CN111363160B - Three-dimensional covalent triazine-based calix [4] arene polymer and preparation method and application thereof - Google Patents
Three-dimensional covalent triazine-based calix [4] arene polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a three-dimensional covalent triazine-based calix [4] arene polymer and a preparation method and application thereof, wherein the preparation method comprises the steps of reacting 4-amino calix [4] arene with s-triazine under an ice bath condition to obtain an intermediate; then, carrying out functional polymerization on the intermediate and 1,3,5- (4-aminophenyl) benzene under an alkaline condition to obtain a triazine-based calix [4] arene polymer; the triazine-based calix [4] arene polymer can be used for adsorbing and treating organic micro-pollutants in a water body. Compared with the prior art, the triazine-based calix [4] arene polymer prepared by the invention has better stability to humidity and water, has the advantages of high adsorption efficiency, large adsorption capacity per unit mass, good desorption effect, long cycle service life, good heat resistance of the polymer and the like, and has wider application prospect in the aspect of quickly treating wastewater.
Description
Technical Field
The invention belongs to the technical field of organic supramolecular polymer preparation, relates to a three-dimensional covalent triazine-based calix [4] arene polymer, a preparation method and application thereof, and particularly relates to a triazine-based calix [4] arene polymer rich in nitrogen atoms, a preparation method and application thereof.
Background
The industrial wastewater contains various toxic and harmful substances, particularly aromatic organic dyes such as rhodamine B, methylene blue and the like, and after the industrial wastewater is discharged into the environment, the transparency of the water body is reduced, the growth of aquatic organisms is hindered, the self-purification function of the water body is damaged, and the balance of the whole water body ecological system is broken. Therefore, the reduction of the dye concentration in the wastewater and the standard discharge of the wastewater become the hot topic in the field of material research. The traditional dye wastewater treatment technology mainly comprises two technologies, one is a physical method, but due to the defects of high regeneration cost, low removal rate and the like, the application range of the dye wastewater treatment technology has certain limitation; the other is a chemical method, but the chemical method is not only expensive but also suffers from secondary pollution, and thus is also limited in the range of application.
In the research on effective removal of organic pollutants in water, the adsorption method has been the most interesting dye wastewater treatment method due to its advantages of low cost, simple operation, etc. According to reports, various adsorbents such as activated carbon, zeolite, chitosan, clay and the like can effectively remove organic micropollutants in water, but the problems of low treatment capacity, low adsorption speed and the like still exist. Therefore, designing alternative adsorbents for wastewater treatment is of urgent and important significance for practical applications.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a three-dimensional covalent triazine-based calix [4] arene polymer, a preparation method and application thereof, which are used for solving the problems of a common adsorbent for adsorbing organic micro-pollutants in a water body; such as low processing capacity, slow adsorption rate, difficult regeneration process, etc.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a three-dimensional covalent triazine-based calix [4] arene polymer comprises the steps of reacting 4-amino calix [4] arene with s-triazine under an ice bath condition to obtain an intermediate; then, the intermediate and 1,3,5- (4-aminophenyl) benzene are functionally polymerized under the alkaline condition to obtain the three-dimensional covalent triazine-based calix [4] arene polymer.
Further, the method specifically comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran, stirring and reacting for 6-12h under an ice bath condition, stopping the reaction, sequentially removing the solvent, washing for a plurality of times by using n-hexane, and drying to obtain an intermediate;
2) and dissolving the intermediate and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting under a heating condition, cooling to room temperature after the reaction is finished, centrifugally separating, washing, and drying in vacuum to obtain the three-dimensional covalent triazine-based calix [4] arene polymer.
Further, in the step 1), the molar ratio of the 4-aminocalixarene to s-triazine is (1-2) to (2-4).
Further, the intermediate obtained in the step 1) is washed by n-hexane and then subjected to the step 2).
Further, in the step 2), the molar ratio of the intermediate, 1,3,5- (4-aminophenyl) benzene and potassium carbonate is 1 (2-3.5) to (5-15).
Further, in the step 2), the heating reaction temperature is 105-115 ℃ and the heating reaction time is 60-84 h.
Further, in the step 2), in the washing process, the used washing agents are water, methanol and DMF in sequence.
