A kind of two-component fungicide containing fluoxastrobin and its preparation method

Abstract

The application discloses a kind of two-component fungicide containing fluoximide, effective component includes fluoximide and propiconazole, and the weight ratio of fluoximide and propiconazole is 1 :(0.2-3).The application has good control effect on banana leaf spot disease, and is safe to banana, can delay the process of drug resistance of drug resistance;And the combination of aryl phenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether is used as emulsifying agent, and the prepared pesticide microemulsion has good stability and short foaming time.Fluoximide and propiconazole mixed preparation have good synergistic effect, can reduce the amount of drug, delay and control the drug resistance of pathogenic bacteria, and also make the mixed preparation have protection, treatment and internal absorption, realize the purpose of taking long and short, complementary advantages, expand the control spectrum and use range.

Description

Technical Field

[0001] This invention relates to a two-component fungicide containing fluopyram and its preparation method, and relates to A01N, specifically to the field of biocides. Background Technology

[0002] Fluopyram is a carboxylic acid amide fungicide, while propiconazole is a sterol inhibitor. By affecting the biosynthesis of sterols, propiconazole disrupts the cell membrane function of pathogens, ultimately leading to cell death, thus achieving the effects of fungicide, disease prevention, and treatment. Combining fluopyram and propiconazole, which have different drug mechanisms, can delay the development of drug resistance in diseases. However, fluopyram and propiconazole have poor compatibility with water, resulting in low stability of the prepared agent. Long-term storage in high-temperature environments can lead to oil floating, causing the active ingredients to dissolve, reducing the uniformity of efficacy, and compromising the use of the agent.

[0003] Chinese invention patent CN201010512138.1 discloses a fungicide composition containing fluopyram and propiconazole, which shows good control effects on cucumbers and zucchini through synergistic action. However, the concentration of the agents used is relatively high, which may cause certain pesticide residues on crops. Chinese invention patent CN201610057887.7 discloses a ternary fungicide and nematicide composition with synergistic effects, using a combination of fluopyram, abamectin and its derivatives, and triazole fungicides. It has the effects of low dosage, environmental friendliness, and low pesticide residues. However, the prepared suspension or microcapsule suspension has poor storage stability and is not suitable for long-term storage. Summary of the Invention

[0004] In order to improve the efficacy of fungicides, reduce the dosage of fungicides, and improve the stability of fungicides, the first aspect of the present invention provides a two-component fungicide containing fluopyram, wherein the active ingredients include fluopyram and propiconazole, and the weight ratio of fluopyram to propiconazole is 1:(0.2-3).

[0005] In a preferred embodiment, the weight ratio of fluopyram to propiconazole is 1:(1-3), and more preferably, the weight ratio of fluopyram to propiconazole is 1:2.

[0006] The applicant discovered that using fluopyram and propiconazole as the active ingredients in a fungicide, with a weight ratio of 1:2, provides good control of banana leaf spot disease and is safe for bananas, without causing phytotoxicity. The speculated reason is that propiconazole inhibits sterol biosynthesis, disrupting the cell membrane function of the pathogen. Fluopyram inhibits succinate dehydrogenase in complex II of the mitochondrial respiratory chain. After propiconazole disrupts the cell membrane, fluopyram further enhances its fungicidal effect, more effectively inhibiting fungal spore germination, germ tube, and mycelial growth. The applicant further found that a weight ratio of 1:2 for fluopyram and propiconazole achieves the highest toxicity against banana leaf spot disease without causing phytotoxicity. This may be because fluopyram and propiconazole have different mechanisms of action; at an appropriate weight ratio, a higher lethality rate can be achieved, and the proportion of biological screening is reduced, thus lowering the likelihood of phytotoxicity.

[0007] In a preferred embodiment, the bactericide is selected from one of the following formulations: microemulsion, emulsifiable concentrate, suspension emulsion, microcapsule suspension-suspension, and water emulsion.

[0008] In a preferred embodiment, the active ingredient in the microemulsion accounts for 10-35% of the total mass of the microemulsion.

