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CN115067340A - Bactericidal composition, preparation method and application thereof - Google Patents

Bactericidal composition, preparation method and application thereof Download PDF

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Publication number
CN115067340A
CN115067340A CN202110269432.2A CN202110269432A CN115067340A CN 115067340 A CN115067340 A CN 115067340A CN 202110269432 A CN202110269432 A CN 202110269432A CN 115067340 A CN115067340 A CN 115067340A
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Prior art keywords
bactericide
composition
preparation
mass
fluazinam
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CN115067340B (en
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李义涛
梁任龙
刘新烁
刘杨润琪
陈锦昌
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Dongguan Hec Pesticides R&d Co ltd
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Dongguan Hec Pesticides R&d Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G13/00Protecting plants
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G7/00Botany in general
    • A01G7/06Treatment of growing trees or plants, e.g. for preventing decay of wood, for tingeing flowers or wood, for prolonging the life of plants
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647Triazoles; Hydrogenated triazoles
    • A01N43/6531,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

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  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Ecology (AREA)
  • Forests & Forestry (AREA)
  • Botany (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to a sterilization composition, a preparation method and application thereof. In particular, the invention relates to a composition and a preparation containing fluazinam (bactericide A) and triazole sulfonamide bactericide (bactericide B), and a preparation method and application thereof. Wherein, the bactericide B is at least one of bromocyproconazole and triflumizole or the combination thereof. The synergistic effect of fluazinam and epoxiconazole or fluazinam and triflumizole is utilized to expand the bactericidal spectrum, delay the generation of drug resistance and reduce the production and use costs. The composition and the preparation of the invention are mainly used for preventing and treating late blight, downy mildew, powdery mildew, gray mold, gibberellic disease, rice blast, sheath blight, scab, leaf spot and/or target spot of cereal crops, melons and fruits and/or vegetable crops.

Description

Bactericidal composition, preparation method and application thereof
Technical Field
The invention relates to the technical field of pesticides, in particular to a sterilization composition, a preparation method and an application thereof, and more particularly relates to a composition and a preparation which comprise fluazinam (bactericide A) and at least one triazole sulfonamide bactericide (bactericide B) selected from epoxiconazole bromide or epoxiconazole, and an application of the composition or the preparation in preventing and treating plant-related diseases caused by fungi and a method for preventing and treating plant diseases.
Background
The azaconazole is a triazole sulfonamide bactericide created by Dongyuang pesticide research and development Limited company of Dongyuan city in Guangdong province, has excellent control effect on potato late blight and cucumber downy mildew, has high activity on free spores of germs in particular, and is a preparation mainly used for control. The medicine has strong lasting effect, is resistant to rain wash, and has stable effect on various diseases. Chemical name: n is a radical of 3 - (3-bromobenzyl) -N 3 -cyclopropyl-N 1 ,N 1 -dimethyl-1H-1,2,4-triazole-1,3-disulfonamide, english name: n is a radical of 3 -(3-bromobenzyl)-N 3 -cyclopropyl-N 1 ,N 1 -dimethyl-1H-1,2,4-triazole-1, 3-disulphonamide; CAS accession number: 2247022-00-8, having the formula:
Figure BDA0002973628210000011
the triflumizole is a triazole sulfonamide bactericide created by Dongyuang pesticide research and development Limited company of Dongyuan city of Guangdong province, has excellent control effect on potato late blight and cucumber downy mildew, and simultaneously has good persistence and rain resistance. Chemical name: n is a radical of 3 -cyclopropyl-N 1 ,N 1 -dimethyl-N 3 - (3- (trifluoromethyl) benzyl) -1H-1,2,4-triazole-1,3-disulfonamide, english name: n is a radical of 3 -cyclopropyl-N 1 ,N 1 -dimethyl-N 3 -(3-(trifluoromethyl)benzyl)-1H-1,2,4-triazole-1, 3-disulphonamide; the structural formula is as follows:
Figure BDA0002973628210000021
fluazinam is a pyridylamine derivative, and a dinitroaniline bactericide is a broad-spectrum and efficient protective bactericide. Is very effective against alternaria, phytophthora, plasmopara, sclerotinia and cladosporium. Has good effect on resisting botrytis cinerea of benzimidazole and dicarboximide bactericides and also has good effect on rice damping-off caused by rhizopus. The fluazinam is extremely resistant to rain wash and has long residual effect period. In addition, it also has the function of controlling phytophagous mites. Chemical name: 3-chloro-N- (3-chloro-2,6-dinitro-4- (trifluoromethyl) phenyl) -5- (trifluoromethyl) pyridin-2-amine; the name of English: 3-chloro-N- (3-chloro-2,6-dinitro-4- (trifluoromethyl) phenyl) -5- (trifluoromethyl) pyridine-2-amine, CAS registry number: 79622-59-6, the structural formula of fluazinam is:
Figure BDA0002973628210000022
the chemical agent is an effective means for preventing and treating potato late blight. Because the potato late blight has stronger and stronger resistance to pesticides at present, the using amount of the pesticides is increased year by year, so that the environmental pollution is more and more serious.
Therefore, the reasonable use of pesticides and the preparation of formulated fungicides to expand the fungicidal spectrum and reduce the resistance to diseases are imminent.
Disclosure of Invention
The invention aims to provide a composition, the pharmacodynamic active components of the composition comprise fluazinam (bactericide A) and triazole sulfonamide bactericide (bactericide B), and the composition not only solves the problems of overhigh dosage and insufficient control effect in the prior art, but also has the effects of wider bactericidal spectrum, higher quick action, longer lasting period and the like.
The invention also aims to provide a preparation which has wide preparation types, can also solve the problems of overhigh dosage and insufficient control effect in the prior art, and can achieve the effects of enlarging bactericidal spectrum, improving quick action and prolonging lasting period.
In order to achieve the above purpose, the invention provides the following technical scheme:
in a first aspect, the present invention provides a composition comprising the pharmacodynamically active components: a bactericide A and a bactericide B; the bactericide A is fluazinam, and the bactericide B is triazole sulfonamide bactericide.
In some embodiments, the present invention provides a composition wherein the pharmaceutically active ingredients are fungicide a and fungicide B; the bactericide A is fluazinam, and the bactericide B is triazole sulfonamide bactericide.
In some embodiments, the bactericide B is selected from at least one of bromocyproconazole and cyfluconazole or a combination thereof.
In some embodiments, the mass ratio of the bactericide A to the bactericide B in the composition is (1-20) to (20-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the composition is (1-15): (20-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the composition is (1-15): 15-1;
preferably, the mass ratio of the bactericide A to the bactericide B in the composition is (1-10) to (10-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the composition is (1-10) to (5-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the composition is (1-5) to (3-1);
more preferably, the mass ratio of the bactericide A to the bactericide B in the composition is (1-3) to (2-1).
Specifically, the mass ratio of the bactericide A to the bactericide B in the composition is 1:20, 1:15, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1 or 20: 1. In the present invention, when the mass ratio of the bactericide a to the bactericide B in the composition is within the above range, a synergistic effect of sterilization is exhibited.
Further, the mass ratio of fluazinam to azaconazole in the composition is 1:20, 1:15, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1 or 20: 1; the mass ratio of fluazinam to triflumizole in the composition is 1:20, 1:15, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1 or 20: 1.
