Glyphosate soluble concentrate and preparation method thereof

Abstract

The invention discloses a glyphosate soluble concentrate and a preparation method, and the glyphosate soluble concentrate comprises the following raw material components in parts by weight: 30-40 parts of glyphosate, 10-15 parts of isopropylamine, 8-12 parts of a composite synergist, 2-3 parts of an anti-freezing agent, 0.05-0.1 part of a pH regulator, 2-3 parts of an additive, 0.1-0.5 part of a defoaming agent, 1-2 parts of a loading agent and 40-50 parts of water. Compared with the prior art, the glyphosate soluble concentrate prepared by the invention has the advantages that the propoxylated quaternary ammonium salt and the ethyoxyl alkyl phosphate are mixed according to a certain mass ratio to form the synergist, so that the pesticide effect of glyphosate is remarkably improved. Meanwhile, the aluminum pillared clay is introduced to load the glyphosate and is cooperatively used with the polydopamine-sodium alginate compound, so that the prepared glyphosate soluble concentrate has relatively high leaf deposition rate and rain wash resistance and also has excellent ultraviolet resistance.

Description

Technical Field

[0001] This invention relates to the field of pesticide formulation technology, and in particular to a glyphosate soluble concentrate and its preparation method. Background Technology

[0002] Glyphosate, chemically known as N-(phosphonocarboxymethyl)glycine, is a colorless crystal in its pure form and belongs to the systemic, broad-spectrum, non-selective organophosphorus herbicide class. As a non-selective organophosphorus herbicide, glyphosate is absorbed and translocated through the leaves after foliar spraying, inhibiting the synthesis of amino acids in weeds to achieve its weed-controlling effect. When converted to the equivalent dosage of glyphosate acid, glyphosate isopropylamine salt soluble concentrates are more effective than ammonium salts, potassium salts, dimethylamine salts, and sodium salts. However, due to the low surface energy hydrophobic layer and rough micro / nanostructure of plant leaves, pesticide droplets are lost through evaporation, permeation, dripping, and rainwater runoff, reducing pesticide effectiveness and causing environmental pollution. Furthermore, by spraying pesticide droplets directly onto plants, glyphosate is easily degraded under ultraviolet light, leading to a decrease in its weed-controlling efficacy. Therefore, improving the adhesion and deposition persistence of pesticide droplets on leaf surfaces and enhancing the UV resistance of glyphosate are directions worth exploring and developing.

[0003] CN117256620A discloses a low-temperature resistant glyphosate isopropylamine salt soluble concentrate, its preparation method, and its application. The soluble concentrate comprises the following components by weight: 50-60 parts of 62% glyphosate isopropylamine salt soluble concentrate, 1-5 parts of stretching agent, 3-7 parts of retention agent, 0.3-0.7 parts of synergist, 5-12 parts of organosilicon modified polyoxyethylene ether additive, 1-3 parts of stabilizer microemulsion, and 30-40 parts of water. The low-temperature resistant glyphosate isopropylamine salt soluble agent of this invention has good stability in low-temperature environments and is not prone to deterioration, aggregation, turbidity, or stratification. This can improve the weeding effect of glyphosate isopropylamine salt at low temperatures. Moreover, it can dissolve the waxy layer of the epidermis of weed stems and leaves, improve the penetration ability of glyphosate isopropylamine salt into weed stems and leaves, and enhance the conduction ability of glyphosate isopropylamine salt in weeds, thereby achieving a high-efficiency weed removal effect. However, this soluble agent has a low leaf deposition rate and is prone to pesticide loss during application through rebound, splashing, and other means, reducing efficacy.

[0004] CN114680130B discloses a glyphosate isopropylamine salt soluble concentrate and its preparation method. By mass percentage, the components of the glyphosate isopropylamine soluble concentrate are: glyphosate isopropylamine salt 62-72%, compound adjuvants 1-5%, and deionized water to 100%. The preparation method of the glyphosate isopropylamine salt soluble concentrate provided by this invention is simple, requires little equipment investment, and generates no waste. The resulting high-content liquid product is transparent and shows no crystallization after 90 days of storage at 0℃. Furthermore, the use of compound adjuvants produces a synergistic effect in weed control. At a dosage of 180-240 g / mu, this liquid concentrate has high efficacy against grasses and broadleaf weeds in non-cultivated land and citrus orchards. However, this soluble concentrate has poor photostability, and the active pesticide component is easily degraded by ultraviolet light, leading to reduced pesticide efficacy and preventing long-term weed control. Summary of the Invention

[0005] In view of the above-mentioned deficiencies of the prior art, the present invention provides a glyphosate soluble concentrate that exhibits high control efficacy against weeds in non-cultivated land and is safe for other organisms. By using the raw material components synergistically and in a reasonable ratio, the prepared soluble concentrate possesses excellent leaf deposition rate and resistance to rain washout, while also exhibiting good UV resistance, thus achieving long-term glyphosate efficacy and extending the control time against weeds.