The three-dimensional covalent triazine-based calix [4] arene polymer is prepared by adopting the method.
The application of a three-dimensional covalent triazine-based calix [4] arene polymer is characterized in that the triazine-based calix [4] arene polymer is used as an adsorbent for adsorbing and treating organic micro-pollutants in a water body.
Further, in the process of adsorbing and treating organic micro-pollutants in a water body by the triazine-based calix [4] arene polymer, the adsorption temperature is room temperature.
The invention firstly utilizes s-triazine to modify 4-amino calix [4] arene to form an intermediate, then 1,3,5- (4-aminophenyl) benzene with a three-dimensional structure reacts with the intermediate to form C-N bonds to complete grafting, and a novel three-dimensional calixarene porous polymer, namely the triazine calix [4] arene polymer, is obtained. The invention specifically relates to a method for modifying and polymerizing amino calixarene by using s-triazine to generate a strong covalent bond, thereby improving the thermal stability of the material and improving the nitrogen content in the polymer. The specific reaction principle is as follows: firstly, 4-aminocyclopcalix [4] arene reacts with s-triazine to form a substitution reaction, and because the activity of the s-triazine is high, the reaction process adopts an ice bath condition, the 4-aminocyclopcalix [4] arene is used as a nucleophilic reagent, firstly, nucleophilic attack is carried out on a carbon atom connected with one chlorine atom on a triazine ring to obtain an intermediate addition product with polarity, then the addition product is quickly converted into amine salt, the aromaticity of the ring is recovered, and potassium carbonate is used as alkali in a system to adsorb hydrogen chloride generated in the reaction; due to the low reaction temperature, only active intermediate can be obtained by controlling the reaction. Secondly, in the polymerization reaction of the intermediate and 1,3,5- (4-aminophenyl) benzene, the temperature is 110 ℃, the reaction mechanism is similar to that of the previous step, at the moment, the 1,3,5- (4-aminophenyl) benzene is used as a nucleophilic reagent, the potassium carbonate is still used as an acid-applying agent, and the halogen atoms on the active intermediate are sequentially replaced by the 1,3,5- (4-aminophenyl) benzene to generate the polymer.
Compared with the prior art, the invention has the following characteristics:
1) the nitrogen atom-rich triazine-based cup [4] prepared by the invention]The aromatic hydrocarbon polymer shows good stability to humidity and water, can be used as an organic pollutant adsorbing material to adsorb organic dye in water, has high adsorption efficiency (the adsorption efficiency to methylene blue and toluidine blue can reach 99.9 percent) and large unit mass adsorption capacity (the maximum adsorption capacity to the methylene blue and the toluidine blue can reach 251.9mg g-1、225.7mg·g-1) Good desorption effect and long cycle service life (i.e. moreThe novel nitrogen atom-rich triazine-based cup [4] is proved by the good pollutant removal capability of the novel nitrogen atom-rich triazine-based cup]The aromatic hydrocarbon polymer has a wide application prospect in the aspect of rapidly treating wastewater;
2) the triazine-based calix [4] aromatic hydrocarbon polymer prepared by the invention belongs to an organic microporous polymer, and compared with adsorbents such as activated carbon, zeolite, chitosan, clay and the like, the organic microporous polymer is a novel porous material with high specific surface area, porous structure, high thermal stability and light weight, has a large number of open sites and wider pore size distribution after construction is completed, and compared with traditional microporous materials such as organic framework compound Materials (MOFs) and the like, the organic microporous polymer-based adsorbent not only has flexible and targeted pore size design capability consistent with the MOFs, but also can solve the disadvantage that the MOFs can not maintain a spatial structure in environments such as high temperature, acid and alkali and the like, and shows good adsorption performance and high selectivity;
3) compared with an adsorbent taking beta-cyclodextrin (beta-CD) as a main component, the adsorbent is widely concerned due to the advantages of strong affinity, low cost and simple design of the beta-CD, but the application range of the adsorbent is limited due to the defect of poor water solubility of the beta-CD.
