CN115181249A - Electron-withdrawing group functionalized hypercrosslinked polymer and preparation method and application thereof - Google Patents
Electron-withdrawing group functionalized hypercrosslinked polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of organic porous materials, and particularly relates to an electron-withdrawing group functionalized super-crosslinked microporous organic polymer material, a preparation method thereof and a preparation method thereof in CO 2 Use in capture and separation. The invention takes carbonic ester as a construction unit, dichloromethane as a solvent and an external cross-linking agent, and anhydrous aluminum chloride as a Lewis acid catalyst to synthesize the electron-withdrawing group functionalized hypercrosslinked polymer. The polymer has higher BET specific surface area and Langmuir specific surface area and good CO 2 Adsorption and separation performance. The invention can also effectively realize the dual regulation and control of the pore structure and the gas adsorption performance of the functionalized hypercrosslinked polymer by changing the molecular structure of the initial monomer.
Description
Technical Field
The invention belongs to the field of organic porous materials, and particularly relates to an electron-withdrawing group functionalized super-crosslinked polymer, and a preparation method and application thereof.
Background
The rapid growth of global populations, urbanization, and industrialization has dramatically increased energy demand. To meet this energy demand, fossil fuels such as coal, oil, natural gas, etc. are burned in large quantities and release large quantities of CO 2 . Higher CO in the atmosphere 2 Concentration causes phenomena such as glacier melting, sea level rising, sea water acidification, flood tsunami, global warming, disease transmission and the like through the greenhouse effect, so that the world faces great challenges related to climate problems. How to realize CO 2 The capture and separation of (a) has become a significant problem that needs to be solved urgently.
To better address this problem, a variety of adsorbent materials having different pore structures have been developed. The traditional adsorbing materials mainly comprise zeolite, clay, silicon dioxide, diatomite, activated carbon, carbon nano tubes and alkali carbonate, and the emerging adsorbing materials mainly comprise metal organic frameworks and microporous organic polymers including covalent organic networks, conjugated polymers, self-microporous polymers and super-crosslinked polymers. Among these materials, the hypercrosslinked polymers have a wide range of monomer sources, a variety of catalysts, an effective synthesis strategy, a high yield and simple synthesis steps, and can be efficiently prepared by Friedel-crafts reaction. Based on low preparation cost, high specific surface area, narrow pore size distribution, controllable pore size distribution, good rigidity and stability, the hypercrosslinked polymer is in CO 2 The fields of capture and separation exhibit good application prospects and attract a great deal of research interest.
The literature shows that by introducing different contents of heteroatoms such as nitrogen atoms, oxygen atoms, sulfur atoms, silicon atoms, phosphorus atoms and the like and functional groups such as methyl, phenyl, naphthyl, hydroxyl, amino, fluorine atoms, sulfonic groups and the like into a super-crosslinked polymer structure, the interaction between a guest molecule and a polymer framework is regulated and controlled, so that the material quality can be effectively improvedCO 2 Capture and separation performance. For example, N4' -di-1-naphthyl-N4, N4' -di-2-naphthyl- [1,1' -biphenyl, having a high specific surface area and enriched with naphthyl functionality]The-4,4' -diamine organic porous material can absorb 18.85wt% of CO at 273.15K/1.00bar 2 . Pyrrole-based polymers with higher nitrogen content CO at 273.15K 2 /N 2 The adsorption selectivity is as high as 117. It is noteworthy that among these functional groups, the carbonyl group in the polymer structure, as a Lewis base, may react with CO 2 The molecules interact specifically and cause swelling of the polymer, which contributes to an increased overall degree of expansion, CO 2 Solubility in and CO of polymers 2 Performance is captured.
