Herbicidal composition and herbicide suitable for low temperature environment

Abstract

The present application relates to a kind of herbicidal composition suitable for low temperature environment, including herbicidal active ingredient A, herbicidal active ingredient B and pyrrolidone carboxylate;The herbicidal active ingredient A is glufosinate ammonium or glufosinate-P, and the herbicidal active ingredient B is butroxydim.The present application uses pyrrolidone carboxylate (especially sodium pyrrolidone carboxylate), glufosinate ammonium / glufosinate-P and butroxydim in combination, utilizes the synergistic effect of two different action mechanisms of herbicide active ingredient and sodium pyrrolidone carboxylate, and then the herbicidal activity of glufosinate ammonium / glufosinate-P at low temperature is improved to 2 times and more than the prior art.

Description

Technical Field

[0001] The invention belongs to the field of agricultural herbicides, and particularly relates to a herbicidal composition and a herbicide suitable for low-temperature environments. Background Art

[0002] Glufosinate is a non-selective herbicide that inhibits the activity of glutamine synthetase in plants, leading to blocked glutamine synthesis, disrupted nitrogen metabolism, and ammonium ion accumulation, thus disrupting plant metabolism and causing plant death. Glufosinate is chiral and typically produces racemic forms, L- and D-forms. Subsequent studies have shown that L-glufosinate exhibits herbicidal activity, while D-glufosinate lacks herbicidal activity, leading to the designation of L-glufosinate as refined glufosinate. Glufosinate boasts a broad spectrum of activity, high activity, low toxicity, easy degradation in soil, crop safety, minimal drift, good environmental compatibility, and rapid weed control. It can control and rapidly kill over 100 species of annual and perennial broadleaf weeds and grasses, including crabgrass and ryegrass. With the widespread adoption of glufosinate-based transgenic technology, glufosinate has become the second most popular herbicide for genetically modified crops worldwide.

[0003] While glufosinate possesses these advantages and has become the second most effective herbicide after glyphosate, its use still presents numerous challenges. For example, glufosinate's efficacy is susceptible to external factors. Unsuitable temperature, humidity, and light levels can reduce its herbicidal activity, significantly diminishing its effectiveness in certain environments. At low temperatures, glufosinate's ability to penetrate the cuticle and cell membranes is reduced, thus impacting its effectiveness. It is generally recommended that glufosinate be used at temperatures above 15°C. In droughts, plants reduce transpiration by closing their stomata, curling their leaves, and thickening their bark, hindering their absorption and thus their efficacy. Consequently, glufosinate's use is limited in northern China during winter and early spring, when temperatures are low and drought-prone. Even when it can be used, higher dosages are required, increasing costs and potentially leading to weed resistance.

[0004] In summary, it is of great significance to further study the herbicide composition that can make glufosinate-ammonium exert better efficacy at low temperatures. Summary of the Invention

[0005] The present invention aims to overcome the problem in the prior art that the efficacy of glufosinate ammonium is affected by the environment, and provides a compound herbicide composition, which can not only improve the efficacy of glufosinate ammonium under low temperature and drought conditions, but also reduce the amount of glufosinate used and alleviate environmental pressure.

[0006] The basic concept of the technical solution adopted in the present invention is as follows:

[0007] A herbicide composition suitable for low-temperature environments comprises a herbicide active ingredient A, a herbicide active ingredient B and a pyrrolidone carboxylate; the herbicide active ingredient A is glufosinate ammonium or glufosinate-ammonium, and the herbicide active ingredient B is clodinafop-propargyl.

[0008] As an example, the pyrrolidone carboxylate is one of sodium pyrrolidone carboxylate, potassium pyrrolidone carboxylate, copper pyrrolidone carboxylate, zinc pyrrolidone carboxylate or calcium pyrrolidone carboxylate, preferably sodium pyrrolidone carboxylate.

[0009] As an example, the mass ratio of the herbicidal active ingredient A, the herbicidal active ingredient B and sodium pyrrolidonecarboxylate is (0.75-12):(0.1875-3):1.

