Acrylic Copolymer Agricultural Formulations

Abstract

The agricultural formulation comprises a copolymer comprising (i) 20% to 50% by weight, based on the total weight of the copolymer, of monomeric structural units derived from a first acrylic monomer having a log Kow of 1.0 or less, and (ii) 50% to 80% by weight, based on the total weight of the copolymer, of monomeric structural units derived from a second acrylic monomer having a log Kow of 2.0 to 6.0. The agricultural formulation also comprises an active ingredient having a log Kow greater than 1.0.

Description

[Technical field]

[0001] The present disclosure relates generally to agricultural formulations, and more specifically, to agricultural formulations comprising acrylic copolymers. [Background technology]

[0002] Introduction Agricultural formulations containing active ingredients (e.g., pesticides, insecticides, fertilizers, herbicides, etc.) used for crop applications are traditionally sprayed onto the crop tissue. Water in the form of rain and irrigation can wash the active ingredients out of the crop tissue, thereby polluting waterways and simultaneously depriving the crop of the intended active ingredients. The ability of a formulation to retain the active ingredient on the crop tissue is called rainfastness. The ability of a formulation to provide rainfastness often depends on the Log octanol / water partition coefficient ("logKow") of the active ingredient. Not all formulations can provide adequate rainfastness, since even active ingredients with a logKow greater than 1 (i.e., hydrophobic) are susceptible to being washed away by small amounts of water. If a formulation can retain 80% or more of the active ingredient on the simulated leaves after 5 minutes of simulated rainfall ("successful rainfastness"), the formulation can be considered to provide successful rainfastness for the above active ingredients.

[0003] Agricultural formulations typically contain wetting agents (e.g., polyethylene glycol), spreading and adhesion agents, rheology modifiers, rain resistance additives, nutrients, and many other adjuvants, resulting in complex formulations. One material that has been attempted in forming agricultural formulations is acrylic polymers. For example, US Patent Publication No. 20180360045(A1) discloses an agrochemical formulation that uses an acrylic latex to achieve improved rain resistance performance. Similarly, EP 2793573(B1) discloses an agrochemical composition that utilizes a latex emulsion of hydrophobically modified acrylate containing a polymer that exhibits improved adhesion properties. As demonstrated by the prior art, acrylic polymers are often added to agricultural formulations as emulsions of polymers because of the ease of combining liquid emulsions with other liquids and because acrylic polymers are often formed using emulsion polymerization.

[0004] Despite the research carried out to implement acrylic polymers into agrochemical formulations, challenges remain. For example, acrylic polymer emulsions suffer from instability caused by the addition of other additives / adjuvants, water and / or active ingredients. Emulsion instability and subsequent agglomeration in the formulation can shorten the shelf life of the formulation and cause uneven distribution in crop tissues. These challenges affect the ability of compositions containing acrylic polymers to achieve successful rain resistance.

[0005] In view of the above-mentioned problems, it would be surprising to discover an agricultural formulation including an acrylic polymer that exhibits successful rain resistance and is not subject to flocculation or instability. Summary of the Invention

[0006] The present inventors have discovered agricultural formulations containing acrylic copolymers that exhibit successful rain resistance and are not subject to flocculation or instability.

[0007] The inventors of the present application have discovered that agricultural formulations utilizing copolymers comprising 20% ​​to 50% by weight of monomeric structural units derived from a first acrylic monomer having a logKow of 1.0 or less and 50% to 80% by weight of monomeric structural units derived from a second acrylic monomer having a logKow of 2.0 to 6.0 can achieve successful rainfastness for active ingredients having a logKow of greater than 1.0. In addition to imparting successful rainfastness for active ingredients having a logKow of greater than 1.0, the incorporation of 20% to 50% by weight of monomeric structural units derived from a first acrylic monomer having a logKow of 1.0 or less allows the copolymer to be water soluble. The water soluble nature of the copolymer means that it does not need to be present in an emulsion, thus eliminating the risk of flocculation and instability and allowing increased shelf life stability.

[0008] The present invention is particularly useful for agricultural uses.

