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WO2024218770A1 - Non-aqueous herbicidal formulations - Google Patents

Non-aqueous herbicidal formulations
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WO2024218770A1
WO2024218770A1PCT/IL2024/050379IL2024050379WWO2024218770A1WO 2024218770 A1WO2024218770 A1WO 2024218770A1IL 2024050379 WIL2024050379 WIL 2024050379WWO 2024218770 A1WO2024218770 A1WO 2024218770A1
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oil
effective amount
agrochemical formulation
aqueous agrochemical
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Lior ZISERMAN
Victoria ABRAMOV
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Adama Agan Ltd
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Adama Agan Ltd
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Abstract

The present invention provides an efficient non-aqueous herbicide formulations comprising a sulfonylamino-carbonyl triazolinone compound; at least one additional herbicide; one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety, and one or more vegetable oils or derivatives thereof; and also relates to methods for controlling undesired plant species by applying the said environment-friendly and physically stable formulation after dilution with water to the plant species.

Description

NON-AQUEOUS HERBICIDAL FORMULATIONS
RELATED APPLICATION/S
This application claims benefits of US Provisional Application Numbers 63/460,618 and 63/468,013 filed on April 20, 2023 and May 22, 2023, respectively; the entire content of which is hereby incorporated by reference herein. Throughout this application, various publications are cited. Disclosures of the documents and publications referred to herein are hereby incorporated in their entireties by references into this application.
FIELD OF INVENTION
The present invention relates to stable and efficient non-aqueous herbicide formulations comprising a sulfonylamino-carbonyl triazolinone compound; at least one additional herbicide; one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety, and one or more vegetable oils or derivatives thereof; and also relates to methods for controlling undesired plant species by applying the said environment-friendly and physically stable formulation after dilution with water to the plant species, by way of increasing physical and chemical stability of the herbicides within the formulation, thereby enhancing efficiency.
BACKGROUND OF INVENTION
Sulfonylamino-carbonyl triazolinone controls weeds through by inhibiting photosynthesis in the target plant. Sulfonylamino-carbonyl triazolinone disrupts membranes and inhibits photosynthesis in plants by blocking the ALS enzyme which is necessary for plant growth. Sulfonylamino-carbonyl triazolinone, such as Thiencarbazone-methyl is taken up into the plant through the roots. Plants that do happen to emerge from the soil, die after being exposed to sunlight. It also works on foliar contact causing rapid desiccation.
Sulfonylamino-carbonyl triazolinone compounds are herbicide active ingredients that control grass and broadleaf weeds. A sulfonylamino-carbonyl triazolinone compound such as Thiencarbazone methyl is a low-use-rate herbicide, with use limited to just about 20 gm per acre as a maximum seasonal use rate on corn, turf, and ornamentals. It is readily absorbed by both roots and leaves of susceptible weeds, but not apparent until several days after treatment. Symptoms that are present after treatment include chlorotic, crinkled, stunted, and distorted leaves, dead tissue, and gradual death.
Despite the benefits derived from the use of herbicides in general, and the sulfonylamino-carbonyl triazolinone herbicides in particular, in agriculture such as protection of crops and improved productivity, it is always a challenge to make judicious spreading and application of herbicide formulations which give both chemical stability as well as physical stability while diluting the formulation with water before applying to the field. The chemical stability as well as the physical stability of a sulfonylamino-carbonyl triazolinone herbicide in a formulation are observed to be matters of great concern when one or more active herbicides are attempted to be accommodated in a non-aqueous formulation. These makes the task of making suitable physically stable formulations of a sulfonylamino-carbonyl triazolinone specially without phase separation and sedimentation in combination with other compatible herbicides even more difficult. The compatible partners for sulfonylaminocarbonyl triazolinone compounds in herbicidal formulations in the prior art are inter alia a N- sulfonylurea herbicide and Chloroacetamide compounds.
Furthermore, there still exists serious concern over use of regular organic solvents in both aqueous and non-aqueous agricultural formulations due to their cost, flammability, and contribution to environmental pollution. Moreover, a sulfonylamino-carbonyl triazolinone compound, in combination with other compatible herbicides have further challenges with regard to chemical stability and physical stability especially with regard to sedimentation and phase separation, which makes the use of a suitable solvent mandatory to develop a stable formulation of sulfonylamino-carbonyl triazolinone herbicide.
