Fluoroglycofen-ethyl, quizalofop-p-ethyl and glufosinate-ammonium microemulsion as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of pesticides, and discloses a fluoroglycofen-ethyl, quizalofop-p-ethyl and glufosinate-ammonium microemulsion as well as a preparation method and application thereof. The invention relates to a microemulsion containing fluoroglycofen-ethyl, quizalofop-p-ethyl and glufosinate-ammonium. Comprising the following components in percentage by weight: 0.5 to 2 percent of fluoroglycofen-ethyl, 1.0 to 5.0 percent of quizalofop-p-ethyl, 15 to 30 percent of glufosinate-ammonium, 0.5 to 10 percent of styryl polyoxyethylene ether phosphate monoester, 0.5 to 10 percent of styryl polyoxyethylene ether phosphate diester, 2 to 5 percent of fatty alcohol polyoxyethylene ether sodium sulfate, 15 to 20 percent of alkyl glycoside, 8 to 15 percent of solvent and the balance of deionized water. According to the microemulsion disclosed by the invention, by adding the styryl polyoxyethylene ether phosphate monoester and the styryl polyoxyethylene ether phosphate diester, the microemulsion can be stably stored at the temperature of-15 to 54 DEG C, and the influence of precipitation of effective components or a surfactant of a product on the quality of the product in extreme weather is avoided.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticides, and specifically relates to a fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion and a preparation method and application thereof. Background Art

[0002] Glufosinate is a broad-spectrum contact herbicide suitable for weed control in farmland, orchards, fields and roads. It has the advantages of high efficiency, broad spectrum and safety, and has a good control effect on various common weeds. If glufosinate is used alone for a long time, more and more weeds will become resistant to glufosinate. In order to prevent this phenomenon, glufosinate is often mixed with other herbicides. The most common is the combination of glufosinate with fluazifop-butyl and quizalofop-P-ethyl.

[0003] The patent document with the publication number CN115104625A discloses a low foaming adjuvant for glufosinate-fluoropyralid microemulsion, comprising the following components, in weight percentage: 10%-25% of isooctyl alcohol polyoxyethylene polyoxypropylene ether phosphate; 1%-10% of isooctyl amidopropyl-N-methyl-N-(2-hydroxyethyl) tertiary amine; 30%-50% of methyl octanoate polyoxyethylene polyoxypropylene ether; 10%-30% of cosolvent; and the balance of water. The adjuvant is used to prepare the glufosinate-fluoropyralid microemulsion preparation, which has low foaming and fast defoaming, and is more convenient for production, filling, transportation and use, greatly improving the production efficiency and product qualification rate. The storage temperature range of the glufosinate-fluoropyralid microemulsion preparation prepared using the low foaming adjuvant is (0±2) to (54±2)°C.

[0004] The patent document with publication number CN117770242A discloses an emulsifier suitable for a ternary compound microemulsion of glufosinate, quizalofop-ethyl and fluazifop-butyl. The emulsifier is made of the following raw materials in mass percentage: 10%-30% of styrylphenol polyoxyethylene ether phosphate, 50%-75% of alkyl glycoside, 10%-30% of alkyl aryl polyoxypropylene polyoxyethylene ether, and 5%-10% of urea. The emulsifier can have a significant synergistic effect on the herbicide combination, the raw material source is easy to obtain, the preparation is simple, and the production cost of the preparation is reduced. The storage temperature range of the microemulsion of glufosinate, quizalofop-ethyl and fluazifop-butyl prepared using the emulsifier is (0±1) to (54±2)°C.

[0005] The microemulsion of fluazifop-butyl, quizalofop-P-ethyl and glufosinate-ammonium has a wide range of uses and is applicable throughout the country. The ideal storage temperature range is -15 to 50°C to ensure stable storage under extreme conditions. If the product is crystallized or turbid at around -15°C or 50°C, it will affect the product quality and reduce the herbicidal effect. However, the existing microemulsion of fluazifop-butyl, quizalofop-P-ethyl and glufosinate-ammonium can only be stably stored at temperatures of 0°C or above. The preparation of a microemulsion of fluazifop-butyl, quizalofop-P-ethyl and glufosinate-ammonium that can be stably stored under extreme conditions has become a technical problem that needs to be solved urgently. Summary of the invention

