Herbicide composition

Abstract

The present invention relates to various pesticide compositions including non-aqueous continuous herbicide dispersion compositions and methods for preparing these compositions. The present invention further relates to herbicide application mixtures including water-continuous dispersion compositions, methods for preparing these application mixtures, and various methods of use. In addition, the present invention relates to various herbicide compositions with improved application properties.

Description

Technical Field

[0001] The present invention relates to various pesticide compositions including non-aqueous continuous herbicide dispersion compositions and methods for preparing these compositions. The present invention further relates to herbicide application mixtures including water-continuous dispersion compositions, methods for preparing these application mixtures, and various methods of use. In addition, the present invention relates to various herbicide compositions with improved application properties. Background Art

[0002] In order to improve the efficiency of applying herbicide active ingredients, it is highly desirable to combine two or more active ingredients in a single formulation. Combinations of active ingredients with different modes of action can provide better pest control. Similarly, concentrated compositions containing high loads of active ingredients are more economical in transportation and storage. Concentrated compositions containing high loads of multiple active ingredients (i.e., premixed concentrates) are also useful in avoiding or reducing mixing errors when preparing application mixtures in the field.

[0003] Preparation of chemically stable mixtures of active ingredients that may be chemically unstable and / or react with each other can be challenging. In addition, agricultural active substances can vary from water-soluble ionic compounds and oils or oil-soluble substances to water or oil-insoluble solids. Due to their different solubility, mixing these different types of active ingredients into mixtures may require preparation of multiphase mixtures such as dispersions, i.e., emulsions or suspensions. However, unlike single-phase mixtures such as true solutions, dispersions are not physically stable in nature.

[0004] Typically, a dispersion is a multiphase mixture of two or more immiscible components, including a liquid component having a continuous liquid phase and one or more dispersed phases (also referred to as an internal phase). The continuous liquid phase includes a liquid component that is partially or completely immiscible with other components, which may be solids and / or liquids present as dispersed phases, such as solid and / or liquid particles dispersed in the continuous liquid phase. When the dispersed phase is dispersed in water as the continuous phase, the dispersion is typically classified as a water-continuous dispersion, and when the continuous phase is an oily liquid rather than water, it is classified as an oil dispersion or an oil-continuous dispersion (i.e., a non-aqueous continuous dispersion).

[0005] In water continuous dispersions, high levels of ionic compounds dissolved in the aqueous phase tend to render the dispersion stabilizing components even if the dispersant / emulsifier / suspending agent is ineffective. Thus, obtaining good physical stability by combating the aggregation of emulsified oil droplets or suspended solid particles, coalescence of oil droplets leading to substantial separation of the emulsified oil phase, and sedimentation of dispersed particles / droplets may be challenged by water-based dispersions having high loadings of ionic active materials dissolved in their aqueous phase. However, once dissolved in a suitable polar liquid, the ionic nature of the ionic materials is only revealed when they dissociate into their constituent ions.

[0006] The solubility and ion dissociation of polar ionic compounds in non-polar liquids such as oils are generally very low, and the physical stability of oil-based dispersions may not be adversely affected by the presence of polar ionic active substances contained therein. However, the efficacy of agricultural active ingredients depends on the bioavailability of their soluble or molecular forms. Therefore, it may be challenging to develop bio-effective agricultural formulations that are oil dispersions (non-aqueous continuous dispersions) of polar ionic herbicide active ingredients such as glyphosate, dicamba and 2,4-D.

[0007] Furthermore, since they are usually used in large quantities, herbicidal compositions must have a high degree of stability against settling (since redispersion of any settled material is difficult for any large formulation), while having a low apparent viscosity (i.e., high shear rate viscosity) so that they can be easily dispersed. Obtaining opposing rheological properties, such as having a high low shear rate viscosity (for high stability) and a low high shear rate viscosity (for high flowability) is challenging, and there is a compromise level of stability and flowability.

[0008] In view of these problems, there remains a need for effective strategies to formulate stable herbicide compositions having high loadings of various lipophilic, oil-soluble herbicides and / or insoluble solid herbicides. SUMMARY OF THE INVENTION

[0009] Various herbicide dispersion compositions of the present invention comprise an oil continuous phase and a dispersed phase in the oil continuous phase and comprising a solid phase herbicide, wherein the oil continuous phase comprises an acetamide herbicide and a non-aqueous liquid, wherein the weight ratio of the non-aqueous liquid to the acetamide herbicide is at least about 1: 1, at least about 1.1: 1, at least about 1.2: 1, at least about 1.3: 1, at least about 1.4: 1, or at least about 1.5: 1. These compositions can be classified as solid-in-oil suspensions.

[0010] Other herbicide dispersion compositions of the present invention include an oil continuous phase comprising a non-aqueous liquid; a first bulk dispersed phase in the oil continuous phase, wherein the first bulk dispersed phase comprises an auxin herbicide that is at least partially soluble in the acetamide herbicide and / or an affinity solvent for the auxin herbicide; and a second bulk dispersed phase in the oil continuous phase and comprising a solid phase herbicide. Therefore, these compositions can be classified as oil-in-oil emulsions-co-solid-in-oil suspensions. In some of these compositions, the second bulk dispersed phase also comprises a second bulk dispersed phase oil, and wherein the solid phase herbicide is dispersed in the second bulk dispersed phase oil. These compositions can be classified as oil-in-oil emulsions-co-solid-in-oil emulsions.

[0011] The present invention also relates to various methods of preparing these herbicide dispersion compositions. Some methods include mixing a non-aqueous liquid, a solid phase herbicide, and an acetamide herbicide to form a herbicide dispersion composition, the composition including an oil continuous phase and a dispersed phase, the oil continuous phase comprising the non-aqueous liquid and the acetamide herbicide, and the dispersed phase in the oil continuous phase and comprising the solid phase herbicide, wherein the weight ratio of the non-aqueous liquid to the acetamide herbicide is at least about 1:1, at least about 1.1:1, at least about 1.2:1, at least about 1.3:1, at least about 1.4:1, or at least about 1.5:1. Other methods include mixing an acetamide herbicide and an auxin herbicide to form a first mixture, wherein the auxin herbicide is at least partially soluble in the acetamide herbicide; and mixing the first mixture with a second mixture to form a herbicide dispersion composition comprising an oil continuous phase comprising a non-aqueous liquid, a first bulk dispersed phase comprising the acetamide herbicide and the auxin herbicide at least partially soluble in the acetamide herbicide, and a second bulk dispersed phase comprising a solid phase herbicide.

[0012] Embodiments of the present invention also relate to various pesticide dispersion compositions comprising: (a) an oil continuous phase comprising a non-aqueous liquid having a dielectric constant of about 10 or less and having little solubility for ionic insecticidal active ingredients; (b) a dispersed phase comprising the ionic insecticidal active ingredients suspended in the oil continuous phase; (c) a rheology modifier; and (d) a dispersant.

[0013] Some embodiments of the present invention also relate to various co-emulsions, including oil-in-oil co-emulsion pesticide compositions, which comprise: (a) an oil continuous phase comprising a first non-aqueous liquid; (b) a first dispersed phase emulsified in the oil continuous phase, wherein the first dispersed phase comprises a second non-aqueous liquid and a pesticidal active ingredient dissolved in the second non-aqueous liquid; (c) a second dispersed phase emulsified in the oil continuous phase, wherein the second dispersed phase comprises a third non-aqueous liquid and a solid-phase pesticidal active ingredient dispersed in the third non-aqueous liquid; (d) a rheology modifier; (e) an emulsifier; and (f) a dispersant, wherein the dispersant is insoluble in the first non-aqueous liquid, and wherein the first non-aqueous liquid, the second non-aqueous liquid, and the third non-aqueous liquid are different and substantially immiscible with each other.

[0014] Other embodiments of the present invention are directed to polar liquid-in-oil and oil-in-oil co-emulsion pesticide compositions comprising: (a) an oil continuous phase comprising a first liquid, the first liquid comprising a non-aqueous liquid that is substantially immiscible with water; (b) a first dispersed phase emulsified in the oil continuous phase, wherein the first dispersed phase comprises a second liquid and a pesticidal active ingredient dissolved in the second liquid; (c) a second dispersed phase emulsified in the oil continuous phase, wherein the second dispersed phase comprises a third liquid and a solid-phase pesticidal active ingredient dispersed in the third liquid; (d) a rheology modifier; (e) an emulsifier; and (f) a dispersant, wherein the dispersant is insoluble in the first liquid, and wherein the first liquid, the second liquid, and the third liquid are different and substantially immiscible with each other.

[0015] Other embodiments of the present invention are directed to various wax-in-oil and oil-in-oil co-emulsion pesticide compositions comprising: (a) an oil continuous phase comprising a first liquid comprising a non-aqueous liquid that is substantially immiscible with water; (b) a first dispersed phase emulsified in the oil continuous phase, wherein the first dispersed phase comprises (i) a second liquid that is substantially immiscible with the first liquid, and (ii) a waxy solid, and optionally a molten form of an insecticidal active ingredient that is soluble in the second liquid and / or soluble in the waxy solid; (c) a second dispersed phase emulsified in the oil continuous phase, wherein the second dispersed phase comprises (i) a third liquid that is substantially immiscible with the first liquid and (ii) an insecticidal active ingredient dispersed in the third liquid; (d) a third dispersed phase emulsified in the oil continuous phase, wherein the third dispersed phase comprises a fourth liquid and a solid-phase insecticidal active ingredient dispersed in the fourth liquid; (e) a rheology modifier; (f) an emulsifier; and (g) a dispersant, wherein the dispersant is insoluble in the first liquid.

[0016] Other embodiments of the present invention include wax-in-oil emulsion pesticide compositions. In some embodiments, the pesticide dispersion composition is a herbicide dispersion composition comprising an oil continuous phase comprising a non-aqueous liquid (as described herein); and a dispersed phase comprising particles of a solid matrix comprising an acetamide herbicide and a waxy solid. In other embodiments, these herbicide compositions comprise particles of a solid matrix comprising an acetamide herbicide and a waxy solid, wherein the particles are dispersed in water (e.g., an application mixture).

[0017] The present invention also relates to methods of preparing herbicide application mixtures. Various methods include mixing water with the herbicide dispersion composition described herein to form a herbicide application mixture, wherein the herbicide application mixture is a water continuous dispersion.

[0018] The present invention is directed to a method for controlling weeds in a field of crop plants, the method comprising mixing water with a composition as described herein and applying the herbicide application mixture to the field in a herbicidally effective amount.

[0019] The present invention further relates to various herbicide compositions comprising an auxinic herbicide acid, a quaternary ammonium compound and / or a reaction product of an auxinic herbicide and a quaternary ammonium compound, wherein the quaternary ammonium compound has the structure of formula (I):

[0020]

[0021] Where R 1 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene; each R 3 R is independently hydrogen, or a straight or branched chain alkyl group having 1 to about 4 carbon atoms; 4 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; x and y are independently a number from 0 to about 10; X - is an agriculturally acceptable anion, provided that when x and y are each 0 and R 1 , R 2 , R 3 and R 4 When at least one of X is an alkyl or aralkyl group having 2 to 4 carbon atoms, - is not a hydroxide anion, and / or (ii) an affine solvent for an auxin herbicide acid, wherein the solvent satisfies at least one of the following:

[0022] (1) a molecular weight of at least about 300 grams per mole, at least about 600 grams per mole, or at least about 900 grams per mole,

[0023] (2) at least one double bond group per solvent molecule, and / or

[0024] (3) Each solvent molecule contains at least four hydrogen bonding groups.

[0025] The present invention includes various methods for controlling weeds in a field of crop plants, comprising applying any one of the herbicidal compositions described herein, or a dilution thereof, to the field in a herbicidally effective amount.

[0026] Other objects and features will be in part apparent and in part pointed out hereinafter. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention relates to various non-aqueous continuous (i.e., oil continuous) herbicide dispersion compositions and methods of preparing these herbicide dispersion compositions. The present invention further relates to herbicide application mixtures that are water continuous dispersion compositions, methods of preparing these application mixtures, and various methods of using the application mixtures.

[0029] In various aspects, the present invention provides non-aqueous or oil-continuous dispersion compositions for mixtures of herbicidal active ingredients with improved chemical and physical stability. It has been discovered that: i) certain chemically unstable herbicidal active ingredients exhibit increased chemical stability when formulated into oil-continuous dispersions, wherein the oil-continuous phase of these dispersions contains a large amount of an oily liquid with a relatively low dielectric constant; ii) certain chemically reactive herbicidal active ingredients exhibit increased chemical stability in oil-continuous dispersion compositions, wherein the active ingredients are physically separated from each other by one or more oily liquid phases with a relatively low dielectric constant; and iii) high loadings of certain ionic herbicide active ingredients can be incorporated into herbicide formulations in the form of oil-continuous dispersion compositions, wherein the oil-continuous phase of these dispersions contains a large amount of an oily liquid with a relatively low dielectric constant. Methods for incorporating high loadings of highly polar surfactants into oil-continuous herbicide dispersion compositions without the addition of any polar solvents have also been discovered. The herbicide dispersion compositions described herein may be in various forms, including solid-in-oil suspension compositions, oil-in-oil emulsion compositions, solid-in-oil-in-oil emulsion compositions, and combinations thereof, wherein the net hydrophilic-lipophilic balance (HLB) value of the surfactant mixture contained therein is suitable for a physically stable oil continuous dispersion composition.

[0030] Various aspects of the invention relate to formulation strategies that allow for stable mixtures of chemically unstable and / or ionic agricultural active ingredients to be biologically effective. Further aspects of the invention relate to strategies to overcome the shortcomings of oil dispersion compositions for agricultural formulations, including the shortcomings of oil dispersions in stabilizing unstable active ingredients and / or mixtures of reactive active ingredients, the high demand for surfactants, and the need for polar diluents for incorporating hydrophilic surfactants into the composition.

[0031] Applicants have discovered that herbicidal active ingredients can be mixed in biologically effective surfactant-poor physically and chemically stable mixtures by formulating the active ingredients into various types of strongly non-polar non-aqueous continuous dispersion compositions. These strongly non-polar non-aqueous continuous dispersion compositions contain strongly non-polar oils, meaning that a significant portion of the oil continuous phase is hydrocarbons, silicone oils, esters (i.e., having a carbon atom content of at least 12) and mixtures thereof. In various embodiments, the strong non-polar oil comprises a silicone oil having a viscosity of about 5 cst to about 100,000 cst, about 5 cst to about 10,000 cst, about 5 cst to about 1,000 cst, about 5 cst to about 500 cst, about 10 cst to about 100,000 cst, about 10 cst to about 10,000 cst, about 10 cst to about 1,000 cst, about 10 cst to about 500 cst, about 20 cst to about 100,000 cst, about 20 cst to about 10,000 cst, about 20 cst to about 1,000 cst, or about 20 cst to about 500 cst.

[0032] Other aspects of the present invention include providing a herbicide dispersion composition that is stable to composition changes caused by chemical degradation of ingredients such as herbicidal active ingredients and surfactants. Providing a chemically stable herbicide composition advantageously enables the efficacy of the composition to be maintained under extended storage and varying temperature conditions. For example, the present invention provides a herbicide dispersion composition with improved chemical stability that can be maintained over an extended period of time and a wide temperature range. The herbicide composition can be exposed to elevated and / or subfreezing temperatures during storage and transportation. Therefore, it is highly advantageous to provide a herbicide composition that is stable over a wide temperature range (e.g., as high as 40°C to 54°C or as low as -5°C to -20°C).

[0033] End-use applications of concentrated herbicide dispersion compositions typically require dilution of the composition with water prior to application. Thus, another aspect of the present invention relates to providing a herbicide dispersion composition comprising a relatively high loading of herbicide that can be diluted with water to readily form a water-continuous dispersion. Non-aqueous continuous herbicide dispersion compositions that readily form a water-continuous dispersion upon sufficient dilution do not require high shear mixing for emulsification.

[0034] Other aspects of the invention provide bio-effective premix formulations of oil dispersions with high loadings of ionic active ingredients. Another aspect of the invention provides for the use of a single dispersing and / or emulsifying polymer (rather than multiple polymers) to disperse multiple active ingredients (in solid and / or liquid form), which avoids the potential problems of thermodynamic incompatibility often faced by mixtures of polymers. Other aspects of the invention provide non-aqueous continuous dispersion compositions that are easily emulsified in dilution water for final application by incorporating high HLB surfactants into the non-aqueous continuous dispersion compositions while ensuring that these added surfactants do not adversely affect the physical and chemical stability of the dispersion compositions.

[0035] As described above, the various herbicide dispersion compositions of the present invention are non-aqueous continuous dispersion compositions (i.e., oil dispersions) comprising an oil continuous phase and a dispersed phase which may be a solid phase substantially insoluble in the oil continuous phase and / or an oil phase completely or partially immiscible with the oil continuous phase. Thus, the non-aqueous continuous dispersion composition may be a solid-in-oil dispersion composition, an oil-in-oil dispersion composition, a solid-in-oil-in-oil emulsion composition, and combinations thereof.

[0036] Generally, the various non-aqueous continuous herbicide dispersion compositions of the present invention contain relatively high total herbicide concentrations, such that in various embodiments, these compositions can be considered herbicide concentrates. For example, in various embodiments, the total herbicide loading of the dispersion composition is at least about 10 wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, at least about 50 wt.%, or at least about 60 wt.%. In some embodiments, the total herbicide loading of the composition is about 10 wt.% to about 80 wt.%, about 20 wt.% to about 80 wt.%, about 30 wt.% to about 80 wt.%, about 40 wt.% to about 80 wt.%, about 50 wt.% to about 80 wt.%, about 60 wt.% to about 80 wt.%, about 10 wt.% to about 70 wt.%, about 20 wt.% to about 70 wt.%. %, about 30 wt.% to about 70 wt.%, about 40 wt.% to about 70 wt.%, about 50 wt.% to about 70 wt.%, about 60 wt.% to about 70 wt.%, about 10 wt.% to about 60 wt.%, about 20 wt.% to about 60 wt.%, about 30 wt.% to about 60 wt.%, about 40 wt.% to about 60 wt.%, or about 50 wt.% to about 60 wt.%. If applicable, the herbicide concentration is calculated based on acid equivalents.

[0037] In addition, the oil continuous phase can constitute a significant portion of the total volume of the non-aqueous continuous herbicide dispersion composition. In various embodiments, the volume fraction of the oil continuous phase is greater than about 0.6, greater than about 0.7, or greater than about 0.8, based on the total volume of the dispersion composition. In some embodiments, the volume fraction of the oil continuous phase is 0.5 to about 0.9, 0.5 to about 0.8, 0.5 to about 0.7, 0.6 to about 0.9, 0.6 to about 0.8, or 0.6 to about 0.7, based on the total volume of the dispersion composition.

[0038] Pesticide dispersion composition

[0039] Various non-aqueous continuous pesticide dispersion compositions of the present invention include compositions comprising: (a) an oil continuous phase comprising a non-aqueous liquid having a dielectric constant of about 10 or less and having a very low solubility for the ionic insecticidal active ingredient (e.g., a solubility of less than 1 wt.%, less than about 0.1 wt.%, or even less than about 0.01 wt.%); (b) a dispersed phase comprising the ionic insecticidal active ingredient suspended in the oil continuous phase; (c) a rheology modifier; and (d) a dispersant.

[0040] In various embodiments, the ionic insecticidal active ingredient is a solid phase insecticidal active ingredient. For example, the ionic insecticidal active ingredient comprises a solid phase ionic herbicide (for example, as described herein), and the dispersion is an oil-in-solid suspension. In some embodiments, the ionic insecticidal active ingredient is dissolved in a polar liquid immiscible with the non-aqueous liquid of the continuous phase, and the resulting solution is emulsified in the continuous phase to form an oil-in-polar liquid emulsion. In certain embodiments, the polar liquid is selected from water, alcohol, polyol, ether, polar ester, polar amide and mixtures thereof.

[0041] In various embodiments, the non-aqueous liquid comprises a strongly non-polar non-aqueous liquid as defined herein. For example, in some embodiments, the non-aqueous liquid can be selected from the group consisting of an oily pesticidal active ingredient (e.g., an oil-phase herbicide as described herein), a hydrocarbon-based liquid, a vegetable oil, an ester oil, an amide oil, an aromatic oil, a silicone oil, and mixtures thereof (all described in more detail herein).

[0042] Various non-aqueous continuous herbicide dispersion compositions of the present invention include solid herbicide dispersion compositions in oil. Typically, these compositions comprise an oil continuous phase containing an oil phase herbicide and a dispersed phase containing a solid phase herbicide. In these compositions, the dispersed phase is completely or partially immiscible in the oil continuous phase. The term "partially immiscible" means that no more than about 10 wt.%, no more than about 5 wt.%, no more than about 1 wt.%, no more than about 0.1 wt.%, or no more than about 0.01 wt.% of the components are miscible in the corresponding solvent (e.g., oil continuous phase).

[0043] Examples of oil phase herbicides include acetamide herbicides. Typically, acetamide herbicides are relatively polar oily herbicides. Acetamide herbicides include, for example, acetochlor, alachlor, butachlor, butachlor, sulfamethoxazole, decachloramine, norformyl, dimethochlor, dimethochlor, dimethochlor-P, mefenacet, metazachlor, isopropyl metolachlor, S-isopropyl metolachlor, enamid, pretilachlor, natrium, promethachlor, isopropyl metolachlor, clarithromycin, terbutachlor, dimethenamid and dimethylbenzene, its ester and mixture thereof. In some embodiments, acetamide herbicides are selected from acetochlor, alachlor, isopropyl metolachlor, S-isopropyl metolachlor and mixture thereof. In certain embodiments, acetamide herbicides include acetochlor. Therefore, various herbicide dispersion compositions of the present invention include an oil continuous phase comprising acetamide herbicides and a dispersed phase comprising a solid phase herbicide.

[0044] These compositions can contain relatively high concentrations of acetamide herbicides. In various embodiments, the concentration of acetamide herbicides can be at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, or at least about 40 wt.%. For example, the concentration of the acetamide herbicide can be about 10 wt.% to about 65 wt.%, about 20 wt.% to about 65 wt.%, about 30 wt.% to about 65 wt.%, about 40 wt.% to about 65 wt.%, about 50 wt.% to about 65 wt.%, about 10 wt.% to about 60 wt.%, about 20 wt.% to about 60 wt.%, about 30 wt.% to about 60 wt.%, about 40 wt.% to about 60 wt.%, about 50 wt.% to about 60 wt.%, about 10 wt.% to about 55 wt.%, about 20 wt.% to about 55 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 50 wt.% to about 55 wt.%, or about 40 wt.% to about 50 wt.%.

[0045] Solid phase herbicides include herbicides that are completely or partially immiscible in the oil continuous phase. Examples of solid phase herbicides include hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, such as benitosulfuron, cypermethrin, flubutyric acid amine, pyraclostrobin, clomazone, pyraclostrobin, flupyralid, fluazifop, flufenacet, chlorpyrifos, isoxaflutole, mesotrione, norbatrimide, flupyralid, pyrazol, benzylpyrazone, sulfotrione, cyclosulfuron, torapiramide, teflonone, its salts and esters and mixtures thereof. In some embodiments, solid phase herbicides include mesotrione. Other solid phase herbicides include solid phase ionic herbicides, such as glyphosate, glufosinate and its salts. Other solid phase ionic herbicides as described herein include auxin herbicides and their salts. Other solid herbicides include various protoporphyrinogen oxidase (PPO) inhibitors, including, for example, acifluorfen, fenpyralid, fenpyralid, fluazifop-butyl, foramsulfuron, flupyridazine, flufenacet-butyl, flufenacet-butyl, fluazifop-butyl, flufenacet-butyl, fluazifop-butyl, fluazifop-butyl, lactofen, oxadiazine, oxadiazine, oxyfluorfen, pyraclostrobin, saflufenacil and sulfamethoxam, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimid-3-yl)phenoxy]-2-pyridyloxy]acetate, its salts and esters, and mixtures thereof. In some embodiments, the solid phase herbicide comprises ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridinyloxy]acetate.

[0046] These compositions can contain relatively high concentrations of solid-phase herbicides. In various embodiments, the concentration of the solid-phase herbicide can be at least about 1 wt.%, at least about 2 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, or at least about 30 wt.%. For example, the concentration of the solid-phase herbicide can be about 1 wt.%-about 40 wt.%, about 1 wt.%-about 30 wt.%, about 1 wt.%-about 20 wt.%, about 1 wt.%-about 10 wt.%, about 1 wt.%-about 5 wt.%, about 2 wt.%-about 40 wt.%, about 2 wt.%-about 30 wt.%, about 2 wt.%-about 20 wt.%, about 2 wt.%-about 10 wt.%, about 2 wt.%-about 5 wt.%. .%, about 5wt.%-about 40wt.%, about 5wt.%-about 30wt.%, about 5wt.%-about 20wt.%, about 5wt.%-about 10wt.%, about 10wt.%-about 40wt.%, about 10wt.%-about 30wt.%, about 10wt.%-about 20wt.%, about 15wt.%-about 40wt.%, about 15wt.%-about 30wt.%, or about 15wt.%-about 20wt.%.

