AU2019360278A1 - Dinotefuran oil-based suspension concentrate and preparation method therefor - Google Patents
Dinotefuran oil-based suspension concentrate and preparation method therefor Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
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Abstract
A dinotefuran oil-based suspension concentrate and a preparation method therefor, comprising: a) under heating, mixing dinotefuran, a first emulsifier, a dispersant, and water, and dissolving to obtain a dinotefuran aqueous solution; b) mixing a second emulsifier, a thickener, and an oil to obtain a mixed oil solution; and c) under high-speed mixing, adding the dinotefuran aqueous solution of step a) into the mixed oil solution of step b), and emulsifying to obtain a W/O emulsion. By means of the described method, dinotefuran can be pre-dissolved in water, and then emulsified and dispersed into oil to form a W/O emulsion, allowing for a nanoscopic grain diameter of dinotefuran particles precipitating inside droplets, excellent storage stability, rapid diffusion, and high efficacy.
Description
DINOTEFURAN DISPERSIBLE OIL SUSPENSION AND PREPARATION METHOD THEREOF TECHNICAL FIELD The present application relates to the technical field of pesticide formation processing, and particularly relates to a dinotefuran dispersible oil suspension and a preparation method thereof. BACKGROUND TECHNOLOGY Dinotefuran, a third-generation nicotinic insecticide developed by Mitsui Chemicals, Japan, is a broad-spectrum insecticide. It is a stimulant for nicotinic acetylcholine receptors and affects the synapses of the insect central nervous system through spinal nerve transmission. It has contact and stomach toxicity and has excellent internal absorption and osmotic effects. Dinotefuran is very safe to mammals, birds and aquatic organisms, and has no phytotoxicity to crops. It can control Hemiptera, Lepidoptera, Coleoptera, Diptera, Hymenoptera and other pests, and it prevents against rice brown planthopper, white-backed planthoppers, Laodelphax striatellus, and black night tail cicadas with high effect. Dinotefuran relates to a class of poorly soluble active ingredients. It is neither easy to dissolve in polar solvents such as water, nor is it easy to dissolve in small and medium polar solvents and its solubility in water at 25°C is only 40g/L. For poorly soluble active ingredients, the smaller the particle size in the suspension, the greater the number of dispersed particles, the greater the surface area, and the greater the contact area with the target organism, the greater the efficacy of the drug. Dispersible oil suspension is a highly dispersed and stable suspension system with non-aqueous system (oil-based) as the dispersion medium. It is a formulation that uses a type of oil that has been tested as a synergist and does not pollute crops as a dilution carrier and improves the permeability and internal absorption of pesticide active ingredients, and has a good improvement effect. At present, the dispersible oil suspension with dinotefuran as the main active ingredient mainly adopts direct grinding method or sand grinding method. The active ingredient of pesticide, dispersant and other additives are mixed, and are then grounded after pre-dispersing, or are placed into a sand mill for grinding and dispersing after pre-dispersing. However, the active ingredient in the dispersible oil suspension prepared by the above method has a wide particle size distribution, the particle size is often above 0.5[tm, the efficacy is low, the storage stability is poor, and, the collision and friction between the sanding medium (glass beads, zirconium beads) and the collision and friction between the sanding medium and the inner wall of the cavity will produce mechanical impurities which cannot be removed by the filter. The introduced impurities affect the stability of the dispersible oil suspension. Chinese patent 201610739132.5 discloses a dinotefuran dispersible oil suspension and a preparation method thereof. The direct grinding method is adopted, and the particle size of the preparation is 2 to 4 m. TECHNICAL PROBLEM The embodiment of the present application provides a preparation method of dinotefuran dispersible oil suspension, so as to solve the technical problems of dinotefuran dispersible oil suspension obtained by the prior preparation process, such as large particle size of dinotefuran, low efficacy, and introduction of mechanical impurities. BRIEF SUMMARY The embodiment of the present application is achieved in this way. In the first aspect, a preparation method of dinotefuran dispersible oil suspension is provided, including: a) mixing and dissolving the dinotefuran, the first emulsifier, dispersant and water to obtain a dinotefuran aqueous agent under heating conditions; b) mixing the second emulsifier, thickener and oil base to obtain a mixed oil agent; c) adding the dinotefuran aqueous agent of step a) to the mixed oil agent of step b) under high-speed stirring and emulsifying to obtain a W/O emulsion. In the second aspect, the present application also provides a dinotefuran dispersible oil suspension, which is a W/O emulsion, and the droplets of the W/O emulsion contain nanometer-scale dinotefuran crystal particles; Based on 100 parts by weight of its raw materials, the dinotefuran dispersible oil suspension includes: 5-30 parts of dinotefuran; 0-30 parts of second active ingredient; 8-20 parts of emulsifier; 2-4 parts of dispersant; 5-15 parts of water; 0 to 3 parts of thickener; 0 to 1 part of antioxidant; 0 to 0.3 part of pH regulator; the balance is oil base. BENEFICIAL EFFECT In the embodiments of the present application, by taking advantage of the rapid increase in solubility of dinotefuran in hot water, water is used as a solvent to dissolve dinotefuran, and then the first emulsifier and dispersant are added to the aqueous solution of dinotefuran for pre-dispersion to form a homogeneous phase of dinotefuran aquatic agent, and then add the dinotefuran aquatic agent to the mixed oil agent under high-speed stirring to mix and stir; during the stirring process, dinotefuran aquatic agent emulsifies in the mixed oil and form a W/O emulsion with ultra-fine nano-scale droplets. At the same time, dinotefuran forms crystal nuclei in the nano-scale droplets due to the temperature drop, thereby making the particle size of the active ingredient in the present application formulation smaller, reaching nanometer level. The present application uses water as solvent to pre-dissolve dinotefuran, and then emulsify and disperse them into an oil base to form W/O emulsion droplets, making dinotefuran particles of nanometer size, good storage stability, fast diffusion speed, and high efficacy; the present application uses water as a solvent, reduces environmental pollution, saves