A nanoscale fungicide containing fluazinam and a preparation method thereof

Abstract

The application relates to the technical field of pesticides, and particularly discloses a nanoscale fungicide containing fluquinconazole and a preparation method thereof. The nanoscale fungicide containing fluquinconazole is mainly prepared from the following raw materials in percentage by weight: fluquinconazole 10-15%, tripeptide-1 derivative 1-3%, 1,3-dimethyl-2-imidazolidinone 0.3-0.7%, lauryl alcohol polyoxyethylene ether sulfate sodium salt 1-3%, polyphosphate sodium salt 2-4%, thickening agent 0.5-0.9%, preservative 0.001-0.003%, antifreezing agent 3-5%, organic silicon defoaming agent 0.1-0.5%, and water as the balance; the tripeptide-1 derivative is obtained by treating tripeptide-1 with ethyl oleate. The nanoscale fungicide has the characteristics of high fluquinconazole suspension rate, easy pouring, easy cleaning, good storage stability, good control effect and high efficacy, and meets the market demand.

Description

Technical Field

[0001] This application relates to the field of pesticide technology, and more specifically, to a nanoscale fungicide containing fluopyram and its preparation method. Background Technology

[0002] Fluticasone is a systemic triazole fungicide that inhibits the biosynthesis of ergosterol in the cell membrane of pathogens, thus hindering cell wall formation. It exhibits significant control effects against various fungal diseases, including wheat powdery mildew, rice false smut, and corn rust. Due to its broad spectrum of activity and strong systemic properties, it has become one of the core agents for controlling fungal diseases in agricultural production. Currently available fluticasone fungicides generally consist of fluticasone and water. The chemical name of fluticasone is (2RS,3SR)-1-[3-(2-chlorophenyl)-2,3-epoxy-2-(4-fluorophenyl)propyl]-1H-1,2,4-triazole, and it is primarily suspended in particulate form within the system. When applied to control rice false smut, this fluticasone fungicide showed a field control efficacy of approximately 80% after 14 days of spraying, indicating that the field control effect is unsatisfactory and requires further improvement. Summary of the Invention

[0003] To improve the field control effect of nano-scale fungicides, this application provides a nano-scale fungicide containing flutriafol and its preparation method.

[0004] In a first aspect, this application provides a nanoscale fungicide containing fluopyram, employing the following technical solution:

[0005] A nano-scale bactericide containing flutriafol is mainly composed of 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.

[0006] The flutriafol-containing nano-scale fungicide of this application, through the synergistic effect of the raw materials, achieves a flutriafol suspension rate >96%, a residue content <3% after pouring, a residue content <0.2% after washing, and satisfactory low-temperature stability and thermal storage stability. It features high flutriafol suspension rate, easy pouring, easy washing, and good storage stability. When applied to rice for the control of rice false smut, the field control effect is >73% after 7 days of spraying and >90% after 14 days, demonstrating excellent control efficacy and high efficacy, meeting market demand.

[0007] The nanoscale fungicide of this application uses flutriafol as the active ingredient, which is suspended in the system in particulate form. Flutriafol inhibits the biosynthesis of ergosterol in the bacterial cell membrane, hindering cell wall formation. Furthermore, flutriafol induces increased chitinase activity, which directly decomposes chitin in the bacterial cell wall, leading to cell wall defects, cell membrane exposure, and ultimately bacterial death, thus achieving the desired efficacy. Based on this, a tripeptide-1 derivative and 1,3-dimethyl-2-imidazolinone are added. The tripeptide-1 derivative is obtained by treating tripeptide-1 with ethyl oleate. The synergistic effect between the tripeptide-1 derivative and 1,3-dimethyl-2-imidazolinone not only aids in the dispersion of the active ingredient but also reduces surface tension, increases wetting ability, enhances the affinity between the active ingredient and leaves, and acts on the leaf surface, disrupting the waxy or cuticle layer to form delivery channels, accelerating the penetration of the active ingredient, ensuring full absorption and efficacy, and improving field control effectiveness.

[0008] 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.

[0009] Optionally, the weight ratio of tripeptide-1 to ethyl oleate is 10:(3-4).

