High-permeability glufosinate-ammonium compounded flumioxazin nano suspending agent and preparation method thereof

Abstract

The invention belongs to the field of pesticides, and particularly relates to a high-permeability glufosinate-ammonium compounded flumioxazin nano suspending agent and a preparation method thereof, and the suspending agent comprises the following components: 5wt%-10wt% of glufosinate-ammonium and flumioxazin, 2.32 wt%-6.78 wt% of a functional additive, a pH regulator, 3wt%-7wt% of a nano carrier and the balance of water. The preparation method comprises the following steps: stirring a compound solution of glufosinate-ammonium and flumioxazin, loading the compound solution to the nano-porous silicon dioxide, mixing with a functional additive solution by taking water as a solvent, adjusting the pH value, and effectively sanding to prepare the nano-suspending agent. Compared with a common suspending agent, the nano suspending agent has high permeability, the preparation method is simple and efficient, the particle size is as small as nanoscale, the nano suspending agent has high biocompatibility and bioavailability, and druggability, preparation stability, biological activity and the like of pesticide compounds can be improved to a great extent. The lasting action time of the pesticide and the permeability and the adhesiveness of the pesticide on the leaf surfaces of plants are enhanced, so that the use amount of the pesticide is reduced.

Description

Technical Field

[0001] The invention relates to the field of pesticides, in particular to a glufosinate-ammonium compound fluazifop-propylamine nano suspension and a preparation method thereof. Background Art

[0002] Glufosinate, also known as glufosinate, is a broad-spectrum contact herbicide with a chemical formula of C5H 15 N2O4P, molecular weight is 198.16, chemical name is 4-[hydroxy(methyl)phosphonyl]-DL-homoalanine or 2-amino-4-[hydroxy(methyl)phosphonyl]butyrate ammonium, crystal is white. Melting point is 210℃, boiling point is 519.1℃ at 760mmHg. It is easily soluble in water, but not easily soluble in organic solvents. It is a broad-spectrum contact-killing herbicide successfully developed by the former German Aigfor company in the 1980s. It belongs to the phosphonic acid herbicide, which can inhibit glutamine synthetase in the nitrogen metabolism pathway of plants, thereby interfering with plant metabolism and causing plant death. When glufosinate enters the plant body, it can combine with ATP and occupy the reaction site of glutamine synthetase, thereby hindering the synthesis of glutamine, reducing the synthesis of substances such as proteins and nucleotides, leading to hindered photosynthesis, increased intracellular ammonium ion content, severe damage to its biological membrane and causing chloroplast disintegration. Therefore, it kills weeds quickly and has a long action time. It also has a wide spectrum of weed control and can remove almost all annual and even perennial weeds in farmland.

[0003] Flumioxazin, commonly known as flumioxazin in English, is a white powdery solid. It was developed and marketed by Sumitomo Chemical Co., Ltd. in Japan in 1993 and is used to control grass weeds and broad-leaved weeds on various crops such as soybeans, cotton, and grapes. It is a N-phenylpeptide imide selective contact herbicide, a broad-spectrum, high-efficiency, broad-market and high-growth dryland herbicide. It has been registered in many countries including Brazil, the United States, China, France, Canada, Thailand, Mexico, Chile, Japan, Australia, Germany, the Czech Republic, Uruguay, Argentina, Russia, Hungary, Romania, Spain, South Africa, Bulgaria, Slovakia, and South Korea, and has broad application prospects.

[0004] Fluazifop-butyl is a protoporphyrinogen oxidase inhibitor. PPO is an enzyme in the biosynthesis of chlorophyll. It can be absorbed by the young shoots and leaves of plants and transmitted in the plant body, inhibiting the biosynthesis of chlorophyll, causing sensitive weeds to wilt and die quickly. It is a contact-type selective herbicide. Fluazifop-butyl can be transmitted in the plant body, causing protoporphyrin accumulation, enhancing the lipid peroxidation of the cell membrane, and thus causing irreversible damage to the cell membrane structure and cell function of sensitive weeds. Weeds generally wilt, whiten and die within 24-48 hours. It can effectively control annual broadleaf weeds and some grass weeds, and has a good control effect on weeds that have developed resistance to glyphosate in genetically modified cotton and soybean fields; therefore, it is often used in combination with glyphosate. It is also easy to degrade and has little impact on crops grown later.

