CN108849952B - Pyraclostrobin water-dispersible solid composition and preparation method thereof - Google Patents
Pyraclostrobin water-dispersible solid composition and preparation method thereof Download PDFInfo
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
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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
- A01N25/08—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 solids as carriers or diluents
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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
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
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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
- A01N25/22—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 ingredients stabilising the active ingredients
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
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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
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Abstract
The invention provides a pyraclostrobin water dispersible solid composition, which comprises the following components in percentage by weight: 5-50% of pyraclostrobin, 0.1-15% of alkyl sulfonate, 5-80% of porous carrier and 1-45% of functional auxiliary agent; the invention also provides a preparation method of the composition, which comprises the following steps: firstly, mixing pyraclostrobin and alkyl naphthalene sulfonate according to a ratio; then coarsely crushing the obtained mixture at the temperature of below 35 ℃ to obtain a homogeneous mixture; and adding a porous carrier and a functional auxiliary agent into the obtained homogeneous mixture, and finely crushing to obtain the pyraclostrobin water-dispersible solid composition. The pyraclostrobin water-dispersible solid composition prepared by the invention has good heat storage and normal storage stability, does not aggregate or agglomerate, and does not block a sprayer filter or a sprayer head, thereby being convenient for users to use and improving the pesticide effect.
Description
Technical Field
The invention relates to the field of agricultural chemistry, in particular to a water dispersible solid composition and a preparation method thereof, and especially relates to a pyraclostrobin water dispersible solid composition and a preparation method thereof.
Background
Pyraclostrobin is a strobilurin fungicide with pyrazole structure developed in 1993 by basf, germany, and is a mitochondrial respiration inhibitor. It inhibits mitochondrial respiration by blocking electron transfer between cytochrome b and c1, rendering mitochondria unable to produce and supply energy (ATP) required for normal cellular metabolism, ultimately leading to cell death.
Pyraclostrobin (pyraclosterobin) has the chemical name: n- [2- [ [1- (4-chlorphenyl) pyrazol-3-yl ] oxymethyl ] phenyl ] -N-methoxy methyl carbamate belongs to methoxy acrylic ester broad-spectrum bactericides. The pyraclostrobin can be used for various crops such as wheat, peanut, rice, vegetables, fruit trees, tobacco, tea trees, ornamental plants, lawns and the like, and can be used for preventing and treating a plurality of diseases such as leaf blight, rust disease, powdery mildew, downy mildew, epidemic disease, anthracnose, scab, brown spot, damping off and the like caused by ascomycetes, basidiomycetes, deuteromycetes and oomycetes fungi. At present, pyraclostrobin missible oil and an aqueous emulsion product are mainly used in the market. However, these formulations all have a common disadvantage in that emulsifiable concentrate formulations contain large amounts of organic solvents, which are extremely harmful to the ecological environment and aquatic organisms. As people's consciousness on environmental protection is strengthened gradually, the products are eliminated gradually. At present, various agricultural and chemical companies develop the formulations of pyraclostrobin, such as suspending agent, seed coating agent, granules and the like gradually towards the development of environment-friendly formulation aqueous preparation and granulated products so as to reduce the harm of organic solvent to the environment.
However, in the case of the water-dispersible formulation, the particle size of a solid formulation such as Wettable Powder (WP) or water-dispersible granules (WDG) has a great influence on the stability and suspension rate of the formulation. In order to obtain a solid preparation having a particle size of 1 to 15 μm, various types of pulverization are necessary. However, direct pulverization is difficult due to the low melting point of the active, particularly when the melting point is not more than 70 ℃, because the active is easily melted or softened during the pulverization process, and finally, the problems of risk of physical and chemical quality of the product, unqualified heat storage stability and suspension rate and the like are caused.
The melting point of the pyraclostrobin is low and is only 56-64 ℃, so that the prepared pyraclostrobin composition is easy to agglomerate and cake after being stored hot. For the preparation stored for a long time, when the pesticide is sprayed for use, the filter and the spray head are blocked due to agglomeration, so that inconvenience is brought to users, the absorption of the pyraclostrobin active substance by the plants is influenced, and the pesticide effect is reduced. These technical difficulties have made water dispersible formulations of pyraclostrobin less widely available.
