WO2013059288A1 - Stable formulations containing fumed aluminum oxide - Google Patents
Stable formulations containing fumed aluminum oxide Download PDFInfo
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- WO2013059288A1 WO2013059288A1 PCT/US2012/060571 US2012060571W WO2013059288A1 WO 2013059288 A1 WO2013059288 A1 WO 2013059288A1 US 2012060571 W US2012060571 W US 2012060571W WO 2013059288 A1 WO2013059288 A1 WO 2013059288A1
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Classifications
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- 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
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
- A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
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- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- 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
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
Definitions
- the present invention relates to the field of agrochemical formulations.
- compositions containing two or more herbicides are desirable in agricultural, specialty applications and related endeavors due to broadening the spectrum or range of unwanted plant species killed or controlled.
- Tank mixing In which the ingredients in their commercially available form are mixed together by the user in a quantity of water. Tank mixes require the end user to purchase two or more commercial formulations, store them, calculate the correct amount of each active ingredient, measure those amounts into the mix and when empty, properly dispose of a number of containers.
- Tank mixing two or three different commercial formulations often results in physical instabilities causing precipitation of active ingredients, flocculation, phase separation and the like, providing uneven distribution of the active ingredients.
- Combining active ingredients into one formulation is beneficial but frequently more complex due to widely different physical properties of the active ingredients in which chemical and physical stability are problems.
- the present invention relates to a novel aqueous suspoemulsion composition containing an herbicidal agent comprised of atrazine, pyroxasulfone and fluthiacet-methyl that has superior chemical and physical stability as well as superior re-dispersion.
- Still another embodiment of the present invention is a process for the preparation of an aqueous suspoemulsion composition
- a process for the preparation of an aqueous suspoemulsion composition comprising:
- Another embodiment of the present invention is an aqueous suspension concentrate composition
- aqueous suspension concentrate composition comprising:
- an agriculturally active component comprising fluthiacet-methyl, atrazine and pyroxasulfone
- a surfactant component comprising an acrylic graft copolymer and a
- fumed alumina provides exceptional physical and chemical stability to the compositions.
- Other stabilizing agents for example, fumed silica, when used in the present suspoemulsion or suspension concentrate compositions, provide good chemical stability but lack physical stability (e.g. precipitates form after 24 hours at room temperature, re-dispersion difficulties).
- Adding fumed alumina to the present suspoemulsion or suspension concentrate compositions provides chemically and physically stable compositions.
- fumed alumina can be added to the suspension concentrate composition portion, or may be added to the final formulation composition; preferably it is added to the suspension concentrate portion of the composition.
- a suspoemulsion composition is formed by combining a suspension concentrate composition with an emulsion in water composition.
- a suspension concentrate (SC) is a formulation in which a solid active ingredient(s) is suspended in a liquid carrier.
- the aqueous suspension concentrate composition portion of the suspoemulsion further comprises a surfactant component, a pH adjuster (optional), an anti-freeze agent, an antifoam agent and an anti-microbial (biocide) agent.
- Atrazine is present in an amount of from 40% to 55% by weight, preferably in an amount of from 44% to 51% by weight of all the components in the SC composition.
- An emulsion in water is a formulation in which droplets of a non-water soluble phase (oil or non-water soluble solvent) is evenly distributed in water.
- the EW portion of the suspoemulsion composition of the present invention further comprises a solvent that is not water soluble, a surfactant component, a pH adjuster, an anti-freeze agent, an antifoam agent and an anti-microbial (biocide) agent.
- Fluthiacet- methyl is present in an amount of 1% to 2% by weight of all the components in the EW composition.
- the solvent is preferably an aromatic solvent, for example, Aromatic 200 or Aromatic 200 ND, available from ExxonMobilTM Chemicals, and is present in an amount of from 45% to 50% by weight of all the components in the EW composition.
- the surfactant component is comprised of at least two surfactants; a non-ionic polymeric surfactant and a polyalkylene oxide block copolymer.
- the non-ionic polymeric surfactant is preferably, for example, AtloxTM 4914, available from Crodia Crop Care and is present in an amount of from 4% to 5% by weight of all the components in the EW composition.
- polyalkylene oxide block copolymer is preferably, for example, AtlasTM G-5000, available from Crodia Crop Care and is present in amount of from 4.5% to 5.5% by weight of all the components in the EW composition.
- the pH adjuster is preferably an acid, for example, glacial acetic acid, and is present in an amount of from 0.01% to 0.1 % by weight of all the components in the EW composition.
- the anti-freeze agent is preferably propylene glycol and is present in an amount of from 5% to 10% by weight, preferably 6% by weight of all the components in the EW composition.
- the antifoam agent is preferably a silicone emulsion, for example,
- DOWCORNING ® AF Emulsion available from Dow ® Chemical Company and is present in an amount of 0.05% to 0.5% by weight, preferably 0.1% by weight of all the components in the EW composition.
- the biocide is preferably, for example, KATHONTM CG or LEGEND ® MK both available from Dow ® Chemical Company or Acticide ® MV available from Thor Specialties, Inc. and is present in an amount of from 0.05% to 0.1% by weight of all the components in the EW composition.
- an aqueous suspension concentrate is formed using fumed alumina as the stability agent.
- the aqueous suspension concentrate composition comprises an active ingredient component comprising fluthiacet-methyl, pyroxasulfone and atrazine; a surfactant component comprising an acrylic graft copolymer and a polyalkylene oxide copolymer; an antifoam agent; a biocide; a pH adjusting agent; an antifreeze agent; and a stabilization agent.
- Fluthiacet-methyl is present in an amount of from 0.1% to 0. 2% by weight of all the components in the SC composition.
- Pyraxosulfone is present in an amount of from 5% to 7% by weight of all the components in the SC
- the pH adjuster is preferably an acid, for example, glacial acetic acid, and is present in an amount of from 0.01% to 0.1% by weight of all the components in the SC composition.
- the anti-freeze agent is preferably propylene glycol and is present in an amount of from 5% to 10% by weight, preferably 5.5% to 6% by weight of all the components in the SC composition.