[0010] As an example, the mass ratio of the herbicidal active ingredient A, the herbicidal active ingredient B and sodium pyrrolidonecarboxylate is (1.5-6): (0.375-1.5):1.

[0011] As an example, the mass ratio of the herbicidal active ingredient A, the herbicidal active ingredient B and sodium pyrrolidonecarboxylate is (0.75-3):(.1875-1.5):1.

[0012] As an example, the mass ratio of the herbicidal active ingredient A, the herbicidal active ingredient B and sodium pyrrolidonecarboxylate is 1.5:0.1875:1, 1.5:0.375:1 or 0.75:0.375:1.

[0013] The present invention also provides a herbicide suitable for low temperature environments, comprising the herbicide composition according to any one of the above items and an adjuvant.

[0014] As an example, the mass content of the herbicidal composition is 1% to 95% of the mass of the preparation, preferably 5% to 90%.

[0015] As an example, the auxiliary agent is a combination of one or more surfactants, carriers or excipients.

[0016] Optionally, the herbicide is in the form of a soluble solution, an aqueous emulsion, a wettable powder, a soluble powder, a soluble granule, a water-dispersible granule, an aqueous suspension, an oil suspension, a microcapsule suspension, a tablet or an effervescent granule.

[0017] As an example, the surfactant is selected from N-carboxyethyl fatty amide salts, perfluoroalkyl carboxylates, alkyl sulfonates, fatty alcohol ether sulfates, alkylbenzene sulfonates, fatty acid ethylene sulfonates, alkyl sulfonates, olefin sulfonates, alkyl phosphate salts, butylnaphthalenesulfonic acid sodium salts, naphthalenesulfonic acid formaldehyde condensate (NNO), fatty alcohol ether phosphate salts, long-chain alkylamines and salts thereof, polyoxyethylene etherified long-chain amines and salts thereof, long-chain quaternary ammonium salts, polyoxyethylene etherified quaternary ammonium salts, N-alkyl-β-aminopropionic acid, N-alkylaminodipropionic acid, N-alkyl betaine, sulfobetaine, 2-undecyl-N-carboxymethyl-N-hydroxyethyl One or more of the following additives: imidazoline, sucrose ester, fatty acid sorbitan, alkyl polyglucoside, phenylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, fatty acid polyoxyethylene ether ester, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, polyethylene glycol oleate, glycerol oleate, polyglycerol oleate, ethoxylated fatty acid sorbitan ester, sorbitan laurate, polyoxyethyl oleate, polysorbitol oleate, tristyrylphenol ethoxylate, ethylene oxide and phenylene oxide block copolymer, EO-PO butyl ether block copolymer, and tallow amine.

[0018] Optionally, the carrier or auxiliary material is selected from one or more of clay, diatomaceous earth, kaolin, activated white clay, bentonite, talc, silica powder, ammonium sulfate, potassium sulfate, soluble starch, leaf wax oil, light calcium, white carbon black, attapulgite, sepiolite, montmorillonite, xanthan gum, gum arabic, pectin, agar, gelatin, alginate, carrageenan, dextrin, polysaccharide derivatives, carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene, polyvinyl pyrrolidone, defoaming agent, mineral oil, soybean oil, methyl oleate, toluene, xylene, solvent oil, N,N-dimethylformamide, cyclohexanone, ethyl acetate, methanol, ethanol, ethylene glycol, polyethylene glycol, propylene glycol, glycerol, isopropanol or water.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] (1) The present invention uses a combination of pyrrolidone carboxylates (especially sodium pyrrolidone carboxylates), glufosinate / glufosinate-ammonium and clodinafop-propargyl, and utilizes two types of herbicide active ingredients with different mechanisms of action and sodium pyrrolidone carboxylates to synergistically enhance the herbicidal activity of glufosinate / glufosinate-ammonium at low temperatures to 2 times or more of that of the prior art.

[0021] (2) Compared with traditional single-agent pesticides, the herbicidal composition of the present invention can significantly reduce the amount of pesticides used. It can achieve the same or even better weed control effect while reducing the amount of pesticides used by 30%. It is not only convenient to use, but also reduces the cost of pesticides for farmers.

