A formula for a synthetic biotechnology-enabled net-capturing and loss-controlling medicine-fertilizer and its preparation process

Abstract

The present invention discloses a formulation of a network capture and loss control medicine fertilizer empowered by synthetic biotechnology and its preparation process, which relates to the technical field of fertilizers. The loss control medicine fertilizer is prepared from the following components in parts by weight: 60-80 parts of compound fertilizer, 10-20 parts of diammonium phosphate, 2-10 parts of trace elements, 2-8 parts of modified attapulgite, 1-4 parts of insecticide, 0.5-3 parts of polyglutamic acid, and 1-5 parts of polyvinyl alcohol. Through the empowerment of polyglutamic acid and the synergistic effect of multiple components, the present invention forms an efficient network capture and loss control system, which not only solves the problems of easy nutrient loss and poor pesticide stability in traditional medicine fertilizers, but also realizes the synergistic slow release of nutrients and pesticides, significantly improves the fertilizer utilization rate and the pesticide efficacy period, and has good application value.

Description

Technical Field

[0001] The present invention relates to the technical field of fertilizers, and particularly relates to a formula of a net-capturing and loss-controlling medicine-fertilizer empowered by synthetic biotechnology and a preparation process thereof. Background Art

[0002] Fertilizers are the basic conditions for crop growth and also an important factor restricting the sustainable development of agriculture in China. At present, China is a large agricultural country, and the amount of fertilizer applied ranks among the top in the world, but the fertilizer utilization efficiency is generally low. A large amount of unused fertilizers enter water bodies through surface runoff, groundwater infiltration and other ways, causing serious non-point source pollution problems.

[0003] To solve the problem of low fertilizer utilization efficiency, currently, two main technical routes of slow-release fertilizers and loss-controlling fertilizers are mainly adopted. Slow-release fertilizers are a new type of fertilizers, and their core is to control the release rate and time of fertilizer nutrients through technologies such as coating and resin encapsulation, so that the nutrient release process matches the growth requirements of crops. However, such fertilizers have the following problems: 1) The nutrient release mode is relatively fixed and it is difficult to dynamically regulate according to the fertilizer demand of crops; 2) Existing coating materials such as sulfur, resin, paraffin, polyethylene, etc. are difficult to degrade in the soil and are easy to cause environmental pollution; 3) The production cost is relatively high, which is not conducive to large-scale popularization and application.

[0004] Loss-controlling fertilizers adopt different technical principles, mainly by adding special loss-controlling agents to form a protective structure in the soil. Loss-controlling materials represented by attapulgite can fix nutrients through chemical and physical adsorption by utilizing its nano-pore structure, high specific surface area and ion exchange capacity. This method can effectively reduce nutrient loss and the production cost is relatively low.

[0005] As a new type of preparation that combines fertilizers and pesticides, medicine-fertilizers can achieve "fertilizer-driven pesticides", and can achieve the purpose of preventing and controlling pests and diseases while providing nutrients, which is an important direction for the development of modern agriculture. However, there are still many technical bottlenecks in the current medicine-fertilizer products on the market: First, physical and chemical reactions are likely to occur between fertilizers and pesticides, affecting their respective efficacy; Second, due to the lack of effective carriers and stable systems, the active ingredients of pesticides are easily degraded and lost; Third, the release rates of nutrients and pesticides are difficult to be coordinated and matched, and continuous and stable control effects cannot be achieved.

[0006] Although the common compound fertilizers on the market at present can provide multiple nutrients, due to the lack of effective synergistic effects between their components, the nutrient release is uneven and it is difficult to meet the nutritional requirements of crop growth. At the same time, when applying compound fertilizers alone, it is often necessary to additionally supplement quick-acting fertilizers such as diammonium phosphate, which increases the fertilization cost and labor intensity.

[0007] CN117658733A discloses a special corn controlled-release compound fertilizer and its preparation method, belonging to the technical field of fertilizers. The special corn controlled-release compound fertilizer disclosed by the present invention comprises the following raw materials in parts by weight: 30-50 parts of urea, 5-10 parts of diammonium hydrogen phosphate, 15-20 parts of superphosphate, 10-15 parts of potassium chloride, 2-6 parts of zinc sulfate, 2-5 parts of organic acid, and 1-5 parts of controlled-release agent.

[0008] The research and development of new fertilizers is developing towards the direction of high nutrient efficiency and diverse functions. Research shows that by using new materials and new processes to improve traditional fertilizers, their nutritional functions can be significantly enhanced or new characteristics can be imparted. Among them, functional polymer materials show good application prospects in improving fertilizer utilization efficiency due to their unique structural characteristics and performance advantages. Such materials mainly include three categories: synthetic polymers, natural polymers, and modified natural polymers. Among them, modified natural polymers not only have excellent functionality but also maintain the cost advantage of being relatively low.

