Nanoscale bactericide containing epoxiconazole and preparation method thereof

Abstract

The invention relates to the technical field of pesticides, and particularly discloses an epoxiconazole-containing nanoscale bactericide and a preparation method thereof. The epoxiconazole-containing nanoscale bactericide is mainly prepared from the following raw materials in percentage by weight: 10 to 15 percent of epoxiconazole active compound, 1 to 3 percent of tripeptide-1 derivative, 0.3 to 0.7 percent of 1, 3-dimethyl-2-imidazolinone, 1 to 3 percent of sodium lauryl polyoxyethylene ether sulfate, 2 to 4 percent of sodium polyphosphate, 0.5 to 0.9 percent of thickening agent, 0.001 to 0.003 percent of preservative, 3 to 5 percent of antifreezing agent, 0.1 to 0.5 percent of organic silicon defoaming agent and the balance of water. The tripeptide-1 derivative is obtained by treating tripeptide-1 with ethyl oleate. The nanoscale bactericide has the characteristics of being high in epoxiconazole suspension rate, easy to pour and clean, good in storage stability, good in prevention and treatment effect and high in pesticide effect, and meets market requirements.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of pesticides, more particularly, it relates to a nano fungicide containing fluquinconazole and a preparation method thereof. BACKGROUND

[0002] Fluquinconazole is an endosporal triazole fungicide, which can inhibit the biosynthesis of ergosterol in the cell membrane of pathogenic fungi, hinder the formation of pathogenic fungal cell wall, and has a significant control effect on various fungal diseases such as wheat powdery mildew, rice smut, corn rust and the like. Due to its wide fungicidal spectrum and strong systemicity, fluquinconazole has become one of the core fungicides for preventing and controlling fungal diseases in agricultural production. The raw materials of the fluquinconazole fungicide on the market generally include fluquinconazole and water, the chemical name of fluquinconazole is (2RS, 3SR)-1-[3-(2-chlorophenyl)-2, 3-epoxy-2-(4-fluorophenyl) propyl]-1H-1, 2, 4-triazole, and it is mainly suspended in the system in the form of particles. The fluquinconazole fungicide is applied to rice to control smut, and the field control effect is about 80% 14 days after spraying, which is not good enough and needs to be further improved. SUMMARY

[0003] In order to improve the field control effect of the nano fungicide, the present application provides a nano fungicide containing fluquinconazole and a preparation method thereof.

[0004] In the first aspect, the present application provides a nano fungicide containing fluquinconazole, which adopts the following technical scheme: A nano fungicide containing fluquinconazole is mainly made of the following raw materials by weight percentage: fluquinconazole technical material 10-15%, tripeptide-1 derivative 1-3%, 1, 3-dimethyl-2-imidazolinone 0.3-0.7%, sodium lauryl sulfate 1-3%, sodium polyphosphate 2-4%, thickening agent 0.5-0.9%, preservative 0.001-0.003%, antifreeze 3-5%, silicone defoaming agent 0.1-0.5%, and the balance is water; the tripeptide-1 derivative is obtained by treating tripeptide-1 with ethyl oleate.

[0005] The nano fungicide containing fluquinconazole of the present application has the characteristics of high fluquinconazole suspension rate, easy pouring, easy cleaning and good storage stability, through the mutual cooperation between the raw materials, the fluquinconazole suspension rate is >96%, the residual content after pouring is <3%, the residual content after washing is <0.2%, the low-temperature stability is qualified, and the thermal storage stability is qualified. The nano fungicide is applied to rice to control smut, and the field control effect is >73% 7 days after spraying and >90% 14 days after spraying, which has the advantages of good control effect and high efficacy, and meets the market demand.

