Biological synergistic formula for preventing and treating thrips and application of biological synergistic formula

Abstract

The invention discloses a biological synergistic formula for preventing and treating thrips and application of the biological synergistic formula, and belongs to the technical field of biological prevention and treatment. According to the formula, tolfenpyrad is used as a core active component, synergistic ether, white sugar, a modified photolysis-resistant agent and other components are added, and the control rate of the thrip pests is 90% or above through optimization of the proportion of the tolfenpyrad, the synergistic ether, the white sugar, the modified photolysis-resistant agent and the like. The cerium nitrate doped titanium dioxide composite carrier is creatively adopted to prepare the anti-photolysis agent, and the silane coupling agent KH-550 is matched for surface modification, so that the stability of the active component is still kept at 88.7% after 14 days under the strong light condition. According to the preparation process, a homogeneous oil phase is formed through premixing at 20 DEG C, and nanoscale coating with the particle size D90 smaller than or equal to 5 microns is achieved by combining a high-pressure shearing emulsification system and two-section type high-pressure homogenization treatment. The lasting period of single application of the formula reaches 14-21 days and is prolonged by 2-3 times compared with that of a traditional pesticide, the control cost per hectare is reduced by 20-30%, no phytotoxicity is caused to crops such as tomatoes and rice, the pesticide residue is lower than the international standard, and high efficiency and environment friendliness are achieved.

Description

Technical Field

[0001] The invention belongs to the technical field of biological control, and in particular relates to a biological synergistic formula for controlling thrips and an application thereof. Background Art

[0002] Thrips are a type of agricultural pest with a small body and rapid reproduction. They are widely distributed around the world and pose a threat to a variety of economic crops and horticultural plants. Thrips directly damage the leaves, floral organs, fruits and tender branches of plants through their rasp-sucking mouthparts, causing leaf damage, mottled petals, and deformed fruits, which affects the yield and quality of crops. They can also spread a variety of plant viral diseases, such as Tomato spotted wilt virus (TSWV), further exacerbating their harmfulness. Thrips are particularly harmful to high-value crops such as vegetables, fruit trees and flowers cultivated in protected areas. Therefore, the development of efficient and environmentally friendly thrips control technology has become an important issue that needs to be urgently addressed in modern agriculture. Thrips belong to the order Thysanoptera, with more than 7,400 known species worldwide. The life cycle of thrips includes four stages: egg, nymph, pupa and adult. Both nymphs and adults can feed on plant tissues. Thrips have a strong reproductive capacity and can reproduce multiple generations in a year. The life span of female adults is generally 8-10 days, and the egg stage is only 5-6 days under suitable conditions. In addition, thrips are highly concealed and have a wide host range. They often hide in flowers, on the back of leaves or in the soil, making them difficult to detect and control in a timely manner.

[0003] At present, the control of thrips mainly relies on chemical pesticides such as imidacloprid and avermectin. These chemical control methods can effectively control thrips populations in the short term, but long-term use has brought significant negative effects: Environmental pollution: The extensive use of chemical pesticides has led to the pollution of soil, water sources, and air, causing harm to non-target organisms (such as natural enemy insects and bees) and disrupting the ecological balance. According to research, pesticide residues can also accumulate through the food chain, affecting the stability of the ecosystem. Pest resistance: Due to the fast reproduction rate and frequent generation alternation of thrips, they have developed strong resistance to a variety of chemical pesticides. For example, the resistance of western flower thrips to imidacloprid has reached more than 1000 times, severely weakening the control effect of chemical pesticides. Food safety issues: The accumulation of pesticide residues in agricultural products poses a threat to consumer health, attracting widespread social attention. Given the many drawbacks of chemical pesticides, biological control, as an environmentally friendly and safe alternative method, has gradually received attention. Biological control mainly includes using natural enemy insects (such as predatory mites and parasitic wasps) and microbial agents (such as Beauveria bassiana and Metarhizium anisopliae) to control thrips populations. However, biological control also faces some challenges in practical applications: Unstable effect: The activity of biological control agents is greatly affected by environmental conditions (such as temperature and humidity). For example, under high temperature or low humidity conditions, the insecticidal activity of microbial agents significantly decreases, making it difficult to maintain a stable control effect. Slow action speed: Compared with the rapid insecticidal effect of chemical pesticides, biological control agents usually take a longer time to significantly reduce the density of pests, making it difficult to cope with the explosive damage of thrips. High application cost: The production, transportation, and field release costs of natural enemy insects and microbial agents are relatively high, restricting their popularization and application in large-scale agricultural production.

[0004] To overcome the deficiencies of traditional biological control methods, in recent years, bio-enhanced formulations, as a new type of pest management technology, have received extensive attention. Bio-enhanced formulations aim to improve the activity and stability of biological control agents, enhance their control effect on target pests, and reduce the impact on the environment and non-target organisms by scientifically combining bioactive substances (such as microbial metabolites and plant extracts) with chemical pesticides or adjuvants. However, in the field of thrips control, the research and application of bio-enhanced formulations are still in their infancy, but they have shown good development prospects. For example, research has shown that combining microbial agents with low-dose chemical pesticides can not only significantly improve the control effect but also delay the emergence of pest resistance.

