Agricultural synergist containing menthol and application thereof

Abstract

The invention discloses an agricultural synergist containing menthol and application of the agricultural synergist, and belongs to the technical field of biocides containing natural plant or animal source substances. The synergist comprises menthol, a plant-derived nonionic surfactant, a chitin derivative adhesive, a natural phenol antioxidant stabilizer, a nisin modification accelerant and the balance of deionized water. Through a triple synergistic mechanism that the surfactant enhances the permeability of liquid medicine, the adhesive prolongs the retention time of leaves, and the stabilizer inhibits decomposition of active components, the field lasting period of menthol is prolonged to 2.3 times of that of a conventional preparation, and the degradation rate is increased by 97% compared with that of a chemical synergist.

Description

Technical Field

[0001] The present invention relates to the technical field of biological pesticides, in particular to an agricultural synergist containing menthol and application thereof. Background Art

[0002] Menthol, a natural monoterpene compound extracted from mint plants (such as peppermint or peppermint), is renowned for its unique cooling effect and diverse biological activities. Menthol possesses a variety of properties, including antibacterial, insecticidal, analgesic, and anti-inflammatory properties, and has been widely used in the pharmaceutical, food, and cosmetic industries. For example, in medicine, menthol is used as a topical analgesic and antibacterial agent; in the food industry, it is often used as a flavoring to impart a refreshing taste to products. However, while research and application of menthol in these fields are relatively mature, its development and utilization in agriculture is still in its infancy. In recent years, preliminary studies have demonstrated that menthol has some inhibitory effects on certain agricultural pests (such as aphids and mites) and pathogens (such as fungi and bacteria), providing theoretical support for its potential as a botanical pesticide active ingredient. Despite this, menthol faces numerous challenges in its agricultural application, including poor chemical stability, volatilization or decomposition in the natural environment, and a short-lasting effect. These limitations significantly restrict its practical value and promotion prospects as a pesticide.

[0003] To overcome the aforementioned shortcomings of biopesticide active ingredients, the application of synergists has become a key technological approach to improving their efficacy. Synergists are a class of auxiliary substances that enhance the biological activity of pesticides, prolong their duration of action, and improve their stability and permeability. By compounding with active ingredients, synergists not only improve the control efficacy of pesticides but also reduce pesticide usage, thereby reducing negative impacts on the environment and ecosystems. The application of synergists is relatively mature in traditional chemical pesticides. Common types include surfactants (such as Tween compounds), adhesives (such as plant oil derivatives), and stabilizers (such as antioxidants). However, research on synergists for plant-derived active ingredients (such as menthol) is still lacking. Existing synergists are mostly general-purpose formulations designed for chemical pesticides, which fail to fully utilize the unique advantages of natural compounds like menthol. Furthermore, most synergists currently used on the market are chemically synthesized substances. While they may improve pesticide performance to some extent, their potential environmental toxicity and threats to human health are contrary to the sustainable development concept of green agriculture. Therefore, developing an efficient and environmentally friendly special enhancer based on the characteristics of menthol not only has important scientific value, but also meets the urgent needs of modern agriculture for safe and eco-friendly products.

[0004] While there have been a few studies on the application of menthol in agriculture, most of these studies have been limited to preliminary validation of the insecticidal or antibacterial effects of menthol as a single active ingredient. For example, some experiments have shown that menthol can achieve a feeding repellency rate of over 60% against certain agricultural pests and an inhibition rate of around 50% against specific fungi. However, these studies often lack systematicity and in-depth analysis, and exploration of combining menthol with other ingredients to enhance efficacy is particularly limited. Furthermore, the synergist formulations used in existing technologies are mostly general-purpose chemical formulations that are not optimized for menthol's physical and chemical properties (such as volatility and low water solubility), significantly reducing their effectiveness in field applications. More importantly, the use of chemical synergists may introduce new environmental risks, such as soil residues and water pollution, which runs counter to the original "green and environmentally friendly" nature of biopesticides. Therefore, existing technologies cannot fully meet the needs of large-scale menthol application in agriculture, and the development of new synergists is urgently needed to fill this technological gap. Summary of the Invention

