阅读说明：本技术 一种可分散的杀菌组合物及其制备方法和应用 (Dispersible bactericidal composition and preparation method and application thereof ) 是由 罗昌炎 詹姆斯·T·布里斯托 于 2021-02-10 设计创作，主要内容包括：本发明涉及一种包含甲基硫菌灵和吡唑醚菌酯的杀菌组合物,该组合物中包含如本文所定义的式(I)的嵌段共聚物,以提升组合物制剂产品的悬浮率。本发明进一步涉及一种制备所述杀菌组合物的方法；一种可以通过混合甲基硫菌灵、吡唑醚菌酯、式(I)的嵌段共聚物、任选的功能性助剂湿法砂磨得到含水的悬浮液,进一步加工后得到所需的水悬浮剂、干悬浮剂、可分散颗粒剂、可湿性粉剂等剂型的产品。(The invention relates to a bactericidal composition containing thiophanate methyl and pyraclostrobin, which contains a block copolymer of a formula (I) as defined in the specification, so as to improve the suspension rate of a composition preparation product. The invention further relates to a method for preparing the bactericidal composition; a product which can be prepared by mixing thiophanate methyl, pyraclostrobin, the block copolymer of the formula (I) and optional functional auxiliary agent, performing wet sanding to obtain an aqueous suspension, and further processing to obtain required formulations such as aqueous suspension, dry suspension, dispersible granules, wettable powder and the like.)

1. A dispersible bactericidal composition, which is characterized by comprising thiophanate methyl, pyraclostrobin and a block copolymer shown as a formula (I),

wherein R is H or C₂-C₁₈X is more than or equal to 0 and less than 500, y is more than 0 and less than 500, z is more than or equal to 0 and less than 500, and x and z are not 0 at the same time.

2. The germicidal composition as claimed in claim 1, wherein the block copolymer of formula (I) is contained in an amount of 0.5-10 wt%, preferably 0.8-8 wt%, more preferably 1-6 wt%, based on 100 wt% of the germicidal composition.

3. The bactericidal composition of claim 1 or 2, wherein R is H or C₄-C₁₆An alkyl group.

4. The bactericidal composition of any one of claims 1-3, wherein R is H or C₄-C₁₂An alkyl group.

5. The fungicidal composition according to any one of claims 1 to 4, characterized in that the block copolymer represented by formula (I) has a molar molecular weight of 3000-50000, preferably of 5000-30000.

6. The germicidal composition as claimed in any one of claims 1 to 5, wherein the block copolymer of formula (I) has an HLB value of 15 to 30, preferably an HLB of 17 to 28.

7. The bactericidal composition according to any one of claims 1 to 6, wherein the thiophanate-methyl is contained in an amount of 5 to 80 wt% based on 100% by weight of the sum of the bactericidal composition.

8. The bactericidal composition according to any one of claims 1 to 7, wherein the composition comprises 1 to 50 wt% of pyraclostrobin, based on 100% of the total weight of the bactericidal composition.

9. The bactericidal composition according to any one of claims 1 to 8, wherein the weight ratio of thiophanate methyl to pyraclostrobin is 1:2 to 10:1, preferably 1:1 to 8: 1.

10. The germicidal composition of any of claims 1-9, wherein the germicidal composition comprises: 10-65 wt% thiophanate methyl, 5-30 wt% pyraclostrobin and 1-6 wt% of a block copolymer represented by formula (I), wherein the amounts of these components together total 16-80 wt%.

11. A method of preparing a fungicidal composition according to any of claims 1 to 10, comprising:

mixing thiophanate methyl, pyraclostrobin, a block copolymer shown in a formula (I) and water, and performing wet sanding to obtain a suspension mother solution containing the bactericidal composition; then adding functional auxiliary agents to prepare a formulation preparation containing the sterilizing composition.

12. A stable aqueous suspension spray liquid comprising the fungicidal composition according to any one of claims 1 to 10 and water.

