GB2267825A - Herbicide microemulsion concentrate - Google Patents
Herbicide microemulsion concentrate Download PDFInfo
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- GB2267825A GB2267825A GB9211141A GB9211141A GB2267825A GB 2267825 A GB2267825 A GB 2267825A GB 9211141 A GB9211141 A GB 9211141A GB 9211141 A GB9211141 A GB 9211141A GB 2267825 A GB2267825 A GB 2267825A
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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
- 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
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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
- 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
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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
- 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
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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
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
- A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
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- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A stable water-dispersible herbicide microemulsion concentrate composition contains as the active ingredient a water- insoluble herbicide, such as fluroxypyr-1-methylheptyl ester, combined with a water-soluble salt of N-phosphonomethyl- glycine, for example the isopropylamine salt; together with at least one amino ethoxylate containing 2 to 5 moles of ethylene oxide; at least one amino ethoxylate surfactant containing from 8 to 20 moles of ethylene oxide; and at least one cosurfactant which is a glycol ether, a C4-C12 aliphatic alcohol, an alcohol ether based on ethylene, propylene or butylene oxide, or a nonionic surfactant with an HLB value of less than 10.
Description
HERBICIDAL AQUEOUS-BASED MICROEMULSION COMPOSITIONS
The present invention relates to novel oil-in -water microemulsions of herbicidal chemicals and methods for preparing and using said microemulsions for controlling undesirable plant species.
It is a practice within agriculture directed to the growing of crop plants to use a range of products containing a variety of active ingredients to obtain a broad spectrum of control of undesirable plant species.
When applying two or more products to a crop, preparation containing two or more active ingredients are usually mixed in a tank shortly before their field application.
Such mixtures are often referred to as tank-mixtures and normally contain two or more active ingredients where the combined spectra of activity makes up for any deficiencies of each of the individual components.
Tank-mixtures suffer from the disadvantage in that the farmer must purchase and store each separate herbicide until the actual preparation of such tankmixture in the field. The farmer is also required to measure out varying amounts of each different herbicideused in the tank-mixture allowing for the possibility of mixing errors. Accordingly, a prepackaged mixture, i.e., concentrate, containing a mixture of herbicides in one container is highly desirable since the farmer only has to purchase and store the single prepackaged mixture containing the active ingredients and the possibility of mixing errors is eliminated. An appropriate amount of the prepackaged concentrate can be added directly to the tank used for application, and the concentrate diluted with the addition of water for the in situ preparation of the tank-mixture.
However, difficulties in preparing a prepackaged concentrate occurs when one of the herbicides is immiscible with water, or when the composition contains a mixture of herbicides, which are not both miscible in the same desired solvent. To overcome solvent incompatibility, a concentrated emulsion formulation can be used. A concentrated emulsion formulation consists of two phases and is a dispersion of one immiscible liquid (the discontinuous phase) in a second liquid (the continuous phase). If the continuous phase is water, the emulsion is an oil-in-water type emulsion and the water-immisible liquid or solution is generally referred to as the "oil" regardless of its nature. In a concentrated emulsion formulation the active ingredient is usually dissolved in an organic solvent along with added emulsifiers or dispersants.
When the concentrate is added to water, the active ingredient becomes dispersed throughout the water.
Formulations have also been developed where a sparingly water-soluble herbicide or mixture of such herbicides is dissolved within the oil phase and a watersoluble herbicide is carried within the aqueousphase. A water-dispersible herbicide emulsion composition containing the water-soluble herbicide
N-phosphonomethylglycine in the aqueous phase and the water-insoluble herbicide 2-haloacetanilide herbicide in the oil phase is disclosed in U.S. Patent 4,440,562. The emulsifier system in such a formulation is an anionicnonionic blend containing alkylaryl sulfonate, phosphate esters of nonylphenol ethoxylates and polyalkyleneglycol ethers.
The formation of an emulsion, where the particle size is generally greater than 0.4 microns and opaque to light, requires the input of a considerable amount of mechanical energy in the form of high shear mixing. Such emulsions are kinetically stable due to the mechanical energy required to form the emulsion. To prevent the emulsion from separating into separate phases, gels or thickening surfactants are added.
Microemulsions, on the other hand, present a unique class of thermodynamically-stable liquid dispersions where the dispersed particles are less than 0.1 microns in diameter. Microemulsions are transparent to light and have a low interfacial tension which makes microemulsions thermodynamically stable without the need to add a large amount of mechanical energy to form the microemulsion, or addition of gels to thicken and stabilize it. To achieve the low interfacial tension necessary to form a microemulsion, they are generally prepared with more than one surfactant or with a mixture of a surfactant and a cosurfactant (e.g., a polar compound of intermediate chain length). This combination of surfactants is usually required to provide the proper balance between hydrophilic andlipophilic properties (HLB, hydrophile- lipophile balance) for the required oil and water phases.
