CN121057505A - Nonaqueous herbicidal formulations - Google Patents

Abstract

The present invention provides a highly effective non-aqueous herbicide formulation comprising a sulfonylamino-carbonyl triazolinone compound, at least one additional herbicide, one or more rheology modifiers based on silica having a specific surface area of at least 160 m ²/g, wherein the silica is free of hydrophobic moieties, and one or more vegetable oils or derivatives thereof, and also relates to methods for controlling undesirable plant species by applying the environmentally friendly and physically stable formulation to plant species after dilution with water.

Description

Non-aqueous herbicides

Related applications

This application claims the benefit of U.S. Provisional Applications Nos. 63/460,618 and 63/468,013, filed on April 20, 2023, and May 22, 2023, respectively; the entire contents of which are hereby incorporated herein by reference. Various publications are cited throughout this application. The disclosures of the documents and publications cited herein are hereby incorporated in their entirety.

Technical Field

This invention relates to stable and efficient non-aqueous herbicide formulations comprising a sulfonylamino-carbonyltriazolinone compound; at least one additional herbicide; one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and one or more vegetable oils or derivatives thereof; and also relates to methods for controlling unwanted plant species, which improve efficiency by applying the environmentally friendly and physically stable formulation to the plant species after dilution with water, thereby increasing the physical and chemical stability of the herbicide within the formulation.

Background Technology

Sulfonylamino-carbonyltriazolones are used to control weeds by inhibiting photosynthesis in target plants. They work by blocking ALS enzymes essential for plant growth, disrupting membranes and inhibiting photosynthesis. Sulfonylamino-carbonyltriazolones (such as thiazosulfonate) are absorbed by plants through the roots. Plants emerging from the soil die upon exposure to sunlight. They also act on leaf surfaces, causing rapid drying.

Sulfonylamino-carbonyltriazolinone compounds are herbicide active ingredients used to control grassy and broadleaf weeds. Sulfonylamino-carbonyltriazolinone compounds (such as thiamethoxam) are low-application herbicides, with the highest seasonal application rate on corn, turf, and ornamental plants, limited to only about 20 gm/acre. They are readily absorbed by the roots and leaves of susceptible weeds, but symptoms do not appear until several days after treatment. Symptoms following treatment include yellowing, wrinkling, stunted and deformed leaves, tissue death, and gradual death.

While the benefits of using general herbicides, and especially sulfonylamino-carbonyltriazolone herbicides, in agriculture (such as crop protection and increased productivity) have been observed, the careful application and dispensing of herbicide formulations to ensure chemical and physical stability when diluted with water before application to the field remains a challenge. The chemical and physical stability of sulfonylamino-carbonyltriazolone herbicides in formulations is a significant concern when attempting to incorporate one or more active herbicides into non-aqueous formulations. This makes the task of manufacturing suitable, physically stable formulations of sulfonylamino-carbonyltriazolones, particularly those that do not undergo phase separation and sedimentation when combined with other compatible herbicides, even more difficult. In the prior art, compatibility of sulfonylamino-carbonyltriazolone compounds in herbicide formulations, particularly N-sulfonylurea herbicides and chloroacetamide compounds, is a key concern.

Furthermore, the use of conventional organic solvents in aqueous and non-aqueous agricultural formulations remains a serious concern due to their cost, flammability, and environmental impact. In addition, the combination of sulfonylamino-carbonyltriazolone compounds with other compatible herbicides presents further challenges in terms of chemical and physical stability, particularly in terms of sedimentation and phase separation. Therefore, suitable solvents must be used to develop stable formulations of sulfonylamino-carbonyltriazolone herbicides.

Therefore, there is a need for highly efficient herbicide formulations of sulfonylamino-carbonyltriazolinone compounds that typically broaden the control spectrum in environmentally friendly media without compromising the chemical stability of the herbicide, while simultaneously enhancing its chemical and physical stability. Although many formulations of sulfonylamino-carbonyltriazolinone herbicides have been studied, the preparation of stable and highly efficient herbicide formulation systems of sulfonylamino-carbonyltriazolinone herbicides with another herbicide (such as N-sulfonylureas and chloroacetamide compounds) remains a challenge, as these herbicides provide good chemical and physical stability to the formulation. In the absence of highly efficient options for co-formulant in the formulation, the application effect of the formulation is believed to be not very significant.