CN102469775A discloses a method for preparing aqueous suspension of pyraclostrobin, which comprises the steps of dispersing a large amount of pyraclostrobin in an aqueous phase in an amorphous liquid drop form, then adding a small amount of suspension of single crystal type particles of pyraclostrobin, and inducing the amorphous liquid drop of pyraclostrobin to rapidly crystallize to form final particle water dispersion suspension. The process requires melting the pyraclostrobin and is carried out at a temperature at which the heated aqueous phase exceeds the melting point of the pyraclostrobin active. Therefore, the method has the advantages of high energy consumption in actual production and processing, complex operability and high equipment requirement. Therefore, how to provide an economical and simple method to solve the technical problems is urgently needed at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides the pyraclostrobin water-dispersible solid composition and the preparation method thereof, and the pyraclostrobin water-dispersible solid composition which improves the heat storage stability and avoids agglomeration meets the requirements.
To achieve the purpose, the invention provides the following technical scheme:
in a first aspect, the invention provides a pyraclostrobin water dispersible solid composition, which comprises the following components in percentage by weight: 5-50% of pyraclostrobin, 0.1-15% of alkyl sulfonate, 5-80% of porous carrier and 1-45% of functional auxiliary agent.
In the invention, the pyraclostrobin accounts for 5-50% of the composition by weight, such as 5%, 8%, 10%, 12%, 15%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 40%, 42%, 45% or 50%.
In the present invention, the alkyl sulfonate accounts for 0.1-15% of the composition, such as 0.1%, 0.5%, 1%, 2%, 3%, 3.5%, 4%, 5.2%, 6%, 7%, 8.5%, 9%, 10%, 11%, 12%, 13%, 14% or 15%.
In the present invention, the porous carrier is 5 to 80% by weight of the composition, for example, 5%, 8%, 10%, 12%, 13%, 15%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 48%, 52%, 60%, 65%, 72%, 79% or 80%.
In the invention, the functional auxiliary agent accounts for 1-45% of the composition by weight, such as 1%, 2%, 3%, 5%, 8%, 10%, 15%, 20%, 22%, 25%, 30%, 35%, 40%, 42%, 43% or 45%.
The pyraclostrobin water dispersible solid composition prepared by the method has good thermal storage and normal storage stability, does not aggregate or agglomerate, and does not block a sprayer filter or a sprayer head.
The pyraclostrobin water-dispersible solid composition can contain other active ingredients besides the pyraclostrobin which is an active ingredient, such as tebuconazole, dinotefuran or sedaxane and the like, and can contain one or more of the active ingredients, and the invention is not limited in particular.
Preferably, the pyraclostrobin water-dispersible solid composition consists of the following components in percentage by weight:
6-30% of pyraclostrobin, 2-5% of alkyl sulfonate, 10-70% of porous carrier and the balance of functional auxiliary agent.
Preferably, the alkyl sulfonate is selected from any one or a mixture of at least two of alkyl naphthalene sulfonate, alkyl naphthalene sulfonate formaldehyde polycondensate, alkyl benzene sulfonate, alkyl ethyl sulfonate or secondary alkyl sulfonate, wherein a typical but non-limiting mixture is: a mixture of alkyl naphthalene sulfonate and alkyl naphthalene sulfonate formaldehyde polycondensate, a mixture of alkyl naphthalene sulfonate and alkyl benzene sulfonate, a mixture of alkyl ethyl sulfonate and alkyl naphthalene sulfonate formaldehyde polycondensate, a mixture of secondary alkyl sulfonate and alkyl benzene sulfonate; preferred are alkyl naphthalene sulfonate formaldehyde polycondensates.
Preferably, the porous carrier is selected from any one or a mixture of at least two of kaolin, montmorillonite clay, attapulgite, synthetic silicon, plant fiber, mineral fiber or magnesium aluminum silicate, wherein a typical but non-limiting mixture is: mixtures of kaolin and montmorillonite clay, mixtures of montmorillonite clay and attapulgite, mixtures of synthetic silicon and kaolin, mixtures of vegetable fibers, mineral fibers and synthetic silicon, mixtures of magnesium aluminum silicate and montmorillonite clay.
