Railway herbicide composition and application thereof

Abstract

The invention relates to a railway herbicide composition and application thereof, and the railway herbicide composition is prepared from the following components in parts by weight: 60 to 120 parts of ammonium glyphosate or isopropylamine salt, 15 to 60 parts of hexazinone, and 15 to 45 parts of 4-amino-3, 5-dichloro-6-fluoro-pyridine-2-oxyacetic acid derivative or quaternary ammonium salt of the 4-amino-3, 5-dichloro-6-fluoro-pyridine-2-oxyacetic acid derivative. All the components of the railway herbicide disclosed by the invention are combined in a certain ratio range to show a remarkable synergistic interaction effect, so that the pesticide cost is greatly reduced on the whole.

Description

TECHNICAL FIELD

[0001] The present application relates to a railway herbicide composition and its application. BACKGROUND

[0002] With the continuous development of railway transportation, the maintenance and management of railway subgrade become particularly important. Among them, weeding is an important task to keep the subgrade clean and ensure the safe operation of trains.

[0003] Railway subgrade weeding is to maintain the reliability and safety of the line. The growth of grass and trees not only affects the stability of the subgrade, but also blocks the view of signal equipment, increasing the workload of maintenance and cleaning. In addition, if the vehicle encounters a subgrade full of grass during driving, not only will it affect the running speed of the train, but also will cause damage to the power system of the train. Therefore, timely and effective weeding is crucial for railway operation.

[0004] The methods of railway weeding are: physical weeding, which is a method of using mechanical equipment or manual labor to weed. Common physical weeding methods include lawn mowers, weeding hoes, etc. This method is suitable for areas where grass and trees grow more densely, and can quickly cut or remove grass and trees. However, physical weeding requires manual operation, and for large areas of railway subgrade, the workload is large. Chemical weeding is a method of spraying or scattering chemical herbicides on grass and trees to inhibit or kill them through the action of drugs. This method can be carried out in a larger range and has good effect. With the progress of science and technology and the continuous introduction of high-efficiency, low-toxicity and low-residue chemical herbicide varieties, more and more chemical herbicide varieties can be applied to railway weeding, and people pay more attention to and rely on railway chemical weeding. However, the thoroughness, persistence and safety to surrounding crops of chemical weeding are the key problems of railway weeding.

[0005] At present, the single component preparation or two component combination of glyphosate, glufosinate-ammonium, hexazinone or mesosulfuron-methyl is usually used for weed control on railway. Glyphosate or glufosinate-ammonium belongs to organic phosphorus herbicide, which is passivated after entering the soil, has a short persistence period and does not have the effect of closing seed germination, so that the railway weed control work has to be repeated, which is time-consuming and labor-intensive, and the dosage of glyphosate or glufosinate-ammonium per mu is also increasing. After that, the single component preparation represented by hexazinone and mesosulfuron-methyl is used, the weed control effect is improved, and the number of spraying construction per year is reduced. However, the single component preparation has defects and limitations in some aspects due to the complex types of weeds on the railway, the mixed growth of annual and perennial weeds, and the coexistence of grasses and broadleaf weeds. Moreover, with the long-term use of these single components or two component combinations, the problem of weed resistance is becoming more and more serious, and the effect is getting worse. The common response of the spraying workers is to increase the dosage and use frequency, which not only increases the total amount of herbicide and the cost of herbicide, but also has an important impact on the safety of surrounding green plants and crops, and does not fundamentally solve the problem. Moreover, the frequent rainfall in spring and summer will directly affect the absorption and efficacy of the herbicide, and the railway department is more worried that the rainwater will cause the herbicide to invade the farmland beside the railway, resulting in pesticide damage accidents, which has become a major problem that has been bothering the railway department.

[0006] Therefore, it is necessary to develop a herbicide combination scheme that can solve the problems of resistance, killing speed, high dosage, short persistence period, and impact on surrounding crops and environment of the current railway herbicide. SUMMARY

[0007] In order to solve the above technical problems, the present application provides a railway herbicide composition and its application. The herbicide composition of the present application is used for the prevention and treatment of harmful vegetation along the railway.

[0008] The present application uses glyphosate or its salt, hexazinone and 4-amino-3, 5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt with different structural types and action mechanisms in combination, and it is found that at a specific ratio, not only there is no drug resistance or other side effects, but also there is a significant synergistic effect, which can significantly improve the prevention and treatment effect on annual and perennial grass weeds and broadleaf weeds, shrubs, trees and the like, especially on the difficult-to-prevent shrubs, trees, vines, reeds and resistant weeds along the railway, etc. At the same time, the herbicidal spectrum and the killing speed are expanded.

[0009] In addition, on the basis of the above-mentioned combination, further adding 4-trifluoromethyl benzyl caffeine succinate dioctyl sulfonate ammonium salt can not only reduce the dosage of the herbicide composition, but also improve the weed killing speed, increase the persistence period of weed control. In the case of reasonable application, it is also beneficial to reduce the residual amount of hexazinone in surface runoff water, and increase the safety of the combination to surrounding crops. After application, the surface runoff test shows that the effective components contained in the water flowing into the crop field along the railway are safe to corn and wheat, and have low toxicity to aquatic organisms and warm-blooded animals.