Existing technologies have never solved the problems of chemical stability and physical stability against phase separation and sedimentation in non-aqueous formulations of sulfonylamino-carbonyltriazolinone herbicides (alone or in combination with other compatible herbicides). Careful selection of appropriate solvents, formulation adjuvants, and rheology modifiers in the formulation may yield unexpectedly high efficiency results.

In view of the above, the present invention is dedicated to novel, stable and efficient non-aqueous formulations of sulfonylamino-carbonyltriazolinone and another herbicide; suitable solvents and suitable rheology modifiers are used to increase the desired chemical and physical stability of the active substance and its better effectiveness on the target plant surface, thereby enhancing the overall efficiency of the formulation.

Summary of the Invention

We have reasonably addressed, in whole or in part, the challenges described above by obtaining novel, stable, non-aqueous agrochemical formulations (as defined below) with suitable rheology modifiers.

This invention relates to a physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of at least one additional herbicide selected from the group consisting of N-sulfonylurea herbicides and chloroacetamide compounds; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; 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-carbonyltriazolinone compound, which is thiazosulfonate; (b) an effective amount of an N-sulfonylurea compound, which is nicosulfonate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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-carbonyltriazolinone compound, which is thiamethoxam; (b) an effective amount of a chloroacetamide compound, which is dimethylphenidate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; 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 thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) one or more vegetable oils or derivatives thereof.

More specifically, this invention relates to a physically stable, non-aqueous agrochemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica having a specific surface area of at least 160 ^m² /g and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

More specifically, this invention relates to a physically stable, non-aqueous agrochemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica having a specific surface area of at least 160 ^m² /g and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) one or more vegetable oils or derivatives thereof.

More specifically, this invention relates to a physically stable, non-aqueous agrochemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from the group consisting of Aerosil 200 and Sipernat 22S; and (d) one or more vegetable oils or derivatives thereof.

More specifically, the present invention relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more rheology modifiers selected from the 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-carbonyltriazolinone compound; (b) an effective amount of at least one additional herbicide selected from the group consisting of N-sulfonylurea herbicides and chloroacetamide compounds; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) an effective amount of one or more vegetable oils as a solvent selected from the group consisting of rapeseed oil, soybean oil, olive oil, castor oil, sunflower 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-carbonyltriazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) an effective amount of a vegetable oil, which is rapeseed oil, specifically refined low-erucic acid rapeseed oil.

The present invention also relates to a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of a chloroacetamide compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) an effective amount of a vegetable oil, which is rapeseed oil, specifically refined low-erucic acid rapeseed oil.

The present invention also provides a method for treating plants against undesirable vegetation, the method comprising applying a non-aqueous agricultural chemical formulation disclosed herein, after dilution with water, to a target site in a field to treat the plants against undesirable vegetation.

This invention further provides the use of the non-aqueous agricultural chemical formulations disclosed herein for controlling gramineous and broadleaf weeds in fields, such as species of the genera *Digitaria*, *Echinochloa*, *Setaria*, *Eriochloa*, *Sorghum*, *Lolium*, *Panicum*, *Poa*, *Agropyron*, *Amaranthus*, *Abutilon*, *Ambrosia*, *Chenopodium*, *Datura*, and *Mercurialis*. ssp.), species of the genera *Fallopia*, *Portulaca*, *Solanum*, *Stellaria*, *Thlaspi*, *Viola*, *Geranium*, *Matricaria*, *Polygonum*, *Cirsium*, *Xanthium*, and *Hibscus*.

The present invention also provides a method for preparing the non-aqueous agrochemical formulation disclosed herein from a single component portion.

The present invention further provides a method for controlling undesirable vegetation, the method comprising applying the non-aqueous agricultural chemical formulation disclosed herein to a site. The present invention also provides a method for controlling gramineous weeds and broadleaf weeds, the method comprising diluting the non-aqueous agricultural chemical formulation disclosed herein with water and applying the formulation to the site where the plants are located.