[0006] In order to solve the defects of the above-mentioned prior art, the present invention provides a fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion that can be stably stored even under extreme conditions, and specifically adopts the following technical solutions:

[0007] A fluazifop-butyl·quizalofop-P-ethyl·glufosinate microemulsion comprises, by weight percentage, 0.5-2% of fluazifop-butyl, 1.0-5.0% of quizalofop-P-ethyl, 15-30% of glufosinate, 0.5-10% of styryl polyoxyethylene ether phosphate monoester, 0.5-10% of styryl polyoxyethylene ether phosphate diester, 2-5% of sodium polyoxyethylene fatty alcohol ether sulfate, 15-20% of alkyl glycoside and 8-15% of solvent, and the content of the mixture is supplemented to 100% with deionized water.

[0008] Preferably, the weight ratio of the styrene-based polyoxyethylene ether phosphate monoester to the styrene-based polyoxyethylene ether phosphate diester is 2 to 5: 1. The fluazifop-butyl·quizalofop-P-ethyl·phosphinothricin microemulsion prepared at this time remains clear after cold storage at -15°C for 14 days without crystallization or turbidity, and the transparent temperature range of the product can be expanded to -15 to 54°C.

[0009] Further, the solvent includes N-methyl-2-pyrrolidone and 150# solvent oil, or the solvent includes N,N-dimethylacetamide and 200# solvent oil. The combination of polar solvent and non-polar solvent can dissolve fluazifop-butyl and quizalofop-ethyl technical faster on the one hand, and it is also convenient to adjust the hydrophilic and lipophilic directions of the system, making it easier to obtain a stable system.

[0010] Furthermore, the weight ratio of the N-methyl-2-pyrrolidone to 150# solvent oil is 1:1-3.

[0011] Furthermore, the optimal addition amount of fatty alcohol polyoxyethylene ether sodium sulfate is 2%.

[0012] Furthermore, the optimal addition ratio of alkyl glycoside is 17%. Too low an addition ratio of alkyl glycoside will lead to poor thermal storage stability of the product and stratification, while too high an addition ratio will affect low temperature stability, especially at -15°C, crystallization is more likely to precipitate.

[0013] The present invention also discloses a method for preparing any of the above-mentioned fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsions, comprising the following steps:

[0014] After measuring each raw material according to weight percentage, add fluazifop-butyl and quizalofop-P-ethyl into the solvent, stir thoroughly until completely dissolved, then add styryl polyoxyethylene ether phosphate monoester, styryl polyoxyethylene ether phosphate diester, fatty alcohol polyoxyethylene ether sodium sulfate and alkyl glycoside, stir well, then add glufosinate-ammonium, stir thoroughly until the solution is clear, and thus obtain fluazifop-butyl·quizalofop-P-ethyl·glufosinate-ammonium microemulsion.

[0015] The invention also discloses the application of any of the above-mentioned fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsions, which is used as a herbicide and has good control effects on weeds such as foxtail grass, fleabane, sonchus oleraceus, crabgrass and goosegrass.

[0016] Compared with the prior art, the present invention has the following beneficial effects:

[0017] The fluazifop-butyl·quizalofop-P-ethyl·phosphinothricin ammonium microemulsion of the present invention can ensure stable storage at a temperature of -15 to 54° C. by adding styryl polyoxyethylene ether phosphate monoester and styryl polyoxyethylene ether phosphate diester, and can quickly return to a clear state at room temperature after crystallization at -15° C., thereby avoiding the influence of the precipitation of the active ingredients or surfactants of the product on the product quality under extreme weather.

[0018] The surfactant used in the fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion of the present invention is low in price and easy to degrade, and the amount of organic solvent used is reduced, so that the production cost is reduced and the environment is more friendly. Therefore, the fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion of the present invention has great advantages in terms of product quality and price, strong market competitiveness and broad application prospects. DETAILED DESCRIPTION

[0019] The technical solutions in the embodiments of the present invention are described clearly and completely below.