The carbonic ester is a micromolecule compound in which hydrogen atoms of two hydroxyl groups in a carbonic acid molecule are partially or completely substituted by alkyl, can be used as an important industrial raw material for preparing polycarbonate with good mechanical property, heat aging resistance, solvent resistance, arc resistance, insulating property, forming processing and other properties, and can be widely applied to the fields of glass assembly industry, automobile industry, electronics industry, electrical industry, optical disks, packaging, computers, medical treatment, health care, films, leisure, building materials, protective equipment and the like. Due to the rich carbonyl in the molecular structure, the carbonate is expected to become a proper rigid monomer for weaving the functionalized hypercrosslinked polymer and passing through the carbonyl and CO in the polymer chain 2 The interaction between molecules, and further improve the CO of the material 2 Capture and separation performance. In addition, reaction of phosgene with alcohols or phenols, epoxides and CO in the presence of zinc halides 2 Reactions between molecules, etc., also contribute to the large-scale preparation of the desired carbonates. However, CO with carbonate based hypercrosslinked polymers 2 The study on capture and separation performance is lack of relevant reports so far.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a series of functionalized hypercrosslinked polymers with high specific surface area and various structures based on carbonic ester and apply the hypercrosslinked polymers to CO 2 Efficient capture and separation, and demonstrationBased on the commonly used Friedel-crafts reaction, the feasibility of directly weaving various electron-withdrawing functional group functionalized hypercrosslinked polymers by adopting a proper construction monomer. Specifically, the functionalized hypercrosslinked polymer with a novel structure is prepared by using cheap carbonic ester under the catalysis of anhydrous aluminum chloride and through a Friedel-crafts alkylation reaction under mild conditions. Compared with the traditional post-synthesis modification method, the method has the defects of complex operation, low yield, poor stability, high toxicity, multiple potential safety hazards and the like, and is often related to flammable and explosive dangerous medicines or reagents.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the super cross-linked polymer is formed by weaving carbonate ester rich in electron-withdrawing group functional groups as a construction monomer based on a Friedel-crafts reaction, and has a structural general formula as follows:
wherein the content of the first and second substances,
n is the degree of polymerization;
the invention also provides a preparation method of the hypercrosslinked polymer, which is characterized in that under the condition of Lewis acid catalyst (preferably anhydrous aluminum chloride), carbonic ester is selected as a polymerization monomer, and the hypercrosslinked polymer with the functionalized electron-withdrawing group is prepared through Friedel-crafts alkylation reaction.
Further, the carbonate is 9-fluorenylmethyl pentafluorophenyl carbonate, 9-fluorenylmethyl 1-benzotriazolyl carbonate or 9-fluorenylmethyl succinimidyl carbonate.
Further, the preparation method comprises the following specific steps:
dissolving carbonate in an organic solvent (the organic solvent is preferably dichloromethane) in a nitrogen atmosphere, immediately adding a Lewis acid catalyst, reacting for 4 hours at 20 ℃ under stirring, heating to 30 ℃ for reaction for 8 hours, heating to 40 ℃ for reaction for 12 hours, heating to 60 ℃ for reaction for 12 hours, heating to 80 ℃ for reaction for 24 hours, quenching the reaction (preferably with hydrochloric acid with the concentration of 24 wt%), washing, performing Soxhlet extraction with absolute ethyl alcohol for 48 hours, and drying in a vacuum drying oven at 70 ℃ to constant weight to obtain the hypercrosslinked polymer.
The invention also provides the use of the hypercrosslinked polymer in CO 2 Use in capture and separation.
The completion of the work of the invention depends on the national youth natural science fund project (No 22005349), the capital project special for the basic scientific research business cost of the central colleges and universities (No CZQ 21009) and the support plan project of the national folk committee innovation team (No MZR 20006).
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention can smoothly realize the direct and efficient preparation of various electron-withdrawing functional group functionalized hypercrosslinked polymers under mild conditions based on carbonate with different structures and simple one-step Friedel-crafts reaction, and the polymer material has low synthesis cost, is easy for large-scale production and has good application value.
