CN111149805A - Pyrimethanil nanoemulsion and preparation method thereof - Google Patents
Pyrimethanil nanoemulsion and preparation method thereof Download PDFInfo
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- CN111149805A CN111149805A CN201911376207.8A CN201911376207A CN111149805A CN 111149805 A CN111149805 A CN 111149805A CN 201911376207 A CN201911376207 A CN 201911376207A CN 111149805 A CN111149805 A CN 111149805A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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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 pyrimethanil nanoemulsion, which comprises 1 wt% -10 wt% of pyrimethanil, 20 wt% -40 wt% of solvent, cosolvent: 10-15 wt% of an emulsifier, 10-15 wt% of an antifreeze agent and the balance of water, wherein the solvent is a mixture of ethyl acetate and N-methyl pyrrolidone. The solvent is ethyl acetate and N-methyl pyrrolidone, and the weight ratio of the ethyl acetate to the N-methyl pyrrolidone is 2: 2, by weight. The preparation has the prevention and treatment effects on the gray mold of cucumber and tomato of more than 80 percent, has the prevention and treatment effects on the blight of cotton of more than 80 percent, and has obvious yield increasing effect. The pyrimethanil nanoemulsion disclosed by the invention is simple to prepare, can be produced and applied in large batch, and greatly improves the yield.
Description
Technical Field
The invention belongs to the field of plant protection, and particularly relates to a bactericide composition, in particular to pyrimethanil nanoemulsion and a preparation method thereof.
Background
Pyrimethanil (N- (4, 6-dimethyl pyrimidine-2-yl) aniline) belongs to anilinopyrimidine synthetic bactericide, colorless crystals or white or yellowish crystals can be dissolved in an organic solvent and are slightly soluble in water, the solubility of the compound in water at room temperature is 0.121g/L, the melting point is 96.3 ℃, the vapor pressure is 2.2 x 10 < -3 > Pa, and the compound is stable under weak acid-weak alkaline conditions; the chemical structural formula is shown as formula 1. The pyrimethanil is a traditional agricultural fungicide, has high control activity on gray mold of cucumber, gray mold of tomato and fusarium wilt, and is a current variety for controlling gray mold. It has unique action mechanism, prevents germ infection by inhibiting the generation of pathogen infecting enzyme, and has the characteristics of low toxicity, no teratogenesis, carcinogenesis and mutagenesis, etc. Has the functions of protecting and treating crops, has the functions of internal absorption and fumigation, and can quickly reach parts of plants, such as flowers, young fruits and the like, which can not be reached by spraying after the pesticide is applied, so as to kill germs.
The pyrimethanil as a novel bactericide has unique action mechanism, and can prevent the infection of germs and kill the germs by inhibiting the generation of germ-infecting enzyme. The action mechanism of the pyrimethanil is different from that of other bactericides, so that the pyrimethanil is particularly effective to the germs with drug resistance of the commonly used non-anilinopyrimidine bactericides, and has no cross resistance. The pyrimethanil has the effects of systemic conduction and fumigation, quickly reaches parts of plants such as flowers and young fruits which can not be reached by spraying after application, kills germs, and has quicker and more stable drug effect. The pyrimethanil has better crop disease treatment effects such as gray mold and the like, and has good quick action. However, the pyrimethanil is sensitive to some crops, and the use amount of the active ingredients exceeds 90 g/ha, which causes serious phytotoxicity. If the pyrimethanil is improperly used, phytotoxicity is easy to occur on crops, a plurality of dark brown spots appear on leaves, and the leaves are irregular in shape or yellow and fall off. When phytotoxicity spots appear, many vegetable farmers also consider crops to have 'spot defoliation', and as a result, the phytotoxicity is aggravated again, and a large amount of phytotoxicity accidents are reported every year, for example, in a Shandong Shougueu vegetable district in 2016, when farmers use 20% of pyrimethanil SC single dose, the phenomenon of tomato defoliation and fruit drop in the harvest period of more than 1000 mu is caused, and farmers are disastrous. The farmer has the advantages of pain and love for pyrimethanil, ideal prevention effect, but great risk of phytotoxicity.
Disclosure of Invention
Aiming at the technical problems, the invention provides the pyrimethanil nanoemulsion with better sterilization effect and the preparation method thereof. The specific technical scheme is as follows:
the invention provides pyrimethanil nanoemulsion, which comprises 1 wt% -10 wt% of pyrimethanil, 20 wt% -40 wt% of solvent, cosolvent: 10 to 15 weight percent of emulsifier, 10 to 15 weight percent of antifreeze agent and the balance of water.
Preferably, the solvent is a mixture of ethyl acetate and N-methylpyrrolidone.
