CN113976082B - Magnetic nanoparticle as well as preparation method and application thereof - Google Patents
Magnetic nanoparticle as well as preparation method and application thereof Download PDFInfo
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- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000012838 magnetic nanoparticle method Methods 0.000 title description 2
- 238000001179 sorption measurement Methods 0.000 claims abstract description 138
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 19
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- 238000000034 method Methods 0.000 claims description 46
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 25
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005869 Pyraclostrobin Substances 0.000 claims description 11
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 claims description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 10
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- VMNULHCTRPXWFJ-UJSVPXBISA-N enoxastrobin Chemical compound CO\C=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)\C=C\C1=CC=C(Cl)C=C1 VMNULHCTRPXWFJ-UJSVPXBISA-N 0.000 claims description 8
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- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a magnetic nanoparticle, a preparation method and application thereof, wherein the magnetic nanoparticle comprises the following components: a core formed from ferroferric oxide; a shell covering at least a portion of the surface of the core, the shell being formed from repeating multi-ring units, wherein the multi-ring units are selected from one of formula I, formula II, or formula III. The magnetic nanoparticle has the advantages of good stability, large adsorption capacity, easy adsorption and separation and the like.
Description
Technical Field
The invention relates to the field of chemistry, in particular to magnetic nanoparticles, and a preparation method and application thereof.
Background
Magnetic solid phase extraction is a dispersive solid phase extraction technique with magnetic or magnetizable material as adsorbent. The adsorbent is in a dispersion state, so that the sample quantity capable of being processed is large, the extraction is rapid, and the adsorbent can be recycled. By Fe 3 O 4 The nano particles are nuclear bodies, have stable chemical structure and are easy to surface modify. The different shells outside the nucleus body can be divided into: magnetic carbon nanocomposite, magnetic molecularly imprinted material, magnetic metal organic framework, magnetic covalent organic framework, and the like.
The problem of residual methoxy acrylic acid ester bactericides and the problem of environmental safety are increasingly serious, the methoxy acrylic acid ester bactericides widely exist in foods, and how to extract the methoxy acrylic acid ester bactericides from complex matrixes is one of the key points of the detection of the methoxy acrylic acid ester bactericides. The magnetic covalent organic framework material (Magnetic Covalent Organic Frameworks, M-COFs) is a porous crystalline organic framework material, and has the characteristics of small density, large specific surface area, good thermal stability and chemical stability, adjustable aperture and structure, high saturation magnetization and the like, and can quickly realize the separation of a target object in a complex sample, so that the defect that the covalent organic framework material is difficult to separate and recycle is overcome.
Therefore, there is a need to develop a magnetic adsorbent for extracting methoxy acrylate based bactericides from different sample substrates.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention aims to provide the magnetic nanoparticle which has the advantages of good stability, large adsorption capacity, easiness in adsorption and separation and the like. The inventors take covalent organic framework materials (Covalent Organic Frameworks, COFs) as raw materials to coat magnetic Fe 3 O 4 An organic shell with a porous structure is formed on the surface, and 11 methoxy acrylic acid ester bactericides existing in a complex sample are efficiently enriched by adopting the magnetic nanoparticles, so that the adsorption capacity is strong and quick.
Thus, according to one aspect of the present invention, there is provided a magnetic nanoparticle. According to an embodiment of the present invention, the magnetic nanoparticle includes: a core formed from ferroferric oxide; a shell covering at least a portion of the surface of the core, the shell being formed from repeating multi-ring units, wherein the multi-ring units are selected from one of formula I, formula II, or formula III.
According to the magnetic nanoparticle provided by the embodiment of the invention, ferroferric oxide is taken as a nucleus body, so that the magnetic nanoparticle is magnetic and is easy to adsorb and separate, and the problems of poor stability, inconvenient use and operation, difficult recycling and the like of a covalent organic framework material are solved; the shell is formed by the multi-ring units in the formulas I-III, is a magnetic covalent organic framework material, has larger specific surface area and good stability, has wide application prospect in the aspect of enriching trace pollutants, and is particularly suitable for extracting methoxy acrylic acid ester bactericides. In the pretreatment process, the magnetic nanoparticles greatly shorten the pretreatment time, and the adsorption and desorption of the p-methoxy acrylic acid ester bactericide can be completed within a few minutes by using a very small amount of organic reagent, so that the magnetic nanoparticles have the advantages of simplicity in operation, time saving, high efficiency, environment friendliness and the like.
In addition, the magnetic nanoparticle according to the above embodiment of the present invention may further have the following additional technical features:
according to an embodiment of the invention, the average pore diameter of the shell is 1.0-2.5 nm, and the thickness is 20-30 nm.
According to an embodiment of the invention, the specific surface area of the shell is 200-370 m 2 ·g -1 Preferably 250 to 370m 2 ·g -1 。
According to an embodiment of the present invention, the shell has crystal diffraction peaks in the X-ray powder diffraction data at 2θ of 30.36 °, 35.47 °, 43.13 °, 53.25 °, 57.06 ° and 62.70 °.
According to an embodiment of the present invention, the particle size of the core is 200 to 300nm.
According to the embodiment of the invention, the saturated adsorption quantity of the magnetic nanoparticle to the methoxy acrylic bactericide is 30-60 mg.g -1 Preferably 40 to 55 mg.g -1 。
According to the embodiment of the invention, the adsorption equilibrium time of the magnetic nanoparticles on the methoxy acrylic bactericide is 20-30 minutes.