[0005] In view of the needs and deficiencies of the existing technology, the present invention provides an agricultural synergist containing menthol and its application. The bottlenecks of the existing technology are: poor stability: the photolysis half-life of conventional menthol preparations is only 3.2h (λ=365nm), the field persistence period is generally ≤3d, and the penetration efficiency is low: the contact angle of the liquid is 73°, the surface tension is 32.8mN / m, resulting in an effective ingredient penetration rate of only 0.12μg / cm 2 ·h, high environmental risk: The 96h-LD50 of the chemical enhancer NP-10 to zebrafish is 6.7 mg / L, which is significantly ecotoxic. Innovative solution: Use plant-derived nonionic surfactants (glycosides, etc.) to reduce surface tension to 28.5 mN / m, optimize the contact angle to 42°, and increase the penetration rate to 0.34 μg / cm 2 h. A 20-50nm mesh membrane structure constructed with a chitin derivative adhesive achieves a 72-hour drug retention of 81%, a 113% improvement over traditional formulations. Natural phenolic compounds such as rosmarinic acid extend the photolysis half-life to 18.7 hours. The synergistic mechanism of this invention is shown in Table 1 below:

[0006] Table 1

[0007]

[0008]

[0009] In order to solve the above technical problems and achieve the above technical effects, the present invention is carried out through the following technical solutions.

[0010] A menthol-containing agricultural synergist comprises, by mass percentage, 5-15% menthol (CAS No. 2216-51-5), 0.1-5% surfactant, 0.5-3% adhesive, 0.1-2% stabilizer, and 0.5-2% modification accelerator, with the balance being deionized water; wherein the surfactant is a plant-derived nonionic surfactant; the adhesive is a chitin derivative; and the stabilizer is a natural phenolic antioxidant.

[0011] Preferably, the menthol-containing agricultural synergist comprises, by mass percentage, 8-12% menthol, 0.5-3% surfactant, 1.5-2% adhesive, 0.5-1.5% stabilizer and 1-2% modification promoter, with the balance being deionized water; wherein: the surfactant is a plant-derived nonionic surfactant; the adhesive is a chitin derivative; and the stabilizer is a natural phenolic antioxidant.

[0012] Preferably, the menthol-containing agricultural synergist comprises, by mass percentage, 10% menthol, 2% surfactant, 1.8% adhesive, 1% stabilizer and 1.5% modification promoter, with the balance being deionized water; wherein: the surfactant is a plant-derived nonionic surfactant; the adhesive is a chitin derivative; and the stabilizer is a natural phenolic antioxidant.

[0013] Preferably, the plant-derived nonionic surfactant is cocoyl glucoside (CAS No. 141464-42-8), decyl glucoside (CAS No. 68515-73-1) or lauryl glucoside (CAS No. 27836-64-2); the chitin derivative is carboxymethyl chitosan (CAS No. 83512-85-0), chitosan hydrochloride (CAS No. 70694-72-7) or hydroxypropyl chitosan (CAS No. 129063-61-0); and the natural phenolic antioxidant is gallic acid (CAS No. 149-91-7), epigallocatechin gallate (CAS No. 989-51-5) or rosmarinic acid (CAS No. 20283-92-5).

[0014] Preferably, the preparation method of the modified accelerator is as follows: menthol and 4-fluoro-styrene are reacted in an N,N-dimethylformamide solvent under the catalysis of sodium hydride to obtain an intermediate through a nucleophilic substitution reaction; then, the intermediate is reacted with ethyl acrylate under the action of a photocatalyst and irradiated with a blue LED lamp to produce a free radical reaction to obtain a product.

[0015] The agricultural synergist containing menthol as described above is used in the preparation of insecticides.

[0016] The menthol-containing agricultural synergist is used in the preparation of an insecticide. The agricultural synergist is compounded with the insecticide at a compounding mass ratio of 1:(2-10); and the insecticide is selected from at least one of chlorantraniliprole, deltamethrin, and pymetrozine.

[0017] The menthol-containing agricultural synergist is used in the preparation of insecticides. The dosage form of the agricultural synergist is a pharmaceutically acceptable dosage form, including but not limited to emulsifiable concentrate, suspension, water-dispersible granules or soluble powder.

[0018] The menthol-containing agricultural synergist is used in the preparation of an insecticide, and the insecticide is used to control the two-spotted spider mite, whose Latin name is Tetranychus urticae.

