Fluopyram-containing composition and preparation method and application thereof
阅读说明：本技术 一种含氟吡菌酰胺的组合物及其制备方法和应用 (Fluopyram-containing composition and preparation method and application thereof ) 是由 崔晶 杨冬梅 于楠楠 刘跃怡 于 2020-12-16 设计创作，主要内容包括：本发明涉及农药技术领域,更具体地,本发明涉及一种含氟吡菌酰胺的组合物及其制备方法和应用。所述组合物的制备原料包括氟吡菌酰胺、噻虫嗪和戊唑醇。本发明提供一种组合物,通过氟吡菌酰胺、噻虫嗪和戊唑醇共同作用,有好的杀菌和杀虫效果,对玉米金针虫和丝黑穂病等具有高的防治效果；且申请人通过限定成膜剂、增稠剂、润湿分散剂等助剂,可促进氟吡菌酰胺、噻虫嗪和戊唑醇在液体制剂,如种子处理悬浮剂中的贮存稳定性,并保持一定粘度,促进长时间流动,并促进组合物制成的包衣膜的耐水性,从而提高耐雨水冲刷和浸水能力。(The invention relates to the technical field of pesticides, and particularly relates to a fluopyram-containing composition and a preparation method and application thereof. The raw materials for preparing the composition comprise fluopyram, thiamethoxam and tebuconazole. The invention provides a composition which has good sterilization and insecticidal effects and high control effects on corn needle worm and silk black ear diseases and the like under the combined action of fluopyram, thiamethoxam and tebuconazole; the applicant defines auxiliary agents such as a film forming agent, a thickening agent, a wetting dispersant and the like, can promote the storage stability of the fluopyram, the thiamethoxam and the tebuconazole in a liquid preparation such as a seed treatment suspending agent, maintain a certain viscosity, promote long-time flowing and promote the water resistance of a coating film prepared from the composition, thereby improving the rain wash resistance and the water immersion resistance.)
1. The composition containing fluopyram is characterized in that raw materials for preparing the composition comprise fluopyram, thiamethoxam and tebuconazole.
2. The composition containing fluopyram according to claim 1, wherein the weight ratio of the fluopyram to the thiamethoxam to the tebuconazole is (0.5-5): (20-30): (1-5).
3. The composition containing fluopyram according to claim 2, wherein the weight ratio of the fluopyram to the thiamethoxam to the tebuconazole is (0.5-3): (20-25): (1-5).
4. The composition containing fluopyram according to claim 1, wherein the total weight of the fluopyram, the thiamethoxam and the tebuconazole accounts for 20-30 wt% of the composition.
5. A fluopyram-containing composition according to any one of claims 1 to 4, wherein the composition is in the form of a liquid preparation for seed treatment or a solid preparation for seed treatment.
6. A fluopyram-containing composition according to claim 5, wherein the liquid seed treatment formulation is selected from one or more of a liquid seed treatment formulation, an emulsion seed treatment, a suspension seed treatment, and a suspension seed treatment microcapsules.
7. The fluopyram-containing composition according to claim 5, wherein the seed treatment solid formulation is selected from one or more of a dry seed treatment powder, a seed treatment dispersable agent, and a seed treatment soluble powder.
8. The fluopyram-containing composition according to claim 5, wherein raw materials for preparing the composition further comprise at least one wetting and dispersing agent, at least one thickening agent and at least one film forming agent.
9. A method for preparing a fluopyram-containing composition according to any one of claims 1 to 8, comprising the steps of:
mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
10. Use of a fluopyram-containing composition according to any one of claims 1 to 8 for controlling crop diseases.
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a fluopyram-containing composition and a preparation method and application thereof.
Background
Fluopyram (ISO common name: Fluopyram), trade name: lufuda; CAS No: 658066-35-4, chemical name: n- {2- [ 3-chloro-5- (trifluoromethyl) -2-pyridinyl ] ethyl } -alpha, alpha-ortho-trifluoromethylbenzamide. Fluopyram is a SDHI (succinate dehydrogenase inhibitor) type sterilization and nematicide developed by Bayer crop science corporation, is used for preventing and controlling alternaria leaf spot, gray mold, powdery mildew, sclerotinia, early blight and the like on vegetables such as grapes, pear trees, bananas, apples, cucumbers, tomatoes, field crops and the like, can be registered on various crops for preventing and controlling various nematodes, and is a high-efficiency, green and low-toxicity nematicide. Fluopyram is not only a new generation of excellent nematicide, but also a broad-spectrum bactericide, a seed treatment agent, an agricultural product storage preservative and the like, and has multiple functions.
When the preparation prepared by using the single raw pesticide has good sterilization and insecticidal effects, but the single raw pesticide can bring the problems of drug resistance and large dosage, so that the development of a green pesticide preparation with wider spectrum and smaller dosage is the current development direction. And the lower solubility of fluopyram also causes resistance to the formulation of seed treatment liquid formulations.
Disclosure of Invention
In order to solve the problems, the invention provides a composition containing fluopyram in a first aspect, and raw materials for preparing the composition comprise fluopyram, thiamethoxam and tebuconazole.
As a preferable technical scheme, the weight ratio of the fluopyram, the thiamethoxam and the tebuconazole is (0.5-5): (20-30): (1-5).
As a preferable technical scheme, the weight ratio of the fluopyram, the thiamethoxam and the tebuconazole is (0.5-3): (20-25): (1-5).
As a preferable technical scheme, the total weight of the fluopyram, the thiamethoxam and the tebuconazole accounts for 20-30 wt% of the composition.
As a preferable technical scheme, the dosage form of the composition is a seed treatment liquid preparation or a seed treatment solid preparation.
In a preferred embodiment of the present invention, the liquid preparation for seed treatment is one or more selected from a liquid preparation for seed treatment, an emulsion for seed treatment, a suspension for seed treatment, and a suspension for seed treatment microcapsules.
As a preferred technical scheme, the seed treatment solid preparation is selected from one or more of seed treatment dry powder, seed treatment dispersible agent and seed treatment soluble powder.
As a preferred technical scheme, the preparation raw materials of the composition also comprise at least one wetting dispersant, at least one thickening agent and at least one film forming agent.
In a second aspect, the present invention provides a method for preparing a fluopyram-containing composition as described above, comprising the following steps:
mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
The third aspect of the invention provides an application of the fluopyram-containing composition for preventing and treating crop diseases.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a composition which has good sterilization and insecticidal effects and high control effects on corn needle worm and silk black ear diseases and the like under the combined action of fluopyram, thiamethoxam and tebuconazole; the applicant defines auxiliary agents such as a film forming agent, a thickening agent, a wetting dispersant and the like, can promote the storage stability of the fluopyram, the thiamethoxam and the tebuconazole in a liquid preparation such as a seed treatment suspending agent, maintain a certain viscosity, promote long-time flowing and promote the water resistance of a coating film prepared from the composition, thereby improving the rain wash resistance and the water immersion resistance.
