Suspending agent as well as preparation method and application thereof
By using tannic acid modified nanosilicon dioxide in seed treatment suspension agent, the problem of water permeability and breathability reduction caused by excessive film-forming agent content is solved, and better seed germination and seedling growth, as well as pest control and disease control Effect.
Patent Information
- Application Number
- CN202411699907.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-26
- Publication Date
- 2024-12-27
- Estimated Expiration
- Not applicable · inactive patent
AI Technical Summary
Excessive content of film-forming agents in existing seed treatment suspension agents leads to a decrease in seed water permeability and breathability, affecting seed germination and seedling growth.
Using tanninic acid modified nano-silica, by improving the antioxidant and antibacterial properties of the suspension agent, reducing the amount of film-forming agent, improving the spread uniformity of active components on the plant surface, enhancing the prevention and control effect of diseases and pests, and improving Permeability of the plant surface.
It effectively improves the water permeability and breathability of seeds, promotes the germination of seeds and the growth of seedlings, and reduces the amount of agents used in pest control and environmental pollution.
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Figure CN119184073A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of pesticides, and in particular to a suspension concentrate and a preparation method and application thereof. Background Art
[0002] Suspension concentrate refers to a preparation in which the pesticide technical is dispersed into microparticles and evenly dispersed in a dispersion such as water, including seed treatment suspension concentrate. Seed treatment suspension concentrate is a pesticide preparation specially used for seed treatment, which suspends active ingredients and other auxiliary materials in a liquid, and is designed to promote uniform coverage of the pesticide on the surface of seeds to protect seeds from diseases and pests, while promoting seed germination and seedling growth. Due to its advantages of increasing germination and emergence rates, promoting seedling growth, reducing environmental pollution, reducing seed treatment costs, long-term protection, reducing pesticide usage, and increasing crop yield and quality, the share of seed treatment suspension concentrate in the pesticide market has shown an upward trend in recent years, and with technological advances and increased market demand, the market for seed treatment suspension concentrates is expected to continue to maintain steady growth.
[0003] However, there are some technical problems in the existing seed treatment suspensions that affect seed germination and inhibit plant growth. Common problems include the inhibition of seed germination due to the use of a single agent. For example, myclobutanil is a broad-spectrum, highly effective and safe pesticide active ingredient, which is widely used in the prevention and control of diseases of various crops. However, myclobutanil seed treatment suspension may inhibit seed germination when treating seeds. In order to alleviate the negative impact of myclobutanil seed treatment suspension, myclobutanil can be combined with other fungicides with different mechanisms of action to reduce the inhibitory effect of a single agent on seeds; it can also be added by adding protective agents to improve seed tolerance and adding plant hormones to activate the antioxidant and detoxification enzyme activities in seeds to alleviate seed growth inhibition; it can also be adjusted by other auxiliary materials in the myclobutanil seed treatment suspension to alleviate the inhibition of seed growth by the myclobutanil seed treatment suspension.
[0004] In addition, in order to improve the film-forming property of the seed treatment suspension, it is often necessary to add a film-forming agent to the seed treatment suspension. When the content of the film-forming agent in the seed treatment suspension is low, the film-forming property of the seed treatment suspension is poor, the coating uniformity of the seeds is poor, and the coating shedding rate is high. In order to improve the film-forming property and coating uniformity and reduce the coating shedding rate, it is often necessary to increase the amount of the film-forming agent. For example, the amount of film-forming agent in some seed treatment suspensions even needs to reach 12%. However, excessive use of the film-forming agent will affect the water permeability and air permeability of the seeds, thereby affecting the germination of the seeds and the growth of the seedlings. Summary of the invention
[0005] The purpose of the present application is to provide a suspension concentrate and a preparation method and application thereof, so as to solve the technical problem in the prior art that the water permeability and air permeability of seeds are reduced due to excessively high content of film-forming agent in the suspension concentrate.
[0006] In order to achieve the above application purpose, the technical solution adopted in this application is as follows: In the first aspect, the embodiment of the present application provides a suspension agent. Taking the mass content of the suspension agent as 100%, the suspension agent of the embodiment of the present application includes the following components: Active ingredient 1%~50% Tannic acid modified nano-silica 3%~15% Emulsifying dispersant 3%~10% Film former 2%~10% Water 20%~60%.
[0007] The suspension of the present application example effectively improves the antioxidant and antibacterial properties of the suspension by adding tannic acid-modified nano-silica, increases the adhesion of the suspension, improves the uniformity of the active component spreading on the plant surface, improves the control effect of the suspension on pests and diseases, and reduces the amount of the film-forming agent. When the suspension is applied to the plant surface, the water permeability and air permeability of the plant surface are improved. When the suspension is applied to seed treatment, the seeds have good water permeability and air permeability after coating treatment, which effectively promotes seed germination and seedling growth.
[0008] In a second aspect, the present invention provides a method for preparing the suspension concentrate mentioned above. The method for preparing the suspension concentrate in the present invention comprises the following steps: The active component, tannic acid modified nano silicon dioxide, an emulsifying dispersant, a film-forming agent and water are mixed in proportion to obtain a suspension.
[0009] The method for preparing the suspension concentrate of the embodiment of the present application has few process steps, controllable process parameters, and is suitable for large-scale industrial production. At the same time, the suspension concentrate prepared by the method for preparing the suspension concentrate of the embodiment of the present application has good antioxidant and antibacterial properties, good adhesion performance, good spreading uniformity of the active component on the plant surface, less partial deposition of the active component, and good control effect on pests and diseases; in addition, the amount of film-forming agent in the suspension concentrate is small, and when the suspension concentrate is used on the plant surface, the water permeability and air permeability of the plant surface are good, which is conducive to the growth of the plant.
[0010] In a third aspect, the embodiments of the present application provide the use of the above-mentioned suspending agent or the suspending agent prepared by the above-mentioned suspending agent preparation method as a seed treatment agent.
[0011] Since the amount of the suspension concentrate film-forming agent used in the above-mentioned text is low, the active ingredients have good dispersibility and less local precipitation, and the active ingredients have good adhesion to the plant surface such as the seed surface, when the suspension concentrate is used as a seed treatment agent, it not only has a good prevention and control effect on pests and diseases, but also the treated seeds have good water permeability and air permeability, which is beneficial to seed germination and seedling growth. BRIEF DESCRIPTION OF THE DRAWINGS
[0012] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained like these drawings without paying any creative work.
[0013] Picture 1 The diagram shows the growth status of rice treated with the seed treatment suspension of Example 1, the control sample after coating, and the blank control without coating treatment. DETAILED DESCRIPTION
[0014] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
[0015] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.
[0016] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, a~b (i.e. a and b), a~c, b~c, or a~b~c, where a, b, and c can be single or multiple.
[0017] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
[0018] The terms used in the embodiments of the present application are only for the purpose of describing specific embodiments, and are not intended to limit the present application. The singular forms "a", "an" and "the" used in the embodiments of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.
[0019] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also indicate the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass in the embodiment description of the present application can be a mass unit known in the chemical industry such as µg, mg, g, kg, etc.
[0020] The terms "first" and "second" are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. For example, without departing from the scope of the embodiments of the present application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Thus, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features.
[0021] In order to solve the technical problem in the prior art that the water permeability and air permeability of seeds are reduced due to the excessively high content of the suspending agent and film-forming agent, the present application proposes the following technical solution.
[0022] In the first aspect, the embodiment of the present application provides a suspension agent. Taking the mass content of the suspension agent as 100%, the suspension agent of the embodiment of the present application includes the following components: Active ingredient 1%~50% Tannic acid modified nano-silica 3%~15% Emulsifying dispersant 3%~10% Film former 2%~10% Water 20%~60%.
[0023] Tannic acid is a natural polyphenol compound, which is an ester compound formed by multiple gallic acid molecules and polyols such as glucose. Due to the multiple phenolic hydroxyl structures contained in the tannic acid structure, these phenolic hydroxyl structures can form hydrogen bond structures with plant leaves or seed epidermis to enhance adhesion. The embodiment of the present application uses tannic acid to modify nano-silicon dioxide, so that the adhesion performance of nano-silicon dioxide is further improved, thereby further promoting the spreading of active components on the surface of plants, and effectively reducing the amount of polyacrylic acid film-forming agent on the basis of making the suspending agent have good film-forming properties, so that the amount of film-forming agent is only 2%~10%, effectively improving water permeability and air permeability. When the suspending agent is used, for example, when used as a seed treatment agent, the tannic acid-modified nano-silicon dioxide can also form a loose porous structure on the surface of the seed, thereby further improving the air permeability and water permeability of the seed, effectively alleviating the problem of poor water permeability and air permeability caused by adding a large amount of film-forming agent to the seed treatment suspending agent, creating a good environment to promote seed germination, and reducing the negative impact of the treatment of the agent on the seed.
[0024] The tannic acid-modified nano-silica in the suspension of the present application can also effectively adsorb the active components in the suspension. When the suspension is used, the active components in the suspension can be evenly spread on the plant surface, effectively improving the control effect of the suspension of the present application on plant diseases and insect pests. Tannic acid molecules can also form a supramolecular structure. The use of tannic acid-modified nano-silica can further improve the loading capacity of nano-silica for drugs, thereby improving the stability of the suspension.
[0025] In addition, the polyphenol structure of tannic acid gives tannic acid good antioxidant and antibacterial properties. In the embodiment of the present application, tannic acid-modified nano-silica is added to the suspension of the embodiment of the present application. When the suspension is used for seed treatment, the tannic acid-modified nano-silica can further improve the antioxidant and antibacterial capabilities of the seeds.
[0026] It should be noted that the suspension concentrate of the present application can not only be used for seed treatment, but can also be applied to the leaves, rhizomes, etc. of plants, without specific limitation.
