CN115530160B

CN115530160B - Propanil dry suspending agent and preparation method thereof

Info

Publication number: CN115530160B
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: 2023-08-18
Anticipated expiration: 2042-09-22
Also published as: CN115530160A

Abstract

The application provides a propanil dry suspending agent and a preparation method thereof. The propanil dry suspension comprises a mixture of mist coat growth particles, powder agglomerate growth particles and spray dried particles. The preparation method comprises the following steps: preparing a dry suspending agent mother solution of propanil; preparing dry suspending agent mother powder containing propanil; and (3) carrying out fluidization treatment on the dry suspending agent mother powder to form fluidized powder, and carrying out spray treatment on the dry suspending agent mother liquid to enable atomized dry suspending agent mother liquid drops and the fluidized powder to carry out mixed granulation treatment and drying treatment to obtain the propanil dry suspending agent. The propanil dry suspending agent has the characteristics of good dispersion stability, high suspension rate and the like, and can fully exert the drug effect of active ingredients such as propanil and the like. The preparation method and the preparation process are easy to control, the stability of the prepared propanil dry suspending agent in particle morphology, drug effect and other performances is effectively ensured, the production efficiency is effectively improved, and the production cost is reduced.

Description

Propanil dry suspending agent and preparation method thereof

Technical Field

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

Background

According to the inquiry, the current propanil original medicine and single-dose and compound-dose product registration of the propanil original medicine in 8 months of the China market in 2022 are totally 39, wherein the original medicine registration is 10, the emulsifiable concentrate product registration is 25, the dispersible oil suspending agent is 3, the water dispersible granule is 1 (is extrusion granulating cylindrical particles), and the registration of the propanil single-dose and compound-dose water suspending agent or suspension spray 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; as a formulation which has been increasingly used in recent years, the dry suspending agent has all the advantages of granules and has high dispersion property of the suspending agent. The current preparation process of pesticide dry suspending agent is that the water suspension slurry is prepared by wet grinding, which is similar to the preparation of water suspending agent, and then the product is prepared by spray drying in a spray tower.

In general, the preparation of the compounds as dry suspensions requires the following conditions: the melting point is higher than 100 ℃, the solubility in water is lower than 200mg/L, and the product is stable in aqueous solution.

The solubility of propanil raw medicine in water of 130mg/L (20 ℃) meets the first condition that the solubility is less than 200mg/L, but the conditions of melting point and stability in aqueous solution cannot be met, because although propanil pure raw medicine is white needle-like crystal, the raw medicine content of commercial goods on the market is in the range of 92% -98%, even the raw medicine with the highest 98% content, and the appearance is not powder or granular but brown slice-shaped, as shown in figure 1.

The paraffin slice-like morphology is formed because the non-pure propanil raw medicine is a coexisting mixture of crystalline particles and amorphous particles, so the non-pure propanil raw medicine has the characteristic of certain amorphous solid, namely, as the temperature rises, substances soften first, the non-pure propanil raw medicine begins to soften when the temperature rises to 50 ℃, and the softening degree is obvious after reaching more than 60 ℃ (although the melting point of the propanil raw medicine is 91.5 ℃, 98% of the propanil raw medicine actually produced and supplied commercially is obviously softened at 60 ℃); in addition, while the propanil stock is stable at normal pH in the range of 4 to 7, it is rapidly hydrolyzed to 3, 4-dichloroaniline and propionic acid in strong acidic and alkaline media, and propanil rapidly degrades in water in sunlight: and photolytic DT for 12-13 h. Therefore, the low-melting softening property of the non-pure propanil raw material causes that the propanil raw material is flocculated and thickened in the grinding process of preparing the water suspending agent and is difficult to grind, and the factor determines that the propanil cannot be made into a stable water suspension with high solid content of more than 40 percent. In addition, in a spray drying section in a rear spray tower for preparing the dry suspending agent, the air inlet temperature is generally required to be in the range of 120-180 ℃, the air outlet temperature is required to be in the range of 70-90 ℃, and for the melting point of the propanil pure product raw material only 91.5 ℃ (98% of the propanil raw material which is actually commercially produced for supply is obviously softened at 60 ℃), although the temperature of the particle surface can be reduced due to instantaneous high-temperature evaporation heat absorption during high-temperature spray drying, the phenomena of difficult particle disintegration and a large number of dead particles are easily caused by the softening and melting of the propanil raw material particles in the particles due to the continuous air inlet temperature of 120-180 ℃ and the air outlet temperature of 70-90 ℃ which are higher than the melting point softening point of the propanil raw material.

At present, the conventional preparation process route of the pesticide dry suspending agent comprises the following steps:

wet grinding (wet grinding to prepare water suspension mother liquor with high solid content of more than 40%), high tower spraying (spraying mother liquor into spray tower to form dispersed fog drops), high tower drying (the fog drops are subjected to strong heat exchange with hot air flow with the temperature of more than 120 ℃ to be dried and granulated).

Therefore, the first step of the conventional preparation process route of the pesticide dry suspending agent at the present stage is to mix all the required materials together to prepare an aqueous suspension, then the aqueous suspension enters a grinder for grinding, in addition to the required fineness of particles in the wet grinding process, the prepared suspension is required to have higher solid content (generally above 40 percent, because the low solid content can bring about the problems that the active ingredients of the product cannot be high and cannot be dried in the spray drying process, the product water content is too high, the appearance fluidity of the dry suspending agent is poor, the quality problem that the dry suspending agent is easy to agglomerate is caused, the high solid content has positive key effects on improving the content of the active ingredients of the product, saving energy in the drying process, improving the grinding efficiency, increasing the granulating rate and increasing the granularity of the particles of the product, but the increase of the solid content also brings about the viscosity of the suspension, and causes troubles to the increase and transportation of the ground particles of Cheng Liaowen, especially, the low melting point of the non-pure propanil raw material and the obvious softening property above 60 ℃ are caused, in the process of grinding the aqueous suspension with the high solid content, the water content is difficult to melt the propanil raw material to melt in the wet grinding process, the aqueous suspension is easy to cause flocculation in the discharge point of the suspension, the aqueous suspension can not be stable, and the dry suspending agent cannot be stably prepared, and the dry suspending agent cannot be subjected to the stable temperature is difficult to the softening point of the dry suspending agent is not higher than 40 percent because the solid content is difficult to be stably prepared.

In addition, propanil rapidly degrades in water under sunlight: and the photolysis DT is 50-13 h, if the water suspending agent is taken as the water suspending agent and needs to be stored for 2 years on the market, the water suspending agent must be packaged by a completely light-proof closed container, and the packaging cost is too high in industrialization. Thus, these factors have led to the fact that no pesticide enterprises currently have propanil single or formulated aqueous and dry suspension products on the domestic and international markets by 2022, month 8.

Disclosure of Invention

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

In order to achieve the aim of the application, the application provides a preparation method of propanil dry suspending agent. 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 the dry suspending agent mother liquid to mix atomized dry suspending agent mother liquid drops with the fluidized powder, granulating and drying to obtain propanil dry suspending agent;

The propanil dry suspending agent comprises a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray drying particles.

In a second aspect of the application, there is provided a propanil dry suspension. The propanil dry suspending agent comprises a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray drying particles; wherein,,

the fog grain 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;

the particle agglomeration growth granules comprise at least two agglomerated second propanil dry suspending agent granules, and solid bridges are formed between two adjacent second propanil dry suspending agent granules.

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

according to the preparation method of the propanil dry suspending agent, part of propanil is firstly prepared into the dry suspending agent mother liquor, part of propanil is firstly prepared into dry suspending agent mother powder, in the mixing granulation treatment, atomized dry suspending agent mother liquor drops and fluidized powder dry suspending agent mother powder particles can be contacted, in the drying treatment process, the propanil dry suspending agent is formed, and the formed propanil dry suspending agent comprises particles with morphology and structure such as fog particle coating growth particles, particle agglomeration growth particles and spray drying particles, and the propanil dry suspending agent is endowed with the characteristics of good dispersion stability, high suspension rate and the like, and the pesticide effect of active ingredients such as propanil and the like can be fully exerted. In addition, the preparation method of the propanil dry suspending agent has the advantages that the preparation process is easy to control, the stability of the morphology, the drug effect and other performances of the prepared propanil dry suspending agent particles is effectively ensured, the production efficiency is effectively improved, and the production cost is reduced.

