CN115530174A - Dispersible oil suspending agent containing fipronil and pyriproxyfen and preparation method and application thereof - Google Patents

Dispersible oil suspending agent containing fipronil and pyriproxyfen and preparation method and application thereof Download PDF

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CN115530174A
CN115530174A CN202110725353.8A CN202110725353A CN115530174A CN 115530174 A CN115530174 A CN 115530174A CN 202110725353 A CN202110725353 A CN 202110725353A CN 115530174 A CN115530174 A CN 115530174A
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pyriproxyfen
dispersible oil
fipronil
suspending agent
emulsifier
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袁良国
王建伟
张小兵
赵保臣
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Qingdao Runnong Chemical Co ltd
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Qingdao Runnong Chemical 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
    • A01N47/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • 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
    • A01N25/00Biocides, 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
    • A01N25/02Biocides, 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
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a dispersible oil suspending agent containing fipronil and pyriproxyfen, a preparation method and application thereof, wherein the dispersible oil suspending agent comprises the following components in percentage by weight: 5-30% of active ingredients, 6-20% of emulsifier, 1-8% of dispersant, 1-8% of thickener, 0.5-2% of stabilizer and the balance of dispersion medium to 100%. The dispersible oil suspending agent disclosed by the invention is simple in preparation process, easy to operate, environment-friendly and safe in preparation process, free of pollution problem, low in cost and easy for industrial production. The obtained dispersible oil suspending agent has good emulsifying dispersibility, low liability to thickening, bottom precipitation, crystallization and delamination, less residue after pouring, high suspension rate, and good heat storage stability. Through the optimization of each auxiliary agent, the residue of the obtained dispersible oil suspending agent after pouring is lower than 1.2%, and the suspension rate before and after heat storage can reach more than 95%.

Description

Dispersible oil suspending agent containing fipronil and pyriproxyfen and preparation method and application thereof
Technical Field
The invention relates to a pesticide dispersible oil suspending agent, in particular to a dispersible oil suspending agent containing fipronil and pyriproxyfen, a preparation method and application thereof, and belongs to the technical field of pesticides.
Background
Fipronil is a novel broad-spectrum insecticide of phenylpyrazole type developed by original French Rona-Planck company in 1981, has the chemical name of (RS) -5-amino-1- (2, 6-dichloro-a, a, a-trifluoro-p-tolyl) -4-trifluoromethyl sulfinyl pyrazole-3-nitrile, has the action mechanism of combining with a gamma-aminobutyric acid receptor, effectively blocks a chloride ion channel regulated by systemic gamma-aminobutyric acid in the insect center, interferes with the insect center nervous system, and causes the overexcitation of insect nerves and muscles until death. The pesticide composition has stomach poisoning effect on pests, has contact killing and certain systemic effect, has high activity on important pests such as aphids, leafhoppers, plant hoppers, lepidoptera larvae, flies, coleoptera and the like, and has no pesticide damage on crops.
Pyriproxyfen, also known as Mianbao and pyriproxyfen, has a chemical name of 4-phenoxyphenyl- (RS) -2- (2-pyridyloxy) propyl ether, is an alkoxy pyridine juvenile hormone type chitin synthesis inhibitor which is created and developed by Nippon Sumitomo company in 1983, can be used for controlling homoptera, thysanoptera, diptera and lepidoptera pests, and is widely applied to fruits, vegetables, cotton, ornamental plants and public health.
Pesticide varieties containing a single active ingredient often have different degrees of defects in agricultural pest control, such as: the insecticidal spectrum is narrow, the insecticide resistance is easy to generate after continuous use, and the environmental pollution is aggravated by a plurality of use times. The above disadvantages can be effectively overcome by compounding active ingredients with different mechanisms of action. Meanwhile, the synergistic effect generated by mixing the two active components can improve the control effect, expand the insecticidal spectrum, delay the generation of the drug resistance of pests and reduce the environmental pollution, thereby being an important means for comprehensively controlling the pests. Currently, fipronil and pyriproxyfen are used in combination for killing insects, for example, patent CN103355324A.
