Soluble concentrate containing aquacide dichloride and refined glufosinate ammonium and preparation method thereof

Abstract

The invention relates to the technical field of pesticides, in particular to a soluble concentrate containing aquacide dichloride and refined glufosinate ammonium and a preparation method of the soluble concentrate. The herbicide comprises the following components: diquat dichloride, refined glufosinate ammonium, a dispersing agent and water, the dispersing agent comprises a plant alkyl betaine mixture and alkylamine polyoxyethylene ether quaternary ammonium salt. The dispersing agent comprises a plant alkyl betaine mixture and alkylamine polyoxyethylene ether quaternary ammonium salt, and can improve the normal temperature stability of the soluble concentrate of diquat dichloride and refined glufosinate ammonium salt; the weight ratio of the alkylamine polyoxyethylene ether quaternary ammonium salt to the plant alkyl betaine mixture is 1: (2-5), so that the low-temperature and high-temperature storage stability of the soluble concentrate can be further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticides, and in particular to a soluble solution containing diquat dichloride and glufosinate ammonium and a preparation method thereof. Background Art

[0002] Amidst the ongoing advancements in pesticide formulation technology, soluble concentrates, as a highly effective and environmentally friendly formulation, are widely used in the formulation of herbicides, fungicides, and other pesticides due to their excellent dispersibility, stability, and ease of dilution. However, traditional soluble concentrate formulations often suffer from issues such as poor dispersibility, insufficient stability, high foaming, and crystallization at low temperatures, which compromise efficacy and product performance. Diquat dichloride and glufosinate ammonium are two important herbicide ingredients, each with distinct mechanisms of action and application characteristics. Combining these two can broaden the herbicide spectrum and provide more comprehensive control of various annual weeds in non-arable land.

[0003] Chinese invention patent application CN117562068A discloses a herbicidal composition and its use. The composition comprises active ingredients A and B, wherein active ingredient A is diquat dichloride and active ingredient B is glufosinate ammonium salt, selected from glufosinate ammonium salt and glufosinate sodium salt. The mass ratio of active ingredient A to active ingredient B is 1:15 to 15:1. The herbicidal composition has good control effects on various weeds, maintains good stability in low-temperature environments, and has a long-lasting effect. However, the composition does not involve research on the stability of soluble solutions, which limits its scope of application. Summary of the Invention

[0004] The first aspect of the present invention provides a soluble solution containing diquat dichloride and glufosinate ammonium, the components of which include: diquat dichloride, glufosinate ammonium, a dispersant, and water.

[0005] The total weight of the diquat dichloride and glufosinate ammonium in the soluble solution is ≥10 wt%.

[0006] Optionally, the total weight of the diquat dichloride and glufosinate ammonium in the soluble solution is ≥20 wt%.

[0007] Optionally, the total weight of the diquat dichloride and glufosinate ammonium in the soluble solution is ≥30 wt%.

[0008] Optionally, the total weight of the diquat dichloride and glufosinate ammonium salt in the soluble solution is 30-40 wt%.

[0009] The weight ratio of diquat dichloride to glufosinate ammonium is (1.5-2.5):1.

[0010] Optionally, the weight ratio of diquat dichloride to glufosinate ammonium is (1.7-2):1.

[0011] The dispersant comprises a mixture of alkylamine polyoxyethylene ether quaternary ammonium salt and plant alkyl betaine.

