CN113336604A - Recyclable self-repairing elastic bio-based coating material and preparation method thereof - Google Patents
Recyclable self-repairing elastic bio-based coating material and preparation method thereof Download PDFInfo
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- CN113336604A CN113336604A CN202110659530.7A CN202110659530A CN113336604A CN 113336604 A CN113336604 A CN 113336604A CN 202110659530 A CN202110659530 A CN 202110659530A CN 113336604 A CN113336604 A CN 113336604A
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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
- 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
- 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
Abstract
The invention discloses a recyclable self-repairing elastic bio-based coating material and a preparation method thereof. The recyclable self-repairing elastic bio-based coating material is prepared from the following raw materials in parts by weight: 100 parts of bio-based resin, 5-20 parts of dynamic modified material and 0.1-0.3 part of magnetic nano cellulose. The bio-based coating material can be applied to various different types of bio-based coated controlled release fertilizers, and the problem that holes and cracks are easy to appear in the production and use processes of the controlled release fertilizers to influence the controlled release effect is solved through the dynamic covalent bond self-repairing technology. Meanwhile, the preparation process is simple, the production cost is low, the controlled release fertilizer coating can be recycled, the production cost of the controlled release fertilizer is reduced, the waste of resources is avoided, and the pollution to the environment is reduced.
Description
Technical Field
The invention relates to the technical field of production of controlled release fertilizers, in particular to a recyclable self-repairing elastic bio-based coating material and a preparation method thereof.
Background
The fertilizer is the most basic and important substance input in agricultural production activities, and a large amount of fertilizers are applied to agricultural production every year in China, so that the soil fertility and the crop yield are greatly improved. However, the unreasonable application mode and the low nutrient utilization rate not only waste more fertilizer resources, but also cause a series of problems of soil degradation, environmental pollution and the like. The slow-release fertilizer prepared by wrapping a layer of high-molecular waterproof polymer film on the surface of the fertilizer can slowly release the nutrients of the fertilizer to the outside, and is an important technical way for improving the quality and the efficiency of the fertilizer. Most of film materials of the traditional sustained and controlled release fertilizer come from petrochemical products, and have the problems of high cost, non-renewable resources, difficult degradation and the like, thereby restricting the sustainable development of the industry. In recent years, the development of low-cost, renewable resources and easily degradable bio-based material coated controlled release fertilizer is expected to improve the problems, but still has the following problems:
(1) the coating material of the bio-based coated controlled release fertilizer is derived from biological materials such as vegetable oil, straws and the like, the bio-based coated coating has high brittleness, easy tearing and poor compactness, and most of the preparation processes of the bio-based coated controlled release fertilizer are that a fertilizer core is put in a coating machine to rotate, and then the coating material is continuously sprayed on the surface of the fertilizer so as to be uniformly coated on the surface of the fertilizer and cured to form a film. During the semi-solidification of the coating material, the fertilizer and the fertilizer are adhered together by the coating material and then separated, and the separation process can cause the tearing of the coating material or the uneven coating. On the other hand, the coating material can continuously rub and collide with the inner wall of the coating machine in the curing process, so that the fertilizer film shell is abraded, large pores and cracks appear, and the controlled release effect of the fertilizer is finally influenced;
(2) in order to obtain excellent nutrient controlled-release capacity, the bio-based controlled-release fertilizer coating mostly adopts thermosetting resin with a highly cross-linked structure, and the cured cross-linked structure makes the thermosetting resin coating material difficult to recycle, and the thermosetting resin coating material is remained in soil after the nutrients are released, thereby causing serious resource waste. Meanwhile, even if the coating is a degradable bio-based coating material, the degradation process is very slow, and the degradation process can generate harmful substances such as micro-plastics and the like, so that the environment is polluted, the human health is harmed, and the like.