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 addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a composition containing fluopyram in a first aspect, and raw materials for preparing the composition comprise fluopyram, thiamethoxam and tebuconazole. In a preferred embodiment, the weight ratio of the fluopyram, the thiamethoxam and the tebuconazole is (0.5-5): (20-30): (1-5); in a preferred embodiment, the weight ratio of the fluopyram, the thiamethoxam and the tebuconazole is (0.5-3): (20-25): (1-5); in a preferred embodiment, the weight ratio of the fluopyram, the thiamethoxam and the tebuconazole is 1:21: 2.
Fluopyram
Fluopyram (ISO common name: Fluopyram), trade name: lufuda; CAS No: 658066-35-4, chemical name: n- {2- [ 3-chloro-5- (trifluoromethyl) -2-pyridinyl ] ethyl } -alpha, alpha-ortho-trifluoromethylbenzamide. Fluopyram is a SDHI (succinate dehydrogenase inhibitor) type sterilization and nematicide developed by Bayer crop science corporation, is used for preventing and controlling alternaria leaf spot, gray mold, powdery mildew, sclerotinia, early blight and the like on vegetables such as grapes, pear trees, bananas, apples, cucumbers, tomatoes, field crops and the like, can be registered on various crops for preventing and controlling various nematodes, and is a high-efficiency, green and low-toxicity nematicide. Fluopyram is not only a new generation of excellent nematicide, but also a broad-spectrum bactericide, a seed treatment agent, an agricultural product storage preservative and the like, and has multiple functions. Fluopyram interferes with the respiratory action of the target succinate dehydrogenase by inhibiting its activity. After the nematodes are treated by the fluopyram, the bodies of the nematodes become needle-shaped and the activity is reduced rapidly. Fluopyram selectively inhibits complex II of the respiratory chain in the mitochondria of nematodes. Mitochondria are the energy plant of nematodes, and inhibition results in a rapid depletion of energy (ATP) in the nematode cells. It is the first nematicide to act on this target, representing a new class of nematicides with a new mechanism of action, also the first nematicides that are less toxic to the user and the environment. In one embodiment, the fluopyram of the present invention is available from furun biochemical technologies, ltd, Jiangsu.
Thiamethoxam
Thiamethoxam is a second generation nicotine high-efficiency low-toxicity insecticide, has a chemical formula of C8H10ClN5O3S, has stomach toxicity, contact toxicity and systemic activity on pests, and is used for foliar spray and soil root irrigation treatment. After the pesticide is applied, the pesticide is absorbed quickly and is conducted to each part of the plant, and the pesticide has good control effect on piercing-sucking pests such as aphids, plant hoppers, leafhoppers, whiteflies and the like. Thiamethoxam is also a nicotinic acetylcholine receptor (nAChR) agonist. The pesticide has better control effect on most pests than or equal to other registered neonicotinoid insecticides, has contact poisoning, stomach poisoning and systemic effects, can be quickly absorbed by roots, stems and leaves of plants and conducted to the top of xylem, and has the characteristics of better safety, wider insecticidal spectrum, high action speed, long lasting period and the like. The water solubility is 4.1g/L, and the water solubility is higher. In one embodiment, the thiamethoxam of the present invention is purchased from Jiangsu Suabine bio-farming, Inc.
Tebuconazole
Tebuconazole is an organic compound, has a molecular formula of C16H22ClN3O, is a triazole bactericidal pesticide with high efficiency, broad spectrum and systemic property, has three functions of protection, treatment and eradication, and has wide bactericidal spectrum and long lasting period. Like all triazole fungicides, tebuconazole is able to inhibit the biosynthesis of fungal ergosterol. Tebuconazole is used as a seed treatment agent and foliar spray all over the world, has a wide bactericidal spectrum, and not only has high activity but also has a long lasting period. Tebuconazole is mainly used for preventing and treating various fungal diseases of crops such as wheat, rice, peanuts, vegetables, bananas, apples, pears, corn sorghum and the like, and is registered and widely applied to more than 60 crops in more than 50 countries all over the world. The product is used for preventing and treating sclerotinia rot of colza, has good prevention effect, and has the characteristics of lodging resistance, obvious yield increase effect and the like, and has the action mechanism on pathogenic bacteria of inhibiting the demethylation of ergosterol on the cell membrane of the pathogenic bacteria, so that the pathogenic bacteria can not form the cell membrane, thereby killing the pathogenic bacteria, and the solubility (20 ℃): 32mg/L of water. In one embodiment, the tebuconazole of the present invention is purchased from Jiangsu Fengden pesticide, Inc.
In one embodiment, the composition of the present invention is in the form of a liquid seed treatment formulation or a solid seed treatment formulation. In a preferred embodiment, the liquid formulation for seed treatment according to the present invention is selected from one or more of a liquid formulation for seed treatment, an emulsion for seed treatment, a suspension for seed treatment microcapsules; in a preferred embodiment, the seed treatment solid formulation of the present invention is selected from one or more of a dry seed treatment powder, a dispersable seed treatment powder, a soluble seed treatment powder; in a more preferred embodiment, the composition of the present invention is in the form of a seed treatment suspension.
In one embodiment, the total weight of the fluopyram, the thiamethoxam and the tebuconazole accounts for 20-30 wt% of the composition.
In one embodiment, the raw materials for preparing the composition of the present invention further comprise at least one wetting and dispersing agent, at least one thickener, and at least one film forming agent.
Thickening agent
In one embodiment, the thickener of the present invention comprises 0.1 to 1 wt% of the composition; in a preferred embodiment, the thickener of the present invention comprises 0.2 to 0.6 wt% of the composition; in a preferred embodiment, the thickener of the present invention comprises 0.3 to 0.5 wt% of the composition.
The applicant finds that the flupyrad, the thiamethoxam and the tebuconazole have good bactericidal effect when acting together, and particularly have high control effect on the corn head smut, the flammulina velutipes and the like, but the applicant finds that the flupyrad, the thiamethoxam and the tebuconazole have large solubility difference when preparing pesticide preparations of the flupyrad, the thiamethoxam and the tebuconazole, particularly the thiamethoxam has high solubility in water, the ionization degree and the adsorbed water content in the water are increased, when more thiamethoxam content is added, the viscosity of a system and the aggregation between the thiamethoxam are obviously increased, the processing is difficult, and the deposition and precipitation are easy to occur in the storage process. The applicant finds that when magnesium aluminum silicate and polyvinylpyrrolidone are used together as the thickening agent, clayey magnesium aluminum silicate and polyvinylpyrrolidone molecular chains can be linked together to form a dense cross network, and thiamethoxam and other active compounds can be contained between three-dimensional frameworks, so that gravity settlement and aggregation are reduced, and storage stability is improved. Preferably, the thickener of the present invention is selected from one or more of xanthan gum, arabic gum, magnesium aluminum silicate, chitosan, sodium alginate and polyvinylpyrrolidone. In a preferred embodiment, the thickener of the present invention comprises magnesium aluminum silicate and polyvinylpyrrolidone.
