CN106279698B - 2, 4-dinitrophenol surface molecularly imprinted polymer and preparation method and application thereof - Google Patents

2, 4-dinitrophenol surface molecularly imprinted polymer and preparation method and application thereof Download PDF

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CN106279698B
CN106279698B CN201610725212.5A CN201610725212A CN106279698B CN 106279698 B CN106279698 B CN 106279698B CN 201610725212 A CN201610725212 A CN 201610725212A CN 106279698 B CN106279698 B CN 106279698B
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dinitrophenol
imprinted polymer
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methanol
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CN106279698A (en
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朱桂芬
于文娜
王培云
张霞
茹祥莉
程国浩
赵轩
樊静
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Henan Normal University
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Abstract

The invention discloses a 2, 4-dinitrophenol surface molecularly imprinted polymer and a preparation method and application thereof. The technical scheme provided by the invention has the key points that: activated silica gel is used as a carrier, absolute ethyl alcohol is used as a solvent, 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent, glacial acetic acid is used as an initiator, the mixture is oscillated and initiated to polymerize for 9 to 30 hours in a water bath at 30 ℃, the template molecule is eluted or soxhlet extraction is carried out, and the mixture is cleaned by methanol and then dried in vacuum at 60 ℃ to obtain the target product, namely the 2, 4-dinitrophenol surface molecularly imprinted polymer. The 2, 4-dinitrophenol surface molecularly imprinted polymer prepared by the method has the advantages of uniform particle size, excellent mechanical property, strong selective adsorption capacity, large adsorption capacity and easy regeneration and recycling, and can be used for high-selectivity separation and enrichment pretreatment of 2, 4-dinitrophenol and 2,4, 6-trinitrophenol in a complex environment sample solution.

Description

2, 4-dinitrophenol surface molecularly imprinted polymer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adsorbents for 2, 4-dinitrophenol in the environment, and particularly relates to a 2, 4-dinitrophenol surface molecularly imprinted polymer and a preparation method and application thereof.
Background
Nitrophenol is an important and commonly used chemical raw material, and is widely applied to the production of explosives, medicines, pesticides, dyes, wood preservatives, rubber and the like as a raw material or an intermediate, so that industrial wastewater containing nitrophenol is discharged in large quantity. The phenol compound is a substance with cytotoxicity, is difficult to biodegrade, and can also react with protein in the cell protoplasm to form denatured protein, so that the cell loses activity and great toxicity is caused. Although the local damage of the low-concentration phenol substances is not obvious in a short time, the low-concentration phenol substances have strong penetrability and can bring more serious harm by permeating and accumulating to deep tissues. Therefore, the method has important significance for effectively removing and purifying the phenol pollutants in the water environment.
At present, although methods for removing phenols in water bodies, such as chemical oxidation, ozone oxidation, photolysis and the like, are effective, the implementation process cost is too high, and the methods are difficult to apply to the field of large-scale wastewater purification treatment engineering; the physical method mainly based on adsorption mainly adopts activated carbon particles, which are difficult to realize regeneration and cyclic utilization while efficiently purifying phenol pollutants in water and are easy to cause new environmental pollution. Therefore, the development of the efficient, cheap, green and recyclable phenol pollutant purifying material is the key for effectively purifying the phenol substances.
The molecularly imprinted polymer is a recently developed material with high selective adsorption capacity for a specific target substance, and has the advantages of strong recognition capacity, good stability, severe environment resistance, recyclability and the like, so that the molecularly imprinted polymer serving as an effective adsorbent material is rapidly developed in the field of separation and purification pretreatment of pollutants in a complex system. The existing molecularly imprinted polymer is mostly prepared in a high-toxicity organic solvent, the preparation process is complex, the reaction period is long, the post-treatment of the obtained polymer is relatively complicated, and the application of the molecularly imprinted polymer material in the environmental field is restricted to a certain extent.
