A synergistic tebuconazole and a preparation method and application thereof

Abstract

The present application provides a synergistic metiram and a preparation method and application thereof, and belongs to the technical field of chemical pesticides. The metiram technical material, emulsifier, thickening agent and solvent are mixed, and then subjected to shearing and sand milling in sequence to obtain metiram dispersible oil suspending agent. The adhesion and anti-washing capacity of the liquid droplets of the pesticide liquid can be greatly improved, the persistence thereof is enhanced, and the control effect of metiram is facilitated to a certain extent. Meanwhile, the penetration performance of the metiram dispersible oil suspending agent is improved, so that more effective components enter crops and various loss conditions are reduced, and the metiram dispersible oil suspending agent has good stability. The physicochemical properties of the metiram dispersible oil suspending agent are determined by the CIPAC method, and all indexes meet the requirements of pesticide preparations. The metiram dispersible oil suspending agent can be used for unmanned aerial vehicle spraying, overcomes the shortcomings of water-based formulations, such as easy evaporation and drift, when used for unmanned aerial vehicle spraying, so that the unmanned aerial vehicle spraying is more efficient and convenient, and has good applicability for some areas limited by topography and landform. The metiram dispersible oil suspending agent can be used for controlling wheat scab, and the control effect can reach 86.89%. The occurrence of diseases is reduced, the income of planters is improved, and the metiram dispersible oil suspending agent is suitable for popularization and application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of chemical pesticides, in particular to a synergistic metconazole and a preparation method and application thereof. BACKGROUND

[0002] Pesticides play an extremely important role in the struggle against harmful organisms and the protection of crop production safety, and are important production materials. Wheat, as a world food crop, has many diseases and pests in its production, which harm the yield and quality of wheat. Common diseases and pests include sheath blight, powdery mildew, rust, scab, aphids, and wheat spiders. Scab is a disease that has a greater impact on wheat production, and the control effect of this disease will directly affect the yield and quality of wheat grains. At the present stage, chemical control is still the main method for controlling scab.

[0003] Chemical pesticides have high costs and long development cycles. It is very difficult to synthesize commercially available and innovative pesticide compounds, and it is necessary to develop them into suitable dosage forms to facilitate their long-term development. Therefore, in recent years, the research and development of pesticide dosage forms, especially the development of green, efficient, and labor-saving new dosage forms, have received widespread attention from various industries. The choice of dosage form is not only determined by the physical and chemical properties of the original drug, but also takes into account its safety, stability, and convenience. Traditional dosage forms such as emulsifiable concentrates and wettable powders use a large amount of organic solvent or are prone to dust pollution, drug damage, short duration, and environmental impact. Therefore, it is necessary to develop environmentally friendly water-based and labor-saving dosage forms such as suspension concentrates, water dispersible granules, and dispersible oil suspensions. Among them, the registration proportion of dispersible oil suspensions is increasing, and the market potential and research value in the future are very promising.

[0004] Metconazole is a new type of triazole fungicide with broad-spectrum systemicity, good protection and treatment effects, low toxicity to non-target organisms, low dosage, and green control requirements. Its market prospect is very broad. Therefore, in order to improve the deposition efficiency of the target and reduce the loss of the drug, it is necessary to develop an efficient formulation. SUMMARY

[0005] Therefore, the present application aims to provide a synergistic metconazole and a preparation method and application thereof. Based on the physical and chemical properties of the metconazole formulation for high-efficiency control of wheat scab and the low-volume spraying method of the plant protection unmanned aerial vehicle, the present application has the best performance with methyl oleate as the dispersing medium, low cost, no dust pollution, safety, and environmental protection. The present application improves the utilization rate of pesticides and reduces the loss of liquid droplets during the spraying process.

[0006] In order to achieve the above-mentioned purpose, the present application provides the following technical solutions:

[0007] In a first aspect, the present application provides a synergistic metconazole, wherein the synergistic metconazole is prepared by using metconazole technical to prepare metconazole dispersible oil suspension.

