CN111841509A - High CO2Selective polymer adsorbent and preparation method thereof - Google Patents

High CO2Selective polymer adsorbent and preparation method thereof Download PDF

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CN111841509A
CN111841509A CN202010651832.5A CN202010651832A CN111841509A CN 111841509 A CN111841509 A CN 111841509A CN 202010651832 A CN202010651832 A CN 202010651832A CN 111841509 A CN111841509 A CN 111841509A
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aromatic
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ketone
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廖耀祖
曾沁若
程中桦
何颜
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Donghua University
National Dong Hwa University
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    • 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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
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Abstract

The invention relates to a high CO2Selective polymeric adsorbents and methods for making the same. The adsorbent is prepared by performing aldehyde-ketone condensation and conjugate addition on aromatic aldehyde, aromatic ketone and ammonium acetate under pyridine and cyclizing with ammonia to form a pyridine ring. The method comprises the following steps: mixing aromatic aldehyde and aromatic ketone, adding ammonium acetate and pyridine, performing aldehyde ketone condensation, conjugate addition and cyclization reaction with ammonia, filtering, washing and drying. The adsorbent can selectively adsorb CO2Increase CO2The amount of adsorption of (3).

Description

High CO2Selective polymer adsorbent and preparation method thereof
Technical Field
The invention belongs to CO2The field of adsorbents and preparation thereof, in particular to a high CO adsorbent2Selective polymeric adsorbents and methods for making the same.
Background
The conjugated microporous polymer has the characteristics of high specific surface area, various synthesis methods, excellent physical and chemical stability, controllable pore structure, functional adjustability and the like, and has wide application prospects in the fields of gas adsorption and separation, energy storage, catalysis, electrochemistry and the like. Is currently used for CO2The adsorbed porous material is prepared by a C-C metal coupling method, is expensive and has CO resistance 2The selectivity is poor and the adsorption capacity needs to be improved. Example Timur Islamog et al construction of nanoporous organic frameworks NPOF-1 via nickel-catalyzed 1,3, 5-tris (4-bromophenyl) benzene, NPOF-1-NH at 298K2To CO2/N2The selectivity of (3) is 25.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high CO2Selective polymer adsorbent and preparation method thereof to overcome the defect of CO application in the prior art2Adsorbed porous material to CO2Poor selectivity, low adsorption capacity and the like.
The invention provides CO2The selective polymer adsorbent is prepared by performing aldehyde-ketone condensation and conjugate addition on aromatic aldehyde, aromatic ketone and ammonium acetate in the presence of pyridine and cyclizing the aldehyde-ketone condensation and conjugate addition and ammonia to form a pyridine ring, so that the pyridine nitrogen-doped conjugated microporous polymer is obtained.
The aromatic aldehyde includes 1,3, 5-tris (p-formylphenyl) benzene, 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine or tris (4-formylphenyl) amine.
The aromatic ketone comprises: 1, 4-diacetylbenzene or 1,3, 5-triacetylbenzene.
The invention also provides CO2A method of making a selective polymeric adsorbent comprising:
mixing aromatic aldehyde and aromatic ketone, adding ammonium acetate and pyridine, performing aldehyde ketone condensation and conjugate addition and cyclization reaction with ammonia, filtering, washing and drying to obtain the pyridine nitrogen-doped conjugated microporous polymer, namely CO 2A selective polymeric adsorbent, wherein the molar ratio of aldehyde groups of aromatic aldehydes to ketone groups of aromatic ketones is from 1:2 to 2:1, and the molar amount of ammonium acetate isThe total molar weight of the aromatic aldehyde and the aromatic ketone is 9-11 times, and the ratio of the aromatic aldehyde to the pyridine is 0.5mmol: 30-100 mL.
The reaction temperature of the aldehyde ketone condensation, the conjugate addition and the ammonia cyclization is 110-120 ℃, and the reaction time is 12-24 hours.
The filtration adopts suction filtration, the suction filtration needs to be carried out in a sand core funnel, and the suction filtration process is washed by deionized water.
The washing is as follows: washing the mixture by deionized water and an organic solvent at 60-80 ℃ for 24 hours.
The organic solvent comprises methanol and chloroform or DMSO, methanol and chloroform.
The drying comprises the following steps: vacuum drying at 60-100 ℃ for 20-24 h.
