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CN116355344B - Intelligent controlled release fertilizer capable of realizing temperature response and preparation method thereof - Google Patents

Intelligent controlled release fertilizer capable of realizing temperature response and preparation method thereof Download PDF

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Publication number
CN116355344B
CN116355344B CN202310398729.8A CN202310398729A CN116355344B CN 116355344 B CN116355344 B CN 116355344B CN 202310398729 A CN202310398729 A CN 202310398729A CN 116355344 B CN116355344 B CN 116355344B
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temperature
controlled release
mixed solution
polymer
fertilizer
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CN116355344A (en
Inventor
杨越超
刘嘉慧
刘成豪
岳东晓
于震
赵姗姗
解加卓
张淑刚
姚媛媛
王淳
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Shandong Agricultural University
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Shandong Agricultural University
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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
    • 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
    • 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
    • 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
    • C05G5/38—Layered or coated, e.g. dust-preventing coatings layered or coated with wax or resins
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Fertilizers (AREA)

Abstract

The invention discloses an intelligent controlled release fertilizer capable of responding to temperature and a preparation method thereof, and belongs to the technical field of controlled release fertilizers. According to the invention, the temperature response nanogel is synthesized by the polymer A containing dynamic covalent bonds and the temperature-sensitive polymer B, and the temperature response nanogel and a base membrane material are mixed to be used as a coating material, so that the intelligent controlled-release fertilizer capable of responding to temperature is prepared. The coating material can intelligently respond to the change of the environmental temperature of the root system, realizes autonomous switching and control of nutrient release, is an important part of the intellectualization of the controlled release fertilizer, and has great significance for improving the utilization rate of the fertilizer and realizing the synchronization of the release of the fertilizer nutrient and the requirement rule of crops.

Description

Intelligent controlled release fertilizer capable of realizing temperature response and preparation method thereof
Technical Field
The invention relates to the technical field of controlled release fertilizers, in particular to an intelligent controlled release fertilizer capable of responding to temperature and a preparation method thereof.
Background
The contribution of the fertilizer to grain yield increase is up to 55%, but the nutrients are completely released within a short time after the conventional fertilizer is applied, the crops cannot be fully absorbed and utilized, and the fertilizer is easy to run off along with a large amount of water, so that the nutrient utilization rate is very low, and serious problems of fertilizer resource waste, environmental pollution and the like are caused. As one of the most effective methods for reducing nutrient loss, controlled release fertilizers play a vital role, while petroleum-based polymer coated controlled release fertilizers have been widely used in agricultural production, bringing about revolutionary changes. In recent decades, different types of controlled release fertilizers, such as polyurethane coated controlled release fertilizers, sulfur coated controlled release fertilizers, paraffin-based coated controlled release fertilizers, epoxy resin coated controlled release fertilizers, phenolic resin coated controlled release fertilizers and bio-based polyurethane coated controlled release fertilizers, have been researched, and the controlled release fertilizers have a great deal of application in the agricultural field, some of the controlled release fertilizers can greatly prolong the controlled release period, some of the controlled release fertilizers greatly reduce the preparation cost of the membrane materials, and some of the controlled release fertilizers adopt environment-friendly biological materials to prepare the degradable bio-based coated controlled release fertilizers, so that the pollution to the environment is reduced. However, these coated controlled release fertilizers generally have some problems:
(1) The coating coated on the surface of the fertilizer core has a plurality of micropores which are main channels for water and nutrients to enter and exit, so the quantity of the micropores directly influences the controlled release performance of the controlled release fertilizer. In the production process of the traditional coated controlled release fertilizer, a plurality of micropores are inevitably generated, so that nutrients are released too quickly.
(2) The fertilizer nutrient can only be released through the micropores on the membrane material, but the existing coated slow-release fertilizer coating only slows down the release of the nutrient, and does not relate the release of the nutrient with the absorption of crops, so that the release of the fertilizer nutrient and the requirement rule of the crops cannot be synchronized, and sufficient nutrient cannot be provided in the nutrient sensitive period of the crops.
The law of nutrient absorption by crops is closely related to temperature. Generally, when the soil temperature reaches a certain value, the growth and development process of crops can be normally carried out; and when the soil temperature is too low, the growth and development of crops are slowed down, and the crops hardly absorb nutrients. At this time, if the soil contains nutrients, the nutrients cannot be absorbed and utilized by plants, so that a large amount of nutrients are lost and wasted. Therefore, if the prepared fertilizer can sense the change of the environmental temperature of the soil, the on-off of the release of the fertilizer nutrients can be regulated and controlled autonomously, and the method has great significance for realizing the synchronization of the release of the fertilizer nutrients and the requirement rules of crops.