[0009] In a preferred embodiment, the raw materials for preparing the microemulsion further include, by weight percentage, 20-30% emulsifier, 5-15% cosolvent, 10-30% solvent, 8-15% compatibility agent, and diluent to 100%.

[0010] In a preferred embodiment, the diluent is water.

[0011] During the experiment, the applicant discovered that after heat storage, the prepared pesticide underwent a wet sieving test (passing through a 75μm sieve). The microcapsule suspension failed to meet the requirement of at least 98% passing through the 75μm sieve, with a large amount of white flaky residue remaining on the sieve, while the microemulsion met the standard. The reason may be that the microemulsion, composed of liquid pesticide, surfactant, water, and stabilizer, is a thermodynamically stable dispersion system. Using water as a medium, it contains little or no organic solvents, offering advantages such as non-flammability, non-explosiveness, safe production and storage, low environmental pollution, and significant savings in organic solvents. Furthermore, the pesticide dispersion is extremely high, reaching a micronized level, with pesticide particles typically ranging from 0.1 to 0.01 micrometers, appearing as a transparent or semi-transparent liquid. It exhibits good dispersibility in water, strong penetration into the target, and good adhesion.

[0012] In a preferred embodiment, the emulsifier is a nonionic surfactant, which is selected from one or a combination of several of polyoxyethylene nonionic surfactants, polyol nonionic surfactants, alkanolamide nonionic surfactants, and polyether nonionic surfactants.

[0013] In a preferred embodiment, the polyoxyethylene nonionic surfactant is selected from one or a combination of several of fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid polyoxyethylene esters, and arylphenol polyoxyethylene ethers.

[0014] In a preferred embodiment, the fatty alcohol in the fatty alcohol polyoxyethylene ether has 8-15 carbon atoms and an EO value of 5-9.

[0015] In a preferred embodiment, the fatty alcohol polyoxyethylene ether is a dodecyl alcohol polyoxyethylene ether.

[0016] In a preferred embodiment, the arylphenol polyoxyethylene ether is tristyrylphenol polyoxyethylene ether, and the emulsifier is a combination of fatty alcohol polyoxyethylene ether and arylphenol polyoxyethylene ether.

[0017] In a preferred embodiment, the weight ratio of the fatty alcohol polyoxyethylene ether to the arylphenol polyoxyethylene ether is 1:(3-7).

[0018] In a preferred embodiment, the weight ratio of the fatty alcohol polyoxyethylene ether to the arylphenol polyoxyethylene ether is 1:5.

[0019] During the experiment, the applicant discovered that using tristyrylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether with an EO value of 5-9 as emulsifiers resulted in good stability of the agent and a short foaming time. The applicant speculates that this is because the long-chain fatty alcohol polyoxyethylene ether with an EO value of 5-9 works synergistically with the arylphenol polyoxyethylene ether, with the long chain and benzene ring structure interpenetrating to form a stable interwoven network. However, due to the large steric hindrance of the tristyrylphenol structure, mutual repulsion occurs between the emulsion particles, preventing particle aggregation and thus ensuring good system stability. The applicant further discovered that a 5:1 weight ratio of arylphenol polyoxyethylene ether to fatty alcohol polyoxyethylene ether maintains a good rapid defoaming effect. This may be because arylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether can disrupt the stable surface tension at the system interface, causing a rapid change in surface tension, thereby achieving a good rapid defoaming effect.

[0020] During the experiment, the applicant further discovered that by adjusting the emulsification system and the HLB value of the formulation, the thermal stability of the system was significantly improved. After 14 days of thermal storage at 54℃, the formulation passed the thermal storage test and no turbidity was observed.

[0021] During the experiment, the applicant also found that the particle size of the microemulsion is generally between 0.1-0.01 μm, and it should be transparent or fluorescent after a 200-fold dilution in water. However, during the research and development process, it was found that the non-optimal emulsion system sample was milky white after a 200-fold dilution in water, similar to emulsified oil. The reason may be that the emulsifier's emulsification effect was insufficient. Then we adjusted the emulsifier, and after improvement, the formulation was transparent and fluorescent after a 200-fold dilution in water.