The aluminum magnesium silicate has a unique three-dimensional chain structure and a special needle and rod crystal structure, so that the aluminum magnesium silicate has unusual colloid and adsorption properties. The excellent thickening property, suspension property and colloid shaking melting property of the composite material are widely applied to the paint coating industry. Form an association network structure in a 'card palace' type in an aqueous medium. Can be immediately dispersed in water without soaking. Both high shear and low shear mixers can be used to prepare the aqueous dispersion thereof, as can hot and cold water. Non-moving binders, unlike other organic binders, do not move to the surface of the tablet or rod during drying. Examples of the magnesium aluminum silicate include, but are not limited to, MA21 (apparent viscosity of 800 mPas in 5% aqueous solution), MA28 (apparent viscosity of 300 mPas in 5% aqueous solution), MA28T (apparent viscosity of 200 mPas in 5% aqueous solution), and MA28A (apparent viscosity of 200 mPas in 5% aqueous solution) from Goodpasture's encyclopedia technology (Beijing).
The apparent viscosity is the quotient of the corresponding shear stress divided by the shear rate at a certain velocity gradient. The apparent viscosity may be greater than the true viscosity or less than the true viscosity. The apparent viscosity was measured as the viscosity reading of the NDJ viscometer spindle 4 at 60rpm after 24 hours of aging in a 5% water dispersion.
Polyvinylpyrrolidone, PVP for short, is a non-ionic polymer compound, is the most distinctive of N-vinylamide polymers, and has been studied the deepest and most extensive fine chemicals. PVP is classified into four grades based on its average molecular weight, which is conventionally represented by the K value, with different K values representing the respective PVP average molecular weight ranges. The K value is actually a characteristic value related to the relative viscosity of the aqueous solution of PVP, which in turn is a physical quantity related to the molecular weight of the high polymer, and thus the K value can be used to characterize the average molecular weight of PVP. In general, the larger the K value, the higher the viscosity, and the stronger the adhesiveness. Examples of the polyvinylpyrrolidone include, but are not limited to, K15(K value: 13-17), K17(K value: 15-19), K25(K value: 22-28), K30(K value: 27-32), K60(K value: 58-68), and K90(K value: 85-97) from Ronghong grass New materials science and technology, Inc.
And the applicant finds that the amount of magnesium aluminum silicate and polyvinylpyrrolidone should be in a proper ratio, when the amount of magnesium aluminum silicate is more, the magnesium aluminum silicate is easy to precipitate or even agglomerate after being stored for a long time because of the inorganic structure of the magnesium aluminum silicate, the structure supporting the magnesium aluminum silicate can be promoted by adding polyvinylpyrrolidone, especially polyvinylpyrrolidone with certain viscosity and magnesium aluminum silicate, and the stabilization of the magnesium aluminum silicate in a water system can be further promoted by the action of flexible cyclic structure and hetero atom in the polyvinylpyrrolidone. More preferably, the weight ratio of the magnesium aluminum silicate to the polyvinylpyrrolidone in the invention is 1: (3-4).
In addition, the applicant finds that the viscosity of the thickener needs to be controlled because the system has higher viscosity due to higher content and larger solubility of the thiamethoxam, so that the excessive viscosity of the thickener is avoided, and the influence on the fluidity and the stability of the system caused by the excessive viscosity of the thickener is avoided. And when the viscosity of the thickening agent is too low, the molecular chain of the polyvinylpyrrolidone is broken, and the density of the cross network and the interaction between the polyvinylpyrrolidone and the magnesium aluminum silicate are not facilitated. Further preferably, the apparent viscosity of the magnesium aluminum silicate in a 5% aqueous solution is 100-400 mPa & s; examples thereof include 100 mPas, 150 mPas, 200 mPas, 250 mPas, 300 mPas, 350 mPas and 400 mPas; further preferably, the K value of the polyvinylpyrrolidone is 13-32; there may be mentioned, for example, 13, 15, 18, 20, 25, 28, 30, 32; further preferably, the K value of the polyvinylpyrrolidone is 20-32.
Film forming agent
Although the current film forming agent such as polyvinyl alcohol and the like has good film forming performance, the affinity to water is higher, and a seed coating film formed by the preparation is not resistant to long-time soaking and scouring, the applicant finds that the prepared film forming agent emulsion is used in the composition of the invention by using lipophilic alkyl acrylate as a main component of a film forming agent molecular chain and copolymerizing N-vinyl pyrrolidone, sodium vinyl benzene sulfonate and the like with stronger hydrophilicity, the prepared seed coating film has good water resistance, and probably because the alkyl acrylate and other structures in a seed coating film cross-linking network reduce a water contact angle, the sodium vinyl benzene sulfonate, the N-vinyl pyrrolidone and the like in the film forming agent molecular chain act with other components of the composition to increase the film forming density and the adsorbability to seeds, so that the good water resistance is obtained. In one embodiment, the raw materials for preparing the film forming agent of the present invention include alkyl acrylate, sodium vinylbenzene sulfonate and N-vinyl pyrrolidone. In a preferred embodiment, the film forming agent of the present invention comprises 2 to 8 wt% of the composition, which may be, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%.
And the applicant finds that the proportion and the type of raw materials for preparing the film forming agent need to be controlled, when the amount of the alkyl acrylate is excessive compared with the amount of the vinyl pyrrolidone, the sodium vinyl benzene sulfonate and the like, the viscosity of the preparation is obviously increased even precipitation or paste-like phenomenon is generated due to poor hydrophilicity of the alkyl acrylate, and when the amount of the alkyl acrylate is less, the water resistance is poor. And the applicant has found that the chain of alkyl ester substituents in the alkyl acrylate cannot be too long, which would result in poor compatibility with the raw materials of the composition such as the thickener, etc., affecting the storage stability and the uniformity of film formation. Preferably, the molar ratio of the alkyl acrylate, the sodium vinylbenzene sulfonate and the N-vinyl pyrrolidone is 1: (0.05-0.1): (0.05-0.1); more preferably, the alkyl acrylate of the present invention is a C3-C6 alkyl acrylate, such as propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, and hexyl acrylate.
