Special pesticide-fertilizer granules for soil-borne diseases and preparation method of special pesticide-fertilizer granules

Abstract

The invention belongs to the technical field of medical fertilizers, and particularly relates to a special medical fertilizer granule for soil-borne diseases and a preparation method of the special medical fertilizer granule. The granule is composed of a pesticide sterilization effective component, a zinc-based slow-release material mixed carrier, a fertilizer effective component and the like, wherein the zinc-based slow-release material mixed carrier is a compound of at least one of polysaccharides such as chitosan, carboxymethyl chitosan and pectin, a chelate of calcium chloride and a zinc-based slow-release material metal organic framework-zeolite imidazate framework ZIF-8. The pesticide-fertilizer granule has the advantages that the zinc-based slow-release material metal organic framework ZIF-8 is used as a main slow-release carrier, the lasting period of pesticide and fertilizer effective components is prolonged, the prevention and treatment effect on soil-borne diseases is enhanced, the preparation method is simple, disease prevention and treatment and topdressing are synchronously performed during application, and the pesticide and fertilizer application strength and frequency of farmers are reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of medicinal fertilizers, and in particular relates to a preparation method and application of a special medicinal fertilizer granule for soil-borne diseases. Background Art

[0002] With the continuous planting of crops and the development of protected areas, the damage caused by soil-borne diseases of crops has become more serious year by year. Soil-borne diseases include diseases caused by pathogenic bacteria, fungi, nematodes, viruses, etc., which usually have the characteristics of many pathogen types, wide host range, strong concealment, fast transmission speed, large damage area, and difficult control. If not intervened in time, it will lead to crop failure in severe cases, which will cause serious yield and economic losses. Effectively preventing and controlling the occurrence of soil-borne diseases of crops has become an urgent problem to be solved in order to increase crop yields.

[0003] Due to the strong infectiousness and concealment of soil-borne diseases, their prevention and control is very difficult. The current methods for preventing and controlling soil-borne diseases include screening of disease-resistant crop varieties, biological control, physical disinfection of soil, chemical control, etc. The resistant varieties currently screened do not have permanent disease resistance, and new pathogen strains are easily produced under conditions that are conducive to soil-borne diseases. Biological control is environmentally friendly and can replace or reduce the use of chemical agents, but its field application is relatively rare. Physical disinfection of soil will mostly cause other pollution to the soil.

[0004] At present, the most effective way to prevent and control soil-borne diseases is chemical pesticides. Seed dressing with seed dressing agents is a relatively effective prevention and control method, but the effect will weaken in the later stages of crop growth. It is necessary to carry out comprehensive prevention and control by pre-sowing seed dressing, post-spraying treatment and other prevention and control methods. However, the long-term use of chemical pesticides can easily lead to negative problems such as drug resistance and environmental ecology.

[0005] In the traditional crop growth cycle, disease prevention and control and fertilizer application are carried out in parallel. The two agricultural operations increase farmers' workload and easily lead to unreasonable application of pesticides and fertilizers, poor disease prevention and control effects, etc. Summary of the invention

[0006] In view of this, in order to solve this problem, the purpose of the present invention is to provide a special medicinal fertilizer granule for soil-borne diseases and a preparation method thereof.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] The first technical purpose of the present invention is to provide a special fertilizer granule for soil-borne diseases, comprising the following components: pesticide bactericidal active ingredients, zinc-based slow-release material mixed carriers, fertilizer active ingredients, etc., wherein the zinc-based slow-release material mixed carrier is a complex of at least one of chitosan, carboxymethyl chitosan, pectin and other polysaccharides and a chelate of calcium chloride and a zinc-based slow-release material metal organic framework-zeolite imidazolate skeleton ZIF-8.

[0009] Optionally, the pesticide bactericidal active ingredient refers to a systemic bactericidal pesticide active ingredient, and its mass percentage is 0.15%-0.4%.

[0010] Optionally, the fertilizer active ingredients include macroelements (nitrogen, phosphorus, potassium) and other trace elements, the mass percentage of which accounts for 15%-21%; the macroelements can be selected from potassium dihydrogen phosphate, potassium chloride, urea, ammonium nitrate, etc.

[0011] Furthermore, the trace element contained is zinc, which is contained in the zinc-based sustained-release material component.

[0012] Optionally, the raw materials for synthesizing the metal organic framework-zeolite imidazolate framework ZIF-8 are dimethylimidazole and zinc salt, and the zinc salt can be zinc nitrate or zinc acetate and their corresponding hydrates.

