Quaternary ammonium salt for herbicide synergistic agent and preparation method and application thereof

Abstract

The invention relates to a quaternary ammonium salt for a herbicide synergistic aid as well as a preparation method and application of the quaternary ammonium salt. As the quaternary ammonium salt has a great charge adsorption effect, the quaternary ammonium salt can be deposited on the surface of weeds, and when the quaternary ammonium salt is used in the herbicide synergistic aid, the effect of the aid can be greatly improved, the dosage of a herbicide is further reduced, and the herbicide synergistic effect is improved. The control effect and the lasting period are improved.

Description

Technical Field

[0001] The invention relates to the technical field of railway weed control, and in particular to a quaternary ammonium salt used for a herbicide synergist, a preparation method and an application thereof, and in particular provides a herbicide synergist added with quaternary ammonium salt of 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate, a preparation method and an application thereof. Background Art

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

[0003] Railway roadbed weeding is to maintain the reliability and safety of the line. The growth of grass and trees will not only affect the stability of the roadbed, but also block the view of the signal equipment and increase the workload of maintenance and cleaning. In addition, if the vehicle encounters a grassy roadbed during driving, it will not only affect the running speed of the train, but also damage the power system of the train. Therefore, timely and effective weeding is essential for railway operations. The methods of railway weeding are: physical weeding, which is a method of weeding using mechanical equipment or manual labor. Common physical weeding methods include lawn mowers, weeding hoes, etc. This method is suitable for areas where grass and trees grow densely, and grass and trees can be cut or removed quickly. However, physical weeding requires manual operation, and for large areas of railway roadbeds, the workload is large. Chemical weeding is to spray or spread chemical herbicides on grass and trees to inhibit or kill grass and trees through the action of drugs. This method can be carried out over a large range with good results. With the advancement of science and technology and the continuous introduction of high-efficiency, low-toxic and low-residue chemical herbicide varieties, more and more chemical herbicides can be used for railway weed control. People pay more attention to and rely on chemical weed control on railways. However, the thoroughness and duration of chemical weed control are key issues in railway weed control. Synergistic adjuvants are one of the most effective ways to reduce the amount of railway herbicides, reduce costs and improve prevention and duration. It is also in line with the national policy of zero growth in pesticides and fertilizers.

[0004] Existing synergistic additives include vegetable oils, mineral oils, silicones, azones, thiophenes, isomeric alcohol ether wetting agents, penetrants T, etc., but most of them are general additives. No additive or composite additive is designed based on the properties and action mechanism of a specific original drug, so they rarely achieve excellent results.

[0005] Therefore, it is imperative to provide a synergistic adjuvant that can improve the weed control effect of railway herbicides. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a quaternary ammonium salt for a herbicide synergist, a preparation method and an application thereof. The quaternary ammonium salt of the present invention as a herbicide synergist can greatly improve the effect of prevention and treatment, further reduce the amount of herbicide used, and improve the prevention effect and the lasting effect. The herbicide synergist using the quaternary ammonium salt of the present invention can enable the herbicide liquid to quickly destroy the wax layer on the target, quickly penetrate into the cell, improve the absorption of the liquid, and thus improve the prevention effect.

[0007] To this end, an object of the present invention is to provide a quaternary ammonium salt for use as a herbicide synergist: 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonic acid quaternary ammonium salt.

[0008] Another object of the present invention is to provide a method for preparing the quaternary ammonium salt.

[0009] Another object of the present invention is to provide a use of the above quaternary ammonium salt in the preparation of a herbicide synergistic adjuvant.

[0010] Still another object of the present invention is to provide a herbicide synergistic adjuvant.

[0011] Another object of the present invention is to provide an application of a herbicide synergistic adjuvant.

[0012] The technical solution adopted by the present invention is as follows:

[0013] In one aspect, the present invention provides a quaternary ammonium salt for use as a herbicide synergist, the chemical name of which is: 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonic acid quaternary ammonium salt, and the structural formula is as follows:

[0014]

[0015] On the other hand, the present invention provides a method for preparing the above-mentioned quaternary ammonium salt, the preparation method comprising the steps of:

[0016] 1) reacting caffeine with trifluoromethylbenzyl bromide in a first organic solvent to form a compound shown in formula 1:

[0017]

[0018] 2) reacting the compound represented by formula 1 with sodium diisooctyl sulfosuccinate in a second organic solvent to obtain the product.

