Oil-based preparation for controlling thrips pests, preparation process and application thereof

Abstract

This invention provides an oil-based formulation for controlling thrips pests, the active ingredients of which are bromocyanamide and insecticidal ring, with a mass ratio of 1:(8-11). The oil-based formulation provided by this invention has stable physicochemical properties, high suspension rate, and excellent storage stability. This invention takes into account the characteristics of the active ingredient, the overall coordination of the formulation, and the characteristics of the pests, and solves the problem of active ingredient resistance to a certain extent through physical means. In solving the problem of active ingredient resistance, this invention not only improves efficacy but also takes into account production process costs and time, and has industrial-grade production conditions.

Description

Technical Field

[0001] This invention relates to the field of pesticide technology, and in particular to an oil-based formulation for controlling thrips pests, its preparation process, and its application. Background Technology

[0002] Thrips are a general term for insects belonging to the order Thysanoptera. Larvae are white, yellow, or orange, while adults are yellow, brown, or black; they feed on plant sap or fungi. They are tiny, ranging from 0.5 to 2 mm in length, rarely exceeding 7 mm.

[0003] Thripidae, belonging to the superfamily Thripoidea of ​​the order Thysanoptera, comprises over 2,000 species in 276 genera worldwide. It includes four subfamilies: Panchaetothripinae, Dendrothripinae, Sericothripinae, and Thripinae. These insects are widely distributed globally, exhibiting a complex diet that includes herbivorous, fungivorous, and predatory feeding habits, with herbivorous feeding accounting for more than half. They are a significant economic pest.

[0004] Cyantraniliprole was the first broad-spectrum diamide insecticide, effective against not only chewing insects but also piercing-sucking insects such as aphids and planthoppers (Umetsu and Shira 2020). These diamide insecticides have quickly become the preferred choice for pest control due to their broad spectrum, safety, and low likelihood of cross-resistance. Cyantraniliprole is currently registered for use in several countries and is widely applied to various crops for the control of a variety of pests, including aphids, beet armyworm (Spodoptera exigua Hübner), and whitefly (Bemisia tabaci Gennadius). Cyantraniliprole targets the ryanodine receptor (RyR) in insects, which regulates the calcium levels in insects. 2+ The release of [certain substances] affects the normal contraction of the insect's muscles. Bromhexidine binds to ryanodine receptors within the insect, causing it to continuously release Ca2+. 2+ During this process, the insect's muscles remain in an abnormal contracted state until they deplete their calcium stores. 2+ Eventually, the muscles become paralyzed and unable to function normally, which restricts the insect's behavior and activity, causing it to quickly stop feeding and eventually die.

[0005] It is worth noting that resistance to cyanamide develops rapidly. The 2021 National Agricultural Pest Resistance Monitoring Report issued by the National Agricultural Technology Extension Center shows that whitefly populations in some parts of my country have developed moderate to high levels of resistance to cyanamide, with whitefly eggs exhibiting resistance multiples of 11 to 1,002 times.

[0006] In response to this phenomenon, the present invention provides an oil-based formulation containing bromocyanamide, which can solve the resistance problem of bromocyanamide to a certain extent. Summary of the Invention

[0007] This invention provides an oil-based formulation for controlling thrips pests, the active ingredients of which are bromocyanamide and chlorpyrifos, and the mass ratio of the two is 1:(8-11).

[0008] In one embodiment of the present invention, the active ingredients of the oil-based formulation are bromocyanamide and chlorpyrifos, and the mass ratio of the two is 1:9.

[0009] In one embodiment of the present invention, the oil-based formulation is one of emulsifiable concentrate, oil suspension, or oil formulation.

[0010] In one embodiment of the present invention, the oil-based formulation uses ethylenediaminetetraacetic acid as a synergistic agent.

[0011] In one embodiment of the present invention, when the oil-based formulation is an oil suspension, its mass percentage composition is: 20-60% active ingredient, 1-2% dispersant, 10-25% emulsifier, 0.2-5% thickener, 0.1-1% synergist, and the balance being a dispersion medium.

[0012] In one embodiment of the present invention, when the synergist is ethylenediaminetetraacetic acid, the emulsifier contains anionic surfactant.

[0013] In one embodiment of the present invention, the dispersant comprises a block copolymer dispersant.

[0014] In one embodiment of the present invention, the dispersion medium comprises methyl oleate and / or a polar solvent.