The applicant finds that by using a vinyl compound containing benzene sulfonate and pyrrolidone substitution as a hydrophilic component in a film forming agent, the stability of the film forming agent and raw medicines such as fluopyram, thiamethoxam and tebuconazole in a hot storage process can be further promoted while the stability of the film forming agent in a water system is promoted, wherein a large entropy value at a high temperature can promote the dissolution and aggregation of the raw medicines such as fluopyram, thiamethoxam and tebuconazole and the movement of magnesium aluminum silicate and the like to be intensified, so that the stability of a cross network of the film forming agent is poor, and particles are more easily separated out compared with the normal temperature The thiamethoxam and tebuconazole have good adsorption and compatibility to form an adsorption film, and the lipophilic alkyl acrylate covers the adsorption film to promote the thickness of the adsorption film, so that the aggregation of original drug molecules is reduced at high temperature, and the stability of the preparation at higher temperature is improved. More preferably, the preparation method of the film forming agent comprises the following steps:
adding alkyl acrylate, N-vinyl pyrrolidone and an emulsifier into water, adding an initiator, reacting for 2-3 h at 10-15 ℃, adding sodium vinyl benzene sulfonate, and continuing to react for 0.5-1 h to obtain the film-forming agent emulsion. In a preferred embodiment, the total weight of the alkyl acrylate, the N-vinyl pyrrolidone and the sodium vinylbenzene sulfonate accounts for 10 to 15 wt% of water.
More preferably, the initiator of the present invention is present in an amount of 0.005 to 0.03 mol% based on the alkyl acrylate, and may be, for example, 0.005%, 0.01%, 0.02% or 0.03 mol%. The initiator of the present invention is not particularly limited, and is an initiator commonly used for emulsion polymerization, including, but not limited to, azo-type initiators such as azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, azobisdicyclohexylcarbonitrile, dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride (V-50 initiator), azobisisobutyrimidazoline hydrochloride (VA-044 initiator), azobisisobutyrimidazoline (VA061 initiator), azobiscyanovaleric acid initiator, peroxy-type initiators such as persulfate, redox initiation systems such as persulfate-mercaptan redox initiation system, persulfate-bisulfite redox initiation system, chlorate-bisulfite redox initiation system, hydrogen peroxide-ferrite redox initiation system, organohydroperoxide-ferrite redox initiation system, preferably from a hydrogen peroxide-ferrous salt redox initiation system.
More preferably, the emulsifier of the present invention accounts for 1 to 5 mol% of the alkyl acrylate, and may be, for example, 1%, 2%, 3%, 4%, 5%. The emulsifier is not specifically limited in the present invention, and is an initiator commonly used for emulsion polymerization, including, but not limited to, sodium tetradecyl benzenesulfonate, dodecyltrimethylammonium chloride, polyoxyethylene lauryl ether, sodium lauryl sulfate, polyoxyethylene ether or polyoxyethylene amine.
Wetting and dispersing agent
The applicant finds that when the film forming agent provided by the invention is added, the film forming agent is mainly composed of lipophilic alkyl acrylate, and the strong hydrophilicity of sulfonate in the film forming agent causes the increase of bound water and bound water near an adsorption film, and the decrease of free water, so that the viscosity of the composition prepared by the invention is obviously increased, especially when the composition is stored for a long time, the film forming agent and the thickening agent are entangled due to the action of substituent groups such as pyrrolidone, and when the composition is subjected to movement or shearing, the cross network in the system can not be rapidly disassembled, and the free water can not be rapidly released, so that the flowability is reduced. In one embodiment, the wetting and dispersing agent of the present invention is selected from one or more of phenylethylphenol polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether, sorbitan fatty acid ester, styrylphenol-ethylene oxide condensate, castor oil-ethylene oxide condensate, polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, alkyl naphthalene sulfonate, dodecyl benzene sulfonate, lignosulfonate, sodium naphthalene sulfonate formaldehyde condensate, polyethylene glycol, and alkylolamide polyoxyethylene ether. In one embodiment, the wetting and dispersing agent of the present invention comprises 4 to 8 wt% of the composition, and may be exemplified by 4 wt%, 5 wt%, 6 wt%, 7 wt%, and 8 wt%.
The applicant has found that when a polyoxyethylene sorbitan fatty acid ester is used as a wetting dispersant, because the fatty acid ester structure and the alkyl acrylate structure have better compatibility and can mutually penetrate, the contact between the sorbitan structure of the polyhydric alcohol and the benzene sulfonate is promoted, the competitive adsorption with water is generated, the volume of free water in a system is increased, the viscosity of the system is reduced, and the fluidity is increased. Preferably, the wetting and dispersing agent of the present invention comprises polyoxyethylene sorbitan fatty acid ester.
In addition, the applicant finds that by adding the styrylphenol-ethylene oxide condensation compound, on one hand, due to the adsorbability of the styrylphenol and the original drug in the styrylphenol-ethylene oxide condensation compound, an aryl plane of the styrylphenol in an adsorption layer on the surface of the original drug is contacted with the original drug, the binding degree of the bound water and the bound water around the original drug is further reduced, and when a system is subjected to the action of external force, the bound water and the bound water in gaps can be released easily, so that the resistance among original drug particles is reduced, the viscosity is reduced, and the fluidity is increased. On the other hand, because of the hydrophilic ethylene oxide condensate, the resistance to intermolecular entanglement is increased, and the destruction of the cross-network structure by entanglement upon the action of external force is reduced, thereby increasing the fluidity. More preferably, the wetting and dispersing agent of the present invention comprises a styrylphenol-ethylene oxide condensate.
The applicant finds that the dosage of the wetting dispersant needs to be controlled, when the polyoxyethylene sorbitan fatty acid ester is excessive, the higher competitive adsorption results in less bound water on the outer side of the adsorption film, and because the polyoxyethylene sorbitan fatty acid ester and the film-forming agent have stronger interaction, the cross network disintegration is not favorable when external force is applied, the stability and the fluidity are influenced, and when the styrylphenol-ethylene oxide condensation compound is excessive, the higher hydrophilicity influences the water resistance of the formed seed coating film. More preferably, the weight ratio of the polyoxyethylene sorbitan fatty acid ester to the styrylphenol-ethylene oxide condensate is (2-3): 1.
the polyoxyethylene sorbitan fatty acid ester is a hydrophilic compound formed by reacting a sorbitan fatty acid ester with ethylene oxide, and examples of the polyoxyethylene sorbitan fatty acid ester include, but are not limited to, T-20 (hydroxyl value is 90 to 110mgKOH/g), T-40 (hydroxyl value is 85 to 100mgKOH/g), T-60 (hydroxyl value is 80 to 105mgKOH/g), and T-80 (hydroxyl value is 65 to 82mgKOH/g) of Hainan petrochemical plant of Jiangsu province. In a preferred embodiment, the polyoxyethylene sorbitan fatty acid ester has a hydroxyl value of 85 to 110 mgKOH/g.