[0009] Under the background of the increasingly serious agricultural non-point source pollution in China, it is urgent to develop a synergistic controlled-release pesticide-fertilizer that can not only meet the growth needs of crops, effectively control nutrient loss, but also be environmentally friendly, economical, and practical. This is of great significance for improving fertilizer utilization efficiency, reducing agricultural non-point source pollution, and promoting the sustainable development of agriculture. Summary of the Invention

[0010] In order to solve the deficiencies of the existing technology, the purpose of the present invention is to provide a formula and preparation process of a net-trapping controlled-release pesticide-fertilizer empowered by synthetic biotechnology. Through the empowerment of polyglutamic acid and the synergistic effect of multiple components, an efficient net-trapping controlled-release system is formed, which not only solves the problems of easy nutrient loss and poor pesticide stability in traditional pesticide-fertilizers, but also realizes the synergistic slow release of nutrients and pesticides, significantly improving the fertilizer utilization rate and the pesticide efficacy period, and having good application value.

[0011] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0012] A formula of a net-trapping controlled-release pesticide-fertilizer empowered by synthetic biotechnology, in parts by weight, is made up of the following components: 60-80 parts of compound fertilizer, 10-20 parts of diammonium phosphate, 2-10 parts of trace elements, 2-8 parts of modified attapulgite, 1-4 parts of insecticide, 0.5-3 parts of polyglutamic acid, and 1-5 parts of polyvinyl alcohol.

[0013] Preferably, the preparation method of the modified attapulgite comprises the following steps:

[0014] (1) Disperse attapulgite into a methanol / water mixed solution, perform ultrasonic treatment, adjust the pH of the dispersion liquid, add KH570, raise the temperature for reaction, centrifuge, wash, and dry the product to obtain pretreated attapulgite;

[0015] Silanization modification: The methoxy groups of KH570 hydrolyze under acidic conditions to form silanol groups (-Si-OH). These silanol groups undergo a condensation reaction with the hydroxyl groups (-OH) on the surface of attapulgite to form stable Si-O-Si covalent bonds. At the same time, the double bond groups in the KH570 molecules are exposed on the surface of attapulgite, providing active sites for subsequent grafting reactions. This step realizes the organic modification of the attapulgite surface and increases its compatibility with organic monomers.

[0016] Preferably, in step (1), the particle size of the attapulgite is 200 - 400 mesh.

[0017] Preferably, in step (1), the volume ratio of methanol to deionized water in the methanol / water mixture is 7 - 9:3 - 1; the dosage ratio of attapulgite, methanol / water mixture, and KH570 is 10 g:80 - 150 mL:0.3 - 1 g.

[0018] Preferably, in step (1), ultrasonic treatment is carried out for 15 - 30 min, and the pH of the dispersion is adjusted to 4 - 5 with glacial acetic acid; the heating reaction conditions are heating to 60 - 75 °C and reacting at 400 - 600 r / min for 12 - 18 h.

[0019] (2) Disperse the pretreated attapulgite in deionized water, carry out ultrasonic treatment, add L-allylglycine, introduce nitrogen and add ammonium persulfate, stir and react, centrifuge, wash, and dry the product to obtain grafted attapulgite;

[0020] Free radical graft polymerization: Ammonium persulfate decomposes under heating conditions to generate free radicals, which initiate the free radical polymerization of the double bonds introduced in the first step. The double bonds in the L-allylglycine molecules are activated and gradually grow through the free radical addition mechanism to form graft polymer chains on the surface of attapulgite. The amino groups on the polymer chains serve as active groups, providing reaction sites for subsequent modification. Nitrogen protection prevents oxygen from inhibiting the free radical polymerization process.

[0021] Preferably, in step (2), the dosage ratio of pretreated attapulgite, deionized water, L-allylglycine, and ammonium persulfate is 10 g:80 - 150 mL:1 - 2 g:0.02 - 0.1 g.

[0022] Preferably, in step (2), ultrasonic treatment is carried out for 15 - 30 min; the stirring reaction conditions are reacting at 55 - 70 °C and 300 - 400 r / min for 4 - 8 h; wash with warm water at 70 - 90 °C for 3 - 4 times.

[0023] (3) Disperse the grafted attapulgite in DMF, perform ultrasonic treatment, add 2-hydroxyphosphonoacetic acid, add EDC and NHS under light protection, stir and react, centrifuge, wash, and dry the product to obtain modified attapulgite.

[0024] Amidation reaction: EDC first reacts with the carboxyl group of 2-hydroxyphosphonoacetic acid to form an O-acylurea intermediate, and then NHS reacts with this intermediate to generate an active ester intermediate. This active ester intermediate can undergo a nucleophilic substitution reaction with the amino group introduced in the second step to form a stable amide bond, covalently linking the phosphorus-containing group to the surface of attapulgite.