[0015] The second aspect of the present invention provides an oil-based formulation for controlling thrips pests, applicable to rice thrips, western flower thrips, melon thrips, onion thrips, ginger thrips and mango thrips.

[0016] The third aspect of this invention provides an oil-based formulation for controlling thrips pests, the preparation process of which is as follows: the required active ingredient, synergistic agent and dispersion medium are accurately weighed according to mass fraction, stirred evenly with a magnetic stirrer, and the remaining synergistic agent is weighed and put into a sand mill for sand milling for 1 hour. The uniform slurry is then transferred to a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling, samples are taken for testing of particle size, suspension rate and other indicators. After passing the test, the sample is filtered and filled.

[0017] Beneficial effects

[0018] 1. The oil-based formulation provided by this invention has stable physicochemical properties, high suspension rate, and excellent storage stability;

[0019] 2. This invention takes into account the characteristics of the active ingredient, the overall coordination of the formulation, and the characteristics of pests, and solves the problem of resistance to the active ingredient to a certain extent through physical means;

[0020] 3. In addressing the problem of drug resistance, this invention not only improves efficacy but also takes into account production process costs and time, and possesses industrial-grade production conditions. Detailed Implementation

[0021] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] The first aspect of this invention improves an oil-based formulation for controlling thrips pests, the active ingredients of which are bromocyanamide and insecticidal ring, and the mass ratio of the two is 1:(8-11).

[0023] Oil-based formulations

[0024] Oil-based formulations use oily solvents as dispersion media and can be any type of oil-based formulation in the art.

[0025] Considering the pharmacological properties of the original drug of the present invention, the oil-based formulation of the present invention is preferably one of emulsifiable concentrate, oil suspension, or oil formulation.

[0026] Raw material

[0027] The active ingredients in this invention are cyantraniliprole and chlorantraniliprole. Cyantraniliprole is the first broad-spectrum diamide insecticide, effective not only against chewing insects but also against piercing-sucking insects such as aphids and planthoppers. These diamide insecticides have quickly become the preferred choice for pest control due to their broad-spectrum, safe, and low-risk cross-resistance properties. Cyantraniliprole is currently registered for use in several countries and is widely applied to various crops for the control of a variety of pests, including aphids, beet armyworms, and whiteflies. Cyantraniliprole targets insect ryanodine receptors, which regulate the calcium levels in insects. 2+ The release of [certain substances] affects the normal contraction of the insect's muscles. Bromhexidine binds to ryanodine receptors within the insect, causing it to continuously release Ca2+. 2+ During this process, the insect's muscles remain in an abnormal contracted state until they deplete their calcium stores. 2+Eventually, the muscles become paralyzed and unable to function normally, which restricts the insect's behavior and activity, causing it to quickly stop feeding and eventually die.

[0028] Although broflanilide has been developed rapidly, some regions in my country have already developed relatively high levels of resistance.

[0029] To address this phenomenon, ethylenediaminetetraacetic acid (EDTA) is added as a synergistic adjuvant to the formulation system of this invention. This is because EDTA provides a variety of polar groups, allowing it to function not only as a dispersant in the system, improving the overall suspension rate, but also, the inventors have discovered that adding EDTA to oil-based systems can enhance the insecticidal effect of the compound system against diamides, especially systemic pesticides like broflanilide. This may be because broflanilide is a systemic pesticide, and the addition of EDTA can alter cell membrane permeability to some extent, thereby increasing the pesticide's stimulation of pests and accelerating calcium absorption. 2+ This reduces losses and thus increases efficiency.

[0030] Insecticide ring

[0031] Insecticidal ring, also known as Evichal, is N,N-dimethyl-1,2,3-trithionecyclohexane-5-amine and its oxalate, with a molecular weight of 271.26 and a melting point of 125-128°C.

[0032] The insecticidal ring was first synthesized by Sandoz AG of Switzerland in 1970 and commercialized in 1975. Its pure form is a colorless and odorless crystal with a vapor pressure of 5.45 × 10⁻⁶ at 20°C. -4 Pa, hydrolyzes slowly in acidic media and faster in alkaline media. It is sensitive to light and heat, and is relatively stable when stored at room temperature and away from light. It is soluble in water, slightly soluble in acetone and ethanol, and almost insoluble in organic solvents such as ether, chloroform, kerosene, and xylene.

