A vegetable oil-based interfacial modifier for macrolide pesticide suspensions

Abstract

The present application relates to a kind of plant oil-based interface modification adjuvant for macrolide pesticide suspending agent, belong to pesticide preparation technical field, adopt cashew phenol, phytosterol, chitosan natural plant oil-based biomass as core raw material, first phytosterol is pre-compounded with cashew phenol-PEG amphiphilic adjuvant, then combined with chitosan by electrostatic self-assembly and homogenization emulsification to construct ternary composite modification system, produce significant synergistic effect, effectively inhibit pesticide particle aggregation, phytosterol has strong hydrophobic interface adsorption capacity, can improve the effect of liquid leaf adhesion, cashew phenol-PEG amphiphilic segment gives system excellent wetting and spreading performance, on the one hand, all use natural biomass base material, biodegradability and ecological compatibility are excellent, meet the green pesticide low-carbon development requirement, on the other hand, single adjuvant can have dispersion, stable, wet, multiple functions such as adhesion, without additional multiple adjuvant, simplify formula composition.

Description

Technical Field

[0001] This invention belongs to the field of pesticide formulation technology and relates to a plant oil-based interface modifier for macrolide pesticide suspensions. Background Technology

[0002] Against the backdrop of green agricultural development and increasingly stringent environmental regulations on pesticides, water-based pesticide suspensions are gradually becoming the mainstream pesticide formulation due to their advantages such as being solvent-free, safe, environmentally friendly, and easy to use. Macrolide pesticides, represented by abamectin and emamectin benzoate, have high insecticidal activity and a broad control range, making them widely used in crop pest and disease control. However, the technical grade of these pesticides is highly hydrophobic, has extremely poor water solubility, and exhibits prominent crystallinity. When preparing suspensions, the solid-liquid interface compatibility is poor, grinding and dispersion are difficult, and the finished product is prone to problems such as particle agglomeration, sedimentation and stratification, high-temperature clumping, and low-temperature water separation, resulting in poor storage stability. Furthermore, the formulation's wetting and spreading effect on leaves is poor, adhesion is weak, and resistance to rain washout is poor, leading to low field utilization. Currently, there are many general-purpose plant oil adjuvants on the market, but specialized interface-modified products specifically adapted to macrolide pesticide suspensions are scarce, making it difficult to simultaneously meet the multiple requirements of formulation stability, wetting enhancement, and environmental protection. Therefore, the development of specialized plant oil-based interface modifiers can effectively improve the interface properties of the system, enhance the quality of formulations and field efficacy, and help the pesticide industry achieve green and low-carbon transformation, thus possessing high research and application value.

[0003] Chinese invention patent application CN122030381A discloses a polymeric suspending agent for anti-precipitation pesticide suspension and its preparation method. The raw materials of the polymeric suspending agent are in the following weight ratios: abamectin 10%-16%; pyridaben 10%-17%; chlorantraniliprole 5.0%-12.0%; a special polymeric suspending agent 0.5%-1.5%; modified magnesium aluminum silicate 0.3%-1.0%; a wetting agent 2.0%-4.0%; a phosphate ester dispersant 2.0%-4.0%; urea 4.0%-6.0%; and carbamate. Pine 0.1%-0.3%; silicone defoamer 0.1%-0.5%; citric acid / sodium citrate buffer 2%-8%; anti-hydrolysis agent 0%-1.0%, with the remaining deionized water to make up to 100%. By introducing a polycarboxylate-g-polyoxypropylene ether / polyoxyethylene ether graft copolymer with a comb-like structure as a special polymeric suspending agent, the prepared polymeric suspending agent achieves a triple stabilization mechanism of anchoring-steric hindrance-hydrophobic association network at the molecular level, giving the suspending agent excellent long-term anti-sedimentation ability and good pourability from the root.

[0004] The polymeric suspending agents in the above-mentioned technical solutions mainly use petrochemical synthetic additives and do not use natural plant oil-based biomass raw materials. The products have poor biodegradability and poor ecological compatibility, making it difficult to meet the requirements of green pesticide development and low-carbon environmental protection in the industry. At the same time, this solution also requires the additional compounding of a variety of dispersants and wetting agents for synergistic use, resulting in complex formulation components and cumbersome system compatibility design. Summary of the Invention

[0005] The purpose of this invention is to provide a plant oil-based interface modifier for macrolide pesticide suspensions. An amphiphilic intermediate is prepared by modifying and grafting cashew phenol, and then combined with phytosterols and chitosan through electrostatic self-assembly to improve the dispersibility, storage stability and leaf wetting and adhesion of pesticide suspensions, thus meeting the application requirements of macrolide pesticides in a green way.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A plant oil-based interface modifier for macrolide pesticide suspension concentrates is prepared by the following steps:

[0008] Step 1: Cashew nutmeg and 3-mercapto-1-propanol are grafted together via a free radical thiol-ene click reaction to obtain cashew nutmeg polyol; under the phase transfer catalysis of tetrabutylammonium bromide, the hydroxyl group of the cashew nutmeg polyol undergoes nucleophilic substitution with methyl epichlorohydrin to generate a chlorohydrin intermediate, and then undergoes a dehydrochlorination ring-closure reaction to obtain cashew nutmeg glycidyl ether.

