WO2022199267A1 - 一种除草组合物、制剂及其应用 - Google Patents

一种除草组合物、制剂及其应用 Download PDF

Info

Publication number
WO2022199267A1
WO2022199267A1 PCT/CN2022/075774 CN2022075774W WO2022199267A1 WO 2022199267 A1 WO2022199267 A1 WO 2022199267A1 CN 2022075774 W CN2022075774 W CN 2022075774W WO 2022199267 A1 WO2022199267 A1 WO 2022199267A1
Authority
WO
WIPO (PCT)
Prior art keywords
herbicidal composition
polyoxyethylene ether
oil
weight ratio
emulsifier
Prior art date
Application number
PCT/CN2022/075774
Other languages
English (en)
French (fr)
Inventor
杜辉
任新峰
朱艳梅
樊梅云
董垒
许映蓉
Original Assignee
南通江山农药化工股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南通江山农药化工股份有限公司 filed Critical 南通江山农药化工股份有限公司
Priority to JP2023544452A priority Critical patent/JP2024505859A/ja
Priority to EP22773929.9A priority patent/EP4230041A1/en
Priority to CA3204749A priority patent/CA3204749A1/en
Priority to BR112023007701A priority patent/BR112023007701A2/pt
Priority to AU2022244795A priority patent/AU2022244795B2/en
Priority to KR1020237013491A priority patent/KR20230070297A/ko
Publication of WO2022199267A1 publication Critical patent/WO2022199267A1/zh
Priority to ZA2023/05792A priority patent/ZA202305792B/en
Priority to CONC2023/0008684A priority patent/CO2023008684A2/es

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • 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
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides

Definitions

  • the invention relates to the technical field of pesticides, in particular to a herbicidal composition, preparation and application thereof.
  • Fenfluazole chemical name: 3-(2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidine-1 (2H)-yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, the unique structure is the combination of uracil and isoxazole structure, and saflufenacil Amines have better herbicidal activity and can effectively control annual and perennial weeds in garden and non-arable land, but the cost is higher. At present, herbicide varieties containing a single active ingredient have different degrees of defects in the agricultural weeding process.
  • continuous use is easy to produce drug resistance, and the herbicidal spectrum is not broad enough. It can only control monocotyledonous weeds or dicotyledonous weeds, or only Control of emerging weeds or weeds that have not emerged, not both.
  • the control effect can be improved, the amount of active ingredients used can be reduced, the cost of control can be saved, the generation of weed resistance can be delayed, the service life of the medicament can be prolonged, and the pollution to the environment can be reduced. .
  • Dispersible oil suspension agent is the oil phase suspension system of the original drug and auxiliary agent (such as emulsifier, dispersant and viscosity modifier, etc.), which is made of oil phase as a carrier and is stable in a non-aqueous medium for a certain period of time. , in which at least one component is insoluble in non-aqueous medium and used after dilution with water.
  • auxiliary agent such as emulsifier, dispersant and viscosity modifier, etc.
  • the present invention provides a herbicidal composition containing saflufenacil and a dispersible oil suspending agent prepared therefrom.
  • auxiliary agents By selecting auxiliary agents, the existing stability of the dispersible oil suspending agent is solved. question.
  • a first aspect of the present invention provides a herbicidal composition
  • the composition comprises saflufenacil and glyphosate; the weight ratio of saflufenacil and glyphosate is: 1:(10-100).
  • the second aspect of the present invention provides a herbicidal composition formulation, which is composed of the above-mentioned herbicidal composition and agrochemically acceptable adjuvants.
  • the formulation of the herbicidal composition is selected from the group consisting of a solution, a microemulsion, a dispersible oil suspension, a wettable powder, and a water dispersible granule.
  • the weight percentage of the herbicidal composition in the herbicidal composition preparation is 5%-90%.
  • the formulation of the herbicidal composition is in the form of a dispersible oil suspension;
  • the agrochemically acceptable auxiliary materials include emulsifiers, wetting agents, dispersants, stabilizers, defoaming agents At least one of the agent, the viscosity modifier and the base oil.
  • the emulsifier is selected from castor oil polyoxyethylene ether, calcium dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol formaldehyde resin Polyoxyethylene ether, sorbitan monostearate, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, alkane In oxypolyoxyethylene ether sulfonate, fatty alcohol sulfate, alkyl phosphate ester, fatty alcohol polyoxyethylene ether sulfate, EO-PO block copolymer and phenethylphenol polyoxyethylene ether sulfonate at least one of.
  • the emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate, and the weight ratio is 1:(0.1-0.5).
  • the dispersant is selected from polycarboxylates, lignosulfonates, EO-PO block copolymers, phosphates and their salts, sulfonates, alkylnaphthalenes At least one of sulfonate, alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
  • the viscosity modifier is a combination of organic bentonite and magnesium aluminum silicate, and the weight ratio is 1:(0.5-2).
  • the third aspect of the present invention provides the use of the herbicidal composition for controlling weeds in non-arable land.
  • the invention provides a herbicidal composition and a dispersible oil suspension agent comprising the herbicidal composition, which have the following beneficial effects:
  • the mechanism of action is unique and there is no cross-resistance, resulting in a synergistic effect, expanding the herbicidal spectrum, improving the control effect, and making up for the single use of the agent on the main weeds.
  • the defect of poor control effect improve the persistence of each component of the composition, delay the generation of weed resistance, reduce the repeated use of pesticides, reduce the use amount and cost; can be mainly used in the prevention of non-arable weeds, especially Control of glyphosate-resistant weeds, such as P.
  • the dispersible oil suspension agent prepared is stable in quality and good in performance, which is more conducive to the exertion of efficacy. At the same time, it has excellent low-temperature fluidity, dispersion stability, thermal storage stability, etc.; and its raw materials are readily available, the preparation process is simple, and it is easy to industrialize production.
  • compositions, step, method, article or device comprising the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such composition, step, method, article or device elements.
  • a first aspect of the present invention provides a herbicidal composition
  • the composition comprises saflufenacil and glyphosate; the weight ratio of saflufenacil and glyphosate is: 1:(10-100).
  • the weight ratio of saflufenacil and glyphosate is 1:(20-60).
  • the weight ratio of saflufenacil and glyphosate is 1:40.
  • arable weeds, especially glyphosate-resistant weeds, such as small flies, ox tendon grass, etc. can be controlled.
  • the second aspect of the present invention provides a herbicidal composition formulation, which is composed of the above-mentioned herbicidal composition and agrochemically acceptable adjuvants.
  • the formulation of the herbicidal composition is selected from the group consisting of a solution, a microemulsion, a dispersible oil suspension, a wettable powder, and a water dispersible granule.
  • the herbicidal composition accounts for 5-90% by weight of the herbicidal composition formulation.
  • the formulation of the herbicidal composition is in the form of a dispersible oil suspension;
  • the agrochemically acceptable adjuvants include emulsifiers, wetting agents, dispersing agents, stabilizers, and defoaming agents , at least one of viscosity modifier and base oil.
  • the raw materials for the preparation of the herbicide dispersible oil suspension agent at least include the following components: 5-50% of herbicide composition, 5-20% of emulsifier, 0-5% of wetting agent , 1-5% of dispersant, 0-5% of defoamer, 2-10% of viscosity modifier, and base oil supplemented by 100%.
  • Emulsifiers are a class of compounds that enable a mixture of two or more immiscible components to form a stable emulsion. Its principle of action is that in the emulsification process, the dispersed phase is dispersed in the continuous phase in the form of microdroplets (micron scale), and the emulsifier reduces the interfacial tension of each component in the mixed system and forms a firmer film on the surface of the droplet. Or due to the charge given by the emulsifier, an electric double layer is formed on the surface of the droplets, preventing the droplets from agglomerating with each other, and maintaining a uniform emulsion. From a phase point of view, emulsions are still heterogeneous systems.
  • the dispersed phase in the emulsion can be water phase or oil phase, most of which are oil phase; the continuous phase can be oil phase or water phase, most of which are water phase.
  • Emulsifier is a surfactant with hydrophilic and lipophilic groups in the molecule.
  • the hydrophilicity or lipophilicity of the emulsifier the "hydrophilic-lipophilic balance value (HLB value)" is usually used.
  • HLB value hydrophilic-lipophilic balance value
  • the lower the HLB value the stronger the lipophilicity; on the contrary, the higher the HLB value, the more hydrophilic powerful.
  • the HLB value of various emulsifiers is different. In order to obtain a stable emulsion, an appropriate emulsifier must be selected.
  • the emulsifier is selected from castor oil polyoxyethylene ether, calcium dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol formaldehyde resin polyoxyethylene ether, sorbitan Alkyd anhydride monostearate, sorbitan monostearate polyoxyethylene ether, phenethylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, alkoxy polyoxyethylene ether At least one of sulfonate, fatty alcohol sulfate, alkyl phosphate ester salt, fatty alcohol polyoxyethylene ether sulfate, EO-PO block copolymer and phenethylphenol polyoxyethylene ether sulfonate.
  • the emulsifier is a combination of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate in a weight ratio of 1:(0.1-0.5).
  • the weight ratio of castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonate is 1:0.35.
  • the HLB value of the castor oil polyoxyethylene ether is 9-14.
  • the HLB value of the castor oil polyoxyethylene ether is 11-13.
  • the saponification value of the castor oil polyoxyethylene ether is 30-100 mgKOH/g.
  • the saponification value of the castor oil polyoxyethylene ether is 50-70 mgKOH/g.
  • the source of the castor oil polyoxyethylene ether is not particularly limited, and it can be mentioned the Jiangsu Haian Petrochemical Plant, with specifications EL20, HEL20, EL30, HEL30, EL40, HEL40, etc.
  • the source of the phenethylphenol polyoxyethylene ether sulfonate is not particularly limited, and Shandong Tiandao Bioengineering Co., Ltd., model 602# can be mentioned.
  • phenethylphenol polyoxyethylene ether sulfonate can generate a diffusion electric double layer on the surface of the particles, so that the original drug ions have a repulsive effect, and can also increase the particle size by increasing the particle size.
  • the steric hindrance of inter-coalescing can further improve the stability of the system; especially when the weight ratio of the castor oil polyoxyethylene ether and the phenethylphenol polyoxyethylene ether sulfonate is 1: (0.1-0.5), The suspension stability of the dispersible oil suspension agent obtained is the best, and no particles are precipitated even if it is stored for a long time.
  • the inventor also unexpectedly found that the dispersing performance of the dispersible oil suspending agent after being dissolved in water can also be improved by the compounding of the emulsifier.
  • the inventor believes that the possible reason is that the emulsion has a large number of interfaces, belongs to a thermodynamically unstable system, and has the tendency of automatic coalescence, stratification, sedimentation, etc., so as to reduce the interface, and the emulsifier used in this system can produce synergistic effects. It can effectively reduce the oil-water interfacial tension, so that the original drug particles should also have the ability to maintain dispersion in water, which is conducive to the emulsification and improves the stability of the emulsion.
  • Wetting agent also known as wetting agent.
  • One of the pesticide adjuvants Substances that can wet solid pesticides that are insoluble or not wettable by water. The main function is to reduce the surface tension or interfacial tension of water, so that the solid surface can be wetted by water. Water-insoluble pesticides can be mixed with water to form a suspension for use, and the liquid can be wetted and spread on the surface of crops, insects and pathogens, thereby improving the control effect and reducing the occurrence of phytotoxicity.
  • the wetting agent is not particularly limited, and is well known to those skilled in the art.
  • the wetting agent is selected from alkylphenol polyoxyethylene At least one of ether formaldehyde condensate sulfate, alkylphenol polyoxyethylene ether phosphate, phenethylphenol polyoxyethylene ether phosphate, alkyl sulfate, alkylsulfonate, and naphthalenesulfonate.
  • the weight ratio of the emulsifier and the wetting agent is 1:(0.05-0.5).
  • the weight ratio of the emulsifier and the wetting agent is 1:0.2.
  • Dispersant is a surfactant with two opposite properties, lipophilic and hydrophilic, in the molecule.
  • the dispersant is selected from polycarboxylates, lignosulfonates, EO-PO block copolymers, phosphate esters and their salts, sulfonates, alkylnaphthalenesulfonates, alkyl At least one of phenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