[0022] In a preferred embodiment, both the co-solvent and the solvent are organic solvents, selected from one or a combination of several of alcohol solvents, phenol solvents, ethyl acetate, amide solvents, and dimethyl sulfoxide.

[0023] In a preferred embodiment, the co-solvent is N,N-dimethyldecanoamide.

[0024] In a preferred embodiment, the solvent is N-methylpyrrolidone.

[0025] In a preferred embodiment, the weight ratio of N,N-dimethyldecanoamide to N-methylpyrrolidone is (0.5-1.5):2, and more preferably, the weight ratio of N,N-dimethyldecanoamide to N-methylpyrrolidone is 1:2.

[0026] During the experiment, the applicant discovered that the microemulsion formed by the synergistic effect of ADMA10 (N,N-dimethyldecylamide) and N-methylpyrrolidone exhibited good stability. After spraying onto leaves, the pesticide adhered well to the leaves, demonstrating a good control effect on the target leaves. The applicant speculated that this might be because fluopyram and propiconazole have poor water compatibility. By introducing N,N-dimethyldecylamide and N-methylpyrrolidone, the nonpolar groups approach the pesticide, while the polar groups are compatible with water, forming emulsion particles with nonpolar groups facing inwards and polar groups facing outwards. This significantly improved the water compatibility when dispersed in a solvent. The applicant further found that the prepared microemulsion adhered well to plant leaves. This might be because the surface of plant leaves is covered with a layer of villi. After the microemulsion falls onto the leaf surface, the polar structure is unstable, and after demulsification, the nonpolar pesticide structure is exposed, resulting in good systemic absorption on the leaves, thus achieving good control of banana leaf spot disease.

[0027] During the low-temperature stability test, the applicant found that crystal precipitation occurred during 7 days of cold storage at 0℃. This was caused by the precipitation of fluopyram technical material crystals, which was due to the insufficient solubility of fluopyram in the solvent. We improved the solubility of the system by using ADMA10 and N-methylpyrrolidone in a synergistic effect. The improved formulation did not show crystal precipitation during 7 days of cold storage at 0℃. In the subsequent test phase, it remained homogeneous, clear and transparent after being stored at -10℃ for 14 days, without any crystal precipitation.

[0028] In a preferred embodiment, the compatibility agent is a plant-based polyether polyol.

[0029] The introduction of plant-based polyether polyol compatibility agents in this application further improves the interaction between the fungicide and the plant. Plant-based polyether polyols can reduce the surface tension of the fungicide, increase the wetting and penetration effect on plant leaves, and also have a certain degree of adhesion to plant leaves, thus achieving long-lasting and long-acting fungicide. The compatibility agent is a plant-based compatibility agent with good biocompatibility, which reduces the occurrence of phytotoxicity while enhancing efficacy.

[0030] A second aspect of the present invention provides a method for preparing a two-component fungicide containing fluopyram, comprising the following steps:

[0031] (1) Add the co-solvent and solvent to the preparation tank, turn on the stirrer, add fluopyram and propiconazole to the preparation tank, and dissolve and mix for 30-50 minutes;

[0032] (2) Weigh the emulsifier accurately according to the feeding ratio and add it to the preparation tank. Turn on the stirrer to mix for more than 30 minutes.

[0033] (3) Finally, add deionized water and mix for 30-50 minutes.

[0034] (4) The mixed materials are sampled and analyzed. Once they meet the standard requirements, they can be discharged.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The two-component fungicide containing fluopyram described in this invention has an effective control effect on banana leaf spot disease and is safe for bananas, which can delay the process of developing resistance to pesticide damage.

[0037] (2) The two-component bactericide containing fluopyram as described in this invention uses a combination of arylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether as emulsifiers. The prepared microemulsion has good stability and short foaming time.

