CN110090633B - Nitrogen-rich hypercrosslinked porous polymer material and preparation method and application thereof - Google Patents
Nitrogen-rich hypercrosslinked porous polymer material and preparation method and application thereof Download PDFInfo
- Publication number
- CN110090633B CN110090633B CN201910480412.2A CN201910480412A CN110090633B CN 110090633 B CN110090633 B CN 110090633B CN 201910480412 A CN201910480412 A CN 201910480412A CN 110090633 B CN110090633 B CN 110090633B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- porous polymer
- polymer material
- rich
- hypercrosslinked
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a nitrogen-rich hypercrosslinked porous polymer material and a preparation method and application thereof, which are characterized in that the nitrogen-rich hypercrosslinked porous polymer material is synthesized by a one-step Friedel-crafts alkylation reaction method; triptycene and 2, 4-diamino-6-phenyl-1, 3, 5-triazine are used as a nitrogen source and a carbon source of a synthetic product; the X-ray diffraction analysis shows that the nano-silver-doped titanium dioxide has an obvious dispersion peak in a range of 10-30 degrees, is an amorphous porous structure and has a BET specific surface area of 57-58 m2(ii)/g; the pore size distribution is mainly within the range of 10-20 nm. The preparation method and the obtained product (1) are simple to synthesize: one-step friedel-crafts alkylation, (2) high porosity, and (3) high Malachite Green (MG) adsorption capacity; the N-HCPP shows higher MG adsorption capacity, and the maximum adsorption capacity is 150MG g‑1. In addition, the N-HCPP prepared by the invention has excellent recycling property. The N-HCPP has great modification and application prospects in the aspect of adsorbing MG in water.
Description
Technical Field
The invention belongs to the technical field of chemical adsorption materials, and particularly relates to a nitrogen-rich super-crosslinked porous polymer material, a nitrogen-rich super-crosslinked porous polymer material synthesized by one-step Friedel-crafts alkylation reaction, and adsorption of the nitrogen-rich super-crosslinked porous polymer material on malachite green.
Background
Malachite green is a widely used fungicide in aquaculture worldwide and is very effective against important protozoa and fungal infections. The malachite green is popular in the aquaculture industry because the malachite green can prevent amino acids in bacterial cells from being converted into protein peptides when bacteria divide, and the sterilization effect of the malachite green is shown because the division of the bacteria is prevented; and secondly, the aquatic products are easy to deteriorate and decay in the long-distance transportation process, and the malachite green can play a good role in keeping fresh. At the same time, it is also used as a food colorant, food additive, medical disinfectant and insect repellent and as a dye in the silk, wool, jute, leather, cotton, paper and acrylic industries. The molecular structural formula of malachite green is as follows:
malachite green, however, poses an inevitable risk to consumers and has become a controversial compound on an international scale due to its ability to pose a major hazard to the human immune and reproductive systems. Furthermore, while some countries have been banned from the use of malachite green as a dye, malachite green continues to be used for ornamental fish in many parts of the world due to its low cost, ready availability and availability. Although malachite green has been listed in the list of forbidden veterinary drugs for food animals for a long time in China, many enterprises still use the malachite green privately.
In order to reduce and eliminate the potential risk of malachite green, in recent years, researchers at home and abroad mostly adopt porous carbon materials, gel materials and other natural biological materials to adsorb the malachite green, and obtain good experimental effects.
Disclosure of Invention
Aiming at the defects of the prior art, the inventor researches the synthesis and adsorption application aspects of N-HCPPs prepared by nitrogen, and surprisingly finds that the adsorption performance of the adsorption material on a specific substance is greatly improved and enhanced by nitrogen-rich N-HCPPs. Based on the method, a novel N-HCPP (Nitrogen-bonded Hyper cross linked porous polymer) is synthesized by adopting one-step Friedel-crafts alkylation reaction.