[0022] (3) The herbicidal composition described in the application has a wide herbicidal spectrum and can effectively prevent and control Gramineae weeds, broadleaf weeds and sedge weeds such as Eupatorium adenophorum, Digitaria sanguinalis, Poa annua, Conyza canadensis, Sonchus oleraceus, Eclipta prostrata, Amaranthus retroflexus, Portulaca oleracea and Cyperus iria, Cyperus odoratus and the like. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the application will be apparently and completely described below in combination with the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0024] Glufosinate-ammonium is a racemate of L-glufosinate-ammonium and D-glufosinate-ammonium, and each of L-glufosinate-ammonium and D-glufosinate-ammonium accounts for 50%. L-glufosinate-ammonium and D-glufosinate-ammonium are both shown as the content of glufosinate-ammonium in analysis, for example, 45% of D-glufosinate-ammonium in 90% of glufosinate-ammonium does not play a drug effect, and all of the glufosinate-ammonium is L-glufosinate-ammonium playing a drug effect, therefore, the drug effect of the glufosinate-ammonium is twice that of the glufosinate-ammonium when the amounts are equal.

[0025] In the specific case provided in the application, the pyrrolidone carboxylate used is taken as an example of sodium pyrrolidone carboxylate, which is preferentially adopted under the condition of further comprehensive consideration of multiple factors such as the cost of actual production, whether the raw material is easy to obtain and the like, but it does not mean that the application only carries out the test of sodium pyrrolidone carboxylate. The application also carries out the test in the laboratory research stage for potassium pyrrolidone carboxylate, copper pyrrolidone carboxylate, zinc pyrrolidone carboxylate or calcium pyrrolidone carboxylate, and all of them can achieve the basic excellent effect claimed by the application.

[0026] Herbicidal composition case

[0027] The case provides several example formulations of the herbicidal composition of the application suitable for low-temperature environments (see Tables 1-3), and carries out joint toxicity tests.

[0028] (1) Test purpose

[0029] The inhibition effects of the compositions obtained by mixing glufosinate-ammonium, clopyralid and sodium pyrrolidone carboxylate in different proportions on Eupatorium adenophorum, Conyza canadensis and Cyperus iria were determined under the greenhouse potting conditions, and the joint action was evaluated. The relevant results are shown in Tables 1-3.

[0030] (2) Test method

[0031] Using Eleocharis serrata, Erigeron candidum, and Cyperus rotundus as research subjects, 7 / 9 cm diameter plastic pots were filled 4 / 5 of the pot with air-dried fine soil. The pots were placed in a water-filled plastic container and the soil was thoroughly moistened using bottom irrigation. Twenty seeds were evenly sown per pot. When the weeds reached the 2-3 leaf stage, stem and foliage treatments were performed using a spray tower. Each treatment was replicated four times, with a blank control. After the solution dried, the test materials were incubated in a greenhouse under a simulated low-temperature environment with a minimum temperature of 5°C and a maximum temperature of 10°C, a humidity of 75%, and a 14-hour light / 10-hour dark cycle. Twenty days after treatment, weed damage was observed, and the fresh weight of the aboveground portion was weighed. Toxicity to the target weeds was evaluated using the inhibition rate of the target weeds. The synergistic effect of the three-way combination was evaluated using the Golby method for the synergistic effect of the combination as described in the Guidelines for Indoor Pesticide Bioassays.

[0032] Fresh weight inhibition rate % = (blank control fresh weight - treatment fresh weight) / blank control fresh weight × 100

[0033] E0=XYZ / 10000

[0034] In the above formula, E0 is the theoretical fresh weight survival rate after the combination of the herbicide glufosinate ammonium + clodinafop-propargyl + sodium pyrrolidone carboxylate, X is the measured fresh weight survival rate of a single dose of the herbicide glufosinate ammonium, Y is the measured fresh weight survival rate of a single dose of the herbicide clodinafop-propargyl, and Z is the measured fresh weight survival rate of sodium pyrrolidone carboxylate.

