A composition, its preparation method and application

Abstract

This invention belongs to the field of pesticide formulation technology, and relates to a composition, its preparation method, and its application. This invention provides a composition formed by compounding octochlor chelate, a high molecular weight compound, and kasugamycin. This invention solves the technical problems of octochlor degradation and inactivation, as well as precipitation, crystallization, and flocculation during storage, when octochlor and kasugamycin are directly mixed and compounded to prepare pesticide formulations.

Description

Technical Field

[0001] This invention belongs to the field of pesticide formulation technology, and relates to a composition, its preparation method and application. Background Technology

[0002] N-octyl-N'-[2-(octylamino)ethyl]ethylenediamine is a low-toxicity, broad-spectrum fungicide that significantly kills and inhibits various plant fungi, bacteria, and viruses that cause crop diseases. N-octyl-N'-[2-(octylamino)ethyl]ethylenediamine strongly inhibits mycelial growth and spore germination of pathogens, destroying their cell membranes, inhibiting their respiratory systems, coagulating proteins, and denaturing enzymes, thus exerting its bacteriostatic and bactericidal effects. N-octyl-N'-[2-(octylamino)ethyl]ethylenediamine has good water solubility and systemic properties, making it suitable for controlling various diseases in apples, rice, tomatoes, peppers, and cotton, especially viral diseases.

[0003] Kasugamycin, also known as kasugamycin, is an agricultural antibiotic fungicide produced by the actinomycete *Streptomyces kasugaensis*. Kasugamycin has strong systemic and penetrating properties; after spraying, it is quickly absorbed by plants and translocated within the plant body. It effectively inhibits mycelial growth and development, and has a killing effect on bacteria and fungi of the Deuteromycetes, preventing and treating various bacterial and fungal diseases. Kasugamycin is stable in acidic solutions with a pH of 4.0–5.0, but is unstable under alkaline conditions and is easily destroyed and inactivated.

[0004] The combination of octochlor and kasugamycin is a superior formulation that significantly enhances the bactericidal spectrum and efficacy. However, due to the formal differences between the two active ingredients, octochlor and kasugamycin are prone to chemical ionic bond reactions, leading to the decomposition and inactivation of the active ingredients. Directly mixing octochlor and kasugamycin results in decomposition, crystallization, and the inability to separate peaks in chromatographic detection. The decomposition rate of octochlor immediately exceeds 20%, and that of kasugamycin immediately exceeds 10%, making it difficult to obtain stable octochlor and kasugamycin compound formulations. Summary of the Invention

[0005] The purpose of this invention is to solve the technical problems that occur when octochlor and kasugamycin are mixed, both of which immediately degrade, and precipitation, crystallization, and flocculation occur during storage. To address this, this invention provides a composition, its preparation method, and its application.

[0006] On one hand, the present invention relates to a composition formed by compounding octochlor, a polymeric compound and kasugamycin;

[0007] The compound octochlor is an octochlor chelate that has been aminated after the pH has been adjusted to 4-6 by a pH adjuster.

[0008] The octenamine chelate is prepared by chelating octenamine and a chelating agent.

[0009] Generally, the pH adjuster is selected from at least one of phosphoric acid, hydrochloric acid, acetic acid, formic acid, lactic acid, citric acid, nitric acid, boric acid, sulfuric acid, oxalic acid, carbonic acid, tartaric acid, and malic acid.

[0010] Furthermore, in the composition provided by the present invention, the octenylamine chelate is formed after octenylamine and a chelating agent undergo chelation.

[0011] The chelating agent is an inorganic salt chelating agent and / or an organic chelating agent.

[0012] Furthermore, in the composition provided by the present invention, the inorganic salt chelating agent is selected from at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, sodium gluconate, potassium tartrate, and sodium citrate.

[0013] Furthermore, in the composition provided by the present invention, the organic chelating agent is selected from at least one of the following: chelating agents containing carboxyl and amino coordination groups, chelating agents containing hydroxyl and carboxyl coordination groups, hydroxyaminocarboxylic acid chelating agents, organic polyphosphonic acid chelating agents, polycarboxylic acid chelating agents, thiol-containing chelating agents, and Schiff base chelating agents.

