CN112075436A - Weeding composition, preparation and preparation method thereof - Google Patents
Weeding composition, preparation and preparation method thereof Download PDFInfo
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- CN112075436A CN112075436A CN202011020663.1A CN202011020663A CN112075436A CN 112075436 A CN112075436 A CN 112075436A CN 202011020663 A CN202011020663 A CN 202011020663A CN 112075436 A CN112075436 A CN 112075436A
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- Prior art keywords
- herbicide
- dispersible oil
- emulsifier
- agent
- clodinafop
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—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 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
Abstract
The invention relates to the technical field of pesticides, and particularly relates to a weeding composition, a preparation and a preparation method thereof. A herbicidal composition comprising metamifop and clodinafop-propargyl. The invention also provides a herbicide dispersible oil suspension agent containing the composition. The herbicide composition adopts the metamifop and the clodinafop-propargyl for compounding, has low toxicity, wide herbicide controlling spectrum, quick response and good persistence, has extremely strong herbicide controlling activity on broadleaf weeds and grassy weeds, is safe to crops, overcomes the defect of single active component herbicide, reduces the application dosage, delays the drug resistance, and lightens the drug burden of farmers and the pollution to the environment. The invention also provides a herbicide dispersible oil suspending agent containing the weeding composition, the particle size is small, the oil suspending agent can be well dispersed after being emulsified and wetted, the suspension rate is high, the physical stability is good, the adhesion capability on the surface of a plant is strong, the rain wash resistance is realized, and the pesticide effect is durable.
Description
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a weeding composition, a preparation and a preparation method thereof.
Background
Aryloxy phenoxy propionic Acid (APP) herbicide is one of important herbicide types for preventing and killing gramineous weeds, but after a single agent is used for a long time, weeds generate strong drug resistance, and the weeding effect is poor. And a single agent generally only aims at one type of weeds to be prevented and removed, and if a plurality of types of weeds, such as broadleaf weeds and annual gramineous weeds, need to be prevented and removed simultaneously, two or more than two herbicides need to be sprayed simultaneously, so that the application amount is large, and the application burden of farmers is increased.
The dispersible oil suspending agent is a liquid preparation with active ingredients stably suspended in liquid incompatible with water, is diluted and prepared by water and is used by spraying weeds, and has the advantages of safety, environmental protection, good drug effect, good adhesiveness, strong spreadability, strong rain erosion resistance and the like. However, under the influence of the emulsifier, the emulsion obtained by diluting the original drug with water is not uniform, so that the concentration of active ingredients in the obtained emulsion is not uniform, the concentration of the active ingredients sprayed on the surfaces of weeds is not uniform, so that the active ingredients on the surfaces of some weeds are too low to kill, and the expected weeding effect cannot be achieved in the actual use. The method is particularly urgent for better exerting the control effect of the active ingredients of the pesticide, particularly the dispersible oil suspending agent is not ideal as a new formulation, and the existing dispersible oil suspending agent has the defects of poor emulsifying dispersibility, serious layering, easy thickening or bottom forming.
Aiming at the technical problems, the invention provides a weeding composition and a herbicide dispersible oil suspension agent prepared from the weeding composition, which not only have better emulsion dispersibility and stability, but also overcome the defect of single active component herbicide, realize the prevention and control of broadleaf weeds and annual gramineous weeds, simultaneously reduce the application dosage, and reduce the medication burden of farmers and the pollution to the environment.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a herbicidal composition comprising metamifop and clodinafop-propargyl.
As a preferred embodiment of the present invention, the weight ratio of metamifop to clodinafop-propargyl is 100: 1-1: 100.
as a preferred embodiment of the present invention, the formulation of the herbicidal composition is at least one selected from the group consisting of oil suspension, aqueous suspension, emulsifiable concentrate, aqueous emulsion, microemulsion, concentrated emulsion, microcapsule, wettable powder, soluble powder, water dispersible granule, and effervescent tablet.
The second aspect of the present invention provides a herbicide dispersible oil suspension agent containing the herbicidal composition, which is prepared from the following raw materials in percentage by weight: 5-35% of weeding composition, 5-15% of emulsifier, 5-20% of dispersant, 1-5% of wetting agent, 1-5% of thickening agent and the balance of dispersion medium to 100%.
As a preferred embodiment of the present invention, the emulsifier is selected from hydrophilic emulsifiers having an HLB value of 3-6 and/or lipophilic emulsifiers having an HLB value of 9-12.
In a preferred embodiment of the present invention, the emulsifier is a mixture of polyoxyethylene sorbitan trioleate and sorbitan monooleate, and the weight ratio of the polyoxyethylene sorbitan trioleate to the sorbitan monooleate is (1-5): 1.
in a preferred embodiment of the present invention, the dispersant is at least one selected from the group consisting of alkylphenol ethoxylate formaldehyde condensates, lignosulfonates, polycarboxylates, naphthalene sulfonate formaldehyde condensates, p-methoxy fatty amido benzene sulfonic acid, and alkylphenol ethoxylate phosphate esters.