At present, the common formulations of the pesticide comprise wettable powder, water dispersible granules, missible oil, aqueous solution, suspending agent and the like, the main formulation of the fipronil is the water suspending agent, and the main formulation of the pyriproxyfen is the missible oil. The missible oil contains low-boiling-point toxic and harmful solvents such as dimethylbenzene and benzene, and the water suspending agent is easy to generate unstable phenomena such as deposition, layering and the like, so that the pesticide effect is seriously influenced. The dispersible Oil suspending agent is a pesticide preparation with development prospect, the dispersible Oil suspending agent refers to a liquid preparation with active ingredients stably suspended in liquid immiscible with water, the Oil suspending agent is diluted and prepared by water, and the English name of the dispersible Oil suspending agent is Oil-based dispersion concentrations or Oil dispersion, called OD for short. The dispersible oil suspending agent is directly diluted by water before use, and is different from the oil suspending agent in that the dispersible oil suspending agent needs to be diluted by an organic solvent before use. The dispersible oil suspending agent selects oil auxiliary agents with good adhesion and spreadability as dispersing and diluting carriers, and is easy to adhere to waxy or smooth leaf surfaces, so that the dispersible oil suspending agent has the advantages of good adhesion and spreadability, strong permeation conductivity, strong rain wash resistance and the like when in use. The dispersible oil suspending agent is more stable than a water suspending agent in performance, has no dust in the production and use processes, uses environment-friendly solvent oil, is not easy to cause pollution to the environment, people and livestock, is more environment-friendly than missible oil and wettable powder, and has better drug effect. At present, fipronil and pyriproxyfen are not reported in dispersible oil suspending agents.
Disclosure of Invention
The invention aims to provide a dispersible oil suspending agent containing fipronil and pyriproxyfen, which has the characteristics of good emulsifying dispersibility, high suspension rate and good stability by matching and selecting auxiliaries and is more beneficial to the exertion of the drug effects of the fipronil and the pyriproxyfen.
Fipronil is a white solid with a melting point of 200-201 ℃ and a density of 1.477-1.626 (20 ℃), a pyriproxyfen original drug is a light yellow crystal with a melting point of 45-47 ℃ and a relative density of 1.23. The fipronil and the pyriproxyfen have high lipophilicity, the melting point of the pyriproxyfen is low, the two components are difficult to be prepared into dispersible oil suspending agents in a mixing mode, and the original drug particles are easy to crystallize and stratify in a suspension dispersion system. In addition, the pyriproxyfen is easy to decompose under the high-temperature storage condition due to the low melting point of the technical material and the chiral pesticide property, and the fipronil and the pyriproxyfen dispersible oil suspending agent are easy to degrade under the high-temperature storage condition, so that the pesticide effect is influenced. In order to solve these problems, it is difficult to select an auxiliary, and if the auxiliary is not properly selected, the resulting preparation tends to suffer from problems such as delamination, crystallization, and degradation of the active ingredient of the drug, which may affect the efficacy of the drug. The inventor carries out a large amount of screening work on an auxiliary system, finally obtains the optimal auxiliary composition, greatly reduces the processing difficulty of the preparation formulation through the synergistic matching of all the auxiliaries, particularly the synergistic matching of 3 auxiliaries of an emulsifier, a dispersing agent and a thickening agent, improves the stability of the preparation formulation, and inhibits the degradation of active ingredients of medicaments through the addition of a stabilizer.
The dispersible oil suspending agent containing fipronil and pyriproxyfen comprises the following components in percentage by weight: 5-30% of active ingredients, 6-20% of emulsifier, 1-8% of dispersant, 1-8% of thickener, 0.5-2% of stabilizer and the balance of dispersion medium to 100%.
Further, the dispersible oil suspending agent preferably consists of the following components in percentage by weight: 5-30% of active ingredients of the medicine, 10-20% of emulsifier, 4-7% of dispersant, 2-6% of thickening agent, 0.8-2% of stabilizing agent and dispersion medium which is added to 100%.
Further, the effective components are fipronil and pyriproxyfen. Preferably, the mass ratio of the fipronil to the pyriproxyfen is 0.05-20.
Further, the emulsifier is one or more of polyoxyethylene sorbitan monooleate, styryl phenol polyoxyethylene ether, castor oil polyoxyethylene ether, calcium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether.
Further, the dispersant is one or more of calcium lignosulfonate, sodium alkylphenol sulfonate, polyoxyethylene-polyoxypropylene block copolymer and alkyl naphthalene sulfonate formaldehyde condensate.
Further, the thickener is one or more of fumed silica, organic bentonite, attapulgite and urea.