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

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.

FIG. 1 is a diagram of the morphology of a commercial propanil original drug;

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

FIG. 3 is a schematic diagram of the formation of fog particle coating growth particles contained in propanil dry suspension;

FIG. 4 is a schematic diagram of the formation of agglomerated grain granules of the particles contained in the propanil dry suspension;

fig. 5 is a schematic illustration of spray-dried granule formation contained in propanil dry suspension.

Detailed Description

In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.

In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.

In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of 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, c may be single or multiple, respectively.

It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of 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 functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in 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 weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be mass units known in the chemical industry field such as mu g, mg, g, kg.

The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. 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 application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.

Based on the characteristics of propanil and the existing preparation process of the dry suspending agent, no pesticide enterprises exist in the domestic and international markets at present, and single-dose or compound water suspending agent and dry suspending agent products of propanil are produced. 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, the technological process of which is shown in figure 2, comprising the following steps:

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

s02: preparing dry suspending agent mother powder containing propanil;

s03: and (3) carrying out fluidization treatment on the dry suspending agent mother powder to form fluidized powder, and carrying out spray treatment on the dry suspending agent mother liquid to enable atomized dry suspending agent mother liquid drops and the fluidized powder to carry out mixed granulation treatment and drying treatment to obtain the propanil dry suspending agent.

In step S01, a dry suspension mother solution of propanil is prepared first, that is, an active ingredient portion contained in the propanil dry suspension of the embodiment of the present application is prepared first into a suspension, so that the propanil dry suspension is atomized in step S03. The method for preparing the dry suspending agent mother solution can be to prepare the dry suspending agent mother solution according to the existing suspending agent preparation method, for example, after mixing the components according to the proportion, wet ball milling treatment is adopted to obtain the dry suspending agent mother solution. In an embodiment, the particle size of the solid particles contained in the dry suspension mother liquor may be controlled to Dv ₉₀ Less than or equal to 5 mu m. The particle size of the solid particles contained in the dry suspending agent mother liquor can be controlled, for example, the wet ball milling treatment can be realized, for example, the freezing circulation liquid can be started for cooling in the wet ball milling treatment process, and the grinding is repeated until the particle size Dv of the solid particles contained in the dry suspending agent mother liquor ₉₀ Less than or equal to 5 mu m. By controlling the solid particles contained in the dry suspension concentrate mother liquor, the stability and uniformity of the dry suspension concentrate mother liquor, i.e. the suspension, can be improved, and the atomization effect in step S03 can be 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%. The solid content concentration of the dry suspending agent mother liquor is controlled in the range, so that the components of the dry suspending agent mother liquor are uniformly dispersed to form uniform suspending liquor, the viscosity is relatively low, the atomization treatment effect in the step S03 is improved, and the uniformity of droplets and the processing efficiency of the atomization treatment are improved. The solid content concentration overcomes the technical prejudice of the existing spray drying treatment that the solid content of the suspension liquid is required to be more than 40wt%, and the reverse thinking adopts the suspension liquid which is obviously lower than the solid content of the industry and is required to be more than 40wt% to carry out atomization treatment, so that the preparation method of the embodiment of the application can effectively prepare the propanil dry suspension agent, and the proportion of the mixture of the fog particle coating growth particles, the particle agglomeration growth particles and the spray drying particles in the prepared propanil dry suspension agent is improved, so that the stability of the propanil dry suspension agent is improved and the drug effect of the propanil dry suspension agent is fully exerted.

In an embodiment, the dry suspension agent mother liquor may be provided as a suspension of the following formulation, such as comprising the following components in mass percent:

wherein the first active ingredient contained in the dry suspension concentrate contains propanil active ingredient. Of course, other active ingredients may also be present. The other active ingredients can be ingredients which can independently exert the pharmaceutical activity of the other active ingredients, and can also be ingredients which can play a role in enhancing the pharmaceutical activity with propanil. As in the examples, the other active ingredient may include at least one of quinclorac, bispyribac-sodium, bensulfuron-methyl, cyhalofop-butyl, oxazoxamide. The content of the first active ingredient may be adjusted according to the actual situation, and may be, for example, 5 to 20%, specifically 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 23%, etc., and typical but not limiting contents are also possible.

The first wetting agent contained in the dry suspension mother liquor may include at least one of fatty alcohol polyoxyethylene ether, succinate sulfonate, and isomeric alcohol polyoxyethylene ether, wherein succinate sulfonate is a further choice, and in a specific embodiment, the succinate sulfonate may be sodium bis (2-ethylhexyl) sulfosuccinate (trade name: GR-7M). The wetting agents can improve the efficiency and dispersibility of the first active ingredient dispersed in the solvent. And the atomization performance of the dry suspending agent mother solution is improved, and the contact performance of droplets 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 ratio of the particles is regulated. In addition, the content of the first wetting agent may be adjusted according to the actual situation, and may be, for example, 2 to 4%, 2 to 3%, and specifically, 1%, 2%, 3%, 4%, 5%, etc., which are typical but not limited thereto.

The first dispersant contained in the dry suspension concentrate may include at least one of tristyrylphenol phosphate, arylpolyoxyalkyl sulfate, and styrene sodium acrylate copolymer, wherein styrene sodium acrylate copolymer (trade name: ATLOX METASERE 100L-LQ) is a relatively further option. The dispersing agents can effectively play roles in anti-layering and anti-precipitation, improve the stability of the first active component and the like in the dispersion state of the dry suspending agent mother liquor, and improve the suspension stability of the dry suspending agent mother liquor, so that the efficiency and the effect of atomization treatment in the step S03 are improved, and the stability of propanil dry suspending agent particles is improved. And the addition of the viscous agent can be effectively avoided due to the existence of the first dispersing agent. The content of the first dispersant may be adjusted according to the actual situation, and may be, for example, 2 to 8%, specifically 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, etc., and typical but not limiting contents are also possible.

The first defoamer contained in the dry suspending agent mother solution comprises at least one of organosilicon defoamer and polyoxypropylene polyoxyethylene glyceryl ether defoamer. Among them, silicone-based antifoaming agents (trade name: SAG-1572) are relatively further options. The defoamers can effectively avoid bubbles generated in the preparation or atomization treatment of the dry suspending agent mother solution, and improve the stability of a dispersion system of the dry suspending agent mother solution and the stability of droplets in the atomization treatment. The content of the first defoaming agent may be adjusted according to the actual conditions, and specifically may be a typical but not limited content such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.

Because the dry suspending agent mother liquor contains the first active ingredient of propanil, when the dry suspending agent mother liquor is prepared based on the specification of propanil, such as wet ball milling treatment, the temperature of the mother liquor is obviously increased and the viscosity is increased to be thickened due to grinding heat release, so that the mother liquor is flocculated and thickened in a grinder to be difficult to grind and discharge, the first active ingredient is difficult to uniformly disperse, namely the suspension formed by the dry suspending agent mother liquor is unstable, the dispersibility is reduced, and the stable suspension is difficult to prepare. In this case, the presence of the stabilizer contained in the dry suspension agent can effectively improve the dispersion stability and uniformity of the first active ingredient, particularly propanil, in the suspension. In an embodiment, the stabilizer comprises an ABA type EO/PO block polyether structured polymer, wherein the ABA type EO/PO block polyether structured polymer has a number average molecular weight of 2.0-3.0 ten thousand, specifically 2.6 ten thousand. Compared with the existing dry suspending agent prepared in industry, the low molecular weight surfactant with the molecular weight lower than 1000 and the molecular weight surfactant with the molecular weight between 1000 and 10000 are more used, the high molecular weight surfactant with the molecular weight higher than 10000 is less used, and particularly the molecular weight more than 2 is very high molecular weight grade and is almost not used. In the embodiment of the application, the polymer of an ABA type EO/PO block polyether structure with the molecular weight higher than 2 ten thousand and the ultra-high molecular weight is creatively selected as a stabilizer in combination with the first active ingredient, particularly propanil, the polymer of the ABA type EO/PO block polyether structure contains a molecular skeleton with a hydrophobic group and long chain, and a plurality of anchoring groups, can be strongly and firmly adsorbed on the surface of the first active ingredient, particularly propanil particles, form a perfect irreversible coating layer on active ingredient, particularly propanil raw drug particles, and simultaneously extend into a solvent like comb teeth to form strong steric hindrance, effectively prevent coalescence among the first active ingredient, particularly propanil particles, reduce the viscosity of a dry suspension mother solution, particularly in the grinding process, greatly improve the stability of the dry suspension mother solution, and can effectively improve the storage stability of the propanil dry suspension, for example, can keep a crystallization-free stable state after being thermally stored for 14 days at 54+/-2 ℃. The content of the stabilizer may be adjusted according to the actual conditions, and may be, for example, 2 to 5%, specifically, 1%, 2%, 3%, 4%, 5%, etc., which are typical but not limited thereto.