[0047] It has been found that acetamide herbicides (such as acetochlor) and solid phase herbicides (such as mesotrione) tend to react or degrade with each other when mixed, especially at relatively high concentrations. Applicants have found that improved chemical stability can be achieved by adding a relatively high concentration of non-aqueous liquid (especially a strongly non-polar non-aqueous liquid) to the oil continuous phase relative to the concentration of the acetamide herbicide. In various embodiments, the weight ratio of non-aqueous liquid to acetamide herbicide is at least about 1:1, at least about 1.1:1, at least about 1.2:1, at least about 1.3:1, at least about 1.4:1, or at least about 1.5:1. For example, the weight ratio of the non-aqueous liquid to the acetamide herbicide can be from about 1:1 to about 10:1, from about 1:1 to about 5:1, from about 1:1 to about 3:1, from about 1:1 to about 2:1, from about 1:1 to about 1.5:1, from about 1.1:1 to about 10:1, from about 1.1:1 to about 5:1, from about 1.1:1 to about 3:1, from about 1.1:1 to about 2:1, from about 1.1:1 to about 1.5:1, from about 1.2:1 to about 10:1, from about 1.2:1 to about 5:1, from about 1.2:1 to about 3:1, from about 1.2:1 to about 2:1, or from about 1.2:1 to about 1.5:1.

[0048] In various embodiments, the non-aqueous liquid constitutes a significant portion of the composition. For example, the non-aqueous liquid concentration can be at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, at least about 40 wt.%, or at least about 50 wt.%. In certain embodiments, the concentration of the non-aqueous liquid is about 10 wt.%-about 75 wt.%, about 20 wt.%-about 75 wt.%, about 30 wt.%-about 75 wt.%, about 40 wt.%-about 75 wt.%, about 50 wt.%-about 75 wt.%, about 10 wt.%-about 65 wt.%, about 20 wt.%-about 65 wt.%, about 30 wt.%-about 65 wt.%, about 40 wt.%-about 65 wt.%, about 50 wt.%-about 65 wt.% %, about 10wt.% to about 60wt.%, about 20wt.% to about 60wt.%, about 30wt.% to about 60wt.%, about 40wt.% to about 60wt.%, about 50wt.% to about 60wt.%, about 10wt.% to about 55wt.%, about 20wt.% to about 55wt.%, about 30wt.% to about 55wt.%, about 40wt.% to about 55wt.%, about 50wt.% to about 55wt.%, or about 40wt.% to about 50wt.%.

[0049] It has been found that strong non-polar non-aqueous liquids can provide enhanced chemical stability. Chemical stability is assessed by measuring the weight % recovery of acetamide herbicides and / or solid phase herbicides (e.g., mesotrione) after storage for a period of time at a fixed temperature. For example, in one stability test, the composition is stored at 40°C for 8 weeks. In another stability test, the composition is stored at 54°C for 8 weeks, 4 weeks, 2 weeks, or 1 week. The concentration of the herbicide is measured at the beginning of the storage period and at the end of the storage period. The weight % recovery of acetamide herbicides and / or solid phase herbicides is calculated by dividing the final concentration of acetamide herbicides and / or solid phase herbicides (e.g., weight % after the storage period) by the initial concentration (e.g., weight % at the beginning of the storage period) and multiplying by 100%. The higher the weight % recovery of the herbicide, the higher the chemical stability of the composition. Enhanced chemical stability can be, for example, after the composition is stored at 54°C for 2 weeks, at least 95 weight % of the solid phase herbicide (e.g., mesotrione) is recovered.

[0050] In various embodiments, the strongly non-polar, non-aqueous liquids that can provide enhanced chemical stability have a dielectric constant of about 10 or less, about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less, or about 2 or less measured at 25° C. Examples of non-aqueous liquids include various hydrocarbon-based liquids, such as paraffinic and aliphatic hydrocarbon solvents (e.g., containing C5-C 25 Branched and / or straight chain alkanes or C 10 -C 20 The paraffinic and aliphatic hydrocarbon liquids include normal paraffin oils (e.g., NORPAR 15 available from ExxonMobil); and isoparaffinic oils (e.g., ISOPAR V, ISOPAR L and ISOPAR M available from ExxonMobil); mineral oils; and aliphatic fluids or oils (e.g., EXXSOL D110 and EXXSOL D130 available from ExxonMobil). Other non-polar, non-aqueous liquids include ester oils having a carbon atom content of at least 12 (e.g., isopropyl myristate), triglycerides (e.g., vegetable oils), and silicone oils (e.g., relatively high molecular weight dimethicone). In various embodiments, the viscosity of the silicone oil is from about 5 cst to about 100,000 cst, from about 5 cst to about 10,000 cst, from about 5 cst to about 1,000 cst, from about 5 cst to about 500 cst, from about 10 cst to about 100,000 cst, from about 10 cst to about 10,000 cst, from about 10 cst to about 1,000 cst, from about 10 cst to about 500 cst, from about 20 cst to about 100,000 cst, from about 20 cst to about 10,000 cst, from about 20 cst to about 1,000 cst, or from about 20 cst to about 500 cst.

[0051] Composite pesticide dispersion composition

[0052] Other non-aqueous continuous pesticide dispersion compositions of the present invention include various composite insecticide oil dispersion compositions. Various compositions are co-emulsions, which refer to emulsions containing multiple dispersed phases, wherein each dispersed phase independently contains a liquid phase that is immiscible with each liquid phase of other dispersed phases, wherein each different liquid phase of the multiple dispersed phases is dispersed in an oil continuous phase.

[0053] For example, various co-emulsions include oil-in-oil co-emulsion pesticide compositions. In some embodiments, these compositions include: (a) an oil continuous phase comprising a first non-aqueous liquid; (b) a first dispersed phase emulsified in the oil continuous phase, wherein the first dispersed phase comprises a second non-aqueous liquid and a pesticidal active ingredient dissolved in the second non-aqueous liquid; (c) a second dispersed phase emulsified in the oil continuous phase, wherein the second dispersed phase comprises a third non-aqueous liquid, and the solid phase pesticidal active ingredient is dispersed in the third non-aqueous liquid; (d) a rheology modifier; (e) an emulsifier; and (f) a dispersant, wherein the dispersant is insoluble in the first non-aqueous liquid, and wherein the first non-aqueous liquid, the second non-aqueous liquid, and the third non-aqueous liquid are different and substantially immiscible with each other. As used herein, the phrase "substantially immiscible" or "substantially insoluble" means that the miscibility of one component with another component measured at room temperature (20°C) is less than 10 wt.%, less than 5 wt.%, less than 1 wt.%, less than 0.1 wt.% or even less than 0.01 wt.%.

[0054] In various embodiments of these oil-in-oil co-emulsion pesticide compositions, the dielectric constant of the first non-aqueous liquid measured at 25° C. is about 10 or less, about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less, or about 2 or less. In some embodiments, the first non-aqueous liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof (as described herein). Similarly, in certain embodiments, the second non-aqueous liquid is selected from oily insecticidal active ingredients, vegetable oils, ester oils, amide oils, aromatic oils, and mixtures thereof (as described herein). In various embodiments, the third non-aqueous liquid is selected from silicone oils, hydrocarbon-based liquids, vegetable oils, and mixtures thereof (as described herein). In some embodiments, the third non-aqueous liquid comprises silicone oil (as described herein). In a specific embodiment, the second dispersed phase comprises a dispersant comprising a copolymer of acrylates / ethylhexyl acrylate / dimethicone methacrylate.

[0055] Other composite pesticide oil dispersion compositions include polar liquids in oil and oil-in-oil co-emulsion pesticide compositions. In various embodiments, these compositions include: (a) an oil continuous phase comprising a first liquid, the first liquid comprising a non-aqueous liquid that is substantially immiscible with water; (b) a first dispersed phase emulsified in the oil continuous phase, wherein the first dispersed phase comprises a second liquid and an insecticidal active ingredient dissolved in the second liquid; (c) a second dispersed phase emulsified in the oil continuous phase, wherein the second dispersed phase comprises a third liquid and a solid-phase insecticidal active ingredient dispersed in the third liquid; (d) a rheology modifier; (e) an emulsifier; and (f) a dispersant, wherein the dispersant is insoluble in the first liquid, and wherein the first liquid, the second liquid, and the third liquid are different and substantially immiscible with each other.

[0056] In various embodiments of these oil-in-polar liquid and oil-in-oil co-emulsion pesticide compositions, the dielectric constant of the first liquid measured at 25° C. is about 10 or less, about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less, or about 2 or less. In some embodiments, the first liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof (as described herein). Similarly, in certain embodiments, the second liquid is selected from polar liquids, vegetable oils, ester oils, amide oils, aromatic oils, and mixtures thereof (as described herein). For example, the polar liquid can be selected from water, alcohols, polyols, ethers, polar esters, polar amides, and mixtures thereof. In various embodiments, the third liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof (as described herein). In some embodiments, the third liquid comprises silicone oil (as described herein). In a specific embodiment, the second dispersed phase comprises a dispersant comprising a copolymer of acrylates / ethylhexyl acrylate / methicone esters.

[0057] Other composite pesticide oil dispersion compositions include various wax-in-oil and oil-in-oil co-emulsion pesticide compositions. In various embodiments, these compositions include: (a) an oil continuous phase comprising a first liquid, the first liquid comprising a non-aqueous liquid substantially immiscible with water; (b) a first dispersed phase emulsified in the oil continuous phase, wherein the first dispersed phase comprises (i) a second liquid substantially immiscible with the first liquid, and (ii) a waxy solid, and optionally a molten form of an insecticidal active ingredient soluble in the second liquid and / or soluble in the waxy solid; (c) a second dispersed phase emulsified in the oil continuous phase, wherein the second dispersed phase comprises (i) a third liquid substantially immiscible with the first liquid and (ii) an insecticidal active ingredient dispersed in the third liquid; (d) a third dispersed phase emulsified in the oil continuous phase, wherein the third dispersed phase comprises a fourth liquid and a solid-phase insecticidal active ingredient dispersed in the fourth liquid; (e) a rheology modifier; (f) an emulsifier; and (g) a dispersant, wherein the dispersant is insoluble in the first liquid.

[0058] In various embodiments of these wax-in-oil and oil-in-oil co-emulsion pesticide compositions, the dielectric constant of the first liquid measured at 25°C is about 10 or less, about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less, or about 2 or less. In some embodiments, the first liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof (as described herein). Similarly, in certain embodiments, the second liquid is selected from polar liquids, vegetable oils, ester oils, amide oils, aromatic oils, and mixtures thereof (as described herein). For example, polar liquids can be selected from water, alcohols, polyols, ethers, polar esters, polar amides, and mixtures thereof. In some embodiments, the amount of the second liquid in the first dispersed phase is not greater than about 95% by weight of the first dispersed phase. In various embodiments, the second liquid and the third liquid are the same. In certain embodiments, the fourth liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof. In some embodiments, the fourth liquid comprises silicone oil (as described herein). In a particular embodiment, the third dispersed phase comprises a dispersant comprising a copolymer of acrylates / ethylhexyl acrylate / dimethicone methacrylate.

[0059] In various embodiments, when the mixture of waxy solid and second liquid is heated to more than the melting point of waxy solid, above-mentioned waxy solid can be miscible with second liquid.In some embodiments, the mixture of waxy solid and second liquid is prepared by melting waxy solid and mixing the molten waxy solid with second liquid.In further embodiments, the first dispersed phase comprises solid particles at a temperature lower than the melting point of waxy solid.In various embodiments, the second liquid is present in a solid matrix comprising waxy solid.

[0060] In various embodiments, the waxy solids referred to herein can be selected from high molecular weight polymer waxes (e.g., polyethylene glycol, polyethylene), hydrocarbon waxes (paraffin wax, microcrystalline wax), natural waxes (carnauba wax, beeswax), triglyceride waxes (hydrogenated castor oil wax), silicone waxes, ester waxes and mixtures thereof. In some embodiments, the high molecular weight polymer wax comprises polyethylene glycol wax. For example, the polyethylene glycol wax can have an average molecular weight of about 1000Da or higher or about 1000Da-about 9000Da. In various embodiments, the melting point of the waxy solid (e.g., polyethylene glycol wax) is about 35°C-about 95°C, about 40°C-about 95°C, about 50°C-about 95°C or about 60°C-about 95°C.

[0061] In various wax-in-oil and oil-in-oil co-emulsion pesticide compositions, the homogeneous solution comprises a mixture of: i) an oily insecticidal active ingredient and / or an oil-soluble insecticidal active ingredient dissolved in an oily solvent, and ii) heating the mixture to above the melting point of the wax can prepare a wax that is completely miscible with the oily insecticidal active ingredient or the oily solvent. The heated oil-wax mixture can be emulsified in a strong non-polar oil, which must be a poor solvent for both the oil and wax components. The resulting emulsion is cooled to below the melting point of the wax to produce an oil-in-wax emulsion, wherein due to the solidification / crystallization of the wax, the emulsion droplets exist as condensed wax droplets (i.e., solid matrix particles containing insecticidal active ingredients and waxy solids). In fact, the oily insecticidal active ingredient and / or the oil-soluble insecticidal active ingredient are captured in a hard, porous solid matrix of interconnected wax crystals.

[0062] These compositions can exhibit slower diffusion rates of active ingredients in and out of the emulsified wax droplets than in the absence of wax. Likewise, these compositions can exhibit enhanced physical segregation of active ingredients in the composition; improved chemical stability by minimizing intermixing of reactive active ingredients; and improved crop safety due to reduced diffusion / release rates of active ingredients.

[0063] Other composite insecticidal oil dispersion compositions include various wax-in-oil emulsion pesticide compositions. In some embodiments, the pesticide dispersion composition is a herbicide dispersion composition. In various embodiments, these compositions comprise an oil continuous phase containing a non-aqueous liquid (as described herein); and a dispersed phase of solid matrix particles containing acetamide herbicides and waxy solids. In other embodiments, these herbicide compositions comprise particles of a solid matrix containing acetamide herbicides and waxy solids, wherein the particles are dispersed in water (e.g., an application mixture).

[0064] In these and other embodiments, the concentration of the acetamide herbicide is at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, or at least about 40 wt.%. For example, the concentration of the acetamide herbicide can be about 10 wt.% to about 65 wt.%, about 20 wt.% to about 65 wt.%, about 30 wt.% to about 65 wt.%, about 40 wt.% to about 65 wt.%, about 50 wt.% to about 65 wt.%, about 10 wt.% to about 60 wt.%, about 20 wt.% to about 60 wt.%, about 30 wt.% to about 60 wt.%, about 40 wt.% to about 60 wt.%, about 50 wt.% to about 60 wt.%, about 10 wt.% to about 55 wt.%, about 20 wt.% to about 55 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 50 wt.% to about 55 wt.%, or about 40 wt.% to about 50 wt.%.

[0065] In some embodiments, the weight ratio of acetamide herbicide to waxy solids is at least about 1: 1, at least about 1.5: 1, at least about 2: 1, or at least about 3: 1. For example, the weight ratio of acetamide herbicide to waxy solids is from about 1: 1 to about 5: 1, from about 1: 1 to about 4: 1, from about 1: 1 to about 3: 1, from about 1.5: 1 to about 5: 1, from about 1.5: 1 to about 4: 1, from about 1.5: 1 to about 3: 1, from about 2: 1 to about 5: 1, from about 2: 1 to about 4: 1, or from about 2: 1 to about 3: 1.

[0066] As described herein, acetamide herbicides include, for example, acetochlor, alachlor, butachlor, butenetrachlor, sulfamethoxazole, decachloramine, norformyl, dimethochlor, dimethochlor, dimethochlor-P, mefenacet, metazachlor, isopropyl metolachlor, S-isopropyl metolachlor, naproxen, pretilachlor, natrium, promethachlor, isopropyl metolachlor, clarithromycin, terbutachlor, dimethenamid and dimethochlor, their salts and esters and mixtures thereof. In some embodiments, the acetamide herbicide is selected from acetochlor, alachlor, isopropyl metolachlor, S-isopropyl metolachlor and mixtures thereof. In certain embodiments, the acetamide herbicide comprises acetochlor.

[0067] As described herein, waxy solids can be selected from high molecular weight polymer waxes (e.g., polyethylene glycol, polyethylene), hydrocarbon waxes (paraffin wax, microcrystalline wax), natural waxes (carnauba wax, beeswax), triglyceride waxes (hydrogenated castor oil wax), silicone waxes, ester waxes, and mixtures thereof. In some embodiments, the high molecular weight polymer wax comprises polyethylene glycol wax. For example, the polyethylene glycol wax can have an average molecular weight of about 1000Da or higher or about 1000Da-about 9000Da. In various embodiments, the melting point of the waxy solid (e.g., polyethylene glycol wax) is about 35°C-about 95°C, about 40°C-about 95°C, about 50°C-about 95°C, or about 60°C-about 95°C. 40°C-about 95°C, about 50°C-about 95°C, or about 60°C-about 95°C.

[0068] In some embodiments, these emulsion compositions also include a second dispersed phase comprising a solid phase herbicide dispersed in, for example, silicone oil. The viscosity of the silicone oil may be about 5 cst to about 100,000 cst, about 5 cst to about 10,000 cst, about 5 cst to about 1,000 cst, about 5 cst to about 500 cst, about 10 cst to about 100,000 cst, about 10 cst to about 10,000 cst, about 10 cst to about 1,000 cst, about 10 cst to about 500 cst, about 20 cst to about 100,000 cst, about 20 cst to about 10,000 cst, about 20 cst to about 1,000 cst, or about 20 cst to about 500 cst. The solid-phase herbicide, for example, comprises at least one hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor selected from the group consisting of fenpyroximate, fenpyroximate, fluazifop, pyraclostrobin, clomazone, pyrafluanid, flupyrazone, fluazifop, fluazifop, chlorpyrifos, isoxaflutole, mesotrione, norfadoxime, fluazifop, pyrazoline, benzylpyrazone, sulfotrione, cyproconazole, torapiramide, teflonone, salts and esters thereof, and mixtures thereof. In some embodiments, the solid-phase herbicide comprises isoxaflutole or mesotrione.

[0069] Other non-aqueous continuous herbicide dispersion compositions of the present invention include various composite herbicide oil dispersion compositions, which include acetamide herbicides, auxin herbicides and solid phase herbicides. Typically, these compositions include multiple different bulk dispersed phases in the oil continuous phase. Having multiple dispersed phases is intended to keep the reactive components that react with each other separated from each other in the discrete phase or the physical separation phase. The physical separation of the dispersed oil phase is achieved by providing a repulsive force between the emulsion droplets of each dispersed phase, wherein the repulsive force between the droplets is strong enough to prevent the agglomeration or coalescence of the emulsion droplets and the subsequent fusion or coalescence. This in turn keeps the dispersed phases physically separated from each other, while providing enhanced physical stability for the dispersion composition.

[0070] In various embodiments, the herbicide dispersion composition comprises an oil continuous phase comprising a non-aqueous liquid; a first bulk dispersed phase in the oil continuous phase, wherein the first bulk dispersed phase comprises an auxin herbicide (e.g., an auxin herbicide acid) at least partially soluble in an acetamide herbicide and / or an affinity solvent for the auxin herbicide; and a second bulk dispersed phase in the oil continuous phase and comprising a solid phase herbicide. In these compositions, the bulk dispersed phase is completely or partially immiscible in the oil continuous phase.

[0071] In these embodiments, the non-aqueous liquid used for the oil continuous phase generally has no or low solubility or miscibility with the acetamide herbicide. For example, silicone oil, mineral oil, and mixtures thereof are found to have no or low solubility for acetamide herbicides such as acetochlor.

[0072] In some embodiments, non-aqueous liquids constitute a significant portion of these composite herbicide dispersion compositions. For example, the concentration of non-aqueous liquids in these dispersion compositions can be at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, at least about 40 wt.%, or at least about 50 wt.%. In certain embodiments, the concentration of non-aqueous liquid is about 10 wt.%-about 75 wt.%, about 20 wt.%-about 75 wt.%, about 30 wt.%-about 75 wt.%, about 40 wt.%-about 75 wt.%, about 50 wt.%-about 75 wt.%, about 10 wt.%-about 65 wt.%, about 20 wt.%-about 65 wt.%, about 30 wt.%-about 65 wt.%, about 40 wt.%-about 65 wt.%, about 50 wt.%-about 65 wt.% %, about 10wt.% to about 60wt.%, about 20wt.% to about 60wt.%, about 30wt.% to about 60wt.%, about 40wt.% to about 60wt.%, about 50wt.% to about 60wt.%, about 10wt.% to about 55wt.%, about 20wt.% to about 55wt.%, about 30wt.% to about 55wt.%, about 40wt.% to about 55wt.%, about 50wt.% to about 55wt.%, or about 40wt.% to about 50wt.%.

[0073] In various embodiments, the auxin herbicide is dissolved in an affinity solvent. When a solution of an auxin herbicide acid in an affinity solvent is mixed into a liquid phase that is immiscible with the auxin herbicide acid solution, the liquid phase comprises a chemically reactive component with the auxin herbicide acid and / or a certain amount of an auxin herbicide anion, and when the anion is in chemical equilibrium with the auxin herbicide acid in the solution, the chemical reactivity may be hindered. This in turn may result in the chemical stability of the aforementioned mixture being higher than otherwise.

[0074] In various embodiments, the affinity solvent for the auxinic herbicide satisfies at least one of the following:

[0075] (1) a molecular weight of at least about 300 grams per mole, at least about 600 grams per mole, or at least about 900 grams per mole (e.g., from about 900 grams per mole to about 1500 grams per mole),

[0076] (2) at least one double bond group per solvent molecule, and / or

[0077] (3) Each solvent molecule contains at least four hydrogen bonding groups.

[0078] In some embodiments, the affinity solvent comprises an alkanediol as described herein. In certain embodiments, the affinity solvent comprises a triglyceride. In various embodiments, the affinity solvent comprises castor oil.

[0079] In some embodiments, the second bulk dispersed phase further comprises a second bulk dispersed phase oil, and wherein the solid phase herbicide is dispersed in the second bulk dispersed phase oil. In these embodiments, the non-aqueous liquid and the second bulk dispersed phase oil are different. Examples of oils that can be used include silicone oils and mineral oils. In various embodiments, the second bulk dispersed phase comprises a silicone oil having a viscosity of about 5 cst to about 100,000 cst, about 5 cst to about 10,000 cst, about 5 cst to about 1,000 cst, about 5 cst to about 500 cst, about 10 cst to about 100,000 cst, about 10 cst to about 10,000 cst, about 10 cst to about 1,000 cst, about 10 cst to about 500 cst, about 20 cst to about 100,000 cst, about 20 cst to about 10,000 cst, about 20 cst to about 1,000 cst, or about 20 cst to about 500 cst.

[0080] The composite herbicide oil dispersion composition may comprise any acetamide herbicide described herein and a solid phase herbicide. In a particular embodiment, the acetamide herbicide comprises acetochlor and the solid phase herbicide comprises mesotrione.

[0081] In various embodiments, these dispersion compositions may contain relatively high concentrations of acetamide herbicides. The concentration of acetamide herbicides may be at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, or at least about 40 wt.%. For example, the concentration of the acetamide herbicide can be about 10 wt.% to about 65 wt.%, about 20 wt.% to about 65 wt.%, about 30 wt.% to about 65 wt.%, about 40 wt.% to about 65 wt.%, about 50 wt.% to about 65 wt.%, about 10 wt.% to about 60 wt.%, about 20 wt.% to about 60 wt.%, about 30 wt.% to about 60 wt.%, about 40 wt.% to about 60 wt.%, about 50 wt.% to about 60 wt.%, about 10 wt.% to about 55 wt.%, about 20 wt.% to about 55 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 50 wt.% to about 55 wt.%, or about 40 wt.% to about 50 wt.%.

[0082] These compositions may also include relatively high concentrations of solid-phase herbicides. In various embodiments, the concentration of the solid-phase herbicide may be at least about 1 wt.%, at least about 2 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, or at least about 30 wt.%. For example, the concentration of the solid-phase herbicide may be about 1 wt.%-about 40 wt.%, about 1 wt.%-about 30 wt.%, about 1 wt.%-about 20 wt.%, about 1 wt.%-about 10 wt.%, about 1 wt.%-about 5 wt.%, about 2 wt.%-about 40 wt.%, about 2 wt.%-about 30 wt.%, about 2 wt.%-about 20 wt.%, about 2 wt.%-about 10 wt.%, about 2 wt.%-about 5 wt.%. .%, about 5wt.%-about 40wt.%, about 5wt.%-about 30wt.%, about 5wt.%-about 20wt.%, about 5wt.%-about 10wt.%, about 10wt.%-about 40wt.%, about 10wt.%-about 30wt.%, about 10wt.%-about 20wt.%, about 15wt.%-about 40wt.%, about 15wt.%-about 30wt.%, or about 15wt.%-about 20wt.%.

[0083] The composite herbicide oil dispersion composition comprises one or more auxin herbicides which are at least partially dissolved in an affinity solvent for an acetamide herbicide and / or an auxin herbicide. The auxin herbicides include 3,6-dichloro-2-methoxybenzoic acid (dicamba); 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); dichloropropionic acid; 2-methyl-4-chlorophenoxyacetic acid (MCPA); 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB); 4-chlorophenoxyacetic acid; 2,4,5-trichlorophenoxyacetic acid (2,4,5-T); Clopyralid; Clopyralid; silanol; triclopyr; 2-4-methoprop; piclopirox; quick-kill barnyard; amiflocpyr; chloranil; chloranil; chloranil; chloranil; chloranil; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; 4-Amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester; 4-Amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylic acid methyl ester; 4-Amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl)- 1H-indol-6-yl] pyridine-2-carboxylic acid methyl ester; 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl) pyridine-2-carboxylic acid potassium; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl) pyridine-2-carboxylic acid butyl ester; its salts and esters; and mixtures thereof. In various embodiments, the auxin herbicide includes an auxin herbicide acid, such as dicamba acid and / or 2,4-D acid.