Preferably, the kaolin is selected from any one or a mixture of at least two of kaolinite, dickite, nacrite, anauxite, halloysite, or a mixture of halloysite, wherein a typical but non-limiting mixture is: mixtures of kaolinite and dickite, mixtures of nacrite and anauxite, mixtures of halloysite and nacrite; the montmorillonite clay is selected from any one or a mixture of at least two of beidellite, hectorite, saponite or bentonite, wherein a typical but non-limiting mixture is: mixtures of beidellite and hectorite, mixtures of saponite and bentonite, mixtures of hectorite and saponite; the attapulgite is selected from bleaching earth and/or sepiolite; the synthetic silicon is selected from white carbon black and/or fumed silica.
Preferably, the functional auxiliary agent is selected from any one or a mixture of at least two of a dispersing agent, a wetting agent, an antifoaming agent and an inert carrier, namely the pyraclostrobin water-dispersible solid composition can contain any one of the functional auxiliary agents, and can also adopt a mixed form of two or more.
Preferably, the dispersant is selected from any one or a mixture of at least two of lignosulfonate, polycarboxylate, fatty alcohol polyoxyethylene ether or ethylene oxide propylene oxide block copolymer, wherein a typical but non-limiting mixture is: mixtures of lignosulfonates and polycarboxylates, mixtures of polycarboxylates and fatty alcohol polyoxyethylene ethers, mixtures of ethylene oxide propylene oxide block copolymers and lignosulfonates.
Preferably, the wetting agent is selected from any one or a mixture of at least two of nonylphenol polyoxyethylene ether, K12 or polyoxyethylene fatty alcohol ether, with a typical but non-limiting mixture being a mixture of nonylphenol polyoxyethylene ether and K12, and a mixture of K12 and polyoxyethylene fatty alcohol ether.
Preferably, the defoaming agent is selected from siloxane defoaming agents, and as for the specific siloxane defoaming agent, the skilled person can select the defoaming agent according to actual needs, and the invention is not limited in particular.
Preferably, the inert carrier is selected from any one or a mixture of at least two of corn starch, talc, sucrose, potassium sulfate, kaolin, or diatomaceous earth, wherein a typical but non-limiting mixture is: a mixture of corn starch and talc, a mixture of sucrose and potassium sulfate, and a mixture of kaolin and corn starch.
The pyraclostrobin water-dispersible solid composition is prepared into wettable powder or water-dispersible granules.
The pyraclostrobin water-dispersible solid composition has good stability under the conditions of heat storage and normal storage, does not agglomerate or block, and does not block a filter or a spray head.
In order to realize the technical effects, the preparation method of the pyraclostrobin water-dispersible solid composition comprises the following steps:
(1) mixing pyraclostrobin and alkyl sulfonate according to a ratio;
(2) coarsely pulverizing the obtained mixture at below 35 deg.C to obtain homogeneous mixture;
(3) and adding a porous carrier and a functional auxiliary agent into the obtained homogeneous mixture, and finely crushing to obtain the pyraclostrobin water-dispersible solid composition.
Unlike previously disclosed methods of preparation, the present invention first mixes only pyraclostrobin with alkylsulfonate in step (1) without mixing all components together or with dispersant and defoamer and carrier.
According to the invention, the pyraclostrobin and the alkyl sulfonate are mixed in the step (1), the pyraclostrobin and the alkyl sulfonate are mixed more sufficiently through primary coarse crushing, the alkyl sulfonate is more effectively attached and adsorbed on the surface of the pyraclostrobin particles, and the contact aggregation between the particles in the storage process is effectively prevented.
The inventor has also surprisingly found that when only pyraclostrobin and alkylsulfonate are mixed first, by adopting coarse crushing below 35 ℃, pyraclostrobin can be presented as a paste with a softening phenomenon, thereby helping to avoid agglomeration of the finished water-dispersible solid particulate product.
The mixture obtained by mixing pyraclostrobin and alkylsulfonate is pulverized at a low temperature, specifically at a low temperature of 35 ℃ or lower, for example, at a temperature of 0 ℃, 4 ℃, 8 ℃, 10 ℃, 12 ℃, 15 ℃, 20 ℃, 22 ℃, 25 ℃, 28 ℃, 30 ℃ or 35 ℃, but may be at a temperature of 0 ℃ or lower.
