Bromic cyhalothrin and insecticidal ring dispersible oil suspensions, their preparation and use

Abstract

The present application relates to bromocyclen and chlorantraniliprole dispersible oil suspension and its preparation and application, including the following components and weight percentage: bromocyclen 0.1-20%, chlorantraniliprole 0.1-30%, emulsifier 15-25%, dispersant 0.1-5%, thickening agent 0.1-3%, viscosity reducer 0.1-3%, stabilizer 0.1-10%, synergist 0.1-50%, oil phase carrier to 100%. Compared with the prior art, the bromocyclen and chlorantraniliprole dispersible oil suspension of the present application is environmentally friendly, has good stability, high prevention effect and good safety on vegetable phyllotreta striolata, and its preparation method is simple and easy to industrialized mass production. In addition, the screened block polymeric carboxylate compound 100# provides a good viscosity reduction idea and selection for the development of dispersible oil suspension products containing soybean oil and other plant oil systems in the later stage.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of insecticides, and relates to an agricultural insecticidal dispersible oil suspension, in particular to a dispersible oil suspension containing brofenvalerate and insecticidal ring and a preparation method and application thereof. BACKGROUND

[0002] In the aspect of farmland pest control, pesticide compounding is an important means to delay and solve the problem of pest resistance. Pesticide compounding composition with synergistic effect can expand the control spectrum, reduce the dose, improve the biological characteristics, reduce environmental pollution, have good environmental compatibility, and make pests more difficult to develop resistance.

[0003] Phyllotreta vittata Fabr. is the most common one. It mainly harms Brassicaceae such as Chinese cabbage, cabbage and radish, and can also harm solanaceous and cucurbitaceous vegetables and legume vegetables. At present, the main yellow striped flea beetle control agents on the market are mainly nicotine compounds such as acetamiprid, dinotefuran, nitenpyram, nithiazine, pyrethrin such as bifenthrin, lambda-cyhalothrin and deltamethrin, organophosphorus compounds such as malathion, dichlorvos and pyridaben, and their compound products. With the use of these agents for many years, the yellow striped flea beetle has developed high resistance to many of them.

[0004] Brofenvalerate belongs to the class of diamide insecticides, has a wide insecticidal spectrum, good systemicity, and both stomach toxicity and contact toxicity. It can not only control Lepidoptera pests, but also control Hemiptera, Coleoptera and Diptera pests. Insecticidal ring belongs to the class of nereistoxin insecticides, has a wide insecticidal spectrum, has contact toxicity, stomach toxicity, systemicity and fumigation effect, and can kill eggs, and can be used to control Lepidoptera, Coleoptera, Hemiptera and Diptera pests. Because insecticidal ring has been used for many years, many pests have developed resistance to it, and because of its structure, its insecticidal duration is relatively short, generally 7-10 days. Reasonable compounding of brofenvalerate and insecticidal ring can expand the insecticidal spectrum, improve the insecticidal activity of the agent, and prolong the duration. At present, there is no registered product or related report on the compounding of the two for controlling yellow striped flea beetles in vegetables on the market.

[0005] It is found in practice that endosulfan is easily decomposed by visible light, which is the main reason for its short persistence period in the field. The solubility of endosulfan in water reaches 84 g / L, and endosulfan is decomposed by water. Therefore, endosulfan is not suitable for preparing dosage forms containing aqueous systems such as suspensions, emulsions, microemulsions, soluble liquids (liquids) and the like. It can be seen that solving the decomposition problem of endosulfan and improving its chemical stability is one of the technical difficulties in preparing the dispersible oil suspension of chlorantraniliprole and endosulfan. In order to prepare a dispersible oil suspension, the solubility of the oil phase carrier to the active ingredient should be as low as possible. It is found in experiments that many commonly used oil phase carriers have different degrees of solubility to chlorantraniliprole, which easily leads to the growth of particle size during storage, thereby causing the product to be creamed, bottomed or even non-flowing. Therefore, the selection of suitable oil phase carriers is another technical difficulty in preparing the dispersible oil suspension of chlorantraniliprole and endosulfan. At present, there is no related report on the dispersible oil suspension containing chlorantraniliprole and endosulfan and its preparation method.

[0006] Patent document CN103109826A relates to a combination of chlorantraniliprole and nereistoxin insecticide, which includes a combination of chlorantraniliprole and endosulfan. The dosage forms involved include granules, emulsions, microemulsions, suspensions, wettable powders and water dispersible granules, but do not include dispersible oil suspensions. CN104542605A relates to a granule of a sprayable nereistoxin insecticide and chlorantraniliprole, the nereistoxin insecticide being endosulfan. The dosage form involved is granules, but no mention is made of dispersible oil suspensions. SUMMARY

[0007] The purpose of the present application is to provide a dispersible oil suspension containing chlorantraniliprole and endosulfan and its preparation method and application, for solving the problem of poor chemical stability of endosulfan in the dispersible oil suspension containing chlorantraniliprole and endosulfan.