[0084] In some embodiments, the auxin herbicide comprises an auxin herbicide salt comprising an auxin herbicide anion and a salt-forming cation. For example, the salt-forming cation may comprise a cation of an amine / alkali metal or a mixture thereof. In various embodiments, the salt-forming cation comprises a cation selected from the group consisting of ammonia, monoethanolamine, diethanolamine, triethanolamine, dimethylamine, diglycolamine, isopropylamine, and mixtures thereof. In these and other embodiments, the salt-forming cation comprises an alkali metal cation selected from sodium, potassium, and mixtures thereof.

[0085] In certain embodiments, the auxin herbicide salt is only partially neutralized by the base. For example, the molar ratio of the salt-forming cation to the auxin herbicide anion may be no greater than about 0.8:1, no greater than about 0.75:1, no greater than about 0.7:1, no greater than about 0.65:1, or no greater than about 0.6:1. In some embodiments, the molar ratio of the salt-forming cation to the auxin herbicide anion is no greater than about 0.55:1, no greater than about 0.5:1, no greater than about 0.45:1, no greater than about 0.4:1, no greater than about 0.35:1, no greater than about 0.3:1, no greater than about 0.25:1, or no greater than about 0.2:1. In various embodiments, the molar ratio of the salt-forming cation to the auxin herbicide anion is about 0.2:1-0.8:1, about 0.2:1-0.75:1, about 0.2:1-0.7:1, about 0.2:1-0.65:1, about 0.2:1-0.6:1, about 0.2:1-0.55:1, about 0.2:1-0. ...6:1, about 0.2:1-0.6:1, about 0.2:1-0.7:1, about 0.2:1-0.7:1, about 0.2:1-0.7:1, about 0.45:1, about 0.2:1-0.4:1, about 0.2:1-0.35:1, about 0.2:1-0.3:1, about 0.3:1-0.8:1, about 0.3:1-0.75:1, about 0.3:1-0.7:1, about 0.3:1-0.65:1, about 0.3:1-0.6:1, about 0.3:1-0.55:1, about 0.3 :1-0.5:1, about 0.3:1-0.45:1, about 0.3:1-0.4:1, about 0.4:1-0.8:1, about 0.4:1-0.75:1, about 0.4:1-0.7:1, about 0.4:1-0.65:1, about 0.4:1-0.6:1, about 0.4:1-0.55:1, about 0.4:1-0.5:1, about 0 .5:1-0.9:1, about 0.5:1-0.8:1, about 0.5:1-0.75:1, about 0.5:1-0.7:1, about 0.5:1-0.65:1, about 0.6:1-0.9:1, about 0.6:1-0.8:1, about 0.6:1-0.75:1, about 0.6:1-0.7:1 or about 0.6:1-0.65:1.

[0086] Specific salts of dicamba include sodium dicamba, potassium dicamba, diglycolamine dicamba, monoethanolamine dicamba, diethanolamine dicamba, triethanolamine dicamba, dimethylamine dicamba, and mixtures thereof. In some embodiments, the auxin herbicide is selected from sodium dicamba, diglycolamine dicamba, monoethanolamine dicamba, and mixtures thereof.

[0087] Other agronomically acceptable salts of auxin herbicides include polyamine salts, such as those described in U.S. Patent Application Publication No. 2012 / 0184434, which is incorporated herein by reference. The polyamines described in U.S. 2012 / 0184434 include those of formula (A)

[0088]

[0089] Where R 14 , R 15 , R 17 , R 19 and R 20 are independently H or C1-C6-alkyl, which is optionally substituted by OH, R 16 and R 18 are independently C2-C4-alkylene, X is OH or NR 19 R 20 , and n is 1-20; and those of formula (B)

[0090]

[0091] Where R 21 and R 22 are independently H or C1-C6-alkyl, R 23 C1-C 12 -alkylene, and R 24 is an aliphatic C5-C8 ring system which contains nitrogen in the ring or is replaced by at least one unit NR 21 R 22 Specific examples of these polyamines include tetraethylenepentamine, triethylenetetramine, diethylenetriamine, pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-dipropylenetriamine, N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propylenediamine, N,N-bis(3-aminopropyl)methylamine, N-(3-dimethylaminopropyl)-N,N-diisopropanolamine, N,N,N'-trimethylaminoethyl-ethanolamine, aminopropylmonomethylethanolamine and aminoethylethanolamine, and mixtures thereof.

[0092] In the various compositions described herein, the concentration of the auxin herbicide on an acid equivalent basis is at least about 1 wt.%, at least about 2 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, or at least about 45 wt.%. In some embodiments, the concentration of the auxin herbicide based on acid equivalent is about 0.5 wt.% to about 10 wt.%, about 0.5 wt.% to about 5 wt.%, about 0.5 wt.% to about 3 wt.%, about 10 wt.% to about 55 wt.%, about 15 wt.% to about 55 wt.%, about 20 wt.% to about 55 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 45 wt.% to about 55 wt.%, about 10 wt.% to about 50 wt.%, about 15 wt.% to about 50 wt.%, about 20 wt.% to about 50 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 45 wt.% to about 55 wt.%, about 10 wt.% to about 50 wt.%, about 15 wt.% to about 50 wt.%, about 20 wt.% to about 50 wt.%, about 30 wt.% to about About 50wt.%, about 40wt.%-about 50wt.%, about 45wt.%-about 50wt.%, 10wt.%-about 45wt.%, about 15wt.%-about 45wt.%, about 20wt.%-about 45wt.%, about 30wt.%-about 45wt.%, about 40wt.%-about 45wt.%, 10wt.%-about 40wt.%, about 15wt.%-about 40wt.%, about 20wt.%-about 40wt.%, about 30wt.%-about 40wt.%, 10wt.%-about 25wt.%, about 15wt.%-about 25wt.%, or about 10wt.%-about 20wt.%.

[0093] Dispersants

[0094] In the dispersion compositions described herein, the dispersed phase is generally in the form of suspended solid particles or emulsified oil droplets. In order to maintain stability, these dispersed phases require strong and long-term repulsive forces acting between them. Polymeric dispersants are suitable for providing or enhancing such inter-particle repulsive forces. Therefore, in various embodiments, the dispersion compositions of the present invention also include a polymeric dispersant.

[0095] Typically, the HLB (hydrophile-lipophile balance) value of the dispersant is less than about 7. Polymeric dispersants include, for example, block copolymers or graft copolymers comprising a nominally insoluble comonomer and a second comonomer that is highly soluble in the oil continuous phase. In some embodiments, the polymeric dispersant comprises a triblock copolymer having a molecular structure that can be represented as an ABA block copolymer, wherein "A" represents a soluble comonomer and "B" represents a nominally insoluble comonomer.

[0096] In certain embodiments, the polymeric dispersant comprises at least one polymer selected from the group consisting of PEG-30 dipolyhydroxystearate, polyglyceryl-2 dipolyhydroxystearate, PEG-polyethylene block copolymer, PEG-polystyrene block copolymer, PEG-3 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxane ethyl dimethicone, lauryl PEG-9 polydimethylsiloxane ethyl dimethicone, polyglyceryl-3 polydimethylsiloxane ethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxane ethyl dimethicone. Methicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, polyglyceryl-3 disiloxane dimethicone, acrylate / ethylhexyl / methacrylate dimethicone, polyglyceryl-3 lauryl polydimethylsiloxyethyl dimethicone crosspolymer, PEG-15 lauryl polydimethylsiloxyethyl dimethicone crosspolymer, PEG-15 / lauryl dimethicone crosspolymer, polydimethicone / PEG-10 / 15 crosspolymer, polydimethicone / polyglyceryl-3 crosspolymer, lauryl dimethicone / polyglyceryl-3 crosspolymer, trimethylsiloxysilicate, and mixtures thereof. In some embodiments, the dispersant comprises PEG 30-dipolyhydroxystearate (CAS No. 827596-80-5).

[0097] Typically, in order for a polymer to function as a dispersant, it is necessary to adsorb the polymer on the surface of a particle (e.g., a suspended solid phase particle or an emulsified oil droplet). The affinity or interaction of the polymer with the surface can drive the polymer to be adsorbed on the particle surface. Due to specific polymer-surface interactions, such as hydrogen bonds, hydrophobic interactions, and ionic interactions, the polymer has an affinity for the particle surface. In the case of a given particle mixture, the polymer may have an affinity or not for each particle component. Therefore, a single polymer may not be sufficient as a dispersant for a dispersion composition comprising a mixture of particles with different surface properties. A mixture of multiple polymer dispersants may be effective for a mixture of particles, but only if the polymer is thermodynamically compatible in its mixture. However, in a polymer mixture, the thermodynamic incompatibility of polymers is normal, not an exception. Therefore, in various embodiments, the oil continuous phase comprises a single polymer dispersant. In these embodiments, the dispersant is capable of dispersing each bulk dispersed phase contained in the composition.

[0098] In various embodiments, the concentration of the dispersant (e.g., a polymeric dispersant) is from about 0.1% to about 50%, from about 0.1% to about 40%, from about 0.1% to about 30%, from about 0.1% to about 25%, from about 0.1% to about 20%, from about 0.1% to about 15%, from about 0.1% to about 10%, from about 0.1% to about 5%, from about 1% to about 50%, from about 1% to about 40%, from about 1% to about 30%, from about 1% to about 25%, from about 0.1% to about 20%, from about 1% to about 15%, from about 1% to about 10%, or from about 1% to about 5%, by weight of each dispersed phase.

[0099] Rheology Modifiers

[0100] The dispersion composition of the present invention may further comprise a rheology modifier. Typically, the rheology modifier minimizes the sedimentation of the dispersed phase. Typically, suitable rheology modifiers are effective in a temperature range of about -20°C to about 54°C. Rheology modifiers include, for example, particulate rheology modifiers and polymeric rheology modifiers. In some embodiments, the particulate rheology modifier is selected from montmorillonite clay (e.g., organoclay), silica, paraffin and natural waxes, crystalline cellulose, and mixtures thereof.

[0101] Typically, the polymer rheology modifier should be thermodynamically compatible with the dispersant. Polymer rheology modifiers include, for example, polyamide polymers available from Croda Inc., and polyethylene. Other suitable polymer rheology modifiers include various oil-soluble hydrophobic cross-linked polymers. In some embodiments, the polymer rheology modifier is selected from dimethicone / vinyl dimethicone cross-linked polymers, dimethicone / phenyl vinyl dimethicone cross-linked polymers, dimethicone / lauryl dimethicone cross-linked polymers and lauryl polydimethylsiloxane ethyl dimethicone / bisvinyl dimethicone cross-linked polymers and mixtures thereof. Mixtures of particles and polymer rheology modifiers can also be used.

[0102] The particulate rheology modifier may be in a surface-modified form, wherein the surface modifier is selected from C 12 –C 18Alkyl or aryl quaternary ammonium compounds, polymers and mixtures thereof. The rheology modifier is preferably capable of providing a high yield stress and a highly shear-thinning rheology, wherein even a gelled oil dispersion, once stirred or sheared, exhibits thinning or viscosity reduction to the extent that it can be easily poured or pumped and / or diluted for final application. In various embodiments, the rheology modifier comprises a surface-modified montmorillonite clay. In certain embodiments, the surface-modified montmorillonite clay has multiple surface modifications imparted by a combination of a plurality of surface-modified surfactants, at least one of which is a polymeric surfactant having a molecular weight greater than 2,000 Daltons. In some embodiments, the rheology modifier is a surface-modified montmorillonite clay ground into a smaller particle size to increase the yield stress and shear-thinning properties of the clay.

[0103] In various embodiments, the concentration of the rheology modifier is about 0.025 wt.% to about 30 wt.%, about 0.025 wt.% to about 20 wt.%, about 0.025 wt.% to about 25 wt.%, about 0.025 wt.% to about 15 wt.%, about 0.025 wt.% to about 10 wt.%, about 0.025 wt.% to about 5 wt.%, about 0.025 wt.% to about 1 wt.%, about 0.1 wt.% to about 30 wt.%, about 0.1 wt.% to about 25 wt.%, about 0.1 wt.% to about 20 wt.%, about 0.1 wt.% to about 15 wt.%, about 0.1 wt.% to about 10 wt.%, about 0.1 wt.% to about 5 wt.%, or about 0.1 wt.% to about 1 wt.%. Furthermore, the average particle size of the rheology modifier can be less than about 5 microns, less than about 2.5 microns, less than about 1 micron, less than about 0.5 microns, or less than about 0.1 microns. In some embodiments, the rheology modifier is ground to an average particle size of less than about 5 microns, less than about 2.5 microns, less than about 1 micron, less than about 0.5 microns, or less than about 0.1 microns.

[0104] Surfactants / emulsifiers

[0105] The dispersion composition of the present invention may further include one or more surfactants. Typically, the HLB value of a suitable surfactant is greater than 7. In various embodiments, the dispersion composition includes a surfactant that acts as an emulsifier, which can emulsify the non-aqueous continuous dispersion composition into a water-continuous dispersion by diluting with sufficient water. In some embodiments, the surfactant is present in the dispersion composition in a soluble form. If one or more surfactants are insoluble in the oil continuous phase and soluble in the oil phase of any dispersed phase, it can be added to any oil-containing dispersed phase instead of the oil continuous phase. In other embodiments, the amount of one or more surfactants is substantially less than the amount of the dispersant (for example, if the surfactant is added to the oil continuous phase). For example, the amount of the surfactant can be 50%, 40%, 30% or less than the amount of the dispersant. In further embodiments, the total amount of the surfactant can be equal to or slightly greater than the amount of the dispersant, but the amount of a single surfactant is preferably much less than the amount of the dispersant (for example, if the surfactant is added to the oil continuous phase containing a surfactant mixture). On the other hand, if the surfactant is added to any oil-containing dispersed phase, its amount can be higher than the amount of the dispersant.

[0106] Surfactant can be selected from anionic surfactant, cationic surfactant, zwitterionic surfactant and mixture thereof. Preferred examples of ionic surfactant include alkyl / aryl ether sulfate, alkyl / aryl ether sulfonate, alkyl / aryl ether carboxylate, alkyl / aryl ether phosphate, dialkyl sulfosuccinate, ethoxylated etheramine, ethoxylated-propoxylated etheramine, alkyl / aryl quaternary ammonium compound, alkyl / aryl quaternary phosphonium compound, ethoxylated alkyl / aryl quaternary ammonium compound, ethoxylated alkyl / aryl quaternary phosphonium compound, betaine, sulfobetaine, phospholipid and mixture thereof.

[0107] The surfactant may further comprise a nonionic surfactant, since nonionic surfactants are generally more effective than ionic surfactants in emulsifying oil in water in the presence of hard water cations.

[0108] In various embodiments, the concentration of the surfactant is about 0.1 wt.% to about 25 wt.%, about 0.1 wt.% to about 20 wt.%, about 0.1 wt.% to about 15 wt.%, about 0.1 wt.% to about 10 wt.%, about 0.1 wt.% to about 5 wt.%, about 0.1 wt.% to about 3 wt.%, about 0.1 wt.% to about 2 wt.%, about 0.5 wt.% to about 25 wt.%, about 0.5 wt.% to about 20 wt.%, about 0.5 ... % - about 15wt.%, 0.5wt.% - about 10wt.%, about 0.5wt.% - about 5wt.%, about 0.5wt.% - about 3wt.%, about 0.5wt.% - about 2wt.%, about 1wt.% - about 25wt.%, about 1wt.% - about 20wt.%, about 1wt.% - about 15wt.%, about 1wt.% - about 10wt.%, about 1wt.% - about 5wt.%, about 1wt.% - about 3wt.%, or about 1wt.% - about 2wt.%.

[0109] Other additives

[0110] The compositions described herein may further comprise various additives or adjuvants, including safeners, adjuvants to reduce drift, volatility control additives, soil residue enhancers, pH adjusters or pH buffers, antifreeze agents, biocides or preservatives (e.g., PROXEL commercially available from Avecia), foliar penetration enhancers, stabilizers (e.g., antioxidants), UV absorbers, light stabilizers, chelating agents, and antifoaming agents (e.g., Antifoam SE23 from Wacker Silicones Corp.).

[0111] In some embodiments, the compositions described herein further comprise one or more safeners. Suitable safeners (e.g., for making acetamide herbicides safe) include, for example, furazolidone ((RS)-3-(dichloroacetyl)-5-(2-furyl)-2,2-dimethyl-1,3-oxazolidine 95%) commercially available from Monsanto Company; AD 67 (4-(dichloroacetyl)-1-oxa-4-azaspiro[4,5]decane); benoxacin (CGA 154281, (RS)-4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine); clofoxyl (CGA 184927, (5-chloroquinoline-8-acyloxy)acetic acid); oxaclostrobin (CGA 14666, (5-chloroquinoline-8-acyloxy)acetic acid); 43089, (Z)-cyanomethoxyimino(phenyl)acetonitrile); cyclopropanesulfonamide (N-[4-(cyclopropylcarbamoyl)phenylsulfonyl]-o-anisamide); dichloroamine (DDCA, R25788, N,N-diallyl-2,2-dichloroacetamide); bicyclic ketone ((RS)-1-dichloroacetyl-3,3,8a-trimethylperhydropyrrolo[1,2-a]pyrimidin-6-one); synergistoxal (O,O-diethyl O-phenylthiophosphate); chlorpyrifos (HOE 70542, 1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylic acid); chlorpyrifos (CGA 1234074,6-dichloro-2-phenylpyrimidine); fluoxazolidinone (2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylic acid benzyl ester); fluazifop (CGA 133205,4′-chloro-2,2,2-trifluoroacetophenone (EZ)-O-1,3-dioxolan-2-ylmethyl oxime); isoxadifen (4,5-dihydro-5,5-diphenyl-1,2-oxazole-3-carboxylic acid); pyrazolidine oxalate ((RS)-1-(2,4-dichlorophenyl)-5-methyl-2-pyrazoline-3,5-dicarboxylic acid); toluene (4-chlorophenyl methyl carbamate); MG 191; naphthalene dicarboxylic anhydride (CGA 92194, (Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile); and other safeners known in the art.

[0112] The compositions of the present invention may further comprise one or more adjuvants that reduce drift. Adjuvants that reduce drift include, for example, GARDIAN, GARDIAN PLUS, DRI-GARD, and PRO-ONEXL available from Van Diest Supply Co.; COMPADRE available from Loveland Products, Inc.; BRONC MAXEDT, BRONC PLUS DRY EDT, EDT CONCENTRATE, and IN-PLACE from Wilbur-Ellis; STRIKE ZONE DF available from Helena Chemical Co.; INTACT and INTACT XTRA available from Precision Laboratories, LLC; and AGRHO DR 2000 and AGRHO DEP 775 available from Solvay Group. Suitable adjuvants that reduce drift also include, for example, guar-based (e.g., containing guar or derived guar) adjuvants that reduce drift. Various drift-reducing products may also include one or more water conditioners combined with one or more adjuvants that reduce drift.

[0113] The compositions described herein may further comprise one or more volatility control additives to control or reduce potential herbicide volatility. Under certain application conditions, certain herbicides (e.g., auxin herbicides) may evaporate into the surrounding atmosphere and migrate from the application site to adjacent crop plants (e.g., soybeans and cotton), where contact damage may be caused to sensitive plants. For example, as described in U.S. Application Publication Nos. 2014 / 0128264 and 2015 / 0264924, which are incorporated herein by reference, additives that control or reduce potential herbicide volatility include monocarboxylic acids or salts thereof (e.g., acetic acid and / or agriculturally acceptable salts thereof).

[0114] Representative monocarboxylic acids and monocarboxylates generally comprise hydrocarbons or unsubstituted hydrocarbons selected from, for example, unsubstituted or substituted straight or branched chain alkyl groups (e.g., C1-C 20 Alkyl, such as methyl, ethyl, n-propyl, isopropyl, etc.); unsubstituted or substituted straight-chain or branched alkenyl (e.g. C2-C 20The monocarboxylic acid may be selected from formic acid, acetic acid, propionic acid and benzoic acid. The monocarboxylate may be selected from formate, acetate, propionate and benzoate. The monocarboxylate may include, for example, an alkali metal salt selected from sodium and potassium. Preferred monocarboxylates include sodium acetate and potassium acetate. The molar ratio of the herbicide (e.g., auxin herbicide) to the monocarboxylic acid or its monocarboxylate may generally be about 1:10 to about 10:1, about 1:5 to about 5:1, about 3:1 to about 1:3 or about 2:1 to about 1:2 (e.g., about 1:1).

[0115] Other volatility control additives that can be used in the compositions of the present invention to control or reduce the volatility of potential herbicides include various quaternary ammonium compounds. The quaternary ammonium compounds include various alkyl / aryl quaternary ammonium compounds and alkoxylated alkyl / aryl quaternary ammonium compounds.

[0116] Typically, the molecular weight of the quaternary ammonium compound is no greater than about 1,000 Da, no greater than about 750 Da, or no greater than about 500 Da. For example, in various embodiments, the molecular weight of the quaternary ammonium compound is from about 100 Da to about 1,000 Da, from about 100 Da to about 750 Da, from about 100 Da to about 500 Da, from about 200 Da to about 1,000 Da, from about 200 Da to about 750 Da, from about 200 Da to about 500 Da, from about 250 Da to about 1,000 Da, from about 250 Da to about 750 Da, or from about 250 Da to about 500 Da.

[0117] In some embodiments, the quaternary ammonium compound has the structure of Formula (I):

[0118]

[0119] Where R 1 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene; each R 3 R is independently hydrogen, or a straight or branched chain alkyl group having 1 to about 4 carbon atoms; 4 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; x and y are independently a number from 0 to about 10; X - It is an agriculturally acceptable anion.

[0120] In various embodiments, R 1 and R 4Each of the hydrocarbon groups is independently a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, straight chain or branched chain alkynyl, straight chain or branched chain alkoxy, aryl or aralkyl group having 1 to about 30 carbon atoms. 1 and R 4 each independently is a straight or branched chain alkyl, straight or branched chain alkenyl, or straight or branched chain alkoxy having 1 to about 25 carbon atoms, 1 to about 22 carbon atoms, 1 to about 20 carbon atoms, 1 to about 18 carbon atoms, 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, 3 to about 18 carbon atoms, 3 to about 16 carbon atoms, 3 to about 14 carbon atoms, 3 to about 12 carbon atoms, 3 to about 10 carbon atoms, 3 to about 8 carbon atoms, or 3 to about 6 carbon atoms. In some embodiments, R 1 and R 4 have the same number of carbon atoms and / or the same substituents (e.g., R 1 and R 4 Each is butyl).

[0121] In some embodiments, R 1 is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, or about 3 to 18 carbon atoms. In these and other embodiments, R 4 is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 1 to about 12 carbon atoms, 1 to about 10 carbon atoms, 1 to about 8 carbon atoms, 1 to 6 carbon atoms, about 1 to 4 carbon atoms, 3 to about 12 carbon atoms, 3 to -10 carbon atoms, 3 to about 8 carbon atoms, or about 3 to 6 carbon atoms.

[0122] As noted, (R 2 O) x and (R 2 O) y Each R in each of the groups 2 is independently a C2-C4 straight or branched alkylene. For example, the quaternary ammonium compound of formula (I) includes various alkoxylated compounds, including ethoxylated quaternary ammonium compounds, propoxylated quaternary ammonium compounds, and quaternary ammonium compounds of various polymers or copolymers containing ethylene oxide (EO) and propylene oxide (PO). In some embodiments, (R 2 O) x and (R 2 O) y Each R in each of the groups 2 is independently a linear or branched C2-C4 alkylene group. 2 O) x and (R2 O) y Each R in each of the groups 2 In certain embodiments, the EO of the quaternary ammonium compound (i.e., wherein R 2 is ethylene) and PO (i.e., R 2 is propylene) in a molar ratio of about 1:3 to about 3:1, about 1:3 to about 2:1, about 1:3 to about 1.5:1, about 1:3 to about 1:1, about 1:3 to about 1:2, about 1:2 to about 3:1, about 1:2 to about 2:1, about 1:2 to about 1.5:1, about 1:2 to about 1:1, about 1:1 to about 3:1, about 1:1 to about 2:1, or about 1:1 to about 1.5:1.

[0123] In various embodiments, x and y are independently a number from 0 to about 8, 0 to about 6, 0 to about 4, about 0 to about 2, 1 to about 8, 1 to about 6, 1 to about 4, 1 to 2. In some embodiments, x and y are each 0. In other embodiments, x and y are each 1.

[0124] In various embodiments, each R 3 is independently hydrogen, methyl or ethyl. 3 is independently hydrogen or methyl. In certain embodiments, each R 3 For hydrogen.

[0125] X - X is a charge balancing counter anion, such as sulfate, hydroxide, chloride, bromide, nitrate, etc. In some embodiments, X - is a chloride or hydroxide anion. In certain embodiments, when x and y are each 0 and R 1 , R 2 , R 3 and R 4 When at least one of X is an alkyl group or an arylalkyl group having 2 to 4 carbon atoms, - Not the hydroxide anion.

