Nanometer herbicide and preparation method thereof

Abstract

The application discloses a kind of nano herbicide and preparation method thereof, which belongs to the technical field of agricultural chemicals preparation.The preparation method is to process non-water-soluble herbicide technical material, quaternary ammonium salt, alkaline compound, solvent and other additives by stirring and dispersing to prepare nano water agent.The preparation process of the application is simple, green and environmentally friendly.Compared with traditional dosage forms, the obtained nano preparation improves the herbicidal effect and safety of herbicides, reduces energy consumption, material resources during production process, reduces dosage, reduces the impact on agricultural environment and non-target organisms due to large-scale use of pesticides, achieves the purpose of increasing yield and income, and provides protection for safe production of crops.

Description

Technical Field

[0001] This invention belongs to the field of agricultural chemicals technology, and particularly relates to a nano herbicide and its preparation method. Background Technology

[0002] Herbicides offer advantages such as time and labor saving, cost-effectiveness, and high efficiency, effectively reducing weeding costs and ensuring crop quality and yield. They are currently the primary means of weed control. Herbicides are typically processed into formulations such as wettable powders, suspensions, and oil suspensions. However, these products suffer from problems such as large particle size, thermodynamic instability, susceptibility to stratification and sedimentation, complex processing techniques, and high costs.

[0003] Chinese patent CN116806817A discloses a type of quinoline carboxylic acid ionic liquid W / O / W double emulsion and its preparation and application. The herbicidal ionic liquid obtained by pairing dichloroquinoline acid as an anion with a structurally modified quaternary ammonium cation is used as the active component and emulsifier to prepare a W / O / W type double emulsion, which can effectively control barnyard grass in paddy fields. In the preparation process, an equimolar quaternary ammonium salt and an emulsifier with a mass percentage of 20-25% are added. The preparation process requires heating and has problems such as large amount of adjuvants used, complex preparation process, energy consumption, and large product particle size. Chinese patent CN 109699639 A discloses a nicosulfuron dispersible oil suspension and its preparation method. The method involves mixing nicosulfuron, oily filler, emulsifying dispersant, and thickener, followed by sand milling to obtain a suspension with a particle size of 6.85-7.52 μm. While this preparation method significantly improves production efficiency, the oily filler and complex adjuvant system used account for over 90% of the total mass, and the product particle size is greater than 5.0 μm. Chinese patent CN 109964946 A discloses a herbicidal composition containing atrazine, quinclorac acid, and clopyralid. The active ingredients are added in a certain proportion and then mixed with dispersants, emulsifiers, thickeners, stabilizers, and carriers. The mixture is then subjected to mechanical pulverization, air jet milling, or sand milling to obtain a wettable powder or suspension. Although the use of a ternary component compound significantly improves the herbicidal effect, it also employs a relatively complex adjuvant system, and the processing technology is very energy-intensive, resulting in a large product particle size. Although the herbicide suspensions and wettable powders prepared by the above methods have good weed control effects, there are still problems such as large product particle size, complex preparation process, high energy consumption and high cost.

[0004] Nanopesticides, due to their superior physicochemical properties such as small particle size and large specific surface area, exhibit small size and surface tunneling effects, resulting in better deposition, spreading, and penetration of target organisms. They represent a direction for the green development of pesticides and are widely praised and welcomed. The nano-scale herbicide prepared in this invention is an amphiphilic nanomicelle formed by the spontaneous aggregation and assembly of herbicide and quaternary ammonium salt in an aqueous phase. It features small particle size and high surface energy, which can alter the way pesticides act on their targets, improve their bioactivity, and reduce their environmental impact. Therefore, developing nano-scale herbicides through simple and green preparation methods to improve their herbicidal activity and bioavailability is of great significance. Summary of the Invention

[0005] To address the aforementioned problems, this invention provides a nano-herbicide and its method. The nano-herbicide is prepared by mixing and dispersing a non-water-soluble herbicide technical, quaternary ammonium salt, alkaline compound, solvent, and other adjuvants. This improves the herbicidal effect and safety of the herbicide, reduces energy and material consumption during production, lowers dosage, and minimizes the impact of excessive pesticide use on the agricultural environment and human health, thereby increasing yield and income.