[0027] In some embodiments, the mass content of tannic acid modified nano silicon dioxide in the embodiment of the present application suspension can be 3% to 10%, which can be selected as 3% to 8%, 5% to 10%, 8% to 15%, 10% to 15%, and 12% to 15%. In the exemplary embodiment, the mass content of tannic acid modified nano silicon dioxide can be 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% and other typical but non-restrictive sizes, or any size between any two numerical ranges. Controlling the mass content of tannic acid modified nano silicon dioxide within this range further improves the adhesion performance of the suspension, reduces the amount of polypropylene film-forming agent in the suspension, improves water permeability and air permeability, and further improves the adsorption of active components, reduces the local deposition of active components, and improves the dispersibility and dispersion stability of active components of the suspension.
[0028] In some embodiments, tannic acid modified nano-silica is nano-silica with tannic acid groups bound to its surface. Nano-silica, as a new type of inorganic functional material, has excellent mechanical properties, high specific surface area, high crystallinity, high transparency, low density, good biocompatibility and stable chemical properties. When nano-silica is added to a suspending agent and the suspending agent is used for seed treatment, the absorption and utilization of silica on the seeds can improve the germination environment of the seeds, improve stress resistance, promote growth and improve the soil environment. Tannic acid groups are combined on the surface of nano-silica to form tannic acid modified nano-silica, which further improves the adhesion and adsorption properties of nano-silica, effectively reduces the amount of acrylic film-forming agents in the suspending agent, and improves the dispersibility and dispersion stability of the active pharmaceutical ingredients in the suspending agent.
[0029] In some embodiments, the nano-silica and the tannic acid group can also be connected through a connecting bridge molecular chain. By connecting the nano-silica and the tannic acid group through the connecting bridge molecular chain, the difficulty of the tannic acid group and the nano-silica can be reduced, the stability of the combination between the tannic acid group and the nano-silica can be further improved, and the content of the tannic acid group bound to the surface of the nano-silica can be increased, thereby further improving the adhesion performance and adsorption capacity of the tannic acid modified nano-silica, further reducing the amount of film-forming agent in the suspending agent, and improving the stability of the suspending agent.
[0030] In some embodiments, the connecting bridge molecular chain may include a first molecular chain and a second molecular chain, wherein the first molecular chain may be the residual group of the silane coupling agent after the reaction of nano-silicon dioxide and an amino-containing silane coupling agent, and the second molecular chain may be the residual group of the linker after the reaction of an amino group and a linker molecule containing two aldehyde groups and tannic acid.
[0031] In some embodiments, the content of tannic acid groups bound to the surface of nano-silica in tannic acid-modified nano-silica can be 0.09-0.14 g / g, optionally 0.10-0.14 g / g, 0.10-0.13 g / g, 0.12-0.14 g / g. Among them, the content of tannic acid groups bound to the surface of nano-silica in tannic acid-modified nano-silica of 0.1 g / g means that the content of tannic acid groups in each gram of tannic acid-modified nano-silica can be 0.1 g. In the exemplary example, the content of tannic acid groups bound to the surface of nano-silica in tannic acid-modified nano-silica can be 0.09 g / g, 0.10 g / g, 0.11 g / g, 0.12 g / g, 0.13 g / g, 0.14 g / g and other typical but non-limiting sizes, or any size between any two numerical ranges. The content of tannic acid groups in tannic acid modified nano-silica is controlled within this range, and the adhesion and adsorption properties of tannic acid modified nano-silica are further improved, thereby further reducing the use of film-forming agents in the suspension, improving water permeability and air permeability, and improving the drug dispersibility and dispersion stability of the suspension. It should be noted that the content of tannic acid groups bound to the surface of nano-silica in tannic acid modified nano-silica is calculated based on the groups remaining on the surface of nano-silica after the tannic acid reaction.
[0032] In some embodiments, the particle size D90 of the tannic acid modified nano-silica can be 200-400 nm, optionally 200-350 nm, 250-400 nm, 300-400 nm. In an exemplary embodiment, the particle size of the tannic acid modified nano-silica can be 200 nm, 210 nm, 220 nm, 230 nm, 240 nm, 250 nm, 260 nm, 270 nm, 280 nm, 290 nm, 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, 400 nm, etc., which are typical but non-limiting sizes, or any size between any two values. By controlling the particle size of the tannic acid modified nano-silica within this range, the specific surface area of the tannic acid modified nano-silica is further increased, the adsorption capacity of the tannic acid modified nano-silica for active pharmaceutical ingredients is increased, and the adhesion performance of the tannic acid modified nano-silica on the plant surface is increased.
[0033] In some embodiments, the tannic acid-modified nano-silica has a porous structure. The porous structure in the tannic acid-modified nano-silica can further improve the adsorption of the tannic acid-modified nano-silica to the active pharmaceutical ingredient. At the same time, the tannic acid-modified nano-silica has a porous structure so that when the tannic acid-modified nano-silica is evenly spread on the surface of plants such as seeds, a loose porous structure can be formed, further improving the air permeability and water permeability of the surface of plants such as seeds.
[0034] In some embodiments, the specific surface area of the tannic acid modified nano-silica can be 300-400 m 2 / g, optional: 300~350 m 2 / g 350~400 m 2 / g, 380~400 m 2 / g, 400~450 m 2 / g. In the exemplary embodiment, the specific surface area of tannic acid modified nano-silica can be 300 m 2 / g, 310 m 2 / g, 320 m 2 / g, 330 m 2 / g, 340 m 2 / g, 350 m 2 / g, 360 m 2 / g, 370 m 2 / g, 380 m 2 / g, 390 m 2 / g, 400 m 2 / g and other typical but non-limiting sizes, or any size between any two numerical ranges. Controlling the specific surface area of tannic acid modified nano-silica within this range further improves the adsorption performance of tannic acid modified nano-silica, improves the dispersibility and dispersion stability of drugs in suspensions, and reduces local deposition of drugs.
[0035] In some embodiments, tannic acid-modified nano-silica can be prepared by a method comprising the following steps: Step A10: performing a first modification treatment on the nano-silica using a coupling agent containing an amino group to obtain amino-modified nano-silica; Step A20: combining tannic acid groups on the surface of the amino-modified nano-silica to obtain tannic acid-modified nano-silica.
[0036] The nano-silica is subjected to a first modification treatment by a coupling agent containing an amino group to obtain amino-modified nano-silica, so that the surface of the nano-silica is connected with amino groups that are easy to react, so that the subsequent tannic acid groups can be better combined with the surface of the amino-modified nano-silica.
[0037] Step A10: Nano-silica is provided in step A10, and a coupling agent containing an amino group is used to perform a first modification treatment on the nano-silica, so that the coupling agent reacts with the nano-silica, thereby connecting the amino group to the surface of the nano-silica, and obtaining amino-modified nano-silica.
[0038] In some embodiments, the nano-silica may have a porous structure. The nano-silica is controlled to have a porous structure, so that the subsequently prepared tannic acid-modified nano-silica has a porous structure, so as to improve the adsorption performance of the tannic acid-modified nano-silica on active components, and after the tannic acid-modified nano-silica is attached to the surface of the plant, the water permeability and air permeability of the plant are further improved.
[0039] In some embodiments, the specific surface area of nano-silicon dioxide can be 350-450 m 2 / g, optional: 350~400m 2 / g, 380~400 m 2 / g, 400~450 m 2 / g. In the exemplary embodiment, the specific surface area of nano-silicon dioxide can be 350 m 2 / g, 360 m 2 / g, 370 m 2 / g, 380 m 2 / g, 390 m 2 / g, 400 m 2 / g, 410 m 2 / g, 420 m 2 / g, 430 m 2 / g, 440 m 2 / g, 450 m 2 / g and other typical but non-limiting sizes, or any size between any two numerical ranges. The specific surface area of the nano-silica is controlled within this range to further increase the specific surface area of the tannic acid-modified nano-silica.
[0040] In some embodiments, nano-silica can be purchased commercially.
[0041] In other embodiments, nano-silicon dioxide can also be prepared by a method comprising the following steps: dispersing a template in a first solvent to obtain a template mixture, mixing the template mixture with ammonia water and tetraethyl silicate, performing a precipitation reaction, and removing the template to obtain nano-silicon dioxide.
[0042] Wherein, the template agent includes a surfactant, and the first solvent includes water.
[0043] The preparation method of the nano-silicon dioxide uses a surfactant as a template agent, disperses the template agent in a first solvent containing water to form microparticles, and ammonia water and tetraethyl silicate can undergo a precipitation reaction in water to form a silicon dioxide precipitate. After the template agent mixed liquid is mixed with ammonia water and tetraethyl silicate, the ammonia water and tetraethyl silicate use the microparticles in the reaction system as templates to form a precipitate on the surface of the microparticles, thereby preparing nano-silicon dioxide with a porous structure.
[0044] In some embodiments, the template can be dispersed in the first solvent by stirring. In a further embodiment, the stirring speed of the template dispersed in the first solvent can be 200 to 400 rpm, optionally 200 to 300 rpm. In the exemplary embodiment, the speed of the template dispersed in the first solvent can be 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, etc., which are typical but non-limiting speeds, or any speed size between any two numerical ranges. Controlling the speed of the template dispersed in the first solvent within this range is conducive to forming uniform and stable microparticles.
[0045] In some embodiments, the precipitation reaction process can also be stirred so that nano silicon dioxide is uniformly deposited on the surface of the particles formed by the template. In a further embodiment, the stirring speed during the precipitation reaction process can be 200 to 400 revolutions, and can be optionally 200 to 300 revolutions. In the exemplary embodiment, the stirring speed during the precipitation reaction process can be 200 revolutions, 250 revolutions, 300 revolutions, 350 revolutions, 400 revolutions, etc., which are typical but non-restrictive rotation speeds, or any rotation speed size between any two numerical ranges. Controlling the rotation speed of the precipitation reaction within this range further promotes the uniform deposition of silicon dioxide on the surface of the particles.
