A water-soluble medicated fertilizer containing metalaxyl-M and ipconazole and its preparation method

Abstract

A water-soluble fertilizer-pesticide containing metalaxyl-M and ipconazole and its preparation method. The active ingredients of the water-soluble fertilizer-pesticide are metalaxyl-M and ipconazole, and the carrier is selected from one or more of macronutrient fertilizers, micronutrient fertilizers, and trace element fertilizers; the carrier can also be amino acids, humic acids, etc.; the dosage form is a soluble powder; β-cyclodextrin is used as an inclusion material to prepare an inclusion complex of metalaxyl-M and ipconazole, so as to improve the solubility of metalaxyl-M and ipconazole in water and have better drug efficacy; the inclusion complex material contains citric acid phosphoric anhydride, and citric acid phosphoric anhydride can promote the absorption and conduction of the drug, and can achieve the effect of carrying the pesticide with the fertilizer and the pesticide promoting the fertilizer efficiency; the water-soluble fertilizer-pesticide can be sprayed on the leaves or used in the soil, with a wide range of applications and is easy to promote and apply.

Description

Technical Field

[0001] The present invention relates to the technical field of medicated fertilizers, and particularly relates to a water-soluble medicated fertilizer containing metalaxyl-M and ipconazole and a preparation method thereof. Background Art

[0002] A "medicated fertilizer mixture" is a functional fertilizer that has one or more functions of killing or suppressing crop pests and diseases or regulating crop growth, and can provide nutrients for crops, or simultaneously has the functions of providing nutrients and improving the utilization rates of fertilizers and pesticides. It has nine major advantages, including balanced fertilization and complete nutrition; broad-spectrum high efficiency and one-time completion; pre-control and post-promotion to enhance stress resistance; combination of fertilizer and medicine with synergistic effects; simple operation and safe use; labor saving and cost reduction, increasing production and income; using fertilizer instead of materials, safe and environmentally friendly; convenient storage and transportation, low-carbon and energy-saving; multiple benefits, beneficial to the country and the people. It unifies the two most important agricultural chemicals, pesticides and fertilizers, used in agriculture, and considering the possible decrease in their respective effects after natural encounter, it combines the two field operations of plant protection by pesticides and nutrient supply by fertilizers into one, saving labor and reducing production costs. When both pesticides and fertilizers are in the optimal application period, the drug efficacy and fertilizer efficiency can be improved. Some developed countries in the world have launched medicated fertilizer mixtures on the market. The most promising medicated fertilizer mixture (KAC) considered by the Second International Fertilizer Conference is to add herbicides, trace elements and hormones to it. The manufacturing of medicated fertilizer mixtures abroad has developed into a huge branch of the fertilizer industry, while the domestic medicated fertilizer industry is still imperfect and there is a large gap.

[0003] Cyclodextrin (CD for short) is a non-toxic, odorless white powdery solid, which is a general term for a series of cyclic oligosaccharides generated by the action of cyclodextrin glucosyltransferase produced by Bacillus on amylose. Since the glycosidic bond connecting glucose units cannot rotate freely, cyclodextrin forms a slightly conical ring. The primary hydroxyl groups of cyclodextrin surround the small mouth of the cone, and its secondary hydroxyl groups surround the large mouth of the cone. Based on the structural characteristics of cyclodextrin itself, it has a hydrophobic inner cavity and a hydrophilic surface. Among them, β-cyclodextrin (β-CD) is widely used as a molecular carrier in the pharmaceutical industry, food and other industrial fields.

[0004] Metalaxyl-M is the R isomer of metalaxyl and is a systemic fungicide with a protective effect. It can be absorbed by the roots, stems and leaves of plants and has the efficacy of preventing and controlling crop diseases caused by downy mildew, Phytophthora and Pythium. Ipconazole has good control effects on diseases caused by ascomycetes, basidiomycetes, deuteromycetes and zygomycetes except oomycetes. At present, there is no reported medicated fertilizer with metalaxyl-M and ipconazole as two active ingredients and coated with cyclodextrin for the two active ingredients. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole, which is effective against a variety of fungal diseases, has high control efficacy and long-lasting drug effect, and a preparation method thereof.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is as follows: A water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole, the water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole comprises the following components by weight percentage: metalaxyl-M 0.01% - 5%, ipconazole 0.01% - 1%, β-cyclodextrin 1% - 5%, citric acid phosphoric anhydride 0.1% - 5%, and the balance is water-soluble fertilizer; the water-soluble fertilizer is one or more of macronutrient fertilizers, secondary nutrient fertilizers, and micronutrient fertilizers.

[0007] Further, a water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole, the water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole comprises the following components by weight percentage: metalaxyl-M 0.05% - 5%, ipconazole 0.05% - 1%, β-cyclodextrin 2% - 5%, citric acid phosphoric anhydride 0.3% - 5%, and the balance is water-soluble fertilizer; the water-soluble fertilizer is one or more of macronutrient fertilizers, secondary nutrient fertilizers, and micronutrient fertilizers.

[0008] Further, a water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole, the water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole comprises the following components by weight percentage: metalaxyl-M 0.25% - 5%, ipconazole 0.25% - 1%, β-cyclodextrin 3% - 5%, citric acid phosphoric anhydride 0.5% - 5%, and the balance is water-soluble fertilizer; the water-soluble fertilizer is one or more of macronutrient fertilizers, secondary nutrient fertilizers, and micronutrient fertilizers.

