A herbicide composition containing glufosinate-ammonium

Abstract

The present application provides a kind of complex herbicide containing glufosinate-ammonium, which includes effective component and auxiliary material, and the effective component includes glufosinate-ammonium and fluroxypyr-methyl at a mass ratio of 0.5-10:1.The complex herbicide of the present application forms a mutual synergistic effect between glufosinate-ammonium and fluroxypyr-methyl, and the price of fluroxypyr-methyl is significantly lower than that of glufosinate-ammonium raw material.Compared with the same amount of glufosinate-ammonium herbicide, the complex herbicide of the present application can reduce the cost of drug use while improving the weed control effect, and can reduce the drug resistance of weeds to glufosinate-ammonium.The present application also optimizes the formula of different dosage forms, selects the auxiliary material and the components of the complex, uses fewer types of auxiliary materials while ensuring the efficacy of the preparation, and the auxiliary materials are commonly available and can further reduce the cost, so that the complex herbicide of the present application has higher market promotion value and economic benefits.

Description

Technical Field

[0001] This invention belongs to the field of herbicides, specifically relating to a compound herbicide containing glufosinate-ammonium. Background Technology

[0002] Glufosinate is a highly effective, low-toxicity, non-selective contact phosphate herbicide. Glufosinate is an L-type glufosinate, with twice the herbicidal activity of racemic DL-type glufosinate mixtures. It has excellent water solubility, structural stability, and is easy to process and mix. In the context of reducing pesticide use while increasing efficiency, glutfosinate is a good alternative to non-selective herbicides. However, long-term use of glutfosinate alone can lead to herbicide resistance, reducing weed control effectiveness. Furthermore, the current price of glutfosinate is relatively high compared to traditional non-selective herbicides such as glyphosate, limiting its market potential.

[0003] Different herbicides have varying biological activities and weed-killing spectra, and theoretically, their combined use can have a complementary and synergistic effect. Combining glufosinate with other herbicides may achieve better weed control while reducing the amount of glufosinate used, thereby improving weed control efficacy while lowering herbicide prices, ensuring safe crop growth, and reducing environmental pollution. Therefore, it is necessary to develop more compound herbicides containing glufosinate. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a compound herbicide containing glufosinate-ammonium.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A compound herbicide containing glufosinate-ammonium, comprising an active ingredient and excipients, wherein the active ingredient comprises glufosinate-ammonium and isooctyl clopyralid, and the mass ratio of glufosinate-ammonium to isooctyl clopyralid is 0.5–10:1, for example 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1. More preferably, the ratio is 1–5:1.

[0007] Preferably, the active ingredient consists of glufosinate and isooctyl clopyralid.

[0008] Preferably, the active ingredient accounts for 15% to 75% of the total mass of the compound herbicide, for example, 15%, 20%, 25%, 30%, 235%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, and 75%.

[0009] Preferably, the excipients include surfactants comprising 5% to 40% of the total weight of the compound herbicide.

[0010] More preferably, the surfactant is one or more of the following: wetting agent, emulsifier, and dispersant.

[0011] More preferably, the surfactant is one or a combination of fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate, polycarboxylate, ammonium polyether sulfonate, phenethylphenol polyoxyethylene ether phosphate triethanolamine salt, sodium lauryl ether sulfate, alkyl sulfate, and N,N-dimethyldecylamide.

[0012] More preferably, the excipients further include one or more combinations of antifreeze, solvent, filler, disintegrant, and binder.

[0013] More preferably, the antifreeze is one or a combination of glycerol, propylene glycol, and ethylene glycol.

[0014] More preferably, the solvent is one or a combination of water, ethanol, methanol, N,N-dimethylformamide, dimethyl sulfoxide, cyclohexanone, methyl oleate, and vegetable oil.

[0015] More preferably, the filler is one or a combination of diatomaceous earth, kaolin, bentonite, silica, and light calcium carbonate.

[0016] More preferably, the disintegrant is one or more of the following: ammonium sulfate, urea, sodium sulfate, starch and its derivatives, cellulose, sodium bicarbonate, sodium lauryl sulfate, sodium alginate, and sodium chloride.

