is no need to take them out, and they are taken out until after 14 d of storage; during the 14 d storage period of freeze-thaw storage, it is necessary to experience repeated freeze-thaw cycles of freezing for 2 - 3 d and then taking out and melting for 2 - 3 d three times.

[0051] Step 3: Observe the appearance properties, fluidity, and whether there is stratification of 28% clothianidin·chlorfenapyr SC after 14 d of storage, and then perform particle size analysis (hot storage, cold storage and freeze-thaw) using a laser particle size distribution analyzer respectively.

[0052] Example 2

[0053] The difference from Example 1 is that EDTA is not used in the dispersant, numbered g.

[0054] Comparative Example 1

[0055] The difference from Example 1 is that the dispersant is replaced with the following polymer, numbered b.

[0056]

[0057] Comparative Example 2

[0058] The difference from Comparative Example 2 is that the dispersant also includes DETA, and the molar ratio of DETA to the polymer is 1:1, numbered b / D.

[0059] Comparative Example 3

[0060] The difference from Example 1 is that the dispersant is replaced with a commercially available dispersant SP-SC29 + SP-27001.

[0061] Result analysis:

[0062] The results of the appearance properties of 28% clothianidin·chlorfenapyr SC at room temperature and after 14 days of storage are shown in Table 2. Among them, the appearance property textures of the SP-SC29 + SP-27001 group, b group, b / D group, g group, and g / D group were all relatively thin after 2 hours of grinding (at room temperature), without stratification, without pasting, and had good fluidity, meeting the appearance property requirements of pesticide suspension concentrates. The appearance property textures of the SP-SC29 + SP-27001 group and b group were all relatively thin after heat storage, cold storage, and freeze-thaw storage for 14 days, without pasting, and had good fluidity, but there was a little stratification at a certain height above the suspension concentrate. The appearance property textures of the b / D group were relatively viscous after heat storage and cold storage for 14 days, without stratification, without pasting, and had a certain fluidity; after freeze-thaw storage for 14 days, the appearance property textures were relatively viscous, without stratification, without pasting, and had a certain fluidity, but there was a little stratification at a certain height above the suspension concentrate. The appearance property textures of the g group and g / D group were all relatively thin after heat storage, cold storage, and freeze-thaw storage for 14 days, without stratification, without pasting, and had good fluidity, meeting the appearance property requirements of pesticide suspension concentrates.

[0063] Table 2 Results of the appearance properties of 28% clothianidin·chlorfenapyr SC before and after storage

[0064]

[0065] The results of the particle size of 28% clothianidin·chlorfenapyr SC at room temperature and after 14 days of storage are as Figure 1 、 Figure 2 and Figure 3As shown in the figure. Among them, the particle size of the SP-SC29 + SP-27001 group was relatively large after grinding for 2 h (at room temperature), at 7.465 μm; the particle size increased significantly after 14 days of heat storage, cold storage, and freeze-thaw storage, and the increase was in the range of 1.3 - 3.3 μm. The particle size of group b was less than 5 μm after grinding for 2 h (at room temperature), meeting the particle size requirements of pesticide suspending agents; the particle size increased significantly after 14 days of heat storage, with an increase of 7.3 μm; the particle size was less than 5 μm after 14 days of cold storage and freeze-thaw storage, and there was no significant difference in particle size before and after storage, and the particle size change was small, with the particle size change amount less than 1 μm. The particle size of group b / D was less than 5 μm after grinding for 2 h (at room temperature), meeting the particle size requirements of pesticide suspending agents; the particle size increased slightly after 14 days of heat storage, with an increase of 1.5 μm; the particle size was less than 5 μm after 14 days of cold storage and freeze-thaw storage, and there was no significant difference in particle size before and after storage, and the particle size change was small. The particle sizes of groups g and g / D were less than 5 μm after grinding for 2 h (at room temperature) and after 14 days of storage, meeting the particle size requirements of pesticide suspending agents, and there was no significant difference in particle size before and after storage, and the particle size change was small.

[0066] In summary, the polymer dispersants g and g / D have the best effect on maintaining the stability of 28% clothianidin·chlorfenapyr SC before and after heat storage, cold storage, and freeze-thaw storage, with better effects than the commercially available dispersant SP-SC29 + SP-27001. They can effectively maintain the good fluidity and viscosity of the suspending agent system of 28% clothianidin·chlorfenapyr SC before and after storage, and there is no layering or pasting phenomenon before and after storage; the polymer dispersants b and b / D have relatively poor effects on maintaining the stability of 28% clothianidin·chlorfenapyr SC before and after heat storage, cold storage, and freeze-thaw storage.

[0067] Comparative Example 4

[0068] The difference from Example 1 is that the thickener is a composition of magnesium aluminum silicate and precipitated silica, where magnesium aluminum silicate accounts for 10% of the total mass of the suspending agent, and precipitated silica accounts for 12.1% of the total mass of the suspending agent.