[0005] Suspension concentrate is a mixture of pesticide original drug, carrier and dispersant. It is composed of insoluble or slightly soluble original drug and certain adjuvants in water, which are dispersed in water relatively evenly through ultrafine grinding to form a stable liquid-solid system with fine particles, high suspension and flowability. Suspension concentrate is usually composed of active ingredients, dispersants, thickeners, anti-precipitants, defoamers, antifreeze agents and water. The content of active ingredients is generally 5%-50%. The average particle size is generally about 3 microns. It is a new dosage form for pesticide processing. Nano suspension concentrate is a suspension liquid with a particle size between 10-400 nanometers. Its particle size is smaller than that of ordinary suspension concentrate, so it has better therapeutic effect. It has high biocompatibility and bioavailability, and is widely used in the fields of medicine, cosmetics and environment. It has high biocompatibility and bioavailability, thereby reducing the dosage and frequency of drugs, reducing the side effects caused by drugs, and can control the release rate of drugs, improve bioavailability, enhance drug absorption, and prolong the half-life of drugs. In addition, it is also widely used in cancer treatment, tumor targeting and in vivo imaging.

[0006] In summary, since the long-term single use of glufosinate often leads to weed resistance, it is usually used in combination with fluazifop-butyl. Glufosinate-ammonium combined with fluazifop-butyl is currently widely used in the market. The common glufosinate-ammonium and fluazifop-butyl compounds on the market are mainly wettable powders and oil suspensions. The dust generated by the preparation of powders is large, and the energy consumption of the production process is large, which is not good for the health of the staff engaged in production and pollutes the environment. The production of oil suspensions requires a large amount of organic solvents, which will increase production costs, further increase agricultural production costs, and the waste liquid generated affects the ecological environment. Therefore, it is necessary to produce an efficient and economical preparation process for the development of agriculture. Making it into a nano suspension can greatly improve the utilization efficiency of pesticides and reduce the use of pesticides, thereby achieving the purpose of protecting the environment. Summary of the invention

[0007] The present invention mainly provides a method for preparing a high-permeability glufosinate-ammonium compound fluazifop-propyl group suspension, which can solve the problems that the current glufosinate-ammonium compound fluazifop-propyl group suspension has low permeability, large drug usage leads to serious environmental pollution, and the drug is not easily absorbed due to rapid volatilization when spraying the drug at high temperature, in particular.

[0008] In order to solve the above technical problems, the present invention provides a high-permeability glufosinate-ammonium compound fluazifop-propyl acetate nano suspension, which is composed of the following components: 5wt%-10wt% of glufosinate-ammonium and fluazifop-propyl acetate, 2.32wt%-6.78wt% of functional additives, a pH regulator, 3wt%-7wt% of nanocarriers, and the balance is water.

[0009] The active ingredients are glufosinate ammonium and fluazifop-propyl acetate, and the mass ratio of glufosinate ammonium to fluazifop-propyl acetate is 40:1-80:1; the functional additives are 1.0wt%-1.5wt% of alkylnaphthalene sulfonate, 1.0wt%-4.0% of modified polycarboxylate, 0.1wt%-0.2% of ESAFLOR X 80, 0.02wt%-0.08% of ANTIFOAM AP 188, and 0.2wt%-1.0wt% of one of s-triazines and isothiazolinones; the pH regulator is phosphoric acid, and the pH of the system is adjusted to 6-7; and the nanocarrier is nanoporous silica.