[0009] According to a first aspect of the present disclosure, an agricultural formulation comprises: (i) a copolymer comprising 20% ​​to 50% by weight, based on the total weight of the copolymer, of monomeric structural units derived from a first acrylic monomer having a log Kow of 1.0 or less, and (ii) 50% to 80% by weight, based on the total weight of the copolymer, of monomeric structural units derived from a second acrylic monomer having a log Kow of 2.0 to 6.0; and an active ingredient having a log Kow greater than 1.0.

[0010] According to a second aspect of the present disclosure, the agricultural formulation comprises 0.5% to 4.0% by weight of the copolymer, based on the total weight of the agricultural formulation.

[0011] According to a third aspect of the present disclosure, the agricultural formulation further comprises 0.5% to 3.0% by weight of glycol.

[0012] According to a fourth aspect of the present disclosure, the active ingredient is a pesticide having a log Kow of 2.5 or greater.

[0013] According to a fifth aspect of the present disclosure, the copolymer is a random copolymer of first and second acrylic monomers and has a weight average molecular weight of 15,000 Daltons to 30,000 Daltons as measured by gel permeation chromatography.

[0014] According to a sixth aspect of the present disclosure, the first acrylic monomer is methacrylic acid.

[0015] According to a seventh aspect of the present disclosure, the second acrylic monomer has a log Kow of 2.0 to 3.0.

[0016] According to an eighth embodiment of the present disclosure, the second acrylic monomer is butyl methacrylate.

[0017] According to a ninth aspect of the present disclosure, the copolymer comprises, based on the total weight of the copolymer, 60% to 70% by weight of monomer structural units derived from butyl methacrylate and 30% to 40% by weight of monomer structural units derived from methacrylic acid.

[0018] According to a tenth aspect of the present disclosure, an agricultural mixture comprises water and an agricultural formulation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] As used herein, the term "and / or," when used with a list of two or more items, means that any one of the listed items can be used by itself, or any combination of two or more of the listed items can be used. For example, if a composition is described as containing components A, B, and / or C, the composition can contain A alone, B alone, C alone, A and B in combination, A and C in combination, B and C in combination, or A, B, and C in combination.

[0020] As used herein, "wt %" or "weight percent" or "percent by weight" of a component is based on the total weight of the composition or article in which the component is included, unless specifically stated to the contrary. As used herein, all percentages are by weight unless specifically stated otherwise.

[0021] Agricultural formulations The present disclosure is directed to an agricultural formulation. The agricultural formulation comprises a copolymer and an active ingredient. The agricultural formulation may also comprise one or more glycols and water.

[0022] Copolymer As explained above, the agricultural formulation comprises a copolymer. As used herein, a "copolymer" has two or more of the same or different monomeric structural units derived from two or more different monomers. A "monomer structural unit" as used herein with respect to a copolymer refers to a portion of a copolymer structure resulting from the reaction of a monomer or monomers to form the copolymer. When referring to a monomeric structural unit, "different" indicates that the monomeric structural units differ from each other at least one atom or are isomerically different. An embodiment of the present disclosure provides that the monomeric structural units of the copolymer result from, i.e., are formed from, a polymerization reaction of the monomers. The copolymer may be either a random copolymer (i.e., the order of monomer polymerization is random), a block copolymer (i.e., the copolymer contains alternating sections of a single monomer type), or may contain both block copolymers and random portions. The monomeric structural units may undergo one or more reactions following the polymerization reaction, such as a hydrolysis reaction.

[0023] The copolymer comprises monomer structural units derived from a first acrylic monomer. As used herein, an "acrylic monomer" is a monomer comprising an acrylic acid moiety or a salt, ester and / or conjugate base of an acrylic acid moiety. The copolymer comprises 20% to 50% by weight of monomer structural units derived from the first acrylic monomer, based on the total weight of the copolymer. For example, the copolymer comprises 20% by weight or more, or 25% by weight or more, or 30% by weight or more, or 35% by weight or more, or 40% by weight or more, or 45% by weight or more, while simultaneously comprising 50% by weight or less, or 45% by weight or less, or 40% by weight or less, or 35% by weight or less, or 30% by weight or less, or 25% by weight or less of the first acrylic monomer, based on the total weight of the copolymer.