[0008] In a second aspect, the present application provides a preparation method of metconazole dispersible oil suspension, comprising the following steps:

[0009] After mixing metconazole technical, emulsifier, thickening agent and solvent, the mixture is subjected to shearing and sanding in sequence to obtain metconazole dispersible oil suspension.

[0010] Preferably, the mass ratio of metconazole technical, emulsifier, thickening agent and solvent is 8:8-15:1-3:74-81.

[0011] Preferably, the emulsifier is one or more of N600, EF68 and EF69.

[0012] Further preferably, the emulsifier is N600.

[0013] Preferably, the thickening agent is one or more of organic bentonite, white carbon black and modified hydrogenated castor oil.

[0014] Preferably, the solvent is methyl oleate or S-150 mineral oil.

[0015] Further preferably, the solvent is methyl oleate.

[0016] Preferably, the sanding parameters are as follows:

[0017] The grinding rate is 1800 r / min.

[0018] The grinding time is 60 min.

[0019] Preferably, the particle size Dv50 of the metconazole dispersible oil suspension is ≤5 μm. 50

[0020] In a third aspect, the present application provides application of the above metconazole dispersible oil suspension in unmanned aerial vehicle pesticide application.

[0021] Beneficial technical effects:

[0022] ​The present application develops metconazole into dispersible oil suspensions, which can greatly improve the adhesion and anti-washing ability of liquid droplets, enhance the effective period, and to some extent, help to play the control effect of metconazole; at the same time, the penetration performance is improved, so that more effective components enter the crops and reduce various loss conditions; the agent is stable in cold storage (0±2℃) and hot storage (54±2℃) tests, and the decomposition rate of the effective component is less than 5%. In addition, after 6 months of storage, the liquid has no creaming, bottoming and other phenomena; it is shown that the emulsion has good stability; the physical and chemical properties of metconazole dispersible oil suspensions are determined by CIPAC method, and all indexes meet the requirements of pesticide formulations.

[0023] After metconazole is developed into dispersible oil suspensions, it can be used for unmanned aerial vehicle spraying, overcoming the shortcomings of water-based formulations, such as easy evaporation and drift when used in unmanned aerial vehicle spraying, making unmanned aerial vehicle spraying more efficient and convenient, and having good applicability in some areas limited by topography and landform.

[0024] The metconazole dispersible oil suspensions of the present application can be used for preventing and treating wheat scab, and the control effect can reach 86.89%; the occurrence of diseases is reduced, the income of planters is improved, and the present application is suitable for popularization and application. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 It is a preparation process flow chart;

[0026] Figure 2 It is the distribution of liquid particle size, wherein (a) methyl oleate is used as the solvent; (b) S-150 is used as the solvent;

[0027] Figure 3 It is a graph of the surface tension of different pesticide solutions changing with dilution multiple;

[0028] Figure 4 It is a contact angle diagram of different concentrations of pesticide solutions on wheat leaves;

[0029] Figure 5 It is an image of the change of OD system pesticide droplet morphology with time when methyl oleate is used as the solvent;

[0030] Figure 6 It is an image of the change of OD system pesticide droplet morphology with time when S-150 is used as the solvent;

[0031] Figure 7 It is an image of the change of SC system pesticide droplet morphology with time. DETAILED DESCRIPTION

[0032] Now, a variety of exemplary embodiments of the present application will be described in detail, which should not be considered as limiting the present application, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present application.

[0033] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. In addition, where particular ranges of values are given, understand that each intervening value, to the upper or lower limit of the ranges is also specifically included. Each smaller range that falls within the broader ranges is also specifically included in the present application. The upper and lower limits of these smaller ranges can independently be included or excluded in the range.

[0034] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the documents are cited. In case of conflict, the present specification will control.

