A water dispersible granule containing abamectin and chlorantraniliprole and a method for preparing the same

Abstract

The present application relates to a kind of water dispersible granules containing abamectin and chlorantraniliprole and its preparation method, the water dispersible granules include chlorantraniliprole inclusion compound and abamectin.The effective utilization rate of pharmaceutical ingredients of the present application is high, the amount of application is less, and it is friendly to ecological environment.The water dispersible granules prepared in the present application disintegrates fast in water, and is easy to disperse uniformly in water, with good synergistic insecticidal effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of biological pesticides, in particular to a water dispersible granule containing abamectin and chlorantraniliprole and a preparation method thereof. BACKGROUND

[0002] Abamectin, the main active ingredient of which is abamectin B1 and abamectin B2, is a kind of sixteen-membered macrocyclic lactone compound with insecticidal, miticidal and nematicidal activity developed by Japan Kitasato University Dacun Zhi et al. and American Merck Company. It is a secondary metabolite produced by Streptomyces avermitilis and mainly exists in the mycelium of Streptomyces avermitilis. Chlorantraniliprole is a kind of insecticide developed by Dupont Company, which belongs to ryanodine receptor activator. It can be used for preventing and treating pests such as Lepidoptera, Diptera, Coleoptera and Isoptera on fruit trees, vegetables, cotton, sugarcane, rice, wheat, corn and other crops.

[0003] At present, since the target points of abamectin and chlorantraniliprole are different, they can coordinate, promote and make up for each other in insecticidal mechanism, so as to kill pests in multiple mechanisms. Therefore, they have been made into a compound preparation for application. For example, the patent application CN103651420A discloses a suspension concentrate containing abamectin and chlorantraniliprole and a preparation method thereof. However, the inventors of the present application found that there are many problems in the insecticidal effect verification, such as easy settlement, stratification and caking after long time storage, difficult to resuspend by using conventional methods, unreasonable proportion of effective components, difficult to achieve synergistic insecticidal effect, and large amount of manpower required for stirring during the use of the suspension concentrate due to the poor solubility of chlorantraniliprole in water. In addition, due to the relatively large proportion of chlorantraniliprole and the much smaller solubility of chlorantraniliprole in water than that of abamectin, it is difficult to select a pesticide preparation for the combination of the two. SUMMARY

[0004] The present application aims at overcoming the defects of the prior art, and provides a water dispersible granule containing abamectin and chlorantraniliprole and a preparation method thereof, which has high effective utilization rate, requires less amount of pesticide, has good effect on killing rice leaf roller and is friendly to ecological environment.

[0005] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0006] The present application provides a water dispersible granule containing abamectin and chlorantraniliprole, which comprises the following raw materials by percentage weight:

[0007]

[0008]

[0009] and the chlorantraniliprole is chlorantraniliprole included by cyclodextrin, the mass ratio of the chlorantraniliprole to chlorantraniliprole-cyclodextrin inclusion is 15-25%, preferably 20%; wherein the active ingredient chlorantraniliprole accounts for 1-5% of the total mass of the water dispersible granules of abamectin and chlorantraniliprole; the cyclodextrin is preferably β-cyclodextrin;

[0010] Further, the wetting agent of the present application uses one or both of Morwet EFW and modified sodium lignosulfonate.

[0011] Further, the disintegrating agent of the present application is selected from urea;

[0012] Further, the filler of the present application uses one or more of organic soil, light calcium carbonate, white carbon black, talcum powder, anhydrous sodium sulfate, and corn starch.

[0013] Further, a water dispersible granule containing abamectin and chlorantraniliprole comprises the following ingredients in percentage by weight:

[0014]

[0015] Preferably, the preparation method of the chlorantraniliprole included by cyclodextrin of the present application comprises the following steps:

[0016] The chlorantraniliprole is dissolved in an organic solvent, and the obtained chlorantraniliprole solution is added dropwise to a saturated aqueous solution of cyclodextrin at a temperature of 40-60°C; continue stirring at a temperature of 40-60°C for 1-3 hours, cool to 10°C and stir for 0.5-1.5 hours, filter, and dry; preferably the organic solvent is selected from one or more of water-miscible organic solvents, preferably methanol, ethanol, and acetone.