[0006] To achieve the above objectives, the present invention provides a method for preparing glyphosate soluble concentrate, comprising the following steps: Glyphosate and water are mixed and stirred until a slurry is formed at a temperature of 35-45℃. Isopropylamine is then added, and the mixture is stirred at 55-65℃ for 1.5-3.5 hours until the material is homogeneous, yielding a glyphosate isopropylamine salt aqueous solution. A compound synergist, pH adjuster, and defoamer are added to the above glyphosate isopropylamine salt aqueous solution, and stirring continues for 10-15 minutes until homogeneous. Antifreeze is then added, and the mixture is stirred for 20-30 minutes to obtain a transparent homogeneous solution. The above transparent homogeneous solution is tested, and if it passes the test, it is filled into the final product: a glyphosate solution soluble concentrate. Alternatively, at a temperature of 35-45℃, glyphosate and water are mixed and stirred until a slurry is formed; then isopropylamine is added, and the mixture is stirred at 55-65℃ for 1.5-3.5 hours until the material is uniformly stirred to obtain an aqueous solution of glyphosate isopropylamine salt; a compound synergist, pH adjuster, additive, and defoamer are added to the above aqueous solution of glyphosate isopropylamine salt and stirring is continued for 10-15 minutes until the mixture is uniform; then the loading agent and antifreeze are added and stirred for 20-30 minutes to obtain a transparent homogeneous solution; the above transparent homogeneous solution is tested, and after passing the test, it is filled to obtain the finished glyphosate solution soluble concentrate.

[0007] Preferably, the weight ratio of each raw material component is as follows: 30-40 parts glyphosate, 10-15 parts isopropylamine, 8-12 parts compound synergist, 2-3 parts antifreeze, 0.05-0.1 parts pH adjuster, 0.1-0.5 parts defoamer, and 40-50 parts water; Alternatively, glyphosate 30-40 parts, isopropylamine 10-15 parts, compound synergist 8-12 parts, antifreeze 2-3 parts, pH adjuster 0.05-0.1 parts, additives 2-3 parts, defoamer 0.1-0.5 parts, loading agent 1-2 parts, water 40-50 parts.

[0008] Preferably, the composite synergist is a mixture of propoxylated quaternary ammonium salt and ethoxyalkyl phosphate in a mass ratio of 1:1-1.5.

[0009] Preferably, the antifreeze is selected from ethylene glycol, propylene glycol, and glycerol.

[0010] Preferably, the defoamer is selected from one of butyl phosphate, isobutyl phosphate, n-octanol, and organosilicon defoamers.

[0011] Preferably, the pH adjuster is selected from formic acid, acetic acid, and citric acid.

[0012] Preferably, the loading agent is selected from one of aluminum pillar clay, magnesium aluminum silicate, and carboxymethyl cellulose.

[0013] Preferably, the additive is a polydopamine-sodium alginate complex, and its preparation method includes the following steps: Sodium alginate was dissolved in water to prepare a homogeneous sodium alginate solution of 1-2 wt%. N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added to the sodium alginate solution, and the mixture was stirred at 24-26℃ for 3-4 h to obtain mixed solution A. Dopamine hydrochloride was added to mixed solution A, and after stirring until homogeneous, the pH was adjusted to 4.5-5 with 2-2.5 mol / L hydrochloric acid. The mixture was then stirred at 24-26℃ for 24-26 h to obtain mixed solution B. Mixed solution B was placed in a dialysis bag and dialyzed in water for 72-96 h, followed by freeze-drying to obtain a solid crude product. The solid crude product was redissolved in water to obtain a crude product solution. The solution was then treated with 2-3 mol / L hydrochloric acid... The pH of the crude product solution was adjusted to 8-8.5 using NaOH aqueous solution, and stirred at 25°C for 4-5 hours. Then, it was dialyzed again for 24-26 hours and then freeze-dried to obtain the final product, polydopamine-sodium alginate complex.

[0014] Preferably, the additive is a polydopamine-sodium alginate complex, and its preparation method includes the following steps, in parts by weight: Dissolve 2-3 parts of sodium alginate in 200-250 parts of water to prepare a 1-2 wt% homogeneous sodium alginate solution; add 1-2 parts of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and 1-1.5 parts of N-hydroxysuccinimide to the above sodium alginate solution, stir at 24-26℃ for 3-4 h to obtain mixed solution A; add 1.5-2 parts of dopamine hydrochloride to mixed solution A, stir evenly, adjust the pH to 4.5-5 with 2-2.5 mol / L hydrochloric acid, and then stir at 24-26℃ for 24-26 h to obtain mixed solution B; place mixed solution B in a dialysis bag and dialyze in water for 72-96 h, then freeze-dry to obtain a solid crude product; take 0.02-0.05 parts of the above solid crude product and redissolve it in 10-20 parts of water to obtain a crude product solution; use 2-3 mol / L... The pH of the crude product solution was adjusted to 8-8.5 using NaOH aqueous solution, and stirred at 25°C for 4-5 hours. Then, it was dialyzed again for 24-26 hours and then freeze-dried to obtain the final product, polydopamine-sodium alginate complex.

[0015] The second objective of this invention is to provide a glyphosate soluble concentrate, prepared by the above-described preparation method.

[0016] In this invention, propylene glycol acts as an antifreeze agent, helping to ensure that glyphosate soluble concentrate maintains its fluidity and stability at low temperatures. Propylene glycol can lower the freezing point of the solution, preventing glyphosate soluble concentrate from crystallizing or freezing in cold climates, thus increasing its effectiveness and efficacy, and allowing it to remain effective under a wider range of climatic conditions.

[0017] In this invention, the organosilicon defoamer can quickly defoam and prevent foam regeneration, improve the spraying effect of the pesticide solution, and ensure that the pesticide solution is evenly distributed on the plant leaves, thereby improving the utilization rate and efficacy of glyphosate soluble concentrate.