[0005] In summary, as an important agricultural pest, thrips control faces multiple challenges such as chemical pesticide pollution, increased resistance, and unstable biological control effects. The present invention provides an innovative solution for the efficient, safe, and environmentally friendly control of thrips by developing a new type of bio-enhanced formulation, which has important theoretical significance and practical value. Summary of the Invention

[0006] Problems to be Solved

[0007] The persistence of existing formulations is poor, requiring frequent spraying, which increases the labor and cost burden. Existing formulations usually require spraying once every 6 - 7 days to maintain the control effect. This need for frequent application significantly increases the labor intensity and time input of farmers, while also increasing the control cost and reducing the economic benefits. The adaptability of existing technologies to different crops is insufficient, and they fail to effectively address the widespread thrips damage. The performance of existing control methods varies greatly on different crops (such as fruits, vegetables, rice, corn, sorghum), and they do not fully meet the thrips damage requirements of multiple crops, resulting in limited application scope and inability to meet the diverse needs of agricultural production. The proportion of components in existing formulations may be unreasonable, and the synergistic effect is limited, leading to low control efficiency. The proportion of components used in existing formulations (such as 30% imidacloprid, 3% alum, 5% synergistic base, etc.) may not achieve the best synergistic effect, resulting in insufficient synergistic effect and limiting the overall control potential of the formulation, making the control efficiency lower than expected. Through optimizing the formulation components and their proportions, the present invention aims to provide a highly efficient, long-lasting and adaptable bio-enhanced thrips control formulation to overcome the above problems, thereby enhancing the economy, practicability and wide applicability of thrips control.

[0008] Technical Solution

[0009] To solve the above problems, the present invention adopts the following technical solution.

[0010] A bio-enhanced formulation for controlling thrips, in parts by weight, the components are as follows: 30 - 46 parts of tolfenpyrad, 3 - 6 parts of white sugar, 2 - 5 parts of piperonyl butoxide, 2 - 10 parts of dispersant, 3 - 8 parts of wetting agent, 2 - 6 parts of penetrant, 1 - 10 parts of modified photodegradation inhibitor, 0.1 - 0.6 parts of preservative, 1.2 - 3.4 parts of magnesium aluminum silicate, deionized water, making up to 100 parts.

[0011] The synergistic ether is selected from one or more of piperonyl butoxide (CAS No.: 51-03-6), octachlorodipropyl ether (CAS No.: 127-90-2), methoxyphenyl ether (CAS No.: 91-16-7), and pulegone (CAS No.: 494-90-6); the dispersant is selected from one or more of sodium naphthalenesulfonate formaldehyde condensate (CAS No.: 9084-06-4), sodium lignosulfonate (CAS No.: 8061-51-6), and sodium polycarboxylate (CAS No.: 62601-60-9); the wetting agent is selected from one or more of polysorbate 20 (CAS No.: 9005-64-5), alkylnaphthalenesulfonates (CAS No.: 25417-20-3), and sophorolipid (CAS No.: 148409-20-5); the penetrant is selected from one or more of polyether-modified polysiloxane (CAS No.: 67674-67-3), ethyl oleate (CAS No.: 111-62-6), lauryl polyoxyethylene ether (CAS No.: 9002-92-0), and decyl glucoside (CAS No.: 68515-73-1).

[0012] The preparation method of the modified photodegradation inhibitor is as follows: titanium dioxide and a metal salt precursor are mixed at a mass ratio of 1:(0.1-0.5), and a 0.1-1.0 mol / L hydrofluoric acid solution is added. The added mass of the hydrofluoric acid solution is 10 times that of titanium dioxide, and ultrasonic dispersion is carried out for 30-60 min to form a uniform suspension. The metal salt precursor is cerium nitrate; the obtained suspension is transferred to a high-pressure reaction kettle, and hydrothermal reaction is carried out at 120-180 °C for 12-48 h. After the reaction is completed, it is naturally cooled to room temperature, centrifuged at 6000 rpm for 10 min, and after separation, it is washed 3 times with deionized water and anhydrous ethanol in sequence, and dried at 80 °C for 6 h to obtain a metal-doped composite support; the metal-doped composite support and an ethanol solution containing 1-5% by mass of silane coupling agent KH-550 (CAS No.: 919-30-2) are mixed at a solid-liquid mass ratio of 1:10, and stirred and reacted at 60-80 °C for 4-8 h under nitrogen protection to obtain a functional support. Then, 2-hydroxy-4-methoxybenzophenone (CAS No.: 131-57-7) and the functional support are dissolved in acetone at a mass ratio of 1:(0.5-2.0), ultrasonic treatment is carried out for 30 min, and then the solvent is removed by rotary evaporation at 40 °C; the preservative is selected from one or more of sodium benzoate, potassium sorbate, and isothiazolinones (CAS No.: 2682-20-4).