[0126] Specific examples of quaternary ammonium compounds include tetrabutylammonium salts (e.g., tetrabutylammonium chloride and tetrabutylammonium chloride hydroxide) and trimethyl-tetradecylammonium salts (e.g., trimethyl-tetradecylammonium chloride). Other examples include the Tomamine series of quaternary ammonium compounds available from Evonik, especially the Tomamine Q series, which are represented by formula (II):

[0127]

[0128] Where R is an alkyl group (e.g. C1-C 20alkyl), n is the total number of moles of EO(CH2CH2O), and n+z is a number from 0 to 15. Specific examples of tommamines include Q-14-2 (isodecyloxypropyl dihydroxyethyl methyl ammonium chloride), Q-17-2 (isotridecyloxypropyl dihydroxyethyl methyl ammonium chloride), Q-17-5 (isotridecyloxypropyl poly(5)oxyethylene methyl ammonium chloride) and Q-18-2 (octadecyl dihydroxyethyl methyl ammonium chloride).

[0129] In various embodiments, the amount of the quaternary ammonium compound depends on the amount of auxin herbicide present in the composition. For example, in some embodiments, the molar ratio of the quaternary ammonium compound to the auxin herbicide is at least about 0.25:1, at least about 0.5:1, at least about 0.75:1, or at least about 1:1. In certain embodiments, the molar ratio of the quaternary ammonium compound to the auxin herbicide is 0.25:1 to about 2:1, about 0.25:1 to about 1.75:1, about 0.25:1 to about 1.5:1, about 0.25:1 to about 1.25:1, about 0.25:1 to about 1:1, about 0.5:1 to about 2:1, about 0.5:1 to about 1.75:1, about 0.5:1 to about 1.5:1, about 0. In some embodiments, the present invention relates to a polyurethane foam containing at least one amine group consisting of: a polyamide group, a polyamide group having a polyamide content of at least 1:1 to about 1.5:1, a polyamide group having a polyamide content of at least 1:1 to about 2:1, a polyamide group having a polyamide content of at least 1:1 to about 1.25:1, a polyamide group having a polyamide content of at least 1:1 to about 1.5:1, a polyamide group having a polyamide content of at least 1:1 to about 2:1, a polyamide group having a polyamide content of at least 1:1 to about 1.7 ... or a polyamide group having a polyamide content of at least 1:1 to about 1.25:1.

[0130] Another volatility control additive for controlling or reducing the volatility of potential herbicides for the compositions of the present invention includes various affinity solvents (i.e. non-aqueous affinity solvents). For a given solute, when the solute is dissolved in a solvent, if strong intermolecular interactions can be provided between solvent molecules and solute molecules, the solvent is an affinity solvent. The intensity of these intermolecular interactions (i.e. dispersion force, hydrogen bond and polar interactions) depends on one or more intrinsic parameters of the solvent, including for example the molecular weight of the solvent and the number of double bonds and hydrogen bonding groups present in the solvent. The higher the value of these parameters, the stronger the solute-solvent interaction, so that the solute molecules overcome these interactions to be distributed to any surrounding fluid phase immiscible with the solution phase. Therefore, affinity solvents are intended to minimize the dissipation or distribution of auxin herbicide acid from its solution in affinity solvent to the surrounding immiscible fluid phase that can be air, water, oil or its combination.

[0131] Therefore, when auxin herbicide acid such as dicamba acid is dissolved in affinity solvent, it may not be easily volatilized to surrounding air material as when there is no affinity solvent.When the solution of auxin herbicide acid in affinity solvent with limited miscibility of water is exposed to water flow (for example, irrigation water and / or rainwater flowing through soil hole), herbicide may not be easily transported by soil as common solvent.And then, this can cause the duration of weed control with auxin herbicide longer.In addition, when the solution of auxin herbicide acid in affinity solvent is mixed in the liquid phase immiscible with auxin herbicide acid solution, the liquid phase comprises the composition with auxin herbicide acid and / or a certain amount of auxin herbicide anion having chemical reactivity, and when the anion is in chemical equilibrium with the auxin herbicide acid in solution, chemical reactivity may be hindered.This and then can cause the chemical stability of aforementioned mixture to be higher than other situations.

[0132] Therefore, various embodiments of the present invention relate to a herbicidal composition comprising an auxinic herbicide acid; and a (non-aqueous) affinity solvent for the auxinic herbicide acid. Typically, the solvent satisfies at least one of the following:

[0133] (1) a molecular weight of at least about 300 grams per mole, at least about 600 grams per mole, or at least about 900 grams per mole (e.g., from about 900 grams per mole to about 1500 grams per mole),

[0134] (2) at least one double bond group per solvent molecule, and / or

[0135] (3) Each solvent molecule contains at least four hydrogen bonding groups.

[0136] In some embodiments, the affinity solvent comprises an alkanediol as described herein. In certain embodiments, the affinity solvent comprises a triglyceride. In various embodiments, the affinity solvent comprises castor oil.

[0137] In various embodiments, the weight ratio of the affinity solvent to the auxinic herbicide acid is at least about 1: 1, at least about 1.5: 1, at least about 2: 1, or at least about 3: 1. For example, the weight ratio of the affinity solvent to the auxinic herbicide acid is from about 1: 1 to about 5: 1, from about 1: 1 to about 4: 1, from about 1: 1 to about 3: 1, from about 1.5: 1 to about 5: 1, from about 1.5: 1 to about 4: 1, from about 1.5: 1 to about 3: 1, from about 2: 1 to about 5: 1, from about 2: 1 to about 4: 1, or from about 2: 1 to about 3: 1.

[0138] Chemical stability can be further improved by adding an effective amount of an alkanediol. Without being bound by theory, it is believed that the alkanediol forms a complex with the auxin herbicide, particularly the auxin herbicide in acid form. Theoretically, this complex is both non-reactive and relatively non-volatile. In various embodiments, the alkanediol comprises C2-C 10 In some embodiments, the alkane diol comprises a branched C2-C6 diol. 10 A diol or a branched C2-C6 diol. In some cases, branched diols have been found to provide greater improvements in reducing the volatility of auxin herbicides. In certain embodiments, the alkane diol is selected from propylene glycol; hexylene glycol; 1,3-propanediol; 1,4-butanediol; 1,3-butanediol; and mixtures thereof.

[0139] Typically, at least an equimolar ratio of alkanediol to auxin herbicide is required to impart improved chemical stability, and even greater stability is provided for higher amounts. In various embodiments, the molar ratio of alkanediol to auxin herbicide is at least about 1:1, at least about 2:1, at least about 3:1, at least about 4:1, at least about 5:1, at least about 6:1, at least about 7:1, at least about 8:1, or at least about 9:1. In some embodiments, the molar ratio of alkanediol to auxin herbicide is about 1:1-about 20:1, about 2:1-about 20:1, about 5:1-about 20:1, about 7:1-about 20:1, about 1:1-about 10:1, about 2:1-about 10:1, about 5:1-about 10:1, or about 7:1-about 10:1. In other aspects, the alkanediol concentration can be at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, or at least about 30 wt.%. For example, the alkanediol concentration can be about 5 wt.% to about 40 wt.%, about 5 wt.% to about 35 wt.%, about 5 wt.% to about 30 wt.%, about 5 wt.% to about 25 wt.%, about 5 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, about 5 wt.% to about 10 wt.%, about 10 wt.% to about 40 wt.%, about 10 wt.% to about 35 wt.%, about 10 wt.% to about % - about 30wt.%, about 10wt.% - about 25wt.%, about 10wt.% - about 20wt.%, about 10wt.% - about 15wt.%, about 15wt.% - about 40wt.%, about 15wt.% - about 35wt.%, about 15wt.% - about 30wt.%, about 20wt.% - about 40wt.%, about 20wt.% - about 35wt.%, or about 20wt.% - about 30wt.%.

[0140] In some embodiments, the composition described herein also comprises one or more soil residual promoters. It has been found that incorporating a small amount of cationic flocculant polymers in the composition can provide commercially acceptable weed control rates of at least 28 days, at least 35 days, at least 42 days or longer. Without being bound by theory, it is believed that cationic polymers are combined with droplets of soil and oil phase. Therefore, it is believed that the transportation of oil phase herbicides such as acetamide herbicides through the holes in the soil matrix is ​​reduced, thereby increasing the amount of time of herbicides on the soil surface. Cationic flocculant polymers are known in the field of wastewater conditioning. These polymers can have a high molecular weight exceeding, for example, about 100,000Da, about 500,000Da, about 1,000,000Da or even 10,000,000Da.

[0141] In various embodiments, the cationic flocculant polymer comprises at least one polymer selected from the group consisting of cationic polysaccharides, cationic derivatized polysaccharides, cationically modified acrylate polymers and copolymers, cationically modified acrylamide polymers and copolymers, high molecular weight proteins (e.g., gelatin), poly(diallyldimethylammonium chloride), cationically modified polyvinylpyrrolidone. In some embodiments, the cationic flocculant polymer comprises a cationic polysaccharide and / or a cationically derivatized polysaccharide. The polysaccharide may be selected from guar gum, chitosan, a cellulose polymer, a galactomannan, and combinations thereof.

[0142] The concentration of the cationic flocculant polymer generally depends on the molecular weight of the polymer. Higher molecular weight polymers can be used at lower concentrations. Likewise, the amount of the cationic flocculant polymer is enough to cause weak flocculation. Therefore, in various embodiments, the concentration of the cationic flocculant polymer is about 0.001wt.%-about 1wt.%, about 0.01wt.%-about 1wt.%, about 0.1wt.%-about 1wt.%, about 0.001wt.%-about 0.1wt.%, about 0.001wt.%-about 0.01wt.%, or about 0.01wt.%-about 0.1wt.%.

[0143] The compositions of the present invention may comprise one or more of the features described herein in various combinations.

[0144] Method for preparing various herbicide dispersion compositions

[0145] The present invention also relates to various methods of making the various non-aqueous continuous insecticide / herbicide dispersion compositions described herein.

[0146] A method for preparing the compositions described herein, particularly the solid herbicide-in-oil dispersion compositions, comprises mixing a non-aqueous liquid, an ionic insecticidal active ingredient as a solid herbicide, and an acetamide herbicide to form a herbicide dispersion composition comprising an oil continuous phase containing the non-aqueous liquid and the acetamide herbicide and a dispersed phase containing the solid phase herbicide, wherein the weight ratio of the non-aqueous liquid to the acetamide herbicide is at least about 1:1, at least about 1.1:1, at least about 1.2:1, at least about 1.3:1, at least about 1.4:1, or at least about 1.5:1. In some embodiments, the non-aqueous liquid and the acetamide herbicide are mixed prior to mixing with the solid phase herbicide. In other embodiments, the non-aqueous liquid and the solid phase herbicide are mixed prior to mixing with the acetamide herbicide.

[0147] A method for preparing various complex herbicide dispersion compositions described herein includes mixing an acetamide herbicide and an auxin herbicide to form a first mixture, wherein the auxin herbicide is at least partially dissolved in the acetamide herbicide; mixing a non-aqueous liquid and a solid phase herbicide to form a second mixture; and mixing the first mixture with the second mixture to form a herbicide dispersion composition, the composition comprising an oil continuous phase containing a non-aqueous liquid, a first bulk dispersed phase containing the acetamide herbicide and the auxin herbicide, and a second bulk dispersed phase containing the solid phase herbicide. In some embodiments, the second bulk dispersed phase also comprises a second bulk dispersed phase oil as described herein. In these embodiments, the solid phase herbicide is dispersed in the second bulk dispersed phase oil. In certain embodiments, the solid phase herbicide is mixed with the second bulk dispersed phase oil before the non-aqueous liquid is mixed with the solid phase herbicide.

[0148] In various embodiments of these methods, the herbicide dispersion composition further comprises a dispersant as described herein. In some embodiments, the dispersant is mixed with the non-aqueous liquid prior to mixing the non-aqueous liquid with the solid-phase herbicide.

[0149] Solid-phase herbicides and / or dispersion compositions can be ground using a grinding / milling device (e.g., a ball mill) equipped with suitable grinding media (e.g., ceramic grinding beads) to obtain the solid-phase herbicides / dispersed phase required particle size. In various embodiments of these methods, the solid-phase herbicides and / or dispersed phase can be ground to an average particle size of less than about 5 microns, less than about 2.5 microns, less than about 1 micron, less than about 0.5 micron or less than about 0.1 micron. When grinding, surfactants and / or other additives can be added after grinding.

[0150] Herbicide compositions comprising an auxin herbicide acid and a volatility control additive

[0151] The present invention also relates to herbicidal compositions comprising an auxin herbicide and one or more volatility control additives. In various embodiments, the herbicidal composition comprises an auxin herbicide, a quaternary ammonium compound, and / or a reaction product of an auxin herbicide and a quaternary ammonium compound.

[0152] It has been found that certain quaternary ammonium compounds can be used as volatility control additives to control or reduce the volatility of potential auxin herbicides. Various herbicidal compositions according to the present invention comprise an auxin herbicide acid, a quaternary ammonium compound and / or a reaction product of an auxin herbicide and a quaternary ammonium compound, wherein the quaternary ammonium compound has the structure of formula (I):

[0153]

[0154] Where R 1 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene; each R 3 R is independently hydrogen, or a straight or branched chain alkyl group having 1 to about 4 carbon atoms; 4 is a hydrocarbon or substituted hydrocarbon group having 1 to about 30 carbon atoms; x and y are independently a number from 0 to about 10; and X - is an agriculturally acceptable anion, provided that when x and y are each 0 and R 1 , R 2 , R 3 and R 4 When at least one of X is an alkyl or aralkyl group having 2 to 4 carbon atoms, - Not the hydroxide anion.

[0155] In various embodiments, R 1 and R 4 Each of the hydrocarbon groups is independently a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, straight chain or branched chain alkynyl, straight chain or branched chain alkoxy, aryl or aralkyl group having 1 to about 30 carbon atoms. 1 and R 4each independently is a straight or branched chain alkyl, straight or branched chain alkenyl, or straight or branched chain alkoxy having 1 to about 25 carbon atoms, 1 to about 22 carbon atoms, 1 to about 20 carbon atoms, 1 to about 18 carbon atoms, 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, 3 to about 18 carbon atoms, 3 to about 16 carbon atoms, 3 to about 14 carbon atoms, 3 to about 12 carbon atoms, 3 to about 10 carbon atoms, 3 to about 8 carbon atoms, or 3 to about 6 carbon atoms. In some embodiments, R 1 and R 4 have the same number of carbon atoms and / or the same substituents (e.g., R 1 and R 4 Each is butyl).

[0156] In some embodiments, R 1 is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, or about 3 to 18 carbon atoms. In these and other embodiments, R 4 is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 1 to about 12 carbon atoms, 1 to about 10 carbon atoms, 1 to about 8 carbon atoms, about 1 to 6 carbon atoms, about 1 to 4 carbon atoms, 3 to about 12 carbon atoms, 3 to about 10 carbon atoms, 3 to about 8 carbon atoms, or about 3 to 6 carbon atoms.

[0157] As noted, (R 2 O) x and (R 2 O) y Each R in each of the groups 2 is independently a C2-C4 straight or branched alkylene. For example, the quaternary ammonium compound of formula (I) includes various alkoxylated compounds, including ethoxylated quaternary ammonium compounds, propoxylated quaternary ammonium compounds, and quaternary ammonium compounds of various polymers or copolymers containing ethylene oxide (EO) and propylene oxide (PO). In some embodiments, (R 2 O) x and (R 2 O) y Each R in each of the groups 2 is independently a straight chain or branched C2-C4 alkylene group. 2 O) x and (R 2 O) y Each R in each of the groups 2 In certain embodiments, the EO of the quaternary ammonium compound (i.e., wherein R 2is ethylene) and PO (i.e., R 2 is propylene) in a molar ratio of about 1:3 to about 3:1, about 1:3 to about 2:1, about 1:3 to about 1.5:1, about 1:3 to about 1:1, about 1:3 to about 1:2, about 1:2 to about 3:1, about 1:2 to about 2:1, about 1:2 to about 1.5:1, about 1:2 to about 1:1, about 1:1 to about 3:1, about 1:1 to about 2:1, or about 1:1 to about 1.5:1.

[0158] In various embodiments, x and y are independently a number from 0 to about 8, 0 to about 6, 0 to about 4, about 0 to about 2, 1 to about 8, 1 to about 6, 1 to about 4, 1 to 2. In some embodiments, x and y are each 0. In other embodiments, x and y are each 1.

[0159] In various embodiments, each R 3 is independently hydrogen, methyl or ethyl. 3 is independently hydrogen or methyl. In certain embodiments, each R 3 For hydrogen.

[0160] X - X is a charge balancing counter anion, such as sulfate, hydroxide, chloride, bromide, nitrate, etc. In some embodiments, X - is a chloride or hydroxide anion. In certain embodiments, when x and y are each 0 and R 1 , R 2 , R 3 and R 4 When at least one of X is an alkyl group or an arylalkyl group having 2 to 4 carbon atoms, - Not the hydroxide anion.

[0161] Specific examples of quaternary ammonium compounds include tetrabutylammonium salts (e.g., tetrabutylammonium chloride and tetrabutylammonium chloride hydroxide) and trimethyl-tetradecylammonium salts (e.g., trimethyl-tetradecylammonium chloride). Other examples include the Tomamine series of quaternary ammonium compounds available from Evonik, especially the Tomamine Q series, which are represented by formula (II):

[0162]

[0163] Where R is an alkyl group (e.g. C1-C 20alkyl), n is the total number of moles of EO (CH2CH2O), and n+z is usually a number from 0 to 15. Specific examples of tommamines include Q-14-2 (isodecyloxypropyl dihydroxyethyl methyl ammonium chloride), Q-17-2 (isotridecyloxypropyl dihydroxyethyl methyl ammonium chloride), Q-17-5 (isotridecyloxypropyl poly (5) oxyethylene methyl ammonium chloride) and Q-18-2 (octadecyl dihydroxyethyl methyl ammonium chloride).

[0164] The auxin herbicide acid may comprise one or more of those described herein. For example, the auxin herbicide acid may be selected from the group consisting of: 3,6-dichloro-2-methoxybenzoic acid (dicamba); 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); dichloropropionic acid; 2-methyl-4-chlorophenoxyacetic acid (MCPA); 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB); 4-chlorophenoxyacetic acid; 2,4,5-trichlorophenoxyacetic acid (2, 4,5-T); clopyralid; clopyralid; sulfaquinoxaline; triclopyr; 2-4-methoprop; chlorpyrifos; chloranil; chloranil; chloranil; chloranil; chloranil; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; methyl 4-amino-3-chloro-5-fluoro-6 Benzyl-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxyacetyl) )-1H-indol-6-yl] pyridine-2-carboxylic acid methyl ester; 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl) pyridine-2-carboxylic acid potassium; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl) pyridine-2-carboxylic acid butyl ester; its salts and esters; and mixtures thereof. In some embodiments, the auxin herbicide acid comprises dicamba acid. In certain embodiments, the auxin herbicide comprises 2,4-D acid.

[0165] In various embodiments, the amount of the quaternary ammonium compound depends on the amount of auxinic herbicide acid present in the composition. For example, in some embodiments, the molar ratio of the quaternary ammonium compound to the auxinic herbicide is at least about 0.25:1, at least about 0.5:1, at least about 0.75:1, or at least about 1:1. In certain embodiments, the molar ratio of the quaternary ammonium compound to the auxinic herbicide is 0.25:1 to about 2:1, about 0.25:1 to about 1.75:1, about 0.25:1 to about 1.5:1, about 0.25:1 to about 1.25:1, about 0.25:1 to about 1:1, about 0.5:1 to about 2:1, about 0.5:1 to about 1.75:1, about 0.5:1 to about 1.5:1, about 0. In some embodiments, the present invention relates to a polyurethane foam containing at least one amine group consisting of: a polyamide group, a polyamide group having a polyamide content of at least 1:1 to about 1.5:1, a polyamide group having a polyamide content of at least 1:1 to about 2:1, a polyamide group having a polyamide content of at least 1:1 to about 1.25:1, a polyamide group having a polyamide content of at least 1:1 to about 1.5:1, a polyamide group having a polyamide content of at least 1:1 to about 2:1, a polyamide group having a polyamide content of at least 1:1 to about 1.7 ... or a polyamide group having a polyamide content of at least 1:1 to about 1.25:1.

[0166] In the various compositions described herein, the concentration of the auxin herbicide acid is at least about 1 wt.%, at least about 2 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, or at least about 45 wt.%. In some embodiments, the concentration of the auxin herbicide acid is about 0.5 wt.% to about 10 wt.%, about 0.5 wt.% to about 5 wt.%, about 0.5 wt.% to about 3 wt.%, about 10 wt.% to about 55 wt.%, about 15 wt.% to about 55 wt.%, about 20 wt.% to about 55 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 45 wt.% to about 55 wt.%, about 10 wt.% to about 50 wt.%, about 15 wt.% to about 50 wt.%, about 20 wt.% to about 50 wt.%, about 30 wt.% to about 50 wt.%, about 40wt.% to about 50wt.%, about 45wt.% to about 50wt.%, 10wt.% to about 45wt.%, about 15wt.% to about 45wt.%, about 20wt.% to about 45wt.%, about 30wt.% to about 45wt.%, about 40wt.% to about 45wt.%, 10wt.% to about 40wt.%, about 15wt.% to about 40wt.%, about 20wt.% to about 40wt.%, about 30wt.% to about 40wt.%, 10wt.% to about 25wt.%, about 15wt.% to about 25wt.%, or about 10wt.% to about 20wt.%.

[0167] The herbicidal compositions containing auxin herbicides, quaternary ammonium compounds and / or the reaction products of auxin herbicides and quaternary ammonium compounds may further contain one or more of the other ingredients and additives described herein. For example, these compositions may further contain an effective amount of an alkanediol. In various embodiments, the alkanediol comprises C2-C 10 In some embodiments, the alkane diol comprises a branched C2-C6 diol. 10 or C2-C6 diols. In some cases, branched diols have been found to provide greater improvements in reducing the volatility of auxin herbicides. In certain embodiments, the alkane diol is selected from propylene glycol; hexylene glycol; 1,3-propanediol; 1,4-butanediol; 1,3-butanediol; and mixtures thereof.

[0168] In various embodiments, the molar ratio of the alkanediol to the auxin herbicide is at least about 1: 1, at least about 2: 1, at least about 3: 1, at least about 4: 1, at least about 5: 1, at least about 6: 1, at least about 7: 1, at least about 8: 1, or at least about 9: 1. In some embodiments, the molar ratio of the alkanediol to the auxin herbicide is from about 1: 1 to about 20: 1, from about 2: 1 to about 20: 1, from about 5: 1 to about 20: 1, from about 7: 1 to about 20: 1, from about 1: 1 to about 10: 1, from about 2: 1 to about 10: 1, from about 5: 1 to about 10: 1, or from about 7: 1 to about 10: 1. In other aspects, the alkanediol concentration can be at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, or at least about 30 wt.%. For example, the alkanediol concentration can be about 5 wt.% to about 40 wt.%, about 5 wt.% to about 35 wt.%, about 5 wt.% to about 30 wt.%, about 5 wt.% to about 25 wt.%, about 5 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, about 5 wt.% to about 10 wt.%, about 10 wt.% to about 40 wt.%, about 10 wt.% to about 35 ... % - about 30wt.%, about 10wt.% - about 25wt.%, about 10wt.% - about 20wt.%, about 10wt.% - about 15wt.%, about 15wt.% - about 40wt.%, about 15wt.% - about 35wt.%, about 15wt.% - about 30wt.%, about 20wt.% - about 40wt.%, about 20wt.% - about 35wt.%, or about 20wt.% - about 30wt.%.

[0169] These compositions may also include a solvent. In some embodiments, the solvent is water.

[0170] In a further embodiment, the herbicide composition comprises an auxin herbicide acid and an affinity solvent. It has been found that certain affinity solvents can be used as volatility control additives to control or reduce potential auxin herbicide volatility. As described herein, when an auxin herbicide acid such as dicamba acid is dissolved in an affinity solvent, it may not be as easy to volatilize to surrounding air matter as when there is no affinity solvent. When a solution of an auxin herbicide acid in an affinity solvent with limited miscibility with water is exposed to a stream (for example, irrigation water and / or rainwater flowing through a soil hole), the herbicide may not be as easy to transport through the soil as a common solvent. And then, this can result in a longer duration of weed control with an auxin herbicide. Furthermore, when a solution of an auxinic herbicide acid in an affinity solvent is mixed into a liquid phase that is immiscible with the auxinic herbicide acid solution, the liquid phase comprising components that are chemically reactive with the auxinic herbicide acid and / or an amount of auxinic herbicide anions that are in chemical equilibrium with the auxinic herbicide acid in solution, chemical reactivity may be hindered. This in turn may result in a higher chemical stability of the aforementioned mixture than would otherwise be the case.

[0171] Therefore, various embodiments of the present invention are directed to herbicidal compositions comprising an auxinic herbicide acid; and an affinity solvent for the auxinic herbicide acid. Typically, the solvent satisfies at least one of the following:

[0172] (1) a molecular weight of at least about 300 grams per mole, at least about 600 grams per mole, or at least about 900 grams per mole (e.g., from about 900 grams per mole to about 1500 grams per mole),

[0173] (2) at least one double bond group per solvent molecule, and / or

[0174] (3) Each solvent molecule contains at least four hydrogen bonding groups.

[0175] In some embodiments, the affinity solvent comprises an alkanediol. In certain embodiments, the affinity solvent comprises a triglyceride. In various embodiments, the affinity solvent comprises castor oil.