[0010] The herbicide composition of the present application successfully solves the problems of comprehensive management of weeds along the railway, that is, the prevention and control effect, safety to crops along the railway and safety to aquatic organisms, and the problems of quick-acting and long-acting of the herbicide.

[0011] The active ingredients of the herbicide composition of the present application are: glyphosate ammonium salt or isopropylamine salt, hexazinone, 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt, and optionally a synergistic additive containing 4-trifluoromethyl benzyl caffeine succinate dioctyl sulfonate ammonium salt.

[0012] One of the advantages of the present application is low toxicity, broad spectrum, high efficiency, and can prevent and control weeds with serious resistance to existing railway herbicides;

[0013] The second advantage of the present application is environmentally friendly water-soluble, friendly to the environment along the railway and application;

[0014] The third advantage of the present application is that it has the advantages of quick-acting and long-acting, and the herbicidal persistence period is up to 90 days;

[0015] The fourth advantage of the present application is that it is relatively safe to surrounding crops along the railway after reasonable application.

[0016] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0017] A railway herbicide composition, wherein the railway herbicide composition comprises, by weight fraction, 60-120 parts of glyphosate ammonium salt or isopropylamine salt, 15-60 parts of hexazinone, and 15-45 parts of 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt.

[0018] Preferably, the railway herbicide composition comprises, by weight fraction, 60-120 parts of glyphosate ammonium salt or isopropylamine salt, 37.5-60 parts of hexazinone, and 15-45 parts of 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt. More preferably, the railway herbicide composition comprises, by weight fraction, 90 parts of glyphosate ammonium salt or isopropylamine salt, 37.5 parts of hexazinone, and 30 parts of 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt.

[0019] Preferably, the structural formula of the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative is shown in general formula (I):

[0020]

[0021] in:

[0022] X represents an oxygen or sulfur atom; n = an integer; R represents H or an alkyl group; R 1 R 2 Selected independently from C 1-6 alkyl, C 1-6 alkoxy, C 2-6 The alkenyl and aryl groups.

[0023] Preferably, in formula (Ⅰ), X represents an oxygen atom;

[0024] Preferably, in formula (Ⅰ), n is an integer from 1 to 6, more preferably an integer from 1 to 4;

[0025] Preferably, in formula (Ⅰ), R represents H or a C1-6 alkyl group, more preferably H;

[0026] Preferably, in formula (Ⅰ), R 1 and R 2 Alkyl groups independently selected from H and C1-C4 (e.g., methyl, ethyl, propyl, butyl, isopropyl, isobutyl, etc.);

[0027] Preferably, in formula (Ⅰ), X represents an oxygen atom; n is an integer from 1 to 4; R represents H; R 1 and R 2 It is independently selected from methyl, ethyl, propyl, and butyl.

[0028] Preferably, the quaternary ammonium salt of the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative has the structural formula shown in general formula (II):

[0029]

[0030] Where X represents an oxygen or sulfur atom; n = an integer; R represents H or an alkyl group; R 1 R 2 Selected independently from C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl and aryl groups; It represents Cl-, Br-, F-, I-, acetate, acetylsalicylate, citrate, salicylate, p-toluenesulfonate, hydrogen sulfate, or other acid radicals.

[0031] Preferably, in formula (II), X represents an oxygen atom;

[0032] Preferably, in formula (II), n is an integer from 1 to 6, more preferably an integer from 1 to 4;

[0033] Preferably, in formula (II), R represents H or C. 1-6 Alkyl groups, more preferably representing H;

[0034] Preferably, in formula (II), R 1 and R 2 Alkyl groups independently selected from H and C1-C4 (e.g., methyl, ethyl, propyl, butyl, isopropyl, isobutyl, etc.);

[0035] Preferably, in formula (II), X represents an oxygen atom; n is an integer from 1 to 4; R represents H; R 1 and R 2 It is independently selected from methyl, ethyl, propyl, and butyl.

[0036] Preferably, in formula (II), Represents Cl-, Br-, F-, I-, acetate, acetylsalicylate, citrate, or salicylate;

[0037] Preferably, in formula (II), X represents an oxygen atom; n is an integer from 1 to 4; R represents H; R 1 and R 2 Independently selected from methyl, ethyl, propyl, and butyl; It represents Cl-.

[0038] Preferably, the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt is selected from...

[0039]

[0040]

[0041]

[0042]

[0043] Preferably, the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt is

[0044]

[0045] The structure and preparation method of the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt are described in Chinese patent application CN 118026924 A.

[0046] Preferably, the herbicide composition further includes 10-40 parts by weight of a synergistic adjuvant.

[0047] Preferably, the herbicide composition further includes 20-30 parts by weight of a synergistic adjuvant.