2. The functionalized hypercrosslinked polymer prepared by the invention has higher specific surface area and hierarchical pore structure, and is particularly beneficial to improving CO 2 Microporous structure with adsorption properties, good CO 2 Capture, H 2 Adsorption and CH 4 Storage performance and CO 2 /N 2 And CO 2 /CH 4 Separation performance.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a functionalized hypercrosslinked polymer of the present invention.
FIG. 2 is an infrared spectrum of the functionalized hypercrosslinked polymers obtained in examples 1-3.
FIG. 3 is a solid state carbon spectrum of the functionalized hypercrosslinked polymers obtained in examples 1-3.
FIG. 4 is a scanning electron microscope of the functionalized hypercrosslinked polymers obtained in examples 1 to 3, wherein FIG. 4 (a) is Polymer 1, FIG. 4 (b) is Polymer 2 and FIG. 4 (c) is Polymer 3. Scanning electron microscope pictures show that the obtained polymer has a rough surface and is formed by loosely stacking irregular blocky solids with different sizes.
FIG. 5 shows TEM images of functionalized hypercrosslinked polymers obtained in examples 1-3, wherein FIG. 5 (a) shows Polymer 1, FIG. 5 (b) shows Polymer 2 and FIG. 5 (c) shows Polymer 3. The transmission electron microscope picture shows that the obtained polymer is in an amorphous structure.
FIG. 6 is a thermogravimetric plot of the functionalized hypercrosslinked polymers obtained in examples 1-3 under nitrogen atmosphere.
FIG. 7 (a) shows the nitrogen adsorption/desorption curve for the functionalized hypercrosslinked polymers obtained in examples 1 to 3 at 77.3K/1.00bar and FIG. 7 (b) shows the pore size and pore size distribution for the functionalized hypercrosslinked polymers obtained in examples 1 to 3, in which polymer 3-polymer 1, respectively, are shown from top to bottom.
FIG. 8 (a) CO of functionalized hypercrosslinked polymers obtained in examples 1-3 at 273.15K/1.00bar 2 Adsorption/desorption curves, FIG. 8 (b) at 298.15K/1.00bar, CO of the functionalized hypercrosslinked polymers obtained in examples 1-3 2 FIG. 8 (c) is a graph showing the adsorption and desorption curves for CO in the functionalized hypercrosslinked polymers obtained in examples 1-3 2 FIG. 8 (d) is 77.3K/1.00bar according to the heat of adsorption curve, H for the functionalized hypercrosslinked polymers obtained in examples 1-3 2 Adsorption and desorption curves.
FIG. 9 (a) is at 273.15K/0.25bar, N of functionalized hypercrosslinked polymers obtained in examples 1-3 2 Adsorption-desorption curves, FIG. 9 (b) at 298.15K/0.25bar, N for functionalized hypercrosslinked polymers obtained in examples 1-3 2 FIG. 9 (c) shows the adsorption/desorption curves at 273.15K/1.00bar for CH of the functionalized hypercrosslinked polymers obtained in examples 1 to 3 4 Adsorption-desorption curves, FIG. 9 (d) at 298.15K/1.00bar, CH of functionalized hypercrosslinked polymers obtained in examples 1-3 4 Adsorption and desorption curves.
FIGS. 10a, c, e are CO values for functionalized hypercrosslinked polymers obtained in examples 1-3 based on 273.15K/0.3bar 2 (●)、
And CH 4 (. Diamond.) adsorption Curve, CO calculated by Henry's law initial slope method 2 /N 2 And CO 2 /CH 4 Adsorption Selectivity, where (a) is Polymer 1, (c) is Polymer 2 and (e) is Polymer 3, FIGS. 10b, d, f are CO based on 298.15K/0.3bar, functionalized hypercrosslinked polymers from examples 1-3 2 (●)、
And CH 4 (. Diamond.) adsorption Curve for CO calculated by the initial slope method of Henry's law 2 /N 2 And CO 2 /CH 4 Adsorption selectivity, wherein (b) is polymer 1, (d) is polymer 2 and (f) is polymer 3.