[0018] In this invention, citric acid is used as a pH adjuster to adjust the pH value of glyphosate soluble concentrate to an appropriate range, which helps to improve the solubility and stability of glyphosate, reduce its possible degradation or transformation during storage, and promote compatibility with other components. This helps to prepare high-quality, stable glyphosate soluble concentrate products.

[0019] The beneficial effects of this invention are: 1. Compared with existing technologies, this invention uses a combination of propoxylated quaternary ammonium salt and ethoxyalkyl phosphate as a synergist. By enhancing the permeability and conductivity of glyphosate molecules within plants, it significantly improves the efficacy of glyphosate, making the prepared soluble concentrate more effective in inhibiting weed growth. Field efficacy trials have demonstrated that the soluble concentrate prepared by this invention is superior to other commercially available products in controlling weeds. Furthermore, this product has low toxicity, minimal negative impact on the environment and crops, and possesses a certain degree of safety.

[0020] 2. This invention improves the utilization rate and control effect of glyphosate by using aluminum-supported clay to load glyphosate, while reducing pesticide drift and volatility, thereby minimizing the impact on non-target organisms. Furthermore, the introduction of a polydopamine-sodium alginate complex for synergistic use not only increases the leaf deposition rate and rain washout resistance of glyphosate soluble concentrate, but also enhances its UV resistance. The increased leaf deposition rate allows glyphosate to adhere more effectively to the leaf surface, improving pesticide utilization and weed control. Simultaneously, the enhanced rain washout resistance allows the pesticide to maintain its effectiveness even in rainy seasons or humid environments, reducing runoff and extending the effective period. This reduces the need for repeated applications and alleviates labor intensity. In addition, the improved UV resistance of glyphosate protects its active ingredient from the degradation of ultraviolet rays in sunlight, ensuring its effective action time on the leaves and further enhancing efficacy. These improvements collectively enhance the overall performance of the glyphosate soluble concentrate prepared in this invention, making it more efficient and economical in agricultural production and providing farmers with a more reliable weed control solution. Detailed Implementation

[0021] The parameters and sources of the specific chemical substances used.

[0022] Aluminum column support clay: Manufacturer is Shanghai Yingxin Laboratory Equipment Co., Ltd., EINECS No.: 629-654-0; Carboxymethyl cellulose: Purity: 99%, Manufacturer: Hubei Qifei Pharmaceutical Chemical Co., Ltd., Product No.: QF2782; Magnesium aluminum silicate: Purity: 99%, Manufacturer: Hubei Xinhongli Chemical Co., Ltd., Product No.: XHL0498; Silicone defoamer: Brand: Momentive (USA), Grade: SAG1572; Propoxylated quaternary ammonium salt: Brand: Klein, Grade: SYNERGEN™ B3155; Ethoxyalkyl phosphate: Brand: Lamberti, Grade: ROLFEN BIO.

[0023] Example 1 A method for preparing a glyphosate soluble concentrate includes the following steps: At a temperature of 40℃, 30 kg of glyphosate and 45.35 kg of water were mixed and stirred until a slurry was formed. Then, 12.5 kg of isopropylamine was added, and the mixture was stirred at 55℃ for 3 hours until the material was uniformly mixed, resulting in an aqueous solution of glyphosate isopropylamine salt. 10 kg of compound synergist, 0.05 kg of citric acid, and 0.1 kg of organosilicon defoamer were added to the above aqueous solution of glyphosate isopropylamine salt, and the mixture was stirred for 10 minutes until it was uniformly mixed. Then, 2 kg of propylene glycol was added and stirred for 20 minutes to obtain a transparent homogeneous solution. The above transparent homogeneous solution was tested, and after passing the test, it was filled into the final product, which is a glyphosate solution soluble concentrate.

[0024] The composite synergist is composed of 4.5 kg of propoxylated quaternary ammonium salt and 5.5 kg of ethoxyalkyl phosphate.

[0025] Example 2 Field efficacy trials This experiment complied with the Ministry of Agriculture of the People's Republic of China Announcement No. 2570 "Good Manufacturing Practice for Pesticide Registration Trials", "Guidelines for Field Efficacy Testing of Pesticides (I) Control of Weeds in Non-Cultivated Land with Herbicides" (GB / T17980.51-2000) and Yunnan Kewang Biotechnology Co., Ltd. "Standard Operating Procedures for Field Efficacy Testing of Herbicides for Control of Weeds in Non-Cultivated Land" (SOP-JS-2-007). The experiment was conducted strictly in accordance with the experimental protocol.

[0026] Experimental location: Xincun Village, Tangchi Street, Yiliang County, Kunming City, Yunnan Province, longitude 103.056838, latitude 24.965327, altitude: 1769m.

[0027] Target weeds: Weeds in non-cultivated land, mainly including: Cynodon dacrylon (L.) Pers.; Digitaria sanguinalis L.Scop; Alternanthera philoxeroides (Mart.) Griseb.; Polygonum nepalense Meisn.

[0028] The test substance was the glyphosate soluble concentrate prepared in Example 1 of this invention; the control reagent was 41% glyphosate isopropylamine saline concentrate (commissioned by Jilin Bangnong Bio-Agriculture Co., Ltd., and contracted by Guangxi Lumingbao Chemical Co., Ltd.).

[0029] Dosage: Table 1 Experimental Design of Test Reagents

[0030] Community Arrangements: The neighborhoods are arranged using a randomized block arrangement; the neighborhood area is 30m². 2 The number of repetitions was 4, covering a total of 20 cells, as detailed in Table 2 below: Table 2 Field plot arrangement

[0031] A 1m protective barrier was set up around the test area and test site.

