Preparation method and application of amphiphilic multi-component covalent organic polymer SLEL-4

Abstract

The invention discloses a preparation method and application of an amphiphilic multi-component covalent organic polymer SLEL-4, and belongs to the field of preparation of environmental materials and nano materials. An amphiphilic multi-component covalent organic polymer material SLEL-4 is prepared through a rapid and convenient solvothermal method, the metering amount of the SLEL-4 in a water body is 1.0 g / L, the adsorption temperature is 298 K, the reaction time is 12 hours, and removal of OPD in the water body is completed. Due to the multi-component system, the SLEL-4 has multi-stage pore channels and excellent stability, has good tolerance, can promote the adsorption performance on pollutants and is suitable for different site environments; the prolonged alkyl chain and aromatic chain endow one side of SLEL-4 with hydrophobicity, and the other side of SLEL-4 keeps hydrophilic due to the existence of the amide chain and sulfonic acid group, and has hydrophilic and oleophylic amphiphilic characteristics, so that more possibilities are provided for applying COPs to the aquifer; the production cost is low, and rapid and large-scale production can be realized.

Description

Technical Field

[0001] The invention belongs to the field of environmental materials and nanomaterial preparation, and particularly relates to a preparation method and application of an amphiphilic multi-component covalent organic polymer SLEL-4. Background Art

[0002] O-phenylenediamine (OPD) is a typical aniline compound widely used in the pesticide and dye industries. A large amount of OPD can enter water bodies through industrial wastewater discharge or as a decomposition product of pesticides. In view of its carcinogenicity, persistent residue and bioaccumulation, the U.S. Environmental Protection Agency (EPA) has listed it as one of the priority controlled pollutants. In recent years, with the rapid development of the dye, pesticide and pharmaceutical industries, the demand for OPD has increased year by year, and the resulting environmental pollution problems have become increasingly severe. Therefore, research on the treatment of OPD-contaminated water bodies has gradually become a focus. At present, there is still a lack of efficient and economical means to treat water bodies containing OPD, so there is an urgent need to find effective methods to remove OPD from environmental water bodies.

[0003] Covalent organic polymers (COPs) are an emerging class of porous materials assembled by strong covalent bonds, with a multi-level pore structure, abundant active sites and excellent chemical stability. However, most COPs still adopt a two-component system, which has the defects of single structure and low efficiency. In addition, traditional COPs usually exhibit hydrophilicity and are mainly used for antibiotics or gas adsorption, while their application in the adsorption of aniline pollutants still faces challenges. At the same time, the limited dispersion stability of COPs greatly limits its practical application effectiveness in aquifers. Therefore, it has become an urgent need to develop amphiphilic materials with both particle and surfactant properties. Summary of the invention

[0004] The purpose of the present invention is to provide a preparation method and application of an amphiphilic multi-component covalent organic polymer SLEL-4 for treating OPD-contaminated water.

[0005] A method for preparing an amphiphilic multi-component covalent organic polymer SLEL-4 comprises the following steps: Step 1: dissolving benzene-1,3,5-trihydrazide in an organic solvent, dimethyl sulfoxide, to a concentration of 0.04 mol / L. The mixed solution is named solution A; Step 2: dissolving 4,4'-diaminobiphenyl-3,3'-disulfonic acid in solution A to a concentration of 0.06 mol / L, and the mixed solution is named solution B; Step 3: Dissolve 4-n-butylaniline in solution B to a concentration of 0.012 mol / L. The mixed solution is named solution C; Step 4: dissolving terephthalaldehyde in solution C to a concentration of 0.12 mol / L, and the mixed solution is named solution D; At this time, the molar ratio of the above D solution is: benzene-1,3,5-trihydrazide: 4,4'-diaminobiphenyl-3,3'-disulfonic acid: 4-n-butylaniline: terephthalaldehyde = 2:3:0.6:6; Step 5: Place the above D solution in a constant temperature oil bath and heat at 100 °C for 30 minutes to obtain a gray-brown polymer; Step 6: The gray-brown polymer obtained in step 5 is placed in a dialysis bag, distilled water is used as the dialysis fluid, and the organic solvent is removed. After 2-3 days, when obvious stratification occurs in the dialysis bag, the polymer is taken out to obtain the obtained product; Step 7: Pour the product obtained in step 6 into a beaker and freeze-dry it at -40°C to obtain the amphiphilic multi-component covalent organic polymer material SLEL-4.

[0006] An amphiphilic multi-component covalent organic polymer SLEL-4 is used. The dosage of SLEL-4 in water is 1.0 g / L, the adsorption temperature is 298 K, and the reaction time is 12 hours, which completes the removal of OPD in water.

[0007] Beneficial effects of the present invention: The present invention prepares an amphiphilic multi-component covalent organic polymer material SLEL-4 by a fast and convenient solvothermal method, which has the following advantages: (1) The multi-component system enables SLEL-4 to have multi-level pores and excellent stability, with good tolerance, which can promote the adsorption performance of pollutants and adapt to different site environments; (2) The extended alkyl chain and aromatic chain endow SLEL-4 with hydrophobicity on one side, while the other side remains hydrophilic due to the presence of amide chain and sulfonic acid group. It has both hydrophilic and lipophilic amphiphilic properties, which provides more possibilities for the application of COPs in aquifers.