There is therefore a need of an efficient herbicide formulation of a sulfonylaminocarbonyl triazolinone compound which typically broaden spectrum of control in an environmentally friendly medium without compromising chemical stability of the herbicide with enhancement of chemical and physical stability. Although many formulations of sulfonylamino-carbonyl triazolinone herbicides have been studied, the challenge remains to prepare a stable and efficient herbicide formulation system of a sulfonylamino-carbonyl triazolinone herbicide with another herbicides such as N-sulfonylurea and Chloroacetamide compound which provide good chemical stability and physical stability of the formulation. In the absence of efficient choice of co-formulants in the formulation, the application of formulation is said to be not well pronounced.
No prior art has ever addressed the problem of non-aqueous formulations of sulfonylamino-carbonyl triazolinone herbicide, either alone or in combination with other compatible herbicides, of chemical stability as well as physical stability against the phase separation and sedimentation. The meticulous choice of suitable solvents, co-formulants and rheology modifier in the formulation may result in surprising outcome to the efficiency of the said formulation.
In light of the above, there is endeavor in the present invention for novel stable and efficient non-aqueous formulations of a sulfonylamino-carbonyl triazolinone and another herbicide; suitable solvents and suitable rheology modifier, for increasing the desirable chemical stability as well as physical stability of the active substances and better effectiveness of the active substances on the target surface of plant, thereby enhancing overall efficiency of the formulation.
SUMMARY OF THE PRESENT SUBJECT MATTER
We have reasonably addressed the challenges as described above as a whole or in part by arriving at a novel stable non-aqueous agrochemical formulation with suitable rheology modifier, as defined below.
The present invention relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound, (b) an effective amount of at least one additional herbicide, wherein the additional herbicide is selected from a group comprising a N-sulfonylurea herbicide and a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention also relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound, which is Thiencarbazone methyl; (b) an effective amount of an N-sulfonylurea compound, which is Nicosulfuron; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention also relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound, which is Thiencarbazone methyl; (b) an effective amount of a Chloroacetamide compound, which is Dimethenamid; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention specifically relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention specifically relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention also relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention also relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention more specifically relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed silica with a specific surface area of at least 160 m2/g and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention more specifically relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed silica with a specific surface area of at least 160 m2/g and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention more specifically relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from a group comprising Aerosil 200 and Sipernat 22S; and (d) one or more vegetable oils or derivatives thereof.
The present invention more specifically relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more rheology modifiers selected from a group comprising Aerosil 200 and Sipernat 22S; and (d) one or more vegetable oils or derivatives thereof.
The present invention further relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of at least one additional herbicide, wherein the additional herbicide is selected from a group comprising a N-sulfonylurea herbicide and a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) an effective amount of one or more vegetable oils as solvents are selected from a group comprising rapeseed oil, soybean oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, kapok oil, papaya oil, camellia oil, rice bran oil or derivatives thereof.
The present invention also relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) an effective amount of the vegetable oil is rapeseed oil, which is a refined canola oil.
The present invention also relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) an effective amount of the vegetable oil is rapeseed oil, which is a refined canola oil.
The present invention also provides a method of treating a plant against undesired vegetation comprising applying non-aqueous agrochemical formulation disclosed herein, after dilution with water, to the target sites of the field, so as to treat the plant against undesired vegetation.
The present invention further provides use of the non-aqueous agrochemical formulation disclosed herein for controlling grassy and broadleaf weeds such as Digitaria ssp., Echinochloa ssp., Setaria ssp., Eriochloa ssp., Sorghum ssp., Lolium ssp., Panicum ssp, Poa ssp, Agropyron ssp, Amaranthus ssp., Abutilon ssp., Ambrosia ssp., Chenopodium SSP., Datura Ssp., Mercurialis ssp., Fallopia ssp., Portulaca ssp., Solanum ssp., Stellaria ssp., Thlaspi ssp, Viola ssp., Geranium ssp, Matricaria ssp, Polygonum ssp, Cirsium ssp, Xanthium ssp and Hibscus ssp on fields. The present invention also provides a process for the preparation of the non-aqueous agrochemical formulation disclosed herein from individual component parts.
