MXPA06001850A - Herbicidal composition - Google Patents

Abstract

A dehydration step provides a good storage stability to clethodium formulation. A herbicidal composition comprising clethodim as an active ingredient, wherein the content of water in the herbicidal composition is less than approximately 0.20%by weight provides a good storage stability of the clethodim in the composition.

Description

HERBICIDE COMPOSITION Field of the Invention The present invention relates to a 5-herbicide-and-a-pesticide composition for producing a herbicidal composition.

BACKGROUND OF THE INVENTION Some compositions containing a compound of cyclohexanedione herbicide are known from USP-4, 626, 276, USP- 4,741,768, USP-5,084,087 and USP-5, 554,576.

Brief Description of the Invention The present invention provides a herbicidal composition comprising clethodim as an active ingredient, wherein the water content is less than about 0.20% by weight. In addition, the present invention provides a compound for producing a herbicidal composition containing clethodim as an active ingredient, which comprises a dehydration step. In accordance with the present invention, the herbicidal composition of the present invention or the herbicidal composition produced by the present process provides a adequate stability under storage of clethodim in REF .: 169145 composition.

DETAILED DESCRIPTION OF THE INVENTION In the present invention, clethodim is a herbicidal ingredient, and the chemical name of clethodim is (±) -2- [(E) -1- t (E) -3-chloroalyloxyimino] ropil] -5 - [2- (ethylthio) propyl] -3-hydroxycyclohex-2-enone of the formula: It can be obtained in the market, for example, it is supplied by Valent U.S.A. Corporation or Arvestá Corporation. The herbicidal composition of the present invention generally comprises: i) clethodim, ii) an anionic surfactant, iii) a nonionic surfactant and iv) an aromatic hydrocarbon. The content of the clethodim in the herbicidal composition is generally from 5% to 40% by weight, preferably 10% to 30% by weight. The sulfonate surfactant is generally used as the anionic surfactant. The sulfonate surfactant means an anionic surfactant having at least one sulfonic acid salt group in the molecule. Examples of the sulfonate surfactant include salts of alkylbenzenesulfonic acid (for example, alkylbenzenesulfone-to-of-C8-C15), - alkylnaphthalenesulfonic acid salts, salts of alkylsulfonic acid, salts of alkylether sulfonic acid, salts of alkylether sulfonic acid acid fatty acid and salts of polyoxyalkylene tristyrylphenylether sulphonic acid. Typical examples of the "salt are calcium, sodium and potassium salts Typical examples of the sulfonate are dodecylbenzenesulfonate, diisopropylnaphthalenesulfonate, diisobutylnaphthalenesulfonate, α-olefinsulfonate and dialkylsulfosuccinate, among which calcium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate and potassium dodecylbenzenesulfonate are preferably used. The content of the sulfonate surfactant in the herbicidal composition is generally from 0.1% to 10% by weight, preferably 0.1% to 5% by weight. Typical examples of nonionic surfactant include polyoxyalkylene polyaryl ethers, polyoxyethylene vegetable oils , polyoxyalkylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene fatty alcohol ethers and polyoxyethylenealkanolamides Polyoxyalkylene polyarylene ether means a nonionic surfactant having two or more aromatic rings, wherein at least one aromatic ring has a polyoxyalkylene group, and an ether structure in the molecule. Typical examples of the polyoxyalkylene polyaryl ether include polyoxyalkylene styrylphenyl ether, polyoxyalkylene styryl phenylphenyl ether, polyoxyalkylene benzylphenyl ether, polyoxyalkylene benzylphenylphenyl ether and polyoxyalkylene bisphenyl ether. The polyoxyalkylene part is generally polyoxyethylene, polyoxypropylene or copolymer in polyoxyethylene and polyoxypropylene blocks. Typical examples are polyoxyalkylene tristyrylphenyl ether - (for example, polyoxyalkylene tristyrylphenyl ether, polyoxyalkylene-polyoxypropylene tristyrylphenyl ether) and polyoxyalkylene distillyphenyl ether (for example, polyoxyalkylene disrylyphenyl ether). The HLB of the polyoxyalkylene polyaryl ether is preferably 12 to 15. HLB stands for Hydrophilic-Lipophilic Balance which is well known in the field of surfactants. The polyoxyethylene vegetable oil is a product of the addition of ethylene oxide to vegetable oil. A typical example is polyoxyethylene castor oil. The polyoxyalkylene fatty acid ester is a nonionic surfactant which is generally given by the formula: - --- - - RCOO (AO) nH or RCOO (AO) nCOR wherein R is an alkyl or alkenyl group having 6 to 21 carbon atoms; AO is polyoxyethylene, polyoxypropylene or block copolymer of polyoxyethylene and polyoxypropylene and n is 2 to 30. The polyoxyalkylene fatty acid ester is obtained commercially or is produced by known methods.