One of the objects of the present invention is to provide a nitrogen-rich hypercrosslinked porous polymeric material;
the second purpose of the invention is to provide a preparation method of the nitrogen-rich hypercrosslinked porous polymer material;
the invention also provides a nitrogen-rich hypercrosslinked porous polymer material used as an adsorbent;
the fourth purpose of the invention is to provide the application of the nitrogen-rich hypercrosslinked porous polymer material as the polymer adsorbent for separating and enriching malachite green;
the fifth purpose of the invention is to provide a method for separating and enriching malachite green by utilizing a nitrogen-rich hypercrosslinked porous polymer material.
The nitrogen-rich super-crosslinked porous polymer material adsorbent provided by the invention has the advantages of high adsorption capacity and high adsorption rate, and can effectively separate and enrich malachite green. The preparation method is simple and convenient and has low cost.
One of the technical schemes of the invention is as follows:
a nitrogen-rich hypercrosslinked porous polymer material is synthesized by a one-step Friedel-crafts alkylation reaction method; triptycene and 2, 4-diamino-6-phenyl-1, 3, 5-triazine are used as a nitrogen source and a carbon source of a synthetic product; the X-ray diffraction analysis shows that the nano-silver-doped titanium dioxide has an obvious dispersion peak in a range of 10-30 degrees, is an amorphous porous structure and has a BET specific surface area of 57-58 m2(ii)/g; the pore size distribution is mainly within the range of 10-20 nm.
The second technical scheme of the invention is as follows: is prepared by the following steps
1) Selecting triptycene (A1) and 2, 4-diamino-6-phenyl-1, 3, 5-triazine (A2) as pre-functionalized monomers, and dissolving the two in anhydrous 1, 2-dichloroethane;
2) under the nitrogen atmosphere, adding dimethoxymethane and anhydrous ferric chloride into the solution by using an injector, heating the obtained mixture to 45 +/-5 ℃, refluxing at constant temperature for 5 +/-0.5 h, then slowly heating to 80 +/-5 ℃, heating at the rate of 5 ℃/min, and refluxing at constant temperature for 19 +/-0.5 h;
3) and cooling the reacted mixture to room temperature, filtering and collecting a crude product, repeatedly washing the product by using a methanol solution until the filtrate is colorless, and then putting the product into a vacuum drying oven at the temperature of 60 +/-5 ℃ for drying to obtain brown solid triazine hypercrosslinked porous polymer powder.
Further, the mole ratio of the triptycene to the 2, 4-diamino-6-phenyl-1, 3, 5-triazine is 3: 1; the molar ratio of dimethoxymethane to anhydrous ferric chloride was 4: 3.
The third technical scheme of the invention is as follows: a nitrogen-rich hypercrosslinked porous polymer material is used as adsorbent.
The fourth technical scheme of the invention is as follows: an application of a nitrogen-rich hypercrosslinked porous polymer material as a polymer adsorbent for separating and enriching malachite green.
The fifth technical scheme of the invention is as follows: a method for adsorbing, separating and enriching malachite green by a nitrogen-rich hypercrosslinked porous polymer material is characterized in that the nitrogen-rich hypercrosslinked porous polymer material is added as an adsorbent for a malachite green-containing aqueous solution with the concentration of 1-800ppm and the pH value of 2-9, the oscillation and the adsorption are carried out, and the volume of the malachite green-containing aqueous solution and the mass ratio of the adsorbent are 5 mL: 2.5 +/-0.2 mg, the adsorption temperature of 25-45 ℃, the adsorption time of 5 min-24 h and the oscillation speed of 170 +/-5 r/min.
Further, the adsorption temperature is 25 ℃, the adsorption time is 3h, and the pH value is 8.
Further, the solution H is respectively adjusted by 1mol/L HCl solution and 1mol/L NaOH solution+And (4) concentration.
The invention has the beneficial effects that:
(1) the nitrogen-rich hypercrosslinked porous polymer material prepared by the invention is prepared by adopting a one-step Friedel-crafts alkylation method, and has the advantages of simplicity, easiness in operation, reusability and the like;
(2) the nitrogen-rich super-crosslinked porous polymer material adsorbent prepared by the invention has high adsorption rate (adsorption capacity is 150mg.g < -1 >) on malachite green in an aqueous solution, and can effectively adsorb and recover the malachite green in the aqueous solution.
