Triclopyr·glufosinate·flusilazole microemulsion and its preparation method and application

Abstract

The present application relates to the field of pesticide technology, and specifically discloses a triclopyr oxyacetic acid·fine glufosinate·flusilazole microemulsion and its preparation method and application, wherein the microemulsion comprises the following components in parts by weight: 104.27-1042.7 parts of triclopyr oxyacetic acid, 100.49-602.97 parts of glufosinate, 23.18-115.9 parts of flusilazole, 60-160 parts of cosolvent, 130-530 parts of emulsifier, and 670-870 parts of water. The triclopyr oxyacetic acid·fine glufosinate·flusilazole microemulsion prepared in the present application has good herbicidal effect, good control effect, good stability, simple preparation method, and is easy to produce.

Description

Technical Field

[0001] The present application relates to the technical field of pesticides, and in particular to a triclopyr-succinic acid-glufosinate-ammonium-flusilazole microemulsion and a preparation method and application thereof. Background Art

[0002] Triclopyr is a systemic selective herbicide that is absorbed by the leaves and roots of plants and conducted throughout the plant, gradually killing it. Gramineae crops are resistant to it. It is suitable for weeding and irrigating before forest afforestation, maintaining fire lines, nurturing pine trees and forest stand transformation, and for controlling broadleaf weeds and woody plants in non-arable land. It can also be used to control broadleaf weeds in fields of gramineous crops such as wheat, corn, oats, sorghum, etc. Its chemical name is [(3,5,6-trichloro-2-pyridyl)oxy]acetic acid; 3,5,6-triclopyroxyacetic acid, and its structural formula is as follows:

[0003]

[0004] Glufosinate-ammonium is a highly effective form of glufosinate-ammonium, with the characteristics of broad herbicidal spectrum, low toxicity, high activity and good environmental compatibility, and has excellent control effect on most weeds. Its chemical name is (D,L)-2-amino-4-[hydroxy(methyl)phosphonyl]butyric acid, and its structural formula is as follows:

[0005]

[0006] Combining triclopyr with glufosinate ammonium to make a microemulsion can effectively make up for the poor efficacy of triclopyr against grass weeds, increase the control effect on non-arable weeds and shrubs, and more effectively carry out weed control and irrigation control before afforestation, maintain firebreaks, etc. However, when using triclopyr and glufosinate microemulsion, its stability and weed control performance need to be further improved. Summary of the invention

[0007] In order to improve the problems existing in the prior art, the present application provides a triclopyr·glufosinate·flusilazole microemulsion and a preparation method and application thereof.

[0008] In the first aspect of the present invention, the present application provides a triclopyr·glufosinate·flusilazole microemulsion, which adopts the following technical scheme:

[0009] A triclopyr·glufosinate·flusilazole microemulsion is prepared from the following components in parts by weight: 104.27-1042.7 parts of triclopyr, 100.49-602.97 parts of glufosinate, 23.18-115.9 parts of flusilazole, 60-160 parts of cosolvent, 130-530 parts of emulsifier and 670-870 parts of water.

[0010] The present application prepares a triclopyroxyacetic acid·glufosinate-ammonium·flusilazole microemulsion by compounding triclopyroxyacetic acid, glufosinate-ammonium, flusilazole, a solubilizer and an emulsifier. Compared with the triclopyroxyacetic acid·glufosinate-ammonium microemulsion in the related art, triclopyroxyacetic acid·glufosinate-ammonium and flusilazole are compounded to improve the efficacy of the microemulsion on weeds. At the same time, by changing the components and ratios of the solubilizer and the emulsifier, the low-temperature stability, time stability and heat storage stability of the microemulsion are improved.

[0011] Triclopyr is absorbed by the leaves and roots of the plant and transmitted throughout the plant, causing deformities in the roots, stems, and leaves, depletion of storage substances, embolism or rupture of the vascular bundles, and gradual death of the plant.

[0012] Glufosinate is transferred in the leaves of weeds, and after glutamine synthesis is inhibited, ammonium ions accumulate and the photosynthetic layer is destroyed. It is a broad-spectrum contact herbicide with weak systemic effect. Glufosinate kills leaves first and can be conducted in the xylem of plants through plant transpiration. Flusilazole is a triazole systemic fungicide that can be used for systemic fungicide. It can be used to control some fungi. After adding glufosinate and triclopyr compound herbicide, flusilazole can increase the conduction rate of triclopyr and glufosinate between leaves, and has a significant synergistic effect on weed control within a certain mixing ratio range.

[0013] Preferably, the co-solvent includes one or more of N-methylpyrrolidone and p-aminobenzoic acid.

[0014] Preferably, the co-solvent is composed of N-methylpyrrolidone and p-aminobenzoic acid in a weight ratio of (1-4):1.

[0015] By changing the composition and ratio of N-methylpyrrolidone and p-aminobenzoic acid in the cosolvent, the time stability and heat storage stability of the triclopyr·glufosinate·flusilazole microemulsion can be improved. Among them, N-methylpyrrolidone is a colorless, transparent, oily liquid that can dissolve most organic and inorganic compounds, polar gases, natural and synthetic polymer compounds, does not affect the performance of triclopyr·glufosinate·flusilazole and has good solubility; p-aminobenzoic acid has a certain wetting and dispersing effect, and can enhance the dissolution effect of N-methylpyrrolidone when added in a certain proportion.