[0019] Preferably, in step 1), the first organic solvent is selected from N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, etc., preferably DMF (N,N-dimethylformamide).

[0020] Preferably, in step 1), the reaction temperature is 20°C-90°C, preferably 60°C-65°C.

[0021] Preferably, in step 1), the reaction time is 5-24 hours, preferably 13-15 hours.

[0022] Preferably, in step 2), the second organic solvent is selected from dioxane, methyl tert-butyl ether, tetrahydrofuran, isopropyl ether, etc., preferably THF (tetrahydrofuran).

[0023] Preferably, in step 2), the reaction temperature is 20°C-45°C, preferably room temperature.

[0024] Preferably, in step 2), the reaction time is 15-30 hours, preferably 22-24 hours.

[0025] Preferably, the preparation method further comprises a desalting operation (removing inorganic salts, NaBr) after step 2).

[0026] In a specific embodiment, the preparation method of the above-mentioned quaternary ammonium salt of the present invention is as follows: the first step is to use caffeine as a raw material to react with trifluoromethylbenzyl bromide, and heat the reaction in a solvent DMF (N,N-dimethylformamide) for 15 hours to form a compound of formula 1. The second step is to react the obtained compound of formula 1 with sodium diisooctyl sulfosuccinate in THF (tetrahydrofuran) at room temperature for 24 hours, remove inorganic salts, and purify to obtain.

[0027] The specific reaction equation is as follows:

[0028]

[0029] In another aspect, the present invention provides use of the quaternary ammonium salt in preparing a herbicide synergistic adjuvant.

[0030] Preferably, the herbicide synergist is a railway herbicide synergist.

[0031] In yet another aspect, the present invention provides a herbicide synergistic adjuvant comprising the above-mentioned quaternary ammonium salt.

[0032] Preferably, the herbicide synergistic adjuvant of the present invention is composed of the following components in terms of weight percentage:

[0033] 1-Ethyl-3-methylimidazole acetate 1-30%, algae oil 5-20%, the above quaternary ammonium salt: 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate ammonium salt 1-5%, mineral oil emulsifier 10-25%, white oil 2# supplemented to 100%.

[0034] Preferably, in terms of weight percentage, the 1-ethyl-3-methylimidazolium acetate is 25.0%.

[0035] Preferably, the algae oil is 10.0% by weight.

[0036] Preferably, the content of quaternary ammonium 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate is 2.0% by weight.

[0037] Preferably, the mineral oil emulsifier is 15.0% by weight.

[0038] The 1-ethyl-3-methylimidazolium acetate, CAS: 143314-174, chemical formula: C8H14N2O2, is a colorless transparent liquid. The algae oil is an extract of Schizochytrium autophyllum, a brown oil. The mineral oil emulsifier is a mineral oil emulsifier produced by Jiangsu Qingyu Chemical Technology Co., Ltd. The white oil 2# is SKALN 2#.

[0039] Preferably, the herbicide synergistic adjuvant of the present invention is composed of the following components in terms of weight percentage:

[0040]

[0041] Preferably, the herbicide synergist is a railway herbicide synergist.

[0042] In another aspect, the present invention provides a method for preparing the above-mentioned herbicide synergistic adjuvant, which comprises the following steps: according to the above-mentioned formula, 1-ethyl-3-methylimidazole acetate, algae oil, quaternary ammonium salt of 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate, mineral oil emulsifier and white oil 2# are weighed and mixed evenly and transparently to obtain the herbicide synergistic adjuvant.

[0043] In yet another aspect, the present invention provides a use of the above-mentioned herbicide synergistic adjuvant in herbicides.

[0044] Preferably, the application amount of the herbicide synergist is 1 / 1000 to 10 / 1000 of the mass of the spray liquid after final water mixing. When used for railway herbicides, it is generally used in a tank mix form, and the addition amount is 1 / 1000 to 10 / 1000 of the mass of the spray liquid after final water mixing. The application amount varies with weather conditions and weed occurrence conditions, and increases or decreases according to the specific application method.