[0013] The biological synergistic formula for controlling thrips, by weight, has the following components: 35-44 parts of tolfenpyrad, 3-6 parts of white sugar, 2-5 parts of piperonyl butoxide, 4-8 parts of dispersant, 3-8 parts of wetting agent, 2-6 parts of penetrant, 4-8 parts of modified photodegradation inhibitor, 0.2-0.6 parts of preservative, 1.5-2.5 parts of magnesium aluminum silicate, and deionized water to make up 100 parts.

[0014] The biological synergistic formula for controlling thrips, by weight, has the following components: 40 parts of tolfenpyrad, 5 parts of white sugar, 4 parts of piperonyl butoxide, 6 parts of dispersant, 5 parts of wetting agent, 4 parts of penetrant, 6 parts of modified photodegradation inhibitor, 0.4 parts of preservative, 2.0 parts of magnesium aluminum silicate, and deionized water to make up 100 parts.

[0015] The CAS number of the tolfenpyrad is 129558-76-5; the white sugar is food-grade sucrose with a purity ≥99.5%, CAS number 57-50-1, and molecular weight 342.30; the CAS number of the magnesium aluminum silicate is 1327-43-1.

[0016] The mixing and treatment method of the biological synergistic formula is as follows: Pretreatment stage: Tolfenpyrad and piperonyl butoxide are premixed at 20°C to form a homogeneous oil phase with a particle size D90≤5μm, and then a modified photodegradation inhibitor is added for nano-scale coating; Main mixing stage: Use a GHS-5000 high-pressure shear emulsification system, and successively add deionized water, dispersant, wetting agent, penetrant, and preservative, with a rotation speed of 1000 rpm, control the system temperature at 35°C, and pH = 6.5-7.5; Post-treatment stage: Add magnesium aluminum silicate and white sugar, stir at low speed and then process through a homogenizer to obtain the product.

[0017] Specifically, the equipment parameters in the pretreatment stage: for the premixing equipment, a magnetic stirring constant temperature reactor (volume 50 - 200L) is used, equipped with: a double-layer 316L stainless steel jacket, through which circulating cooling water is passed to maintain 20°C; the rotation speed is 600 rpm (equipped with a variable frequency control system); for nano-level coating, an MSK-SFM-500D-S high-shear emulsifier is used: the rotor linear velocity is 20.5 m / s, the processing capacity is 500 mL / batch, a 304 stainless steel stator head (pore diameter 20 mm² adjustable), and the time is 45 min. The key equipment in the post-treatment stage: a homogenization treatment system, configured with a two-stage high-pressure homogenizer: the working pressure is 100 MPa, the processing capacity is 5 t / h, the homogenization chamber adopts a Y-shaped diamond microporous structure (pore diameter 75 μm), equipped with a two-stage cooling system (the material outlet temperature ≤ 40°C), and a supporting automatic lubrication device (oil pressure maintained at 0.3 - 0.5 MPa). Auxiliary system configuration, material transportation: a 316L stainless steel screw pump is used (flow rate error ≤ ±2%), temperature control: a plate heat exchanger (heat transfer area 10 m², ΔT ≤ 3°C), automation system: an integrated PLC control module is implemented to achieve: real-time recording of process parameters (temperature, pressure, pH, etc.).

[0018] As described above, the application of the bio-enhanced formulation in the preparation of a medicament for controlling thrips, the dosage form of the medicament is a pharmaceutically acceptable dosage form, the dosage form of the medicament is a suspension, an emulsion or a spray, and the application method of the medicament is spraying or soaking.

[0019] Beneficial effects

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] The control efficiency is significantly improved: through the synergistic effect of tolfenpyrad and piperonyl butoxide, the indoor toxicity test shows that the LC50 value is as low as 0.89 mg / L, which is about 7 - 8 times lower than that of traditional imidacloprid (6.57 mg / L) and abamectin (7.24 mg / L). Comparative analysis shows that after removing piperonyl butoxide or the modified photolysis-resistant agent, the LC50 values rise to 2.15 mg / L and 2.78 mg / L respectively, verifying the synergistic effect of the key components. The breakthrough in photolysis resistance stability: The cerium nitrate-doped titanium dioxide composite carrier combined with the modification of silane coupling agent KH-550 enables the residual amount of the active ingredient to reach 88.7% after 14 days under strong light (340 nm ultraviolet irradiation), which is significantly higher than 51.8% of the unmodified system. The modified photolysis-resistant agent delays photodegradation through nano-level coating, and the effective period is extended to 14 - 21 days, which is 2 - 3 times longer than that of traditional pesticides (6 - 7 days).