Further, the stabilizer is one or more of butyl hydroxy anisole, triphenyl phosphite, epichlorohydrin and soybean lecithin.
Furthermore, the dispersion medium is one or more of soybean oil, methyl oleate, rapeseed oil and soybean oil methyl ester, and the dispersion medium used in the invention is an environment-friendly solvent, so that the environment is protected, the compatibility of the components is good, and the stability of the product is improved.
Furthermore, the dispersible oil suspending agent solves or reduces the defects existing when fipronil and pyriproxyfen are prepared into the preparation through the selection of the emulsifying agent, the dispersing agent, the thickening agent, the stabilizing agent and the dispersing medium, and the obtained dispersible oil suspending agent has the advantages of good dispersion stability, high suspension rate, good heat storage stability and the like. Preferably, the emulsifier is prepared by mixing polyoxyethylene sorbitan monooleate and calcium dodecylbenzene sulfonate according to the mass ratio of 1-3; the dispersing agent is formed by mixing a polyoxyethylene-polyoxypropylene segmented copolymer and an alkyl naphthalene sulfonate formaldehyde condensate according to the mass ratio of 2-4; the thickener is formed by mixing fumed silica and organic bentonite according to the mass ratio of 1; the stabilizer is triphenyl phosphite; the dispersion medium is methyl oleate. The optimization of the auxiliary agents is more beneficial to the optimization of the performance of the preparation and the exertion of the drug effect of the active ingredients, particularly, the optimization of the emulsifying agent, the dispersing agent and the thickening agent has better promotion effect on the performance and the exertion of the drug effect of the preparation, and the optimization of the stabilizing agent can better inhibit the degradation of the active ingredients.
The invention also provides a preparation method of the dispersible oil suspending agent, which comprises the following steps: adding a dispersion medium, an emulsifier, a dispersant and a stabilizer into a reaction kettle, and fully mixing and uniformly dispersing; adding the thickening agent, fipronil and pyriproxyfen into the reaction kettle under the high-speed shearing state, shearing for 10-30 minutes, and then grinding until the particle diameter D of the mixture is 90 And (5) obtaining the dispersible oil suspending agent containing fipronil and pyriproxyfen, wherein the particle size of the dispersible oil suspending agent is less than 4 mu m.
In the preparation method, the shearing speed of high-speed shearing is 1000-10000r/min.
In the above preparation method, the grinding can be carried out as disclosed in the prior artFor example, grinding may be performed under zirconia bead grinding media. After grinding, detecting by a laser particle size distribution instrument until the particle diameter D 90 Less than 4 mu m.
The dispersible oil suspending agent can improve the insecticidal effect of the agent, expand the insecticidal spectrum and improve the safety of crops by compounding the fipronil and the pyriproxyfen according to a specific ratio; by selecting the auxiliary agent, the emulsifying dispersibility, the suspension rate and the stability of the preparation are improved. The dispersible oil suspending agent has a good application prospect in the aspect of preventing and treating crop pests, and has a good prevention and treatment effect on aphids, plant hoppers, whiteflies, thrips and the like.
The invention has the following beneficial effects:
1. the active ingredients fipronil and pyriproxyfen of the pesticide belong to two insecticides with different action mechanisms, and the two insecticides are mixed with each other without conflict, so that the insecticidal spectrum is expanded, the insecticidal efficiency is improved, and the pesticide has obvious synergistic effect.
2. According to the invention, through the screening and matching of the emulsifier, the dispersant and the thickener, the stability of the product is improved, and the problems of crystallization and layering of the preparation are reduced or solved.
3. The invention effectively inhibits the degradation of the pyriproxyfen under high-temperature storage by adding the stabilizer.
4. The dispersible oil suspending agent is convenient to use, can be used for conventional spraying and spraying of a plant protection unmanned aerial vehicle, and has the advantages of difficult volatilization of liquid medicine, drift resistance, strong permeation conductivity, rain wash resistance and high target bioactivity.
5. The dispersible oil suspending agent disclosed by the invention is simple in preparation process, easy to operate, environment-friendly and safe in preparation process, free of pollution problem, low in cost and easy for industrial production. The obtained dispersible oil suspending agent has good emulsifying dispersibility, low probability of thickening, bottom precipitation, crystallization and delamination, less residue after pouring, high suspension rate and good heat storage stability. Through the optimization of each auxiliary agent, the residue of the obtained dispersible oil suspending agent after pouring is lower than 1.2%, and the suspension rate before and after heat storage can reach more than 95%.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be purely exemplary and are not intended to be limiting.
