A pyraclostrobin-clofoconazole fungicide composition and its microemulsion and application

Abstract

The present invention belongs to the technical field of A01N pesticides, and more specifically relates to a bactericidal composition and its microemulsion, preparation method and application. A bactericidal composition, the preparation raw materials include: pyraclostrobin and / or clofoconazole; the weight ratio of pyraclostrobin and clofoconazole is 1: (3-5). The microemulsion prepared by the present invention not only improves the stability of the active ingredient under the compound use of triphenyl phenol polyoxyethylene ether polyoxypropylene ether and naphthalenesulfonic acid sodium salt formaldehyde condensate, but also avoids the turbidity phenomenon of the microemulsion caused by the decrease of the bonding ability between the hydrophilic group and the water molecule in the system when used under high temperature conditions after compounding, thereby ensuring the normal use of the microemulsion.

Description

Technical Field

[0001] The present invention belongs to the technical field of A01N pesticides, and more specifically relates to a bactericidal composition and a microemulsion thereof, a preparation method and an application thereof. Background Art

[0002] In recent years, the development of pesticide technology has shown a rapid trend, but the efficiency and safety of pesticides have always been the most concerned issues for researchers and users.

[0003] With the development of pesticide technology, more and more slogans such as green, environmental protection, safety, non-toxic, and tasteless are appearing on the market, but with the increase of additional functions, the price of pesticides is also changing. Now in addition to common insecticides, herbicides, and various targeted preventive drugs for treating crop pathogens, there are more and more pesticides on the market. Among them, the pesticide preparation with pyraclostrobin and cyfluthrin as active ingredients discloses the excellent effect of the fungicidal composition containing cyfluthrin and pyraclostrobin in the prevention and treatment of banana leaf spot fungus in the patent CN109362759A disclosed in the prior art, but only two active ingredients are disclosed in the disclosed patent, but in the process of actual application, the dosage form of the agent has a greater impact on the use of subsequent products.

[0004] In order to further study the excellent stability and other properties of the agent prepared with pyraclostrobin and clofothiazolin as active ingredients during use, researchers still need to conduct a lot of research on this process. Summary of the invention

[0005] In order to solve the above technical problems, the first aspect of the present invention provides a fungicide composition, the preparation raw materials include: pyraclostrobin and / or mesotrione; the weight ratio of pyraclostrobin to mesotrione is 1: (3-5).

[0006] In some preferred embodiments, the weight ratio of pyraclostrobin to mesotrione is 1:4.5.

[0007] The second aspect of the present invention provides a microemulsion, comprising a bactericidal composition and auxiliary materials; the bactericidal composition accounts for 10-50% of the total weight of the raw materials of the microemulsion.

[0008] In some preferred embodiments, the auxiliary materials include one or more combinations of dispersants, thickeners, emulsifiers, defoamers, preservatives, pH regulators, stabilizers, antifreeze agents, film formers, and dispersants.

[0009] In some preferred embodiments, the raw materials for preparation include, by weight percentage: 10-50% of the bactericidal composition, 1-18% of the emulsifier, 1-5% of the stabilizer, 0.5-3% of the defoaming agent, and the dispersant is supplemented to make up the balance to 100%.

[0010] In some preferred embodiments, the raw materials for preparation include, by weight percentage: 20-40% of the bactericidal composition, 2-15% of the emulsifier, 1-3% of the stabilizer, 0.5-2% of the defoaming agent, and the dispersant is supplemented to make up the balance to 100%.

[0011] In some preferred embodiments, the HLB value of the emulsifier is 10-18; preferably, the HLB value of the emulsifier is 13-17.

[0012] In some preferred embodiments, the emulsifier is selected from at least one of triphenyl phenol polyoxyethylene ether polyoxypropylene ether, nonylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, glycerol polyoxyethylene ether polyoxypropylene ether fatty acid ester, sorbitan fatty acid ester, sorbitan fatty acid ester ethylene oxide adduct, and fatty amide polyoxyethylene ether. Further preferably, the emulsifier is selected from triphenyl phenol polyoxyethylene ether polyoxypropylene ether; further preferably, the triphenyl phenol polyoxyethylene ether polyoxypropylene ether is selected from 1602# triphenyl phenol polyoxyethylene ether polyoxypropylene ether of Haian Petrochemical.

[0013] Further preferably, the HLB value of the triphenyl phenol polyoxyethylene ether polyoxypropylene ether is 16.

[0014] More preferably, the emulsifier also includes naphthalenesulfonic acid sodium salt formaldehyde condensate.

[0015] Naphthalenesulfonic acid sodium salt formaldehyde condensate was purchased from Anyang Shuanghuan Auxiliary Agent Co., Ltd.