[0048] Preferably, the synergistic agent, by weight percentage, comprises the following components:

[0049]

[0050]

[0051] The quaternary ammonium salt of 4-trifluoromethylbenzyl caffeine succinate dioctyl sulfonate has the following structural formula:

[0052]

[0053] The synergistic agent and its preparation method are described in Chinese patent application CN119143762A.

[0054] The herbicide composition of the present invention can be prepared by direct mixing. The herbicide composition of the present invention can be used directly after dilution; for example, the above-mentioned herbicide composition can be added to water to prepare an aqueous solution for direct spraying. The mass ratio of the above-mentioned herbicide composition to water is 1:60-80.

[0055] On the other hand, the present invention provides an application of a railway herbicide composition in the chemical weeding of railway subgrade and shoulders.

[0056] The beneficial effects of this invention are as follows:

[0057] The railway herbicide composition provided by this invention belongs to the broad-spectrum, systemic, non-selective compound herbicide class, possessing advantages such as good water solubility, high efficiency and low toxicity, broad-spectrum non-selective action, rapid onset of action, and long-lasting effect. The use of synergistic adjuvants, including 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivatives or their quaternary ammonium salts and novel 4-trifluoromethylbenzyl caffeine succinate dioctyl sulfonate quaternary ammonium salt, enhances the herbicide's spreadability, penetration, adhesion, and resistance to rain washout on weed stems and leaves, improving efficacy while reducing phytotoxicity. It further accelerates the herbicide's onset of action and improves its utilization efficiency. Under appropriate application conditions, runoff experiments after application show that the active ingredients in the water flowing into crop fields along the railway line are safe for corn and wheat, and these herbicide components have low toxicity to aquatic organisms and warm-blooded animals. The herbicide composition of the present invention successfully solves the problem of integrated management of weeds along railway lines: the control effect of herbicides, their safety to crops and aquatic organisms along the line, and the rapid or sustained effects of the herbicide. It is of great significance for the efficient and safe control of railway weeds.

[0058] Compared with the prior art, the present invention has the following advantages:

[0059] (1) Significant synergistic effect. The components of this invention exhibit a significant synergistic effect when combined within a certain ratio range, which greatly reduces the overall cost of medication.

[0060] (2) Significantly improved speed and duration of action. The optimal formulation of this invention shows that the control effect on railway weeds is significantly improved 3 days, 7 days and 90 days after application, which improves the speed of efficacy and extends the duration of action to more than 90 days. This is an effect that is difficult to achieve by the individual components themselves. It can reduce the number of applications, save time and labor and improve economic benefits.

[0061] (3) The formulation of this invention expands the control spectrum and effectively solves the problem of railway weeds developing resistance to conventional herbicides such as glyphosate and glufosinate. The inventors unexpectedly discovered that it effectively controls railway weeds that are difficult to control with conventional herbicides, such as goosegrass, fleabane, horsetail, wild oats, reeds, and cogongrass.

[0062] (4) The present invention incorporates a specific combination of synergistic adjuvants, which significantly improves the extensibility, penetration, adhesion and resistance to rain washout of the herbicide on the stems and leaves of weeds, significantly increases the speed at which the herbicide takes effect (the effect is obvious in 3 days), reduces the loss of the herbicide, and significantly improves the utilization efficiency of the herbicide. At the same time, it solves the problem of herbicide damage to surrounding crops caused by railway weeding.

[0063] (5) The formula of this invention selects two effective ingredients with high content and excellent water solubility, which can be directly dissolved in water and used to greatly reduce the transportation cost of the product and the difficulty of application in special sections of railway, thereby saving a significant amount of comprehensive treatment costs. Detailed Implementation

[0064] The present invention will be further illustrated below with reference to specific embodiments, but these embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field. Unless otherwise specified, all reagents and materials used in the present invention are commercially available.

[0065] In the following examples, the preparation method of 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoethyl acetate quaternary ammonium salt is described in specific examples 1-3 of Chinese patent application CN 118026924 A.

[0066] The structure and 1H NMR spectrum of this substance are characterized as follows:

[0067]

[0068] In the following embodiments, the synergistic agent, by weight percentage, consists of the following components:

[0069]

[0070]

[0071] The structural formula of 4-trifluoromethylbenzyl caffeine succinate dioctyl sulfonate quaternary ammonium salt is as follows:

[0072]

[0073] For the preparation method of the synergistic agent, please refer to Examples 1-2 of Chinese Patent Application CN119143762A.

[0074] The characterization data of 4-trifluoromethylbenzylcaffeine dioctyl succinate quaternary ammonium salt are as follows:

[0075] 1H NMR spectrum:

[0076] ¹H NMR (400MHz, DMSO-d6) δ (ppm): 8.94 (s, ¹H), 7.52 (d, 2H), 7.26 (d, 2H), 5.93 (s, 2H), 3.93–3.85 (m, 4H), 3.73 (s, 3H), 3.56 (t, ¹H), 3.37 (s, 3H), 3.31 (s, 3H), 2.94–2.77 (m, 2H), 1.50 (br, 2H), 1.24 (br, 16H), 0.83–0.81 (m, 12H). Mass spectrometry: HRMS (ESI) C36 H54 F3 N4 O9S+[M+H]+ Theoretical value: 775.3558, Measured value: 775.3554

[0077] In the following examples, 98% cycloazinone technical grade was purchased from Anhui Huaxing Chemical Co., Ltd.