[0024] The first acrylic monomer has a log Kow of 1.0 or less, as determined by the Kow test, as described in more detail below. The first acrylic monomer has a log Kow of 1.0 or less, or 0.95 or less, or 0.90 or less, or 0.85 or less, or 0.80 or less, or 0.75 or less, or 0.70 or less, or 0.65 or less, or 0.60 or less, or 0.55 or less, or 0.50 or less, or 0.45 or less, or 0.40 or less, or 0.35 or less, or 0.30 or less, or 0.25 or less, while simultaneously having a log Kow of 0.20 or more, or 0.25 or more, or 0.30 or more, or 0.35 or more, or 0.40 or more, or 0.45 or more, or 0.50 or more, or 0.55 or more, or 0.60 or more, or 0.65 or more, or 0.70 or more, or 0.75 or more, or 0.80 or more, or 0.85 or more, or 0.90 or more, or 0.95 or more. Examples of monomers suitable for use as the first acrylic monomer include methacrylic acid (log Kow 0.93), acrylic acid (log Kow 0.35), methyl acrylate (log Kow 0.73), and / or combinations thereof.

[0025] The copolymer comprises monomeric structural units derived from a second acrylic monomer. The copolymer comprises 50% to 80% by weight of monomeric structural units derived from a second acrylic monomer, based on the total weight of the copolymer. For example, the copolymer comprises 50% by weight or more, or 55% by weight or more, or 60% by weight or more, or 65% by weight or more, or 70% by weight or more, or 75% by weight or more, while at the same time 80% by weight or less, or 75% by weight or less, or 70% by weight or less, or 65% by weight or less, or 60% by weight or less, or 55% by weight or less, of monomeric structural units derived from a second acrylic monomer, based on the total weight of the copolymer.

[0026] The second acrylic monomer has a log Kow of 2.0 to 6.0 as determined by the Kow test. For example, the second acrylic monomer has a log Kow of 2.0 or more, or 2.2 or more, or 2.4 or more, or 2.6 or more, or 2.8 or more, or 3.0 or more, or 3.2 or more, or 3.4 or more, or 3.6 or more, or 3.8 or more, or 4.0 or more, or 4.2 or more, or 4.4 or more, or 4.6 or more, or 4.8 or more, or 5.0 or more, or 5.2 or more, or 5.4 or more, or 5.6 or more, or 5.8 or more. w while simultaneously having a log Kow of 6.0 or less, or 5.8 or less, or 5.6 or less, or 5.4 or less, or 5.2 or less, or 5.0 or less, or 4.8 or less, or 4.6 or less, or 4.4 or less, or 4.2 or less, or 4.0 or less, or 3.8 or less, or 3.6 or less, or 3.4 or less, or 3.2 or less, or 3.0 or less, or 2.8 or less, or 2.6 or less, or 2.4 or less, or 2.2 or less. Exemplary second acrylic monomers for use in the copolymer include, but are not limited to, butyl methacrylate (logP 2.75), butyl acrylate (logP 2.20), 2-ethylhexyl acrylate (logP 4.09), and / or combinations thereof.

[0027] The agricultural formulation may contain 0.5% to 4.0% by weight of the copolymer, based on the total weight of the agricultural formulation. For example, the agricultural formulation may contain 0.5% by weight or more, or 1.0% by weight or more, or 1.5% by weight or more, or 2.0% by weight or more, or 2.5% by weight or more, or 3.0% by weight or more, or 3.5% by weight or more of the copolymer, based on the total weight of the agricultural formulation, while simultaneously containing 4.0% by weight or less, or 3.5% by weight or less, or 3.0% by weight or less, or 2.5% by weight or less, or 2.0% by weight or less, or 1.5% by weight or less, or 1.0% by weight or less of the copolymer.