[0038] (3) The two-component bactericide containing fluopyram as described in this invention, with the synergistic effect of tristyrylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether with an EO value of 5-9, can give the agent good thermal storage stability and achieve good rapid defoaming effect.

[0039] (4) The two-component bactericide containing fluopyram as described in this invention uses a 1:2 weight ratio of cosolvent ADMA10 and solvent N-methylpyrrolidone, so that the agent can be made into a microemulsion or soluble liquid, which has good compatibility with water and the active ingredient can be sprayed evenly during use.

[0040] (5) The two-component fungicide containing fluopyram described in this invention has a good control effect on banana leaf spot disease. It can be diluted with water and sprayed evenly in the field, and is suitable for large-scale use. Fluopyram and propiconazole have a good synergistic effect, which can reduce the amount of drug used, delay and control the drug resistance of pathogens, and at the same time make the mixture have protective, curative and systemic effects, so as to achieve the purpose of complementing each other's strengths and weaknesses, and expanding the control spectrum and application range. Attached Figure Description

[0041] Figure 1 The graph shows the results of the thermal storage stability test in Example 1.

[0042] Figure 2 This is a graph showing the results of the thermal storage stability test in Example 2;

[0043] Figure 3 The graph shows the low-temperature stability test results of Example 1;

[0044] Figure 4 The graph shows the low-temperature stability test results for Example 4;

[0045] Figure 5 The graph shows the stability test results of the emulsion in Example 1 after being diluted 200 times.

[0046] Figure 6 The graph shows the stability test results of the emulsion in Example 3 after being diluted 200 times.

[0047] Figure 7 The image shows the test results of a wet sieving test after thermal storage in Example 5. Detailed Implementation

[0048] Example 1

[0049] A two-component fungicide containing fluopyram, wherein the active ingredients include fluopyram and propiconazole, wherein the weight ratio of fluopyram to propiconazole is 1:2.

[0050] The bactericide is formulated as a microemulsion, wherein the active ingredient accounts for 22.5% of the total mass of the bactericide in the microemulsion.

[0051] The raw materials for preparing the microemulsion also include, by weight percentage, 24% emulsifier, 10% cosolvent, 20% solvent, 10% compatibility agent, and deionized water to bring the total to 100%.

[0052] The emulsifier is tristyrene-phenol polyoxyethylene ether and dodecyl alcohol polyoxyethylene ether, with a weight ratio of 5:1. The dodecyl alcohol polyoxyethylene ether has an EO value of 9 and was purchased from Jiangsu Kaiyuan Technology Co., Ltd.

[0053] The co-solvent is N,N-dimethyldecanoamide. The solvent is N-methylpyrrolidone.

[0054] The compatibility agent is a plant-based polyether polyol, purchased from Guangzhou Fangzhong Chemical Co., Ltd., model V490.

[0055] A method for preparing a two-component fungicide containing fluopyram includes the following steps:

[0056] (1) Add the co-solvent and solvent to the preparation tank, turn on the stirrer, add fluopyram and propiconazole to the preparation tank, and dissolve and mix for 50 min;

[0057] (2) Weigh the emulsifier accurately according to the feeding ratio and add it to the preparation vessel. Turn on the stirrer to mix for 40 minutes.

[0058] (3) Finally, add deionized water and mix for 50 minutes.

[0059] (4) The mixed materials are sampled and analyzed. Once they meet the standard requirements, they can be discharged.

[0060] Example 2

[0061] A two-component fungicide containing fluopyram, with the same steps as in Example 1, except that the emulsifier is a combination of dodecylphenol polyoxyethylene ether and dodecyl alcohol polyoxyethylene ether in a weight ratio of 5:1, and the dodecylphenol polyoxyethylene ether was purchased from Shandong Yongwang Chemical Co., Ltd.

[0062] Example 3

[0063] A two-component fungicide containing fluopyram, with the same steps as in Example 1, except that the weight ratio of the tristyrylphenol polyoxyethylene ether and the dodecyl alcohol polyoxyethylene ether is 1:1.

