Liquid agricultural adjuvants

Abstract

The present disclosure provides alkyl (C 12 ~C 16 The present invention provides a liquid agricultural adjuvant comprising at least one alkyl (C1-C8) ester of alkyl (C) acid; at least one anionic surfactant; and at least one nonionic surfactant. The liquid agricultural adjuvant has a flash point of greater than about 100°C and is 12 ~C 16 The at least one alkyl (C1-C8) ester of a) acid has a paraffin wax dissolving capacity of 2% to 20% by weight at 25° C. The present disclosure extends to methods of making the liquid agricultural adjuvant according to the first aspect and methods of use, typically in agricultural endeavors.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present disclosure relates to adjuvants, and in particular, the disclosure relates to liquid agricultural adjuvants having a flash point above about 100° C. The adjuvants are alkyl (C 12 ~C 16 at least one alkyl (C1-C8) ester of an alkyl (C) acid, an anionic surfactant, and a nonionic surfactant; 12 ~C 16 At least one alkyl (C1-C8) ester of the ) acid is safe for human and / or animal use. [Background technology]

[0002] Background of the Invention Adjuvants are commonly used in agriculture to improve the performance of pesticides and may be added to the spray tank to improve pesticidal activity or properties during application. Spray adjuvants generally fall into two broad categories: (i) activator adjuvants, which are commonly used to enhance postemergence performance, increase activity, aid absorption into plant tissues, and rainfastness, and may include surfactants, oil crop concentrates, nitrogen fertilizers, spreading-sticking agents, wetting agents, and penetrating agents; and (ii) water conditioning adjuvants, which extend the range of conditions under which a particular formulation can be used and further modify the physical properties of the spray solution, and may include compatibilizers, buffers, pH adjusters, antifoam agents, and drift control agents.

[0003] Insecticides, fungicides, acaricides, nematicides, herbicides, plant growth regulators, insect growth regulators, and nutrients are typically formulated into various types of agricultural compositions for use on crops, such as as health-improving or disease-controlling agents, insect control agents, or weed control agents. Agricultural compositions can be formulated as water-based or solvent-based liquids, alternatively as soluble or insoluble powders, and further alternatively as granules and / or other solid forms. Fillers, padding agents, solvents and cosolvents, emulsifiers, dispersants, and wetting agents are typically incorporated into such compositions to ensure that the pesticidal composition disperses, dissolves, or emulsifies in the mixture tank or bath and provides sustained stability before and during application. They also function to ensure optimal delivery and improve the effectiveness of the pesticidal active ingredient when the pesticidal agricultural composition is used. Surfactants and adjuvants, when utilized, can affect many properties of agricultural compositions, such as solubility, volatility, dispersibility, viscosity, particle size, efficacy, and freezing and flash points. Summary of the Invention [Problem to be solved by the invention]

[0004] It is known that surfactants often incorporated into pesticidal agricultural compositions are not sufficient to completely ensure the stability of tank mixes containing multiple components. Therefore, adding an adjuvant to a tank mix may be necessary for better stability. A certain adjuvant may improve certain physicochemical properties of an agricultural composition, but may also deteriorate other physicochemical properties. For example, without being limited by theory, improved solubility may be accompanied by increased volatility, decreased viscosity, increased particle size, decreased efficacy, a change in freezing point, and / or a lowered flash point. In one example, the flash point is generally known as the lowest temperature at which a liquid can form an ignitable mixture in air near its surface. Therefore, if the flash point is lowered, the resulting composition will pose an increased risk during use. The lower the flash point, the more easily the mixture and / or surface may ignite. Furthermore, the lower the flash point, the faster the evaporation rate, which in turn reduces the efficiency of the agricultural composition when used.

[0005] Surfactants are important and widely used in adjuvants or co-formulations utilized with pesticides. The addition of surfactant-based adjuvants to tank mixes is widely known to provide stabilization of pesticidal agricultural compositions.

[0006] Surfactant and oil-based adjuvants are also known to improve the performance of chemicals dissolved, emulsified, or dispersed in water or other solvent media. There is a need for new, innovative adjuvants for agricultural compositions that are environmentally friendly and at the same time provide a low flash point and / or a low evaporation rate during use. Furthermore, there is a general need to at least improve upon the known shortcomings of the prior art. [Means for solving the problem]

[0007] Summary of the Invention According to a first aspect of the present disclosure, Alkyl (C 12 ~C 16) acid; and at least one alkyl (C1-C8) ester of at least one anionic surfactant; at least one nonionic surfactant; A liquid agricultural adjuvant comprising: The liquid agricultural adjuvant has a flash point above about 100°C; Alkyl (C 12 ~C 16 At least one alkyl (C1-C8) ester of a) acid has a paraffin wax dissolving ability of about 2% by weight to about 20% by weight at 25°C; A liquid agricultural adjuvant is provided.

[0008] It should be understood that the liquid agricultural adjuvants may be provided in a concentrated form that can be diluted with water and / or other solvents. The concentrates may be formulated as emulsifiable and / or microemulsified concentrates.

[0009] The term "microemulsified" as used herein refers to a dispersion made of water and / or oil and / or surfactant that is an isotropic and thermodynamically stable system. The adjuvant can be diluted for use in water or other chemicals, such as solutions of water, glycols and alcohols or other water-miscible liquids, such as methanol, ethanol, monoethylene glycol, propylene glycol, etc.