[0035] Various modifications and changes can be made to the specific embodiments described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those of ordinary skill in the art from consideration of the description and practice of the application. The description and examples are illustrative only.

[0036] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or variations thereof, are intended to be open-ended terms that mean including, but not limited to.

[0037] The "room temperature" or "normal temperature" described in the present application is 25±2°C unless otherwise specified.

[0038] The equipment or raw materials used in the following examples are commercially available unless otherwise specified.

[0039] Example 1

[0040] 1.1 Materials and instruments

[0041] 1.1.1 Test materials

[0042] 98% tebuconazole technical (Zhejiang Yulong Biotechnology Co., Ltd.); N600 (Dacheng High-tech Research Center Co., Ltd.); EF68 (Beijing Green Team Technology Co., Ltd.); EF69 (Beijing Green Team Technology Co., Ltd.); methyl oleate (Suzhou Fengbei Biotechnology Co., Ltd.); S-150 mineral oil (Jiangsu Huaren Chemical Co., Ltd.); organic bentonite (Shandong Kesaikeng Holding Co., Ltd.).

[0043] 1.1.2 Test instrument

[0044] Sand mill RTSM-0.2BJ (Shanghai Rute Electrical Equipment Co., Ltd.); electronic balance with an accuracy of 0.0001 g (Tianjin Hui Feng Green Instrument Co., Ltd.); DCAT25 surface interfacial tension instrument (Dataphysics, Germany); OCA25 video optical contact angle measuring instrument (Dataphysics, Germany); air drying oven (Shanghai Yiheng Scientific Instrument Co., Ltd.); laser particle size distribution instrument (Dandong Baitai Instrument Co., Ltd.).

[0045] 1.2 Test method

[0046] 1.2.1 Preparation of test sample

[0047] Method scheme:

[0048] According to the following formula, (calculated with 250 g) tebuconazole technical material 20 g (8%), emulsifier 20 g (8%), organic soil 5 g (2%), solvent oil to 250 g, cut according to the proportion, shear uniformly, then add a certain proportion of zirconium beads (0.8-1.0 μm), grind at a speed of 1800 r / min for 60 min, sand mill to particle size D 50 ≤5 μm, bottle for standby. The process flow is shown in Figure 1 .

[0049] 1.2.2 Selection of emulsifier and thickening agent

[0050] According to the formula in Table 1, prepare dispersible oil suspension, emulsifier 8%-15%, thickening agent 1%-3% and technical material, then add solvent oil to 250 g, and then measure the stability of the liquid after preparation.

[0051] Table 1 Preparation of tebuconazole dispersible oil suspension

[0052]

[0053] 1.3 Stability determination

[0054] 1.3.1 Determination of heat storage stability

[0055] The heat storage stability test method is referred to GB / T 19136-2021, 20 g of test sample is added to a transparent sample bottle, and placed in a constant temperature air drying oven at (54±2)℃, after 14 d, the appearance change of the test sample is observed, and the content of the active ingredient is determined within 24 h. The evaluation standard is that the test sample is uniformly stable in appearance, no precipitate is precipitated, no oil is separated (or restored to its original state after shaking), etc. At the same time, the decomposition rate of the active ingredient is ≤5%, which is qualified. Each test sample is repeated 6 times, and the test results are shown in Tables 2-3.

[0056] Table 2 Effect of different amounts of emulsifier on the stability of the preparation in hot storage (using methyl oleate as solvent)

[0057]

[0058]

[0059] Table 3 Effect of different amounts of emulsifier on the stability of the preparation in hot storage (using S-150 as solvent)

[0060]

[0061]

[0062] 1.3.2 Low temperature stability determination

[0063] The low temperature stability test method is described in GB / T 19137-2003. The test sample is added to a sample bottle, which is then sealed and stored at (0±2) °C for 7 days. The appearance of the sample is observed for any changes such as oil separation or precipitation. If there is no change, the sample is considered to be qualified. Each sample is repeated 6 times, as shown in Table 4.