In some embodiments, the total amount of biocide a and biocide B in the composition is 1 to 90 mass%;
preferably, the total content of the bactericide A and the bactericide B in the composition is 10-70 mass%;
preferably, the total content of the bactericide A and the bactericide B in the composition is 10-60 mass%;
preferably, the total content of the bactericide A and the bactericide B in the composition is 10-50 mass%;
more preferably, the total content of the bactericide A and the bactericide B in the composition is 12 to 50% by mass.
Specifically, the total content of the bactericide a and the bactericide B in the composition is 12 mass%, 22 mass%, 30 mass%, 32 mass%, or 50 mass%. In the present invention, when the total content of the bactericide a and the bactericide B in the composition is within the above range, the synergistic effect of the bactericide is further enhanced.
Further, the total content of fluazinam and azaconazole in the composition is 12 mass%, 22 mass%, 30 mass%, 32 mass%, or 50 mass%; alternatively, the total content of fluazinam and cyfluconazole in the composition is 12 mass%, 22 mass%, 30 mass%, 32 mass%, or 50 mass%.
The composition of the invention can contain auxiliary agents acceptable in pesticide besides the pharmacodynamic active components, the auxiliary agents are auxiliary substances added in the processing or using of pesticide preparations and used for improving the physicochemical property of the pesticide, and the auxiliary agents basically have no biological activity but can influence the prevention and treatment effect. The adjuvant may include at least one of a wetting agent, a dispersing agent, an emulsifier, a thickener, a disintegrant, an antifreeze, a defoamer, a solvent, a preservative, a stabilizer, a synergist, a carrier, etc., and the above adjuvant may be appropriately added according to the needs of the composition, and may be changed according to different situations, and is not particularly limited.
Preferably, the wetting agent is selected from one or more of alkylphenol ethoxylates (e.g., nonylphenol ethoxylates, octylphenol ethoxylates, dodecylphenol ethers, dinonylphenol ethers, mixed alkylphenol ethers, and the like), fatty acid or fatty acid ester sulfates, alkylnaphthalene sulfonates (e.g., sodium dibutylnaphthalene sulfonate, sodium isopropylnaphthalene sulfonate), alkylbenzene sulfonates (e.g., sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulfonate), alkyl sulfates and lignosulfonates (e.g., sodium lignosulfonate, calcium lignosulfonate), and the like. Suitable wetting agents are
Figure BDA0002973628210000055
OTB (dioctyl sulfosuccinate),
Figure BDA0002973628210000057
EFW (alkylated naphthalenesulfonates),
Figure BDA0002973628210000056
BX (alkylated naphthalene sulfonates), GY-WS10 or Galryl
Figure BDA0002973628210000058
804 (alkylated naphthalene sulfonate).
The dispersing agent is selected from one or more of naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, lignosulfonate, alkylbenzene sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, high-molecular polycarboxylate, alkylbenzene polyoxyethylene ether, ethylene oxide propylene oxide, EO-PO block copolymer, block polyether, organic phosphate and the like. For wettable powder formulations, a common dispersing agent is sodium lignosulfonate (sodium lignosulphonate). For suspension concentrates, polyelectrolytes (polyelectrolytes) such as sodium naphthalene sulfonate formaldehyde condensation are usedA sodium naphthalene sulfonate for a molecular sieve to obtain adsorption and stabilization. Tristyrylphenol ethoxylate phosphate ester (tristyrylphenol ethoxylate phosphate ester) is also used. Suitable dispersants are
Figure BDA0002973628210000052
2700、
Figure BDA0002973628210000053
2500、
Figure BDA0002973628210000054
2510、YUS-EP60P、SP-3498D、
Figure BDA0002973628210000051
4894. Ufoxane NA, Morwet D425, GY-900, GY-D800, Antraox B/848, Morwet D425, or Ethylan NS-500 LQ.
The emulsifier is selected from one or more of castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene polyoxypropylene ether, fatty amine, ethylene oxide addition product of fatty amide, fatty acid polyoxyethylene ester, castor oil ethylene oxide addition product and derivatives thereof, rosin acid ethylene oxide addition product and analogs, polyol fatty acid and ethylene oxide addition product thereof, polyoxyethylene polyoxypropylene block copolymer and the like. Suitable emulsifier is lignin A, 3A high-purity modified wood sodium, Nongru 500#, Nongru 601#, Nongru 602#, Nongru 700#, Nongru 1601#, Nongru 1602#, SP-OF3462, TERMUL2507, TERMULR 3016, EMULPON CO-360 or Ethylan 992.
The thickening agent is one or more selected from white carbon black, kaolin, bentonite, xanthan gum, Arabic gum, polyacrylic acid, sodium carboxymethylcellulose and the like.
The disintegrating agent is selected from one or more of urea, modified starch, bentonite, aluminum chloride, ammonium sulfate, succinic acid, sodium bicarbonate, etc.
The antifreezing agent is one or more selected from glycerol, ethylene glycol, propylene glycol and the like.
The defoaming agent is selected from silicone defoaming agent, silicone defoaming agent (such as ETXP-40), and C 8-10 And one or more of fatty alcohol antifoaming agents, polyureas, polyethylene glycol fatty acid esters, and the like.
The solvent is one or more of toluene, xylene, cyclohexanone, aromatic solvent, methanol, ethyl acetate, soybean oil, epoxidized soybean oil, castor oil, corn oil, epoxidized corn oil, methyl oleate, rapeseed oil, N-octyl pyrrolidone and the like.
The preservative is selected from one or more of sodium benzoate, benzoic acid, potassium sorbate, kasong, and the like.
The stabilizer is selected from one or more of phosphoric acid, pyrophosphoric acid, phthalic acid, benzoic acid, triphenyl phosphite, acetic anhydride, epichlorohydrin, magnesium aluminum silicate, resorcinol, sodium citrate and the like.
The synergist has no bioactivity, but can inhibit detoxifying enzyme in organism, and when mixed with some pesticides, can greatly improve the toxicity and the efficacy of the pesticides, such as one or more of synergistic phosphorus, synergistic ether and the like.
The carrier is selected from one or more of kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, silica, alumina, natural or artificial silicates, resins, waxes, solid fertilizers, water, alcohols (especially butanol), organic solvents, mineral and vegetable oils and their derivatives, and the like.
In addition, if appropriate, further additional components may also be present, such as protective colloids, binders, adhesives, thixotropic substances, penetrants, chelating agents, complexing agents, colorants and the like. In general, the pharmacodynamically active component can be combined with any solid or liquid additive commonly used for formulation purposes.
In a second aspect, the present invention provides a formulation, wherein the formulation is prepared from the composition of the present invention.
In some embodiments, the mass ratio of the bactericide A to the bactericide B in the preparation is (1-20): 20-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the preparation is (1-15) to (20-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the preparation is (1-15): 15-1;
preferably, the mass ratio of the bactericide A to the bactericide B in the preparation is (1-10) to (10-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the preparation is (1-10) to (5-1);
preferably, the mass ratio of the bactericide A to the bactericide B in the preparation is (1-5) to (3-1);
more preferably, the mass ratio of the bactericide A to the bactericide B in the preparation is (1-3) to (2-1).
Specifically, the mass ratio of the bactericide A to the bactericide B in the preparation is 1:20, 1:15, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1 or 20: 1. In the present invention, when the mass ratio of the bactericide a to the bactericide B in the preparation is within the above range, a synergistic effect of sterilization is exhibited.
Further, the mass ratio of fluazinam to azaconazole in the preparation is 1:20, 1:15, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1 or 20: 1; or the mass ratio of fluazinam to triflumizole in the preparation is 1:20, 1:15, 1:10, 1:5, 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1 or 20: 1.