[0020] Fluorosulfuron used in the examples and comparative examples was purchased from Qingdao Hansheng Biotechnology Co., Ltd. with a content of 97.00%, quizalofop-p-ethyl was purchased from Shandong Jingbo Agrochemical Technology Co., Ltd. with a content of 97.50%, glufosinate-ammonium was purchased from Inner Mongolia Lingsheng Crop Technology Co., Ltd. with a content of 97.80%, N-methyl-2-pyrrolidone was purchased from Shandong Quark Chemical Co., Ltd., 150# solvent oil was purchased from Jiangsu Hualun Chemical Co., Ltd., styrene-based polyoxyethylene ether monoester and styrene-based polyoxyethylene ether diester were purchased from Wuxi Yijingfeng Technology Co., Ltd., sodium sulfate of fatty alcohol polyoxyethylene ether was purchased from Shandong Tiannong New Materials Development Co., Ltd., and alkyl glycoside was purchased from Yangzhou Chenhua New Materials Co., Ltd.

[0021] The 0℃ low temperature stability test method refers to the standard GB 19137-2003. The 54℃ stability test method refers to the standard GB / T19136-2021. The -15℃ stability test method is as follows: Take 100ml of sample and put it into a 100ml transparent PET bottle, seal it and put it in a -15℃ refrigerator. Store it for 15 days and observe the sample status once a day to see if it is clear, whether crystallization or stratification occurs, etc.

[0022] Example 1

[0023] This embodiment discloses a fluazifop-butyl·quizalofop-P-ethyl·phosphinothricin ammonium microemulsion and a preparation method thereof:

[0024] In terms of weight percentage: 0.9% of fluazifop-butyl and 2.1% of quizalofop-ethyl are added to 4% of N-methyl-2-pyrrolidone and 6% of 150# solvent oil, and the mixture is stirred thoroughly until dissolved. Then, 6% of styrene-polyoxyethylene ether phosphate monoester, 2% of styrene-polyoxyethylene ether phosphate diester, 2% of fatty alcohol polyoxyethylene ether sodium sulfate and 17% of alkyl glycoside are added. Finally, 20% of glufosinate ammonium is added and stirred thoroughly, and then deionized water is added to 100% to obtain a clear fluazifop-butyl, quizalofop-ethyl and glufosinate ammonium microemulsion sample.

[0025] After 14 days of hot storage at 54℃, the solution became clear, and the decomposition rate of the active ingredients was less than 2%. After 7 days of cold storage at 0℃, no precipitate was observed by centrifugation. After 14 days of cold storage at -15℃, the solution became clear without any crystallization.

[0026] Example 2

[0027] This embodiment discloses a fluazifop-butyl·quizalofop-P-ethyl·phosphinothricin ammonium microemulsion and a preparation method thereof:

[0028] In terms of weight percentage: 0.9% of fluazifop-butyl and 2.1% of quizalofop-ethyl are added to 4% of N-methyl-2-pyrrolidone and 6% of 150# solvent oil, and the mixture is stirred thoroughly until dissolved. Then, 9% of styrene polyoxyethylene ether phosphate monoester, 3% of styrene polyoxyethylene ether phosphate diester, 2% of fatty alcohol polyoxyethylene ether sodium sulfate and 19% of alkyl glycoside are added. Finally, 20% of glufosinate ammonium is added and stirred thoroughly, and then deionized water is added to 100% to obtain a clear fluazifop-butyl, quizalofop-ethyl and glufosinate ammonium microemulsion sample.

[0029] The fluazifop-butyl·quizalofop-P-ethyl·glufosinate microemulsion sample prepared in this example was clarified after heat storage at 54°C for 14 days, and the decomposition rate of the active ingredients was <2%; no precipitate was found after centrifugation after cold storage at 0°C for 7 days; and no crystals were found after cold storage at -15°C for 14 days.

[0030] Example 3

[0031] This embodiment discloses a fluazifop-butyl·quizalofop-P-ethyl·glufosinate-ammonium microemulsion and a preparation method thereof:

[0032] In terms of weight percentage: 1.5% of fluazifop-butyl and 3.0% of quizalofop-ethyl are added to 2% of N-methyl-2-pyrrolidone and 6% of 150# solvent oil, and the mixture is stirred thoroughly until dissolved. Then, 10% of styrene polyoxyethylene ether phosphate monoester, 2% of styrene polyoxyethylene ether phosphate diester, 5% of fatty alcohol polyoxyethylene ether sodium sulfate and 25% of alkyl glycoside are added. Finally, 15% of glufosinate ammonium is added and stirred thoroughly, and then deionized water is added to 100% to obtain a clear fluazifop-butyl, quizalofop-ethyl and glufosinate ammonium microemulsion sample.

