Agrochemical compositions

Abstract

An agrochemical composition comprising: a linear fatty acid having a C8 to C10 alkyl chain; and an additive selected from the group consisting of a diluent, an alkoxylated phosphate ester surfactant, and combinations thereof, wherein the alkoxylated phosphate ester surfactant has an alkoxylate degree of from about 10 to about 100 and is selected from the group consisting of an alkoxylated C12-C22 alkyl phosphate ester, an alkoxylated phosphate ester formed from an alkoxylated triglyceride having at least one pendant hydroxyl group, an alkoxylated phosphate ester formed from an alkoxylated alkyl amine, and combinations thereof; and wherein the diluent is selected from the group consisting of C4-C10 linear or branched alcohols and propoxylates thereof, branched C5-C10 monocarboxylic acids, methyl and ethyl esters of linear or branched C8-C10 fatty acids, tall oil fatty acids, C2-C8 linear or branched trialkyl phosphates, aromatic solvents, mineral oils, methyl benzoate, methyl salicylate, octyl acetate, octyl lactate, alkyl nitriles, and combinations thereof.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefits of U.S. Provisional Application No. 63 / 200,637, filed March 19, 2021, and U.S. Provisional Application No. 63 / 201,866, filed May 17, 2021, each of which is incorporated herein by reference in its entirety. Technical Field

[0003] In general, this disclosure relates to agrochemical compositions comprising linear fatty acids and additives selected from diluents, alkoxylated phosphate surfactants, and combinations thereof. More specifically, this disclosure provides compositions suitable for agricultural applications, wherein the linear fatty acid is valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, or combinations thereof. Background Technology

[0004] Emulsifiable concentrates (ECs) suitable for agricultural applications are clear liquid formulations containing an emulsifier and a hydrophobic liquid (as a continuous phase), with the emulsifier dissolved in the hydrophobic liquid. Industrially acceptable ECs must be stable during storage and, more importantly, must form an emulsion once diluted in water. This emulsion should also remain stable during spraying (typically from 30 minutes to 24 hours) without significant phase separation, flocculation, etc.

[0005] ECs used in agricultural applications are agrochemical products. Some ECs are adjuvant ECs, while others are pesticide ECs. Linear C8-C10 acids are registered as pesticides (primarily as herbicides) in various countries. Nonanoic acid is registered as both a pesticide and an adjuvant in the United States. The use of other short-chain (C2-C7) monocarboxylic acids as herbicides has also been mentioned on the internet, but to the inventor's knowledge, their use as pesticides has not been approved because short-chain fatty acids are not as effective as C8-C10 fatty acids. It is well known that, in addition to pesticides and generally suitable solvents, three common surfactants can be used as emulsifiers to formulate many pesticide ECs: nonionic surfactants such as castor oil ethoxylates (Emulpon CO-360) or alcohol ethoxylates; calcium alkylbenzene sulfonates such as calcium dodecylbenzene sulfonate (Witconate P-1220EH); and block copolymers of alkyl polyethylene oxide and polypropylene oxide such as Ethylan NS-500LQ. However, these common emulsifiers are unsuitable for formulating emulsions containing linear fatty acids such as valeric acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid. Instead, other chemicals, such as emulsifiers derived from nonylphenol, have been used, but these chemicals are considered undesirable due to potential environmental and health concerns. Therefore, opportunities for improvement remain. Summary of the Invention

[0006] This disclosure provides an agricultural chemical composition comprising:

[0007] At least one linear fatty acid, said linear fatty acid being selected from valeric acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid; and

[0008] Additives, wherein the additives are selected from diluents, alkoxylated phosphate surfactants, and combinations thereof.

[0009] The alkoxylated phosphate surfactant described herein has an alkoxylation degree of about 10 to about 100 and is selected from alkoxylated C12-C22 alkyl phosphates, alkoxylated phosphates formed from alkoxylated triglycerides having at least one side hydroxyl group, alkoxylated phosphates formed from alkoxylated alkylamines, and combinations thereof; and

[0010] The diluent is selected from C4-C10 linear or branched alcohols and their propoxylates, branched C5-C10 monocarboxylic acids, methyl and ethyl esters of linear or branched C8-C10 fatty acids, tall oil fatty acids, C2-C8 linear or branched trialkyl phosphate esters, aromatic solvents, mineral oils, methyl benzoate, methyl salicylate, octyl acetate, octyl lactate, alkyl nitrile, and combinations thereof.

[0011] This disclosure also provides the aforementioned agrochemical composition plus one or more liquid or solid pesticides.

[0012] This disclosure also provides compositions of pesticides that are substantially composed of:

[0013] Nonanoic acid; and

[0014] diluent,

[0015] The composition contains less than 1% by weight of water and less than 1% by weight of surfactant, each based on the total weight of the composition.

[0016] This disclosure also provides canned compositions comprising the aforementioned agrochemical compositions. This disclosure also provides a method comprising the steps of providing an agrochemical composition and applying the pesticide composition to a target. Detailed Implementation

[0017] The following detailed description of the invention is merely exemplary in nature and is not intended to limit the agrochemical compositions disclosed herein. Furthermore, it is not intended to be limited by any theory presented in the foregoing background or the following detailed description of the invention.

[0018] The embodiments of this disclosure generally relate to agrochemical compositions and methods for forming the same. For the sake of brevity, conventional techniques associated with the formation of such compositions may not be described in detail herein. Furthermore, the various tasks and method steps described herein can be combined into a more comprehensive process or method with additional steps or functions not described in detail herein. Specifically, the various steps in the manufacture of agrochemical compositions are well known; therefore, for the sake of brevity, many conventional steps will be mentioned only briefly or omitted entirely without providing well-known process details.

[0019] In one embodiment, this disclosure relates to a stable pesticide composition comprising nonanoic acid and at least one component selected from surfactants, diluents, and combinations thereof. The surfactant may be at least one phosphate ester having an alkoxylation degree of about 10 to about 100. The surfactant may be selected from alkoxylated C12-C22 alkyl phosphates, phosphate esters of alkoxylated triglycerides having at least one side hydroxyl group, phosphate esters formed from alkoxylated alkylamines, and combinations thereof. The diluent may be any liquid capable of lowering the melting point of nonanoic acid.

[0020] Nonanoic acid, also known as pelargonic acid, is a linear C9 carboxylic acid with a melting point of approximately 14°C. It occurs naturally in geranium oil as an ester. Using nonanoic acid as a herbicide is ideal because it is a biopesticide and can be used as a substitute for glyphosate, glufosinate, and paraquat.

[0021] In other embodiments, this disclosure provides a pesticide composition comprising:

[0022] Linear fatty acids with C5-C10 alkyl chains; and

[0023] Additives, wherein the additives are selected from diluents, alkoxylated phosphate surfactants, and combinations thereof.

[0024] The alkoxylated phosphate surfactant described herein has an alkoxylation degree of about 10 to about 100 and is selected from alkoxylated C12-C22 alkyl phosphates, alkoxylated phosphates formed from alkoxylated triglycerides having at least one side hydroxyl group, alkoxylated phosphates formed from alkoxylated alkylamines, and combinations thereof; and

[0025] The diluent is selected from C4-C10 linear or branched alcohols and their propoxylates, branched C5-C10 monocarboxylic acids, methyl and ethyl esters of linear or branched C8-C10 fatty acids, tall oil fatty acids, C2-C8 linear or branched trialkyl phosphate esters, aromatic solvents, mineral oils, methyl benzoate, methyl salicylate, octyl acetate, octyl lactate, alkyl nitrile, and combinations thereof.

[0026] In one embodiment, the composition consists of linear fatty acids and additives.