[0009] Step 2: Under the catalysis of boron trifluoride-tetrahydrofuran, the terminal epoxy group of cashew phenol glycidyl ether undergoes a ring-opening etherification addition reaction with the terminal hydroxyl group of polyethylene glycol to obtain cashew phenol-PEG grafted amphiphilic interface modifier.

[0010] Step 3: First, phytosterols are compounded with cashew phenol-PEG grafted amphiphilic interface modifiers. Then, phytosterols and chitosan are electrostatically self-assembled and homogenized emulsified to obtain plant oil-based interface modifiers for macrolide pesticide suspensions.

[0011] Furthermore, the specific preparation process of cashew nut polyol is as follows:

[0012] Cashew nut alcohol, 3-mercapto-1-propanol and azobisisobutyronitrile were added to a reaction vessel and reacted at 80-90℃, under nitrogen protection and at 300-500 r / min for 24-26 h. The mixture was then filtered, washed and purified to obtain cashew nut alcohol polyol.

[0013] Furthermore, the mass ratio of cashew phenol, 3-mercapto-1-propanol and azobisisobutyronitrile is 30.10-40.10: 11.01-19.01: 0.53-0.77.

[0014] Furthermore, the specific preparation process of cashew phenolic glycidyl ether is as follows:

[0015] Cashew phenol polyol, methyl epichlorohydrin and tetrabutylammonium bromide were added to a reaction vessel and reacted at 80-90℃ and 300-500 r / min for 3-4 h. A 40wt% sodium hydroxide solution was then added dropwise and reacted at 0-5℃ for 4-5 h. After washing and purification, cashew phenol glycidyl ether was obtained.

[0016] Furthermore, the mass ratio of cashew phenol polyol, methyl epichlorohydrin, tetrabutylammonium bromide and sodium hydroxide solution is 35.00-43.00: 36.80-46.80: 0.35-0.55: 33-40.

[0017] Furthermore, the specific preparation process of the cashew phenol-PEG grafted amphiphilic interface modifier is as follows:

[0018] Polyethylene glycol and cashew phenol-based glycidyl ether were added to a reaction vessel and mixed evenly. Lewis acid boron trifluoride-tetrahydrofuran was added as a catalyst, and the reaction was carried out at a constant temperature of 40-45℃ in a sealed environment for 4-6 hours. After cooling to room temperature, cashew phenol-PEG grafted amphiphilic interface modifier was obtained.

[0019] Furthermore, the mass ratio of polyethylene glycol, cashew phenol glycidyl ether, and Lewis acid boron trifluoride-tetrahydrofuran is 150-200:100-120:0.75-0.87.

[0020] Furthermore, the molecular weight of polyethylene glycol is 200-800.

[0021] Furthermore, the specific preparation process of the plant oil-based interface-modifying adjuvant for macrolide pesticide suspension concentrates is as follows:

[0022] Chitosan powder and a 2.0 vol% acetic acid solution were added to a reaction vessel and stirred for 10-12 hours. The pH was adjusted to 4.2, then deionized water was added and stirred for 5-7 minutes. Mixture A was then added dropwise and stirred for 30-40 minutes. The mixture was then homogenized and emulsified at 800-900 r / min for 5-7 minutes to obtain a plant oil-based interface modifier for macrolide pesticide suspensions.

[0023] Furthermore, the ratio of chitosan powder, acetic acid solution, deionized water and mixture A is 10-14g: 990-1100mL: 500-600mL: 30-45g.

[0024] Furthermore, the specific preparation process of mixture A is as follows:

[0025] Plant sterol particles and cashew phenol-PEG grafted amphiphilic interface modifier were added to a reaction vessel and stirred for 20-30 minutes at 80-90℃ and 300-500 r / min to obtain mixture A.

[0026] Furthermore, the mass ratio of phytosterol particles to cashew phenol-PEG grafted amphiphilic interface modifier is 10-18:20-30.