[0045] Preferably, the herbicides include glyphosate, glufosinate, glufosinate-ammonium, diquat, paraquat, hexazinone, triclopyr, triclopyr butoxyethyl, erythritic acid, metazachlor, sulfamethoxam, ethametsulfuron-methyl, quizalofop-p-ethyl, herbicide, cypermethrin, promethazine, promethazine, ametryn, ametryn, terbuthylazine, 2,4-D, 2-methyl-4-chlorophenoxyacetic acid and other original drugs and their salts and various preparations processed therefrom.

[0046] Compared with the prior art, this application has at least the following beneficial technical effects:

[0047] The invention provides a novel quaternary ammonium salt. The quaternary ammonium salt of the invention can be deposited on the surface of weeds due to its great charge adsorption effect. The quaternary ammonium salt is used in a herbicide synergistic adjuvant, which can greatly improve the effect of the adjuvant, further reduce the amount of the herbicide, and improve the prevention effect and the lasting effect.

[0048] The quaternary ammonium salt of the invention is designed according to the physical and chemical properties and application method of the railway herbicide, has strong specificity, good functionality, long lasting effect, and can maximize the effect of the railway herbicide.

[0049] The synergistic adjuvants of traditional herbicides are mainly surfactants, which only improve the wetting and spreading of weed targets. The present invention is different from this. The main component of the present invention is quaternary ammonium salt of 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate, which has the following special properties: it can self-assemble into micelles in water, with a micelle particle size of 35.8nm, a Zeta potential of 32.0mV, and an equivalent spherical specific surface area of ​​199.93m 2 / g, has a great charge adsorption effect, thus greatly promoting the deposition of drugs on the surface of weeds; main component two: ionic liquid 1-ethyl-3-methylimidazolium acetate as a synergistic aid, which is a colorless liquid with low volatility and good solubility, can quickly destroy the wax layer and cell wall of weeds, and improve the permeability of the liquid medicine into the body; main component three: algae oil, excellent moisturizing effect, delays the drying time of the liquid medicine on weeds; in addition, the white oil and mineral oil emulsifier filled can well mix several active ingredients, and the white oil itself can also improve the moisturizing function on weeds. In short, through the study of the adsorption, deposition and conduction behavior of the synergistic aid of the railway herbicide of the present invention on the weed target during the spraying process, it is issued that the synergistic aid of the present invention has a better effect on the transmission of the target (weed). BRIEF DESCRIPTION OF THE DRAWINGS

[0050] Figure 1 This is a dryness analysis diagram for different treatments in Example 7.

[0051] Figure 2 This is a dryness analysis chart of the synergistic aids with different formulations in Example 8. DETAILED DESCRIPTION

[0052] The present invention is further described below in conjunction with the embodiments. These embodiments are intended to help illustrate the content of the present invention rather than to limit the scope of the present invention.

[0053] Example 1: Preparation of the quaternary ammonium salt of the present invention: 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate quaternary ammonium salt

[0054] Firstly, easily available caffeine is used as a raw material to react with trifluoromethylbenzyl bromide to form a novel quaternary ammonium salt compound of formula I (the first step); then the intermediate novel quaternary ammonium salt compound of formula I is reacted with sodium diisooctyl sulfosuccinate, and after purification, a novel quaternary ammonium salt compound II is obtained (the second step).

[0055] 4-Trifluoromethylbenzyl caffeine dioctyl succinate sulfonate quaternary ammonium salt (quaternary ammonium salt compound II) Characterization: H NMR spectrum: 1 H 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 spectrum: HRMS (ESI) C 36 H 54 F3N4O9S + [M+H] + Theoretical value: 775.3558, measured value: 775.3554

[0056] The specific reaction equation is as follows:

[0057] First step reaction:

[0058]

[0059] Second step reaction:

[0060]

[0061] The specific process conditions are as follows:

[0062] Synthesis process conditions Example 1-1

[0063] Feeding molar ratio:

[0064] Caffeine: p-Trifluoromethylbenzyl bromide: sodium diisooctyl sulfosuccinate = 1:1.1:1.2

[0065] Solvent:

[0066] The first step is solvent DMF (N,N-dimethylformamide), the amount of solvent used is 5 times that of caffeine (mass ratio);

[0067] The second step uses THF (tetrahydrofuran) as solvent, and the amount of solvent used is 8 times that of caffeine (mass ratio).

