Formamidosulfuron nano dispersible oil suspending agent and preparation method thereof

Abstract

The invention discloses a foramsulfuron nano dispersible oil suspending agent and a preparation method thereof, and relates to the technical field of herbicides. The invention relates to a foramsulfuron nano dispersible oil suspending agent which comprises the following components in percentage by weight: 1-5% of foramsulfuron, 20-30% of an emulsifier and the balance of a dispersion medium, the dispersion medium is prepared from methyl oleate and diethylene glycol diethyl ether according to the mass ratio of 1: 1; the emulsifying agent in the foramido-sulfuron nano dispersible oil suspending agent is prepared from one or two of 7200-F and sitosterol formyl arginyl-glycyl-aspartic acid dipotassium salt, and the emulsifying agent is prepared from one or two of 7200-F and sitosterol formyl arginyl-glycyl-aspartic acid dipotassium salt. The foramsulfuron nano dispersible oil suspending agent prepared by the invention is stable in performance, environment-friendly and green, and has excellent characteristics of small granularity, high dispersity and low decomposition rate.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of herbicides, in particular to a foramsulfuron nano dispersible oil suspension and a preparation method thereof. BACKGROUND

[0002] Foramsulfuron is a branched chain amino acid synthesis enzyme inhibitor herbicide, which can inhibit the biosynthesis of branched chain amino acids such as leucine, valine and isoleucine in sensitive weeds, block cell division and plant growth, and has a significant effect on grass weeds such as barnyard grass and dogtail grass.

[0003] At present, the mainstream dosage form of foramsulfuron is dispersible oil suspension (OD), which disperses solid technical material in non-aqueous medium such as methyl oleate. Although it has certain field applicability, it still has the following significant limitations: first, the conventional dispersible oil suspension is usually micron-sized, which limits the solubility and bioavailability of the drug, affecting the release efficiency of the drug effect; second, the stability of the conventional dispersible oil suspension is poor, and long-term storage is prone to oil separation, precipitation or caking, which needs to be frequently shaken to restore the dispersed state, and the user convenience is poor. In the prior art, the emulsifier or dispersing medium is usually adjusted to improve the limitations. However, the conventional emulsifier or dispersing medium is insufficient in the balance between the synergistic effect and the stability of foramsulfuron, and the related performance still needs to be further improved. At the same time, if the dispersible oil suspension is adjusted to be nano-sized, there are problems of aggregation or degradation of nano particles due to high surface energy, and it is difficult to inhibit the increase of particle size during storage in the conventional formula, resulting in the defect of thermodynamic instability.

[0004] In summary, it is of great significance to develop a high-stability, nano-sized foramsulfuron nano dispersible oil suspension to overcome the defects of existing suspending oil and to comply with the trend of pesticide greenness and high efficiency. SUMMARY

[0005] The present application aims to provide a foramsulfuron nano dispersible oil suspension and a preparation method thereof to solve the problems raised in the background.

[0006] In order to solve the above technical problems, the present application provides the following technical scheme: A foramsulfuron nano dispersible oil suspension, the raw materials of the foramsulfuron nano dispersible oil suspension include the following components: 1-5% foramsulfuron, 20-30% emulsifier, and the rest is a dispersing medium.

[0007] More preferably, the dispersing medium includes one or both of methyl oleate and diethylene glycol diethyl ether.

[0008] The methyl oleate is a plant oil derivative, has a long-chain unsaturated fatty acid methyl ester structure, strong hydrophobicity, low viscosity and excellent biodegradability; the diethylene glycol diethyl ether is a polar ether solvent, has high boiling point, low viscosity and strong solubility.

[0009] More preferably, the dispersing medium is methyl oleate and diethylene glycol diethyl ether at a mass ratio of 1:1.

[0010] More preferably, the raw materials of the foramsulfuron nano-dispersible oil suspension include the following components: 1-5% of foramsulfuron, 20-30% of an emulsifier, 30-40% of methyl oleate and 30-40% of diethylene glycol diethyl ether.

[0011] More preferably, the emulsifier includes one or both of 7200-F and stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium.

[0012] The stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium uses stigmasterol and tripeptide as natural biomass materials, has strong hydrophobicity and intermolecular van der Waals force, and can realize precise regulation of hydrophobicity-hydrophilicity through hydrogen bond network, thereby reducing the critical micelle concentration.

[0013] More preferably, the emulsifier is composed of 7200-F and stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium, and the mass ratio of the two is 25: (1-5).