raw material costs, and is safe and convenient. And water is also an interface stabilizer, has a thickening effect, enhances the storage stability of the formulation, replaces part of the oil base, and reduces costs. DETAILED DESCRIPTIONS In order to make the purpose, technical solutions and advantages of the present application clearer, the present application will be further described in detail below in combination with embodiments. It should be understood that the specific embodiments described here are only used to explain the present application, and are not used to limit the present application. In order to solve the technical problems of large particle size, low efficacy and introduction of mechanical impurities of dinotefuran in the formulation obtained by the existing preparation process. The embodiment of the present applications provide a preparation method of dinotefuran dispersible oil suspension, in which it uses water as a solvent and prepares a formulation containing dinotefuran particles with ultra-fine particle size, which has good storage stability, fast diffusion speed, and high efficacy. A preparation method of dinotefuran dispersible oil suspension in the present application, including: a) mixing and dissolving the dinotefuran, the first emulsifier, dispersant and water to obtain a dinotefuran aquatic agent under heating conditions; b) mixing the second emulsifier, thickener and oil base to obtain a mixed oil agent; c) adding the dinotefuran aquatic agent of step a) to the mixed oil agent of step b) and emulsifying to obtain a W/O emulsion under high-speed stirring. In the above technical solution, the solubility of dinotefuran in water at 25°C is only 40g/L. When the water temperature is greater than 60°C, the solubility is greater than 2000g/L. The embodiment of the present application uses characteristics of dinotefuran to have a sharp increased solubility in hot water, using water as a solvent to dissolve dinotefuran is environmentally friendly and of high production and application safety. The present application is pre-dispersed by adding the first emulsifier and dispersant to the aqueous solution of dinotefuran to prepare a homogeneous dinotefuran aquatic agent; then, adding the dinotefuran aquatic agent to the mixed oil agent under high-speed stirring and continue stirring; during the stirring process, dinotefuran aquatic agent emulsifies in the mixed oil agent and forms a W/O emulsion with ultra-fine nanometer droplets. At the same time, the dinotefuran forms into crystal nucleus inside nanometer droplets due to temperature drop. It overcomes the problems of wide active ingredient particle size distribution and poor storage stability in the dispersible oil suspension prepared by direct sand milling in the prior art, and avoids the introduction of mechanical impurities, has high production efficiency and good stability. Therefore, the formulation prepared by the above-mentioned preparation method has the active ingredient of nanometer particle size, narrow particle size distribution, good storage stability, fast diffusion speed and high efficacy. Furthermore, the sequence of adding dinotefuran, emulsifier and dispersant to water in step a) of the present application is not limited; moreover, the water can be heated in advance as a solvent, or the water can be heated after dinotefuran and water are mixed or the water can be heated after dinotefuran, emulsifier and dispersant were mixed with water. In some optional embodiments of the present application, step a) is specifically: heating dinotefuran to dissolve dinotefuran in water, adding the first emulsifier and dispersant and mixing to obtain dinotefuran aquatic agent. In some other optional embodiments, step a) is specifically: mixing dinotefuran, first emulsifier, dispersant and water, heating to dissolve to form dinotefuran aquatic agent; or adding the first emulsifier, dispersant, dinotefuran into hot water sequentially and dissolving and mixing to form dinotefuran aquatic agent. The high-speed stirring is mainly to enable the dinotefuran aquatic agent to be fully emulsified in the mixed oil agent and to form W/O emulsion droplets with a sufficiently small particle size to improve the stability of the dinotefuran dispersible oil suspension in the embodiments of present application. Optionally, in step c), the rotation speed of high-speed stirring is above 500-10000 rpm; and the stirring time is above 0.5 h. When stirring at a high speed of more than 10000 rpm for 0.5h, the emulsification effect is the best, and the W/O emulsion system is relatively stable, and it is not prone to particle sedimentation and stratification. If the linear velocity of adding the dinotefuran aquatic agent into the mixed oil agent is too high, the shear emulsification will be insufficient and the droplet size will be too large. However, if the linear velocity of adding the dinotefuran aquatic agent into the mixed oil agent is too small, it will reduce the production efficiency. Optionally, the linear velocity of adding the dinotefuran aquatic agent into the mixed oil agent in step c) is 10-50m/min. The dinotefuran has poor water solubility. When the temperature is lower than °C, its solubility in water is low and dissolving dinotefuran requires more water. Too much water may easily cause the dispersible oil suspension of the present application too thick, and cause the droplet size to be too large, reducing the stability of the W/O emulsion. Optionally, the temperature of heating and dissolving in step a) is 50-80°C. In the emulsification process, too much water is used, which will easily cause problems such as demulsification, large droplets, thick system, etc. When the mass ratio of water to the first emulsifier is (5-15): (8-12), it can avoid problems such as demulsification, excessively large droplets and thick system caused by excessive moisture, and ensure the stability and particle size of the formulation, thereby ensuring that the dinotefuran particles in the droplets are ultra-fine. When the mass ratio of water to the first emulsifier is greater than 15:8, the W/O emulsion is too thick, the droplet size is too large, and the stability is reduced. Optionally, the mass ratio of the dinotefuran, water, the first emulsifier and the dispersant is (5-30):(5-15):(8-12):(2-4). Furthermore, the mass ratio of the mixed oil agent and the dinotefuran aquatic agent is 1:(0.1-1), which facilitates the formation of W/O emulsion, ensures complete water emulsification, and obtains nano-scale particles. In the embodiment of the present application, step b) further includes: adding the second active ingredient, antioxidant and pH adjuster; Optionally, the mass ratio of the second active ingredient, antioxidant, pH adjuster, second emulsifier and thickener is 1:(0~2):(0~0.5):(0.1~-10):(0.1~ -2) .