The surface molecularly imprinted polymer is prepared by polymerizing macromolecules on the surface of a carrier, and the obtained surface molecularly imprinted polymer material has uniform granularity, high target object recognition rate and high regeneration efficiency. The 'sol-gel' method which takes silica gel as a main body is mostly carried out in ethanol, a large amount of volatile toxic organic solvent is not needed, the operation is simple and convenient, and the high molecular polymerization reaction can be initiated at normal temperature. Therefore, the preparation process of the molecularly imprinted polymer can be greenized and simplified by combining the sol-gel technology and the molecular imprinting technology, the obtained imprinted polymer material has excellent adsorption performance, the preparation time of the polymer is greatly shortened, the material is simple and easy to regenerate, and the application of the molecularly imprinted polymer in the field of environmental pollutant treatment can be favorably expanded.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the 2, 4-dinitrophenol surface molecularly imprinted polymer and the preparation method thereof, the prepared 2, 4-dinitrophenol surface molecularly imprinted polymer has uniform particle size, excellent mechanical property, strong selective adsorption capacity and large adsorption capacity, is easy to regenerate and recycle, and can be used for high-selectivity separation and enrichment pretreatment of 2, 4-dinitrophenol and 2,4, 6-trinitrophenol in a complex environment sample solution.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the 2, 4-dinitrophenol surface molecularly imprinted polymer is characterized by comprising the following steps of: activated silica gel is used as a carrier, absolute ethyl alcohol is used as a solvent, 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent, glacial acetic acid is used as an initiator, the mixture is oscillated and initiated to polymerize for 9 to 30 hours in a water bath at the temperature of 30 ℃, the obtained product is oscillated and eluted by using a methanol/ethanol mixed solution with the volume ratio of 9/1 or the obtained product is subjected to Soxhlet extraction by using a methanol/ethanol mixed solution with the volume ratio of 9/1, and the methanol is used for cleaning and then is dried in vacuum at the temperature of 60 ℃ to obtain the target product, namely the 2, 4-dinitrophenol surface molecularly imprinted polymer.
Further preferably, the ratio of the mass of the carrier activated silica gel to the molar weight of the template molecule 2, 4-dinitrophenol is 1g:1mmol, and the feeding molar ratio of the template molecule 2, 4-dinitrophenol, the functional monomer 3-aminopropyltriethoxysilane and the cross-linking agent tetraethyl orthosilicate is 1:2-12: 10-35.
The 2, 4-dinitrophenol surface molecularly imprinted polymer is characterized by being prepared by the method, and the structural formula of the 2, 4-dinitrophenol surface molecularly imprinted polymer is as follows:
Figure DEST_PATH_IMAGE001
the 2, 4-dinitrophenol surface molecularly imprinted polymer is applied to selective separation and enrichment of 2, 4-dinitrophenol and 2,4, 6-trinitrophenol in a complex environment sample solution.
Further preferably, the application of the 2, 4-dinitrophenol surface molecularly imprinted polymer in selective separation and enrichment of 2, 4-dinitrophenol and 2,4, 6-trinitrophenol in a complex environment sample solution is characterized by comprising the following specific steps: adding the 2, 4-dinitrophenol surface molecularly imprinted polymer into a complex environment sample solution, and standing for 3 hours at room temperature to complete the adsorption process; and (2) performing solid-liquid separation on the 2, 4-dinitrophenol surface molecularly imprinted polymer after adsorption, adding a methanol/water/ethanol mixed solution with the volume ratio of 40/40/20 into the solid obtained by separation, standing and soaking for 1h at room temperature, repeatedly soaking for 3-5 times after solid-liquid separation, cleaning and drying to obtain the regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer for repeated recycling.
More preferably, the molar concentration of the 2, 4-dinitrophenol in the complex environment sample solution is 0.5-3mol/L, and the removal rate of the 2, 4-dinitrophenol in the complex environment sample solution by the 2, 4-dinitrophenol surface molecularly imprinted polymer is over 71 percent.
The invention preferably adopts a method combining 'sol-gel' and 'surface molecular imprinting', wherein the sol-gel is a milder method, only needs lower synthesis temperature (25-30 ℃), and the components in the sol-gel system diffuse in a nanometer range, so that the polymerization reaction is easy to initiate. The 2, 4-dinitrophenol surface molecularly imprinted polymer is prepared under the conditions of initiation of glacial acetic acid (1 mol/L) and water bath oscillation at 30 ℃, and the obtained 2, 4-dinitrophenol surface molecularly imprinted polymer has the characteristics of uniform particle size, large specific surface area, large adsorption capacity to 2, 4-dinitrophenol, strong selective adsorption capacity and the like. The preparation process of the 2, 4-dinitrophenol surface molecularly imprinted polymer is simple, the polymerization time is short, the selective adsorption capacity is strong, and the 2, 4-dinitrophenol surface molecularly imprinted polymer has a good development prospect in the aspect of treating 2, 4-dinitrophenol pollutants.