[0008] The purpose of the present application can be achieved by the following technical solutions:

[0009] A dispersible oil suspension containing chlorantraniliprole and endosulfan, comprising the following components and weight percentage:

[0010] Chlorantraniliprole 0.1-20%, endosulfan 0.1-30%, emulsifier 15-25%, dispersant 0.1-5%, thickening agent 0.1-3%, viscosity reducer 0.1-3%, stabilizer 0.1-10%, synergist 0.1-50%, oil phase carrier to 100%.

[0011] Further, the weight ratio of chlorantraniliprole and endosulfan is 1.5:1-1:10.

[0012] Further, the emulsifier is at least one of vegetable oil emulsifier OF-4816, octylphenol polyoxyethylene ether OP-4, OP-10, fatty alcohol polyoxyethylene ether AEO-3, castor oil polyoxyethylene ether EL- or EO-PO block copolymer Ethylan 992;

[0013] The dispersant is surfactant SP-OF3472B;

[0014] The thickening agent is at least one of fumed white carbon black and organic bentonite SK-04;

[0015] The viscosity reducer is block polymer carboxylate compound 100#;

[0016] The oil phase carrier is soybean oil.

[0017] Further, the stabilizer is at least one of 2-hydroxy-4-n-octyloxybenzophenone, organic acid or epoxy soybean oil.

[0018] Further, the mixture of 2-hydroxy-4-n-octyloxybenzophenone and organic acid is referred to as the first stabilizer, and the epoxy soybean oil is referred to as the second stabilizer.

[0019] In the first stabilizer, the mass ratio of 2-hydroxy-4-n-octyloxybenzophenone to organic acid is (1-10):1; the mass ratio of the first stabilizer to the second stabilizer is (4:1) to (1:10).

[0020] The organic acid is at least one of citric acid, glacial acetic acid, dodecylbenzenesulfonic acid or benzoic acid.

[0021] Further, the synergist is α-terpineol and soybean lecithin with a mass ratio of (1-3):1.

[0022] A preparation method of a dispersible oil suspension containing bromocyclen and chlorantraniliprole, comprising the following steps:

[0023] S1: Add emulsifier, dispersant, stabilizer and synergist to the oil phase carrier, and stir to mix uniformly; in this step, the amount of oil phase carrier is 70-90% of the total amount of oil phase carrier

[0024] S2: Add thickening agent and viscosity reducer, and stir to mix uniformly;

[0025] S3: Add bromocyclen and chlorantraniliprole, and shear to mix uniformly;

[0026] S4: Sand mill to D90≤5μm;

[0027] S5: adding the rest of the oil phase carrier, shearing and mixing uniformly to obtain bromocyclenam and chlordecone dispersible oil suspension.

[0028] Further, in step S1, the stirring time is 8-12 min;

[0029] In step S2, the stirring time is 8-12 min;

[0030] In step S3, the shearing time is 15-25 min;

[0031] In step S4, the used sand mill is a three-stage series horizontal sand mill, and the filling medium is 95 zirconium oxide beads; the zirconium oxide beads of the first-stage sand mill are selected to be 1.2-1.4 mm, the zirconium oxide beads of the second-stage sand mill are selected to be 1.0-1.2 mm, and the zirconium oxide beads of the third-stage sand mill are selected to be 0.6-0.8 mm; and the material temperature is ≤30 ℃ during sanding;

[0032] In step S5, the shearing time is 18-22 min.

[0033] An application of a bromocyclenam and chlordecone dispersible oil suspension, comprising using the dispersible oil suspension as a pesticide.

[0034] Further, the dispersible oil suspension is used for preventing and treating vegetable phyllotreta striolata.

[0035] Compared with the prior art, the present application has the following characteristics:

[0036] 1) The bromocyclenam and chlordecone dispersible oil suspension of the present application is environmentally friendly, has good stability, and has good use effect and safety;

[0037] 2) The present application uses alpha-terpineol + soybean lecithin as a synergist for preventing and treating phyllotreta striolata, and the two have a good synergistic effect, and the prepared bromocyclenam and chlordecone dispersible oil suspension has good prevention and treatment effect on vegetable phyllotreta striolata and high safety. Because the weight proportion of the two is large, but the solubility of the effective ingredient is low, the two also play the role of the oil phase carrier;

[0038] 3) The screened block polymeric carboxylate compound 100# provides a good viscosity reduction idea and selection for the development of a dispersible oil suspension product containing soybean oil and other plant oil systems in the later stage. DETAILED DESCRIPTION

[0039] The present application will be described in detail below in combination with specific embodiments.