[0014] For example, the chelating agent containing carboxyl and amino coordinating groups is selected from ethylenediaminetetraacetic acid (EDTA), aminotriacetic acid, triethylenetriaminepentaacetic acid, or salts thereof.

[0015] For example, the chelating agent containing hydroxyl and carboxyl coordination groups is selected from citric acid, tartaric acid, and gluconic acid.

[0016] For example, the hydroxyaminocarboxylic acid chelating agent is selected from hydroxyethyl ethylenediamine triacetic acid and dihydroxyethyl glycine.

[0017] For example, the organic polyphosphonic acid chelating agent is selected from hydroxyethylidene-1, 1-diphosphonic acid, aminotrimethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, triethylenetetraminehexamethylenephosphonic acid, bis(1,6-hexylene)triaminepentamethylenephosphonic acid, and polyaminopolyethertetramethylenephosphonic acid.

[0018] For example, the polycarboxylic acid chelating agent is selected from polyacrylic acid, polymethacrylic acid, hydrolyzed polymaleic anhydride, and fumaric acid.

[0019] For example, the thiol-containing chelating agent is selected from thioglycolic acid or sodium diethyl dithiocarbamate (NaDDC).

[0020] For example, the Schiff base chelating agent is selected from salicylaldehyde ethylenediamine, o-vanillin aminoacetic acid, or salicylaldehyde o-aminophenol.

[0021] Furthermore, in the composition provided by the present invention, the mass ratio of the octenylamine to the chelating agent is 5:1 to 1:5.

[0022] Furthermore, in the composition provided by the present invention, the polymeric compound is selected from at least one of polymethyl methacrylate, maltodextrin, propylene glycol monolaurate, polyacrylamide, hydroxypropyl methylcellulose, polyacrylate, polyvinylpyrrolidone, and polyvinyl alcohol.

[0023] Furthermore, in the composition provided by the present invention, the mass ratio of the kasugamycin to the polymer compound is 5:1 to 1:5.

[0024] On the other hand, the present invention relates to a method for preparing the above-mentioned composition, comprising: mixing octenylamine and a chelating agent to obtain the octenylamine chelate;

[0025] The composite octochlor was prepared by mixing the octochlor chelate with a pH adjuster.

[0026] The composition was prepared by mixing the compound octochlor, the polymer compound, and kasugamycin.

[0027] On the other hand, the present invention relates to a pesticide formulation, wherein the raw materials of the pesticide formulation include the aforementioned composition and adjuvants.

[0028] According to practical application needs, the composition provided by this invention can be prepared into one of the following formulations: emulsion, microemulsion, suspension, wettable powder, water-dispersible granule, etc., according to methods known to those skilled in the art. The above formulations also contain adjuvants required for formulating pesticide formulations. These adjuvants can be one or a mixture of several of the following: solvent, emulsifier, wetting agent, stabilizer, dispersant, thickener, pH adjuster, defoamer, antifreeze, filler, etc. The adjuvants described in this invention can all be known substances, such as various adjuvants commonly used in pesticide formulations, and can vary depending on the specific circumstances, without particular limitation.

[0029] On the other hand, the present invention relates to the use of the composition in the preparation of bactericides.

[0030] The composition provided by the present invention does not have a particular limitation on the amount of kasugamycin. As those skilled in the art will readily know, the mass ratio of kasugamycin to cymoxanil is 10:1 to 1:80, and both exhibit good synergistic effects when used as bactericides.

[0031] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages:

[0032] This invention effectively inhibits the decomposition problem caused by ionic bond reactions when octochlor and kasugamycin are combined by using the synergistic effect of chelating agents, polymers, pH adjusters, etc., significantly reducing the decomposition rate of octochlor and kasugamycin. Furthermore, it reduces the direct contact of active ingredients through physical coating and chemical chelation, thus solving the stability problems of crystallization, precipitation, and flocculation in the formulation. Attached Figure Description

[0033] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 This is a schematic diagram of the liquid composition prepared for the formulation example.

[0035] Figure 2 This is a schematic diagram of the liquid composition prepared in Comparative Formulation Example 1.

[0036] Figure 3 This is a schematic diagram of the liquid composition prepared in Comparative Formulation Example 2.