[0027] In one embodiment, the composition consists essentially of linear fatty acids and additives.

[0028] In another embodiment, the composition consists of linear fatty acids and additives.

[0029] In a further embodiment, the composition comprises linear fatty acids and additives, wherein the additives include alkoxylated phosphate surfactants and may or may not contain a diluent.

[0030] In a further embodiment, the composition consists essentially of linear fatty acids and additives, wherein the additives include alkoxylated phosphate surfactants and may or may not contain a diluent.

[0031] In a further embodiment, the composition comprises linear fatty acids and additives, wherein the additives include alkoxylated phosphate surfactants and may or may not contain a diluent.

[0032] Alternatively, the composition comprises linear fatty acids and additives, wherein the additives include diluents and may or may not contain alkoxylated phosphate surfactants.

[0033] Alternatively, the composition consists essentially of linear fatty acids and additives, wherein the additives include diluents and may or may not contain alkoxylated phosphate surfactants.

[0034] Alternatively, the composition consists of linear fatty acids and additives, wherein the additives include diluents and may or may not contain alkoxylated phosphate surfactants.

[0035] In one embodiment, the composition comprises nonanoic acid and alkoxylated C12-C22 phosphate esters.

[0036] In one embodiment, the composition consists essentially of nonanoic acid and alkoxylated C12-C22 phosphate esters.

[0037] In one embodiment, the composition comprises nonanoic acid and alkoxylated C12-C22 phosphate esters.

[0038] In another embodiment, the composition comprises nonanoic acid and alkoxylated triglyceride phosphate.

[0039] In another embodiment, the composition consists essentially of nonanoic acid and alkoxylated triglyceride phosphate.

[0040] In another embodiment, the composition comprises nonanoic acid and alkoxylated triglyceride phosphate.

[0041] In another embodiment, the composition comprises nonanoic acid and alkoxylated alkylamine phosphate.

[0042] In another embodiment, the composition consists essentially of nonanoic acid and alkoxylated alkylamine phosphate.

[0043] In another embodiment, the composition comprises nonanoic acid and alkoxylated alkylamine phosphate.

[0044] In another embodiment, the composition comprises nonanoic acid and a diluent.

[0045] In another embodiment, the composition consists essentially of nonanoic acid and a diluent.

[0046] In another embodiment, the composition consists of nonanoic acid and a diluent.

[0047] In a further embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated C12-C22 phosphate ester of this disclosure.

[0048] In a further embodiment, the composition consists essentially of nonanoic acid, a diluent, and the alkoxylated C12-C22 phosphate esters of this disclosure.

[0049] In a further embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated C12-C22 phosphate ester of this disclosure.

[0050] In another embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated triglyceride phosphate of this disclosure.

[0051] In another embodiment, the composition consists essentially of nonanoic acid, a diluent, and the alkoxylated triglyceride phosphate of this disclosure.

[0052] In another embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated triglyceride phosphate of this disclosure.

[0053] In another embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated alkylamine phosphate of this disclosure.

[0054] In another embodiment, the composition consists essentially of nonanoic acid, a diluent, and the alkoxylated alkylamine phosphate of this disclosure.

[0055] In another embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated alkylamine phosphate of this disclosure.

[0056] In yet another embodiment, the composition comprises nonanoic acid, another pesticide, and the alkoxylated phosphate ester disclosed herein.

[0057] In yet another embodiment, the composition comprises nonanoic acid, another pesticide, a diluent, and the alkoxylated phosphate ester of this disclosure.

[0058] In another embodiment, the composition comprises nonanoic acid and alkoxylated alkylamine phosphate.

[0059] In another embodiment, the composition consists essentially of nonanoic acid and alkoxylated alkylamine phosphate.

[0060] In another embodiment, the composition comprises nonanoic acid and alkoxylated alkylamine phosphate.

[0061] In another embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated alkylamine phosphate of this disclosure.

[0062] In another embodiment, the composition consists essentially of nonanoic acid, a diluent, and the alkoxylated alkylamine phosphate of this disclosure.

[0063] In another embodiment, the composition comprises nonanoic acid, a diluent, and the alkoxylated alkylamine phosphate of this disclosure.

[0064] In another embodiment, the composition is a stable, ready-to-use emulsion comprising at least one linear C5-C10 fatty acid, at least one phosphate ester of the present disclosure, and water, wherein the concentration of the at least one C5-C10 fatty acid is from about 2% to about 15% by weight, from about 3% to about 12% by weight, or from about 4% to about 10% by weight; wherein the concentration of the at least one phosphate ester is from about 0.1% to about 2% by weight or from about 0.4% to about 1% by weight; and wherein the concentration of water is from about 80% to about 98% by weight or from about 85% to about 95% by weight, each based on the total weight of the emulsion. In various embodiments, the concentration of the at least one C5-C10 fatty acid is from about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15% by weight, based on the total weight of the emulsion. In other embodiments, the concentration of the at least one phosphate ester is about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 1.9, or 2% by weight, based on the total weight of the emulsion. In other embodiments, the concentration of water is about 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, or 98% by weight, based on the total weight of the emulsion. The term "consistently composed of" describes various embodiments that generally do not contain one or more of pesticides, surfactants other than the aforementioned surfactants, additives, solvents, water, adjuvants, etc., selected by those skilled in the art. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly intended to be used herein.

[0065] Linear fatty acids:

[0066] To recap, linear fatty acids have C5 to C10 alkyl chains. In various embodiments, linear fatty acids have five, six, seven, eight, nine, or ten carbon atoms in the alkyl chain, or include mixtures of compounds containing eight, nine, or ten carbon atoms in the alkyl chain.

[0067] For example, a linear fatty acid can be nonanoic acid. Commercially available examples of nonanoic acid include Matrilox AP001M (98%) from Matrica, Emerion W 90 PA (90%) from Emery Olechemicals, and Emery 1202 (90%) from BASF / Cognis. In some cases, alternatively, a mixture of linear C8-C10 fatty acids (octanoic acid / capric acid) can be used, or it can be used in combination with nonanoic acid. The terms pelargonic acid, nonanoic acid, and C9 acid are used interchangeably throughout the specification. The terms fatty acid and monocarboxylic acid are used interchangeably throughout the specification.

[0068] In various embodiments, the linear fatty acid is nonanoic acid and is present in an amount of about 20 to about 95, about 35 to about 90, or about 50 to about 90% by weight of the active substance based on the total weight of the composition. This amount can be about 25 to about 90, about 30 to about 85, about 35 to about 80, about 40 to about 75, about 45 to about 70, about 50 to about 65, or about 55 to about 60% by weight of the active substance based on the total weight of the composition. The linear fatty acid can also be a C5-C7 acid. They can be used alone or in combination with C8-C10 acids. When used with nonanoic acid, the C5-C7 acid acts primarily as an adjuvant by lowering the melting point of the EC formulation. In this sense, the C5-C7 acid can be described as a diluent. The monocarboxylic acid can be any monocarboxylic acid known in the art that contains 5, 6, 7, 8, or 9 carbon atoms. Some products include mixtures of C5-C9 monocarboxylic acids (and other minor impurities). Typical examples include Matrilox IL001M and Emery 1210. In various embodiments, fatty acids are present in the composition in any one or more amounts just described above. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​described above and values ​​in between, are expressly intended to be used herein.

[0069] additive:

[0070] Now consider the additive, which is selected from diluents, alkoxylated phosphate surfactants, and combinations thereof. For example, the additive may include a diluent. Alternatively, the additive may include an alkoxylated phosphate surfactant. Alternatively, the additive may include both a diluent and an alkoxylated phosphate surfactant. Furthermore, the additive may include a diluent and not contain an alkoxylated phosphate surfactant. Alternatively, the additive may contain an alkoxylated phosphate surfactant and not contain a diluent.