The present invention further provides a method of controlling undesired vegetation comprising applying to the locus the non-aqueous agrochemical formulation disclosed herein. The present invention also provides a method for controlling grassy and broadleaf weeds comprising diluting with water non-aqueous agrochemical formulation disclosed herein, and applying the formulation to the locus of the plant.
The present invention provides a method of controlling undesired vegetation comprising applying to the locus the physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention also provides a method of controlling undesired vegetation comprising applying to the locus physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention provides a method of controlling undesired vegetation comprising applying to the locus the physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The present invention also provides a method of controlling undesired vegetation comprising applying to the locus physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
DETAILED DESCRIPTION OF THE PRESENT SUBJECT MATTER
Definitions
Prior to setting forth the present subject matter in detail, it may be helpful to provide definitions of certain terms to be used herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains.
Certain exemplary embodiments are described to provide an overall understanding of the principles of the invention disclosed herein. It is assumed that those skilled in the art will understand that the inventive features and methods specifically described herein and illustrated in the experimental section are non-limiting exemplary embodiments and that the scope of the present invention is defined solely by the claims. The features illustrated or described in one exemplary embodiment may be combined with the features of other embodiments. Such modifications and variations are intended to be included within the scope of the present invention.
Reference will now be made in detail to embodiments, which are illustrated in the subsequent paragraphs, wherein reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below to explain aspects of the present disclosure.
As used herein, the term "pesticide" in general broadly refers to an agent that can be used to control and/or kill a pest. The term is understood to include but is not limited to fungicides, insecticides, nematicides, herbicides, acaricides, parasiticides or other control agents. For chemical classes and applications, as well as specific compounds of each class, see "The Pesticide Manual Thirteenth Edition" (British Crop Protection Council, Hampshire, UK, 2003), as well as "The e-Pesticide Manual, Version 3" (British Crop Protection Council, Hampshire, UK, 2003-04), the contents of each of which are incorporated herein by reference in their entirety.
As used herein, the term "system" means but is not limited to an assemblage of active ingredients and/or acceptable coformulants for application either by simultaneous, contemporaneous and/or succession application. It also means a combination in any time of application of the individual components e.g. succession and/or in any physical form, e.g. blend, solution, suspension, dispersion, emulsion, alloy, or the like. "System" also may refer to combining and applying the active components and acceptable coformulants as one composition and/or formulating each of the active component in the mixture or combination as separated compositions and application at the same time or in separated applications at the same time or different times.
The admixture or individual components may be in any physical form, e.g. blend, solution, suspension, dispersion, emulsion, alloy, or the like.
As used herein, the term "agrochemically effective amount" refers to an amount of the active component that is commercially recommended for use to control weed. The commercially recommended amount for each active component, often specified as application rates of the commercial formulation, may be found on the label accompanying the commercial formulation. The commercially recommended application rates of the commercial formulation may vary depending on factors such as the plant species and the weeds to be controlled.
As used herein, the term "more effective" includes, but is not limited to, increasing efficacy of weed control, prolonging protection and reducing the amount of time needed to achieve a given level of weed control, prolonging the duration of protection against weeds after application and extending the protection period against weeds and/or reducing the amount of time needed to achieve a level of weed control compared to the herbicide formulation without suitable coformulants therein.
As used herein, the term "effective" when used in connection with any mixture or formulation system may be but is not limited to increase in controlling weeds, decrease time for effective controlling weeds, decrease the amount of the herbicide(s) which is required for effective controlling weed, extend the controlling effect of the individual herbicide active in the mixture in terms of type of crop and weed, prolong the time of controlling effect of the formulation. In particular, the term "effective" may refer to, increasing efficacy of weed control in untreated plant area, reducing the amount of time needed to achieve a given level of weed control, extending the protection period against weed and/or reducing the amount of time needed to achieve a level of weed control.