(3) The nitrogen-rich super-crosslinked porous polymer material adsorbent prepared by the invention comprises the following components in percentage by weight: large specific surface area, high Malachite Green (MG) adsorption capacity and short adsorption time.
Drawings
FIG. 1 is a schematic diagram of the synthesis of N-HCPP, a nitrogen-rich hypercrosslinked porous polymer material;
FIG. 2 XRD pattern of N-HCPP as a nitrogen-rich hypercrosslinked porous polymeric material;
FIG. 3 SEM images (a) and (b) of N-HCPP; (c) (d) TEM images;
FIG. 4N-enrichment of hypercrosslinked porous polymer material N-HCPP 77K2Adsorption-desorption isotherms, the inset of which is its pore size distribution;
FIG. 5(a) is a graph of adsorption capacity of N-HCPP against MG as a function of time; (b) an adsorption quasi-secondary dynamics model diagram of the MG by the N-HCPP;
FIG. 6(a) adsorption isotherm (298K) of N-HCPP on MG; (b) freundlich isotherm model linear fitting experimental data plot (298K);
FIG. 7 Effect of pH on adsorption Properties of HCATPP (T298K, C)0＝10mg/L，t＝24h)
FIG. 8 Recycling test of N-HCPP.
The specific implementation mode is as follows:
the technical solutions of the present invention are described below by specific embodiments, but the scope of the present invention is not limited thereto.
Example 1: preparation method of nitrogen-rich super-crosslinked porous polymer material
Selection of triptycene (A) for the experiment1) And 2, 4-diamino-6-phenyl-1, 3, 5-triazine (A)2) As a pre-functionalized monomer. Briefly, solid reactant A is prepared1(0.03mol, 7.63g) and A2(0.01mol, 1.87g) was dissolved in 15mL of anhydrous 1, 2-dichloroethane. Dimethoxymethane (0.08mol, 7.06mL) and nothing were added to the above solution using a syringe under a nitrogen atmosphereFerric chloride hydrate (0.06mol, 9.75 g). The mixture was heated to 45 ℃ and refluxed at constant temperature for 5h, then slowly heated to 80 ℃ and refluxed at constant temperature for 19 h. After cooling to room temperature, the crude product was collected by filtration and washed repeatedly with methanol solution until the filtrate was almost colorless. And finally, putting the product into a vacuum drying oven at 60 ℃ for drying to obtain brown solid triazine hypercrosslinked porous polymer particles.
The synthetic route of the N-HCPP is shown in figure 1; through X-ray diffraction, the polymer adsorbent has an obvious dispersion peak within the range of 10-30 degrees, and the polymer material prepared by experiments can be proved to have an obvious amorphous porous structure, which is shown in figure 2; by analyzing the characterization results of SEM and TEM, the structure of the HCATPP material is further proved to contain a certain mesopore and macropore structure, and the structure is mainly the macropore structure, which is shown in figure 3; the pore performance of N-HCPP was analyzed as shown in FIG. 4.
