Foliar fertilizer with high nitrogen fertilizer utilization rate and preparation method thereof

Abstract

The invention belongs to the field of fertilizers, and particularly relates to a foliar fertilizer with a high nitrogen fertilizer utilization rate and a preparation method thereof.The preparation method comprises the steps that glycidyl methacrylate is adopted for preparing a polymer, then polyarginine is adopted for modification, and a composite matrix is obtained; taking part of the composite matrix to be combined with 3, 4, 9, 10-perylenetetracarboxylic dianhydride to obtain a photosensitive matrix; the photosensitive matrix is used as a ligand, and metal ions are combined with the ligand to form a complex; and compounding the complex with a composite matrix and a soluble compound of nutrient elements to obtain the foliar fertilizer. The foliar fertilizer with the high nitrogen fertilizer utilization rate can promote photosynthesis of plants, promote root growth and improve nitrogen absorption and utilization of the plants.

Description

Technical Field

[0001] The invention belongs to the field of fertilizers, and in particular relates to a foliar fertilizer with high nitrogen fertilizer utilization rate and a preparation method thereof. Background Art

[0002] The rice field ecosystem is not only the basis of food production, but also an important carrier of biodiversity conservation. It occupies an important position in the global biogeochemical cycle and agricultural carbon sink. Diversified planting patterns can significantly improve the stability and productivity of the ecosystem. Higher species diversity not only helps to improve rice field productivity, but also enhances the system's adaptability to environmental changes. When biological activities and organic matter cycles in rice field ecosystems are insufficient to provide the nutrients required for crop growth, appropriate fertilizer application becomes a necessary measure. Fertilization is a key means to quickly and effectively supplement crop nutrients, promote rice plant growth, and increase grain yield. However, different fertilization methods have different effects on crop growth and soil carbon, nitrogen, and phosphorus cycles. Traditional single fertilization methods may lead to inefficient nutrient utilization and even environmental pollution.

[0003] Traditional fertilization methods mainly apply carbon, nitrogen, phosphorus and potassium to the roots, and leaves are the most important nutrient absorption organs besides the roots, and they also play a key role in nutrient absorption and utilization. Foliar fertilization can effectively improve the efficiency of nutrient absorption by spraying the nutrients required by plants directly onto the leaf surface. Compared with root fertilization, it has a faster absorption speed and higher utilization rate. The effect of foliar fertilizer application depends on the absorption and transport capacity of crop leaves for nutrients. Whether the nutrients can smoothly enter the mesophyll cells is the key factor that determines the efficiency of nutrient absorption and utilization by the leaves. At the same time, different functional types of foliar fertilizers will also have a significant impact on the growth characteristics of crops and the characteristics of plant communities. While optimizing nutrient supply, they can also regulate the physiological processes of crops and improve overall production efficiency.

[0004] The contribution rate of nitrogen fertilizer application to grain production increase is as high as 30% to 50%, which is the most effective way to increase grain production. The current demand for nitrogen fertilizer in production is very high, but the utilization rate of nitrogen fertilizer is much lower than that in developed countries in Europe and the United States. To improve this situation, precise regulation of the growth of the aboveground part of crops, such as foliar spraying of plant growth regulators, biostimulants, organic acids, sugars and nutrients, is an important way to promote the absorption of nutrients by crop roots, reduce fertilizer usage, and improve the utilization rate of nitrogen fertilizer. However, existing foliar fertilizer products generally have the disadvantages of low technical content, poor quality, and unqualified nutrient content. Therefore, how to improve the technical means of foliar fertilizer preparation and product functionality, scientifically improve the utilization rate of nitrogen fertilizer in rice field ecosystems, improve rice field nutrient circulation and promote the sustainable development of biodiversity agriculture has become a very important research topic at this stage. Summary of the invention

[0005] The present invention mainly provides a foliar fertilizer with high nitrogen utilization rate, strong affinity with plants and easy absorption. The technical scheme is as follows:

[0006] A method for preparing a foliar fertilizer with high nitrogen fertilizer utilization rate comprises the following steps: preparing a polymer by using glycidyl methacrylate, and then modifying it by using polyarginine to obtain a composite matrix; combining a part of the composite matrix with 3,4,9,10-perylenetetracarboxylic dianhydride to obtain a photosensitive matrix; using the photosensitive matrix as a ligand, combining metal ions with the ligand to form a complex; and compounding the complex with the composite matrix and a soluble compound of nutrient elements to obtain a foliar fertilizer.

