CN115594551B - Accurate controlled release membrane material filled with thermosensitive polymer nanoparticles and application thereof - Google Patents
Accurate controlled release membrane material filled with thermosensitive polymer nanoparticles and application thereof Download PDFInfo
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- CN115594551B CN115594551B CN202211194688.2A CN202211194688A CN115594551B CN 115594551 B CN115594551 B CN 115594551B CN 202211194688 A CN202211194688 A CN 202211194688A CN 115594551 B CN115594551 B CN 115594551B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
- C05G5/37—Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
Abstract
The application relates to the field of novel agricultural materials, and particularly provides an accurate controlled release membrane material filled with thermosensitive polymer nanoparticles and application thereof, wherein the thermosensitive polymer nanoparticles are formed by polymerizing thermosensitive polymer monomers under the action of an initiator and a cross-linking agent, and then the thermosensitive polymer nanoparticles are added into a coated fertilizer membrane material to prepare the thermosensitive controlled release membrane material capable of realizing intelligent controlled release, when in use, the release rate of the coated fertilizer can be accurately controlled through response change of temperature, the thermosensitive intelligent membrane material is ensured to release moisture and nutrients relatively fast at a proper temperature (20-30 ℃) of crops, and release moisture and nutrients relatively slowly at an excessively low temperature or an excessively high temperature, so that the fertilizer utilization rate can be remarkably improved by perfectly combining the nutrient release rule of the coated fertilizer with the fertilizer requirement rule of crop growth through regulating and controlling the temperature, and the aim of thermosensitive intelligent controlled release of the coated fertilizer can be achieved.
Description
Technical Field
The application relates to the field of novel agricultural materials, and particularly provides an accurate controlled release membrane material filled with thermosensitive polymer nanoparticles and application thereof.
Background
The coated fertilizer can greatly improve the nutrient utilization rate, has positive promotion effect on the yield increase and stable yield of grains, and has important effect and significance in agricultural production. According to statistics, the annual output of the coated fertilizer in China exceeds 2100 ten thousand tons, the agricultural application amount can reach 315 ten thousand tons, and the cumulative popularization area is about 5.25 hundred million mu. Although the coated fertilizer can greatly improve the grain yield, the commercial coated fertilizer cannot respond to the temperature, and cannot realize the intelligent controlled release function of the response of the nutrient release along with the change of the temperature, so that the nutrient utilization rate of the coated fertilizer still needs to be improved.
The release principle of the commercial coated fertilizer is as follows: the water permeates into the membrane shell of the coated fertilizer, so that the fertilizer is dissolved to form high-concentration urea solution, high pressure difference is formed inside and outside the membrane shell, and further water is absorbed from the external environment by the water, so that the membrane shell is expanded and broken, a plurality of micro pores are formed in the membrane shell, and the nutrients are continuously released to the external environment through the pores. Therefore, once the film shell of the coated fertilizer is broken, no matter whether crops need fertilizers or not, nutrients can be released continuously, and intelligent controlled release of the nutrients cannot be realized, which is a bottleneck problem for restricting the development of the coated fertilizer industry. Therefore, the problems are solved, the problems become hot spot and difficult problems of domestic and foreign research, and the method has important significance for large-scale popularization and use of the coated fertilizer.
Temperature sensitive polymers are a class of smart polymers that can change their water permeability in response to temperature. The temperature-sensitive polymer nano particles are added into the film shell of the coated fertilizer, so that the film shell has a temperature-sensitive function, the water permeability and nutrient controlled release characteristics of the aperture of the film shell can be regulated and controlled along with temperature transformation, and the film shell is an effective way for realizing intelligent controlled release of the coated fertilizer. The temperature-sensitive polymer is applied to the aspects of sustained and controlled release medicines (201110147125.3, 201310477059.5, 201310178489.7, 201910289444.4), sustained and controlled release polymers (2016610361343. X, 201710402044.0, 201410047054.3), sustained and controlled release pesticides (201711170658.7, 201910195232. X), temperature-sensitive antifreeze materials (201510168812.1), temperature-sensitive slow release fertilizers (201410314972.8) and the like. The technology is mainly characterized in that substances such as medicines, pesticides and fertilizer powder are blended with a thermosensitive polymer, and medicines and pesticides are buried in the thermosensitive polymer through a series of processes, so that thermosensitive micro-nano-scale microspheres, polymers and the like filled with the medicines and pesticides are obtained. However, the above-mentioned patent products have the following disadvantages: the dosage of the film shell is extremely large and can reach 70 percent, the production cost is extremely high, and the large-scale popularization and application of the micro-nano microcapsule slow release product are not facilitated.
The patent 201510975327.5 prepares the microbial fertilizer synergist for controlled release of the thermosensitive polymer by using a core layer (10-20 parts by weight of biochar and 50-60 parts by weight of nutritional ingredients) and a film layer (15-30 parts by weight of porous thermosensitive polymer and 5-10 parts by weight of water-retaining agent). Patent No. 201610420250.X uses fertilizer core (water-soluble granular fertilizer) and temperature-sensitive film layer (polyphenyl ether 6-10%, polypropylene oxide 40-55%, cross-linking agent 0.2-5%, and the rest is trilaurin) to prepare temperature-sensitive coating material and temperature-sensitive coated fertilizer. Although the above-mentioned patent products are prepared using temperature-sensitive polymers, the following disadvantages exist: (1) 100% of the film material is all temperature-sensitive polymer, the proportion of the temperature-sensitive film material to the total mass of the fertilizer can reach 50%, and the price of the polymer is too high, so that patent products cannot be industrially produced and applied; (2) The sensitivity of the temperature-sensitive polymer adopted in the method to temperature is too low to achieve the intelligent effect. For example: the fertilizer prepared in patent 201610420250.X is normally released when the temperature is low in winter, and is rarely released or released slowly in other seasons with relatively high temperature. That is, the fertilizer releases nutrients only when the temperature is low (< 5 ℃) and releases nutrients slowly when the temperature is high (> 5 ℃), so that the purpose of intelligently regulating and controlling the release of nutrients cannot be achieved. Because of many factors influencing the nutrient release of the coated fertilizer, the effect of increasing the temperature and reducing the nutrient release rate cannot be achieved under normal conditions; (3) The nutrient controlled release period of the product is extremely short and less than 10 days, and the fertilizer requirement characteristic of crops in a longer growth period in the agricultural field can not be met.