[0071] In various embodiments, the additive is present in the composition at an amount of about 5 to about 80, about 8 to about 60, or about 10 to about 40% by weight of active substance, based on the total weight of the composition. In various embodiments, this amount is about 10 to about 75, about 15 to about 70, about 20 to about 65, about 25 to about 60, about 30 to about 55, about 35 to about 50, or about 40 to about 45% by weight of active substance, based on the total weight of the composition. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​above and values ​​between the values ​​above, are expressly intended to be used herein.

[0072] Diluent:

[0073] Regarding diluents, the composition may or may not contain one or more diluents. For example, in one embodiment using nonanoic acid, and because nonanoic acid has a melting point of about 12°C to 14°C, the composition may ideally contain a diluent (or solvent) capable of lowering the melting point of nonanoic acid. In various embodiments, the diluent preferably provides an adjunct to nonanoic acid. To effectively lower the melting point of nonanoic acid, suitable diluents typically have a melting point below about 5, 0, -5, or -10°C. The degree of reduction in the melting point of nonanoic acid typically depends on the concentration of the added diluent. In various embodiments, the melting point of the composition as a whole may be less than about 5, 0, -5, or -10°C. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​described above and values ​​between the values ​​described above, are expressly considered for use herein.

[0074] In various embodiments, the diluent is selected from C4-C10 linear or branched alcohols and their propoxylated derivatives, branched C5-C10 monocarboxylic acids, methyl and ethyl esters of linear or branched C8-C10 fatty acids, tall oil fatty acids, C2-C8 linear or branched trialkyl phosphate esters, aromatic solvents, mineral oils, methyl benzoate, methyl salicylate, octyl acetate, octyl lactate, alkyl nitrile, cyclic monoterpenes (such as d-limonene), and combinations thereof. More typically, the diluent may be selected from 2-ethylhexanoic acid (2-EH acid), 2-ethylhexanol (2-EH alcohol), hexanol, and combinations thereof. The diluent may include any one or more of these compounds and may include or exclude any one or more other compounds. In various embodiments, the diluent is selected from C4-C10 linear or branched alcohols and their propoxylated derivatives, C5-C10 branched monocarboxylic acids, and tall oil fatty acids. It is expressly contemplated herein that all combinations of these compounds may be used individually, in combination with one or more of other compounds, and in excluding one or more of other compounds in various non-limiting embodiments.

[0075] In various embodiments, the diluent is, contains, or does not contain one or more C4-C10 linear or branched alcohols and their propoxylated derivatives. These alcohols can be or include any alcohol having 4, 5, 6, 7, 8, 9, or 10 carbon atoms, or any range of values ​​between these values. The carbon atoms can be present in any linear or branched isomer configuration known in the art, all of which are explicitly contemplated for use herein. Typical examples of such alcohols include butanol, hexanol, octanol, decanol, 2-EH alcohol, 2-propylheptanol, Exxal 8, Exxa1 9, and Exxal 10.

[0076] In various embodiments, the diluent is, contains, or does not contain one or more branched C5-C10 monocarboxylic acids. These carboxylic acids can be or include any carboxylic acid having 5, 6, 7, 8, 9, or 10 carbon atoms, or any range of values ​​between these values. It is explicitly intended that all isomers be used in the various non-limiting embodiments described herein. Typical examples of such carboxylic acids include 2-EH acids and neodecanoic acid.

[0077] In other embodiments, the diluent is one or more of methyl and / or ethyl esters, comprising or not comprising linear or branched C5-C10 monocarboxylic acids. These carboxylic acids can be or include any carboxylic acid having 5, 6, 7, 8, 9, or 10 carbon atoms, or any range of values ​​between these values. It is explicitly intended that all isomers be used in the various non-limiting embodiments described herein. A typical example of such a fatty acid ester is CE-810K, commercially available from Proctor & Gamble.

[0078] In various embodiments, the diluent does not contain oleic acid, tall oil fatty acids, or a combination thereof. In another embodiment, the diluent is tall oil fatty acids.

[0079] In other embodiments, the diluent is, contains, or does not contain one or more C2-C8 linear or branched trialkyl phosphates. The alkyl group of these phosphates may include any alkyl group having 2, 3, 4, 5, 6, 7, or 8 carbon atoms, or any range of values ​​between these values. Typical examples include triethyl phosphate, tributyl phosphate, and trioctyl phosphate.

[0080] In various embodiments, the diluent may or may not include an aromatic solvent. There are no particular limitations on the aromatic solvent, and it may be any aromatic solvent known in the art. The aromatic solvent may be an aromatic hydrocarbon. Suitable non-limiting examples of aromatic solvents include solvent naphtha (petroleum), heavy aromatic solvents, solvent naphtha (petroleum), light aromatic solvents, C9-C10 aromatic hydrocarbon solvents, and mixtures of two or more thereof, optionally containing additional components. Typical examples of industrial aromatic hydrocarbons include Aromatic 100, Aromatic 150, Aromatic 200, Solvesso 100, Solvesso 150, Solvesso 150ND, Solvesso 200, and Solvesso 200ND, available from ExxonMobil; Shellsol X7B, Shellsol A100, Shellsol A150, and Shellsol A150 ND, available from Shell Chemicals; and Farbasol, available from Orlen Oil.

[0081] In various embodiments, the diluent may or may not contain methyl benzoate, methyl salicylate, octyl acetate, octyl lactate, or combinations thereof. For example, in one embodiment, the diluent may or may not contain methyl benzoate. In another embodiment, the diluent may or may not contain methyl salicylate. In another embodiment, the diluent may or may not contain octyl acetate. In another embodiment, the diluent may or may not contain octyl lactate. In yet another embodiment, the diluent may or may not contain a combination of two or more of the above.

[0082] In various embodiments, the diluent is present in an amount greater than 0 and less than about 80, about 50, or about 30% by weight of the active substance, based on the total weight of the composition. This amount may be less than about 1, 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or about 75% by weight of the active substance, based on the total weight of the composition. In other embodiments, this amount may be about 5 to about 75, about 10 to about 70, about 15 to about 65, about 20 to about 60, about 25 to about 55, about 30 to about 50, about 35 to about 45, or about 40 to about 45% by weight of the active substance, based on the total weight of the composition. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly intended to be used herein.

[0083] In one embodiment, the composition is free of a diluent and contains an alkoxylated phosphate ester. In another embodiment, a diluent is present and the diluent is selected from 2-ethylhexanoic acid, tall oil fatty acids, 2-ethylhexanol, hexanol, and combinations thereof. In another embodiment, a diluent is present and the diluent is selected from d-limonene, mineral oil, and combinations thereof. In yet another embodiment, the composition is free of an alkoxylated phosphate ester and contains a diluent.

[0084] Alkoxylated phosphate esters:

[0085] Alternatively, the additive may be, contain, or not contain an alkoxylated phosphate ester. The phosphate ester may be any phosphate ester known in the art. The term "alkoxylation" as used throughout this disclosure may describe methoxylation, ethoxylation, propoxylation, butoxylation, etc., as known in the art. Furthermore, all isomers are expressly intended for use in the various non-limiting embodiments herein. The number of carbon atoms in the alkoxylated portion is not particularly limited and may include 1, 2, 3, or 4. In the various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​described above and values ​​between the values ​​described above, are expressly intended for use herein.