[0033] The fluazifop-butyl·quizalofop-P-ethyl·phosphinothion microemulsion sample prepared in this example was clarified after heat storage at 54°C for 14 days, and the decomposition rate of the active ingredients was <2%; no precipitate was found after centrifugation after cold storage at 0°C for 7 days; and clarified after cold storage at -15°C for 14 days.

[0034] Example 4

[0035] The difference between this embodiment and embodiment 1 is that the added amount of styrene-polyoxyethylene ether phosphate monoester is 5.5%, and the added amount of styrene-polyoxyethylene ether phosphate diester is 2.5%. The other aspects are exactly the same as embodiment 1.

[0036] The fluazifop-butyl·quizalofop-P-ethyl·phosphinothion microemulsion sample prepared in this example was clarified after heat storage at 54°C for 14 days, and the decomposition rate of the active ingredients was <2%; no precipitate was found after centrifugation after cold storage at 0°C for 7 days; and clarified after cold storage at -15°C for 14 days.

[0037] Example 5

[0038] The difference between this embodiment and embodiment 1 is that the amount of styrene-polyoxyethylene ether phosphate monoester added is 6.5%, and the amount of styrene-polyoxyethylene ether phosphate diester added is 1.5%. The other aspects are exactly the same as embodiment 1.

[0039] The fluazifop-butyl·quizalofop-P-ethyl·phosphinothion microemulsion sample prepared in this example was clarified after heat storage at 54°C for 14 days, and the decomposition rate of the active ingredients was <2%; no precipitate was found after centrifugation after cold storage at 0°C for 7 days; and clarified after cold storage at -15°C for 14 days.

[0040] Example 6

[0041] The difference between this embodiment and embodiment 1 is that the added amount of styrene-polyoxyethylene ether phosphate monoester is 4%, and the added amount of styrene-polyoxyethylene ether phosphate diester is 4%. The other aspects are exactly the same as those of embodiment 1.

[0042] The fluazifop-butyl·quizalofop-P-ethyl·glufosinate microemulsion sample prepared in this example was clarified after hot storage at 54°C for 14 days; clarified after cold storage at 0°C for 7 days; crystallization began to occur after cold storage at -15°C for 10 days. After cold storage for 14 days, the sample could be restored to a clear state within 8 hours at room temperature.

[0043] Example 7

[0044] The difference between this embodiment and embodiment 1 is that the added amount of styrene-polyoxyethylene ether phosphate monoester is 7.5%, and the added amount of styrene-polyoxyethylene ether phosphate diester is 0.5%. The other aspects are exactly the same as embodiment 1.

[0045] The fluazifop-butyl·quizalofop-P-ethyl·glufosinate microemulsion sample prepared in this example was clarified after hot storage at 54°C for 2 weeks; clarified after cold storage at 0°C for 7 days; crystallization began to occur after cold storage at -15°C for 2 days, and after cold storage for 14 days, the sample could be restored to a clear state within 24 hours at room temperature.

[0046] Comparative Example 1

[0047] The difference between this comparative example and Example 1 is:

[0048] Without adding styrene-polyoxyethylene ether phosphate monoester and styrene-polyoxyethylene ether phosphate diester, the other steps are exactly the same as those in Example 1.

[0049] The fluazifop-butyl·quizalofop-P-ethyl·glufosinate microemulsion sample prepared in this example was turbid and stratified after being hot-stored at 54°C for 1 day; turbid and stratified after being cold-stored at 0°C for 1 day; crystals were precipitated after being cold-stored at -15°C for 1 day; and the sample could not be restored to a clear state at room temperature after being cold-stored for 14 days.

[0050] Comparative Example 2

[0051] The difference between this comparative example and Example 1 is:

[0052] The added amount of styrene-polyoxyethylene ether phosphate diester is 8%, and styrene-polyoxyethylene ether phosphate monoester is not added. The other steps are exactly the same as those in Example 1.