[0040] A bromocyclenam and chlordecone dispersible oil suspension, comprising the following components and weight percentage:

[0041] Cyantraniliprole 0.1-20%, insecticidal ring agent 0.1-30%, emulsifier 15-25%, dispersing agent 0.1-5%, thickening agent 0.1-3%, viscosity reducer 0.1-3%, stabilizer 0.1-10%, synergist 0.1-50%, oil phase carrier supplement to 100%;

[0042] The insecticidal ring agent includes one or a combination of insecticidal ring or insecticidal ring oxalate.

[0043] The dispersible oil suspension agent contains two active ingredients a and b. Wherein a is cyantraniliprole, CAS registration number [736994-63-1], and the chemical structural formula is:

[0044]

[0045] b is a thiacyclam, CAS registration number [31895-21-3], and the chemical structural formula is:

[0046]

[0047] In addition, b is a thiacyclam oxalate, CAS registration number [31895-22-4], and the chemical structural formula is:

[0048]

[0049] In some specific embodiments, the weight ratio of cyantraniliprole and insecticidal ring is preferably 1.5:1-1:10.

[0050] In some specific embodiments, the sum of the weights of cyantraniliprole and insecticidal ring accounts for 1-40% of the total weight of the pesticide preparation.

[0051] In some specific embodiments, the emulsifier is at least one of vegetable oil emulsifier OF-4816, octylphenol polyoxyethylene ether OP-4, OP-10, fatty alcohol polyoxyethylene ether AEO-3, castor oil polyoxyethylene ether EL- or EO-PO block copolymer Ethylan 992;

[0052] The dispersing agent is a comb-shaped polymer surfactant SP-OF3472B formed by copolymerization of unsaturated monomers;

[0053] The thickening agent is at least one of fumed silica and organic bentonite SK-04;

[0054] The viscosity reducer is a block polymer carboxylate compound 100#;

[0055] The oil phase carrier is soybean oil.

[0056] In some specific embodiments, the stabilizer is at least one of 2-hydroxy-4-n-octyloxybenzophenone, an organic acid or epoxy soybean oil; wherein (2-hydroxy-4-n-octyloxybenzophenone + organic acid) is referred to as a first stabilizer, and epoxy soybean oil is referred to as a second stabilizer;

[0057] The mass amount of the first stabilizer is 0.1-5%, wherein the mass ratio of 2-hydroxy-4-n-octyloxybenzophenone to the organic acid is (1-10):1; and the mass amount of the second stabilizer is 0.1-8%;

[0058] The mass ratio of the first stabilizer to the second stabilizer is preferably (4:1)-(1:10);

[0059] The organic acid is at least one of citric acid, glacial acetic acid, dodecylbenzenesulfonic acid or benzoic acid.

[0060] In some specific embodiments, the synergist is alpha-terpineol and soybean lecithin with a mass ratio of (1-3):1.

[0061] In the prior art, the chemical stability of the insecticidal ring in the dispersible oil suspension agent containing bromocyclen and the insecticidal ring is poor, but the chemical stability of the insecticidal ring in the dispersible oil suspension agent containing bromocyclen and the insecticidal ring obtained by the present application is good, and the decomposition rate of the insecticidal ring is less than 5% according to the thermal storage stability test (54℃, 14d) of GB / T19136-2021, which benefits from:

[0062] 1) According to the physical and chemical properties, the insecticidal ring is easy to degrade when it meets water, all the raw materials selected in the formula components of the present application do not contain water, and the water content is strictly controlled to be less than or equal to 0.5%, and at the same time, the workshop humidity is controlled, and the risk of water brought by cleaning and replacement in the production and packaging steps is strictly controlled, which first creates a good water-free stable environment for the insecticidal ring.