The experimental method for adsorbing, separating and enriching malachite green by the nitrogen-rich hypercrosslinked porous polymer material comprises the following steps:
1) preparing a series of MG solutions with different concentrations ranging from 1 ppm to 800ppm for adsorption experiments, adding 2.5 +/-0.2 MG of nitrogen-rich hypercrosslinked porous polymer material (N-HCPP) into 5mL of MG aqueous solution, and continuously oscillating for 24 hours at room temperature; separating the adsorbed N-HCPP from the solution by using a disposable filtering device, and characterizing the concentration of filtrate at 618nm of wavelength by using an ultraviolet-visible spectrum; the adsorption capacity of N-HCPP to MG and the removal rate thereof are calculated by the following formula:
wherein q iseDenotes the adsorption capacity mg.g-1；C0And CeThe initial concentration and the equilibrium concentration ppm of the dye in the aqueous solution respectively; v is the volume mL of the solution, m is the mass mg of the adsorbent; eta represents the poreThe removal rate of malachite green;
2) for the dynamic adsorption study, 2.5 +/-0.2 MG of N-HCPP is added into 5mL of MG aqueous solution with the initial concentration of 10ppm, and the mixture is oscillated for different time at regular intervals; separating the adsorbed N-HCPP from the solution by using a disposable filtering device, and testing the concentration of filtrate by using an ultraviolet-visible spectrum;
3) for the study on the influence of pH value on the adsorption performance, the pH of MG aqueous solution with the initial concentration of 10ppm is respectively adjusted to 2, 3, 4, 5, 6, 7, 8 and 9, then 25 +/-2 MG of N-HCPP is added into the solution, and the solution is shaken for 24 +/-0.5 h; separating the adsorbed N-HCPP from the solution by using a disposable filtering device, and testing the concentration of filtrate by using an ultraviolet-visible spectrum;
4) for cyclic adsorption research, adding 25 +/-2 MG of N-HCPP into 50mL of MG aqueous solution with the concentration of 10ppm, and oscillating for 24 +/-0.5 h; carrying out suction filtration on the adsorbed solution by a circulating water vacuum pump, measuring the absorbance of the filtrate by using an ultraviolet-visible spectrophotometer, washing the adsorbed adsorbate for 5 times by using absolute ethyl alcohol, and then washing the adsorbate for 5 times by using deionized water; and (3) drying the washed adsorbent in an electrothermal blowing drying oven at the temperature of 80 ℃, and carrying out the next round of adsorption experiment on the dried N-HCPP.
See examples 2, 3, 4, 5 for details.
Example 2
The hypercrosslinked porous polymer material N-HCPP (2.5. + -. 0.2MG) was added to different concentrations of aqueous MG solution (5mL) and shaken continuously at 25 ℃ for 24 h. The adsorbed N-HCPP was separated from the solution using a disposable filter unit and the filtrate concentration was measured by UV-visible spectroscopy at 618 nm. With the increase of the concentration before MG adsorption, the adsorption amount of MG by N-HCPP gradually increases until the value is stabilized. At lower concentrations, more adsorption sites are available. With increasing concentration, MG dye molecules occupy available sites on the N-HCPP surface after reaching maximum adsorption capacity. Therefore, the adsorption amount tends to be in equilibrium after the concentration continues to increase. The Freundlich isotherm model is used for fitting the isotherm experimental data, and the linear correlation coefficient R of the fitting of the N-HCPP to the MG can be seen2Up to 0.995 or more, see fig. 5.
Example 3
The hypercrosslinked porous polymer material N-HCPP (2.5. + -. 0.2MG) was added to an aqueous MG solution with an initial concentration of 10ppm and shaken at regular intervals for different times at 25 ℃. The adsorbed N-HCPP was separated from the solution using a disposable filter unit and the filtrate concentration was measured by UV-visible spectroscopy at 618 nm. The results showed that the removal rate of MG by N-HCPP was 60% or more in 5 minutes. Further, after the experimental data are fitted by a quasi-second-order kinetic model, a linear correlation coefficient R is obtained2Up to 0.9997, calculated adsorption rate constant k2The value was 0.00497g mg min-1. The results show that the adsorption of MG by N-HCPP follows the quasi-second order kinetics, FIG. 6.
Example 4
The hypercrosslinked porous polymer material N-HCPP (2.5 + -0.2 MG) was added to an MG aqueous solution with an initial concentration of 10ppm and pH values of 2, 3, 4, 5, 6, 7, 8, 9 and shaken at 25 ℃ for 24 + -0.5 h. The adsorbed N-HCPP was separated from the solution using a disposable filter unit and the filtrate concentration was measured by UV-visible spectroscopy at 618 nm. The results show that the adsorption amount shows a tendency of decreasing and then increasing along with the increase of the pH value, and when the pH value is increased to about 7, the adsorption amount of malachite green by the adsorption substance is basically balanced, see the attached figure 7.