[0010] By adopting the above technical solution, tripeptide-1 contains an amino group and ethyl oleate contains an ester group. By utilizing the reaction between the amino group and the ester group, ethyl oleate is grafted onto tripeptide-1 to obtain tripeptide-1 derivatives, ensuring the stability of tripeptide-1 derivative preparation and ensuring the quality and effectiveness of tripeptide-1 derivatives.

[0011] Optionally, the weight ratio of the tripeptide-1 to the organic solvent is 1:(8-12).

[0012] In several implementations, the weight ratio of tripeptide-1 to organic solvent is 1:10. It can also be set to 1:8, 1:9, 1:11, or 1:12 as needed, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0013] Optionally, the organic solvent is one or more of ethanol, ethylene glycol, propanol, propylene glycol, and glycerol.

[0014] By employing the above technical solution, the organic solvent is limited, facilitating its selection. Furthermore, the organic solvent allows for sufficient contact and reaction between tripeptide-1 and ethyl oleate, ensuring the stability and effectiveness of the prepared tripeptide-1 derivative.

[0015] In several embodiments, the stirring time in the preparation method of the tripeptide-1 derivative is 20 h. The time can also be set to 18 h, 19 h, 21 h, or 22 h as needed, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0016] Optionally, 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).

[0017] By adopting the above technical solution, the thickener is selected from organic and inorganic thickeners. Utilizing the synergistic effect of organic and inorganic thickeners not only increases viscosity and improves flowability, but also stabilizes the active ingredients, prevents their aggregation, reduces sedimentation, and ensures the stability of the nano-scale bactericide.

[0018] In several implementation schemes, the weight ratio of organic thickener to inorganic thickener is 1:2. It can also be set to 1:1, 1:1.5, 1:2.5, or 1:3 as needed, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0019] Optionally, the organic thickener is selected from one or more of xanthan gum, guar gum, and sodium carboxymethyl cellulose;

[0020] The inorganic thickener is selected from one or more of magnesium aluminum silicate, bentonite, and silica.

[0021] By adopting the above technical solutions, organic and inorganic thickeners are optimized, facilitating their selection. Furthermore, the synergistic effect of organic and inorganic thickeners enhances the stability and dispersibility of the nano-scale bactericide, thus improving its effectiveness.

[0022] Optionally, the preservative is selected from one or more of methylisothiazolinone, chloromethylisothiazolinone, sodium benzoate, and potassium sorbate;

[0023] The antifreeze is selected from one or more of ethylene glycol, propylene glycol, glycerol, and sorbitol.

[0024] By adopting the above technical solutions, the preservatives and antifreeze are optimized, facilitating their selection. Furthermore, the preservatives prevent the nano-scale bactericides from deteriorating, extending their shelf life. The antifreeze prevents the nano-scale bactericides from freezing at low temperatures, ensuring their good performance under low-temperature conditions.

[0025] Optionally, 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.

[0026] By adopting the above technical solution, the selection of silicone defoamers is facilitated. Furthermore, silicone defoamers can reduce the surface tension of foam, causing it to break down rapidly and eliminating foam generated during preparation and use, thus contributing to improved stability and quality of nanoscale bactericides.

[0027] Optionally, the flutriafol technical material contains a flutriafol mass concentration ≥95% and an acetone mass concentration ≤0.5%.

[0028] By adopting the above technical solution, the flutriafol content in the flutriafol technical material is limited, ensuring a stable source of flutriafol technical material and a stable content of active ingredients in the nano-scale fungicide, thus ensuring the efficacy and effectiveness of the nano-scale fungicide.

[0029] Secondly, this application provides a method for preparing a nano-scale bactericide containing fluopyram, which adopts the following technical solution:

[0030] A method for preparing a nanoscale fungicide containing fluocinolone acetonide, comprising the following steps:

[0031] 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.

[0032] By adopting the above technical solution, not only is it convenient to prepare nano-sized bactericides, but the raw materials are also fully mixed, ensuring the stability and quality of nano-sized bactericides.

