CN115530160A

CN115530160A - Dry propanil suspending agent and preparation method thereof

Info

Publication number: CN115530160A
Application number: CN202211157719.7A
Authority: CN
Inventors: 任道凯; 倪登辉; 刘小成; 任建荣; 莫知生; 刘晓勇; 谢祥其; 戴色琴
Original assignee: Xianglin Meifeng Biotechnology Huai'an Co ltd
Current assignee: Xianglin Meifeng Biotechnology Huai'an Co ltd
Priority date: 2022-09-22
Filing date: 2022-09-22
Publication date: 2022-12-30
Anticipated expiration: 2042-09-22
Also published as: CN115530160B

Abstract

The invention provides a propanil dry suspending agent and a preparation method thereof. The dry propanil suspending agent comprises a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray-dried particles. The preparation method comprises the following steps: preparing dry suspending agent mother liquor of propanil; preparing dry suspending agent mother powder containing propanil; and fluidizing the dry suspending agent mother powder to form fluidized powder, spraying the dry suspending agent mother liquid to make atomized dry suspending agent mother liquid drops and fluidized powder to be mixed, granulated and dried to obtain the dry suspending agent of propanil. The dry propanil suspending agent has the characteristics of good dispersion stability, high suspension rate and the like, and can fully exert the drug effects of active ingredients such as propanil. The preparation method and the preparation process are easy to control, effectively ensure the stability of the particle morphology, the drug effect and other properties of the prepared propanil dry suspending agent, effectively improve the production efficiency and reduce the production cost.

Description

Dry propanil suspending agent and preparation method thereof

Technical Field

The invention belongs to the technical field of pesticide preparations, and particularly relates to a dry propanil suspending agent and a preparation method thereof.

Background

According to the inquiry, the current propanil technical product and the single-agent and compound-agent products thereof in the domestic market in 8 months by 2022 have 39 registration, wherein 10 technical products are registered, 25 missible oil products are registered, 3 dispersible oil suspending agents are registered, 1 water dispersible granule (which is extruded and granulated cylindrical particles) is registered, and the registering of the propanil single-agent and compound water suspending agent or suspension spraying dry suspending agent product is not available.

The dry suspending agent has good fluidity, dispersibility, spreadability and high biological activity; no organic solvent is used, no dust is generated, and the method is safe for operators, users and the environment; the dry suspending agent is a preparation which is more and more widely applied in recent years, and has all the advantages of granules and high dispersibility of the suspending agent. The preparation process of the pesticide dry suspending agent at the present stage is to prepare water suspension slurry by wet grinding, similar to the preparation of the water suspending agent, and then spray-dry the water suspension slurry in a spray tower to prepare the product.

Generally speaking, the following conditions are required for preparing the compound as a dry suspending agent: the melting point is more than 100 ℃, the solubility in water is less than 200mg/L, and the product is stable in aqueous solution.

The solubility of propanil in water of 130mg/L (20 ℃) meets the first condition of solubility less than 200mg/L, but cannot be achieved at the melting point and under the condition of stability in aqueous solution, because although the pure propanil is white needle-shaped crystals, the commercial propanil content in the market is in the range of 92% -98%, even if the content of the highest 98% is the original, the appearance of the product is not powder or granular but brown flakes, as shown in fig. 1.

The form of the paraffin-like sliced shape is formed because the crude drug of the non-pure product is a coexistent mixture of crystalline particles and amorphous particles, so that the crude drug of the non-pure product has the characteristic of amorphous solid, namely, the material is firstly softened along with the rise of temperature, the crude drug of the non-pure product begins to soften when the temperature is raised to 50 ℃, and the softening degree is obvious after the temperature reaches above 60 ℃ (although the melting point of the crude drug of the pure product of the propanil is 91.5 ℃, 98% of crude drug of the propanil supplied by the actual commercial production supply is obviously softened at 60 ℃); in addition, although propanil is stable at normal pH ranges of 4 to 7, propanil hydrolyses rapidly to 3, 4-dichloroaniline and propionic acid in strongly acidic and alkaline media, propanil rapidly degrades in water in sunlight: photolysis DT50 for 12-13 h. Thus, the low melting softening characteristics of non-pure propanil raw material results in flocculation thickening and difficulty in grinding during the grinding process for preparing the aqueous suspension, which determines that propanil cannot be made into a stable aqueous suspension with a high solid content of more than 40%. In addition, in the spray drying section in the rear end spray tower for preparing the dry suspending agent, the air inlet temperature is generally required to be within 120-180 ℃, the air outlet temperature is within 70-90 ℃, and for the situation that the melting point of a pure product of propanil is only 91.5 ℃ (98% of propanil raw material supplied in actual commercial production is obviously softened at 60 ℃), although the temperature on the surface of the granule is reduced due to instant high-temperature evaporation and heat absorption during high-temperature spray drying, the air inlet temperature of 120-180 ℃ and the air outlet temperature of 70-90 ℃ which continuously exceed the melting point softening point of the propanil raw material are easy to soften and melt to cause the phenomena of difficult granule disintegration and large amount of dead granules.

The conventional preparation process route of the pesticide dry suspending agent at the present stage comprises the following steps:

wet grinding (preparing a high solid content aqueous suspension mother solution with a solid content of more than 40% by wet grinding) → high tower spraying (pumping the mother solution into a spraying tower at a certain pressure to be atomized into dispersed fog drops) → high tower drying (drying and granulating the fog drops by intense heat exchange with hot air flow with a temperature of more than 120 ℃).

Therefore, in the conventional preparation process route of the pesticide dry suspending agent at the present stage, all the required materials are mixed together to prepare an aqueous suspension, and then the aqueous suspension is ground in a grinding machine, in addition to the required fineness of particles in the wet grinding process, the suspension required to be prepared has higher solid content (generally more than 40%, because the low solid content can bring about the quality problems that the active ingredients of the product cannot be high and the product cannot be dried during spray drying to cause overhigh water content, the appearance fluidity of the dry suspending agent is poor, and the product is easy to agglomerate during storage), the high solid content has positive key effects on improving the content of the active ingredients of the product, saving energy during drying, improving the grinding efficiency, increasing the yield and increasing the particle size of the product, but the improvement of the solid content can also bring about the increase of the viscosity of the suspension slurry, causing troubles to the increase of the material temperature during grinding and conveying, particularly the low melting point of non-pure propanil and the obvious softening characteristic of more than 60 ℃, so that the propanil raw material cannot be softened and thicken in the grinding machine due to the low melting point of the propanil, the propanil raw material, and the stable and the propanil suspension cannot be prepared by the continuous grinding temperature, so the flocculation point can not be stably increased.

In addition, propanil degrades rapidly in water in sunlight: when the photolysis DT 50-13 h is prepared into the aqueous suspension agent, the aqueous suspension agent needs to be stored for 2 years on the market, and a completely lightproof closed container is used for packaging, so that the packaging cost is too high in industrialization. Therefore, the factors result in no single or compound aqueous and dry suspending agent product of propanil by 2022 in the current domestic and international markets.

Disclosure of Invention

The application aims to overcome the defects in the prior art and provide the propanil dry suspending agent and the preparation method thereof so as to overcome the technical problem that the existing propanil is difficult to prepare the dry suspending agent.

In order to achieve the purposes of the application, in one aspect of the application, a preparation method of the propanil dry suspending agent is provided. The preparation method of the propanil dry suspending agent comprises the following steps:

preparing a dry suspending agent mother solution of propanil;

preparing dry suspending agent mother powder containing propanil;

fluidizing dry suspending agent mother powder to form fluidized powder, spraying dry suspending agent mother liquor to enable atomized dry suspending agent mother liquor droplets and the fluidized powder to be mixed, granulated and dried to obtain propanil dry suspending agent;

wherein the propanil dry suspending agent comprises a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray-dried particles.

In a second aspect of the application, a dry suspension of propanil is provided. The propanil dry suspending agent comprises a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray-dried particles; wherein, the first and the second end of the pipe are connected with each other,

the fog particle coating growth particles comprise first propanil dry suspending agent particles and propanil dry suspending agent coating layers coated on the surfaces of the first propanil dry suspending agent particles;

the particle agglomeration growth particles comprise at least two agglomerated second propanil dry suspending agent particles, and a solid bridge is formed between every two adjacent second propanil dry suspending agent particles.

Compared with the prior art, the method has the following technical effects:

the preparation method of the dry propanil suspending agent comprises the steps of firstly preparing part of propanil into dry suspending agent mother liquor, firstly preparing dry suspending agent mother powder from part of propanil, enabling atomized dry suspending agent mother liquor droplets to be in contact with fluidized powder dry suspending agent mother powder particles in a mixing granulation process, forming the propanil dry suspending agent in a drying process, enabling the formed propanil dry suspending agent to comprise fog particle coating growth particles, particle agglomeration growth particles, spray drying particles and other particles with shapes and structures, enabling the propanil dry suspending agent to have the characteristics of good dispersion stability, high suspension rate and the like, and being capable of fully playing the drug effects of active ingredients such as propanil and the like. In addition, the preparation method of the propanil dry suspending agent has the advantages that the preparation process is easy to control, the particle morphology, the drug effect and other performances of the prepared propanil dry suspending agent are effectively guaranteed to be stable, the production efficiency is effectively improved, and the production cost is reduced.

The dry propanil suspending agent comprises particles with shapes and structures such as fog particle coating growth particles, particle agglomeration growth particles and spray drying particles, and has the characteristics of good dispersion stability, high suspension rate and the like, and the control effect is good.

Drawings

In order to more clearly illustrate the detailed description of the present application or the technical solutions in the prior art, the drawings used in the detailed description or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is a topography of commercial propanil bulk drug;

FIG. 2 is a schematic flow diagram of a preparation method of a dry propanil suspending agent;

FIG. 3 is a schematic representation of the formation of granules in the fog coating contained in the dry suspending agent of propanil;

FIG. 4 is a schematic diagram showing the particle formation of particle agglomeration growth contained in dry propanil suspending agent;

figure 5 is a schematic representation of the formation of spray-dried particles contained in a dry suspension of propanil.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.