The melting point of the pyraclostrobin original drug is 56-64 ℃, if the pyraclostrobin original drug is directly crushed under the conventional condition, the original drug can be softened, the crushing efficiency is affected, and the pyraclostrobin original drug can be failed to be crushed and cannot be prepared into a qualified product. The adoption of the low-temperature crushing method can effectively solve the problem that the pyraclostrobin original drug is softened by particle collision in the crushing process, and simultaneously, the alkyl sulfonate is fully and uniformly adhered to the surface of the pyraclostrobin particles, so that the influence of the subsequent secondary airflow crushing on the pyraclostrobin particles is solved.
According to the invention, the porous carrier and the functional auxiliary agent are added into the homogeneous mixture obtained after coarse crushing, so that the crushing temperature can be relatively loose, the operation can be carried out at a relatively high temperature, and the functional auxiliary agent can play a certain protection role and can promote the finally formed pyraclostrobin water-dispersible solid composition to avoid agglomeration and caking.
In the preparation method, the operation mode of combining coarse crushing and fine crushing at low temperature is adopted, and the crushing is divided into two steps of coarse crushing and fine crushing, so that the alkyl sulfonate and the pyraclostrobin are mixed more sufficiently, the adsorption is more effectively adhered to the surface of the pyraclostrobin particles, and the contact agglomeration phenomenon between the particles in the storage process is effectively prevented.
In the case of the present invention, when preparing water-dispersible solid compositions of different forms, for example, wettable powders, which can be obtained directly after the fine pulverization in step (3) in the above-mentioned preparation method; when the water dispersible granule is prepared, the water dispersible granule can be obtained after the step (3) is finely crushed and the steps of granulation and drying are also needed. As for the granulation and drying techniques, those skilled in the art should understand that various operation modes such as extrusion granulation, spray granulation, rotary granulation, fluidized bed granulation, etc. can be adopted, and the present invention is not particularly limited thereto.
In the invention, the coarse grinding in the step (2) adopts jet milling, and the specific operation is as follows: the mixture passes through high-speed airflow at a certain speed, so that strong collision is generated between particles and between the particles and the inner wall to achieve the effect of breakage, and finally the particle size D90 after crushing is less than or equal to 20 mu m.
As for the specific air velocity used in the above air jet milling, those skilled in the art can adjust the air jet velocity according to the actual particle size to be milled, and the invention is not particularly limited.
According to the invention, the uniform mixing of the pyraclostrobin and the alkyl sulfonate can be realized by adopting jet milling, and the mixing uniformity and the heat dissipation effect are improved.
In the invention, the fine crushing in the step (3) adopts secondary airflow crushing, and the crushing pressure and the feeding speed can be adjusted to ensure that the particle size after crushing reaches 1-15 microns.
The specific air velocity, pulverizing pressure and feeding rate used in the secondary air-jet pulverization can be adjusted by those skilled in the art according to the actual particle size after pulverization.
The pyraclostrobin water-dispersible solid composition prepared by the method can be wettable powder or water-dispersible granules. The pyraclostrobin water dispersible solid composition has the advantages of good heat storage and normal storage stability, no aggregation, no caking, no blockage of a filter or a spray head and the like, thereby facilitating storage and use by users and improving the pesticide effect of pyraclostrobin.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the pyraclostrobin water dispersible solid composition prepared by the invention has the advantages of good heat storage and normal storage stability, no aggregation, no caking, no blockage of a filter or a spray head and the like, and has good fluidity;
(2) the pyraclostrobin water-dispersible solid composition prepared by the invention is simple and convenient to operate, low in economic cost and strong in realizability.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. Hereinafter, "%" means weight percent.
Example 1: 20% pyraclostrobin wettable powder
The preparation process comprises the following steps: mixing pyraclostrobin original drug and Morwet D425 according to a weight ratio, uniformly stirring, and performing primary coarse crushing at the temperature of 30 ℃ to obtain a homogeneous mixture; and then adding the fumed silica, the Soap L and the corn starch into the coarse crushing mixed material according to the weight ratio, and performing secondary fine crushing until the particle size D90 is less than 10 mu m to obtain a final product.