Although the formation of microemulsions is obtainable using certain surfactant combinations and finite concentrations of these combinations, formulating herbicide microemulsions is still an art. For example, the choice of solvents and emulsifiers should be chosen to keep the herbicides in solution in the concentrate even at low temperatures and emulsifiable when diluted in water. In the preparation of a microemulsion formulation it is also desirable that the herbicide which is soluble in the aqueous phase should be essentially insoluble in the organic phase. Conversely, the herbicide that is soluble or suspended in the organic solvent should be essentially insoluble in the aqueous phase. This is necessary to ensure that over the period of shelf-life of a concentrate product, that the concentrate remain physically stable.Should the water solubility be excessive, crystal growth will occur in the concentrate leading to physical disruption of the concentrate.
Additional difficulties are encountered in the preparation of microemulsions when it is desirable to place active ingredients within both the oil and water phases. When preparing such a combination concentrate product, it is necessary to develop a system containing an appropriate surfactant, or blend of surfactants, and a cosurfactant to maintain the stability of the microemulsion and to maintain the stability of the active ingredients within the two phases.
The present invention is directed to a waterdispersible herbicidal microemulsion composition comprising:
A. from 1 to 30 percent by weight of at least one water insoluble herbicide;
B. optionally, from 0 to 25 percent by weight of a non water-miscible organic solvent in which the water insoluble herbicide is soluble;
C. from 1 to 30 percent by weight of a watersoluble salt of glyphosate;
D. from 0.5 to 35, preferably from 0.5 to 10 percent by weight of at least one amine ethoxylate surfactant containing from 2 to 5 moles of ethylene oxide;
E. from 0.5 to 35, preferably from 0.5 to 10 percent by weight of at least one amine ethoxylate surfactant containing from 8 to 20 moles of ethylene oxide;;
F. from 0.5 to 10 percent by weight of at least one cosurfactant which is a glycol ether, a C4-C12 aliphatic alcohol, an alcohol ether based on ethylene, propylene or butylene oxide, or a nonionic surfactant with an HLB value of less than 10; and,
G. sufficient water to serve as the continuous phase for the emulsion.
The term "herbicide" is used herein to mean an active ingredient which controls or adversely modifies the growth of plants because of phytotoxic or other effects substantial enough to seriously retard the growth of the plant or further to damage the plant sufficiently to kill the plant.
The term "stability" refers to the resistance of emulsions to the coalescence of their dispersed droplets.
The term "plants" is meant to include germinant seeds, emerging seedlings, rhizomes and established vegetation.
The term "water-insoluble" as used herein means having a solubility in water of less than about 0.1 percent by weight at 25"C.
Detailed Description of the Invention
The active herbicidal compound or compounds within the non aqueous or "oil" phase of the present invention are preferably non-water miscible herbicides which are liquid below 30"C or non-water miscible herbicides which are a solid above 30"C and are soluble in non aqueous solvents commonly employed as herbicidal carriers at levels above 30 percent by weight at 20"C.
Examples of non-water miscible herbicides which are a liquid below 30 C are:
3,5,6-trichloro-2-pyridinyloxyacetic acid as
the butoxyethyl ester triclopyr butoxyethyl
ester;(4-chloro-2-methyl phenoxy) acetic acid
as the butoxyethyl or iso-octyl esters (MCPA
butoxy ethyl ester and MCPA-iso-octyl ester); (+)-2-4-(4-chloro-2-methylphenoxy)propionic acid as the iso-octyl ester (Mecoprop-iso
octyl ester);
3,6-dichloro pyridine-2-carboxylic acid as the
iso-octyl ester (clopyralid iso-octyl ester); (+)-2-(4-( (5-(trifluromethyl)-2-pyridil]- oxy]phenoxy] propionic acid as the butyl ester
(fluazifop-butyl); (R)-2-r4-( 5-trifluoromethyl)-2-pyridinyl- oxy)phenoxy] propionic acid as the butyl ester
(fluazifop-P-butyl);;
(2,4-dichlorophenoxy)acetic acid, (2,4-D) as
the 2-butooxyethyl, iso-octyl or butyl esters,
(2,4-D-butoxyethyl ester, 2,4-D-iso-octyl
ester and 2,4-D-butyl ester);
(+)-2-(2,4-dichlorophenoxy)propionic acid,
2,4-DP as the iso-octyl,2-butooxyethyl esters
(2,4-DP-iso-octyl ester and 2,4-DP 2
butyooxyethy ester); and
0-(6-chloro-3-phenyl-4-pyridazinyl)-S-octyl
carbanothioate (pyridate); all of which are commercially available. Preferably, the liquid non-water miscible herbicide is trichlopyr oran ester thereof such as triclopyr butoxyethyl ester (available from DowElanco under the Trade Mark
CROSSBOW).