[0010] A method for preparing a high-permeability glufosinate-ammonium combined with fluazifop-propylamine nano suspension comprises the following steps: S1, mixing the nano calcium carbonate suspension with the sodium silicate solution, adding dilute hydrochloric acid to react completely, and then slurrying and filtering with methanol to obtain a filter cake, calcining the filter cake in a muffle furnace at 500-800°C for 3-6h, and cooling in a nitrogen flow to obtain a porous powder solid; S2, crushing the solid in step S1 by a hammer mill, and then crushing it by a needle mill to prepare a porous silica carrier; S3, mixing glufosinate-ammonium and fluazifop-propyl acetate and stirring to form an aqueous solution, and then loading the aqueous solution onto nanoporous silica to obtain slurry A; S4, mixing the functional additive and water to obtain slurry B, and uniformly dispersing the slurry; S5. Slurry A and slurry B are stirred and mixed evenly, the balance is supplemented with water, and the pH is adjusted to 6-7 with phosphoric acid to obtain slurry C; S6. The slurry C and the grinding medium are firstly ground in a secondary sand mill, and then placed in a nano-scale sand mill for grinding, during which the temperature is controlled at 25° C.-50° C. to obtain the composite nano suspension.

[0011] Wherein, the homogenization and dispersion time in step S4 is 30min-60min, and the homogenization and dispersion speed is 1500rpm-2000rpm; the grinding medium in step S6 is one of 95TZP zirconium beads and 65 zirconium beads, which are sand-milled with secondary and nano-grade sand mills in sequence, the particle size of the zirconium beads of the secondary sand mill is 0.2mm-0.4mm, and the particle size of the zirconium beads of the nano-grade sand mill is 0.1mm-0.15mm; the grinding time of the nano-grade sand mill is 0.5h-1h, and the speed is 8000rpm-10000rpm, and a nano suspension is prepared, and the particle size D of the nano suspension is 90 <300nm, suspension rate ≥90%.

[0012] The nano-carrier in the present invention enables the effective ingredients to be loaded on the carrier, so that the drug is not easy to precipitate, the modified polycarboxylate can inhibit the growth of crystals, the functional additive is used to control the foam of the nano-suspension agent and increase the viscosity of the suspension agent system to increase the sand milling efficiency and reduce the particle sedimentation rate, thereby enhancing the stability of the suspension agent, and the pH regulator ensures that the effective ingredients are not degraded due to the increase in temperature during the grinding of the preparation, prevents the drug efficacy from being reduced, and ensures that the microbial limit of the drug within the validity period does not exceed the standard.

[0013] The invention greatly improves the permeability of the glufosinate-ammonium compound fluazifop, improves the utilization rate of the pesticide, reduces the usage amount of the pesticide, reduces the usage cost, and reduces the environmental pollution of the pesticide. The preparation method of the invention is simple, the nano-silica-loaded glufosinate-ammonium compound fluazifop has a high drug loading rate, stable product quality, is not easy to precipitate, has a long continuous action time of the drug, is easy to store, and has a good weed control effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is the chemical structure of glufosinate ammonium. DETAILED DESCRIPTION

[0015] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0016] Example 1 In this embodiment, a nano calcium carbonate suspension is mixed with a sodium silicate solution, diluted hydrochloric acid is added, and after the reaction is complete, methanol is used for pulping and filtering to obtain a filter cake, and the filter cake is calcined in a muffle furnace at 500-800° C. for 3-6 hours, and placed in a nitrogen flow to cool to a porous powder solid; the solid is then crushed by a hammer mill, and then crushed by a needle mill to prepare a porous silica carrier; 50g of glufosinate (chemical structure as Figure 1 As shown in the figure), 0.75g fluazifop-butyl was mixed with 70g nanoporous silica and 300g water to form an aqueous solution, and water was added to make up to 500g to obtain a slurry A of nanoporous silica loaded with active ingredients; then 10g modified polycarboxylate, 10g isopropylnaphthalene sulfonate, 2g ESAFLOR X 80, 0.8g ANTIFOAMAP 188, 2g s-triazine, add water to make up to 500g, stir evenly to obtain slurry B, and then homogenize and disperse for 40min, with the speed set to 1500rpm; then stir and mix slurry A and slurry B evenly, adjust the pH to 6-7 with phosphoric acid to obtain slurry C; slurry C and zirconium beads with a diameter of 0.2mm are used as grinding media in a secondary sand mill for secondary grinding and sand milling for 1h, with the speed set to 3000rpm, and then use a nano-scale sand mill with zirconium beads with a diameter of 0.1mm as grinding media for grinding for 1h, with a speed of 10000rpm, and the temperature is controlled at 50°C during this period.