[0009] Further, the weight ratio of the two active ingredients of metalaxyl-M and ipconazole is: metalaxyl-M: ipconazole = 1:2 - 10:1.

[0010] Further, the weight ratio of the two active ingredients of metalaxyl-M and ipconazole is: metalaxyl-M: ipconazole = 1:1 - 5:1.

[0011] Further, the cumulative mass percentage of the two active ingredients of metalaxyl-M and ipconazole is 0.2% - 5%.

[0012] Further, the cumulative mass percentage of the two active ingredients of metalaxyl-M and ipconazole is 1.25% - 5%.

[0013] The present invention also provides a preparation method of a water-soluble fertilizer and pesticide containing metalaxyl-M and ipconazole, comprising the following steps:

[0014] (1) Weighing of raw materials: Weigh each component of the water-soluble medicine fertilizer containing metalaxyl-M and flutriafol according to weight percentage;

[0015] (2) Preparation of the original drug organic solution: Dissolve metalaxyl-M and flutriafol in methanol to obtain the original drug organic solution;

[0016] (3) Preparation of the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride: Dissolve β-cyclodextrin and citric acid phosphoric anhydride in distilled water, mix evenly to obtain the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride;

[0017] (4) Preparation of the inclusion complex solution: Stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride, and under the condition of continuous stirring, add the original drug organic solution, continue to stir continuously for 0.5 - 24 h, and let it stand to obtain the inclusion complex solution;

[0018] (5) Preparation of the β-cyclodextrin inclusion complex containing metalaxyl-M and flutriafol: Remove methanol from the inclusion complex solution to obtain a filtrate; Spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing metalaxyl-M and flutriafol;

[0019] (6) Mix the β-cyclodextrin inclusion complex containing metalaxyl-M and flutriafol with the water-soluble fertilizer evenly to obtain the water-soluble medicine fertilizer containing metalaxyl-M and flutriafol.

[0020] Further, in step (4), first heat the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride to 35 - 40 °C; then stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride at a rate of 100 - 200 r / min; Control the temperature of the original drug organic solution at 15 - 20 °C, and the temperature difference between the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride and the original drug organic solution is 15 - 20 °C. Under the condition of continuous stirring, add the original drug organic solution, continue to stir continuously for 0.5 - 24 h, and let it stand to obtain the inclusion complex solution.

[0021] Further, the spray-drying process in step (5) is: the inlet temperature is 70 - 85 °C, the feeding rate is 500 - 600 ml / h, the air inlet volume is 85 - 100 m 3 / h, and the outlet temperature is 50 - 55 °C.

[0022] A water-soluble medicine fertilizer containing metalaxyl-M and ipconazole and its preparation method. The active components of the medicine fertilizer are composed of metalaxyl-M and ipconazole. Metalaxyl-M is the R isomer of metalaxyl, which is a systemic fungicide with a protective effect. It can be absorbed by the roots, stems and leaves of plants and has the efficacy of preventing and controlling crop diseases caused by downy mildew, Phytophthora and Pythium. Ipconazole has good control effects on diseases caused by ascomycetes, basidiomycetes, deuteromycetes and zygomycetes except oomycetes. After compounding with metalaxyl or metalaxyl-M, it is effective against almost all fungal diseases.

[0023] A water-soluble medicine fertilizer containing metalaxyl-M and ipconazole and its preparation method. Some studies have shown that citric acid is a small molecule organic acid containing carbon. Such organic acids are produced by plants in a phosphorus-deficient soil environment. When the available phosphorus in the soil is insufficient, the organic acids exuded from the roots of plants can combine with the phosphorus that cannot be utilized in the soil, and then be transported to the roots of plants in the form of citric acid phosphoanhydride and be quickly absorbed, which can make phosphorus more effectively absorbed. Citric acid phosphoanhydride is also added to the water-soluble medicine fertilizer of this application. The oxygen-containing functional groups with negative charges on the citric acid phosphoanhydride molecule can adsorb the metal ions with positive charges in the soil. At the same time, specific sites on the citric acid phosphoanhydride can complex the active ingredients of the water-soluble medicine fertilizer, so as to carry the medicine and fertilizer together to the roots of the plants and be quickly absorbed, thus realizing the effect of promoting the efficacy of the fertilizer with the medicine. After compounding with metalaxyl or metalaxyl-M, the added citric acid phosphoanhydride becomes an enhancer, which can greatly improve the control effect of fungal diseases.

[0024] A water-soluble medicine fertilizer containing metalaxyl-M and ipconazole and its preparation method. The active ingredients of the water-soluble medicine fertilizer are metalaxyl-M and ipconazole. The carrier is selected from one or more of large element fertilizers, medium element fertilizers and trace element fertilizers; the carrier can also be amino acids, humic acids, etc.; the dosage form is a soluble powder; β-cyclodextrin is used as an inclusion material to prepare an inclusion complex of metalaxyl-M and ipconazole to improve the solubility of metalaxyl-M and ipconazole in water and the drug efficacy is better; the inclusion complex material contains citric acid phosphoanhydride, which can promote the absorption and conduction of the drug and can realize the effect of promoting the efficacy of the fertilizer with the medicine; the water-soluble medicine fertilizer can be sprayed on the leaves or used in the soil, with a wide range of applications and is easy to popularize and apply.