[0176] In various embodiments, the weight ratio of the affinity solvent to the auxinic herbicide acid is at least about 1: 1, at least about 1.5: 1, at least about 2: 1, or at least about 3: 1. For example, the weight ratio of the affinity solvent to the auxinic herbicide acid is from about 1: 1 to about 5: 1, from about 1: 1 to about 4: 1, from about 1: 1 to about 3: 1, from about 1.5: 1 to about 5: 1, from about 1.5: 1 to about 4: 1, from about 1.5: 1 to about 3: 1, from about 2: 1 to about 5: 1, from about 2: 1 to about 4: 1, or from about 2: 1 to about 3: 1.

[0177] Herbicide application mixture

[0178] The present invention further relates to various herbicide application mixtures and methods for preparing these mixtures. Generally, the method comprises mixing water with the composition described herein to form the herbicide application mixture. In various embodiments, the herbicide application mixture is a water-continuous dispersion. That is, after sufficient dilution with water, the non-aqueous continuous herbicide dispersion composition is converted to a water-continuous dispersion composition. For example, the non-aqueous continuous herbicide dispersion composition can be diluted with about 5 to about 75 times or about 10 to about 50 times its weight of water.

[0179] Typically, the herbicide loading in the application mixture does not exceed about 5% by weight, or is from about 0.1% to about 5% by weight, or from about 1% to about 5% by weight, if applicable, for example, 5%, 4%, 3%, 2%, 1%, 0.5% or 0.1% on an acid weight equivalent basis.

[0180] The application mixtures described herein may include one or more additional herbicides. As described above, the application mixtures may be prepared by diluting the compositions described herein. Additional herbicides may be "tank mixed" to provide an application mixture comprising multiple herbicides.

[0181] Other herbicides include other auxin herbicides, acetyl CoA carboxylase (ACCase) inhibitors, enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, photosystem I (PS I) inhibitors, photosystem II (PS II) inhibitors, acetolactate synthase (ALS) or acetohydroxyacid synthase (AHAS) inhibitors, mitotic inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, cellulose inhibitors, oxidative phosphorylation uncouplers, dihydropterin synthase inhibitors, fatty acid and lipid biosynthesis inhibitors, auxin transport inhibitors, salts and esters thereof, racemic mixtures thereof and isomers of resolution and mixtures thereof. Examples of herbicides in these categories are as follows. When herbicides are generally referred to by name herein, unless otherwise limited, herbicides include all commercially available forms known in the art, such as salts, esters, free acids and free bases and stereoisomers thereof.

[0182] In some embodiments, other herbicides include auxin herbicides (i.e., synthetic auxin herbicides), including, for example, 3,6-dichloro-2-methoxybenzoic acid (dicamba); 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); dichloropropionic acid; 2-methyl-4-chlorophenoxyacetic acid (MCPA); 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB); 4-chlorophenoxy Acetic acid; 2,4,5-trichlorophenoxyacetic acid (2,4,5-T); clopyralid; clopyralid; thiazol; triclopyralid; 2-4-methoprop; chloranil; cypermethrin; chloranil; chloranil; chloranil; chloranil; chloranil; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; 4 -amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid benzyl ester; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(

[0063] methyl 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropicolinate; potassium 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinate; butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinate; salts and esters thereof; and mixtures thereof.

[0183] In some embodiments, other herbicides include PPO inhibitors. PPO inhibitors include, for example, acifluorfen, fenpyridin, fluazifop-butyl, mesotrione, flupyridazine, flufenac, pentanedil flufenac, propanyl flufenac, fluazifop-butyl, flufenac-methyl, fomesafen, lactofen, propanedil, oxadiazine, oxadiazine, oxyfluorfen, pyraclostrobin, bensulfuron and sulfentrazone, [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxy-1,2,3,4-tetrahydropyrimidine-3-yl)phenoxy]-2-pyridyloxy] ethyl acetate, its salts and esters and mixtures thereof. In a specific embodiment, other herbicides include a salt of fomesafen and / or fomesafen, such as fomesafen sodium. In some embodiments, the additional herbicide comprises ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridinyloxy]acetate.

[0184] In various embodiments, other herbicides include HPPD inhibitors. HPPD inhibitors include, for example, benitobar, cypermethrin, fluazifop, pyraclostrobin, clomazone, fluazifop, flupyralid, fluazifop, fluazifop, chlorpyrifos, isoxaflutole, mesotrione, norfadine, fluazifop, pyrazoline, benzylpyridin, sulfotrione, tampron, topamidine, torapiraft, teflon, their salts and esters, and mixtures thereof.

[0185] In some embodiments, the other herbicide comprises a PS II inhibitor. PS II inhibitors include, for example, ametryn, amitriptyline, atrazine, bentazon, herbicide, bromoxynil, chlorotoluron, cypermethrin, betamethrin, dichlorvos, oxazolidinone, diuron, cotton grass, hexazinone, ioxynil, isoproturon, linuron, metamitron, alamethoxam, methoxuron, metribuzin, chlorothiazon, betamethrin, promethazine, promethazine, dimethoate, cypermethrin, cypermethrin, cypermethrin, cypermethrin, cypermethrin, simazine, simethrin, thiocarb, terbuthion, terbuthion, terbuthion and thiocarb, their salts and esters and mixtures thereof.

[0186] In certain embodiments, other herbicides include ACCase inhibitors. ACCase inhibitors include, for example, fenpyroxil, clofodim, clethodim, cypermethrin, pinoxaden, sethoxydim, pyraclostrobin and oxaclostrobin, their salts and esters and mixtures thereof. Another class of ACCase inhibitors includes: dimethoate, clodinafop-butyl, chlorbutia, cyhalofop-butyl, dichlorobutia, dimethoate, oxadiazine, thiazolyl, pyraclostrobin, pyraclostrobin, isoxafoetida-butyl, oxadiazine, oxadiazine, pyraclostrobin, quinazolin, and trifop, their salts and esters and mixtures thereof. ACCase inhibitors also include a mixture of one or more "dims" and one or more "fops", their salts and esters.

[0187] In various embodiments, the other herbicides include ALS or AHAS inhibitors. ALS and AHAS inhibitors include, for example, amidosulfuron, azithromycin, benzylsulfuron, bisulfuron, chlorsulfuron, cinnamonsulfuron, chlorsulfuron, cyclam, diclososulfuron, ethametsulfuron, ethoxysulfuron, primisulfuron, bispyribac, flucarbazine, flutosulfuron ... Imazapyr, imazapic, imazaquin, imazapic, pyrazosulfuron-methyl, iodosulfuron-methyl, metsulfuron-methyl, nicosulfuron-methyl, penoxsulam, primisulfuron-methyl, propensulfuron-methyl, prosulfuron-methyl, pyrazosulfuron-methyl, pyrimidinesulfuron-butyl, pyrimidinesulfuron-butyl, pyrimidinesulfuron-butyl, sulfamethoxam, thiamethoxam, thiamethoxam, sulfamethoxam, thiamethoxam, thifensulfuron-methyl, ether bensulfuron-methyl, bensulfuron-methyl, trifloxysulfuron-methyl and flufenacil, their salts and esters and mixtures thereof.

[0188] In a further embodiment, the other herbicide comprises a mitotic inhibitor.Mitotic inhibitors include thiophanate-methyl, fluazifop, DCPA, dithiopyracil, flufenacet, flufenacet, mefenacet, chloranil, pendimethalin, thiamethoxam and trifloxylin, their salts and esters and mixtures thereof.

[0189] In some embodiments, the other herbicides include PS I inhibitors such as diquat and paraquat, their salts and esters, and mixtures thereof.

[0190] In certain embodiments, other herbicides include cellulose inhibitors such as dichlobenil and isoxadiazole.

[0191] In a further embodiment, the additional herbicide comprises an oxidative phosphorylation uncoupler, such as telofob and its esters.

[0192] In other embodiments, other herbicides include auxin transport inhibitors such as diazinon and chlorpyrifos, their salts and esters, and mixtures thereof.

[0193] In various embodiments, the additional herbicides comprise dihydropterin synthase inhibitors, such as chlorpyrifos and its salts.

[0194] In some embodiments, the other herbicides include fatty acid and lipid biosynthesis inhibitors such as dimethoate, butachlor, cyclohexane, EPTC, pentocarb, chlorpyrifos, chlorpyrifos, bensulfuron, chlorpyrifos, and chlorpyrifos, their salts and esters, and mixtures thereof.

[0195] Applying herbicide combination

[0196] The present invention also relates to various methods of applying the herbicide application mixtures described herein.

[0197] In various embodiments, the herbicide application mixture is a herbicide application mixture for preventing and treating weeds in crop plant fields. Commercially important crop plants include, for example, corn, soybeans, cotton, dry beans, kidney beans and potatoes. Crop plants include hybrids, inbred species and transgenic or genetically modified plants with specific traits or combinations of traits, including but not limited to herbicide resistance (for example, resistance to glyphosate, glufosinate, dicamba, glufosinate, PPO inhibitors, etc.), Bacillus thuringiensis (Bacillus thuringiensis, Bt), high oil, high lysine, high starch, nutrient density and drought resistance. In some embodiments, crop plants are resistant to organophosphorus herbicides, acetolactate synthase (ALS) or acetohydroxyacid synthase (AHAS) inhibitor herbicides, auxin herbicides and / or acetyl CoA carboxylase (ACCase) inhibitor herbicides. In other embodiments, the crop plants are resistant to glyphosate, dicamba, 2,4-D, MCPA, quizalofop, glufosinate and / or diclofenac. In other embodiments, the crop plants are resistant to glyphosate and / or dicamba. In some embodiments of the invention, the crop plants are resistant to glyphosate and / or glufosinate. In other embodiments, the crop plants are resistant to glyphosate, glufosinate and dicamba. In these and other embodiments, the crop plants are resistant to PPO inhibitors.

[0198] The herbicide application mixture can be applied to the field according to practices known to those skilled in the art. In some embodiments, the herbicide application mixture is applied to the field soil before planting the crop plants or after planting but before the crop plants sprout. In other embodiments, the herbicide application mixture is applied to the field after the crop plants sprout and / or before or after the weeds sprout. The herbicidal effective amount of the herbicide application mixture to be applied depends on various factors, including the characteristics of the herbicide, the crop to be treated, and environmental conditions such as soil type and moisture content.

[0199] The herbicide application mixtures of the present invention are useful for controlling a variety of weeds, ie, plants that are considered to be nuisances or competitors to commercially important crop plants. Examples of weeds that can be controlled according to the methods of the present invention include, but are not limited to, meadow foxtail (Alopecurus pratensis) and other weed species within the genus Foxtail, common barnyard grass (Echinochloacrus-galli) and other weed species within the genus Echinochloa, weeds within the genus Digitalis, white clover (Trifolium repens), gray weed (Chenopodium berlandieri), redroot amaranth (Amaranthus retroflexus) and other weed species within the genus Amaranthus, common purslane (Portulaca oleracea) and other weed species within the genus Portulaca, Chenopodium album and other Chenopodium, golden foxtail (Setaria lutescens) and other Setaria, nightshade (Solanum nigrum) and other nightshades, ryegrass (Lolium multiflorum) and other ryegrasses, Brachiaria platyphylla and other Brachiaria, Johnsongrass (Sorghum halepense and other sorghum species, Conyza canadensis and other sorghum species, and Eleusine indica. In some embodiments, the weeds include one or more glyphosate-resistant species, 2,4-D-resistant species, dicamba-resistant species, and / or ALS inhibitor herbicide-resistant species. In some embodiments, the glyphosate-resistant weed species is selected from the group consisting of Amaranthus palmeri, Amaranthus rudis, Ambrosia artemisiifolia, Ambrosia trifida, Conyza bonariensis, Conyza Canadensis, Digitaria insularis, Echinochloa colona, ​​Eleusine indica, Euphorbia heterophylla, Lolium multiflorum, Lolium rigidum, Plantago lancelata, Sorghum halepense, and Urochloa panicoides.

[0200] Although various methods discussed herein refer to applying the application mixture to a "field of crop plants," it is understood that the methods can include applying the mixture to a field where crop plants are to be planted (e.g., for pre-planting applications or burndown of fallow land). Furthermore, even though various methods refer to weeds in a "field," the term includes smaller discrete areas, such as a pot of soil or a planting bed (e.g., in a greenhouse).

[0201] Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims.

[0202] Implementation

[0203] For further illustration, other non-limiting embodiments of the present disclosure are set forth below.

[0204] Embodiment 1 is a herbicide dispersion composition comprising:

[0205] an oil continuous phase comprising an acetamide herbicide and a non-aqueous liquid, wherein the weight ratio of the non-aqueous liquid to the acetamide herbicide is at least about 1:1, at least about 1.1:1, at least about 1.2:1, at least about 1.3:1, at least about 1.4:1, or at least about 1.5:1; and

[0206] A dispersed phase is within the oil continuous phase and contains a solid herbicide.

[0207] Embodiment 2 is the composition of embodiment 1, wherein the weight ratio of the non-aqueous liquid to the acetamide herbicide is from about 1:1 to about 10:1, from about 1:1 to about 5:1, from about 1:1 to about 3:1, from about 1:1 to about 2:1, from about 1:1 to about 1.5:1, from about 1.1:1 to about 10:1, from about 1.1:1 to about 5:1, from about 1.1:1 to about 3:1, from about 1.1:1 to about 2:1, from about 1.1:1 to about 1.5:1, from about 1.2:1 to about 10:1, from about 1.2:1 to about 5:1, from about 1.2:1 to about 3:1, from about 1.2:1 to about 2:1, or from about 1.2:1 to about 1.5:1.

[0208] Embodiment 3 is the composition of embodiment 1 or 2, wherein the non-aqueous liquid comprises a non-polar liquid.

[0209] Embodiment 4 is the composition of any of embodiments 1-3, wherein the non-aqueous liquid has a dielectric constant of less than about 3.5, less than about 3, less than about 2.5, or less than about 2 measured at 25°C.

[0210] Embodiment 5 is the composition of any one of embodiments 1-4, wherein the non-aqueous liquid comprises a paraffinic or aliphatic hydrocarbon liquid and / or a mineral oil.

[0211] Embodiment 6 is the composition of any one of embodiments 1-5, wherein the non-aqueous liquid comprises one or more C5-C 25 Branched and / or straight chain alkanes.

[0212] Embodiment 7 is the composition of any one of embodiments 1-6, wherein the non-aqueous liquid comprises C 10 -C 20 Branched chain alkanes.

[0213] Embodiment 8 is the composition of any one of embodiments 1-7, wherein the non-aqueous liquid comprises an ester having a carbon atom content of at least 12.

[0214] Embodiment 9 is the composition of any one of embodiments 1-8, wherein the non-aqueous liquid comprises isopropyl myristate.

[0215] Embodiment 10 is the composition of any one of embodiments 1-9, wherein the non-aqueous liquid comprises silicone oil.

[0216] Embodiment 11 is the composition of any of embodiments 1-10, wherein the non-aqueous liquid comprises a silicone oil having a viscosity of about 5 cst to about 100,000 cst, about 5 cst to about 10,000 cst, about 5 cst to about 1,000 cst, about 5 cst to about 500 cst, about 10 cst to about 100,000 cst, about 10 cst to about 10,000 cst, about 10 cst to about 1,000 cst, about 10 cst to about 500 cst, about 20 cst to about 100,000 cst, about 20 cst to about 10,000 cst, about 20 cst to about 1,000 cst, or about 20 cst to about 500 cst.

[0217] Embodiment 12 is the composition of any one of embodiments 1-11, wherein the solid-phase herbicide comprises at least one hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor selected from the group consisting of fenpyroximate, cypermethrin, fluazifop, pyraclostrobin, clomazone, pyrafluanid, flupyralid, fluazifop, fluazifop, chlorpyrifos, isoxaflutole, mesotrione, norfadine, fluazifop, pyrazoline, benzylpyridamole, sulfotrione, tembotrione, topamezone, torapiraft, tefurin, their salts and esters, and mixtures thereof.

[0218] Embodiment 13 is the composition of any one of embodiments 1-12, wherein the solid phase herbicide comprises mesotrione.

[0219] Embodiment 14 is the composition of any one of embodiments 1-13, wherein the solid phase herbicide comprises a solid phase ionic herbicide.

[0220] Embodiment 15 is the composition of any one of embodiments 1-14, wherein the solid phase herbicide comprises glyphosate acid or a salt thereof.

[0221] Embodiment 16 is the composition of any one of embodiments 1-15, wherein the solid phase herbicide comprises glufosinate or a salt thereof.

[0222] Embodiment 17 is the composition of any one of embodiments 1-16, wherein the solid phase herbicide comprises a protoporphyrinogen oxidase (PPO) inhibitor.

[0223] Embodiment 18 is a herbicide dispersion composition comprising:

[0224] an oil continuous phase comprising a non-aqueous liquid;

[0225] a first bulk dispersed phase in an oil continuous phase, wherein the first bulk dispersed phase comprises an auxin herbicide at least partially soluble in the acetamide herbicide and / or an affinity solvent for the auxin herbicide; and

[0226] A second bulk dispersed phase is within the oil continuous phase and comprises a solid herbicide.

[0227] Embodiment 19 is the composition of embodiment 18, wherein the non-aqueous liquid comprises silicone oil.

[0228] Embodiment 20 is the composition of embodiment 18 or 19, wherein the non-aqueous liquid comprises mineral oil.

[0229] Embodiment 21 is the composition of any of embodiments 18-20, wherein the second bulk dispersed phase further comprises a second bulk dispersed phase oil, and wherein the solid phase herbicide is dispersed in the second bulk dispersed phase oil.

[0230] Embodiment 22 is the composition of embodiment 21, wherein the second bulk dispersed phase oil comprises silicone oil.

[0231] Embodiment 23 is the composition of embodiment 21, wherein the second bulk dispersed phase oil comprises a silicone oil having a viscosity of about 5 cst to about 100,000 cst, about 5 cst to about 10,000 cst, about 5 cst to about 1,000 cst, about 5 cst to about 500 cst, about 10 cst to about 100,000 cst, about 10 cst to about 10,000 cst, about 10 cst to about 1,000 cst, about 10 cst to about 500 cst, about 20 cst to about 100,000 cst, about 20 cst to about 10,000 cst, about 20 cst to about 1,000 cst, or about 20 cst to about 500 cst.

[0232] Embodiment 24 is the composition of any of embodiments 21-23, wherein the second bulk dispersed phase oil comprises mineral oil.

[0233] Embodiment 25 is the composition of any of embodiments 21-24, wherein the non-aqueous liquid is different from the second bulk dispersed phase oil.

[0234] Embodiment 26 is the composition of any one of embodiments 18-25, wherein the auxin herbicide is selected from 3,6-dichloro-2-methoxybenzoic acid (dicamba); 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); dichloropropionic acid; 2-methyl-4-chlorophenoxyacetic acid (MCPA); 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB); 4-chlorophenoxyacetic acid; 2,4 ,5-trichlorophenoxyacetic acid (2,4,5-T); clopyralid; clopyralid; silanol; triclopyr; 2-4-methoprop; picloram; quick-kill barnyard; amiloride; chloranil; chloranil; chloranil; chloranil; chloranil; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; 4-amino- 3-Chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylic acid benzyl ester; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylic acid methyl ester; 4-amino-3-chloro-5-fluoro-6-[7-fluoro-1-(methoxy

[0013] In some embodiments, the present invention relates to methyl 6-(1-acetyl)-1H-indol-6-yl)-pyridine-2-carboxylate; methyl 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate; potassium 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; salts and esters thereof; and mixtures thereof.

[0235] Embodiment 27 is the composition of any one of embodiments 18-26, wherein the auxinic herbicide comprises an auxinic herbicide acid.

[0236] Embodiment 28 is the composition of any one of embodiments 18-27, wherein the auxin herbicide comprises dicamba acid.

[0237] Embodiment 29 is the composition of any one of embodiments 18-28, wherein the auxin herbicide comprises 2,4-D acid.

[0238] Embodiment 30 is the composition of any one of embodiments 18-29, wherein the composition comprises an affinity solvent.

[0239] Embodiment 31 is the composition of any one of embodiments 18-30, wherein the affinity solvent for the auxin herbicide acid satisfies at least one of the following:

[0240] (1) a molecular weight of at least about 300 grams per mole, at least about 600 grams per mole, or at least about 900 grams per mole (e.g., from about 900 grams per mole to about 1500 grams per mole),

[0241] (2) at least one double bond group per solvent molecule, and / or

[0242] (3) Each solvent molecule contains at least four hydrogen bonding groups.

[0243] Embodiment 32 is the composition of any one of embodiments 18-31, wherein the composition comprises an affinity solvent.

[0244] Embodiment 33 is the composition of any one of embodiments 18-32, wherein the affinity solvent comprises an alkanediol.

[0245] Embodiment 34 is the composition of any one of embodiments 18-33, wherein the affinity solvent comprises a triglyceride.

[0246] Embodiment 35 is the composition of any one of embodiments 18-34, wherein the affinity solvent comprises castor oil.

[0247] Embodiment 36 is the composition of any of embodiments 18-35, wherein the weight ratio of affinity solvent to auxin herbicide is at least about 1:1, at least about 1.5:1, at least about 2:1, or at least about 3:1.

[0248] Embodiment 37 is the composition of any of embodiments 18-35, wherein the weight ratio of affinity solvent to auxin herbicide is about 1:1 to about 5:1, about 1:1 to about 4:1, about 1:1 to about 3:1, about 1.5:1 to about 5:1, about 1.5:1 to about 4:1, about 1.5:1 to about 3:1, about 2:1 to about 5:1, about 2:1 to about 4:1, or about 2:1 to about 3:1.

[0249] Embodiment 38 is the composition of any of embodiments 1-37, wherein the concentration of non-aqueous liquid is at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, at least about 40 wt.% or at least about 50 wt.%.

[0250] Embodiment 39 is the composition of any of embodiments 1-37, wherein the concentration of the non-aqueous liquid is about 10 wt.% to about 75 wt.%, about 20 wt.% to about 75 wt.%, about 30 wt.% to about 75 wt.%, about 40 wt.% to about 75 wt.%, about 50 wt.% to about 75 wt.%, about 10 wt.% to about 65 wt.%, about 20 wt.% to about 65 wt.%, about 30 wt.% to about 65 wt.%, about 40 wt.% to about 65 wt.%, about 50 wt.% to about 75 wt.%, -about 65wt.%, about 10wt.%-about 60wt.%, about 20wt.%-about 60wt.%, about 30wt.%-about 60wt.%, about 40wt.%-about 60wt.%, about 50wt.%-about 60wt.%, about 10wt.%-about 55wt.%, about 20wt.%-about 55wt.%, about 30wt.%-about 55wt.%, about 40wt.%-about 55wt.%, about 50wt.%-about 55wt.%, or about 40wt.%-about 50wt.%.

[0251] Embodiment 40 is the composition of any of embodiments 1-39, wherein the volume fraction of the oil continuous phase is greater than about 0.6, greater than about 0.7, or greater than about 0.8 based on the total volume of the composition.

[0252] Embodiment 41 is the composition of any of embodiments 1-39, wherein the volume fraction of the oil continuous phase is 0.5 to about 0.9, 0.5 to about 0.8, 0.5 to about 0.7, 0.6 to about 0.9, 0.6 to about 0.8, or 0.6 to about 0.7 based on the total volume of the composition.

[0253] Embodiment 42 is the composition of any of embodiments 1-41, wherein the composition further comprises a polymeric dispersant.

[0254] Embodiment 43 is the composition of embodiment 42, wherein the polymeric dispersant has an HLB (hydrophile-lipophile balance) value of less than about 7.

[0255] Embodiment 44 is the composition of embodiment 42 or 43, wherein the polymeric dispersant comprises a block copolymer or a graft copolymer comprising a nominally insoluble comonomer and a second comonomer that is soluble in the oil continuous phase.

[0256] Embodiment 45 is the composition of any of embodiments 42-44, wherein the polymeric dispersant comprises a triblock copolymer having a molecular structure that can be represented as an ABA block copolymer, wherein "A" represents a soluble comonomer and "B" represents a nominally insoluble comonomer.

[0257] Embodiment 46 is the composition of any of embodiments 42-45, wherein the polymeric dispersant comprises at least one polymer selected from the group consisting of PEG-30 dipolyhydroxystearate, polyglyceryl-2 dipolyhydroxystearate, PEG-polyethylene block copolymer, PEG-polystyrene block copolymer, PEG-3 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, polyglyceryl-3 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl-3 polydimethylsiloxyethyl dimethicone. Ethyl Dimethicone, Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone, Polyglyceryl-3 Disiloxane Dimethicone, Acrylate / Ethylhexyl / Methacrylate Dimethicone, Polyglyceryl-3 Lauryl Dimethicone Oxyethyl Dimethicone Crosspolymer, PEG-15 Lauryl Dimethicone Ethyl Dimethicone Crosspolymer, PEG-15 / Lauryl Dimethicone Crosspolymer, Dimethicone / PEG-10 / 15 Crosspolymer, Dimethicone / Polyglyceryl-3 Crosspolymer, Lauryl Dimethicone / Polyglyceryl-3 Crosspolymer, Trimethylsiloxysilicate, and mixtures thereof.

[0258] Embodiment 47 is the composition of any of embodiments 42-46, wherein the oil continuous phase comprises a single polymeric dispersant.

[0259] Embodiment 48 is the composition of any of embodiments 42-47, wherein the concentration of the polymer dispersant is about 0.1% to about 50%, about 0.1% to about 40%, about 0.1% to about 30%, about 0.1% to about 25%, about 0.1% to about 20%, about 0.1% to about 15%, about 0.1% to about 10%, about 0.1% to about 5%, about 1% to about 50%, about 1% to about 40%, about 1% to about 30%, about 1% to about 25%, about 0.1% to about 20%, about 1% to about 15%, about 1% to about 10%, or about 1% to about 5%, by weight of each dispersed phase.

