Process for promoting early maturity of crops by using abamectin finished product liquid fertilizer

Abstract

The invention discloses a process for promoting early maturing of crops by using an abamectin finished product liquid fertilizer, and relates to the technical field of fertilizer preparation, the process comprises the following specific steps: step 1, selecting 3-amino-5-sulfydryl-1, 2, 4-triazolyl phenol as an antioxidant, and mixing the 3-amino-5-sulfydryl-1, 2, 4-triazolyl phenol and the antioxidant; the preparation method comprises the following steps: extracting natural antibacterial components from clove by using a supercritical carbon dioxide extraction technology, and selecting a chitosan derivative. The preparation method has the advantages that 3-amino-5-sulfydryl-1, 2, 4-triazolyl phenol is selected as an antioxidant, and a special molecular structure of the 3-amino-5-sulfydryl-1, 2, 4-triazolyl phenol contains a plurality of active sites, so that the antibacterial activity of the chitosan derivative is improved; sulfydryl and phenolic hydroxyl groups can provide reactive hydrogen atoms, free radicals generated due to contact with air and the like in the storage and use processes of the liquid fertilizer are effectively captured, so that the oxidation reaction of abamectin is prevented, the natural antibacterial component eugenol extracted from the clove can inhibit the growth and reproduction of microorganisms, and the growth and reproduction of the microorganisms are promoted. The problem that the activity of abamectin in the liquid fertilizer is reduced can be solved comprehensively, and the comprehensive performance of the abamectin finished product liquid fertilizer is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of fertilizer preparation, and specifically to a process for promoting the early maturity of crops by using an avermectin finished liquid fertilizer. Background Art

[0002] Fertilizers play a crucial role in the growth and development of crops. Liquid fertilizers have been widely used in the agricultural field in recent years due to their advantages such as fast nutrient release, high absorption and utilization rate, and convenient precise fertilization. Avermectin, as an efficient and low-toxic biological pesticide, not only has a significant control effect on various pests and mites, but also can, to a certain extent, regulate the growth and development process of crops and promote the early maturity of crops; There are certain defects in the existing technology. Firstly, during the storage and use of the existing avermectin finished liquid fertilizer, avermectin will gradually reduce its activity due to factors such as contact with air and microbial action. After the activity is reduced, the control effect of avermectin on pests and diseases is greatly reduced, and at the same time, its synergistic effect on promoting the early maturity of crops is also affected. Secondly, the existing avermectin finished liquid fertilizer is prone to photolysis reaction under light conditions, resulting in the loss of its active ingredients and reducing the control effect of pests and diseases and the effect of promoting early maturity of the liquid fertilizer, especially in areas with strong sunlight in summer. Therefore, we propose a process for promoting the early maturity of crops by using an avermectin finished liquid fertilizer. Summary of the Invention

[0003] The purpose of the present invention is to provide a process for promoting the early maturity of crops by using an avermectin finished liquid fertilizer.

[0004] To solve the problems raised in the above background art, the present invention provides the following technical solution: A process for promoting the early maturity of crops by using an avermectin finished liquid fertilizer, the process comprising the following specific steps: Step 1: Select 3-amino-5-mercapto-1,2,4-triazolylphenol as an antioxidant, and then use supercritical carbon dioxide extraction technology to extract natural antibacterial components from cloves. Select a chitosan derivative, the amino and hydroxyl groups on its molecular chain help to form a protective film on the surface of avermectin and exert antibacterial properties, and at the same time prepare deionized water as a solvent; Step 2: Add 3-amino-5-mercapto-1,2,4-triazolylphenol to deionized water, then stir to form a uniform solution, then slowly add the extracted natural antibacterial extract and continue to stir. After stirring, add the chitosan derivative, heat up and stir to react. The chitosan derivative interacts with other components through hydrogen bonds and van der Waals forces to form a stable complex. After the reaction is completed, cool the solution to room temperature and filter it through an ultrafiltration membrane to remove unreacted impurities and large particulate matter, obtaining a clear and transparent antioxidant antibacterial protective liquid, which is filled into a brown bottle and stored in the dark; Step 3: Use pyrrole and benzaldehyde as starting materials, react in a propionic acid solvent to obtain a crude product. Separate and purify the crude product, use a mixed solution of petroleum ether and dichloromethane as the eluent, collect the target eluent, concentrate it under reduced pressure to obtain a porphyrin derivative. Dissolve the obtained porphyrin derivative in dichloromethane, add zinc acetate to it, react to obtain a solid product, and then recrystallize the solid product with ethanol to obtain a metal complex based on the porphyrin derivative. Wash the blueberry peel, dry it, crush it into powder, then add an ethanol solution, put it into an ultrasonic extractor for extraction. After the extraction is completed, centrifuge the extract and take the supernatant. Pass the supernatant through a macroporous resin column, wash the macroporous resin column with deionized water until the effluent is colorless to remove impurities, and then elute with an ethanol solution. Collect the eluate, concentrate the eluate under reduced pressure to remove ethanol to obtain a high-purity anthocyanin compound. At the same time, prepare poly(lactic-co-glycolic acid) as a polymer carrier. In addition, mix dichloromethane and ethanol as the reaction solvent; Step 4: Add the metal complex based on the porphyrin derivative to the mixed reaction solvent of dichloromethane and ethanol, then carry out a stirring reaction, then add the anthocyanin compound to the solution and continue stirring to ensure that the two components are fully mixed. Then slowly add poly(lactic-co-glycolic acid), raise the temperature and continue the stirring speed reaction under nitrogen protection. Poly(lactic-co-glycolic acid) will wrap the light stabilizer and ultraviolet absorber to form nano-scale composite particles. After the reaction is completed, cool the reaction solution to room temperature, remove the solvent through a rotary evaporator to obtain a viscous paste, then disperse the paste in deionized water to form a stable aqueous colloidal solution, and finally make a powdered light-stable protective agent through spray drying technology, collect and reserve it; Step 5: Mix the basic raw materials including abamectin technical, nitrogen source fertilizer, phosphorus source fertilizer, potassium source fertilizer, trace element fertilizer and additives evenly to obtain a preliminary liquid fertilizer mixture, then add an antioxidant and antibacterial protection liquid for a stirring reaction to preliminarily mix the protection liquid with the basic raw materials. After the reaction is completed, add the powdered light-stable protective agent to the mixture for a high-speed stirring reaction to obtain an abamectin finished liquid fertilizer that promotes the early maturity of crops.