The related patent CN113105604A discloses a bio-based polymer coating material, a coated controlled release fertilizer and a preparation method thereof, wherein a core of the fertilizer is coated by hydroxyl-containing components and isocyanate, but the synthesized controlled release fertilizer has a plurality of micropores even though the influence of moisture is reduced through a prepolymerization reaction, so that the controlled release performance is influenced; the related patent CN108675857A discloses a coated sustained-release fertilizer based on Sanzan gum and a preparation method thereof, wherein a crosslinked Sanzan gum solution is applied to a coating material, and the prepared gel structure is irreversible and has no responsiveness to temperature. Although the related patent CN115594551a discloses an accurate controlled release membrane material filled with thermosensitive polymer nanoparticles and application thereof, the polymer nanoparticles are obtained by polymerization reaction through a one-step synthesis method, the synthesis efficiency is low, and the scale use of the polymer nanoparticles is affected.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide an intelligent controlled release fertilizer capable of responding to temperature and a preparation method thereof. The response temperature of the intelligent controlled release fertilizer is 25-35 ℃, the condensation reflux is adopted for polymerization reaction, and the polymer A containing dynamic covalent bonds and the temperature-sensitive polymer B are used for jointly synthesizing temperature response nanogel, so that the intelligent response of opening and closing of the film holes along with the temperature change is more flexible and sensitive when the fertilizer film material recognizes the temperature change of soil.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a temperature response nanogel is provided, which is prepared from a polymer A containing dynamic covalent bonds and a temperature-sensitive polymer B according to a mass ratio of 1: (1-10) preparing the material;
the polymer A containing dynamic covalent bonds is prepared by the following method:
dissolving 1-vinylimidazole in water, adding sodium hydroxide, stirring uniformly, heating to 90-100 ℃, adding cyclohexanol dissolved in ethanol, dripping a cross-linking agent solution under the condition of cooling and refluxing, continuing heating and stirring for 15-20min after dripping, and removing ethanol to obtain a polymer A containing dynamic covalent bonds;
the temperature-sensitive polymer B is prepared by the following method:
adding N-vinyl caprolactam and a cross-linking agent into deionized water to obtain a first mixed solution; dissolving diallyl ether in ethanol, adding ammonium persulfate, and uniformly mixing to obtain a second mixed solution; heating the first mixed solution to 75-85 ℃, adding the second mixed solution into the first mixed solution, and stirring for reaction for 4-5h to obtain the temperature-sensitive polymer B.
Preferably, in the preparation method of the polymer A containing dynamic covalent bonds, the mass ratio of the added cyclohexyl alcohol to the added 1-vinyl imidazole is 1: (1-5).
Preferably, in the preparation method of the temperature-sensitive polymer B, the mass ratio of the N-vinyl caprolactam, the diallyl ether and the ammonium persulfate is (5-10): (2.5-3): 1.
preferably, the cross-linking agent is one or more of trimethylolpropane, vinyl triethoxysilane, N-methylene bisacrylamide, vinyl trimethoxysilane, triethylene diamine and 3-diethylaminopropylamine.
In a second aspect of the present invention, there is provided a method for preparing the above temperature responsive nanogel, comprising the steps of:
dissolving a polymer A containing dynamic covalent bonds in tetrahydrofuran solution, and heating to 75-85 ℃ to obtain a mixed solution A; dissolving the temperature-sensitive polymer B in absolute ethyl alcohol, and heating to 75-85 ℃ to obtain a mixed solution B; and (3) uniformly mixing the mixed solution A and the mixed solution B, adding a cross-linking agent under the stirring condition, keeping the temperature of 75-85 ℃ for reaction for 8-10h, filtering, washing and drying the product, and thus obtaining the temperature response nanogel.
Preferably, the cross-linking agent is one or more of trimethylolpropane, vinyl triethoxysilane, N-methylene bisacrylamide, vinyl trimethoxysilane, triethylene diamine and 3-diethylaminopropylamine; the addition amount of the cross-linking agent is 3-10% of the total weight of the polymer A and the temperature-sensitive polymer B.
In a third aspect of the present invention, there is provided the use of the above temperature responsive nanogel in (1) or (2) as follows:
(1) Preparing a coating material capable of intelligently identifying the change of the rhizosphere environmental temperature;
(2) And preparing the intelligent controlled release fertilizer for controlling nutrient release in response to temperature.
The fourth aspect of the invention provides a coating material capable of intelligently identifying the change of the rhizosphere ambient temperature, which is prepared from the following raw materials in parts by weight:
10 parts of base film material and 1-5 parts of temperature response nano gel.
Preferably, the base film material is selected from one or more of polyurethane, sulfur, paraffin, epoxy resin, phenolic resin and bio-based phenolic resin.
In a fifth aspect of the invention, an intelligent controlled release fertilizer capable of temperature response is provided, and the intelligent controlled release fertilizer is prepared by the following method:
spraying the coating material capable of intelligently identifying the change of the rhizosphere environmental temperature on the surface of the fertilizer particles; the spraying amount of the coating material is 1.0-10.0% of the weight of the fertilizer particles.
The invention has the beneficial effects that:
(1) According to the invention, the temperature response nanogel is prepared by crosslinking the polymer containing the dynamic covalent bond and the temperature response polymer, and the temperature response nanogel can sense the environmental temperature change by using the temperature-sensitive polymer and realize the automatic control of the opening and closing of the pore of the membrane by using the dynamic covalent bond.