According to the embodiment of the invention, the methoxy acrylic bactericide is at least one selected from azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, kresoxim-methyl, trifloxystrobin, enestroburin, coumoxystrobin and chloropyrifos.
According to another aspect of the present invention, there is provided a method of preparing the aforementioned magnetic nanoparticles. According to an embodiment of the invention, the method comprises: first contacting a solution containing an amino monomer with ferroferric oxide nanoparticles and performing first stirring so as to obtain a first mixture; and contacting the first mixture with aldehyde-based monomers and a catalyst for the second time and performing the second stirring so as to obtain the magnetic nanoparticles.
According to the preparation method provided by the embodiment of the invention, the shell synthesized by the amino monomer and the aldehyde monomer is used for coating the magnetic ferroferric oxide nano particles to form the magnetic covalent organic framework shell, and the prepared magnetic nano particles have magnetism and are easy to adsorb and separate, so that the problems of poor stability, inconvenient use and operation, difficult recycling and the like of covalent organic framework materials are solved, and the magnetic nano particles have larger specific surface area, good stability and wide application prospect in the aspect of enriching trace pollutants. In addition, the method has simple requirements on test equipment, is simple to operate, and is easy to popularize and apply.
According to an embodiment of the invention, the amino monomer is 4,4' -triaminetrityl methane (TAPM) or tetra- (4-aminostyrene) Ethylene (ETTA),
according to an embodiment of the invention, the aldehyde monomer is 3,3', 5' -tetra-aldehyde Biphenyl (BTA), 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde (Tp) or 2, 5-dihydroxyterephthalaldehyde (Dt),
according to an embodiment of the present invention, the molar ratio of the amino monomer to the aldehyde monomer is (1-2): 1, preferably 4:3.
According to an embodiment of the present invention, the mass concentration of the solution containing the amino monomer is 1 to 2%.
According to the embodiment of the invention, the mass ratio of the amino monomer to the ferroferric oxide is (0.5-1): 1.
according to an embodiment of the invention, the catalyst is acetic acid.
According to the embodiment of the invention, the second contact is ultrasonic oscillation for 15-30 minutes.
According to an embodiment of the present invention, the first stirring time is 15 to 45 minutes.
According to an embodiment of the present invention, the second stirring time is 100 to 140 minutes.
According to an embodiment of the invention, the temperature of both the first stirring and the second stirring is 50-70 ℃, preferably 60 ℃; the rotation speed is 400 to 1000rpm, preferably 500 to 800rpm.
According to yet another aspect of the present invention, there is provided a method of adsorbing a methoxy acrylate based bactericide. According to an embodiment of the invention, the method is performed using the aforementioned magnetic nanoparticles. Therefore, the method has the advantages of large adsorption capacity and high adsorption speed, is easy to adsorb and separate, and can rapidly and efficiently extract the methoxy acrylic acid ester bactericide from complex samples. In the pretreatment process, the magnetic nanoparticles greatly shorten the pretreatment time, and the adsorption and desorption of the p-methoxy acrylic acid ester bactericide can be completed within a few minutes by using a very small amount of organic reagent, so that the magnetic nanoparticles have the advantages of simplicity in operation, time saving, high efficiency, environment friendliness and the like.
According to an embodiment of the present invention, the saturated adsorption amount of the magnetic nanoparticles is 30 to 60 mg.g -1 Preferably 40 to 55 mg.g -1 。
According to the embodiment of the invention, the adsorption equilibrium time of the magnetic nanoparticles on the methoxy acrylic bactericide is 20-30 minutes.
According to the embodiment of the invention, the methoxy acrylic bactericide is at least one selected from azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, kresoxim-methyl, trifloxystrobin, enestroburin, coumoxystrobin and chloropyrifos.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows a schematic representation of a magnetic nanoparticle according to one embodiment of the present invention, wherein A and B are Fe 3 O 4 And Fe (Fe) 3 O 4 SEM image of BTA-TAPM; c and D are Fe 3 O 4 And Fe (Fe) 3 O 4 TEM image of @ BTA-TAPM; e is FT-IR spectrogram; f is a hysteresis loop diagram; g is an X-ray diffraction pattern; h is a thermogravimetric analysis chart; i and J are respectively a nitrogen adsorption-desorption isotherm diagram and a pore size distribution diagram;
FIG. 2 shows a magnetic nanoparticle attraction according to one embodiment of the invention, wherein A is a static attraction and B is a dynamic attraction;
FIG. 3 shows a schematic diagram of a Langmuir isotherm adsorption model of a methoxy acrylate biocide in accordance with one embodiment of the invention;
FIG. 4 shows a schematic diagram of a Freundlich isotherm adsorption model of a methoxy acrylate based biocide in accordance with one embodiment of the invention;
figure 5 shows a schematic representation of the magnetic nanoparticle recovery results according to one embodiment of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
It should be noted that the terms "first," "second," and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying a number of technical features being indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. Further, in the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
According to one aspect of the present invention, there is provided a magnetic nanoparticle. According to an embodiment of the present invention, the magnetic nanoparticle includes: a core formed from ferroferric oxide; a shell covering at least a portion of the surface of the core, the shell being formed from repeating multi-ring units, wherein the multi-ring units are selected from one of formula I, formula II, or formula III.