[0005] As a further solution of the present invention: In the said Step 1, 10 - 15 parts by mass of antioxidant are prepared, the extraction pressure for extracting the natural antibacterial component is controlled at 20 MPa - 30 MPa, the temperature is maintained at 40°C - 50°C, the extraction time is 3 h - 4 h, 8 - 12 parts of natural antibacterial extract are collected, and 5 - 8 parts of chitosan derivative are selected.

[0006] As a further solution of the present invention: in the second step, the addition amount of deionized water is 50-80 parts, stirring is carried out at 40°C - 50°C, at a stirring speed of 200 r / min - 300 r / min for 30 min - 40 min, the extracted natural antibacterial extract is added and stirring continues for 30 min - 40 min, after adding the chitosan derivative, the temperature is raised to 60°C - 70°C, and stirring reaction is carried out at a stirring speed of 150 r / min - 200 r / min for 2 h - 3 h, and filtration is carried out through an ultrafiltration membrane with a pore size of 0.1 μm - 0.2 μm.

[0007] As a further solution of the present invention: in the third step, pyrrole and benzaldehyde are added to the reaction vessel according to the molar ratio of 4 - 5:3, under the oil bath condition of 130°C - 140°C, reflux reaction is carried out for 4 h - 6 h, after the reaction is completed, it is cooled to room temperature, propionic acid is removed by vacuum distillation to obtain a crude product, the crude product is separated and purified by silica gel column chromatography, a mixed solution with a volume ratio of petroleum ether and dichloromethane of 3 - 4:1 is used as the eluent, the target eluent is collected, after vacuum concentration, a porphyrin derivative is obtained, the obtained porphyrin derivative is dissolved in dichloromethane to prepare a solution with a concentration of 0.05 mol / L - 0.1 mol / L, zinc acetate is added thereto, the molar ratio of the porphyrin derivative to zinc acetate is 1:3 - 4, at a temperature of 60°C - 70°C, stirring reaction is carried out for 6 h - 8 h to fully coordinate the porphyrin derivative with zinc ions, after the reaction is completed, the reaction solution is cooled to room temperature, dichloromethane is removed by a rotary evaporator to obtain a solid product, and the solid product is recrystallized with ethanol to obtain a metal complex based on the porphyrin derivative, and 12 - 18 parts are prepared by mass fraction.

[0008] As a further solution of the present invention: in the third step, to the powdery blueberry peel, an ethanol solution with a volume fraction of 60% - 70% is added according to the solid-liquid ratio of 1:10 - 15, the ultrasonic power of the ultrasonic extractor is set to 300 W - 400 W, the extraction temperature is 50°C - 60°C, the extraction time is 2 h - 3 h, the centrifugation speed of the extract is 4000 r / min - 5000 r / min, the centrifugation time is 10 min - 15 min, the flow rate of the supernatant passing through the macroporous resin column is controlled to be 1 mL / min - 2 mL / min, the volume fraction of the eluting ethanol solution is 70% - 80%, 10 - 15 parts of high-purity anthocyanin compounds are collected, 8 - 12 parts of the prepared poly(lactic-co-glycolic acid) as a polymer carrier are prepared, and in addition, dichloromethane and ethanol are mixed according to the volume ratio of 3 - 3.5:2 as the reaction solvent.

[0009] As a further solution of the present invention: in the step four, the added mixed reaction solvent is 15-20 times the mass of the metal complex. In an environment of room temperature 20°C - 25°C, it is stirred at a stirring speed of 300 r / min - 400 r / min for 30 min - 45 min. After adding the anthocyanin compounds, it is continuously stirred for 20 min - 30 min. After adding the copolymer, the temperature is raised to 50°C - 60°C. Under nitrogen protection, it reacts at a stirring speed of 180 r / min - 220 r / min for 4 h - 6 h. After the reaction is completed, the reaction solution is cooled to room temperature, and the solvent is removed by a rotary evaporator under the conditions of a temperature of 40°C - 50°C and a vacuum degree of -0.08 MPa to -0.06 MPa to obtain a viscous paste. Then the paste is dispersed in deionized water to form a stable aqueous colloidal solution. Finally, through spray drying technology, the inlet air temperature is controlled at 180°C - 200°C, and the outlet air temperature is maintained at 80°C - 100°C to prepare a powdery light stabilizer protector, which is collected for standby.

[0010] As a further solution of the present invention: in the step four, the solvent is removed by a rotary evaporator under the conditions of a temperature of 40°C - 50°C and a vacuum degree of -0.08 MPa to -0.06 MPa. The inlet air temperature of the spray drying technology is controlled at 180°C - 200°C, and the outlet air temperature is maintained at 80°C - 100°C.

[0011] As a further solution of the present invention: in the step five, an antioxidant and antibacterial protective liquid is added according to 3% - 5% of the mass of the liquid fertilizer premix, and it is stirred at a stirring speed of 100 r / min - 150 r / min for 15 min - 20 min to preliminarily mix the protective liquid with the basic raw materials. Subsequently, a powdery light stabilizer protector accounting for 3% - 4% of the mass of the mixture is added to the mixture, and it is stirred with a high-speed stirrer at 1000 r / min - 1500 r / min for 10 min - 15 min.