As used herein, the term "effective amount" refers to an amount of the individual components in an agrochemical formulation system or of the mixture which is critical for manufacturing effective formulation as well as for controlling harmful weed on crop plants and does not cause any significant damage to the treated crop plants.
As used herein, the term "agriculturally acceptable carrier" means carriers which are known and accepted in the art for the formation of compositions for agricultural or horticultural use.
As used herein, the term "coformulants" is defined as any substance that itself is not an active ingredient but is added to the composition or formulation such as additives, thickening agent, sticking agents, wetting agent, surfactants, anti-oxidation agent, antifoaming agents and thickeners.
As used herein, the term "Rheology modifiers" is defined as substances that alter the rheological properties of a material. In general, rheology modifiers are added to formulations to increase viscosity and to control the finished product's properties and characteristics in a desired manner.
The "specific surface area" of the silica based rheology modifier as referred herein, are measured by Brunauer-Emmett-Teller (BET) surface area analysis which is the multi-point measurement of an analyte's specific surface area (m2/g) through gas adsorption.
As used herein, the term "at least" means minimum value in a range of numbers. For example, "specific surface area of at least 160 m2/g" means the surface area is always 160 m2/g or above. As used herein the term "plant" or "crop" includes reference to agricultural crops including field crops (soybean, maize, wheat, rice, etc.), vegetable crops (potatoes, cabbages, etc.), fruits (peach, etc.), semi-perennial crops (sugarcane) and perennial crops (coffee and guava).
As used herein the term "plant" or "crop" includes reference to whole plants, plant organs (e.g. leaves, stems, twigs, roots, trunks, limbs, shoots, fruits etc.), plant cells, seedling or plant seeds. This term also encompasses plant crops such as fruits.
The term "plant" may also include the propagation material thereof, which may include all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers, which can be used for the multiplication of the plant. It may also include spores, corms, bulbs, rhizomes, sprouts, basal shoots, stolons, and buds and other parts of plants, including seedlings and young plants, which are to be transplanted after germination, rooting or after emergence from soil or any other kind of substrate, be it artificial or natural.
As used herein, the term "locus" includes not only areas where weeds may already be shown, but also areas where undesired vegetation have yet to show and also area under cultivation. Locus include but is not limited to soil and other plant growth medium.
As used herein, the terms "control" or "controlling" or "treating" refers but is not limited to preventing weeds, protecting plants from weeds, delaying the onset of undesired vegetation, and combating weeds.
The term "applying" or "application", as used herein, refers but is not limited to applying the compounds and compositions of the invention to the plant, to a site of weeds, to a potential site of weeds, which may require protection from undesired vegetation, or the environment around the habitat or potential habitat of the weeds. The application may be by methods described in the present invention such as by spraying, dipping, etc.
Throughout the application, descriptions of various embodiments the term "comprising" is used; however, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language "consisting essentially of" or "consisting of." The term "a" or "an" as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms "a," "an", "one or more" or "at least one" can be used interchangeably in this application.
Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
In this regard, use of the term "about" herein specifically includes ±10% from the indicated values in the range. In addition, the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. Expressions such as "at least one of," when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. I n this regard, used of the term "about" herein specifically includes ±10% from the indicated values in the range. In addition, the endpoints of all ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include all intermediate points and ranges.
Herbicide formulations
The formulation of the present invention comprises a non-aqueous solvent system. The term "non-aqueous solvent system" means that one or more solvents other than water are used as the liquid carrier in the liquid composition. This does not mean to say that the solvent system must necessarily be completely free of water. Trace amounts of water may be present in the components that are used to prepare the non-aqueous solvent system. For instance, trace amounts of water may be introduced into the solvent system by organic solvents, surfactants or salts that are used to prepare the liquid herbicidal composition. While the term "non-aqueous solvent system" can be taken to mean that the liquid composition comprises water in an amount of 5 wt.% or less of the composition, preferably 3 wt.% or less, more preferably 2 wt.% and most preferably 1 wt.% or less.