- the antifoam agent is preferably a silicone emulsion, for example, DOWCORNING ® AF Emulsion available from Dow ® Chemical Company and is present in an amount of 0.05% to 0.1% by weight of all the components in the SC composition.
- the biocide is preferably, for example, KATHONTM CG or
- LEGEND ® MK both available from Dow ® Chemical Company or Acticide ® MV available from Thor Specialties, Inc., and is present in an amount of from 0.01% by weight to 0.1% by weight of all components in the total composition.
- the stabilization component is fumed alumina, preferably as an aqueous dispersion that is acidic, for example, AERODISP® W 630, available from Evonik Industries, and is present in an amount of from 0.5% to 2% by weight of all the components in the SC composition.
- the weight ratio of fluthiacet-methyl to pyraxosulfone to atrazine can vary over a wide range but is usually in the range of 1:33:284 to 1:40:325.
- a particular embodiment of the present invention is a method for the control of unwanted plants comprising applying a pesticidally effective amount of the composition of the present invention to an area where such control is desired.
- ambient temperature and "room temperature” as utilized herein shall generally mean any suitable temperature found in a laboratory or other working quarter, and is generally neither below about 15° C nor above about 30° C.
- by weight of components in the composition includes the wt % of all liquid and solid components in the composition.
- a suspoemulsion concentrate was formed by combining 367.82 grams of atrazine/pyroxasulfone SC from Step A with 51.84 grams of the fluthiacet-methyl EW from Step B and 4.67 grams of deionized water. The resultant composition was stirred until a uniform mixture was obtained. The resultant suspoemulsion concentrate composition was evenly distributed into eight ounce glass jars, sealed and stored for stability testing either at an elevated temperature of 54° C for two weeks.
- SC Atrazine/Pyroxasulfone Suspension Concentrate
- EW Fluthiacet-methyl emulsion in Water
- Tersp 2500 Tersperse® 2500 from Huntsman Performance Products
- Thickener Veegum® Magnesium Aluminum Silicate from R.T. Vanderbilt Company Inc.
- Atlox AtloxTM 4914 from Crodia Crop Care
- Thickener Kelzan® ASX Xanthan Gum form CPKelco A Huber Company
- Step A Atrazine/Pyroxasulfone Suspension Concentrate (SC)
- Portion wise additions of pyroxasulfone (480.0 grams, 99.3% purity) and Atrazine (3.862.0 kilograms, 97.0% purity) were made to the tank allowing each addition to mix in thoroughly before adding the next portion.
- the mixture was transferred to an attritor mill and milled, keeping the temperature at less than 30°C, until a particle size of D90 ⁇ 3 ⁇ was attained.
- the milled mixture was transferred to a blending tank and 138.9 grams of an aqueous dispersion of fumed alumina (Aerodisp ® W630 from Evonic Industries) was added. The mixture was stirred for one hour to provide 6.79 kilograms of a suspension concentrate.
- Step B Fluthiacet- methyl Emulsion in Water (EW)
- An organic phase was prepared by adding 141.4 grams of fluthiacet-methyl (99.1% purity) and 544.5 grams of a nonionic polymeric surfactant (AtloxTM 4914 from Crodia Crop Care) to 5.4446 kilograms of an aromatic naphthalene depleted solvent (Aromatic 200 ND from ExxonMobil Chemicals). The mixture was stirred and heated to about 55°C, in a 15 liter jacketed vessel with an in-line homogenizer, forming a solution.
- a nonionic polymeric surfactant AtloxTM 4914 from Crodia Crop Care
- An aqueous phase was prepared by adding 5.7 grams of glacial acetic acid, 687.7 grams of propylene glycol, 573.1 grams of a polyalkylene oxide block copolymer (AtlasTM G5000 from Crodia Crop Care), 5.70 gram of anti foam agent (Dow ® Antifoam AF from The Dow Chemical Company) and 4.0492 kilograms of deionized water into a mixing vessel and heated at 55°C until a homogenous mixture was obtained.
- the warm organic phase was added to the aqueous phase through the recirculation line of an in-line homogenizer. Once the addition was complete, the homogenization continued until a particle size of less than 3 microns at D90 was achieved.
- the mixture was allowed to cool to room temperature and 10.3 grams of a preservative (Acticide ® MV from Thor Specialties, Inc.) was added and stirred until a uniform mixture, about 11.2 kilograms, was obtained.
- a suspoemulsion concentrate was formed by combining 6.658 kiolgrams grams of atrazine/pyroxasulfone SC from Step A with 941.0 grams of the fluthiacet- methyl EW from Step B and 186.0 grams of deionized water. The resultant composition was stirred until a uniform mixture, 7.77 kilograms, was obtained. This suspoemulsion formulation was stored in separate sealed glass containers.
- a suspoemulsion concentrate was formed by combining 449.3 grams of atrazine/pyroxasulfone SC from Step A with 50.8 grams of the fluthiacet-methyl EW from Step B and 4.67 grams of deionized water. The resultant composition was stirred until a uniform mixture was obtained. This suspoemulsion formulation was stored in separate sealed glass containers.
- Example 3 and Example 4 were analyzed for physical and chemical stability at 24hours (Initial), Freeze/Thaw (F/T) cycle (three cycles of two days at minus 30°C/two days at room temperature) and 54°C for two weeks.
- the suspoemulsion of Example 3 was also analyzed for physical and chemical stability at one and three months at 50°C and one month at room temperature. Sample viscosity (centipoise) was measured using a Brookfield RVT viscometer, spindle number 3, spindle speed of 50.
- Particle size was measured using a particle size distribution analyzer (Horiba Particle Scattering Particle Size Distribution Analyzer LA-910) at D90 (90% of the particles were of the size reported in microns). Percent separation was measured visually by measuring the height of the separated layer and dividing that number by the total height of the container. Analysis for the active ingredients was performed by HPLC analysis on a % by weight basis. These data are summarized in Table 4B below. Table 4B
- compositions are formed by the addition of fumed alumina to agricultural compositions such as suspoemulsion formulations and suspension concentrate formulations as compared to similar compositions employing commonly used stabilizers such as fumed silica.