[0012] This study found that a dispersant comprising a mixture of plant-based alkyl betaines and quaternary ammonium salts of alkylamine polyoxyethylene ethers can improve the room-temperature stability of soluble solutions of diquat dichloride and glufosinate ammonium. Plant-based alkyl betaines, as zwitterionic surfactants, possess excellent wettability and emulsification properties, reducing the surface tension of the solution and improving its adhesion to plant surfaces. Alkylamine polyoxyethylene ether quaternary ammonium salts, on the other hand, as cationic surfactants, exhibit strong hard water resistance and low-temperature stability. When combined, these two agents create a synergistic effect, improving the stability of the solution under various environmental conditions. Further research revealed that a weight ratio of the quaternary ammonium salts to the plant-based alkyl betaine mixture of 1:2-5 further improved the low- and high-temperature storage stability of the soluble solution. Plant-based alkyl betaines exhibit good water solubility at low temperatures, effectively reducing the viscosity of the solution and improving its fluidity. Alkylamine polyoxyethylene ether quaternary ammonium salts, on the other hand, exhibit excellent stability at high temperatures, preventing stratification or precipitation of the solution at high temperatures. The combined use of the two can significantly improve the dispersion stability of the drug solution under low and high temperature conditions.

[0013] Optionally, the brand of the alkylamine polyoxyethylene ether quaternary ammonium salt is WS-302, purchased from Nanjing Well Biochemical Co., Ltd.; the brand of the plant alkyl betaine mixture is WS-301, purchased from Nanjing Well Biochemical Co., Ltd.

[0014] The weight ratio of the alkylamine polyoxyethylene ether quaternary ammonium salt and the plant alkyl betaine mixture is 1:(2-5).

[0015] Optionally, the weight ratio of the alkylamine polyoxyethylene ether quaternary ammonium salt and the plant alkyl betaine mixture is 1:(2-4).

[0016] Optionally, the weight ratio of the alkylamine polyoxyethylene ether quaternary ammonium salt and the plant alkyl betaine mixture is 1:2.5.

[0017] The content of the dispersant in the soluble solution is ≤30 wt%.

[0018] Optionally, the content of the dispersant in the soluble solution is 10-30 wt%.

[0019] Optionally, the content of the dispersant in the soluble solution is 20-30 wt%.

[0020] The second aspect of the present invention provides a soluble agent containing diquat dichloride and glufosinate ammonium, comprising the following steps: adding a dispersant to water, mixing uniformly, and then adding diquat dichloride and glufosinate ammonium to obtain a soluble agent containing diquat dichloride and glufosinate ammonium.

[0021] Beneficial effects

[0022] 1. The dispersant includes a plant alkyl betaine mixture and an alkylamine polyoxyethylene ether quaternary ammonium salt, which can improve the room temperature stability of the soluble solution of diquat dichloride and glufosinate ammonium.

[0023] 2. The weight ratio of the mixture of alkylamine polyoxyethylene ether quaternary ammonium salt and plant alkyl betaine is 1: (2-5), which can further improve the low-temperature and high-temperature storage stability of the soluble solution.

[0024] 3. The weight ratio of the mixture of alkylamine polyoxyethylene ether quaternary ammonium salt and plant alkyl betaine is 1: (2-4), which can improve the dilution stability of the soluble solution. When diluted 20 times, the dilution liquid is uniform and there is no precipitate.

[0025] 4. The soluble solution of diquat dichloride and glufosinate ammonium in the present application has excellent long-lasting foaming properties.

[0026] 5. The soluble preparation of diquat dichloride and glufosinate ammonium in the present application maintains stability while the active ingredient content can reach 30 wt%. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 This is a photo of the soluble preparation containing diquat dichloride and glufosinate ammonium after heat storage according to Example 1.

[0028] Figure 2 This is a photo of the soluble solution containing diquat dichloride and glufosinate ammonium in Comparative Example 3 after heat storage. DETAILED DESCRIPTION

[0029] Example 1

[0030] A soluble agent containing diquat dichloride and glufosinate ammonium salt, comprising: diquat dichloride (42 wt% of diquat dichloride mother liquor, solvent is water), glufosinate ammonium salt (50 wt% of glufosinate ammonium salt mother liquor, solvent is water), a dispersant, and deionized water. The sum of the mass of the diquat dichloride and the mass of the glufosinate ammonium salt in the soluble agent is 30.9 wt%, and the mass of the dispersant in the soluble agent is 21 wt%.

[0031] The weight ratio of diquat dichloride to glufosinate ammonium is 20:10.9.

