A suspending agent containing fluazinam and its preparation method

Abstract

This invention relates to the field of pesticide technology, specifically to a suspension containing fluazinam and its preparation method. To enhance the stability of the fluazinam suspension, the raw material components of the suspension are strictly limited, and modified bentonite is prepared and added. First, the bentonite is sodium-treated, and then further modified with 2-methyl-2-acrylic acid ammonium salt to introduce acrylic acid double bonds into the bentonite. Subsequently, this application further prepares a fluorinated compound with a long carbon chain, and uses benzoyl peroxide to react at high temperature, thereby reacting the fluorinated compound with the acrylic acid double bonds, ultimately introducing a long carbon chain compound containing fluorine into the bentonite, thus significantly enhancing the hydrophobicity of the bentonite.

Description

Technical Field

[0001] This invention relates to the field of pesticide technology, specifically to a suspension containing fluazinam and its preparation method. Background Technology

[0002] Fluazinam is an agricultural protective fungicide that has a good inhibitory effect on common agricultural pathogens such as Alternaria, Botrytis, and Phytophthora. Fluazinam is also resistant to rain washout and can maintain its control effect for a long time, providing good control for most agricultural diseases.

[0003] In response to the domestic call for reducing pesticide use, fluazinam is often prepared as a pesticide suspension to enhance its dispersibility in pesticide formulations and ensure its effectiveness during use. However, suspensions are not resistant to long-term storage. After being stored at high temperatures or for extended periods, they often settle, resulting in a decrease in their effectiveness. Therefore, it is necessary to conduct research to address this deficiency in order to meet market demands. Summary of the Invention

[0004] The purpose of this invention is to provide a suspension containing fluazinam and its preparation method, so as to solve the problems mentioned in the background art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a suspension containing fluazinam, having the following technical features: by weight percentage, the suspension comprises the following components: 25-35% fluazinam, 0.8-1.5% antifreeze, 6-12% wetting agent, 0.6-1.1% modified bentonite, 0.1-0.5 parts thickener, 0.2-0.6% defoamer, and the balance being water.

[0006] Furthermore, the wetting agent is a fatty alcohol polyoxyethylene ether; the antifreeze agent is any one or more of ethylene glycol, polyethylene glycol, glycerol, and benzoic acid.

[0007] Furthermore, the thickener is either xanthan gum or hydroxypropyl cellulose ether; the defoamer is an organosilicon defoamer.

[0008] A method for preparing a suspension containing fluazinam includes the following steps:

[0009] S1. Preparation of modified bentonite;

[0010] S11. The bentonite is pulverized and passed through an 80-120 mesh sieve. The resulting bentonite is dispersed in deionized water and stirred for 5-10 minutes. Then, it is subjected to ultrasonic vibration for 2-4 hours. The temperature is raised to 75-85℃, sodium carbonate is added, and the mixture is stirred and reacted for 4-12 hours. The mixture is then centrifuged, and the precipitate is washed with deionized water 3-5 times. It is then vacuum dried to constant weight and dispersed again in dimethyl sulfoxide. After ultrasonic dispersion for 30-45 minutes, 2-methyl-2-acrylic acid ammonium salt is added. The temperature is raised to 100-105℃, and the reaction is carried out for 4-8 hours. The mixture is then centrifuged and vacuum dried to constant weight to obtain organic modified bentonite.

[0011] S12. Disperse 4,4'-diaminodiphenyl ether in DMF, mix thoroughly, and cool to 5-8℃ to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, treat 1,6-hexanediol diglycidyl ether in an ice-water bath to a constant temperature, then add the 4,4'-diaminodiphenyl ether solution dropwise while stirring. After the addition is complete, heat the mixed solution to 10-15℃ and react for 30-45 min. Then, heat the solution to 80-90℃ and continue the reaction for 2-4 h. Finally, evaporate under vacuum to constant weight to obtain a long-chain epoxy compound.