[0032] Application: Targeted foliar spraying was used; water usage was 40 liters / mu (600 liters / hectare); the experimental plot was divided into uniform 30m² areas. 2 For each of the 20 plots, a certain amount of the test substance was accurately measured into centrifuge tubes, labeled, and brought to the test site. Before application, the drug solution was prepared using a two-stage dilution method. The blank control area was first sprayed with an equal amount of water. In the drug treatment area, each plot was sprayed uniformly and at a constant speed, from low concentration to high concentration, without overlapping or missing any areas. Before applying different drug treatments, the sprayer was washed according to the standard operating procedure.

[0033] investigation: Frequency and timing: The weed population (species and number of plants) was investigated before application; the plant control efficacy was investigated 15 days after application; and the plant control efficacy and fresh weight control efficacy were investigated 40 days after application.

[0034] Investigation methods: During the baseline survey before pesticide application, 4 points were randomly selected from each plot, with each point covering 0.25 square meters, to investigate the types and number of weeds. Subsequent surveys were conducted at fixed points. 40 days after pesticide application, in addition to investigating the types and number of weeds, the fresh weight of surviving weeds after root removal was also investigated, and the plant control efficacy and fresh weight control efficacy of the test pesticide against the target weeds were calculated.

[0035] The efficacy calculation method involves retaining the result to two decimal places. The control effect is calculated using the following formula: Control efficacy (%) = [Number of residual weeds (fresh weight) in the blank control area - Number of residual weeds (fresh weight) in the treatment area] / Number of residual weeds (fresh weight) in the blank control area × 100 The experimental data were processed and analyzed using the DPS7.05 data processing system and the Duncan's New Multiple Range (DMRT) method.

[0036] The experimental results are shown in Table 3 below (the data in the table are the average of four replicates, where uppercase and lowercase letters represent significance levels of 0.01 and 0.05, respectively): Table 3. Experimental Results

[0037] The significance analysis showed that the control efficacy of total fresh weight of weeds was extremely significant between treatment 1 and treatments 2 and 3, and significant between treatments 2 and 3. There was no significant difference in the control efficacy of total fresh weight of weeds between treatment 2 and control treatment 4, while the control efficacy of total fresh weight of weeds between treatment 3 and control treatment 4 was extremely significant. In terms of overall efficacy, when the dosage of the test agent was 200.00~400.00 mL / mu (i.e., the effective ingredient dosage was 1230.00~2460.00 g / ha), the control efficacy against total weeds in non-cultivated land increased with the increase of the dosage of the test agent (i.e., the soluble concentrate prepared in this invention). At 15 days post-application, the control efficacy against total weeds in non-cultivated land increased from 79% to over 90% with increasing dosage. At 40 days post-application, the control efficacy against total weeds in non-cultivated land remained above 90%, and the control efficacy against the fresh weight of total weeds was above 91%. This indicates that the test agent used in this experiment had a good control effect on weeds in non-cultivated land. Meanwhile, the glyphosate soluble concentrate prepared in this invention, at a dosage of 200-400 ml / mu (active ingredient dosage of 1230.0~2460.0 g / ha), showed no adverse effects on neighboring organisms and is safe for neighboring crops and other non-target organisms, demonstrating good safety.

[0038] Example 3 Field efficacy trials This experiment was conducted in accordance with the "Good Manufacturing Practice for Pesticide Registration Trials" and with reference to the "Guidelines for Field Efficacy Trials of Pesticides (I) Herbicides for Control of Weeds in Non-Cultivated Land" (GB / T17980.51-2000) and the relevant standard operating procedures of Gansu Jinsu Agricultural Technology Co., Ltd. At the time of application, the weeds were in their vigorous growth stage, with a rich variety of weeds and a uniform distribution, meeting the requirements for conducting the experiment.

[0039] Experimental location: Jiangjiaping Village, Taishi Town, Lintao County, Dingxi City, Gansu Province (E: 103.781695, N: 35.652741).

[0040] Target weeds for control: Annual and perennial non-cultivated land weeds include: Inula japonica Thunb., Setaria viridis (Linn.) Beauv., Elymus dahuricus Turcz., and Polygonum lapathifolium Linn.

[0041] The test substance was the glyphosate soluble concentrate prepared in Example 1 of this invention; the control agent was 41% glyphosate isopropylamine salt solution (Lianyungang Liben Crop Technology Co., Ltd.).

[0042] The dosage of the reagent and the experimental design of the test reagent are as described in Example 2.

[0043] The community arrangement is based on Example 2.

[0044] The application method is the same as in Example 2.

[0045] Number of surveys and timeframes: Weed population (type and number of plants) was surveyed before application; plant control efficacy was surveyed 15 days after application; and plant control efficacy and fresh weight control efficacy were surveyed 35 days after application.

[0046] The investigation methods and calculation of prevention and control effects are based on Example 2.