Detailed Description
The following inventors will clearly and completely describe the technical solution of the present invention with reference to the embodiments and the accompanying drawings. The described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention adopts infrared spectrum and solid carbon spectrum to determine the structural composition of the polymer, element analysis is used to determine the element composition of the polymer, thermogravimetric analysis is used to determine the thermal stability of the polymer, scanning electron microscope is used to observe the surface appearance of the polymer, transmission electron microscope is used to observe the internal pore structure of the polymer, the specific surface area and pore size analyzer are used to determine the specific surface area, pore size and pore size distribution of the polymer and CO 2 、N 2 、H 2 And CH 4 And (4) adsorption performance.
Characterization of the product structure in the following examples the apparatus used was as follows: infrared spectroscopy (VERTEX 70 spectrometer), solid-state carbon spectroscopy (WB 400MHz Bruker Avance II spectrometer), elemental analysis (vacuum Micro tube electric Analyzer), scanning electron microscopy (FEI silicon 200 field-emission scanning electron microscope), transmission electron microscopy (Tecnai G2F 30 microscope), thermogravimetric analysis (Perkin Electron Instrument theory 1 TGA), surface-specific gravity analysis (Becky-Zehnder interferometer)Volume analyzer (Micromeritics ASAP2460 surface area and porosity analyzer), CO 2 、N 2 、H 2 And CH 4 Adsorption curves (Micromeritics ASAP2020 surface area and location analyzer).
Example 1:
the specific preparation steps of the 9-fluorenylmethyl pentafluorophenyl carbonate based hypercrosslinked polymer are as follows:
2.0mmol of 9-fluorenylmethyl pentafluorophenylcarbonate (0.8120 g) was added to a 100mL one-neck flask charged with 8mL of methylene chloride under a nitrogen atmosphere, and after sufficiently stirring for 30 minutes, 32mmol of anhydrous aluminum chloride (4.272 g) was immediately added thereto. The mixture is reacted for 4 hours at 20 ℃ under strong stirring, then the temperature is firstly increased to 30 ℃ for 8 hours, then the temperature is increased to 40 ℃ for 12 hours, then the temperature is increased to 60 ℃ for 12 hours, and finally the temperature is increased to 80 ℃ for 24 hours. After the reaction is finished, quenching the reaction product by 25mL of hydrochloric acid (24 wt%), sequentially washing the reaction product twice by deionized water and ethanol respectively, performing Soxhlet extraction for 48 hours by using absolute ethyl alcohol, and finally drying the reaction product for 48 hours in a vacuum drying oven at 70 ℃ until the weight is constant. The polymer obtained was a black solid with a yield of about 126% (yield calculation formula:
wherein m is 1 (g) Denotes the mass of the resulting polymer, m 2 (g) Representing the mass of monomer used to build the polymeric material. Thus, in the art, yields in excess of 100% are normal. Hereinafter, not repeated), as Polymer 1, polymer 1. 13 C NMR(400MHz):130,29ppm.
The structural formula of polymer 1 is:
example 2:
the specific preparation steps of the 9-fluorenylmethyl 1-benzotriazolyl carbonate based hypercrosslinked polymer material are as follows:
2.0mmol of 9-fluorenylmethane under a nitrogen atmosphere1-Benzotriazolyl carbonate (0.7140 g) was charged into a 100mL one-neck flask containing 8mL of methylene chloride, and after stirring thoroughly for 30 minutes, 48mmol of anhydrous aluminum chloride (6.4080 g) was immediately added thereto. The mixture was reacted at 20 ℃ for 4 hours with vigorous stirring, then first warmed to 30 ℃ for 8 hours, then warmed to 40 ℃ for 12 hours, then warmed to 60 ℃ for 12 hours, and finally warmed to 80 ℃ for 24 hours. After the reaction is finished, the reaction solution is quenched by 25mL of hydrochloric acid (24 wt%), washed by deionized water and ethanol respectively twice in sequence, subjected to Soxhlet extraction by ethanol for 48 hours, and finally dried in a vacuum drying oven at 70 ℃ for 48 hours until the weight is constant. The resulting polymer was a black solid at about 124% yield, reported as polymer 2, polymer 2. 13 C NMR(400MHz):130,29ppm.