[0078] 98% glyphosate ammonium salt was purchased from Nantong Jiangshan Agrochemical Co., Ltd.

[0079] The 20% glufosinate-ammonium salt solution was purchased from Sichuan Lier Chemical Co., Ltd.

[0080] 95% glyphosate ammonium salt was purchased from Nantong Jiangshan Agrochemical Co., Ltd.

[0081] 25% cycloazinone soluble concentrate was purchased from Anhui Huaxing Chemical Co., Ltd.

[0082] Example 1: Indoor Formula Screening

[0083] This embodiment aims to screen for cost-effective formulation combinations and investigate whether the synergistic effect of mixing two or three herbicide active ingredients in different proportions is present. Typical resistant broadleaf weeds found in railway environments, such as morning glory and goosegrass (a type of grass), were selected as test targets, and relevant indoor experiments were conducted. The specific experimental implementation methods are as follows:

[0084] Test reagents: Using an electronic balance (sensitivity 0.1 mg), weigh out 0.1202 g, 0.3004 g, and 0.4806 g of 98% cycloazinone technical grade, respectively. Dissolve each grade in 5 ml of acetone, then dilute to 500 ml with a 0.1% (v / v) Tween-80 aqueous solution. Prepare cycloazinone solutions of 150 g / ml each. 2 375g.ai / hm 2 600g.ai / hm 2Solutions: Weigh out 0.4806 g, 0.7209 g, and 0.9612 g of 98% glyphosate ammonium salt sequentially, dissolve each in 50 ml of deionized water, and then dilute to 500 ml with a 0.1% Tween-80 aqueous solution. Prepare solutions of 600 g.ai / hm² and 900 g.ai / hm² of glyphosate ammonium salt sequentially. 2 1200g.ai / hm 2 Solution: Weigh out 0.1202 g, 0.2403 g, and 0.3605 g of 98% ethyl 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl acetate technical grade, respectively, and dissolve each in 50 ml of deionized water. Then dilute to 500 ml with deionized water to prepare 150 g of ethyl 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl acetate quaternary ammonium salt. 2 300g.ai / hm 2 450g.ai / hm 2 The dosage of the active ingredient mentioned above is calculated based on the amount of active ingredient required to spray 2 ml of the drug solution onto the soil area of ​​a culture pot with a diameter of 20 cm. According to the above single-agent preparation method or using the above single-agent solution as the stock solution for the treatment group, a series of ratios were set according to the purpose of mixing. The following treatments were set up (the blank control did not add any active ingredient, i.e., only 5 ml of acetone was added and diluted to 500 ml with 0.1% Tween-80 aqueous solution, which served as the blank control stock solution). Details of each treatment are shown in Table 1 below.

[0085] Table 1: Dosage and Preparation Table for Each Treatment

[0086]

[0087]

[0088] Experimental soil: Neutral pH, well-drained non-cultivated topsoil was used, naturally air-dried, sieved, and quantitatively filled to 4 / 5 of the culture pot.

[0089] Culture of test materials: Seeds of the target weeds (Fleabane and Goosegrass) produced from railway sites were stratified to promote germination. After the seeds showed signs of sprouting, they were sown. The pretreated test seeds were evenly sown in soil at a rate of 12 seeds per pot in the culture pot, covered with 0.5-1.0 cm of soil, and placed in a tray containing water. The water was allowed to gradually seep in from the bottom. After the water reached the soil surface, the pot was transferred to a culture room for further cultivation.

[0090] Chemical treatment: When the weed seedlings have grown to the 2-3 leaf stage, the stems and leaves are sprayed using a Potter spray tower. 2 ml of the solution is sprayed per pot, and each treatment is repeated 4 times. A blank control is set up with no active ingredient in the chemical. After treatment, the test materials are placed in a culture room for cultivation.

[0091] Investigation Methods: After treatment, the growth status of the target plants was observed and recorded regularly, and the symptoms of damage to weed seedlings were recorded. Twenty-one days after treatment, the activity of the herbicide was investigated and recorded using the growth inhibition method, and the fresh weight of the weed seedlings was weighed. Data Statistical Methods: Based on the survey data, the fresh weight control efficacy (fresh weight inhibition rate) of each treatment was calculated according to the formula, expressed as a percentage (%).