Examples of non-water miscible herbicides which are a solid above 30 C are:
[4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)]
acetic acid, as 1-methyl heptyl ester (fluoxypry
l-methyl heptyl ester);
N-benzoyl-N-(3,4-dichlorophenyl)-DL-alanine ethyl
ester (benzoyl pro-ethyl);
2,6-dichloro-4-cyanophenyl octanoate (bromoxynil
octanoate); 2-E1-(ethoxyimino)butyl]-3-hydroxy-5-(tetrahydro-
2H-thiopyran-3-yl ) -2-cyclohexane-1-one (cycloxydim);
S-(2,3-dichloro-2-propenyl)bis(1-methylethyl)
carbamothioate (di-allate); (RS-2- (4- (2,4- dichlorophenoxy)phenoxyl]propanoic acid, methyl ester (diclofop methyl); (#)-2-[4-[(6-chloro-2- benzoxazolyl)oxy]phenoxy]
propanoic acid, ethyl ester (fenoxaprop ethyl);;
N-benzoyl-N-(3-chloro-4-fluorophenyl)-D-alnine,
methyl and isopropl esters (flamprop-M-isopropyl
and flamprop-M-methyl); (#)-2-[4-[(3-chloro-5-(trifluoromethyl)-2- pyridinyl]oxy]phenoxy]propionic acid, as methyl
and ethoxy ethyl esters (haloxyfop- methyl and
haloxyfop-ethoxyethyl);
2,6-diiodo-4-cyanophenyl octanoate (ioxynil
octanoate);
N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitro
benzenamine (pendimethalin) and ()-2-4-(6-chloro-2-quinoxalinyloxy)- phenoxy]propanoic acid as ethyl ester
(Quizalofop-ethyl); all of which are commercially available.
Preferably, the non-water miscible herbicide which is a solid above 30 C is fluroxypyr, or an ester thereof. Fluroxypyr is described in U.S. Patent 3,761,486 and is represented by the formula
Esters of fluroxypyr are disclosed in U.S.
Patent 3,755,339. Fluroxypyr-l-methyl heptyl ester is available from DowElanco under the Trade Mark STARANE.
The water-insoluble herbicides, such as fluroxypyr or triclopyr will be present in the emulsion composition at a concentration of from about 1 to about 30 percent by weight, preferably from about 2 to about 20 percent by weight, and more preferably from about 2 to about 15 percent by weight.
Any organic solvent in which the fluroxypyr or triclopyr are soluble, and which is non-reactive withglyphosate and which is essentially waterinsoluble (solubility less than 1 percent by weight) may be employed in the emulsions of the present invention. Suitable organic solvents include, for example, xylene, kerosene, Cg aromatics, Nalkylpyrrolidines such as N-octyl or N-dodecyl esters derived from naturally occurring fatty acids, monochlorobenzene and the like, or a blend of two or more such materials. Organic solvents which have a high flash point and which are of low toxicity to man will be preferably utilized in the emulsion compositions of the present invention. The organic solvent is present in the emulsion composition at a concentration of from 2 to 25 percent by weight, preferably at from 5 to 20 percent by weight of the total emulsion composition.
The water-soluble herbicide active ingredient of the present invention is a salt of Nphosphonomethyl glycine (glyphosate). Suitable salts of glyphosate are those selected from the group consisting of Group I and Group II metals having an atomic number up to 30, hydrochloride, pyridine, ammonium, aniline, lower aliphatic hydrocarbon amines and lower alkanol amines, wherein "lower" designates aliphatic radicals which have up to 4 carbon atoms in a straight or branched chain. The preferable salt of glyphosate for use in the present invention is the isopropylamine salt. The concentration of the glyphosate salt present in the emulsion of the present invention is from 1 to 30 percent by weight, preferably from 10 to 25 percent by weight of the total composition.The isopropylamine salt of Nphosphonomethyl glycine is commercially available from
Monsanto Company as a concentrate under the Trade Mark
ROUNDUP.