[0016] Preferably, the emulsifier is selected from one or more of sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyoxyethylene lauryl alcohol ether, castor oil polyoxyethylene ether, sodium dodecyl sulfonate, C12-C1 alkyl alcohol polyoxyethylene ether sulfate, and fatty alcohol ethylene oxide adduct sulfonate.

[0017] Preferably, the emulsifier is composed of calcium dodecylbenzene sulfonate, phenethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, and castor oil polyoxyethylene ether in a weight ratio of (1.22-2.44):1:(0.65-2.5):(0.78-1.22).

[0018] Calcium dodecylbenzene sulfonate is the main component of the mixed emulsifier of compound herbicide pesticide emulsion, and phenylethylphenol polyoxyethylene ether has good wetting and permeability;

[0019] Since the fatty alcohol polyoxyethylene ether is a surfactant with a good hydrophilic-lipophilic balance value, it has good emulsification and thickening effects. The castor oil polyoxyethylene ether is a non-ionic solubilizer, which can be used with the fatty alcohol polyoxyethylene ether to enhance the solubility. It can be used as a solvent for water-insoluble drugs in the triclopyr·glufosinate-ammonium·flusilazole microemulsion, and can also increase the fat solubility of fat-soluble components, so that the stability of the microemulsion at room temperature is improved. When calcium dodecylbenzene sulfonate, phenethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, and castor oil polyoxyethylene ether are added to the triclopyr·glufosinate-ammonium·flusilazole microemulsion in a suitable ratio, the adhesion between the microemulsions can be enhanced, the dispersion between different dissolving media can be stabilized, and the low-temperature stability, time stability, and heat storage stability of the microemulsion can be improved.

[0020] Preferably, the microemulsion further comprises an active agent, and the active agent is sodium lignin sulfonate; the weight portion of the sodium lignin sulfonate is 12-16 parts.

[0021] After using sodium lignin sulfonate, the dispersibility of each effective ingredient in the triclopyr·glufosinate·flusilazole microemulsion can be significantly improved, so that the coagulation effect between each component of the emulsifier is improved, and the low-temperature stability, time stability and heat storage stability of the microemulsion are all enhanced. Preferably, the microemulsion also includes an antifreeze agent, and the antifreeze agent is selected from one or more of ethylene glycol, glycerol, and urea, and the weight portion of the antifreeze agent is 10-15 parts.

[0022] After adding the antifreeze agent, the time stability of the microemulsion is improved, and the decomposition rate of the microemulsion after long-term storage can be reduced, thereby improving the storage stability of its effective ingredients.

[0023] In the second aspect of the present invention, the present application provides a method for preparing the triclopyr·glufosinate·flusilazole microemulsion provided in the first aspect of the present invention, and the method for preparing the triclopyr·glufosinate·flusilazole microemulsion comprises the following steps:

[0024] S1: Add glufosinate-ammonium, a cosolvent, triclopyr, flusilazole, an emulsifier, and water into a reaction container, and stir until dissolved to obtain the triclopyr·glufosinate-ammonium·flusilazole microemulsion.

[0025] Preferably, step S1 comprises the following steps:

[0026] S11: Preparation of refined glufosinate ammonium aqueous solution; dissolving refined glufosinate ammonium in water to prepare a refined glufosinate ammonium aqueous solution, wherein the mass concentration of the refined glufosinate ammonium aqueous solution is 45-55%;

[0027] S12: preparing the oil phase; putting the cosolvent into the reaction vessel, starting stirring, adding triclopyr and flusilazole, and stirring until dissolved;

[0028] S13: adding emulsifier; adding emulsifier to the reaction container and stirring evenly;

[0029] S14: adding the refined glufosinate-ammonium aqueous solution obtained in S11; adding the refined glufosinate-ammonium aqueous solution obtained in S11 to the reaction container; the preparation method further comprises:

[0030] S2: sodium lignin sulfonate addition: sodium lignin sulfonate is added into the reaction vessel and stirred evenly.

[0031] S3: adding antifreeze; adding antifreeze to the reaction vessel and stirring evenly to obtain the triclopyr·glufosinate·flusilazole microemulsion.

[0032] On the one hand, the refined glufosinate ammonium is first dissolved into a refined glufosinate ammonium aqueous solution and then added step by step, thereby improving the dispersion effect of the mixed slurry, so that the solubility and dispersibility of the refined glufosinate ammonium, triclopyr and flusilazole in the emulsifier and the cosolvent are improved, and the uniformity of the drug efficacy during use is guaranteed; on the other hand, the refined glufosinate ammonium and triclopyr are stably dispersed in the cosolvent and the emulsifier, thereby improving the stability of the microemulsion, so that the active ingredients in the microemulsion will not be decomposed and lost during a certain storage period or in a special environment of low temperature / high temperature.

[0033] Preferably, the preparation method further comprises packaging the triclopyr·glufosinate·flusilazole microemulsion in a packaging bottle, and the material of the packaging bag is PET or PEPA, preferably PET.

[0034] In the third aspect of the present invention, the present application provides the use of the triclopyraclostrobin·glufosinate-ammonium·flusilazole microemulsion provided in the first aspect of the present invention in the preparation of a herbicide.