(2) The temperature response nano gel provided by the invention is mixed with the existing basic film material, so that the film coating material capable of intelligently identifying the change of the rhizosphere environmental temperature can be prepared. The coating material can intelligently respond to the change of the environmental temperature of the root system, realizes autonomous switching and control of nutrient release, is an important part of the intellectualization of the controlled release fertilizer, and has great significance for improving the utilization rate of the fertilizer and realizing the synchronization of the release of the fertilizer nutrient and the requirement rule of crops.
(3) The coating material of the intelligent controlled-release fertilizer capable of responding to temperature, which is prepared by the invention, can be applied to any coated thermosetting controlled-release fertilizer production, and has simple production process and low energy consumption.
Drawings
Fig. 1: infrared spectra of the coating materials prepared in examples 1 to 4 of the present invention; as shown in FIG. 1, the coating material contains C-H 3 And C-O, demonstrating successful preparation of the polymeric polyurethane coating.
Fig. 2: film shell section of the coating material prepared in example 4 of the present invention observed under a Scanning Electron Microscope (SEM).
Fig. 3: the coating material prepared in the embodiment 4 of the invention has a dynamic covalent network structure diagram at 25 ℃ and 10 ℃, and at 25 ℃, a dynamic covalent bond is broken, a copolymer chain is contracted, micropores of a membrane network are exposed, and nutrients are released; at 10 ℃, the copolymer chain is restored, the dynamic covalent bond is restored to a crosslinked state, micropores are blocked, and nutrient release is inhibited.
Fig. 4: the coated controlled release fertilizer prepared in the embodiment 4 of the invention and the release rate curve of the controlled release fertilizer without adding the temperature response nanogel under different temperature conditions. The release rate curve can prove that the prepared temperature response type controlled release fertilizer has different nutrient release rates under different temperature conditions. The nutrient release rate is slower at 10 ℃ and 40 ℃, and the nutrient release is accelerated at 25 ℃. And compared with the controlled release fertilizer without the temperature response nano gel, the controlled release fertilizer has slower nutrient release at 10 ℃ but faster nutrient release at 40 ℃ under the condition of 25 ℃.
Fig. 5: the nutrient release curve of the intelligent controlled release fertilizer prepared in the embodiment 4 of the invention is compared with the cumulative nutrient absorption curve of winter wheat; the result shows that the nutrient release trend of the intelligent controlled-release fertilizer is synchronous with the nutrient absorption trend of winter wheat.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described above, in order to realize the intellectualization of the fertilizer, the invention develops and designs the intelligent controlled release fertilizer capable of responding to temperature. The invention firstly designs a temperature response nano gel, which is obtained by reacting a polymer A containing dynamic covalent bonds with a temperature-sensitive polymer B. Then, compounding the prepared temperature response nano gel with a basic film material to prepare a film coating material capable of intelligently identifying the change of the rhizosphere environmental temperature; and (3) coating the fertilizer particles by the coating material to finally prepare the intelligent controlled release fertilizer capable of responding to temperature.
When the soil temperature of the intelligent controlled-release fertilizer is too low or too high, the intelligent nanogel in the controlled-release fertilizer coating material is crosslinked with the membrane material, so that micropores in the membrane material are blocked, and nutrient release is reduced; when the soil environment temperature is proper, the internal conformation of the gel is changed, and the blocked micropores are opened to release nutrients. By adding the temperature response nanogel into the fertilizer membrane material, the temperature change in the rhizosphere environment can be intelligently identified, and the membrane holes on the surface of the fertilizer can be intelligently responded to on-off along with the temperature change, so that the release of nutrients is controlled, and the effect of intelligent controlled release is achieved. The specific principle is as follows:
when the soil environment temperature is proper (25-35 ℃), the long chain of the intelligent nano gel spontaneously contracts, partial crosslinking between the gel and the gel, and partial crosslinking between the gel and the coating material are cut off by stress, fine micropores are exposed, and nutrients are released to the outside through the micropores. And when the temperature is lower, the cut-off cross links are connected again under the action of dynamic covalent bonds to block the pores, so that a layer of compact shell is formed on the surface of the fertilizer core again, and the release of nutrients is slowed down.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples and comparative examples of the present invention are conventional in the art and are commercially available. The experimental procedure, without specifying the detailed conditions, was carried out according to the conventional experimental procedure or according to the operating instructions recommended by the suppliers. Wherein:
the biobased polyurethanes used are materials known from the prior art and can be prepared, for example, by the method of the reference "Novel environment-friendly superhydrophobic bio-based polymer derived from liquefied corncob for controlled-released reference in Organic Coatings,2021,151:106018 (1-10)".
The paraffin-based polyurethanes used are those known from the prior art and can be prepared, for example, by the method of the reference "Synthesis and Performance of Polyurethane Coated Urea as Slow/controlled Release Fertilizer [ J ]. Journal of Wuhan University of Technology (Materials Science Edition), 2012,27 (01): 126-129 ].
Example 1: preparation of intelligent controlled release fertilizer capable of responding to temperature
1. Preparing temperature response nanogel:
(1) 0.3g of cross-linking agent N, N-methylene bisacrylamide is dissolved in 50ml of absolute ethyl alcohol, the pH value is regulated to 6.5-7.5, nitrogen is introduced for 30min, and oxygen is removed, so as to obtain cross-linking agent solution.