  • the dispersant is a combination of a sulfonate and a phosphate in a weight ratio of 1:(0.1-1.5).
  • the weight ratio of the sulfonates and the phosphates is 1:0.85.
  • the sulfonates are selected from at least one of naphthalenesulfonic acid formaldehyde condensate, alkylnaphthalenesulfonic acid formaldehyde condensate, lignin acid sulfonate, and sulfamate.
  • the sulfonates are preferably compounds with an aryl group in the molecular structure, preferably naphthalenesulfonic acid formaldehyde condensate and alkylnaphthalenesulfonic acid formaldehyde condensate.
  • the sources of the naphthalenesulfonic acid formaldehyde condensate and the alkylnaphthalenesulfonic acid formaldehyde condensate are not limited by specific ratio, and Jinan Hongboli Chemical Co., Ltd. can be mentioned.
  • the phosphoric acid esters are preferably compounds with amino groups and amide groups in the molecular structure.
  • alkylamide polyoxyethylene ether phosphoric acid esters can be mentioned.
  • the source of the alkylamide polyoxyethylene ether phosphate is not particularly limited, and Guangzhou Bifeng Trading Co., Ltd. can be mentioned.
  • the weight ratio of the emulsifier and the dispersant is 1:(0.1-0.5).
  • the weight ratio of the emulsifier and the dispersant is 1:0.4.
  • the system adopts the sulfonate dispersant with an aryl group in the structure and the phosphate ester surfactant with an amino group or an amide group in the structure, which can effectively improve the high temperature/low temperature storage of the dispersible oil suspension agent. stability.
  • the inventor believes that the possible reason is that the surface of the original drug particle has a relatively hydrophobic structure, especially the melting point of saflufenacil is lower, which makes it easier to aggregate, and the dispersant molecule used in the present invention can pass through van der Waals attraction, hydrogen and van der Waals surface with the pesticide surface.
  • Viscosity modifiers are mainly used to adjust the viscosity and consistency of products, generally there are two types of viscosity reducers and viscosity increasers.
  • the viscosity modifier is not particularly limited, and is well known to those skilled in the art.
  • the viscosity modifier can be mentioned gum arabic, xanthan gum, polyvinylpyrrolidone, organic bentonite, hydroxymethyl cellulose, polyvinyl alcohol, silicon dioxide, magnesium aluminum silicate and the like.
  • the viscosity modifier is a combination of organic bentonite and magnesium aluminum silicate in a weight ratio of 1:(0.5-2).
  • the weight ratio of the organobentonite to magnesium aluminum silicate is 1:0.76.
  • a two-dimensional three-dimensional structure is formed, thereby making the system thixotropic and increasing the structural strength of the suspension system.
  • the base oil is not particularly limited, it is well known to those skilled in the art, and vegetable oil, vegetable oil ester compound, mineral oil and the like can be mentioned.
  • the base oil is selected from soybean oil, corn oil, rapeseed oil, cottonseed oil, castor oil, turpentine oil, palm oil, coconut oil, sunflower oil, methyl oleate, diesel oil, motor oil , at least one of mineral oil.
  • the base oil includes at least methyl oleate.
  • the base oil is a combination of castor oil and methyl oleate in a weight ratio of 1:(0.1-10).
  • the system improves the dispersion stability of the emulsifier and the dispersant in the base oil on the one hand through the compounding of castor oil and methyl oleate, thereby improving the suspension and stability of the system and its dispersion in water, On the other hand, it can reduce the oil separation rate of the system under normal temperature and thermal storage state, and further improve the suspension rate.
  • the inventor believes that the possible reason is that the organic bentonite and aluminum magnesium silicate can absorb oil and swell to form a network gel structure in methyl oleate, which encapsulates a large number of oily medium molecules in the network voids. The chance of overlapping and covering the organic carbon chains increases, which increases the ability of the structure to resist damage, the yield value of the system increases, the oil separation rate of the system decreases, and the suspension rate increases.
  • the preparation method of the dispersible oil suspension agent is as follows: mixing the herbicidal composition, emulsifier, wetting agent, dispersant, defoamer, viscosity modifier and base oil, and dispersing at high speed for 10-60min; Then grind until D97 is 1-10 ⁇ m, that is, it is obtained.
  • the D97 is 3 ⁇ 1 ⁇ m.
  • D97 refers to the particle size value corresponding to when the cumulative distribution percentage from small to large reaches 97% in the particle size distribution. That is to say, in a certain powder, the number of particles with a particle size smaller than D97 accounts for 97% of the total number of particles. It is usually used to represent the coarse end particle size index of powder, and it is a key indicator in powder production and application.
  • the third aspect of the present invention provides the use of the herbicidal composition for controlling weeds in non-arable land.
  • the non-arable land can be mentioned as woodland, lawn, highway, railway, warehouse, ridge, water ditches, forest fire protection avenues and the like.
  • Embodiment 1 provides a herbicide dispersible oil suspension agent, which at least comprises the following components by weight percentage: 30% of herbicide composition, 10% of emulsifier, 2% of wetting agent, 4% of dispersant, viscosity adjustment 6% of the herbicide and base oil to make up 100%;
  • the herbicidal combination is a combination of saflufenacil and glyphosate, and the weight ratio is 1:40;
  • the emulsifier is castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene
  • the combination of oxyethylene ether sulfonate, the weight ratio is 1: 0.35;
  • the castor oil polyoxyethylene ether purchased from Jiangsu Haian Petrochemical Plant, specification EL30;
  • the phenethylphenol polyoxyethylene ether sulfonate purchased from Shandong Tiandao Biological Engineering Co., Ltd., model 602#;
  • the wetting agent is alkylphenol polyoxyethylene ether
  • the preparation method of the dispersible oil suspension agent is as follows: mixing the herbicidal composition, emulsifier, wetting agent, dispersing agent, defoaming agent, viscosity regulator and base oil, and dispersing at high speed for 30 min; then grinding to a D97 of 5 ⁇ m , that is.
  • Embodiment 2 provides a herbicide dispersible oil suspension agent, which at least comprises the following components by weight percentage: 30% of herbicide composition, 5% of emulsifier, 1% of dispersant, 2% of viscosity modifier, basic
  • the oil supplement is 100%;
  • the herbicidal combination is a combination of saflufenacil and glyphosate, and the weight ratio is 1:40;
  • the emulsifier is castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene ether sulfonic acid
  • the combination of salt, the weight ratio is 1: 0.1;
  • the castor oil polyoxyethylene ether is purchased from Jiangsu Haian Petrochemical Plant, specification EL30;
  • the phenethylphenol polyoxyethylene ether sulfonate is purchased from Shandong Tiandao Bioengineering Co., Ltd., model 602#;
  • the wetting agent is alkylphenol polyoxyethylene ether formaldehyde con
  • the preparation method of the dispersible oil suspension agent is as follows: mixing the herbicidal composition, emulsifier, wetting agent, dispersing agent, defoaming agent, viscosity regulator and base oil, and shearing and dispersing for 30 minutes; then grinding until D97 is 5 ⁇ m , that is.
  • Embodiment 3 provides a herbicide dispersible oil suspension agent, which at least comprises the following components by weight percentage: 50% of herbicide composition, 20% of emulsifier, 5% of wetting agent, 5% of dispersant, viscosity adjustment
  • the herbicidal combination is a combination of saflufenacil and glyphosate, and the weight ratio is 1:40;
  • the emulsifier is castor oil polyoxyethylene ether and phenethylphenol polyoxyethylene
  • the combination of oxyethylene ether sulfonate, the weight ratio is 1: 0.5; the castor oil polyoxyethylene ether, purchased from Jiangsu Haian Petrochemical Plant, specification EL30; the phenethylphenol polyoxyethylene ether sulfonate , purchased from Shandong Tiandao Biological Engineering Co., Ltd., model 602#;
  • the wetting agent is alkylphenol polyoxyethylene ether formaldehyde condensate sulfate,
  • the preparation method of the dispersible oil suspension agent is as follows: mixing the herbicidal composition, emulsifier, wetting agent, dispersing agent, defoaming agent, viscosity modifier and base oil, and dispersing at high speed for 30 min; then grinding to D97 of 1 -10 ⁇ m, that is.
  • Example 4 The difference between Example 4 and Example 1 is that the emulsifier does not include castor oil polyoxyethylene ether.
  • Example 5 The difference between Example 5 and Example 1 is that the emulsifier does not include phenethylphenol polyoxyethylene ether sulfonate.
  • Example 6 The difference between Example 6 and Example 1 is that in the emulsifier, phenethylphenol polyoxyethylene ether sulfonate is replaced with alkylphenol polyoxyethylene ether.
  • Example 7 The difference between Example 7 and Example 1 is that the dispersant does not include alkylnaphthalenesulfonic acid formaldehyde condensate.
  • Example 8 The difference between Example 8 and Example 1 is that the dispersant does not include alkylamide polyoxyethylene ether phosphate.
  • Example 9 The difference between Example 9 and Example 1 is that in the dispersant, the alkylnaphthalenesulfonic acid formaldehyde condensate is replaced by sodium lignosulfonate.
  • Example 10 The difference between Example 10 and Example 1 is that the alkyl amide polyoxyethylene ether phosphate in the dispersant is replaced with an alkylphenol polyoxyethylene ether phosphate.
  • Example 11 The difference between Example 11 and Example 1 is that the viscosity modifier does not include magnesium aluminum silicate.
  • Example 12 The difference between Example 12 and Example 1 is that the base oil does not include methyl oleate.
  • Example 13 The difference between Example 13 and Example 1 is that the herbicidal combination is a combination of saflufenacil and glyphosate, and the weight ratio is 1:30.
  • Viscosity At room temperature, the viscosity of the dispersible oil suspension was measured with an NDJ-1 rotational viscometer, and each sample was repeatedly measured three times, and the average value was taken.
  • the spray treatment was carried out on a crawler-type crop sprayer (designed and produced by Engineer Research Ltd., UK) (spray pressure 1.95kg/cm 2 , spray volume 500L/hm 2 , crawler speed 1.48km/h), and the experiment Set 3 repetitions.
  • the test materials are processed, they are placed in the operation hall. After the liquid is naturally air-dried, it is placed in the greenhouse for management according to conventional methods. The response of the tested weeds to the drug is observed and recorded. Weed control effect.
  • PA is the proportion of agent A in the active ingredients of the mixture
  • PB is the proportion of agent B in the active ingredients of the mixture, if the co-toxicity coefficient is less than 80, it is an antagonistic effect; if the co-toxicity coefficient is greater than 120, it is Synergistic effect; co-toxicity coefficient between 80-120 is additive effect.
  • Table 2 The results of the control effect test of the mixed use of saflufenacil and glyphosate against glyphosate-resistant P.
  • weeds are oxtenoid grass and small fly pods, which grow vigorously and grow densely, with an average plant height of 10-30 cm when treated; there are others such as annual pods, water celery, crabgrass, bermudagrass, lychee A small amount of weeds such as grass, motherwort, cnidium, etc.
  • the spray equipment is 3WBD-20L electric sprayer
  • the nozzle is a fan nozzle
  • the working pressure is 0.2-0.4Mpa
  • the spray volume is 45kg/mu
  • the spray is uniform.
  • the pesticides are mainly mixed with glyphosate, dimethyltetrachloride and dicamba.
  • Meteorological data The day of application was sunny, with an average temperature of 20.4°C, a maximum temperature of 25.3°C, and a slight breeze. During the test period, there were many rainy days, but there was no obvious harsh environment.