[0028] The copolymer has a weight average molecular weight of 15,000 daltons to 30,000 daltons. For example, the weight average molecular weight of the copolymer is 15,000 daltons or more, or 16,000 daltons or more, or 17,000 daltons or more, or 18,000 daltons or more, or 19,000 daltons or more, or 20,000 daltons or more, or 21,000 daltons or more, or 22,000 daltons or more, or 23,000 daltons or more, or 24,000 daltons or more, or 25,000 daltons or more, or 26,000 daltons or more, or 27,000 daltons or more, or 28,000 daltons or more, or 29,000 daltons or more. The weight average molecular weight of the copolymer may be 30,000 daltons or less, or 29,000 daltons or less, or 28,000 daltons or less, or 27,000 daltons or less, or 26,000 daltons or less, or 25,000 daltons or less, or 24,000 daltons or less, or 23,000 daltons or less, or 22,000 daltons or less, or 21,000 daltons or less, or 20,000 daltons or less, or 19,000 daltons or less, or 18,000 daltons or less, or 17,000 daltons or less, or 16,000 daltons or less. The weight average molecular weight of the copolymer is determined using gel permeation chromatography and is measured by gel permeation chromatography (GPC) against a poly(methyl methacrylate) standard.

[0029] The copolymers can be prepared by solution polymerization. Solution polymerization of the monomers can be carried out, for example, in a non-aqueous solvent. Suitable solvents include, but are not limited to, toluene, xylene, propylene glycol, methyl ethyl ketone, and combinations thereof. Solution polymerization can include a solvent-soluble initiator. Examples of initiators include, but are not limited to, t-butyl peroctoate, t-butyl hydroperoxide, AIBN, 2,2-azobis(2,4-dimethyl-pentanenitrile), t-butyl peroxybenzoate, and combinations thereof. Initiators can be used, for example, at 0.01% to 1.00% by weight, based on the total weight of monomers utilized in the solution polymerization.

[0030] The copolymers can be prepared by emulsion polymerization, which involves the use of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and the ethoxylation of sulfosuccinic acid [C 10 Surfactants such as anionic surfactants such as sodium alcohol half esters, and / or combinations thereof may be utilized. Surfactants may be used, for example, at 0.5% to 6.0% by weight based on the total weight of monomers utilized in the emulsion polymerization. Initiators may be utilized in the emulsion polymerization, for example, water-soluble initiators. Examples of initiators include, but are not limited to, alkali metal persulfates, ammonium persulfate, and combinations thereof. Initiators may be utilized at 0.01% to 1.00% by weight based on the total weight of monomers utilized in the emulsion polymerization. Chain transfer mercaptans may be utilized in the emulsion polymerization. Examples of chain transfer mercaptans include, but are not limited to, 2-mercaptopropionic acid, 3-methylmercaptopropionic acid, alkyl mercaptans having 4 to 20 carbon atoms, and combinations thereof. Chain transfer mercaptans may be utilized at 0.01% to 5.00% by weight based on the total weight of monomers utilized in the emulsion polymerization. The use of mercaptan modifiers may reduce the molecular weight of the polymer. Other known ingredients may be utilized in the emulsion polymerization. Different amounts of these other known ingredients may be utilized for various applications.

[0031] The monomer structural units of the copolymer may undergo one or more reactions subsequent to the polymerization reaction, such as a hydrolysis reaction, which may include, for example, hydrolysis of an ester to an acid, or ring opening of an anhydride to an acid.

[0032] The copolymers are available from The Dow Chemical Company, Midland, Michigan.

[0033] Active ingredient Agricultural formulations contain an active ingredient. The active ingredient has a log Kow greater than 1.0 as determined by the Kow test. For example, the active ingredient can have a log Kow of 1.1 or greater, or 1.2 or greater, or 1.4 or greater, or 1.6 or greater, or 1.8 or greater, or 2.0 or greater, or 2.2 or greater, or 2.4 or greater, or 2.6 or greater, or 2.8 or greater, or 3.0 or greater, or 3.2 or greater, or 3.4 or greater, or 3.6 or greater, or 3.8 or greater, or 4.0 or greater, or 4.2 or greater, or 4.4 or greater, or 4.6 or greater, or 4.8 or greater, or 5.0 or greater, or 5.2 or greater, or 5.4 or greater, or 5.6 or greater, or 5.8 or greater. , while simultaneously having a log Kow of 6.0 or less, or 5.8 or less, or 5.6 or less, or 5.4 or less, or 5.2 or less, or 5.0 or less, or 4.8 or less, or 4.6 or less, or 4.4 or less, or 4.2 or less, or 4.0 or less, or 3.8 or less, or 3.6 or less, or 3.4 or less, or 3.2 or less, or 3.0 or less, or 2.8 or less, or 2.6 or less, or 2.4 or less, or 2.2 or less, or 2.0 or less, or 1.8 or less, or 1.6 or less, or 1.4 or less, or 1.2 or less. Exemplary active ingredients include, but are not limited to, atrazine, chlorothalonil, diuron, terbuthylazine, abamectin, azinphos-methyl, bifenthrin, chlorpyrifos, clofentezine, endosulfan, bupirimate, captan, folpet, tebuconazole, novaluron, tau-fluvalinate, bifenthrin, chlorpyrifos, lambda-cyhalothrin, bifenthrin, chlorpyrifos, metallic copper, endosulfan, and combinations thereof.