[0006] The nanoscale fungicide of the present application takes fluquinconazole as the active ingredient, and the fluquinconazole is suspended in the system in the form of particles. The fluquinconazole can inhibit the biosynthesis of ergosterol in the cell membrane of the pathogenic bacteria, hinder the formation of the cell wall of the pathogenic bacteria, and can also induce the enhancement of chitinase activity. The chitinase can directly decompose the chitin of the cell wall of the pathogenic bacteria, resulting in the defect of the cell wall and the exposure of the cell membrane, and finally leading to the death of the pathogenic bacteria and realizing the drug efficacy. On this basis, the tripeptide-1 derivative and 1,3-dimethyl-2-imidazolidinone are added. The tripeptide-1 derivative is obtained by treating the tripeptide-1 with ethyl oleate. The synergistic effect between the tripeptide-1 derivative and 1,3-dimethyl-2-imidazolidinone not only helps the dispersion of the active ingredient, but also can reduce the surface tension, increase the wetting capacity, enhance the affinity of the active ingredient and the leaf, and act on the surface of the leaf to destroy the wax layer or the cuticle layer, form a transmission channel, accelerate the penetration of the active ingredient, make the active ingredient be fully absorbed and exert the drug efficacy, and improve the field control effect.

[0007] Optionally, the tripeptide-1 derivative is prepared by the following method: mixing an organic solvent and tripeptide-1, adding ethyl oleate, stirring for 18-22 hours, and distilling under reduced pressure to obtain the tripeptide-1 derivative.

[0008] Optionally, the weight ratio of the tripeptide-1 to ethyl oleate is 10:(3-4).

[0009] By adopting the above technical solution, the tripeptide-1 contains an amino group, and the ethyl oleate contains an ester group. The ethyl oleate is grafted onto the tripeptide-1 by using the reaction of the amino group and the ester group, and the tripeptide-1 derivative is obtained, which ensures the stability of the preparation of the tripeptide-1 derivative and ensures the quality and use effect of the tripeptide-1 derivative.

[0010] Optionally, the weight ratio of the tripeptide-1 to the organic solvent is 1:(8-12).

[0011] In multiple embodiments, the weight ratio of the tripeptide-1 to the organic solvent is 1:10, and the weight ratio can also be set to 1:8, 1:9, 1:11, 1:12, or the like according to needs, but is not limited to the listed values. Other values not listed in the range are also applicable.

[0012] Optionally, the organic solvent is one or more of ethanol, ethylene glycol, propanol, propylene glycol, and glycerol.

[0013] By adopting the above technical solution, the organic solvent is limited, which facilitates the selection of the organic solvent. Moreover, the organic solvent can make the tripeptide-1 and the ethyl oleate fully contact and react, which ensures the stability of the preparation of the tripeptide-1 derivative and the use effect.

[0014] In multiple embodiments, the time for stirring treatment in the preparation method of the tripeptide-1 derivative is 20h, which can also be set to 18h, 19h, 21h, 22h as required, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0015] Optionally, the thickening agent is selected from organic thickening agent and inorganic thickening agent, and the weight ratio of the organic thickening agent to the inorganic thickening agent is 1:(1-3).

[0016] By adopting the above technical solution, the thickening agent is selected from organic thickening agent and inorganic thickening agent. The synergistic effect of the organic thickening agent and the inorganic thickening agent not only increases the viscosity and improves the flowability, but also stabilizes the active ingredients, prevents the active ingredients from agglomerating, reduces the sedimentation, and ensures the stability of the nanoscale bactericide.

[0017] In multiple embodiments, the weight ratio of the organic thickening agent to the inorganic thickening agent is 1:2, which can also be set to 1:1, 1:1.5, 1:2.5, 1:3 as required, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0018] Optionally, the organic thickening agent is selected from one or more of xanthan gum, guar gum, and sodium carboxymethyl cellulose. The inorganic thickening agent is selected from one or more of magnesium aluminum silicate, bentonite, and white carbon black.

[0019] By adopting the above technical solution, the organic thickening agent and the inorganic thickening agent are optimized, which facilitates the selection of the organic thickening agent and the inorganic thickening agent. Moreover, the synergistic effect of the organic thickening agent and the inorganic thickening agent enables the nanoscale bactericide to have good stability and dispersibility, which helps to improve the use effect of the nanoscale bactericide.

[0020] Optionally, the preservative is selected from one or more of methyl isothiazolinone, chloromethyl isothiazolinone, sodium benzoate, and potassium sorbate. The antifreezing agent is selected from one or more of ethylene glycol, propylene glycol, glycerol, and sorbitol.