[0027] The beneficial effects of this invention are:

[0028] 1. This invention innovatively uses cashew phenol, phytosterol, and chitosan, natural plant oil-based biomass, as core raw materials. First, phytosterol is pre-compounded with cashew phenol-PEG amphiphilic adjuvant, and then combined with chitosan through electrostatic self-assembly and homogenization to construct a ternary composite modified system, which produces a significant synergistic effect. Under acidic conditions, chitosan is protonated and positively charged, forming electrostatic repulsion with negatively charged phytosterol, effectively inhibiting pesticide particle aggregation. Phytosterol has a strong hydrophobic interface adsorption capacity, which can improve the adhesion effect of pesticide solution to the leaf surface. The cashew phenol-PEG amphiphilic segment gives the system excellent wetting and spreading properties. The three components work together to form a triple stabilization mechanism of steric hindrance, electrostatic repulsion, and interfacial adsorption and wetting. On the one hand, the entire process uses natural biomass substrates, which have excellent biodegradability and ecological compatibility, meeting the requirements of green pesticide low-carbon development. On the other hand, a single adjuvant can have multiple functions such as dispersion, stabilization, wetting, and adhesion, without the need for additional compounding of multiple adjuvants, simplifying the formulation composition. At the same time, it can significantly improve the long-term storage stability of macrolide pesticide suspensions at high and low temperatures, eliminate clumping, water separation, and stratification, and enhance the adhesion of the pesticide solution to the leaf surface and its resistance to rain washout, effectively improving the utilization rate of pesticides in the field.

[0029] 2. This invention first utilizes a thiol-ene click reaction to directionally introduce hydroxyl groups onto the cashew phenol molecule to obtain cashew phenol polyol. Then, through nucleophilic substitution and dehydrochlorination ring closure, cashew phenol glycidyl ether is generated. Finally, it is ring-opened grafted with polyethylene glycol epoxy to form an amphiphilic molecular structure of a hydrophobic cashew phenol backbone and a hydrophilic polyethylene glycol segment. This structure can be directionally anchored on the surface of hydrophobic macrolide pesticide technical particles, relying on steric hindrance to prevent particle collision and aggregation. Simultaneously, it effectively reduces the pesticide-water solid-liquid interfacial tension, improves the system's interfacial compatibility, and fundamentally solves the inherent defects of macrolide pesticide technical particles, such as difficulty in grinding, easy aggregation, and easy sedimentation and stratification in suspension systems.

[0030] 3. This invention uses natural plant oils and biomass derivatives such as cashew phenol, phytosterol, and chitosan as core raw materials throughout the entire process, completely replacing traditional petrochemical interface additives. The raw materials are widely available, biodegradable, and leave no ecological residues, which meets the requirements of green agriculture and low-carbon development of pesticides. At the same time, it relies on free radical thiol-ene click reaction to achieve molecular directional grafting, with precise and controllable reaction sites and few side reactions. Subsequent epoxy ring-closing, ring-opening etherification, and self-assembly compounding are all carried out under mild temperature and conventional stirring conditions, without the need for highly corrosive and polluting reagents. The overall preparation process is simple, mild, green and environmentally friendly, and easy to industrialize.

[0031] 4. This invention utilizes a structural matching design based on the hydrophobic properties of macrolide pesticide molecules such as abamectin and emamectin benzoate. Compared to commercially available plant oil adjuvants, it exhibits better interfacial compatibility with the active ingredients of these pesticides. It eliminates the need for additional compounding of multiple dispersants and wetting agents, as a single adjuvant can simultaneously fulfill multiple functions such as dispersion, stabilization, wetting, and adhesion. It has strong formulation adaptability and can be directly applied to the preparation of macrolide pesticide suspensions with different ratios, simplifying formulation design and production processes, and offering high cost-effectiveness. Detailed Implementation

[0032] To further illustrate the technical means and effects of the present invention in achieving the intended purpose, the following detailed description of the specific implementation methods, features and effects of the present invention, in conjunction with preferred embodiments, is provided below.

[0033] Example 1: This example provides a plant oil-based interface modifier for macrolide pesticide suspensions, prepared through the following steps:

[0034] S1: 35.10g of cashew nut alcohol, 15.01g of 3-mercapto-1-propanol and 0.65g of azobisisobutyronitrile were added to a reaction vessel and reacted at 85℃, under nitrogen protection and at 400r / min for 25h. After the reaction was completed, the mixture was filtered, and ethyl acetate was added to the filtrate to dilute it completely. The mixture was washed 7 times with saturated sodium chloride aqueous solution to completely remove unreacted 3-mercapto-1-propanol. The washed organic phase was placed in a rotary evaporator to remove ethyl acetate, and cashew nut alcohol polyol with a hydroxyl value of 510.25mg KOH / g was obtained.