Drawings
FIG. 1 is a FT-IR spectrum of intermediate (e), 1,3,5- (4-aminophenyl) benzene, triazinyl calix [4] arene polymer (CaCOP) in example 1;
FIG. 2 is an SEM photograph of a triazine based calix [4] arene polymer in example 1;
FIG. 3 is a TEM image of the triazine based calix [4] arene polymer in example 1;
FIG. 4 is a thermogravimetric plot of the triazine based calix [4] arene polymer of example 1;
FIG. 5 shows a triazine-based cup [4] in example 1]Aromatic polymerizationN of matter2Adsorption and desorption isotherm diagram;
FIG. 6 is the triazine based cup [4] of example 1]CPMAS of aromatic polymers (CaCOP)13C NMR spectrum chart;
FIG. 7 shows CaCOP (1.00 mg. multidot.mL) in example 2-1) Time-dependent adsorption process profiles for each organic micropollutant (0.100 mM);
FIG. 8 is a graph comparing the removal rates of CaCOP to different organic micropollutants after 30min contact in example 2;
FIG. 9 is a diagram of a device for testing the flow adsorption capacity of CaCOP in example 3;
FIG. 10 is a diagram of an experimental apparatus for the regeneration of CaCOP in example 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
this example is used to prepare a three-dimensional covalent triazine-based calix [4] arene polymer (CaCOP).
The preparation method comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:2, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, sequentially removing the solvent, washing for a plurality of times by using n-hexane, and drying to obtain an intermediate (e), wherein the yield is 80%;
2) dissolving the intermediate (e) and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting at 110 ℃ for 72 hours, cooling the product to room temperature after the reaction is finished, sequentially performing centrifugal separation, washing with water, methanol and DMF (dimethyl formamide), and drying in vacuum to obtain the three-dimensional covalent triazine base calix [4] arene polymer (CaCOP), wherein the molar ratio of the intermediate (e) to the 1,3,5- (4-aminophenyl) benzene to the potassium carbonate is 1:2.7:10, and 600mg of the triazine base calix [4] arene polymer is obtained, and the yield is 60%.
The characterization of the reactants and products is as follows:
shown in figure 1 are intermediate (e), 1,3,5- (4-aminophenyl) benzene, triazinyl calix [4]]FT-IR spectrum of aromatic hydrocarbon polymer (CaCOS), from which intermediate (e) and-CH of CaCOS can be seen2The tensile vibration absorption peak is from 2960cm-1To 2850cm-1And disappearance of the C-Cl peak on the CaCOP (750-700 cm)-1)；
As shown in fig. 2 and fig. 3, the SEM image and TEM image of the triazine based calix [4] arene polymer are shown, and the triazine based calix [4] arene polymer is shown as a three-dimensional structure in the TEM image;
as shown in FIG. 4, which is a thermogravimetric graph of the triazine-based calix [4] arene polymer, it can be seen that the decomposition temperature of the triazine-based calix [4] arene polymer is about 372 ℃, which indicates that the triazine-based calix [4] arene polymer has better heat resistance;
as shown in FIG. 5, is a triazine-based cup [4]]N of aromatic hydrocarbon polymer2Adsorption and desorption isotherm diagram with a surface area of 122m2·g-1；
As shown in figure 6 is a triazine based cup [4]]CPMAS of aromatic polymers (CaCOP)13C NMR spectrum of the sample, from which 1,3,5- (4-aminophenyl) benzene (TAB) and CaCOP at 3350cm-1The characteristic absorption peak of (A) is-CH2The C-Cl peak on CaCOP (170ppm) disappeared significantly, indicating that intermediate (e) reacted with TAB with a nucleophilic aromatic substitution.
Example 2:
this example is intended to examine the static adsorption capacity of the triazine-based calix [4] arene polymer (CaCOP) prepared in example 1 for dyes.
The specific experimental process is as follows:
at the experimental ambient temperature of 25 ℃, the cacos (50.00mg) were first washed with 8mL of deionized water for 5.00min and then filtered through a PTFE membrane filter (0.45 μm), after which the cacos, a stock solution of dye (0.100mM, 50.00mL) were added sequentially to a 100.0mL round bottom flask and the mixture was stirred immediately after the addition of the stock solution of dye and the suspension in the flask (2.00mL) was removed with a syringe at regular intervals of time and then immediately filtered using a PTFE membrane filter (0.45 μm) and the residual concentration of dye in each filtrate sample was determined by uv-vis spectroscopy.