[0034] The agricultural formulation may contain 30% to 99% by weight of the active ingredient, based on the total weight of the agricultural formulation. For example, the agricultural formulation may comprise 30% or more, or 35% or more, or 40% or more, or 45% or more, or 50% or more, or 55% or more, or 60% or more, or 65% or more, or 70% or more, or 75% or more, or 80% or more, or 85% or more, or 90% or more, or 95% or more, or 98% or more by weight, while at the same time 99% or less, or 95% or less, or 90% or less, or 85% or less, or 80% or less, or 75% or less, or 70% or less, or 65% or less, or 60% or less, or 55% or less, or 50% or less, or 45% or less, or 40% or less, or 35% or less by weight of the active ingredient, based on the total weight of the agricultural formulation.

[0035] Glycol. The agricultural formulation may include one or more glycols. For example, the agricultural formulation may include ethylene glycol, propylene glycol, butylene glycol, higher glycols, and / or combinations thereof. The agricultural formulation may include 0.5% by weight or more, or 1.0% by weight or more, or 1.5% by weight or more, or 2.0% by weight or more, or 2.5% by weight or more, while at the same time 3.0% by weight or less, or 2.5% by weight or less, or 2.0% by weight or less, or 1.5% by weight or less, or 1.0% by weight or less of glycol, based on the total weight of the agricultural formulation.

[0036] agricultural mixture The agricultural formulation may be diluted with one or more solvents or liquids to produce an agricultural mixture. For example, the agricultural formulation may be diluted with water to form an agricultural mixture. In such a scenario, the agricultural formulation may be known as a "mix in a can" that is diluted with additional water to form an agricultural mixture that is applied to a field containing a crop. The agricultural mixture may contain at least 0.5% by weight, or at least 1.0% by weight, or at least 5% by weight, or at least 10% by weight, or at least 15% by weight, or at least 20% by weight, or at least 25% by weight, or at least 30% by weight, or at least 35% by weight, or at least 40% by weight, or at least 45% by weight, or at least 50% by weight, or at least 55% by weight, or at least 60% by weight, or at least 65% by weight, or at least 70% by weight, or at least 75% by weight, or at least 80% by weight, based on the total weight of the agricultural mixture. may comprise 85% or more by weight, while at the same time not more than 90% by weight, or not more than 85% by weight, or not more than 80% by weight, or not more than 75% by weight, or not more than 70% by weight, or not more than 65% by weight, or not more than 60% by weight, or not more than 55% by weight, or not more than 50% by weight, or not more than 45% by weight, or not more than 40% by weight, or not more than 35% by weight, or not more than 30% by weight, or not more than 25% by weight, or not more than 20% by weight, or not more than 15% by weight, or not more than 10% by weight, or not more than 5% by weight of the agricultural formulation. EXAMPLES

[0037] material The following materials were used in forming and testing the examples:

[0038] Atrazine is an atrazine (log Kow 2.61) based herbicide commercially available as Hi-Yield™ Atrazine Herbicide from Voluntary Purchasing Group, Bonham, Texas.

[0039] Chlorothalonil is a chlorothalonil (log Kow 2.88) based herbicide and is commercially available as Chlorothalonil 720 from Drexel Chemical, Memphis, Tennessee.