13. A process for the preparation of a stable aqueous suspension spray according to claim 12 which comprises: mixing water and the germicidal composition of any one of claims 1-10 to obtain the stable aqueous suspension spray.

Technical Field

The invention relates to the technical field of pesticides, in particular to a bactericidal composition containing thiophanate-methyl and pyraclostrobin, more particularly relates to a dispersible bactericidal composition containing thiophanate-methyl and pyraclostrobin, and particularly relates to a water suspending agent, a dry suspending agent, a water dispersible granule and a wettable powder containing thiophanate-methyl and pyraclostrobin, wherein the product has a high suspension rate when diluted by water.

Background

Thiophanate-methyl (thiophanate-methyl), chemical name: 1, 2-bis (3-methoxycarbonyl-2-thioureido) benzene. Thiophanate methyl belongs to benzimidazole, is a broad-spectrum systemic low-toxicity fungicide, and has systemic, preventive and therapeutic effects. It is developed by Nippon Caoda corporation and can effectively prevent and treat diseases of various crops. It is transformed into carbendazim in plants, interferes with the formation of spindle in the mitosis of the bacterium, and affects cell division. Has better prevention and treatment effect on various diseases of cereals, vegetables and fruit trees. For example, the composition can be used for preventing and treating powdery mildew and anthracnose of cucumber, gray mold, anthracnose and sclerotinia of eggplant, onion, celery, tomato, kidney bean and the like, and diseases of fruit trees such as ring spot and anthracnose of pear tree; brown spot, anthracnose, gray mold, peach brown rot, etc. of grape and strawberry, and blue mold and green mold in orange storage; wheat smut, gibberellic disease, powdery mildew, rice blast, etc.

Pyraclostrobin (pyraclostrobin), chemical name: n- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl ] oxymethyl ] phenyl ] -N-methoxycarbamic acid methyl ester. Pyraclostrobin is a broad-spectrum bactericide for strawberry powdery mildew and cucumber downy mildew; pear scab, leaf spot, grape downy mildew, anthracnose and powdery mildew, and early blight, late blight, powdery mildew and leaf blight of tomatoes and potatoes; wheat powdery mildew, banded sclerotial blight, rust disease and the like have better control effects. Is widely used for preventing and controlling diseases of fruit trees, vegetables, tea trees, tobacco, ornamental plants, lawns and other field crops. In addition, the melting point of the pyraclostrobin is lower, generally 63.7-65.2 ℃, and the pyraclostrobin is usually directly subjected to air flow crushing or pressure granulation, so that the pyraclostrobin raw pesticide is easily softened or melted to cause processing failure.

In addition, US8859607B2 also describes that thiophanate-methyl and pyraclostrobin can form a thiophanate-pyraclostrobin eutectic compound due to the molecular structural characteristics of the compounds. Therefore, when the preparation containing thiophanate-methyl and pyraclostrobin granules, such as an aqueous suspension, a dry suspension, a water dispersible granule and a wettable powder containing thiophanate-methyl and pyraclostrobin, is prepared, the thiophanate-methyl and pyraclostrobin granules are subjected to eutectic phenomena in the processes of processing, preparation and storage, so that the physical and chemical properties of the product are obviously changed, and particularly the suspension rate of the product is greatly reduced.

Disclosure of Invention

In order to solve the technical problems, the invention aims to provide a bactericidal composition containing thiophanate-methyl and pyraclostrobin and a preparation method and application thereof, which overcome the defects.

To achieve the purpose, the invention adopts the following technical means:

in a first aspect, the invention provides a dispersed bactericidal composition comprising thiophanate methyl, pyraclostrobin and a block copolymer shown as a formula (I),

wherein R is H or C₂-C₁₈X is more than or equal to 0 and less than 500, y is more than 0 and less than 500, z is more than or equal to 0 and less than 500, and x and z are not 0 at the same time.

