A pesticide stabilizing nano-adjuvant, its preparation method and application

Abstract

This invention provides a pesticide-stabilizing nano-adjuvant, its preparation method, and its application, belonging to the field of pesticide adjuvant technology. The nano-dispersant in the pesticide-stabilizing nano-adjuvant provided by this invention includes amino-modified attapulgite, which can utilize the interaction between amino groups and pesticide particles to form a protective layer on the surface of the pesticide particles, thereby physically isolating the interaction between pesticides. The nano-dispersant also includes a metal-organic framework loaded on the surface of the amino-modified attapulgite; the metal-organic framework can increase the specific surface area of ​​the nano-dispersant, increase the contact area with pesticide particles, and thus further improve the stability of the pesticide particles. The pesticide-stabilizing nano-adjuvant also includes a dispersing stabilizer, which enables the nano-dispersant to be stably dispersed in water. Because this invention utilizes the nano-dispersant to physically isolate pesticide particles, it can improve the stability of mixed pesticides.

Description

Technical Field

[0001] This invention relates to the field of pesticide adjuvant technology, and in particular to a pesticide stabilizing nano-adjuvant, its preparation method, and its application. Background Technology

[0002] In agricultural production, the mixed use of different pesticide formulations is a key means to reduce labor costs and improve the timeliness of pest control. However, due to incompatibility or interactions between different formulations, problems such as flocculation, precipitation, clumping, and even phytotoxicity often occur after mixing, leading to mixing failures. Currently, most solutions rely on agricultural experience to avoid these issues (such as avoiding acid-base mixing or mixing anion-cationic formulations). However, with the wide variety and frequent updates of pesticides, coupled with the extremely high requirements for pesticide stability from new technologies such as aerial spraying and automated dosing, traditional experience is no longer sufficient to meet practical needs.

[0003] Commercially available agricultural nano-adjuvants (such as the Youzhu® series) improve the foliar spread and adhesion of pesticides by preparing nanoemulsions from methyl vegetable oil. However, due to their structural characteristics, they cannot improve the stability of mixtures and are mainly designed for aerial application. Furthermore, these products are labeled as flammable, posing safety hazards. In addition, Chinese patent CN112851430A discloses a formulation system using seaweed fertilizer mixed with pesticides, but this method is only applicable to oil suspensions, limiting its scope and failing to meet the mixing needs of various pesticide formulations.

[0004] Attapulgite is a natural one-dimensional nano-hydrated magnesium-aluminate silicate clay mineral with a nanorod-like crystal structure, abundant surface-active groups, and excellent adsorption properties. It has been widely studied for its functional applications, including pesticide slow-release carriers, pesticide formulation suspension stabilizers, and soil conditioners. Metal-organic frameworks (MOFs) are porous crystalline materials formed by the self-assembly of metal ions and organic ligands through coordination bonds. Due to their ultra-high specific surface area and tunable pore structure, they have attracted widespread attention in recent years for targeted pesticide delivery and pH-responsive controlled release. However, current applications of both types of materials in agriculture mainly focus on the slow-release / delivery or environmental behavior regulation of single pesticides, and have not yet addressed the interfacial compatibility and stability improvement when mixing different pesticide formulations.

[0005] In the field of MOF-based nanopesticides, Li et al. (Small, 2026, e14881) constructed cellulose nanocrystals / Zn-MOF nanocarriers, achieving pH-responsive release and enhanced leaf adhesion of pesticides. However, this method requires adding pesticide molecules directly to the material during the preparation process, which is complex and has not been proven to be directly used for synergistic effects in commercially available pesticide formulations. In this field, MOFs are mainly designed as pesticide delivery carriers (targeted / controlled release) and have not yet been applied to solve the compatibility problem when mixing pesticides of different formulations.

[0006] In the field of attapulgite modification, Hou et al. (Environ Pollut, 2023, 336:122408) constructed a glyphosate slow-release carrier by modifying attapulgite with dopamine, while Wang et al. (J Nanosci Nanotechnol, 2016, 16(6):5869-5874) used biochar to improve the dispersibility of attapulgite to reduce pesticide environmental runoff. Chinese patent CN121420970A discloses the use of modified attapulgite for thickening and suspending single pesticides. However, the method is complex, and the patent does not actually demonstrate the thickening and suspending effects on pesticides, making it impossible to confirm whether it can be applied to stabilize compound pesticides and enhance their efficacy. In the field of attapulgite composite MOFs, Niu et al. (Food Chem, 2020, 317:126425) prepared ATP@Fe3O4@ZIF-8 magnetic solid-phase extraction materials, and Chinese patent CN119059849A disclosed the use of aminated attapulgite for fertilizer slow release. The aforementioned attapulgite-related work focuses on pesticide slow release / dispersion / suspension / detection and fertilizer applications, respectively, but has not yet utilized attapulgite and its composite structures for improving the stability of mixtures of different pesticide formulations.

[0007] Therefore, there is an urgent need to provide a safe pesticide-stabilizing nano-adjuvant that can improve the stability of pesticide mixtures of different formulations. Summary of the Invention

[0008] The purpose of this invention is to provide a pesticide stabilizing nano-adjuvant, its preparation method, and its application. The pesticide stabilizing nano-adjuvant provided by this invention has high safety and can improve the stability of pesticide mixtures of different formulations.

[0009] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a pesticide stabilizing nano-adjuvant, comprising a nano-dispersant, a dispersing stabilizer, and water; the mass ratio of the nano-dispersant, the dispersing stabilizer, and the water volume is (0.3~1.0) g : (0.5~2.5) g : 100 mL; The nano-dispersant comprises amino-modified attapulgite and a metal-organic framework supported on the surface of the amino-modified attapulgite.

[0010] Preferably, the diameter of the attapulgite in the amino-modified attapulgite is 10~30nm; and the length is 800~1000nm.

[0011] Preferably, the amount of chemically bonded amino groups in the amino-modified attapulgite is 0.4~1.0 mmol / g.

[0012] Preferably, the metal-organic framework comprises one or more of ZIF-8, copper-benzene-1,3,5-tricarboxylic acid, copper-lignin, and zinc-lignin.

[0013] Preferably, the particle size of the metal-organic framework is 3~15nm.

[0014] Preferably, the metal-organic framework content in the nano-dispersant is 3-10% by mass.

[0015] Preferably, the dispersion stabilizer comprises one or more of hexadecyl ammonium chloride, Tween 20, and Span 80.

[0016] This invention also provides a method for preparing the pesticide stabilizing nano-adjuvant described in the above technical solution, comprising the following steps: (1) Mix attapulgite, amino modifier and solvent to carry out modification reaction to obtain amino-modified attapulgite; (2) The amino-modified attapulgite obtained in step (1) is mixed with a metal ion solution, centrifuged, washed and collected, redispersed in water and mixed with a ligand solution to carry out a coordination modification reaction to obtain a nano-dispersant; (3) The nano-dispersant obtained in step (2) is mixed with the dispersant stabilizer and water to obtain a pesticide-stabilizing nano-adjuvant.

[0017] Preferably, the amino modifier in step (1) includes one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, guanidopropyltriethoxysilane and guanidopropyltrimethoxysilane.

[0018] The present invention also provides the application of the pesticide stabilizing nano-adjuvants described in the above technical solutions or the pesticide stabilizing nano-adjuvants prepared by the preparation methods described in the above technical solutions in the mixing of water-soluble, water-emulsion and water-suspended pesticide formulations.