[0260] Embodiment 49 is the composition of any of embodiments 1-48, wherein the oil continuous phase further comprises a viscous shear thinning oil having a high low shear rate viscosity even when heated.

[0261] Embodiment 50 is the composition of any of embodiments 1-49, wherein the composition further comprises a rheology modifier.

[0262] Embodiment 51 is the composition of embodiment 50, wherein the rheology modifier comprises a particulate rheology modifier selected from the group consisting of montmorillonite clay, silica, paraffin and natural waxes, crystalline cellulose, and mixtures thereof.

[0263] Embodiment 52 is the composition of embodiment 51, wherein the particulate rheology modifier is in a surface-modified form, wherein the surface modifier is selected from C 12 –C 18 Alkyl or aryl quaternary ammonium compounds, polymers and mixtures thereof.

[0264] Embodiment 53 is the composition of any of embodiments 50-52, wherein the rheology modifier comprises a polymeric rheology modifier.

[0265] Embodiment 54 is the composition of embodiment 53, wherein the polymeric rheology modifier comprises an oil-soluble, hydrophobic, cross-linked polymer.

[0266] Embodiment 55 is the composition of embodiment 53 or 54, wherein the rheology modifier comprises at least one polymeric rheology modifier selected from the group consisting of polyamide, polyethylene, dimethicone / vinyl dimethicone crosspolymer, dimethicone / phenyl vinyl dimethicone crosspolymer, dimethicone / lauryl dimethicone crosspolymer, and lauryl dimethicone ethyl dimethicone / bisvinyl dimethicone crosspolymer, and mixtures thereof.

[0267] Embodiment 56 is the composition of any of embodiments 53-55, wherein the rheology modifier comprises a mixture of particulates and polymeric rheology modifiers.

[0268] Embodiment 57 is the composition of any of embodiments 50-56, wherein the concentration of the rheology modifier is about 0.025wt.% to about 30wt.%, about 0.025wt.% to about 20wt.%, about 0.025wt.% to about 25wt.%, about 0.025wt.% to about 15wt.%, about 0.025wt.% to about 10wt.%, about 0.025wt.% to about 5wt.%, about 0.025wt.% to about 1wt.%, about 0.1wt.% to about 30wt.%, about 0.1wt.% to about 25wt.%, about 0.1wt.% to about 20wt.%, about 0.1wt.% to about 15wt.%, about 0.1wt.% to about 10wt.%, about 0.1wt.% to about 5wt.%, or about 0.1wt.% to about 1wt.%.

[0269] Embodiment 58 is the composition of any of embodiments 50-57, wherein the average particle size of the rheology modifier is less than about 5 microns, less than about 2.5 microns, less than about 1 micron, less than about 0.5 microns, or less than about 0.1 microns.

[0270] Embodiment 59 is the composition of any of embodiments 50-58, wherein the rheology modifier is ground to an average particle size of less than about 5 microns, less than about 2.5 microns, less than about 1 micron, less than about 0.5 microns, or less than about 0.1 microns.

[0271] Embodiment 60 is the composition of any of embodiments 1-59, wherein the composition further comprises one or more surfactants having an HLB value greater than 7.

[0272] Embodiment 61 is the composition of embodiment 60, wherein the surfactant comprises a nonionic surfactant.

[0273] Embodiment 62 is the composition of embodiment 60 or 61, wherein the surfactant comprises an ionic surfactant.

[0274] Embodiment 63 is a composition of embodiment 62, wherein the ionic surfactant is selected from alkyl / aryl ether sulfates / esters, alkyl / aryl ether sulfonates / esters, alkyl / aryl ether carboxylates / esters, alkyl / aryl ether phosphates / esters, dialkyl sulfosuccinates / esters, ethoxylated ether amines, ethoxylated-propoxylated ether amines, alkyl / aryl quaternary ammonium compounds, alkyl / aryl quaternary phosphonium compounds, ethoxylated alkyl / aryl quaternary ammonium compounds, ethoxylated alkyl / aryl quaternary phosphonium compounds, betaines, sulfobetaines, phospholipids and mixtures thereof.

[0275] Embodiment 64 is the composition of any of embodiments 60-63, wherein the concentration of the surfactant is about 0.1wt.% to about 25wt.%, about 0.1wt.% to about 20wt.%, about 0.1wt.% to about 15wt.%, about 0.1wt.% to about 10wt.%, about 0.1wt.% to about 5wt.%, about 0.1wt.% to about 3wt.%, about 0.1wt.% to about 2wt.%, about 0.5wt.% to about 25wt.%, about 0.5wt.% to about 20wt.% %, about 0.5wt.% to about 15wt.%, 0.5wt.% to about 10wt.%, about 0.5wt.% to about 5wt.%, about 0.5wt.% to about 3wt.%, about 0.5wt.% to about 2wt.%, about 1wt.% to about 25wt.%, about 1wt.% to about 20wt.%, about 1wt.% to about 15wt.%, about 1wt.% to about 10wt.%, about 1wt.% to about 5wt.%, about 1wt.% to about 3wt.%, or about 1wt.% to about 2wt.%.

[0276] Embodiment 65 is the composition of any of embodiments 1-64, wherein the composition further comprises a quaternary ammonium compound.

[0277] Embodiment 66 is the composition of embodiment 65, wherein the quaternary ammonium compound comprises an alkyl quaternary ammonium compound, an aryl quaternary ammonium compound, an alkoxylated alkyl quaternary ammonium compound, and / or an alkoxylated aryl quaternary ammonium compound.

[0278] Embodiment 67 is the composition of embodiment 65 or 66, wherein the molecular weight of the quaternary ammonium compound is no greater than about 1,000 Da, no greater than about 750 Da, or no greater than about 500 Da.

[0279] Embodiment 68 is the composition of embodiment 65 or 66, wherein the molecular weight of the quaternary ammonium compound is about 100 Da to about 1,000 Da, about 100 Da to about 750 Da, about 100 Da to about 500 Da, about 200 Da to about 1,000 Da, about 200 Da to about 750 Da, about 200 Da to about 500 Da, about 250 Da to about 1,000 Da, about 250 Da to about 750 Da, or about 250 Da to about 500 Da.

[0280] Embodiment 69 is the composition of any one of embodiments 65-68, wherein the quaternary ammonium compound has the structure of formula (I):

[0281]

[0282] Where R 1 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene; each R 3 R is independently hydrogen, or a straight or branched chain alkyl group having 1 to about 4 carbon atoms; 4 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; x and y are independently a number from 0 to about 10; X - It is an agriculturally acceptable anion.

[0283] Embodiment 70 is the composition of embodiment 69, wherein R 1 and R 4 The hydrocarbyl groups are each independently a straight chain or branched alkyl group, a straight chain or branched alkenyl group, a straight chain or branched alkynyl group, a straight chain or branched alkoxy group, an aryl group or an aralkyl group having from 1 to about 30 carbon atoms.

[0284] Embodiment 71 is the composition of embodiment 69 or 70, wherein R 1 and R 4Each is independently a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 1 to about 25 carbon atoms, 1 to about 22 carbon atoms, 1 to about 20 carbon atoms, 1 to about 18 carbon atoms, 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, 3 to about 18 carbon atoms, 3 to about 16 carbon atoms, 3 to about 14 carbon atoms, 3 to about 12 carbon atoms, 3 to about 10 carbon atoms, 3 to about 8 carbon atoms, or 3 to about 6 carbon atoms.

[0285] Embodiment 72 is the composition of any one of embodiments 69-71, wherein R 1 and R 4 have the same number of carbon atoms and / or are the same substituents.

[0286] Embodiment 73 is the composition of any one of embodiments 69-72, wherein R 1 and R 4 Each is a butyl group.

[0287] Embodiment 74 is the composition of any one of embodiments 69-73, wherein R 1 It is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl or straight chain or branched chain alkoxy having 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, or about 3 to 18 carbon atoms.

[0288] Embodiment 75 is the composition of any one of embodiments 69-74, wherein R 4 is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 1 to about 12 carbon atoms, 1 to about 10 carbon atoms, 1 to about 8 carbon atoms, 1 to 6 carbon atoms, about 1 to 4 carbon atoms, 3 to about 12 carbon atoms, 3 to -10 carbon atoms, 3 to about 8 carbon atoms, or about 3 to 6 carbon atoms.

[0289] Embodiment 76 is the composition of any one of embodiments 69-75, wherein (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently C2-C4 straight or branched chain alkylene groups.

[0290] Embodiment 77 is the composition of any one of embodiments 69-76, wherein the quaternary ammonium compound of formula (I) comprises an alkoxylated quaternary ammonium compound selected from ethoxylated quaternary ammonium compounds, propoxylated quaternary ammonium compounds, and quaternary ammonium compounds comprising various polymers or copolymers of ethylene oxide (EO) and propylene oxide (PO).

[0291] Embodiment 78 is the composition of any one of embodiments 69-77, wherein (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene groups.

[0292] Embodiment 79 is the composition of any one of embodiments 69-78, wherein (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently ethylene or propylene.

[0293] Embodiment 80 is the composition of any of embodiments 69-79, wherein the quaternary ammonium compound has a molar ratio of EO:PO of about 1:3 to about 3:1, about 1:3 to about 2:1, about 1:3 to about 1.5:1, about 1:3 to about 1:1, about 1:3 to about 1:2, about 1:2 to about 3:1, about 1:2 to about 2:1, about 1:2 to about 1.5:1, about 1:2 to about 1:1, about 1:1 to about 3:1, about 1:1 to about 2:1, or about 1:1 to about 1.5:1.

[0294] Embodiment 81 is the composition of any of embodiments 69-80, wherein x and y are independently numbers from 0 to about 8, 0 to about 6, 0 to about 4, about 0 to about 2, 1 to about 8, 1 to about 6, 1 to about 4, 1-2.

[0295] Embodiment 82 is the composition of any one of embodiments 69-81, wherein x and y are each 0 or 1.

[0296] Embodiment 83 is the composition of any one of embodiments 69-82, wherein each R 3 are independently hydrogen, methyl or ethyl.

[0297] Embodiment 84 is the composition of any one of embodiments 69-83, wherein each R 3 For hydrogen.

[0298] Embodiment 85 is the composition of any one of embodiments 69-84, wherein X - is an anion selected from sulfate, hydroxide, chloride, bromide and nitrate.

[0299] Embodiment 86 is the composition of any one of embodiments 69-85, wherein X - It is the chloride or hydroxide anion.

[0300] Embodiment 87 is the composition of any of embodiments 65-86, wherein the quaternary ammonium compound is selected from tetrabutylammonium salts and trimethyl-tetradecylammonium salts.

[0301] Embodiment 88 is the composition of any one of embodiments 65-87, wherein the quaternary ammonium compound has the structure of formula (II):

[0302]

[0303] Where R is an alkyl group (e.g. C1-C 20 alkyl), n is the total number of moles of (CH2CH2O), and n+z is a number from 0 to 15.

[0304] Embodiment 89 is the composition of any one of embodiments 65-88, wherein the quaternary ammonium compound is selected from isodecanyloxypropyl dihydroxyethyl methyl ammonium chloride, isotridecyloxypropyl dihydroxyethyl methyl ammonium chloride, isotridecyloxypropyl poly(5)oxyethylene methyl ammonium chloride, octadecyl dihydroxyethyl methyl ammonium chloride, and mixtures thereof.

[0305] Embodiment 90 is the composition of any one of embodiments 65-89, wherein the composition comprises an auxinic herbicide and the molar ratio of the quaternary amine compound to the auxinic herbicide is at least about 0.25:1, at least about 0.5:1, at least about 0.75:1, or at least about 1:1.

[0306] Embodiment 91 is the composition of any one of embodiments 65-89, wherein the composition comprises an auxin herbicide and the molar ratio of the quaternary amine compound to the auxin herbicide is 0.25:1 to about 2:1, about 0.25:1 to about 1.75:1, about 0.25:1 to about 1.5:1, about 0.25:1 to about 1.25:1, about 0.25:1 to about 1:1, about 0.5:1 to about 2:1, about 0.5:1 to about 1.75:1, about 1 to about 1:1, about 0.5:1 to about 1.5:1, about 0.5:1 to about 1.25:1, about 0.5:1 to about 1:1, about 0.75:1 to about 2:1, about 0.75:1 to about 1.75:1, about 0.75:1 to about 1.5:1, about 0.75:1 to about 1.25:1, about 0.75:1 to about 1:1, about 1:1 to about 2:1, about 1:1 to about 1.75:1, about 1:1 to about 1.5:1, or about 1:1 to about 1.25:1.

[0307] Embodiment 92 is the composition of any of embodiments 1-91, wherein the total herbicide loading of the composition is at least about 10 wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, at least about 50 wt.%, or at least about 60 wt.%.

[0308] Embodiment 93 is the composition of any of embodiments 1-91, wherein the total herbicide loading of the composition is about 10 wt.% to about 80 wt.%, about 20 wt.% to about 80 wt.%, about 30 wt.% to about 80 wt.%, about 40 wt.% to about 80 wt.%, about 50 wt.% to about 80 wt.%, about 60 wt.% to about 80 wt.%, about 10 wt.% to about 70 wt.%, about 20 wt.% to about 80 wt.%, about 10 wt.% to about 80 wt.%, about 20 wt.% to about 80 wt.%, about 30 wt.% to about 80 wt.%, about 40 wt.% to about 80 wt.%, about 50 wt.% to about 80 wt.%, about 60 wt.% to about 80 wt.%, about 10 wt.% to about 70 wt.%, about 20 wt.% to about 80 wt. % - about 70wt.%, about 30wt.% - about 70wt.%, about 40wt.% - about 70wt.%, about 50wt.% - about 70wt.%, about 60wt.% - about 70wt.%, about 10wt.% - about 60wt.%, about 20wt.% - about 60wt.%, about 30wt.% - about 60wt.%, about 40wt.% - about 60wt.%, or about 50wt.% - about 60wt.%.

[0309] Embodiment 94 is the composition of any of embodiments 1-93, wherein the concentration of the acetamide herbicide is at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, or at least about 40 wt.%.

[0310] Embodiment 95 is the composition of any one of embodiments 1-93, wherein the concentration of the acetamide herbicide is about 10 wt.% to about 65 wt.%, about 20 wt.% to about 65 wt.%, about 30 wt.% to about 65 wt.%, about 40 wt.% to about 65 wt.%, about 50 wt.% to about 65 wt.%, about 10 wt.% to about 60 wt.%, about 20 wt.% to about 60 wt. %, about 30wt.%-about 60wt.%, about 40wt.%-about 60wt.%, about 50wt.%-about 60wt.%, about 10wt.%-about 55wt.%, about 20wt.%-about 55wt.%, about 30wt.%-about 55wt.%, about 40wt.%-about 55wt.%, about 50wt.%-about 55wt.%, or about 40wt.%-about 50wt.%.

[0311] Embodiment 96 is the composition of any one of embodiments 1-95, wherein the acetamide herbicide is selected from acetochlor, alachlor, butachlor, butenetrachlor, sulfamethoxam, decachloramine, norformyl, dimethochlor, dimethochlor, dimethochlor-P, mefenacet, metazachlor, isopropyl metolachlor, S-isopropyl metolachlor, naproxen, pretilachlor, naprofil, promethachlor, isopropyl metolachlor, clarithromycin, terbutaline, dimethenamid and dimethochlor, their salts and esters, and mixtures thereof.

[0312] Embodiment 97 is the composition of any one of embodiments 1-96, wherein the acetamide herbicide is selected from acetochlor, alachlor, isopropyl metolachlor, S-isopropyl metolachlor, and mixtures thereof.

[0313] Embodiment 98 is the composition of any one of embodiments 1-97, wherein the acetamide herbicide comprises acetochlor.

[0314] Embodiment 99 is the composition of any of embodiments 1-98, wherein the concentration of the solid-phase herbicide is at least about 1 wt.%, at least about 2 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, or at least about 30 wt.%.

[0315] Embodiment 100 is the composition of any of embodiments 1-98, wherein the concentration of the solid phase herbicide is about 1 wt.% to about 40 wt.%, about 1 wt.% to about 30 wt.%, about 1 wt.% to about 20 wt.%, about 1 wt.% to about 10 wt.%, about 1 wt.% to about 5 wt.%, about 2 wt.% to about 40 wt.%, about 2 wt.% to about 30 wt.%, about 2 wt.% to about 20 wt.%, about 2 wt.% to about 10 wt.%, about About 2wt.% - about 5wt.%, about 5wt.% - about 40wt.%, about 5wt.% - about 30wt.%, about 5wt.% - about 20wt.%, about 5wt.% - about 10wt.%, about 10wt.% - about 40wt.%, about 10wt.% - about 30wt.%, about 10wt.% - about 20wt.%, about 15wt.% - about 40wt.%, about 15wt.% - about 30wt.%, or about 15wt.% - about 20wt.%.

[0316] Embodiment 101 is the composition of any of embodiments 1-100, wherein the composition further comprises a safener.

[0317] Embodiment 102 is a method for preparing a herbicide dispersion composition, comprising:

[0318] A non-aqueous liquid, a solid phase herbicide, and an acetamide herbicide are mixed to form a herbicide dispersion composition, the composition comprising an oil continuous phase and a dispersed phase, the oil continuous phase comprising the non-aqueous liquid and the acetamide herbicide, and the dispersed phase comprising the solid phase herbicide, wherein the weight ratio of the non-aqueous liquid to the acetamide herbicide is at least about 1:1, at least about 1.1:1, at least about 1.2:1, at least about 1.3:1, at least about 1.4:1, or at least about 1.5:1.

[0319] Embodiment 103 is the method of embodiment 102, wherein the non-aqueous liquid and the acetamide herbicide are mixed prior to mixing with the solid phase herbicide.

[0320] Embodiment 104 is the method of embodiment 102, wherein the non-aqueous liquid and the solid phase herbicide are mixed prior to mixing with the acetamide herbicide.

[0321] Embodiment 105 is a method for preparing a herbicide dispersion composition, comprising:

[0322] mixing an acetamide herbicide and an auxin herbicide to form a first mixture, wherein the auxin herbicide is at least partially soluble in the acetamide herbicide;

[0323] mixing the non-aqueous liquid and the solid-phase herbicide to form a second mixture; and

[0324] The first mixture is mixed with the second mixture to form a herbicide dispersion composition comprising an oil continuous phase comprising a non-aqueous liquid, a first bulk dispersed phase comprising an acetamide herbicide and an auxin herbicide at least partially soluble in the acetamide herbicide, and a second bulk dispersed phase comprising a solid phase herbicide.

[0325] Embodiment 106 is the method of embodiment 105, wherein the second bulk dispersed phase further comprises a second bulk dispersed phase oil, and wherein the solid phase herbicide is dispersed in the second bulk dispersed phase oil.

[0326] Embodiment 107 is the method of embodiment 105, further comprising mixing the solid phase herbicide with a second bulk dispersed phase oil prior to mixing the non-aqueous liquid with the solid phase herbicide.

[0327] Embodiment 108 is the method of any of embodiments 105-107, wherein the herbicide dispersion composition further comprises a dispersant.

[0328] Embodiment 109 is the method of embodiment 108, further comprising mixing a dispersant with the non-aqueous liquid prior to mixing the non-aqueous liquid with the solid-phase herbicide.

[0329] Embodiment 110 is the method of any of embodiments 102-109, further comprising grinding the solid-phase herbicide.

[0330] Embodiment 111 is the method of any of embodiments 102-110, further comprising grinding the herbicide dispersion composition.

[0331] Embodiment 112 is a method of preparing a herbicide application mixture, the method comprising mixing water with the composition of any of embodiments 1-101 to form the herbicide application mixture.

[0332] Embodiment 113 is a herbicide composition comprising an auxin herbicide acid and

[0333] (i) a quaternary ammonium compound and / or a reaction product of an auxin herbicide and a quaternary ammonium compound, wherein the quaternary ammonium compound has the structure of formula (I):

[0334]

[0335] Where R 1 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene; each R 3 R is independently hydrogen, or a straight or branched chain alkyl group having 1 to about 4 carbon atoms; 4 is a hydrocarbon group or a substituted hydrocarbon group having 1 to about 30 carbon atoms; x and y are independently a number from 0 to about 10; X - is an agriculturally acceptable anion, provided that when x and y are each 0 and R 1 , R 2 , R 3 and R 4 When at least one of X is an alkyl or aralkyl group having 2 to 4 carbon atoms, - is not a hydroxide anion, and / or

[0336] (ii) an affinity solvent for the auxin herbicide acid, wherein the solvent satisfies at least one of the following:

[0337] (1) a molecular weight of at least about 300 grams per mole, at least about 600 grams per mole, or at least about 900 grams per mole (e.g., from about 900 grams per mole to about 1500 grams per mole),

[0338] (2) at least one double bond group per solvent molecule, and / or

[0339] (3) Each solvent molecule contains at least four hydrogen bonding groups.

[0340] Embodiment 114 is the composition of embodiment 113, wherein the composition comprises a quaternary ammonium compound and / or a reaction product of an auxin herbicide and a quaternary ammonium compound.

[0341] Embodiment 115 is the composition of embodiment 113 or 114, wherein the molecular weight of the quaternary ammonium compound is no greater than about 1,000 Da, no greater than about 750 Da, or no greater than about 500 Da.

[0342] Embodiment 116 is the composition of embodiment 113 or 114, wherein the molecular weight of the quaternary ammonium compound is about 100 Da to about 1,000 Da, about 100 Da to about 750 Da, about 100 Da to about 500 Da, about 200 Da to about 1,000 Da, about 200 Da to about 750 Da, about 200 Da to about 500 Da, about 250 Da to about 1,000 Da, about 250 Da to about 750 Da, or about 250 Da to about 500 Da.

[0343] Embodiment 117 is the composition of any one of embodiments 113-116, wherein R 1 and R 4 The hydrocarbyl groups are each independently a straight chain or branched alkyl group, a straight chain or branched alkenyl group, a straight chain or branched alkynyl group, a straight chain or branched alkoxy group, an aryl group or an aralkyl group having from 1 to about 30 carbon atoms.

[0344] Embodiment 118 is the composition of any one of embodiments 113-117, wherein R 1 and R 4 Each is independently a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 1 to about 25 carbon atoms, 1 to about 22 carbon atoms, 1 to about 20 carbon atoms, 1 to about 18 carbon atoms, 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, 3 to about 18 carbon atoms, 3 to about 16 carbon atoms, 3 to about 14 carbon atoms, 3 to about 12 carbon atoms, 3 to about 10 carbon atoms, 3 to about 8 carbon atoms, or 3 to about 6 carbon atoms.

[0345] Embodiment 119 is the composition of any one of embodiments 113-118, wherein R 1 and R 4 have the same number of carbon atoms and / or are the same substituents.

[0346] Embodiment 120 is the composition of any one of embodiments 113-119, wherein R 1 and R 4 Each is a butyl group.

[0347] Embodiment 121 is the composition of any one of embodiments 113-120, wherein R 1 It is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl or straight chain or branched chain alkoxy having 3 to about 25 carbon atoms, 3 to about 22 carbon atoms, 3 to about 20 carbon atoms, or about 3 to 18 carbon atoms.

[0348] Embodiment 122 is the composition of any one of embodiments 113-121, wherein R 4is a straight chain or branched chain alkyl, straight chain or branched chain alkenyl, or straight chain or branched chain alkoxy having 1 to about 12 carbon atoms, 1 to about 10 carbon atoms, 1 to about 8 carbon atoms, 1 to 6 carbon atoms, about 1 to 4 carbon atoms, 3 to about 12 carbon atoms, 3 to -10 carbon atoms, 3 to about 8 carbon atoms, or about 3 to 6 carbon atoms.

[0349] Embodiment 123 is the composition of any one of embodiments 113-122, wherein (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently C2-C4 straight or branched chain alkylene groups.

[0350] Embodiment 124 is the composition of any one of embodiments 113-123, wherein the quaternary ammonium compound of formula (I) comprises an alkoxylated quaternary ammonium compound selected from ethoxylated quaternary ammonium compounds, propoxylated quaternary ammonium compounds, and quaternary ammonium compounds comprising various polymers or copolymers of ethylene oxide (EO) and propylene oxide (PO).

[0351] Embodiment 125 is the composition of any one of embodiments 113-124, wherein (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently linear or branched C2-C4 alkylene groups.

[0352] Embodiment 126 is the composition of any one of embodiments 113-125, wherein (R 2 O) x and (R 2 O) y Each R in each of the groups 2 are independently ethylene or propylene.

[0353] Embodiment 127 is the composition of any of embodiments 113-126, wherein the molar ratio of EO:PO of the quaternary ammonium compound is from about 1:3 to about 3:1, from about 1:3 to about 2:1, from about 1:3 to about 1.5:1, from about 1:3 to about 1:1, from about 1:3 to about 1:2, from about 1:2 to about 3:1, from about 1:2 to about 2:1, from about 1:2 to about 1.5:1, from about 1:2 to about 1:1, from about 1:1 to about 3:1, from about 1:1 to about 2:1, or from about 1:1 to about 1.5:1.

[0354] Embodiment 128 is the composition of any of embodiments 113-127, wherein x and y are independently numbers from 0 to about 8, 0 to about 6, 0 to about 4, about 0 to about 2, 1 to about 8, 1 to about 6, 1 to about 4, 1-2.