There is always a challenge to formulate an herbicide formulation comprising a sulfonylamino-carbonyl triazolinone compound and at least one additional herbicide having a suitable rheology modifier, for increasing the desirable chemical stability as well as physical stability, resulting enhancement of overall efficiency of the formulation.
In this endeavor, the inventors have attempted several options to make a stable and efficient formulation system by judiciously choosing conglomerate of coformulants which may result in creating a conducive environment for the active ingredients to have desirable chemical stability as well as physical stability in the formulation without any undesirable sedimentation or phase separations. Several combinations of inert components or coformulants along with viscosity modifiers were tried, and eventually the desired results were arrived at.
Many commercially available rheology modifiers were tried in the formulation to achieve desirable chemical stability as well as physical stability in the formulation without any undesirable sedimentation or phase separations. The silica based rheology modifiers which were experimented upon, include Tixosil 38A, Aerosil R805, Aerosil R972, Aerosil 200 and Sipernat 22S. During the extensive research it has been found out that the physical characteristics, such as specific surface area and the structural moieties of the rheology modifiers played a decisive role in bringing about desirable chemical stability as well as physical stability in the formulation without any undesirable sedimentation or phase separations in the formulation.
After several experimentations, it is surprisingly found that in the non-aqueous formulation of mixtures of active substances, the chemical stability of a sulfonylaminocarbonyl triazolinone (e.g. Thiencarbazone methyl) and an N-sulfonylurea compound (e.g. Nicosulfuron) in the formulation and their performance (e.g. physical stability) was significantly improved by incorporation of one or more rheology modifiers, such as Aerosil 200 and Sipernat 22S selected from a group comprising fumed and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety.
Furthermore, after several experimentations, it is also surprisingly found that in the non-aqueous formulation of mixtures of active substances, the chemical stability of a sulfonylamino-carbonyl triazolinone (e.g. Thiencarbazone methyl) and a Chloroacetamide compound (e.g. Dimethenamid) in the formulation and their performance (e.g. physical stability) was significantly improved by incorporation of one or more rheology modifiers, such as Aerosil 200 and Sipernat 22S selected from a group comprising fumed and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety.
In most cases in the prior arts, the non-aqueous formulations such as Oil Dispersion (OD) formulations contain surfactants such as fatty alcohol ethoxylate alkyl ether, calcium dodecylbenzenesulphonates, Docusate sodium, and Castor oil, ethoxylated, oleate based (e.g. Alkamuls VO 2003). It is observed during the course of experimentations that these classic methodologies did not work in maintaining the chemical and physical of the formulations. However, the meticulous use of these rheology modifiers (either as fumed silica or precipitated silica or both) with a certain range of specific surface area, helping in physical stability as well as chemical stability in the invented formulation is very unusual.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of at least one additional herbicide, wherein the additional herbicide is selected from a group comprising a N-sulfonylurea herbicide and a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In another embodiment, the present invention provides a physically stable nonaqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylaminocarbonyl triazolinone compound, which is Thiencarbazone methyl; (b) an effective amount of an N-sulfonylurea compound, which is Nicosulfuron; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In a further embodiment, the present invention provides a physically stable nonaqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In another embodiment, the present invention provides a physically stable nonaqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylaminocarbonyl triazolinone compound, which is Thiencarbazone methyl; (b) an effective amount of a Chloroacetamide compound, which is Dimethenamid; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In a further embodiment, the present invention provides a physically stable nonaqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed silica with a specific surface area of at least 160 m2/g and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from a group comprising Aerosil 200 and Sipernat 22S; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more rheology modifiers selected from a group comprising fumed silica with a specific surface area of at least 160 m2/g and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more rheology modifiers selected from a group comprising Aerosil 200 and Sipernat 22S; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of at least one additional herbicide, wherein the additional herbicide is selected from a group comprising a N-sulfonylurea herbicide and a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) an effective amount of one or more vegetable oils as solvents are selected from a group comprising rapeseed oil, soybean oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil kapok oil, papaya oil, camellia oil, rice bran oil or derivatives thereof.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) an effective amount of the vegetable oil is rapeseed oil, which is a refined canola oil.
In an embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) an effective amount of the vegetable oil is rapeseed oil, which is a refined canola oil.