[0016] In some preferred embodiments, the weight ratio of the triphenyl phenol polyoxyethylene ether polyoxypropylene ether to the naphthalenesulfonic acid sodium salt formaldehyde condensate is 1: (0.1-0.8).

[0017] Further preferably, the weight ratio of the triphenyl phenol polyoxyethylene ether polyoxypropylene ether to the naphthalenesulfonic acid sodium salt formaldehyde condensate is 1:0.4.

[0018] During the experiment, after a large number of creative experimental explorations, the inventors found that the selection of dispersants in the process of preparing microemulsions not only promotes the uniform dispersion of active ingredients, but also has a great impact on ensuring the wetting between the preparation raw materials during use and the stability during subsequent storage. After a lot of careful exploration, it was found that by using triphenyl phenol polyoxyethylene ether polyoxypropylene ether and naphthalenesulfonic acid sodium salt formaldehyde condensate as emulsifiers and ensuring that their weight ratio is within the range of 1: (0.1-0.8), the phenomenon of weakening the interaction ability between hydrophilic groups and water molecules in the system caused by excessively high temperature can be avoided. In addition, due to the steric hindrance in the structure of triphenyl phenol polyoxyethylene ether polyoxypropylene ether, a relatively balanced state can be formed between the molecules of the naphthalenesulfonic acid sodium salt formaldehyde condensate, thereby avoiding the precipitation of the active ingredients and ensuring their stability when used in a high temperature environment.

[0019] In some preferred embodiments, the stabilizer is azone.

[0020] In some preferred embodiments, the defoaming agent is selected from silicone defoaming agents.

[0021] Defoaming agent, model ZY-5731A, was purchased from Shanghai Ziyi Chemical Co., Ltd.

[0022] In some preferred embodiments, the dispersant includes at least water.

[0023] Further preferably, the dispersant also includes an organic solvent.

[0024] Further preferably, the organic solvent is selected from cyclohexanone and solvent naphtha 200.

[0025] Further preferably, the weight ratio of the cyclohexanone to the solvent oil 200 is 1:1.5.

[0026] More preferably, the organic solvent accounts for 20-30% of the total weight of the raw materials for preparing the microemulsion.

[0027] The third aspect of the present invention provides a method for preparing a microemulsion, comprising the following steps:

[0028] The bactericidal composition and the preparation raw materials are stirred and dissolved, and after they are completely dissolved, an emulsifier, a defoamer, a stabilizer and a dispersant are added, and the mixture is stirred and mixed to obtain a microemulsion.

[0029] The fourth aspect of the present invention provides an application of a microemulsion for the prevention and treatment of grape powdery mildew, downy mildew, grape black pox and powdery mildew.

[0030] Beneficial effects: The microemulsion prepared by the present invention has the following advantages:

[0031] 1. The microemulsion prepared by the present invention can further ensure the stability of pyraclostrobin and clofoconazole during use, avoid the sedimentation phenomenon in the microemulsion, and avoid the decrease of drug efficacy.

[0032] 2. The microemulsion prepared by the present invention, when used in combination with triphenyl phenol polyoxyethylene polyoxypropylene ether and naphthalenesulfonic acid sodium salt formaldehyde condensate, not only improves the stability of the active ingredient, but also avoids the turbidity of the microemulsion caused by the decrease in the bonding ability between the hydrophilic groups in the system and the water molecules when used under high temperature conditions, thereby ensuring the normal use of the microemulsion.

[0033] 3. The microemulsion prepared by the present invention promotes the formation of a stable equilibrium state between the systems under the mutual cooperation of the organic solvent and the water dispersant, ensures that the active ingredients form a transparent state, and at the same time, reduces pollution to the environment, is suitable for long-distance transportation, and improves its use value. DETAILED DESCRIPTION

[0034] Example

[0035] Example 1

[0036] A microemulsion, the preparation raw materials of which include, by weight percentage, 38% of a bactericidal composition, 14% of an emulsifier, 1.5% of a stabilizer, 1% of a defoaming agent, and the remainder of a dispersant to 100%.

[0037] The bactericidal composition comprises pyraclostrobin and clofoconazole, and the weight ratio thereof is 1:4.5.

[0038] The emulsifier is a condensate of triphenylethylphenol polyoxyethylene ether polyoxypropylene ether and naphthalenesulfonic acid sodium salt formaldehyde, and the weight ratio is 1:0.4;

[0039] The described triphenyl phenol polyoxyethylene ether polyoxypropylene ether has a model number of 1602# and an HLB value of 16;

[0040] The naphthalenesulfonic acid sodium salt formaldehyde condensate was purchased from Anyang Shuanghuan Auxiliary Agent Co., Ltd.;

[0041] The stabilizer is azone.