[0007] Furthermore, the nutrient elements include phosphorus, potassium and calcium, and may or may not contain one or more of magnesium, iron, zinc, boron, aluminum, manganese, copper or sulfur; and the degree of polymerization of the polyarginine is 2 to 10.

[0008] Furthermore, 1 to 5 parts of the complex are compounded with 120 to 200 parts of the composite matrix, 60 to 100 parts of nutrient elements and water to obtain foliar fertilizer, based on parts by mass.

[0009] Further, the following steps are included:

[0010] a. Under nitrogen atmosphere, vinyl acetate and glycidyl methacrylate were dissolved in N,N-dimethylformamide, azobisisobutyronitrile was added, and the reaction was carried out at 60-80°C for 6-8h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, filtered and dried to obtain a polymer;

[0011] b. Then, the polymer and polyarginine are added to N,N-dimethylformamide, and then 4-dimethylaminopyridine and dicyclohexylcarbodiimide are added, and the reaction is carried out at room temperature for 10 to 16 hours. After the reaction is terminated, the composite matrix is ​​precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0012] c. Mix a portion of the composite matrix with 3,4,9,10-perylenetetracarboxylic dianhydride and imidazole, react at 160-170°C for 18-24 hours under a nitrogen atmosphere, cool to room temperature, add an equal volume of ethanol and concentrated hydrochloric acid, react for 8-12 hours, collect the precipitate, elute and purify to obtain a photosensitive matrix;

[0013] d. The photosensitive matrix and the soluble zinc salt are dispersed in an aqueous solution of ethanol, and mixed and reacted at 50-70°C until the ethanol evaporates. After cooling to room temperature, stirring is continued for 20-40 minutes, and the precipitate is collected, washed thoroughly, and dried to obtain a complex.

[0014] e. Compounding the foliar fertilizer base, the composite base and the nutrient elements to obtain the foliar fertilizer.

[0015] Furthermore, the mass ratio of vinyl acetate to glycidyl methacrylate in step a is 2.5-3.5:1; the mass ratio of vinyl acetate to azobisisobutyronitrile in step a is 80-100:1.

[0016] Furthermore, the mass ratio of the polymer to polyarginine in step b is 6-8:1; the mass ratio of polyarginine to 4-dimethylaminopyridine in step b is 10-13:1; the mass ratio of 4-dimethylaminopyridine to dicyclohexylcarbodiimide in step b is 1:2-3.

[0017] Furthermore, in step c, the mass ratio of the composite matrix to 3,4,9,10-perylenetetracarboxylic acid dianhydride is 2-3:1; and the mass ratio of 3,4,9,10-perylenetetracarboxylic acid dianhydride to imidazole in step c is 1:8-10.

[0018] Furthermore, the mass ratio of the soluble zinc salt to the photosensitive matrix in step d is 0.8 to 2:1.

[0019] Furthermore, the soluble zinc salt in step d includes one or more of zinc chloride, zinc nitrate and zinc acetate.

[0020] A foliar fertilizer with high nitrogen fertilizer utilization rate prepared by the above preparation method.

[0021] By adopting the above scheme, the method of the present invention has the following advantages:

[0022] 1. The present invention combines polymers with amino acids, so that the amino acids are evenly dispersed in foliar fertilizers, and the amino acids are bound to reduce the activity of the amino acids, thereby preventing them from being destroyed in subsequent treatments. After application, the amino acids are reduced from being consumed by microorganisms in the air, thereby promoting the absorption and utilization of nitrogen by plants.

[0023] 2. The present invention combines polyarginine with zinc ions to form an organic complex, which can greatly improve the solubility of zinc ions, making zinc ions easier to be absorbed by plants and avoiding the loss of elements. The force formed by the complex and the wrapping effect of the ligand will form a certain slow-release effect, avoiding the damage to the plant caused by a transient increase in zinc ions. Zinc ions form a synergistic effect with nitrogen in amino acids, promoting nitrogen absorption and further optimizing the quality of foliar fertilizers.