Example 5
The hypercrosslinked porous polymer material N-HCPP (25. + -.2 MG) was added to 50mL of 10ppm starting MG aqueous solution and shaken at 25 ℃ for 24. + -. 0.5 h. The adsorbed N-HCPP was separated from the solution using a disposable filter unit and the filtrate concentration was measured by UV-visible spectroscopy at 618 nm. Washing the adsorbed adsorbate with anhydrous ethanol for 5 times, and then washing with deionized water for 5 times; and (3) drying the washed adsorbent in an electrothermal blowing drying oven at 80 ℃, carrying out the next round of adsorption experiment on the dried N-HCPP, and keeping the removal percentage of HCATPP to be more than 70% after 5 adsorption-desorption cycle experiments. The results show that the material has good reusability, and can effectively remove the dye from the aqueous solution, see figure 8.
The product of the invention is characterized as follows:
1) an X-ray powder diffractometer (XRD) used a D/Max2550VB/PC diffractometer, Cu K alpha rays, an operating voltage of 40kV and an operating current of 200 mA. The polymer adsorbent has an obvious dispersion peak within a range of 10-30 degrees, and can show that the polymer material prepared by experiments has an obvious amorphous porous structure.
2) Scanning Electron Microscopy (SEM) characterization adopted Nova NanoS 450 from FEI of the Netherlands, and samples were not required to be treated and accelerated at a voltage of 5kV before testing.
3) Characterization of the porous Properties in N2Adsorption-desorption ASAP 2020 (micromeritics, USA) and degassing treatment at 120 deg.C under vacuum for 12 hours before sample testing. Under high pressure (0.8-1.0) environment, the adsorbent exhibits a typical type IV isotherm, indicating the presence of mesoporous and microporous structures in the adsorbent. The specific surface area of the adsorbent is calculated to be 57.8904m through the fitting result of the BET equation and the BJH equation2(ii) in terms of/g. The pore size distribution of the adsorbent can be seen to be mainly within the range of 10-20 nm.
The adsorbent material according to the invention is characterized as follows: the ultraviolet-visible absorption spectrum (UV-Vis) is measured on a new century ultraviolet-visible spectrometer by a general instrument T6 of Beijing Puproud analysis.
Example 6: the preparation method of the nitrogen-rich hypercrosslinked porous polymer material has good effect in the following range.
Selection of triptycene (A) for the experiment1) And 2, 4-diamino-6-phenyl-1, 3, 5-triazine (A)2) As a pre-functionalized monomer. Briefly, solid reactant A is prepared1(0.03mol) and A2(0.01mol) was dissolved in 15mL of anhydrous 1, 2-dichloroethane. Dimethoxymethane (0.08mol) and anhydrous ferric chloride (0.06mol) were added to the above solution using a syringe under a nitrogen atmosphere. Heating the obtained mixture to 45 + -5 deg.C, refluxing at constant temperature for 5 + -0.5 h, then slowly heating to 80 + -5 deg.C, and refluxing at constant temperature for 19 + -0.5 h. After cooling to room temperature, the crude product was collected by filtration and washed repeatedly with methanol solution until the filtrate was almost colorless. Finally, the product is put into a vacuum drying oven with the temperature of 60 +/-0.5 ℃ for drying, and the brown solid triazine hypercrosslinked porous polymer particles are obtained。
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A nitrogen-rich hypercrosslinked porous polymer material is characterized in that the nitrogen-rich hypercrosslinked porous polymer material is synthesized by a one-step Friedel-crafts alkylation reaction method; triptycene and 2, 4-diamino-6-phenyl-1, 3, 5-triazine are used as a carbon source and a nitrogen source of a synthetic product; the X-ray diffraction analysis shows that the nano-silver-doped titanium dioxide has an obvious dispersion peak in a range of 10-30 degrees, is an amorphous porous structure and has a BET specific surface area of 57-58 m2(ii)/g; the pore size distribution is mainly within the range of 10-20 nm.
