Prohexadione plant growth regulator composition

Abstract

An aqueous suspension concentrate composition of prohexadione comprising prohexadione calcium, ammonium sulfate and an amine.

Description

[Technical field]

[0001] The present invention relates to an aqueous suspension concentrate of the plant growth regulator prohexadione, a method for its preparation and the use of prohexadione in weed control. [Background technology]

[0002] Prohexadione calcium (IUPAC name: calcium 3,5-dioxo-4-propionylcyclohexane carboxylate (CA): calcium 3,5-dioxo-4-(1-oxopropyl)cyclohexane carboxylate) is a foliar plant regulator that inhibits the synthesis of the plant hormone gibberellins, thereby suppressing internodal elongation and vegetative growth. Prohexadione calcium is used, for example, for plant growth control in cereals including barley, oats, and wheat, as well as in turf, apple, pear, cherry, and peanut. When applied to apple and pear leaves, it increases the resistance of the leaves to two major diseases: fire blight (caused by Erwinia amylovora) and apple scab (caused by Venturia inaequalis).

[0003] Prohexadione calcium is available as a dry flowable formulation. Dry flowable formulations, such as water dispersible granules, are often mixed with ammonium sulfate in the spray tank to improve the activity of the composition and reduce mixing issues with hard water in the spray tank. End users of dry flowable formulations must mix and effectively disperse the dry flowable formulation in water, and the diluted composition is typically applied to foliage with spray equipment. Poor dispersion of the dry flowable or use of a hard water source can result in settling of the product or clogging of the spray nozzle, resulting in a risk of underdosing.

[0004] Prohexadione calcium has a solubility of approximately 786 mg / l in distilled water at 20° C. and is susceptible to decomposition over time in aqueous compositions. Prohexadione calcium has a reported hydrolysis rate of 4.4 to 65 days at pH 5-7 and contains a chromophore that absorbs at wavelengths greater than 290 nm, and may be susceptible to direct photodegradation by sunlight (Pesticide Manual 15th Edition ver.5.1 Alton British Crop Protection Counsel).

[0005] Therefore, customers often prefer liquid formulations over dry flowable compositions due to ease of handling, dilution in the spray tank, and reduced dust hazards. However, there is a need for a suspension concentrate composition of prohexadione calcium. Summary of the Invention

[0006] The present inventors have discovered that prohexadione calcium can be formulated as a stable aqueous suspension concentrate in the presence of ammonium sulfate and an organic amine proton scavenger.

[0007] We provide an aqueous suspension concentrate composition of prohexadione comprising prohexadione calcium, ammonium sulfate, and an amine, the amine preferably having a water solubility of at least 4 g / L at 20° C.

[0008] The compositions of the present invention offer the significant advantage of including ammonium sulfate in a liquid composition containing prohexadione calcium that exhibits excellent storage stability, provides the improved activity provided by ammonium sulfate without the need to handle solid powders or granules and does not require tank mixing of ammonium sulfate prior to field use.

[0009] The organic amine may be a primary, secondary, tertiary amine or may be a sterically hindered amine such as DABCO. In one embodiment, the amine comprises at least one of the following formula (I): [ka]

[0010] In the formula, R 1 , R 2 and R 3 are independently selected from hydrogen; C1-C6 alkyl; aryl; C1-C6 alkyl substituted with a substituent selected from the group consisting of hydroxyl, C1-C6 alkoxy, amino, C1-C6 alkylamino, amino-substituted alkylamino, amino-substituted C1-C6 alkoxy, and di-(C1-C6 alkyl)amino; R 1 , R 2 and R 3 is other than hydrogen; and R 1 , R 2 and R 3 two of which together form a 5 or 6 membered ring incorporating the amine nitrogen, optionally having methylene and optionally further heteroatom ring members (in addition to the amine nitrogen) selected from -O-, oxo (C=O), -N(H)- and -N(C1-C6-alkyl)-; R 1 , R 2 and R 3 The other is selected from hydrogen, C1-C6 alkyl, and C1-C6 alkyl substituted with a substituent selected from the group consisting of hydroxyl, C1-C6 alkoxy, amino, and amino-(C1-C6 alkyl).

[0011] Preferred amines of formula I include R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen; C1-C6 alkyl; C1-C6 alkyl substituted with a substituent selected from the group consisting of hydroxyl, C1-C6 alkoxy, amino, C1-C6 alkylamino, amino-substituted alkylamino, amino-substituted C1-C6 alkoxy, and di-(C1-C6 alkyl)amino; R 1 , R 2 and R 3at least one of which is other than hydrogen.

[0012] In one set of embodiments, the amine is of formula I, where R 1 , R 2 and R 3 is independently selected from the group consisting of hydrogen and C1-C6 alkyl; R 1 , R 2 and R 3 at least one of which is C1-C6 alkyl. Preferred amines in this group are mono-, di- and tri-(C1-C6 alkyl)amines, preferably tri-(C1-C4 alkyl)amines such as triethylamine. Examples of specific amines in this group include dimethylamine, trimethylamine, ethylamine, and triethylamine.