[0033] In summary, this application has at least the following beneficial effects:

[0034] 1. The flutriafol-containing nano-scale bactericide of this application, through the synergistic effect between raw materials, achieves a flutriafol suspension rate >96%, a residue content <3% after pouring, a residue content <0.2% after washing, qualified low-temperature stability, and qualified heat storage stability. It has the characteristics of high flutriafol suspension rate, easy pouring, easy cleaning, and good storage stability.

[0035] 2. The flutriafol-containing nano-scale fungicide of this application uses flutriafol as the active ingredient and utilizes the synergistic effect between tripeptide-1 derivative and 1,3-dimethyl-2-imidazolinone. This not only helps the dispersion of the active ingredient but also increases its wetting ability and affinity to leaves. It acts on the leaf surface, forming delivery channels and accelerating the penetration of the active ingredient, allowing flutriafol to be fully absorbed and exert its efficacy, thus improving field control. Furthermore, the field control efficacy is >90% 14 days after spraying, demonstrating advantages of good control effect and high efficacy, meeting market demand. Detailed Implementation

[0036] The present application will be further described in detail below with reference to the embodiments.

[0037] Preparation Example

[0038] Preparation Example 1

[0039] A tripeptide-1 derivative, prepared by the following method:

[0040] 100 g of tripeptide-1 was added to 1000 g of ethanol at a rotation speed of 500 r / min and stirred for 5 min. Then 38 g of ethyl oleate was added and stirred for 20 h. Afterward, the tripeptide-1 derivative was obtained by vacuum distillation.

[0041] Preparation Example 2

[0042] A tripeptide-1 derivative, which differs from Preparation Example 1 in that the amount of ethyl oleate added is different, with the amount of ethyl oleate added being 30g.

[0043] Preparation Example 3

[0044] A tripeptide-1 derivative, which differs from Preparation Example 1 in that the amount of ethyl oleate added is different, with the amount of ethyl oleate added being 40g. Example

[0045] Table 1. Amount of each raw material used in nano-scale bactericides (unit: ×10g)

[0046] .

[0047] Example 1

[0048] A nanoscale bactericide containing fluopyram is described in Table 1, and its raw materials and proportions are shown in Table 1.

[0049] The flutriafol technical material contained 97% flutriafol by mass and 0.2% acetone by mass; sodium lauryl ether sulfate was selected from Jinan Century Tongda Chemical Co., Ltd.; sodium polyphosphate was selected from sodium polycarboxylate HT-5040; the preservative was selected from methylisothiazolinone; the antifreeze was selected from ethylene glycol; the silicone defoamer was selected from silicone defoamer AFE-7610; and the tripeptide-1 derivative was prepared using the method described in Preparation Example 1.

[0050] The thickener is selected from two types: organic thickener and inorganic thickener, and the weight ratio of organic thickener to inorganic thickener is 1:2. The organic thickener is xanthan gum, which is instant xanthan gum and is selected from Jiangsu Aofu Biotechnology Co., Ltd. The inorganic thickener is magnesium aluminum silicate.

[0051] A method for preparing a nanoscale fungicide containing fluopyram includes the following steps:

[0052] Fluticasone technical, sodium lauryl polyoxyethylene ether sulfate, sodium polyphosphate, antifreeze, thickener, and preservative were added to water and stirred for 10 minutes. Then, the mixture was ground for 8 hours at 2500 rpm and 15°C. Afterward, a tripeptide-1 derivative, 1,3-dimethyl-2-imidazolinone, and an organic defoamer were added, and the mixture was stirred for 30 minutes to obtain a nano-sized bactericide.

[0053] Example 2

[0054] A nano-scale fungicide containing fluopyram is different from that in Example 1 in that the raw material ratio of the nano-scale fungicide is different, and the raw material ratio of the nano-scale fungicide is shown in Table 1.

[0055] Example 3

[0056] A nano-scale fungicide containing fluopyram is different from that in Example 1 in that the raw material ratio of the nano-scale fungicide is different, and the raw material ratio of the nano-scale fungicide is shown in Table 1.

[0057] Example 4

[0058] A nano-scale fungicide containing fluopyram is different from that in Example 1 in that the raw material ratio of the nano-scale fungicide is different, and the raw material ratio of the nano-scale fungicide is shown in Table 1.

