CN112715569A - Pesticide preparation, preparation method thereof and application thereof in pest control - Google Patents
Pesticide preparation, preparation method thereof and application thereof in pest control Download PDFInfo
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- CN112715569A CN112715569A CN202110066789.0A CN202110066789A CN112715569A CN 112715569 A CN112715569 A CN 112715569A CN 202110066789 A CN202110066789 A CN 202110066789A CN 112715569 A CN112715569 A CN 112715569A
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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
- A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
- A01N45/02—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring having three carbocyclic 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
- 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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Abstract
The invention provides an insecticide preparation, a preparation method thereof and application thereof in pest control, and relates to the technical field of insect control. In the invention, the pesticide preparation is wettable powder, a suspending agent or an aqueous emulsion, and the effective component is (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate; the active ingredients have excellent biological activity and good control effect on lepidoptera pests, can delay the drug resistance of the lepidoptera pests to other insecticides, has the characteristics of high stability, long-acting property and low toxicity, can reduce the dosage, reduce the environmental pollution and agricultural product residue, meets the requirement of green pesticides, and has strong market competitiveness; meanwhile, the preparation forms of wettable powder, suspending agent and aqueous emulsion can improve the deposition, diffusion and permeability of effective components on the surface of the leaf surface, and further improve the drug effect.
Description
Technical Field
The invention relates to the technical field of insect control, in particular to an insecticide preparation, a preparation method thereof and application thereof in pest control.
Background
At present, lepidoptera pests in China are mainly controlled by chemical pesticides, and available medicaments comprise organic phosphorus, carbamates, pyrethroids, benzoylureas and the like. However, the improper use of pesticides results in the development of resistance to these commonly used agents, and some of the insecticides (such as pyrethroids, carbamates, benzoylureas) have even achieved higher resistance, and thus are not effective against lepidopteran pests. Moreover, these agents are generally highly toxic and are likely to cause environmental pollution.
Disclosure of Invention
The invention aims to provide a pesticide preparation, a preparation method thereof and application thereof in pest control. The pesticide preparation provided by the invention has good control effect on lepidoptera pests, and has the characteristics of low toxicity and long-acting property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an insecticide preparation which is wettable powder, a suspending agent or an emulsion in water;
the wettable powder comprises the following components in percentage by mass:
15-40% of active ingredients, 3-20% of a wetting agent, 3-20% of a first dispersing agent, 2-20% of an adsorbent and the balance of a filler;
the suspending agent comprises the following components in percentage by mass:
15-40% of active ingredients, 2-30% of second dispersing agents, 0.5-20% of first thickening agents, 0.01-20% of first stabilizing agents, 1-5% of first defoaming agents, 1-5% of penetrating agents, 0.1-15% of anti-freezing agents and the balance of water; the pH value of the suspending agent is 5-9;
the aqueous emulsion comprises the following components in parts by weight:
5-10 parts of active ingredients, 10-15 parts of organic solvents, 4-8 parts of emulsifiers, 1-3 parts of surfactants, 5-10 parts of bentonite, 3-6 parts of third dispersing agents, 1-3 parts of second thickeners, 1-3 parts of second stabilizers, 0.6-1 part of methyl palmitate octoate, 0.3-0.7 part of second antifoaming agents, 5-10 parts of coating materials and 80-100 parts of water;
the effective components of the wettable powder, the suspending agent and the aqueous emulsion are (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate.
Preferably, the wettable powder comprises the following components in percentage by mass:
15-20% of active ingredients, 7-12% of a wetting agent, 3-10% of a first dispersing agent, 5-15% of an adsorbent and the balance of a filler.
Preferably, the wetting agent is one or more of saponin powder, sodium lignin sulfonate and sodium dodecyl benzene sulfonate; the first dispersant is sodium methylene dinaphthalene sulfonate; the adsorbent is white carbon black; the filler is kaolin and/or attapulgite.
Preferably, the suspending agent comprises the following components in percentage by mass:
the anti-freezing agent comprises 15-20% of active ingredients, 10-20% of a second dispersing agent, 1-10% of a first thickening agent, 2-10% of a first stabilizing agent, 1-3% of a first defoaming agent, 1-2% of a penetrating agent, 5-12% of an anti-freezing agent and the balance of water.
Preferably, the second dispersing agent is one or more of sodium lignosulfonate, sodium laureth sulfate, sodium alkylnaphthalene formaldehyde condensate sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, potassium oleate, sodium oleate, alkyl polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer, nekal, sodium polyoxyethylene carboxylate and dodecyl polyoxyethylene ether phosphate;
the first thickening agent is one or more of xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose and polyvinyl alcohol;
the first stabilizer is one or more of catechol, butyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, polyvinyl ethylene glycol diglycidyl ether, epichlorohydrin, sodium sorbate, sodium benzoate, epoxidized soybean oil, linseed oil, anthraquinone, eugenol, citric acid, hydroxybenzoate and propyl p-hydroxybenzoate;
the first defoaming agent is silicone oil, silicone compound and C10～20Saturated fatty acid compound, C8～10One or more of fatty alcohol compound and 2-ethyl hexanol;
the penetrating agent is organic siloxane; the organic siloxane is one or more of trisiloxane, tetrasiloxane and polysiloxane;
the antifreezing agent is one or more of ethylene glycol, glycerol, propylene glycol, polyethylene glycol, sorbitol and urea.
Preferably, the aqueous emulsion comprises the following components in parts by weight:
5-8 parts of active ingredients, 10-13 parts of organic solvents, 4-6 parts of emulsifiers, 1-2 parts of surfactants, 5-7.5 parts of bentonite, 3-5 parts of third dispersing agents, 1-2 parts of second thickeners, 1-2 parts of second stabilizers, 0.6-0.8 part of methyl palmitate, 0.3-0.5 part of second antifoaming agents, 5-8 parts of coating materials and 80-90 parts of water.