[0025] In summary, a water-soluble medicine fertilizer containing metalaxyl-M and ipconazole and its preparation method of the present invention has the following beneficial effects:

[0026] 1. There is no compound of metalaxyl-M and ipconazole in the existing medicine fertilizer products. After ipconazole is compounded with metalaxyl-M, it is effective against almost all fungal diseases;

[0027] 2. Metalaxyl-M and prothioconazole have low solubility in water and it is difficult to prepare them into water-soluble formulations. The present invention improves the solubility of the two agents in water by preparing inclusion compounds and prepares soluble powders. Most of the existing medicine-fertilizer products are granular or water-soluble medicine-fertilizers. The dosage form of this invention is soluble powder, which can be used for root irrigation, broadcasting, and liquid spraying, with a wider scope of application.

[0028] 3. To improve the utilization rate of medicine and fertilizer, citric acid phosphoanhydride is added to the medicine-fertilizer of the present invention. The oxygen-containing functional groups with negative charges on the small molecule of citric acid can adsorb the metal ions with positive charges in the soil. At the same time, specific sites on citric acid can also complex the active ingredients of pesticides, so as to carry the medicine and fertilizer to the root of the plant together and be quickly absorbed, thus achieving the effect of promoting the effect of medicine with fertilizer and promoting the fertilizer efficiency with medicine.

[0029] 4. Citric acid phosphoanhydride is also added to the water-soluble medicine-fertilizer. The oxygen-containing functional groups with negative charges on the citric acid phosphoanhydride molecule can adsorb the metal ions with positive charges in the soil. At the same time, specific sites on the citric acid phosphoanhydride can complex the active ingredients of the water-soluble medicine-fertilizer, so as to carry the medicine and fertilizer to the root of the plant together and be quickly absorbed, thus achieving the effect of promoting the effect of medicine with fertilizer and promoting the fertilizer efficiency with medicine. After compounding with metalaxyl or metalaxyl-M, the added citric acid phosphoanhydride becomes an enhancer, which can greatly improve the control effect of fungal diseases.

[0030] The present invention relates to a water-soluble medicine-fertilizer containing metalaxyl-M and prothioconazole and its preparation method, and also optimizes the preparation process of the inclusion compound solution, reasonably controls the stirring rate, the temperature of the β-cyclodextrin aqueous solution containing citric acid phosphoanhydride, the temperature of the original drug organic solution, and the temperature difference between the two. With the advantages of stirring and temperature difference, the saturation effect of β-cyclodextrin is significantly enhanced, and the inclusion rate of the β-cyclodextrin inclusion compound containing metalaxyl-M and prothioconazole increases by more than 10%. Detailed implementation mode

[0031] The following examples can help those skilled in the art to understand the present invention more comprehensively, but cannot limit the present invention in any way.

[0032] The present invention relates to a water-soluble medicine-fertilizer containing metalaxyl-M and prothioconazole and its preparation method. The carrier is selected from one or more of fertilizers, macronutrient fertilizers, micronutrient fertilizers, and medium nutrient fertilizers; the carrier can also be amino acids, humic acids, etc.; more specifically, the carrier can be selected from nitrogen fertilizers: urea, ammonium bicarbonate, ammonium nitrate, ammonium sulfate, ammonium chloride, monoammonium phosphate, diammonium phosphate; it can be selected from phosphate fertilizers: monoammonium phosphate, diammonium phosphate, potassium dihydrogen phosphate; it can be selected from potassium fertilizers: potassium chloride, potassium sulfate, potassium nitrate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, etc.

[0033] Example 1: 0.5% Metalaxyl-M + 0.25% Prothioconazole soluble powder

[0034] Formula:

[0035] Metalaxyl-M 0.5%

[0036] Cyproconazole 0.75%

[0037] β-Cyclodextrin 3%

[0038] Citric acid phosphoric anhydride 3%

[0039] Water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer supplemented

[0040] Process: Preparation method of 0.5% Metalaxyl-M + 0.25% Cyproconazole soluble powder, including the following steps:

[0041] (1) Weighing of raw materials: Weigh each component of the water-soluble medicated fertilizer containing Metalaxyl-M and Cyproconazole according to the weight percentage;

[0042] (2) Preparation of the original drug organic solution: Dissolve 0.5% Metalaxyl-M + 0.25% Cyproconazole in methanol to obtain the original drug organic solution;

[0043] (3) Preparation of β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride: Dissolve β-cyclodextrin and citric acid phosphoric anhydride in distilled water and mix evenly to obtain β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride;

[0044] (4) Preparation of the inclusion complex solution: First, heat the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride to 35°C; then stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride at a rate of 100 r / min; control the temperature of the original drug organic solution at 15°C, and the temperature difference between the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride and the original drug organic solution is 20°C. Under continuous stirring, add the original drug organic solution and continue to stir continuously for 4 h, and then let it stand to obtain the inclusion complex solution;

[0045] (5) Preparation of β-cyclodextrin inclusion complex containing Metalaxyl-M and Cyproconazole: Evaporate methanol in the inclusion complex solution under reduced pressure to obtain a filtrate; spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing Metalaxyl-M and Cyproconazole; The spray-drying process is: the inlet temperature is 70°C, the feeding rate is 500 ml / h, the air intake is 85 m 3 / h, and the outlet temperature is 50°C;

[0046] (6) Mix the β-cyclodextrin inclusion complex containing Metalaxyl-M and Cyproconazole with the water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain 0.5% Metalaxyl-M + 0.25% Cyproconazole soluble powder.