[0047] The experimental results are shown in Table 4 below (the data in the table are the average of four replicates, where uppercase and lowercase letters represent significance levels of 0.01 and 0.05, respectively): Table 4. Test Results

[0048] The significance analysis showed that the control efficacy of total fresh weight of weeds was extremely significant between treatment 1 and treatments 2 and 3, and significant between treatments 2 and 3. There was no significant difference in the control efficacy of total fresh weight of weeds between treatment 2 and control treatment 4, while the control efficacy of total fresh weight of weeds between treatment 3 and control treatment 4 was extremely significant. In terms of overall efficacy, when the dosage of the test agent was 200.00~400.00 mL / mu (i.e., the effective ingredient dosage was 1230.00~2460.00 g / ha), the control efficacy against total weeds in non-cultivated land increased with the increase in the dosage of the test agent (i.e., the soluble concentrate prepared in this invention). At 15 days post-application, the control efficacy against total weeds in non-cultivated land remained above 92%; at 35 days post-application, the control efficacy remained above 90%; and at 35 days post-application, the control efficacy against total fresh weight of weeds was above 91%. This indicates that the test agent used in this experiment had good control efficacy against weeds in non-cultivated land. Meanwhile, no effects on other non-target organisms were observed visually at 15 days post-application, indicating good safety.

[0049] Example 4 Field efficacy trials This experiment was conducted in accordance with the "Good Manufacturing Practice for Pesticide Registration Trials" (Announcement No. 2570 of the Ministry of Agriculture of the People's Republic of China), with reference to the "Good Manufacturing Practice for Field Efficacy Trials of Pesticide Registration" (NY / T2085-2016), the "Guidelines for Field Efficacy Trials of Pesticides (I) Herbicides for Controlling Weeds in Non-Cultivated Land" (GB / T17980.51-2000), and the standard operating procedures of "Efficacy Trials of Herbicides for Controlling Weeds in Non-Cultivated Land" (SOP-QW-3-007) issued by Anhui Huachen Testing Technology Research Institute Co., Ltd.

[0050] Experimental location: Sanfanggang Village, Wushitou Community, Xinzhan District, Hefei City, Anhui Province (E: 117.383124, N: 32.044136).

[0051] Target weeds for control: The main dominant weeds in non-cultivated land include: Conyza canadensis (L.) Cronq., Sonchus brachyotus DC., Setaria viridis (L.) Beauv., and other weeds (Viciasativa L., Imperata cylindrica (L.) Beauv.). Reagents: The test substance was the glyphosate soluble concentrate prepared in Example 1 of this invention; the control reagent was 43% glyphosate isopropylamine saline concentrate (Zhejiang Xin'an Chemical Group Co., Ltd.).

[0052] Dosage: Table 5 Experimental Design of Test Reagents

[0053] The community arrangement is based on Example 2.

[0054] The application method is the same as in Example 2.

[0055] Number of surveys and time period: The control efficacy was investigated 15 days after application; and the control efficacy and fresh weight control efficacy were investigated 35 days after application.

[0056] The investigation methods and calculation of prevention and control effects are based on Example 2.

[0057] The experimental results are shown in Table 6 below (the data in the table are the average of four replicates, where uppercase and lowercase letters represent significance levels of 0.01 and 0.05, respectively): Table 6. Experimental Results

[0058] The significance analysis showed that the control efficacy of total fresh weight of weeds was extremely significant between treatment 1 and treatments 2 and 3, and significant between treatments 2 and 3. There was no significant difference in the control efficacy of total fresh weight of weeds between treatment 2 and control treatment 4, while the control efficacy of total fresh weight of weeds between treatment 3 and control treatment 4 was extremely significant. From the overall efficacy perspective, when the dosage of the test agent was 200.00~400.00 mL / mu (i.e., the effective ingredient dosage was 1230.00~2460.00 g / ha), the control efficacy against total weeds in non-cultivated land increased with increasing dosage of the test agent (i.e., the soluble concentrate prepared in this invention). At 15 days post-application, the control efficacy against total weeds in non-cultivated land increased from 89% to over 97% with increasing dosage. At 35 days post-application, the control efficacy against total weeds in non-cultivated land increased from 87% to over 95% with increasing dosage. Furthermore, at 35 days post-application, the control efficacy against total fresh weight of weeds increased from 88% to over 95% with increasing dosage. This indicates that the test agent used in this experiment had good control efficacy against weeds in non-cultivated land. Meanwhile, no effects on other non-target organisms were observed visually 15 days after drug administration, indicating good safety.

[0059] Example 5 A method for preparing a glyphosate soluble concentrate includes the following steps: At a temperature of 40℃, 30 kg of glyphosate and 41.35 kg of water were mixed and stirred until a slurry was formed. Then, 12.5 kg of isopropylamine was added, and the mixture was stirred at 55℃ for 3 hours until the material was uniformly mixed, resulting in a glyphosate isopropylamine salt aqueous solution. 10 kg of compound synergist, 0.05 kg of citric acid, 2 kg of additive, and 0.1 kg of organosilicon defoamer were added to the above glyphosate isopropylamine salt aqueous solution, and the mixture was stirred for 10 minutes until uniformly mixed. Then, 2 kg of aluminum pillar clay and 2 kg of propylene glycol were added and stirred for 20 minutes to obtain a transparent homogeneous solution. The above transparent homogeneous solution was tested, and after passing the test, it was filled into the final product, a glyphosate solution soluble concentrate.

[0060] The composite synergist is composed of 4.5 kg of propoxylated quaternary ammonium salt and 5.5 kg of ethoxyalkyl phosphate.