[0014] More preferably, the preparation method of the stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium is as follows: S1-1: arginyl-glycyl-aspartic acid is added to anhydrous ethanol, dichlorosulfoxide is added dropwise under ice bath, the temperature is set to 78-82℃, and the reaction is carried out for 6-8 hours to obtain arginyl-glycyl-aspartic acid hydrochloride; S1-2: β-stigmasterol and 1,1'-carbonyl diimidazole are added to tetrahydrofuran, the temperature is set to 65-72℃, and stirring is carried out for 1-2 hours to obtain stigmasterol formyl imidazole; S1-3: arginyl-glycyl-aspartic acid hydrochloride and stigmasterol formyl imidazole are sequentially added to N,N-dimethylformamide, the temperature is set to 145-150℃, stirring is carried out for 1-1.5 hours, and then the temperature is lowered; potassium hydroxide-ethanol aqueous solution is added and stirred uniformly, hydrochloric acid solution is used to adjust the pH to 1.2-1.8; filtration, washing and drying are carried out to obtain stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium.

[0015] More preferably, in the raw material of the arginyl-glycyl-aspartic acid hydrochloride, the mass ratio of arginyl-glycyl-aspartic acid and dichloro sulfenyl is 1: (2.8-3.2); in the raw material of the beta-sitosterol, the mass ratio of beta-sitosterol and 1,1'-carbonyl diimidazole is 1: (1.8-2.2); and in the raw material of the beta-sitosterol formyl arginyl-glycyl-aspartic acid dipotassium, the mass ratio of beta-sitosterol formyl imidazole and arginyl-glycyl-aspartic acid hydrochloride is 1: (1.8-2.2).

[0016] A preparation method of a foramsulfuron nano-dispersible oil suspension agent, comprising the following steps: S1-1: mixing an emulsifier and a dispersion medium to obtain a mixed solution; S1-2: adding foramsulfuron to the mixed solution to obtain a raw material solution; and stirring and sand milling the raw material solution to obtain the foramsulfuron nano-dispersible oil suspension agent.

[0017] More preferably, in the stirring process, the stirring paddle speed is 0.5-1 revolutions per second; and in the sand milling process, the sand milling bead filling amount is 60-80% of the volume of the raw material solution, and the sand milling time is 1.5-2.5 hours.

[0018] Compared with the prior art, the present application has the following beneficial effects: by adjusting the dispersion medium and the emulsifier, using the complex of formic acid oil and diethylene glycol diethyl ether as the dispersion medium, and using 7200-F and beta-sitosterol formyl arginyl-glycyl-aspartic acid dipotassium as the emulsifier, the nanometerization degree, stability and dispersibility of the foramsulfuron nano-dispersible oil suspension agent are effectively improved.

[0019] In the dispersion medium, the formic acid oil provides a hydrophobic environment, improves the solubility of foramsulfuron, inhibits particle aggregation, and effectively solves the problem of low nanometerization degree of particle size; diethylene glycol diethyl ether increases polarity, optimizes emulsifier dissolution, and thus promotes the stable suspension of foramsulfuron particles, so that the dispersibility of the dispersible oil suspension agent is improved; the complex of the two balances the polarity of the system, forms a "hydrophobic core-hydrophilic shell" structure, reduces the surface energy of the particles, inhibits particle aggregation, forms a moderate viscosity system, ensures the sand milling efficiency and reduces energy consumption, and avoids rapid particle sedimentation, so that the kinetic stability is further enhanced.

[0020] Compared with the conventional diethylene glycol ethyl ether acetate, 7200-F has better balance of active ingredient solubility and interface regulation; meanwhile, in the further scheme, the introduction of stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium and 7200-F is compounded and synergized to produce better performance. Among them, the stable hydrophobic interface layer formed by the steryl hydrophobic group of stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium and the long-chain alkyl structure of methyl oleate reduces the oil-water interfacial tension, and the long-chain structure of methyl oleate inhibits micelle aggregation through steric hindrance, realizes the uniform distribution of foramsulfuron at the nanometer level, and improves the stability; the ether bond of diethylene glycol diethyl ether is combined with the amide group of stigmasterol formyl arginyl-glycyl-aspartic acid dipotassium through hydrogen bond action, which enhances the adsorption strength of the oil-water interface, and the flexible segment of the ether bond adjusts the fluidity of the interface film, prevents the film layer from being brittle at high temperature, and effectively improves the stability of the dispersible oil suspension concentrate during storage; further, the three form a continuous high-strength elastic interface film at the interface, inhibits molecular thermal motion, reduces the decomposition of foramsulfuron at high temperature, and improves the thermodynamic stability.