The present invention provides a method for controlling undesirable vegetation, the method comprising applying a physically stable, non-aqueous agricultural chemical formulation to a site, the physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

The present invention also provides a method for controlling undesirable vegetation, the method comprising applying a physically stable, non-aqueous agricultural chemical formulation to a site, the physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

The present invention provides a method for controlling undesirable vegetation, the method comprising applying a physically stable, non-aqueous agricultural chemical formulation to a site, the physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of a chloroacetamide compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

The present invention also provides a method for controlling undesirable vegetation, the method comprising applying a physically stable non-aqueous agrochemical formulation to a site, the physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

Detailed Implementation

definition

Before detailing the subject matter of this invention, it may be helpful to provide definitions for certain terms used herein. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this subject matter pertains.

Certain exemplary embodiments are described to provide a general 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 invention is defined only by the claims. Features illustrated or described in one exemplary embodiment may be combined with features of other embodiments. Such modifications and variations are intended to be included within the scope of the invention.

Reference will now be made in detail to the embodiments described in the following paragraphs, wherein reference numerals throughout refer to similar elements. In this respect, embodiments of the invention may take different forms and should not be construed as limiting to the description set forth herein. Therefore, only embodiments are described below to explain various aspects of this disclosure.

As used herein, the term “pesticide” generally refers in a broad sense to any agent that can be used to control and/or kill pests. This term is understood to include, but is not limited to, fungicides, insecticides, nematicides, herbicides, acaricides, parasiteicides, or other control agents. For chemical categories and applications, and specific compounds in each category, see “The Pesticide Manual Thirteenth Edition” (British Crop Protection Council, Hampshire, UK, 2003) and “The e-Pesticide Manual, Version 3” (British Crop Protection Council, Hampshire, UK, 2003-04), each of which is incorporated herein by reference in its entirety.

As used herein, the term "system" means, but is not limited to, a collection of active ingredients and/or acceptable formulation adjuvants intended for simultaneous, concurrent, and/or sequential application. It also means a combination of individual components at any time of application (e.g., sequentially), and/or a combination in any physical form (e.g., blends, solutions, suspensions, dispersions, emulsions, alloys, etc.). "System" can also refer to the combination and application of an active ingredient and acceptable formulation adjuvants as a single composition and/or the formulation of each active ingredient in a mixture or combination as a separate composition for simultaneous or sequential application at the same or different times in separate applications.

Blends or individual components can be in any physical form, such as blends, solutions, suspensions, dispersions, emulsions, and admixtures.

As used herein, the term "agrochemically effective amount" refers to the amount of an active ingredient commercially recommended for weed control. The commercially recommended amount (usually specified as the application rate for a commercial formulation) for each active ingredient can be found on the label accompanying the commercial formulation. The commercially recommended application rate for a commercial formulation can vary depending on factors such as the plant species and the weed to be controlled.

As used herein, the term “more effective” includes, but is not limited to, increasing weed control efficacy, extending protection and reducing the amount of time required to achieve a given weed control level compared to herbicide formulations that do not contain suitable formulation adjuvants, extending the duration of post-application weed protection and extending the period of weed protection, and/or reducing the amount of time required to achieve weed control levels.

As used herein, when used with any mixture or formulation system, the term "effective" can mean, but is not limited to, increasing weed control, reducing the time required for effective weed control, reducing the amount of one or more herbicides required for effective weed control, prolonging the control effect of a single herbicide active in a mixture on crops and weed types, and prolonging the time of action of a control formulation. In particular, the term "effective" can mean increasing weed control efficacy in untreated vegetated areas, reducing the amount of time required to achieve a given weed control level, prolonging the period of protection against weeds, and/or reducing the amount of time required to achieve a weed control level.

As used herein, the term "effective amount" refers to the amount of a single component or mixture in an agrochemical formulation system that is essential for the manufacture of an effective formulation and for the control of weeds harmful to crop plants, without causing any significant damage to the treated crop plants.

As used herein, the term “agriculturally acceptable carrier” means a carrier known and accepted in the art for forming compositions for agricultural or horticultural purposes.

As used herein, the term "formulation aid" is defined as any substance that is not an active ingredient but is added to a composition or formulation, such as additives, thickeners, adhesives, wetting agents, surfactants, antioxidants, defoamers, and thickeners.