[0046] In some embodiments, the surfactant may include at least one of a cationic surfactant and a nonionic surfactant. In an exemplary embodiment, the cationic surfactant includes at least one of Cetyl TrimethylAmmonium Chloride (CTAC) and Cetyl TrimethylAmmoniumBromide (CTAB). The nonionic surfactant includes at least one of fatty alcohol polyoxyethylene ether and polyoxyethylene ether polyoxypropylene ether block copolymer. The stable particles that these surfactants can form in water are conducive to the formation of nano-silica with a porous structure.
[0047] In some embodiments, the mass concentration of the template in the reaction system of the precipitation reaction can be 0.1% to 0.5%, and can be optionally 0.1% to 0.4%, 0.2 to 0.5%, 0.3 to 0.4%, 0.3 to 0.5%. In the exemplary embodiment, the mass concentration of the template can be 0.1%, 0.25%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5% and other typical but non-limiting sizes, or any size within any two numerical ranges. Controlling the mass concentration of the template within this range effectively controls the size of the particles in the reaction system, thereby controlling the size of the pores in the porous structure of the nano-silica and the particle size of the nano-silica, and increasing the specific surface area of the tannic acid-modified nano-silica obtained by the nano-silica.
[0048] In some embodiments, the coupling agent containing an amino group may include at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a boric acid coupling agent.
[0049] In a further embodiment, the silane coupling agent includes at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane. These silane coupling agents have good reactivity with nano-silicon dioxide and can effectively react with nano-silicon dioxide, so that amino groups are connected to the surface of nano-silicon dioxide.
[0050] In some embodiments, the mass ratio of nano-silica and the coupling agent containing amino groups in the first modification treatment can be 1: (0.4-1), optionally 1: (0.5-1), 1: (0.6-1). In the exemplary embodiment, the mass ratio of nano-silica and the coupling agent containing amino groups can be 1: 0.5, 1: 0.6, 1: 0.7, 1: 0.8, 1: 0.9, 1: 1 and other typical but non-limiting mass ratios, or any mass ratio between any two ratio ranges. The mass ratio of nano-silica and the coupling agent containing amino groups is controlled within this range to further increase the amino content in the amino-modified nano-silica, thereby increasing the content of tannic acid groups subsequently bound to the surface of the nano-silica, so as to improve the adhesion performance of the tannic acid-modified nano-silica and the adsorption performance of drugs.
[0051] In some embodiments, the solvent of the first modification treatment may include a non-polar solvent, and in further embodiments, the non-polar solvent may include at least one of toluene, xylene, and n-hexane. These non-polar solvents have good solubility for coupling agents such as silane coupling agents and do not react with silane coupling agents. It should be noted that the solvent of the first modification treatment is one, or two or more, and is not specifically limited.
[0052] In some embodiments, the temperature of the first modification treatment may be 40-100°C, optionally 40-80°C, 60-100°C, 60-80°C. In an exemplary embodiment, the temperature of the first modification treatment may be 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, etc., which are typical but non-limiting temperatures, or any temperature between any two numerical ranges. The temperature of the first modification treatment is controlled within this range to further increase the reaction rate of the coupling agent and the nano-silica, while reducing the volatilization of the solvent.
[0053] In some embodiments, the time of the first modification treatment can be 8 to 24 hours, and can be 8 to 12 hours, 8 to 16 hours. In the exemplary embodiment, the time of the first modification treatment can be 8 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc., which are typical but non-limiting times, or any time within any two numerical ranges. Controlling the time of the first modification treatment within this range further promotes the sufficient reaction between the coupling agent and the nano-silica, and improves the yield of the amino-modified nano-silica.
[0054] Step A20: Through step A20, tannic acid is combined with amino-modified nano-silica, so that the surface of the amino-modified nano-silica is combined with tannic acid groups, thereby obtaining tannic acid-modified nano-silica.
[0055] In some embodiments, tannic acid groups can be bound to the surface of amino-modified nano-silica by a method comprising the following steps: Step A21: subjecting the amino-modified nano-silica to a first condensation reaction with a linker to obtain aldehyde-modified nano-silica; Step A22: subjecting the aldehyde-modified nano-silica to a second condensation reaction with tannic acid to obtain tannic acid-modified nano-silica.
[0056] The linker molecule contains two or more aldehyde groups.
[0057] Step A21: Through the first condensation reaction in step A21, the amino group on the aminated modified nano-silica and an aldehyde group in the linker are condensed, so that the surface of the nano-silica is connected with an aldehyde group, thereby obtaining the aldehyde-modified nano-silica.
[0058] In certain embodiments, the aldehyde group in the linker molecule can be two. In further embodiments, the atomic number of the molecular segment between two aldehyde groups in the linker molecule can be 3 to 5, which can be optionally 3 to 4, 3 to 5. In the exemplary embodiment, the atomic number of the molecular segment between two aldehyde groups in the linker molecule can be 3, 4, 5 typical but non-restrictive sizes. The atomic number of the molecular segment between two aldehyde groups in the linker molecule refers to the atomic number of the shortest segment between the two aldehyde groups, such as 3 in glutaraldehyde, and 2 in the molecular chain atomic number between two aldehyde groups in the succinaldehyde molecule. Control the atomic number of the molecular segment between two aldehyde groups in the linker molecule within the range, further promote the second condensation reaction between aldehyde-modified nano silica and tannic acid, and improve the yield of tannic acid modified nano silica.
[0059] It is understandable that the first condensation reaction may include only one linking agent or two or more linking agents. When the first condensation reaction includes two or more connections, the number of aldehyde groups in the linking agent may be the same or different. When the first condensation reaction includes two or more linking agents and the linking agent molecules all contain two aldehyde groups, the number of atoms of the molecular segment between the two aldehyde groups in the linking agent molecules may be the same or different.
[0060] In some embodiments, the linking agent includes at least one of glutaraldehyde, dialdehyde polyethylene glycol, adipaldehyde, and heptanedialdehyde. These linking agents can effectively formaldehyde the surface of the amino-modified nano-silica, and can further promote the obtained formaldehyde-modified nano-silica to undergo a second condensation reaction with tannic acid, thereby further improving the yield of the tannic acid-modified nano-silica.
[0061] In some embodiments, the reaction solvent of the first condensation reaction includes water.
[0062] In some embodiments, the temperature of the first condensation reaction can be 20-60°C, optionally 20-50°C, 30-60°C, 30-50°C. In the exemplary embodiment, the temperature of the first condensation reaction can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, etc., which are typical but non-limiting temperatures, or any temperature between any two numerical ranges. The temperature of the first condensation reaction is controlled within this range to further increase the reaction rate of the first condensation reaction and promote the full progress of the first condensation reaction.
[0063] In some embodiments, the reaction time of the first condensation reaction can be typical but non-limiting time such as 3 h, 5 h, 10 h, etc., and is not specifically limited as long as the first condensation reaction is fully carried out.
[0064] Step A22: Through step A22, the aldehyde groups bound to the surface of the aldehyde-modified nano-silica and the hydroxyl groups in the tannic acid undergo a second condensation reaction, so that the tannin groups are bound to the surface of the nano-silica to obtain tannic acid-modified nano-silica. It should be noted that the tannic acid groups in the embodiments of the present application refer to the groups obtained after the reaction of some hydroxyl groups in the tannic acid.
[0065] In some embodiments, the solvent for the second condensation reaction includes water.
[0066] In some embodiments, the temperature of the second condensation reaction can be 20-60°C, optionally 20-50°C, 30-60°C, 30-50°C. In the exemplary embodiment, the temperature of the second condensation reaction can be 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, etc., which are typical but non-limiting temperatures, or any temperature between any two numerical ranges. The temperature of the second condensation reaction is controlled within this range to further increase the reaction rate of the second condensation reaction and promote the full progress of the second condensation reaction.
[0067] In some embodiments, the time for the second condensation reaction can be typical but non-limiting time such as 8 h, 10 h, 12 h, 24 h, etc., and is not specifically limited, as long as the second condensation reaction is fully carried out.
[0068] It can be understood that in the preparation method of tannic acid-modified nano-silica in the embodiment of the present application, the residual groups of the linker after the first condensation reaction and the second condensation reaction, and the residual groups of the coupling agent after the reaction above constitute the connecting bridge molecular chain between the nano-silica and the tannic acid group above. Among them, the residual groups of the coupling agent molecules after the reaction can be the first molecular chain, and the residual groups of the linker molecules after the reaction can be the second molecular chain.
[0069] In some embodiments, the mass content of the active component in the suspension of the present application embodiment can be 5% to 40%, which can be optionally 20% to 40%, 20% to 30%, 30% to 40%. In the exemplary embodiment, the mass content of the active component in the suspension of the present application embodiment can be 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% and other typical but non-restrictive sizes, or any size between any two numerical ranges. Controlling the mass content of the active component within this range further promotes the full dispersion of the active component, improves the dispersion stability of the active component, and reduces the local sedimentation of the active component.
[0070] In some embodiments, the active component may include at least one of azoxystrobin, oxadiazine, metalaxyl, imidacloprid, fludioxonil, tebuconazole, metalaxyl-M, and thiofuran. These pesticide active components are widely used in the field of crop pest control, and can effectively control the occurrence and spread of diseases and pests, and improve the yield and quality of crops. Among them, azoxystrobin is a methoxyacrylate fungicide with high efficiency, broad spectrum, prevention, low toxicity, penetration, and systemic activity, and shows good activity against almost all fungal diseases. Oxadiazine is a phenylamide fungicide, which has a unique mechanism of action and a broad-spectrum fungicidal activity specifically for oomycete fungi, as well as low toxicity, systemic, prevention, and treatment. Metalaxyl belongs to phenylamide compounds and is widely used in the prevention and treatment of various plant diseases, especially diseases caused by oomycetes. Imidacloprid is a neonicotinoid insecticide, which is widely used in pest control of various crops and has the characteristics of broad spectrum, low toxicity, and long lasting effect. Fludioxonil is a broad-spectrum, highly effective fungicide, mainly used to control fungal diseases of various crops, and widely used in seed treatment and control of soil-borne diseases in the seedling stage. Tebuconazole is a highly effective, broad-spectrum, systemic triazole fungicide with three functions: protection, treatment, and eradication. It has a broad fungicide spectrum and a long lasting effect. Metalaxyl-M, also known as Metalaxyl-M, is a broad-spectrum, highly effective phenylamide fungicide, mainly used to control diseases caused by Oomycetes. Thifluzamide, as a succinate dehydrogenase inhibitor fungicide, has important application value in modern agriculture due to its unique mechanism of action and broad-spectrum control effect. Its systemic, systemic, long-lasting effect and good protection and treatment effects make it an ideal choice for controlling fungal diseases of various crops.