[0063] 2) The stabilizer combination provided by the present application is one of the keys to the stability of the insecticide. The insecticide is easily decomposed by visible light. Therefore, the 2-hydroxy-4-n-octyloxybenzophenone selected in the stabilizer has good ultraviolet light absorption performance, the absorption wavelength range is 280-340 nm, the light stability is good, and it is beneficial to improve the heat storage stability of the insecticide and the anti-photolysis performance in the field use environment. The principle is that the compound can form an intramolecular hydrogen bond ring, strongly and selectively absorb ultraviolet light, and the absorbed high energy will destroy the hydrogen bond and convert it into heat energy. The intramolecular hydrogen bond ring can be repeatedly formed and opened. In addition, it is found through experiments that the chemical stability of the insecticide is different under different pH environments, and the chemical stability is relatively good when the pH is between 5.0-6.0. The present application adjusts the pH of the product to be between 5.0-6.0 by using an organic acid, effectively controls the decomposition rate of the insecticide in the dispersible oil suspension concentrate containing bromocyanthricamide and the insecticide. On the basis of the stabilizer 2-hydroxy-4-n-octyloxybenzophenone + organic acid, a large number of stabilizer combination screening tests are carried out, and it is found that the combination of 2-hydroxy-4-n-octyloxybenzophenone + organic acid + epoxy soybean oil has good stabilizing effect on the insecticide. The possible reason is that the epoxy soybean oil can react with the residual trace amount of water in the formula raw material system or the trace amount of water absorbed during storage to consume water and reduce the adverse effects of residual water on the insecticide. In the water removal function, epichlorohydrin also has this function, but it has a certain solubility for bromocyanthricamide technical material, which is not conducive to the physical stability of the system, and the product will appear creaming and bottoming problems, so it is not selected as a stabilizer; and the epoxy soybean oil has almost no solubility for the active ingredients bromocyanthricamide and the insecticide, which meets the basic condition that the solubility of the active ingredient in the preparation of the dispersible oil suspension concentrate is low. The stabilizer combination of 2-hydroxy-4-n-octyloxybenzophenone + organic acid + epoxy soybean oil plays a synergistic stabilizing role.

[0064] 3) The components in the formula provided by the present application, the oil phase carrier soybean oil and the synergist α-terpineol + soybean lecithin, which account for a large proportion by weight, are important factors for the stability of the insecticide. Through a large number of screening tests, the oil phase carrier soybean oil and the synergist α-terpineol + soybean lecithin provided by the present application have good compatibility with the insecticide and will not cause degradation of the insecticide.

[0065] In order to prepare a dispersible oil suspension concentrate, the solubility of the oil phase carrier for the active ingredient should be as low as possible. Common dispersible oil suspension concentrate oil phase carriers can be divided into several categories such as methyl ester oils, vegetable oils and mineral oils. Through a large number of screening tests, the oil phase carrier screening results are as follows:

[0066] 1) Test method: 1.0 g of the original drug (94% bromocyclen amide original drug) was weighed with a percentage balance, 50.0 g or so of different oil phase carriers (media) were added, the bottle cap was covered, 54°C was heated and shaken for 24 h, then it was cooled (15°C) and placed to take the supernatant for testing.

[0067] 2) The test results are shown in Table 1:

[0068] Table 1

[0069]

[0070]

[0071] 3) From the above screening test results, it can be seen that the smallest solubility of bromocyclen amide is α-terpineol and soybean lecithin, followed by soybean oil, rapeseed oil and corn oil, and other oil phase carriers have different degrees of solubility of bromocyclen amide, so they are not suitable as oil phase carriers for this system. For soybean oil, rapeseed oil and corn oil, firstly, soybean oil is the cheapest in terms of price, secondly, soybean oil is relatively easier to emulsify in terms of emulsification difficulty, and thirdly, the soybean oil system has relatively smaller viscosity. Therefore, soybean oil is selected as the oil phase carrier of the present application. α-terpineol and soybean lecithin are also suitable as oil phase carriers, but they are classified as synergists in the present application.

[0072] The striped flea beetle is highly mobile and jumping, and the main synergistic means is to reduce the dynamic surface tension of the pesticide solution to achieve spreading, penetration and adhesion functions. The synergist described in the present application is a combination of α-terpineol and soybean lecithin, which has good synergistic effect, and the bromocyclen amide and chlorobenzil dispersible oil suspension agent prepared has good prevention and control effect on vegetable striped flea beetles and high safety. This is mainly due to:

[0073] 1) Soybean lecithin mainly increases the adhesion of the pesticide solution, improves the deposition amount of the pesticide solution, reduces the drift amount of the pesticide solution, and increases the efficacy by loading the drug into the target body in the form of liposomes to directly act. Lecithin, also known as phosphatidylcholine, is an ester formed by connecting the phosphate group in phosphatidic acid with choline. It is an amphiphilic molecule composed of a hydrophilic head and a hydrophobic tail, can form a phospholipid bilayer, and is an important component of biological membranes. Lecithin is a component of cell membranes, so it has excellent biocompatibility and safety. The biocompatibility of lecithin can be used to achieve direct penetration without damaging the cuticle, and the safety is high. The drug loading effect of soybean lecithin in this synergistic method also helps to prolong the efficacy of chlorobenzil.

[0074] 2) α-terpineol itself has good wetting, penetrating and adhering ability, and is currently mainly used in the agricultural field for the synergistic effect of killing fruit and vegetable pathogens, and no related reports on the control of Phyllotreta striolata are found. The surface tension of 1% α-terpineol aqueous solution (25℃) is only 33.6 mN / m, which shows that it has excellent surface tension reducing ability. α-terpineol exists in many natural plants, and therefore it also has good biocompatibility and high safety.