As used herein, the term "rheology modifier" is defined as a substance that alters the rheological properties of a material. Typically, rheology modifiers are added to formulations to increase viscosity and control the properties and characteristics of the finished product in a desired manner.

As mentioned in this article, the "specific surface area" of silica-based rheology modifiers was measured by Brunauer-Emmett-Teller (BET) surface area analysis, which is a multi-point measurement of the specific surface area ( ^m² /g) of the analyte by gas adsorption.

As used herein, the term “at least” refers to the minimum value within a numerical range. For example, “at least 160 ^m² /g specific surface area” means that the surface area is always 160 ^m² /g or higher.

As used in this article, the terms “plant” or “crop” include references to agricultural crops, including field crops (soybeans, corn, wheat, rice, etc.), vegetable crops (potatoes, cabbage, etc.), fruit crops (peaches, etc.), semi-perennial crops (sugarcane), and perennial crops (coffee and guava).

As used herein, the terms “plant” or “crop” include references to whole plants, plant organs (e.g., leaves, stems, twigs, roots, trunks, branches, buds, fruits, etc.), plant cells, seedlings, or plant seeds. This term also includes plant crops such as fruit crops.

The term "plant" may also include its propagation material, which may include all reproductive parts of the plant (such as seeds) and nutrient plant material (such as cuttings and tubers) that can be used to propagate the plant. The term may also include spores, bulbs, tubers, rhizomes, new shoots, basal branches, stolons, and buds, as well as other parts of the plant (including seedlings and young plants) that will be transplanted after germination, rooting, or after emergence from soil or any other kind of substrate (artificial or natural).

As used herein, the term "site" includes not only areas that may already be infested with weeds, but also areas that have not yet developed undesirable vegetation, as well as areas that are being cultivated. Sites include, but are not limited to, soil and other plant growth media.

As used in this article, the terms “control/controlling” or “treatment” refer to, but are not limited to, preventing weeds, protecting plants from weed infestation, delaying the appearance of unwanted vegetation, and combating weeds.

As used herein, the term "applying/application" means, but is not limited to, applying the compounds and compositions of the present invention to a site of a plant or weed, a potential site of a weed (a site that may require protection from unwanted vegetation), or the environment surrounding a weed habitat or potential habitat. This application can be carried out by the methods described in the present invention, such as by spraying, dipping, etc.

Throughout this application, the description of various embodiments uses the term "comprising"; however, those skilled in the art will understand that in certain specific cases, the language "substantially consisting of" or "consisting of" may be used alternatively to describe embodiments. Unless otherwise specifically stated, the term "a/an" as used herein includes both singular and plural forms. Therefore, the terms "a/an," "one or more," or "at least one" are used interchangeably in this application.

Therefore, unless otherwise stated, the numerical parameters listed in the following description and appended claims are approximate values and may vary depending on the desired characteristics sought to be obtained. At a minimum, each numerical parameter should be interpreted according to the number of significant figures reported and by applying common rounding techniques.

In this regard, the use of the term "about" in this document specifically includes ±10% of the indicated value within the range. Furthermore, the endpoints of all ranges relating to the same component or property herein include endpoints that 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 listed related items. When expressions such as "at least one/of..." precede the list of elements, they modify the entire list of elements and not individual elements within the list.

For the purpose of better understanding this teaching and by no means limiting its scope, each numerical parameter should be interpreted according to the number of significant figures reported and by applying common rounding techniques. In this regard, the term "about" as used herein specifically includes ±10% of the indicated value within the range. Furthermore, the endpoints of all ranges relating to the same component or property herein include endpoints that are independently combinable, and include all intermediate points and ranges.

Herbicide formulations

The formulations of this invention comprise a non-aqueous solvent system. The term "non-aqueous solvent system" means that one or more solvents other than water are used as a liquid carrier in the liquid composition. This does not mean that the solvent system must be completely water-free. Trace amounts of water may be present in the components used to prepare the non-aqueous solvent system. For example, trace amounts of water may be introduced into the solvent system through organic solvents, surfactants, or salts used to prepare the liquid herbicidal composition. The term "non-aqueous solvent system" can be understood to mean that the liquid composition contains 5 wt.% or less, preferably 3 wt.% or less, more preferably 2 wt.% and most preferably 1 wt.% or less of water in the composition.