In some optional embodiments, step b) further includes: adding the second active ingredient, antioxidant and pH adjuster at the same time; the mass ratio of the second active ingredient, the antioxidant, the pH adjuster, the second emulsifier and the thickener is 1:(0.1~2):(0.01-0.5):(.1~ -10):(O.1~ -2). In other optional embodiments, in step b) further includes, adding the second active ingredient and antioxidant at the same time; the mass ratio of the second active ingredient, antioxidant, second emulsifier and thickener is 1:(0.1 ~ 2):(O.1 ~ ):(0.1~2); Or: in step b), adding the second active ingredient and pH adjuster at the same time; the mass ratio of the second active ingredient, the pH adjuster, the second emulsifier and the thickener is 1:(0.01~0.5):( 0.1~10): (0.1~2). Further, the second active ingredient of the embodiment of the present application is optionally any one selected from the group consisting of emamectin benzoate, abamectin, pyriproxyfen, lambda-cyhalothrin and chlorpyrifos. After optimization and screening of preliminary experiments, emamectin benzoate, abamectin, pyriproxyfen, lambda-cyhalothrin and chlorpyrifos are oil-soluble, could dissolve in oil, and has a synergistic effect with dinotefuran. Adding antioxidants can prevent active ingredients from being oxidized and being decomposed by air. Optionally, the antioxidant in the embodiment of the present application is at least one selected from the group consisting of dibutylhydroxytoluene, butylhydroxyanisole and tert-butyl hydroquinone. Dibutyl hydroxytoluene, butyl hydroxyanisole and tert-butyl hydroquinone have strong antioxidant capacity, good oil solubility, and can be dissolved in oil base. Some active ingredients are stable in a specific pH range, and are easily decomposed beyond the pH range. Optionally, the pH adjuster in the embodiment of the present application is at least one selected from the group consisting of hydrochloric acid, glacial acetic acid and citric acid. Hydrochloric acid, glacial acetic acid and citric acid have good acid adjustment effects, and hydrochloric acid and glacial acetic acid are liquids with good fluidity at room temperature, and citric acid is solid at room temperature. It is convenient to measure and use, and is easy to operate. In the embodiment of the present application, the first emulsifier and the second emulsifier are at least one independently selected from the group consisting of alkylbenzene sulfonate, dioctyl sulfosuccinate, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, Sorbitol polyoxyethylene ether, styryl phenyl polyoxyethylene ether and styrene phenol formaldehyde resin polyoxyethylene ether; The first emulsifier is different from the second emulsifier. Further, the first emulsifier is any one selected from the group consisting of alkylbenzene sulfonate, dioctyl sulfosuccinate, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, Sorbitol polyoxyethylene ether, styryl phenyl polyoxyethylene ether and styrene phenol formaldehyde resin polyoxyethylene ether. The second emulsifier is at least one selected from the group consisting of alkylbenzene sulfonate, dioctyl sulfosuccinate, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, Sorbitol polyoxyethylene ether, styryl phenyl polyoxyethylene ether and styrene phenol formaldehyde resin polyoxyethylene ether. In the embodiment of the present application, the dispersant is at least one selected from the group consisting of lignosulfonate, polycarboxylate, naphthalene sulfonate, and polyoxyethylene polyoxypropylene block copolymer. Lignosulfonate, polycarboxylate, naphthalene sulfonate and polyoxyethylene polyoxypropylene block copolymer have good viscosity-reducing and dispersing effects on dinotefuran, and are compatible with most emulsifiers. In the embodiment of the present application, the thickener is at least one selected from the group consisting of white carbon black, attapulgite, magnesium aluminum silicate and organic bentonite. The white carbon black, attapulgite, magnesium aluminum silicate and organic bentonite can adjust the viscosity of dispersible oil suspension, form a three-dimensional network structure, stabilize solid particles, and delay sedimentation. In the embodiment of the present application, the oil base is at least one selected from the group consisting of trimethyl benzene, S-100 (No. 100 solvent oil), S-150 (No. 150 solvent oil), S-200 (No. 200 solvent oil), sec-butyl acetate, methyl oleate, turpentine-based vegetable oil, soybean oil, corn oil and mineral oil, with stable properties, wide sources, low viscosity and high safety. Based on the above preparation method, the present application also provides a dinotefuran dispersible oil suspension, which is a W/O emulsion, and the droplets of the W/O emulsion contain nanometer-level dinotefuran crystal particles; Based on 100 parts by weight of its raw materials, the dinotefuran dispersible oil suspension includes: 5-30 parts of dinotefuran; 0-30 parts of second active ingredient; 8-20 parts of emulsifier; 2-4 parts of dispersant; 5-15 parts of water; 0~3 parts of thickener; 0~1 parts of antioxidant; 0~0.3 parts of pH adjuster; the balance is oil base; The second active ingredient is any one selected from the group consisting of emamectin benzoate, abamectin, pyriproxyfen, lambda-cyhalothrin and chlorpyrifos. Furthermore, the particle size of the dinotefuran crystal particles in the droplets in the W/O emulsion of the embodiments of the present application