[0022] For the modified photodegradation inhibitor, its preparation process realizes the improvement of photodegradation resistance through the triple synergistic effects of metal doping, surface modification, and functional assembly. The specific mechanism is as follows: Lattice reconstruction of cerium-doped titanium dioxide, and the following effects are produced by hydrofluoric acid during ultrasonic dispersion: Surface etching: ions and react with the lattice to form complexes, exposing more highly active crystal planes; Lattice doping: Cerium nitrate dissociates into under hydrothermal conditions at 120 °C, and forms a solid solution by substituting , triggering lattice distortion; Energy band regulation: The redox pair of introduces impurity energy levels in the forbidden band, reducing the band gap from 3.2 eV to 2.8 eV; Silane coupling interface engineering, KH-550 (γ-aminopropyltriethoxysilane) undergoes a stepwise reaction under nitrogen protection: Hydrolysis: Ethoxy groups ( ) hydrolyze in an ethanol solution to form silanols ( ), Condensation: The silanols dehydrate and condense with the surface hydroxyl groups to form bonds, Directed assembly: The amino group ( ) binds to the hydroxyl group of 2-hydroxy-4-methoxybenzophenone through hydrogen bonds. The anchoring mechanism of the ultraviolet absorber is as follows. 2-Hydroxy-4-methoxybenzophenone is loaded in the following ways: Physical adsorption: The benzene ring and the long-chain alkyl group of KH-550 produce stacking; Chemical bonding: The phenolic hydroxyl group forms a hydrogen bond with the amino group; Steric hindrance protection: The modified carrier forms a three-dimensional network structure to restrict the migration of photosensitive molecules. Photodegradation inhibition is achieved through a triple mechanism: Electron trap effect: captures photo-generated electrons, Radical quenching: Benzophenone derivatives convert the excited-state energy into heat through intersystem crossing, Light screening effect: The reflectance is increased to 85% in the wavelength range of 300 - 400 nm. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the transmission electron microscope image of the modified photodegradation inhibitor in Example 5 of the present invention.

[0024] Figure 2 is the actual image of the indoor toxicity test in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] The present invention will be further described below in conjunction with specific embodiments.

[0026] Unless otherwise defined, the technical and scientific terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art to which the present invention belongs. In actual applications, the parts by weight involved in the present invention can be set to kilograms.

[0027] Example 1

[0028] A biological synergistic formulation for controlling thrips, in parts by weight, the components are as follows: 30 parts of tolfenpyrad, 6 parts of white sugar, 2 parts of piperonyl butoxide, 10 parts of dispersant, 3 parts of wetting agent, 6 parts of penetrant, 1 part of modified photolysis-resistant agent, 0.6 part of preservative, 1.2 parts of magnesium aluminum silicate, deionized water, to make up to 100 parts; the piperonyl butoxide is selected from piperonyl butoxide; the dispersant is selected from sodium salt of naphthalene sulfonic acid formaldehyde condensate; the wetting agent is selected from polysorbate 20; the penetrant is selected from polyether-modified polysiloxane; the preparation method of the modified photolysis-resistant agent is as follows: titanium dioxide and metal salt precursor are mixed at a mass ratio of 1:0.1, 1.0 mol / L hydrofluoric acid solution is added, and ultrasonic dispersion is carried out for 30 min to form a uniform suspension, and the metal salt precursor is cerium nitrate; the obtained suspension is transferred to a high-pressure reaction kettle, and hydrothermal reaction is carried out at 120 °C for 48 h. After the reaction is completed, it is naturally cooled to room temperature, and after centrifugal separation, it is washed 3 times with deionized water and absolute ethanol in sequence, and dried at 80 °C for 6 h to obtain a metal-doped composite support; the metal-doped composite support and an ethanol solution containing 1% by mass of silane coupling agent KH-550 are mixed at a solid-liquid mass ratio of 1:10, and stirred and reacted at 60 °C for 8 h under nitrogen protection to obtain a functional support. Then, 2-hydroxy-4-methoxybenzophenone and the functional support are dissolved in acetone at a mass ratio of 1:0.5, and after ultrasonic treatment for 30 min, the solvent is removed by rotary evaporation at 40 °C; the preservative is selected from sodium benzoate. The CAS number of the tolfenpyrad is 129558-76-5; the white sugar is food-grade sucrose with a purity ≥ 99.5%, CAS number 57-50-1, and molecular weight 342.30; the CAS number of the magnesium aluminum silicate is 1327-43-1. The mixing and treatment method of the biological synergistic formulation is as follows: Pretreatment stage: Tolfenpyrad and piperonyl butoxide are premixed at 20 °C to form a homogeneous oil phase, and then the modified photolysis-resistant agent is added for nano-level coating; Main mixing stage: Use a shear emulsifier, and successively add deionized water, dispersant, wetting agent, penetrant and preservative, control the system temperature at 35 °C, pH = 6.5; Post-treatment stage: Add magnesium aluminum silicate and white sugar, stir at low speed and then treat with a homogenizer to obtain the product.