[0032] The dispersant is: a mixture of alkylamine polyoxyethylene ether quaternary ammonium salt and plant alkyl betaine; the brand of the alkylamine polyoxyethylene ether quaternary ammonium salt is WS-302, purchased from Nanjing Well Biochemical Co., Ltd.; the brand of the plant alkyl betaine mixture is WS-301, purchased from Nanjing Well Biochemical Co., Ltd.; the weight ratio of the alkylamine polyoxyethylene ether quaternary ammonium salt and the plant alkyl betaine mixture is 1:2.5.

[0033] The second aspect of the present invention provides a soluble preparation containing diquat dichloride and refined glufosinate ammonium salt, comprising the following steps: adding a mixture of alkylamine polyoxyethylene ether quaternary ammonium salt and plant alkyl betaine to deionized water, mixing uniformly, and then adding a mother liquor of diquat dichloride with a content of 42 wt% and a mother liquor of refined glufosinate ammonium salt with a content of 50 wt%, such as Figure 1 As shown, a soluble solution containing diquat dichloride and glufosinate ammonium is obtained.

[0034] Example 2

[0035] The specific implementation is the same as that of Example 1; except that the total weight of diquat dichloride and glufosinate ammonium in the soluble solution in Example 2 is 20 wt%.

[0036] Example 3

[0037] The specific embodiment is the same as Example 1; except that the sum of the mass of diquat dichloride and glufosinate ammonium in the soluble solution in Example 3 is 10 wt%.

[0038] Comparative Example 1

[0039] The specific implementation is the same as Example 1; the difference is that the dispersant in Comparative Example 1 is calcium dodecylbenzenesulfonate, and the content of the dispersant in the soluble solution is 2 wt%.

[0040] Comparative Example 2

[0041] The specific implementation is the same as Example 1; the difference is that the dispersant in Comparative Example 2 is styrene phenol polyoxyethylene ether, and the content of the dispersant in the soluble solution is 3 wt %.

[0042] Comparative Example 3

[0043] The specific embodiment is the same as in Example 1; except that the dispersant in Comparative Example 3 is castor oil polyoxyethylene ether, and the content of the dispersant in the soluble solution is 2.5wt%, such as Figure 2 As shown, a soluble solution containing diquat dichloride and glufosinate ammonium is obtained.

[0044] Comparative Example 4

[0045] The specific implementation is the same as Example 1; the difference is that the dispersant in Comparative Example 4 is alkylnaphthalene sulfonate, and the content of the dispersant in the soluble solvent is 3 wt%.

[0046] Comparative Example 5

[0047] The specific implementation is the same as Example 1; the difference is that the dispersant in Comparative Example 3 is a polyol fatty acid ester, and the content of the dispersant in the soluble solution is 4 wt%.

[0048] Comparative Example 6

[0049] The specific implementation is the same as Example 1; the difference is that the dispersant in Comparative Example 4 is alkylphenol polyoxyethylene ether, and the content of the dispersant in the soluble solution is 2.5 wt%.

[0050] Performance testing methods and data

[0051] 1. The embodiment was subjected to field test, and the test data are listed in Table 1.

[0052] The experiment was conducted in August 2024 at Laodaohe Road, Yong'an Town, Liuyang City, Changsha City, Hunan Province. The experimental site was surrounded by non-arable land. The experiment was repeated 4 times per treatment, and the plot area was 30m 2 , a total of 20 plots, arranged in random blocks. Using the stem-leaf spray method, the pesticide was applied during the period of vigorous weed growth. Using the stem-leaf spray method, the test substance was sprayed uniformly in each plot one by one, from the control substance, and from low dose to high dose. An electric sprayer was used, and the spray volume was 40 liters per mu, and 600 liters per hectare. A clear water treatment was also set as a blank control. The weed control efficacy and fresh weight control efficacy were investigated 30 days after the application. Efficacy calculation method: The efficacy was calculated according to formula 1:

[0053]

[0054] Where: PT---the number of remaining grasses (or fresh weight) in the pesticide-treated area;

[0055] CK---number of live grasses (or fresh weight) in the blank control area.