The styrylphenol-ethylene oxide condensate is a hydrophilic compound formed by reacting styrylphenol with ethylene oxide, and examples of the styrylphenol-ethylene oxide condensate include, but are not limited to, 600# (HLB value 12-16), 600-1# (HLB value 12-16), 600-2# (HLB value 12-16), and 600-3# (HLB value 12-16) of Haian petrochemical plant of Jiangsu province. In one embodiment, the styrylphenol-ethylene oxide condensate of the present invention has an HLB value of 12 to 16. HLB value: the surfactant is an amphiphilic molecule with a hydrophilic group and a lipophilic group, and the amount of the size and the force balance degree between the hydrophilic group and the lipophilic group in the surfactant molecule is defined as the hydrophilic-lipophilic balance value of the surfactant.
The applicant finds that the addition of the wetting dispersant and the film-forming agent which are compatible and adsorptive with the raw materials is beneficial to forming a thicker adsorption film, and more water is adsorbed on the periphery of the adsorption film to form a hydrated film, so that the collision and the increase of the particle size of the raw pesticide are further reduced, and the raw pesticide is coated in a three-dimensional cross network through the effects of the wetting dispersant, the film-forming agent and the thickening agent, so that the particle sedimentation in the storage process can be reduced, and the long-time fluidity and viscosity of the system are maintained in a certain range, thereby ensuring good processing and storage performances. In one embodiment, the starting material for the preparation of the composition of the present invention comprises the balance water.
In one embodiment, the composition of the present invention further comprises one or more of a stabilizer, an anti-freeze agent, an anti-foam agent, a ph adjusting agent. Examples of defoaming agents include, but are not limited to, silicones, C8-C10 fatty alcohols, C10-C20 saturated aliphatic carboxylic acids and their esters and ester-ether type compounds, in one embodiment, the defoaming agent of the present invention comprises 0 to 1 wt% of the composition; as examples of anti-freeze agents, including, but not limited to, ethylene glycol, propylene glycol, and glycerin, in one embodiment, the anti-freeze agent of the present invention comprises 1 to 10 wt% of the composition; examples of the pH adjusting agent include, but are not limited to, those selected from acetic acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide and ammonium salts and triethanolamine, and in one embodiment, the pH adjusting agent of the present invention is 0 to 2 wt% of the composition.
In a second aspect, the present invention provides a method for preparing a fluopyram-containing composition as described above, comprising the steps of:
mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
The invention provides an application of the fluopyram-containing composition for preventing and treating crop diseases. The composition provided by the present invention is capable of controlling various plant diseases such as gold needle pests and silk black ear diseases to be controlled in corn, and when used for controlling silk black ear diseases, the use amounts of the composition are: 300-500g/100kg of seeds, when the composition is used for preventing and treating the wireworms, the use amount of the composition is as follows: 400-600/100 kg of seeds.
Examples
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.
Example 1
The embodiment provides a composition, which is prepared from the following raw materials, by weight, 1% of fluopyram, 21% of thiamethoxam, 2% of tebuconazole, 0.4% of thickening agent, 6% of film-forming agent, 5% of wetting dispersant and the balance of water; the thickening agent comprises magnesium aluminum silicate and polyvinylpyrrolidone, and the weight ratio is 1: 3; the film forming agent is polyvinyl alcohol; the wetting and dispersing agent comprises a styrylphenol-ethylene oxide condensate; the composition is in the form of a seed treatment suspension.
The fluopyram is purchased from Jiangsu Furun Biochemical technology Co.
The thiamethoxam is purchased from Jiangsu Suabine biological agriculture Co.
The tebuconazole was purchased from Jiangsu Fengden pesticide Co.
The magnesium aluminum silicate is available from MA28 of goodberg source ring and technology (beijing) limited.
The polyvinyl alcohol was purchased from PVA-217 of Coly, Japan.
The polyvinylpyrrolidone was purchased from K25 of Roche New materials science Co., Ltd, hong Kong.
The styrylphenol-ethylene oxide condensate was purchased from 600-3# of Haian petrochemical plant of Jiangsu province.
This example also provides a method of preparing a composition as described above, comprising the steps of: mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
Example 2
The embodiment provides a composition, which is prepared from the following raw materials, by weight, 1% of fluopyram, 21% of thiamethoxam, 2% of tebuconazole, 0.4% of thickening agent, 6% of film-forming agent, 5% of wetting dispersant and the balance of water; the thickening agent comprises magnesium aluminum silicate and polyvinylpyrrolidone, and the weight ratio is 1: 3; the raw materials for preparing the film forming agent comprise alkyl acrylate, sodium vinylbenzene sulfonate and N-vinyl pyrrolidone, and the molar ratio of the raw materials is 1: 0.08: 0.08, the alkyl acrylate comprises propyl acrylate and hexyl acrylate, and the molar ratio is 1: 0.5, the preparation method of the film forming agent comprises the following steps: adding alkyl acrylate, N-vinyl pyrrolidone and dodecyl trimethyl ammonium chloride into water, adding sodium persulfate, reacting at 13 ℃ for 2.5 hours, adding sodium vinyl benzene sulfonate, and continuing to react for 1 hour to obtain a film-forming agent emulsion, wherein the total weight of the alkyl acrylate, the N-vinyl pyrrolidone and the sodium vinyl benzene sulfonate accounts for 12 wt% of the water, the sodium persulfate accounts for 0.01 mol% of the alkyl acrylate, and the dodecyl trimethyl ammonium chloride accounts for 4 mol% of the alkyl acrylate; the wetting and dispersing agent comprises a styrylphenol-ethylene oxide condensate; the composition is in the form of a seed treatment suspension.
The fluopyram is purchased from Jiangsu Furun Biochemical technology Co.
The thiamethoxam is purchased from Jiangsu Suabine biological agriculture Co.
The tebuconazole was purchased from Jiangsu Fengden pesticide Co.
The magnesium aluminum silicate is available from MA28 of goodberg source ring and technology (beijing) limited.
The polyvinylpyrrolidone was purchased from K25 of Roche New materials science Co., Ltd, hong Kong.
The styrylphenol-ethylene oxide condensate was purchased from 600-3# of Haian petrochemical plant of Jiangsu province.