[0012] S13. Disperse 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing a long-chain epoxy compound. After the addition is complete, heat to 85-90℃ and react for 1-1.5 h. Then cool to 3-8℃, add methyl 4-aminobenzoate, mix well, heat to 80-95℃, and continue the reaction for 2-4 h. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0013] S14. After grinding the organic modified bentonite obtained in step S11 with benzoyl peroxide for 15-30 min, xylene is added, and the mixture is ultrasonically vibrated for 5-10 min to obtain an organic modified bentonite dispersion. The fluorinated compound is dispersed in DMF, mixed evenly, and the organic modified bentonite dispersion is added dropwise. After the addition is complete, the temperature is raised to 120-125℃ and reacted for 1-1.5 h. The precipitate is separated by centrifugation, washed 3-5 times with pure xylene, vacuum dried to constant weight, ground, and passed through an 80-120 mesh sieve to obtain modified bentonite.

[0014] S2. Mix fluazinam, antifreeze, wetting agent, thickener, defoamer and water. After mixing for 3-5 minutes, add modified bentonite and continue mixing for 8-15 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspension.

[0015] Furthermore, in step S11, the mass ratio of bentonite, sodium carbonate, and 2-methyl-2-acrylic acid ammonium salt is 1:(0.1-0.3):(0.15-0.4).

[0016] Furthermore, in step S12, the mass ratio of 4,4'-diaminodiphenyl ether to 1,6-hexanediol diglycidyl ether is 1:(1.8-2.35).

[0017] Furthermore, in step S13, the mass ratio of 4-fluoro-2-methylbenzoic acid, long-chain epoxy compound, and methyl 4-aminobenzoate is (0.23-0.28):1:(0.22-0.25).

[0018] Furthermore, in step S14, the mass ratio of organic modified bentonite, benzoyl peroxide, and fluorinated compound is 1:(0.02-0.04):(0.1-0.4).

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] 1. In order to enhance the stability of fluazinam suspension, the present invention strictly limits the raw material components of the suspension and uses different components such as wetting agents, thickeners and defoamers to compound the suspension. The fluazinam suspension prepared by the present invention has good stability and dispersibility. In order to further enhance the storage stability of fluazinam suspension, the present invention further prepares and adds modified bentonite, thereby ensuring the storage stability of fluazinam suspension prepared by the present invention.

[0021] 2. Bentonite is a type of high-molecular-weight clay mineral with a large specific surface area and contains a significant amount of soluble metal ions. Therefore, this invention first uses sodium carbonate solution to sodium-modify it, using sodium ions to replace some of the metal ions. Then, the sodium-modified bentonite is further mixed with 2-methyl-2-ammonium acrylate to organically modify the bentonite, introducing organic cations to replace sodium ions in the bentonite lattice and introducing reactive double bonds. Based on this, this invention further utilizes 4,4'-diaminodi... The reaction of phenyl ether with 1,6-hexanediol diglycidyl ether, under controlled reaction conditions, ultimately produces an epoxy compound with an epoxy group at the end and a long carbon chain. This invention then reacts the epoxy compound with 4-fluoro-2-methylbenzoic acid, introducing highly electronegative fluorine into the long-chain epoxy compound. Finally, the compound is mixed with organically modified bentonite, and under the action of benzoyl peroxide, the reactivity of the double bond is utilized to introduce a fluorine-containing compound into the bentonite, enhancing its hydrophobicity, improving its suspension stability, and ultimately improving the storage stability of the suspending agent. Detailed Implementation

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] The bentonite used in this application is MZ-100 type calcium-based bentonite provided by Hebei Mingzhe Mineral Products Co., Ltd.; the 2-methyl-2-acrylate ammonium salt used is provided by Shanghai Kaiyin Chemical Co., Ltd.; the 4,4'-diaminodiphenyl ether, 1,6-hexanediol diglycidyl ether, and 4-fluoro-2-methylbenzoic acid used are provided by Shanghai Aladdin Biochemical Technology Co., Ltd.; the fatty alcohol polyoxyethylene ether used is AEO-3 type fatty alcohol polyoxyethylene ether provided by Nanjing Taihua Chemical Co., Ltd.; and the organosilicon defoamer used is AT-470 type defoamer provided by Datian Chemical.