is 200 nm to 500 nm. Furthermore, the emulsifier is at least one selected from the group consisting of alkylbenzene sulfonate, dioctyl sulfosuccinate, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, Sorbitol polyoxyethylene ether, styrene phenyl polyoxyethylene ether and styrene phenol formaldehyde resin polyoxyethylene ether; and/or The dispersant is at least one selected from the group consisting of lignosulfonate, polycarboxylate, naphthalene sulfonate and polyoxyethylene polyoxypropylene block copolymer; and/or The thickener is at least one selected from the group consisting of white carbon black, attapulgite, magnesium aluminum silicate and organic bentonite; and/or The antioxidant is at least one selected from the group consisting of dibutyl hydroxytoluene, butyl hydroxyanisole and tert-butyl hydroquinone; and/or The pH adjuster is at least one selected from the group consisting of hydrochloric acid, glacial acetic acid and citric acid; and/or The oil base is at least one selected from the group consisting of trimethylbenzene, S-100, S-150, S-200, sec-butyl acetate, methyl oleate, turpentine-based vegetable oil, soybean oil, corn oil and mineral oil. In order to make the technical problems, technical solutions and beneficial effects to be understood clearer, the present application will be further described in detail below in combination with specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present application, and are not used to limit the present application. In order to illustrate the technical solution described in the present application, specific embodiments are used for description below. Embodiment 1: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 1: Table 1: Composition Content Remarks Dinotefuran 5% Active ingredient Deionized water 5% Solvent Fatty alcohol polyoxyethylene ether 8% The first emulsifier Alkylbenzene sulfonate 3% The second emulsifier Lignosulfonate 2% Dispersant Organic bentonite 1% Thickener White carbon black 2% Thickener Methyl oleate Balance Oil base The preparation method includes the following steps: S11. mixing the dinotefuran and deionized water and heating a resulting mixture to 56°C under stirring at 1000 rpm so that dinotefuran was completely dissolved in the deionized water; adding the first emulsifier and dispersant and continuing to stir to obtain dinotefuran aquatic agent; S12. mixing the second emulsifier, thickener and oil base, and mechanically stirring at 800 rpm until being uniform to obtain a mixed oil agent; S13. adding the dinotefuran aquatic agent of step S11dropwise to the mixed oil agent of step S12 at a linear speed of 10 m/min under stirring at a high speed of 10000 rpm, and continue stirring to obtain a dispersible oil suspension with 5% of dinotefuran. Embodiment 2: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 2: Table 2 Composition Content Remarks Dinotefuran 5% The first active ingredient Emamectin benzoate 1% The second active ingredient Deionized water 5% Solvent Fatty alcohol polyoxyethylene ether 8% The first emulsifier Alkylbenzene sulfonate 3% The second emulsifier Lignosulfonate 2% Dispersant
Organic bentonite 1% Thickener White carbon black 2% Thickener Dibutylhydroxytoluene 1% Antioxidant Trimethylbenzene 5% Oil base Methyl oleate Balance Oil base The preparation method includes the following steps: S21. mixing dinotefuran and deionized water, and heating the resulting mixture to 56°C under stirring at 500 rpm, so that dinotefuran was completely dissolved in the deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S22. mixing the second active ingredient, the second emulsifier, the thickener, the antioxidant, and the oil base, and mechanically stirring at 1000 rpm until being uniform to obtain a mixed oil agent; S23. adding the dinotefuran aquatic agent of step S21 dropwise to the mixed oil agent of step S22 at a linear speed of 30m/min under stirring at high speed at 8000rpm and continue stirring to obtain a dispersible oil suspension with 6% of dinotefuran-emamectin benzoate. Embodiment3: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 3: Table 3 Composition Content Remarks Dinotefuran 10% The first active ingredient Distilled water 8% Solvent Styrene phenyl polyoxyethylene ether 10% The first emulsifier Alkylbenzene sulfonate 4% The second emulsifier Polycarboxylate 2% Dispersant Attapulgite 2% Thickener Soybean oil Balance Oil base The preparation method includes the following steps: S31. mixing dinotefuran and a solvent, and heating the resulting mixture to 58°C under stirring at 500 rpm so that dinotefuran was completely dissolved in deionized water; adding the first emulsifier and dispersant and continue stirring to obtain dinotefuran aquatic agent; S32. mixing the second emulsifier, thickener and oil base, and mechanically stirring at 700 rpm until being uniform to obtain a mixed oil agent; S33.adding the dinotefuran aquatic agent of step S31 into the mixed oil agent of step S32 at a linear speed of 50 m/min under stirring at a high speed at 10000 rpm to obtain a dispersible oil suspension with 10% of dinotefuran. Embodiment 4: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 4: Table 4 Composition Content Remarks