[0355] Embodiment 129 is the composition of any one of embodiments 113-128, wherein x and y are each 0 or 1.

[0356] Embodiment 130 is the composition of any one of embodiments 113-129, wherein each R 3 are independently hydrogen, methyl or ethyl.

[0357] Embodiment 131 is the composition of any one of embodiments 113-130, wherein each R 3 For hydrogen.

[0358] Embodiment 132 is the composition of any one of embodiments 113-131, wherein X - is an anion selected from sulfate, hydroxide, chloride, bromide and nitrate.

[0359] Embodiment 133 is the composition of any one of embodiments 113-132, wherein X - It is a chloride ion or a hydroxide anion.

[0360] Embodiment 134 is the composition of any of embodiments 113-133, wherein the quaternary ammonium compound is selected from tetrabutylammonium salts and trimethyl-tetradecylammonium salts.

[0361] Embodiment 135 is the composition of any one of embodiments 113-134, wherein the quaternary ammonium compound has the structure of formula (II):

[0362]

[0363] Where R is an alkyl group (e.g. C1-C 20 alkyl), n is the total number of moles of (CH2CH2O), and n+z is a number from 0 to 15.

[0364] Embodiment 136 is the composition of any one of embodiments 113-135, wherein the quaternary ammonium compound is selected from isodecanoxypropyl dihydroxyethyl methyl ammonium chloride, isotridecyloxypropyl dihydroxyethyl methyl ammonium chloride, isotridecyloxypropyl poly(5)oxyethylene methyl ammonium chloride, octadecyl dihydroxyethyl methyl ammonium chloride, and mixtures thereof.

[0365] Embodiment 137 is the composition of any of embodiments 113-136, wherein the molar ratio of the quaternary ammonium compound to the auxin herbicide is at least about 0.25:1, at least about 0.5:1, at least about 0.75:1, or at least about 1:1.

[0366] Embodiment 138 is the composition of any of embodiments 113-137, wherein the molar ratio of the quaternary ammonium compound to the auxin herbicide is 0.25:1 to about 2:1, about 0.25:1 to about 1.75:1, about 0.25:1 to about 1.5:1, about 0.25:1 to about 1.25:1, about 0.25:1 to about 1:1, about 0.5:1 to about 2:1, about 0.5:1 to about 1.75:1, about 0.5:1 to about 1.5:1, about 0.25:1 to about 1.25:1, about 0.25:1 to about 1:1, about 0.5:1 to about 2:1, about 0.5:1 to about 1.75:1, about 0.5:1 to about about 1.5:1, about 0.5:1-about 1.25:1, about 0.5:1-about 1:1, about 0.75:1-about 2:1, about 0.75:1-about 1.75:1, about 0.75:1-about 1.5:1, about 0.75:1-about 1.25:1, about 0.75:1-about 1:1, about 1:1-about 2:1, about 1:1-about 1.75:1, about 1:1-about 1.5:1, or about 1:1-about 1.25:1.

[0367] Embodiment 139 is the composition of embodiment 113, wherein the composition comprises an affinity solvent.

[0368] Embodiment 140 is the composition of any one of embodiments 114-138, wherein the composition comprises an affinity solvent.

[0369] Embodiment 141 is the composition of any one of embodiments 113-140, wherein the affinity solvent comprises an alkanediol.

[0370] Embodiment 142 is the composition of any one of embodiments 113-141, wherein the affinity solvent comprises a triglyceride.

[0371] Embodiment 143 is the composition of any one of embodiments 113-142, wherein the affinity solvent comprises castor oil.

[0372] Embodiment 144 is the composition of any of embodiments 113-143, wherein the weight ratio of affinity solvent to auxin herbicide acid is at least about 1:1, at least about 1.5:1, at least about 2:1, or at least about 3:1.

[0373] Embodiment 145 is the composition of any of embodiments 113-143, wherein the weight ratio of affinity solvent to auxin herbicide acid is about 1:1 to about 5:1, about 1:1 to about 4:1, about 1:1 to about 3:1, about 1.5:1 to about 5:1, about 1.5:1 to about 4:1, about 1.5:1 to about 3:1, about 2:1 to about 5:1, about 2:1 to about 4:1, or about 2:1 to about 3:1.

[0374] Embodiment 146 is the composition of any one of embodiments 113-145, wherein the auxin herbicide is selected from 3,6-dichloro-2-methoxybenzoic acid (dicamba); 2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB); dichloropropionic acid; 2-methyl-4-chlorophenoxyacetic acid (MCPA); 4-(4-chloro-2-methylphenoxy)butyric acid (MCPB); 4-chlorophenoxyacetic acid; 2 ,4,5-trichlorophenoxyacetic acid (2,4,5-T); clopyralid; clopyralid; silanol; triclopyr; 2-4-methoprop; piclopirox; quick-kill barnyard; chloranil; chloranil; chloranil; chloranil; chloranil; chloranil; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; Benzyl-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1-isobutyryl-1H-indol-6-yl)pyridine-2-carboxylate; methyl 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylate; methyl 4-amino-3-chloro-6-[1-(2,2-dimethylpropanoyl)-7-fluoro-1H-indol-6-yl]-5-fluoropyridine-2-carboxylate;

[0063] In some embodiments, the present invention relates to methyl 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate; methyl 6-(1-acetyl-7-fluoro-1H-indol-6-yl)-4-amino-3-chloro-5-fluoropyridine-2-carboxylate; potassium 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; butyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)pyridine-2-carboxylate; salts and esters thereof; and mixtures thereof.

[0375] Embodiment 147 is the composition of any one of embodiments 113-146, wherein the auxin herbicide acid comprises dicamba acid.

[0376] Embodiment 148 is the composition of any one of embodiments 113-147, wherein the auxinic herbicide acid comprises 2,4-D acid.

[0377] Embodiment 149 is the composition of any of embodiments 113-148, wherein the concentration of the auxin herbicide acid is at least about 1 wt.%, at least about 2 wt.%, at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 30 wt.%, at least about 40 wt.%, or at least about 45 wt.%.

[0378] Embodiment 150 is the composition of any of embodiments 113-148, wherein the concentration of the auxin herbicide acid is about 0.5 wt.% to about 10 wt.%, about 0.5 wt.% to about 5 wt.%, about 0.5 wt.% to about 3 wt.%, about 10 wt.% to about 55 wt.%, about 15 wt.% to about 55 wt.%, about 20 wt.% to about 55 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 45 wt.% to about 55 wt.%, about 10 wt.% to about 50 wt.%, about 15 wt.% to about 50 wt.%, about 20 wt.% to about 50 wt.%, about % to about 40wt.%, about 30wt.% to about 50wt.%, about 40wt.% to about 50wt.%, about 45wt.% to about 50wt.%, 10wt.% to about 45wt.%, about 15wt.% to about 45wt.%, about 20wt.% to about 45wt.%, about 30wt.% to about 45wt.%, about 40wt.% to about 45wt.%, 10wt.% to about 40wt.%, about 15wt.% to about 40wt.%, about 20wt.% to about 40wt.%, about 30wt.% to about 40wt.%, 10wt.% to about 25wt.%, about 15wt.% to about 25wt.%, or about 10wt.% to about 20wt.%.

[0379] Embodiment 151 is the composition of any of embodiments 113-150, further comprising an alkanediol.

[0380] Embodiment 152 is the composition of embodiment 151, wherein the alkanediol comprises C2-C 10 Diol or C2-C6 diol.

[0381] Embodiment 153 is the composition of embodiment 151 or 152, wherein the alkanediol comprises a branched C2-C 10 Diol or branched C2-C6 diol.

[0382] Embodiment 154 is the composition of any of embodiments 151-153, wherein the alkane diol is selected from propylene glycol; hexylene glycol; 1,3-propanediol; 1,4-butanediol; 1,3-butanediol; and mixtures thereof.

[0383] Embodiment 154 is the composition of any of embodiments 151-154, wherein the molar ratio of alkanediol to auxin herbicide is at least about 1:1, at least about 2:1, at least about 3:1, at least about 4:1, at least about 5:1, at least about 6:1, at least about 7:1, at least about 8:1, or at least about 9:1.

[0384] Embodiment 156 is the composition of any of embodiments 151-154, wherein the molar ratio of alkanediol to auxin herbicide is about 1:1 to about 20:1, about 2:1 to about 20:1, about 5:1 to about 20:1, about 7:1 to about 20:1, about 1:1 to about 10:1, about 2:1 to about 10:1, about 5:1 to about 10:1, or about 7:1 to about 10:1.

[0385] Embodiment 157 is the composition of any of embodiments 151-156, wherein the alkanediol concentration is at least about 5 wt.%, at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, or at least about 30 wt.%.

[0386] Embodiment 158 ​​is the composition of any of embodiments 151-156, wherein the alkanediol concentration is about 5 wt.% to about 40 wt.%, about 5 wt.% to about 35 wt.%, about 5 wt.% to about 30 wt.%, about 5 wt.% to about 25 wt.%, about 5 wt.% to about 20 wt.%, about 5 wt.% to about 15 wt.%, about 5 wt.% to about 10 wt.%, about 10 wt.% to about 40 wt.%, about 10 wt.% to about 3 % - about 5wt.%, about 10wt.% - about 30wt.%, about 10wt.% - about 25wt.%, about 10wt.% - about 20wt.%, about 10wt.% - about 15wt.%, about 15wt.% - about 40wt.%, about 15wt.% - about 35wt.%, about 15wt.% - about 30wt.%, about 20wt.% - about 40wt.%, about 20wt.% - about 35wt.%, or about 20wt.% - about 30wt.%.

[0387] Embodiment 159 is the composition of any one of embodiments 151-158, further comprising a solvent.

[0388] Embodiment 160 is the composition of embodiment 159, wherein the solvent is water.

[0389] Embodiment 161 is a pesticide dispersion composition comprising:

[0390] (a) an oil continuous phase comprising a non-aqueous liquid having a dielectric constant of about 10 or less as measured at 25°C and having little solubility for the ionic insecticidal active ingredient;

[0391] (b) a dispersed phase comprising the ionic insecticidal active ingredient suspended in an oil continuous phase;

[0392] (c) rheology modifiers; and

[0393] (d) Dispersant.

[0394] Embodiment 162 is the composition of embodiment 161, wherein the ionic insecticidal active ingredient is a solid-phase insecticidal active ingredient.

[0395] Embodiment 163 is the composition of embodiment 161 or 162, wherein the ionic insecticidal active ingredient comprises a solid-phase ionic herbicide selected from glyphosate, glufosinate, auxin herbicides or salts thereof.

[0396] Embodiment 164 is the composition of any one of embodiments 161-163, wherein the ionic insecticidal active ingredient is dissolved in a polar liquid immiscible with the non-aqueous liquid of the continuous phase, and the resulting solution is emulsified in the continuous phase to form a polar liquid-in-oil emulsion.

[0397] Embodiment 165 is the composition of embodiment 164, wherein the polar liquid is selected from the group consisting of water, alcohols, polyols, ethers, polar esters, polar amides, and mixtures thereof.

[0398] Embodiment 166 is the composition of any one of embodiments 161-165, wherein the non-aqueous liquid is selected from the group consisting of oily pesticidal active ingredients, hydrocarbon-based liquids, vegetable oils, ester oils, amide oils, aromatic oils, silicone oils, and mixtures thereof.

[0399] Embodiment 167 is the composition of any one of embodiments 161-166, wherein the dielectric constant of the non-aqueous liquid measured at 25°C is about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less, or about 2 or less.

[0400] Embodiment 168 is the composition of any one of embodiments 161-168, wherein the non-aqueous liquid comprises an acetamide herbicide selected from the group consisting of acetochlor, alachlor, butachlor, butenesulfonamide, decachloramine, norformyl, dimethochlor, dimethochlor, dimethochlor-P, mefenacet, metazachlor, isopropyl metolachlor, S-isopropyl metolachlor, naproxen, pretilachlor, naclostrobin, promethachlor, isopropyl metolachlor, clarithromycin, terbutaline, dimethenamid and dimethochlor, their salts and esters, and mixtures thereof.

[0401] Embodiment 169 is an oil-in-oil co-emulsion pesticide composition comprising: an oil continuous phase comprising a first non-aqueous liquid;

[0402] (b) a first dispersed phase emulsified in an oil continuous phase, wherein the first dispersed phase comprises a second non-aqueous liquid and a pesticidally active ingredient dissolved in the second non-aqueous liquid;

[0403] (c) a second dispersed phase emulsified in an oil continuous phase, wherein the second dispersed phase comprises a third non-aqueous liquid and the solid-phase pesticidal active ingredient is dispersed in the third non-aqueous liquid;

[0404] (d) rheology modifiers;

[0405] (e) emulsifiers; and

[0406] (f) a dispersant, wherein the dispersant is insoluble in the first non-aqueous liquid, and wherein the first non-aqueous liquid, the second non-aqueous liquid, and the third non-aqueous liquid are different and substantially immiscible with each other.

[0407] Embodiment 170 is a composition of embodiment 169, wherein the dielectric constant of the first non-aqueous liquid measured at 25°C is about 10 or less, about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less or about 2 or less.

[0408] Embodiment 171 is the composition of embodiment 169 or 170, wherein the first non-aqueous liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof.

[0409] Embodiment 172 is the composition of any one of embodiments 169-171, wherein the second non-aqueous liquid is selected from the group consisting of oily pesticidal active ingredients, vegetable oils, ester oils, amide oils, aromatic oils, and mixtures thereof.

[0410] Embodiment 173 is the composition of any one of embodiments 169-172, wherein the third non-aqueous liquid is selected from the group consisting of silicone oils, hydrocarbon-based liquids, vegetable oils, and mixtures thereof.

[0411] Embodiment 174 is the composition of any one of embodiments 169-173, wherein the third non-aqueous liquid comprises castor oil.

[0412] Embodiment 175 is the composition of any one of embodiments 169-174, wherein the third non-aqueous liquid comprises silicone oil.

[0413] Embodiment 176 is the composition of any of embodiments 169-175, wherein the second dispersed phase comprises a dispersant comprising a copolymer of acrylates / ethylhexyl acrylate / dimethicone methacrylate.

[0414] Embodiment 177 is the composition of any one of embodiments 169-176, wherein the pesticidally active ingredient dissolved in the second non-aqueous liquid comprises an auxin herbicide.

[0415] Embodiment 178 is the composition of any one of embodiments 169-177, wherein the solid-phase pesticidal active ingredient comprises at least one solid-phase herbicide selected from the group consisting of hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, auxin herbicides, protoporphyrinogen oxidase (PPO) inhibitors, glyphosate, glufosinate and salts thereof.

[0416] Embodiment 179 is a polar liquid-in-oil and oil-in-oil co-emulsion pesticide composition comprising:

[0417] (a) an oil continuous phase comprising a first liquid comprising a non-aqueous liquid that is substantially immiscible with water;

[0418] (b) a first dispersed phase emulsified in an oil continuous phase, wherein the first dispersed phase comprises a second liquid and a pesticidally active ingredient dissolved in the second liquid;

[0419] (c) a second dispersed phase emulsified in an oil continuous phase, wherein the second dispersed phase comprises a third liquid and a solid-phase pesticidal active ingredient dispersed in the third liquid;

[0420] (d) rheology modifiers;

[0421] (e) emulsifiers; and

[0422] (f) a dispersant, wherein the dispersant is insoluble in the first liquid, and

[0423] Wherein the first liquid, the second liquid and the third liquid are different and substantially immiscible with each other.

[0424] Embodiment 180 is the composition of embodiment 179, wherein the dielectric constant of the first liquid measured at 25°C is about 10 or less, about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less or about 2 or less.

[0425] Embodiment 181 is the composition of embodiment 179 or 180, wherein the first liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof.

[0426] Embodiment 182 is the composition of any one of embodiments 179-181, wherein the second non-aqueous liquid is selected from the group consisting of polar liquids, vegetable oils, ester oils, amide oils, aromatic oils, and mixtures thereof.

[0427] Embodiment 183 is the composition of any one of embodiments 179-182, wherein the second liquid comprises castor oil.

[0428] Embodiment 184 is the composition of embodiment 183, wherein the polar liquid is selected from the group consisting of water, alcohols, polyols, ethers, polar esters, polar amides, and mixtures thereof.

[0429] Embodiment 185 is the composition of any one of embodiments 179-184, wherein the third liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof.

[0430] Embodiment 186 is the composition of any one of embodiments 179-185, wherein the third liquid comprises silicone oil.

[0431] Embodiment 187 is the composition of any of embodiments 179-186, wherein the second dispersed phase comprises a dispersant comprising a copolymer of acrylates / ethylhexyl acrylate / dimethicone methacrylate.

[0432] Embodiment 188 is the composition of any one of embodiments 179-187, wherein the pesticidally active ingredient dissolved in the second non-aqueous liquid comprises an auxin herbicide.

[0433] Embodiment 189 is the composition of any one of embodiments 179-188, wherein the solid-phase pesticidal active ingredient comprises at least one solid-phase herbicide selected from the group consisting of hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, and combinations thereof.

[0434] Embodiment 190 is a wax-in-oil and oil-in-oil co-emulsion pesticide composition comprising:

[0435] (a) an oil continuous phase comprising a first liquid comprising a non-aqueous liquid that is substantially immiscible with water;

[0436] (b) a first dispersed phase emulsified in an oil continuous phase, wherein the first dispersed phase comprises (i) a second liquid that is substantially immiscible with the first liquid, and (ii) a waxy solid, and optionally a pesticidally active ingredient in molten form that is soluble in the second liquid and / or in the waxy solid;

[0437] (c) a second dispersed phase emulsified in the oil continuous phase, wherein the second dispersed phase comprises (i) a third liquid that is substantially immiscible with the first liquid and (ii) a pesticidally active ingredient dispersed in the third liquid;

[0438] (d) a third dispersed phase emulsified in an oil continuous phase, wherein the third dispersed phase comprises a fourth liquid and a solid-phase pesticidal active ingredient dispersed in the fourth liquid;

[0439] (e) rheology modifiers;

[0440] (f) emulsifiers; and

[0441] (g) a dispersant, wherein the dispersant is insoluble in the first liquid.

[0442] Embodiment 191 is a composition of embodiment 190, wherein the dielectric constant of the first liquid measured at 25°C is about 10 or less, about 5 or less, about 4 or less, about 3.5 or less, about 3 or less, about 2.5 or less or about 2 or less.

[0443] Embodiment 192 is the composition of embodiment 190 or 191, wherein the first liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof.

[0444] Embodiment 193 is the composition of any of embodiments 190-192, wherein the second non-aqueous liquid is selected from the group consisting of polar liquids, vegetable oils, ester oils, amide oils, aromatic oils, and mixtures thereof.

[0445] Embodiment 194 is the composition of embodiment 193, wherein the polar liquid is selected from the group consisting of water, alcohols, polyols, ethers, polar esters, polar amides, and mixtures thereof.

[0446] Embodiment 195 is the composition of any one of embodiments 190-194, wherein the waxy solid is miscible with the second liquid when the mixture of the waxy solid and the second liquid is heated above the melting point of the waxy solid.

[0447] Embodiment 196 is the composition of embodiment 195, wherein the mixture of the waxy solid and the second liquid is prepared by melting the waxy solid and mixing the molten waxy solid with the second liquid.

[0448] Embodiment 197 is the composition of any of embodiments 190-196, wherein the first dispersed phase comprises solid particles at a temperature below the melting point of the waxy solid.

[0449] Embodiment 198 is the composition of any one of embodiments 190-197, wherein the second liquid is present in a solid matrix comprising a waxy solid.

[0450] Embodiment 199 is the composition of any one of embodiments 190-198, wherein the waxy solid is selected from the group consisting of high molecular weight polymer waxes, hydrocarbon waxes, natural waxes, triglyceride waxes, ester waxes, and mixtures thereof.

[0451] Embodiment 200 is the composition of embodiment 199, wherein the high molecular weight polymer wax comprises polyethylene glycol wax.

[0452] Embodiment 201 is the composition of embodiment 200, wherein the polyethylene glycol wax has an average molecular weight of about 1000 Da or more or about 1000 Da to about 9000 Da.

[0453] Embodiment 202 is the composition of embodiment 200 or 201, wherein the waxy solid has a melting point of about 35°C to about 95°C, about 40°C to about 95°C, about 50°C to about 95°C, or about 60°C to about 95°C.

[0454] Embodiment 203 is the composition of any of embodiments 190-202, wherein the amount of the second liquid in the first dispersed phase is no greater than about 95 wt. % of the first dispersed phase.

[0455] Embodiment 204 is the composition of any one of embodiments 190-203, wherein the second liquid and the third liquid are the same.

[0456] Embodiment 205 is the composition of any one of embodiments 190-204, wherein the second liquid and / or the third liquid comprises castor oil.

[0457] Embodiment 206 is the composition of any one of embodiments 190-205, wherein the fourth liquid is selected from hydrocarbon-based liquids, vegetable oils, silicone oils, and mixtures thereof.

[0458] Embodiment 207 is the composition of any one of embodiments 190-206, wherein the fourth liquid comprises silicone oil.

[0459] Embodiment 208 is the composition of any of embodiments 190-207, wherein the third dispersed phase comprises a dispersant comprising a copolymer of acrylates / ethylhexyl acrylate / dimethicone methacrylate.

[0460] Embodiment 209 is the composition of any one of embodiments 190-208, wherein the pesticidally active ingredient soluble in the second liquid and / or soluble in the molten form of the waxy solid comprises an acetamide herbicide.

[0461] Embodiment 210 is the composition of any one of embodiments 190-209, wherein the pesticidally active ingredient dispersed in the third liquid comprises an auxin herbicide.

[0462] Embodiment 211 is the composition of any one of embodiments 190-210, wherein the solid-phase pesticidal active ingredient comprises at least one solid-phase herbicide selected from the group consisting of hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, auxin herbicides, protoporphyrinogen oxidase (PPO) inhibitors, glyphosate, glufosinate and their salts.

[0463] Embodiment 212 is the composition of any of embodiments 161-211, wherein the rheology modifier is effective in a temperature range of about -20°C to about 54°C.

[0464] Embodiment 213 is the composition of any of embodiments 161-212, wherein the rheology modifier comprises a surface-modified montmorillonite clay.

[0465] Embodiment 214 is the composition of any of embodiments 161-213, wherein the rheology modifier comprises a surface-modified montmorillonite clay having multiple surface modifications imparted by a combination of a plurality of surface-modifying surfactants, at least one of which is a polymeric surfactant having a molecular weight greater than 2,000 Daltons.

[0466] Embodiment 215 is the composition of embodiment 213 or 214, wherein the surface-modified montmorillonite clay is ground to a smaller particle size to increase the yield stress and shear thinning properties of the clay.

[0467] Embodiment 216 is the composition of any of embodiments 161-215, wherein the dispersant comprises a block copolymer or a graft copolymer comprising a nominally insoluble comonomer and a second comonomer that is highly soluble in the oil continuous phase.

[0468] Embodiment 217 is the composition of any one of embodiments 161-216, wherein the dispersing agent comprises PEG 30-dipolyhydroxystearate.

[0469] Embodiment 218 is the composition of any of embodiments 161-217, wherein the emulsifier comprises one or more surfactants having an HLB value greater than 7.

[0470] Embodiment 219 is the composition of embodiment 218, wherein the surfactant comprises a nonionic surfactant.

[0471] Embodiment 220 is the composition of embodiment 218 or 219, wherein the surfactant comprises an ionic surfactant.

[0472] Embodiment 221 is a composition of embodiment 220, wherein the ionic surfactant is selected from alkyl / aryl ether sulfates / esters, alkyl / aryl ether sulfonates / esters, alkyl / aryl ether carboxylates / esters, alkyl / aryl ether phosphates / esters, dialkyl sulfosuccinates / esters, ethoxylated ether amines, ethoxylated-propoxylated ether amines, alkyl / aryl quaternary ammonium compounds, alkyl / aryl quaternary phosphonium compounds, ethoxylated alkyl / aryl quaternary ammonium compounds, ethoxylated alkyl / aryl quaternary phosphonium compounds, betaines, sulfobetaines, phospholipids and mixtures thereof.

[0473] Embodiment 222 is a herbicide dispersion composition comprising:

[0474] an oil continuous phase comprising a non-aqueous liquid; and

[0475] A dispersed phase comprising particles of a solid matrix comprising the acetamide herbicide and a waxy solid.

[0476] Embodiment 223 is the composition of embodiment 222, wherein the concentration of the acetamide herbicide is at least about 10 wt.%, at least about 15 wt.%, at least about 20 wt.%, at least about 25 wt.%, at least about 30 wt.%, at least about 35 wt.%, or at least about 40 wt.%.

[0477] Embodiment 224 is the composition of embodiment 222, wherein the concentration of the acetamide herbicide is about 10 wt.% to about 65 wt.%, about 20 wt.% to about 65 wt.%, about 30 wt.% to about 65 wt.%, about 40 wt.% to about 65 wt.%, about 50 wt.% to about 65 wt.%, about 10 wt.% to about 60 wt.%, about 20 wt.% to about 60 wt.%, about 30 wt.% to about 60 wt.%, about 40 wt.% to about 60 wt.%, about 50 wt.% to about 60 wt.%, about 10 wt.% to about 55 wt.%, about 20 wt.% to about 55 wt.%, about 30 wt.% to about 55 wt.%, about 40 wt.% to about 55 wt.%, about 50 wt.% to about 55 wt.%, or about 40 wt.% to about 50 wt.%.