Unless otherwise specified, the following percentages are by weight.
The insecticidal compounding synergistic ratio of the fipronil and the pyriproxyfen is measured by an indoor toxicity experiment. Indoor toxicity determination is carried out according to the Sun Yunpei method, the co-toxicity coefficient (CTC) of the two medicaments compounded according to a certain proportion is determined, the CTC is less than 80 and is antagonistic, the CTC is more than or equal to 80 and is less than or equal to 120 and is additive, and the CTC is more than 120 and is synergistic.
Indoor toxicity determination of fipronil and pyriproxyfen compounded on rice planthopper nymphs
The test agents were provided by Shandong Weifang Runfeng Feng chemical company Limited.
And (3) experimental design: after the effective inhibition concentration range of each medicament is determined through pre-test, each medicament is respectively treated with a series of concentrations according to the content of effective components, and clear water is used for comparison. The method is carried out according to the standard pesticide for indoor bioassay of pesticides, the lethal medium concentration of the pesticide and the mixed pesticide is measured by adopting an insect soaking method, and the cotoxicity coefficient is obtained by a method for calculating the combined toxicity provided by Sun Yunpei et al (1960).
The calculation formula is as follows (using fipronil as standard medicament, the virulence index is 100)
Figure 962155DEST_PATH_IMAGE001
Figure 410453DEST_PATH_IMAGE002
In the formula: m is a mixture of fipronil and pyriproxyfen in different proportions;
P fipronil Is the proportion of fipronil in the compound composition;
P pyriproxyfen Is the proportion of the pyriproxyfen in the compound composition.
The test results are shown in table 1:
Figure 203573DEST_PATH_IMAGE004
as can be seen from Table 1, the LC of fipronil and pyriproxyfen for the nymphs of rice planthoppers 50 1.18mg/L and 74.10mg/L, respectively. When the mass ratio of fipronil to pyriproxyfen is within the range of 20-1 to 20, the cotoxicity coefficient is more than 120, and the synergistic effect is shown, but the additive effect is shown when the mass ratio of fipronil to pyriproxyfen is 1.
In the following, several examples of dispersible oil suspensions of the present invention are listed to further illustrate the invention.
Example 1
The formula is as follows: 1% of fipronil, 4% of pyriproxyfen, 4% of castor oil polyoxyethylene ether serving as an emulsifier, 6% of alkylphenol polyoxyethylene, 1% of calcium lignosulfonate serving as a dispersant, 1% of polyoxyethylene-polyoxypropylene block copolymer, 2% of fumed silica serving as a thickener, 4% of attapulgite, 1.5% of butyl hydroxy anisole serving as a stabilizer and the balance of soybean oil serving as a dispersion medium to 100%.
The preparation method comprises the following steps: adding a dispersion medium, an emulsifier, a dispersant and a stabilizer into a reaction kettle, and fully mixing and uniformly dispersing; adding the thickening agent, fipronil and pyriproxyfen into the reaction kettle under the high-speed shearing state of 1000r/min, shearing for 10-30 minutes, and then grinding until the particle diameter D of the mixture is 90 And (5) obtaining the dispersible oil suspending agent containing fipronil and pyriproxyfen, wherein the particle size of the dispersible oil suspending agent is less than 4 mu m.
Example 2
The formula is as follows: fipronil 5%, pyriproxyfen 5%, emulsifier polyoxyethylene sorbitan monooleate 6%, calcium dodecylbenzene sulfonate 6%, dispersant polyoxyethylene-polyoxypropylene block copolymer 3%, alkyl naphthalene sulfonate formaldehyde condensate 1%, thickener fumed silica 1%, organic bentonite 4%, stabilizer triphenyl phosphite 1.2%, and dispersing medium methyl oleate complement 100%. The preparation method is the same as example 1.
Example 3
The formula is as follows: fipronil 5%, pyriproxyfen 7%, emulsifier styrylphenol polyoxyethylene ether 8%, fatty alcohol polyoxyethylene ether 9%, dispersant sodium alkyl phenol sulfonate 2%, polyoxyethylene-polyoxypropylene block copolymer 1%, thickener organic bentonite 3%, urea 1%, stabilizer epichlorohydrin 1.0%, and dispersion medium rapeseed oil complement 100%. The preparation method is the same as example 1.