[0047] Example 2: 1% Metalaxyl-M + 1.25% Cyproconazole soluble powder

[0048] Formula:

[0049] Metalaxyl-M 1%

[0050] Picoxystrobin 1.25%

[0051] β-Cyclodextrin 5%

[0052] Citric acid phosphoric anhydride 5%

[0053] Water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer supplemented

[0054] Process: Preparation method of 1% Metalaxyl-M + 1.25% Picoxystrobin soluble powder, including the following steps:

[0055] (1) Weighing of raw materials: Weigh each component of the water-soluble medicine fertilizer containing Metalaxyl-M and Picoxystrobin according to the weight percentage;

[0056] (2) Preparation of original drug organic solution: Dissolve 1% Metalaxyl-M + 1.25% Picoxystrobin in methanol to obtain the original drug organic solution;

[0057] (3) Preparation of β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride: Dissolve β-cyclodextrin and citric acid phosphoric anhydride in distilled water and mix evenly to obtain β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride;

[0058] (4) Preparation of inclusion complex solution: First, heat the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride to 40°C; then stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride at a rate of 200 r / min; control the temperature of the original drug organic solution at 20°C, and the temperature difference between the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride and the original drug organic solution is 20°C. Under continuous stirring, add the original drug organic solution and continue to stir continuously for 5 h, and then let it stand to obtain the inclusion complex solution;

[0059] (5) Preparation of β-cyclodextrin inclusion complex containing Metalaxyl-M and Picoxystrobin: Evaporate methanol in the inclusion complex solution under reduced pressure to obtain a filtrate; spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing Metalaxyl-M and Picoxystrobin; the spray-drying process is: the inlet temperature is 85°C, the feeding rate is 600 ml / h, the air inlet volume is 100 m 3 / h, and the outlet temperature is 55°C;

[0060] (6) Mix the β-cyclodextrin inclusion complex containing Metalaxyl-M and Picoxystrobin with water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain 1% Metalaxyl-M + 1.25% Picoxystrobin soluble powder.

[0061] Example 3: 0.05% Metalaxyl-M + 0.05% Fludioxonil Soluble Powder

[0062] Formulation:

[0063] Metalaxyl-M 0.05%

[0064] Fludioxonil 0.05%

[0065] β-Cyclodextrin 3%

[0066] Citric acid phosphoric anhydride 3%

[0067] Water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer to make up the balance

[0068] Process: Preparation method of 0.05% Metalaxyl-M + 0.05% Fludioxonil soluble powder, including the following steps:

[0069] (1) Weighing of raw materials: Weigh each component of the water-soluble medicated fertilizer containing Metalaxyl-M and Fludioxonil according to the weight percentage;

[0070] (2) Preparation of the original drug organic solution: Dissolve 0.05% Metalaxyl-M + 0.05% Fludioxonil in methanol to obtain the original drug organic solution;

[0071] (3) Preparation of the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride: Dissolve β-cyclodextrin and citric acid phosphoric anhydride in distilled water, mix evenly to obtain the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride;

[0072] (4) Preparation of the inclusion complex solution: First, heat the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride to 35°C; then stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride at a rate of 150 r / min; control the temperature of the original drug organic solution at 20°C, with a temperature difference of 15°C between the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride and the original drug organic solution, and under continuous stirring, add the original drug organic solution and continue to stir continuously for 7 h, then let it stand to obtain the inclusion complex solution;

[0073] (5) Preparation of the β-cyclodextrin inclusion complex containing Metalaxyl-M and Fludioxonil: Evaporate the methanol in the inclusion complex solution under reduced pressure to obtain a filtrate; spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing Metalaxyl-M and Fludioxonil; the spray-drying process is: the inlet temperature is 75°C, the feeding rate is 550 ml / h, the air intake is 90 m 3 / h, and the outlet temperature is 52°C;

[0074] (6) Mix the β-cyclodextrin inclusion complex containing Metalaxyl-M and Fludioxonil with the water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain 0.05% Metalaxyl-M + 0.05% Fludioxonil soluble powder.

[0075] Example 4: 0.25% metalaxyl-M + 0.25% ipconazole soluble powder

[0076] Formulation:

[0077] Metalaxyl-M 0.25%

[0078] Ipconazole 0.25%

[0079] β-cyclodextrin 4%

[0080] Citric acid phosphoric anhydride 4%

[0081] Water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer to make up

[0082] Process: Preparation method of 0.25% metalaxyl-M + 0.25% ipconazole soluble powder, including the following steps:

[0083] (1) Weighing of raw materials: Weigh each component of the water-soluble medicine fertilizer containing metalaxyl-M and ipconazole according to the weight percentage;

[0084] (2) Preparation of original drug organic solution: Dissolve 0.25% metalaxyl-M + 0.25% ipconazole in methanol to obtain the original drug organic solution;

[0085] (3) Preparation of β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride: Dissolve β-cyclodextrin and citric acid phosphoric anhydride in distilled water, mix evenly to obtain β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride;

[0086] (4) Preparation of inclusion complex solution: Stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride at room temperature with magnetic force, and under the condition of continuous stirring, add the original drug organic solution, continue to stir continuously for 4 h, and let it stand to obtain the inclusion complex solution;

[0087] (5) Preparation of β-cyclodextrin inclusion complex containing metalaxyl-M and ipconazole: Evaporate methanol in the inclusion complex solution under reduced pressure to obtain a filtrate; Spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing metalaxyl-M and ipconazole; The spray-drying process is: the inlet temperature is 72 °C, the feeding rate is 550 ml / h, the air inlet volume is 95 m 3 / h, and the outlet temperature is 55 °C;

[0088] (6) Mix the β-cyclodextrin inclusion complex containing metalaxyl-M and ipconazole with water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain 0.25% metalaxyl-M + 0.25% ipconazole soluble powder.