[0037] Figure 4 This is a schematic diagram of the liquid composition prepared in Comparative Formulation Example 3. Detailed Implementation

[0038] The technical solution of the present invention will be described below with reference to embodiments; however, the present invention is not limited to the following embodiments. Unless otherwise specified, the experimental and detection methods described in each embodiment are conventional methods; the reagents and materials described are commercially available unless otherwise specified. Unless otherwise specified, all percentages in the following embodiments refer to mass percentages. Unless otherwise specified, all proportions in the following embodiments refer to mass ratios.

[0039] The technical grade of cymoxanil was purchased from Xi'an Dingsheng Biochemical Co., Ltd.

[0040] Kasugamycin technical grade was purchased from Shaanxi Maikelu Biotechnology Co., Ltd.

[0041] For example, the composition of the active ingredients in the composition provided by the present invention, by weight percentage, is as follows:

[0042]

[0043] Example 1

[0044] This embodiment provides a method for preparing a composition.

[0045] This example is for solid dosage forms.

[0046] Step 1: Mix the technical grade octochlor with a solid carrier, add a chelating agent, and react to obtain octochlor chelate.

[0047] Step 2: Add a pH adjuster to the octenamine chelate to ammonium salts.

[0048] Step 3: Add a high molecular weight compound, kasugamycin technical, adjuvants and fillers to the ammonium salt octopamine chelate to finally obtain the composition.

[0049] Example 2

[0050] This embodiment provides a method for preparing a composition.

[0051] This example is for a liquid formulation.

[0052] Step 1: Mix the technical grade octenamine and solvent, add a chelating agent, and react to obtain octenamine chelate.

[0053] Step 2: In another reaction vessel, the polymer compound, kasugamycin technical, solvent, antifreeze, and emulsifier are mixed and reacted to obtain the kasugamycin coating.

[0054] Step 3: Mix the octochlor chelate and the kasugamycin coating, then add a pH adjuster to adjust the pH of the product to between 4 and 6, and finally obtain the composition.

[0055] Formulation Example 1

[0056] This formulation example provides a 40% kasugamycin·cyprodinil wettable powder, comprising the following components by weight of active ingredient:

[0057]

[0058] Weigh the above materials according to the ratio, first use fumed silica to stir and adsorb octochlor, then add dihydroxyethylglycine and mix evenly to chelate, add citric acid and stir to mix, and obtain compound octochlor; add polymethyl methacrylate, kasugamycin, sodium dodecyl sulfate, sodium dioctyl succinate sulfonate and kaolin to the compound octochlor, and then pulverize the above premix under high pressure airflow to obtain 40% kasugamycin·octochlor wettable powder.

[0059] Formulation Example 2

[0060] This formulation example provides a 25% kasugamycin·cyprodinil wettable powder, comprising the following components by weight of active ingredient:

[0061]

[0062] Weigh the above materials according to the formula, first use fumed silica to stir and adsorb octochlor, then add diethylenetriamine pentamethylphosphonic acid and mix evenly to chelate, add citric acid and stir to prepare composite octochlor; add polyvinyl alcohol, kasugamycin, sodium dodecyl sulfate, sodium dioctyl succinate sulfonate and kaolin to the composite octochlor, and then pulverize the above premix under high pressure airflow to obtain 25% kasugamycin·octochlor wettable powder.

[0063] Formulation Example 3

[0064] This formulation example provides a 35% kasugamycin·cyprodinil water-dispersible granule, comprising the following components by weight of active ingredient:

[0065]

[0066] Weigh the above materials according to the formula, first use fumed silica to stir and adsorb octochlor, then add hydroxyethyl ethylenediamine triacetic acid and mix evenly to chelate, add citric acid and stir to mix, to obtain composite octochlor; add polyvinylpyrrolidone, kasugamycin, naphthalene sulfonate formaldehyde condensate, polyethylene glycol copolymer carboxylate, fatty alcohol polyoxyethylene ether sulfate salt and kaolin to the composite octochlor and mix evenly, then pulverize the above premix under high pressure airflow, knead and granulate, and sieve to obtain 35% kasugamycin·octochlor water dispersible granules.