[0071] It is understandable that in the suspension concentrate of the present application, the active component may be one, two or more than one. For example, in the embodiment, the active component may be azoxystrobin; in another embodiment, the active component may include azoxystrobin and metalaxyl-M.
[0072] In some embodiments, the mass content of the emulsifying dispersant can be 4% to 10%, optionally 4% to 9%, 5% to 8%, 6% to 10%, etc. In the exemplary embodiment, the mass content of the emulsifying dispersant can be 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc., which are typical but non-limiting values, or any value between any two numerical ranges. Controlling the mass content of the emulsifying dispersant within this range further promotes the dispersion of the active component in the suspension of the embodiment of the present application, improves the suspension degree of the active component, improves the dispersion stability of the active component, reduces the local deposition of the active component, and improves the stability of the suspension and the control effect of the pests and diseases.
[0073] In some embodiments, the emulsifying dispersant may include at least one of fatty alcohol polyoxyethylene ether phosphate, sodium lignin sulfonate, polycarboxylate, EO-PO block polyether, and polyoxyethylene polyoxypropylene ether copolymer. These emulsifying dispersants can improve the stability and suspension of active components, reduce the loss of active components, improve the utilization rate of active components, and improve the stability of active components, and extend the shelf life of the suspension. These emulsifying dispersants also help the active components to be better dispersed and penetrated into the plant surface, further improving the control effect of the suspension. Among them, fatty alcohol polyoxyethylene ether phosphate, as an emulsifier and dispersant, can improve the solubility and stability of pesticides, help pesticides better penetrate into the surface of plant leaves, and improve the control effect. Sodium lignin sulfonate has good emulsification, dispersion, suspension and stability properties, and can be used as a dispersant for pesticides to improve the suspension and stability of pesticides, reduce the loss of liquid medicine, and improve the control effect. Polycarboxylate is a high-performance dispersant and emulsifier that can help pesticides better disperse and penetrate into the plant surface and improve the control effect. EO-PO block polyether is a highly efficient emulsifier and dispersant that can help pesticides better penetrate into the surface of plant leaves and improve the control effect. Polyoxyethylene polyoxypropylene ether copolymer is a high-performance emulsifier and dispersant that can help pesticides better disperse and penetrate into the surface of plants and improve the control effect.
[0074] In some embodiments, the mass content of the film-forming agent can be 5% to 10%, and can be optionally 2% to 9%, 2% to 8%, 2% to 5%, 5% to 9%, 6% to 9%, 7% to 10%, and 8% to 10%. In the exemplary embodiment, the mass content of the film-forming agent can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, and other typical but non-limiting values, or any value between any two numerical ranges. When the mass content of the film-forming agent is controlled within this range, when the suspending agent is applied to seed treatment, the film-forming property and coating uniformity can be further improved, the coating shedding rate can be reduced, and the water permeability and air permeability of the seeds can be improved.
[0075] In some embodiments, the film former may include at least one of styrene-acrylic emulsion, acrylate emulsion, polyacrylate, polyvinyl alcohol, chitosan and its derivatives, cellulose and its derivatives.
[0076] In certain embodiments, the mass content of water in the suspending agent of the present application can be 20% to 50%, which can be optionally 20% to 40%, 25% to 60%, 30% to 50%, 60% to 50%, 50% to 60%. In the exemplary embodiment, the mass content of water can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% and other typical but non-restrictive sizes, or any size between any two numerical ranges. Controlling the content of water in the suspending agent of the present application embodiment within this range further improves the stability of the suspending agent, and improves the film-forming effect and coating uniformity of the suspending agent.
[0077] In some embodiments, the suspension concentrate of the present application also includes a wetting agent. The addition of the wetting agent can effectively wet the surface of the active component particles, improve the stability and suspension of the active component, and improve the efficiency of the suspension concentrate preparation. At the same time, it can also help the active component to spread better on plant surfaces such as seeds and leaves, which is conducive to further improving the control effect.
[0078] In some embodiments, the mass content of the wetting agent can be 0.5% to 5%, optionally 1% to 3%, 1% to 2.5%, 1.5% to 2%. In the exemplary examples, the mass content of the wetting agent can be 0.5%, 1%, 1.5%, 2%, 5.5%, 3%, 5.5%, 4%, 4.5%, 5%, etc., which are typical but non-limiting values, or any value between any two numerical ranges. Controlling the mass content of the wetting agent within this range further promotes the attachment of the active component to the seed surface and improves the utilization rate of the active component.
[0079] In some embodiments, the wetting agent may include at least one of alkylphenol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, and 5,6-dibutylnaphthalene-2-sodium sulfonate. These wetting agents can improve the stability and suspension of active components, improve the utilization rate of active components, and reduce the possibility of excessive local concentration of active components causing pesticide damage. For example, alkylphenol polyoxyethylene ether (APEO) can make the active components spread better on the seed surface and improve the control effect. Isomeric alcohol polyoxyethylene ether (ISO) can improve the solubility and stability of active components, help the active components spread better on the seed surface, and improve the control effect. 5,6-dibutylnaphthalene-2-sodium sulfonate (DBS) can help pesticides spread better on the seed surface and improve the control effect.
[0080] In some embodiments, the suspension of the present invention may further include a thickener. The addition of the thickener effectively improves the stability of the suspension and increases the degree of suspension of the active component.
[0081] In some embodiments, the mass content of the thickener can be 0.1% to 0.5%, optionally 0.1% to 0.4%, 0.2% to 0.5%, 0.3% to 0.5%. In the exemplary embodiment, the content of the thickener can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5% and other typical but restrictive values, or any value between any two numerical ranges. Controlling the mass of the thickener to be contained within this range further improves the stability and fluidity of the suspension and improves the control effect of the suspension.
[0082] In some embodiments, the thickener may include at least one of xanthan gum, magnesium aluminum silicate, white carbon black, and cellulose derivatives. The addition of these thickeners can effectively adjust the viscosity of the suspension, making the suspension more stable, thereby improving the control effect of the suspension.
[0083] It should be noted that the tannic acid-modified nano-silica in the suspension of the present application also has a certain thickening effect, which can improve the dispersion stability of the active components in the suspension and adjust the fluidity of the suspension.
[0084] In some embodiments, the suspending agent of the present application embodiment may further include a defoamer. In a further embodiment, the defoamer may include at least one of a polyether-modified silicone defoamer, a polyether-polysiloxane copolymer, and a polyether silane. These defoamers can effectively reduce the surface tension of the liquid, destroy the stability of the bubbles, and make the bubbles dissipate quickly. Adding these defoamers to the suspending agent of the present application embodiment can effectively reduce the formation of foam in the suspending agent, so as to alleviate the foam problem of the suspending agent during preparation and use, and improve the prevention and control effect and utilization rate of the suspending agent.
[0085] In some embodiments, the mass content of the defoamer can be 0.1% to 0.8%, optionally 0.1% to 0.7%, 0.1% to 0.6%, 0.2% to 0.8%, 0.3% to 0.8%. In the exemplary embodiment, the mass content of the defoamer can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% and other typical but non-limiting values, or any value between any two numerical ranges. Controlling the mass content of the defoamer within this range further alleviates the foam problem of the suspension agent during preparation and use, and improves the control effect and utilization rate of the suspension agent.
[0086] In some embodiments, the suspension agent of the present application also includes an antifreeze agent. In a further embodiment, the mass content of the antifreeze agent can be 2% to 4%, optionally 2.5% to 4%, 2.5% to 3%, 2% to 3%. In the exemplary embodiment, the mass content of the antifreeze agent can be 2%, 2.5%, 3%, 3.5%, 4% and other typical but non-restrictive sizes, or any size between any two numerical ranges. In the exemplary embodiment, the antifreeze agent can include at least one of ethylene glycol, propylene glycol, and glycerol. Controlling the mass content of the antifreeze agent within this range, these antifreeze agents can cooperate with other components in the suspension agent, so that the suspension agent maintains good stability in a wider temperature range, thereby further improving the prevention and control effect of the suspension agent and improving the safety of the use of the suspension agent.
[0087] In some embodiments, the suspending agent of the present application also includes a color paste. In further embodiments, the content of the color paste can be 5% to 20%, and can be optionally 5% to 15%, 5% to 10%, or 10% to 20%. In the exemplary embodiment, the mass content of the color paste can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc., which are typical but non-limiting values, or any value between any two numerical ranges. The addition of the color paste can give the suspending agent different colors, thereby playing a warning role.
[0088] In some embodiments, the suspending agent of the present application also includes a preservative. In a further embodiment, the mass content of the preservative can be 0.1% to 0.3%, optionally 0.1% to 0.2%, 0.2% to 0.3%. In the exemplary embodiment, the mass content of the preservative can be 0.1%, 0.15%, 0.2%, 0.25%, 0.3% and other typical but non-restrictive values, or any value between any two numerical ranges. Controlling the mass content of the preservative within this range can effectively inhibit the growth of microorganisms, maintain the stability and effectiveness of the suspending agent, and extend the shelf life of the suspending agent.