There is always a challenge in formulating a herbicide formulation containing a sulfonylamino-carbonyltriazolinone compound and at least one other herbicide with a suitable rheology modifier to improve the desired chemical and physical stability, thereby leading to enhanced overall efficiency of the formulation.

In this endeavor, the inventors explored various options to prepare stable and efficient formulation systems by carefully selecting polymers of formulation aids. This resulted in creating a favorable environment for the active ingredient, enabling it to exhibit the desired chemical and physical stability in the formulation without any undesirable sedimentation or phase separation. Multiple combinations of inert components or formulation aids with viscosity modifiers were explored, ultimately achieving the desired results.

Numerous commercially available rheology modifiers were explored in formulations to achieve the desired chemical and physical stability without any undesirable sedimentation or phase separation. Experimental silica-based rheology modifiers included Tixosil 38A, Aerosil R805, Aerosil R972, Aerosil 200, and Sipernat 22S. During extensive research, physical characteristics, such as the specific surface area and structural moiety of the rheology modifier, have been found to play a decisive role in achieving the desired chemical and physical stability in formulations without any undesirable sedimentation or phase separation.

Following several experiments, it was unexpectedly found that the chemical stability and properties (e.g., physical stability) of sulfonylamino-carbonyltriazolinones (e.g., thiazosulfonyl) and N-sulfonylurea compounds (e.g., nicosulfonyl) in non-aqueous formulations of mixtures of active substances were significantly improved by incorporation with one or more rheology modifiers (e.g., Aerosil 200 and Sipernat 22S) selected from the group consisting of fumed silica and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica does not contain a hydrophobic portion.

Furthermore, following several experiments, it was unexpectedly found that the chemical stability and properties (e.g., physical stability) of sulfonylamino-carbonyltriazolinones (e.g., thiazosulfonyl) and chloroacetamide compounds (e.g., dimethylphenidate) in non-aqueous formulations of mixtures of active substances were significantly improved by incorporation with one or more rheology modifiers (e.g., Aerosil 200 and Sipernat 22S), selected from the group consisting of fumed silica and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica does not contain a hydrophobic portion.

In most cases in the prior art, non-aqueous formulations such as oil dispersions (OD) contain surfactants such as fatty alcohol ethoxylated alkyl ethers, calcium dodecylbenzenesulfonate, sodium docusate, and castor oil (ethoxylated, oleate-based (e.g., Alkamuls VO 2003)). During experiments, it was observed that these classical methods were ineffective in maintaining the chemical and physical properties of the formulations. However, the rigorous use of rheology modifiers with a defined range of specific surface areas (as fumed silica or precipitated silica, or both) contributes significantly to the physical and chemical stability of the formulations of this invention.

In embodiments, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of at least one additional herbicide selected from the group consisting of N-sulfonylurea herbicides and chloroacetamide compounds; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

In another embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound, which is thiazosulfonate; (b) an effective amount of an N-sulfonylurea compound, which is nicosulfonate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) one or more vegetable oils or derivatives thereof.

In another embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) one or more vegetable oils or derivatives thereof.

In another embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound, which is thiamethoxam; (b) an effective amount of a chloroacetamide compound, which is dimethylphenidate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) one or more vegetable oils or derivatives thereof.

In another embodiment, the present invention provides a physically stable non-aqueous agrochemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica having a specific surface area of at least 160 ^m² /g and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more rheology modifiers selected from the group consisting of 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 thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more rheology modifiers selected from the group consisting of fumed silica having a specific surface area of at least 160 ^m² /g and precipitated silica having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; 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 thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more rheology modifiers selected from the group consisting of Aerosil 200 and Sipernat 22S; and (d) one or more vegetable oils or derivatives thereof.