[0035] Assume that E is the measured fresh weight survival rate after the combination of glufosinate ammonium + clodinafop-propargyl + sodium pyrrolidone carboxylate. When E0-E≥10, it indicates a synergistic effect; when -10<E0-E<10, it indicates an additive effect; when E0-E≤-10, it indicates an antagonistic effect.

[0036] Table 1 Results of the combined toxicity test on Eleutherodactylus

[0037]

[0038]

[0039] The results in Table 1 show that the herbicidal composition of the present invention has a synergistic effect on Gnaphalium truncatum when the mass ratio of glufosinate-ammonium:clodinafop-butyl:sodium pyrrolidonecarboxylate is in the range of (0.75-12):(0.1875-3):1, and is most obvious when the ratio is 1.5:0.1875:1.

[0040] Table 2 Results of combined toxicity test on Erigeron spp.

[0041]

[0042]

[0043] Table 2 results show that the herbicidal composition of the present application has synergistic effect on the control of P. lindleyi when glufosinate-ammonium: clodinafop-propargi: sodium pyrrolidone carboxylate is in the range of (1.5-6):(0.375-1.5):1, especially most obvious at the ratio of 1.5:0.375:1.

[0044] Table 3 results of joint toxicity test on E. crus-galli

[0045]

[0046]

[0047] Table 3 results show that the herbicidal composition of the present application has synergistic effect on the control of E. crus-galli when glufosinate-ammonium: clodinafop-propargi: sodium pyrrolidone carboxylate is in the range of (0.75-3):(0.1875-1.5):1, especially most obvious at the ratio of 0.75:0.375:1.

[0048] Herbicide cases

[0049] Example 1

[0050] A herbicide in the form of microemulsion is provided, and the raw materials for preparation, by mass percentage, include:

[0051] Glufosinate-ammonium 20%, clodinafop-propargi 5%, sodium pyrrolidone carboxylate 8%, cyclohexanone 5%, fatty alcohol polyoxyethylene ether 20%, antifoaming agent 0.05%, and ethylene glycol 4%, deionized water is added to 100%.

[0052] Example 2

[0053] A herbicide in the form of microemulsion is provided, and the raw materials for preparation, by mass percentage, include:

[0054] Glufosinate-ammonium 10%, clodinafop-propargi 10%, sodium pyrrolidone carboxylate 10%, polyoxyethylene oleate 18%, antifoaming agent 0.05%, polyethylene glycol 3%, deionized water is added to 100%.

[0055] Example 3

[0056] A herbicide in the form of dispersible oil suspension is provided, and the raw materials for preparation, by mass percentage, include:

[0057] Glufosinate-ammonium 12%, clodinafop-propargi 2%, sodium pyrrolidone carboxylate 4%, polyoxyethylene ether quaternary ammonium salt 8%, N-alkyl aminodipropionic acid 7%, antifoaming agent 0.05%, glycerol 5%, methyl oleate is added to 100%.

[0058] Example 4

[0059] A herbicide in the form of dispersible oil suspension is provided, and the raw materials for preparation, by mass percentage, include:

[0060] Glufosinate 15%, clodinafop-propargyl 5%, sodium pyrrolidone carboxylate 5%, phenylphenol polyoxyethylene ether 10%, sulfobetaine 5%, defoamer 0.05%, ethylene glycol 5%, soybean oil added to 100%.

[0061] Example 5

[0062] Provided is a water suspension formulation of a herbicide, wherein the raw materials for preparation include, by mass percentage:

[0063] Glufosinate 6%, clodinafop-propargyl 1%, sodium pyrrolidone carboxylate 1%, alkyl sulfonate 2%, EO-PO butyl ether block copolymer 1%, defoamer 0.05%, propylene glycol 5%, deionized water added to 100%.

[0064] Example 6

[0065] Provided is a water suspension formulation of a herbicide, the preparation raw materials of which include, by mass percentage:

[0066] Glufosinate-ammonium 15%, clodinafop-propargyl 6%, sodium pyrrolidonecarboxylate 9%, alkyl phosphate ester 1.5%, ethylene oxide and phenylene oxide block copolymer 0.5%, defoamer 0.05%, ethylene glycol 5%, deionized water added to 100%.