[0089] Example 5: 2% metalaxyl-M + 0.25% ipconazole soluble powder

[0090] Formula:

[0091] Metalaxyl-M 2%

[0092] Tebuconazole 0.25%

[0093] β-Cyclodextrin 3%

[0094] Citric acid phosphoric anhydride 3%

[0095] Water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer supplemented

[0096] Process: Preparation method of 2% metalaxyl-M + 0.25% tebuconazole soluble powder, including the following steps:

[0097] (1) Weighing of raw materials: Weigh each component of the water-soluble pharmaceutical fertilizer containing metalaxyl-M and tebuconazole according to the weight percentage;

[0098] (2) Preparation of the original drug organic solution: Dissolve 2% metalaxyl-M + 0.25% tebuconazole in methanol to obtain the original drug organic solution;

[0099] (3) Preparation of β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride: Dissolve β-cyclodextrin and citric acid phosphoric anhydride in distilled water and mix evenly to obtain β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride;

[0100] (4) Preparation of inclusion complex solution: Magnetically stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride at room temperature, and under continuous stirring conditions, add the original drug organic solution, continue to stir continuously for 6 h, and let it stand to obtain the inclusion complex solution;

[0101] (5) Preparation of β-cyclodextrin inclusion complex containing metalaxyl-M and tebuconazole: Evaporate methanol in the inclusion complex solution under reduced pressure to obtain a filtrate; Spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing metalaxyl-M and tebuconazole; The spray-drying process is: the inlet temperature is 75 °C, the feeding rate is 600 ml / h, the air inlet volume is 90 m 3 / h, and the outlet temperature is 53 °C;

[0102] (6) Mix the β-cyclodextrin inclusion complex containing metalaxyl-M and tebuconazole with water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain 2% metalaxyl-M + 0.25% tebuconazole soluble powder.

[0103] Comparative example 1: 2% metalaxyl-M + 0.25% tebuconazole soluble powder

[0104] Formula:

[0105] Metalaxyl-M 2%

[0106] Tebuconazole 0.25%

[0107] β - Cyclodextrin 3%

[0108] Humic acid 3%

[0109] Water - soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer made up

[0110] Process: Preparation method of 2% metalaxyl - M + 0.25% ipconazole soluble powder, including the following steps:

[0111] (1) Weighing of raw materials: Weigh each component of the water - soluble medicament fertilizer containing metalaxyl - M and ipconazole according to the weight percentage;

[0112] (2) Preparation of the original drug organic solution: Dissolve 2% metalaxyl - M + 0.25% ipconazole in methanol to obtain the original drug organic solution;

[0113] (3) Preparation of the β - cyclodextrin aqueous solution containing humic acid: Dissolve β - cyclodextrin and humic acid in distilled water, mix evenly to obtain the β - cyclodextrin aqueous solution containing humic acid;

[0114] (4) Preparation of the inclusion complex solution: Magnetically stir the β - cyclodextrin aqueous solution containing humic acid at room temperature, and under the condition of continuous stirring, add the original drug organic solution, continue to stir continuously for 6 h, and then let it stand to obtain the inclusion complex solution;

[0115] (5) Preparation of the β - cyclodextrin inclusion complex containing metalaxyl - M and ipconazole: Evaporate methanol in the inclusion complex solution under reduced pressure to obtain a filtrate; Spray - dry the filtrate to obtain a white powder, which is the β - cyclodextrin inclusion complex containing metalaxyl - M and ipconazole; The spray - drying process is: the inlet temperature is 75 °C, the feeding rate is 600 ml / h, the air intake volume is 90 m 3 / h, and the outlet temperature is 53 °C;

[0116] (6) Mix the β - cyclodextrin inclusion complex containing metalaxyl - M and ipconazole with the water - soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain 2% metalaxyl - M + 0.25% ipconazole soluble powder.

[0117] Comparative example 2: 2% metalaxyl - M + 0.25% ipconazole soluble powder

[0118] Formulation:

[0119] Metalaxyl - M 2%

[0120] Ipconazole 0.25%

[0121] β - Cyclodextrin 3%

[0122] Citric acid 3%

[0123] Water - soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer made up

[0124] Process: Preparation method of 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder, including the following steps:

[0125] (1) Weighing of raw materials: Weigh each component of the water-soluble fertilizer containing metalaxyl-M and fluxapyroxad according to the weight percentage;

[0126] (2) Preparation of original drug organic solution: Dissolve 2% metalaxyl-M + 0.25% fluxapyroxad in methanol to obtain the original drug organic solution;