[0012] Adopting the above technical solutions, compared with the prior art, the beneficial effects of the present invention are as follows: 1. The present invention selects 3-amino-5-mercapto-1,2,4-triazolylphenol as an antioxidant. Its special molecular structure contains multiple active sites. The mercapto group and phenolic hydroxyl group can provide active hydrogen atoms, effectively capture free radicals generated during the storage and use of liquid fertilizer due to contact with air, etc., thereby preventing the oxidation reaction of avermectin, maintaining its chemical structure stability, and maintaining its activity. Eugenol, a natural antibacterial component extracted from cloves, has broad-spectrum antibacterial properties, can inhibit the growth and reproduction of microorganisms, reduce the decomposition and damage of avermectin by microorganisms, and reduce the problem of reduced activity of avermectin caused by microbial action. The selected chitosan derivative has amino and hydroxyl groups on its molecular chain, enabling it to form a dense protective film on the surface of avermectin. This not only enhances the stability of the antioxidant and antibacterial protective liquid but also forms a protective film on the surface of avermectin to further prevent oxidation and microbial erosion. The finally prepared antioxidant and antibacterial protective liquid can avoid the gradual reduction of the activity of avermectin liquid fertilizer due to factors such as contact with air and microbial action, comprehensively solve the problem of reduced activity of avermectin in liquid fertilizer, and improve the comprehensive performance of the avermectin finished liquid fertilizer; 2. The present invention constructs a unique molecular structure by introducing specific substituents into the porphyrin ring and coordinating with zinc ions, endowing it with efficient light energy absorption and conversion capabilities, which can effectively convert light energy into other forms of energy, reducing the activity loss of avermectin caused by photolysis reaction. Anthocyanin compounds extracted from blueberry peels, as natural ultraviolet absorbers, can selectively absorb ultraviolet light and prevent its damage to avermectin. In cooperation with metal complexes, it broadens the protection range for light of different wavelengths and enhances the overall light stability effect. Poly(lactic-co-glycolic acid) forms hydrogen bonds with other components through the ester groups and hydroxyl groups on its molecular chain. During the preparation of the solution, it is slowly added and reacted, and finally wraps the light stabilizer and ultraviolet absorber to form nanoscale composite particles. This nanoscale structure greatly improves the dispersibility and stability of the protective agent in liquid fertilizer, enabling it to be more evenly distributed around avermectin, forming a comprehensive and lasting protection barrier. Predispersion and high-speed stirring homogenization ensure the uniform distribution of the light-stable protective agent in the avermectin finished liquid fertilizer, comprehensively improving the stability of avermectin under light, avoiding the photolysis reaction of avermectin under light conditions and affecting the loss of its active ingredients, and greatly improving the pest control and early ripening effects of the liquid fertilizer. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a schematic flow chart of the process steps in the embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0014] The following further describes the specific embodiments of the present invention with reference to the drawings. It should be noted here that the description of these embodiments is for helping to understand the present invention but does not constitute a limitation to the present invention.

[0015] In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0016] Please refer to the attached Figure 1 , a process for promoting the early maturity of crops by an avermectin finished liquid fertilizer of the present invention, the process comprising the following specific steps: Step 1: Select 3-amino-5-mercapto-1,2,4-triazolylphenol as an antioxidant, and then use supercritical carbon dioxide extraction technology to extract natural antibacterial components from cloves. Select a chitosan derivative, the amino and hydroxyl groups on its molecular chain are helpful to form a protective film on the surface of avermectin and play an antibacterial performance. At the same time, prepare deionized water as a solvent; Step 2: Add 3-amino-5-mercapto-1,2,4-triazolylphenol to deionized water, then stir to form a uniform solution, then slowly add the extracted natural antibacterial extract and continue to stir. After stirring is completed, add the chitosan derivative, heat up and stir to react. The chitosan derivative and other components interact through hydrogen bonds and van der Waals forces to form a stable complex. After the reaction is completed, cool the solution to room temperature, filter through an ultrafiltration membrane to remove unreacted impurities and large particulate matter, obtain a clear and transparent antioxidant antibacterial protective liquid, and store it in a brown bottle away from light; Step 3: Prepare pyrrole and benzaldehyde as starting materials, react in a propionic acid solvent to obtain a crude product, separate and purify the crude product, use a mixed solution of petroleum ether and dichloromethane as an eluent, collect the target eluent, obtain a porphyrin derivative after concentration under reduced pressure. Dissolve the obtained porphyrin derivative in dichloromethane, add zinc acetate to it, react to obtain a solid product, and then recrystallize the solid product with ethanol to obtain a metal complex based on the porphyrin derivative. Wash and dry the blueberry peel, crush it into powder, then add an ethanol solution, put it into an ultrasonic extractor for extraction. After the extraction is completed, centrifuge the extract to take the supernatant, pass the supernatant through a macroporous resin column, wash the macroporous resin column with deionized water until the effluent is colorless to remove impurities, and then elute with an ethanol solution, collect the eluate, concentrate the eluate under reduced pressure to remove ethanol, obtain a high-purity anthocyanin compound. At the same time, prepare a poly(lactic-co-glycolic acid) copolymer as a polymer carrier. In addition, mix dichloromethane and ethanol as a reaction solvent; Step 4: Add the metal complex based on porphyrin derivative into the mixed reaction solvent of dichloromethane and ethanol, then carry out a stirring reaction. Next, add anthocyanin compounds into the solution and continue stirring to ensure full mixing of the two components. Subsequently, slowly add poly(lactic-co-glycolic acid), and after heating, continue the stirring speed reaction under nitrogen protection. Poly(lactic-co-glycolic acid) will wrap the light stabilizer and ultraviolet absorber to form nano-scale composite particles. After the reaction ends, cool the reaction solution to room temperature, remove the solvent through a rotary evaporator to obtain a viscous paste. Then disperse the paste in deionized water to form a stable aqueous colloidal solution. Finally, use spray drying technology to make a powdered light-stable protective agent, and collect it for standby; Step 5: Mix the basic raw materials including abamectin technical, nitrogen source fertilizer, phosphorus source fertilizer, potassium source fertilizer, trace element fertilizer and auxiliary agent evenly to obtain a preliminary liquid fertilizer mixture. Subsequently, add an antioxidant and antibacterial protection liquid for a stirring reaction to preliminarily mix the protection liquid with the basic raw materials. After the reaction ends, add the powdered light-stable protective agent to the mixture for a high-speed stirring reaction to obtain an abamectin finished liquid fertilizer that promotes early maturity of crops.