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FIG. 1 is a schematic diagram of the preparation process of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
20mL of absolute ethyl alcohol is used as a solvent, 0.2g of activated silica gel is used as a carrier, 0.037g of 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent (the feeding molar ratio of the 2, 4-dinitrophenol, the 3-aminopropyltriethoxysilane and the tetraethoxysilane is 1:2: 10), 0.5mL of glacial acetic acid (1 mol/L) is used as an initiator, the oscillation initiation polymerization is carried out in a water bath at 30 ℃ for 9h, the obtained product is subjected to Soxhlet extraction for 48h by using a methanol/acetic acid mixed solution with the volume ratio of 9/1, and the obtained product is cleaned by using methanol and then is subjected to vacuum drying at 60 ℃ to obtain the 2, 4-dinitrophenol surface molecularly imprinted polymer.
Example 2
20mL of absolute ethyl alcohol is used as a solvent, 0.2g of activated silica gel is used as a carrier, 0.037g of 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent (wherein the feeding molar ratio of the 2, 4-dinitrophenol, the 3-aminopropyltriethoxysilane and the tetraethoxysilane is 1:6: 20), 0.5mL of glacial acetic acid (1 mol/L) is used as an initiator, the oscillation initiation polymerization is carried out for 30h in a water bath at 30 ℃, the obtained product is oscillated and eluted for 5 times (1 h/time) by using a methanol/acetic acid mixed solution with the volume ratio of 9/1, and the methanol is used for cleaning and then is dried in vacuum at 60 ℃ to obtain the 2, 4-dinitrophenol surface molecularly imprinted polymer.
Example 3
20mL of absolute ethyl alcohol is used as a solvent, 0.2g of activated silica gel is used as a carrier, 0.037g of 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent (the feeding molar ratio of the 2, 4-dinitrophenol, the 3-aminopropyltriethoxysilane and the tetraethoxysilane is 1:12: 35), 0.5mL of glacial acetic acid (1 mol/L) is used as an initiator, the mixture is oscillated and polymerized in a water bath at 30 ℃ for 16h, the obtained product is subjected to Soxhlet extraction for 48h by using a methanol/acetic acid mixed solution with the volume ratio of 9/1, and is cleaned by using methanol and then is dried in vacuum at 60 ℃ to obtain the 2, 4-dinitrophenol surface molecularly imprinted polymer.
Example 4
20mL of absolute ethyl alcohol is used as a solvent, 0.2g of activated silica gel is used as a carrier, 0.037g of 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent (the feeding molar ratio of the 2, 4-dinitrophenol, the 3-aminopropyltriethoxysilane and the tetraethoxysilane is 1:8: 20), 0.5mL of glacial acetic acid (1 mol/L) is used as an initiator, the oscillation and the polymerization are initiated in a water bath at 30 ℃ for 15h, the obtained product is oscillated and eluted 6 times (1 h/time) by using a methanol/acetic acid mixed solution with the volume ratio of 9/1, and the product is cleaned by methanol and then dried in vacuum at 60 ℃ to obtain the 2, 4-dinitrophenol surface molecularly imprinted polymer.
Example 5
10mg of the prepared 2, 4-dinitrophenol surface molecular imprinted polymer and non-imprinted polymer are respectively added into 2mL of 2, 4-dinitrophenol ethanol solution with the molar concentration of 0.5mmol/L (92 mg/L), and the mixture is kept still and soaked for 3 hours at room temperature. The detection result shows that under the adsorption equilibrium condition, the adsorption capacity of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol reaches 89 mu mol/g (16 mg/g), the removal rate is 89%, while the adsorption capacity of the corresponding non-imprinted polymer to the 2, 4-dinitrophenol is 11 mu mol/g (2 mg/g), and the removal rate is only 11%. And (3) after solid-liquid separation of the material used for adsorption, adding 1mL of methanol/water/acetic acid mixed solution with the volume ratio of 40/40/20, standing and soaking for 1h at room temperature, repeatedly soaking for 3 times after solid-liquid separation, and cleaning and drying to obtain regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer and non-imprinted polymer, wherein the adsorption quantity and adsorption efficiency of the regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer and non-imprinted polymer are not obviously changed.