Preferably, the organic solvent is one or more of toluene, xylene and cyclohexanone;
the emulsifier is one or more of sorbitan laurate, polyoxyethylene lauryl ether, polyoxypropylene lanolin alcohol ether, polyoxyethylene monopalmitate, polyoxyethylene sorbitol lanolin, polyoxyethylene monostearate and polyoxyethylene castor oil;
the surfactant comprises an anionic surfactant and a nonionic surfactant, and the mass ratio of the anionic surfactant to the nonionic surfactant is 65-72: 28-35; the anionic surfactant is one or more of alpha-olefin sulfonate, lignosulfonate and tristyrylphenol polyoxyethylene ether phosphate; the nonionic surfactant is one or more of polysorbate-80, alkyl glycoside, vinyl pyrrolidone and polyvinyl acetate;
the third dispersant is aromatic sulfonate, acrylic acid-acrylate copolymer, cresol-formaldehyde condensate sulfonate, C4～11One or more of olefin and maleic anhydride copolymer sodium salt, maleic anhydride-isobutylene copolymer sodium salt, styrene-succinic anhydride copolymer sodium salt, polymeric carboxylic acid sodium salt and alkyl pyrrolidone;
the second thickening agent is one or more of hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose;
the second stabilizer is one or more of 2, 6-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole and tert-butyl hydroquinone;
the second defoaming agent is polyalkyl silicon ethylene oxide and/or tributyl phosphate;
the coating material comprises methyl methacrylate, attapulgite, N-methylene bisacrylamide and polyethylene glycol ether; the mass ratio of the methyl methacrylate to the attapulgite to the N, N-methylene bisacrylamide to the polyethylene glycol ether is 8-10: 5-6: 2-3: 1.
the invention provides a preparation method of the pesticide preparation,
the preparation method of the wettable powder comprises the following steps:
mixing the effective component, the wetting agent, the first dispersing agent, the adsorbent and the filler, and carrying out airflow crushing to obtain the wettable powder;
the preparation method of the suspending agent comprises the following steps:
mixing the effective component, a second dispersing agent, a first thickening agent, a first stabilizing agent, a first defoaming agent, a penetrating agent, an antifreezing agent and water, and carrying out ball milling to obtain the suspending agent;
the preparation method of the aqueous emulsion comprises the following steps:
heating the coating material to 85-95 ℃ to obtain a coating liquid;
preheating the effective components to 85-95 ℃, and spraying the coating liquid on the surfaces of the preheated effective components for coating to obtain a coating agent;
mixing the coating agent, the solvent, the third dispersant and the surfactant to obtain an oil phase;
mixing the emulsifier, the second thickener, the second stabilizer, the second defoaming agent and water at 40-50 ℃ to obtain a water phase;
and adding an oil phase into the water phase, mixing the obtained mixture with bentonite and methyl palm oil methyl caprylate, and performing ultrasonic emulsification treatment to obtain the water emulsion.
Preferably, the particle size of the wettable powder is 10-30 μm; the ball milling time is 2-3 h, and the particle size of the suspending agent is less than 5 mu m.
The invention provides an application of the pesticide preparation in the technical scheme or the pesticide preparation prepared by the preparation method in the technical scheme in the lepidoptera pest control.
The invention provides an insecticide preparation which is wettable powder, a suspending agent or an aqueous emulsion, wherein the effective components of the wettable powder, the suspending agent and the aqueous emulsion are (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate. The pesticide preparation provided by the invention takes (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tertiary butyl) benzoate as an effective component, the (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tertiary butyl) benzoate has excellent biological activity, has good control effect on lepidoptera pests (such as corn armyworm, chilo suppressalis, cruciferous vegetable diamond back moth, cotton bollworm eating sunflower and the like), can delay the drug resistance of the lepidoptera pests to other insecticides, the pesticide has the characteristics of high stability, long-acting property and low toxicity, can reduce the dosage, reduce the environmental pollution and the residue of agricultural products, meets the requirement of green pesticides, and has strong market competitiveness; meanwhile, the wettable powder, the suspending agent and the aqueous emulsion can improve the deposition, diffusion and permeability of (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate on the surface of the leaf surface, and further improve the pesticide effect.
The preparation method of the pesticide preparation provided by the invention is simple in process, low in production cost and easy to realize large-scale production.
Detailed Description
The invention provides an insecticide preparation which is wettable powder, a suspending agent or an emulsion in water;
the wettable powder comprises the following components in percentage by mass:
15-40% of active ingredients, 3-20% of a wetting agent, 3-20% of a first dispersing agent, 2-20% of an adsorbent and the balance of a filler;
the suspending agent comprises the following components in percentage by mass:
15-40% of active ingredients, 2-30% of second dispersing agents, 0.5-20% of first thickening agents, 0.01-20% of first stabilizing agents, 1-5% of first defoaming agents, 1-5% of penetrating agents, 0.1-15% of anti-freezing agents and the balance of water; the pH value of the suspending agent is 5-9;
the aqueous emulsion comprises the following components in parts by weight:
5-10 parts of active ingredients, 10-15 parts of organic solvents, 4-8 parts of emulsifiers, 1-3 parts of surfactants, 5-10 parts of bentonite, 3-6 parts of third dispersing agents, 1-3 parts of second thickeners, 1-3 parts of second stabilizers, 0.6-1 part of methyl palmitate octoate, 0.3-0.7 part of second antifoaming agents, 5-10 parts of coating materials and 80-100 parts of water;
the effective components of the wettable powder, the suspending agent and the aqueous emulsion are (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate.
In the present inventionIn the invention, the effective components in the wettable powder, the suspending agent and the aqueous emulsion are (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1]]Heptane-2-yl-4- (tert-butyl) benzoate; the (1S,2R,4S) -1,3, 3-trimethyl bicyclo [2.2.1]Heptane-2-yl-4- (tert-butyl) benzoate having the formula C21H30O2Molecular weight is 314.47, and the structural formula is shown in formula 1. The (1S,2R,4S) -1,3, 3-trimethyl bicyclo [2.2.1]Heptane-2-yl-4- (tert-butyl) benzoate belongs to a contact stomach poisoning type insecticide, is absorbed by insect epidermis, spiracles and mouthparts, conducts in vivo, acts on insect epidermis structures, inhibits chitin synthesis and metabolism, prevents insects from developing and growing, fails to molt and can not pupate, and finally causes the insects to die. The invention provides a pesticide preparation which is (1S,2R,4S) -1,3, 3-trimethyl bicyclo [2.2.1]Heptane-2-yl-4- (tert-butyl) benzoate as effective component, wherein the (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] is]The heptane-2-yl-4- (tert-butyl) benzoate has excellent biological activity, good control effect on lepidoptera pests (such as corn armyworm, chilo suppressalis, cruciferous vegetable diamond back moth, mallow cotton bollworm and the like), can delay the drug resistance of the lepidoptera pests to other insecticides, has the characteristics of high stability, long-acting property and low toxicity, can reduce the dosage, reduce environmental pollution and agricultural product residue, meets the requirement of green pesticides, and has strong market competitiveness.
Formula 1
In the present invention, the (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptan-2-yl-4- (tert-butyl) benzoate is preferably prepared by:
mixing a compound having a structure represented by formula 2, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and an organic solvent, and carrying out an esterification reaction to obtain the (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate.
Formula 2
In the present invention, the sources of the compound having the structure represented by the above formula 2, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and an organic solvent are not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, the molar ratio of the compound having the structure represented by formula 2, (+) -fenchyl alcohol, 4-dimethylaminopyridine and dicyclohexylcarbodiimide is preferably 1:1:0.2: 0.8; the 4-dimethylaminopyridine and the dicyclohexylcarbodiimide act as catalysts for the esterification reaction.