According to the magnetic nanoparticle provided by the embodiment of the invention, ferroferric oxide is taken as a nucleus body, so that the magnetic nanoparticle is magnetic and is easy to adsorb and separate, and the problems of poor stability, inconvenient use and operation, difficult recycling and the like of a covalent organic framework material are solved; the shell is formed by the multi-ring units in the formulas I-III, is a magnetic covalent organic framework material, has larger specific surface area and good stability, has wide application prospect in the aspect of enriching trace pollutants, and is particularly suitable for extracting methoxy acrylic acid ester bactericides. In the pretreatment process, the magnetic nanoparticles greatly shorten the pretreatment time, and the adsorption and desorption of the p-methoxy acrylic acid ester bactericide can be completed within a few minutes by using a very small amount of organic reagent, so that the magnetic nanoparticles have the advantages of simplicity in operation, time saving, high efficiency, environment friendliness and the like.
The shell of the embodiment of the invention is of a porous net structure, and the thicker the thickness is, the more the layer number among the repeated units of the shell material is, and the larger the adsorption capacity is. According to an embodiment of the invention, the average pore diameter of the shell is 1.0-2.5 nm, and the thickness is 20-30 nm. Therefore, the p-methoxy acrylic acid ester bactericide has a good adsorption effect, wherein the average pore diameter is 1.0-2.5 nm and is larger than the molecular diameter of a target object, a space embedding effect can be formed between the p-methoxy acrylic acid ester bactericide and the target object, and the p-methoxy acrylic acid ester bactericide is easy to adsorb.
According to an embodiment of the invention, the specific surface area of the shell is 200-370 m 2 ·g -1 Preferably 250 to 370m 2 ·g -1 . Thus, the specific surface area is large and the adsorption capacity is high.
According to an embodiment of the present invention, the shell has crystal diffraction peaks in the X-ray powder diffraction data at 2θ of 30.36 °, 35.47 °, 43.13 °, 53.25 °, 57.06 ° and 62.70 °. The characteristic peaks and Fe with spinel structure 3 O 4 Matching with each other, thereby proving Fe 3 O 4 Is successfully synthesized and Fe 3 O 4 The original crystal structure is still maintained after the shell is coated. Thus, the magnetic nanoparticle has both ferroferric oxide and a stable crystal form of a magnetic covalent organic framework material.
According to an embodiment of the present invention, the particle size of the core is 200 to 300nm. Thus, the magnetic nanoparticles have large specific surface area and strong adsorption capacity.
According to the embodiment of the invention, the saturated adsorption quantity of the magnetic nanoparticle to the methoxy acrylic bactericide is 30-60 mg.g -1 Preferably 40 to 55 mg.g -1 . Therefore, the magnetic nanoparticles have strong adsorption capacity, and can efficiently extract methoxy acrylic acid ester bactericides in complex samples.
According to the embodiment of the invention, the adsorption equilibrium time of the magnetic nanoparticles on the methoxy acrylic bactericide is 20-30 minutes. Therefore, the magnetic nanoparticles have high adsorption rate, and can rapidly extract methoxy acrylic acid ester bactericides in complex samples.
According to the embodiment of the invention, the methoxy acrylic bactericide is at least one selected from azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, kresoxim-methyl, trifloxystrobin, enestroburin, coumoxystrobin and chloropyrifos.
According to another aspect of the present invention, there is provided a method of preparing the aforementioned magnetic nanoparticles. According to an embodiment of the invention, the method comprises: first contacting a solution containing an amino monomer with ferroferric oxide nanoparticles and performing first stirring so as to obtain a first mixture; and contacting the first mixture with aldehyde-based monomers and a catalyst for the second time and performing the second stirring so as to obtain the magnetic nanoparticles.
According to the preparation method provided by the embodiment of the invention, the shell synthesized by the amino monomer and the aldehyde monomer is used for coating the magnetic ferroferric oxide nano particles to form the magnetic covalent organic framework shell, and the prepared magnetic nano particles have magnetism and are easy to adsorb and separate, so that the problems of poor stability, inconvenient use and operation, difficult recycling and the like of covalent organic framework materials are solved, and the magnetic nano particles have larger specific surface area, good stability and wide application prospect in the aspect of enriching trace pollutants. In addition, the method has simple requirements on test equipment, is simple to operate, and is easy to popularize and apply.
According to an embodiment of the invention, the amino monomer is 4,4' -triaminetrityl methane (TAPM) or tetra- (4-aminostyrene) Ethylene (ETTA). According to an embodiment of the invention, the aldehyde monomer is 3,3', 5' -tetra-aldehyde Biphenyl (BTA), 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde (Tp) or 2, 5-dihydroxyterephthalaldehyde (Dt),
according to an embodiment of the present invention, the molar ratio of the amino monomer to the aldehyde monomer is (1-2): 1, preferably 4:3. The two monomers which participate in the reaction in this ratio are able to react to the greatest extent to completion.
According to an embodiment of the present invention, the mass concentration of the solution containing the amino monomer is 1 to 2%. The mass concentration can ensure that the Schiff base reaction can be smoothly carried out.
According to the embodiment of the invention, the mass ratio of the amino monomer to the ferroferric oxide is (0.5-1): 1. the mass concentration can ensure that the Schiff base reaction can be smoothly carried out.
According to an embodiment of the invention, the catalyst is acetic acid. Therefore, the catalyst has good catalytic effect and high reaction rate. According to some embodiments of the invention, acetic acid is added in an amount of 200. Mu.L to 1mL.
According to the embodiment of the invention, the second contact is ultrasonic oscillation for 15-30 minutes. Thereby, a stable amino monomer solution is formed.