In some embodiments, the total content of biocide a and biocide B in the formulation is 1 to 90 mass%;
preferably, the total content of the bactericide A and the bactericide B in the preparation is 10-70 mass%;
preferably, the total content of the bactericide A and the bactericide B in the preparation is 10-60 mass%;
preferably, the total content of the bactericide A and the bactericide B in the preparation is 10-50 mass%;
more preferably, the total content of the bactericide A and the bactericide B in the preparation is 12-50 mass%.
Specifically, the total content of the bactericide a and the bactericide B in the preparation is 12 mass%, 22 mass%, 30 mass%, 32 mass%, or 50 mass%. In the present invention, when the total content of the bactericide a and the bactericide B in the formulation is within the above range, the synergistic effect of the bactericide is further enhanced.
Further, the total content of fluazinam and azaconazole in the preparation is 12 mass%, 22 mass%, 30 mass%, 32 mass%, or 50 mass%; alternatively, the total content of fluazinam and cyfluconazole in the preparation is 12 mass%, 22 mass%, 30 mass%, 32 mass%, or 50 mass%.
In some embodiments, the compositions and/or formulations comprising fungicide a and fungicide B provided by one or more embodiments of the present invention can be used as such or in their formulation form or use forms prepared therefrom according to their respective physical and/or chemical properties, such as aerosols, capsule suspensions, cold atomized concentrates, hot atomized concentrates, particles encapsulated with capsules, fine particles, flowable concentrates for treating seeds, ready to use solutions, sprayable powders, emulsifiable concentrates, oil-in-water emulsions, water-in-oil emulsions, large particles, microparticles, oil dispersible powders, oil soluble flowable concentrates, oil soluble liquids, foams, pastes, pesticide coated seeds, suspension concentrates, suspoemulsions concentrates, soluble concentrates, suspensions, wettable powders, soluble powders, Dusts and granules, seed coatings, smoke agents, water-soluble granules or tablets, water-soluble powders for the treatment of seeds, wettable powders impregnated with active compounds, microcapsules in natural and synthetic substances and coatings of polymeric substances and seeds, and ULV cold-and hot-fogging formulations. Typical formulation formulations include powders, wettable powders, microcapsules, water dispersible granules, aqueous solutions, suspensions, emulsifiable concentrates, microemulsions, aqueous emulsions, ultra-low volume sprays, seed coatings and/or smoking agents.
The powder (DP) is prepared by adding a certain amount of inert powder such as clay, kaolin, and pulvis Talci into the composition, and mechanically processing into powder with particle diameter below 100 μm.
Wettable Powders (WP) are mixtures of the compositions in a certain proportion with suitable surfactants and inert substances (kaolin powders). Wettable powders are formulations which are uniformly dispersible in water and which contain, in addition to the active ingredient and inert substances (kaolin powder), a certain amount of an anionic or nonionic surfactant (dispersant, wetting agent).
The Microcapsule (MC) is prepared by coating the composition in binder, film-forming agent, etc. to form micro capsule, and processing into desired dosage form; the microcapsule suspension is divided into microcapsule suspending agents (CS), microcapsule granules (CG), microcapsule Dry suspending agents (CDF) and the like.
Water Dispersible Granules (WDG) means a mixture of the composition in a certain proportion with a suitable surfactant and an inert substance (kaolin powder). Pulverizing with air flow to make the fineness of powder meet the requirement, mixing with a double helix mixer and a colter mixer for several times to make the product mix uniformly, and granulating with conventional method such as fluidized bed granulation, spray granulation, and disc granulation.
Granules (GR) are mixtures of the composition in certain proportions with suitable surfactants, diluents and inerts (kaolin powder). Granulation by a granulator, for example, a fluidized bed granulation method, is a granulation method in which a binder solution is sprayed to coagulate a powder while keeping the powder in a fluid state. The method can complete the procedures of mixing, kneading, granulating, drying, grading and the like in a device in a closed state for a short time.
The aqueous Agent (AS) is a liquid prepared by directly using water by utilizing the characteristic that some raw medicines can be dissolved in the water without decomposition.
The suspending agent (SC) is prepared by mixing the composition with proper surfactant, water or organic solvent according to a certain proportion, uniformly grinding by a colloid mill, and grinding for 1-2 times by a sand mill to a certain fineness.
Oil suspensions (OD/OF) are solid pesticidal active ingredients that are insoluble in oil solvents, dispersed in non-aqueous media (i.e., oils), relying on surfactants to form highly dispersion stable suspension formulations. The oil suspending agent is divided into water dispersion and oil-based medium dispersion according to different using modes. The oil suspending agent used in water is OD; the oil suspension used for dispersion in oil-based media is OF.
Emulsifiable Concentrates (EC) are prepared by dissolving the composition in a certain proportion in an organic solvent such as benzene, toluene, xylene, cyclohexanone, and adding a certain amount of a mixture of anionic or nonionic surfactants (emulsifiers).
Microemulsions (ME) generally consist of a liquid pesticide, a surfactant (emulsifier), water, a stabilizer, etc.; it features that water is used as medium and contains no or less organic solvent. The droplet size in microemulsions is typically from a few nanometers to tens of nanometers, less than a quarter of the wavelength of visible light.
The aqueous Emulsion (EW) is a pesticide formulation in which a water-insoluble raw drug liquid or a solution obtained by dissolving a raw drug in a water-insoluble organic solvent is dispersed in water. The aqueous emulsion is a preparation prepared by dispersing a liquid pesticide raw pesticide prepared by mixing with an organic solvent into water in small drops of 0.5-1.5 mu m, and the appearance of the aqueous emulsion is milky white milk-like liquid.
Ultra-low volume spray (ULV) refers to a liquid medicine sprayed onto target crops, which is sprayed in extremely fine droplets with extremely low dosage, and is a special preparation for ultra-low volume spray application.
The seed coating agent (SD) is formed by grinding and mixing the composition and an auxiliary agent, and can be directly coated on the surface of seeds or be diluted to form a protective film with certain strength and permeability.
The smoke agent (FU) is also called aerosol, and is a medicament which is prepared by mixing the composition with combustible substances, burning, condensing the gasified pesticide into aerosol or directly dispersing the pesticide into aerosol.
The meaning of each adjuvant and each preparation will cause a difference in understanding due to a difference in expression. It should be understood that various adjuvants and formulations disclosed in the art are within the scope of the present invention, such as pesticide formulation processing technology, hunyan plane, songwang, chemical industry publishers, 2015; "pesticide formulation science, king shipment, chinese agriculture press, 2009; the "processing technology of modern pesticide formulation works, liu guang text, chemical industry press, 2018; agricultural chemical formulations and methods of use, tunzhi, jindun press, 2008; chinese pesticide, China Association for the pesticide industry; and the like. Methods of preparation of various formulations, including but in no way limited to those described herein.
The above-mentioned formulations can be prepared in a known manner, for example by mixing the active compound or active compound combination with at least one additive. Suitable additives are all customary formulation auxiliaries, such as organic solvents, fillers, solvents or diluents, solid carriers and fillers, surfactants (e.g. adjuvants, emulsifiers, dispersants, protective colloids, wetting agents and tackifiers), dispersants and/or binders or fixatives, preservatives, dyes and pigments, defoamers, inorganic and organic thickeners, hydrophobicizers and, if appropriate, siccatives and UV stabilizers, gibberellins and also water and other processing auxiliaries. In each case, depending on the type of formulation to be prepared, further processing steps may be required, such as wet grinding, dry grinding or granulation.
