[go: up one dir, main page]

US20220132854A1 - Stable liquid compositions and methods of using the same - Google Patents

Stable liquid compositions and methods of using the same Download PDF

Info

Publication number
US20220132854A1
US20220132854A1 US17/432,025 US202017432025A US2022132854A1 US 20220132854 A1 US20220132854 A1 US 20220132854A1 US 202017432025 A US202017432025 A US 202017432025A US 2022132854 A1 US2022132854 A1 US 2022132854A1
Authority
US
United States
Prior art keywords
surfactant
pesticide composition
liquid pesticide
liquid
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US17/432,025
Inventor
James Franklin Essinger, Jr.
Lin Gan
Nihal Johnny BEHRENS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gowan Co LLC
Original Assignee
Gowan Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gowan Co LLC filed Critical Gowan Co LLC
Priority to US17/432,025 priority Critical patent/US20220132854A1/en
Assigned to GOWAN COMPANY, L.L.C. reassignment GOWAN COMPANY, L.L.C. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GAN, LIN, BEHRENS, NIHAL JOHNNY, ESSINGER, James Franklin
Publication of US20220132854A1 publication Critical patent/US20220132854A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms

Definitions

  • Liquid pesticide compositions having enhanced stability, and methods of using the same are provided.
  • Liquid compositions are desirable since they facilitate easy volumetric measurement and transfer. This advantage can be realized for in-process liquid intermediates or final liquid compositions.
  • Liquid compositions can be single-phase or multi-phase compositions, including emulsions, suspensions, solutions, etc.
  • Common ingredients in liquid compositions contain hydroxy-functionality in the diluents, solvents, surfactants, and/or rheology modifiers, etc. These common ingredients which contain hydroxy-functionality include water, alcohols, glycols, alkoxylated surfactants, etc.
  • Certain pesticides are known to be chemically unstable. These pesticides exhibit unacceptable loss in stored liquid compositions.
  • a chemically unstable pesticide generally has a greater than 5% (w/w) relative loss of that pesticide after storing the liquid composition for 8 weeks at 40° C. (measured using quantitative chromatography, such as HPLC).
  • Chemically unstable liquid compositions are usually not commercially successful since liquid compositions are typically stored at 40° C. or higher.
  • compositions such as a water-dispersible powder (WP), water-soluble powder (SP), water-dispersible granule (WG), water-soluble granule (SG), or broadcast-type ready-to-use granule (G).
  • WP water-dispersible powder
  • SP water-soluble powder
  • WG water-dispersible granule
  • SG water-soluble granule
  • G broadcast-type ready-to-use granule
  • These compositions seek to avoid/minimize liquid-based contact of the pesticide with ingredients commonly used to make liquid compositions, and thereby maximize chemical stability of the pesticide by avoiding liquid compositions.
  • the existence of commercially successful solid compositions for chemically unstable pesticides implies that liquid compositions do not have acceptable storage stability.
  • U.S. Publication No. 2011/0166023 discloses an herbicidal composition comprising a) at least one ALS-inhibiting herbicide; b) at least one HPPD-inhibiting herbicide; and c) at least one saturated or unsaturated fatty acid.
  • the publication asserts that the use of a saturated or unsaturated fatty acid may chemically stabilize an herbicidal composition comprising at least one sulfonylurea herbicide and at least one HPPD-inhibiting herbicide.
  • certain fatty acids showed improved stability for several HPPD-inhibiting herbicides, almost every sulfonylurea herbicide tested had an unacceptable storage stability (over 5% (w/w) relative loss after storage for 47 days at 40° C.).
  • a stable liquid pesticide e.g. herbicidal compositions particularly sulfonylurea herbicides exhibiting less than 5% (w/w) relative loss of the active herbicide upon storage at least 47 days at 40° C.
  • the liquid pesticide composition comprises a) halosulfuron-methyl; b) one or more diluent(s), where the diluent(s) is a liquid comprising: i) a first carbon structure of at least six carbon atoms optionally including one or more heteroatom(s), the first carbon structure being linear, branched, cyclic or aromatic; ii) optionally one or more glyceryl, carbonyl, phenyl, sulfonyl, or phosphonyl group(s) on the first carbon structure, wherein the organic diluent(s) lack hydroxyl group(s) on the first carbon structure unless they are part of the optional carbonyl, phenyl, sulfonyl, or phosphonyl group(s); c) optionally, one or more surfactant(s), wherein the one or more surfactant(s) comprise: i) a second carbon structure
  • the liquid pesticide composition may include 0.01-40% (w/w) of one or more pesticide(s), 40-95% (w/w) of one or more diluent(s), 0-20% (w/w) of one or more surfactant(s), and 0-10% (w/w) of one or more rheology modifier(s).
  • the liquid pesticide composition may include 5-30% (w/w) of one or more pesticide(s), 40-90% (w/w) of one or more diluent(s), 5-10% (w/w) of one or more surfactant(s), and 0-5% (w/w) of one or more rheology modifier(s).
  • the liquid pesticide composition may include 20-30% (w/w) of one or more pesticide(s), 40-82% (w/w) of one or more diluent(s), 5-10% (w/w) of one or more surfactant(s), and 3-8% (w/w) of one or more rheology modifier(s).
  • the liquid pesticide composition may include one or more chemically stable pesticide(s), including Benzobicyclon, Dicamba, and/or Prosulfuron.
  • the rheology modifier may comprise silica.
  • the surfactant is an acid selected from oleic, caprylic, decanedioic, or linolenic, or a salt thereof.
  • the surfactant may also be a salt of the acid selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid.
  • the surfactant comprises at least one glyceryl group.
  • the surfactant may be selected from tricaprylate glycerol, trioleate glycerol, tristearate glycerol, di-lineolate/monostearate glycerol, or mixtures thereof.
  • the glyceryl may include a salt of carbonyl, sulfonyl, or phosphonyl, in which case any OH groups associated with the carbonyl, sulfonyl, or phosphonyl would not lead to degradation. However, an OH group associated with the glyceryl-moiety itself, such as in the case of a mono- or di-glyceride would lead to instability.
  • the surfactant may comprise a sulfonyl group.
  • the surfactant may be selected from mono/di oleyl sulfate, lauryl sulfate, dodecylbenzene sulfonate, oleyl sulfonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenesulfonate, or a salt thereof.
  • the surfactant may also be a salt of the sulfate or sulfonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the sulfate or sulfonate.
  • the surfactant may comprise at least one phosphonyl group.
  • the surfactant may be a phosphate or phosphonate selected from mono/di oleyl phosphonate, lauryl phosphonate, dodecylbenzene phosphonate, oleyl phosphonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenephosphonate, and salts thereof.
  • the surfactant may also be a salt of the phosphate or phosphonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the phosphate or phosphonate.
  • the liquid pesticide composition may comprise 0.01-40% (w/w) halosulfuron-methyl; 40-95% (w/w) of one or more diluent(s); 0-20% (w/w) of one or more surfactant(s) wherein the surfactant is selected from sodium oleate, mono-C 10-16 -alkylesters, calcium lignosulfonate, sodium dioctyl sulfosuccinate, potassium phosphate monobasic/potassium phosphate dibasic, phosphate ester, sodium dodecylbenzene sulfonate, acrylic-styrene copolymer salt, or mono tertiary amine-PEG-trimerate, or mixtures thereof; and 0-10% (w/w) rheology modifier.
  • the surfactant is selected from sodium oleate, mono-C 10-16 -alkylesters, calcium lignosulfonate, sodium dioctyl sulfo
  • the liquid pesticide composition may comprise 20-30% (w/w) halosulfuron-methyl; 40-82% (w/w) of one or more diluent(s); 5-10% (w/w) of one or more surfactant(s), wherein the surfactant is selected from sodium oleate, mono-C 10-16 -alkylesters, calcium lignosulfonate, sodium dioctyl sulfosuccinate, potassium phosphate monobasic/potassium phosphate dibasic, phosphate ester, sodium dodecylbenzene sulfonate, acrylic-styrene copolymer salt, or mono tertiary amine-PEG-trimerate, or mixtures thereof; and 3-8% (w/w) of one or more rheology modifier(s).
  • the surfactant is selected from sodium oleate, mono-C 10-16 -alkylesters, calcium lignosulfonate, sodium dioctyl sul
  • Methods for controlling pest(s) in a lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals are also provided.
  • the method comprises applying any of the liquid pesticide compositions described herein to the lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals.
  • the crop field may be selected from field corn, field corn grown for seed, grain sorghum (milo), rice, sugarcane, fallow ground, cotton, or dry beans, or combinations thereof.
  • the liquid pesticide composition comprises halosulfuron-methyl and the pests may include undesired vegetation selected from Alfalfa ( Medicago sativa ); Alligator weed ( Alternanthera philoxeroides ); Amaranth , palmer ( Amaranthus palmeri ); Amaranth , spiny ( Amaranth spinosus ); Artichoke, Jerusalem ( Helianthus tuberosus ); Barnyardgrass ( Echinochloa crusgalli ); Beggarweed, Florida ( Desmodium tortuosum ); Bindweed ( Calystegia sepium ); Bindweed, field ( Convolvulus arvensis ); Bindweed, hedge ( Calystegia sepium ); Buckwheat, wild; Polygonum convolvulus ); Buffalobur ( Solanum rostratum ); Burcucumber ( Sicyos angulatus ); Buttercup, hairy ( Ranunculus sard
  • FIG. 1 shows trial data of two inventive compositions and a commercial herbicide for control of Yellow Nutsedge ( Cyperus esculentus ).
  • halosulfuron-methyl may be made more stable in liquid compositions by formulating those pesticides with particular diluents and/or surfactants.
  • the liquid compositions generally comprise halosulfuron-methyl and at least one diluent, and optionally at least one surfactant and/or rheology modifier.
  • the diluent, surfactant, and rheology modifier are generally inert ingredients.
  • the inventors have found, however, that the presence of certain types of hydroxyl groups on these components leads to unstable compositions.
  • the compositions described herein lose less than 5% (w/w) of halosulfuron-methyl after storing the liquid composition for 8 weeks at 40° C. in a sealed container.
  • the compositions may be applied to any desired environment, such as a lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals.
  • halosulfuron-methyl pesticide compositions The presence of certain hydroxyl groups leads to instability of halosulfuron-methyl pesticide compositions. However, this instability does not result from the presence of OH components that are acidic due to adjacent electron withdrawing groups (e.g., carbonyl, sulfonyl, phosphonyl), or groups where negative charge is spread over a large volume of the group (e.g., phenyl). Rather, particular OH groups having a pKa above 13 have been found to lead to instability when present in a halosulfuron-methyl composition.
  • adjacent electron withdrawing groups e.g., carbonyl, sulfonyl, phosphonyl
  • groups where negative charge is spread over a large volume of the group e.g., phenyl
  • the pKa may be estimated by looking to standard charts showing estimated pKa values for specific OH groups, such as the following table:
  • the following surfactant compounds include the type of alcohol or hydroxyl group that the inventors have found leads to instability of halosulfuron-methyl pesticide compositions:
  • Each of the compounds above includes a hydroxyl group present on a carbon chain suggesting a pKa comparable to that of ethanol.
  • the inventors have observed that such compounds, whether used as a surfactant on their own, or present as an impurity or other component in a surfactant or other component of the composition, leads to instability of a halosulfuron-methyl composition containing such compound or compounds.
  • the following table shows seven compositions where the amount of halosulfuron-methyl lost was greater than 5% of the pesticide after storing the liquid composition for 8 weeks at 40° C. in a sealed container.
  • compositions were sealed in a container and stored for 8 weeks at 40° C.
  • the relative percentage loss of halosulfuron-methyl was calculated using high performance liquid chromatography (HPLC).
  • HPLC high performance liquid chromatography
  • the samples were extracted with solvents and then analyzed with reverse phase HPLC equipped with UV detector. The response from the detector are peak areas (mAu*s). The peak areas were correlated with percentage active ingredients through a standard calibration curve. The percentage of pesticide was calculated through the calibration curve.
  • Chemically stable compositions are those compositions that had less than 5% (w/w) relative loss of halosulfuron-methyl after 8 weeks of storage at 40° C.
  • compositions that failed can be described as follows: (1) contains unacceptable alcoholic-hydroxy; (2) contains unacceptable hydroxy-termination from polyethylene glycol synthesis; (3) contains unacceptable alcoholic-hydroxy; (4) contains CAS #67674-67-3 (Silwet L-77) with unacceptable hydroxy functionality; (5) contains unacceptable hydroxy-termination of the alkoxylate; (6) contains unacceptable hydroxy-termination from polyethylene glycol synthesis; and (7) contains unacceptable hydroxy-termination from polyethylene glycol synthesis.
  • inventive compositions described herein lack such alcohols in any of the components, particularly the surfactant where such alcohols are a common feature or are present as a result of the manufacturing process, or incomplete purification. These alcohol-containing compounds need to be removed or avoided in order to achieve a stable halosulfuron-methyl composition.
  • the present inventors have found that molecules having instability-producing OH groups even if present in small quantities can render the entire composition unstable.
  • the composition Silwet L-77 siloxane polyalkyleneoxide copolymer, >50% methyl-terminated
  • methyl-terminated siloxanes should not have instability producing OH groups.
  • the inventors have found that methyl-terminated siloxanes contain some OH-terminated siloxane molecules. Even if present in small amounts, the OH-terminated siloxanes result in instability of the overall composition.
  • the instability producing OH groups lead to instability regardless of whether they are a minor component in a much larger molecule.
  • the inventors have observed instability for polyethylene glycol 8000 (PEG8000) even though the entire 8000 MW polymer has only a single instability producing OH group.
  • PEG and polypropylene glycol (PPG) are known impurities in many compounds such as fatty alcohol ethoxylates (FAEs). See Lee et al., “Quantification of Poly (Ethylene Glycol) and Poly (Propylene Glycol) in Alkoxylated Surfactants.” Accordingly, it is important to ensure that these OH groups are not present as part of an impurity molecule.
  • the liquid compositions of the present invention which are described herein comprise halosulfuron-methyl (CAS 100784-20-1) either alone or in combination with another pesticide, such as a combination of halosulfuron-methyl and Benzobicyclon (CAS 156963-66-5).
  • Other pesticides may be used in combination with halosulfuron-methyl, such as for example Prosulfuron (CAS 94125-34-5) or Dicamba (CAS 1918-00-9).
  • the halosulfuron-methyl comprises at least 0.01%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, or 40% (w/w) by weight of the total weight of the composition.
  • the chemically unstable pesticide is less than 40%, 35%, 30%, 25%, 20%, 15%, or 10% (w/w) of by weight of the total weight of the composition.
  • the liquid compositions described herein comprise one or more diluents.
  • the diluent is a liquid contributing toward dissolving or suspending the halosulfuron-methyl active ingredient into an overall liquid herbicidal composition.
  • the diluent may optionally have a functional group providing surfactant properties, or other desired properties.
  • the diluent may simply be a liquid capable of dissolving or carrying the halosulfuron-methyl.
  • the diluent must lack hydroxyl groups except those associated with an electron withdrawing or electron dense functional group such as a carbonyl, sulfonyl, phosphonyl or phenyl group.
  • the diluent therefore may comprise at least one of alkyl carboxylic acids, alkyl carboxylate salts, alkenyl carboxylic acids, alkenyl carboxylate salts, aryl carboxylic acids, aryl carboxylate salts, alkyl sulfuric acids, alkyl sulfate salts, alkenyl sulfuric acids, alkenyl sulfate salts, aryl sulfuric acids, aryl sulfate salts, alkyl sulfonic acids, alkyl sulfonate salts, alkenyl sulfonic acids, alkenyl sulfonate salts, aryl sulfonic acids, aryl sulfonate salts, alkyl phosphate ester with free acids, alkyl phosphate ester with salts, alkenyl phosphate ester with free acids, alkenyl phosphate ester with salts, aryl phosphate ester with free acids, ary
  • the diluent is oleic acid, oleic salt, sodium oleate, lauryl sulfate, sodium lauryl sulfate, lignosulfonate acid, lignosulfonate salt, calcium lignosulfonate, dioctyl sulfosuccinate sodium salt in methyl oleate, sodium dioctyl sulfosuccinate, phosphate ester, ethoxylated phosphate ester, methyl ester, triglyceride, or a mixture thereof.
  • the diluent comprises at least 35%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 97% (w/w) by weight of the total weight of the composition.
  • the liquid compositions described herein may include one or more surfactants.
  • the surfactant may be as described above both a diluent and a surfactant. In that case, the surfactant must be a liquid. Alternatively, the surfactant may be a solid surfactant that can be added to the liquid diluent. In general, a surfactant will have a non-polar and polar (often ionic) group. The surfactant allows the overall composition to be more readily dispersed in water at the point of use. As with other components of the invention, the surfactant must lack hydroxyl groups except those associated with an electron withdrawing functional group such as a carbonyl, sulfonyl, phosphonyl or phenyl group.
  • the surfactant comprises at least one of alkyl carboxylic acids, alkyl carboxylate salts, alkenyl carboxylic acids, alkenyl carboxylate salts, aryl carboxylic acids, aryl carboxylate salts, alkyl sulfuric acids, alkyl sulfate salts, alkenyl sulfuric acids, alkenyl sulfate salts, aryl sulfuric acids, aryl sulfate salts, alkyl sulfonic acids, alkyl sulfonate salts, alkenyl sulfonic acids, alkenyl sulfonate salts, aryl sulfonic acids, aryl sulfonate salts, alkyl phosphate ester with free acids, alkyl phosphate ester with salts, alkenyl phosphate ester with free acids, alkenyl phosphate ester with salts, aryl phosphate ester with free acids, aryl phosphate
  • the surfactant is oleic acid, oleic salt, sodium oleate, lauryl sulfate, sodium lauryl sulfate, lignosulfonate acid, lignosulfonate salt, calcium lignosulfonate, dioctyl sulfosuccinate sodium salt in methyl oleate, sodium dioctyl sulfosuccinate, phosphate ester, ethoxylated phosphate ester, mono tertiary amine-PEG-trimerate, or a mixture thereof.
  • the surfactant comprises at least 1%, 2%, 3%, 4%, 5%, or 10% (w/w) by weight of the total weight of the composition. In other aspects, the surfactant is less than 20%, 15%, 10%, or 5% (w/w) by weight of the total weight of the composition.
  • the cation may be sodium, potassium, lithium, magnesium, calcium, zinc and/or aluminum.
  • the compositions described herein may comprise at least one inorganic or C 1 -C 12 organic lithium salt has a molecular weight of 250 or less.
  • the compositions described herein may comprise lithium acetate, lithium carbonate, lithium formate, lithium sulfate, lithium citrate, lithium octanoate, lithium salicylate, lithium benzoate and/or lithium chloride.
  • compositions described herein do not comprise lithium salts, such as lithium acetate, lithium carbonate, lithium formate, lithium sulfate, lithium citrate, lithium octanoate, lithium salicylate, lithium benzoate and/or lithium chloride.
  • lithium salts such as lithium acetate, lithium carbonate, lithium formate, lithium sulfate, lithium citrate, lithium octanoate, lithium salicylate, lithium benzoate and/or lithium chloride.
  • the liquid compositions described herein may include one or more rheology modifiers.
  • the rheology modifier according to the present invention lack hydroxyl groups having a pKa above 13, tested in water at 25° C.
  • the rheology modifier is silica, silicate, or precipitated silica.
  • the rheology modifier comprises at least 1%, 2%, 3%, 4%, 5%, or 10% (w/w) by weight of the total weight of the composition. In other aspects, the rheology modifier is less than 20%, 15%, 10%, or 5% (w/w) by weight of the total weight of the composition.
  • the methods generally comprise mixing the pesticide with at least one or more inert ingredients (e.g., diluent, surfactant, and/or rheology modifier).
  • inert ingredients e.g., diluent, surfactant, and/or rheology modifier.
  • the ingredients are blended to ensure complete solubilization.
  • multi-phase liquid compositions sufficient energy is applied, to the ingredients or liquid composition or both, to achieve an average size of droplet or particle size of less than 50 microns, or more preferably less than 20 microns, or most preferably less than 10 microns.
  • the final liquid composition is achieved by mixing until homogeneous.
  • the pesticide compositions of the present invention are either (1) not diluted at the point of use (ready-to-use composition), or (2) diluted at the point of use and used immediately (concentrate composition).
  • the typical water dilution amounts prior to use range from 50:1 to 500:1.
  • Halosulfuron-methyl is particularly susceptible to degradation in water, and cannot be stored for any significant period of time.
  • the pesticide compositions of the invention could be an intermediate or a manufacture use product, used to formulate other pesticide compositions.
  • compositions described herein may be applied (e.g., via spraying, broadcast) to an area in need of the pesticide, such as a lawn, garden, turf grass, agriculture crops (e.g., corn, rice), non-crop areas, or ornamentals.
  • the pesticide such as a lawn, garden, turf grass, agriculture crops (e.g., corn, rice), non-crop areas, or ornamentals.
  • compositions may be applied pre-emergence or post-emergence to control undesirable vegetation, such as Alfalfa ( Medicago sativa ); Alligator weed ( Alternanthera philoxeroides ); Amaranth , palmer ( Amaranthus palmeri ); Amaranth , spiny ( Amaranth spinosus ); Artichoke, Jerusalem ( Helianthus tuberosus ); Barnyardgrass ( Echinochloa crusgalli ); Beggarweed, Florida ( Desmodium tortuosum ); Bindweed ( Calystegia sepium ); Bindweed, field ( Convolvulus arvensis ); Bindweed, hedge ( Calystegia sepium ); Buckwheat, wild; Polygonum convolvulus ); Buffalobur ( Solanum rostratum ); Burcucumber ( Sicyos angulatus ); Buttercup, hairy (
  • Alfalfa Medicago sativa
  • compositions described herein lose 5% (w/w) or less of the pesticide after storing the liquid composition for 8 weeks at 40° C. in a sealed container.
  • the compositions described herein comprise at least 95% (w/w) of the pesticide after storing the liquid composition for 8 weeks at 40° C. in a sealed container.
  • the percent loss is measured by quantitative chromatography, such as High Performance Liquid Chromatography (HPLC).
  • RADIA 7118 is 100% methyl laurate (CAS 111-82-0).
  • STEPOSOL C-48 is methyl laurate 55%, or Stepan C-48.
  • EMERSOL 213 is oleic acid, crude and single distilled.
  • the components include oleic acid 73%, C 14-17 fatty acid; 9%, linoleic acid 8%, palmitoleic acid 6%, myristoleic acid 3%, linolenic acid 1%, 2,6-Di-tert-butyl-4-methylphenol 0.01-0.02%
  • Radia 7060 is 100% methyl oleate, C 16-18 and C 18 unsaturated methyl esters.
  • Stepan 108 is caprylic/capric triglycerides (mixed decanoate and octanoate), 90-100% purity.
  • Stepanol ME-DRY is sulfuric acid, mono-C 10-16 -alkylesters, sodium salts (90-100%).
  • Stepwet 60 OE is sodium dioctyl sulfosuccinate (DOSS) (55-65%), methyl oleate (35-45%).
  • KPhosphate MB/DB is abbreviation for Potassium Phosphate Monobasic+Potassium Phosphate Dibasic. As noted by the asterisk in the table, this component is a buffering agent, not a surfactant.
  • Polyethylene glycol monotridecyl ether phosphate (90-100%); phosphoric acid (1- ⁇ 3%); and other compounds below reportable levels (1- ⁇ 3%).
  • Nanocol 90G is sodium dodecylbenzene sulfonate.
  • the components are Sodium (C 10-16 ) benzenesulfonate 90-93%; Sodium sulfate 5%; Sodium chloride ⁇ 1%; Other components below reportable levels (1- ⁇ 3%).
  • Atlox Metasperse 550-5-PW (WD) is acrylic-styrene copolymer salt.
  • Hi-Sil T600 is silica, amorphous, precipitated and gel.
  • the inventors sought to determine whether two sulfonylurea pesticides, thifensulfuron-methyl and halosulfuron-methyl, exhibit the same or different stability when formulated with the same inert ingredients.
  • the diluent(s), surfactant(s), and rheology modifier(s) were added to a suitable container and mixed. During mixing, thifensulfuron-methyl technical powder was slowly added, achieving a slightly viscous, opaque, off-white liquid. This composition was aged for 8 weeks at 40° C. Thifensulfuron-methyl was found to be stable in this composition (i.e., less than 5% w/w relative loss), contrary to the result with halosulfuron-methyl (Composition #7, Table 3).
  • the diluent(s), surfactant(s), and rheology modifier(s) were added to a suitable container and mixed. During mixing, halosulfuron-methyl technical powder was slowly added, achieving a slightly viscous, opaque, off-white liquid.
  • the testing was performed in California, USA at a controlled facility utilizing 2 ft 2 microplots of established bermudagrass ( Cyperus esculentus , var. TIF 419) sod.
  • Five Cyperus esculentus nutlets were transplanted into each of six microplots, representing six replications of each treatment.
  • the yellow nutsedge were allowed to mature to a stage consisting of three to six leaves prior to application of the treatment.
  • the components of each of the chemical treatments were formed as tank mixes in water, and applied as a foliar application to the microplots utilizing a backpack mounted hand held sprayer, pressurized with CO 2 .

