WO2024217654A1 - Liquid herbicidal composition and compounds for stabilizing same - Google Patents

Abstract

The invention relates to compounds selected from the class of carbonate esters and/or from the class of dicarboxylic acid esters, which can be used for stabilizing compositions based on pinoxaden. The claimed herbicidal compositions are prepared in the following forms: an emulsion concentrate, a microemulsion concentrate, a nanoemulsion concentrate, a microemulsion, and an oil-in-water emulsion. The compositions are physically and chemically stable and exhibit an improved herbicidal effect on a broader spectrum of annual grassy weeds.

Description

Liquid herbicide composition and compounds for its stabilization

The present invention relates to the field of agriculture and can be used to control weeds in spring and winter grain crops.

Pinoxaden is used routinely to protect wheat and barley crops from annual cereal weeds. The active ingredient is an acetyl-CoA carboxylase inhibitor, a post-emergence, systemic herbicide (see the reference book "The Pesticide Manna!", 19 ^l edition, VSRS, (Zh, 2021, pp. 925-926).

In practice, various formulations based on pinoxaden are used to treat grain crops, most often these are emulsion concentrates (EC). The creation of such formulations is a complex task due to the chemical and physical instability of pinoxaden. Over time, innoxaden in preparations decomposes as a result of a hydrolysis reaction, which reduces their biological effectiveness. To increase the shelf life of formulations, various stabilizers are added to their composition. Such compounds include iairimer, tris-esters of phosphoric acid.

A herbicide composition in the form of an emulsifying concentrate based on pnoxaden is known from the prior art (EA .01865481, cd. A01N 43/90, published on 30.09.2013). To stabilize the known preparation, an alcohol solvent is used, including benzyl alcohol, tstrahydrofurfuryl alcohol or 2-methyl-2,4-pyridinol. The formulation may also contain castor oil ethoxylate, fish oil or methyl ester of rapeseed oil. A disadvantage of this composition is the use of flammable and toxic co-solvents: toluene, xylene, cumene.

Chinese application CN 111296464 A (published on 19.06.2020, class A0U 13 /00) describes a herbicide composition containing ninoxadeins, an antidote, an emulsifier, a stabilizer, an alcohol solubilizer, and a solvent. Various tri~(C2-C6 alkyl] esters of phosphoric acid can be used as stabilizers, including triethyl phosphate, tripropyl phosphate, tributyl phosphate, trihexyl phosphate.

For complete solubilization of active substances in multi-component liquid agrochemical compositions, an alcohol solvent is used together with a co-solvent. For example, in the Russian patent RU 2637524 C2 (published 05.12.2017, cl. A01N 43/90) describes emulsion concentrates containing a combination of pinoxaden and florasulam or a combination of pinoxadene, florasulam and clodinafon-propargyl, a solvent system containing an alcohol solvent (hexylene glycol, benzyl alcohol and others) and a solvent based on heavy aromatic hydrocarbons. In addition, the compositions of these compositions also include castor oil ethoxylate and tris-(2-ethylhexyl)-phosphate. However, the working emulsion of this preparation is not sufficiently stable - the shelf life does not exceed 2 hours after dilution.

The closest analogue of the invention is a liquid herbicide composition based on shockeaden (patent EA 0G6230 B1, class A01N 43/90, published on 30.03.2012). To stabilize the preparation, tris-esters of phosphoric acid are used together with aliphatic or aromatic alcohols. Also, the known composition contains an emulsifier, a solvent and/or an auxiliary substance for the preparation of such a preparation as an emulsion concentrate, an oil dispersion, a suspoemulsion or an emulsion of the "oil in water" type. The specified formulations are used to protect grain crops, controlling mainly such weeds as foxtail (species), millet (species), wild oats, field broom, foxtail. The disadvantage of these preparations is their insufficient effectiveness against annual cereal weeds.

Since there are no clearly established patterns that allow selecting suitable stabilizers and their optimal amount that ensures the production of liquid formulations that are stable during long-term storage in a wide temperature range (from minus 15 °C to +35 °C), it should be recognized that such selection is a difficult task, especially when it comes to the possibility of using such an active substance as pinoxaden. Therefore, there is still a need to develop new, more stable emulsion preparations.

The present invention is based on the task of developing a liquid herbicide composition that is characterized by increased stability during long-term storage, over a wide temperature range.