As a preferred embodiment of the invention, the dispersant is a mixture of a polycarboxylate and a naphthalene sulphonate formaldehyde polycondensate in a weight ratio of 1: (0.5-1.5).
As a preferred embodiment of the present invention, the dispersion medium includes at least methyl oleate.
The third aspect of the present invention provides a preparation method of the herbicide dispersible oil suspension concentrate, comprising the steps of:
(1) mixing the dispersion medium, emulsifier, dispersant and wetting agent, and stirring;
(2) adding the weeding composition and the thickening agent, and shearing for 10-40 minutes at the rotating speed of 1000-10000 r/min; and then the mixture is put into a sand mill and ground until the particle size D90 is less than 8 mu m, thus obtaining the product.
Advantageous effects
The invention provides a weeding composition, which is prepared by compounding metamifop and clodinafop-propargyl, has low toxicity, wide weeding spectrum, quick action and good persistence, has extremely strong weeding activity on broadleaf weeds and gramineous weeds, is safe to crops, overcomes the defect of a herbicide containing a single active component, reduces the application dosage, delays the drug resistance, and reduces the drug burden of farmers and the pollution to the environment. The invention also provides a herbicide dispersible oil suspending agent containing the weeding composition, the particle size is small, the oil suspending agent can be well dispersed after being emulsified and wetted, the suspension rate is high, and the physical stability is good; the plant disinfectant can be directly prepared into spray liquid for use, has strong adhesion capability on the surface of a plant, is rain-wash resistant, and has lasting drug effect; the preparation method is simple, no dust pollution is caused in the production process, flammable and explosive organic solvents are not used, the production method is safe for producers, users and environment, the storage and the transportation are convenient and safe, and the processing and the packaging cost is low.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The term "prepared from …" as used herein is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In a first aspect of the present invention there is provided a herbicidal composition comprising metamifop and clodinafop-propargyl.
In a preferred embodiment, the weight ratio of metamifop to clodinafop-propargyl is 100: 1-1: 100.
in a more preferred embodiment, the weight ratio of metamifop to clodinafop-propargyl is 1: (0.1-10).
The inventor finds that the timeliness and the weeding effect of the herbicide can be remarkably improved by compounding the metamifop and the clodinafop-propargyl, and the weeding effect on grassy and broadleaf weeds is particularly optimal. The inventors believe that the possible reason is that fatty acids have important physiological roles in the plant body, being the basic structural components of triglycerides, which are the main energy-storing and-supplying substances, and the phospholipids converted from them are also constituents of cell membranes, and fatty acids can also be converted into metabolic hormone-like substances, of which acetyl-coa carboxylase (ACCase) is a key enzyme in fatty acid biosynthesis. The molecular structures of the metamifop and the clodinafop-propargyl both have active group F atoms, and the molecular structures also contain ester groups, so that the metamifop and the clodinafop-propargyl are easier to absorb by weeds. The effective components are absorbed by leaves and leaf sheaths of plants, transmitted by phloem, accumulated in meristems of plants, can inhibit biosynthesis of lipid into acetyl-coenzyme A hydroxylase inhibitor, inhibit acetyl-coenzyme A carboxylase (ACCase), stop fatty acid synthesis, and hinder processes of further synthesizing fatty acid, so that the processes of forming oleic acid, linoleic acid, linolenic acid, a wax layer and a cuticle are hindered, thus cell growth and division can not be normally carried out, a membrane structure is rapidly destroyed, permeability is enhanced, and finally plant death is caused. The inventor finds in the process of experiments that if only a single agent is used, the weeding range has certain limitation, and the weeds are easy to generate drug resistance, so that the weeding effect is poor. By compounding the metamifop and the clodinafop-propargyl, the defects and limitations of a single agent in use are overcome, particularly the major hazard of the clodinafop-propargyl to crops is relieved, the herbicidal spectrum can be enlarged, the herbicidal effect is improved, the application period is prolonged, the phytotoxicity is reduced, the occurrence and development of the drug resistance of the herbicide are delayed, the problem of low prevention effect of the single clodinafop-propargyl agent to the poa annua is solved, the excellent herbicidal effect on broad-leaved weeds and gramineous weeds is shown, and particularly the optimal removal effect on annual gramineous weeds is achieved. The inventor also unexpectedly finds that clodinafop-propargyl is quickly degraded into free acid phenyl and pyridine parts in soil to enter the soil and mineralize, metamifop has low toxicity and environment-friendly effect, and after the two agents are compounded, the using dosage of pesticide is reduced, and the adverse effect of the pesticide on the ecological environment is reduced.