The structural formula of polymer 2 is:
example 3:
the specific preparation steps of the 9-fluorenylmethylsuccinimidocarbonate-based hypercrosslinked polymer material are as follows:
2.0mmol of 9-fluorenylmethylsuccinimidyl carbonate (0.6740 g) was charged in a 100mL single-neck flask containing 8mL of methylene chloride under a nitrogen atmosphere, and after stirring sufficiently for 30 minutes, 32mmol of anhydrous aluminum chloride (4.2720 g) was immediately added thereto. The mixture was reacted at 20 ℃ for 4 hours with vigorous stirring, then first heated to 30 ℃ for 8 hours, then heated to 40 ℃ for 12 hours, then heated to 60 ℃ for 12 hours, and finally heated to 80 ℃ for 24 hours. After the reaction is finished, the reaction solution is quenched by 25mL of hydrochloric acid (24 wt%), washed by deionized water and ethanol respectively twice in sequence, subjected to Soxhlet extraction by ethanol for 48 hours, and finally dried in a vacuum drying oven at 70 ℃ for 48 hours until the weight is constant. The resulting polymer was a black solid at about 128% yield, reported as polymer 3, polymer 3. 13 C NMR(400MHz):130,29ppm.
The structural formula of polymer 3 is:
FIGS. 2 and 3 are an infrared spectrum and a solid state carbon spectrum of the polymer prepared in examples 1 to 3, respectively, in which polymer 3-polymer 1 was shown from the top down, respectively, and the structural formulae of polymers 1 to 3 were determined as the above formulae (1) to (3) based on the analysis result of the binding elements.
FIG. 7 (a) shows the nitrogen adsorption/desorption curve of the functionalized hypercrosslinked polymers obtained in examples 1 to 3 at 77.3K/1.00bar and FIG. 7 (b) shows the pore size and pore size distribution of the functionalized hypercrosslinked polymers obtained in examples 1 to 3, in which polymer 3-polymer 1, respectively, are shown from top to bottom.
FIG. 8 (a) CO of functionalized hypercrosslinked polymers obtained in examples 1-3 at 273.15K/1.00bar 2 Adsorption-desorption curves, FIG. 8 (b) at 298.15K/1.00bar, CO of functionalized hypercrosslinked polymers obtained in examples 1-3 2 FIG. 8 (c) is a graph showing the adsorption and desorption curves for CO in the functionalized hypercrosslinked polymers obtained in examples 1-3 2 FIG. 8 (d) is 77.3K/1.00bar according to the heat of adsorption curve, H for the functionalized hypercrosslinked polymers obtained in examples 1-3 2 Adsorption and desorption curves.
FIG. 9 (a) is at 273.15K/0.25bar, N of functionalized hypercrosslinked polymers obtained in examples 1-3 2 Adsorption/desorption curves, 298.15K/0.25bar in FIG. 9 (b), N of the functionalized hypercrosslinked polymers obtained in examples 1 to 3 2 FIG. 9 (c) shows the adsorption/desorption curves at 273.15K/1.00bar for CH of the functionalized hypercrosslinked polymers obtained in examples 1 to 3 4 Adsorption-desorption curves, FIG. 9 (d) at 298.15K/1.00bar, CH of functionalized hypercrosslinked polymers obtained in examples 1-3 4 Adsorption and desorption curves.