For example, polyoxyethylene fatty acid esters can be produced by an addition of ethylene oxide to fatty acid or a fatty acid esterification with polyethylene glycol. The polyoxyalkylene fatty acid ester has a HLB preferably in the range of 8 to 16. Typical examples of the polyoxyalkylene fatty acid ester include polyoxyethylene monooleate, polyoxyethylene dioleate, polyoxyethylene monolaurate, polyoxyethylene dilaurate and polyoxyethylene monostearate. The polyoxyethylene sorbitan fatty acid ester is a product of adding ethylene oxide to sorbitan fatty acid ester, wherein the fatty acid is generally a saturated or unsaturated C8-C22 aliphatic acid. Examples of the polyoxyethylene sorbitan fatty acid ester include polyoxyethylene sorbitan monooleate, polyoxyethylen-sorbitan monostearate, polyoxyethylene sorbitan monomethyl-steroate and polyoxyethylene sorbitan monotalate. The block copolymer of ethylene oxide (EO) and propylene oxide (PO) is also called a polyoxyethylene-polyoxypropylene block copolymer. Examples of the block copolymer of ethylene oxide and propylene oxide are (PO) x- (EO) y, (EO) x- (PO) y, (PO) x- (EO) y- (PO) zy (EO) ) x- (PO) y- (EO) z. Among them, they are used namely (PO) x- (EO) and- (PO) E, for example: and (EO) x- (PO) y- (EO) z, namely: The polyoxyalkylene alkylphenyl ether is also known as polyoxyalkylene alkylphenol and means a nonionic surfactant which is polyoxyalkylated alkylphenol. It is typically given by the formula: R-C6H4-0- (AO) nH, wherein R is an alkyl, (AO) n is polyoxyethylene, polyoxypropylene or polyoxyethylene-polyoxypropylene block copolymer and n is 2 to 50. Typical examples of the Polyoxyalkylene alkylphenyl ether include polyoxyalkylene nonylphenyl ether and polyoxyalkylene octylphenyl ether. The polyoxyalkylene fatty alcohol ether means a nonionic surfactant which is polyoxyalkylated fatty alcohol. It is also known as polyoxyalkylene alkyl ether. It is typically given by the formula: R-0- (AO) mH, wherein R is a higher alkyl containing one or more carbon-carbon double bonds therein, in other words, R may be alkenyl, (A0) m is polyoxyethylene, polyoxypropylene or block copolymer of polyoxyethylene-polyoxypropylene and is 2 to 20. Typical examples of the polyoxyalkylene alkyl ether include polyoxyalkylene lauryl ether, polyoxyalkylene octyl ether, polyoxyalkylene myristyl ether, polyoxyalkylene stearyl ether and polyoxyalkylene oleyl ether . It is prepared by the addition of alkylene oxide (for example, ethylene oxide, propylene oxide) of fatty alcohols, for example a C10-C22 aliphatic alcohol. The polyoxyalkylene alkanolamide is a polyoxyalkylenated fatty acid amide in general. It is typically given by the formula: RC0NH (A0) nH or