[0035] The side chain of cashew phenol contains unsaturated carbon-carbon double bonds. Under the initiation of azobisisobutyronitrile, free radicals are generated. The double bonds of cashew phenol undergo a free radical thiol-ene click reaction with 3-mercapto-1-propanol. The double bonds are completely added and transformed and hydroxyl functional groups are introduced in a directional manner to generate cashew phenol polyol with a polyhydroxy structure.

[0036] S2: 39.00g of cashew nut polyol, 41.80g of methyl epichlorohydrin and 0.45g of tetrabutylammonium bromide were added to a reaction vessel and reacted at 85℃ and 400r / min for 3.5h. Then, 36.5g of 40wt% sodium hydroxide solution was added dropwise and the reaction was carried out at 2℃ for 4.5h. After the reaction was completed, the sodium chloride was removed by filtration. Twice the volume of ethyl acetate solution was added to the filtrate and the mixture was washed five times with saturated sodium chloride solution to remove methyl epichlorohydrin. The organic phase was then evaporated using a rotary evaporator to remove ethyl acetate, yielding cashew nut polyglycidyl ether with an epoxy value of 0.3215mol / 100g.

[0037] Under the phase transfer catalysis of tetrabutylammonium bromide, the hydroxyl groups in cashew phenol polyol first undergo a nucleophilic substitution etherification reaction with methyl epichlorohydrin to generate a chlorohydrin intermediate. Subsequently, under the action of a low temperature of 2°C and a strong base of 40wt% sodium hydroxide, the chlorohydrin intermediate rapidly undergoes a dehydrochlorination ring-closure reaction to form a stable terminal epoxy group.

[0038] S3: 175g of dried PEG200 (polyethylene glycol 200) and 110g of dried cashew phenol-based glycidyl ether were added to a reaction vessel and mixed evenly at 22℃ and 400r / min. 0.81g of Lewis acid boron trifluoride-tetrahydrofuran was added as a catalyst, and the reaction was carried out at a constant temperature of 42℃ in a sealed environment for 5h. After cooling to room temperature, cashew phenol-PEG grafted amphiphilic interface modifier was obtained.

[0039] Under the catalysis of Lewis acid boron trifluoride-tetrahydrofuran, the terminal epoxy group of cashew phenol glycidyl ether undergoes a ring-opening etherification addition reaction with the terminal hydroxyl group of PEG200, and hydrophilic polyethylene glycol segments are covalently grafted onto the hydrophobic cashew phenol backbone to form an amphiphilic (hydrophilic and lipophilic) molecular structure of "hydrophobic anchoring group-hydrophilic polyether chain". This structure can be directionally enriched at the solid-liquid interface between macrolide pesticide technical and water, reducing interfacial tension, inhibiting particle aggregation, and improving the storage stability of suspension concentrate and the ability to wet and spread on leaves.

[0040] S4: Add 14g of phytosterol granules (90% purity, purchased from Xi'an Guobang Industrial Co., Ltd.) and 25g of cashew phenol-PEG grafted amphiphilic interface modifier to the reactor and stir for 25min at 85℃ and 400r / min to obtain mixture A.

[0041] S5: Add 12g of chitosan powder and 1045mL of acetic acid solution with a concentration of 2.0 vol% to the reactor, stir for 11h at 22℃ and 400r / min, adjust the pH to 4.2, add 550mL of deionized water, stir for 6min, then add 37.5g of mixed solution A dropwise, stir for 35min, and homogenize and emulsify for 6min at 850r / min to obtain a plant oil-based interface modifier for macrolide pesticide suspension.

[0042] Under acidic conditions, the amino groups of chitosan undergo protonation and become positively charged, which can generate strong electrostatic interactions with negatively charged phytosterol particles. They rely on non-covalent self-assembly to form stable composite colloidal particles. The pre-mixed phytosterol and cashew phenol-PEG grafted amphiphilic interface modifier achieve affinity coating through hydrophobic interactions. After homogenization and emulsification, they are further uniformly dispersed. The composite system simultaneously possesses the electrostatic repulsion effect of chitosan, the hydrophobic interface adsorption characteristics of phytosterol, and the steric hindrance and hydrophilic spreading ability of cashew phenol-PEG segments.