[0067] Example 7

[0068] Provided is a water-dispersible granule herbicide, wherein the raw materials for its preparation include, by mass percentage:

[0069] Glufosinate 45%, clodinafop-butyl 10%, sodium pyrrolidone carboxylate 15%, olefin sulfonate 2.5%, naphthalenesulfonic acid formaldehyde condensate (NNO) 2.5%, defoamer 0.05%, kaolin added to 100%.

[0070] Example 8

[0071] Provided is a wettable powder herbicide, wherein the raw materials for its preparation include, by mass percentage:

[0072] Glufosinate-ammonium 50%, clodinafop-propargyl 10%, sodium pyrrolidonecarboxylate 10%, butylnaphthalenesulfonic acid sodium salt 4%, EO-PO butyl ether block copolymer 1%, defoamer 0.05%, ammonium sulfate 5%, diatomaceous earth added to 100%.

[0073] Example 9

[0074] Provided is a microemulsion herbicide, wherein the raw materials for preparation include, by mass percentage:

[0075] Glufosinate ammonium 30%, clodinafop-propargyl 10%, sodium pyrrolidone carboxylate 10%, castor oil polyoxyethylene ether 14%, alkyl polyglucoside 16%, defoamer 0.05%, polyethylene glycol 2%, deionized water added to 100%.

[0076] Example 10

[0077] Provided is a water-emulsion herbicide, wherein the raw materials for its preparation include, by mass percentage:

[0078] Glufosinate-ammonium 12%, clodinafop-propargyl 4%, sodium pyrrolidonecarboxylate 3%, cyclohexanone 5%, N-alkyl-β-aminopropionic acid 6%, fatty alcohol ether phosphate 9%, defoamer 0.05%, propylene glycol 5%, deionized water added to 100%.

[0079] Comparative Example 1

[0080] Provided is a herbicide containing glufosinate-ammonium and clodinafop-propargyl, which is a microemulsion. The raw materials for preparation include, by mass percentage, 20% glufosinate-ammonium, 5% clodinafop-propargyl, 5% cyclohexanone, 20% fatty alcohol polyoxyethylene ether, 0.05% defoamer, 4% ethylene glycol, and deionized water added to 100%.

[0081] Comparative Example 2

[0082] Provided is a herbicide containing glufosinate-ammonium and sodium pyrrolidone carboxylate, which is a microemulsion. The raw materials for preparation include, by mass percentage, 20% glufosinate-ammonium, 8% sodium pyrrolidone carboxylate, 5% cyclohexanone, 20% fatty alcohol polyoxyethylene ether, 0.05% defoamer, 4% ethylene glycol, and deionized water added to 100%.

[0083] Comparative Example 3

[0084] Provided is a herbicide containing clodinafop-propargyl and sodium pyrrolidone carboxylate, which is a microemulsion. The preparation raw materials include, by mass percentage, 5% clodinafop-propargyl, 8% sodium pyrrolidone carboxylate, 5% cyclohexanone, 20% fatty alcohol polyoxyethylene ether, 0.05% defoamer, 4% ethylene glycol, and deionized water added to 100%.

[0085] Comparative Example 4

[0086] Provided is a herbicide containing glufosinate-ammonium and clodinafop-propargyl, which is a microemulsion. The raw materials for preparation include, by mass percentage, 30% of glufosinate-ammonium, 10% of clodinafop-propargyl, 14% of castor oil polyoxyethylene ether, 16% of alkyl polyglucoside, 0.05% of defoamer, 2% of polyethylene glycol, and deionized water added to 100%.

[0087] Comparative Example 5

[0088] Provided is a herbicide containing refined glufosinate ammonium and sodium pyrrolidone carboxylate, which is a microemulsion. The preparation raw materials include, by mass percentage, 30% refined glufosinate ammonium, 10% sodium pyrrolidone carboxylate, 14% castor oil polyoxyethylene ether, 16% alkyl polyglucoside, 0.05% defoamer, 2% polyethylene glycol, and deionized water added to 100%.