Related patent CN112409077A discloses a bio-based coating material prepared by uniformly mixing agricultural straw liquefied matter and isocyanate according to different proportions, but the coating material has high brittleness, and a membrane shell is abraded due to friction and collision in the coating process; related patent CN108503427A discloses an interpenetrating network polymer polyurea/polyurethane resin coating material and a preparation method thereof, wherein liquid urea and a curing agent are firstly adopted to react to prepare a polyurea prepolymer, and then the polyurea prepolymer, polyol and the curing agent are uniformly mixed according to a proportion to be used as a coating material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a recyclable self-repairing elastic bio-based coating material and a preparation method thereof. The bio-based coating material can be applied to various different types of bio-based coated controlled release fertilizers, and the problem that holes and cracks are easy to appear in the production and use processes of the controlled release fertilizers to influence the controlled release effect is solved through the dynamic covalent bond self-repairing technology. Meanwhile, the preparation process is simple, the production cost is low, the controlled release fertilizer coating can be recycled, the production cost of the controlled release fertilizer is reduced, the waste of resources is avoided, and the environmental pollution is reduced.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a recyclable self-repairing elastic bio-based coating material, which is prepared from the following raw materials in parts by weight:
100 parts of bio-based resin, 5-20 parts of dynamic modified material and 0.1-0.3 part of magnetic nano cellulose.
Preferably, the bio-based resin is selected from one or more of bio-based polyurethane, bio-based epoxy resin and bio-based phenolic resin.
Preferably, the dynamic modification material is prepared by mixing a small molecular monomer A and a small molecular monomer B according to a molar ratio of 1: (1-5) preparing;
the micromolecule monomer A is one or more of phenylboronic acid, p-benzoquinone dioxime, diacetyl dioxime, bis (2-aminophenyl) disulfide and isophorone diisocyanate;
the micromolecular monomer B is one or more of calcium sulfate, copper chloride, magnesium sulfate and magnesium chloride.
More preferably, the preparation conditions of the dynamic modified material are as follows: placing the small molecular monomer A and the small molecular monomer B into a reaction bottle, dissolving the small molecular monomer A and the small molecular monomer B by acetone, stirring the mixture at the temperature of 40-80 ℃ for reaction for 10-15h, continuously introducing nitrogen to remove air and volatile acetone in the system, pouring out the residual mixed solution after the acetone is completely volatilized, and cooling the mixed solution to room temperature.
Preferably, the magnetic nanocellulose is prepared by the following method:
dissolving hydroxypropyl methylcellulose into water, adding mesoporous nano iron oxide powder, performing ultrasonic oscillation for 10 hours, taking out the hydroxypropyl methylcellulose-mesoporous nano iron oxide composite material, washing and drying to obtain the magnetic nano cellulose.
More preferably, the weight ratio of the hydroxypropyl methyl cellulose to the mesoporous nano iron oxide powder is (1-2): (0.1-0.5).
More preferably, the method for dissolving hydroxypropylmethylcellulose in water is: dispersing 1-2g hydroxypropyl methylcellulose in 20mL hot water, stirring to swell completely, adding 80mL cold water, and stirring to water temperature below room temperature to dissolve hydroxypropyl methylcellulose in water.
In a second aspect of the invention, the application of the self-repairing elastic bio-based coating material in preparing a controlled release fertilizer is provided.
The third aspect of the invention provides a coated controlled-release fertilizer, which comprises a fertilizer core and the self-repairing elastic bio-based coating material sprayed on the surface of the fertilizer core; the self-repairing elastic bio-based coating material accounts for 2-7% of the weight of the fertilizer core.
In a fourth aspect of the present invention, there is provided a method for preparing the coated controlled release fertilizer, comprising the steps of:
the self-repairing elastic bio-based coating material is placed in a spraying device, is uniformly sprayed on the surface of a rotating fertilizer core under the pressure of 0.2-0.4MPa, and is cured for 5-15 min.
The invention has the beneficial effects that:
(1) the bio-based coating material prepared by the invention has self-repairing capability, high elasticity and good toughness, effectively reduces the generation of holes and cracks in the production, transportation and application processes of the controlled release fertilizer, and greatly improves the controlled release effect.
(2) The preparation method has the advantages of simple preparation process, low energy consumption and cheap and easily-obtained modified materials, and is beneficial to promoting the further development of the controlled-release fertilizer industry.
(3) The bio-based coating material prepared by the invention can be recycled and reused after being used, so that the waste of resources is reduced, the harm to the environment is reduced, and the requirement of sustainable development is met. Meanwhile, the bio-based coating material can still maintain higher mechanical property in the process of recycling for many times, and provides a new direction for the treatment of the residual film shell of the bio-based controlled release fertilizer.
Drawings
FIG. 1: the infrared spectrum of the recyclable self-repairing elastic bio-based polyurethane coating material prepared in the embodiment 1 of the invention; as shown in figure 1, the coating material contains two characteristic groups of N-H and C-O, and the successful preparation of the bio-based polyurethane coating material is proved.