Landscapes

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

Abstract

本发明涉及农药技术领域，具体涉及一种除草组合物、制剂及其应用。一种除草组合物，所述组合物包括组苯嘧草唑和草甘膦；所述苯嘧草唑和草甘膦的重量比为1∶(10-100)。本发明还提供了一种包括上述除草组合物的可分散油悬浮剂，通过对乳化剂、分散剂、增效剂、黏度调节剂以及分散介质的种类和含量进行筛选优化，使制得的可分散油悬浮剂质量稳定、性能良好，更有利于药效的发挥，同时具有优异的低温流动性、分散稳定性、热储稳定性等；且其原料易得，制备工艺简单，易于工业化生产，适用于防除非耕地杂草。

Description

一种除草组合物、制剂及其应用 技术领域
本发明涉及农药技术领域，具体涉及一种除草组合物、制剂及其应用。
背景技术
苯嘧草唑，化学名：3-(2-氯-4-氟-5-(3-甲基-2，6-二氧-4-三氟甲基-3，6-二氢嘧啶-1(2H)-基)苯基)-5-甲基-4，5-二氢异恶唑-5-羧酸乙酯，结构独特是脲嘧啶与异恶唑结构的结合，与苯嘧磺草胺比较具有更好的除草活性，可以有效地防除园林地和非耕地中的一年生及多年生杂草，但成本较高。目前，含有单一活性成分的除草剂品种在农业除草过程中存在不同程度的缺陷，如连续使用容易产生抗药性，除草谱不够广，只能防除单子叶杂草或双子叶杂草，或者只能防除出苗的杂草或未出苗的杂草，不能兼防。而通过两种或两种以上活性组分的复配，可以提高防效，减少有效成分的使用量，节约防除成本，延缓杂草抗药性的产生，延长药剂使用寿命，并减少对环境的污染。
可分散油悬浮剂是原药与助剂(如乳化剂、分散剂和黏度调节剂等)，以油相为载体制成的高分散的、一定时间内稳定的非水介质的油相悬浮体系，其中至少有一种成分不溶于非水介质，用水稀释后使用。相对于其他的剂型，可分散油悬浮剂具有安全环保，且药效好的特点，体现在生产过程中无粉尘污染，也不使用易燃易爆的有机溶剂，对生产者和使用者比较安全，贮存和运输也方便安全，对环境也比较安全，因此在国际上被大量推广应用。鉴于某些原药的物理化学性质或者原药与助剂之间缺乏良好的协同作用，例如某些亲油性差的原药，他们很难透过作物表皮而进入植物内部，很难发挥它们的内吸作用，渗透性粘附性较差，难以发挥药效，因而对于亲油性差的原药，特别是不溶于油相的除草剂，制成可分散油悬浮剂，可起到增效作用。由于不同的农药原药的理化性质有着很大的区别，筛选的各种助剂的性能、助剂相互之间的作用及其对原药的影响差异较大，目前，可分散油悬浮剂存在低温流动性差、分散稳定性变差、热储稳定性差(制剂热储后出现析油、分解、变色、黏稠、结晶)等问题，导致使用时容易堵塞喷嘴或过滤网，直接影响可分散油悬浮剂的质量和应用效果。
针对上述技术问题，本发明提供了一种含苯嘧草唑的除草组合物及其制得的可分散油悬浮剂，通过对助剂的选择，解决了目前可分散油悬浮剂存在的稳定性问题。
发明内容
为了解决上述技术问题，本发明的第一个方面提供了一种除草组合物，所述组合物包括组苯嘧草唑和草甘膦；所述苯嘧草唑和草甘膦的重量比为1∶(10-100)。
本发明的第二个方面提供了一种除草组合物制剂，由上述的除草组合物和农药学上可接受的辅料组成。
作为本发明一种优选的技术方案，所述除草组合物制剂的剂型选自可溶液剂、微乳剂、可分散油悬浮剂、可湿性粉剂、水分散粒剂中的一种。
作为本发明一种优选的技术方案，所述除草组合物占所述除草组合物制剂的重量百分比为5％-90％。
作为本发明一种优选的技术方案，所述除草组合物制剂的剂型为可分散油悬浮剂；所述农药学上可接受的辅料包括乳化剂、润湿剂、分散剂、稳定剂、消泡剂、黏度调节剂、基础油中的至少一种。
作为本发明一种优选的技术方案，所述乳化剂选自蓖麻油聚氧乙烯醚、十二烷基苯磺酸钙、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、烷基酚甲醛树脂聚氧乙烯醚、山梨醇酐单硬脂酸酯、失水山梨醇单硬脂酸酯聚氧乙烯醚、苯乙基酚聚氧乙烯醚、苯乙基苯酚聚氧乙烯聚氧丙烯醚、烷氧基聚氧乙烯醚磺酸盐、脂肪醇硫酸盐、烷基磷酸酯盐、脂肪醇聚氧乙烯醚硫酸盐、EO-PO嵌段共聚物和苯乙基酚聚氧乙烯醚磺酸盐中的至少一种。
作为本发明一种优选的技术方案，所述乳化剂为蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的组合，重量比为1∶(0.1-0.5)。
作为本发明一种优选的技术方案，所述分散剂选自聚羧酸盐、木质素磺酸盐、EO-PO嵌段共聚物、磷酸酯及其盐类、磺酸盐类、烷基萘磺酸盐、烷基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚中的至少一种。
作为本发明一种优选的技术方案，所述黏度调节剂为有机膨润土和硅酸镁铝的组合，重量比为1∶(0.5-2)。
本发明的第三个方面提供了所述除草组合物的应用，应用于防除非耕地杂草。
有益效果
本发明提供了一种除草组合物及包含该除草组合物的可分散油悬浮剂，具有以下有益效果：
1.通过苯嘧草唑和草甘膦的复配，作用机理独特不存在交互抗性，产生协同增效的作用，扩大了杀草谱，提高了防效，弥补单用药剂对主要杂草防效效果差的缺陷；提高组合物各成分的持效性，延缓杂草抗药性的产生，减少农药反复使用次数，降低使用量及成本；可主要应用于防除非耕地杂草，尤其是能够防除草甘膦抗性杂草，如小飞蓬、牛筋草等；
2.通过对乳化剂、分散剂、增效剂、黏度调节剂以及分散介质的种类和含量进行筛选优化，使制得的可分散油悬浮剂质量稳定、性能良好，更有利于药效的发挥，同时具有优异的低温流动性、分散稳定性、热储稳定性等；且其原料易得，制备工艺简单，易于工业化生产。
具体实施方式
参选以下本发明的优选实施方法的详述以及包括的实施例可更容易地理解本发明的内容。除非另有限定，本文使用的所有技术以及科学术语具有与本发明所属领域普通技术人员通常理解的相同的含义。当存在矛盾时，以本说明书中的定义为准。
如本文所用术语“由...制备”与“包含”同义。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
连接词“由...组成”排除任何未指出的要素、步骤或组分。如果用于权利要求中，此短语将使权利要求为封闭式，使其不包含除那些描述的材料以外的材料，但与其相关的常规杂质除外。当短语“由...组成”出现在权利要求主体的子句中而不是紧接在主题之后时，其仅限定在该子句中描述的要素；其它要素并不被排除在作为整体的所述权利要求之外。
当量、浓度、或者其它值或参数以范围、优选范围、或一系列上限优选值和下限优选值限定的范围表示时，这应当被理解为具体公开了由任何范围上限或优选值与任何范围下限或优选值的任一配对所形成的所有范围，而不论该范围是否单独公开了。例如，当公开了范围“1至5”时，所描述的范围应被解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。当数值范围在本文中被描述时，除非另外说明，否则该范围意图包括其端值和在该范围内的所有整数和分数。
单数形式包括复数讨论对象，除非上下文中另外清楚地指明。“任选的”或者“任意一种”是指其后描述的事项或事件可以发生或不发生，而且该描述包括事件发生的情形和事件不发生的情形。
说明书和权利要求书中的近似用语用来修饰数量，表示本发明并不限定于该具体数量，还包括与该数量接近的可接受的而不会导致相关基本功能的改变的修正的部分。相应的，用“大约”、“约”等修饰一个数值，意为本发明不限于该精确数值。在某些例子中，近似用语可能对应于测量数值的仪器的精度。在本申请说明书和权利要求书中，范围限定可以组合和/或互换，如果没有另外说明这些范围包括其间所含有的所有子范围。
为了解决上述技术问题，本发明的第一个方面提供了一种除草组合物，所述组合物包括组苯嘧草唑和草甘膦；所述苯嘧草唑和草甘膦的重量比为1∶(10-100)。
在一种优选的实施方式中，所述苯嘧草唑和草甘膦的重量比为1∶(20-60)。
在一种更优选的实施方式中，所述苯嘧草唑和草甘膦的重量比为1∶40。
发明人发现，苯嘧草唑与草甘膦复配使用后，由于两种有效成分的作用机理独特不存在交互抗性，产生协同增效的作用，扩大了杀草谱，提高了防效，弥补单用药剂对主要杂草防效效果差的缺陷；提高组合物各成分的持效性，延缓杂草抗药性的产生，减少农药反复使用次数，降低使用量及成本；可主要应用于防除非耕地杂草，尤其是能够防除草甘膦抗性杂草，如小飞蓬、牛筋草等。
本发明的第二个方面提供了一种除草组合物制剂，由上述的除草组合物和农药学上可接受的辅料组成。
在一种优选的实施方式中，所述除草组合物制剂的剂型选自可溶液剂、微乳剂、可分散油悬浮剂、可湿性粉剂、水分散粒剂中的一种。
在一种优选的实施方式中，所述除草组合物占所述除草组合物制剂的重量百分比为5-90％。
在一种优选的实施方式中，所述除草组合物制剂的剂型为可分散油悬浮剂；所述农药学上可接受的辅料包括乳化剂、润湿剂、分散剂、稳定剂、消泡剂、黏度调节剂、基础油中的至少一种。
可分散油悬浮剂
本发明中，所述除草剂可分散油悬浮剂的制备原料，按重量百分比计，至少包括以下组分：除草剂组合物5-50％、乳化剂5-20％、湿润剂0-5％、分散剂1-5％、消泡剂0-5％、黏度调节剂2-10％、基础油补足100％。
乳化剂
乳化剂是能使两种或两种以上互不相溶的组分的混合液体形成稳定的乳状液的一类化合物。其作用原理是在乳化过程中，分散相以微滴(微米级)的形式分散在连续相中，乳化剂降低了混合体系中各组分的界面张力，并在微滴表面形成较坚固的薄膜或由于乳化剂给出的电荷而在微滴表面形成双电层，阻止微滴彼此聚集，而保持均匀的乳状液。从相的观点来说，乳状液仍是非均相体系。乳状液中的分散相可以是水相，也可以是油相，大多数为油相；连续相可以是油相，也可以是水相，大多数为水相。乳化剂是一种表面活性剂，分子中有亲水基和亲油基。为了表示乳化剂的亲水性或亲油性，通常采用“亲水亲油平衡值(HLB值)”，HLB值愈低，其亲油性愈强；反之，HLB值愈高，其亲水性愈强。各种乳化剂的HLB值不同，为了获得稳定的乳状液，必须选择合适的乳化剂。