[0019] Compared with the existing technology, the technical solution of this application has the following beneficial effects:

[0020] Triple synergistic mechanism: (1) Penetration enhancement mechanism. The plant-derived glucoside surfactant (coconut oil base / decyl / lauryl) reduces the surface tension of the drug solution to 28.5±1.3mN / m, reducing the contact angle from 73° in the conventional formula to 42°. This property enables the drug solution to form a homogeneous spreading film on the leaf surface, increasing the penetration rate by 2.8 times. Nuclear magnetic resonance data show that the hydroxyl groups contained in the surfactant molecules form a hydrogen bond network with menthol, promoting the transport of active ingredients across the cuticle. (2) Retention enhancement mechanism. The chitosan derivative adhesive works in the following ways: carboxymethyl chitosan forms a three-dimensional network structure on the leaf surface, forming ionic bonds with the carboxyl groups of the leaf wax layer through the amino group. Drug retention rate: 81% of the initial amount is retained after 72 hours, which is 63% higher than that of conventional plant oil adhesives. (3) Stable protection mechanism: natural phenolic antioxidants (such as rosmarinic acid) quench singlet oxygen (quantum yield Φ = 0.89), chelate metal ions (binding constant log K = 5.7), and extend the photolysis half-life of menthol from 3.2h to 18.7h (λ = 365nm).

[0021] Chemical modification innovation: The synthesis and function of the modified accelerator TM, which achieves molecular transformation through a two-step reaction: Nucleophilic substitution: The menthol hydroxyl group reacts with the fluorine atom of 4-fluorostyrene (yield 82%) to introduce a styrene group. Photocatalytic grafting: The intermediate ZJT is added to the ethyl acrylate free radical (initiated by a blue LED) to form a TM molecule with an amphiphilic structure. The modified molecular properties: The octanol / water partition coefficient logP is reduced from 3.1 to 2.4, enhancing leaf adsorption, reducing the critical micelle concentration (CMC) to 0.12mM, improving penetration efficiency, and increasing the thermal decomposition temperature from 156°C to 218°C.

[0022] Furthermore, additional testing confirmed that the duration of action was extended by 4.8 times. While the duration of menthol preparations reported in existing literature is generally 2-3 days (e.g., 2.5 days as reported in CN112616833A), this technical solution extends the duration to 11.5 days through a triple synergistic mechanism. This breakthrough stems from: An innovative adhesive system: A chitin derivative (hydroxypropyl chitosan) forms a nanoscale mesh film on the leaf surface (SEM shows a pore size of 20-50 nm), retaining 81% of the drug after 72 hours (data from Example 3), a 113% increase over the 38% retention rate of traditional plant oil adhesives; and controlled release: The acrylate group of the modified accelerator TM triggers controlled release under ultraviolet light (λ = 365 nm). Experimental data show a 24-hour release rate of 37%, significantly lower than the 62% of conventional preparations. Photostability increased by 5.8 times: The introduction of natural phenolic antioxidants extended the photolysis half-life (t1 / 2) of menthol from 3.2h to 18.7h (λ=365nm). The specific mechanisms of action include: free radical scavenging: the phenolic hydroxyl group of rosmarinic acid (characteristic peak of δ6.96) can capture singlet oxygen (quantum yield Φ=0.89); UV shielding: carboxymethyl chitosan forms a light absorption barrier in the 280-320nm band (UV-Vis shows a 2.3-fold increase in absorbance); molecular encapsulation: surfactant micelles (CMC=0.12mM) encapsulate menthol molecules in a hydrophobic core (DLS measured particle size 18.3nm); and the penetration efficiency doubled from 0.12μg / cm 2 h increased to 0.34 μg / cm 2 The key breakthroughs are: surface tension optimization: lauryl glucoside reduces the surface tension of the drug solution to 28.5 mN / m (compared to 32.8 mN / m for the existing Tween 80); structural modification and synergistic enhancement: the logP value of the modified accelerator TM is reduced from 3.1 to 2.4, enhancing cuticle penetration (contact angle reduced from 73° to 42°); dynamic penetration control: during the period of maximum stomatal opening (10:00-14:00), the penetration rate reaches 0.51 μg / cm 2h (circadian rhythm experimental data). Significantly improved environmental friendliness: acute toxicity was reduced 15-fold, and the 96-hour LD50 for zebrafish increased from 6.7 mg / L to >100 mg / L. This is attributed to: natural ingredient substitution: plant-derived surfactants replaced traditional nonylphenol polyoxyethylene ether (NP-10); controlled degradation: the chitosan derivative achieved a 28-day soil degradation rate of 97.3% (OECD 307 standard); optimized metabolic pathways: the modified product TM has a hydrolysis half-life of only 3.2 hours in organisms; improved ecological compatibility and natural enemy protection: the LC50 value for predatory mites (Phytoseiulus persimilis) reached 356 μg / g, a 17-fold increase compared to chemical formulations; soil improvement: after three consecutive seasons of use, soil organic matter content increased by 29%; and the bioconcentration factor: the log BCF decreased from 1.8 to 0.4. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a sample picture of the product prepared in Example 6 of the present invention. DETAILED DESCRIPTION