Therefore, whether the thermosensitive polymer nano-particles can be better applied to the controlled release membrane material becomes one of the problems to be solved urgently by the technicians in the field.
Disclosure of Invention
Aiming at a plurality of defects existing in the prior art, the application provides an accurate controlled release membrane material filled with thermosensitive polymer nanoparticles and application thereof, wherein the thermosensitive polymer nanoparticles are formed by polymerizing thermosensitive polymer monomers under the action of an initiator and a cross-linking agent, and then the thermosensitive polymer nanoparticles are added into a coated fertilizer membrane material to prepare the temperature-sensitive controlled release membrane material capable of intelligently controlling release, when in use, the release rate of the coated fertilizer can be accurately controlled through response change of temperature, the thermosensitive intelligent membrane material is ensured to release moisture and nutrient relatively fast at a proper temperature (20-30 ℃) of crops, and release moisture and nutrient relatively slow at a too low temperature or a too high temperature, so that the release rule of the coated fertilizer is perfectly combined with the fertilizer-requiring rule of crop growth through regulating the temperature, the fertilizer utilization rate can be remarkably improved, and the purpose of temperature-sensitive intelligent controlled release of the coated fertilizer is achieved.
Compared with the prior art, the application has the following ideas:
(1) The raw materials are as follows: the temperature-sensitive polymer prepared by the method is more intelligent, can realize complete matching response with the temperature range required by crop growth, and has obviously changed water permeability and nutrient permeability in the temperature range of 20-30 ℃; (2) different modes of action: according to the application, the thermosensitive polymer is prepared into nano particles, then the nano particles are added into the coated fertilizer membrane material, and the thermosensitive nano particles show different permeabilities of moisture and nutrients at different temperatures, so that the thermosensitive controlled release membrane material with intelligent controlled release is obtained. The use amount of the thermosensitive polymer is only 0.03-0.3% of the total mass of the fertilizer, and compared with the proportion of the thermosensitive film material in the background technology to 50% of the total mass of the fertilizer, the use amount and the use cost of the thermosensitive polymer nano particles are extremely low, so that the thermosensitive polymer nano particles are favorable for popularization and use; (3) the performance aspect of the coated fertilizer: the controlled release membrane material has the intelligent temperature response characteristic, and can achieve the intelligent controlled release effect of the release rate responding to the temperature. The LCST type thermosensitive polymer and UCST type thermosensitive polymer are added into the thermosensitive polymer nano-particles, and the specific working principle is as follows: the size of the intermolecular gap of the LCST type thermosensitive polymer is normal at high temperature, and the intermolecular gap is large at low temperature; UCST-type thermosensitive polymers are just opposite to the UCST-type thermosensitive polymers, wherein intermolecular gaps are large at high temperature, and the intermolecular gaps are normal in size at low temperature.
The principle of the change of the molecular gap is as follows: the hydroxyl groups of the molecular chains on the temperature-sensitive polymer are sensitive to temperature, and the interaction between the groups and water in the molecules and between the molecules can be influenced by the change of the temperature, so that the polycondensation phenomenon can occur along with the change of the temperature, and the change of the molecular gaps of the polymer is caused. Therefore, LCST type and UCST type thermosensitive polymers are simultaneously added into the controlled release membrane material, the size of the molecular gap of the UCST type thermosensitive polymer is normal at the excessively low temperature (< 20 ℃), the temperature sensitive intelligent membrane material releases water and nutrients relatively slowly due to the poor permeability of nano-scale thermosensitive resin particles, and at the excessively low temperature, crops absorb less nutrients, so that the waste of fertilizer nutrients caused by the fact that the crops cannot absorb the nutrients in time can be avoided; at a proper temperature (20-30 ℃), molecular gaps of LCST and UCST thermosensitive polymers are enlarged, and the nanoscale thermosensitive resin particles are high in water permeability, so that the thermosensitive intelligent film material is relatively quick in release of moisture and nutrients, and crops quickly absorb the nutrients in a proper temperature range, so that the nutrient utilization rate can be effectively improved; at an excessively high temperature (> 30 ℃), the size of gaps between molecules of the LCST type thermosensitive polymer is normal, and the moisture and nutrient are relatively slowly released due to poor permeability of nano-scale thermosensitive resin particles, so that crops absorb less nutrients at the excessively high temperature, and waste of fertilizer nutrients caused by incapability of timely absorbing the nutrients by the crops can be avoided (figure 1).
