CN113491269A - Dispersible oil suspending agent of herbicide composition and preparation method thereof - Google Patents

Dispersible oil suspending agent of herbicide composition and preparation method thereof Download PDF

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Publication number
CN113491269A
CN113491269A CN202010199543.6A CN202010199543A CN113491269A CN 113491269 A CN113491269 A CN 113491269A CN 202010199543 A CN202010199543 A CN 202010199543A CN 113491269 A CN113491269 A CN 113491269A
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oil
dispersible oil
percent
active component
suspending agent
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CN113491269B (en
Inventor
丑靖宇
米双
董广新
崔东亮
李洋
卢政茂
杨吉春
刘长令
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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Jiangsu Yangnong Chemical Co Ltd
Shenyang Sinochem Agrochemicals R&D Co Ltd
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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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

Abstract

The invention belongs to the field of agricultural herbicides, and relates to a dispersible oil suspending agent of a herbicide composition and a preparation method thereof. The invention also relates to the use of the dispersible oil suspension agent for preventing undesired plant growth. The dispersible oil suspending agent comprises, by weight, 0.1-20% of an active component A, 1-60% of an active component B, 1-30% of a surfactant, 0.1-5% of a pH regulator, 0.5-5% of a structure stabilizer, 0-20% of a solvent and the balance of an oil base; wherein the active component A is a compound shown as a formula I, and the active component B is selected from glyphosate and agriculturally suitable salt or glyphosate thereofAnd (3) an ester. The dispersible oil suspending agent provided by the invention is stable, has no physical instability phenomena such as creaming and bottom forming during hot storage, and has difficult decomposition of effective components. The herbicide composition can be used for controlling various weeds, and particularly has excellent control effect on broadleaf weeds such as abutilon and zinnia.

Description

Dispersible oil suspending agent of herbicide composition and preparation method thereof
Technical Field
The invention belongs to the field of agricultural herbicides, and relates to a dispersible oil suspending agent of a herbicide composition and a preparation method thereof. The invention also relates to the use of the dispersible oil suspension agent for preventing undesired plant growth.
Background
Patent WO2016095768 reports isoxazoline-containing urea pyrimidines a of general formula I:
Figure BDA0002418876550000011
the compound A in the general formula I has good herbicidal activity.
Glyphosate, english name glyphosate, CA accession number: 1071-83-6, chemical name N- (phosphonomethyl) glycine, molecular formula C3H8NO5P, molecular weight 169.09. Glyphosate is a high-effective, low-toxic and broad-spectrum biocidal herbicide, and has the functions of systemic transmission and broad weed-killing spectrum, and can be used for preventing and killing 40 multifamily plantsAnd can be used for monocotyledon and dicotyledon, annual and perennial, herbaceous and shrub plants, etc. The glyphosate is absorbed by stem leaves and then is transmitted to each part of the plant, has strong destructive power to underground tissues of perennial deep-rooted weeds and can reach the depth which can not be reached by common agricultural machinery. The weeding composition is widely applied to chemical weeding in orchards, mulberry gardens, tea gardens, rubber gardens, grasslands, forest fire-proof roads, railways, expressway wastelands, no-tillage lands and the like.
Patent CN108207997A reports that compound a of formula I and glyphosate can be prepared into aqueous solution, suspension, microemulsion, wettable powder, soluble granules or water dispersible granules, and these preparations do not contain or only contain a small amount of oily substances. The dispersible oil suspending agent takes oil as a medium, can better play the efficacy of pesticide ingredients due to the help of the oil medium in practical application, and simultaneously avoids the problems of flammability, explosiveness and toxicity in production due to the use of environment-friendly oil-based substances as the medium and the absence of low-flash-point organic solvents, so that the dispersible oil suspending agent is safe for operators and users and has lower toxicity and irritation. Although dispersible oil suspensions have many of the above advantages, there are many problems in development, including physical instability due to settling and creaming of suspended particles during long-term storage or storage at elevated temperatures, and the tendency to precipitate crystalline materials during storage.