2. The nitrogen-enriched hypercrosslinked porous polymer material of claim 1, wherein the nitrogen-enriched hypercrosslinked porous polymer material is synthesized by a one-step friedel-crafts alkylation reaction method; triptycene and 2, 4-diamino-6-phenyl-1, 3, 5-triazine are used as a carbon source and a nitrogen source of a synthetic product, and the preparation method comprises the following steps:
1) selecting triptycene (A)1) And 2, 4-diamino-6-phenyl-1, 3, 5-triazine (A)2) As pre-functionalized monomers, both were dissolved in anhydrous 1, 2-dichloroethane;
2) under the nitrogen atmosphere, adding dimethoxymethane and anhydrous ferric chloride into the solution by using an injector, heating the obtained mixture to 45 +/-5 ℃, refluxing at constant temperature for 5 +/-0.5 h, then slowly heating to 80 +/-5 ℃, heating at the rate of 5 ℃/min, and refluxing at constant temperature for 19 +/-0.5 h;
3) and cooling the reacted mixture to room temperature, filtering and collecting a crude product, repeatedly washing the product by using a methanol solution until the filtrate is almost colorless, and then putting the product into a vacuum drying oven at the temperature of 60 +/-5 ℃ for drying to obtain brown solid triazine hypercrosslinked porous polymer powder.
3. The nitrogen-enriched hypercrosslinked porous polymer material of claim 2, wherein the molar ratio of triptycene to 2, 4-diamino-6-phenyl-1, 3, 5-triazine is 3: 1; the molar ratio of dimethoxymethane to anhydrous ferric chloride was 4: 3.
4. Use of a nitrogen-rich hypercrosslinked porous polymeric material according to claim 1 or 2 as an adsorbent.
5. Use of a nitrogen-rich hypercrosslinked porous polymeric material of claim 1 or 2 as a polymeric adsorbent for the separation and enrichment of malachite green.
6. A method for adsorbing, separating and enriching malachite green by using the nitrogen-enriched hypercrosslinked porous polymer material as claimed in claim 1 or 2,
adding a nitrogen-rich super-crosslinked porous polymer material as an adsorbent for a malachite green-containing aqueous solution with the concentration of 1-800ppm and the pH value of 2-9, oscillating, and adsorbing, wherein the volume of the malachite green-containing aqueous solution and the mass ratio of the adsorbent are 5 mL: 2.5 +/-0.2 mg, the adsorption temperature of 25-45 ℃, the adsorption time of 5 min-24 h and the oscillation speed of 170 +/-5 r/min.
7. The process according to claim 6, wherein the adsorption temperature is 25 ℃, the adsorption time is 3h and the pH is 8.
8. Process according to claim 6 or 7, characterized in that the pH is adjusted by means of a 1mol/L HCl solution and a 1mol/L NaOH solution, respectively, of solution H+And (4) concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910480412.2A CN110090633B (en) | 2019-06-04 | 2019-06-04 | Nitrogen-rich hypercrosslinked porous polymer material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910480412.2A CN110090633B (en) | 2019-06-04 | 2019-06-04 | Nitrogen-rich hypercrosslinked porous polymer material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110090633A CN110090633A (en) | 2019-08-06 |
| CN110090633B true CN110090633B (en) | 2022-02-22 |
Family
ID=67450161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910480412.2A Active CN110090633B (en) | 2019-06-04 | 2019-06-04 | Nitrogen-rich hypercrosslinked porous polymer material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110090633B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114023573B (en) * | 2021-11-02 | 2023-11-10 | 南京信息工程大学 | Preparation method of triazinyl aza two-dimensional electrode material |
| CN115090269B (en) * | 2022-06-02 | 2023-09-19 | 齐鲁工业大学 | Application of super-crosslinked polyaniline with good chemical stability in wastewater treatment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371112A (en) * | 2014-10-17 | 2015-02-25 | 中国科学院上海有机化学研究所 | Organic porous polymer based on triptycene skeleton as well as preparation method and application of organic porous polymer |
| CN107488261A (en) * | 2017-06-14 | 2017-12-19 | 中南大学 | A kind of rich carboxylic micropore organic polymer material and preparation method thereof |
| CN107759796A (en) * | 2017-11-21 | 2018-03-06 | 齐鲁工业大学 | The preparation method of a kind of porous super cross-linked polymer |
| CN108585100A (en) * | 2018-04-18 | 2018-09-28 | 福州大学 | A method of adsorbing water Malachite Green using metal-organic framework materials MIL-100 (Fe) |