Example 6
10mg of the prepared 2, 4-dinitrophenol surface molecular imprinted polymer and non-imprinted polymer are respectively added into 2mL of 2, 4-dinitrophenol ethanol solution with the molar concentration of 1mmol/L (184 mg/L), and the mixture is kept stand and soaked for 3 hours at room temperature. The detection result shows that under the adsorption equilibrium condition, the adsorption capacity of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol reaches 165 mu mol/g (31 mg/g), the removal rate is 83 percent, and the adsorption quantity of the corresponding non-imprinted polymer to the 2, 4-dinitrophenol is 16 mu mol/g (8 mg/g), and the removal rate is only 8 percent. Separating the solid and liquid of the adsorbed and used material
After separation, 1mL of methanol/water/acetic acid mixed solution with the volume ratio of 40/40/20 is added, standing and soaking are carried out for 1h at room temperature, soaking is carried out for 3 times after solid-liquid separation, and regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer and non-polymer are obtained after cleaning and drying, wherein the adsorption quantity and the adsorption efficiency of the polymer to 2, 4-dinitrophenol are not obviously changed.
Example 7
10mg of the prepared 2, 4-dinitrophenol surface molecular imprinted polymer and non-imprinted polymer are respectively added into 2mL of 2, 4-dinitrophenol ethanol solution with the molar concentration of 3mmol/L (552 mg/L), and the mixture is kept stand and soaked for 3 hours at room temperature. The detection result shows that under the adsorption equilibrium condition, the adsorption capacity of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol reaches 424 mu mol/g (78 mg/g), the removal rate is 71 percent, while the adsorption capacity of the corresponding non-imprinted polymer to the 2, 4-dinitrophenol is 17 mu mol/g (3 mg/g), and the removal rate is only 3 percent. And (3) after solid-liquid separation of the material used for adsorption, adding 1mL of methanol/water/acetic acid mixed solution with the volume ratio of 40/40/20, standing and soaking for 1h at room temperature, repeatedly soaking for 3 times after solid-liquid separation, and cleaning and drying to obtain the regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer and non-polymer material, wherein the adsorption quantity and the adsorption efficiency of the regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer and non-polymer material are not obviously changed.
Example 8
10mg of the prepared 2, 4-dinitrophenol surface molecular imprinted polymer and non-imprinted polymer are respectively added into 2mL of ethanol solution of 2, 4-dinitrophenol with the molar concentration of 6mmol/L (1105 mg/L), and the mixture is kept stand and soaked for 3 hours at room temperature. The detection result shows that under the adsorption equilibrium condition, the adsorption capacity of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol reaches 625 mu mol/g (115 mg/g), the removal rate is 45 percent, while the adsorption capacity of the corresponding non-imprinted polymer to the 2, 4-dinitrophenol is 23 mu mol/g (4 mg/g), and the removal rate is only 1 percent. And (3) after solid-liquid separation of the material used for adsorption, adding 1mL of methanol/water/acetic acid mixed solution with the volume ratio of 40/40/20, standing and soaking for 1h at room temperature, repeatedly soaking for 3 times after solid-liquid separation, and cleaning and drying to obtain the regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer and non-polymer material, wherein the adsorption quantity and the adsorption efficiency of the regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer and non-polymer material are not obviously changed.
Example 9
Respectively adding 2mL of ethanol solution of 13 substrates with the molar concentration of 1mmol/L, such as 2, 4-dinitrophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4, 6-trinitrophenol, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, phenol, N-butylpyridine chloride, metronidazole, o-aminophenol, sulfanilamide or brominated-1-butyl-3-vinyl imidazole, into 10mg of the prepared 2, 4-dinitrophenol surface molecularly imprinted polymer and non-imprinted polymer, and standing and soaking for 3 hours at room temperature. The detection result shows that under the adsorption equilibrium condition, the adsorption amounts of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol and the 2,4, 6-trinitrophenol are 165 [ mu ] mol/g (31 mg/g) and 187 [ mu ] mol/g (42 mg/g), the removal rates are 83% and 93%, while the adsorption amounts to the other 11 substrates are smaller, and the removal rates are all less than 15%.