Patent CN109418286A reports that the problem of heat-storage creaming and caking of glufosinate-propyzamide in an oil-dispersible oil suspension of glufosinate-propyzamide is solved by using anionic surfactant ammonium alkyl benzene sulfonate and fatty alcohol polyoxyethylene ether ammonium sulfate. Patent 201611013569.7 reports that the problem of heat-storage creaming and caking of aminophosphine in an aminophosphine-clethodim dispersible oil suspension is solved by using an anionic surfactant, namely ammonium alkylbenzene sulfonate. Patent CN102651971B reports that the presentation of high physical and chemical stability over extended storage periods of liquid suspension concentrate formulations containing specific mixed ingredients of saflufenacil and glyphosate is achieved by using a diluent selected from esters and amides of fatty acids, hydrocarbon solvents, nonionic surfactants with polyalkoxylate moieties, and anionic surfactants with sulfonate or sulfate groups. The above-mentioned problems solved are all the corresponding problems existed in the specific dosage form under the specific active component, and their respective effects are different, at the same time, because the self-characteristics of active material can not implement mutual system replacement to attain its desired effect.
Disclosure of Invention
The invention aims to provide a herbicide composition (active component A and active component B) dispersible oil suspending agent and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a herbicide composition dispersible oil suspending agent comprises, by weight, 0.1-20% of an active component A, 0-60% of an active component B1, 1-30% of a surfactant, 0.1-5% of a pH regulator, 0-5% of a structure stabilizer, 0-20% of a solvent, and the balance of an oil base;
wherein the active component B is selected from glyphosate and salt or ester thereof suitable for agriculture, and the active component A is a compound shown as a formula I
Figure BDA0002418876550000021
In formula I:
R1is selected from methyl;
R2、R3can be the same or different and is respectively selected from hydrogen, fluorine or chlorine;
R4selected from CO2R6；
R5Selected from hydrogen, methyl, ethyl, tert-butyl or trifluoromethyl;
R6selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, allyl, propargyl, methoxyethyl, ethoxyethyl, 2-tetrahydrofurylidene or 3-tetrahydrofurylidene.
The surfactant is an emulsifier and/or a wetting dispersant.
The emulsifier is one or more of sorbitan fatty acid ester polyoxyethylene ether, sorbitan fatty acid ester, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, ethylene oxide propylene oxide block copolymer, alkylbenzene sulfonate, phenethyl phenol polyoxyethylene ether, phosphate ester salt, alkylphenol polyoxyethylene polyoxypropylene ether, phenethyl phenol polyoxyethylene polyoxypropylene ether and formaldehyde condensation compound;
the wetting dispersant is one or more of carboxylate, polyacrylate, naphthalene sulfonate, lignosulfonate, alkyl naphthalene sulfonate formaldehyde condensate, sulfate and sulfosuccinate.
Preferably, the emulsifier is one or more of sorbitan fatty acid ester polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene oxide propylene oxide block copolymer, alkylbenzene sulfonate, phenethyl phenol polyoxyethylene polyoxypropylene ether and formaldehyde condensate;
the wetting dispersant is one or more of carboxylate, polyacrylate and sulfosuccinate.
Further preferably, the surfactant is an emulsifier and a wetting dispersant; wherein the emulsifier is a mixture of alkyl benzene sulfonate and at least one of the following substances; preferably a mixture of calcium alkyl benzene sulfonate and at least one of the following; the following substances are sorbitan fatty acid ester polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene oxide propylene oxide block copolymer, phenethyl phenol polyoxyethylene polyoxypropylene ether and formaldehyde condensation compound; the wetting dispersant is one or more of carboxylate, polyacrylate and sulfosuccinate.
The pH range of the dispersible oil suspending agent system of the herbicide composition is controlled to be 3.0-4.5.
The pH regulator is one or more of citric acid, glacial acetic acid and phosphoric acid.
The active component A is shown in the formula I: r1Is selected from methyl; r2Selected from fluorine; r3Selected from chlorine; r4Selected from CO2R6；R5Is selected from methyl; r6Is selected from ethyl;
the active component B is selected from N- (phosphonomethyl) glycine, organic salts of N- (phosphonomethyl) glycine, inorganic salts of N- (phosphonomethyl) glycine or esters of N- (phosphonomethyl) glycine.
The structure stabilizer is one or more of organic bentonite, magnesium aluminum silicate and fumed silica.
The solvent is one or more of toluene, xylene, solvent oil, fatty acid methyl ester, methyl oleate, liquid paraffin, epoxidized soybean oil, N-dimethylformamide, N-dimethyldecanamide, sec-butyl acetate, cyclohexanone and dimethyl sulfoxide.
The oil base is one or more of mineral oil, vegetable oil and ester thereof.
A preparation method of a dispersible oil suspending agent of a herbicide composition,
(1) dissolving the active component A into a uniform and transparent state by using a solvent according to the proportion;
(2) and (2) shearing and stirring the solution (1), the active component B, the surfactant, the pH regulator, the structural stabilizer and the oil base until the mixture is uniform, then introducing the mixture into a sand mill for sand milling until the particle size D90 is less than 10 mu m, and thus obtaining the dispersible oil suspending agent.