Said C is₂-C₁₈The alkyl group of (b) means an alkyl group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 16, 18 carbon atoms; x may be selected from 0, 1,2, 5, 10, 30, 50, 100, 220, 250, 275, 312, 350, 400, 425, or 500; y may be selected from 1,2, 5, 12, 28, 50, 110, 220, 250, 275, 312, 350, 400, 425, or 500; z may be selected from 0, 1,2, 5, 10, 30, 50, 100, 220, 250, 275, 312, 350, 400, 425, or 500.

Surprisingly, the problem that the suspension rate of a product is reduced due to the formation of eutectic substances in the processing and preparation process and the storage process of the product of the bactericidal composition containing thiophanate methyl and pyraclostrobin is effectively solved by adding the block copolymer shown in the formula (I).

Preferably, the block copolymer of formula (I) is wherein R is H or C₄-C₁₆Alkyl groups and a molar molecular weight of 3000-50000. Particularly preferred block copolymers of the formula (I) are those in which R is H or C₄-C₁₆Alkyl group with a molar molecular weight of 5000-Those of (a). In particular, the block copolymer of formula (I) is such that R is H or C₄-C₁₂Alkyl groups and a molar molecular weight of 5000-30000 while having an HLB value of from 15 to 30, more particularly, from 17 to 28.

Preferably, the fungicidal composition may comprise up to 10% by weight, preferably up to 8% by weight, in particular up to 6% by weight, of the block copolymer of formula (I), based on 100% by weight of the sum of the fungicidal composition. The fungicidal compositions may comprise at least 0.5% by weight, preferably at least 0.8% by weight, in particular at least 1% by weight, of a block copolymer of the formula (I).

Potentially suitable fungicidal compositions comprise from 0.5 to 10% by weight, especially from 0.8 to 8% by weight, more especially from 1 to 6% by weight, of a block copolymer of the formula (I).

In the bactericidal composition, the weight content of the block copolymer represented by the formula (I) may be, for example: 0.5 wt%, 0.8 wt%, 1 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, or 10 wt%.

Possibly suitable fungicide compositions comprise 5 to 80% by weight, in particular 10 to 70% by weight, more in particular 10 to 65% by weight, of thiophanate methyl.

In the bactericidal composition, the content of thiophanate methyl can be, for example: 5, 7, 10, 12, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 wt%.

Possibly suitable fungicide compositions comprise from 1 to 50% by weight, especially from 2 to 45% by weight, more especially from 5 to 30% by weight of pyraclostrobin.

In the bactericidal composition, the content of the pyraclostrobin can be, for example: 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%.

In the present invention, the weight ratio of thiophanate methyl to pyraclostrobin can be 1:2-10:1, such as 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2.5:1, 2:1, 1:1 or 1:2, preferably 1:1-8:1, more preferably 2:1-5: 1.

The germicidal composition may include 0.5-10 wt% of a block copolymer of formula (I) (e.g., where R is hydrogen or C)₄-C₁₂Alkyl and a molar molecular weight of 5000-30000 with an HLB value of 17 to 28), 5 to 80% by weight of thiophanate-methyl and 1 to 50% by weight of pyraclostrobin, wherein the amounts of these components add up to a total of 6.5 to 90% by weight.

Preferably, the germicidal composition may comprise 0.8-8 wt% of a block copolymer of formula (I) (e.g., where R is hydrogen or C)₄-C₁₂Alkyl and a molar molecular weight of 5000-30000 with an HLB value of 17-28), 10-70% by weight thiophanate-methyl and 2-45% by weight pyraclostrobin, wherein the amounts of these components add up to a total of 12.8-85% by weight.

In particular, the germicidal composition may include 1-6 wt% of a block copolymer of formula (I) (e.g., where R is hydrogen or C)₄-C₁₂Alkyl and a molar molecular weight of 5000-30000 with an HLB value of 17 to 28), 10 to 65% by weight of thiophanate-methyl and 5 to 30% by weight of pyraclostrobin, wherein the amounts of these components add up to a total of 16 to 80% by weight.