Example 10
10mg of the 2, 4-dinitrophenol surface molecularly imprinted polymer and the non-imprinted polymer prepared above were taken, 2mL of an ethanol mixed solution containing 2, 4-dinitrophenol (0.025 mmol/L), N-butylpyridine chloride (0.02 mmol/L), 2-nitrophenol (0.08 mmol/L) and phenol (0.3 mmol/L) was added, and the mixture was allowed to stand and soak at room temperature for 3 hours. The detection result shows that under the adsorption equilibrium condition, the 2, 4-dinitrophenol surface molecularly imprinted polymer has an adsorption amount of 4.5 [ mu ] mol/g (8 mg/g) for 2, 4-dinitrophenol, the removal rate reaches 91%, and the N-butylpyridine chloride, the 2-nitrophenol and the phenol which coexist are not adsorbed. The corresponding non-imprinted polymer hardly adsorbs the coexisting 2, 4-dinitrophenol, N-butylpyridine chloride, 2-nitrophenol and phenol.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.

Claims (3)

  1. The application of the 2, 4-dinitrophenol surface molecularly imprinted polymer in selectively separating and enriching 2, 4-dinitrophenol and 2,4, 6-trinitrophenol in a complex environment sample solution is characterized by comprising the following specific steps: taking 10mg of 2, 4-dinitrophenol surface molecularly imprinted polymer, respectively adding 2mL of ethanol solution of 13 substrates of 1mmol/L of 2, 4-dinitrophenol, 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4, 6-trinitrophenol, 2, 4-dichlorophenol, 2,4, 6-trichlorophenol, phenol, N-butylpyridine chloride, metronidazole, o-aminophenol, sulfanilamide or brominated-1-butyl-3-vinylimidazole, standing and soaking for 3h at room temperature, wherein the detection result shows that the adsorption amounts of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol and the 2,4, 6-trinitrophenol are 165 mu mol/g and 187 mu mol/g respectively under the adsorption equilibrium condition, the removal rates are 83 percent and 93 percent respectively, the adsorption capacity to other 11 substrates is small, and the removal rates are all less than 15 percent;
    the structural formula of the 2, 4-dinitrophenol surface molecularly imprinted polymer is as follows:
    Figure DEST_PATH_IMAGE002
    the specific synthetic process comprises the following steps: activated silica gel is used as a carrier, absolute ethyl alcohol is used as a solvent, 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent, glacial acetic acid is used as an initiator, the mixture is oscillated and polymerized for 9 to 30 hours in a water bath at the temperature of 30 ℃, the obtained product is oscillated and eluted by using a methanol/acetic acid mixed solution with the volume ratio of 9/1, or the obtained product is subjected to Soxhlet extraction by using a methanol/ethanol mixed solution with the volume ratio of 9/1, then the product is cleaned by using methanol and dried in vacuum at the temperature of 60 ℃ to obtain a target product, namely, 2, 4-dinitrophenol surface molecularly imprinted polymer, the ratio of the mass of the carrier activated silica gel to the molar mass of the template molecule 2, 4-dinitrophenol is 1g:1mmol, and the template molecule 2,4, The feeding molar ratio of the functional monomer 3-aminopropyltriethoxysilane to the cross-linking agent tetraethyl orthosilicate is 1:2-12: 10-35.