[0067] Formulation Example 4

[0068] This formulation example provides a 30% kasugamycin·cyprodinil water-dispersible granule, comprising the following components by weight of active ingredient:

[0069]

[0070] Weigh the above materials according to the proportions, first use fumed silica to stir and adsorb octochlor, then add sodium tripolyphosphate and polymethacrylic acid to mix evenly and chelate, add citric acid and stir to mix, and obtain composite octochlor; add polyvinylpyrrolidone, kasugamycin, naphthalene sulfonate formaldehyde condensate, polyethylene glycol copolymer carboxylate, fatty alcohol polyoxyethylene ether sulfate salt and kaolin to the composite octochlor and mix evenly, then pulverize the above premix under high pressure, knead and granulate, and sieve to obtain 30% kasugamycin·octochlor water dispersible granules.

[0071] Formulation Example 5

[0072] This formulation example provides a 40% kasugamycin·cyprodinil water-dispersible granule, comprising the following components by weight of active ingredient:

[0073]

[0074] Weigh the above materials according to the formula, first use fumed silica to stir and adsorb octochlor, then add sodium diethyldithiocarbamate (NaDDC) and mix evenly to chelate, add citric acid and stir to mix, to obtain composite octochlor; add hydroxypropyl methylcellulose, kasugamycin, naphthalene sulfonate formaldehyde condensate, polyethylene glycol copolymer carboxylate, fatty alcohol polyoxyethylene ether sulfate salt and kaolin to the composite octochlor and mix evenly, then pulverize the above premix under high pressure airflow, add water to knead and granulate, granulate and sieve to obtain 40% kasugamycin·octochlor water dispersible granules.

[0075] Formulation Example 6

[0076] This formulation example provides a 2.8% kasugamycin·cyprodinil soluble concentrate, comprising the following components by weight of active ingredient:

[0077]

[0078]

[0079] Weigh the above materials according to the proportions and proceed in two steps: ① First, dissolve octochlor in a portion of water by stirring, then add a solution of o-vanillin glycine in dimethylacetamide and mix thoroughly to obtain octochlor chelate; ② Dissolve kasugamycin in the remaining water, then add polyvinylpyrrolidone, Tween 80, and glycerol, and stir thoroughly to obtain kasugamycin coating; ③ Add the liquid from step ① to step ② while stirring, and mix thoroughly until clear and transparent; ④ Finally, add lactic acid to adjust the pH of the product to between 4 and 6 to obtain a 2.8% kasugamycin·octochlor soluble concentrate.

[0080] Formulation Example 7

[0081] This formulation example provides a 5% kasugamycin·cyprodinil soluble concentrate, comprising the following components by weight of active ingredient:

[0082]

[0083] Weigh the above materials according to the proportions and proceed in two steps: ① First, dissolve octochlor in a portion of water by stirring, then add a solution of o-vanillin glycine and decylamide and mix thoroughly to obtain octochlor chelate; ② Dissolve kasugamycin in the remaining water, then add polyvinylpyrrolidone, Tween 80, and glycerol, and stir thoroughly to obtain kasugamycin coating; ③ Add the liquid from step ① to step ② while stirring, and mix thoroughly until clear and transparent; ④ Finally, add lactic acid to adjust the pH of the product to between 4 and 6 to obtain a 5% kasugamycin·octochlor soluble concentrate.

[0084] Formulation Example 8

[0085] This formulation example provides a 7% kasugamycin·cyprodinil soluble concentrate, comprising the following components by weight of active ingredient:

[0086]

[0087] Weigh the above materials according to the proportions and proceed in two steps: ① First, dissolve octochlor in a portion of the water by stirring, then add sodium pyrophosphate and sodium EDTA and mix evenly to obtain octochlor chelate; ② Dissolve kasugamycin in the remaining water, then add propylene glycol monolaurate, Tween 80, and glycerol, and stir evenly to obtain kasugamycin coating; ③ Add the liquid from step ① to step ② while stirring, and mix thoroughly until clear and transparent; ④ Finally, add lactic acid to adjust the pH of the product to between 4 and 6 to obtain a 7% kasugamycin·octochlor soluble concentrate.