FIG. 2: the laser confocal fluorescence picture of the recyclable self-repairing elastic bio-based coating material prepared in the embodiment 1 of the invention; as can be seen from fig. 2, the magnetic nanocellulose was successfully added to the bio-based coating material and uniformly dispersed, and thus the bio-based coating material can be easily recovered and reused by magnetism.
FIG. 3: SEM pictures before and after the repair of the recyclable self-repairing elastic bio-based coating material prepared in the embodiment 1 of the invention; through SEM pictures, the existence of repair areas on the surface of the coating material, including the areas after repair and the areas undergoing repair, can be obviously observed. The good intermolecular fluidity enables molecules to spontaneously approach each other when the coating material is damaged, and dynamic bonds are reestablished, so that the damaged area is repaired.
FIG. 4: AFM schematic diagrams of an unmodified bio-based coating material (A) and a recyclable self-repairing elastic bio-based coating material (B); the micro-region Young's modulus of the bio-based coating material before and after modification by using the dynamic modification material and the magnetic nanocellulose is measured, and the Young's modulus is a representation of the difficulty degree of elastic deformation of an object, and the result shows that the Young's modulus of the recyclable elastic bio-based coating material prepared in the embodiment 1 of the invention is lower than that of an unmodified bio-based coating material (i.e. a bio-based polyurethane coating material), and the elasticity of the recyclable elastic bio-based coating material is obviously improved.
FIG. 5: the nutrient release curve of the recoverable self-repairing elastic bio-based coated controlled release fertilizer; through the nutrient release curve, the release period of the bio-based polyurethane coated controlled release fertilizer in example 1 is 49 days, and the release period of the bio-based epoxy resin coated controlled release fertilizer in example 2 is 70 days.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 introduced in the background art, the existing bio-based coating material has the problems of high brittleness, easy tearing, poor compactness and the like, and the coating is easy to tear, pores and cracks in the preparation process of the coated fertilizer; in addition, most of the existing bio-based controlled release fertilizer coatings are thermosetting resin with a highly cross-linked structure, the cured cross-linked structure makes the thermosetting resin coating material difficult to recycle, and the thermosetting resin coating material is remained in soil after nutrients are released, thereby causing serious resource waste.
Aiming at the problems, the invention realizes the original technical breakthrough from the following points:
(1) aiming at the limitations that the bio-based coating material has high brittleness, is easy to tear and has poor compactness and large pores and cracks are easy to appear due to tearing and collision of a coating in the preparation process of the bio-based coated controlled release fertilizer, the invention initiatively grafts the modifier containing one or more systems of dynamic covalent bonds, non-covalent bonds, metal coordination bonds and the like into the bio-based coating material to prepare the self-repairing elastic bio-based coating material which has good toughness and elasticity and can spontaneously repair the large pores and cracks. The molecules of the traditional thermosetting resin coating material are in a solid state and have poor fluidity, which is the main reason that the traditional thermosetting resin coating material has high brittleness and cannot be repaired after being damaged. Therefore, by grafting one or more of dynamic covalent bonds, non-covalent bonds and metal coordination bonds in the thermosetting resin network, the molecules with good fluidity and dynamics increase the toughness and elasticity of the bio-based material and reduce friction and breakage in the preparation process of the bio-based coated controlled release fertilizer. Meanwhile, the self-repairing capability of the bio-based coating is given, and the molecules with good fluidity can approach each other to re-establish dynamic bonds when large pores and cracks are formed, so that the damaged part is repaired.
(2) Aiming at the limitation that the crosslinked thermosetting resin coating cannot be recycled and reused, the invention creatively adds the magnetic nano-cellulose into the bio-based coating material. The added magnetic nano-cellulose not only improves the compactness of the bio-based coating, but also can recover residual fertilizer film shells applied in soil by magnetic action when ploughing, for example, a magnet with magnetism is added on the upper part of a rotary plough during ploughing, and the residual fertilizer film shells can be recovered by magnetic adsorption during ploughing due to the light texture of the fertilizer film shells. The dynamic covalent bond, non-covalent bond, metal coordination bond and other systems grafted in the bio-based membrane shell endow good fluidity among the membrane shell molecules, and the recovered membrane shell can be reused by simple cleaning, drying and pyrolysis of a membrane forming solution or bio-based resin products with other purposes.