[0006] This invention is achieved through the following technical solution: herbicides, quaternary ammonium salts, alkaline compounds, solvents, and adjuvants are mixed and then stirred and dispersed to prepare a nano-aqueous solution (i.e., nano-herbicides). The effective ingredient of the herbicide has a mass percentage content of 0.2-30%, and the total mass percentage content of the quaternary ammonium salt, alkaline compound, solvent, and adjuvants is 70-99.8%.

[0007] The preparation method of the nano-herbicide of this invention is as follows: In deionized water, a quaternary ammonium salt is first mixed and dissolved with a certain amount of alkaline compound by stirring, then the herbicide technical material is added, and the mixture is stirred thoroughly until nano-micelles are formed, thus obtaining a stable nano-aqueous herbicide. The particle size of the nano-herbicide does not exceed 200 nanometers, preferably 10-160 nm. The reaction formula in the above steps is as follows:

[0008]

[0009] The Y in the above reaction formula is Cl or Br; and / or R1, R2, R3 and R4 are independent C1 to C2 groups. 18 Alkyl or benzyl.

[0010] In some preferred embodiments, the molar ratio of the alkaline compound: quaternary ammonium salt: herbicide is 1.0:(1.0-3.0):(1.0-4.0);

[0011] In some more preferred embodiments, the molar ratio of the alkaline compound: quaternary ammonium salt: herbicide is 1.0:(1.5-3.0):(1.0-2.0).

[0012] In some preferred embodiments, the herbicide is one or a mixture of several of the following: 2,4-D, bentazon, bensulfuron-methyl, benzosulfuron-methyl, pyrimisulfuron-methyl, bensulfuron-methyl, pyrimisulfuron-methyl, methyl methoxysulfuron, dichloropyridine acid, dichloroquinoline acid, sulfadiazon-methyl, fluazin, flusulfanilamide, cyclosulfanilamide, sulfadiazine, mesosulfuron-methyl, methoxysulfuron-methyl, chlorpyrifos, chlorpyrifos, dicamba, imazin, trifluralin, trichloropyrifos, thifensulfuron-methyl, bispyribac-sodium, diflusulfuron-methyl, diflusulfuron-methyl, penoxsulam, mesosulfuron-methyl, cyprosulfuron-methyl, bromobenzonitrile, nicosulfuron-methyl, and pyrimisulfuron-methyl.

[0013] In some preferred embodiments, the quaternary ammonium salt is n-hexyltrimethylammonium chloride, n-hexyltrimethylammonium bromide, n-octyltrimethylammonium chloride, n-octyltrimethylammonium bromide, n-decyltrimethylammonium chloride, n-decyltrimethylammonium bromide, lauryltrimethylammonium chloride, lauryltrimethylammonium bromide, myristylalkyltrimethylammonium chloride, myristylalkyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, dioctyldimethylammonium chloride, dioctyldimethylammonium bromide, didecyldimethylammonium chloride, didecyldimethylammonium bromide, didodecyldimethylammonium chloride, didodecyldimethylammonium bromide, dihexadecyldimethylammonium chloride ... A mixture of one or more of the following: octadecyl dimethyl ammonium chloride, octadecyl dimethyl ammonium chloride, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrahexyl ammonium chloride, tetrahexyl ammonium bromide, octylbenzyl dimethyl ammonium chloride, octylbenzyl dimethyl ammonium bromide, benzyldecyl dimethyl ammonium chloride, benzyldecyl dimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium bromide, hexadecyl dimethyl benzyl ammonium chloride, hexadecyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium chloride, octadecyl dimethyl benzyl ammonium bromide, dodecyl pyridine chloride, dodecyl pyridine bromide, hexadecyl pyridine chloride, and hexadecyl pyridine bromide.

[0014] In some preferred embodiments, the alkaline compound is one or a mixture of several of the following: ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium hydrogen phosphate, potassium hydrogen phosphate, ethanolamine, diethanolamine, triethanolamine, methylamine, ethylamine, and isopropylamine.