[0127] (3) Preparation of β-cyclodextrin aqueous solution containing citric acid: Dissolve β-cyclodextrin and citric acid in distilled water, mix evenly to obtain β-cyclodextrin aqueous solution containing citric acid;

[0128] (4) Preparation of inclusion complex solution: Magnetically stir the β-cyclodextrin aqueous solution containing citric acid at room temperature, and under the condition of continuous stirring, add the original drug organic solution, continue to stir continuously for 6 h, and let it stand to obtain the inclusion complex solution;

[0129] (5) Preparation of β-cyclodextrin inclusion complex containing metalaxyl-M and fluxapyroxad: Evaporate methanol in the inclusion complex solution under reduced pressure to obtain a filtrate; Spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing metalaxyl-M and fluxapyroxad; The spray-drying process is: the inlet temperature is 75 °C, the feeding rate is 600 ml / h, the air inlet volume is 90 m 3 / h, and the outlet temperature is 53 °C;

[0130] (6) Mix the β-cyclodextrin inclusion complex containing metalaxyl-M and fluxapyroxad with water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder.

[0131] Comparative Example 3

[0132] 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder

[0133] Formulation:

[0134] Metalaxyl-M 2%

[0135] Fluxapyroxad 0.25%

[0136] β-Cyclodextrin 3%

[0137] Water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer to make up

[0138] Process: Preparation method of 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder, including the following steps:

[0139] (1) Weighing of raw materials: Weigh each component of the water-soluble fertilizer and pesticide containing metalaxyl-M and fluxapyroxad according to the weight percentage;

[0140] (2) Preparation of the technical material organic solution: Dissolve 2% metalaxyl-M + 0.25% fluxapyroxad in methanol to obtain the technical material organic solution;

[0141] (3) Preparation of the β-cyclodextrin aqueous solution: Dissolve β-cyclodextrin in distilled water and mix evenly to obtain the β-cyclodextrin aqueous solution;

[0142] (4) Preparation of the inclusion complex solution: Stir the β-cyclodextrin aqueous solution magnetically at room temperature, and under continuous stirring, add the technical material organic solution, continue continuous stirring for 6 h, and then let it stand to obtain the inclusion complex solution;

[0143] (5) Preparation of the β-cyclodextrin inclusion complex containing metalaxyl-M and fluxapyroxad: Remove methanol from the inclusion complex solution under reduced pressure to obtain a filtrate; Spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing metalaxyl-M and fluxapyroxad; The spray-drying process is as follows: the inlet temperature is 75 °C, the feeding rate is 600 ml / h, the air inlet volume is 90 m 3 / h, and the outlet temperature is 53 °C;

[0144] (6) Mix the β-cyclodextrin inclusion complex containing metalaxyl-M and fluxapyroxad with a water-soluble macronutrient (nitrogen, phosphorus, potassium) fertilizer evenly to obtain a 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder.

[0145] Bioassay verification 1: Controlling potato late blight by spraying

[0146] The test object is potato late blight; the test crop is potato.

[0147] Test agents: 0.5% metalaxyl-M + 0.25% fluxapyroxad soluble powder prepared in Example 1;

[0148] 1% metalaxyl-M + 1.25% fluxapyroxad soluble powder prepared in Example 2;

[0149] 0.05% metalaxyl-M + 0.05% fluxapyroxad soluble powder prepared in Example 3;

[0150] 0.25% metalaxyl-M + 0.25% fluxapyroxad soluble powder prepared in Example 4;

[0151] 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder prepared in Example 5;

[0152] 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder with citric acid phosphoric anhydride replaced by fulvic acid prepared in Comparative Example 1;

[0153] The citric acid phosphoric anhydride prepared in Comparative Example 2 was replaced with 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder containing citric acid;

[0154] 2% metalaxyl-M + 0.25% fluxapyroxad soluble powder without citric acid phosphoric anhydride prepared in Comparative Example 3.

[0155] Each test agent was tested separately. The experimental group was the soluble powder group of the test agent, and the control group was the corresponding suspension agent group and the water control;

[0156] Specifically, taking the 1% metalaxyl-M + 1.25% fluxapyroxad soluble powder in Example 2 as an example: the control group was the corresponding suspension agent group; there were 6 treatments in total for the test, which were 1000 g, 1500 g, and 2000 g of 1% metalaxyl-M + 1.25% fluxapyroxad soluble powder respectively. The control agents were 100 g, 150 g, and 200 g per mu of the 10% metalaxyl-M + 12.5% fluxapyroxad suspension agent prepared in the laboratory, and the water control. There were 4 plots in each treatment, and the plot area was 30 m2. Each plot was randomly arranged. At the initial stage of potato late blight, it was evenly sprayed in plots. When applying the medicine, the potato was in the flowering and tuber-forming stage, and the potato late blight was in the initial stage. The medicine was sprayed twice continuously, and the interval between the two sprays was 7 days.