[0061] The additive is a polydopamine-sodium alginate complex, and its preparation method includes the following steps: 2 g of sodium alginate was dissolved in 200 g of water to prepare a 1 wt% homogeneous sodium alginate solution. 1.725 g of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and 1.036 g of N-hydroxysuccinimide were added to the sodium alginate solution, and the mixture was stirred at 25 °C for 3 h to obtain mixed solution A. 1.7 g of dopamine hydrochloride was added to mixed solution A, and after stirring until homogeneous, the pH was adjusted to 4.5 with 2 mol / L hydrochloric acid. The mixture was then stirred at 25 °C for 24 h to obtain mixed solution B. Mixed solution B was placed in a dialysis bag (MWCO). The crude product was dissolved in 3.5 kDa water and dialyzed in deionized water for 72 h, then freeze-dried to obtain a solid crude product. 40 mg of the above solid crude product was redissolved in 10 g of water to obtain a crude product solution. The pH of the crude product solution was adjusted to 8.5 with 2 mol / L NaOH aqueous solution, stirred at 25 °C for 5 h, dialyzed again for 24 h, and then freeze-dried to obtain the final product, polydopamine-sodium alginate complex.

[0062] Example 6 A method for preparing glyphosate soluble concentrate, the main difference from Example 5 is that 2 kg of aluminum pillar clay is replaced with 2 kg of magnesium aluminum silicate.

[0063] Example 7 A method for preparing a glyphosate soluble concentrate, the main difference from Example 5 is that 2 kg of aluminum pillar clay is replaced with 2 kg of carboxymethyl cellulose.

[0064] Comparative Example 1 A method for preparing a glyphosate soluble concentrate includes the following steps: At a temperature of 40℃, 30 kg of glyphosate and 43.35 kg of water were mixed and stirred until a slurry was formed. Then, 12.5 kg of isopropylamine was added, and the mixture was stirred at 55℃ for 3 hours until the material was uniformly mixed, resulting in a glyphosate isopropylamine salt aqueous solution. 10 kg of compound synergist, 0.05 kg of citric acid, and 0.1 kg of organosilicon defoamer were added to the above glyphosate isopropylamine salt aqueous solution, and the mixture was stirred for 10 minutes until uniformly mixed. Then, 2 kg of aluminum pillar clay and 2 kg of propylene glycol were added and stirred for 20 minutes to obtain a transparent homogeneous solution. The above transparent homogeneous solution was tested, and after passing the test, it was filled into the final product, a glyphosate solution soluble concentrate.

[0065] The composite synergist is composed of 4.5 kg of propoxylated quaternary ammonium salt and 5.5 kg of ethoxyalkyl phosphate.

[0066] Comparative Example 2 A method for preparing a glyphosate soluble concentrate includes the following steps: At a temperature of 40℃, 30 kg of glyphosate and 43.35 kg of water were mixed and stirred until a slurry was formed. Then, 12.5 kg of isopropylamine was added, and the mixture was stirred at 55℃ for 3 hours until the material was uniformly mixed, resulting in an aqueous solution of glyphosate isopropylamine salt. 10 kg of compound synergist, 0.05 kg of citric acid, 2 kg of additive, and 0.1 kg of organosilicon defoamer were added to the above aqueous solution of glyphosate isopropylamine salt, and the mixture was stirred for another 10 minutes until it was uniformly mixed. Then, 2 kg of propylene glycol was added and stirred for 20 minutes to obtain a transparent homogeneous solution. The above transparent homogeneous solution was tested, and after passing the test, it was filled into the final product, which is a glyphosate solution soluble concentrate.

[0067] The composite synergist is composed of 4.5 kg of propoxylated quaternary ammonium salt and 5.5 kg of ethoxyalkyl phosphate.

[0068] The preparation method of the additive is the same as that in Example 5.

[0069] Test Example 1 Blade adhesion performance test Fresh, viable seedlings of *Sonchus oleraceus* were selected. The leaves were washed with deionized water to remove dust while maintaining the integrity of the leaf structure, and then allowed to air dry. Sample solutions were prepared by diluting 1 mL of the soluble solvents used in Examples 1, 5-7, and Comparative Examples 1-2 with 10 mL of water. These sample solutions were then evenly sprayed onto the leaf surface using a spray gun and allowed to air dry. The leaves were divided into two parts along the main vein. One part was rinsed with 100 mL of deionized water under pressure, simulating rainfall, while the other part was left unrinsed. After the droplets on the leaf surface dried, both parts of the leaf were cut into smaller pieces with scissors and extracted with 2.0 mL of dichloromethane for 12 h. Then, dichloromethane was transferred to centrifuge tubes using a disposable dropper. The leaves were rinsed with 1.0 mL of dichloromethane three times. The dichloromethane used for rinsing was transferred to the centrifuge tubes mentioned above, and the tubes were placed in a fume hood to evaporate the dichloromethane. Then, 0.2 mL of methanol was added to dissolve the dichloromethane, and the solution was analyzed by high-performance liquid chromatography (HPLC). Based on the standard curve, the peak areas of glyphosate before and after simulated rainwater runoff were calculated. The retention rate was calculated using the following formula: Retention rate (%) = [(S1-S2) / S1] × 100% Where S1 is the simulated peak area before rainfall erosion; S2 is the simulated peak area after rainfall erosion.

[0070] The test results are averaged, and the details are shown in Table 1.

[0071] Table 7. Test results of soluble solvent adhesion performance on leaf surfaces for each group.