[0024] Example 1. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0025] S1. Preparation of modified bentonite;

[0026] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, 0.1 parts of sodium carbonate were added, and the mixture was stirred and reacted for 4 hours. The mixture was centrifuged, and the precipitate was washed three times with deionized water. It was then vacuum dried to constant weight and dispersed again in 5 parts of dimethyl sulfoxide. After ultrasonic dispersion for 30 minutes, 0.15 parts of 2-methyl-2-acrylic acid ammonium salt were added, and the temperature was raised to 100°C. The mixture was reacted for 4 hours, centrifuged, and vacuum dried to constant weight to obtain organic modified bentonite.

[0027] S12. By weight, 1 part of 4,4'-diaminodiphenyl ether was dispersed in DMF, mixed evenly, and then cooled to 5°C to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, 1.8 parts of 1,6-hexanediol diglycidyl ether were treated in an ice-water bath to a constant temperature, and then the 4,4'-diaminodiphenyl ether solution was added dropwise while stirring. After the addition was completed, the mixed solution was heated to 10°C, reacted for 30 min, then heated to 80°C, and reacted for another 2 h. Finally, the mixture was vacuum evaporated to constant weight to obtain a long-chain epoxy compound.

[0028] S13. Disperse 0.23 parts of 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing 1 part of a long-chain epoxy compound. After the addition is complete, heat to 85°C and react for 1 hour. Then cool the mixed solution to 3°C, add 0.22 parts of methyl 4-aminobenzoate, mix well, heat to 80°C, and continue to react for 2 hours. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0029] S14. Mix and grind 1 part of the organic modified bentonite prepared in step S11 with 0.02 parts of benzoyl peroxide for 15 min, add 5 parts of xylene, and sonicate for 5-10 min to obtain an organic modified bentonite dispersion. Disperse 0.1 parts of the fluorine-containing compound into 1 part of DMF, mix evenly, and add the organic modified bentonite dispersion dropwise. After the addition is complete, heat to 120℃ and react for 1 h. Centrifuge to separate the precipitate, wash 3 times with pure xylene, vacuum dry to constant weight, grind, and pass through an 80-mesh sieve to obtain modified bentonite.

[0030] S2. By weight, mix 25 parts of fluazinam, 0.8 parts of ethylene glycol, 6 parts of fatty alcohol polyoxyethylene ether, 0.1 parts of xanthan gum, 0.2 parts of silicone defoamer and 67.3 parts of water. After mixing for 3 minutes, add 0.6 parts of modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0031] Example 2. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0032] Compared with Example 1, this example increases the amount of modified bentonite added in step S2;

[0033] S1. Preparation of modified bentonite;

[0034] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, 0.1 parts of sodium carbonate were added, and the mixture was stirred and reacted for 4 hours. The mixture was centrifuged, and the precipitate was washed three times with deionized water. It was then vacuum dried to constant weight and dispersed again in 5 parts of dimethyl sulfoxide. After ultrasonic dispersion for 30 minutes, 0.15 parts of 2-methyl-2-acrylic acid ammonium salt were added, and the temperature was raised to 100°C. The mixture was reacted for 4 hours, centrifuged, and vacuum dried to constant weight to obtain organic modified bentonite.

[0035] S12. By weight, 1 part of 4,4'-diaminodiphenyl ether was dispersed in DMF, mixed evenly, and then cooled to 5°C to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, 1.8 parts of 1,6-hexanediol diglycidyl ether were treated in an ice-water bath to a constant temperature, and then the 4,4'-diaminodiphenyl ether solution was added dropwise while stirring. After the addition was completed, the mixed solution was heated to 10°C, reacted for 30 min, then heated to 80°C, and reacted for another 2 h. Finally, the mixture was vacuum evaporated to constant weight to obtain a long-chain epoxy compound.