[0042] The defoamer is an organosilicon defoamer, model ZY-5731A, purchased from Shanghai Ziyi Chemical Co., Ltd.

[0043] The dispersant comprises an organic solvent and water, wherein the organic solvent accounts for 25% of the total weight of the raw materials for preparing the microemulsion, and the water supplements the balance to 100%.

[0044] The organic solvent comprises cyclohexanone and solvent oil 200, and the weight ratio thereof is 1:1.5.

[0045] A method for preparing a microemulsion comprises the following steps:

[0046] The bactericidal composition and the preparation raw materials are stirred and dissolved, and after they are completely dissolved, an emulsifier, a defoamer, a stabilizer and a dispersant are added, and the mixture is stirred and mixed to obtain a microemulsion.

[0047] Example 2

[0048] A microemulsion, the preparation raw materials of which include, by weight percentage, 38% of a bactericidal composition, 14% of an emulsifier, 1.5% of a stabilizer, 1% of a defoaming agent, and the remainder of a dispersant to 100%.

[0049] The bactericidal composition comprises pyraclostrobin and clofoconazole, and the weight ratio thereof is 1:4.5.

[0050] The emulsifier is a condensate of triphenylethylphenol polyoxyethylene ether polyoxypropylene ether and naphthalenesulfonic acid sodium salt formaldehyde, and the weight ratio is 1:1;

[0051] The described triphenyl phenol polyoxyethylene ether polyoxypropylene ether has a model number of 1602# and an HLB value of 16;

[0052] The naphthalenesulfonic acid sodium salt formaldehyde condensate was purchased from Anyang Shuanghuan Auxiliary Agent Co., Ltd.;

[0053] The stabilizer is azone.

[0054] The defoamer is an organosilicon defoamer, model ZY-5731A, purchased from Shanghai Ziyi Chemical Co., Ltd.

[0055] The dispersant comprises an organic solvent and water, wherein the organic solvent accounts for 25% of the total weight of the raw materials for preparing the microemulsion, and the water supplements the balance to 100%.

[0056] The organic solvent comprises cyclohexanone and solvent oil 200, and the weight ratio thereof is 1:1.5.

[0057] A method for preparing a microemulsion comprises the following steps:

[0058] The bactericidal composition and the preparation raw materials are stirred and dissolved, and after they are completely dissolved, an emulsifier, a defoamer, a stabilizer and a dispersant are added, and the mixture is stirred and mixed to obtain a microemulsion.

[0059] Example 3

[0060] A microemulsion, the preparation raw materials of which include, by weight percentage, 38% of a bactericidal composition, 14% of an emulsifier, 1.5% of a stabilizer, 1% of a defoaming agent, and the remainder of a dispersant to 100%.

[0061] The bactericidal composition comprises pyraclostrobin and clofoconazole, and the weight ratio thereof is 1:4.5.

[0062] The emulsifier is triphenyl ethyl phenol polyoxyethylene ether polyoxypropylene ether;

[0063] The described triphenyl phenol polyoxyethylene ether polyoxypropylene ether has a model number of 1602# and an HLB value of 16;

[0064] The stabilizer is azone.

[0065] The defoamer is an organosilicon defoamer, model ZY-5731A, purchased from Shanghai Ziyi Chemical Co., Ltd.

[0066] The dispersant comprises an organic solvent and water, wherein the organic solvent accounts for 25% of the total weight of the raw materials for preparing the microemulsion, and the water supplements the balance to 100%.

[0067] The organic solvent comprises cyclohexanone and solvent oil 200, and the weight ratio thereof is 1:1.5.

[0068] A method for preparing a microemulsion comprises the following steps:

[0069] The bactericidal composition and the preparation raw materials are stirred and dissolved, and after they are completely dissolved, an emulsifier, a defoamer, a stabilizer and a dispersant are added, and the mixture is stirred and mixed to obtain a microemulsion.

[0070] Example 4

[0071] A microemulsion, the preparation raw materials of which include, by weight percentage, 38% of a bactericidal composition, 14% of an emulsifier, 1.5% of a stabilizer, 1% of a defoaming agent, and the remainder of a dispersant to 100%.

[0072] The bactericidal composition comprises pyraclostrobin and clofoconazole, and the weight ratio thereof is 1:4.5.

[0073] The emulsifier is naphthalenesulfonic acid sodium salt formaldehyde condensate

[0074] The naphthalenesulfonic acid sodium salt formaldehyde condensate was purchased from Anyang Shuanghuan Auxiliary Agent Co., Ltd.;

[0075] The stabilizer is azone.