[0075] 3) In addition to the emulsifying performance, the selected emulsifiers, i.e. octylphenol polyoxyethylene ether OP-4, OP-10, fatty alcohol polyoxyethylene ether AEO-3, and EO-PO block copolymer Ethylan 992, themselves have good wetting and penetrating performance, and play a good auxiliary role in improving the wetting and penetrating performance of the pesticide.

[0076] 4) The selected oil phase carrier, i.e. soybean oil, is a plant oil, and itself also has certain viscosity and biocompatibility, and plays a good auxiliary role in improving the adhering performance of the pesticide.

[0077] The bromocyclenam and chlordecone dispersible oil suspension prepared in the application has good physical stability, and the dispersant SP-OF3472B is an important factor for the physical stability. The dispersant SP-OF3472B is a high molecular surfactant with a comb structure formed by the copolymerization of unsaturated monomers, the good solvated side chain maintains the compatibility of the dispersed particles and the continuous phase, the high charge density of the side chain increases the ability of multi-point adsorption on the particle surface, and at the same time, the sanding efficiency can be effectively improved, the particle size is reduced, and thus the physical stability of the product is improved. It is found that under the same conditions, the bromocyclenam and chlordecone dispersible oil suspension containing 2% SP-OF3472B is sanded for 1 h, the product particle size D90 is 4.186 μm, the oil separation rate is <5% after heat storage (54℃, 14d), the particle size D90 is 4.993 μm, no bottoming is caused, and the flowability is good; while the control group without SP-OF3472B is sanded for 1 h, the product particle size D90 is 8.942 μm, the oil separation rate is >10% after heat storage (54℃, 14d), the particle size D90 is 14.122 μm, and the bottoming is about 10%.

[0078] Plant oils such as soybean oil, rapeseed oil and corn oil as the oil phase carrier of dispersible oil suspension agent, although the solubility of the active ingredient is very low or even no solubility, but its shortcomings are also obvious, high viscosity, finding effective viscosity reducer is a big problem in the industry. The weight percentage of the oil phase carrier soybean oil and the synergist soybean lecithin is large in the formulation of the dispersible oil suspension agent containing bromocyclen and insecticidal ring prepared by the application, the viscosity of the two is relatively large, which can cause the viscosity of the product to be large, and the pourability index is unqualified. Through a large number of viscosity reduction screening tests, the viscosity reducer obtained by the application is block polymer carboxylate compound 100#. Adding an appropriate amount of block polymer carboxylate compound 100# can effectively reduce the viscosity of the product, ensure that the pourability index of the product is qualified, and also will not cause the product to separate oil due to the reduction of the viscosity in the collocation with the thickening agent of the application. The block polymer carboxylate compound 100# screened by the application also provides a good viscosity reduction idea and selection for the dispersible oil suspension agent product containing soybean oil and other plant oil systems in the future.

[0079] The preparation method of the dispersible oil suspension agent containing bromocyclen and insecticidal ring of the application comprises the following steps:

[0080] S1: The emulsifier, dispersant, stabilizer and synergist are sequentially added to the reaction kettle containing the quantitative carrier oil phase according to the formula proportion, the stirring is turned on and stirred for 8-12 min (preferably 10 min) until the materials are uniformly mixed; wherein the amount of the oil phase carrier in this step is 70-90% of the total amount of the oil phase carrier;

[0081] S2: The thickening agent and the viscosity reducer are sequentially added, and the stirring is continued for 8-12 min (preferably 10 min) until the materials are uniformly mixed;

[0082] S3: Bromocyclen and insecticidal ring are sequentially added, and the shearing is started and sheared for 15-25 min until the materials are uniformly mixed;

[0083] S4: The sheared material is transferred to a horizontal sand mill for sand milling (three-stage series connection, the filling medium is 95 zirconium oxide beads, the zirconium bead selection type of the first-stage sand mill is 1.2-1.4 mm, the zirconium bead selection type of the second-stage sand mill is 1.0-1.2 mm, and the zirconium bead selection type of the third-stage sand mill is 0.6-0.8 mm, and the material temperature is ≤30 ℃ during sand milling), and the particle size control range of the material after sand milling is D90≤5 μm (the detection dispersion medium is the corresponding carrier oil phase);

[0084] S5: The sand-milled material is transferred to a transfer kettle, the remaining amount of the carrier oil phase is added, the shearing is carried out for 18-22 min (preferably 20 min) until the materials are uniformly mixed, and the dispersible oil suspension agent containing bromocyclen and insecticidal ring is obtained through detection and packaging.

[0085] The application of a bromocyclen and chlordecone dispersible oil suspension agent, comprising using the dispersible oil suspension agent to control agricultural pests.