Preferably, the solvent is ethyl acetate and N-methylpyrrolidone in a ratio of 2: 2, by weight.
Preferably, the cosolvent is lactic acid.
Preferably, the emulsifier is nonylphenol polyoxyethylene ether emulsifier.
Preferably, the antifreeze agent is hexanediol.
The invention also provides a preparation method of the pyrimethanil nanoemulsion, which comprises the following steps:
(1) dissolving pyrimethanil original drug in a mixed solution of ethyl acetate and N-methyl pyrrolidone;
(2) mixing and fully stirring the solution obtained in the step (1), a cosolvent and an emulsifier to form a uniform oil phase;
(3) and (3) under the stirring condition, adding water into the oil phase obtained in the step (2), adding an antifreeze agent, and freely dispersing to obtain the homogeneous transparent pyrimethanil nanoemulsion.
Preferably, the ratio of ethyl acetate to N-methylpyrrolidone is 2: 2, by weight.
Preferably, the cosolvent is lactic acid.
Preferably, the emulsifier is nonylphenol polyoxyethylene ether emulsifier.
Preferably, the antifreeze agent is hexanediol.
The invention has the following beneficial effects:
(1) the bactericide composition has good synergistic effect in a certain range and small dosage;
(2) the preparation belongs to a thermodynamic stable system, the preparation method is simple and convenient, strong shearing action is not needed, and the prepared product has stability and can be placed for a long time without demulsification, coalescence, delamination and other phenomena;
(3) the preparation has solubilization, the two pesticide components in the preparation have low solubility in water, and the selected emulsifier plays a role in solubilizing the main component, so that the pesticide is convenient to use, the dissolution rate of the pesticide is increased, and the physiological efficiency of the pesticide is improved;
(4) the preparation has high transfer efficiency, low viscosity, small average size below 100nm, easy dilution, low surface tension, less spray, excellent spreading performance and wetting performance and high transfer efficiency;
(5) the preparation enhances the imbibition of the plant to the pesticide, overcomes the capillary resistance in the epidermal tissue of the plant due to the reduction of the interfacial tension of the liquid medicine, and generates higher permeation rate to permeate into the tissue; due to solubilization, the concentration gradient between the liquid medicine and the plant epidermis is increased, so that the diffusion rate of pesticide ingredients is enhanced, and the transfer effect through diffusion is promoted;
(6) the preparation improves the pharmacological performance and the utilization efficiency of the pesticide, reduces the concentration of the liquid medicine, reduces the dosage, reduces the cost because the solvent of the preparation is water, and is favorable from the aspects of economy and ecological environment;
(7) the preparation has prevention effect on pathogenic substances in the prevention range of main drug components, has wide prevention range and delays the generation of resistance;
(8) the preparation has the prevention and treatment effects on the gray mold of cucumber and tomato of more than 80 percent, has the prevention and treatment effects on the blight of cotton of more than 80 percent, and has obvious yield increasing effect.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a 2000 times liquid processing electron microscope picture of pyrimethanil nanoemulsion;
FIG. 2 is a 4000-fold liquid processing electron microscope picture of pyrimethanil nanoemulsion;
FIG. 3 is an electron micrograph of water control treatment.
Detailed Description
The preparation method of the pyrimethanil nanoemulsion comprises the following steps:
example 1
Dissolving 97% pyrimethanil original drug 1g in a mixed solvent of ethyl acetate 2mL and N-methylpyrrolidone 2mL, adding a proper amount of lactic acid auxiliary agent 2mL, and mixing and stirring fully with emulsifier 2mL (nonylphenol polyoxyethylene ether emulsifier) to form a uniform oil phase. Under the condition of stirring, adding water into the oil phase, simultaneously adding 0.5mL of an appropriate amount of antifreeze agent (hexanediol), and freely dispersing to obtain a uniform and transparent pyrimethanil nanoemulsion preparation.
The contents are as follows: 7.2 wt% of pyrimethanil, 29.6 wt% of solvent, and cosolvent: 14.8 wt%, 14.8 wt% of emulsifier, 3.7 wt% of antifreeze agent and the balance of water.
Example two:
dissolving 97% pyrimethanil original drug 1g in a mixed solvent of ethyl acetate 1.5mL and N-methylpyrrolidone 1.5mL, adding a proper amount of lactic acid auxiliary agent 1.8mL, and fully mixing and stirring with emulsifier 1.8mL (nonylphenol polyoxyethylene ether emulsifier) to form a uniform oil phase. Under the condition of stirring, adding water into the oil phase, simultaneously adding 0.5mL of an appropriate amount of antifreeze agent (hexanediol), and freely dispersing to obtain a uniform and transparent pyrimethanil nanoemulsion preparation.