[0010] Alkyl (C 12 ~C 16 The at least one alkyl (C1-C8) ester of a ) acid may be selected from the group including, but not limited to, natural or synthetic, straight chain or branched, saturated or unsaturated, modified or unmodified, and the alkyl ester may be a compound selected from the group including, but not limited to, methyl ester, ethyl ester, propyl ester, butyl ester, isopropyl ester, isobutyl ester, isopentyl ester, 2-ethylhexyl ester, or components or combinations thereof.

[0011] Alkyl (C 12 ~C 16 The at least one alkyl (C1-C8) ester of a hydroxycarboxylic acid may be derived from an alkyl acid selected from the group including, but not limited to, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid, palmitic acid, and combinations thereof.

[0012] Alkyl (C 12 ~C 16 The at least one alkyl (C1-C8) ester of hydroxypropyl laurate may be selected from the group including, but not limited to, isobutyl laurate, isopentyl laurate, methyl laurate, 2-ethylhexyl laurate, 2-ethylhexyl palmitate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, and combinations thereof.

[0013] The at least one anionic surfactant may be, but is not limited to, (C6 to C 18 ) Alkylbenzenesulfonate, calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, amines (C6-C 18 ) Alkylbenzene sulfonate, Triethanolamine dodecylbenzene sulfonate, (C6-C 18 ) Alkyl ether sulfate, (C6-C 18 ) Alkyl ethoxylated ether sulfate, (C6-C 18 ) Alkyl sulfate, lauryl ether polyethoxylated sodium sulfate, (C6-C 18 ) Alkyl phosphate esters, (C6-C 18 ) Alkoxylated sulfates, (C6-C 18 ) alkoxylated phosphate esters, xylene sulfonate salts, cumene sulfonate salts, and combinations thereof.

[0014] The at least one nonionic surfactant may be, but is not limited to, natural and / or synthetic (C8-C9 22 ) alkoxylated fatty alcohols, (C8-C22 ) Ethoxylated fatty alcohols, (C8-C 22 ) Propoxylated fatty alcohols, (C8-C 22 ) Ethoxylated and propoxylated fatty alcohols, linear (C4-C 10 ) Alkyl (poly)glycosides, branched chain (C4-C 10 ) alkyl (poly)glycosides; and alkoxylated sorbitan fatty esters, alkoxylated sorbitol fatty esters, ethoxylated sorbitan fatty esters, ethoxylated sorbitol fatty esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and combinations thereof.

[0015] The ethoxylated fatty alcohols of fatty acids may have a degree of ethoxylation of 1 to 50, more preferably 2 to 30, and most preferably 3 to 10.

[0016] Some alkoxylated alcohols contemplated for use are branched alcohols, such as Guerbet alcohols, e.g., 2-propylheptanol and 2-ethylhexanol, and C 10 -oxo-alcohol or C 13 Oxo-alcohols, i.e., predominantly at least one branched C 10 -Alcohol or C 13 - Includes alcohol mixtures formed by alcohols and those based on alcohols commercially available as Exxal alcohols from Exxon Mobile Chemicals and Neodol alcohols from Shell Chemicals.

[0017] The liquid agricultural adjuvant may further comprise additives selected from the group including, but not limited to, preservatives, clarifying agents, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidifying agents, chelating agents, complexing agents, dyes, rheology modifiers, antifoaming agents, anti-drift agents, and water, oil, or other solvents, and combinations thereof. The acidifying agent may be citric acid and / or a derivative of citric acid.

[0018] In certain embodiments of the present disclosure, alkyl (C 12 ~C 16 The at least one alkyl (C1-C8) ester of a hydroxypropyl methylcellulose acid may be present in an amount of about 0.1% to about 30% by weight, the at least one anionic surfactant may be present in an amount of about 1% to about 50% by weight, and the at least one nonionic surfactant may be present in an amount of about 1% to about 50% by weight. This embodiment may provide a liquid agricultural adjuvant in the form of a concentrate. It should be understood that the liquid agricultural adjuvant may be further diluted with water or other solvents.

[0019] In another embodiment of the present disclosure, alkyl (C 12 ~C 16 The at least one alkyl (C1-C8) ester of a hydroxypropyl methylcellulose acid may be present in an amount of about 0.1% to about 20% by weight, preferably about 2% to about 15% by weight, the at least one anionic surfactant may be present in an amount of about 3% to about 20% by weight, and the at least one nonionic surfactant is present in an amount of about 5% to about 30% by weight. This embodiment may provide a liquid agricultural adjuvant in the form of a concentrate. It should be understood that the liquid agricultural adjuvant may be further diluted with water or other solvents.

[0020] Liquid agricultural adjuvants typically contain from about 0.1 to about 20% by weight of alkyl (C 12 ~C 16at least one alkyl (C1-C8) ester of a hydroxypropyl methylcellulose (C1-C8) acid; about 1 to about 50% by weight of at least one anionic surfactant; about 1 to about 50% by weight of at least one nonionic surfactant; and about 2 to about 80% by weight of water and / or other additives. This embodiment may still provide a liquid agricultural adjuvant in concentrate form.