[0043] Example 2: This example provides a plant oil-based interface modifier for macrolide pesticide suspensions, prepared through the following steps:

[0044] S1: 30.10 g cashew nut alcohol, 11.01 g 3-mercapto-1-propanol and 0.53 g azobisisobutyronitrile were added to a reaction vessel and reacted at 80 °C, under nitrogen protection and at 300 r / min for 24 h. After the reaction was completed, the mixture was filtered, and ethyl acetate was added to the filtrate to dilute it completely. The mixture was washed 6 times with saturated sodium chloride aqueous solution to completely remove unreacted 3-mercapto-1-propanol. The washed organic phase was placed in a rotary evaporator to remove ethyl acetate, and cashew nut alcohol polyol with a hydroxyl value of 520.12 mg KOH / g was obtained.

[0045] S2: 35.00g of cashew nut polyol, 36.80g of methyl epichlorohydrin and 0.35g of tetrabutylammonium bromide were added to a reaction vessel and reacted at 80℃ and 300r / min for 3h. Then, 33g of 40wt% sodium hydroxide solution was added dropwise and the reaction was carried out at 0℃ for 4h. After the reaction was completed, the sodium chloride was removed by filtration. Twice the volume of ethyl acetate solution was added to the filtrate to dilute it. The solution was washed 5 times with saturated sodium chloride solution to remove methyl epichlorohydrin. The organic phase was then removed by rotary evaporation to remove ethyl acetate, yielding cashew nut polyglycidyl ether with an epoxy value of 0.3221mol / 100g.

[0046] S3: Add 150g of dried PEG200 (polyethylene glycol 200) and 100g of dried cashew phenol-based glycidyl ether to a reaction vessel, mix them evenly at 20℃ and 300r / min, add 0.75g of Lewis acid boron trifluoride-tetrahydrofuran as a catalyst, and react at a constant temperature of 40℃ in a sealed environment for 4h. Cool to room temperature to obtain cashew phenol-PEG grafted amphiphilic interface modifier.

[0047] S4: Add 10g of phytosterol granules (90% purity, purchased from Xi'an Guobang Industrial Co., Ltd.) and 20g of cashew phenol-PEG grafted amphiphilic interface modifier to the reactor and stir for 20min at 80℃ and 300r / min to obtain mixture A.

[0048] S5: Add 10g of chitosan powder and 990mL of 2.0vol% acetic acid solution to the reactor, stir for 10h at 20℃ and 300r / min, adjust the pH to 4.2, add 500mL of deionized water, stir for 5min, then add 30g of mixture A dropwise, stir for 30min, and homogenize and emulsify for 5min at 800r / min to obtain a plant oil-based interface modifier for macrolide pesticide suspension.

[0049] Example 3: This example provides a plant oil-based interface modifier for macrolide pesticide suspensions, prepared through the following steps:

[0050] S1: 40.10 g of cashew nut alcohol, 19.01 g of 3-mercapto-1-propanol and 0.77 g of azobisisobutyronitrile were added to a reaction vessel and reacted at 90 °C, under nitrogen protection and at 500 r / min for 26 h. After the reaction was completed, the mixture was filtered, and ethyl acetate was added to the filtrate to dilute it completely. The mixture was washed 8 times with saturated sodium chloride aqueous solution to completely remove unreacted 3-mercapto-1-propanol. The washed organic phase was placed in a rotary evaporator to remove ethyl acetate, and cashew nut alcohol polyol with a hydroxyl value of 518.12 mg KOH / g was obtained.

[0051] S2: 43.00g of cashew phenol polyol, 46.80g of methyl epichlorohydrin and 0.55g of tetrabutylammonium bromide were added to a reaction vessel and reacted at 90℃ and 500r / min for 4h. 40g of 40wt% sodium hydroxide solution was added dropwise and reacted at 5℃ for 5h. After the reaction was completed, sodium chloride was removed by filtration. Twice the volume of ethyl acetate solution was added to the filtrate to dilute it. The solution was washed 6 times with saturated sodium chloride solution to remove methyl epichlorohydrin. The organic phase was then evaporated using a rotary evaporator to remove ethyl acetate, yielding cashew phenol glycidyl ether with an epoxy value of 0.3187mol / 100g.

[0052] S3: Add 200g of dried PEG200 (polyethylene glycol 200) and 120g of dried cashew phenol-based glycidyl ether to a reactor and mix them evenly at 25℃ and 500r / min. Add 0.87g of Lewis acid boron trifluoride-tetrahydrofuran as a catalyst and react at a constant temperature of 45℃ in a sealed environment for 6h. Cool to room temperature to obtain cashew phenol-PEG grafted amphiphilic interface modifier.

[0053] S4: Add 18g of phytosterol granules (90% purity, purchased from Xi'an Guobang Industrial Co., Ltd.) and 30g of cashew phenol-PEG grafted amphiphilic interface modifier to the reactor and stir for 30min at 90℃ and 500r / min to obtain mixture A.