[0092] Reference absolute value method: Actual fresh weight control efficacy E (%) = (Fresh weight of weed seedlings in the control area - Fresh weight of weed seedlings in the treatment area) / Fresh weight of weed seedlings in the control area × 100%

[0093] Referring to the Colby method: Taking the mixture of three agents A, B, and C as an example, the theoretical fresh weight inhibition effect of the mixture in the above proportions is calculated by the formula: E0(%) = A + B + C + ... + N = Inhibition effect of agent 1 + Inhibition effect of agent 2 + Inhibition effect of agent 3 + ... + Inhibition effect of agent n.

[0094] In this table, A, B, C, ..., N represent the actual fresh weight inhibitory effects of single agents (e.g., agent 1, agent 2, agent 3, ..., agent N), and n represents the number of mixed agents. E-E0 > 10% indicates synergistic effect; E-E0 < -10% indicates antagonistic effect; and E-E0 values ​​between ±10% indicate additive effect. The treatment results are shown in Table 2 below.

[0095] Table 2. Statistical table of fresh weight inhibition rate data.

[0096]

[0097]

[0098]

[0099] The statistical results in Table 2 show that when cycloazinone, glyphosate ammonium salt, and 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoethyl ethyl quaternary ammonium salt are used in combination, all combinations of these three components show synergistic or additive effects on both *Eleusine indica* (a grass) and *Erigeron brevis* (a broadleaf fleabane). Specifically, for *Eleusine indica*, seven groups (treatments 10, 12, 22, and 25–28) showed synergistic effects, while the rest showed additive effects. For *Erigeron brevis*, seven groups (treatments 10, 12, 25–28, and 35) showed synergistic effects, while the rest showed additive effects. It should be noted that the synergistic effect of the ternary combination formulation is greater than that of the binary combination formulation, and the E-E0 values ​​of the dosage ratio of treatment 26 (A2+B2+C2) are significantly higher than those of other combinations, namely cycloazinone, glyphosate ammonium salt, and 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoethyl acetate quaternary ammonium salt 375+900+300 (gai / hm) 2 The combined treatment showed the most significant synergistic effect on the control efficacy of goosegrass and fleabane, with E-E0 values ​​of 16.2% and 16.3%, respectively.

[0100] Example 2-8 Field Efficacy Trials

[0101] To verify the field weeding effect of the synergistic effect of the ternary components in the above embodiments, we set up the experimental schemes of Examples 2-8, as detailed in Table 3.

[0102] Test area: The test subjects were selected as the main resistant weeds in railway fields, such as goosegrass, fleabane, horsetail, wild oats, reeds, and redbud, which are difficult to control effectively with conventional herbicides. The application time was spring 2024 (mid-May), and the test site was the subgrade and shoulders of the railway line in the vicinity of the Zhongshan Engineering Section under the Guangzhou Railway Bureau of China Railway.

[0103] Examples 2-8 are herbicide formulations containing two or more of the following active ingredients: commercially available 95% glyphosate ammonium salt, commercially available 25% cyclophosphamide soluble concentrate, and 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl ethyl quaternary ammonium salt, and synergistic adjuvants. The formulations of each active ingredient are different. Comparative Examples 1-3 are single-ingredient formulations containing one of the three active ingredients: 95% glyphosate ammonium salt, 25% cyclophosphamide soluble concentrate, and 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl ethyl quaternary ammonium salt. Comparative Example 4 is a single-ingredient formulation of commercially available 20% glufosinate. Treatments without any of the above active ingredients serve as blank controls.

[0104] The method for preparing the railway herbicide formulations in Examples 2-8 is as follows: weigh the ingredients according to the proportions in Table 3, then mix and dissolve them in a measured amount of water to prepare an aqueous solution for spraying.

[0105] Comparative Examples 1-4 are commercially available formulations of the above three components and glyphosate, namely, commercially available 25% cycloazinone soluble concentrate, 95% glyphosate ammonium salt soluble granules, 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoethyl acetate quaternary ammonium salt, and commercially available 20% glufosinate ammonium salt (see Table 4).

[0106] Table 3: Weight parts of each component in specific herbicide formulation examples

[0107]

[0108] Note: The data in parentheses are cycloazinone (100% concentration).

[0109] Table 4: Components corresponding to each comparative example

[0110]

[0111] Each treatment in each embodiment and comparative example was repeated four times, with 30m samples taken from each cell. 2 The treatments were arranged in a randomized block design. Except for the different component ratios applied according to the above scheme, all other conditions in each treatment area were identical; the growth status of the weeds to be treated was basically the same within each area. Application was carried out by railway workers using shoulder-mounted sprayers (model: Wanhuilin 3WBD-20), spraying every 30m². 2 The effective ingredient dosage (referring to the actual dosage of the corresponding component of cyclomethazine, glyphosate ammonium salt, or ethyl 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetate quaternary ammonium salt) was 4.10 g (equivalent to 90 g / mu of effective ingredient). To ensure uniform spraying and control the single variable in the experiment, each treatment was applied using a 250-fold dilution of the total effective ingredient, i.e., per 30 m² 2 The amount of diluted solution used was 2.02 kg. Observations and measurements were conducted three times, 7 days, 30 days, and 90 days after the application of the railway herbicide. The weed control rate of the treated area was investigated and recorded. During the investigation, five random samples were taken from each plot, with a sample area of ​​5 m². 2 The weed control effects of each embodiment and comparative example are detailed in Table 3. The weed control effects in the table are calculated based on the control effect per plant area. That is, weed control rate % = (number of normally growing weeds in the blank control area - number of surviving weeds in the treatment area) / number of normally growing weeds in the blank control area × 100%.