In addition, the fungicidal compositions may also comprise adjuvants customarily employed in crop protection products. Suitable auxiliaries are solvents, liquid carriers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetrants, protective colloids, adhesives, thickeners, bactericides, antifreeze agents, antifoam agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are organic solvents such as oils of vegetable or animal origin; alcohols, such as ethanol, propanol, butanol, cyclohexanol; a diol; a ketone; an ester; and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetrants, protective colloids, or adjuvants.

Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonic acids, sulfuric acids, phosphoric acids, carboxylic acids and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl-and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols or sulfates of fatty acid esters. An example of a phosphate is a phosphate ester. Examples of carboxylates are alkyl carboxylates and also carboxylated alcohol or alkylphenol ethoxylates. Preferred anionic surfactants are sulfates and sulfonates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated by 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be used for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitan, sucrose and glucose esters or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol or vinyl acetate. Preferred nonionic surfactants are alkoxylates. Nonionic surfactants such as alkoxylates may also be used as adjuvants.

Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having 1 or 2 hydrophobic groups, or salts of long chain primary amines.

Suitable amphoteric surfactants are alkyl betaines and imidazolines.

Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyoxyethylene and polyoxypropylene, or block polymers of the A-B-C type comprising alkanols, polyoxyethylene and polyoxypropylene.

Suitable polyelectrolytes are polyacids or polybases, with polyacids being preferred. Examples of polybases are polyvinylamine or polyvinylamine. Examples of the polyacid are acrylic acid copolymers or AMPS (2-acrylamido-2-methylpropanesulfonic acid) copolymers. Preferably the polyelectrolyte is a copolymer comprising, in polymerized form, an amide comprising at least one monomer selected from the group consisting of N-vinyllactam, N-C1-C6 alkylacrylamides and N, N-di-C1-C6 alkylacrylamides; poly (C2-6 alkylene glycol) (meth) acrylate and/or mono C1-22 alkyl terminated poly (C2-6 alkylene glycol) (meth) acrylate; C1-C8 alkyl (meth) acrylate; and (meth) acrylic acid. More preferably, the polyelectrolyte is a copolymer comprising, in polymerized form, an amide comprising at least one monomer chosen from N-vinyl lactams; mono C1-22 alkyl terminated poly (C2-6 alkylene glycol) (meth) acrylate; C1-C8 alkyl (meth) acrylate; and (meth) acrylic acid. In another preferred form, the polyelectrolyte is a copolymer comprising, in polymerized form, from 25 to 85% by weight of an amide containing at least one monomer chosen from N-vinyllactams; 1 to 40 weight percent mono C1-22 alkyl terminated poly (C2-6 alkylene glycol) (meth) acrylate; 5-50 wt% of a C1-C8 alkyl (meth) acrylate; and up to 15 wt% (meth) acrylic acid, wherein the sum of the monomers equals 100%. In another preferred form, the polyelectrolyte is a copolymer comprising, in polymerized form, from 30 to 85% by weight of an amide containing at least one monomer chosen from N-vinyllactams; 5 to 20 weight percent mono C1-22 alkyl terminated poly (C2-6 alkylene glycol) (meth) acrylate; 8-35 wt% C1-C8 alkyl (meth) acrylate; and 0.5 to 10% by weight of (meth) acrylic acid, the sum of the monomers being equal to 100%. In another preferred form, the polyelectrolyte is a copolymer comprising, in polymerized form, at least one ethylenically unsaturated monomer containing a sulfonic acid group, at least one monomer selected from the group consisting of C1-C4 alkyl (meth) acrylates, and at least one monomer selected from the group consisting of C6-C22 alkyl (meth) acrylates. In another preferred form, the polyelectrolyte is a copolymer which, in polymerized form, contains from 5 to 50% by weight of at least one ethylenically unsaturated monomer containing sulfonic acid groups, from 20 to 70% by weight of at least one monomer from the group consisting of C1-C4 alkyl (meth) acrylates and from 5 to 30% by weight of at least one monomer from the group consisting of C6-C22 alkyl (meth) acrylates, based on the total weight of the monomers. The concentrate may comprise from 0.5 to 40% by weight, preferably from 2 to 30% by weight, in particular from 5 to 25% by weight, of a polyelectrolyte (for example a polyacid such as an acrylic copolymer or an AMPS copolymer).