[0024] To make the original intention, technical solutions, and technical effects of the embodiments of the present invention more clear, the technical solutions are described clearly and completely below in conjunction with the embodiments. Obviously, the embodiments described are only a portion of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0025] The preparation method of the modified accelerator is as follows: menthol and 4-fluoro-styrene are reacted in an N,N-dimethylformamide solvent under the catalysis of sodium hydride to obtain an intermediate through a nucleophilic substitution reaction; then, the intermediate is reacted with ethyl acrylate under the action of a photocatalyst and irradiated with a blue LED lamp to produce a free radical reaction to obtain a product.

[0026] Specifically, the first step involves the nucleophilic substitution reaction of menthol with 4-fluorostyrene. The starting materials and reagents are: 5.0 g (32 mmol) of menthol (S2), 4.7 g (38.4 mmol, 1.2 equivalents) of 4-fluorostyrene (S1), 1.54 g (60% oil dispersion, 38.4 mmol, 1.2 equivalents) of sodium hydride (NaH), and 50 mL (anhydrous grade) of N,N-dimethylformamide (DMF). The procedure is as follows: Sodium hydride is added to a 100 mL three-necked round-bottom flask, cooled to 0°C in an ice bath, and stirred under nitrogen. Menthol is dissolved in 20 mL of anhydrous DMF and slowly added dropwise to the mixture via syringe, maintaining the temperature at 0°C for 30 minutes. After the addition is complete, stirring is continued at this temperature for 30 minutes, then the mixture is warmed to room temperature and stirred for 1 hour to ensure complete deprotonation of the menthol. Dissolve 4-fluoro-styrene in 10 mL of anhydrous DMF and slowly add it dropwise to the reaction mixture via syringe over 15 minutes. After the addition is complete, raise the reaction temperature to 50°C and stir at this temperature for 12 hours. After the reaction is complete, cool the mixture to room temperature, and slowly add 30 mL of water to quench the excess sodium hydride. Pour the mixture into a separatory funnel, add 50 mL of ethyl acetate, separate the organic layer, and extract the aqueous layer three times with 20 mL of ethyl acetate. Combine the organic layers, wash three times with saturated brine, dry over anhydrous sodium sulfate, filter, and remove the solvent by rotary evaporation. The crude product is purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio 20:1) to obtain intermediate ZJT. Step 2: Photocatalytic reaction of the intermediate with ethyl acrylate: Raw materials and reagents, intermediate ZJT: 3.0 g (10 mmol), ethyl acrylate (S3): 1.5 g (15 mmol, 1.5 equivalents), photocatalyst 4CzIPN: 78.5 mg (0.1 mmol, 1 mol%), acetonitrile: 30 mL (HPLC grade); Instruments, blue light LED lamp: 14 W, wavelength 460 nm, light intensity 0.16 W / cm 2The photocatalytic reactor was equipped with a cooling system to maintain the reaction temperature at 25±2°C. The procedure was as follows: In a 50 mL transparent reaction flask, the intermediate ZJT, the photocatalyst 4CzIPN, and acetonitrile were added and deoxygenated by bubbling nitrogen for 5 minutes. Ethyl acrylate was added, the flask was tightly sealed, and the reaction was placed 6 cm from a blue LED light. The blue LED light was turned on, and the reaction mixture was irradiated at 25°C for 12 hours with magnetic stirring. The reaction progress was monitored by TLC until the conversion of the starting material was nearly complete. After the reaction was complete, the light was turned off, and the reaction mixture was removed by rotary evaporation to remove the solvent. The residue was dissolved in 30 mL of dichloromethane and washed sequentially with 5% sodium bicarbonate solution (20 mL x 2) and saturated brine (20 mL x 1). The organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by silica gel column chromatography (petroleum ether:ethyl acetate, volume ratio: 10:1) to obtain the final product, TM, in a yield of 77.3%.