The application of the herbicide composition dispersible oil suspending agent in controlling various weeds.
The dispersible oil suspending agent has the following advantages:
1. the dispersible oil suspending agent overcomes the difficult problems of creaming of the dispersible oil suspending agent after sanding and creaming after heat storage by adding the specific surfactant calcium alkyl benzene sulfonate, so that the product forms a stable suspension system in a medium. At present, the calcium alkyl benzene sulfonate is mostly used as a dispersing additive of textile oil, grinding oil, diesel oil and engine oil, and the calcium alkyl benzene sulfonate is added into a specific mixed preparation to play the role of an emulsifier and have good dispersing effect on carrier oil base, so that the preparation is prevented from being creamed; meanwhile, the addition of polyacrylate in the surfactant has a synergistic effect.
2. The pH regulator is added into the dispersible oil suspending agent, so that a preparation system is maintained under a proper acidic condition, the problem that the active component A is easy to decompose is solved, and the stable contents of two effective components are ensured.
3. The dispersible oil suspension of the present invention exhibits good physical and chemical stability over extended periods of storage.
4. The dispersible oil suspending agent can be used for controlling various weeds, and is particularly suitable for controlling broadleaf weeds such as abutilon and zinnia.
Detailed Description
For a better understanding of the nature of the present invention, reference should be made to the following examples, which are included to illustrate, but are not to be construed as limiting the present invention, and all changes, substitutions and alterations that do not depart from the spirit and principles of the present invention are intended to be within the scope of the invention as claimed. The structures of the compounds A used in the preparation examples of the formulations described below are shown in Table 1, in which R is the compound1＝CH3。
TABLE 1 Structure of Compound A
Figure BDA0002418876550000031
Figure BDA0002418876550000041
Figure BDA0002418876550000051
Active ingredient B includes glyphosate and various forms of its salts and esters for agricultural use. The percentage of all preparation ratios is mass percentage, and the active components are calculated by effective content.
Formulation examples of formulations
Example 1
According to the weight percentage, 1% of compound A-6 and 2% of solvent cyclohexanone are uniformly stirred at normal temperature, the liquid mixture, 30% of glyphosate acid, 4% of calcium dodecyl benzene sulfonate, 3% of EL-20 (chentai yanchen), 2% of SK560EP (star flying chemical industry), 2% of Yus-FS7PG (bamboo grease), 0.4% of citric acid, 1% of organic bentonite and the balance of methyl oleate (the balance is up to 100%) are added into a mixing kettle, stirring and mixing are carried out by a high shear machine, and then sanding is carried out by a sand mill, so that the oil suspending agent with good dispersibility can be obtained.
Example 2
According to weight percentage, 1 percent of compound A-6 and 3 percent of solvent N, N-dimethyl capramide are evenly stirred at normal temperature, and the liquid mixture, 30 percent of glyphosate acid, 6 percent of calcium dodecyl benzene sulfonate, 2 percent of T-80 (Jiangsu Haian), and 4 percent of Duramax are mixedTMD-205 (Dow chemical), 0.2% of glacial acetic acid, 1% of organic bentonite and the balance of methyl oleate (the balance is up to 100%) are added into a mixing kettle, stirred and mixed by a high-shear machine, and then sanded by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 3
According to weight percentage, 1 percent of compound A-6 and 3 percent of solvent N, N-dimethyl capramide are evenly stirred at normal temperature, and the liquid mixture, 30 percent of glyphosate acid, 6 percent of calcium dodecyl benzene sulfonate, 2 percent of T-80 (Jiangsu Haian), and 4 percent of Duramax are mixedTMD-205 (Dow chemical), 3% HT210 (break Thailand chemical), 0.2% glacial acetic acid, 1% organobentonite and the balance methyl oleate (complement to 100%) are added into a mixing kettle, stirred and mixed by a high shear machine, and then sanded by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 4
According to weight percentage, 18 percent of compound A-6 and 9 percent of solvent xylene are evenly stirred at normal temperature, and the liquid mixture, 2 percent of glyphosate acid, 4 percent of calcium dodecyl benzene sulfonate, 3 percent of Ethylan NS-500LQ (Nanjing Jiemon), 2 percent of Morwet D-500 (Nanjing Jiemon) and 3 percent of Duramax are mixedTMD-518 (Dow chemical), 0.1 percent of citric acid, 1 percent of organic bentonite and the balance of methyl oleate (the complement is 100 percent) are added into a mixing kettle, stirred and mixed by a high-shear machine, and then sanded by a sand mill to obtain the dispersible oil with good dispersibilityA suspending agent.