Suitable adjuvants are compounds which have negligible or even no pesticidal activity per se and which improve the biological properties of the pesticide on the target. Examples are surfactants, mineral or vegetable oils and other auxiliaries.

Suitable fungicides are bronopol and isothiazolinone derivatives such as alkylisothiazolinone and benzisothiazolinone. Suitable anti-freeze agents are ethylene glycol, propylene glycol, urea and glycerol. Suitable antifoams are polysiloxanes, long-chain alcohols and fatty acid salts. Suitable colorants (e.g., red, blue or green colored) are pigments and water-soluble dyes of low water solubility. Examples are inorganic colorants (e.g., iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g., alizarin colorants, azo colorants and phthalocyanine colorants).

The germicidal composition preferably includes at least one anionic surfactant. The germicidal composition generally comprises not less than 0.1% by weight, preferably not less than 0.5% by weight, especially not less than 1% by weight, of anionic surfactant. The germicidal composition may contain no more than 20 wt%, preferably no more than 10 wt%, especially no more than 5 wt% of anionic surfactant.

The germicidal composition preferably includes at least one nonionic surfactant (e.g., alkoxylate). The germicidal composition generally comprises not less than 0.1% by weight, preferably not less than 0.5% by weight, especially not less than 1% by weight, of nonionic surfactant. The concentrate may contain not more than 15 wt%, preferably not more than 10 wt%, especially not more than 5 wt% of nonionic surfactant.

In addition, in most cases, the bactericidal composition of the present invention is applied by spraying with dilution with water, for example, the bactericidal composition is diluted 100 times, 200 times, 500 times, 1000 times, etc. with water. The spray liquid after dilution with water is in the form of a suspension containing particles of the bactericidal active. Formulations suitable for the fungicidal composition of the present invention include aqueous Suspensions (SC), dry suspensions (DF), Water Dispersible Granules (WDG), Wettable Powders (WP).

Therefore, the invention also relates to a method for preparing the bactericidal composition by wet grinding the block copolymer containing thiophanate methyl, pyraclostrobin and formula (I).

The method comprises the following steps:

mixing thiophanate-methyl, pyraclostrobin and a block copolymer shown as a formula (I) with water;

secondly, wet grinding the mixture obtained in the first step under the condition of optional functional auxiliary agent to obtain particle suspension mother liquor with certain granularity;

thirdly, adding functional additives (such as a defoaming agent, a thickening agent or an anti-freezing agent and the like) into the suspension mother liquor obtained in the second step to obtain the water suspending agent (SC) containing thiophanate-methyl and pyraclostrobin; or adding functional additives (such as a defoaming agent, an inert carrier and the like) into the suspension obtained in the step two, drying and granulating to obtain a solid preparation containing thiophanate methyl and pyraclostrobin, such as dry suspending agents (DF), Water Dispersible Granules (WDG), Wettable Powder (WP) and the like.

Wet milling as used in the present process means sanding of the active particles in the presence of water by a sand mill such that the particle size D90 is 10 μm or less, e.g., 0.4 μm, 0.8 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm, preferably D90 is 5 μm or less. The sanding is carried out at 10-45 deg.C, e.g., 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C or 50 deg.C, preferably 15-45 deg.C.