本发明中，所述乳化剂选自蓖麻油聚氧乙烯醚、十二烷基苯磺酸钙、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、烷基酚甲醛树脂聚氧乙烯醚、山梨醇酐单硬脂酸酯、失水山梨醇单硬脂酸酯聚氧乙烯醚、苯乙基酚聚氧乙烯醚、苯乙基苯酚聚氧乙烯聚氧丙烯醚、烷氧基聚氧乙烯醚磺酸盐、脂肪醇硫酸盐、烷基磷酸酯盐、脂肪醇聚氧乙烯醚硫酸盐、EO-PO嵌段共聚物和苯乙基酚聚氧乙烯醚磺酸盐中的至少一种。
在一种优选的实施方式中，所述乳化剂为蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的组合，重量比为1∶(0.1-0.5)。
在一种更优选的实施方式中，所述蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚 磺酸盐的重量比为1∶0.35。
蓖麻油聚氧乙烯醚
本发明中，所述蓖麻油聚氧乙烯醚的HLB值为9-14。
在一种优选的实施方式中，所述蓖麻油聚氧乙烯醚的HLB值为11-13。
在一种优选的实施方式中，所述蓖麻油聚氧乙烯醚的皂化值为30-100mgKOH/g。
在一种更优选的实施方式中，所述蓖麻油聚氧乙烯醚的皂化值为50-70mgKOH/g。
本发明中，所述蓖麻油聚氧乙烯醚的来源，没有特别的限制，可提及江苏省海安石油化工厂，规格EL20、HEL20、EL30、HEL30、EL40、HEL40等。
苯乙基酚聚氧乙烯醚磺酸盐
本发明中，所述苯乙基酚聚氧乙烯醚磺酸盐的来源，没有特别的限制，可提及山东天道生物工程有限公司，型号602#。
发明人发现，本体系采用蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的复配，能够有效防止原药粒子的絮凝，从而提高可分散油悬浮剂的悬浮稳定性和贮存稳定性。发明人认为可能的原因是蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的复配能够显著降低原药离子的表面自由能，一方面蓖麻油聚氧乙烯醚能够对粒子进行吸附，形成厚的吸附层；另一方面，苯乙基酚聚氧乙烯醚磺酸盐能够在粒子表面生成扩散双电层，使原药离子间具有排斥作用的同时，还能够通过增加粒子间聚结的空间位阻，进一步提高体系的稳定性；尤其当所述蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的重量比为1∶(0.1-0.5)时，制得可分散油悬浮剂的悬浮稳定性达到最佳，即使长时间存放，也不会有颗粒析出。发明人在研究过程中还意外发现，通过乳化剂的复配，还能够提高该可分散油悬浮剂溶于水后的分散性能。发明人认为可能的原因是，乳状液有大量的界面存在，属于热力学不稳定体系，有自动聚结、分层、沉降等趋势，以使界面减少，而本体系所用乳化剂能够产生协同增效的作用，有效降低油水界面张力，使原药粒子在水中也应具有保持分散的能力，有利于乳化作用进行和提高乳状液的稳定性。
湿润剂
湿润剂，又称润湿剂。农药助剂之一。能使不溶于水或不为水湿润的固体农 药被水浸湿的物质。主要作用是降低水的表面张力或界面张力，使固体表面能被水所润湿。可使不溶于水的农药，兑水后配成悬浮液使用，并能使药液在作物、虫体和病菌体表上湿润和展开，从而提高防治效果，减少药害的发生。
本发明中，所述湿润剂，没有特别的限制，为本领域技术人员熟知。
在一种优选的实施方式中，为了进一步提高原药粒子在水中保持分散成细微个体粒子的能力，同时提高原药粒子在水中的分散能力，所述湿润剂选自烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐、烷基酚聚氧乙烯醚磷酸酯、苯乙基酚聚氧乙烯基醚磷酸酯、烷基硫酸盐、烷基磺酸盐、萘磺酸盐中的至少一种。
本发明中，所述乳化剂和湿润剂的重量比为1∶(0.05-0.5)。
在一种优选的实施方式中，所述乳化剂和湿润剂的重量比为1∶0.2。
分散剂
分散剂(Dispersant)是一种在分子内同时具有亲油性和亲水性两种相反性质的界面活性剂。
本发明中，所述分散剂选自聚羧酸盐、木质素磺酸盐、EO-PO嵌段共聚物、磷酸酯及其盐类、磺酸盐类、烷基萘磺酸盐、烷基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚中的至少一种。
在一种优选的实施方式中，所述分散剂为磺酸盐和磷酸酯的组合，重量比为1∶(0.1-1.5)。
在一种更优选的实施方式中，所述磺酸盐类和磷酸酯的重量比为1∶0.85。
磺酸盐类
本发明中，所述磺酸盐类选自萘磺酸甲醛缩合物、烷基萘磺酸甲醛缩合物、木质素酸磺酸盐、氨基磺酸盐中的至少一种。
在一种优选的实施方式中，所述磺酸盐类优选分子结构中带有芳基的化合物，优选萘磺酸甲醛缩合物、烷基萘磺酸甲醛缩合物。
本发明中，所述萘磺酸甲醛缩合物、烷基萘磺酸甲醛缩合物的来源，没有特比的限制，可提及济南宏博利化工有限公司。
磷酸酯类
本发明中，所述磷酸酯类优选分子结构中带有氨基、酰胺基的化合物。
在一种优选的实施方式中，所述磷酸酯类，可提及烷基酰胺聚氧乙烯醚磷酸 酯。
本发明中，所述烷基酰胺聚氧乙烯醚磷酸酯的来源，没有特别的限制，可提及广州碧峰贸易有限公司。
本发明中，所述乳化剂和分散剂的重量比为1∶(0.1-0.5)。
在一种优选的实施方式中，所述乳化剂和分散剂的重量比为1∶0.4。
发明人发现，本体系采用结构中带有芳基的磺酸盐类分散剂和结构中带有氨基或酰胺基的磷酸酯类表面活性剂，能够有效提高可分散油悬浮剂高温/低温贮存后的稳定性。发明人认为可能的原因是，原药粒子表面是相对疏水的结构，尤其是苯嘧草唑其熔点较低，更容易聚集，而本发明采用的分散剂分子能够与农药表面通过范德华引力、氢键作用力、静电排斥力和空间位阻作用力协同作用，使原药粒子不受温度的影响，更好的分散。然而，当所述分散剂的用量低于1％时，分散剂在原药粒子表面未达到饱和吸附，农药颗粒不能被分散剂分子充分包覆，颗粒在范德华作用力和重力场的作用下，聚结、沉降，使得制剂的粘度增大；当分散剂用量高于10％时，体系中过剩的分散剂分子与有效成分颗粒表面的包覆层相互缠结，引起颗粒之间的桥接，导致絮凝，使得制剂的粘度增大，流动性变差，进而影响制剂的外观。
黏度调节剂
黏度调节剂主要是调节产品的黏度与稠度，一般有降黏剂与增粘剂两种。
本发明中，所述黏度调节剂，没有特别的限制，为本领域技术人员熟知。
在一种优选的实施方式中，为了进一步提高体系的悬浮稳定性，抑制原药颗粒的沉降，既保持体系的流动性，又要保证体系在热储过程中不分层、不发生奥氏熟化现象，所黏度调节剂，可提及阿拉伯胶、黄原胶、聚乙烯吡咯烷酮、有机膨润土、羟甲基纤维素、聚乙烯醇、二氧化硅、硅酸镁铝等。
在一种更优选的实施方式中，所述黏度调节剂为有机膨润土和硅酸镁铝的组合，重量比为1∶(0.5-2)。
在一种最优选的实施方式中，所述有机膨润土和硅酸铝镁的重量比为1∶0.76。
发明人认为，本体系通过有机膨润土和硅酸铝镁的复配，在水中吸水膨胀形成水凝胶网状结构，同时还能够通过共价键和氢键或离子间的斥力使聚合物链展开形成二维立体结构，从而使体系具有触变性，增加悬浮体系的结构强度。
基础油
本发明中，所述基础油，没有特别的限制，为本领域技术人员熟知，可提及植物油、植物油酯化合物、矿物油等。
在一种优选的实施方式中，所述基础油选自大豆油、玉米油、菜籽油、棉籽油、蓖麻油、松节油、棕榈油、椰子油、向日葵油、油酸甲酯、柴油、机油、矿物油中的至少一种。
在一种更优选的实施方式中，所述基础油至少包括油酸甲酯。
在一种更优选的实施方式中，所述基础油为蓖麻油和油酸甲酯的组合，重量比为1∶(0.1-10)。
发明人发现，本体系通过蓖麻油和油酸甲酯的复配，一方面提高乳化剂、分散剂在基础油中的分散稳定性，从而提高体系及其分散于水中的悬浮性和稳定性，另一方面能够降低体系在常温及热储状态下的析油率，进一步提高悬浮率。发明人认为可能的原因是，有机膨润土和硅酸铝镁在油酸甲酯中可以吸油膨胀形成一种网络凝胶结构，将大量的油性介质分子包裹在网状空隙中，随着有机膨润土的有机碳链相互交叠、覆盖的机会增大，使得结构抗破坏的能力增大，体系的屈服值增大，体系的析油率降低，悬浮率增大。
本发明中，所述可分散油悬浮剂的制备方法为：将除草组合物、乳化剂、湿润剂、分散剂、消泡剂、黏度调节剂和基础油混合，高速剪切分散10-60min；然后研磨至D97为1-10μm，即得。
在一种更优选的实施方式中，所述D97为3±1μm。
D97是指颗粒粒度分布中，从小到大累积分布百分数达到97％时对应的粒径值。即指某一粉体中，粒径小于D97的颗粒数占总颗粒数的97％。它通常被用来表示粉体粗端粒度指标，是粉体生产和应用中一个被重点关注的指标。
发明人发现，控制体系的D97为1-10μm，能够显著提高体系的分散性和贮存稳定性。
本发明的第三个方面提供了所述除草组合物的应用，应用于防除非耕地杂草。
在一种优选的实施方式中，所述非耕地，可提及林地、草坪、公路、铁路、仓库、田埂、水沟、森林防火大道等。
下面通过实施例对本发明进行具体描述。有必要在此指出的是，以下实施例 只用于对本发明作进一步说明，不能理解为对本发明保护范围的限制，该领域的专业技术人员根据上述本发明的内容做出的一些非本质的改进和调整，仍属于本发明的保护范围。
实施例
实施例1