This example also provides a method of preparing a composition as described above, comprising the steps of: mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
Example 3
The embodiment provides a composition, which is prepared from the following raw materials, by weight, 0.5% of fluopyram, 20% of thiamethoxam, 1% of tebuconazole, 0.2% of a thickening agent, 4% of a film forming agent, 4% of a wetting dispersant and the balance of water; the thickening agent comprises magnesium aluminum silicate and polyvinylpyrrolidone, and the weight ratio is 1: 3; the raw materials for preparing the film forming agent comprise alkyl acrylate, sodium vinylbenzene sulfonate and N-vinyl pyrrolidone, and the molar ratio of the raw materials is 1: 0.05: 0.1, the alkyl acrylate comprises butyl acrylate, and the preparation method of the film forming agent comprises the following steps: adding alkyl acrylate, N-vinyl pyrrolidone and dodecyl trimethyl ammonium chloride into water, adding sodium persulfate, reacting at 13 ℃ for 2.5 hours, adding sodium vinyl benzene sulfonate, and continuing to react for 1 hour to obtain a film-forming agent emulsion, wherein the total weight of the alkyl acrylate, the N-vinyl pyrrolidone and the sodium vinyl benzene sulfonate accounts for 10 wt% of the water, the sodium persulfate accounts for 0.01 mol% of the alkyl acrylate, and the dodecyl trimethyl ammonium chloride accounts for 4 mol% of the alkyl acrylate; the wetting dispersant comprises polyoxyethylene sorbitan fatty acid ester and styryl phenol-ethylene oxide condensation compound, and the weight ratio is 2: 1; the composition is in the form of a seed treatment suspension.
The fluopyram is purchased from Jiangsu Furun Biochemical technology Co.
The thiamethoxam is purchased from Jiangsu Suabine biological agriculture Co.
The tebuconazole was purchased from Jiangsu Fengden pesticide Co.
The magnesium aluminum silicate is available from MA28T of goodberg source ring and technology (beijing) limited.
The polyvinylpyrrolidone was purchased from K15 of Roche New materials science Co., Ltd, hong Kong.
The polyoxyethylene sorbitan fatty acid ester is purchased from T-20 of the Haian petrochemical plant of Jiangsu province.
The styrylphenol-ethylene oxide condensate was purchased from 600# of Haian petrochemical plant of Jiangsu province.
This example also provides a method of preparing a composition as described above, comprising the steps of: mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
Example 4
The embodiment provides a composition, which is prepared from the following raw materials in percentage by weight, 2 wt% of fluopyram, 24 wt% of thiamethoxam, 4 wt% of tebuconazole, 0.5 wt% of thickening agent, 8 wt% of film-forming agent, 7 wt% of wetting dispersant and the balance of water; the thickening agent comprises magnesium aluminum silicate and polyvinylpyrrolidone, and the weight ratio is 1: 4; the raw materials for preparing the film forming agent comprise alkyl acrylate, sodium vinylbenzene sulfonate and N-vinyl pyrrolidone, and the molar ratio of the raw materials is 1: 0.1: 0.05, wherein the alkyl acrylate comprises butyl acrylate and propyl acrylate, and the molar ratio is 1: the preparation method of the film forming agent comprises the following steps: adding alkyl acrylate, N-vinyl pyrrolidone and dodecyl trimethyl ammonium chloride into water, adding sodium persulfate, reacting at 13 ℃ for 2.5 hours, adding sodium vinyl benzene sulfonate, and continuing to react for 1 hour to obtain a film-forming agent emulsion, wherein the total weight of the alkyl acrylate, the N-vinyl pyrrolidone and the sodium vinyl benzene sulfonate accounts for 12 wt% of the water, the sodium persulfate accounts for 0.01 mol% of the alkyl acrylate, and the dodecyl trimethyl ammonium chloride accounts for 4 mol% of the alkyl acrylate; the wetting dispersant comprises polyoxyethylene sorbitan fatty acid ester and styryl phenol-ethylene oxide condensation compound, and the weight ratio is 3: 1; the composition is in the form of a seed treatment suspension.
The fluopyram is purchased from Jiangsu Furun Biochemical technology Co.
The thiamethoxam is purchased from Jiangsu Suabine biological agriculture Co.
The tebuconazole was purchased from Jiangsu Fengden pesticide Co.
The magnesium aluminum silicate is available from MA28 of goodberg source ring and technology (beijing) limited.
The polyvinylpyrrolidone was purchased from K30 of Roche New materials science Co., Ltd, hong Kong.
The polyoxyethylene sorbitan fatty acid ester is purchased from T-40 of the Haian petrochemical plant of Jiangsu province.
The styrylphenol-ethylene oxide condensate was purchased from 600-3# of Haian petrochemical plant of Jiangsu province.
This example also provides a method of preparing a composition as described above, comprising the steps of: mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
Example 5
The embodiment provides a composition, which is prepared from the following raw materials, by weight, 1% of fluopyram, 21% of thiamethoxam, 2% of tebuconazole, 0.4% of thickening agent, 6% of film-forming agent, 5% of wetting dispersant and the balance of water; the thickening agent comprises magnesium aluminum silicate and polyvinylpyrrolidone, and the weight ratio is 1: 3; the raw materials for preparing the film forming agent comprise alkyl acrylate, sodium vinylbenzene sulfonate and N-vinyl pyrrolidone, and the molar ratio of the raw materials is 1: 0.08: 0.08, the alkyl acrylate comprises propyl acrylate and hexyl acrylate, and the molar ratio is 1: 0.5, the preparation method of the film forming agent comprises the following steps: adding alkyl acrylate, N-vinyl pyrrolidone and dodecyl trimethyl ammonium chloride into water, adding sodium persulfate, reacting at 13 ℃ for 2.5 hours, adding sodium vinyl benzene sulfonate, and continuing to react for 1 hour to obtain a film-forming agent emulsion, wherein the total weight of the alkyl acrylate, the N-vinyl pyrrolidone and the sodium vinyl benzene sulfonate accounts for 12 wt% of the water, the sodium persulfate accounts for 0.01 mol% of the alkyl acrylate, and the dodecyl trimethyl ammonium chloride accounts for 4 mol% of the alkyl acrylate; the wetting dispersant comprises polyoxyethylene sorbitan fatty acid ester and styryl phenol-ethylene oxide condensation compound, and the weight ratio is 2.5: 1; the composition is in the form of a seed treatment suspension.
The fluopyram is purchased from Jiangsu Furun Biochemical technology Co.
The thiamethoxam is purchased from Jiangsu Suabine biological agriculture Co.
The tebuconazole was purchased from Jiangsu Fengden pesticide Co.
The magnesium aluminum silicate is available from MA28 of goodberg source ring and technology (beijing) limited.
The polyvinylpyrrolidone was purchased from K25 of Roche New materials science Co., Ltd, hong Kong.
The polyoxyethylene sorbitan fatty acid ester is purchased from T-20 of the Haian petrochemical plant of Jiangsu province.
The styrylphenol-ethylene oxide condensate was purchased from 600-3# of Haian petrochemical plant of Jiangsu province.
This example also provides a method of preparing a composition as described above, comprising the steps of: mixing, grinding and filtering the preparation raw materials of the composition to obtain the composition.
Example 6
This example provides a composition which is substantially the same as example 1 except that the magnesium aluminum silicate is available from MA21 of Goodpasture science and technology, Beijing.
This example also provides a method for preparing the composition described above, in the same manner as in example 1.
Example 7
This example provides a composition, which is similar to example 1, except that the polyvinylpyrrolidone is available from K90 of Roche New materials science and technology, Inc., hong Kong, Liang.