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Liquid compositions of chemically unstable pesticides and methods of using the same are provided.

Description

    FIELD
  • Liquid pesticide compositions having enhanced stability, and methods of using the same are provided.
    • BACKGROUND
  • Liquid compositions are desirable since they facilitate easy volumetric measurement and transfer. This advantage can be realized for in-process liquid intermediates or final liquid compositions. Liquid compositions can be single-phase or multi-phase compositions, including emulsions, suspensions, solutions, etc. Common ingredients in liquid compositions contain hydroxy-functionality in the diluents, solvents, surfactants, and/or rheology modifiers, etc. These common ingredients which contain hydroxy-functionality include water, alcohols, glycols, alkoxylated surfactants, etc.
  • Certain pesticides are known to be chemically unstable. These pesticides exhibit unacceptable loss in stored liquid compositions. A chemically unstable pesticide generally has a greater than 5% (w/w) relative loss of that pesticide after storing the liquid composition for 8 weeks at 40° C. (measured using quantitative chromatography, such as HPLC). Chemically unstable liquid compositions are usually not commercially successful since liquid compositions are typically stored at 40° C. or higher.
  • The most common composition types for chemically unstable pesticides are solid compositions, such as a water-dispersible powder (WP), water-soluble powder (SP), water-dispersible granule (WG), water-soluble granule (SG), or broadcast-type ready-to-use granule (G). These compositions seek to avoid/minimize liquid-based contact of the pesticide with ingredients commonly used to make liquid compositions, and thereby maximize chemical stability of the pesticide by avoiding liquid compositions. The existence of commercially successful solid compositions for chemically unstable pesticides implies that liquid compositions do not have acceptable storage stability.
  • U.S. Publication No. 2011/0166023 discloses an herbicidal composition comprising a) at least one ALS-inhibiting herbicide; b) at least one HPPD-inhibiting herbicide; and c) at least one saturated or unsaturated fatty acid. The publication asserts that the use of a saturated or unsaturated fatty acid may chemically stabilize an herbicidal composition comprising at least one sulfonylurea herbicide and at least one HPPD-inhibiting herbicide. However, while the use of certain fatty acids showed improved stability for several HPPD-inhibiting herbicides, almost every sulfonylurea herbicide tested had an unacceptable storage stability (over 5% (w/w) relative loss after storage for 47 days at 40° C.).
  • A need exists for a stable liquid pesticide (e.g. herbicidal) compositions particularly sulfonylurea herbicides exhibiting less than 5% (w/w) relative loss of the active herbicide upon storage at least 47 days at 40° C.
    • SUMMARY OF VARIOUS ASPECTS OF THE DISCLOSURE
  • Liquid pesticide compositions and methods of making and using the same are provided. The liquid pesticide composition comprises a) halosulfuron-methyl; b) one or more diluent(s), where the diluent(s) is a liquid comprising: i) a first carbon structure of at least six carbon atoms optionally including one or more heteroatom(s), the first carbon structure being linear, branched, cyclic or aromatic; ii) optionally one or more glyceryl, carbonyl, phenyl, sulfonyl, or phosphonyl group(s) on the first carbon structure, wherein the organic diluent(s) lack hydroxyl group(s) on the first carbon structure unless they are part of the optional carbonyl, phenyl, sulfonyl, or phosphonyl group(s); c) optionally, one or more surfactant(s), wherein the one or more surfactant(s) comprise: i) a second carbon structure of at least six carbon atoms optionally including one or more heteroatom(s), wherein the second carbon structure is linear, branched, cyclic or aromatic; ii) optionally one or more glyceryl, carbonyl, phenyl, sulfonyl, or phosphonyl group(s) on the second carbon structure, wherein the surfactant(s) lack hydroxyl group(s) on the second carbon structure unless they are part of the optional phenyl, carbonyl, sulfonyl, or phosphonyl group(s); d) optionally, one or more rheology modifier(s); e) optionally, one or more buffering agent(s); wherein the liquid pesticide composition exhibits 5% (w/w) or less loss of halosulfuron-methyl upon storage for 8 weeks at 40° C. measured using quantitative chromatography.
  • The liquid pesticide composition may include 0.01-40% (w/w) of one or more pesticide(s), 40-95% (w/w) of one or more diluent(s), 0-20% (w/w) of one or more surfactant(s), and 0-10% (w/w) of one or more rheology modifier(s). In another embodiment, the liquid pesticide composition may include 5-30% (w/w) of one or more pesticide(s), 40-90% (w/w) of one or more diluent(s), 5-10% (w/w) of one or more surfactant(s), and 0-5% (w/w) of one or more rheology modifier(s). In another embodiment, the liquid pesticide composition may include 20-30% (w/w) of one or more pesticide(s), 40-82% (w/w) of one or more diluent(s), 5-10% (w/w) of one or more surfactant(s), and 3-8% (w/w) of one or more rheology modifier(s).
  • In addition to halosulfuron-methyl, the liquid pesticide composition may include one or more chemically stable pesticide(s), including Benzobicyclon, Dicamba, and/or Prosulfuron. In one embodiment, the rheology modifier may comprise silica.
  • In one embodiment, the surfactant is an acid selected from oleic, caprylic, decanedioic, or linolenic, or a salt thereof. The surfactant may also be a salt of the acid selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid.
  • In one embodiment, the surfactant comprises at least one glyceryl group. The surfactant may be selected from tricaprylate glycerol, trioleate glycerol, tristearate glycerol, di-lineolate/monostearate glycerol, or mixtures thereof. The glyceryl may include a salt of carbonyl, sulfonyl, or phosphonyl, in which case any OH groups associated with the carbonyl, sulfonyl, or phosphonyl would not lead to degradation. However, an OH group associated with the glyceryl-moiety itself, such as in the case of a mono- or di-glyceride would lead to instability.
  • In one embodiment, the surfactant may comprise a sulfonyl group. The surfactant may be selected from mono/di oleyl sulfate, lauryl sulfate, dodecylbenzene sulfonate, oleyl sulfonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenesulfonate, or a salt thereof. The surfactant may also be a salt of the sulfate or sulfonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the sulfate or sulfonate.
  • In one embodiment, the surfactant may comprise at least one phosphonyl group. The surfactant may be a phosphate or phosphonate selected from mono/di oleyl phosphonate, lauryl phosphonate, dodecylbenzene phosphonate, oleyl phosphonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenephosphonate, and salts thereof. The surfactant may also be a salt of the phosphate or phosphonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the phosphate or phosphonate.
  • In a particular embodiment, the liquid pesticide composition may comprise 0.01-40% (w/w) halosulfuron-methyl; 40-95% (w/w) of one or more diluent(s); 0-20% (w/w) of one or more surfactant(s) wherein the surfactant is selected from sodium oleate, mono-C10-16-alkylesters, calcium lignosulfonate, sodium dioctyl sulfosuccinate, potassium phosphate monobasic/potassium phosphate dibasic, phosphate ester, sodium dodecylbenzene sulfonate, acrylic-styrene copolymer salt, or mono tertiary amine-PEG-trimerate, or mixtures thereof; and 0-10% (w/w) rheology modifier.
  • In a particular embodiment, the liquid pesticide composition may comprise 20-30% (w/w) halosulfuron-methyl; 40-82% (w/w) of one or more diluent(s); 5-10% (w/w) of one or more surfactant(s), wherein the surfactant is selected from sodium oleate, mono-C10-16-alkylesters, calcium lignosulfonate, sodium dioctyl sulfosuccinate, potassium phosphate monobasic/potassium phosphate dibasic, phosphate ester, sodium dodecylbenzene sulfonate, acrylic-styrene copolymer salt, or mono tertiary amine-PEG-trimerate, or mixtures thereof; and 3-8% (w/w) of one or more rheology modifier(s).
  • Methods for controlling pest(s) in a lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals are also provided. In one aspect, the method comprises applying any of the liquid pesticide compositions described herein to the lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals. In one aspect, the crop field may be selected from field corn, field corn grown for seed, grain sorghum (milo), rice, sugarcane, fallow ground, cotton, or dry beans, or combinations thereof.
  • In a particular aspect, the liquid pesticide composition comprises halosulfuron-methyl and the pests may include undesired vegetation selected from Alfalfa (Medicago sativa); Alligator weed (Alternanthera philoxeroides); Amaranth, palmer (Amaranthus palmeri); Amaranth, spiny (Amaranth spinosus); Artichoke, Jerusalem (Helianthus tuberosus); Barnyardgrass (Echinochloa crusgalli); Beggarweed, Florida (Desmodium tortuosum); Bindweed (Calystegia sepium); Bindweed, field (Convolvulus arvensis); Bindweed, hedge (Calystegia sepium); Buckwheat, wild; Polygonum convolvulus); Buffalobur (Solanum rostratum); Burcucumber (Sicyos angulatus); Buttercup, hairy (Ranunculus sardous); California arrowhead (Sagittaria montevidensis); Carpetweed (Mollugo verticillata); Chamomile, mayweed (Anthemis cotula); Chervil, bur (Anthriscus scandicina); Chickweed, common (Stellaria media); Chickweed, mouse ear (Cerastium vulgatum); Clover, white (Dutch) (Trifolium repens); Cocklebur, common (Xanthium strumarium); Copperleaf, hophornbeam (Acalypha ostryifolia); Corn Spurry (Spergula arvensis); Cutleaf groundcherry (Physalis angulata); Dandelion, common (Taraxacum officinale); Dayflower (Commelina erecta); Dayflower, spreading (Commelina diffusa); Deadnettle, purple (Lamium purpureum); Devils Claw (Proboscidea louisianica); Dogbane, hemp (Apocynum cannabinum); Ducksalad (Heteranthera limosa); Early Water grass (Echinochloa oryzoides); Eclipta (Ecilpta prostrata); Eveningprimrose, cutleaf (Oenothera laciniata); Fiddleneck, coast (Amsinckia intermedia); Fleabane, Philadelphia (Erigeron philadelphicus); Flixweed (Descurainia Sophia); Galinsoga (Galinsoga spp.); Galinsoga (Galinsoga); Galinsoga, hairy (Galinsoga quadriradiata); Garlic, wild (Allium vineale); Golden crownbeard (Verbesina encelioides); Goose foot (Chenopodium californicum); Gromwell, corn (Lithospermum arvense); Groundsel, common (Senecio vulgaris); Henbit (Lamium amplexicaule); Horsenettle (Solanum carolinense); Horsetail (Equisetum arvense); Horseweed (Marestail) (Conyza canadensis); Horseweed/Marestail (Erigeron canadensis); Jimsonweed (Datura stramonium); Jointvetch (Aeschynomene virginica); Knotweed, prostrate (Polygonum aviculare); Kochia (Kochia scoparia); Kyllinga, Annual (Kyllinga sesquiflorus); Kyllinga, Green (Kyllinga breviflora); Ladysthumb (Polygonum persicaria); Lambsquarter, common (Chenopodium album); Late Watergrass/Rice Mimic (Echinochloa phyllopogon); Lettuce, miners (Claytonia perfoliata); Lettuce, prickly (Lactuca serriola); Mallow, common (Malva neglecta); Mallow, Venice (Hibiscus trionum); Mayweed chamomile (dog fennel) (Anthemis cotula); Milkweed, common (Asclepias syriaca); Milkweed, honeyvine (Ampelamus albidus); Monochoria (Monochoria spp); Morningglory, ivyleaf (Ipomoea hederacea); Morningglory, pitted (Ipomoea lacunosa); Morningglory, smallflower (Jacquemontia tamnifolia); Morningglory, tall & Ivyleaf (Ipomoea spp.); Morningglory, tall (Ipomoea purpurea); Mustard, blue (Chorispora tenella); Mustard, tumble (Sisymbrium altissimum); Mustard, wild (Sinapis arevensis); Nightshade, black (Solanum spp.); Nutsedge, Purple (Cyperus rotundus); Nutsedge, Yellow (Cyperus esculentus); Passionflower, maypop (Passiflora incarnata); Pennycress, field (Thlaspi arvense); Pepperweed, field (Lepidium campestre); Pepperweed, Virginia (Lepidium virginicum); Pigweed, redroot (Amarunthus retrofiexus); Pigweed, smooth (Amaranthus hybridus); Pigweed, tumbl (Amaranthus hybridus); Pineappleweed (Matricaria discoidea); Plantain (Plantago major); Pokeweed, common (Phytolacca Americana); Puncturevine (Tibulus terrestris); Purslane (Portulaca oleracea); Purslane, common (Portulaca oleracea); Purslane, horse (Trianthema portulacastrum); Pursley, Florida (Richardia scabra); Radish, wild (Raphanus raphanistrum); Ragweed, common (Ambrosia artemisiifolia); Ragweed, giant (Ambrosia trifida); Redstem (Ammania auriculata); Ricefield bulrush (Scirpus mucronatus); Sesbania, hemp (Sesbania exaltata); Sharppoint fluvellin*, (Kickxia elatine); Shepherd's purse (Capsella bursa-pastoris); Sicklepod (Cassia obtusifolia); Sida, prickly (Sida spinosa); Smallflower umbrella sedge (Cyperus difformis); Smartweed, Annual (Polygonum spp.); Smartweed, Pennsylvania (Polyfonum pennsylvanicum); Sowthistle, annual (Sonchus oleraceus); Sprangletop (Leptochloa fascicularis); Sun flower (Helianthus annuus); Sun flower (Helianthus spp.); Tansymustard (Descurainia pinnata); Texasweed (Caperonia palustris); Thistle, Canada (Cirsium arvense); Thistle, Russian (Salsola iberica); Velvetleaf (Abutilan theophrasti); Wallflower, bushy (Erysimum repandum); Water hyssop (Bacopa. spp); Waterhemp, common (Amaranthus rudis); Waterhemp, tall2 (Amaranthus tuberculatus); Waterhemp (Amaranthus spp); Willow herb, common (Epilobium ciliatum); Willowherb (Epilobium ciliatum); Yellowcress, creeping (Rorippa sylvestris), or combinations thereof.
    • BRIEF DESCRIPTION OF THE FIGURES