[0025] Preferably, in step (3), the dosage ratio of the grafted attapulgite, DMF, 2-hydroxyphosphonoacetic acid, EDC, and NHS is 10 g: 80 - 150 mL: 0.6 - 1.5 g: 0.8 - 1.2 g: 0.4 - 0.6 g.

[0026] Preferably, in step (3), the stirring reaction conditions are to stir and react at 20 - 30 °C and 200 - 300 r / min for 12 - 24 h; wash successively with DMF, absolute ethanol, and deionized water.

[0027] Preferably, in the compound fertilizer, the content ratio of nitrogen fertilizer, phosphate fertilizer, and potassium fertilizer is 12 - 16: 12 - 16: 12 - 16; the content of the nitrogen fertilizer is calculated based on the nitrogen element in the nitrogen fertilizer, the content of the phosphate fertilizer is calculated based on phosphorus pentoxide, and the content of the potassium fertilizer is calculated based on potassium oxide; the trace elements are made by mixing chelated ferrous, chelated copper, and chelated zinc according to a weight ratio of 1: 0.4 - 0.6: 0.8 - 1.2.

[0028] Preferably, the nitrogen fertilizer is one or more of urea, ammonium sulfate, ammonium bicarbonate, ammonium nitrate, ammonium chloride, sodium nitrate, calcium nitrate, and ammonium thionitrate; the phosphate fertilizer is one or more of monoammonium phosphate, diammonium phosphate, calcium magnesium phosphate fertilizer, superphosphate, triple superphosphate, sodium phosphate, enriched superphosphate, and ammonium phosphate; the potassium fertilizer is one or more of potassium sulfate, potassium chloride, potassium nitrate, and potassium dihydrogen sulfate.

[0029] Preferably, the trace elements are made by mixing ferrous sulfate, copper sulfate, and zinc sulfate according to a weight ratio of 1: 0.4 - 0.6: 0.8 - 1.2.

[0030] Preferably, the molecular weight of the polyvinyl alcohol is 3500 - 7000.

[0031] Preferably, the preparation method of the insecticide comprises the following steps: dispersing mesoporous silica in a pesticide ethanol solution at 5-20 mg / L, oscillating in a constant temperature water bath oscillator at 25-40 °C for 18-24 h, filtering the product with a sand core, washing with deionized water, and drying in vacuum to obtain the insecticide; the pesticide is one or more of chlorantraniliprole, clothianidin, dinotefuran, azoxystrobin, prothioconazole, thifluzamide; the dosage ratio of the mesoporous silica to the pesticide ethanol solution is 8-14 g:10 mL.

[0032] The present invention also claims to protect a preparation process of the network-trapping and loss-controlling medicine-fertilizer empowered by synthetic biotechnology, comprising the following steps: mixing compound fertilizer, diammonium phosphate, trace elements, modified attapulgite, insecticide, and polyglutamic acid, stirring for 10-20 min, grinding through a 40-60 mesh sieve, adding polyvinyl alcohol, stirring for 10-30 min, and granulating to obtain the network-trapping and loss-controlling medicine-fertilizer.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. The present invention provides a polyglutamic acid-empowered network-trapping and loss-controlling medicine-fertilizer. The abundant carboxyl functional groups on the polyglutamic acid molecular chain have excellent chelating ability, and can form stable complexes with nutrient ions. Its network structure and modified attapulgite form an interpenetrating network, enhancing the coating effect on nutrients and pesticides; the attapulgite modified by three steps has excellent organic compatibility and dispersibility, and its large specific surface area and the introduction of functional groups improve the loading capacity for nutrients; mesoporous silica is used as a pesticide carrier, and directional loading is achieved through the porous structure, improving stability; the ratio optimization of compound fertilizer and diammonium phosphate realizes the reasonable ratio of quick-acting and long-acting nutrients; the chelated trace elements and polyglutamic acid form a secondary chelation to improve biological effectiveness; polyvinyl alcohol is used as a film-forming agent and synergistically acts with polyglutamic acid to form a dense coating layer. Through these designs, the present invention realizes the integration of medicine and fertilizer, the efficient utilization of nutrients, and the synergistic release of nutrients and pesticides, and has good processing performance and product stability.