The emulsifying system essential to the present invention is a blend of amine-ethoxylate surfactants which create the proper hydrophile to lipophile balance (HLB) to maintain the herbicides of the present invention as an emulsion. According to the HLB system, surfactants are classified by the size and strength of the hydrophilic and lipophilic portions of the molecule. The balance in the size and strength of these two opposing groups is called the hydrophile-lipophile balance or HLB. An emulsifier that is lipophilic in character is assigned a low HLB number, while an emulsifier that is hydrophilic in character is assigned a high number. The values that have been assigned to emulsifiers range from one to forty with the midpoint being about ten. A thorough explanation of hydrophilic- lipophilic balance can be found in L. I. Osipov, Surface Chemistry (1962).
Suitable ethoxylated amine surfactants for use in the present invention include, for example, ethoxylated primary amines derived from animal and vegetable fatty acids; ethoxylated synthetic C12-C18 primary, secondary or tertiary amines; ethoxylated diand polyamines; polyoxyethylenated alkylamines, quaternized polyoxyethylenated amines (eg.
alkylamines) and alkyldimethylamine oxides.
Particularly useful are ethoxylated amines such as oleylamine, cocamine or tallow amine, all with 1 to 20 moles of ethylene oxide; and hydrogenated tallow amines with 1 to 20 moles ethylene oxide. The total amount of emulsifier will generally be in the range of from 1 to 30 percent, preferably from 2 to 25 percent, and more preferably from 2 to 15 percent by weight of the total composition. The preferred combination of surfactants being an amineethoxylate containing 2 to 5 moles of ethylene oxide and being a cocoamine ethoxylate containing between 10 to 20 moles of ethylene oxide.
Commercially available ethoxylated amines are generally a mixture of ethoxy chain lengths. For example, a commercial product which is nominally 2 mole ethoxylated will normally contain small amounts of a product which is 1 or 3 mole ethoxylated. As the degree of ethoxylation increases, the "spread" of ethoxylate chain length also increases. However, the spread of ethoxylate chain length in such commercial products is not generally very broad, and a material with a nominal ethoxylate content of 15 moles of ethylene oxide per molecule will not normally contain any significant amount of material with less than 13 or more than 17 ethylene oxide units.
The ethoxylated amine surfactants employed in the present invention are commercially available from a number of manufactures as described in
McCutcheon's Emulsifiers and Detergents", North
American Edition, 1989, McCutcheon Division, MC
Publishing Co., 175 Rock Rd., Glen Rock, N.J. 07452,
U.S.A.
The emulsifier blend is such as to produce a microemulsion wherein the droplet size is between 5 and 500 nanometers, preferably between 5 and 250 nanometers, and more preferably between 5 and 100 nanometers.
The present invention also requires the presence of a cosurfactant to provide the proper balance between the hydrophilic and lipophilic properties for the required oil and water phases under the conditions of use. Cosurfactants suitable for use in the present invention are, for example, primary C4
C12 aliphatic alcohols, such as butanol and nonanol; alcohol ethers based on ethylene, propylene or butylene oxides such as, 2-butoxy ethanol and dipropylene glycol monomethylether; and nonionic surfactants with HLB values less than 10. Examples of suitable nonionic surfactants are, for example, Cg-C16 alcohol ethoxylates and block copolymers of propylene oxide or ethylene oxide. Other suitable nonionic surfactants include alkyl phenol ethoxylates having 1 to 5 moles of ethylene oxide such as nonyl phenol with 1 mole of ethylene oxide.The amount of cosurfactant in the present invention is from 0.5 to 10 percent by weight, preferably 2 to 5 percent by weight of the total composition.
Suitable cosurfactants are commercially available, such as dipropylene glycol methyl ether, sold by The Dow Chemical Company under the Trade Mark
DOWANOL.
In the emulsions of the present invention, water is present in varying amounts, depending upon the quantities employed of the other ingredients and is present in sufficient quantity to serve as the continuous phase for the water-insoluble dispersed herbicide component.
The herbicidal emulsions of the present invention can contain minor quantities of one or more inert formulation adjuvants, such as antifoaming agents, anti-caking agents, biocides, dyes, anticorrosion agents, freeze point depressents and the like, especially if the compositions are to be stored for any extended period of time prior to use, particularly under acverse storage conditions.