[0021] In summary, the present application successfully realizes nanoscale particle size control, significantly improves drug solubility, replaces traditional mineral oil medium with environmentally friendly vegetable oil, reduces environmental risk, and realizes industrial production feasibility under the premise of controlling energy consumption. The preparation has high efficiency, stability and environmental friendliness, and provides an innovative solution for the development of pesticide nanotechnology. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described below. Obviously, the described embodiments are only part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0023] It should be noted that, according to the weight percentage, there is no special limitation on the purchase manufacturer of all raw materials involved in the present application, which exemplarily includes: in the following embodiments, formylaminopyrimidine, methyl oleate, diethylene glycol diethyl ether, 7200-F (mass ratio of phenylethyl phenol formaldehyde resin polyoxyethylene ether sulfonate and castor oil polyoxyethylene ether sulfonate is 1:1), and the above surfactants are produced by Nanjing Taihua Chemical Co., Ltd.

[0024] Embodiment 1: A formylaminopyrimidine nano-dispersible oil suspension agent, comprising the following steps: S1: mixing methyl oleate and diethylene glycol diethyl ether to obtain a dispersion medium; using 7200-F as an emulsifier; mixing the emulsifier and the dispersion medium to prepare a mixed solution; S2: Stir the foramsulfuron and the mixed solution uniformly, the stirring paddle speed is 0.8 revolutions per second, to obtain a raw material solution; S3: Fill 70% of sand milling beads according to the volume of the raw material solution, and perform sand milling for 2 hours to obtain the foramsulfuron nano dispersible oil suspension.

[0025] In this embodiment, the following components are included: 36% of methyl oleate, 36% of diethylene glycol diethyl ether, 25% of 7200-F, and 3% of foramsulfuron.

[0026] Embodiment 2: A foramsulfuron nano dispersible oil suspension includes the following steps: S1: Mix methyl oleate and diethylene glycol diethyl ether to obtain a dispersion medium; use 7200-F as an emulsifier; mix the emulsifier and the dispersion medium to obtain a mixed solution; S2: Stir the foramsulfuron and the mixed solution uniformly, the stirring paddle speed is 0.8 revolutions per second, to obtain a raw material solution; S3: Fill 70% of sand milling beads according to the volume of the raw material solution, and perform sand milling for 2 hours to obtain the foramsulfuron nano dispersible oil suspension.

[0027] In this embodiment, the following components are included: 36% of methyl oleate, 36% of diethylene glycol diethyl ether, 25% of 7200-F, and 3% of foramsulfuron.

[0028] Embodiment 3: A foramsulfuron nano dispersible oil suspension includes the following steps: S1: Mix methyl oleate and diethylene glycol diethyl ether to obtain a dispersion medium; use 7200-F as an emulsifier; mix the emulsifier and the dispersion medium to obtain a mixed solution; S2: Stir the foramsulfuron and the mixed solution uniformly, the stirring paddle speed is 0.8 revolutions per second, to obtain a raw material solution; S3: Fill 70% of sand milling beads according to the volume of the raw material solution, and perform sand milling for 2 hours to obtain the foramsulfuron nano dispersible oil suspension.

[0029] In this embodiment, the following components are included: 36% of methyl oleate, 36% of diethylene glycol diethyl ether, 25% of 7200-F, and 3% of foramsulfuron.

[0030] Embodiment 4: Based on the further scheme of embodiment 1, specifically includes the following steps: S1: mixing methyl oleate and diethylene glycol diethyl ether to obtain a dispersion medium; mixing 7200-F and stigmasterol formylarginyl-glycyl-aspartic acid dipotassium to obtain an emulsifier; mixing the emulsifier and the dispersion medium to obtain a mixed solution; S2: mixing forminamoyl sulfonilurea and the mixed solution to obtain a raw material solution; S3: filling 70% of sand milling beads according to the volume of the raw material solution, sand milling for 2h to obtain a forminamoyl sulfonilurea nano-dispersible oil suspension.

[0031] In this example, the following components are included: methyl oleate 34.5%, diethylene glycol diethyl ether 34.5%, 7200-F 25%, stigmasterol formylarginyl-glycyl-aspartic acid dipotassium 1%, and forminamoyl sulfonilurea 5% by weight percentage.

[0032] Comparative Example 1: based on Example 1, adjusting the dispersion medium, single methyl oleate as the dispersion medium, specifically including the following steps: S1: using methyl oleate as the dispersion medium; 7200-F as the emulsifier; mixing the emulsifier and the dispersion medium to obtain a mixed solution; S2: mixing forminamoyl sulfonilurea and the mixed solution to obtain a raw material solution; S3: filling 70% of sand milling beads according to the volume of the raw material solution, sand milling for 2h to obtain a forminamoyl sulfonilurea nano-dispersible oil suspension.