  2. The application of the 2, 4-dinitrophenol surface molecularly imprinted polymer in selectively separating and enriching 2, 4-dinitrophenol and 2,4, 6-trinitrophenol in a complex environment sample solution is characterized by comprising the following specific steps: taking 10mg of 2, 4-dinitrophenol surface molecularly imprinted polymer, respectively adding 2mL of ethanol mixed solution containing 0.025mmol/L of 2, 4-dinitrophenol, 0.02mmol/L of N-butylpyridine chloride, 0.08mmol/L of 2-nitrophenol and 0.3mmol/L of phenol, standing and soaking for 3h at room temperature, and detecting results show, under the adsorption equilibrium condition, the adsorption amount of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol is 4.5 mu mol/g, the removal rate reaches 91 percent, the corresponding non-imprinted polymer hardly adsorbs the coexisting 2, 4-dinitrophenol, N-butylpyridine chloride, 2-nitrophenol and phenol;
    the structural formula of the 2, 4-dinitrophenol surface molecularly imprinted polymer is as follows:
    Figure 647091DEST_PATH_IMAGE002
    the specific synthetic process comprises the following steps: activated silica gel is used as a carrier, absolute ethyl alcohol is used as a solvent, 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent, glacial acetic acid is used as an initiator, the mixture is oscillated and polymerized for 9 to 30 hours in a water bath at the temperature of 30 ℃, the obtained product is oscillated and eluted by using a methanol/acetic acid mixed solution with the volume ratio of 9/1, or the obtained product is subjected to Soxhlet extraction by using a methanol/ethanol mixed solution with the volume ratio of 9/1, then the product is cleaned by using methanol and dried in vacuum at the temperature of 60 ℃ to obtain a target product, namely, 2, 4-dinitrophenol surface molecularly imprinted polymer, the ratio of the mass of the carrier activated silica gel to the molar mass of the template molecule 2, 4-dinitrophenol is 1g:1mmol, and the template molecule 2,4, The feeding molar ratio of the functional monomer 3-aminopropyltriethoxysilane to the cross-linking agent tetraethyl orthosilicate is 1:2-12: 10-35.
  3. The application of the 2, 4-dinitrophenol surface molecularly imprinted polymer in selectively separating and enriching 2, 4-dinitrophenol and 2,4, 6-trinitrophenol in a complex environment sample solution is characterized by comprising the following specific steps: taking 10mg of 2, 4-dinitrophenol surface molecularly imprinted polymer, respectively adding the 10mg of 2, 4-dinitrophenol surface molecularly imprinted polymer into 2mL of 2, 4-dinitrophenol ethanol solution with the molar concentration of 0.5mmol/L, standing and soaking for 3 hours at room temperature, and detecting results show, under the condition of adsorption equilibrium, the adsorption capacity of the 2, 4-dinitrophenol surface molecularly imprinted polymer to the 2, 4-dinitrophenol reaches 89 mu mol/g, the removal rate is 89 percent, after the material after adsorption is separated by solid-liquid, adding 1mL of methanol/water/acetic acid mixed solution with the volume ratio of 40/40/20, standing and soaking for 1h at room temperature, repeatedly soaking for 3 times after solid-liquid separation, and washing and drying to obtain a regenerated 2, 4-dinitrophenol surface molecularly imprinted polymer, wherein the adsorption amount and the adsorption efficiency of the polymer to 2, 4-dinitrophenol are not obviously changed;
    the structural formula of the 2, 4-dinitrophenol surface molecularly imprinted polymer is as follows:
    Figure 829811DEST_PATH_IMAGE002
    the specific synthetic process comprises the following steps: activated silica gel is used as a carrier, absolute ethyl alcohol is used as a solvent, 2, 4-dinitrophenol is used as a template molecule, 3-aminopropyltriethoxysilane is used as a functional monomer, tetraethoxysilane is used as a cross-linking agent, glacial acetic acid is used as an initiator, the mixture is oscillated and polymerized for 9 to 30 hours in a water bath at the temperature of 30 ℃, the obtained product is oscillated and eluted by using a methanol/acetic acid mixed solution with the volume ratio of 9/1, or the obtained product is subjected to Soxhlet extraction by using a methanol/ethanol mixed solution with the volume ratio of 9/1, then the product is cleaned by using methanol and dried in vacuum at the temperature of 60 ℃ to obtain a target product, namely, 2, 4-dinitrophenol surface molecularly imprinted polymer, the ratio of the mass of the carrier activated silica gel to the molar mass of the template molecule 2, 4-dinitrophenol is 1g:1mmol, and the template molecule 2,4, The feeding molar ratio of the functional monomer 3-aminopropyltriethoxysilane to the cross-linking agent tetraethyl orthosilicate is 1:2-12: 10-35.
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