The inventor also unexpectedly finds that the weight ratio of the metamifop to the clodinafop-propargyl in the invention is not higher than 1: 1, the weeding composition is suitable for removing annual weeds, particularly grassy weeds, and has the best removal effect; with the increasing of the amount of clodinafop-propargyl, the weeding spectrum of the clodinafop-propargyl is gradually increased, and the clodinafop-propargyl can be used for removing perennial malignant weeds and deepening the phytotoxicity degree of the clodinafop-propargyl on crops. Thus, the amount of clodinafop-propargyl in the formulation cannot exceed 35%.
In the invention, the dosage form of the weeding composition is at least one selected from oil suspending agent, water suspending agent, missible oil, aqueous emulsion, microemulsion, concentrated emulsion, microcapsule, wettable powder, soluble powder, water dispersible granule, granule and effervescent tablet.
The inventor finds that the metamifop and the clodinafop-propargyl adopted by the invention are solid pesticides, and the lipophilicity, the membrane permeability, the anti-metabolic stability, the volatility, the thermal stability and the chemical stability of the compound are increased due to the introduction of fluorine atoms, so that the biological activity of the compound can be improved, and the resistance of organisms to the compound is difficult to generate. The structures of the metamifop and the clodinafop-propargyl contain fluorine atoms, so that the lipophilicity of the active ingredient is greatly enhanced. If the pesticide is processed into the aqueous suspension, when the aqueous suspension is diluted by water and sprayed on a target, particularly on rice leaf surfaces, the pesticide is not easy to wet and spread due to large surface tension and poor adhesiveness, and is easy to roll off, so that the pesticide effect is reduced. The metamifop and the clodinafop-propargyl are systemic conduction herbicides, and the use of the oil can quickly help the active ingredients to conduct and penetrate through the epidermis of crops to enter the interior of the plants, so that the permeability, the adhesiveness and the absorption capacity of the active ingredients are improved, and the aim of improving the pesticide effect is fulfilled.
The second aspect of the present invention provides a herbicide dispersible oil suspension agent containing the herbicidal composition, which is prepared from the following raw materials in percentage by weight: 5-35% of weeding composition, 5-15% of emulsifier, 5-20% of dispersant, 1-5% of wetting agent, 1-5% of thickening agent and the balance of dispersion medium to 100%.
In a more preferred embodiment, the herbicide dispersible oil suspension comprises the following components in percentage by weight: 24% of weeding composition, 10% of emulsifier, 8% of dispersant, 2% of wetting agent, 3% of thickening agent and the balance of dispersion medium to 100%.
Emulsifier
In the present invention, the emulsifier is a nonionic emulsifier, and there is no particular limitation, and a hydrophilic emulsifier and a lipophilic emulsifier can be mentioned.
As the hydrophilic emulsifier, there may be mentioned polyoxyethylene sorbitan monooleate, polyoxypropylene stearate, polyoxyethylene lanonol ester, sorbitan laurate, polyoxyethylene fatty acid, polyoxyethylene oxypropylene oleate, polyoxyethylene sorbitol beeswax derivatives, tetraethylene glycol mono-and silicate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monostearate, hexaethylene glycol monostearate, polyoxyethylene lanolin ether, polyoxyethylene cetyl ether, polyoxyethylene sorbitan tristearate, polyoxyethylene lauryl ether, polyoxyethylene sorbitan trioleate, polyoxyethylene oxypropylene oleate, polyoxyethylene lanolin derivatives, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monooleate, polyoxyethylene monostearate, polyoxyethylene monopalmitate, polyoxyethylene monolaurate, polyoxyethylene sorbitan monolaurate, Alkylaryl sulfonates, triethanolamine oleate, polyoxyethylene monolaurate, polyoxyethylene alkylphenols, polyoxyethylene acetylated lanolin derivatives, polyoxyethylene sorbitol lanolin derivatives, polyoxyethylene alkylaryl ethers, polyoxyethylene monolaurate, polyoxyethylene lauryl ether, polyoxyethylene castor oil, polyoxyethylene vegetable oils, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monolaurate, and the like.
As the lipophilic emulsifier, there may be mentioned propylene glycol fatty acid ester, propylene glycol monostearate, sorbitan sesquioleate, polyethylene sorbitol, glyceryl monostearate, polyoxyethylene sorbitol beeswax derivative, propylene glycol fatty acid ester, sorbitan monooleate, propylene glycol laurate, propylene glycol monolaurate, propylene glycol fatty acid ester, sorbitan monostearate, diethylene glycol monooleate, diethylene glycol monostearate, diethylene glycol fatty acid ester, polyoxyethylene oleyl ether, polyoxyethylene sorbitol beeswax derivative, ethylene glycol fatty acid ester, glyceryl monostearate, diethylene glycol fatty acid ester, tetraethylene glycol monostearate, tetraethylene glycol monooleate, and the like.
In a preferred embodiment, the emulsifier is selected from hydrophilic emulsifiers having an HLB value of from 3 to 6 and/or lipophilic emulsifiers having an HLB value of from 9 to 12.