Example 2: 50% pyraclostrobin water dispersible granule
The preparation process comprises the following steps: mixing pyraclostrobin original drug and Morwet EFW according to a weight ratio, uniformly stirring, and performing primary coarse crushing at the temperature of 25 ℃ to obtain a homogeneous mixture; and then adding the white carbon black, the EO/PO block copolymer, the Soap L and the diatomite into the coarse crushing mixed material according to the weight ratio, performing secondary fine crushing to obtain mother powder with the particle size D90 being less than 10 mu m, adding a proper amount of water into the mother powder, kneading, and performing extrusion, granulation and drying to obtain the final product.
Example 3: 10% pyraclostrobin wettable powder
The preparation process comprises the following steps: mixing pyraclostrobin original drug and sodium dodecyl sulfate according to a weight ratio, uniformly stirring, and performing primary coarse crushing at the temperature of 22 ℃ to obtain a homogeneous mixture; and then adding calcined kaolin, nonylphenol polyoxyethylene ether phosphate, Soap L and potassium sulfate into the coarse crushed mixture according to the weight ratio, and performing secondary fine crushing until the particle size D90 is less than 10 mu m to obtain the final product.
Example 4: 5% pyraclostrobin and 10% boscalid wettable powder
The preparation process comprises the following steps: mixing pyraclostrobin original drug and alkyl ethyl sulfonate according to a weight ratio, uniformly stirring, and performing primary coarse crushing at the temperature of 35 ℃ to obtain a homogeneous mixture; and then adding boscalid, plant fiber, fatty alcohol-polyoxyethylene ether, Soap L and talcum powder into the coarse crushing mixed material according to the weight ratio, and performing secondary fine crushing until the particle size D90 is less than 10 mu m to obtain the final product.
Example 5: 5% pyraclostrobin and 40% chlorothalonil water dispersible granule
The preparation process comprises the following steps: mixing pyraclostrobin original drug and alkyl naphthalene sulfonate formaldehyde polycondensate according to a weight ratio, uniformly stirring, and carrying out primary coarse crushing at the temperature of 10 ℃ to obtain a homogeneous mixture; then adding chlorothalonil, mineral fiber, polycarboxylate, sodium sulfosuccinate, Soap L and kaolin into the coarse crushing mixed material according to the weight ratio, carrying out secondary fine crushing to obtain mother powder with the particle size D90 being less than 10 mu m, adding a proper amount of water into the mother powder, kneading, extruding, granulating and drying to obtain the final product.
Comparative example 1
Compared with example 1, except that the preparation process is different, the method is the same as example 1.
The preparation process comprises the following steps: mixing pyraclostrobin original drug, Morwet D425, fumed silica, Soap L and corn starch according to a weight ratio at 30 ℃, and only performing coarse crushing to enable D90 to reach 20 mu m to obtain a final product.
Comparative example 2
Compared with example 1, except that the preparation process is different, the method is the same as example 1.
The preparation process comprises the following steps: mixing pyraclostrobin original drug, Morwet D425, fumed silica, Soap L and corn starch according to a weight ratio at 30 ℃, and only finely crushing to ensure that D90 is less than 10 mu m to obtain a final product.
Comparative example 3
Compared with example 1, except that the preparation process is different, the method is the same as example 1.
The preparation process comprises the following steps: mixing pyraclostrobin original drug, Morwet D425, fumed silica, Soap L and corn starch according to a weight ratio, firstly carrying out coarse grinding at the temperature of 30 ℃ to enable D90 to reach 20 mu m, and then carrying out fine grinding until the particle size D90 is less than 10 mu m, thus obtaining the final product.
Comparative example 4
Compared with example 1, except that the preparation process is different, the method is the same as example 1.
The preparation process comprises the following steps: mixing pyraclostrobin original drug, Morwet D425, fumed silica, Soap L and corn starch according to a weight ratio, firstly carrying out coarse grinding at the temperature of 40 ℃ to enable D90 to reach 20 mu m, and then carrying out fine grinding until the particle size D90 is less than 10 mu m, thus obtaining the final product.
Comparative example 5
Compared with example 2, except for the preparation process, the method is the same as example 2.
The preparation process comprises the following steps: mixing pyraclostrobin original drug, Morwet EFW, white carbon black, EO/PO block copolymer, Soap L and diatomite according to a weight ratio, performing jet milling to obtain mother powder with the particle size D90 being less than 10 mu m, adding a proper amount of water into the mother powder, kneading, and performing extrusion, granulation and drying to obtain the final product.