[0027]

[0028] Through characterization tests, S1's 1H NMR: δ7.51 (2H), 7.08 (2H), 6.68 (1H), 5.58 (2H), and its 13C NMR: δ162.90 (1C), 136.29 (1C), 136.08 (1C), 128.30 (2C), 115.50 (2C), 114.11 (1C). Among them, the 1H NMR of S2: δ5.37(1H), 3.41(1H), 1.91(1H), 1.46(2H), 1.45(1H), 1.29(2H), 1.26(2H), 1.11(1H), 0.88(3H), 0.86(6H), and its 13C NMR: δ71.50(1C), 50.20(1C), 45.10(1C), 34.60(1C), 31.60(1C), 25.80(1C), 23.20(1C), 22.00(1C), 20.65(1C), 17.45(1C). Among them, 1HNMR of ZJT: δ7.41(2H), 6.91(2H), 6.68(1H), 5.58(2H), 5.17(1H), 1.91(1H), 1.46(2H), 1.45(1H), 1.38(1H), 1.37(2H), 1.26(2H), 0.88(3H), 0.86(6H), its 13C NMR: δ157.20(1C),136.29(1C),130.34(1C),127.22(2C),122.10(2C),114.11(1C),74.20(1C),47.2 3(1C),41.17(1C),34.31(1C),31.40(1C),26.23(1C),23.45(1C),22.00(1C),20.70(1C),20.57(1C). Among them, the 1H NMR of S3: δ6.15 (1H), 6.13 (2H), 4.24 (2H), 1.29 (3H), and its 13C NMR: δ165.95 (1C), 131.00 (1C), 129.65 (1C), 60.40 (1C), 14.10 (1C).TM's 1H NMR: δ6.96(2H), 6.91(2H), 5.17(1H), 4.24(2H), 2.59(2H), 2.44(1H), 1.91(1H), 1.46(2H), 1.45(1H), 1.44(2H), 1.38(1H), 1.37(2H), 1.29(3H), 1.26(2H), 1.15(3H), 0.88(3H), 0.86(6H), its 13C NMR: δ176.86(1C),157.20(1C),140.70(1C),131.00(2C),129.95(2C),74.20(1C),61.20(1C),47.00(1C),40.87(1C),39.49(1C), 34.20(1C),32.40(1C),31.40(1C),28.60(1C),26.06(1C),23.40(1C),22.00(1C),20.65(1C),17.45(1C),17.12(1C),14.10(1C).

[0029] Example 1

[0030] Formula (mass percentage): menthol: 5%, surfactant: coconut glucoside 0.1%, adhesive: carboxymethyl chitosan 0.5%, stabilizer: gallic acid 0.1%, modification accelerator: 0.5%, deionized water: 93.8%.

[0031] Preparation method: Weigh menthol, coco-glucoside, carboxymethyl chitosan, gallic acid, and a modified accelerator according to the above mass percentages. Add menthol, coco-glucoside, and gallic acid to deionized water and stir evenly. Slowly add carboxymethyl chitosan and continue stirring until completely dissolved. Finally, add the modified accelerator and mix thoroughly to obtain an agricultural synergist.

[0032] Example 2

[0033] Formula (mass percentage): menthol: 8%, surfactant: decyl glucoside 0.5%, adhesive: chitosan hydrochloride 1.5%, stabilizer: epigallocatechin gallate 0.5%, modification accelerator: 1%, deionized water: 88.5%.

[0034] Preparation method: Weigh menthol, decyl glucoside, chitosan hydrochloride, epigallocatechin gallate, and a modified accelerator according to the above mass percentages. Add menthol, decyl glucoside, and epigallocatechin gallate to deionized water and stir evenly. Slowly add chitosan hydrochloride and continue stirring until completely dissolved. Finally, add the modified accelerator and mix thoroughly to obtain an agricultural synergist.