[0036] S13. Disperse 0.23 parts of 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing 1 part of a long-chain epoxy compound. After the addition is complete, heat to 85°C and react for 1 hour. Then cool the mixed solution to 3°C, add 0.22 parts of methyl 4-aminobenzoate, mix well, heat to 80°C, and continue to react for 2 hours. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0037] S14. Mix and grind 1 part of the organic modified bentonite prepared in step S11 with 0.02 parts of benzoyl peroxide for 15 min, add 5 parts of xylene, and sonicate for 5-10 min to obtain an organic modified bentonite dispersion. Disperse 0.1 parts of the fluorine-containing compound into 1 part of DMF, mix evenly, and add the organic modified bentonite dispersion dropwise. After the addition is complete, heat to 120℃ and react for 1 h. Centrifuge to separate the precipitate, wash 3 times with pure xylene, vacuum dry to constant weight, grind, and pass through an 80-mesh sieve to obtain modified bentonite.

[0038] S2. By weight, mix 25 parts of fluazinam, 0.8 parts of ethylene glycol, 6 parts of fatty alcohol polyoxyethylene ether, 0.1 parts of xanthan gum, 0.2 parts of silicone defoamer with 66.8 parts of water. After mixing for 3 minutes, add 1.1 parts of modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0039] Example 3. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0040] Compared with Example 2, this example increases the amount of 2-methyl-2-ammonium acrylate added in step S11;

[0041] S1. Preparation of modified bentonite;

[0042] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was then dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, and 0.1 parts of sodium carbonate were added. After mixing evenly, the mixture was stirred and reacted for 4 hours. The mixture was then centrifuged, and the precipitate was washed three times with deionized water. After vacuum drying to constant weight, the precipitate was dispersed again in 5 parts of dimethyl sulfoxide and ultrasonically dispersed for 30 minutes. Then, 0.4 parts of 2-methyl-2-acrylic acid ammonium salt were added, the temperature was raised to 100°C, and the mixture was reacted for 4 hours. After centrifugation, the mixture was vacuum dried to constant weight to obtain organically modified bentonite.

[0043] S12. By weight, 1 part of 4,4'-diaminodiphenyl ether was dispersed in DMF, mixed evenly, and then cooled to 5°C to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, 1.8 parts of 1,6-hexanediol diglycidyl ether were treated in an ice-water bath to a constant temperature, and then the 4,4'-diaminodiphenyl ether solution was added dropwise while stirring. After the addition was completed, the mixed solution was heated to 10°C, reacted for 30 min, then heated to 80°C, and reacted for another 2 h. Finally, the mixture was vacuum evaporated to constant weight to obtain a long-chain epoxy compound.

[0044] S13. Disperse 0.23 parts of 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing 1 part of a long-chain epoxy compound. After the addition is complete, heat to 85°C and react for 1 hour. Then cool the mixed solution to 3°C, add 0.22 parts of methyl 4-aminobenzoate, mix well, heat to 80°C, and continue to react for 2 hours. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0045] S14. Mix and grind 1 part of the organic modified bentonite prepared in step S11 with 0.02 parts of benzoyl peroxide for 15 min, add 5 parts of xylene, and sonicate for 5-10 min to obtain an organic modified bentonite dispersion. Disperse 0.1 parts of the fluorine-containing compound into 1 part of DMF, mix evenly, and add the organic modified bentonite dispersion dropwise. After the addition is complete, heat to 120℃ and react for 1 h. Centrifuge to separate the precipitate, wash 3 times with pure xylene, vacuum dry to constant weight, grind, and pass through an 80-mesh sieve to obtain modified bentonite.

[0046] S2. By weight, mix 25 parts of fluazinam, 0.8 parts of ethylene glycol, 6 parts of fatty alcohol polyoxyethylene ether, 0.1 parts of xanthan gum, 0.2 parts of silicone defoamer with 66.8 parts of water. After mixing for 3 minutes, add 1.1 parts of modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0047] Example 4. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0048] Compared with Example 2, this example increases the amount of 4-fluoro-2-methylbenzoic acid added in step S13;

[0049] S1. Preparation of modified bentonite;

[0050] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, 0.1 parts of sodium carbonate were added, and the mixture was stirred and reacted for 4 hours. The mixture was centrifuged, and the precipitate was washed three times with deionized water. It was then vacuum dried to constant weight and dispersed again in 5 parts of dimethyl sulfoxide. After ultrasonic dispersion for 30 minutes, 0.15 parts of 2-methyl-2-acrylic acid ammonium salt were added, and the temperature was raised to 100°C. The mixture was reacted for 4 hours, centrifuged, and vacuum dried to constant weight to obtain organic modified bentonite.