Abstract
The present invention provides novel herbicidal aqueous suspoemulsion or aqueous suspension concentrate compositions containing an herbicidal active agent and fumed alumina as a stabilization agent that have superior chemical and physical stability as well as superior re-dispersion properties.
Description
STABLE FORMULATIONS CONTAINING FUMED ALUMINUM OXIDE FIELD OF THE INVENTION
[0001] The present invention relates to the field of agrochemical formulations. BACKGROUND OF THE INVENTION
[0002] To enable the efficient elimination or controlling of unwanted plants, it is desirable to use effective chemical formulations of herbicides. Compositions containing two or more herbicides are desirable in agricultural, specialty applications and related endeavors due to broadening the spectrum or range of unwanted plant species killed or controlled.
[0003] Due to the desirability of having a composition with the above-mentioned properties, it is useful to use combinations of herbicides to obtain enhanced control of numerous weeds with a single herbicidal application. Combinations of pesticides are known and available as mixed solutions of the active ingredients in their commercially available formulations. One method of preparing such a composition is referred to as "tank mixing" in which the ingredients in their commercially available form are mixed together by the user in a quantity of water. Tank mixes require the end user to purchase two or more commercial formulations, store them, calculate the correct amount of each active ingredient, measure those amounts into the mix and when empty, properly dispose of a number of containers. Tank mixing two or three different commercial formulations often results in physical instabilities causing precipitation of active ingredients, flocculation, phase separation and the like, providing uneven distribution of the active ingredients. Combining active ingredients into one formulation is beneficial but frequently more complex due to widely different physical properties of the active ingredients in which chemical and physical stability are problems.
SUMMARY OF THE INVENTION
[0004] The present invention provides novel herbicidal aqueous suspoemulsion or aqueous suspension concentrate compositions containing an herbicidal active agent and fumed alumina as a stabilization agent that have superior chemical and physical stability as well as superior re-dispersion properties.
DETAILED DESCRIPTION OF THE INVENTION
[0005] The present invention provides novel herbicidal aqueous suspoemulsion or aqueous suspension concentrate compositions containing an herbicidal active agent and fumed alumina as a stabilization agent that have superior chemical and physical stability as well as superior re-dispersion properties.
[0006] In one aspect the present invention relates to a novel aqueous suspoemulsion composition containing an herbicidal agent comprised of atrazine, pyroxasulfone and fluthiacet-methyl that has superior chemical and physical stability as well as superior re-dispersion.
[0007] In particular the aqueous suspoemulsion composition of the present invention comprises:
i) an aqueous suspension concentrate composition containing pyroxasulfone and atrazine;
ii) an emulsion in water composition containing fluthiacet-methyl; and iii) fumed alumina.
[0008] Another embodiment of the present invention is a process for the preparation of an aqueous suspoemulsion composition comprising:
i) forming an aqueous suspension concentrate composition containing pyroxasulfone and atrazine;
ii) forming an emulsion in water composition containing fluthiacet-methyl;
iii) blending the suspension concentrate and emulsion in water compositions together and
iv) adding fumed alumina and blending the mixture to form a homogenous
mixture.
[0009] Still another embodiment of the present invention is a process for the preparation of an aqueous suspoemulsion composition comprising:
i) forming an aqueous suspension concentrate composition containing pyroxasulfone and atrazine and fumed alumina;
ii) forming an emulsion in water composition containing fluthiacet- methyl;
iii) blending the suspension concentrate and emulsion in water compositions together to form a homogenous mixture.
[0010] Another embodiment of the present invention is an aqueous suspension concentrate composition comprising:
i) an agriculturally active component comprising fluthiacet-methyl, atrazine and pyroxasulfone;
ii) a surfactant component comprising an acrylic graft copolymer and a
polyalkylene oxide block copolymer;
iii) an antifoam agent;
iv) a biocide;
v) a pH adjusting agent;
vi) an antifreeze agent; and
vii) fumed alumina.
[0011] It has been surprisingly discovered that the addition of fumed alumina to a suspoemulsion or suspension concentrate compositions provides exceptional physical and chemical stability to the compositions. Other stabilizing agents, for example, fumed silica, when used in the present suspoemulsion or suspension concentrate compositions, provide good chemical stability but lack physical stability (e.g. precipitates form after 24 hours at room temperature, re-dispersion difficulties). Adding fumed alumina to the present suspoemulsion or suspension concentrate compositions provides chemically and physically stable compositions. In preparing a suspoemulsion composition, fumed alumina can be added to the suspension concentrate composition portion, or may be added to the final formulation composition; preferably it is added to the suspension concentrate portion of the
composition.
[0012] In one aspect of the present invention a suspoemulsion composition is formed by combining a suspension concentrate composition with an emulsion in water composition. A suspension concentrate (SC) is a formulation in which a solid active ingredient(s) is suspended in a liquid carrier. The aqueous suspension concentrate composition portion of the suspoemulsion further comprises a surfactant component, a pH adjuster (optional), an anti-freeze agent, an antifoam agent and an anti-microbial (biocide) agent. Atrazine is present in an amount of from 40% to 55% by weight, preferably in an amount of from 44% to 51% by weight of all the components in the SC composition. Pyraxosulfone is present in an amount of from 5% to about 7% by weight of all the components in the SC composition. The surfactant component is comprised of at least two surfactants; an alkyl EO/PO copolymer and an acrylic graft copolymer. The alkyl EO/PO copolymer is preferably, for example, TERGITOL™ XD Surfactant, available from Dow® Chemicals and is present in an amount of from 2% to 3% by weight of all the components in the SC composition. The acrylic graft copolymer is preferably, for example, TERSPERSE® 2500 Dispersant, available from Huntsman Performance Products and is present in amount of from 3% to 4% by weight of all the components in the SC composition. The pH adjuster is preferably an acid, for example, glacial acetic acid, and is present in an amount of from 0% to 0.13% by weight of all the components in the SC composition. The anti-freeze agent is preferably propylene glycol and is present in an amount of from 5% to 10% by weight, preferably 6% by weight of all the components in the SC composition. The antifoam agent is preferably a silicone emulsion, for example, DOWCORNING® AF Emulsion available from Dow® Chemical Company and is present in an amount of 0.05% to 0.5% by weight, preferably 0.1% by weight of all the components in the SC composition. The biocide is preferably, for example, KATHON™ CG or LEGEND® MK both available from Dow® Chemical Company or Acticide® MV available from Thor Specialties, Inc., and is present in an amount of from 0.05% to 0.5% by weight, preferably 0.1% by weight of all the components in the SC composition. The stabilization component is fumed alumina, preferably as an aqueous dispersion that is acidic, for example, AERODISP® W 630, available from
Evonik Industries, and is present on an amount of from 0.5% to 2% by weight of all the components in the SC composition. The SC composition can further comprise a thickening agent, for example, magnesium aluminum silicate (Veegum®
Magnesium Aluminum Silicate from R.T.Vanderbilt Company)
[0013] An emulsion in water (EW) is a formulation in which droplets of a non-water soluble phase (oil or non-water soluble solvent) is evenly distributed in water. The EW portion of the suspoemulsion composition of the present invention further comprises a solvent that is not water soluble, a surfactant component, a pH adjuster, an anti-freeze agent, an antifoam agent and an anti-microbial (biocide) agent.