The technical result consists in creating a physically and chemically stable liquid herbicide composition that has an improved herbicidal effect against an extended spectrum of annual cereal weeds (compared to preparations known from the prior art). The object of the claimed invention is the use of a compound selected from the class of organocarbonates and/or from the class of esters of dacarboxylic acids as a stabilizer for a herbicide composition based on nioxadene

Another object of the claimed invention is a stable herbicidal composition containing pinoxaden, an emulsifier, a liquid diluent, and at least one stabilizer selected from the class of organocarbonates and/or from the class of dicarboxylic acid esters (saturated, unsaturated or aromatic), wherein the stabilizer is present in an amount that enhances the herbicidal activity of pinoxaden. The wording "at least one stabilizer" means that the stabilizer may include one, two or more chemical compounds belonging to the above-mentioned classes. In particular, the stabilizer may be a mixture of two compounds, one of which is selected from the class of organocarbonates and the other from the class of dicarboxylic acid esters.

As an organocarbonate, dimethyl carbonate, ethyl carbonate, propylene carbonate, diphenyl carbonate or doxycarbonate are used.

DabutylmaleaT, bis-(2-ethylhexium)-maleate, diisotridecyl adipate, bis-(2-ethyl1exyl)-adipag, bis~(2-ethylhecaic)-sebacynate, bis-(2-ethylhexyl)-phthalate are used as dicarboxylic acid esters. , butyl dodecyl phthalate, dibutyl decyl phthalate, didodecyl phthalate or dibutyl phthalate.

It was unexpectedly found that the stabilizers used in combination with pinoxaden provide an increase in the effectiveness of its action in relation to weed vegetation, which is most likely achieved by improving wetting, adhesion and increasing penetration. In addition, stabilizers from the specified classes of chemical compounds increase the physical stability of herbicide Compositions by controlling the crystallization of pinoxaden, and also maintain the proper degree of dispersion, dilution and emulsification.

The herbicidal composition according to the present invention additionally comprises an antidote selected from cloquintoest-mexnia, mephene-diethyl and yuoxadifen-ethia.

The emulsifier according to the present invention is a combination of at least two surfactants selected from the group: ethoxylated or propoxyethylated alkyl phenol, polyoxyethylated alcohol or amine, ethoxylated hydroxypropyl ether, polyoxyethylated alcohol sulfate or phosphate or their salts, ethoxylated tristyrylphenol, ethoxylated or propoxylated tristyrylphenol sulfate or phosphate or their salts, alkyl sulfate or aryl sulfate or their salts, alkyl sulfonate or aryl sulfonate or condensed alkyl sulfonates or alkyl aryl sulfonates, lysulfonate or its salt, condensed alkyl aryl sulfonate, polycarboxylate salt, sulfosuccinate derivative, polymeric surfactants based on acrylates and their derivatives, tweens.

The liquid diluent according to the invention is an organic solvent, oil and/or water,

A hydrophilic solvent (in particular, petroleum products) or a hydrophilic solvent (in particular, substituted pyrrolidones, substituted amides of organic acids) is used as an organic solvent.

The following oils are used: mineral, vegetable oil and/or its esters, esters of unsaturated high molecular weight acids (methyl esters of oils, methylated derivative of vegetable oil).

The herbicide composition according to the invention may additionally contain an auxiliary substance, in particular, an antifoaming agent, a thickener, an antifreeze, a biocide, a UV stabilizer.

The herbicide composition according to the invention does not contain, in particular, such components as alpha/aromatic alcohols, tris-ester phosphates, cyclohexane, tetraphenylfurfuryl acetate, tetrahydrofurfuryl acetate.

The proposed herbicide composition can be made in the form of an emulsion concentrate (EC), an oil emulsion concentrate (OEC), a microemulsion (ME), a microemulsion concentrate (MEC), a nanoemulsion concentrate (NEC), or an oil-in-water emulsion (OIW).

The herbicide composition in the form of an emulsion concentrate or in the form of a microemulsion concentrate or in the form of a nanoemulsion concentrate, according to the invention, contains 0.5-40 wt.% shjoxadeina, 0.5-50 wt.% emulsifier, 0.5-50 wt.% stabilizer, 0-10 wt.% antidote, 0-10 wt.% auxiliary substance, the rest is an organic solvent.

The herbicidal composition in the form of a microemulsion or in the form of an "oil-in-water" emulsion, according to the invention, contains 0.5-40 wt.% pinoxaden, 0.5-50 wt.% emulsifier, 0.5-50 wt.% stabilizer, 0-10 wt.% antidote, 0-10 wt.% auxiliary substance, 5-30 wt.% organic solvent, 0-30 wt.% oil. The rest is water.