[0089] In some embodiments, the preservative may include at least one of 1,2-benzisothiazolin-3-one, isothiazolinone, and sodium benzoate. These preservatives have a good inhibitory effect on the growth of microorganisms, can effectively extend the shelf life of the suspension, and these preservatives have no obvious inhibitory effect on the growth of plants. For example, 1,2-benzisothiazolin-3-one (BIT) has a good inhibitory effect on microorganisms such as bacteria, molds, and yeasts. When used in suspensions, it can effectively extend the shelf life of the product and prevent deterioration caused by microbial contamination. Isothiazolinone (MIT) has a good inhibitory effect on a variety of microorganisms. When used in suspensions, MIT can effectively inhibit the growth of microorganisms such as bacteria and molds, and maintain the stability and effectiveness of the suspension. Sodium benzoate is mainly used to inhibit the growth of bacteria and molds, can play a preservative role, and can prevent the suspension from being contaminated by microorganisms during storage and use.
[0090] In some embodiments, the particle size of the particles contained in the suspension may be less than 5 μm. Controlling the particle size of the particles contained in the suspension to be less than 5 μm can further promote the uniform dispersion of the active components in the suspension, and when the suspension is used for seed treatment, the active components can be better dispersed and spread evenly on the seed surface, thereby improving the control effect of the suspension on pests and diseases, reducing local deposition of active components, and reducing the possibility of phytotoxicity.
[0091] In a second aspect, the present invention provides a method for preparing the suspension concentrate mentioned above. The method for preparing the suspension concentrate in the present invention comprises the following steps: The active component, tannic acid modified nano silicon dioxide, an emulsifying dispersant, a film-forming agent and water are mixed in proportion to obtain a suspension.
[0092] It should be noted that the suspending agent, active component, tannic acid-modified nano-silica and film-forming agent in the preparation method of the embodiment of the present application are the suspending agent, active component, tannic acid-modified nano-silica and film-forming agent mentioned above, which will not be repeated here.
[0093] The suspension prepared by the suspension preparation method of the present application embodiment effectively improves the antioxidant and antibacterial abilities of the suspension, improves the adhesion performance of the suspension, and reduces the amount of the film-forming agent due to the addition of tannic acid-modified nano-silicon dioxide. When the suspension is used for seed treatment, it has a good effect on preventing and controlling plant diseases and insect pests, and the surface of the seed has good water permeability and air permeability, which is conducive to promoting the germination of the seed and the growth of the seedling. In addition, the suspension preparation method of the present application embodiment has few process steps, controllable process parameters, and is suitable for large-scale industrial production.
[0094] In some embodiments, the mixing process may further include the following steps: Step S10: performing a first mixing treatment on the emulsifying dispersant, the tannic acid-modified nano-silicon dioxide and water to obtain a first premixed material; Step S20: performing a second mixing process on the first premixed material and the active component to obtain a second premixed material; Step S30: performing a third mixing process on the second premixed material and the film-forming agent to obtain a suspension.
[0095] By adopting the method of batch mixing treatment, emulsifiers, tannic acid modified nano-silica, active components and film-forming agents are added respectively, so that the solubility, dispersibility and mixing uniformity of the components such as emulsifiers, tannic acid modified nano-silica, active components and film-forming agents in the suspension are further improved.
[0096] Step S10: In step S10, the emulsifier dispersant, tannic acid modified nano silicon dioxide and water are subjected to a first mixing treatment, so that the emulsifier dispersant and tannic acid modified nano silicon dioxide are dispersed in the water to obtain a first premixed material.
[0097] In some embodiments, the water added in the first mixing process may be 60% to 70% of the prescribed amount. In the exemplary embodiment, the water added in the first mixing process may be a typical but non-limiting amount such as 60%, 65%, 70% of the prescribed amount, or any amount between any two numerical ranges. The water content added in the first mixing process is controlled within this range to promote the full dispersion of the emulsifying dispersant and the tannic acid-modified nano-silica.
[0098] In some embodiments, at least one of a wetting agent, a preservative, and a defoaming agent may be added to the first mixing treatment. The addition of these components such as wetting agents, preservatives, and defoaming agents further improves the physical and chemical properties of the prepared suspension. For example, the addition of a wetting agent can effectively wet the active component and improve the preparation efficiency of the suspension preparation method of the embodiment of the present application; the addition of a preservative can effectively extend the shelf life of the prepared suspension; the addition of a defoaming agent can effectively reduce the foam generated during the preparation process, transportation, and use. These wetting agents, preservatives, and defoaming agents are the wetting agents, preservatives, and defoaming agents mentioned above, and will not be repeated here.
[0099] In some embodiments, when a defoamer is added in the first mixing process, the amount of the defoamer added can be 30wt% to 80wt% of the prescription amount. In an exemplary embodiment, when a defoamer is added in the first mixing process, the amount of the defoamer added can be a typical but non-limiting amount such as 30wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt% of the prescription amount, or any amount between any two numerical ranges. The amount of the defoamer added in the first mixing process is controlled within this range to further reduce bubbles in the first premix material and improve the mixing uniformity of the first premix material.
[0100] In some embodiments, the speed of the first mixing process can be 2000-3000 rpm, and the time can be 10-20 minutes. In the exemplary embodiment, the speed of the first mixing process can be 2000 rpm, 2500 rpm, 3000 rpm, etc., which are typical but non-limiting values, or any value between any two numerical ranges; the time of the first mixing process can be 10 minutes, 15 minutes, 20 minutes, etc., which are typical but non-limiting values, or any time between any two numerical ranges. Controlling the speed and time of the first mixing process within this range further promotes the dispersion and mixing of the materials and improves the mixing uniformity of the first premixed material.
[0101] Step S20: In step S20, the first premix material and the active component are subjected to a second mixing process, so that the active component is dispersed in the first premix material to obtain a second premix material.
[0102] In some embodiments, a thickener may be added during the second mixing process, and the viscosity of the second premixed material is effectively adjusted by adding the thickener, thereby improving the stability of the suspending agent. The thickener is the thickener mentioned above, and will not be described in detail here.
[0103] In some embodiments, the speed of the second mixing process can be 2000-3000 rpm, and the time can be 30-60 minutes. In the exemplary embodiment, the speed of the second mixing process can be 2000 rpm, 2500 rpm, 3000 rpm, etc., which are typical but non-limiting values, or any value between any two numerical ranges; the time of the second mixing process can be 30 minutes, 40 minutes, 60 minutes, etc., which are typical but non-limiting values, or any time between any two numerical ranges. Controlling the speed and time of the second mixing process within this range further promotes the dispersion and mixing of the materials and improves the mixing uniformity of the second premixed material.
[0104] In some embodiments, after the second mixing process, the material may be ground. In a further embodiment, the material may be ground using zirconium oxide beads with a particle size of 0.6 to 0.8 mm until the particle size of the material is less than 5 μm. The grinding process further reduces the particle size of the material in the suspension, improves the dispersibility of the active component in the second premixed material, and thus improves the dispersibility of the active component in the suspension.
[0105] Step S30: In step S30, the second premix material and the film-forming agent are subjected to a third mixing treatment, so that the film-forming agent is dissolved and / or swelled and mixed with the second premix material to obtain a suspension.
[0106] In some embodiments, at least one of an antifreeze agent, a color paste neutralizer, and a defoamer can be added to the third mixing process. By adding an antifreeze agent, the applicable temperature range of the suspension agent is further broadened, and the use range of the suspension agent prepared by the preparation method of the embodiment of the present application is expanded; the addition of the color paste can effectively play an identification and warning role; and the addition of the defoamer can further reduce the bubbles generated during the third mixing process, as well as the bubbles generated during the transportation and use of the suspension agent. The antifreeze agent, the color paste neutralizer and the defoamer are the antifreeze agent, the color paste neutralizer and the defoamer mentioned above, and will not be repeated here.
[0107] In some embodiments, the amount of the defoamer added during the third mixing process can be 20wt% to 70wt% of the defoamer prescription amount. In an exemplary embodiment, the amount of the defoamer added during the third mixing process can be a typical but non-limiting amount of 20wt%, 30wt%, 40wt%, 50wt%, 60wt%, 70wt% of the defoamer prescription amount, or any amount between any two numerical ranges. The content of the defoamer during the third mixing process is controlled within this range to further reduce the foam generated during the third mixing process.
[0108] In some embodiments, water may be added in the third mixing process. In a further embodiment, the amount of water added in the third mixing process is 30% to 40% of the prescribed amount. In an exemplary embodiment, the amount of water added in the third mixing process may be 30%, 35%, 40% of the prescribed amount, which is a typical but non-limiting amount, or any amount between any two numerical ranges. Controlling the content of water added in the third mixing process to be within this range further promotes the dissolution and mixing of components such as the film-forming agent in the third mixing process, and further improves the uniformity of the suspension.
[0109] In a third aspect, the embodiments of the present application provide the use of the above-mentioned suspending agent or the suspending agent prepared by the above-mentioned suspending agent preparation method as a seed treatment agent.
[0110] Since the dosage of the film-forming agent in the above suspension concentrate is low, the active ingredients have good dispersion and less local precipitation, and the active ingredients have good adhesion to the plant surface, such as the seed surface, when the suspension concentrate is used as a seed treatment agent, it not only has a good prevention and control effect on pests and diseases, but also the treated seeds have good water permeability and air permeability, which is beneficial to seed germination and seedling growth.
[0111] In some embodiments, when the suspension is used as a seed treatment agent, the treated seeds may include at least one of crop seeds, tree seeds, gardening seeds, grass seeds, and flower seeds. For example, the crop seeds may include at least one of soybean seeds, wheat seeds, rice seeds, corn seeds, sorghum seeds, mung bean seeds, and broad bean seeds; the gardening seeds may include at least one of flower seeds and grass seeds.