In a preferred embodiment, the emulsifier is a mixture of polyoxyethylene sorbitan trioleate and sorbitan monooleate in a weight ratio of (1-5): 1.
in a more preferred embodiment, the emulsifier is a mixture of polyoxyethylene sorbitan trioleate and sorbitan monooleate in a weight ratio of 3: 1.
the inventor finds that the dispersible oil suspending agent takes oil as a dispersing medium, the density of the oil is lower than that of water, and if the oil is directly dropped into the water, the oil can float on the water surface and seriously affect the dispersion of the agent in the water, thereby affecting the weeding effect, so whether an oily preparation can be fully emulsified to form a good secondary dispersing system when the oily preparation is used for water or not can remarkably affect the weeding effect of the dispersible oil suspending agent. The inventor finds that the compounding of polyoxyethylene sorbitan trioleate and sorbitan monooleate can play a role in synergy, so that after the prepared dispersible oil suspending agent is diluted by water, oil drops are not easy to form on the surface of an emulsion, the emulsion with uniform texture can be formed, and therefore when weeds are sprayed, active ingredients of pesticides on the surfaces of the weeds are uniformly attached to the surfaces of stems and leaves of the weeds, and the weeding effect is improved. The inventor believes that the possible reasons are that the interfacial tension of the micro-droplets of the dispersible oil suspending agent is greatly reduced after the dispersible oil suspending agent is diluted by water, the volume of the droplets formed by scattering in the water is small, the dispersion suspension property is good, and the obtained emulsion is uniform in texture and stable; because the compound emulsifier of the polyoxyethylene sorbitan trioleate and the sorbitan monooleate contains ester structures, the emulsifier has better affinity with the original medicines of the metamifop and the clodinafop-propargyl, the molecules are crosslinked through chemical bonds, the small-molecular original medicine is firmly wrapped in the emulsifier, meanwhile, a plurality of long chains of the polyoxyethylene sorbitan trioleate are entangled into a net structure, a layer of water film is formed on the surface of the original medicine, the fixing effect is achieved, the distribution uniformity and stability of the effective components in the emulsion are improved, the clotted and separated-out and settled clodinafop-propargyl in water are prevented, and particularly under the low-temperature condition, the dispersibility, the suspension property and the stability of the effective components are obviously improved. Because the concentration of the effective components is an important factor for the control effect of the weeds, the compound emulsifier is adopted, so that the concentration of the effective components sprayed on the stems and leaves of the weeds is uniform, and the insecticidal effect can be improved. The inventor also unexpectedly finds that the compounding of the polyoxyethylene sorbitan trioleate and the sorbitan monooleate can improve the adhesion, wetting, spreading, permeation and other properties of the liquid medicine on the plant leaf surfaces.
Dispersing agent
In the invention, the dispersant is at least one selected from alkylphenol polyoxyethylene ether formaldehyde condensate, lignosulfonate, polycarboxylate, naphthalenesulfonate formaldehyde condensate, p-methoxy fatty amido benzene sulfonic acid and alkylphenol polyoxyethylene ether phosphate.
In a preferred embodiment, the dispersant is a mixture of a polycarboxylate and a naphthalene sulfonate formaldehyde polycondensate in a weight ratio of 1: (0.5-1.5).
In a more preferred embodiment, the weight ratio of the polycarboxylate and naphthalene sulfonate formaldehyde polycondensate is 1: 0.8.
in a most preferred embodiment, the polycarboxylate has a comb-like structure; the naphthalene sulfonate formaldehyde polycondensate is a modified naphthalene sulfonate formaldehyde polycondensate.
In the present invention, the polycarboxylate may be obtained from Beijing broad-source agricultural chemical company of the limited liability of agricultural chemistry under the model numbers GY-D800, GY-D900, GY-D600, GY-D04, GY-D06, GY-D08, etc.; GY-D800 and GY-D900 are preferred.
In the present invention, as the source of the naphthalene sulfonate formaldehyde polycondensate, Beijing, Guangyuan agricultural chemical, LLC (Gy-D10), NDS (NDS) and the like can be mentioned.
In the invention, the weight ratio of the emulsifier to the dispersant is 1: (0.3-1.5).
In a preferred embodiment, the weight ratio of emulsifier to dispersant is 1: 0.8.