[0033] Insecticidal rings are highly effective against lepidopteran and coleopteran pests, and are commonly used to control pests on rice, vegetables, fruit trees, tea trees, and other crops, including the rice stem borer, rice leaf roller, corn borer, cabbage caterpillar, diamondback moth, cabbage aphid, citrus leafminer, apple leafminer, and pear leafminer. They can also be used to control parasitic nematodes, such as the parasitic rice whitetip nematode, and have some effect on controlling rust and whiteheads in some crops.

[0034] Dosage form

[0035] In this invention, the oil-based formulation is one of emulsifiable concentrate, oil suspension, or oil formulation.

[0036] In a preferred embodiment of the present invention, when the oil-based formulation is an oil suspension, its mass percentage composition is: 20-60% active ingredient, 1-2% dispersant, 10-25% emulsifier, 0.2-5% thickener, 0.1-1% synergist, and the balance being a dispersion medium.

[0037] The active ingredients are bromocyanamide and chlorpyrifos, and the mass ratio of the two is 1:(8-11), more preferably 1:9.

[0038] Dispersant:

[0039] A dispersant is a substance that reduces the aggregation of solid (or liquid) particles in a dispersion system. It is a type of surfactant that, when added to a dispersion system, improves the dispersion performance of solid or liquid materials. Dispersants can be classified into three main categories based on their charge type: anionic dispersants, cationic dispersants, and nonionic dispersants.

[0040] Anionic dispersants mainly include sulfonate dispersants, carboxylate dispersants, phosphate dispersants, and sulfate dispersants. They have good detergency, foaming, dispersing, emulsifying, and wetting properties. They stabilize the dispersion system through electrostatic repulsion and steric hindrance.

[0041] Commonly used cationic dispersants are quaternary ammonium salts. They are adsorbed onto the negatively charged particle surface through the electrostatic interaction of ammonium ions, while the lipophilic segments extend into the medium. The entire system is dispersed through steric hindrance.

[0042] Nonionic surfactants do not dissociate when dissolved in water, and the hydrophilic groups in their molecules are roughly the same as the lipophilic groups in ionic surfactants.

[0043] In this invention, the dispersant is selected from nonionic surfactants, and more preferably from the block copolymer dispersant Zephrym PD 2206.

[0044] Emulsifier:

[0045] Emulsifiers enable immiscible components to form a relatively stable and homogeneous emulsion. They act as a link between the lipophilic and hydrophilic phase molecules. From a mechanistic perspective, emulsifiers function primarily in two ways: first, they form a thick interfacial film at the interface between the two phases, preventing particle aggregation; second, the charge carried by the emulsifier itself, or its ionization, forms a diffuse electric double layer, which, through the repulsion of like charges, inhibits particle aggregation, thus ensuring the stability of the entire system.

[0046] Commonly used emulsifiers include nonionic, anionic, and cationic types. From the perspective of improving emulsification effect, anionic surfactants can be selected; from the perspective of system stability, nonionic surfactants can be selected.

[0047] From the perspective of overall formulation, when using diethylaminetetraacetic acid (DEA) as a synergistic agent in the system of this invention, an anionic emulsifier is selected. This is because the inventors found that while using DEA as a synergistic agent increases efficacy, this is only achieved within a certain high concentration range. When the concentration of DEA increases, the physical properties of the entire system change significantly, and the suspension rate decreases. The inventors found that using anionic emulsifiers can significantly improve the above phenomenon compared to using nonionic or cationic emulsifiers. Further research revealed that selecting emulsifiers with significant steric hindrance yields superior results. Therefore, in this invention, the emulsifier is more preferably an emulsifier containing an aromatic ring. Furthermore, considering the emulsification effect, designing an emulsifier containing a long carbon chain would also yield better results. Therefore, the emulsifier in this invention is selected from emulsifiers containing both aromatic rings and long carbon chains. A further emulsifier can be calcium dodecylbenzenesulfonate, specifically Clariant's Phenylsulfonat-CA.

[0048] As a more preferred embodiment, the emulsifier of the present invention also includes castor oil polyoxyethylene ether, specifically Solvay's ALKAMULS EW / 36.

[0049] Thickener:

[0050] By adding an appropriate amount of thickener, the structural strength of the system can be enhanced, and the viscosity of the system can be adjusted. It exhibits relatively high viscosity under low shear force, and the viscosity decreases accordingly as the shear rate increases, thereby inhibiting the flocculation of solid drug particles caused by gravity and molecular thermal motion during storage. Thickeners can be classified according to their materials, including inorganic, cellulose derivatives, natural products, modified polyacrylates, and polyester derivatives.