[0068] Reaction temperature:

[0069] The first step reaction temperature: 90°C; the second step reaction temperature: 40°C.

[0070] Reaction time:

[0071] First step reaction time: 10 hours; second step reaction time: 20 hours

[0072] Reaction yield: 75%.

[0073] Synthesis process conditions Example 1-2

[0074] Feeding molar ratio:

[0075] Caffeine: p-Trifluoromethylbenzyl bromide: sodium diisooctyl sulfosuccinate = 1:1.1:1.2

[0076] Solvent:

[0077] The first step is solvent DMSO (dimethyl sulfoxide), the amount of solvent used is 5 times that of caffeine (mass ratio);

[0078] The second step uses THF (tetrahydrofuran) as solvent, and the amount of solvent used is 8 times that of caffeine (mass ratio).

[0079] Reaction temperature:

[0080] The first step reaction temperature: 90°C; the second step reaction temperature: 40°C.

[0081] Reaction time:

[0082] First step reaction time: 10 hours; second step reaction time: 22 hours

[0083] Reaction yield: 70%.

[0084] Synthesis process conditions Examples 1-3

[0085] Feeding molar ratio:

[0086] Caffeine: p-Trifluoromethylbenzyl bromide: sodium diisooctyl sulfosuccinate = 1:1.1:1.2

[0087] Solvent:

[0088] The first step is solvent DMF (N,N-dimethylformamide), the amount of solvent used is 5 times that of caffeine (mass ratio);

[0089] The second step uses THF (tetrahydrofuran) as solvent, and the amount of solvent used is 8 times that of caffeine (mass ratio).

[0090] Reaction temperature:

[0091] The first step reaction temperature is 65°C; the second step reaction temperature is 25°C.

[0092] Reaction time:

[0093] First step reaction time: 15 hours; second step reaction time: 24 hours

[0094] Reaction yield: 90%.

[0095] Synthesis process conditions Examples 1-4

[0096] Feeding molar ratio:

[0097] Caffeine: p-trifluoromethylbenzyl bromide: sodium diisooctyl sulfosuccinate = 1:1.1:1.2;

[0098] Solvent:

[0099] The first step is solvent DMF (N,N-dimethylformamide), the amount of solvent used is 5 times that of caffeine (mass ratio);

[0100] The second step uses THF (tetrahydrofuran) as solvent, and the amount of solvent used is 8 times that of caffeine (mass ratio).

[0101] Reaction temperature:

[0102] The first step reaction temperature is 40°C; the second step reaction temperature is 25°C.

[0103] Reaction time:

[0104] First step reaction time: 30 hours; second step reaction time: 24 hours

[0105] Reaction yield: 70%.

[0106] Synthesis process conditions Examples 1-5

[0107] Feeding molar ratio:

[0108] Caffeine: p-Trifluoromethylbenzyl bromide: sodium diisooctyl sulfosuccinate = 1:1.1:1.2

[0109] Solvent:

[0110] The first step is solvent DMF (N,N-dimethylformamide), the amount of solvent used is 5 times that of caffeine (mass ratio);

[0111] The second step is to use the solvent dioxane, the amount of which is 8 times that of caffeine (mass ratio).

[0112] Reaction temperature:

[0113] The first step reaction temperature is 65°C; the second step reaction temperature is 25°C.

[0114] Reaction time:

[0115] First step reaction time: 15 hours; second step reaction time: 24 hours

[0116] Reaction yield: 80%.

[0117] The quaternary ammonium salt of 4-trifluoromethylbenzyl caffeine dioctyl sulfosuccinate used in the following examples was prepared by the method of Example 1-1.

[0118] Example 2: Herbicide synergist

[0119]

[0120] According to the above weight percentages, 1-ethyl-3-methylimidazole acetate, algae oil, 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate quaternary ammonium salt, mineral oil emulsifier, and white oil 2# were weighed and mixed to make them uniform and transparent, thus preparing the railway herbicide synergistic adjuvant.

[0121] Example 3: Herbicide synergist

[0122]

[0123] According to the above weight percentages, 1-ethyl-3-methylimidazole acetate, algae oil, 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate quaternary ammonium salt, mineral oil emulsifier, and white oil 2# were weighed and mixed to make them uniform and transparent, thus preparing the railway herbicide synergistic adjuvant.