Preparation of the emulsion composition described herein can be carried out using standard procedures in the industry. Generally, the waterinsoluble herbicide is first dissolved in the organic solvent and then blended with the emulsifying surfactants. Glyphosate isopropylamine concentrate (Trade Mark ROUNDUP) is then blended under low shear with the solution containing the water-insoluble herbicide. The cosurfactant is then added followed by water to bring the composition to the desired concentration. The complete mixture is then blended until homogeneity is achieved. Advantageously, when using an herbicide such as fluroxypyr, which is a solid below 30"C, the herbicide is added in the molten state to the organic solvent.
An embodiment of the invention is illustrated by the following Example.
Example I
The following composition is an example of the formulation of the present invention.
Inqredient Grams/Liter Percent w/w Fluroxypyr-1-methylheptyl ester 72 6.58 C9 aromatic solvent (Trade Mark SOLVESSO 150) 118 10.05 Glyphosate - isopropylamine salt 250 22.86 2 mole ethoxylated oleyl amine (Trade Mark ETHOMEEN S-12) 62 5.67 15 mole ethoxylated cocoamine (Trade Mark ETHOMEEN C-25) 38 3.47 Dipropylene glycol monomethylether (Trade Mark DOWANOL DPM) 30 2.74 Water Balance to 1 liter Balance The above formulation was prepared in the following manner:
A.Molten fluroxypyr-1-methylheptyl ester was dissolved in Solvesso 150, and then blended with the two surfactants, Ethomeen S-12 and C-25.
B. The solution prepared in (A) was added to a glyphosate isopropylamine concentrate. The glyphosate isopropylamine concentrate was added as 614g of the commercial herbicidal concentrate ROUNDUP.
C. Dowanol DPM was then added to the mixture in B above followed by water and the complete mixture blended until homogeneity was achieved.
Example IA
The chemical stability of an emulsion formulation as prepared in Example I under various storage temperatures is given in Table IA. The emulsion samples were stored in glass and the data given as acid equivalents of the fluroxypyr acid as measured by high performance chromatography using a 24 cm x 4.6 mm column coated with APEX ODS (5 micron), stationary phase eluting with 65:35 acetonitrile:water. The data indicates only up to about a 3 percent loss after one month storage at 55"C.
TABLE IA
Chemical Stability
Storage period Storage Grams Fluroxypyr temperature (Starane) Acid Equivalents/Liter One month -10 C 47.1 40"C 46.6 55"C 45.6 Example IB
The dilution characteristics of the emulsion formulation as prepared in Example I in soft (20 ppm CaC03) and hard (500 ppm CaC03) waters as defined by the
World Health Organization are given in Table IB, and after storage for one month at various temperatures in
Table IC.The dilution test was done using a 2 percent v/v dilution in 20 and 500 ppm CaCO3 equivalents water at 20 C utilizing the Collaborative International
Pesticides Analytical Committee (CIPAC) test method,
MT36.1.
TABLE IB
Dilution Characteristics
Time 20 ppm CaCOR = 500 ppm CaCO 1/2 hour Trace1 Nil2 1 hour Trace Nil 2 hours Trace Nil Re-dispersion Complete Complete 2 hours Nil Nil 1Trace means less than 0.05 percent by volume cream.
2Nil means no visible cream. TABLE IC
Dilution Characteristics after Storage for one month
Time Storage at -10 C Storage at 40 C Storage at 55 C 20 500 20 500 20 500 hour Nil* Nil Nil Nil Nil Nil 1 hour Nil Nil Nil Nil Nil Nil 2 hours Nil Nil Nil Nil Nil Nil Re-dispersion Complete Complete Complete Complete Complete Complete 2 hours Nil Nil Nil Nil Nil Nil Nil* means no visible cream Example ID
The variation in the pH of an emulsion formulation as prepared in Example I after storage in glass under various conditions is given in Table 1D.
TABLE ID
Variation of pH
Store Time Store | Neat 5 Percent Temperature (v/v) Dilution Initial - 5.76 5.08 1 month -10 C 6.35 5.48 40 C 6.29 5.63 55 C 6.26 5.58 Example II
Microemulsion containing Haloxyfop ethyoxyethyl ester and Glyphosate as the isopropylamine salt.