[0064] 1.4 Formulation optimization

[0065] In order to optimize the formulation of the liquid medicine, orthogonal experiments were conducted on formulations containing different concentrations (15%-6%) of different surfactants (emulsifiers N600, EFR68 and EF69). The stability of the liquid medicine was preliminarily evaluated by monitoring the appearance changes from 0h to 14d. The results of the orthogonal experiment are shown in Tables 4-6.

[0066] Table 4 Effect of different amounts of thickening agent on the stability of the preparation

[0067]

[0068] Table 5 Screening of emulsifiers (using methyl oleate as solvent)

[0069]

[0070]

[0071] Table 6 Screening of emulsifiers (using S-150 as solvent)

[0072]

[0073]

[0074] The results of Table 3 and Table 4 show that the suspensions using emulsifier N600 are stable and uniform in both selected solvents within 14 days, and the appearance of the liquid has no obvious change, indicating that it has long-term physical stability, and the effect of emulsifier EF68 is weaker than that of emulsifier N600 in both solvents.

[0075] 2 Performance measurement

[0076] 2.1 Performance characterization

[0077] The most stable liquid was tested for physical and chemical indicators by CIPAC method. The formulation of 8% metconazole dispersible oil suspension was obtained by grinding metconazole active ingredient and 8% N600 into methyl oleate or S-150 solvent to make a homogeneous phase, and its storage stability, pouring test, persistent foaming, pH and other indicators were tested (the average of the two was recorded in Table 7).

[0078] Table 7 Test results of quality standards of stable liquid

[0079]

[0080]

[0081] The data analysis in Table 5 shows that at 0℃, the suspension does not precipitate or emulsify, and after 14 days of hot storage at 54±2℃, a small amount of stratification appears in the bottle, but the liquid becomes uniform after shaking, indicating that the stability of the liquid system is qualified. The determination results of other indicators meet the requirements of pesticide formulations.

[0082] 2.2 Particle size measurement

[0083] The particle size of each sample was tested by laser particle size analyzer, and the test was repeated 5 times to calculate D 50 average value, see Figure 2 .

[0084] 2.3 Measurement of wettability

[0085] 2.3.1 Static surface tension (SST)

[0086] The 8% metconazole dispersible oil suspension was diluted with deionized water to 10, 100, 500 and 1000 times aqueous solution; the static surface tension of the diluted solution was measured by DCAT25 surface interfacial tension instrument (Germany dataphysics company), each sample was measured 3 times, and the average value was taken. The test temperature was 20±1℃, and the test results are shown in Figure 3 .

[0087] As Figure 3As shown, regardless of the dilution ratio (10x, 100x, 500x, 1000x), the surface tension of the formulations prepared with the two solvent oils gradually increased with increasing dilution ratio. Compared with the other two drug solutions, the suspension system prepared with methyl oleate as the solvent oil (8% tebuconazole OD) had the lowest surface tension value. When the solution was undiluted (Control), this value was approximately 25.37 mN / m.

[0088] 2.3.2 Dynamic Contact Angle (DCA)

[0089] 8% tebuconazole dispersible oil suspension was diluted with deionized water to prepare aqueous solutions of 10, 100, 500, and 1000 times. One drop of the solution was placed on a wheat leaf using a needle with an inner diameter of φ = 0.8 mm. The contact angle was measured every 1 second using an OCA25 video optical contact angle meter (Dataphysics, Germany) for 0–6 minutes, repeated 3–4 times. The droplet shape was photographed at 0, 1, 2, 3, 4, 5, and 6 minutes. The experimental temperature was 20 ± 1℃. The results are shown in […]. Figure 4 .