The compositions of the invention comprise not only ready-to-use compositions, which can be applied to plants or seeds with a suitable device, but also commercial concentrates, which have to be diluted with water before use.
The above preferable formulation type composition can improve physicochemical properties of the agent, such as stability, uniformity, quick-acting or sustained-release property, and can also improve the control effect.
In a third aspect, the present invention provides the use of a composition according to the invention and/or a formulation according to the invention for controlling plant diseases caused by fungi.
Preferably, the plant diseases comprise potato late blight, cucumber downy mildew, cucumber powdery mildew, cucumber gray mold, wheat scab, rice blast, rice sheath blight, pear scab, melon leaf spot and/or cucumber target spot.
Preferably, the potato late blight is caused by phytophthora infestans. The composition and/or the preparation show more remarkable synergistic effect on preventing and treating diseases caused by phytophthora infestans.
In a fourth aspect, the present invention provides a method for controlling plant diseases, the method comprising: an effective amount of the composition according to the invention and/or the preparation according to the invention is applied to the plant and/or plant part to be treated.
Preferably, the plant comprises a cereal, melon, fruit and/or vegetable crop.
More preferably, the plant comprises potato, grape, cucumber, wheat, rice, pear, melon, corn, soybean, cotton, canola, sugar beet, sugar cane and/or oat.
Further, the present invention provides a method for controlling plant diseases by applying the pharmacologically active ingredients fungicide a and fungicide B simultaneously, or separately, or successively to the plant or plant part to be treated.
The simultaneous application can be directly applied after the pharmacodynamically active component bactericide A and the pharmacodynamically active component bactericide B are uniformly mixed, or can be prepared into a preparation for application after the bactericide A and the bactericide B are uniformly mixed.
The separate application can be realized by separately applying the pharmacodynamically active component bactericide A and the pharmacodynamically active component bactericide B, or by separately applying the bactericide A and the bactericide B after being respectively prepared into preparations.
The successive application may be a successive application of the pharmacologically active ingredient bactericide a and the pharmacologically active ingredient bactericide B, or may be a successive application of the bactericide a and the bactericide B each prepared as a preparation. When the application is performed successively, the bactericide a (pharmacologically active ingredient or formulation) may be applied first and then the bactericide B (pharmacologically active ingredient or formulation), or the bactericide B (pharmacologically active ingredient or formulation) may be applied first and then the bactericide a (pharmacologically active ingredient or formulation).
In practice, the compositions and/or formulations of the present invention may be used to treat all plants and/or plant parts. Plants are understood to mean all plants and plant populations, such as desired and undesired wild plants, cultivars and plant varieties (whether protected by plant variety rights or plant breeding rights). Cultivars and plant varieties may be plants obtained by conventional propagation and breeding methods (assisted or supplemented by one or more biotechnological methods, for example by using dihaploids, protoplast fusions, random and directed mutagenesis, molecular or genetic markers), or by methods of bioengineering and genetic engineering. Plant parts refer to all parts and organs of the plant above and below the ground, such as shoots, leaves, flowers and roots, for example leaves, needles, stems, branches, flowers, fruit bodies, fruits and seeds as well as roots, bulbs and rhizomes, to name a few. Crops and vegetative and generative propagation material, for example cuttings, bulbs, rhizomes, cork tree and seeds, also belong to the plant parts.
In the present invention, the term "effective amount" means the total amount of each active ingredient in an amount sufficient to exhibit a desired controlling effect. This amount varies within wide limits depending on the fungus to be controlled, the plant species, the climatic conditions and the compounds contained in the composition according to the invention.
In the present invention, the terms "comprising", "including" or "containing" are open-ended expressions, i.e. include what is indicated by the present invention, but do not exclude other aspects.
In the present invention, "prevention" means prevention and/or treatment.
In the treatment of plants and/or plant parts with the compositions and/or preparations provided by the invention, the treatment can be carried out directly or by acting on their surroundings, habitat or storage area using customary treatment methods, for example by dipping, spraying, misting, irrigating, evaporating, dusting, atomizing, broadcasting, foaming, painting, coating, watering (pouring), dripping, and in the case of propagation material, in particular in the case of seeds, also by treating dry seeds with a powder, by treating the seeds with a solution, by treating the slurry with a water-soluble powder by encrustation, coating one or more coats or the like. The composition or formulation may also be applied to soil.
The invention also provides a method for treating seeds. The compositions and/or formulations of the present invention may be administered directly, i.e., without the inclusion of other components and without dilution. Generally, it is preferred that the compositions of the present invention are applied to seeds in a suitable formulation. Suitable formulations and methods for treating seeds are conventional in the art. The compositions of the invention can be converted into conventional seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other coating materials for seeds, and ULV formulations.
In addition to the synergistic activity of the fungicide, the compositions and/or formulations comprising fungicide A and fungicide B provided by the present invention have other surprising properties which can bring about effects beyond those actually expected, and in a broad sense these properties can also be referred to as synergy. For example: reduced application rates, broader spectrum of activity, broader spectrum of kill, higher quick-acting properties, longer duration, increased activity, increased tolerance to high or low temperatures, increased tolerance to drought and/or water and/or soil salt content, better plant growth, easier harvesting, earlier ripening, higher harvest yields, larger fruits, more developed root systems, higher plant height, greener leaf color, larger leaf area, higher flowering performance, stronger shoots, less seed demand, lower toxicity in cereal crops, better compatibility with cereal crops, higher quality and/or higher nutritional value of harvested products, higher sugar concentration in the fruits, better storage stability and/or processability of harvested products; more importantly, the composition can play a role in synergy after being combined in a proper proportion; meanwhile, the generation of drug resistance can be delayed, the safety of crops is improved, the drug cost is reduced and the labor force is saved by compounding the two pesticides.
In summary, compared with the prior art, the invention has at least one of the following technical effects:
(1) the bactericide A and the bactericide B are combined to play a role in synergy, and have certain quick-acting property and long-acting property;
(2) the generation of drug resistance is delayed, and the safety of crops is improved;
(3) the dosage is reduced, and the cost and labor consumption are reduced;
(4) the bactericidal spectrum is expanded.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. In the following examples, a raw epoxiconazole bromide and a raw epoxiconazole are prepared by the preparation method of example 8 in PCT/CN 2018/081979; the cyfluconazole is prepared by the preparation method of example 12 in PCT/CN 2019/108170; the fluazinam raw drug is purchased from Lintai pesticide industry Co., Ltd. The rest of the reagents or instruments used are not indicated by manufacturers, and are all conventional products which can be prepared by the methods described in the prior art or obtained by commercial purchase.
Synthesis and characterization of triflumizole:
Figure BDA0002973628210000141
will N 3 - (3- (trifluoromethyl) benzyl) -N 1 ,N 1 Adding dimethyl-1H-1,2,4-triazole-1,3-disulfonamide (0.41g,1.0mmol), potassium carbonate (0.28g,2.0mmol) and N, N-dimethylformamide (10mL) into a 100mL three-neck flask, slowly adding bromo-cyclopropane (0.24g,2.0mmol) into the reaction system, and reacting at room temperature for 8 hours; quenching with water (20mL), extraction with ethyl acetate (15mL × 3), washing of the organic phase with saturated brine, drying over anhydrous magnesium sulfate, filtration, removal of the solvent from the filtrate under reduced pressure with a rotary evaporator, and column chromatography purification (ethyl acetate/petroleum ether (v/v) ═ 1/3) gave 0.24g of a white solid in yield: 53 percent.