[0051] S12. By weight, 1 part of 4,4'-diaminodiphenyl ether was dispersed in DMF, mixed evenly, and then cooled to 5°C to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, 1.8 parts of 1,6-hexanediol diglycidyl ether were treated in an ice-water bath to a constant temperature, and then the 4,4'-diaminodiphenyl ether solution was added dropwise while stirring. After the addition was completed, the mixed solution was heated to 10°C, reacted for 30 min, then heated to 80°C, and reacted for another 2 h. Finally, the mixture was vacuum evaporated to constant weight to obtain a long-chain epoxy compound.

[0052] S13. Disperse 0.28 parts of 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing 1 part of a long-chain epoxy compound. After the addition is complete, heat to 85°C and react for 1 hour. Then cool the mixed solution to 3°C, add 0.22 parts of methyl 4-aminobenzoate, mix well, heat to 80°C, and continue to react for 2 hours. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0053] S14. Mix and grind 1 part of the organic modified bentonite prepared in step S11 with 0.02 parts of benzoyl peroxide for 15 min, add 5 parts of xylene, and sonicate for 5-10 min to obtain an organic modified bentonite dispersion. Disperse 0.1 parts of the fluorine-containing compound into 1 part of DMF, mix evenly, and add the organic modified bentonite dispersion dropwise. After the addition is complete, heat to 120℃ and react for 1 h. Centrifuge to separate the precipitate, wash 3 times with pure xylene, vacuum dry to constant weight, grind, and pass through an 80-mesh sieve to obtain modified bentonite.

[0054] S2. By weight, mix 25 parts of fluazinam, 0.8 parts of ethylene glycol, 6 parts of fatty alcohol polyoxyethylene ether, 0.1 parts of xanthan gum, 0.2 parts of silicone defoamer with 66.8 parts of water. After mixing for 3 minutes, add 1.1 parts of modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0055] Example 5. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0056] S1. Preparation of modified bentonite;

[0057] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, 0.3 parts of sodium carbonate were added, and the mixture was stirred and reacted for 4 hours. The mixture was centrifuged, and the precipitate was washed three times with deionized water. It was then vacuum dried to constant weight and dispersed again in 5 parts of dimethyl sulfoxide. After ultrasonic dispersion for 30 minutes, 0.4 parts of 2-methyl-2-acrylic acid ammonium salt were added, and the temperature was raised to 100°C. The mixture was reacted for 4 hours, centrifuged, and vacuum dried to constant weight to obtain organic modified bentonite.

[0058] S12. By weight, 1 part of 4,4'-diaminodiphenyl ether was dispersed in DMF, mixed evenly, and then cooled to 5°C to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, 2.35 parts of 1,6-hexanediol diglycidyl ether were treated in an ice-water bath to a constant temperature, and then the 4,4'-diaminodiphenyl ether solution was added dropwise while stirring. After the addition was completed, the mixed solution was heated to 10°C, reacted for 30 min, then heated to 80°C, and reacted for another 2 h. Finally, the mixture was vacuum evaporated to constant weight to obtain a long-chain epoxy compound.

[0059] S13. Disperse 0.28 parts of 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing 1 part of a long-chain epoxy compound. After the addition is complete, heat to 85°C and react for 1 hour. Then cool the mixed solution to 3°C, add 0.25 parts of methyl 4-aminobenzoate, mix well, heat to 80°C, and continue to react for 2 hours. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0060] S14. After grinding 1 part of the organic modified bentonite prepared in step S11 with 0.04 parts of benzoyl peroxide for 15 min, add 5 parts of xylene and sonicate for 5-10 min to obtain an organic modified bentonite dispersion. Disperse 0.4 parts of the fluorine-containing compound into 1 part of DMF, mix evenly, and then add the organic modified bentonite dispersion dropwise. After the addition is complete, heat to 120℃ and react for 1 h. Centrifuge to separate the precipitate, wash 3 times with pure xylene, vacuum dry to constant weight, grind, and pass through an 80-mesh sieve to obtain modified bentonite.