[0040] The copolymer was formed using solution polymerization to form a random copolymer having about 60% to 70% by weight of monomer structural units derived from butyl methacrylate and about 30% to 40% by weight of monomer structural units derived from methacrylic acid, based on the total weight of the copolymer. The copolymer was neutralized with ammonia to form the ammonia salt of the acrylic copolymer and had a weight average molecular weight of about 27,000 Daltons as measured by GPC. The copolymer is available from The Dow Chemical Company, Midland, Michigan.

[0041] Pinene is a pinene-based rain-resistant adjuvant containing diterpene polymers, hydrocarbon resins, petrolatum, and α-(p-dodecylphenyl)-ω-hydroxypoly(oxyethylene), and is commercially available as Nu-Film 17™ from Miller Chemical and Fertilizer Corporation, Hanover, Pennsylvania.

[0042] Propylene glycol is a solvent diol and is available from The Dow Chemical Company, Midland, Michigan.

[0043] Sample preparation The samples were prepared by weighing all ingredients (except water) separately, then combining the two materials in a vial and vortex mixing at 2800 rpm for 30 seconds. The resulting formulation was then diluted to a dilution ratio appropriate for the active ingredient used, as listed in Table 1. Water was used as the diluent.

[0044] [Table 1]

[0045] Test Method Kow Testing: The log Kow values ​​of the first and second acrylic monomers and the active ingredient are determined by utilizing the Estimation Programs Interface (EPI) Suite™, (KOWWIN version 1.68), available at https: / / www.epa.gov / tsca-screening-tools / epi-suitetm-estimation-program-interface.

[0046] Rainfastness test: Three replicates per sample were used to calculate the average performance and standard deviation. Formulations were prepared at the desired concentration with the desired rainfastness adjuvant, and once the formulations were made, they were further diluted based on the average dilution rate determined from the label of each active ingredient. A control without pinene and copolymer was included in the experiment. A 2" x 4" piece of Parafilm® sheet (i.e., used to mimic plant leaves) was cut and placed on a black Leneta card. Before the experiment was performed, the Parafilm® sheet was carefully wiped with a Kimwipe® cloth. Using an automatic pipette, 15 x 30 μL droplets of the prepared formulation were placed on the Parafilm® following a pattern of 3 rows x 5 columns. The formulation was vortex mixed after depositing each set of 5 droplets to ensure that the formulation remained homogenous and that the composition of each droplet was the same. The resulting samples were then stacked in a container and placed in a hood overnight. After the samples were completely dried, they were exposed to simulated rainfall using an Exo Terra Monsoon RS400 Rainfall System™ rainfall simulator fitted with two Exo Terra standard nozzles for the indicated extended periods of time. The samples were positioned 33 centimeters from the nozzles and the spray flow rate was 6 liters per hour. Once dry, the Parafilm® sheets were cut into 15 individual sections and further analyzed according to the Atrazine and Chlorothalonil Test Methods described below.

[0047] Atrazine Test Method: An ultra-performance liquid chromatograph coupled with an ultraviolet detector was used to determine the concentration of atrazine present on Parafilm® sheets before and after exposure to simulated rain. Each of the Parafilm® sheet sections was added to a separate glass vial containing 15 grams of methanol. The samples were shaken for at least 30 minutes on a horizontal shaker and 1 milliliter ("mL") of each solvent was transferred to an autosampler vial. Samples were quantified on a 2.1 millimeter ("mm") x 50 mm C18 ultra-performance liquid chromatograph column using an isocratic flow profile (i.e., 40:60 water:methanol, 0.05% formic acid, 0.4 mL / min) and UV detection (222 nanometers) was referenced to an atrazine calibration curve.

[0048] Chlorothalonil Test Method: An ultra-performance liquid chromatograph coupled with a UV detector was used to determine the concentration of chlorothalonil present on Parafilm® sheets before and after exposure to simulated rain. Each of the Parafilm® sheet sections was added to a separate glass vial containing 15 g of acetone. Samples were shaken for at least 30 minutes on a horizontal shaker and 1 mL of each solvent was transferred to an autosampler vial. Samples were quantified on a 2.1 x 50 mm C18 ultra-performance liquid chromatograph column using an isocratic flow profile (i.e., 40:60 water:methanol, 0.05% formic acid, 0.4 mL / min) and UV detection (222 nanometers) was referenced to a chlorothalonil calibration curve.