[0021] In exemplary embodiments of the present disclosure, alkyl (C 12 ~C 16 at least one alkyl (C1-C8) ester of a hydroxybenzoate (C1-C8) acid; at least one anionic surfactant present in an amount of about 3% to about 20% by weight; and at least one nonionic surfactant present in an amount of about 5% to about 30% by weight; Alkyl (C 12 ~C 16 ) acid, wherein the at least one alkyl (C1-C8) ester is selected from the group including, but not limited to, isobutyl laurate, isopentyl laurate, methyl laurate, 2-ethylhexyl laurate, 2-ethylhexyl palmitate, isopropyl laurate, isopropyl myristate, isopropyl palmitate, and combinations thereof; The at least one anionic surfactant may be, but is not limited to, (C6 to C 18 ) Alkylbenzenesulfonate, calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, amines (C6-C 18 ) Alkylbenzene sulfonate, Triethanolamine dodecylbenzene sulfonate, (C6-C 18 ) Alkyl ether sulfate, (C6-C 18 ) Alkyl ethoxylated ether sulfate, (C6-C 18 ) Alkyl sulfate, lauryl ether polyethoxylated sodium sulfate, (C6-C 18 ) Alkyl phosphate esters, (C6-C18 ) Alkoxylated sulfates, (C6-C 18 ) selected from the group including alkoxylated phosphate esters, xylene sulfonate salts, cumene sulfonate salts, and combinations thereof; The at least one nonionic surfactant may be, but is not limited to, (C8 to C 22 ) alkoxylated fatty alcohols, (C8-C 22 ) Ethoxylated fatty alcohols, (C8-C 22 ) Propoxylated fatty alcohols, (C8-C 22 ) Ethoxylated and propoxylated fatty alcohols, linear (C4-C 10 ) Alkyl (poly)glycosides, branched chain (C4-C 10 ) alkyl (poly)glycosides; and selected from the group comprising alkoxylated sorbitan fatty esters, alkoxylated sorbitol fatty esters, ethoxylated sorbitan fatty esters, ethoxylated sorbitol fatty esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, and combinations thereof.

[0022] Exemplary embodiments of the present disclosure may further include water as a diluent and / or other additives, and the liquid agricultural adjuvant may comprise from about 0.1% by weight to about 20% by weight of alkyl(C 12 ~C 16 at least one alkyl (C1-C8) ester of a hydroxypropyl methylcellulose (C1-C8) acid; from about 1% to about 50% by weight of at least one anionic surfactant; from about 1% to about 50% by weight of at least one nonionic surfactant; and from about 2% to about 80% by weight of water and / or other additives. This embodiment may still provide a liquid agricultural adjuvant in concentrate form.

[0023] The additive may be at least one selected from the group including, but not limited to, preservatives, clarifying agents, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidifying agents, chelating agents, complexing agents, dyes, rheology modifiers, antifoaming agents, anti-drift agents, and water, oil or other solvents, and combinations thereof. The acidifying agent may be citric acid and / or its derivatives.

[0024] The oil may be a natural compound modified by esterification or transesterification, such as alkyl fatty acid esters, e.g., methyl esters, ethyl esters, propyl esters, butyl esters, 2-ethylhexyl esters or dodecyl esters, preferably glycol or glycerol fatty acids, e.g., (C 10 ~C 22 ) Fatty acid esters, such as those from vegetable oils, preferably oil-producing plant species, such as soybean, corn, sunflower, rapeseed, cottonseed, linseed, palm, safflower, coconut, castor, olive, canola oil, among others, mixed with essential or edible oils extracted from various plants or plant parts, such as trees, shrubs, leaves, flowers, grasses, fluids, herbs, fruits and seeds, either pure or in combination with one or more oils, or mixed with each other.

[0025] In further embodiments, the oil may be a natural compound, such as an essential oil, a citrus oil, a component of a citrus oil, a terpene oil (the terpene oil comprises D-limonene), or one or more terpene-containing natural oils (the one or more terpene-containing natural oils comprise at least 50% terpenes and are selected from the group consisting of orange oil, grapefruit oil, lemon oil, lime oil, tangerine oil, pine oil, pure, combined with other oils, or in any combination).

[0026] The liquid agricultural adjuvant (in concentrate form) may have a flash point of more than 100°C as measured in a closed cup device and may contain alkyl (C 12 ~C 16The at least one alkyl (C1-C8) ester of a) acid may have a dissolving capacity of at least 2% by weight of paraffin wax (CAS No. 8002-74-2) at 25°C, and the emulsifiable and / or microemulsified liquid adjuvant may be diluted to provide a diluted liquid agricultural adjuvant that is mixed with water and / or other chemicals in a ratio of 1:5000 to 1:10 in a tank mix or applied in an irrigation system and may be applied by air-assisted sprayers, conventional sprayers, ultra-low volume equipment such as aerial spraying, electrostatic spraying, fogger and mist spray equipment, and chemigation systems such as pivots and sprinklers.

[0027] The liquid agricultural adjuvant according to the first aspect of the present disclosure provides a stable emulsifiable and / or microemulsified liquid safe adjuvant concentrate with a high flash point (above about 100°C) and epicuticular wax compatibility that promotes bioefficacy for use in industrial, turf, ornamental, horticultural and agricultural endeavors. The liquid agricultural adjuvant provides improved penetration of active ingredients (nutrients, pesticides, etc.) through the epicuticle of target crops or pests.

[0028] According to a second aspect of the present disclosure, there is provided a method for diluting a liquid agricultural adjuvant, comprising: A method is provided, comprising the step of diluting the adjuvant concentrate prepared as described in the first aspect of the present disclosure above with water at a weight ratio of liquid agricultural adjuvant to water of 1:5000 to 1:10 to produce a stable diluted emulsion and / or microemulsion. It should be understood that the water may further comprise at least one agricultural compound selected from the group including, but not limited to, insecticides, fungicides, herbicides, desiccants, defoliants, acaricides, nutrients, miticides, bactericides, biocides, ovicides, nematicides, insect growth regulators, plant growth regulators, and combinations thereof.