[0017] The high permeability glufosinate-ammonium combined with fluazifop-propylamine nanosuspension prepared in this example has an appearance of a viscous white homogeneous suspension liquid, a suspension rate of 93%, and a particle size of D 90 The nanostructured carbonyl group was 123 nm and there was no stratification, precipitation or creaming when stored at 50°C for six months, indicating good stability.

[0018] Example 2 In this embodiment, a nano calcium carbonate suspension is mixed with a sodium silicate solution, diluted hydrochloric acid is added, and after the reaction is complete, methanol is used for pulping and filtering to obtain a filter cake, and the filter cake is calcined in a muffle furnace at 500-800° C. for 3-6 hours, and placed in a nitrogen flow to cool to a porous powder solid; the solid is then crushed by a hammer mill, and then crushed by a needle mill to prepare a porous silica carrier; 50g of glufosinate (chemical structure as Figure 1 As shown in the figure, 0.75g fluazifop-butyl was mixed with 70g nanoporous silica and 300g water to form an aqueous solution, and water was added to make up to 500g to obtain a slurry A of nanoporous silica loaded with active ingredients; then 20g modified polycarboxylate, 15g isopropylnaphthalene sulfonate, 1g ESAFLOR X 80, 0.5g ANTIFOAMAP 188, 3g isothiazolinone, add water to make up to 500g, stir evenly to obtain slurry B, and then homogenize and disperse for 40min, the speed is set to 1500rpm; then slurry A and slurry B are stirred and mixed evenly, and the pH is adjusted to 6-7 with phosphoric acid to obtain slurry C; slurry C and zirconium beads with a diameter of 0.2mm are used as grinding media in a secondary sand mill for secondary grinding and sand milling for 1h, the speed is set to 3000rpm, and then a nano-scale sand mill is used with zirconium beads with a diameter of 0.1mm as grinding media for 0.5h, the speed is 8000rpm, and the temperature is controlled at 50°C during the period.

[0019] The high permeability glufosinate-ammonium combined with fluazifop-propylamine nanosuspension prepared in this example has an appearance of a viscous white homogeneous suspension liquid, a suspension rate of 92%, and a particle size of D 90 The molecular weight is 146 nm. There is no stratification, precipitation or creaming when stored at 50°C for six months, and the stability is qualified.

[0020] Example 3 In this embodiment, a nano calcium carbonate suspension is mixed with a sodium silicate solution, diluted hydrochloric acid is added, and after the reaction is complete, methanol is used for pulping and filtering to obtain a filter cake, and the filter cake is calcined in a muffle furnace at 500-800° C. for 3-6 hours, and placed in a nitrogen flow to cool to a porous powder solid; the solid is then crushed by a hammer mill, and then crushed by a needle mill to prepare a porous silica carrier; 50g of glufosinate (chemical structure as Figure 1 As shown), 0.75g fluazifop-butyl was compounded with 70g nanoporous silica and 300g water and stirred to form an aqueous solution, and water was added to 500g to obtain a slurry A loaded with active ingredients of nanoporous silica; 10g modified polycarboxylate, 10g isopropylnaphthalene sulfonate, 2g ESAFLOR X 80, 0.8g ANTIFOAMAP 188, 2g s-triazine were weighed, water was added to 500g, and stirred to obtain slurry B, which was then homogenized and dispersed for 40min, and the speed was set to 1500rpm; then slurry A and slurry B were stirred and mixed to obtain slurry C; slurry C and zirconium beads with a diameter of 0.2mm were used as grinding media in a secondary sand mill for secondary grinding and sand milling for 1h, and the speed was set to 3000rpm, and then a nano-scale sand mill was used with zirconium beads with a diameter of 0.1mm as grinding media for 0.5h, and the speed was 8000rpm, during which the temperature was controlled at 50°C. The high permeability glufosinate-ammonium combined with fluazifop-propylamine nanosuspension prepared in this example has an appearance of a viscous white homogeneous suspension liquid, a suspension rate of 79%, and a particle size of D 90 The molecular weight is 298nm. There is no stratification, precipitation or creaming when stored at 50°C for six months, and the stability is qualified.