[0112]

[0113] As shown in Table 5 above, comparing Examples 2-8 reveals that Examples 3, 4, 5, 6, 7, and 8 all achieved ideal weed control efficacy (over 90%) within approximately 30 days. In terms of weed-killing speed, Examples 5, 7, and 8 were the best, with Example 8 being the most effective. Regarding the duration of effect, Example 8 was significantly superior to the other examples. Comparing Examples 7 and 8, the active ingredients and proportions of the herbicides were the same. However, after adding a certain amount of adjuvants, Example 8 showed significantly better weed-killing speed and duration of effect than Example 7. Example 8, with its optimal synergistic ratio of the three components, exhibited superior rapid and lasting effects compared to other examples due to the addition of adjuvants. Comparing Examples 2-8 with Comparative Examples 1-4 shows that compared to individual agents, the weed control rate of the compound mixture was significantly improved, demonstrating a synergistic or additive effect.

[0114] As can be seen from Examples 2-8 and Comparative Examples 1-4, the weed control efficacy of each single-component formulation is generally average, with certain defects and limitations. For example, the 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoethyl acetate quaternary ammonium salt has a moderate effect on grass weeds and is relatively selective. However, unusually, the common non-selective herbicide components glyphosate (Comparative Example 2) and glufosinate (Comparative Example 4) have weak control efficacy at all stages, especially after 30 days, and are far from achieving their expected effects, with significant weed resistance problems. However, when the three components are combined, the control efficacy at all stages increases significantly and reaches the optimal level under appropriate ratios.

[0115] Based on the effects of the above embodiments, the three active ingredients involved in this invention have complementary and synergistic effects. Reducing one or two of the ingredients will significantly decrease the weed control efficacy. Only when the three ingredients are combined simultaneously in an appropriate ratio can the overall weed control effect be optimal. When the ratio of the three active ingredients is optimal, the synergistic adjuvant of this invention significantly improves both the weeding speed and the residual effect of the herbicide combination.

[0116] Example 9

[0117] To further illustrate the promoting effect of synergistic adjuvants on the efficacy and safety of the above-mentioned preferred railway herbicide formulations, a related field application test was set up. Test location: The subgrade and shoulders of the railway line near the Zhongshan Engineering Section under the Guangzhou Railway Bureau of China Railway. The test section is located directly below a section of farmland (paddy field) where herbicide damage has historically been frequent. Test time: Mid-July 2024. The test formulation was based on the formulation combination corresponding to the most preferred embodiment (Example 7): 150 parts of 25% cyclomethazine soluble concentrate (37.5% concentration), 94.7 parts of 95% glyphosate triethylamine salt, 31.6 parts of 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoethyl acetate quaternary ammonium salt, 30 parts of a specific synergistic adjuvant, and the dosage corresponding to the optimal treatment (treatment 26) in Example 1 of the indoor test. Five treatments were set up with different amounts of the specific synergistic adjuvant added. Treatment 1: Railway herbicide combination formulation: 150 parts of 25% cyclophosphamide soluble concentrate, 94.7 parts of 95% glyphosate triethylamine salt, 31.6 parts of 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl acetate quaternary ammonium salt + 20 parts of specific synergistic adjuvant; Treatment 2: Railway herbicide combination formulation: 150 parts of 25% cyclophosphamide soluble concentrate, 94.7 parts of 95% glyphosate triethylamine salt, 31.6 parts of 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl acetate quaternary ammonium salt + 30 parts of specific synergistic adjuvant; Treatment 3: Railway herbicide combination formulation: 150 parts of 25% cyclophosphamide soluble concentrate... Treatment 1: 94.7 parts of 95% glyphosate triethylamine salt, 31.6 parts of 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl ethyl quaternary ammonium salt + 40 parts of specific synergistic adjuvant; Treatment 4: Railway herbicide combination formulation: 150 parts of 25% cycloazinone soluble concentrate, 94.7 parts of 95% glyphosate triethylamine salt, 31.6 parts of 95% 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxyethyl ethyl quaternary ammonium salt + without specific synergistic adjuvant; Conventional control treatment CK: Conventional railway non-cultivated land herbicide (10% methamidosulfuron suspension); An equal volume of water without any of the above active ingredients was used as a blank control. The above 25% cycloazinone soluble concentrate and 95% glyphosate ammonium salt granules were purchased from the market. The 10% mefensulfuron suspension used in the standard control treatment CK was purchased from the market.