In the present invention, the organic solvent is preferably dichloromethane, trichloromethane, carbon tetrachloride, tetrahydrofuran, hexane, acetonitrile, benzene, toluene or xylene; the invention has no special limitation on the dosage of the organic solvent, and can fully dissolve the materials.
In the present invention, the compound of formula 2, (+) -fenchyl alcohol, 4-dimethylaminopyridine, dicyclohexylcarbodiimide, and an organic solvent are preferably mixed in the following manner: adding an organic solvent into a mixture of a compound with a structure shown in a formula 2, (+) -fenchyl alcohol and 4-dimethylaminopyridine, stirring and mixing, and cooling to 0-10 ℃ in an ice bath to obtain a mixed solution; dissolving dicyclohexylcarbodiimide in the same organic solvent, and dropwise adding the obtained dicyclohexylcarbodiimide solution into the mixed solution under the ice bath condition. The concentration of the dicyclohexylcarbodiimide solution is not particularly limited, and the dicyclohexylcarbodiimide can be completely dissolved; the stirring and dropping process is not particularly limited in the present invention, and may be carried out according to a process well known in the art.
After the mixing is completed, the ice bath is preferably removed, and the reaction solution obtained by mixing is cooled to room temperature for esterification reaction. The process of cooling to room temperature is not specially limited, and the temperature is naturally cooled.
In the invention, the temperature of the esterification reaction is preferably room temperature, and the time is preferably 3-24 h, and more preferably 6-18 h. The esterification reaction is preferably carried out under the condition of stirring, and the stirring process is not particularly limited, so that the reaction can be carried out smoothly. The present invention preferably detects the reaction by Thin Layer Chromatography (TLC) and stops the reaction until the reaction raw materials are completely disappeared.
After the esterification reaction is finished, preferably, the obtained reaction system is subjected to suction filtration, the obtained liquid part is collected, and a solvent is removed to obtain a crude product; the crude product is then subjected to column chromatography. In the invention, the suction filtration is preferably carried out by adopting a reduced pressure suction filtration funnel, and solid substances are removed by suction filtration; the desolventization is preferably carried out by a rotary evaporator; the developing solvent used for column chromatography separation is preferably a mixture of petroleum ether and ethyl acetate, and the volume ratio of the petroleum ether to the ethyl acetate is preferably (60-80): 1. After the column chromatography separation is completed, the present invention preferably collects the eluates in sequence to obtain the (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate. The process of suction filtration, collection and desolvation is not particularly limited in the present invention, and may be performed according to a process well known in the art. The present invention preferably further comprises drying the collected eluate, and the drying process is not particularly limited in the present invention and may be performed according to a process well known in the art.
In the present invention, the esterification reaction proceeds as follows:
the pesticide preparation provided by the invention comprises wettable powder, wherein the wettable powder comprises the following components in percentage by mass: 15-40% of active ingredients, 3-20% of a wetting agent, 3-20% of a first dispersing agent, 2-20% of an adsorbent and the balance of a filler. In the invention, the wettable powder comprises 15-40 wt% of effective components, preferably 15-20 wt%; the effective component is (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate described in the technical scheme, and details are not repeated herein.
In the invention, the wettable powder comprises 3-20 wt% of wetting agent, preferably 7-12 wt%. In the present invention, the wetting agent is preferably one or more of powdered saponin, sodium lignin sulfonate, sodium dodecylbenzene sulfonate, more preferably sodium dodecylbenzene sulfonate and/or sodium lignin sulfonate; when the wetting agent is a mixture of several kinds, the present invention does not particularly require a mixing ratio, and can be mixed in any ratio.
In the invention, the wettable powder comprises 3-20 wt% of the first dispersant, preferably 3-10 wt%. In the present invention, the first dispersant is preferably sodium methylenedinaphthalenesulfonate (NNO).
In the invention, the wettable powder comprises 2-20 wt% of adsorbent, preferably 5-15 wt%. In the invention, the adsorbent is preferably white carbon black.
In the present invention, the wettable powder includes a filler balance. In the present invention, the filler is preferably kaolin and/or attapulgite; when the filler is a mixture of kaolin and attapulgite, the present invention has no particular requirement on the mixing ratio of the kaolin and the attapulgite.
The source of the wetting agent, the first dispersing agent, the adsorbent and the filler in the wettable powder is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
The pesticide preparation provided by the invention comprises a suspending agent, wherein the suspending agent comprises the following components in percentage by mass: 15-40% of active ingredients, 2-30% of second dispersing agents, 0.5-20% of first thickening agents, 0.01-20% of first stabilizing agents, 1-5% of first defoaming agents, 1-5% of penetrating agents, 0.1-15% of anti-freezing agents and the balance of water; the pH value of the suspending agent is 5-9. In the invention, the suspending agent comprises 15-40 wt% of effective components, preferably 15-20 wt%; the effective component is (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate described in the technical scheme, and details are not repeated herein.
In the invention, the suspending agent comprises 2-30 wt% of the second dispersing agent, preferably 10-20 wt%. In the invention, the second dispersing agent is preferably one or more of sodium lignosulfonate, sodium laureth sulfate, sodium alkylnaphthalene formaldehyde condensate sulfonate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, potassium oleate, sodium oleate, alkyl polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer, nekal, sodium polyoxyethylene carboxylate and dodecyl polyoxyethylene ether phosphate; when the second dispersing agent is a mixture of several kinds, the second dispersing agent has no special requirement on the mixing proportion and can be mixed in any proportion; in an embodiment of the invention, the second dispersant is preferably sodium lignosulfonate.
In the invention, the suspending agent comprises 0.5-20 wt% of the first thickening agent, preferably 1-10 wt%. In the invention, the first thickening agent is preferably one or more of xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose and polyvinyl alcohol; when the first thickener is preferably a mixture of several kinds, the present invention does not particularly require the mixing ratio, and the first thickener may be mixed in any ratio. In an embodiment of the present invention, the first thickener is preferably xanthan gum.
In the invention, the suspending agent comprises 0.01-20 wt% of the first stabilizing agent, preferably 2-10 wt%. In the invention, the first stabilizer is preferably one or more of catechol, butyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, polyvinyl ethylene glycol diglycidyl ether, epichlorohydrin, sodium sorbate, sodium benzoate, epoxidized soybean oil, linseed oil, anthraquinone, eugenol, citric acid, hydroxybenzoate and propyl p-hydroxybenzoate; when the first stabilizer is preferably a mixture of several kinds, the present invention has no particular requirement on the mixing ratio, and the first stabilizer may be mixed in any ratio. In an embodiment of the present invention, the first stabilizer is preferably catechol.