[0086] In various embodiments, the alkoxylated phosphate surfactant has an alkoxylation degree of about 10 to about 100. In other words, the phosphate ester is typically alkoxylated with about 10 to about 100 moles of an epoxide such as ethylene oxide, propylene oxide, butane oxide, or combinations thereof. In various embodiments, the degree of alkoxylation is about 10 to about 44, about 15 to about 50, about 20 to about 45, about 25 to about 40, about 30 to about 35, about 12 to about 36, about 14 to about 34, about 16 to about 32, about 18 to about 30, about 20 to about 28, about 22 to about 26, about 24 to about 26, about 15 to about 23, about 16 to about 22, about 17 to about 21, about 18 to about 20, about 19 to about 20, about 15 to about 40, about 20 to about 35, about 25 to about 30, about 20 to about 36, about 22 to about 34, about 24 to about 32, about 26 to about 30, or about 28 to about 30. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly intended to be used herein.

[0087] In other embodiments, the phosphate ester is selected from alkoxylated C12-C22 alkyl phosphates, alkoxylated phosphates formed from alkoxylated triglycerides having at least one side hydroxyl group, alkoxylated phosphates formed from alkoxylated alkylamines, and combinations thereof. For example, the phosphate ester can be any alkoxylated alkyl phosphate ester, wherein the alkyl group has 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22 carbon atoms. In various embodiments, the range of carbon atoms is 12 to 22, 13 to 21, 14 to 20, 15 to 19, 16 to 18, 16 to 18, 12 to 14, 12 to 16, 12 to 18, 12 to 20, 12 to 22, 14 to 16, 14 to 18, 14 to 20, 14 to 22, 16 to 18, 16 to 20, 16 to 22, 18 to 20, 18 to 22, or 20 to 22. Alkyl groups can be linear or branched. All isomers are explicitly intended for use in the various non-limiting embodiments described herein. Typical examples include lauryl, tridecyl, cetyl, stearyl, and mustardyl. In the various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including those listed above and those in between, are explicitly intended for use herein.

[0088] Consider alkoxylated phosphate esters formed from alkoxylated triglycerides having at least one side hydroxyl group; this compound can also be any compound known in the art. Alkoxylation can be as described above. Furthermore, the triglyceride itself is not particularly limited and can be any triglyceride known in the art. Triglycerides can be described as triesters comprising glycerol bound to three fatty acid molecules, wherein each fatty acid molecule or chain has 14 to 22 carbon atoms. Naturally, only castor oil triglycerides have side hydroxyl groups. However, other triglycerides with double bonds can also have side OH groups, as the double bond can be epoxidized and hydrolyzed to side OH groups. Typically, each chain independently has 14 to 22, 14 to 20, 18 to 22, 20 to 22, 16 to 20, 16 to 18, or 18 to 20 carbon atoms. Each chain may independently contain or not contain one or more side hydroxyl groups and one or more carbon-carbon double bonds. Typical examples of triglycerides having at least one side hydroxyl group include castor oil alkoxylates and alkoxylates derived from epoxidized soybean oil. In all non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and those in between, are hereby explicitly considered for use.

[0089] In other embodiments, consider alkoxylated phosphate esters formed from alkoxylated alkylamines, compounds known in the art. Alkoxylation and alkylation can be as described above. Typical examples of alkylamines include cocoylamine, laurylamine, palmitamine, soyamine, tallowamine, stearamine, oleylamine, and rapeseedamine.

[0090] In various embodiments, the alkoxylated phosphate surfactants are primarily mixtures of monophosphates and diphosphates. They may have the following general formula:

[0091]

[0092]

[0093] Each of M and M′ is independently selected from a hydrogen atom (H) or a cation; (AO) is an alkoxy group; and R 1 and R 2 Each of the following is selected independently:

[0094] (a) An alkyl hydrocarbon (e.g., saturated or unsaturated, branched or linear) group having 12 to 22 carbon atoms as described above; wherein each of m and n is independently about 10 to about 100;

[0095] (b) An alkoxylated triglyceride group, wherein the triglyceride is derived from castor oil or an epoxidized / hydrolyzed triglyceride. An example of a triglyceride group is:

[0096]

[0097] When the triglycerides are derived from castor oil, R 3 and R 4 R is a hydrogen group, and when the triglyceride is derived from an epoxidized triglyceride, 4 for

[0098]

[0099] Where R 5 It is a hydrocarbon group.

[0100] And each of m, n, a, b, c, x, y, and z can be 0 or any value, such that m+a+b+c+x+y+z and n+a+b+c+x+y+z are less than approximately 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5, or less.

[0101] Since both alkoxylated triglycerides and phosphating agents have more than one reactive hydroxyl group, they can form oligomers or polymers.

[0102] (c) An alkoxylated alkylamine group having about 12 to 22 carbon atoms; wherein each of m and n is previously defined. An example of an alkoxylated alkylamine group has the following general formula:

[0103]

[0104] Where R 1 As described above, since both alkoxylated alkylamine phosphating agents have more than one reactive hydroxyl group, they may form oligomers or polymers.

[0105] In all non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and those in between, are hereby explicitly considered for use.

[0106] The AO group refers to an alkoxy group that can be any of the above-mentioned alkoxy groups.

[0107] Alkoxylated phosphate esters can be prepared by methods known in the art. Examples of the synthesis of phosphate esters are disclosed in various publications, including (1) US3346670; (2) WO2019162353A; (3) WO200111958; (4) Journal of Surfactants and Detergents volume 5, 169-172 pages (2002) and references therein; and (5) Tenside Surfactants Detergents 55(4):266-272, July 2018 (DOI:10.3139 / 113.110570) and references therein, each of which is expressly incorporated herein by reference into various non-limiting embodiments. Typically, alkoxylated phosphate esters include most monoalkyl phosphate esters and dialkyl phosphate esters, some unreacted starting C12-C22 alcohol alkoxylates, castor oil alkoxylates or alkylamine alkoxylates, and some phosphoric acid.

[0108] Alkoxylated phosphates can be prepared by reacting C12-C22 alcohol alkoxylates, triglyceride alkoxylates having at least one side hydroxyl group, or alkylamine alkoxylates with P2O5, polyphosphoric acid (PPA), or both. Each can be in acidic form, neutralized or partially neutralized with various neutralizing bases. Alkoxylated phosphates can also be prepared by reacting a mixture of C12-C22 alcohol alkoxylates, triglyceride alkoxylates having at least one side hydroxyl group, and alkylamine alkoxylates.

[0109] In various embodiments, the alkoxylated phosphate ester has an alcohol group with a chain length of C12-C18. More typically, the alcohol is primarily a C12-16 alcohol, a branched C13 alcohol, a cetyl (C16) alcohol, or a stearyl (C18) alcohol, or a mixture of cetyl alcohol and stearyl alcohol.

[0110] When alkoxylated phosphate esters are formed from alkoxylated triglycerides having at least one side hydroxyl group, typical triglycerides are castor oil and epoxidized triglycerides. More typically, the triglyceride is castor oil.

[0111] When alkoxylated phosphate esters are formed from alkylamine alkoxylates, the alkyl chain length is typically C12-C22. More typically, the alkyl chain length is C12-C18, such as triglycerides derived from cocoa, palm, tallow, soybean, rapeseed, corn, sunflower, and canola.

[0112] The typical alkoxylating group in the alkoxylated phosphates of this disclosure is an ethoxylating group (EO). The number of EOs is typically between about 10 and about 100, more typically between about 12 and about 64, and most typically between about 15 and about 30. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly intended to be used herein.