[0013] It should be noted that the present invention combines the slow-release material - metal organic framework - zeolite imidazolate skeleton ZIF-8 with fertilizer particles. Based on the compounding of fungicide and fertilizer, when used, it increases the prevention and control effect and prevention period of soil-borne diseases while being able to enhance the disease prevention ability and growth promotion function of crops, thereby enhancing the ability of crops to resist soil-borne diseases.

[0014] The preparation method of the medicinal fertilizer granules is as follows:

[0015] Step 1) firstly, a polysaccharide selected from chitosan, carboxymethyl chitosan, pectin, etc. is prepared into a polysaccharide aqueous solution with a mass percentage of 2%-3%, and potassium dihydrogen phosphate, potassium chloride, urea, ammonium nitrate, etc., fertilizer active ingredients containing nitrogen, phosphorus, potassium, etc., zinc nitrate or zinc acetate and its corresponding zinc salt of hydrate, Tween 80 or Span 80 are added into the polysaccharide solution at a mass percentage of 15%-21%, 2.2%-4.4% (relative to the mass of the polysaccharide aqueous solution), and 0.5%, respectively, and fully dissolved to obtain a solution 1;

[0016] Step 2) weighing 0.15%-0.4% of the active ingredient of the pesticide by mass and dissolving it in a small amount of dimethyl sulfoxide, slowly adding it to the solution 1 under high-speed stirring, and stirring it thoroughly to obtain solution 2;

[0017] Step 3) Weigh 12.5 g of dimethylimidazole and dissolve it in 200 mL of saturated calcium chloride aqueous solution to obtain solution 3;

[0018] Step 4) adding solution 2 dropwise to solution 3 to react and form microspheres and continuing the reaction for 3-5 hours to allow the reaction to be fully completed;

[0019] Step 5) collecting the microspheres prepared in step (4) and drying them to obtain the special fertilizer granules for soil-borne diseases.

[0020] By changing the amount of zinc salt added, fertilizer granules with different internal structures can be obtained; and by changing the size of the dripping pipe outlet in step 4, fertilizer granules of different sizes can be obtained.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The invention discloses a special soil-borne disease medicine-fertilizer granule and a preparation method thereof. By utilizing a metal organic framework-zeolite imidazolate skeleton ZIF-8 as a slow-release carrier of the medicine-fertilizer granule, the migration speed of the effective components of the pesticide and the fertilizer in the environment is slowed down, a longer-lasting soil-borne disease prevention and control effect is achieved, and the application times of the corresponding pesticides and fertilizers are slowed down. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0024] Figure 1 This is a diagram showing the effects of different zinc salt types and addition amounts on the internal structure of particles.

[0025] Figure 2 The fertilizer granules of different sizes are obtained by controlling the outlet of the dripping pipe. DETAILED DESCRIPTION

[0026] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] The word "embodiment" used here as an "exemplary" does not necessarily mean that any embodiment described is superior to or better than other embodiments. Unless otherwise specified, the performance index tests in the embodiments of this application are performed using conventional test methods in the art. It should be understood that the terms described in this application are only used to describe specific implementation methods and are not used to limit the content disclosed in this application.

[0028] Unless otherwise specified, the technical and scientific terms used in this document have the same meanings as commonly understood by ordinary technicians in the technical field to which this application belongs; other experimental methods and technical means not specifically specified in this application refer to experimental methods and technical means commonly used by ordinary technicians in this field.

[0029] In order to better illustrate the content of the present application, numerous specific details are provided in the specific examples below. It should be understood by those skilled in the art that the present application can also be implemented without certain specific details. In the embodiments, some methods, means, instruments, equipment, etc. well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present application.

[0030] Under the premise of no conflict, the technical features disclosed in the embodiments of the present application can be combined arbitrarily, and the resulting technical solutions belong to the contents disclosed in the embodiments of the present application.

[0031] The invention discloses a special medicinal fertilizer granule for soil-borne diseases and a preparation method thereof.

[0032] In order to better understand the present invention, the present invention is further specifically described below through the following examples, but it should not be understood as a limitation of the present invention. Some non-essential improvements and adjustments made by technicians in this field based on the above invention content are also considered to fall within the protection scope of the present invention.

[0033] Example 1: 0.2% Thifluzamide fertilizer granules

[0034] The above-mentioned medicated fertilizer granules include the following components in percentage by weight: 0.2% of thiothiocarb, 5% of urea, 4% of dipotassium hydrogen phosphate, 6% of potassium chloride, and the carrier makes up 100%.