In the invention, the suspending agent comprises 1-5 wt% of the first defoaming agent, and preferably 1-3 wt%. In the present inventionIn the above aspect, the first defoaming agent is preferably silicone oil, silicone compound, or C10～20Saturated fatty acid compound, C8～10One or more of fatty alcohol compound and 2-ethyl hexanol; when the first defoaming agent is a mixture of several kinds, the mixing ratio is not particularly required, and the first defoaming agent can be mixed in any ratio. In the present invention, the silicone-based compound is preferably an organosilicon, such as trisiloxane, tetrasiloxane; said C is10～20The saturated fatty acid compound is preferably one or more of undecanoic acid, tridecanoic acid and pentadecanoic acid; said C is8～10The fatty alcohol compound is preferably pelargonic alcohol. In the embodiment of the present invention, the first antifoaming agent is preferably silicone oil.
In the invention, the suspending agent comprises 1-5 wt% of penetrating agent, preferably 1-2 wt%. In the invention, the penetrating agent is preferably an organosiloxane, and the organosiloxane is preferably one or more of trisiloxane, tetrasiloxane and polysiloxane.
In the invention, the suspending agent comprises 0.1-15 wt% of antifreezing agent, preferably 5-12 wt%. In the invention, the antifreezing agent is preferably one or more of ethylene glycol, glycerol, propylene glycol, polyethylene glycol, sorbitol and urea; more preferably ethylene glycol.
In the present invention, the suspending agent comprises water; the water is not particularly required in the present invention, and water well known to those skilled in the art may be used.
The sources of the second dispersant, the first thickener, the first stabilizer, the first defoamer, the penetrant and the antifreeze in the suspending agent are not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used.
The pesticide preparation provided by the invention comprises an aqueous emulsion; the aqueous emulsion comprises the following components in parts by weight: 5-10 parts of active ingredients, 10-15 parts of organic solvents, 4-8 parts of emulsifiers, 1-3 parts of surfactants, 5-10 parts of bentonite, 3-6 parts of third dispersing agents, 1-3 parts of second thickeners, 1-3 parts of second stabilizers, 0.6-1 part of methyl palmitate octoate, 0.3-0.7 part of second antifoaming agents, 5-10 parts of coating materials and 80-100 parts of water. In the invention, the aqueous emulsion comprises 5-10 parts by mass of effective components, preferably 5-8 parts by mass; the effective component is (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate described in the technical scheme, and details are not repeated herein.
In the invention, the aqueous emulsion comprises 10-15 parts by mass of an organic solvent, preferably 10-13 parts by mass. In the invention, the organic solvent is preferably one or more of toluene, xylene and cyclohexanone; more preferably cyclohexanone.
In the invention, the aqueous emulsion comprises 4-8 parts by mass of an emulsifier, preferably 4-6 parts by mass. In the present invention, the emulsifier is preferably one or more of sorbitan laurate, polyoxyethylene lauryl ether, polyoxypropylene lanolin ether, polyoxyethylene monopalmitate, polyoxyethylene sorbitol lanolin, polyoxyethylene monostearate and polyoxyethylene castor oil, and more preferably polyoxyethylene castor oil.
In the invention, the aqueous emulsion comprises 1-3 parts by mass of a surfactant, preferably 1-2 parts by mass. In the invention, the surfactant preferably comprises an anionic surfactant and a nonionic surfactant, and the mass ratio of the anionic surfactant to the nonionic surfactant is preferably 65-72: 28-35; the anionic surfactant is preferably one or more of alpha-olefin sulfonate, lignosulfonate and tristyrylphenol polyoxyethylene ether phosphate, and more preferably alpha-olefin sulfonate or tristyrylphenol polyoxyethylene ether phosphate; the nonionic surfactant is preferably one or more of polysorbate-80, alkyl glycoside, vinyl pyrrolidone and polyvinyl acetate, and more preferably polyvinyl acetate.
In the invention, the aqueous emulsion comprises 5-10 parts by mass of bentonite, preferably 5-7.5 parts by mass; the type of the bentonite is preferably TY-260.
In the present inventionThe aqueous emulsion comprises 3-6 parts by mass of a third dispersing agent, and preferably 3-5 parts by mass. In the present invention, the third dispersant is preferably an aromatic sulfonate, an acrylic acid-acrylic ester copolymer, a cresol-formaldehyde condensate sulfonate, C4～11The olefin and maleic anhydride copolymer sodium salt, maleic anhydride-isobutylene copolymer sodium salt, styrene-succinic anhydride copolymer sodium salt, polymeric carboxylic acid sodium salt and alkyl pyrrolidone are one or more of, and more preferably, the styrene-succinic anhydride copolymer sodium salt or the maleic anhydride-isobutylene copolymer sodium salt.
In the invention, the aqueous emulsion comprises 1-3 parts by mass of the second thickening agent, preferably 1-2 parts by mass. In the invention, the second thickening agent is preferably one or more of hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, and is more preferably hydroxymethyl cellulose.
In the invention, the aqueous emulsion comprises 1-3 parts by mass of the second stabilizer, preferably 1-2 parts by mass. In the invention, the second stabilizer is preferably one or more of 2, 6-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole and tert-butylhydroquinone, and is more preferably tert-butylhydroquinone.
In the invention, the aqueous emulsion comprises 0.6-1 part by mass of palm oil methyl caprylate, preferably 0.6-0.8 part by mass. In the invention, the palm oil methyl caprylic acid methyl ester has a synergistic effect, and the control effect of the effective components is improved.
In the invention, the aqueous emulsion comprises 0.3-0.7 part by mass of the second defoaming agent, preferably 0.3-0.5 part by mass. In the present invention, the second defoaming agent is preferably polyalkylsiloxaneoxide and/or tributyl phosphate.
In the invention, the aqueous emulsion comprises 5-10 parts by mass of a coating material, preferably 5-8 parts by mass. In the present invention, the coating material preferably includes methyl methacrylate, attapulgite, N-methylenebisacrylamide, and polyethylene glycol ether; the mass ratio of the methyl methacrylate to the attapulgite to the N, N-methylene bisacrylamide to the polyethylene glycol ether is preferably 8-10: 5-6: 2-3: 1. in the present invention, the coating material is used for coating the active ingredient.
In the invention, the aqueous emulsion comprises 80-100 parts by mass of water, preferably 80-90 parts by mass of water. The water is not particularly required in the present invention, and water well known to those skilled in the art may be used.
The invention has no special requirements on the sources of the solvent, the emulsifier, the surfactant, the bentonite, the third dispersant, the second thickener, the second stabilizer, the methyl palmitate octoate, the second defoamer and the coating material in the aqueous emulsion, and can adopt commercial products well known by the technical personnel in the field.
In the invention, the wettable powder, the suspending agent and the aqueous emulsion can improve the deposition, diffusion and permeability of (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate on the surface of the leaf surface, and further improve the pesticide effect.
The invention provides a preparation method of the pesticide preparation in the technical scheme, and the preparation method of the wettable powder comprises the following steps:
and mixing the effective component, the wetting agent, the first dispersing agent, the adsorbent and the filler, and carrying out air flow crushing to obtain the wettable powder.