Dinotefuran 10% The first active ingredient Abamectin 2% The second active ingredient Distilled water 8% Solvent styrene phenyl polyoxyethylene ether 10% The first emulsifier Alkylbenzene sulfonate 4% The second emulsifier Polycarboxylate 2% Dispersant Attapulgite 2% Thickener Dibutylhydroxytoluene 1% Antioxidant Sec-butyl acetate 10% Oil base Soybean oil Balance Oil base The preparation method includes the following steps: S41. mixing the dinotefuran and solvent, and heating the resultant mixture to 58°C under stirring at 1000 rpm, so that the dinotefuran was completely dissolved in deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S42. mixing the second active ingredient, the second emulsifier, the thickener, the antioxidant, and the oil base, and mechanically stirring at 600 rpm until being uniform to obtain a mixed oil agent; S43.adding the dinotefuran aquatic agent of step S41 dropwise to the mixed oil agent of step S42 at a linear speed of 40 m/min under stirring at a high-speed of 8000 rpm and continue stirring to obtain a dispersible oil suspension with 12% of dinotefuran-abamectin. Embodiment 5: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 5 below: Table 5 Composition Content Remarks Dinotefuran 15% The first active ingredient Distilled water 10% Solvent Fatty alcohol polyoxyethylene ether 8% The first emulsifier Sorbitol polyoxyethylene ether 4% The second emulsifier Alkylbenzene sulfonate 3% The third emulsifier Naphthalene sulfonate 2% Dispersant Organic bentonite 1.5% Thickener Mineral oil Balance Oil base The preparation method includes the following steps: S51. mixing the dinotefuran and solvent, and heating the resulting mixture to 58°C under stirring at 9000 rpm so that dinotefuran was completely dissolved in deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S52. mixing the second emulsifier, thickener and oil base, and mechanically stirring at 1000 rpm until being uniform to obtain a mixed oil agent;
S53.adding the dinotefuran aquatic agent of step S31 into the mixed oil agent of step S32 at a linear speed of 30 m/min under stirring at a high speed of 20000 rpm to obtain a dispersible oil suspension with 15% of dinotefuran. Embodiment 6: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 6 below: Table 6
Composition Content Remarks
Dinotefuran 15% The first active ingredient
Pyriproxyfen 5% The second active ingredient
Distilled water 10% Solvent
Fatty alcohol polyoxyethylene ether 8% The first emulsifier
Sorbitol polyoxyethylene ether 4% The second emulsifier
Alkylbenzene sulfonate 3% The third emulsifier
Naphthalene sulfonate 2% Dispersant
Organic bentonite 1% Thickener
Corn oil 20% Oil base
Turpentine-based vegetable oil Balance Oil base The preparation method includes the following steps: S61. Mixing the dinotefuran and a solvent, and heating the resultant mixture to 58°C under stirring at 700 rpm to completely dissolve dinotefuran in deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S62. Mixing the second active compound, the second emulsifier, the thickener and the oil base, and mechanically stirring at 600 rpm until being uniform to obtain a mixed oil agent; S63.adding the dinotefuran aquatic agent of step S61 dropwise to the mixed oil agent of step S62 at a linear speed of 40 m/min under stirring with a high-speed of 10000 rpm to obtain a dispersible oil suspension with 20% of dinotefuran-pyriproxyfen. Embodiment 7: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 7: Table 7 Composition Content Remarks Dinotefuran 15% The first active ingredient Pyriproxyfen 5% The second active ingredient Distilled water 10% Solvent
Fatty alcohol polyoxyethylene ether 8% The first emulsifier Sorbitol polyoxyethylene ether 4% The second emulsifier Alkylbenzene sulfonate 3% The third emulsifier Naphthalene sulfonate 2% Dispersant Organic bentonite 1% Thickener Corn oil 20% Oil base Turpentine-based vegetable oil Balance Oil base The preparation method includes the following steps: S71. mixing the dinotefuran and a solvent, and heating the resulting mixture to 62°C under stirring at 500 rpm to completely dissolve dinotefuran in deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S72. mixing the second emulsifier, thickener and oil base, and mechanically stirring at 700 rpm until being uniform to obtain a mixed oil agent; S73. adding the dinotefuran aquatic agent of step S71 dropwise into the mixed oil agent of step S72 at a linear speed of 30 m/min under stirring with a high-speed of 20000 rpm to obtain a dispersible oil suspension with 20% of dinotefuran. Embodiment 8: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 8 below: Table 8 Composition Content Remarks Dinotefuran 16% The first active ingredient Lambda-cyhalothrin 8% The second active ingredient Distilled water 10% Solvent Fatty alcohol polyoxyethylene ether 8% The first emulsifier Alkylbenzene sulfonate 5% The second emulsifier Polyoxyethylene polyoxypropylene block copolymer 4% Dispersant White carbon black 1% Thickener Citric acid 0.3% pH iPJ S-100 10% Oil base Mineral oil Balance Oil base The preparation method includes the following steps: S81. mixing the dinotefuran and a solvent, and heating the resulting mixture to 62°C under stirring at 500 rpm to completely dissolve the dinotefuran in deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S82. mixing the second active compound, the second emulsifier, the thickener, the pH adjuster, and the oil base, and mechanically stirring at 1000 rpm until being uniform to obtain a mixed oil agent; S83. adding the dinotefuran aquatic agent of step S81 dropwise to the mixed oil agent of step S82 at a linear speed of 20 m/min under stirring with a high-speed of 10000 rpm to obtain a dispersible oil suspension with 24% of dinotefuran-lambda-cyhalothrin.