The solid preparation containing thiophanate methyl and pyraclostrobin prepared by the method adopts wet grinding, so that the processing temperature is easier to control than that of the traditional method of using airflow grinding or mechanical grinding particles, and the risk that pyraclostrobin original drug is softened and even melted due to overhigh temperature is prevented.

The invention also provides a stable aqueous suspension spray liquid which contains the bactericidal composition and water.

The preparation method of the stable aqueous suspension spray liquid comprises the following steps: mixing water and the germicidal composition as described above to obtain the stable aqueous suspension spray.

Compared with the prior art, the invention has at least the following beneficial effects:

the invention has the main advantages of solving the problem that the physical and chemical stability of the product is obviously changed due to spontaneous formation of eutectic substances in the processing process and the storage process of the thiophanate methyl and pyraclostrobin compound product, and particularly improving the suspension rate of the product. On the other hand, the wet-method grinding particles are adopted, the grinding temperature is better controlled than that of the traditional airflow grinding or mechanical grinding particles, the risk of softening or melting the pyraclostrobin particles is prevented, and the processing stability of the product is improved.

Detailed Description

For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The technical solution of the present invention is further illustrated by the specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Block copolymer A: atlas G-5000(Croda Inc), HLB: 17, molecular weight: about 5000;

block copolymer B: synperonic PET 127(Croda Inc), HLB: 22, molecular weight: about 12000;

a block copolymer C: synperonic T908 (Croda Inc), HLB: 28, molecular weight: about 26000;

block copolymer D: meroxapol 174(Stepan Inc), HLB: 12, molecular weight: about 2650;

block copolymer E: poloxamer 182(Stepan Inc), HLB: 7, molecular weight: about 2500 a.

Example 1

Thiophanate-methyl and pyraclostrobin 30% + 5% aqueous suspension

The thiophanate-methyl, the pyraclostrobin, Atlas G-5000, Soprophor SC (ethoxylated ammonium phosphate), Genaol T250P (fatty alcohol polyoxyethylene ether), propylene glycol, silicone oil (part) and water are subjected to sand grinding by a sand grinder to enable the particle size D90 of a sand grinding suspension to be about 4 mu m, and then the rest silicone oil, xanthan gum and Proxel GXL (bactericide) are added and uniformly stirred to obtain the thiophanate-methyl-pyraclostrobin-containing 30% + 5% aqueous suspension.

Example 2

Thiophanate-methyl and pyraclostrobin 60% + 20% water dispersible granule

Mixing thiophanate methyl, pyraclostrobin, Synperonic PET 127, Morwet D450 (naphthalenesulfonate formaldehyde polycondensate), Genapol T250P (fatty alcohol polyoxyethylene ether), silicone oil and a proper amount of water, sanding by a sanding machine to enable the grain diameter D90 of the sanded suspension to be about 4 mu m, then adding crushed kaolin, and carrying out spray drying and granulation on the suspension to obtain the water dispersible granule containing thiophanate methyl and pyraclostrobin 60% + 20%.

Example 3

Thiophanate-methyl and pyraclostrobin 50% + 30% wettable powder

Mixing thiophanate-methyl, pyraclostrobin, Synperonic T908, Reax88A (lignosulfonate), Atlax 4913 (acrylic acid copolymer) and silicone oil with a proper amount of water, sanding by a sanding machine to enable the particle size D90 of the sanded suspension to be about 4 mu m, then adding crushed white carbon black and diatomite, and spray-drying the suspension to prepare 50% + 30% wettable powder containing thiophanate-methyl and pyraclostrobin.

Example 4

Thiophanate-methyl and pyraclostrobin 20% + 10% aqueous suspension

The thiophanate-methyl, the pyraclostrobin, Synperonic PET 127, Geropon T/36 (polyacrylic acid sodium salt), Soprophor BSU (tristyrylphenol polyoxyethylene ether), propylene glycol, silicone oil (part of) and water are subjected to sand grinding by a sand grinder to enable the particle size D90 of a sand grinding suspension to be about 4 mu m, and then the rest silicone oil, xanthan gum and Peoxel GXL (bactericide) are added and stirred uniformly to obtain the thiophanate-methyl and pyraclostrobin 20% + 10% aqueous suspension.