The recyclable self-repairing elastic bio-based coating material prepared by the invention can be applied to different types of bio-based coated controlled release fertilizers such as polyurethanes, epoxy resins and the like. The dynamic covalent bond self-repairing technology creatively solves the problem that holes and cracks are easy to appear in the production and use processes of the controlled release fertilizer to influence the controlled release effect, meanwhile, the preparation process is simple, the production cost is low, the controlled release fertilizer coating can be recycled, the production cost of the controlled release fertilizer is reduced, the waste of resources is avoided, the pollution to the environment is reduced, and the method is an original bio-based coating controlled release material modification method with great technical breakthrough.
The invention provides a preparation method of a recyclable self-repairing elastic bio-based coating material, aiming at the problems which are difficult to solve in the existing modification method of the bio-based coating material introduced above, the recyclable self-repairing elastic bio-based coating material is prepared by adding a dynamic modification material which is similar to a rope structure and contains one or more systems of reversible dynamic covalent bonds, non-covalent bonds, metal coordination bonds and the like into the bio-based coating material, grafting the dynamic modification material to a main chain of the bio-based coating material as a side chain, and finally adding magnetic nano-cellulose.
The preparation method of the magnetic nanocellulose comprises the following steps: specifically, 1-2g of hydroxypropyl methyl cellulose is fully dispersed in 20mL of hot water, the mixture is stirred to completely swell the added product, then 80mL of cold water is added, the mixture is stirred until the water temperature is below room temperature, the hydroxypropyl methyl cellulose is dissolved in the water, then 0.1-0.5g of mesoporous nano iron oxide powder is added, ultrasonic oscillation is carried out for 10 hours, the hydroxypropyl methyl cellulose-mesoporous nano iron oxide composite material is taken out, washed and dried, and the magnetic nano cellulose is prepared.
The magnetic nano cellulose prepared by the method has good compatibility with the bio-based coating material, can be uniformly dispersed in the bio-based coating material, and is uniformly dispersed, so that the bio-based coating material can be easily recycled and reused through magnetism (figure 2).
The dynamic modified material is prepared by mixing the following components in a molar ratio of 1: and (1) preparing the micromolecule monomer A and the micromolecule monomer B. The method specifically comprises the following steps: placing the small molecular monomer A and the small molecular monomer B into a reaction bottle, dissolving the small molecular monomer A and the small molecular monomer B by acetone, stirring the mixture at the temperature of 40-80 ℃ for reaction for 10-15h, continuously introducing nitrogen to remove air and volatile acetone in the system, pouring out the residual mixed solution after the acetone is completely volatilized, and cooling the mixed solution to room temperature.
The micromolecule monomer A is one or more of phenylboronic acid, p-benzoquinone dioxime, diacetyl dioxime, bis (2-aminophenyl) disulfide and isophorone diisocyanate;
the micromolecular monomer B is one or more of calcium sulfate, copper chloride, magnesium sulfate and magnesium chloride.
For the dynamic modified material of the invention, the selection of the small molecular monomer A and the small molecular monomer B and the preparation method of the dynamic modified material are very key. According to the invention, the micromolecule monomer A and the micromolecule monomer B are optimized, the prepolymer containing dynamic covalent bonds is generated firstly by the polycondensation reaction of hydroxyl, amino and isocyanic acid radical groups in the micromolecule monomer A, metal ions in the micromolecule monomer B generate metal coordination at the dynamic covalent bonds, and the self-repairing and recycling capability of the bio-based coating material is endowed by the synergistic effect of the dynamic covalent bonds, the hydrogen bonds and the metal coordination bonds (figure 3). If the small molecular monomer A or the small molecular monomer B is added into the bio-based coating material independently, or the small molecular monomer A and the small molecular monomer B are added into the bio-based coating material according to the molar ratio of 1: (1-5) after simple physical mixing and coating treatment, it was found that coating tears, pores and cracks still occur during the preparation of the coated fertilizer, and the tears, pores and cracks that occur cannot be self-repaired.