[0017] The binder is one or more of the following: starch, gelatin, pregelatinized starch, gum arabic, polyvinylpyrrolidone, methylcellulose, hydroxypropyl methylcellulose, polyethylene glycol, polyvinyl alcohol, glucose, and sucrose.

[0018] According to some preferred embodiments, the compound herbicide is formulated as an oil suspension, which includes an active ingredient, a surfactant, a filler, and an organic solvent. The surfactant is at least two of fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate, polycarboxylate, and ammonium polyether sulfonate.

[0019] According to some preferred embodiments, the formulation of the compound herbicide is a suspension emulsion, which includes an active ingredient, a surfactant, cyclohexanone, and water. The surfactant is at least two of fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate, polycarboxylate, phenethylphenol polyoxyethylene ether phosphate triethanolamine salt, and sodium lauryl ether sulfate.

[0020] According to some preferred embodiments, the compound herbicide is formulated as an emulsifiable powder, which includes an active ingredient, a surfactant, and a filler, wherein the surfactant is at least two of polycarboxylate, alkyl sulfate, and phenethylphenol polyoxyethylene ether.

[0021] Emulsifiable powders are formulated by dissolving the active ingredients in the oil phase with surfactants and solvents, then adsorbing them onto a solid wettable powder, followed by high-speed shearing to obtain a qualified emulsifiable powder formulation. Due to the finer particle size of the active ingredients and the presence of solvents, emulsifiable powders have better efficacy than conventional wettable powders.

[0022] According to some embodiments, the compound herbicide is formulated as an oil suspension, and by mass percentage, it comprises the following components:

[0023]

[0024] According to other embodiments, the compound herbicide is formulated as a suspension emulsion, and by mass percentage, it comprises the following components:

[0025]

[0026]

[0027] According to some other embodiments, the compound herbicide is formulated as an emulsifiable powder, and by mass percentage, it comprises the following components:

[0028] Active ingredient content: 35%–75%;

[0029] Surfactant 10%–25%;

[0030] N,N-dimethylformamide 5%–15%;

[0031] Filler content: 10%–40%.

[0032] Preferably, when the formulation of the compound herbicide is an oil suspension, the surfactants are a combination of fatty alcohol polyoxyethylene ether and alkylbenzene sulfonate.

[0033] Preferably, when the formulation of the compound herbicide is a suspension emulsion, the surfactant is a composition of fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate and polycarboxylate.

[0034] Preferably, when the formulation of the compound herbicide is an emulsifiable powder, the surfactant is a composition of polycarboxylate, alkyl sulfate and fatty alcohol polyoxyethylene ether.

[0035] According to some specific and preferred embodiments, the compound herbicide is formulated as an oil suspension, and by mass percentage, it comprises the following components:

[0036]

[0037] According to some other specific and preferred embodiments, the compound herbicide is formulated as a suspension emulsion, and by mass percentage, it comprises the following components:

[0038]

[0039] According to some specific and preferred embodiments, the compound herbicide is formulated as an emulsifiable powder, and by mass percentage, it comprises the following components:

[0040]

[0041] The present invention also provides the application of the above-mentioned compound herbicide in controlling one or more of barnyard grass, foxtail grass, crabgrass, purslane, goosegrass, lambsquarters, tuft of grass or fleabane.

[0042] Preferably, the compound herbicide of the present invention is used to control weeds in grape fields.

[0043] Due to the implementation of the above technical solutions, the present invention has the following advantages compared with the prior art:

[0044] In this invention, the compound herbicide contains glufosinate and isooctyl clopyralid, which have a synergistic effect. Compared to glufosinate herbicides with the same or similar active ingredient dosages, this compound herbicide significantly improves the control efficacy against barnyard grass, foxtail, crabgrass, purslane, and fleabane in grapevines. Reducing the dosage of glufosinate can decrease the development of glufosinate resistance in weeds. Furthermore, the price of isooctyl clopyralid technical grade is significantly lower than that of glufosinate technical grade, thus improving weed control efficacy while reducing application costs. Further, this invention optimizes the formulation of different formulations by selecting appropriate excipients for compounding the components. This ensures efficacy while using fewer excipient types. Since the excipients are common and readily available, costs can be further reduced, thus giving this compound herbicide higher market value and economic benefits. Detailed Implementation

[0045] The present invention will be further described in detail below with reference to specific embodiments. It should be understood that these embodiments are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to specific requirements, and the implementation conditions not specified are generally the conditions in conventional experiments.