FIGS. 10a, c, e are CO values for functionalized hypercrosslinked polymers obtained in examples 1-3 based on 273.15K/0.3bar 2 (●)、
And CH 4 (. Diamond.) adsorption Curve, CO calculated by the initial slope method of Henry's law 2 /N 2 And CO 2 /CH 4 Adsorption Selectivity, where (a) is Polymer 1, (c) is Polymer 2 and (e) is Polymer 3, FIGS. 10b, d, f are CO based on 298.15K/0.3bar, functionalized hypercrosslinked polymers from examples 1-3 2 (●)、
And CH 4 (. Diamond.) adsorption Curve CO calculated by Henry's law initial slope method 2 /N 2 And CO 2 /CH 4 Adsorption selectivity, wherein (b) is Polymer 1, (d) is Polymer 2 and (f) is Polymer 3.
TABLE 1 pore structure Properties of functionalized hypercrosslinked polymers
a According to N at 77.3K 2 And (4) calculating the specific surface area of the adsorption isotherm by adopting a BET equation. b According to N at 77.3K 2 The adsorption isotherm was calculated as the specific surface area using the Langmuir equation. c t-Plot pore area. d According to P/P 0 N of 0.050 2 And (5) adsorbing the t-Plot micropore volume calculated by the isotherm.
TABLE 2 CO of functionalized hypercrosslinked polymers 2 And H 2 Adsorption Property and CO 2 Heat of adsorption
a CO at 273.15K/1.00bar was determined using a Micromeritics ASAP 2020M analyzer 2 The amount of adsorption. b The CO at 298.15K/1.00bar was determined using a Micromeritics ASAP 2020M Analyzer 2 The amount of adsorption. c The H at 77.3K/1.00bar was determined using a Micromeritics ASAP 2020M Analyzer 2 And (4) adsorption capacity. d CO according to Polymer samples at 273.15K and 298.15K 2 Adsorption isotherm CO determined using a Micromeritics ASAP 2020M Analyzer 2 The heat of adsorption.
TABLE 3N of functionalized hypercrosslinked polymers 2 And CH 4 Adsorption Property
a The N at 273.15K/0.25bar was determined using a Micromeritics ASAP 2020M analyzer 2 And (4) adsorption capacity. b The N at 298.15K/0.25bar was determined using a Micromeritics ASAP 2020M Analyzer 2 The amount of adsorption. c The CH at 273.15K/1.00bar was determined using a Micromeritics ASAP 2020M Analyzer 4 The amount of adsorption. d The CH at 298.15K/1.00bar was determined using a Micromeritics ASAP 2020M Analyzer 4 The amount of adsorption.
TABLE 4 CO of functionalized hypercrosslinked polymers 2 /N 2 And CO 2 /CH 4 Adsorption selectivity performance
The detection results show that: the polymer prepared by the preparation method has a permanent micropore structure, wherein the BET specific surface area and the Langmuir specific surface area of the functionalized polymer prepared based on 9-fluorenylmethylsuccinimidyl carbonate are as high as 1367m 2 ·g -1 And 2058m 2 ·g -1 852m of micropore area 2 ·g -1 Maximum micropore volume of 0.34cm 3 ·g -1 Pore volume 0.84cm 3 ·g -1 CO at 273.15K/1.00bar 2 Capture 14.61wt%, 77.3K/H at 1.00bar 2 The adsorption quantity was 1.28% by weight, CH at 273.15K/1.00bar 4 The storage amount was 1.79wt%. The obtained polymer has various electron-withdrawing functional groups and electron-donating hetero atoms,CO at 273.15K and 298.15K is calculated based on the initial slope method theory of Henry's law 2 /CH 4 The separation performance is respectively as high as 41.84 and 36.14. In addition, the polymer porosity and CO can be realized by regulating and controlling the molecular structure of the building monomer 2 Double regulation and control of adsorption performance. This is mainly because the chemical structure and stacking structure of the monomer are closely related to the porous structure of the polymer, and slight changes in the chemical structure and stacking structure of the monomer may have a large influence on the porosity of the polymer. It has been found that the three building monomers used, such as 9-fluorenylmethyl pentafluorophenyl carbonate, 