The recyclable self-repairing elastic bio-based coating material has high elasticity and good toughness. The Young's modulus of the coating material is measured by using an atomic force microscope, the Young's modulus of a micro-area of the recyclable self-repairing elastic bio-based coating material is obviously lower than that of an unmodified bio-based coating material, the Young's modulus is a representation of the difficulty degree of elastic deformation of an object, and the modified Young's modulus is lower, so that the elasticity of the coating material is obviously improved, and the coating material can be bent and deformed without brittle fracture (figure 4). The used recyclable self-repairing elastic bio-based coating material is collected, can be made into a coating liquid or a bio-based resin product with other purposes after being cleaned, dried and pyrolyzed, and the mechanical property of the coating liquid can be recovered to be more than 80-90% of the original mechanical property after being recycled and reused for 5-10 times.
In conclusion, the recyclable self-repairing elastic bio-based coating material disclosed by the invention has the main innovation that: the modified bio-based coating material has the advantages of self-repairing capability, high elasticity and good toughness, effectively reduces the generation of holes and cracks in the production, transportation and application processes of the slow and controlled release fertilizer, and greatly improves the controlled release effect. And the prepared bio-based coating material can be recycled and reused after being used, so that the waste of resources is reduced, the harm to the environment is reduced, and the requirement of sustainable development is met. Meanwhile, the bio-based coating material can still maintain higher mechanical property in the process of recycling for many times.
The invention also provides a self-repairing elastic bio-based coated controlled release fertilizer with a recyclable coating, which is prepared by spraying the self-repairing elastic bio-based coated material on the surface of a fertilizer core; the self-repairing elastic bio-based coating material accounts for 2-7% of the weight of the fertilizer core.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, 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 of the present invention are all conventional in the art and commercially available. Wherein:
the bio-based polyurethane raw material, the bio-based phenolic resin raw material and the bio-based epoxy resin raw material can be prepared by the existing reported method or purchased as a commercial product. For example: the bio-based polyurethane raw material can be prepared from bio-based polyol and isocyanate by the method reported in the prior art.
Example 1:
in the embodiment, the recyclable self-repairing elastic bio-based polyurethane coating material is prepared by introducing dynamic oxime urethane bonds, hydrogen bonds and calcium coordination bonds into the bio-based polyurethane coating material, and the recyclable self-repairing elastic bio-based polyurethane coating controlled release fertilizer with the recyclable coating is provided. The preparation method comprises the following steps:
(1) fully dispersing 1g of hydroxypropyl methyl cellulose in 20mL of hot water, stirring to completely swell the added product, then adding 80mL of cold water, stirring until the water temperature is below room temperature, dissolving the hydroxypropyl methyl cellulose in the water, then adding 0.1g of mesoporous nano iron oxide powder, ultrasonically stirring for 10 hours, taking out the hydroxypropyl methyl cellulose-mesoporous nano iron oxide composite material, washing twice with deionized water, and then carrying out vacuum drying at 60 ℃ for 24 hours to prepare the magnetic nano cellulose.
(2) Mixing a mixture of 1:1 (the small molecular monomer A is composed of p-benzoquinone dioxime and isophorone diisocyanate according to a molar ratio of 1: 1) and a small molecular monomer B (calcium sulfate) are placed in a reaction bottle, dissolved by acetone, stirred and reacted for 10 hours at 50 ℃, nitrogen is continuously introduced to remove air and volatile acetone in the system, and after the acetone is completely volatilized, the residual mixed solution is poured out and cooled to room temperature to be used as a dynamic modification material for later use.
(3) Adding a dynamic modification material and magnetic nanocellulose into a bio-based polyurethane raw material, wherein the addition amount of the dynamic modification material is 5% of the mass of the bio-based polyurethane raw material, and the addition amount of the magnetic nanocellulose is 0.1% of the mass of the bio-based polyurethane raw material, mixing the components, and uniformly stirring to obtain the recyclable self-repairing elastic bio-based polyurethane coating material.
(4) 500g of urea is placed in a coating machine, preheating is carried out for 10min under the process conditions that the rotation speed is 30r/min and the temperature is 60 ℃, the recyclable self-repairing elastic bio-based coating material is placed in a spraying device, the recyclable self-repairing elastic bio-based coating material is uniformly sprayed on the surface of rotating urea under the pressure of 0.2MPa, curing is carried out for 5min, spraying is carried out for 3 times in total, the spraying amount of each time is 1% of the mass of the urea, and the recyclable self-repairing elastic bio-based polyurethane coated controlled release fertilizer with the coating thickness of 3% is obtained, wherein the controlled release period of the fertilizer is 49 days (figure 5).