[0024] 3. The present invention combines photosensitizers with substrates to artificially capture and convert solar energy, thereby solving the problem of natural conditions limiting the efficiency of photosynthesis, increasing the chlorophyll content of plants, enhancing photosynthesis, and improving the light absorption efficiency of plants. It can also optimize the morphology of plant roots, enhance root activity and root absorption area, thereby enhancing the absorption and utilization of nitrogen nutrients by rice and improving the utilization rate of nitrogen in basal fertilizers.

[0025] 4. The composite matrix of the present invention has both hydrophobic segments and hydrophilic segments, and can be used as an active agent on the leaf surface to improve the wettability of foliar fertilizer on the leaf surface, and can improve the dispersibility between raw materials in aqueous solution and improve the fluidity of foliar fertilizer.

[0026] 5. The foliar fertilizer of the present invention is in liquid form, and the composite matrix formed by the polymer and the amino acid has a strong adhesion ability to the leaves and good affinity with the leaf surface. The fertilizer nutrients are more easily absorbed by the plants, solving the problem that solid compound fertilizers are not easily absorbed and have poor effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A comparison diagram of the effects of foliar fertilizer on nitrogen accumulation in rice in various embodiments;

[0028] Figure 2 A comparison diagram of the effects of foliar fertilizer on agronomic utilization rate of nitrogen in rice in various embodiments;

[0029] Figure 3 A comparison diagram of the effects of foliar fertilizers of various embodiments on the physiological utilization rate of nitrogen in rice;

[0030] Figure 4 A comparison diagram of the effects of foliar fertilizers on nitrogen absorption and utilization rate of rice in various embodiments; DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Example 1: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0033] (2) Then 1.2 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0034] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0035] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0036] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0037] Example 2: (1) Under a nitrogen atmosphere, 29 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0038] (2) Then 1.2 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0039] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0040] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0041] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0042] Example 3: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0043] (2) Then 1.5 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0044] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0045] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0046] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0047] Example 4: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0048] (2) Then, 1.2 g of the polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 10 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0049] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0050] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0051] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0052] Example 5: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0053] (2) Then 1.2 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0054] (3) 1.5 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0055] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0056] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0057] Example 6: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0058] (2) Then 1.2 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0059] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0060] (4) Dispersing 1 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0061] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0062] Example 7: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0063] (2) Then 1.2 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0064] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0065] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 50° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0066] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0067] Example 8: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0068] (2) Then 1.2 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0069] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0070] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 20 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0071] (5) 2.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 377.5 g of water to prepare a foliar fertilizer.

[0072] Example 9: (1) Under a nitrogen atmosphere, 21 g of vinyl acetate and 8.5 g of glycidyl methacrylate were dissolved in 250 mL of N,N-dimethylformamide, and 0.3 g of azobisisobutyronitrile was added. The mixture was reacted at 70° C. for 7 h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, and filtered and dried to obtain a polymer.

[0073] (2) Then 1.2 g of polymer and 0.2 g of polyarginine were added to 20 mL of N,N-dimethylformamide, and then 0.02 g of 4-dimethylaminopyridine and 0.04 g of dicyclohexylcarbodiimide were added, and the reaction was carried out at room temperature for 16 h. After the reaction was terminated, the composite matrix was precipitated with n-hexane, filtered and dried to obtain a composite matrix;

[0074] (3) 1 g of the composite matrix was mixed with 0.5 g of 3,4,9,10-perylenetetracarboxylic dianhydride and 4 g of imidazole, and reacted at 160° C. for 20 h under a nitrogen atmosphere. After cooling to room temperature, 35 mL of ethanol and 35 mL of concentrated hydrochloric acid were added, and the reaction was continued for 10 h. After collecting the precipitate, it was eluted and purified to obtain a photosensitive matrix;

[0075] (4) Dispersing 0.4 g of the photosensitive matrix and 0.5 g of zinc chloride in 75 mL of a 50% ethanol aqueous solution, mixing and reacting at 70° C. until the ethanol evaporates, and stirring for 40 min after cooling to room temperature, collecting the precipitate, washing it thoroughly, and drying it to obtain a complex;

[0076] (5) 0.5 g of the complex was mixed with 80 g of the composite matrix, 20 g of phosphorus pentoxide, 20 g of potassium oxide and 379.5 g of water to prepare a foliar fertilizer.