[0054] S5: Add 14g of chitosan powder and 1100mL of 2.0vol% acetic acid solution to the reactor, stir for 12h at 25℃ and 500r / min, adjust the pH to 4.2, add 600mL of deionized water, stir for 7min, then add 45g of mixture A dropwise, stir for 40min, and homogenize and emulsify for 7min at 900r / min to obtain a plant oil-based interface modifier for macrolide pesticide suspension.

[0055] Example 4: This example provides a plant oil-based interface modifier for macrolide pesticide suspensions. The difference from Example 1 is that polyethylene glycol 400 is used instead of polyethylene glycol 200 in step S3.

[0056] Example 5: This example provides a plant oil-based interface modifier for macrolide pesticide suspensions. The difference from Example 1 is that polyethylene glycol 600 is used instead of polyethylene glycol 200 in step S3.

[0057] Example 6: This example provides a plant oil-based interface modifier for macrolide pesticide suspensions. The difference from Example 1 is that polyethylene glycol 800 is used instead of polyethylene glycol 200 in step S3.

[0058] Example 7: This example provides a macrolide pesticide suspension, prepared through the following steps:

[0059] 3.0% of 99% abamectin technical, 12.0% of 95% bromocyanamide technical, 10.0% of the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 1, 0.5% organosilicon defoamer, 0.2% xanthan gum thickener, 0.1% Kathon preservative, 3.0% propylene glycol antifreeze, 2.0% magnesium aluminum silicate, and the balance deionized water were added together in the specified proportions to a high-shear emulsifier for high-speed shearing and homogenization emulsification. The mixture was then ground in a sand mill for 2 hours until more than 98% of the suspended particles had a particle size of less than 10 μm. Finally, the mixture was transferred to a mixer and mixed evenly to obtain the macrolide pesticide suspension.

[0060] Example 8: This example provides a macrolide pesticide suspension, which differs from Example 7 in that the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 2 is used instead of the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 1.

[0061] Example 9: This example provides a macrolide pesticide suspension, which differs from Example 7 in that the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 3 is used instead of the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 1.

[0062] Example 10: This example provides a macrolide pesticide suspension, which differs from Example 7 in that the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 4 is used instead of the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 1.

[0063] Example 11: This example provides a macrolide pesticide suspension, which differs from Example 7 in that the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 5 is used instead of the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 1.

[0064] Example 12: This example provides a macrolide pesticide suspension, which differs from Example 7 in that the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 6 is used instead of the plant oil-based interface modifier for macrolide pesticide suspension prepared in Example 1.

[0065] The sources of the raw materials involved in the above embodiments are as follows:

[0066] Cashew nut shell extract: 93.47% active ingredient content, density 0.910; purchased from Boxing County Deyi Trading Co., Ltd.; Polyethylene glycol 200: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; 3-Mercapto-1-propanol: ≥97%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Azobisisobutyronitrile: ≥95%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Methyl epichlorohydrin: 99% purity, purchased from Hubei Qiansheng Biotechnology Co., Ltd.; Tetrabutylammonium bromide: ≥99%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Polyethylene glycol 400: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Polyethylene glycol 600: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Chemical Technology Co., Ltd.; Polyethylene glycol 800: purchased from Henan Wanshan New Material Technology Co., Ltd.; Boron trifluoride-tetrahydrofuran: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; Chitosan powder: 80-100 mesh, purchased from Baichuan Kangze Biotechnology; Phytosterol granules: 90% purity, purchased from Xi'an Guobang Industrial Co., Ltd.; Avermectin technical grade: purchased from Jiangsu Huirun Pharmaceutical Co., Ltd.; Bromnisin technical grade: purchased from Wuhan Rongcan Biotechnology Co., Ltd.; Organosilicon defoamer: purchased from Momentive Advanced Materials Co., Ltd.; Thickener xanthan gum: purchased from Zibo Zhongxuan Biochemical Co., Ltd.; Kathon: purchased from Shanghai Taizi Chemical Co., Ltd.; Magnesium aluminum silicate: purchased from Lingshou County Zhongxin Mineral Products Processing Plant.

[0067] Comparative Example 1: This comparative example provides a plant oil-based interface modifier for macrolide pesticide suspensions. The difference from Example 1 is that steps S4 and S5 are omitted. The cashew phenol-PEG grafted amphiphilic interface modifier prepared in step S3 is the plant oil-based interface modifier for macrolide pesticide suspensions.

[0068] Comparative Example 2: This comparative example provides a plant oil-based interface modifier for macrolide pesticide suspensions. The difference from Example 1 is that step S5 is omitted. The mixture A prepared in step S4 is the plant oil-based interface modifier for macrolide pesticide suspensions.