[0072] As shown in Table 7, compared with Examples 1, 5-7, and Comparative Examples 1-2, the glyphosate retention of Example 1 after rainwater washing was significantly lower than that of Examples 5-7 and Comparative Examples 1-2. Comparing Examples 5-7 and Comparative Examples 1-2, the retention of Example 5-7 was higher than that of Comparative Examples 1-2, with Example 5 exhibiting the highest glyphosate retention. This may be because the aluminum-pillared clay has a unique layered structure, providing a large adsorption surface for glyphosate, and has a narrow particle size distribution, allowing it to better fill the depressions and pores on the leaf surface, increasing the coverage area of ​​glyphosate on the leaf surface. Furthermore, during the preparation of the polydopamine-sodium alginate complex, dopamine is oxidized to dopaquinone under alkaline conditions and further rearranged to form 5,6-dihydroxyindole. However, dopamine, dopaquinone, and 5,6-dihydroxyindole are easily oxidized and copolymerized to form dimers or polymers, ultimately polymerizing to form polydopamine with an irregular self-assembled particle structure. Polydopamine is rich in functional groups such as catechols and amino groups, which can adhere to other materials through covalent and non-covalent bonds. Therefore, when pesticide-containing droplets fall onto the leaf surface, the abundant catechol and amino groups in the polydopamine-sodium alginate complex interact with the hydrophobic waxy layer of the leaf to form strong hydrogen bonds, enhancing the adhesion between the droplet surface and the waxy layer, allowing the pesticide droplets to effectively adhere to the crop leaf surface. Al on aluminum-pillared clay loaded with glyphosate... 3+ The ions complex with a large number of catechol groups in the polydopamine-sodium alginate complex to form a dense cross-linked network, while the sodium alginate contained therein can combine with Al 3+ Ion dynamic coordination forms a gel material. The interpenetrating structure and the formation of the gel material effectively encapsulate glyphosate and increase its contact area with the leaves. This not only improves the stability of glyphosate but also increases its adhesion to the leaves, facilitating more uniform and stable deposition on the leaf surface. Simultaneously, the polydopamine-sodium alginate complex and the Al on the aluminum-pillared clay... 3+ Ions can also crosslink on the leaf surface through catechol-metal and carboxyl-metal coordination bonds, forming a dense supramolecular polymer network with topological and strong cohesion. This not only bridges the gap between intermolecular interactions and pesticide deposition performance, but also effectively reduces the damage to the structure caused by water swelling, further improving the leaf deposition rate of pesticide droplets and the ability to resist rain erosion.

[0073] Test Example 2 UV stability test Take 1 mL of each of the soluble solutions prepared in Examples 1, 5-7, and Comparative Examples 1-2, and dilute with 10 mL of deionized water. Record these as Group 1 (Example 1), Group 5-7 (Example 5-7), and Group 1-2 (Comparative Examples 1-2), respectively. Expose each group of samples to a 36W germicidal lamp (254 nm) at a distance of 20 cm for 24 h, 48 h, and 96 h to test the stability against ultraviolet radiation. Analyze the changes in glyphosate content in each group using high-performance liquid chromatography (HPLC) with 270 nm ultraviolet detection (Agilent HP1260, USA). The chromatographic conditions are as follows: a reversed-phase Welch Ultimate XB-C18 column (250 × 4.6 mm inner diameter, 5 μm) was used, with methanol and water (80:20, v / v) as the mobile phase. Analyze using an injection volume of 20 μL and a flow rate of 1.0 mL / min. All solvents were filtered through a 0.45 μm membrane filter before use.

[0074] The test results are averaged, and the details are shown in Table 8.

[0075] Table 8. Glyphosate degradation rate for each group

[0076] As shown in Table 8, compared with Examples 1, 5-7, and Comparative Examples 1-2, the degradation rate of glyphosate in Example 1 was significantly higher than that in Examples 5-7 and Comparative Examples 1-2. Comparing Examples 5-7 and Comparative Examples 1-2, the degradation rate of Examples 5-7 was higher than that in Comparative Examples 1-2, with Example 5 exhibiting the lowest glyphosate degradation rate. This indicates that the soluble agent prepared in this invention possesses excellent UV resistance. The reason for this may be that the layered structure and large specific surface area of ​​the aluminum-pillared clay provide a large amount of adsorption surface, which helps to form a tight bond with glyphosate molecules. This tight bond helps reduce the decomposition of glyphosate molecules under ultraviolet light, thereby improving its UV resistance. Furthermore, polydopamine has good antioxidant and UV resistance properties, absorbing ultraviolet light and converting it into heat energy, thus reducing the destructive effect of ultraviolet light on glyphosate. Simultaneously, it reduces oxidative damage to glyphosate molecules by capturing and neutralizing free radicals generated under light conditions. Meanwhile, the Al on the glyphosate-loaded aluminum-pillared clay... 3+ The ions complex with a large number of catechol groups in the polydopamine-sodium alginate complex solution to form a dense cross-linked network, while the sodium alginate contained therein can react with Al 3+ Ion dynamic coordination forms a gel material. The interpenetrating structure and the formation of the gel material can effectively encapsulate glyphosate, forming a protective barrier to isolate glyphosate molecules from the external environment. At the same time, it promotes the aggregation between glyphosate molecules, forming a "cage" structure, thereby further reducing the direct contact between ultraviolet light and glyphosate molecules, reducing the photolysis rate, and improving the UV resistance of glyphosate.