(2) Placing a three-neck round bottom flask filled with 100ml of deionized water in an oil bath, adding 2g of 1-vinylimidazole, connecting and opening a stirring device, adding 5ml of NaOH solution (2 mol/L), setting the temperature of the oil bath to 100 ℃, opening a cooling reflux device, uniformly stirring and reacting for 20min, dissolving 2g of cyclohexanol in 10ml of absolute ethyl alcohol, adding the 10ml of absolute ethyl alcohol, and completely dripping the cross-linking agent solution in the step (1) under continuous stirring. And after the dripping is finished, continuously heating and stirring for 15-20min, removing ethanol, and finally obtaining the polymer A containing dynamic covalent bonds.
(3) Adding 5g of N-vinyl caprolactam and 0.3g of N, N-methylene bisacrylamide into 80ml of deionized water, carrying out ultrasonic vibration dissolution, and purging with nitrogen for 1h to obtain a first mixed solution;
2.5g of diallyl ether was dissolved in 50ml of absolute ethanol, and 1g of ammonium persulfate was added to the solution and mixed uniformly to obtain a second mixed solution.
And heating the first mixed solution to 80 ℃, adding the second mixed solution, continuously stirring for 4.5 hours, and then slightly cooling the solution, and maintaining the temperature at 50 ℃ to obtain the temperature-sensitive polymer B.
(4) Weighing 5g of the polymer A obtained in the step (2), dissolving in 50ml of tetrahydrofuran solution, and heating to 80 ℃ to obtain a mixed solution A;
weighing 5g of the temperature-sensitive polymer B prepared in the step (3), dissolving in 50ml of absolute ethyl alcohol, performing ultrasonic dispersion for 2 hours, and heating to 80 ℃ to obtain a mixed solution B;
and (3) uniformly mixing the mixed solution A and the mixed solution B, adding 0.3g of cross-linking agent N, N-methylene bisacrylamide under continuous stirring, keeping the temperature at 80 ℃ unchanged, reacting for 9 hours, filtering the product, washing with absolute ethyl alcohol, and drying under vacuum condition to obtain the temperature response nanogel.
2. Preparing an intelligent controlled release fertilizer:
500g of granular urea is added into a continuous rolling drum coating machine, preheating is carried out for 30min at 65 ℃, then 4.46g of bio-based polyurethane and 0.54g of temperature response nanogel prepared in the embodiment are evenly mixed and then poured into a coating pot, continuous rotation reaction is carried out for about 10min at 65 ℃, the urea particles are separated again after adhesion, and the coating liquid is solidified on the surfaces of the urea particles to form a film, thus obtaining the bio-based coated intelligent controlled release fertilizer with the coating thickness of 1%. And the coating thickness is increased by 1% every time the sample is added in the sample adding process, and the process is repeated for 3 times, so that the intelligent controlled release fertilizer with the coating thickness of 3.0% and capable of realizing temperature response is obtained.
Example 2: preparation of intelligent controlled release fertilizer capable of responding to temperature
1. Preparing temperature response nanogel:
(1) 0.5g of trimethylolpropane as a crosslinking agent is dissolved in 50ml of absolute ethyl alcohol, the pH is adjusted to 6.5-7.5, and nitrogen is introduced for 30min to obtain a crosslinking agent solution.
(2) Placing a three-neck round bottom flask filled with 100ml of deionized water in an oil bath, adding 3g of 1-vinylimidazole, connecting and opening a stirring device, adding 5ml of NaOH solution (2 mol/L), setting the temperature of the oil bath to 100 ℃, opening a cooling reflux device, uniformly stirring and reacting for 20min, dissolving 2g of cyclohexanol in 10ml of absolute ethyl alcohol, adding the 10ml of absolute ethyl alcohol, and completely dripping the cross-linking agent solution in the step (1) under continuous stirring. And after the dripping is finished, continuously heating and stirring for 15-20min, removing ethanol, and finally obtaining the polymer A containing dynamic covalent bonds.
(3) Adding 5g of N-vinyl caprolactam and 0.5g of trimethylolpropane into 80ml of deionized water, carrying out ultrasonic vibration dissolution, and purging with nitrogen for 1h to obtain a first mixed solution;
3g of diallyl ether was dissolved in 50ml of absolute ethanol, and 1g of ammonium persulfate was added to the solution and mixed uniformly to obtain a second mixed solution.
The first mixed solution is heated to 80 ℃, the second mixed solution is added, the solution is slightly cooled after continuous stirring for 4 hours, and the temperature-sensitive polymer B is obtained after the temperature of the solution is maintained at 50 ℃.
(4) Weighing 3g of the polymer A obtained in the step (2), dissolving in 50ml of tetrahydrofuran solution, and heating to 75 ℃ to obtain a mixed solution A;
9g of the temperature-sensitive polymer B obtained in the step (3) is weighed and dissolved in 50ml of absolute ethyl alcohol, and is subjected to ultrasonic dispersion for 2 hours and heating to 75 ℃ to obtain a mixed solution B.
And (3) uniformly mixing the mixed solution A and the mixed solution B, adding 0.5g of cross-linking agent N, N-methylene bisacrylamide under continuous stirring, keeping the temperature at 75 ℃ unchanged, reacting for 10 hours, filtering the product, washing with absolute ethyl alcohol, and drying under vacuum condition to obtain the temperature response nanogel.