[0124] Example 4: Herbicide synergist

[0125]

[0126] According to the above weight percentages, 1-ethyl-3-methylimidazole acetate, algae oil, 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate quaternary ammonium salt, mineral oil emulsifier, and white oil 2# were weighed and mixed to make them uniform and transparent, thus preparing the railway herbicide synergistic adjuvant.

[0127] Example 5: Herbicide synergist

[0128]

[0129] According to the above weight percentages, 1-ethyl-3-methylimidazole acetate, algae oil, 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate quaternary ammonium salt, mineral oil emulsifier, and white oil 2# were weighed and mixed to make them uniform and transparent, thus preparing the railway herbicide synergistic adjuvant.

[0130] Example 6: Herbicide synergist

[0131]

[0132] According to the above weight percentages, 1-ethyl-3-methylimidazole acetate, algae oil, 4-trifluoromethylbenzyl caffeine dioctyl succinate sulfonate quaternary ammonium salt, mineral oil emulsifier, and white oil 2# were weighed and mixed to make them uniform and transparent, thus preparing the railway herbicide synergistic adjuvant.

[0133] Example 7: Characterization of anti-evaporation test

[0134] The dynamic dryness analysis tester is used to characterize the anti-evaporation process of the spray droplets. It uses the principle of dynamic multiple light scattering to detect the changes in the light spots caused by the Brownian motion of the particles in the sample. The drying process of the sample can be detected based on the movement of the particles. Because if the drug dries very quickly after spraying, it is not conducive to drug absorption, so the drying time and degree of drying after spraying the drug should be controlled. The specific test process is as follows:

[0135] Table 1 Test treatment (the amount of adjuvant is one thousandth of the spray liquid)

[0136]

[0137] Note: The dilution water volume for each treatment test is 30000 grams

[0138] The test results are as follows Figure 1 shown.

[0139] It can be seen from the dryness analysis diagram that in terms of anti-evaporation (moisture retention time), the effects are: treatment 2>treatment 1>treatment 3>treatment 5>treatment 4>treatment 6 (glyphosate), indicating that after the herbicide synergist of the present invention is added to glyphosate, the anti-evaporation ability (moisture retention time) is increased to varying degrees, and is greater than glyphosate without the herbicide synergist of the present invention. Among them, treatment 2 has the longest moisture retention time and the best effect.

[0140] Example 8: Anti-evaporation test of synergists with different formulations

[0141] In order to investigate the anti-evaporation effect of synergists with different formulations, the following experiment was conducted. The formulations of the synergists used are shown in Table 2.

[0142] Table 2 Anti-evaporation effect of synergistic additives

[0143]

[0144] The test results are as follows Figure 2 As shown. From the dryness analysis chart, it can be seen that the anti-evaporation (moisture retention time) of the herbicide synergist of the present invention is the best. Since the synergists A, B, and C lack a certain component of the present invention in the adjuvant formula, they show slightly better or equivalent anti-evaporation performance as glyphosate (without synergist). Although the composition of synergist D is the same as that of the present invention, the ratio is different, and the anti-evaporation effect is only slightly better than that of glyphosate. Moreover, the anti-evaporation performance of synergists A, B, C, and D is far less good than that of the herbicide synergist of the present invention. It shows that the herbicide synergist of the present invention has good anti-evaporation performance.

[0145] Example 9: Characterization test of deposition amount of builder with different formulations

[0146] The spray gravimetric method was used for measurement, and the sprayer used for spraying was a WS-18D electric sprayer. First, a hydrophobic paraffin plate was used to simulate the leaf surface for spraying, and the deposition of the liquid on it was observed and measured. The greater the deposition amount, the better the retention and adhesion effect of the liquid on the target. The test scheme is as shown in Table 1 of Example 7. The test results are shown in Table 3 below.

[0147] Table 3 Leaf surface deposition of each treatment in Table 1 in Example 7

[0148] Sample name Process 1 Process 2 Process 3 Process 4 Process 5 Process 6 <![CDATA[Deposition amount (mg / cm 2 )]]> 2.37 2.54 2.20 2.09 2.19 1.1

[0149] The results show that the deposition amount of the drug solution with the synergist of the present invention on the paraffin plate is much greater than that of the drug solution without the synergist, showing good deposition performance.