In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.

It should be understood that, in various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass described in the specification of the examples of the present application may be a mass unit known in the chemical field such as μ g, mg, g, kg, etc.

The terms "first" and "second" are used for descriptive purposes only and are used for distinguishing purposes such as substances from one another, and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the present application. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature.

Based on the characteristics of propanil and the preparation process of the existing dry suspending agent as stated in the background art, no single or compound aqueous suspending agent or dry suspending agent product of propanil is available in the current domestic and international markets. Based on the above, the embodiment of the application provides a propanil dry suspending agent and a preparation method thereof. The embodiment of the application provides a preparation method of propanil dry suspending agent, which has the process flow shown in figure 2 and comprises the following steps:

s01: preparing a dry suspending agent mother solution of propanil;

s02: preparing dry suspending agent mother powder containing propanil;

s03: and fluidizing the dry suspending agent mother powder to form fluidized powder, spraying the dry suspending agent mother liquid to make atomized dry suspending agent mother liquid drops and fluidized powder to be mixed, granulated and dried to obtain the dry suspending agent of propanil.

In step S01, the propanil dry suspending agent mother liquor is prepared first, that is, the active ingredient part contained in the propanil dry suspending agent of the embodiment of the present application is prepared into a suspension, so as to be atomized in step S03. The method for preparing the dry suspending agent mother liquor can be prepared according to the existing preparation method of the suspension, for example, after the components are mixed according to the proportion, the wet ball milling treatment is adopted to obtain the dry suspending agent mother liquor. In the examples, the particle size of the solid particles contained in the mother liquor of the dry suspending agent can be controlled by Dv ₉₀ Less than or equal to 5 mu m. The method can be controlled by wet ball millingPreparing the particle size of solid particles contained in the mother liquor of the dry suspending agent, for example, in the wet ball milling process, the refrigeration circulating liquid can be started for cooling, and the mother liquor of the dry suspending agent can be repeatedly ground until the particle size Dv of the solid particles contained in the mother liquor of the dry suspending agent ₉₀ Less than or equal to 5 mu m. By controlling the solid particles contained in the dry suspending agent mother liquor, the stability and uniformity of the dry suspending agent mother liquor, namely the suspension, can be improved, and the atomization effect in the step S03 is improved.

In the embodiment, the solid content of the dry suspending agent mother liquor can be controlled to be 6-35%, further controlled to be 15-35%, and further controlled to be 25-35%. By controlling the solid concentration of the dry suspending agent mother liquor within the range, the components of the dry suspending agent mother liquor can be uniformly dispersed to form uniform suspension, and the dry suspending agent mother liquor has relatively low viscosity, so that the atomization effect of the dry suspending agent mother liquor in the step S03 is improved, and the uniformity of liquid drops subjected to atomization treatment and the processing efficiency of atomization treatment are improved. And the solid content overcomes the technical prejudice that the solid content of the suspension liquid needs to be more than 40wt% in the existing spray drying treatment, and the reverse thinking adopts the suspension liquid which is obviously lower than the solid content of 40wt% and needs to be higher than the industry solid content for atomization treatment, so that the preparation method of the embodiment of the application can effectively prepare the propanil dry suspending agent, and the proportion of the mixture of the fog particle coating growth particles, the particle agglomeration growth particles and the spray drying particles contained in the prepared propanil dry suspending agent is improved, thereby improving the stability of the propanil dry suspending agent and fully playing the drug effect of the propanil dry suspending agent.

In an embodiment, the suspension of the following formula can be prepared from the dry suspending agent mother liquor, for example, the suspension comprises the following components in percentage by mass:

wherein the first active ingredient contained in the dry suspending agent mother liquor contains propanil active ingredient. Of course, other active ingredients may also be present. The other active ingredients can be ingredients which exert the pharmaceutical activity of the other active ingredients independently, and can also be ingredients which can play a role in the synergy of the pharmaceutical activity with propanil. As in the examples, the other active ingredient may include at least one of quinclorac, bispyribac, bensulfuron-methyl, cyhalofop-butyl, metamifop. In addition, the content of the first active ingredient can be adjusted according to actual conditions, such as 5 to 20%, and specifically, can be a typical but non-limiting content such as 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 23%, and the like.

The first wetting agent contained in the dry suspending agent mother liquor can comprise at least one of fatty alcohol-polyoxyethylene ether, succinate sulfonate and isomeric alcohol-polyoxyethylene ether, wherein the succinate sulfonate is a further choice, and in a specific embodiment, the succinate sulfonate can be sodium bis (2-ethylhexyl) sulfosuccinate (trade name: GR-7M). These wetting agents can enhance the efficiency and dispersibility properties of the first active ingredient dispersed in the solvent. And the atomization performance of the dry suspending agent mother liquor is improved, and the contact performance of liquid drops formed by atomization and dry suspending agent mother powder particles can be improved, so that the formation of particles such as fog particle coating growth particles, particle agglomeration growth particles, spray drying particles and the like contained in the propanil dry suspending agent is improved, and the content proportion of the particles is adjusted. In addition, the content of the first wetting agent may be adjusted as the case may be, and may be, for example, 2 to 4%, further 2 to 3%, and specifically may be a typical but non-limiting content such as 1%, 2%, 3%, 4%, 5%, and the like.

The first dispersant contained in the dry suspending agent mother liquor can comprise at least one of tristyrylphenol phosphate, aryl polyoxyalkyl sulfate and styrene acrylic acid sodium salt copolymer, wherein the styrene acrylic acid sodium salt copolymer (trade name: ATLOX METASPERSE 100L-LQ) is a relatively further choice. The dispersing agents can effectively play roles of anti-layering and anti-precipitation, the stability of the first active ingredients and the like in the dispersion state of the dry suspending agent mother liquor is improved, and the suspension stability of the dry suspending agent mother liquor is improved, so that the efficiency and the effect of atomization treatment in the step S03 are improved, and the stability of the propanil dry suspending agent particles is improved. And because of the existence of the first dispersing agent, the addition of a viscous agent can be effectively avoided. The content of the first dispersant may be adjusted as needed, and may be, for example, 2 to 8%, specifically, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, and other typical but non-limiting contents.

The first defoaming agent contained in the dry suspending agent mother liquor comprises at least one of a silicone defoaming agent and a polyoxypropylene polyoxyethylene glycerol ether defoaming agent. Among them, silicone-based antifoaming agents (trade name: SAG-1572) are relatively further selected. The defoaming agents can effectively prevent the dry suspending agent mother liquor from generating bubbles in the preparation or atomization treatment, and improve the stability of the dry suspending agent mother liquor dispersion system and the stability of liquid drops in the atomization treatment. In addition, the content of the first defoaming agent can be adjusted according to actual conditions, and specifically, the content can be typical but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, and the like.

Because the dry suspending agent mother liquor contains the first active ingredient of the propanil, based on the specificity of the propanil, when the dry suspending agent mother liquor is prepared, for example, when wet ball milling is adopted, the temperature of the mother liquor is obviously raised and the viscosity of the mother liquor is increased and thickened due to grinding heat release, the mother liquor is flocculated and thickened in a grinder to be difficult to grind and discharge, so that the first active ingredient is difficult to uniformly disperse, namely, the suspension formed by the dry suspending agent mother liquor is unstable, the dispersity is reduced, and the stable suspension is difficult to prepare. In this case, the presence of the stabilizer contained in the dry suspending agent is effective for improving the dispersion stability and uniformity of the first active ingredient, particularly propanil, in the suspension. In the examples, the stabilizer comprises a polymer having an ABA-type EO/PO block polyether structure, wherein the number average molecular weight of the polymer having an ABA-type EO/PO block polyether structure is 2.0 to 3.0 ten thousand, and specifically, 2.6 ten thousand. Compared with the existing dry suspending agent prepared by the industry, the low molecular weight surfactant with the molecular weight of less than 1000 and the molecular weight surfactant with the molecular weight of 1000-10000 are used more, the high molecular weight surfactant with the molecular weight of more than 10000 is used less, and particularly, the high molecular weight surfactant with the molecular weight of more than 2 ten thousand belongs to the ultrahigh molecular weight grade and is hardly used. In the embodiment of the application, a first active ingredient, particularly propanil, is combined, a polymer with an ABA type EO/PO block polyether structure with a molecular weight of more than 2 ten thousand high molecular weight grades is creatively selected as a stabilizer, the polymer with the ABA type EO/PO block polyether structure contains a molecular skeleton with a long hydrophobic group, has a plurality of anchoring groups, can be strongly and firmly adsorbed on the surface of the first active ingredient, particularly propanil particles, forms a perfect irreversible coating layer on the active ingredient, particularly propanil raw drug particles, and simultaneously extends into a solvent like comb teeth to form strong steric hindrance, so that agglomeration of the first active ingredient, particularly propanil particles is effectively prevented, the viscosity of a dry suspending agent mother solution, particularly during grinding, is greatly improved, the stability of the dry suspending agent mother solution is greatly improved, and the storage stability of the propanil dry suspending agent in the embodiment of the application can be effectively improved, for example, the stable state without devitrification can be maintained for 14 days at 54 ℃ +/-2 ℃. In addition, the content of the stabilizer may be adjusted according to the actual situation, and may be, for example, 2 to 5%, specifically, 1%, 2%, 3%, 4%, 5%, and the like, which are typical but not limiting contents.

The solvent contained in the mother liquor of the dry suspending agent can be used as a solvent carrier, such as water, and can also be other solvents, such as harmless volatile solvents.

The dry suspending agent mother powder in the step S02 is prepared by preparing dry powder base materials from part of the active ingredients of the propanil contained in the propanil dry suspending agent in the embodiment of the application, and the dry suspending agent mother liquid in the step S01 is matched, so that the propanil dry suspending agent can be formed by the dry suspending agent mother powder and the dry suspending agent mother liquid in the step S01 in the step S03.