[0035] 2. The present invention provides a modified attapulgite. First, natural attapulgite is selected as the carrier. Its unique layer-chain structure, large specific surface area, and excellent adsorption performance provide a good foundation for nutrient controlled release. The silicon-oxygen bonds (Si-O-Si) introduced by KH570 on its surface provide a stable organic modification interface, enhancing the grafting stability of subsequent functional groups. Secondly, L-allylglycine grafted through free radical polymerization has a large number of negative charges on the carboxyl group of its molecular chain, which can form complexes with metal cations such as calcium, magnesium, and iron. This not only reduces the probability of the combination of anions and cations to produce insoluble substances, but also protects and activates phosphate ions, improving the biological availability of nutrients. At the same time, the carboxyl and amino groups on its molecular chain also have good water absorption and water retention properties, and can slowly release nutrients by activating the fixed nutrients in the later stage of crop growth, avoiding premature senescence and fertilizer deficiency. Finally, the phosphoryl group introduced through amidation reaction has strong coordination ability, forming a double coordination effect with the carboxyl group on the polymer chain, and can form stable complexes with metal ions in the soil. This complexation effect reduces the fixation of metal ions on phosphate on the one hand, improving the phosphorus utilization rate, and on the other hand, the formed reversible complex can temporarily fix nutrients to prevent loss, and can also be gradually released according to the needs of crops. At the same time, it can also improve the cation exchange capacity and aggregate structure of the soil, creating a good soil environment for crop growth. This progressive structural design enables the modified attapulgite to form a flocculent network structure in the soil, which can effectively encapsulate and control nutrient release without affecting the absorption of fertilizers by crops, significantly improving the fertilizer utilization efficiency, reducing the pollution of nutrients such as nitrogen and phosphorus to the soil and water bodies, and achieving the dual goals of increasing production and efficiency and environmental friendliness. Detailed implementation manners

[0036] In order to make the objectives, technical solutions and advantages of the present invention clearer, the following further elaborates on the present invention in conjunction with embodiments. Of course, the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0037] Unless otherwise specified, the chemical reagents and materials in the present invention are purchased through market channels or synthesized from raw materials purchased through market channels.

[0038] Attapulgite was purchased from Xingshou County Xingzhou Mineral Products Processing Factory;

[0039] Mesoporous silica was purchased from Nanjing Xianfeng Nano Materials Technology Co., Ltd., model: XFF29, with a specific surface area of 133.3 m 2 / g and a diameter of 70 nm - 90 nm;

[0040] The molecular weight of polyglutamic acid is 70 - 2 million Da and was purchased from Shandong Qianfeng Agricultural Technology Co., Ltd.;

[0041] The polyvinyl alcohol was purchased from Hai'an Petrochemical Factory in Jiangsu Province, with the grade of PVA-4000.

[0042] A preparation process of a net-capturing and loss-controlling drug-fertilizer empowered by synthetic biotechnology includes the following steps:

[0043] (1) Disperse 10 g of attapulgite into 80-150 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 7-9:3-1), ultrasonically treat for 15-30 min, adjust the pH of the dispersion to 4-5 with glacial acetic acid, add 0.3-1 g of KH570, raise the temperature to 60-75 °C, react at 400-600 r / min for 12-18 h, centrifuge, wash, and dry the product to obtain pretreated attapulgite;

[0044] (2) Disperse 10 g of pretreated attapulgite in 80-150 mL of deionized water, ultrasonically treat for 15-30 min, add 1-2 g of L-allylglycine, introduce nitrogen and add 0.02-0.1 g of ammonium persulfate, react at 55-70 °C and 300-400 r / min for 4-8 h, centrifuge the product, wash it 3-4 times with warm water at 70-90 °C, and dry to obtain grafted attapulgite;

[0045] (3) Disperse 10 g of grafted attapulgite in 80-150 mL of DMF, ultrasonically treat, add 0.6-1.5 g of 2-hydroxyphosphonoacetic acid, add 0.8-1.2 g of EDC and 0.4-0.6 g of NHS in the dark, stir and react at 20-30 °C and 200-300 r / min for 12-24 h, centrifuge the product, wash it successively with DMF, absolute ethanol, and deionized water, and dry to obtain modified attapulgite;

[0046] (4) Disperse 8-14 g of mesoporous silica in 10 mL of a 5-20 mg / L pesticide ethanol solution, oscillate in a constant temperature water bath oscillator at 25-40 °C for 18-24 h, filter the product with a sand core, wash it with deionized water, and dry it under vacuum to obtain the insecticide; the pesticide is one or more of chlorantraniliprole, clothianidin, dinotefuran, azoxystrobin, prothioconazole, and thifluzamide;

[0047] (5) Mix 60-80 parts of compound fertilizer, 10-20 parts of diammonium phosphate, 2-10 parts of trace elements (chelated ferrous, chelated copper, and chelated zinc are mixed in a weight ratio of 1:0.4-0.6:0.8-1.2), 2-8 parts of modified attapulgite, 1-4 parts of insecticide, and 0.5-3 parts of polyglutamic acid, stir for 10-20 min, grind through a 40-60 mesh sieve, add 1-5 parts of polyvinyl alcohol, stir for 10-30 min, and granulate to obtain the net-capturing and loss-controlling drug-fertilizer.