[0029] The method may include diluting the liquid agricultural adjuvant in at least one of the following groups, including but not limited to, a mixing tank, a spray tank, a container, or an in-line irrigation system, to provide a diluted liquid agricultural adjuvant, which may be a stable diluted emulsion or microemulsion that promotes rain tolerance by accelerated uptake into plants, for example, due to the wax-dissolving ability of the adjuvant.

[0030] The method may involve applying the stable diluted emulsion and / or microemulsion to at least one member of the group including, but not limited to, plants, weeds, seeds, soil, urban spaces, and forests with equipment selected from the group including, but not limited to, air-assisted sprayers, conventional sprayers, aerial spraying, electrostatic spraying, ultra-low volume equipment such as foggers and mist spraying equipment, chemigation systems, pivots, sprinklers, and combinations thereof. The present disclosure also extends to the use of liquid agricultural adjuvants. DETAILED DESCRIPTION OF THE INVENTION

[0031] Detailed Description The contents of the Summary of the Disclosure are repeated herein for reference purposes to avoid repetition. Generally, stable emulsifiable and / or microemulsified liquid adjuvants with high flash points above 100°C are provided that have epicuticular wax compatibility to promote bioefficacy and provide improved penetration of active ingredients (nutrients, pesticides, etc.) through the epicuticle of target crops or pests.

[0032] In general, a first aspect of the present disclosure provides a cycloalkyl group comprising an alkyl (C 12 ~C 16 The present invention provides a liquid agricultural adjuvant comprising at least one alkyl (C1-C8) ester of alkyl (C) acid; at least one anionic surfactant; and at least one nonionic surfactant. The liquid agricultural adjuvant has a flash point of greater than about 100°C and is 12 ~C 16At least one alkyl (C1-C8) ester of a hydroxypropyltrimonial acid has a dissolving capacity of 2% to 20% by weight of paraffin wax (CAS number 8002-74-2) at 25°C.

[0033] The present disclosure extends to methods of making the liquid agricultural adjuvant according to the first aspect and methods of use, typically in agricultural endeavors.

[0034] definition The term "adjuvant," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those skilled in the art (and is not limited to any particular or special meaning), and refers, without limitation, to an agent used to modulate the effect of other agents, and more specifically to enhance the effectiveness of pesticides, such as herbicides, insecticides, fungicides, and other agents.

[0035] The term "stable," as used herein, is a broad term associated with or related to the term "emulsion" and is given its ordinary and customary meaning to those skilled in the art (and is not limited to any specific or special meaning). It refers, without limitation, to emulsion stability, i.e., the ability of an emulsion to resist changes in its properties over time, such that the size of the droplets in the emulsion does not change significantly over time, more specifically, during application to a target mixed with water, and is thus given its ordinary and customary meaning to those skilled in the art. The term "stable," as used herein, is a broad term associated with or related to the term "accelerated storage stability," and means that a formulation maintains similar performance in terms of physicochemical properties after samples are stored for 15 days at at least three conditions: room temperature (approximately 20°C), low temperature (0°C or 5°C), and high temperature (54°C). Storage stability testing was performed according to the CIPAC MT 36 method.

[0036] The term "solvent", as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those skilled in the art (and is not limited to any specific or particular meaning), and refers to compounds that may be polar or non-polar, straight-chain or branched, cyclic or aliphatic, aromatic, naphthenic, and that possess some characteristic of solubility in other compounds or means, including, but not limited to, alcohols, esters, diesters, ketones, acetates, terpenes, sulfoxides, glycols, paraffins, hydrocarbons, anhydrides, heterocyclics, among others.

[0037] When a group is described as "optionally substituted," the group can be unsubstituted or substituted with one or more of the indicated substituents. Similarly, when a group is described as "unsubstituted or substituted" and is substituted, the substituents can be selected from one or more of the indicated substituents. When no substituents are indicated, the indicated "optionally substituted" or "substituted" group can be any of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, heteroaralkyl, (heteroalicyclyl)alkyl, hydroxy, protected hydroxyl, alkoxy, aryloxy, acyl, mercapto, alkylthio, arylthio, cyano, halogen, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N- It means that the amino group may be optionally substituted with one or more groups independently selected from thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, protected C-carboxy, O-carboxy, isocyanato, thiocyanato, isothiocyanato, nitro, silyl, sulfenyl, sulfinyl, sulfonyl, haloalkyl, haloalkoxy, trihalomethanesulfonyl, trihalomethanesulfonamido, amino, monosubstituted amino, and disubstituted amino groups, and protected derivatives thereof.

[0038] The term "alkyl," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those of ordinary skill in the art (and is not limited to a specific or particular meaning), and refers, without limitation, to a straight-chain or branched, acyclic or cyclic, unsaturated or saturated aliphatic hydrocarbon containing 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 or more carbon atoms; the term "lower alkyl" has the same meaning as alkyl, but containing 1, 2, 3, 4, 5, or 6 carbon atoms. Representative saturated straight-chain alkyls include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, etc., while saturated branched alkyls include isopropyl, sec-butyl, isobutyl, tert-butyl, isopentyl, etc. Unsaturated alkyls contain at least one double or triple bond between adjacent carbon atoms (referred to as "alkenyl" or "alkynyl," respectively). Representative straight-chain and branched alkenyls include ethylenyl, propylenyl, 1-butenyl, 2-butenyl, isobutylenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 2-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, etc., while representative straight-chain and branched alkynyls include acetylenyl, propynyl, 1-butynyl, 2-butynyl, 1-pentynyl, 2-pentynyl, 3-methyl-1 butynyl, etc. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, henatetriacontyl, dotriacontyl, tritriacontyl, tetratriacontyl, pentatriacontanyl, and hexatriacontane.The alkyl group may be substituted or unsubstituted.