Fluthiacet- methyl is present in an amount of 1% to 2% by weight of all the components in the EW composition. The solvent is preferably an aromatic solvent, for example, Aromatic 200 or Aromatic 200 ND, available from ExxonMobil™ Chemicals, and is present in an amount of from 45% to 50% by weight of all the components in the EW composition. The surfactant component is comprised of at least two surfactants; a non-ionic polymeric surfactant and a polyalkylene oxide block copolymer. The non-ionic polymeric surfactant is preferably, for example, Atlox™ 4914, available from Crodia Crop Care and is present in an amount of from 4% to 5% by weight of all the components in the EW composition. The
polyalkylene oxide block copolymer is preferably, for example, Atlas™ G-5000, available from Crodia Crop Care and is present in amount of from 4.5% to 5.5% by weight of all the components in the EW composition. The pH adjuster is preferably an acid, for example, glacial acetic acid, and is present in an amount of from 0.01% to 0.1 % by weight of all the components in the EW composition. The anti-freeze agent is preferably propylene glycol and is present in an amount of from 5% to 10% by weight, preferably 6% by weight of all the components in the EW composition. The antifoam agent is preferably a silicone emulsion, for example,
DOWCORNING® AF Emulsion available from Dow® Chemical Company and is present in an amount of 0.05% to 0.5% by weight, preferably 0.1% by weight of all the components in the EW composition. The biocide is preferably, for example, KATHON™ CG or LEGEND® MK both available from Dow® Chemical Company or Acticide® MV available from Thor Specialties, Inc. and is present in an amount of from 0.05% to 0.1% by weight of all the components in the EW composition.
[0014] In another embodiment of the present invention an aqueous suspension concentrate is formed using fumed alumina as the stability agent. The aqueous suspension concentrate composition comprises an active ingredient component comprising fluthiacet-methyl, pyroxasulfone and atrazine; a surfactant component comprising an acrylic graft copolymer and a polyalkylene oxide copolymer; an antifoam agent; a biocide; a pH adjusting agent; an antifreeze agent; and a stabilization agent. Fluthiacet-methyl is present in an amount of from 0.1% to 0. 2% by weight of all the components in the SC composition. Pyraxosulfone is present in an amount of from 5% to 7% by weight of all the components in the SC
composition. Atrazine is present in an amount of from 40% to 45% by weight of all the components in the SC composition. The surfactant component is comprised of an acrylic graft copolymer and a polyalkylene oxide block copolymer. The acrylic graft copolymer is preferably, for example, TERSPERSE® 2500 Dispersant, available from Huntsman Performance Products and is present in amount of from 2.5% to 3.0% by weight of all the components in the SC composition. The polyalkylene oxide block copolymer is preferably, for example, Atlas™ G-5000, available from Crodia Crop Care and is present in an amount of from 2.5% to 2.75% by weight of all the components in the SC composition. The pH adjuster is preferably an acid, for example, glacial acetic acid, and is present in an amount of from 0.01% to 0.1% by weight of all the components in the SC composition. The anti-freeze agent is preferably propylene glycol and is present in an amount of from 5% to 10% by weight, preferably 5.5% to 6% by weight of all the components in the SC composition. The antifoam agent is preferably a silicone emulsion, for example, DOWCORNING® AF Emulsion available from Dow® Chemical Company and is present in an amount of 0.05% to 0.1% by weight of all the components in the SC composition. The biocide is preferably, for example, KATHON™ CG or
LEGEND® MK both available from Dow® Chemical Company or Acticide® MV available from Thor Specialties, Inc., and is present in an amount of from 0.01% by weight to 0.1% by weight of all components in the total composition. The stabilization component is fumed alumina, preferably as an aqueous dispersion that is acidic, for example, AERODISP® W 630, available from Evonik Industries, and is present in an amount of from 0.5% to 2% by weight of all the components in the
SC composition.
[0015] The weight ratio of fluthiacet-methyl to pyraxosulfone to atrazine can vary over a wide range but is usually in the range of 1:33:284 to 1:40:325.
[0016] A particular embodiment of the present invention is a method for the control of unwanted plants comprising applying a pesticidally effective amount of the composition of the present invention to an area where such control is desired.
[0017] As used in this specification and, unless otherwise indicated, the term "herbicide" refers to a molecule or combination of molecules that inhibits or otherwise kills unwanted plants, such as, but not limited to, deleterious or annoying weeds, broadleaf plants, grasses and sedges and can be used for crop protection, edifice protection or turf protection. The term "herbicidally effective amount" means an amount necessary to produce an observable herbicidal effect on unwanted plant growth, including the effects of necrosis, death, growth inhibition, reproduction inhibition, inhibition of proliferation, and removal, destruction, or otherwise diminishing the occurrence and activity of unwanted plants.