[0017] Preferably, the mass ratio of abamectin to chlorantraniliprole in the water dispersible granule of abamectin and chlorantraniliprole of the present application is 1:10-30, based on chlorantraniliprole.

[0018] Further, the present application also provides the use of the water dispersible granule of abamectin and chlorantraniliprole in the prevention and control of rice leaf roller.

[0019] Further, the present application also provides a preparation method of a water dispersible granule containing abamectin and chlorantraniliprole, comprising the following steps:

[0020] Step 1: weigh the dispersing agent modified starch sulfobutyric acid sodium starch, dispersing agent calcium dodecylbenzenesulfonate, wetting agent, disintegrating agent, and filler according to the proportion, and stir and mix uniformly to obtain a premix;

[0021] Step 2: The premix is crushed by a super micro airflow crusher to a particle size of less than or equal to 4 μm, and the mixture powder is obtained;

[0022] Step 3: Avil is dissolved in ethanol to obtain a saturated solution of avil-ethanol, which is ready for use;

[0023] Step 4: The mixture powder is added with chlorantraniliprole wrapped by cyclodextrin, stirred uniformly, and then water and the saturated solution of avil-ethanol are added, and then extrusion granulation and drying are performed by using a granulator.

[0024] Further, in step 1, the stirring speed is 60 revolutions / min.

[0025] Further, in step 4, the amount of water added is 10%-40% of the weight of the mixture powder, preferably 20%-30%, and most preferably 25%.

[0026] Further, in step 4, the stirring speed is 60 revolutions / min.

[0027] Further, the drying temperature is 80-100℃.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] The present application successfully prepares a water dispersible granule meeting the requirements by screening and optimizing the adjuvant, which is not only environmentally friendly, but also has low disintegration times, low disintegration times, and high dispersibility. Compared with the traditional emulsion formulation, the amount of organic solvent is greatly reduced, the effective utilization rate of the drug is improved, and the amount of drug application is reduced. DETAILED DESCRIPTION

[0030] The present application is further described in detail below in combination with examples.

[0031] In the present application,

[0032] Avil raw drug (B1 content 96.1%): provided by Hebei Xingbai Pharmaceutical Group;

[0033] Chlorantraniliprole raw drug (content 99.0%): purchased from Wuhu Wosheng Biological Technology Co., Ltd.;

[0034] Modified starch sulfobutyric acid starch sodium: purchased from Hangzhou Xinyuan Industry and Trade Co., Ltd.;

[0035] Morwet EFW: purchased from AkzoNobel;

[0036] Urea: purchased from Tianjin Damao Chemical Reagent Factory;

[0037] Corn starch: provided by Hebei Xingbai Pharmaceutical Group Co., Ltd.;

[0038] Sodium sulfate: purchased from Xilong Scientific Co., Ltd.;

[0039] Polycarboxylate TERSPERSE 2500: purchased from Huntsman Polyurethanes (China) Co., Ltd.;

[0040] Other chemical reagents are commercially available products.

[0041] Example 1: Chlorantraniliprole and abamectin indoor toxicity test

[0042] The synergistic effect test of abamectin and chlorantraniliprole on Cnaphalocrocis medinalis Guenee was carried out by using three instar larvae as test objects, and the specific method was as follows:

[0043] (1) Test agents:

[0044] The technical agents were prepared according to the conventional method.

[0045] (2) Test objects:

[0046] The insect sources were collected in the rice field in Hainan Province, and then fed with rice seedlings for two generations indoors. Then, the Cnaphalocrocis medinalis Guenee three instar larvae with normal growth and development, active body and body length of 10-15 mm were selected as the toxicity test insect sources.