[0064] Example 4

[0065] A two-component fungicide containing fluopyram, with the same steps as in Example 1, except that the weight ratio of N,N-dimethyldecylamide to N-methylpyrrolidone is 0.1:2.

[0066] Example 5

[0067] A two-component fungicide containing fluopyram is provided. The specific raw materials are the same as in Example 1, except that the preparation method is based on existing technology to prepare a microcapsule suspension-suspension agent. Fluopyram is the suspension agent, propiconazole is microencapsulated, and the weight percentage of the capsule material is 1.5%. It was purchased from Nanjing Gutian Chemical Co., Ltd., with the brand name GT-27.

[0068] Performance testing

[0069] 1. Virulence test: The virulence of fluopyram and propiconazole, as well as their mixtures at volume ratios of 1:1, 1:2, 2:3, 3:2 and 2:1, against the banana leaf spot pathogen was determined using the drug-containing culture medium method according to the standards of NY / T1156.2-2006 and NY / T1156.6-2006.

[0070] Test method:

[0071] Fluopyram solution: Weigh 0.0100g of 98% fluopyram technical grade, dissolve it in 0.5mL LDM, add 97.5mL of sterile water containing 0.1% Tween 80 emulsifier, stir well, and prepare a 100mg / L stock solution. Then dilute it with sterile water containing 0.1% Tween 80 emulsifier to concentrations of 50, 10, 5, 1, and 0.5mg / L for later use.

[0072] Propiconazole solution: Weigh 0.0100g of 95% propiconazole technical grade, dissolve it in 0.5mL of DMF, add 94.5mL of sterile water containing 0.1% Tween 80 emulsifier to prepare a 100mg / L stock solution, and then dilute it with sterile water containing 0.1% Tween 80 emulsifier to concentrations of 50, 10, 5, 1, and 0.5mg / L for later use;

[0073] Each mixed solution: Take 10, 10, 10, 15, and 20 mL of 100 mg / L fluopyram solution and add it to 10, 20, 15, 10, and 10 mL of 100 mg / L propiconazole solution to prepare 100 mg / L fluopyram·propiconazole 1:1, 1:2, 2:3, 3:2, and 2:1 solutions, respectively. Then dilute with sterile water containing 0.1% Tween80 emulsifier to concentrations of 50, 10, 5, 1, and 0.5 mg / L for later use.

[0074] Control solution: 0.5 mL of DMF and 95 mL of sterile water containing 0.1% (v / v) Tween 80 emulsifier.

[0075] 98% fluxapyroxad technical, purchased from BASF Europe Company; 95% propiconazole technical, purchased from Jiangsu Youjia Plant Protection Co., Ltd.

[0076] Refer to the standard bioassay method NY / T 1156.2 - 2006, using the method of medicated medium: Take 3 mL of the liquid medicine of each single agent and mixture series concentration, add it to 27 mL of PDA medium cooled to 45 °C, and make a medicated medium plate with the required final concentration. Then, take a 6 - mm - diameter mycelial block from the edge of the banana leaf spot pathogen colony cultured for 7 days and transfer it to each series of medicated medium, with the mycelial surface facing down. After the treatment, place it in an intelligent artificial climate incubator at 28 °C for cultivation. Refer to the standard bioassay method NY / T 1156.6 - 2006, and evaluate the synergistic effect of the mixture of pesticides according to the co - toxicity coefficient method (CTC) of Sun & Johnson (1960), that is, CTC ≤ 80 is antagonistic effect, 80 < CTC < 120 is additive effect, and CTC ≥ 120 is synergistic effect.

[0077] The test results are shown in Table 1.

[0078] Table 1

[0079]

[0080] 2. Field experiment: Refer to "Pesticide Field Efficacy Test Guidelines (Part 2)" GB / T 17980.95 - 2004, Part 95: Fungicides for Controlling Banana Leaf Spot, and conduct a field efficacy test of fluxapyroxad · propiconazole microemulsion for controlling banana leaf spot in Example 1. The dosages of each treatment agent are shown in Table 2.