[0059] Example 5

[0060] A nano-scale fungicide containing fluopyram is different from that in Example 1 in that the raw material ratio of the nano-scale fungicide is different, and the raw material ratio of the nano-scale fungicide is shown in Table 1.

[0061] Example 6

[0062] A nanoscale fungicide containing fluocinolone sulfadiazine differs from Example 3 in that the source of the tripeptide-1 derivative in the raw materials of the nanoscale fungicide is different, and the tripeptide-1 derivative is prepared by the method of Preparation Example 2.

[0063] Example 7

[0064] A nanoscale fungicide containing flucyclopyrazole differs from Example 3 in that the source of the tripeptide-1 derivative in the raw materials of the nanoscale fungicide is different, and the tripeptide-1 derivative is prepared by the method of Example 3.

[0065] Comparative Example

[0066] Comparative Example 1

[0067] A nanoscale fungicide containing flutriafol, which uses commercially available 12.5% ​​flutriafol suspension and is selected from Jiangsu Gengyun Chemical Co., Ltd.

[0068] Comparative Example 2

[0069] A nano-scale bactericide containing fluocinolone sulfadiazine differs from Example 3 in that, in the raw materials of the nano-scale bactericide, an equal amount of water is used to replace the tripeptide-1 derivative and 1,3-dimethyl-2-imidazolinone.

[0070] Comparative Example 3

[0071] A nano-scale fungicide containing fluocinolone differs from Example 3 in that an equal amount of 1,3-dimethyl-2-imidazolinone is used to replace the tripeptide-1 derivative in the raw materials of the nano-scale fungicide.

[0072] Comparative Example 4

[0073] A nano-scale fungicide containing fluocinolone differs from Example 3 in that an equal amount of tripeptide-1 derivative is used to replace 1,3-dimethyl-2-imidazolinone in the raw materials of the nano-scale fungicide.

[0074] Comparative Example 5

[0075] A nano-scale bactericide containing fluocinolone acetonide differs from Example 3 in that an equal amount of tripeptide-1 derivative is used instead of tripeptide-1 in the raw materials of the nano-scale bactericide.

[0076] Comparative Example 6

[0077] A nano-scale bactericide containing fluocinolone ether differs from Example 3 in that an equal amount of ethyl oleate is used to replace the tripeptide-1 derivative in the raw materials of the nano-scale bactericide.

[0078] Performance testing

[0079] (1)Take the nano-scale bactericides obtained in Examples 1-7 and Comparative Examples 1-6 as samples respectively, and conduct the following performance tests on the nano-scale bactericides. The test results are shown in Table 2.

[0080] Among them, according to GB / T14825-2006 "Determination Method for Suspension Rate of Pesticides", the suspension rate of epoxiconazole in the nano-scale bactericide was detected.

[0081] According to GB / T31737-2015 "Determination Method for Pourability of Pesticides", the residue content after pouring and the residue content after washing of the nano-scale bactericide were detected.

[0082] The low-temperature stability was tested by the following method: at a temperature of 2°C, the nano-scale bactericide was allowed to stand for 14 days. If no crystallization occurred and no stratification was observed, it was considered qualified; otherwise, it was unqualified.

[0083] The thermal storage stability was tested by the following method: at a temperature of 54°C, the nano-scale bactericide was allowed to stand for 14 days. If no crystallization occurred and no stratification was observed, it was considered qualified; otherwise, it was unqualified.

[0084] The field control effect was tested by the following method: Rice was pre-planted in the experimental field, and the rice variety was 19xiang rice. The control object in the experimental field was false smut of rice. The nano-scale bactericide was applied to the paddy field to control false smut of rice. The application rate of the nano-scale bactericide was 45 mL / mu, and the nano-scale bactericide was diluted 1000 times with water and then sprayed. And it was sprayed once 7 days before the occurrence of false smut of rice, and sprayed again after an interval of 10 days, that is, sprayed twice in total during the growth period of rice. Sampling was carried out at fixed points 7 days and 14 days after the end of the two spray applications, and the field control effect was calculated. At the same time, a blank control group was set up. In the blank control group, water was used to replace the nano-scale bactericide.