[0090] Depend on Figure 4 It can be seen that for pesticide solutions with different dispersion media, the initial contact angle decreases with increasing concentration. At the same dilution ratio, the initial contact angle of the OD suspension is smaller than that of the SC suspension. At the same formulation and concentration, the initial contact angle of the suspension prepared using methyl oleate as the solvent is smaller than that prepared using S-150. The 10-fold dilution has the lowest contact angle, indicating excellent wettability on wheat leaves. The contact angles of the 10-fold and 100-fold dilutions gradually decrease over 30 seconds. For the 500-fold and 1000-fold dilutions, the contact angle remains almost constant, with an initial value of approximately 100°, indicating poor wettability on wheat leaves. The difference in contact angle between different dilutions is more pronounced for suspensions prepared using methyl oleate as the solvent.

[0091] 3. Jump Test

[0092] Figures 5-7The figure is the image of the change of the droplet form with time after the 10 times, 100 times, 500 times and 1000 times dilution liquid of the suspension agent hit the wheat leaf. It is known that the wheat leaf is a hydrophobic interface. The droplets of the OD and SC systems and the undiluted droplets of the control group are separated and rolled off from the edge of the droplets with the increase of time after the droplets are spread and retracted in the SC system. However, the droplets prepared by using methyl oleate and S-150 as the solvent oil are spread, retracted and bounced back from the leaf surface after hitting the wheat leaf. The droplets are spread to the maximum at 1.5 ms to 2.0 ms, and then retracted. There is almost no droplet separation from the edge of the droplets. The droplets prepared by using methyl oleate as the solvent oil are spread the fastest, which indicates that the OD system can effectively inhibit the bounce and roll-off of the droplets.

[0093] 4Control effect on fusarium blight of wheat

[0094] Table 8 Control effect of ipconazole different formulations on fusarium blight of wheat

[0095]

[0096] Note: The same column in the table represents the significant difference at the level of P < 0.05 by the LSD method.

[0097] The indoor control effect determination results are shown in Table 8. Each pesticide has a control effect on fusarium blight of wheat. The control effect of each pesticide gradually increases with the increase of the application mass concentration. The control effect of the formulation prepared by using methyl oleate as the solvent oil is significantly higher than that of the S-150 pesticide and the commercially available pesticide. When the effective component mass concentration of the pesticide is 160 μg / mL, the control effect of the methyl oleate system is 86.89%. The control effect of the S-150 pesticide and the commercially available pesticide is 73.77% and 67.21%, respectively.

[0098] The above only describes the preferred embodiments of the present application. It should be noted that the ordinary skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A synergistic mixture of metconazole, characterized in that, The synergistic metiram is prepared by using metiram technical material to prepare metiram dispersible oil suspension; The metiram dispersible oil suspension is prepared by using metiram technical material, emulsifier, thickening agent and solvent; The mass ratio of the metiram technical material, emulsifier, thickening agent and solvent is 8:8-15:1-3:74-81.

2. A process for the preparation of a dispersible oil suspension of metconazole characterized in that, The method comprises the following steps: The metiram dispersible oil suspension is prepared by mixing the metiram technical material, emulsifier, thickening agent and solvent and then shearing and sanding them in sequence; The mass ratio of the metiram technical material, emulsifier, thickening agent and solvent is 8:8-15:1-3:74-81.

3. The preparation method according to claim 2, characterized in that, The emulsifier is one or more of N600 and EF68.

4. The production method according to claim 3, characterized by, The emulsifier is N600.

5. The preparation method according to claim 2, characterized in that, The thickening agent is one or more of organic bentonite, white carbon black and modified hydrogenated castor oil.

6. The preparation method according to claim 2, characterized in that, The solvent is methyl oleate or S-150 mineral oil.

7. The preparation method according to claim 2, characterized in that, The solvent is methyl oleate.

8. The preparation method according to claim 2, characterized in that, The particle size D of the metconazole dispersible oil suspension is 50 ≤ 5 μm.

9. The synergistic metiram of claim 1 is applied in unmanned aerial vehicle pesticide application.

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