Embodiment 9: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 9 below: Table 9 Composition Content Remarks Dinotefuran 25% The first active ingredient Deionized water 13% Solvent styrene phenyl polyoxyethylene ether 8% The first emulsifier Alkylbenzene sulfonate 4% The second emulsifier Castor oil polyoxyethylene ether 3% The third emulsifier Polycarboxylate 2% Dispersant Organic bentonite 1% Thickener Soybean oil 15% Oil base Mineral oil Balance Oil base The preparation method includes the following steps: S91. mixing the dinotefuran and deionized water, and heating the resulting mixture to 70° C under stirring at 500 rpm to completely dissolve the dinotefuran in the deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S92. mixing the second emulsifier, thickener and oil base, and mechanically stirring at 600 rpm until being uniform to obtain a mixed oil agent; S93. adding the dinotefuran aquatic agent of step S91 is dropwise to the mixed oil agent of step S92 at a linear speed of 40 m/min under stirring with a high-speed of 20000 rpm to obtain a dispersible oil suspension with 25% of dinotefuran. Embodiment 10: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 10 below: Table 10 Composition Content Remarks Dinotefuran 20% The first active ingredient The second active Pyriproxyfen 10% ingredient Deionizedwater 12% Solvent
Styrene phenyl polyoxyethylene ether 8% The first emulsifier Alkylbenzene sulfonate 4% The second emulsifier Castor oil polyoxyethylene ether 3% The third emulsifier Polycarboxylate 2% Dispersant Organic bentonite 1% Thickener
S-150 15% Oil base
Methyl oleate Balance Oil base
The preparation method includes the following steps: S101. Mixing the dinotefuran and deionized water, and heating the resulting mixture to 70°C under stirring at 700 rpm to completely dissolve dinotefuran in the deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S102. mixing the second active ingredient, the second emulsifier, the thickener and the oil base, and mechanically stirring at 900 rpm until being uniform to obtain a mixed oil agent; S103: adding the dinotefuran aquatic agent of step S101 dropwise to the mixed oil agent of step S102 under stirring with a high-speed of 20000 rpm to obtain a dispersible oil suspension with 30% of dinotefuran-pyriproxyfen. Embodiment 11: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 11: Table 11
Composition Content Remarks
Dinotefuran 30% The first active ingredient
Deionized water 15% Solvent
Fatty alcohol polyoxyethylene ether 12% The first emulsifier
Dioctyl sulfosuccinate 8% The second emulsifier
Polyoxyethylene polyoxypropylene block copolymer 2% Dispersant
Lignosulfonate 2% Dispersant
Organic bentonite 0.5% Thickener
Mineral oil 15% Oil base
Methyl oleate Balance Oil base
The preparation method includes the following steps: SI11. mixing the dinotefuran and deionized water, and heating the resulting mixture to 70°C under stirring at 700 rpm to completely dissolve the dinotefuran in the deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S112. mixing the second emulsifier, thickener and oil base, and mechanically stirring at 900 rpm until being uniform to obtain a mixed oil agent; S113. adding the dinotefuran aquatic agent of step Silldropwise to the mixed oil agent of step S112 at a linear speed of 50 m/min under stirring with a high-speed of 15000 rpm to obtain a dispersible oil suspension with 30% of dinotefuran. Embodiment 12:
This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 12: Table 12 Composition Content Remarks Dinotefuran 15% The first active ingredient
Chlorpyrifos 15% The second active ingredient Deionized water 8% Solvent Fatty alcohol polyoxyethylene ether 12% The first emulsifier Dioctyl sulfosuccinate 8% The second emulsifier Polyoxyethylene polyoxypropylene block copolymer 2% Dispersant Lignosulfonate 2% Dispersant Organic bentonite 1.5% Thickener S-200 15% Oil base
Methyl oleate Balance Oil base The preparation method includes the following steps: S121. mixing the dinotefuran and deionized water, and heating the resulting mixture to 65°C under stirring at 1000 rpm to completely dissolve the dinotefuran in the deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S122. mixing the second active ingredient, the second emulsifier, the thickener and the oil base, and mechanically stirring at 900 rpm until being uniform to obtain a mixed oil agent; S123. adding the dinotefuran aquatic agent of step S121 dropwise to the mixed oil agent of step S122 at a linear speed of 40 m/min under stirring with a high-speed of 10000 rpm to obtain a dispersible oil suspension with 30% of dinotefuran-chlorpyrifos. Embodiment 13: This embodiment provides a dinotefuran dispersible oil suspension, the formulation of which is shown in Table 13 below:
Table 13 Composition Content Remarks
Dinotefuran 10% The first active ingredient Chlorpyrifos 30% The second active ingredient Deionized water 8% Solvent Fatty alcohol polyoxyethylene ether 12% The first emulsifier
Alkylbenzene sulfonate 8% The second emulsifier
Polyoxyethylene polyoxypropylene block copolymer 2% Dispersant
Lignosulfonate 2% Dispersant
Organic bentonite 1.5% Thickener
White carbon black 1.5% Thickener
S-200 20% Oil base
Turpentine-based vegetable oil Balance Oil base
The preparation method includes the following steps: S131. mixing the dinotefuran and deionized water, and heating the resulting mixture to 60°C under stirring at 1000 rpm to completely dissolve dinotefuran in the deionized water; adding the first emulsifier and dispersant and continue stirring to obtain a dinotefuran aquatic agent; S132. mixing the second active ingredient, the second emulsifier, the thickener, and the oil base, and mechanically stirring at 700 rpm until being uniform to obtain a mixed oil agent; S133. adding the dinotefuran aquatic agent of step S131 dropwise to the mixed oil agent of step S132 at a linear speed of 30 m/min under stirring with a high-speed of 10000 rpm to obtain a dispersible oil suspension with 40% of dinotefuran-chlorpyrifos.