[0046] The glufosinate-ammonium TC (purity > 97%) was purchased from Qizhou Green Chemical Co., Ltd.

[0047] 10% glufosinate-ammonium aqueous solution (Jingtianxia) was purchased from Shandong Yisheng Industrial Co., Ltd.

[0048] Isooctyl chloropyroxyacetate TC (purity > 97%) was purchased from Hubei Deante Chemical Technology Co., Ltd.

[0049] 200g / L clopyralid isooctyl ester emulsifiable concentrate (pesticide registration certificate number: PD20081316) was purchased from Jiangxi Jiangnan Lv'an Ecological Technology Co., Ltd.

[0050] Fatty alcohol polyoxyethylene ether (AEO-9) was purchased from Haian Petrochemical Plant in Jiangsu Province;

[0051] Alkylbenzene sulfonate (sodium dodecylbenzene sulfonate, Rhodacal DS-10) was purchased from Shanghai Zhenlishi Network Technology Co., Ltd.

[0052] The polycarboxylate (SD-816) was purchased from Shanghai Shida Polymer Materials Co., Ltd.

[0053] Ammonium polyether sulfonate (222) was purchased from Jiangsu Haolong Chemical Co., Ltd.;

[0054] Alkyl sulfate (VT859) was purchased from Spiessart Chemicals (Shanghai) Co., Ltd.

[0055] Phenethylphenol polyoxyethylene ether (601) was purchased from Yixing Jiateng Chemical Co., Ltd.

[0056] Phenethylphenol polyoxyethylene ether phosphate triethanolamine salt (agricultural emulsion 600P) was purchased from Linyi Guoli Chemical Co., Ltd.

[0057] Sodium lauryl ether sulfate (KLY663) was purchased from Klein (Shandong) Biotechnology Co., Ltd.

[0058] N,N-DimethylN,N-Dimethyldecylamide (CM) was purchased from Jiangsu Wannianchang Pharmaceutical Co., Ltd.

[0059] Cyclohexanone was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0060] Methyl oleate was purchased from Shandong Zhouhe Chemical Co., Ltd.

[0061] Silica (DL-620, 300 mesh) was purchased from Jinan Delan Chemical Co., Ltd.

[0062] Kaolin (particle size: 2.34μm) was purchased from Shanghai Guyan Industrial Co., Ltd.

[0063] In the early development of compound herbicides containing glufosinate, it was found that not all herbicides combined with glufosinate achieve better weed control. Furthermore, the weed control effect of compound herbicides is not only related to the active ingredient, but also to the selection and ratio of other components. Through extensive research and experimental verification, the inventors of this application selected the combination of clopyralid isooctyl ester and clopyralid isooctyl ester, which can improve weed control while reducing the amount of glufosinate required. Currently, the commercially available price of glufosinate technical grade is approximately 110,000 RMB / ton, and the commercially available price of clopyralid isooctyl ester technical grade is approximately 70,000 RMB / ton. The combined use of these two can reduce the cost of the technical grade while improving weed control. Furthermore, this application also provides different formulations and optimized formulations for each formulation, offering users more choices.

[0064] Before developing different formulations, the effects of a compound composition of glufosinate and isooctyl clopyralid on weed activity under room temperature pot conditions were studied using the foliar spray method, referring to "Pesticide Bioassay Technology" (edited by Chen Nianchun, published by Beijing Agricultural University Press) and "Agricultural Industry Standards of the People's Republic of China" (Indoor Bioassay Test Guidelines for Pesticides, Herbicides NY / T1155.3-2006, 1155.4-2006). The target weeds tested were goosegrass, crabgrass, lambsquarters, and tuft of grass. The indoor pot test results showed that the combinations of glufosinate and isooctyl clopyralid at different ratios exhibited varying degrees of additive or synergistic effects on the efficacy of the herbicides in indoor pots, without any significant antagonistic effects. In the early room temperature pot experiment, the inventors of this application also tried to combine acetochlor, metolachlor, glyphosate, dicamba, bispyribac-sodium and other compounds with glufosinate-ammonium, but the control effect was not as good as the combination with glufosinate-ammonium and isooctyl clopyralid.