The solvent contained in the dry suspension concentrate serves as a solvent carrier, such as water, but may, of course, be other solvents, such as solvents that are not harmful to the environment.

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

In order to enhance the combination of the dry suspension concentrate powder with the dry suspension concentrate in step S01 and form a propanil dry suspension, in an embodiment, the dry suspension concentrate powder has a particle size Dv ₉₀ Can be controlled to be 6-10 mu m. The dry suspending agent mother powder with the particle size range can improve the fluidization treatment effect in the step S03 and improve the combination uniformity of the fluidized state powder and the dry suspending agent mother liquid in the step S01.

The method for preparing the dry suspending agent mother powder can be to prepare the dry suspending agent mother powder according to the prior dry suspending agent mother powder, such as granulating or pelleting after mixing the components according to the proportion. In the embodiment, all materials are mixed according to the proportion of the components contained in the dry suspending agent mother powder, then mixed in a conical double-screw mixer, and subjected to superfine grinding or jet milling 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 6-10 μm.

In an embodiment, the dry suspension agent mother powder may include the following components in percentage by mass:

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 can independently exert the pharmaceutical activity of the other active ingredients, and can also be ingredients which can play a role in enhancing the pharmaceutical activity with propanil. As in the examples, the other active ingredient may include at least one of quinclorac, bispyribac-sodium, bensulfuron-methyl, cyhalofop-butyl, oxazoxamide. The content of the first active ingredient may be adjusted according to the actual situation, and may be, for example, 40 to 77.8%, specifically 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, etc., and typical but not limiting contents are also possible.

The second wetting agent contained in the dry suspension master powder may include at least one of sodium dodecyl sulfate (K12) and sodium alkyl naphthalene sulfate (EFW), wherein sodium dodecyl sulfate is a further option. The wetting agents can improve the contact performance and the combination rate of dry suspending agent mother powder and atomized dry suspending agent mother liquid drops, thereby improving 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 and adjusting the content ratio of the particles. In addition, the content of the second wetting agent may be adjusted according to the actual situation, and may be further 1 to 3%, further 1 to 2%, specifically 1%, 2%, 3%, 4%, 5%, etc., which are typical but not limited thereto.

The second dispersant contained in the dry suspension master powder may include at least one of a polyacrylate polymer, a sodium salt of a polycarboxylic acid (CAS: 62601-60-9), and an ammonium salt of an alkyl naphthalene sulfonate, wherein the polyacrylate polymer (trade name: agrilan 782) is a relatively further option. Because the dry suspending agent mother powder contains propanil, the second active ingredient such as propanil is easy to melt in the process of mixing the dry suspending agent mother powder and the like, so that the dispersion of the second active ingredient is uneven, therefore, the dispersing agent second active ingredient, especially propanil, has special affinity for structural reasons, and the second dispersing agent can effectively coat the second active ingredient, especially propanil, in the process of mixing the dry suspending agent mother powder and the like, thus, when the dry suspending agent mother powder contacts with the atomizing 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 form a film layer on the surfaces of the dry suspending agent mother powder particles rapidly, and meanwhile, the stability of the suspension prepared by the prepared propanil dry suspending agent in use is improved, and the drug effect of the propanil dry suspending agent is improved. Meanwhile, the inventors found in the study that the dispersion effect of conventional dispersants such as sodium lignin sulfonate, naphthalene sulfonate NNO, etc. in the dry suspension master powder is not ideal or the dispersion effect is not substantially achieved, resulting in the unsatisfactory dispersion effect of the second active ingredient such as propanil contained in the dry suspension master powder. The content of the second dispersant may be adjusted according to the actual situation, and may be, for example, 8 to 18%, 10 to 18%, or more specifically, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc., and typical but not limiting contents are also possible.

The second defoamer contained in the dry suspending agent mother powder comprises at least one of beef tallow fatty acid sodium salt and fatty acid salt. Of these, tallow fatty acid sodium salt (trade name: agnique SOAP L) is a relatively further option. The defoamers can maintain defoaming performance after crushing and granulating in the mixing step, and can still maintain good defoaming function when the prepared propanil dry suspending agent is prepared into suspension, for example, after the dry suspending agent mother powder is completely disintegrated in hard water, the defoamer is turned upside down for 30 times and still has the defoaming function. In addition, the content of the second defoaming agent may be adjusted according to the actual situation, and may be further 0 to 0.5%, and may be further 0.3 to 0.5%. Specifically, the content may be, but not limited to, typical content of 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc.

Because the dry suspending agent mother powder contains the second active ingredient of propanil, the second active ingredient is difficult to uniformly disperse because the temperature of the dry suspending agent mother powder 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, based on the specific propanil. In this case, the presence of the glidant contained in the dry suspension master powder can effectively improve the dispersion stability and uniformity of the second active ingredient, particularly propanil, in the dry suspension master powder. In an embodiment, the flow agent comprises at least one of precipitated silica, fumed silica, and modified fumed silica, wherein fumed silica and modified fumed silica are relatively further choices, and modified fumed silica, i.e., synthetic X-ray amorphous silica (trade name: HDK N20), is relatively further choices. Because of the unique production process, the modified gas-phase white carbon black has larger surface area of the X-ray amorphous silicon dioxide and unique hollow structure, so that the modified gas-phase white carbon black can be firmly adhered to the surfaces of active ingredient particles such as propanil and the like, thereby achieving the flow-assisting effect, enabling the dry suspending agent mother powder to be more easily crushed, and enabling the active dispersion of each component of the dry suspending agent mother powder, particularly the second active ingredient, to be uniform. The content of the glidant may be adjusted according to the actual conditions, and may be 3 to 5%, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or the like, and is typically but not limited thereto.

The filler contained in the dry suspension master powder is at least one of calcined kaolin and water-washed kaolin, wherein the water-washed kaolin is a relatively further choice. The writing filler, in particular the kaolin, particularly the water-washed kaolin, can improve the dispersion uniformity of each component of the dry suspending agent mother powder in the mixture, improve the vulcanization treatment effect of the dry suspending agent mother powder in the step S03, and simultaneously improve the affinity between the dry suspending agent mother powder and droplets of the dry suspending agent mother liquid formed by atomization treatment.

In step S03, after the dry suspension agent mother powder in fluidized state and the atomized dry suspension agent mother liquid are mixed and granulated, the atomized dry suspension agent mother liquid droplets will contact with fluidized state powder particles of the dry suspension agent mother powder to infiltrate the surfaces of the dry suspension agent mother powder particles. In this way, when the solvent contained in the liquid drops is evaporated in the drying process, the precipitated solids are coagulated on the surface of the fluidized powder particles to form a coating, 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. The fluidized powder particles which are partially excessively infiltrated are connected together through a liquid bridge, the liquid bridge forms a solid bridge after being dried, and the solid bridge gradually agglomerates and grows up, so that the powder particle agglomerated growth particles are obtained, and the powder particle agglomerated growth particles are shown in figure 4. The remaining droplets of the atomized dry suspension concentrate, which do not infiltrate the surface of the fluidized powder particles, are dried gradually during the drying process, such as falling down in a fluidized bed, to dry fine particles, large droplets are dried to semi-dry particles, and the latter particles are infiltrated by the droplets during the fluidization cycle, and the dry fine particles agglomerate or adhere to the larger semi-dry particles to form cumulatively grown 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 mist-coated growth granules, powder agglomerated growth granules and spray-dried granules.