Claims

1. A method for preparing a glyphosate soluble concentrate, characterized in that, Includes the following steps: Glyphosate and water are mixed and stirred until a slurry is formed at a temperature of 35-45℃. Isopropylamine is then added, and the mixture is stirred at 55-65℃ for 1.5-3.5 hours until the material is homogeneous, yielding a glyphosate isopropylamine salt aqueous solution. A compound synergist, pH adjuster, and defoamer are added to the above glyphosate isopropylamine salt aqueous solution, and stirring continues for 10-15 minutes until homogeneous. Antifreeze is then added, and the mixture is stirred for 20-30 minutes to obtain a transparent homogeneous solution. The above transparent homogeneous solution is tested, and if it passes the test, it is filled into the final product: a glyphosate solution soluble concentrate. Alternatively, at a temperature of 35-45℃, glyphosate and water are mixed and stirred until a slurry is formed; then isopropylamine is added, and the mixture is stirred at 55-65℃ for 1.5-3.5 hours until the material is uniformly stirred to obtain an aqueous solution of glyphosate isopropylamine salt; a compound synergist, pH adjuster, additive, and defoamer are added to the above aqueous solution of glyphosate isopropylamine salt and stirring is continued for 10-15 minutes until the mixture is uniform; then the loading agent and antifreeze are added and stirred for 20-30 minutes to obtain a transparent homogeneous solution; the above transparent homogeneous solution is tested, and after passing the test, it is filled to obtain the finished glyphosate solution soluble concentrate.

2. The method for preparing glyphosate soluble concentrate as described in claim 1, characterized in that, The weight proportions of each raw material component are as follows: 30-40 parts glyphosate, 10-15 parts isopropylamine, 8-12 parts compound synergist, 2-3 parts antifreeze, 0.05-0.1 parts pH adjuster, 0.1-0.5 parts defoamer, and 40-50 parts water; Alternatively, glyphosate 30-40 parts, isopropylamine 10-15 parts, compound synergist 8-12 parts, antifreeze 2-3 parts, pH adjuster 0.05-0.1 parts, additives 2-3 parts, defoamer 0.1-0.5 parts, loading agent 1-2 parts, water 40-50 parts.

3. The method for preparing glyphosate soluble concentrate as described in claim 1 or 2, characterized in that: The composite synergist is a mixture of propoxylated quaternary ammonium salt and ethoxyalkyl phosphate in a mass ratio of 1:1-1.

5.

4. The method for preparing glyphosate soluble concentrate as described in claim 1 or 2, characterized in that: The antifreeze is selected from one of ethylene glycol, propylene glycol, and glycerol.

5. The method for preparing glyphosate soluble concentrate as described in claim 1 or 2, characterized in that: The defoamer is selected from one of butyl phosphate, isobutyl phosphate, n-octanol, and organosilicon defoamers.

6. The method for preparing glyphosate soluble concentrate as described in claim 1 or 2, characterized in that: The pH adjuster is selected from formic acid, acetic acid, and citric acid.

7. The method for preparing glyphosate soluble concentrate as described in claim 1 or 2, characterized in that, The loading agent is selected from one of aluminum pillar clay, magnesium aluminum silicate, and carboxymethyl cellulose.

8. The method for preparing glyphosate soluble concentrate as described in claim 1 or 2, characterized in that, The additive is a polydopamine-sodium alginate complex, and its preparation method includes the following steps: Sodium alginate was dissolved in water to prepare a 1-2 wt% homogeneous sodium alginate solution; N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added to the above sodium alginate solution, and the mixture was stirred at 24-26℃ for 3-4 h to obtain mixed solution A; dopamine hydrochloride was added to mixed solution A, and after stirring evenly, 2-2.5 g of water was used to prepare the solution. Adjust the pH to 4.5-5 with mol / L hydrochloric acid, then stir at 24-26℃ for 24-26 h to obtain mixed solution B; place mixed solution B in a dialysis bag and dialyze in water for 72-96 h, then freeze-dry to obtain a solid crude product; redissolve the above solid crude product in water to obtain a crude product solution; adjust the pH of the crude product solution to 8-8.5 with 2-3 mol / L NaOH aqueous solution, stir at 25℃ for 4-5 h, then dialyze again for 24-26 h, then freeze-dry to obtain the final product polydopamine-sodium alginate complex.

9. The method for preparing glyphosate soluble concentrate as described in claim 8, characterized in that, The additive is a polydopamine-sodium alginate complex, and its preparation method includes the following steps, by weight: Dissolve 2-3 parts of sodium alginate in 200-250 parts of water to prepare a 1-2 wt% homogeneous sodium alginate solution; add 1-2 parts of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride and 1-1.5 parts of N-hydroxysuccinimide to the above sodium alginate solution, and stir at 24-26℃ for 3-4 hours to obtain mixed solution A; add 1.5-2 parts of dopamine hydrochloride to mixed solution A, stir evenly, and then use 2-2.5... Adjust the pH to 4.5-5 with mol / L hydrochloric acid, then stir at 24-26℃ for 24-26 h to obtain mixed solution B; place mixed solution B in a dialysis bag and dialyze in water for 72-96 h, then freeze-dry to obtain a solid crude product; take 0.02-0.05 parts of the above solid crude product and redissolve it in 10-20 parts of water to obtain a crude product solution; adjust the pH of the crude product solution to 8-8.5 with 2-3 mol / L NaOH aqueous solution, stir at 25℃ for 4-5 h, then dialyze again for 24-26 h, then freeze-dry to obtain the final product polydopamine-sodium alginate complex.

10. A glyphosate soluble concentrate, characterized in that: Prepared by the method described in any one of claims 1-9.

Images