Example 5
According to the weight percentage, 0.5 percent of compound A-6 and 1 percent of solvent sec-butyl acetate are evenly stirred at normal temperature, and the liquid mixture, 55 percent of glyphosate acid, 4 percent of calcium dodecyl benzene sulfonate, 2 percent of EL-20 (Swchenet swallow Cheng), 3 percent of 600 percent of#(Jinpeng chemical industry), 1% OP-10 (chenchen Taiwan), 2% Atlox LP-1 (England standing grain), 0.2% citric acid, 0.5% organic bentonite and the balance methyl oleate (complement to 100%) are added into a mixing kettle, stirred and mixed by a high shear cutter, and then sanded by a sand mill to obtain the dispersible oil suspending agent with good dispersibility.
Example 6
According to the weight percentage, 4% of compound A-6 and 6% of solvent methyl oleate are uniformly stirred at normal temperature, the liquid mixture, 45% of glyphosate ammonium salt, 6% of calcium dodecyl benzene sulfonate, 4% of 1601 (Nanjing Taihua), 1% of 0201B (Nanjing Taihua), 2% of Yus EP60P (bamboo grease), 0.8% of citric acid, 0.8% of fumed silica and the balance of rapeseed oil (the balance is 100%) are added into a mixing kettle, stirred and mixed by a high shear machine, and then sand grinding is carried out by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 7
According to the weight percentage, 5 percent OF compound A-6 and 5 percent OF solvent N, N-dimethyl capramide are uniformly stirred at normal temperature, the liquid mixture, 5 percent OF glyphosate potassium salt, 6 percent OF calcium dodecyl benzene sulfonate, 3 percent OF 1602 (Jinpeng chemical industry), 1 percent OF AEO3 (Schchentai swallow), 4 percent OF SP-OF3472 (Chinese chemical industry), 1.0 percent OF citric acid, 0.5 percent OF fumed silica and the balance OF soybean oil (the balance is up to 100 percent) are added into a mixing kettle, stirred and mixed by a high shearing machine, and then sand milling is carried out by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 8
According to weight percentage, 0.5 percent of compound A-6 and 3 percent of solvent dimethyl sulfoxide are evenly stirred at normal temperature, and the liquid mixture, 50 percent of glyphosate isopropylamine salt, 5 percent of calcium dodecyl benzene sulfonate and 4 percent of Etocas are mixedTM40 (UK)Standing grain), 1% of S-20 (chensie swallow), 2% of Yus RXB (bamboo grease), 3% of Greensperse BD55 (Grignard), 0.1% of citric acid, 0.5% of fumed silica and the balance of castor oil (the balance is up to 100%) are added into a mixing kettle, stirred and mixed by a high shear machine, and then sanded by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 9
According to the weight percentage, 1% of compound A-8 and 2% of solvent cyclohexanone are uniformly stirred at normal temperature, the liquid mixture, 40% of glyphosate isopropylamine salt, 5% of calcium dodecyl benzene sulfonate, 3% of T-20 (chentai yancheng), 3% of SP-2728 (engine chemical), 0.5% of glacial acetic acid, 0.5% of fumed silica and the balance of methyl oleate (the balance is 100%) are added into a mixing kettle, a high shearing machine is used for stirring and mixing, and then a sand mill is used for sand milling, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 10
According to the weight percentage, 10 percent of compound A-8 and 6 percent of solvent xylene are uniformly stirred at normal temperature, the liquid mixture, 25 percent of glyphosate ammonium salt, 4 percent of calcium dodecyl benzene sulfonate, 3 percent of EL-80 (Jiangsu Haian), 1 percent of 1601 (Nanjing Taihua), 4 percent of SK560EP (star flying chemical industry), 0.2 percent of phosphoric acid, 0.4 percent of organic bentonite and the balance of soybean oil (the balance is 100 percent) are added into a mixing kettle, a high shearing machine is used for stirring and mixing, and then a sand mill is used for sand milling, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 11
According to weight percentage, 12 percent of compound A-10 and 14 percent of solvent N, N-dimethyl capramide are evenly stirred at normal temperature, and the liquid mixture, 20 percent of glyphosate isopropylamine salt, 5 percent of calcium dodecyl benzene sulfonate, 2 percent of Ethylan NS-500LQ (Nanjing Jieron), and 4 percent of Duramax are mixedTMD-305 (Dow chemical), 1% YusEP60P (bamboo oil), 0.5% glacial acetic acid, 0.4% fumed silica and the balance rapeseed oil (the balance is up to 100%) are added into a mixing kettle, stirred and mixed by a high shear machine, and then sanded by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Example 12