The herbicidal composition in the form of an oil concentrate emulsion, according to the invention, contains 0.5-40 wt.% pinoxaden, 0.5-50 wt.% emulsifier, 05-50 wt.% stabilizer, 0-10 wt.% antidote, 0-10 wt.% auxiliary substance, 5-30 wt.% organic solvent, the rest is oil.

Emulsion concentrate (EC) is a system obtained by dissolving the active substance and emulsifiers (surface-active substances) in a solvent that does not change with water. If necessary, EC also contains other auxiliary substances (antidote, stabilizer, antifoam, UV stabilizer, etc.).

Oil emulsion concentrate (OEC) is a special case of emulsion concentrate. Instead of solvent, natural and artificial oils are used. It is used after dilution with water.

Microemulsion (ME) is a thermodynamically stable homogeneous mixture of the active substance, hydrophobic solvent, water and emulsifier system (surfactants). If necessary, the microemulsion also contains other auxiliary substances (antidote, stabilizer, antifoam, UV stabilizer, etc.). The working emulsion based on ME can be either transparent or in the form of an opalescent emulsion.

Microemulsion concentrate (MEC) or namoemulsion concentrate (NEC) is a system containing an active substance, emulsifiers (11 AB), and a solvent, which forms a microemulsion when diluted with water.

An oil-in-water emulsion is a heterogeneous system in the form of droplets of an active substance solution in an organic solvent emulsified in water. This formulation also includes an emulsifier, stabilizer, antifreeze, thickener, biocide, UV stabilizer and/or antidote. Herbicide compositions in the form of the above-mentioned ready-made formulations (KE, MKE, ME, KME, KNE, EMV) do not delaminate during storage, are easily are mixed with water and form stable diluted emulsions, nano- or microemulsions used on agricultural vegetation. The resulting working emulsions remain homogeneous without stirring for up to 24 hours.

Another object of the invention is a method for protecting grain crops from weeds, which consists in diluting the herbicide composition according to the present invention with water to obtain a working emulsion, an effective amount of which is used to treat weeds or their growing areas. Spraying of crops is carried out in the post-emergence period for vegetative cereal weeds (from 2-3 leaves to the end of tillering) regardless of the phase of crop development. Weed growth stops after 2 days after spraying. Phytotoxic symptoms appear within 1-3 weeks after application. The described composition does not have a negative effect on cultivated plants.

The present herbicide composition is suitable for use on non-oat cereals, such as spring and winter wheat, spring and winter barley, rye, triticale. The patented composition has a herbicidal effect primarily on weed cereals, grasses, such as foxtail (geniculate, mouse-tailed, etc.), common broom, wild oats (species), ryegrass, foxtail (green, glaucous, whorled), millet (chicken, field weed), pigweed, couch grass, etc.

The following are examples illustrating the invention.

Example 1. Studied samples of herbicide composition

The following samples of the herbicide composition were tested (see Table G):

1 ~ concentrate emulsin (CE), containing stabilized bis(2-ethylhexyl)-phthalate;

2 - emulsion concentrate (EC), without stabilizer;

3 - oil concentrate emulsifier (OCE) containing ethyl carbonate stabilizer;

4 ■- microemulsion (ME) containing a combination of stabilizers dibutyl maleate and propylene carboxymethyl sulfoxide,

5 ~ microemulsion concentrate (MEC) containing dioctyl carbonate stabilizer; 6 •••• konsefat neutroemulsion (KNE) containing the stabilizer dibutyl dodecyl phthalate and ethylene carbonate;

7 - a composition in the form of oil-in-water (OIW) emulsions containing a combination of dibutylbenzene and dimethyl sulfoxide stabilizers.

Sample No. 1 was prepared as follows. The solvent was loaded into the reactor and the calculated amount of emulsifiers heated to a temperature of 45-50°C was added while stirring, then pinoksaden, antidote, and stabilizer were added. The resulting mass was stirred for 20-30 minutes until a homogeneous transparent liquid was obtained. Then it was filtered and the physicochemical parameters of the composition were determined.

Samples of emulsions K„№ 2-7 were obtained in a similar manner. Table №1 presents the compositions of the obtained samples of herbicidal agents.

Example 2. Evaluation of the stability of different types of formulations during storage

The stability of samples No. 1-7 during storage was assessed under various conditions using international methods (see Table 2).

To assess the possibility of storing the preparations for 2 years at temperatures from minus 15 to plus 35 °C, the following tests were carried out:

1. Accelerated storage test: the preparations were kept in a thermostat at plus 54°C for two weeks (CIPAC MT 46.3 method).