The invention also provides CO2The selective polymer adsorbent is applied to gas adsorption and photocatalysis.
The invention also provides CO2Use of a selective polymeric adsorbent for carbon dioxide adsorption and separation.
The nitrogenous porous organic polymer is a nitrogenous conjugated microporous polymer prepared by a Chichibabin reaction, continuous aldehyde-ketone condensation and conjugated addition (Michael addition) and cyclization with ammonia (carbonyl and amino form an imine group) form a pyridine ring, and the existence of the pyridine ring provides rigidity, thermal stability and chemical stability for the polymer. The nitrogen atom incorporated in the carbon skeleton can be used as CO 2Can increase CO2Thereby achieving the purpose of separating the gas from other gases. And (3) deoxidizing carbonyl to form a ring, forming pyridyl and constructing a conjugated microporous network structure.
The invention improves the adsorption capacity by changing the construction unit and optimizing the specific surface area and the pore structure; and the cost is low due to nonmetal coupling.
Advantageous effects
(1) The invention adopts two aromatic compounds containing carbonyl groups to perform condensation and conjugate addition in a pyridine environment, and simultaneously cyclizes with ammonia to form a pyridine ring to synthesize the pyridine nitrogen-doped conjugated microporous polymer, and the synthetic method has simple operation and lower cost.
(2) The conjugated microporous polymer selectively adsorbs CO2Increase CO2The adsorption capacity of the catalyst has potential application value in the fields of gas adsorption and separation, energy storage, catalysis, electrochemistry and the like.
Drawings
FIG. 1 is an XPS plot of pyridyl conjugated microporous polymer-1 synthesized in example 1;
FIG. 2 shows the N at 77.4K of the pyridyl conjugated microporous polymer-1 synthesized in example 12Adsorption-desorption curve of (a);
FIG. 3 shows the CO at 298K of the pyridyl conjugated microporous polymer-1 synthesized in example 12And N2Initial adsorption slope curve of (1);
FIG. 4 is a schematic representation of pyridyl conjugated microporous polymer-2 synthesized in example 2 13C-NMR chart;
FIG. 5 shows the CO at 273K of pyridyl conjugated microporous polymer-2 synthesized in example 22Adsorption-desorption curves;
FIG. 6 is a CO at 273K of the pyridine/bipyridine conjugated microporous polymer 2 synthesized in example 22And N2Initial adsorption slope curve of (1);
FIG. 7 is an XPS plot of pyridyl conjugated microporous polymer-3 synthesized in example 3;
FIG. 8 shows the N at 77.4K of the pyridyl conjugated microporous polymer-3 synthesized in example 32Adsorption-desorption curve of (a);
FIG. 9 shows the CO at 298K of the pyridyl conjugated microporous polymer-3 synthesized in example 32Adsorption-desorption curves;
FIG. 10 shows the CO at 298K of the pyridyl conjugated microporous polymer-3 synthesized in example 32And N2Initial adsorption slope curve of (1);
FIG. 11 is a schematic representation of pyridyl conjugated microporous polymer-4 synthesized in example 413C-NMR chart;
FIG. 12 shows the N at 77.4K of pyridyl conjugated microporous polymer-4 synthesized in example 42Adsorption-desorption curve of (a);
FIG. 13 shows the CO at 298K of the pyridyl conjugated microporous polymer-4 synthesized in example 42Adsorption-desorption curves;
FIG. 14 shows the CO at 298K of the pyridyl conjugated microporous polymer-4 synthesized in example 42And N2Initial adsorption slope curve of (1);
FIG. 15 is an XPS plot of pyridyl conjugated microporous polymer-5 synthesized in example 5;
FIG. 16 shows the N at 77.4K of pyridyl conjugated microporous polymer-5 synthesized in example 52Adsorption-desorption curve of (a);
FIG. 17 shows the CO at 298K of the pyridyl conjugated microporous polymer-5 synthesized in example 52Adsorption-desorption curves;
FIG. 18 shows the CO at 298K of the pyridyl conjugated microporous polymer-5 synthesized in example 52And N2Initial adsorption slope curve of (1).
FIG. 19 shows the CO at 298K of the pyridyl conjugated microporous polymer-5 synthesized in comparative example 12Adsorption-desorption curve.
FIG. 20 shows the CO at 298K of the pyridyl conjugated microporous polymer-5 synthesized in comparative example 12And N2Initial adsorption slope curve of (1).
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Aromatic aldehydes were purchased from keyulin, aromatic ketones from TCI, and pyridine and ammonium acetate from the national pharmaceutical group. Both the polymer pore size and the selective adsorption test were determined by micromeritics ASAP 2460.
Example 1