[0021] Comparative Example 1 In this embodiment, a nano calcium carbonate suspension is mixed with a sodium silicate solution, diluted hydrochloric acid is added, and after the reaction is complete, methanol is used for pulping and filtration to obtain a filter cake, and the filter cake is air-dried; the solid is then crushed by a hammer mill, and then crushed by a needle mill to prepare a silica carrier; 50g of glufosinate (chemical structure as Figure 1As shown in the figure, 0.75g of fluazifop-butyl, 70g of nanoporous silica and 300g of water are mixed and stirred to form an aqueous solution, and water is added to make up to 500g to obtain slurry A of nanoporous silica loaded with active ingredients; then 10g of modified polycarboxylate, 10g of isopropylnaphthalene sulfonate, 2g of ESAFLOR X 80, 0.8g of ANTIFOAMAP 188, and 2g of s-triazine are weighed, and water is added to make up to 500g, and stirred to obtain slurry B, which is then homogenized and dispersed for 40min, and the speed is set to 1500rpm; then slurry A and slurry B are stirred and mixed evenly, and the pH is adjusted to 6-7 with phosphoric acid to obtain a suspension.

[0022] The high permeability glufosinate-ammonium combined with fluazifop-propylamine nanosuspension prepared in this example has an appearance of a viscous white homogeneous suspension liquid, a suspension rate of 79%, and a particle size of D 90 The particle size is 20 μm. After being stored at 20°C for half a month, a small amount of stratification, precipitation and creaming occurred, and the stability was worse than the previous three.

[0023] Field efficacy test Targets of control: Erigeron candidum, Purslane, etc. Experimental design: The experiment was set up in 4 groups to compare the efficacy of each implementation example result under high temperature weather.

[0024] Application and investigation methods: Use a backpack automatic sprayer to divide the area into four areas with similar weed growth as evenly as possible, spray each area evenly for 2 seconds, investigate the type and number of weeds 20 days after application, calculate the drug effect and the precipitation and stratification of the drug after being placed at an ambient temperature of 50°C for 180 days.

[0025] Control effect = (number of weeds before spraying pesticides - number of weeds 20 days after spraying pesticides) / number of weeds before spraying pesticides * 100% Table 1 The control effect of different groups on weeds after 20 days serial number Erigeron sphaerocephala purslane Other weeds Precipitation after 180 days at 50°C Stratification after 50°C and 180 days Example 1 95.1% 93.4% 92.1% none none Example 2 90.1% 91.2% 91.5% none none Example 3 73.7% 81.2% 85.5% none none Example 4 70.5% 65.3% 78.2% Large amount of precipitation have As can be seen from the above test data results, the herbicidal effect of embodiment 1 and 2 is good, and the medicine is stable, stable during the high temperature acceleration, wherein the herbicidal effect of embodiment 1 is the best, and the herbicidal effect of embodiment 3 is affected by the degradation of the effective ingredient and the agglomeration of a small amount of particles due to the lack of pH adjustment. And embodiment 4 is not made into nano-scale suspended particles, resulting in poor nano-carrier loading effect, large particles, making it easier to produce precipitation and stratification, unstable liquid medicine, and the speed of plant absorption of pesticide is slow due to large particles, and the volatilization of medicine is much in high temperature weather, which greatly reduces the utilization rate of pesticide, making it poor herbicidal effect. In summary, it can be concluded that in this test, the use of the composite fluazifop-butyl nano suspension of high-permeability glufosinate-ammonium of the present invention has better herbicidal effect, longer drug action time, and high drug stability. Although the preparation process is slightly more complicated than that of the solution, the advantages outweigh the disadvantages overall. Combining glufosinate ammonium with fluazifop-butyl to make a nano-particle suspension greatly improves the permeability of the drug, allowing it to enter the weeds faster and stay longer, reducing the number of times the pesticide is used and making the drug more sensitive. This is of great significance to reducing the use of pesticides and protecting the ecological environment.