2. Frost resistance test: the preparations were kept in a thermostat at minus 15 °C for 10 days (method S1RAS MT 46.3, STR AC MT 39.2).

3. Heat aging test: the preparations were kept in a thermostat at plus 45 °C for 60 days (Surfactants and Specialties for Plant Production, section 2.2.5).

The results in Table 2 show that samples 1, 3-7 are stable during storage. The appearance of the preparations remained unchanged after storage: samples 1, 3-6 are light yellow, and sample 7 is white. The pinoxaden content in the samples under study remained virtually unchanged (the degree of pinoxaden decomposition does not exceed 3%). In turn, sample 2 (without stabilizer) changed color from light yellow to yellow-brown as a result of storage. and the pinoxaden content in it significantly reduced the axis (by 13-25% depending on the test). Thus, emulsion preparations based on pioxadeia do not lose their properties during long-term storage under conditions of high and low ambient temperatures. And working emulsions obtained after diluting the compositions with water are highly stable: homogeneous, no crystallization is observed, no cream or oil is formed, and are ready for use within 24 hours.

Example 3. Evaluation of the biological activity of a herbicide composition

The biological efficiency of various formulations of the patented herbicide composition was studied in comparison with the standard Axnal 50, EC (50 g/l pinoxaden, 12.5 g/l cloquintocet-mexil). The consumption rate of the preparation is 0.3 l/ha and 0.6 l/ha.

For conducting biological experiments, samples No. Nsl-7 were used.

According to GOST 32627-2014, agricultural crops (in this case, oats, a representative of iconic plants) were used as test plants to determine herbicidal activity in laboratory conditions to obtain more reliable results.

In the laboratory studies, Fasko-Universal soil was used as a substrate for growing test objects. Soil composition: high-moor peat, lowland peat, sand, limestone flour (dolomite), a complex of mineral fertilizers N 350 mg / kg, P3O3 400 mg / kg, K2O 500 mg / kg, soil acidity pH 6-7. To obtain the most uniform substrate, before filling the vessels, the soil was poured into a large container for sifting on sieves. After that, the vessels were filled. In the experiment, disposable paper cups with internal lamination, with a volume of 0.5 yt, were used as vessels. The same amount of soil was placed in each vessel (300 g of soil + 50 g for sprinkling seeds on top).

The seeds of the test plants were evenly spread on the compacted soil layer (300 g), taking into account their germination. For sowing, 6-8 seeds of the test oat plants of the Skakun variety were planted in each vessel. Subsequently, the seeds were sprinkled with soil (50 g), and the upper soil layer was compacted. After arranging the vessels on the shelves of the vegetation chamber, watering was carried out with 100 seeds in each vessel with tap water. Subsequently, the soil moisture in the experiment was maintained at one level by watering the vessels by weight 3 times a week.

The experiment was repeated five times.

The temperature and relative humidity were maintained at 24 °C and 70% during the day, and 20 ⁽ 'C and 80% at night, the length of the photoperiod was 16 hours, illumination at the level of 18,500 lux. The specified level of parameters was provided by a precision air conditioner SUAC0151, as well as 8 DRIZ 400W/220V lamps.

At the time of spraying, the oats were in the 2-4 leaf phase.

The treatments were carried out in a horizontal sprayer chamber (Poland) with a working fluid flow rate of 206 l/ha, at a pressure of 3 atm., nozzle capacity of 0.79 l/min, sprayer mode 5, spraying height 55 cm. Spraying speed 4.6 km/h. Droplet size F (fine). Distilled water was used to prepare working solutions.

The biological mass of plants was recorded on the 10th day after plant treatment. The above-ground part of plants from each vessel was cut and weighed on an OHAUS ScoutPro analytical scale of class 2 accuracy with a resolution of 0.01 g. The herbicidal action (biological effectiveness) of the variants was assessed by the percentage reduction in the above-ground biomass of treated plants relative to the control (without treatment), where 0 corresponds to the absence of damage, and 100 corresponds to the complete destruction of the test plant. The results of biological effectiveness (BE) are presented in Table 3.

Samples 1, 3-7 have high biological efficiency, which reaches 93% (at the consumption rate (Kb l/ra), The biological efficiency of the standard Azial 50 at the same consumption rate is 82%, and for sample 2 (without stabilizer) the value is even lower (BE - 77%),

Thus, the present invention has an improved herbicidal effect on annual cereal weeds (compared to preparations known from the prior art) due to the presence in the compositions of stabilizers selected from the class of organocarbonates and/or from the class of dicarboxylic acid esters.