[0017] In one embodiment of the present invention: In Step 1, 10 - 15 parts by mass of antioxidant are prepared, the extraction pressure for extracting natural antibacterial components is controlled at 20 MPa - 30 MPa, the temperature is maintained at 40°C - 50°C, the extraction time is 3 h - 4 h, 8 - 12 parts of natural antibacterial extract are collected, and 5 - 8 parts of chitosan derivative are selected.

[0018] In one embodiment of the present invention: In Step 2, the addition amount of deionized water is 50 - 80 parts, stirring is carried out at 40°C - 50°C at a stirring speed of 200 r / min - 300 r / min for 30 min - 40 min, add the extracted natural antibacterial extract and continue stirring for 30 min - 40 min, after adding chitosan derivative, heat up to 60°C - 70°C, and stir and react at a stirring speed of 150 r / min - 200 r / min for 2 h - 3 h, and filter through an ultrafiltration membrane with a pore size of 0.1 μm - 0.2 μm.

[0019] In one embodiment of the present invention: In step three, pyrrole and benzaldehyde are added to the reaction vessel in a molar ratio of 4 - 5:3. Under the condition of an oil bath at 130°C - 140°C, reflux reaction is carried out for 4h - 6h. After the reaction is completed, it is cooled to room temperature, and propionic acid is removed by vacuum distillation to obtain a crude product. The crude product is separated and purified by silica gel column chromatography, and a mixed solution of petroleum ether and dichloromethane with a volume ratio of 3 - 4:1 is used as the eluent. The target eluent is collected, and after concentration under reduced pressure, a porphyrin derivative is obtained. The obtained porphyrin derivative is dissolved in dichloromethane to prepare a solution with a concentration of 0.05mol / L - 0.1mol / L. Zinc acetate is added thereto, and the molar ratio of the porphyrin derivative to zinc acetate is 1:3 - 4. At a temperature of 60°C - 70°C, stirring reaction is carried out for 6h - 8h to fully coordinate the porphyrin derivative with zinc ions. After the reaction is completed, the reaction solution is cooled to room temperature, dichloromethane is removed by a rotary evaporator to obtain a solid product, and the solid product is recrystallized with ethanol to obtain a metal complex based on the porphyrin derivative, which is prepared in 12 - 18 parts by mass.

[0020] In one embodiment of the present invention: In step three, to the powdered blueberry peel, an ethanol solution with a volume fraction of 60% - 70% is added according to a solid-liquid ratio of 1:10 - 15. The ultrasonic power of the ultrasonic extractor is set to 300W - 400W, the extraction temperature is 50°C - 60°C, the extraction time is 2h - 3h, the centrifugation speed of the extract is 4000r / min - 5000r / min, the centrifugation time is 10min - 15min, the flow rate of the supernatant through the macroporous resin column is controlled to be 1mL / min - 2mL / min, the volume fraction of the eluting ethanol solution is 70% - 80%, 10 - 15 parts of high-purity anthocyanin compounds are collected, 8 - 12 parts of the prepared poly(lactic-co-glycolic acid) copolymer is used as the polymer carrier, and in addition, dichloromethane and ethanol are mixed in a volume ratio of 3 - 3.5:2 as the reaction solvent.

[0021] In one embodiment of the present invention: In step four, the added mixed reaction solvent is 15 - 20 times the mass of the metal complex. Under the environment of room temperature 20°C - 25°C, it is stirred at a stirring speed of 300 r / min - 400 r / min for 30 min - 45 min. After adding the anthocyanin compounds, it is continuously stirred for 20 min - 30 min. After adding the copolymer, the temperature is raised to 50°C - 60°C. Under nitrogen protection, it reacts at a stirring speed of 180 r / min - 220 r / min for 4 h - 6 h. After the reaction ends, the reaction solution is cooled to room temperature, and the solvent is removed by a rotary evaporator under the conditions of a temperature of 40°C - 50°C and a vacuum degree of -0.08 MPa to -0.06 MPa to obtain a viscous paste. Then the paste is dispersed in deionized water to form a stable aqueous colloidal solution. Finally, through spray drying technology, the inlet air temperature is controlled at 180°C - 200°C, and the outlet air temperature is maintained at 80°C - 100°C to prepare a powdery light stabilizer, which is collected for standby.

[0022] In one embodiment of the present invention: In step four, the solvent is removed by a rotary evaporator under the conditions of a temperature of 40°C - 50°C and a vacuum degree of -0.08 MPa to -0.06 MPa. The inlet air temperature of the spray drying technology is controlled at 180°C - 200°C, and the outlet air temperature is maintained at 80°C - 100°C.

[0023] In one embodiment of the present invention: In step five, an antioxidant and antibacterial protective liquid is added according to 3% - 5% of the mass of the liquid fertilizer premix, and it is stirred at a stirring speed of 100 r / min - 150 r / min for 15 min - 20 min to preliminarily mix the protective liquid with the basic raw materials. Subsequently, a powdery light stabilizer accounting for 3% - 4% of the mass of the mixture is added to the mixture, and it is stirred with a high-speed stirrer at 1000 r / min - 1500 r / min for 10 min - 15 min.