[0035] Preferably, the herbicide is a herbicide targeting Alternanthera philoxeroides.

[0036] In summary, this application includes the following beneficial technical effects:

[0037] 1 The present invention provides a triclopyr·glufosinate·flusilazole microemulsion. Compared with the triclopyr·glufosinate microemulsion in the related art, triclopyr·glufosinate and flusilazole are compounded to improve the efficacy of the microemulsion on weeds, and flusilazole and triclopyr·glufosinate can produce a synergistic effect in weed control;

[0038] 2. The present invention provides a triclopyr·glufosinate·flusilazole microemulsion, which improves the low temperature stability, time stability and heat storage stability of the microemulsion by changing the components and ratios of the cosolvent and the emulsifier; when calcium dodecylbenzenesulfonate, phenethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and castor oil polyoxyethylene ether are added to the triclopyr·glufosinate·flusilazole microemulsion in a suitable ratio, the adhesion between the microemulsions can be enhanced, the dispersion between different dissolving media can be stabilized, the low temperature stability, time stability and heat storage stability of the microemulsion can be improved, and further 1. The present invention further improves the low temperature stability, time stability and heat storage stability of the microemulsion by adding sodium lignin sulfonate and antifreeze; 2. The present invention provides a method for preparing a triclopyr·glufosinate·flusilazole microemulsion, wherein the glufosinate original powder is dissolved into a glufosinate aqueous solution and then added in steps, thereby improving the dispersion effect of the mixed slurry, so that the solubility and dispersibility of glufosinate, triclopyr and flusilazole in the emulsifier and the co-solvent are improved, so that the active ingredients in the microemulsion will not be decomposed and lost during a certain storage period or in a special environment of low temperature / high temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is a flow chart of the preparation method of triclopyraclostrobin·glufosinate-ammonium·flusilazole microemulsion provided in the present application. DETAILED DESCRIPTION

[0040] The present application is further described in detail below in conjunction with examples. The following examples are only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. In the following examples, if specific conditions are not specified, they are carried out according to normal conditions or conditions recommended by the manufacturer. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise specified, the professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any method or material similar or equivalent to the recorded content may also be applied to the present invention.

[0041] The embodiments of the present application disclose a triclopyr·glufosinate·flusilazole microemulsion. In the following embodiments, glufosinate uses 98.5% pure glufosinate technical drug, triclopyr uses 95% pure triclopyr butoxyethyl ester, and flusilazole uses 95% pure flusilazole technical drug.

[0042] The triclopyraclostrobin·glufosinate·flusilazole microemulsion comprises the following components in parts by weight:

[0043] 104.27-1042.7 parts of triclopyr, 100.49-602.97 parts of glufosinate ammonium, 23.18-115.9 parts of flusilazole, 60-160 parts of cosolvent, 130-530 parts of emulsifier. Furthermore, the triclopyr·glufosinate ammonium·flusilazole microemulsion may also include 12-16 parts of sodium lignin sulfonate and 10-15 parts of antifreeze.

[0044] The present application is further described in detail below in conjunction with Examples 1-20, Comparative Examples 1-2 and the accompanying drawings.

[0045] Example

[0046] Examples 1-7

[0047] Examples 1-7 respectively provide a triclopyr·glufosinate·flusilazole microemulsion.

[0048] The preparation method of triclopyr oxyacetic acid, glufosinate ammonium and flusilazole microemulsion in Examples 1-7 is as follows: Figure 1 , including the following steps:

[0049] S1:

[0050] S11: Preparation of refined glufosinate ammonium aqueous solution: Take refined glufosinate ammonium and an appropriate amount of soft water, mix, and stir for 1 hour to obtain a refined glufosinate ammonium solution, wherein the mass concentration of the refined glufosinate ammonium solution is 50%, and set aside;

[0051] S12: Preparation of oil phase; take the cosolvent into the modulation kettle, start stirring, add triclopyr butoxyethyl ester, stir for 30 minutes, then add flusilazole, stir for 20 minutes, and fully dissolve;

[0052] S13: emulsifier addition: add emulsifier to the mixing kettle and continue stirring for 30 minutes;

[0053] S14: Add the refined glufosinate ammonium aqueous solution obtained in S11; add the remaining soft water into the preparation kettle, stir, add the refined glufosinate ammonium solution prepared in step S11 into the preparation kettle and continue stirring for 30 minutes to obtain the triclopyraclostrobin·refined glufosinate ammonium·flusilazole microemulsion.

[0054] The cosolvent is composed of N-methylpyrrolidone and p-aminobenzoic acid in a weight ratio of 60:40.

[0055] The emulsifier is composed of calcium dodecylbenzene sulfonate, phenethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and castor oil polyoxyethylene ether in a weight ratio of 110:60:150:60.

[0056] The difference between the above embodiments is that the weight proportions of the components in the triclopyr·glufosinate-ammonium·flusilazole microemulsion are specifically shown in Table 1.

[0057] Table 1 Weight parts of each component in the microemulsion provided by Examples 1-7

[0058]

[0059] Embodiment 8-11

[0060] Examples 8-11 respectively provide a triclopyr·glufosinate·flusilazole microemulsion.

[0061] The difference between the above embodiments and embodiment 2 is that the weight ratio of each component of the cosolvent in the triclopyr·glufosinate·flusilazole microemulsion is specifically shown in Table 2.