The method of mixing is not particularly required in the present invention, and a mixing method known to those skilled in the art may be used. In the present invention, the jet milling is preferably performed in a jet mill, which is not particularly required in the present invention, and a jet mill well known to those skilled in the art may be used. In the invention, the granularity of the wettable powder is preferably 10-30 μm.
The preparation method of the suspending agent comprises the following steps:
and mixing the effective component, a second dispersing agent, a first thickening agent, a first stabilizing agent, a first defoaming agent, a penetrating agent, an antifreezing agent and water, and carrying out ball milling to obtain the suspending agent.
The method of mixing is not particularly required in the present invention, and a mixing method known to those skilled in the art may be used. In the invention, in order to ensure that the pH value of the suspending agent is 5-9, preferably, the pH value of the obtained mixture is measured after the mixing; when the pH value of the mixture is not within the range of 5-9, preferably adding a pH value regulator into the mixture to regulate the pH value; the pH value regulator is preferably one or more of sodium hydroxide, ammonia water, acetic acid, citric acid and phosphoric acid. The invention has no special requirements on the ball milling equipment, and the ball mill which is well known by the technicians in the field can be adopted; the ball milling time is preferably 2-3 h, and the particle size of the suspending agent is preferably less than 5 mu m.
The preparation method of the aqueous emulsion comprises the following steps:
heating the coating material to 85-95 ℃ to obtain a coating liquid;
preheating the effective components to 85-95 ℃, and spraying the coating liquid on the surfaces of the preheated effective components for coating to obtain a coating medicament;
mixing the coating agent, the organic solvent, the third dispersant and the surfactant to obtain an oil phase;
mixing the emulsifier, the second thickener, the second stabilizer, the second defoaming agent and water at 40-50 ℃ to obtain a water phase;
and adding an oil phase into the water phase, mixing the obtained mixture with bentonite and methyl palm oil methyl caprylate, and performing ultrasonic emulsification treatment to obtain the water emulsion.
The coating material is heated to 85-95 ℃ to obtain a coating liquid. The invention preferably adds the raw materials of the coating material into a sealed reaction kettle for heating; the temperature of the heating is preferably 90 ℃. After heating, the invention also preferably performs dispersion treatment on the heated material to obtain a coating liquid; the rotation speed of the dispersion treatment is preferably 400-450 r/min, and the time is preferably 10-14 min.
The active ingredients are preheated to 85-95 ℃, and the coating liquid is sprayed on the surfaces of the preheated active ingredients for coating, so that the coating agent is obtained. In the present invention, the preheating is preferably carried out in a coating apparatus, and the temperature of the preheating is preferably 90 ℃. The spraying method of the present invention is not particularly limited, and may be a spraying method known to those skilled in the art. After the spraying, the obtained material is preferably dried to obtain the coating agent; the conditions for the drying are not particularly critical in the present invention, and conventional conditions well known to those skilled in the art may be used.
The coating agent, the organic solvent, the third dispersant and the surfactant are mixed to obtain the oil phase. In the present invention, the method of mixing is preferably: adding the organic solvent and the third dispersing agent into a dispersion kettle for first mixing and dispersing to obtain a first dispersion liquid; and then adding the coated medicament and the surfactant into the first dispersion liquid for second mixing and dispersion to obtain an oil phase. In the invention, the rotating speed of the first mixing dispersion and the second mixing dispersion is preferably 450-550 r/min; the invention has no special requirement on the time of the first mixing and dispersing and the second mixing and dispersing, and can ensure that all the components are uniformly mixed.
The emulsifier, the second thickener, the second stabilizer, the second defoamer and water are mixed at 40-50 ℃ to obtain a water phase. In the present invention, the temperature of the mixing is preferably 45 ℃; the mixing time is preferably 6-8 min.
After a water phase and an oil phase are obtained, the oil phase is added into the water phase, and the obtained mixture is mixed with bentonite and palm oil methyl caprylate for ultrasonic emulsification treatment to obtain the aqueous emulsion. The present invention does not require any particular method for carrying out the ultrasonic emulsification treatment, and any method known to those skilled in the art may be used. In the invention, the time of ultrasonic emulsification treatment is preferably 18-22 min.
The preparation method of the pesticide preparation provided by the invention is simple in process, low in production cost and easy to realize large-scale production.
The invention provides an application of the pesticide preparation in the technical scheme or the pesticide preparation prepared by the preparation method in the technical scheme in the lepidoptera pest control. The method of application of the present invention is not particularly limited, and the application method known to those skilled in the art may be used.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The effective component (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoic acid in each example was prepared according to the following method:
accurately weighing 1.78g (0.01mol) of p-tert-butylbenzoic acid, 1.54g (0.01mol) of (+) -fenchyl alcohol and 0.244g (0.002mol) of 4-Dimethylaminopyridine (DMAP) in a 50mL single-neck round-bottom flask, adding 25mL Dichloromethane (DCM) for dissolving and stirring, and cooling to 0 ℃ in ice bath to obtain a mixed solution; accurately weighing 1.648g of Dicyclohexylcarbodiimide (DCC) (0.008mol), dissolving in 5mL of dichloromethane, slowly dripping into the mixed solution in an ice bath, removing the ice bath after dripping is finished, cooling to room temperature, carrying out esterification reaction for 6 hours under the stirring condition, carrying out Thin Layer Chromatography (TLC) detection reaction, completely eliminating the raw materials, and stopping the reaction; removing solid substances from the obtained reaction system by adopting a decompression suction filter funnel, collecting a liquid part, and removing a solvent by using a rotary evaporator to obtain a crude product; and (2) performing column chromatography on the crude product, eluting by a developing agent (petroleum ether: ethyl acetate, 60:1), sequentially collecting eluates by using test tubes, merging and drying to obtain a white powdery solid, namely (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoic acid, wherein the mass is 2.76g, and the yield is 88%.
1H NMR data (400MHz, Chloroform-d): 8.06-8.02 (m,2H), 7.52-7.48 (m,2H),4.64(d, J ═ 1.9Hz,1H), 2.02-1.93(m,1H),1.85–1.77(m,2H),1.69(dd,J＝10.3,1.7Hz,1H),1.59–1.51(m,1H),1.37(s,9H),1.27(dd,J＝10.4,1.5Hz,1H),1.21(s,3H),1.13(s,3H),0.87(s,3H).
In each example, (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptan-2-yl-4- (tert-butyl) benzoic acid was noted as ZQ-8.
Example 1
The 15 wt% ZQ-8 wettable powder comprises the following components in parts by mass:
the preparation method comprises the following steps:
the effective component ZQ-8 is fully mixed with sodium dodecyl benzene sulfonate, sodium methylene dinaphthalene sulfonate, white carbon black, sodium lignin sulfonate and kaolin, and the mixture is crushed by an airflow crusher to obtain wettable powder with the granularity of 10-30 mu m.