[0019] This invention provides a pesticide-stabilizing nano-adjuvant, comprising a nano-dispersant, a dispersion stabilizer, and water; the mass ratio of the nano-dispersant, the dispersion stabilizer, and the water volume is (0.3~1.0) g : (0.5~2.5) g : 100 mL; the nano-dispersant comprises amino-modified attapulgite and a metal-organic framework loaded on the surface of the amino-modified attapulgite. The nano-dispersant in the pesticide-stabilizing nano-adjuvant provided by this invention includes amino-modified attapulgite, which can utilize the interaction between amino groups and pesticide particles to form a protective layer on the surface of pesticide particles, thereby physically isolating the interaction between pesticides; the nano-dispersant also includes a metal-organic framework loaded on the surface of the amino-modified attapulgite; the metal-organic framework can increase the specific surface area of ​​the nano-dispersant, increase the contact area with pesticide particles, and thus better improve the stability of pesticide particles; the pesticide-stabilizing nano-adjuvant also includes a dispersion stabilizer, which enables the nano-dispersant to be stably dispersed in water. This invention utilizes nano-dispersants to physically isolate pesticide particles, thus making it applicable to the mixing of pesticides of different formulations. The results of the examples show that the pesticide-stabilizing nano-adjuvants provided by this invention, when mixed with pesticides of different formulations, can significantly improve the stability of the pesticides. Attached Figure Description

[0020] Figure 1 This is a schematic diagram illustrating the working principle of the pesticide stabilizing nano-adjuvant of the present invention; Figure 2 A schematic diagram illustrating the reasons for sedimentation in pesticide formulations; Figure 3 This is a SEM image of the attapulgite soil used in Embodiment 1 of the present invention; Figure 4 This is a SEM image of the nano-dispersant prepared in Example 1 of the present invention; Figure 5 Infrared spectra of the attapulgite clay and the prepared nano-dispersant used in Example 1 of this invention; Figure 6 A photograph of the pesticide stabilizing nano-adjuvant prepared in Example 1 of this invention; Figure 7 These are photographs of the pyraclostrobin mixtures obtained in Application Examples 1-4 and Comparative Application Example 1 after standing for 0h, 2h, and 24h. Figure 8 These are photographs of the abamectin-spirodiclofen mixtures obtained in Application Examples 5-8 and Comparative Application Example 2 after standing for 0h, 2h, and 24h. Figure 9 These are photographs of the thiophanate-methyl mixtures obtained in Application Examples 9-12 and Comparative Application Example 3 after standing for 0h, 2h, and 24h. Figure 10These are photographs of the thiamethoxam mixtures obtained in Application Examples 13-16 and Comparative Application Example 4 after standing for 0h, 2h, and 24h. Figure 11 Photographs of the abamectin-perchloride-fluoride mixture obtained in Application Examples 17-20 and Comparative Application Example 5 after standing for 0h, 2h and 24h. Figure 12 These are photographs of the mixtures of chlorfenapyr and chlorfenapyr obtained in Application Examples 21-24 and Comparative Application Example 6 after standing for 0h, 2h, and 24h. Figure 13 These are photographs of the tebuconazole mixtures obtained in Application Examples 25-28 and Comparative Application Example 7 after standing for 0h, 2h, and 24h. Figure 14 Photographs of the octochlor acetate mixtures obtained in Application Examples 29-32 and Comparative Application Example 8 after standing for 0h, 2h, and 24h. Figure 15 Photographs of the compound solutions obtained from Application Examples 33-36 and Comparative Application Example 9 after standing for 0h, 2h, and 24h; Figure 16 Photographs of the compound solutions obtained from Application Examples 37-40 and Comparative Application Example 10 after standing for 0h, 2h, and 24h; Figure 17 These are photographs of the compound solutions obtained from Application Examples 41-44 and Comparative Application Example 11 after standing for 0h, 2h, and 24h. Figure 18 Photographs of the compound solutions obtained from Application Examples 45-48 and Comparative Application Example 12 after standing for 0h, 2h, and 24h; Figure 19 Photographs of the compound solutions obtained from Application Examples 49-52 and Comparative Application Example 13 after standing for 0h, 2h, and 24h; Figure 20 The graph shows the antibacterial rate test results obtained from application examples 53-68 and comparative application examples 14-17 of the present invention. Figure 21 The graph shows the antibacterial rate test results obtained from application examples 69-80 and comparative application examples 18-20 of the present invention. Detailed Implementation

[0021] This invention provides a pesticide stabilizing nano-adjuvant, comprising a nano-dispersant, a dispersing stabilizer, and water; the mass ratio of the nano-dispersant, the dispersing stabilizer, and the water volume is (0.3~1.0) g : (0.5~2.5) g : 100 mL; The nano-dispersant comprises amino-modified attapulgite and a metal-organic framework supported on the surface of the amino-modified attapulgite.

[0022] The pesticide stabilizing nano-adjuvant provided by this invention includes a nano-dispersant. In this invention, the nano-dispersant includes amino-modified attapulgite and a metal-organic framework supported on the surface of the amino-modified attapulgite.

[0023] In this invention, the diameter of the attapulgite in the amino-modified attapulgite is preferably 10-30 nm, more preferably 15-25 nm; the length of the attapulgite in the amino-modified attapulgite is preferably 800-1000 nm, more preferably 900-1000 nm. The amino-modified attapulgite provided by this invention has the above-mentioned diameter and length, and consists of nanoscale particles with a smaller particle size, which is more conducive to forming a protective layer on the surface of pesticide particles.

[0024] In this invention, the chemical bonding amount of amino groups in the amino-modified attapulgite is preferably 0.4~1.0 mmol / g, more preferably 0.8~1.0 mmol / g. This invention utilizes amino modification to alter the surface charge of the attapulgite, thereby enhancing its interaction with pesticide particles. In this invention, the chemical bonding amount of amino groups in the amino-modified attapulgite within the above-mentioned range results in a stronger interaction with pesticide particles, further improving the stability of pesticide mixtures.

[0025] In this invention, the metal-organic framework preferably comprises one or more of ZIF-8, copper-benzene-1,3,5-tricarboxylic acid, copper-lignin, and zinc-lignin, more preferably ZIF-8. This invention improves the specific surface area of ​​the nano-dispersant by loading a metal-organic framework onto the surface of amino-modified attapulgite.

[0026] In this invention, the particle size of the metal-organic framework is preferably 3-15 nm, more preferably 5-12 nm. The metal-organic framework provided by this invention has a particle size within the above range, possessing a nanoscale size, which can improve the specific surface area of ​​the nano-dispersant.

[0027] In this invention, the mass content of the metal-organic framework in the nano-dispersant is preferably 3-10%, more preferably 5-8%. Controlling the mass content of the metal-organic framework within the above range in this invention is more conducive to increasing the specific surface area of ​​the nano-dispersant.

[0028] The pesticide-stabilizing nano-adjuvant provided by this invention includes a dispersing stabilizer. By adding a dispersing stabilizer, this invention enables the nano-dispersant to be stably dispersed in water, thus giving the pesticide-stabilizing nano-adjuvant good stability.