In order to improve the combination of the dry suspending agent mother powder and the dry suspending agent mother liquor in the step S01 and form the propanil dry suspending agent, in the embodiment, the particle size Dv of the dry suspending agent mother powder ₉₀ Can be controlled to 6-10 μm. The dry suspending agent mother powder with the particle size range can improve the fluidization treatment effect in the step S03 and improve the dry suspension between the fluidized powder and the dry suspension in the step S01Uniformity of agent mother liquor combination.

The method for preparing the dry suspending agent mother powder can be used for preparing the existing dry suspending agent mother powder, such as mixing the components according to the proportion and then granulating or prilling. In the embodiment, all materials are mixed according to the components contained in the dry suspending agent mother powder according to the proportion, then the materials are mixed in a conical twin-screw mixer, and then the materials are subjected to superfine grinding or air flow grinding to obtain the dry suspending agent mother powder, and the particle size Dv of the dry suspending agent mother powder is controlled ₉₀ In the range of 6 to 10 μm.

In an embodiment, the dry suspending agent mother powder may include the following components by mass percent:

wherein the second active ingredient contained in the dry suspending agent mother powder contains propanil active ingredient. Of course, other active ingredients may also be present. The other active ingredients can be ingredients which exert the pharmaceutical activity of the other active ingredients independently, and can also be ingredients which can play a role in the synergy of the pharmaceutical activity with propanil. As in the examples, the other active ingredient may include at least one of quinclorac, bispyribac, bensulfuron-methyl, cyhalofop-butyl, metamifop. In addition, the content of the first active ingredient may be adjusted as appropriate, and may be, for example, 40 to 77.8%, specifically, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, and the like, which are typical but not limiting.

The second wetting agent contained in the dry suspending agent mother powder can comprise at least one of sodium dodecyl sulfate (K12) and alkyl naphthyl sulfate (EFW), wherein the sodium dodecyl sulfate is further selected. The wetting agents can improve the contact performance and the combination rate of the dry suspending agent mother powder and atomized dry suspending agent mother liquid drops, so that the formation of particles such as fog particle coating growth particles, particle agglomeration growth particles, spray drying particles and the like contained in the propanil dry suspending agent is improved, and the content ratio of the particles is adjusted. In addition, the content of the second wetting agent may be adjusted according to the actual situation, and may be, for example, 1 to 3%, 1 to 2%, and specifically, 1%, 2%, 3%, 4%, 5%, and the like, which are typical but not limiting.

The second dispersing agent contained in the dry suspending agent mother powder body can comprise at least one of polyacrylate polymer, polycarboxylate sodium salt (CAS: 62601-60-9) and alkyl naphthalene sulfonate ammonium salt, wherein the polyacrylate polymer (trade name: agrilan 782) is a relatively further choice. The dry suspending agent mother powder contains propanil, so that the second active ingredient such as propanil is easy to melt in the processes of mixing the dry suspending agent mother powder and the like, and the dispersing agent is not uniform in dispersion, therefore, the second active ingredient of the dispersing agent, particularly propanil, has special affinity due to the structure, and the second dispersing agent can effectively coat the second active ingredient, particularly propanil, in the processes of mixing the dry suspending agent mother powder and the like, so that when the dry suspending agent mother powder is contacted with the atomization treatment dry suspending agent mother liquid, the combination between the dry suspending agent mother powder and liquid drops can be effectively enhanced, the liquid drops can quickly form a film layer on the surface of the dry suspending agent mother powder particles, the stability of a suspension prepared during use of the dry suspending agent is improved, and the efficacy of the propanil dry suspending agent is improved. Meanwhile, the inventor finds in research that the dispersion effect of the conventional dispersing agent such as sodium lignosulfonate, naphthalenesulfonate NNO and the like in the dry suspending agent mother powder is not ideal or the dispersing effect can not be basically realized, so that the dispersion effect of the second active ingredient such as propanil contained in the dry suspending agent mother powder is not ideal. The content of the second dispersant may be adjusted as needed, and may be, for example, 8 to 18%, 10 to 18%, and specifically, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, and other typical but non-limiting contents.

The second defoaming agent contained in the dry suspending agent mother powder comprises at least one of sodium salt of tallow fatty acid and fatty acid salt. Of these, tallow fatty acid sodium salt (trade name: agnique SOAP L) is a relatively further choice. The antifoaming agents can maintain antifoaming performance after crushing and granulating in the mixing step, and can still maintain good antifoaming function when the prepared propanil dry suspending agent is prepared into suspension liquid when being used, for example, after the dry suspending agent mother powder is completely disintegrated in hard water, the dry suspending agent mother powder is inverted up and down for 30 times, and still has antifoaming function. In addition, the content of the second defoaming agent may be adjusted to be 0 to 0.5%, and more preferably 0.3 to 0.5% in accordance with actual circumstances. Specifically, the content may be typically but not limited to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.

Because the master powder of the dry suspending agent contains the second active ingredient of the propanil, the temperature of the master powder of the dry suspending agent is obviously increased and the viscosity is increased and thickened due to heat release generated in the preparation process, such as mixing, granulating and the like, so that the second active ingredient is difficult to uniformly disperse. In this case, the presence of the flow aid contained in the dry suspending agent master powder can effectively improve the dispersion stability and uniformity of the second active ingredient, particularly propanil, in the dry suspending agent master powder. In an embodiment, the flow aid comprises at least one of precipitated silica, fumed silica, and modified fumed silica, wherein fumed silica and modified fumed silica are relatively further selected, and modified fumed silica, i.e., synthetic X-ray amorphous silica (trade name: HDK N20), is relatively further selected. The modified fumed silica has larger X-ray amorphous silicon dioxide surface area due to the unique production process, and the unique hollow structure enables the modified fumed silica to be firmly adhered to the surfaces of active ingredient particles such as propanil and the like, so that the flow-assisting effect is achieved, the dry suspending agent mother powder is easier to crush, and each component of the dry suspending agent mother powder, particularly the activity of the second active ingredient, is uniformly dispersed. The content of the flow aid may be adjusted as needed, and may be, for example, 3 to 5%, specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and other typical but non-limiting contents.

The filler contained in the mother powder of the dry suspending agent comprises at least one of calcined kaolin and washed kaolin, wherein the washed kaolin is a relatively further choice. The writing filler, particularly the washing kaolin, can improve the dispersion uniformity of each component of the dry suspending agent mother powder in the mixed material, improve the vulcanization treatment effect of the dry suspending agent mother powder in the step S03, and simultaneously can improve the affinity between the dry suspending agent mother powder and the dry suspending agent mother liquid drops formed by atomization treatment.

In step S03, after the dry suspension agent mother powder in fluidized powder and the atomized dry suspension agent mother liquid are mixed and granulated, the atomized dry suspension agent mother liquid droplets contact with the fluidized powder particles of the dry suspension agent mother powder to infiltrate the surfaces of the dry suspension agent mother powder particles. Thus, when the solvent contained in the liquid drops is evaporated during the drying process, part of the fluidized powder particles with moderate infiltration degree can precipitate solids to be condensed on the surfaces of the fluidized powder particles to form coatings, and the formed particles gradually increase outwards layer by layer in a coating growth mode, and finally, the fog particle coating growth particles are obtained, as shown in fig. 3. And connecting part of the excessively infiltrated fluidized powder particles together through a liquid bridge, drying the liquid bridge to form a solid bridge, and gradually agglomerating and growing to obtain powder agglomeration growth particles, wherein the particle agglomeration growth particles are shown in fig. 4. The remainder of the atomized dry suspension mother liquor droplets, particularly the small droplets, which do not wet the surface of the fluidized powder particles, are gradually dried into dry fine-particle spheres during the drying process, such as falling in a fluidized bed, the large droplets are dried into semi-dry-particle spheres, which are then re-wetted with droplets during the fluidization cycle, and the dry fine particles agglomerate or adhere to the larger semi-dry particles to form cumulatively growing spray-dried particles, as shown in fig. 5. Thus, after the drying treatment in step S03, the resulting propanil dry suspension comprises a mixture of fog coated growth particles, powder agglomerated growth particles and spray dried particles.

In the examples, the total amount of the atomized dry suspending agent mother liquor and the fluidized dry suspending agent mother powder can be mixed and granulated according to the following ratio:

the mass ratio of the propanil contained in the mother liquor of the dry suspending agent to the propanil contained in the mother powder of the dry suspending agent is 20-60: (80-40) mixing and granulating. The ratio may further be 15 to 25: (85 to 75), and further, 20 to 25: (85-80). That is, the mass of the propanil contained in the total amount of the atomized dry suspending agent mother liquor accounts for 20-60 percent of the total mass of the propanil contained in the prepared propanil dry suspending agent, and further can be 15-25 percent, and further can be 20-25 percent. The weight of the propanil contained in the total amount of the fluidized dry suspending agent mother powder accounts for 80-40 percent of the total weight of the propanil contained in the prepared propanil dry suspending agent, and further can be 85-75 percent, and further can be 85-80 percent. By controlling the mixing ratio of the total amount of the atomized dry suspending agent mother liquor to the total amount of the fluidized dry suspending agent mother powder, the dry suspending agent mother liquor and the dry suspending agent mother powder can be fully mixed, granulated and contacted in the step S03, so that the mixture ratio of fog particle coating growth particles, particle agglomeration growth particles and spray drying particles contained in the generated dry suspending agent can be effectively adjusted, and the pesticide effect of the dry suspending agent of propanil can be effectively improved.

In an embodiment, the fluidization treatment includes at least any one of the following conditions:

the ratio of the distance between the fluidized bed nozzle and the bottom screen to the diameter of the bottom screen can be controlled to be 2-4: 1, further controllable in a range of 2.5 to 3.5:1, and further, 2.8 to 3.2:1.

the wind speed of the bottom net wind is 1.8-3.5 m/s, and can be further controlled to be 2.2-3.0 m/s, and can be further controlled to be 2.5-2.8 m/s.

The air temperature of the inlet air is below the melting point and/or softening point of the propanil technical, for example, the air temperature of the fluidization treatment can be controlled to be 45-58 ℃, further can be controlled to be 50-58 ℃ and further can be controlled to be 53-55 ℃.