[0047] (3) Test method:

[0048] The test agents were dissolved and diluted with acetone to different concentrations, and then diluted with distilled water added with a small amount of surfactant (Tween 80) to 5-7 concentrations. Each concentration was repeated 3 times, and 30 test insects were used. The test insects were gently clamped with tweezers and immersed in the drug solution for 5 s, then taken out and placed on the absorbent paper to let them crawl freely. After drying slightly, they were moved into a beaker with fresh rice leaves and fed at 25℃. After 48 h, the death of the test insects was investigated, the mortality and corrected mortality were calculated, the toxicity regression equation was obtained, and the LC 50 value was calculated, which was in milligrams per liter (mg / L).

[0049] (4) Statistical analysis:

[0050] The co-toxicity coefficient (CTC value) of the compound (M) was calculated according to the following formula (with abamectin as the standard agent, and the toxicity index being 100):

[0051] The toxicity index (TI) of chlorantraniliprole = (LC 50 of abamectin / LC 50 of chlorantraniliprole) x 100;

[0052] Actual toxicity index (ATI) of the compound preparation (M) = LC 50 of chlorantraniliprole 50 / LC

[0053] Theoretical toxicity index (TTI) of the compound preparation (M) = TI of chlorantraniliprole x P + TI of abamectin x P 氯虫苯甲酰胺 阿维菌素

[0054] Co-toxicity coefficient (CTC) of M = (ATI of M / TTI of M) x 100

[0055] In the formula, M is the compound of chlorantraniliprole and abamectin in different proportions; P is the proportion of chlorantraniliprole in the mixture; and P is the proportion of abamectin in the mixture. 氯虫苯甲酰胺 阿维菌素

[0056] The co-toxicity coefficient (CTC) of the compound is greater than or equal to 120, which shows synergistic effect; the CTC is less than or equal to 80, which shows antagonistic effect; and 80 < CTC < 120, which shows additive effect.

[0057] (5) The toxicity determination results of the compound of chlorantraniliprole and abamectin on Cnaphalocrocis medinalis Guenee are shown in Table 1:

[0058]

[0059]

[0060] Example 2: Preparation of chlorantraniliprole encapsulated by cyclodextrin

[0061] Chlorantraniliprole (1 mol, 483 g) was dissolved in 4.83 L of ethanol; and β-cyclodextrin (1.2 mol, 1362 g) was dissolved in distilled water at 50°C to prepare a saturated solution. The ethanol solution of chlorantraniliprole was slowly added to the β-cyclodextrin solution at 50°C under stirring, and the dropping time was not less than 3 hours. After the addition, the solution was continuously stirred at 50°C for 2 hours, and then cooled to 10°C and stirred for 1 hour. Filtration was performed, the filter cake was compacted, washed with 2 times the volume of water for 3 times, washed with 2 times the volume of ethanol for 3 times, and dried to constant weight to obtain 1793 g of loose saturated powder.

[0062] 1 g of the product was taken, dissolved in 100 ml of purified water, and shaken at room temperature for 1 minute. No obvious undissolved substances were observed under naked eye observation. The content of chlorantraniliprole was determined by HPLC (external standard method) under the following chromatographic conditions: C 18 ​​​​Column (150 mm x 4.6 mm, 5 μm), room temperature (25-30 °C), mobile phase methanol-water (70:30), volume flow 1 mL / min, detection wavelength 425 nm, injection volume 10 μL.

[0063] The relative mass ratio of chlorantraniliprole in the inclusion product is about 20.8%.