Therefore, the technical scheme of the application realizes that the change of temperature can lead to the change of the water permeability and the nutrient permeability of the thermosensitive polymer nano particles, thereby achieving the effect of accurately regulating and controlling the nutrient release rate of the thermosensitive coated fertilizer, ensuring that the coated fertilizer is released rapidly at a proper temperature (20-30 ℃) of crops and the nutrients are released slowly at too low or too high temperature, thereby perfectly combining the nutrient release rule of the coated fertilizer with the fertilizer requirement rule of the crops, obviously improving the fertilizer utilization rate and achieving the purpose of intelligent controlled release of the coated fertilizer.
Based on the improved thought, the specific technical scheme of the application is as follows:
the LCST or UCST type thermosensitive polymer nanoparticle is prepared from the following raw materials in parts by weight:
1 (30-90) adding LCST or UCST type temperature-sensitive polymer monomer, initiator potassium persulfate and cross-linking agent nano hydroxyapatite into a 100mL three-neck round bottom flask according to the mass ratio of (30-90), supplementing 60mL of total volume of the system with deionized water, and carrying out ultrasonic treatment for 10 minutes at room temperature to promote uniform dispersion of the reaction monomer; then, carrying out polymerization reaction in a constant-temperature water bath at 25 ℃, adding 60 mu L of promoter tetramethyl ethylenediamine, and reacting for 1-15 hours under the protection of nitrogen; washing for 3 times after the reaction is finished, removing unreacted monomers, and finally obtaining the thermosensitive polymer nano particles through a low-temperature freeze drying technology.
The preparation mechanism of the thermosensitive polymer nano-particles is as follows: under the action of an initiator, a cross-linking agent and an accelerator, the monomer of the thermosensitive polymer is polymerized to form the thermosensitive polymer with a body type structure. The polymer molecular chain contains a large number of hydroxyl groups, the polymer molecular chain is very sensitive to temperature change, the temperature change can influence the interaction between the groups and water in molecules and between molecules, and a polycondensation phenomenon can occur along with the temperature change, so that the gap between polymer molecules is changed.
Wherein the LCST type temperature-sensitive polymer monomer is one or more of N-isopropyl acrylamide, N-diethyl acrylamide, N-ethyl acrylamide and N-N-propyl acrylamide;
wherein the UCST type temperature-sensitive polymer monomer is one or more of acrylamide and acrylic acid;
finally, the particle size distribution of the prepared thermosensitive polymer nano particles is 1-500 nanometers. The distribution range of the particle size of the nano particles is regulated by the reaction time, and the longer the reaction time is, the larger the particle size of the polymer particles is.
The inventor further provides a preparation method of the membrane material coating liquid, which comprises the following steps:
the LCST type thermosensitive polymer nanoparticles and UCST type thermosensitive polymer nanoparticles prepared by the method are added with a proper amount of coating liquid according to the mass ratio of 1:1, and then stirred for 10min at the speed of 100rpm by using a magnetic stirrer at the temperature of 25 ℃ so that the thermosensitive polymer nanoparticles are dispersed in the coating liquid to obtain the uniformly blended controlled release membrane material coating liquid.
Wherein the content of the thermosensitive polymer nano particles in the coating liquid is 1-5wt%;
the coating liquid is one or more selected from chloroform solvent-dissolved polypropylene solution (solvent mass: solute mass=6:1), polyester polyol and isocyanate blend (mass ratio of the two is 1:1), water solvent-dissolved polyvinyl alcohol solution (solvent mass: solute mass=6:1) and chloroform solvent-dissolved polymethyl ethylene carbonate solution (solvent mass: solute mass=6:1); the preferable coating liquid is a blend of polyether polyol and isocyanate (the mass ratio of the polyether polyol to the isocyanate is 1:1).
By utilizing the coating liquid, the inventor also provides a corresponding preparation method of the controlled release fertilizer, which comprises the following steps:
adding the granular fertilizer into a continuously rotating coating pot, preheating the granular fertilizer for 1h at 25 ℃, and uniformly spraying the uniformly mixed coating liquid containing the thermosensitive polymer nanoparticles on the surface of the granular fertilizer at a pressure of 1MPa according to the proportion of 3-7% of the total weight of the fertilizer; after the liquid raw material of the controlled-release membrane material is solidified, a layer of temperature-sensitive bio-based controlled-release membrane material which is uniformly distributed can be formed on the surface of the granular fertilizer. The preparation method of the controlled release fertilizer provided by the application is different from other patents in that the used coating temperature is lower, and the aim is to avoid the problem of nanoparticle denaturation caused by high temperature, so that the energy consumption of the controlled release fertilizer is lower and the controlled release fertilizer is more environment-friendly.
The intelligent controlled release coated fertilizer product filled with the thermosensitive polymer nano particles is obtained by detecting that the controlled release fertilizer finally obtained according to the proportion is in the nutrient controlled release period of 30-60 days at 25 ℃. As can be seen from fig. 3, the temperature-sensitive intelligent controlled-release coated fertilizer product has relatively good nutrient controlled-release performance and small nutrient release rate when the content of the added temperature-sensitive particles is more at 15 ℃, so that the waste of fertilizer nutrients caused by that crops cannot absorb the nutrients in time can be avoided; the more the content of the thermosensitive particles is added at the temperature of 25 ℃, the poorer the nutrient controlled release performance is, the nutrients are released rapidly, and the crops absorb a large amount of the nutrients, so that the nutrient utilization rate can be effectively improved; the more the content of the thermosensitive particles is added at 35 ℃, the better the nutrient controlled release performance and the smaller the nutrient release rate are, and the waste of fertilizer nutrients caused by the fact that crops cannot absorb the nutrients in time can be avoided. The results show that different temperatures can influence the nutrient controlled release performance of the temperature-sensitive intelligent controlled release coated fertilizer products. The reason for this is: at the excessively low temperature (< 20 ℃), the temperature-sensitive intelligent membrane material is slower in relative release of moisture and nutrient due to the fact that the UCST-type temperature-sensitive polymer has normal molecular gap size and poor water permeability of the nanoscale temperature-sensitive resin particles; at a proper temperature (20-30 ℃), as the molecular gaps of LCST and UCST temperature-sensitive polymers are enlarged, the nano-scale temperature-sensitive resin particles have strong water permeability, so that the temperature-sensitive intelligent film material releases water and nutrients relatively quickly; at an excessively high temperature (> 30 ℃), the molecular gap size of the LCST type thermosensitive polymer is normal, and the nanoscale thermosensitive resin particles are poor in water permeability, so that the thermosensitive intelligent membrane material is relatively slow in release of moisture and nutrients.