[0048] In the compound fertilizer, the content ratio of nitrogen fertilizer, phosphate fertilizer, and potassium fertilizer is 12-16:12-16:12-16; the content of the nitrogen fertilizer is calculated based on nitrogen element in the nitrogen fertilizer, the content of the phosphate fertilizer is calculated based on phosphorus pentoxide, and the content of the potassium fertilizer is calculated based on potassium oxide.

[0049] The following will further illustrate the present invention through specific embodiments.

[0050] Example 1

[0051] A preparation process of a network-capturing and loss-controlling medicine-fertilizer empowered by synthetic biotechnology includes the following steps:

[0052] (1) Disperse 10 g of attapulgite into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 1 g of KH570, raise the temperature to 75 °C, react at 500 r / min for 12 h, centrifuge, wash, and dry the product to obtain pretreated attapulgite;

[0053] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonically treat for 20 min, add 2 g of L-allylglycine, introduce nitrogen and add 0.1 g of ammonium persulfate, react at 70 °C and 350 r / min for 4 h, centrifuge the product, wash it 3 times with warm water at 80 °C, and dry to obtain grafted attapulgite;

[0054] (3) Disperse 10 g of grafted attapulgite in 100 mL of DMF, ultrasonically treat, add 1.5 g of 2-hydroxyphosphonoacetic acid, add 1.2 g of EDC and 0.6 g of NHS under light protection, stir and react at 30 °C and 250 r / min for 12 h, centrifuge the product, wash it successively with DMF, absolute ethanol, and deionized water, and dry to obtain modified attapulgite;

[0055] (4) Disperse 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillate in a 35 °C constant temperature water bath oscillator for 20 h, filter the product with a sand core, wash it with deionized water, and vacuum dry to obtain the insecticide;

[0056] (5) Mix 800 g of compound fertilizer (prepared by mixing urea, sodium phosphate, and potassium sulfate according to an effective content ratio of 16:12:15), 200 g of diammonium phosphate, 100 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate, and zinc sulfate according to a weight ratio of 1:0.5:1), 80 g of modified attapulgite, 40 g of insecticide, and 30 g of polyglutamic acid, stir for 15 min, grind through a 50-mesh sieve, add 50 g of polyvinyl alcohol, stir for 20 min, and granulate to obtain the network-capturing and loss-controlling medicine-fertilizer.

[0057] Example 2

[0058] A preparation process of a net-capturing and loss-controlling drug-fertilizer empowered by synthetic biotechnology, comprising the following steps:

[0059] (1) Disperse 10 g of attapulgite in 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 0.8 g of KH570, raise the temperature to 70 °C, react at 500 r / min for 14 h, centrifuge, wash, and dry the product to obtain pretreated attapulgite;

[0060] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonically treat for 20 min, add 1.6 g of L-allylglycine, introduce nitrogen and add 0.08 g of ammonium persulfate, react at 65 °C and 350 r / min for 5 h, centrifuge the product, wash 3 times with warm water at 80 °C, and dry to obtain grafted attapulgite;

[0061] (3) Disperse 10 g of grafted attapulgite in 100 mL of DMF, ultrasonically treat, add 1.2 g of 2-hydroxyphosphonoacetic acid, add 1.0 g of EDC and 0.5 g of NHS under light avoidance, stir and react at 28 °C and 250 r / min for 16 h, centrifuge the product, wash successively with DMF, absolute ethanol, and deionized water, and dry to obtain modified attapulgite;

[0062] (4) Disperse 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillate in a 35 °C constant temperature water bath oscillator for 20 h, filter the product with a sand core, wash with deionized water, and vacuum dry to obtain the insecticide;

[0063] (5) Mix 720 g of compound fertilizer (prepared by mixing urea, sodium phosphate, and potassium sulfate according to an effective content ratio of 16:12:15), 180 g of diammonium phosphate, 80 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate, and zinc sulfate according to a weight ratio of 1:0.5:1), 60 g of modified attapulgite, 30 g of insecticide, and 25 g of polyglutamic acid, stir for 15 min, grind through a 50-mesh sieve, add 40 g of polyvinyl alcohol, stir for 20 min, and granulate to obtain the net-capturing and loss-controlling drug-fertilizer.