[0021] By adopting the above technical solution, the preservative and the antifreezing agent are optimized, which facilitates the selection of the preservative and the antifreezing agent. Moreover, the preservative can prevent the nanoscale bactericide from deteriorating and prolong the shelf life. The antifreezing agent can prevent the nanoscale bactericide from freezing in a low-temperature environment and ensure that it has good performance in a low-temperature environment.

[0022] Optionally, the organic silicon defoaming agent is selected from one or more of organic silicon defoaming agent AFE-1410, organic silicon defoaming agent AFE-7610, organic silicon defoaming agent BYK-022, and organic silicon defoaming agent BYK-093.

[0023] By adopting the above technical solution, the organic silicon defoaming agent is limited, which facilitates the selection of the organic silicon defoaming agent. Moreover, the organic silicon defoaming agent can reduce the surface tension of the foam, make the foam break quickly, eliminate the foam generated during preparation and use, and help improve the stability and quality of the nanoscale bactericide.

[0024] Optionally, the mass concentration of fluquinconazole in the fluquinconazole technical material is ≥95%, and the mass concentration of acetone is ≤0.5%.

[0025] By adopting the above technical solution, the content of fluquinconazole in the fluquinconazole technical material is limited, which ensures the stability of the fluquinconazole technical material source and the stability of the active ingredient content in the nanoscale bactericide, and ensures the efficacy and use effect of the nanoscale bactericide.

[0026] In a second aspect, the application provides a preparation method of the nanoscale bactericide containing fluquinconazole. The preparation method of the nanoscale bactericide containing fluquinconazole comprises the following steps: The water, fluquinconazole technical material, sodium lauryl polyoxyethylene ether sulfate, sodium polyphosphate, antifreeze, thickening agent, and preservative are mixed and ground, and then the tripeptide-1 derivative, 1,3-dimethyl-2-imidazolidinone, and organic silicon defoaming agent are added to obtain the nanoscale bactericide.

[0027] By adopting the above technical solution, not only is the preparation of the nanoscale bactericide facilitated, but also the raw materials are fully mixed, which ensures the stability and quality of the nanoscale bactericide.

[0028] In summary, the application has at least the following beneficial effects: 1. The nanoscale bactericide containing fluquinconazole has the characteristics of high fluquinconazole suspension rate, easy pouring, easy cleaning, and good storage stability, because the fluquinconazole suspension rate is >96%, the residual content after pouring is <3%, the residual content after washing is <0.2%, the low-temperature stability is qualified, and the heat storage stability is qualified.

[0029] 2、The fluquinconazole-containing nanoscale fungicide of the application takes fluquinconazole as the active ingredient and utilizes the synergistic effect between the tripeptide-1 derivative and 1,3-dimethyl-2-imidazolidinone, which not only helps the dispersion of the active ingredient, but also increases the wetting capacity and the affinity to the leaves, and acts on the leaf surface to form a transmission channel, accelerates the penetration of the active ingredient, makes the fluquinconazole fully absorbed and exerts the drug efficacy, and improves the field control effect. The field control effect is >90% 14 days after spraying, has the advantages of good control effect and high drug efficacy, and meets the market demand. DETAILED DESCRIPTION

[0030] The application will be further described in detail below in combination with examples.

[0031] Preparation Example Preparation Example 1 A tripeptide-1 derivative is prepared by the following method: 100 g of tripeptide-1 is added to 1000 g of ethanol under the rotation speed of 500 r / min, and stirred for 5 min. Then 38 g of ethyl oleate is added, and stirred for 20 h. Subsequently, vacuum distillation is performed to obtain the tripeptide-1 derivative.

[0032] Preparation Example 2 A tripeptide-1 derivative, which is different from that of Preparation Example 1, is different in the amount of ethyl oleate added, and the amount of ethyl oleate added is 30 g.

[0033] Preparation Example 3 A tripeptide-1 derivative, which is different from that of Preparation Example 1, is different in the amount of ethyl oleate added, and the amount of ethyl oleate added is 40 g. Example

[0034] Table 1 Dosage of each raw material of the nanoscale fungicide (unit: ×10 g) .

[0035] Example 1 A fluquinconazole-containing nanoscale fungicide, the raw materials and the raw material ratio of which are shown in Table 1.