[0062] Table 2 Addition amount of each component of the cosolvent in the microemulsion provided in Example 2, Example 8-11

[0063]

[0064] Examples 12-16

[0065] Examples 12-16 respectively provide a triclopyr·glufosinate·flusilazole microemulsion.

[0066] The difference between the above embodiments and embodiment 2 is that the weight ratio of each component of the emulsifier in the triclopyr·glufosinate·flusilazole microemulsion is specifically shown in Table 3.

[0067] Table 3 Addition amount of each component in the emulsifier provided in Example 2, Examples 12-16

[0068]

[0069] Embodiment 17

[0070] Example 17 provides a triclopyr·glufosinate·flusilazole microemulsion.

[0071] The difference between the above embodiment and embodiment 2 is that calcium dodecylbenzenesulfonate in the emulsifier is replaced by polyvinyl pyrrolidone.

[0072] Embodiment 18

[0073] Example 18 provides a triclopyr·glufosinate·flusilazole microemulsion.

[0074] The difference between the above embodiment and embodiment 2 is that sodium lignin sulfonate is further added to the triclopyr·glufosinate·flusilazole microemulsion, and the amount of sodium lignin sulfonate added is 15 kg.

[0075] In Example 18, the preparation method of triclopyr oxypyraclostrobin·glufosinate·flusilazole microemulsion is as follows Figure 1 , including the following steps:

[0076] S1:

[0077] S11: Preparation of refined glufosinate solution: soft water was added to a stirred tank, stirring was started, refined glufosinate was added, and stirred for 1 hour to obtain a refined glufosinate solution, wherein the mass concentration of the refined glufosinate solution was 50%, and the solution was set aside;

[0078] S12: Preparation of oil phase; take the cosolvent and put it into the modulation kettle, start stirring, add triclopyr butoxyethyl ester, stir for 30 minutes, then add flusilazole, stir for 20 minutes to fully dissolve it;

[0079] S13: emulsifier addition: add emulsifier to the mixing kettle and continue stirring for 30 minutes;

[0080] S14: adding the refined glufosinate-ammonium aqueous solution obtained in S11;

[0081] The remaining soft water was added to the preparation kettle, and the refined glufosinate ammonium solution prepared in step S11 was added to the preparation kettle, and stirring was continued for 30 minutes;

[0082] S2: adding sodium lignin sulfonate; standing for 10 minutes, adding 15 kg of sodium lignin sulfonate to the preparation kettle and stirring evenly to obtain the triclopyr·fine glufosinate·flusilazole microemulsion.

[0083] Embodiment 19

[0084] Example 19 provides a triclopyr·glufosinate·flusilazole microemulsion.

[0085] The difference between the above embodiment and embodiment 2 is that: 13 kg of antifreeze is added to the triclopyr·glufosinate·flusilazole microemulsion, and the antifreeze is urea.

[0086] In Example 19, the preparation method of triclopyr oxypyraclostrobin·glufosinate-ammonium·flusilazole microemulsion is as follows: Figure 1 , including the following steps:

[0087] S1:

[0088] S11: Preparation of refined glufosinate solution: soft water was added to a stirred tank, stirring was started, refined glufosinate was added, and stirred for 1 hour to obtain a refined glufosinate solution, wherein the mass concentration of the refined glufosinate solution was 50%, and the solution was set aside;

[0089] S12: Preparation of oil phase; take the cosolvent and put it into the modulation kettle, start stirring, add triclopyr butoxyethyl ester, stir for 30 minutes, then add flusilazole, stir for 20 minutes to fully dissolve it;

[0090] S13: emulsifier addition: add emulsifier to the mixing kettle and continue stirring for 30 minutes;

[0091] S14: adding the refined glufosinate-ammonium aqueous solution obtained in S11;

[0092] The remaining soft water was added to the preparation kettle, and the refined glufosinate ammonium solution prepared in step S11 was added to the preparation kettle, and stirring was continued for 30 minutes;

[0093] S2: sodium lignin sulfonate addition; let stand for 10 minutes, add 15Kg sodium lignin sulfonate to the preparation kettle and stir evenly;

[0094] S3: adding antifreeze; adding 13 kg of antifreeze to the preparation kettle and stirring evenly to obtain triclopyr·glufosinate-ammonium·flusilazole microemulsion.

[0095] Embodiment 20

[0096] Example 20 provides a triclopyr·glufosinate·flusilazole microemulsion.

[0097] The difference between the above embodiment and embodiment 19 is that the microemulsion preparation method is different. Embodiment 20 includes the following preparation steps:

[0098] S1: Add soft water, put the refined glufosinate and the cosolvent into a modulation kettle, start stirring, then add the emulsifier, triclopyr and flusilazole, and stir until completely dissolved;

[0099] S2: Let stand for 10 minutes, add 15 kg of sodium lignin sulfonate to the preparation kettle and stir evenly;

[0100] S3: Add 13 kg of antifreeze into the preparation kettle and stir evenly to obtain the triclopyr·glufosinate-ammonium·flusilazole microemulsion.

[0101] Comparative Example

[0102] Comparative Example 1

[0103] Comparative Example 1 provides a triclopyr-glufosinate-ammonium microemulsion.

[0104] The difference between the above comparative example and Example 2 is that: the microemulsion does not contain flusilazole.