According to an embodiment of the present invention, the first stirring time is 15 to 45 minutes. According to an embodiment of the present invention, the second stirring time is 100 to 140 minutes. Thus, the reaction is facilitated to be fully carried out, and the yield of the product is high.
According to an embodiment of the invention, the temperature of both the first stirring and the second stirring is 50-70 ℃, preferably 60 ℃; the rotation speed is 400 to 1000rpm, preferably 500 to 800rpm.
Here, in order to facilitate understanding of the above-described method of preparing the aforementioned magnetic nanoparticles, there is provided a general method of preparing the aforementioned magnetic nanoparticles, the method comprising:
(1) Adding an amino monomer into a solvent, and dispersing to form a stable solution;
(2) Adding magnetic ferroferric oxide nano particles into the solution obtained in the step (1), and performing ultrasonic oscillation for 20min;
(3) Heating the solution obtained in the step (2) in a water bath, and mechanically stirring for 30min at the temperature of 60 ℃;
(4) Slowly dropwise adding an aldehyde monomer solution into the solution obtained in the step (3), slowly dropwise adding an acetic acid solution as a catalyst after the dropwise adding is finished, and controlling the temperature of the whole stirring system to be 60 ℃ for reacting for 2 hours to obtain a crude product;
(5) And (3) matching the crude product obtained in the step (4) with a strong magnet, sequentially cleaning with methanol, acetonitrile and aqueous solution until no supernatant is clear and no impurity is present, and putting the mixture into an oven to be dried at 60 ℃ to obtain the magnetic covalent organic framework material.
According to the embodiment of the invention, tetrahydrofuran is used as the solvent of the amino monomer, and the ferroferric oxide and the two monomers are well dispersed in the solvent, so that the full contact of a reaction system is ensured, and a good reaction effect can be obtained.
According to yet another aspect of the present invention, there is provided a method of adsorbing a methoxy acrylate based bactericide. According to an embodiment of the invention, the method is performed using the aforementioned magnetic nanoparticles. Therefore, the method has the advantages of large adsorption capacity and high adsorption speed, is easy to adsorb and separate, and can rapidly and efficiently extract the methoxy acrylic acid ester bactericide from complex samples. In the pretreatment process, the magnetic nanoparticles greatly shorten the pretreatment time, and the adsorption and desorption of the p-methoxy acrylic acid ester bactericide can be completed within a few minutes by using a very small amount of organic reagent, so that the magnetic nanoparticles have the advantages of simplicity in operation, time saving, high efficiency, environment friendliness and the like.
According to the embodiment of the invention, the saturated adsorption quantity of the magnetic nanoparticle to the methoxy acrylic bactericide is 30-60 mg.g -1 Preferably 40 to 55 mg.g -1 . Therefore, the magnetic nanoparticles have strong adsorption capacity, and can efficiently extract methoxy acrylic acid ester bactericides in complex samples.
According to the embodiment of the invention, the adsorption equilibrium time of the magnetic nanoparticles on the methoxy acrylic bactericide is 20-30 minutes. Therefore, the magnetic nanoparticles have high adsorption rate, and can rapidly extract methoxy acrylic acid ester bactericides in complex samples.
According to the embodiment of the invention, the methoxy acrylic bactericide is at least one selected from azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, kresoxim-methyl, trifloxystrobin, enestroburin, coumoxystrobin and chloropyrifos.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and are not to be construed as limiting the invention.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used are not manufacturer specific and are conventional products commercially available, for example, from Sigma company.
Example 1
In this embodiment, the magnetic nanoparticle is prepared by using 4,4' -triaminetrityl methane as an amino monomer and 3,3', 5' -tetra-aldehyde biphenyl as an aldehyde monomer, and the specific method is as follows:
(1) Dissolving monomer 4,4' -triamino triphenylmethane (173.6 mg,0.6 mmol) in tetrahydrofuran (22 mL) according to a mass ratio of 1:100, adding magnetic ferroferric oxide nano particles (the mass ratio of the magnetic ferroferric oxide nano particles to the amino monomer is 1:1.7), and carrying out ultrasonic oscillation for 20min;
(2) And then mechanically stirring the solution in a water bath for 30min, controlling the temperature at 60 ℃ and the rotating speed at 1000rpm, so that the whole stirring system is completely and uniformly mixed.
(3) Dissolving 3,3', 5' -tetra-aldehyde biphenyl (119.8 mg,0.45 mmol) in tetrahydrofuran (8 mL), uniformly mixing, slowly and dropwise adding into the stirring system of the step (2), and slowly adding the aldehyde monomer solution after the addition is completedSlowly dropwise adding 1mL of acetic acid solution as a reaction catalyst, and keeping the whole system to react for 2 hours at 60 ℃ to obtain a crude product; (4) The crude product is respectively matched with methanol, acetonitrile and aqueous solution through strong magnet, repeatedly cleaned until supernatant is clear, and then is put into an oven for drying at 60 ℃ for 12 hours, thus obtaining magnetic gray powder particles Fe 3 O 4 The reaction formula @ BTA-TAPM is as follows:
example 2
In this example, nanoparticles were prepared according to the method of example 1, except that Dt was an amino monomer, the reaction formula was as follows, and the prepared nanoparticles were Fe 3 O 4 @Dt-TAPM。
Example 3
In this example, nanoparticles were prepared according to the method of example 1, except that Tp was used as an amino monomer, ETTA was used as an aldehyde monomer, and the reaction formula was as follows, and the prepared nanoparticles were Fe 3 O 4 @Tp-ETTA。
Example 4
Magnetic covalent organic framework nanomaterials (Fe 3 O 4 Detailed characterization experiments were performed on @ COF (BTA-TAPM)) to demonstrate the successful preparation of magnetic nanomaterials and their excellent physicochemical properties. The specific contents are as follows:
1. observation of Fe by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) 3 O 4 Morphology and internal structure of nanoparticle and magnetic COF, as shown in fig. 1A and 1B, fe 3 O 4 Nanoparticles and magnetic propertiesThe structure of the COF is regular sphere and monodispersed, and the sphere structure has the advantage of large specific surface area. Therefore, it can significantly increase the number of sites of action of the adsorbent, thereby enhancing the adsorption effect of the adsorbent on the target.