[0077] Example sample performance test:

[0078] Cultivate rice seedlings of the same size and growth in a seedling tray, transplant them to the field when they have 3 leaves and 1 heart, and plant them at a conventional density. Apply 240kg of pure nitrogen, 12kg of pure phosphorus, and 72kg of pure potassium per hectare throughout the growth period. Foliar fertilizers are sprayed at the heading stage and the filling stage of rice, respectively, and 400L of diluted solution is sprayed per hectare each time. Clear water is used as a control example, and a blank control without fertilization is set. Each embodiment is repeated 10 times and the average value is taken. After the harvest at maturity, the grain yield, plant nitrogen accumulation, nitrogen agronomic utilization rate, nitrogen physiological utilization rate, and nitrogen absorption utilization rate of rice are determined, and each sample is measured 3 times and the average value is taken. An isotope mass spectrometer (Elementar) was used to measure the nitrogen content of the collected plants and soil, and the agronomic nitrogen utilization rate was calculated by the formula (grain yield of the fertilized treatment-grain yield of the unfertilized treatment) / nitrogen application amount; the physiological nitrogen utilization rate was calculated by the formula (grain yield of the fertilized treatment-grain yield of the unfertilized treatment) / (total nitrogen accumulation of plants treated with fertilizers-total nitrogen accumulation of plants treated with unfertilizers); (total nitrogen accumulation of plants treated with fertilizers-total nitrogen accumulation of plants treated with unfertilizers) / nitrogen application amount × 100%.

[0079] The results are as follows:

[0080]

[0081]

[0082] Compared with Example 1, Example 2 has a higher content of vinyl acetate, and the content of glycidyl methacrylate is naturally reduced. In the final complex, polyarginine and 3,4,9,10-perylenetetracarboxylic dianhydride are naturally less, and the growth of the treated rice plants is not as good as that of Example 1. At the same time, the rice grain yield, nitrogen absorption and utilization rate, and agronomic utilization rate of Example 9 in which the content of the complex is significantly reduced are not as good as those of Example 1. The growth of the rice plants in Example 6, which adds more photosensitive substrates, is significantly better than that of Example 1, especially the grain yield is significantly increased, and the nitrogen fertilizer utilization rate is also increased, indicating that the composite 3,4,9,10-perylenetetracarboxylic dianhydride can increase the photosynthesis of the plant and the growth of the root system, thereby improving the utilization of nitrogen by the plant. The foliar fertilizer prepared by the method of the present invention is beneficial to the growth of the plant and promotes the absorption and utilization of nitrogen by the plant.

[0083] In the process of compounding the polymer and polyarginine in Example 4, the reaction time was shorter, and the growth of the rice plants was not as good as in Example 1, which may be because the combination of the two was not yet complete. When preparing the complex, the rice plants in Example 7 with a lower reaction temperature grew better and the nitrogen fertilizer utilization rate was significantly increased, which may be because the ethanol evaporated more slowly at a lower temperature, the combination was more complete and stable, and more zinc ions were released evenly, which improved the nitrogen absorption and utilization of the plants. The plant growth of Example 8 with a shorter stirring time after room temperature did not change significantly, which may be because the reaction was relatively sufficient.

[0084] For those skilled in the art, various other corresponding changes and deformations can be made according to the technical solutions and concepts described above, and all of these changes and deformations should fall within the protection scope of the claims of the present invention.

Claims

1. A method for preparing foliar fertilizer with high nitrogen fertilizer utilization rate, characterized in that: The following steps are involved: The polymer is prepared by using glycidyl methacrylate, and then modified by using polyarginine to obtain a composite matrix; a part of the composite matrix is ​​combined with 3,4,9,10-perylenetetracarboxylic dianhydride to obtain a photosensitive matrix; the photosensitive matrix is ​​used as a ligand, and the metal ions are combined with the ligand to form a complex; the complex is compounded with the composite matrix and a soluble compound of nutrient elements to obtain a foliar fertilizer.