[0105] Comparative Example 2

[0106] Comparative Example 2 provides a flusilazole microemulsion.

[0107] The difference between the above comparative example and Example 2 is that: the microemulsion does not contain triclopyr and glufosinate-ammonium.

[0108] Performance detection

[0109] Colby method

[0110] (1) Test method: Compare the actual survival rate of Alternanthera philoxeroides (measured relative inhibition rate; %) E when single agents A and B are mixed with the theoretical survival rate (theoretical relative inhibition rate; %) E0.

[0111] Binary mixture:

[0112] Multiple mixture:

[0113] X1, Y1, A, and B are the survival rates (relative inhibition rates) of Alternanthera philoxeroides when each agent is used alone.

[0114] E < E0, synergistic effect

[0115] E > E0, antagonistic effect

[0116] E = E0, additive effect

[0117] (2) Test time: 2 months.

[0118] (3) Test results: The test results of the microemulsions provided in Example 2 and Comparative Examples 1-2 are shown in Table 4.

[0119] Table 4 Test results of Colby method

[0120]

[0121] According to the test results of Comparative Examples 1-2 and Example 2 in Table 4, it can be seen that after adding flusilazole, the survival rate of Alternanthera philoxeroides decreased significantly. Flusilazole can improve the inhibitory ability of triclopyr·glufosinate-ammonium microemulsion alone or flusilazole alone against Alternanthera philoxeroides, thereby enhancing the drug efficacy.

[0122] Drug efficacy detection

[0123] Field efficacy trials were conducted on the picloram·glufosinate-ammonium·flusilazole microemulsion provided in Examples 1-5 of the present application, the picloram·glufosinate-ammonium microemulsion provided in Comparative Example 1, and the flusilazole microemulsion provided in Comparative Example 2 for controlling Alternanthera philoxeroides in non-cultivated land and shrubs in forest land.

[0124] Test conditions: The test plot was non-cultivated land that had been abandoned for about 2 years. The land was flat, with medium soil fertility, good drainage, and no irrigation facilities.

[0125] Selection of test object weeds: Alternanthera philoxeroides.

[0126] Cultivation conditions: Loam soil, pH value of 6.7, medium fertility, and organic matter content of 0.9%. No pesticides, fungicides, herbicides, or plant growth regulators had been applied before the test.

[0127] Test design and arrangement:

[0128] The picloram·glufosinate-ammonium·flusilazole microemulsion provided in Examples 1-5, the picloram·glufosinate-ammonium microemulsion provided in Comparative Example 1, and the flusilazole microemulsion provided in Comparative Example 2 were selected; the treatment concentration was 1600 (g.a.i. / hm 2 ). The control effects on Alternanthera philoxeroides after 15 days and 45 days of application of each agent are shown in Table 5 below:

[0129] Table 5 Control effects at 15d / 45d

[0130]

[0131] According to the test results in Table 10, comparing Examples 1-5, the mass ratio of picloram, glufosinate-ammonium, and flusilazole microemulsion affects the control effect. Within a certain range, the control effect is positively correlated with the addition amount of glufosinate-ammonium but not linearly changed. Therefore, the addition amount of glufosinate-ammonium should be controlled within a certain range, and the control effect is the best when the mass ratio of the three is 3.98:11.49:1.

[0132] Comparing Example 2 with Comparative Examples 1-2, it can be seen that the control effect of Example 2 is better than the sum of the control effects of Comparative Examples 1-2, and E < E0. Thus, it can be seen that flusilazole can improve the inhibitory ability of picloram·glufosinate-ammonium microemulsion alone or flusilazole alone on Alternanthera philoxeroides, thereby enhancing the efficacy of controlling Alternanthera philoxeroides.

[0133] Stability test

[0134] (1) Test standard:

[0135] GB / T 19137-2003 Determination method for low temperature stability of pesticides

[0136] NY / T 1427-2007 General Rules for Storage Stability Test of Pesticides at Room Temperature

[0137] GB / T 19136-2003 General Standard Methods for Pesticides

[0138] (2) Test method:

[0139] Low temperature stability: Pipette 100 ml of the sample into a centrifuge tube, cool it to (0±2)℃ in a refrigerator, keep the centrifuge tube and its contents at (0±2)℃ for 1 hour, and stir every 15 minutes for 15 seconds each time. Check and record whether there is any solid or oily precipitation; the sample is qualified if it is stored at 0℃±1℃ for 7 days without precipitation of crystals or stratification.

[0140] Stability over time: Refer to NY / T 1427-2007, when stored at (30±2)℃ for 2 years, the decomposition rate of active ingredients is less than 5%, which is acceptable.

[0141] Thermal storage stability: When stored at 54℃±2℃ for 14 days, the thermal storage decomposition rate of the active ingredient is less than 10%, which is acceptable.

[0142] The above-mentioned active ingredients refer to the content of triclopyraclostrobin, glufosinate-ammonium and flusilazole.