[0478] Embodiment 225 is the composition of any one of embodiments 222-224, further comprising a second dispersed phase comprising a solid herbicide dispersed in silicone oil.

[0479] Embodiment 226 is the composition of embodiment 225, wherein the viscosity of the silicone oil is about 5 cst to about 100,000 cst, about 5 cst to about 10,000 cst, about 5 cst to about 1,000 cst, about 5 cst to about 500 cst, about 10 cst to about 100,000 cst, about 10 cst to about 10,000 cst, about 10 cst to about 1,000 cst, about 10 cst to about 500 cst, about 20 cst to about 100,000 cst, about 20 cst to about 10,000 cst, about 20 cst to about 1,000 cst, or about 20 cst to about 500 cst.

[0480] Embodiment 227 is the composition of embodiment 225 or 226, wherein the solid phase herbicide comprises at least one hydroxyphenylpyruvate dioxygenase (HPPD) inhibitor selected from the group consisting of fenpyroximate, cypermethrin, fluazifop, pyraclostrobin, clomazone, pyrafluanid, flupyralid, fluazifop, fluazifop, chlorpyrifos, isoxaflutole, mesotrione, norfadine, fluazifop, pyrazoline, benzaclostrobin, sulfamethoxam, tembotrione, topamezone, torapiraft, tefurin, their salts and esters, and mixtures thereof.

[0481] Embodiment 228 is the composition of any one of embodiments 225-227, wherein the solid phase herbicide comprises isoxaflutole.

[0482] Embodiment 229 is a herbicidal composition comprising particles comprising an acetamide herbicide and a solid matrix of a waxy solid, wherein the particles are dispersed in water.

[0483] Embodiment 230 is the composition of any of embodiments 222-229, wherein the weight ratio of acetamide herbicide to waxy solids is at least about 1:1, at least about 1.5:1, at least about 2:1, or at least about 3:1.

[0484] Embodiment 231 is the composition of any of embodiments 222-229, wherein the weight ratio of acetamide herbicide to waxy solids is about 1:1 to about 5:1, about 1:1 to about 4:1, about 1:1 to about 3:1, about 1.5:1 to about 5:1, about 1.5:1 to about 4:1, about 1.5:1 to about 3:1, about 2:1 to about 5:1, about 2:1 to about 4:1, or about 2:1 to about 3:1.

[0485] Embodiment 232 is the composition of any one of embodiments 222-231, wherein the acetamide herbicide is selected from acetochlor, alachlor, butachlor, butenetrachlor, sulfamethoxam, decachloramine, norformyl, dimethochlor, dimethochlor, dimethochlor-P, mefenacet, metazachlor, isopropyl metolachlor, S-isopropyl metolachlor, naproxen, pretilachlor, naprofil, promethachlor, isopropyl metolachlor, clarithromycin, terbutaline, dimethenamid and dimethochlor, their salts and esters, and mixtures thereof.

[0486] Embodiment 233 is the composition of any one of embodiments 222-232, wherein the acetamide herbicide is selected from the group consisting of acetochlor, alachlor, isopropyl metolachlor, S-isopropyl metolachlor, and mixtures thereof.

[0487] Embodiment 234 is the composition of any one of embodiments 222-233, wherein the acetamide herbicide comprises acetochlor.

[0488] Embodiment 235 is the composition of any of embodiments 222-234, wherein the waxy solid is selected from the group consisting of high molecular weight polymer waxes, hydrocarbon waxes, natural waxes, triglyceride waxes, ester waxes, and mixtures thereof.

[0489] Embodiment 236 is the composition of embodiment 235, wherein the high molecular weight polymer wax comprises polyethylene glycol wax.

[0490] Embodiment 237 is the composition of embodiment 236, wherein the polyethylene glycol wax has an average molecular weight of about 1000 Da or more or about 1000 Da to about 9000 Da.

[0491] Embodiment 238 is the composition of embodiment 237, wherein the waxy solid has a melting point of about 35°C to about 95°C, about 40°C to about 95°C, about 50°C to about 95°C, or about 60°C to about 95°C.

[0492] Embodiment 239 is a method for controlling weeds in a field of crop plants, the method comprising:

[0493] mixing water with the herbicide dispersion composition of any of embodiments 1-101 or 161-238 to form a herbicide application mixture, wherein the herbicide application mixture is a water continuous dispersion; and

[0494] The herbicide application mixture is applied to the field in a herbicidally effective amount.

[0495] Embodiment 240 is a method of controlling weeds in a field of crop plants, the method comprising:

[0496] The herbicide composition according to any one of embodiments 1-101 or 113-238 or a dilution thereof is applied to a field in a herbicidally effective amount. DETAILED DESCRIPTION

[0497] The following non-limiting examples are provided to further illustrate the present invention. Unless otherwise stated, the amounts specified in the examples are by weight.

[0498] Example 1

[0499] This example shows that the chemical stability of mesotrione is improved when combined with the second herbicidal active agent acetochlor in liquid hydrocarbons. After a certain amount of liquid hydrocarbons (such as Isopar M and Isopar V) is added to the oil phase containing acetochlor, the mesotrione granules are solidly dispersed in the oil continuous phase containing acetochlor. The details of each composition are shown in Table I. The stability test was carried out for 4 weeks at 54°C. These tests show that for samples 1 and 2 with an oil continuous phase consisting only of acetochlor, the recovery % of mesotrione is about 67-68%, and for compositions 3-10 with an oil continuous phase consisting of various mixtures of acetochlor and hydrocarbons, it has a recovery % of about 95% or more. Improvements in chemical stability were observed after adding hydrocarbons in the oil continuous phase.

[0500] Table I

[0501]

[0502] Example 2

[0503] This example shows that PEG-30 dipolyhydroxystearate is an effective dispersant for a variety of particulate active ingredients. The oil dispersion containing the polymer dispersant exhibited a free-flowing consistency, even at a relatively high loading of solid particulate active ingredients: i) mesotrione solids (61 wt.%); ii) glyphosate solids (50 wt.%); and iii) sodium salt of dicamba solids (60 wt.%). Without the addition of a dispersant, the corresponding oil dispersion showed a gel-like consistency, probably due to the large amount of flocculation of the suspended solids. The above findings show that PEG-30 dipolyhydroxystearate can be an effective dispersant for a variety of particulate active ingredients with different surface properties.

[0504] Example 3

[0505] This example shows that the strategy described in Example 1 for improving the chemical stability of mesotrione in the presence of acetochlor is still effective even in the presence of formulation ingredients such as dispersants, rheology modifiers and emulsifiers. The dispersant is a triblock copolymer PEG-30 dipolyhydroxystearate (PG-30 DPHS) and the emulsifier is an ethoxylated phosphate surfactant in acid form, tristyrylphenol EO (ethylene oxide) phosphate from Oxiteno under the trade name SURFOM 1323 SC. The rheology modifier is a surface-modified montmorillonite clay, referred to herein as an organoclay. Table II-B gives the recovery % of mesotrione in various samples of Table II-A after storage at 54°C for 2 weeks. Table III gives the composition of the organoclay-based gel used as a rheology modifier.

[0506] Table II-A

[0507]

[0508] 1 96.1% active

[0509] 2 98.3% active

[0510] 3 A mixture of acetochlor and MON 13900 (safener) in a weight ratio of 75.44:19.56

[0511] 4 Organoclay gel in Isopar M

[0512] 5 Organoclay gel in a mixture of acetochlor and safener mixture 3

[0513] Table II-B

[0514] sample Weight ratio of hydrocarbon to acetochlor Mesotrione recovery % 1 0.00(only acetochlor) 76.92 2 No Acetochlor 94.87 3 No Acetochlor 99.15 4 No Acetochlor 97.15 5 2.50 95.73 6 2.01 94.73 7 1.50 96.01 8 0.81 86.89 9 0.00(only acetochlor) 82.05

[0515] As is apparent from Tables II-A and II-B, mesotrione degraded when the oil continuous phase consisted entirely of acetochlor (Sample 1), but was substantially stable to degradation when the oil continuous phase consisted entirely of hydrocarbons (Samples 2-4). Furthermore, even in the presence of the above formulation ingredients, mesotrione had improved stability when the oil continuous phase consisted of hydrocarbons (Sample 4) or a certain mixture of hydrocarbons and acetochlor (Samples 5-7), but not when the oil continuous phase consisted entirely of acetochlor (Sample 9).

[0516] Table III

[0517]

[0518] Example 4

[0519] Dielectric modified oil suspensions containing ionic herbicidal active ingredient glyphosate and relatively polar oily herbicidal active ingredient acetochlor were prepared. Table IV gives the details of these compositions. The oil continuous phase contains a mixture of oily active substances acetochlor and ester isopropyl myristate, which has a dielectric constant of about 3.24 at 25°C. The internal phase of the bulk is solid glyphosate particles dispersed in the aforementioned oil continuous phase. A Retsch PM400 ball mill is used as a grinding device for grinding glyphosate solid particles when preparing an oil suspension. The emulsifiers in samples 1 and 2 are dialkyl sulfosuccinate surfactants, i.e., sodium bis(2-ethylhexyl) sulfosuccinate and ethoxylated phosphate surfactants, i.e., tristearylphenol ethoxylate, polyoxyethylene-16 phosphate. The emulsifier in sample 3 is an ethoxylated ether amine surfactant, i.e., polyoxyethylene-5 isotridecyloxypropylamine.

[0520] Table IV

[0521]

[0522] 1 The organoclay compositions are provided in Table V

[0523] 2 Used as a 70 wt.% solution in Isopar M

[0524] Table V

[0525] Element weight% Industrial acetochlor (96% active agent) 85.04 Organoclay Solids 12.06 Propylene carbonate 2.90

[0526] Example 5

[0527] Prepare an oil dispersion composition containing three herbicidal active ingredients, namely, acetochlor, dicamba and mesotrione, as a high dielectric oil-in-oil suspension emulsion (sample 1) or a high dielectric oil-in-oil co-oil-in-oil suspension emulsion (samples 2 and 3). In Table VI, sample 1 can be described as a high dielectric oil-in-oil suspension emulsion, while samples 2 and 3 can be described as high dielectric oil-in-oil co-oil-in-oil suspension emulsions. The oil continuous phase comprises a mixture of light and heavy mineral oils. The solubility of dicamba in mineral oil is limited, and although acetochlor is an oily liquid, its miscibility with mineral oil is limited. Sample 1 comprises two bulk dispersed phases: i) a dicamba solution in emulsified acetochlor (i.e., dicamba solids are dissolved in acetochlor); and ii) dispersed mesotrione solid particles, all in the above-mentioned oil continuous phase. When preparing sample 1, the mesotrione solid particles are first ground into a highly concentrated oil dispersion in light mineral oil, and then the resulting oil dispersion is mixed into a mixture of light and heavy mineral oils. The Retsch PM400 ball mill is used as a grinding device for grinding mesotrione solid particles in the preparation of oil suspensions. This is intended to increase the grinding efficiency, because the grinding efficiency generally increases with the increase in the load of the ground particles. Samples 2 and 3 also contain two bulk dispersed phases: i) a solution of dicamba in emulsified acetochlor; and ii) an oil suspension of mesotrione solid particles in emulsified silicone oil (prepared using a Retsch PM400 ball mill), all in the above-mentioned oil continuous phase. It should be noted that the silicone oil composed of relatively high molecular weight dimethicone has limited miscibility with mineral oil and acetochlor. Each oil-containing bulk internal phase is emulsified using the aforementioned grinding equipment. As shown in Table II-B, when mesotrione was combined with acetochlor in a conventional oil dispersion composition (Sample 1 in Table II-B), the recovery % of mesotrione at 54° C. for 2 weeks was less than 80%. As shown in Table IX, the chemical stability was significantly improved with the oil dispersion composition prepared in this example.

[0528] Table VI

[0529]

[0530] 1 Industrial solid dicamba (containing 98.3% dicamba) was dissolved in industrial acetochlor (containing 96% acetochlor), wherein the resulting solution contained 78.75wt.% acetochlor and 17.66wt.% dicamba

[0531] 2 The suspension composition is provided in Table VII

[0532] 3 The composition of the organoclay gel is provided in Table VIII

[0533] 4 Used as a 70 wt.% solution in Isopar M

[0534] Table VII

[0535]

[0536] 1 The molecular weight of 20cst dimethicone (polymer) is about 2,000 Daltons

[0537] 2 The molecular weight of 100cst dimethicone (polymer) is about 6,000 Daltons

[0538] Table VIII

[0539] Element weight% Heavy mineral oil 81.00 Organoclay Solids 14.88 Propylene carbonate 4.12

[0540] Table IX

[0541]

[0542] Example 6

[0543] An oil dispersion composition was prepared with a higher loading of a quaternary ammonium compound (QAC), namely isotridecyloxypropyl bis-(2-hydroxyethyl)methylammonium chloride (Tomamine Q-17-2PG from Evonik), a polar quaternary ammonium surfactant. The composition is detailed in Table X.

[0544] Table X

[0545]

[0546] 1: The composition is provided in Table XI

[0547] 2: The composition is provided in Table XII

[0548] 3: The composition is provided in Table XIII

[0549] The oil dispersion composition was prepared according to the following steps:

[0550] 1) Combine Phase 1 ingredients in a suitable container and mix until homogeneous.

[0551] 2) Combine Phase 2 ingredients in a suitable container and mix using a dispersion blade stirrer.

[0552] 3) Combine Phase 3 ingredients and mix in a Retsch ball mill using appropriate grinding media for a given time

[0553] 4) Slowly add the combined Phase 1 to the combined Phase 2 while stirring with a dispersion blade stirrer and continue mixing until uniform.

[0554] 5) The mixture was transferred to a Retsch ball mill filled with suitable grinding media and stirred for a given time.

[0555] 6) Add phase 3 to the mixture of step (5) and continue mixing for a given time

[0556] Table XI

[0557]

[0558] Table XII

[0559]

[0560] Table XIII

[0561]

[0562]

[0563] Example 7

[0564] This embodiment shows that even when dicamba exists in the form of dicamba acid rather than dicamba salt, adding quaternary ammonium compounds has a beneficial effect on reducing the volatility of dicamba from the prepared application mixture. Prepare a test sample, wherein dicamba acid is dissolved in acetochlor, to which a propylene glycol solution of a quaternary ammonium compound (QAC) is added. The amount of propylene added with QAC corresponds to about 9.2-9.4 times the number of dicamba moles in the corresponding test sample. A test sample (control sample) is prepared without adding any QAC, but with the amount of propylene glycol corresponding to about 9.4 times the number of dicamba moles in the sample. Table XIV shows the composition of these test samples. Relative to the amount of dicamba acid solution in acetochlor contained in any given sample, the respective contents of the two surfactants added to the test sample are comparable for all test samples.

[0565] Table XIV

[0566]

[0567] The prepared compositions were diluted with water to a concentration of 1.2 wt % of dicamba acid. The diluted compositions were tested for dicamba volatility by the process described in ASTM publication STP1587 entitled "Pesticide Formulation and Delivery Systems: 35th Volume, Pesticide Formulations, Adjuvants, and Spray Characterization in 2014" (published in 2016, which is incorporated herein by reference). The general process is briefly described below.

[0568] The humidity tester from Hummert International (for humidity tester: Part Nos 14-3850-2 and for 1020 flat trays: 11-3050-1) was modified by cutting a hole of 2.2 cm in diameter at one end about 5 cm from the top to allow the glass air sampling tube (22 mm OD) of the polyurethane foam (PUF) filter to be inserted. The sampling tube was fixed to each side of the humidity tester wall with a VITON o-ring. The air sampling tube outside the humidity tester was installed with a pipeline connected to the vacuum manifold just before sampling. The flat tray below the humidity tester was filled with 1 liter of sieved dry or wet 50 / 50 soil (50% Redi-Earth and 50% US 10 field soil) to a depth of about 1 cm. The composition was applied to the soil of each humidity tester using a tracking sprayer at a dicamba application rate of 1.0 lb / A ae at 10 gallons / acre (GPA).

[0569] The bottom of the flat tray containing the auxin herbicide formulation on the soil was covered with a humidity tester cover and the cover was secured with a clip. The growth chamber was set at 35°C and 40% relative humidity (RH). The assembled humidity tester was placed in a temperature and humidity controlled environment and connected to the vacuum manifold via an air sampling line. Air was pumped through the humidity tester and PUF at a rate of 2 liters per minute (LPM) for 24 hours, at which time air sampling was stopped. The humidity tester was then removed from the controlled environment and the PUF filter was removed. The PUF filter was extracted with 20 mL of methanol, and the concentration of auxin herbicide in the solution was analyzed using LC-MS methods known in the art.

[0570] The results of the volatility testing are shown in Table XV below. The results are expressed as a percentage reduction in volatility relative to the test sample without the QAC. The results show that volatility is significantly reduced by including the quaternary ammonium compound.

[0571] Table XV

[0572]

[0573] Example 8

[0574] This embodiment shows the beneficial effect of adding quaternary ammonium compounds on reducing the volatility of dicamba in the application mixture prepared by the oil dispersion composition. The oil dispersion composition is prepared according to Example 6. Tables XVI, XVII, XVIII and XIX detail the ingredients of the oil dispersion composition. The sample of the oil dispersion composition is diluted with water to a concentration of dicamba acid of 1.2 weight %. The diluted composition is tested for dicamba volatility by the procedure described in Example 7. The results of the volatility test are shown in the following table XIX. The results are expressed as a percentage reduction in volatility relative to the test sample 3 without QAC. The results show that volatility is significantly reduced by including a quaternary ammonium compound.

[0575] Table XVI

[0576]

[0577] Table XVII

[0578]

[0579] Table XVIII

[0580]

[0581] Table XIX

[0582]

[0583]

[0584] Example 9

[0585] Prepare a solution of dicamba acid and an affinity solvent. Detailed information is shown in Table XX. Also prepare a solution of dicamba acid dissolved in acetochlor. Using the method described in Example 7, these solutions are used alone to prepare samples for evaluating the volatility of dicamba. No volatility control agent is added to any of these samples. The volatility test results of dicamba are given in Table XXI, which shows that the volatility of dicamba in each dicamba solution in propylene glycol and castor oil (affinity solvent) is significantly lower than that of the dicamba solution sample in acetochlor.

[0586] Table XX

[0587]

[0588] Table XXI

[0589]

[0590] Example 10

[0591] This example shows the composition of the emulsion for the dicamba-mesotrione premix concentrate, which comprises the dicamba acid solution in the affinity solvent of Example 9. Depending on whether the affinity solvent is a polar liquid (propylene glycol) or an oil (castor oil), the emulsion is prepared as an oil-in-oil co-emulsion or an oil-in-polar liquid or an oil-in-oil co-emulsion. Table XXII gives the composition of the organoclay gel used to prepare these emulsions.

[0592] The emulsions listed in Table XXIII were prepared as follows:

[0593] a) Combine the ingredients of the continuous phase in a suitable container and prepare a homogeneous mixture using a dispersion blade stirrer.

[0594] b) Separately in a suitable container combine the ingredients of dispersed phase 1 and prepare a homogeneous mixture using a stirrer.

[0595] c) Slowly add the dispersed phase 1 mixture to the continuous phase mixture while keeping the continuous phase mixture under vigorous stirring using a dispersion blade stirrer; stirring is continued for a period of time depending on the volume of the emulsion to be prepared.

[0596] d) The ingredients of dispersed phase 2 were combined separately in the grinding vessel of a Retsch PM100 planetary ball mill equipped with appropriate amounts of grinding media. The resulting mixture was ground to reduce the particle size of the mesotrione solid particles.

[0597] e) The ground dispersion from step (d) is slowly added to the dispersed phase 1 emulsion previously prepared according to step (c) under vigorous stirring; stirring is continued for a period of time depending on the volume of the emulsion to be prepared.

[0598] Table XXII

[0599] Element Organoclay gel 1 Organoclay Gel 2 <![CDATA[Heavy mineral oil 1 1 > 81 <![CDATA[Heavy mineral oil 2 2 > 91.79 Organoclay 1 5.13 Organic Clay 2 12.00 PEG 30-dipolyhydroxystearate 1.85 2.85 Propylene carbonate 1.23 4.15 100.00 100.00

[0600] 1: Drakeol 35 mineral oil

[0601] 2: Drakeol 19 mineral oil

[0602] Table XXIII

[0603]

[0604] 1:Drakeol 9

[0605] 2:Drakeol 35

[0606] 3:Drakeol 19

[0607] 4: Ethoxylated quaternary amine surfactant

[0608] 5: Ethoxylated nonionic surfactant

[0609] 6: Acrylates / Ethylhexyl Acrylate / Dimethicone Methacrylate Copolymer

[0610] Embodiment 11

[0611] This example shows the composition of an emulsion for an acetochlor-dicamba-mesotrione premix concentrate, wherein dispersed phase 1 is a mixture of acetochlor and a waxy solid (i.e., a polyethylene glycol having a molecular weight of 30,000 Daltons). The acetochlor and the waxy solid are heated to about 85°C, respectively, and then these heated materials are mixed together in a suitable container under heating and stirring, and combined with all the remaining ingredients of dispersed phase 1. The method for preparing the emulsion is similar to the method described in Example 10. However, the continuous phase mixture is cooled to about 0-5°C, and the heated mixture of the above-mentioned dispersed phase 1 is slowly added to the cooled continuous phase mixture under strong stirring and cooling for emulsification. After the emulsification is completed, the temperature of the resulting emulsion is 15-20°C. This is to ensure rapid coagulation of the waxy emulsion droplets. The details of the emulsion are provided in Table XXIV.

[0612] Table XXIV

[0613]

[0614] 1:Drakeol 19

[0615] 2: Organoclay gel 1 from Table XXII

[0616] Example 12

[0617] The compositions of Examples 10 and 11 were evaluated for dicamba volatility using the method described in Example 7. The results are provided in Table XXV.

[0618] Table XXV

[0619]

[0620]

[0621] Embodiment 13

[0622] This example shows the composition of an emulsion for an acetochlor-dicamba-isoxazone premix concentrate, wherein the first dispersed phase is a mixture of acetochlor and a waxy solid (ie, polyethylene glycol having a molecular weight of 30,000 Daltons). Table XXVI provides details of the composition.

[0623] Table XXVI

[0624]

[0625] 1:Drakeol 19

[0626] 2: Organoclay gel 2 from Table XXIII

[0627] Embodiment 14

[0628] The compositions described in the above examples are prepared, wherein mesotrione is replaced by aclonifen, cypermethrin, fluazifop, pyraclostrobin, clomazone, fluazifop, flupyralid, fluazifop, fluazifop, chlorpyrifos, isoxaflutole, mesotrione, norfadoxime, fluazifop, pyrazoline, pyrazoline, sulfamethoxazole, cyproconazole, tampron, topamizone, torapiraft, tefurin or ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate.

[0629] When introducing elements of the present invention or the preferred embodiments thereof, the articles "a," "an," "the," and "said" are intended to mean that there are one or more of the elements. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements besides the listed elements.

[0630] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0631] As various changes could be made in the above compositions and methods without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not limiting.

Claims

1. A herbicide composition comprising an auxin herbicide acid and an affinity solvent, wherein the affinity solvent comprises castor oil, and wherein the weight ratio of the affinity solvent to the auxin herbicide acid is 1:1-5:1, wherein the auxin herbicide acid is dicamba acid.

2. The composition of claim 1, wherein the weight ratio of affinity solvent to auxin herbicide acid is at least 1.5:

1.

3. The composition of claim 1, wherein the weight ratio of affinity solvent to auxinic herbicide acid is at least 2:

1.

4. The composition of claim 1, wherein the weight ratio of the affinity solvent to the auxin herbicide acid is 1:1 to 4:

1.

5. The composition of claim 1, wherein the weight ratio of the affinity solvent to the auxin herbicide acid is 1.5:1 to 4:

1.

6. The composition of claim 1, wherein the weight ratio of the affinity solvent to the auxin herbicide acid is 1.5:1 to 3:

1.

7. The composition according to any one of claims 1 to 6, wherein the concentration of the auxin herbicide acid is 0.5 wt.% to 5 wt.%.

8. The composition according to any one of claims 1 to 6, wherein the concentration of the auxin herbicide acid is 10 wt.% to 50 wt.%.

9. The composition of claim 1, further comprising an alkanediol.

10. The composition of claim 9, wherein the alkane diol comprises a C2-C6 diol.

11. The composition of claim 9 or 10, wherein the alkane diol comprises a branched C2-C6 diol.

12. The composition of claim 9 or 10, wherein the alkane diol is selected from propylene glycol; hexylene glycol; 1,3-propanediol; 1,4-butanediol; 1,3-butanediol; and mixtures thereof.

13. The composition of claim 9 or 10, wherein the molar ratio of alkanediol to auxinic herbicide acid is at least 1:

1.

14. The composition of claim 9 or 10, wherein the molar ratio of alkanediol to auxin herbicide acid is 2:1 to 10:

1.

15. The composition of claim 9 or 10, wherein the alkanediol concentration is at least 10 wt.%.

16. The composition according to claim 9 or 10, wherein the alkanediol concentration is 15 wt.% to 40 wt.%.

17. The composition according to claim 9 or 10, further comprising a solvent.

18. The composition of claim 17, wherein the solvent is water.

19. A method of preparing a herbicide application mixture, the method comprising mixing water with the composition of any one of claims 1-18 to form the herbicide application mixture, wherein the herbicide application mixture is a water continuous dispersion.

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