[0013] In a further series of amines of formula I, R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, C1-C6 alkyl, and C1-C6 alkyl substituted with a substituent selected from the group consisting of hydroxyl, C1-C6 alkoxy, amino, C1-C6 alkylamino, amino-substituted alkylamino, amino-substituted C1-C6 alkoxy, (C1-C6 alkyl)amino, and di-(C1-C6 alkyl)amino; R 1 , R 2 and R 3At least one of is other than hydrogen and C1-C6 alkyl. More specific examples of this compound group include C1-C6 alkanolamine, di-(C1-C6 alkanol)amine, tri-(C1-C6 alkanol)amine, di-(C1-C6 alkyl)-C1-C6 alkanolamine, (amino C1-C6 alkyl)-di-(C1-C6 alkyl)amine, di-(amino C1-C6 alkyl)(C1-C6 alkyl)amine, diamino C2-C6 alkyl, and amino-(C1-C4 alkoxy)-(C2-C4 alkyl)amine. In this preferred group, compounds such as ethanolamine, dimethylethanolamine, diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, and ethylenediamine (ethane-1,2-diamine) are particularly preferred.

[0014] In one embodiment, R 1 , R 2 and R 3 two of which taken together are selected from the group consisting of methylene, incorporating the amine nitrogen, and optionally, a further heteroatom ring member (in addition to the amine nitrogen) selected from -O-, -N(H)- and -N(C1-C6-alkyl)-; R 1 , R 2 and R 3 The other is selected from hydrogen, C1-C6 alkyl and C1-C6 alkyl substituted with a substituent selected from the group consisting of hydroxyl, C1-C6 alkoxy, amino and (C1-C6 alkyl)amino. Examples of amines in this group include morpholine and oxazolidones. It will be appreciated that certain carbamates such as oxazolidones are produced in solution by adding carbon dioxide to ethanolamine.

[0015] In a further set of embodiments, R 1 is aryl, and R 2 and R 3 is selected from hydrogen and C1-C4 alkyl.

[0016] Examples of preferred amines include ethanolamine, dimethylethanolamine, diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanolamine, and the most preferred amine is triethanolamine.

[0017] The compositions can, and typically will, include adjuvants such as surfactants.

[0018] The composition will normally include a dispersant, which may typically be present in the composition in an amount of up to 80g per litre of suspension concentrate composition, for example in an amount of from 0.5 to 60g per litre of composition.

[0019] In a further embodiment, the present invention provides a method for preparing a spray mixture comprising diluting an aqueous suspension concentrate composition of prohexadione with water.

[0020] In yet another embodiment, the present invention provides a method for regulating plant growth comprising applying an aqueous suspension concentrate composition of prohexadione, optionally after dilution, to the foliage of a plant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] When the terms "comprise", "included" or "comprising" are used in this specification (including the claims), they are to be construed as specifying the presence of stated features, integers, steps or components, but not excluding the presence of one or more other features, integers, steps or components, or groups thereof.

[0022] The term "wt%" means percent by weight, typically percent by weight of the suspension concentrate, unless otherwise specified.

[0023] The term "non-volatile", as used herein, unless otherwise specified, refers to a material that is liquid at ordinary temperature and pressure, has no significant vapor pressure at 20°C, and typically has an average boiling point greater than about 200°C.

[0024] In one embodiment, the amine is present in the composition in an amount such that the pH of the composition is in the range of 7.5-9.5, preferably in the range of 7.5-9, such as 7.8-9.0, 7.8-8.5, and most preferably about 8.

[0025] The presence of the amine allows aqueous suspension concentrates of prohexadione calcium to be formulated in the same composition with the activity enhancing ammonium sulfate, with the great convenience and safety of an aqueous composition. The amine preferably has an aqueous solubility of at least 4 g / L at 20°C.

[0026] The aqueous suspension concentrate composition may comprise prohexadione calcium in an amount of at least 5% by weight, preferably at least 6% by weight, such as at least 7% by weight or at least 8% by weight. In some embodiments, the amount of prohexadione calcium is in the range of 5% to 30% by weight, preferably 5% to 15% by weight, such as 7% to 15% by weight, 8% to 15% by weight, or about 10% by weight.

[0027] The weight ratio of ammonium sulfate to prohexadione calcium may be 3:1 to 1:1, preferably 2.5:1 to 1:1, for example about 2.5 to 1.5 to about 2:1.

[0028] The weight ratio of prohexadione calcium to the amine is preferably in the range of 10:1 to 1:1, preferably 8:1 to 2:1, for example 7:1 to 3:1 or about 5:1.

[0029] Typically, the amount of amine is in the range of 0.1% to 10% by weight, preferably 0.5% to 5% by weight, for example about 1% to about 5% by weight.

[0030] In one embodiment, the composition comprises: 5% to 15% by weight of prohexadione calcium, a weight ratio of ammonium sulfate to prohexadione sulfate ranging from 6:1 to 1:1 by weight; and 0.5% to 5% by weight of non-volatile amines.