实施例1提供了一种除草剂可分散油悬浮剂，按重量百分比计，至少包括以下组分：除草剂组合物30％、乳化剂10％、湿润剂2％、分散剂4％、黏度调节剂6％、基础油补足100％；所述除草组合为苯嘧草唑和草甘膦的组合，重量比为1∶40；所述乳化剂为蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的组合，重量比为1∶0.35；所述蓖麻油聚氧乙烯醚，购买于江苏省海安石油化工厂，规格EL30；所述苯乙基酚聚氧乙烯醚磺酸盐，购买于山东天道生物工程有限公司，型号602#；所述湿润剂为烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐，购买于江苏省海安石油化工厂；所述分散剂为烷基萘磺酸甲醛缩合物和烷基酰胺聚氧乙烯醚磷酸酯的组合，重量比为1∶0.85；所述烷基萘磺酸甲醛缩合物，购买于济南宏博利化工有限公司；所述烷基酰胺聚氧乙烯醚磷酸酯，购买于广州碧峰贸易有限公司；所述黏度调节剂为有机膨润土和硅酸镁铝的组合，重量比为1∶0.76；所述有机膨润土，购买于拓亿新材料(广州)有限公司；所述基础油为蓖麻油和油酸甲酯的组合，重量比为1∶0.8。
所述可分散油悬浮剂的制备方法为：将除草组合物、乳化剂、湿润剂、分散剂、消泡剂、黏度调节剂和基础油混合，高速剪切分散30min；然后研磨至D97为5μm，即得。
实施例2
实施例2提供了一种除草剂可分散油悬浮剂，按重量百分比计，至少包括以下组分：除草剂组合物30％、乳化剂5％、分散剂1％、黏度调节剂2％、基础油补足100％；所述除草组合为苯嘧草唑和草甘膦的组合，重量比为1∶40；所述乳化剂为蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的组合，重量比为1∶0.1；所述蓖麻油聚氧乙烯醚，购买于江苏省海安石油化工厂，规格EL30；所述苯乙基酚聚氧乙烯醚磺酸盐，购买于山东天道生物工程有限公司，型号602#； 所述湿润剂为烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐，购买于江苏省海安石油化工厂；所述分散剂为烷基萘磺酸甲醛缩合物和烷基酰胺聚氧乙烯醚磷酸酯的组合，重量比为1∶0.1；所述烷基萘磺酸甲醛缩合物，购买于济南宏博利化工有限公司；所述烷基酰胺聚氧乙烯醚磷酸酯，购买于广州碧峰贸易有限公司；所述黏度调节剂为有机膨润土和硅酸镁铝的组合，重量比为1∶0.5；所述有机膨润土，购买于拓亿新材料(广州)有限公司；所述基础油为蓖麻油和油酸甲酯的组合，重量比为1∶0.1。
所述可分散油悬浮剂的制备方法为：将除草组合物、乳化剂、湿润剂、分散剂、消泡剂、黏度调节剂和基础油混合，告诉剪切分散30min；然后研磨至D97为5μm，即得。
实施例3
实施例3提供了一种除草剂可分散油悬浮剂，按重量百分比计，至少包括以下组分：除草剂组合物50％、乳化剂20％、湿润剂5％、分散剂5％、黏度调节剂10％、基础油补足100％；所述除草组合为苯嘧草唑和草甘膦的组合，重量比为1∶40；所述乳化剂为蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的组合，重量比为1∶0.5；所述蓖麻油聚氧乙烯醚，购买于江苏省海安石油化工厂，规格EL30；所述苯乙基酚聚氧乙烯醚磺酸盐，购买于山东天道生物工程有限公司，型号602#；所述湿润剂为烷基酚聚氧乙烯基醚甲醛缩合物硫酸盐，购买于江苏省海安石油化工厂；所述分散剂为烷基萘磺酸甲醛缩合物和烷基酰胺聚氧乙烯醚磷酸酯的组合，重量比为1∶1.5；所述烷基萘磺酸甲醛缩合物，购买于济南宏博利化工有限公司；所述烷基酰胺聚氧乙烯醚磷酸酯，购买于广州碧峰贸易有限公司；所述黏度调节剂为有机膨润土和硅酸镁铝的组合，重量比为1∶2；所述有机膨润土，购买于拓亿新材料(广州)有限公司；所述基础油为蓖麻油和油酸甲酯的组合，重量比为1∶10。
所述可分散油悬浮剂的制备方法为：将除草组合物、乳化剂、湿润剂、分散剂、消泡剂、黏度调节剂和基础油混合，高速剪切分散30min；然后研磨至D97为1-10μm，即得。
实施例4
实施例4与实施例1的区别在于，所述乳化剂不包括蓖麻油聚氧乙烯醚。
实施例5
实施例5与实施例1的区别在于，所述乳化剂不包括苯乙基酚聚氧乙烯醚磺酸盐。
实施例6
实施例6与实施例1的区别在于，所述乳化剂中苯乙基酚聚氧乙烯醚磺酸盐被替换成烷基酚聚氧乙烯醚。
实施例7
实施例7与实施例1的区别在于，所述分散剂不包括烷基萘磺酸甲醛缩合物。
实施例8
实施例8与实施例1的区别在于，所述分散剂不包括烷基酰胺聚氧乙烯醚磷酸酯。
实施例9
实施例9与实施例1的区别在于，所述分散剂中烷基萘磺酸甲醛缩合物被替换成木质素磺酸钠。
实施例10
实施例10与实施例1的区别在于，所述分散剂中烷基酰胺聚氧乙烯醚磷酸酯被替换成烷基酚聚氧乙烯醚磷酸酯。
实施例11
实施例11与实施例1的区别在于，所述黏度调节剂不包括硅酸铝镁。
实施例12
实施例12与实施例1的区别在于，所述基础油不包括油酸甲酯。
实施例13
实施例13与实施例1的区别在于，所述除草组合为苯嘧草唑和草甘膦的组合，重量比为1∶30。
性能测试
1.热储稳定性：
用吸管吸取大约10g左右的油悬浮剂样品，注入到干净的安瓿瓶中，高温密封后放入恒温(54土2℃)的恒温箱中，热储14天后取出，分别检测可分散油悬浮剂的悬浮率和粘度等各项指标，如果热储前后的各项指标均达到国家标准， 那么热储合格，视样品常温贮存2年合格。合格用“√”表示；不合格用“×”表示。
2.冷贮稳定性：
用吸管吸取大约80mL的油悬浮剂置于100mL烧杯中，在(0±2℃)冰箱中冷藏，放置一个小时，每15分钟搅拌一次，每次搅拌时间为15s，观察外观的变化，再将烧杯持续放置在冰箱中7天，7天后取出，放置至室温分别检测油悬浮剂的悬浮率和粘度等各项指标，如果冷贮前后的各项指标均达到国家标准，则冷贮合格，视样品常温贮存2年合格。合格用“√”表示；不合格用“×”表示。
3.粘度：在室温下，用NDJ-1型旋转粘度计测定可分散油悬剂的粘度，每个样品重复测定三次，取其平均值。
4.悬浮率：测试参考HG/T 2467.5-2003。
测试结果见表1。
表1.实施例的性能测试结果
Figure PCTCN2022075774-appb-000001
5.防效试验：
供试样品：
苯嘧草唑，草甘膦。
供试靶标：
小飞蓬[Conyzacanadensis(L.)Cronq.]，具草甘膦抗性，采自湖南省常德市白鹤山；
牛筋草[Eleusineindica(L.)Gaertn.]，具草甘膦抗性，采自广东省惠州市马鞍镇。
试验方法：
靶标试材的室内培养
将小飞蓬和牛筋草种子混土播种在育苗盘中，待幼苗10cm左右进行移栽，每纸杯1株，置于温室内正常培养，移栽后约15天进行茎叶喷雾处理。
处理方法：
按试验设计剂量，在履带式作物喷雾机(英国Engineer Research Ltd.设计生产)上进行喷雾处理(喷雾压力1.95kg/cm 2，喷液量500L/hm 2，履带速度1.48km/h)，试验设3次重复。试材处理后置于操作大厅，待药液自然风干后，放于温室内按常规方法管理，观察并记录供试杂草对药剂的反应情况，处理后定期目测或鲜重调查供试药剂对杂草的防除效果。
试验结果统计分析方法：
供试药剂ED 50/ED 90值计算
采用DPS统计分析软件进行计算
共毒系数计算：
Figure PCTCN2022075774-appb-000002
其中：PA为药剂A在混剂有效成分中所占的比例，PB为药剂B在混剂有效成分中所占的比例，若共毒系数小于80，为拮抗作用；共毒系数大于120，为增效作用；共毒系数在80-120之间为相加作用。
结果见表2、3，其中A为苯嘧草唑，B为草甘膦。
表2苯嘧草唑与草甘膦混用对草甘膦抗性小飞蓬的防效试验结果
Figure PCTCN2022075774-appb-000003
Figure PCTCN2022075774-appb-000004
表3苯嘧草唑与草甘膦混用对草甘膦抗性牛筋草的防效试验结果
Figure PCTCN2022075774-appb-000005
6.田间药效试验：
测试药剂：
实施例13的除草剂可分散油悬浮剂对照药剂：
10％苯嘧草唑水乳剂(南通江山农药化工股份有限公司)、30％草甘膦可溶液剂(商品名：农达)
试验地点：
池州的长江大堤
防除对象：
杂草以牛筋草、小飞蓬为主的优势种群，生长旺盛，生长较密，处理时平均株高10-30厘米；还有其他的如一年蓬、水芹菜、马唐、狗牙根、荔枝草、益母草、蛇床子等少量杂草。
试验方法：
小区划分：每个处理重复3次，随机编排，每个小区20m 2。
使用方法：2020年5月份23日进行茎叶喷雾处理，喷雾器械为3WBD-20L电动喷雾器，喷头为扇形喷头，工作压力为0.2-0.4Mpa，喷雾量为45kg/亩，均匀喷雾。
(常规大堤杂草防除需要开展2-3次防治，药剂主要用草甘膦与二甲四氯、麦草畏等混配喷雾，小飞蓬抗性较强。)
调查、记录和测量方法：
气象资料：施药当天为晴天，平均气温20.4℃，最高温度为25.3℃，微风。试验期间雨日数较多，但无明显恶劣环境。
杂草调查：用药后3天、6天、9天、12天、16天目测杂草死亡症状与速度；药后16天每小区3点取样，每点调查0.25m 2小飞蓬残留株数，计算株防效。
对小飞蓬杂草的防除效果(处理后16天)如下：
Figure PCTCN2022075774-appb-000006
前述的实例仅是说明性的，用于解释本发明所述方法的一些特征。所附的权利要求旨在要求可以设想的尽可能广的范围，且本文所呈现的实施例仅是根据所有可能的实施例的组合的选择的实施方式的说明。因此，申请人的用意是所附的权利要求不被说明本发明的特征的示例的选择限制。在权利要求中所用的一些数值范围也包括了在其之内的子范围，这些范围中的变化也应在可能的情况下解释为被所附的权利要求覆盖。