in order to ensure the long-term stable uniform dispersion of solid original drug particles in an oil dispersion medium and prevent the problems of flocculation, large particle size, storage caking and the like of a sample. The inventor finds that the dispersibility and stability of the dispersible oil suspending agent in an oil dispersion medium can be remarkably improved by compounding the polycarboxylate dispersing agent and the naphthalenesulfonate formaldehyde polycondensate. The inventor thinks that the possible reason is that the surface of the original drug particles has a hydrophobic structure, while the polycarboxylate dispersing agent adopted by the invention has an amphiphilic structure, so that the polycarboxylate dispersing agent can be adsorbed on the surface of the original drug particles, reduce the interfacial free energy of the original drug particles and weaken the merging tendency among the pesticide particles, and on the other hand, an electric double layer is formed on the surface of the original drug particles through self ionization, and the dispersed original drug particles are stably dispersed in an oily dispersing medium by virtue of the steric hindrance formed by the electric double layer and the macromolecules; when the dispersible oil suspending agent is diluted by water, the conjugated system in the naphthalene ring of the modified naphthalene sulfonate formaldehyde polycondensate has strong deformability, is easy to be adsorbed on the surface of pesticide particles, and the hydrophilic group of the modified naphthalene sulfonate formaldehyde polycondensate is easy to form hydrogen bonds with water to generate association, so that a stable water film is formed on the surface of the pesticide particles, the fluidity and the suspension property of pesticide particles are obviously improved, and the dispersible oil suspending agent has good salt resistance, hard water resistance and thermal stability. After the polycarboxylate dispersant and the naphthalenesulfonate formaldehyde polycondensate are compounded for use, the original drug molecules have good stability in an oily dispersion medium and water. In the test process, the inventor finds that when the dosage of the dispersing agent is less than 5%, the dispersing agent does not reach saturated adsorption on the surface of original drug particles, pesticide particles cannot be fully coated by dispersing agent molecules, and the particles are agglomerated and settled under the action of van der waals acting force and gravity field, so that the viscosity of the preparation is increased. When the amount of the dispersant is about 5%, the viscosity is reduced to a value range which is relatively small and suitable for pourability. When the amount of the dispersant is further increased to more than 10%, the excessive dispersant molecules in the suspension are entangled with the coating layer on the surface of the active ingredient particles, causing bridging between the particles, resulting in flocculation, resulting in an increase in the viscosity of the formulation. Meanwhile, in the sanding process, the compounding of the polycarboxylate and the naphthalenesulfonate formaldehyde polycondensate has the obvious viscosity reducing effect and improves the sanding efficiency. In addition, the inventors have surprisingly found that the compounding of a comb-like polycarboxylate structure with a naphthalene sulphonate formaldehyde polycondensate also effectively alleviates the problems of oil bleeding and hot-storage viscous creaming of a dispersible oil suspension. The inventor thinks that the invention selects the emulsifier with ester group, which has better compatibility with the oily dispersion medium, and the polyoxyethylene sorbitan trioleate has four long-chain structures, which can be entangled with the comb-shaped polycarboxylate to form a network structure, thus improving the stability of the system and keeping the rheological property; particularly, the naphthalenesulfonate formaldehyde condensate can be adsorbed on the surface of the original medicine, the steric hindrance of molecules is increased, the charge is cooperated, and the migration, aggregation and sedimentation of the original medicine molecules are inhibited.
Thickening agent
In the present invention, the thickener is not particularly limited.
In a preferred embodiment, the thickener is selected from bentonite, silica, xanthan gum, attapulgite, anti-settling thixotropic agents and the like.
In a preferred embodiment, the thickener is a mixture of bentonite and white carbon black.
In a more preferred embodiment, the weight ratio of bentonite to white carbon black is 1: (0.05-0.4).
In a most preferred embodiment, the weight ratio of bentonite to white carbon black is 1: 0.2.
the inventor believes that the addition of the thickener in the present invention increases the viscosity of the suspension system, and maintains the stability of the dispersion system by adsorbing the dispersion medium with the thickener. However, as the temperature rises, the dispersion medium adsorbed in the thickener is released, resulting in the occurrence of oil bleeding. In the invention, the bentonite and the white carbon black are compounded, and the dispersing medium contains the methyl oleate, so that the oil bleeding problem of the dispersible oil suspending agent under the high-temperature condition can be better solved. The inventor believes that the possible reason is that the bentonite can absorb oil in methyl oleate to expand to form a network gel structure, so that a large amount of oily dispersion medium molecules are wrapped in network gaps, and the viscosity of the system is increased. However, as the shear rate increases, the structure is broken, and a large amount of the encapsulated oily dispersion medium is released again, thus showing a shear-thinned state. However, a certain amount of white carbon black is added, and the white carbon black can form a three-dimensional structure after oil absorption and expansion, so that the overlapping and covering opportunities of organic carbon chains of bentonite are increased, the structural damage resistance is increased, the yield value of a system is increased, and the oil separation rate of the dispersible oil suspending agent in the normal temperature and heat storage states is reduced; meanwhile, as the carbon chains of the bentonite are mutually overlapped to form a network structure, the structure can support pesticide particles and enable the pesticide particles to be well suspended in a dispersion system.
Dispersion medium
In the present invention, the dispersion medium is not particularly limited.
In a preferred embodiment, the dispersion medium comprises at least methyl oleate.
In a more preferred embodiment, the amount of methyl oleate present in the dispersion medium is from 20 to 60% by weight.
In a more preferred embodiment, the amount of methyl oleate present in the dispersion medium is 40% by weight.