1 H NMR(400MHz,CDCl 3 ):δ(ppm)8.76(s,1H),7.49-7.16(m,4H),3.82(s,2H),2.67(s,6H),1.36-1.32(m,1H),0.71-0.68(m,2H),0.22-0.19(m,2H)。
LC-MS:(M+1)m/z=454.0。
Synthesis and characterization of bromocyproconazole:
Figure BDA0002973628210000151
potassium carbonate (0.276g,2.0mmol), N 3 -cyclopropyl-N 1 ,N 1 -dimethyl-1H-1,2,4-triazole-1,3-disulfonamide (0.40g,1.36mmol), 1-bromo-3- (bromomethyl) benzene (0.48g,2.0mmol) and N, N-dimethylformamide (15mL) were added to a 50mL three-necked flask and the reaction was stirred at room temperature for 12 hours. Water (30mL) was added, extraction was performed with ethyl acetate (20mL × 3), the organic phase was washed with saturated brine (10mL), dried over magnesium sulfate, filtered, the solvent was removed from the filtrate under reduced pressure using a rotary evaporator, and the residue was purified by column chromatography (ethyl acetate/petroleum ether (v/v) ═ 1/5) to give 0.287g of a white solid in 45% yield.
1 H NMR(400MHz,CDCl 3 )δ(ppm):8.63(s,1H),7.52(s,1H),7.44(d,J=7.9Hz,1H),7.33(d,J=7.7Hz,1H),7.21(t,J=7.8Hz,1H),4.54(s,2H),3.08(s,6H),2.58-2.53(m,1H),0.87-0.83(m,2H),0.77-0.73(m,2H)。
LC-MS:(M+1)m/z=464.0。
Indoor bioassay test
Measuring the inhibition effect of different agents on the growth of the potato late blight (Mont.) de Bary, strain source: Single satellite teacher laboratory of northwest agriculture and forestry science and technology university) hypha by adopting a hypha growth rate method, and calculating the EC of each agent on pathogenic bacteria 50 The value is obtained.
Rye medium (RSA) medium: 60g of rye; 20g of cane sugar; 15g of agar powder. Soaking rye in 200mL of distilled water for 36h, filtering with 2 layers of gauze, and storing the filtrate; stirring rye for 2min, adding distilled water 400mL, heating in 50 deg.C water bath for 3h, filtering with 4 layers of gauze, mixing the filtrates, adding sucrose and agar powder, diluting to 1000mL, and sterilizing with 121 deg.C high pressure steam for 15 min.
After dissolving the single dose or each composition (see Table 1 and Table 2) in DMSO as a solvent, 0.1 wt% Tween 80 was added to dilute the solution to a suitable concentration gradient (5mg/L, 2.5mg/L, 1.25mg/L, 0.625mg/L, 0.3125mg/L, 0.15625mg/L) for use.
In a clean bench, 5mL of sterilized sample is added into 45mL of RSA culture medium (cooled to 45-50 ℃) (sterilization mode: ultraviolet sterilization), the mixture is uniformly mixed, the mixture is poured into a flat plate (diameter is 90mm), cooling is carried out, the final concentration of the medicine contained in the flat plate is respectively in a certain gradient, the RSA culture medium added with the same amount of sterile water spitting water is used as a control, and each treatment is carried out for 3 times.
Inoculating late blight bacterium block (diameter 6mm) is poured into the center of the culture plate containing toxin, and cultured in a constant temperature incubator at 20 deg.C for 10 d. The colony diameter was measured by the cross method, and the relative inhibition rate was calculated according to the formulas (2.1) and (2.2).
Colony spread diameter (mm) ═ average colony diameter (mm) -6(mm) (2.1)
Figure BDA0002973628210000161
Making corresponding regression analysis according to the concentrations of the single agents and the compositions and the corresponding relative inhibition rates to obtain the EC of each composition 50 Values and 95% confidence intervals.
The biometric data values are obtained by looking up a table based on the relative inhibition rates. And taking the logarithm of concentration as an abscissa, and converting the inhibition percentage into a biological rate value according to a biological statistic probability value conversion table as an ordinate to draw a toxicity regression equation. The mass concentration when the value of the several degrees is 5 is obtained by the equation and is the EC 50 (Millot M,Girardot M,Dutreix L,et al..Antifungal and anti-biofilm activities of acetone lichen extracts against Candida albicans.[J].Molecules,2017,22(4):651.)。
And (3) calculating the co-toxicity coefficient (CTC) of the mixture by adopting a co-toxicity coefficient calculation method of the Sun Yunpei, and determining the synergy of the mixture.
Using a single dosage of the mixture as a standard medicament (EC is usually selected) 50 Lower), the calculation is performed:
single agent virulence index (EC of standard agent) 50 A certain single agent EC 50 )×100
Theoretical virulence index (TTI) ═ A virulence index of single agent, x proportion of single agent in mixed agent + B virulence index, x proportion of single agent in mixed agent
Measured virulence index (ATI) ═ EC (standard single dose) 50 EC of value/blend 50 Value) × 100
Co-toxicity coefficient (CTC) ═ (measured/theoretical virulence index) × 100
When the CTC is more than 120, the mixture has synergistic effect (namely, the addition is obviously improved compared with the simple addition of single dose), when the CTC is less than 80, the antagonism is realized, and the addition effect of the CTC is realized between 80 and 120.
Table 1: determination result of co-toxicity coefficients of potato late blight by different proportions of fluazinam and azaconazole bromide
Figure BDA0002973628210000171
Figure BDA0002973628210000181
Table 2: determination result of co-toxicity coefficients of potato late blight by different proportions of fluazinam and cyfluconazole
Figure BDA0002973628210000182
Figure BDA0002973628210000191
As can be seen from the results in tables 1 and 2, the compound bactericide which takes fluazinam and epoxiconazole as pharmacodynamic active ingredients and the compound bactericide which takes fluazinam and epoxiconazole as pharmacodynamic active ingredients have obvious control effect on the potato late blight when compounded according to different mass ratios. When the mass ratio of fluazinam to epoxiconazole is (1-15) to (20-1), the co-toxicity coefficient is greater than 120, and the synergistic effect on potato late blight is obvious; when the mass ratio of the fluazinam to the triflumizole is (1-15): (20-1), the cotoxicity coefficient is greater than 120, the synergistic effect on the potato late blight is obvious, and the composition of the fluazinam, the bromocyproconazole, the fluazinam and the triflumizole can be an ideal medicament for preventing and treating the potato late blight.
Example 1: 50% fluazinam-bromocyproconazole water dispersible granule (1:1)
25g of bromocyproconazole raw drug, 25g of fluazinam raw drug, 5g of comb polycarboxylate dispersant (trade name: GY-D900, Beijing broad-source agricultural chemistry Limited liability company), 5g of calcium lignosulfonate (trade name: Borreperse NA, Nanjing Jieron science and technology Limited company), 4g of ammonium sulfate, 0.4g of magnesium aluminum silicate, 0.1g of high-efficiency organic silicon defoamer and 100g of kaolin are added, pre-crushed and uniformly mixed, crushed by air flow to required particle size and granulated by a rotary granulator to prepare the fluazinam-bromocyproconazole water dispersible granule with the mass content of the effective component of 50%.