Example 5

30% + 30% water dispersible granule of thiophanate methyl and pyraclostrobin

Mixing thiophanate methyl, pyraclostrobin, Synperonic T908, Morwet D450 (naphthalenesulfonate formaldehyde polycondensate), Atlox 4913 (acrylic acid copolymer), silicone oil and a proper amount of water, sanding by a sanding machine to enable the grain diameter D90 of the sanded suspension to be about 4 mu m, then adding crushed talcum powder, spray-drying the suspension and granulating to obtain the water dispersible granule containing 30% + 30% of thiophanate methyl and pyraclostrobin.

Example 6

10% + 20% aqueous suspending agent containing thiophanate-methyl and pyraclostrobin

The thiophanate-methyl, the pyraclostrobin, the Synperonic T908, the Reax88A (lignosulfonate), the Genapol T250P (fatty alcohol polyoxyethylene ether), the glycerol, the silicone oil (part) and the water are subjected to sanding by a sanding machine to enable the grain diameter D90 of the sanded suspension to be about 4 mu m, and then the rest silicone oil, the xanthan gum and the Proxel GXL (bactericide) are added and stirred uniformly to obtain the thiophanate-methyl + pyraclostrobin 10% + 20% aqueous suspension.

Example 7

Thiophanate-methyl and pyraclostrobin 70% + 10% dry suspending agent

Mixing thiophanate methyl, pyraclostrobin, Synperonic PET 127, Morwet D450 (naphthalene sulfonate formaldehyde polycondensate), Tersperse2700 (polyacrylate salt) and silicone oil with a proper amount of water, sanding by a sanding machine to enable the particle size D90 of sanded suspension to be about 4 mu m, then adding crushed anhydrous lactose, and spray-drying the suspension to obtain the dry suspending agent containing 70% + 10% of thiophanate methyl and pyraclostrobin.

Example 8

Thiophanate-methyl and pyraclostrobin 30% + 5% aqueous suspension

The method comprises the following steps of sanding thiophanate methyl, pyraclostrobin, Meroxapol 174, Soprophor SC (ethoxylated ammonium phosphate), Genaol T250P (fatty alcohol polyoxyethylene ether), propylene glycol, silicone oil (part of) and water by a sanding machine to enable the grain diameter D90 of sanding suspension liquid to be about 4 mu m, then adding the rest silicone oil, xanthan gum and Proxel GXL (bactericide), and uniformly stirring to obtain the suspension containing thiophanate methyl and pyraclostrobin 30% + 5% water.

Example 9

Thiophanate-methyl and pyraclostrobin 60% + 20% water dispersible granule

Mixing thiophanate methyl, pyraclostrobin, Poloxamer 182, Morwet D450 (naphthalene sulfonate formaldehyde polycondensate), Genapol T250P (fatty alcohol polyoxyethylene ether), silicone oil and a proper amount of water, sanding by a sanding machine to enable the grain diameter D90 of sanded suspension to be about 4 mu m, then adding crushed kaolin, and carrying out spray drying and granulation on the suspension to obtain the water dispersible granule containing thiophanate methyl and pyraclostrobin 60% + 20%.

Comparative example 1

Thiophanate-methyl and pyraclostrobin 30% + 5% suspending agent

According to the preparation method of example 1, 30% + 5% aqueous suspending agent of thiophanate methyl + pyraclostrobin of comparative example 1 is prepared.

Comparative example 2

Thiophanate-methyl and pyraclostrobin 60% + 20% water dispersible granule

According to the preparation method of example 2, 60% + 20% water dispersible granules of thiophanate methyl + pyraclostrobin of comparative example 2 were prepared.