[0031] The composition will preferably include a surfactant component comprising one or more surfactants.

[0032] In a further embodiment, the aqueous suspension concentrate composition comprises: 5% to 15% by weight (preferably 7% to 15% by weight) of prohexadione calcium, 10% to 30% by weight of ammonium sulfate, 0.5% to 5% by weight of an amine, preferably triethanolamine, and 2% to 20% by weight of a surfactant.

[0033] Surfactants may include dispersing agents and wetting agents. In some embodiments, the dispersing or wetting agent is selected from organosilicon, alkyl polyoxyethylene ethers, alkylphenol ethoxylates and alcohol alkoxylate surfactants; fatty acids, fatty acid esters and fatty acid amine ethoxylates, sorbitan and ethoxylated sorbitan esters; ethoxylated vegetable oils, alkyl, glycol and glycerol esters and glycol ethers, tristyrylphenol ethoxylates; copolymers of glycerol, dicarboxylic acids and monocarboxylic acids; and glucamides.

[0034] The surfactant component of the composition preferably comprises a dispersant. Examples of dispersants include lignin sulfonic acid, naphthalene sulfonic acid condensates, sulfates and phosphates of polyarylphenol ethoxylates, sulfates and phosphates of polyaryl ethers, polycarboxylates and their salts, esters of alkoxylated di(C1-C4 alkyl)diethanolamines (especially trimellarate esters), and comb-graft polymer dispersants.

[0035] In one set of embodiments, the dispersant comprises a naphthalene sulfonic acid condensate, such as the sodium salt of a sodium alkyl naphthalene sulfonate-formaldehyde condensate, for example a sodium methyl naphthalene sulfonate-formaldehyde condensate. Further examples of dispersants are naphthalenesulfonic acid condensates, such as sodium alkylnaphthalenesulfonate-formaldehyde condensates (eg Morwet™ D425).

[0036] A further group of dispersants is selected from the sulfates and phosphates of polyarylphenol ethoxylates. These sulfates and phosphates may be present in acid form or as salts, such as amine salts, such as ammonium salts or triethanolamine salts. Examples of such products include Soprophor BSU, Soprophor S25, Soprophor TS / 10, Soprophor 4D384, Soprophor 3D33, Soprophor FL.

[0037] The dispersant may comprise at least one selected from the group consisting of polyarylether sulfates and phosphates. For example, ethoxylated tristyrylphenols such as ethoxylated tristyrylphenol sulfates, e.g., 2,4,6-tris[1-(phenyl)ethyl]phenyl-omega-hydroxypoly(oxyethylene) sulfate (Soprophor® 4D384), and ethoxylated tristyrylphenol phosphates, e.g., polyethylene glycol 2,4,6-tristyrylphenyl ether phosphate triethanolamine salt (Soprophor® FL), provide excellent storage stability. In one embodiment of the aqueous suspension concentrate, the second surfactant component comprises a sulfonated or phosphated di- or tristyrenephenol ethoxylate.

[0038] Further examples of dispersant components include ethoxylated tristyrenephenol sulfates, such as Soprophor® FL or ethoxylated tristyrylphenol sulfates, such as 2,4,6-tris[1-(phenyl)ethyl]phenyl-omega-hydroxypoly(oxyethylene) sulfate (Soprophor™ 4D384).

[0039] In one embodiment, the dispersant comprises a salt of a polyaryl ether sulfate and / or phosphate, for example an ammonium salt of a tristyryl ether sulfate.

[0040] In one set of embodiments, the dispersant of the suspension concentrate composition comprises a polycarboxylate or salt thereof. Polycarboxylates include acrylic and / or methacrylic acid polymers and reaction products of unsaturated dicarboxylic acids or dicarboxylic acid derivatives with linear or branched alkenes, such as polycarboxylates having a molecular weight ranging from about 600 to about 12,000. An example of a polycarboxylate surfactant is Geropon T / 36, which is a reaction product of maleic anhydride and 2,4,4-trimethylpentene.

[0041] In one set of embodiments, the dispersant is selected from esters (particularly trimelate esters) of alkoxylated di(C1-C4 alkyl)diethanolamines, such as trimelate esters of alkoxylated diethylethanolamines, including polyoxyethylene(12) diethylethanolamine monotrimerate (e.g., alkoxylated diethylethanolamine monotrimerate). Examples of such amphoteric polymeric surfactants include those available under the trade name Atlox™ 4915. The amount of amphoteric polymeric surfactant, preferably alkoxylated diethylethanolamine monotrimerate such as polyoxyethylene(12) diethylethanolamine monotrimerate, is preferably 10-80 g per liter of concentrate, more preferably 20 g / L-80 g / L.

[0042] The dispersant may include a comb-grafted polymer dispersant, which may also function as a wetting agent. A comb-grafted polymer is a material having a polymer or oligomer chain of one chemical composition branched off from a polymer backbone of a different chemical composition. A preferred comb-grafted polymer surfactant for use in the present invention has a polymer backbone and a polyether group attached to the polymer backbone. Comb-grafted polymers that may be used in accordance with the present invention include, but are not limited to, (meth)acrylic acid, (meth)acrylate or methyl (meth)acrylate polymers, which have a chain of another polymer, such as a polyether (e.g., polyethylene glycol), extending from a (meth)acrylate polymer backbone.