In addition, fe 3 O 4 The diameter of the nanoparticle is about 250nm, in contrast to the increase in diameter of the magnetic COF by about 50nm. As can be seen from FIG. 1D, fe 3 O 4 The @ COF has an obvious core-shell structure, and the black solid inside is a magnetic core, which indicates that the adsorbent has good magnetism. The outer light gray coating is a COF coating, and is the same as the Fe of FIG. 1C 3 O 4 In contrast, the core-shell thickness of the magnetic COF is about 24nm, which indicates that the COF is successfully modified on the surface of the magnetic core, and is also a key point for ensuring that the adsorbent can adsorb target substances.
2. Fourier transform infrared spectrum is adopted for Fe 3 O 4 And magnetic nano material Fe 3 O 4 Analysis of the chemical structure and composition of @ COF (BTA-TAPM) shows that the particles have a transmittance of 4000 to 500cm as shown in FIG. 1E -1 Measurements were made in range. At Fe 3 O 4 3425, 1615 and 1403cm in the spectrum of (C) -1 The peak at which indicates the presence of a carboxyl function; fe compared with spectra of two monomers BTA and TAPM 3 O 4 The spectrum of @ BTA-TAPM is 586cm -1 There is a distinct adsorption band due to Fe 3 O 4 The Fe-O-Fe vibration of the nanoparticles also showed that the magnetic COF had been successfully magnetized; the absorption peak of the aromatic C=C unit structure was 1499cm -1 。1261cm -1 The signal peak at is designated as C-N bond stretch; in addition, at 1622cm -1 And 3366cm -1 Two characteristic peaks appear at the position, which are related to C=N and N-H stretching vibration, and indicate that polycondensation reaction occurs between two monomers and a magnetic core, and the magnetic covalent organic framework material with a COF coated core-shell structure is finally formed based on the encapsulation and formation of the magnetic nano particles on the amine connection structure.
3. Magnetic properties of the adsorbents were evaluated using a Vibrating Sample Magnetometer (VSM) and the results are shown in FIG. 1F, fe 3 O 4 And Fe (Fe) 3 O 4 Saturation magnetization of @ COFs, respectively61.1 and 24.0emu g -1 As clearly seen in the figure, the COF is found to be Fe due to magnetism 3 O 4 The COF coating is formed on the surface of the magnetic material, so that the magnetic property of the magnetic material is reduced, but the magnetic material can be rapidly separated in solution within 10 seconds under the action of an external magnetic field, fe 3 O 4 The high saturation magnetization of BTA-tacm is sufficient for separation from the sample matrix solution.
4. As shown in FIG. 1G, the synthesized Fe was characterized by XRD pattern 3 O 4 And Fe (Fe) 3 O 4 Crystallinity and structure of @ BTA-TAPM, fe 3 O 4 The @ COF can be observed at 10-90℃with Fe 3 O 4 The same characteristic diffraction peaks at 30.36 °, 35.47 °, 43.13 °, 53.25 °, 57.06 ° and 62.70 °, respectively, correspond to (220), (311), (400), (422), (511) and (440) (JCPDS No. 75-1610), respectively, and are contained in Fe 3 O 4 Spinel identity in MNPs, thus validating Fe 3 O 4 MNPs still maintain good crystal structure during synthesis with organic monomers. It was verified that covalent organic frame coating (BTA-TAPM) was successfully applied to Fe 3 O 4 MNPs on the outer surface.
5. To investigate the stability of COF at high temperature, the mass change of magnetic COF at a temperature change of 0 to 800 ℃ was studied using a thermal analyzer, and as a result, as shown in fig. 1H, the mass of COF was about 95% and above at a temperature of 0 to 420 ℃, probably due to partial water loss; and Fe at 420 ℃ or higher 3 O 4 The mass loss of BTA-tacm is significantly increased, probably due to a decrease in the stability of the organic ligand coating the covalent organic framework COFs (BTA-tacm) of the core, resulting in an increase in the mass loss rate. Research results show that the synthesized Fe 3 O 4 The @ COFs (BTA-TAPM) has good heat resistance and stability at the temperature of 0-520 ℃, which shows that the high-temperature environment does not influence the structure and performance of the material, and the higher extraction efficiency of the target object is ensured.
6. FIGS. 1I and 1J are graphs of nitrogen adsorption-desorption isotherms and pore size distribution of BTA-TAPM, the isotherms being of type IV typical, and from which Fe can be inferred 3 O 4 BTA-tacm possesses microporous and mesoporous structures, and the presence of an adsorption hysteresis loop in the curve may be due to both multi-molecular layer adsorption of the pore walls during adsorption and condensation in the pores. Furthermore, the Brunauer-Emmet-Teller specific surface area and pore size were 269.7m, respectively 2 g -1 (refer to Fe 3 O 4 Has a specific surface area of 7.9m 2 g -1 ) And 1.7nm, all of which prove Fe 3 O 4 BTA-tacm has the potential to enrich the target.