Comparative Embodiment 1: 10% dinotefuran dispersible oil suspension, prepared by sand milling method, the formulation is as follows: According to 100% by weight, weighing 10% dinotefuran, 2% polycarboxylate, 8% styrylphenol polyoxyethylene ether, 4% alkylbenzene sulfonate, 3% castor oil polyoxyethylene ether, 2%organic bentonite, 2%white carbon black, balance is methyl oleate. Preparation method: the above components were thoroughly mixed and then placed in a sand mill to grind and disperse, and were further milled to a particle size of about 5 m, and then were filtered to obtain 10% dinotefuran dispersible oil suspension. Comparative Embodiment 2: 20% dinotefuran dispersible oil suspension, prepared by sand milling method, the formulation is as follows: According to 100% by weight, weighing 20% dinotefuran, 2% naphthalene sulfonate, 2% polyoxyethylene polyoxypropylene block copolymer, 8% fatty alcohol polyoxyethylene ether, and 4% sorbitol polyoxyethyl ether, 3% alkylbenzene sulfonate, 1% organic bentonite, 1% white carbon black, the balance is soybean oil. Preparation method: the above components were thoroughly mixed and then placed in a sand mill to grind and disperse, and were further milled to a particle size of about 5 m, and then were filtered to obtain 20% dinotefuran dispersible oil suspension.
Test Embodiment: Taking the dinotefuran dispersible oil suspension of Embodiments 1-13 for stability test, including hot storage test and frozen storage test. The hot storage test and frozen storage test were conducted after storage at 54°C for 14 days and at -5°C for 7 days, respectively, observing the appearance, suspension rate, dispersibility, particle size. In which, 10% dinotefuran dispersible oil suspension and 20% dinotefuran dispersible oil suspension obtained in Comparative Embodiment 1 and Comparative Embodiment 2 were used as positive reference for comparison. Table 14 and Table 15 are the test results. As shown in the results, the dinotefuran dispersible oil suspension in the embodiments of the present application has uniform appearance, good fluidity, and qualified cold and hot storage stability. Compared with the positive reference, the storage stability of the dinotefuran dispersible oil suspension in the embodiments of the present application is better than that of the dinotefuran dispersible oil suspension prepared by the sand milling method. The dinotefuran dispersible oil suspension in the embodiments of the present application has excellent cold and hot storage stability, particle size, suspension rate and other project indicators which is also superior to dinotefuran dispersible oil suspension prepared by sand milling method. Table 14
NO. Test Sample Hot Storage Test (54°C,14days)
Particle size Suspension Dispersity Appearance
D50 rate
S 10Odinotefuran 5.284 m 96.7% Qualified Around 12% of oil precipitation
dispersible oil
suspension
2 20%dinotefuran 5.362 m 95.3% Qualified Around 10% of oil precipitation
dispersible oil
suspension
3 Embodimentl 462 nm 100% Qualified Trace amount of oil precipitation
4 Embodiment2 468 nm 100% Qualified Trace amount of oil precipitation
Embodiment3 486 nm 100% Qualified Trace amount of oil precipitation
6 Embodiment4 487 nm 100% Qualified Trace amount of oil precipitation
7 Embodiment5 492 nm 99.9% Qualified Trace amount of oil precipitation
8 Embodiment6 494 nm 100% Qualified Trace amount of oil precipitation
9 Embodiment7 475 nm 100% Qualified Trace amount of oil precipitation
10 Embodiment8 472 nm 100% Qualified Trace amount of oil precipitation
11 Embodiment9 469 nm 100% Qualified Trace amount of oil precipitation
12 Embodiment10 466 nm 100% Qualified Trace amount of oil precipitation
13 Embodimentl 1 478 nm 100% Qualified Trace amount of oil precipitation
14 Embodiment12 475 nm 100% Qualified Trace amount of oil precipitation
15 Embodiment13 488 nm 100% Qualified Trace amount of oil precipitation
Table 15
NO. Test Sample Frozen Storage Test (54°C, l4days)
Particle size Suspension Dispersity Appearance
D50 rate
1 10odinotefuran 4.863 m 97.7% Qualified Around 1% of oil precipitation
dispersible oil
suspension
2 20%dinotefuran 4.947 m 97.1% Qualified Around 10.6% of oil precipitation
dispersible oil
suspension
3 Embodiment1 457nm 100% Qualified Trace amount of oil precipitation
4 Embodiment2 454 nm 100% Qualified Trace amount of oil precipitation
Embodiment3 466 nm 100% Qualified Trace amount of oil precipitation
6 Embodiment4 462 nm 100% Qualified Trace amount of oil precipitation
7 Embodiment5 475 nm 100% Qualified Trace amount of oil precipitation
8 Embodiment6 476 nm 100% Qualified Trace amount of oil precipitation
9 Embodiment7 458 nm 100% Qualified Trace amount of oil precipitation
Embodiment8 459 nm 100% Qualified Trace amount of oil precipitation
S1 Embodiment9 446 nm 100% Qualified Trace amount of oil precipitation
12 Embodiment10 447nm 100% Qualified Trace amount of oil precipitation
13 Embodiment11 463nm 100% Qualified Trace amount of oil precipitation
14 Embodiment12 460nm 100% Qualified Trace amount of oil precipitation
Embodiment13 467nm 100% Qualified Trace amount of oil precipitation
The above-mentioned embodiments are only used to illustrate the technical solutions of the present application, but not to limit the technical solutions of the present application; although the present application is described in detail with reference to the above embodiments, an ordinary person skilled in the art should understand that: the technical solutions recorded in the above embodiments are modified, or some of the technical features are equivalently replaced; and these modifications or replacements do not cause the corresponding technical solutions to deviate from the spirit and scope of the technical solutions in the embodiments of the present application and should be included in the scope of protection of the present application.