[0043] In one set of embodiments, the comb graft polymers have a polymer backbone formed from polymers such as (meth)acrylic acid, acrylate, (meth)acrylate or methyl (meth)acrylate polymers and copolymers, with polyethylene glycol (PEG) branches extending from the backbone. In a two-dimensional representation, the PEG branches are depicted perpendicular to the (usually linear) acrylate polymer backbone and resemble the teeth of a comb, hence the name "comb graft polymers". Because comb graft polymers are proprietary materials, specific details regarding their composition and manufacture are unknown to the applicant.

[0044] Suitable comb graft polymers include, but are not limited to, Tersperse™ 2500 (approximately a 35% comb graft copolymer solution from Huntsman), Ethacryl P™ (35-45% comb graft copolymer solution from Lyondell Chemical), and the like.

[0045] The composition may contain one or more thickeners to provide the concentrate with a suitable viscosity, for example a viscosity in the range of 200 cP to 1500 cP (Brookfield viscosity measured at 20 rpm using spindle 2 at room temperature, such as 20° C.). Examples of thickeners include polysaccharides such as xanthan gum, rhamsan gum, locust bean gum, carrageenan or welan gum; synthetic polymers such as sodium polyacrylate, semi-synthetic polysaccharides such as carboxymethylcellulose; mineral fine powders such as aluminum magnesium silicate, smectite, bentonite, hectorite or fumed silica; or alumina sol. The amount of thickener used in the suspension of the present invention is usually 0.01% by weight or more, preferably 0.05% by weight or more, and at the same time usually 5.0% by weight or less, preferably 1.0% by weight or less, the weight percentage being based on the weight of the agrochemical suspension concentrate composition. The amount of thickener is generally about 0.1 g / L to 20 g / L.

[0046] In one embodiment, an inorganic thickener such as smectite clay is used at 3 to 25 g / L, preferably 3 to 15 g / L, more preferably 8 to 12 g / L. In a preferred embodiment, an organic thickener such as xanthan gum is used at 0.5 to 10 g / L, preferably 0.5 to 5 g / L, for example 1 to 2.5 g / L.

[0047] The composition may, and typically will, contain other additives such as preservatives and antifoaming agents. Preferred preservatives that may be used in accordance with some embodiments of the present invention include 1,2-benzisothiazolin-3-one, commercially available, for example, as Proxel GXL (trademark, Zeneca AG). The amount of preservative used in the suspension of the present invention is typically 0.01% by weight or more, preferably 0.05% by weight or more, while at the same time 1.0% by weight or less, preferably 0.3% by weight or less, the weight percentage being based on the weight of the agrochemical suspension concentrate formulation. Typically, the amount is about 0.5 g / L to about 8 g / L, preferably 1.5 g / L to 4 g / L.

[0048] Examples of preferred dispersants that can be used in the compositions of the present invention include copolymers of glycerol, dicarboxylic acid and monocarboxylic acid. Surfactants of this type are described in US20090156407. A preferred surfactant of this type is a copolymer of glycerol, phthalic anhydride and coconut fatty acid. A commercially available example of a preferred dispersant is available from Clariant under the trade name "Synergen GL 5", which contains about 70% surfactant copolymer in water and has an HLB of about 18.

[0049] The surfactant preferably also includes a non-ionic wetting agent. A wide variety of alkoxylate wetting agents are known and commercially available. The preferred wetting agents for use in the compositions of the present invention are glucamides in aqueous / glycolic solutions, such as capryloyl / caproyl methyl glucamide.

[0050] More preferably, the composition of the invention comprises as component e) a mixture of octyl-N-methylglucamide and decyl-N-methylglucamide. This product is available from Clariant under the name Synergen® GA. The proportion of octyl-N-methylglucamide in this mixture may be 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 30% to 70% by weight, based on the total amount of alkylglucamides present in this mixture. The proportion of decyl-N-methylglucamide in this mixture may be 10% to 90% by weight, preferably 20% to 80% by weight, more preferably 30% to 70% by weight, based on the total amount of alkylglucamides present in this mixture.

[0051] The composition may be prepared by milling prohexadione calcium particulate matter, preferably with a mixture of ammonium sulfate, water, amine, dispersant and optionally other ingredients, to reduce the particle size of the prohexadione calcium to a d90 of 10 microns or less, preferably a d90 of 8 microns or less. The d90 particle size of the prohexadione calcium in the composition may be, for example, in the range of 2 microns to 10 microns, preferably 2 microns to 8 microns, for example 5 microns to 8 microns. Air milling of the prohexadione calcium may also be used as an alternative to wet milling.

[0052] In one embodiment, the composition comprises 0.5% to 10% by weight (e.g. 0.5% to 5% by weight) of a surfactant selected from copolymers of glycerol, dicarboxylic acids and monocarboxylic acids. Particularly preferred are copolymers of glycerol, phthalic anhydride and coconut fatty acids.