This example also provides a method for preparing the composition described above, in the same manner as in example 1.
Example 8
The present example provides a composition, which is similar to example 1, except that the thickening agent comprises magnesium aluminum silicate and polyvinylpyrrolidone in a weight ratio of 1: 0.05.
this example also provides a method for preparing the composition described above, in the same manner as in example 1.
Example 9
The present example provides a composition, which is similar to example 1, except that the thickening agent comprises magnesium aluminum silicate and polyvinylpyrrolidone in a weight ratio of 1: 6.
this example also provides a method for preparing the composition described above, in the same manner as in example 1.
Example 10
This example provides a composition, which is similar to example 2, except that the film-forming agent is prepared from alkyl acrylate, sodium vinylbenzenesulfonate and N-vinylpyrrolidone in a molar ratio of 1: 0.13: 0.03.
this example also provides a method for preparing the composition described above, as embodied in example 2.
Example 11
This example provides a composition, which is similar to example 2, except that the film-forming agent is prepared from alkyl acrylate, sodium vinylbenzenesulfonate and N-vinylpyrrolidone in a molar ratio of 1: 0.03: 0.13.
this example also provides a method for preparing the composition described above, as embodied in example 2.
Example 12
This example provides a composition, which is similar to example 2, except that the alkyl acrylate is lauryl acrylate.
This example also provides a method for preparing the composition described above, as embodied in example 2.
Example 13
This example provides a composition which is specifically embodied in the same manner as example 2 except that sodium vinylbenzenesulfonate is replaced with sodium vinylbenzenesulfonate.
This example also provides a method for preparing the composition described above, as embodied in example 2.
Example 14
This example provides a composition as in example 5, except that the wetting and dispersing agent comprises a polyoxyethylene sorbitan fatty acid ester and a styrylphenol-ethylene oxide condensate in a weight ratio of 0.5: 1.
this example also provides a method for preparing the composition described above, as embodied in example 5.
Example 15
This example provides a composition as in example 5, except that the wetting and dispersing agent comprises a polyoxyethylene sorbitan fatty acid ester and a styrylphenol-ethylene oxide condensate in a weight ratio of 5: 1.
this example also provides a method for preparing the composition described above, as embodied in example 5.
Example 16
This example provides a composition, which is similar to example 5, except that the polyoxyethylene sorbitan fatty acid ester is obtained from T-8 of Haian petrochemical plant of Jiangsu province.
This example also provides a method for preparing the composition described above, as embodied in example 5.
Example 17
This example provides a composition, which is similar to example 5, except that the polyoxyethylene sorbitan fatty acid ester is replaced with a sorbitan fatty acid ester, available from S-80 of Haian petrochemical plant, Jiangsu province.
This example also provides a method for preparing the composition described above, as embodied in example 5.
Example 18
This example provides a composition, which is similar to example 5, except that a styrylphenol-ethylene oxide condensate was replaced with a castor oil-ethylene oxide condensate, BY112(HLB value 10 to 16) obtained from heian petrochemical plant of Jiangsu province.
This example also provides a method for preparing the composition described above, as embodied in example 5.
Evaluation of Performance
1. And (3) field test: the 24% fluopyram, thiamethoxam and tebuconazole seed treatment suspending agent provided by the embodiment 5 of the invention is respectively subjected to field efficacy tests for preventing and treating corn wireworms in Henan Heyi crop science, Inc., and for preventing and treating corn head smut in agricultural colleges of Shihe university, and the specific experimental method and results are as follows:
field efficacy test of 24% fluopyram, thiamethoxam and tebuconazole seed treatment suspending agent for preventing and controlling corn wireworms
(1) The 24% flupyrad-thiamethoxam-tebuconazole seed treatment suspending agent provided by the invention is used as an experimental agent, and a contrast agent is arranged, wherein the contrast agent is a 30% thiamethoxam suspension seed coating agent of Shenyang chemical research institute (Nantong) chemical technology development Limited company.
(2) The application method comprises the following steps: coating seeds, wherein the ratio of the seeds to the seeds is 1: 50, the pesticide is applied once 1 day (4 months and 13 days in 2020) before sowing.
(3) Investigation time and number of times: the corn was investigated 1 time 20 days after sowing (5/4/2020) and at harvest (7/25/2020), and 2 times in total.
(4) And (3) yield investigation: all ears in the whole cell are investigated at the time of harvest (7 months and 25 days in 2020), which is equivalent to hectare yield.
(5) Safety investigation: the visual safety investigation of the corn seedling emergence rate (4 and 27 days 2020) and the visual safety investigation of the corn seedling emergence rate (5 and 3 days 2020) are carried out 7 days after the emergence of the corn seedlings once and 2 times in total
(6) The test results are shown in table 1:
results of 124% Fluopyram, thiamethoxam and tebuconazole seed treatment suspending agent for preventing and controlling corn wireworms
Note: the control (%) in the table is the average value of each repetition; the same letters after the same column of data are not significantly different. The variance analysis method comprises the following steps: DPS Duncan's new double offset method (DMRT) was used.
As can be seen from Table 1, when 24% fluopyram-thiamethoxam-tebuconazole seed treatment suspending agent is applied to control corn wireworms, the recommended dosage of the effective components of the seed coating before corn sowing is between 120 and 144 g/100kg of seeds, and the control effect of the seed treatment with the same dosage of the experimental medicament preparation is higher than that of the control medicament preparation. And the corns in each test area grow normally, and no phytotoxicity symptom or other adverse effects are found.
Two, 24% fluopyram, thiamethoxam and tebuconazole seed treatment suspending agent field efficacy test for preventing and treating maize head smut
(1) Test agents: the 24% fluopyram-thiamethoxam-tebuconazole seed treatment suspending agent provided by the invention is used as a tested object, the 41.7% fluopyram suspending agent of Bayer corporation is used as a reference 1, and the 60 g/l tebuconazole suspending seed coating agent of Shenyang chemical research institute (Nantong) chemical technology development Limited company is used as a reference 2 to carry out a field efficacy test.
(2) The application method and the water consumption are as follows: weighing the dose required by each cell, fully diluting the dose with distilled water, fixing the volume to 10mL, and fully mixing the dose with 150 g of corn seeds required by each cell for seed dressing.
(3) Investigation time and number of times: recording the time of emergence and rate of emergence (5 months and 17 days 2020); after the ears are full, the disease is investigated when the symptoms are obvious (24/8/2020). The total number of surveys was 2.
(4) The test results are shown in Table 2
Results of preventing and treating maize head smut by using 224% of fluopyram, thiamethoxam and tebuconazole seed treatment suspending agent
Note: different upper and lower case letters in the table indicate significance of difference to the 1% and 5% levels.