The contents are as follows: 7.7 wt% of pyrimethanil, 23.8 wt% of solvent, and cosolvent: 14.3 wt%, 14.3 wt% of emulsifier, 3.9 wt% of antifreeze agent and the balance of water.
Example three:
dissolving 97% pyrimethanil original drug 1g in a mixed solvent of ethyl acetate 2.5mL and N-methyl pyrrolidone 1.5mL, adding a proper amount of lactic acid auxiliary agent 2mL, and mixing and stirring fully with emulsifier 2mL (nonylphenol polyoxyethylene ether emulsifier) to form a uniform oil phase. Under the condition of stirring, adding water into the oil phase, simultaneously adding 0.5mL of an appropriate amount of antifreeze agent (hexanediol), and freely dispersing to obtain a uniform and transparent pyrimethanil nanoemulsion preparation.
The contents are as follows: pyrimethanil 6.9 wt%, solvent 28.6 wt%, cosolvent: 14.3 wt%, 14.3 wt% of emulsifier, 3.6 wt% of antifreeze agent and the balance of water.
Example four:
1g of 97% pyrimethanil original drug is dissolved in a mixed solvent of 1.8mL of ethyl acetate and 1.8mL of N-methyl pyrrolidone, 1.5mL of lactic acid auxiliary agent is added, and the mixture is fully mixed and stirred with 1.5mL of emulsifier (nonylphenol polyoxyethylene ether emulsifier) to form a uniform oil phase. Under the condition of stirring, adding water into the oil phase, simultaneously adding a proper amount of 0.4mL of antifreeze agent (hexanediol), and freely dispersing to obtain a uniform and transparent pyrimethanil nanoemulsion preparation.
The contents are as follows: 7.8 wt% of pyrimethanil, 28.8 wt% of solvent, and cosolvent: 12 wt% of emulsifier, 12 wt% of antifreeze agent and the balance of water.
Example five:
dissolving 97% pyrimethanil original drug 1g in a mixed solvent of ethyl acetate 2.2mL and N-methylpyrrolidone 1.8mL, adding a proper amount of lactic acid auxiliary agent 1.8mL, and fully mixing and stirring with emulsifier 1.8mL (nonylphenol polyoxyethylene ether emulsifier) to form a uniform oil phase. Under the condition of stirring, adding water into the oil phase, simultaneously adding a proper amount of 0.4mL of antifreeze agent (hexanediol), and freely dispersing to obtain a uniform and transparent pyrimethanil nanoemulsion preparation.
The contents are as follows: 7.8 wt% of pyrimethanil, 32 wt% of solvent, and cosolvent: 14.4 wt%, 14.4 wt% of emulsifier, 3.2 wt% of antifreeze agent and the balance of water.
The control test data of the pyrimethanil nanoemulsion on cucumber gray mold are as follows:
TABLE 1 inhibition of Botrytis cinerea after 3 days of treatment at different concentrations
As shown in Table 1, the pyrimethanil nanoemulsion has the inhibition effect of more than 82% on the growth of botrytis cinerea at different doses compared with clear water (sterile water).
As can be seen from the graphs 1 and 2, the hyphae were severely atrophied under the treatment of the pyrimethanil nanoemulsion of 2000X and 4000X, and there were no electron microscope pictures of spore growth.
The test result of the pyrimethanil nanoemulsion on cucumber gray mold in the field control is as follows:
TABLE 2 field control of cucumber Botrytis cinerea by different treatments of pyrimethanil nanoemulsion
As can be seen from Table 2, the pyrimethanil nanoemulsion has the effect of preventing and treating cucumber gray mold in fields of more than 80%, and the control medicament 80% carbendazim wp has the effect of preventing and treating cucumber gray mold of more than 70%, so that the prevention effect is obvious.
The control test data of the pyrimethanil nanoemulsion on the tomato gray mold are as follows:
TABLE 1 inhibition of Botrytis cinerea after treatment for 3d at different concentrations
As shown in Table 1, the pyrimethanil nanoemulsion has the inhibiting effect of more than 84% on the growth of botrytis cinerea at different doses compared with clear water (sterile water).