[0008] (3) The production cost is low and can be produced quickly and on a large scale. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 This is the Fourier transform-infrared spectrum of SLEL-4 synthesized by the present invention.

[0010] Figure 2 This is the thermogravimetric curve of SLEL-4 synthesized in the present invention under a nitrogen atmosphere.

[0011] Figure 3 This is the nitrogen adsorption-desorption curve of SLEL-4 synthesized in the present invention.

[0012] Figure 4This is a diagram showing the adsorption effect of SLEL-4 synthesized in the present invention on OPD in water. DETAILED DESCRIPTION

[0013] The raw materials used in the synthesis of SLEL-4 are all commercially available products. The OPD-containing simulated liquid is prepared in the laboratory, and the chemical reagents used are commercially available analytical grade products. Example 1

[0014] A method for preparing an amphiphilic multi-component covalent organic polymer SLEL-4 comprises the following steps: Step 1: dissolving benzene-1,3,5-trihydrazide in an organic solvent, dimethyl sulfoxide, to a concentration of 0.04 mol / L. The mixed solution is named solution A; Step 2: Dissolve 4,4'-diaminobiphenyl-3,3'-disulfonic acid in solution A to a concentration of 0.06 mol / L. The mixed solution is named solution B. Step 3: Dissolve 4-n-butylaniline in solution B to a concentration of 0.012 mol / L. The mixed solution is named solution C; Step 4: dissolving terephthalaldehyde in solution C to a concentration of 0.12 mol / L, and the mixed solution is named solution D; At this time, the molar ratio of the above D solution is: benzene-1,3,5-trihydrazide: 4,4'-diaminobiphenyl-3,3'-disulfonic acid: 4-n-butylaniline: terephthalaldehyde = 2:3:0.6:6; Step 5: Place the above D solution in a constant temperature oil bath and heat at 100 °C for 30 minutes to obtain a gray-brown polymer; Step 6: The gray-brown polymer obtained in step 5 is placed in a dialysis bag, distilled water is used as the dialysis fluid, and the organic solvent is removed. After 2-3 days, when obvious stratification occurs in the dialysis bag, the polymer is taken out to obtain the obtained product; Step 7: Pour the product obtained in step 6 into a beaker and freeze-dry it at -40°C to obtain the amphiphilic multi-component covalent organic polymer material SLEL-4. Example 2

[0015] Application of SLEL-4 as adsorbent to remove OPD from water: Step 1: Prepare 20 mg / L, 30 mg / L, 50 mg / L, 110 mg / L, 170 mg / L, and 250 mg / L OPD solutions, add the synthesized SLEL-4 of the present invention at a stoichiometric ratio of 1.0 g / L, and quickly place them in a constant temperature water bath oscillator for oscillation adsorption at 298 K for 12 hours.

[0016] Step 2: Take the supernatant in step 1, filter it with a 0.22 µm filter head, and take the clarified liquid. Use an acetylacetone visible spectrophotometer to detect the residual OPD concentration at a wavelength of 450 nm.

[0017] Step 3: According to the initial concentration and equilibrium concentration of OPD, the equilibrium adsorption capacity of the SLEL-4 synthesized by the present invention for different concentrations of OPD is calculated. In addition, the maximum adsorption capacity of the SLEL-4 synthesized by the present invention for LEV is calculated using the Langmuir isotherm model to be 83.13 mg / g.

Claims

1. A method for preparing an amphiphilic multi-component covalent organic polymer SLEL-4, characterized in that: The following steps are involved: Step 1: dissolving benzene-1,3,5-trihydrazide in an organic solvent, dimethyl sulfoxide, to a concentration of 0.04 mol / L. The mixed solution is named solution A; Step 2: dissolving 4,4'-diaminobiphenyl-3,3'-disulfonic acid in solution A to a concentration of 0.06 mol / L, and the mixed solution is named solution B; Step 3: Dissolve 4-n-butylaniline in solution B to a concentration of 0.012 mol / L. The mixed solution is named solution C; Step 4: dissolving terephthalaldehyde in solution C to a concentration of 0.12 mol / L, and the mixed solution is named solution D; At this time, the molar ratio of the above D solution is: benzene-1,3,5-trihydrazide: 4,4'-diaminobiphenyl-3,3'-disulfonic acid: 4-n-butylaniline: terephthalaldehyde = 2:3:0.6:6; Step 5: Place the above D solution in a constant temperature oil bath and heat at 100 °C for 30 minutes to obtain a gray-brown polymer; Step 6: The gray-brown polymer obtained in step 5 is placed in a dialysis bag, distilled water is used as the dialysis fluid, and the organic solvent is removed. After 2-3 days, when obvious stratification occurs in the dialysis bag, the polymer is taken out to obtain the obtained product; Step 7: Pour the product obtained in step 6 into a beaker and freeze-dry it at -40°C to obtain the amphiphilic multi-component covalent organic polymer material SLEL-4.

2. An application of an amphiphilic multi-component covalent organic polymer SLEL-4, characterized in that: The dosage of SLEL-4 in water was 1.0 g / L, the adsorption temperature was 298 K, and the reaction time was 12 hours, completing the removal of OPD in water.

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