[0018] The terms "ambient temperature" and "room temperature" as utilized herein shall generally mean any suitable temperature found in a laboratory or other working quarter, and is generally neither below about 15° C nor above about 30° C.
[0019] As used herein, " by weight of components in the composition" includes the wt % of all liquid and solid components in the composition.
[0020] The process and compositions of the present invention are further illustrated by the examples below. The examples serve only to illustrate the invention and should not be interpreted as limiting since further modifications of the disclosed invention will be apparent to those skilled in the art. All such modifications are deemed to be within the scope of the invention as defined in the claims.
Example 1
Preparation of a Suspoemulsion Concentrate Formulation of Atrazine, Pyroxasulfone and Fluthiacet-methyl with Fumed Alumina as the Stabilization
Agent
Step A: Atrazine/Pyroxasulfone Suspension Concentrate (SC)
[0021] A mixture of 179.90 grams of deionized water, 0.10 grams of glacial acetic acid, 36.00 grams of polyethylene glycol, 0.60 gram of anti foam agent (Dow® Antifoam AF from The Dow Chemical Company), 0.60 gram of a preservative (Kathon™ CG/ICP from The Dow Chemical Company), 14.10 grams of an alkyl EO/PO copolymer nonionic surfactant (Tergitol™ XD from The Dow Chemical Company), 20.10 grams of an acrylic graft copolymer surfactant (Tersperse® G- 2500 from Huntsman Performance Products), 7.80 grams of an aqueous dispersion of fumed alumina (Aerodisp® W630 from Evonic Industries), 37.50 grams of pyroxasulfone (99.3% purity) and 303.0 grams of Atrazine (97.0% purity) was added to a 1 liter beaker and blended for five minutes at 4500 rpm using a Silverson homogenizer. The mixture was transferred to an Eiger mill and milled for 15 minutes at 3000 rpm, achieving a particle size of D90 < 3μιη.
Step B: Fluthiacet-methyl Emulsion in Water (EW)
[0022] Fluthiacet-methyl, 12.36 grams (99.1% purity) and 47.50 grams of a nonionic polymeric surfactant (Atlox™ 4914 from Crodia Crop Care) was added to 475.00 grams of an aromatic naphthalene depleted solvent (Aromatic 200 ND from ExxonMobile Chemicals). The mixture was stirred and heated to about 65 °C, forming a solution. This solution was added to a warm (about 65 °C) solution of 0.50 gram of glacial acetic acid, 60.00 grams of propylene glycol, 50.00 grams of a polyalkylene oxide block copolymer (Atlas™ G5000 from Crodia Crop Care), 0.50 gram of anti foam agent (Dow® Antifoam AF from The Dow Chemical Company) and 1.00 gram of a preservative (Kathon™ CG/ICP from The Dow Chemical Company) in 353.00 grams of deionized water. This mixture homogenized using a Silverson homogenizer until a uniform mixture was formed.
Step C: Suspoemulsion Concentrate (SE) Formation
[0023] A suspoemulsion concentrate was formed by combining 367.82 grams of atrazine/pyroxasulfone SC from Step A with 51.84 grams of the fluthiacet-methyl EW from Step B and 4.67 grams of deionized water. The resultant composition was stirred until a uniform mixture was obtained. The resultant suspoemulsion concentrate composition was evenly distributed into eight ounce glass jars, sealed and stored for stability testing either at an elevated temperature of 54° C for two weeks. Analysis by High Performance Liquid Chromatography (HPLC) indicated the following after two weeks at elevated temperature: initial analysis - atrazine 42.33%; pyroxasulfone 5.40%; fluthiacet-methyl 0.16%; elevated temperature atrazine 42.48%; pyroxasulfone 5.42%; fluthiacet-methyl 0.16%; indicating that the composition was chemically stable.
[0024] Visual inspection of the suspoemulsion concentrate composition at two weeks indicated no phase separation or sedimentation indicating the composition was physically stable.
Example 2
Atrazine/Pyroxasulfone Suspension Concentrate (SC) and Fluthiacet-methyl emulsion in Water (EW) preparations with Fumed Alumina as the Stabilization
Agent
[0025] In a manner similar to Step A of Example 1, additional SC compositions containing atrazine and pyroxasulfone were prepared. In a manner similar to Step B of Example 1 , additional EW compositions containing fluthiacet-methyl were prepared. Table 2A below summarizes additional SC compositions; Table 2B summarizes additional EW compositions.
TABLE 2A
SC Compositions Containing Atrazine and Pyroxasulfone
Pyroxasulfone 99.3% purity
Atrazine 97% purity
Terg XD = Tergitol™ XD from The Dow Chemical Company
Tersp 2500 = Tersperse® 2500 from Huntsman Performance Products
Areodisp = Aerodisp® W630 from Evonic Industries
Glycol= Propylene glycol
Dow AF = Dow® Antifoam AF from The Dow Chemical Company
Kathon = Kathon™ CG/ICP from The Dow Chemical Company
Thickener = Veegum® Magnesium Aluminum Silicate from R.T. Vanderbilt Company Inc.
TABLE 2B
EW Compositions Containing Fluthiacet-methyl
*Fluthiacet- methyl 99.1% assay
Aromatic 200 ND from ExxonMobile Chemicals
Atlox = Atlox™ 4914 from Crodia Crop Care
Atlas = Atlas™ G5000 from Crodia Crop Care
Kathon = Kathon™ CG/ICP from The Dow Chemical Company
Acticide = Acticide® MV from Thor Specialties, Inc.