Example 2
20 wt% ZQ-8 wettable powder, which comprises the following components in percentage by mass:
the preparation method comprises the following steps:
the effective component ZQ-8 is fully mixed with sodium dodecyl benzene sulfonate, sodium methylene dinaphthalene sulfonate, white carbon black, sodium lignin sulfonate and kaolin, and the mixture is crushed by an airflow crusher to obtain wettable powder with the granularity of 10-30 mu m.
Example 3
The ZQ-8 wettable powder with the content of 40 wt% comprises the following components in parts by mass:
the preparation method comprises the following steps:
the effective component ZQ-8 is fully mixed with sodium dodecyl benzene sulfonate, sodium methylene dinaphthalene sulfonate, white carbon black, sodium lignin sulfonate and kaolin, and the mixture is crushed by an airflow crusher to obtain wettable powder with the granularity of 10-30 mu m.
Example 4
15 wt% of ZQ-8 suspending agent, which comprises the following components in percentage by mass:
uniformly mixing the effective component ZQ-8 with sodium lignosulfonate, ethylene glycol, xanthan gum, catechol, silicone oil, trisiloxane and water according to the proportion, adding a pH value regulator to adjust the pH value to 7, and then ball-milling in a ball mill for 2.5 hours to ensure that the particle size is below 5 mu m to obtain the suspending agent.
Example 5
20 wt% of ZQ-8 suspending agent, which comprises the following components in percentage by mass:
uniformly mixing the effective component ZQ-8 with sodium lignosulfonate, ethylene glycol, xanthan gum, catechol, silicone oil, tetrasiloxane and water according to the proportion, adding a pH value regulator to adjust the pH value to 7, and then ball-milling in a ball mill for 2.5 hours to ensure that the particle size is below 5 mu m to obtain the suspending agent.
Example 6
40 wt% of ZQ-8 suspending agent, which comprises the following components in percentage by mass:
uniformly mixing the effective component ZQ-8 with sodium lignosulfonate, ethylene glycol, xanthan gum, catechol, silicone oil, tetrasiloxane and water according to the proportion, adding a pH value regulator to adjust the pH value to 7, and then ball-milling in a ball mill for 2.5 hours to ensure that the particle size is below 5 mu m to obtain the suspending agent.
Example 7
The aqueous emulsion containing ZQ-8 comprises the following raw materials in parts by mass:
ZQ-86 parts, 10 parts of organic solvent, 4 parts of emulsifier, 1 part of surfactant, 5 parts of bentonite (TY-260), 3 parts of dispersant, 1 part of thickener, 1 part of stabilizer, 0.6 part of methyl palm oil methyl caprylate, 0.4 part of defoamer and 83 parts of deionized water; the coating material is prepared from methyl methacrylate, attapulgite, N-methylene bisacrylamide and polyethylene glycol ether according to a mass ratio of 10: 6: 2: 1.
Wherein the organic solvent is cyclohexanone; the emulsifier is polyoxyethylene castor oil; the surfactant comprises the following components in percentage by mass: 35 anionic surfactant and nonionic surfactant: the anionic surfactant is tristyrylphenol polyoxyethylene ether phosphate, and the nonionic surfactant is polyvinyl acetate; the dispersing agent is styrene-succinic anhydride copolymer sodium; the thickening agent is hydroxymethyl cellulose; the stabilizer is tert-butyl hydroquinone; the defoaming agent is polyalkyl silicon ethylene oxide.
The preparation method of the ZQ-8 aqueous emulsion comprises the following steps:
(1) preparing each component of the coating material according to the mass portion, adding the component raw materials into a sealed reaction kettle, heating to 85 ℃, and performing dispersion treatment for 10min at the rotating speed of 400r/min to obtain a coating liquid for later use;
(2) putting the ZQ-8 in coating equipment for heating, then spraying the coating liquid prepared in the step (1) on the preheated (85 ℃) ZQ-8 surface, coating, and drying to obtain a coating agent for later use;
(3) adding an organic solvent and a dispersing agent into a dispersion kettle according to the mass parts, uniformly dispersing at the rotating speed of 450r/min, then adding a coating agent and a surfactant into the dispersion kettle, and continuing to disperse for 5min to obtain an oil phase;
(4) mixing an emulsifier, a thickening agent, a stabilizer, a defoaming agent and deionized water, adding into a reaction kettle, and performing dispersion treatment at the temperature of 40 ℃ for 6min to obtain a water phase;
(5) and sequentially adding the water phase and the oil phase into a dispersion kettle, then adding bentonite and palm oil methyl caprylate, and carrying out ultrasonic emulsification treatment for 18min to obtain the aqueous emulsion containing ZQ-8.
Example 8
The aqueous emulsion containing ZQ-8 comprises the following raw materials in parts by mass:
ZQ-810 parts, 15 parts of organic solvent, 8 parts of emulsifier, 3 parts of surfactant, 10 parts of bentonite (TY-260), 6 parts of dispersant, 3 parts of thickener, 3 parts of stabilizer, 1 part of methyl palm oil methyl caprylate, 0.7 part of defoamer and 100 parts of deionized water; the coating material is prepared from methyl methacrylate, attapulgite, N-methylene bisacrylamide and polyethylene glycol ether according to a mass ratio of 10: 6: 2: 1, preparing a composition;
wherein the organic solvent is cyclohexanone; the emulsifier is polyoxyethylene castor oil; the surfactant comprises the following components in percentage by mass: 35 anionic surfactant and nonionic surfactant: the anionic surfactant is alpha-olefin sulfonate, and the nonionic surfactant is polyvinyl acetate; the dispersant is maleic anhydride-isobutylene copolymer sodium salt; the thickening agent is hydroxymethyl cellulose; the stabilizer is tert-butyl hydroquinone; the defoaming agent is polyalkyl silicon ethylene oxide.
The preparation method of the ZQ-8 aqueous emulsion comprises the following steps:
(1) preparing each component of the coating material according to the mass portion, adding the component raw materials into a sealed reaction kettle, heating to 85 ℃, and performing dispersion treatment for 10min at the rotating speed of 400r/min to obtain a coating liquid for later use;
(2) putting ZQ-8 in coating equipment for heating, then spraying the coating liquid prepared in the step (1) on the preheated (85 ℃) surface of ZQ-8, coating and drying to obtain a coating agent for later use;
(3) adding an organic solvent and a dispersing agent into a dispersion kettle according to the mass parts, uniformly dispersing at the rotating speed of 450r/min, then adding a coating agent and a surfactant into the dispersion kettle, and continuing to disperse for 5min to obtain an oil phase;
(4) mixing an emulsifier, a thickening agent, a stabilizer, a defoaming agent and deionized water, adding into a reaction kettle, and performing dispersion treatment at the temperature of 40 ℃ for 6min to obtain a water phase;
(5) and sequentially adding the water phase and the oil phase into a dispersion kettle, then adding bentonite and palm oil methyl caprylate, and carrying out ultrasonic emulsification treatment for 18min to obtain the aqueous emulsion containing ZQ-8.