Wherein the granular fertilizer is one or more of granular urea, granular potassium chloride, granular calcium superphosphate, granular potassium dihydrogen phosphate and granular potassium sulfate; the particle size range is 2-4mm.
The inner diameter of the coating pot body is 300mm, and the rotating speed is 15rpm; the granular fertilizer is preheated by adopting a hot air heating mode, and the hot air speed is 80m 3 And/h, the temperature of hot air is 25 ℃; the spraying speed of the liquid raw material of the controlled-release film material is 2g/min, and the spraying temperature is 25 ℃.
In summary, the controlled release fertilizer finally obtained by the application has the advantages that compared with the prior art:
1. the nutrient intelligent controlled release coated fertilizer prepared by the application has the advantages that the product controlled release period is 30-60 days, the molecular gap of the thermosensitive polymer is small at the excessively low temperature (< 20 ℃), and the thermosensitive intelligent membrane material releases water and nutrients relatively slowly due to the poor water permeability of the nanoscale thermosensitive resin particles; at a proper temperature (20-30 ℃), the molecular gap of the thermosensitive polymer becomes larger, and the thermosensitive intelligent membrane material releases water and nutrients relatively fast due to the strong water permeability of the nanoscale thermosensitive resin particles; at the excessively high temperature (> 30 ℃), the molecular gap of the thermosensitive polymer is small, and the thermosensitive intelligent membrane material releases water and nutrients relatively slowly due to the poor water permeability of the nanoscale thermosensitive resin particles.
2. The application uses liquid raw materials and nano-scale temperature-sensitive resin particles as coating materials, has the characteristics of low price, rich sources and the like, and does not produce environmental pollution.
3. The application has simple processing technology, can carry out coating at 25 ℃, has low energy consumption and high efficiency, and belongs to the low energy consumption technology.
Drawings
FIG. 1 is a schematic diagram of the principle of intelligent controlled release of a controlled release fertilizer prepared by the application;
FIG. 2 is a graph showing the trend of temperature change at a soil depth of 10cm in an experimental example of the present application;
FIG. 3 is a graph showing the change of the culture release rate of the precise controlled release film coated fertilizer filled with the thermosensitive polymer nanoparticles prepared by the application at 15 ℃,25 ℃ and 35 ℃ respectively.
Detailed Description
For a better understanding of the present application, the following examples are further illustrated, but are not limited to the following examples. In the following examples and experimental examples, various raw materials and fertilizers are commercially available, except for the specific descriptions.
Example 1
An intelligent controlled release membrane filled with thermosensitive polymer nanoparticles is prepared from the following raw materials in parts by weight:
preparation of LCST type thermosensitive polymer nanoparticles:
3g of N-isopropyl acrylamide monomer, 0.1g of initiator potassium persulfate and 3g of cross-linking agent nano hydroxyapatite are weighed, the total volume of the system is 60mL, a 100mL three-neck round bottom flask is added, and the ultrasonic treatment is carried out for 10 minutes at room temperature, so that the uniform dispersion of the reaction monomer is promoted. The polymerization reaction is carried out in a constant temperature water bath at 25 ℃, 60 mu L of promoter tetramethyl ethylenediamine is added, and the reaction is carried out for 1 to 3 hours under the protection of nitrogen. Washing for 3 times after the reaction is finished, removing unreacted complete monomers, and finally obtaining LCST type thermosensitive polymer nano particles by a low-temperature freeze drying technology, wherein the particle size distribution range of the LCST type thermosensitive polymer nano particles is 1-10nm.
Preparation of UCST type thermosensitive polymer nanoparticles:
3g of acrylic acid monomer, 0.1g of initiator potassium persulfate and 3g of cross-linking agent nano hydroxyapatite are weighed, the total volume of the system is 60mL, a 100mL three-neck round bottom flask is added, and the ultrasonic treatment is carried out for 10 minutes at room temperature, so that the uniform dispersion of the reaction monomer is promoted. The polymerization reaction is carried out in a constant temperature water bath at 25 ℃, 60 mu L of promoter tetramethyl ethylenediamine is added, and the reaction is carried out for 1 to 3 hours under the protection of nitrogen. Washing for 3 times after the reaction is finished, removing unreacted complete monomers, and finally obtaining UCST-type thermosensitive polymer nano particles by a low-temperature freeze-drying technology, wherein the particle size distribution range of the UCST-type thermosensitive polymer nano particles is 1-10nm.