[0033] In this example, the following components are included: methyl oleate 34.5%, diethylene glycol diethyl ether 34.5%, 7200-F 25%, stigmasterol formylarginyl-glycyl-aspartic acid dipotassium 1%, and forminamoyl sulfonilurea 5% by weight percentage.

[0034] Comparative Example 2: based on Example 1, adjusting the dispersion medium, single diethylene glycol diethyl ether acetate as the dispersion medium, specifically including the following steps: S1: using diethylene glycol diethyl ether acetate as the dispersion medium; 7200-F as the emulsifier; mixing the emulsifier and the dispersion medium to obtain a mixed solution; S2: mixing forminamoyl sulfonilurea and the mixed solution to obtain a raw material solution; S3: filling 70% of sand milling beads according to the volume of the raw material solution, sand milling for 2h to obtain a forminamoyl sulfonilurea nano-dispersible oil suspension.

[0035] In this example, the following components are included: diethylene glycol diethyl ether acetate 72%, 7200-F 25%, and forminamoyl sulfonilurea 3% by weight percentage.

[0036] Comparative Example 3: Based on Example 1, adjusting emulsifier, triethanolamine dodecylbenzenesulfonate: tristyrylphenol ethoxylate sulfate: fatty alcohol polyoxyethylene ether as emulsifier, specifically comprising the following steps: S1: Methyl oleate and diethylene glycol diethyl ether were mixed to obtain a dispersion medium; triethanolamine dodecylbenzenesulfonate, tristyrylphenol ethoxylate sulfate, and fatty alcohol polyoxyethylene ether were mixed to obtain an emulsifier; the emulsifier and the dispersion medium were mixed and stirred to prepare a mixed solution; S2: Formylaminopyrimidinesulfonate was uniformly stirred with the mixed solution at a stirring paddle speed of 0.8 revolutions per second to prepare a raw material solution; S3: 70% of sand milling beads were filled according to the volume of the raw material solution, and sand milling was performed for 2 hours to prepare formylaminopyrimidinesulfonate nano-dispersible oil suspension.

[0037] In this example, the following components were included: by weight percentage: formic acid oil 36%, diethylene glycol ethyl ether acetate 36%, triethanolamine dodecylbenzenesulfonate 12%, tristyrylphenol ethoxylate sulfate 8%, fatty alcohol polyoxyethylene ether 5%, and formylaminopyrimidinesulfonate 3%.

[0038] Comparative Example 4: Based on Example 1, adjusting sand milling time, sand milling time 1h, specifically comprising the following steps: S1: Methyl oleate and diethylene glycol diethyl ether were mixed to obtain a dispersion medium; 7200-F was used as an emulsifier, and the emulsifier and the dispersion medium were mixed and stirred to prepare a mixed solution; S2: Formylaminopyrimidinesulfonate was uniformly stirred with the mixed solution at a stirring paddle speed of 0.8 revolutions per second to prepare a raw material solution; S3: 70% of sand milling beads were filled according to the volume of the raw material solution, and sand milling was performed for 1 hour to prepare formylaminopyrimidinesulfonate nano-dispersible oil suspension.

[0039] In this example, the following components were included: by weight percentage: methyl oleate 36%, diethylene glycol diethyl ether 36%, 7200-F 25%, and formylaminopyrimidinesulfonate 3% Performance test: The formylaminopyrimidinesulfonate nano-dispersible oil suspensions prepared in the examples and comparative examples were tested for related performance, (1) particle size detection; (2) decomposition rate detection; (3) oil separation rate detection; (4) viscosity detection. The data obtained from the performance test are shown in Table 1: Table 1. Performance test related data of examples and comparative examples

[0040] Conclusion: By comparing the performance test data of the examples and the comparative examples, it can be seen from Examples 1-3 that using a single emulsifier can result in larger particle size of the foramsulfuron nanodispersible oil suspension, insufficient nanometerization efficiency, increased decomposition rate of foramsulfuron, and thus reduced release efficiency, and increased oil separation rate of the foramsulfuron nanodispersible oil suspension, resulting in poor stability. In Example 4, using 7200-F and stigmasterol formylarginyl-glycyl-aspartic acid dipotassium as emulsifiers, the foramsulfuron nanodispersible oil suspension prepared has smaller particle size, higher nanometerization degree, and lower decomposition rate of foramsulfuron, making the active ingredient content more stable. Compared with Example 1, Comparative Examples 1-4 have further increased particle size of the foramsulfuron dispersible oil suspension, increased decomposition rate and oil separation rate, and increased viscosity, making the foramsulfuron nanodispersible oil suspension more viscous. In summary, by synergistically optimizing the dispersion medium, emulsifier, and process parameters, the examples obtain a foramsulfuron nanodispersible oil suspension with smaller particle size, higher nanometerization degree, stable active ingredient content, low decomposition rate and oil separation rate, moderate viscosity, and stable emulsification and dispersion.