In a further embodiment, the present invention provides the said stable non-aqueous agrochemical formulation additionally comprises a safener, wherein the safener is selected from a group comprising Cyprosulfamide and Mefenpyr-diethyl.
In an embodiment, the present invention provides the said stable non-aqueous agrochemical formulation additionally comprises a safener, which is Cyprosulfamide.
In a further embodiment, the present invention provides the said stable non-aqueous agrochemical formulation additionally comprises one or more additives comprising an emulsifier. In an embodiment, the present invention provides the said stable non-aqueous agrochemical formulation additionally comprises emulsifier, wherein the emulsifier is polyethylene glycol ester of fatty acid.
In an embodiment, the present invention provides a method of treating a plant against undesired vegetation comprising applying non-aqueous agrochemical formulation disclosed herein, after dilution with water, to the target sites of the field, so as to treat the plant against undesired vegetation.
In an embodiment, the present invention provides a use of the non-aqueous agrochemical formulation disclosed herein for controlling grassy and broadleaf weeds such as Digitaria ssp., Echinochloa ssp., Setaria ssp., Eriochloa ssp., Sorghum ssp., Lolium ssp., Panicum ssp, Poa ssp, Agropyron ssp, Amaranthus ssp., Abutilon ssp., Ambrosia ssp., Chenopodium SSP., Datura Ssp., Mercurialis ssp., Fallopia ssp., Portulaca ssp., Solanum ssp., Stellaria ssp., Thlaspi ssp, Viola ssp., Geranium ssp, Matricaria ssp, Polygonum ssp, Cirsium ssp, Xanthium ssp and Hibscus ssp on fields, more particularly in corn (maize) field.
In an embodiment, the present invention provides a process for the preparation of the non-aqueous agrochemical formulation disclosed herein from individual component parts.
In an embodiment, the present invention provides a method of controlling undesired vegetation comprising applying to the locus the non-aqueous agrochemical formulation disclosed herein. The present invention also provides a method for controlling grassy and broadleaf weeds comprising diluting with water non-aqueous agrochemical formulation disclosed herein, and applying the formulation to the locus of the plant.
In an embodiment, the present invention provides a method of controlling undesired vegetation comprising applying to the locus the physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof. In an embodiment, the present invention provides a method of controlling undesired vegetation comprising applying to the locus physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Nicosulfuron; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a method of controlling undesired vegetation comprising applying to the locus the physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a Sulfonylamino-carbonyl triazolinone compound; (b) an effective amount of a Chloroacetamide compound; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
In an embodiment, the present invention provides a method of controlling undesired vegetation comprising applying to the locus physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of Thiencarbazone methyl; (b) an effective amount of Dimethenamid; (c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and (d) one or more vegetable oils or derivatives thereof.
The following examples illustrate the practice of the present invention in some of its embodiments but should not be construed as limiting the scope of the invention. Other embodiments will be apparent to one skilled in the art from consideration of the specification and examples. It is intended that the specification, including the examples, is considered exemplary only without limiting the scope and spirit of the invention.
PREPARATORY EXAMPLES:
Some exemplary embodiments of the formulations of the present invention* along with the comparative formulations# are illustrated in the following tables with their respective Physico-chemical data:
Formulation type 1: Nicosulfuron 30 + Thiencarbazone 15 + Cyprosulfamide 22.5 OD
Figure imgf000021_0001
1TS54 2W = accelerated shelf life incubation method at 54°C for 2 weeks
2TS408W = accelerated shelf life incubation method at 40°C for 8 weeks
3RT = Ambient temperature
Formulation type 2*: Thiencarbazone 15+ Dimethenamid-p 250 + Cyprosulfamide 22.5 OD
Formulation type 3**: Thiencarbazone 30+ Dimethenamid-p 500 + Cyprosulfamide 45 OD
Figure imgf000022_0001
1TS54 2W - accelerated shelf life incubation method at 54°C for 2 weeks 2TS408W = accelerated shelf life incubation method at 40°C for 8 weeks 3RT = Ambient temperature
It has been found from the data of some exemplary recipes of the present invention, when compared with the other comparative recipes that the formulations of the present invention with a rheology modifier, either a fumed silica with a specific surface area of between 175-225 m2/g (Aerosil 200) or a precipitated silica with a specific surface area of between 160-210 m2/g (Sipernat 22S) exhibited enhanced physical stability (significantly consistent low amount of separations) as well as chemical stability of the active ingredients compared to the formulations where any of them is absent.