[0035] Step 1) 2.0 g of chitosan, 95.5 g of deionized water, 0.5 g of Tween 80 and 2.0 g of acetic acid are mixed to form a 2% chitosan aqueous solution; 3.5 g of urea, 2.8 g of dipotassium hydrogen phosphate and 4.2 g of potassium chloride are added to the solution, dissolved and stirred evenly, and then 2.2 g of zinc acetate dihydrate is added and stirred and dispersed evenly to obtain a solution 1;

[0036] Step 2) weigh 0.61 g of thiothiophene original drug, dissolve it in 3 mL of dimethyl sulfoxide, slowly add it dropwise to the rapidly stirred solution 1, stir thoroughly and perform ultrasound to remove all bubbles in the solution to obtain solution 2;

[0037] Step 3) Weigh 12.5 g of dimethylimidazole and dissolve it in 200 mL of saturated calcium chloride aqueous solution to obtain solution 3;

[0038] Step 4) under room temperature, solution 2 is added dropwise to solution 3 in a stirring state to react and form microspheres, and stirring is continued for 3-5 hours to allow the reaction to be fully completed;

[0039] Step 5) collecting the microspheres, removing the surface liquid and then drying to obtain the fertilizer granules.

[0040] Example 2: 0.4% Thifluzamide fertilizer granules

[0041] The above-mentioned medicated fertilizer granules include the following components in percentage by weight: 0.4% of thiothiocarb, 5% of ammonium nitrate, 4% of dipotassium hydrogen phosphate, 6% of potassium chloride, and the carrier is supplemented to 100%.

[0042] Step 1) 2.0 g of carboxymethyl chitosan, 95.5 g of deionized water, 0.5 g of Tween 80 and 2.0 g of acetic acid are mixed to form a 2% by mass carboxymethyl chitosan aqueous solution; 3.5 g of ammonium nitrate, 2.8 g of dipotassium hydrogen phosphate and 4.2 g of potassium chloride are added to the solution, dissolved and stirred evenly, and then 2.2 g of zinc acetate dihydrate is added and stirred and dispersed evenly to obtain a solution 1;

[0043] Step 2) Weigh 1.22 g of thiothiocarb original drug, dissolve it in 3 mL of dimethyl sulfoxide, slowly add it dropwise to the rapidly stirred solution 1, stir thoroughly and then sonicate until all bubbles in the solution are removed to obtain solution 2;

[0044] Step 3) Weigh 12.5 g of dimethylimidazole and dissolve it in 200 mL of saturated calcium chloride aqueous solution to obtain solution 3;

[0045] Step 4) under room temperature, solution 2 is added dropwise to solution 3 in a stirring state to react and form microspheres, and stirring is continued for 3-5 hours to allow the reaction to be fully completed;

[0046] Step 5) collecting the microspheres, removing the surface liquid and then drying to obtain the fertilizer granules.

[0047] Example 3: 0.15% Tebuconazole Fertilizer Granules

[0048] The above-mentioned medicated fertilizer granules include the following components in percentage by weight: 0.15% of tebuconazole, 5% of urea, 5% of dipotassium hydrogen phosphate, 6% of potassium chloride, and the carrier supplements 100%.

[0049] Step 1) 3.0 g of chitosan, 94.5 g of deionized water, 0.5 g of Tween 80 and 2.0 g of acetic acid are mixed to form a chitosan aqueous solution with a mass percentage of 3%; 3.5 g of urea, 3.5 g of dipotassium hydrogen phosphate and 4.2 g of potassium chloride are added to the solution, dissolved and stirred evenly, and then 3.5 g of zinc nitrate hexahydrate is added and stirred and dispersed evenly to obtain a solution 1;

[0050] Step 2) Weigh 0.46 g of tebuconazole original drug, dissolve it in 3 mL of dimethyl sulfoxide, slowly add it dropwise to the rapidly stirred solution 1, stir thoroughly and then perform ultrasound to remove all bubbles in the solution to obtain solution 2;

[0051] Step 3) Weigh 12.5 g of dimethylimidazole and dissolve it in 200 mL of saturated calcium chloride aqueous solution to obtain solution 3;

[0052] Step 4) under room temperature, solution 2 is added dropwise to solution 3 in a stirring state to react and form microspheres, and stirring is continued for 3-5 hours to allow the reaction to be fully completed;

[0053] Step 5) collecting the microspheres, removing the surface liquid and then drying to obtain the fertilizer granules.