[0024] In one embodiment of the present invention: In step five, the abamectin technical material is added in an amount of 1 - 5 parts by mass. The nitrogen source fertilizer is urea and is added in an amount of 10 - 20 parts by mass. The phosphorus source fertilizer is potassium dihydrogen phosphate and is added in an amount of 8 - 15 parts by mass. The potassium source fertilizer is potassium sulfate and is added in an amount of 8 - 15 parts by mass. The trace element fertilizer includes compounds of trace elements such as iron, zinc, manganese, boron, etc., including ferrous sulfate, zinc sulfate, etc., and is added in a total amount of 1 - 3 parts by mass. The auxiliary agents include surfactants and dispersants and are added in an amount of 0.5 - 2 parts by mass.

[0025] In one embodiment of the present invention: In step two, during the stirring reaction with the addition of the chitosan derivative, a trace amount of inert gas is simultaneously introduced. The inert gas is argon or helium, and the introduction rate is 5 mL / min - 10 mL / min. By introducing the inert gas, the oxygen content in the system is further reduced, the possible oxidation reaction is inhibited, the stability of the antioxidant and antibacterial protective solution is enhanced, and the activity of abamectin is more effectively maintained.

[0026] In one embodiment of the present invention: In step three, the obtained porphyrin derivative is subjected to secondary purification treatment. Specifically, the porphyrin derivative obtained by vacuum concentration is dissolved again in a specific mixed solvent. The mixed solvent is composed of dichloromethane and acetonitrile mixed in a volume ratio of 2 - 3:1, and then secondary purification is carried out by recrystallization. The purity of the porphyrin derivative after secondary purification reaches more than 98%, so that the metal complex based on the porphyrin derivative prepared subsequently has more excellent photo-stable performance, thereby improving the protection effect of the photo-stable protectant on abamectin.

[0027] In one embodiment of the present invention: In step four, during the process of poly(lactic-co-glycolic acid) encapsulating the photo-stabilizer and the ultraviolet absorber to form nano-scale composite particles, ultrasonic wave-assisted treatment is introduced. The frequency of the ultrasonic wave is set to 20 kHz - 30 kHz, the power is 100 W - 200 W, and the treatment time is 30 min - 45 min. By ultrasonic wave-assisted treatment, poly(lactic-co-glycolic acid) can encapsulate the photo-stabilizer and the ultraviolet absorber more uniformly, optimize the structure of the nano-scale composite particles, further improve the dispersibility and stability of the photo-stable protectant in the liquid fertilizer, and enhance the photo-stable protection effect on abamectin.

[0028] In one embodiment of the present invention: In step five, the final abamectin finished product liquid fertilizer is subjected to microencapsulation treatment. The interfacial polymerization method is adopted, and gelatin and gum arabic are used as wall materials to encapsulate the abamectin finished product liquid fertilizer to form microcapsules. The specific process is as follows: The abamectin finished product liquid fertilizer and the wall material solution are mixed in a mass ratio of 1:2 - 3, stirred evenly at 40°C - 50°C, and then the curing agent glutaraldehyde is added. The addition amount of glutaraldehyde is 1% - 3% of the mass of the wall material, and the stirring reaction is continued for 1 h - 2 h to form the microencapsulated abamectin finished product liquid fertilizer. The average particle size of the microcapsules is controlled within 10 μm - 20 μm. By microencapsulation treatment, the release of abamectin and other nutrient components can be delayed, the long-acting property of the liquid fertilizer can be improved, the effect of promoting early maturity of crops can be further enhanced, and nutrient loss and environmental pollution can be reduced.