As can be seen from the table 2, the 24% fluopyram-thiamethoxam-tebuconazole seed treatment suspending agent has a good prevention and treatment effect on the maize head smut, and when the maize seed is coated, the dosage of the suspending agent is 96-120 g of effective component per 100kg of seeds, and the dosage of the suspending agent is 400-500 g per 100kg of seeds, good prevention effect and emergence rate can be obtained. And in the range of the experimental dosage, the corn pesticide is safe and has no phytotoxicity.
2. And (3) testing toxicity: toxicity tests were carried out on corn silk black ear diseases using the spore germination method, using fluopyram-thiamethoxam-tebuconazole provided by the present invention as a test group, and 2% tebuconazole and 1% fluopyram as a control group, respectively:
(1) selection of test
Head smut: the spores were harvested from harvested Sphaerotheca zeae tissue and a suspension of the spores (approximately 7X 106 spores/mL) was prepared.
(2) Test agent
Test agents: 1% of fluopyram, 6% of tebuconazole and more than 24% of thiamethoxam, fluopyram and tebuconazole are all purchased from Jilin Jinqiu pesticide Co.
(3) Virulence determination of maize head smut pathogenic bacteria
Preparing a mother solution: the concentration of the fluopyram mother liquor is 1 percent, the concentration of the tebuconazole mother liquor is 2 percent, the concentration of the mother liquor of the compound medicament of thiamethoxam, fluopyram and tebuconazole (the ratio of the three is 21: 1: 2) is 24 percent, and the concentrations of the three medicaments are respectively diluted to 10-1, 10-2, 10-3, 10-4 and 10-5 times for later use.
Medicament treatment: according to the experimental design, 20 mu L of liquid medicine with different series of concentrations of the medicine is respectively taken and put into a 50mL sterilized triangular flask containing 20mL of bacterial liquid, and the bacterial liquid without the medicine is taken as a reference. Each treated spore suspension was incubated at 25 ℃ in a 90r/min rotary shaking incubator.
The investigation method comprises the following steps: when the germination rate of the blank control spores reaches more than 90%, microscopic examination is carried out on the germination condition of the treated winter spores, 3 visual fields are observed randomly without repetition, the total number of the spores is not less than 100, the germination number and the total number of the spores are respectively recorded, and the germination is regarded as the germination when the length of a spore germ tube is larger than the short radius of the spores.
The calculation method comprises the following steps: spore germination rate (%) ═ spore germination number/survey spore total number × 100
Treatment corrected spore germination rate (%) -treated spore germination rate/blank control spore germination rate x 100
Relative inhibition ratio (%) of spore germination (blank control spore germination ratio-treatment corrected spore germination ratio)/blank control spore germination ratio × 100
And (3) data statistics: respectively establishing a toxicity regression equation by taking the logarithm value of the concentration (mg/L) of the medicament as an independent variable x and the probability value of the relative inhibition rate of spore germination as a dependent variable y, solving the co-toxicity coefficients of different test medicaments, and comparing the spore germination inhibition effects of the preparations with the same dosage of active ingredients under different concentrations on the maize head smut.
(4) Results of virulence determination
The virulence determination results are shown in table 3.
TABLE 324% Fluopyram, thiamethoxam, tebuconazole virulence test result for maize head smut
As can be seen from Table 3, the combination of the fluopyram, the thiamethoxam and the tebuconazole provided by the invention has high synergistic effect, and the EC50 value of the mixed medicament of 2% of tebuconazole and 1% of fluopyram is 0.012mg/L, and the cotoxicity coefficient value is 188, which shows that the combination of the tebuconazole and the fluopyram has obvious synergistic effect.
2. Storage stability at normal temperature: the compositions provided in the examples were placed in a glass container, sealed at (23 ± 2) ° c for 6 months, 9 months, and 12 months, and observed whether solid matter was deposited on the side wall of the container or whether precipitation occurred on the bottom of the container, wherein grade 1 showed no wall deposition and precipitation, grade 2 showed slight wall deposition and no precipitation, grade 3 showed wall deposition, slight precipitation, grade 4 showed wall deposition and precipitation, and grade 5 showed wall deposition and precipitation, and the results are shown in table 4.
Table 4 characterization test of properties
3. Heat storage stability: after the compositions provided in the examples were placed in a glass container and sealed at (54 ± 2) ° c for 7 days, 14 days, 28 days and 35 days, whether solid matter was adhered to the side wall of the container or whether precipitation occurred at the bottom of the container was observed, wherein grade 1 shows no wall adhesion and precipitation, grade 2 shows slight wall adhesion and no precipitation, grade 3 shows general wall adhesion and slight precipitation, grade 4 shows general wall adhesion and precipitation, and grade 5 shows remarkable wall adhesion and precipitation, and the results are shown in table 5.
Table 5 characterization test of properties
4. Heat storage fluidity: placing the composition provided in the example in a glass container, sealing at (54 + -2) ° c, storing for 28 days, shaking the container, and observing the flow state, wherein grade 1 is that the composition can recover the flow by slightly shaking the container, the container is vertical, and the bottom is free from caking; grade 2, slightly shaking the container, the composition can flow again, the container is vertical, and a small amount of lumps are on the bottom; grade 3, shaking the container with force to recover the flow of the composition, making the container vertical and having a small amount of lumps at the bottom; the 4-stage is that the container is shaken vigorously, and the composition can not flow again and is in a flocculation state. The results are shown in Table 6.
Table 6 characterization test of properties
Examples
Fluidity in heat storage
1
Stage 2
2
Grade 3
3
Level 1
4
Level 1
5
Level 1
10
Grade 3
11
Stage 2
12
4 stage
13
Grade 3
14
Stage 2
15
Grade 3
16
Stage 2
17
Stage 2
18
Stage 2
5. Water resistance: putting a certain amount of corn seeds in a culture dish, respectively sucking the same amount of the composition provided in the embodiment by using a syringe, injecting the composition into the culture dish, covering and shaking the culture dish, flatly spreading the coated seeds, placing the coated seeds to obtain a sample of the corn seeds coated with a coating film, immersing the sample in water at the temperature of (23 +/-2) DEG C, observing whether the coating film is damaged or not every 5 days, such as falling, breakage and the like, continuously observing for 60 days, and recording the time of falling and breakage. The results are shown in Table 7.
Table 7 characterization test of properties
Examples
Water resistance
1
20 days
2
50 days
3
50 days
4
55 days
5
60 days
10
45 days
11
40 days
12
20 days
13
40 days
As is clear from the test results in tables 4 to 7, the compositions provided by the present invention can control various plant diseases such as the control subject of corn, i.e., the needle worm and silk black ear diseases, etc., and the compositions provided by the present invention have high storage stability and fluidity, can improve the service life, and when used for seed treatment, the obtained seed coating films have high resistance to rain erosion and water immersion.
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.