9-fluorenylmethyl 1-benzotriazolyl carbonate and 9-fluorenylmethyl succinimidyl carbonate, have similar chemical structures but differ primarily in the terminal functionality. Since the end functional group has no or less reactive sites, and increasing the length of the molecular structure is not favorable for improving the rigidity, BET specific surface area and porosity of the polymer by increasing the flexibility of the monomer molecule. Therefore, as the molecular structure length of 9-fluorenylmethyl pentafluorophenyl carbonate to 9-fluorenylmethyl succinimidyl carbonate decreases, the BET specific surface area of polymers 1 to 3 shows a tendency to increase and the porosity can be well controlled. At the same time, the BET specific surface area, micropore volume, pore size and pore size distribution of the polymer and its CO 2 The adsorption performance is also closely related, and the CO of the polymer with the controllable porous structure 2 The adsorption performance can be well regulated and controlled.
Claims (5)
1. The super cross-linked polymer is formed by weaving carbonate ester rich in electron-withdrawing group functional groups as a construction monomer based on a Friedel-crafts reaction, and has a structural general formula as follows:
wherein the content of the first and second substances,
and n is the degree of polymerization.
2. A method for preparing the hypercrosslinked polymer according to claim 1, wherein the method comprises: under the condition of Lewis acid catalyst, carbonate is selected as a polymerization monomer, and the electron-withdrawing group functionalized super-crosslinked polymer is prepared through Friedel-crafts alkylation reaction.
3. The method according to claim 2, wherein the carbonate is 9-fluorenylmethyl pentafluorophenyl carbonate, 9-fluorenylmethyl 1-benzotriazolyl carbonate or 9-fluorenylmethyl succinimidyl carbonate.
4. The preparation method according to claim 3, comprising the following specific steps:
dissolving carbonate in an organic solvent in a nitrogen atmosphere, immediately adding a Lewis acid catalyst, reacting for 4 hours at 20 ℃ under stirring, then heating to 30 ℃ for reacting for 8 hours, then heating to 40 ℃ for reacting for 12 hours, then heating to 60 ℃ for reacting for 12 hours, finally heating to 80 ℃ for reacting for 24 hours, quenching the reaction after the reaction is finished, washing, performing Soxhlet extraction with absolute ethyl alcohol for 48 hours, and finally drying in a vacuum drying oven at 70 ℃ to constant weight to obtain the super-crosslinked polymer.
5. A hypercrosslinked polymer as claimed in claim 1 in CO 2 Use in capture and separation.
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| CN117861457A (en) * | 2024-03-12 | 2024-04-12 | 兰州大学 | Super-crosslinked polysulfate composite membrane and preparation method and application thereof |
| CN117861457B (en) * | 2024-03-12 | 2024-05-31 | 兰州大学 | Super-crosslinked polysulfate composite membrane and preparation method and application thereof |
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| CN115746270A (en) * | 2022-11-30 | 2023-03-07 | 中南民族大学 | Porosity-controllable high-specific-surface-area super-crosslinked polymer and preparation method and application thereof |
| CN115746270B (en) * | 2022-11-30 | 2024-01-30 | 中南民族大学 | High-specific-surface-area super-crosslinked polymer with controllable porosity and preparation method and application thereof |
| CN117861457A (en) * | 2024-03-12 | 2024-04-12 | 兰州大学 | Super-crosslinked polysulfate composite membrane and preparation method and application thereof |
| CN117861457B (en) * | 2024-03-12 | 2024-05-31 | 兰州大学 | Super-crosslinked polysulfate composite membrane and preparation method and application thereof |
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