[0051] In this invention, the thickener is organobentonite and silica in a ratio of 2:1. The organobentonite was purchased from Suzhou Guojian Huitou Mineral New Materials Co., Ltd. (SK-04); the silica was purchased from Evonik's AEROSIL200.

[0052] Synergistic additives:

[0053] In this invention, the synergist is ethylenediaminetetraacetic acid (EDTA).

[0054] Dispersion medium:

[0055] The dispersion medium of the oil suspension is mainly solvent, such as dimethyl malonate, diethyl malonate, etc.; as an embodiment of the present invention, the dispersion medium includes methyl oleate and / or a polar solvent.

[0056] In a preferred embodiment of the present invention, the dispersion medium is a mixture of methyl oleate and ethylene glycol, and considering the issues of system stability and crystal precipitation, the mass ratio of methyl oleate to ethylene glycol is 13:1.

[0057] A second aspect of the present invention provides an oil-based formulation for controlling thrips pests, applicable to rice thrips, western flower thrips, melon thrips, onion thrips, ginger thrips, and mango thrips.

[0058] The third aspect of the present invention provides an oil-based formulation for controlling thrips pests, the preparation process of which is as follows: the required technical grade, synergistic adjuvant and dispersion medium are accurately weighed by mass fraction, stirred evenly with a magnetic stirrer, and the remaining adjuvant is weighed and put into a sand mill for sand milling for 1 hour. The uniform slurry is then transferred to a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling is completed, samples are taken for testing of particle size, suspension rate and other indicators. After passing the test, the sample is filtered and filled.

[0059] The present invention will be further explained below with reference to specific embodiments.

[0060] Example 1:

[0061] This embodiment provides an oil suspension for controlling thrips pests, the raw materials for which are composed of the following by mass percentage:

[0062]

[0063] The dispersion medium is composed of methyl oleate and ethylene glycol in a mass ratio of 13:1.

[0064] This embodiment provides an oil suspension for controlling thrips pests, the preparation process of which is as follows: The required active ingredient, synergist, and dispersion medium are accurately weighed by mass fraction, stirred evenly with a magnetic stirrer, and the remaining synergist is weighed. The mixture is then fed into a sand mill for 1 hour of sand milling. The uniform slurry is then transferred to a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling, samples are taken for testing of particle size, suspension rate, and other indicators. Once qualified, the mixture is filtered and packaged.

[0065] Example 2:

[0066] This embodiment provides an oil suspension for controlling thrips pests, the raw materials for which are composed of the following by mass percentage:

[0067]

[0068] The dispersion medium is composed of methyl oleate and ethylene glycol in a mass ratio of 13:1.

[0069] This embodiment provides an oil suspension for controlling thrips pests, the preparation process of which is as follows: The required active ingredient, synergist, and dispersion medium are accurately weighed by mass fraction, stirred evenly with a magnetic stirrer, and the remaining synergist is weighed. The mixture is then fed into a sand mill for 1 hour of sand milling. The uniform slurry is then transferred to a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling, samples are taken for testing of particle size, suspension rate, and other indicators. Once qualified, the mixture is filtered and packaged.

[0070] Example 3:

[0071] This embodiment provides an oil suspension for controlling thrips pests, the raw materials for which are composed of the following by mass percentage:

[0072]

[0073] The dispersion medium is composed of methyl oleate and ethylene glycol in a mass ratio of 13:1.

[0074] This embodiment provides an oil suspension for controlling thrips pests, the preparation process of which is as follows: The required active ingredient, synergist, and dispersion medium are accurately weighed by mass fraction, stirred evenly with a magnetic stirrer, and the remaining synergist is weighed. The mixture is then fed into a sand mill for 1 hour of sand milling. The uniform slurry is then transferred to a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling, samples are taken for testing of particle size, suspension rate, and other indicators. Once qualified, the mixture is filtered and packaged.

[0075] Example 4:

[0076] This embodiment provides an oil suspension for controlling thrips pests, the raw materials for which are composed of the following by mass percentage:

[0077]

[0078] The dispersion medium is composed of methyl oleate and ethylene glycol in a mass ratio of 13:1.

[0079] This embodiment provides an oil suspension for controlling thrips pests, the preparation process of which is as follows: The required active ingredient, synergist, and dispersion medium are accurately weighed by mass fraction, stirred evenly with a magnetic stirrer, and the remaining synergist is weighed. The mixture is then fed into a sand mill for 1 hour of sand milling. The uniform slurry is then transferred to a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling, samples are taken for testing of particle size, suspension rate, and other indicators. Once qualified, the mixture is filtered and packaged.