[0069] Comparative Example 3: This comparative example provides a plant oil-based interface modifier for macrolide pesticide suspensions. The difference from Example 7 is that the plant oil-based interface modifier for macrolide pesticide suspensions prepared in Comparative Example 1 is used instead of the plant oil-based interface modifier for macrolide pesticide suspensions prepared in Example 1.

[0070] Comparative Example 4: This comparative example provides a plant oil-based interface modifier for macrolide pesticide suspensions. The difference from Example 7 is that the plant oil-based interface modifier for macrolide pesticide suspensions prepared in Comparative Example 2 is used instead of the plant oil-based interface modifier for macrolide pesticide suspensions prepared in Example 1.

[0071] The performance of the plant oil-based interface-modifying adjuvants for macrolide pesticide suspensions prepared in Examples 7-12 and Comparative Examples 3-4 was tested:

[0072] Suspension rate, pourability, and cold / hot storage stability were all determined according to GB / T 14825-2006 "Determination of Suspension Rate of Pesticides". Particle size was determined using a BT-9300S laser particle size analyzer.

[0073] Table 1 Performance Test Overview

[0074] project Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 3 Comparative Example 4 Suspension rate (%) 99.84 99.81 99.89 99.82 99.87 99.85 93.26 95.73 <![CDATA[D 50 / µm]]> 1.21 1.22 1.19 1.17 1.13 1.11 2.38 1.95 Formulation stability after 14 days of heat storage qualified qualified qualified qualified qualified qualified Slight stratification and aggregation Small amount of water separation Formulation stability after 14 days of cold storage qualified qualified qualified qualified qualified qualified Obvious water separation and clumping Slight water separation Dumping excellent excellent excellent excellent excellent excellent good good

[0075] As shown in Table 1, the suspension rates of Examples 7-12 are higher than those of Comparative Examples 3-4. 50 The smaller size of the particles compared to Comparative Examples 3 and 4 indicates that Examples 7-12 exhibit better dispersion performance. This may be because the plant oil-based interface modifiers used in Examples 7-12 were first prepared by thiol-olefin click and ring-opening grafting to obtain cashew phenol-PEG amphiphilic molecules, which can form a hydrophobic anchoring and hydrophilic extension interface structure on the surface of pesticide particles. Then, combined with the electrostatic self-assembly of phytosterols and chitosan, a composite colloid is formed. Relying on the dual effects of steric hindrance and electrostatic repulsion, the collision and aggregation of pesticide particles are effectively inhibited, resulting in finer and more uniform particle size after grinding. This makes the particles less prone to flocculation and sedimentation in the aqueous phase, thus significantly improving the suspension and dispersion ability.

[0076] As shown in Table 1, the stability of the formulations in Examples 7-12 after 14 days of hot and cold storage was better than that in Comparative Examples 3-4. This may be because the plant oil-based interface modifiers used in Examples 7-12 formed a triple synergistic stabilizing system of cashew phenol-PEG steric hindrance, phytosterol interface adsorption, and chitosan electrostatic repulsion. During high-temperature storage, this system can inhibit particle thermal motion aggregation and stratification, and during low-temperature storage, it can prevent water separation, crystallization, and agglomeration. In contrast, the comparative examples lacked chitosan electrostatic self-assembly or phytosterol compound modification, resulting in a single stabilization mechanism that could not adapt to changes in high and low temperature environments, making them prone to aggregation, water separation, stratification, and even agglomeration.

[0077] As shown in Table 1, the pourability of Examples 7-12 is better than that of Comparative Examples 3-4. This may be because the plant oil-based interface modifiers used in Examples 7-12 can reasonably regulate the rheological properties of pesticide suspensions, the hydrophilic segments of cashew phenol-PEG improve the interfacial fluidity of the system, and the chitosan and phytosterol composite colloid makes the system viscosity uniform and moderate, without local flocculation and thickening. In contrast, the components of the comparative examples have a single structure and lack the synergistic rheological regulation effect of multiple components. The system is prone to local aggregation, uneven viscosity distribution, more pouring residue, and poor flowability.