[0118] Each treatment consisted of four road sections, each 1 km long with a shoulder width of approximately 1 m, serving as four replicates arranged in a randomized block design. Aside from applying different component ratios according to the above scheme, other conditions in each treatment area were basically the same, and the weed population was largely similar. Application was carried out by railway workers using shoulder-mounted sprayers (model: Wanhuilin 3WBD-20). The total effective ingredient (total amount of the three effective ingredients—glyphosate, glyphosate ammonium salt, and 2'-N,N-diethyl-4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoethyl acetate quaternary ammonium salt, or total effective ingredient amount of mefensulfuron-methyl) was applied at a rate of 90 g per acre (equivalent to 1350 g.ai / hm²). 2 To ensure uniform spraying and control the single variable in the experiment, each treatment was carried out by diluting the total effective ingredients with water at a ratio of 500:1, i.e., the amount of diluted solution sprayed per acre was 45 kg. The synergistic adjuvant was added when diluting the railway herbicide formulation with water.

[0119] Three days after each treatment was applied, the pharmacological symptoms of weed damage were observed and recorded to characterize the speed of effectiveness. The pharmacological symptoms of weeds were divided into five levels: ① Level 0: No obvious curling or chlorosis was observed in the weeds, and the treated area appeared bluish-green overall, with almost no difference from the blank control; ② Level I: Some leaves (less than 50%) of the weeds showed curling or slight yellowing and chlorosis, and the treated area appeared predominantly green; ③ Level II: Most leaves (more than 50%) of the weeds showed curling or moderate yellowing and chlorosis, and the treated area appeared predominantly yellow; ④ Level III: Almost all leaves of the weeds showed curling or severe yellowing and chlorosis, and the treated area appeared ashen yellow; ⑤ Level IV: All leaves of the weeds were withered and completely faded, and the treated area appeared wilted.

[0120] Forty-five days after the application of pesticides in each treatment area, the weed control rate was investigated and recorded. During the investigation, five random samples were taken from each plot, with a sample area of ​​5m². 2 The weed control effect was statistically calculated based on the control effect per plant in a fixed area, i.e., weed control rate % = (number of normally growing weeds in the blank control area - number of surviving weeds in the treatment area) / number of normally growing weeds in the blank control area × 100%. Weed control effect data processing: data statistics and mean calculation were performed using Excel, and significance analysis of differences was conducted using DPS7.05 software (LSD method).

[0121] Within six months (182 days) after each treatment was applied, local rainfall and the occurrence of pesticide damage in farmland and green plants directly below each treated road section were continuously recorded. The number of times pesticide damage occurred in each treated area within six months was recorded (pesticide damage occurring at different points directly below each road section within the same treated area was counted as one occurrence, and the total number was calculated by summing the results). The above observations and statistical results are shown in Table 6 below.

[0122] Table 6: Statistics on herbaceous symptoms of weeds 3 days after application, weed control rate at 45 days, and occurrence of herbicide damage within 6 months for each treatment.

[0123]

[0124] Note: The 45-day weed control rate counted here includes the total weed control rate, including all grass and broadleaf weeds. For the same indicator, the five treatments are marked with lowercase letters and the differences between different representations are significant (P<0.05), and the treatments are marked with uppercase letters and the differences between different representations are extremely significant (P<0.01).

[0125] Table 6 shows that: (1) the pharmacological symptoms of weed damage varied to some extent among the treatments 3 days after application. Among them, the conventional herbicide group CK showed the mildest pharmacological symptoms of weed damage and had not yet shown obvious effects; the railway herbicide formulation treatment 4 without added synergistic adjuvants showed only mild pharmacological symptoms of grade I; the railway herbicide treatment 1 with 20 parts of low-dose synergistic adjuvants showed aggravated pharmacological symptoms of weeds, which were grade II; the railway herbicide treatments 2 and 3 with 30 parts and 40 parts of medium and high-dose synergistic adjuvants, respectively, showed the most severe pharmacological symptoms of weeds, which were grade III. In summary, the railway herbicide formulation of the present invention showed a significantly faster effect in 3 days than the conventional non-cultivated land herbicide 10% methamidosulfuron suspension. The efficacy of the railway herbicide formulation was further enhanced after the addition of synergistic adjuvants, but the effect of adding more than 40 parts of synergistic adjuvants on further improving the rapid effect was no longer significant.

[0126] (2) The weed control rates of each treatment showed highly significant differences at 45 days after application (P<0.01). Among them, the railway herbicide formulation and its treatments with added synergistic adjuvants showed significantly better weed control effects than the conventional non-cultivated land herbicide CK, and the weed control rate showed an increasing trend with the increase of the amount of synergistic adjuvant, but there was no significant difference between treatments 2 and 3 (same letters). The above data indicate that the railway herbicide formulation of the present invention has significantly better weed control effects than conventional non-cultivated land herbicides at 45 days after application, and the addition of appropriate doses of synergistic adjuvants further improved the weed control effect of the railway herbicide formulation.