[0113] In one embodiment, the alkoxylated alkyl phosphate is present and selected from alkoxylated branched C13 alkyl phosphates, alkoxylated linear C12-C16 alkyl phosphates, alkoxylated linear C16-C18 alkyl phosphates, and combinations thereof. In another embodiment, the alkoxylated phosphate is present and formed from alkoxylated triglycerides selected from alkoxylated castor oil, alkoxylated epoxidized triglycerides, and combinations thereof. In a further embodiment, the alkoxylated phosphate is present and formed from alkoxylated tallow amine. In a further embodiment, the alkoxylated phosphate is present and ethoxylated to a degree of ethoxylation of about 10 to about 100, about 12 to about 60, about 15 to about 60, or about 12 to about 30. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly intended to be used herein.

[0114] In various embodiments, the alkoxylated phosphate ester is present and formed using a phosphorylating agent and hydroxyl groups with an initial molar equivalent ratio of about 1:3 to about 1:1, for example about 1:1.5, 1:2, 1:2.5. The phosphorylating agent can be any phosphorylating agent known in the art or described herein. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​above and values ​​between the values ​​above, are expressly intended to be used herein.

[0115] In other embodiments, the alkoxylated phosphate ester is present and comprises a monophosphate and a diphosphate in a molar ratio of about 12:1 to about 1:1. The monophosphate and diester are selected based on the specific chemical properties described above, as is well known in the art. In various embodiments, the ratio is about 16:1, 11.5:1, 11:1, 10.5:1, 10:1, 9.5:1, 9:1, 8.5:1, 8:1, 7.5:1, 7:1, 6.5:1, 6:1, 5.5:1, 5:1, 4.5:1, 4:1, 3.5:1, 3:1, 2.5:1, 2:1, or 1.5:1. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​described above and values ​​between the values ​​described above, are expressly intended to be used herein.

[0116] In other embodiments, alkoxylated phosphates are present and, based on the total weight of the alkoxylated phosphates, contain less than about 40, 35, 30, 25, 20, 15, 10, or 5% by weight of the active substance of unreacted alkoxylated alcohols, alkoxylated triglycerides, or alkoxylated alkylamines. In all non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​described above and those between the values ​​described above, are expressly intended to be used herein.

[0117] In various embodiments, the alkoxylated phosphate ester is present in an amount greater than about 0 to about 40, about 5 to about 30, or about 8 to about 20% by weight of active substance, based on the total weight of the composition. For example, this amount may be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, or 40% by weight of active substance, based on the total weight of the composition. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and values ​​between the values ​​mentioned above, are expressly intended to be used herein.

[0118] Supplemental additives:

[0119] In various embodiments, one or more supplementary additives (different from the aforementioned additives) are also included in the composition. For example, in one embodiment, the composition comprises a second surfactant that is different from the alkoxylated phosphate surfactant. The second surfactant is not particularly limited and can be any anionic, cationic, nonionic, and / or amphoteric / amphoionic surfactant known in the art. In various embodiments, the second surfactant is selected from alkylbenzene sulfonic acids such as dodecylbenzene sulfonic acid and its isopropylamine salt, isopropylamine salts of C8-C10 linear or branched carboxylic acids, isopropylamine salts of tall oil fatty acids, alkylamine alkoxylates, alcohol ethoxylates, and combinations thereof.

[0120] In various embodiments, the second surfactant is selected from alkylbenzene sulfonic acids (and their salts); amine salts of C8-C10 linear or branched carboxylic acids and tall oil fatty acids (TOFA); alkylamine alkoxylates (e.g., Ethomeen SV / 25 and Ethomeen C / 12), alcohol alkoxylates; castor oil ethoxylates; polyethylene glycol dehydrated sorbitan monolaurate (e.g., Tween 20) and POE(20) dehydrated sorbitan monooleate (e.g., Tween 80); polyoxyethylene sorbitan tall oleate; and alkyl polyglucosides (e.g., AG 6210, Agnique PG-9116). Preferably, the second surfactant is selected from isopropylamine salts of alkylbenzene sulfonic acids (e.g., dodecylbenzene sulfonic acid), isopropylamine salts of C8-C10 linear or branched carboxylic acids, isopropylamine salts of tall oil fatty acids (TOFA), and alcohol ethoxylates.

[0121] In other embodiments, the supplementary additive includes a base. Any base known in the art can be used. For example, the base can be an organic or inorganic base, such as a metal hydroxide. In various embodiments, the base is selected from isopropylamine (IPA), dimethylaminopropylamine (DMAPA), monoethanolamine, ammonium hydroxide, and combinations thereof.

[0122] Alternatively, supplementary additives may include or include preservatives, colorants, odor markers, defoamers, water, or combinations thereof.

[0123] Pesticides and / or growth inhibitors:

[0124] In other embodiments, the composition comprises or is combined with pesticides and / or growth inhibitors that are different from linear fatty acids. In various embodiments, the pesticide is a liquid pesticide and may be selected from phenoxy herbicides such as 2,4-D octyl ester and MCPA; benzoic acid herbicides such as dicamba; chloroacetanilide herbicides such as acetochlor; cyclohexene oxime herbicides such as clethodim; aliphatic organothiophosphate insecticides such as malathion; thiamethoxam fungicides such as tebufenozide; thiocarbamate herbicides such as glyphosate; and combinations thereof. In other embodiments, the pesticide and / or growth inhibitor is a solid having sufficient solubility in linear C5-C10 fatty acids with or without a diluent, and the solid pesticide and / or growth inhibitor may be selected from 2,4-D acid, dicamba acid, imidazolinone herbicides such as methomyl and imazalil, maleic hydrazine, or combinations thereof.

[0125] Additional implementation plan:

[0126] In various embodiments, the composition comprises nonanoic acid, one or more alkoxylated phosphates, and a diluent. In other embodiments, the concentration of nonanoic acid in the composition is about 20 to about 95, about 35 to about 90, or about 50 to about 90% by weight of active substance, based on the total weight of the composition. In other embodiments, the concentration is about 25 to about 90, about 30 to about 85, about 35 to about 80, about 40 to about 75, about 45 to about 70, about 50 to about 65, or about 55 to about 60% by weight of active substance, based on the total weight of the composition. In various related embodiments, the concentration of alkoxylated phosphates in the composition is about 0 to about 40, greater than about 0 and at most about 30, about 5 to about 40, about 5 to about 30, about 8 to about 20, or about 10 to about 15% by weight of active substance, based on the total weight of the composition. In other relevant embodiments, the concentration of the diluent in the composition is less than about 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10, or 5% by weight of the active substance, based on the total weight of the composition. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​mentioned above and those between the values ​​mentioned above, are expressly intended to be used herein.

[0127] Emulsifiable concentrate:

[0128] In other embodiments, when the composition contains linear C5-C10 fatty acids and surfactants and with or without a diluent, the composition may be described as an emulsifiable concentrate (EC). When EC is diluted in water, a gentle agitation is sufficient to form an emulsion. As will be understood by those skilled in the art, EC generally exhibits good frosting (i.e., the ability to form an emulsion without excessive agitation when added to water) and acceptable stability. In various embodiments, an acceptable emulsion generally does not flocculate within approximately 24 hours. In various embodiments, as will be understood by those skilled in the art, after approximately 24 hours, the emulsion exhibits less than approximately 2% separation, as measured based on top cream or sediment. In some embodiments, 2-hour emulsion stability with approximately 2-3% cream is acceptable. If cream or sediment forms, the bulk emulsion whiteness can be maintained within an acceptable range, and the emulsion can be restored to its original form by gentle agitation or mixing.

[0129] In various implementations, EC exhibits acceptable performance when prepared using water with a mineral hardness of approximately 34 ppm (soft water) to approximately 1000 ppm (hard water). However, the emulsion properties of EC (such as frosting and separation) may vary with water hardness.