[0086] In some specific embodiments, the dispersible oil suspension agent is used to control vegetable phyllotreta striolata. The application method is generally stem-leaf spraying, and other application techniques used in agriculture can also be used as needed.

[0087] The following examples are implemented on the basis of the above technical solutions of the application, and give detailed implementation modes and specific operation processes, but the protection scope of the application is not limited to the following examples.

[0088] Examples 1-6:

[0089] A preparation method of a bromocyclen and chlordecone dispersible oil suspension agent, comprising the following steps:

[0090] Table 2

[0091]

[0092]

[0093] Table 3

[0094]

[0095]

[0096] S1: The emulsifier, dispersant, stabilizer and synergist are sequentially added to the reaction kettle containing the quantitative carrier oil phase according to the formulation ratio shown in Tables 2-3, the stirring is turned on and stirred for 10 min until the materials are uniformly mixed; wherein the amount of the oil phase carrier in this step is about 80% of the total amount of the oil phase carrier;

[0097] S2: The thickening agent and viscosity reducer are sequentially added, and the stirring is continued for 10 min until the materials are uniformly mixed;

[0098] S3: Bromocyclen and chlordecone are sequentially added, and the shearing is turned on and sheared for about 20 min until the materials are uniformly mixed;

[0099] S4: The sheared material is transferred to a horizontal sand mill for sand milling (three-stage series, the filling medium is 95 zirconia beads, the first-stage sand mill zirconia beads are selected to be 1.2-1.4 mm, the second-stage sand mill zirconia beads are selected to be 1.0-1.2 mm, and the third-stage sand mill zirconia beads are selected to be 0.6-0.8 mm, and the material temperature is ≤30°C during sand milling), and the particle size control range of the material after sand milling is D90≤5 μm (the detection dispersion medium is the corresponding carrier oil phase);

[0100] S5: The sand-milling material was transferred to a transfer kettle, the remaining carrier oil phase was added, and shearing was carried out for 18-22 min (preferably 20 min) until the material was uniformly mixed, and the bromocyclenam and chlorantraniliprole dispersible oil suspension concentrate containing the same was obtained by detection and packaging.

[0101] The bromocyclenam and chlorantraniliprole dispersible oil suspension concentrate obtained was tested for its suspension rate, pourability, wet sieve test, persistent foaming property, low-temperature stability and heat storage stability, and the test methods were as follows:

[0102] Active ingredient content: determined by HPLC method;

[0103] Suspension rate: according to GB / T 14825-2006;

[0104] pH value: according to GB / T 1601-1993;

[0105] Moisture content: according to GB / T 1600-2021;

[0106] Fineness determination method (i.e. wet sieve test): according to GB / T 16150-1995;

[0107] Dispersion stability: according to GB 28155-2011;

[0108] Pourability: according to GB / T 31737-2015;

[0109] Persistent foaming property: according to GB / T 28137-2011;

[0110] Heat storage stability: according to GB / T 19136-2021;

[0111] Low-temperature stability: according to GB / T 19137-2003.

[0112] The test data are shown in Table 4.

[0113] Table 4

[0114]

[0115]

[0116]

[0117] As can be seen from Table 4, the dispersibility, suspensibility, pourability, wet sieve test, persistent foaming property, cold storage stability (0°C, 7d) and heat storage stability (54°C, 14d) of the products prepared in Examples 1-6 are excellent, wherein the products have good heat storage stability, no bottoming and good flowability, and the degradation rates of both brofenvalerate and chlorpyrifos are less than 5%. The preparation processes of Examples 1-6 are simple and easy for industrial production.

[0118] Example 7:

[0119] The insecticidal compositions prepared in Examples 1-6 were used to control Phyllotreta striolata in this example, and the test standard referred to GB / T 17980.18-2000 "Guidelines of Field Test for Pesticides (I) Phyllotreta striolata on Cruciferous Vegetables".

[0120] The 9% brofenvalerate·chlorpyrifos dispersible oil suspension prepared in Example 1 was used to control Phyllotreta striolata, and the effective ingredient dosage was 100, 150 g / ha, the average control effect was 74.22% and 79.17% at 2d after treatment, and the average control effect was 81.43% and 86.46% at 7d after treatment.

[0121] The 20% brofenvalerate·chlorpyrifos dispersible oil suspension prepared in Example 2 was used to control Phyllotreta striolata, and the effective ingredient dosage was 100, 150 g / ha, the average control effect was 74.67% and 79.78% at 2d after treatment, and the average control effect was 82.04% and 87.33% at 7d after treatment.

[0122] The 22% brofenvalerate·chlorpyrifos dispersible oil suspension prepared in Example 3 was used to control Phyllotreta striolata, and the effective ingredient dosage was 100, 150 g / ha, the average control effect was 74.56% and 78.73% at 2d after treatment, and the average control effect was 80.93% and 86.54% at 7d after treatment.