[0054] Example 4: 0.3% Tebuconazole Fertilizer Granules

[0055] The above-mentioned medicated fertilizer granules include the following components in percentage by weight: 0.3% of tebuconazole, 7% of urea, 7% of dipotassium hydrogen phosphate, 7% of potassium chloride, and the carrier is supplemented to 100%.

[0056] Step 1) 2.0 g of pectin, 95.5 g of deionized water, 0.5 g of Span 80 and 2.0 g of acetic acid were mixed to form a 2% by mass pectin aqueous solution; 4.9 g of urea, 4.9 g of dipotassium hydrogen phosphate and 4.9 g of potassium chloride were added to the solution, dissolved and stirred evenly, and then 3.5 g of zinc acetate was added and stirred and dispersed evenly to obtain a solution 1;

[0057] Step 2) weighing 0.92 g of tebuconazole original drug, dissolving it in 3 mL of dimethyl sulfoxide, slowly adding dropwise to the rapidly stirred solution 1, stirring thoroughly and ultrasonicating until all bubbles in the solution are removed, to obtain solution 2;

[0058] Step 3) Weigh 12.5 g of dimethylimidazole and dissolve it in 200 mL of saturated calcium chloride aqueous solution to obtain solution 3;

[0059] Step 4) under room temperature, solution 2 is added dropwise to solution 3 in a stirring state to react and form microspheres, and stirring is continued for 3-5 hours to allow the reaction to be fully completed;

[0060] Step 5) collecting the microspheres, removing the surface liquid and then drying to obtain the fertilizer granules.

[0061] like Figure 1It can be seen that when the zinc salt is added at a lower concentration, a large number of large cavity structures are formed inside the granules, and the internal space distribution of the granules is uneven. When the addition amount is 4.4%, whether it is zinc acetate dihydrate or zinc nitrate hexahydrate, the granules have a uniform honeycomb pore structure inside, which can keep the granules uniform and the fine and uniform cavity can ensure the uniformity of the release dynamics of the active ingredients of the pesticide or the fertilizer elements, which is conducive to the stable performance of the product's slow-release performance.

[0062] In order to further demonstrate the beneficial effects of the present invention and to better understand the present invention, the following application test examples are used to further illustrate the technical features disclosed in the present invention, but they should not be understood as limiting the present invention. Other improvements made by those skilled in the art based on the above invention content without creative work are also considered to fall within the scope of protection of the present invention.

[0063] Test Example 1: Field test of the efficacy of thiophanate-methyl fertilizer granules against peanut white rot

[0064] Experimental site: A peanut field of a farmer in Rudong Town, Yangxi County, Yangjiang City, Guangdong Province. The land is flat and peanuts have been planted there for more than 5 years. In recent years, the damage caused by peanut white rot has been quite serious.

[0065] Experimental design: Simultaneous application with a certain brand of thiothiazide granules on the market, with a plot area of ​​50m 2 , randomly arrange the test area groups, and repeat three times for each treatment. Apply the fertilizer by broadcasting at the seedling stage, and measure Example 1 (10kg) and Example 2 (5kg) per mu. The control group maintains the same application amount of thiothiocarb as Example 1 and Example 2. Irrigate and supply water normally, and investigate 30d, 45d and 60d after the application of the fertilizer, and randomly sample five points to calculate the control effect of peanut white rot.

[0066] The disease index grading standards are as follows: Level 0: Plants are asymptomatic; Level 1: Lesions appear at the base of the inoculated stems; Level 3: The base of the stems wilt and shrink, less than 1 / 3 of the plants show systemic symptoms (wilt, death, wilting, etc.), and there are fewer hyphae on the soil surface; Level 5: Less than 2 / 3 of the plants show systemic symptoms (wilt, death, wilting, etc.), and a large number of hyphae or sclerotia appear on the soil surface; Level 7: More than 2 / 3 of the plants show systemic symptoms (wilt, death, wilting, etc.); Level 9: The plants completely wilt and die.

[0067] Incidence rate (%) = number of diseased plants / total number of plants surveyed × 100%

[0068] Disease index = Σ(number of diseased plants × corresponding level) / (total number of plants surveyed × highest level) × 100

[0069] Control effect (%) = (clear water control disease index - treatment disease index / clear water control disease index) × 100

[0070] Table 1 Field efficacy of thiophanate-methyl fertilizer granules against peanut white rot

[0071] Treatment / prevention effect 30 days after medication 45 days after medication 60 days after medication Control group 85.4％ 79.3％ 73.9％ Example 1 89.5％ 85.4％ 79.6％ Example 2 88.7％ 84.6％ 80.1％

[0072] As shown in Table 1, the medicated fertilizer granules of the present invention are based on a slow-release material as a carrier. When used for the prevention and treatment of the soil-borne disease peanut white rot, they can demonstrate a long-term disease control effect, reduce the total usage of active ingredients of pesticides, reduce the physical expenditure of farmers in disease prevention and control, and ensure the yield and quality of agricultural products.