[0061] S2. By weight, mix 35 parts of fluazinam, 1.5 parts of ethylene glycol, 12 parts of fatty alcohol polyoxyethylene ether, 0.5 parts of xanthan gum, 0.6 parts of silicone defoamer and 49.3 parts of water. After mixing for 3 minutes, add 1.1 parts of modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0062] Comparative Example 1. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0063] Compared to Example 2, this comparative example did not use 2-methyl-2-acrylic acid ammonium salt to treat bentonite;

[0064] S1. Preparation of modified bentonite;

[0065] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, 0.1 parts of sodium carbonate were added, and the mixture was stirred and reacted for 4 hours. After centrifugation, the precipitate was washed three times with deionized water to obtain organic modified bentonite.

[0066] S12. By weight, 1 part of 4,4'-diaminodiphenyl ether was dispersed in DMF, mixed evenly, and then cooled to 5°C to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, 1.8 parts of 1,6-hexanediol diglycidyl ether were treated in an ice-water bath to a constant temperature, and then the 4,4'-diaminodiphenyl ether solution was added dropwise while stirring. After the addition was completed, the mixed solution was heated to 10°C, reacted for 30 min, then heated to 80°C, and reacted for another 2 h. Finally, the mixture was vacuum evaporated to constant weight to obtain a long-chain epoxy compound.

[0067] S13. Disperse 0.23 parts of 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing 1 part of a long-chain epoxy compound. After the addition is complete, heat to 85°C and react for 1 hour. Then cool the mixed solution to 3°C, add 0.22 parts of methyl 4-aminobenzoate, mix well, heat to 80°C, and continue to react for 2 hours. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0068] S14. Mix and grind 1 part of the organic modified bentonite prepared in step S11 with 0.02 parts of benzoyl peroxide for 15 min, add 5 parts of xylene, and sonicate for 5-10 min to obtain an organic modified bentonite dispersion. Disperse 0.1 parts of the fluorine-containing compound into 1 part of DMF, mix evenly, and add the organic modified bentonite dispersion dropwise. After the addition is complete, heat to 120℃ and react for 1 h. Centrifuge to separate the precipitate, wash 3 times with pure xylene, vacuum dry to constant weight, grind, and pass through an 80-mesh sieve to obtain modified bentonite.

[0069] S2. By weight, mix 25 parts of fluazinam, 0.8 parts of ethylene glycol, 6 parts of fatty alcohol polyoxyethylene ether, 0.1 parts of xanthan gum, 0.2 parts of silicone defoamer with 66.8 parts of water. After mixing for 3 minutes, add 1.1 parts of modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0070] Comparative Example 2. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0071] Compared to Example 2, this comparative example only prepared organically modified bentonite;

[0072] S1. Preparation of organically modified bentonite;

[0073] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, 0.1 parts of sodium carbonate were added, and the mixture was stirred and reacted for 4 hours. The mixture was centrifuged, and the precipitate was washed three times with deionized water. It was then vacuum dried to constant weight and dispersed again in 5 parts of dimethyl sulfoxide. After ultrasonic dispersion for 30 minutes, 0.15 parts of 2-methyl-2-acrylic acid ammonium salt were added, and the temperature was raised to 100°C. The mixture was reacted for 4 hours, centrifuged, and vacuum dried to constant weight to obtain organic modified bentonite.

[0074] S2. By weight, mix 25 parts of fluazinam, 0.8 parts of ethylene glycol, 6 parts of fatty alcohol polyoxyethylene ether, 0.1 parts of xanthan gum, 0.2 parts of silicone defoamer with 66.8 parts of water. After mixing for 3 minutes, add 1.1 parts of organic modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0075] Comparative Example 3. A method for preparing a suspension containing fluazinam, comprising the following steps:

[0076] Compared to Example 2, this comparative example used benzoic acid instead of 4-fluoro-2-methylbenzoic acid;

[0077] S1. Preparation of modified bentonite;