[0130] The composition may be a clear solution or a slightly turbid product, provided that the composition or EC does not separate during storage. Depending on the geological location, an acceptable composition should be stable between about 10°C and about 54°C, typically between about 0°C and about 54°C, more typically between about -10°C and about 54°C, and most typically between about -20°C and about 54°C. In various non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​above and those between the values ​​above, are expressly intended to be used herein.

[0131] The composition can be applied as is without dilution with water. The composition can be used with backpack sprayers, tractor sprayers, or drone sprayers without dilution with water. However, when the composition is EC, it is desirable to dilute it with water before use. It is typically diluted to 1-10% C9 acid equivalent, depending on the weed species. In all non-limiting embodiments, all numerical values ​​(including integers and decimals) and their ranges, including the values ​​above and those between the values ​​above, are expressly intended to be used herein.

[0132] One embodiment provides a high-load EC with more than about 60% by weight of the active ingredient nonanoic acid. Another embodiment provides a high-load EC with 80% or more of the active ingredient nonanoic acid.

[0133] Formulations with high loading rates save on packaging, storage, and transportation costs. Furthermore, if a formulation has a high loading rate, the end user doesn't need to purchase large quantities when going to the store, freeing up space for other supplies.

[0134] One embodiment provides a stable nonanoic acid type EC containing less than about 20% by weight of active material in total emulsifiers comprising the alkoxylated phosphate esters of this disclosure.

[0135] One embodiment provides a stable nonanoic acid-type EC having an alkoxylated phosphate ester of the present disclosure and a diluent that lowers the melting point, wherein the combination of the alkoxylated phosphate ester and the diluent provides adjuvant properties to the nonanoic acid.

[0136] One implementation provides a stable nonanoic acid type EC that can be mixed with a variety of canning additives.

[0137] One embodiment provides a pesticide composition comprising nonanoic acid, a liquid pesticide, and an alkoxylated phosphate ester of the present disclosure.

[0138] Canned Mixture:

[0139] This disclosure also provides a can-mix composition comprising the aforementioned agrochemical composition and a can-mixing additive. The can-mixing additive is not particularly limited and can be any additive known in the art. In various embodiments, the can-mixing additive is selected from ammonium sulfate, potassium sulfate, ammonium nitrate, drift control agents, and pesticide formulations. Typical can-mixing additives are ammonium sulfate and aqueous pesticide formulations containing glyphosate, glufosinate, and dicamba.

[0140] method:

[0141] This disclosure also provides a method comprising the steps of: providing an agrochemical composition and applying the composition to a target, said target being any plant, crop, pest, etc. In one embodiment, the composition is not diluted with water prior to the application step. However, in alternative embodiments, the composition may be diluted with water prior to the application step.

[0142] Example

[0143] Phosphate ester samples

[0144] Various alkoxylated phosphate samples were prepared using well-known methods. The starting alkoxylate was reacted with a phosphoric acid agent. The phosphoric acid agent used was P₂O₅, polyphosphoric acid (PPA), or a combination of PPA followed by P₂O₅ to convert the residual starting alcohol ethoxylate. The molar ratio of alkyl alcohol ethoxylate to phosphoric acid was between 1:1 and 3:1. The molar ratio of castor oil ethoxylate to phosphoric acid was 1:3 (i.e., ROH:phosphoric acid = 1:1). The molar ratio of tallow amine ethoxylate to phosphoric acid was 1:2 (i.e., ROH:phosphoric acid = 1:1). The sample could be hydrolyzed with water (a few weight percentages) to convert the pyrophosphate, unreacted P₂O₅, or PPA to phosphoric acid. Generally, the emulsifying properties were not affected by this final hydrolysis step.

[0145]

[0146]

[0147] a: Total acidity = 1.35 meq / g, strong acidity = 0.81 meq / g, H3PO4 = 0.085 meq / g, MAP = 0.45 meq / g, DAP = 0.26 meq / g, water = 20% by weight, clear at room temperature.

[0148] b: Total acidity = 1.35 meq / g, strong acidity = 0.81 meq / g, H3PO4 = 0.135 meq / g, MAP = 0.28 meq / g, DAP = 0.10 meq / g, water = 20% by weight, free-flowing at 25°C.

[0149] The weight percentage of H3PO4 in the sample is usually about one-tenth of the molar percentage in the sample.

[0150] Emulpon CO-360 is an ethoxylated castor oil compound with approximately 36-44 EO groups. Emulpon CO-200 is an ethoxylated castor oil compound with approximately 20 EO groups.

[0151] Except for the phosphate esters of castor oil ethoxylates (PE20, PE21, and PE22), PE1 (containing approximately 20% water added after the reaction), PE14, PE17, and PE24, all samples were solids or pastes at room temperature. PE2 contained approximately 17% water added after the reaction. If the product underwent a final hydrolysis step, it may contain several percentage points of water by weight.

[0152] Commercially available nonanoic acid EC

[0153] Comparative examples of the emulsions were formed using commercially available products. For example, Scythe and Beloukha were used as comparative examples. Scythe is known to contain 57% C9 acid, 3% other fatty acids, 30% petroleum mineral oil, and 10% emulsifier. Beloukha contains 51.9% C9 acid and other undisclosed ingredients. Scythe and Beloukha were diluted at various concentrations in water of different hardnesses, and the resulting emulsions were observed. The emulsions were placed in long emulsion tubes (approximately 400 mm). After adding the product to water, the emulsion tubes were inverted 10 to 15 times. The emulsion results are shown below.

[0154]

[0155]

[0156] The data indicates that the performance of these commercially available benchmark emulsions is not ideal. In the case of Beloukha, the emulsions in moderately hard water (342 ppm) and hard water (1000 ppm) are unacceptable.

[0157] Example 1 – Diluent for Nonanoic Acid

[0158] Hexanol was Alfol 6 from Sasol. CE-810K and C8-C10 methyl esters were from P&G. Sylfat 2LT was from Kraton. Aromatic 200 and Isopar L were from ExxonMobil Chemicals. Nonanoic acid (C9 acid) was purchased from Sigma-Aldrich (97%) or obtained from Matrica (Matrilox AP001M, 98%) or Emery Oleochemicals (EmerionW 90PA, 90%). Other chemicals were purchased from Sigma-Aldrich.

[0159] The following diluents were evaluated to determine whether each diluent could lower the melting point of nonanoic acid. The term "crystals" refers to nonanoic acid crystals that are visually observed. "Clarity" refers to a solution that is clear to the naked eye.

[0160]

[0161]

[0162] Data indicates that to lower the melting point of nonanoic acid to 0°C (or lower), the following solutions are required: 25% ethyl acetate, heptanoic acid, or neoheptanoic acid; 30% 2-EH acid, 2-EH alcohol, Exxal 9 (branched C9 alcohol), hexanol, d-limonene, octyl lactate, Matrilox IL001M, methyl benzoate, valeric acid, or Aromatic 200; 33.3% triethyl phosphate; or 35% CE-810K (C8-10 methyl ester), methyl salicylate, tributyl phosphate, tall oil fatty acids (TOFA), or Arneel C (coconitrile). The data also indicate that the melting point of Emerion W 90PA (90% nonanoic acid and 6% C8-C10 acid) is more easily lowered compared to nonanoic acid grades with >97% concentration.

[0163] Low-melting-point nonanoic acid compositions with suitable diluents can be used in backpack and drone applications without dilution with water. Low-melting-point nonanoic acid compositions with suitable diluents can also be used as a base for formulating low-melting-point nonanoic acid emulsion concentrates.