In the embodiment, the total amount of the atomized dry suspension agent mother liquor and the total amount of the fluidized dry suspension agent mother powder may be subjected to the mixing granulation treatment according to the following proportion:

the mass ratio of propanil contained in the dry suspending agent mother liquor to propanil contained in the dry suspending agent mother powder is 20-60: (80-40) is to carry out mixing granulation treatment in proportion. The ratio may further be 15 to 25: (85-75), and further may be 20-25: (85-80). Namely, the mass of propanil contained in the total amount of the dry suspending agent mother solution subjected to atomization treatment accounts for 20% -60% of the total mass of propanil contained in the prepared propanil dry suspending agent, and can be 15% -25% or more, and can be 20% -25% or more. The mass of the propanil contained in the total amount of the dry suspending agent mother powder subjected to fluidization treatment accounts for 80-40% of the total mass of the propanil contained in the prepared propanil dry suspending agent, and can be 85-75% or more, and can be 85-80% or more. By controlling the mixing ratio of the total amount of the atomized dry suspending agent mother solution and the total amount of the fluidized dry suspending agent mother powder, the dry suspending agent mother solution 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 propanil dry suspending agent can be effectively regulated, and the drug effect of the propanil dry suspending agent is 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 net to the diameter of the bottom net can be controlled to be 2-4: 1, further can be controlled to 2.5-3.5: 1, and further can be controlled to be 2.8-3.2: 1.

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

The air temperature of the air inlet is lower than the melting point and/or softening point of the propanil raw material, for example, the air temperature of 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 ℃.

Through controlling and optimizing the conditions of the fluidization treatment, the fluidization treatment effect of the dry suspending agent mother powder can be effectively regulated, 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 air temperature can effectively ensure the morphology of propanil particles and avoid melting. Thus, by controlling the above-mentioned conditions of the fluidization treatment as described above, the quality of the particles formed by the propanil dry suspension is improved.

In a specific embodiment, when the dry suspension agent mother powder is fluidized by a fluidized bed and is in a fluidized state, the conventional fluidized bed and the control process conditions thereof are specifically improved with respect to the dry suspension agent mother powder in step S02, such as the distance from the nozzle of the conventional fluidized bed to the bottom screen: bottom net diameter = 0.8-1.2: 1, the distance from the fluidized bed nozzle to the boiling bottom net is increased: the diameter ratio of the bottom net is 2-4: 1, further 2.8 to 3.2:1. the improvement of the parameters of conventional fluidized bed equipment increases the dropping stroke of dry suspending agent mother powder particles in fluidized state powder and atomized dry suspending agent mother liquid, thereby increasing the contact probability of the fluidized state powder and atomized dry suspending agent mother liquid drops and increasing the drying residence time, leading the generated propanil dry suspending agent to comprise a mixture of fog particle coating growth particles, particle agglomeration growth particles and spray drying particles, being beneficial to the drying and balling of the drops, avoiding too wet when the fog drops fall to a fluidized bed bottom net, being unfavorable to the growth of the drops and even sticking the bottom net when serious.

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

The fluidization treatment such as the improvement of the pertinence of the control process condition of the fluidized bed can be controlled and regulated in addition to the improvement and regulation of the air inlet speed, such as the reduction of the air inlet temperature of the fluidization treatment of the fluidized bed to the melting point of propanil and the softening point temperature such as below 60 ℃. The air inlet temperature of the spray granulation of the conventional spray tower is 120-180 ℃, and the air inlet temperature of the conventional fluidized bed granulation is 50-80 ℃. In the embodiment of the application, in order to achieve both granulation and quality, the temperature of the air inlet after improvement is below 60 ℃, for example, the air temperature of fluidization treatment is controlled to be 45-58 ℃, further controlled to be 50-58 ℃, and further controlled to be 53-55 ℃. Therefore, the air inlet temperature does not exceed the melting point and softening point of the propanil raw material, and further, the upper limit of a redundant space which is considered to be kept for long-time operation deviation of the device in actual production is controlled within 58 ℃. In addition, the air inlet temperature of the fluidized bed is not too low, so that the moisture evaporation of mist drops is not facilitated, the particles in the bed are easy to be too wet to cause dead beds, or the quality or stability of particles forming a propanil dry suspending agent is not ideal.

In the embodiment, the atomizing pressure of the spraying treatment can be controlled to be 0.30-0.50 Mpa, further controlled to be 0.35-0.45 Mpa, and further controlled to be 0.40-0.45 Mpa. While the atomization pressure of the spray of the conventional fluidized bed spray gun is controlled between 0.10 and 0.15Mpa at present, in the embodiment of the application, the atomization pressure is increased, for example, the atomization pressure of the spray gun is increased to 0.30 to 0.50Mpa, further 0.35 to 0.45Mpa, further 0.40 to 0.45Mpa, so that the diameter of the atomized dry suspension agent mother liquor drops is relatively small, the contact between the dry suspension agent mother liquor drops and the powder particles in a fluidized state is increased, and the drying rate of the dry suspension agent mother liquor drops 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 propanil dry suspension can be regulated, and the stability and the drug effect exertion during application of the propanil dry suspension are improved.

According to the preparation method of the propanil dry suspending agent, the propanil is firstly prepared into the dry suspending agent mother liquor, part of propanil is firstly prepared into the dry suspending agent mother powder, and the spray-state liquid drops of the dry suspending agent mother liquor and the fluidized state powder of the dry suspending agent mother liquor are contacted and mixed to carry out granulation treatment, so that the propanil dry suspending agent is formed, the propanil dry suspending agent prepared by the preparation method has the characteristics of good dispersion stability, high suspension rate and the like, and the pesticide effect of active ingredients such as propanil and the like can be fully exerted. In addition, the preparation method of the propanil dry suspending agent has the advantages that the preparation process is easy to control, the stability of the morphology, the drug effect and other performances of the prepared propanil dry suspending agent is effectively ensured, the production efficiency is effectively improved, and the production cost is reduced.

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

Wherein the fog-particle coating growth particles comprise a nucleus body of dry suspending agent mother powder particles and a coating layer formed by atomized dry suspending agent mother liquid drops on the surface of the nucleus body, as shown in figure 3. Further detection, particle diameter Dv of nuclei contained in mist coating growth particles ₉₀ 6-30 mu m; the coating layer may be at least one layer, and the thickness of the coating layer may be 0.2 to 30 μm. The mist coat growth particles may be primary particles formed of the core body and the coating layer, or may be cluster particles (secondary particles) formed by agglomerating at least two primary particles. Thus, the overall particle size of the whole mist coating growth particle may be Dv ₉₀ 6.2-600 μm.

The powder particle agglomeration growth granules comprise at least two agglomerated dry suspending agent granules, and solid bridges are formed between two adjacent dry suspending agent granules, as shown in figure 4; further detection, particle diameter Dv of powder particle agglomeration growth particles ₉₀ Is 12-800 mu m, and the particle diameter Dv of the dry suspending agent particles contained in the suspension concentrate is 12-800 mu m ₉₀ May be 6 to 60. Mu.m.

The spray-dried particles have a particle diameter Dv as shown in FIG. 5 ₉₀ 8-150 μm. The spray-dried particles may be primary particles, or may be cluster particles (secondary particles) formed by agglomerating at least two primary particles.

In a second aspect, based on the preparation method of the propanil dry suspension, the embodiment of the application also provides a propanil dry suspension. The propanil dry suspension comprises a mixture of mist coating growth particles, powder particle agglomeration growth particles and spray drying particles. Because the propanil dry suspending agent provided by the embodiment of the application comprises particles with morphology and structure such as fog particle coating growth particles, particle agglomeration growth particles, spray drying particles and the like, the propanil dry suspending agent has the characteristics of good dispersion stability, high suspension rate and the like, and has good prevention and control effects. And the suspension is a dry suspension agent, does not contain solvent and does not generate phytotoxicity. According to the biological measurement data, even if the dosage is three times higher than that of the emulsion, the pesticide injury can not occur, and the prevention and control safety is high.