[0085] False smut of rice is divided into 5 grades, and the grading standard is as follows:

[0086] Grade 0: No disease spots, completely healthy;

[0087] Grade 1: The disease spot area accounts for ≤ 5% of the total leaf area;

[0088] Grade 2: The disease spot area accounts for 6-25% of the total leaf area;

[0089] Grade 3: The disease spot area accounts for 26-50% of the total leaf area;

[0090] Grade 4: The disease spot area accounts for > 50% of the total leaf area.

[0091] Disease index / (%) = (Σ number of diseased leaves at each level × corresponding disease level) / (total number of leaves surveyed × highest disease level) × 100%.

[0092] Field control effect (%) = (disease index of blank control area - disease index of sprayed area) / disease index of blank control area × 100%.

[0093] Table 2 Test Results

[0094]

[0095] As shown in Table 2, the nano-scale fungicide of this application exhibits a flutriafol suspension rate >96%, residue content after pouring <3%, residue content after washing <0.2%, sustained foaming volume <20mL, and satisfactory low-temperature and thermal storage stability. It possesses the characteristics of high flutriafol suspension rate, easy pouring, easy washing, and good storage stability. Furthermore, when applied to control rice false smut in rice, the field control efficacy is >73% after 7 days of spraying and >90% after 14 days, demonstrating excellent control effect and high efficacy, meeting market demand.

[0096] Example 3 was compared with Comparative Example 1. Comparative Example 1 used a commercially available 12.5% ​​flutriafol suspension concentrate; Example 3 used the nano-scale fungicide of this application. It can be seen that the commercially available 12.5% ​​flutriafol suspension concentrate is less effective in controlling rice false smut than the nano-scale fungicide of this application. This may be because the nano-scale fungicide of this application has a high flutriafol suspension rate and good stability, enabling flutriafol to fully exert its efficacy.

[0097] Comparative Examples 2-4 and Example 3 were compared. In Comparative Example 3, compared to Comparative Example 2, 1,3-dimethyl-2-imidazolinone was added to the raw materials of the nano-scale fungicide. In Comparative Example 4, compared to Comparative Example 2, a tripeptide-1 derivative was added to the raw materials of the nano-scale fungicide. In Example 3, compared to Comparative Example 2, both 1,3-dimethyl-2-imidazolinone and a tripeptide-1 derivative were added to the raw materials of the nano-scale fungicide. This demonstrates that simultaneously adding 1,3-dimethyl-2-imidazolinone and a tripeptide-1 derivative to the raw materials, and utilizing their synergistic effect, significantly improves the field control effect and enhances the efficacy and application effect of the nano-scale fungicide.

[0098] Comparative Examples 5-6 and Example 3 were compared. In Comparative Example 5, tripeptide-1 was added to the raw material of the nano-scale fungicide; in Comparative Example 6, ethyl oleate was added to the raw material of the nano-scale fungicide; and in Example 3, a tripeptide-1 derivative was added to the raw material of the nano-scale fungicide. This demonstrates that grafting ethyl oleate onto tripeptide-1 using the reaction between tripeptide-1 and ethyl oleate effectively increases the compatibility between ethyl oleate and the raw material, improves thermal storage stability, and significantly enhances the field control effect of the nano-scale fungicide.

[0099] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A nanoscale fungicide containing fluocinolone acetonide, characterized in that: It is 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; The thickener is selected from two types: organic thickener and inorganic thickener, and the weight ratio of organic thickener to inorganic thickener is 1:2; the organic thickener is selected from xanthan gum; the inorganic thickener is selected from magnesium aluminum silicate. The tripeptide-1 derivative was prepared by the following method: organic solvent and tripeptide-1 were mixed, ethyl oleate was added, the mixture was stirred for 18-22 h, and the tripeptide-1 derivative was obtained by vacuum distillation. The weight ratio of tripeptide-1 to ethyl oleate is 10:(3-4); the organic solvent is ethanol.

2. 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.

3. 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.

4. 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%.

5. A method for preparing a nanoscale fungicide containing fluopyram as described in any one of claims 1-4, 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.

Images