  • FIG. 1 shows trial data of two inventive compositions and a commercial herbicide for control of Yellow Nutsedge (Cyperus esculentus).
    •  DETAILED DESCRIPTION OF VARIOUS ASPECTS OF THE DISCLOSURE
  • The present inventors have found that halosulfuron-methyl, may be made more stable in liquid compositions by formulating those pesticides with particular diluents and/or surfactants. The liquid compositions generally comprise halosulfuron-methyl and at least one diluent, and optionally at least one surfactant and/or rheology modifier. The diluent, surfactant, and rheology modifier are generally inert ingredients. The inventors have found, however, that the presence of certain types of hydroxyl groups on these components leads to unstable compositions. The compositions described herein lose less than 5% (w/w) of halosulfuron-methyl after storing the liquid composition for 8 weeks at 40° C. in a sealed container. The compositions may be applied to any desired environment, such as a lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals.
  • The presence of certain hydroxyl groups leads to instability of halosulfuron-methyl pesticide compositions. However, this instability does not result from the presence of OH components that are acidic due to adjacent electron withdrawing groups (e.g., carbonyl, sulfonyl, phosphonyl), or groups where negative charge is spread over a large volume of the group (e.g., phenyl). Rather, particular OH groups having a pKa above 13 have been found to lead to instability when present in a halosulfuron-methyl composition. In the case of surfactants, where the OH group resembles ethanol (pKa=16), as in an OH found on a hydrocarbon chain or at any position on a fatty acid except the carbonyl group, the inventors have found instability. Thus, stability may be predicted by the lack of OH groups on a surfactant compound having an estimated pKa (from tables) of greater than 13.
  • As used herein, the pKa may be estimated by looking to standard charts showing estimated pKa values for specific OH groups, such as the following table:
  • TABLE 1
    Group Estimated pKa
    Sulfuric Strong Acid
    Carboxylic 4
    Phosphoric 2.2, 7.2, 12.4
    Phenol 10
    Glycerol 14.4
    Alkanol 15-18
  • The following surfactant compounds include the type of alcohol or hydroxyl group that the inventors have found leads to instability of halosulfuron-methyl pesticide compositions:
  • TABLE 2
    Compounds Leading to Instability
    Compound Name Formula
    Ricinoleic Acid
    Figure US20220132854A1-20220505-C00001
    3-Hydroxyoctadecanoic acid
    Figure US20220132854A1-20220505-C00002
    Polyglycerol-10 distearate
    Figure US20220132854A1-20220505-C00003
    Alcohol ethoxylate CH3—[CH2]y—[OCH2CH2]x—OH
    Nonylphenol Ethoxylate
    Figure US20220132854A1-20220505-C00004
    Poly(oxy-1,2-ethanediyl), α-[3-[1,3,3,3-tetramethyl1- [(trimethylsilyl)oxy]-1- disiloxanyl]propyl]-ω- hydroxyl
    Figure US20220132854A1-20220505-C00005
    Tristyrylphenol ethoxylate
    Figure US20220132854A1-20220505-C00006
  • Each of the compounds above includes a hydroxyl group present on a carbon chain suggesting a pKa comparable to that of ethanol. The inventors have observed that such compounds, whether used as a surfactant on their own, or present as an impurity or other component in a surfactant or other component of the composition, leads to instability of a halosulfuron-methyl composition containing such compound or compounds.
  • The following table shows seven compositions where the amount of halosulfuron-methyl lost was greater than 5% of the pesticide after storing the liquid composition for 8 weeks at 40° C. in a sealed container.
  • TABLE 3
    Unstable Halosulfuron-Methyl Compositions
    Surfactant
    Diluent (liquid) Caprol PGE 860 Silwet L-77
    Stepan 108 (1,2,3-Propanetriol, (siloxane
    Halosulfuron- RADIA 7118 (>90% caprylic/ homopolymer, PEG 8000 Polyaldo 3-1-S polyalkyleneoxide
    methyl (>95% Methyl capric (9Z)-9- (Polyethylene (Polyglyceryl-3 copolymer, >50%
    (purity 99%) Laurate) triglyceride) octadecenoate) glycol) stearate) methyl-terminated)
    1 13.6 86.4
    2 12.5 87.5
    3 15.0 85.0
    4 5.0 90.0 5.0
    5 5.0 90.0
     6* 20.0 69.0
    7 20.0 69.0
    Surfactant
    SOPROPHOR ® Cirrasol G 1086
    TSP 724 Hypermer NV-LQ-AP RM
    (alkoxylated B210 Altox (polyoxyethylene Hi-Sil T600
    polyaryl STEPFAC (ABA block Metasperse (40) sorbitol (silica,
    phenol, >99%) 8181 copolymer) 550 S-PW(WD) hexaoleate) amorphous)
    1
    2
    3
    4
    5 5.0
     6* 5.0 2.0 4.0
    7 2.0 5.0 4.0
    *This composition was not tested for the full eight weeks due to physical instability.
    “RM” stands for rheology modifier.
  • To test stability, the compositions were sealed in a container and stored for 8 weeks at 40° C. The relative percentage loss of halosulfuron-methyl was calculated using high performance liquid chromatography (HPLC). The samples were extracted with solvents and then analyzed with reverse phase HPLC equipped with UV detector. The response from the detector are peak areas (mAu*s). The peak areas were correlated with percentage active ingredients through a standard calibration curve. The percentage of pesticide was calculated through the calibration curve. Chemically stable compositions are those compositions that had less than 5% (w/w) relative loss of halosulfuron-methyl after 8 weeks of storage at 40° C.
  • The seven compositions (described above) that failed can be described as follows: (1) contains unacceptable alcoholic-hydroxy; (2) contains unacceptable hydroxy-termination from polyethylene glycol synthesis; (3) contains unacceptable alcoholic-hydroxy; (4) contains CAS #67674-67-3 (Silwet L-77) with unacceptable hydroxy functionality; (5) contains unacceptable hydroxy-termination of the alkoxylate; (6) contains unacceptable hydroxy-termination from polyethylene glycol synthesis; and (7) contains unacceptable hydroxy-termination from polyethylene glycol synthesis. The inventive compositions described herein lack such alcohols in any of the components, particularly the surfactant where such alcohols are a common feature or are present as a result of the manufacturing process, or incomplete purification. These alcohol-containing compounds need to be removed or avoided in order to achieve a stable halosulfuron-methyl composition.
  • The present inventors have found that molecules having instability-producing OH groups even if present in small quantities can render the entire composition unstable. For example, the composition Silwet L-77 (siloxane polyalkyleneoxide copolymer, >50% methyl-terminated) leads to instability. In theory, methyl-terminated siloxanes should not have instability producing OH groups. However, the inventors have found that methyl-terminated siloxanes contain some OH-terminated siloxane molecules. Even if present in small amounts, the OH-terminated siloxanes result in instability of the overall composition.
  • The instability producing OH groups lead to instability regardless of whether they are a minor component in a much larger molecule. For example, the inventors have observed instability for polyethylene glycol 8000 (PEG8000) even though the entire 8000 MW polymer has only a single instability producing OH group. In addition, PEG and polypropylene glycol (PPG) are known impurities in many compounds such as fatty alcohol ethoxylates (FAEs). See Lee et al., “Quantification of Poly (Ethylene Glycol) and Poly (Propylene Glycol) in Alkoxylated Surfactants.” Accordingly, it is important to ensure that these OH groups are not present as part of an impurity molecule.
  • The liquid compositions of the present invention which are described herein comprise halosulfuron-methyl (CAS 100784-20-1) either alone or in combination with another pesticide, such as a combination of halosulfuron-methyl and Benzobicyclon (CAS 156963-66-5). Other pesticides may be used in combination with halosulfuron-methyl, such as for example Prosulfuron (CAS 94125-34-5) or Dicamba (CAS 1918-00-9). The halosulfuron-methyl comprises at least 0.01%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, or 40% (w/w) by weight of the total weight of the composition. In other aspects, the chemically unstable pesticide is less than 40%, 35%, 30%, 25%, 20%, 15%, or 10% (w/w) of by weight of the total weight of the composition.
  • The liquid compositions described herein comprise one or more diluents. The diluent is a liquid contributing toward dissolving or suspending the halosulfuron-methyl active ingredient into an overall liquid herbicidal composition. The diluent may optionally have a functional group providing surfactant properties, or other desired properties. Alternatively, the diluent may simply be a liquid capable of dissolving or carrying the halosulfuron-methyl. As with other components of the invention, the diluent must lack hydroxyl groups except those associated with an electron withdrawing or electron dense functional group such as a carbonyl, sulfonyl, phosphonyl or phenyl group. The diluent therefore may comprise at least one of alkyl carboxylic acids, alkyl carboxylate salts, alkenyl carboxylic acids, alkenyl carboxylate salts, aryl carboxylic acids, aryl carboxylate salts, alkyl sulfuric acids, alkyl sulfate salts, alkenyl sulfuric acids, alkenyl sulfate salts, aryl sulfuric acids, aryl sulfate salts, alkyl sulfonic acids, alkyl sulfonate salts, alkenyl sulfonic acids, alkenyl sulfonate salts, aryl sulfonic acids, aryl sulfonate salts, alkyl phosphate ester with free acids, alkyl phosphate ester with salts, alkenyl phosphate ester with free acids, alkenyl phosphate ester with salts, aryl phosphate ester with free acids, aryl phosphate ester with salts, alkyl phosphonate ester with free acids, alkyl phosphonate ester with salts, alkenyl phosphonate ester with free acids, alkenyl phosphonate ester with salts, aryl phosphonate ester with free acids, aryl phosphonate ester with salts, or a mixture thereof. In particular aspects, the diluent is oleic acid, oleic salt, sodium oleate, lauryl sulfate, sodium lauryl sulfate, lignosulfonate acid, lignosulfonate salt, calcium lignosulfonate, dioctyl sulfosuccinate sodium salt in methyl oleate, sodium dioctyl sulfosuccinate, phosphate ester, ethoxylated phosphate ester, methyl ester, triglyceride, or a mixture thereof. The diluent comprises at least 35%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 97% (w/w) by weight of the total weight of the composition.
  • The liquid compositions described herein may include one or more surfactants. The surfactant may be as described above both a diluent and a surfactant. In that case, the surfactant must be a liquid. Alternatively, the surfactant may be a solid surfactant that can be added to the liquid diluent. In general, a surfactant will have a non-polar and polar (often ionic) group. The surfactant allows the overall composition to be more readily dispersed in water at the point of use. As with other components of the invention, the surfactant must lack hydroxyl groups except those associated with an electron withdrawing functional group such as a carbonyl, sulfonyl, phosphonyl or phenyl group. In other aspects, the surfactant comprises at least one of alkyl carboxylic acids, alkyl carboxylate salts, alkenyl carboxylic acids, alkenyl carboxylate salts, aryl carboxylic acids, aryl carboxylate salts, alkyl sulfuric acids, alkyl sulfate salts, alkenyl sulfuric acids, alkenyl sulfate salts, aryl sulfuric acids, aryl sulfate salts, alkyl sulfonic acids, alkyl sulfonate salts, alkenyl sulfonic acids, alkenyl sulfonate salts, aryl sulfonic acids, aryl sulfonate salts, alkyl phosphate ester with free acids, alkyl phosphate ester with salts, alkenyl phosphate ester with free acids, alkenyl phosphate ester with salts, aryl phosphate ester with free acids, aryl phosphate ester with salts, alkyl phosphonate ester with free acids, alkyl phosphonate ester with salts, alkenyl phosphonate ester with free acids, alkenyl phosphonate ester with salts, aryl phosphonate ester with free acids, aryl phosphonate ester with salts, or a mixture thereof. In particular aspects, the surfactant is oleic acid, oleic salt, sodium oleate, lauryl sulfate, sodium lauryl sulfate, lignosulfonate acid, lignosulfonate salt, calcium lignosulfonate, dioctyl sulfosuccinate sodium salt in methyl oleate, sodium dioctyl sulfosuccinate, phosphate ester, ethoxylated phosphate ester, mono tertiary amine-PEG-trimerate, or a mixture thereof. The surfactant comprises at least 1%, 2%, 3%, 4%, 5%, or 10% (w/w) by weight of the total weight of the composition. In other aspects, the surfactant is less than 20%, 15%, 10%, or 5% (w/w) by weight of the total weight of the composition.
  • In any of the inert ingredients described herein (e.g., diluent, surfactant) where the ingredient is a salt, the cation may be sodium, potassium, lithium, magnesium, calcium, zinc and/or aluminum. In one aspect, the compositions described herein may comprise at least one inorganic or C1-C12 organic lithium salt has a molecular weight of 250 or less. In other aspects, the compositions described herein may comprise lithium acetate, lithium carbonate, lithium formate, lithium sulfate, lithium citrate, lithium octanoate, lithium salicylate, lithium benzoate and/or lithium chloride. Alternatively, the compositions described herein do not comprise lithium salts, such as lithium acetate, lithium carbonate, lithium formate, lithium sulfate, lithium citrate, lithium octanoate, lithium salicylate, lithium benzoate and/or lithium chloride.