The spray coating growth particles contained in the propanil dry suspending agent are the spray coating growth particles described in the preparation method of the propanil dry suspending agent, and as shown in fig. 3, the spray 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 fluidization treatment of dry suspending agent mother powder, and the propanil dry suspending agent coating layer is a coating layer formed by fluidization treatment of dry suspending agent mother liquid drops formed by atomization treatment of dry suspending agent mother liquid on particles formed by fluidization treatment. Thus, in an embodiment, the composition of the first propanil dry suspension particles may be the component contained in the dry suspension master powder above. The coating may comprise the components of the dry suspension concentrate described above. For economy of space, the ingredients of the first propanil dry suspension particles and the coating layer will not be described in detail herein.

In other embodiments, the first propanil dry suspension particles have a particle size Dv ₉₀ 6-30 mu m; 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 whole fog particle coating growth particles ₉₀ May be 6.2 to 600. Mu.m. The fog particle coating growth particles can be primary particles formed by the first propanil dry suspending agent particles and a propanil dry suspending agent coating layer, and can also be cluster particles formed by agglomeration of at least two primary particles.

The grain agglomerated growth particles contained in the propanil dry suspending agent comprise at least two agglomerated second propanil dry suspending agent particles, and a solid bridge is formed between two adjacent second propanil dry suspending agent particles, as shown in figure 4. Wherein, the second propanil dry suspending agent particles are composite particles formed by contacting particles formed by fluidization treatment of upper Wen Gan suspending agent mother powder with atomized dry suspending agent mother liquid drops. The second propanil dry suspension particles should be a composition comprising the above dry suspension mother liquor and dry suspension mother powder.

In other embodiments, the particle size Dv of the agglomerated particle size growth particles ₉₀ Is 12-800 mu m, and the particle diameter Dv of the second propanil dry suspending agent particles contained in the suspension is 12-800 mu m ₉₀ May be 6 to 60. Mu.m.

The spray-dried particles contained in the propanil dry suspension are shown in FIG. 5, and the particle size Dv of the spray-dried particles ₉₀ 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 can be effectively improved, and the drug effect of the propanil dry suspending agent can be improved.

In other embodiments, the mass ratio of the spray coating growth particles, the powder particle agglomeration growth particles and the spray drying particles contained in the propanil dry suspension agent of the embodiment of the application can be (25% -35%): (50% -70%): (5% -15%). The dispersion stability, the suspension rate and other characteristics of the propanil dry suspending agent of the embodiment of the application can be effectively improved by adjusting the content ratio of the fog particle coating growth particles, the particle agglomeration growth particles and the spray drying particles, and the drug effect of the propanil dry suspending agent of the embodiment of the application can be improved.

The application will now be described in further detail by taking specific propanil dry suspending agents and methods of preparation as examples.

Example 1

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

s1, preparing 1 kg of mother liquor with 6% of solid content (propanil content is 3%).

938.39 g of deionized water is weighed, 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9) and dispersing agent tristyrylphenol phosphate (SOPROPHOR SC, supplied by Solvay Co.) are added while stirring, 20 g of stabilizer methacrylate copolymer (ATLOX 4913-LQ- (MV), supplied by Croda Co.) are added, 10 g of defoamer polyoxypropylene polyoxyethylene glycerol ether (X-7823, supplied by Jinan Ruan An technology Co.) are added, 1 g of 98% propanil raw material is sheared for 3-5 minutes, and the ground materials Dv are controlled ₉₀ Particle size is less than or equal to 5 mu m;

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

365.86 g of calcined kaolin, 10 g of sodium dodecyl sulfate (K12) serving as a wetting agent, 50 g of a dispersing agent polyacrylate polymer (Agrilan 782 provided by Nouryon company), 50 g of flow aid precipitation method white carbon black, 3 g of defoaming agent fatty acid salt (DDF), 402.04 g of 98% of propanil original drug and 119.1 g of 89% of quinclorac are sequentially weighed, mixed and crushed, and Dv is controlled ₉₀ The particle size is within the range of 6-10 mu m, 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%) in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of 3% propanil mother liquid prepared in the step S1 into the fluidized bed through atomization and dispersion fog drops, wherein a nozzle in the fluidized bed is at a distance from a bottom net: the diameter of the bottom net is 2:1, the wind speed is 1.8-3.5 m/s, the spray gun atomization pressure is 0.30-0.50 Mpa, the air inlet temperature is 45-58 ℃, and 50% propanil-quinclorac dry suspending agent (40% +10%) is obtained after fog particle coating, particle agglomeration and spray drying.

Example 2

s1, preparing 1 kg of mother solution with 15% of solid content (propanil is 5% and quinclorac is 3%):

844.27 g of deionized water is weighed, 50 g of wetting agent succinate sulfonate (GR-7M provided by Nanjing Gutian chemical industry), 10 g of dispersant aryl polyoxyalkyl sulfate (SK-34 SC provided by Starfly chemical industry Co., ltd.), 10 g of stabilizer ABA type EO/PO block polyether (SYNPERONIC T/908-FL- (CQ) provided by Croda company, 10 g of defoamer organic silicon defoamer (SAG-1572 provided by Momentive company) 1 g, 51.02 g of 98% propanil raw material, 33.71 g of 89% quinclorac raw material are added while stirring, shearing is carried out for 3-5 minutes, and grinding is carried out to control the ground material Dv ₉₀ Particle size 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, 50 g of wetting agent sodium alkylnaphthalene sulfate (EFW), dispersant sodium polycarboxylate (CAS:62601-60-9) 200 g of glidant modified gas-phase white carbon black (HDK N20, supplied by WACKER company) 10 g, 535.71 g of 98% propanil original drug and 95.51 g of 89% quinclorac, and after mixing, crushing, controlling Dv ₉₀ The particle size is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

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

adding 1 kg of 61% propanil quinclorac mother powder (52.5% + 8.5%) in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of 8% propanil quinclorac mother solution prepared in the step S1 into the fluidized bed through atomization and dispersion, wherein a nozzle in the fluidized bed is separated from a bottom net by a distance: the diameter of the bottom net is 4:1, the air 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% propanil quinclorac dry suspending agent (50% +10%) is obtained after fog particle coating, particle agglomeration and spray drying.

Example 3

s1, preparing 1 kg of mother solution with 35% of solid content (20% of propanil and 5% of quinclorac):

636.74 g of deionized water is weighed, 20 g of wetting agent isomeric alcohol polyoxyethylene ether, 20 g of dispersing agent styrene sodium acrylate copolymer (ATLOX METASERRE 100L-LQ- (AP) supplied by Croda company), 30 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ supplied by Nanjing Jieron company), 50 g of defoamer polyoxypropylene polyoxyethylene glyceryl ether (X-7823 supplied by Jinan Runshan technology Co., ltd.) and 3 g of 98% propanil original drug 204.08 g and 89% quinclorac original drug 56.18 g are added while stirring, shearing is carried out for 3-5 minutes, and grinding is controlled Is (d) the material Dv ₉₀ Particle size is less than or equal to 5 mu m;

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

37.04 g of water-washed kaolin, 10 g of sodium dodecyl sulfate (K12) as a wetting agent, 180 g of a dispersing agent polyacrylate polymer (Agrilan 782, supplied by Nouryon corporation), 50 g of a glidant gas-phase white carbon black (AEROSIL 200, supplied by Ying Chuang specialty Chemie, shanghai Co., ltd.), 5 g of sodium salt of beef tallow fatty acid (Agnique SOAP L, supplied by BASF Co.) as an antifoaming agent, 622.45 g of propanil stock with 98% content, 95.51 g of 89% quinclorac, and pulverizing after mixing to control Dv ₉₀ The particle size 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 69.5% propanil-quinclorac mother powder (61% + 8.5%) in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of 25% propanil-quinclorac mother solution prepared in the step S1 into the fluidized bed through atomization and dispersion, wherein a nozzle in the fluidized bed is separated from a bottom net by a distance: 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 the 70% propanil quinclorac dry suspending agent (60% +10%) is obtained after fog particle coating, particle agglomeration and spray drying.