Dow AF = Dow® Antifoam AF from The Dow Chemical Company
Thickener = Kelzan® ASX Xanthan Gum form CPKelco A Huber Company
Example 3
Preparation of a Suspoemulsion Concentrate Formulation of Atrazine, Pyroxasulfone and Fluthiacet-methyl with Fumed Alumina as the Stabilization
Agent
Step A: Atrazine/Pyroxasulfone Suspension Concentrate (SC)
[0026] A mixture of 2.311 kilograms of deionized water, 7.7 grams of glacial acetic acid, 463.0 grams of polyethylene glycol, 7.7 gram of anti foam agent (Dow® Antifoam AF from The Dow Chemical Company), 6.9 gram of a preservative (Acticide® MV from Thor Specialties, Inc.), 181.4 grams of an alkyl EO/PO copolymer nonionic surfactant (Tergitol™ XD from The Dow Chemical Company), 258.5 grams of an acrylic graft copolymer surfactant (Tersperse® G-2500 from Huntsman Performance Products) was added to a slurry tank and mixed until uniform. Portion wise additions of pyroxasulfone (480.0 grams, 99.3% purity) and
Atrazine (3.862.0 kilograms, 97.0% purity) were made to the tank allowing each addition to mix in thoroughly before adding the next portion. The mixture was transferred to an attritor mill and milled, keeping the temperature at less than 30°C, until a particle size of D90 < 3μιη was attained. The milled mixture was transferred to a blending tank and 138.9 grams of an aqueous dispersion of fumed alumina (Aerodisp® W630 from Evonic Industries) was added. The mixture was stirred for one hour to provide 6.79 kilograms of a suspension concentrate.
Step B: Fluthiacet- methyl Emulsion in Water (EW)
[0027] An organic phase was prepared by adding 141.4 grams of fluthiacet-methyl (99.1% purity) and 544.5 grams of a nonionic polymeric surfactant (Atlox™ 4914 from Crodia Crop Care) to 5.4446 kilograms of an aromatic naphthalene depleted solvent (Aromatic 200 ND from ExxonMobil Chemicals). The mixture was stirred and heated to about 55°C, in a 15 liter jacketed vessel with an in-line homogenizer, forming a solution. An aqueous phase was prepared by adding 5.7 grams of glacial acetic acid, 687.7 grams of propylene glycol, 573.1 grams of a polyalkylene oxide block copolymer (Atlas™ G5000 from Crodia Crop Care), 5.70 gram of anti foam agent (Dow® Antifoam AF from The Dow Chemical Company) and 4.0492 kilograms of deionized water into a mixing vessel and heated at 55°C until a homogenous mixture was obtained. The warm organic phase was added to the aqueous phase through the recirculation line of an in-line homogenizer. Once the addition was complete, the homogenization continued until a particle size of less than 3 microns at D90 was achieved. The mixture was allowed to cool to room temperature and 10.3 grams of a preservative (Acticide® MV from Thor Specialties, Inc.) was added and stirred until a uniform mixture, about 11.2 kilograms, was obtained.
Step C: Suspoemulsion Concentrate (SE) Formation
[0028] A suspoemulsion concentrate was formed by combining 6.658 kiolgrams grams of atrazine/pyroxasulfone SC from Step A with 941.0 grams of the fluthiacet- methyl EW from Step B and 186.0 grams of deionized water. The resultant
composition was stirred until a uniform mixture, 7.77 kilograms, was obtained. This suspoemulsion formulation was stored in separate sealed glass containers.
Reference Example A
Preparation of a Suspoemulsion Concentrate Formulation of Atrazine, Pyroxasulfone and Fluthiacet-methyl with Fumed Silica as the Stabilization Agent
Step A: Atrazine/Pyroxasulfone Suspension Concentrate (SC)
[0029] A mixture of 186.8 grams of deionized water, 0.50 gram of glacial acetic acid, 30.00 grams of polyethylene glycol, 0.50 gram of anti foam agent (Dow® Antifoam AF from The Dow Chemical Company), 0.75 gram of a preservative (Kathon™ CG/ICP from The Dow Chemical Company), 11.75 grams of an alkyl EO/PO copolymer nonionic surfactant (Tergitol™ XD from The Dow Chemical Company), 16.75 grams of an acrylic graft copolymer surfactant (Tersperse® G- 2500 from Huntsman Performance Products), 2.50 grams of an aqueous dispersion of fumed silica (Aerodisp® W 7512 S from Evonic Industries, a commonly used emulsion stabilizer), 25.75 grams of pyroxasulfone (99.3% purity) and 222.50 grams of Atrazine (97.0% purity) was added to a 1 liter beaker and blended for five minutes at 4500 rpm using a Silverson homogenizer. The mixture was transferred to an Eiger mill and milled for 15 minutes at 3000 rpm, achieving a particle size of D90 < 3μιη.
Step B: Fluthiacet-methyl Emulsion in Water (EW)
[0030] Fluthiacet-methyl, 18.54 grams (99.1% purity) and 71.25 grams of a nonionic polymeric surfactant (Atlox™ 4914 from Crodia Crop Care) was added to
712.50 grams of an aromatic naphthalene depleted solvent (Aromatic 200 ND from
ExxonMoblie Chemicals). The mixture was stirred and heated to about 65 °C, forming a solution. This solution was added to a warm (about 65 °C) solution of
0.75 gram of glacial acetic acid, 90.00 grams of propylene glycol, 75.00 grams of a polyalkylene oxide block copolymer (Atlas™ G5000 from Crodia Crop Care),
0.75gram of anti foam agent (Dow® Antifoam AF from The Dow Chemical
Company) and 2.25 grams of a preservative (Kathon™ CG/ICP from The Dow
Chemical Company) in 527.61 grams of deionized water. This mixture was homogenized using a Silverson homogenizer until a uniform mixture was formed.
Step C: Suspoemulsion Concentrate (SE) Formation
[0031] A suspoemulsion concentrate was formed by combining 449.3 grams of atrazine/pyroxasulfone SC from Step A with 50.8 grams of the fluthiacet-methyl EW from Step B and 4.67 grams of deionized water. The resultant composition was stirred until a uniform mixture was obtained. This suspoemulsion formulation was stored in separate sealed glass containers.