A microemulsion preparation was prepared utilising the following ingredients:
Composition Ingredient g/Litre % w/w Haloxyfop ethoxy ethyl ester 35.0 3.19 C9 Aromatic solvent 65.0 5.92 (Trade Mark Solvesso 150)
Composition Ingredient g/Litre % w/w Glyphosate 225 20.48 (as isopropylamine salt) 5 mole ethoxylated cocoamine 50.0 4.55 (Trade Mark Ethomeen C-15) 15 mole ethoxylated cocoamine 250 22.76 (Trade Mark Ethomeen C-25) Dipropylene glycol monomethyl 60 5.46 ether (Trade Mark Dowanol DPM) Water Balance to 1 Balance litre The formulation was prepared in the following manner. Molten Haloxyfop ethoxyethyl ester was dissolved in Solvesso 150 and then blended with the two surfactants, Ethomeens C-15 and C-25. The resulting solution was added to a glyphosate isopropylamine concentrate. The glyphosate concentrate was added as 553g of the commercial herbicidal concentrate, ROUNDUP. DOWANOL DPM was then added to the mixture above, followed by water and the complete mixture blended until homogeneity was achieved.
Example III
Microemulsion concentrate containing triclopyr butoxy-ethyl ester and Glyphosate as the isopropylamine salt.
A microemulsion composition was employed utilising the following ingredients:
Composition Ingredient g/Litre % w/w Triclopyr butoxy ethyl ester 139 12.32 Glyphosate 225 19.94 (as Isopropylamine salt) (Trade Mark Solvesso 150) 5 mole ethoxylated cocoamine 50.0 4.43 (Trade Mark Ethomeen C-15) 15 mole ethoxylated cocoamine 235 20.82 (Trade Mark Ethomeen C-25) Dipropylene glycol monomethyl 50 4.43 ether (Trade Mark Dowanol DPM) Water Balance to 1 Balance litre The formulation was prepared in the following manner.
Ethomeens C-15 and C-25 were blended with triclopyr butoxy ester. The resulting solution was added to 553 grams of the commercial herbicidal concentrate, ROUND
UP. DOWANOL DPM was then added to the mixture followed by water and the complete mixture blended until homogeneity was achieved.
Example IV
Microemulsion concentrate containing 2,4-D iso-octyl ester and glyphosate as the isopropylamine salt.
A microemulsion was prepared, utilising the following ingredients:
Composition Ingredient g/Litre % w/w 2,4-D iso octyl ester 151 13.57 Glyphosate 225 20.22 (as Isopropylamine salt) 2 mole ethoxylated cocoamine 40 3.59 (Trade Mark Ethomeen C-12) 15 mole ethoxylated cocoamine 320 28.76 (Trade Mark Ethomeen C-25) Dipropylene glycol monomethyl 60 5.39 ether (Trade Mark Dowanol DPM) Water Balance to 1 Balance litre The formulation was prepared in the following manner.
Ethomeens C-12 and C-25 were blended with 2,4-D isooctyl ester. The resulting solution was added to 553 grams of the commercial herbicidal concentrate, ROUND
UP. DOWANOL DPM was then added to the mixture followed by water and the complete mixture blended until homogeneity was achieved.
The sprayable herbicide composition formulated from the microemulsion concentrate from this invention may be applied from all types of presently used equipment with no plugging of the spray nozzle or other malfunction of the spray equipment.
The herbicide emulsions described herein produce weed control comparable to the conventional tank mixtures of the active herbicidal ingredients.
When the emulsion of Example 1 was compared with a comparable tank mix containing active ingredients sourced from commercial products, no significant differences in weed control were observed.
As can be seen from the foregoing, the preferred embodiments of this invention provide a flowable, herbicidal microemulsion concentrate composition containing the water-soluble isopropylamine salt of N-phosphonomethylglycine (glyphosate) and a water-insoluble fluroxypyr or triclopyr herbicide within a novel emulsifier system as a pre-packaged, one- container mixture which can be conveniently stored and handled and which has enhanced storage-stability.
Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the
Examples be considered as exemplary only, with the scope of the invention being indicated by the following claims.
Claims (10)
1. A water-dispersible herbicidal microemulsion concentrate composition comprising:
A. from 1 to 30 percent by weight of at least one water-insoluble herbicide;
B. optionally, from 0 to 25 percent by weight of a non-water miscible organic solvent in which the water-insoluble herbicide is soluble;
C. from 1 to 30 percent by weight of a water-soluble salt of glyphosate;
D. from 0.5 to 35 percent by weight of at least one amine ethoxylate surfactant containing from 2 to 5 moles of ethylene oxide;
E. from 0.5 to 35 percent by weight of at least one amine ethoxylate surfactant containing from 8 to 20 moles of ethylene oxide;;
F. from 0.5 to 10 percent by weight of at least one cosurfactant which is a glycol ether, a C4 C12 aliphatic alcohol, an alcohol ether based on ethylene, propylene or butylene oxide, or a nonionic surfactant with an HLB value of less than 10; and,
G. sufficient water to serve as the continuous phase for the emulsion.
2. A composition as claimed in Claim 1, wherein the said at least one water-insoluble herbicide is at least one of fluroxypry, triclopyr or an ester thereof.