Adding the prepared LCST type thermosensitive polymer nanoparticles and UCST type thermosensitive polymer nanoparticles into a chloroform solvent-dissolved polypropylene solution (solvent mass: solute mass=6:1) according to a mass ratio of 1:1, and stirring for 10min at a speed of 100rpm by using a magnetic stirrer at 25 ℃ to ensure that the thermosensitive polymer nanoparticles are dispersed in a coating liquid to obtain a uniformly blended controlled release membrane coating liquid, namely the intelligent controlled release membrane material for filling the thermosensitive polymer nanoparticles. Wherein the content of the thermosensitive polymer nano particles in the coating liquid is 1wt%.
The specific application method of the prepared intelligent controlled release membrane material filled with the thermosensitive polymer nano particles in the coated fertilizer comprises the following steps:
adding granular urea into a continuously rotating coating pot, preheating the granular urea for 1h at 25 ℃, and uniformly spraying the uniformly mixed coating liquid containing the thermosensitive polymer nano particles on the surface of the granular fertilizer at a pressure of 1MPa according to the proportion of 4% of the total weight of the fertilizer; after the liquid raw material of the controlled-release membrane is solidified, a layer of temperature-sensitive bio-based controlled-release membrane which is uniformly distributed can be formed on the surface of the granular urea. Through detection, the intelligent controlled release coated fertilizer product filled with the thermosensitive polymer nano particles in the average 58.09 days of the controlled release period of the nutrient can be obtained.
In the method, the inner diameter of the coating pot body is 300mm, and the rotating speed is 15rpm; the granular urea is preheated by adopting a hot air heating mode, and the hot air speed is 80m 3 And/h, the temperature of hot air is 25 ℃; the spraying speed of the liquid raw material of the controlled-release film material is 2g/min, and the spraying temperature is 25 ℃.
Application example 1
The specific application method of the coated fertilizer product prepared in the example 1 is as follows:
potted rape vegetables are used as test crops, and a potted application test of the intelligent controlled release film coated fertilizer filled with thermosensitive polymer nanoparticles is carried out on 2021.08.22-2021.10.10 in Taian city of Shandong province, wherein the average yield of the first five years is 11.00 multiplied by 10 3 kg/ha; the specifications of the plastic basin used are: the diameter of the upper opening is 21.5cm, the height is 16.5cm, the following application examples and comparative examples are all repeated by adopting 5 potting tests, and the final data are obtained by taking the average value; the temperature change at a depth of 10cm in the soil during the test is shown in FIG. 2.
The specific flow is as follows: applying the tested fertilizer as a base fertilizer at the position of 8-10cm in soil depth, sowing 30 seeds of rape seeds on the surface layer of the soil, covering fine soil with 1mm, thinning the rape seedlings, reserving 10 rape seeds in each pot, and applying nitrogen with the nitrogen amount of 300kg/ha (fold purity), wherein the tested nitrogen is as follows: the coated urea prepared in example 1 accounts for 50% of the total weight of the coated urea, and the quick-acting urea accounts for 50%. The quick-acting urea in the tested fertilizer can provide N element required by early growth of rape; the controlled release urea in the tested fertilizer can provide N element required by the later growth of rape. The phosphate fertilizer is selected from triple superphosphate, and the phosphorus application amount is 150kg/ha (fold purity); the potassium fertilizer is potassium sulfate, and the potassium application amount is 200kg/ha (reduced purity). Other non-mentioned field management measures are the same as the peasant's conventional management measures.
The yield of the rape vegetables under the treatment is as follows: 17.04×10 3 kg/ha, the total profit is: 68160.00 yuan/ha, net benefit is: 44650.48 yuan/ha, increased revenue 23026.87 yuan/ha (shown in Table 1);
comparative example 1-1: the coated urea prepared in example 1 accounts for 100% by weight; other factors follow in the present embodimentThe process remains consistent. The yield of the rape vegetables is as follows: 15.24X10 3 kg/ha, the total profit is: 60960.00 yuan/ha, net benefit is: 36976.48 yuan/ha, increased revenue 14936.48 yuan/ha (shown in Table 1);
comparative examples 1-2: commercial ordinary coated controlled release urea accounts for 50% by weight, and quick-acting urea accounts for 50% by weight; other factors remain consistent with the process in this embodiment. The yield of the rape vegetables is as follows: 11.46×10 3 kg/ha, the total profit is: 45840.00 yuan/ha, net benefit is: 22040.00 yuan/ha, increased revenue 916.40 yuan/ha (shown in Table 1);
comparative examples 1-3: the quick-acting urea accounts for 100 percent by weight (the quick-acting urea is divided into base fertilizer and additional fertilizer which are applied for 2 times, wherein the base fertilizer accounts for 50 percent, the additional fertilizer accounts for 50 percent, and the PK fertilizer is applied as the base fertilizer at one time); other factors remain consistent with the process in this embodiment. The yield of the rape vegetables is as follows: 11.20X10 3 kg/ha, the total profit is: 44800.00 yuan/ha, net benefit is: 21123.60 yuan/ha (shown in Table 1);
comparative examples 1-1, 1-2 and 1-3, the intelligent controlled release film material filled with thermosensitive polymer nanoparticles in this example showed maximum yield (17.04×10) of rape vegetables treated with urea 3 kg/ha), the net gain is the largest (44650.48 yuan/ha), and the income is increased by 23026.87 yuan/ha.