[0029] In this invention, the dispersant stabilizer preferably comprises one or more of hexadecyl ammonium chloride, Tween 20, and Span 80, more preferably a mixture of hexadecyl ammonium chloride, Tween 20, and Span 80. In this invention, the mass ratio of hexadecyl ammonium chloride, Tween 20, and Span 80 in the mixture is preferably (0.5~1):0.5:1.0, more preferably (0.8~1):0.5:1.0. The use of the above-mentioned dispersant stabilizer in this invention is more conducive to achieving good stability in pesticide-stabilized nano-adjuvants.

[0030] In this invention, the mass ratio of the nano-dispersant, the mass of the dispersing stabilizer, and the volume of water is (0.3~1.0) g : (0.5~2.5) g : 100 mL, preferably (0.4~0.8) g : (2.0~2.5) g : 100 mL. By controlling the mass ratio of the nano-dispersant, the dispersing stabilizer, and the volume of water within the above range, this invention is more conducive to obtaining a stable pesticide-stabilized nano-adjuvant.

[0031] The pesticide stabilizing nano-adjuvant provided by this invention utilizes the interaction between amino groups and pesticide particles to form a protective layer on the surface of pesticide particles, thereby physically isolating the interaction between pesticides; the metal-organic framework can increase the specific surface area of ​​the nano-dispersant and increase the contact area with pesticide particles, which is more conducive to improving the stability of pesticide particles; the pesticide stabilizing nano-adjuvant provided by this invention also includes a dispersing stabilizer, which enables the nano-dispersant to be stably dispersed in water.

[0032] This invention also provides a method for preparing the pesticide stabilizing nano-adjuvant described in the above technical solution, comprising the following steps: (1) Mix attapulgite, amino modifier and solvent to carry out modification reaction to obtain amino-modified attapulgite; (2) The amino-modified attapulgite obtained in step (1) is mixed with the metal ion solution, centrifuged, washed and collected, redispersed in water and mixed with the ligand solution to carry out coordination modification reaction to obtain nano-dispersant; (3) The nano-dispersant obtained in step (2) is mixed with the dispersant stabilizer and water to obtain a pesticide-stabilizing nano-adjuvant.

[0033] This invention involves mixing attapulgite, an amino modifier, and a solvent to carry out a modification reaction, thereby obtaining amino-modified attapulgite.

[0034] In this invention, the diameter of the attapulgite is preferably 10-30 nm, more preferably 15-25 nm; the length of the attapulgite in the amino-modified attapulgite is preferably 800-1000 nm, more preferably 900-1000 nm. The attapulgite of the above particle size used in this invention, being nano-sized particles, is more conducive to forming a protective layer on the surface of pesticide particles.

[0035] In this invention, the amino modifier preferably includes one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, guanidinopropyltriethoxysilane, and guanidinopropyltrimethoxysilane, more preferably 3-aminopropyltriethoxysilane. By using the above-mentioned amino modifier to modify attapulgite, this invention enables the neutral attapulgite surface to carry a large number of positive charges and active groups that can coordinate with metal ions. These groups can support the formation of MOFs on the particle surface and further increase the number of hydrophilic or hydrophobic groups or regions on the surface that can generate hydrogen bonds or hydrophobic regions. These regions can interact with negatively charged or hydrophobic pesticide molecules through one or more of electrostatic interactions, hydrogen bonds, and hydrophilic-hydrophobic interactions, thereby forming a physical isolation layer on the surface of the pesticide particles.

[0036] In this invention, the preferred mass ratio of attapulgite to amino modifier is (0.4~1):(0.8~1.5), more preferably (0.4~0.6):(0.8~1.2). By controlling the mass ratio of attapulgite to amino modifier within the above range, this invention enables sufficient amino groups to be modified onto the attapulgite, which is more conducive to improving the interaction between amino-modified attapulgite and pesticide particles.

[0037] In this invention, the solvent is preferably a mixed solution of water and ethanol, wherein the volume ratio of water to ethanol in the mixed solution is preferably (9~5):(1~5), more preferably 8:2. This invention uses the above-mentioned mixed solution as the solvent for the modification reaction, which ensures the uniform dissolution of the amino modifier while allowing the attapulgite clay to be stably dispersed and settled and washed after the reaction.

[0038] In this invention, the method of mixing attapulgite, amino modifier and solvent preferably includes: mixing attapulgite with solvent to obtain attapulgite suspension; and adding amino modifier dropwise into attapulgite suspension.

[0039] In this invention, the preferred ratio of the mass of the attapulgite clay to the volume of the solvent is (0.3~1.0) g: (50~100) mL, more preferably (0.5~0.8) g: (70~100) mL.

[0040] In this invention, the preferred method for mixing the attapulgite with the solvent is ultrasound. This invention does not impose specific limitations on the power and duration of the ultrasound, as long as it is sufficient to fully disperse the attapulgite in the solvent. In an embodiment of this invention, the ultrasound duration can be 30 minutes.

[0041] This invention does not impose a particular limitation on the rate at which the amino modifier is added, as long as it is added dropwise to the attapulgite suspension. By adding the amino modifier dropwise, this invention facilitates a more uniform mixing of the amino modifier and the attapulgite, thereby promoting a more complete modification reaction.

[0042] In this invention, the amino modifier is preferably added dropwise under stirring. Stirring allows the amino modifier added to the attapulgite suspension to disperse rapidly. In an embodiment of this invention, the stirring speed can be 300 rpm.

[0043] In this invention, the temperature of the modification reaction is preferably 25-40°C, more preferably 25-30°C; the pH of the modification reaction is preferably 7-10, more preferably 7.5-8.5; and the time of the modification reaction is preferably 1-6 hours, more preferably 2-4 hours. The above-mentioned temperature and time conditions are more conducive to promoting a more complete modification reaction.

[0044] In this invention, the modification reaction is preferably carried out under stirring. In an embodiment of this invention, the stirring speed can be 300 rpm. Stirring allows the modification reaction to be more complete, resulting in a more uniform distribution of the amino modifier on the surface of the attapulgite clay in the obtained product.

[0045] Preferably, after the modification reaction, the system obtained from the modification reaction is subjected to centrifugation, washing, and drying sequentially to obtain amino-modified attapulgite. The present invention does not impose any particular limitation on the operation methods of centrifugation, washing, and drying; conventional centrifugation, washing, and drying methods are acceptable. In the embodiments of the present invention, the washing reagent can be water, and the washing can be performed three times; the drying temperature can be 60°C, and the drying time can be 8 hours. The present invention can remove impurities from amino-modified attapulgite through centrifugation, washing, and drying.

[0046] After obtaining amino-modified attapulgite, the present invention mixes the amino-modified attapulgite with a metal ion solution, centrifuges and washes it, collects the mixture, redisperses it in water, mixes it with a ligand solution, and carries out a coordination modification reaction to obtain a nano-dispersant.

[0047] In this invention, the preferred method for mixing the amino-modified attapulgite with the metal ion solution, centrifuging and washing to collect the mixture, redispersing it in water, and then mixing it with the ligand solution is as follows: the amino-modified attapulgite is impregnated in the metal ion solution and then washed with water to obtain amino-modified attapulgite containing metal ions; the amino-modified attapulgite containing metal ions is dispersed in water and then mixed with the ligand solution.

[0048] In this invention, the metal ions in the metal ion solution are preferably Zn. 2+ Cu2+ One or more of them.

[0049] In this invention, the concentration of the metal ion solution is preferably 0.02~0.2 mol / L, more preferably 0.05~0.1 mol / L.