1, 4-diacetophenone (243.3mg, 1.5mmol), tris (4-formylphenyl) amine (164.7mg, 0.5mmol) were combined and placed in a 200mL round bottom flask, ammonium acetate (1.54g, 20mmol) was added, then100ml of pyridine was added to dissolve the above mixed powder completely, and finally the mixture was stirred at an oil bath temperature of 115 ℃ for 24 hours. After the reaction is finished, performing suction filtration, respectively stirring and washing the mixture by deionized water, methanol and chloroform at 60 ℃ for 24 hours, performing suction filtration, and then drying the mixture in a vacuum oven at 60 ℃ for 24 hours to obtain the pyridyl-containing conjugated microporous polymer, which is marked as polymer-1 and has the BET specific surface area of 304m2/g。
The XPS nitrogen spectrum of polymer-1 obtained in this example is shown in FIG. 1, where the nitrogen is present in the monomer only in the form of C-N at 399.8 eV. XPS spectra showed that, in addition to the C-N peak present in the monomer itself, a new peak at 398.5eV was identified, where the peak was the peak for pyridine N. It was thus confirmed that the polymer contained a pyridine ring. The successful synthesis of polymer-1 was confirmed.
Polymer 1 obtained in this example has an N value of 77.4K2As shown in FIG. 2, it can be seen that the adsorption isotherm is in the low relative pressure region (P/P)0<0.001), the curve rises rapidly, indicating that gas adsorption is faster due to the presence of micropores, indicating that a certain microporous structure exists in polymer-1; in the middle and high relative pressure region (P/P) 00.1 to 1.0), the curve rises at a relatively slow rate, indicating the presence of macropores in polymer-1. While the final desorption and adsorption curves were not completely closed, probably due to small amounts of N2Remained in the pores of the polymer-1 and could not be completely desorbed.
Polymer-1 obtained in this example had CO at 298K2And N2The initial adsorption slope curve of (A) is shown in FIG. 3, and the fitted CO is calculated2And N2The ratio of the initial adsorption curve slopes indicates the CO2/N2The adsorption selectivity is 35.7, and the adsorption selectivity is good.
Example 2
1, 4-diacetophenone (243.3mg, 1.5mmol), 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine (196.7mg, 0.5mmol) were combined and placed in a 200ml round bottom flask, ammonium acetate (1.54g, 20mmol) was added, 100ml pyridine was added to dissolve all the above mixed powder, and the mixture was brought to 115 deg.CThe reaction was stirred at the oil bath temperature for 24 h. After the reaction is finished, performing suction filtration, respectively stirring and washing with deionized water (60 ℃), DMSO (80 ℃), methanol (60 ℃) and chloroform (60 ℃) for 24 hours, performing suction filtration, and then placing in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the pyridyl-containing conjugated microporous polymer, which is marked as polymer-2, and the BET specific surface area of the polymer-2 is 325m 2/g。
Preparation of Polymer-2 obtained in this example13The results of the C-NMR measurement are shown in FIG. 4, and it is found that the peak at 170.1ppm is C in the chemical environment of the triazine ring, which proves the existence of the triazine ring; the peak at 137.1ppm chemical shift is the peak for C at the para position in the pyridine ring, demonstrating the reaction to form a pyridyl group; the peak at 127.7ppm chemical shift is the peak of C in the chemical environment of the benzene ring, demonstrating the presence of a conjugated structure. This result confirms the successful synthesis of polymer-2.
CO at 273K for Polymer-2 obtained in this example2The adsorption-desorption curve is shown in FIG. 5, and it can be seen that the adsorption curve rapidly increases in the low pressure region, indicating that the microporous structure of the polymer is responsible for CO2Has certain effect on the adsorption of the active ingredients. CO of Polymer-2 at 273K, 1Bar2The adsorption amount reaches 7.09 wt%. CO at this temperature2The desorption curve and the adsorption curve are completely coincided, which shows that the obtained polymer-2 has CO content2The adsorption of (b) is reversible.
Polymer 2 obtained in this example has CO at 273K2And N2The initial adsorption slope curve of (A) is shown in FIG. 6, and the fitted CO is calculated2And N2The ratio of the initial adsorption curve slopes indicates the CO2/N2The adsorption selectivity is 32.4, and the adsorption selectivity is good.
Example 3
1,3, 5-triacetylbenzene (408.5mg, 2mmol) and 1,3, 5-tris (p-formylphenyl) benzene (390.4mg, 1mmol) were mixed and placed in a 200ml round-bottomed flask, ammonium acetate (2.31g, 30mmol) was added, then 100ml of pyridine was added to dissolve all the above mixed powder, and finally the mixture was stirred at 115 ℃ oil bath temperature for 24 hours. After the reaction is finished, performing suction filtration, respectively stirring and washing with deionized water, methanol and chloroform at 60 ℃ for 24 hours, performing suction filtration, and then placing at 60 DEG CDrying in a vacuum oven for 24h to obtain the pyridyl-containing conjugated microporous polymer, which is marked as polymer-3 and has the BET specific surface area of 511m2/g。