[0123] The 24% brofenvalerate·chlorpyrifos dispersible oil suspension prepared in Example 4 was used to control Phyllotreta striolata, and the effective ingredient dosage was 100, 150 g / ha, the average control effect was 74.94% and 80.03% at 2d after treatment, and the average control effect was 82.44% and 87.57% at 7d after treatment.

[0124] The 30% brofenvalerate·chlorpyrifos dispersible oil suspension prepared in Example 5 was used to control Phyllotreta striolata, and the effective ingredient dosage was 100, 150 g / ha, the average control effect was 75.33% and 80.98% at 2d after treatment, and the average control effect was 83.24% and 88.18% at 7d after treatment.

[0125] The 40% bromocyclenam + chlordecone dispersible oil suspending agent prepared in Example 6 is used to control Phyllotreta striolata, and the effective component is used in an amount of 100, 150 g / m2, the average control effect is 75.11% and 80.45% at 2 d after treatment, and the average control effect is 82.71% and 87.66% at 7 d after treatment.

[0126] In the experiment, the commercially available 10% bromocyclenam suspending agent (Fumexin (Shanghai) Agricultural Technology Co., Ltd.) is used to control Phyllotreta striolata, and the effective component is used in an amount of 36, 42 g / m2, the average control effect is 67.23% and 71.84% at 2 d after treatment, and the average control effect is 72.66% and 77.49% at 7 d after treatment. The commercially available 50% chlordecone soluble powder (Hunan Hao Hua Chemical Co., Ltd.) is used to control Phyllotreta striolata, and the effective component is used in an amount of 375, 500 g / m2, the average control effect is 68.17% and 72.62% at 2 d after treatment, and the average control effect is 70.35% and 74.83% at 7 d after treatment.

[0127] Compared with the commercially available 10% bromocyclenam suspending agent and 50% chlordecone soluble powder, the dispersible oil suspending agent containing bromocyclenam and chlordecone prepared in the application has obvious improvement in the speed of action (2 d after treatment) and the persistence (7 d after treatment) for controlling Phyllotreta striolata, and the amount of the product used is obviously reduced.

[0128] The dispersible oil suspending agent containing bromocyclenam and chlordecone prepared in the application has good effect for controlling Phyllotreta striolata, and no phytotoxicity is observed during the experiment, and the product is safe to Brassica.

[0129] Example 8:

[0130] This example is used to investigate the influence of the viscosity reducer on the pourability of the dispersible oil suspending agent containing bromocyclenam and chlordecone, and the control experiment used in this example is the same as Example 1, except that the viscosity reducer is not added. The results are shown in Table 5 (the pourability test standard is the same as that in Examples 1-6).

[0131] Table 5

[0132]

[0133] From the above results, it can be seen that the viscosity of the dispersible oil suspending agent containing bromocyclenam and chlordecone is effectively reduced by adding the viscosity reducer of the application, so that the pourability index of the product is qualified (the pourability standard: residual material after pouring ≤5.0%, residual material after washing ≤0.5%).

[0134] Example 9:

[0135] The present example is used to investigate the influence of stabilizers and their compositions on the heat storage property and control effect of the bromocyclen and chlordecone dispersible oil suspension agent product. The respective control experiments compared with Example 3 differ only in that:

[0136] Control group 1: no stabilizer is added;

[0137] Control group 2: the light stabilizer butylated hydroxyanisole is used instead of 2-hydroxy-4-n-octyloxybenzophenone;

[0138] Control group 3: oxalic acid is used instead of the organic acid in the present application;

[0139] The rest is the same as Example 1. The results are shown in Table 6 (the heat storage property test standards are the same as Examples 1-6, and the control effect test standards are the same as Example 7).

[0140] Table 6

[0141]

[0142]

[0143] From the above results, it can be seen that the addition of the stabilizer of the present application can effectively improve the control effect and field persistence of the bromocyclen and chlordecone dispersible oil suspension agent product. The main reason is that the stabilizer combination system effectively controls the degradation of the effective ingredient chlordecone (the heat storage decomposition rate standard is ≤5.0%), thereby improving its chemical stability.

[0144] At the same time, based on Example 3, the light stabilizer butylated hydroxyanisole is used instead of the light stabilizer 2-hydroxy-4-n-octyloxybenzophenone of the present application; or oxalic acid is used instead of the organic acid in the present application, which cannot achieve the good stabilizing effect of 2-hydroxy-4-n-octyloxybenzophenone + organic acid + epoxy soybean oil combination on chlordecone.

[0145] Example 10:

[0146] The present example is used to investigate the influence of viscosity reducing agents on the pouring property of the bromocyclen and chlordecone dispersible oil suspension agent product. The control experiment used compared with Example 1 differs only in that no synergist is added. The results are shown in Table 7 (the control effect test standards are the same as Example 7).