[0050] In this invention, the preferred ratio of the mass of the amino-modified attapulgite to the volume of the metal ion solution is (0.3~1.0) g: (50~100) mL, more preferably (0.5~0.8) g: (60~80) mL.

[0051] In this invention, the immersion temperature is preferably 25~60℃, more preferably 25~40℃; the immersion time is preferably 1~4h, more preferably 2~3h.

[0052] The present invention does not specifically limit the water washing method, as long as it can wash away the unadsorbed metal ions in the amino-modified attapulgite containing metal ions.

[0053] In this invention, the ligands in the ligand solution preferably include one or more of 2-methylimidazole, 1,3,5-benzenetricarboxylic acid, sodium lignosulfonate, and tannic acid.

[0054] In this invention, the concentration of the ligand in the total reaction system is preferably 0.05~0.5 mol / L, more preferably 0.1~0.3 mol / L.

[0055] In this invention, the concentration of the amino-modified attapulgite containing metal ions in the total reaction system is preferably 0.3~1.0% (w / v), more preferably 0.5~0.8% (w / v).

[0056] In this invention, the temperature of the coordination modification reaction is preferably 25~80℃, more preferably 40~60℃; the time of the coordination modification reaction is preferably 2~8h, more preferably 4~6h.

[0057] The present invention preferably involves sequentially centrifuging, washing, and drying the system obtained from the coordination modification reaction to obtain a nano-dispersant. The present invention does not impose any particular limitation on the centrifugation, washing, and drying methods; conventional centrifugation, washing, and drying methods are acceptable. In embodiments of the present invention, the washing reagent can be water, and the washing can be performed three times; the drying temperature can be 60°C, and the drying time can be 8 hours. The present invention can remove impurities from the nano-dispersant through centrifugation, washing, and drying.

[0058] After obtaining the nano-dispersant, the present invention mixes the nano-dispersant with a dispersing stabilizer and water to obtain a pesticide-stabilizing nano-adjuvant.

[0059] In this invention, the dispersion stabilizer is the same as the dispersion stabilizer described in the above technical solution, and will not be repeated here.

[0060] In this invention, the ratio of the mass of the nano-dispersant, the mass of the dispersing stabilizer, and the volume of water is (0.3~1.0) g : (0.5~2.5) g : 100 mL, preferably (0.4~0.8) g : (2.0~2.5) g : 100 mL.

[0061] In this invention, the method of mixing the nano-dispersant with the dispersing stabilizer and water preferably includes: mixing the nano-dispersant with water to obtain a nano-dispersant suspension; and shearing and emulsifying the nano-dispersant suspension with the dispersing stabilizer to obtain a pesticide-stabilizing nano-adjuvant.

[0062] The present invention does not have any particular limitation on the method of mixing the nano-dispersant with water, as long as the nano-dispersant can be fully dispersed in water.

[0063] In this invention, the shear emulsification promotes the formation of a stable suspension system between the nano-dispersant suspension and the dispersant stabilizer. In an embodiment of this invention, the shear emulsification device can be a shear emulsifier, the rotation speed of the shear emulsifier can be 10,000 rpm, and the stirring time of the shear emulsifier can be 3 minutes.

[0064] The method provided by this invention is simple to operate and can obtain stable and dispersed pesticide-stabilized nano-adjuvants.

[0065] The present invention also provides the application of the pesticide stabilizing nano-adjuvant described above in the mixing of water-soluble, water-emulsion and water-suspended pesticide formulations.

[0066] In this invention, the preferred mechanism for the application of the pesticide-stabilizing nano-adjuvant in the mixing of water-soluble, water-emulsion, and water-suspended pesticide formulations is as follows: Figure 1 As shown in the diagram; preferred method for sedimentation of pesticide formulations is as follows. Figure 2 As shown. From Figure 2 It can be seen that sedimentation in mixtures of common pesticides is due to the interaction between different pesticides; from Figure 1 As can be seen, this invention utilizes the interaction between pesticide stabilizing nano-adjuvants and pesticide particles or molecules to form a protective layer on their surface, thereby physically isolating the interaction between pesticides and maintaining the stability of the pesticide compound system.

[0067] This invention does not specifically limit the type of pesticide formulation; any conventional pesticide formulation can be used. In this invention, the pesticide stabilizing nano-adjuvant forms a physical isolation layer on the surface of pesticide particles, thus making it applicable to pesticides of different formulations.

[0068] In this invention, the preferred method for applying the pesticide stabilizing nano-adjuvant in the mixing of water-soluble, water-emulsion, and water-suspended pesticide formulations is to mix the pesticide stabilizing nano-adjuvant with the pesticide formulation to be mixed evenly.

[0069] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0070] Example 1 A pesticide stabilizing nano-adjuvant is composed of a nano-dispersant, a dispersing stabilizer, and water; the mass ratio of the nano-dispersant, the dispersing stabilizer, and the water is 0.8 g: 2 g: 100 mL. The nano-dispersant is composed of amino-modified attapulgite and ZIF-8 loaded on the surface of the amino-modified attapulgite; the chemical bonding amount of amino groups in the amino-modified attapulgite is 0.6 mmol / g; the particle size of the ZIF-8 is 10 nm; the diameter of the attapulgite is 12 nm and the length is 800 nm; the mass content of the metal-organic framework in the nano-dispersant is 9%. The dispersing stabilizer is hexadecyl ammonium chloride, Tween 20, and Span 80, with a mass ratio of hexadecyl ammonium chloride, Tween 20, and Span 80 of 0.7:0.5:1.0; The preparation method of the pesticide stabilizing nano-adjuvant includes the following steps: (1) 0.8 g of attapulgite with a particle size of 12 × 800 nm was dispersed in a mixed solution of H2O:EtOH (ethanol) (volume ratio of 8:2) (volume of 100 mL) and sonicated for 30 min until uniformly dispersed to obtain an attapulgite suspension. 1.6 g of 3-aminopropyltriethoxysilane was added dropwise to the attapulgite suspension under stirring. Ammonia was added dropwise to adjust the pH of the solution to 8.5. The modification reaction was carried out under stirring at a temperature of 25 °C for 1 h. The mixture was then centrifuged, washed with water 3 times and dried to obtain amino-modified attapulgite. (2) 0.5g of the amino-modified attapulgite obtained in step (1) was immersed in 50mL of an aqueous solution containing 1g of zinc sulfate. After stirring for 1h, the mixture was centrifuged and washed with water 3 times to obtain amino-modified attapulgite that adsorbed zinc ions. The amino-modified attapulgite that adsorbed zinc ions was dispersed in 50mL of water, and then 50mL of an aqueous solution containing 4g of 2-methylimidazole (concentration of 0.97mol / L) was added. The mixture was stirred at 25℃ for 4h, then centrifuged, washed with water 3 times, and dried at 60℃ for 8h to obtain a nano-dispersant. (3) Mix 0.8g of the nano-dispersant obtained in step (2) with 70mL of water until homogeneous, and mix with 2g of dispersant stabilizer. Stir at 10000rpm for 3min until homogeneous emulsification. Add the mixture to 100mL to obtain the pesticide stabilized nano-adjuvant.

[0071] The SEM image of the attapulgite soil used in this embodiment is as follows: Figure 3 As shown, the SEM image of the prepared nano-dispersant is as follows. Figure 4 As shown. From Figure 3 and Figure 4 It can be seen that the dispersibility of attapulgite in the nano-dispersant prepared by this invention is not significantly different, but obvious nanoparticles, namely ZIF-8, appear on the surface of attapulgite.