2. Preparing an intelligent controlled release fertilizer:
500g of granular urea is added into a continuous rolling drum coating machine, preheating is carried out for 30min at 65 ℃, then 4.0g of epoxy resin and 1.0g of the temperature response nanogel prepared in the embodiment are evenly mixed and then poured into a coating pot, continuous rotation reaction is carried out for about 10min at 65 ℃, the urea particles are separated again after adhesion, and the coating liquid is solidified on the surfaces of the urea particles to form a film, thus obtaining the epoxy resin coated intelligent controlled-release fertilizer with the coating thickness of 1%. And the coating thickness is increased by 1% every time the sample is added in the sample adding process, and the process is repeated for 5 times, so that the intelligent controlled release fertilizer with the coating thickness of 5.0% and capable of realizing temperature response is obtained.
Example 3: preparation of intelligent controlled release fertilizer capable of responding to temperature
1. Preparing temperature response nanogel:
(1) 0.8g of cross-linking agent vinyl trimethoxy silane is dissolved in 50ml of absolute ethyl alcohol, the pH is adjusted to 6.5-7.5, nitrogen is introduced for 30min, and cross-linking agent solution is obtained.
(2) Placing a three-neck round bottom flask filled with 100ml of deionized water in an oil bath, adding 4g of 1-vinylimidazole, connecting and opening a stirring device, adding 5ml of NaOH solution (2 mol/L), setting the temperature of the oil bath to 100 ℃, opening a cooling reflux device, uniformly stirring and reacting for 20min, dissolving 2g of cyclohexanol in 10ml of absolute ethyl alcohol, adding the 10ml of absolute ethyl alcohol, and completely dripping the cross-linking agent solution in the step (1) under continuous stirring. And after the dripping is finished, continuously heating and stirring for 15-20min, removing ethanol, and finally obtaining the polymer A containing dynamic covalent bonds.
(3) 8g of N-vinylcaprolactam and 0.8g of vinyltrimethoxysilane are added into 80ml of deionized water, dissolved by ultrasonic vibration and purged with nitrogen for 1 hour, and a first mixed solution is obtained;
2.8g of diallyl ether was dissolved in 50ml of absolute ethanol, and 1g of ammonium persulfate was added to the solution and mixed uniformly to obtain a second mixed solution.
The first mixed solution is heated to 80 ℃, the second mixed solution is added, the solution is slightly cooled after continuous stirring for 5 hours, and the temperature-sensitive polymer B is obtained after the temperature of the solution is maintained at 50 ℃.
(4) Weighing 2g of the polymer A obtained in the step (2), dissolving in 50ml of tetrahydrofuran solution, and heating to 85 ℃ to obtain a mixed solution A;
weighing 10g of the temperature-sensitive polymer B obtained in the step (3), dissolving in 50ml of absolute ethyl alcohol, performing ultrasonic dispersion for 2 hours, and heating to 85 ℃ to obtain a mixed solution B.
And (3) uniformly mixing the mixed solution A and the mixed solution B, adding 0.8g of cross-linking agent N, N-methylene bisacrylamide under continuous stirring, keeping the temperature of 85 ℃ unchanged, reacting for 8 hours, filtering the product, washing with absolute ethyl alcohol, and drying under vacuum condition to obtain the temperature response nanogel.
2. Preparing an intelligent controlled release fertilizer:
500g of granular urea is added into a continuous rolling drum coating machine, preheating is carried out for 30min at 65 ℃, then 3.71g of paraffin-based polyurethane and 1.29g of temperature response nanogel prepared in the embodiment are evenly mixed and then poured into a coating pot, continuous rotation reaction is carried out for about 10min at 65 ℃, the urea particles are separated again after adhesion, and the coating liquid is solidified on the surfaces of the urea particles to form a film, thus obtaining the paraffin-coated intelligent controlled-release fertilizer with the coating thickness of 1%. And the coating thickness is increased by 1% every time the sample is added in the sample adding process, and the process is repeated for 6 times, so that the intelligent controlled release fertilizer with the coating thickness of 6.0% and capable of realizing temperature response is obtained.
Example 4: preparation of intelligent controlled release fertilizer capable of responding to temperature
1. Preparing temperature response nanogel:
(1) 1g of cross-linking agent vinyl trimethoxy silane is dissolved in 50ml of absolute ethyl alcohol, the pH is adjusted to 6.5-7.5, and nitrogen is introduced for 30min, so as to obtain cross-linking agent solution.
(2) A250 ml three-neck round bottom flask filled with 100ml deionized water is placed in an oil bath pot, 5g of 1-vinylimidazole is added, a stirring device is connected and opened, 5ml of NaOH solution (2 mol/L) is added, the temperature of the oil bath pot is set to 100 ℃, a cooling reflux device is opened, after stirring uniformly for 20min, 1g of cyclohexanol is dissolved in 10ml of absolute ethanol and added, and the cross-linking agent solution in the step (1) is completely dripped under continuous stirring. And after the dripping is finished, continuously heating and stirring for 15-20min, removing ethanol, and finally obtaining the polymer A containing dynamic covalent bonds.