The stock solution of the dye used contained one of the dyes shown below.
The detection wavelengths of the characteristic absorption peaks of the above dyes are as follows: methylene blue (Methylene blue,663nm), Toluidine blue (Toluidine blue,630nm), Methyl orange (Methyl orange,464nm), crystal violet (Purple crystal,591nm), Rhodamine B (Rhodamine B,550nm), Sodium fluorescein (Sodium fluoroscein, 490 nm).
The experimental results are as follows:
shown in FIG. 7 is CaCOP (1.00 mg. mL)-1) The time-dependent adsorption process diagram of each organic micropollutant (0.100mM) mainly adsorbs methylene blue, toluidine blue, methyl orange, crystal violet, rhodamine B and fluorescein sodium, and the CaCOP shows excellent adsorption capacity to the methylene blue and the toluidine blue.
TABLE 1
aThe concentration of the adsorbent CaCOP is 0.1 mg/mL-1。
As shown in fig. 8, which is a graph comparing the removal rates of the cacos after 30min contact with different organic micropollutants (the specific data are shown in table 1), it can be seen from fig. 8 and table 1 that the cacos exhibit excellent adsorption capacities for methylene blue and toluidine blue, the adsorption efficiencies of the cacos reach 99.9%, and the maximum adsorption amounts are 251.9mg · g%, respectively-1、225.7mg·g-1。
Example 3:
this example is intended to examine the flow adsorption capacity of the triazine-based calix [4] arene polymer (CaCOP) prepared in example 1 for dyes.
Specifically, a flow-through adsorption separation experiment was performed using a 5mL syringe (inner diameter of 1cm, total length of 5cm, and a layer of cotton wool was filled at the inner outlet of the syringe to prevent mass loss), and the experimental procedure was as follows:
as shown in fig. 9, at an experimental environment temperature of 25 ℃, cacos (100.00mg) were first washed with 15mL of deionized water for 5.00min, and then filtered through a PTFE membrane filter (0.45 μm), after which the cacos were transferred to a 5mL syringe (filling height of 2mm), after which 2mL of a dye stock solution (solution properties same as in example 2) was added to the syringe, and the dye stock solution was filtered through a cacos adsorption layer by pushing a piston for 30s (flow rate of 3-4 mL/min), and filtrates were collected, and the residual concentration of the dye in each filtrate sample was determined using the method of example 2, thereby determining the removal efficiency of each organic trace contaminant, wherein each dye was repeated 3 times.
The experimental results are as follows: by utilizing a flow adsorption experiment, the adsorption efficiencies of the CaCOP to methylene blue, toluidine blue, methyl orange, crystal violet and rhodamine B are respectively 100 percent and 70 percent.
Example 4:
this example is intended to examine the cycle life of the triazine-based calix [4] arene polymer (CaCOP) prepared in example 1.
The specific experimental process is as follows:
as shown in fig. 10, a syringe filled with capos (filling height of 2mm) was obtained by the same method as in example 3, 10mL of dye stock solution was filtered through the syringe at a flow rate of 3-4mL/min (the solution was methylene blue, toluidine blue, methyl orange, crystal violet, rhodamine B, and fluorescein sodium in example 2, respectively), and then the capos were removed and subjected to methanol washing, centrifugation, and drying in sequence, and then the adsorption/desorption cycles were repeated, and the removal efficiency during each cycle was examined by the same method as in example 2, and it was found that the removal efficiency of the capos during 5 adsorption/desorption cycles was equivalent to and substantially unchanged from the results in example 3, indicating that the capos had excellent regeneration ability.
Example 5:
this example was conducted to conduct a batch adsorption kinetics study of the triazine-based calix [4] arene polymer (CaCOP) prepared in example 1 for methylene blue, toluidine blue, and methyl orange.
Specific experimental procedures are described in the literature (Shi, B.et al. A pilar [5] arene-based 3D network polymer for Rapid removal of organic micropollutants from water.J. Mater. chem.A. 5, 24217-24222 (2017)), where the initial concentrations of methylene blue, toluidine blue and methyl orange are 0.1 mmol/L.