  • The liquid compositions described herein may include one or more rheology modifiers. In one aspect, the rheology modifier according to the present invention lack hydroxyl groups having a pKa above 13, tested in water at 25° C. In particular aspects, the rheology modifier is silica, silicate, or precipitated silica. The rheology modifier comprises at least 1%, 2%, 3%, 4%, 5%, or 10% (w/w) by weight of the total weight of the composition. In other aspects, the rheology modifier is less than 20%, 15%, 10%, or 5% (w/w) by weight of the total weight of the composition.
  • Methods of making the compositions described herein are provided. The methods generally comprise mixing the pesticide with at least one or more inert ingredients (e.g., diluent, surfactant, and/or rheology modifier). For single-phase liquid compositions, the ingredients are blended to ensure complete solubilization. For multi-phase liquid compositions, sufficient energy is applied, to the ingredients or liquid composition or both, to achieve an average size of droplet or particle size of less than 50 microns, or more preferably less than 20 microns, or most preferably less than 10 microns. The final liquid composition is achieved by mixing until homogeneous.
  • The pesticide compositions of the present invention are either (1) not diluted at the point of use (ready-to-use composition), or (2) diluted at the point of use and used immediately (concentrate composition). The typical water dilution amounts prior to use range from 50:1 to 500:1. Halosulfuron-methyl is particularly susceptible to degradation in water, and cannot be stored for any significant period of time.
  • The pesticide compositions of the invention could be an intermediate or a manufacture use product, used to formulate other pesticide compositions.
  • Methods of using the compositions described herein are provided. For example, the compositions described herein may be applied (e.g., via spraying, broadcast) to an area in need of the pesticide, such as a lawn, garden, turf grass, agriculture crops (e.g., corn, rice), non-crop areas, or ornamentals. For example, the compositions (e.g., comprising halosulfuron-methyl) may be applied pre-emergence or post-emergence to control undesirable vegetation, such as Alfalfa (Medicago sativa); Alligator weed (Alternanthera philoxeroides); Amaranth, palmer (Amaranthus palmeri); Amaranth, spiny (Amaranth spinosus); Artichoke, Jerusalem (Helianthus tuberosus); Barnyardgrass (Echinochloa crusgalli); Beggarweed, Florida (Desmodium tortuosum); Bindweed (Calystegia sepium); Bindweed, field (Convolvulus arvensis); Bindweed, hedge (Calystegia sepium); Buckwheat, wild; Polygonum convolvulus); Buffalobur (Solanum rostratum); Burcucumber (Sicyos angulatus); Buttercup, hairy (Ranunculus sardous); California arrowhead (Sagittaria montevidensis); Carpetweed (Mollugo verticillata); Chamomile, mayweed (Anthemis cotula); Chervil, bur (Anthriscus scandicina); Chickweed, common (Stellaria media); Chickweed, mouse ear (Cerastium vulgatum); Clover, white (Dutch) (Trifolium repens); Cocklebur, common (Xanthium strumarium); Copperleaf, hophornbeam (Acalypha ostryifolia); Corn Spurry (Spergula arvensis); Cutleaf groundcherry (Physalis angulata); Dandelion, common (Taraxacum officinale); Dayflower (Commelina erecta); Dayflower, spreading (Commelina diffusa); Deadnettle, purple (Lamium purpureum); Devils Claw (Proboscidea louisianica); Dogbane, hemp (Apocynum cannabinum); Ducksalad (Heteranthera limosa); Early Water grass (Echinochloa oryzoides); Eclipta (Ecilpta prostrata); Eveningprimrose, cutleaf (Oenothera laciniata); Fiddleneck, coast (Amsinckia intermedia); Fleabane, Philadelphia (Erigeron philadelphicus); Flixweed (Descurainia Sophia); Galinsoga(Galinsoga spp.); Galinsoga(Galinsoga); Galinsoga, hairy (Galinsoga quadriradiata); Garlic, wild (Allium vineale); Golden crownbeard (Verbesina encelioides); Goosefoot (Chenopodium californicum); Gromwell, corn (Lithospermum arvense); Groundsel, common (Senecio vulgaris); Henbit (Lamium amplexicaule); Horsenettle (Solanum carolinense); Horsetail (Equisetum arvense); Horseweed (Marestail) (Conyza canadensis); Horseweed/Marestail (Erigeron canadensis); Jimsonweed (Datura stramonium); Jointvetch (Aeschynomene virginica); Knotweed, prostrate (Polygonum aviculare); Kochia(Kochia scoparia); Kyllinga, Annual (Kyllinga sesquiflorus); Kyllinga, Green (Kyllinga breviflora); Ladysthumb (Polygonum persicaria); Lambsquarter, common (Chenopodium album); Late Watergrass/Rice Mimic (Echinochloa phyllopogon); Lettuce, miners (Claytonia perfoliata); Lettuce, prickly (Lactuca serriola); Mallow, common (Malva neglecta); Mallow, Venice (Hibiscus trionum); Mayweed chamomile (dog fennel) (Anthemis cotula); Milkweed, common (Asclepias syriaca); Milkweed, honeyvine (Ampelamus albidus); Monochoria(Monochoria spp); Morningglory, ivyleaf (Ipomoea hederacea); Morningglory, pitted (Ipomoea lacunosa); Morningglory, smallflower (Jacquemontia tamnifolia); Morningglory, tall & Ivyleaf (Ipomoea spp.); Morningglory, tall (Ipomoea purpurea); Mustard, blue (Chorispora tenella); Mustard, tumble (Sisymbrium altissimum); Mustard, wild (Sinapis arevensis); Nightshade, black (Solanum spp.); Nutsedge, Purple (Cyperus rotundus); Nutsedge, Yellow (Cyperus esculentus); Passionflower, maypop (Passiflora incarnata); Pennycress, field (Thlaspi arvense); Pepperweed, field (Lepidium campestre); Pepperweed, Virginia (Lepidium virginicum); Pigweed, redroot (Amarunthus retrofiexus); Pigweed, smooth (Amaranthus hybridus); Pigweed, tumbl (Amaranthus hybridus); Pineappleweed (Matricaria discoidea); Plantain (Plantago major); Pokeweed, common (Phytolacca Americana); Puncturevine (Tibulus terrestris); Purslane (Portulaca oleracea); Purslane, common (Portulaca oleracea); Purslane, horse (Trianthema portulacastrum); Pursley, Florida (Richardia scabra); Radish, wild (Raphanus raphanistrum); Ragweed, common (Ambrosia artemisiifolia); Ragweed, giant (Ambrosia trifida); Redstem (Ammania auriculata); Ricefield bulrush (Scirpus mucronatus); Sesbania, hemp (Sesbania exaltata); Sharppoint fluvellin*, (Kickxia elatine); Shepherd's purse (Capsella bursa pastoris); Sicklepod (Cassia obtusifolia); Sida, prickly (Sida spinosa); Smallflower umbrella sedge (Cyperus difformis); Smartweed, Annual (Polygonum spp.); Smartweed, Pennsylvania (Polyfonum pennsylvanicum); Sowthistle, annual (Sonchus oleraceus); Sprangletop (Leptochloa fascicularis); Sunflower (Helianthus annuus); Sun flower (Helianthus spp.); Tansymustard (Descurainia pinnata); Texasweed (Caperonia palustris); Thistle, Canada (Cirsium arvense); Thistle, Russian (Salsola iberica); Velvetleaf (Abutilan theophrasti); Wallflower, bushy (Erysimum repandum); Water hyssop (Bacopa. spp); Waterhemp, common (Amaranthus rudis); Waterhemp, tall (Amaranthus tuberculatus); Waterhemp (Amaranthus spp); Willow herb, common (Epilobium ciliatum); Willowherb (Epilobium ciliatum); and/or Yellowcress, creeping (Rorippa sylvestris), or combinations thereof.
  • Various aspects of the disclosure will now be particularly described by way of examples. The following descriptions of specific aspects are presented for purposes of illustration and description, and are not intended to be exhaustive of or to limit the disclosure to the precise compositions disclosed.
    • Examples 1-17
  • The compositions described herein lose 5% (w/w) or less of the pesticide after storing the liquid composition for 8 weeks at 40° C. in a sealed container. Alternatively, the compositions described herein comprise at least 95% (w/w) of the pesticide after storing the liquid composition for 8 weeks at 40° C. in a sealed container. The percent loss is measured by quantitative chromatography, such as High Performance Liquid Chromatography (HPLC).
  • The tradenames used in the following table describe particular products on the market at the time of filing this application. The following descriptions describe the content of these commercial compositions.
  • RADIA 7118 is 100% methyl laurate (CAS 111-82-0).
  • STEPOSOL C-48 is methyl laurate 55%, or Stepan C-48.
  • EMERSOL 213 is oleic acid, crude and single distilled. The components include oleic acid 73%, C14-17 fatty acid; 9%, linoleic acid 8%, palmitoleic acid 6%, myristoleic acid 3%, linolenic acid 1%, 2,6-Di-tert-butyl-4-methylphenol 0.01-0.02%
  • Radia 7060 is 100% methyl oleate, C16-18 and C18 unsaturated methyl esters.
  • Stepan 108 is caprylic/capric triglycerides (mixed decanoate and octanoate), 90-100% purity.
  • Stepanol ME-DRY is sulfuric acid, mono-C10-16-alkylesters, sodium salts (90-100%).
  • Borresperse CA, calcium lignosulfonate (≥92%).
  • Stepwet 60 OE is sodium dioctyl sulfosuccinate (DOSS) (55-65%), methyl oleate (35-45%).
  • KPhosphate MB/DB is abbreviation for Potassium Phosphate Monobasic+Potassium Phosphate Dibasic. As noted by the asterisk in the table, this component is a buffering agent, not a surfactant.
  • STEPFAC 8181 is a phosphate ester, n=6 of the formula:
  • Figure US20220132854A1-20220505-C00007
  • Polyethylene glycol monotridecyl ether phosphate (90-100%); phosphoric acid (1-<3%); and other compounds below reportable levels (1-<3%).
  • Nanocol 90G is sodium dodecylbenzene sulfonate. The components are Sodium (C10-16) benzenesulfonate 90-93%; Sodium sulfate 5%; Sodium chloride <1%; Other components below reportable levels (1-<3%).
  • Atlox Metasperse 550-5-PW (WD) is acrylic-styrene copolymer salt.
  • Mono Tertiary Amine-PEG-trimerate.
  • Hi-Sil T600 is silica, amorphous, precipitated and gel.
  • TABLE 4
    Stable Halosulfuron-Methyl Compositions
    Diluent (liquid)
    Active RADIA 7118 Surfactant/Buffering Agent
    Halosulfuron- or Steposol Emersol RADIA Stepan Sodium Stepanol
    Benzobicyclon methyl C-48 213 7060 108 Oleate ME-DRY
    1 5 95
    2 5 76 19
    3 5 90 5
    4 5 90
    5 5 90
    6 5 90
    7 5 92
    8 19 73
    9 30 56
    10 15 85
    11 5 5 90
    12 5 90
    13 20 69
    14 30 58
    15 25.5 5 60.5
    16 20 34 34
    17 30.4 6.1 51
    Surfactant/Buffering Agent
    Atlox Mono Tertiary RM
    Borresperse Stepwet KPhosphate STEPFAC Nanocol Metasperse Amine PEG Hi-Sil
    CA 60 OE MB/DB* 8181 90G 550-5-PW(WD) trimerate T600
    1
    2
    3
    4 5
    5 5
    6 5
    7 3
    8 5 3
    9 5 3 6
    10
    11
    12 5
    13 5 2 4
    14 4 3 5
    15 5 4
    16 5 2 5
    17 7 2.5 3
    “RM” stands for rheology modifier
    • Example 18
  • The inventors sought to determine whether two sulfonylurea pesticides, thifensulfuron-methyl and halosulfuron-methyl, exhibit the same or different stability when formulated with the same inert ingredients.
  • As shown in Table 3 (Unstable Halosulfuron-Methyl Compositions), Composition #7, halosulfuron-methyl was unstable. This composition was prepared again, except halosulfuron-methyl was replaced with thifensulfuron-methyl 98% as shown in Table 5:
  • TABLE 5
    Ingredient Weight
    Halosulfuron-methyl, 99% 20.0
    Diluent 69.0
    Surfactants 7.0
    Rheology Modifier 4.0
    Total 100%
  • The diluent(s), surfactant(s), and rheology modifier(s) were added to a suitable container and mixed. During mixing, thifensulfuron-methyl technical powder was slowly added, achieving a slightly viscous, opaque, off-white liquid. This composition was aged for 8 weeks at 40° C. Thifensulfuron-methyl was found to be stable in this composition (i.e., less than 5% w/w relative loss), contrary to the result with halosulfuron-methyl (Composition #7, Table 3).
    • Example 19
  • A study was conducted to evaluate the comparative efficacy of commercial SedgeHammer® (a solid composition of halosulfuron-methyl) and two liquid compositions corresponding to embodiments of the invention using components described in Table 4, for control of Cyperus esculentus, commonly referred to as “yellow nutsedge.” The inventive compositions tested are shown in Tables 6 and 7 below:
  • TABLE 6
    Inventive Composition A
    Ingredient Weight
    Halosulfuron-methyl 27
    Technical
    Diluent 60
    Surfactants 10
    Rheology Modifier 3
    Total 100%
  • TABLE 7
    Inventive Composition B
    Ingredient Weight
    Halosulfuron-methyl 22
    Technical
    Diluent 66
    Surfactants 7
    Rheology Modifier 5
    Total 100%
  • These two compositions used components shown in Table 4, and meet the criteria for stable compositions described herein.
  • The diluent(s), surfactant(s), and rheology modifier(s) were added to a suitable container and mixed. During mixing, halosulfuron-methyl technical powder was slowly added, achieving a slightly viscous, opaque, off-white liquid.
  • The testing was performed in California, USA at a controlled facility utilizing 2 ft2 microplots of established bermudagrass (Cyperus esculentus, var. TIF 419) sod. Five Cyperus esculentus nutlets were transplanted into each of six microplots, representing six replications of each treatment. The yellow nutsedge were allowed to mature to a stage consisting of three to six leaves prior to application of the treatment. The components of each of the chemical treatments were formed as tank mixes in water, and applied as a foliar application to the microplots utilizing a backpack mounted hand held sprayer, pressurized with CO2.
  • As shown in FIG. 1, similar efficacy was observed for the inventive liquid compositions A and B, and the commercially available solid halosulfuron-methyl composition, SedgeHammer®.
  • Other embodiments and uses of the compositions described herein will be apparent to those skilled in the art from consideration of the specification and methods disclosed herein. All references cited herein, including all U.S. and foreign patents and patent applications, are specifically and entirely hereby incorporated herein by reference. It is intended that the specification and examples be considered exemplary only.