(3) 10g of N-vinyl caprolactam and 1g of N, N-methylene bisacryloyl are added into 80ml of deionized water, ultrasonic oscillation is used for dissolution, and nitrogen is used for purging for 1h, so as to obtain a first mixed solution;
3g of diallyl ether was dissolved in 50ml of absolute ethanol, and 1g of ammonium persulfate was added to the solution and mixed uniformly to obtain a second mixed solution.
The first mixed solution is heated to 80 ℃, the second mixed solution is added, the solution is slightly cooled after continuous stirring for 4 hours, and the temperature-sensitive polymer B is obtained after the temperature of the solution is maintained at 50 ℃.
(4) Weighing 1g of the polymer A obtained in the step (2), dissolving in 50ml of tetrahydrofuran solution, and heating to 80 ℃ to obtain a mixed solution A; weighing 10g of the temperature-sensitive polymer B obtained in the step (3), dissolving in 50ml of absolute ethyl alcohol, performing ultrasonic dispersion for 2 hours, and heating to 80 ℃ to obtain a mixed solution B.
And (3) uniformly mixing the mixed solution A and the mixed solution B, adding 1g of cross-linking agent N, N-methylene bisacrylamide under continuous stirring, keeping the temperature at 80 ℃ unchanged, reacting for 9 hours, filtering the product, washing with absolute ethyl alcohol, and drying under vacuum condition to obtain the temperature response nanogel.
2. Preparing an intelligent controlled release fertilizer:
500g of granular urea is added into a continuous rolling drum coating machine, preheating is carried out for 30min at 65 ℃, then 3.57g of phenolic resin and 1.43g of the temperature response nanogel prepared in the embodiment are evenly mixed and then poured into a coating pot, continuous rotation reaction is carried out for about 10min at 65 ℃, the urea particles are separated again after adhesion, and the coating liquid is solidified on the surfaces of the urea particles to form a film, thus obtaining the phenolic resin coated intelligent controlled release fertilizer with the coating thickness of 1%. And the coating thickness is increased by 1% every time the sample is added in the sample adding process, and the process is repeated for 8 times, so that the intelligent controlled release fertilizer with the coating thickness of 8.0% and capable of realizing temperature response is obtained.
Comparative example 1: preparation of controlled release fertilizer without adding temperature-corresponding nanogel
Adding 500g of granular urea into a continuous rolling drum coating machine, preheating for 30min at 65 ℃, pouring 5g of phenolic resin into a coating pot, continuously rotating at 65 ℃ for reaction for about 10min, separating again after urea particles adhere, and solidifying the coating liquid on the surfaces of the urea particles to form a film, thereby obtaining the phenolic resin coated controlled release fertilizer with the coating thickness of 1%, wherein the coating thickness is increased by 1% every time during the sample adding process, and the process is repeated for 8 times to obtain the nano gel controlled release fertilizer with the thickness of 8.0% and corresponding to the non-added temperature.
Comparative example 2: preparation of controlled Release Fertilizer with addition of nanogel prepared from Polymer A alone
1. Preparing a nano gel:
(1) 1g of cross-linking agent vinyl trimethoxy silane is dissolved in 50ml of absolute ethyl alcohol, the pH is adjusted to 6.5-7.5, and nitrogen is introduced for 30min, so as to obtain cross-linking agent solution.
(2) A250 ml three-neck round bottom flask filled with 100ml deionized water is placed in an oil bath pot, 5g of 1-vinylimidazole is added, a stirring device is connected and opened, 5ml of NaOH solution (2 mol/L) is added, the temperature of the oil bath pot is set to 100 ℃, a cooling reflux device is opened, after stirring uniformly for 20min, 1g of cyclohexanol is dissolved in 10ml of absolute ethanol and added, and the cross-linking agent solution in the step (1) is completely dripped under continuous stirring. And after the dripping is finished, continuously heating and stirring for 15-20min, removing ethanol, and finally obtaining the polymer A containing dynamic covalent bonds.
(3) Weighing 1g of the polymer A obtained in the step (2), dissolving in 50ml of tetrahydrofuran solution, and heating to 80 ℃ to obtain a mixed solution A; adding 1g of cross-linking agent N, N-methylene bisacrylamide into the mixed solution A under continuous stirring, keeping the temperature at 80 ℃ unchanged, reacting for 9 hours, filtering the product, washing with absolute ethyl alcohol, and drying under vacuum condition to obtain the nanogel A.
2. Preparing an intelligent controlled release fertilizer:
500g of granular urea is added into a continuous rolling drum coating machine, preheating is carried out for 30min at 65 ℃, then 3.57g of phenolic resin and 1.43g of nanogel A are evenly mixed and then poured into a coating pot, continuous rotation reaction is carried out for about 10min at 65 ℃, the urea particles are separated again after adhesion, and the coating liquid is solidified on the surfaces of the urea particles to form a film, thus obtaining the phenolic resin coated intelligent controlled-release fertilizer with the coating thickness of 1%. The coating thickness is increased by 1% every time the sample is added in the sample adding process, and the process is repeated for 8 times, so that the controlled release fertilizer with the coating thickness of 8.0% is obtained.