[0053] In one embodiment, the composition may comprise from 0.5 to 10% by weight of the glucamide surfactant, for example from 0.5% to 5% by weight of the glucamide surfactant.

[0054] Thus, in one embodiment of an aqueous composition of prohexadione, the composition comprises: 5% to 15% by weight of prohexadione calcium; 10% to 30% by weight of ammonium sulfate; 0.5% to 5% by weight of an amine, preferably triethanolamine; and 0.5% to 10% by weight, for example 0.5% to 5% by weight, of a surfactant that is a copolymer of glycerol, a dicarboxylic acid, and a monocarboxylic acid, and 0.5% to 10% by weight of the glucamide surfactant, for example 0.5% to 5% by weight of the glucamide surfactant.

[0055] The composition may also include a wetting surfactant. Preferred wetting surfactants include nonionic polyglycol ether derivatives of aliphatic alcohols having 8-18 carbon atoms in the aliphatic group. More preferred surfactants have an HLB in the range of 5-14, and even more preferred in the range of 9-14. An example of a useful surfactant is an aliphatic alcohol having 8-18 carbon atoms ethoxylated with 2-15 ethylene oxide (EO) units. Specific examples include isotridecyl alcohol polyglycol ethoxylate ethoxylated with 2, 5, 6, 8 or 15 moles. Commercially available surfactants of this type include "Genapol" X020, Genapol X050, Genapol X060, Genapol X080, Genapol X090, Genapol X100 and Genapol X150, respectively. These surfactants have an HLB in the range of 5-14. Genapol X050, Genapol X060 and Genapol X080 contain surfactants in which isodecyl alcohol is ethoxylated with 5 to 10 EO units and has an HLB in the range of 9 to 14.

[0056] The inventors have found that some prohexadione calcium compositions are prone to forming calcium salt precipitates during storage or when combined with water containing calcium salts, such as calcium chloride, commonly present in municipal water sources as a result of water treatment. We have found that chelating agents significantly improve storage and handling of suspension concentrate compositions by reducing the tendency for calcium salts to form during storage or field use of the composition. Dilution of concentrates by end users, such as farmers, may use water with varying water quality and mineral content. The use of chelating agents has been found to significantly improve stability in this situation as well. The content of chelating agents typically ranges from 0.5% to 8% by weight of the concentrate, preferably 0.5% to 5% by weight. Specific examples of chelating agents include EDTA and salts such as its disodium salt, amine polycarboxylates, glucuronates, salts such as nitrilotriacetic acid (NTA) and its trisodium salt, methylglycine diacetic acid (MGDA) and salts, particularly the trisodium salt of methylglycine diacetic acid (MGDA-Na3). The most preferred chelating agent is methylglycine diacetic acid (MGDA) and its salts, especially the trisodium salt of methylglycine diacetic acid (MGDA-Na3). MGDA-Na3 is preferred in an amount of 0.5% to 8% by weight of the concentrate, especially 0.5% to 5% by weight. MGDA-Na3 is commercially available from Nouryon, The Netherlands, under the trade names DISSOLVINE® M-40 and DISSOLVINE® MS.

[0057] The composition may include an odor masking agent to reduce odors from amines such as triethanolamine. An example of an odor masking agent is a mixture containing 30-70% by weight of nonylphenol polyethylene glycol ether and 20-40% by weight of methyl salicylate in 10-30% by weight of polyethylene glycol.

[0058] The composition may include an antifreeze agent. Propylene glycol is a typical antifreeze agent. Glycerin is another typical antifreeze agent. The amount of the antifreeze agent is usually about 2% to 10% by weight, for example, 5% to 8% by weight, of the composition.

[0059] Typically, the content of the water-soluble organic solvent is 10% or less by weight of the composition, for example 5% or less by weight. The water solubility of the organic solvent typically allows for a single phase of the composition at 20° C.

[0060] The composition may also include an antifoaming agent, such as a modified silicone-based antifoaming agent, for example a polydimethylsiloxane emulsion believed to include a siloxane silol alkylene oxide copolymer. Such an antifoaming agent is available from Momentive under the trade name SAG 1572.

[0061] The present invention further provides a method for regulating plant growth by spraying the composition on leaves, optionally after dilution.Preferred plants are fruit trees (especially apple, pear and cherry), grasses (especially wheat, triticella, barley, oats and rye, as well as corn, rice, sugarcane and lawn).Other suitable plants include cotton, soybean, foxtail millet, sunflower, rapeseed, peanut, coffee, rice, ornamental plants, lawn grasses (e.g. Kentucky bluegrass, annual and perennial ryegrass, tall fescue, red fescue, white ostrich grass, annual bluegrass, turfgrass, bermuda grass, Saint Pied grass, Saint Augustine grass), etc.

[0062] An advantage of the present invention is that prohexadione calcium and ammonium sulfate can be combined in an aqueous formulation.