[0157] Pharmacodynamic investigation

[0158] The disease index was investigated before the first application of the medicine, and the second, third, and fourth investigations were carried out before the second application of the medicine, 7 days after the second application of the medicine, and 10 days after the second application of the medicine respectively. Five points were sampled along the diagonal of each plot, and 2 plants were selected at each point to investigate the occurrence of potato late blight on all the leaves on the main stem to determine the disease grade. The grading standard for potato late blight: Grade 0: no disease spots; Grade 1: the disease spot area accounts for less than 5% of the entire leaf area; Grade 3: the disease spot area accounts for 6% - 10% of the entire leaf area; Grade 5: the disease spot area accounts for 11% - 20% of the entire leaf area; Grade 7: the disease spot area accounts for 21% - 50% of the entire leaf area; Grade 9: the disease spot area accounts for more than 50% of the entire leaf area. The disease index and control effect were calculated by the following formula:

[0159]

[0160]

[0161] In the formula: CK0 is the disease index before applying the medicine in the blank control area; CK1 is the disease index after applying the medicine in the blank control area; PT0 is before applying the medicine in the agent treatment area;

[0162] Disease index; PT1 is the disease index after applying the medicine in the agent treatment area.

[0163] The experimental results are shown in Tables 1 - 8 below;

[0164] Table 1

[0165]

[0166] Table 2

[0167]

[0168]

[0169] Table 3

[0170]

[0171] Table 4

[0172]

[0173]

[0174] Table 5

[0175]

[0176] Table 6

[0177]

[0178] Table 7

[0179]

[0180]

[0181] Table 8

[0182]

[0183] Bioassay Experiment 2: Control of Rhizoctonia Solani on Potato by Mixing with Soil and Applying in Furrows

[0184] The experiment was conducted in Tengzhou, Shandong. The soil fertility was medium, the tillage conditions were good, the previous crop was wheat, and the potato growth was good. The soil type, cultivation conditions, water and fertilizer management, etc. of each experimental plot were uniform. Pesticides were applied before potato sowing. The tested pesticides were 1% metalaxyl-M + 1.25% fludioxonil soluble powder at 1000g, 1500g, and 2000g per mu, applied by mixing with soil and ditch application. The control pesticides were 10% metalaxyl-M + 12.5% fludioxonil suspension prepared in the laboratory at 100g, 150g, and 200g per mu, applied by soil spraying. The stem disease situation was investigated 70 days after potato emergence. At harvest, the incidence and disease index of black dot disease of 100 potato tubers were investigated in each plot. The grading method was as follows: Grade 0: No sclerotia on the tuber surface; Grade 1: The sclerotia area accounted for 0% - 5% of the total tuber area; Grade 2: The sclerotia area accounted for 6% - 35% of the total tuber area; Grade 3: The sclerotia area accounted for 36% - 65% of the total stem area in the field; Grade 4: The sclerotia area accounted for 66% - 95% of the total stem area in the field; Grade 5: The sclerotia area accounted for more than 96% of the total tuber area.

[0185]

[0186]

[0187] The detection results of the inclusion rates of metalaxyl-M and fludioxonil in Examples 1 - 5 and Comparative Examples 1 - 3 are shown in the following table:

[0188] Project Metalaxyl-M inclusion rate / % Epoxiconazole inclusion rate / % Example 1 95.6 87.6 Example 2 96.7 88.5 Example 3 96.8 88.7 Example 4 84.5 73.2 Example 5 83.6 72.5

[0189] It can be seen from this that for a water-soluble medicine-fertilizer containing metalaxyl-M and ipconazole and its preparation method according to the present invention, the active components of the medicine-fertilizer are composed of metalaxyl-M and ipconazole. Metalaxyl-M is the R isomer of metalaxyl, and it is a systemic fungicide with a protective effect. It can be absorbed by the roots, stems and leaves of plants, and has the efficacy of preventing and controlling crop diseases caused by downy mildew pathogens, Phytophthora pathogens and Pythium pathogens. Ipconazole has good control effects on diseases caused by ascomycetes, basidiomycetes, deuteromycetes and zygomycetes except oomycetes. After being compounded with metalaxyl or metalaxyl-M, it is effective against almost all fungal diseases. In the water-soluble medicine-fertilizer of this application, citric acid phosphoric anhydride is also added. The oxygen-containing functional groups with negative charges on the citric acid phosphoric anhydride molecule can adsorb the positively charged metal ions in the soil. At the same time, specific sites on the citric acid phosphoric anhydride can complex the active ingredients of the water-soluble medicine-fertilizer, so as to carry the medicine and fertilizer to transfer to the implanted roots together and be quickly absorbed, thus realizing the effect of promoting the efficacy of fertilizer with medicine. After being compounded with metalaxyl or metalaxyl-M, the added citric acid phosphoric anhydride becomes an enhancer, which can greatly improve the control effect of fungal diseases. The active ingredients of the water-soluble medicine-fertilizer are metalaxyl-M and ipconazole, and the carrier is selected from one or more of macronutrient fertilizers, secondary nutrient fertilizers and micronutrient fertilizers; the carrier can also be amino acids, humic acids, etc.; the dosage form is a soluble powder; β-cyclodextrin is used as an inclusion material to prepare an inclusion complex of metalaxyl-M and ipconazole to improve the solubility of metalaxyl-M and ipconazole in water and have better drug efficacy; the inclusion complex material contains citric acid phosphoric anhydride, and citric acid phosphoric anhydride can promote the absorption and conduction of drugs, and can realize the effect of promoting the efficacy of fertilizer with medicine; the water-soluble medicine-fertilizer can be sprayed on the leaves or used in the soil, with a wide application range and is easy to promote and apply; the preparation process of the inclusion complex solution is also optimized, and the stirring rate, the temperature of the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride, the temperature of the original drug organic solution and the temperature difference between the two are reasonably controlled. With the advantages of stirring and temperature difference, the saturation effect of β-cyclodextrin is significantly enhanced, and the inclusion rate of the β-cyclodextrin inclusion complex containing metalaxyl-M and ipconazole increases by more than 10%.