[0072] The infrared spectra of the attapulgite clay and the prepared nano-dispersant used in this embodiment are as follows: Figure 5 As shown. From Figure 5 It can be seen that the nano-dispersant (i.e., the composite attapulgite shown in the figure) is superior to the attapulgite 3200~2800cm³. -1 The decrease in absorbance at the nano-dispersant indicates a reduction in the number of hydroxyl groups on the surface of the nano-dispersant, and the fusion of absorption peaks at the carboxyl groups, both of which indicate that the nano-dispersant was successfully synthesized.

[0073] A photograph of the pesticide-stabilizing nano-adjuvant prepared in this embodiment is shown below. Figure 6 As shown. From Figure 6 It can be seen that the pesticide stabilizing nano-adjuvant prepared by this invention is a stable dispersion.

[0074] Example 2 A pesticide stabilizing nano-adjuvant is composed of a nano-dispersant, a dispersing stabilizer, and water; the mass ratio of the nano-dispersant, the dispersing stabilizer, and the water is 0.4 g: 2 g: 100 mL. The nano-dispersant is composed of amino-modified attapulgite and ZIF-8 loaded on the surface of the amino-modified attapulgite; the chemical bonding amount of amino groups in the amino-modified attapulgite is 0.4 mmol / g; the diameter of the ZIF-8 is 10 nm; the diameter of the attapulgite is 12 nm and the length is 800 nm; the mass content of the metal-organic framework in the nano-dispersant is 6%. The dispersing stabilizer is hexadecyl ammonium chloride, Tween 20, and Span 80, with a mass ratio of hexadecyl ammonium chloride, Tween 20, and Span 80 of 0.5:0.5:1. The preparation method of the pesticide stabilizing nano-adjuvant includes the following steps: (1) 0.8 g of attapulgite with a particle size of 12 × 800 nm was ultrasonically dispersed in a mixed solution of H2O:EtOH (volume ratio of 8:2) (volume of 100 mL) for 30 min until it was uniformly dispersed to obtain an attapulgite suspension. 0.8 g of 3-aminopropyltriethoxysilane was added dropwise to the attapulgite suspension under stirring. Ammonia was added dropwise to adjust the pH of the solution to 8.5. The modification reaction was carried out under stirring at a temperature of 25 °C for 1 h. The mixture was then centrifuged, washed with water 3 times and dried to obtain amino-modified attapulgite. (2) 0.5g of the amino-modified attapulgite obtained in step (1) was immersed in 50mL of an aqueous solution containing 0.6g of zinc sulfate. After stirring for 1h, the mixture was centrifuged and washed three times with water to obtain amino-modified attapulgite that adsorbed zinc ions. The amino-modified attapulgite that adsorbed zinc ions was dispersed in 50mL of water, and then 50mL of an aqueous solution containing 2.5g of 2-methylimidazole was added. The mixture was stirred and reacted at 25℃ for 4h, then centrifuged, washed three times with water, and dried at 60℃ for 8h to obtain a nano-dispersant. (3) Mix 0.4g of the nano-dispersant obtained in step (2) with 70mL of water until homogeneous, and mix with 2g of dispersant stabilizer. Stir at 10000rpm in a shear emulsifier for 3min until homogeneous. Add the mixture to 100mL to obtain the pesticide stabilized nano-adjuvant.

[0075] Application Example 1 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to pyraclostrobin and mixed evenly by mechanical stirring at 200-300 rpm to obtain a pyraclostrobin mixture; wherein the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of pyraclostrobin.

[0076] Application Example 2 The difference from Application Example 1 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 10% of the mass of pyraclostrobin.

[0077] Application Example 3 The difference from Application Example 1 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 15% of the mass of pyraclostrobin.

[0078] Application Example 4 The difference from Application Example 1 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 20% of the mass of pyraclostrobin.

[0079] Comparative Application Example 1 The difference from Application Example 1 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 0% of the mass of pyraclostrobin.

[0080] Test Example 1 Photos of the pyraclostrobin mixture obtained from Application Examples 1-4 and Comparative Application Example 1 after standing for 0h, 2h, and 24h are shown below. Figure 7 As shown. In Figure 7 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 7 (a) to (c) show, from left to right, the pyraclostrobin mixtures obtained from Application Examples 1 to 4 and Comparative Application Example 1.

[0081] Application Example 5 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to abamectin and spirodiclofen, and the mixture was stirred mechanically at 200-300 rpm to obtain an abamectin-spirodiclofen mixture; wherein the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of abamectin-spirodiclofen.

[0082] Application Example 6 The difference from Application Example 5 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of abamectin-spirodiclofen.

[0083] Application Example 7 The difference from Application Example 5 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of abamectin-spirodiclofen.

[0084] Application Example 8 The difference from Application Example 5 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 20% of the mass of abamectin-spirodiclofen.

[0085] Comparative Application Example 2 The difference from Application Example 5 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 0% of the mass of abamectin-spirodiclofen.

[0086] Test Example 2 Photos of the abamectin-spirodiclofen mixture obtained from Application Examples 5-8 and Comparative Application Example 2 after standing for 0h, 2h, and 24h are shown below. Figure 8 As shown. In Figure 8 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 8 (a) to (c) show, from left to right, the abamectin-spirodiclofen mixtures obtained from Application Examples 5 to 8 and Comparative Application Example 2.

[0087] Application Example 9 The pesticide stabilizing nano-adjuvant prepared in Example 1 was added to thiophanate-methyl and mixed evenly by mechanical stirring at 200-300 rpm to obtain a thiophanate-methyl mixture; wherein, the mass of the pesticide stabilizing nano-adjuvant accounted for 5% of the mass of thiophanate-methyl.

[0088] Application Example 10 The difference from Application Example 9 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of thiophanate-methyl.

[0089] Application Example 11 The difference from Application Example 9 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of thiophanate-methyl.

[0090] Application Example 12 The difference from Application Example 9 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of thiophanate-methyl.

[0091] Comparative Application Example 3 The difference from Application Example 9 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the mass of thiophanate-methyl.

[0092] Test Example 3 Photos of the thiophanate-methyl mixture obtained from Application Examples 9-12 and Comparative Application Example 3 after standing for 0h, 2h, and 24h are shown below. Figure 9 As shown. In Figure 9 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 9 (a) to (c) show, from left to right, the methyl thiophanate mixtures obtained from Application Examples 9 to 12 and Comparative Application Example 3.

[0093] Application Example 13 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to thiamethoxam and mixed evenly by mechanical stirring at 200-300 rpm to obtain a thiamethoxam mixture; wherein the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of thiamethoxam.

[0094] Application Example 14 The difference from Application Example 13 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of thiamethoxam.

[0095] Application Example 15 The difference from Application Example 13 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of thiamethoxam.

[0096] Application Example 16 The difference from Application Example 13 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of thiamethoxam.

[0097] Comparative Application Example 4 The difference from Application Example 13 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the mass of thiamethoxam.

[0098] Test Example 4 Photos of the thiamethoxam mixtures obtained from Application Examples 13-16 and Comparative Application Example 4 after standing for 0h, 2h, and 24h are shown below. Figure 10 As shown. In Figure 10 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 10(a) to (c) show, from left to right, the thiamethoxam mixtures obtained from Application Examples 13 to 16 and Comparative Application Example 4.

[0099] Application Example 17 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to abamectin·high-chlorine-fluoride and mixed evenly by mechanical stirring at 200~300 rpm to obtain a mixture of abamectin·high-chlorine-fluoride; wherein, the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of abamectin·high-chlorine-fluoride.

[0100] Application Example 18 The difference from Application Example 17 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 10% of the mass of abamectin-chlorofluorocarbon.

[0101] Application Example 19 The difference from Application Example 17 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of abamectin·perchlorofluorocarbon.

[0102] Application Example 20 The difference from Application Example 17 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of abamectin·perchlorofluorocarbon.

[0103] Comparative Application Example 5 The difference from Application Example 17 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the mass of abamectin-chlorofluorocarbon.

[0104] Test Example 5 The photographs of the abamectin-high chlorofluorocarbon mixture obtained from Application Examples 17-20 and Comparative Application Example 5 after standing for 0h, 2h, and 24h are shown below. Figure 11 As shown. In Figure 11 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 11 (a) to (c) show, from left to right, the abamectin-perchloride-fluoride mixtures obtained from application examples 17 to 20 and comparative application example 5.

[0105] Application Example 21 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to chlorfenapyr and mixed evenly by mechanical stirring at 200-300 rpm to obtain a chlorfenapyr-chlorfenapyr mixture; wherein the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of chlorfenapyr-chlorfenapyr.

[0106] Application Example 22 The difference from Application Example 21 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 10% of the mass of chlorfenapyr·tebufenozide.

[0107] Application Example 23 The difference from Application Example 21 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 15% of the mass of chlorfenapyr·tebufenozide.

[0108] Application Example 24 The difference from Application Example 21 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 20% of the mass of chlorfenapyr·tebufenozide.

[0109] Comparative Application Example 6 The difference from Application Example 21 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 0% of the mass of chlorfenapyr·tebufenozide.

[0110] Test Example 6 Photos of the lufenuron-chlorfenapyr mixture obtained from Application Examples 21-24 and Comparative Application Example 6 after standing for 0h, 2h, and 24h are shown below. Figure 12 As shown. In Figure 12 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 12 (a) to (c) show, from left to right, the solutions of chlorfenapyr and chlorfenapyr obtained from application examples 21 to 24 and comparative application example 6, respectively.

[0111] Application Example 25 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to tebuconazole and mixed evenly by mechanical stirring at 200-300 rpm to obtain a tebuconazole mixture; wherein the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of tebuconazole.

[0112] Application Example 26 The difference from Application Example 25 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of tebuconazole.

[0113] Application Example 27 The difference from Application Example 25 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of tebuconazole.

[0114] Application Example 28 The difference from Application Example 25 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of tebuconazole.

[0115] Comparative Application Example 7 The difference from Application Example 25 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the mass of tebuconazole.

[0116] Test Example 7 Photos of the tebuconazole mixtures obtained from Application Examples 25-28 and Comparative Application Example 7 after standing for 0h, 2h, and 24h are shown below. Figure 13 As shown. In Figure 13 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 13 (a) to (c) show, from left to right, the tebuconazole mixtures obtained from Application Examples 25 to 28 and Comparative Application Example 7.

[0117] Application Example 29 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to octochlor acetate and mixed evenly by mechanical stirring at 200-300 rpm to obtain an octochlor acetate mixture; wherein, the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of octochlor acetate.

[0118] Application Example 30 The difference from Application Example 29 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of octochlor acetate.

[0119] Application Example 31 The difference from Application Example 29 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of octochlor acetate.

[0120] Application Example 32 The difference from Application Example 29 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of octochlor acetate.

[0121] Comparative Application Example 8 The difference from Application Example 29 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 0% of the mass of octochlor acetate.

[0122] Test Example 8 The photographs of the octochlor acetate mixture obtained from Application Examples 29-32 and Comparative Application Example 8 after standing for 0h, 2h, and 24h are shown below. Figure 14 As shown. In Figure 14 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 14 (a) to (c) show, from left to right, the octochlor acetate mixtures obtained from Application Examples 29 to 32 and Comparative Application Example 8.

[0123] from Figures 7-14 It can be seen that when the pesticide stabilizing nano-adjuvant prepared in this invention is added to single pesticides such as pyraclostrobin, abamectin-spirodiclofen, thiophanate-methyl, thiamethoxam, abamectin-chlorfenapyr, chlorfenapyr-tebuconazole, tebuconazole, and cymoxanil acetate, the pesticides can be stably dispersed. When the amount added is 5% to 20%, the effect increases with the amount added, and it will not cause pesticide flocculation or precipitation.

[0124] Application Example 33 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was mixed with octochlor acetate and then compounded with abamectin-spirodiclofen (the ratio of octochlor acetate to abamectin-spirodiclofen formulation was 1:4). The mixture was stirred mechanically at 200-300 rpm to obtain a compound solution. The mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the total mass of octochlor acetate and abamectin-spirodiclofen.

[0125] Application Example 34 The difference from Application Example 33 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of cymoxanil acetate and abamectin-spirodiclofen.

[0126] Application Example 35 The difference from Application Example 33 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the total mass of cymoxanil acetate and abamectin-spirodiclofen.

[0127] Application Example 36 The difference from Application Example 33 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of cymoxanil acetate and abamectin-spirodiclofen.

[0128] Comparative Application Example 9 The difference from Application Example 33 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the total mass of cymoxanil acetate and abamectin-spirodiclofen.

[0129] Test Example 9 Photos of the compound solutions obtained from Application Examples 33-36 and Comparative Application Example 9 after standing for 0h, 2h, and 24h are shown below. Figure 15 As shown. In Figure 15 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 15 From left to right in (a) to (c) are the compound solutions obtained from Application Examples 33 to 36 and Comparative Application Example 9.

[0130] Application Example 37 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was mixed with octochlor acetate and then compounded with pyraclostrobin (the ratio of octochlor acetate to pyraclostrobin formulation was 1:4). The mixture was stirred mechanically at 200-300 rpm to obtain a compound solution. The mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the total mass of octochlor acetate and pyraclostrobin.

[0131] Application Example 38 The difference from Application Example 37 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of cymoxanil acetate and pyraclostrobin.

[0132] Application Example 39 The difference from Application Example 37 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 15% of the total mass of cymoxanil acetate and pyraclostrobin.

[0133] Application Example 40 The difference from Application Example 37 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of cymoxanil acetate and pyraclostrobin.

[0134] Comparative Application Example 10 The difference from Application Example 37 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the total mass of cymoxanil acetate and pyraclostrobin.

[0135] Test Case 10 Photos of the compound solutions obtained from Application Examples 37-40 and Comparative Application Example 10 after standing for 0h, 2h, and 24h are shown below. Figure 16 As shown. In Figure 16 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 16 From left to right in (a) to (c) are the compound solutions obtained from application examples 37 to 40 and the comparative application example 10.

[0136] Application Example 41 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was mixed with octochlor acetate and then compounded with thiophanate-methyl (the ratio of octochlor acetate to thiophanate-methyl was 1:4). The mixture was stirred mechanically at 200-300 rpm to obtain a compound solution. The mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the total mass of octochlor acetate and thiophanate-methyl.

[0137] Application Example 42 The difference from Application Example 41 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of cymoxanil acetate and thiophanate-methyl.

[0138] Application Example 43 The difference from Application Example 41 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the total mass of cymoxanil acetate and thiophanate-methyl.

[0139] Application Example 44 The difference from Application Example 41 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of cymoxanil acetate and thiophanate-methyl.

[0140] Comparative Application Example 11 The difference from Application Example 41 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the total mass of cymoxanil acetate and thiophanate-methyl.

[0141] Test Example 11 Photos of the compound solutions obtained from Application Examples 41-44 and Comparative Application Example 11 after standing for 0h, 2h, and 24h are shown below. Figure 17 As shown. In Figure 17 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 17 (a) to (c) show, from left to right, the compound solutions obtained from application examples 41 to 44 and comparative application example 11.

[0142] Application Example 45 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was mixed with octochlor acetate and then compounded with tebuconazole (the ratio of octochlor acetate to tebuconazole was 1:4). The mixture was stirred mechanically at 200-300 rpm to obtain a compound solution. The mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the total mass of octochlor acetate and tebuconazole.

[0143] Application Example 46 The difference from Application Example 45 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of cymoxanil acetate and tebuconazole.

[0144] Application Example 47 The difference from Application Example 45 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the total mass of cymoxanil acetate and tebuconazole.

[0145] Application Example 48 The difference from Application Example 45 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of cymoxanil acetate and tebuconazole.

[0146] Comparative Application Example 12 The difference from Application Example 45 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the total mass of cymoxanil acetate and tebuconazole.

[0147] Test Example 12 Photos of the compound solutions obtained from Application Examples 45-48 and Comparative Application Example 12 after standing for 0h, 2h, and 24h are shown below. Figure 18 As shown. In Figure 18 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 18 (a) to (c) show, from left to right, the compound solutions obtained from Application Examples 45 to 48 and Comparative Application Example 12.

[0148] from Figures 15-19 It can be seen that, due to its inherent properties, octochlor acetate is prone to flocculation and sedimentation when compounded with various pesticide formulations (abamectin·spirodiclofen, pyraclostrobin, thiophanate-methyl, tebuconazole, abamectin·chlorpyrifos). When the pesticide-stabilizing nano-adjuvant prepared in this invention is added at 5%~20% of the total mass of the compound, the dispersibility of the compound system significantly increases, with the effect improving with increasing addition amount. This indicates that the pesticide-stabilizing nano-adjuvant of this invention significantly improves the stability of compound pesticides and can meet the spraying requirements.

[0149] Application Example 49 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was mixed with octochlor acetate and then compounded with abamectin-chlorofluorocarbon (the ratio of octochlor acetate to abamectin-chlorofluorocarbon is 1:4). The mixture was stirred mechanically at 200-300 rpm to obtain a compound solution. The mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the total mass of octochlor acetate and abamectin-chlorofluorocarbon.

[0150] Application Example 50 The difference from Application Example 49 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of octochlor acetate and abamectin·chlorofluorocarbon.

[0151] Application Example 51 The difference from Application Example 49 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the total mass of cymoxanil acetate and abamectin-chlorofluorocarbon.

[0152] Application Example 52 The difference from Application Example 49 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of octochlor acetate and abamectin-high chlorofluorocarbon.

[0153] Comparative Application Example 13 The difference from Application Example 49 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the total mass of octochlor acetate and abamectin·chlorofluorocarbon.

[0154] Test Example 13 Photos of the compound solutions obtained from Application Examples 49-52 and Comparative Application Example 13 after standing for 0h, 2h, and 24h are shown below. Figure 19 As shown. In Figure 19 In the table, (a) represents 0 hours of settling; (b) represents 2 hours of settling; and (c) represents 24 hours of settling. Figure 19 (a) to (c) show, from left to right, the compound solutions obtained from Application Examples 49 to 52 and Comparative Application Example 13.

[0155] Application Example 53 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was added to pyraclostrobin and mixed thoroughly by mechanical stirring at 200-300 rpm to obtain a pyraclostrobin mixture; wherein the mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the mass of pyraclostrobin. The pyraclostrobin mixture was added to a liquid culture medium at a concentration of 50% inhibition rate of the pyraclostrobin technical grade, and approximately 0.1 g of *Botrytis cinerea* was inoculated. After culturing in the liquid culture medium for 3 days, the mixture was removed, washed, and dried to determine its dry weight. The inhibition rate was calculated as (blank dry weight - experimental group dry weight) / blank dry weight, where the blank group consisted of bacteria obtained from culture without pesticide addition.

[0156] Application Example 54 The difference from Application Example 53 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 10% of the mass of pyraclostrobin.

[0157] Application Example 55 The difference from Application Example 53 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 15% of the mass of pyraclostrobin.

[0158] Application Example 56 The difference from Application Example 53 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 20% of the mass of pyraclostrobin.

[0159] Comparative Application Example 14 The difference from Application Example 53 is that the mass of the pesticide-stabilizing nano-adjuvant accounts for 0% of the mass of pyraclostrobin.

[0160] Application Example 57 The difference from Application Example 53 is that the agent used is thiophanate-methyl, and the mass of the pesticide stabilizing nano-adjuvant accounts for 5% of the mass of thiophanate-methyl.

[0161] Application Example 58 The difference from Application Example 53 is that the agent used is thiophanate-methyl, and the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of thiophanate-methyl.

[0162] Application Example 59 The difference from Application Example 53 is that the agent used is thiophanate-methyl, and the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of thiophanate-methyl.

[0163] Application Example 60 The difference from Application Example 53 is that the agent used is thiophanate-methyl, and the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of thiophanate-methyl.

[0164] Comparative Application Example 15 The difference from Application Example 53 is that the agent used is thiophanate-methyl, and the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the mass of thiophanate-methyl.

[0165] Application Example 61 The difference from Application Example 53 is that the agent used is tebuconazole, and the mass of the pesticide stabilizing nano-adjuvant accounts for 5% of the mass of tebuconazole.

[0166] Application Example 62 The difference from Application Example 53 is that the agent used is tebuconazole, and the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of tebuconazole.

[0167] Application Example 63 The difference from Application Example 53 is that the agent used is tebuconazole, and the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of tebuconazole.

[0168] Application Example 64 The difference from Application Example 53 is that the agent used is tebuconazole, and the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of tebuconazole.

[0169] Comparative Application Example 16 The difference from Application Example 53 is that the agent used is tebuconazole, and the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the mass of tebuconazole.

[0170] Application Example 65 The difference from Application Example 53 is that the agent used is octochlor acetate, and the mass of the pesticide stabilizing nano-adjuvant accounts for 5% of the mass of octochlor acetate.

[0171] Application Example 66 The difference from Application Example 53 is that the agent used is octochlor acetate, and the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the mass of octochlor acetate.

[0172] Application Example 67 The difference from Application Example 53 is that the agent used is octochlor acetate, and the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the mass of octochlor acetate.

[0173] Application Example 68 The difference from Application Example 53 is that the agent used is octochlor acetate, and the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the mass of octochlor acetate.

[0174] Comparative Application Example 17 The difference from Application Example 53 is that the agent used is octochlor acetate, and the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the mass of octochlor acetate.

[0175] Test Example 14 The antibacterial rate results obtained from Application Examples 53-68 and Comparative Application Examples 14-17 are as follows: Figure 20 As shown.

[0176] Application Example 69 The pesticide-stabilizing nano-adjuvant prepared in Example 1 was mixed with octochlor acetate and then compounded with pyraclostrobin (the ratio of octochlor acetate to pyraclostrobin formulation was 1:4). The mixture was stirred mechanically at 200-300 rpm until homogeneous, yielding a compound solution. The mass of the pesticide-stabilizing nano-adjuvant accounted for 5% of the total mass of octochlor acetate and pyraclostrobin. The compound solution was added to a liquid culture medium at a concentration that achieved a 50% inhibition rate of pyraclostrobin technical grade, and approximately 0.1 g of *Botrytis cinerea* was inoculated. After culturing in the liquid culture medium for 3 days, the mixture was removed, washed, and dried to determine its dry weight. The inhibition rate was calculated as (blank dry weight - experimental group dry weight) / blank dry weight, where the blank group consisted of bacteria obtained from culture without pesticide addition.

[0177] Application Example 70 The difference from Application Example 69 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of cymoxanil acetate and pyraclostrobin.

[0178] Application Example 71 The difference from Application Example 69 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the total mass of cymoxanil acetate and pyraclostrobin.

[0179] Application Example 72 The difference from Application Example 69 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of cymoxanil acetate and pyraclostrobin.

[0180] Comparative Application Example 18 The difference from Application Example 69 is that the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the total mass of cymoxanil acetate and pyraclostrobin.

[0181] Application Example 73 The difference from application example 69 is that it is combined with thiophanate-methyl (the ratio of octochlor acetate to thiophanate-methyl is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 5% of the total mass of octochlor acetate and thiophanate-methyl.

[0182] Application Example 74 The difference from application example 69 is that it is combined with thiophanate-methyl (the ratio of octochlor acetate to thiophanate-methyl is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of octochlor acetate and thiophanate-methyl.

[0183] Application Example 75 The difference from application example 69 is that it is combined with thiophanate-methyl (the ratio of octochlor acetate to thiophanate-methyl is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the total mass of octochlor acetate and thiophanate-methyl.

[0184] Application Example 76 The difference from application example 69 is that it is combined with thiophanate-methyl (the ratio of octochlor acetate to thiophanate-methyl is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of octochlor acetate and thiophanate-methyl.

[0185] Comparative Application Example 19 The difference from application example 69 is that when combined with thiophanate-methyl (the ratio of octochlor acetate to thiophanate-methyl is 1:4), the mass of the pesticide-stabilizing nano-adjuvant accounts for 0% of the total mass of octochlor acetate and thiophanate-methyl.

[0186] Application Example 77 The difference from application example 69 is that it is combined with tebuconazole (the ratio of octochlor acetate to tebuconazole is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 5% of the total mass of octochlor acetate and tebuconazole.

[0187] Application Example 78 The difference from application example 69 is that it is combined with tebuconazole (the ratio of octochlor acetate to tebuconazole is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 10% of the total mass of octochlor acetate and tebuconazole.

[0188] Application Example 79 The difference from Application Example 69 is that it is combined with tebuconazole (the ratio of octochlor acetate to tebuconazole is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 15% of the total mass of octochlor acetate and tebuconazole.

[0189] Application Example 80 The difference from application example 69 is that it is combined with tebuconazole (the ratio of octochlor acetate to tebuconazole is 1:4), and the mass of the pesticide stabilizing nano-adjuvant accounts for 20% of the total mass of octochlor acetate and tebuconazole.

[0190] Comparative Application Example 20 The difference from Application Example 69 is that when combined with tebuconazole (the ratio of octochlor acetate to tebuconazole is 1:4), the mass of the pesticide stabilizing nano-adjuvant accounts for 0% of the total mass of octochlor acetate and tebuconazole.

[0191] In application examples 33-52 and 69-80, the octochlor acetate was a water-soluble (SL) formulation, pyraclostrobin, abamectin·spirodiclofen, and abamectin·chlorfenapyr were suspension concentrates (SC), thiophanate-methyl was a wettable powder (WP), and tebuconazole was a water-dispersible granule (WG). The mixing ratio of octochlor acetate with each pesticide formulation was 1:4.

[0192] Test Example 15 The antibacterial rate results obtained from Application Examples 69-80 and Comparative Application Examples 18-20 are as follows: Figure 21 As shown.

[0193] from Figures 20-21 It can be seen that after adding the pesticide-stabilizing nano-adjuvant prepared in this invention, the inhibition rate of Botrytis cinerea is significantly improved in both single-agent and compound systems, indicating that the pesticide-stabilizing nano-adjuvant prepared in this invention can effectively improve the inhibitory effect of pesticides on Botrytis cinerea.

[0194] The results above show that the pesticide stabilizing nano-adjuvant prepared by the present invention can significantly improve the stability of pesticides after mixing. This is because the pesticide stabilizing nano-adjuvant prepared by the present invention utilizes the interaction between modified attapulgite and pesticide particles or molecules to form a protective layer on their surface, thereby physically isolating the interaction between pesticides. Therefore, it can be used to improve the stability of pesticide mixtures of various formulations, and the improvement of the suspension stability has a significant effect on the antibacterial performance of the agent.

[0195] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A pesticide stabilizing nano-adjuvant, comprising a nano-dispersant, a dispersing stabilizer, and water; wherein the mass ratio of the nano-dispersant, the dispersing stabilizer, and the water is (0.3~1.0) g : (0.5~2.5) g : 100 mL; The nano-dispersant comprises amino-modified attapulgite and a metal-organic framework supported on the surface of the amino-modified attapulgite.

2. The pesticide stabilizing nano-adjuvant according to claim 1, characterized in that, The attapulgite in the amino-modified attapulgite has a diameter of 10~30nm and a length of 800~1000nm.

3. The pesticide stabilizing nano-adjuvant according to claim 1 or 2, characterized in that, The amount of chemically bonded amino groups in the amino-modified attapulgite is 0.4~1.0 mmol / g.

4. The pesticide stabilizing nano-adjuvant according to claim 1, characterized in that, The metal-organic framework includes one or more of ZIF-8, copper-benzene-1,3,5-tricarboxylic acid, copper-lignin, and zinc-lignin.

5. The pesticide stabilizing nano-adjuvant according to claim 1, characterized in that, The particle size of the metal-organic framework is 3~15nm.

6. The pesticide stabilizing nano-adjuvant according to claim 1, characterized in that, The metal-organic framework in the nano-dispersant has a mass content of 3-10%.

7. The pesticide stabilizing nano-adjuvant according to claim 1, characterized in that, The dispersion stabilizer includes one or more of hexadecyl ammonium chloride, Tween 20, and Span 80.

8. A method for preparing the pesticide stabilizing nano-adjuvant according to any one of claims 1 to 7, comprising the following steps: (1) Mix attapulgite, amino modifier and solvent to carry out modification reaction to obtain amino-modified attapulgite; (2) The amino-modified attapulgite obtained in step (1) is mixed with the metal ion solution, centrifuged, washed and collected, redispersed in water and mixed with the ligand solution to carry out coordination modification reaction to obtain nano-dispersant; (3) The nano-dispersant obtained in step (2) is mixed with the dispersant stabilizer and water to obtain a pesticide-stabilizing nano-adjuvant.

9. The preparation method according to claim 8, characterized in that, The amino modifier in step (1) includes one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, guanidopropyltriethoxysilane and guanidopropyltrimethoxysilane.

10. The application of the pesticide-stabilizing nano-adjuvant according to any one of claims 1 to 7 or the pesticide-stabilizing nano-adjuvant prepared by the preparation method according to any one of claims 8 to 9 in the mixing of water-soluble, water-emulsion and water-suspended pesticide formulations.

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