[0150] Example 10: Indoor bioassay experiment

[0151] 1) Experimental design: The experimental design is shown in Table 4

[0152] Table 4: Experimental design

[0153]

[0154] 2) Analysis of indoor fresh weight efficacy data of each treatment: The results are shown in Table 5.

[0155] Table 5: Fresh weight control effect of indoor weeds in each treatment in the test - 21 days after application

[0156]

[0157] The fresh weight data of the 5 glyphosate products 21 days after application in the above table show that the 5 glyphosate products plus synergists have good control effects on Chloris and Purslane, while the glyphosate isopropylamine salt without synergists has poor control effect. This shows that the synergists have a good synergistic effect on glyphosate weed control, and the overall glyphosate dosage can be reduced by 20% after adding the synergists.

[0158] Example 11: Field test of 18.5% glufosinate aqueous solution + synergist

[0159] Verify the control effect of 18.5% glufosinate aqueous solution + synergistic adjuvant on weeds, and compare the control effect differences on weeds. Test site: both sides of a freight transportation railway in Tianjin; the test weeds are spontaneous weeds, and the main weeds are broad-leaved weeds: morning glory, lettuce, aster, kochia, inula, goose down vine, yellow top chrysanthemum, wild lentil, purslane, prickly lettuce, and tooth fruit sorrel. Gramineae weeds: crabgrass, barnyard grass, foxtail grass, millet, goose tendon grass, three-angled grass, and teff (the weeds are all large weeds, belonging to the stage of more vigorous weed growth, mostly in the heading and flowering stages). The pesticide treatment test plan is shown in Table 6.

[0160] Table 6: Chemical treatment test plan

[0161]

[0162] The results of the efficacy test are as follows:

[0163] Observation 2 days after application showed that treatments 1 to 5 had a faster effect on grass weeds, with leaves losing green and turning yellow, while no change was observed in treatments 6 and 7. Broadleaf weeds showed a slightly slower effect, with no obvious loss of green or wilting in treatment 7. The treatments with synergistic adjuvants had a faster weed control effect and action speed.

[0164] Four days after application, broadleaf weeds began to show obvious chlorosis and withering, and some weeds (Eryngium serrata) died completely. Visually, treatments 1 to 5 showed better chlorosis and withering degrees, which were significantly higher than treatments 6 and 7.

[0165] The protective effect 14 days after the medication is shown in Table 7:

[0166] Table 7: Control effect of each treatment on weeds 14 days after each treatment

[0167]

[0168] 14 days after application, treatments 1 to 5 had good weed control effects, treatment 2 had a 99% weed control effect on grass weeds and a 96% weed control effect on broadleaf weeds. The control effects of treatments 1 to 5 were significantly higher than those of control treatment 6 and were equivalent to those of control treatment 7. This indicates that the addition of the railway herbicide synergist significantly reduced the amount of glufosinate herbicide used, with a reduction of 20%.

[0169] Example 12: Field efficacy test of railway herbicide TKEI-01 + synergist

[0170] The railway herbicide composition TKEI-01 comprises: 30% glyphosate aqueous solution (code: I) + 25% cyclohexanone soluble solution (code: II) + 62% triclopyr butoxyethyl ester (code: III).

[0171] This experiment verifies the weed control effect of TKEI-01 + synergistic adjuvants and verifies the synergistic effect of different synergistic adjuvants on the TKEI-01 herbicide combination.

[0172] The test site is located next to the railway at Yangliuqing Farm, Xiqing District, Tianjin. The test weeds are spontaneous weeds. The weed conditions are as follows:

[0173] Grass weeds: reed (perennial reed), foxtail grass (annual foxtail), barnyard grass (annual Echinochloa), goosegrass (annual millet), alfalfa (Aegilops genus, annual herb)