The XPS nitrogen spectrum of Polymer-3 from this example is shown in FIG. 7, where no nitrogen is present in either monomer, and the XPS spectrum has a peak at 398.5, which is consulted as the peak for pyridine N. It was thus confirmed that the polymer contained a pyridine ring structure. The successful synthesis of polymer-3 was confirmed.
Polymer 3 obtained in this example has an N value at 77.4K2As shown in FIG. 8, it can be seen that the adsorption isotherm is in the low relative pressure region (P/P)0<0.001), the curve rises rapidly, indicating that gas adsorption is faster due to the presence of micropores, indicating that a certain microporous structure exists in polymer-3; in the middle and high relative pressure region (P/P) 00.1 to 1.0), the curve rises at a relatively slow rate, indicating the presence of macropores in polymer-3. While the final desorption and adsorption curves were not completely closed, probably due to small amounts of N2Remained in the pores of the polymer-3 and could not be completely desorbed.
CO at 298K for Polymer-3 obtained in this example2The adsorption-desorption curve is shown in FIG. 9, and it can be seen that the adsorption curve rapidly increases in the low pressure region, indicating that the microporous structure of the polymer is responsible for CO2Has certain effect on the adsorption of the active ingredients. CO of Polymer-3 at 298K, 1Bar2The adsorption amount reaches 5.74 wt%. CO at this temperature2The desorption curve and the adsorption curve are completely coincided, which shows that the obtained polymer-3 has CO content2The adsorption of (b) is reversible.
Polymer-3 obtained in this example had CO at 298K2And N2The initial adsorption slope curve of (A) is shown in FIG. 10, and the fitted CO is calculated2And N2The ratio of the initial adsorption curve slopes indicates the CO2/N2The adsorption selectivity is 29.1, and the adsorption selectivity is good.
Example 4
Mixing 1,3, 5-triacetylbenzene (408.5mg, 2mmol) and tris (4-formylphenyl) amine (329.4mg, 1mmol), and standingAmmonium acetate (2.31g, 30mmol) was added to a 200ml round bottom flask, then 100ml pyridine was added to dissolve the above mixed powder completely, and finally the mixture was stirred at 115 ℃ oil bath temperature for 24 h. After the reaction is finished, performing suction filtration, respectively stirring and washing the mixture for 24 hours at the temperature of 60 ℃ by using deionized water, methanol and chloroform, performing suction filtration, and then drying the mixture for 24 hours in a vacuum oven at the temperature of 60 ℃ to obtain the pyridyl-containing conjugated microporous polymer, which is marked as polymer-4 and has the BET specific surface area of 523m 2/g。
Preparation of Polymer-4 obtained in this example13C-NMR measurement results As shown in FIG. 11, the peak at 137.1ppm chemical shift is the peak of C at the para position in the pyridine ring, confirming that the reaction forms a pyridyl group; the peak at 127.7ppm chemical shift is the peak of C in the chemical environment of the benzene ring, demonstrating the presence of a conjugated structure. The peak at 146.4ppm chemical shift is the peak for C attached to a single N atom. This result confirmed the successful synthesis of polymer-4.
Polymer 4 obtained in this example has an N value of 77.4K2As shown in FIG. 12, it can be seen that the adsorption isotherm is in the low relative pressure region (P/P)0<0.001), the curve rises rapidly, indicating that gas adsorption is faster due to the presence of micropores, indicating that a certain microporous structure exists in polymer-4; in the middle and high relative pressure region (P/P)00.1 to 1.0), the curve rises at a relatively slow rate, indicating the presence of macropores in polymer-4. While the final desorption and adsorption curves were not completely closed, probably due to small amounts of N2Remained in the pores of polymer-4 and could not be completely desorbed.
CO at 298K for Polymer-4 obtained in this example2The adsorption-desorption curve is shown in FIG. 13, and it can be seen that the adsorption curve rapidly increases in the low pressure region, indicating that the microporous structure of the polymer is responsible for CO 2Has certain effect on the adsorption of the active ingredients. CO of Polymer-4 at 298K, 1Bar2The adsorption amount reaches 4.90 wt%. CO at this temperature2The desorption curve and the adsorption curve are completely coincided, which shows that the obtained polymer-4 has CO content2The adsorption of (b) is reversible.
Polymer-4 obtained in this exampleCO at 298K2And N2The initial adsorption slope curve of (A) is shown in FIG. 14, and the fitted CO is calculated2And N2The ratio of the initial adsorption curve slopes indicates the CO2/N2The adsorption selectivity is 40.6, and the adsorption selectivity is good.