Claims

1. A high-permeability glufosinate-ammonium compound fluazifop-propylamine nano suspension, characterized in that: The suspending agent is specifically composed of the following components: 5wt%-10wt% of glufosinate-ammonium and fluazifop-propyl acetate, 2.32wt%-6.78wt% of functional additives, a pH regulator, 3wt%-7wt% of nano-carriers, and the balance is water.

2. The high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 1, characterized in that: The mass ratio of glufosinate-ammonium to fluazifop-butyl is 40:1-80:

1.

3. The high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 1, characterized in that: The functional assistant contains 1.0wt%-1.5wt% of alkylnaphthalene sulfonate.

4. The high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 1, characterized in that: The functional auxiliary agent contains 1.0 wt%-4.0 wt% of modified polycarboxylate, 0.1 wt%-0.2 wt% of ESAFLOR X 80, 0.02 wt%-0.08 wt% of ANTIFOAM AP 188, and 0.2 wt%-1.0 wt% of one of s-triazines and isothiazolinone.

5. The high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 1, characterized in that: The pH regulator is phosphoric acid, which adjusts the pH of the system to 6-7.

6. The high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 1, characterized in that: The nano-carrier is a nano-porous silica carrier.

7. A method for preparing a highly permeable nano suspension of glufosinate-ammonium combined with fluazifop-propyl acetate as claimed in any one of claims 1 to 6, characterized in that: The steps include: S1. Mix the nano calcium carbonate suspension with the sodium silicate solution, add dilute hydrochloric acid, and then slurry and filter with methanol to obtain a filter cake. The filter cake is calcined in a muffle furnace at 500-800° C. for 3-6 hours, and cooled in a nitrogen flow to obtain a porous powder solid; S2, crushing the solid in step S1 by a hammer mill, and then crushing it by a needle mill to prepare a porous silica carrier; S3, mixing glufosinate-ammonium and fluazifop-propyl acetate and stirring to form an aqueous solution, and then loading the aqueous solution onto nanoporous silica to obtain slurry A; S4, mixing the functional additive and water to obtain slurry B, and uniformly dispersing the slurry; S5. Slurry A and slurry B are stirred and mixed evenly, the balance is supplemented with water, and the pH is adjusted to 6-7 with phosphoric acid to obtain slurry C; S6. Grind the slurry C and the grinding medium in a secondary sand mill, and then grind them in a nano-grade sand mill, during which the temperature is controlled at 25° C.-50° C. to obtain the composite nano suspension.

8. The method for preparing the high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 7, characterized in that: The homogenization time in step S4 is 30 min-60 min, and the homogenization speed is 1500 rpm-2000 rpm.

9. The method for preparing the high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 7, characterized in that: The grinding medium in step S6 is one of 95TZP zirconium beads and 65 zirconium beads, which are sand-milled in turn using a secondary sand mill and a nano-grade sand mill. The particle size of the zirconium beads in the secondary sand mill is 0.2mm-0.4mm, and the particle size of the zirconium beads in the nano-grade sand mill is 0.1mm-0.15mm.

10. The method for preparing the high-permeability glufosinate-ammonium compound fluazifop-propylamine nanosuspension according to claim 7, characterized in that: In step S6, the grinding time of the nano-scale sand mill is 0.5h-1h, the rotation speed is 8000rpm-10000rpm, and the particle size D of the nano suspension is 90 <300nm, suspension rate ≥90%.

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