[0174] Broad-leaved weeds: plantain (Plantaginaceae, Plantago, annual or biennial herb), wild sunflower (annual Chrysanthemum), yellowtop (annual Flaveria), sowthistle (annual Chimonanthus), Erigeron candidum (annual Ligusticum), drill-leaved aster (annual Aster), mugwort (perennial Artemisia), and ragweed, also known as small-flowered creeper or small-flowered false ragweed. It is a perennial herb or shrubby climbing vine (pseudo-Eupatorium); Chenopodiaceae: Kochia (annual Kochia), Chenopodiaceae (annual Chenopodiaceae); Moraceae: Humulus (perennial Humulus); Cruciferae: Cardamine (annual Cardamine); Lamiaceae: Leonurus (annual or biennial Leonurus); Litsea: Rumex (annual Polygonum); Asclepiadaceae: Anemarrhena (perennial Anemarrhena); Convolvulaceae: Morning Glory (annual Morning Glory), Vitaceae: Parthenocissus (perennial Parthenocissus)

[0175] Description of main weeds before spraying: reeds have more than 7 leaves, with an average plant height of about 1.2 meters. Setaria and Goosegrass have 3 to 4 tillers, Aegilops tauschii has headed, broadleaf weeds have bloomed, and the average number of weeds per square meter is about 100.

[0176] The experimental design is shown in Table 8:

[0177] Table 8 Treatment schemes for each test agent

[0178] deal with Pharmacy Synergist Dosage of I+II+III+adjuvant (g / mu) 1 I+II+III The synergist of Example 2 200+200+120+30 2 I+II+III The synergist of Example 3 200+200+120+30 3 I+II+III The synergist of Example 4 200+200+120+30 4 I+II+III The synergist of Example 3 200+200+120+100 5 I+II+III The synergist of Example 3 200+200+120+150 6 I+II+III No builder 240+240+160 7 I+II+III No builder 300+300+200

[0179] Note: The amount of water used for each treatment dilution is 30000 grams

[0180] The test results are as follows:

[0181] On the third day after the application, the broadleaf weeds, annual weeds, perennial broadleaf weeds, and vine weeds in treatments 1, 2, 3, 4, 5, 6, and 7 began to wilt and lose their green color. There was no obvious symptom of the drug damage to the reeds.

[0182] Observation was performed 7 days after the application. Annual broadleaf weeds and grass weeds, annual vine weed morning glory, perennial vine weed goose down vine, and humulus were basically dead in treatments 1, 2, 3, 4, 5, 6, and 7. The mortality rate of annual weeds was more than 80%. The malignant weed reed stopped growing, with leaves wilting and losing green, and some reed stems were bent and lodged. There was no significant difference in the weed control effect among the treatments.

[0183] Observation after 14 days of treatment showed that almost all annual weeds, perennial weeds and vine weeds in treatments 1, 2, 3, 4, 5 and 7 died, and the weed mortality rate was over 90%. The leaves of reeds lost their green color, some leaves dried up and stopped growing, and most reeds showed symptoms of broken stems and lodging, and the reeds were close to death. In treatment 6, most annual weeds died, and the annual weed mortality rate was over 90%. A small number of perennial vine weeds and reeds survived, and the overall weed control effect was about 80%.

[0184] 21 days after the application, the number of weeds surviving in each treatment was investigated, and the weed control efficiency in each treatment was calculated (data are shown in Table 9). Treatments 1, 2, 3, 4, 5, and 7 had similar weed control effects, with annual weeds, perennial weeds, grass weeds, and vine weeds basically dead, and the weed control efficiency in terms of number of weeds was 96.3%, 97.2%, 94.1%, 98.2%, 98.9%, and 98.5%, respectively. In treatment 6, a small number of reeds and vine weeds, Parthenocissus tricuspidata, still survived, and the total weed control efficiency was 80.0%. The weed control efficiency in treatment 6 was significantly lower than that in treatments 1, 2, 3, 4, 5, and 7.

[0185] In this experiment, the dosage of treatment 7 is the same as the recommended dosage for actual application of railway weed control. Adding synergistic adjuvants (treatments 1, 2, 3, 4, and 5) can achieve a similar weed control effect as treatment 7 when the dosage is reduced by 30%.

[0186] At the same time, it can be seen that when the amount of the synergistic adjuvant used in Example 3 of Treatments 4 and 5 was significantly increased, the control effect on the number of weeds was only slightly improved. When the amount of the adjuvant was increased to 100 grams and 150 grams, there was no significant difference in the synergistic effect on the weed control effect when the amount of the adjuvant was 30 grams.