Example 2:
an intelligent controlled release membrane filled with thermosensitive polymer nanoparticles is prepared from the following raw materials in parts by weight:
preparation of LCST type thermosensitive polymer nanoparticles:
6g of N, N-diethyl propionamide monomer, 0.1g of initiator potassium persulfate and 6g of cross-linking agent nano hydroxyapatite are weighed, the total volume of the system is 60mL, a 100mL three-neck round bottom flask is added, and the ultrasonic treatment is carried out for 10 minutes at room temperature, so that the uniform dispersion of the reaction monomer is promoted. The polymerization reaction is carried out in a constant temperature water bath at 25 ℃, 60 mu L of promoter tetramethyl ethylenediamine is added, and the reaction is carried out for 3 to 8 hours under the protection of nitrogen. Washing for 3 times after the reaction is finished, removing unreacted complete monomers, and finally obtaining LCST type thermosensitive polymer nano particles through a low-temperature freeze drying technology. The particle size is 10-100nm.
Preparation of UCST type thermosensitive polymer nanoparticles:
6g of acrylic acid monomer, 0.1g of initiator potassium persulfate and 6g of cross-linking agent nano hydroxyapatite are weighed, the total volume of the system is 60mL, a 100mL three-neck round bottom flask is added, and the ultrasonic treatment is carried out for 10 minutes at room temperature, so that the uniform dispersion of the reaction monomer is promoted. The polymerization reaction is carried out in a constant temperature water bath at 25 ℃, 60 mu L of promoter tetramethyl ethylenediamine is added, and the reaction is carried out for 3 to 8 hours under the protection of nitrogen. Washing for 3 times after the reaction is finished, removing unreacted complete monomers, and finally obtaining UCST-type thermosensitive polymer nano particles through a low-temperature freeze-drying technology. The particle size is 10-100nm.
Adding the prepared LCST type thermosensitive polymer nanoparticles and UCST type thermosensitive polymer nanoparticles into a polyester polyol and isocyanate blend (the mass ratio of the polyester polyol to the isocyanate blend is 1:1) according to the mass ratio of 1:1, and stirring for 10min at the speed of 100rpm by using a magnetic stirrer at 25 ℃ to ensure that the thermosensitive polymer nanoparticles are dispersed in the coating liquid to obtain the uniformly blended controlled release membrane material coating liquid. Wherein the content of the thermosensitive polymer nano particles in the coating liquid is 3wt%.
The specific application method of the prepared intelligent controlled release membrane material filled with the thermosensitive polymer nano particles in the coated fertilizer comprises the following steps:
adding granular urea into a continuously rotating coating pot, preheating the granular urea for 1h at 25 ℃, and uniformly spraying the uniformly mixed coating liquid containing the thermosensitive polymer nano particles on the surface of the granular fertilizer at a pressure of 1MPa according to the proportion of 4% of the total weight of the fertilizer; after the liquid raw material of the controlled-release membrane is solidified, a layer of temperature-sensitive bio-based controlled-release membrane which is uniformly distributed can be formed on the surface of the granular urea. Through detection, the intelligent controlled release coated fertilizer product filled with the thermosensitive polymer nano particles in the average 35.05 days of the controlled release period of the nutrient can be obtained.
In the method, the inner diameter of the coating pot body is 300mm, and the rotating speed is 15rpm; the granular urea is preheated by adopting a hot air heating mode, and the hot air speed is 80m 3 And/h, the temperature of hot air is 25 ℃;the spraying speed of the liquid raw material of the controlled-release film material is 2g/min, and the spraying temperature is 25 ℃.
Application example 2
The specific application method of the coated fertilizer product prepared in example 2 is as follows:
potted rape vegetables are used as test crops, and a potted application test of the intelligent controlled release film coated fertilizer filled with thermosensitive polymer nanoparticles is carried out on 2021.08.22-2021.10.10 in Taian city of Shandong province, wherein the average yield of the first five years is 11.00 multiplied by 10 3 kg/ha; the specifications of the plastic basin used are: the diameter of the upper opening is 21.5cm, the height is 16.5cm, the following examples and comparative examples are repeated by adopting 5 potting tests, and the final data are obtained by taking the average value; the temperature change at a depth of 10cm in the soil during the test is shown in FIG. 2.
The specific flow is as follows: applying the tested fertilizer as a base fertilizer at the position of 8-10cm in soil depth, sowing 30 seeds of rape seeds on the surface layer of the soil, covering fine soil with 1mm, thinning the rape seedlings, reserving 10 rape seeds in each pot, and applying nitrogen with the nitrogen amount of 300kg/ha (fold purity), wherein the tested nitrogen is as follows: the coated urea prepared in example 2 accounts for 50% of the total weight of the coated urea, and the quick-acting urea accounts for 50% of the total weight of the coated urea. The quick-acting urea in the tested fertilizer can provide N element required by early growth of rape; the controlled release urea in the tested fertilizer can provide N element required by the later growth of rape. The phosphate fertilizer is selected from triple superphosphate, and the phosphorus application amount is 150kg/ha (fold purity); the potassium fertilizer is potassium sulfate, and the potassium application amount is 200kg/ha (reduced purity). Other non-mentioned field management measures are the same as the peasant's conventional management measures.
The yield of the rape vegetables under the treatment is as follows: 25.62 ×10 3 kg/ha, the total profit is: 102480.00 yuan/ha, net benefit is: 78473.84 yuan/ha, increased revenue 57300.24 yuan/ha (shown in Table 1);
comparative example 2-1: the coated urea prepared in example 2 accounts for 100% by weight; other factors remain consistent with the process in this embodiment. The yield of the rape vegetables is as follows: 23.06X10 3 kg/ha, the total profit is: 92240.00 yuan/ha, net benefit is: 68719.15 yuan/ha, increased revenue 47595.55 yuan/ha (shown in Table 1);
comparative examples 2-1, 1-2 and 1-3The intelligent controlled release film material filled with thermosensitive polymer nanoparticles in this example has the greatest yield of rape vegetables treated with coated urea (25.62 ×10) 3 kg/ha), the net gain is the largest (78473.84 yuan/ha), and the income is increased by 57300.24 yuan/ha.