3. A composition as claimed in Claim 2, wherein the water-insoluble herbicide is fluroxypyr-1-methylheptyl ester.
4. A composition as claimed in any one of the preceding Claims, wherein the salt of glyphosate is the isopropylamine salt.
5. A composition as claimed in any one of the preceding claims, wherein the amount of component D is from 0.5 to 10 percent by weight of the composition.
6. A composition as claimed in any one of the preceding claims, wherein the amount of component E is from 0.5 to 10 percent by weight of the composition.
7. A composition as claimed in Claim 1, comprising:
A. from 2 to 20 percent by weight of fluroxypyr l-methylheptyl ester;
B. from 5 to 20 percent by weight of a nonwater miscible organic solvent in which the fluroxypyr is soluble;
C. from 10 to 25 percent by weight of the isopropylamine salt of glyphosate;
D. from 0.5 to 10 percent by weight of at least one amine ethoxylate containing 2 moles of ethylene oxide;
E. from 0.5 to 10 percent by weight of at least one cocamine ethoxylate surfactant containing from 10 to 20 moles of ethylene oxide;
F. from 2 to 5 percent by weight of at least one cosurfactant which is a glycol ether, a 04- C12 aliphatic alcohol, an alcohol ether based on ethylene, propylene or butylene oxide, or a nonionic surfactant with an HLB value of less than 10; and,
G. sufficient water to serve as the continuous phase for the emulsion.
8. A composition as claimed in Claim 7, consisting essentially of
A. from 2 to 20 percent by weight of fluroxypyr 1-methylheptyl ester;
B. from 5 to 20 percent by weight of a nonwater miscible organic solvent in which the fluroxypyr is soluble;
C. from 10 to 25 percent by weight of the isopropylamine salt of glyphosate;
D. from 0.5 to 10 percent by weight of at least one amine ethoxylate containing 2 moles of ethylene oxide;
E. from 0.5 to 10 percent by weight of at least one cocamine ethoxylate surfactant containing from 10 to 20 moles of ethylene oxide;
F. from 2 to 5 percent by weight of at least one cosurfactant which is a glycol ether, a C4 C12 aliphatic alcohol, an alcohol ether based on ethylene, propylene or butylene oxide, or a nonionic surfactant with an HLB value of less than 10.
9. A herbicidal composition prepared by diluting a herbicidal microemulsion concentrate composition as claimed in any one of the preceding claims to a dilution suitable for application to weeds.
10. A method for the control or prevention of weed infestation, which method comprises applying to the weeds, or to a locus in which the growth of weeds is to be prevented, a composition as claimed in Claim 9.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9211141A GB2267825B (en) | 1992-05-26 | 1992-05-26 | Herbicidal aqueous-based microemulsion compositions |
| TW082103765A TW259688B (en) | 1992-05-26 | 1993-05-13 | |
| KR1019930008934A KR100232030B1 (en) | 1992-05-26 | 1993-05-24 | Herbicidal aqueous-based microemulsion compositions |
| MYPI93000976A MY113265A (en) | 1992-05-26 | 1993-05-24 | Herbicidal aqueous-based microemulsion compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9211141A GB2267825B (en) | 1992-05-26 | 1992-05-26 | Herbicidal aqueous-based microemulsion compositions |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9211141D0 GB9211141D0 (en) | 1992-07-08 |
| GB2267825A true GB2267825A (en) | 1993-12-22 |
| GB2267825B GB2267825B (en) | 1995-08-30 |
Family
ID=10716039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9211141A Expired - Fee Related GB2267825B (en) | 1992-05-26 | 1992-05-26 | Herbicidal aqueous-based microemulsion compositions |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100232030B1 (en) |
| GB (1) | GB2267825B (en) |
| MY (1) | MY113265A (en) |
| TW (1) | TW259688B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0617894A1 (en) * | 1993-04-02 | 1994-10-05 | Monsanto Europe S.A./N.V. | Liquid concentrated herbicidal glyphosate compositions |
| WO1999027781A1 (en) * | 1997-11-27 | 1999-06-10 | Aventis Cropscience Gmbh | Surfactant systems for liquid aqueous preparations |