[0064] Example 3

[0065] A preparation process of a net-capturing and loss-controlling drug-fertilizer empowered by synthetic biotechnology, comprising the following steps:

[0066] (1) Disperse 10 g of attapulgite clay into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), sonicate for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 0.5 g of KH570, raise the temperature to 65 °C, and react at 500 r / min for 16 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite clay;

[0067] (2) Disperse 10 g of pretreated attapulgite clay in 100 mL of deionized water, sonicate for 20 min, add 1.5 g of L-allylglycine, introduce nitrogen, and add 0.05 g of ammonium persulfate. React at 60 °C and 350 r / min for 7 h. Centrifuge the product, wash it three times with warm water at 80 °C, and dry it to obtain grafted attapulgite clay;

[0068] (3) Disperse 10 g of grafted attapulgite clay in 100 mL of DMF, sonicate, add 1 g of 2-hydroxyphosphonoacetic acid, add 1 g of EDC and 0.5 g of NHS under light protection, and stir and react at 24 °C and 250 r / min for 20 h. Centrifuge the product, wash it successively with DMF, absolute ethanol, and deionized water, and dry it to obtain modified attapulgite clay;

[0069] (4) Disperse 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillate in a 35 °C constant temperature water bath oscillator for 20 h, filter the product with a sintered filter, wash it with deionized water, and dry it under vacuum to obtain the pesticide;

[0070] (5) Mix 640 g of compound fertilizer (prepared by mixing urea, sodium phosphate, and potassium sulfate in an effective content ratio of 16:12:15), 140 g of diammonium phosphate, 50 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate, and zinc sulfate in a weight ratio of 1:0.5:1), 40 g of modified attapulgite clay, 20 g of pesticide, and 15 g of polyglutamic acid, stir for 15 min, grind through a 50-mesh sieve, add 30 g of polyvinyl alcohol, stir for 20 min, and granulate to obtain the net-capturing and loss-controlling medicine fertilizer.

[0071] Example 4

[0072] A preparation process of a net-capturing and loss-controlling medicine fertilizer empowered by synthetic biotechnology comprises the following steps:

[0073] (1) Disperse 10 g of attapulgite clay into 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), sonicate for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 0.3 g of KH570, raise the temperature to 60 °C, and react at 500 r / min for 18 h. Centrifuge, wash, and dry the product to obtain pretreated attapulgite clay;

[0074] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonically treat for 20 min, add 1 g of L-allylglycine, introduce nitrogen and add 0.02 g of ammonium persulfate, react at 55 °C and 350 r / min for 8 h, centrifuge the product, wash it 3 times with warm water at 80 °C, and dry it to obtain grafted attapulgite;

[0075] (3) Disperse 10 g of grafted attapulgite in 100 mL of DMF, ultrasonically treat it, add 0.6 g of 2-hydroxyphosphonoacetic acid, add 0.8 g of EDC and 0.4 g of NHS under light avoidance, stir and react at 20 °C and 250 r / min for 24 h, centrifuge the product, wash it successively with DMF, absolute ethanol, and deionized water, and dry it to obtain modified attapulgite;

[0076] (4) Disperse 10 g of mesoporous silica in 10 mL of a 10 mg / L dinotefuran ethanol solution, oscillate it in a constant temperature water bath oscillator at 35 °C for 20 h, filter the product with a sintered filter, wash it with deionized water, and dry it under vacuum to obtain the insecticide;

[0077] (5) Mix 600 g of compound fertilizer (prepared by mixing urea, sodium phosphate, and potassium sulfate in an effective content ratio of 16:12:15), 100 g of diammonium phosphate, 20 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate, and zinc sulfate in a weight ratio of 1:0.5:1), 20 g of modified attapulgite, 10 g of insecticide, and 5 g of polyglutamic acid, stir for 15 min, grind it through a 50-mesh sieve, add 10 g of polyvinyl alcohol, stir for 20 min, and granulate to obtain the net-capturing and loss-control medicine fertilizer.

[0078] Comparative Example 1

[0079] A preparation process of a loss-control medicine fertilizer includes the following steps:

[0080] (1) Disperse 10 g of attapulgite in a 100 mL methanol / water mixture (volume ratio of methanol to deionized water is 8:2), ultrasonically treat for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 1 g of KH570, raise the temperature to 75 °C and react at 500 r / min for 12 h, centrifuge, wash, and dry the product to obtain pretreated attapulgite;

[0081] (2) Disperse 10 g of pretreated attapulgite in 100 mL of deionized water, ultrasonically treat for 20 min, add 2 g of L-allylglycine, introduce nitrogen and add 0.1 g of ammonium persulfate, react at 70 °C and 350 r / min for 4 h, centrifuge the product, wash it 3 times with warm water at 80 °C, and dry it to obtain grafted attapulgite;

[0082] (3) Mix 800 g of compound fertilizer (prepared by mixing urea, sodium phosphate, and potassium sulfate in an effective content ratio of 16:12:15), 200 g of diammonium phosphate, 100 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate, and zinc sulfate in a weight ratio of 1:0.5:1), 80 g of grafted attapulgite, 40 g of insecticide, and 30 g of polyglutamic acid, stir for 15 min, grind through a 50-mesh sieve, add 50 g of polyvinyl alcohol, stir for 20 min, and granulate to obtain the controlled-release medicine fertilizer.