RC0N (A0) nH] 2 wherein R is an alkyl group having 6 to 21 carbon atoms; (A0) n is polyoxyethylene, polyoxypropylene or block copolymer of polyoxyethylene and polyoxypropylene and n is 2 to 30. The type RCONH (AO) nH is preferably used. Examples of the polyoxyalkylene alkanolamide surfactant include polyoxyethylenelauramide, polyoxyethylene diastere, polyoxyethylenecocamide, polyoxypropylenecocamide, polypropylene glycol 2-hydroxyethylisostearamide and ~ 5"polypropylene glycol 2 ^ hl-drOxiet-ilcocamide - The content of nonionic surfactant in the herbicidal composition is generally from 0.1% to 30% by weight, preferably 1% to 20% by weight Examples of the aromatic hydrocarbon include xylene, -phenylxylylethane, Hisol SAS-296 (a mixture of 1-phenyl-1-xylylethane and 1-phenyl-1-ethylphenylethane, trade name of Nippon Petroleum Company), Cactus Solvent HP-DMN (containing 80% dimethylnaphthalene, trade name from Nikko Petrochemical Company), Cactus Solvent P-100 (alkylbenzene that has 9 to 10 carbon atoms, trade name of Nikkp Petrochemical Company), Aromatic 150 (aromatic hydrocarbon, trade name of ExxonMobil Chemical) and Aromatic 200 (aromatic hydrocarbon, trade name of ExxonMobil Chemical). The content of the aromatic hydrocarbon in the herbicidal composition of the present invention is generally from 10% to 89.8% by weight. In addition, the herbicidal composition optionally comprises the other solvent, auxiliaries such as esters of fatty acid, antioxidant, fungicide, perfume, dye and others. Fatty acid esters can generally function as a bioefficacy enhancer. The formula of fatty acid esters is RCOOR '; wherein R is a "" alkyl group "" having "™ 7" ~~ "2" -carbon atoms "" or alkenyl group having 7 to 21 carbon atoms and R 'is an alkyl group having 1 to 8 carbon atoms Examples of the group given by the formula RCO include palmitoyl, myristoyl, stearoyl, lauroyl and oleoyl Examples of R 'are methyl, ethyl, isopropyl, butyl, isobutyl and octyl. Typical of the fatty acid esters are methyl oleate, methyl palmitate, methyl laurate, isopropyl myristate, isopropyl palmitate, octyl laurate, octyl palmitate and butyl stearate.When the fatty acid ester is used, the The content of the fatty acid ester in the herbicidal composition is generally from 0.1% to 79.8% by weight, preferably from -10% to 50% by weight.In addition, when the fatty acid ester is used, the content of the hydrocarbon The aromatic composition in the herbicidal composition of the present invention is preferably from 10% to 60% by weight. In addition, propyl gallate is used for antioxidant; the content of the propyl gallate in the herbicidal composition is generally from 0.01% to 10% by weight, preferably 0.1% to 3% by weight.