[0029] Example 2

[0030] Biological synergistic formula for controlling thrips, calculated by weight, the components are as follows: 46 parts of tolfenpyrad, 3 parts of white sugar, 5 parts of piperonyl butoxide, 2 parts of dispersant, 8 parts of wetting agent, 2 parts of penetrant, 10 parts of modified anti-photolysis agent, 0.1 part of preservative, 3.4 parts of magnesium aluminum silicate, deionized water, to make up to 100 parts; the piperonyl butoxide is selected from octachlorodipropyl ether; the dispersant is selected from sodium lignosulfonate; the wetting agent is selected from alkylnaphthalene sulfonates; the penetrant is selected from ethyl oleate; the preparation method of the modified anti-photolysis agent is as follows: titanium dioxide and metal salt precursor are mixed at a mass ratio of 1:0.5, 0.1 mol / L hydrofluoric acid solution is added, and ultrasonic dispersion is carried out for 60 min to form a uniform suspension, and the metal salt precursor is cerium nitrate; the obtained suspension is transferred to a high-pressure reaction kettle, and hydrothermal reaction is carried out at 180 °C for 12 h, after the reaction is completed, it is naturally cooled to room temperature, and after centrifugal separation, it is washed 3 times with deionized water and anhydrous ethanol in turn, and dried at 80 °C for 6 h to obtain a metal-doped composite support; the metal-doped composite support and an ethanol solution containing 5% by mass of silane coupling agent KH-550 are mixed at a solid-liquid mass ratio of 1:10, and stirred and reacted at 80 °C for 4 h under nitrogen protection to obtain a functional support, and then 2-hydroxy-4-methoxybenzophenone and the functional support are dissolved in acetone at a mass ratio of 1:2.0, after ultrasonic treatment for 30 min, the solvent is removed by rotary evaporation at 40 °C; the preservative is selected from potassium sorbate. The CAS number of the tolfenpyrad is 129558-76-5; the white sugar is food-grade sucrose with a purity ≥99.5%, CAS number 57-50-1, and molecular weight 342.30; the CAS number of the magnesium aluminum silicate is 1327-43-1. The mixing and treatment method of the biological synergistic formula is as follows: Pretreatment stage: Tolfenpyrad and piperonyl butoxide are premixed at 20 °C to form a homogeneous oil phase, and then the modified anti-photolysis agent is added for nano-coating; Main mixing stage: Use a shear emulsifier, and successively add deionized water, dispersant, wetting agent, penetrant and preservative, control the system temperature at 35 °C, pH = 7; Post-treatment stage: Add magnesium aluminum silicate and white sugar, stir at low speed and then treat with a homogenizer to obtain the product.

[0031] Example 3

[0032] Biological synergistic formulation for controlling thrips, calculated by weight, the components are as follows: 35 parts of tolfenpyrad, 6 parts of white sugar, 2 parts of piperonyl butoxide, 8 parts of dispersant, 3 parts of wetting agent, 6 parts of penetrant, 4 parts of modified anti-photodegradant, 0.6 parts of preservative, 1.5 parts of magnesium aluminum silicate, deionized water, to make up to 100 parts; the piperonyl butoxide is selected from methoxyphenyl ether; the dispersant is selected from sodium polycarboxylate; the wetting agent is selected from sophorolipid; the penetrant is selected from polyoxyethylene lauryl ether; the preparation method of the modified anti-photodegradant is as follows: titanium dioxide and metal salt precursor are mixed at a mass ratio of 1:0.2, 0.8 mol / L hydrofluoric acid solution is added, and ultrasonic dispersion is carried out for 40 min to form a uniform suspension, and the metal salt precursor is cerium nitrate; the obtained suspension is transferred to a high-pressure reaction kettle, and hydrothermal reaction is carried out at 130 °C for 40 h, after the reaction is completed, it is naturally cooled to room temperature, and after centrifugal separation, it is washed 3 times with deionized water and anhydrous ethanol in sequence, and dried at 80 °C for 6 h to obtain a metal-doped composite support; the metal-doped composite support and an ethanol solution containing 1% by mass of silane coupling agent KH-550 are mixed at a solid-liquid mass ratio of 1:10, and stirred and reacted at 65 °C for 5 h under nitrogen protection to obtain a functional support, and then 2-hydroxy-4-methoxybenzophenone and the functional support are dissolved in acetone at a mass ratio of 1:0.8, after ultrasonic treatment for 30 min, the solvent is removed by rotary evaporation at 40 °C; the preservative is selected from isothiazolinones. The CAS number of the tolfenpyrad is 129558-76-5; the white sugar is food-grade sucrose with a purity ≥ 99.5%, CAS number 57-50-1, and molecular weight 342.30; the CAS number of the magnesium aluminum silicate is 1327-43-1. The mixing treatment method of the biological synergistic formulation is as follows: Pretreatment stage: Tolfenpyrad and piperonyl butoxide are pre-mixed at 20 °C to form a homogeneous oil phase, and then the modified anti-photodegradant is added for nano-level coating; Main mixing stage: Use a shear emulsifier, and successively add deionized water, dispersant, wetting agent, penetrant and preservative, control the system temperature at 35 °C, pH = 7.5; Post-treatment stage: Add magnesium aluminum silicate and white sugar, stir at low speed and then treat with a homogenizer to obtain the product.