[0041] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art can modify the technical solutions described in the foregoing embodiments or make equivalent replacements to some technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A nicosulfuron nano dispersible oil suspension characterized in that: The raw material of the foramsulfuron nano dispersible oil suspension includes the following components: 1-5% foramsulfuron, 20-30% emulsifier, and the rest is a dispersion medium.

2. The nicosulfuron nano dispersible oil suspension according to claim 1, characterized in that: The dispersion medium includes one or both of methyl oleate and diethylene glycol diethyl ether.

3. The nicosulfuron nano dispersible oil suspension according to claim 2, characterized in that: The dispersion medium is a mixture of methyl oleate and diethylene glycol diethyl ether in a mass ratio of 1:

1.

4. The nicosulfuron nano dispersible oil suspension of claim 2, characterized in that: The raw material of the foramsulfuron nano dispersible oil suspension includes the following components: 1-5% foramsulfuron, 20-30% emulsifier, 30-40% methyl oleate, and 30-40% diethylene glycol diethyl ether.

5. The formamidosulfuron nano-dispersible oil suspension according to claim 1, characterized in that: The emulsifier includes one or both of 7200-F and dipotassium stigmasterol formylarginyl-glycyl-aspartate.

6. The nicosulfuron nano dispersible oil suspension according to claim 5, characterized in that: The emulsifier consists of 7200-F and dipotassium stigmasterol formylarginyl-glycyl-aspartate in a mass ratio of 25: (1-5); the 7200-F is a mixture of phenylethyl phenol formaldehyde resin polyoxyethylene ether sulfonate and castor oil polyoxyethylene ether sulfonate in a mass ratio of 1:

1.

7. The nicosulfuron nano dispersible oil suspension of claim 5, characterized in that: The preparation method of the dipotassium stigmasterol formylarginyl-glycyl-aspartate includes the following steps: S1-1: adding arginyl-glycyl-aspartic acid into anhydrous ethanol, and adding dichloro sulfoxide dropwise under ice bath; setting the temperature to 78-82°C and reacting for 6-8 hours; obtaining arginyl-glycyl-aspartic acid hydrochloride; S1-2: adding β-stigmasterol and 1,1'-carbonyl diimidazole into tetrahydrofuran, and setting the temperature to 65-72°C and stirring for 1-2 hours; obtaining stigmasterol formyl imidazole; S1-3: adding arginyl-glycyl-aspartic acid hydrochloride and stigmasterol formyl imidazole into N,N-dimethylformamide in sequence, setting the temperature to 145-150°C and stirring for 1-1.5 hours, and then cooling; adding potassium hydroxide-ethanol aqueous solution and stirring until uniform; adjusting the pH to 1.2-1.8 using hydrochloric acid solution; filtering, washing, and drying to obtain dipotassium stigmasterol formylarginyl-glycyl-aspartate.

8. The nicosulfuron nano dispersible oil suspension according to claim 7, characterized in that: In the raw material of the arginyl-glycyl-aspartic acid hydrochloride, the mass ratio of arginyl-glycyl-aspartic acid to dichloro sulfoxide is 1:(2.8-3.2); in the raw material of the stigmasterol formyl imidazole, the mass ratio of β-stigmasterol to 1,1'-carbonyl diimidazole is 1:(1.8-2.2); and in the raw material of the dipotassium stigmasterol formylarginyl-glycyl-aspartate, the mass ratio of stigmasterol formyl imidazole to arginyl-glycyl-aspartic acid hydrochloride is 1:(1.8-2.2).

9. A process for the preparation of a nicosulfuron nano dispersible oil miscible suspension concentrate according to claim 1, characterized in that: The method includes the following steps: S1-1: mixing the emulsifier and the dispersion medium to obtain a mixed solution; S1-2: adding foramsulfuron into the mixed solution to obtain a raw material solution; stirring and sand milling the raw material solution to obtain the foramsulfuron nano dispersible oil suspension.

10. A process for the preparation of a nicosulfuron nano dispersible oil miscible suspension concentrate according to claim 9, characterized in that: During the stirring process, the stirring speed of the stirring paddle is 0.5-1 revolutions per second; and during the sand milling process, the filling amount of the sand milling beads is 60-80% of the volume of the raw material solution, and the sand milling time is 1.5-2.5 hours.

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