[0143] (3) Test results

[0144] Take the triclopyraclostrobin·glufosinate·flusilazole microemulsion provided in Example 2 and Examples 8-19, respectively fill 200 mL, and after hot-melt sealing packaging, the stability test results of the active ingredients of each agent are as follows:

[0145] Table 6 Stability test results

[0146]

[0147]

[0148] By comparing the test results of Example 2 and Examples 6-7, it can be seen that the total mass fraction of the cosolvent and the emulsifier is in the range of 1211-1360. Adjusting the mass fraction of the cosolvent, the emulsifier and the water can improve the temporal stability and the thermal storage stability of the microemulsion; when the total mass fraction weight ratio of the cosolvent, the emulsifier and the water is 100:380:731, the temporal stability and the thermal storage stability of the microemulsion are optimal.

[0149] Comparing the test results of Example 2 and Example 8-11, it can be seen that by adjusting the addition amount of N-methylpyrrolidone and p-aminobenzoic acid, the decomposition rate of the microemulsion is controlled between 1.57-4.23% after 2 years, and the decomposition rate of the microemulsion is controlled between 1.74-3.95% after 14 days of heat storage; compared with adding N-methylpyrrolidone and p-aminobenzoic acid separately and adding them together, the microemulsion has better stability performance when the two are mixed. In addition, by increasing the addition ratio of N-methylpyrrolidone, preferably when the addition ratio of N-methylpyrrolidone to p-aminobenzoic acid is (1-4): 1, the low temperature stability, time stability and heat storage stability of the microemulsion are optimized. This may be because p-aminobenzoic acid can enhance the dissolution of the active ingredients triclopyr, glufosinate ammonium and flusilazole at a certain addition ratio, so that the time stability and heat storage stability of the microemulsion are affected.

[0150] By comparing the test results of Example 2 and Examples 12-13, it can be seen that by adjusting the addition ratio of calcium dodecylbenzenesulfonate, phenethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, and castor oil polyoxyethylene ether in the emulsifier within 110: (45-90): (110-170): (55-70), the low-temperature stability, time stability, and heat storage stability of the microemulsion can reach the qualified level and the stabilization effect is better.

[0151] This may be because the relative density and viscosity of fatty alcohol polyoxyethylene ether at this ratio are relatively increased, the auxiliary dissolving power of other ingredients is improved, the adhesion between emulsifiers is improved, and the stability is added with phenethylphenol polyoxyethylene ether and castor oil polyoxyethylene ether at this ratio, so that the stability of the microemulsion at room temperature is improved; since fatty alcohol polyoxyethylene ether itself is a surfactant with a hydrophilic-lipophilic balance value, it has a good emulsifying and thickening effect, and has a strengthening effect on the adhesion of other ingredients in the emulsifier, and castor oil polyoxyethylene ether is a non-ionic solubilizer, which can cooperate with fatty alcohol polyoxyethylene ether to enhance the solubility performance, so that the solvent for water-insoluble drugs in the microemulsion is further dissolved; at the same time, after using N-methylpyrrolidone and p-aminobenzoic acid in a weight ratio of 3:2 as solvents, fatty alcohol polyoxyethylene ether is combined with castor oil polyoxyethylene ether to assist the solubility rate of fat-soluble components.

[0152] By comparing the test results of Example 2 and Examples 14-16, it can be seen that when the mass fraction of calcium dodecylbenzenesulfonate remains unchanged, when phenethylphenol polyoxyethylene ether is replaced by C12-C1 alkyl alcohol polyoxyethylene ether sulfate / fatty alcohol polyoxyethylene ether is replaced by sorbitol polyoxyethylene ether / castor oil polyoxyethylene ether is replaced by polyoxyethylene lauryl alcohol ether, the low temperature stability, time stability and heat storage stability of the microemulsion will be reduced to varying degrees; especially when fatty alcohol polyoxyethylene ether is replaced by sorbitol polyoxyethylene ether, the time stability of the microemulsion will be worse.

[0153] By comparing the test results of Example 2 and Example 17, it can be seen that when calcium dodecylbenzenesulfonate in the emulsifier is replaced by polyvinyl pyrrolidone, the microemulsion emulsifier will appear agglomeration and turbidity at low temperatures, and a small amount of solid will precipitate, thereby affecting its low-temperature stability. In addition, its stability will also decrease after hot storage or long-term storage. This may be because calcium dodecylbenzenesulfonate can increase the wettability of the microemulsion.

[0154] By comparing the test results of Example 2 and Example 18, it can be seen that the addition of sodium lignin sulfonate has a reinforcing effect on the low temperature stability, time stability and heat storage stability of the microemulsion. This may be because sodium lignin sulfonate, as an active agent, can improve the dispersion uniformity of each effective ingredient in the triclopyr·glufosinate·flusilazole microemulsion, so that triclopyr, glufosinate, flusilazole, etc. are fully dissolved and emulsified in the cosolvent and dispersant, and finally enhance the emulsification and coagulation effect.

[0155] By comparing the results of Example 18 and Example 19, it can be seen that after adding the antifreeze, the time-dependent decomposition rate of the microemulsion can be reduced to 1.13. This may be because the antifreeze improves the internal structure of the microemulsion, so that the time stability and thermal storage stability of triclopyr, glufosinate ammonium and flusilazole in the microemulsion are optimized in the state of adding the antifreeze, and the decomposition rate of the microemulsion is reduced after long-term storage or under high / low temperature conditions.