[0187] Table 9 Control effect of each treatment on the number of weeds 21 days after application

[0188]

[0189] The detailed description of the railway herbicide synergistic adjuvant and its preparation method with reference to the above-mentioned embodiment is illustrative rather than restrictive, and several embodiments can be listed according to the limited scope. Therefore, changes and modifications without departing from the overall concept of the present invention should fall within the scope of protection of the present invention.

Claims

1. A quaternary ammonium salt used as a herbicide synergist, the structural formula of which is as follows:

2. a method for preparing the quaternary ammonium salt according to claim 1, the method comprising the steps of: 1) reacting caffeine with trifluoromethylbenzyl bromide in a first organic solvent to form a compound shown in formula 1: 2) reacting the compound represented by formula 1 with sodium diisooctyl sulfosuccinate in a second organic solvent to obtain the product.

3. The method according to claim 2, wherein: In step 1), the first organic solvent is selected from N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, etc., preferably DMF (N,N-dimethylformamide); Preferably, in step 1), the reaction temperature is 20°C-90°C, preferably 60°C-65°C.

4. The method according to claim 2 or 3, wherein: In step 1), the reaction time is 5-24 hours, preferably 13-15 hours; Preferably, in step 2), the second organic solvent is selected from dioxane, methyl tert-butyl ether, tetrahydrofuran, isopropyl ether, etc., preferably THF (tetrahydrofuran); Preferably, in step 2), the reaction temperature is 20°C-45°C, preferably room temperature; Preferably, in step 2), the reaction time is 15-30 hours, preferably 22-24 hours; Preferably, the preparation method further comprises a desalting operation (removing inorganic salts, NaBr) after step 2).

5. The method according to any one of claims 2 to 4, wherein the preparation method is as follows: a first step, using caffeine as a raw material to react with trifluoromethylbenzyl bromide, heating the reaction in a solvent DMF (N,N-dimethylformamide) for 15 hours to form a compound of formula 1; a second step, reacting the obtained compound of formula 1 in sodium diisooctyl sulfosuccinate in THF (tetrahydrofuran) at room temperature for 24 hours, removing inorganic salts, and purifying to obtain; The reaction equation is as follows:

6. Use of the quaternary ammonium salt according to claim 1 or the quaternary ammonium salt prepared by the method of any one of claims 2 to 5 in the preparation of a herbicide synergistic adjuvant; Preferably, the herbicide synergist is a railway herbicide synergist.

7. A herbicide synergistic adjuvant, comprising the quaternary ammonium salt according to claim 1 or the quaternary ammonium salt prepared by the method according to any one of claims 2 to 5.

8. The herbicide synergist according to claim 7, wherein: The herbicide synergistic adjuvant is composed of the following components according to weight percentage: 1-ethyl-3-methylimidazolium acetate 1-30%, algae oil 5-20%, the quaternary ammonium salt according to claim 1 or the quaternary ammonium salt prepared by the method of any one of claims 2 to 5 1-5%, mineral oil emulsifier 10-25%, white oil 2# supplemented to 100%; Preferably, in terms of weight percentage, 1-ethyl-3-methylimidazolium acetate is 25.0%; Preferably, the algae oil is 10.0% by weight; Preferably, the quaternary ammonium salt according to claim 1 or the quaternary ammonium salt prepared by the method according to any one of claims 2 to 5 is 2.0% by weight; Preferably, the mineral oil emulsifier is 15.0% by weight.

9. The herbicide synergist according to claim 7 or 8, wherein: The herbicide synergistic adjuvant is composed of the following components according to weight percentage:

10. Use of the herbicide synergist according to any one of claims 7 to 9 in herbicides; Preferably, the herbicides include glyphosate, glufosinate, glufosinate-ammonium, diquat, paraquat, hexazinone, triclopyr, triclopyr butoxyethyl, erythritic acid, metazachlor, sulfamethoxam, ethametsulfuron-methyl, quizalofop-p-ethyl, herbicide, promethazine, promethazine, ametryn, ametryn, terbuthylazine, 2,4-D, 2-methyl-4-chlorophenoxyacetic acid and other original drugs and their salts and various preparations processed therefrom; Preferably, the herbicide is a railroad herbicide.

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