[0147] Table 7

[0148]

[0149]

[0150] From the above results, it can be seen that, compared with no synergist, the addition of the synergist of the present application can effectively improve the control effect of the product of the bromocyclen dispersible oil suspension agent containing bromocyanomide, and the synergistic effect is increased by more than 15%. In addition, under the same dosage conditions, the control effect of the synergist of the present application is better than that of the two single synergists (soybean lecithin and α-terpineol), which shows that soybean lecithin + α-terpineol can play a synergistic effect.

[0151] The above description of the embodiments is for the convenience of the ordinary skilled in the art to understand and use the invention. Those skilled in the art can obviously easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without having to go through creative labor. Therefore, the present application is not limited to the above embodiments, and improvements and modifications made by those skilled in the art according to the disclosure of the present application without departing from the scope of the present application should be within the scope of protection of the present application.

Claims

1. A dispersible oil suspension containing bromocyanamide and cyclophosphamide, characterized in that, Includes the following components and their weight percentages: 0.1-20% bromocyanamide, 0.1-30% cyclic insecticide, 15-25% emulsifier, 0.1-5% dispersant, 0.1-3% thickener, 0.1-3% viscosity reducer, 0.1-10% stabilizer, 0.1-50% synergist, and oil phase carrier to 100%; The insecticidal cyclic reagents include one or a combination of two of insecticidal cyclic or insecticidal oxalate; The stabilizer includes a first stabilizer and a second stabilizer; The first stabilizer is a mixture of 2-hydroxy-4-n-octyloxybenzophenone and organic acids; the second stabilizer is epoxidized soybean oil. In the first stabilizer, the mass ratio of 2-hydroxy-4-n-octyloxybenzophenone to organic acid is (1~10):1; the mass ratio of the first stabilizer to the second stabilizer is (4:1)~(1:10); The organic acid is at least one of citric acid, glacial acetic acid, dodecylbenzenesulfonic acid, or benzoic acid; The synergist is α-terpineol and soybean lecithin in a mass ratio of (1~3):

1.

2. The oil-dispersible suspension containing bromocyanamide and cyclophosphamide according to claim 1, characterized in that, The weight ratio of bromocyanamide to insecticidal ring is 1.5:1 to 1:

10.

3. The oil-dispersible suspension containing bromocyanamide and cyclophosphamide according to claim 1, characterized in that, The emulsifier is at least one of the following: vegetable oil emulsifier OF-4816, octylphenol polyoxyethylene ether OP-4, OP-10, fatty alcohol polyoxyethylene ether AEO-3, castor oil polyoxyethylene ether EL-20, or EO-PO block copolymer Ethylan 992. The dispersant is surfactant SP-OF3472B; The thickener is at least one of fumed silica and organobentonite SK-04; The viscosity reducer is a block polymer carboxylate compound 100#; The oil phase carrier is soybean oil.

4. A method for preparing a dispersible oil suspension containing bromocyanamide and chlorpyrifos as described in any one of claims 1 to 3, characterized in that, Includes the following steps: S1: Add the emulsifier, dispersant, stabilizer, and synergist to the oil phase carrier and mix thoroughly; the amount of oil phase carrier used in this step is 70-90% of the total amount of oil phase carrier. S2: Add thickener and viscosity reducer, and stir until well mixed; S3: Add bromocyanamide and insecticidal ring, and mix thoroughly by shearing; S4: Grind to D90≤5μm; S5: Add the remaining oil phase carrier, shear and mix evenly to obtain a dispersible oil suspension containing bromocyanamide and insecticidal ring.

5. The method for preparing a dispersible oil suspension containing bromocyanamide and chlorpyrifos according to claim 4, characterized in that, In step S1, the stirring time is 8~12 min; In step S2, the stirring time is 8~12 min; In step S3, the cutting time is 15~25 min; In step S4, the grinding mill used is a three-stage series horizontal grinding mill, and the filling medium is 95% zirconia beads. The zirconia beads selected for the first stage grinding mill are 1.2~1.4mm, the zirconia beads selected for the second stage grinding mill are 1.0~1.2mm, and the zirconia beads selected for the third stage grinding mill are 0.6~0.8mm. The material temperature during grinding is ≤30℃. In step S5, the shearing time is 18~22 min.

6. The application of a dispersible oil suspension containing bromocyanamide and chlorpyrifos as described in any one of claims 1 to 3, characterized in that, The dispersible oil suspension is used as an insecticide.

7. The application of the dispersible oil suspension containing bromocyanamide and chlorpyrifos according to claim 6, characterized in that, The dispersible oil suspension is used to control flea beetles on vegetables.

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