In embodiments, the present invention provides a physically stable non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of at least one additional herbicide selected from the group consisting of N-sulfonylurea herbicides and chloroacetamide compounds; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) an effective amount of one or more vegetable oils as a solvent selected from the group consisting of rapeseed oil, soybean oil, olive oil, castor oil, sunflower 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 the embodiments, the present invention provides a physically stable non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) an effective amount of a vegetable oil, which is rapeseed oil, specifically refined low-erucic acid rapeseed oil.

In the embodiments, the present invention provides a physically stable non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of a chloroacetamide compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of hydrophobic portions; and (d) an effective amount of a vegetable oil, which is rapeseed oil, specifically refined low-erucic acid rapeseed oil.

In another embodiment, the present invention provides the stable non-aqueous agrochemical formulation, which further comprises a safener selected from the group consisting of cyclopropanesulfonamide and pyrazosulfuron.

In the embodiments, the present invention provides the stable non-aqueous agricultural chemical formulation, which further comprises a safener, namely cyclopropanesulfonamide.

In another embodiment, the present invention provides the stable non-aqueous agricultural chemical formulation, which further comprises one or more additives, including emulsifiers.

In the embodiments, the present invention provides the stable non-aqueous agricultural chemical formulation, which further comprises an emulsifier, wherein the emulsifier is a polyethylene glycol ester of a fatty acid.

In an embodiment, the present invention provides a method for treating plants against undesirable vegetation, the method comprising applying a non-aqueous agrochemical formulation disclosed herein, after dilution with water, to a target site in a field to treat the plants against undesirable vegetation.

In the embodiments, the present invention provides the use of the non-aqueous agricultural chemical formulations disclosed herein for controlling grassy and broadleaf weeds in fields, more particularly in maize (corn) fields, such as species of the genera *Digitaria*, *Barnyardgrass*, *Setaria*, *Sorghum*, *Sorghum*, *Rhizophora*, *Sorghum*, *Poa*, *Amaranthus*, *Abutilon*, *Raphanus*, *Chenopodium*, *Datura*, *Indigofera*, *Polygonum*, *Portulaca*, *Solanum*, *Stellaria*, *Iris*, *Viola*, *Geranium*, *Matricaria*, *Polygonum*, *Thistle*, *Xanthium*, and *Hibiscus*.

In an embodiment, the present invention provides a method for preparing the non-aqueous agrochemical formulation disclosed herein from a single component portion.

In embodiments, the present invention provides a method for controlling unwanted vegetation, the method comprising applying a non-aqueous agricultural chemical formulation disclosed herein to a site. The present invention also provides a method for controlling gramineous and broadleaf weeds, the method comprising diluting a non-aqueous agricultural chemical formulation disclosed herein with water and applying the formulation to the site where the plants are located.

In an embodiment, the present invention provides a method for controlling undesirable vegetation, the method comprising applying a physically stable, non-aqueous agricultural chemical formulation to a site, the physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of an N-sulfonylurea compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

In an embodiment, the present invention provides a method for controlling undesirable vegetation, the method comprising applying a physically stable, non-aqueous agricultural chemical formulation to a site, the physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of nicosulfuron; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

In an embodiment, the present invention provides a method for controlling undesirable vegetation, the method comprising applying a physically stable, non-aqueous agricultural chemical formulation to a site, the physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of a sulfonylamino-carbonyltriazolinone compound; (b) an effective amount of a chloroacetamide compound; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

In an embodiment, the present invention provides a method for controlling undesirable vegetation, the method comprising applying a physically stable, non-aqueous agricultural chemical formulation to a site, the physically stable, non-aqueous agricultural chemical formulation comprising (a) an effective amount of thiamethoxam; (b) an effective amount of dimethylphenidate; (c) an effective amount of one or more silica-based rheology modifiers having a specific surface area of at least 160 ^m² /g, wherein the silica is free of a hydrophobic portion; and (d) one or more vegetable oils or derivatives thereof.

The following examples illustrate the practice of the invention in some of its embodiments, but should not be construed as limiting the scope of the invention. Other embodiments will be apparent to those skilled in the art based on consideration of the specification and examples. The specification (including examples) is intended to be exemplary only and does not limit the scope and spirit of the invention.