[0015] In some preferred embodiments, the solvent includes one or a mixture of several of the following: water, methanol, ethanol, isopropanol, dimethylformamide, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, acetone, ethylene glycol, propylene glycol, glycerol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, and propylene glycol butyl ether.

[0016] In some preferred embodiments, the adjuvant includes C 12 ~C 18 The fatty alcohol polyoxyethylene ether, alkylolamide, fatty acid polyoxyethylene ester, sorbitan monooleate, sorbitan laurate, glyceryl monostearate, cocoyl glucoside, alkyl glycoside, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, carboxyethyl cellulose, pectin, xanthan gum, gum arabic, gelatin, alginic acid, octanol, and silicone are one or more of these compounds.

[0017] This application also provides a nano herbicide obtained by the preparation method described above.

[0018] In addition, this application also provides the use of the nano herbicide described herein in controlling grassy weeds and / or broadleaf weeds in farmland.

[0019] In some preferred embodiments, the farmland is selected from any one or more of the following: corn, wheat, rice, and soybean crop farmland.

[0020] In some preferred embodiments, the grassy weeds are selected from any one or more of the following: foxtail grass, barnyard grass, goosegrass, crabgrass, jointed goatgrass, sedge, duckweed, wild oat, and wild oat.

[0021] In some preferred embodiments, the broadleaf weeds are selected from any one or more of the following: lambsquarters, black nightshade, velvetleaf, amaranth, cocklebur, cleavers, shepherd's purse, and shepherd's purse.

[0022] The beneficial effects of this invention are as follows:

[0023] 1. The nano herbicide prepared in this invention has a small particle size, not exceeding 200 nanometers, preferably 10-160 nm, and has good deposition and spreading performance on the target, thereby improving pesticide utilization and reducing the amount of pesticide used.

[0024] 2. The preparation method of the nano herbicide provided in this invention is simple and green, and does not require energy-consuming equipment such as large-scale airflow pulverizers, sand mills, and ball mills, thus reducing production energy consumption.

[0025] 3. Indoor and field efficacy tests have shown that the nano herbicide prepared in this invention has excellent weed control effects, with a plant control efficacy of over 91-96% against broadleaf weeds and over 81-96% against grass weeds; and it is safe for crops. Detailed Implementation

[0026] The following provides several preferred embodiments of the compounds described in this invention. However, this invention is not limited to the specific examples given below. The field efficacy trials employed a completely randomized block design with each plot measuring 20m. 2 The control effect was investigated 14 days after application, and the control effect was investigated using the absolute value method. The calculation formula is: control effect per plant = (number of a certain weeds in the control area - number of a certain weeds in the pesticide-treated area) / number of a certain weeds in the control area * 100%. The invention will be further described in detail below with reference to specific embodiments.

[0027] Example 1

[0028] 1.06 g (10 mmol) of sodium carbonate and 5.28 g (20 mmol) of lauryltrimethylammonium chloride were weighed and dissolved in 60 g of 1% ethanol aqueous solution. The solution was stirred until completely dissolved. 8.07 g (20 mmol) of 98% benzsulfuron technical grade was added to the above solution system and stirred until completely dissolved. The solution was then made up to 100 g with 0.2% polyvinyl alcohol aqueous solution and stirred thoroughly until nanomicelles were formed, resulting in a benzsulfuron nano aqueous solution with a mass percentage of 8%. After diluting 200 times with water, the average particle size was 160 nm.

[0029] According to the methods for determining the thermal storage / low temperature stability of pesticides as described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After being stored at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0030] Comparative Example 1

[0031] 10% benzyl sulfide wettable powder was purchased from Qiaochang Modern Agriculture Co., Ltd.

[0032] weed control effect

[0033] Field efficacy trials were conducted using the agents from Example 1 and Comparative 1, respectively, during the wheat tillering to jointing stage and the weed 2-4 leaf stage.

[0034] The application concentration of the 8% bensulfuron nano aqueous solution in Example 1 and the 10% bensulfuron wettable powder in Comparative Example 1 was 50 mg / L. Each treatment was repeated 3 times, and the treatment was carried out manually and uniformly using a pneumatic sprayer.