By controlling and optimizing the conditions of the fluidization treatment, the fluidization treatment effect of the dry suspending agent mother powder can be effectively adjusted, the falling distance and time of the fluidized powder are increased, the contact probability between the fluidized powder and atomized dry suspending agent mother liquid drops can be improved, and the drying time is prolonged. The control and optimization of the wind temperature can effectively ensure the appearance of propanil particles and avoid melting. Therefore, the quality of the particles formed by the propanil dry suspending agent is improved by controlling the conditions of the fluidization treatment as described above.

In the specific embodiment, when the fluidized bed is used for fluidizing the dry suspending agent mother powder and the dry suspending agent mother powder is in a fluidized state, the conventional fluidized bed and the control process conditions thereof are specifically improved for the dry suspending agent mother powder in step S02, such as the distance from the nozzle of the conventional fluidized bed to the bottom screen: bottom mesh diameter = 0.8-1.2: 1, improving the distance from a fluidized bed nozzle to a boiling bottom net: the diameter ratio of the bottom net is 2-4: 1, further 2.8 to 3.2:1. the improvement of the parameters of the conventional fluidized bed equipment increases the falling stroke of the dry suspending agent mother powder particles of fluidized powder and the dry suspending agent mother liquid drops of atomized powder, thereby increasing the contact probability of the fluidized powder and the dry suspending agent mother liquid drops of atomized powder and increasing the drying retention time, leading the generated propanil dry suspending agent to comprise a mixture of fog particle coating growing particles, particle agglomeration growing particles and spray drying particles, being beneficial to drying and balling of the liquid drops, avoiding the phenomenon that the fog drops are too wet when falling to a bottom net of the fluidized bed, being not beneficial to growing the particles and even sticking the bottom net seriously.

The targeted improvement of the fluidization treatment such as the control process condition of the fluidized bed is specifically to improve the bottom net wind speed of the fluidized bed, namely the wind speed of the inlet wind, from 1.2-1.5 m/s to 1.8-3.5 m/s, further 2.2-3.0 m/s, and further 2.5-2.8 m/s. Because the airflow direction in the fluidized bed is opposite to the falling direction of the fog drops, the atomized dry suspending agent mother liquid drops with the same diameter are heavier than the fog drops, the falling speed of the atomized dry suspending agent mother liquid drops can be effectively reduced by increasing the air inlet speed, the contact probability of fluidized powder and the atomized dry suspending agent mother liquid drops is improved, the drying residence time is increased, and the generated propanil dry suspending agent comprises a mixture of fog particle coating growing particles, particle agglomeration growing particles and spray drying particles.

The targeted improvement of the fluidization treatment, such as the control of the process conditions of the fluidized bed, can control and adjust the stabilization of the fluidization treatment and the temperature of the drying treatment, such as reducing the temperature of the inlet air for the fluidization treatment of the fluidized bed to below the melting point and softening point temperature of propanil, such as 60 ℃, in addition to the improvement and adjustment of the inlet air speed as described above. The air inlet temperature of the conventional spray tower for spray granulation is 120-180 ℃, and the air inlet temperature of the conventional fluidized bed for granulation is 50-80 ℃. In the embodiment of the application, in order to take granulation and quality into consideration, the inlet air temperature after improvement is below 60 ℃, for example, the air temperature for fluidization treatment is controlled to be 45-58 ℃, further, the air temperature can be controlled to be 50-58 ℃, and further, the air temperature can be controlled to be 53-55 ℃. Therefore, the air inlet temperature does not exceed the melting point and the softening point of the propanil raw material, and furthermore, the upper limit of a redundant space for reserving the deviation of the device in long-time operation in actual production is controlled within 58 ℃. In addition, the air inlet temperature of the fluidized bed is not too low, the air inlet temperature is too low to be beneficial to the evaporation of moisture of fog drops, particles in the bed are easy to wet and die, or the quality or stability of the particles forming the propanil dry suspending agent is not ideal.

In the examples, the atomization pressure in the spray treatment may be controlled to 0.30 to 0.50MPa, further 0.35 to 0.45MPa, and further 0.40 to 0.45MPa. The atomizing pressure of the conventional fluidized bed spray gun is controlled between 0.10 Mpa and 0.15Mpa at present, but in the embodiment of the present application, the diameter of the dry suspending agent mother liquid droplets in an atomized state is relatively small by increasing the atomizing pressure of the spray gun, for example, to 0.30 Mpa to 0.50Mpa, further 0.35 Mpa to 0.45Mpa, and further 0.40 Mpa to 0.45Mpa, so that the contact between the dry suspending agent mother liquid droplets and fluidized powder particles is increased, and the drying rate of the dry suspending agent mother liquid droplets is increased. More importantly, the proportion of particles such as fog particle coating growth particles, particle agglomeration growth particles, spray drying particles and the like contained in the generated dry propanil suspending agent can be adjusted, and the stability of the dry propanil suspending agent and the drug effect exertion during application are improved.

Therefore, the preparation method of the dry propanil suspending agent provided by the embodiment of the application prepares the propanil into the dry suspending agent mother liquor, part of the propanil is prepared into the dry suspending agent mother powder, and the dry suspending agent mother liquor in an atomized liquid drop is contacted with the dry suspending agent mother powder in a fluidized powder and is mixed and granulated, so that the propanil dry suspending agent is formed, the prepared propanil dry suspending agent is endowed with the characteristics of good dispersion stability, high suspension rate and the like, and the drug effects of active ingredients such as propanil and the like can be fully exerted. In addition, the preparation method of the propanil dry suspending agent in the embodiment of the application has easily-controlled preparation process, effectively ensures the stability of the particle morphology, the drug effect and other properties of the prepared propanil dry suspending agent, effectively improves the production efficiency and reduces the production cost.

Through detection, the propanil dry suspending agent prepared by the preparation method of the propanil dry suspending agent disclosed by the embodiment of the application comprises a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray drying particles. In the embodiment, the mass ratio of the fog particle coating growth particles, the powder particle agglomeration growth particles and the spray drying particles can be (25-35%): (50-70%): (5% to 15%).

The fog particle coating growth particles comprise a core body of dry suspending agent mother powder particles and a coating layer formed by atomized dry suspending agent mother liquid droplets on the surface of the core body, and are shown in figure 3. Further testing, the particle size Dv of the nucleus body contained in the fog particle coating growth particles ₉₀ 6-30 μm; the coating layer may be at least one layer, and the thickness of the coating layer may be 0.2 to 30 μm. In addition, the mist grain coating growth particles may be primary particles formed by the core body and the coating layer, or cluster particles (secondary particles) formed by agglomeration of at least two primary particles. Thus, the overall particle size of the entire haze coating grown particle may be Dv ₉₀ 6.2 to 600 mu m.

The particle agglomeration growth particles comprise at least two agglomerated dry suspending agent particles, and a solid bridge is formed between every two adjacent dry suspending agent particles, as shown in figure 4; further detecting the particle size Dv of the particle agglomeration growth particles ₉₀ 12 to 800 mu m, and the particle diameter Dv of the dry suspending agent particles contained in the suspension ₉₀ May be 6 to 60 μm.

The spray-dried particles having a particle size Dv as shown in FIG. 5 ₉₀ 8 to 150 mu m. Wherein the spray-dried particles may be primary particles, or at least two primary particles may be agglomeratedFormed cluster particles (secondary particles).

In a second aspect, based on the preparation method of the propanil dry suspending agent, the embodiment of the application also provides a propanil dry suspending agent. The propanil dry suspending agent comprises a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray-dried particles. The dry propanil suspending agent provided by the embodiment of the application comprises particles with shapes and structures such as fog particle coating growth particles, particle agglomeration growth particles and spray drying particles, and has the characteristics of good dispersion stability, high suspension rate and the like, and the control drug effect is good. And the suspending agent is a dry suspending agent, does not contain solvent and does not cause phytotoxicity. According to the bioassay data, even if the dosage is three times higher than that of missible oil, the pesticide damage can not occur, and the control safety is high.

Wherein the foggy particle coating growth particles contained in the propanil dry suspending agent are the foggy particle coating growth particles described in the above preparation method of the propanil dry suspending agent, and as shown in fig. 3, the foggy particle coating growth particles comprise first propanil dry suspending agent particles and a propanil dry suspending agent coating layer coated on the surfaces of the propanil dry suspending agent particles. The first propanil dry suspending agent particles are particles formed by fluidizing the above suspending agent mother powder, and the propanil dry suspending agent coating layer is a coating layer formed by dripping dry suspending agent mother liquid formed by atomizing the dry suspending agent mother liquid into particles formed by fluidizing. Thus, in an embodiment, the ingredients of the first propanil dry suspension granule may be components contained in the above dry suspension concentrate. The coating layer may contain ingredients that are contained in the above dry suspension concentrate. For economy of space, the composition of the first dry suspending agent particles and the coating will not be described in detail herein.

In other embodiments, the first propanil dry suspending agent particles have a particle size Dv ₉₀ 6-30 μm; the coating layer may be at least one layer, and the thickness of the coating layer may be 0.2 to 30 μm. Overall particle size Dv of the whole spray grain coating grown particle ₉₀ May be 6.2 to 600 μm. Wherein the fog particle coating growth particles can be primary particles formed by the first propanil dry suspending agent particles and the propanil dry suspending agent coating layer, or can be primary particles formed by at least two propanil dry suspending agent particlesAnd (4) cluster particles formed by agglomeration of the primary particles.

The particle agglomeration growth particles contained in the dry propanil suspending agent comprise at least two agglomerated second dry propanil suspending agent particles, and a solid bridge is formed between every two adjacent second dry propanil suspending agent particles, as shown in figure 4. Wherein, the second propanil dry suspending agent particles are composite particles formed by contacting the particles formed by fluidizing the dry suspending agent mother powder with atomized dry suspending agent mother liquid drops. Then the second propanil dry suspending agent particles should be the components contained in the above dry suspending agent mother liquor and dry suspending agent mother powder.