[0035] Example 3

[0036] Formula (mass percentage): menthol: 10%, surfactant: lauryl glucoside 2%, adhesive: hydroxypropyl chitosan 1.8%, stabilizer: rosmarinic acid 1%, modification accelerator: 1.5%, deionized water: 83.7%.

[0037] Preparation method: Weigh menthol, lauryl glucoside, hydroxypropyl chitosan, rosmarinic acid, and a modified accelerator according to the above mass percentages. Add menthol, lauryl glucoside, and rosmarinic acid to deionized water and stir evenly. Slowly add hydroxypropyl chitosan and continue stirring until completely dissolved. Finally, add the modified accelerator and mix thoroughly to obtain an agricultural synergist.

[0038] Example 4

[0039] Formula (mass percentage): menthol: 12%, surfactant: coconut glucoside 3%, adhesive: carboxymethyl chitosan 2%, stabilizer: gallic acid 1.5%, modification accelerator: 2%, deionized water: 79.5%.

[0040] Preparation method: Weigh menthol, coco-glucoside, carboxymethyl chitosan, gallic acid, and a modified accelerator according to the above mass percentages. Add menthol, coco-glucoside, and gallic acid to deionized water and stir evenly. Slowly add carboxymethyl chitosan and continue stirring until completely dissolved. Finally, add the modified accelerator and mix thoroughly to obtain an agricultural synergist.

[0041] Example 5

[0042] Formula (mass percentage): menthol: 15%, surfactant: decyl glucoside 5%, adhesive: chitosan hydrochloride 3%, stabilizer: epigallocatechin gallate 2%, modification accelerator: 2%, deionized water: 73%.

[0043] Preparation method: Weigh menthol, decyl glucoside, chitosan hydrochloride, epigallocatechin gallate, and a modified accelerator according to the above mass percentages. Add menthol, decyl glucoside, and epigallocatechin gallate to deionized water and stir evenly. Slowly add chitosan hydrochloride and continue stirring until completely dissolved. Finally, add the modified accelerator and mix thoroughly to obtain an agricultural synergist.

[0044] Example 6

[0045] Formula (mass percentage): menthol: 10%, surfactant: lauryl glucoside 2%, adhesive: hydroxypropyl chitosan 1.8%, stabilizer: rosmarinic acid 1%, modification accelerator: 1.5%, deionized water: 83.7%.

[0046] Preparation method: Weigh menthol, lauryl glucoside, hydroxypropyl chitosan, rosmarinic acid and modified accelerator according to the above mass percentages. Add menthol, lauryl glucoside and rosmarinic acid to deionized water and stir evenly. Slowly add hydroxypropyl chitosan and continue stirring until completely dissolved. Finally, add the modified accelerator and mix thoroughly to obtain an agricultural synergist, such as Figure 1 shown.

[0047] Test plan

[0048] The prepared agricultural synergist (Examples 1-6) is compounded with an insecticide, wherein the compounding mass ratio is 1:(2-10); the insecticide is chlorantraniliprole. The dosage form of the agricultural synergist is a suspension concentrate. The pest to be controlled is the two-spotted spider mite, whose Latin name is Tetranychus urticae. Using the leaf dipping method, different compounded agents (combinations of synergists and insecticides) are applied to the leaves of the host plant (potato, Solanum tube rosum L.). Adult two-spotted spider mites are inoculated onto the treated leaves, with no less than 3 repetitions per group. Control groups are set up: an untreated group (clear water), a group using chlorantraniliprole alone, and a group using the compounded agent without a modified accelerator.

[0049] Observation indicators: Record mite mortality (number of dead individuals / total number of individuals × 100%) 24, 48, and 72 hours after application. Observe changes in mite activity. Conditions: Temperature: 25 ± 2°C, relative humidity: 60%, daylight: 16 hours light / 8 hours dark.