[0164] Example 2 – Nonanoic acid EC with various alkoxylated alkyl phosphates and its emulsion

[0165] Emulsion concentrates (ECs) are obtained by mixing nonanoic acid, the alkoxylated alkyl phosphates of this disclosure, and optionally other emulsifiers and a neutralizing base. The composition of the EC without diluent is shown below.

[0166]

[0167]

[0168] (e) indicates that EC was diluted in water and the resulting emulsion data was obtained.

[0169] (c) represents a comparative example.

[0170] The surfactants used in the comparative examples were emulsifiers well-known in various applications. However, all comparative examples showed poor emulsification when diluted at 5% in water. Emphos CS-141 is a nonylphenol-10EO phosphate and is a product similar to Stepfac 8170 (used in Table II of US4975110).

[0171] The emulsion of nonanoic acid EC without diluent is described below.

[0172]

[0173] Emulsions are graded based on their whiteness: Excellent, Very Good, Good, Average, and Fair. Semi-transparent with no separation falls into the "Excellent" category.

[0174] Example 3 - Nonanoic acid EC and its emulsion containing diluents and various alkoxylated alkyl phosphates

[0175] The composition of EC with diluent is shown below.

[0176]

[0177]

[0178]

[0179] (e) indicates that EC was diluted in water and the resulting emulsion data was obtained.

[0180] (c) represents a comparative example.

[0181] Sylfat is tall oil fatty acid. Witconate 93S is the isopropylamine salt of Witconic 1298S (C10-16-alkyl ester of benzenesulfonic acid). Matrilox IL001M is a mixture of C5-C9 monocarboxylic acids (C9 acid <15%). Emulpon CO-550 and Emulpon CO-360 are ethoxylated castor oils with 55 and 36 EOs, respectively. Ethomeen SV / 25 is ethoxylated soybean amine with 15 EOs. Sponto EC-452 is an emulsifier blend. Ethylan NS-500LQ is an emulsifier composed of a polymer of methyl-ethylene oxide (propylene oxide), ethylene oxide, and mono[2-(2-butoxyethoxy)ethyl] ether. Phospholan PS-131 is a C13-6EO phosphate ester.

[0182] Sometimes EC samples may become cloudy. It has been found that adding some water improves the appearance of the sample. Therefore, it is advantageous to add water.

[0183] An example of an emulsion of nonanoic acid EC and alkyl phosphate is shown below. An emulsion was obtained by adding EC to water in an emulsion tube and then inverting the tube 10 to 15 times. Emulsion stability was observed at different time intervals. Water hardness was 34 ppm (soft water), tap water (similar to soft water), 342 ppm, or 1000 ppm.

[0184] The emulsion whiteness grade (visually) is excellent, very good, good, average, and acceptable.

[0185]

[0186]

[0187]

[0188] * Indicates that the separation did not occur 30 minutes after being flipped back.

[0189] ** indicates that EC was aged at room temperature for 14 days before being diluted in water.

[0190] It appears that ECs containing the phosphate esters disclosed herein exhibit better emulsion performance in hard water at 343 ppm and 1000 ppm than in water at 34 ppm (and tap water).

[0191] Almost all aged emulsions (>20 hours) will separate, but they can be remixed back into the original emulsion by one or two flips.

[0192] Example 4 - Nonanoic acid EC and its emulsion using other nonanoic acid sources

[0193] Some commercially available products contain less than 97% nonanoic acid. Examples include EmerionW 90 PA (90% C9 acid) from Emery Oleochemicals, Emery 1202 (90% C9 acid) and Emery 1210 (27% C9 acid) from BASF / Cognis, and PRIFRAC 2914 (90% C9 acid) from Croda.

[0194] Emulsion concentrates (ECs) are obtained by mixing Emerion W 90 PA or Emery 1202 with the alkoxylated phosphate esters of this disclosure. The composition of ECs is shown below. In the table below, C9 represents nonanoic acid.

[0195]

[0196] The ECs described above were used to form the following emulsions. The emulsions were obtained by adding ECs to water and then inverting the emulsion 10 times. Emulsion stability was observed at different time intervals. The table below lists the ECs prepared using nonanoic acid (90% purity) and alkyl phosphates.

[0197]

[0198]

[0199] All aged emulsions (16-24 hours) separated, but were remixed back into white emulsions by one or two inversions.

[0200] Example 5 – Tank Mixing Application of Nonanoic Acid EC

[0201] It is a common practice for end users to mix tank-mixed additives with emulsions. Examples of tank-mixed additives used in this disclosure include ammonium sulfate (AMS), Base Camp Amine 4 (46.8% 2,4-drop DMA), Roundup PowerMax (540 g ae / l K-glyphosate), Clarity (58% dicamba salt), and Liberty 280 (24.5% NH4 glufosinate). They can be added to the water first or after the emulsion is formed. The tank-mixing compatibility results, i.e., the mixed emulsion, are shown below.

[0202] Dilute 5% EC56 in water (containing various herbicides) with hardnesses of 34 ppm, 342 ppm, and 1000 ppm in a long tube (approximately 400 mm in length). Observe for blooming and emulsification after 10 inversions.

[0203]

[0204] No flocculation was observed in any of the samples listed in the table above. This means that EC is compatible with Base camp Amine4 (2,4-drop salt), Roundup PowerMax (glyphosate salt), Roundup WeatherMax (glyphosate salt), Clarity (dicamba salt), Liberty 280 (glufosinate salt), and ammonium sulfate. All aged emulsions returned to good condition after one or two inversions.

[0205] Example 6 - Synergistic wetting effect between nonanoic acid and alkyl phosphate esters

[0206] Unexpectedly, a synergistic effect was found between C9 acid and phosphate esters, such as PE2 (C1216-30 phosphate ester), in terms of wetting / spreading. Neither aqueous solutions of C9 acid nor PE2 (0.5-3.7%) could wet hydrophobic polystyrene dishes. That is, a drop of solution clumped together with a large contact angle on the dish. However, when 3.3% C9 acid was blended with 3.3% PE2, for example, 90% (3.3% C9 acid) + 10% (3.3% PE2), better wetting and a larger coverage area were observed.

[0207] 6.1 100％ 0％ Poor wettability 6.2 90％ 10％ Good wetting and spreading properties 6.3 0％ 100％ Poor wettability

[0208] Good wetting is crucial for contact pesticides like nonanoic acid, as they need to cover as large an area as possible.

[0209] Example 7 - Greenhouse Biological Efficacy

[0210] A greenhouse trial was conducted to compare the bioavailability of the baseline Scythe with that of the nonanoic acid EC disclosed herein. Two species were used—spring wheat and morning glory. The trial was conducted in quadruplicate for each weed species. Ratings were performed 3 days after treatment. The composition of the samples is shown in the table below.

[0211]

[0212] The efficacy results showed that samples 7.2 and 7.3 with 5.56% concentration had equivalent efficacy to Scythe with 8.33% concentration. In other words, the combination of the diluent 2-EH acid in sample 7.2 and the diluent hexanol in sample 7.3 with phosphate ester PE15 enhanced the efficacy of nonanoic acid.

[0213] Example 8—Further Efficacy Study

[0214] A dip-in experiment was conducted to compare the efficacy of the baseline Scythe with various nonanoic acid ECs disclosed herein. Live leaves from plants growing on the ground were dipped (or soaked) in both the test and control samples. The live leaves could come from the same plant—one could be dipped in the test sample, and another in the control sample. After dip-in, the samples were removed, leaving the leaves on the plants. After a period of time, symptoms (damage to the leaves) were visually assessed and photographed. This dip-in method has advantages over traditional spraying methods. It provides more consistent results across different trials. It eliminates potential errors associated with traditional spraying methods, such as inaccurate spray volume, wind speed, weed variability due to growth in different pots, and canopy shading effects. This dip-in method is particularly suitable for contact herbicides such as nonanoic acid because damage symptoms appear very rapidly (from minutes to hours, depending on the weed species).