According to the weight percentage, 6 percent of compound A-10 and 12 percent of solvent cyclohexanone are evenly stirred at normal temperature, and the liquid mixture, 35 percent of glyphosate acid, 4 percent of calcium dodecyl benzene sulfonate and 2 percent of DOWFAX are mixedTMD-850 (Dow chemical), 4% HT210 (break Thailand chemical), 0.3% phosphoric acid, 0.5% organobentonite and the balance of castor oil (complement to 100%) are added into a mixing kettle, stirred and mixed by a high shear machine, and then sanded by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Comparative example 1
According to the weight percentage, 1% of compound A-6 and 2% of solvent cyclohexanone are uniformly stirred at normal temperature, the liquid mixture, 30% of glyphosate acid, 4% of ammonium dodecylbenzene sulfonate, 3% of EL-20 (chentai yanchen), 2% of SK560EP (star flying chemical industry), 2% of Yus-FS7PG (bamboo grease), 0.4% of citric acid, 1% of organic bentonite and the balance of methyl oleate (the balance is up to 100%) are added into a mixing kettle, stirring and mixing are carried out by a high shear machine, and then sanding is carried out by a sand mill, so that the oil suspending agent with good dispersibility can be obtained.
Comparative example 2
According to the weight percentage, 1 percent of compound A-6 and 3 percent of solvent N, N-dimethyl capramide are evenly stirred at normal temperature, and the liquid mixture, 30 percent of glyphosate acid, 6 percent of dodecyl benzene sulfonic acid ammonium, 4 percent of fatty alcohol polyoxyethylene ether ammonium sulfate, 2 percent of T-80 (Jiangsu sea), 4 percent of Duramax are mixedTMD-205 (Dow chemical), 0.2% of glacial acetic acid, 1% of organic bentonite and the balance of methyl oleate (the balance is up to 100%) are added into a mixing kettle, stirred and mixed by a high-shear machine, and then sanded by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Comparative example 3
According to the weight percentage, 1% of compound A-6 and 2% of solvent cyclohexanone are uniformly stirred at normal temperature, the liquid mixture, 30% of glyphosate acid, 3% of EL-20 (chenchenge swallow sincerity), 2% of SK560EP (star flying chemical industry), 2% of Yus-FS7PG (bamboo grease), 0.4% of citric acid, 1% of organic bentonite and the balance methyl oleate (complement to 100%) are added into a mixing kettle, stirring and mixing are carried out by a high-shear machine, and then a sand mill is used for sand milling, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Comparative example 4
According to the weight percentage, 5% OF compound A-6 and 5% OF solvent N, N-dimethyl capramide are uniformly stirred at normal temperature, the liquid mixture, 5% OF glyphosate potassium salt, 6% OF ammonium dodecylbenzene sulfonate, 3% OF fatty alcohol polyoxyethylene ether ammonium sulfate, 3% OF 1602 (Jinpeng chemical industry), 1% OF AEO3 (Schchentai swallow Cheng), 4% OF SP-OF3472 (engine chemical industry), 1.0% OF citric acid and 0.5% OF fumed silica are added into a mixing kettle, the rest soybean oil (supplemented to 100%) is stirred and mixed by a high shear machine, and then a sand mill is used for sand grinding, so that the dispersible oil suspending agent with good dispersibility is obtained.
Comparative example 5
According to the weight percentage, 1% of compound A-8 and 2% of solvent cyclohexanone are uniformly stirred at normal temperature, the liquid mixture, 40% of glyphosate isopropylamine salt, 5% of dodecylbenzene sulfonic acid ammonium, 3% of T-20 (chentai yanchen), 3% of SP-2728 (engine chemical), 0.5% of glacial acetic acid, 0.5% of fumed silica and the balance of methyl oleate (the balance is 100%) are added into a mixing kettle, a high shearing machine is used for stirring and mixing, and then a sand mill is used for sand milling, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Comparative example 6
According to weight percentage, 12 percent of compound A-10 and 14 percent of solvent N, N-dimethyl capramide are evenly stirred at normal temperature, and the liquid mixture, 20 percent of glyphosate isopropylamine salt, 2 percent of Ethylan NS-500LQ (Nanjing Jiemon) and 4 percent of Duramax are mixedTMD-305 (Tao's chemical), 1% Yus EP60P (bamboo oil), 0.5% glacial acetic acid, 0.4% fumed silica and the balance rapeseed oil (the balance is up to 100%) are added into a mixing kettle, stirred and mixed by a high shear machine, and then sanded by a sand mill to obtain the dispersible oil suspending agent with good dispersibility.