Test of drug efficacy
Test one of the drug effects: in the field efficacy test of the 5 wt% ZQ-8 aqueous emulsion prepared in example 7 for controlling cabbage diamondback moth
The experiment is carried out in three fields and two fields of the eighth Master Stone farm of the military community in the production and construction of Xinjiang in 2020, vegetables are planted in the experimental field for many years, the vegetables in the current year are cabbages, the soil fertility is medium, and the cabbage diamondback moth pests are medium.
A random block experiment design is adopted, and 3 treatments including a clear water control, a lufenuron suspending agent with the content of 10 wt% and an aqueous emulsion with the content of ZQ-8 with the content of 5 wt% are arranged, wherein each treatment is repeated for 3 times, and the total number is 9 cells. Each cell 20m2The length of the cell is 9m, and the width of the cell is 2.3 m. (Note: lufenuron is a lepidoptera insect growth regulator with better using effect on the market at present, so a lufenuron suspending agent is selected as a contrast)
The population number was investigated before the administration of the drug and 1 time was investigated 5, 7 and 14 days after the administration of the drug. Sampling is carried out at 5 random points in each cell, 3 cabbages with plutella xylostella are fixed on each point, 15 cabbages are counted, the number of live insects is recorded before the medicine is taken, and the number of residual insects is recorded after the medicine is taken. The pesticide effect is calculated according to a formula specified in national standard of the people's republic of China (pesticide field efficacy test criteria, first) in preventing and treating lepidoptera larvae (GB/T17980.13-2000) of cabbage by using the pesticide. The test results are shown in table 1:
TABLE 1 prevention and treatment effects of ZQ-8 aqueous emulsion on cabbage diamondback moth
Note: the population reduction rate is (number of pre-control insects-number of post-control insects)/number of pre-control insects, the control effect is obtained by correcting the population reduction rate by using an Abbott formula, the control effect is (population reduction rate in a control area-population reduction rate in a control area)/(population reduction rate in a control area) x 100, and the population reduction rates in the control area are the population reduction rates of the control area one day after being treated with clear water.
As can be seen from Table 1, the control effects of the 5d postemergence, 10% lufenuron suspending agent and 5% ZQ-8 aqueous emulsion on diamond back moth are respectively 35.11% and 28.18%, the differences between the two are not significant, but the control effects are very significant (1.39%) in a clear water control group; after the pesticide is applied, the control effects of the 10% lufenuron suspending agent and the 5% ZQ-8 aqueous emulsion on the plutella xylostella are respectively 68.64% and 68.86%, the control effects of the two have no significant difference, but the control effects of the two are very significant in a clear water control group (1.33%), the control effects of the 14d after the pesticide, the 10% lufenuron suspending agent and the 5% ZQ-8 aqueous emulsion on the plutella xylostella are respectively 79.44% and 78.79%, the control effects of the two have no significant difference, and the two have the advantages of good control effect and long lasting effect.
Test two of the drug effect: in-field efficacy test of 5 wt% ZQ-8 aqueous emulsion prepared in example 7 for controlling Helianthus annuus Linnaeus
The test is arranged in six teams of the small campuses, town, two villages and six villages in Bole, City, Uygur autonomous region in Xinjiang, and the sunflower variety is sunflower 363. Setting clear water as reference, a lufenuron suspending agent with the content of 10 wt% and an aqueous emulsion with the content of 5 wt% of ZQ-8, wherein the number of the treatments is 3, the treatment is 9, and the number of the treatments is 50m2Each treatment area was 3 spots, the number of plants per spot was 100, and regular investigation was conducted on the spots. Picking off all the worm-eaten fruits at the sampling points before the medicine, and investigating 1d and 3d after the medicine. And respectively picking up the worm-eaten fruits of each sample point in each investigation, converting the worm-eaten fruits into the percentage of hundreds of plants after counting, and calculating the control effect. The test results are shown in table 2:
TABLE 2 prevention and treatment of Helianthus annuus Linnaeus by ZQ-8 aqueous emulsion
Note: the population reduction rate is (number of pre-control insects-number of post-control insects)/number of pre-control insects, the control effect is obtained by correcting the population reduction rate by using an Abbott formula, the control effect is (population reduction rate in a control area-population reduction rate in a control area)/(population reduction rate in a control area) x 100, and the population reduction rates in the control area are the population reduction rates of the control area one day after being treated with clear water.
As can be seen from Table 2, the ZQ-8 aqueous emulsion of the invention has good control effect on cotton bollworm, and the dosage of the effective component of the ZQ-8 aqueous emulsion is 22.5g/hm2The control effect of the pesticide on the cotton bollworms in three days reaches 48.95 percent, and the dosage of the pesticide is 30g/hm compared with the effective component of lufenuron2The prevention and treatment effect is excellent.
As can be seen from the above examples, the insecticide preparation of the present invention, which uses [ (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate ] as an active ingredient, is used for lepidoptera pest control, has excellent biological activity, has the characteristics of long-lasting effect and lower toxicity compared with the currently used lufenuron, meets the requirements of green pesticides, and has strong market competitiveness.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The pesticide preparation is characterized in that the pesticide preparation is wettable powder, suspending agent or emulsion in water;
the wettable powder comprises the following components in percentage by mass:
15-40% of active ingredients, 3-20% of a wetting agent, 3-20% of a first dispersing agent, 2-20% of an adsorbent and the balance of a filler;
the suspending agent comprises the following components in percentage by mass:
15-40% of active ingredients, 2-30% of second dispersing agents, 0.5-20% of first thickening agents, 0.01-20% of first stabilizing agents, 1-5% of first defoaming agents, 1-5% of penetrating agents, 0.1-15% of anti-freezing agents and the balance of water; the pH value of the suspending agent is 5-9;
the aqueous emulsion comprises the following components in parts by weight:
5-10 parts of active ingredients, 10-15 parts of organic solvents, 4-8 parts of emulsifiers, 1-3 parts of surfactants, 5-10 parts of bentonite, 3-6 parts of third dispersing agents, 1-3 parts of second thickeners, 1-3 parts of second stabilizers, 0.6-1 part of methyl palmitate octoate, 0.3-0.7 part of second antifoaming agents, 5-10 parts of coating materials and 80-100 parts of water;
the effective components of the wettable powder, the suspending agent and the aqueous emulsion are (1S,2R,4S) -1,3, 3-trimethylbicyclo [2.2.1] heptane-2-yl-4- (tert-butyl) benzoate.
2. The pesticide formulation as claimed in claim 1, wherein the wettable powder comprises the following components in percentage by mass:
15-20% of active ingredients, 7-12% of a wetting agent, 3-10% of a first dispersing agent, 5-15% of an adsorbent and the balance of a filler.