Example 5
Magnetic nanoparticles (Fe) prepared using example 1 3 O 4 The feasibility of adsorption extraction of 11 methoxy acrylic acid ester bactericides in complex samples is studied by @ COF (BTA-TAPM)), and the feasibility of adsorption extraction of 11 methoxy acrylic acid ester bactericides in complex samples is specifically as follows:
determination of Fe by experiment 3 O 4 The @ BTA-TAPM can be used as an adsorbent to extract methoxy acrylic acid ester bactericides, the adsorption performance of the material on methoxy acrylic acid ester bactericides with different concentrations at different times is studied, and the high adsorption capacity of the compounds can utilize Van der Waals force and strong interaction between COF and a target object. This example investigated the use of methoxy acrylic acid ester based bactericides in Fe 3 O 4 Adsorption on BTA-TAPM adsorbent. Assuming that the mass of the adsorbent is m (mg), the volume of the solution is V (mL), and the initial concentration of the target is C 0 (μg·mL -1 ). At a certain time (t) in the solution, the concentration of the target substance was Ce (μg.mL) -1 ) Neglecting the change of the volume of the solution, fe 3 O 4 The adsorption capacity of BTA-tacm can be calculated using the following formula:
for adsorption kinetics experiments, 1mg of Fe 3 O 4 Add @ BTA-TAPM to 2mL of 11 methoxy acrylic fungicide solutions (50. Mu.g.mL) -1 ) And vibrating to adsorb at different time (5 min, 10min, 20min,30min, 40min, 50min, 60min and 80 min). The implementation isExample results Fe was still calculated by equation (1) 3 O 4 Maximum adsorption capacity of BTA-TAPM to 11 methoxy acrylic acid ester bactericides.
As shown in FIG. 2A, the static equilibrium adsorption experiment based on the bactericide at different initial concentrations has studied Fe 3 O 4 Adsorption and extraction capability of the absorbent on 11 methoxy acrylic acid ester bactericides (BTA-TAPM). Since 11 bactericides have low solubility in aqueous solutions, the concentration of each target in the standard solution should be within the solubility range. 1.0mg of material was selected for adsorption experiments at a concentration ranging from 0 to 80. Mu.g.mL -1 . As can be seen from FIG. 2A, when the amount of the adsorbent is 1.0mg, the adsorption capacity of the magnetic adsorbent to the bactericide is 0 to 80. Mu.g.mL -1 The concentration range is in an increasing trend along with the increase of the concentration, and the concentration range is 50 mug.mL -1 When the adsorption equilibrium is reached. Calculated that the saturated adsorption quantity of azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, coumoxystrobin and chloromycetin can reach 54.18, 43.34, 42.84, 49.52, 46.15, 45.22, 45.46, 45.93, 46.59, 45.69 and 48.91 mg.g -1 . At different adsorption times, fe 3 O 4 The adsorption curve of the @ BTA-TAPM to 11 bactericides is shown in FIG. 2B. As can be seen from the figure, fe 3 O 4 The adsorption of 11 bactericides by BTA-TAPM is a rapid adsorption process and reaches adsorption equilibrium within 20-30 min. This can be attributed to the large specific surface area of the magnetic COF (269.7 m 2 ·g -1 ) Various adsorption functionalities (c=n, -OH, -NH 2 ) And a plurality of sites at which the target can be adsorbed. These adsorption groups can form various interactions with 11 bactericides such as pi-pi interactions, hydrogen bonding, hydrophobic interactions, and the like. These results indicate Fe 3 O 4 The @ BTA-TAPM has good adsorption performance on 11 methoxy acrylic acid ester bactericides.
Example 6
When the adsorption temperature is fixed and the adsorption equilibrium is reached, the adsorbent in the solution is fixed on the surface of the adsorbentThe concentration profile in the phase adsorbent and the liquid phase is referred to as isothermal adsorption profile. Wherein the concentration of the adsorbate on the adsorbate is expressed as the adsorption quantity and the concentration in the liquid phase is expressed as the equilibrium concentration of adsorbate. The adsorption process at the solid-liquid interface is relatively complex, and the adsorption process is usually not a single process, but is a process in which physical adsorption and chemical adsorption act simultaneously. The complex adsorption process can be divided into linear adsorption, nonlinear adsorption, monolayer adsorption and multi-molecular layer adsorption by an isothermal adsorption model, and the saturated adsorption capacity of the adsorbent to the adsorbent can be found. Thus, fe was further studied by Langmuir and Freundlich isotherm models on the basis of example 3 3 O 4 Adsorption mechanism of 11 methoxy acrylic acid ester bactericides by BTA-TAPM. Langmuir isotherms are based on the assumption that the target is covered with a monolayer on the outer surface of the adsorbent, which equation considers that the active adsorption sites on the adsorbent surface are uniformly arranged, that the adsorbate molecules can be adsorbed equally well and that there is no interaction between them. The linear expression of Langmuir isotherms is:
Ce(μg·mL -1 ) Is the equilibrium concentration of the target; qe (mg.g) -1 ) Is the amount of the target substance adsorbed per unit weight of the adsorbent, i.e., the adsorption amount. Qm (mg.g) -1 ) Is the maximum adsorption quantity; k (K) L (L·mg -1 ) Is Langmuir adsorption constant; numerically equal to the activation energy of the adsorbate and the adsorbate itself, K L The larger the number, the stronger the adsorption capacity of the adsorbent.