[0083] Comparative Example 2

[0084] A preparation process of a controlled-release medicine fertilizer includes the following steps:

[0085] (1) Disperse 10 g of attapulgite in 100 mL of a methanol / water mixture (the volume ratio of methanol to deionized water is 8:2), perform ultrasonic treatment for 20 min, adjust the pH of the dispersion to 4.5 with glacial acetic acid, add 1 g of KH570, raise the temperature to 75 °C, react at 500 r / min for 12 h, centrifuge, wash, and dry the product to obtain pretreated attapulgite.

[0086] (2) Mix 800 g of compound fertilizer (prepared by mixing urea, sodium phosphate, and potassium sulfate in an effective content ratio of 16:12:15), 200 g of diammonium phosphate, 100 g of trace elements (prepared by mixing ferrous sulfate, copper sulfate, and zinc sulfate in a weight ratio of 1:0.5:1), 80 g of pretreated attapulgite, 40 g of insecticide, and 30 g of polyglutamic acid, stir for 15 min, grind through a 50-mesh sieve, add 50 g of polyvinyl alcohol, stir for 20 min, and granulate to obtain the controlled-release medicine fertilizer.

[0087] Perform a water absorption ratio test on the modified attapulgite prepared in Examples 1 to 4, the grafted attapulgite prepared in Comparative Example 1, and the pretreated attapulgite prepared in Comparative Example 2. Weigh the sample W0, put it into a 400-mesh nylon bag, place it in 1000 mL of deionized water, fully absorb water and expand. After taking out the sample after the water absorption and expansion reach equilibrium, drain it, and weigh the mass W1 of the sample saturated with water. Calculate the water absorption ratio S of the sample according to the formula:

[0088] S = (W1 - W0) / W0 × 100%;

[0089] In the same way, use physiological saline instead of deionized water to measure the saline absorption ratio of the sample. The specific data are shown in Table 1.

[0090] Table 1 Results of the water absorption ratio of the samples

[0091]

[0092] The controlled-release fertilizers prepared in Examples 1-4 and Comparative Examples 1-2 were subjected to performance tests. According to GB / T 23348-2009 "Slow-Release Fertilizers", the 24-hour release rate, 7-day cumulative release rate, 28-day cumulative release rate of the fertilizer, and the time required for the fertilizer to release 80% were detected; the water retention in the soil was measured by the soil column method to determine the influence of the fertilizer on the infiltration amount at the same infiltration distance, and the infiltration amount was based on the height (cm) of the water level drop in the Mariotte bottle; the specific test results are shown in Table 2.

[0093] Table 2 Performance Test Results of Controlled-Release Fertilizers

[0094]

[0095] The controlled-release fertilizers prepared in Examples 1-4 and Comparative Examples 1-2 were used in the plot rice experiment. Each plot was 10 m long and 4 m wide, with a protective row set around. The fertilizer application rate was 40 kg / mu as basal application. The growth and yield of rice are shown in Table 3.

[0096] Table 3 Influence of Controlled-Release Fertilizers on the Growth and Yield of Rice

[0097]

[0098] An experiment on the primary insecticidal efficiency and secondary insecticidal efficiency of the insecticides prepared in the examples of the present invention was carried out. The specific experimental steps were as follows: Collect pollution-free agricultural surface soil (20-40 cm), air-dry it naturally for several days, remove impurities and then grind it through a 60-mesh sieve to obtain the test soil. Add the insecticides prepared in Examples 1-4 and pure dinotefuran pesticide to the test soil at 0.2 g / kg to obtain the experimental soil and the control soil. Select cabbage caterpillars with the same instar and randomly place them in the experimental soil and the control soil. After 48 h, count the number of surviving cabbage caterpillars in the soil and calculate the insecticidal rate to obtain the primary insecticidal rate; Wash the soil matrix containing pure pesticide and insecticide in the primary insecticidal stage with deionized water, dry it and then put cabbage caterpillars again. After 72 h, calculate the secondary insecticidal rate. The specific data are shown in Table 4.

[0099] Insecticidal rate (%) = (N1 - N0) / N1 × 100%;

[0100] N1 is the number of cabbage caterpillars placed in the soil before the test; N0 is the number of surviving cabbage caterpillars in the soil after the test.

[0101] Table 4 Insecticidal Rate Results of Insecticides

[0102]

[0103] The data in Table 4 show that the insecticides of the present invention can extend the effective period of pesticides and improve the utilization rate of pesticides.

[0104] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes should be covered within the protection scope of the present invention.