[0076] The defoamer is an organosilicon defoamer, model ZY-5731A, purchased from Shanghai Ziyi Chemical Co., Ltd.

[0077] The dispersant comprises an organic solvent and water, wherein the organic solvent accounts for 25% of the total weight of the raw materials for preparing the microemulsion, and the water supplements the balance to 100%.

[0078] The organic solvent comprises cyclohexanone and solvent oil 200, and the weight ratio thereof is 1:1.5.

[0079] A method for preparing a microemulsion comprises the following steps:

[0080] The bactericidal composition and the preparation raw materials are stirred and dissolved, and after they are completely dissolved, an emulsifier, a defoamer, a stabilizer and a dispersant are added, and the mixture is stirred and mixed to obtain a microemulsion.

[0081] Example 5

[0082] A microemulsion, the preparation raw materials of which include, by weight percentage, 38% of a bactericidal composition, 14% of an emulsifier, 1.5% of a stabilizer, 1% of a defoaming agent, and the remainder of a dispersant to 100%.

[0083] The bactericidal composition comprises pyraclostrobin and clofoconazole, and the weight ratio thereof is 1:4.5.

[0084] The emulsifier is a condensate of triphenylethylphenol polyoxyethylene ether polyoxypropylene ether and naphthalenesulfonic acid sodium salt formaldehyde, and the weight ratio is 1:0.4;

[0085] The described triphenyl phenol polyoxyethylene ether polyoxypropylene ether has a model of 1601# and an HLB value of 16.9;

[0086] The naphthalenesulfonic acid sodium salt formaldehyde condensate was purchased from Anyang Shuanghuan Auxiliary Agent Co., Ltd.;

[0087] The stabilizer is azone.

[0088] The defoamer is an organosilicon defoamer, model ZY-5731A, purchased from Shanghai Ziyi Chemical Co., Ltd.

[0089] The dispersant comprises an organic solvent and water, wherein the organic solvent accounts for 25% of the total weight of the raw materials for preparing the microemulsion, and the water supplements the balance to 100%.

[0090] The organic solvent comprises cyclohexanone and solvent oil 200, and the weight ratio thereof is 1:1.5.

[0091] A method for preparing a microemulsion comprises the following steps:

[0092] The bactericidal composition and the preparation raw materials are stirred and dissolved, and after they are completely dissolved, an emulsifier, a defoamer, a stabilizer and a dispersant are added, and the mixture is stirred and mixed to obtain a microemulsion.

[0093] Performance Testing

[0094] 1. Stability: The microemulsions prepared in Examples 1-5 were subjected to stability tests. The test method was carried out in accordance with GB / T1603. The product of the example was diluted 200 times with 342 mg / L standard hard water and allowed to stand at 30°C for 30 min. The product remained transparent. If there was no floating oil on the surface and no precipitation on the bottom, and the product could be mixed with water in any proportion, the stability was qualified. Otherwise, the product was unqualified. The results are recorded in the following table.

[0095] 2. Thermal storage stability: The samples prepared in Examples 1-5 were placed in ampoules and placed in a thermostat at 54° C. for 14 days. Changes in appearance were observed and the results are recorded in the table below.

[0096]

[0097]

Claims

1. A microemulsion, characterized in that: The raw materials for preparation include, by weight percentage: 38% of bactericidal composition, 14% of emulsifier, 1.5% of stabilizer, 1% of defoamer, and the remaining amount of dispersant is supplemented to 100%; The bactericidal composition is pyraclostrobin and clofoconazole, and the weight ratio thereof is 1:4.5; The emulsifier is a condensate of triphenylethylphenol polyoxyethylene ether polyoxypropylene ether and naphthalenesulfonic acid sodium salt formaldehyde, and the weight ratio is 1:0.4; The described triphenyl phenol polyoxyethylene ether polyoxypropylene ether has a model number of 1602# and an HLB value of 16; The stabilizer is azone; The defoamer is a silicone defoamer, model ZY-5731A; The dispersant comprises an organic solvent and water, wherein the organic solvent accounts for 25% of the total weight of the raw materials for preparing the microemulsion, and the water supplements the balance to 100%; The organic solvent comprises cyclohexanone and solvent oil 200, and the weight ratio thereof is 1:1.

5.

2. A method for preparing a microemulsion according to claim 1, characterized in that: The steps include: The bactericidal composition and the preparation raw materials are stirred and dissolved, and after they are completely dissolved, an emulsifier, a defoamer, a stabilizer and a dispersant are added, and the mixture is stirred and mixed to obtain a microemulsion.

3. A use of the microemulsion according to claim 1, characterized in that: Used for the prevention and control of grape powdery mildew, downy mildew, grape black pox and powdery mildew.

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