Claims (43)

What is claimed is:
1. A liquid pesticide composition comprising:
a) halosulfuron-methyl;
b) one or more diluent(s), where the diluent(s) is a liquid comprising:
i) a first carbon structure of at least six carbon atoms optionally including one or more heteroatom(s), the first carbon structure being linear, branched, cyclic or aromatic;
ii) optionally one or more glyceryl, carbonyl, phenyl, sulfonyl, or phosphonyl group(s) on the first carbon structure,
wherein the organic diluent(s) lack hydroxyl group(s) on the first carbon structure unless they are part of the optional carbonyl, phenyl, sulfonyl, or phosphonyl group(s);
c) optionally, one or more surfactant(s), wherein the one or more surfactant(s) comprise:
i) a second carbon structure of at least six carbon atoms optionally including one or more heteroatom(s), wherein the second carbon structure is linear, branched, cyclic or aromatic;
ii) optionally one or more glyceryl, carbonyl, phenyl, sulfonyl, or phosphonyl group(s) on the second carbon structure,
wherein the surfactant(s) lack hydroxyl group(s) on the second carbon structure unless they are part of the optional carbonyl, phenyl, sulfonyl, or phosphonyl group(s);
d) optionally, one or more rheology modifier(s);
e) optionally, one or more buffer(s);
wherein the liquid pesticide composition exhibits 5% (w/w) or less loss of halosulfuron-methyl upon storage for 8 weeks at 40° C. measured using quantitative chromatography.
2. The liquid pesticide composition of claim 1, wherein the first carbon structure includes from 6 to 66 carbon atoms.
3. The liquid pesticide composition of claim 1 or 2, comprising:
0.01-40% (w/w) of one or more pesticide(s),
40-95% (w/w) of one or more diluent(s)
0-20% (w/w) of one or more surfactant(s), and
0-10% (w/w) of one or more rheology modifier(s).
4. The liquid pesticide composition according to any of the previous claims, comprising:
5-30% (w/w) of one or more pesticide(s),
40-90% (w/w) of one or more diluent(s)
5-10% (w/w) of one or more surfactant(s), and
0-5% (w/w) of one or more rheology modifier(s).
5. The liquid pesticide composition according to any of the previous claims, comprising:
20-30% (w/w) of one or more pesticide(s),
40-82% (w/w) of one or more diluent(s)
5-10% (w/w) of one or more surfactant(s), and
3-8% (w/w) of one or more rheology modifier(s).
6. The liquid pesticide composition according to any of the previous claims, further comprising one or more chemically stable pesticide(s).
7. The liquid pesticide composition according to any of the previous claims, wherein the chemically stable pesticide is Benzobicyclon.
8. The liquid pesticide composition according to any of the previous claims, wherein the rheology modifier comprises silica.
9. The liquid pesticide composition according to any one of claims 1-8, wherein the surfactant is an acid selected from oleic, caprylic, decanedioic, or linolenic, mono tertiary amine-PEG-trimerate, or a salt thereof.
10. The liquid pesticide composition of claim 9, wherein the surfactant is a salt of the acid selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid.
11. The liquid pesticide composition according to any one of claims 1-8, wherein the surfactant comprises at least one glyceryl group.
12. The liquid pesticide composition of claim 11, wherein the surfactant is selected from tricaprylate glycerol, trioleate glycerol, tristearate glycerol, di-lineolate/monostearate glycerol, or mixtures thereof.
13. The liquid pesticide composition according to any one of claims 1-8, wherein the surfactant comprises at least one sulfonyl group.
14. The liquid pesticide composition of claim 13, wherein the surfactant is a sulfate or a sulfonate selected from mono/di oleyl sulfate, lauryl sulfate, dodecylbenzene sulfonate, oleyl sulfonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenesulfonate, or a salt thereof.
15. The liquid pesticide composition of claim 13, wherein the surfactant is the salt of the sulfate or sulfonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the sulfate or sulfonate.
16. The liquid pesticide composition according to any one of claims 1-8, wherein the surfactant comprises at least one phosphonyl group.
17. The liquid pesticide composition of claim 16, wherein the surfactant is a phosphate or phosphonate selected from mono/dioleyl phosphonate, lauryl phosphonate, dodecylbenzene phosphonate, oleyl phosphonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenephosphonate, and salts thereof.
18. The liquid pesticide composition of claim 16, wherein the surfactant is salt of the phosphate or phosphonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the phosphate or phosphonate.
19. A liquid pesticide composition comprising:
0.01-40% (w/w) halosulfuron-methyl;
40-95% (w/w) of one or more diluent(s)
0-20% (w/w) of one or more surfactant(s) wherein the surfactant is selected from sodium oleate, mono-C10-16-alkylesters, calcium lignosulfonate, sodium dioctyl sulfosuccinate, potassium phosphate monobasic/potassium phosphate dibasic, phosphate ester, sodium dodecylbenzene sulfonate, acrylic-styrene copolymer salt, or mono tertiary amine-PEG-trimerate, or mixtures thereof; and
0-10% (w/w) rheology modifier.
20. A liquid pesticide composition comprising:
20-30% (w/w) halosulfuron-methyl
40-82% (w/w) of one or more diluent(s)
5-10% (w/w) of one or more surfactant(s), wherein the surfactant is selected from sodium oleate, mono-C10-16-alkylesters, calcium lignosulfonate, sodium dioctyl sulfosuccinate, potassium phosphate monobasic/potassium phosphate dibasic, phosphate ester, sodium dodecylbenzene sulfonate, acrylic-styrene copolymer salt, or mono tertiary amine-PEG-trimerate, or mixtures thereof; and
3-8% (w/w) of one or more rheology modifier(s).
21. A liquid pesticide composition comprising:
a) halosulfuron-methyl;
b) one or more diluent(s), where the diluent(s) is a liquid comprising:
i) a first carbon structure of at least six carbon atoms optionally including one or more heteroatom(s), the first carbon structure being linear, branched, cyclic or aromatic;
ii) optionally one or more glyceryl, carbonyl, phenyl, sulfonyl, or phosphonyl group(s) on the first carbon structure,
wherein the organic diluent(s) lack hydroxyl group(s) on the first carbon structure unless they are part of the optional carbonyl, phenyl, sulfonyl, or phosphonyl group(s);
c) one or more surfactant(s), wherein the one or more surfactant(s) comprise:
i) a second carbon structure of at least six carbon atoms optionally including one or more heteroatom(s), wherein the second carbon structure is linear, branched, cyclic or aromatic;
ii) optionally one or more glyceryl, carbonyl, phenyl, sulfonyl, or phosphonyl group(s) on the second carbon structure,
wherein the surfactant(s) lack hydroxyl group(s) on the second carbon structure unless they are part of the optional carbonyl, phenyl, sulfonyl, or phosphonyl group(s);
d) optionally, one or more rheology modifier(s);
e) optionally, one or more buffering agents(s);
wherein the liquid pesticide composition exhibits 5% (w/w) or less loss of halosulfuron-methyl upon storage for 8 weeks at 40° C. measured using quantitative chromatography.
22. The liquid pesticide composition of claim 21, wherein the first carbon structure includes from 6 to 66 carbon atoms.
23. The liquid pesticide composition of claim 21 or 22, comprising:
0.01-40% (w/w) of one or more pesticide(s),
50-97% (w/w) of one or more surfactant(s), and
0-10% (w/w) of one or more rheology modifier(s).
24. The liquid pesticide composition of claims 21-23, comprising:
5-30% (w/w) of one or more pesticide(s),
65-95% (w/w) of one or more surfactant(s), and
0-5% (w/w) of one or more rheology modifier(s).
25. The liquid pesticide composition of claims 21-24, comprising:
20-30% (w/w) of one or more pesticide(s),
67-80% (w/w) of one or more surfactant(s), and
3-5% (w/w) of one or more rheology modifier(s).
26. The liquid pesticide composition of claims 21-25, further comprising one or more chemically stable pesticide(s).
27. The liquid pesticide composition of claims 21-26 wherein the chemically stable pesticide is Benzobicyclon, Dicamba, or Prosulfuron.
28. The liquid pesticide composition of claims 21-27, wherein the rheology modifier comprises silica.
29. The liquid pesticide composition according to any one of claims 21-28, wherein the surfactant is an acid selected from oleic, caprylic, decanedioic, or linolenic, mono tertiary amine-PEG-trimerate, or a salt thereof.
30. The liquid pesticide composition of claim 29, wherein the surfactant is salt of the acid selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid.
31. The liquid pesticide composition according to any one of claims 21-28, wherein the surfactant comprises at least one glyceryl group.
32. The liquid pesticide composition of claim 21, wherein the surfactant is selected from tricaprylate glycerol, trioleate glycerol, tristearate glycerol, di-lineolate/monostearate glycerol, or mixtures thereof.
33. The liquid pesticide composition according to any one of claims 21-28, wherein the surfactant comprises at least one sulfonyl group.
34. The liquid pesticide composition of claim 33, wherein the surfactant is a sulfate or a sulfonate selected from mono/dioleyl sulfate, lauryl sulfate, dodecylbenzene sulfonate, oleyl sulfonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenesulfonate, or a salt thereof.
35. The liquid pesticide composition of claim 33, wherein the surfactant is the salt of the sulfate or sulfonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the sulfate or sulfonate.
36. The liquid pesticide composition according to any one of claims 21-28, wherein the surfactant comprises at least one phosphonyl group.
37. The liquid pesticide composition of claim 36, wherein the surfactant is a phosphate or phosphonate selected from mono/di oleyl phosphonate, lauryl phosphonate, dodecylbenzene phosphonate, oleyl phosphonate, 2-propenoic acid butyl ester polymer with ethenyl acetate and ethyenephosphonate, and salts thereof.
38. The liquid pesticide composition of claim 36, wherein the surfactant is salt of the phosphate or phosphonate selected from sodium, potassium, lithium, magnesium, calcium, zinc, or aluminum salt, or a mixture of one or more of the foregoing salts and the acid form of the phosphate or phosphonate.
39. A method for controlling pest(s) in a lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals comprising applying the liquid pesticide composition of any of the previous claims to the lawn, garden, turf grass, agriculture crops, non-crop areas, or ornamentals.
40. The method for controlling pest(s) of claim 39, wherein the crop field is selected from field corn, field corn grown for seed, grain sorghum (milo), rice, sugarcane, fallow ground, cotton, or dry beans, or combinations thereof.
41. The method for pests of claim 39, wherein the pest(s) include undesired vegetation selected from Alfalfa (Medicago sativa); Alligator weed (Alternanthera philoxeroides); Amaranth, palmer (Amaranthus palmeri); Amaranth, spiny (Amaranth spinosus); Artichoke, Jerusalem (Helianthus tuberosus); Barnyardgrass (Echinochloa crusgalli); Beggarweed, Florida (Desmodium tortuosum); Bindweed (Calystegia sepium); Bindweed, field (Convolvulus arvensis); Bindweed, hedge (Calystegia sepium); Buckwheat, wild; Polygonum convolvulus); Buffalobur (Solanum rostratum); Burcucumber (Sicyos angulatus); Buttercup, hairy (Ranunculus sardous); California arrowhead (Sagittaria montevidensis); Carpetweed (Mollugo verticillata); Chamomile, mayweed (Anthemis cotula); Chervil, bur (Anthriscus scandicina); Chickweed, common (Stellaria media); Chickweed, mouse ear (Cerastium vulgatum); Clover, white (Dutch) (Trifolium repens); Cocklebur, common (Xanthium strumarium); Copperleaf, hophornbeam (Acalypha ostryifolia); Corn Spurry (Spergula arvensis); Cutleaf groundcherry (Physalis angulata); Dandelion, common (Taraxacum officinals); Dayflower (Commelina erecta); Dayflower, spreading (Commelina diffusa); Deadnettle, purple (Lamium purpureum); Devils Claw (Proboscidea louisianica); Dogbane, hemp (Apocynum cannabinum); Ducksalad (Heteranthera limosa); Early Water grass (Echinochloa oryzoides); Eclipta (Ecilpta prostrata); Eveningprimrose, cutleaf (Oenothera laciniata); Fiddleneck, coast (Amsinckia intermedia); Fleabane, Philadelphia (Erigeron philadelphicus); Flixweed (Descurainia Sophia); Galinsoga(Galinsoga spp.); Galinsoga(Galinsoga); Galinsoga, hairy (Galinsoga quadriradiata); Garlic, wild (Allium vineale); Golden crownbeard (Verbesina encelioides); Goose foot (Chenopodium californicum); Gromwell, corn (Lithospermum arvense); Groundsel, common (Senecio vulgaris); Henbit (Lamium amplexicaule); Horsenettle (Solanum carolinense); Horsetail (Equisetum arvense); Horseweed (Marestail) (Conyza canadensis); Horseweed/Marestail (Erigeron canadensis); Jimsonweed (Datura stramonium); Jointvetch (Aeschynomene virginica); Knotweed, prostrate (Polygonum aviculare); Kochia(Kochia scoparia); Kyllinga, Annual (Kyllinga sesquiflorus); Kyllinga, Green (Kyllinga breviflora); Ladysthumb (Polygonum persicaria); Lambsquarter, common (Chenopodium album); Late Watergrass/Rice Mimic (Echinochloa phyllopogon); Lettuce, miners (Claytonia perfoliata); Lettuce, prickly (Lactuca serriola); Mallow, common (Malva neglecta); Mallow, Venice (Hibiscus trionum); Mayweed chamomile (dog fennel) (Anthemis cotula); Milkweed, common (Asclepias syriaca); Milkweed, honeyvine (Ampelamus albidus); Monochoria(Monochoria spp); Morningglory, ivyleaf (Ipomoea hederacea); Morningglory, pitted (Ipomoea lacunosa); Morningglory, smallflower (Jacquemontia tamnifolia); Morningglory, tall & Ivyleaf (Ipomoea spp.); Morningglory, tall (Ipomoea purpurea); Mustard, blue (Chorispora tenella); Mustard, tumble (Sisymbrium altissimum); Mustard, wild (Sinapis arevensis); Nightshade, black (Solanum spp.); Nutsedge, Purple (Cyperus rotundus); Nutsedge, Yellow (Cyperus esculentus); Passionflower, maypop (Passiflora incarnata); Pennycress, field (Thlaspi arvense); Pepperweed, field (Lepidium campestre); Pepperweed, Virginia (Lepidium virginicum); Pigweed, redroot (Amarunthus retrofiexus); Pigweed, smooth (Amaranthus hybridus); Pigweed, tumbl (Amaranthus hybridus); Pineappleweed (Matricaria discoidea); Plantain (Plantago major); Pokeweed, common (Phytolacca Americana); Puncturevine (Tibulus terrestris); Purslane (Portulaca oleracea); Purslane, common (Portulaca oleracea); Purslane, horse (Trianthema portulacastrum); Pursley, Florida (Richardia scabra); Radish, wild (Raphanus raphanistrum); Ragweed, common (Ambrosia artemisiifolia); Ragweed, giant (Ambrosia trifida); Redstem (Ammania auriculata); Ricefield bulrush (Scirpus mucronatus); Sesbania, hemp (Sesbania exaltata); Sharppoint fluvellin*, (Kickxia elatine); Shepherd's purse (Capsella bursa-pastoris); Sicklepod (Cassia obtusifolia); Sida, prickly (Sida spinosa); Smallflower umbrella sedge (Cyperus difformis); Smartweed, Annual (Polygonum spp.); Smartweed, Pennsylvania (Polyfonum pennsylvanicum); Sowthistle, annual (Sonchus oleraceus); Sprangletop (Leptochloa fascicularis); Sun flower (Helianthus annuus); Sun flower (Helianthus spp.); Tansymustard (Descurainia pinnata); Texasweed (Caperonia palustris); Thistle, Canada (Cirsium arvense); Thistle, Russian (Salsola iberica); Velvetleaf (Abutilan theophrasti); Wallflower, bushy (Erysimum repandum); Water hyssop (Bacopa. spp); Waterhemp, common (Amaranthus rudis); Waterhemp, tall (Amaranthus tuberculatus); Waterhemp (Amaranthus spp); Willow herb, common (Epilobium ciliatum); Willowherb (Epilobium cihatum); Yellowcress, creeping (Rorippa sylvestris), or combinations thereof.
42. The liquid pesticide composition of claim 1, wherein the glyceryl includes salt of carbonyl, sulfonyl, or phosphonyl, and where the glyceryl includes OH groups they are associated with the carbonyl, sulfonyl, or phosphonyl group(s).
43. The liquid pesticide composition of claim 21, wherein the glyceryl includes salt of carbonyl, sulfonyl, or phosphonyl, and where the glyceryl includes OH groups they are associated with the carbonyl, sulfonyl, or phosphonyl group(s).
US17/432,025 2019-02-19 2020-02-19 Stable liquid compositions and methods of using the same Abandoned US20220132854A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/432,025 US20220132854A1 (en) 2019-02-19 2020-02-19 Stable liquid compositions and methods of using the same

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201962807670P 2019-02-19 2019-02-19
PCT/US2020/018860 WO2020172305A1 (en) 2019-02-19 2020-02-19 Stable liquid compositions and methods of using the same
US17/432,025 US20220132854A1 (en) 2019-02-19 2020-02-19 Stable liquid compositions and methods of using the same

Publications (1)

Publication Number Publication Date
US20220132854A1 true US20220132854A1 (en) 2022-05-05