Claims (10)

  1. 一种除草组合物，其特征在于，所述组合物包括组苯嘧草唑和草甘膦；所述苯嘧草唑和草甘膦的重量比为1∶(10-100)。
  2. 一种除草组合物制剂，其特征在于，由权利要求1所述的除草组合物和农药学上可接受的辅料组成。
  3. 根据权利要求2所述的除草组合物制剂，其特征在于，所述除草组合物制剂的剂型选自可溶液剂、微乳剂、可分散油悬浮剂、可湿性粉剂、水分散粒剂中的一种。
  4. 根据权利要求2所述的除草组合物制剂，其特征在于，所述除草组合物占所述除草组合物制剂的重量百分比为5％-90％。
  5. 根据权利要求2所述的除草组合物制剂，其特征在于，所述除草组合物制剂的剂型为可分散油悬浮剂；所述农药学上可接受的辅料包括乳化剂、润湿剂、分散剂、稳定剂、消泡剂、黏度调节剂、基础油中的至少一种。
  6. 根据权利要求5所述的除草组合物制剂，其特征在于，所述乳化剂选自蓖麻油聚氧乙烯醚、十二烷基苯磺酸钙、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯酯、烷基酚甲醛树脂聚氧乙烯醚、山梨醇酐单硬脂酸酯、失水山梨醇单硬脂酸酯聚氧乙烯醚、苯乙基酚聚氧乙烯醚、苯乙基苯酚聚氧乙烯聚氧丙烯醚、烷氧基聚氧乙烯醚磺酸盐、脂肪醇硫酸盐、烷基磷酸酯盐、脂肪醇聚氧乙烯醚硫酸盐、EO-PO嵌段共聚物和苯乙基酚聚氧乙烯醚磺酸盐中的至少一种。
  7. 根据权利要求6所述的除草组合物制剂，其特征在于，所述乳化剂为蓖麻油聚氧乙烯醚和苯乙基酚聚氧乙烯醚磺酸盐的组合，重量比为1∶(0.1-0.5)。
  8. 根据权利要求5所述的除草组合物制剂，其特征在于，所述分散剂选自聚羧酸盐、木质素磺酸盐、EO-PO嵌段共聚物、磷酸酯及其盐类、磺酸盐类、烷基萘磺酸盐、烷基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚中的至少一种。
  9. 根据权利要求5所述的除草组合物制剂，其特征在于，所述黏度调节剂为有机膨润土和硅酸镁铝的组合，重量比为1∶(0.5-2)。
  10. 一种根据权利要求1所述的除草组合物的应用，其特征在于，应用于防除非耕地杂草。
PCT/CN2022/075774 2021-03-22 2022-02-10 一种除草组合物、制剂及其应用 WO2022199267A1 (zh)

Priority Applications (8)

Application Number Priority Date Filing Date Title
JP2023544452A JP2024505859A (ja) 2021-03-22 2022-02-10 除草組成物、製剤およびその応用
EP22773929.9A EP4230041A1 (en) 2021-03-22 2022-02-10 Herbicidal composition, preparation, and application thereof
CA3204749A CA3204749A1 (en) 2021-03-22 2022-02-10 Herbicidal composition, preparation, and application thereof
BR112023007701A BR112023007701A2 (pt) 2021-03-22 2022-02-10 Um tipo de composição herbicida, preparação e sua aplicação
AU2022244795A AU2022244795B2 (en) 2021-03-22 2022-02-10 Herbicidal composition, preparation, and application thereof
KR1020237013491A KR20230070297A (ko) 2021-03-22 2022-02-10 일종 제초 조성물, 제제 및 그 응용
ZA2023/05792A ZA202305792B (en) 2021-03-22 2023-05-30 Herbicidal composition, preparation and its application
CONC2023/0008684A CO2023008684A2 (es) 2021-03-22 2023-06-30 Un tipo de composición herbicida, y su formulación y aplicación