Example 4
Preparation of an Aqueous Suspension Concentrate Formulation of Atrazine, Pyroxasulfone and Fluthiacet-methyl with Fumed Alumina as the Stabilization
Agent
[0032] A mixture of 308.72 grams of deionized water, 0.72 gram of glacial acetic acid, 46.88 grams of polyethylene glycol, 0.72 gram of anti foam agent (Dow® Antifoam AF from The Dow Chemical Company), 0.72 gram of a preservative (Acticide® MV from Thor Specialties, Inc.), 22.96 grams of an acrylic graft copolymer surfactant (Tersperse® G-2500 from Huntsman Performance Products), 20.88 grams of a polyalkylene oxide block copolymer (Atlas™ G5000 from Crodia Crop Care), 12.32 grams of an aqueous dispersion of fumed silica (Aerodisp® W 7512 S from Evonic Industries, a commonly used emulsion stabilizer), 42.56 grams of pyroxasulfone (99.3% purity), 342.40 grams of Atrazine (97.0% purity) and 1.20 grams of fluthiacet-methyl (99.1% purity) was added to a 2 liter beaker and blended for five minutes at 4500 rpm using a Silverson homogenizer. The mixture was transferred to an Eiger mill and milled until a particle size of D90 < 3μιη was achieved. This SC formulation was stored in separate sealed glass containers.
Example 5
Physical and Chemical Stability Data
[0033] A dilution re-dispersion study was conducted using either 1.0 gram (1%) or 3.0 grams (3%) of the suspoemulsion concentrate compositions from Example 3 and Reference Example A added to 99.0 mL or 97.0 mL of water with either 20 ppm or 500 ppm hardness in a 100 mL Nessler tube. The Nessler tube was sealed with a rubber stopper and the contents mixed by inverting the tube ten times. The test samples so produced were maintained at ambient temperature. Re-suspension assessment of the formulation was performed at 24 hours and the number of inversions needed to produce a homogenous mixture was recorded. Table 4A below summarizes the re-dispersion data.
Table 4A
Re-suspension Data From Example 3 and Reference Example
[0034] The suspoemulsion concentrate compositions of Example 3 and Example 4 were analyzed for physical and chemical stability at 24hours (Initial), Freeze/Thaw (F/T) cycle (three cycles of two days at minus 30°C/two days at room temperature) and 54°C for two weeks. The suspoemulsion of Example 3 was also analyzed for physical and chemical stability at one and three months at 50°C and one month at room temperature. Sample viscosity (centipoise) was measured using a Brookfield RVT viscometer, spindle number 3, spindle speed of 50. Particle size was measured using a particle size distribution analyzer (Horiba Particle Scattering Particle Size Distribution Analyzer LA-910) at D90 (90% of the particles were of the size reported in microns). Percent separation was measured visually by measuring the height of the separated layer and dividing that number by the total height of the container. Analysis for the active ingredients was performed by HPLC analysis on a % by weight basis. These data are summarized in Table 4B below.
Table 4B
Physical and Chemical Stability Data For Example 3 Suspoemulsion
[0035] As can be seen by the data provided above, physically and chemically stable compositions are formed by the addition of fumed alumina to agricultural compositions such as suspoemulsion formulations and suspension concentrate formulations as compared to similar compositions employing commonly used stabilizers such as fumed silica.
[0036] While this invention has been described with an emphasis upon preferred embodiments, it will be obvious to those of ordinary skill in the art that variations in the preferred devices and methods may be used and that it is intended that the invention may be practiced otherwise than as specifically described herein.
Accordingly, this invention includes all modifications encompassed within the spirit and scope of the invention as defined by the claims that follow.
Claims
1. A suspoemulsion concentrate composition comprising:
i) an aqueous suspension concentrate composition containing pyroxasulfone and atrazine;
ii) an emulsion in water composition containing fluthiacet-methyl; and iii) fumed alumina.
2. The suspoemulsion concentrate composition of claim 1 wherein the aqueous suspension concentrate further comprises one or more of a surfactant component, a pH adjuster, an anti-freeze agent, an antifoam agent, a thickening agent and antimicrobial agent.
3. The suspoemulsion concentrate composition of claim 1 wherein the emulsion in water concentrate further comprises one or more of a surfactant component, a pH adjuster, an anti-freeze agent, an antifoam agent, a thickening agent and antimicrobial agent.
4. The composition of claim 1 wherein the weight ratio of fluthiacet-methyl to pyraxosulfone to atrazine is from 1:33:284 to 1:40:325.
5. A process for the preparation of a suspoemulsion composition comprising: i) forming an aqueous suspension concentrate composition containing pyroxasulfone and atrazine;
ii) forming an emulsion in water composition containing fluthiacet-methyl; iii) blending the suspension concentrate and emulsion in water compositions together and
iv) adding fumed alumina and blending the mixture to form a homogenous mixture.
6. A process for the preparation of a suspoemulsion composition comprising: i) forming an aqueous suspension concentrate composition containing pyroxasulfone and atrazine and fumed alumina; ii) forming an emulsion in water composition containing fluthiacet-methyl; iii) blending the suspension concentrate and emulsion in water compositions together to form a homogenous mixture.
7. An aqueous suspension concentrate composition comprising:
i) an agriculturally active component comprising fluthiacet-methyl, atrazine and pyroxasulfone;
ii) a surfactant component comprising an acrylic graft copolymer and a polyalkylene oxide block copolymer;
iii) an antifoam agent;
iv) a biocide;
v) a pH adjusting agent;
vi) an antifreeze agent; and
vii) fumed alumina.