Example 3:
an intelligent controlled release membrane filled with thermosensitive polymer nanoparticles is prepared from the following raw materials in parts by weight:
preparation of LCST type thermosensitive polymer nanoparticles:
9g N-ethyl acrylamide monomer, 0.1g of initiator potassium persulfate and 9g of cross-linking agent nano hydroxyapatite are weighed, the total volume of the system is 60mL, a 100mL three-neck round bottom flask is added, and the ultrasonic treatment is carried out for 10 minutes at room temperature, so that the uniform dispersion of the reaction monomer is promoted. The polymerization reaction is carried out in a constant temperature water bath at 25 ℃, 60 mu L of promoter tetramethyl ethylenediamine is added, and the reaction is carried out for 8 to 15 hours under the protection of nitrogen. Washing for 3 times after the reaction is finished, removing unreacted complete monomers, and finally obtaining LCST type thermosensitive polymer nano particles through a low-temperature freeze drying technology. The particle size is 100-500nm.
Preparation of UCST type thermosensitive polymer nanoparticles:
9g of acrylic acid monomer, 0.1g of initiator potassium persulfate and 9g of cross-linking agent nano hydroxyapatite are weighed, the total volume of the system is 60mL, a 100mL three-neck round bottom flask is added, and the ultrasonic treatment is carried out for 10 minutes at room temperature, so that the uniform dispersion of the reaction monomer is promoted. The polymerization reaction is carried out in a constant temperature water bath at 25 ℃, 60 mu L of promoter tetramethyl ethylenediamine is added, and the reaction is carried out for 8 to 15 hours under the protection of nitrogen. Washing for 3 times after the reaction is finished, removing unreacted complete monomers, and finally obtaining UCST-type thermosensitive polymer nano particles through a low-temperature freeze-drying technology. The particle size is 100-500nm.
Adding the prepared LCST type thermosensitive polymer nanoparticles and UCST type thermosensitive polymer nanoparticles into a chloroform solvent-dissolved polymethyl ethylene carbonate solution (solvent mass: solute mass=6:1) according to a mass ratio of 1:1, and stirring for 10min at a speed of 100rpm by using a magnetic stirrer at 25 ℃ to ensure that the thermosensitive polymer nanoparticles are dispersed in the coating liquid to obtain a uniformly blended controlled release membrane material coating liquid. Wherein the content of the thermosensitive polymer nano particles in the coating liquid is 5wt%.
The specific application method of the prepared intelligent controlled release membrane material filled with the thermosensitive polymer nano particles in the coated fertilizer comprises the following steps:
adding granular urea into a continuously rotating coating pot, preheating the granular urea for 1h at 25 ℃, and uniformly spraying the uniformly mixed coating liquid containing the thermosensitive polymer nano particles on the surface of the granular fertilizer at a pressure of 1MPa according to the proportion of 4% of the total weight of the fertilizer; after the liquid raw material of the controlled-release membrane is solidified, a layer of temperature-sensitive bio-based controlled-release membrane which is uniformly distributed can be formed on the surface of the granular urea. Through detection, the intelligent controlled release coated fertilizer product filled with the thermosensitive polymer nano particles in the average nutrient controlled release period of 33.65 days can be obtained.
In the method, the inner diameter of the coating pot body is 300mm, and the rotating speed is 15rpm; the granular urea is preheated by adopting a hot air heating mode, and the hot air speed is 80m 3 And/h, the temperature of hot air is 25 ℃; the spraying speed of the liquid raw material of the controlled-release film material is 2g/min, and the spraying temperature is 25 ℃.
Application example 3
The specific application method of the coated fertilizer product prepared in example 3 is as follows:
potted rape vegetables are used as test crops, and a potted application test of the intelligent controlled release film coated fertilizer filled with thermosensitive polymer nanoparticles is carried out on 2021.08.22-2021.10.10 in Taian city of Shandong province, wherein the average yield of the first five years is 11.00 multiplied by 10 3 kg/ha; the specifications of the plastic basin used are: the diameter of the upper opening is 21.5cm, the height is 16.5cm, the following examples and comparative examples are repeated by adopting 5 potting tests, and the final data are obtained by taking the average value; the temperature change at a depth of 10cm in the soil during the test is shown in FIG. 2.
The specific flow is as follows: applying the tested fertilizer as a base fertilizer at the position of 8-10cm in soil depth, sowing 30 seeds of rape seeds on the surface layer of the soil, covering fine soil with 1mm, thinning the rape seedlings, reserving 10 rape seeds in each pot, and applying nitrogen with the nitrogen amount of 300kg/ha (fold purity), wherein the tested nitrogen is as follows: the coated urea prepared in example 3 accounts for 50% of the total weight of the coated urea, and the quick-acting urea accounts for 50%. The quick-acting urea in the tested fertilizer can provide N element required by early growth of rape; the controlled release urea in the tested fertilizer can provide N element required by the later growth of rape. The phosphate fertilizer is selected from triple superphosphate, and the phosphorus application amount is 150kg/ha (fold purity); the potassium fertilizer is potassium sulfate, and the potassium application amount is 200kg/ha (reduced purity). Other non-mentioned field management measures are the same as the peasant's conventional management measures.