The relevant balance parameters can be determined by a corresponding linear fit (as shown in table 2). The adsorption kinetics can be quantitatively described through a quasi-first-order kinetic model and a quasi-second-order kinetic model, so that an apparent rate constant K is obtained1And K2And a correlation number R2By comparison, the pseudo-second order kinetic model was found to be more suitable than the quasi-first order kinetic model for describing the adsorption process, indicating that the adsorption behavior between the nitrogen-rich atoms, CaCOP, and methylene blue, toluidine blue, and methyl orange is primarily due to chemical interactions.
TABLE 2
Example 6:
this example was used to perform a batch adsorption thermodynamic study of the triazine-based calix [4] arene polymer (CaCOP) prepared in example 1 on methylene blue, toluidine blue and methyl orange.
Specific experimental procedures are described in the literature (Shi, B.et al. A pilar [5] arene-based 3D network polymer for Rapid removal of organic micropollutants from water.J. Mater. chem.A. 5, 24217-24222 (2017)), where the initial concentrations of methylene blue, toluidine blue and methyl orange are 0.1 mmol/L.
Equilibrium isotherm data are described by two well-known Langmuir and Freundlich isotherm models. The relevant balance parameters can be determined by a corresponding linear fit (as shown in table 3). Adsorption by LangmuirAnd (5) obtaining the maximum adsorption amount of the adsorbent in the equilibrium state of the methylene blue, the toluidine blue and the methyl orange. Higher correlation coefficient (R) of Langmuir isothermal model2) It is shown that the adsorption data more closely matches the Langmuir isothermal model, indicating that the adsorption process is predominantly a relatively uniform monolayer adsorption. The maximum adsorption capacities (qm) of the nitrogen-atom-rich CaCOs to methylene blue, toluidine blue and methyl orange are 1806.82mg/g, 2161.321mg/g and 242.131mg/g respectively, which are higher than that of the existing Calixane polymer. The higher adsorption capacity may be attributed to the formation of a mesoporous structure and multiple adsorption sites, allowing the dye molecules to rapidly enter the cavities within the nitrogen-rich atoms of the CaCOP, forming guest-guest complexes.
TABLE 3
Example 7:
in this example, a three-dimensional covalent triazine-based calix [4] arene polymer is prepared by the following three methods, specifically, the preparation method and steps are as follows:
the first method comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:2, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying, and washing with n-hexane to obtain an intermediate with a yield of 80%;
2) dissolving the intermediate and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting at 110 ℃ for 72h, cooling the product to room temperature after the reaction is finished, sequentially performing centrifugal separation, washing with water, methanol and DMF (dimethyl formamide), and drying in vacuum to obtain the three-dimensional covalent triazine-based calix [4] arene polymer (CaCOP), wherein the molar ratio of the intermediate to the 1,3,5- (4-aminophenyl) benzene to the potassium carbonate is 1:2:5, so that 600mg of the triazine-based calix [4] arene polymer is obtained, and the yield is 60%.
And the second method comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 3:5, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying, and washing with n-hexane to obtain an intermediate with a yield of 75%;
2) dissolving the intermediate and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting at 110 ℃ for 72h, cooling the product to room temperature after the reaction is finished, sequentially performing centrifugal separation, washing with water, methanol and DMF (dimethyl formamide), and drying in vacuum to obtain the three-dimensional covalent triazine-based calix [4] arene polymer (CaCOP), wherein the molar ratio of the intermediate to the 1,3,5- (4-aminophenyl) benzene to the potassium carbonate is 1:2.7:10, and 500mg of the triazine-based calix [4] arene polymer is obtained, and the yield is 50%.
And the third is that:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:4, stirring and reacting for 8 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying, and washing with n-hexane to obtain an intermediate with a yield of 78%;
2) dissolving the intermediate and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting at 110 ℃ for 72h, cooling the product to room temperature after the reaction is finished, sequentially performing centrifugal separation, washing with water, methanol and DMF (dimethyl formamide), and drying in vacuum to obtain the three-dimensional covalent triazine-based calix [4] arene polymer (CaCOP), wherein the molar ratio of the intermediate to the 1,3,5- (4-aminophenyl) benzene to the potassium carbonate is 1:3.5:15, and 480mg of the triazine-based calix [4] arene polymer is obtained, and the yield is 48%.