[0033] Example 4

[0034] A biological synergistic formulation for controlling thrips, in parts by weight, the components are as follows: 44 parts of tolfenpyrad, 3 parts of white sugar, 5 parts of piperonyl butoxide, 4 parts of dispersant, 8 parts of wetting agent, 2 parts of penetrant, 8 parts of modified anti-photodegradant, 0.6 part of preservative, 1.5 parts of magnesium aluminum silicate, deionized water, to make up to 100 parts; the piperonyl butoxide is selected from methoxyphenyl ether; the dispersant is selected from sodium polycarboxylate; the wetting agent is selected from alkylnaphthalene sulfonates; the penetrant is selected from ethyl oleate; the preparation method of the modified anti-photodegradant is as follows: titanium dioxide and a metal salt precursor are mixed in a mass ratio of 1:0.4, and a 0.3 mol / L hydrofluoric acid solution is added, and ultrasonic dispersion is carried out for 50 min to form a uniform suspension, and the metal salt precursor is cerium nitrate; the obtained suspension is transferred to a high-pressure reaction kettle, and hydrothermal reaction is carried out at 170 °C for 18 h, and after the reaction is completed, it is naturally cooled to room temperature, and after centrifugal separation, it is washed 3 times with deionized water and absolute ethanol in sequence, and dried at 80 °C for 6 h to obtain a metal-doped composite support; the metal-doped composite support and an ethanol solution containing 1% by mass of silane coupling agent KH-550 are mixed in a solid-liquid mass ratio of 1:10, and stirred and reacted at 75 °C for 7 h under nitrogen protection to obtain a functional support, and then 2-hydroxy-4-methoxybenzophenone and the functional support are dissolved in acetone in a mass ratio of 1:1.5, and after ultrasonic treatment for 30 min, the solvent is removed by rotary evaporation at 40 °C; the preservative is selected from potassium sorbate. The CAS number of the tolfenpyrad is 129558-76-5; the white sugar is food-grade sucrose with a purity of ≥99.5%, the CAS number is 57-50-1, and the molecular weight is 342.30; the CAS number of the magnesium aluminum silicate is 1327-43-1. The mixing and treatment method of the biological synergistic formulation is as follows: Pretreatment stage: Tolfenpyrad and piperonyl butoxide are premixed at 20 °C to form a homogeneous oil phase, and then the modified anti-photodegradant is added for nano-level coating; Main mixing stage: Use a shear emulsifier, and successively add deionized water, dispersant, wetting agent, penetrant and preservative, and control the system temperature at 35 °C and pH = 7.5; Post-treatment stage: Add magnesium aluminum silicate and white sugar, stir at low speed and then treat with a homogenizer to obtain the product.

[0035] Example 5

[0036] Biological synergistic formula for controlling thrips, in parts by weight, the components are as follows: 40 parts of tolfenpyrad, 5 parts of white sugar, 4 parts of piperonyl butoxide, 6 parts of dispersant, 5 parts of wetting agent, 4 parts of penetrant, 6 parts of modified anti-photolysis agent, 0.4 part of preservative, 2.0 parts of magnesium aluminum silicate, deionized water, to make up to 100 parts; the piperonyl butoxide is selected from methoxyphenyl ether; the dispersant is selected from sodium lignosulfonate; the wetting agent is selected from alkylnaphthalene sulfonates; the penetrant is selected from lauryl alcohol polyoxyethylene ether; the preparation method of the modified anti-photolysis agent is as follows: titanium dioxide and metal salt precursor are mixed at a mass ratio of 1:0.3, 0.5 mol / L hydrofluoric acid solution is added, and ultrasonic dispersion is carried out for 45 min to form a uniform suspension, and the metal salt precursor is cerium nitrate; the obtained suspension is transferred to a high-pressure reaction kettle, and hydrothermal reaction is carried out at 150 °C for 24 h. After the reaction is completed, it is naturally cooled to room temperature, and after centrifugal separation, it is washed 3 times with deionized water and anhydrous ethanol in sequence, and dried at 80 °C for 6 h to obtain a metal-doped composite support; the metal-doped composite support and an ethanol solution containing 3% by mass of silane coupling agent KH-550 are mixed at a solid-liquid mass ratio of 1:10, and stirred and reacted at 70 °C for 6 h under nitrogen protection to obtain a functional support. Then, 2-hydroxy-4-methoxybenzophenone and the functional support are dissolved in acetone at a mass ratio of 1:1, and after ultrasonic treatment for 30 min, the solvent is removed by rotary evaporation at 40 °C. The transmission electron micrograph of the modified anti-photolysis agent is as shown in Figure 1 shown; the preservative is selected from potassium sorbate. The CAS number of tolfenpyrad is 129558-76-5; the white sugar is food-grade sucrose with a purity ≥ 99.5%, CAS number 57-50-1, and molecular weight 342.30; the CAS number of magnesium aluminum silicate is 1327-43-1. The mixing and treatment method of the biological synergistic formula is as follows: Pretreatment stage: Tolfenpyrad and piperonyl butoxide are pre-mixed at 20 °C to form a homogeneous oil phase, and then the modified anti-photolysis agent is added for nano-level coating; Main mixing stage: A shear emulsifier is used, and deionized water, dispersant, wetting agent, penetrant and preservative are added in sequence, and the system temperature is controlled at 35 °C and pH = 7; Post-treatment stage: Magnesium aluminum silicate and white sugar are added, and after low-speed stirring, it is treated by a homogenizer to obtain the product.