Comparative example 3: preparation of controlled release fertilizer added with nanogel prepared only from temperature-sensitive polymer B
1. Preparing a nano gel:
(1) 10g of N-vinyl caprolactam and 1g of N, N-methylene bisacryloyl are added into 80ml of deionized water, ultrasonic oscillation is used for dissolution, and nitrogen is used for purging for 1h, so as to obtain a first mixed solution;
3g of diallyl ether was dissolved in 50ml of absolute ethanol, and 1g of ammonium persulfate was added to the solution and mixed uniformly to obtain a second mixed solution.
The first mixed solution is heated to 80 ℃, the second mixed solution is added, the solution is slightly cooled after continuous stirring for 4 hours, and the temperature-sensitive polymer B is obtained after the temperature of the solution is maintained at 50 ℃.
(2) Weighing 10g of the temperature-sensitive polymer B obtained in the step (1), dissolving in 50ml of absolute ethyl alcohol, performing ultrasonic dispersion for 2 hours, and heating to 80 ℃ to obtain a mixed solution B. Adding 1g of cross-linking agent N, N-methylene bisacrylamide into the mixed solution B under continuous stirring, keeping the temperature at 80 ℃ unchanged, reacting for 9 hours, filtering the product, washing with absolute ethyl alcohol, and drying under vacuum condition to obtain the nanogel B.
2. Preparing an intelligent controlled release fertilizer:
500g of granular urea is added into a continuous rolling drum coating machine, preheating is carried out for 30min at 65 ℃, then 3.57g of phenolic resin and 1.43g of nanogel B are evenly mixed and then poured into a coating pot, continuous rotation reaction is carried out for about 10min at 65 ℃, the urea particles are separated again after adhesion, and the coating liquid is solidified on the surfaces of the urea particles to form a film, thus obtaining the phenolic resin coated intelligent controlled-release fertilizer with the coating thickness of 1%. The coating thickness is increased by 1% every time the sample is added in the sample adding process, and the process is repeated for 8 times, so that the controlled release fertilizer with the coating thickness of 8.0% is obtained.
Test example:
the performance of the temperature-responsive intelligent controlled release fertilizers prepared in examples 1 to 4 was examined, and the specific examples were as follows:
1. and (3) infrared spectrum detection:
infrared spectrum detection is carried out on the coating materials of the intelligent controlled release fertilizers of the examples 1-4, and the results are shown in figure 1. The results show that: the coating material contains C-H 3 And C-O, demonstrating successful preparation of the polymeric polyurethane coating.
2. Scanning electron microscope observation:
the intelligent controlled release fertilizer capable of responding to temperature prepared in the example 4 is soaked in water, after the fertilizer is completely dissolved and released, the membrane shell is recovered, washed and dried and cut into proper sizes, and the proper sizes are respectively kept in an oven at 10 ℃ and 25 ℃ for 1 hour and then immediately observed under SEM, wherein the magnification is 20000 times.
The results are shown in FIG. 2, where at 25deg.C, the cross section has many micropores due to the conformational change of the temperature responsive nanogel, while the cross section at 10deg.C is significantly smooth and flat, indicating that these micropores are blocked by the re-cross-linking under the action of dynamic covalent bonds. The existence of micropores can enable water to enter the membrane shell more quickly, so that urea is dissolved and released, and the quantity of the micropores directly influences the controlled release performance of the membrane material.
The simulation schematic diagram of the dynamic covalent network structure of the coating material at 25 ℃ and 10 ℃ is shown in figure 3, the dynamic covalent bond is broken at 25 ℃, and the copolymer chain is contracted to expose the network micropores of the coating material and release nutrients; at 10 ℃, the copolymer chain is restored, the dynamic covalent bond is restored to a crosslinked state, micropores are blocked, and nutrient release is inhibited.
3. Determination of the release rate under different temperature conditions:
the non-added temperature-responsive nanogel controlled-release fertilizer obtained in comparative example 1 and the intelligent controlled-release fertilizer prepared in example 4 (added temperature-responsive nanogel) were respectively placed at 10 ℃, 25 ℃ and 40 ℃ for still water culture, and samples were taken at regular intervals to determine the nutrient release rate.
The results are shown in fig. 4, which shows: the temperature response type controlled release fertilizer prepared by the invention has different nutrient release rates under different temperature conditions. The nutrient release rate is slower at 10 ℃ and 40 ℃, and the nutrient release is accelerated at 25 ℃. And compared with the controlled release fertilizer without the temperature response nano gel, the controlled release fertilizer has slower nutrient release at 10 ℃ but faster nutrient release at 40 ℃ under the condition of 25 ℃.
4. Nutrient release compared to winter wheat nutrient absorption trend:
the nutrient release curve of the intelligent controlled-release fertilizer of example 4 is compared with the cumulative nutrient absorption curve of winter wheat, and the result is that the nutrient release trend of the controlled-release fertilizer and the nutrient absorption trend of winter wheat are synchronous as shown in fig. 5.