[0035] The main weeds in the field were broadleaf weeds such as lambsquarters, amaranth, and cocklebur, and grassy weeds such as foxtail, crabgrass, and jointed goatgrass, accounting for about 90% of the total weed density. The results showed that the weed control efficacy of the herbicide 14 days after application is shown in the table below. Specifically, Example 1 showed a plant control efficacy of 94.9–96.4% against broadleaf weeds and 81.6–84.5% against grassy weeds, representing increases of 7.8–12.2% and 7.2–8.6% respectively compared to Comparative Example 1.

[0036] Table 1. Control effects of Example 1 and Comparative Example 1 on different types of weeds in wheat fields.

[0037]

[0038] Example 2

[0039] 0.56 g (10 mmol) of potassium hydroxide and 6.4 g (20 mmol) of hexadecyltrimethylammonium chloride were weighed and dissolved in 80 g of deionized water. The mixture was stirred until completely dissolved. 3.75 g (10 mmol) of 97% benzoxazine technical grade was added to the above solution system and stirred until completely dissolved. The solution was then made up to 100 g with 0.1% gum arabic aqueous solution and stirred thoroughly until nano-micelles were formed, resulting in a benzoxazine nano-aqueous agent with a mass percentage of 3.6%. After diluting 200 times with water, the average particle size was 125 nm.

[0040] According to the methods for determining the thermal storage / low temperature stability of pesticides as described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After being stored at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0041] Comparative Example 2

[0042] 4% benzoyl sulfadiazine oil suspension concentrate, purchased from Qiaochang Modern Agriculture Co., Ltd.

[0043] weed control effect

[0044] Field efficacy trials were conducted using the agents from Example 2 and Comparative Example 2 at the 3-5 leaf stage of summer maize and the 2-4 leaf stage of weeds, respectively.

[0045] The application concentration of the 3.6% benzoxazine nano aqueous solution in Example 2 and the 4% benzoxazine oil suspension in Comparative Example 2 was 100 mg / L. Each treatment was repeated 3 times, and the treatment was carried out by manual uniform spraying using a pneumatic sprayer.

[0046] The main weeds in the field were broadleaf weeds such as lambsquarters, velvetleaf, and amaranth, and grassy weeds such as foxtail, crabgrass, and goosegrass, accounting for about 90% of the total weed density. The results showed that the herbicide's control effect on weeds 14 days after application is shown in the table below. Among them,

[0047] Example 2 showed a plant control efficacy of 91.3–93.4% against broadleaf weeds and 82.3–86.2% against grass weeds, which were 8.8–10.5% and 5.2–16.2% higher than those of Comparative Example 2, respectively.

[0048] Table 2 shows the control effects of Example 2 and Comparative Example 2 on different types of weeds in cornfields.

[0049]

[0050] Example 3

[0051] 1.2 g (30 mmol) of sodium hydroxide and 9.43 g (30 mmol) of n-decyltrimethylammonium chloride were weighed and dissolved in 50 g of 2% methanol aqueous solution. The solution was stirred until completely dissolved. 12.7 g (30 mmol) of 98% pyrimisulfuron technical grade was added to the above solution system and stirred until completely dissolved. Deionized water was added to make up to 100 g and stirred thoroughly until nano micelles were formed, resulting in a pyrimisulfuron nano aqueous solution with a mass percentage of 12.4%. After diluting 200 times with water, the average particle size was 75 nm.

[0052] According to the methods for determining the thermal storage / low temperature stability of pesticides as described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After being stored at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0053] Comparative Example 3

[0054] 15% pyrimisulfuron dispersible oil suspension was purchased from Qiaochang Modern Agriculture Co., Ltd.

[0055] weed control effect

[0056] Field efficacy trials were conducted using the agents from Example 3 and Comparative Example 3, respectively, three weeks after rice seedling emergence and when weeds were at the 2-4 leaf stage.