[0063] Aqueous compositions are typically diluted with water prior to application. After dilution, the compositions can be applied to vigorous trees at rates of 50 ppm prohexadione calcium active ingredient (ai) to 1000 ppm (ai) to effectively control vegetation growth. The optimum rate of prohexadione calcium ai required to effectively control vegetation growth depends on the vigor, age, pruning system, fruit set, and other factors affecting vegetation growth of the plant. Typically, concentrations of 50 ppm (ai) to 500 ppm (ai) can effectively control vegetation growth.

[0064] The present invention is described with reference to the following examples, which are provided to further understand the embodiments of the invention and are not intended to limit the scope or applicability of the invention to the specific examples. EXAMPLES

[0065] Example 1 - Part 1 Prohexadione Calcium Suspension Concentrate Suspension concentrates were prepared by combining the ingredients shown in Table 1 in the amounts shown in Table 1. Common methods: Add water, ammonium sulfate, base, surfactant, and active ingredient. Transfer contents to mill and grind material until particle size distribution is less than 8 microns. Remove from mill and add gelling agent, defoamer, and water for letdown. [Table 1]

[0066] Synergen® GL5 is a glycerol / coconut fatty acid / phthalic anhydride copolymer from Clariant. Synergen™ GA is a glucamide [1-deoxy-1(methyl-C8-10 (even number)-alkanoyl)amino)-D-glucitol] in an aqueous / glycolic acid solution. Kelzan is a xanthan gum polysaccharide. SAG1572- Polydimethylsiloxane Emulsion-Siloxanesilol Alkylene Oxide Copolymer Proxel™ BN - an aqueous dispersion of 13.5% 1,2-benzisothiazolin-3-one (BIT) and 6.5% 2-bromo-2-nitropane-1,3-diol Aromex™ WG28 - 30-70% nonylphenol polyethylene glycol ether and 20-40% methyl salicylate in polyethylene glycol

[0067] Composition Examples 2-6 According to Example 1, compositions according to the invention were prepared using the ingredients in the amounts by weight shown in Table 2. [Table 2]

[0068] MIPA- Monoisopropylamine TEOA - Triethanolamine AMP 95 - 95% 2-amino-2-methyl-1-propanol in water

[0069] The composition of Example 1 was a suspension concentrate and was easily dispersed in the application water. Test results showing the excellent stability of this composition are shown in Table 3 below. [Table 3]

[0070] Efficacy - The efficacy of the composition of Example 1 was tested using the following procedure, with the results shown in Table 5.

[0071] Title: A plant growth regulator for kikuyu grass turf maintained as golf course fairways and playing fields.

[0072] Materials and Methods: A trial comparing Anuew 27.5 WDG, NUP-19022, and Primo Maxx for growth regulation of kikuyu grass (Pennisetum clandestinum) was initiated at the University of California, Riverside Agricultural Management Station. The trial was conducted on high-quality sward soil with Hanford fine sandy loam soil. The trial plots were mowed to a height of 0.5 inches three days per week during growth for the duration of the trial. The trial plots were fertilized with 0.5 pounds of nitrogen monthly and irrigated as needed to avoid drought stress. The trial was conducted in a randomized complete block design with four replications. Treatments were applied using a CO2 backpack sprayer at a spray rate of 44 gallons per acre on four spray dates (A, C, E, G) approximately 14 days apart (June 25, 2020 (A), July 9, 2020 (C), July 23, 2020 (E), August 6, 2020 (G)).

[0073] Evaluation items included visual turf quality, turf damage, NDVI, DGCI, and cutting weight (fresh and dry weight). Data were analyzed using ANOVA and treatment means were separated using Fisher's LSD at the p ≤ 0.05 level.

[0074] Table 4 - Processing List [Table 4]

[0075] Table 5 - Cutting weight results [Table 5]

[0076] † A p-value > 0.05 indicates dates where there is no significant difference between treatments. 1 Means with different letters within a column are significantly different from each other (P=0.05, LSD). 2 Indicates the number of days (DA) from the nearest applicable date (-A = 6 / 25, -C = 7 / 9, -E = 7 / 23, -G = 8 / 6 / 2020).

[0077] Anuew™ plant growth regulator is an extruded, granular plant growth regulator containing prohexadione calcium (27.5% by weight) as the active ingredient, available from Nufarm Americas.

[0078] Primo Maxx™ is a turf growth regulator containing the active ingredient trinexapac-ethyl (120 g / L) as a microemulsion concentrate (available from Syngenta).

[0079] Summary of harvest weight

[0080] Anuew 27.5 WDG, Example 1, and Primo Maxx all demonstrated statistically significant lower mowing weights compared to the untreated control on all evaluation dates after application began, demonstrating consistent growth regulation over the two month study period. Anuew 27.15 WDG and Example 1 demonstrated a predictable dose response with the higher doses being numerically more effective at modulating growth (lower mowing weights) than the lower doses on 7 of 8 and 8 of 8 mowing evaluation dates after application began, respectively, although not statistically significantly so.

[0081] The trial demonstrated effective and consistent growth regulation of kikuyugrass by each PGR.