Claims

1. A formulation of a net-capturing and loss-preventing drug-fertilizer empowered by synthetic biotechnology, characterized in that, It is made of the following components by weight parts: 60 - 80 parts of compound fertilizer, 10 - 20 parts of diammonium phosphate, 2 - 10 parts of trace elements, 2 - 8 parts of modified attapulgite, 1 - 4 parts of insecticide, 0.5 - 3 parts of polyglutamic acid, 1 - 5 parts of polyvinyl alcohol; The preparation method of the said modified attapulgite includes the following steps: (1) Disperse attapulgite into a methanol / water mixed solution, conduct ultrasonic treatment, adjust the pH of the dispersion, add KH570, raise the temperature for reaction, centrifuge, wash, and dry the product to obtain pretreated attapulgite; (2) Disperse the pretreated attapulgite in deionized water, conduct ultrasonic treatment, add L - allylglycine, introduce nitrogen and add ammonium persulfate, stir for reaction, centrifuge, wash, and dry the product to obtain grafted attapulgite; (3) Disperse the grafted attapulgite in DMF, conduct ultrasonic treatment, add 2 - hydroxyphosphonoacetic acid, add EDC and NHS under light avoidance, stir for reaction, centrifuge, wash, and dry the product to obtain modified attapulgite.

2. The formulation of the net-capturing and loss-controlling medicine fertilizer according to claim 1, wherein, In step (1), the volume ratio of methanol to deionized water in the methanol / water mixed solution is 7 - 9:3 - 1; the dosage ratio of attapulgite, methanol / water mixed solution, and KH570 is 10g:80 - 150mL:0.3 - 1g.

3. The formulation of the net-capturing and loss-controlling medicine fertilizer according to claim 1, wherein, In step (1), conduct ultrasonic treatment for 15 - 30min, adjust the pH of the dispersion to 4 - 5 with glacial acetic acid; the temperature - raising reaction conditions are to raise the temperature to 60 - 75°C and react at 400 - 600r / min for 12 - 18h.

4. The formulation of the net-capturing and loss-controlling medicine fertilizer according to claim 1, wherein, In step (2), the dosage ratio of pretreated attapulgite, deionized water, L - allylglycine, and ammonium persulfate is 10g:80 - 150mL:1 - 2g:0.02 - 0.1g.

5. The formulation of the net-capturing and loss-controlling medicine fertilizer according to claim 1, characterized in that In step (2), conduct ultrasonic treatment for 15 - 30min; the stirring reaction conditions are 55 - 70°C and 300 - 400r / min for 4 - 8h; wash with 70 - 90°C warm water for 3 - 4 times.

6. The formulation of the net-capturing and loss-controlling medicine fertilizer according to claim 1, wherein In step (3), the dosage ratio of grafted attapulgite, DMF, 2 - hydroxyphosphonoacetic acid, EDC, and NHS is 10g:80 - 150mL:0.6 - 1.5g:0.8 - 1.2g:0.4 - 0.6g; the stirring reaction conditions are 20 - 30°C and 200 - 300r / min for 12 - 24h; wash successively with DMF, absolute ethanol, and deionized water.

7. The formulation of the net-capturing and loss-controlling medicine fertilizer according to claim 1, wherein, The preparation method of the said insecticide includes the following steps: Disperse mesoporous silica in a 5 - 20mg / L pesticide ethanol solution, oscillate in a 25 - 40°C constant - temperature water - bath oscillator for 18 - 24h, filter the product with a sand - core filter, wash with deionized water, and vacuum - dry to obtain the said insecticide; the pesticide is one or more of chlorantraniliprole, clothianidin, dinotefuran, azoxystrobin, prothioconazole, thifluzamide; the dosage ratio of mesoporous silica to the pesticide ethanol solution is 8 - 14g:10mL.

8. The formulation of the net-capturing and loss-preventing medicated fertilizer according to claim 1, wherein, In the compound fertilizer, the content ratio of nitrogen fertilizer, phosphate fertilizer and potassium fertilizer is 12-16:12-16:12-16; the content of the nitrogen fertilizer is calculated based on nitrogen element in the nitrogen fertilizer, the content of the phosphate fertilizer is calculated based on phosphorus pentoxide, and the content of the potassium fertilizer is calculated based on potassium oxide; the trace elements are made by mixing chelated ferrous, chelated copper and chelated zinc according to the weight ratio of 1:0.4-0.6:0.8-1.

2.

9. A preparation process of a drug-fertilizer formula based on synthetic biotechnology empowered network capture and loss control as described in any one of claims 1 to 8, characterized in that, It includes the following steps: mixing the compound fertilizer, diammonium phosphate, trace elements, modified attapulgite, insecticide and polyglutamic acid, stirring for 10-20 min, grinding and passing through a 40-60 mesh sieve, adding polyvinyl alcohol, stirring for 10-30 min, and granulating to obtain the net-capturing and loss-controlling medicine fertilizer.

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