[0112] In order to make the above implementation details and operations of the present application clearly understood by those skilled in the art, and to demonstrate the significant improvement in performance of the suspension concentrate of the present application and its preparation method and application, the above technical solution is illustrated by multiple embodiments below.
[0113] 1. Suspension concentrate and its preparation method Example 1 This embodiment provides a suspension agent, which is a 10% azoxystrobin seed treatment suspension agent. In terms of mass percentage, the suspension agent of this embodiment includes the components shown in Table 1. Among them, the tannic acid-modified nano-silica gel of this embodiment has a porous structure and a specific surface area of 350 m 2 / g, the particle size D90 is 400 nm, and the tannic acid group content is 0.14 g / g.
[0114] The preparation method of tannic acid modified nano-silicon dioxide contained in Table 1 Example 1 comprises the following steps: Step A1: Under low-speed stirring at 200 rpm, 0.45 g of the template hexadecyltrimethylammonium chloride (CTAC) was dissolved in 180 mL of 16.7% ethanol aqueous solution at 70 °C to prepare a template mixture. Subsequently, 3.4 mL of 25% ammonia water was added to the template mixture, and 1.5 mL of tetraethyl silicate (TEOS) was added dropwise after the solution was clarified. The speed was adjusted to 230 rpm to continue the reaction. After 24 h of reaction, the solid product was collected by centrifugation and washed with deionized water and ethanol three times to remove the residual reactants. The collected solid product was then placed in a methanol solution containing 0.5% hydrochloric acid and washed overnight to remove the template, taken out, and dried to obtain nano-silica.
[0115] Step A2: Take 1.2 g of nano-silica in the above step A1, disperse it in 30 mL of toluene, add 600 μL of 3-aminopropyltriethoxysilane (KH550) at room temperature, stir the reaction solution for half an hour, heat it to 60 °C, and continue the reaction for 8 hours. After the reaction is completed, collect the product by centrifugation, wash it with deionized water and ethanol three times to remove the residual reactants, and dry it at room temperature to obtain amino-modified nano-silica.
[0116] Step A3: Take 2.0 g of the amino-modified nano-silica in step A2 above and disperse it in 50 mL of deionized water to obtain an amino-modified nano-silica dispersion. Subsequently, add 2 g of a 25% glutaraldehyde aqueous solution to the amino-modified nano-silica dispersion for a first condensation reaction. After stirring the reaction at 40 °C for 3 h, add 5 g of tannic acid to the reaction solution for a second condensation reaction, and stir the reaction for 8 h. After the reaction is completed, collect the solid product by centrifugation, wash it three times with water and ethanol to remove the residual reactants, and dry it at room temperature to obtain tannic acid-modified nano-silica.
[0117] The preparation method of the suspension concentrate of this embodiment comprises the following steps: Step S1: 70% of the water in the prescription amount is mixed with the emulsifying dispersant fatty alcohol polyoxyethylene ether phosphate and polycarboxylate, the wetting agent alkylphenol polyoxyethylene ether, the preservative isothiazolinone, tannic acid modified nano-silica, and half of the modified polyether silicone defoamer (0.2%) in the prescription amount, and cyclically shear-mixed at a temperature below 30° C. and a speed of 2500 rpm for 10 minutes to obtain a first premixed material.
[0118] Step S2: After adding the azoxystrobin technical and the thickener xanthan gum to the first premixed material obtained in step S1, cyclically shearing and mixing at a speed of 2500 rpm for 30 minutes to obtain a uniform mixed solution; zirconium oxide beads with a particle size of 0.6-0.8 mm are added to the mixed solution for sand grinding, and when the particle size of the sand grinding liquid is detected to be less than 5 μm, the material is discharged to obtain a second premixed material.
[0119] Step S3: Add red color paste, the other half of the modified polyether silicone defoamer (0.2%) in the prescription, 0062 film-forming agent and the remaining 30% of water in the prescription to the second premix obtained in step S2, mix and stir for 30 minutes to obtain the 10% myclobutanil seed treatment suspension of the embodiment of the present application.
[0120]
[0121] Example 2 This embodiment provides a suspension concentrate, which is a 10% metalaxyl·azoxystrobin seed treatment suspension concentrate (4%+6%). In terms of mass percentage, the suspension concentrate of this embodiment includes the components shown in Table 1. Among them, the tannic acid modified nano-silica used in this embodiment is the same as the tannic acid modified nano-silica in Example 1.
[0122] The preparation method of the suspension concentrate of this embodiment comprises the following steps: Step S1: 65% of the water in the prescription amount is mixed with the emulsifying dispersant EO-PO block polyether and polycarboxylate, the wetting agent alkylphenol polyoxyethylene ether, the preservative 1,2-benzisothiazolin-3-one, tannic acid-modified nano-silica and half of the modified polyether silicone defoamer in the prescription amount, and cyclically shear-mixed at a temperature below 30° C. and a speed of 2500 rpm for 10 minutes to obtain a first premixed material.
[0123] Step S2: After adding metalaxyl technical, azoxystrobin technical and thickener xanthan gum to the first premix obtained in step S1, cyclically shearing and mixing at a speed of 2500 rpm for 30 minutes to obtain a uniform mixed solution; adding zirconium oxide beads with a particle size of 0.6-0.8 mm to the mixed solution for sand grinding, and discharging when the particle size of the sand grinding liquid is detected to be less than 5 μm to obtain a second premix.
[0124] Step S3: Add red color paste, the other half of the modified polyether silicone defoamer (0.2%) in the prescription amount, 0062 film-forming agent and the remaining 35% of water in the prescription amount to the second premix obtained in step S2, mix and stir for 30 minutes to obtain the 10% metalaxyl·myclobutanil seed treatment suspension (4%+6%) of the embodiment of the present application.
[0125] Example 3 This embodiment provides a suspension concentrate, which is a 11% metalaxyl-m-fludioxonil-azoxystrobin seed treatment suspension concentrate (3.3%+1.1%+6.6%). In terms of mass percentage, the suspension concentrate of this embodiment includes the components shown in Table 1. Among them, the tannic acid-modified nano-silica used in this embodiment is the same as the tannic acid-modified nano-silica in Example 1.
[0126] The preparation method of the suspension concentrate of this embodiment comprises the following steps: Step S1: 60% of the water in the prescription, the emulsifying dispersant EO-PO block polyether and polycarboxylate, the wetting agent isomeric alcohol polyoxyethylene ether, the preservative 1,2-benzisothiazolin-3-one, tannic acid modified nano-silica, and half of the modified polyether silicone defoamer (0.2%) in the prescription are mixed, and the mixture is cyclically sheared and mixed at a speed of 2500 rpm for 10 minutes at a temperature below 30° C. to obtain a first premixed material.
[0127] Step S2: adding metalaxyl-M, fludioxonil and azoxystrobin technical, as well as thickeners xanthan gum and aluminum magnesium silicate to the first premix obtained in step S1, and performing cyclic shear mixing at a speed of 2500 rpm for 30 minutes to obtain a uniform mixed solution; adding zirconium oxide beads with a particle size of 0.6-0.8 mm to the mixed solution for sand grinding, and discharging when the particle size of the sand grinding solution is detected to be less than 5 μm to obtain a second premix.
[0128] Step S3: Add red color paste, the other half of the modified polyether silicone defoamer (0.2%) in the prescription, 0062 film-forming agent and the remaining 40% of water in the prescription to the second premix obtained in step S2, and mix and stir for 30 minutes to obtain the 11% metalaxyl-m-fluthrin-myclobutanil seed treatment suspension of the embodiment of the present application.
[0129] Example 4 This embodiment provides a suspension, which is a 9% azoxystrobin·fludioxonil·thiophanate-methyl (3%+1%+5%) seed treatment suspension. In terms of mass percentage, the suspension includes the components shown in Table 1. The tannic acid-modified nano-silica used in this embodiment is the same as the tannic acid-modified nano-silica in Example 1.
[0130] The preparation method of the suspension concentrate of this embodiment comprises the following steps: Step S1: 70% of the water in the prescription, the emulsifying dispersant polyoxyethylene polyoxypropylene ether copolymer, the wetting agent isobutyl alcohol polyoxyethylene ether and 5,6-dibutylnaphthalene-2-sodium sulfonate, the preservative 1,2-benzisothiazolin-3-one, tannic acid-modified nano-silica, and half of the modified polyether silicone defoamer (0.2%) in the prescription are mixed, and the mixture is cyclically sheared and mixed at a speed of 2500 rpm for 10 minutes at a temperature below 30° C. to obtain a first premixed material.
[0131] Step S2: Add azoxystrobin, fludioxonil and thiophanate-methyl technical drugs, as well as thickeners xanthan gum and magnesium aluminum silicate to the first premixed material obtained in step S1, and circulate shear mixing at a speed of 2500 rpm for 30 minutes to obtain a uniform mixed solution; add zirconium oxide beads with a particle size of 0.6-0.8 mm to the mixed solution for sand grinding, and when the particle size of the sand grinding liquid is detected to be less than 5 μm, discharge the material to obtain a second premixed material.
[0132] Step S3: Add red color paste, the other half of the modified polyether silicone defoamer (0.2%) in the prescription, 0062 film-forming agent and the remaining 30% of water in the prescription to the second premix obtained in step S2, and mix and stir for 30 minutes to obtain the 9% myclobutanil-chlordane-thiophanate-methyl seed treatment suspension of the embodiment of the present application.
[0133] Example 5 This embodiment provides a suspension, which is a 11% imidacloprid·fludioxonil·azoxystrobin (9%+0.3%+1.7%) seed treatment suspension. In terms of mass percentage, the suspension includes the components shown in Table 1. The tannic acid modified nano-silica used in this embodiment is the same as the tannic acid modified nano-silica in Example 1.