[0088] Formulation Example 9

[0089] This formulation example provides a 5% kasugamycin·cyprodinil soluble concentrate, comprising the following components by weight of active ingredient:

[0090]

[0091] Weigh the above materials according to the proportions and proceed in two steps: ① Dissolve octochlor in a portion of the water by stirring, then add sodium hexametaphosphate and mix evenly to obtain octochlor chelate; ② Dissolve kasugamycin in the remaining water, then add propylene glycol monolaurate, Tween 80, and glycerol, and stir evenly to obtain kasugamycin coating; ③ Add the liquid from step ① to step ② while stirring, and mix thoroughly until clear and transparent; ④ Finally, add lactic acid to adjust the pH of the product to between 4 and 6 to obtain a 5% kasugamycin·octochlor soluble concentrate.

[0092] Formulation Example 10

[0093] This formulation example provides a 4% kasugamycin·cyprodinil soluble concentrate, comprising the following components by weight of active ingredient:

[0094]

[0095] Weigh the above materials according to the proportions and proceed in two steps: ① Dissolve octochlor in a portion of the water by stirring, then add polyacrylic acid and mix evenly to obtain octochlor chelate; ② Dissolve kasugamycin in the remaining water, then add maltodextrin glucoside, Tween 80, and glycerol, and stir evenly to obtain kasugamycin coating; ③ Add the liquid from step ① to step ② while stirring, and mix thoroughly until clear and transparent; ④ Finally, add lactic acid to adjust the pH of the product to between 4 and 6 to obtain a 4% kasugamycin·octochlor soluble concentrate.

[0096] Formulation Example 11

[0097] This formulation example provides a 5% kasugamycin·cyprodinil soluble concentrate, comprising the following components by weight of active ingredient:

[0098]

[0099] Weigh the above materials according to the proportions and proceed in two steps: ① First, dissolve octochlor in a portion of the water by stirring, then add sodium hexametaphosphate and polymethacrylic acid and mix evenly to obtain octochlor chelate; ② Dissolve kasugamycin in the remaining water, then add polyacrylamide, Tween 80, and glycerol, and stir evenly to obtain kasugamycin coating; ③ Add the liquid from step ① to step ② while stirring, and mix thoroughly until clear and transparent; ④ Finally, add lactic acid to adjust the pH of the product to between 4 and 6 to obtain a 5% kasugamycin·octochlor soluble concentrate.

[0100] Comparative Formulation Example 1

[0101] This formulation example is the same as Formulation Example 4, except that no chelating agent is added, such as... Figure 4 As shown, precipitation occurs.

[0102] Comparative Formulation Example 2

[0103] This formulation example is the same as Formulation Example 4, except that no polymeric compound is added, such as... Figure 3 As shown, crystallization occurs.

[0104] Comparative Formulation Example 3

[0105] This formulation example is the same as Formulation Example 4, except that no chelating agent and polymeric compound are added, such as Figure 2 As shown, flocculation occurs.

[0106] The pesticides prepared in Formulation Examples 1-13 and the pesticides prepared in Comparative Formulation Examples 1-3 were subjected to liquid chromatography detection, and the detection results are shown in Table 1.

[0107] The degradation rate of kasugamycin, DK (%), is calculated as follows: (Initial concentration of kasugamycin raw material - Remaining concentration) ÷ Initial concentration of kasugamycin raw material × 100%.

[0108] The degradation rate of octochlor (DE) (%) = (initial concentration of octochlor raw material - remaining concentration) ÷ initial concentration of octochlor raw material × 100%;

[0109] Current degradation rate: For liquid formulations, the concentrations of kasugamycin and octochlor in the liquid were immediately measured after preparation as the residual concentration; for solid formulations, the mixture was immediately dispersed in 10 times its volume of deionized water after preparation, and the concentrations of kasugamycin and octochlor in the mixture were immediately measured as the residual concentration.

[0110] Thermal degradation rate: For liquid formulations, the concentrations of kasugamycin and octochlor in the liquid were measured after the prepared liquid was stored at 54℃ for 14 days as the residual concentration; for solid formulations, the concentrations of kasugamycin and octochlor in the mixture were measured after the prepared liquid was stored at 54℃ for 14 days and then dispersed in 10 times the volume of deionized water as the residual concentration.