Example 2: 50% fluazinam-triflumizole water dispersible granule (1:1)
25g of cyflufenazole raw drug, 25g of fluazinam raw drug, 6g of comb polycarboxylate dispersant (trade name: HMK-D1008, Moke chemical technology Co., Ltd. in Hehan, Beijing), 4g of sodium lignosulfonate (trade name: Ufoxane 3A, Jieliun technology Co., Ltd. in Nanjing), 4g of ammonium sulfate, 0.4g of magnesium aluminum silicate, 0.1g of high-efficiency organic silicon defoamer and 100g of kaolin, wherein the raw materials are pre-crushed and uniformly mixed, crushed into required particle size by air flow and granulated by a rotary granulator to prepare the fluazinam-cyfluconazole water dispersible granule with the effective component mass content of 50%.
Example 3: 32% fluazinam-bromocyclozole suspending agent (1:3)
1. Preparation of comminuted slurry
Adding 2g of non-alkylphenol high-efficiency dispersing agent (trade name: TERSPERSE4894, Huntsman)2g, 2g of high molecular compound dispersing agent with comb-shaped structure (trade name: GY-D900, Beijing Guangyuan Yinong chemical Limited liability company) 2g, 2g of wetting agent (trade name: GY-WS10, Beijing Guangyuan Yinong chemical Limited liability company) and 0.3g of high-efficiency organic silicon defoaming agent (trade name: ETXP-40, Hangzhou left soil new material Limited company) into 41.7g of water, dispersing 24g of epoxiconazole raw material and 8g of fluazinam raw material therein, and ensuring that the pesticide is fluazinamBy using
Figure BDA0002973628210000201
The glass beads were subjected to wet pulverization for 2.0 hours using a sand mill (Shenyang New micro-electric machine Mill) to obtain 80g of a pulverized slurry.
2. Preparation of Dispersion Medium
In 15.2g of water were dispersed 0.3g of xanthan gum (avadin reagent), 0.4g of magnesium aluminum silicate (avadin reagent), 4g of ethylene glycol (avadin reagent) and 0.1g of sodium benzoate (avadin reagent) to obtain 20g of a dispersion medium.
3. Preparation of aqueous suspension pesticide composition
100g of an aqueous suspension-type agricultural chemical composition was obtained by mixing 80g of the above-mentioned pulverized slurry with 20g of a dispersion medium, and the resultant mixture was subjected to high shear (4000 rpm) for 30 minutes in a high-speed disperser (trade name: TG25, IKA, Germany) to obtain a fluazinam-bromocyclozole suspension having an active ingredient content of 32% by mass.
Example 4: 32% fluazinam-triflumizole suspension (1:3)
1. Preparation of comminuted slurry
Adding 1.5g polycarboxylate dispersant (trade name: Dispersol 589, clainn), 1.5g comb-structured polymer dispersant (trade name: SP-SC3, Yongsu Optimus chemical science and technology Co., Ltd.), 4g wetting agent (trade name: GY-WS10, Beijing broad-source agricultural chemical Co., Ltd.) and 0.3g high-efficiency organosilicon defoamer (trade name: ETXP-40, Hangzhou left soil new material Co., Ltd.) into 40.7g water, dispersing 24g cyfluconazole and 8g fluazinam, and using
Figure BDA0002973628210000202
The glass beads were subjected to wet pulverization for 2.0 hours by a sand mill (Shenyang New micro electric machine Mill) to obtain 80g of a pulverized slurry.
2. Preparation of Dispersion Medium
In 15.2g of water were dispersed 0.3g of xanthan gum (avadin reagent), 0.4g of magnesium aluminum silicate (avadin reagent), 4g of ethylene glycol (avadin reagent) and 0.1g of sodium benzoate (avadin reagent) to obtain 20g of a dispersion medium.
3. Preparation of aqueous suspension pesticide composition
100g of an aqueous suspension-type agricultural chemical composition was obtained by mixing 80g of the above-mentioned pulverized slurry with 20g of a dispersion medium, and a fluazinam-cyfluconazole suspension having an active ingredient content of 32% by mass was obtained under high shear (4000 rpm) for 30 minutes using a high-speed disperser (trade name: TG25, IKA, Germany).
Example 5: 30% fluazinam-azaconazole water emulsion (5:1)
1. Preparation of the oil phase
5g of epoxiconazole bromide and 25g of fluazinam are added into a mixed solvent of 9g of cyclohexanone (an avermectin reagent) and 7g of xylene (an avermectin reagent), after uniform ultrasonic mixing, 2g of emulsifier (trade name: TERMUL2507, Huntsman) and 2g of castor oil polyoxyethylene ether (trade name: EMULPON CO-360, Acksonobel) are added and slowly stirred until complete dissolution.
2. Preparation of aqueous phase
4g of ethylene glycol (Aladdin reagent), 0.2g of magnesium aluminum silicate (Aladdin reagent), 0.1g of high-efficiency organic silicon defoamer (trade name: ETXP-40, New Material Co., Ltd. left in Hangzhou province) and 45.7g of water are added and stirred uniformly.
3. Blending of pesticide composition aqueous emulsion
Slowly adding the water phase into the oil phase, continuously stirring until the water phase is completely added, and then performing high shear (4000 rpm) for 30 minutes in a high-speed dispersion machine (trade name: TG25, Germany IKA) to obtain the fluazinam-epoxiconazole water emulsion with the active ingredient mass content of 30%.
Example 6: 30% fluazinam-triflumizole aqueous emulsion (5:1)
1. Preparation of the oil phase
5g of epoxiconazole and 25g of fluazinam are added to a mixed solvent of 5g of cyclohexanone (an avermectin reagent) and 11g of a capramide solvent (trade name: Genagen 4296, Clariant), and after uniform mixing by ultrasonic, 3g of an emulsifier (trade name: TERMUL2507, Huntsman) and 2g of castor oil polyoxyethylene ether (trade name: EMULPON CO-360, Acksonobel) are added and slowly stirred until complete dissolution.
2. Preparation of aqueous phase
4g of ethylene glycol (Aladdin reagent), 0.2g of magnesium aluminum silicate (Aladdin reagent), 0.1g of high-efficiency organic silicon defoamer (trade name: ETXP-40, New Material Co., Ltd. left in Hangzhou province) and 44.7g of water are added and stirred uniformly.
3. Blending of pesticide composition aqueous emulsion
Slowly adding the water phase into the oil phase, continuously stirring until the water phase is completely added, and then performing high shear (4000 rpm) for 30 minutes in a high-speed dispersion machine (trade name: TG25, Germany IKA) to obtain the fluazinam-cyfluconazole water emulsion with the active ingredient mass content of 30%.
Example 7: 22% fluazinam-bromocyproconazole microemulsion (3:1)
Weighing 16.5g of fluazinam technical product, 5.5g of epoxiconazole technical product, 10g of solvent dimethylbenzene (an avertin reagent), 5g of solvent cyclohexanone (the avertin reagent), 9g of emulsifier phenethylphenol polyoxyethylene ether (trade name: Nongru No. 602, from Swiss chen chemical auxiliary company Limited), 5g of emulsifier dodecylbenzene sulfonate (trade name: Nongru No. 500, from Swiss chen chemical auxiliary company Limited), 5g of antifreezing agent propylene glycol (the avertin reagent) and 39g of water. After the bromocyproconazole and the fluazinam are fully dissolved by using a solvent, the emulsifier and the antifreeze are added and uniformly mixed, and finally 5g of deionized water is added and uniformly stirred, so that the fluazinam-bromocyproconazole microemulsion with the active ingredient mass content of 22% can be obtained.