[0190] The foregoing description of the specific exemplary embodiments of the present invention is for purposes of illustration and exemplification. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is obvious that many changes and variations are possible in light of the above teaching. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical applications, so that those skilled in the art can implement and utilize various different exemplary embodiments of the present invention as well as various different selections and changes. The scope of the present invention is intended to be defined by the claims and their equivalents.

Claims

1. A water-soluble medicine fertilizer containing metalaxyl-M and fluxapyroxad, characterized in that: The water-soluble medicated fertilizer containing metalaxyl-M and ipconazole comprises the following components by weight percentage: metalaxyl-M 0.01% - 5%, ipconazole 0.01% - 1%, β-cyclodextrin 1% - 5%, citric acid phosphoric anhydride 0.1% - 5%, and the balance is water-soluble fertilizer; the water-soluble fertilizer is one or more of macronutrient fertilizers, secondary nutrient fertilizers, and micronutrient fertilizers. The preparation method of a water-soluble medicated fertilizer containing metalaxyl-M and ipconazole comprises the following steps: (1) Weighing of raw materials: Weigh each component of the water-soluble medicated fertilizer containing metalaxyl-M and ipconazole according to the weight percentage. (2) Preparation of the original drug organic solution: Dissolve metalaxyl-M and ipconazole in methanol to obtain the original drug organic solution. (3) Preparation of the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride: Dissolve β-cyclodextrin and citric acid phosphoric anhydride in distilled water, mix evenly to obtain the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride. (4) Preparation of the inclusion complex solution: Stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride, and under the condition of continuous stirring, add the original drug organic solution, continue to stir continuously for 0.5 - 24 h, and let it stand to obtain the inclusion complex solution. (5) Preparation of the β-cyclodextrin inclusion complex containing metalaxyl-M and ipconazole: Remove methanol from the inclusion complex solution to obtain a filtrate; spray-dry the filtrate to obtain a white powder, which is the β-cyclodextrin inclusion complex containing metalaxyl-M and ipconazole. (6) Mix the β-cyclodextrin inclusion complex containing metalaxyl-M and ipconazole with the water-soluble fertilizer evenly to obtain the water-soluble medicated fertilizer containing metalaxyl-M and ipconazole. In the step (4), first heat the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride to 35 - 40 °C; then stir the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride at a rate of 100 - 200 r / min; control the temperature of the original drug organic solution at 15 - 20 °C, and the temperature difference between the β-cyclodextrin aqueous solution containing citric acid phosphoric anhydride and the original drug organic solution is 15 - 20 °C. Under the condition of continuous stirring, add the original drug organic solution, continue to stir continuously for 0.5 - 24 h, and let it stand to obtain the inclusion complex solution.

2. A water-soluble medicine fertilizer containing metalaxyl-M and fluxapyroxad according to claim 1, characterized in that: The water-soluble medicated fertilizer containing metalaxyl-M and ipconazole comprises the following components by weight percentage: metalaxyl-M 0.05% - 5%, ipconazole 0.05% - 1%, β-cyclodextrin 2% - 5%, citric acid phosphoric anhydride 0.3% - 5%, and the balance is water-soluble fertilizer; the water-soluble fertilizer is one or more of macronutrient fertilizers, secondary nutrient fertilizers, and micronutrient fertilizers.

3. A water-soluble medicine fertilizer containing metalaxyl-M and fluxapyroxad according to claim 1, characterized in that: The water-soluble medicated fertilizer containing metalaxyl-M and ipconazole comprises the following components by weight percentage: metalaxyl-M 0.25% - 5%, ipconazole 0.25% - 1%, β-cyclodextrin 3% - 5%, citric acid phosphoric anhydride 0.5% - 5%, and the balance is water-soluble fertilizer; the water-soluble fertilizer is one or more of macronutrient fertilizers, secondary nutrient fertilizers, and micronutrient fertilizers.

4. A water-soluble medicated fertilizer containing metalaxyl-M and ipconazole according to claim 1, characterized in that: The weight ratio of the two active ingredients of metalaxyl-M and ipconazole is: metalaxyl-M: ipconazole = 1:2 to 10:

1.

5. A water-soluble medicated fertilizer containing metalaxyl-M and flutriafol according to claim 4, characterized in that: The weight ratio of the two active ingredients of metalaxyl-M and ipconazole is: metalaxyl-M: ipconazole = 1:1 to 5:

1.

6. A water-soluble medicated fertilizer containing metalaxyl-M and ipconazole according to claim 1, characterized in that: The cumulative mass percentage of the two active ingredients of metalaxyl-M and ipconazole is 0.2% to 5%.

7. A water-soluble medicated fertilizer containing metalaxyl-M and ipconazole according to claim 6, characterized in that: The cumulative mass percentage of the two active ingredients of metalaxyl-M and ipconazole is 1.25% to 5%.

8. A water-soluble medicine fertilizer containing metalaxyl-M and ipconazole according to claim 1, characterized in that: In the step (5), the spray drying process is as follows: the inlet temperature is 70 - 85°C, the feeding rate is 500 - 600 ml / h, the air intake is 85 - 100 m 3 / h, and the outlet temperature is 50 - 55°C.

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