[0036] Among them, the mass concentration of fluquinconazole in fluquinconazole technical material is 97%, and the mass concentration of acetone is 0.2%; the lauryl alcohol polyoxyethylene ether sulfate sodium salt is selected from Jinan Shiji Tongda Chemical Co., Ltd.; the polyphosphate sodium salt is selected from polycarboxylate sodium salt HT-5040; the preservative is selected from methylisothiazolinone; the antifreeze is selected from ethylene glycol; the organic silicon defoaming agent is selected from organic silicon defoaming agent AFE-7610; and the tripeptide-1 derivative is prepared by the method of Preparation Example 1.

[0037] The thickening agent is selected from organic thickening agent and inorganic thickening agent, and the weight ratio of the organic thickening agent and the inorganic thickening agent is 1:2, the organic thickening agent is selected from xanthan gum, the xanthan gum is instant xanthan gum, and is selected from Jiangsu Aofu Biological Technology Co., Ltd., and the inorganic thickening agent is selected from magnesium aluminum silicate.

[0038] A preparation method of a nano fungicide containing fluconazole, comprising the following steps: Fluconazole, sodium lauryl polyoxyethylene ether sulfate, sodium polyphosphate, antifreeze, thickening agent, preservative are added in water, and stirred for 10 min. Then, grinding treatment is carried out at a rotation speed of 2500 r / min and a temperature of 15℃ for 8h. Then, tripeptide-1 derivative, 1,3-dimethyl-2-imidazolidinone and organic defoaming agent are added, and stirred for 30 min to obtain the nano fungicide.

[0039] Example 2 A nano fungicide containing fluconazole, which is different from example 1 in that the raw material ratio of the nano fungicide is different, and the raw material ratio of the nano fungicide is shown in table 1.

[0040] Example 3 A nano fungicide containing fluconazole, which is different from example 1 in that the raw material ratio of the nano fungicide is different, and the raw material ratio of the nano fungicide is shown in table 1.

[0041] Example 4 A nano fungicide containing fluconazole, which is different from example 1 in that the raw material ratio of the nano fungicide is different, and the raw material ratio of the nano fungicide is shown in table 1.

[0042] Example 5 A nano fungicide containing fluconazole, which is different from example 1 in that the raw material ratio of the nano fungicide is different, and the raw material ratio of the nano fungicide is shown in table 1.

[0043] Example 6 A nano fungicide containing fluconazole, which is different from example 3 in that the source of tripeptide-1 derivative in the raw material of the nano fungicide is different, and the tripeptide-1 derivative is prepared by the method of preparation example 2.

[0044] Example 7 A nano fungicide containing fluconazole, which is different from example 3 in that the source of tripeptide-1 derivative in the raw material of the nano fungicide is different, and the tripeptide-1 derivative is prepared by the method of preparation example 3.

[0045] Comparative example Comparative example 1 A nanoscale fungicide containing fluquinconazole, which uses commercially available 12.5% fluquinconazole suspension concentrate, and is selected from Jiangsu Gengyun Chemical Co., Ltd.

[0046] Comparative Example 2 A nanoscale fungicide containing fluquinconazole, which is different from Example 3 in that in the raw material of the nanoscale fungicide, an equal amount of 1,3-dimethyl-2-imidazolidinone is used to replace the tripeptide-1 derivative.

[0047] Comparative Example 3 A nanoscale fungicide containing fluquinconazole, which is different from Example 3 in that in the raw material of the nanoscale fungicide, an equal amount of 1,3-dimethyl-2-imidazolidinone is used to replace the tripeptide-1 derivative.

[0048] Comparative Example 4 A nanoscale fungicide containing fluquinconazole, which is different from Example 3 in that in the raw material of the nanoscale fungicide, an equal amount of 1,3-dimethyl-2-imidazolidinone is used to replace the tripeptide-1 derivative.

[0049] Comparative Example 5 A nanoscale fungicide containing fluquinconazole, which is different from Example 3 in that in the raw material of the nanoscale fungicide, an equal amount of 1,3-dimethyl-2-imidazolidinone is used to replace the tripeptide-1 derivative.