Example 8:
a three-dimensional covalent triazine-based calix [4] arene polymer is prepared by the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:1, stirring and reacting for 12 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying, and washing with n-hexane to obtain an intermediate;
2) dissolving the intermediate and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting at 115 ℃ for 60 hours, cooling the product to room temperature after the reaction is finished, and sequentially carrying out centrifugal separation, washing with water, methanol and DMF (dimethyl formamide) and vacuum drying to obtain the three-dimensional covalent triazine-based calix [4] arene polymer, wherein the molar ratio of the intermediate to the 1,3,5- (4-aminophenyl) benzene to the potassium carbonate is 1:2.7: 10.
Example 9:
a three-dimensional covalent triazine-based calix [4] arene polymer is prepared by the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran in a molar ratio of 1:2, stirring and reacting for 6 hours under an ice bath condition, stopping the reaction, standing overnight at room temperature, filtering, drying and washing with n-hexane in sequence to obtain an intermediate (yield is 78%);
2) dissolving the intermediate and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting at 105 ℃ for 84h, cooling the product to room temperature after the reaction is finished, and sequentially performing centrifugal separation, washing with water, methanol and DMF (dimethyl formamide) and vacuum drying to obtain the three-dimensional covalent triazine-based calix [4] arene polymer, wherein the molar ratio of the intermediate to the 1,3,5- (4-aminophenyl) benzene to the potassium carbonate is 1:2.7: 10.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A method for preparing a three-dimensional covalent triazine-based calix [4] arene polymer, comprising: reacting 4-aminocalix [4] arene with s-triazine in a molar ratio of (1-2) to (2-4) under an ice bath condition to obtain an intermediate; then, the intermediate and 1,3,5- (4-aminophenyl) benzene are functionally polymerized under the alkaline condition according to the molar ratio of 1 (2-3.5), and the three-dimensional covalent triazine-based calix [4] arene polymer is obtained.
2. The method for preparing a three-dimensional covalent triazine-based calix [4] arene polymer according to claim 1, wherein the method specifically comprises the following steps:
1) adding 4-aminocalix [4] arene and s-triazine into tetrahydrofuran, stirring and reacting for 6-12h under an ice bath condition, stopping the reaction, and removing the solvent to obtain an intermediate;
2) and dissolving the intermediate and 1,3,5- (4-aminophenyl) benzene in dioxane containing potassium carbonate, reacting under a heating condition, and after the reaction is finished, sequentially carrying out cooling, centrifugal separation, washing and vacuum drying processes to obtain the three-dimensional covalent triazine-based calix [4] arene polymer.
3. The method for preparing a three-dimensional covalent triazine-based calix [4] arene polymer according to claim 2, wherein the intermediate obtained in the step 1) is washed with n-hexane and then subjected to the step 2).
4. The method for preparing a three-dimensional covalent triazine-based calix [4] arene polymer according to claim 2, wherein in the step 2), the molar ratio of the intermediate, 1,3,5- (4-aminophenyl) benzene and potassium carbonate is 1 (2-3.5) to (5-15).
5. The method as claimed in claim 2, wherein the heating conditions in step 2) are 105 ℃ to 115 ℃ and 60-84 h.
6. The method for preparing a three-dimensional covalent triazine-based calix [4] arene polymer according to claim 2, wherein in the step 2), the washing agent used in the washing process comprises water and an organic solvent.
7. A three-dimensional covalent triazine-based calix [4] arene polymer, prepared by the method of any one of claims 1 to 6.
8. Use of the three-dimensional covalent triazine-based calix [4] arene polymer according to claim 7, wherein the triazine-based calix [4] arene polymer is used as an adsorbent for the adsorption treatment of organic micropollutants in a body of water.
9. The use of the three-dimensional covalent triazine-based calix [4] arene polymer according to claim 8, wherein in the process of adsorbing and treating organic micropollutants in a water body, the adsorption temperature is room temperature.
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