Comparative example 7
According to the weight percentage, 1% of compound A-6 and 2% of solvent cyclohexanone are uniformly stirred at normal temperature, the liquid mixture, 30% of glyphosate acid, 4% of calcium dodecyl benzene sulfonate, 3% of EL-20 (chentai yanchen), 2% of SK560EP (star flying chemical industry), 2% of Yus-FS7PG (bamboo grease), 1.5% of citric acid, 1% of organic bentonite and the balance of methyl oleate (the balance is up to 100%) are added into a mixing kettle, stirring and mixing are carried out by a high shear machine, and then sanding is carried out by a sand mill, so that the oil suspending agent with good dispersibility can be obtained.
Comparative example 8
According to weight percentage, 1 percent of compound A-6 and 3 percent of solvent N, N-dimethyl capramide are evenly stirred at normal temperature, and the liquid mixture, 30 percent of glyphosate acid, 6 percent of calcium dodecyl benzene sulfonate, 2 percent of T-80 (Jiangsu Haian), and 4 percent of Duramax are mixedTMD-205 (Dow chemical), 1.0% of citric acid, 1% of organic bentonite and the balance of methyl oleate (the balance is up to 100%) are added into a mixing kettle, stirred and mixed by a high-shear machine, and then sanded by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Comparative example 9
According to the weight percentage, 1% of compound A-8 and 2% of solvent cyclohexanone are uniformly stirred at normal temperature, the liquid mixture, 40% of glyphosate isopropylamine salt, 5% of calcium dodecyl benzene sulfonate, 3% of T-20 (chentai yancheng), 3% of SP-2728 (engine chemical), 0.5% of fumed silica and the balance of methyl oleate (the balance is 100%) are added into a mixing kettle, stirring and mixing are carried out by a high shearing machine, and then sanding is carried out by a sand mill, so that the dispersible oil suspending agent with good dispersibility can be obtained.
Comparative example 10
According to weight percentage, 12 percent of compound A-10 and 14 percent of solvent N, N-dimethyl capramide are evenly stirred at normal temperature, and the liquid mixture, 20 percent of glyphosate isopropylamine salt, 5 percent of calcium dodecyl benzene sulfonate, 2 percent of Ethylan NS-500LQ (Nanjing Jieron), and 4 percent of Duramax are mixedTMD-305 (Tao's chemical), 1% YusEP60P (bamboo oil), 1.0% triethanolamine, 0.4% fumed silica and the balance rapeseed oil (make up to 100%) are added into a mixing kettle, stirred and mixed by a high shear machine, and then sanded by a sand mill to obtain the final productA dispersible oil suspending agent with good dispersibility.
Physical stability observation and content analysis of examples and comparative examples
The samples obtained in examples 1 to 12 were sealed in an ampoule and subjected to a storage test at ordinary temperature (25 ℃ C., 60 d). Meanwhile, a heat storage experiment is carried out, and the mixture is stored for 14 days in a constant temperature box at the temperature of 54 +/-2 ℃. Physical stability of the different example samples was observed under normal temperature and heat storage experimental conditions (results are shown in table 2). The content change of the effective component A and the effective component B before and after heat storage is analyzed and detected by a liquid chromatography analysis method (the result is shown in Table 3).
The samples obtained in comparative examples 1 to 6 were sealed with an ampoule and subjected to a storage test at ordinary temperature (25 ℃ C., 60 d). Meanwhile, a heat storage experiment is carried out, and the mixture is stored for 14 days in a constant temperature box at the temperature of 54 +/-2 ℃. Physical stability was observed for different comparative samples under normal temperature and heat storage experimental conditions (results are shown in table 2).
The samples of comparative examples 7 to 10 thus obtained were sealed with ampoules, subjected to a heat-storage test and stored at 54. + -. 2 ℃ for 14 days in an incubator. The content change of the effective component A and the effective component B before and after heat storage is analyzed and detected by a liquid chromatography analysis method (the result is shown in Table 3).
The physical stability profiles of the samples of the formulations of the examples and comparative examples are shown in Table 2.