[0029] Example 1. Please refer to the appendix Figure 1, first, select 15 portions of 3-amino-5-mercapto-1,2,4-triazolylphenol as antioxidants, and use supercritical carbon dioxide extraction technology to extract natural antibacterial components from cloves. Control the extraction pressure at 30 MPa, maintain the temperature at 50 °C, and the extraction time is 4 h. Collect 12 portions of natural antibacterial extracts. Select 8 portions of chitosan derivatives, and simultaneously prepare 80 portions of deionized water as a solvent. Then add 3-amino-5-mercapto-1,2,4-triazolylphenol to 80 portions of deionized water, and stir at a stirring speed of 300 r / min for 40 min at 50 °C to form a homogeneous solution. Slowly add the extracted natural antibacterial extract, and continue to stir for 40 min to promote full mixing. Then add chitosan derivatives, raise the temperature to 70 °C, and stir and react at a stirring speed of 200 r / min for 3 h to form a stable complex through hydrogen bonds and van der Waals forces. After the reaction, cool to room temperature, filter through a ultrafiltration membrane with a pore size of 0.2 μm to obtain a clear and transparent antioxidant and antibacterial protective liquid, fill it into a brown bottle and store it in the dark. Then prepare pyrrole and benzaldehyde as starting materials, add them to the reaction vessel in a molar ratio of pyrrole:benzaldehyde = 5:3 in a propionic acid solvent, and reflux and react for 6 h under an oil bath condition of 140 °C. After the reaction, cool to room temperature, distill off propionic acid under reduced pressure to obtain a crude product, and use silica gel column chromatography to separate and purify it with a mixed solution of petroleum ether and dichloromethane in a volume ratio of 4:1 as an eluent, collect the target eluent, and obtain a porphyrin derivative after concentration under reduced pressure. Dissolve it in dichloromethane to prepare a solution with a concentration of 0.1 mol / L, add zinc acetate to it, and the molar ratio of porphyrin derivative to zinc acetate is 1:4. Stir and react at a temperature of 70 °C for 8 h to fully coordinate the porphyrin derivative with zinc ions. After the reaction, cool to room temperature, remove dichloromethane with a rotary evaporator, and then recrystallize with ethanol to obtain a metal complex based on the porphyrin derivative, and prepare 18 portions by mass. Wash the blueberry peel, dry it, and crush it into a powder. Add an ethanol solution with a volume fraction of 70% according to a solid-liquid ratio of 1:15, put it into an ultrasonic extractor, set the ultrasonic power to 400 W, the extraction temperature to 60 °C, and the extraction time to 3 h. After the extraction, centrifuge the extract at a speed of 5000 r / min for 15 min, take the supernatant, pass the supernatant through a macroporous resin column, control the flow rate at 2 mL / min, wash it with deionized water until the effluent is colorless, and then elute it with an ethanol solution with a volume fraction of 80%. Collect the eluate and concentrate it under reduced pressure to obtain 15 portions of high-purity anthocyanin compounds. At the same time, prepare 12 portions of poly(lactic-co-glycolic acid) as a polymer carrier, and mix dichloromethane and ethanol in a ratio of 3.Mix in a volume ratio of 5:2 as the reaction solvent. Add 18 parts of the metal complex based on porphyrin derivatives to the mixed reaction solvent of dichloromethane and ethanol that is 20 times its mass. Stir at a speed of 400 r / min for 45 min at room temperature of 25°C. Then add 15 parts of anthocyanin compounds and continue stirring for 30 min. Subsequently, slowly add 12 parts of poly(lactic-co-glycolic acid). Heat up to 60°C and react for 6 h under nitrogen protection at a stirring speed of 220 r / min. The poly(lactic-co-glycolic acid) encapsulates the light stabilizer and ultraviolet absorber to form nanoscale composite particles. After the reaction ends, cool the reaction solution to room temperature and remove the solvent through a rotary evaporator under the conditions of a temperature of 50°C and a vacuum degree of -0.06 MPa to obtain a viscous paste. Then disperse the paste in deionized water to form a stable aqueous colloidal solution. Through spray drying technology, control the inlet air temperature at 200°C and maintain the outlet air temperature at 100°C to make and collect the powdery light stability protective agent for standby. Finally, mix the basic raw materials avermectin technical, nitrogen source fertilizer, phosphorus source fertilizer, potassium source fertilizer, trace element fertilizer, and additives evenly to obtain a preliminary mixture of liquid fertilizer. Add the antioxidant and antibacterial protective liquid at 5% of the mass of the preliminary mixture of liquid fertilizer and stir at a speed of 150 r / min for 20 min to preliminarily mix the protective liquid with the basic raw materials. Subsequently, add the powdery light stability protective agent at 4% of the mass of the mixture to the mixture and stir with a high-speed stirrer at 1500 r / min for 15 min to obtain the avermectin finished liquid fertilizer that promotes the early maturity of crops.

[0030] Example 2. Please refer to the attached Figure 1, first select 10 portions of 3-amino-5-mercapto-1,2,4-triazolylphenol as antioxidants, and use supercritical carbon dioxide extraction technology to extract natural antibacterial components from cloves. Control the extraction pressure at 20 MPa, maintain the temperature at 40 °C, and the extraction time is 3 h. Collect 8 portions of natural antibacterial extracts, select 5 portions of chitosan derivatives, and prepare 50 portions of deionized water as a solvent. Then add 3-amino-5-mercapto-1,2,4-triazolylphenol to 50 portions of deionized water, and stir at a stirring speed of 200 r / min for 30 min at 40 °C to form a homogeneous solution. Slowly add the extracted natural antibacterial extract, and continue to stir for 30 min to promote full mixing. Then add chitosan derivatives, heat up to 60 °C, and stir and react at a stirring speed of 150 r / min for 2 h to form a stable complex through hydrogen bonds and van der Waals forces. After the reaction, cool to room temperature, filter through a ultrafiltration membrane with a pore size of 0.1 μm to obtain a clear and transparent antioxidant antibacterial protective liquid, fill it into a brown bottle and store it away from light. Then prepare pyrrole and benzaldehyde as starting materials, add them to the reaction vessel in a molar ratio of pyrrole:benzaldehyde = 4:3 in a propionic acid solvent, and reflux and react for 4 h under an oil bath condition of 130 °C. After the reaction, cool to room temperature, distill off propionic acid under reduced pressure to obtain a crude product, and use silica gel column chromatography to separate and purify it with a mixed solution of petroleum ether and dichloromethane in a volume ratio of 3:1 as the eluent. Collect the target eluent, concentrate it under reduced pressure to obtain a porphyrin derivative, and dissolve it in dichloromethane to prepare a concentration of 0.A 0.05 mol / L solution was prepared, and zinc acetate was added thereto. The molar ratio of the porphyrin derivative to zinc acetate was 1:3. At a temperature of 60 °C, the mixture was stirred and reacted for 6 h to allow the porphyrin derivative to fully coordinate with zinc ions. After the reaction, it was cooled to room temperature, and dichloromethane was removed using a rotary evaporator. Then, recrystallization was carried out with ethanol to obtain 12 parts by mass of a metal complex based on the porphyrin derivative. The blueberry peels were washed, dried, and crushed into a powder. According to a solid-liquid ratio of 1:10, a 60% (v / v) ethanol solution was added, and the mixture was placed in an ultrasonic extractor. The ultrasonic power was set to 300 W, the extraction temperature was 50 °C, and the extraction time was 2 h. After extraction, the extract was centrifuged at 4000 r / min for 10 min, and the supernatant was taken. The supernatant was passed through a macroporous resin column with a flow rate controlled at 1 mL / min and rinsed with deionized water until the effluent was colorless. Then, it was eluted with a 70% (v / v) ethanol solution, and the eluate was collected and concentrated under reduced pressure to obtain 10 parts by mass of high-purity anthocyanin compounds. At the same time, 8 parts by mass of poly(lactic-co-glycolic acid) were prepared as a polymer carrier. Dichloromethane and ethanol were mixed as a reaction solvent at a volume ratio of 3:2. 12 parts by mass of the metal complex based on the porphyrin derivative were added to a mixed reaction solvent of dichloromethane and ethanol that was 15 times its mass. At room temperature (20 °C), the mixture was stirred at a speed of 300 r / min for 30 min. Then, 10 parts by mass of the anthocyanin compounds were added, and stirring was continued for 20 min. Subsequently, 8 parts by mass of poly(lactic-co-glycolic acid) were slowly added, and the temperature was raised to 50 °C. Under nitrogen protection, the reaction was carried out at a stirring speed of 180 r / min for 4 h. The poly(lactic-co-glycolic acid) encapsulated the light stabilizer and ultraviolet absorber to form nanoscale composite particles. After the reaction, the reaction solution was cooled to room temperature, and the solvent was removed using a rotary evaporator at a temperature of 40 °C and a vacuum degree of -0.08 MPa to obtain a viscous paste. Then, the paste was dispersed in deionized water to form a stable aqueous colloidal solution. Through spray drying technology, the inlet air temperature was controlled at 180 °C, and the outlet air temperature was maintained at 80 °C to prepare a powdered light-stable protective agent for collection and standby. Finally, the basic raw materials, i.e., abamectin technical, nitrogen source fertilizer, phosphorus source fertilizer, potassium source fertilizer, trace element fertilizer, and additives, were mixed evenly to obtain a preliminary liquid fertilizer mixture. An antioxidant and antibacterial protective solution was added at 3% by mass of the preliminary liquid fertilizer mixture, and the mixture was stirred at a speed of 100 r / min for 15 min to preliminarily mix the protective solution with the basic raw materials. Subsequently, 3% by mass of the powdered light-stable protective agent was added to the mixture, and the mixture was stirred at a high speed of 1000 r / min for 10 min to obtain an abamectin finished liquid fertilizer that promotes the early maturity of crops.