[0049] result Referring now to Table 2, results of the atrazine and chlorothalonil test methods are provided after rain resistance testing for various periods of time.

[0050] [Table 2]

[0051] As is evident from Table 2, the incorporation of the copolymer into the agricultural formulation can dramatically increase the retention of both atrazine and chlorothalonil retention compared to the comparative example, achieving successful rain resistance. CE1 demonstrates that the lack of rain resistance agent in the agricultural formulation results in unacceptably low atrazine retention regardless of rain exposure time. The incorporation of pinene rain resistance additive in CE2 demonstrates that even with the rain resistance adjuvant, the atrazine retention is unacceptably low at about 41% after only 5 minutes. In contrast to CE1 and CE2, both IE1 and IE2 containing the copolymer can achieve successful rain resistance by showing 80% or more atrazine retention after 5 minutes of simulated rain. In fact, both IE1 and IE2 can show 80% or more atrazine retention after 30 minutes of simulated rain, which far exceeds the successful rain resistance parameters.

[0052] With respect to IE3, IE4 and CE3-CE5, it is clear that the use of copolymers in agricultural formulations provides successful rain resistance. As can be seen, the addition of copolymers at concentrations as low as 1.1 wt% (i.e., IE3) can achieve successful rain resistance. IE4 demonstrates that an increased copolymer concentration of about 2.6 wt% allows the agricultural formulation to retain more than 90% of the chlorothalonil even 30 minutes after a simulated rainfall. In contrast, none of CE3-CE5 can achieve successful rain resistance. CE3, which does not have a rain resistance adjuvant, shows that chlorothalonil is easily washed off under a simulated rainfall. CE3 and CE4 show that increasing the amount of pinene rain resistance adjuvant increases chlorothalonil retention, but is still insufficient to achieve successful rain resistance. Despite similar loadings of copolymer and pinene, IE3 and IE4 are able to achieve successful rainfastness, whereas CE4 and CE5 do not demonstrate the effectiveness of the copolymer in retaining active ingredients with a log Kow above 1.

Claims

1. An agricultural formulation comprising: A copolymer comprising: (i) 20% to 50% by weight, based on the total weight of the copolymer, of monomer structural units derived from a first acrylic monomer having a log Kow of 1.0 or less; and (ii) a copolymer comprising 50% to 80% by weight, based on the total weight of the copolymer, of monomeric structural units derived from a second acrylic monomer having a log Kow of 2.0 to 6.0; and and an active ingredient having a log Kow greater than 1.

0.

2. 10. The agricultural formulation of claim 1, wherein the agricultural formulation comprises 0.5% to 4.0% by weight of the copolymer, based on the total weight of the agricultural formulation.

3. 3. The agricultural formulation according to claim 1 or 2, The agricultural formulation further comprises 0.5% to 3.0% by weight of a glycol.

4. 3. The agricultural formulation according to claim 1 or 2, wherein the active ingredient is a pesticide having a log Kow of 2.5 or greater.

5. 3. The agricultural formulation of claim 1 or 2, wherein the copolymer is a random copolymer of the first and second acrylic monomers and has a weight average molecular weight of from 15,000 Daltons to 30,000 Daltons as measured by gel permeation chromatography.

6. 3. The agricultural formulation of claim 1 or 2, wherein the first acrylic monomer is methacrylic acid.

7. 7. The agricultural formulation of claim 6, wherein the second acrylic monomer has a log Kow of 2.0 to 3.

0.

8. 3. The agricultural formulation of claim 1 or 2, wherein the second acrylic monomer is butyl methacrylate.

9. 3. Agricultural formulation according to claim 1 or 2, wherein the copolymer comprises from 60% to 70% by weight of monomeric structural units derived from butyl methacrylate and from 30% to 40% by weight of monomeric structural units derived from methacrylic acid, based on the total weight of the copolymer.

10. 1. An agricultural mixture comprising: Water, 3. An agricultural mixture comprising the agricultural formulation according to claim 1 or 2.