[0078] S11. By weight, 1 part of bentonite was pulverized and passed through an 80-mesh sieve. The resulting bentonite was dispersed in 5 parts of deionized water, stirred for 5 minutes, and then subjected to ultrasonic vibration for 2 hours. The temperature was raised to 75°C, 0.1 parts of sodium carbonate were added, and the mixture was stirred and reacted for 4 hours. The mixture was centrifuged, and the precipitate was washed three times with deionized water. It was then vacuum dried to constant weight and dispersed again in 5 parts of dimethyl sulfoxide. After ultrasonic dispersion for 30 minutes, 0.15 parts of 2-methyl-2-acrylic acid ammonium salt were added, and the temperature was raised to 100°C. The mixture was reacted for 4 hours, centrifuged, and vacuum dried to constant weight to obtain organic modified bentonite.

[0079] S12. By weight, 1 part of 4,4'-diaminodiphenyl ether was dispersed in DMF, mixed evenly, and then cooled to 5°C to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, 1.8 parts of 1,6-hexanediol diglycidyl ether were treated in an ice-water bath to a constant temperature, and then the 4,4'-diaminodiphenyl ether solution was added dropwise while stirring. After the addition was completed, the mixed solution was heated to 10°C, reacted for 30 min, then heated to 80°C, and reacted for another 2 h. Finally, the mixture was vacuum evaporated to constant weight to obtain a long-chain epoxy compound.

[0080] S13. Disperse 0.23 parts of benzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing 1 part of a long-chain epoxy compound. After the addition is complete, heat to 85°C and react for 1 hour. Then cool the mixed solution to 3°C, add 0.22 parts of methyl 4-aminobenzoate, mix well, heat to 80°C, and continue to react for 2 hours. Remove excess solvent by rotary evaporation to obtain a fluorinated compound.

[0081] S14. Mix and grind 1 part of the organic modified bentonite prepared in step S11 with 0.02 parts of benzoyl peroxide for 15 min, add 5 parts of xylene, and sonicate for 5-10 min to obtain an organic modified bentonite dispersion. Disperse 0.1 parts of the fluorine-containing compound into 1 part of DMF, mix evenly, and add the organic modified bentonite dispersion dropwise. After the addition is complete, heat to 120℃ and react for 1 h. Centrifuge to separate the precipitate, wash 3 times with pure xylene, vacuum dry to constant weight, grind, and pass through an 80-mesh sieve to obtain modified bentonite.

[0082] S2. By weight, mix 25 parts of fluazinam, 0.8 parts of ethylene glycol, 6 parts of fatty alcohol polyoxyethylene ether, 0.1 parts of xanthan gum, 0.2 parts of silicone defoamer with 66.8 parts of water. After mixing for 3 minutes, add 1.1 parts of modified bentonite and continue mixing for 8 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspending agent.

[0083] Testing: The dispersibility of the fluazinam suspensions prepared in Examples 1-5 and Comparative Examples 1-3 was tested according to the FAO standard CIPAC method; the suspension rate of the fluazinam suspensions prepared in Examples 1-5 and Comparative Examples 1-3 was tested according to GB / T14825-2006; the thermal storage stability of the fluazinam suspensions prepared in Examples 1-5 and Comparative Examples 1-3 at 14 days and 28 days was tested according to GB / T19136-2003; the test results are shown in the table below.

[0084] Dispersion Suspension rate (%) 14-day thermal storage stability 28-day thermal storage stability Example 1 good 91 B B Example 2 excellent 94 A B Example 3 excellent 96 A B Example 4 excellent 95 A B Example 5 good 86 B C Comparative Example 1 good 85 C C Comparative Example 2 Poor 75 C C Comparative Example 3 good 88 B C