[0031] According to the content of the above two groups of embodiments, by selecting special antioxidants 3-amino-5-mercapto-1,2,4-triazolylphenol, natural antibacterial ingredient eugenol and chitosan derivatives, introducing specific substituents into the porphyrin ring and coordinating with zinc ions, and using anthocyanin compounds extracted from blueberry peels and poly(lactic-co-glycolic acid), etc., the problem of the reduced activity of avermectin in liquid fertilizer is effectively solved, the stability of avermectin in liquid fertilizer is improved, and with the synergistic cooperation of various technologies in each link, the good effect of preparing a highly efficient and stable avermectin liquid fertilizer can be achieved. This process has significant technical advantages and broad application prospects.

[0032] Although the present invention is disclosed above in a preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art can make possible changes and modifications without departing from the spirit and scope of the present invention. Therefore, any modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention without departing from the technical solution of the present invention shall fall within the protection scope defined by the claims of the present invention.

Claims

1. A process for promoting the early maturity of crops by using avermectin finished liquid fertilizer, characterized in that: The process comprises the following specific steps: Step 1: Select 3-amino-5-mercapto-1,2,4-triazolylphenol as an antioxidant, then use supercritical carbon dioxide extraction technology to extract natural antibacterial components from cloves, select chitosan derivatives, and prepare deionized water as a solvent; Step 2: Add 3-amino-5-mercapto-1,2,4-triazolylphenol to deionized water, and then stir to form a uniform solution, then slowly add the extracted natural antibacterial extract and continue stirring, add the chitosan derivative after stirring, heat and stir to react, cool the solution to room temperature after the reaction, filter through an ultrafiltration membrane to obtain a clear and transparent antioxidant antibacterial protective solution, and store it in a brown bottle away from light; Step 3: prepare pyrrole and benzaldehyde as starting materials, react in propionic acid solvent to obtain a crude product, separate and purify the crude product, use a mixture of petroleum ether and dichloromethane as an eluent, collect the target eluate, and concentrate under reduced pressure to obtain a porphyrin derivative. The obtained porphyrin derivative is dissolved in dichloromethane, zinc acetate is added thereto, and a solid product is obtained by reaction. The solid product is recrystallized with ethanol to obtain a metal complex based on a porphyrin derivative. The blueberry peel is washed and dried, and then crushed into a powder, and then an ethanol solution is added and extracted in an ultrasonic extractor. After the extraction is completed, the extract is centrifuged to obtain a supernatant, and the supernatant is passed through a macroporous resin column. The macroporous resin column is rinsed with deionized water until the effluent is colorless, and then eluted with an ethanol solution, the eluate is collected, and the eluate is concentrated under reduced pressure to remove ethanol to obtain a high-purity anthocyanin compound. At the same time, polylactic acid-glycolic acid copolymer is prepared as a polymer carrier. In addition, dichloromethane and ethanol are mixed as a reaction solvent; Step 4: adding a metal complex based on a porphyrin derivative to a mixed reaction solvent of dichloromethane and ethanol, followed by stirring for reaction, then adding anthocyanin compounds to the solution and continuing to stir, then slowly adding polylactic acid-glycolic acid copolymer, heating and continuing to react at a stirring speed under nitrogen protection, after the reaction is completed, cooling the reaction solution to room temperature, removing the solvent by a rotary evaporator to obtain a viscous paste, and then dispersing the paste in deionized water to form a stable water-based colloidal solution, and finally preparing a powdered light-stabilizing protective agent by spray drying technology, and collecting for later use; Step 5, the basic raw materials including avermectin original drug, nitrogen source fertilizer, phosphorus source fertilizer, potassium source fertilizer, trace element fertilizer and adjuvant are mixed evenly to obtain a liquid fertilizer primary mixture, and then an antioxidant antibacterial protective liquid is added to carry out stirring reaction, and after the reaction is completed, a powdered light-stable protective agent is added to the mixture to carry out high-speed stirring reaction to obtain an avermectin finished liquid fertilizer that promotes early maturity of crops.