Preparation example:

The formulation of the present invention Together with some exemplary embodiments of the comparative formulation ^# , their respective physicochemical data are shown in the table below:

Formulation Type 1 : Nicosulfuron 30 + Thiazosulfonamide 15 + Cyproteronamide 22.5 OD

¹ TS54 2W = Accelerated shelf-life incubation method at 54°C for 2 weeks.

² TS40 8W = Accelerated shelf-life incubation method at 40°C for 8 weeks.

^3RT = Ambient temperature

Preparation type 2 Thiamethoxam 15 + dimethylphenidate-p 250 + cyclopropanesulfonamide 22.5 OD

Preparation type 3 Thiamethoxam 30 + dimethylphenidate-p 500 + cyclopropanesulfonamide 45 OD

¹ TS54 2W = Accelerated shelf-life incubation method at 54°C for 2 weeks.

² TS40 8W = Accelerated shelf-life incubation method at 40°C for 8 weeks.

^3RT = Ambient temperature

Data from some exemplary formulations of the present invention have shown that, when compared with other comparative formulations, formulations of the present invention with a rheology modifier exhibit enhanced physical stability (significantly consistent low separation) and chemical stability of the active ingredient compared with formulations without any rheology modifier, which is either fumed silica (Aerosil 200) having a specific surface area between 175 and 225 ^m² /g or precipitated silica (Sipernat 22S) having a specific surface area between 160 and 210 ^m² /g.

Claims (15)

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 the group consisting of N-sulfonylurea compounds and chloroacetamide compounds;

(c) An effective amount of one or more rheology modifiers based on silica having a specific surface area of at least 160 m ²/g, wherein the silica is free of hydrophobic moieties, and

(D) One or more vegetable oils or derivatives thereof.

2. The non-aqueous agrochemical formulation according to claim 1, wherein the sulfonylamino-carbonyl triazolinone compound is thidiazuron and the additional herbicide is nicosulfuron.

3. The non-aqueous agrochemical formulation according to claim 1, wherein the sulfonylamino-carbonyl triazolinone compound is thifensulfuron-methyl and the additional herbicide is dimethenamid.

4. A non-aqueous agrochemical formulation as claimed in any of claims 1 to 3, wherein the one or more rheology modifiers are selected from the group comprising fumed silica and precipitated silica having a specific surface area of at least 160 m ²/g, wherein the silica is free of hydrophobic moieties.

5. The non-aqueous agrochemical formulation of claim 4, wherein the one or more rheology modifiers are selected from the group comprising fumed silica having a specific surface area between 175-225 m ²/g and precipitated silica having a specific surface area between 160-210 m ²/g.

6. The non-aqueous agrochemical formulation of claim 5, wherein the one or more rheology modifiers are selected from the 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 said safener is selected from the group comprising cyclopropanesulfonamide and pyraclostrobin.

8. The non-aqueous agrochemical formulation of claim 7, wherein the safener is cyclopropanesulfonamide.

9. The non-aqueous agrochemical formulation of any one of claims 1-8, further comprising one or more additives, said one or more additives comprising an emulsifier.

10. The non-aqueous agrochemical formulation of claim 9, wherein the emulsifier is a polyethylene glycol ester of a fatty acid.

11. The non-aqueous agrochemical formulation according to any one of claims 1 to 10, wherein the vegetable oil or derivative thereof is selected from the group comprising rapeseed oil, soybean oil, olive oil, castor oil, sunflower 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 the vegetable oil is canola oil, which is refined canola oil.

13. A method of treating plants to combat undesirable weeds, the method comprising applying the herbicide formulation system of any one of claims 1-12 to a locus of interest after dilution with water, so as to treat the plants to combat undesirable weeds.

14. The method of claim 13, wherein the undesirable weeds are selected from the group consisting of grassy weeds and broadleaf weeds.

15. The method of any one of claims 13-14, wherein the undesirable weeds are selected from the group consisting of crabgrass species, barnyard species, green bristlegrass species, wild millet species, sorghum species, rye grass species, millet species, bluegrass species, wheatgrass species, amaranthus species, abutilon species, ragweed species, quinoa species, stramonium species, indigoid species, tenuifolia species, portulaca species, solanum species, chickweed species, pennywort species, laspium species, viola species, geranium species, chamomile species, polygonum species, thistle species, siberian species, and hibiscus species.