Example 4

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

734.31 g of deionized water is weighed, 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9), 10 g of dispersing agent tristyrylphenol phosphate (SOPROPHOR SC, supplied by Solvay Co.), 10 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ, supplied by Nanjing Jieron technology Co., ltd.) 10 g, 1 g of defoaming agent silicone defoamer (SAG-1572, supplied by Momentive Co., ltd.) and 98% of propanil234.69 g of raw medicine is sheared for 3-5 minutes, grinding is carried out, and the Dv of the ground material is controlled ₉₀ Particle size is less than or equal to 5 mu m;

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

6.12 g of water-washed kaolin, 10 g of sodium dodecyl sulfate (K12) serving as a wetting agent, 150 g of dispersing agent polyacrylate polymer (Agrilan 782 provided by Nouryon company), 35 g of flow aid precipitation white carbon black, 5 g of beef tallow fatty acid sodium salt serving as an antifoaming agent (Agnique SOAP L provided by BASF company) and 793.88 g of propanil raw material with 98 percent content are sequentially weighed, mixed and crushed, and Dv is controlled ₉₀ The particle size 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 in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of 23% propanil mother liquid prepared in the step S1 into the fluidized bed through atomization and dispersion fog drops, wherein a nozzle in the fluidized bed is away from a bottom net: 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% propanil dry suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Example 5

s1, preparing 1 kg of mother solution with 25% of solid content (5% of propanil and 10% of quinclorac):

736.62 g of deionized water is weighed, 40 g of wetting agent succinate sulfonate (GR-7M provided by Nanjing Gutian chemical industry), 20 g of dispersing agent styrene sodium acrylate copolymer (ATLOX METASERE 100L-LQ- (AP) provided by Croda company), 30 g of stabilizer ABA type EO/PO block polyether (SYNPERONIC T/908-FL- (CQ) provided by Croda company), 10 g of antifoaming agent organic silicon defoamer (SAG-1572 provided by Momentive company), 51.02 g of 98% content of propanil raw medicine and 112.36 g of 89% of quinclorac raw medicine are added while stirring, shearing is carried out for 3-5 minutes, and grinding is controlled Is (d) the material Dv ₉₀ Particle size is less than or equal to 5 mu m;

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

386.26 g of calcined kaolin, 20 g of wetting agent alkyl naphthalene sodium sulfate (EFW), 80 g of dispersant alkyl naphthalene sulfonate ammonium salt (DISESOL PSR 19-PW- (TH) provided by Croda company), 100 g of glidant modified gas-phase white carbon black (HDK N20 provided by WACKER company), 3 g of defoamer beef tallow fatty acid sodium salt (Agnique SOAP L provided by BASF company), 382.65 g of 98% of propanil raw material and 28.09 g of 89% of quinclorac raw material are weighed in sequence, and are crushed after mixing, and Dv is controlled ₉₀ The particle size 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 to serve as a bottom material, and spraying 1 kg of 15% propanil-quinclorac mother solution prepared in the step S1 into the fluidized bed through atomization and dispersion, wherein a nozzle in the fluidized bed is separated from a bottom net by a distance: the bottom net diameter is 2.8:1, 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 50-55 ℃, and 40% propanil-quinclorac dry suspending agent (30% +10%) is obtained after fog particle coating, particle agglomeration and spray drying.

Example 6

s1, preparing 1 kg of mother solution with 25% of solid content (10% of propanil and 2% of quinclorac):

742.49 g of deionized water is weighed, 30 g of wetting agent succinate sulfonate (GR-7M, supplied by Nanjing Gutian chemical) and dispersing agent styrene sodium acrylate copolymer (ATLOX METASPERSE 100L-LQ- (AP), supplied by Croda company) are added with stirring, 80 g of stabilizer ABA type EO/PO block polyether (SYNPERONIC T/908-FL- (CQ), supplied by Croda company) is added, 20 g of defoaming agent organic silicon (SAG-1572, supplied by Croda company)Supplied by Momentive company) 3 g, 102.04 g of 98% propanil original drug and 22.47 g of 89% quinclorac original drug, shearing for 3-5 min, grinding, and controlling the Dv of the ground material ₉₀ Particle size 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%:

169.41 g of water-washed kaolin, 30 g of sodium dodecyl sulfate (K12) as a wetting agent, 100 g of polyacrylate polymer (Agrilan 782, supplied by Nouryon corporation), 30 g of modified fumed silica (HDK N20, supplied by WACKER corporation), 30 g of sodium salt of beef tallow fatty acid (Agnique SOAP L, supplied by BASF corporation) as a defoaming agent, 4 g of propanil stock with 98% content 408.16 g, and 89% of quinclorac stock 258.43 are weighed in sequence, mixed and pulverized to control Dv ₉₀ The particle size is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing a 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 to serve as a bottom material, and spraying 1 kg of 12% propanil quinclorac mother solution prepared in the step S1 into the fluidized bed through atomization and dispersion, wherein a nozzle in the fluidized bed is separated from a bottom net by a distance: the bottom net diameter 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 50-55 ℃, and 60% propanil quinclorac dry suspending agent (40% + 20%)

Example 7

734.31 g of deionized water is weighed, 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9) and 10 g of dispersing agent tristyrylphenol phosphate (SOPROPHOR SC, supplied by Solvay company) are added with stirring, and 10 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ, supplied by south China) Supplied by jingjie Runchi technology Co., ltd.) 10 g, an antifoaming agent silicone antifoaming agent (SAG-1572 supplied by Momentive Co., ltd.) 1 g, and a propanil crude drug 234.69 g with 98% content, shearing for 3-5 minutes, grinding, and controlling the Dv of the ground material ₉₀ Particle size 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 in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of 23% propanil mother liquid prepared in the step S1 into the fluidized bed through atomization and dispersion fog drops, wherein a nozzle in the fluidized bed is away from a bottom net: the bottom net diameter 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 45-55 ℃, and 80% propanil dry suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Example 8

734.31 g of deionized water is weighed, 10 g of wetting agent fatty alcohol polyoxyethylene ether (AEO-9) and dispersing agent tristyrylphenol phosphate (SOPROPHOR SC, supplied by Solvay Co.) are added while stirring, 10 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ, supplied by Nanjing Jie Runner technology Co., ltd.) is added, 10 g of defoamer organosilicon defoamer (SAG-1572, supplied by Momentive Co.) is added, 1 g of 98% of propanil raw medicine 234.69 g, and 3-5 g of stabilizer is shearedMinute, grinding, and controlling Dv of the ground material ₉₀ Particle size 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 in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of 23% propanil mother liquid prepared in the step S1 into the fluidized bed through atomization and dispersion fog drops, wherein a nozzle in the fluidized bed is away from a bottom net: the bottom net diameter 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 45-55 ℃, and 80% propanil dry suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Example 9

This example provides an 80% propanil dry suspension and 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 dispersing agent tristyrylphenol phosphate (SOPROPHOR SC, supplied by Solvay Co.), 10 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ, supplied by Nanjing Jie Runchi technology Co., ltd.) and 10 g of defoamer organic silicon defoamer (SAG-1572, supplied by Momentive Co.) with stirring, adding 234.69 g of 98% propanil 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.

s3, preparing 80% propanil dry suspending agent

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

Example 10

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, supplied by Solvay Co.), 10 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ, supplied by Nanjing Jie Runchi technology Co., ltd.) and 10 g of defoamer organic silicon defoamer (SAG-1572, supplied by Momentive Co.) with stirring, adding 234.69 g of 98% propanil raw material, shearing for 3-5 minutes, grinding, and controlling the ground material Dv ₉₀ Particle size 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) and dispersant polypropylene are weighed in turn150 g of acid ester polymer (Agrilan 782, supplied by Nouryon company), 35 g of white carbon black by a flow aid precipitation method, 5 g of defoaming agent beef tallow fatty acid sodium salt (Agnique SOAP L, supplied by BASF company) and 793.88 g of 98% propanil raw material, and after mixing, crushing, controlling Dv ₉₀ The particle size 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 in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of 23% propanil mother liquid prepared in the step S1 into the fluidized bed through atomization and dispersion fog drops, wherein a nozzle in the fluidized bed is away from a bottom net: the diameter of the bottom net is 1.2:1, the wind speed is 1.2-1.5 m/s, the spray gun atomization pressure is 0.1-0.15 Mpa, the air inlet temperature is 60-80 ℃, and 80% propanil dry suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Comparative example 1