[0039] The term "alkoxy," as used herein, is a broad term and is to be given the ordinary and accustomed meaning to those of ordinary skill in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to an alkyl moiety attached through an oxygen bridge (i.e., --O-alkyl), e.g., methoxy, ethoxy, and the like.

[0040] The term "thioalkyl," as used herein, is a broad term and is to be given the ordinary and accustomed meaning to those of skill in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to an alkyl moiety attached through a sulfur bridge (i.e., -S-alkyl), e.g., methylthio, ethylthio, and the like.

[0041] The term "alcohol," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those of skill in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to any compound described herein that incorporates one or more hydroxy groups or is substituted with or functionalized to include one or more hydroxy groups.

[0042] The term "ester," as used herein, is a broad term and is given its ordinary and accustomed meaning to those of skill in the art (and is not limited to any specific or particular meaning), and refers to any compound described herein that incorporates, or is substituted with or functionalized to include, one or more ester groups, such as, without limitation, monoesters, diesters, triesters, or polyesters. Esters include, but are not limited to, fatty acid esters.

[0043] The term "acetate," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those of skill in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to any compound described herein that incorporates one or more acetate groups, e.g., a salt, ester, or other compound incorporating a CHCOO- moiety.

[0044] The term "terpene," as used herein, is a broad term and is to be given its ordinary and customary meaning to those skilled in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to any compound derived from the resin of a plant, such as a conifer, or a synthetically produced compound having the same structure as a plant-derived terpene. Terpenes can include hydrocarbons and terpenoids containing additional functional groups, as well as essential oils. Terpenes can be any compound of the formula (C5H8) n where n is the number of linked isoprene units (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more).

[0045] The term "terpene-containing natural oil," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those skilled in the art (and is not limited to a specific or particular meaning), and refers, without limitation, to natural oils that may contain at least 50% terpenes selected from the group consisting of orange oil, grapefruit oil, lemon oil, lime oil, tangerine oil, and pine oil, or components thereof.

[0046] The term "sulfoxide," as used herein, is a broad term and is given its ordinary and accustomed meaning to those of ordinary skill in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to any compound described herein that incorporates, or is substituted with or functionalized to include, one or more sulfinyl (SO) groups.

[0047] The term "glycol", as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those skilled in the art (and is not limited to any specific or particular meaning), and includes diols, such as polyalkylene glycols, e.g., polyethylene glycols (formula H(OCHCH) n The copolymer may include polymers having OH (where n is greater than 3), polypropylene glycol, or glycols incorporating monomers containing longer hydrocarbon chains.

[0048] The term "paraffin," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those skilled in the art (and is not limited to any particular or special meaning), and refers, without limitation, to heavier alkanes, e.g., alkanes that form liquids or waxes at room temperature, and functionalized paraffins, e.g., chlorinated paraffins, as well as mineral or synthetic oils, including hydrocarbons. Room temperature, as used herein, refers to ambient conditions, e.g., in a temperature and humidity controlled building, e.g., approximately 20°C.

[0049] The term "hydrocarbon," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those of ordinary skill in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to any compound containing only carbon and hydrogen atoms. Functionalized or substituted hydrocarbons have one or more substituents as described elsewhere herein.

[0050] The term "anhydride," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those of skill in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to any compound described herein that incorporates, or is substituted with or functionalized to include, one or more anhydride groups (of the formula (RC(O))O).

[0051] The term "sulfonic acid," as used herein, is a broad term and is to be given its ordinary and accustomed meaning to those skilled in the art (and is not limited to a specific or particular meaning), and refers, without limitation, to formic acid, acetic acid, succinic acid, lactic acid, malic acid, tartaric acid, citric acid, ascorbic acid, nicotinic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, salicylic acid, or naphthalenesulfonic acid. Sulfonic acids can include hydrocarbyl sulfonic acids, such as arylsulfonic acids, alkylbenzenesulfonic acids, among others.

[0052] The term "vegetable oil," as used herein, is a broad term and is given its ordinary and accustomed meaning to those skilled in the art (and is not limited to any specific or particular meaning), and refers, without limitation, to the oily fatty acid constituents of vegetable matter, such as saturated fatty acids, monounsaturated fatty acids, polyunsaturated fatty acids, etc. Vegetable oils may be functionalized, such as alkoxylated, hydroxylated, aminated, etc. Functionalized vegetable oils are derivatives of vegetable oils or other fatty substances, or substances with similar compositions regardless of the source of the substance. In some embodiments, the functionalized vegetable oil is an epoxidized unsaturated triglyceride. An epoxidized unsaturated triglyceride is a tri-ester of glycerin. Glycerin is linked to three linear or branched carboxylic acids, at least one of which contains an epoxide moiety. For example, an epoxidized unsaturated triglyceride may be a derivative of an unsaturated fatty acid triglyceride, such as a vegetable or animal fat or oil, in which at least one C=C moiety of the parent unsaturated fatty acid triglyceride has been replaced with an epoxide moiety (i.e., a three-membered ring containing oxygen). If the parent unsaturated fatty acid triglyceride has two or more C=C moieties, one, some, or all of the C=C moieties may be replaced with epoxide moieties. When the term "vegetable oil" is used herein, it is understood to include animal fats having the same chemical structure as vegetable oils, or oils of synthetic origin. Examples of vegetable or animal fats or oils include coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanut oil, rapeseed oil, canola oil, safflower oil, sesame oil, soybean oil, sunflower oil, castor oil, tallow oil, etc.