Priority Applications (7)
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| CN201280051258.3A CN103957718B (en) | 2011-10-18 | 2012-10-17 | Include gaseous oxidation aluminium (FUMED ALUMINUM OXIDE) stabilization formulations |
| US14/351,974 US8962525B2 (en) | 2011-10-18 | 2012-10-17 | Stable formulations containing fumed aluminum oxide |
| CA2852240A CA2852240A1 (en) | 2011-10-18 | 2012-10-17 | Stable formulations containing fumed aluminum oxide |
| MX2014004697A MX351568B (en) | 2011-10-18 | 2012-10-17 | Stable formulations containing fumed aluminum oxide. |
| AU2012326246A AU2012326246B2 (en) | 2011-10-18 | 2012-10-17 | Stable formulations containing fumed aluminum oxide |
| KR1020147013034A KR101931846B1 (en) | 2011-10-18 | 2012-10-17 | Stable formulations containing fumed aluminum oxide |
| JP2014537170A JP5964441B2 (en) | 2011-10-18 | 2012-10-17 | Stable formulation containing fumed aluminum oxide |
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| PCT/US2012/060571 WO2013059288A1 (en) | 2011-10-18 | 2012-10-17 | Stable formulations containing fumed aluminum oxide |
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| JP (1) | JP5964441B2 (en) |
| KR (1) | KR101931846B1 (en) |
| CN (1) | CN103957718B (en) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104094945A (en) * | 2014-06-25 | 2014-10-15 | 广东中迅农科股份有限公司 | Herbicide for corn field |
| CN106028810A (en) * | 2014-02-28 | 2016-10-12 | 组合化学工业株式会社 | Agrochemical composition for foliage treatment |
| WO2019072602A1 (en) * | 2017-10-09 | 2019-04-18 | Basf Se | New agrochemical pesticide compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106259362A (en) * | 2015-06-09 | 2017-01-04 | 江苏龙灯化学有限公司 | A kind of Synergistic herbicide compositions |
| US20200198157A1 (en) | 2017-08-31 | 2020-06-25 | Kawasaki Jukogyo Kabushiki Kaisha | Gripping device |
| CN107509733A (en) * | 2017-09-12 | 2017-12-26 | 河南省农业科学院植物保护研究所 | A kind of cornfield weeding composition containing atrazine and sulfone pyrrole grass azoles |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2240691C2 (en) * | 1996-09-23 | 2004-11-27 | Байер Акциенгезелльшафт | Herbicide agent based on arylsulfonylaminocarbonyltriazolinones |
| US20100210704A1 (en) * | 2007-10-18 | 2010-08-19 | Kumiai Chemical Industry Co., Ltd. | 3-alkoxy-1-phenylpyrazole derivatives and pesticides |
| EA201001430A1 (en) * | 2008-03-11 | 2011-04-29 | Басф Се | HERBICIDE COMPOSITIONS CONTAINING PYROXASSULPHONE |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU774112B2 (en) * | 2000-03-14 | 2004-06-17 | Sumitomo Chemical Company, Limited | Aqueous pesticidal composition |
| UA78071C2 (en) * | 2002-08-07 | 2007-02-15 | Kumiai Chemical Industry Co | Herbicidal composition |
| JP4752182B2 (en) * | 2004-03-01 | 2011-08-17 | 住友化学株式会社 | Insect growth regulator |
| CN101052301A (en) | 2004-09-06 | 2007-10-10 | 巴斯福股份公司 | (hetero) cyclylcarboxamide for preventing and controlling pathogenic fungi |
| CA2594998A1 (en) * | 2005-01-25 | 2006-08-03 | Neurogen Corporation | Substituted pyridazinyl-and pyrimidinyl-quinolin-4-ylamine analogues |
| US20060270559A1 (en) * | 2005-05-26 | 2006-11-30 | Nippon Soda Co., Ltd. | Method of producing suspended agricultural chemical composition |
| TW201433263A (en) * | 2005-07-04 | 2014-09-01 | Sumitomo Chemical Co | Method for producing pesticidal composition and method for controlling weeds |
| US8110530B2 (en) * | 2006-12-21 | 2012-02-07 | Kumiai Chemical Industry Co., Ltd. | Herbicidal composition |
| CL2009001251A1 (en) * | 2008-05-21 | 2010-08-13 | Basf Se | Herbicidal composition comprising glyphosate and its salts, pyroxasulfone and imazamox and their agriculturally acceptable salts; and method to combat undesirable vegetation. |
-
2012
- 2012-10-17 AU AU2012326246A patent/AU2012326246B2/en active Active
- 2012-10-17 CN CN201280051258.3A patent/CN103957718B/en active Active
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- 2012-10-17 CA CA2852240A patent/CA2852240A1/en not_active Abandoned
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2240691C2 (en) * | 1996-09-23 | 2004-11-27 | Байер Акциенгезелльшафт | Herbicide agent based on arylsulfonylaminocarbonyltriazolinones |
| US20100210704A1 (en) * | 2007-10-18 | 2010-08-19 | Kumiai Chemical Industry Co., Ltd. | 3-alkoxy-1-phenylpyrazole derivatives and pesticides |
| EA201001430A1 (en) * | 2008-03-11 | 2011-04-29 | Басф Се | HERBICIDE COMPOSITIONS CONTAINING PYROXASSULPHONE |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106028810A (en) * | 2014-02-28 | 2016-10-12 | 组合化学工业株式会社 | Agrochemical composition for foliage treatment |
| EP3111761A4 (en) * | 2014-02-28 | 2017-08-09 | Kumiai Chemical Industry Co., Ltd. | Agrochemical composition for foliage treatment |
| US10091999B2 (en) | 2014-02-28 | 2018-10-09 | Kumiai Chemical Industry Co. | Agrochemical composition for foliage treatment |
| CN104094945A (en) * | 2014-06-25 | 2014-10-15 | 广东中迅农科股份有限公司 | Herbicide for corn field |
| WO2019072602A1 (en) * | 2017-10-09 | 2019-04-18 | Basf Se | New agrochemical pesticide compositions |
| CN111200934A (en) * | 2017-10-09 | 2020-05-26 | 巴斯夫欧洲公司 | Novel agrochemical pesticide composition |
| CN111200934B (en) * | 2017-10-09 | 2022-12-20 | 巴斯夫欧洲公司 | Novel agrochemical pesticide composition |
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| KR101931846B1 (en) | 2018-12-21 |
| KR20140079483A (en) | 2014-06-26 |
| CN103957718B (en) | 2017-10-24 |
| AU2012326246B2 (en) | 2015-09-17 |
| JP5964441B2 (en) | 2016-08-03 |
| MX351568B (en) | 2017-10-19 |
| AU2012326246A1 (en) | 2014-05-01 |
| MX2014004697A (en) | 2014-10-17 |
| CN103957718A (en) | 2014-07-30 |
| JP2014530252A (en) | 2014-11-17 |
| CA2852240A1 (en) | 2013-04-25 |
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