Example 5
1,3, 5-triacetylbenzene (204.3mg, 1mmol), 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine (196.7mg, 0.5mmol) were mixed and placed in a 200ml round-bottomed flask, ammonium acetate (1.15g, 15mmol) was added, then 100ml of pyridine was added to dissolve the above mixed powder completely, and finally the mixture was stirred at 115 ℃ oil bath temperature for 24 hours. After the reaction is finished, performing suction filtration, stirring and washing the mixture for 24 hours in deionized water (60 ℃), DMSO (80 ℃), methanol (60 ℃) and chloroform (60 ℃), performing suction filtration, and then placing the mixture in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the pyridyl-containing conjugated microporous polymer, namely the polymer-5, wherein the BET specific surface area of the polymer-5 is 515m2/g。
The XPS nitrogen spectrum of the polymer-5 obtained in this example is shown in FIG. 15, and the XPS spectrum was examined for a peak at 398.5eV, which is the peak of pyridine N. It was thus confirmed that the polymer contained a pyridine ring structure. Meanwhile, the peak of the triazine ring exists at 398.8eV, and the triazine ring structure in the monomer is reserved. The successful synthesis of polymer-3 was confirmed.
Polymer 5 obtained in this example has an N value at 77.4K2As shown in FIG. 16, it can be seen that the adsorption isotherm is in the low relative pressure region (P/P)0<0.001), the curve rises rapidly, indicating that gas adsorption is faster due to the presence of micropores, indicating that a certain microporous structure exists in polymer-5; in the middle and high relative pressure region (P/P)00.1 to 1.0), the curve rises at a relatively slow rate, indicating the presence of macropores in polymer-5. While the final desorption and adsorption curves were not completely closed, probably due to small amounts of N2Remained in the pores of the polymer-5 and could not be completely desorbed.
CO at 298K for Polymer-5 obtained in this example2As shown in FIG. 17, it can be seen that the adsorption curve is fast in the low pressure regionThe rise indicates that the microporous structure of the polymer is towards CO2Has certain effect on the adsorption of the active ingredients. CO of Polymer-5 at 298K, 1Bar2The adsorption amount reaches 4.7 wt%. CO at this temperature2The desorption curve and the adsorption curve are completely coincided, which shows that the obtained polymer-5 has CO content2The adsorption of (b) is reversible.
Polymer 5 obtained in this example has CO at 298K2And N2The initial adsorption slope curve of (A) is shown in FIG. 18, and the fitted CO is calculated 2And N2The ratio of the initial adsorption curve slopes indicates the CO2/N2The adsorption selectivity is 47.0, and the adsorption selectivity is good.
Comparative example 1
1, 4-diacetophenone (162.2mg, 1.0mmol) and 2,2 '-bipyridine-5, 5' dicarbaldehyde (106.1mg, 0.5mmol) were mixed and placed in a 200ml round bottom flask, ammonium acetate (1.15g, 15mmol) was added, then 100ml of pyridine was added to dissolve all the above mixed powders, and finally the mixture was stirred at 115 ℃ oil bath temperature for 24 hours. And after the reaction is finished, performing suction filtration, stirring and washing the mixture respectively with deionized water (60 ℃), methanol (60 ℃) and chloroform (60 ℃) for 24 hours, performing suction filtration, and then placing the mixture in a vacuum oven at 60 ℃ for drying for 24 hours to obtain the pyridyl-containing conjugated microporous polymer, which is marked as polymer-6.
CO at 298K for Polymer-6 obtained in this comparative example2As shown in FIG. 19, the adsorption/desorption curves show that the adsorption curve rises in the low-pressure region, indicating that the microporous structure of the polymer is responsible for CO2Has certain effect on the adsorption of the active ingredients. CO of Polymer-6 at 298K, 1Bar2The adsorption amount was 0.6 wt%, and the adsorption amount was low. CO at this temperature2The desorption curve and the adsorption curve do not completely coincide, indicating that the resulting polymer-6 is CO2Is not fully reversible.
Polymer-6 obtained in this comparative example CO at 298K2And N2The initial adsorption slope curve of (A) is shown in FIG. 20, and the fitted CO is calculated2And N2The ratio of the initial adsorption curve slopes indicates the CO2/N2The adsorption selectivity is 4.7, and the adsorption selectivity is higher than that of other polymersThe reason is that the specific surface area of the polymer-6 is low, so that the polymer can react with CO2Less active sites are bound, resulting in CO2The adsorption selectivity is not good. In addition, compared with CN110218295A, it is probably because the higher amount of solvent has an effect on the formation of network structure of polymer-6.