Claims (10)
- CLAIM What is claimed is: 1. A preparation method of dinotefuran dispersible oil suspension, comprising: a) mixing and dissolving the dinotefuran, the first emulsifier, dispersant and water to obtain a dinotefuran aquatic agent under heating conditions; b) mixing the second emulsifier, thickener and oil base to obtain a mixed oil agent; c) adding the dinotefuran aquatic agent of step a) to the mixed oil agent of step b) and emulsifying to obtain a W/O emulsion under high-speed stirring.
- 2. The preparation method according to claim 1, wherein the rotation speed of high-speed stirring is above 500-10000 rpm; and the stirring time is above 0.5 h in step c).
- 3. The preparation method according to claim 1, wherein the temperature of heating and dissolving in step a) is 50-80°C.
- 4. The preparation method according to any one of claim 1-3, wherein the mass ratio of the dinotefuran, the water, the first emulsifier and the dispersant is (5 30):(5~ ):(8~ 12):(2~4).
- 5. The preparation method according to any one of claim 1-3, wherein the mass ratio of the mixed oil agent and the dinotefuran aquatic agent is 1:(0.1 1).
- 6. The preparation method according to any one of claim 1-3, wherein the step b) further comprises: adding the second active ingredient, antioxidant and pH adjuster; the mass ratio of the second active ingredient, the antioxidant, the pH adjuster, the second emulsifier and the thickener is 1:(0.1~- 2):(0.01~- 0.5):(0.1 10):(0.1~-2).
- 7. The preparation method according to claim 6, wherein the second active ingredient is any one selected from the group consisting of emamectin benzoate, abamectin, pyriproxyfen, lambda-cyhalothrin and chlorpyrifos; and the antioxidant is at least one selected from the group consisting of dibutyl hydroxytoluene, butyl hydroxyanisole and tert-butyl hydroquinone; and the pH adjuster is at least one selected from the group consisting of hydrochloric acid, glacial acetic acid and citric acid.
- 8. The preparation method according to any one of claim 1-3, wherein the first emulsifier and the second emulsifier are at least one independently selected from the group consisting of alkylbenzene sulfonate, dioctyl sulfosuccinate, fatty alcohol polyoxyethylene ether, castor oil polyoxyethylene ether, Sorbitol polyoxyethylene ether, styryl phenyl polyoxyethylene ether and styrene phenol formaldehyde resin polyoxyethylene ether;the first emulsifier is different from the second emulsifier.
- 9. The preparation method according to any one of claim 1-3, wherein the dispersant is at least one selected from the group consisting of lignosulfonate, polycarboxylate, naphthalene sulfonate, and polyoxyethylene polyoxypropylene block copolymer; and the thickener is at least one selected from the group consisting of white carbon black, attapulgite, magnesium aluminum silicate and organic bentonite; and the oil base is at least one selected from the group consisting of trimethyl benzene, S-100, S-150, S-200, sec-butyl acetate, methyl oleate, turpentine-based vegetable oil, soybean oil, corn oil and mineral oil.
- 10. A dinotefuran dispersible oil suspension, wherein the dinotefuran dispersible oil suspension is a W/O emulsion, and the droplets of the W/O emulsion contain nanometer-level dinotefuran crystal particles; based on 100 parts by weight of the raw materials, the dinotefuran dispersible oil suspension comprises: 5-30 parts of dinotefuran; 0-30 parts of second active ingredient; 8-20 parts of emulsifier; 2-4 parts of dispersant; 5-15 parts of water; 0~3 parts of thickener; 0~1 parts of antioxidant; 0~0.3 parts of pH adjuster; the balance is oil base.
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AP2014008101A0 (en) * | 2012-05-16 | 2014-12-31 | Bayer Cropscience Ag | Insecticidal water-in-oil (W/O) formulation |
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CN109221226B (en) * | 2018-10-15 | 2021-03-12 | 深圳诺普信农化股份有限公司 | Dinotefuran dispersible oil suspending agent for flight control and preparation method thereof |
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