[0080] Example 5:

[0081] This embodiment provides an oil suspension for controlling thrips pests, the raw materials for which are composed of the following by mass percentage:

[0082]

[0083]

[0084] The dispersion medium is methyl oleate.

[0085] This embodiment provides an oil suspension for controlling thrips pests, the preparation process of which is as follows: The required active ingredient, synergist, and dispersion medium are accurately weighed by mass fraction, stirred evenly with a magnetic stirrer, and the remaining synergist is weighed. The mixture is then fed into a sand mill for 1 hour of sand milling. The uniform slurry is then transferred to a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling, samples are taken for testing of particle size, suspension rate, and other indicators. Once qualified, the mixture is filtered and packaged.

[0086] Performance testing:

[0087] Suspension rate: GB / T14825-2006 Determination of Suspension Rate of Pesticides;

[0088] Low-temperature stability: 《GB / T 19137-2003 Method for Determination of Low-Temperature Stability of Pesticides》

[0089] Thermal storage stability: 《GB / T 19136-2003 Test Method for Thermal Storage Stability of Pesticides》

[0090] Dispersibility: Standards such as GB / T32775-2016 Determination of Dispersibility of Pesticides.

[0091] Table 1 Test Results

[0092]

[0093] Field test

[0094] The experimental site was the Wumei Fruit Planting Cooperative in Juntian Village, Huaigao Town, Huaiyin District, Huai'an City, Jiangsu Province. The test crop was scallions, and the target animal was thrips.

[0095] Table 2 Processing Methods

[0096] Processing group Dosage per mu 1 10% bromocyanamide 20 2 Example 2 30 3 Example 1 30 4 Example 4 30 5 50% Insecticidal Ring WP 40 6 CK /

[0097]

[0098]

[0099] Table 3 records the number of insects before pesticide application for each plot of 20 onion stalks.

[0100]

[0101]

[0102] Table 4 records the number of insects one day after pesticide application for each plot of 20 onion stalks.

[0103]

[0104]

[0105] Table 5 shows the number of insects recorded 3 days after pesticide application for each plot of 20 onion stalks.

[0106]

[0107]

[0108] Table 6 records the number of insects 7 days after pesticide application for each plot of 20 onion stalks.

[0109]

[0110]

[0111] Table 7 records the number of insects 10 days after pesticide application for each plot of 20 onion stalks planted.

[0112]

[0113]

[0114] Table 8. Prevention and efficacy data

[0115] Processing group 1d 3d 7d 10d Processing Group 1 77.05083 78.36106 77.64543 75.2505 Processing Group 2 79.51168 83.11124 81.86592 83.08953 Processing Group 3 83.95266 86.06192 86.72333 87.88106 Processing Group 4 82.43519 83.38282 82.5947 83.34468 Processing Group 5 80.20572 81.6171 82.85068 83.60317

[0116] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An oil-based formulation for controlling a thrips pest, characterized by, The raw materials for its preparation are composed of the following components by mass percentage: 2.5% bromocyanamide technical, 22.5% chlorpyrifos technical, 1.5% dispersant, 18% emulsifier, 3% thickener, 3% synergist, and the balance being dispersion medium; The dispersant is a block copolymer dispersant; The emulsifier is calcium dodecylbenzenesulfonate and castor oil polyoxyethylene ether, wherein the mass ratio of the two is 2% and 16%; The thickener is organic bentonite and precipitated silica, wherein the mass ratio of the two is 2% and 1% respectively. The synergistic agent is ethylenediaminetetraacetic acid; The dispersion medium is methyl oleate and ethylene glycol in a mass ratio of 13:

1.

2. The oil-based formulation for controlling thrips pests as described in claim 1 is applicable to rice thrips, western flower thrips, melon thrips, onion thrips, ginger thrips, and mango thrips.

3. A process for the preparation of an oil-based formulation for the control of thrips pests according to claim 1, characterized in that, The preparation process is as follows: Calculate by mass fraction, accurately weigh the required raw material, synergistic agent and dispersion medium, stir evenly with a magnetic stirrer, then weigh the remaining synergistic agent, put it into a sand mill for sand milling for 1 hour, then transfer the uniform slurry into a vertical sand mill for secondary sand milling for 2-3 hours at a speed of 1400 r / min. After sand milling, take a sample for particle size and suspension rate testing, and filter and fill after passing the test.

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