[0085] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a suspension containing fluazinam, characterized in that, Includes the following steps: S1. Preparation of modified bentonite; S11. The bentonite is pulverized and passed through an 80-120 mesh sieve. The resulting bentonite is dispersed in deionized water and stirred for 5-10 minutes. Then, it is subjected to ultrasonic vibration for 2-4 hours. The temperature is raised to 75-85℃, sodium carbonate is added, and the mixture is stirred and reacted for 4-12 hours. The mixture is then centrifuged, and the precipitate is washed with deionized water 3-5 times. It is then vacuum dried to constant weight and dispersed again in dimethyl sulfoxide. After ultrasonic dispersion for 30-45 minutes, 2-methyl-2-acrylic acid ammonium salt is added. The temperature is raised to 100-105℃, and the reaction is carried out for 4-8 hours. The mixture is then centrifuged and vacuum dried to constant weight to obtain organic modified bentonite. S12. Disperse 4,4'-diaminodiphenyl ether in DMF, mix thoroughly, and cool to 5-8℃ to obtain a 4,4'-diaminodiphenyl ether solution; under a nitrogen atmosphere, treat 1,6-hexanediol diglycidyl ether in an ice-water bath to a constant temperature, then add the 4,4'-diaminodiphenyl ether solution dropwise while stirring. After the addition is complete, heat the mixed solution to 10-15℃ and react for 30-45 min. Then, heat the solution to 80-90℃ and continue the reaction for 2-4 h. Finally, evaporate under vacuum to constant weight to obtain a long-chain epoxy compound. S13. Disperse 4-fluoro-2-methylbenzoic acid in xylene, mix well, and then add it dropwise to a xylene solution containing a long-chain epoxy compound. After the addition is complete, heat to 85-90℃ and react for 1-1.5 h. Then cool to 3-8℃, add methyl 4-aminobenzoate, mix well, heat to 80-95℃, and continue the reaction for 2-4 h. Remove excess solvent by rotary evaporation to obtain a fluorinated compound. S14. After grinding the organic modified bentonite obtained in step S11 with benzoyl peroxide for 15-30 min, xylene is added, and the mixture is ultrasonically vibrated for 5-10 min to obtain an organic modified bentonite dispersion. The fluorinated compound is dispersed in DMF, mixed evenly, and the organic modified bentonite dispersion is added dropwise. After the addition is complete, the temperature is raised to 120-125℃ and reacted for 1-1.5 h. The precipitate is separated by centrifugation, washed 3-5 times with pure xylene, vacuum dried to constant weight, ground, and passed through an 80-120 mesh sieve to obtain modified bentonite. S2. Mix fluazinam, antifreeze, wetting agent, thickener, defoamer and water. After mixing for 3-5 minutes, add modified bentonite and continue mixing for 8-15 minutes. Grind the mixture until the solid particle size in the mixture is 3-5 micrometers. Stop grinding and cool to room temperature to obtain a suspension. The suspending agent, by weight percentage, comprises the following components: 25-35% fluazinam, 0.8-1.5% antifreeze, 6-12% wetting agent, 0.6-1.1% modified bentonite, 0.1-0.5 parts thickener, 0.2-0.6% defoamer, and the balance being water.

2. The method for preparing a suspension containing fluazinam according to claim 1, characterized in that: The wetting agent is fatty alcohol polyoxyethylene ether; the antifreeze agent is any one or more of ethylene glycol, polyethylene glycol, glycerol, and benzoic acid.

3. The method for preparing a suspension containing fluazinam according to claim 1, characterized in that: The thickener is either xanthan gum or hydroxypropyl cellulose ether; the defoamer is an organosilicon defoamer.

4. The method for preparing a suspension containing fluazinam according to claim 1, characterized in that: In step S11, the mass ratio of bentonite, sodium carbonate, and 2-methyl-2-acrylic acid ammonium salt is 1:(0.1-0.3):(0.15-0.4).

5. The method for preparing a suspension containing fluazinam according to claim 1, characterized in that: In step S12, the mass ratio of 4,4'-diaminodiphenyl ether to 1,6-hexanediol diglycidyl ether is 1:(1.8-2.35).

6. The method for preparing a suspension containing fluazinam according to claim 1, characterized in that: In step S13, the mass ratio of 4-fluoro-2-methylbenzoic acid, long-chain epoxy compound, and methyl 4-aminobenzoate is (0.23-0.28):1:(0.22-0.25).

7. The method for preparing a suspension containing fluazinam according to claim 1, characterized in that: In step S14, the mass ratio of organic modified bentonite, benzoyl peroxide, and fluorinated compound is 1:(0.02-0.04):(0.1-0.4).