2. The method for preparing foliar fertilizer with high nitrogen fertilizer utilization rate according to claim 1, characterized in that, The nutrient elements include phosphorus, potassium and calcium, and may or may not contain one or more of magnesium, iron, zinc, boron, aluminum, manganese, copper or sulfur; the polymerization degree of the polyarginine is 2-10.

3. The preparation method of foliar fertilizer with high nitrogen fertilizer utilization rate according to claim 1, characterized in that, By weight, 1 to 5 parts of the complex are compounded with 120 to 200 parts of a composite matrix, 60 to 100 parts of nutrient elements and water to make 1000 parts to obtain a foliar fertilizer.

4. The method for preparing a foliar fertilizer with high nitrogen fertilizer utilization rate according to any one of claims 1 to 3, characterized in that: The following steps are involved: a. Under nitrogen atmosphere, vinyl acetate and glycidyl methacrylate were dissolved in N,N-dimethylformamide, azobisisobutyronitrile was added, and the reaction was carried out at 60-80°C for 6-8h, then the reaction was terminated, cooled to room temperature, precipitated with n-hexane, filtered and dried to obtain a polymer; b. Then, the polymer and polyarginine are added to N,N-dimethylformamide, and then 4-dimethylaminopyridine and dicyclohexylcarbodiimide are added, and the reaction is carried out at room temperature for 10 to 16 hours. After the reaction is terminated, the composite matrix is ​​precipitated with n-hexane, filtered and dried to obtain a composite matrix; c. Mix a portion of the composite matrix with 3,4,9,10-perylenetetracarboxylic dianhydride and imidazole, react at 160-170°C for 18-24 hours under a nitrogen atmosphere, cool to room temperature, add an equal volume of ethanol and concentrated hydrochloric acid, react for 8-12 hours, collect the precipitate, elute and purify to obtain a photosensitive matrix; d. The photosensitive matrix and the soluble zinc salt are dispersed in an aqueous solution of ethanol, and mixed and reacted at 50-70°C until the ethanol evaporates. After cooling to room temperature, stirring is continued for 20-40 minutes, and the precipitate is collected, washed thoroughly, and dried to obtain a complex. e. Compounding the foliar fertilizer base, the composite base and the nutrient elements to obtain the foliar fertilizer.

5. The method for preparing foliar fertilizer with high nitrogen fertilizer utilization rate according to claim 4, characterized in that, The mass ratio of vinyl acetate to glycidyl methacrylate in step a is 2.5-3.5:1; the mass ratio of vinyl acetate to azobisisobutyronitrile in step a is 80-100:

1.

6. The method for preparing foliar fertilizer with high nitrogen fertilizer utilization rate according to claim 4, characterized in that, The mass ratio of the polymer to polyarginine in step b is 6-8:1; the mass ratio of polyarginine to 4-dimethylaminopyridine in step b is 10-13:1; the mass ratio of 4-dimethylaminopyridine to dicyclohexylcarbodiimide in step b is 1:2-3.

7. The method for preparing foliar fertilizer with high nitrogen fertilizer utilization rate according to claim 4, characterized in that, In step c, the mass ratio of a portion of the composite matrix to 3,4,9,10-perylenetetracarboxylic acid dianhydride is 2-3:1; and the mass ratio of 3,4,9,10-perylenetetracarboxylic acid dianhydride to imidazole is 1:8-10.

8. The method for preparing foliar fertilizer with high nitrogen fertilizer utilization rate according to claim 4, characterized in that, The mass ratio of the soluble zinc salt to the photosensitive matrix in step d is 0.8 to 2:

1.

9. The method for preparing foliar fertilizer with high nitrogen fertilizer utilization rate according to claim 4, characterized in that, The soluble zinc salt in step d includes one or more of zinc chloride, zinc nitrate and zinc acetate.

10. A foliar fertilizer with high nitrogen fertilizer utilization rate prepared by the preparation method according to any one of claims 1 to 3.

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