[0037] Comparative Examples 1-3

[0038] Comparative Example 1: Commercially available imidacloprid suspension concentrate (50% active ingredient), Hailier "imidacloprid 50% suspension concentrate" (registration number PD20110322).

[0039] Comparative Example 2: Abamectin emulsifiable concentrate (1.8% active ingredient), Nanjing Runjie "1.8% abamectin EC" (registered crop: diamondback moth on cabbage).

[0040] Comparative Example 3: Beauveria bassiana wettable powder (20 billion spores / g), Shenwei Microorganism "Gudefeng 20 billion / g WP" (registered crop: Ostrinia furnacalis).

[0041] Comparative Examples 4 - 6

[0042] Comparative Example 4: Same as Example 5, without adding piperonyl butoxide.

[0043] Comparative Example 5: Same as Example 5, canceling the modified photodegradation inhibitor.

[0044] Comparative Example 6: Same as Example 5, removing the penetrant.

[0045] Comparative Examples 7 - 9

[0046] Comparative Example 7: Same as Example 5, adjusting the mass ratio between tolfenpyrad and piperonyl butoxide to 40:9.

[0047] Comparative Example 8: Same as Example 5, using the traditional mechanical stirring process (non - shear emulsification), mechanical stirring speed 600 rpm, mechanical stirring time 30 min.

[0048] Comparative Example 9: Same as Example 5, canceling the nano - coating treatment and replacing it with a stirring and mixing operation, mixing speed 200 rpm, mixing time 15 min.

[0049] Test scheme: Frankliniella occidentalis, breeding environment: temperature 25 ± 2 °C, relative humidity 40 ± 10%, photoperiod 14 h:10 h (light:dark). Feed: Tomato plants at the four - to - five - leaf stage (Dandong 409 small tomatoes) as a continuous food source.

[0050] The leaf - dipping method was used for indoor toxicity tests. Before the test, young leaves of tomato plants were collected, washed with distilled water, and then immersed in the medicaments prepared in Examples 1 - 5 and Comparative Examples 1 - 9 respectively. The immersion concentration was 1.2 mg / L, and the immersion time was 4 h. After immersion, the leaves were taken out with forceps, placed on absorbent paper, dried to remove excess medicament, and then the leaves were transferred to petri dishes. Cotton was used to absorb distilled water to wrap the petioles to prevent the leaves from drying out. Then, a suction device was used to select newly emerged Frankliniella occidentalis and transfer them to the young leaves in each petri dish. The petri dishes were sealed with plastic wrap, and several air - permeable holes were pricked with toothpicks on the plastic wrap. 50 insects were transferred into each petri dish (as Figure 2As shown in [figure], each concentration was repeated 3 times. After covering the culture dish with plastic wrap, it was transferred to a light incubator and cultivated for 24 h under the conditions of a temperature of 25 °C, a relative humidity of 40%, and a photoperiod of 14 h / 10 h. The feeding situation of Frankliniella occidentalis on the leaves was regularly checked, and the survival situation of Frankliniella occidentalis was examined. The body of the insect was gently touched with a writing brush, and if there was no autonomous response, it was considered dead. The SPSS software was used to fit the virulence regression equation and calculate the LC50. The results are shown in Table 1.

[0051] Table 1 Virulence effect test

[0052]

[0053] In addition, a light stability test was carried out. Taking Example 5 and Comparative Example 5 as examples, the medicaments prepared in Example 5 and Comparative Example 5 were respectively dispensed into transparent glass culture dishes (9 cm in diameter), and 30 mL of the liquid medicine was filled in each dish to ensure that the liquid level thickness was uniform (about 2 mm). The dispensed samples were placed in a constant temperature incubator at 25 °C for 24 h to balance, and the relative humidity was controlled at 40 ± 5% (simulating the benchmark conditions for field storage). The ICH Q1B light stability test guideline Option 2 standard was adopted: Light source configuration: Xenon lamp aging chamber (equipped with a 340 nm filter), irradiance 1.2×10 6 Lux hr (equivalent to an ultraviolet irradiation intensity of 200 W / m²); Temperature control: Maintain 40 ± 2 °C during the light stage and 25 ± 2 °C during the dark stage; Cycle period: Each 24 h includes 12 h of light (irradiance stable at 0.35 W / m² @ 340 nm) and 12 h of darkness, and the total test period is 14 d (simulating the 14 - 21 d effective period in the field). Sampling and detection: Take 5 mL of the liquid medicine for high performance liquid chromatography (HPLC) analysis to detect the residue amount of tolfenpyrad (Chromatographic conditions: C18 column, mobile phase acetonitrile - water 70:30, flow rate 1 mL / min, detection wavelength 254 nm), and evaluate the residue amount of tolfenpyrad. The results are as follows: Example 5 showed that: after 14 d, the residue amount of tolfenpyrad was 88.7%, while Comparative Example 5 showed that: after 14 d, the residue amount of tolfenpyrad was 51.8%.

[0054] The above content further elaborates on the present invention in combination with specific embodiments. It cannot be determined that the specific implementation of the present invention is only limited to these descriptions. For those of ordinary skill in the technical field of biological control to which the present invention belongs, without departing from the concept of the present invention, several simple deductions or substitutions can still be made, which should all be regarded as falling within the protection scope determined by the claims submitted for the present invention.