[0082] Comparative Example 1

[0083] A composition similar to Example 1 was prepared containing the ingredients in the amounts shown in Table 6.

[0084] Table 6 - Millbases [Table 6]

[0085] Table 7 - Letdowns [Table 7]

[0086] The resulting pH stock solution was recorded as 6.52. HPLC data showed decomposition.

[0087] Comparative Example 2

[0088] Using the method of Comparative Example 1, compositions were prepared using the following components in the amounts specified in Table 8. [Table 8]

[0089] The pH was recorded as not stable after 3 days. The pH instability may be due to residual sulfuric acid in the AMS.

[0090] Comparative Example 3

[0091] The composition of Comparative Example 3 (CE-3) was prepared by combining the ingredients shown in the following table in the amounts by weight shown in Table 9. [Table 9]

[0092] The resulting product was found to be non-viable.

[0093] Example 7 – Tank Mix Compatibility

[0094] Prohexadione formulations are generally not mixable with many things.

[0095] Tank mixes of the composition of Example 1 were tested with various commercial herbicides and compared to an existing prohexadione composition*. [Table 10]

[0096] A comparison was made with Nufarm Americas' ANUEW™ brand prohexadione calcium 27.5% by weight granular composition, which was not compatible with the tank mix partners listed above.

[0097] Example 8 – Prohexadione Suspension Concentrate

[0098] In some water sources in combination with prohexadione calcium, precipitates may form. The inventors have found that chelating agents, particularly MGDA, are useful in inhibiting the formation of crystalline material during or after preparation of the suspension concentrate, improving the product in waters of different qualities.

[0099] Compositions of the present invention were prepared using MGBA of Dissolvine®-M composition having the composition shown in Table 11.

[0100] Table 11 - Theoretical composition [Table 11]

[0101] Dissolvine®-M is a product of Nouryon, Netherlands, that contains approximately 40% by weight of the trisodium salt of methylglycine diacetic acid (MGDA-Na3) in water.

[0102] Table 12 - Millbases [Table 12]

[0103] Two compositions were prepared, compositions A and B differing in the addition of a chelating agent.

[0104] Table 13 - Let Down A [Table 13]

[0105] Composition A [Table 14]

[0106] Let Down B [Table 15]

[0107] Composition B [Table 16]

[0108] Both compositions are stable.

Claims

1. An aqueous suspension concentrate composition of prohexadione comprising prohexadione calcium, ammonium sulfate and an amine.

2. 2. The aqueous suspension concentrate composition of claim 1, wherein the amine has a water solubility of at least 4 g / L at 20°C.

3. 2. The aqueous suspension concentrate composition of claim 1, wherein the amine comprises at least one of the following formula (I): 【Chemistry 1】 (In the formula, R １ , R ２ and R ３ are independently hydrogen; C １ ~C ６ Alkyl; Aryl; Hydroxyl, C １ ~C ６ Alkoxy, amino, C １ ~C ６ Alkylamino, amino-substituted alkylamino, amino-substituted C １ ~C ６ Alkoxy and di-(C １ ~C ６ C substituted with a substituent selected from the group consisting of １ ~C ６ is selected from the group consisting of alkyl, R １ , R ２ and R ３ is other than hydrogen, R １ , R ２ and R ３ two of which taken together form a methylene incorporating an amine nitrogen and optionally (in addition to the amine nitrogen) -O-, oxo (C=O), -N(H)- and -N(C １ ~C ６ -alkyl)-, forming a ring of 5 or 6 ring members with an additional heteroatom ring member selected from R １ , R ２ and R ３ The other one is hydrogen, C １ ~C ６ Alkyl and hydroxyl groups, C １ ~C ６ Alkoxy, amino and (C １ ~C ６ C substituted with a substituent selected from the group consisting of １ ~C ６ alkyl.)

4. In formula I, the group R １ , R ２ and R ３ are independently hydrogen; １ ~C ６ Alkyl; Hydroxyl, C １ ~C ６ Alkoxy, amino, C １ ~C ６ Alkylamino, amino-substituted alkylamino, amino-substituted C １ ~C ６ Alkoxy and di-(C １ ~C ６ C substituted with a substituent selected from the group consisting of １ ~C ６ is selected from the group consisting of alkyl, R １ , R ２ and R ３ 4. The aqueous suspension concentrate composition of claim 3, wherein at least one of is other than hydrogen.

5. In formula I, the group R １ , R ２ and R ３ are independently hydrogen; １ ~C ６ Alkyl; Hydroxyl, C １ ~C ６ Alkoxy, amino, C １ ~C ６ Alkylamino, amino-substituted alkylamino, amino-substituted C １ ~C ６ Alkoxy and di-(C １ ~C ６ C substituted with a substituent selected from the group consisting of １ ~C ６ is selected from the group consisting of alkyl, R １ , R ２ and R ３ 4. The aqueous suspension concentrate composition of claim 3, wherein at least one of is other than hydrogen.