[0056] 2. The soluble solutions of Example 1 and the comparative example were subjected to physical and chemical tests. The test results of Example 1 are shown in Table 2, and the test results of the comparative example are shown in Table 3.

[0057] The thermal storage stability test method is as follows: according to 4.4.1 of GB / T19136-2021, the evaluation method is: after thermal storage, the mass fraction of diquat dichloride, refined glufosinate ammonium, and refined glufosinate ammonium salt should not be less than 95% of the mass fraction measured before thermal storage, and the ratio of refined glufosinate enantiomers, the mass fraction of 2,2′-bipyridine, the mass fraction of dichloroethane, the mass fraction of total terpyridine, the pH value, and the dilution stability are qualified if they meet the requirements of Table 2. Figure 1 As shown, there is no change after thermal storage in the embodiment, as shown in FIG. Figure 2 As shown, Comparative Example 3 exhibited obvious crystallization precipitation.

[0058] The cold storage stability test method is: according to 4.4.1 of GB / T19136-2021, and the evaluation method is: after cold storage, the volume of the precipitate at the bottom of the centrifuge tube is no more than 0.3mL, which is qualified.

[0059] Performance test data

[0060] Table 1

[0061]

[0062]

[0063] Table 2

[0064]

[0065] Table 3

[0066] Comparative Example Thermal storage stability Cold storage stability Comparative Example 1 qualified Crystallization precipitation Comparative Example 2 Crystallization precipitation qualified Comparative Example 3 Crystallization precipitation Crystallization precipitation Comparative Example 4 Crystallization precipitation qualified Comparative Example 5 qualified Crystallization precipitation Comparative Example 6 Crystallization precipitation qualified

Claims

1. A soluble preparation containing diquat dichloride and glufosinate ammonium, characterized in that: The components include: diquat dichloride, glufosinate ammonium, dispersant and water; the dispersant includes a plant alkyl betaine mixture and alkylamine polyoxyethylene ether quaternary ammonium salt.

2. The soluble agent containing diquat dichloride and glufosinate ammonium according to claim 1, characterized in that: The total weight of the diquat dichloride and glufosinate ammonium in the soluble solution is ≥10 wt%.

3. The soluble solution containing diquat dichloride and glufosinate ammonium according to claim 2, characterized in that: The total weight of the diquat dichloride and glufosinate ammonium in the soluble solution is ≥30 wt%.

4. The soluble solution containing diquat dichloride and glufosinate ammonium according to claim 1 or 3, characterized in that: The weight ratio of diquat dichloride to glufosinate ammonium is (1.5-2.5):

1.

5. The soluble solution containing diquat dichloride and glufosinate ammonium according to claim 4, characterized in that: The weight ratio of diquat dichloride to glufosinate ammonium is (1.7-2):

1.

6. The soluble solution containing diquat dichloride and glufosinate ammonium according to claim 1 or 5, characterized in that: The weight ratio of the alkylamine polyoxyethylene ether quaternary ammonium salt and the plant alkyl betaine mixture is 1:(2-5).

7. The soluble solution containing diquat dichloride and glufosinate ammonium according to claim 6, characterized in that: The weight ratio of the alkylamine polyoxyethylene ether quaternary ammonium salt and the plant alkyl betaine mixture is 1: (2-4)。 8. The soluble solution containing diquat dichloride and glufosinate ammonium according to claim 7, characterized in that: The content of the dispersant in the soluble solution is ≤30 wt%.

9. The soluble solution containing diquat dichloride and glufosinate ammonium according to claim 8, characterized in that: The content of the dispersant in the soluble solution is 10-30 wt%.

10. A soluble concentrate containing diquat dichloride and glufosinate ammonium according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: adding a dispersant into water, mixing the mixture evenly, and then adding diquat dichloride and glufosinate ammonium to obtain a soluble solution containing diquat dichloride and glufosinate ammonium.

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