| CN109317120A (en) * | 2018-10-19 | 2019-02-12 | 福州大学 | A kind of super crosslinked polymeric materials and preparation method thereof |
-
2019
- 2019-06-04 CN CN201910480412.2A patent/CN110090633B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104371112A (en) * | 2014-10-17 | 2015-02-25 | 中国科学院上海有机化学研究所 | Organic porous polymer based on triptycene skeleton as well as preparation method and application of organic porous polymer |
| CN107488261A (en) * | 2017-06-14 | 2017-12-19 | 中南大学 | A kind of rich carboxylic micropore organic polymer material and preparation method thereof |
| CN107759796A (en) * | 2017-11-21 | 2018-03-06 | 齐鲁工业大学 | The preparation method of a kind of porous super cross-linked polymer |
| CN108585100A (en) * | 2018-04-18 | 2018-09-28 | 福州大学 | A method of adsorbing water Malachite Green using metal-organic framework materials MIL-100 (Fe) |
| CN109317120A (en) * | 2018-10-19 | 2019-02-12 | 福州大学 | A kind of super crosslinked polymeric materials and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Hydroxyl-Based Hyper-Cross-Linked Microporous Polymers and Their Excellent Performance for CO2 Capture;Yin Liu et al.;《Ind. Eng. Chem. Res.》;20181130;第57卷;第17259-17265页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110090633A (en) | 2019-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104703689B (en) | Magnetic activated carbons and the method for being used to prepare and regenerating such material | |
| Zhang et al. | Enhancement of CO2 adsorption on high surface area activated carbon modified by N2, H2 and ammonia | |
| CN108201878B (en) | Preparation method of carbon-point-modified metal organic framework adsorption material and application of carbon-point-modified metal organic framework adsorption material in treatment of water pollutants | |
| CN102784624B (en) | Preparation method and use of carbon coated magnetic adsorption material | |
| CN105233802B (en) | One kind doping arginic copper base metal organic framework materials of L and preparation method thereof | |
| CN109499529A (en) | A kind of magnetic porous carbon material of N doping and its preparation method and application | |
| CN110237820B (en) | Preparation method and application of microwave-assisted magnetic hollow Zn/Co zeolite imidazole nanocage material | |
| CN111647184B (en) | Covalent organic framework film material for removing triclosan in environmental water and preparation method and application thereof | |
| CN110090633B (en) | Nitrogen-rich hypercrosslinked porous polymer material and preparation method and application thereof | |
| CN106044744B (en) | A kind of preparation method and its usage of graphene/lignin-base combined multi-stage hole carbon plate material | |
| CN106824090B (en) | Preparation method and application of novel magnetic metal organic framework composite material | |
| CN113929905B (en) | Preparation method and application of imine bond-connected fluorescent covalent organic framework | |
| CN113842889A (en) | Microwave synthesis metal organic framework material DUT-5(Al) and synthesis method and application thereof | |
| CN116371388B (en) | Magnetic sponge carbon for adsorbing microplastic and preparation method and application thereof | |
| CN111298761B (en) | Modified sepiolite adsorbent and preparation method and application thereof | |
| CN114471450B (en) | g-C 3 N 4 @SiO 2 Preparation method of (1) | |
| Kusrini et al. | Enrichment process of biogas using simultaneous absorption-adsorption methods | |
| CN109608652A (en) | MOFs crystalline material and its preparation, application | |
| CN114749149A (en) | Carbon material for formaldehyde purification and preparation method thereof | |
| CN115318254B (en) | Sodium lignin sulfonate/chitosan @ ZIF-8 composite material and preparation method and application thereof | |
| CN117229524B (en) | Green preparation method and application of defective metal organic frame material | |
| CN117123199B (en) | Acetic acid modified metal-organic framework adsorption material and preparation method and application thereof | |
| RU2794181C1 (en) | Porous composite absorbent for selective gas separation and method for its production | |
| CN116120574B (en) | Preparation method and application of cobalt-based amorphous metal organic framework material Co-aMOF | |
| CN116925344B (en) | Porous triazinyl sulfur-containing polyamide material, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |