A spray adjuvant for improving the stability of barrel mixing of pesticides for aerial spraying and its preparation method

Abstract

The present invention discloses a spray adjuvant for improving the tank mix stability of pesticides in aerial spraying and its preparation method, belonging to the technical field of aerial spraying adjuvants. The above-mentioned spray adjuvant for improving the tank mix stability of pesticides in aerial spraying is composed of the following components in parts by weight: 1.5 - 2 parts of dextrin; 0.5 - 1 part of Carbopol ETD 2020; 0.1 - 0.5 part of PAMAM solution; 0.01 - 0.05 part of Bis-MPA polyester-64-hydroxy; 5 - 12 parts of non-ionic surfactant; 0.1 - 0.5 part of thickener; 0.9 - 2.5 parts of ethylene glycol; 81.45 - 91.89 parts of water. The three-dimensional network structure synergistically cross-linked by dextrin, Carbopol ETD 2020, PAMAM and Bis-MPA polyester-64-hydroxy in the present invention has a good coating and suspension effect on pesticide particles, and has a very good stabilizing effect on most pesticide formulations, foliar fertilizers and their tank mix solutions.

Description

Technical Field

[0001] The present invention relates to the technical field of aerial spraying adjuvants, and particularly relates to a spray adjuvant for improving the tank mixing stability of aerial spraying pesticides and a preparation method thereof. Background Art

[0002] In current and future agricultural production in China, the shortage of labor has become one of the key factors restricting agricultural development. With the development of urbanization in China, rural labor has been continuously transferred to cities and towns. Therefore, the aerial spraying plant protection technology with safe operation, high spraying efficiency, less labor, water and pesticide conservation, and applicable to various terrains and crop growth periods has developed rapidly in China. Compared with countries such as Europe and America with concentrated arable land and high agricultural mechanization, the aerial spraying plant protection technology is more suitable for the small-scale operation environment in China with scattered arable land and diverse and complex terrains, especially suitable for food crops. For the same reason, the aerial spraying plant protection technology has also been widely applied in small-scale farming countries such as Japan and South Korea. In recent years, the aerial spraying plant protection technology in China has developed rapidly. As of mid-November 2020, according to preliminary statistics in 26 provinces, the number of plant protection drones in China has exceeded 100,000, and the total operation area is nearly 1 billion mu-times.

[0003] In actual aerial spraying operations, farmers often mix multiple pesticide formulations or foliar fertilizers in the tank. This can not only reduce the number of spraying times, reduce the loss of spraying equipment, save labor costs, but also achieve the purpose of delaying drug resistance and improving the control effect. The tank mixing technology of the "adjuvant + pesticide + fertilizer" system is becoming more and more popular among farmers. However, aerial spraying belongs to low-volume spraying, with an acreage liquid volume of only 1-2 L and a dilution ratio of only 30-50 times (the conventional spraying dilution ratio is 3000-5000 times). Therefore, for the tank mixing of conventional pesticide formulations, especially the tank mixing of pesticides of different dosage forms and foliar fertilizers, on the one hand, due to the high concentration of the liquid medicine, the spatial repulsive force between pesticide molecules is insufficient, resulting in the aggregation and instability of particles and oil droplets; on the other hand, a large number of positively and negatively charged ions are dispersed in the high-salt system containing foliar fertilizer, which will affect the charge balance of the pesticide system and reduce the electrostatic repulsion force of pesticide molecules, resulting in emulsion demulsification, reduction of the suspension rate of suspension, etc. In summary, unstable phenomena such as floating oil, flocculation, and precipitation (physical incompatibility) often occur in the aerial spraying pesticide tank mixing system, which may cause nozzle blockage, reduced drug efficacy, and even phytotoxicity. In addition, chemical reactions may also occur between the active ingredients of different pesticide formulations, resulting in the chemical inactivation of the active ingredients of pesticides (chemical incompatibility). Therefore, when mixing multiple pesticides in the tank, the ion type, ion concentration, interfacial tension, density, viscosity, and chargeability of the system should be fully considered.

[0004] However, compared with the booming development of the domestic plant protection UAV industry, the progress of some problems that urgently need to be solved in the field of low-altitude agricultural spraying is slow. Among them, an important problem is that the types and quality of preparations involved in low-altitude spraying are far from sufficient for actual use, and the functions of adjuvants are incomplete. At present, the number of ultra-low volume liquid agents registered in the pesticide market for aerial application is very small. As of April 2023, there are only 24, and the applicable crop types are few and the application scenarios are single, which severely limits the application of ultra-low volume liquid agents in the field of low-altitude spraying for plant protection. Therefore, in order to better play the role of conventional pesticide preparations in the field of low-altitude spraying for plant protection, pesticide preparations suitable for conventional spraying are often selected for low-fold dilution and supplemented with tank mix adjuvants during actual field application. At present, the functions of aerial application adjuvants on the market mainly focus on improving the anti-evaporation, anti-drift, deposition penetration and wetting absorption properties of the liquid medicine, such as CN107251895A, CN109699640A and CN110999903A, but there are few aerial application adjuvants in patents for the research and development of the stability of pesticide tank mix systems. Most of the commercially available aerial application adjuvants for stabilizing pesticide tank mix systems achieve the purpose of reducing the sedimentation of the liquid medicine and stabilizing the liquid medicine by adding a large amount of high molecular compounds to increase the viscosity of the liquid medicine. This kind of liquid medicine stabilization mechanism usually has poor stabilization effect and short stabilization time, and is not suitable for high-salt systems. If synthetic polymers are selected, there are also problems such as high cost and easy environmental residues. At the same time, the increase in the viscosity of the liquid medicine system is not conducive to liquid medicine spraying, and it is easy to cause nozzle blockage and the generation of large droplets. Therefore, there is an urgent need for an aerial application adjuvant in aerial application plant protection operations with a novel stabilization mechanism, suitable for the aerial application pesticide tank mix system, low cost, good stabilization effect (stable for more than 8 hours), suitable for high-salt systems, and natural ingredients, safe and biodegradable. Summary of the Invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a spray adjuvant for improving the stability of aerial application pesticide tank mix and its preparation method, which solves the problem of low stability of the high-salt pesticide tank mix system in the process of multi-drug mixing during aerial application under low-volume spraying in the prior art.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] On the one hand, the present invention provides a spray adjuvant for improving the stability of aerial application pesticide tank mix, abbreviated as aerial application adjuvant, which is composed of the following components in parts by weight:

[0008]

[0009] The content of the active ingredient in the PAMAM solution is 5-20 wt%.

[0010] Preferably, the non-ionic surfactant is fatty alcohol polyoxyethylene ether phosphate and / or Tween 80;

[0011] The thickener is guar gum and / or xanthan gum.

[0012] Preferably, the spray adjuvant for improving the tank mix stability of aerial spraying pesticides is composed of the following components in parts by weight:

[0013]

[0014] On the other hand, the present invention provides a preparation method of the above-mentioned spray adjuvant for improving the tank mix stability of aerial spraying pesticides, including:

[0015] Step 1: Add a thickener and ethylene glycol into a glass bottle according to a weight ratio, stir for 2 min - 10 min, and the rotation speed is 100 RPM;

[0016] Step 2: Add water to the mixture obtained in Step 1 according to a weight ratio, and then add dextrin, Carbopol ETD 2020, PAMAM solution, Bis-MPA polyester-64-hydroxy and a non-ionic surfactant according to a weight ratio and stir for 2 min - 30 min, with a rotation speed of 100 - 500 RPM; stir and dissolve until evenly dispersed to obtain the spray adjuvant for improving the tank mix stability of aerial spraying pesticides, abbreviated as aerial spraying adjuvant.

[0017] On yet another aspect, the present invention provides a pesticide composition, including the above-mentioned aerial spraying adjuvant. Specifically, it is composed of the following components in parts by weight:

[0018]

[0019] Furthermore, the pesticide formulation is one or more of soluble powder, wettable powder, water dispersible granule, suspension concentrate, microemulsion, soluble concentrate, emulsion in water, aqueous solution, emulsifiable concentrate; the phosphorus and potassium fertilizers are potassium dihydrogen phosphate and / or dipotassium hydrogen phosphate.

[0020] Preferably, the above-mentioned pesticide composition is composed of the following components in parts by weight:

[0021]

[0022] On still another aspect, the present invention provides a preparation method of the above-mentioned pesticide composition, including:

[0023] Step 1: Add water into a container according to a weight;

[0024] Step 2: Sequentially add the aerial spraying adjuvant, pesticide formulation and phosphorus and potassium fertilizers according to a weight and stir evenly to obtain the said liquid medicine.

[0025] Preferably, in the step 2, the addition order of the pesticide formulations is soluble powder, wettable powder, water dispersible granule, suspension concentrate, microemulsion, soluble solution, emulsion in water, aqueous solution, emulsifiable concentrate; after adding each pesticide formulation, it is immediately stirred and dispersed evenly, and then the next pesticide formulation is added.

[0026] The three-dimensional network structure formed by the polymer chains of dextrin, Carbopol ETD 2020, PAMAM and Bis-MPA polyester-64-hydroxy in water can be intertwined and cross-linked through hydrogen bonds and hydrophobic interactions, etc., coating and suspending pesticide particles, playing a role in synergistically stabilizing the aerial spraying pesticide tank mixing system; in addition, the sprayed liquid medicine contains polymer molecules such as dextrin, which can increase the droplet size, making the pesticide droplets have a certain anti-drift ability; the three-dimensional space network structure formed in the liquid medicine can increase the energy dissipation when the pesticide droplets collide with the target leaf surface, and at the same time form a hydrophilic polymer film layer on the target leaf surface, building a hydrophilic trap, increasing the hydrophilicity and water absorption performance of the leaf surface, reducing the interfacial energy, reducing the contact angle of the droplets on the target leaf surface, and helping to realize the transformation of the wetting and adhesion behavior of the droplets on the leaf surface from the Cassie mode to the Wenzel mode (see attachment Figure 5 ).), thereby achieving the purpose of inhibiting droplet bounce, promoting the wetting and spreading of the liquid medicine and increasing the deposition amount of the liquid medicine; reducing the surface tension of the liquid medicine and improving the utilization efficiency of the pesticide. At the same time, the protective layer formed on the surface of the target crop can block the invasion of pests and diseases to the plant, achieving the purpose of improving the control effect. After being formulated into a liquid medicine, due to the coating and suspension effect of the three-dimensional network structure formed by the synergistic cross-linking of polymer molecules such as dextrin on the pesticide particles, and the adsorption effect on phosphorus and potassium fertilizers, the liquid medicine also has a certain slow-release function after being sprayed.

[0027] Thickeners, also known as gelling agents, are substances that can increase the viscosity of latex and liquids. Thickeners can increase the system viscosity, keep the pesticide tank mixing system in a uniform and stable suspension state or emulsion state, or form a gel to improve the stability of the pesticide tank mixing system; most thickeners have an emulsifying effect at the same time. Thickeners can be divided into two categories: natural and synthetic. The thickeners selected in the present invention are natural products, which are prepared from plants and seaweeds containing polysaccharide viscous substances, such as guar gum, xanthan gum, β-cyclodextrin, sodium alginate, gelatin, arabic gum and agar.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The preparation process of the present invention is simple, the equipment requirements are low, and the raw materials are easy to obtain. Among them, dextrin is an intermediate product of starch decomposition, which is safe and biodegradable. The three-dimensional network structure formed by the polymer chains of dextrin, Carbopol ETD 2020, PAMAM and Bis-MPA polyester-64-hydroxy in water can be intertwined and cross-linked through hydrogen bonds and hydrophobic interactions, etc., playing a role in synergistically stabilizing the aerial spraying pesticide tank mixing system.

[0030] The aerial spraying adjuvant prepared by the present invention has diverse functions. When applied to a pesticide tank-mixed liquid containing multiple pesticides including phosphorus and potassium fertilizers, the antagonistic destructive effect of the phosphorus and potassium fertilizers on the pesticide system can be effectively reduced, thereby improving the stability of the liquid. Since the aerial spraying adjuvant of the present invention hardly increases the viscosity of the system at the use concentration, the liquid has good fluidity and can be sprayed as finer droplets. At the same time, the sprayed liquid droplets have a certain anti-drift ability. The present invention can achieve the purposes of suppressing droplet bouncing, promoting liquid wetting and spreading, and increasing liquid deposition, reducing liquid surface tension, and improving the utilization efficiency of the agent. At the same time, the protective layer formed on the surface of the target crop can block the invasion of pests and diseases on the plant, thereby achieving the purpose of improving the prevention effect. Finally, due to the coating and suspension effect of the three-dimensional network structure of the synergistic cross-linked polymer molecules such as dextrin on the pesticide particles, and the adsorption effect on the phosphorus and potassium fertilizers, the liquid after spraying also has a certain slow-release function.

[0031] The present invention first dissolves the thickener in ethylene glycol and stirs uniformly; then dissolves the mixture of the thickener and ethylene glycol in water and stirs uniformly. This method can increase the speed of thickener dispensing, achieve rapid release of thickener viscosity, and further improve the stability of the pesticide mixing system. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 Schematic diagram of the molecular structure of dextrin;

[0033] Figure 2 This is the general structural formula of Carbopol ETD 2020;

[0034] Figure 3 Schematic diagram of the molecular structure of PAMAM;

[0035] Figure 4 Schematic diagram of the molecular structure of Bis-MPA polyester-64-hydroxy;

[0036] Figure 5 Schematic diagram of the contact angle model of a liquid droplet on a rough solid surface. DETAILED DESCRIPTION

[0037] In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, a detailed description will be given below with reference to the accompanying drawings and specific embodiments.

[0038] Unless otherwise specified, the reagents and materials used in the examples and comparative examples were commercially available. Dextrin was purchased from Beijing Bailingwei Technology Co., Ltd.; Carbopol ETD 2020 was purchased from Lubrizol Corporation; PAMAM solution (10 wt%) and Bis-MPA polyester-64-hydroxy (≥97%) were purchased from Sigma-Aldrich; the relevant results are shown inFigures 1-4 ; The non-ionic surfactant is selected from at least one of AEO-9P and TW80, purchased from Shanghai Yuanye Bio-Technology Co., Ltd. and Aladdin respectively, both of which are chemically pure; the thickener is selected from at least one of GG and XG, both purchased from Beijing Vokai Biotechnology Co., Ltd., both of which are chemically pure; ethylene glycol is purchased from Aladdin and is chemically pure. The 25% pymetrozine suspension, 2% emamectin benzoate * 10% chlorfenapyr suspension and 10% thifluzamide * 22% tebuconazole suspension can be purchased from Shaanxi Biostar Crop Science Co., Ltd.; the 14% trifloxystrobin * 28% tebuconazole suspension can be purchased from Shenzhen Noposion Agrochemicals Co., Ltd.; the 5% chlorantraniliprole suspension can be purchased from FMC Corporation; the 0.01% brassinolide emulsifiable concentrate can be purchased from Fujian Xinnong Dazheng Biotechnology Co., Ltd.; potassium dihydrogen phosphate or dipotassium hydrogen phosphate can be purchased from Sinopharm Chemical Reagent Co., Ltd., etc.

[0039] A spray adjuvant for improving the tank mix stability of aerial application pesticides and its preparation method are as follows in specific embodiments.

[0040] Example 1

[0041] A spray adjuvant 1# for improving the tank mix stability of aerial application pesticides, which is composed of the following components in parts by weight:

[0042] Dextrin 1.5 parts by weight, Carbopol ETD 2020 0.5 parts by weight, PAMAM solution 0.1 parts by weight, Bis-MPA polyester-64-hydroxy 0.01 parts by weight, AEO-9P 5 parts by weight, GG 0.1 parts by weight, dispersion medium ethylene glycol 0.9 parts by weight, water 91.89 parts by weight.

[0043] Preparation method:

[0044] Step 1: Add 0.1 parts by weight of GG and 0.9 parts by weight of ethylene glycol into a glass bottle, stir for 2 min at a rotation speed of 100 RPM;

[0045] Step 2: Add 91.89 parts by weight of water to the mixture in "Step 1", then add 1.5 parts by weight of dextrin, 0.5 parts by weight of Carbopol ETD 2020, 0.1 parts by weight of PAMAM solution, 0.01 parts by weight of Bis-MPA polyester-64-hydroxy and 5 parts by weight of AEO-9P, stir for 2 min at a rotation speed of 100 RPM; stir and dissolve until evenly dispersed, then the spray adjuvant 1# for improving the tank mix stability of aerial application pesticides is obtained.

[0046] Example 2

[0047] A spray adjuvant 2# for improving the tank mix stability of aerial application pesticides, which is composed of the following components in parts by weight:

[0048] 2 parts by weight of dextrin, 1 part by weight of Carbopol ETD 2020, 0.5 part by weight of PAMAM solution, 0.05 part by weight of Bis-MPA polyester-64-hydroxy, 12 parts by weight of AEO-9P, 0.5 part by weight of XG, 2.5 parts by weight of dispersing medium ethylene glycol, 81.45 parts by weight of water.

[0049] Preparation method:

[0050] Step 1: Add 0.5 part by weight of XG and 2.5 parts by weight of ethylene glycol into a glass bottle, stir for 10 min at a rotation speed of 100 RPM;

[0051] Step 2: Add 81.45 parts by weight of water to the mixture in "Step 1", then add 2 parts by weight of dextrin, 1 part by weight of Carbopol ETD 2020, 0.5 part by weight of PAMAM solution, 0.05 part by weight of Bis-MPA polyester-64-hydroxy and 12 parts by weight of AEO-9P, stir for 30 min at a rotation speed of 500 RPM; stir until dissolved and dispersed evenly, thus obtaining the spray adjuvant 2# for improving the tank mixing stability of unmanned aerial vehicle (UAV) pesticides.

[0052] Example 3

[0053] A spray adjuvant 3# for improving the tank mixing stability of UAV pesticides, which is composed of the following components in parts by weight:

[0054] 1.8 parts by weight of dextrin, 0.8 part by weight of Carbopol ETD 2020, 0.3 part by weight of PAMAM solution, 0.03 part by weight of Bis-MPA polyester-64-hydroxy, 10 parts by weight of AEO-9P, 0.2 part by weight of GG, 1.8 parts by weight of dispersing medium ethylene glycol, 85.07 parts by weight of water.

[0055] Preparation method:

[0056] Step 1: Add 0.2 part by weight of GG and 1.8 parts by weight of ethylene glycol into a glass bottle, stir for 5 min at a rotation speed of 100 RPM;

[0057] Step 2: Add 85.07 parts by weight of water to the mixture in "Step 1", then add 1.8 parts by weight of dextrin, 0.8 part by weight of Carbopol ETD 2020, 0.3 part by weight of PAMAM solution, 0.03 part by weight of Bis-MPA polyester-64-hydroxy and 10 parts by weight of AEO-9P, stir for 15 min at a rotation speed of 300 RPM; stir until dissolved and dispersed evenly, thus obtaining the spray adjuvant 3# for improving the tank mixing stability of UAV pesticides.

[0058] Example 4

[0059] Replace AEO-9P in Example 3 with non-ionic surfactant TW80 and keep others unchanged, then the spray adjuvant for improving the stability of aerial spraying pesticide tank mixing, i.e., aerial spraying adjuvant 4# is obtained.

[0060] To further illustrate the beneficial effects of the present invention, due to limited space, only Example 3 of the aerial spraying adjuvant is taken as an example to construct Comparative Examples 1-4 as follows.

[0061] Comparative Example 1

[0062] Replace dextrin, Carbopol ETD 2020, PAMAM solution and Bis-MPA polyester-64-hydroxy in Example 3 with maltose and keep others unchanged, then aerial spraying adjuvant 1’ is obtained.

[0063] Comparative Example 2

[0064] Replace dextrin, Carbopol ETD 2020, PAMAM solution and Bis-MPA polyester-64-hydroxy in Example 3 with chitin and keep others unchanged, then aerial spraying adjuvant 2’ is obtained.

[0065] Comparative Example 3

[0066] Replace dextrin, Carbopol ETD 2020, PAMAM solution and Bis-MPA polyester-64-hydroxy in Example 3 with chitosan and keep others unchanged, then aerial spraying adjuvant 3’ is obtained.

[0067] Comparative Example 4

[0068] Replace AEO-9P in Example 3 with anionic surfactant SDBS and keep others unchanged, then aerial spraying adjuvant 4’ is obtained.

[0069] Comparative Example 5

[0070] Replace dextrin in Example 3 with water and keep others unchanged, then aerial spraying adjuvant 5’ is obtained.

[0071] Comparative Example 6

[0072] Replace Carbopol ETD 2020 in Example 3 with water and keep others unchanged, then aerial spraying adjuvant 6’ is obtained.

[0073] Comparative Example 7

[0074] Replace PAMAM solution in Example 3 with water and keep others unchanged, then aerial spraying adjuvant 7’ is obtained.

[0075] Comparative Example 8

[0076] Replace Bis-MPA polyester-64-hydroxy in Example 3 with water and keep others unchanged, then aerial spraying adjuvant 8’ is obtained.

[0077] The performance of the samples prepared in Examples 1-4 and Comparative Examples 1-8 was detected. The appearance of the aerial spraying adjuvant was observed, the surface tension of its 4 wt% dispersion was measured using a DCAT 21 (Dufey) surface and interfacial tension meter, and the ζ-potential of its 4 wt% dispersion was measured using a Nano ZS90 (Malvern) laser particle size analyzer. The results are shown in Table 1.

[0078] Table 1

[0079]

[0080]

[0081] As can be seen from the data in Table 1, the aerial spraying adjuvants prepared in Examples 1-4 have no stratification, no bubble generation, moderate viscosity, and are uniformly dispersed in water, meeting the usage requirements of pesticide adjuvants. The aerial spraying adjuvants prepared in Comparative Examples 1-3 generate a large number of bubbles after shaking, and their ability to reduce the surface tension at the same concentration (4 wt%) is lower than that of Examples 1-4 (the surface tension of water (25 °C) = 71.970 mN / m), and the absolute value of the ζ-potential is lower than that of Examples 1-4 (the greater the absolute value of the ζ-potential, the greater the electrostatic repulsion between particles and the more stable the system). Among them, there are insoluble suspended particles in Comparative Examples 2 and 3. Based on the comprehensive data analysis in Table 1, the state, surface activity, and ζ-potential of the aerial spraying adjuvants in Examples 1-4 are all better than those in Comparative Examples 1-3. After adding them to the aerial spraying liquid, lower surface tension and higher electrostatic repulsion can be obtained, which is more conducive to the stability of the liquid. It can be seen that the physicochemical properties of aerial spraying adjuvants with different formulations vary greatly. In particular, the aerial spraying adjuvant in Comparative Example 4 has good state, surface activity, and ζ-potential, which are the best in Table 1. However, in subsequent experiments, the addition of the aerial spraying adjuvant in Comparative Example 4 to the liquid resulted in an increase in the particle size of pesticide particles (see Table 2). For Comparative Examples 5-8, the effects of four kinds of high molecular polymers on the physicochemical properties of the adjuvant were investigated respectively. It was found that the addition of high molecular polymers has no significant effect on the surface tension and ζ-potential of the adjuvant, but may affect the construction of the three-dimensional network structure of the adjuvant in the solution, thereby affecting the effect of the adjuvant on the stable pesticide tank mixing system.

[0082] The present invention also provides a pesticide composition using the above-mentioned aerial spraying adjuvant, which will be described in detail below in combination with specific examples.

[0083] To verify the specific practical performance of the aerial spraying adjuvant of the present invention, Examples 5-8 and Comparative Examples 9-18 are listed for comparative illustration. The following Examples or Comparative Examples of the pesticide composition are the aerial spraying pesticide tank mixing liquid with the addition of the aerial spraying adjuvant. All the aerial spraying adjuvants come from Examples 1-4 and Comparative Examples 1-8. To obtain the best stability of the pesticide tank mixing liquid, all the aerial spraying pesticide packages are tank mixed in a certain order of adding agents (water - aerial spraying adjuvant - soluble powder - wettable powder - water dispersible granule - suspension - microemulsion - soluble liquid - emulsion in water - aqueous solution - emulsifiable concentrate - phosphorus and potassium fertilizers). After adding each agent, it is immediately stirred and dissolved until evenly dispersed, and then the next agent is added. After all the agents are added, the aerial spraying pesticide tank mixing liquid (pesticide composition) is obtained. The composition of the agents in 1 kg of the liquid medicine (about 1 L) of the pesticide composition used in the following Examples and Comparative Examples is as follows:

[0084] 1. Rice aerial spraying package A: 780 g of water, 40 g of aerial spraying adjuvant, 20 g of 25% pymetrozine suspension, 15 g of 2% emamectin benzoate * 10% chlorfenapyr suspension, 25 g of 14% tricyclazole * 28% tebuconazole suspension, 20 g of 10% thifluzamide * 22% tebuconazole suspension, 40 g of 5% chlorantraniliprole suspension, 20 g of 0.01% brassinolide emulsifiable concentrate, 40 g of potassium dihydrogen phosphate.

[0085] 2. Rice aerial spraying package B: 785 g of water, 40 g of aerial spraying adjuvant, 20 g of 25% pymetrozine suspension, 15 g of 2% emamectin benzoate * 10% chlorfenapyr suspension, 20 g of 25% tricyclazole suspension, 20 g of 10% thifluzamide * 22% tebuconazole suspension, 40 g of 5% chlorantraniliprole suspension, 20 g of 0.01% brassinolide emulsifiable concentrate, 40 g of potassium dihydrogen phosphate.

[0086] 3. Wheat aerial spraying package A: 835 g of water, 40 g of aerial spraying adjuvant, 15 g of 25% pyraclostrobin microemulsion, 10 g of 0.01% 24-epibrassinolide soluble liquid, 60 g of 5% oligosaccharins aqueous solution, 40 g of potassium dihydrogen phosphate.

[0087] 4. Wheat aerial spraying package B: 846 g of water, 40 g of aerial spraying adjuvant, 20 g of 60% pyraclostrobin * metiram water dispersible granule, 10 g of 10% difenoconazole water dispersible granule, 10 g of 0.01% brassinolide aqueous solution, 34 g of 18 g / L abamectin emulsifiable concentrate, 40 g of potassium dihydrogen phosphate.

[0088] 5. Wheat aerial spraying package C: 921.4 g of water, 10 g of aerial spraying adjuvant, 30 g of 56% MCPA-Na soluble powder, 5 g of 70% imidacloprid water dispersible granule, 3.6 g of 75% flucarbazone sodium water dispersible granule, 20 g of 5% florasulam suspension, 10 g of potassium dihydrogen phosphate.

[0089] 6. Wheat aerial spraying package D: 856.4 g of water, 40 g of aerial spraying adjuvant, 30 g of 56% MCPA-Na soluble powder, 10 g of 25% thiamethoxam water dispersible granule, 3.6 g of 75% flucarbazone sodium water dispersible granule, 20 g of 5% diflufenican suspension, 40 g of potassium dihydrogen phosphate.

[0090] 7. Sugarcane aerial spraying package: 614 g of water, 60 g of aerial spraying adjuvant, 6 g of 20% chlorantraniliprole suspension, 80 g of 50% thiophanate-methyl suspension, 40 g of 25% pyraclostrobin suspension, 150 g of 30% emamectin benzoate and monosultap microemulsion, 50 g of dipotassium hydrogen phosphate.

[0091] Example 5

[0092] In this example, rice aerial spraying package A is selected, and the aerial spraying adjuvant is aerial spraying adjuvant 1# in Example 1. The aerial spraying pesticide tank mixture liquid is obtained by tank mixing according to the above-mentioned pesticide addition sequence.

[0093] Example 6

[0094] In this example, rice aerial spraying package A is selected, and the aerial spraying adjuvant is aerial spraying adjuvant 2# in Example 2. The aerial spraying pesticide tank mixture liquid is obtained by tank mixing according to the above-mentioned pesticide addition sequence.

[0095] Example 7

[0096] In this example, rice aerial spraying package A is selected, and the aerial spraying adjuvant is aerial spraying adjuvant 3# in Example 3. The aerial spraying pesticide tank mixture liquid is obtained by tank mixing according to the above-mentioned pesticide addition sequence.

[0097] Example 8

[0098] In this example, rice aerial spraying package A is selected, and the aerial spraying adjuvant is aerial spraying adjuvant 4# in Example 4. The aerial spraying pesticide tank mixture liquid is obtained by tank mixing according to the above-mentioned pesticide addition sequence.

[0099] Comparative Example 9 (blank group)

[0100] In this comparative example, rice aerial spraying package A is selected, and the aerial spraying adjuvant is replaced with water. The aerial spraying pesticide tank mixture liquid is obtained by tank mixing according to the above-mentioned pesticide addition sequence.

[0101] Comparative Example 10

[0102] In this comparative example, rice aerial spraying package A is selected, and the aerial spraying adjuvant is aerial spraying adjuvant 1' in Comparative Example 1. The aerial spraying pesticide tank mixture liquid is obtained by tank mixing according to the above-mentioned pesticide addition sequence.

[0103] Comparative Example 11

[0104] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was aerial spraying adjuvant 2' in Comparative Example 2. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0105] Comparative Example 12

[0106] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was aerial spraying adjuvant 3' in Comparative Example 3. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0107] Comparative Example 13

[0108] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was aerial spraying adjuvant 4' in Comparative Example 4. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0109] Comparative Example 14

[0110] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was aerial spraying adjuvant 5' in Comparative Example 5. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0111] Comparative Example 15

[0112] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was aerial spraying adjuvant 6' in Comparative Example 6. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0113] Comparative Example 16

[0114] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was aerial spraying adjuvant 7' in Comparative Example 7. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0115] Comparative Example 17

[0116] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was aerial spraying adjuvant 8' in Comparative Example 8. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0117] Comparative Example 18

[0118] In this comparative example, rice aerial spraying package A was selected, and the aerial spraying adjuvant was replaced with a solution prepared by uniformly stirring 1.8 parts by weight of dextrin, 0.8 parts by weight of Carbopol ETD2020, 0.3 parts by weight of PAMAM solution, 0.03 parts by weight of Bis-MPA polyester-64-hydroxy, and 97.07 parts by weight of water. The aerial spraying pesticide tank mixture was obtained by tank mixing according to the above-mentioned order of adding the medicaments.

[0119] The performance of the samples prepared in Examples 5-8 and Comparative Examples 9-18 was detected. The state of the liquid medicine was observed within 8 h, and the median particle size D50 at 0 h and 8 h was measured with an LS-609 (Omec) laser particle size analyzer. The results are shown in Table 2.

[0120] Table 2

[0121]

[0122]

[0123] It can be seen from the data in Table 2 that the aerial spraying pesticide tank mixing liquid medicine prepared in Examples 5-8 did not show unstable phenomena such as precipitation and stratification within 8 h, and the particle size D50 measured within 0 h and 8 h was 2-4 μm, which was significantly lower than that of Comparative Example 9 (blank group, 35-42 μm) without adding additives. This shows that the pesticide particles in Examples 5-8 did not agglomerate and were well dispersed; at the same time, the liquid medicine had a good suspension effect and good stability. Among them, the median particle size D50 of the aerial spraying pesticide tank mixing liquid medicine prepared in Example 8 was the smallest, indicating that the aerial spraying adjuvant 4# formula in Example 4 was the best.

[0124] In Comparative Example 9 (blank group) without adding additives, the particles agglomerated rapidly at 0 h, the particle size increased, which was significantly larger than that in Examples 5-8, and it precipitated and stratified rapidly within 0.5 h, with the worst stability. In Comparative Examples 10-12, they were all completely stratified and precipitated within 8 h and could not be applied to actual aerial spraying operations, indicating that maltose, chitin and chitosan could not replace the role of dextrin, Carbopol ETD2020, PAMAM and Bis-MPA polyester-64-hydroxy in synergistically cross-linking and suspending pesticide particles. This is because maltose cannot form a three-dimensional network structure at the nanoscale in the solution, while although chitin and chitosan can form a network structure in aqueous solution, their solubility in the liquid medicine is very low, and the formed network structure has low strength and cannot suspend the pesticide particles well; however, the particle size within 8 h in Comparative Examples 10-12 was less than 4 μm, because the non-ionic surfactants contained in them played a dispersing role.

[0125] Although the system of Comparative Example 13 has good suspension without sedimentation, the pesticide particles agglomerate, and the particle size D50 at 0 h and 8 h is greater than 24 μm, which is significantly greater than that of Examples 5-8. This is because in the high-salt system, the synergistic cross-linking of dextrin, Carbopol ETD 2020, PAMAM, and Bis-MPA polyester-64-hydroxy is not affected by the high ionic strength and can still form a three-dimensional network structure, which can play a good role in suspending pesticide particles. However, in the high-salt system, on the one hand, the solubility of the anionic surfactant SDBS decreases, and on the other hand, the adsorption on the surface of pesticide particles is competitively inhibited by salt ions, resulting in reduced activity. SDBS fails in the high-salt system and cannot play a role in reducing particle aggregation. Therefore, the dispersion function of the additive in Comparative Example 13 is insufficient, the pesticide particles agglomerate, and the particle size increases. In contrast, the nonionic surfactants used in Examples 5-8 are not affected by high salt and show good dispersion effects.

[0126] Comparative Examples 14-17 are all stable within 6 h, but slightly delaminate within 8 h, indicating that the compounding of dextrin, Carbopol ETD 2020, PAMAM, and Bis-MPA polyester-64-hydroxy can construct a stable three-dimensional network structure in the system and form sufficient steric hindrance effect force, which is the key to stabilizing the pesticide tank mixing system.

[0127] The liquid medicine of Comparative Example 18 only has the suspension effect of the synergistic cross-linking network of dextrin, Carbopol ETD 2020, PAMAM, and Bis-MPA polyester-64-hydroxy, but without adding a nonionic surfactant, the effect of the additive in dispersing pesticide particles is poor. Therefore, the particles agglomerate, and the particle size D50 at 0 h and 8 h is significantly greater than that of Examples 5-8.

[0128] Based on the data analysis in Table 2, Examples 5-8 not only have the function of suspending pesticide particles by the synergistic cross-linking network of dextrin, Carbopol ETD 2020, PAMAM, and Bis-MPA polyester-64-hydroxy, but also have the function of dispersing pesticide particles by nonionic surfactants. The combination of the two can achieve a good effect of stabilizing the pesticide tank mixing system for aerial spraying, so that the liquid medicine does not produce precipitation, particle agglomeration, or increase in particle size within 8 h, and the stability effect is significantly better than that of Comparative Examples 6-11. For Comparative Examples 9-18, due to the lack of the synergistic cross-linking network of dextrin, Carbopol ETD 2020, PAMAM, and Bis-MPA polyester-64-hydroxy or nonionic surfactants, or due to the failure of anionic surfactants in the high-salt system, precipitation delamination or particle enlargement occurs, and the stability of the liquid medicine is poor, which is likely to cause nozzle blockage, reduced drug efficacy, and even phytotoxicity. In summary, the stability of Examples 5-8 is better than that of Comparative Examples 9-18.

[0129] To verify the universality of the aerial spraying adjuvant of the present invention when applied to various aerial spraying pesticide compositions, Examples 9-14 are listed for illustration. The following examples are aerial spraying pesticide tank-mixed liquid medicines added with the aerial spraying adjuvant. The aerial spraying adjuvants are all the aerial spraying adjuvant 3# described in Example 3. To make the pesticide tank-mixed liquid medicine obtain the best stability, the aerial spraying pesticides need to be tank-mixed in a certain order of agent addition (water - aerial spraying adjuvant - soluble powder - wettable powder - water dispersible granule - suspension concentrate - microemulsion - soluble solution - emulsion in water - aqueous solution - emulsifiable concentrate - phosphorus and potassium fertilizers), and immediately stir and dissolve after adding each agent, disperse evenly, and then add the next agent. After all the agents are added, the described aerial spraying pesticide tank-mixed liquid medicine (aerial spraying pesticide package) is obtained.

[0130] Example 9

[0131] In this example, the wheat aerial spraying package C is selected. The aerial spraying adjuvant is the aerial spraying adjuvant 3# in Example 3. The aerial spraying pesticide tank-mixed liquid medicine is obtained by tank-mixing according to the above-mentioned order of agent addition.

[0132] Example 10

[0133] In this example, the sugarcane aerial spraying package is selected. The aerial spraying adjuvant is the aerial spraying adjuvant 3# in Example 3. The aerial spraying pesticide tank-mixed liquid medicine is obtained by tank-mixing according to the above-mentioned order of agent addition.

[0134] Example 11

[0135] In this example, the wheat aerial spraying package A is selected. The aerial spraying adjuvant is the aerial spraying adjuvant 3# in Example 3. The aerial spraying pesticide tank-mixed liquid medicine is obtained by tank-mixing according to the above-mentioned order of agent addition.

[0136] Example 12

[0137] In this example, the wheat aerial spraying package B is selected. The aerial spraying adjuvant is the aerial spraying adjuvant 3# in Example 3. The aerial spraying pesticide tank-mixed liquid medicine is obtained by tank-mixing according to the above-mentioned order of agent addition.

[0138] Example 13

[0139] In this example, the wheat aerial spraying package D is selected. The aerial spraying adjuvant is the aerial spraying adjuvant 3# in Example 3. The aerial spraying pesticide tank-mixed liquid medicine is obtained by tank-mixing according to the above-mentioned order of agent addition.

[0140] Example 14

[0141] In this example, the rice aerial spraying package B is selected. The aerial spraying adjuvant is the aerial spraying adjuvant 3# in Example 3. The aerial spraying pesticide tank-mixed liquid medicine is obtained by tank-mixing according to the above-mentioned order of agent addition.

[0142] The performance of the liquid medicines prepared in Examples 9 - 14 was detected, and their states at 8 h were observed. The median particle sizes D50 at 0 h and 8 h were measured using an LS 609 (Omec) laser particle size analyzer. The results are shown in Table 3.

[0143] Table 3

[0144]

[0145]

[0146] As can be seen from the data in Table 3, no precipitation, layering or other unstable phenomena occurred in the aerial spraying pesticide tank - mixed liquid medicines prepared in Examples 9 - 14 within 8 h, indicating good suspension of pesticide particles; and the particle sizes D50 measured at 0 h and 8 h were both below 7 μm, indicating that no agglomeration of pesticide particles occurred within 8 h and the dispersion effect was good. The suspension stability and dispersion stability of its pesticide particles were significantly better than those of Comparative Example 9 (blank group) which quickly layered and had particle agglomeration within 0.5 h. Based on the data analysis in Table 3, the aerial spraying assistant 3# of the present invention showed good suspension and dispersion effects for various aerial spraying pesticide tank - mixed formulations, and the stabilizing effect was significantly better than that of Comparative Example 9 (blank group) without adding an assistant, having universality for aerial spraying pesticide formulations and being applicable to aerial spraying scenarios for various crops.

[0147] The present invention also conducted a field efficacy experiment for controlling Chilo suppressalis. Specifically:

[0148] Test site: Longwangmiao Village, Chunhua Town, Changsha County, Hunan Province;

[0149] Test time: June 3, 2022;

[0150] Test liquid medicines:

[0151] Test group: The liquid medicine of Example 7 was selected (the addition amount of aerial spraying assistant 3# was 40 g / L);

[0152] Commercially available group: The aerial spraying assistant 3# in the liquid medicine of Example 7 was replaced with a commercially available assistant, and the others remained unchanged;

[0153] Control group: The liquid medicines of Comparative Examples 10 - 18 were selected, and the others remained unchanged;

[0154] Blank group: The aerial spraying assistant 3# in the liquid medicine of Example 7 was replaced with water, and the others remained unchanged;

[0155] Clear water group: The liquid medicine of the clear water group was water.

[0156] Note: The nozzle of the blank group was blocked immediately during spraying, resulting in spraying failure, so it was not listed in Table 4.

[0157] Test method: Spraying was carried out by using the UAV aerial spraying method. The flight parameters for UAV spraying and applying pesticides are as follows: nozzle No. 02#, height 1 - 1.5 m, speed 3 - 5 m / s, and spraying liquid volume 1 L / mu. During the operation, the temperature was 32°C and the wind speed was 2 - 5 m / s. The UAV sprayed the corresponding pesticides onto the rice crops at a dosage of 1.0 L / mu, with an area of 3 * 667 m 2 as a plot for the pesticide application comparison test, and the spraying was carried out once.

[0158] Investigation method: The fixed-point investigation method was adopted. The pest population base was investigated before pesticide application, and then investigated once each at 3 days, 7 days, 14 days, and 28 days after pesticide application. For each plot, samples were taken at two diagonal points, and the rice in half of the plot area was investigated. The control effects of each group of pesticides on Chilo suppressalis were observed and counted. According to the number of Chilo suppressalis after pesticide application in the treatment area (experimental group and commercial group) and the control area (clear water group), the relative control effect was calculated, and the pest population reduction rate and control effect were calculated according to the following formulas.