3. The pesticidal formulation according to claim 1 or 2, wherein the wetting agent is one or more of powdered saponin, sodium lignin sulfonate, sodium dodecylbenzene sulfonate; the first dispersant is sodium methylene dinaphthalene sulfonate; the adsorbent is white carbon black; the filler is kaolin and/or attapulgite.
4. The pesticide formulation as claimed in claim 1, wherein the suspending agent comprises the following components in percentage by mass:
the anti-freezing agent comprises 15-20% of active ingredients, 10-20% of a second dispersing agent, 1-10% of a first thickening agent, 2-10% of a first stabilizing agent, 1-3% of a first defoaming agent, 1-2% of a penetrating agent, 5-12% of an anti-freezing agent and the balance of water.
5. The insecticide formulation according to claim 1 or 4, wherein said second dispersing agent is one or more selected from the group consisting of sodium lignosulfonate, sodium lignosulfate, sodium laureth sulfate, sodium alkylnaphthalene formaldehyde condensate sulfonate, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, potassium oleate, sodium oleate, alkyl polyoxyethylene ether sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate, alkylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, polyoxyethylene polyoxypropylene ether block copolymer, nekal, sodium polyoxyethylene carboxylate salt and polyoxyethylene dodecyl phosphate;
the first thickening agent is one or more of xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose and polyvinyl alcohol;
the first stabilizer is one or more of catechol, butyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether, polyvinyl ethylene glycol diglycidyl ether, epichlorohydrin, sodium sorbate, sodium benzoate, epoxidized soybean oil, linseed oil, anthraquinone, eugenol, citric acid, hydroxybenzoate and propyl p-hydroxybenzoate;
the first defoaming agent is silicone oil, silicone compound and C10～20Saturated fatty acid compound, C8～10One or more of fatty alcohol compound and 2-ethyl hexanol;
the penetrating agent is organic siloxane; the organic siloxane is one or more of trisiloxane, tetrasiloxane and polysiloxane;
the antifreezing agent is one or more of ethylene glycol, glycerol, propylene glycol, polyethylene glycol, sorbitol and urea.
6. The pesticide preparation as claimed in claim 1, wherein the aqueous emulsion comprises the following components in parts by mass:
5-8 parts of active ingredients, 10-13 parts of organic solvents, 4-6 parts of emulsifiers, 1-2 parts of surfactants, 5-7.5 parts of bentonite, 3-5 parts of third dispersing agents, 1-2 parts of second thickeners, 1-2 parts of second stabilizers, 0.6-0.8 part of methyl palmitate, 0.3-0.5 part of second antifoaming agents, 5-8 parts of coating materials and 80-90 parts of water.
7. The insecticide formulation according to claim 1 or 6, wherein said organic solvent is one or more of toluene, xylene and cyclohexanone;
the emulsifier is one or more of sorbitan laurate, polyoxyethylene lauryl ether, polyoxypropylene lanolin alcohol ether, polyoxyethylene monopalmitate, polyoxyethylene sorbitol lanolin, polyoxyethylene monostearate and polyoxyethylene castor oil;
the surfactant comprises an anionic surfactant and a nonionic surfactant, and the mass ratio of the anionic surfactant to the nonionic surfactant is 65-72: 28-35; the anionic surfactant is one or more of alpha-olefin sulfonate, lignosulfonate and tristyrylphenol polyoxyethylene ether phosphate; the nonionic surfactant is one or more of polysorbate-80, alkyl glycoside, vinyl pyrrolidone and polyvinyl acetate;
the third dispersant is aromatic sulfonate, acrylic acid-acrylate copolymer, cresol-formaldehyde condensate sulfonate, C4～11One or more of olefin and maleic anhydride copolymer sodium salt, maleic anhydride-isobutylene copolymer sodium salt, styrene-succinic anhydride copolymer sodium salt, polymeric carboxylic acid sodium salt and alkyl pyrrolidone;
the second thickening agent is one or more of hydroxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose;
the second stabilizer is one or more of 2, 6-tert-butyl-p-cresol, tert-butyl-4-hydroxyanisole and tert-butyl hydroquinone;
the second defoaming agent is polyalkyl silicon ethylene oxide and/or tributyl phosphate;
the coating material comprises methyl methacrylate, attapulgite, N-methylene bisacrylamide and polyethylene glycol ether; the mass ratio of the methyl methacrylate to the attapulgite to the N, N-methylene bisacrylamide to the polyethylene glycol ether is 8-10: 5-6: 2-3: 1.
8. a process for the preparation of the pesticidal formulation of any one of claims 1 to 7,
the preparation method of the wettable powder comprises the following steps:
mixing the effective component, the wetting agent, the first dispersing agent, the adsorbent and the filler, and carrying out airflow crushing to obtain the wettable powder;
the preparation method of the suspending agent comprises the following steps:
mixing the effective component, a second dispersing agent, a first thickening agent, a first stabilizing agent, a first defoaming agent, a penetrating agent, an antifreezing agent and water, and carrying out ball milling to obtain the suspending agent;
the preparation method of the aqueous emulsion comprises the following steps:
heating the coating material to 85-95 ℃ to obtain a coating liquid;
preheating the effective components to 85-95 ℃, and spraying the coating liquid on the surfaces of the preheated effective components for coating to obtain a coating medicament;
mixing the coating agent, the organic solvent, the third dispersant and the surfactant to obtain an oil phase;
mixing the emulsifier, the second thickener, the second stabilizer, the second defoaming agent and water at 40-50 ℃ to obtain a water phase;
and adding an oil phase into the water phase, mixing the obtained mixture with bentonite and methyl palm oil methyl caprylate, and performing ultrasonic emulsification treatment to obtain the water emulsion.
9. The preparation method according to claim 8, wherein the particle size of the wettable powder is 10 to 30 μm; the ball milling time is 2-3 h, and the particle size of the suspending agent is less than 5 mu m.
10. Use of the pesticidal preparation according to any one of claims 1 to 7 or the pesticidal preparation produced by the production method according to any one of claims 8 to 9 for the control of lepidopteran pests.
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| CN117413828A (en) * | 2023-12-19 | 2024-01-19 | 济南兄弟作物科学有限公司 | Emamectin benzoate-chlorfenapyr suspending agent for preventing cabbage beet armyworm and preparation method thereof |
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| CN106866419A (en) * | 2017-04-14 | 2017-06-20 | 石河子大学 | One terpenoid ester compounds and its production and use |
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| 孟繁浩等: "《药物化学》", 31 January 2016, 中国医药科技出版社 * |
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| CN117413828A (en) * | 2023-12-19 | 2024-01-19 | 济南兄弟作物科学有限公司 | Emamectin benzoate-chlorfenapyr suspending agent for preventing cabbage beet armyworm and preparation method thereof |
| CN117413828B (en) * | 2023-12-19 | 2024-03-29 | 济南兄弟作物科学有限公司 | Emamectin benzoate-chlorfenapyr suspending agent for preventing cabbage beet armyworm and preparation method thereof |
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