Family

ID=72042539

Family Applications (2)

Application Number Title Priority Date Filing Date
US17/432,025 Abandoned US20220132854A1 (en) 2019-02-19 2020-02-19 Stable liquid compositions and methods of using the same
US16/795,372 Active US11109588B2 (en) 2019-02-19 2020-02-19 Stable liquid formulations and methods of using the same

Family Applications After (1)

Application Number Title Priority Date Filing Date
US16/795,372 Active US11109588B2 (en) 2019-02-19 2020-02-19 Stable liquid formulations and methods of using the same

Country Status (4)

Country Link
US (2) US20220132854A1 (en)
CA (1) CA3130265A1 (en)
MX (1) MX2021009954A (en)
WO (1) WO2020172305A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20220132854A1 (en) 2019-02-19 2022-05-05 Gowan Company, L.L.C. Stable liquid compositions and methods of using the same
BR112022006658A2 (en) * 2021-03-04 2023-09-26 Upl Ltd Liquid herbicide compositions

Family Cites Families (159)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59106466D1 (en) 1990-08-15 1995-10-19 Ciba Geigy Ag Sulfonylureas as herbicides.
DE69321439T2 (en) 1992-11-18 1999-03-04 Ishihara Sangyo Kaisha Ltd., Osaka Process for increasing heroicidal activity and herbicidal compositions with increased activity
UA63884C2 (en) 1995-04-12 2004-02-16 Singenta Participations Ag Herbicidal composition and a method of controlling the emergence of undesirable plants
US6046134A (en) 1996-06-21 2000-04-04 E. I. Du Pont De Nemours And Company Herbicidal mixtures
ES2159859T3 (en) 1996-09-03 2001-10-16 Syngenta Participations Ag AGROCHEMICAL COMPOSITIONS.
US6130186A (en) 1996-10-25 2000-10-10 Monsanto Company Composition and method for treating plants with exogenous chemicals
CA2269726A1 (en) 1996-10-25 1998-04-30 Monsanto Company Composition and method for treating plants with exogenous chemicals
AU708918B2 (en) 1997-01-28 1999-08-19 Syngenta Participations Ag Herbicidal synergistic composition and method of weed control
US6114283A (en) 1998-07-28 2000-09-05 E. I. Du Pont De Nemours And Company Herbicidal mixtures
CA2340241C (en) 1998-08-13 2011-10-04 Aventis Cropscience Gmbh Herbicidal compositions with acylated aminophenylsulfonylureas
RS49988B (en) 1998-08-13 2008-09-29 Bayer Cropscience Ag., HERBICIDES FOR CORN TOLERANT OR RESISTANT CULTURES
DE19842894A1 (en) 1998-09-18 2000-03-23 Hoechst Schering Agrevo Gmbh Synergistic herbicidal combination useful for selective weed control in crops, especially cereals, comprising amino-triazine herbicide and another herbicide
JP4189612B2 (en) * 1998-09-24 2008-12-03 日産化学工業株式会社 Stabilizing suspension herbicidal formulation
US20010051175A1 (en) 1999-04-12 2001-12-13 Strom Robert M. Aqueous dispersions of agricultural chemicals
DE19951427A1 (en) 1999-10-26 2001-05-17 Aventis Cropscience Gmbh Non-aqueous or low-water suspension concentrates of active ingredient mixtures for crop protection
DK1277405T3 (en) 2000-04-26 2007-11-05 Ishihara Sangyo Kaisha Stabilization of solid herbicidal compositions comprising flazasulfuron
DE10020671A1 (en) 2000-04-27 2001-11-08 Aventis Cropscience Gmbh Liquid formulations
DE10022989A1 (en) 2000-05-11 2001-11-22 Aventis Cropscience Gmbh Use of enveloped agrochemical, especially herbicide, safener, growth regulator, insecticide or fungicide, for suppression of antagonistic interactions in agrochemical mixtures
DE10022990A1 (en) 2000-05-11 2001-11-22 Aventis Cropscience Gmbh Combination of agrochemical and a polymer linked via hydrogen bridges, useful especially for application of herbicides, preferably sulfonylureas
WO2001087064A1 (en) 2000-05-15 2001-11-22 Imperial Chemical Industries Plc Agrochemical spray treatment and spray formulations
US6992045B2 (en) * 2000-05-19 2006-01-31 Monsanto Technology Llc Pesticide compositions containing oxalic acid
DE10108472A1 (en) 2001-02-22 2002-09-05 Aventis Cropscience Gmbh Agrochemical formulations
DE10117508A1 (en) 2001-04-07 2002-10-17 Bayer Cropscience Gmbh Synergistic herbicidal composition, useful particularly for selective weed control in cereals, comprises an aminotriazine and second herbicide
DE10135641A1 (en) 2001-07-21 2003-02-06 Bayer Cropscience Gmbh Herbicide combinations with special sulfonylureas
DE10135642A1 (en) 2001-07-21 2003-02-27 Bayer Cropscience Gmbh Herbicide combinations with special sulfonylureas
DE60218707T2 (en) 2001-09-14 2007-06-28 Basf Ag HERBICIDAL MIXTURES ON 3 PHENYLURACIL BASIS
TWI245601B (en) 2001-09-26 2005-12-21 Kumiai Chemical Industry Co Granular agricultural chemical preparations and its scattering method with uniformly diffusivity
TW200305368A (en) 2001-12-19 2003-11-01 Basf Ag Herbicidal mixtures based on 7-pyrazolylbenzoxazoles
DE10209478A1 (en) 2002-03-05 2003-09-18 Bayer Cropscience Gmbh Herbicide combinations with special sulfonylureas
DE10209468A1 (en) 2002-03-05 2003-09-18 Bayer Cropscience Gmbh Herbicide combinations with special sulfonylureas
US20040023802A1 (en) 2002-05-16 2004-02-05 Monsanto Technology, L.L.C. Increasing plant yield and/or vigor by seed treatment with a neonicotinoid compound
US20040023801A1 (en) 2002-05-16 2004-02-05 Monsanto Technology, L.L.C. Increasing plant yield and/or vigor by seed treatment with a neonicotinoid compound
CA2486881A1 (en) 2002-05-20 2003-11-27 Chemstop Pty Ltd Process for the preparation and activation of substances and a means of producing same
AU2003213473A1 (en) 2002-08-07 2004-02-26 Syngenta Participations Ag Herbicidal composition
MXPA05006211A (en) 2002-12-13 2005-08-19 Bayer Cropscience Gmbh Oil suspension concentrate.
WO2004095926A2 (en) 2003-04-28 2004-11-11 Monsanto Technology, Llc Treatment of plants and plant propagation materials with an antioxidant to improve plant health and/or yield
CA2531213C (en) 2003-07-25 2013-02-19 Ishihara Sangyo Kaisha, Ltd. Herbicidal composition having the herbicidal effect enhanced, and method for enhancing the herbicidal effect
DE10334301A1 (en) 2003-07-28 2005-03-03 Bayer Cropscience Gmbh Liquid formulation
DE10334304A1 (en) 2003-07-28 2005-03-10 Bayer Cropscience Gmbh Herbicide combinations with special sulfonamides
DE10334302A1 (en) 2003-07-28 2005-03-03 Bayer Cropscience Gmbh Herbicide combinations with special sulfonamides
DE10334303A1 (en) 2003-07-28 2005-03-10 Bayer Cropscience Gmbh Herbicide combinations with special sulfonamides
TWI355894B (en) 2003-12-19 2012-01-11 Du Pont Herbicidal pyrimidines
AR047293A1 (en) 2003-12-19 2006-01-11 Basf Ag METHOD TO CONTROL CONIFERANT PLANTS
BRPI0509244A (en) 2004-03-27 2007-09-04 Bayer Cropscience Gmbh herbicidal combination
US20050252408A1 (en) 2004-05-17 2005-11-17 Richardson H W Particulate wood preservative and method for producing same
EP1941798B1 (en) 2004-12-17 2012-05-23 Devgen NV Nematicidal compositions
PT1858330T (en) 2005-03-14 2017-07-13 Ishihara Sangyo Kaisha Herbicidal suspension
JP5137348B2 (en) 2005-08-10 2013-02-06 石原産業株式会社 Aqueous suspension herbicidal composition
ATE544861T1 (en) 2005-08-24 2012-02-15 Pioneer Hi Bred Int METHODS AND COMPOSITIONS FOR EXPRESSING A POLYNUCLEOTIDE OF INTEREST
ZA200802442B (en) * 2005-09-01 2010-02-24 Du Pont Liquid sulfonylurea herbicide formulations
CN101262772A (en) 2005-09-08 2008-09-10 拜尔作物科学股份公司 Novel sulfonamide-containing solid formulations
CA2622071A1 (en) 2005-09-08 2007-03-15 Bayer Cropscience Ag Novel sulfonamide-containing solid formulations
CA2622568A1 (en) * 2005-09-16 2007-03-22 Nufarm Australia Limited Herbicide composition
UA90757C2 (en) 2005-10-12 2010-05-25 Басф Се Herbicidal composition, method for controlling undesired vegetation and method for protecting crops from phytotoxic action of 3-phenyluracils
MY149916A (en) 2006-01-13 2013-10-31 Dow Agrosciences Llc 2-(poly-substituted aryl)-6-amino-5-halo-4-pyrimidinecarboxylic acids and their use as herbicides
CA2646143A1 (en) 2006-04-10 2007-10-25 E. I. Du Pont De Nemours And Company Herbicidal mixtures
AR063704A1 (en) 2006-09-14 2009-02-11 Makhteshim Chem Works Ltd PESTICIDE NANOPARTICLES OBTAINED OBTAINED FROM MICROEMULSIONS AND NANOEMULSIONS
EP3067425A1 (en) 2006-10-31 2016-09-14 E. I. du Pont de Nemours and Company Soybean event dp-305423-1 and constructs for the generation thereof
EA018275B1 (en) 2007-02-01 2013-06-28 Сол-Джел Текнолоджиз Лтд. METHOD OF OBTAINING PARTICLES CONTAINING COATING FROM METAL OXIDE AND COATED PARTICLES WITH METAL OXIDE
TW200843642A (en) 2007-03-08 2008-11-16 Du Pont Liquid sulfonylurea herbicide formulations
EP1974609A1 (en) 2007-03-29 2008-10-01 Bayer CropScience GmbH Method for manufacturing water dispersible granules (WG)
ES2659991T3 (en) 2007-04-04 2018-03-20 Basf Agrochemical Products, B.V. Herbicide resistant sunflower plants with multiple AHASL1 herbicide resistant alleles and methods of use
US10017827B2 (en) 2007-04-04 2018-07-10 Nidera S.A. Herbicide-resistant sunflower plants with multiple herbicide resistant alleles of AHASL1 and methods of use
GB0709710D0 (en) 2007-05-21 2007-06-27 Syngenta Ltd Herbicidal compositions
AU2008263903A1 (en) 2007-06-12 2008-12-18 Basf Se Herbicidally effective composition
CN101835373B (en) 2007-07-23 2015-03-04 高恩公司 Improved method for controlling unwanted plants
EP2052606A1 (en) 2007-10-24 2009-04-29 Bayer CropScience AG Herbicide combination
CU20070254A7 (en) 2007-11-13 2009-06-25 Bayer Cropscience Gmbh HERBICIDES
WO2009113093A1 (en) 2008-01-22 2009-09-17 United Phosphorus Limited Herbicidal composition
US8404260B2 (en) 2008-04-02 2013-03-26 Bayer Cropscience Lp Synergistic pesticide compositions
WO2010009005A2 (en) * 2008-07-16 2010-01-21 Gowan Comercio Internacional E Servicos L Herbicidal treatment compositions and methods for improved control of undesired vegetation in rice crops
DE102008037620A1 (en) 2008-08-14 2010-02-18 Bayer Crop Science Ag Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides
AU2009300571B2 (en) 2008-10-02 2012-09-13 Farmhannong Co., Ltd. Uracil-based compounds, and herbicides comprising same
EP2193712A1 (en) 2008-12-05 2010-06-09 Bayer CropScience AG Dispersions containing Hydroxyphenylpyruvate-Dioxygenase inhibitors
US9066516B2 (en) 2008-12-31 2015-06-30 Marrone Bio Innovations, Inc. Uses of thaxtomin and thaxtomin compositions as herbicides
MX2011007310A (en) 2009-01-09 2011-08-03 Syngenta Participations Ag Stabilized agrochemical composition.
GB0901834D0 (en) 2009-02-04 2009-03-11 Syngenta Ltd Novel herbicides