[0057] The application concentration of the 12.4% pyrimisulfuron nano aqueous solution in Example 3 and the 15% pyrimisulfuron dispersible oil suspension in Comparative Example 3 was 75 mg / L. Each treatment was repeated 3 times, and the treatment was carried out by manual uniform spraying using a pneumatic sprayer.

[0058] The main weeds in the field were barnyard grass, sedge, and duckweed, accounting for about 90% of the total weed density. The results showed that the weed control efficacy of the herbicide 14 days after application is shown in the table below. Specifically, Example 3 showed a plant control efficacy of 90.2%–96.6% against grassy weeds, which was 5.0%–10.8% higher than that of Comparative Example 3.

[0059] Table 3. Control effects of Example 3 and Comparative Example 3 on different grass weeds in paddy fields.

[0060] medicine barnyard grass Cyperus divaricata duck tongue grass Example 3 93.1％ 96.6％ 90.2％ Comparative Example 3 88.7％ 87.2％ 84.3％

[0061] Example 4

[0062] 3.2 g (80 mmol) of sodium hydroxide and 22.71 g (80 mmol) of octylbenzyldimethylammonium chloride were weighed and dissolved in 40 g of 0.2% methanol aqueous solution. The solution was stirred until completely dissolved. 15.84 g of 97% dichloropyridine acid (80 mmol) technical grade was added to the above solution system, and the mixture was stirred until completely dissolved. Deionized water was added to make up to 100 g, and the mixture was stirred thoroughly until nanomicelles formed, resulting in a dichloropyridine acid nano-aqueous agent with a mass percentage of 15.4%. After diluting 200 times with water, the average particle size was 90 nm. According to the pesticide thermal storage / low temperature stability determination methods described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After storage at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0063] Comparative Example 4

[0064] 25% dichloroquinoline suspension concentrate, purchased from Shandong Xianda Agrochemical Co., Ltd.

[0065] weed control effect

[0066] Field efficacy trials were conducted two weeks after rice transplanting, when weeds were at the 2-4 leaf stage, using the agents from Example 4 and Comparative Example 4, respectively.

[0067] The application concentration of the 15.4% dichloroquinoline acid nano-aqueous agent in Example 4 and the 25% dichloroquinoline acid suspension in Comparative Example 4 was 600 mg / L. Each treatment was repeated 3 times, and the treatment was carried out by manual uniform spraying using a pneumatic sprayer.

[0068] The dominant weed in the field was barnyard grass, accounting for approximately 85% of the total weed density. The results showed that the herbicide's control efficacy against weeds 14 days after application is shown in the table below. Specifically, Example 4 achieved a plant control efficacy of 96.1% against barnyard grass, a 9.7% increase compared to Comparative Example 4.

[0069] Table 4 shows the control efficacy of Example 4 and Comparative Example 4 on barnyard grass in paddy fields.

[0070] medicine barnyard grass Example 4 96.1％ Comparative Example 4 87.6％

[0071] Example 5

[0072] 0.8 g (20 mmol) of sodium hydroxide and 5.6 g (20 mmol) of tetrabutylammonium chloride were weighed and dissolved in 60 g of deionized water. The solution was stirred until completely dissolved. 8.6 g of 98% fluoxetine (20 mmol) technical grade was added to the solution, and the mixture was stirred until completely dissolved. The solution was then brought to a final volume of 100 g with deionized water and stirred thoroughly until nanomicelles formed, yielding a fluoxetine nano-aqueous agent with a mass percentage of 8.4%. After diluting the solution 200 times with water, the average particle size was 55 nm. According to the pesticide thermal storage / low temperature stability determination methods described in GB / T 19136-2021 and GB / T 19137-2003, after storing the sample at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After storing the sample at 0℃ for 7 days, no precipitate was observed at the bottom after centrifugation.

[0073] Comparative Example 5

[0074] 5% fluoxetine dispersible oil suspension was purchased from Qiaochang Modern Agriculture Co., Ltd.

[0075] weed control effect

[0076] Field efficacy trials were conducted using the agents from Example 5 and Comparative Example 5 at the 3-5 leaf stage of corn and the 2-4 leaf stage of weeds, respectively.