In other embodiments, the agglomerated particles have a Dv ₉₀ 12-800 μm, and the particle diameter Dv of the second propanil dry suspending agent particles contained in the suspension is ₉₀ May be 6 to 60 μm.

The dry suspension of propanil contains spray-dried particles having a particle size Dv as shown in FIG. 5 ₉₀ Is 8-150 μm.

By controlling the particle sizes of the fog particle coating growth particles, the particle agglomeration growth particles and the spray drying particles, the dispersion stability, the suspension rate and other characteristics of the propanil dry suspending agent in the embodiment of the application can be effectively improved, and the drug effect of the propanil dry suspending agent in the embodiment of the application can be improved.

In other examples, the dry suspending agent for propanil in the examples of the present application may contain the following spray-coated growth particles, agglomerated particle growth particles and spray-dried particles in a mass ratio of (25% to 35%): (50-70%): (5% to 15%). By adjusting the content ratio of the fog particle coating growth particles, the particle agglomeration growth particles and the spray drying particles, the dispersion stability, the suspension rate and other characteristics of the propanil dry suspending agent in the embodiment of the application can be effectively improved, and the drug effect of the propanil dry suspending agent in the embodiment of the application can be improved.

The application will now be described in further detail with reference to specific dry propanil suspending agents and methods of preparation.

Example 1

This example provides a dry suspension of propanil and a method of preparation. The preparation method of the dry propanil suspending agent comprises the following steps:

s1, preparing 1 kg of mother liquor with solid content of 6 percent (propanil content of 3 percent):

weighing 938.39 g of deionized water, adding 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9), 20 g of dispersant tristyrylphenol phosphate (SOPROPHOR SC, provided by Solvay company), 10 g of stabilizer methacrylate copolymer (ATLOX 4913-LQ- (MV, provided by Croda company), 1 g of defoamer polyoxypropylene polyoxyethylene glycerol ether (X-7823, provided by Jinnan scientific and technology Limited company), 30.61 g of 98% propanil raw material, shearing for 3-5 minutes, grinding, and controlling the grinded material Dv ₉₀ The grain diameter is less than or equal to 5 mu m;

s2, 1 kg of mother powder (39.4% + 10.6%) of propanil-quinclorac with the active ingredient content of 50% is prepared:

365.86 g of calcined kaolin, 10 g of wetting agent sodium dodecyl sulfate (K12), 50g of dispersant polyacrylate polymer (Agrilan 782, provided by Nouyon company), 50g of flow aid precipitation white carbon black, 3 g of defoamer fatty acid salt (DDF), 402.04 g of raw drug of 98% of propanil and 119.1 g of 89% quinclorac are weighed in sequence, mixed and crushed, and the Dv is controlled ₉₀ The grain diameter is within the range of 6-10 μm, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 50% propanil-quinclorac dry suspending agent (40% + 10%):

adding 1 kg of 50% propanil-quinclorac mother powder (39.4% + 10.6%) obtained in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 3% propanil mother solution prepared in the step S1 into the fluidized bed through atomization, dispersion and fog drops, wherein the distance between a nozzle in the fluidized bed and a bottom screen is as follows: the diameter of the bottom net is 2:1, the wind speed is 1.8-3.5 m/s, the atomization pressure of a spray gun is 0.30-0.50 Mpa, the air inlet temperature is selected to be 45-58 ℃, and 50 percent dry suspending agent (40 percent +10 percent) of propanil-quinclorac is obtained after fog particle coating, particle agglomeration and spray drying.

Example 2

s1, preparing 1 kg of mother liquor with the solid content of 15 percent (5 percent of propanil and 3 percent of quinclorac):

weighing 844.27 g of deionized water, adding 50g of a wetting agent succinate sulfonate (GR-7M provided by Nanjing Gutian chemical industry), 10 g of a dispersing agent aryl polyoxyalkyl sulfate (SK-34 SC provided by Star-Fei chemical company), 10 g of a stabilizer ABA type EO/PO block polyether (SYNPERONIC T/908-FL- (CQ) provided by Croda company), 1 g of a defoaming agent organosilicon defoaming agent (SAG-1572 provided by Momentive company), 51.02 g of 98% of propanil raw material, 33.71 g of 89% of quinclorac raw material while stirring, shearing for 3-5 minutes, grinding, and controlling the ground material Dv ₉₀ The grain diameter is less than or equal to 5 mu m;

s2, preparing 1 kg of propanil-quinclorac mother powder (52.5% + 8.5%) with the active ingredient content of 61%:

108.78 g of water-washed kaolin, 50g of wetting agent alkyl naphthyl sodium sulfate (EFW), dispersant sodium polycarboxylate salt (CAS:62601-60-9) 200 g of flow aid modified fumed silica (HDK N20, supplied by WACKER company) 10 g, 98 percent propanil raw material 535.71 g and 89 percent quinclorac 95.51 g, the mixture is crushed, and the Dv is controlled ₉₀ The grain diameter is within the range of 6-10 μm, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 60% propanil-quinclorac dry suspending agent (50% + 10%):

adding 1 kg of 61% propanil-quinclorac mother powder (52.5% + 8.5%) obtained in step S2 into a fluidized bed as a base material, and spraying 1 kg of the prepared 8% propanil-quinclorac mother solution obtained in step S1 into the fluidized bed through atomized dispersed droplets, wherein a nozzle in the fluidized bed is spaced from a bottom screen: the diameter of the bottom net is 4:1, the wind speed is 2.2-3.0 m/s, the spray gun atomization pressure is 0.35-0.45 Mpa, the air inlet temperature is 50-58 ℃, and 60 percent dry suspending agent (50% + 10%) of propanil-quinclorac is obtained after fog particle coating, particle agglomeration and spray drying.

Example 3

s1, preparing 1 kg of mother liquor with the solid content of 35 percent (the propanil content is 20 percent, and the quinclorac content is 5 percent):

weighing 636.74 g of deionized water, adding 20 g of isomeric alcohol polyoxyethylene ether serving as a wetting agent, 30 g of styrene acrylic acid sodium salt copolymer serving as a dispersant (ATOX METASPERSE 100L-LQ- (AP) provided by Croda) while stirring, 50g of polyoxyethylene glycol monobutyl ether serving as a stabilizer (Ethylan NS-500LQ provided by Nanjing Jie) and 3 g of polyoxypropylene polyoxyethylene glycerol ether serving as a defoaming agent (X-7823) provided by Jinnan Ruan science and technology Limited, 204.08 g of propanil with the content of 98 percent and 56.18 g of quinclorac with the content of 89 percent, shearing for 3-5 minutes, grinding, and controlling the Dv of the ground material ₉₀ The grain diameter is less than or equal to 5 mu m;

s2, 1 kg of propanil-quinclorac mother powder (61% + 8.5%) with the active ingredient content of 69.5% is prepared:

37.04 g of water-washed kaolin, 10 g of sodium dodecyl sulfate (K12) as a wetting agent, 180 g of polyacrylate polymer (Agrilan 782, available from Nouryon corporation) as a dispersant, 50g of fumed silica (AEROSIL 200, available from Shanghai Special chemical (Shanghai) Co., ltd.) as a flow aid, 5 g of sodium salt of tallow fatty acid as a defoaming agent (Agnique SOAP L, available from BASF Co., ltd.), 622.45 g of 98% propanil as a raw material and 95.51 g of 89% quinclorac were weighed in this order, mixed and pulverized to control Dv ₉₀ The grain diameter is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 70% propanil-quinclorac dry suspending agent (60% + 10%):

adding 1 kg of mother powder (61% + 8.5%) of 69.5% propanil quinclorac in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 25% propanil quinclorac mother solution prepared in the step S1 into the fluidized bed through atomized dispersed fog drops, wherein a nozzle in the fluidized bed is spaced from a bottom screen: the diameter of the bottom net is 3:1, the wind speed is 2.5-2.8 m/s, the spray gun atomization pressure is 0.40-0.45 Mpa, the air inlet temperature is 53-55 ℃, and 70 percent dry suspending agent (60 percent +10 percent) of propanil-quinclorac is obtained after fog particle coating, particle agglomeration and spray drying.

Example 4

s1, preparing 1 kg of mother liquor with the solid content of 26 percent (the propanil content is 23 percent):

weighing 734.31 g of deionized water, adding 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9), 10 g of dispersing agent tristyrylphenol phosphate (SOPROPHOR SC, provided by Solvay company) while stirring, 10 g of stabilizing agent polyoxyalkylene glycol monobutyl ether (Ethyllan NS-500LQ, provided by Nanjing Jiuirun technologies, inc.), 10 g of defoaming agent organosilicon defoaming agent (SAG-1572, provided by Momentive company), 1 g of 98% content propanil raw drug 234.69 g, shearing for 3-5 minutes, grinding, and controlling the grinded material Dv to be ₉₀ The grain diameter is less than or equal to 5 mu m;

s2, preparing 1 kg of propanil mother powder with an active ingredient content of 77.8 percent:

6.12 g of water-washed kaolin, 10 g of wetting agent sodium dodecyl sulfate (K12), 150 g of dispersant polyacrylate polymer (Agrilan 782, provided by Nouyon company), 35 g of flow aid precipitation white carbon black, 5 g of antifoaming agent tallow fatty acid sodium salt (Agnique SOAP L, provided by BASF company) and 793.88 g of raw drug with 98% content of propanil are weighed in sequence, mixed and crushed, and the Dv is controlled ₉₀ The grain diameter is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 80% dry propanil suspending agent:

adding 1 kg of 77.8% propanil mother powder obtained in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 23% propanil mother powder prepared in the step S1 into the fluidized bed through atomized dispersed fog drops, wherein the distance between a nozzle in the fluidized bed and a bottom screen is as follows: the diameter of the bottom net is 3:1, the wind speed is 2.5-2.8 m/s, the spray gun atomization pressure is 0.40-0.45 Mpa, the air inlet temperature is 53-55 ℃, and 80% dry propanil suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Example 5

s1, preparing 1 kg of mother liquor with the solid content of 25 percent (the propanil content is 5 percent, and the quinclorac content is 10 percent):

weighing 736.62 grams of deionized water, adding 40 grams of a wetting agent succinate sulfonate (GR-7M provided by Nanjing Gutian chemical industry) while stirring, 20 grams of a dispersing agent styrene acrylic acid sodium salt copolymer (ATOX METASPERSE 100L-LQ- (AP) provided by Croda corporation), 30 grams of a stabilizer ABA type EO/PO block polyether (SYNPERONIC T/908-FL- (CQ) provided by Croda corporation, 10 grams of a defoaming agent organosilicon defoaming agent (SAG-1572 provided by Momentive corporation), 51.02 grams of 98 percent content propanil amide raw material, 112.36 grams of 89 percent quinclorac raw material, shearing for 3-5 minutes, grinding, and controlling the ground material Dv ₉₀ The grain diameter is less than or equal to 5 mu m;

s2, preparing 1 kg of mother powder (37.5% + 2.5%) of propanil-quinclorac with the active ingredient content of 40%:

386.26 g of calcined kaolin, 20 g of wetting agent alkyl naphthyl sodium sulfate (EFW), 80 g of dispersant alkyl naphthalene sulfonic acid ammonium salt (DISPERSOL PSR 19-PW- (TH) provided by Croda corporation), 100 g of flow aid modified fumed silica (HDK N20 provided by WACKER corporation), 3 g of defoaming agent tallow fatty acid sodium salt (Agnique SOAP L provided by BASF corporation), 382.65 g of 98% propanil raw drug and 28.09 g of 89% quinclorac raw drug are weighed in sequence, mixed and crushed, and the Dv is controlled ₉₀ The grain diameter is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 40% propanil-quinclorac dry suspending agent (30% + 10%):

adding 1 kg of 40% propanil-quinclorac mother powder (37.5% + 2.5%) in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 15% propanil-quinclorac mother solution prepared in the step S1 into the fluidized bed through atomized dispersed droplets, wherein a nozzle in the fluidized bed is away from a bottom screen: the diameter of the bottom net is 2.8:1, the wind speed is 2.2-3.0 m/s, the atomization pressure of a spray gun is 0.35-0.45 Mpa, the air inlet temperature is selected to be 50-55 ℃, and 40 percent dry suspending agent (30 percent +10 percent) of propanil-quinclorac is obtained after fog particle coating, particle agglomeration and spray drying.

Example 6

s1, preparing 1 kg of mother liquor with a solid content of 25 percent (the propanil content is 10 percent, and the quinclorac content is 2 percent):

742.49 g of deionized water is weighed, 30 g of wetting agent succinate sulfonate (GR-7M provided by Nanjing Gutian chemical industry), 80 g of dispersant styrene acrylic acid sodium salt copolymer (ATOOX METASPERSE 100L-LQ- (AP) provided by Croda corporation), 20 g of stabilizer ABA type EO/PO block polyether (SYNPERONIC T/908-FL- (CQ) provided by Croda corporation, 3 g of defoamer organosilicon (SAG-1572 provided by Momentive corporation), 102.04 g of 98% content propanil amide raw material and 22.47 g of 89% quinclorac raw material are added while stirring, shearing is carried out for 3-5 minutes, grinding is carried out, and the ground material Dv is controlled ₉₀ The grain diameter is less than or equal to 5 mu m;

s2, preparing 1 kg of propanil-quinclorac mother powder (52.5% + 10.5%) with the active ingredient content of 63 percent:

169.41 g of water-washed kaolin, 30 g of wetting agent sodium dodecyl sulfate (K12), 100 g of dispersant polyacrylate polymer (Agrilan 782, provided by Nouyon company), 30 g of flow aid modified fumed silica (HDK N20, provided by WACKER company), 4 g of antifoaming agent tallow fatty acid sodium salt (Agnique SOAP L, provided by BASF company), 408.16 g of 98% propanil raw drug and 258.43% quinclorac raw drug are weighed in sequence, mixed and crushed, and Dv is controlled ₉₀ The grain diameter is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 60% propanil-quinclorac dry suspending agent (40% + 20%):

adding 1 kg of 63% propanil-quinclorac mother powder (52.5% + 10.5%) in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 12% propanil-quinclorac mother solution prepared in the step S1 into the fluidized bed through atomized dispersed fog drops, wherein a nozzle in the fluidized bed is spaced from a bottom screen: the diameter of the bottom net is 3.2:1, the wind speed is 2.5-2.8 m/s, the spray gun atomization pressure is 0.35-0.45 Mpa, the air inlet temperature is selected to be 50-55 ℃, and 60 percent dry suspending agent (40 percent +20 percent) of propanil-quinclorac is obtained after the atomized particle coating, particle agglomeration and spray drying

Example 7

s3, preparing 80% propanil dry suspending agent:

adding 1 kg of 77.8% propanil mother powder obtained in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 23% propanil mother powder prepared in the step S1 into the fluidized bed through atomized dispersed fog drops, wherein the distance between a nozzle in the fluidized bed and a bottom screen is as follows: the diameter of the bottom net is 2.8:1, the wind speed is 2.5-3.0 m/s, the spray gun atomization pressure is 0.40-0.45 Mpa, the air inlet temperature is selected to be 45-55 ℃, and 80 percent dry propanil suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Example 8

s2, preparing 1 kg of propanil mother powder with the active ingredient content of 77.8 percent:

weighing 6.12 g of water-washed kaolin, 10 g of wetting agent sodium dodecyl sulfate (K12), 150 g of dispersant polyacrylate polymer (Agrilan 782, provided by Nourcon corporation), 35 g of white carbon black prepared by flow aid precipitation method, 5 g of defoamer tallow fatty acid sodium salt (Agnique SOAP L, provided by BASF corporation) and 793.88 g of raw material drug with 98% of propanil in sequence, mixing, crushing, and controlling Dv ₉₀ The grain diameter is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 80% propanil dry suspending agent:

adding 1 kg of 77.8% propanil mother powder obtained in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 23% propanil mother powder prepared in the step S1 into the fluidized bed through atomized dispersed fog drops, wherein the distance between a nozzle in the fluidized bed and a bottom screen is as follows: the diameter of the bottom net is 3.2:1, the wind speed is 2.5-2.8 m/s, the spray gun atomization pressure is 0.35-0.45 Mpa, the air inlet temperature is selected to be 45-55 ℃, and 80 percent dry propanil suspending agent is obtained after the atomized particle coating, particle agglomeration and spray drying.

Example 9

This example provides an 80% dry suspension of propanil and a method of preparation. The preparation method of the 80% propanil dry suspending agent comprises the following steps:

weighing 734.31 g of deionized water, adding 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9), 10 g of dispersant tristyrylphenol phosphate (SOPROPHOR SC, provided by Solvay company) while stirring, 10 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ, provided by Nanjing Jietong technology Limited), 1 g of defoamer silicone defoamer (SAG-1572, provided by Momentive company), 234.69 g of 98% content propanil raw drug, shearing for 3-5 minutes, grinding, and controlling the ground material Dv to be ₉₀ The grain diameter is less than or equal to 5 mu m.

s3, preparing 80% propanil dry suspending agent

Adding 1 kg of 77.8% propanil mother powder obtained in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 23% propanil mother powder prepared in the step S1 into the fluidized bed through atomized dispersed fog drops, wherein the distance between a nozzle in the fluidized bed and a bottom screen is as follows: the diameter of the bottom net is 0.8 percent, the wind speed is 1.2 to 1.5m/s, the atomization pressure of a spray gun is 0.1 to 0.15Mpa, the air inlet temperature is selected to be 50 to 60 ℃, and 80 percent dry suspending agent of propanil is obtained after fog particle coating, particle agglomeration and spray drying.

Example 10

734.31 grams of deionized water was weighed,adding 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9) while stirring, 10 g of dispersant tristyrylphenol phosphate (SOPROPHOR SC, provided by Solvay company), 10 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ, provided by Nanjing Jieron science and technology Co., ltd.), 1 g of defoaming agent organosilicon defoaming agent (SAG-1572, provided by Momentive company), 234.69 g of raw material with 98% content of propanil, shearing for 3-5 minutes, grinding, and controlling the grinded material Dv ₉₀ The grain diameter is less than or equal to 5 mu m;

6.12 g of water-washed kaolin, 10 g of wetting agent sodium dodecyl sulfate (K12), 150 g of dispersant polyacrylate polymer (Agrilan 782, provided by Nouyon company), 35 g of flow aid precipitation white carbon black, 5 g of antifoaming agent tallow fatty acid sodium salt (Agnique SOAP L, provided by BASF company) and 793.88 g of raw drug with 98% content of propanil are weighed in sequence, mixed and crushed, and the Dv is controlled ₉₀ The grain diameter is within the range of 6-10 μm, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 80% dry propanil suspending agent:

adding 1 kg of 77.8% propanil mother powder obtained in the step S2 into a fluidized bed as a base material, and spraying 1 kg of 23% propanil mother powder prepared in the step S1 into the fluidized bed through atomized dispersed fog drops, wherein the distance between a nozzle in the fluidized bed and a bottom screen is as follows: the diameter of the bottom net is 1.2, the wind speed is 1.2-1.5 m/s, the atomization pressure of the spray gun is 0.1-0.15 Mpa, the air inlet temperature is 60-80 ℃, and 80% dry propanil suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Comparative example 1

This comparative example provides a dry suspension of propanil and a method of preparation. The preparation method of the dry propanil suspending agent of the comparative example comprises the following steps:

s1, preparing 1 kg of mother liquor with the solid content of 35 percent (the content of quinclorac is 25 percent):

616.1 g of deionized water was weighed, and 20 g of a wetting agent, i.e., an isomeric alcohol polyoxyethylene ether, and a dispersant, i.e., styrene acrylic acid sodium salt copolymer (ATOLOX METASPERSE 100L-LQ- (AP), supplied by Croda corporation), were added under stirring30 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethyllan NS-500LQ, provided by Nanjing Jieron Co., ltd.), 50g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethyllan NS-500LQ, provided by Nanjing Jieron Co., ltd.), 3 g of defoamer polyoxypropylene polyoxyethylene glycerol ether (X-7823, provided by Jinnan Ruan technology Co., ltd.), 280.9 g of 89% quinclorac original drug, shearing for 3-5 minutes, grinding, and controlling the ground material Dv ₉₀ The grain diameter is less than or equal to 5 mu m;

s2, preparing 1 kg of quinclorac mother powder with the active ingredient content of 76.25 percent:

18.3 g of water-washed kaolin, 10 g of wetting agent sodium dodecyl sulfate (K12), 60 g of dispersant polyacrylate polymer (Agrilan 782, provided by Nouyon company), 50g of flow aid fumed silica (AEROSIL 200, provided by Yingchuang specialty Chemicals, inc.), 5 g of defoamer tallow fatty acid sodium salt (Agnique SOAP L, provided by BASF company) and 856.7 g of 89% quinclorac are weighed in sequence, mixed and crushed, and the Dv is controlled to be controlled ₉₀ The grain diameter is within the range of 6-10 μm, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing a 75% quinclorac dry suspending agent:

adding 1 kg of 76.25% quinclorac mother powder in the step S2 into a fluidized bed as a base material, spraying 1 kg of 25% quinclorac mother solution prepared in the step S1 into the fluidized bed through atomizing, dispersing and fogdropping, wherein the distance between a nozzle in the fluidized bed and a bottom screen is as follows: the diameter of the bottom net is 1.2, the wind speed is 1.2-1.5 m/s, the atomization pressure of a spray gun is 0.1-0.15 Mpa, the air inlet temperature is 60-80 ℃, and the 75% quinclorac dry suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Comparative example 2

The comparative example provides a propanil dry suspending agent and a preparation method. The preparation method of the dry propanil suspending agent of the comparative example comprises the following steps:

s1, preparing 1 kg of mother liquor with the solid content of 46 percent (the propanil content is 23 percent) according to the step S1 in the embodiment 4;

s2, preparing and preparing 50% propanil dry suspending agent:

spraying 1 kg of 23% propanil mother liquor prepared in the step S1 into a fluidized bed through atomization, dispersion and fog drop, wherein the distance between a nozzle in the fluidized bed and a bottom net is as follows: the diameter of the bottom net is 4.

Comparative example 3

the method comprises the following steps: 1 kg of mother liquor with a solid content of 50% (propanil content of 40%) was prepared:

weighing 500 g of deionized water, adding 20 g of isomeric alcohol polyoxyethylene ether serving as a wetting agent, 68.8 g of sodium lignosulfonate serving as a dispersing agent, 3 g of polyoxypropylene polyoxyethylene glycerol ether serving as a defoaming agent (X-7823 provided by Jinan Ruan science and technology Co., ltd.) and 408.2 g of 98% propanil raw material while stirring, shearing for 3-5 minutes, grinding, and controlling the grinded material Dv ₉₀ The grain diameter is less than or equal to 5 mu m;

step two: preparing 80% propanil dry suspending agent:

and (3) carrying out spray drying on 1 kg of 40% propanil mother liquor obtained in the step one by using a spray tower at the air inlet temperature of 120-180 ℃ to obtain 80% propanil dry suspending agent.

Comparative example 4

The comparative example provides a conventional extrusion granulation and preparation method of propanil water dispersible granules. The preparation method of the propanil water dispersible granule comprises the following steps:

the method comprises the following steps: preparing 1 kg of mother powder with 80 percent of propanil:

weighing 500 g of water-washed kaolin, 20 g of wetting agent sodium dodecyl sulfate (K12), 68.8 g of dispersant polyacrylate polymer (Agrilan 782, provided by Nouyon company), 3 g of antifoaming agent tallow fatty acid sodium salt (Agnique SOAP L, provided by BASF company) and 408.2 g of 98% propanil raw material, mixing for 3-5 minutes, and carrying out jet milling;

step two: preparing 80% propanil water dispersible granules (conventional extrusion granulation):

and (3) adding 120 g of water into 1 kg of the 80% propanil mother powder obtained in the step one, kneading, extruding, granulating and drying to obtain the 80% propanil water dispersible granule (conventional extrusion granulation).

Dry suspending agent related test and efficacy experiment

1. And (3) carrying out related performance test on the propanil dry suspending agent:

the dry suspending agents of propanil in examples 1 to 10 and the dry suspending agents of comparative examples 1 to 4 were respectively subjected to the following correlation performance tests in table 1 (correlation performance test methods were carried out according to corresponding row standards or national standards), and the correlation performance test parameters are shown in table 1:

TABLE 1

As can be seen from table 1, the dry propanil suspending agent provided in each of examples 1 to 8 of the present application has high granulation quality, and the dry propanil suspending agent contains granule growth granules with fog-particle coating, granule agglomeration growth granules and spray-dried granules, and has stable proportion, no phenomenon that the granules stick to a bottom net or harden, high product suspension rate and good heat storage quality. Examples 9 to 10 provided dry propanil suspending agents having relatively poor granulation quality, a certain sticky bottom net or occurrence of plate hardening, etc., as compared with examples 1 to 8, and a product suspension rate lower than those of examples 1 to 8, but still substantially enabled the preparation of dry propanil suspending agents, and the granulation quality and suspension rate were significantly superior to those of comparative examples 2 and 3. Comparative example 1, although it was possible to produce a relatively good granule quality, did not show the formation of a sticky bottom net or sheeting, due to the absence of propanil as an active ingredient. In contrast, the comparative example 2, which is prepared by a direct spray drying method of mother liquor in a fluidized bed, has poor granulation quality, low suspension rate, the phenomena of sticking a bottom net, hardening and the like, and more importantly, cannot prepare a mixture of mist coating growing granules, particle agglomeration growing granules and spray-dried granules at the same time. Comparative example 3 is that the mother liquor in the conventional spray tower is directly sprayed, dried and granulated, and has the problems of poor suspension rate and unqualified heat storage. Comparative example 4 is a conventional master powder extrusion granulation, and has a problem of low dispersibility.

2. And (3) carrying out related performance test on the propanil dry suspending agent:

the respective effect experiments of the propanil suspending agents of examples 1 to 10 and the respective dry suspending agents of comparative examples were conducted in accordance with the following methods, and the difference in the effect of each dry suspending agent on controlling barnyard grass in paddy fields was measured. Among them, 80% propanil dry suspending agent (example 4), 80% propanil dry suspending agent (example 7), 80% propanil dry suspending agent (example 8), 70% propanil-dichloro dry suspending agent (60 +, example 3), 80% propanil dry suspending agent (examples 9 and 10), 80% propanil WDG (boiling fluidized bed granulation) 80% propanil farm chemical company Limited, 75% quinclorac WDG (conventional extrusion granulation) 75% quinclorac from Jiangsu province center of engineering technical research, 80% propanil dry suspending agent (comparative example 1), 80% propanil dry suspending agent (comparative example 3), 80% propanil water dispersible granules (conventional extrusion granulation, comparative example 4) were selected as test agents. The test is carried out in a five-star reclamation farm early rice direct seeding field in Nanchang city, jiangxi province.

2.1 design of the experiment

2.1.1 test treatment: the details are shown in table 2 below.

TABLE 2 test design

2.1.2 test investigation

The safety and the prevention and treatment effect of the rice are observed by a visual inspection method 3 and 7 days after the application of the pesticide.

Investigating the control effect of the plant 15 and 30 days after the application; the fresh weight control effect is investigated for 30 days.

2.2 test results

2.2.1 visual inspection

2.2.1.1 days after drug administration

The rice grows normally after each treatment for 3 days after the application. Treating part A and part D, wherein the leaves begin to wilt and shed, the upper part is slightly carbonized and the leaves are burnt, and the carbonized area of the leaves is relatively largest; b and C, little leaves begin to wilt and shed, and the leaves are slightly carbonized to occupy a small area; while the remaining treatments were performed on barnyard grass with no signs of intoxication.

2.2.1.2 days after drug administration

After 7 days, the rice is safe and has no phytotoxicity after each treatment. Treating A and D, starting to wilting and scattering in large area, carbonizing and burning leaves, and enabling leaves to be carbonized in the largest specific area; treating the leaf parts of the leaf parts B and C to be wilted and scattered, wherein the leaf parts are slightly carbonized and occupy small area; and treating E, F and H, wherein only small parts of the leaves are wilted and faked, carbonized and burned, and the leaf carbonization area is the minimum; while the leaves have extremely small specific area due to charring and leaf burning when J and K are extremely small, and the symptoms of poisoning G and I are only slightly dwarfed and the leaves are normal.

2.2.2 plant control Effect

The method is carried out according to the pesticide field efficacy test rule (I) GB/T17980.40-2000. The test results are calculated as follows, and the test results are shown in tables 3 and 4 below.

TABLE 3 Dry suspending agent with different formulations and different concentration gradients for preventing and controlling barnyard grass in paddy fields

TABLE 4 statistical table of the control effect of dry suspending agents with different formulations and different concentration gradients for preventing and removing barnyard grass in paddy fields

2.3 conclusion

According to the observation of the whole experiment, the propanil dry suspending agent (example 4) and the propanil-dichloro dry suspending agent (example 3) are safe for the growth of rice. Compared with dry propanil suspending agents (different processing technologies) in other embodiments, the effect of the compound suspending agent on the propanil is quickly exerted, the control effect is obviously preferred, and the early visual inspection control effect is high. And the dry suspending agent of propanil, the dry suspending agent of quinclorac 75% and the water dispersible granule of propanil 80% in the comparative examples 1, 3 and 4 are obviously lower than those in the examples of the application.