[0050] Table 2

[0051]

[0052] Table 3

[0053]

[0054] The results were analyzed as follows: Dose-Effect Relationship: Examples 1-3 showed a clear dose-effect relationship, with efficacy increasing significantly with increasing concentration of each component. Optimal Formula: Examples 3 / 6 demonstrated the best overall efficacy, achieving a 72-hour mortality rate of 92.7% and a long-lasting effect of 11.5 days. High-Concentration Saturation: Despite higher concentrations of each component, Examples 4 and 5 exhibited slightly lower efficacy than Examples 3 / 6, indicating a concentration saturation effect. Excessive concentrations can lead to decreased dispersibility or antagonistic effects. Contribution of Modified Accelerator: Comparing the unmodified accelerator formulation with Examples 3 / 6, the modified accelerator significantly contributed to the improved efficacy, increasing it by approximately 13.3 percentage points. Overall Contribution of Synergists: Compared to the chlorantraniliprole alone, the complete synergist formulation increased mortality by 24.5 percentage points and extended the long-lasting effect by 130%. These results confirm the effectiveness of the patented triple synergistic mechanism and demonstrate that this synergist formulation can significantly enhance the field application value of menthol-based biopesticides.

[0055] The above description is merely a preferred embodiment of the present application and an illustration of the technical principles employed. Those skilled in the art should understand that the scope of the invention involved in this application is not limited to the technical solutions formed by the specific combination of the above-mentioned technical features, but also encompasses reasonable modifications that can be made by those skilled in the art without departing from the inventive concept.

Claims

1. An agricultural synergist containing menthol, characterized in that: The composition comprises, by mass percentage, 5-15% menthol, 0.1-5% surfactant, 0.5-3% adhesive, 0.1-2% stabilizer and 0.5-2% modification accelerator, with the balance being deionized water; wherein the surfactant is a plant-derived nonionic surfactant; the adhesive is a chitin derivative; and the stabilizer is a natural phenolic antioxidant.

2. The agricultural synergist containing menthol according to claim 1, characterized in that The composition comprises, by mass percentage, 8-12% menthol, 0.5-3% surfactant, 1.5-2% adhesive, 0.5-1.5% stabilizer and 1-2% modification accelerator, with the remainder being deionized water; wherein the surfactant is a plant-derived nonionic surfactant; the adhesive is a chitin derivative; and the stabilizer is a natural phenolic antioxidant.

3. The agricultural synergist containing menthol according to claim 2, characterized in that The composition comprises, by mass percentage, 10% menthol, 2% surfactant, 1.8% adhesive, 1% stabilizer, 1.5% modification accelerator, and the balance deionized water; wherein the surfactant is a plant-derived nonionic surfactant; the adhesive is a chitosan derivative; and the stabilizer is a natural phenolic antioxidant.

4. The agricultural synergist containing menthol according to claim 1, characterized in that The plant-derived nonionic surfactant is coconut glucoside, decyl glucoside or lauryl glucoside; the chitin derivative is carboxymethyl chitosan, chitosan hydrochloride or hydroxypropyl chitosan; and the natural phenolic antioxidant is gallic acid, epigallocatechin gallate or rosmarinic acid.

5. The agricultural synergist containing menthol according to claim 1, characterized in that: The preparation method of the modified accelerator is as follows: Menthol and 4-fluoro-styrene are reacted by nucleophilic substitution in N,N-dimethylformamide solvent under the catalysis of sodium hydride to obtain an intermediate; then, the intermediate is reacted with ethyl acrylate under the action of a photocatalyst and irradiated with a blue LED lamp to produce a free radical reaction to obtain the product.

6. Use of the menthol-containing agricultural synergist according to any one of claims 1 to 5 in the preparation of insecticides.

7. Use of the menthol-containing agricultural synergist according to claim 6 in the preparation of insecticides, characterized in that: The agricultural synergist is compounded with an insecticide, wherein the compounding mass ratio is 1:(2-10); the insecticide is selected from at least one of chlorantraniliprole, deltamethrin and pymetrozine.

8. Use of the menthol-containing agricultural synergist according to claim 7 in the preparation of insecticides, characterized in that: The dosage form of the agricultural synergist is a pharmaceutically acceptable dosage form, including but not limited to emulsifiable concentrate, suspension, water-dispersible granules or soluble powder.

9. Use of the menthol-containing agricultural synergist according to claim 8 in the preparation of insecticides, characterized in that: The pest controlled by the insecticide is the two-spotted spider mite, whose Latin name is Tetranychus urtic ae.

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