TABLE 2 comparison of physical stability of formulation samples
Figure BDA0002418876550000091
Figure BDA0002418876550000101
The data presented in Table 2 show that the formulations of examples 1-12, all containing calcium dodecylbenzenesulfonate, were physically stable after storage both at hot (54 deg.C, 14d) and ambient (25 deg.C, 60d), and had good flow properties and no creaming. However, the formulations of comparative examples 1-6 (calcium dodecylbenzenesulfonate was replaced with ammonium dodecylbenzenesulfonate, or calcium dodecylbenzenesulfonate was replaced with ammonium dodecylbenzenesulfonate and ammonium fatty alcohol-polyoxyethylene ether sulfate, or calcium dodecylbenzenesulfonate was removed from the formulations) were creamed after being stored for 14 days in hot air, and creamed after being stored for 60 days at room temperature. The results of the comparison of the physical stability of the preparation show that the dispersible oil suspending agent with good physical stability can be obtained by adding the surfactant calcium dodecyl benzene sulfonate.
The decomposition of the active ingredient after storage of each formulation sample at 54 ℃ for 14 days is shown in Table 3.
TABLE 3 Effect of formulation sample pH on the decomposition Rate of active ingredients
Figure BDA0002418876550000102
The data results in Table 3 show that the decomposition rates of both active ingredients in examples 1 to 12 after storage at 54 ℃ for 14d were < 5%, and the decomposition rates of active ingredient A in comparative examples 7 to 10 were > 5%, indicating that the decomposition rate of active ingredient A can be effectively reduced by controlling the pH of the formulations in the range of 3.0 to 4.5 using a pH adjusting agent.
Examples of biological Activity test
1. Purpose of the experiment
Under the greenhouse condition, the test method of pot culture is utilized to compare the herbicidal activity of the herbicide composition dispersible oil suspension (OD) sample provided by the formulation research and development department of Shenyang chemical pesticide chemical research and development Limited.
2. Reagent for testing
Example 1: 31% herbicide composition OD
Example 2: 31% herbicide composition OD
Example 3: 31% herbicide composition OD
Compound A-6+ Glyphosate acid (1:30)
(all the above test samples were provided by the research and development department of the formulations)
3. Weed to be tested
Echinochloa crus-galli (L.) Beauv, Abutilon theophrasti Medic), and Zinnia elegans (Zinnia elegans Jacq.).
4. Test method
Abutilon, cockspur grass and zinnia are sowed in disposable paper cups with the height of 9cm by adopting a direct sowing method, covered with soil of 0.5cm, pressed, placed in a greenhouse for cultivation, and subjected to stem leaf spraying treatment (the spraying pressure is 1.95 kg/cm) by using a crawler-type crop sprayer (designed and produced by Engineer Research Ltd. in British) according to the dosage designed by the test when the 4-6 leaf stage of weeds is generated2The spraying liquid amount is 500L/ha, the track speed is 1.48km/h), the treated mixture is placed in an operation hall, after the liquid medicine is naturally dried, the mixture is placed in a greenhouse to be managed according to a conventional method, the reaction condition of weeds to the pesticide is observed and recorded, and the weed control effect of the pesticide is visually investigated after 15 days.
TABLE 4.31% dispersible oil suspension of herbicide composition the control effect on weeds
Figure BDA0002418876550000111
As can be seen from the data in table 4, example 3 of all the tested agents had the best control effect on weeds, which was superior to the control effect of the herbicidal composition applied directly, especially on abutilon and zinnia. The invention prepares the raw pesticide into the dispersible oil suspending agent, can improve the utilization rate of effective components, achieves the aim of reducing the dosage and is more beneficial to protecting the ecological environment. The pesticide effect of the herbicide composition in example 3 is better than that of example 2, and the formula of the herbicide composition in comparative example 3 and example 2 shows that the polyacrylate HT210 is added in the formula of example 3 compared with that of example 2, and analysis shows that polyacrylate macromolecular substances wrap the surfaces of active ingredient particles to form barriers to prevent the particles from aggregating, so that the active ingredient particles are stably maintained in a fine particle state for a long time, the absorption of weeds to the active ingredient is facilitated, and the control effect is improved.
Those not described in detail in this specification are within the skill of the art.

Claims (10)

1. A dispersible oil suspension concentrate of a herbicidal composition characterized by: the dispersible oil suspending agent comprises, by weight, 0.1-20% of an active component A, 0.1-60% of an active component B1-30%, 1-30% of a surfactant, 0.1-5% of a pH regulator, 0-5% of a structure stabilizer, 0-20% of a solvent and the balance of an oil base;
wherein the active component B is selected from glyphosate and salt or ester thereof suitable for agriculture, and the active component A is a compound shown as a formula I
Figure FDA0002418876540000011
In formula I:
R1is selected from methyl;
R2、R3can be the same or different and is respectively selected from hydrogen, fluorine or chlorine;
R4selected from CO2R6；
R5Selected from hydrogen, methyl, ethyl, tert-butyl or trifluoromethyl;
R6selected from hydrogen, methyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl, trifluoroethyl, allyl, propargyl, methoxyethyl, ethoxyethyl, 2-tetrahydrofurylidene or 3-tetrahydrofurylidene;
the surfactant is an emulsifier and/or a wetting dispersant.