[0050] Comparative Example 6 A nanoscale fungicide containing fluquinconazole, which is different from Example 3 in that in the raw material of the nanoscale fungicide, an equal amount of 1,3-dimethyl-2-imidazolidinone is used to replace the tripeptide-1 derivative.

[0051] Performance detection (1) The nanoscale fungicides obtained in Examples 1-7 and Comparative Examples 1-6 were taken as samples, respectively, and the following performance detection was carried out on the nanoscale fungicides, and the detection results are shown in Table 2.

[0052] Among them, according to GB / T14825-2006 "Pesticide Suspension Rate Determination Method", the fluquinconazole suspension rate of the nanoscale fungicide was detected.

[0053] According to GB / T31737-2015 "Pesticide Pouring Property Determination Method", the residual content after pouring and the residual content after washing of the nanoscale fungicide were detected.

[0054] Low temperature stability was detected by the following method: the nanoscale fungicide was placed and treated at a temperature of 2℃ for 14 days, and no crystallization and no stratification were observed to be qualified, otherwise unqualified.

[0055] The heat storage stability is determined by the following method: the nano fungicide is placed at a temperature of 54°C for 14 days, and is observed for no crystallization and no delamination, and is qualified, otherwise, is unqualified.

[0056] The field control effect is determined by the following method: rice is pre-planted in the test field, and the rice variety is 19 fragrant rice. The test field control object is smut. The nano fungicide is applied to the rice field to control smut. The application amount of the nano fungicide is 45 mL / acre, and the nano fungicide is diluted 1000 times with water before spraying. And spraying is carried out once 7 days before the occurrence of smut in rice, and spraying is carried out again after 10 days, that is, a total of twice in the growth cycle of rice. After the two times of spraying, the fixed-point sampling is carried out 7 days and 14 days later, and the field control effect is calculated. At the same time, a blank control group is set up. In the blank control group, water is used instead of the nano fungicide.

[0057] The smut of rice is divided into 5 levels, and the grading standard is: 0 level: no disease spot, completely healthy; 1 level: disease spot area accounts for ≤5% of total leaf area; 2 level: disease spot area accounts for 6-25% of total leaf area; 3 level: disease spot area accounts for 26-50% of total leaf area; 4 level: disease spot area accounts for >50% of total leaf area.

[0058] Disease index (%) = (Σ number of leaves at each level × corresponding level number) / (total number of leaves surveyed × highest level number) × 100%.

[0059] Field control effect (%) = (disease index of blank control area - disease index of spraying area) / disease index of blank control area × 100%.

[0060] Table 2: test results

[0061] As can be seen from Table 2, the nano fungicide of the application has a fluquinconazole suspension rate of >96%, a residual content after pouring of <3%, a residual content after washing of <0.2%, a persistent foaming volume of <20 mL, good low-temperature stability, and good heat storage stability. It has the characteristics of high fluquinconazole suspension rate, easy pouring, easy cleaning, and good storage stability. Moreover, when it is applied to rice to control smut, the field control effect is >73% 7 days after spraying, and the field control effect is >90% 14 days after spraying, which has the advantages of good control effect and high efficacy, and meets the market demand.

[0062] Example 3 and Comparative Example 1 are compared. Comparative Example 1 uses commercially available 12.5% epoxiconazole suspension concentrate; Example 3 uses the nanoscale fungicide of the present application. It can be seen that the commercially available 12.5% epoxiconazole suspension concentrate has a lower control effect on rice sheath blight than the nanoscale fungicide of the present application. This can be due to the fact that the nanoscale fungicide of the present application has high epoxiconazole suspension rate and good stability, which can enable epoxiconazole to fully exert its efficacy.

[0063] Comparative Examples 2-4 and Example 3 are compared. Comparative Example 3, compared with Comparative Example 2, adds 1,3-dimethyl-2-imidazolinone to the raw material of the nanoscale fungicide; Comparative Example 4, compared with Comparative Example 2, adds tripeptide-1 derivative to the raw material of the nanoscale fungicide; Example 3, compared with Comparative Example 2, adds 1,3-dimethyl-2-imidazolinone and tripeptide-1 derivative to the raw material of the nanoscale fungicide. It can be seen that the simultaneous addition of 1,3-dimethyl-2-imidazolinone and tripeptide-1 derivative to the raw material and the use of synergistic effect between the two can significantly improve the field control effect, and enhance the efficacy and use effect of the nanoscale fungicide.