In a preferred embodiment, vegetable light oil, rosin oil, palm oil, mineral oil, fatty acid methyl ester, and the like can also be mentioned as the dispersion medium.
According to the invention, the addition of the methyl oleate not only can be used for coordinating with the thickener, reducing the oil bleeding phenomenon of the dispersible oil suspending agent, and improving the suspension rate of the effective components; meanwhile, the inventor also finds that the dispersing agent polyoxyethylene sorbitan trioleate and sorbitan monooleate used in the invention have poor compatibility and dispersibility, and the problem can be well solved by adding methyl oleate.
The second aspect of the present invention provides a method for preparing the herbicide dispersible oil suspension concentrate, comprising the steps of:
(1) mixing the dispersion medium, emulsifier, dispersant and wetting agent, and stirring;
(2) adding the weeding composition and the thickening agent, and shearing for 10-40 minutes at the rotating speed of 1000-10000 r/min; and then the mixture is put into a sand mill and ground until the particle size D90 is less than 8 mu m, thus obtaining the product.
The particle size measuring method comprises the following steps:
1. laser particle size method: and (3) measuring the average particle size Dav of the suspension sample by using a laser particle size analyzer, wherein the sample introduction is carried out for 3 times during the particle size measurement, the measurement is repeated for 3 times each time, and the average value is taken.
2. Microscopy: accurately taking 1mL of dispersible oil suspending agent by using an injector, dripping the dispersible oil suspending agent into a beaker, adding methyl oleate for diluting by 250 times, coating the mixture on a glass slide, observing under a microscope, and taking a picture, recording and analyzing.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Example 1 provides a herbicide dispersible oil suspension agent, which is prepared from the following raw materials in percentage by weight: 24% of weeding composition, 10% of emulsifier, 8% of dispersant, 2% of wetting agent, 3% of thickening agent and the balance of dispersion medium to 100%.
The weeding composition comprises metamifop and clodinafop-propargyl in a weight ratio of 1: 4; the emulsifier is a mixture of polyoxyethylene sorbitan trioleate and sorbitan monooleate, and the weight ratio of the polyoxyethylene sorbitan trioleate to the sorbitan monooleate is 3: 1; the dispersant is a mixture of polycarboxylate and naphthalene sulfonate formaldehyde polycondensate, and the weight ratio of the polycarboxylate to the naphthalene sulfonate formaldehyde polycondensate is 1: 0.8; the thickening agent is a combination of bentonite and white carbon black, and the weight ratio is 1: 0.2; the dispersion medium is a combination of methyl oleate and soybean oil, and the weight ratio is 2: 3.
the preparation method of the herbicide dispersible oil suspending agent comprises the following steps:
(1) mixing the dispersion medium, emulsifier, dispersant and wetting agent, and stirring;
(2) adding the weeding composition and the thickening agent, and shearing for 30 minutes at the rotating speed of 8000 revolutions per minute; and then the mixture is put into a sand mill and ground until the particle size D90 is less than 8 mu m, thus obtaining the product.
Example 2
Embodiment 2 provides a herbicide dispersible oil suspension agent, which comprises the following raw materials in percentage by weight: 5% of weeding composition, 5% of emulsifier, 5% of dispersant, 1% of wetting agent, 1% of thickening agent and the balance of dispersion medium to 100%.
The weeding composition comprises metamifop and clodinafop-propargyl in a weight ratio of 10: 1; the emulsifier is a mixture of polyoxyethylene sorbitan trioleate and sorbitan monooleate, and the weight ratio of the polyoxyethylene sorbitan trioleate to the sorbitan monooleate is 1: 0.5; the dispersant is a mixture of polycarboxylate and naphthalene sulfonate formaldehyde polycondensate, and the weight ratio of the polycarboxylate to the naphthalene sulfonate formaldehyde polycondensate is 1: 0.8; the thickening agent is a combination of bentonite and white carbon black, and the weight ratio is 1: 0.05; the dispersion medium is a combination of methyl oleate and soybean oil, and the weight ratio is 1: 4.
the preparation method of the herbicide dispersible oil suspending agent comprises the following steps:
(1) mixing the dispersion medium, emulsifier, dispersant and wetting agent, and stirring;
(2) adding the weeding composition and the thickening agent, and shearing for 30 minutes at the rotating speed of 8000 revolutions per minute; and then the mixture is put into a sand mill and ground until the particle size D90 is less than 8 mu m, thus obtaining the product.
Example 3
Example 3 provides a herbicide dispersible oil suspension agent, which is prepared from the following raw materials in percentage by weight: 35% of weeding composition, 15% of emulsifier, 20% of dispersant, 5% of wetting agent, 5% of thickening agent and the balance of dispersion medium to 100%.