EP2225940B1 (en) 2009-03-05 2014-03-12 GAT Microencapsulation GmbH Oil dispersions of nAChR binding neonicotinoids
JP2013504575A (en) 2009-09-09 2013-02-07 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Herbicidal pyrimidone derivatives
WO2011046867A2 (en) 2009-10-13 2011-04-21 Fmc Corporation Herbicidal composition in granular form
US8120543B2 (en) 2009-10-19 2012-02-21 Oleksandr Sulima Transmission line slot antenna
US8791049B2 (en) 2009-12-17 2014-07-29 Gowan Co. Plant treatment compositions particularly effective in the control of Heteranthera limosa on rice crops, and methods for their use
PL2563115T3 (en) 2010-04-26 2018-04-30 Dow Agrosciences, Llc Stabilized agricultural oil dispersions
PT2592929T (en) 2010-07-15 2020-05-29 Dow Agrosciences Llc Solid herbicide compositions with built-in adjuvant
CA2810525A1 (en) 2010-09-17 2012-03-22 Dow Agrosciences Llc Liquid agricultural formulations of improved stability
EP2627183B2 (en) 2010-10-15 2021-08-25 Bayer CropScience Aktiengesellschaft Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant beta vulgaris plants
PT2632265T (en) 2010-10-28 2017-04-18 Dow Agrosciences Llc Synergistic herbicidal composition containing penoxsulam and oryzalin
CN103260401B (en) 2010-11-12 2016-08-10 罗地亚管理公司 Composition pesticide
US20120208700A1 (en) 2011-02-11 2012-08-16 Dow Agrosciences Llc Stable agrochemical oil dispersions
WO2012150333A1 (en) 2011-05-04 2012-11-08 Bayer Intellectual Property Gmbh Use of als inhibitor herbicides for control of unwanted vegetation in als inhibitor herbicide tolerant brassica, such as b. napus, plants
CN103717076B (en) 2011-08-10 2016-04-13 拜耳知识产权股份有限公司 Active compound combinations containing specific tetramic acid derivatives
CN103958686A (en) 2011-09-13 2014-07-30 孟山都技术公司 Methods and compositions for weed control
PH12014500930A1 (en) 2011-10-26 2014-06-09 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
MY172385A (en) 2012-01-25 2019-11-22 Dow Agrosciences Llc Improved solid herbicide compositions with built-in adjuvant
AU2013225125A1 (en) 2012-02-29 2014-09-18 Bayer Cropscience Ag ALS inhibitor herbicide tolerant B. napus mutants
GB2503416B (en) 2012-04-20 2017-07-19 Rotam Agrochem Int Co Ltd Method for spray tank cleanout
US9708288B2 (en) 2012-04-27 2017-07-18 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
HUE032666T2 (en) 2012-05-24 2017-10-30 Bayer Cropscience Ag Herbicide compositions containing n-(tetrazol-5-yl)aryl carboxylic acid amides
PL2854543T3 (en) 2012-05-25 2017-03-31 Bayer Cropscience Ag Chemical stabilisation of iodosulfuron-methyl-sodium salt using hydroxystearates
KR102424031B1 (en) 2012-06-06 2022-07-22 코르테바 애그리사이언스 엘엘씨 High strength herbicidal suspension concentrates
US8809232B2 (en) 2012-07-24 2014-08-19 Dow Agroscience Llc Herbicidal compositions comprising 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl) pyridine-2-carboxylic acid or a derivative thereof and halosulfuron, pyrazosulfuron and esprocarb
RS57806B2 (en) 2012-12-13 2022-07-29 Bayer Cropscience Ag USE OF ALS INHIBITOR HERBICIDE FOR CONTROL OF UNDESIRABLE VEGETATION IN BETA VULGARIS PLANTS TOLERANT TO ALS INHIBITOR HERBICIDE
BR112015014555A2 (en) 2012-12-19 2017-07-11 Dow Agrosciences Llc pesticide compositions and related processes
WO2014120355A1 (en) 2012-12-19 2014-08-07 Dow Agrosciences Llc Pesticidal compositions and processes related thereto
EP2934147B1 (en) 2012-12-20 2019-11-27 BASF Agro B.V. Compositions comprising a triazole compound
CN105246331B (en) 2013-03-15 2018-10-12 美国陶氏益农公司 Synergistic weed control by application of penoxsulam and benzobicyclone or clomazone and benzobicyclone
BR112015018853B1 (en) 2013-03-20 2021-07-13 Basf Corporation MIXTURE, AGROCHEMICAL COMPOSITION, METHOD FOR CONTROLLING PHYTOPATHOGENIC FUNDS, METHOD FOR PROTECTING VEGETABLE PROPAGATION MATERIAL AND COATED SEED
WO2014206835A1 (en) 2013-06-26 2014-12-31 Basf Se Methods for improving the efficacy of anionic herbicides under hard water conditions and suitable compositions
AU2014289184A1 (en) 2013-07-12 2016-02-04 Bayer Cropscience Lp ALS inhibitor herbicide tolerant mutant plants
US20160208277A1 (en) 2013-08-21 2016-07-21 Bayer Cropscience Nv Als inhibitor herbicide tolerant mutant plants
CN103444752A (en) 2013-09-06 2013-12-18 广西壮族自治区农业科学院植物保护研究所 Synergism composition of weed killer for sugarcane field
CN103493838B (en) 2013-09-27 2015-04-29 江苏省农业生产资料集团农用化学有限公司 Pesticide composition containing isoproturon, pretilachlor and halosulfuron-methyl and application thereof
JP6452687B2 (en) 2013-10-25 2019-01-16 バイエル・クロップサイエンス・アクチェンゲゼルシャフト Herbicidal composition containing N- (1,3,4-oxadiazol-2-yl) -arylcarboxylic amides
US20150148234A1 (en) 2013-11-22 2015-05-28 Nidera S.A. Herbicide-resistant sunflower plants with multiple herbicide resistant alleles of ahasl1 and methods of use
US20150148235A1 (en) 2013-11-22 2015-05-28 Nidera S.A. Herbicide-resistant sunflower plants with multiple herbicide resistant alleles of ahasl1 and methods of use
WO2015078828A2 (en) 2013-11-28 2015-06-04 Bayer Cropscience Ag Use of 2-chloro-3-(methylsulfanyl)-n-(1-methyl-1h-tetrazol-5-yl)-4-(trifluoromethyl)benzamide or its salts for controlling unwanted plants in areas of transgenic crop plants being tolerant to hppd inhibitor herbicides
WO2015082413A1 (en) 2013-12-02 2015-06-11 Bayer Cropscience Nv Als inhibitor herbicide tolerant mutant plants
EP3077374B1 (en) 2013-12-03 2020-02-05 FMC Corporation Pyrrolidinones as herbicides
CN103651482A (en) * 2013-12-30 2014-03-26 孙蒙蒙 Corn field herbicide
AU2015218838B2 (en) 2014-02-23 2018-03-22 Fmc Corporation Use of 3-isoxazolidinones compounds as selective herbicides
CN104094954A (en) 2014-03-21 2014-10-15 江苏省农业科学院 Pesticide composition comprising ethoxysulfuron and halosulfuron-methyl and application thereof
CN103960266A (en) 2014-03-21 2014-08-06 江苏省农业科学院 Pesticide composition containing chlortoluron, pretilachlor and halosulfuron-methyl and application of pesticide composition
WO2015153210A1 (en) 2014-03-31 2015-10-08 Fmc Corporation Controlling red rice with mesotrione
AU2015250895B2 (en) 2014-04-23 2018-11-01 Basf Se Herbicidal combination comprising azines
ES2886441T3 (en) 2014-04-29 2021-12-20 Fmc Corp Pyridazinone herbicides
DE102014012022A1 (en) 2014-08-13 2016-02-18 Clariant International Ltd. Organic ammonium salts of anionic pesticides
CN104285994B (en) * 2014-09-19 2016-08-24 河南中天恒信生物化学科技有限公司 Compound herbicide and application thereof containing azoles oxadiazon, halosulfuronmethyl and fluroxypyr
CN104522017A (en) 2014-09-30 2015-04-22 浙江天丰生物科学有限公司 Paddy field binary compound herbicide
EP3236750B1 (en) 2014-12-22 2019-10-30 Mitsui AgriScience International S.A./N.V. Herbicidal oil dispersion
CN111713504A (en) 2014-12-22 2020-09-29 三井农业化学国际有限公司 Liquid herbicidal composition containing sulfonylurea
AU2015374407A1 (en) 2014-12-29 2017-07-20 Fmc Corporation Compositions and methods for use of insecticide with Bacillus sp. D747
GB201502164D0 (en) 2015-02-10 2015-03-25 Syngenta Participations Ag Herbicidal compounds
CN104738069A (en) 2015-03-18 2015-07-01 陕西上格之路生物科学有限公司 Weeding composition containing halosulfuron-methyl and fluroxypyr
GB201505740D0 (en) 2015-04-02 2015-05-20 Syngenta Participations Ag Herbicidal mixtures
GB201505852D0 (en) 2015-04-07 2015-05-20 Syngenta Participations Ag Herbicidal mixtures
TWI828952B (en) 2015-06-05 2024-01-11 美商艾佛艾姆希公司 Pyrimidinyloxy benzene derivatives as herbicides
CN104996447A (en) 2015-06-25 2015-10-28 江苏省农业科学院 Pesticide composition containing halosulfuron-methyl and fluroxypyr and its use in prevention and control of lemnaceae plants
CN104920362A (en) 2015-06-25 2015-09-23 江苏省农业科学院 Pesticide composite comprising benzobicyclon and dicamba and application of pesticide composite in prevention of lemnaceae plants
BR112018000490A2 (en) 2015-07-10 2018-09-11 Basf Agro Bv use of (±) -2-exo- (2-methylbenzyloxy) -1-methyl-4-isopropyl-7-oxabicyclo [2.2.1] heptane, undesirable vegetation control method, use and herbicidal composition
US10477863B2 (en) 2015-08-06 2019-11-19 Basf Se Use of herbicidal compositions for controlling unwanted vegetation
WO2017063973A1 (en) 2015-10-14 2017-04-20 Syngenta Participations Ag Fungicidal compositions
CN106689170A (en) 2015-11-16 2017-05-24 江苏龙灯化学有限公司 Weeding composition
CN105532703B (en) 2016-02-06 2018-03-27 江苏省农用激素工程技术研究中心有限公司 For preventing and treating the Herbicidal combinations of sugarcane field weed
EP3205208A1 (en) 2016-02-09 2017-08-16 Basf Se Mixtures and compositions comprising paenibacillus strains or fusaricidins and chemical pesticides
WO2017153200A1 (en) 2016-03-10 2017-09-14 Basf Se Fungicidal mixtures iii comprising strobilurin-type fungicides
CN105831123B (en) 2016-04-15 2018-01-23 青岛清原抗性杂草防治有限公司 A kind of cornfield weeding composition and its application
CN105941448A (en) 2016-05-03 2016-09-21 河南省农业科学院植物保护研究所 Herbicide for capsicum annuum field and application thereof
EP3454658B1 (en) 2016-05-11 2024-11-27 Monsanto Technology LLC Glyphosate formulations containing amidoalkylamine surfactants
PL3416486T3 (en) 2016-06-21 2019-11-29 Battelle Uk Ltd Liquid herbicidal compositions containing a sulfonylurea and a Li salt
RU2746121C2 (en) 2016-07-08 2021-04-07 Кумиай Кемикал Индастри Ко., Лтд. Herbicide composition
AU2018208526B2 (en) 2017-01-10 2022-12-22 BASF Agro B.V. Composition comprising cinmethylin-containing microparticles and a further herbicide
TWI772367B (en) 2017-02-16 2022-08-01 瑞士商先正達合夥公司 Fungicidal compositions
EP3378315A1 (en) 2017-03-24 2018-09-26 Bayer CropScience Aktiengesellschaft Herbicidal mixtures comprising 2-[2,4-dichlorophenyl)methyl]-4,4-dimethyl-3-isoxazolidinone
WO2019034934A1 (en) 2017-08-14 2019-02-21 Adama Agan Ltd. DISPERSABLE FORMULATION IN OIL
US11234437B2 (en) 2017-09-13 2022-02-01 Syngenta Participations Ag Fungicidal compositions
WO2019244088A1 (en) 2018-06-21 2019-12-26 Pi Industries Ltd. Agrochemical composition comprising a pyrimidyloxybenzoate in a synergistic combination with sulfonylureas
BR102018072160B1 (en) 2018-10-26 2024-02-27 Agrivalle Brasil Indústria E Comércio De Produtos Agrícolas S.A. BIOLOGICAL COMPOSITION OF MULTIPLE FUNCTIONS
US20200236925A1 (en) 2019-01-24 2020-07-30 Bayer Cropscience Lp Methods and formulations for preventing downward migration of agricultural materials
US20220132854A1 (en) 2019-02-19 2022-05-05 Gowan Company, L.L.C. Stable liquid compositions and methods of using the same