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

s1, preparing 1 kg of mother solution with 35% of solid content (25% of quinclorac):

616.1 g of deionized water is weighed, 20 g of wetting agent isomeric alcohol polyoxyethylene ether, 20 g of dispersing agent styrene sodium acrylate copolymer (ATLOX METASERRE 100L-LQ- (AP) supplied by Croda company), 30 g of stabilizer polyoxyalkylene glycol monobutyl ether (Ethylan NS-500LQ supplied by Nanjing Jieron company), 50 g of defoamer polyoxypropylene polyoxyethylene glycerol ether (X-7823 supplied by Jinan Runshan technology Co., ltd.) and 280.9 g of 89% quinclorac original drug are added while stirring, shearing is carried out for 3-5 minutes, grinding is carried out, and the ground material Dv is controlled ₉₀ Particle size 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 sodium dodecyl sulfate (K12) as wetting agent, 60 g of dispersing agent polyacrylate polymer (Agrilan 782, supplied by Nouryon Co.) and 60 g of glidant gas-phase white carbon black (AEROSIL 200, specially formulated by Ying)50 g of butter fatty acid sodium salt (Agnique SOAP L, available from BASF) as defoamer, 5 g of 89% quinclorac 856.7 g, and pulverizing after mixing to control Dv ₉₀ The particle size is within the range of 6-10 mu m, and the mixture is mixed for 10-30 minutes after being crushed;

s3, preparing 75% quinclorac dry suspending agent:

adding 1 kg of the 76.25% quinclorac mother powder in the step S2 into a fluidized bed to serve as a bottom material, and spraying 1 kg of the 25% quinclorac mother solution prepared in the step S1 into the fluidized bed through atomization and dispersion, wherein the distance between a nozzle in the fluidized bed and a bottom net is: the diameter of the bottom net is 1.2:1, 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 the 75% quinclorac dry suspending agent is obtained after fog particle coating, particle agglomeration and spray drying.

Comparative example 2

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

s2, 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 and dispersion of fog drops, wherein the distance between a nozzle in the fluidized bed and a bottom net is: the diameter of the bottom net is 4:1, 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 120-150 ℃, and the 50% propanil dry suspending agent is prepared after fluidized bed spray drying.

Comparative example 3

step one: 1 kg of mother liquor with a solids content of 50% (propanil content 40%) was prepared:

500 g of deionized water is weighed, 20 g of wetting agent isomeric alcohol polyoxyethylene ether and 68.8 g of dispersing agent sodium lignin sulfonate (M-9) are added while stirring3 g of foamer polyoxypropylene polyoxyethylene glyceryl ether (X-7823, supplied by Jinan Ruan technology Co., ltd.) and 408.2 g of 98% propanil raw material, shearing for 3-5 min, grinding, and controlling the material Dv after grinding ₉₀ Particle size 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 through 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 of the comparative example comprises the following steps:

step one: 1 kg of master batch with propanil content of 80% is prepared:

500 g of water-washed kaolin, 20 g of sodium dodecyl sulfate (K12) as a wetting agent, 68.8 g of a dispersant polyacrylate polymer (Agrilan 782, supplied by Nouryon corporation), 3 g of a sodium salt of a beef tallow fatty acid (Agnique SOAP L, supplied by BASF corporation), 408.2 g of 98% propanil stock solution, and mixing for 3-5 minutes, and carrying out jet milling;

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

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

Relevant test and efficacy experiment of Dry suspension

1. Propanil dry suspension related performance test:

the propanil dry suspension in examples 1 to 10 and the dry suspension in comparative examples 1 to 4 were subjected to the following correlation properties in table 1 (the correlation properties detection method was performed according to the corresponding line standard or national standard method), respectively, and the correlation properties detection parameters are shown in table 1:

TABLE 1

As can be seen from Table 1, the propanil dry suspending agent provided in each of examples 1 to 8 of the present application has high granulation quality, the propanil dry suspending agent contains fog particle coating growth particles, particle agglomeration growth particles and spray drying particles, the proportion is stable, the phenomena of sticking the particles to the bottom net or hardening and the like are avoided, the product suspension rate is high, and the heat storage quality is good. The propanil dry suspending agent provided in examples 9 to 10 is relatively poor in granulating quality compared with examples 1 to 8, has a certain phenomenon of sticking with a bottom net or hardening, and is low in product suspension rate compared with examples 1 to 8, but still basically can be prepared, and is obviously superior to comparative examples 2 and 3 in granulating quality and suspension rate. Although comparative example 1 can produce a relatively good granule quality, there is no occurrence of sticking to the bottom net or hardening, etc., because it does not contain the cause of the propanil active ingredient. In contrast, comparative example 2 was prepared by direct spray drying of the mother liquor in a fluidized bed, which had poor granulation quality and low suspension rate, had a sticking of the bottom net and occurrence of hardening, and more importantly, failed to simultaneously prepare a mixture of mist coating growth particles, powder agglomerated growth particles and spray dried particles. Comparative example 3 is a direct spray drying granulation of mother liquor in a conventional spray tower, and has the problems of poor suspension rate and unqualified heat storage. Comparative example 4 is a conventional masterbatch extrusion granulation, which has a problem of low dispersibility.

2. Propanil dry suspension related performance test:

the dry suspending agents for propanil in examples 1 to 10 and the dry suspending agents for comparative example were each subjected to a pharmacodynamic test as follows, and differences in the control effect of each dry suspending agent on propanil in paddy fields were each tested. The test agents were selected from 80% propanil dry suspension (example 4), 80% propanil dry suspension (example 7), 80% propanil dry suspension (example 8), 70% propanil-dichloro dry suspension (60+10, example 3), 80% propanil dry suspension (examples 9 and 10), 80% propanil WDG (boiling fluidized bed granulation) of the company of the He-senso-Lignomonic acid Co., ltd, 75% quinclorac WDG (conventional extrusion granulation), 75% quinclorac dry suspension (comparative example 1), 80% propanil dry suspension (comparative example 3), and 80% propanil water dispersible granule (conventional extrusion granulation, comparative example 4) of the company of the Jiangsu agricultural hormone engineering research center. The test was carried out in the early rice direct seeding field of the five-star reclamation farm in Nanchang city of Jiangxi province.

2.1 design of experiments

2.1.1 test treatments: as shown in table 2 below.

Table 2 test design

2.1.2 test investigation

The safety and the control effect of the rice are observed by visual inspection 3 and 7 days after the application.

Investigation of plant control effect 15 and 30 days after drug application; fresh weight control effect was investigated for 30 days.

2.2 test results

2.2.1 visual inspection

2.2.1.1 days after the administration

The rice treated each day 3 after the medicine grows normally. Treating A, D part of leaves to start wilting and draping, slightly carbonizing the upper part of the leaves to burn the leaves, and ensuring that the carbonization area of the leaves is relatively maximum; the leaves are seldom processed B, C to start wilting and draping, and the carbonization occupied area of the leaves is slightly smaller; while the remaining individual treatments of barnyard grass were temporarily devoid of toxic symptoms.

2.2.1.2 days after the administration

7 days after the medicine, each treatment has safety and no harm to the rice. Processing A, D, namely starting to wilt and spread in a large area, carbonizing the burnt leaves, and ensuring that the carbonization area of the leaves is the largest; processing B, C begins to partially wilt and spread, and leaves carbonization occupies a slightly smaller area; while E, F, H is only little wilted and scattered, carbonized and burned leaves, and the carbonization area of the leaves is the smallest; while the treatment J, K has very small wilting and scattering parts, charred leaves and small leaf charring area, and the treatment G, I has the toxic symptoms of only slightly dwarfing and normal leaves.