The present invention also provides a process for producing a herbicidal composition containing clethodim as an active ingredient, which comprises a dehydration step. The herbicidal composition obtained by the ^ -5-p-rooeso-hasna-adequate-storage stability of the clethodim in the composition and the water content is generally less than about 0.20 wt%. The process of the present invention is described in detail below. . .

The dehydration step can be applied to a mixture or a raw material and carried out, for example, by bubbling dry gas such as air and nitrogen through liquid; causing the liquid to make contact with a water-absorbing material such as crystalline-porous zeolite (such as molecular sieve 3A, molecular sieve 4A, molecular sieve 5A), anhydrous sodium sulfate, anhydrous calcium sulfate, anhydrous magnesium sulfate, calcium chloride and calcium oxide; or by azeotropic distillation using toluene, xylene, benzene, ethylbenzene and others. The dry .gas can Prepare by causing a gas (eg, nitrogen, compressed air) to pass through a desiccant such as calcium chloride, silica and so on. Dry nitrogen may be available from the cylinder on the market as is. Namely, a typical procedure is to mix Clethodim, an anionic surfactant, a non-ionic surfactant, an aromatic hydrocarbon and optionally the other solvent, auxiliaries and the like, and then bubbling dry gas through the mixture or causing the mixture to make contact with a water-absorbing material . Another typical method is to mix clethodim, an anionic surfactant, a nonionic surfactant, an aromatic hydrocarbon and optionally the other solvent, auxiliaries and so on, after bubbling dry gas through at least one raw material or causing less a raw material makes contact with a water absorbing material.The raw material or raw material to which the dehydration step is applied is generally the non-ionic surfactant, or both the nonionic surfactant and the solvent including the aromatic hydrocarbon. The herbicidal composition of the present invention is used as an emulsifiable concentrate in general, for example, it is diluted with water to give an emulsion and applied to weeds, especially gramineous weeds such as Agropyron tsukushiense, barnyard grass (Echinochloa crus). galli), green fox tail. { Setaria viridis), giant foxtail (Setaria faberi), large garranchuelo (Digitaria sang? Inalis), annual bluegrass. { Poa annua), black grass. { Alopec? Rus myosuroides), oats (Avena sativa), wild oats. { Avena fatua), Johnson grass. { Sorghum halepense), grass. { Agropyron repens), villous bromine. { Bromus tectorum) and Bermuda grass (Cynodon dactylon) in broadleaf crop fields (eg, soybeans, cotton, sugarcane, peanuts). The dose of application is generally from 10 g to 1000 g per hectare in the amount of clethodim, although it can , 5-var-i-a-r ^ - -con- - the-types-of-wings-herbs objective, climatic conditions and others. The dilution of the herbicidal composition can also be used for aerial application by helicopter, aircraft or radio-controlled helicopter. The herbicidal composition of the present invention can be diluted with water containing 0 a spreading agent. Examples of the spreading agent include Agridex (trade name of Helena Chemical Corporation), Dynamic (trade name of Helena Chemical Corporation), Induce (trade name of Helena Chemical Corporation) and Silwet L-77 (manufactured by Nihon 5 Unicar).

Examples Hereinafter, the present invention is explained in more detail with reference to the examples, but the present invention should not be limited to the following examples.

Example 1 A mixture was obtained by carefully mixing 21.5% by weight of clethodim (purity: 93%), 1.7% by weight of calcium dodecylbenzenesulfonate (60% calcium dodecylbenzenesulfonate in 2-ethylhexanol, Agnique ABS 60C supplied by Cognis), 2.0% by weight of polyoxyethylene-polyoxyethylene tristyrylphenyl ether (HLB 13.5, Soprophor 796P supplied by Rhodia), 4.0% by weight of "5" "oil" for- "d" e_-po "l ±" oxyethylene (HLB 13), -4.-0% - by weight of polyoxyethylene castor oil (HLB 10.8), 40.0% by weight of methyl oleate (Agnique ME 181-U supplied by Cognis) and 26.8% by weight of Aromatic 150 (aromatic hydrocarbon, trade name of ExxonMobil Chemical).

Water in the mixture was 0.23% by weight (reference composition 1). Approximately 150 ml of reference composition 1 was charged into a 300 ml flask and about 40 ml / sec dry nitrogen was bubbled-for two hours.

The water content in the mixture was brought to 0.01% by weight. (Composition 1).

Example 2 A mixture was obtained by carefully mixing 21.5% by weight of clethodim (purity: 93%), 1.7% by weight of calcium dodecylbenzenesulfonate (60% calcium dodecylbenzenesulfonate in 2-ethylhexanol, Agnique ABS 60C supplied by Cognis) , 2.0% by weight of polyoxyethylene-polyoxypropylene tristyrylphenyl ether (HLB 13.5, Soprophor 796P 25 supplied by Rhodia), 11.0% by weight of polyoxyethylene castor oil (HLB 10.8), 40.0% by weight of butyl stearate and 23.8% by weight of Aromatic. 150 (aromatic hydrocarbon, trade name of ExxonMobil Chemical). The water content in the mixture was brought to 0.33% by weight (-composition-of-reference - ^ -) .- ---- = - - _ ... - - Approximately 150 ml of the reference composition 2 they were charged into a 300 ml flask and about 40 l / sec of dry nitrogen were bubbled for three hours. The water content in the mixture was brought to 0..02% by weight. (Composition 2-1). About 80 ml of the reference composition 2 were loaded into a capped bottle and about 15 g of 3A molecular sieve were added and left for three hours. The water content in the mixture was brought to '0.07% by weight. (Composition 2-2).