Comparative example 6
Compared with the example 2, the preparation method disclosed in CN102726379A is adopted.
The preparation process comprises the following steps: uniformly mixing pyraclostrobin original drug, Morwet D425, fumed silica, Soap L and corn starch in a weight ratio to obtain a mixture, and performing superfine grinding on the mixture by using a jet mill to obtain mother powder; weighing a certain amount of mother powder obtained after superfine grinding, and putting the mother powder into a rotary fluidized bed; opening the rotary fluidized bed and slowly adding an aqueous solution of a binder into the rotary fluidized bed for granulation; drying after granulation is finished; and screening, analyzing and inspecting the dried granular substances to obtain the pyraclostrobin water dispersible granule.
The samples prepared in examples 1 to 5 and comparative examples 1 to 6 described above were tested for heat storage stability. The heat storage stability test was carried out in an oven at 54 ℃.
After heat storage in an oven at 54 ℃, the samples were removed from the oven. After cooling to room temperature, each test sample was poured out and the sample was observed for flowability. Then directly sieving the wettable powder sample through a 325-mesh sieve; the water-dispersible granule sample was diluted with water and sieved through a 325 mesh sieve. The results of the tests are shown in table 1.
TABLE 1
The test results in table 1 show that the pyraclostrobin water-dispersible solid composition prepared according to the invention has good heat storage fluidity, no caking, no screen blockage and good physical properties, thereby having the outstanding advantages of being more convenient for users to use and improving the pesticide effect of pyraclostrobin.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (16)
1. The pyraclostrobin water dispersible solid composition is characterized by comprising the following components in percentage by weight: 5-50% of pyraclostrobin, 0.1-15% of sulfonate, 5-80% of porous carrier and 1-45% of functional auxiliary agent;
the sulfonate is any one or a mixture of at least two of alkyl naphthalene sulfonate, alkyl naphthalene sulfonate formaldehyde polycondensate, alkyl benzene sulfonate, alkyl ethyl sulfonate or secondary alkyl sulfonate;
the pyraclostrobin water dispersible solid composition is prepared by the following method, and the method comprises the following steps:
(1) mixing the pyraclostrobin and the sulfonate according to a ratio;
(2) coarsely pulverizing the obtained mixture at below 35 deg.C to obtain homogeneous mixture;
(3) and adding a porous carrier and a functional auxiliary agent into the obtained homogeneous mixture, and finely crushing to obtain the pyraclostrobin water-dispersible solid composition.
2. The pyraclostrobin water dispersible solid composition is characterized by comprising the following components in percentage by weight: 6-30% of pyraclostrobin, 2-5% of sulfonate, 10-70% of porous carrier and the balance of functional auxiliary agent;
the sulfonate is any one or a mixture of at least two of alkyl naphthalene sulfonate, alkyl naphthalene sulfonate formaldehyde polycondensate, alkyl benzene sulfonate, alkyl ethyl sulfonate or secondary alkyl sulfonate;
the pyraclostrobin water dispersible solid composition is prepared by the following method, and the method comprises the following steps:
(1) mixing the pyraclostrobin and the sulfonate according to a ratio;
(2) coarsely pulverizing the obtained mixture at below 35 deg.C to obtain homogeneous mixture;
(3) and adding a porous carrier and a functional auxiliary agent into the obtained homogeneous mixture, and finely crushing to obtain the pyraclostrobin water-dispersible solid composition.
3. The pyraclostrobin water-dispersible solid composition according to claim 1 or claim 2, wherein the sulphonate is an alkyl naphthalene sulphonate formaldehyde polycondensate.
4. The pyraclostrobin water-dispersible solid composition according to claim 1 or claim 2, wherein the porous carrier is selected from the group consisting of kaolin, montmorillonite clay, attapulgite, synthetic silica, vegetable fibres, mineral fibres and magnesium aluminium silicate, or a mixture of at least two thereof.
5. The pyraclostrobin water-dispersible solid composition according to claim 4, wherein the kaolin is selected from any one or a mixture of at least two of dickite, nacrite, anauxite or halloysite; the montmorillonite clay is selected from one or mixture of at least two of beidellite, hectorite, saponite and bentonite; the attapulgite is selected from bleaching earth and/or sepiolite; the synthetic silicon is selected from white carbon black.