[0069] Comparative Example 5

[0070] The difference from Example 1 is that the thickener is a composition of magnesium aluminum silicate and 1 wt% xanthan gum aqueous solution, where magnesium aluminum silicate accounts for 10% of the total mass of the suspending agent, and 1 wt% xanthan gum aqueous solution accounts for 12.1% of the total mass of the suspending agent.

[0071] Comparative Example 6

[0072] The difference from Example 1 is that the thickener is a composition of precipitated silica and 1 wt% xanthan gum aqueous solution, where precipitated silica accounts for 10% of the total mass of the suspending agent, and 1 wt% xanthan gum aqueous solution accounts for 12.1% of the total mass of the suspending agent.

[0073] Result analysis:

[0074] The results of the appearance properties of 28% clothianidin·chlorfenapyr SC at room temperature and after 14 days of storage are shown in Table 3. Among them, for Comparative Examples 4-6, after grinding for 2 h (at room temperature), the appearance properties and texture were relatively thin, without stratification, without pasting, with good fluidity, meeting the requirements for the appearance properties of pesticide suspension concentrates. After 14 days of hot storage, cold storage, and freeze-thaw storage, the appearance properties and texture were viscous, without stratification, with pasting, and without fluidity. It shows that if the proportion of the thickener is changed or the thickener component is reduced, the stability effect of the finally prepared 28% clothianidin·chlorfenapyr SC before and after hot storage, cold storage, and freeze-thaw storage will become worse.

[0075] Table 3 Results of the appearance properties of 28% clothianidin·chlorfenapyr SC before and after storage

[0076]

[0077] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the inventive concept, several modifications and improvements can be made, and these all belong to the protection scope of the present invention.

Claims

1. A pesticide suspension containing clothianidin and chlorfenapyr, characterized in that, The components and their mass percentages are as follows: Clothianidin, 10% - 30%; Chlorfenapyr, 5% - 25%; Thickener, 10% - 35%; Dispersant, 2% - 15%; The balance is water; The thickener is a mixture of magnesium aluminum silicate, precipitated silica, and 1wt% xanthan gum aqueous solution; The dispersant is an aqueous solution of a high molecular polymer or a mixed aqueous solution of a high molecular polymer and DETA. The high molecular polymer is: (x = 10 - 350, y = 7 - 750, n = 3 - 130).

2. The pesticide suspension agent containing clothianidin and chlorfenapyr according to claim 1, characterized in that The molar ratio of DETA to the high molecular polymer is 0.01:1 - 1:0.05; the concentration of the high molecular polymer in the aqueous solution is 0.5wt% - 12wt%.

3. The pesticide suspension concentrate containing clothianidin and chlorfenapyr according to claim 1, characterized in that, The magnesium aluminum silicate accounts for 0.1% - 2% of the total mass of the suspending agent, the precipitated silica accounts for 0.5% - 3% of the total mass of the suspending agent, and the 1wt% xanthan gum aqueous solution accounts for 10% - 30% of the total mass of the suspending agent.

4. The pesticide suspension agent containing clothianidin and chlorfenapyr according to claim 1, characterized in that, It also includes an antifreeze agent, which is one or both of ethylene glycol and propylene glycol, and the dosage is 1% - 8% of the total mass of the pesticide suspending agent.

5. The pesticide suspension concentrate containing clothianidin and chlorfenapyr according to claim 4, wherein, The antifreeze agent is ethylene glycol, and the dosage is 4% of the total mass of the pesticide suspending agent.

6. The pesticide suspension agent containing clothianidin and chlorfenapyr according to claim 1, characterized in that, It also includes an antifoaming agent, which is one or both of AF1501 and AFE2010; the dosage is 0.05% - 1% of the total mass of the pesticide suspending agent.

7. The pesticide suspension concentrate containing clothianidin and chlorfenapyr according to claim 6, wherein, The antifoaming agent is AF1501, and the dosage is 0.3% of the total mass of the pesticide suspending agent.

8. The pesticide suspension concentrate containing clothianidin and chlorfenapyr according to claim 1, characterized in that, It also includes a pH stabilizer, which is one or more of citric acid, sorbic acid, and tartaric acid, and the dosage is 0.04% - 1% of the total mass of the pesticide suspending agent.

9. The pesticide suspension concentrate containing clothianidin and chlorfenapyr according to claim 8, wherein, The pH stabilizer is citric acid, and the dosage is 0.2% of the total mass of the pesticide suspending agent.

10. The pesticide suspension agent containing clothianidin and chlorfenapyr according to any one of claims 1 to 3, characterized in that, It also includes an antifreeze agent, an antifoaming agent, and a pH stabilizer. The antifreeze agent is one or both of ethylene glycol and propylene glycol, and the dosage is 1% - 8% of the total mass of the pesticide suspending agent; the antifoaming agent is one or both of AF1501 and AFE2010; the dosage is 0.05% - 1% of the total mass of the pesticide suspending agent; the pH stabilizer is one or more of citric acid, sorbic acid, and tartaric acid, and the dosage is 0.04% - 1% of the total mass of the pesticide suspending agent.

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