Example 4
The formula is as follows: fipronil 10%, pyriproxyfen 5%, emulsifier polyoxyethylene sorbitan monooleate 8%, calcium dodecylbenzene sulfonate 6%, dispersant polyoxyethylene-polyoxypropylene block copolymer 3%, alkyl naphthalene sulfonate formaldehyde condensate 1.5%, thickener fumed silica 1%, organic bentonite 3%, stabilizer triphenyl phosphite 1.1%, and dispersing medium methyl oleate complement 100%. The preparation method is the same as example 1.
Example 5
The formula is as follows: fipronil 10%, pyriproxyfen 1%, emulsifier calcium dodecylbenzene sulfonate 10%, polyoxyethylene sorbitan monooleate 4%, dispersant sodium alkyl phenol sulfonate 2%, polyoxyethylene-polyoxypropylene block copolymer 1%, thickener attapulgite 2%, urea 2%, stabilizer soybean lecithin 0.8%, and dispersion medium soybean oil methyl ester complement 100%. The preparation method is the same as example 1.
Example 6
The formula is as follows: 12% of fipronil, 8% of pyriproxyfen, 12% of emulsifier polyoxyethylene sorbitan monooleate, 4% of calcium dodecyl benzene sulfonate, 4% of dispersant polyoxyethylene-polyoxypropylene block copolymer, 1% of alkyl naphthalene sulfonate formaldehyde condensate, 1.5% of thickener fumed silica, 1.5% of organic bentonite, 1% of stabilizer triphenyl phosphite and the balance of dispersion medium methyl oleate to 100%. The preparation method is the same as example 1.
Example 7
The formula is as follows: 10% of fipronil, 12% of pyriproxyfen, 11% of emulsifier styryl phenol polyoxyethylene ether, 6% of castor oil polyoxyethylene ether, 3% of dispersant calcium lignosulfonate, 2% of alkyl naphthalene sulfonate formaldehyde condensate, 2% of thickener organic bentonite, 1% of urea, 0.9% of stabilizer epichlorohydrin, and the balance of dispersion medium methyl oleate for 100%. The preparation method is the same as example 1.
Example 8
The formula is as follows: fipronil 10%, pyriproxyfen 15%, emulsifier calcium dodecylbenzene sulfonate 12%, styrylphenol polyoxyethylene ether 6%, dispersant calcium lignosulfonate 3%, polyoxyethylene-polyoxypropylene block copolymer 3%, thickener fumed silica 1.5%, organic bentonite 0.5%, stabilizer triphenyl phosphite 0.8%, and dispersion medium soybean oil methyl ester make up to 100%. The preparation method is the same as example 1.
Example 9
The formula is as follows: fipronil 15%, pyriproxyfen 15%, emulsifier polyoxyethylene sorbitan monooleate 15%, calcium dodecylbenzene sulfonate 5%, dispersant polyoxyethylene-polyoxypropylene block copolymer 4%, alkyl naphthalene sulfonate formaldehyde condensate 3%, thickener fumed silica 0.5%, organic bentonite 1.5%, stabilizer triphenyl phosphite 2%, and dispersing medium methyl oleate complement 100%. The preparation method is the same as example 1.
Comparative example 1
The formula is as follows: fipronil 10%, pyriproxyfen 5%, emulsifier polyoxyethylene ether carboxylate 8%, fatty acid polyoxyethylene ester phosphate 6%, dispersant naphthalenesulfonic acid formaldehyde condensate sodium salt 3%, alkylphenol polyoxyethylene ether phosphate 2%, thickener magnesium aluminum silicate 3%, common white carbon black 1%, stabilizer triphenyl phosphite 1.1%, and dispersing medium methyl oleate complement 100%. The preparation method is the same as example 1.
Comparative example 2
The formula is as follows: fipronil 10%, pyriproxyfen 5%, emulsifier polyoxyethylene sorbitan monooleate 8%, calcium dodecylbenzene sulfonate 6%, dispersant polyoxyethylene-polyoxypropylene block copolymer 3%, alkyl naphthalene sulfonate formaldehyde condensate 1.5%, thickener fumed silica 1%, organic bentonite 3%, and dispersing medium methyl oleate to make up 100%. The preparation method is the same as example 1.