Claims (9)

1. CO (carbon monoxide)2A selective polymer adsorbent is characterized in that aromatic aldehyde, aromatic ketone and ammonium acetate are subjected to aldehyde ketone condensation and conjugate addition in the presence of pyridine and cyclized with ammonia to form a pyridine ring.
2. The adsorbent of claim 1, wherein the aromatic aldehyde comprises 1,3, 5-tris (p-formylphenyl) benzene, 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine, or tris (4-formylphenyl) amine.
3. The adsorbent of claim 1, wherein the aromatic ketone comprises: 1, 4-diacetylbenzene or 1,3, 5-triacetylbenzene.
4. CO (carbon monoxide)2A method of making a selective polymeric adsorbent comprising:
Mixing aromatic aldehyde and aromatic ketone, adding ammonium acetate and pyridine, performing aldehyde ketone condensation and conjugate addition and cyclization reaction with ammonia, filtering, washing and drying to obtain the pyridine nitrogen-doped conjugated microporous polymer, namely CO2The selective polymer adsorbent comprises a selective polymer adsorbent, wherein the molar ratio of aldehyde groups of aromatic aldehyde to ketone groups of aromatic ketone is 1:2-2:1, the molar amount of ammonium acetate is 9-11 times of the total molar amount of the aromatic aldehyde and the aromatic ketone, and the ratio of the aromatic aldehyde to pyridine is 0.5mmol: 30-100 mL.
5. The method according to claim 4, wherein the aldehyde ketone condensation, conjugate addition and cyclization with ammonia are carried out at a temperature of 110-120 ℃ for 12-24 hours.
6. The method of claim 4, wherein the washing is: washing the mixture by deionized water and an organic solvent at 60-80 ℃ for 24 hours.
7. The method of claim 6, wherein the organic solvent comprises methanol and chloroform or DMSO, methanol and chloroform.
8. The method of claim 4, wherein the drying is: vacuum drying at 60-100 ℃ for 20-24 h.
9. Use of the adsorbent of claim 1 for carbon dioxide adsorption and separation.
CN202010651832.5A 2020-07-08 2020-07-08 High CO2Selective polymer adsorbent and preparation method thereof Pending CN111841509A (en)

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CN112480132A (en) * 2020-12-02 2021-03-12 哈尔滨理工大学 Preparation and application of covalent organic framework material based on Salen structure
CN114957685A (en) * 2022-05-11 2022-08-30 东南大学 Covalent organic framework material containing pyridyl and preparation method and application thereof

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CN110218295A (en) * 2019-05-31 2019-09-10 东华大学 A kind of pyridine/bipyridyl conjugation microporous polymer and its preparation method and application
CN111269417A (en) * 2019-11-26 2020-06-12 镇江猎盾特种材料有限公司 Pyridyl-containing conjugated microporous polymer and preparation method and application thereof

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CN110218295A (en) * 2019-05-31 2019-09-10 东华大学 A kind of pyridine/bipyridyl conjugation microporous polymer and its preparation method and application
CN111269417A (en) * 2019-11-26 2020-06-12 镇江猎盾特种材料有限公司 Pyridyl-containing conjugated microporous polymer and preparation method and application thereof

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CN112480132A (en) * 2020-12-02 2021-03-12 哈尔滨理工大学 Preparation and application of covalent organic framework material based on Salen structure
CN114957685A (en) * 2022-05-11 2022-08-30 东南大学 Covalent organic framework material containing pyridyl and preparation method and application thereof
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