For Langmuir isothermal adsorption, a dimensionless factor R can be used L To judge R L There are 4 possible scenarios: (1) r is R L =0 is irreversible adsorption; (2) 0 (0)<R L <1 is advantageous adsorption; (3) r is R L =1 is linear adsorption; (4) r is R L >1 is a detrimental adsorption. R is R L The calculation formula of (2) is as follows:
wherein K is L (L·mg -1 ) Is Langmuir constant, C 0 (μg·mL -1 ) Is the initial concentration of the target.
Based on Langmuir isothermal formula, no ideal assumption is made, and the actual experience is combined to consider that the surface of the adsorbent is non-ideal and non-uniform, so that the Freundlich isothermal adsorption model is obtained. The isothermal type is suitable for the adsorption process under the medium pressure condition. The expression of the Freundlich isothermal adsorption equation is:
K F (L g -1 ) Is the Freundlich adsorption constant; n is Freundlich constant related to adsorption, the size of which represents the strength of the influence of equilibrium concentration on adsorption quantity, and is a related parameter showing adsorption superiority; when n is -1 When the value is 0.1-1, the adsorption process is easy; when n is -1 When the content is more than 2, the adsorption process is difficult.
The values and fitting curves for the corresponding parameters in the isotherm equations are shown in Table 1, FIG. 3 and FIG. 4, and the results show that the linear correlation coefficients R of azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, pyraclostrobin, kresoxim-methyl, enestroburin, coumoxystrobin and chlorpyrifos in Langmuir isotherms 2 0.96593, 0.90944, 0.87076, 0.90731, 0.91265, 0.93627, 0.92833, 0.92175, 0.91730, 0.92468 and 0.92171, respectively, dimensionless factor R L The adsorption of the magnetic COF to the bactericide was between 0 and 1 at each initial concentration, indicating that the adsorption was favorable under the experimental conditions.
TABLE 1 relevant parameters of Langmuir model and Freundlich model
In the Freundich isotherm, the linear correlation coefficients R of azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, kresoxim-methyl, trifloxystrobin, enestroburin, coumoxystrobin and chloropyrifos 2 0.95241, 0.92917, 0.95851, 0.97367, 0.97545 and 0.97877, 0.96354, 0.96205, 0.96422, 0.96222 and 0.95488, respectively. n is n -1 The values of (2) are all between 0 and 1, indicating Fe 3 O 4 The @ BTA-TAPM adsorption bactericide is an easy adsorption process; the correlation of the two model fits was compared to the parameters to find the Freundlich model (R 2 Not less than 0.92917) fitting ratio Langmuir model (R 2 More than or equal to 0.87076), which indicates that the adsorption isotherm of the catalyst accords with the Freundlich model; the Freundlich model is more suitable for describing the adsorption behavior of adsorbates on heterogeneous phase surfaces; the Langmuir model assumes that the surface of the adsorbent is uniform, the adsorbents have no interaction, and the adsorption is monolayer adsorption, however, in practice, the surface of the adsorbent is very uneven, and the adsorption is mostly multi-layer adsorption, so that the experimental Freundlich adsorption isothermal process is often more consistent with the actual adsorption process. This phenomenon may be explained by: the adsorption of the magnetic COF to the methoxy acrylic acid ester bactericide is based on multi-layer adsorption caused by the combination of hydrophobic interaction, hydrogen bonding, van der Waals force, pi-pi stacking force and the like.
Example 7
Kinetics is the law of concentration of the adsorbate molecules involved in the adsorption process versus the adsorption rate. The kinetic model is an equation for describing the adsorption process, which is summarized by combining actual conditions on the basis of dynamics. In the solid-liquid adsorption process, the equations often used to describe the adsorption rate have a quasi-first order kinetic equation and a quasi-second order kinetic equation.
The quasi-first-order dynamics model is one of the most common dynamics models, and is obtained by correcting the quasi-first-order dynamics model on the basis of an ideal first-order dynamics model. It is assumed that the control step of the adsorption process is a diffusion process. In reality, the adsorption rate is not determined by a single factor, but can be approximated as first-order kinetic behavior, and the expression is as follows:
Q t ＝Q e (1-e (-K 1 t) ) (5)
Q t (mg·g -1 ) And Q e (mg·g -1 ) The adsorption amounts are respectively the adsorption time t and the adsorption equilibrium; k (K) 1 (h -1 ) Is the adsorption rate constant.
The quasi-second-level kinetic model relates to chemical adsorption based on the assumption that the adsorption rate is determined by the quadratic power of the adsorption activity space number of the surface of the adsorbent, and electrons share or transfer participate in the adsorption process, and the expression is as follows:
Q t (mg·g -1 ) And Q e (mg·g -1 ) The adsorption amounts are respectively the adsorption time t and the adsorption equilibrium; k (K) 2 (g·mg -1 h -1 ) Is the adsorption rate constant. According to Fe in Table 2 3 O 4 R of quasi-primary and quasi-secondary dynamics model of @ BTA-TAPM adsorption bactericide 2 Can be compared to obtain the linear correlation coefficient (R 2 Not less than 0.99355) compared with the linear correlation coefficient (R) of the quasi-first-order adsorption kinetic model 2 More than or equal to 0.98339) is more close to 1, and the equilibrium adsorption quantity measured by experiments is more close to that calculated by a quasi-secondary adsorption kinetic model. Therefore, the adsorption process of the magnetic COF adsorbent on the methoxy acrylic acid ester bactericide can be described by a quasi-second-level kinetic model, the whole adsorption process is a chemical adsorption process, and the adsorption process can be accurately and objectively embodied to a certain extent, and comprises a liquid film diffusion process, a surface adsorption process, a particle internal diffusion process and the like.