Example 8: 22% fluazinam-triflumizole microemulsion (3:1)
Weighing 16.5g of fluazinam raw drug, 5.5g of cyfluconazole raw drug, 12g of solvent capramide solvent (trade name: ADMA 810, Claine), 3g of solvent cyclohexanone (Aladdin reagent), 10g of emulsifier phenethyl phenol polyoxyethylene polyoxypropylene ether (trade name: Nongru 1601#, Schchentai Yancheng chemical auxiliary agent Co., Ltd.), 3g of emulsifier phenethyl phenol polyoxyethylene ether (trade name: Nongru 500#, Schchentai Yancheng chemical auxiliary agent Co., Ltd.), 5g of antifreezing agent propylene glycol (Aladdin reagent), and 39g of water. And (2) after the triflumizole and the fluazinam are fully dissolved by using a solvent, adding an emulsifier and an antifreezing agent, uniformly mixing, finally adding 6g of deionized water, and uniformly stirring to obtain the fluazinam-triflumizole microemulsion with the active ingredient mass content of 22%.
Example 9: 12% fluazinam bromocyproconazole dispersible oil suspending agent (2:1)
1. Preparation of the oil phase
Adding emulsifier (trade name: SP-OF3462, Jiangsu engine) 15g and polycarboxylate dispersant (trade name: SP-OF3498D, Jiangsu engine chemical science and technology Co., Ltd.) 6g into 63g OF methyl oleate (Aladdin reagent), stirring and mixing, adding fluazinam original drug 8g and bromocyprole original drug 4g, and using
Figure BDA0002973628210000231
The glass beads were subjected to wet pulverization for 2.0 hours using a sand mill (Shenyang New micro-electric machine Mill) to obtain 96g of a pulverized slurry.
2. Thickener composition formulation
2g of hydrophilic white carbon black (an avadin reagent) and 2g of organic bentonite (Hangzhou left soil new material Co., Ltd.) are weighed and added into an oil phase to obtain 100g of an oily suspended pesticide composition, and the oily suspended pesticide composition is subjected to high shear (4000 revolutions per minute) for 20 minutes by a high-speed dispersion machine (trade name: TG25, Germany IKA) to prepare the fluazinam bromocyproconazole dispersible oil suspending agent with the active ingredient mass content of 12%.
Example 10: 12% fluazinam-triflumizole dispersible oil suspending agent (2:1)
1. Preparation of the oil phase
Adding 18g of emulsifier (trade name: SUPER-3000, JINANCHENJINHENXINGJIAO Co., Ltd.) and 3g of polycarboxylate dispersant (trade name: Geropon Ultrasperse, Solvay) into 63g of methyl oleate (Aladdin reagent), stirring, mixing, adding 8g of fluazinam original drug and 4g of cyfluconazole original drug, and using
Figure BDA0002973628210000232
The glass beads were subjected to wet pulverization for 2.0 hours by a sand mill (Shenyang New micro electric machine Mill) to obtain 96g of a pulverized slurry.
2. Thickener composition formulation
2g of hydrophilic white carbon black (Aladdin reagent) and 2g of organic bentonite (Hangzhou left soil new material Co., Ltd.) are weighed and added into an oil phase to obtain 100g of an oily suspended pesticide composition, and the oily suspended pesticide composition is subjected to high shear (4000 revolutions per minute) for 20 minutes in a high-speed dispersion machine (trade name: TG25, Germany IKA) to prepare the fluazinam and cyfluconazole dispersible oil suspension with the active ingredient mass content of 12%.
Example 11: 30% fluazinam-bromocyproconazole emulsifiable concentrate (1:2)
Adding 10g of emulsifier (trade name: TERMULR 3016, Huntsman), 10g of fluazinam raw drug and 20g of azaconazole raw drug into 60g of fluquinamide solvent (trade name: ARMID DM10, Nanjing Jiemon), and fully stirring at 35 ℃ in a warm water bath until the raw drugs are completely dissolved to prepare fluazinam azaconazole emulsifiable concentrate with the active ingredient mass content of 30%.
Example 12: 30% fluazinam-triflumizole emulsifiable concentrate (1:2)
15g of emulsifier (trade name: TERMULR 2507, Huntsman), 10g of fluazinam original drug and 20g of cyfluconazole original drug are added into 55g of fluquinamide solvent (trade name: ADMA 810, Kelaien) and fully stirred in a warm water bath at the temperature of 35 ℃ until the original drugs are completely dissolved, and the fluazinam cyfluconazole emulsifiable concentrate with the mass content of the active ingredients of 30 percent is prepared.
Comparative example 1: 50% fluazinam suspension
1. Preparation of comminuted slurry
2g of a non-alkylphenol type high-efficiency dispersant (trade name: TERSPERSE4894, Huntsman), 1.5g of a comb-structured polymer dispersant (trade name: GY-D900, Beijing Guangyuan agricultural chemistry, Ltd.), 4g of a wetting agent (trade name: GY-WS10, Beijing Guangyuan agricultural chemistry, Ltd.) and 0.3g of a high-efficiency silicone antifoaming agent (Hangzhou left soil new material Co., Ltd.) were dispersed in 22.2g of water, 50g of a fluazinam base material was used, and the mixture was stirred and stirred
Figure BDA0002973628210000241
The glass beads were subjected to wet pulverization for 1.5 hours using a sand mill (Shenyang New micro-electric machine Mill) to obtain 80g of a pulverized slurry.
2. Preparation of Dispersion Medium
In 15.2g of water, 0.3g of xanthan gum (avadin reagent), 0.4g of magnesium aluminum silicate (avadin reagent), 4g of ethylene glycol (avadin reagent) and 0.1g of sodium benzoate (avadin reagent) were dispersed to obtain 20g of a dispersion medium.
3. Preparation of aqueous suspension pesticide composition
80g of the above-mentioned pulverized slurry and 20g of a dispersion medium were mixed to obtain 100g of an aqueous suspension-type agricultural chemical composition, and the obtained mixture was subjected to high shear (4000 rpm) for 30 minutes using a high-speed disperser (trade name: TG25, IKA, Germany). The fluazinam suspending agent with the mass content of the effective component of 50 percent is prepared.
Comparative example 2: 50% bromocyclozole suspension
1. Preparation of comminuted slurry
Dispersing 2.5G of block copolymer dispersant (trade name: G-5000, UK grass size) in 22.1G of water, 2G of comb-structured polymer dispersant (trade name: KY555, Jiangsu Kaiyuan scientific Co., Ltd.), 3G of wetting agent (trade name: GY-WS10, Beijing broad-source agricultural chemistry Co., Ltd.) and 0.4G of high-efficiency organic silicon defoamer (trade name: ETXP-40, Hangzhou left soil New Material Co., Ltd.) in water, dispersing 50G of crude drug of azaconazole, and using
Figure BDA0002973628210000252
The glass beads were subjected to wet pulverization for 1.5 hours using a sand mill (Shenyang New micro-electric machine Mill) to obtain 80g of a pulverized slurry.
2. Preparation of Dispersion Medium
In 15.2g of water, 0.25g of xanthan gum (avadin reagent), 0.45g of magnesium aluminum silicate (avadin reagent), 4g of ethylene glycol (avadin reagent) and 0.1g of sodium benzoate (avadin reagent) were dispersed to obtain 20g of a dispersion medium.