[0064] Comparative Examples 5-6 and Example 3 are compared. Comparative Example 5 adds tripeptide-1 to the raw material of the nanoscale fungicide; Comparative Example 6 adds ethyl oleate to the raw material of the nanoscale fungicide; Example 3 adds tripeptide-1 derivative to the raw material of the nanoscale fungicide. It can be seen that the reaction of tripeptide-1 and ethyl oleate can graft ethyl oleate onto tripeptide-1, which can effectively increase the compatibility between ethyl oleate and the raw material, improve the thermal storage stability, and significantly improve the field control effect of the nanoscale fungicide.

[0065] The specific embodiments are merely illustrative of the present application, and are not intended to limit the present application. Those skilled in the art can make modifications to the embodiments without creative contribution after reading the present specification, and the modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A nanoscale fungicide containing fluocinolone acetonide, characterized in that: It is mainly made from the following raw materials in weight percentages: 10-15% flutriafol technical grade, 1-3% tripeptide-1 derivative, 0.3-0.7% 1,3-dimethyl-2-imidazolinone, 1-3% sodium lauryl polyoxyethylene ether sulfate, 2-4% sodium polyphosphate, 0.5-0.9% thickener, 0.001-0.003% preservative, 3-5% antifreeze, 0.1-0.5% silicone defoamer, and the balance being water; the tripeptide-1 derivative is obtained by treating tripeptide-1 with ethyl oleate.

2. The nanoscale bactericide containing fluocinolone acetonide according to claim 1, characterized in that: The tripeptide-1 derivative was prepared by the following method: an organic solvent and tripeptide-1 were mixed, ethyl oleate was added, the mixture was stirred for 18-22 hours, and then distilled under reduced pressure to obtain the tripeptide-1 derivative.

3. The nanoscale bactericide containing fluocinolone acetonide according to claim 2, characterized in that: The weight ratio of tripeptide-1 to ethyl oleate is 10:(3-4).

4. The nanoscale bactericide containing fluocinolone acetonide according to claim 2, characterized in that: The organic solvent is one or more of ethanol, ethylene glycol, propanol, propylene glycol, and glycerol.

5. The nanoscale bactericide containing fluocinolone acetonide according to claim 1, characterized in that: The thickener is selected from two types: organic thickener and inorganic thickener, and the weight ratio of organic thickener to inorganic thickener is 1:(1-3).

6. The nanoscale bactericide containing fluocinolone acetonide according to claim 5, characterized in that: The organic thickener is selected from one or more of xanthan gum, guar gum, and sodium carboxymethyl cellulose. The inorganic thickener is selected from one or more of magnesium aluminum silicate, bentonite, and silica.

7. The nanoscale bactericide containing fluocinolone acetonide according to claim 1, characterized in that: The preservative is selected from one or more of methylisothiazolinone, chloromethylisothiazolinone, sodium benzoate, and potassium sorbate; The antifreeze is selected from one or more of ethylene glycol, propylene glycol, glycerol, and sorbitol.

8. The nanoscale bactericide containing fluocinolone acetonide according to claim 1, characterized in that: The silicone defoamer is selected from one or more of silicone defoamer AFE-1410, silicone defoamer AFE-7610, silicone defoamer BYK-022, and silicone defoamer BYK-093.

9. The nanoscale bactericide containing fluocinolone acetonide according to claim 1, characterized in that: The flutriafol technical material contains a flutriafol mass concentration ≥95% and an acetone mass concentration ≤0.5%.

10. A method for preparing a nanoscale fungicide containing fluopyram as described in any one of claims 1-9, characterized in that: Includes the following steps: Water, flutriafol technical, sodium lauryl polyoxyethylene ether sulfate, sodium polyphosphate, antifreeze, thickener, and preservative are mixed and ground. Then, tripeptide-1 derivative, 1,3-dimethyl-2-imidazolinone, and organosilicon defoamer are added and mixed to obtain a nano-scale bactericide.

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