The test result of the pyrimethanil nanoemulsion on the field control of the tomato gray mold is as follows:
TABLE 2 Pyrimidinenanoemulsion different treatment effects on field control of tomato gray mold
| Treatment of | Dosage g/667m2 | Average survey total number of fruits | Finger for disease | Control effect (%) |
| Example 1 | 75 | 189 | 3.1 | 84.1 |
| Example 2 | 75 | 179 | 3.2 | 83.6 |
| Example 3 | 75 | 199 | 3.1 | 84.1 |
| Example 4 | 75 | 191 | 3.1 | 84.1 |
| Example 5 | 75 | 195 | 3.0 | 84.6 |
| 80% carbendazim wp | 75 | 196 | 5.4 | 71.9 |
| CK (Water) | — | 190 | 19.5 | — |
As can be seen from Table 2, the pyrimethanil nanoemulsion has the effect of preventing and treating the tomato gray mold in the field of over 80 percent, and the control medicament 80 percent of carbendazim wp has the effect of preventing and treating the tomato gray mold of over 70 percent, so the control effect is obvious.
The field control test result of the pyrimethanil nanoemulsion on cotton wilt disease is as follows:
TABLE 3 field control of cotton wilt with pyrimethanil nanoemulsion different treatments
As shown in Table 3, the amount of pyrimethanil nanoemulsion used is 199.5g/hm2The effects of preventing and treating cotton wilt are all above 87%, and the test has no pollution to the growth of cotton, the best application is carried out at the initial stage of the disease of the cotton wilt, and the better effect is achieved after the cotton wilt is sprayed 7 days after the first application.
Claims (10)
1. The pyrimethanil nanoemulsion comprises 1-10 wt% of pyrimethanil, 20-40 wt% of solvent, and cosolvent: 10 to 15 weight percent of emulsifier, 10 to 15 weight percent of antifreeze agent and the balance of water.
2. The pyrimethanil nanoemulsion of claim 1, characterized in that: the solvent is a mixture of ethyl acetate and N-methyl pyrrolidone, and the solvent is a mixture of ethyl acetate and N-methyl pyrrolidone, wherein the weight ratio of ethyl acetate to N-methyl pyrrolidone is 2: 2, by weight.
3. The pyrimethanil nanoemulsion of claim 1, characterized in that: the cosolvent is lactic acid.
4. The pyrimethanil nanoemulsion of claim 1, characterized in that: the emulsifier is nonylphenol polyoxyethylene ether emulsifier.
5. The pyrimethanil nanoemulsion of claim 1, characterized in that: the antifreeze agent is hexanediol.
6. A preparation method of pyrimethanil nanoemulsion comprises the following steps:
(1) dissolving pyrimethanil original drug in a mixed solution of ethyl acetate and N-methyl pyrrolidone;
(2) mixing and fully stirring the solution obtained in the step (1), a cosolvent and an emulsifier to form a uniform oil phase;
(3) and (3) under the stirring condition, adding water into the oil phase obtained in the step (2), adding an antifreeze agent, and freely dispersing to obtain the homogeneous transparent pyrimethanil nanoemulsion.
7. The method of preparing pyrimethanil nanoemulsion of claim 6, characterized in that: the ethyl acetate and the N-methyl pyrrolidone are mixed according to the weight ratio of 2: 2, by weight.
8. The pyrimethanil nanoemulsion of claim 6, characterized in that: the cosolvent is lactic acid.
9. The method of preparing pyrimethanil nanoemulsion of claim 6, characterized in that: the emulsifier is nonylphenol polyoxyethylene ether emulsifier.
10. The method of preparing pyrimethanil nanoemulsion of claim 6, characterized in that: the antifreeze agent is hexanediol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994084A (en) * | 2007-01-09 | 2007-07-11 | 海南博士威农用化学有限公司 | Oil-like transparent liquid antifungal composition containing pyrimethanil |
| CN102217607A (en) * | 2011-04-27 | 2011-10-19 | 河北工程大学 | Hymexazol nanoemulsion and formulation method |
| CN102224818A (en) * | 2011-04-22 | 2011-10-26 | 河北工程大学 | Benziothiazolinone nanoemulsion and preparation method thereof |
| CN106577684A (en) * | 2016-11-04 | 2017-04-26 | 东莞市联洲知识产权运营管理有限公司 | Pesticide nano emulsion in water and preparing method thereof |
-
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- 2019-12-27 CN CN201911376207.8A patent/CN111149805A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1994084A (en) * | 2007-01-09 | 2007-07-11 | 海南博士威农用化学有限公司 | Oil-like transparent liquid antifungal composition containing pyrimethanil |
| CN102224818A (en) * | 2011-04-22 | 2011-10-26 | 河北工程大学 | Benziothiazolinone nanoemulsion and preparation method thereof |
| CN102217607A (en) * | 2011-04-27 | 2011-10-19 | 河北工程大学 | Hymexazol nanoemulsion and formulation method |
| CN106577684A (en) * | 2016-11-04 | 2017-04-26 | 东莞市联洲知识产权运营管理有限公司 | Pesticide nano emulsion in water and preparing method thereof |
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