3. Preparation of aqueous suspension pesticide composition
The above-mentioned pulverized slurry (80 g) and a dispersion medium (20 g) were mixed together to obtain 100g of an aqueous suspension-type agricultural chemical composition, which was then subjected to high shear (5000 rpm) for 30 minutes using a high-speed disperser (trade name: TG25, IKA, Germany). The bromocyclozole suspending agent with the mass content of the effective component of 50 percent is prepared.
Comparative example 3: 50% triflumizole suspension
1. Preparation of comminuted slurry
Dispersing a polycarboxylate dispersant (commercial product) in 22.1g of waterName: SP-27001, guzhi science and technology ltd, jiangsu), 2g, a high molecular compound dispersant of comb type structure (trade name: TERSPERSE 2612, Huntsman)2.5g, wetting agent (trade name: GY-WS10, beijing, guangyaoyi agrichemical llc) 3g and a high-efficiency silicone defoamer (trade name: ETXP-40, Hangzhou left soil new materials Co., Ltd.) 0.4g, 50g of cyfluconazole raw drug is dispersed therein for use
Figure BDA0002973628210000251
The glass beads were subjected to wet pulverization for 1.5 hours by a sand mill (Shenyang New micro electric machine Mill) to obtain 80g of a pulverized slurry.
2. Preparation of Dispersion Medium
In 15.2g of water, 0.25g of xanthan gum (avadin reagent), 0.45g of magnesium aluminum silicate (avadin reagent), 4g of ethylene glycol (avadin reagent) and 0.1g of sodium benzoate (avadin reagent) were dispersed to obtain 20g of a dispersion medium.
3. Preparation of aqueous suspension pesticide composition
80g of the above-mentioned pulverized slurry and 20g of a dispersion medium were mixed to obtain 100g of an aqueous suspension-type agricultural chemical composition, and the obtained mixture was subjected to high shear (5000 rpm) for 30 minutes using a high-speed disperser (trade name: TG25, IKA, Germany). The cyfluconazole suspending agent with the effective component mass content of 50 percent is prepared.
Comparative example 4:
and (5) blank clear water control.
Test of field drug effect
Setting a cell: each treatment was repeated 4 times; the cell area is 30m 2 Random block permutation.
The application time and the application method are as follows: the agent is applied to the early stage of the late blight of the potatoes, and sprayed on leaf surfaces, and the spraying amount is mainly no water drops. The medicine is applied for 2 times, the disease condition base is investigated before the first medicine application, the medicine is applied for 1 time every 7 days, the disease condition index is investigated 7 days after each medicine application, and the prevention effect is calculated.
The investigation method comprises the following steps: and (4) classifying according to the damage symptom degrees of the potato leaf sheaths and the potato leaves, taking the plants as a unit, sampling five points on the diagonal line of each cell, taking two plants at each point, and investigating all the leaves.
The concrete grading is as follows:
level 0: no disease;
stage 1: the lesion area accounts for 5 percent of the whole leaf area;
and 3, level: the area of the lesion spots accounts for 6 to 10 percent of the area of the whole leaf;
and 5, stage: the area of the lesion spots accounts for 11 to 20 percent of the area of the whole leaf;
and 7, stage: the area of the lesion spots accounts for 21 to 50 percent of the area of the whole leaf;
and 9, stage: the area of the lesion spots accounts for more than 50 percent of the area of the whole leaf.
And (3) calculating the drug effect:
Figure BDA0002973628210000261
Figure BDA0002973628210000262
in the formula: CK (CK) 0 -pre-drug disease index of the placebo zone; CK (CK) 1 -post-drug disease index in the placebo zone;
PT 0 -pre-drug disease index in the drug treatment area; PT 1 -post-drug disease index in the drug treatment area.
The test results are detailed in tables 3 and 4.
Table 3: prevention effect of different medicaments on potato late blight
Figure BDA0002973628210000271
Figure BDA0002973628210000281
Table 4: prevention effect of different medicaments on potato late blight
Figure BDA0002973628210000282
Figure BDA0002973628210000291
And (4) conclusion: from the results in tables 3 and 4, it can be seen that the control effect of the compound of fluazinam and bromocyproconazole or fluazinam and cyfluconazole on potato late blight is obviously better than that of the control medicament after the compound of fluazinam and bromocyproconazole in a certain proportion, and the compound of the two components in a certain proportion improves the quick action and has a synergistic effect compared with the single use of the control medicament. In addition, no phytotoxicity of the pesticide composition and/or the preparation to the potatoes is found in the application range, and the bactericidal composition is good in safety to crops and has practical and popularization values.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (10)

1. A composition comprising pharmaceutically active ingredients: a bactericide A and a bactericide B;
the bactericide A comprises fluazinam, and the bactericide B comprises triazole sulfonamide bactericide.
2. The composition according to claim 1, wherein the bactericide B is at least one selected from the group consisting of epoxiconazole and epoxiconazole, or a combination thereof.
3. The composition as claimed in claim 1 or 2, wherein the mass ratio of the bactericide A to the bactericide B is (1-15): (20-1); preferably, the mass ratio of the bactericide A to the bactericide B is (1-15): 15-1.
4. The composition as claimed in any one of claims 1 to 3, wherein the mass ratio of the bactericide A to the bactericide B is (1-10) to (5-1); preferably, the mass ratio of the bactericide A to the bactericide B is (1-5) to (3-1).
5. The composition according to any one of claims 1 to 4, wherein the total content of the bactericide A and the bactericide B in the composition is 1 to 90% by mass, and preferably the total content of the bactericide A and the bactericide B in the composition is 10 to 70% by mass.
6. The composition according to any one of claims 1 to 5, wherein the total content of the bactericide A and the bactericide B in the composition is 10 to 60 mass%; preferably, the total content of the bactericide A and the bactericide B in the composition is 10-50 mass%.
7. A formulation prepared from the composition of any one of claims 1-6.
8. The preparation of claim 7, wherein the preparation is in the form of powder, wettable powder, microcapsule, water dispersible granule, aqueous solution, suspension, oil suspension, emulsifiable concentrate, microemulsion, aqueous emulsion, ultra-low volume spray, seed coating and/or smoke agent.
9. Use of a composition according to any one of claims 1 to 6 or a formulation according to claim 7 or 8 for controlling plant diseases caused by fungi;
preferably, the plant diseases comprise potato late blight, cucumber downy mildew, cucumber powdery mildew, cucumber gray mold, wheat scab, rice blast, rice sheath blight, pear scab, melon leaf spot and/or cucumber target spot.
10. A method for controlling plant diseases, characterized in that an effective amount of the composition according to any one of claims 1 to 6 or the formulation according to claim 7 or 8 is applied to the plant or plant part to be treated;
preferably, the plant comprises a cereal, melon, fruit and/or vegetable crop.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106212471A (en) * 2016-07-22 2016-12-14 重庆东永植保技术有限责任公司 A kind of containing amisulbrom and the bactericidal composition of fluazinam and application
CN106577680A (en) * 2016-12-01 2017-04-26 青岛东生药业有限公司 Bactericide and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106212471A (en) * 2016-07-22 2016-12-14 重庆东永植保技术有限责任公司 A kind of containing amisulbrom and the bactericidal composition of fluazinam and application
CN106577680A (en) * 2016-12-01 2017-04-26 青岛东生药业有限公司 Bactericide and application thereof

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