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110304261.2A CN113412840A (zh) 2021-03-22 2021-03-22 一种除草组合物、制剂及其应用
CN202110304261.2 2021-03-22

Publications (1)

Publication Number Publication Date
WO2022199267A1 true WO2022199267A1 (zh) 2022-09-29

Family

ID=77711983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/075774 WO2022199267A1 (zh) 2021-03-22 2022-02-10 一种除草组合物、制剂及其应用

Country Status (13)

Country Link
EP (1) EP4230041A1 (zh)
JP (1) JP2024505859A (zh)
KR (1) KR20230070297A (zh)
CN (1) CN113412840A (zh)
AR (1) AR125135A1 (zh)
AU (1) AU2022244795B2 (zh)
BR (1) BR112023007701A2 (zh)
CA (1) CA3204749A1 (zh)
CO (1) CO2023008684A2 (zh)
TW (1) TWI809770B (zh)
UY (1) UY39679A (zh)
WO (1) WO2022199267A1 (zh)
ZA (1) ZA202305792B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118084571A (zh) * 2024-03-08 2024-05-28 山东爱福地生物股份有限公司 一种聚谷氨酸络合组合物及其制备方法和应用

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113412840A (zh) * 2021-03-22 2021-09-21 南通江山农药化工股份有限公司 一种除草组合物、制剂及其应用
CN113455513A (zh) * 2021-06-26 2021-10-01 南通江山农药化工股份有限公司 一种除草组合物、制剂及其应用
CN115316386A (zh) * 2021-10-29 2022-11-11 南通江山农药化工股份有限公司 一种除草组合物、制剂及其制备方法和应用
CN115281212B (zh) * 2022-04-27 2024-07-23 南通江山农药化工股份有限公司 一种含有苯嘧草唑的可分散油悬浮剂及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107318884A (zh) * 2017-08-24 2017-11-07 陕西上格之路生物科学有限公司 一种含草甘膦的三元除草组合物
CN108207997A (zh) * 2016-12-21 2018-06-29 沈阳中化农药化工研发有限公司 一种除草剂组合物及其应用
CN110692643A (zh) * 2018-07-09 2020-01-17 沈阳中化农药化工研发有限公司 一种除草剂及其应用
CN110786323A (zh) * 2019-10-12 2020-02-14 惠州市银农科技股份有限公司 一种以草甘膦为有效成分的可分散油悬浮剂及其制备方法
CN113412840A (zh) * 2021-03-22 2021-09-21 南通江山农药化工股份有限公司 一种除草组合物、制剂及其应用
CN113491269A (zh) * 2020-03-20 2021-10-12 沈阳中化农药化工研发有限公司 一种除草剂组合物可分散油悬浮剂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9424353D0 (en) * 1994-12-02 1995-01-18 Ici Plc Surfactants
GB9714907D0 (en) * 1997-07-16 1997-09-17 Ici Plc Production of aromatic carboxylic acids
CN112075436B (zh) * 2020-09-25 2022-11-15 江苏富田农化有限公司 一种除草组合物、制剂及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108207997A (zh) * 2016-12-21 2018-06-29 沈阳中化农药化工研发有限公司 一种除草剂组合物及其应用
CN107318884A (zh) * 2017-08-24 2017-11-07 陕西上格之路生物科学有限公司 一种含草甘膦的三元除草组合物
CN110692643A (zh) * 2018-07-09 2020-01-17 沈阳中化农药化工研发有限公司 一种除草剂及其应用
CN110786323A (zh) * 2019-10-12 2020-02-14 惠州市银农科技股份有限公司 一种以草甘膦为有效成分的可分散油悬浮剂及其制备方法
CN113491269A (zh) * 2020-03-20 2021-10-12 沈阳中化农药化工研发有限公司 一种除草剂组合物可分散油悬浮剂及其制备方法
CN113412840A (zh) * 2021-03-22 2021-09-21 南通江山农药化工股份有限公司 一种除草组合物、制剂及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANG, JICHUN ET AL.: "Creation of Biocidal Herbicide SY-1604", PROCEEDINGS OF THE 18TH ANNUAL MEETING OF PESTICIDES SPECIALIZED COMMITTEE OF THE CHEMICAL INDUSTRY AND ENGINEERING SOCIETY OF CHINA, CHEMICAL INDUSTRY AND ENGINEERING SOCIETY OF CHINA, CN, 15 August 2018 (2018-08-15), CN, pages 113 - 118, XP009541487 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118084571A (zh) * 2024-03-08 2024-05-28 山东爱福地生物股份有限公司 一种聚谷氨酸络合组合物及其制备方法和应用

Also Published As

Publication number Publication date
EP4230041A1 (en) 2023-08-23
CO2023008684A2 (es) 2023-07-21
BR112023007701A2 (pt) 2023-10-03
AU2022244795A1 (en) 2023-06-01
CA3204749A1 (en) 2022-09-29
AU2022244795B2 (en) 2024-06-06
AU2022244795A9 (en) 2024-05-02
UY39679A (es) 2022-04-29
CN113412840A (zh) 2021-09-21
AR125135A1 (es) 2023-06-14
JP2024505859A (ja) 2024-02-08
TWI809770B (zh) 2023-07-21
KR20230070297A (ko) 2023-05-22
TW202236964A (zh) 2022-10-01
ZA202305792B (en) 2023-12-20

Similar Documents

Publication Publication Date Title
WO2022199267A1 (zh) 一种除草组合物、制剂及其应用
CN107969421B (zh) 一种草铵膦可分散油悬浮剂及其制备方法
CN101785455A (zh) 一种农药油悬剂及其制备方法
JP2019504089A (ja) 固体状水溶性担体上の界面活性物質の粉末状調製物、その製造方法およびその使用
CN113491269B (zh) 一种除草剂组合物可分散油悬浮剂及其制备方法
CN111567548A (zh) 一种含联苯菊酯和噻虫嗪的农药组合物及其应用
CN114651823A (zh) 一种砜吡草唑和氯酯磺草胺的悬浮剂及其制备方法和应用
CN108782597B (zh) 一种含草甘膦和丙炔氟草胺的悬浮剂
CN105831147B (zh) 一种含有硫虫酰胺和氯氟氰菊酯的农业杀虫组合物及其用途
CN112335668B (zh) 一种除草组合物、制剂及其制备方法和应用
CN112075436B (zh) 一种除草组合物、制剂及其制备方法
CN114223663A (zh) 一种含氯虫苯甲酰胺和虫螨腈的悬浮剂及其制备方法
CN103238603B (zh) 一种杀虫制剂及其应用
WO2023272463A1 (zh) 一种除草剂组合物可分散油悬浮剂及其制备方法
CN105613511A (zh) 一种农业杀虫组合物及其用途
CN112841189A (zh) 一种水稻田除草剂及其制备方法和应用
CN112042651A (zh) 一种除草组合物及其应用
CN110881473A (zh) 除草组合物及其应用
CN108935451B (zh) 一种噁虫威干悬浮剂及其制备方法
CN105660646A (zh) 一种农业杀虫组合物及其用途
CN112021320A (zh) 一种除草组合物及其应用
CN106417304A (zh) 双酰胺类杀虫剂的油悬剂及其制备方法
CN116869013A (zh) 一种包含异丙隆、甲基二磺隆和吡氟酰草胺的可分散油悬浮剂
CN116098160A (zh) 一种种子处理悬浮剂及其制备方法
WO2022119799A2 (en) An aqueous composition of epyrifenacil, mesotrione and pyroxasulfone

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22773929

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20237013491

Country of ref document: KR

Kind code of ref document: A

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112023007701

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 2022773929

Country of ref document: EP

Effective date: 20230420

WWE Wipo information: entry into national phase

Ref document number: 202327037283

Country of ref document: IN

ENP Entry into the national phase

Ref document number: 2022244795

Country of ref document: AU

Date of ref document: 20220210

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 18270512

Country of ref document: US

ENP Entry into the national phase

Ref document number: 3204749

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2023544452

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202392287

Country of ref document: EA

ENP Entry into the national phase

Ref document number: 112023007701

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20230424

NENP Non-entry into the national phase

Ref country code: DE