Claims

WHAT IS CLAIMED IS:
1. A physically stable non-aqueous agrochemical formulation comprising:
(a) an effective amount of a sulfonylamino-carbonyl triazolinone compound;
(b) an effective amount of at least one additional herbicide, wherein the additional herbicide is selected from a group comprising a N-sulfonylurea compound and a Chloroacetamide compound;
(c) an effective amount of one or more silica based rheology modifier with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety; and
(d) one or more vegetable oils or derivatives thereof.
2. The non-aqueous agrochemical formulation of claim 1, wherein the sulfonylamino-carbonyl triazolinone compound is Thiencarbazone methyl; and the additional herbicide is Nicosulfuron.
3. The non-aqueous agrochemical formulation of claim 1, wherein the sulfonylamino-carbonyl triazolinone compound is Thiencarbazone methyl; and the additional herbicide is Dimethenamid.
4. The non-aqueous agrochemical formulation of any one of claims 1-3, wherein one or more rheology modifiers are selected from a group comprising fumed and precipitated silica with a specific surface area of at least 160 m2/g, wherein the silica contains no hydrophobic moiety.
5. The non-aqueous agrochemical formulation of claim 4, wherein one or more rheology modifiers selected from a group comprising fumed silica with a specific surface area of between 175-225 m2/g and precipitated silica with a specific surface area of between 160- 210 m2/g.
6. The non-aqueous agrochemical formulation of claim 5, wherein one or more rheology modifiers selected from a group comprising Aerosil 200 and Sipernat 22S.
7. The non-aqueous agrochemical formulation of any one of claims 1-6 further comprising a safener, wherein the safener is selected from a group comprising Cyprosulfamide and Mefenpyr-diethyl.
8. The non-aqueous agrochemical formulation of claim 7, wherein the safener is Cyprosulfamide.
9. The non-aqueous agrochemical formulation of any one of claims 1-8 further comprising one or more additives comprising an emulsifier.
10. The non-aqueous agrochemical formulation of claim 9, wherein the emulsifier is polyethylene glycol ester of fatty acid.
11. The non-aqueous agrochemical formulation of any one of claims 1-10, wherein vegetable oils or derivatives thereof, are selected from a group comprising rapeseed oil, soybean oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, kapok oil, papaya oil, camellia oil, rice bran oil or derivatives thereof.
12. The non-aqueous agrochemical formulation of claim 11, wherein vegetable oil is a rapeseed oil, which is a refined canola oil.
13. A method of treating a plant against undesired weeds comprising applying herbicide formulation system of any one of claims 1-12, after dilution with water, to the target sites of the field, so as to treat the plant against undesired weeds.
14. The method of claim 13, wherein the undesired weeds are selected from a group comprising grassy and broadleaf weeds.
15. The method of any one of claims 13-14, wherein the undesired weeds are selected from a group comprising Digitaria ssp., Echinochloa ssp., Setaria ssp., Eriochloa ssp., Sorghum ssp., Lolium ssp., Panicum ssp, Poa ssp, Agropyron ssp, Amaranthus ssp., Abutilon ssp., Ambrosia ssp., Chenopodium SSP., Datura Ssp., Mercurialis ssp., Fallopia ssp., Portulaca ssp., Solanum ssp., Stellaria ssp., Thlaspi ssp, Viola ssp., Geranium ssp, Matricaria ssp, Polygonum ssp, Cirsium ssp, Xanthium ssp and Hibscus ssp.
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Citations (4)

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WO2013181090A2 (en)*2012-05-292013-12-05Bayer Cropscience LpMethods and compositions for controlling weed infestation and improving grass quality
WO2021152391A1 (en)*2020-01-292021-08-05Fmc Agricultural Caribe Industries Ltd.Liquid sulfonylurea compositions
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