5. Investigation of nutrient controlled release time under high temperature conditions:
the controlled release fertilizer obtained in comparative examples 1-3 and the intelligent controlled release fertilizer prepared in example 4 are respectively placed at 40 ℃ for hydrostatic cultivation, and the nutrient release rate is measured by sampling at regular intervals; the time required for the cumulative release rate of the nutrient to reach 80% is taken as the controlled release period.
The results were as follows:
the controlled release period of the controlled release fertilizer prepared in comparative example 1 was 80 days; the controlled release period of the controlled release fertilizer prepared in comparative example 2 was 90 days; the controlled release period of the controlled release fertilizer prepared in comparative example 3 was 95 days; the controlled release period of the intelligent controlled release fertilizer prepared in example 4 was 110 days.
For a general coated controlled release fertilizer, the increase in temperature accelerates the release of nutrients in the fertilizer, but under high temperature conditions, the nutrient requirements of plants are not increased with the increase in temperature. Thus, the nutrient controlled release period of the controlled release fertilizer under high temperature conditions is critical. Compared with comparative examples 1-3, the intelligent controlled release fertilizer prepared in example 4 can prolong the release period of nutrients under high temperature conditions.
The above results indicate that: the controlled release fertilizer prepared by the invention can intelligently respond to the change of temperature, and can accelerate the release of nutrients under the conditions of proper soil temperature and higher nutrient demand of plants; can slow down the release of nutrients under the condition of lower or higher soil environment temperature. The intelligent response to temperature change can be used for better synchronization with the nutrient requirements of plants.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims (8)

1. The temperature response nanogel is characterized by comprising a polymer A containing dynamic covalent bonds and a temperature-sensitive polymer B according to a mass ratio of 1: (1-10) preparing the material;
the polymer A containing dynamic covalent bonds is prepared by the following method:
dissolving 1-vinylimidazole in water, adding sodium hydroxide, stirring uniformly, heating to 90-100 ℃, adding cyclohexanol dissolved in ethanol, dripping a cross-linking agent solution under the condition of cooling and refluxing, continuing heating and stirring for 15-20min after dripping, and removing ethanol to obtain a polymer A containing dynamic covalent bonds;
the temperature-sensitive polymer B is prepared by the following method:
adding N-vinyl caprolactam and a cross-linking agent into deionized water to obtain a first mixed solution; dissolving diallyl ether in ethanol, adding ammonium persulfate, and uniformly mixing to obtain a second mixed solution; heating the first mixed solution to 75-85 ℃, adding the second mixed solution into the first mixed solution, and stirring for reacting for 4-5h to obtain a temperature-sensitive polymer B;
in the preparation method of the polymer A containing dynamic covalent bonds, the mass ratio of the added cyclohexyl alcohol to the added 1-vinyl imidazole is 1: (1-5);
in the preparation method of the temperature-sensitive polymer B, the mass ratio of the N-vinyl caprolactam, the diallyl ether and the ammonium persulfate is (5-10): (2.5-3): 1.
2. the temperature-responsive nanogel of claim 1 wherein the cross-linking agent is one or more of trimethylolpropane, vinyltriethoxysilane, N-methylenebisacrylamide, vinyltrimethoxysilane, triethylenediamine, 3-diethylaminopropylamine.
3. The method for preparing the temperature-responsive nanogel according to claim 1 or 2, comprising the steps of:
dissolving a polymer A containing dynamic covalent bonds in tetrahydrofuran solution, and heating to 75-85 ℃ to obtain a mixed solution A; dissolving the temperature-sensitive polymer B in absolute ethyl alcohol, and heating to 75-85 ℃ to obtain a mixed solution B; and (3) uniformly mixing the mixed solution A and the mixed solution B, adding a cross-linking agent under the stirring condition, keeping the temperature of 75-85 ℃ for reaction for 8-10 hours, filtering, washing and drying the product, and thus obtaining the temperature response nanogel.
4. The preparation method according to claim 3, wherein the crosslinking agent is one or more of trimethylolpropane, vinyltriethoxysilane, N-methylenebisacrylamide, vinyltrimethoxysilane, triethylenediamine, and 3-diethylaminopropylamine; the addition amount of the cross-linking agent is 3-10% of the total weight of the polymer A and the temperature-sensitive polymer B.
5. Use of the temperature-responsive nanogel of claim 1 or 2 in (1) or (2) as follows:
(1) Preparing a coating material capable of intelligently identifying the change of the rhizosphere environmental temperature;
(2) And preparing the intelligent controlled release fertilizer for controlling nutrient release in response to temperature.
6. The coating material capable of intelligently identifying the change of the rhizosphere ambient temperature is characterized by being prepared from the following raw materials in parts by weight:
10 parts of base film material and 1-5 parts of temperature response nano gel as claimed in claim 1 or 2.
7. The coating material of claim 6, wherein the base film is selected from one or more of polyurethane, sulfur, paraffin, epoxy, phenolic, bio-based phenolic.
8. The intelligent controlled release fertilizer capable of responding to temperature is characterized by being prepared by the following method:
spraying the coating material for intelligently identifying the change of the rhizosphere environmental temperature on the surface of the fertilizer particles according to the claims 6 or 7; the spraying amount of the coating material is 1.0-10.0% of the weight of the fertilizer particles.
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