| WO2000060940A1 (en) * | 1999-04-12 | 2000-10-19 | Dow Agrosciences Llc | Aqueous dispersions of agricultural chemicals |
| WO2000064256A1 (en) * | 1999-04-23 | 2000-11-02 | Monsanto Technology Llc | Enhanced herbicide compositions |
| WO2001010210A2 (en) * | 1999-08-11 | 2001-02-15 | Monsanto Technology Llc | Microemulsion coformulation of a graminicide and a water-soluble herbicide |
| US6245713B1 (en) | 1996-10-25 | 2001-06-12 | Monsanto Company | Plant treatment compositions having enhanced biological effectiveness |
| WO2002096199A2 (en) * | 2001-05-21 | 2002-12-05 | Monsanto Technology Llc | Stable liquid pesticide compositions |
| US6689719B2 (en) * | 1999-08-11 | 2004-02-10 | Monsanto Technology Llc | Coformulation of carfentrazone-ethyl and glyphasate |
| US6703346B2 (en) | 2001-09-26 | 2004-03-09 | Platte Chemical Co. | Herbicide compositions comprising imidazolinone acid, methods of preparation, and methods of use |
| EP1399019A1 (en) * | 2001-06-01 | 2004-03-24 | Huntsman Petrochemical Corporation | Adjuvant compositions and pesticides |
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| US6825151B2 (en) * | 2002-01-30 | 2004-11-30 | Nufarm Americas Inc. | Liquid herbicidal compositions and use thereof in a granular herbicide |
| EP1592299A1 (en) * | 2003-01-10 | 2005-11-09 | Battelle Memorial Institute | Sprayable non-aqueous, oil-continuous microemulsions and methods of making same |
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| EP1648226A2 (en) * | 2003-03-11 | 2006-04-26 | Cognis IP Management GmbH | Microemulsions as adjuvants for agricultural chemicals |
| US7049270B2 (en) | 2000-05-19 | 2006-05-23 | Monsanto Technology Llc | Potassium glyphosate formulations |
| WO2008091746A1 (en) * | 2007-01-23 | 2008-07-31 | Pbi/Gordon Corporation | An auxin acid-catalyzed stable microemulsion pesticide formulation |
| WO2009006169A2 (en) | 2007-06-29 | 2009-01-08 | Dow Agrosciences Llc | Synergistic herbicidal composition containing a substituted phenoxy alkanoic acid derivative and a glyphosate derivative |
| EP2068623A2 (en) * | 2006-09-22 | 2009-06-17 | Huntsman Petrochemical Corporation | Pesticide formulation with streaming birefringence |
| WO2010026127A1 (en) * | 2008-09-04 | 2010-03-11 | Akzo Nobel N.V. | Viscoelastic system for drift reduction |
| US8232230B2 (en) | 2000-12-01 | 2012-07-31 | Helena Holding Company | Manufacture and use of a herbicide formulation |
| WO2012151455A1 (en) * | 2011-05-05 | 2012-11-08 | Dow Agrosciences Llc | Stable high strength oil-in-water emulsions |
| US8426341B2 (en) | 2005-05-27 | 2013-04-23 | Helena Holding Company | Herbicide formulation |
| US8536094B2 (en) | 1998-08-13 | 2013-09-17 | Bayer Intellectual Property Gmbh | Herbicidal compositions for tolerant or resistant rice crops |
| US8586504B2 (en) | 2003-04-22 | 2013-11-19 | Monsanto Technology Llc | Herbicidal compositions containing glyphosate and a pyridine analog |
| JP2015500881A (en) * | 2011-12-20 | 2015-01-08 | ダウ アグロサイエンシィズ エルエルシー | Synergistic herbicidal composition comprising fluroxypyr and glyphosate |
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| WO2021205222A1 (en) * | 2020-04-08 | 2021-10-14 | Red Surcos Colombia Ltda. | Phytosanitary herbicide composition in the form of a microemulsion with low surfactant content and high compatibility in ultra-low volume spray liquids, and method for obtaining it |
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-
1992
- 1992-05-26 GB GB9211141A patent/GB2267825B/en not_active Expired - Fee Related
-
1993
- 1993-05-13 TW TW082103765A patent/TW259688B/zh active
- 1993-05-24 KR KR1019930008934A patent/KR100232030B1/en not_active IP Right Cessation
- 1993-05-24 MY MYPI93000976A patent/MY113265A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| KR940005219A (en) | 1994-03-21 |
| TW259688B (en) | 1995-10-11 |
| MY113265A (en) | 2002-01-31 |
| GB2267825B (en) | 1995-08-30 |
| KR100232030B1 (en) | 1999-12-01 |
| GB9211141D0 (en) | 1992-07-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20030526 |