6. 2. The aqueous suspension concentrate composition of claim 1, wherein the amine is selected from the group consisting of ethanolamine, dimethylethanolamine, diethanolamine, diisopropanolamine, triethanolamine, triisopropanolamine, ethylenediamine, morpholine, and 2-amino-2-methyl-1-propanol.

7. 2. The aqueous suspension concentrate composition of claim 1, wherein the tertiary amine is triethanolamine or triisopropanolamine.

8. 2. The aqueous suspension concentrate composition of claim 1, wherein prohexadione calcium is present in an amount of at least 5% by weight.

9. 2. The aqueous suspension concentrate composition of claim 1, wherein the prohexadione calcium is present in an amount of from 5% to 20% by weight of the composition.

10. 2. The aqueous suspension concentrate composition of claim 1, wherein the weight ratio of ammonium sulfate to prohexadione calcium is from 3:1 to 1:

1.

11. 2. The aqueous suspension concentrate composition of claim 1, wherein the amine is present in the composition in an amount such that the pH of the composition is in the range of from 7.5 to 9.5, preferably in the range of from 7.5 to 9, such as from 7.8 to 9.0, such as from 7.8 to 8.5, and most preferably about 8.

12. 2. The aqueous suspension concentrate composition of claim 1, wherein the amine is present in an amount ranging from 1% to 10% by weight of the composition.

13. 2. The aqueous suspension concentrate composition of claim 1, wherein the amine is present in an amount ranging from 0.5% to 5% by weight of the composition.

14. 5% to 15% by weight of prohexadione calcium; Ammonium sulfate and prohexadione sulfate in a weight ratio ranging from 6:1 to 1:1; 0.5% to 5% by weight of a non-volatile tertiary amine; 2. The aqueous suspension concentrate composition of claim 1, comprising:

15. 7% to 15% by weight of prohexadione calcium; 15% to 30% by weight of ammonium sulfate; 0.5% to 5% by weight of an amine, preferably triethanolamine, and 2% to 20% by weight of a surfactant 2. The aqueous suspension concentrate composition of claim 1, comprising:

16. Organosilicone, alkyl polyoxyethylene ether, alkylphenol ethoxylate and alcohol alkoxylate surfactants; Fatty acids, fatty acid esters and fatty acid amine ethoxylates, sorbitan and ethoxylated sorbitan esters; Ethoxylated vegetable oils, alkyl, glycol and glycerol esters and glycol ethers; Tristyrylphenol ethoxylate; Copolymers of glycerol, dicarboxylic acids and monocarboxylic acids; and Glucamide 2. The aqueous suspension concentrate composition of claim 1, comprising a surfactant selected from the group consisting of:

17. including a surfactant which is a copolymer of glycerol, phthalic anhydride and coconut fatty acid; 2. The aqueous suspension concentrate composition of claim 1.

18. 10. The aqueous suspension concentrate composition of claim 1 comprising a non-ionic wetting agent.

19. 16. The aqueous suspension concentrate composition of claim 15, comprising a surfactant that is a wetting agent selected from glucamides.

20. 16. The aqueous suspension concentrate composition of claim 15, wherein the surfactant composition comprises capryloyl / caproyl methyl glucamide.

21. 2. An aqueous suspension concentrate composition according to claim 1, comprising from 0.5% to 10% by weight, such as from 0.5% to 5% by weight, of a copolymer of glycerol, a dicarboxylic acid and a monocarboxylic acid.

22. 2. The aqueous suspension concentrate composition of claim 1, wherein the surfactant composition comprises 0.5 to 10% by weight of the aqueous suspension concentrate composition of a glucamide surfactant.

23. 5% to 15% by weight of prohexadione calcium; 10% to 30% by weight of ammonium sulfate; 0.5% to 5% by weight of an amine, preferably triethanolamine; 0.5% to 10%, e.g., 0.5% to 5%, by weight of a surfactant that is a copolymer of glycerol, a dicarboxylic acid, and a monocarboxylic acid; and 0.5% to 10% by weight of a glucamide surfactant, for example 0.5% to 5% by weight of a glucamide surfactant; 2. The aqueous suspension concentrate composition of claim 1, comprising:

24. 1% to 10% by weight of propylene glycol antifreeze; The composition of claim 1.

25. 10. The method of claim 1, comprising applying the composition, optionally after dilution, to foliage. A method for regulating plant growth.

26. 26. The method according to claim 25, wherein the plant is selected from the group consisting of fruit trees (especially apple, pear and cherry), grasses (especially wheat, triticella, barley, oats and rye, but also maize, rice, sugarcane and turf), cotton, soybean, foxtail millet, sunflower, rapeseed, peanut, coffee, rice, ornamental plants, turf grasses (e.g. Kentucky bluegrass, annual and perennial ryegrass, tall fescue, red fescue, white ostrich grass, annual bluegrass, turfgrass, bermuda grass, St. Vide grass, St. Augustine grass).

27. 26. The method of claim 25, wherein the aqueous composition is diluted with water prior to foliar application and applied to a target plant at a concentration of from 50 ppm (ai) to 1000 ppm.