According to the observation of the whole experiment, the propanil dry suspending agent (example 4) and the propanil-dichloro dry suspending agent (example 3) are safe for the growth of rice in the whole growth period. After 3 days, the barnyard grass will wither and spread, and part of the leaves will be carbonized and burned. 7 days after the application, the barnyard grass leaves will be wilted and the spreading will be aggravated, and a large area of leaves will be carbonized and burned. The barnyard grass died thoroughly 15 days after the application. Compared with the dry propanil suspending agent (different processing technologies) and the dry propanil-dichloro suspending agent (different processing technologies) in other examples, the dry propanil suspending agent is safe to rice and has no difference. Few leaves of the barnyard grass are carbonized and burnt 3 days after the application. 7 days after the application, the leaves of the low-age barnyard grass are carbonized, the upper parts of part of the large-age barnyard grass only show leaf burning, the stem base parts are normal, the part of the barnyard grass after 15 days after the application restores to normal growth, and the control effect on the barnyard grass is obviously lower than that of a barnyard grass dry suspending agent (example 4) and a propanil-dichloro dry suspending agent (example 3). The propanil dry suspending agent (example 4) and the propanil dichloro dry suspending agent (example 3) are relatively safe to the propanil dry suspending agent (different processing technologies) and the propanil dichloro dry suspending agent (different processing technologies), but have the characteristics of high effect on propanil control and the like. The propanil dry suspending agent in each embodiment of the application is obviously superior to the propanil dry suspending agent, the quinclorac dry suspending agent with the concentration of 75% and the propanil water dispersible granule with the concentration of 80% in the comparative examples 1, 3 and 4 (conventional extrusion granulation and comparative example 4).

When the rice has 4 leaves and 1 core and the barnyard grass has 4 leaves, 80 percent of propanil dry suspending agent (example 4) is applied, 250g of propanil is applied per mu, and the control effect on the barnyard grass plants is 89.96 percent after 15 days; compared with other propanil dry suspending agents (different processing technologies) and a control propanil dry suspending agent (comparative example 3), the amount of the propanil dry suspending agent is 250g per mu, and the control effect of the propanil dry suspending agent is only 83.13% (B), 81.93% (C), 73.49% (E), 71.49% (F), 69.88% (H) and 57.03% (J) 15 days after the propanil dry suspending agent is applied. 80% of propanil dry suspending agent (example 4) is applied, the application amount per mu is 250g respectively, and the control effect on the propanil plants after 30 days is 95.22%; the fresh weight control effect is 96.15 percent. Compared with other dry propanil suspending agents (different processing technologies) and a control dry propanil suspending agent (comparative example 3), the amount of 250g of the suspending agent per mu is only 87.25 percent (B), 85.66 percent (C), 76.89 percent (E), 74.50 percent (F), 72.91 percent (H) and 59.76 percent (J) of the control effect of the plants 30 days after the application, and the fresh weight control effects are 91.07 percent (B), 90.54 percent (C), 80.26 percent (E), 78.91 percent (F), 75.43 percent (H) and 63.12 percent (J) respectively.

70 percent of propanil and dichloro-dry suspending agent is applied, the application amount per mu is 250g respectively, and the effect of preventing the propanil from being applied to the propanil plants is 87.95 percent after 15 days (D). The dosage of the contrast medicament 80 percent propanil dry suspending agent (E, F, H, J) per mu and the dosage of the 75 percent quinclorac dry suspending agent (G, I) per mu are 250G, and the control effect of the plants 15 days after the medicament is only 73.49 percent (E), 71.49 percent (F), 69.88 percent (H), 57.03 percent (J), 43.37 percent (G) and 45.38 percent (I). The control effect on barnyard grass plants is 92.43 percent after 30 days (D); the fresh weight control effect is 94.29 percent (D). The dosage of the contrast medicament 80% propanil dry suspending agent (E, F, H, J) per mu and the dosage of the 75% quinclorac dry suspending agent (G, I) per mu are 250G, the control effect of the plants 30 days after the medicament is only 76.89% (E), 74.50% (F), 72.91% (H), 59.76% (J), 49.00% (G) and 50.20% (I), and the fresh weight control effect is respectively 80.26% (E), 78.91% (F), 75.43% (H), 63.12% (J), 52.13% (G) and 55.16% (I).

In conclusion, the propanil dry suspending agent (example 4) is safe for rice, and the control effect on the propanil is significantly higher than that of the propanil dry suspending agent (different processing techniques) and the control propanil dry suspending agent (comparative example 3). The same is safe to rice, and the effect of preventing and curing barnyard grass is obviously higher than 80% of dry suspending agent (E, F, H, J) and 75% of dry suspending agent (G, I) of quinclorac.

According to the embodiments, the propanil and the compound dry suspending agent thereof provided by the embodiment of the application can prevent and kill the propanil in the paddy field, and are high in control effect, high in control effect and safe for rice. The experimental results show that: when the rice has 4 leaves and 1 core and the barnyard grass has 4 leaves, 80 percent of propanil dry suspending agent (example 4) is applied, and the application amount per mu is as follows: 250g, is safe to rice; the control effect on barnyard grass plants after 15 days is 89.96 percent; after 30 days, the control effect on barnyard grass plants is 95.22 percent; the fresh weight control effect is 96.15 percent. 70 percent of propanil and dichloro-dry suspending agent is applied, the application amount per mu is 250g, the control effect on the barnyard grass plants after 15 days is 87.95 percent, and the control effect on the barnyard grass plants after 30 days is 92.43 percent; the fresh weight control effect is 94.29 percent.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims

1. A preparation method of propanil dry suspending agent comprises the following steps:

preparing dry suspending agent mother liquor of propanil;

preparing dry suspending agent mother powder containing propanil;

fluidizing the dry suspending agent mother powder to form fluidized powder, and spraying the dry suspending agent mother liquid to enable atomized dry suspending agent mother liquid drops and the fluidized powder to be mixed, granulated and dried to obtain the propanil dry suspending agent;

wherein the propanil dry suspending agent comprises a mixture of fog particle coating growth particles, powder particle agglomeration growth particles and spray-dried particles.

2. The production method according to claim 1, characterized in that: the atomization pressure of the spray treatment is 0.30-0.50 Mpa; and/or

The fluidization treatment at least comprises any one of the following conditions:

the ratio of the distance from the nozzle of the fluidized bed to the bottom screen to the diameter of the bottom screen is 2-4: 1;

the wind speed of the bottom net wind is 1.8-3.5 m/s;

the air temperature of the inlet air is below the melting point and/or softening point temperature of the propanil raw medicine.

3. The production method according to claim 2, characterized in that: the air temperature of the fluidization treatment is 45-58 ℃.

4. The production method according to any one of claims 1 to 3, characterized in that: the solid content of the dry suspending agent mother liquor is 6-35 wt%; and/or

The particle size Dv of solid particles contained in the dry suspending agent mother liquor ₉₀ Less than or equal to 5 mu m; and/or

The particle size Dv of the dry suspending agent mother powder ₉₀ 6-10 μm; and/or

The total amount of the dry suspending agent mother liquor subjected to atomization treatment and the total amount of the dry suspending agent mother powder subjected to fluidization treatment are 20-60% according to the mass ratio of propanil contained in the dry suspending agent mother liquor to propanil contained in the dry suspending agent mother powder: (80-40) the mixing granulation treatment is carried out in the ratio.

5. The production method according to any one of claims 1 to 3, characterized in that: the dry suspending agent mother liquor comprises the following components in percentage by mass:

wherein the first active ingredient comprises propanil;

and/or the dry suspending agent mother powder comprises the following components in percentage by mass:

wherein the second active ingredient comprises propanil.

6. The production method according to claim 5, characterized in that: at least one of the first active ingredient and the second active ingredient also comprises other active ingredients, and the other active ingredients comprise at least one of quinclorac, bispyribac-sodium, bensulfuron-methyl, cyhalofop-butyl and metamifop; and/or

The first wetting agent comprises at least one of fatty alcohol-polyoxyethylene ether, succinate sulfonate and isomeric alcohol-polyoxyethylene ether; and/or

The first dispersing agent comprises at least one of tristyrylphenol phosphate, aryl polyoxyalkyl sulfate and styrene acrylic acid sodium salt copolymer; and/or

The first defoaming agent comprises at least one of a silicone defoaming agent and a polyoxypropylene polyoxyethylene glycerol ether defoaming agent; and/or

The stabilizer comprises an ABA type EO/PO block polyether structure polymer, and the number average molecular weight of the polymer is 2.0-3.0 ten thousand; and/or

The second wetting agent comprises at least one of sodium dodecyl sulfate and sodium alkyl naphthyl sulfate; and/or

The second dispersing agent comprises at least one of polyacrylate polymer, sodium polycarboxylate and ammonium alkyl naphthalene sulfonate; and/or

The second defoaming agent comprises at least one of sodium salt and fatty acid salt of tallow fatty acid; and/or

The flowing agent comprises at least one of precipitated white carbon black, fumed white carbon black and modified fumed white carbon black; and/or

The filler comprises at least one of calcined kaolin and water-washed kaolin.

7. The dry propanil suspending agent is characterized in that: a mixture comprising spray-coated growth granules, particle agglomeration growth granules and spray-dried granules; wherein the content of the first and second substances,

the fog particle coating growth particles comprise first propanil dry suspending agent particles and a propanil dry suspending agent coating layer coated on the surfaces of the first propanil dry suspending agent particles;

8. Propanil dry suspension according to claim 7, characterized in that: the fog grain coating growth particles have at least one of the following characteristics:

the particle size Dv of the first propanil dry suspending agent particles ₉₀ 6-30 μm;

the number of the coating layers of the propanil dry suspending agent at least comprises one layer;

the thickness of the coating layer of the dry suspending agent of the propanil is 0.2 to 30 mu m;

the particle diameter Dv of the fog particle coating growth particles ₉₀ 6.2 to 600 mu m.

9. Dry suspending agent of propanil as claimed in claim 7 or 8, characterized in that: the particle size Dv of the second propanil dry suspending agent particles ₉₀ 6-60 μm; and/or

The particle diameter of the particle agglomeration growth particles is Dv ₉₀ 12-800 μm; and/or

The particle size Dv of the spray-dried particles ₉₀ Is 8-150 μm.

10. Dry suspending agent of propanil as claimed in claim 7 or 8, characterized in that: the mass ratio of the fog particle coating growth particles to the powder particle agglomeration growth particles to the spray drying particles is (25-35%): (50-70%): (5% to 15%).