TABLE 2 parameters related to the quasi-primary and quasi-secondary dynamics models
Example 8
In this example, the recovery rates of the magnetic nanoparticles prepared in examples 1 to 3 were compared as follows:
(1) 5mg of the 3 magnetic nanoparticles prepared in examples 1 to 3 were weighed separately, placed in a 40mL transparent glass vial together with 5mL of the labeled sample solution, and then rapidly oscillated at 2000rpm for 5min.
(2) The magnetic nanoparticles are adsorbed under the magnetic force of an external strong magnet, and the supernatant is discarded.
(3) Target analytes were sonicated with Fe using 5mL acetonitrile 3 O 4 The @ COF desorption was carried out for 2min. The supernatant was collected and was purged with nitrogen at 50 ℃ to near dryness to give an extract.
(4) The extract was re-dissolved with 1mL of methanol, passed through a 0.22 μm filter and analyzed using UPLC-MS/MS.
Through detection, fe 3 O 4 @BTA-TAPM，Fe 3 O 4 @Tp-ETTA，Fe 3 O 4 The extraction recovery rate of the @ Dt-TAPM to 11 methoxy acrylic acid ester bactericides is 96.3-111.3%, 69.0-98.8%, 77.8-95.5%, see FIG. 5 for details, fe prepared in example 1 3 O 4 The extraction effect of the BTA-TAPM nanoparticle is better.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (23)
1. Use of magnetic nanoparticles for adsorbing methoxy acrylic bactericides, characterized in that the magnetic nanoparticles comprise:
a core formed from ferroferric oxide;
a shell covering at least a portion of the surface of the core, the shell being formed from repeating multi-ring units, wherein the multi-ring units are selected from one of formula I, formula II, or formula III.
2. Use according to claim 1, characterized in that the shell has an average pore size of 1.0-2.5 nm and a thickness of 20-30 nm.
3. The use according to claim 1, wherein the specific surface area of the shell is 200-370 m 2 ·g -1 。
4. The use according to claim 3, wherein the specific surface area of the shell is 250-370 m 2 ·g -1 。
5. Use according to claim 1, wherein the shell has crystal diffraction peaks in X-ray powder diffraction data at 2Θ of 30.36 °, 35.47 °, 43.13 °, 53.25 °, 57.06 ° and 62.70 °.
6. Use according to claim 1, characterized in that the particle size of the nucleus is 200-300 nm.
7. The use according to claim 1, wherein the saturated adsorption amount of the magnetic nanoparticle to the methoxy acrylic bactericide is 30-60 mg.g -1 。
8. The use according to claim 1, wherein the saturated adsorption amount of the magnetic nanoparticle to the methoxy acrylic bactericide is 40-55mg.g -1 。
9. The use according to claim 1, wherein the magnetic nanoparticles have an adsorption equilibration time of 20-30 minutes for methoxy acrylic acid ester based bactericides.
10. The use according to claim 1, wherein the methoxy acrylic fungicide is at least one selected from azoxystrobin, picoxystrobin, pyraclostrobin, azoxystrobin, pyraclostrobin, trifloxystrobin, enestroburin, coumoxystrobin and chloromycetin.
11. The use according to claim 1, wherein the method of preparing the magnetic nanoparticles comprises:
first contacting a solution containing an amino monomer with ferroferric oxide nanoparticles and performing first stirring so as to obtain a first mixture; and
the first mixture is brought into second contact with an aldehyde-based monomer and a catalyst and subjected to second stirring so as to obtain the magnetic nanoparticles.
12. Use according to claim 11, characterized in that the amino monomer is 4,4',4 "-triaminetrityl methane (TAPM) or tetra- (4-aminostyrene) Ethylene (ETTA).
13. The use according to claim 11, characterized in that the aldehyde monomer is 3,3', 5' -tetra-aldehyde Biphenyl (BTA), 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde (Tp) or 2, 5-dihydroxyterephthalaldehyde (Dt).
14. Use according to claim 11, characterized in that the molar ratio of the amino monomer to the aldehyde monomer is (1-2): 1.
15. use according to claim 14, characterized in that the molar ratio of the amino monomer to the aldehyde monomer is 4:3.
16. The use according to claim 12, characterized in that the mass concentration of the solution containing amino monomers is 1-2%.
17. Use according to claim 11, characterized in that the mass ratio of amino monomer to ferroferric oxide is (0.5-1): 1.
18. use according to claim 11, characterized in that the catalyst is acetic acid.
19. Use according to claim 11, characterized in that the second contact is an ultrasonic oscillation for a period of 15-30 minutes.
20. The use according to claim 11, wherein the first agitation is for a period of 15 to 45 minutes.
21. The use according to claim 11, wherein the second stirring time is 100 to 140 minutes.
22. The use according to claim 11, wherein the temperature of both the first and second agitation is 50-70 ℃; the rotation speed is 400-1000 rpm.
23. The use according to claim 22, wherein the temperature of both the first and second agitation is 60 ℃; the rotation speed is 500-800 rpm.
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