[0077] The application concentration of the 8.4% fluoxetine nano-aqueous agent in Example 5 and the 5% fluoxetine dispersible oil suspension in Comparative Example 5 was 100 mg / L. Each treatment was repeated 3 times, and the treatment was carried out by manual uniform spraying using a pneumatic sprayer.

[0078] Wild oats, bromegrass, and foxtail grass were the main weeds in the field, accounting for about 90% of the total weed density. The results showed that the herbicide's control efficacy against weeds 14 days after application is shown in the table below. Specifically, Example 5 showed a plant control efficacy of 93.6–95.2% against grassy weeds, an increase of 8.3–12.7% compared to Comparative Example 5.

[0079] Table 5. Control efficacy of Example 5 and Comparative Example 5 against different grassy weeds in cornfields.

[0080] medicine wild oats brome foxtail grass Example 5 93.6％ 95.2％ 94.8％ Comparative Example 5 86.4％ 84.5％ 87.2％

[0081] Example 6

[0082] 3.36 g (60 mmol) of potassium hydroxide and 20.4 g (60 mmol) of hexadecylpyridine chloride were weighed and dissolved in 50 g of 2% acetone aqueous solution. The solution was stirred until completely dissolved. 15.8 g (60 mmol) of 97% clopyralid technical grade was added to the above solution system and stirred until completely dissolved. Deionized water was added to make up to 100 g and stirred thoroughly until nanomicelles were formed, resulting in a clopyralid nano aqueous solution with a mass percentage of 15.3%. After diluting 200 times with water, the average particle size was 110 nm.

[0083] According to the methods for determining the thermal storage / low temperature stability of pesticides as described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After being stored at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0084] Comparative Example 6

[0085] 20% clopyralid emulsifiable concentrate, purchased from Jiangsu Futian Agricultural Chemical Co., Ltd.

[0086] weed control effect

[0087] Field efficacy trials were conducted using the agents from Example 6 and Comparative Example 6, respectively, during the wheat tillering to jointing stage and the weed 2-4 leaf stage.

[0088] The application concentration of the 15.3% clopyralid nano aqueous solution in Example 6 and the 20% clopyralid emulsifiable concentrate in Comparative Example 6 was 400 mg / L. Each treatment was repeated 3 times, and the treatment was carried out by manual uniform spraying using a pneumatic sprayer.

[0089] The main weeds in the field were lambsquarters, amaranth retroflexus, and cocklebur, accounting for about 85% of the total weed density. The results showed that the weed control efficacy of the herbicide 14 days after application is shown in the table below. Specifically, Example 6 showed a plant control efficacy of 92.4–96.3% against broadleaf weeds, which was 9.5–10.8% higher than that of Comparative Example 6.

[0090] Table 6 shows the control effects of Example 6 and Comparative Example 6 on different broadleaf weeds in wheat fields.

[0091] medicine quinoa Amaranth cocklebur Example 6 93.7％ 92.4％ 96.3％ Comparative Example 6 85.6％ 84.3％ 86.9％

[0092] Example 7

[0093] 1.68 g (30 mmol) of potassium hydroxide and 9.25 g (30 mmol) of dodecyltrimethylammonium bromide were weighed and dissolved in 60 g of 1% dimethyl sulfoxide aqueous solution. The solution was stirred until completely dissolved. 11.54 g (30 mmol) of 97% thifensulfuron technical grade was added to the above solution system and stirred until completely dissolved. Deionized water was added to make up to 100 g and stirred thoroughly until nano micelles were formed, resulting in a thifensulfuron nano aqueous solution with a mass percentage of 11.2%. After diluting 200 times with water, the average particle size was 150 nm.

[0094] According to the methods for determining the thermal storage / low temperature stability of pesticides as described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After being stored at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0095] Comparative Example 7

[0096] 15% thifensulfuron wettable powder was purchased from Jiangsu Futian Agricultural Chemical Co., Ltd.