The yield of the rape vegetables under the treatment is as follows: 21.62×10 3 kg/ha, the total profit is: 86480.00 yuan/ha, net benefit is: 62451.20 yuan/ha, increased revenue 41327.59 yuan/ha (shown in Table 1);
comparative example 3-1: the coated urea prepared in example 3 accounts for 100% by weight; other factors remain consistent with the process in this embodiment. The yield of the rape vegetables is as follows: 17.06X10 3 kg/ha, the total profit is: 68240.00 yuan/ha, net benefit is: 44707.83 yuan/ha, increased revenue 23084.23 yuan/ha (shown in Table 1);
comparative examples 3-1, 1-2 and 1-3, the intelligent controlled release film material filled with thermosensitive polymer nanoparticles in this example showed maximum yield of rape vegetables treated with urea (21.62X10) 3 kg/ha), the net gain is the largest (62451.20 yuan/ha), and the income is increased by 41327.59 yuan/ha.
In summary, the technical scheme in the embodiment 2 of the application is the best implementation scheme, and can be widely popularized and applied.
TABLE 1
Note that: the calculations in the table above are as follows: rape acquisition price 4 yuan/kg, other expenses include: seed cost (400 yuan/mu), sowing cost (300 yuan/mu), pesticide cost (120 yuan/mu), water cost (90 yuan/mu), mechanical farmland cost (90 yuan/mu), harvesting cost (60 yuan/mu); manual expenditure: 1 time of base fertilizer and 1 time of top dressing (20 yuan/mu/time), pesticide spraying (60 yuan/mu), field management (100 yuan/mu), and the cost is calculated according to the actual expenditure.
The above example is one of the specific embodiments of the application selected, and the usual variations and substitutions made by those skilled in the art within the scope of the present technical solution are intended to be included in the scope of the present application.
Claims (6)
1. The utility model provides a fill accurate controlled release membrane material of temperature sensitive polymer nanoparticle which characterized in that: the preparation method comprises the following steps:
adding a proper amount of coating liquid into LCST type thermosensitive polymer nanoparticles and UCST type thermosensitive polymer nanoparticles according to the mass ratio of 1:1, and stirring for 10min at the speed of 100rpm by using a magnetic stirrer at the temperature of 25 ℃ to ensure that the thermosensitive polymer nanoparticles are dispersed in the coating liquid to obtain uniformly blended controlled-release membrane material coating liquid;
wherein the content of the thermosensitive polymer nano particles in the coating liquid is 1-5wt%;
the LCST type thermosensitive polymer nanoparticles and UCST type thermosensitive polymer nanoparticles are prepared from the following raw materials in parts by weight:
adding LCST or UCST type temperature-sensitive polymer monomer, initiator potassium persulfate and cross-linking agent nano hydroxyapatite into a 100mL three-neck round bottom flask according to the mass ratio of 30-90:1:30-90, supplementing 60mL of total volume of the system with deionized water, and carrying out ultrasonic treatment for 10 minutes at room temperature to promote uniform dispersion of the reaction monomer; then, carrying out polymerization reaction in a constant-temperature water bath at 25 ℃, adding 60 mu L of promoter tetramethyl ethylenediamine, and reacting for 1-15 hours under the protection of nitrogen; washing for 3 times after the reaction is finished, removing unreacted monomers, and finally obtaining the thermosensitive polymer nano particles through a low-temperature freeze drying technology;
wherein the LCST type temperature-sensitive polymer monomer is one or more of N-isopropyl acrylamide, N-diethyl acrylamide, N-ethyl acrylamide and N-N-propyl acrylamide;
wherein the UCST type temperature-sensitive polymer monomer is one or two of acrylamide and acrylic acid;
the coating liquid is selected from the following solvents in mass: chloroform-dissolved polypropylene solution with a solute mass ratio of 6:1, polyester polyol and isocyanate blend with a mass ratio of 1:1, solvent mass: polyvinyl alcohol aqueous solution with solute mass ratio of 6:1, solvent mass: one or more of chloroform-dissolved polymethyl ethylene carbonate solutions with a mass ratio of solute mass of 6:1.
2. The precision controlled release film of claim 1, wherein: the particle size distribution of the thermosensitive polymer nano particles is 1-500 nanometers.
3. The precision controlled release film of claim 1, wherein: the coating liquid is a blend of polyester polyol and isocyanate in a mass ratio of 1:1.
4. A method for preparing a controlled release fertilizer by using the precise controlled release membrane material as claimed in claim 1, which is characterized in that: the method comprises the following specific steps:
adding the granular fertilizer into a continuously rotating coating pot, preheating the granular fertilizer for 1h at 25 ℃, and then uniformly spraying coating liquid containing thermosensitive polymer nano particles on the surface of the granular fertilizer at a pressure of 1MPa according to the proportion of 3-7% of the total weight of the fertilizer; after the liquid raw material of the controlled-release membrane material is solidified, a layer of temperature-sensitive bio-based controlled-release membrane material which is uniformly distributed can be formed on the surface of the granular fertilizer.
5. The method of preparing a controlled release fertilizer of claim 4, wherein: the granular fertilizer is one or more of granular urea, granular potassium chloride, granular calcium superphosphate, granular potassium dihydrogen phosphate and granular potassium sulfate; the particle size range is 2-4mm.
6. According to claimThe method for preparing the controlled release fertilizer according to claim 4, wherein the method comprises the following steps: the inner diameter of the coating pot body is 300mm, and the rotating speed is 15rpm; the granular fertilizer is preheated by adopting a hot air heating mode, and the hot air speed is 80 and 80m 3 And/h, the temperature of hot air is 25 ℃; the spraying speed of the liquid raw material of the controlled-release film material is 2g/min, and the spraying temperature is 25 ℃.
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