The properties of the dispersible oil suspension concentrates prepared in the above examples and comparative examples were measured, and the results are shown in table 2 below. Wherein, the suspension percentage is detected according to a method for measuring the suspension percentage of the pesticide GB/T14825-2006, the pourability is detected according to a method for measuring the pourability of the pesticide GB/T31737-2015, the dispersion stability is detected according to CIPAC MT 180 measuring the dispersion stability of the suspoemulsion by the International Council of pesticide analysis and collaboration, and the heat storage stability is detected according to a method for measuring the heat storage stability of the pesticide GBT 19136-2003.
Figure 129940DEST_PATH_IMAGE006
As can be seen from table 2, the products of examples 2, 4, 6, and 9 using the preferred adjuvants are stable in quality before and after hot storage, and maintain high suspension percentage, low pouring residue, and good dispersion stability, while the products of examples 1, 3, 5, 7, and 8 using non-preferred adjuvants are slightly inferior in hot storage stability to those of examples 2, 4, 6, and 9, but are also superior in performance, while comparative example 1 is poor in dispersion stability of the formulation and low in suspension percentage due to improper selection of the emulsifier, dispersant, and thickener. In addition, from examples 1-9, the formulations maintained better performance over 5-30% drug content.
Fipronil and pyriproxyfen dispersible oil suspending agents prepared in example 4 and comparative example 2 were subjected to drug stability testing: placing the dispersible oil suspending agent in a closed container, standing at 65 deg.C for 14 days, detecting the content difference of effective components of the medicine before and after standing by high performance liquid chromatography, and calculating the decomposition rate.
Figure 272209DEST_PATH_IMAGE007
As can be seen from Table 3, in comparative example 2, the decomposition of pyriproxyfen is severe and reaches 21.57% without adding the stabilizer, while the decomposition of pyriproxyfen in example 4 with the stabilizer is slight (2.00%) and meets the product quality requirement.
Experiment of drug effect
Field test example: pesticide effect test for preventing and controlling tomato whitefly through field test
The test is carried out in vegetable bases of Shouguang city, shandong province, and the control agents are 5% fipronil suspending agent and 10% pyriproxyfen emulsifiable concentrate (purchased from the market). The total 4 treatments are respectively as follows: treatment 1: spraying with clear water, and blank control; and (3) treatment 2: fipronil pyriproxyfen dispersible oil suspension obtained in examples 4 and 7 and comparative example 1; and (3) treatment: 5% fipronil suspending agent; and (4) treatment: 10% pyriproxyfen emulsifiable concentrate.
In the examples 4 and 7 and the comparative example 1, the fipronil-pyriproxyfen dispersible oil suspension obtained in the example 3 was subjected to stem and leaf spraying treatment according to the effective component amount of 60 g/ha, the stem and leaf spraying treatment according to the effective component amount of 105 g/ha in the treatment 3 was subjected to stem and leaf spraying treatment according to the effective component amount of 90 g/ha in the treatment 4.
The tomato whitefly was in the prime stage when tested. The pesticide is applied for 1 time by a worker-farm-16 knapsack manual sprayer, 750kg of water is added to prepare the pesticide liquid according to the dosage of the preparation per hectare, and the uniform spraying is carried out according to the amount of the pesticide liquid in the community. The weather during the test is good, and the daily average temperature is 22-30.0 ℃. No rain appears on the day of drug application, and no rain appears within 21 days after drug application.
Investigating population base before applying the pesticide, investigating live insect quantity in 3 rd, 14 th and 21 th days after the pesticide, calculating population decline rate, and observing the safety of the test medicament to crops.
The survey statistical method comprises the following steps: at each survey of 15 crops identified per plot, the leaf backs were carefully examined without frightening the insects, the number of live adults was recorded, and the leaves were examined in the morning when the adults were less active.
Figure 642141DEST_PATH_IMAGE008
Figure DEST_PATH_IMAGE010
As can be seen from the test results in the above table 4, the combination of fipronil and pyriproxyfen has good control effect on tomato whitefly, and the population reduction rate is superior to that of fipronil suspending agent and pyriproxyfen missible oil contrast agent. As can be seen from the comparison of the drug effects of the examples and the comparative examples, the selection of the auxiliary agent has an important influence on the exertion of the effective components, and improper selection of the auxiliary agent can influence the compounding effect of the fipronil and the pyriproxyfen. According to the observation of the whole field test process, the tomatoes have good growth vigor within the test dose range, and the pesticide damage phenomenon does not occur in each treatment agent, which indicates that the tomatoes are safe.