[0097] weed control effect

[0098] Field efficacy trials were conducted using the agents from Example 7 and Comparative Example 7, respectively, during the wheat tillering to jointing stage and the weed 2-4 leaf stage. The application concentration of the 11.2% thifensulfuron nano aqueous solution of Example 7 and the 15% thifensulfuron wettable powder of Comparative Example 7 was 100 mg / L. Each treatment was repeated three times, and the treatment was carried out manually and uniformly using a pneumatic sprayer.

[0099] The main weeds in the field were lambsquarters, amaranth retroflexus, and cocklebur, accounting for about 90% of the total weed density. The results showed that the weed control efficacy of the herbicide 14 days after application is shown in the table below. Specifically, Example 7 showed a plant control efficacy of 93.8–97.1% against broadleaf weeds, an increase of 8.4–13.1% compared to Comparative Example 7.

[0100] Table 7 shows the control effects of Example 7 and Comparative Example 7 on different broadleaf weeds in wheat fields.

[0101] medicine quinoa Amaranth cocklebur Example 7 97.1％ 95.4％ 93.8％ Comparative Example 7 89.6％ 87.3％ 82.9％

[0102] Example 8

[0103] Weigh 0.62 g (10 mmol) of ethanolamine and 4.63 g (15 mmol) of dodecyltrimethylammonium bromide and dissolve them in 70 g of deionized water. Stir until completely dissolved. Add 3.7 g (10 mmol) of 97% diflubenzuron technical grade to the above solution system and continue stirring until completely dissolved. Make up the volume to 100 g with 0.1% polyvinylpyrrolidone aqueous solution and stir thoroughly until nano micelles are formed to obtain a diflubenzuron nano aqueous solution with a mass percentage of 3.6%. Dilute with water 200 times and the average particle size is 60 nm.

[0104] According to the methods for determining the thermal storage / low temperature stability of pesticides as described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After being stored at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0105] Comparative Example 8

[0106] 10% diflubenzuron suspension concentrate, purchased from Shandong Binnong Technology Co., Ltd.

[0107] weed control effect

[0108] Field efficacy trials were conducted using the agents from Example 8 and Comparative Example 8, respectively, before the wheat jointing stage and when the weeds were at the 2-4 leaf stage.

[0109] The application concentration of the 3.6% diflubenzuron nano-aqueous agent in Example 8 and the 10% diflubenzuron suspension in Comparative Example 8 was 10 mg / L. Each treatment was repeated 3 times, and the treatment was carried out by manual uniform spraying using a pneumatic sprayer.

[0110] The main weeds in the field were cleavers, shepherd's purse, and capernaum, accounting for about 90% of the total weed density. The results showed that the weed control efficacy of the herbicide 14 days after application is shown in the table below. Specifically, Example 8 showed a plant control efficacy of 92.5%–96.3% against broadleaf weeds, an increase of 9.7%–10.9% compared to Comparative Example 8.

[0111] Table 8 shows the control effects of Example 8 and Comparative Example 8 on different broadleaf weeds in wheat fields.

[0112] medicine Pig calamus Sow thistle shepherd's purse Example 8 92.5％ 96.3％ 94.4％ Comparative Example 8 84.3％ 86.9％ 85.1％

[0113] Example 9

[0114] 0.56 g (10 mmol) of potassium hydroxide and 5.28 g (20 mmol) of dodecyltrimethylammonium chloride were weighed and dissolved in 80 g of deionized water. The mixture was stirred until completely dissolved. 4.19 g (10 mmol) of 98% nicosulfuron technical grade was added to the above solution system and stirred until completely dissolved. The solution was then made up to 100 g with deionized water and stirred thoroughly until nano-micelles were formed, resulting in a nicosulfuron nano-aqueous agent with a mass percentage of 4.1%. After diluting the nano-aqueous agent 200 times with water, the average particle size was 135 nm.

[0115] According to the methods for determining the thermal storage / low temperature stability of pesticides as described in GB / T 19136-2021 and GB / T 19137-2003, after the sample was stored at 54℃ for 14 days, the degradation rate of the active ingredient content was less than 5% as detected by high performance liquid chromatography. After being stored at 0℃ for 7 days, no precipitate was found at the bottom after centrifugation.