[0111] Low-temperature degradation rate: For liquid formulations, the concentrations of kasugamycin and octochlor in the liquid were measured after the prepared liquid was stored at 0℃ for 7 days as the residual concentration; for solid formulations, the concentrations of kasugamycin and octochlor in the mixture were measured after the prepared liquid was stored at 0℃ for 7 days and then dispersed in 10 times the volume of deionized water as the residual concentration.

[0112] Table 1 Degradation Improvement

[0113]

[0114] As shown in Table 1, this invention, by chelating octochlor and a chelating agent to form octochlor chelates, and combining them with polymeric compounds as formulation raw materials, effectively inhibits the decomposition problem caused by ionic bond reactions when octochlor and kasugamycin are combined, significantly reducing the decomposition rate of octochlor and kasugamycin. Furthermore, by reducing direct contact between the active ingredients through physical coating and chemical chelation, it solves the stability problems of crystallization, precipitation, and flocculation in the formulation. In contrast, using octochlor chelates or polymeric compounds alone has a limited effect on improving the decomposition rate of octochlor and kasugamycin, and still results in problems such as crystallization, precipitation, and flocculation.

[0115] As described above, the basic principles, main features, and advantages of the present invention have been well described. The above embodiments and specifications are merely descriptions of preferred embodiments of the present invention, and the present invention is not limited to the above embodiments. Various changes and improvements made to the technical solutions of the present invention by those skilled in the art without departing from the spirit and scope of the present invention should fall within the protection scope defined by the present invention.

Claims

1. A composition, characterized in that, The composition is formed by compounding octochlor chelate, a high molecular weight compound and kasugamycin; The octenamine chelate is prepared by chelating octenamine and a chelating agent.

2. The composition according to claim 1, characterized in that, The chelating agent is an inorganic salt chelating agent and / or an organic chelating agent.

3. The composition according to claim 2, characterized in that, The inorganic salt chelating agent is selected from at least one of sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, sodium gluconate, potassium tartrate, and sodium citrate.

4. The composition according to claim 2, characterized in that, The organic chelating agent is selected from at least one of the following: chelating agents containing carboxyl and amino coordination groups, chelating agents containing hydroxyl and carboxyl coordination groups, hydroxyaminocarboxylic acid chelating agents, organic polyphosphonic acid chelating agents, polycarboxylic acid chelating agents, thiol-containing chelating agents, and Schiff base chelating agents.

5. The composition according to claim 1, characterized in that, The mass ratio of octochlor to the chelating agent is 5:1 to 1:

5.

6. The composition according to claim 1, characterized in that, The polymer compound is selected from at least one of polymethyl methacrylate, maltodextrin, propylene glycol monolaurate, polyacrylamide, hydroxypropyl methylcellulose, polyacrylate, polyvinylpyrrolidone, and polyvinyl alcohol.

7. The composition according to claim 1, characterized in that, The mass ratio of the kasugamycin to the polymer compound is 5:1 to 1:

5.

8. A method for preparing the composition according to any one of claims 1 to 7, characterized in that, include: The technical grade of octenamine and a solid carrier were mixed, and a chelating agent was added to react and prepare octenamine chelate. A pH adjuster was added to the octochlor chelate to make the octochlor chelate ammonium salt. The composition is prepared by adding a polymeric compound, kasugamycin technical, adjuvants, and fillers to the amine-salted octochlor chelate.

9. A method for preparing the composition according to any one of claims 1 to 7, characterized in that, include: After mixing the technical grade octenamine and the solvent, a chelating agent was added, and the reaction was carried out to obtain octenamine chelate; A kasugamycin-coated compound is prepared by mixing a polymeric compound, kasugamycin technical, a solvent, an antifreeze agent, and an emulsifier, and then reacting the mixture. The composition is prepared by mixing octochlor chelate and kasugamycin coating, and then adding a pH adjuster to adjust the pH of the product to between 4 and 6.

10. A pesticide formulation, characterized in that, The raw materials of the pesticide formulation include the composition and adjuvants described in any one of claims 1 to 7.

11. Use of the composition according to any one of claims 1 to 7 in the preparation of a bactericide.

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