Example 2:
in the embodiment, the recyclable self-repairing elastic bio-based epoxy resin coating material is prepared by introducing dynamic borate bonds, hydrogen bonds and magnesium coordination bonds into the bio-based epoxy resin coating material, and the recyclable self-repairing elastic bio-based epoxy resin coating controlled release fertilizer with the recyclable coating is provided. The preparation method comprises the following steps:
(1) fully dispersing 1.5g of hydroxypropyl methyl cellulose in 20mL of hot water, stirring to completely swell the added product, then adding 80mL of cold water, stirring until the water temperature is below room temperature, dissolving the hydroxypropyl methyl cellulose in the water, then adding 0.2g of mesoporous nano iron oxide powder, ultrasonically stirring for 10 hours, taking out the hydroxypropyl methyl cellulose-mesoporous nano iron oxide composite material, washing with deionized water twice, and then vacuum-drying at 60 ℃ for 24 hours to prepare the magnetic nano cellulose.
(2) Mixing a mixture of 1: 2, placing the small molecular monomer A (phenylboronic acid) and the small molecular monomer B (magnesium chloride) in a reaction bottle, dissolving the small molecular monomer A and the small molecular monomer B with acetone, stirring the mixture at the temperature of 60 ℃ for reaction for 12 hours, continuously introducing nitrogen to remove air and volatile acetone in the system, pouring out the residual mixed solution after the acetone is completely volatilized, and cooling the mixed solution to room temperature to be used as a dynamic modification material for later use.
(3) Adding a dynamic modification material and magnetic nanocellulose into a bio-based epoxy resin raw material, wherein the addition amount of the dynamic modification material is 10% of the mass of the bio-based epoxy resin raw material, the addition amount of the magnetic nanocellulose is 0.2% of the mass of the bio-based epoxy resin raw material, mixing the components of the bio-based epoxy resin raw material, the dynamic modification material and the magnetic nanocellulose, uniformly stirring, and taking the mixture as a recyclable elastic bio-based epoxy resin coating material.
(4) 500g of urea is placed in a coating machine, preheating is carried out for 15min under the process conditions that the rotation speed is 40r/min and the temperature is 65 ℃, the recyclable self-repairing elastic bio-based coating material is placed in a spraying device, the recyclable self-repairing elastic bio-based coating material is uniformly sprayed on the surface of rotating urea under the pressure of 0.3MPa, curing is carried out for 10min, 5 times of spraying are carried out in total, the spraying amount of each time is 1% of the mass of the urea, and the recyclable self-repairing elastic bio-based epoxy resin coated controlled release fertilizer with the coating thickness of 5% is obtained, wherein the controlled release period of the fertilizer is 70 days (figure 5).
Example 3:
in the embodiment, the recyclable self-repairing elastic bio-based phenolic resin coating material is prepared by introducing dynamic disulfide bonds, hydrogen bonds and copper coordination bonds into the bio-based phenolic resin coating material, and the recyclable self-repairing elastic bio-based phenolic resin coating controlled release fertilizer with the recyclable coating is provided. The preparation method comprises the following steps:
(1) fully dispersing 2g of hydroxypropyl methyl cellulose in 20mL of hot water, stirring to completely swell the added product, then adding 80mL of cold water, stirring until the water temperature is below room temperature, dissolving the hydroxypropyl methyl cellulose in the water, then adding 0.3g of mesoporous nano iron oxide powder, ultrasonically stirring for 10 hours, taking out the hydroxypropyl methyl cellulose-mesoporous nano iron oxide composite material, washing twice with deionized water, and then carrying out vacuum drying at 60 ℃ for 24 hours to obtain the magnetic nano cellulose.
(2) Mixing a mixture of 1: 3 (the small molecular monomer A is composed of bis (2-aminophenyl) disulfide and isophorone diisocyanate according to a molar ratio of 1: 1) and the small molecular monomer B (copper sulfate) are placed in a reaction bottle, dissolved by acetone, stirred and reacted for 15 hours at 50 ℃, nitrogen is continuously introduced to remove air and volatile acetone in the system, and after the acetone is volatilized, the residual mixed solution is poured out and cooled to room temperature to be used as a dynamic modification material for later use.