[0127] (3) Upon verification, within six months of application, the area under the jurisdiction of the Zhongshan Engineering Section of the Guangzhou Railway Bureau experienced 10 heavy rains or above, 15 moderate rains or above, and frequent heavy to torrential rains. As shown in Table 6, the frequency of phytotoxicity with the conventional non-arable land herbicide 10% methamidosulfuron suspension was high (5 times); while the frequency of phytotoxicity with the railway herbicide formulation of this invention (treatment 4) was significantly reduced to 1 time, a reduction of 80%; and no phytotoxicity incidents were observed in the three treatments (treatments 1 to 3) using the railway herbicide formulation of this invention plus synergistic adjuvants. Therefore, the railway herbicide formulation of this invention and its combined use with synergistic adjuvants can effectively reduce or avoid phytotoxicity to farmland and vegetation along railway lines caused by rainwater erosion and other factors.

Claims

1. A railway herbicide composition, wherein, The railway herbicide composition comprises, by weight, 60-120 parts of glyphosate ammonium salt or isopropylamine salt, 15-60 parts of cycloazinone, and 15-45 parts of a 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt.

2. The railway herbicide composition according to claim 1, wherein, The railway herbicide composition comprises, by weight, 60-120 parts of glyphosate ammonium salt or isopropylamine salt, 37.5-60 parts of cycloazinone, and 15-45 parts of the quaternary ammonium salt of a 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative. Preferably, the railway herbicide composition comprises, by weight, 90 parts of glyphosate ammonium salt or isopropylamine salt, 37.5 parts of cycloazinone, and 30 parts of a 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt.

3. The railway herbicide composition according to claim 1 or 2, wherein, The structural formula of the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative is shown in general formula (Ⅰ): in: X represents an oxygen or sulfur atom; n = an integer; R represents H or an alkyl group; R 1 R 2 Selected independently from C 1-6 alkyl, C 1-6 alkoxy, C 2-6 The alkenyl and aryl groups.

4. The railway herbicide composition according to claim 3, wherein, In formula (Ⅰ), X represents an oxygen atom; Preferably, in formula (Ⅰ), n is an integer from 1 to 6, more preferably an integer from 1 to 4; Preferably, in formula (Ⅰ), R represents H or C. 1-6 Alkyl groups, more preferably representing H; Preferably, in formula (Ⅰ), R 1 and R 2 Alkyl groups independently selected from H and C1-C4 (e.g., methyl, ethyl, propyl, butyl, isopropyl, isobutyl, etc.); Preferably, in formula (Ⅰ), X represents an oxygen atom; n is an integer from 1 to 4; R represents H; R 1 and R 2 It is independently selected from methyl, ethyl, propyl, and butyl.

5. The railway herbicide composition according to claim 1 or 2, wherein, The structural formula of the quaternary ammonium salt of the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative is shown in general formula (II): Where X represents an oxygen or sulfur atom; n = an integer; R represents H or an alkyl group; R 1 R 2 Selected independently from C 1-6 alkyl, C 1-6 alkoxy, C 2-6 alkenyl and aryl groups; It represents Cl-, Br-, F-, I-, acetate, acetylsalicylate, citrate, salicylate, p-toluenesulfonate, hydrogen sulfate, or other acid radicals.

6. The railway herbicide composition according to claim 5, wherein, In formula (II), X represents an oxygen atom; Preferably, in formula (II), n is an integer from 1 to 6, more preferably an integer from 1 to 4; Preferably, in formula (II), R represents H or C. 1-6 Alkyl groups, more preferably representing H; Preferably, in formula (II), R 1 and R 2 Alkyl groups independently selected from H and C1-C4 (e.g., methyl, ethyl, propyl, butyl, isopropyl, isobutyl, etc.); Preferably, in formula (II), X represents an oxygen atom; n is an integer from 1 to 4; R represents H; R 1 and R 2 Independently selected from methyl, ethyl, propyl, and butyl; Preferably, in formula (II), Represents Cl-, Br-, F-, I-, acetate, acetylsalicylate, citrate, or salicylate; Preferably, in formula (II), X represents an oxygen atom; n is an integer from 1 to 4; R represents H; R 1 and R 2 Independently selected from methyl, ethyl, propyl, and butyl; It represents Cl-.

7. The railway herbicide composition according to any one of claims 1 to 6, wherein, The 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt is selected from... Preferably, the 4-amino-3,5-dichloro-6-fluoro-pyridine-2-oxoacetic acid derivative or its quaternary ammonium salt is 8. The railway herbicide composition according to any one of claims 1 to 7, wherein, The herbicide composition further includes 10-40 parts by weight of a synergistic adjuvant; Preferably, the herbicide composition further includes 20-30 parts by weight of a synergistic adjuvant.

9. The railway herbicide composition according to claim 8, wherein, The synergistic agent, by weight percentage, consists of the following components: The quaternary ammonium salt of 4-trifluoromethylbenzyl caffeine succinate dioctyl sulfonate has the following structural formula:

10. The application of the railway herbicide composition according to any one of claims 1 to 9 in the chemical weeding of railway subgrade and shoulders.

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