[0064] Example 3

[0065] A water dispersible granule containing chlorantraniliprole and abamectin comprises the following ingredients by weight percentage:

[0066]

[0067] A preparation method of a water dispersible granule containing chlorantraniliprole and abamectin comprises the following steps:

[0068] The dispersant modified starch sulfobutyric acid starch sodium, dispersant calcium dodecyl benzene sulfonate, wetting agent, disintegrating agent, and filler are weighed in proportion, mixed uniformly at a stirring speed of 60 rpm, and a premix is obtained;

[0069] Step 2: The premix is pulverized by a super micro airflow pulverizer until the particle size is less than or equal to 4 μm, and a mixed material powder is obtained;

[0070] Step 3: Abamectin is dissolved in ethanol to obtain a saturated abamectin ethanol solution, which is ready for use

[0071] Step 4: The mixed material powder is added with chlorantraniliprole inclusion by cyclodextrin, the saturated abamectin ethanol solution, and 25% of the mixed material powder by mass of water, and stirred uniformly at a stirring speed of 60 rpm. Then, the mixture is extruded and granulated by a granulator, and dried at 80-100 °C.

[0072] Example 4

[0073] A water dispersible granule containing chlorantraniliprole and abamectin comprises the following ingredients by weight percentage:

[0074]

[0075] A preparation method of a water dispersible granule containing chlorantraniliprole and abamectin is the same as that of Example 3.

[0076] Example 5

[0077] A water dispersible granule containing chlorantraniliprole and abamectin comprises the following ingredients by weight percentage:

[0078]

[0079] A method for preparing water-dispersible granules containing chlorantraniliprole and abamectin comprises the following steps: the same as in Example 3.

[0080] Comparative Example 1

[0081] A water dispersible granule containing chlorantraniliprole and abamectin, comprising the following raw materials by weight:

[0082]

[0083]

[0084] A method for preparing water-dispersible granules containing chlorantraniliprole and abamectin comprises the following steps:

[0085] Step 1: Weigh the raw materials in proportion, stir and mix them evenly at a speed of 60 rpm to obtain a premix;

[0086] Step 2: crush the premixed material using an ultrafine airflow mill to a particle size of 4 μm or less to obtain a mixed material powder;

[0087] Step 3: Add water to the mixed powder according to 25% of the weight of the mixed powder, stir evenly at a speed of 60 rpm, then use a granulator to extrude granules, and dry at 80-100°C.

[0088] Comparative Example 2

[0089] A commercially available emulsifiable concentrate preparation containing chlorantraniliprole and abamectin, wherein the mass content of abamectin B1 is 0.2% and the mass content of chlorantraniliprole is 4%.

[0090] Effect Example 1: Performance Test

[0091] The water dispersible granules prepared in each example and comparative example were measured for disintegration times, disintegration times, and suspension rates. The results are shown in Table 2.

[0092] Determination of disintegration frequency: Add standard hard water to a 250ml stoppered graduated cylinder, weigh 0.5g of the sample to be tested, pour it 5cm away from the liquid surface, cover the cylinder with the stopper, turn it upside down once / second, and observe how many times it takes for it to dissolve completely.

[0093] Determination of disintegration time: Add 1.0 g of sample to a stoppered graduated cylinder containing 250 mL of standard hard water at 25°C. Shake the cylinder clockwise at 8 rpm, centering on the middle of the cylinder. Record the time it takes for the sample to completely disintegrate.

[0094] Determination of suspension rate: carried out in accordance with T / CCPIA 003-2019 standard.

[0095] Table 2

[0096] Disintegration number Disintegration time min Dispersion % Example 3 2 3 96.2 Example 4 2 4 92.1 Example 5 3 6 89.2 Comparative Example 1 8 16 73.5

[0097] Example 2: Field test

[0098] Select 80 m2 of rice field in the test field of Hebei Xingbai Agricultural Technology Co., Ltd., and plant rice for testing the effect of controlling rice leaf roller. The test field is divided into two groups, and spraying is carried out at the 3rd instar larval stage. The number of insects in each group is counted at 6 pm before spraying, and then the mortality rate of rice leaf roller is observed on the 1st day, the 3rd day and the 7th day after spraying, respectively. The results are shown in Table 3.