The weeding composition comprises metamifop and clodinafop-propargyl in a weight ratio of 1: 10; the emulsifier is a mixture of polyoxyethylene sorbitan trioleate and sorbitan monooleate, and the weight ratio of the polyoxyethylene sorbitan trioleate to the sorbitan monooleate is 5: 1; the dispersant is a mixture of polycarboxylate and naphthalene sulfonate formaldehyde polycondensate, and the weight ratio of the polycarboxylate to the naphthalene sulfonate formaldehyde polycondensate is 1: 1.5; the thickening agent is a combination of bentonite and white carbon black, and the weight ratio is 1: 0.4; the dispersion medium is a combination of methyl oleate and soybean oil, and the weight ratio is 3: 2.
the preparation method of the herbicide dispersible oil suspending agent comprises the following steps:
(1) mixing the dispersion medium, emulsifier, dispersant and wetting agent, and stirring;
(2) adding the weeding composition and the thickening agent, and shearing for 30 minutes at the rotating speed of 8000 revolutions per minute; and then the mixture is put into a sand mill and ground until the particle size D90 is less than 8 mu m, thus obtaining the product.
Example 4
Example 4 differs from example 1 in that the sorbitan monooleate is replaced by sorbitan tristearate; the HLB value of the sorbitan monooleate is 4.3; the HLB value of the sorbitan tristearate is 1.8.
Example 5
Example 5 differs from example 1 in that the polyoxyethylene sorbitan trioleate is replaced by polyoxyethylene sorbitan monolaurate; the HLB value of the polyoxyethylene sorbitan trioleate is 11; the HLB value of the polyoxyethylene sorbitan monolaurate is 13.3.
Example 6
Example 6 differs from example 1 in that the sorbitan monooleate is replaced with calcium dodecylbenzene sulfonate.
Example 7
Example 7 differs from example 1 in that the dispersant is a polycarboxylate.
Example 8
Example 8 differs from example 1 in that the dispersant is a naphthalene sulfonate formaldehyde condensate.
Example 9
Example 9 differs from example 1 in that the thickener is bentonite.
Example 10
Example 10 differs from example 1 in that the thickener is xanthan gum.
Example 11
Example 11 differs from example 1 in that the dispersion medium is soybean oil.
Performance testing
1. Determination of the suspension Rate
The test of the suspension ratio can refer to HG/T2467.5-2003. Accurately weighing 1.0 + -0.02 g (m)1) The dispersible oil suspension sample prepared in example was poured into a stoppered graduated cylinder containing 250mL of standard hard water, and the stoppered graduated cylinder was closed and inverted 30 times (1 time of up-down 180 °). The measuring cylinder with the plug is placed in a constant-temperature water bath device with no fluctuation at 25 +/-1 ℃, timing is started, the measuring cylinder is taken out of a water bath kettle after 30min, a micro vacuum pump is used for slowly pumping out 225mL (namely 9/10) of solution at the upper layer, the measuring cylinder is not shaken in the process, the tail end of a suction pipe is kept attached to the liquid level as far as possible, and the phenomenon that the latex pipe stretches into the measuring cylinder too long to suck out sediment at the bottom of the measuring cylinder is avoided, so that the accuracy of a test result is influenced. The remaining 25mL of sample at the bottom of the cylinder was transferred to a weighed clean petri dish, and the mass of the clean petri dish was recorded (m)2) Placing the culture dish containing the solution in a drying oven at 74 +/-1 ℃ to dry to constant weight, and weighing the mass (m) of the dried culture dish3) The mean was taken 3 times. The suspension ratio W (%) is calculated as follows: w ═ 1- (m)3-m2)/m1]X 9/10 x 100%; wherein m is1Is the mass, m, of the sample2Mass m of the culture dish before drying3The mass of the dried culture dish.
2. Measurement of oil bleeding Rate
And (3) centrifuging 5mL of the dispersible oil suspending agent prepared in the embodiment for 30min at 3000r/min, taking out, observing and recording the oil separation and precipitation conditions, and calculating the oil separation rate according to the ratio of the oil separation volume to the total volume.
3. Stability determination
1. And (3) testing the heat storage stability:
sucking 10g of the dispersible oil suspending agent prepared in the embodiment by using a suction pipe, injecting the dispersible oil suspending agent into a clean ampoule bottle, sealing the ampoule bottle at high temperature, putting the ampoule bottle into a constant-temperature (54 +/-2 ℃) incubator, carrying out hot storage for 14 days, taking out, respectively detecting various indexes such as the suspension rate, the viscosity and the like of the dispersible oil suspending agent, and if the indexes before and after the hot storage reach the national standard, carrying out the hot storage for 2 years, and determining that the dispersible oil suspending agent is qualified.