[0078] It should be noted that, in this document, terms such as “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0079] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. A plant oil-based interface modifier for macrolide pesticide suspension concentrates, characterized in that, Prepared by the following steps: Step 1: Cashew nutmeg and 3-mercapto-1-propanol are grafted together via a free radical thiol-ene click reaction to obtain cashew nutmeg polyol; under the phase transfer catalysis of tetrabutylammonium bromide, the hydroxyl groups of the cashew nutmeg polyol undergo nucleophilic substitution with methyl epichlorohydrin to generate a chlorohydrin intermediate, and then undergo a dehydrochlorination ring-closure reaction to obtain cashew nutmeg glycidyl ether. Step 2: Under the catalysis of boron trifluoride-tetrahydrofuran, the terminal epoxy group of cashew phenol glycidyl ether undergoes a ring-opening etherification addition reaction with the terminal hydroxyl group of polyethylene glycol to obtain cashew phenol-PEG grafted amphiphilic interface modifier. Step 3: First, phytosterols are compounded with cashew phenol-PEG grafted amphiphilic interface modifiers. Then, phytosterols and chitosan are electrostatically self-assembled and homogenized emulsified to obtain plant oil-based interface modifiers for macrolide pesticide suspensions.

2. The vegetable oil-based interface modifier for macrolide pesticide suspensions according to claim 1, characterized in that, The specific preparation process of the cashew phenol polyol mentioned in step one is as follows: Cashew nut alcohol, 3-mercapto-1-propanol and azobisisobutyronitrile were added to a reaction vessel and reacted at 80-90℃, under nitrogen protection and at 300-500 r / min for 24-26 h. The mixture was then filtered, washed and purified to obtain cashew nut alcohol polyol.

3. The vegetable oil-based interface modifier for macrolide pesticide suspensions according to claim 2, characterized in that, The mass ratio of cashew phenol, 3-mercapto-1-propanol and azobisisobutyronitrile is 30.10-40.10: 11.01-19.01: 0.53-0.

77.

4. The vegetable oil-based interface modifier for macrolide pesticide suspensions according to claim 1, characterized in that, The specific preparation process of the cashew phenolic glycidyl ether described in step one is as follows: Cashew phenol polyol, methyl epichlorohydrin and tetrabutylammonium bromide were added to a reaction vessel and reacted at 80-90℃ and 300-500 r / min for 3-4 h. A 40wt% sodium hydroxide solution was then added dropwise and reacted at 0-5℃ for 4-5 h. After washing and purification, cashew phenol glycidyl ether was obtained.

5. A plant oil-based interface modifier for macrolide pesticide suspensions according to claim 4, characterized in that, The mass ratio of cashew phenol polyol, methyl epichlorohydrin, tetrabutylammonium bromide and sodium hydroxide solution is 35.00-43.00: 36.80-46.80: 0.35-0.55: 33-40.

6. The vegetable oil-based interface modifier for macrolide pesticide suspensions according to claim 1, characterized in that, The specific preparation process of the cashew phenol-PEG grafted amphiphilic interface modifier mentioned in step two is as follows: Polyethylene glycol and cashew phenol-based glycidyl ether were added to a reaction vessel and mixed evenly. Lewis acid boron trifluoride-tetrahydrofuran was added as a catalyst, and the reaction was carried out at a constant temperature of 40-45℃ in a sealed environment for 4-6 hours. After cooling to room temperature, cashew phenol-PEG grafted amphiphilic interface modifier was obtained.

7. A plant oil-based interface modifier for macrolide pesticide suspensions according to claim 6, characterized in that, The mass ratio of polyethylene glycol, cashew phenol glycidyl ether, and Lewis acid boron trifluoride-tetrahydrofuran is 150-200:100-120:0.75-0.

87. The molecular weight of the polyethylene glycol is 200-800.

8. A plant oil-based interface modifier for macrolide pesticide suspensions according to claim 1, characterized in that, The specific preparation process of the plant oil-based interface-modifying adjuvant for macrolide pesticide suspension concentrates is as follows: Chitosan powder and a 2.0 vol% acetic acid solution were added to a reaction vessel and stirred for 10-12 hours. The pH was adjusted to 4.2, then deionized water was added and stirred for 5-7 minutes. Mixture A was then added dropwise and stirred for 30-40 minutes. The mixture was then homogenized and emulsified at 800-900 r / min for 5-7 minutes to obtain a plant oil-based interface modifier for macrolide pesticide suspensions.

9. A plant oil-based interface modifier for macrolide pesticide suspensions according to claim 8, characterized in that, The ratio of chitosan powder, acetic acid solution, deionized water and mixture A is 10-14g: 990-1100mL: 500-600mL: 30-45g.

10. A plant oil-based interface modifier for macrolide pesticide suspensions according to claim 9, characterized in that, The specific preparation process of the mixture A is as follows: Plant sterol particles and cashew phenol-PEG grafted amphiphilic interface modifier were added to a reaction vessel and stirred for 20-30 min at 80-90℃ and 300-500 r / min to obtain mixture A. The mass ratio of the phytosterol particles to the cashew phenol-PEG grafted amphiphilic interface modifier is 10-18:20-30.