[0053] The fluazifop-butyl·quizalofop-P-ethyl·glufosinate microemulsion sample prepared in the comparative example became turbid and stratified after being hot-stored at 54°C for 1 day; became turbid and stratified after being cold-stored at 0°C for 1 day; crystals precipitated after being cold-stored at -15°C for 1 day and could not be restored to a clear state at room temperature after being frozen for 14 days.

[0054] Comparative Example 3

[0055] The difference between this comparative example and Example 1 is:

[0056] The added amount of styrene-polyoxyethylene ether phosphate monoester was 8%, and styrene-polyoxyethylene ether phosphate diester was not added. The other steps were exactly the same as those in Example 1.

[0057] The fluazifop-butyl·quizalofop-P-ethyl·glufosinate microemulsion sample prepared in this comparative example was clarified after heat storage at 54°C for 14 days; became turbid and stratified after cold storage at 0°C for 2 days; and began to crystallize after cold storage at -15°C for 7 days. After cold storage for 14 days, the sample could not return to a clear state at room temperature.

[0058] According to the comparison of Examples 1 to 7 and Comparative Examples 1 to 3, it can be seen that the fluazifop-butyl·quizalofop-ethyl·phosphinothric acid microemulsion to which styryl polyoxyethylene ether phosphate monoester and styryl polyoxyethylene ether phosphate diester are added can be stably stored at 54°C and 0°C, and can also quickly restore the clear state at room temperature after cold storage crystallization at -15°C, without affecting the quality of the product. According to the comparison of Examples 1 to 5 and Examples 6 to 7, it can be seen that when the weight ratio of styryl polyoxyethylene ether phosphate monoester:styryl polyoxyethylene ether phosphate diester is controlled at 2 to 5:1, the stability of the prepared fluazifop-butyl·quizalofop-ethyl·phosphinothric acid microemulsion is better, and it can also be stably stored at -15°C, and no crystallization will occur after 14 days.

[0059] In Comparative Examples 1 to 3, styrene-based polyoxyethylene ether phosphate monoester and styrene-based polyoxyethylene ether phosphate diester were not added simultaneously, and the stability at -15°C was not satisfactory, and crystallization could not be restored at room temperature.

Claims

1. A fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion, characterized in that: Calculated by weight percentage, the invention comprises 0.5-2% of fluazifop-butyl, 1.0-5.0% of quizalofop-p-ethyl, 15-30% of glufosinate-ammonium, 0.5-10% of styrene-polyoxyethylene ether phosphate monoester, 0.5-10% of styrene-polyoxyethylene ether phosphate diester, 2-5% of sodium polyoxyethylene fatty alcohol ether sulfate, 15-20% of alkyl glycoside and 8-15% of solvent, and the balance is deionized water.

2. The fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion according to claim 1, characterized in that: The weight ratio of the styrene-based polyoxyethylene ether phosphate monoester to the styrene-based polyoxyethylene ether phosphate diester is 2 to 5:

1.

3. The fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion according to claim 1, characterized in that: The solvent includes N-methyl-2-pyrrolidone and 150# solvent oil.

4. The fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion according to claim 3, characterized in that: The weight ratio of the N-methyl-2-pyrrolidone to 150# solvent oil is 1:1-3.

5. The fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion according to claim 1, characterized in that: The added amount of the fatty alcohol polyoxyethylene ether sodium sulfate is 2%.

6. The fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion according to claim 1, characterized in that: The added amount of the alkyl glycoside is 17%.

7. A method for preparing the fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion according to any one of claims 1 to 6, characterized in that: The steps include: After measuring each raw material according to weight percentage, add fluazifop-butyl and quizalofop-P-ethyl into the solvent and stir thoroughly until they are completely dissolved. Then add styryl polyoxyethylene ether phosphate monoester, styryl polyoxyethylene ether phosphate diester, fatty alcohol polyoxyethylene ether sodium sulfate and alkyl glycoside. Finally, add glufosinate-ammonium and stir thoroughly until the solution is clear to obtain fluazifop-butyl·quizalofop-P-ethyl·glufosinate-ammonium microemulsion.

8. Use of the fluazifop-butyl-quizalofop-P-ethyl-glufosinate microemulsion according to any one of claims 1 to 6, characterized in that: Used as a herbicide.