[0065] Based on the results of indoor potted plant tests, the inventors of this application have conducted extensive research and experimental verification on the selection of excipients and dosage form formulations, which can provide users with more choices. The following examples show some preferred formulations and efficacy evaluations of different dosage forms.

[0066] Examples 1 to 9 provide different formulations of glufosinate-ammonium phosphate-clopyralid isooctyl ester oil suspensions. The specific components are shown in Table 1, where "%" represents the mass percentage.

[0067] Table 1

[0068]

[0069] The preparation method of oil suspension is as follows:

[0070] Based on 1 kg of glufosinate-ammonium·clopyralid isooctyl ester oil suspension, weigh each component according to Table 1. First, add methyl oleate to the stirring device, then add each component to methyl oleate, stir at 180 rpm until the original drug is moistened, and then grind through a sand mill to obtain glufosinate-ammonium·clopyralid isooctyl ester oil suspension.

[0071] Referring to GB / T 17980.46-2000 Guidelines for Field Efficacy Testing of Pesticides, the efficacy of glufosinate-ammonium·clopyralid isooctyl ester oil suspension in Examples 1 to 9 for controlling weeds in grape fields was tested.

[0072] The experiment was conducted in Daxin Town, Zhangjiagang City, Jiangsu Province, on a 5-year-old vineyard. The experimental field was flat with sandy loam soil. The pesticide was applied on the afternoon of June 16, 2021, when the grapes were in flowering stage. The row spacing in the vineyard was 1.5 meters. The weeds between the rows included annual weeds (goosegrass, crabgrass, lambsquarters) and perennial weeds (mainly fleabane), all in the 3-4 leaf stage, with plant heights ranging from 15 to 30 cm. The weather on the day of application was cloudy, with a high of 25°C and a low of 16°C, and no wind. There was no rainfall for three days after the application.

[0073] Test area division: Each area is 66 square meters, and areas with weed coverage of 80% or more are selected.

[0074] Application method: Weigh the pesticide according to the dosage per acre in Table 2, and dilute it with 30L of water per acre. After dilution, use a backpack electric sprayer to spray the pesticide on weeds between the grape rows, avoiding spraying the pesticide directly onto the grapes as much as possible. The pesticide dosage for each test plot is shown in Table 2. Each formulation was set up with three replicates, and the average value was calculated. Plots with different reagent treatments were arranged in a completely randomized block design. Two untreated test plots were set up as blank controls, using 10% glufosinate-ammonium aqueous solution and 200g / L clopyralid isooctyl ester emulsifiable concentrate as controls. The dosage of the control pesticides is shown in Table 2. Each control was set up with three replicate plots.

[0075] Investigation methods and efficacy evaluation methods: The control effect of each plot was investigated 14 days and 30 days after application. A three-point sampling method was used, with 0.5 square meters selected at each point. The types and number of weeds were recorded, and the weed control effect was calculated and statistically summarized in Table 2. Annual weeds included goosegrass, crabgrass, and lambsquarters, while perennial weeds included fleabane. The impact on grape growth was also visually assessed.

[0076]

[0077] Table 2

[0078]

[0079] Table 2 shows that, under essentially the same active ingredient dosage, glufosinate-ammonium·clopyralid isooctyl ester oil suspension exhibits higher weed control efficacy in grape fields than glufosinate-ammonium aqueous solution and clopyralid isooctyl ester emulsifiable concentrate. Among these, the glufosinate-ammonium·clopyralid isooctyl ester oil suspension, composed of glufosinate-ammonium, clopyralid isooctyl ester, fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate, bentonite, and methyl oleate, demonstrates even better weed control efficacy.

[0080] Examples 10 to 18 provide different formulations of glufosinate-ammonium phosphate-clopyralid isooctyl ester suspension emulsions. The specific components are shown in Table 3, where "%" represents the mass percentage.