[0053] As used herein, any compound abbreviation follows its common usage, recognized abbreviation, or the IUPAC-IUB Biochemical Nomenclature Commission (see Biochem. 11:942-944 (1972)) unless otherwise specified.

[0054] All percentages, ratios or other amounts referred to herein are by weight unless otherwise specified.

[0055] The ring systems referred to herein include fused, bridged, and spirocyclic moieties as well as separate monocyclic moieties. [Example]

[0056] Example The following examples should not be construed as limiting the present disclosure. The broad disclosure made in the Summary of Disclosure and Detailed Description herein above is repeated for reference purposes.

[0057] Wax Solubility Test How to prepare for the Paraffin Wax Solubility Test We developed a method to evaluate the ability of solvents to dissolve paraffin wax, which helps us understand how a particular solvent will perform when applied to the epicuticular surface of a plant.

[0058] The method for preparing a paraffin wax solubility test defines the rate at which a solvent dissolves paraffin wax (CAS No. 8002-74-2) over a period of at least 24 hours. The steps for conducting the test are as follows: a) Weigh 98 grams of solvent into an 8 oz glass bottle; b) Place the bottle with the solvent on a laboratory balance and zero out the weight; c) Add 2 grams of molten (110°F or 43.3°C) paraffin wax to the solvent and place a 1-inch magnetic stir bar in it and cap; d) Place the bottle containing the solvent and paraffin wax sample on a magnetic stir plate and begin stirring at 350 rpm—start a clock counter for each sample; e) Observe whether the entire amount of paraffin wax has dissolved and record the time.

[0059] [Table 1]

[0060] Examples of Products According to the Disclosure Methods for preparing adjuvant concentrates For illustrative purposes, a method for preparing the liquid agricultural adjuvant (in concentrate form) used in the non-limiting examples may include the steps of: (i) mixing in a tank with a portion of water and / or oil; (ii) adding at least one anionic surfactant, such as sodium lauryl ether sulfate; (iii) adding at least one nonionic surfactant, such as an ethoxylated fatty alcohol; and (iv) adding at least one alkyl (C 12 ~C 16and (v) adding at least one solvent from the group of alkyl (C1-C8) esters of acids, such as isopropyl myristate and / or isopropyl laurate. The method may optionally include an additional step (v) of adding at least one additive, such as, but not limited to, a preservative and / or a colorant. Typically, the steps are performed in the order of steps (i) to (iv), with the optional further step (v). The mixture is continuously stirred. Heating is not necessary, but may be advantageously used depending on the physical state of each compound. Lower or higher temperatures may be used for certain components. The temperature may be selected to promote mixing within a desired period while avoiding component decomposition or undesired reactions. For specific purposes, other additives may also be added, such as, but not limited to, clarifying agents, antifoaming agents, antifreeze agents, hydrotropes, acidifying agents, UV stabilizers, colorants, nutrients, amino acids, marine extracts, anti-drift agents, antifreeze agents, and water, oil, or other solvents, as well as combinations thereof.

[0061] The agricultural adjuvant composition may contain various ratios of the components, typically the adjuvant in its concentrated liquid form, and may contain from about 1 to about 30% alkyl (C 12 ~C 16 at least one alkyl (C1-C8) ester of a hydroxybenzoate; from about 1 to about 30% by weight of at least one anionic surfactant; from about 1 to about 40% by weight of one or more nonionic surfactants; and from about 2 to about 80% of water, oil, or other additives.

[0062] More specifically, the agricultural adjuvant composition in its concentrated liquid form contains 1 to 30% by weight, preferably 3 to 12% by weight, of alkyl (C 12 ~C 16at least one alkyl(C1-C8) ester of alkyl(C1-C8) acid; at least one anionic surfactant constituting 1 to 30% by weight, preferably 3 to 20% by weight; at least one nonionic surfactant constituting 1 to 40% by weight, preferably 5 to 30% by weight; and water, oil or other additives constituting 20 to 70% by weight, preferably 30 to 65% by weight. In other words, the agricultural adjuvant composition, when weighing 100 g, contains 1 to 30 g, preferably 3 to 12 g, of alkyl(C1-C8) ester of alkyl(C1-C8) acid. 12 ~C 16 at least one alkyl (C1-C8) ester of a hydroxypropyl methylcellulose (C1-C8) acid; 1 to 30 g, preferably 3 to 20 g, of at least one anionic surfactant; 1 to 40 g, preferably 5 to 30 g, of at least one nonionic surfactant; and 20 to 70 g, preferably 30 to 65 g, of water, oil, or other additives. Any percentages, ratios, or other amounts referred to herein are by weight in grams unless otherwise specified.

[0063] Adjuvant Preparation Four different agricultural adjuvant compositions in concentrate form were prepared according to several embodiments of the present disclosure. Concentrate adjuvants with high flash points and epicuticular wax compatibility are represented by ORO-009-K, ORO-009-T, ORO-079-FB, and ORO-340. Details of specific embodiments are provided in Table 2. Various ingredients were used in the different formulations, including soybean methyl ester-oil; cold-pressed orange oil-oil; polyoxyethylene sorbitan monolaurate-anionic surfactant; alcohol ethoxylated POE-6-nonionic surfactant; triethanolamine dodecylbenzenesulfonate-anionic surfactant; calcium dodecylbenzenesulfonate-anionic surfactant; sodium dodecylbenzenesulfonate-anionic surfactant; sodium lauryl ether sulfate-anionic surfactant; alcohol ethoxylated and propoxylated EOPO6 / 9-nonionic surfactant; isopropyl myristate-oil, methyl laurate-oil, and isopropyl laurate-oil.