[0116] Comparative Example 9

[0117] 8% nicosulfuron dispersible oil suspension was purchased from Qiaochang Modern Agriculture Co., Ltd.

[0118] weed control effect

[0119] Field efficacy trials were conducted using the agents from Example 9 and Comparative Example 9 at the 3-5 leaf stage of corn and the 2-4 leaf stage of weeds, respectively.

[0120] The application concentration of the 4.1% nicosulfuron nano aqueous solution in Example 1 and the 10% nicosulfuron dispersible oil suspension in Comparative Example 1 was 100 mg / L. Each treatment was repeated 3 times, and the treatment was carried out by manual uniform spraying using a pneumatic sprayer.

[0121] The main weeds in the field were barnyard grass, crabgrass, and foxtail grass (all belonging to the gramineous family), and broadleaf weeds such as lambsquarters, amaranth, and cocklebur, accounting for approximately 90% of the total weed density. The results showed that the weed control efficacy of the herbicide 14 days after application is shown in the table below. Specifically, Example 9 showed a plant control efficacy of 93.6–94.2% against broadleaf weeds and 91.3–93.7% against gramineous weeds, representing increases of 9.9–13.6% and 4.4–11.2% respectively compared to Comparative Example 9.

[0122] Table 9 shows the control effects of Example 9 and Comparative Example 9 on different types of weeds in cornfields.

[0123]

[0124] While the aforementioned primary implementation of this intellectual property right is permitted, no other forms of implementation of this new product and / or method are restricted. Those skilled in the art will utilize this important information to modify the above content to achieve similar implementations. However, all modifications or alterations based on this new product invention are reserved rights.

[0125] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a nano-herbicide, comprising the following steps: dispersing the herbicide, quaternary ammonium salt, alkaline compound, solvent, and other adjuvants in deionized water; in, The herbicide's active ingredient content is 0.2-30% by mass, while the content of quaternary ammonium salts, alkaline compounds, solvents, and other adjuvants is 70-99.8% by mass. In the above steps, in deionized water, the quaternary ammonium salt and alkaline compound are mixed first, then the herbicide is added and stirred until nanomicelles are formed; The herbicide is selected from any one or more of the following group: bensulfuron-methyl, benzosulfuron-methyl, pyrimisulfuron-methyl, dichloropyridine acid, fluazolidone, clopyralid, thifensulfuron-methyl, diflubenzuron, and nicosulfuron-methyl; The quaternary ammonium salt is selected from any one or more of the following groups: lauryltrimethylammonium chloride, hexadecyltrimethylammonium chloride, n-decyltrimethylammonium chloride, octylbenzyldimethylammonium chloride, tetrabutylammonium chloride, hexadecylpyridine chloride, dodecyltrimethylammonium bromide, and dodecyltrimethylammonium chloride; The alkaline compound is selected from any one or more of the following group: sodium carbonate, potassium hydroxide, sodium hydroxide, and ethanolamine; The molar ratio of the alkaline compound, quaternary ammonium salt, and herbicide is 1.0:(1.0-3.0):(1.0-4.0).

2. The preparation method according to claim 1, wherein, The solvent is selected from any one or more of the following groups: water, methanol, ethanol, isopropanol, dimethylformamide, dioxane, dimethyl sulfoxide, N-methylpyrrolidone, acetone, ethylene glycol, propylene glycol, glycerol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, and propylene glycol butyl ether.

3. The preparation method according to claim 1, wherein, The adjuvant is selected from any one or more of the following group: C 12 ~C 18 Fatty alcohol polyoxyethylene ethers, alkylolamides, fatty acid polyoxyethylene esters, sorbitan monooleate, sorbitan laurate, glyceryl monostearate, cocoyl glucoside, alkyl glycosides, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose, carboxyethyl cellulose, pectin, xanthan gum, gum arabic, gelatin, alginic acid, octanol, and silicone.

4. A nano herbicide obtained by the preparation method according to any one of claims 1 to 3.

5. The use of the nano herbicide according to claim 4 in controlling grassy weeds and / or broadleaf weeds in farmland.

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