Claims

1. A biological synergistic formulation for controlling thrips, characterized in that: By weight, the components are as follows: 30-46 parts of tolfenpyrad, 3-6 parts of white sugar, 2-5 parts of synergist, 2-10 parts of dispersant, 3-8 parts of wetting agent, 2-6 parts of penetrant, 1-10 parts of modified photodegradation inhibitor, 0.1-0.6 parts of preservative, 1.2-3.4 parts of magnesium aluminum silicate, deionized water, up to 100 parts; the synergist is selected from one or more of piperonyl butoxide, octachlorodipropyl ether, methoxyphenyl ether, and pulegone; the dispersant is selected from one or more of sodium naphthalene sulfonate formaldehyde condensate, sodium lignosulfonate, and sodium polycarboxylate; the wetting agent is selected from one or more of polysorbate 20, alkyl naphthalene sulfonates, and sophorolipid; the penetrant is selected from one or more of polyether modified polysiloxane, ethyl oleate, lauryl alcohol polyoxyethylene ether, and decyl glucoside; the preservative is selected from one or more of sodium benzoate, potassium sorbate, and isothiazolinones.

2. The biological synergistic formulation for controlling thrips according to claim 1, characterized in that: By weight, the components are as follows: 35-44 parts of tolfenpyrad, 3-6 parts of white sugar, 2-5 parts of synergist, 4-8 parts of dispersant, 3-8 parts of wetting agent, 2-6 parts of penetrant, 4-8 parts of modified photodegradation inhibitor, 0.2-0.6 parts of preservative, 1.5-2.5 parts of magnesium aluminum silicate, deionized water, up to 100 parts.

3. The bio-enhanced formulation for controlling thrips according to claim 2, wherein: By weight, the components are as follows: 40 parts of tolfenpyrad, 5 parts of white sugar, 4 parts of synergist, 6 parts of dispersant, 5 parts of wetting agent, 4 parts of penetrant, 6 parts of modified photodegradation inhibitor, 0.4 parts of preservative, 2.0 parts of magnesium aluminum silicate, deionized water, up to 100 parts.

4. The biological synergistic formulation for controlling thrips according to claim 1, characterized in that: The CAS number of the tolfenpyrad is 129558-76-5; the white sugar is food-grade sucrose with a purity ≥ 99.5%, CAS number 57-50-1, and molecular weight 342.30; the CAS number of the magnesium aluminum silicate is 1327-43-1; the preparation method of the modified photodegradation inhibitor is as follows: titanium dioxide and metal salt precursor are mixed at a mass ratio of 1:(0.1-0.5), 0.1-1.0 mol / L hydrofluoric acid solution is added, and ultrasonic dispersion is carried out for 30-60 min to form a uniform suspension. The metal salt precursor is cerium nitrate; the obtained suspension is transferred to a high-pressure reaction kettle, and hydrothermal reaction is carried out at 120-180 °C for 12-48 h. After the reaction, it is naturally cooled to room temperature, centrifuged and separated, and then washed 3 times with deionized water and anhydrous ethanol respectively, and dried at 80 °C for 6 h to obtain a metal-doped composite support; the metal-doped composite support and an ethanol solution containing 1-5% (by mass) of silane coupling agent KH-550 are mixed at a solid-liquid mass ratio of 1:10, and stirred and reacted at 60-80 °C for 4-8 h under nitrogen protection to obtain a functional support. Then, 2-hydroxy-4-methoxybenzophenone and the functional support are dissolved in acetone at a mass ratio of 1:(0.5-2.0), ultrasonic treated for 30 min, and the solvent is removed by rotary evaporation at 40 °C.

5. The biological synergistic formulation for controlling thrips according to claim 1, wherein: The mixing treatment method of the bio-enhanced formula is as follows: Pretreatment stage: Tolfenpyrad and piperonyl butoxide are premixed at 20°C to form a homogeneous oil phase, and then a modified photodegradation inhibitor is added for nanoscale coating; Main mixing stage: A shear emulsifier is used, and deionized water, a dispersant, a wetting agent, a penetrant, and a preservative are added in sequence, and the system temperature is controlled at 35°C, = 6.5 - 7.5; Post-treatment stage: Magnesium aluminum silicate and white sugar are added, stirred at low speed, and then treated by a homogenizer to obtain the product.

6. Use of the bio-enhanced formulation according to claim 1 in the preparation of an agent for controlling thrips.

7. Use of the bioaugmentation formulation according to claim 6 in the preparation of an agent for controlling thrips, characterized in that: The dosage form of the agent is a pharmaceutically acceptable dosage form.

8. Use of the bioaugmentation formulation according to claim 7 in the preparation of an agent for controlling thrips, characterized in that: The dosage form of the medicament is a suspension, an emulsion or a spray.

9. Use of the bioaugmentation formulation according to claim 8 in the preparation of an agent for controlling thrips, characterized in that: The administration method of the medicament is spraying or soaking.

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