[0099] Statistical method: 5-point statistical method is used, 198 rice leaf rollers are investigated in each group, the average of the insect population base of 5-point sampling is calculated as the number of insects in each group;

[0100] Test group: spraying the water dispersible granules prepared in Example 3, the amount of drug used per mu is 20.1 g, and spraying is mixed with 35 kg of water per mu;

[0101] Control group: spraying the emulsifiable concentrate of Comparative Example 2, the amount of drug used per mu is 20.1 g, and spraying is mixed with 35 kg of water per mu;

[0102] Table 3

[0103]

[0104] The above-described embodiments are only preferred embodiments of the present application, and are not exhaustive of the feasible implementations of the present application. Any obvious modifications made by those skilled in the art without departing from the principles and spirit of the present application should be considered to be included in the protection scope of the claims of the present application.

Claims

1. An aqueous dispersible granule of abamectin and chlorantraniliprole, characterized in that Comprise the following components by percentage weight: Abamectin 0.12-0.45%; Beta-cyclodextrin-included chlorantraniliprole, 1-5% by chlorantraniliprole; Dispersant: modified starch sulfobutyric acid sodium starch 3-7%; Dispersant: calcium dodecyl benzene sulfonate 0.5-5%; Wetting agent 1-5%; Disintegrant: 20-35%; Filler balance; And in the beta-cyclodextrin-included chlorantraniliprole, the mass ratio of chlorantraniliprole is 15%-25% of the chlorantraniliprole-cyclodextrin inclusion; The mass ratio of abamectin and chlorantraniliprole in the water dispersible granules of abamectin and chlorantraniliprole is 1:10-30 by chlorantraniliprole; The wetting agent uses Morwet EFW; The disintegrant is selected from urea; The filler uses one or more of anhydrous sodium sulfate and corn starch; The preparation method of the beta-cyclodextrin-included chlorantraniliprole comprises the following steps: Dissolve chlorantraniliprole in an organic solvent, and drop the obtained chlorantraniliprole solution into a saturated aqueous solution of cyclodextrin at a temperature of 40-60℃; continue stirring at a temperature of 40-60℃ for 1-3 hours, cool to 10℃ and stir for 0.5-1.5 hours, filter and dry; the organic solvent is selected from water-miscible organic solvents.

2. The water dispersible granules of abamectin and chlorantraniliprole according to claim 1, characterized in that Comprise the following components by percentage weight: Abamectin 0.2%; Beta-cyclodextrin-included chlorantraniliprole, 4% by chlorantraniliprole; Dispersant: modified starch sulfobutyric acid sodium starch 5%; Dispersant: calcium dodecyl benzene sulfonate 1%; Wetting agent: Morwet EFW 2%; Disintegrant: urea 30%; Filler: corn starch 20%; Filler: anhydrous sodium sulfate balance.

3. Process for the preparation of a water dispersible granule of avermectin and chlorantraniliprole according to any one of claims 1 to 2, characterized in that Comprise the following steps: Step 1: weigh the dispersant modified starch sulfobutyric acid sodium starch, dispersant calcium dodecyl benzene sulfonate, wetting agent, disintegrant, filler according to the proportion, and stir and mix uniformly to obtain a premix; Step 2: use a super micro airflow pulverizer to pulverize the premix to a particle size of less than or equal to 4μm, and discharge to obtain a mixed powder; Step 3: dissolve abamectin in ethanol to obtain a saturated abamectin-ethanol solution for standby; Step 4: add the beta-cyclodextrin-included chlorantraniliprole to the mixed powder, stir uniformly, add water and the saturated abamectin-ethanol solution, and then use a granulator to extrude and granulate, and dry.

4. The method of producing a water dispersible granule of abamectin and chlorantraniliprole according to claim 3, characterized by The amount of water added in step 4 is 10%-40% of the weight of the mixed powder.

5. The method of producing the water dispersible granules of abamectin and chlorantraniliprole according to claim 3, characterized by The stirring speed in step 1 is 60 revolutions / min; the stirring speed in step 4 is 60 revolutions / min; and the drying temperature is 80-100℃.

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