6. The pyraclostrobin water-dispersible solid composition of claim 5, wherein the synthetic silicon is selected from fumed silica.
7. The pyraclostrobin water-dispersible solid composition according to claim 1 or claim 2, wherein the functional adjuvant is selected from any one of a dispersant, a wetting agent, an antifoaming agent or an inert carrier other than the porous carrier or a mixture of at least two of them.
8. The pyraclostrobin water-dispersible solid composition according to claim 7, wherein the dispersant is selected from the group consisting of lignosulphonates, polycarboxylates, fatty alcohol polyoxyethylene ethers or ethylene oxide propylene oxide block copolymers, and mixtures of any one or at least two thereof.
9. The pyraclostrobin water-dispersible solid composition according to claim 7, wherein the wetting agent is selected from any one of nonylphenol polyoxyethylene ether, K12 or polyoxyethylene fatty alcohol ether or a mixture of at least two thereof.
10. The pyraclostrobin water-dispersible solid composition according to claim 7, wherein the antifoaming agent is selected from silicone-based antifoaming agents.
11. The pyraclostrobin aqueous dispersion solid composition of claim 7, wherein the inert carrier is selected from the group consisting of corn starch, talc, sucrose, potassium sulphate and diatomaceous earth, or a mixture of any one or at least two thereof.
12. The pyraclostrobin water-dispersible solid composition according to claim 1 or 2, wherein the composition is formulated as a wettable powder or a water-dispersible granule.
13. The process for the preparation of the pyraclostrobin aqueous dispersion solid composition according to any one of claims 1 to 12, comprising the steps of:
(1) mixing pyraclostrobin and the sulfonate according to a ratio;
(2) coarsely pulverizing the obtained mixture at below 35 deg.C to obtain homogeneous mixture;
(3) and adding a porous carrier and a functional auxiliary agent into the obtained homogeneous mixture, and finely crushing to obtain the pyraclostrobin water-dispersible solid composition.
14. The method of claim 13, wherein pyraclostrobin water dispersible granule is obtained by performing granulation and drying after fine crushing in step (3).
15. The method as claimed in claim 13 or 14, wherein the coarse pulverization in the step (2) is carried out by jet milling, and the particle size D90 after the milling is 20 μm or less.
16. The method according to claim 13, wherein the fine pulverization in the step (3) is carried out by a secondary air stream pulverization to a particle size of 1 to 15 μm after the pulverization.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710324705.2A CN108849952B (en) | 2017-05-10 | 2017-05-10 | Pyraclostrobin water-dispersible solid composition and preparation method thereof |
| TW107115522A TWI772416B (en) | 2017-05-10 | 2018-05-08 | A pyraclostrobin water dispersible solid composition and the process for preparing the same |
| PCT/CN2018/086270 WO2018205966A1 (en) | 2017-05-10 | 2018-05-10 | Pyraclostrobin aqueous dispersion solid composition and preparation method therefor |
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| CN201710324705.2A CN108849952B (en) | 2017-05-10 | 2017-05-10 | Pyraclostrobin water-dispersible solid composition and preparation method thereof |
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| CN109792987A (en) * | 2019-01-21 | 2019-05-24 | 深圳诺普信农化股份有限公司 | Dry suspending agent and preparation method thereof |
| CN111345294A (en) * | 2020-04-02 | 2020-06-30 | 张惠明 | Butylbenzone-ethyl water dispersible granule and preparation method thereof |
| CN113647404A (en) * | 2021-07-27 | 2021-11-16 | 惠州市银农科技股份有限公司 | Water dispersible granule and preparation method thereof |
| CN115918652A (en) * | 2022-10-27 | 2023-04-07 | 中国医学科学院生物医学工程研究所 | Preparation method and application of halloysite nanotube coated drug-loaded naphthylacetic acid and pyraclostrobin nanoparticles |
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| WO2010051607A1 (en) * | 2008-11-06 | 2010-05-14 | Oxiteno S.A. Indústria E Comércio | Water dispersible agrochemical formulations |
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| TW201900025A (en) | 2019-01-01 |
| CN108849952A (en) | 2018-11-23 |
| WO2018205966A1 (en) | 2018-11-15 |
| TWI772416B (en) | 2022-08-01 |
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