[0156] By comparing the test results of Example 19 and Example 20, it can be seen that the various stabilities of Example 20 are lower than those of Example 19. This may be because the step-by-step preparation method plays an auxiliary role in the stability of the microemulsion; in Example 20, the refined glufosinate ammonium is directly put into the modulation kettle to react with the cosolvent, etc., so that the dispersion effect is affected. When the preparation method in Implementation 19 is used to first configure the refined glufosinate ammonium powder into an aqueous solution, the dispersion performance of each component in the microemulsion can be improved to a certain extent, and finally the time stability and heat storage stability of the microemulsion are improved, so that the active ingredients in the microemulsion will not be decomposed and lost during a certain storage period or in a special environment of low temperature / high temperature.

[0157] Efficacy test

[0158] Field efficacy tests for controlling non-cultivated weeds and forest shrubs were conducted on the triclopyr·glufosinate·flusilazole microemulsion provided in Example 19 of the present application and the triclopyr·glufosinate microemulsion provided in Comparative Example 1.

[0159] Purpose of the experiment: To determine the efficacy, safety and application technology of triclopyraclostrobin·glufosinate-ammonium·flusilazole microemulsion in controlling weeds in non-arable land at different application doses.

[0160] Experimental conditions: The experimental field was non-arable land that had been abandoned for about 2 years. The land was flat, the soil fertility was medium, the drainage was smooth, and there were no irrigation facilities.

[0161] Selection of experimental weeds: Alternanthera philoxeroides.

[0162] Cultivation conditions: loam, pH 6.7, medium fertility, organic matter content 0.9%. No pesticides, fungicides, herbicides or plant growth regulators were applied before the experiment.

[0163] Experimental design and arrangement:

[0164] The triclopyraclostrobin·glufosinate·flusilazole microemulsion prepared in Example 19 was selected; dosage form: microemulsion; numbered 1-5 according to different application dosages.

[0165] Triclopyr·glufosinate-ammonium microemulsion; content: 30%; dosage form: microemulsion; number: 6.

[0166] The experimental design of the test drug is as follows:

[0167] Table 7 Microemulsion Experimental Design Provided in Example 19

[0168]

[0169]

[0170] The cell arrangement is as follows:

[0171] Table 8 Experimental design plot arrangement table

[0172] 1 2 3 4 5 6 7 6 7 1 2 3 4 5 4 5 6 7 1 2 3 3 4 5 6 7 1 2

[0173] Plot size and repetition: Plot size: 20m 2 ; Number of repetitions: 4 times.

[0174] Usage: Use the spray method. First add a small amount of clean water to the sprayer, take the test drug and dilute it in a large cup, then pour it into the sprayer, add enough water and mix well, then spray evenly in the whole area.

[0175] Application equipment: The test used a Luyou 3wd-16 backpack electric sprayer with a water consumption of 30kg / 667m 2 The same agent was sprayed from a low concentration. After each spray, the sprayer was cleaned with clean water for 3 times before spraying another treatment agent.

[0176] Application time and frequency: The application time is May 7, 2021, and the application is once.

[0177] Dosage: The dosage of triclopyr·glufosinate·flusilazole microemulsion is 300-400g / mu. The recommended dosage of 30% triclopyr·glufosinate microemulsion is 300g / mu.

[0178] Meteorological data: spray once at 15:00 on May 7, 2021, with a water consumption of 450kg / hm 2 It was cloudy when the pesticide was applied, the temperature was 13.4-20.1℃, the air humidity was 70%, and the southeast wind was level 1.

[0179] Field management information: No pesticides, fungicides, herbicides or plant growth regulators were applied before the experiment.

[0180] Time and frequency of Alternanthera philoxeroides survey: The experiment conducted two surveys, 15 days and 30 days after application of pesticides.

[0181] Survey method: According to GB / T17980.51-2000, the estimated value survey method was used, that is, each treatment was compared with the adjacent blank control area to estimate the relative population of Alternanthera philoxeroides. The classification standards are as follows:

[0182] Level 0: no grass;

[0183] Level 1: 0% to 2.5% relative to the blank control area;

[0184] Level 2: 2.6% to 5% relative to the blank control area;

[0185] Level 3: 5.1% to 10% relative to the blank control area;

[0186] Level 4: 10.1% to 15% relative to the blank control area;

[0187] Level 5: 15.1% to 25% relative to the blank control area;

[0188] Level 6: 25.1% to 35% relative to the blank control area;

[0189] Level 7: 35.1% to 50% relative to the blank control area;

[0190] Level 8: 50.1% to 67.5% relative to the blank control area;

[0191] Level 9: 67.6% to 100% relative to the blank control area.

[0192] Efficacy calculation method: Control effect (%) = [1-PT / CK] × 100

[0193] Where: PT-the number of weeds in the area treated with pesticides; CK-the number of weeds in the control area.

[0194] The control effect of triclopyraclostrobin·glufosinate·flusilazole microemulsion (%) - 15 days after application, as shown in the following table:

[0195] Table 9 15-day control effect

[0196] Chemical treatment Weed control effect % and significant difference Alternanthera philoxeroides 1 80.2f 2 85.1e 3 89.7d 4 93.4c 5 95.7b 6 72.2f 7 100a

[0197] The control effect of triclopyraclostrobin·glufosinate·flusilazole microemulsion (%) - 30 days after application, as shown in the following table:

[0198] Table 10 30-day control effect

[0199] Chemical treatment Weed control effect % and significant difference Alternanthera philoxeroides 1 76.2g 2 79.7f 3 85.2d 4 88.1c 5 90.4b 6 67.2g 7 100a

[0200] Note: The significant differences in the table are variance analysis of the number of Alternanthera philoxeroides plants surveyed in the experimental field, with a 5% significant difference, where a, b, c, d, e, f, and g are used to represent the differences between the data and the blank control group data, and the differences increase from a to g.