Table 1

Таблица 3Compositions of herbicide compositions

Table 3

Comparative assessment of biological activity of herbicide composition samples on oats

Claims

Formula of Tobrstenium L Use of a compound selected from the class of organocarbonates and/or from the class of dicarboxylic acid esters as a stabilizer for a pinoxaden-based herbicide composition. 2. A stable herbicide composition comprising pinoxaden, a jugator, a liquid diluent, and at least one compound according to ND as a stabilizer. 3. A stable herbicidal composition according to claim 2, in which the stabilizer is contained in an amount that enhances the herbicidal activity of pinokeaden. 4. A stable herbicide composition according to n.2, which additionally includes an antidote selected from cloquintocetomequil, mefenpyr-diethyl, isoxadifen-egyl. 5. A stable herbicidal composition according to claim 2, characterized in that the emulsifier comprises a combination of at least two surfactants selected from the group: an ethoxylated or propoxylated alkylphenol, a polysulfone or diamine, an ethoxypropoxy block copolymer, a polysulfone or phosphate or their salts, an ethoxylated tristyrylphenol, an ethoxylated or propoxylated tristyrylphenol sulfate or phosphate or their salts, an alkyl sulfate or aryl sulfate or their salts, an alkyl sulfonate or aryl sulfonate or condensed alkyl sulfonates or alkyl aryl sulfate, a lignosulfonate or a salt thereof, a condensed alkyl aryl sulfonate, a polycarboxylate salt, a sulfosuccinate derivative, polymeric surfactants based on acrylates and their derivatives, tweens. 6. A stable herbicide composition according to n.2, characterized in that the liquid diluent is an organic solvent, oil and/or water. 7. A stable herbicide composition according to claim 6, characterized in that the organic solvent is selected from a hydrophobic or hydrophilic solvent. 8. A stable herbicidal composition according to claim 6, characterized in that the oil used is mineral, vegetable oil and/or its esters, esters of unsaturated high-molecular acids, in particular methyl esters of oils, a methylated derivative of vegetable oil. 9. A stable herbicidal composition according to claim 2, characterized in that the organocarbonate is selected from dimethyl carbonate, diethyl ether carbonate, ethylene carbonate, pronylene carbonate, diphenyl carbonate, and methyl ether carbonate. 10. A stable herbicidal composition according to claim 2, characterized in that the dicarboxylic acid ester is selected from dibutyl maleate, bis-(2-ethylhexyl) maleate, diisotridecyl adipate, bis-(2-ethylhexyl) adipate, bis-(2-ethylhexyl) sebacate, bis-(2-ethylhexyl) phthalate, dibutyl dodecyl phthalate, butyl dodecyl phthalate, didodecyl phthalate, dibutyl phthalate. 11. A stable herbicide composition according to item 2, characterized in that it additionally contains an auxiliary substance. 12. A stable herbicide composition according to item 11, characterized in that the auxiliary substance is selected from the group: defoamer, thickener, antifreeze, biocide, UV stabilizer. 13. A stable herbicide composition according to any one of paragraphs 2~12 in the form of an emulsion concentrate or in the form of a microemulsion concentrate or in the form of a nanoemulsion concentrate contains 0.5-40 wt.% pinokeaden, 0.5-50 wt.% emulsifier, 0.5-50 wt.% stabilizer, 0-10 wt.% antidote, 0-10 wt.% auxiliary substance, and an organic solvent - the rest. 14. A stable herbicide composition according to any of Inventions 2-12 in the form of a microemulsion or in the form of an oil-in-water emulsion contains 0.5-40 wt.% pinokeaden, 0.5-50 wt.% emulsifier, 0.5-50 wt.% stabilizer, 0-10 wt.% antidote, 0-10 wt.% auxiliary substance, 5-30 wt.% organic solvent, 0-30 wt.% oil, water is the rest. 15. A stable herbicide composition according to any one of claims 2-12 in the form of an oil emulsion concentrate contains 0.5-40 wt.% pinokeaden, 0.5-50 wt.% emulsifier, 0.5-50 wt.% stabilizer, 0-10 wt.% antidote, 0-10 wt.% auxiliary substance, 5-30 wt.% organic solvent, oil ~ the rest. Gb. A method for protecting grain crops from weeds, which consists in diluting the herbicide composition according to any of paragraphs 2-15 with water to obtain a working emulsion, an effective amount of which is used to treat weeds or their growing areas.