[0064] [Table 2]

[0065] Physicochemical and accelerated stability testing Samples of certain embodiment agricultural adjuvant compositions were compared to commercially available products and analyzed to determine their physicochemical properties and their behavior when diluted in water, such as pH and stability of the emulsions formed. Additionally, studies on pure (concentrate) adjuvants were performed, such as determining the flash point using the closed cup method described in CIPAC Handbook F - Collaborative International Pesticide Analytical Ltd, 1994, 2007 reprint, the entire contents of which are incorporated herein by reference. These commercially available products included the following products from Oro Agri®: WETCIT® (an adjuvant based on ethoxylated alcohol and orange oil), ORO-HSMSO® (a high-surfactant methylated seed oil-based adjuvant), and TRANSFORMER® (a secondary ethoxylated alcohol-based adjuvant soil conditioner); and LI7X1: LI700, a soybean oil-derived nonionic penetrating surfactant, from Loveland Products; and DNX1: Dyne-Amic, a blend of highly refined methylated seed oils combined with a specialty organosilicone-based nonionic surfactant, from Helena Chemicals; and CXU1: Succeed Ultra, an available high-surfactant methylated seed oil adjuvant, from Winfield® United. Agricultural adjuvant compositions prepared according to embodiments demonstrated stability in accelerated storage stability tests, with all samples determined to be stable even under low-temperature conditions (0°C for 14 days) or high-temperature conditions (54°C for 14 days). The stability results are shown in Tables 3, 4 and 5.

[0066] [Table 3]

[0067] [Table 4]

[0068] [Table 5]

[0069] Field trials to evaluate agricultural adjuvant compositions made in accordance with the present disclosure and comparison with existing products Study 1. Effect of adjuvant x adjuvant ratio on wheat cover crop burndown by glyphosate at full tillering stage.

[0070] Method summary: A bifactorial study was conducted consisting of 29 treatments, including 10 adjuvant (factor A) and 2 adjuvant ratio (factor B) combinations, as well as 3 reference treatments (Table 6).

[0071] Two plots per block were selected before treatment application to record wheat height and the number of tillers per plant. In each plot, the height of the tallest and shortest plants was measured and the tillers were counted.

[0072] Herbicide applications were made using a single-nozzle boom connected to a backpack CO2 pressurization system. Each plot was 3 ft x 20 ft. 14 and 28 days after application, wheat was visually assessed for dryness using a 0 to 100% scale, with 0 corresponding to no damage symptoms and 100% corresponding to plant death. Additional information on herbicide applications and other variables is provided in Tables 6 through 10.

[0073] [Table 6]

[0074] [Table 7]

[0075] [Table 8]

[0076] [Table 9]

[0077] [Table 10]

[0078] Because the interaction effect was not significant, the main effects were analyzed separately and their means are presented in Tables 11 and 12.

[0079] [Table 11]

[0080] [Table 12]

[0081] Conclusions—This test was conducted using half the glyphosate rate to detect differences between adjuvant formulations at suboptimal herbicide doses. Under these conditions, the following can be concluded: Three adjuvants made according to the present disclosure performed numerically better than the commercial standards Dyne-Amic® and Succeed Ultra® and Oro Agri's products: OR-079-FB; OR-009-K; and OR-340. The adjuvant according to the present disclosure that performed similarly to other commercial products was OR-009-T. In terms of adjuvant concentration, 0.125% by volume was generally better than 0.25% by volume. This is highly advantageous.

[0082] Some advantages of the agricultural adjuvant compositions according to the present disclosure include a high flash point and a low evaporation rate, which solubilize leaf or root epicuticular waxes that cover the surface during use, which in turn substantially improves the biological performance of insecticides, fungicides, acaricides, nematicides, herbicides, plant growth regulators, insecticide growth regulators, nutrients, and other pesticides.

[0083] Unless otherwise specified, all terms (including technical and scientific terms) are to be given their ordinary and accustomed meanings to those skilled in the art and are not limited to any particular or special meaning unless expressly defined herein. It should be noted that the use of a particular terminology in describing a particular feature or embodiment of the present disclosure should not be construed as suggesting that the terminology is herein redefined to be limited to include any particular characteristic of the feature or embodiment of the present disclosure to which the terminology pertains. Terms and phrases used in this application, and variations thereof, particularly in the appended claims, should be construed as open-ended rather than limiting, unless expressly specified otherwise.As examples of the above, the term "including" should be read to mean "including without limitation," "including but not limited to," etc.; the term "comprising," as used herein, is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps; the term "having" should be interpreted as "having at least"; the term "includes" should be interpreted as "includes but not limited to," etc. The term "example" is used to provide an illustrative example of the item being discussed, not to exhaustively or limit the listing; adjectives such as "known," "standard," "typical," and similar terms should not be construed as limiting the described items to those available in a given period or at a given time, but instead should be read as embracing known, standard, or standard technology that may be available or known at any time now or in the future; the use of terms such as "preferably," "preferred," "desired," or "desirable," and words of similar meaning, should not be understood to suggest that a particular feature is critical, essential, or even important to the structure or function of the invention, but instead should be understood as merely intended to highlight alternative or additional features that may or may not be utilized in a particular embodiment of the invention. Similarly, a group of items connected by the conjunction "and" should not be read as requiring that every single item be present in the group, but rather as "and / or" unless expressly specified otherwise. Similarly, groups of items joined by the conjunction "or" should not be read as requiring mutual exclusivity among the groups, but rather as "and / or" unless expressly specified otherwise.

[0084] When a range of values is given, it is understood that the upper and lower limits of that range, and each intervening value between the upper and lower limits, are encompassed within an embodiment.