Claims (9)

1. A dispersible oil suspending agent containing fipronil and pyriproxyfen is characterized by comprising the following components in percentage by weight: 5-30% of active ingredients, 6-20% of emulsifier, 1-8% of dispersant, 1-8% of thickener, 0.5-2% of stabilizer and 100% of dispersion medium, wherein the active ingredients are fipronil and pyriproxyfen.
2. The dispersible oil suspension concentrate of claim 1, consisting of the following components in weight percent: 5-30% of active ingredients of the medicine, 10-20% of emulsifier, 4-7% of dispersant, 2-6% of thickening agent, 0.8-2% of stabilizing agent and dispersion medium which is added to 100%.
3. The dispersible oil suspension as claimed in claim 1 or 2, characterized in that: the mass ratio of fipronil to pyriproxyfen is 0.05-20.
4. The dispersible oil suspension of claim 1, wherein: the emulsifier is one or more of polyoxyethylene sorbitan monooleate, styryl phenol polyoxyethylene ether, castor oil polyoxyethylene ether, calcium dodecyl benzene sulfonate, fatty alcohol polyoxyethylene ether and alkylphenol polyoxyethylene ether; the dispersing agent is one or more of calcium lignosulfonate, sodium alkylphenol sulfonate, polyoxyethylene-polyoxypropylene block copolymer and alkyl naphthalene sulfonate formaldehyde condensate; the thickening agent is one or more of fumed silica, organic bentonite, attapulgite and urea; the stabilizer is one or more of butyl hydroxy anisole, triphenyl phosphite, epichlorohydrin and soybean lecithin; the dispersion medium is one or more of soybean oil, methyl oleate, rapeseed oil and soybean oil methyl ester.
5. The dispersible oil suspension of claim 1, wherein: the emulsifier is prepared by mixing polyoxyethylene sorbitan monooleate and calcium dodecyl benzene sulfonate according to the mass ratio of 1-3; the dispersing agent is formed by mixing a polyoxyethylene-polyoxypropylene segmented copolymer and an alkyl naphthalene sulfonate formaldehyde condensate according to the mass ratio of 2-4; the thickener is prepared by mixing fumed silica and organic bentonite according to a mass ratio of 1.
6. The dispersible oil suspension of claim 1, wherein: the stabilizer is triphenyl phosphite.
7. The dispersible oil suspension of claim 1, wherein: the dispersion medium is methyl oleate.
8. A method for preparing the dispersible oil suspension containing fipronil and pyriproxyfen of claim 1, which is characterized by comprising the following steps: adding a dispersion medium, an emulsifier, a dispersant and a stabilizer into a reaction kettle, and fully mixing and uniformly dispersing; adding the thickening agent, fipronil and pyriproxyfen into the reaction kettle under the high-speed shearing state, shearing for 10-30 minutes, and then grinding until the particle diameter D of the mixture is 90 Less than 4 mu m to obtain the dispersible oil suspending agent containing fipronil and pyriproxyfen; preferably, the shear rate is 1000 to 10000r/min.
9. The use of a dispersible oil suspension concentrate comprising fipronil and pyriproxyfen according to claim 1 for controlling pests on crops, preferably aphids, plant hoppers, whiteflies and thrips.
CN202110725353.8A 2021-06-29 2021-06-29 Dispersible oil suspending agent containing fipronil and pyriproxyfen and preparation method and application thereof Withdrawn CN115530174A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103355324A (en) * 2013-06-29 2013-10-23 海利尔药业集团股份有限公司 Insecticidal composition containing fipronil and pyriproxyfen
CN107787977A (en) * 2017-08-28 2018-03-13 南通功成精细化工有限公司 A kind of hygienic biocide composition containing Nylar and its application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103355324A (en) * 2013-06-29 2013-10-23 海利尔药业集团股份有限公司 Insecticidal composition containing fipronil and pyriproxyfen
CN107787977A (en) * 2017-08-28 2018-03-13 南通功成精细化工有限公司 A kind of hygienic biocide composition containing Nylar and its application

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