[0134] The preparation method of the suspension concentrate of this embodiment comprises the following steps: Step S1: 65% of the water in the prescription, emulsifying and dispersing agents polyoxyethylene polyoxypropylene ether copolymer and polycarboxylate, wetting agent isomeric alcohol polyoxyethylene ether, preservative 1,2-benzisothiazolin-3-one, tannic acid-modified nano-silica and half of the modified polyether silicone defoamer (0.2%) in the prescription are mixed, and cyclically sheared and mixed at a speed of 2500 rpm for 10 minutes at a temperature below 30° C. to obtain a first premixed material.
[0135] Step S2: adding imidacloprid, fludioxonil and azoxystrobin technical drugs, as well as a thickener xanthan gum to the first premixed material obtained in step S1, and cyclically shearing and mixing at a speed of 2500 rpm for 30 minutes to obtain a uniform mixed solution; adding zirconium oxide beads with a particle size of 0.6-0.8 mm to the mixed solution for sand grinding, and discharging when the particle size of the sand grinding liquid is detected to be less than 5 μm to obtain a second premixed material.
[0136] Step S3: Add red color paste, the other half of the modified polyether silicone defoamer (0.2%) in the prescription, 0062 film-forming agent and the remaining 35% of water in the prescription to the second premix obtained in step S2, and mix and stir for 30 minutes to obtain the 11% imidacloprid·fluanid·myclobutanil seed treatment suspension of the embodiment of the present application.
[0137] Example 6 This embodiment provides a suspension, which is a 10% metalaxyl-M·tebuconazole·azoxystrobin (2%+4%+4%) seed treatment suspension. In terms of mass percentage, the suspension includes the components shown in Table 1. The tannic acid-modified nano-silica used in this embodiment is the same as the tannic acid-modified nano-silica in Example 1.
[0138] The preparation method of the suspension concentrate of this embodiment comprises the following steps: Step S1: 65% of the water in the prescription, emulsifying and dispersing agents polyoxyethylene polyoxypropylene ether copolymer and polycarboxylate, wetting agent isomeric alcohol polyoxyethylene ether, preservative 1,2-benzisothiazolin-3-one, tannic acid-modified nano-silica and half of the modified polyether silicone defoamer (0.2%) in the prescription are mixed, and cyclically sheared and mixed at a speed of 2500 rpm for 10 minutes at a temperature below 30° C. to obtain a first premixed material.
[0139] Step S2: adding metalaxyl-M, tebuconazole and myclobutanil technical drugs, as well as thickener xanthan gum to the first premix obtained in step S1, and performing cyclic shear mixing at a speed of 2500 revolutions per minute for 30 minutes to obtain a uniform mixed solution; adding zirconium oxide beads with a particle size of 0.6 to 0.8 mm to the mixed solution for sand milling, and discharging the material when the particle size of the sand milling solution is detected to be less than 5 μm to obtain a second premix.
[0140] Step S3: Add red color paste, the other half of the modified polyether silicone defoamer (0.2%) in the prescription, 0062 film-forming agent and the remaining 35% of water in the prescription to the second premix obtained in step S2, mix and stir for 30 minutes to obtain the 10% metalaxyl-tebuconazole-myclobutanil seed treatment suspension of the embodiment of the present application.
[0141] Example 7 This embodiment provides a suspension, which is a 10% azoxystrobin seed treatment suspension. The composition and preparation method of the suspension in this embodiment are basically the same as those of the suspension in Example 1, except that the content of tannic acid-modified nano-silica in the suspension in this embodiment is 10%.
[0142] Comparative Example 1 This comparative example provides a 10% azoxystrobin seed treatment suspension. The composition and preparation method of the suspension in this comparative example are basically the same as those of the suspension in Example 1, except that nano silicon dioxide is used in the suspension in this comparative example to replace the tannic acid-modified nano silicon dioxide in the suspension in Example 1.
[0143] The preparation method of nano silicon dioxide used in this comparative example comprises the following steps: Step A1: Under low-speed stirring at 200 rpm, 0.45 g of hexadecyltrimethylammonium chloride (CTAC) was dissolved in 180 mL of 16.7% ethanol aqueous solution at 70 °C to prepare a template mixture. Then, 3.4 mL of 25% ammonia water was added to the template solution. After the solution was clarified, 1.5 mL of tetraethyl silicate (TEOS) was added dropwise, and the speed was adjusted to 230 rpm to continue the reaction. After 24 h of reaction, the solid product was collected by centrifugation and washed with deionized water and ethanol three times to remove the residual reactants. The solid product obtained by mobile phone was then placed in a methanol solution containing 0.5% hydrochloric acid and washed overnight to remove the template, taken out, and dried to obtain nano-silica.
[0144] Comparative Example 2 This comparative example provides a 10% metalaxyl·myclobutanil (4%+6%) seed treatment suspension.
[0145] The composition and preparation method of the suspension concentrate of this comparative example are basically the same as those of the suspension concentrate of Example 2, except that the nano-silicon dioxide same as that of the comparative example 1 is used in the suspension concentrate of this comparative example to replace the tannic acid-modified nano-silicon dioxide in the suspension concentrate of Example 2.
[0146] Comparative Example 3 This comparative example provides an 11% metalaxyl-M·fluanid·myclobutanil (3.3%+1.1%+6.6%) seed treatment suspension.
[0147] The composition and preparation method of the suspension concentrate of this comparative example are basically the same as those of the suspension concentrate of Example 3, except that the tannic acid-modified nano-silicon dioxide in the suspension concentrate of Example 3 is replaced by the nano-silicon dioxide same as that in the comparative example 1.
[0148] Comparative Example 4 This comparative example provides a 9% azoxystrobin·fludioxonil·thiophanate-methyl (3%+1%+5%) seed treatment suspension.
[0149] The composition and preparation method of the suspension concentrate of this comparative example are basically the same as those of the suspension concentrate of Example 4, except that the nano-silicon dioxide same as that of the comparative example 1 is used in the suspension concentrate of this comparative example to replace the tannic acid-modified nano-silicon dioxide in the suspension concentrate of Example 4.
[0150] Comparative Example 5 This comparative example provides an 11% imidacloprid·fluanid·myclobutanil (9%+0.3%+1.7%) seed treatment suspension.
[0151] The composition and preparation method of the suspension concentrate of this comparative example are basically the same as those of the suspension concentrate of Example 5, except that the nano-silicon dioxide same as that of the comparative example 1 is used in the suspension concentrate of this comparative example to replace the tannic acid-modified nano-silicon dioxide in the suspension concentrate of Example 5.
[0152] Comparative Example 6 This comparative example provides a 10% metalaxyl-M·tebuconazole·myclobutanil (2%+4%+4%) seed treatment suspension.
[0153] The composition and preparation method of the suspension concentrate of this comparative example are basically the same as those of the suspension concentrate of Example 6, except that the nano-silicon dioxide same as that of the comparative example 1 is used in the suspension concentrate of this comparative example to replace the tannic acid-modified nano-silicon dioxide in the suspension concentrate of Example 6.
[0154] Comparative Example 7 This comparative example provides a 10% azoxystrobin seed treatment suspension. The composition and preparation method of the suspension in this comparative example are basically the same as those of the suspension in Example 1, except that the content of tannic acid-modified nano-silica in the suspension in this comparative example is 2%.
[0155] 2. Performance Testing 2.1 Physical and chemical tests The seed treatment suspensions of Examples 1 to 6 and Comparative Examples 1 to 6 were taken to measure the active component mass fraction (%), active component suspension rate (%), pH range, pourability, persistent foam (after 1 min) / ml, wet sieve test (through 75 μm test sieve) / %, low temperature stability (0°C ± 2°C) / 7d, heat storage stability (54°C ± 2°C) / 14d, film forming property, coating uniformity (%), coating shedding rate (%) and other performance parameters. Among them, the active component mass fraction and suspension rate of the suspensions of each embodiment and comparative example are shown in Table 2, and the other test results are shown in Table 3.
[0156]
[0157]
[0158] As shown in Table 2 and Table 3, the active ingredient content in the seed treatment suspension in each embodiment and comparative example meets the composite requirements. Compared with the seed treatment suspension of comparative examples 1 to 6, tannic acid-modified nano-silicon dioxide is added to the seed treatment suspension of Examples 1 to 6, which effectively improves the coating uniformity and reduces the coating shedding rate. This shows that the seed treatment suspension of the embodiment of the present application can effectively improve the film-forming property of the seed treatment suspension, improve the coating uniformity, and reduce the coating shedding rate by compounding tannic acid-modified nano-silicon dioxide with other components.
[0159] The main difference between Example 1, Example 7 and Comparative Example 7 is that the content of tannic acid modified nano-silica is different. Among them, Example 1 has the best coating effect. When the content of tannic acid modified nano-silica is reduced, the coating shedding rate is improved. When the content of tannic acid modified nano-silica is too high, the coating film uniformity is poor, which easily leads to coating shedding, thereby increasing the coating shedding rate.
[0160] 2.2 Biosafety Testing The 10% azoxystrobin seed treatment suspension provided in Example 1 was used to investigate its biosafety to rice, and the 10% azoxystrobin seed treatment suspension produced by Nopco Crop Science Co., Ltd. was used as a control sample, and uncoated rice seeds were used as a blank control (CK group).
[0161] The biosafety test method of rice was as follows: the ratio of liquid to seed was 1 g:50 g, and the amount of 10% azoxystrobin suspension seed coating agent was 200 g / 100 kg of seeds for coating. After 7 days, the length of rice seedlings, root length and average weight were measured. Three parallel groups were tested, 20 rice seeds were added to each group, the temperature of the seedling room was set at 26°C, the relative humidity was 80%, and the rice seeds were planted in nutrient soil. The rice seeds were Taiyou Yuehe Silk Seedlings (Guangdong Jindao Seed Co., Ltd.).
[0162] The results of the rice coating biosafety test are shown in Table 4. The rice growth conditions are shown in Picture 1 shown.