Example 3 A mixture was obtained by carefully mixing 21.5% by weight of clethodim (purity: 93%), 1.7% by weight of calcium dodecylbenzenesulfonate (60% calcium dodecylbenzenesulfonate in 2-ethylhexanol, Agnique ABS 60C supplied by Cognis), 2.0 wt% of polyoxyethylene-polyoxypropylene tristyrylphenyl ether (HLB 13.5, Soprophor 796P supplied, by Rhodia), 6.0 wt% of polyoxyethylene castor oil (HLB 13), 6.0 wt% of polyoxyethylene castor oil (HLB) 10.8), 64.8% by weight of Aromatic 150 (aromatic hydrocarbon, trade name of ExxonMobil Chemical). The water content in the mixture was 0.32% by weight (reference composition 3). - ~ - Approximately -1-50 ta.1 of -composition reference 3 were loaded into a 300 ml flask and around 40 ml / sec of dry nitrogen were bubbled for three hours.

The water content in the mixture was brought to 0.03% by weight.

(Composition 3).

Example 4 A water content was measured in a polyoxyethylene-polyoxypropylene tristyrylphenyl ether (HLB 13.5) and the value was 0.14% by weight. 10 grams (10 g) of 3A molecular sieve was added to 25 ml of the polyoxyethylene-polyoxyethylene tristyrylphenyl ether and maintained for 15 hours. The water content was brought to 0.04% by weight. A water content was measured in calcium dodecylbenzenesulfonate (60% calcium dodecylbenzenesulfonate in 2-ethylhexanol, Agnique ABS 60C supplied by Cognis) and the value was 0.68% by weight. 10 grams (10 g) of 3A molecular sieve were added to 25 ml of calcium dodecylbenzenesulfonate and maintained for 15 hours. The water content was brought to 0.04% by weight.

The raw material obtained above can provide a herbicidal composition of the present invention.

Test example = - = --- AtTas ^^ 'or herbicide posters listed in the following table were kept at 60 ° C in an oven for 7 days, and the clethodim contents were measured.

As shown in the table, the storage stability of clethodim was improved by the dehydration step. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (13)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. A herbicidal composition comprising clethodim as an active ingredient, characterized in that the water content in the herbicidal composition is less than about 0.20% by weight.

2. The herbicidal composition according to claim 1, characterized in that it comprises clethodim, an anionic surfactant, a nonionic surfactant and an aromatic hydrocarbon.

3. The herbicidal composition according to claim 2, characterized in that it comprises 10% to 30% by weight of clethodim, 0.1% to 5% by weight of an anionic surfactant, 0.1% to 20% by weight of a non-surface active agent. ionic and 10% to 89.8% by weight of an aromatic hydrocarbon.

4. A process for producing a herbicidal composition containing clethodim as an active ingredient, characterized in that it comprises a dehydration step.

5. The process according to claim 4, characterized in that the water content in the herbicidal composition is less than about 0.20% by weight.

6. The process according to claim 4, characterized in that the herbicidal composition comprises clethodim, an anionic surfactant, a nonionic surfactant and an aromatic hydrocarbon. The process according to claim 4, characterized in that the herbicidal composition comprises 10% to 30% by weight of clethodim, 0.1% to 5% by weight of an anionic surfactant, 0.1% to 20% by weight of an agent nonionic surfactant and 0.1% to 89.8% by weight of an aromatic hydrocarbon. 8. The process according to claim 4, characterized in that the dehydration step comprises bubbling dry gas. 9. The process in accordance with the claim 8, characterized in that the dry gas is nitrogen. The process according to claim 4, characterized in that the dehydration step comprises contacting with a water-absorbing material. 11. The process in accordance with the claim 10, characterized in that the water absorbing material is at least one selected from the group consisting of 3A molecular sieve, 4A molecular sieve, 5A molecular sieve and anhydrous sodium sulfate. 12. The process according to claim 4, characterized in that the dehydration step comprises azeotropic distillation. 13. The process according to claim 12, characterized in that the azeotropic distillation is an azeotropic distillation with toluene, xylene, benzene or ethylbenzene.