2. Cold storage stability test:
sucking 80mL of the dispersible oil suspending agent prepared in the embodiment by using a suction pipe, placing the dispersible oil suspending agent in a 100mL beaker, refrigerating the dispersible oil suspending agent in a refrigerator (0 +/-2 ℃), placing the beaker for one hour, stirring the mixture once every 15 minutes, wherein the stirring time is 15s each time, observing the change of the appearance, continuously placing the beaker in the refrigerator for 7 days, taking out the beaker after 7 days, placing the beaker to room temperature, respectively detecting various indexes such as the suspension rate, the viscosity and the like of the dispersible oil suspending agent, and if the indexes before and after cold storage reach the national standard, judging that the cold storage is qualified, and storing the sample at normal temperature for 2 years.
Test results are shown in table 1.
TABLE 1 results of the Performance test of dispersible oil suspensions obtained in examples 1 to 11
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A herbicidal composition comprising metamifop and clodinafop-propargyl.
2. A herbicidal composition according to claim 1, characterized in that the weight ratio of metamifop to clodinafop-propargyl is 100: 1-1: 100.
3. a herbicidal composition according to claim 1 or 2, wherein the formulation of the herbicidal composition is at least one selected from the group consisting of oil-based suspensions, aqueous suspensions, emulsifiable concentrates, aqueous emulsions, microemulsions, concentrated emulsions, microcapsules, wettable powders, soluble powders, water dispersible granules, granules and effervescent tablets.
4. A herbicide dispersible oil suspension agent comprising the herbicidal composition of claim 1 or 2, wherein the herbicide dispersible oil suspension agent is prepared from raw materials comprising, in weight percent: 5-35% of weeding composition, 5-15% of emulsifier, 5-20% of dispersant, 1-5% of wetting agent, 1-5% of thickening agent and the balance of dispersion medium to 100%.
5. A herbicide dispersible oil suspension concentrate of claim 4 wherein the emulsifier is selected from hydrophilic emulsifiers having an HLB value of 3-6 and/or lipophilic emulsifiers having an HLB value of 9-12.
6. A herbicide dispersible oil suspension concentrate as claimed in claim 5, wherein the emulsifier is a mixture of polyoxyethylene sorbitan trioleate and sorbitan monooleate in a weight ratio of (1-5): 1.
7. a herbicide dispersible oil suspension concentrate as claimed in claim 4, wherein the dispersant is selected from at least one of alkylphenol ethoxylate formaldehyde condensate, lignosulfonate, polycarboxylate, naphthalene sulfonate formaldehyde condensate, p-methoxy fatty amidobenzene sulfonic acid, and alkylphenol ethoxylate phosphate.
8. A herbicide dispersible oil suspension concentrate as claimed in claim 7 wherein the dispersant is a mixture of a polycarboxylate and a naphthalene sulphonate formaldehyde polycondensate in a weight ratio of 1: (0.5-1.5).
9. A herbicide dispersible oil suspension concentrate as claimed in claim 5, wherein the dispersion medium includes at least methyl oleate.
10. A process for preparing a herbicide dispersible oil suspension concentrate as claimed in any one of claims 4 to 9 comprising the steps of:
(1) mixing the dispersion medium, emulsifier, dispersant and wetting agent, and stirring;
(2) adding the weeding composition and the thickening agent, and shearing for 10-40 minutes at the rotating speed of 1000-10000 r/min; and then the mixture is put into a sand mill and ground until the particle size D90 is less than 8 mu m, thus obtaining the product.
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| CN113412840A (en) * | 2021-03-22 | 2021-09-21 | 南通江山农药化工股份有限公司 | Weeding composition, preparation and application thereof |
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| CN104115848A (en) * | 2012-06-28 | 2014-10-29 | 永农生物科学有限公司 | Compound pesticide composition containing florasulam and picloram or salts thereof, preparation thereof and applications of the preparation |
| CN106305750A (en) * | 2016-08-20 | 2017-01-11 | 广东中迅农科股份有限公司 | Dispersible oil suspension containing mesosulfuron and clodinafop-propargyl and preparation method thereof |
| CN110692642A (en) * | 2019-08-05 | 2020-01-17 | 安徽农业大学 | Dispersible oil suspending agent containing metamifop and quinclorac |
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| US5002604A (en) * | 1981-12-31 | 1991-03-26 | Ciba-Geigy Corporation | 2-(4-(5-Chloro-3-fluoropyridin-2-yloxy)-phenoxy)-propionic acid derivatives having herbicidal activity |
| CN1713820A (en) * | 2002-11-21 | 2005-12-28 | 辛根塔参与股份公司 | Herbidical composition |
| CN104115848A (en) * | 2012-06-28 | 2014-10-29 | 永农生物科学有限公司 | Compound pesticide composition containing florasulam and picloram or salts thereof, preparation thereof and applications of the preparation |
| CN106305750A (en) * | 2016-08-20 | 2017-01-11 | 广东中迅农科股份有限公司 | Dispersible oil suspension containing mesosulfuron and clodinafop-propargyl and preparation method thereof |
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| CN113412840A (en) * | 2021-03-22 | 2021-09-21 | 南通江山农药化工股份有限公司 | Weeding composition, preparation and application thereof |
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