[0159] Pest population reduction rate (%) = [(number of pests before application - number of pests after application) / number of pests before application] × 100;

[0160] Control effect (%) = [1 - (number of pests before application in the control area × number of pests after application in the pesticide treatment area) / (number of pests after application in the control area × number of pests before application in the pesticide treatment area)] × 100;

[0161] Safety investigation method: After pesticide application, the growth conditions of the leaves and rice ears of the rice in each plot were investigated irregularly to observe whether there were any abnormal phenomena or phytotoxicity.

[0162] The test results are shown in Tables 4 - 6.

[0163] Table 4

[0164]

[0165] From the above results, it can be seen that the efficacy of the liquid medicine in Example 7 (experimental group) was significantly better than that of the liquid medicine prepared with the commercial aerial spraying adjuvant (commercial group) at 3, 7, 14, and 28 days after application, indicating that the suspension and dispersion performance of the barrel - mixed liquid medicine of the aerial spraying pesticide has a significant impact on the field efficacy. The blank group without adding the aerial spraying adjuvant had the nozzle blocked immediately during pesticide application, resulting in the failure of pesticide application. The above results show that the aerial spraying adjuvant of the present invention has a significant improvement effect on the field control effect of the aerial spraying pesticide package and is significantly better than the commercial aerial spraying adjuvant. During the test period, each pesticide treatment was safe for the rice, and no phytotoxicity was observed, which was basically the same as the control group (clear water group).

[0166] Table 5

[0167]

[0168]

[0169] As can be seen from Table 5, the rapid increase in the particle size of the system significantly reduces the efficacy of the aerial spraying package for rice (Comparative Examples 13 and 18); the stratification of the liquid medicine results in uneven spraying of the liquid medicine, causing a significant reduction in efficacy (Comparative Examples 10-12).

[0170] Table 6

[0171]

[0172] As can be seen from Table 6, the lack of any one of dextrin, Carbopol ETD 2020, PAMAM, and Bis-MPA polyester-64-hydroxy reduces the control efficacy; it may be because the compounding of the four can construct a three-dimensional network structure in the liquid medicine. The lack of any one of the components reduces the suspension stability of the liquid medicine and tends to stratify, thereby leading to a reduction in efficacy. The control efficacy of the experimental group (Example 7) of the present invention against Chilo suppressalis is better than that of Comparative Examples 10-18.

[0173] In summary, the three-dimensional network structure synergistically crosslinked by dextrin, Carbopol ETD 2020, PAMAM, and Bis-MPA polyester-64-hydroxy in the present invention has a good coating and suspension effect on pesticide particles, and has a good stabilizing effect on most commercially available pesticide formulations, foliar fertilizers, and their tank-mixed liquid medicines. When it is applied to the tank-mixed liquid medicine containing phosphorus and potassium fertilizers, it can effectively reduce the antagonistic destruction of phosphorus and potassium fertilizers on the pesticide system and improve the stability of the liquid medicine.

[0174] The above are the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A spray adjuvant for improving the stability of barrel mixing of pesticides in unmanned aerial vehicle spraying, characterized in that, The spray adjuvant for improving the tank mix stability of aerial spraying pesticides, hereinafter referred to as aerial spraying adjuvant, is composed of the following components in parts by weight: The content of the active ingredient in the PAMAM solution is 5-20 wt%; The non-ionic surfactant is fatty alcohol polyoxyethylene ether phosphate AEO-9P and / or Tween 80.

2. The spray adjuvant for improving the stability of barrel mixing of pesticides for aerial spraying according to claim 1, wherein The thickener is guar gum and / or xanthan gum.

3. The spray adjuvant for improving the stability of barrel mixing of pesticides for aerial spraying according to claim 2, characterized in that, It is composed of the following components in parts by weight:

4. The preparation method of the spray adjuvant for improving the barrel mixing stability of pesticides for aerial spraying according to any one of claims 1 to 3, characterized in that, Including: Step 1: Add a thickener and ethylene glycol to a glass bottle according to a weight ratio, and stir for 2 min - 10 min at a rotation speed of 100 RPM; Step 2: Add water to the mixture obtained in Step 1 according to a weight ratio, and then add dextrin, Carbopol ETD2020, PAMAM solution, Bis-MPA polyester-64-hydroxy and non-ionic surfactant according to a weight ratio and stir for 2 min - 30 min at a rotation speed of 100 - 500 RPM; Stir and dissolve until evenly dispersed to obtain the spray adjuvant for improving the tank mix stability of aerial spraying pesticides, hereinafter referred to as aerial spraying adjuvant.

5. A pesticidal composition, characterized in that, Including the aerial spraying adjuvant according to any one of claims 1-3.

6. The pesticidal composition according to claim 5, characterized in that, It is composed of the following components in parts by weight:

7. The pesticidal composition according to claim 6, characterized in that, The pesticide formulation is one or more of soluble powder, wettable powder, water dispersible granule, suspension concentrate, microemulsion, soluble solution, emulsion in water, aqueous solution, emulsifiable concentrate; The phosphorus and potassium fertilizer is potassium dihydrogen phosphate and / or dipotassium hydrogen phosphate.

8. The pesticide composition according to claim 7, wherein, It is composed of the following components in parts by weight:

9. The preparation method of the pesticide composition according to any one of claims 5-8, characterized in that, Including: Step 1: Add water to a container according to a weight ratio; Step 2: Add the aerial spraying adjuvant, pesticide formulation and phosphorus and potassium fertilizer in sequence according to a weight ratio, and stir evenly to obtain the pesticide composition.

10. The preparation method of the pesticide composition according to claim 9, characterized in that, In Step 2, the addition order of the pesticide formulation is soluble powder, wettable powder, water dispersible granule, suspension concentrate, microemulsion, soluble solution, emulsion in water, aqueous solution, emulsifiable concentrate; After adding each pesticide formulation, immediately stir and disperse evenly, and then add the next pesticide formulation.

Images