2. A process for promoting the early maturity of crops by using a finished liquid fertilizer of avermectin according to claim 1, characterized in that: In the step 1, 10-15 parts of antioxidants are prepared by mass, the extraction pressure for extracting natural antibacterial components is controlled at 20MPa-30MPa, the temperature is maintained at 40°C-50°C, the extraction time is 3h-4h, 8-12 parts of natural antibacterial extracts are collected, and 5-8 parts of chitosan derivatives are selected.

3. The process for promoting the early maturity of crops by using a finished avermectin liquid fertilizer according to claim 1, characterized in that: In the step 2, the amount of deionized water added is 50-80 parts, the mixture is stirred at 40°C-50°C, at a stirring speed of 200r / min-300r / min for 30min-40min, the extracted natural antibacterial extract is added and stirring is continued for 30min-40min, after the chitosan derivative is added, the temperature is raised to 60°C-70°C, the mixture is stirred at a stirring speed of 150r / min-200r / min for 2h-3h, and filtered through an ultrafiltration membrane with a pore size of 0.1μm-0.2μm.

4. The process for promoting the early maturity of crops by using a finished liquid fertilizer of avermectin according to claim 1, characterized in that: In the step 3, pyrrole: benzaldehyde is added to the reaction container in a ratio of 4-5:3 in terms of the amount of substance, and the reaction is refluxed for 4h-6h under an oil bath condition of 130°C-140°C. After the reaction is completed, the reaction is cooled to room temperature, and propionic acid is removed by distillation under reduced pressure to obtain a crude product. The crude product is separated and purified by silica gel column chromatography, and a mixed solution of petroleum ether and dichloromethane in a volume ratio of 3-4:1 is used as an eluent, and the target eluent is collected, and the porphyrin derivative is obtained after concentration under reduced pressure, and the obtained porphyrin derivative is dissolved in dichloromethane. A solution with a concentration of 0.05 mol / L-0.1 mol / L is prepared in chloromethane, and zinc acetate is added thereto, with the molar ratio of the porphyrin derivative to zinc acetate being 1:3-4. The reaction is stirred at a temperature of 60°C-70°C for 6h-8h. After the reaction is completed, the reaction solution is cooled to room temperature, and the dichloromethane is removed by a rotary evaporator to obtain a solid product. The solid product is then recrystallized from ethanol to obtain a metal complex based on the porphyrin derivative, and 12-18 parts are prepared by mass.

5. The process for promoting the early maturity of crops by using a finished liquid fertilizer of avermectin according to claim 1, characterized in that: In the step three, a 60%-70% ethanol solution is added to the powdered blueberry peel according to a solid-liquid ratio of 1:10-15, the ultrasonic power of the ultrasonic extractor is set to 300W-400W, the extraction temperature is 50°C-60°C, the extraction time is 2h-3h, the centrifugal speed of the extract is 4000r / min-5000r / min, the centrifugal time is 10min-15min, the flow rate of the supernatant through the macroporous resin column is controlled to be 1mL / min-2mL / min, the volume fraction of the eluted ethanol solution is 70%-80%, 10-15 parts of high-purity anthocyanin compounds are collected, 8-12 parts of the prepared polylactic acid-glycolic acid copolymer as a high molecular weight polymer carrier, and in addition, dichloromethane and ethanol are mixed in a volume ratio of 3-3.5:2 as a reaction solvent.

6. The process for promoting the early maturity of crops by using a finished liquid fertilizer of avermectin according to claim 1, characterized in that: In the step 4, the added mixed reaction solvent is 15-20 times the mass of the metal complex, and the mixture is stirred at a stirring speed of 300r / min-400r / min for 30min-45min at room temperature of 20°C-25°C. After the anthocyanin compound is added, the stirring is continued for 20min-30min. After the copolymer is added, the temperature is raised to 50°C-60°C, and under nitrogen protection, the mixture is reacted at a stirring speed of 180r / min-220r / min for 4h-6h. After the reaction is completed, the reaction solution is cooled to room temperature, and the solvent is removed by a rotary evaporator at a temperature of 40°C-50°C and a vacuum degree of -0.08MPa to -0.06MPa to obtain a viscous paste, and the paste is dispersed in deionized water to form a stable water-based colloidal solution. Finally, the spray drying technology is used to control the inlet temperature at 180°C-200°C and the outlet temperature at 80°C-100°C to prepare a powdered light-stabilizing protective agent, which is collected for later use.

7. The process for promoting the early maturity of crops by using a finished liquid fertilizer of avermectin according to claim 1, characterized in that: In the step 4, the solvent is removed by a rotary evaporator at a temperature of 40°C-50°C and a vacuum degree of -0.08MPa to -0.06MPa. The inlet air temperature of the spray drying technology is controlled at 180°C-200°C, and the outlet air temperature is maintained at 80°C-100°C.

8. The process for promoting the early maturity of crops by using a finished liquid fertilizer of avermectin according to claim 1, characterized in that: In the step 5, an antioxidant and antibacterial protective liquid is added according to 3%-5% of the mass of the liquid fertilizer initial mixture, and the mixture is stirred at a stirring speed of 100r / min-150r / min for 15min-20min, and then 3%-4% of the mass of the mixture is added to the mixture. A powdered light-stabilizing protective agent is stirred for 10min-15min with a high-speed stirrer of 1000r / min-1500r / min.

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