[0089] Comparative Example 6

[0090] Provided is a herbicide containing clodinafop-propargyl and sodium pyrrolidone carboxylate, which is a microemulsion. The preparation raw materials include, by mass percentage, 10% clodinafop-propargyl, 10% sodium pyrrolidone carboxylate, 14% castor oil polyoxyethylene ether, 16% alkyl polyglucoside, 0.05% defoamer, 2% polyethylene glycol, and deionized water added to 100%.

[0091] Field efficacy trials

[0092] (1) Experimental environment: Jiande City experimental base, early spring low temperature (average daily minimum 3.6℃, ​​maximum 13.1℃) conditions, the weeds in the experimental site are mainly bluegrass, coleus, and cyperus, with a small amount of cleavers and Persian speedwells.

[0093] (2) Test agent: the preparations provided in herbicide Examples 1 to 10.

[0094] (3) Control agents: the formulations provided in Comparative Examples 1 to 6, 200 g / L glufosinate aqueous solution (commercially available), 10% refined glufosinate aqueous solution (commercially available), 20% acetyl glufosinate microemulsion (commercially available), and 20% propyne refined glufosinate suspension concentrate. "%" represents the active ingredient content of the corresponding agent.

[0095] (4) Test method: Accurately weigh the various pesticides according to the area of ​​the test plot, dilute them with water, and evenly spray them using a backpack sprayer. Use a fan-shaped nozzle designed for herbicides. When spraying, be sure to evenly spray the pesticide solution into the test plot, avoiding any overlap or omission.

[0096] (5) Results: Weed mortality was observed 35 days after application, and the herbicidal activity of each treatment was compared. The efficacy results are shown in Tables 4 and 5.

[0097] In Tables 4 and 5, the letters af after the protective effect are the labels of significance analysis.

[0098] Table 4 Fresh weight control effect on field weeds

[0099]

[0100] The results in Table 4 show that the low-temperature herbicidal composition of the present invention significantly improves the efficacy of glufosinate-ammonium at low temperatures compared to conventional single-dose formulations. With the same dosage of the active ingredient, its efficacy is twice or more that of a single-dose formulation, and even outperforms single-dose formulations with higher dosages. Compared to commercially available compound formulations, it offers superior efficacy and a wider spectrum of weed control.

[0101] Table 5 Fresh weight control effect on field weeds

[0102]

[0103] The results in Table 5 show that the conclusions are consistent with those in Table 4.

Claims

1. A herbicidal composition suitable for low temperature environments, characterized in that: The invention comprises an herbicidal active ingredient A, an herbicidal active ingredient B and sodium pyrrolidonecarboxylate; the herbicidal active ingredient A is glufosinate-ammonium or glufosinate-ammonium, and the herbicidal active ingredient B is clodinafop-propargyl; the mass ratio of the herbicidal active ingredient A, the herbicidal active ingredient B and sodium pyrrolidonecarboxylate is 0.75:0.375:1, 1.5:0.1875:1, 1.5:0.375:1, 1.5:0.75:1, 3:0.1875:1, 3:0.375:1, 3:0.75:1, 3:1.5:1, 6:0.375:1, 6:0.75:1, 6:1.5:1, 12:0.75:1, 12:1.5:1 or 12:3:

1.

2. A herbicide suitable for low temperature environments, comprising the herbicidal composition according to claim 1 and an adjuvant.

3. The herbicide suitable for low temperature environment according to claim 2, characterized in that: The mass content of the herbicidal composition is 1% to 95% of the mass of the herbicide.

4. The herbicide suitable for low temperature environment according to claim 3, characterized in that: The mass content of the herbicidal composition is 5% to 90% of the mass of the herbicide.

5. The herbicide suitable for low temperature environment according to claim 2, characterized in that: The auxiliary agent is a combination of one or more surfactants and carriers.

6. The herbicide suitable for low temperature environment according to claim 2, characterized in that: The herbicide is in the form of a soluble agent, an aqueous emulsion, a wettable powder, a soluble powder, a soluble granule, a water-dispersible granule, an aqueous suspension, an oil suspension, a microcapsule suspension, a tablet or an effervescent granule.

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