[0163] Table 4
[0164] As shown in Table 4 and Picture 1 As shown, after the rice seeds were coated with the seed treatment suspension of Example 1, 7 days after the rice germinated, the seedling length, root length and average mass were better than those of the rice seeds treated with the control sample, and after the rice seeds were coated with the seed treatment suspension of Example 1, the germination rate of rice and the growth after germination were more similar to those of the blank control group. This shows that the seed treatment suspension provided in the examples of the present application has high biological safety for rice seeds, and the seeds have good water permeability and air permeability after coating.
[0165] 2.3. Investigation of the activity of the pathogen against rice bakanae and wheat take-all disease The seed treatment suspension concentrate of Example 1 was used to test the activity of the seed treatment suspension concentrate against rice bakanae and wheat take-all disease pathogens, and the 10% azoxystrobin seed treatment suspension concentrate of Nopco Crop Science Co., Ltd. under the above 2.2 was used as a control sample.
[0166] Rice Bakanae and Wheat Take-All Test Method: Isolate the Bakanae pathogen from infected rice tissues ( Fusarium fujikuroi) and the isolation of the pathogen of wheat take-all disease from infected wheat tissues ( Fusarium Graminearum ), inoculated onto potato dextrose agar (PDA), and cultured in a constant temperature incubator at 25-28 °C for 5-7 days to obtain fresh mycelium and spores.
[0167] Drug preparation: Dissolve the drug or compound to be tested in an appropriate solvent (such as water, ethanol, etc.) at different concentrations, then add it to the PDA culture medium that has been cooled to about 50°C, mix thoroughly, and pour into a culture dish to prepare the drug-containing culture medium.
[0168] Inoculation of pathogens: Use a borer or inoculation loop to cut a bacterial cake of about 5 mm in diameter from a well-growing pathogen culture medium and place it in the center of the drug-containing culture medium.
[0169] A blank control group without drug was also set up.
[0170] Culture and observation: Place the inoculated culture dish in an incubator at 25-28°C, maintain constant temperature, and culture for 5-7 days. Observe the growth of mycelium and measure the colony diameter of the pathogen every day.
[0171] Calculation of inhibition rate: By comparing the colony diameters of the control group and the treatment group, the inhibition rate of the agent on mycelial growth was calculated.
[0172] Formula: Inhibition rate (%) = (colony diameter of control group - colony diameter of treatment group) / colony diameter of control group * 100% Among them, the indoor activity test results of the seed treatment suspension of Example 1 and the control sample against rice seedling pathogen are shown in Table 5; the indoor activity test results of the seed treatment suspension of Example 1 and the control sample against wheat take-all pathogen are shown in Table 6.
[0173] Table 5
[0174] Table 6
[0175] As shown in Table 5, the EC values of the suspension concentrate of Example 1 and the control sample against the rice seedling pathogen were 50 As shown in Table 6, the EC values of the suspension concentrate of Example 1 and the control sample against wheat take-all pathogen were 0.2140 mg / L and 0.4771 mg / L, respectively. 50 0.5690 mg / L and 1.0211 mg / L respectively. This indicates that the effect of the suspension concentrate of Example 1 on rice bakanae and wheat take-all pathogen is significantly better than that of the control sample, and the activity of the suspension concentrate of Example 1 is increased by about 50%.
[0176] When the suspension provided by the embodiment of the present application is used for seed treatment, the tannic acid modified nano silicon dioxide in the suspension after coating effectively improves the stress resistance of rice as a nutrient element, can effectively alleviate the phytotoxicity caused by the local deposition of azoxystrobin, and alleviate the rice growth inhibition caused by azoxystrobin. At the same time, the high specific surface area of the tannic acid modified nano silicon dioxide in the suspension of the embodiment of the present application can improve the spreading of the active ingredients of the medicine on the seed surface, and while reducing the use of the film-forming agent, under the premise of not affecting the coating rate, coating uniformity, and coating shedding rate, the utilization rate of the active component is effectively improved, and the effect of lasting protection of plants from pests and diseases is achieved. In addition, the suspension provided by the embodiment of the present application also has excellent formula stability, safety of application, and convenient usability.
[0177] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims
1. A suspension concentrate, characterized in that: Taking the mass content of the suspending agent as 100%, the suspending agent includes the following components: Active ingredient 1%~50%; Tannic acid modified nano-silica 3%~15%; Emulsifying dispersant 3%~10%; Film former 2%~10%; Water 20%~60%.
2. The suspending agent according to claim 1, wherein The tannic acid modified nano-silica is a nano-silica having tannic acid groups bonded to its surface, wherein the content of the tannic acid groups in the tannic acid modified nano-silica is 0.09-0.14 g / g; and / or The particle size D90 of the tannic acid modified nano-silica is 200-400 nm; and / or The tannic acid-modified nano-silica has a porous structure; and / or The specific surface area of the tannic acid modified nano-silica is 300-400 m 2 / g.
3. The suspending agent according to claim 2, characterized in that The nano silicon dioxide and the tannic acid group are connected via a connecting bridge molecular chain.
4. The suspension concentrate according to any one of claims 1 to 3, wherein the tannic acid-modified nano-silicon dioxide is prepared by a method comprising the following steps: Using a coupling agent containing an amino group to perform a first modification treatment on the nano-silicon dioxide to obtain amino-modified nano-silicon dioxide; Combining tannic acid groups on the surface of the amino-modified nano-silica to obtain the tannic acid-modified nano-silica; in, The coupling agent includes at least one of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a phosphate coupling agent, and a boric acid coupling agent, and the silane coupling agent includes at least one of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; The specific surface area of the nano-silicon dioxide is 350-450 m 2 / g; The first modification treatment includes at least one of the following (1) to (4): (1) In the first modification treatment, the mass ratio of the nano-silica to the coupling agent is 1:(0.4-1); (2) The reaction temperature of the first modification treatment is 40-100°C; (3) The first modification treatment time is 8 to 24 hours; (4) The solvent of the first modification treatment includes a non-polar solvent, and the non-polar solvent includes at least one of toluene, xylene, and n-hexane.
5. The suspension concentrate according to claim 4, characterized in that The tannic acid groups are bonded to the surface of the amino-modified nano-silica by a method comprising the following steps: The amino-modified nano-silica and the linker are subjected to a first condensation reaction to obtain the aldehyde-modified nano-silica; The aldehyde-modified nano-silica is subjected to a second condensation reaction with tannic acid to obtain the tannic acid-modified nano-silica; Wherein, the temperature of the first condensation reaction and the second condensation reaction are independently 20-60°C; The solvents for the first condensation reaction and the second condensation reaction independently include water; The linking agent includes at least one of the following (1) to (3): (1) The linker molecule contains two or more aldehyde groups; (2) If the linker molecule contains two aldehyde groups, the number of atoms in the molecular segment between the two aldehyde groups is 3 to 5; (3) The linking agent includes at least one of glutaraldehyde, dialdehyde polyethylene glycol, adipaldehyde, and heptanedialdehyde.
6. The suspending agent according to any one of claims 1 to 3, characterized in that The active ingredient comprises at least one of azoxystrobin, dimethomorph, metalaxyl, imidacloprid, fludioxonil, tebuconazole, metalaxyl-M, and thiophanate-methyl; and / or The emulsifying dispersant comprises at least one of fatty alcohol polyoxyethylene ether phosphate, sodium lignin sulfonate, polycarboxylate, EO-PO block polyether, and polyoxyethylene polyoxypropylene ether copolymer; and / or The film former includes at least one of styrene-acrylic emulsion, acrylate emulsion, polyacrylate, polyvinyl alcohol, chitosan and its derivatives, cellulose and its derivatives.
7. The suspending agent according to any one of claims 1 to 3, characterized in that The suspending agent further comprises at least one of a wetting agent, a thickener, a defoaming agent, an antifreeze agent, a color paste and a preservative, and the mass percentage of at least one of the wetting agent, the thickener, the defoaming agent, the antifreeze agent, the color paste and the preservative in the suspending agent is as follows: The mass content of the wetting agent is 0.5%~5%; The mass content of the thickener is 0.1% to 0.5%; The mass content of the defoamer is 0.1% to 0.8%; The mass content of the antifreeze agent is 2%-4%; The mass content of the color paste is 5%-20%; The mass content of the preservative is 0.1%-0.3%; Wherein, the wetting agent includes at least one of alkylphenol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, and 5,6-dibutylnaphthalene-2-sodium sulfonate; The thickener includes at least one of xanthan gum, magnesium aluminum silicate, white carbon black, and cellulose derivatives; The defoamer comprises at least one of a modified polyether silicone defoamer, a polyether polysiloxane copolymer, and a polyether silane; The antifreeze agent includes at least one of ethylene glycol, propylene glycol and glycerol; The preservative includes at least one of 1,2-benzisothiazolin-3-one, isothiazolinone and sodium benzoate.
8. A method for preparing a suspension concentrate, characterized in that: The steps include: The active component, tannic acid-modified nano-silicon dioxide, an emulsifying dispersant, a film-forming agent and water are mixed in proportion to obtain a suspension; Wherein, the suspending agent is the suspending agent according to any one of claims 1-7.
9. The preparation method according to claim 8, characterized in that: The mixing process comprises the following steps: The emulsifying dispersant, tannic acid-modified nano-silicon dioxide and water are subjected to a first mixing treatment to obtain a first premixed material; Performing a second mixing process on the first premixed material and the active component to obtain a second premixed material; The second premixed material is subjected to a third mixing process with a film-forming agent to obtain the suspending agent; Wherein, at least one of a wetting agent, a preservative, and a defoaming agent is also added in the first mixing process; A thickener is also added in the second mixing process; The rotation speeds of the first mixing process and the second mixing process are independently 2000-3000 rpm; After the second mixing process, the material is ground until the particle size is less than 5 μm; In the third mixing process, at least one of an antifreeze agent, a color paste, and a defoaming agent is also added.
10. Use of the suspending agent according to any one of claims 1 to 7 as a seed treatment agent.
Citation Information
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