2. A dispersible oil suspension of herbicide composition as claimed in claim 1 wherein said emulsifier is one or more of sorbitan fatty acid ester polyoxyethylene ether, sorbitan fatty acid ester, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, ethylene oxide propylene oxide block copolymer, alkylbenzene sulfonate, phenethyl phenol polyoxyethylene ether, phosphate ester salt, alkylphenol polyoxyethylene polyoxypropylene ether, phenethyl phenol polyoxyethylene polyoxypropylene ether and formaldehyde condensate;
the wetting dispersant is one or more of carboxylate, polyacrylate, naphthalene sulfonate, lignosulfonate, alkyl naphthalene sulfonate formaldehyde condensate, sulfate and sulfosuccinate.
3. A dispersible oil-suspension herbicide composition as claimed in claim 2, wherein said emulsifier is one or more selected from sorbitan fatty acid ester polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene oxide propylene oxide block copolymer, alkylbenzene sulfonate, phenethylphenol polyoxyethylene polyoxypropylene ether and formaldehyde condensate;
the wetting dispersant is one or more of carboxylate, polyacrylate and sulfosuccinate.
4. A dispersible oil-suspension concentrate of a herbicide composition as claimed in claim 3 wherein said surfactant is an emulsifier and wetting dispersant; wherein the emulsifier is a mixture of alkyl benzene sulfonate and at least one of the following substances; the following substances are sorbitan fatty acid ester polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene oxide propylene oxide block copolymer, phenethyl phenol polyoxyethylene polyoxypropylene ether and formaldehyde condensation compound.
The wetting dispersant is one or more of carboxylate, polyacrylate and sulfosuccinate.
5. The dispersible oil-suspension herbicide composition of claim 1 wherein the pH of said dispersible oil-suspension herbicide composition is controlled to be in the range of 3.0 to 4.5.
6. A dispersible oil suspension concentrate of herbicide composition as claimed in claim 1 wherein said pH adjusting agent is one or more of citric acid, glacial acetic acid and phosphoric acid.
7. A dispersible oil-suspension concentrate of a herbicidal composition according to claim 1, wherein said active ingredient is of formula i: r1Is selected from methyl; r2Selected from fluorine; r3Selected from chlorine; r4Selected from CO2R6；R5Is selected from methyl; r6Is selected from ethyl;
the active component B is selected from N- (phosphonomethyl) glycine, organic salts of N- (phosphonomethyl) glycine, inorganic salts of N- (phosphonomethyl) glycine or esters of N- (phosphonomethyl) glycine.
8. A dispersible oil suspension concentrate of a herbicidal composition as claimed in claim 1 wherein said structure stabilizer is one or more of organobentonite, magnesium aluminum silicate, fumed silica;
the solvent is one or more of toluene, xylene, solvent oil, fatty acid methyl ester, methyl oleate, liquid paraffin, epoxidized soybean oil, N-dimethylformamide, N-dimethyldecanamide, sec-butyl acetate, cyclohexanone and dimethyl sulfoxide;
the oil base is one or more of mineral oil, vegetable oil and ester thereof.
9. A process for preparing a dispersible oil-suspendable herbicide composition as claimed in claim 1,
(1) dissolving the active component A into a uniform and transparent state by using a solvent according to the proportion;
(2) and (2) shearing and stirring the solution (1), the active component B, the surfactant, the pH regulator, the structural stabilizer and the oil base until the mixture is uniform, then introducing the mixture into a sand mill for sand milling until the particle size D90 is less than 10 mu m, and thus obtaining the dispersible oil suspending agent.
10. The use of a dispersible oil suspension concentrate of the herbicidal composition of claim 1 for controlling a wide variety of weeds.
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CN115281212A (en) * 2022-04-27 2022-11-04 南通江山农药化工股份有限公司 A kind of dispersible oil suspension agent containing saflufenacil and preparation method thereof
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WO2022199267A1 (en) * 2021-03-22 2022-09-29 南通江山农药化工股份有限公司 Herbicidal composition, preparation, and application thereof
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