2.2.2 plant control

The pesticide is carried out according to the pesticide field efficacy test criterion (one) GB/T17980.40-2000. The calculation formula of the test results is as follows, and the test results are shown in tables 3 and 4 below.

TABLE 3 Dry suspending agents of different dosage forms and different concentration gradients are shown for controlling barnyard grass in paddy fields

TABLE 4 statistical Table of control efficacy of dry suspending agent against barnyard grass in paddy field with different dosage forms and different concentration gradients

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 rice growth. Compared with the propanil dry suspending agent (different processing technologies) and the medicine effect in other embodiments, the control effect on the propanil is fast, the control effect is obvious and preferential, and the early visual control effect is high. And the propanil dry suspending agent, the 75% quinclorac dry suspending agent and the 80% propanil water dispersible granule in the comparative examples 1, 3 and 4 are obviously lower than the dry suspending agent in the embodiment 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. 3 days after the medicine, barnyard grass wilts and is scattered, and part of leaves are carbonized and burned. 7 days after the medicine, the barnyard grass leaves wilt and are heavily spread, and the large-area leaves are carbonized and burned. Barnyard grass died thoroughly 15 days after the drug. Compared with the propanil dry suspending agent (different processing technologies) and the propanil dichloro dry suspending agent (different processing technologies) in other examples, the propanil dry suspending agent is safe to rice and has no difference. The barnyard grass is carbonized and burned only in a small part of leaves 3 days after the medicine. 7 days after the medicine, the leaves of the low-age barnyard grass are carbonized, part of the large-age barnyard grass only shows the burnt leaves at the upper part, the stem base is normal, and part of barnyard grass recovers to grow normally after 15 days after the medicine, and the control effect on barnyard grass is obviously lower than that of a propanil dry suspending agent (example 4) and a propanil-dichloro dry suspending agent (example 3). The propanil dry suspending agent (example 4), the propanil and dichloro dry suspending agent (example 3) are quite safe compared with the propanil dry suspending agent (different processing technologies) and the propanil and dichloro dry suspending agent (different processing technologies), but have the characteristics of high control effect on the barnyard grass and the like. The propanil dry suspending agent in each embodiment of the application is obviously superior to the propanil dry suspending agent, 75% quinclorac dry suspending agent and 80% propanil water dispersible granule in comparative examples 1, 3 and 4 (conventional extrusion granulation and comparative example 4).

When the rice leaves are 1 core, barnyard grass is in 4 leaf stage, 80% of barnyard grass dry suspending agent (example 4) is applied, the application amount per mu is 250g, and the control effect on barnyard grass plants after 15 days is 89.96% respectively; the dosage of the propanil dry suspending agent is 250g per mu compared with other propanil dry suspending agents (different processing technologies) and control propanil dry suspending agents (comparative example 3), and the plant prevention effect is only 83.13 percent (B), 81.93 percent (C), 73.49 percent (E), 71.49 percent (F), 69.88 percent (H) and 57.03 percent (J) 15 days after the dosage. The 80% propanil dry suspending agent (example 4) is applied, the application amount per mu is 250g, and the control effect on the propanil plant after 30 days is 95.22%; the fresh weight control effect is 96.15 percent. Compared with other propanil dry suspending agents (different processing technologies), the control propanil dry suspending agent (comparative example 3) and the dosage of the propanil dry suspending agent per mu of 250g, the plant prevention effect after 30 days of the medicament 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), and the fresh weight prevention effect is 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.

The dry suspending agent of 70% propanil and dichloro is applied, the application amount of each mu is 250g, and the control effect on the barnyard grass plant after 15 days is 87.95% (D). The dosage of the contrast agent 80% propanil dry suspending agent (E, F, H, J) per mu is 250G, and the dosage of the 75% quinclorac dry suspending agent (G, I) per mu is 40G, and the plant prevention effect after 15 days of the drug is only 73.49% (E), 71.49% (F), 69.88% (H), 57.03% (J), 43.37% (G) and 45.38% (I). The control effect on barnyard grass after 30 days is 92.43 percent (D); the fresh weight control effect is 94.29 percent (D). The dosage of the contrast agent 80% propanil dry suspending agent (E, F, H, J) per mu is 250G, and the dosage of the 75% quinclorac dry suspending agent (G, I) per mu is 40G, the plant prevention effect is only 76.89% (E), 74.50% (F), 72.91% (H), 59.76% (J), 49.00% (G) and 50.20% (I) 30 days after the drug administration, and the fresh weight prevention effect is 80.26% (E), 78.91% (F), 75.43% (H), 63.12% (J) 52.13% (G) and 55.16% (I) respectively.

In conclusion, the propanil dry suspending agent (example 4) is safe for rice, and the control effect on the propanil is obviously higher than that of the propanil dry suspending agent (different processing technologies) and the control propanil dry suspending agent (comparative example 3). The propanil and dichloro dry suspending agent is safe to rice, and the control effect of the propanil and dichloro dry suspending agent on the propanil is obviously higher than that of an 80 percent propanil dry suspending agent (E, F, H, J) and a 75 percent quinclorac dry suspending agent (G, I).

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

The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.

Claims

1. A preparation method of 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 the dry suspending agent mother powder to form fluidized powder, spraying the dry suspending agent mother liquid to mix atomized dry suspending agent mother liquid drops with the fluidized powder, granulating and drying 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 drying particles;

the dry suspending agent mother solution comprises the following components in percentage by mass:

wherein the first active ingredient comprises propanil;

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

wherein the second active ingredient comprises propanil.

2. The method of manufacturing 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 fluidized bed nozzle to the bottom net to the diameter of the bottom net is 2-4: 1, a step of;

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

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

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

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

Particle size Dv of the solid particles contained in the dry suspension mother liquor ₉₀ Less than or equal to 5 mu m; and/or

Particle diameter Dv of the dry suspending agent mother powder ₉₀ Is 6-10 mu m; and/or

The mass ratio of the total amount of the dry suspending agent mother solution subjected to the atomization treatment to the total amount of the dry suspending agent mother powder subjected to the fluidization treatment is 20-60: (80-40) is to carry out the mixing granulation treatment in proportion.

5. A process according to any one of claims 1 to 3, characterized in that: at least one of the first active ingredient and the second active ingredient further comprises other active ingredients, wherein the other active ingredients comprise at least one of quinclorac, bispyribac-sodium, bensulfuron-methyl, cyhalofop-butyl and oxazoxaprop-p-ethyl; 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 sodium acrylate copolymer; and/or

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

The stabilizer comprises an ABA type EO/PO block polyether structure polymer, wherein 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 naphthalene sulfate; and/or

The second dispersant comprises at least one of polyacrylate polymer, polycarboxylic acid sodium salt and alkyl naphthalene sulfonic acid ammonium salt; and/or

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

The flow agent comprises at least one of precipitated white carbon black, gas-phase white carbon black and modified gas-phase white carbon black; and/or

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

6. Propanil dry suspension prepared by the preparation method of propanil dry suspension according to any one of claims 1-5, characterized in that: a mixture comprising mist coat growth particles, powder agglomerate growth particles, and spray dried particles; wherein,,

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;

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

7. Propanil dry suspension according to claim 6, characterized in that: the fog particle coating growth particles have at least any one of the following characteristics:

particle diameter Dv of the first propanil dry suspending agent particles ₉₀ 6-30 mu m;

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

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

the fog particle coating grows particlesParticle diameter Dv of the particles ₉₀ 6.2-600 μm.

8. Propanil dry suspension according to claim 6 or 7, characterized in that: the particle diameter Dv of the second propanil dry suspending agent particles ₉₀ 6-60 mu m; and/or

The particle size of the powder particle agglomeration growth particle is Dv ₉₀ Is 12-800 mu m; and/or

Particle size Dv of the spray-dried particles ₉₀ 8-150 μm.

9. Propanil dry suspension according to claim 7 or 8, characterized in that: the mass ratio of the fog particle coating growth particles to the particle agglomeration growth particles to the spray drying particles is 25% -35%: 50% -70%: 5% -15%.