[0073] Test Example 2: Field test of the efficacy of tebuconazole fertilizer granules against wheat stem rot

[0074] Experimental site: A farmer's wheat field in Shuanghe Town, Queshan County, Zhumadian City, Henan Province. The land is flat and spring wheat has been planted there for more than five years. Three years ago, the damage caused by wheat stem base rot began to worsen.

[0075] Experimental design: Simultaneous application with a certain brand of tebuconazole granules on the market, with a plot area of ​​25m 2 , randomly arrange the test plots, and repeat three times for each treatment. Use pre-sowing furrow application of pesticide fertilizer, and measure Example 4 (20kg) and Example 5 (10kg) per mu. The control group uses the same application amount of tebuconazole as Example 4 and Example 5. Investigate the occurrence of wheat stem base rot once at the wheat heading stage and maturity stage. Each plot adopts a random sampling method of 5 points (excluding the side rows), and selects 100 plants at each point. The number of plants with wheat stem base rot is recorded, and the diseased plant rate and prevention effect are calculated.

[0076] Control effect = (control disease rate - treatment disease rate) / control disease rate × 100%

[0077] Table 2 Field control effect of tebuconazole fertilizer granules on wheat stem rot

[0078] Treatment / prevention effect Booting stage Maturity Control group 74.28％ 71.44％ Example 4 80.43％ 78.96％ Example 5 81.33％ 78.68％

[0079] As shown in Table 2, the medicated fertilizer granules of the present invention are based on a slow-release material as a carrier, and when used for the prevention and treatment of the soil-borne disease wheat stem base rot, they have a good prevention and control effect, and the effect is better than that of the commercial formulation.

[0080] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A special fertilizer granule for soil-borne diseases, characterized in that: It contains the following components: pesticide bactericidal active ingredients, zinc-based slow-release material mixed carrier, and fertilizer active ingredients; among which, The zinc-based sustained-release material mixed carrier is a complex of at least one of chitosan, carboxymethyl chitosan, pectin and other polysaccharides and calcium chloride chelate and zinc-based sustained-release material metal organic framework-zeolite imidazolate framework ZIF-8.

2. The special fertilizer granules for soil-borne diseases according to claim 1, characterized in that: The pesticide bactericidal active ingredient is a systemic bactericidal pesticide active ingredient, and its mass percentage accounts for 0.15%-0.4%.

3. The special fertilizer granules for soil-borne diseases according to claim 1, characterized in that: The effective components of the fertilizer include nitrogen, phosphorus, potassium and other trace elements, and the mass percentage thereof accounts for 15%-21%.

4. The special fertilizer granules for soil-borne diseases according to claim 1, characterized in that: The metal organic framework-zeolite imidazolate framework ZIF-8 is synthesized from dimethylimidazole and zinc salt, and the zinc salt is zinc nitrate or zinc acetate and the corresponding hydrate thereof.

5. A method for preparing the special fertilizer granules for soil-borne diseases as claimed in claim 1, characterized in that: The method specifically comprises the following steps: (1) preparing a polysaccharide aqueous solution with a mass percentage of 2% to 3%, and adding the fertilizer active ingredient, zinc salt, Tween 80 or Span 80 to the polysaccharide solution and fully dissolving them to obtain a solution 1; (2) dissolving the active ingredient of the pesticide in dimethyl sulfoxide, and then slowly adding it to the solution 1 under high-speed stirring, and stirring thoroughly to obtain solution 2; (3) weighing dimethylimidazole and dissolving it in a saturated calcium chloride aqueous solution to obtain solution 3; (4) adding solution 2 dropwise to solution 3 to react and form microspheres and continuing the reaction for 3-5 hours to allow the reaction to be fully completed; (5) collecting the microspheres prepared in step (4) and drying them to obtain the special fertilizer granules for soil-borne diseases.

6. The method for preparing the special fertilizer granules for soil-borne diseases according to claim 5, characterized in that: The dosage of the zinc salt, Tween 80 or Span 80 is 2.2%-4.4% and 0.5% of the mass percentage of the polysaccharide solution respectively; the amount ratio of the dimethylimidazole to the saturated calcium chloride aqueous solution is 12.5g:200mL.

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