Also Published As

Publication number Publication date
US11109588B2 (en) 2021-09-07
MX2021009954A (en) 2021-12-10
WO2020172305A1 (en) 2020-08-27
CA3130265A1 (en) 2020-08-27
US20200260722A1 (en) 2020-08-20

Similar Documents

Publication Publication Date Title
AU2010288528B2 (en) Aqueous suspension concentrate formulations containing saflufenacil
BR102013005302B1 (en) herbicidal composition comprising isoxaflutol, cyprosulfamide, and flumioxazin and weed control method
US11109588B2 (en) Stable liquid formulations and methods of using the same
CZ301651B6 (en) Herbicidal mixture containing a 3-heterocyclyl-substituted benzoyl derivative and an adjuvant
WO2022118821A1 (en) Agrochemical composition
WO2018028324A1 (en) Weeding composition having synergistic effects
CN106386817A (en) Weeding composition with synergism
JP5829044B2 (en) Herbicidal composition
US20230210111A1 (en) Herbicidal mixtures and compositions and methods of use
CN101061803B (en) Herbicidal composition
CN107439579A (en) Weeding in cotton field agent composition and its application containing flumioxazin
WO2016117671A1 (en) Substituted pyrazolyl-pyrazole derivative and use of same as herbicide
WO2016117670A1 (en) Substituted pyrazolyl-pyrazole derivative and use of same as herbicide
WO2016117675A1 (en) Substituted pyrazolyl-pyrazole derivative and use of same as herbicide
CN106135248A (en) Compound herbicide composition
CN111066811A (en) Herbicide composition containing penoxsulam and application thereof
US20060240986A1 (en) Herbicidal method
WO2016117673A1 (en) Substituted pyrazolyl-pyrazole derivative and use of same as herbicide
CN118177197A (en) Weeding composition and application thereof
AU2023379983A1 (en) Aqueous suspension concentrate formulations of agrochemical actives
CN119769525A (en) Herbicide composition and its application
CN117581876A (en) Herbicide and application thereof
WO2016117679A1 (en) Substituted pyrazolyl-pyrazole derivative and use of same as herbicide
CN103202307B (en) Complex herbicidal composition
CN105638694A (en) Agricultural insecticide and bactericide composition and application thereof

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: APPLICATION UNDERGOING PREEXAM PROCESSING

AS Assignment

Owner name: GOWAN COMPANY, L.L.C., ARIZONA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ESSINGER, JAMES FRANKLIN;GAN, LIN;BEHRENS, NIHAL JOHNNY;SIGNING DATES FROM 20200210 TO 20200212;REEL/FRAME:057226/0423

STCB Information on status: application discontinuation

Free format text: ABANDONED -- INCOMPLETE APPLICATION (PRE-EXAMINATION)

STCB Information on status: application discontinuation

Free format text: ABANDONED -- INCOMPLETE APPLICATION (PRE-EXAMINATION)