[0201] As shown in Tables 9 and 10, the effective ingredient content of triclopyr·glufosinate-ammonium microemulsion reached 1350 g / hm2. 2 When the amount of triclopyr·glufosinate·flusilazole microemulsion is less than 1%, its 15-day efficacy can be similar to that of the microemulsion of triclopyr·glufosinate·flusilazole with the same amount of active ingredients. Therefore, a small amount of triclopyr·glufosinate·flusilazole microemulsion can achieve the same effect as a large amount of triclopyr·glufosinate·flusilazole microemulsion. The use of triclopyr·glufosinate·flusilazole can improve the efficacy of weed control and reduce the cost of weed control.

[0202] Triclopyr·glufosinate·flusilazole microemulsion can control non-arable land weeds such as Alternanthera philoxeroides, Vetch, Artemisia selengensis, Digitaria tangutica, Echinochloa crus-galli, etc. It also has a certain control effect on other broad-leaved weeds (Solanum nigrum, Ramie, Salsola, Thistle), but it is particularly suitable for controlling Alternanthera philoxeroides. The control rate of Alternanthera philoxeroides can reach 80.2% to 95.7% within 15 days.

[0203] In this year's test, the comprehensive protective effect of different gradient treatments of the experimental agents on Alternanthera philoxeroides was 81.5% to 92.6%; the investigation 30 days after the application of the agent showed that the comprehensive protective effect on the number of Alternanthera philoxeroides plants was 75.6% to 87.5%; the investigation 45 days after the application of the agent showed that the comprehensive protective effect on the number of Alternanthera philoxeroides plants was 68.3% to 83.1%.

[0204] Effects of different packaging capacities and packaging materials on thermal storage stability

[0205] The 30% triclopyraclostrobin·glufosinate·flusilazole microemulsion in Example 2 was placed in 200 mL, 500 mL, and 1000 mL PET or PEPA bottles, respectively, and sealed by hot melt. A heat storage stability test was conducted according to the general standard method for pesticides GB / T 19136-2003 for determining the heat storage stability of pesticides. The results are as follows:

[0206] Table 11 Hot storage stability test under different packaging materials and guaranteed volumes

[0207]

[0208]

[0209] According to the test results in Table 11, it can be seen that PET and PEPA packaging materials will affect the thermal storage stability of triclopyraclostrobin·glufosinate-ammonium·flusilazole microemulsion, and the thermal storage stability of PET packaging materials is generally better than that of PEPA.

[0210] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A triclopyr oxypyrazone-glufosinate-ammonium-flusilazole microemulsion, characterized in that: The microemulsion comprises the following components in parts by weight: 104.27-1042.7 parts of triclopyr, 100.49-602.97 parts of glufosinate ammonium, Flusilazole 23.18-115.9 parts, Solvent 60-160 parts, Emulsifier 130-530 parts, 670-870 parts of water; The cosolvent is composed of N-methylpyrrolidone and p-aminobenzoic acid in a weight ratio of (1-4):1; The emulsifier is composed of calcium dodecylbenzene sulfonate, phenethylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether and castor oil polyoxyethylene ether in a weight ratio of (1.22-2.44):1:(0.65-2.5):(0.78-1.22).

2. The triclopyr·glufosinate·flusilazole microemulsion according to claim 1, characterized in that: The microemulsion also includes sodium lignin sulfonate.

3. The triclopyr·glufosinate·flusilazole microemulsion according to claim 1, characterized in that: The microemulsion also includes an antifreeze agent, which is selected from one or more of ethylene glycol, glycerol, and urea.

4. A method for preparing the triclopyr·glufosinate·flusilazole microemulsion according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1: Add glufosinate-ammonium, a cosolvent, triclopyr, flusilazole, an emulsifier and water into a reaction container, and stir until dissolved to obtain the triclopyr·glufosinate-ammonium·flusilazole microemulsion.

5. The method for preparing the triclopyr·glufosinate·flusilazole microemulsion according to claim 4, characterized in that: The S1 step includes the following steps: S11: dissolving refined glufosinate ammonium in water to prepare a refined glufosinate ammonium aqueous solution, wherein the mass concentration of the refined glufosinate ammonium aqueous solution is 45-55%; S12: putting a cosolvent into the reaction vessel, adding triclopyr and flusilazole, and stirring until dissolved; S13: adding an emulsifier to the reaction vessel and stirring evenly; S14: Add the refined glufosinate-ammonium aqueous solution obtained in S11 into the reaction container.

6. The method for preparing the triclopyr·glufosinate·flusilazole microemulsion according to claim 4, characterized in that: Further including: S2: adding sodium lignin sulfonate into the reaction vessel and stirring evenly; S3: adding antifreeze to the reaction container and stirring evenly to obtain the triclopyr·glufosinate·flusilazole microemulsion.

7. Use of the triclopyr-succinic acid-glufosinate-ammonium-flusilazole microemulsion according to any one of claims 1 to 3 in the preparation of herbicides.

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