[0081] Table 3

[0082]

[0083]

[0084] The preparation method of the suspension emulsion is as follows:

[0085] Based on 1 kg of glufosinate-ammonium·clopyralid isooctyl ester suspension, weigh each component according to Table 3. First, add cyclohexanone to the stirring device, then add the remaining components to the cyclohexanone. Stir at 180 rpm until uniform, and then grind in a sand mill to obtain glufosinate-ammonium·clopyralid isooctyl ester suspension emulsion.

[0086] Referring to GB / T 17980.46-2000, the guidelines for field efficacy trials of pesticides, the efficacy of glufosinate-ammonium·clopyralid isooctyl ester suspension concentrates (Examples 10-18) in controlling weeds in grape fields was tested. The test methods and calculations of weed control efficacy were the same as for oil suspension concentrates. The pesticide dosage and weed control efficacy results are shown in Table 4.

[0087] Table 4

[0088]

[0089] Table 4 shows that, with similar active ingredient concentrations, glufosinate-ammonium·clopyralid isooctyl ester suspension concentrate is more effective against weeds than glufosinate-ammonium aqueous solution and clopyralid isooctyl ester emulsifiable concentrate. Among them, the glufosinate-ammonium·clopyralid isooctyl ester suspension concentrate, composed of glufosinate-ammonium, clopyralid isooctyl ester, fatty alcohol polyoxyethylene ether, alkylbenzene sulfonate, polycarboxylate, cyclohexanone, and water, exhibits even better weed control.

[0090] Examples 19 to 28 provide emulsifiable powders of glufosinate-ammonium phosphate and clopyralid isooctyl ester with different formulations. The specific components are shown in Table 5, where "%" represents the mass percentage.

[0091] Table 5

[0092]

[0093] The preparation method of emulsifiable powder is as follows:

[0094] Based on 1 kg of glufosinate-ammonium·clopyralid isooctyl ester emulsifiable powder, weigh each component according to Table 5. Mix glufosinate-ammonium and diatomaceous earth evenly, and then perform ultra-fine grinding (98% passing through a 325-mesh sieve) using an air jet mill. Mix and dissolve clopyralid isooctyl ester with N,N-dimethyldecylamide and fatty alcohol polyoxyethylene ether evenly, and then slowly add it to glufosinate-ammonium powder. Stir evenly at a speed of 100-150 rpm to obtain glufosinate-ammonium·clopyralid isooctyl ester emulsifiable powder.

[0095] Referring to GB / T 17980.46-2000, the guidelines for field efficacy trials of pesticides, the efficacy of glufosinate-ammonium·clopyralid isooctyl ester emulsifiable powder (Examples 19-28) in controlling weeds in grape fields was tested. The test methods and calculations of weed control efficacy were based on those for oil suspension formulations. The pesticide dosage and weed control efficacy results are shown in Table 6.

[0096] Table 6

[0097]

[0098]

[0099] Table 6 shows that, with similar active ingredient concentrations, the herbicide-ammonium phosphate·clopyralid isooctyl ester emulsifiable powder is more effective against weeds than ammonium phosphate aqueous solution and clopyralid isooctyl ester emulsifiable concentrate. Among them, the ammonium phosphate·clopyralid isooctyl ester emulsifiable powder, composed of ammonium phosphate, clopyralid isooctyl ester, polycarboxylate, alkyl sulfate, fatty alcohol polyoxyethylene ether, N,N-dimethyldecylamide, silica, and kaolin, exhibits even better herbicidal effect.

[0100] The above embodiments are merely for illustrating the technical concept and features of the present invention. Their purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be used to limit the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A compound herbicide containing glufosinate-ammonium, comprising an active ingredient and excipients, characterized in that: The compound herbicide is an oil suspension, and its formula, by mass percentage, is: 20% glufosinate, 10% isooctyl chlorpyrifos, 15% fatty alcohol polyoxyethylene ether, 5% alkylbenzene sulfonate, 2% bentonite, and 48% methyl oleate.

2. The application of the compound herbicide as described in claim 1 in controlling one or more of barnyard grass, foxtail grass, crabgrass, purslane and fleabane.

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