(3) Adding a dynamic modification material and magnetic nanocellulose into a bio-based phenolic resin raw material, wherein the addition amount of the dynamic modification material is 20% of the mass of the bio-based phenolic resin raw material, the addition amount of the magnetic nanocellulose is 0.3% of the mass of the bio-based phenolic resin raw material, mixing the components of the bio-based phenolic resin raw material, the dynamic modification material and the magnetic nanocellulose, and uniformly stirring to obtain the recyclable elastic bio-based phenolic resin coating material.
(4) 500g of urea is placed in a coating machine, preheating is carried out for 20min under the process conditions that the rotation speed is 45r/min and the temperature is 70 ℃, the recyclable self-repairing elastic bio-based coating material is placed in a spraying device, the recyclable self-repairing elastic bio-based coating material is uniformly sprayed on the surface of rotating urea under the pressure of 0.4MPa, curing is carried out for 15min, spraying is carried out for 7 times in total, the spraying amount of each time is 1% of the mass of the urea, and the recyclable self-repairing elastic bio-based phenolic resin coated controlled release fertilizer with the coating thickness of 7% is obtained, wherein the controlled release period of the fertilizer is 120 days.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A recyclable self-repairing elastic bio-based coating material is characterized by being prepared from the following raw materials in parts by weight:
100 parts of bio-based resin, 5-20 parts of dynamic modified material and 0.1-0.3 part of magnetic nano cellulose.
2. The self-healing elastomeric bio-based coating material of claim 1, wherein the bio-based resin is selected from one or more of bio-based polyurethane, bio-based epoxy, and bio-based phenolic.
3. The self-repairing elastic bio-based coating material of claim 1, wherein the dynamic modification material is prepared by mixing a small molecular monomer A and a small molecular monomer B according to a molar ratio of 1: (1-5) preparing;
the micromolecule monomer A is one or more of phenylboronic acid, p-benzoquinone dioxime, diacetyl dioxime, bis (2-aminophenyl) disulfide and isophorone diisocyanate;
the micromolecular monomer B is one or more of calcium sulfate, copper chloride, magnesium sulfate and magnesium chloride.
4. The self-repairing elastic bio-based coating material of claim 3, wherein the preparation conditions of the dynamic modification material are as follows: placing the small molecular monomer A and the small molecular monomer B into a reaction bottle, dissolving the small molecular monomer A and the small molecular monomer B by acetone, stirring the mixture at the temperature of 40-80 ℃ for reaction for 10-15h, continuously introducing nitrogen to remove air and volatile acetone in the system, pouring out the residual mixed solution after the acetone is completely volatilized, and cooling the mixed solution to room temperature.
5. The self-repairing elastic bio-based coating material of claim 1, wherein the magnetic nanocellulose is prepared by the following method:
dissolving hydroxypropyl methylcellulose into water, adding mesoporous nano iron oxide powder, performing ultrasonic oscillation for 10 hours, taking out the hydroxypropyl methylcellulose-mesoporous nano iron oxide composite material, washing and drying to obtain the magnetic nano cellulose.
6. The self-repairing elastic bio-based coating material of claim 5, wherein the weight ratio of the hydroxypropyl methyl cellulose to the mesoporous nano iron oxide powder is (1-2): (0.1-0.5).
7. The self-repairing elastic bio-based coating material of claim 5, wherein the method for dissolving hydroxypropyl methyl cellulose in water is as follows: hydroxypropyl methylcellulose 1-2g is dispersed in 20mL hot water, stirred to swell completely, then 80mL cold water is added, and stirred until the water temperature is below room temperature, so that hydroxypropyl methylcellulose can be dissolved in water.
8. Use of the self-healing elastic bio-based coating material of any one of claims 1 to 7 in the preparation of controlled release fertilizers.
9. A coated controlled release fertilizer, which is characterized by comprising a fertilizer core and the self-repairing elastic bio-based coating material of any one of claims 1 to 7 sprayed on the surface of the fertilizer core; the self-repairing elastic bio-based coating material accounts for 2-7% of the weight of the fertilizer core.
10. The method of preparing the coated controlled release fertilizer of claim 9, comprising the steps of:
the self-repairing elastic bio-based coating material of any one of claims 1 to 7 is uniformly sprayed on the surface of a rotating fertilizer core under the pressure of 0.2 to 0.4MPa, and is cured for 5 to 15 min.
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