[0215] The composition and results of the samples are shown below. Each comparative experiment was conducted on different dates, comparing the efficacy of 8.33% Scythe emulsion (control sample) with various concentrations of nonanoic acid emulsion (test samples).

[0216]

[0217] EC was diluted with water, and the leaves were immersed in the diluted solution while remaining on the plant. Scythe was used as a baseline. The results of the immersion solution concentration and efficacy after 14–24 hours are shown below:

[0218]

[0219]

[0220] a: Houttuynia cordata

[0221] b: Tomato leaves

[0222] c: Tricolor amaranth

[0223] Example 9 - Nonanoic acid EC containing phosphate esters derived from castor oil ethoxylates

[0224] Various ECs are formed and described below. These ECs include phosphate esters of castor oil ethoxylates.

[0225]

[0226]

[0227] DDBSA stands for dodecylbenzenesulfonic acid (Witconic 1298S). DMAPA stands for dicarboxypropylamine.

[0228] After formation, a nonanoic acid EC emulsion containing phosphate esters of castor oil ethoxylate is formed as described below, and then visually evaluated.

[0229]

[0230] *After 3 days, the bottom cleared at 18%. However, no separation occurred 30 minutes after re-flipping.

[0231] Add 0.3g of ammonium sulfate to 100g of emulsions ID 9b.1b and ID 9b.2, and the cream volume is reduced to 2% (2 hours).

[0232] It appears that the behavior of castor oil ethoxylated phosphate esters PE20 and PE21 is similar to that of the ethoxylated alkyl phosphate esters of this disclosure.

[0233] Example 10 - A pesticide composition comprising nonanoic acid, another pesticide, and an alkoxylated phosphate ester

[0234] The pesticide composition comprising nonanoic acid, another pesticide, and alkoxylated phosphate esters is formed as described below.

[0235]

[0236] MCPA and 2,4-D herbicides are solids at room temperature, while all other pesticides are liquids.

[0237] Example 11 - Nonanoic acid EC containing ethoxylated tallow amine phosphate ester and its emulsion

[0238]

[0239] Data shows that the phosphate ester from tallow amine-40EO is an excellent emulsifier for C9 acid EC. The emulsions shown in the table above are stable and have excellent whiteness.

[0240] The data above indicate that all lotions produced good to excellent creaminess. After 24 hours, the lotions were inverted again, and 30 minutes after inversion, they exhibited similar separation.

[0241] Example 12 - Ready-to-use emulsion

[0242] Ready-to-use products are convenient for non-professional consumers and do not require dilution with water. It has also been found that the phosphate esters of this disclosure can be used to prepare ready-to-use emulsions containing linear C5-C10 fatty acids. In this case, no diluent is needed unless the diluent provides additional benefits.

[0243] Ready-to-use emulsions can be prepared by first manually and vigorously mixing (shaking) the fatty acids and water of this disclosure for 5 to 10 seconds, followed by adding the phosphate ester and manually and vigorously shaking for another 5 to 10 seconds. Heating may be necessary if the phosphate ester or blend of the phosphate ester with other surfactants does not dissolve quickly in water. Additional shaking may be required after 20 to 60 minutes. In a manufacturing plant, mixing can be performed using suitable apparatus and methods known in the art.

[0244] Examples of ready-to-use emulsions are shown below.

[0245] Ready-to-use emulsion

[0246]

[0247] While at least one exemplary embodiment has been presented in the foregoing detailed description, it should be understood that numerous variations exist. It should also be understood that the at least one exemplary embodiment is merely an example and is not intended to limit the scope, applicability, or configuration in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient roadmap for implementing the exemplary embodiments. It should be understood that various changes can be made to the function and arrangement of the elements described in the exemplary embodiments without departing from the scope set forth in the appended claims.

Claims

1. A pesticide emulsion concentrate, comprising: Nonanoic acid, based on the total weight of the concentrate, comprising 50 to 90% by weight of the active substance; and The additives include diluents and alkoxylated phosphate surfactants. The alkoxylated phosphate surfactant, having an ethoxylation degree of 12 to 40 and selected from alkoxylated C12-C22 alkyl phosphates, comprises 5 to 20% by weight of active substance based on the total weight of the concentrate; and The diluent is selected from 2-ethylhexanoic acid, 2-ethylhexanol, hexanol and combinations thereof, and its content is 10 to 40% by weight of active substance based on the total weight of the concentrate.

2. The pesticide emulsion concentrate according to claim 1, wherein the alkoxylated phosphate ester is present and selected from alkoxylated branched C13 alkyl phosphate esters, alkoxylated linear C12-C16 alkyl phosphate esters, alkoxylated linear C16-C18 alkyl phosphate esters, and combinations thereof.

3. The pesticide emulsion concentrate according to claim 1, wherein the alkoxylated phosphate ester is present and formed using a phosphorylating agent and hydroxyl group with an initial molar equivalent ratio of 1:3 to 1:

1.

4. The pesticide emulsion concentrate according to claim 2, wherein the alkoxylated phosphate ester is present and formed using a phosphorylating agent and hydroxyl group with an initial molar equivalent ratio of 1:3 to 1:

1.

5. The pesticide emulsion concentrate according to claim 1, wherein the alkoxylated phosphate ester is present and comprises monophosphate and diphosphate in a molar ratio of 16:1 to 1:

1.

6. The pesticide emulsion concentrate according to any one of claims 1 to 5, wherein the alkoxylated phosphate ester is present and, based on the total weight of the alkoxylated phosphate ester, comprises less than 40% by weight of unreacted alkoxylated alcohol of the active substance.

7. The pesticide emulsion concentrate according to any one of claims 1 to 5, wherein... The diluent is 2-ethylhexanoic acid.

8. The pesticide emulsion concentrate according to any one of claims 1 to 5, wherein the diluent is 2-ethylhexanol.

9. The pesticide emulsion concentrate according to any one of claims 1 to 5, wherein the diluent is hexanol.

10. The pesticide emulsion concentrate according to any one of claims 1 to 5, further comprising a second surfactant selected from alkylbenzene sulfonic acid, isopropylamine salts of C8-C10 linear or branched carboxylic acids, isopropylamine salts of tall oil fatty acids, alkylamine alkoxylates, alcohol ethoxylates, and combinations thereof.

11. The pesticide emulsion concentrate according to any one of claims 1 to 5, further comprising a base selected from isopropylamine, monoethanolamine, dimethylaminopropylamine, ammonium hydroxide, and combinations thereof.

12. The pesticide emulsion concentrate according to any one of claims 1 to 5, having a melting point of less than or equal to 5°C.

13. The pesticide emulsion concentrate according to any one of claims 1 to 5, further comprising a pesticide different from the nonanoic acid.

14. The pesticide emulsion concentrate according to claim 13, wherein... The pesticides include herbicides selected from glyphosate, dicamba, glufosinate, glufosinate, acetochlor, clethodim, imidazolinone, and combinations thereof; The pesticide includes fungicides that optionally contain terbinafine; and / or The pesticide may optionally contain malathion as an insecticide.

15. A canning composition comprising a pesticide emulsion concentrate according to any one of the preceding claims and a canning additive optionally comprising ammonium sulfate.

16. A method comprising the steps of providing a pesticide emulsion concentrate according to any one of the preceding claims and applying the pesticide emulsion concentrate to a target.

17. The method of claim 16, wherein the pesticide emulsion concentrate is not diluted with water prior to the application step.

Images