[0081] Table 2

[0082] <{ <=

[0083] Apply the first dose during the vegetative growth period of bananas (8 - leaf stage); 12 days later, apply the second dose during the vegetative growth period of bananas (11 - leaf stage); 10 days later, apply the third dose during the vegetative growth period of bananas at the 12 - leaf stage, with a total of 3 applications. <{

[0084] Refer to "Pesticide Field Efficacy Test Guidelines (Part 2)" GB / T 17980.95 - 2004, Part : Fungicides for Controlling Banana Leaf Spot. Randomly investigate 3 plants in each plot, and investigate 9 leaves from the top leaf down for each banana plant, and record the total number of leaves investigated and the number of diseased leaves at each level.

[0085] Grading method:

[0086] Grade 0: Disease - free;

[0087] Grade 1: The lesion area accounts for less than 5% of the total leaf area;

[0088] Grade 3: Lesions cover 6% to 15% of the total leaf area;

[0089] Grade 5: Lesions cover 16% to 25% of the total leaf area;

[0090] Level 7: Lesions cover 26% to 50% of the total leaf area;

[0091] Level 9: The lesion area accounts for more than 51% of the total leaf area.

[0092] Referring to Part 95 of GB / T 17980.95-2004, "Guidelines for Field Efficacy Trials of Pesticides (II)": Control of Banana Leaf Spot Disease with Fungicides, the method for calculating the control efficacy is as follows:

[0093] No baseline survey of the patient's condition was conducted before medication.

[0094]

[0095]

[0096] In the formula: CK – disease index of the blank control area;

[0097] PT-1 drug treatment area disease index.

[0098] The test results are shown in Table 3.

[0099] Table 3

[0100]

[0101] In Example 1, the control efficacy of fluopyram·propiconazole microemulsion at dilutions of 600 and 800 times was above 72% 10 days after the second application; the control efficacy was above 78% 7 days after the third application; and although the control efficacy decreased slightly 14 days after the third application, it was still above 73%. The 600 and 800 times dilutions of fluopyram·propiconazole microemulsion in Example 1 demonstrated good control efficacy against banana leaf spot disease.

[0102] 3. Stability performance: The thermal storage stability of Examples 1 and 2 was tested according to standard GB / T 19136-2003. The test results are shown in [see attached table]. Figure 1 2; The low-temperature stability of Examples 1 and 4 was tested according to GB / T 19137-2003, and the test results are shown in […]. Figure 3 4; Refer to GB / T1603-2001 for testing the stability of emulsions from Examples 1 and 3 after dilution by 200 times. The test results are shown in […]. Figure 56; A wet sieve test was conducted on the emulsion of Example 5 after heat storage, referring to the NY / T2989-2016 standard. The test results are shown in […]. Figure 7 .

[0103] Test results are available Figure 1-7 .

Claims

1. A two-component fungicide containing fluopyram, characterized in that, The active ingredients of the fungicide include fluopyram and propiconazole, wherein the weight ratio of fluopyram to propiconazole is 1:(0.2-3). The bactericide is formulated as a microemulsion. The raw materials for preparing the microemulsion also include, by weight percentage, 20-30% emulsifier, 5-15% cosolvent, 10-30% solvent, 8-15% compatibility agent, and diluent to 100%; The emulsifier is a combination of dodecyl alcohol polyoxyethylene ether and tristyrene phenol polyoxyethylene ether in a weight ratio of 1:(3-7), and the EO value of the dodecyl alcohol polyoxyethylene ether is 5-9. The co-solvent is N,N-dimethyldecanoamide, and the solvent is N-methylpyrrolidone; the weight ratio of N,N-dimethyldecanoamide to N-methylpyrrolidone is (0.5-1.5):2; The compatibility agent is a plant-based polyether polyol.

2. The two-component fungicide containing fluopyram according to claim 1, characterized in that, The active ingredient in the microemulsion accounts for 10-35% of the mass of the microemulsion.

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