[0085] For the use of substantially all plural and / or singular terms herein, those skilled in the art can convert from plural to singular and / or from singular to plural as appropriate to the situation and / or application. Various singular / plural permutations may be expressly set forth herein for clarity. The indefinite articles "a" or "an" do not exclude a plurality. A single processor or other unit may fulfill the functions of several items recited in the claims. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be advantageously used. Any reference signs in the claims should not be construed as limiting the scope.

[0086] Those skilled in the art will further understand that if a specific number recitation is intended in an introduced claim, such intention will be explicitly recited in that claim; absent such recitation, no such intention exists. For example, as an aid to understanding, the following appended claims may include the use of the introductory phrases "at least one" and "one or more." However, the use of such phrases should not be construed as suggesting that introducing a claim recitation with the indefinite article "a" or "an" limits any particular claim that includes a claim recitation so introduced to embodiments that include only one such recitation (e.g., "a" and / or "an" should typically be construed to mean "at least one" or "one or more"); the same applies to the use of definite articles used to introduce claim recitations, even if the same claim includes the introductory phrases "one or more" or "at least one" and an indefinite article such as "a" or "an." Also, even when a specific number is explicitly recited in an introduced claim recitation, those skilled in the art will understand that such a recitation should typically be interpreted to mean at least the recited number (e.g., the mere recitation of "two recitations" without other modifiers typically means at least two recitations, or more than two recitations). Furthermore, in instances where a conventional expression similar to "at least one of A, B, and C, etc." is used, such syntax is typically intended in the sense that a person skilled in the art would understand the conventional expression (e.g., "a system having at least one of A, B, and C" includes, but is not limited to, systems having only A, only B, only C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.).In instances where a conventional expression similar to "at least one of A, B, or C, etc." is used, such syntax is typically intended in the sense that one of ordinary skill in the art would understand the conventional expression (e.g., "a system having at least one of A, B, or C" includes, but is not limited to, systems having A only, B only, C only, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.). Those of ordinary skill in the art will further understand that virtually any disjunctive word and / or phrase presenting two or more alternative terms, wherever it appears in the specification, claims, or drawings, should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B."

[0087] All numbers expressing ingredients, quantities of reagents, reaction conditions, and the like used herein are to be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and without intending to limit the application of the doctrine of equivalents to any claims in any application claiming priority to this application, each numerical parameter should be construed in light of the number of significant digits and ordinary rounding approaches.

[0088] Moreover, while the foregoing has been described in some detail by way of illustration and example for purposes of clarity and understanding, it will be apparent to those skilled in the art that certain changes and modifications may be made. Therefore, the descriptions and examples should not be construed as limiting the scope of the invention to the specific embodiments and examples described herein, but rather should be construed to embrace all modifications and alternatives that come within the true scope and spirit of the invention.

Claims

1. A liquid agricultural adjuvant for use in a pesticide, comprising: The liquid agricultural adjuvant is 3% to 12% by weight of alkyl(C １２ ~C １６ ) acid, at least one alkyl (C １ ~C ８ ) esters; 3% to 20% by weight of at least one anionic surfactant; 5% to 30% by weight of at least one nonionic surfactant; 20% to 70% by weight of water and / or other additives; It consists of The alkyl(C １２ ~C １６ ) acid, at least one alkyl (C １ ~C ８ ) esters are selected from the group consisting of methyl laurate, isopropyl laurate, isopropyl myristate, and combinations thereof; the at least one anionic surfactant is selected from the group consisting of sodium alkylbenzene sulfonate, calcium alkylbenzene sulfonate, sodium lauryl ether sulfate, and combinations thereof; the at least one nonionic surfactant is selected from the group consisting of alcohol ethoxylated 6POE, alcohol ethoxylated and propoxylated EOPO9, polyoxyethylene sorbitan monolaurate, and combinations thereof; the liquid agricultural adjuvant has a flash point greater than 100°C; The alkyl(C １２ ~C １６ ) acid, at least one alkyl (C １ ~C ８ ) the ester has a dissolving capacity of 2 to 20% by weight of paraffin wax at 25°C; Liquid agricultural adjuvant.

2. 10. The liquid agricultural adjuvant of claim 1, further comprising an additive selected from the group consisting of preservatives, clarifying agents, antifreeze agents, hydrotropes, stabilizers, antioxidants, acidifying agents, chelating agents, complexing agents, dyes, rheology modifiers, antifoaming agents and anti-drift agents, and combinations thereof.

3. 1. A method for diluting a liquid agricultural adjuvant, comprising:

10. Diluting the liquid agricultural adjuvant of claim 1 with water at a weight ratio of the liquid agricultural adjuvant to water of 1:5000 to 1:10 to produce a stable diluted emulsion and / or microemulsion. A method comprising:

4. 4. The method of claim 3, wherein the water further comprises at least one agricultural compound selected from the group consisting of insecticides, fungicides, herbicides, desiccants, defoliants, acaricides, nutrients, miticides, bactericides, biocides, ovicides, nematicides, insect growth regulators, plant growth regulators, and combinations thereof.

5. 5. The method of claim 4, wherein the liquid agricultural adjuvant is diluted in a mixing tank, a spray tank, a container, or an in-line irrigation system.

6. 6. The method of claim 5, wherein the stable diluted emulsion and / or microemulsion is applied to at least one member of the group consisting of plants, weeds, seeds, soil, urban spaces, and forests with equipment selected from the group including air-assisted sprayers, atomizers, ultra-low volume equipment, chemigation systems, pivots, sprinklers, and combinations thereof.

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