Comparative example 3

Thiophanate-methyl and pyraclostrobin 50% + 30% wettable powder

According to the preparation method of example 3, 50% + 30% wettable powder of thiophanate methyl + pyraclostrobin of comparative example 3 is prepared.

Comparative example 4

Thiophanate-methyl and pyraclostrobin 20% + 10% aqueous suspension

According to the preparation method of example 4, a 20% + 10% aqueous suspension of thiophanate methyl + pyraclostrobin of comparative example 4 is prepared.

Comparative example 5

30% + 30% water dispersible granule of thiophanate methyl and pyraclostrobin

According to the preparation method of example 5, 30% + 30% water dispersible granules of thiophanate methyl + pyraclostrobin of comparative example 5 are prepared.

Comparative example 6

10% + 20% aqueous suspending agent containing thiophanate-methyl and pyraclostrobin

According to the preparation method of example 6, 10% + 20% aqueous suspending agent of thiophanate methyl + pyraclostrobin of comparative example 6 is prepared.

Comparative example 7

Thiophanate-methyl and pyraclostrobin 70% + 10% dry suspending agent

According to the preparation method of example 7, 70% + 10% dry suspension of thiophanate methyl + pyraclostrobin of comparative example 7 is prepared.

And (3) performance test comparison:

the samples of examples 1 to 9 and comparative examples 1 to 7 described above were subjected to a heat-storage test at 54 ℃ for 14 days, and then the samples before and after the heat-storage were subjected to a suspension percentage test.

Suspension percentage: referring to the CIPAC MT184 method, a sufficient amount of sample (bg) is weighed to prepare about 250mL of a concentrated aqueous suspension in a graduated cylinder. The cylinder was turned 30 times within 1min, 180 ° upside down and returned to the original position 1 time. The cylinder was placed vertically in a water bath. After 30min, 225mL (9/10) of the suspension was aspirated with a pipette over 10-15 seconds, ensuring that the tip was always a few millimeters below the liquid surface.

The content of the active ingredient in the original sample and in the 25ml suspension in the measuring cylinder was determined. And (3) calculating:

c: preparing the mass of the effective components in the sample, g, of the suspension.

Q: the mass of active ingredient, g, in 25ml of suspension remaining in the graduated cylinder.

The results of the suspension test are shown in table 1:

TABLE 1

The results shown in table 1 show that the bactericidal composition effectively controls the suspension rate of thiophanate methyl and pyraclostrobin before and after storage, improves the quality stability of products, wherein the suspension rate of thiophanate methyl before heat storage is over 88.4%, and the suspension rate of thiophanate methyl after heat storage at 54 ℃ for 14 days is still over 85.7%; the suspension rate of the pyraclostrobin before heat storage is over 88.1 percent, and the suspension rate of the pyraclostrobin after heat storage for 14 days at 54 ℃ is over 84.8 percent.

Further, as can be seen from the comparison between the example 1 and the example 8 and the comparison between the example 2 and the example 9, the examples 8 to 9 are inferior to the examples 1 and 2 in controlling the suspension rate of thiophanate methyl and pyraclostrobin before and after storage, so that the problem of reduction of the suspension rate of the product due to formation of eutectic substances during processing or storage of the thiophanate methyl and the pyraclostrobin can be further controlled by using the block copolymer represented by the formula (I) with the molecular weight of 3000-50000 and the HLB value of 15 to 30, the suspension rate and the quality stability of the product can be effectively improved, the suspension rate of the thiophanate methyl before thermal storage can reach more than 94.3%, and the suspension rate of the thiophanate methyl after thermal storage at 54 ℃ for 14 days can be maintained at more than 93.3%; the suspension rate of the pyraclostrobin before heat storage is over 93.7 percent, and the suspension rate of the pyraclostrobin after heat storage for 14 days at 54 ℃ is over 92.4 percent.